Sterling Features of

lndia's No. I @rbfl@,@

Selling Book

revised in accordance with

netll syllabus and studded with

1. 13,000 Plus Questions judiciously framed & selected covering each and every aspect of the subject.
2. Authentic and Correct Ansvers make the book almost enor-free.
3. Explanation to each and wery an$ver make the book self-sufficient.
4. Recap consists of an exhaustive list ol results and formulae apart from rele/ant theoretical discussion.
5. Numerous Typical Examples for better understanding of the subject matter.
6. Do Ydu, Know highlighting very important points.
7. Competilion Window containing additional information which help in solving the problems in a short
time through short cuts and tricks.
8. sample Multiple choice Questions for perfect practice of solving the questions.
9. Review Questions crinsist of exclusive and self framed questions.
10. euestions from Competitions contain last 10 year questions of llT Screening, AIEEE and various
other engineering entrance examinations upto 2004.
11. 1000 Plus Brain Storming ouestions in every unit for knowledge test of the highest level.
12. Multiple Choice Questions with more than one correct alternatives.
13. Detailed theoreticaldiscussion on the topics Numerical Methods,
Computing, NumberTheory,
Group Theory, Partial Fractions, Hyperbolic Functions and Partial Differentiation.
14. 17 Assignments each given after every unit for testing the grasp on a particular unit.
15. 6 Cumulative Assignments each given after'every three units for continuous revision
of previous
units along with preparation of additional units,
16. 4 ModelTest Papers based on new style and expected questions for forthcoming
competitive
examinations.
 !.IIr--'-r
-iEE'
I
I
fiffitefti*,i
, SOME BASIC CONCEPTS IN CHEMISTRY
1. Some Basic Concepts in Chemistry
'I /1-1i69
omptition Focus l no-1192
Addllloial U3lul hlornreilon
in
1n9
Multlplo Cholct Oue6tlons 1184
Addltlonal Ouesllon6 1/9'l

OF MATIER
'w@iE
ol Matter 211-2J53

Conpcthlon Fcu 2J54--2178

Arftload tkdul Hoantaton 2154
C.B.S.E PM T (ilalns) Spocial 2t:;7
2t62
216/8
A.lfitqd Oq.do zn

..froMrc srRUcruRE ffiE[E

-'3. Atomic Structure 3/1-3/59
Coqr.tltlon focr.E 316G-3182
Aildilo.t l thaftrl lnfo.tttdon 3rm
C B S.E PM.T. (Marns)SPocial 3/6:'
l.T.
I ins) Special 3/67
Hill Cnoh. OlEdqra 3t72
Addl[oard Oiraldoir 3ao

OT EIIiIENTS AND PENloOrcrIY N PNOPEMES *B@

Elernents and Periodicity ln Propertles 411-4151
4152-4162
Addluqd Lr-tul ln onrI oo &
Sec,nr iSlt
rnr Js
(lo
 4

-FIRST IAW OF THERMODYNAMICS AND

CHEMICAT ENERGETICS
5. First Law of Thermodynamics and Chemical Energetics
Conpctition Focus
Addttlonal t lrsrul lniornraum 959
C.B.S.E. P.M.T. (Mains) Speciat 5/61
l.l.T. (Mains) Special t65
Uultlpb Clrclce Oueadons t69
Addtlonal Qucdors 5n6

CHEMICAT BONDING AND STRUCTURE

6. Chemical Bonding and Molecular'UOTECUIAR
Structure 6/1{/66
Conpctiti,on Focus 6/67--S/86
Arldldonal U.6ftd lnionn0on 6/57
C.B.S.E. P.M.T (Mains) Speciat 6tm
l.l.T. (Mains) Speciat 6171
ltdupl Cholco Ou..don 6ns
Addton l asdons 6/&t

EGIUITIBRIUM--.I
(Equilibrium Processes ond Phose Equilibrio)
7. Equilibriurn{ (Equilibrium Processes and phase Equitibria)
Conpctition Focus
Addtlon l U3.rul lnlbnnaton 7142
C.B.S.E. P.M.T. (Mains) Speciat 7t4
Ll.T. (Mains) Special 714
iluldple Cholce Qllortlms 7t56
Addltloml Oueldon 7til

EQUItIBR.IUfrI--II
(lonic Equilibrium in Solutions)
8. Equilibriunr{l (tonic Equilibrium in Sotutions)
Conpctition Focus
A,rldltonal Us.rul lnlbiluUon 8/60
C.B.S.E. P.M.T. (Mains) Speciat 862
l.l.T. (Mains) Speciat 8158
lluttplc Cholce Omctlons 8y80
AdltlorEl Ouertlom 8/90
 -"..-

REACTIONS
9. Redox Reactions 911-9151

Conpetition Focus 9152-9170

Addltloml Uce{ul lnlomatlon 9/52
C.B.S.E. P.M.T. (Mains) Special 9/55
l.l.T. (Mains) Special 9157
Multaph Cholce Ouestlons 9/61
Addhlonal Ouestions 9/68

PRINCIPLES AND PROCESSES OF

EXTRACTION OF EIE}IENTS
10. Principles and Processes of Extraction of Elements 1011-10125

Conpetition Focus 10126-10130

Addlilonal Uselul ln omatlon lo:m
C.B.S.E. P.M T. (Mains) Special IVZI
muhiple Cholce Ouestlons 10lZl
Addhlonal Glcstions 1U29

FI\TDROGEN
11. Hydrogen

Compctition Focus
Addhlonal Usstul lniornatlon 11145
C.B.S.E. P.M.T. (Mains) SPecial 11147
l.l.T. (Mains) Special 't114nB
irultlPle Cholce Ouestlons 11/50
Addltloflal Ouestlons 1 1/5it

.S.BLOCK
E1EMENTS
12. s-Block Elements 1211-12151

Conpctition Focus 1252-12162

Addltlonal U3etuI lniornation 12/52
C.B.S.E. PM.T. (Mains) SPecial 12lg
I LT. (Mains) SPecial 121il
llultlPle Cholce Ouestions 12/55
Addltlonel ouestlons 12/59
E

SOME p-BtOCK ETEMEMS

13. Some pBlock Etements 13/1-13i59
Corqcetition Focus 13160-13t72
Addhional Useful lnionnatlon 1960
C.B.S.E. PM.T. (Mains) Speciat 13162
l.l.T. (Mains) Speciat 13/63
muEde Choice Ouestlons 1 3/65
Addhional Questions 13170

ORGANIC CHEMISTRY-SOME BASIC PRINCIPTES

14. Organic Chemistry-Some Basic principles
Corpetition Focus
Addhlonal Uselul lnfornatlon 14181
C.B.S.E. P.M.T. (Mains) Speciat fila2
Multiple Choice Ouestlons 14l'y.
Additlonal Ouesflons 14t91

HYDROCARBONS
15. Hydrocarbons
15fi- 15/106
Competition focus 151107-15t134
Addft ional Usefu I lnlbrrEuon 1yl07
C.B.S.E. p,M.T. (Mains) Speciat 151112
l.l.T. (Mains) Speciat 1y118
Muhlple Cholce Ouesdong 15t120
Addiilonal Ouesdons 1si/l31

PURIFICATION AND CHARACTERSATION OF

CARBON COMPOUNDS
16. Purification and Characterisation of Carbon Compounds

Corpetition Focus
Addftloml Useful lniomaUon 1d49
C.B.S E. PM.T. (Mains) Speciar 16i/50
l.l.T. (Mains) Speciat 16152
ilultiple Choice eue.fions 16i/56
Addltlonal Quesfions 16/61
 a

ORGANIC COiAPOUNDS wlTH FUNCTIONAL GROUPS

CONTAINING HATOGENS (Holoqlkones ond llolootenes)
17. Organic Compounds with Functional Groups Containing Halogens 1711-17157

Corpctition Focus 17158_.17n8

Hdthnd t ..lul lrdbtndon 17158
C.B.S.E. P.M.T. (Mains) Special 17159
l.l.T. (Mains) Special 17165
lftlttlCaClrclc.Ou.don 1716a
Addthml Ot!.don 17n5

E NVI RONIVIE NTAI C H EA/II STRY

18. Environmental Chemistry

Conpetition Focus
Addtlon l t lclul lnlonftttlon 1A^l4
C.B.S.E. P.M -T. (Marns) Special 1A,:ls
lruluple Ctlolce Ouestlom 18/It5
Addtlonal Quectlons ,y,

APPENDICES
Appendix 1. - lmportant Name Reactions (ln Alphabetical order)
Appendix 2. - Distinction Between Pairs of Compounds
Appendix 3. - SomeTypica! Conversions

t@ TABI"ES
LogTables (i)- (iv)
 C
Conc rrti=tr3r

Importance ol studying chemistry,

Physical quantities and rheir sl units, dirEnsional analysis, precision and signilicant tigures.
Classification ol matter.
Laws of chemical combination.
Dalton's Atomic Theory.
Mole concepl, alomic, molecular and rnolar rnasses.
Percentage composilion and molecular lormula.
Sloichiometry ot chemical reaclions,

SECTION-I ractions). All measurements involving mass,

(;ENERAL INFORMATION AND volume, lengtb, density etc. require precision or
IMPOR'TANCE OT' STUDYING CHEN{ISTRY accuracy. Further, as chemistry deals with all sub-
starces present in our body and all those present
'1.1. lntroduction around us, it has a great importance and broad
Clumi ry k applications.
ddined as thttt brmch o! sciance
which dealr with thc stttdy otcornposititn, stnnture The aim of this unit is to studv all these ba-sic
and properties of mottzr anil the chanp which lhe coocepts, some of rhem briefly'whcreas some
mztler urulergoes under diferent conditio$ qnd others ir detait-
the laws which govern these changx, '1.2. lEportance ot Studyin g C hemistry,:r:i::r:i::i:::i,:i:::rr:i:

What does the term 'matter' mean in the

above dcfinition ? Though it will be discussed in
detail later in this unit, at the momcot it is sufficient
to mention that all substances (sohd, liquid or
gascous) which are present in our body or present
around us which may be visible or some of which Some of the important applications of
may not be visible (e.g air) are made of matter. _
chemistry are given below :
Furthcr, two blsic units ofwhich all substances are
. (1) Supply of food. With increase in popula-
made up are atoms and molecules. They combine
tion, the need for the overall amount of fooi has
with cach othcr according to certain laws, called
increased manifold. Moreover with increase in the
Laws ofchemi ich standards of life, there has been increase in the
theyundergo be quality and variety of food. Chemistry has helped
physical or c cal to achieve these goals as follows :

ur
112
(i) It has provided chemicol lertilizers sach as
urea, calcium superphosphate, sodium nitrate, am-
monium sulphate etc. which have increased the
feld of crops and fruits.
(ii) It has helped to protect the crops from
insccts and harmtul bacteria by the use o[ certain
elfcctive tsecticides, fungicides ar,d pesticides-
(iii) The use of presenatives has helped to
presewe food products like jam, butter, squashes
etc. for longer periods.
(rv) lt ha.s given me thods to lest the presence of
qdulterdlts thereby eo"suring the supply of pure
food-stuff.
(2) Contribution to better health and sanita'
tion, Chemistry has contributed towards better
health and sadtation in a number of ways as fol-
lows : (i) Sythetic fbres (cloth). ID' addition to the
past.
Similarly, life saving drugs llke cis platin al'd
,arol have been found to be very effective for ca.ncer
therapy and AZT (Aziodothym.idine) is used for
AIDSvictims. These compounds are obtained from
animals and plants or by synthetic methods.
million parts (ppm) is used for steril ization of water
to make it fit for drinking purposes.
has made surgi
(iii) Discovery ofanasJrrrerics
cal operations more and more successful.
(iv) The use of insecticides such as DDT and
(lammexane has reduced the bdzards of diseases
caused by rats, mosquitoes and flies.
and primaquin.
Pradeep's
(vi) Synthetic vitamins and ronics have con-
tributed significantly towards bettor health.
In fact, the use of more effective medicines,
vitamins etc. and better sanitary conditions have
helped to incrcq.se the average life span.
(3) Saving the enviroDment. Refrigerants like
chlorofluorocanbons (CFCs) which destroy the
ozone layer have been replaced by environment-
friendly chemicals. However, Green house gases
like CtIa, CO2 etc. are still posing a challengc to the
chemists.
(4) Increase in comforts, pleasurts and
luxuries. Chemistry has placed a large number of
utility goods at our disposal which have added to
our comforts, pleasures and lururies. A few ofthese
are given below :
natural fibres like cotton, wool, silk etc., chemistry
has helped in the production of synthetic fibres
such as terylene, nylon, rayon etc. which are more
comfortable, durable and attractive. They are easy
to wash, dry quickly and do not need ironing. Fhr-
ther, chemistry has provided a large number of
synthetic dyes which impart bright aad fast colour
to the clothes. It has also provided chemicals to
make these clothes fue-proof and water-proof, if
necessary.
(ii) Build.ing mateials. By supplying steel and
cement, chemistry has helped in the construction of
safer homes and multi-storeyed buildings and dams
and bridges which can last for centuries.
(iii) Supply of metals. Metals like gold, silver,
copper, iron, aluninium, zinc and a large number
of their alloys are used for making ornaments, uten-
sils, coins and many industrial and agricultural im-
plements.
(iv) Atictes of domestic use. Chemistry ha^s
made our homes more comfortable by supplying a
can make our homes cooler in sumner.
(v) Enteftainment. Cinema, one of the com-
mon sources of entertainment and also video-
cameras as well as simple camerasmakeuse of films
which are made of celluloid (a chemical com-
 SOME BASIC CONCEPTS IN CHEMISTRY
113

pound) and coated with suitable chemicals. usefulbut disposal ofnuclear waste poses a serious
Similarly, fire-works which amuse us on festivals problem to
humanity. S
and marriages are chemical products. Phonograph records have added to our
records used for listening music are made of music but they are made
polyvinyl chloride, a chemical compound. produced from vinyl chloride which can cause liver
(5) Thansport and commuuication. Almost cancer in industrial workers. Antibiotics have
all means of tran^sport inclurling automobiles eliminated infectious diseases but their overuse is
(scooter, cars, trucks, buses etc.) aeroplanes, very harmfu l. Likewise, insecticides h ave increased
helicopters, railways use either petrol or diesel
(petroleum products) or coal which are all chemi-
p
cal
Cuality
fuels of ap-
polo Mars. sugar etc. which are proving a curse to the society.
Knowledge of chemistry has also helped in the
Thus though chemistry can be regarded as
development of telephone and telegraph as impor- greatest benefacto
tant means of communication.
be a blessing or a c
(6) Nuclear or Atomic energF. In view of the the uses to whichit
decreasing coal and petroleum resources, the is maintained between benefits and problems
energy crisis. caused by progress in chemistry.
by providing an
s 1..("1't()N_il
nuclear energy.
tion of the com- N{I]AS UREI\{ENTS IN CHI'I\TIS TRY
pound, uranium hexafluoride, made possible the \
1.3. Physical Quantities
enrichment of U-235 which was usLd first for i: :i:::ii:::::::::::::i.:i:::i::::::i:::::::::::::j:j:::::::.:::::::::

making atomic bomb and later in the nuclear reac-
ctricity. Nuclear energy can
diggr"C tunnels, blasting
g as well.
q)
Applications in industry. Chemistry has
played an important and useful role towards the
clevelopment and growth of a number of industries
Similarly, it has helped in the spthesis of new
materials having specific magnetic, electrical and
optical properties which are used in the production
of
. superconducting ceramics, ionducting
polymers, optical fibres etc.
(8) Applications in war. Chemistry has also
increased the striking power of man in war times. It
In everyday life, we come across a number of
ables in kilograms,
c. However during
the measurements
of mass, volumes and lengths, we come across the
measurement of a number of other quantities such
as temperature, pressure, concentration, force,
work, density etc.
All such quantitics whiah we come across during
our scientifrc studies are callcd physical quan-
tilies.
Evidently, the measurement of any physical
quantily consists of two parts :
(i) the number, ernd
(ii) the unit.
For example, if an object weighs 4.5 kg, it
involves rwo parts : (i) a.-5 i.e. the number and
(ii) kgi.e. the unit.
Thus the main aims of this section are :

(i) To see how accurately or precisely the

nu_mber has been expressed i.e. co,ncept of sig_
nificant figtres.
The progress in chemlstry can also cause (ii) To study the units of measurem erfi i.e. the
many problems. For example, nuclear energy is S.I. units.
114
Pradeep's:1,/y;ei4t;:"7,o:;11,ei,,,tChemis-tri.ft^tTn

(rrr) Ii, derive the units of any physical quan-
tity and to check the accuracy of any scientific
equation by seeing that the dimensions of both sides
of tlre equation are same i.e. concept of dilnensional
analysis.
,,A,
lo
Since early times, different types of units of
measurements have been very popular in different
parts of the world e.8'. sers, pounds etc. for mass ;
miles, furlongs, yards etc. for distances. However
these units are quite cumbersome because of no
uniformity in the conversion factors involved e,g.
1 mile : 1760 yards, 1 yard : 3 feet, 1- foot :
12 inches.
ln view of the diffrculties mentioned above,
French Academy of Science, in L791, introduced a
new system of measurements called'metric system'
in which the different units of a physical quantity
are related to each other as multiples of powers of
7O, e.g. L km : 1(P m, 1 cm : 10-2 m etc. This
system was tbund to be so convenient that scientists
all over the world immediately adopted this system
for reporting scientific data and gradually most of
the countries have also switched over to this system
for measurements of everyday use. India started
following metric system since 1,957.
The metric system, as put forward earlier, was
further imporved by the General Conference of
Weights and Measures (Conference Generale des
,:.,
Poids et Mesures, CGPM) which met in October
,,,.,, 1960 in France. The improved system of units has
been accepted internationally and is called Interna-
tional System of Units or in short SI Units (for
Systeme Internationale iu FrencQ.
With greater accuracy in measurement, the
'unit' definitions and hence the system of units is
improved from time to time. To maintain uniformity
all over the world, each nation has National Metrol-
ogy Institute (I.[MI). ln India, this responsibiliry has
been assigned to National Physical Laboratory
(NPL), NewDelhi.
Seven Basic Units. The seven basic physical
quantities on which the International System of
Units is based, their syrrbols, the names of their
units (called the base units) and the symbols of
these units are given in Thble 1.1.

IABLE 1.1. Seven basic physical quantities and their SI units

PT{YSICAL QUANTITY SYMIIOL SI UNIT S}MBOL

I-ength I metre nl
Mass nl kilogram kg
Time t second S

Electric current I amPere A

'fhern:odynanric tenrPerature T kelvin K
Amnunt of the substance n mole mol
Luminous intensity lL) candela cd

The SI unit of mass viz. kilogram has been detincd as the ntass of platinunriidium (Pt-Ir) cylinder
that is storecl in an uirtigltt jar at htteruational Bw'eatt of Weights ancl Measures in France.

Tlre Sl unit of length viz metre was originally defined as the lengtlt between two marks on d Pt-Ir bar
kept ut a temperatlo'e oJ' 0'C (273 K). However, now it has been redefined by CGPM as the length of the
path trove llecl b, tight irt vuarunt duing a tinrc intcnal r[ 11299,792,458 oJ' a second.

Though the S.I. unit of temperature, 'kelvin', yet it is very common to express temperatures in degree
celsius ('C). The two are related to each other as
oc + 273'15'
Tempe.iiuro in degrcc kelvin (K) = Temperature iu
Howcver, it may be remembered that size of l"K : size of 1"C.
SOME BASIC CONCEPTS IN CHEMISTRY 1/s

Similarly, though the S.I. unit of length is metre, yet it is very common to express length in Angstrom
(A) or nanometres (nm) or picometres (pm). These are relaterl to S.I. unit as follows :
1 A = 10-10 rn, lnm : l1-s m, 1pm : 1O-12 nt

Rtrther, it is important to understand that the term 'weight' should not be used ln place of .massr.
Thcv have differcnt meaning. Mass is the quantity of matter contained in the sample and for the given
samplc, it is constant and does not depend upon the place. Weight is the force with which the body is
attracted towards the earth (W : t"S).Thus, it depends upon the acceleration due to gravitv g'which
varies from place to place.
Derived units. The units of all other physical quantities arc clerivcd out of thosc of the basic physical
quantities. The units thus obtained are callcd the derived units. Some commonlv used physical quantities
and their derived units are given in Thble 1.2.

TABLII 1.2. some conrmonly used physical quantities and their derived unit

PIrySICAL DE[INTTION UNIT SYMBOL

QUANTITY

Arca Length square Square metre m2

Vllunte Length cube Cubic metre m3
Density Mass/unit vol. Kilogram per kgm -3
cubic nretre
Vclocity Distance/unit time Metre per second ms_1 '
Acceleration Speed change/unit time Metre per second ms'
_t

per second
Rrrcc Mass x a:celeration Newton N = kB rn s-2+
Pressure Force/unit area Pascal Pa=Nm-2
- _t
(Newton per sq. metre) =kgm -l
Work, energy Force x Distance joule J=N nr:kg 1112 a-2**
Frequenr-y Clcles/sec. Hertz Hz = s-l
Eloctric charge Current x time Coulomb C=As
Potcntial clifference Volt V=kgm2s-3A-l
=JA-l s-l = JC-l
Electric resistance Pot-diff./current ohm C2: V A-l
Elcctric cclnductance Reciprocal of resistance ohm-t O_1 : AV-l

that may be the base

as 1
1d, 1d, as l-0-3,
These are in s. These
mon use, alongrvith their prefixes are given in Thble

*Newtonisdefinedastheforcethatgivesamassof lkganaccelerationof
lms-2sothat f = ma = (lkg)(1 ms-2)
=.lkgms-2=1N.
*+Jouleistheworkdonewhenadisplaccmentoflmetretakespla-cebyaforceoflnewtonsothatw=fxd=(1
N)(1 nr)
= (lkgms-2;1tnr; = I kgm2s-2 = lJ. ThustJ:1Nm= 1L*'-2.-i.
116 . ,t.t ).t; ! Neu, Course ChemistrrllffiID

lltl.l Some commonlv used prefixes rrith the hase units

PREI-IX SYMROI- MULTIPI,YING ExAMPLE

FACTOR

dcci d 10- I
l decimetre(dm) = 10-l m = 0 1 m
cenll c 702 centimetre (cm) = l0-2 tt't = 0 01 t'tl
mrlli n] 10-l 1 millimetre (nrD) = 10-3 m
t'lllcro 10-6 1 n]icrometre (rrn) = 10-6 D]
nat'to n l0 e
I (nm) = 10-9 m
DaDometre
12
prco p 10- 1 picometre (pm) = 10-12 n'l

[emto f 10- l5 1 femtometre (ftn) = t0-15 m

atto a 10- 1E
I atto metre (am) = l0-lEn
zepto z l0-2t I zepto metre (zm) = 10-2lm
y()cto v l0-24 I yocto metre (ym) = t0-24m
dcka da 101 1dekametre (dam) = l0l m = 10 m

kilo k 1d 1 kilometer (km) = 103 n = 1000 m

mcga M 106 1 nregametre (Mm) = 106 nl

glga G 10e 1 gigametre (Gm)= 10e m
tera T 1d2 1 terametre (Tm)
= 1012 n'l
Pcra P 101s I petametre (Pm) = 10ls m
cxa E 1018 I exametre (Em) = 1ol8 m
zella Z 1021 1 zetta Detre (Zm) = 1021m

yotta Y 1024 1 yotta metre (Ym) = 1024D't

As volume is very often expressed in litres, it 2. Symbols o{ the units do not have a plural
is important to note that the equivalence inSI units ending lile 's'. For example we have 10 cm and not
10 cms.
:
I litre (1L) 1dm3 3. Words and symbols should notbe mixed e.g.
we should write either joules per mole ol J mol-l
and I millilitre (l ml) : I cm3*
) and not joules mol-1.
4. Prefixes are rrsed with the basic units e.g
Som lmportant Points to kilometer means 1000 m(becau-se meteris the ba-sic
Remember About S.I. Units unit).
l. The unit named after a scientist is started Erception. Though kilogram is the basic unit
with a small letter and.ot with a capital lctter e.g. of mass, yet prehxes are used with gram because in
unit ol force is written as ncwton and not as New- kilogram, kilo is already a prefix.
ton. 5. a power is
Likewise unit of heat or work is written as a power eans (ccn-
timeter)
iortle and not as Joule.

*From 1901 to 19f)4, a litrcnl"as defrncd as the lolumc of 1 k8 ofwater at 4"C. During this pcriod, a millilitre was very slightly
largerthana cubic clntimetre.Ill 1!b4, the litl! \r"a6 rEd.fincd as era.tlyequalinvolumc io 1m0 clbic centimetrs, theEby removing
the confusion.
 SOI\,IE BASIC CONCEPTS IN CHEMISTRY 1n
1.5. Precision and Signilicant Figures ii::+ititi:ijti:iitiiU;iiri: accurate than pacing off a length. One method to
1.5.1. Dilference betwn Prccision and Ac-
curacy.
whole
banana
r.c. l.hey consist ofara ct numbers. Similarly, defined tlte conect value, tlrc measurenenl is said, to be
accurate (the individual meq$urements may not be
close to each othe).
If the values of different meosurcments qre close
to each other ond hence close to their ayerage value,
the measurement is said to be precise- (The average
(i) the accuracy ofthe measuring device used, value of different measurements may not be close
and (ii) the skill of its operator to the correct va.lue). Tte precislon depends upon
the measuring device as well as the skill of the
asure the lengih
operator.
it off. If we pace
count each time For example, suppose the actual length of the
or to hav left over. Thus the room is 10 . 5 rz . Four different person^s report the
result of xactly correct. Ac- result of their five mea.surements as follows* :
curacyis way the measure-
meot is measure is more
Measurement (m) 1, 2 3 4 5 Average (z)
Person A 10.3 10.4 10.5 10.6 10.7 10.5
Person B 10.0 10. 1 10.2 10.3 10 4 70.2
Pcrson C 10. I 10.3 10'5 to.7 10.9 10.5
Person D 10.0 10.7 10.9 11.1 11.3 10.8
Mea^surement by person A is bo$ accurate
and precise.
Measurement by person B has poor accuracy Average
.but good preq$oD. value
Conecl
Measurement byperson C has poorprecision
.hut good
accuracy (ust by chance/luck)
. Measurement by person D has poor accuracy
and poor precision.
. These results may be represented diagram-
matically as shown in Fig. 1.1. (a) (b) (c) (d)
Both Poor Good Poor
accurate a@uracy accuIacy accuftlcy
and but good but poor and poor
prccrs precision paeclsrcn preclslon
0ust by luck)
FIGURE f ,1. Understanding accuracy and prechion.

mistake is made r
ermrs. They do not
affecl the accuracy

rln the Table gil'en abovE, ftve neasurcrDcn6 of any pclEon

have becfl shown as diffcrcnl In octual practicc somc of thesc
maybe samc also Furthcr, thc \alucs have bccn arranged in asccnding ordcr.
In fact, thc rtsrrt"
not have any order. "ioin"iii-i"*r;#;
118

this means that the actual mass of the object is
14 -5678 '+0 0001 g i.e. it lies between 14 567'7 ar,d
14 5679. Thus in the expressed masi, the first live
digits are certainbutthe last involvos anuncertainty
t
of 1. All measured quantities are reported in
such a way that only thc last digit is uncertain
(usually by t l).
Tlu aulnutnber o! tligi* in a nwnber induding
the la.lt digit whose vafue * uacerlein is ca eiltlu
nunher oJ sigrtifica frgures.
For example, in the above value i.e. 14'56789,
there are six signihcant figurcs. Similarly, the num-
ber 2 5 has two significant figures while the number
2 014 has four signiEcant figures.
1.5J. Rules for determining the number of
signllicant ligures. The following rules arc applied
in determining the number of significant figures in
any rcported quantity :
Rulc I. All non-zero digits u^s
hefueen the non-zero digils
576 cm has thrce signihcant figures
0 48 g has two signiltcant figurcs
5004 has bur significant figurcs
2 05 has three signilicant ltgurcs
Rule 2. Zaros to lhe lelt ol lhe rtr non-zero digit
in a number ue nol signilicunr. (Thq simply indi'
cute thc position of the decimal poinl) .
c.g. {) 05 m has only one signiltcant figurc
0 (X)45 kg has trvo signihcant figures.
For example, 10500 g may have three, four or
five significant figures. This ambiguity is removed
by expressing the value in an exponential form. For
example, the above mass may be written in three
different exponential forms as follows :
1 05 x 104 g, which has ,rrree significant irgures
or I 050x 104 g, which has/our signiEcant figures
or 1 .0500x 104 g, which hasfve signitrcant figures
In these cases, the significant figures of on.[y
the first factor are counted (remembering that all
zeros to the right of a decimal point are signifrcant).
Thus in such cases, the general notation is
Nx10'
where N : a number with a single non-zero digit
to the left of the decimal point
ard :
n an irrteger.
The above method of expressing a number is
called Scientilic or Exponential Notation.
well us 1.5.4. Rules for determinlng th numbr of
signilicant ligures in answers involving calcula-
tions. To get the final result of any experiment,
usually calculations are required which involve ad-
dition, subtraction, multipiication ind division of
different numbers. These numbers may have dif-
ferent accuracies i.e. may contain different number
of significant figures or decimal places. The final
result involving these numbers, therefore, cannot
be more accurate or precise than the least precise
number involved in a particular calculation. The
following rules are applied in determining the num-
ber of significant hgures in the answer of any par-
ticular calculation :

Rule 3. If a numher endr ln *ros Rule l. The resub oJ un afulilinn or suhlmction

are to thz righl ol thc .leimal WinL shoukl be reported lo the sarne numbet oJ decimal
ure si*t ilicanl. pl/lc{lt as th a of the lerm wilh krl namber of
decimal plu* The number of signifwanl figuru
e.& -5 0 m ha.s two significant frgures
2 50 cm has three significant figures
2. 500 g has four signifrcant hgures
2.3
0 02ff kg has three significant figures.
6.24
Rufu 4. Actual sum : 13.063

may or mu! not he significunt.

Reported sum = 13 1*

one alccimalplacc. The digit at the sccond decimal place is 6*,hich is greatel than 5. Hence the di8it at the first plaoc lras
-fhis method is callcd rrutldin' ofi Thc gcneral
been incrcasad by 1. Procedlrre for munding off is as lollows :
(i) If the digrrjust next ro the last digit to be retarned is less thJn 5. the Iast digit rs taken as such and all other diSits on its
right are dropped.
(ii) If rhc di8il js greater than 5, the last digit to be .etained is incrcased by I and all other di8its or its right are droPPed.
(iii) lf the digil rs eqral to 5, the last signilicant figure is teft unchangcd if it is e!,en and is increased by I ifit is odd
ExAlul'LFIS:/ 2.11 =I 21. 1 23(t =1 24, 1 235 - 1 21' I 225=122'
SO[,4E BASIC CONCEPTS IN CHEMISTHY 119

First number has three decimalplaces, second Thr: first number has four significant figurcs
has one and third has two. Hence a-nswer should be while the second has two. Thc actual product has
reported onlyuptoonedecimalplace. Notethatthe been rounded off to give a reported proriuct of l2
significant figures in the three numbers are 4,2 and i.e. containing rrvo signilicant figurcs only. This is
3 respectiYely. becausc thc lcast precise tcrm in the calculatirrn
.621 (viz. 2 8) has only two significant figurcs.
Exumple 2. 7

6.243
Exunryle 2. 0 4(, +- 15 734 gives
Actual quotient : 0.029236
tom
Actual sum : 14.884
Reported quotient should bc 0 02!) contain-
ing only two significant figurcs bccausc thc lcast
Reported sum = L4.884 precise term in calculations (r'iz. 0 216) has two
Each number has tbree decimalplaces. So the significant figurcs only.
answer is also reported upto three decimal places. It may be noted that both the above rules, in
Further note that the significaot figures in each of fact, may be interpreted as follorvs :
the three numbers is 4 but result has five significant
tigures.
.
r'rTht reported answer should not be more precise
lhqn thc least precise lcrm used in lhc ctleulu-
Exantple 3. 154.2 lion."
6.1
This generalization helps to check the
23 reported ansu'cr in cascs whcrc doubt ariscs. Frr
Actual sum : 183 3 example, in cxamplc 1, the precision ol l.hc lcasL
Reported sum : 183 precise lerm is0 lpart in 2 Ri.,. l prrrt in 2li'r
The last number is an exact number (invoh'ing
nearly 35 partrpo- lhousand (i.c. 3-i p.p.t). Thc
precisiun ofthe reporlc(l answer is I purt in l2 oi
no decimal place), Hence answer is also reported
nearly 83 p p-t. Thus the reported resul[ is not more
as an cxact number.
precise than the lcast precise term. If we takc the
Exunryla 4. 78.4215 rcportcd answer as 12 1, thc precision will bc 0.1
-6.01 in 12 1 or 1 part in 121 i.c. ncarly 8 p.p.t. which is
Actual DifL 12.4775 more precise than thc least precise term- Henca thc
rcported result should bc l2 and not 12. 1.
Reported Diff. : 12.47
As the sscond number has two decimalplaces Rulc i. If a qlculution involves a numher ol steps,
onlywhile the first has four, the answer is reported the resuU shouA mntuin the same flumber of sig-
upto the two dccimal places only. nilicanl Jigwet o-t lhot oJ lhe kost precise number
involved, other than,h.e exuct numben.
Exantple 5. 29.25
12.0234 Erample.
- 12-961 x 0.02435 :
Actual Diff. : 17 2: 6 0 7(192988
Rcported Diff. : 0.4 x 4
77 23
(Actuul result)
As lhc Iirst numbcr has two decimal places Lcaving thc cxact number 4. thc loast precise
only whilc the second has four, [hc ansrver is term has trvo significant figures. Hencc aftcr rouncl-
rcported onlv upto two decimal places. ing off, the reportcd rcsult willbe 0 77r.c. contain-
Rult 2. Tfu rcsuk of u multipliculion or division ing two significaot figl:res. Altctlluti t,c/y., thc abovc
shoal.d he repo ed lo lhe same number oJ sig- rulc is applied as follorvs:
nificant.figures us is possessed by the lcasl prec(se Fitfi tha number of signifrcantfrgures tlwt the u6lter
krm .,li(:d in Lhe calcuk tion. sbuAcontainisdctirlctl ( it. it shotdil beequlrl to thdl
Etcutnple 1. of the lan:s precire term, orhfi lhan the qact namber).
4.327 Beforu catrying oa the nwthefidlical operutions,
x 2.8 every rurmher is roundd off ln conbin om sipifimnt

Actual Product = 72-7156 figure nore lhan the unswq would lwve. Tfu unflccr
obuind is ihen rouruleil ofi to conrain thz required
Reported Product :12 number oJ significant tigures-
1110 lccp's Neu, Course Chemistrg$Il)
Thus in the above example, the answer should REMEMBER
have two significant figures. Hence everynumber is
Thc rules lhat h.ave been sto.led above apply only to
first rounded off to contain three sipificant figures.
non-inlegral measured quanlilies because only in
Thus
lhese cases the uncertainty in meu^surement hus
43.0 x O.0243
:0'7683088 signiftsance. These do not apply to exact numbers
0.3210 x4 where uncerlsinty hru no significance e.g. there are
exacl 12 egs in a dozen qf egs, lhere qre exact
After rounding off to two significant figures, 1000 g in I kg, lhere ure exact 3 .feet in I yurd and
reported answer should be 0 .77 .
so on.

F,R @:ts-,[ E f\41.,9'ON

1..\ \\i;'t i I Wrat is the difference be- (vi) Three because the reported sum will be
t'vveen 5.0 g and 5.00 g ? only upto one decimal place i.e. 18.9.
_S_glU!&r.Though they look to be equivalent (vii) Two because the number with least num-
bnt scientifically they are different. 5.0 g has two ber of significant figures involvcd in the calculation
significant figures and hence its precision is 0.1 (i.e. M) has two significant figures.
part irr 5 i.e. 20 p.p.t. -5.00 has three significant '\ Express the Jbllowing to fow'
figtrres and hence its precision is 0.01 parts in 5 i.e. significant ftgures :
2p.p.L. Hence -5'00 g is more precise measurement (i) 6.4s372 (ii) 48.382s0 (iii) 70000
than -5'0 g.
(iv) 2. 65986 x ]F Q) 0. 004687.
L \ \\ II 'l li l. How many significant figures are Solution. (i) 6'4s4 (r,) 48.38
tltere in each oJ' the following numbers ?
(rr,) 7.000 x 104 (iv) 2.660 x tG
(i) 6.00s
(ii) 6-022 x 1d3 (v) 0.00a687.
. A santple of nickel weighs
(iii) 8000
6'54259 and has a density of 8.8 glcm3. mat is the
(iv) 0'0025 volume? Report the answer to cotect decimal place.
(v) n
(vi) the sum lll.5 + 0.4235
(vii) the product 14 x 6.345.
Solution.Volume:
affi : {ffi
: 0'J4 cn3
!q-l-u_tlo1 Q) Fourbecause the zeros between
thc non- zero digits are significant figures. The result should have two significant figures
because the least precise term (8'8) has two sig-
(ii) Four because only the first term gives the
nificant figures.
significant figures and exponential term is not con-
sidered. t.,x{\il,t I i. S. Express the result of the follow-
(iii) Fou'. However, if expressed ir scientihc
ing calculation to the appropiqte number of sig-

notation as 8 x [03, it will have only one significant

3.24 x 0.08666
nificant figures
5.006 (N.C.E.R.T)
figure, as 8'0 x 1iP,8.00 x 1d or 8.000 x 1d, it
will have 2,3 or 4 signihcant figures. 3.24 x 0'08666
Solution. = 0'0560883
(iv) Two because the zeros on the left of the 5.006
lirsl- non-zero digit are not significant. (Actual result)
')) As 3 '24has least number of significant figures
(v) As n =; = 3'142857L...., hence it has viz3, the result should contain 3 significant fi[ures
infinite number of significant hgures. only. Hence the result will be reported as 0.0-561.
(after rounding off).
 SOME BASIC CONCEPTS IN CHEMISTRY 1111

?RO:BLEM9 F,.O,R.Ea ,,\,

1. How rlany significant figures are tirere in each of (ii) Planck's constant .62 x
(6 t o -34 Js;?
thc tbllowing nuntbcrs '.'

(i) {r .200 (r,) 0 .0s2 [,hrs. (i) 2 (ii\ 3l

3. Express the number 45(X[ in exponential notation
(iri) 7.-5 x 104 to shotil
(n,) 0 .00050 (i) two significant figures
(v) 67 .32 - 6.3 (ri) four significant figures.
(vi) 4 .2+7 .589
[,\rs. (i) 4.5 x 10. (ir) 4.500 x ld]
(vii) (s .so)2 (8.24)/ (3.6) Criticize tbe folloning statements :
(tiii)18.567/(8'1x 2) (i) A fmsil was studied 25 years ago and was found
! \ns. (i) 4 (ii) 2 (iii) Z (iv) 2 (v) 3 to be 5fiX)years old. Nw it must be 5025 years
(r,i) 3 (rr'i) 2 (viii) 2l old.
2. What is the number of significant figures in (ri) The population of a city is 605,0fi). A family of
five persons shifts to some other city. The popula-
(i) Avogattro's number (r.oxto23) and
tion of the city must noru be ffi,995.

H INT9 FoR r.tFFtcuLT ?'.or.LEMg

l. (i) Zrros to the right of the decimal
significant.
(ii) Znrc to the left of the first noo-zero digit are
not significant.
(iri) When expressed as 7'5 x ld, ony significant
figuras of 7 .-5 are to be considered.
(rv) Apply rules given in Hints (i) and (n) above.
(v) 67.32-4.3
= 61.02. The result is
reported to same number of decimal places as that
of the term with least number of decimal places (viz
6.3 with only one decimal place). Hence after
rounding off, reported result = 6i.0, (which has
there significant tigu res).
(vl a.2 + 7.589 = 11.789. As it is to be reported
to one decimal place (as in (v) above), after round-
point are ing off, reported result = 11.8 (having three sig-
nificant f,gures).
(r4r) As least precise term (viz 3.6) has two sig-
nificant figures, the reported result should have two
significant figures.
(u:a) Leaving exact number Z the least precise
term (8. 1) has turo significant figures.
2. See Hint to o. 1. (rrr).
to be
3. See Hint to Q. 1. (rr).
4. (r) 25fim 2.5 x 104. It has only two significant
=
tigures. Expressing the new value in terms of same
number of significant figtrres, the age of the fossil
after 25 years can be taken as same.

A:EliP T.@ YO,.U..R KIN:'@'W LED,@'],E

iiiiiiii, l. Quite often the uncertaiDty in measurement is
e.g. 250 + 7Vo etc.If the sarne instrument is use
[o be n]easured, greater is the percentage uncertai
nrent equal to + 1 mg, then ifweweigh lfi)gon it, t
is usecl to weigh 10 g the result reported will be 10 + o.\lvo,and if 1 g is weighed, the result
reported will be
10 + 0'7%,-Hence smaller the quantity to be measurecl, more precise should be t'he instrumeni.
iiiiiili 2. While reporting th_e result to correot significant figures in any calculation, the exact
number (e.g. 4 inexample
crn page 1/10) is left out as it does not affect the number of significant figures. This is because
ai qact number
i,s' conyidered lo have an infinite number of significant
figures.
,:,:,'r':,:.:,::::',,:.:.:::,,,:':,:,:':,:

I
1112 NeuJ Course Chemistrrl
I .6. Di mensional Analysis .::::::::::ii:::i::::iri,i::a:::!:iii;!:!:::::i:i:i
Note. Ifthe conversion factor were not cor-
rectly used, the answer would have absurd units e.g.
Any calculation involving the use of the
if we write
dimensions o[ the different physical quantities in-
volved is called dimensional analysis.
1751b= 175lb x2'295lb
It is used for any one of the following pur- 1kg
poses:
the answer will have the units tb2 kg- 1
.
(1) Tb convert a physical quantity given in one
type of units into some other units. It consists of llx.A,l\ll'l.li 2. How many inches arc tltere in
the tbllowing steps : 3'00km?Giventhar lknt: 1000m, 1m: 1'094
(i) Fint derctmine the 'unit conversion fac- yd, 1 yd : i6 in.
torlfactors'. Solution. The unit conversion factors will be
e.g,. for conversion of pounds (1b) into 1000 m 1km
:1ooo-
kilograms (kg) or vice versa, 1kg : 2'205Lb. l= 1km
2.205Lb
-r:-
1kg
or , - l'094Yd -
lm 1'094yd
Similarly, for conversion of inches into cm or
36in 1vd
- 1yd _
,' _
vice versa,
- 36in
tinch = 2'54cm
-l:.-.-_----or
2'54cm Here the conversion involves a number of
' f. inch steps. Hence the unit conversion factors are ap-
The quantities such as2'2051b per kg or 1 kg plied in such a way that the units of the preceding
per 2' 205 lb, 2 ' 54 cm per inch or one inch per 2 ' 54 factor cancel out. Thus
cnr etc. are called 'urtit conversion factor,s'.
3'00 km : 3'00kff +H
(ii) Multiply the given physical quantitywith the "
rutil c:ot*,ar.sion factors, retaining the units of the
ltlry.ricol quantity as well as that of tlrcunitconversion t l'094v*^ 36 in
factors in sLtch a way tltot all units cancel out leavirtg
-r^- l_yd
ltcltittd only tlrc requiredunirr. If the unit conversion = I .18 x 10s in.
lactor has not been used correctly, the answer will
come out to be in wrong units. Note that the answer has been reported to
contain three significant figures (because 1000 m
(iii) If the
conversion huolves a number of
and 36 in. are exact numbers).
stcp,s, each conversion lactor is used in such a way II)LAN I l' l,l'- 3. Expre s s the fo llowing in S. I. b as e
that tlrc units of the prececlingfactor cancel out.
units using power of 10 notation (example 2'54 rum
As an illustration, a few examples are given : 2'54 x I0-3 m)
bclow:
L\ \1. I t'l.l . : A man weig,hs 175 |b. Express
(a) 1'35 ntm (b) I day (c) 6'a5 mL (d) a8
Itis rt'cigltt itt kg. Given that I kg : 2' 205 lb. pg (e) 0'0426 in (N.C.E.R.T)

Sglltlltft' 1 kg : 2'205 tb (a) S.I. unit of length is 'rz'

1_2-zgsrb:_ls, 1m : 100 cm, 1- cm : 10 mm

1 kg 2'205 tb
.'. Unit conversion factors are
Hence t75lb: tls)b"#* 1m 100cm - 1cm 10mm
100cm- 1m -''10mm lcm -'
:79'41ig.
r crfi 1m
The units 'lb' cancel out from the numerator J) Pm *
.'. 1.35 mm : 1.1-
10 *.6 ' ,oor*
ancl clenonrinator and the answer is in the required
units i.c. kg. = 1'35 x 10-3m
SOME BASIC CONCEPTS IN CHEMISTRY 1/13

(b) S.L unit of time is'sec' (s) lotql mass of o ing in grants and kilogrotns which
ldaY= contsins 0'500 carat diamond snd 7.00 grant gold.
24 hours f)0 miri 60 s (N.C.E.R.T,)
r oay x ------'. ,lhour"
l ryin Solution. The unit conversion factors to be
usedGif6i_
=86400x104r
(c) S.I. unit of volume is 'n3' t_ lcarat _ 3'168grains
' grains I carut
3. lb8
(r.45 mL = fr.45 mL x I Tl . I gram l5'4 grains
IBL ' 15.4 grains I gram
1m x lm lm
" roo* roo.-' ,0,,a- o. soo carar = o.soo erft " a#Hf
= 6 45 x 10-6m3
I rlram
(r.l) S.l. unit of mass is 'kg'
'lo-6g, lkg " t5io"*.
4Eut!= ''
48 uP,
-" tts " ltM)el-
' = 0. 10 gram
.. Total mass of the ring
= 4.8 x t0-t kg
(c) S.I. unit of length is 'm' = 7.00 + 0.109 = 7. t0r

o.(,426 in = tl.o426ia x2 54cd, I

^ . -_5
= 7. ..
tO e x JE
10(n I
= lr.rx,zt le.
I rn l(X) cm
(3) To check th accuracy of any equation.
= 1.082 x 10-3 m
This is done by hnding the dimension"s ofboth sides
(2) ln solving problems, For this purpose, of the equation which must be same.
units are written alongwrth all the numbers. The I \ \\ I l'l,l! Using the method oI dimensiotrul
units are then cancelled in the same mamer as the analysis, veib the vqlidity oIthelollo, ingequotiotts:
numbers. II the problem has been correctly solved,
the answer will have correct units. (i)c = vl 1-
(u)S=ut+rut'
I \ i\ll'l.l.l. 1. Whot i:; the nruss (in granrs ) ol
ur alunriniurtt hktck wltose dimettsiont arc 2 0 in. Solution. (i) Dimensions of L.H.S.
x .1.0 in. x 4.0 in. arul whose de\ity is 2.7 t.e- c=ms'
glcni ? Given thot I in. = 2. 54 cm.
Dimension of R.H.S. i.e.
Solution. Here unit conversion factors are
1= cm
2'54 1 in v 7=s-l x m=ms-l
1in. 2.54 cm Hence from dimensions point of view, thc
Z'7p 1cm3
and -- - - z'le equation is correct.
l,
"rrf (ii) Dimensions of L.H.S.i.e..i = metres (rn)
Hence required mass (in g)

= 2.oin x 3.t)in x 4.oin x2'54cit

1in
Dimensions of R.H.S. i.e. ul + j aP
2.54 cm 2.54rzn
-----:-:- 2.7 s
,1
^ 1'ln' lE '- 1d =ms lxs+rrns-2x12
=11xldg.
li).{l\ l PLla 2. The mass of precious stones is =m+m=metres(rz)
expressed in tetms of 'cqrat'. Given that 1 carut : Hence from dimensioos point of view, the
3'16Sgrainsandlgram = 15 .
4 grains, calculate the equation is correct.
1114 lJradecp's Ncqt Course Chemistrg@

l. Corlvert 16 I km to miles using the following unils 0i) 1 fg (mass of humaD DNA molecule)
cquivalenLs: (NC.E.R.7:)
I kfl = lmn m, 1 ft = 12 inches
(i, 10-rt
I \'rs (i) 5 x 10rs kg kgl
I m = 100 cm. 1 mile = 1760 yd
5. Convert the following iDto metre
I inch = 2 54 cm, 1yd=3ft [\n' 10 0m'les] (i) 40 Em (thickoess of Milky way galaxy)
2, What rs the weight in pounds of a Sold bar 12 0 (ii) 1 4 Gm (diameter ofSuD)
iDches long,6 ff) inches wide and 3 00 inches
(iii) 41 Pm (distanc ofnearest star)
thick? The clensity of gold is 19 3 g cm-3. Given
(N.c.E.R.T.)
I inch = 2 54 cm, 1 lb = 453.6 g. J \ns. 151 lbl
3. fkpress the following in SI unlts : l,\ns (i)4xrOet1, (ii)1.4x109a(iii)41 x 10rs mt
(i) 5'6", thc average height ofaD Indian man. 6. Using the unit conversion factors, express
(ii) tto Driles per hour, the average speed ofa road- 0) l.54ornrr'lntopnrl(r'
wala bus.
(ii)2.66 g cDt-3 to ps pn-3. (N.C.E.R.T.)
(iii) 100 pounds, lhe average weiSht of an lndian
girl. (Tike 1 tu = 4549) I \ns. (i) 1.54xld p-7."-11i4 2.66110-u pg p^-'l
(iv) - I0'c, the lowcst temperature in SiDtla- 7. Vanadium metal is added to steel to intpart
average consumption oI a
(r) 2 lilres ot milk, lhc strength. The density ofvanadium is 5 96 g/cnl3.
family of 4 persons. Blpress rhis io S.I. uDits (kg/ra). N.C.E.R-T)
(vi) l4 pounds per square inch (atmospheric pres- I,\ns 5960 kg/r,t3l
sure)
t. "The star of India" sapphire weiShs 563 carats. If
| \ir- (i) l 6tlrl (ii) 35.tms-r (,ir) 45 4k* one carat is equal to 2m mg, what is the weight of
(iv) 263 15K (r)2dm3(v09E41 3kg,' -21 the gemstooe in grams ? (N.C.E.R.T.)
4. Convert the tbllowiDg into kilograms : lars. r12.6gl
(;) 500 Mg 0nass of loaded jumhoiet)

I000 m lo0 sr(

t. 16 I knt = t6.ttflf , -ik. *-l-la- -...
r"'
80 miles Dilcs l'160 vtt
80
thour - " I r}ils
36{Xlr
I i6dl lt( lW I nril 3Ra 12.i6 2.54qn \m
'' 2 54 crf 12 irchds 3 t( l'160 ya * -18*--E "7mtm
= 10.0 miles. -w*
mt-|
Note that the least precise term (2 54) has three = 35.76 = 35 8 ms-r
signdlcant tigure.s. (,,0 loorD = louax {1! x }fo = $-+*s
2. Wsight in pounds = 72 0)rr x 6 00i8-x 3 00js (iv) + 2'73 15 K = 263 15 K
Ih -10'C = -10
2 54cm I54cnr 2 54cln 19 3r
' t, ' -l1n " --l-;'- *;fr'51:6V
(v)zL
1 dm
= 150 6()491 lb = 151 lb (after roundiDg off be- = L't- x rooo "-J I dmt mA
-1T-'lTcol
I dn
x lI-lrsi
cause least precise term has 3 srgnificaDt figures)
:2dm3
. 2 54cEl
u-r< lm . 14 h I kr I irrcn l+rch-
3. (r) 5 6" = OO" = r'O
l_rn x TffiE (Yr)
Im " Z.aOl$, Zi4cn1'Z.54iii
=1.6764m=1.68m 100-arn- 100 Drf
(after rounding off to have 3 significaDt fiSures as 1m lm
that of the least precise term) = 9841 3 kg per square metre.
SOME BASIC CONCEPTS IN CHEMISTRY 1115

tl.,!j.Jil,ff5-,,;G' .T.,,,D,,

4. (i) I Mg r.e. nregagram : to6 g : I .54 x 103 pm4s-1

.'. -5(n Mg : soo x 106 g : -5 1 105 kg. lrg 1Q0sm-,. l0,Oprrt
tiil2.66{x
. , lfif ,lo-o* ,190*"
t!* Lp- lW
(il) I fgi.e. fenttogram: lo-15g: 1o-18 kg
5. (i) I F.m,.e- exanletre = to18 m to-6 w 70-6 w lo-6 t*
^_-_ rpm tw tprn
.'. 40 Enr: 4o x 1o18 m : z .
66 x to-6 pg pm-3.
:4 x 1019 tn.
(il) 1 Gm r.e. gigametre : tle m
.'. 1.4 Gm = 7,4 x l09 m
rffi"+&"w
- ('l)| .54 nrnr lrfi
o' ,.. 1I w- I om {
"'o-ftm "'oro{
tm = 5e6o kg/m3
r rl-- 'loftm ' looffi-' ,;n; s. s63-caa6 *Mr*rrblfo -- 1.12.6 s
X- 7o-6:s-
I lct

SOME USEFUL CON\tsRSION FACTORS

(c) Ftom given unit to another unit

t mile : 1760 yards l metric ton : 1000 kg
Iyard: 3feet 1kg :10009
I foot : 12 inches 1g : looo mg
linch :2'54cm 1 lb : 453.6 s
t litre : 1000 ml: 1000 cm3
I quart : 0'9463lttre
or 1 litre : 1.056 quarts

(D) From given unit to S.I. unit

r A : 1o-rom l atm
= 1::,T;:::'*--,
: 1.013 x 106 dynes/cm2
l bar : 1d Nm-2 :
1d pa
1a.m.u. : L.66053 x t0-27 kg 1mm or 1 torr : 733-322Pa or Nm-z
t"C=t+273.75K
=t+273K calorie :
1 4.L84 J
1 litre : 10-3 m3 : I dm3 1 erg : 10-7 J
1 dyne : 10-s N l electronvolt (eV) : 1.6022 x 10-1e J.
vl16
Nl,p1p,,; , iur
-l'he
SI unit ol. lenlperature. viz. Kelvin was given in honour of the great British scientist 'Lord Kelvin'
'Tbrrrpcratures in Kelvin irre expressed as 25 K, 35 K etc. and not as 25"K, 35"K etc.
Irern:i is a unit oI length usecl in Nuclear Physias.
sIicl'toN-IIt
I,A-S S TFICATION OF IIIATTER
1.7. What is Matter ?
Everything that is
around us and the
presence of which can be felt with the help of any
of our five senses i.e. sight, touch, smell, hearing and
l"aste is called matter. In fact, this whole univcrse is
macle up of only two things viz. matter and energy.
Expericncc has shown that all types of matter pos-
sess mass and occupy space. Hence
Mauer ir dqfirwd o\ eny thing that qwapiesspsc.e,
m.il the preslncv of whiih ca* be,folt
po.rtecse.r rners
by uny one or mone of dwrlive wnses.
The cxamples of matter are innumerable. A
fcw of these include clothes, iron, gold, plastics,
wood. water, milk, petrol, kerosene oil, air etc.
1.8. Classification of Matter
There are two ways of classifying matter :
(A) Physical Classification
(B) Chemical Classification.
(A) Physical Classification. Based onphysical
wder ordinzry conclitions of temperature and
state
pressure, nlatter is classified into the following
three typcs :
(1) Solids (2) Liquids (3) Gases.
.,1 suhstunce is suitl to be solid if it possesses a
tlt:finite wtlume and u definile shape e g. sugur, iron,
gtltl, n,uxl alc.
A sub,tlrtrtcc is sukl to he liquid, if it possesses a
dclinilc volumc but no dqlinite shape, Thty tuke up
lhe slrupe o.[ thc vessel in which they are put. e.g.
wulcr milk, oil, mercury, ulcohol elc.
A subslunce is suid to be guseout ifit neilherlro.r.rcsses
u definitc volume nor u de.finite slwpe. This is beca$e
fiq.fiU up he wfutle vessel in whith they are put. e.g.
h;-drogen, o^)'gcn, curhon dioxide, air etc.
i,1 ,,1.1 't Neur Course ChemisttalifrlD
;,ffi.,[5,],.@' iLiEiE2,@,':8
1 F-ernri = 16-13 cm : 10-ls rr.
(B) Chemical Classification. Broadly speak-
ing, all kinds of matter may be classified into the
following two types :
(1) Homogeneous (2) Heterogeneous
The word 'material' is commonly used for all
kinds of matter whether homogeneous or
heterogeneous.
A material is sui.d to be lwmogeneous il it ltns
uniform composition and ilIonfiul propertiet
lhrouglnul.
Since any distinct portion of matter that is
uniform throughout in composition and properties
is called a "phase", hence
A rnalerialis sqld to be lwtnogeneous, di, corxists
ol only onc pihax. On tlu othor hsd, il ,naterial it
said lo be heteropncous if it cansir6 of a rutmger
The composition of each phase is uniform
throughout within itself but is quite different from
those of the other phases. The different phases are
separated from each other by ciistinct boundaries.
For example, water, iron, salt, a solution of salt in
water, air (which contains a number of gases),
motor oil (which contains a number of hydrocar-
bons) etc. are homogeneous whereas a mixture of
ice and water, salt and sand, iron and sulphur etc.
are heterogeneous.
However, a more scientific way of classifica-
tion, called the'chemical classification of mattel is
briefly described below : -
All types of materials are believed to be made
up of "substances". A material containiug only one
substance is called a "pure substance.". On the
other hand, materials containing more than one
substance are not pure and are called "mixtures".
Pure substances are further classified into two
types, called "Elements" and "Compounds". Mix-
tures are also of two types, namely "Hdmogeneous
 SOME BASIC CONCEPTS IN CHEMISTRY
nrixturcs" and "Heterogeneous mixtures,,. pure
substalces (i.e. elementJ and compounds) are al-
ways hornogeneous. Hrrmogeneora. or"
^ixo.".
also callcd "solutions,'. The s1n$e phase in which a
solution occurs may be gaseous, fiqlid or soli<I.
1117
salt dissolved in water and brass (an alloy ofcopper
aud zinc) are examples of gaseous, liquid and solid
solutions respectively. Thus the claisification of
matter may be sketched as shown below.
Air,

Physical Chemical
Classitication Classification

Innrgauic
Compounds

Norv wo shall take up a detailed discussion ol.

the thrse main classes ol'mal-tcr i.e. elements.
com_
irllcl mixtttrcs.
l'crt'"'-t

An elernent is defined as o pure substunce that

cotttains only one kirul oJ atoms.

Carbon, sulphur. iron, lcad, gold, mercury,

oxygcn ancl nitrogen are somc pl". oifamiliar
"*on
 )rra arr's NE.l Co tse Chemistrg lffi[)
)fi8
Non-mctals are those elements which do not Inorganic compounds arc the compounds
containing any [wo or more elements out of more
than 1L0 elements known so far. Those are usually
obtainod lrom minerals and rocks.
'! ixtures
.'1
'1
. M

etc. arg gases.

Metaltoi^ aro those elements which possess
the characteristics of both i.e. metals as well as
non-metals. Some important examples of metal-
loids are arsenic, antimony, bismuth etc. of
There are two
of Mixtures. There tYPs
(1) Homogeneous mixtures
(2) Heterogeneous mixtures
A mbture L\ suid to be homogeneous ililscomposi-
tion is unilorm lhroughout'
The components of
with naked eye or even
A contpound L\ a Pure s bstance conki$ing tvo or homogeneous mixture co
morc thtn l\o elen0n8 mmbinsl togfihzr in a The si-uele ohase in which a nomogcrrsuus utalur e
.r""urc iu"i.
o"curr or solid. For example,
srt"ous. liquid or
-ayb" gaseous,liquid examplc,

pouml are completely dffirent Jrom those of i*

consliluent elzme s'

are called sofu-

d in any propor-
liquid and solid
utual solubility.
A m&lare is said to be heterogenmus iI its com'
pttsition is not uniform throughout.

T}pes ofCompounds. All the compounds may

bc divided into the following two catcgorres :
(1) Organic comPounds
(2) Inorganic comPounds.

and plants.
 SOME BASIC CONCEPTS IN CHEMISTRY
./n6
The various characteristics mentiooed in thc
heir solubility in
definition of 'mixture, can be explained taking the
dissolve in carb-
cxamplc of a mixture of iron fiI'ings, sulphur-and
common salt. Firstly, they can be mixed in any salt is soluble irr
water. So ary one of the two ca! be dissolved and
propottron. Secondly, the mixture can be tested t; then filtered.
1.12. Difference b A nd
_and A Mixtu iit;i rn:r.i:r;;:j+i:::.:.i,:;:::::ii:i

The important points of difference between a

mixture and compound are summarizcd below :
MIXTURI' COMPOT'ND
l. The const it uen rs ofa mEt u re may belre.;rlr m ant- Tleconstituents of a 6 Siid?EiiGfrliEGii
ratio. iD a fixed ratio by mass.
2, Mixlurc may or may nor hc homogeneous in na- Compounds arc always homogencous io nature.
Iure.
3. 'tle properties of a mixrure are midway between The pmpenies of a mmpound are entirely ditferent
those of its constituents. ftom those ofils constituenls-
-fhe
coltstitueots of a mixture can be easily
separated by simplc mechanical means.

Mutures are formed as a result of a phlsical

change.
6. When a mixture is formcd, no heat, lighr or electn-
cal eDergy is absorbd or evolved.

'fhc mclttng and botltng pornts of

mixlures are 7.
usually Dot sharp.

,KN.(},WLE.P.@:8, )
20 carat gold is a mHru re of 20 pans by weight of gold and 4 pans
by weighr of copper. i Id is 24 caral.
Iodized salt used as a table salt is a mxture of NaCl and a small
amount of Nal.
Cement is a mixlurc oIa number of silicates
'lhe cxistence ofan element in two
or more chemrca,y simrlar bJl physica,y diffcrent forms
and the drffcrent forms arc called a,oiropes e.g d'iamond, g.u'pfr1r", is callcd arotropy
allotropes ofcarbon.
*l charcoal, lamp bla"k ;;.;;
'l-hc exrstencc ofa compound
in diffcrenr crysrafline forms rs ci,ed porymorphism
called polymorphs e.q. ZnS has rwo polymorphs called and rhc differenl forms arc
zinc bleno.'unO ,ruririt".
:ti+ o. lhc exlstcnce of diffcrent \ith slmirar chemic{r comF)sition in the same crysralrine form
e.s. znso;.7 -;;;" "
:::i1*n1.. rr2o aDd Feso;, iro'
'omrx)und\ irornorpo.. simjlarry,
is calrcd
atums,
IM2SO4M2, (SC)4)], 24II2Ol, are isomorphs.
Subsl.ances which absorb mosrure from thc air are calle.d hyBroscopic substaoces ag.
CuSOa, PzO5, quicklime (C.aO) erc. aDhldrous

:.llj tt solid substances which absorb a Iar*e amount ofmoisture

from the air so that they become wct or pass inlo
i;$',r1.;ii:il|-
dellqucscent and thc phcnomcnun it ;;x;' l-"riqu"""","" c.8r Naorr, Kori,
1l2O
Neut Course

AOO'f O YOUR RN OWLEDGE CONAD'

T H2o etc when exposed to air lose
:,:i r. some crystallinc solids e 6 cusoo. 5 Hro, Nqco3 10 H2o, Nazsoa
rrater partly or wholly. Such subslanccs are called emorescent and this property is called efiores-
their
cencc'
diffusion is called otmolysis e g'
.. ltt- llc separatlon of a mixl u re of Sases bascd on t helr diffcrenct in the ralcs of
which arc gaseousand havediffcrent
Ux5 and 11238 are separaled byconverting thcm into thcir hexafluorides
rates ofdiffusion.

SECTION-IV (o) Whcn matter uEdergos a physical

change. A piece of ice (solid water) is takenin a
I,,\!\'S oF CTIDMICAL COMBINATION smali conicil flask. It is well corked and weighed'
1 -1 3. Introd uctio n :,::r:i,:::ii:r::l:: i i:i J:i:::r:i:' ir:il]l:i:,:i:i:':il:i::ri:i:r'ii:Lli:;i::ri:ir: :
The flask is now heated gently to melt the ice (solid)
into water (liquid).
One of thc most imPortant aspccts of thc
Heat
subiecr of chemistrv is thc study of chcmical rcac- Water
lce --------i
riois. These chemical reactions takc place accorrl-
ing to ths ccrtain laws, called thc 'laws of chcmical Thc flask is again weigbed. It is found that
combiration'. Thesc arc : there is no change in the rveight though a physical
change has taken plact.
l. Law of Conscrvation of Mass
(6) When matter undI3oes a chemical
2. Law o[ ( onstant CrrmPosition change. The following chemical changes illustrate
3. Law oI MultiPle ProPortions the law :

(i) Precipitation Reacrion. Landolt took solu-

4. Law of RcciProcal ProPortions
tions of sodiumchloride andsilver nitrate separate-
5. Law of Combining Volumes (Gay Lussac's ly in the two timbs of the Landoll's tube (Fig. 1'2)'
Law of Gascous Volumcs) ih" ti-b. were then corked and the tube was
weighed. Thcreafter, the tubewas tilted to allow the
Thc hrst four taws dealwith the mass rclation-
ships whcrcas thc hlth larv deals with the volumcs
two-solutions to mix. As a result of thc following
chemical reactioo, a curdy white precipitate of sil-
of iho reacting gascs. Let us now discuss each of
thcse laws one bY one. ver chloride is formed : -
,r r .l ^,' :ri.i il T1:._ NaCl (aq) + AgNO3(aq)
t: ,,._, ,,- --_ t_
+ Agc(s) + NaNOr(aq)
This law which deals with thc masses ofthc
rsactants and thc products of a chemical reaction
(or a physical changc) was studied by thc great
irench chcmistzln toine Lsvoisiarin 1774 This law
may be stated as follows :
-
In all phJsicql and chemical chdnges, lhz lotal
i1-th" reactants is equsl to that oi tLt
^ott
products.
Thus according to this law, there is no incrcasc
or decreasc in the total mass o[ mattsr during a
chemical or a physical change. In other words,
Matkr can naithcr be creald nor deslrqgd'
Honce this larv is also callcd ths Law oJ ir-
des]rucibiliy, of mqtter. Thc lollowing experiments FIGURE 1.2. Landolt's lube.
illustlate thc truth of this law
 SOME BASIC CONCEPTS IN cHEI\,IISTBY
1121

question ariseFwhere is this mass lost ? Accord-

ingto Einstein, this mass is converted ioto energy
accordiog to the equation
E=mc?
where m is the mass lost and c is the velocity of
100I 92 69 light. Heuce the law of conservation ofmassias
7.4g
been modified. Now it is known as law of conser-
Thus, during the above decomposition reac- vatioo of mass and energy. It states as follows :
tion, matter is neither gained nor lost. Thc mas and enerp are interco yrtible hu ttv
tolsl sam oI E ,noss and energ during ary phlsi-
cal or chemical clnage remains constant.
PROBLEMS ON
IjX,L\IPL[. 4.90 g of KC|O, when heated Differcnce betw:on the mass of the rcactant
produced 1 .92 g of orygen and the residtte (KCI) tcft and the total mass of the products
behind weighs 2.96 g. Show that these results il- : 4.90_ 4.88:0.02 g.
lustrate the lah, of consenotion of mass.
This small differencc may he duc to ex_
Solution. Mass of KCIO3 taken : 4.90 g perimental error.
Toral mass ofthe products (KCl + O) Thus Iaw of conservation of mass holds good
within experimental errors.
= 2.96 + 7.92 = 4.988

1. What mass ofsilver nitrare will react with 5.85 g of 12.0 g. Show that thcsc obscrvations flre in agrce_
sodium chloride to produce 14.35 g of si-lver ment wilh the law ofconservalion of mass.
chloride and 8.5 g of sodium nitrate, iathe law of
conservattoD of mass ts true ? [.\lrs. 17.0 g] {N.C.E.R.T)
2. When 4.2 g of NaHCO3 is added [o a sotution of 3. If6.3 g oI NaHCO3 arc added ro 15.0 g of
acetic acid (CH3COOH/ weighing 10.0 g, ir is ob_ CHjCOOH solution, thc resrdue ts found to weigh
served that 2.2 gofCOz is released iDto the atmos- 18.0 g. Whar is ll., mass of CO2 released in rhe
phere. The residue left behind is found to welgh reaction ? (NC.E.R.T.)
L\ns.3.3 gl

H I t{ T5 FoR DrFFr cu:r ?Ror.LE,v,I

l. AgNOj + NaCt + AgC] +NaNOJ z. Na CO3 + CII3COOII_
xE 5 85g 14 35g 8.5I 4 28 10 0g
, CfllCOONa + H"O + CO- r
x+5 85= 14.35 + 8 5
x= t7.O g Residuc = 12
-:_,___-4.--, 0g 2.2g
Total mass ofreactants
= 4.2 + 10.0 g = 14.2 g
'Ibtal mass of products
= 12.0 + 2.2 g = 14.2,

I
16
1.15, Law ol Constant ComPosition orygen, combined togcther in the samo hxed ratio
of12:32orj:SbYmass
Heat
(a) CaCOj CaO + CO2 t
(b) C + 02- Co2 t
(c) CaCO. + 2HCl.'.'.....- CaCl2+CO2 t +H2O
Ileal
(d) 2NaHCOi .........-NazCO:r + CO2 t + H2O

Limitations of Law of Constant Composition

J
e

:
combines, the ratio of C : O is 12 : 32. But if C-14
isotope combines, the ratio of C : O is 14 :32'
The
(2) rc in the same
the
rqtio but aY be different'
For example CTHTOH aod
CH3OCH3 (both having same molecular formula
viz. CrHuO) the ratio of C:H:O : 24:6:16 =
12:3:8bymass.
C ON STANT c OM POSlrlo N
Fw"pffip..r,D* LAW OF

'188of diructlv the Percentage coT?otilioT:i tYq::

leadcombine . . lh:t
in both the samples of PbO2 is identical' the aDove
witlt to\i-i Uoap"'*i* TbOS
Leadperoxideisalsoplo&lcedbyheatingleaddataillustratetholawofcoostantcomposition.
nitrati and it wos found ahat the W,xentage d dygen
present in lead piroxide is
-data
lj'
j8 percenl' Use these
to illusffati the law ol constant comPosition'
Soluilon. Stp 1' Io calculate the Percentage
ol t qetiment . nitak ielded 2 ' 19 g of copper oide'
Mass of Peroxide formed
=6 488+|Wz=7'4fig.
7'490 g of lead peroxide contain 1 0(2 g of
orygen
... 100 g of lead peroxide will contain orygen thid case, 1 .45 g of copper-when
ft) In the
: ffi* 100 = 13'38 e tf##ff., - a cunent of air vietded 1 8j g of
i.e. orygenpresent: 1j'38Vo Show that the Biven data illusfiate lhe law of
SlEp 2. Tb compare the percentage oI dygen in constant comPoition'
both the qetiments ' Solu6on' stf,p l' In the fitst uPeiment'
Percentage of orygen in PbO, in the first ex- opPer oxide contained 1 759ofCu'
periment : 13 38 .'. 100g of coPPer oxide contained
Percentage of orygen in PbO, in the second : 1 .?<
100 ='19 9r9
experiment = 1.3 38 fr"
 SOIVE BASIC CONCEPTS IN CHEN4ISTRY
-ft{
Slep 2.In the second expeiment. .. 1009 of copper oxide containcd
1'43 g of copper oxide contained 1. 14 g r,rf .46
1
copper - l.8t " 100 : 79.789.
. . 1009 of coppcr oxide contained
't -11
Thus the pcrccntagc o[ coppcr in copper
=ffi"100-7e12s. oxidc derived from all the threc expcriments is
Slep 3. In the thitd exp inrcnt. nearly the samc Hence, the abovc data illustratc
1 83g of copper oxidc contained I .46g of copper thc law of constant composition.

1. 2 16gof coppermetalwben trcatedwirh nitricacid fonned. The silver chloride Dreciptlated is

followed ry ignition o[ rhe Dirrate garc 2.70 g ol
copper oxide. In anofier experiment 1 15 g of
coDper cxide upoD reduclioD with h)drogcn gave
O.92 t of cop[)er. Show that the above data jl-
lustrate thc [.aw of Definite hoporrions.
2. Sih,er chloride is prepared by
(,dissoMng 0 5 g of silver wire in nltric acid aod
adding excess ofhydrocbloric acid ro silver nttrate
separatcd, washed and dried. The wcight of silver
clrloride is 0.66 g.
0i) heating I g oI sitver mcial in a currcnr o[ dry
chlorioe gas till lbe mettl is completcly converted
rnto its chloridc. It is found to weigh 1.32g.
Illuslratc thc law of constant composition by the
above data.

100 = 75 '76qo
% of oxy*D = 20%

This law which was first studied bv Dalton

in 1804 may be defined as follows :-

(2) Compounds ofSulphurand Oxygen. Like

carbon, the element sulphur also forms two oxides
The law of multiple proportions is illustrated
by the following examples :
(1) Compounds
element carbon comb
compounds, namely,
mass of
f .;;; phur (32 parrs) in the two oxides are 32 and 48
,u.;";i ;:T::i:?n'J*::bear
a simpre ratio of 32:'r8 or
A (3) Compounds ofNitrogen and Oxygen. The
l;t ttict t,' 5 Netl Course Ch"-

Nitric oxide, Nitrogen trioxide, Nitrogen tetrcide or

i"Agfrm

elements nitrogen and orygen combine to Produce peroxide qnd Nit/ogen penloide.
as many as 5 oxides of nitrogen, viz., Nitrous oxide, The masses of nitrogen and orygen which
combine with one another arc : -
Compound Nitrous Nitric Nitrogen Nitrogn Nitrogen
oxide oxide trloxide ttraoxide pentoxide
(Nzo) (No) (N2()3) (N2O.) (N205)

Nitrogen 2A 74 2A 2A 28 (parts by mass)

Ox)lgen 16 16 ,a 64 80 (parts by ma.ss)

Fixingthemassofnitrogenas14parts,the-masseso-fory^gcnin.thesehveoxidesareS'16'24'32alid'
l8'paitii"ipectinely.Theseirassesbearasimpleratioofl:2:3:4:5tooneanother'
PHOPORTIONS
- . l.'\ \\lf,l.l' t. Carbon is lowtd to form wo Ir\ \\ll'! l. I Two oxides of a cetl^in metal
' oxides, which contafu 42'9Vo and 2737o of carbon ,l
rcspectively. Sltow lhat these figtres illustrqte the lare
2
ol multinle prooorlions. (N.C.E'R'T')
0 2517 garns
grams of each oxide gave respectively
59!ut&L
ind 0'4526 grams of watcr Show lhat these results
Step | . To calculate thc Percentage cotnPosition establish the Law of MultiPle ProPorlions.
of corbon antl orygen in eqch ol the lwo oidcs
Solution.
First oxide Second oxide {ep Im calcutate the mass o[ orygen in eoch
Carbon 42'g% 27 3% (Given) oxida.
Orygen 57 '7 Vo '72 7 Vo Here, wc arc gilen -
(by difference) Mass of each oxidc = 2.0 g
Mass olwatcr produced in case I = 0 2577 C
Step 2, To calculate the mas ses of cqrbon $'|tich.
combine-with a fLred mass i.e., one parl by mass of Mass olwater produced in case II = 0 4526 C
o\':''n it coch oJ lt( two oxides' 18 g of HrO = 16 g of oxygcn
In the first oide,57 1 parts by mass of orygen i.e. L8 g ofwater contain orygen = 16 g
combine with carbon : 42 9 Parts. .. 0 2517 g ofwator contains oxygen
. 1 part by mass of orygen will combinc with
.
= 0 22378
L).O =4x0?sl?g
18
carbon=i;=075r. and 0 4526 g ofwatsr contaios orygen
In the second oide.72.7 parts by mass of = {xo.a526c = o.,ro23s
orygen combine with carbon = 27.3 parts' 18
. . 1 Part by mass of orygen will combine with Step 2. Tb c&lculate thc m^\s of oLYgen which
)1 1, would combine with 1 I of metal ht each oxide'
carbon=;i=0.376 In case I. Mass of metal oxide = 2g
Mass of orygen = 0 2237 C
Step 3, Tb compare the masses ol carborr which
combine with the sime mass of orygen in both lhe
.. Massof metal =2-0'2237=17163C
. . Mass o[ orygen which combines with
oxides.
1 7763 g of metal :
O 2237 g
The ratio o[ the masses of carbon that com-
binc with thc same mass of orygen (1 part) is . . Mass of orygen which combines with 1 g

0.751: 0.316 or 2: 1' of metal : ffic = o'tzsoe

Since this is a simplc whole number ratio, so the ln case II. Mass of metal oxide = 2g
above data illustrate the law of multiple proportions' Mass o[ orygen = 0 4{23 C
SOME BASIC CONCEPTS IN CHEMISTRY 1/25

.. Mass of metal =2-0.4023=7-59775 72.4 parts by mass o[ metal = 3 atoms of

Mass of orygen which combines wilh 1.5977 metal and 4 atoms of orygcn : 27.6 parts by mass.
g of metal : 0.4023 C In the sccond oxide, oxygcn : 30.0 parts
. . Mass of orygen rvhich combincs rvith I g by mass and mctal : 100 - 30: 70 parts by
mass,
of meral =
ffie: o.z5rsc
But 72.4 parts by mass oI mctal :3atoms
Slep 3. To compare the ,trusscs of oxyg)n which of metal
combine with the same mass oI nrctql i tlrc tu*o .. 70 parts by mass of metal
oxides.
The masscs of orygen which cornbinc with I g -- j2. x 70 atoms o[ mctal
oI mctal in the two oxidcs arc respectively 0.1259 g 4
and 0.2515 g. These masses are in the ratio = 2.90 atoms of metal
0.L259 : 0.2575 or 'l : 2 Also, 27 6 parts by mass of orygcn = 4 atoms
of orygcn
Since thisis asimple ratio, so the abovc rcsults .
. 30 parts by mass of orygen
establish the Zaw o/ Multiplc Prcpottions.
4
: :=- x 30 atoms of oxvsen
zt.b
mula of tlrc rtN oide is MrOo, find that ol the
= 4.35 atoms of orygco
second.
Hencc, ratio of M : O in the sccond oxicle
',6i tioo. In the hrst oxids, o rygctr = 27.6,
'metal: 100-27.6 = 72.4 parts by mass. =290:4.35:1:1.-5 = 2:3
As thc formula of the oxide is MrOa, this means . . Formula of the mctal oxide is MrOr.

RO9L EM I F OR'PRACTICE
"
1. T$o oxides of lead were separately reduced lo
merallic lead by heating in a cufient of hydrogen
that lhes results arc iD accordancc with the law of
multiple proportions.
and the follot ing data obtained :
5. Nitrogen forms ive compounds with Gygen in which
(i) Mass of yetlow oxidc taken = 3.45 g 1.0 g of nitrogeD combinswlrb 0.572, 1.14, I .j3,2.28
LGs in mass during reduction = 0.24 g and 285 g of o(ygen respectively. Shc r that thesc
(ii) Mass of brolrn odde taken = 1.227 B li8urcs agree wirh law of mulripls proportions.
6. Elemenb X and Y form two differenr compounds.
Lcas in mass during reduction = 0.16 g
In the first, 0.324 g of X is combined with 0.471 g
Show that thc above data illustrate the l-aw of of Y. In the second, 0.117 g ofX is combiDed wirh
Multiple Proportions. 0.509 gofY. Show that rhese dara illustrate the Law
Z Copper gives two Gides. On heating 1.0 g of each of Mu ltiple Proportioos.
in hydrogengas, 0.888 g and 0.799 g of lhe metal
are produced. Sholf, that the results agree with the
Law of Multiple Proporrions.
3. IWo oxides of nitrogen contain the follo$ing per-
cntage compositions :

(i) Oxide A conEins

E. (i) 10 t oflead on hearing gave l0 78 g oflirharge,
63 .64 Ea oitrogeo a.ltd 36.36 Eo
qygen. Pbo.
(.i) Oxide B contains ,16.67 % nirrogeD and 53.33
(ii) 9.7'15 Eof rcd tcad (pb3o1) yielded oD strong
% c,rygen, heating 9 545 I of litharge.
Esrablish lhe Law of Multiple Proporrions. (ur) 4.87 oflead perdide (pbo2) gave on healing
g

4. A metal forms two qides. One contains 46.6'lVo of 4.545 I of lithargc.

the metal and aDother, 63.94% ofthe metal. Show Showthat theseresults illusrate the lawof multiple
proponions.
 Pratlcay's Ne# Caurse Ch"rni"tr*ltrfrl[

l. Crlculate the mass of lead combined wlth I g of
o,rygen in each case which are 13.375I and 6.669I
ie. iD thc ratio of 2:1.
2. Cialculate the ma$les of copPer combined with 1.0
of orygeo in each case which are 7.93 g and 3.97 8
ie. in tbe ratio 2 : 1.
3. Calculatc the mass of Gygeo combined with
1.0I of nitrogen in each cas which are 0.571 I and
1 .143 g, Le. in the ratio 1 : 2.
4 Masses of metal tbat combine with 1.0 gofcxygen
are 0.875 g and 1.773 8, the ra$o is 1:2.
6. Calculate the masss oI Y which cambine with 1 I
of X in each cas which arc 1.454 EarJd 435 g i.e.
in the ratio 1 : 3.
I 7. 22400 cc of N2 at STP weigh = 28 3- Calculate
the mass of nitrogeD. Then subtract from the
mass ofoxidg ofnitrogeo to calculate the mass of
o)rytco.
E. Using (i), calculate the mass of lead Presnl in
htharge in (ii) and (iir. Then calculate the masses
of qygen in allthe three cases which combine with
1 g of lead. The ratio comes out to be 3 : 4 : 6

5. Malss of orrygen which combine with l gof N are

in the ratio of l:2:i:4:5.

1.17.l-aw of Reciprocal proportions, ,,,,,,,,,,

proporlions,,,,,,,,,,, i.e. they combine directly in the ratio 12:32 or 3:8
. *n"n]:t:"
This law was put forward by Richter ;"
which is the tu:t
same as the first ratio
^-tn,",'"tt,':'lo:
(2) The elements H and O combine sePsrateiy
1792. It states as follows - ;
wilh the lhird element S to form H,"S and SOrand
The ralio of the masses of two elements A and
HxO as
B which combiie separutely with a faed ntass of the thev contbine rcctly wilh each othet form
to

thid elenont C is eith$ the san?e or some simPle shown it Fig. 1.4.
multtple of thc toLio ol the masses in which A qnd B
combine directly with cqch othet.
This lawmay be illustrated with the helpof the
following examples :

(l) The eletnents C and O combinc separately

wittt tlrc third ele,nent H to Iorm CHo and HrO artd 2 32
H
they combine directly with each other lo form COv
as shown in Fig. 1.3.

4 H.2
12 \16
,o
32
FIGURE 1.3.
In CHo, 12 parts by mass of carbon combinc
with 4 parts by urass of hydrogen. In HrO, 2 parts
by mass of hydrogen combine with 16 parts by
masscs oforygen. Thus the weight o{C and owhich
combine wrth lxed mass of hydrogen (say 4 parts
by mass) are 12 arld 32 i.e. lhey arc in the ratio
12: 32 or 3 :8.
Now in CO2, 12 Parts bY mass of carbon
combine dircctly with 32 parts by mass of orygen
As shown in the Fig., the masses of H and O
which combine with the lxed mass of S viz 32 parts
arc 2 ard 32 i-e. they are in the ratio 2 : 32 ot I | 76.
Whcn H and O combine directly to form
HrO, the ratio of thcir combining masses is 2 : 16
or1:8.
The two ratios are rclated to each other as
1.1-,.,
16u
i.e. they are simple multiple of each other.
I,XAIIIPLE. Ammonia contain.r 82 35Vo ol
nitrcgen and 17'65Vo of hydrogen. Water contains
88 90V. of orygen and 1l l0 % of hydrogen.
Nitrogen tioxide contains 63 15 7o of orygen and,
36' 85Vo of nitrogen. Show that lhese data illustrate
the law of reciprocal proPoxions'
SOiIE BASIC CONCEPTS IN CHEl"il|STRY 1127

ln NH3, 17.65 g of H combine with In HrO, 11. 10 g of H combine with O

N=82.35C : 88.90 g

,i2.35 .. lgolHcombinewithO =
1 g of H combine with N
17 .55 6 f#,
: 8.01 g
= 4.67 g ..Ratio oI the masses of N and O which
combine with lxed mass ( = 1 g) of H
:4 67:8.01=1:1.72
In N2C)3, ratio of masses of N and O which
combine with each other = 36.85 : 63.15
:1, : 7.71
Thus the two ratios are the same. Hence it
illustralcs the law of reciprocal proportions.

ROBLE M 3 FO R P,'RACiIII,G.E
"
1. Carbon dioride ml,tains2T .27 qo of carboo, carb-
97 .23 Eo of chlotine. Pree by calcularions, which
oD disulphide mntains 15 79 Va of carbol, and law is illustrated by these data.
sulphur dioxidc contaiDs 507, otsulphur. Arc these
3. 61 8 g of A combine with 80 g of B. 30.9 g of A
figures in agreement with thc law of reciprocal
combine with 106.5 g of C. B and C combine to
proportions ? [turs. Yesl form compound CB2. Aromic weights of C and B
2. Phosphorus trichloride contaios 22 57 Ea ot pbof.-
35 5 and 6 6. Show thar the lau of
arc respectively
phorus, phosphine (PH3) coDrains 91 t8 Vo of
reciprcal proportioDs is obeyed.
phcphorus while trydrogen chloride gas contaiDs

?P..ObLEMS
t. (15.79qo) c (27.21qa)
cs,'/\',/ \ co"
(84 2t%) S 12.1?%)
(soEa) so2 oo%)
(2 x 6 6 t) CBz (35.5 g)
1g -b with s = f+# = 5.33s
cwilt combire
1a 'ra
t g C will combine wi:-h O = 27.n- Mass of B mmbioingw h 1 gof A =
6i%- =
1.2e r
=2 6'7 I tt{ass of CcombiDingwith of A =
.. Ratio of masses of S and O which cambine wilh
1 g
#f = 3.45 S
fixed mass of carbon (viz I g) Ratio of masses of B and C combining with fixed
= 5 33 :2.67 massof A = I 29 : 3.45 = I : 2.67 = 3 : I
= 2:1. Ratio of masscs oIB and C combining direfifywith
Ratio of masscs ofS and O whicb combine directly each other
witheachother = 50: 50 = 1 : 1. l}lusthe tworatios = 13.2:35.5 = 1: 2.6.t = 3 : 3
are simple muldple of each other. Thus the two ratios arc samc.
..dn
1.18. Gay Lussac'5 Law ol GaseouB volumes ,:',1
The ratio between the volumes of the rcac-
tants and the product in this reaction is simple, i.e.,
Gay Lussac invcstigated a large numbcr o[
I : 1 : 2. Hsnce it illustrates the Law of Combining
chemical rcactions occurring in gases. As a rcsult Volunus,
of his experiments, Gay Lussac found that there
cxists a definite relationship among the volumcs of (b) Conbination between hydngen dnd
thc gascous rcactants and thc Products. In 1808, hc oxygen. Tko volumes of hydrogen always combine
put forward a gcneralization knowr as ths Gay with one volumo of orygcn to produce two volumes
Lussac's Law of Combining Volumes.'fhis may bc of steam.
stated as follows : - 2llz + Oz 2HrO (steam)
2 !ol. I vol. 2 !ol.
-
Here also, the ratio betweetr the volumes of
thc reactants and the products is simplei.e.,2:7:2.
(c) Combination between nitrcgen and
hydtogen. Oncvolume of nitrogen a.[ways combines
with three volumes of hydrogen to form two
volumes of ammonia.

arnplcs:
N2 + 3H2 """""- 2NH,
1\ol. 3 !ol. 2 vol.
(a) Comhination between hydrogen ond
chlorine. ()te vollme of hydrogcn and one volumc
This reaction also indicates a simple ratio of
1 : 3 : 2 betwecn the volumes of the reactants and
of chlorine always combinc to form twovolumcs of
hydrochkrric acid gas. the products.

H2 + Cl2 + zHCl It may be emphasized here that the volume

vol' used in the above reactions are exprcssed in similar
1 lol 1 vol 2
lurlrits i.e. , ml or lilres .

I.aw of chemical combinatioD Who proposed it alld when ?

(d) Law ofconservation of mass Lavoisier, 177,1
(b) Law ofdelinite proportions Proust, 1799
(c) I-aw of multiple proportions Dalton, 1804
(d) I-aw ot rcciprGal proportions Richtcr, 1792

SECTION_V (iii) Why is a compound different from a mix-

ture ?
ATOMS AND ]\{OLIICUI-ES_ To answer thc aboyc questions, it is essential
DALTON'S AI'OMIC TTIEORY
to look into the 'structwe of nrutter' i.e. whatarethe
AND AVOGADRO'S HYPOTTIESIS ultimate building blocks of matter. The concept
,i:r:r I I
rI :r: ::i: ':r:l r' I
: ,; , | :
that matter was madc up of small indivisible par-
:: : ::
1 .19. lntroduction : ,l l*:::i: I :ii:: :,iia: ii:ri ::: :

In Section III, we discussed the classifica-

ticlcs was put forward by Greek philosphcrs
(r.otabty Democints) and these ultimate particles
tion of matter intoElements, Compounds and Mix-
wcre called alomo,s which means indivisible. How'
turcs. Howcver, a number of questions arise, e.g.
cver, a real good mental picturc of matter which
(i) Why is one element different from could answer the above questions as well as could
another ? cxplain the laws of chemical combination was put
(ri) Why do elements combine to form com- forward byJohn Dall.on, an English School teacher
pounds ? in 1808. This is knovzn as 'Dalton's atomic theory.'
 SOME BASIC CONCEPTS IN CHEMISTRY
'1.20. Dalton's Atomic
To describe the structure of matter which
could explain the experimental facts known at that
time about elements. compounds and mixtures and
also the laws ofchemical combination, John Dalton
in 1808 put forward a theory known as Dalton,s
atomic theory. The main points ofthis theory are as
follows : --
l. Matter is made up oI eircruely sntall in-
divisiblc pafiicles called atoms.
2. Atoms of the same element qre identical irt
all respects i.e. size, shape and mass.
Atoms of tlifferent elements have dfurent
3.
m6ses, sizes and also possess different chemical
pmpefties.
4.Atoms of the same or dilfercnt elements com-
bine togethet to fom compound atoms (now called
es molecules ) .
5. When aloms combine htith one qnother to
form compound atoms (molecules), they do so in
simple whole numberrqtios, surh as l:1,2:1,2: j
and so on.
6. Atoms oI two eletnents moy combine in dif-
fercnt ratios to fom more than one compotnd. For
etanple, sulphur combines with oxygen to fotm sul-
plrur dioide and sulphur trioide, thc combining
ratios being 1 : 2 and I : 3 respectively.
7- An atom is the smallest panicle lhat lakes
porl in a chemical reaction, lD other words, whole
atoms, rather than fractioDs of atoms take patt in a
chemical reaction.
8.An atom can neither be crealed, not desfioyed
Explanation of the l.aws of Chemical Com-
binatloo by Dalton's Atomic Theora.
1. Law of ConseNation oI Mess. Mattet is
made up of aloms (postulate 1) which can neither
be creatednor destroyed (postulate 8). Hence mat-
ter cau neither be created nor destroyed.
2. Law o! Constqnt Compositlbn. t( lollows
directly from postu-late 5.
3. Law of Mulliple Proponions. It follows
directly from postulate 6.
Dalton's atomic theory was the first mile-
sl.one towards the inner structure ofmatter, It gave
a powerful initative to the ocientists about ths study
of matter during the L9th century. It held thc
ground for about a century. But the brilliant re-
searches conducted in the begiraing of 20th cen-
tury by Sir J.J. Thomson, Lord Rutherford, Neils
Bohr lnd others haye rcvolutionisod our
knowledge about the structure of atom. The main
drap,backs of Dalton's Atomic Theory are :
(i) 1 :ould explain the lawrs of chemicat com-
bination by mass but failed to exploi\ the law of
gaseots vofumes.
(ii) It could not e.rplain why atoms of dfurent
elemenls havc dwrcnl mosses, sizes, valencies elc.
(iii) Why do atoms ol the same or dilfercnt
elements combine at all to fom nnlecules ?
(ir') What is lhe nature of bindingforce betwccn
atoms aad molecules vthich accounts tor the edst-
ence oI tnatter in three ststes i.e., solids, liquids and
goses ?
(v) It makes no distinction between the ul-
timate particles of an element or a compound.
1.22. Modif ied Dalton's Atomic Theory
As a result of the researchcs made bv
various chemists and physicist, Dalton's atomic
theory has undergone radical changes. Neverthc-
less salient points of this theory have bcen rctained
since theysatisfactorily explain the laws ofchcmical
comhination. The main points of the modern thcory
are :
(i) Atom is no longer considercd to be in.
, divisible. It has been found that an atom has a
complex structure. It is made up of a number of
small particles of which the important ones are
elec|ons, protons and neulrons.
Gi') Atoms of the same elcment may hav
difrrnt atomic masses, For examplc, atoms of
hydrogen may have atomic masses of 1 amu, 2 amu
or 3 amu. Similarly, atoms of chlorine may have
atomic masses of 35 amu and 37 amlu. Such atoms
of the same element which possess diflerent atomic
masses arc called lsotopcs. Ttus, atoms of thc same
elcmeut may not be identical in all respects.
(lii) Atoms of dllferent elements may have
same atomlc masses. of cal-
cium and argon have th i.e.,40
arnu. Szc/r atoms ol lh which
have the sone alomic masses arc called isobars.
Thus atoms of the different elements mav be iden-
tical in one or more respects.
,ff6
(iv) The ratio in which the dilferent atoms
combine with one another may b lixed and in-
tegral but may not always be simple. For example,
the ratio inwhich the elements C, H andO combine
to form a molecule of cane sugar (C1rHrrO11) is
ratio isfued and is also ittlcgal.
(v) Atom is th smallest particle that lakes
part in a chemical reaction. Though an atom is
made up of smallcr particles such as electrons,
protons and neutrons yet aron is tlrc smallest par'
ticle that takes pstt in a chemical reaction.
(vi) Atom is no longer iudestr[ctible' By car-
rying out nuclear reaclions, atoms of an element
may be changcd into aoother. For example, atoms
of nitrogen can bc changed into orygen by botl-
bardmeit with c-rays. Similarly, uranium (rrUa5)
can bc convertcd into plutonium ( ,oPu23e) through
interaction with neufiors. The procress of intercon'
venion of elements lhrough changes in alomic nuclei
i.r cal/ed transmutation.
Further during these nuclcar reactions'
into ener'
E= mcz.
ess can be
In other wotds, atoms are no
changed into enetgt.
lon4cr indeslructible. Howcver, in ordiuary
laboratory reactions, atoms remqitt unaffected" i.e.
they can neither be creatcd nor destroyed,
1.23. Avogadro's HyPolhesis/ Law/Principle :r' ,,
According to Gay-Lussac's Law ofgaseous
volumes, ganes a/ways combine wi t one otother in
a slnple ratio by volume- Bua according to Daltou's
Atomic Theory, e/emenB combine with one anothet
in a simple whole number atomic rslio to form com-
pounds . Beruelits, a Swedisb Chemist, tried to cor-
relate Dalton's Atomic Theory and Gay-Lussac's
Law of gaseous volumes. He argued that while
eleurcnts combine fu a s nple ratio by atoms, gdses
combinc in a simple ratio by volurnc, therc must be
some rclationship between the volume of a gas and
number ofatoms it contains. This led Berzelius
the
to put forward his hypothesis callcd Berzelius
Hypothesis. It may be sl.ated as -
E4ualwturn,s
oltet 2rEra.ts/8
oJ dloitu.
Pratlc o 1t's Nett Course Chemistrqlffifi
Let us apply this hypothesis to the gaseous
reaction between hydrogen and chlorine to
produce hydrogen chloride gas. Experimeutally, it
has been found that one volume of hydrogen com-
bines with one volume of chlorine to produce two
volumes of hydrogetr chloride gas.
Hydrogcn + Chlorine HYdrogen
1 vol. 1vol. ---) chloride gas
2 vol'
l, aloms , aloms 2n comPound atom6
(Appllng Berzelius HYPothcsis)
1
1 comPound atom
2 ] ",orn
This impties that one compound atom of
hycl,'ogcn chioridc gas is marJe ttp,,t j atom ot
arolu of chlonne. This is in dircct
hydrogon and
]
conl'lict with Dalton's atomic theory which states
that atonrs ars thc ultimate particlcs of eloments
and are inclivisible. This hypothcsis rvas, there[orc,
reicctc(l
A\ogadro, an ltalian scientist, solvcd this
a
problcm which cropped up as a rcsult oI Bcrzelius
hypothesis by clcarly distinguishing betrveen thc
two r-rltimat(j particles of matte r, i.c., an atom and a
moleculc. Accortling kt him,
An ahm is ,he sntallcsl parriclc o[ at elamcnt which
cun lrrko part in a chomhal rcaction h muy or may
not be caphle of independant exlslence-
A molaule is lhz smsllas, Itarticl$ of an ebmenl or
'
u compourul which is ctPable oI independmt eljst'
ence.
Sincc thc smallest particlo ol a gas which can
exist indepcndcntly is the moleculc and not thg
atom so thc volurne of a gas must be rclated to the
numbcr r>f molcculcs (rather lhan atoms) prcsent
in it. Hc thus put Iorwar d his hypothesis knorvn as
Avogadro's hypolhesis. This stal.es that
Equalvohtmx ol all gases undet simitu condilions
of tumperalwe and Pressurc cont{i3 equAl number
of molecules.
'lhis hypothcsis has hcen fountl 1o explain
clegantly allthc gascous reactions and is nowwide-
ly recoguized as a law or a principlc known as
Avogadro's Law or Avogadro's principle.
Thc above rcaction bc(\a'cen hydrogcn and
chlorino can be cxplainod on ths basis oI
Avogadro's Law as lollorvs :
 SOI\,,IE BASIC CONCEPTS IN CHEI\,4ISTFIY A-f
Hydrogen t Chlorinc __ Hydrogen
l vol l vol
chloride gas
2 vol.
vapourdensiryof a*^ = #Hffiff**
Mass of certain volume of thc sas at S-T.P
(By experiment)
Mass of same volume of H2 at S.T.P
fl moleculcs n molccules 2t moleculcs
_ Mass cf n molecules of the gas
(By Avogadro's Law)
Mass of n molecules of H,
j motecutc
I mobculc 1 molecule
Mass of 1 molecule of the gas
(By dividing throughour by Zr) Mass of 1 moleculc of H2(i.c. 2 atoms of H)
It implics that one molccule o[ hydrogcn Molecular mass
chloride gas is made up of] molecule ot hydrogen

and moleculc o[ chlorine. Sinco a molecule is or I Molecular mass =2 x Vanour density

I
made up of two or more atoms so molecule is Vapour density is also callud 'relative density,
] of thc gas.
possiblc and may contain onc or two atoms. Thus,
(3) To lind therelationship between mass and
this result docs not contradict Dalton's atomic
volume ofa gas.
theory.
Applications of Ayogadro's Law.
Molecular mass = 2 x Vapour density
(l) In the calculation of Atomicity ol'Elemen-
tary Gases.
Mass of lL of the gas at S.TP
AlomiciD oI an elcmEntary suhstancc is deJined as
u umber of aloms d the element present in oru - ". ..^ Mr*;i IL H, ,r stp
"f
,nolecalc ol thE iubstance, e.g. atomiciE of otygen
(O) is two whila lhat of ozone (O) is threc.
. . Mass of .l L of thc gas at S.T.P
0 089 g
)
Ofu ,
Taking thc cxample of oxygen, its atomicity = Mass of 1L of the gas at S.T.P
can be calculated as follows :
-
= 22.4x Mass of lL of the gas at S.Tp
volumes ofhydrogcn combine with l volume
2
of oxygen to lorm two volums5 of 1y31ar vapours : Mass of 22 4 L o[ the gas at S.T.p
Hydrogen + O^ygen ----------+ Water vapours Thus
lolumes 1lolumc
2 2volumes
22 .4 litres of any gr,s al S,T.P, weigh eq*ol to the
.
App$ing Avogadro's hypothesis mobcular mass of tlw gus uprcssed in grams.. This
Hydrogen + Orygen Watcr vapours k cnllcd Crqm-Moluultr Volume (G.M.V) Lav
2n moleculcs r, moleculcs
-----' 2, molcculcs
s t_Ct't( )N_\ I
or I molecule moteculc 1 molecule
] ATOIIIIC AND MOLECUL,{R
Thus 1 molecule o[ water contains 1/2 SES AND MOI-E CONCI'PT
I\{A*S
molecule o[ orygen. But 1 molecule oI watcr con- 1.24. Relaiive Atomic Masses :,lii:i::j:i:i",:r::;:i::ii'r:,:il :rr:l;;r:::::
tains 1 atom of orygen. Hcnce
Having known that matter is made up of
1
j molecule oforygcn : I atom o[orygen atoms, the next immediate interest ofthe scientists
or 1 molecule of orygen was to determine the masses ofthe atoms. However
.
i.c. atomicity of oxygen = 2.
= 2 atoms of oryge n
as an atom is so small a particle that it cannot be
(2) To lind the relationship betren seen or isolated, therefore, it is impossible to deter-
molecular mass and vapour density ofa gas. mine the actual mass o[ a single atom bv weighing

'Earlierthe STP conditions (i e. Sti

. and U"C, Howc!,cr, now these arc

as l bar and 0"C, STP will be takcn a! I atm and OCin thts book.
1132 Pra rlc r :r's Net4 Course Chemistrglftfiffi
it, Alternatively, the mass of ar atom could have t - .
atomit mast anit (anu) is qad to
been calculated by wcighing a large sample oI the One
fi th o!
element and then dividing by the number of atoms E mt,o ol,,n dtom bI carbon-12 isow.
contained in it but unfortunately there was no
mcthod known to count the number of atoms. Thc Thus the atomic mass of hydrogen is 1.008
problcm was hnally solved by A,,ogad.ot am,u-while that of orygen is 15 9994 amu (or taken
irypothesis which states that "Equal volumcs of as16amu)'
diiferent gases under simi.lar conditions of Prior to 1961, two different standards were
tempcratur"e and pressurc contain equal numbcr of ' uscd for. expressing atomic masses wheu orygen
molccutcs." Thus ifcqual volumes oi two different was-used-as the reference Chemists on their scale
o[ (called chemical scale) assigned an exact value oI
oascs are taken undcr similar condil.ions
mass of orygen atoms as theyoccrr
i;;;;.. ;; o'...rt. ""J',r,., *"igi.J, ,r," inlbtothcaverage
nature' on the physical scale' the isotope ioo
rurio of rheir masscs *itt u" equat to ihc;;il;iil;
-rtt", ofin"ir.ingle molecules (because they con- *"t ^.tig"t!
exact value of 16' As naturally
1o consists of three isotopes (with
tained equal num[er of molecuies). For example, occurring.orygen
1? and 18)' the average value for
taking equat volumcs ofhydrogen and otyg"i, th.i, -11t iTb:f.16'
scal comes out to be 16 00214'
-"rrE ,i" always found in thi ."ti;; i;i;. iii. To rcmove this- duality' all atomic masses are- now
orygen on physical
means thal a moicculc of orygen it oii-"ti"*i.,
r
cxprcssed on the l2c scale' tzkitg mass of this
lhan a molecule of hydrogen. F;r',h.r";;;;
molcculc o[ hydrogcn con]tains two atoms o[ isotope as exactly 12. This sca]e k.called unilied
hyrlrogu, and one m6lecule of orygen contains two scale. On this.scale, the symbol 'u' is.used
instead
u,o- amu' though the symbol 'amu' is still used quite
-uto.-oi
,io,n."u1oryg.n, it -uybe intcrpie-ted iiu,un of
often in place of 'u' Thus now we better write are
of orygen iJ rO ti-". fr"uui"i tf,- - 1 that of
the atomic-mass of hydrogen 008 u and
hydrogen. Thus though ,rr" ,"4ri."..".'iiii" as
orygen as 16 u'
aio-Jcould not be d-etermined but their relative
masscs could be determined. It follows that if the The atomic masses of the elements have been
a(omic mass of hydrogen is talen as one, lhe rela- determined- accurately
during the recent years
ioreiccurately lttlg -,i1:Iu.*"'t called "mass spectroneter"' It
tivc atomic mass ofoxigen is ro (or
itcomesouttobe15.88).,isfoundthatinanumberofcases,atomsofthe
rn rhe beginning, thearomicmasses of allrhe ;:[;];.Hi.',f'.T:i.tifl"::li: I:]i: i:i51
clcments wcrc obtained by comparing. with the the eierient is taken as the average value. For cx-
it was the ample, ordinary chlorine is a inixture of two
omrc mas- isotopes with atomic masses 35 u and 37 u and they
elractron- are present in the ratio of 3 : 1. Hence the average
to orygen atomic mass of chlorine would be
takcn as 16. Howevcr, a still better reference which 35x3+37x1
is now widely accepted, has been found to be carb- 3+1 = 35.5 u
on taken as 12. On this basis the relative mass of
Evidently, the word 'average' must be in-
hydrogen comes out to 1.008 and that of orygen as
cluded in the dehnition. Hence atomic mass of an
15.9994 (or 16). Hence atomic mass ofan element
element may more accurately be deltned as under:
may be defined as follows :
-
Thc alomk nlcss oI an elE nent i8 tlw avcmge nla'
The tive,nilssd s aoms as codpatd vilh ttt 0tom oI
limes carbon tulrcn as 12.
utom
Altematively, the average relative atonic mass
It
may be notsd that the atomic masses as ofan element caube calculated from the'fractional
obtained above are the relative atomic masses and abundances' of the isotopes of that elemetrt.
not the actual masses of the atoms. These masses
Fractional abundance of an isotope is the frac-
on the atomic mass scale are expressed in terms of
tion of the tolal nuntber ol aloms thqt is compised
atomic nwss units (abbreviated as amu).
of that paniculat isotoPe.
SOME BASIC CONCEPTS IN CHEMISTRY 1133

For example, naturally occurriog [eon coil- Lastly, it may be pointed out that naturally
sists of three isotopes, the mass numbers of which occurring carbon contains three isotopes of carbon
and thsir fractional abundances are as follows : with atomic masses 12, 13 aod 14 u. It is the carb-
Isotop Fractional Abundance on-12 isotope that is taken as a reference on the
20Ne 0 9051 atomic mass scale.
2lNe 0 0027 The atomicmasses of a fewcommon elements
22N" 0.0922 taking carbon- 12 isotope as the reference are given
Averagc atomic mass of neon in Table 1.4.
= 20 x 0.9051+27 x 0.0027+22 x 0.0922
= 2A 779 tt

tAItLFl 1.4. Atomic masses ofsome corrmon elcments (taking C-12 = 12.000)

EI,EMI.]NT SYMBOL ATOMIC MASS ELEMENT SYMBOL ATOMIC MA"SS

Aluminium AI no Lead Pb 207 .Z

nrgon Ar 39.9 Litbium Li 6.94
Bcryllium Be 901 Magnesium Mg u.3
Boron B 10.8 Neon Ne 2n.2
Calcium Ca 40. 1 Nitrogen N il.o
(larbon C 120 Oxygen o 160
Chlorine CI 35.5 Phosphorus P 31 .0
Copper Cu 63.5 Potassium K 39 1

Flourinc F 19.0 Silicon si 28 1

Helium He 4.O Situer Ag 107.9

Hydrogen H I .008 Sodium Na 23.0
Iodine I t26 9 Sulphur s 32.1
Iron Fe 55.8 Uranium U N.O
Zinc Zn 65.4

f'X \\ ll'l-ll. Use the dala given in the lollowing 1.25. Gram Alomic lrass
table to calculate the molar mass of naturully occut-
The alomic mass of an el ncnt expr*sal in grans
nnq argon.
is ctlled Gram atomic mass,
Isolope Isotopic molqr mass Abudatce
36A, 35 .96755 g mol-1 0'3!7Vo This amount of the element is also called onz
grum atom.
3EA, 37.96272 g nrol-1 0'0637o e.g. Atomic mass of orygen 16 amu :
eA, j9.9624 g mot-l 99.6NEo Gram atomic mass of oxygcn
(N.C.E.R-T) (or one gram atom of orygen) = lg g
, r ',:: i..ir ,r: i, .T::
Solutiot. Molar mass of Ar
= 35.96755 x 0.00337 + 37. 272 Molecular mass of a substance refers to the
x 0.00063 + 39.96924 x 0.99600 relative mass of its molecule and is defined in a
manner similar to the atomfug mass a5 follows :
= 39.948 g mol-r.
?ilu moluulu @.*s o! ti iubiuae (elencnr or
Note. Also see Problems 18 page 1/7 and 29 compouttd) is tk4.ii$nber d tit 6 thz molecub ol
page 7178 of C.B.S.E. PM.T. (Special) Problems lhc substarct tt hlolter lhan 1 112 th thc mass olan
given at the cnd of this unit for calculation of alom ol carbon-L2 isonpe.
average atomic mass.
1lu
The molecular mass of a substance ca! bc
calculated by adding the atomic masses of all the
atoms preseut in one molecule of the substance.
e.g Molecular mass of HrSOo
= 2 x At. mass of H + At. mass of S
+ 4 X At. mass of O.
= 2x1.0+32.0+4 x 16.0 = 98.0 u.
1.?7. c,t"m Molecltlar Mass .. ,
The molccuhr muss of a substance expressed in
grums ir culled iI Gram molccuku mass.
gram molnule .
e.g Molecular mass o[ H2SO4 = 98.0 u
Gram molecular mass of H2SOI
(or one gram molecule of H2SO4) = 98.0 g
1.28- Mole Concept
In section 1.24, we discussed how the relative
atomic masses of the elemeuts could be deter-
mined. However, the problem of finding the ab-
solute masses o[the atoms remained unsolved until
it became possible to count the number of atoms or
molecules in a dcfinite amount of the substance. It
is found that one gram atom of any element con-
tains the same number o[ atoms and one gram
molecule of any substance contairs the same num-
ber oI molecules. This number has been experimen-
tallv determined and found to be equal to
6.d22137 x 104 correct upto seven sigirificanr
figures. However, the value generally used is
6'022 x 104. lt is called as'Avogadro's numbel or
'Avogadro\ constant' il honour of Amedeo
Avogadro, a great pioneer in this held. It is usually
represented by N. Hence
Avogadro's Number (N) : 6'622 Y
Pradeep's
12, score for 144 etc. are used to count different
objects. Since the trm mole is applicable to all
sorts of particles, while using this term, it is very
important to indicate the nature of the particles
under consideration r.e. whether they are atoms,
molecules or something else. For example, it is
wrong to speak 'one mole of hydrogen'. We must
specily whether we are referring to hydrogen atoms
or hydrogen molecules. Thus :
A mok of hJdrogen atoms me.o6 6.022 \ Id3
atoms of hldrogen wh eas a mok oJ lqdrogen
molecules metns 6.022 x 103 mnlccutes oJ
hydmgen, or 2 x 6-022 x 1G3 uoms olhydrogen
(because each hydragen molecule contqins 2 atons
of ltytlrogen) ,
Similarly. a molc of orygen molecules means
t)'o22 x lOzJ molecules of orygen or
2 x 6.022 x 10ts atoms of orygen.
A mole of sand particles means 6.022 x 10?3
sand particles.
A mole of electrons means 6.022x1dj
electrons and so on.
Generally, when we speak of 1 mole of
hydrogen, it implics I mole of hydrogen molecules
i.e. the natural form in which it exists. However to
avoid confusion, in such cascs, the molecular forms
are called dihydrogen (Hr) diorygen (Or),
dinitrogen (Nr) etc.
It is interesting to note that the magnitude of
Avogadro's number is very largc. Its valuc may be
imagined from the fact that this rumber is about
lOlrtimes the populdtion of the entire world or
Avogadro's number of marbles are sufficient to
cover the surface ofthe entire earthwith 5 km thick
layer. Thus, mole u not a uselul measure for things
which are much larger than atoms and molecules in
size or mass. Further, as I mole represents a very
large number of particles, therefore, being SI unit,
it can be used with prelues. For example,
1 mmol = 10-3 mol, 1p mol = 10-6 mol
1 nmol = 10-e mol etc.
It is usually convenient to express large num-
ber of atoms or molecules in terms of moles. For
example, suppose the sample of a substance (e.&
vitamin C) contains 2.L x 1024 atoms ofhydrogen.
Then number of molcs o[ H-atoms present in the
sample= (2.1 x 1G4)/ (6.022 x 1023) = 3.5 mol.
Further, according to Avogadro's hypothesis
'Equal volumes of different gases under similar
conditions of tcmperature and pressure contain
equal number of molecules'. This means that
SOME BASIC CONCEPTS IN CHEI\4ISTRY 1/35

(t.022x 7O23 molscules of any gas at STP (i.c. 3rd Dellnition (in terms of volume), In case o!
standard tsmperature and prcssurs viz 0"C ar,d gases, t mok is deJinul fls tlur qmtu of fte gas
atmospheric pressure) must havs the same volume. whirh hu a volwrw of 22 4 litrcs dt STP
This volur^re has been expcrimentally found to be
22.4 litres at STP (0"C, 1 atm or '1 01 bar e.g. 1 Mole o[ oxygcn gas : 22 4 litrcs of
pressure) and is callcd molar volume* (bccausc oxfgen at STP
6.022 x molcculcs reprcsent onc mole o[ the
lO23 1 Mole of CO, gas : 22 4 litrcs of CO2 at STP
gas, as already di:cusscd).
REMEMBER
Keeping itr view the differcnt aspects dis-
cusscd abovc, a mole may be defined in any one of Iu C.GS, system,
the following three ways :
I g mole = Molerular mass expressed in grams
lst Dcfnition (tn tenns ofmass).;l nole ic.lefind = 6'022 x 1d3 molecules
as tlut omnmlolthe substarce vhich hasmosquol
to gmn aromb mosl iI tte subslalre b atotnie or In M,K.S. slstem,
grum molauhr nutss if thc subfiq!,cc is t olafurl 1 kg mole = Molecular mass expressed in kg
c.g. 1. Mole o[ carbon atoms : 12 g = 6 .O22 x 10x molecules
(. At.massof C = 12u) Mole Concept for Ionic Compounds. The for-
1 Mole of sodiurn atoms : 23 g
mula of an ionic compound does not reprcscnt a
( . At. mass of Na = 23 u) molecule of that compound but expresses only thc
1 Mole of oxygcn atoms = 16 g rclative ratio of their constituent ions. Howcver. the
(. At.massof O = 16u) [erm mole is applicable to thcse compounds also
1 Mole of orygen molecules : 32 g with thc modification that the term'formula mass'
( Mol mass of O, = l2 u) is used in placc of 'molecular mass' and lhe term
'formula unit'is used in placc of 'molecule'. Thus
1 Mole o[ HrO molecules = 1tl g
( . Mol mass of HrO : 18 u) A mob of an ionic com?ound iJ d4irrcd as thal
amounl oJ thc subslanee v'hich l1g's mass equal to
1 Mole of CO, moleculcs : 44 g
gramlormuh mass (i.e-lormub mass e4ressed in
(,' Mol mass of COz = 44u) grams) or vhich cottains Avogadro's number
(6 .022 x 1e3) ollomullt units.
2nd Delinition (in terms of number). .4 zro& rs
definzd as thtt smouit ol the subslsnce vhich e.g. 1 Molc of NaCl = 5U.5 g of NaCl
conlains Avogadro's number (6'022 x lei) o! ( . Formula mass of NaCl : 23+3-5 5
aloms il alu subsnnce is alomix or Avogadro's : 58 5 amu)
number (6 022 x let) oI moltul2s d rhe sub-
Also, 1 Molc of Na C.l : 6 022 x 1G3
statce is ,no[zcllat
formula units of NaCl
1 Mole of carbon atoms
= 6.022 x 1023 Na+ ions
: 6 022 x 1023 atoms of carbon
and (t 022 x 1023 Cl- ions
1 Molc of sodium atoms
Similarly, 1 Mole o[ Na, COr : 196 * u1*uraO.
= (t.022 x 10x atoms of sodium
1 Mole of orygcn atoms ( . Formula mass of NarCO,

= (t.022 x 1023 atoms o[ orygen = 2 x 23 + 12 + 3 x 76 : 106amu)

1 Molc of oxygen molccules Also, 1 Moleof Na2COr= 6.922 x 1023 tbr-
: 6.022 x.1023 molccules of o4,gcn mula units of Na, CO,
1 Mole of HrO molccules : 2 x 6.022 x 1023 Na+ ions
: 6.OZZ x 104 molecules of HrC) and6.022 x 1023 CO3- ions
1 Mole of CO, molccules (which are further equivalent to 6.022 x 1023 carb-
: 6.022 x. 10ts molecules ofC()- on atoms and 3 x 6.022 x 1023 orygcn atoms).
.ln gencral, nolat whtmc of o abswrcc is thc voltan of onc molc ol that $/bstancc.
1/36
SI Delinition of Mole. The Sl definition of
mole is as follows : - a single atom can be obtaiued. Similarly, the ab-
A mole is lhat smount oJ the substance which
contains as nany elementary entities as therc are
atoms in exaclly 0 012 kg (i.e. 12g) of carbon 12
isotope. The eiementary entities mustbe sPecifiedi.e.
whether lhey are qloms, molecules, ions, electrons or
any other entity.
Atomic Mass and Molecular Mass in terms
ofAvosadro's Number and Mole Concept' As one
mole of any atomic substa-nce is equal to its gram
atomic mass and it contains Avogadro's number
(6'022 x l0B) of atoms. Hence
Gram atomic rnass of an element may
dertned ds the mass ol Avogadro's number of atoms.
S imilarly, Grum molecular masso/a subslancc may
be defined qs the mass of Avogadro's number
t6.022x 1F3) of molecules.
The mass of 1 mole ofany substance is usually
called iis molar massr. Evidendy the molar mass is
equal to the atomic mass or the molecular mass
expressed in grams depending upon whether the
substance is atomic or molecular. As molar mass
is the mass of Avogadro's number of atoms if the
Netl Course Chent i stry
substance is atomic, therefore, dividing the molar
mass by Avogadro's number, the absolute mass of
solute mass ofa single molecule can be calculated.
- lmportanc ofAvogadro's Number and Mole
Concept. Avogadro's number and mole concept
help in the chemical calculation in a numberofways
as follows :
-
1. In the calculation of the actual mass of a
single atom of an element or a single molecule of a
substance.
In the calculation of the number of atoms or
2.
molecules in a given mass of the clement or the
be compound.
3. In the calculation of the number of
molecules present in a given volume of the gas
under given conditions.
4. In the calculation of the sizes of the in-
dividual atoms or molecules assuming them to be
spherical.
These calculations can be understood by
going through the solved examples given below :

nvocaoRo's NUMBER AND l,lol-E cor'roEPr

"IE@WW'@N
Recspitulatlon of trorloulas
(i) In cane ol atomic substances ,
1 Mole = Gram atomic mass or 1 Gram atom of
the element

1 I\,IOLE OF ATOMS

(iii) In care of ionic compound-s,

Mole = Gram formula mass of the comPound
1

= 6-022 x 104 formula units of lhe comPound I

= 6.022 xlo8 times the number ;; ill

present in one formula unrt of the compound.
=6 x abms of the element.
(", M'ti8ifei*::f*
022 1023
(ii) In case of molecular substances, = M,,r"'
1 Mole = Gram molecular mass or 1 Gram or Mass of substance*' = Moles x Molar mass
molecule Nunrber of cntities
roT-F[6' =
Morcs
Avogai,
=6 o22 x I023 molecules of the substance
or Numbcr of entitics = Moles x Avogadro's No.
=22 4 litres at STP if lhe suhslancc is a aas

.Obviouslythe units of mollririss are g mot-l orkg mol-1

,.Molar volume of a liquid or a solid can be obtaincd by dividing the molar mass by density of the substance at thc givcn
temperaturc afld Plessure.
SOME BASIC CONCEPTS IN CHEMISTRY 1137

1YPE I. On the calcul tlon ofthe actusl I \ \\11'! i. -\ Calculate the number of
rn ss ofa sitrglc alom or a sitrgle trrolecule molecules present
(i) in 34 20 grams ol cane sugar
\\\i!lI L
Calculate the msss ol (i) an (c t2 H 22o t )
atom of silver (ii) a molecule ol cafuon dioxide.
: -liifin on" litre oI watet essuming thqt thc
Solution. (i) 1 mole of Ag atoms 10tJ g
density of wstet is I glcm].
( . Atomic mass of silvcr = 108 u)
(iii) in one drop of water having mass 0'05 g.
= 6 022 x 1023 atoms
Solution. (i) 1 mole of C,rHrrO 1 : 342 g
6.072 x lF atoms of silver have mass = 108 g
. . Mass of one atom of silver [ .' Molecular mass of cane sugar (C1rHrrO.,,)
lo8 = 12x72+22x7+ 11 x 16 = 342 amul
= 6.022xt0'J., = l'793 x lo-n g
= 6'022 x 104 molecules
(ii) 1 mole of CO, = zt4 g Now 142 g of cane sugar contain
6.022 x 1023 molecules
( . Molecular mass of Co,
. . 34 2 g of cane sugar will contain
=1x12+2x16=44u)
6'022 x rF
Thus, 6 022 x
= 6 OZ2 x 108 molecules
1023 molecules of CO, havc
= -"fi: rU'Z
mass = 44g = 6'022 x 1d2 molecules
. . L molccule of CC), has mass (ii) 1mole of watcr = l8g= 6 022x1e3
moleculcs
44 44 x 1:0-23
Mass of 1 litre of water : volume x density
6.On c
6.022 x 1G3 x 1=
= 1000 1m0C
= 7.307 x lo-ts g
Nou 18 g o[ water contains = 6'022 x 7021
IYPE II. on thc calculatiolr ofnuntbcr ofatonrs moleculcs
or molccules in a girr:n rtrss ofthe substancc
. . 1000 g of watcr will contain
. r. , i" I .:. How marry atoms and molccules
i 6 o22 x 7023 x Y)ao
ol sulphur are present in 64 0 gol sulphut (Ss) ? 18
Solution. Molccular formula of sulphur : S, = 3'346 x 1d5 molecules
. . Molecular mass of sulphur (S*) : 32 x 8 (iii) 1 mole of H2O = l8g = 6'022x 7023
molecules
= 256 0u
l
1 mole ofsulphur mol-culcs = 256 g
Mass of drop ofwater = 0 059
Now 18 g of H2O contain = 6'O22xlF
= 6.022 x 1023 molecules of sulphur
molecules
Now, 256 g of sulphur contain 6 022 x L023
molccules
.. 0 05 g of HrO will contain
.'. 64 g of sulphur will contain
=
6'@11 1r x o.os
_ 6'022 x 1023 x 64
256
= 1.573 x ldt molecules
= 1 506 x lOa molecules. late the number of atoms
1 molecule ofsulphur (Ss) contains 8 atoms of of th in 5j g of NarCO,

sulphur Solulion. By mole concept,

.. 1 506 x 1023 molecules ofsulphur will con- 1 mole of NarCO,
tain sulphur atoms = 8x1506x 103 = Gram formula mass of NarCO,
= 1.2048 x 10u atoms. :2xZi+72+16 x3 = 1069
1/38 Neqt Course Cheaisttq
Now, 106 g of Na2CO, : 1 mole Thus, 22rlo0 cm3 of NH3 at STP contain
1x53 6 022 x 10ts molecules
.'. 53 g of NarCO, = .
106 . ?00 cm3 of NH, at STP will contain
= 0.5 mole of NazCOr _6.022x10 ,!.tm.l
But 1 mole of NarCO, contains 2 moles of 224{fr
.t62 x 1d2 molecules
Na+ ion or 2 x 6.0z2 x 1023 Na+ ions. =l
.'. 0.5 mole of NarCO, will contain 'nPIi I\: ( )n rhr (.rlrnlul i,)r, ,,1
sizt\ of indi\ iriu.rl utonrs or nrolr. Lri"s
2x 6.022 x lor x O.5Na+ iotrs
= 6.022 x 1d3 Na+ ions L\ \\ll'1.1. (. (i) Assuming the density oI
water to be lglcm3, calculate the volume occupied by
Again, 1 mole of NqCO, contains 1 mole of
one molecule of waler
carbon atoms = 6'022x 104 carbon atoms
(ii) Assuming the watet molecule to be sphei-
.'. 0 5 mole of Na2CO3 will contain cal, calculate the dismeler of lhe water molecule,
= 6'A22 x 10u x 0'5 carbon atoms -t)b/*lsunring that orygen atom occupies half
o[ tlrc volunte occupied b)t the water molecule, calcu-
= 3.011 x 104 carbon atoms
late approximately the diameter of lhe otygen atom.
Further, 1 mole of NqCO, contains 3 moles
Solution. (i) 1 mole of HrO : : 13
18g
of orygen atoms or 3 x 6 O22 x 104 orygen "-:
atoms ( . densitY of HrO : | 9cm3)
.'. 0'5 mole of NarCO, will contain = 6.022 x 1d3 molecules of HrO
3 x6 022 x 1023 x 0'5 orygen atoms Thus6'022 x 108 molecules of HrO have
= 9'033 x 1d' oxygen atoms volumc = l8 cm3
'l-\ I'l! tl I. ( )n lhc crlculxlion of rrrnrl'cr .
. 1 molccule of HrO will havc volume
, l rrr,.Lr'ttlcs t,rr\rrt ir.r ti\(Il
vilunrc,,1 :r ras undor gir(n co[rlitioDs 18
= 6.022 x, 7U5
= 2'9t9 x 10-a cm3
(,I) As water molecule is assumed to be
and 2 almospherc pressare.
spherical, if R is its radius, then its volume will be
Solution. First of all, we have to determine -cm-
the volume of the gas at STP. L3 n3 = 2 989 x 10-23 cm3
Given conditions At STP
or
Vr : 350 cm3
R3 = 7'133 x 10-24
or R: (7.13r;t/: y 1g-s
Tt = 273 K Tz = 773 X
= I 925 x 10-8 cm
P, :2atmospheres P2 = latm
. : Pr V, PzYz
Appl),rng gas cquatron
,l = T,
350x2 L x V2
we get
zr=n3 . . Diameter of water molecule
or u,='2A' *! = too"ot = 2x7.925 x 10-8 cm
By molc conccpt, =385xl0-8cm
1 mole of NH, = 6'022 x 1023 molecules (iii) As orygen atom occupies half of the
volume occupiedbywatcr molecule, hcnce ifr is the
= 22,100 crt3 at STP radius of orygen atom, theD
 SOI\4E BASIC CONCEPTS IN CHEI\,4ISTRY 1/39
a-1 (vi)7.9mgof Ca= ?.9 x 10-3gof Ca
I3ZtF =:x2.989x10-tscm3
7.9 x 10-l
or f =3.566 v 1g-ze = mol (Al. mass of Ca : ,10 a)
40
which gives r= 7'528 x 10-8cm (vii) 65.5 pg of C = 65.5 x 10-6 g ofC
.'. Diameter of orygen atom
= Ali4-"1 = s.45r x 1o-Gmot
= 2 x 7-528 x 10-tcm
= 3.056 x l0-l cm.
lf'PIi \: ()ll tLc (,xrl'crsio ol m,)les into rrrr\s-
\lrllrlrc or lirnrhor of rtot s/tnok'culcs arrri ricr: ersa T
and (iii) 112 cnf of hydtogcn at STP
(i) l mole of KNO, = 1Q1g
l:\ \\ll'l-ll i. Cqlculate the number of moles
in each of following : -
the ( .' Formula mass of KNO,
(i) 392 grarns ol sulphuic acid (ii) 44. 6 litres ='tx39 + 1x 14+3x 16= 101 u)
of carbon dioid.e at SfP \ii) 6.022 x 1d3 ..01moleof KNOr = 101 x0.1
molecules of orygen (iv) 9 . 0 grams of aluminium (v)
I metic ton of iron (l metic ton = ld kil (vi) 7 .9 = 10.1 g of KNOr
mg ol Ca (vii) 65 pgof cabon. (ii) 1 mole of CHo - 16 g
Solrtion. (i) 1 mole of HrSOo : 98 g. = 6.022 x 104 molccules
( . Molecular mass of HrSOo i.e. 6'A22 x 1d3 molecules of methane have
:2xt+ 32+4x 16= 98u) mass :
16I
Thus 98 g ofHrSOo =l moleof HrSOo .. 1 x 1023 molecules of methane will havc

.'. 3929otHrSO4=:x392
1
-u." = 6"r;*-r*, x rF = 2.6s7 e.
(tii) 1 mole of H, = 2 g : 22400 cm3 ats fP
= 4 moles of HzSOr.
i.e. 22400 cm3 oIHz at STP have mass = 2 g
(ii) l mole of CO, :22.4litresatSTP
.'. 172 cml of H, at STP will havc mass
i.e.,22. 4 litres of COTatSTP =l mole
)
.. 44.8 lirres of CO zats'tP= M.8 = ffi" l12= 0.0rg.
,hx l'.\.t\ll'l.ll ,). Anange the following in order
= 2 moles COz of lhcir increosing masses in grams ?
(rii) 1 mole of C), molecules : 6.022 x tG2 (i) One
molecules nitrogen, (iii)
x o4gen molec
6'022 Le3 molecules =I mole of orygen
One gram of iron.
molecules.
(iv) 1 mole of Al = 27 gof Al -!98!rm. (i) 1 mole of Ag atoms = 108 g
( . Atomic mass of aluminium = 27 u) = 6.022 x 104 atoms
i.e. Z7 g of aluminium = lmoleofAl i.e. mass of 6.022 x 1d3 atoms of Ag = 108 g

= ! x9
1
.'. 9g of aluminium .
. Mass of 1 atom of
" = ----4q--
Ag
6.022 x 702i
= 0.33 mole of Al
(v) l metric ton ofFe
1d kg : : ld g
= 1'793 x 10-22g
I mole ofFe = 56gofFe (ii ) Mass of one gram atom of N : At. mass
ingrams = 14.0 g .

. . 106 g of Fc = 14 (iti) Mass of one mole of Ca :

-o1"" At. mass in
grams = 40.0 g
= 1.786 x 1d moles.
1140 Neut Course Chemistrrl
(rv) Mass of one mole of orygen molecules
..14gof nitrogen wilt occupy
4ax
:
Mol. na"ss in grams = 32'0 g
= 14

(v) 1 mole of C atorn-s = 12 g = 11.2 litres at STP

:
6.022 x 10F3 atoms (ii) l mole of carbon dioxide : 22.4 litrcs at
t.e., Mass of 6' 022 x 10! atons of C = 12'0 g STP
. . Mass of 1013 atoms of C
.. 1.5 moles of carbon dioxide will occupy
12 x 108 l.99Jg ::)) a,
x 1.5 = 33.6 litres at STP
= 6.o22xIOB'--
=. =
(rri) 1 mole of O, molecules
(vi) Mass of iron = 1 .0 g (Given)
Thus the order of increasing masses is : = 6.022x 104 molecules = 22.4litrcs at STP
i.e 6.022 x 1023 molecules of orygen occupy
C)ne atom of silver < one gram of iron <
108 atoms of carbon < one gram-atom ofnitrogen 22.4 litres at STP
< one mole of orygen < one mole of calcium. 1021 molecules of orygen will occupy
l,lXANIl'l,li lt. Calculate the vofume at STP x 1o2l litres ar STp
occupicd by (i) H C9fuituSct*(ii) I'5 moles of = 6.022"'o ==
x 1O2!
csrbon dioxideiiATiil ldt mokcules of uygen. = 3.72 x
1O-2litres at STP
qo_!f!!gt (i) Molecular ma.ss of nitrogen = 28 u 3.72 x
10-2 x 1d cm3 at STP
=
1 mole of nitrogen = 28 g = 22.4 litres at STP r = 372 cm3 at STP
l'.e. 28 g of nitrogen occupy 22.4 litres at STP

1. (d) What is the mass of (iii) 52I of He tNC.E.R.T )

(i) 1 mole of water (ii) 0.5 mole of CO2 [ ,rns. (4 3.1314 x l# (ii) 13 (iii) 7.t2E6 x rP]
(r)i) 2.5 moles of CI2 'l 5. Which of the following weighs most ?
(i) 50 I of iroD
'.ns (i) 1E.0 g (,,) 22.o g (iii) 117.s gl
I ( )5gatomsofnitroSen
(b) How many moles ofatoms are contaiDed in :
(iii) 0.1 g atom ofsiker
(i) 9.0I of AlunriDium (ii) 0.8 I oflron ?
(iv) 1 x 1P atoms ofcarbon
I r,. (irlmolerii; fimolel I Aus. (i) 50.0 e (ri) 70,0 g (iu) 10.t g (ir) r.992 g.
2. Calculate the number of molcs in each of the fol- IIeDce 5g rtoms of tritrogetr w.igh mo6tl
lowir1g amouIrts of materials
6, Calc:ulate the number of molecrles present in Z2 g
of CO2 ?
(i) 10.0I of CaCO3 [ '.r'. 3.011 x 1d3 moleculesl
7. Calculate themassofCO2 which coDtaios the same
(ii) 1 x 104 moleculcs of CO2 number of molecules as are contained in 40 g of
I ,1n. (i) 0.1 mole (ii) 0.166 moleJ orygen. [ \r.. 55 g]
3, What is the mass in grams of :
E. Calculate the mass of Na2CO3 which will have thc
same number of nolecules as coDtained io 12.3 g
(i) 6.022 x 108 atoms of orygen ?

(ri) 1.0 x 1023 molecules offI2S ?

of MBSOa.?H2O.
I
s.3 s]
9. calculate thc volume occupied by 1(P2 molecule.s
(iii) 6.022 x l(P3 mofecules of oxygen ? of a gas at 300 K and 760 mm pressure.
(rl, 1.5 oroles of H2SOa ? I tr"
40t'9 cm3;
10. Find the number of atoms of each type prcsent in
I \,). (i) 16.0s ('i) b.els g 1ir4 rz.o g 1i,1 rlz.o g1
3.42 grams of cno sugar (C12H22O1t).
4. Calculate the Dumber of atoms ih each of the fol-
lowing I .\n.. C = 7.226 x td2 atonrg
(i) 52 moles of He (ii) 52 11 of He H = 1.325 x lF atomsl
SOME BASIC CONCEPTS IN CHEMISTRY 1141

11, Calculate the mass of 1 molecule of- 16. The mass of 350 cm3 of a diaromic gas at 273 K at
(i) oxygen (ri) ammonia 2 atmospheres pressure is one gram. Calculate thc
mass ofone atom of the gas.
t \,i. (i) 5.314 x 10-23 g (ii) 2.t23 x 10-2r gI
12. (a) Calculate ihc volume occupied ar STP by [ \ns 2'657 x 10-23g]
(i) 16.0 g of orygeo (!i) 1.5 motes of orygen aDd 17. How many atoms and molecules ofphosphorus are
(iii) 6.022 x 104 molecules of carbon diodde preseDr in 124 g of phosphorus (p, ?

I r,,.. (i)
ll.20litres (ii) 33.60|itrcs (iri) 22"4 litrcsl I ru. 24.0Ettld! atoms and 6,022x1F DoleculesJ
13. (i) Ho\" many grams of H2S are conrained in 0.40 lt. What is the mass of a water molecule in gram ?
mole of H2S ? How maDy molecules are presnt in one drop of
L\ns 13.6 gl
purewaterwhich weighs 0.05 g.Ifthe same dropof
(ii) How many tram aroms of H and S are con-
wa tcr evaporates in one hour, calculate the numbr
tained in 0.4O mole of H2S ?
ofmolecules leaving the liquid surfac pr scond.
[,u,s 0.t I otoms ofH ond 0.4 g atoEs ofSl
(rii) Hotp many molecules of H2S are containcd in [ \r)\ 2.989 x lO-23 9,1.673 x l02r moleculcs
x 1017 molecutes/sec.l
and 4.647
0''!0 mole of H2s?[
rns.2.4t8Ex10P molctules] 19. What is rbe mass of carbon present in 0.5 mole of
(iv) How marry atoms of H and S are contained in K1 [Fe (CN)6] ?
lrn. 36 gl
0'40 mole of H2s ?[ 20. The cost of table salt (NaCl) and table
t,r 4.tl76xr0! atoms ofH sugar
and 2.4(BE x lF atoms ofsl
(cr2H22oll) is Rs. 2 per kg and Rs. 6 per kg
14. You are supplied with a gas contaiDiDg 0.32 g of respectively. C.alculate their msts per mole.
cxygen. Calculate the Dumber of moles aDd Dum- [.\Is. Solt = 12 p, Sugsr = Rs. 2.OS p]
ber ofmolecules present in it. 21. Chlorophyll, the green mtouring matter of planrs
[.rrr..0.01 rnote, 6.022 x ldr molecules] responsible for photosynthesis, contains 2.68% of
15. The mass ofa litre oforygen atsrandard conditioDs magnesium by weighi. Calculate the number of
of temperature and pressure is 1.43 g and that ofa magnesium aroms in 2.0 g ofchlorophyll.
litre of SOz is 2.857 g.
(N.C.E.R.T,) [ An".l.34s x tdrt
(i) How many molecules of each gas are there in 22. Ho,v much timEGiidli-iake to disrribure one
this volume ? [ADs.2.6EE x ld, moleculesl Avogadro's number ofwheat grains if 1010 grains
(ii) What is the mass in grams of a single molecule are distributed each scond ?
ofeachgas? [.rrrs.oz 5.320 x t0-,3gand I aD.. 1m,t93 ],rars approx.I
=
23. Calculate the total numbr ofelectrons prescnt in
SO2 = 10'629 x 10-23 gl
I .4 I of nitrogen gas.
(rii) What are rhe molecular masscs of SO2 and
[ &rs.4.214 x ld3 electronst
02 resPectivel} ? [ \nr o: = 32.032 u and
SO2 = 63'D7 ul

FOR DIFFICULT ?R:OE-LEi/'S

4. (ii) 4 u of He = I arom of Hc 0.05 mol NECO3 = 0.05 x 106 8 .3 g
= 5
7, 40 goz = 40,32 moles = I 25 moles
9. Volume occupied by 1022 molecules ar ST?
l25molesofCO2 =125 x44t=55 g
-f4!!-* x toz2 cmi = 3:l2.1 cm3
(Equal moles conrain equal number of molecules) 602x10"
P, Vr '160 xvt
E. 12.3 t Mgsoa. 7 H ro =
6e *n*2*1776i ^or \vz .760 x1iz.l
-T- =-E-' --rm- = ----71-
12.3
= f;6 mol = (l U) mol or Vl = 408.9 cm3
1142- Netl Course Chen,ist l
HINIS CCNI-T:D,

ls. IL Oz or SO2 =
Zii
I

^ol
No. of molccules leavirg p", ,"" = Lffifff4
=fi"u'orxlosmolecules = 4 647 x 1017
19. I mol of K1 [Fb(cN)6] mntaim c = 6 I atom
= 2 688 x 1022 molecules
0 5 molof K1[Fe(CN)6] wilt coDtain C
Mass of 1 molecule of o.' = 1 43 ,, s =3 x1,28=369
2.688 x t0" - =6 x 0.5 gatom = 38atom
x 20. I mole of NaCl = 58 5 g
-- 5 32o 1O-B g
2 E57 .. Cost of NaClper mote =
1ft' x 58 sRs.
Mass of I molecule of So,
' = 2 688x10"..
=0ll7Re=11 1p=12p.
= 1.0629 x 1o-B g 1 mole of sugar (cl2Hz2o:fl) = 342 E
Gram Molecular mass of 02
= Mass of22 4 L at STP
.. Cost ofsugar per mote =
ffi x:lz Rs.
- 1.43 x 22 4 =32 O32g = Rs. 2.05p.
Molecular mass of Oz=32 O32 rt 21. 10Og chloropbyll contains Mg = 2 68 I
Similarly, molecular mass of So2 can be calculated .. 2 g chlorophyll will contaio Mg =ffi "
z
16. (i) Find the volume of the 8as at STP which is
= 0.0536 g
700 cm3
(ii) F-ind the mass of I mole ie. 22.4 litres of I mole of Mg=24g = 6'022 x 1oB atoms
8as at

sry,Le. ffi =es -- o o536BME=9J4;fg xo 0536 atoms

(ii) Calculate the mass of one molecule ie. = 1.345 x to2l atoms
32 .. g and dMde il b,y 2 to get lhe mass of q9-+0'z3 ,
6.022 x 10" 22, Tlme Required = = 6 s2 x to13 s
one atom of the gas.
18. l mol of Hzo = 18 8= 6 022 x 1023 molecules =-;ftffi#lrrrrears
'. Mass of one molecule of H2O 190,893 yeals approx.
=
1.4
= a,----J3 - Ts = z.s1s x to-23I 2J. 149N2=; mol =0 0s mol
o?7 x 10" "

o 05 gof H2o = =0 05 x6 02 x 1023molecules

!,qmor
= 3.01 x 1022 molecules
= 1*1 * u o" x 1oB molecules = 3 01 x 1022 x 14 elcctrons

= 1.673 x 1021 molecules =4 214 x 1023 electrons

callsd the solvent.

o[ a solution can be ex-
A sohrtion k tlefined as a homogeneous mixture oJ -- l-l:-t:l:"""ation
presscd in a number ofways as follows:
tt+o or nnre chemiculty ,rr-*ririi trtirri"i,
tht rela,iye amounts oi which un belaried upto a (1) Strength. Trte srrength oJ a mlution is defined
certain limil. as lheamo d of the solule in grams Presen per
I[ a s,'lutirrn consi\rs ot .nly rwo com- ';::;^%'::riy::;n:i;i:li"::r:;;)r';;:r:,
Ir)n(nr\. ir i' r.rtled r binary s,lution. Tl,. :ll ii t\o eolthe solutioi lcutkd piicent itength
Ili)nenl lr( \(nl in snrrllcr amount is callcd lhc fu
^ori)."
 SOME BASIC CONCEPTS IN CHEMISTRY 1143

(2) MolariBThe mobrit! of a solution isdqincd number of moles in the solution remains thc same,
as thc numbet oJ moles of the solute pfiEsent per we h ave
litre oJ thz sokrtion. It is representcd by the sym-
bol M. M,xV,=MrxV,
(3) Molallty. Tlu nolauty of a nfutim is dcfiictl This equation is called molarity equation.
ar tfu nunbcr ol molts of tlu nlute dissolvcd in
1 0OO E oI lhe solvcnr. It is Eprcsentcd by tlE slmhol,
For a balanced chemical equation involving
m.
,?
r moles of reacta.nt 1 and n, moles of reactant 2,

(4) Normdtty.Tlz nonta@ of a mlution is M,V, M,V,

delind as thc number of gratn equivalents o! the n1
sobte presenrllitn of the solutioL It is representa.t
by thc symhol, N. For exact neutralisation of V, ml of an acid
(5) Mole fractton. The molatraaion ol aay com- having molarity M, and basicity z, by V, ml of a
porwnt in the nhtitn is equal to tlu numher oJ base having molarity M, and aciditynr,
moks o! that corynnent dividcd by the total nun-
her o! molzs of all the ctmlnnc s. For a sohtfun
conlainhg nx molzs of lhe sohttc disrrllved itt n,
noMoYo = nrMoY,
mobs ol ttv solye , Normallty equation. If a solution having
normality N, and volume V, is diluted to volume
Moleftaction qlsol teinthe nhaion
n2 V, so that the new normality is N, or if V, cc of
(r) = nt4nz solution of substance A and normality N, react
exactly with V, cc of solution of substance B and
Mob lraaion S solvent in u solaion
, n, normality N, , then in the first case as the number
fr.)=- ofgram equivalents remains the samc and in the
nr+n2
second case, substances react in equivalent
:r + .t, =1 amounts,

The equivalent masses of acids, bases and Nl xVl =N2xV2

salts are calculated as follows :
- This cquation is callcd normality cquation.
: Mol. mass of the acid
Eq. mass of an acid REMEMBER
Basicity
Mol. mass of the base
Normality ofa solution = No.ofgeq.L-I
Eq. mass of a base =
Acidity = No, of milll eq. ml--l
Eq. mass of a salt
Molarity of I solution = No, of moles L-l
Mol. mass oI the salt
Tbta.l positive valency of metal atoms = No. of milli moles ml--l
Baslcity is the number of displaceable H+ ions lrom l._\\1ll,l.l,l 1. A sollLtion of otalic 0cid,
one molecule oI the acid (e.g. 1 for HCl, 2 for (COOI|, . 2H2O is prcporcd by dissolvittg 0.63 g
HSOa ,3 for HIPOaetc.). ol thc ucid in 250 cnf of (he solution. Calculqtc
Acldity rs lhe number of displaceable OH- ions (a) ntolai\ (b) nomlolity oI the sohttio .
from one molecule of the base (e.g- 1 for NaOH, 2
fot Ca(OH)2etc.). Solution. (s) Calculation of molarity.
Molarity equation. If a solution having Molar mass of oxalic acid,
molarity M, and volume Vr is diluted to volumc CoOH
V2 so that the new molarity is Mr, then as the total | .2H2O = 126 g mol - I

ctooH
1144
Pradeep's i

Molar muss of HCI - 36.5 g mol-l

.. 0.63 g of oxalic acid = Q9mole of oxalic
..38gHCI = _: mttles = 1.04molcs
acid : 0.005 molc of oxalic acid
Thus 84.03 cm3 of the solution contain HCI
IMor",
L"'"-" =,Y?"'n* I
Molar mass l : 1.04 moles
Thus 250 cm3 of thc solution contain oxalic . . 1000 cmr of the solution contain HCI
acid : 0.005 mole 104 x
= 84.03 rooo
. 1000 cm3 of the solution contain oxalic
.
: 12.38 molcs
,"la= ryrrj x 1000 = 0.02mole i.e. Molarity of thesolution: l23EM
(D) Calculation of volume of conc. HCI for
i.e. Molarity of the solution = 0'02 M
1.00Lo10.10M HCl.
(r) Calculation of normality Applying molarity equation, we have
. Mol. mass of oxalic acid
.
Eq. mass ol oxahc acrd: -----;;[ity- M1 xVl = Mzx Vz
HCI) (l '0 L of 0' 10 M HCI)
(conc.

=;= 126
u, 12 38xVr = 010x10
0.r o
or V' = #L = rr-I*-l x tooOcms
1

. 0.63 g of oxalic a"16= : 0.01 g eq.

.
ff c
"t.
-- 8'1cm3
.
I (;ram coulvalcnts
Massingr
A samPle of NI.OHweighing
L = =-
ts,q. mass J
| I.l\,\Nt Pl -l'1.r. (a)
0.40 g is dissolved in watet and lhe sollttion is made
Thus 250 cm3 of the solution contain oxalic to 50.0 cmJ in volumetic flask. Wat is the molaity
acid = 0.019 eq of thc resu ing solution ?
.. 1000 cm3 of the solution contain oxalic (b) How many grams of NuOH should be dis-
solvid to make 100 cm3 ol0 15 M NaOH solution ?
u"id =
$ x 1000 = 0.04geq Solution. (a) 0.,10 g of NaOH =
0.40
Imotes
i.c. Normality of lhe solution : 0'04 N : 0.01 mole
I , . '. l' )- Commercially available con-
centrated lrydnchloic acid contains 38Va HCI by Thus 50.0 cm3 of the solution conLain NaOH
nlass. = 0.01 mole
(a) tuhat is the molaity ol this solution ? The . . 1000 cm3 of the solution contain NaOH
ttcnsity is 1.19 g cm-3. 0 01
(b) Wat volume of concentruted hydrochloric - x looo = 0.2 mole
50
acid is rcEtired to make 1.00 L of 0 10 M HCI ?
. . Motarity of the solution = 0.2 M
(N.C.E.R.T,)
(b) 1ffD cm3 of 0.15 M NaOH contain NaOH
Solution. (a) Calculation ol molarity- 18"/u
HCI by rnxiiiireans that 38 g of HCI arc present in = 0.15 mole
l(n g of thc solution. .
. 100 cm3 of 0.15 M NaOH contain NaOH
Volume of 100 g of the solution : -ffi
= !15-
1000 "
too= 0.015 mole

= # = 84.03cm3 = 0.015 x ,10 g = 0.6 e

 SOI\,4E BASIC CONCEPTS IN CHEI\,4ISTRY
1145

RO BL E M I FO R IPRACT,,l'6_iE
l. A "solution is prepared by dissoMog 18.25 g of
NaOH in distilled warer to givc
4. How many grams of barium chloride (BaCl, arc
2OO cm3 of the necded to prepare lm
solutioD. Calc-rJlate the molarity oftbe 6olution. cm3 of0.250 M Ilach sotu-

IArrs.2.2t Ml
tion ? s.20 gl I
2. How many moles and ho\ many grams ofsodium
5, How many moles and hof, many grams ofsodium
chloridc (NaCI) are presnt in 250 mI. ofa 0 50 M
chloride (NaCI) are prcsent in a50 cm3 of a 0.500 NaClsolution ?
M NaCl soluiion ? [,\rrs. 0 125 mol, 7.32 g]
6. A sample of NaNO3 weighiog 0.38I is placed m a
lArs.0.125 Eolg 7.312 gl 50 0 mL measuring flask. The llask rs then fillcd
3. CrnccntEted aqueous sulphuric acid k ggEa utttwater upto the mark on the neck- What is lhe
lI2SO1 by mass and has a density of 1.84 g cm-r. molarity of the solutron ? (NC.E.R.T.)
What volumc of the concentrated acid is required l-\,;.-:Im66'fri-
to make 5.0lire of 0.500 M H2SO4 sotution ? 7. lD g of NaOH is required
to the reaction. HowmaDy
[,rn,, 135 cm3; mi OI{ solurion shoutdbe
added for this requirement ? (N.(:.8.R.7:)
I 30.7 mt,l

3.98o/o I[7SO4 by nrass means 98 g H2SOa are .. For 100cm3 of0.25 M llacl2, mass needed
prcscnt in 100 g of rhe solurion = 100/l .84 cm3
204
= 54.35 cm3 = iood'loo x 0 25 g
Molar mass of II2SO4 = 98 g mol-l = 5.2O B

98I 6. Lbrmula massof NaNO3 = 23 + 14 + 48 =

I-Iencc [IzSOa =l mole 85

'. Molarity ofthe given solurion 0.38I NaNO3 = = o.oo4s mol

\f 'or
=j?+"rooo=184M Moladty of Ihe solution !+3$ x ,0oo = o.oeo M.
-
Applying M1V1 = M2V2, 18.4 x Vt = 5 x 0 500 7. lmo mL of o. 150 M NaoH c{nrain NaoH
or Vl = 0.1361- = 136 cm3 = 0 150 mol = 0.150 x 40 : 6g
4. Molecular mass of BaCI2 = 137 + 7l = 208 u. re. 6 gin 0 150M MNaOHsolurion
= 1000 ml.
. 0 184 g in 0 150 M NaOH soturion
I.or 1000 cm3 of 1 M Baclz sol., mass of BaCl2
1000
necded = 208 g = -;- x 0.184 = 30.7 mL.

' l lamu(orlu)=#rhofmassotanaromofc-12=$g.ftaris*hyIirmuorluisarsocaflcdlAvogram.
l\o -
2 The number of molecules presenr in 1 cm3 of an idear tas at srp is calred t schmidt number.
rrsvatue = !+ftP = 2.6e x lore.
1146
l1'arlaaS,'5 Neut Course Ch.-itt glfrm
tta ; b| i6: Y tix ii:rirvoirlED 6E-t6'diNfD::r:
::

.1 r\s ionic comPounds are not molecular, lhe terml[ormality, is used in plac of molaty to.exPress the
concenrratio[of thel t solltion. Fotmality is the number of formula weights present in one lifie of lhe sol tion.
No ot formura wcish'' = #*T*#;##H**
ii J Molarity of a solulion does not change wth temperature because it involves masses of the solute aod
Normalityand molarity changewith temperatule because they
solvent
involve
which d; not ohangewirh temperatuie.
volumes which change with tcmperature
:5. Standirrd solutior. A solution whose normality or molarity is koo$'n is callcd a standard solution

, ,',,;, : tt-:'t::: I I :::il:r::')" :i lir

::r

SECTION_\'II Step l. Calculate the molecular mass of the

compound from its formula by adding the atomic
PERCENTAGE COMPOSITION masses of the elements Present.
AND IVIOI ECULAR FORtr,TULAE
Step 2. Calculate the Percentage of the ele-
1.30. Calculation oI Percenlage ment or ihe constituent by applying the following
composiiion lrom Fotmula relation :
Percentage of the element or constituent
No. of parts by mass of the
elomont 0r constituont x 100
ofthe compound.ll can bc cirlculatedby tle follow- Mol. mass of thc comPound
ing two steps :

SOLUED EXAATPLES
IiXAI\{PLE l. (:okulate the perxentage com- Solutioo. Mol. mass ol (luSOo . 5 HrO
position oI the vaious clenrenls in MgSO,
=63'5 + 32 + 4x 76+ 5 x 18 = 249 5
Solutlon, Mol. mass of MgSOa
No. of parts bY mass of H2O =5x 18 = 90
=24+32+4x16=72.4
vo of Mg =.'#f H::i:ffi:'r$;"- " r,
... voorHro = ff3, ,*
= 36'079a.
=fi.rn=zou" l.l.\d\tPl l'l -r. Calculate the percentage of cat-
ion in ammonium dichrcmate.
Solution. Molecular formula of ammonium
zors=ffffi$ffiffixroo dic (NHn)rCrrOT

Mol. mass of (NHo)2CrrO7

no :26'67vo
fix =
= 2 x (14 + 4) + 2 x 52 + 7 x 76 = 252
%oro=\H**ffi#xrco No. of parts by mass of cation viz NHa+

# =2xGa+q=X
= t2t x 100 = 5! 33%,

l.-\.\,\I PLl'l l. Calculate the percentoge ofwater

'.7oofNHn+ =fn"m=ff
of crystallisation in the samP:e of blue vitriol
(CuSOo. 5 HrO). = 14 29Vo.
 SOME BASIC CONCEPTS IN CHEMISTRY 't
147

FORI :CiE';
l. "P..O?LEMS
Find the pcrcntage qjmposition of potassium
chloratc (KCIO3).
4A sample of clay is found ro have the formula
AJ2O3 . KzO . 6 SiO2. Calculate the percntage of
I
rrr. K = 31 t47o, Cl = 2E 9aio, O = 39.taCol alumioa (Al2O3), F,orassium oxide (KzO) and sitica
2. C.alculate thc percenrage of (i) SO?- (x) H2O rn (sio2) in the sample. [ ,\n..Al2or=lt.3s%,
pure cq/stals ofMohr salt vtz.
K2O=16.90yo, SiO2 =64. 7 S%l
FeSO4. (NH4)2SO4. 6II2O.
5. Fe2(SOa)3 is used in water alld sewage treatmenr
I r". SOI- = 4t.9yEo,HzO = 21 ssEol to aid the remo\,ral of suspnded impurities. Calcu-
3. Calculate the percentage ofwater of crtsrallisahon late the mass pcrcenlage of iron, sulphur and
in rhc samplc of washing soda, Na2CO; . l0 H2O. oxygcn in this compound. ,!NC,E.RA_-
l \F 62.94Ea1
[ \n\ Fe = 2t%, S = 24%,O = 48Col

H I N T5 FoR DIFFI cul:r ?r<oe.LErv,o

1. Mol. mass of KCIO3 = 39 + 35.5 + 4a = n2.5. -. voorNro,-ffi \ too - tB3sqa
E" ot K =
# 5x rco. Ea or ct=
#i,,oo.
%oro=ff1xlrlo
V. ot Kro =
lfi x too = 16 .soEo

%ofsior=ffix rco=64.75%
2. Mol. maes of FeSOI . (NH4)2SO1 . 6 H2O
5. Mol. mass of Fez(SOa)3
=56+32+ 64+36+32+@ + 108 = 392
=2x56+(32+64)x3=400
ot Hro = x rco = zi.ssEa
vo
ff E"orFe=# xfio -- 28qo
2 (3?-+ 64)
% of Sol... - x fio = 48.98%
4. Mol. mass of Al2O3 . K2O . 6 SiO2
r.ors=31# xrco=24%
= (2 x 2? + 3 x 16) =(2x39+16) +6 (2a+2x11) ..",o=o "-if6"t x too = 48o,0.
=102+94+360=556

1.31. Empirical and Molecular Forrnul6q

"'"r ,,t, Empirical Formula, rhe qrrryfuiautqorr|$tq oIt
computtd e1prrrlrs tlu sinp&rrt wl*lc nuirber
ruIb q fie afrr',5,{.tltG varfur/(r,,abxiiU pmnu in
otv ,ttot*ub of tlE compoard.

n of one molecule of the

nunrber and kinds of
present in its molecule.
The question is How are these formulas deter-
-
mined ? The determination of the formula of a
substance involves first the determination of its
'Empirical Formula, and then the ,Molecular
Formula-- Let us now explain what we mean by
these different types of formulas aud the method
of their calculation.
1l4A
Netl Course

tf a it. Thus, for glucoso (E.F. : CHrO), the cmpirical

Mnlccular I'ormula. The molecularformuht
lormub oJ ils forrnull mass can be calculatcd as follows :
utbcr of atoms Empiricaltormula mass : At. mass of carbon
mclccule of thz + 2 x At. mass of hydrogcn + At. mass of orygen
compound. :72.0\+2 x 1.0u+16 0 u :30 0u.
For example, the molecular formula of ben-
zene is C5H5, that of hydrogen peroxide is HrO,
The empirical formula of a chemical com-
and that ofglucose is C.HrrOr. pound can be deduced from a knowledge of the
This suggests that one molecule of benzene (a) percentage composition of different ele-
contains six itoms of carbon and six atoms of menls, and (b'1 atomic masses ol the elements.
hydrogen, oue molecule ofhydrogen peroxide con- The following steps are involved in the cal-
tiiqs ivo atoms of hydrogen and two atoms of culation of the emipirical formula'
orygen and one molecule of glucose cortains six
Step 1, To calculate lhe relative nurnber of
atoirs of carbon, welve atoms of hydrogen and six
abms o; abmic ratio- Dwide th percentage of
atoms oI orygen.
each element by its atomic mass. This gives thc
1.32. Helation Between EmPirical and relative number of atoms or the atomic ratio of the
Molecular Formulae va ous elements present in one molecule of the
The molecular formula of a compound is a compound.
. simplc whole number multiple oI its empirical for- Perceotage of an element
mula. Expressing mathematicallS
Atomic ratro =;r- ,n"*;iih;;." el...,t
x Step 2. Tb calculale the simplest atomic rutio'
Molecular formula = n
Divide the atomic ratio obtained in step 1 by the
where n is any integer such as 1, 2, 3 ... etc.. smallest quotient or the least value from amongst
When n = 1, Molecular Formula -- Empiri- the vatueJobtained for each element. This gives the
cal Formula simplest atomic ratio.
Whenn = 2, MolecularFormula = 2 x Em- Step whole number
pirical Formula and so on. ratio. Tlte calculated in
step 2 are If not, then -
The value of 'n' can be obtained from the
Molecular mass (a) raise the values to the nearestwhole num-
following relalion, z = ber, oi (a) multiply all the simPlest atomic ratios by
E-Fc"t ffi;ia ."rs
a suitable integer.
The molecular mass of a volatile compound
can be determined by Victor Meyer's nethod or by 4.
Step rmula' Wtile
employing the relation the symbols side bY side'
Now insert the simPlest
Molecular mass :2 x whole number ratio of each element as obtained
mass can, however, be ob-
in step 3 at the lower right hand corner of each
Empirical formula
symbot. this gives the empiical fomtula of the
tained from its empirical formula simply by adding
compound.
the atomic masses of the various atoms present in
THE CALCULATION OF EMPIRICAL FORMULAS

the salt.
SOI\4E BASIC CONCEPTS IN CHEI.4ISTRY 't 149

!9!!iL", Calculation of empiicat formula

Symhol Percentoge
otelements

Sodium Na 29.|t 23
,nir=r* r'26
-
Sulphur s 40.51 32
*ri'='* r.26
t2tu
1.R=',
',

o 3oift t, 1 .89
Oxygen 30.38 16 =I t.2ts-'' 3

Thus the Empirical Formula is NqSrOr.

Iix\\lI'r.r'r1.2'j8gof uranium h/as heated, strongly in a cunent of air The resulting uide weighed
2.806 g. Determine the empiical formula ol the oide. (At. mass U 2jE ; O :
16). :
Solution. Step l, To calculate the percentage of uranium and oxygen in the oxid.e.
2.806 g of the oxide contain uranium = 2.38 g.

.'. Percenrage of uranium = fi* , 100 = 84.82

Hence, the percentage of orygeD in the oxide= 100.00-84.82= 15.1g.
Step 2. Tb calculate the empirical formula

Element Svmhol Perccntsge Aa Erass Ilelstive lro. Simplest Simplest whole

ofelemetrts ofcleErIb ,f atoms. = no.atomic ratio

UraDium U u82 8A
ffi
r1J8
= oxaz o 3562
T.J562 = | 3

o
Oxygen 15. 18 16 = o elezs {ffi=,u* 8

Hence the empirical formula of the oxide is UrOs.

Aluminium = l0.50Ea; Potassium = 15. lVa ; Sttlphur = 24.96Vo; Orygen = 49.92Vo.

Find the simplest formula of the anhydrous and crystalline salt.
Solution. Step l, To calculate the empiical formula of the anhydtous salt
Elemctrt Symbol Percertlgc AL Eass Relative no.
ofelements ofel.merts atoms. =

Potassium K 15 I 15rio 0.39

39 =o ls o:rq - I 1

Aluminium AI 10.50 27
lHo 039
=o.ss 039-' 1

Sulphur n 0.78 ^
s 24 96 32
\'{ =o 6.19 - '
a

Ory8en o 49.92 49.92_ 1 t.

16
t6 --'' ffi=s 8
1/s0 !'rn / o t' 1t'5 Neut Course Chemistrg lffi[fi
Thus the empirical formula of the anhydrous
= 258=474.3t.
sali is K Al 52 Os #"
Step2.To calculate the empiical fomula mass Step 4. Tb calculate the number of molecules of
oI the anhydrous salt. wqter in the hydrated sqlt.
Empirical formula mass of the anhydrous salt Total loss in mass due to dehydration
(KAlS2O8)
: 474'3-258.0 : 216.3't
= 1x 39.0+1 x27.0+2 x 32.0+8 x 16.0
Loss in mass due to ortc molecule of water
= 258.0 u.
: 18.C u
Step3.Tb calculate the empiical fomtula mass
. . No. of molecules of water iu the hydrated
ol the hydrated salr .

Let the empirical formula mass of the samnle=2763-.D

'18
hydrated salt = 100.0 u.
Step 5. Io calculqte the empiical formula of
Loss of weight due to dehydration:45.67o
the hydrated salt.
.. Empirical formula mass of the anhydrous Empirical formula of the anhydrous salt
salt = 100-45.6 = 54.4n. = KAlSzOs
Now, if the empirical formula mass of thc
anhydrous salt is 54.4 that ofhydrated is 100 : No. of molecules of water of crystallization :12
.. If the empirical formula mass of the an- .. Empirical formula of thc hydrated salt
hydrous salt is 258, that of hydratcd is = KAISrO, .12H2O

l.\\l'll'l.ll L-The percentage composition of fenous ammonium sulphqte is 14.32Vo Fe2+;9.20Vo

NHI p; a9 0% SO2n- and 27 57V. HrO. What is the empiicst fomuta oI the compound ?
Sol tioa. Calculation of empiical formula.
Formula of Percentage Mol. mass/Al mas.s ReletiYe no. Simplest ratio
Percentxpe
the con6tituent ofconstituents or constrtuents =Eol:Effi ofcor!stituents

,o lu2 o 2557
Iie2+ t4 32 56 = o.zss, o-.Nfr = |
eiSo 0 51I I
NH,* 920 18 = o srrr d.-T.l:t- = "
so?- 0.5104 .
49.0
*9 = o t'oo o-\91 - '
Hzo 2'7 5',7 l8 4d= r szz
r.532
o-.557 = 6

Hence the empirical formula of the compound is

(Fe,+) (NHf,)2 (SO1-)2 (HrO)6 or Fe (NHa)2 (SOa)z. 6H2O.

?ROE,'LEiltv{9 F-O,R
An inorganic salt on analysis gave the follo ing 2. An oxideofnitrogen gave the following percentage
perceDtage composition : composition:
Pb=62.6,N=4.4,O=29 N=25 94
What is empiriclformula of rhe compound ? Also and O = 74.06
Dame the compound. (AI. mass Pb = 207, N = 14, Calculate ihe empirical formula of the compound.
o= 16). I rrr., PbN2o6.Pb(No3)t, r-ead Ditratel trr. N2O5l
I
 SOME BASIC CONCEPTS IN CHEMISTRY 1151

3. A sample ofsalt has rhc following percntage com- Calculate the simplest formula. (At. mass of
posltlon: ME= ) [.\ns. MgSO. . 7H2O]
Fe=36 76;S = 21 11 and O=42 14
5. Calculate the empirical formula of told chloride
C-alculate the empirical formula
of the c.ompound. which conrains 35.1% ofchlorine. At. mass of Au
(At. mass Fe = 56, S = 32 and O = 16) = l9'7 - [ \n\ AuCI3l
[,\tr \. FeSO.] 6, Calculate theempirical formula ofa mineralhaving
4. A salt containing water of crystallizarion gave rhe the followrng composition :

following pcrcentage composition : CaO = 4a.OVo ;PzOs= 41 37a ; C-aCl2 = 10 '?%

Mg=9 76; S= 13 01 ;
[,\rrs. 9CaO. 3prOr. CaClr]
O = .01 aod }{rO = 51.22

4.
Con- Eoage Atomic Relaive no. of Simplert . Empirical Formula = Mgsoa . 7 H2O.
shtuenl nasslMoL cotlitti@nts Ratio 6.
m(us Vo
= Mo-l ,.ass Con- Voage MoL Relalive no. of const- Simplest
Mg 9.76 24 9 7624 = 0.407 1
tfihtenl nuus Vo Ratio
= M;1. moss
s 13.01 t3.ot12 I
Cao 48.0 56 48 0/56=0 857 9
=O 407
o 21.o1 l6 .ov16 4 Pzos 41 3 142 41 31142 = O.291 3
=1626 C"C\ 10.7 11i 10.7/111 = 0.()1b 1
Hzo 51 22 t8 sl.zaB 7
= 2.846
Empirical Formula -9 CaO.3 prO5. CaClr.

compound from the given dala'

The molecular formula ofa compound can be
deduced from its (d) Determination of the value of tt' by using
(l) Empiical formula and the relation,
(2) Molecular mass. T\e determination of Molecular Mans
molecular formula involves the following steps ; n= Enpincat Fo^rula Ma",
(a) Calculation of the empirical formulo from
' (e) Detemination of the moleculu
the pircentage composltion- lomula by
using the relal,ion
(b) catculatton of empiical fomula mass by
addingihe atomic motirt ilolt thi oto^, pr"iiirii , Molecular Formula-n x Empirical
mula.
For-
the empiical formula.

f" R@_. E,Lp,g46. ON rH E C A L C U LAI O N O F M O L E C U LA R F O R M U LAS

1. A compound containing oJ lhe crystalline salt ? The moleculat mass of the

hydrogen and orygen gave the Iot_ crystalline salt is 322.

:
analysis :
- Step l' Zo calculate the percent-
Na 14.28Vq S : 9. 92Vq H : 6.2Mo age of orygen. The given compound contains
Calculate the oxygen but its percentage is uot giveu. This can,
hydrous compound,. howevef, be calculated by subtracting the sum of
the compound are percentages of Na, S and H from 100 as shown
orygen as wakt of crystollizttion, what is the sfittctwe below :
1152 Pradeay's Neut Coqrqe Chemistrg W
Sumof percentagc composition of Na,SandH = l4'?S+9'92+6'24=3O'4O
.'. Percetrtage of orygen = 100'00 - 30 ,10 = 69'60
Slcp 2. Tb calculate the empiical fotmula.
Element SyrEbol l'ercentage At mass RelBtive no. Simplest SiEplestwhole
ofelement ofelement ^
ol,lorrs. = _-:a
Percentaae
atomlc ratio no. atomic ratio
/\i- mx\s

Sodium Na M.2A B lff =o ez

0.62
O:1T =
^
Z

a. q, o 31
Sulphur s 9.92 32 -ff=o tr 0.31 - ' 1

Hydrogen H 6.20 1
*= u^ # =ro 20

u'ru* o t
Orygen o 6960 16 = #?i =,0 t4

Hence the empirical formula of the com- Slep6. Tb calculate the numbet of molecules of
pound is NarSHrrOlo water of cryslallizattoz. Since all the H-atoms are
Step 3. 7o cdlculale the empirical fotmula present in thc form of H2O, 20 atoms of hydrogen
mass. Empirical forrnula mass of the compound would combine with 10 oxygen atoms to produce 10
(NqSlIr6O,a) molecu.les of HrO. Thus, the number of molecules
= 2x 23.0 + 1x 32.0 + 20 x 1.0 + 14 x 16'0 of water of crystallization present in the salt
.taa NqSH26 O1a is 10.
-
SIED 4. Tb calculate the value of 'n' Stfjp7 .'Io detetmine the st acture of the crystal'
: mass
Molecular 322
Ime Jarr. Out ofthe 14 oxygen atoms, 10 are present
= ,o= '
' E.piri";l for.ul'u -r.. in form of HrO. The remaining 4 must be a part of
Step 5. Io calcul0te the molecular formula of
the compound. the salt consisting of Na and S. A plausible formula
Molecular formula = z x Empirical formula for this saltis Na5SOo and that of crystalline salt will

= 1x Na2sH2oolo = NarSllro or. be NarSOo .10HrO

!r\ \ttlrl,l- 2. An oryanic substance containing carbon, hydrogen and orygen gave the following
pe rc entage c omposition.
C :40'687Vo;H=5'065Vo and O =54 228%
The vapour density of the compound is 59. Celculate the moleculor lormula of the compound'
Solution. Step l. Tb calculate the empiical formula of the compound-

Element S!mbol Percent!ge AL mass RelstiYe no. Simplest Simplest whole

oI- atoms, =
Perce[taae
ollerDent ofeleEert -m;;a;- atomlc ratio no,atomic r0tio

oolf7 3.390 _
)
Carbon C 40.68',1 12 = z.tso 3.389 -'
5 985 5 .085
Hydrogeo H 5 .085 I = s.oas T3EEi =I) 3

sar? = z 3 389 _
2
Or(ygen o 54.m 16 zee TTtrq= I

. . Empirical Formula is C2H3C),

SOIVE BASIC CONCEPTS IN CHEi/ISTRY 1153

Step 2, % calculate the empiical lormula Mo$cular mass :2 x vapour density

mass.
Zx 59 = l1.8.
The empirical formula of the compound is Step 4. To cala/lafe he value of 'n'
QH:oz. Molecular mass
: E;piriaro;ul";G= 118
. . Empirical formula mass
= (2 x. t2) + (3 x 1) + (2 x 16)
n
6 ='
= s9. Strp 5, To calculate the molecular formula of
Step 3. Tb calculate the moleculat mass of the
the salt.
sak.
The vapour density of the compound
Molecular formula = r x (Empirical formula)
= 59.
(Given) =2 x c.HrO2 =crl{ior
Using the relation between vapour density Thls the moleculor formula is CfirOa.
and molecular mass -

?RACTICr-
l. A cr,stalline salt when heatcd becomes anhydrous 5. A chemicalcompound is found to have the follow-
and lo6es 51.2% of irs weighr. The anhydrous satt ing composition :
on analysis gave the following percentagc mmposi- C = 19.5'1Eo ,Fe = 15.2% ;N = 22 83 %;
tion:
K= 42 19%
ME = ?n OEo ;S = 26 66% arfi O = 53 31% Calculate the empirical formula of the compound.
Calculate the molecular formula of the anhydrous What will be itsmolcc'ular formu la if lhe molecular
salt and the cr)6talline salt. Molecular mass of the mass of the compound is 368 ? Name the com-
anhydrous salt is 120. [,tDs MgSO..7H2OI pound and describe the action of hydrogen
2. A mmpound cootaioing carbon, Irydrogen and perqide on it. [ \ns. K.I'e (CN)61
oxyBen Save the following aDalytical dara :
. 6. But ric acid contains only C, H and O. A4.2A mg
C = 4O O% aodH = 6.61% sample of bur,,ric acid is completety burned.It gives
Calculate the molecular formula of the mmpound 8.45 mg of COz and 3.46 mg of HzO. The
ifits molecular mass is l8O.
[.trs. C5H12O5] molecular mass of buqric acid nas determined by
3. On analysis, a substanc! was found to have the experiment to be 88 amu. What is molecular for-
follo iDg percntage composition : mula ? INC-U-T.) [ \,'s. c.H!o2l
K = 31.84, Cl = 28.98 and O = 39.18 . 7. A welding fuel gas contaios carbon and hydrogen
Cllculate its molecular formula if its molecular only. Buming a smau sample of it iD orygen gives
mass is 122.5. 3 389 carbon diuide, 0 690g of water and Do
[-rrr. KClO3l other products. A volume of 10.0 L (measured at
4. An organic liquid having carboD, hydrogeD, S.TP) of this \+plding gas is found to weigh 11.6g-
nitrogen and orygen was found ro contaiD C.alculate (i) empirical formula (ti) molar mass of
C=41.37%; H =5.757o; N = 16.09% and rhe tbe gas, and (rii) motecuhr formula. (N.C.E.R.T)
rest orygen- Calculate the molecular formulaof the
liquid if its VD. is 43.3. ['rrr.. (4 cH (i0 26 (iri) crHul
[,\)s. CaHrNO2l

2UCr t LEMs
1. Calculate the empirical formula of rhe aDhydrous . 120 g ofanhydrous salt contains ll2o
salt. It comes out to be MgSOa. E.E mass = 120.
Mol. mass = l2n. }Iencf,- molec'ular formula = =
ffi , rrr, = 126 g =
#motecules
MgSO1.
= 7 molecules.
As crystalline salt on becoming anhydrous loss Henc mol. formula ofcrlstalline salt
51 .
2% by mass, this means
,ltl =MgSOr.7HzO.
8 g of anhydrous salt cootains HzO = 5l .2 g
1154 Pralct l,'s Neut Coarse Chemistrgdffi)

5. The molecular formula &FoC6N6 suggests that it .. %ofo = 100-{5a 4+ 9 1)=36 5%

is Poldssium lenocyan dc. It is oxidised by H2O2 to Calculate E.Il If comes out to be qH4C).
potassium ferric,'anide. E.E mass = 44 u, Mol mass = 88 u.
II2O2.+ HzO+O l{encr=Mol.mass/E.Fmass=2
2K4 [Fe (CN)6] + O+ HzO -......- . Mol. fo.mula =2x E.E = CaHrO2
2Iq [Fe (CN)6] + 2KOH 7, Amount of carbon in 3 389 CO2
6. 1 mole CO2 cootains 1g atom ofc =4;x3.38s=0 9218 8
i.e. M g COz coltaiIrs C = 12 g
Amoun t of hydrogen in 0 . 690 I H2O
.. 8.45 mg Co, willcontain C = 12 x a ls mg 7
= -+ x 0.690 8 = O-0761 I
This is present in 4 24 mg ofthe compound. As compound cootaios only C and I-I, thercfore,
.. Toof cinthemmpouno= jlxffixroo total mass of the compound
=o 9278 + 0 07678=0 9985 g
= 54 4Vo 7., of C in the compound
or use the formula directly =ffi" too = s2 32
,. Mass of CO"
'1o otc - 44Y
x grg o1.o,nro166
x loo % ofH in the compouno = ffi x loo = 7 68

Similarly, % of H Now calculate empirical formula. It comesout to

be CH.
, Mass of H.O
= -1
'18x =-----.------:- x 100 * rr'n = 26 t mot-l
Mass ot compouno Molar mass =
ffi
E.E mass = 13 . z = 2. Henc.e M.E = Cztlz
= i,?# " 1oo = e.tvo

trsually no direct method is used for finding the pErcntage of oxy8en in a compound. It is calculated by findiD8
the percnta8es of all elements except o,ry8en. Then %age of ory8en = 100 (Sum of Toages of all other
elements present in the compound).
-

SI'CTION_VIII CaCO, + 2HCl

I Mole 2 Moles
STOICHIOMETRYOF 40+12+3x16 2(l+3s.5)
CHENIICAL REACTIONS =100g =118
CaCl, Hzo coz
Molc1 1 Mole 1 Mole
One of the most important aspects ofachemi- 40+2x35.5 2xl+16 12+2\16
cal equation is that when it is written in thebalanced =1119 =189 =449
form, it gives quantitative relationships between thc or 22 4 litrcs at STP
various reactants and products terms of moles, il Thus, (i) 1 mole of calcium carbonate reacts
masses, molecules and volumes. This is called with 2 moles of hydrochloric acid to give 1 mole of
stoichiometry (Greek word, meaning'to measure an calcium chloride, 1 mole of water and 1 mole of
element'). For example, a balanced chemical equa- carbon dioxide.
tiotr alongwith the qualtitativ information con- (li) 100 g ofcalcium carbonate react with 73 g
veycd by it is given below : hydrochioric acid to give 11i g of calcium chloride,
SOI\,IE BASIC CONCEPTS IN CHEMISTRY 1/s5

18 g of water and ,14 g (or 22.4lilres at STP) of l.))t{\ I l'l-l,l 2. l hat mass oJ slaked lime would
carbon dioxide. be required to decompose completely 4 grams of
The qua-ntitative information conveyed by a qrnmonium chloide a.ad what would be the mass of
chemical equation helps in a number of calcula- eqch ptoduct ?
tions. The problems involving these calculations Solution. The equation reprcsenting the
may be classified into the following different types : decoffFoJtlon of NH.CI by slaked lime, i.e.,
(l) Mass-Mass Relationships i.e. mass of one Ca(OH), is,
of the reactants or products is given and the mass
of some other reactant or product is to be calcu-
ca (oH)2 + 2NH1CI CaCl,
latcd. 40+2 (1+16) 2 (r4+4+35 5) 40+2x35.5
=749 =1079 =1118
(2) Mass-Volume Relationship i.e. masV
volune of one of the reactants or products is given + 2NH3 + zH2O
and the volume/mass of the other is to be calcu- 2(r4+3x1) 2(2t1+16)
lated. =ug = a

(3) Volume-Volume Relationship i.e. volume of (i) calculate the mass of Co (OII), required
To
one of the reactatrts or the products is given and the to decompose 49 of NHoCl.
volume of the other is to be calculated.
From the above equation,
The gencral method ofcalculations for all the
problems of the above t,?es consists ofthe follow- 107 g of NH.CI are decomposed by 74 g of
ing steps : Ca (oH),
(i) Write dowtr the balanced chemical equa- . . 4 g of NH.CI will be decomposed by
tion. 'fa
(i) Write the relative number of moles or the
relative masses (gram atomic or molecular rnasses)
G, o= 2.76gof Ca(OH)2
Thus the mass of slaked lime required
of the reactatrts and the products below their for- :2.766 s.
mu.lae,
(ii) To calculate the mass of CaClrformed,-
(ili) In case of a gaseous substance, write dJwn
?2 4lrtres at STP below the formula in place of I 107 g of NH.CI when reacted with Ca(OH),
mole. produce 111 g of CaClr.
(iv) Apply unitary method to make the re- . . 4 g of NH.CI when reacted with Ca(OH),
quired calculations.
Now we shall tale up a few solved examples will produce
to illustrate the different types of problems.
#"o=415gofcacl,
t'l l'[, L lnvohirlg ]lass-l\lass Rrlatiollship Hence the mass of CaCl, produced

I i\,\1I l'Ll.: L Calculate the mass of ironwhich = 4.15 g.

will be conveted inlo its oxide (iii) To calculate the mass of NHrproduced.
(Fe ,O ) by the action
of 18 g of steam on it. 107 g of NH,CI when reacted with Ca(OH),
Solution, The chcmical equation repre- give 34 g of NH, .

sentin!-tEe-reactionis . . 4 g of NH4CI when reacted with Ca(OH),

3.1"-_
- X 56
+ 4H2O + Fe3C)a + 4H2
will produce
3 4X 18
= 168 g =ng 1t
I.271 gofNH,
Now 72 g of steam react with 168 g of iron ;.r4=
Hence, the mass of NH, produced
.'. 18 g of steam will react with
=1.277 c.
(iv) Tb calculate the mass of H.O fotmed
ffr:n= 42 s of iron
107 g of NH.CI when reacred with Ca(OH),
Thus the mass of iron required : 42 g. yield 36 g of HrO
 1/56 Neut Course Chemistrq
.'. 4 g of NH.CI when reacted with Ca(OH)2 (i) 2Al + 3H2SO4 ........- Al, (SO.),
g
2x27=s4
winfiefd= x 4 = r.345EgofllzO +
ffi 3Hz
3x2=6 g
Sothemassof HrO formed = 1'345EC.
, (ii)
' Zr + H2SO ----------- ZnSOo + H,
. .1r l)XAlvtPl,li 3. 1,5 gol an impure sampk of 658 2A-
' i sodium sulphate dissolved in water was trcated with
acess of baium chloide solution when 1'74 g of
Fe + HrSOo
0lr) 568 -------- FcSOo * H,
2g
., . BaSO rwere obtained os dry prucipitate. Cal&late lhe
'' percentage puity of the sample. Let us supposc that the amount of hydrogen
to be prepared = 100 g.
Solution.
Step l. Tb calcula.te the cost of pleparation of
Treated with 100 g of Hrfrom Al
Giventhatl59 l'74got
of impure Baclz gavc BaSOa 6g ofH, is prepared from Al = 54 g
NarSOo . . 100 g of H, will be obtained from Al
The chemical equation representing the reac-
tion is :?54 x 100 = 9100 g
NarSOa + BaC! --:- BaSOo
Cost of 1.000 g of Al : Rs. 20
2x23+32+4x16 137+32+4><16
= 1428 =233a )i
.'. Cost of 900 g of Al= x 900
Saep l, Tb calculate the mass of NarSO ofrom l0O0_:

1.74 g of BaSOo. From the chemical equation - = Rs. 18

233 g of BaSOo are produced from 142 g of Slep 2. To calculate lhe cosl of preparulion of
100 g of Hrfrom Zn.
NarSOa
2 g of H, is produced from Zn : 65 I
.'. 1,.74 g of it would be obtained from
1L) .'. 100 g of H, will be obtained from Zn
fix r7a = r'06g
The mass of pure NarSOo present in 1 5 g of =;65 x 100 = 3?50 s
impure sample : 1 06 g.
Cost of 1000 g of Zn : Rs. 16
Step 2. Io calculate the percentagc Puity of
impure sample. .. Cost of 3250gof Zn=ffix3250= Rs.52.
1 5 g of impure sample contains 1 06 g of
pure NarSOn St p 3. Tb calculate the cost of PrcParation of
100 g oJHrfrom Fe.
. . 100 g of the impure sample will contain
2 g of H, is produced from Fe = 569
= +ff , lm = 70.67 s of pure NarSOo .'. 100 g of H, will be obtained from Fe

Percentage purity of impure sample = 70'67 =;56 x 100 :28wc

I'.X \IPLli {. Crrent market pices of Al, Zn
and Fe scraps per kg are Rs. 20, Rs. 16 and Rs. 3
Cost of 1000 g of Fe = Rs. 3
respectively. If H 2 is to be prePared by the reaction of 1

would be the
.'. Cost of 2800 g of Fe = ,*_- x 2800
one ol these metals with H plO 4
'9hich
cheapest metal lo use ? Wich would be most ex' = Rs. 8.,10.
pensive ?
Thus Fe is the cheapest ald. Zn is the most
Solution. The various chemical reactions in- erpensive metal to use for the preparalion of H2.
volve n below :
 SOME BASIC CONCEPTS IN CHEMISTRY
1157

. In order to find the strength of a . . .r g of CaCOj will give

sa aci4 lqgweru dilutedwith watet
'weighing 56 xr
and a piece of marble 7 g placed inlyhen
it. -roo- = o s0 xxgofCaO
all aclion had ceased, the mable was rerioved,
washey' died and wos found to weigh Thus the mass of CaO formed = 0.56xg
2.2 g. Wat
was lhe percentage strcngth of sulphuic acid. ? Step 2. To calculale the ma$s oI MgO residue
Solution. Mass oI marble ta_ken = 7.0 g. from ( I . 84 - x) g of magneium carionit" -
Mass of marble left unused = 2.2 g Using the equation
. Mass of marble reacted = j .0 2.2 MgCO, MgO + CO2
.
- UE 408
= 4.8 g. -'
84 g of MgCO, upon decomposition yield a
The chemical equation involved in the above
residue of ,10 g of MgO
problem is
. . (1 .84
CaCO, + H2SOI - -r) g of MgCO, will letd
40+12+16x3 2+12+4x16 g of MgO
=1009 =989
CaSC)a+H2O+CO2 Thus the mass of MgO formed
Step 1. Io calculate the mass of pure HrSOo AN

required to react with 4 .8 g of marble.

= *- (1 84-x)8.
100 g of marble react with HrSOo Step 3. Tb colculate the masses of CaCO3and.
= 9g g
.'. 4.8 g of marble will reacf with HrSOo MgCOrin the mixure.

Total mass of the residue -- 0.96 g.

= __ x 4.8 =
98
4.7049. Equating the total masses of CaO and MgO
-
from Srep I
Step 2. To cqlculate the strength of sulphuic
and Step 2, we have
-
acid.
10 g of dil. H2SOa contaiD pure HrSOo
0.56r +
#(1 84 -r) = 0.e6
: 0.56.rx84+40x7.84-rl0x= 0.96 x 84
4.704 g.
.. g of dil.
or 47.04x - 40x = 80.64-73.60
100 H2SO4 will contain pure
or 7.04x= 7.04 or x= 1
4.70,4
H2SOa = -16- x t00= 47.04 Thus the mass of CaCOa in the mixure
: 1 .00 g and the mass of MgCO, i.n the mixture
. Thus the percentage strength of sulphuric
.
acid : 47 .O4. :1.84 - 1.00 = 0.E4C.
r I'l\.lr\ll)l.li r'. 1.64 g ol a mitture of CaCO, % of CaO, in rhc mixrure = , ,,
and MgCO, is strongly heated tilt no Iwther loss of #
mass tqkes plqce. The residue weighs 0.96 g. Calcu-
= 54.35
late the percentage composition oI the mixturc.
Vo ot MgCO, in the mixture : 100 - 54 . 35

Solution. Let the mass of CaCO, in the =45 65

mixure ber g.
. . The mass of MgCO, in the mixure will be
heatedbelow 600"C until the mass of the residue was
(1 8a-x)g. c.ons_iant. lf the loss of mass is 28Vo,'find the mass oI
Step 1. Io calculate lhe mqss of CaO residue lead nitrate and sod.ium nitratc in the mixnre.
from xg calcium carbonate. (At tlts. of Pb = 207, Na :
23, N 14, O: 16) =
CaCO, CaO + CO. A
100 r 558 Solution. 2 Pb(No3)2 2 pbo
.'. 100 g ofCaCO, upon decomposition give a 2 x 331=
--.
6628 2x223=4469
residue of 56 g of CaO + 4NO, I +q I
 1/58 Neqr Course Chenr istr\l
A
Stcp 2. Tb calculote the votume of COz at 27.C
NaNO.
2 2 NaNO2 + Oz I
2x85 = l10g and 746 ,
7 mm pressure
2x69=138E
Initial conditions Final cortditions
Suppose Pb(NOr) in the mixture = ,I g
Volume V, = 2240cm3 Vz: ?cm3
Then NaNO, in the mixture = (5 - x) g Pressure P1 = 760 mm Pz=7467-26'7
662 g Pb(NO.), give residue = 4,16 g
= 720 mm
Tcmperature T1:273 K 'fz : 27 +273:3N)K
x g Pb(NOr), will give residue =
#." t f By the gas equation, wc have
= 0.674x g -
L70g NaNO, give residue
V2 x 72fr _ ZZtfr x 760
= 138 g
300 273
(5 - x) g NaNO, will give residue
_. 2240x760x 300
vr=ff -zzo = 2598..r cm:

"o-
x) c, = 0.872 (s
= i# - x) c
Thus the volumc of carbon dioxide
Actual residue obtained
= 25983 cm3.
_24 I'l\ \i\lPLI,I9. 1.0gof amimtre of cqrbonates
=5-1OOx5=1.68
of calcium and magnesium gave 240 cm3 of CO, at
.. 0'674x + 0'812 (5-r) : 3.6 STP Cslculste the percentage composition of the
or0 138x:0.216 mixture. (West Bengal J.E.E.2003)
or x = 3.339 Solution. Mass of mixture of carbonates of
Pb(NOr), in the mixure = 3 .33 g
t'.e. Ca and Mg taken = 1.0g

NaNO3 in the mixture : 5 - 3.33 Let the mass ofCaCO3 = rg

. . Mass of MgCO. = (1
= 1.67 E - r) g
-lYPIi ll. Inrolving Mrss-\'ol tnc l{clirliorrslrip The chemical equations involved are :

CaCO3 """""'+ CaO + COz ...(,

, li\A\Il,l,l.l 8.
What volume of cafion dioide 40+ 12 +3x16
224tm cm!
measured at 27"C and 746.7 mm pressure $)ould be = 100 g at STP
obtained by treating 10. 0 g of pure mafile with dilute
hydrochloic acid ? (Aq. tension at 27'C is 26.7 mm).
MgCO: -----------r MgO + CO, ...(ii)
u+12+3x16
Solution. The chemical equation repre- =849
22400 cfi1
at STP
sentin[lf, E-reaction is -
Slfp l. Tocakulate the volume of COrevolved,
CaCO, +2HCl-..........' CaCt+HzO + COz
looc at STP from x g of CaCO ,.
:
""1T#" L00 g of CaCO, evolve COz at STP 22400 cm3
Step l. Tb calculate the volume of COrevolved . . x g of CaCO, will evolvc CO, at STP
from 10 g of CaCO, at STP.
From the chemical equation, : z?ff xr" '= z24xcm3
100 g of marble react to produce 22400 cm3 of
CO2 at STP Slep 2. Tb calculate the volume of COrevolved

. at STP from ( 1 -x)g of MgCO..

. 10g of it would produce
))tnn li4 g o[ MgCO, evolve CO, at STP = 222100 cm3
::IjY - i^- rTrn"^J
. . (1
- x) g of MgCO. will evolve CO, at STP
This is the volume of CO, evolved at STP
=ryx (1 -x)cm3= $tr-,)"-,
 SOME BASIC CONCEPTS IN CHEMISTRY
1159
Slep 3. Tb calculate the value of x
. . Total volume of CO, evolved at STp
2qH2 + 5(),----------+ 4CO2 +ZH|O
2 Vol. 5 Vot. 4 Vol
= 224x * ${r -r)"., Step l. Tb colculqte the volume of Oz qt STp
rcquiredto effect complete combustion of 200 cm3 ol
But total yolume of CO, evolved at STp qcetylene.
= 240 ct# (Given)
- Applyrng Gay Lussac,s Law o[ gaseous
.'. z24x+
S tr -..1 = zlo.
volumes,
2 Vol. of CrH, require O, for complete com-
or 672x+800-&00x=720 bustion : 5 Vol.
or 128.r = 80
. . 200 cm3 of CrH, will require O, for com_

.'. ,= IIt plete combustion = ] x Zn = 500 cm3 ar STp

Thus the volume of O, required

. StrD 4.'fo cslculate
ol"lhe mulutc
the percentoge composition
= 5fi) cm3 at STp.
.. Percentage = ,fi x fOO
ofCaCO, Step 2. To calculate the volume oJ CO,
produced at STP.
= 62.5 Applyrng Gay Lussac's Law
.. Percentage of MgCO: = 100-62.5 . o[ gaseous
volumes,
= 37.5 2 Vol. of CrH, produce CO2 = 4Vol.
. . 200 cm3 ofCrH, at STp will produce CO,
orrgen at sTP
l
ustion oI 200 = ,'2[n = ul00 cm3 at STP
the volume of
Thus the volume of CO, produced
The chemical equation repre_
sent bustion of acctylene is = 4fi) cm3 at STp

9 FOP.- $T1{ I
rate of 25 paise per kilogram to mmplete ly
Deutral-
1. ize 7 kt of caustic poksh ?
[-r,1.. Cct olIICl = Rs, S.70, Coet ofH2SO.
= Rs. f,9fl
3 NO2 (8) + H2O (0- 2 HNO3 (4C) + No G) ? 5. Frxcess of AgNO3 solution nas added
to 2.2 E ot
commercial
water. The
ciloride was
collrmotr salt

decompose 50 g of chalk (calcium carbonare). 6. A sample of dolomite @fiained, 45 of

CaCO3,
40% of M1CA3 artd,15% clay. Calc,ulate
rhe mass
4. which is cheaper: 1# ?l:lrtpluJrc 1c!d of
srrengrh 30
required ro reacr
rate of50 paise pcr the completety witb l0 g of the sample.

[,a1". 30'27 91
1/60 Pradeep's

P;R rf,f pE- lRo ALEM5 qp N rP

" Calculate rhe mass of graphite that must b
7. bumt 14. 2.50 g sample ofsodium bicarbonatewhen strongly
to pJrc" r:.2 g or Cbr. [,r,rs, 3.6 gl heated gave 300 crn3 of co2 measured at 27' and
otculate the pcr
6. one sram of a mixture of potassrum uno rool,, 3f?#33';l:*" ff;flrHl
chlorides on rreatment with excrss of silver nitratc 15. phide(s 2.63)
garr 2 g of AgCl. What Eas the comPosition otthe 'rotumi ultini
tu/o salts in the original mixture ? 25 il
[41t5. Nacl = lA%'KCl = E6%l a 16. The drain cleaner, Drainsx conkins small bits of
aluminium which react with caustic soda to
Droduce trydroqen, What volume of hydrogen at
9,
loeC anO 6ne tlr will be released whcn 0 15 I of
aluminium reacts ? (1VCEn.I)-[,r.ns 203 0 nl]

10. What mass of iodioe is liberated from I solution of

Dotassium iodide when I litrc ofchlorine tas at 10' 17. ed in
'C
and 750 mm presure is Passed through it ? o,rygen gas. Calculate the number of moles of
[n15. 10.7t gl CO2 formed. [,\.r)s. 0.25 mole]
11. of chalk (CaCO3) containing clay
I of a samPle
1.4
lt. Calculate thevolume ofair containing 21% oxygen
as imDuritv were treated with excess of dilute by volume at STP, required in order to convert 294
hydro;hbrlc acid. volume of coz evotved when cm3 of sulphur dioxide to sulphur
de uDder
measured at 15'C and 768 mm Pressure was 282 the same mnditions. [
700 cml]
cm3. Calculate the PerceDtage purity of the sample' 19. What volume of a solution of HCI containing 73
[,s.. t5.1%l Mitre would suffic for the exact ralization of
-NaOH
12. How much matble of 96.5Vo purity would be re- obtained by allo ing 0. of metallic
quired lo prepare l0 litres of carbon dioxide at STP sdium to react with uater. s. 10.0 cElI
when thi marble is acted upon by dilute 20. FiDd out the volume of Cl2 at STP Produced by the
hydrochloric acid ? [ 1u(. 46.26 g]
action ot 100 cm3 of 0.2 N HCI on excss of
13. Calculate the volume of SO2 at STP obtained by
MnOr. 1_r,... 112 cm3l
burning 500 g of S containiDg 4% sand by weiSht'
['s' 336litresl

1, 2 molcs of HNO3 are Produced from 3 moles of 40% HCI acid required = a suzs
#,
NO2 . 7 33 moles of HNO3 will be Producd from
= 11 40625 kg
NO,=]x7 33=10 995 moles. cost = 11.40625 x 50p = Rs 5 70P.
2, Fe2Or = 2Fe. 2KoH + HrSOn .. K2SO1 +2H2O
*'jr'uo'i ro 2x55 2x56kr 98 kg
' = ,2c Proced as above to calculate the cost of 80%
.3. CaCo3 I' Hrsoo t 63590 * H2o + Co2 H2SO1.
1009 98g
50 g chalk will require Purc H2SOa = 49I 9. 2 KCIO3 +2KCl + 3Oz

6070 H2SOa requircd =

100
x a9 = El 67 S 2(39 + 5 5 +48) 3 x22 4LatSTP
ff =u5E
4. KOIi + UCI -. KCI + I12O
clz 'zKcl+
56kg 36 5kg 1o'2KI + 12

x I 22.4 Laast? 254 E

Pure IICI and required for ? ke KOH = {f First convert the given volume to volume at S TP
-- 4 5625 kE
SOME BASIC CONCEPTS IN CHEMISTRY
1/61

11. CaCO3 +2HCl CaO, + HrO

100 C -
*
Ptvr
-T1 =T- PzYz

,r* (STP mnditions) (Rcqui( d conditions)

"33?..rr.
First convert the giveo volume to volume
at S.Tp
Calculate rhe mass of CICO3 from whictl this
.=-----TTK-=-z''R--
_
- I arm x 196.7 ml 0.987 atm x Vz

volume ofCOz at S.Tp. is obtained. Then calculale (l bar = 0.987 atnr)

%a$e pvdty.
or V2 = 203.0 ml
12. CaCO3 + 2 HCI- Cael, 1 1116 1 COz
lt. 2 SOz + Oz SO:.
I00 g 22.4 L aast?
O, rcquireO = x z 94 = 147 cc.
10 L of CO2 ar S'fp wi be obraincd from pure |
caco3 =#+ x n = 44.64 E
Air required - ff*ut-too u.
19.2Na+2H2O- 2NaOH +Hz
Impure marble requireO =
ffi x ll .ra 2x21t 2x41g
46.26 = 46C =tOS
= E
NaOH producd ftom 0.46 g Na 0.80I
=
15. l0 nrl of CS2 =10x2.638=26.38 NaOH .{ HCt NaCt HrO
CS2+302 COz+2SOz 40C 36.5 g -
- HCI required for exact DeutralisatioD of 0.80 g
76g 3 moles 3fos
Nu6rH - ,. o.eo g = 0.73I
=3x22.4 L at STp
73 g HCI are present in l0O0 cm3
16. 2Al + 2NaOH+2H-O-
2x278 .. 0.73I HClwill be preseot in 10 cm3
2 NaAlO2 + 3H2 20. MnO2,+ 4 HCt- MnCt2 + ZH|O + Ch
3 x 22400 mt
ar SIP
4x36.5s zz,roolFlisrp
. . H2 produced at S'I? from 0. 15 g AI HCI prcsenr in 100 cm3 of 0.2 HCt
=,oofi'roog"q'Eo 02sq
=3 " ?laoo * o.rs nrl = 186.7 mt
=012x36.5S=0.739

.A few cxamples solved below will hclp to

understatrd the calculatioos more clearly.
EXAIIIPLE 1. Cakium catbonate reacts with
aqueous HCI according to the reaction
CaCO j (s) + 2HCl (aq)-.+
CaCtr(aq) + Co2@) + HzO (t).
What moss of CaCO3 LJ tequired fo react com-
pletely with 25 mL oI 0.75 M HCI (N.C.E.R,T) ?
. To calarlate mass of HCI in
25
10(X) mL of 0.75 M HCI contain HCI
= 0.75 mol
= 0.75 x 36.5g=V4.375,
25 of 0 ' 75 HCI will contain HCI
"' 'nr
 l)ratlct1t : Neut Coerse Ch"-i"trg@
1162
I,lX \\tl'l lr .1. Calculate the volume o10 05M
r!.r1^'!^5
= x ?sp = 0.6844g. KM\O i solution required to oidise completely
1000
j reacling 2 '70 g of omlic acid (H rC rO ) in acidic medium'
Step 2. Tb calculate mass of CaCO
completel! with 0 9125 g of HCI Solution. The equation representing the
CaCO, (s) + zHCl (aq) chemical change is -
CaCl, (aq) +- COz @) + H2O o 2KMnOa + 3H2SOa
----->
2 mol of HCl i e' 2 x36'5g = 73 g HCI react IQSO. + 2MnSOo + 3H2O + 5 (O)
completely with CaCO3 = 1 mol = 100 g H2qO4+(O) ...........' 2CO2+ H2Olx 5
. . 0 6844 g HCI will react completely with
2KMnOo * 3[I2SO4 + 5H2C2Oa .......-
Caco3 =
ff , o ua** = o'936*. 2 moles 5 moles

I.\\tll'l l. 1. Calculate the volume ol X2SO. + 2MuSOa + 10CO2 + 8H2O

hvdrosen liberated at STP when 500 cm3 of 0'5 N
s'ulphiic acid ,eocls with excess of zinc' (H = l, o Step 1. To calculate the number of moles of-
: 16, S = 32). KMnOoiequired to completely ondise 2'70 g ol
Solution. The chemical equation repre- H rC rO o i n aci dic mc dium.
sen(ing the reactior is :
Molar mass of IITQO,
Zn * HrSOo ---------'.. ZnSOI * Hz
x 16 = go mol-l
=e8 0s =1?$,"' = 2x1I+2x12+ 4 og
.. No. o[molesof HrC2Oo contained in 2 70g
Step l. Tb calculale the amount of HrSOo in -.
otit= rfi;fff
Massin erams
=;:= 2'7O
o 03
500 cm3 o[ 0'5 N HrSOasolution.
From the above equation,
Strength/litre of H2SOo solution
5 moles of HrC2On are oxidised by 2 moles
: x Eq. mass
Normality of KMnOn
= 0.5 x 49 = 24.5 gllitre
Now, 1000 cm3 of the acid solution contain .'. 0 03 mole of HrCrOo will be oxidised by
24 5 g of pure HrSOo
2 x 9 03 KMnor
. . 500 cm3 of the acid solution will contain = o.o 12 mole of
5
g : Step 2. ?o calculate the volume o[ 0 05 M
- 'x
24'5
1000
l2'25gofPureHzSor
KMIO a solution .
Slep 2. Tb calculate the volume of H2liberute d
Now, 0'05 mole of KMnOo are contaiaed in
at STP
98 g of HrSO4 react to liberate 22400 cm3 of 1000 cm3 of the solution.

H, at STP .'. 0 012 mole of KMnOo wil be contained ir

. . 12'25 g of HrSOo would liberate H, at STP lffi xo o12 = 2zl0 cm3 ofsolution.
2N *72'25 = 2800 cm3
0.05
= 98
cm3
Thus ths required volume of 0'05 M
Thus the volume of hydrogen liberated at KMnOo solution : 240 cm3.
STP = 2E00 cm3

acid. Whatvolume of CO2 measured at sTP wll be

evolved lD the abor'e reaction ?

[\ns. 43.E7. and l00E cm3]

 SOME BASIC CONCEPTS IN CHEMISTRY
1/63

M 2. Calculate the volumc of I 0O mol L-l aqueous

sodium hydroxidc thar is neutralized by 200 mL of zBt- (a + c\(aq)- 2Ct- (a!t) + Bh @q)
2.00 mol L-l aqueous hydrochloric a;d and mass Suppoc we havc 50.0 mL of 0.060 M solution of
o[ sodium chloridc produced.
. N qI R T).
NaBr. What volume of 0.050 M solution of Cl2 is
J(
[ .\r\ 400 mI, 23 4 g] needed to react mmpletely with the Br- ?
3. BromiDe is prepared commercially by the reactioir
I Ans.30 rtrl. Cl2 soluaion]

H I NTg Fo'-DtFFtcut:r r{orl-:z,v,s

1. CaCO3 + 2HCl .* CaCtz+HzO + CO2 2
100g 2 x 36.5g ZZqU);, = t oo0-
O
x 2OO = 0.4 nor
at srP I molof Hcl
Marute reacreo-l 5- { 5g = a.5g Producs Nacl = l mol
:. . 0 4 mol of HClwill produce NaCt = 0.4 mot
smarbte = Jl
,oira sg
HCI reacledwith 4 5 _
=0.4x58 5E=23.48.
3. 50 mL of0.060 M NaBr conraiD NaBr
= 3.285 I
% strengn = !ff x rco = 43.87o =ffi"somot=0 003 mot

co2 2i190 ,. 2molof Br- rcact with cl2 = lmol

' evolved ar s.ftP =s.., 100
o
0 03 molof Br- will react with
= lfi)g cm3
Cl2

I
2. MrVr = MrYri.e. 10xV1 =20x200 =tx0 03=0 0015mol
(Naoll) (HCl) 0 05 mot of Cl2 sotution are prcscnt in l00oml_of
or Vt = 400 mL CL solution
NaOH + HCI...- NaCt + l.IzO .. 0 015 molof Cl2 will be prescnt in Clz solution
200mLof 2.0MHCt conrain HCt
=##x0.ools =30mL.

Quite ofteq one of t-he reactants is present in larger amount than the other
as required according to the
balanced equation The amount of th prcduct formEa u"i a"p.n*
up"" the reactant E{rich has reacted
completely. This reactantiscalledtherimiaingrtactantorrimiuo!Gg;.rlr"."r"t-,*rrr"ti.,.1*irr-"a
completely in the reaction is called exctss Eactant as tre excess;f
;s reacta is left unreacted.

SOLYED EXAMPLES

, I.l\..\IIPLE l.Zin c and hydrochloic acid react Thus, 1 mol ofzinc reacts with 2 moles of HCl.
accord.ing lo the reaction . . 0.30 mol of zinc will
Zn (s) + react with HCI
2 HCI (aq)
=7x0.30=0.60moI
ZnCl, (qq) + H2 @) But we have onlyO.52 mol of HCl. Hencc zinc
-
110.30 mol Zn qrc added to hydrcchloic acid cannot react completely and hence is not a limiting
c.ontaining 0. 52 mol of HCt, how many moles o[ reactant.
H, ure produced ? (N.C.E.R.T.) Again, 2 moles of HCI rcact with zinc
= lmol
Solution. The reaction is
. . 0 52 mol of HCI will. react with zinc
I
2;61 + zHCt (aq) =;x 0.52 = 0.26 mol
ZlCt, (aq) + H, (g)
-
 Ne.at Coursc Chent istrg
1164

As we have 0 30 mol of zinc, therefore, HCI Apply"g Gay Lussac's Law of Gaseous

will react completely i.e. HCI is the limiting reactant Volumes,

2 moles of HCI Produce H, = 1 mol 1 Vol. of O, reacts with Co = 2Vol.
.'. 0'52 mol of HCI will Produce H, . . 1 litre of o, witl react with CO : 2 litres

=1x0.52mol=0 26mol at STP

2
But the volume of CO taken : 3 litre at STP
3.0 g ol Hr 'eact wirh 29'0 g ol
l,t\Al\lPLr,l z.
Orto Jorm HrO'
.. Volume or co ,", ttr, ,lTl,l"j
, ,,,,"
(i) Wich is the limiting reactant ? Now by mole concePt,
(ii) Colculate tlw ntaxintum amount of H2O Mass of 22 4litres of CO at STP
that can be formed. = Molecular mass in grams
(iii) Calculate the amount of the resctant left
unreacted-
- t2+ 16=2ag
Molecular mass of Hz = 2.016. .. Massof llitreof COatSTP= *",
Solution.2 H, + Oz .-..+ 2H2O = t.25 g
xz 016 32c 2x(2 016+16) Thus the mass of CO left unused 25 g :1
=a n1)o = 36 032
Step 2. To cqlculote the volunte and mass of
12 COrformed [rom 1 litre of Orat STP.
3gof H, require Or=;fux3 =23 89
Appty,ng GaY Lussac's Law of Gaseous
Thus O, (29 g) is present in excess Hence Volumes,
H2 is the limiting ractaut. 1 Vol. of O, Produces CO, : 2 Vol'

. litre of O, will produce COz = 2 litres

Hro formed =+# x 3s = 26 Eg
at STP
. 1

02 left unreacted :29-23 8 : 5 2C By mole concePt,

Mass of 22 4litresof COzatSTP
= Molecular mass in grams
Cahulale lhe mass ol each substance lutnd allet lhe
= L2+2x76 = 44 g
Wich one is orc limiting rcsclant ?
reaction.
Solution. The chemical equation repre- .'. Mass of 2litres of CO, at STP
sentin g thE-reaction is

2 CO + 02 ""'----- ZCOz = *"2=

22.4
3.92as
2 vol. 1!,ol. 2 rol. :
Thus the mass of CO, produced 3 928 g'
StePl.Tb calculate the volume and mass of CO
SteP 3. As orygen has been completely used
(at STP ) lelt unused alter the reaction .
up, hence oxygen tt the limiting reactant'

FOR .fz CT,'IOE

"e<O?LEM9
1. 500 cm3 of 0.250 M NESOa solution sdded to an
aqueoussolution ot 15.00I of BaCl2 re$llted in the
many moles and how many grams of BaSO4 are
formed ? [,rrrs 0.072 mole, 16.776 g]
2. Ifm 0 gof CaCO is ueated with 20 otof HO, horv
formation of a white precipitate of BaSO4 How
3
marry grams of Co2 wil be produced ?
L\,rs. t.t0 8l
 SOME BASIC CONCEPTS IN CHEMISTRY 1165

1. 50Ocm3of 0.25 M NarSOo =

ffi x soo 2. CaCO3 + 2 HCt
40+12+3x16 2(r+35 s)
=0 125 mole
= 100t =73t
15 I ror" = 0 072mole
BaCl2 =
ffi Caclz+H2O+CO2.
NarSOo + Baclz +BaSOI+2NaCl 12+2 x 16

Evidently, BaCl2 will be rhe limitiDg reaclanr. 44t

Here C.aCO3 will be rhe limiting reacranr.
BaSOr formed = 0 072 mole = 0.072 x 233 E

= 16 '7'76 I

,r I Percentyicld' The actualyield ofa product inany reactioD is usually less than the rhcoretrcal yield (calculated
from the balanced chemical equation) because of certarn sidc reaitions taking place or less idealionditrons
than required. Hence we have percenr
feld = Th*re!!ffEh. x 100

:,i: l Eudiometry' This isa method for finding the molecular formula ofa gaseous hydrocarbon. The apparatus rs
sho'sm in the Fig 1.6. The merhod iDvokes the following sreps:
(i) A ktown volu me of the gaseous hydrocarbon is mued with an excrss (kno*n or un kno\xn volume) of orygen
or ak in the eudiometer over mercury.
(,i) Themixture is exploded by electric sPark and then cooled so that water vapour condense to liquid whose
volume is negligible

Cr H, (ir) +i (r+l) o2e)-xcO2e) +

| nro 1r;
tcc I.*Ii xcc
\ 4./ ".
( i) KOH is introducd which absorbs CO2 and onty
unused 02 is left. Thus decrease in volumeon adding
tr(OH = Volume ot CO2 produed
Iues ofxand yare rhen calculated from the follow-
ing data :

(i) Volume of 02 used per rc of hydrocarbon

= t*r)
I 4./
..
(!r) Volume of CO2 produced = r cc
(iii) Conrraction on explosion and c.oting

=1,.(,.+)]*-(-. )*
r /66
r)radec j,'s Neut Caurse Chemiitryl&ElD

,
' once al
rrlr*rlujfirr.jr:r
egtlono
.r: : : I ri i: r: Inlr"jx+r+tn2'J:rtr:n:rtn

Q. What physical quantities arc rpresented by the follorying units and what are their most common Dsmes ?
(i) kg ms-2 (ii) kg m2 s-2 (iii) dm3
turs. (i) Force (ne$4oD) (ii) Work 0oule) (iii) Volume
(-). ]. Rewrite the following after required corrections :

(i) The letrBth ofa rod is l0 cms. (ii) The work done by a system is l0 Joules.
Ans. (i) The length of a rod is 10 cm (r is not uscd).
(r) The work done ry a system is l0 joules (small lettcr is used in placc ofcapital letter).
(.). -r Classify the follotf,ing substances into elements, compounds and Eixtures :
'
(i) Mitk (n) 22-@rat gold (iii) Iodil2d tsble salt (iy) Diamond (y) smokE (y0 steel (y4) Brass (vin) Dryice
(&) Mercury (.r) Air (E) Aerat d dritrl(s (!r) GluGe (ri.r) PetrovDiesevKer6ene oil (riv) StearD (rv) Cloud.
Ans. Elements (iv), (tt)
- (viii) , @r), (rir), @)
Compounds
- ( i), (v), (vi), (wi), (r), (r),
Mixtures- (,). (d), (11ii)

Q JWhy air is sometim.s considered as.a heterogeneous mixture ?

Ans. This is due to the presence of dust particles which form a separata Phase.
e. S. Why Itw ofcotrserratior o[massshould better be called as I,sw ofconservatioD ofmass aDd energ]r ?
Ans. In nuclgar reactions, it is observed that the mass of the products is less than the mass of the reactants. The
difference of mass, called the mass defect, is converted into eners/ according to Einstein equation, E =
a rn c2. Hcnce we belter call it as a law ofconservation of mass and enerry.
Q r,. ts the larv of constant compo6ition true for all types of compounds ? Explain why or why DoL
Ans. No, Iaw of constant compositioD is not true for all types of mmpounds. It is true only for the compounds
l2C and lac. When it forms
obtained from oDe isotope. For example, carbon exists in two common isotopes,
11C, tbe ratiowill be 14 i32
Coz ftom l2C, the ratio of masses is 12:32 = 3 | 8but from = 7 :16 which is
not same as in the fitst case.
(.) I I L of a ges at S.T.P weighs I 97 g. What is the vaPour density of the gas ?
Ans. 22.4Lof tt]fvgas at S.TP willweigh = 197 x22 4= 44 l gia molecular mass =44 1. Hencevapour density
= 44.1/2 = 22 05.
(,) IWhy ltomic masses arc the average valucs ?
Ans. Most of the elements exist in different isotopes r.c. atoms with diiferent masses e.& Cl has iwo isotops with
mass numbers 35 aDd 37 existing in the ratio 3 : l Heoce average value is taken'
r.) r) Itryo bulbs Br and 82 ofequal caPacity contain 10g orygcn (or) and ozone (o3) resPectively which bulbwill
have greatr nurEber of O-atoms aud which will have Sreater nuEbcr ofmolecules ?

lns tOgO, = $msr, =$x6 02 x 1oB rnolecules

= 1.88 x 1oB molecules = 2 xI 88 x 1023atoms=3 76 x 1023atoms

or x
l0 Smole = ]$ " e oz 104
g = molecules

=1 254 xlodmolecules=3 x1 254 x1023atoms=3 76xloaatoms

Thus both contain the same numbgr of atoms but bulb Bl contains more numbel of molecules.
r., to Deterrrine tbe equiyalentweightoleEch ofthe following compounds assuming the formula weiShts ofthese
comPounds are.tr y snd z resPectively.
(i) Na2SO. (ii) NaIPO. . 12 II2O liii) Ca3(PO4)z (M.L.N.R. Alhhabad 1991)

Ars. Eq wt = Mol. wtflotal positive valensy of metal atoms

(i)r/z (ii)Yt3 (iii)z/6
 SOME BASIC CONCEPTS IN CHEMISTRY 1167

r."' lvhy sre the etomic mosses of ulost of the elemerts fractionol ?
Ans. This is because atomic masses are the relative masses of atoms as compared with aD atom of C-12 isotope
taken as 12.
l-) ll llLite the formulae and nerDes of thrce clEurounds @ntaining ssme Frttrhge.or,rp*ition of q H aDd o.
Atrs. Compounds with the same prceDtage compositioD of C, Il and O will have the same empirical formula. The
compounds with the cmpirical formula CH2O can b
IICHO CH3COOH C5HI2O6
Formaldehydc Acetrc acid Glucqre

Q. 1. What is the nuErber ofsigtrilicant ligxEs ir 1.050 x ld ?

ADs. four
Q. 2. What is the S.I. unit ofdensity ?
Ans" kg m-j
Q. 3. What is AZT ? To rvhich use is it being put ?
Ars Azidothymidine used for AIDS victims.
Q. 4. What is the law called which deals with the ratios of the volumes of the gaseous Eoctants snd products?
Ans Gay Lussac's law ofgaseous volumes
Q. 5. What is one a.m.u. or one.u' ?
I
Ans. 1a.m.u. or I u = l2th oflhe massofan atom otcarbon-12.

Q. 6. Which lsotope ofcarbon is used for gettitrg relative atomic hasses ?

Ans, C-12
Q. 7. Write down tbe empiricsl formula ofscltic acid.
Ans CHrO.
Q. t. What is thc S.I. unit ofholarity ?
Ans. mol dm-3.

CARRYING2oT3MARKS

\r( I l. 1, Chemistry can prove ro b a blessing or a curse depends upoD the uss to which it is put. Crmmcnt.
l,! I -1.
sr( I.J 2. Briefly explain rhe difforence between precision and accuracy.
l0 l.(r
3. What do you mn by 'sigDlficaDt figures, ?
4. Under what conditions the zerG in a oumber are sigDificaDt ?
5. After roundiDg ofl what $'ill be the value of
(i) t.z3s (ii) 1.22s ?
6, What does symbol SI siFiry ? Name the seven basic SI units ?
7. What do you understand by unit conversion factor? Hos, dos it help to coovert height
in feet to
hcight in metres ?
r.. ls t. Define Element, Compound and Mixrure.
to 1.12.
9, Give examples ofhomogeneous mixturcs in different phlsical states (rwo each).
10. Give three main points of dilfereDce betwecn a compound and a miKure.
11. Classiry the following subsrances into elements, compounds aod mixtures.
Further separate the
mixtures into homogcneous or heterogeDeous :
'1168 l'r,. tbt'y's Neut Course Chemistr:g mm
(r) air ( ) milk rrrr) graphite (iv) diamond (v) Sasoline (vi) mp water (vii) distilled water
(viii) qygen (rI) one rupee c
coin (x)22 at Eold (r) steel (ri) iroD (dii) sodium chloride
(.tiv) iodized table salt.
s(.c. I lJ. 12. dive one experiment invoMng a chemical reaction to prove that the law of conser%tion of mass is
t,) L llt true.
13. Copper oxidc obtained by heating coppr carbonate or copper nitrate c.ontains copper and ory8en in
the same ratro by mass. Which law is illustrated by lhis observation ? State the law.
14. Nitrogen forms a number of oxrdes. Wrire their formulae and give their names. GMng apPropriate
calculations, exPlain the law that follows from it.
15. N and O combine with H to form NH3 and HzO and they combine with each other to form NO2-
Which law is illustrated? Explain bricfly.

15. Define Gay Lussac's law of Saseous volumes Explain witb one suitable e)(ample.
Srr. 1.10. 17. What are the postulates ofDalton's Atomic Theory ? How do the laws ofchemical combination follow
to L)) from it ?
lt. What are the postulates of Modern Atomic Theory?
se(. t :l- 19. Which isotope is used as a reference on ihc atomic scale ? What is one amu or one 'u' ?
1,, l.l7
20. Why atomic mass is an average value ? Frplain with a suitable examPle
Slj(. l.lti. 21, How N mole related to
(a) number of atoms/molecules
(b) mass of the substancE
(c) volumc of the Saseous substance ?

22. what is the SI definition of mole ?

2J. Crmment oD the following :-
'1 mole ofhydrogen'
s(-. I 2{) 24. what is thc difference between
(i) Normaliry and Molarity ? 0l) Molanty andlv{olality ?
sr( I .rr 2s. Difine Empiiicat formula and Molecular formula. What is the relatioDship bet*en them ?

1o I -rJ
26. Write the emPirical formulae of the following :
(i) N2 04 (,i) c6 H5 (iii) c6Hrzoe (v)Hro2 (v) Hro (vi) NqCo3 (vii) cHrCooH
Scc. i -r 7. 27. What is a limitiDg reactant ? fsplain with a suiuble example.

Sir ll 1. Briefly explain the imPortance ofstudying chemistry.

i,) l-1.
2. What do you understand by 'significant figures' ? What are the rules for determining thc number of
siSnificant fi8ures? Illustrate with suitable examPles.
3. (a) Whal do you understand by 'RouDding off' ?
(b) What are the rules for determining the number ofsiSnificant fr8ures in answers involving
(i) addition or subtractioD
(ii) multiPlication or divisror
(iii)calculation iDvoMng a number of steps
Explain each case with a suitable example
:r, I 1 a. What is the latest and rhe most scienijfic system of units ? what are the seven basic unils in this
t, , 1 t slstem ? What aie derived units ? Give the derived units of the following Phlsical quaDtities :
Area, Volume, Density, SPeed, Accteration, Force, Pressure and Energy (or work)
5. What do you understaDd by Dimensional Analysis ? ExPlain with a suitable examPle'
SOME BASIC CONCEPTS IN CHEMISTRY 1/69

Scc. 1.7. 6. Define 'matter'. Briefly describ tbe phFical as well as chemical classification of matter.
lo l.tt.
Scc. 1.9. 7. DefiDe Element, Crmpound and Mixture. What arc homogeneous and heterogeneous mixtures ?
to 1.12. Give one example ofeach of the homogencous mifiure in the gaseous phas, liquid phase and solid
phasc.
t. List ibe main points of difference berween a compound and a mixture.
Sec. 1.14. 9. State aDd explaiD the'[aw ofCoDservation of Mass'.
Scc. 1.15. 10. Defioe'Law of Consknt C-omposition or Definite Proponions'. Frplain with a suitable example.
Scc. 1,16. 11. State the Law of Multiple Proponions, Explain wirh two suitable examples.
scc. 1.17. 12. State and explain kw of Reciprocal ProponioDs.
Sec. l.lE. 13. What is Gay Lussac's I-aw of Gaseous Volumes ? Fjplain with two suitable emmples.
Sec. 1.20. 14. What are the main pclulates of DaltoD's Alomic Tbeory ? What were its limitations? Hotp has the
to 1.22. lheory been modi- fied ?
Sec. 1.23. 15. Define tbe follo$,ing :
to 1.27. (D Arom (ri) Molecule (rii) Aromic mass (iv) Gram atomic mass
(e) Molecular mass (vi) Gram molec1rlar mass.
Give suilable examples ilr cach case.
Define Avogadro's la$,. Thking a suirable example prove thai it is nor in conrradiction wirh Dalton,s
16.
Atomic Theory.
Scc, 1.2E. 77. Define Avogadro's Number' and.'Mole'. Whar is rhcir importance ?
Sec. 1.29. It. (a) Define the terms Solution, Solute and Sofvetrt.
(D) Define the differeDt methods used for expressing the concentration of a sotution.
Scc. I30. 19, Wbat are Errpirical and Molc@lar Formulae? Holp are they related io eaci other?
to 1.3.1.
 EUt*l,NjE@,RM"

l. Averrgc Deyiatior. The simple$ way to epress precision is in tenns of average deviation. For this pu rPc,
first the average of the different mssurements is calculated. TbeD the deviadon of each meaaurement from the
average is catqrlated, tahog all deviatioDs as positive. The average of these deviations is called average deviation.
2. Relatlve average d.drtion (r.o.d.). Precisioo is more ftequently exPressed in terrN of relative avcrage
deviation which is equal to average deviation dMded by average value of different measuremeDts.
ExsEplc.
Electronic charpe (esu) of individual maasurements Individual dzviation ftom the average
4.80 x 10-lo 0.01 x 10-10
4.79 x 10-10 0.00 x 10-10
4.81 x 10-10 0.02 x 10-lo
4 76 x 1o-lo 0 03 x 10-lo
'Ibtal = tg to x to-10 Total =o 06 x 10-10
19'1c xto-10
Arcrage - =1.79xt0-l0csu,
0 06 L1o-10 x
Average dev. - - 0 02 10-10 esu

.. Resutt will be reponed as 479xlo-1o to'o2 x 10-10 e.rz

Relariveaveraredcviation(ra.dl=99?"1!=::',*=o(){,42()tO42qoot42oOpartspermillron(ppm)
ls 4.79 x lO- esu
ofthe absolute error or the relative ertor.
3. Rclativc error. Accuracy is expressed iD terms
Absolute enor = ExprimeDtally determined value-Accepted value

Relarive error:ffiiiii#
ExrrEple. Experimentally determined value of electronic charge = 4 '19 x 10- to e.s.u-

Acceptcd value of electronic charge =4 80 x l0-10es.z

Error (or Absolute error) =4 79 t 1o-10 - 4 80 x 10-10 = -0 01 x1o-10esu'

Relatrve error _
- o or, to ]0x lm =_o 2.i
4.80 x l0-lu

1170
SOME BASIC CONCEPTS IN CHEMISTBY 1171

ADDITIONAL UgEFUL INFOtaMATION cart.l

4. Equivalent maes. The equivalent mass of a substancc is defiDed as the oumber of Parts by mass of that
substance which combine wirh or displace directly or iDdirectly I .008 parts by mass of hydrogeo or 8 pans by mass
of oxygen or 35 5 parts by mass of chlorme.
5. Calculation ofequiYaleut Eass

(i) Eq.massoraner"r"o, =ffiffi$ffifl

?.8. Eq. mass of Cu in CuO =
ff =31 8 (Valency of Cu =2)

Eq. mass of CuioCurO =li =63 6 (Valency of Cu=1)

Formula mass of the ion

(ii) Eq. mass of an ion =

e.& Eq. mass of co!- ion = U:]fJ9 = 9! = n

Molccular mass
( i) Eq. mass ofan oddilD&/reducing agent = No. of clcctrons lost or gained by onc molcculc
(Discwsed in unit 9)

Molecular mass of the acid

(rY) Eq.masolanaoo = --- ;;E;?fi;;;E- (Abeo$ discrused\
. Molccular ma65 of tbc basc
(v) 84. masol a Dase = --=.d,ty;I rh-" b"* (Abcady disc'tltsed)

6. Detormlnation of equivalent mass

(i\ mrtlad. Calculate tbe mass of the metalwhich displaces .008 of
Hydmgen displacemeru 1 Parts by mass
hydrogen.
(ii) Oide fomarion or red.uction of the uide method. Calcl)late tbe mas of the metalwhich combines lvith
or displacs 8 parts by mass oforygen.
(iii) CHonde fomotion method. C.alculare rhe mass of the elcment which combines with or disPlaces 35 5
pans by mass of chlorioe.
(iv) Melal di$plicement ethod. WheD a more electropositive metal N added to displac a less electroposi-
live metal from its salt (e.& Zn + CUSOa -- ZnSOa + Cu),
Mass ofmetal added
Eq. mass of metal added
Mass of metal-"ispiactA' = Eq. massE meiaIAEFEcEA
(v) Doubla decompsition melhod. For a reactroD of the t)?e
AB+CB-.+ADJ+BC
(e& A8NO3 + NaCI- AgCl l + NaNO3)
Mass ofAB takcn Eq. mass of AB Eq. mass ofA+Eq. mass ofB
IGss oFID-Errned = Emass oIE = E- mass of-A+E mass ofD
(vi) Elacnolytic ,tgthod. (Fanday's second law). When the same quantity of electricity flows tbrough
Mass of X deposited E4. mass of X
solu(ions of different electrolytes,
Mass ofyTeposiiET = Elmass ofJ-
(vii) Neutraliaion mathod. 'lo calcr')late the equi\ralent mass of an acid, calculare the mass of the acid
Deutralized by 1000 cc of 1N bas solution (which cootains 18 eq). Likewise equivalent mass of a base can be
calculated.
(viii)Silvet rau method (for organic acids only). A knowD mass of silver salt of the organic acid is ignted to
Eq mass ot RCOOAg Mass of siFer sall
8,'e a resrdue ol A8' thcn Ta. -
.ss or. Ag ( ra8i = -liasa ollliner
Eq. mass of acid (RCOOH) = F.q. mass of RCOOA8-1o7.
1n2 Neur Course Chent i strtl

ADDITIONAL U9EFUL INFORMATION car,td

(b) Convenion method. When one mmpound of a metal is converted into another compound of the same
metal (e.g meral carh)nate +metal Gide), then
Mass of compound I Eq. m ass of m etal + Eq. mass of anion of compound I
Mtssofco-mpoundT =@
7. Mcthods ofdetermining stomic mass
(i) By application of the rclation At. mass = Eq. mass x valency
Knowing approx. atomic mass and exact equivalent mass, first vale ncJ is calculated and then the exact atomic
mass.
(ii) Dtlong and Petit\ method. Fot sr,lid dements (e)rcePt Be, B, C and Si), according to Dz long ond. ktirb law
At. massxSpecificheat=6 4 apProx.
.. Apprq. aromic mass =
ffi
Exact atomic mass = Eq. wt. x Valensy

where valency = 4lPqjlggsI3il (Take nearest whole no.)

Eq. m ass

(iii) Ftom rutio of heat caPocities . Fot Easr;, we have

Ratio, 1 66 1.40 1.30 1.26
'1 =Cr/ cu
Atomicity 1

Molecular mass can be found from vaPour density (Mol. mass = 2 x VD)

Aromic mass of the Saseous element =

ffi
(iv) Vobnle chloide rnethod. (FrcmeaDc,ur density measurements forelements formingvolatile chlorides)
Molecular mass of lhe chloride = 2 x VD.
If -r is he valency of the elemenl (M), then formula of its chloride will be MClr . Hence

Mol. mass of the chloride MClr = At. mass of M+, x35 5

= Eq. mass of M x valency of M + .r x 35 5

=Exx+, x 35'5 =.r (E + 35 5)

. x(E+35.5)=2xVD'
2xVD
or r = E-+-35.5
Knowing the equivalent mass E of the element, the value of r can be czlculated. Then atomic mass = Eq'
mass x Valencf.
(v) Isomotphismmerrod. Compounds having similar molecular formulae and identical cq6tal structure are
called ircmorphous. The method is based upoD the fact that elemeots in isomorphous mmPounds have same
valencies, e.&
(a) KrSOo , K2CrOa , IqSeOa are isomorPhous Hence valencl of S, Cr and Se = 6.
(D) ZnSOa.T HzO, FeSOa.T H2O,MgSOa.7H2O are isomorPhous. Hence valency of Zt,Fe'Mg=2'
Xnowing valency, atomic mass = Eq. mass x Valency.
(vi) hom percentage of an element in a given compound. For examPle, potassium chromate (K2C[O1) is
found to contain 26 78/o of Cr. Ils atomic mass can be calcu lated as follo\\'s :

Suppose atomic mass of Cr = a

.. Mol. massof IqCtOo=2 rro +o +4 x16=142+o
.. Eo oto inK2ctoo=ffi = ru'rt
which on solving gives o = 52.O.
SOME BASIC CONCEPTS IN CHEI\iIISTRY 1173

ADOITIONAL UgEFUL INFORMATION co ntd.

E Dtsrm lrrtlon ofAvosadm's Dumber. The simplest method is by studying elecrrollsis of acldu lated water.
The reaction taking plac at the cathode is 2Il+ + 2e- H2
This meanr that chargE crded by 2 moles of electrons produces - 1 mole ie. 2.016 g of Hz gas.
Thus cxPcrimentally the amount of electricity required to produc 2.016 g..f H2 is determined. It is found
tobe193000coulombs.Aschargecarriedbyoneelectron=1.602x10-l9coulombs,thereforeifNisthenumber
of electroDs present in I mole, then

2N x 1.6U2x 10-le = 1!3669 q1 I{- 193000

2x7 6O2 x l0-te =602x1OA.

C",E.S.E. - P.llt. T. U[4 ATAISJ S PEC I A t

A. SUBIECTIW QUESTIONS Q, 3. What ls the dillernce in ihe molar volume ofa
l. What is the differnce betweeo the follotiing
gas if S.T.P cordltloos src
Q. ?
(i) I atm, 0'C (ii) I bar, 0.C ?
(i) 2 5 x ldgand 2.50 x 1dg
ADs. (i) If
S.TP. condirions are I arm,0"C, molar
(ii) 160 cm ard 160.0 cm.
volume = 22400 cm3
Ans (r) 2.5 x 1d has two significant tigures white
(r, If S.TP conditioos are I bar, 0.C, molar
2.5O x lG has rhree significant figures. Hence volume = 22?oo cm3
2 50 x 1d represenrs greater accuracy tbaD
Q.4. Iryhy molality is prcfcrred ovcr Erolsrity in cx-
25xld. prcssiDg thc concentration ofr rolutioD ?
(ii) 160 has rhree significanr flgures while 160 0 Ans, Molality is the number of moles of the solute present
has four significant figures. Henc 160.0 repre- in I kg of the soh/enl whereas molarity is the numbcr
sen$ Sreater accuracy. of moles ofthe solu te present per lire oftbe solulion.
Qf Which of the following has largest nuErber of Thusj molality invoi,rs only masses $,tich do Dot
oxy8en atoms ? change with tempcrature ufierEas molarity invokes
rolume which cianges with temperature. HeDce
1.0 g of O atoms, 1.0 g of 02, 1.0 g ofozone (o3)
molaliry is prefe[d over molarity.
Justlfyyour answer. 5. Takl4 N,aad 02s! main compotrcotc ofthe air
Q.
Ans, I0gof Oatoms=i.garomsof O (79% N2,21% O2W volumc) whst ls the mole-
x 6.02 x tozr aloms cular mas! ofslr ? How has lt been srrlved ot ?
= i Atrs. For a mixture of gases, the average molecular
6 02 x 7023
__-_16_ mass is taken.
= aroms
Average molecular mass =IrrM,
1.0gof02=f mor of or= j. x r.oz x ror ='n2 Mn, *'o, Mo, where rN2 and to2 are
molecules = 2 r 1r!r6 oz x toBaloms mole fractions of N, and O, and Mn, und Mo,
6.02 x 1023
____16_ are their molecular masses. As equal volumcs
= aroms
contain equal number of moles, therefore, thelr
molar ratio is same as ratio oflheir volumes.
10gof O, =f mor of Or=axe .oz x ro23
. ,n, = 0 79, xor= O 21. Also MN2 = 28&,
molecules = f ,. , o.oz x lo3 atoms
ol. or= 32u
e 02 x to23
=----lG-aroms .. Average molecular mass
Thus, all of thcm mntain equal number of -019 x28 +0 x32u 21
atoms. =22.12+612u=2t.a4u
117 4 Ne* Course Chent i s tra
Q.6 What is thc dilIerence betteen the mass of a or 35x+3700-37x=3545
molecule and gram molecular mass ? ot 2x=155 or x=7'1 5/o
Ans. Mass of a molecule rs the actual rirass ofa single 'ftris{cl = 77 .5% and 37c'l - l0o - 71 5 = 22's%.
molecule cxpressed in Srams whcreas gram Pfublr,,, -']. Calculate the temPeraturc at whlch the
molecularmassis the mass ingram ofAvogadro's
value in degrees celsilts ar|d degres FahcrDheit is ssme.
number of molecules.
(.).7. In the coDbustion ofmethane, whatisthe limit- The reacrionshiP beNveen 0'C and T is
itrg reactant and why ? .c=i(F_32)
s

Ans, Mcthane is the limlting reactant because the 5

other rcactant is orygen ofthe airwhich is alwals If .r"C=x.F,rhenr.= 6@ -32)
present in excss. Thus, the amounts oiCO2 and
lI2O formed will dePend upoD the amount of or 9r=5r-160 or 4x=-160
CHa burnt.
or .r= -,10'C
Thus -40'C = -40'F.
(l I What is the equivalent weight of KH(IO3h as an
c,onY.ertz2 4 L into cubic metrcs.
t'ruhbtn 1.
oxidant in presenc of 4 0 (N) HCI when ICI
bemmes the reduced form ? Solution. 22.4L=22.4.'4ff+-*k
(K=39 0,1=127 O). (West Benqall-E.E.2001)
lm a lm
lurs. ln KH(Io3)2, IO3 is present as lot. Oxidation -" 100r{n' 100 r.rr
state of I will be 1000
_ 22 4 x m3 = zz.t x t}-t m3.
x-6=-1 100x100x100
q1 :=+5. I'roblL'n J c,slc]ulat the molar mass ofwater ifit
+5 .-.- +l contains 5{) heaYy vater (D2O).
KH(IO3)2 2 ICI
As water contains 50% D2O, this means
f)ecrease in oddatioD state = + l0-2 = 8 11
that it contains; mole of H2O and imole otD2O. Mass
'. Equii?lcnt wt. of KH(IO3)2

*-39)=lt.zS j mole of H2o =; x lE = e6. Mass of mole of

- 39+l+2(12'l
Mol. wt. of I
9 What is kg.mole ? Fi[d out the totrl trumbcr of
DrO =lx x2 +16) = 10 6. Hence molar mass of
(2
Q
electrons ir a kg' mole ofOt. the given sample ofwater = 9 + lO = 19g mol-l,
(West Bengal t.E.E- 2004) I'roblun 5. The average molar mass of a mixturc
Ans, One k8-mole (or simpty called one kilomole of metha! (cHa) and ethene (crH.) Present in the
(kmol) is the molecular mass of the substanc ratio of a : b is found to be 20'03 mol-!. If the ratio
expressed in kilograms.In CGS system, one gram were rcversedr whst vould be the molsr mass of the
mole ofa substanc contains Avogadro's number mixture ?
MKS s)6tem' one I
tains Avogadro's Molar mass of CH1 = 16I mol-
e is 6'022 x ld5 qHa = 2E t mot-1
Molar mass of
x tain 6'022 1G6
When they are Presnt in the ratio a . b, llrcit
molccules aDd hence 16 x 6 O22 x 1G6 avcragc molar mass
electrons.
B. PR()Rl.li]l\ ="
*'2ll*" = 203 mor-r (Giveo)

!'rohleti l. Calculate the perce[tage of the i.e. 16a+28b =2O(a + b)

lscl and 37cl that sc-
natu.ally occurrilg lsotopes ot 4a+7b=5.(a+b) ot a=2b
counts for the atomic mass ofchlorine tsken as 35 45'
a 2
Suppose 35Cl preseot = xVo. Tlnen37Cl ot E=I=L.^, t
present = (100 - r)7a
If thc ratio is reversed, now thc ratio a : b= 1: 2
Average atomic mass
Average molar mass -
1x16tzx28
_ .( x 3s + (Jgq - r) I31= a5 (given)35 r+2
100 -
SOME BASIC CONCEPTS IN CHEMISTRY 1n5
16 +56 12 6.4
f=zts^"r-l 613' = 1e3 e
=
;',-,,t'irDt o. 20-O mL of a mixturc of oxyger (O2)
.. Valenry of mercury
and orone (O3) was heated till ozone was completely
decomposed. The mixture on cooling was found to ex- = i; - 2 (as valency is a whole no.)
pand to 21 mL Calculate thc percrlt ge ofozone by
volume iE the mixtur. . . Actual atomic mass = Eq. mass x lency
Sjlu-tion. DecJmposition of szone takes place as =1OOx2=2OO
follows : Calculatlon of stomicity
2Ot 3Oz Aromiciry=*#=#3=1
2volumc 3volumc
Suppose ozone in the m[ture = -r nL. Then Thus, mercury molecules are monoatomic.
Oz=(2O-x)mL /'rl,/,/,,,, ,\.Insulir contains 3 4% sulphur. Calcu-
late the miDiDurtr Eolecular rnass ofitrsulin.
2 mL of C]/zrone on des)rnpositron give 02 = 3 ,n L
SolutioD. Minimum molecular mass of insulin will
.. x mL of ozone on decompcition will glve be tbe.t-as
containing at least one atom ofsulphur.
1
o2=;x=1.5xnL One atom of S = 32 a.m.o.
No!v,3.4 a.m.u. of sulphur is present in lma.m.u.
. Tt talvolume of mirure afier de{ompGttion
ofinsuliD.
=1.5x+(20-x)mL .. 32 a.m.u. of sulphur will be presenr in losulin
=20+0 5r _ 100 ,1,'
.. 2O+0.5x=21 (Given) 1-4 ""
or O.5x=1 ot x=zmL = 941 2 a.m.u.
. Percentage of ozone in the miKure Hencc minimum molecular mass of insulin
1 = 9{ r. 2 r,m.u.
=;bx100=r0%. Pruhlttn 9.Hov aary mol.cules rpproxlmately
l'nl'lut 7. Calculste the atomicity of Ecrcury doyou cxpect to beprentin (i) r small sugarcrystal
rDoleculcs from the following data : which weighs l0 mg (ii) one drop olwater with 0.05
cc volume ?
(B) 10.OBof mclturycombinewith 0 6gof oxygcn
to form an oxide. (i) l0 mg sugar (c12H22Ol l)
(b) 500 EL of mercury vopour at S.T:B weigh =
4 465 E
= O.0r g = $mor- = 2.sz x10-5 mote
(c) Specinc heat ofmcrcury is 0 033. xrc-s) x (6.02 x loa)
= (2.s2
Solution. Calculatior of equivalent mass
= 1 7r x l0r9 molecules.
0 899of orygen combine with Hg = 10.0 g
'. 8 g of orygen will combine with Hg (ir) O 05 cc water = 0.05 I more
= $S
l0 = 2 ?8 x 1O-3 mole
=6T-x8=100t
= (2.78 x 10-1x (6.02 x 104) molecutes
.. Equivalent mass of mercury = 100
Cslculation of molar mass = l 6? x l02l molecules.

500 ,n L of mercury rapour at S.TP $righ = 4 . 465 t I'rohlun 10.9 7 x 1017 atoms of ircn ricigh as
. 22400 mL of me1'l(xry vapou r at S.TP wi weigh
Eluch as I cc of H2 at S,T,P What is the atomic mass of
iroE ?
=ffrzzeoot Solution. Mass of I cc of H2 at S.Tp

=200t -13* )24(n =, o x ro-5 g

'Molar mass of mercury = 200 t mol-l Mass of 6.02 x 1023 atoms of Fe
Calcu!ation ofvalency. By Dulong and perit,s law 9 0 x 1o-5 x6.U2x lP
= 55.9 g
Approx- atomic mass oI mercury = --!-3- 9.i x lOrT
Sp. Hcat
Atomic mass of Fe = 55.9 u
1n6 Pradeep's
: ',.1) t,r tI 20 cc of 1 N HCl, 30 cc of I'rohlun 11. 4 g orbon werc heated with t g of
0 s N IlzSOl and 50 cc of 02 N HNO3 8rc mixcd sulphrr. Hot much carbon disulphlde (CSr) will be
toBether. What will be the normsllty of the tinal solu- formed when the reactlon is complete. What will be iLs
tion ? prcentage purlty ?
solution. 20 cc of 1 N HCI coDtains' C +2S CS2
I 128 2tl2 t2+2x32
=--.:_x20 =0 020geq. =aE =769
30 cc of 0 5 N H2sO4 conkins Obviously sulphur will be the limiting reactant.

_ _:__:, x 30 = 0.0t5 geQ 8gsutphurwll produce CS2 = # x8= I 5g

50 cc of 0.2 N IINO3 contains Carbon reacled = x8_1 5g

i;
jr__: x 50 = 0.01 geg. C-arbon lefr = a 1 5 = 2.5 9
-
of producls 9.5 + 2 5
-lbtal Tbtal mass =
no. ofgram equivalents r,
rLb d
--
=002+0.015+0.01 ' % puriry of CS2 in the product = x I00
= 0.045 ii1
'Iotal volume = 20 + 30 + 50 = 100 cc
= 79 2io.
' Normallty of the final solutron i r, i:1, n 1; How many years would it takc to
q:q1l spend Avogadro's number of rupees at thc rate of 10
= r00
, rooo =o.4sN lakh rupees per second ? (M,L.N-R- Allahaba.l 1990)
l' ,l r' )'
Crystalline magnesium sulphate on
', 6.02 x lOx x
heatinB bccomes anhydrous end loscs 51 27o ol its
mass. Calculate the numher ofwatertrrolecules pEsenL
ffiffis
sotution. = 6.02 torTs

So[u1iqn. 100 parts by mass of the hydrated salt = *:#;#k= r eore x loroyears
contain 51 2 parts by mass of water. This means that
ir,'htt Gastric juice contains about 3-0Iof
h ltr
( lfi)-51 .2) = 48 8 Parts by mass of the anhydrous salt
I ICI per litrc. produces obout 2 ' 5 litre ofgastric
Ifr Frson
arc associatcd with water = 5l 2 parts ry mass. juice pcr dalt how many ortacld tsbleb each (ontairing
Molccular mass of anhydrous MgS04 ,{tO mg of Al(OH)r arl needed to neutrelize all the HCI

=24+32+64=12O produced in one day (I.S.M. Dha^bad 1991)

.'. 120 parts ofanhydrous MgSOtPill be associated solution. HCI is neutralized byAI(OH)3 according
to the equation
r ithH2O=ffirtZO = 125 9 Parts
+ 3HCl AlCl3+3H2O
AI(OH)3
= molecules = 7 molecules' 27 t,37g 3x36 5
-
$2 =1Ag =109 58
t': t't,," l;
1 615 g of onhydrous ZnSOa was HCI produced from 2 5 litre of gastric juicc
placed in moist air. Alter a few days its rrlast was found =3Ox25=15t
to be 2 E75 g. What is the molecular forrn[la of the 109 5 g HCI is neutralized by Aj(OH)3 = 78I
hydrxted satt ? (At. masses : Zn = 65 5, S = 32, '.
o= 16).
75 g HCI will be neutralized by AI(OH)3
Solution. Molecular mass of anhydrous ZDSO4 -L*r'tr=s 342t =5342m8
=65 5+32 +64 =161 5
' Number oftablets rcquired = = 13 35 1.,.
I 615 g anhydrous Z.nSOa combine with H2O
ffi
14 tablets.
=2815- 1615 =r 2608 t,t.kh n 17. Whatvolurne at N'T.P ofammonia gas
will be required to b passed into 30 mL of N H2SO4
. 161 5I anhydrous ZnSO4 willcombinewith
solution to bring dorf,n the acid normality to 0 2 N ?
ll2O = l2b g =ftt= 7 moles (M.L.N.R. 1991)

Ilencc the formula of the hydrated salt is SolutioD. Normality is the number of millic-
7.nsot'ltllo. qui q) Perml-
 SOI\,4E BASIC CONCEPTS IN CHEMISTRY
1m
.. Meq of t N H2SO1 presenr origiDaly in 30 rn L Molar mass of miflure = 2 x v.D.
=30x1=30 =2x38.3=76.68mo1-l
Meq of O 2 N H2SOaiD 30 mL = 30 x 0.2 = 6
ExpressiDg all quantities in terms of moles, wc
'. Meq of H2SO4 required to be neutralized by should havc
NHr=36-6=24 r -r 100 l(n
.. Meq ofNH3 required to be passed = 24
4+-'q-=TF6
or92x+460O-46r=5521 8
(. Acid and base react with each other in
or 46x = 92A.8orx = 2O 1g
equivalent amounts)
But I mole of NFI, = 1g eq r.e. l0O0 Meq of
'. No. of moles of NO2 rn rhe mmure =
fl| =o ev
NH, = 22466 -1", 1U.r, I'tt.hlut 11 Naturally occtrring Doron consits
of lwo isolopes L'hose otomic weilhls arc lO Ol and
. ll OL The atomic weitht of natutal Borun is ll]. El.
24 Meq of NH3 - *frP , 24 = si1 .6 mL
Calculale the percealage of each isotope in natural
I'nhltm l,t. Chlorinc has two isotopes of atomic Boron. (M.L.N.R. A&4lu.had Ig94)
mass units 34.97 and 36 97, The relativc abuadances Solution. Supposc the percenlagc ol isotopc w h
of thess two isotopes are 0 TSSand0 245 respectively atom ic-wEilEf io.ot'= r
Find the aversge otoinic mass ofchlorine.
Then perceDtagc of isorop wirh alomic $,ctghr
(B.l.T. Roachi l99l) l1 0l = 100
Average atomlc mass .. -x
Average atomic weight
14.97 x 0 155 t36 9'1 x0.24s _ 10 01.r + (l0O -r) x 11.01
- =J5 46
100
I'nt,l r A gas mixture of 3 .O litres of propane 10 01 r + 1101 ll 0tr
buaane - 1lO1 -.r
and mplete combustior ot 2fC produced loo IOO
l0 litres of CO2. Flnd out the coEpcitior of the gas
mirture. (M.L.N.R. Atbhahd 19921 "9h-'= lo sl or llol -x= tost
Solution. CrH6 + 5Oz 3CO2 + 4H2O or -r = 1101 - l08l = 20
I - .. 96 age of isotopc wtth atomicwcight 10.01
CoHro+ 6 jO, .......- 4CO2 + 5H2O qa
= 20
Suppose propane =rL. % age of isotope with aromicweighr ll.0l =t0alo
Then burane = (3 - r) L ltottt
";t )2
Thc mass of one litre sample of
I L q H8 grves 3L of CO2 and I L Ca Hlo gives ozotriscd oxygeh at N.I:p was fouhd to beI 5 g. }i'hen
l0O mL of this mixture at N.T.p were treated with
4 L of CO2.
turpertine oil, the volume was reduced to 90 mI^ C{l_
Henc CO2 producd = 3r + 4 (3 -r) culat tbc nrolecul.r moss ofozone. (M.L.N.R, 1996\

= 72-x .!g!r!loj. As ozone is absorbed by turpenrinc oil,

therefore volume of ozone io 100,nL of thc mixturc
.. 12-x=10 (Given) 100-90 = 10mL
=
He[ce x = 2L
02 in the mixture = 100 _ tO - 90 L
...
t.e. propane = 2L and butane
= lL As 1 L ot the mixrure wcigh = 1.5 g, lhcrcfore,
) t::httri :tt The vepour density of a Eixture of
average molar mass of the mixlure (mass of ZZ.4 L al
NO2 ond N2O. is 3E 3 at 26 ?.C. Calculate the ruEber
ofmoles ofNO, in 100 g ofthe mixturc, S.TP.) = 1.5 x22 4 = 33 6 t mot-r
Ratio ofozoDe : orygen in the mixlure
(M.L.N.R 19931 = l0 j 90
Ifm is the molecular mass oIozone, thcn
Solutior. Suppos NO2 preseni h lO0 g of the Average mol. mass of mi ure
mD(ure = r 6
10xrr+90x1,
Then N2O4 presenr in the mixture = (100 _r)S = ----l6ii-= 33 6 (c.tlculdted above
)
Molar massof NO2 = l4 +32 = 46 t mot-l
ot m+288=336otm=4E
-hcsti rthlut Lr. One gram of o metal hydroxide on
gives 5.6g ol Eetsl oxide. Culculate the
Molar mass of N2Oa - 92 t mot-r cquivalcDt r"eight ol thc Eetal. (Brlta. C. E.C.E. 2N0l
1n8 Pradeep's

Eo. wt. of metal hvdro0de (HrSOn + 2NaOH.... Na2SOa + 2 H2O,

Eq. w1. ot metaloooe
Wt. of metal hydrcrdde
HrPOo + NaOII- NaII2POa + tI2O),
- al odde equivalent mass of HzS04
E+l7 74
Tl-6- =5'6', Mol. mass
=-.---,-=2=4'
98

or (E+17)x5 6=(E+a)x1 4
or 188=36 or F -20, and equivalent mass of HrPOo - U9f3!! = 03.
I'rohbn 21. C lculatc the mol rrity of rflater in
pure water. (Bihar C.E.C.E- 2000) Henc the ratio of masses ofH2SO4 and H3PO4

I L of Pure water = 1000 cm3 = 10008 =49:48=1t2.

-3) t'rohlon )'\. 10 ml of HCI solutlon gave 0 14358
(assuming densitY = t g cm
of AgCl when treatd iith excess of A8NO!' Find the
.. No. of moles in 1 L of pure water=139=tt tt' trorEolity of the acid solutiotr [Ag = 10E]
I'rohtrn )How many molecules are therc in 10
.< (Wen Bez,sol t.E.E- 2003)
lltres of a gas at s Pressure of 75 crtr at 27 degree ClPresent in 0 1435I AgCI
celsius ? (Bihor C'E'C'E' 2000\
Solution. PV = ,t Rf =#+x0143s8=o o3sst
750 _ ,n
760 "'" IICI containing 0 0355 I Cl
PV
=ffi=
n o;;E6o =o r morc
No. of molecules preseot in 0 4 mole
=ffi'o o"', = o o:ess-ffiseq'
= (6'o23 x1623; x 0 4 = z.lo9 x lo2!' = 0.0018 eq
l'rnhl, , )6 Potassium bromide, KBr contains ie. 10 ml of HCl contain 0 0019 eq
32 b! ..
with 3 60 1000 ml of HCI will cortarn = O 1 g eq. ie.
ofPotassi normality=01N
(N...E.R.T.) I'n,hlt'n 29 To account for atomic mass of
15N
In KBr, 32 9I of K are combined with nitro8etr as 14 (X)67' whst should be the ratio of
14N atoms in nstursl nitrogen ? (atomic Eass o[
61-19 otBt and
..3 68of Kwill combine with Br2 r'N = l4.oo3o7, lsN = tS oot z)
"na (Bih4r 2003) C'E'C'E
=!)
129
*3'6 = t s+6
laN =.t.
Solutiotr. Suppose Toage of
or6 4I or Br2 will combine with K= x6 4
ffi T7rcn Eaa|e ot 15P
= 100 -r
=3.14.s . . According to the definition of average atomic mass,
Thus Br2 is the limiting reactant oo3o? +(1q0 -r) x 1s 001
14.m67-rx14
K reacted = 3 l4g
or 1400 67 = 1500 r (14'00307 - 15 001)
ff$ t3
1+
.. xnrrormec = 14=s s4t
= 1500 1-0 99793'
= ,i fio ," - H.o, = o o8o2 u,ol
)- lko
acids II2SOa and IIIPO4 are
or x=ffi=w aza
!'rrhl, nt
neutralirrd sePorately by the same amount ofan alkali Le. EoaBe of laN = 99 636
\dhen sulphat and dihydrogen orthophosPhate are l5N
formed respectively, Find the mtio of the Easses of and qoage of = 1OO - 99 636 = 0 364
HrSOn and H3POa [P = 3ll. 111"s1 gerrgal J.E.E. 2003) .. Ratio otatoms of 15N and laN
18eq. of alkali(NaOH) willneutralizc I
0 364 L t27! 7r
eq. o and 1 g eq. of
H3POa For the givcD ,;:71=
I 99 .636
neutralization reactions
 SOIVE BASIC CONCEPTS IN CHEMISTHY 1/29

T. T.T. CANATNS ) ST'ECTA L

I'rthl D I 1.O g an alloy ofaluminium and mag- At 6OffC lead nitrate and scdium Ditrate
nesium when treated with excess of dilute HCI form decompode as follows :
magnesiuE chloride and alurnitrium chloride and
hydiogD collected over EeFcury at0'C hos e yolutne of
2Pb (NO3)2 2pbO + 4NOz+ 02
l-20 L aa 0 92 atmocpheric pressuE. Calcuhte the -
2NaNO3 -........- 2NaNO2+O2
compGition of the rlloy,
Suppose Pb (NO3L in rhe mrxrure = r g
Suppose Al in the alloy =-rg Then NaNO3 in rhe mixlure = (5 - .r) g
Then MB in the alloy = (r - ,) s
Al and Mg in rhc alloy will reacr with HCI acid as l moleofPb (NO3)2 gives I mole ofresidue of pbo
follo\trs :
i.e.207 + 62 x 2 = 331 g pb(No3h give residue of
2At + 6IICI 2Atc\+ 3H2 Pbo = m1+rc = 223 g
2 x27 = 54t
- 3xzz.4LatsTp.
Mg + 2HCl -.-.- MgClz + Hz
. r g Pb(No3)z will give residue =ff ", e
ua 22.4 t, at sT.p I mole of NaNO3 gvcs I mole ofrcsidue of NaNO2
I{2 produced fromr g of N = 1}?1L x, i.e. 23 + 74 + 48 = 85 g NaNO3 give rcsidue of
NaNOr=23 +74+32= 698
={frrats.'rp
'. (s - r) s NaNO3 glye rc516ue= x - r;
H2 produced from (1 - r)8 of Mg $ 15 g

)),n
--i'O Totatresidue = ?# - e{;:),
= -'r) Lat s'TP
l,oss in weighr ($ven) = 2aVo of 5E
. lbtal H2 produced at S.TP
2A
22 4x 22 1(l -:)l-u,,..a, =mIx5= 1.49
= 18 * 24
..
Lel us no\p convert the actual volume of
Residueleft = 5 - r.4 = 3.6 8
Hz
producd to volume at S.TP
aenceff16e$2=r6
0.92atm Pz= latm On solving, we getr = 3.32 g
P r=
Pb(NO3h = 3.32 g, NaNO3 = 5 - 3.32 = r 6ts.
vr = 1 20L
I'rthlun t AmiJ<tlureof formic acid andoxalicacid
Tt=273K Tz=273K is heatcd Mth conc II2SOa. The gas produced is col-
Pr vr PzY, o gzxt
2.0 7xv2 lect d aDd on its treatment with KOH solution, the
-T, =-T- ----TT-=-frT yolume of the gas decrcased by l/6 th. Calculate
the
molar ratio ofihe ttro acids in thc original mixture.
or Vz= 1.10+L
(I n*ee 1990)
' 224x 22.4 (7 -l.\ toa Suppose no. of moles of formic acid
lB--*-i-=t and r icacid is/. Then
isx
ot 4 x22.4x + 3 x22.4 (l - t) = 1.1o4 x.t2
C-onc
or 89.6x + 6'l.Z- 67 Zx=79.4U HCOOH + H2O (/) + co G)
.r mole II2SOI
or 22 4x = 12.288 ot x = 0.54a6g r mole
..VoolN=54A6 COOH
co (8) + co2 G) + H2O (t)
aDtJ 7o of Mg = - 54 .86 = 49 COOH / molc y motc
1OO
)'nn)h D J. A solid hixture (S.0 g) consisting of
14.
y mole -
. -
lead nitrate aEd sodium nitratewas heated bclor 60O.C Totalno. of molcs ofgaseous product = .y + 2 y
utrtll the wcight ofthe ttsidue was constanL Ifthe loss As only CO2 is absorbed by KOH, therefore frac_
inweightis2E 0percenglindtheamountofleadnitrate
qnd sodium nitrate in the mixture, tioD of CO2=
(I.r.T. 1990) #, = | or 6y= x+2y
1/80 Pradeep's

4
4Y=x or ;= HeD"e +0.01 = 0 02 or x=0.539
or T k
i3 , tm = zs S*
O
Hencemolar ratio of HCOOH to (COOHtis4:1. Eo ofNaz1os =
I'robleu 4. Colculate the DuEber of oxalic acid
moleculcs in 100 ml of0 02 N oxalic acid solution. 70 of NaHCOT =o {, tm = eZ ot"
(Roortze 1991) % ofN%so4 = 100 - (26 5 + 42 O) = 31 5%
Solution. mlof0 02 N o,Glic acid solution
100
i rablen 6, Upou mixiug 45 0 ml ofO 25 M lead
=O 002g eq =0.OOlmole= 1o-3mole nitrrte solutioD teith 25 0 ml of 0 10 M chroElc sul-
phstc solution, percipitation of lesd sulphste takes
= 6 02 x 10m molecules. place. How many moles of lead sulPhatc ar forEed ?
Problefi 5. A2 Oesample ofa mixture contaitrhg Also calculote the molar concentration of th spcies
sodium carbonote, sodiuE bicarbonate atrd sodium sul' lefl behind in the llnel solutlon. Assum. that lead sul-
phate is gently heet d till the evolution ofCO2 ceascs. phate is complei.ly insotuble (AL wt of Pb = 2(, 2).
The volume ofCO2 at 750 BE Hg pressuie 8nd aa 29t K (I.I.T 199i)
is measured to be 123 9 IIrl. A 1 58 of the same satDPle Solution. 3Pb (NO3)2 + Cr2 (SOl)r
requires 150 ml of W10 HCI for coEPlete neutralizo- 3 moles I mole
tion. Calculate the pcrcent!8e comPo6itiou ofthe coltr' ........
(I.I.T, I 992\ 3Pb SO4 + 2 Cr (NO3)3
ponenLs of the mixture.
3 moles
SuPPoso Na2CO3 = x8, NaHCOT =)8'
45.0 ml of 0 25 M Pb (NO3)2 solution
Tllen Na2SO4 = 2 - (x + f) 8.
x
On heatlng only NaHCO3 will demmpose to give = ffi +5 mole of Pb (NO3)2

CO2 as follows : = 0 01125 mole

2NaHCO3 NECO:+H2O+ COz 25.0 mlof 0 10 Mcrz(so4)3 solution
2(84)c
- ?s[' = -q1 x 25 mole of Cr2 (Soa):= 0.0025 mole

NaHCot will co, = 2# x / ml at sTP Evidently Cr2 (SOr3 will be the limiting reactant.
y I git'e

Actual CO2 producd at STP may be calculated as

0 0025 molc Crz (SO1)3 will react with
folloBr : Pb(No3)2 = 3x0 0025mole=0 007s mole

Pr Vr PrY, 160 xY, '. Pb (NO3)2left in the solution

-71 = -T;'--27J- =
= o 01125 -0 0075 mole = 0 00375mole
Vt = 112 0ml Totalvolume of the solurion = 45 + 25 = 70 ml
. . Molar conc of Pb (NO!)2 left in the sol.
aen".fft = i2 or y=o84g o qoJ75
I .5 g of the mixture requires M/10 HCI = 150 ml - xloooM = o os357M
.. 2.0 g of the mixture will require M/10 HCI PbSOa formed = 3 xo oo25=0 0075 mol

=.!!9rzo=2oomt I'rnblen 7 Amirtweof ethaEe (C2H6) andethenc

1.5
(C2H, occupies litres at 1 0O atEl sril et 400K. The
40
= O 02 mole HCI
mixture rcacts comPlet ly with 130 8 of O, to Produce
Na2CO3 + 2HCl 2NaCl + H2O + CO2
CO2 and H2O, Assuming idial gas behaviour, calculatc
106 g 2 moles
-
+ HCI- NaCl +H2O+COz the mole fractions of C2Ha and C2H6 in thG mixturc.
NaHCO3
UE 1 molc (I.I.T I egs)
, APPlying the ideal Sas equatioo,
r8 Na2 COJ require HCI = t06--1
xrmole.
PV=nRT
xo 0821 L atm K- I mol- I x 4mK
1
0 84I NaHCO3 require HCI= gh x o 84 mole l atm x 40L =n
=0 01 mole or r, =
40
6:[8ri:;Tm = 1.218 mole
 SOME BASIC CONCEPTS IN CHEI\,4ISTRY
1/81
(where z = total no. of motes of qH6 and qHa : a+b - la mL (Civen) .. (rr)
in the mixture) The Iirst given decrease is due to 02 consumed.
Suppose the no. of moles of qH6 in the mixture
=x a mL of CO wlll consume O, =
$mL
Then the no. of moles of ql{a in the mixture b n L of CHa will con srme Oz = Zb ml,
= 1 218 -.r ' O, consumed :f + 2b = t3 mL (Giveh)...(iii)
A.lso 130 g 02 = of O, = 4 0625 motes
$motes tiom cqns. (r) and (ii), c =
The rcactions for complste combustion of C2H6
ZO - L4 = 6 mL
Fiom Eqns. (t) and (iii),
and qHa are
$+ 2 gt - a) = r, orlo = t5 or a = 10 mL
2qH6 + 7 02 4CO2+ 6LlzO ...(r)
.. From eqn. (ii), tO + b = 14 or b = 4 mL,
and qHa + 3O2 -......- 2CO2 + 2HzO ...(r0
CO = l9 p1. 6110 = 4 mla N2 = 6 rrrl
Irrom (i), no. of moles of02 rcquired for complel.e
I'rohl, u r.t.
One litre of a mixture of 02 and OJ at
combustion of.r motes of qH6 =|r, = Z.S, NTP was allorved to react with an exccss of acidilied
solution ofKL The iodinc libcrated required 40 ml of
From (ii), no. of motes ofOz required for complere
NVl0 sodiurn thiosulphate solution for titrotion, What
combusrioD of (1.218 moles of qH1 is the weight perccnt of ozone in the mixture ?
-x) Ultraviolct radiations ofwavelength 300 lIm can d.com-
=3 (1.218 _ x) posc
Hence 3.5r + 3 (1.218 - x) = 4.0625 D decompose
ohe would have
or 0.5r = 4.0625 654 = g 4055 been tion ofozone
oI r=0 -3 in th
8170mole GI.T Dgn
Mole fradioD of qH, =ffi=o lglullgll o: -.- oz + o
oz
2 KI + H2SO4 + (O) + IqSO4 + H2O + I2
and Mole ftacrioD of qH4 = 1 - O 67
2 Na2SO3 + 12 -+ Na2SaO6+2NaI
=0 33
2Na2S2O3 + 2KI + 03 + H2SOa ....-..-
/ /
"r/,.r/ ,l A mixture of 20 mL of CO, CHa and
N2 was bumt in excess of()2 resulting ir the reduction 02 + K2SOa + H2O + Na2S4O6 + 2 Nal
of 13 mL ofvolume. The residual gas was thcn treated 2 moles of NESz03 react wjth one mole of 03
with KOH solution to show a contraction of 14 mL in
volume. Calculate volume of CO, CHl and N2 in the No. of moles of NqS2O3 iD 40 ml of NES2O3
mixture. AII measurements are made at constart pres_ #
sure and tcmprature. 11
= m- x x to-3
e.I.T iggs) Jb;d x ao = 4 mote
Solution.
^-- = D7r1"n6 Slppose volume of CO = a mI_, .
CHo *, = crnl. Then 03 reacted (present) = 2 x l0-3 mole
a+b+c=zomt. (, Volume of O, =2x7O-3 x22.4L=0.0448L
The combustion reactions will be . Volume of 02= I-0.0448 =O9552L
1
CO+i()2-CO2 Weighr of 03 =2x10-3 x 48 = 0.096 g

CHa + 2 o2...- CO2 + 2H2O (/) weight ot o, = ffi x 32 = 1.3646 g

N2 + O, -..- f.Js 1sss116n .. Weight of miKure =0.096 + I.3646

Tbus, a rzl
of CO will produce CO2 = a mL = 1.4606 g
6 n L of CHa will pro du,ce COz = b mL .. % of 03 by weight = , rco = 6.s1r%
f#
Nz will remain
as suchi.e. = c mL No. of molecules in 2 x 10-3 mole of 03
As CO2 is absorbed by KOH, dccrease in volume
=2 x 1O-3 x J.022 x 7O23= 1.2044 \ rc21
on rreating with KoH will b
No. ofphotoos required = 1.2044 x l02r
1la2 !)ra tl,' r :,'. Net{ Co urse Chc m i strg fiffi
!'r,t r, n I't 1 2g mixture of Na2CO3 ord ,'.e, fICl left unreacted = 12 meq

K2CO3 was dissolved in va(er to form 100 cm3 of a HCI used up by MgO and Mg3N2
solution. 20 cm3 of this solutiotr required 40 cm3 of = 6O-12 = 48 meq = 48 millimoles
0.1 N HCI for neutralisation. Calculate the weight of Suppose in thc mixture, there are r millimoles of
NarCO, and K2CO3 in thc mixture. (Rootkee Dgn MgO andy millimoles of Mg3N2
Solution. Suppose weiSht of N%CO3 in the mix- Then 2r + 8), = 48
ture = rg: ot x+4Y=24
. Weight of IqCOr in the mixture = (1'2 x)g Further,
NHaCI + NaOII- NaCl .t H2O + NH3
46 + 17 .+ 148
Eq. wr. of N%CO3 Acid used up by NH3 = 10 6 = 4 meq.
-
?e-t',f48
'" ' ' " -oe . NII3 produced = 4meq = 4 millimoles
Eq. wl. or ryco3 = ; or NH4CI formed in reaction (ii) = 4 mjllimoles
No. ofgeq. ofNa2CO3 and IqCO3 in the mHturc Thiswill be formed from MgjN2 = 2 millimolesi a
x
- 53_l'2-,
_
69 l{ence ,r+4x2=24otx=16
40 cc of0 I N HCI coDtain g eq. ofHCl 2M8+02+2M8O
,1 1
3 Mg + N2........ Mg3N2
=-:-j-x40=4x10,
16 millimoles of MgO are obtained from Mg
Thus 20 cc of the mixture sol neutralize HCI
= 16 millimoles
=4 x 10 'g eq
2 millimoles of Mg3N2 are obtaiDed from Mg
. 100 cc of the mixture sol. will[eutralize HCI
= 6 millimoles
=-#ax1oo=2xlo-28eq Total milliDoles of Mg = 16 + 6 = 2:2
=0 02 I eq. Hencr Mg converted to M83N2 = * ,' 100
As subsmnces react in equivalent amounts,
=27 27co.
x 12-x ^^- h t(n I) How many millilitres of 0 5 M
3f--9_:=002 H2SO4 are needed to dissolve 0 5 g of coPPer (II)
ot 69x+63 6,53t =0 02x53 x69
carbonate ?
=73 14
(At.Eass:H = 1,C = 12, O = 16,S = 32, Cu =
or 16x=9 54 63.s) @LT, 1999)
or x=0 5969 Solution. CUCO3 + H2SO4
Thus Na2CO3-0 596I -..- CuSOa + CO2 + H2O
and IqCO3 = 12-0 596=O 6O4C
I
moleCuCO3 =635 + 2+ rA=12359
i rbit t t I A sample ofmagnesium was burDt iD
requireII2SO4=1mole
air to give a mixture of MgO and Mg3N2. The ash was
0 5I CuCO3 will require HrSOo
dissolvd in 60 meq of HCI and th. resulting solution
back titrated with NaOH. 12 meq of NaOII werc re- 11
quired to reach the end poinL An excess of Naoll was
= r23 j x0 5mole =r;molc
then added alld the solution distilled. ThG ammonia 0.5 mole of 0 5 M H2SOa are prescnt in 1000ml
relersed rYas thcn trapPed in 10 meq of second acid 1
solution. Back titration ofthis solution required 6 meq
2i7 mole of 0 M Ii2SO4 will bc Presenl
5 in
of the base. CalcYlate the Percentagc of magnesium
burnt to the nitride. (Roorkce 1998'l
Solution. M8O + 2HCl- MgCl2 + HzO...(,
ffi,,r|rrnr =t r-r.
t t,tDit ot t i. A Plalt virus is found to consist of
Mg3N2 + SHCl......- 3 MgCl, + 2NHaCl ...64 runiform cylindrical particles of 150 A in dixmeter nnd
5tx)0 A long. The specilic volume of tbe virus is 0 75
12 meq of NaOH = 12 meq of HCI
 SOME BASIC CONCEPTS IN CHEMISTRY
1/83
cm3 /t, If the virus is coDsidered to bc a sirnple paraicle, Molarity of water means number of
find its molecular rpeighL 1t.t.t tOeel moles ofwater in I litre ofwater
Solution. Volume ofone vkus particle = z,2 L l Lof .\rater
= loOO cn3 = l0OOg

=?" (!*"ro-8.m12 x (sooo x lo-Ecm.) 1... d. = tXgtms = t grcm3l

' \z /
l0OOgHzO =
Smoles = ss se mote*
-8839x10-17cm3
Mass of one virus particle I'roble, 16. A Eixture of FeO and FerOn was
heated in air to a conslant mass. It was found to gain
1I
=8 839 x "
10-17cm3,
ons;;,
107, in its Eass. Calculate the prcentag"
ofthe ori8inal mixturc. (West "o-po"ition
BenBatI,E.E. 200{)
= l1 7E5 x 10-r7g On heating in air, both FeO aDd Fe3O4
Molar mass (t.e. mass of Avogadro,s no. of par- are oidtzed to Fe2O3 as follows :
,

= (lr.?85 x 1o-l7g) x (6.023 x lozl)

2 Feo * 1o, Fe2()3,
2 (56 + t6)
=144t
2x56+3x16
= 7 .09t x 107g mol-r. :160s
I'nn,tu tJ The formula rveight ofan acid ist2.0 zF%oa*]or-:r"16,
in a titration. 100 cEt3ofa solution oftbis acidcontain_ 2(3x56+4t16) 3xt6o
ing 39 0 g of the acid per litre were completely = 4At = 48Ot
nutralised bJ' 95.0 cm3 ofaqueous NaOH cootainiDg Suppose FeO in rhe mixrwe = xVo
40.0I of NEOH per litre. \ hat is the basicitv ofthI
acid ? 6oor*.ee 2000)
Then Fe3O4 iD the mitr,twe - (1Oo _ x) Eo

Solution. Suppose lhe equivalent weight of lhc

acid Fe2O3 produce.d lrom x g of FeO = .lf x,g
=E-
. Normality of rhe acid solurion = Fe2O3 produced ftom (r0o _ r) t of Fe3Oa
f;
480
Eq. wr. ofNaOH = 40 = ?34 x (100 _ r)8
.. Normatiry of NaOH sotution = N=IN lbtal Fe2O3 produced from l0Og of the mixture
;3
= 100 + 10 = 1108
Applying NlVl = N2V2
(Acid) (NaoH) ' t& x + ,180 (lo0 _ r.)
JEi- ---;i- = lro
3q
or 19.! + 30 (100 _ x) _ ,,
8x100=1x95 ".-3---_.f'-=tto
or E=41 0 or 29Ox + 27O (lOO -x) = 110 x e x 29
. Bastcity. of the acid - Folmula wr'
- 82 0 ot 20, = 1710
Eq. wt. 4l .0 --.'..
I'rtnthtn t5 Calculate thc molority ofwater ifils or r = 85.5
density is 1000 kg/rz3 (r.r.T 2003) .. FeO present in the mixrure 85.S7a
=
and FerOn = 166 - 85.5 = t4.S%.
 Nerl Course Chem istr'!
1184

ANU LT' PLE CHOI CE wtrsTtoNS

and
10. 2 76 s ofsilver carbonate (at massofAg = 108)on
The number ofsiSnificant fi8ures in 0 050 is
being-heatcd strongly yields a residue weiShing
(o) 1 (b) z
(a) z.16 g (b)2 a8g
(c) 3 (d) 4.
(d)2 64 s
2. Which out of the followin8 is not a homogeneous -4<fz.zz e
mixture ?
11. If 0'5 mol of BaCl2 is mixed with 0 2 mol of
(b) Brass Na3PO4, thc maximum [umbsr of molcs of
(a) Air
(c) Solution ofsugar in water Ba3(Po4)2 that can bc formed is

(d) Smoke. (a) o 1 (b)0 s

3. A compound has the emPirical formuh qI{3O2' (c)0 3 -.@fl.t "I "r\t
Its vaPour density is 59. I$ molecular formula will 12. If 1021 moleculcs are removcd from 200 mg ot
be COz, then the number of moles of COz lsft are
(b) c4H6o4
@)qll3oz (b)l66xl0'
(d) c8H1208.
lafz u * to-r
(c) C5HeO6
(c)4 54 x 10-3 (d)166x1o-2
4. The number of molecules present in 8 g of oxygen
8as are of
13. 'fhc number of gram molccules oxygcn in
(a)6.o22 t lo23 (D)3 011 x 1023
6 .
02 x 104 CO molecules is
(c) 12 (M4 x to23 (d) 1 55 x lo23
10 g molecules -@J3 g molecules
.pJ
5' 112 cm3 of hydrogen gas at STP contain (c) 1g molecule (d)0 5gmolecule.
(a) 0 0O5 mole (b) 0 01 mole

(c) 0 02g (d)3 011x1022 molecules 14, Onc mole of COz contains
6. C-aCO3 oo reaction with 0 1 M HCI acid will x atoms of C
10 I . @6 oz 1023
produc CO2 (b) 6 O2 x t 023 atoms of C)

(a) 1120 cm3 (b) 2240 cm3

(c) 18 1 x 1023 molecules of CO,
(c) 112 efi (d) 224 cm3. (d) 3 I atoms of CO2.
7. One fermi is X (atomic wcrghl = 75) and Y
/1!. {alomicweight = l6) combinc to Sive rt comprtund
fwo ctemenls
(a) 10-13 cm (b) 10-15 cm
iraving 75 8-% ofX. The rormula ofthe compound
(c) 10-10 cm(d) 10-12 cm' is
r-g,Wtrlctr of the following has the largest number of xrY
atoms ? ' 1r; xY (D)

(d) xzv y
(a) 0 5Iatomof cu (6)0 6358ofcu (c) X Y2
(c) 0 25 moles of Cu atom
(LL X 1971 Is in
(d) 1g of Cu. 16. The largesl numbtr o[ moleculcs
9. 27 got N (at mass = 27) will react \\'ith oxYgen (a) 54 g of nitrogen Peroxide
equal to (b) 28 I of carbon dioxide
ltt) U B
(b)88 (d) 46I of ethylalmhol.
(c) 40 g (l) l0 s. '.rl.L \.R lr)lJ

t.d 9.a 10. c

t.b z.d 3.b
11. d 12, a 13.
'
 SOME BASIC CONCEPTS IN CHEMISTRY
1/8s
17. The molecular wEight of Oz and SO2 arc 32 and 64 (a) 0.5 M (6)1.0M
respectively. If one litre of C)2 ar l5.C and 750 mm (c) 1.s M (d)2.oM
contains N molecules, the number ofmolecules in t.t !.t M.,\ t eet'\
two litres of SOz uDder tbe same conditions of 24. Given the numbers : 161 cm, 0. 161 cm, 0.0161 cm.
temprature and pressure will be The number of siglificant figures for the thre
(a) ND (6) N numbers are
142N A*{N. \,v.t. \,.R ro')t \
(o) 3,4 and 5 respcctivety
Five grams of each of the following gases ar 87oC (6) 3, 3 and 3 respectivety
and 750mm pressure are taken. Which ofthem will (c) 3, 3 aDd 4 respeclivcty
have the least volume ?
(d) 3, 4 and 4 respectNely. i.C.tr.,;.t, t!,tt.t: it),),\t
(a) HF (D) IJCI 25, 39
(c) HBr ,.tlTfit. of
ttll L \" lt Itjel um
'
19, Which one of the following is the standard for nt
atomic mass ?
haemoglobin is

(,) lH p'r. (a) 6

(c) 4
(b) |
(d)2.
(") ;tc (d) 160 t t.! t: tss3\
20. Rearrange the following (I to w) in rhe order of 26. In rhe reacrion 4 NH3 (g) r s 02 G)
increasing rDasses and choose the correct answer
from (a) (b) (c) and (d). Aromic masses : N = 14,
4 NO G) + 6 H2O (l), whenI mote of ammonia
-
and I mole of 02 are made to react to complction
O=16,Cu=63)
Ll molecule of orygen , (4) I 0 mote of H2O is produceJ
' IL 1 atom ofoitrogen (6) I 0 mole of NO wi be produced
III. 1 x 1010 g molecular weight of oxygen (c) all rhe orygen wi be consumed

IV 1x l0-18 g aromic weight of copper (d) all the ammonia wlll b consumed.
(a)II < I < III < IV (D)IV < III < II < I
(c) II < III < I < IV (d) tII < tV < I < IL
27. lt)e number of nrolecules in 16 g of methane is
(a)3 0x lOa (b)6 02x 1023
21, The number of moles of H2 in 0 224 litrcs of (c)u$x y
hydrogen gasarSTp(273 K, I atm) (assumingideal
104
' '3-!a0
1d1 16zl

gas behaviour) is
(a) 1 (6) 0. I 24. 50 ml 10 N H2SO4 , 25 mt 12 N HCt aDd 40 mt
$.ot Jd) 0 001 5 N HNO3 were mixed togetherand the volumeof
t,tI L.\.R. 1991) lhe mixlure was madc lO0O ml by adding water.
22. 'Ilvo conEincrs p and e of equalvolume (1 litre The normality of the resultaDt soluiion will be :
each) contain 6g of02 and SO2 respectiirly at 3OO (a)1N (r) 2N
K and I atmosphere. Then (c)3N (d) 4N.
(a) No. of molecules in p is less than that in e
(6) No. of rhe molecules in e is less rhan that in p 'lte number of atoms in 4.25 g ot NII3 is ap_
(c) No. of molccules in p and e arE same proximately
(d) Eirher (4) or (6) tHo!.a nc.E.t:.t tset.\ 1x lF
(a) (\2xrG3
23. The maximum amount of BaSOa precipitated on (c) 4 x 104 @)6 x lofi.
mxing BaCI2 (0.5 M) wirh H2SO1 (1M) wilt mr_
respond to ' i, t l!,14 t tr'),!,

17. c ta. d 19, b 2ll. a 2t. c 22. b 23. a 24. b 25. c 26. c
27. b 2t. a 29. d
1186
lrratleep's Neut Coursc thcmistrg lft[p
30. A molal solution B one tbat coEtaiDs 1 mole of a (a) 6.W x 1dl mohcutec of co,
solute in
(r) 22 . 4 L of CO2 at STP
(4) 1000 I of the sohrnt
(6) 0 44 g of CO2
(6) one litre of the solvent
(c) one litre ofthe sotudon (d) None of these. u.I.PM.Ii.R. 2000\
(d)22 4littes of the solution. (If
P CE E 7999) 3E. Number ofg of oxygeD in 32 28Na2SOa. l0H2O
31, A 1OO ml solution of O 1 N HCI was titrated with IS

o 2 N NaOH solution. The titration was discoD- (a) 20 8 (b) 22 4

tinued after a
remaining titr
(c)2 u (d) 2.o8.
tIln^a ( l' ll l::t)lt/)\
N KOH soluti
completing the titratio8 is
(a) 70 ml (b)32ml
(c) 35 ml (d) 16 ml. (D.C F-. 1ee9) anhydrous enryme is
32. One mole of calcium phosphide on reacdon with
excess of water gives
(a) I 568 x 1d (D) 1 568 x 1d
(a) one mole of PhosPhine (c) 15 68 (d) 3 136 x 104
t('.ll.S.l-.. l!)ll l: )t)tti I

(b) two moles of PhosPhoric acid

(c) two moles of PhosPhine The prcentage ofnitrogen in urea is about
(o) 46 (6) 8s
(d) oDe mole of Phospnorut *r,oxio";r.
a r, , rrq (c) 18 (d)28 tK(.It.T 2oo1\

33. Assuming fuuy decomposd, the volume of CO2 Ho'fl much ofNaOH is required to neutralise 1500
cm3 of O I NHCI ? (Na = 23)
released at STP o,r heating 9 85 of BaCO3 I
(4) 40I (6)4s
(Atomic mass, Ba = 137) willbe
(c)68 (d)60 E tK C. tt l: 2 t)()1 t
(s)o uL (b\ 2.24 L
dz3 of N2 gas and 10 dm3 of 8as X at the same
'10
(c) a.06 L (d) 1.12L.
(C B.s.D I!'V T 2000) temperature ccntain the sa e number of
molecules. The gas X is
34. The sPecitic heat of a metalis0 l6.ltsaryoimate
atomic weight would b
(a)co (b) co2

(a) 32 (b) 16 (")Hz (d)No,^(tt:lit

(c) a0 (d) 64. ti t.l.l[ s.2000) The volume of\ ter to be addcd to 100 cm3 of
35. The weiSht of a molecule of the comPound 0 5 N H2Sot to get deci normal concrntratlon $
C6oH122 is
(a) 100 cm3 (b) 450 cm3
(a)1 4x1O-2tg (6)109x 10-21g (c) 500 cm3 (d) 400 cm3
(c) 5 025 x 10239 (d) 16 O23 x lF g' t K.(.1,,.'l: )tt0l )

t,\ILlIS 2000) 44. The set of numerical coefficieflts that balances the
36. The number oI water molecules present in a drop equation
ofwater (volume0 0018 ml) at room temperature IqCrO4 + HCI IqCr2OT + KCI + H2O is
ls -
(a)6 023 x 101e (a; r.oel x tort (a) r,r,2,2,1 (b) 2,2, 1, 1, 1

(c) 2, 1, 1,2, (d)2,2,1,2,1

(c) 4.84 x 101? @)6 0a x lc. 1
( Kerah li.E li. )0t)l
(D.C.0.2000t 2,2,2" 1, I
(e)
45. 250 ml of a sodium carbonate soludon coDEins
3?, Which of the folowing contains maximum number
2.65 Srams of Na2CO3 If 10 ml of this solution is
of atoms ?

30. a 37..1 32. c 33..1 ?4, c 3t. , x9, a

40. a 41, c 42. a 43..1 44..1
SOME BASIC CONCEPTS IN CHEMISTRY
1187
diluted to one litre, what is the conceDtration ofthe 53. AmoDg FeSO1.7H2O (A), CuSOo.5HrO (B),
rF,sultant solutioD ? (mol. wt. of NECO3
= 106) ZnSOI . 7 H2O (C), MnSOa . 4 H2O (D), isomor-
(a)0.1M (D) 0 001 M phous salts are
(c) 0.01 M (d) 10-1M (a) A and C (D) A and D
(c) C and B (d) A and B
t E./1. lf.c. E.7: 2t)0 1\
I D.l!,tL I: 2t0.t )
46. 7 5 grams of a gas occupy 5.6 lires ofvolume at
Sm The gas is What will be the volume of the mixture after the
reaction ?
(a) No (6) NzO
G) NH3 (1 L) + G) HCt (1 .5 L) ...- NHICI (r)
(c) co (d) coz (a)1sL (6) 0.5 L
\ 1,..1 .11.(.1:.'l: 200t t (c)lL (d)OL tt).t!,r1.'1: 200.1)
47. AD aqueous solution of 6 3 g of oxalii acid 55. A compouod has hacmoglobin like
structure. [thas
dihydrate is made up ro 250 ml. The volumeol0. l one Fe. It coorain 4 .6% of Fe- The apFqimate
N NaOH required to completel,v neutralise t0 ml molerular mass is
of this solution is (a) l0ogmol-t (6) 12oot mol-l
(a) 40 ml (b) 20 mt (c) l,toog mot-r (d) 160O9mol-r
(c) 10 ml (d) 4 ml. (t.1.7: 2001)
(D.PM.T 200i)
4E. Holr| marry moles of electron weigh one kilotram ? 56. In Haber process, 30 litres of dihydrogen and 30
(a)o oB x tP lires of diniuogen were raken for re{aion wtich
(D)
e;{* x rdl yeilded only 50% of the expecred product. Wbat
6 o23 will be the compciton of the gaseaus mixture
t"\
' '9 r lcfa (d) x lOt under the aforesaid conditon in rhe end ?
108 9 108 x 6.023
(4) 20 litres NH3, 25 litres N2, 2, tirres H2
(I.l.T 2002)
49. The prefix (6) l0 litres NH3, 25 liEes N2, 15 tiues H2
1018 is
(a) gi$a (c) 2I) litres NH3, l0litrcs N2, 30 litrer tI2
(D) exa
(c) kilo (d) nano
(d) 20 litr6 NH3, 25 litres N2, 15 litres H2
(e) mega lKctdla ll.E.E. 20021 ( c. R.s.Ii. l! II.T. 200 1t
Number ofatoms in 558.6 g Fe (molar mass Fe 57. What volume of hydrogeD gas ar 273 K and I atm
=
55.86 I mol-l) is be
presrure will .69
elemental boron the
(4) Mce that in 60 g carbon
reduction of boro
(b)6oBxtfz (c) half thar of8I He (a) 67 2L (b) 44.8 L
(d) 558 6 x6.O23 x 1G3 r.1.E.8.E.2002\ G) 22.a L (d) 89.6L
3. 929 of ferrousammoDium sulphate aredissolved t;l.l. I,. L, li. 2 ()t).1 t
in 100 ml ofrvater. 2n ml of this solulion requircs 5E, Which has maximum number of atoms ?
18 ml of potassium permanganate duriDg titratioD
for complete o)ddarion. Tt e weight oa KMDO4 (a)usorc(12) (6) 56s of Fe (56)
present in one litre of the solution is
(c)27 gof N(27) (d) 108gof Ag(108)
(o) 34.76 g (b) 12.38 \l I t: )t)0-1)
E 59. Mixrure X = 0.02 motof (NH3)5 SOo]Br and
(c) 1.238 I @)3.a76 E
[C-o
0.02 motof[Co (NH3)5 Br] SOawas prcpared in 2
( (.8.'t )002
lanil lladu
Iitre ofsolution
3 g of an oxide of a metal is converted ro chloride
completely and it yielded 5 g of chtoride. The 1 litrc of mixture X + excess A8NO3 + y
e4uivalenr wight of the metal is I litre of mixture X + excss BaCl2..... Z
(a)33.?5 (b) 3.32s
Number of moles of y aDdZarc
(c) 12 (d) N iK.L:1.:.L 2002\
(a) 0.01,0.01 (D) 0.02, 0 01

AJSWE
45. b 4.o 49. b 50. a 51. ./ 52. a 53. a 54. b
55. 56.
' '
 1/88 Neur Course Chemistrg
(c) 0.01,0.02 (d)o.o2,o t2 (b) 150 cc of N2 at ST?
t I 1- l: )t)t)l: (c) 50 cc ofSO2 at STP
60. The ma\imum number of molecules is present in
(d) 150 cc oI Oz at STP
.(oits t ottl, gass.TP (b) 5 L of N2 gas at s.TP
(e) 200 cc of NII3 at STP
(c) 0 5gofH2gas (d) l0gof02gas
66. A samplc ofphosphorus rrichloride (PCI3) contains
t( .l].\.1,. l)tl
l: )001\
1 4 mcrlcs of thc substancc. IIow many atoms are
61. 4 g of copper was dissolved in conctntrated nitric there is the sample ?
-fhe copper nitrate on strong heaiing
acid. Save 5g (a) 4 (6)s6
of its oxide. The equivalcnt wcight ofcopper is
(o)?3 (b)32 (c)12 (d)20 (c)8 431 x 108 (d)3 372 x tfa
( 'l l:2ttttlt (e)2.N9 x lfa iKtah l'l.l l:. 2u01)
1ft ouloog and tetir's law is 'M A gas mixture contains 50 helium and 50%
(a) metals (6) non-metals methane byvolume. What is tbe pcrcent byweiSht
(c) gaseous elements (rfsolid elements ofmeihane in the mixture ?
(a) le.e1% (b) 20 osva
(c) 50Vo (d)7s%
/480.$q. (turuln,tl. l'..ll. )0t)1
x \P
(a) 6.U2 (b) t2-04 x 1O22 116 mg compound on vaporisation ln a Victor
of a
Meyer's apparatus displaccs 44 8 ml of air
(c)1806x10P (d) 31.80 x 1028 measured at STP The molccular weight of the
(.1 t K.( .l.:.l.200J1 mmPound is
64, One gram mole cf a gas at NTP occuPies 22 4 (a) 116 (b) 232
litrcs. This fact was derived from llfss (d) u.8
(a) I-aw of gaseous volumes a6.4 i K(rult ill.lr.L:. 21t01)
@)
,15j nvogaoro's hypothesis Number ofwater molecules in the drop ofwater, if
{9}Eerzclius h}'pothesis 1 ml of water has 20 drops aod A is AvoSadro's
(d) DaltoD's atomic theory tI rt L.( l).1) )lrtJ t
number, is
65, Which of the following contains maximum number (a) 0.5 A/ 18 (6) 0.05 A
of moleculcs ? (c)0 5A glfo.os tt ta
(a) 100 cc of CO2 at STP

HINTS/EXPLANATION9 to
2. C-arbon particles (solid phasc) are dispBed iflto air
= :' x L |23 / l0.r mole'culcs
(gasous phas).
9. 4N + 3Oz 2 NzOt = 2 77a x 1021 molecules
4x218 3x3zE - lelt
Atter removing 1021 moleculcs, molecules
10. Ag2Co3 Ag2O + CO2 1

2x1G+12+3x16 2x108+16
= (2.?38 - l) 1021

=2168 = 1 738 x 1021 molocules

11. 3 Baclz + 2 Na3POa ....- Bar(POr), + 6 NaCl lo:l mol rmol

-1738x
6 023 x 10'
=2 88r10
3 moles of BaCl2 reacr with 2 molesof Na3l>O4.
13. I molof CO= l gatomof O
Na3POa will b rhe timiting rea ant.
t2. or6 02x lOBmoleculesof CO = |g moleculc of
20o mg of CO2 = 6 296 g - f,or o2

"4 A/s 66..1 e

59. a 60. a 61. b 62. d 63. c 65. r, 57, 68. c
69. .l
SOi/E BASIC CONCEPTS IN CHEMISTRY 1/89

.. 6 02x 1024 molecules of CO atomic $erght of Se = 78.4, lherefore 1g atom of

Se i d 78 4 g will be prescnr in en4me
I 6.O2 x tO24
:7xffi;fu=5Smolecules too
iigx?84g=l568xto1g
15. X=75 a%,'{ =24 28o. Fitrd er,/piricat formula-
40. NH2CONH2 = 2N
16. 54 g N2O5 = 541108 mol = 0 50 mol
l mol 2gatoms
28 g CO2 = 2f,144 mol = O.@mol
(,oE 2Eg
,a
36gHrO=36/18mol=2mol 'iagcotN -ffix 100 = aoa.
46gqHsOH = 46146 mol = lmol
41. 1500 cm3 of 0 INHCI =ffixrsoo
17. Equal volumes of dilferent gases under same con-
ditioBs o[ temp. aDd pressure contain equal num- =0l-5gcq
ber of molecules. Ir will neurralis Naoft = 0 15 g eq.
lt. 5 g HF = 520 mol,5 g HCI = 566.5 mol,5 g HBr
=015x409=68
= 5181 mol, 5 g III
= 5,/121 mol. Thus III has least 42. No. of moles of N2 and X should be equal 'lhiscan
no. of moles and bence least volume,
bc so ifX has same molccular weight as N2
22. 6 8O2 = 6E2 n,ol, 6 g SO2 = 6/44 mol. Thusvessel
.13. NtVr = NrVrie.0 5 x 100 =0.1 x Vz
Q has less no. of moles.
25, Fe present in 672O0 u - 9j1 xouzoo or V, = JQQ 663

)r) Watcr to be addcd to l0O cm3 solurion

=222u=#=4atoms.
= 500-lO0 = 400 cm3.
26, C)2 flll be Iimiting rcadanr, Hence all oxygeD will 44. 2I<2CIO1+ 2I{Cl....* KzCrzO; + 2 KCI + }l2O
be coosumed. 22r2i
2t, NlVt + NrV, + NrV, = NoVo 45. Molarity of given Na2CO3 sol
lO x 50 + 12 x 25 + 5 x 40 =N4 x 1000 265 r2S0.1000=0lM
l
= 106
or N1 -lN
M,V1 = M2V2, 10x01= 1000xM2
29. 4.25 g NH3 = 4.25111 mol
or M2=0001 M
= 0 25 x 6 022 x IOImolecules
46. Ma.ss of 22.4 L of gas ar STp =fi "rr.o
= (1 + 3) x 0.2S x 6.022 x 1023 atoms
31. NtVt = N2V2 + N3V3 ie =30 g
0.1 x 100:0,2 x 30 + 0,25 Vl i.e. molccular mass of lhe gas = 30. Ileoc gas is
NO.
Ca3P2 + 6 HrO-* 3 Ca(OH)z + 2 pH3
47. Normali& ofoxalic acid soi.
u. Apprcx. atomic weight = 6.4,6pecific heat 3 1000 6
(DubnB aod Pe rifs law)
-250x 63 =oa\
35. l molofC6oIIjzz = 60 x 12 + 122 x1g =Bi2E 10x04=Vx0I or V=40mI
4t. l mol ofclecrrons weigh
= 6.O23 x lo23 molccules
36. 0 0018 ml fI2O = 0.0018I HzO = (9 r08 x 10-31) x (6.023 x 1023; kg
-( d= m1-l;
Ig or 9 108 x 10-31 x 6.023 x lF kg of elcctrons
1 mol II2O = 18 g - 6 023 x 1021 moiecules = 1 molofcleclrons
3E. 1 mol NESOa.IO H2O = 149 aroms of (O) . 1 kg of electrons

i.e. 322 g NalSOa.lO I-I2O conrain (O)=224 g. =--=-!-

=9 x
t08 x 6.023 "
ro8 mol
'" '
50. 558.5 g Fe = 10 motcs
39. 0 5% by weighr means 0.5 g Se is present in 10O g
of peroxidase anhydrous enzrme. As at least one = 10 x 6 023 x 108 aroms
atom of Se muEt be presnl rD the snzyme and 60gC = 5 moles = 5 x 6 023 x to23atoms.
1/90 t:t'atletp's N,e.qr Coarsc Che.m tstrqEI[
51. Eq. mass of ferrous ammonium sulphate = 392 SO?- icns. With cxcess of AgNOr, O.01 mol of
'.' Normality of the salt solution AgBr ie Y is formed. With excess of BaCl2,0.0t
192 l mol of BaSOa rle Z is formed.
=-jr2,t00,1000=0lN
60, At STII22 4I-ofanygas = 6 02 x 1ozj molecules
20 ml ofo l N salt sol
= 18 ml o[KMnO1 sol

. Normality of KMnoo sor = ?9ff-1

' lsLu2=q+#x 15 - 4.03 x1023,
= | N
6 02 x I02J
Ilq. mass of KMnO4 = 31.6 :r r. t.rz = -,2214 ,5 : 1.344 x t0-J
.'. StreDgth of KMnO. sot- : | , tr .o 2 gH, = 1' 02 x lo23 molccules

=3 5 gL-l approx. o s gHr- 9-9-!dB xo 5 molecules

52.
= 1 505 x 1oB molecules
_ Eq. mass of mctal + Eq. mass of oxidc 72gOr= 6 02 x tO23 molccules
Eq- mas5 of met8l + Eq massofchloride
:3 = _:_,r
_ E+8 :_ This
-. give6 E = ,l j .25 rc g ox = gJ+e x 10 molecules

54. 1 L NHI G) reacrs wirh I L HCI k) ro form - 1.88 x 1023 moleculcs

NH4 Cl (r) r hich has negliSible volume. Hence 61. Cu=4g,CuO=5g. oxygen = lg. Thus lg
final mixture will contain only 0 5 L HCl. oxygen combines with Cu ..- 4 g.

55. 1 I atom of Fe (56I Fe) is prescnt in 1 mole of the

8g oxygen will combine with Cu = 4 xA =32t
compoudd. As 4.6 g Fe are presellt in 1009 ofthe Lq wt. of Cu = 32.
compound, 56 g ol Fe will be present in 63. Molar mas.s of NECO3 =2x23+ 12 +3 x16
I
seg = 011 g ol lh compound. Hence = 106t mol
{$ ' l06gNarCOr=0l6el
approximate molecular mass = 1200.
s6. N2 6) + 3 H2 6) i-----r 2 NH3 E) =o.l x6 02 x 1023 molecules
I I- of N2 reacts with 3 L of Hz ro form 2 L of =3 x0l x6 02 x toBatomsof O
NH3. Thus N2 is the limitinng reactaDt. =1806x104.
10 L N2 wiu react with 30 L H2 to form 20 L NH3- 65. 22400 cc ot any gas at S-l'P contains same number

As actual ycld is 50% of the expected value, NlI3 of molecules Lc. 6.02x 10?3. Ilcnce larger the
volume at S'ry greatcr is thc number ofmolecules.
formed = l0I- Nz reacted = 5 L, H2 reacted =
66. I mole of PCl3 contains 4 x 6.02 x 1023 atoms .
15L
1 4 moles will contain -3 31zx 1024 atoms.
'. Mixture will contain 10 L NH3, 25 L N2, 15 L H2.
67. Iiqual volumes contain equal number of moles.
57. 2 BC\ + 3H2 -* 28 +6HCl Heoce molar ratio of [Ie : CIIa = 1 : I . Ralio by
3x22.4L 2 x 10.t
*21 68 weight=4:16=1:4
-67 ?L . CH4 present by weight
)A = x rco = 8oEo.
U gC = limol = 2 mol = 2 x No atoms f
af at ST? will
6a- 22400 ml of be displaced by
569Fe = ffmol = l mol = No atoms =H+,22400s=5sg.
27 gN =;n,ol = I mol = N0atoms 69. 1 drop of water =
fr., = $.t
gag = (dn'o = 18 ml-l)
108
ffi mol = 1 mol = N0atoms
Mixture X will contain 0 02 mol Br- ions and lSgof water = A molecules
0 (}2 mol SOl- iotrs in 2 L solutioD. Hence I L of , Seno,"r= [,f = 9-.9I
n 6o1""u1",
mixture X willcontaid 0-01 mol Br- ard 0.01 mol
SOI\,4E BASIC CONCEPTS IN CHEMISTRY
1/91

ADDITIONAL UESTIO,A,r.$
As rlci o n - Re a e o n Ty
=Li on s
ee p e e,u e
The folloylng n. While ans_wering
thes questionq you are rquired to choose aDy one o
(d) If both Asscrtiotr and Rcssotr sre true o'd the Reason is a correct explaDstioD ofthe
AssertioD.
(r) If both Assertion and Rcoso' oDd true but Reasor is not a corrct expranatioo ofthe Assertion.
(c) IfAssertior is true but the Rlason is false.
(d) Ifthc Assrtion is fals. but the Rcssor is true.
(?) Ifboth Assrtion altd ReasoD orc false.

Assrtion Resson
Cinnabar is a chemicl compound whereas brass is Cinnabar always contains 6.25 times as much
mercuryas
a mixture. sulphur by weight. Brass can be made with widely dif_
ferent ratios of copper and zinc,
A sio$e Cl2 atom has a mass enctly 12 amu and a Amole ofatoms o[any element has a mass in grams equal
mole of these atoms bas a mass of epcrly 12 grams. to its atomicweight.
Pure warer obtained from dlffereDt sourcs such as Mass ofreactaDts and products duriDg
chemical or phlsi,
river, ell, spring, sa etc. alvays contains hydrogen cal change is always the same.
and Gygen in the mtio of I : 8 by mass.

4. In a gaseous reaction, the ratio ofvolumes ofreac- Volume ot gas !s inversly proportional
lo ils moles ct
taDts and gas{us producls is io agremeDt with partrcular temperature aDd pressure.
their molar ratio.
The slandard unit for expressing the mass of atoms amu is also called as avogram.
lll amu.
Both l06tofsodium carbonate and l2gofcarbon Bolh contain I g atom of carbon which contains
have same oumber of carboD atoms.
6.023 x 1023 carbon atoms.
Average aromic mass of boron is 10.3.
Boron has two isotopes B10 and Bl I who6e pcrcenrage
abundances are 19.6% and N.4Eo rcsrF ,tiflvely.
t. Atomlc mass of sodjum is 23.
AD arom of sodium is 23 rimes heavier than of rn"
$,n
mass ofcarbon atom 1cl2;.

True/Falee Statements
Wich of the followidg stdtements @e not true ? 5. Equalvolumes ofdifferent gases undc r srmilar con_
1. The zeros on the right of a decimal point are not olllons ot lemperature and pressure contarn equal
sigDificant. number ofatoms.
2. Petrol is a homogeneous mixlure of a Dumber of
6. Atom is not iDdestructible.
hydrocarbons.
3. Mass of redants is always equal to the mass of the 7. Empiricalformula represents the actualnumber of
products. atoms present in a molecule of the substance.
4, The volumcs of o(ygeo which combine wi$ a f ed &A balanced equation contains equal number of
volume of nitrogen in N2O , NO and NO2 bear a atoms of each elemenr on both sides of the equa_
simple ratio to one another. iion.
1192
Prt:dt:a y's Neut Couvse Chemistrgffi[f)

Fill ln Ahe Dlanks

1. The rotal number of digirs in a number iDcluding
- 7. The atomic ma.s of an element is the averagc
the last whose value is u-nc.erutn is called........ rclative mass of its atoms as compared with an
'lhe S.I. unit of pressure is......... atom of.....,.-,taken as..........

picometrc = .........meire.
1
t. Accordiflg to S.I. a mole is that amount of thc
subslance which contains as many elemontary en-
4. A pure subsunce that contains only one kiDd o[ titics as there arc atoms in gxactly. ...---.kB of.....
atoms is callcd...... isotoPe.
The slrnbol 'u' uscd for exPressing atomic alld 9, 'fhc rcactant whlch reacts completcly aod decides
molecular masses represents............scale based oD lheamountof theProductiscalled.. ....''
-...........isotopc.
The law which state.s that a chemical comPound
10. The welghl of 1 x 1022 moleculos of
always contaios the samc elements comttined in a
CUSOa.5I{2Ois...--...... (l.I.T.1991',
hxcd ratio by mass is ca11ed.........

W atchin O aY ? e G.'u e slio rte

Match erteries ol coltrmn A with aPproPrinte enteries of column Il'
lB
t, Petrol 1. CrmPound
2. Brass 2, Element
3. sugar 3. Mixture
4. Gold 4. Mixture

AJVSWERS
AS SERTION-REASON TYPE OUESTIONS

l.a 2,a 3.b 4.c 5,b 6.a 7'd E'a

TRUUFALSE S'TATEMENTS
r,4,5,7.
FILL IN THE BLANKS OUESTIONS
12 of constant
1- sionifrcant ficurcs 2. N m-2 or kg m-1 s-1 3. 10- 4' elemeot 5' uoified, C-12 6' law
."r"p*iirn oirr* of definite proponions 7' carbon, 12 t' 0 012, C-12 9' limiting reacknt
49 5.-,td7=t
,r.602x10" t+e.

MATCHING TYPE OUESTIONS

t--3,2-4.3-1'L-2.

Aseertio n'Rea 5 on Type G.ueetions

3. lloth Asserlion and lleason are correct s(atements 6. 106 g Na2CO3 = lmol
-1}re
but Rcason is not tic correct explanation = lgatomofC
correct cxplanation is bascd on law of constant 12BC = 1g atom of C,
composltlon-
7. Reason is corect but average atomic mass of B
4. Volumc ot agas is diroctty proportioMl to its moles
at a partlcular tempcrature and pfessure'
10x19.6+11x804
100
5. Both Acsertion aDd Reason arc correct statemcnts
but Reason ls not the corrcd explanation - 10 8
 [J N ITT

3taEes of lv,latter
.i.,.,':.i , l ril:i
Gaseous slate : Meas urable properties, the gas laws, ldeal gas .qu"rtion, kinetic molecular theory,
cieviation of real gases from ideal behaviour, liquefaction of gases, critical temperature and iis
importance.
Liquid state : Properties of liquids, qualitative description of vapour pressure, surlace tension.
viscositlt
Solid state : Classification of solids based on different binding forces.

General lntroductior
In Unit I, Section III, we discussed the
chemical classification of matter into elements,
compounds and mixtures. A passing reference
was made about the physical classification of
matter into solids, liquids and gases rvhich are
called the three states of matter.
The aim of this unit is to discuss some impor-
tant aspects ofeach ofthe three states ofmatter one
by one. Howevcr, before we proceed [o discuss
each of the states, let us try to review what we mean
by a solid, a liquid and a gas and in what important
characteristic properties the three states differ
from each other.
A suhstotce b said ta be soliditits meltingpoint
is above room temryroture under atmospheric
pressare; c liquid if its mehing point is belov
room temperctlute and bolling poinl is dbaw
room lemperdtare and c gas il its hoihng
point is below room temperalure under at-
mospheric pressure.
It has becn found that in most cases, a given
substancc can be made to exist in any one of the
three states under different conditions of tempera-
ture and pressure. For example, water which is a
liquid under ordinary conditions of temperatnrc
and pressure, can be convertcd into stcam (gas) at
100'C and under one atmosphere or into ice (solid)
by cooling to OoC under one atmosphere presstrre.
A given substance can also exist simultaneous-
ly in all the three states under certain speciliccl
conditions of temperature and pressure. For cx-
ample, water exists in all the three phases,viz. icc
(solid), water (liquid) and water vapours (gas)
simultaneously at 0. 0L'C (273. 76 K) and 4. 58 mnr
pressure.
Tlw temperatwe Nwhieh alt tlu lhree phases etu
tqethctis callod frlple pOint.
The change of state is often accompanied by
either absorption or evolution of heat. For example,
a solid can be converted into a liquid or a liquid into
a gas by absorption of heat. This implies that a
substance possesses least energy in the solid state
but maximum in the gaseous state.
l'he essential points of difference between tho
three states of matter, namely, solids, liquids and
gases are given in Thble 2.1.

2fi
 i" ait.ttt's Neut Coutse I

TARLIi 2.1. Comparison of the characteristics ofa solid, a liquid and a gas
SOLID
I. Molecules are closely packed
Mutual forces of attraction are
the strongest.
The density of solids is high.
The positions of molecules in tbe
crystal latdcc are fqed and heD@
solids do not have translatory or
rotatory motioD but only posess
vibratory motiou.
Molecu les of a solid possess least
enerry.
Solids have borh a defiDire shape
and a deinite volume.
7. Solids possess least compressibitity
and thermal expansion.
I,IQUID
Molecules are less closely packed.
Mutual forccs of attraction are
weaker than those in solids.
The density ofliquids is lower than
that of solids but is much higher
than thai of gases.
Molecules of a liquid have greater
freedom of movement. They have
some tmDslatory and rotatory mo-
tiolls iD addition to tbe vibratory
motion.
Molecules of a liquid have higber
energies than those of solids.
Liquids do not have definite
shapes but have definire volumes.
Uquids have slightly higher com-
pressibility and rhermal expansion
than thoso of solids.
GAS
Molecules are sufficieDrly apart
from oDe another.
Mutual forccs of attraction are al-
most negligible.
Gases generally have low densrties.
Molecules of e gas havc largc
rotatory, vibraiory and translatory
motions-
Gas molecules are most energetic.
Gases have neither delinite shapcs
nor definite volumes.
Gases prcrssess hrgh compressibiliry
and thermal expansion.

Qi) thennal energ possessed by the molecules

llyo Morc Statas of Matter, Besides the above
three states of matter, two more states of mattor
have been found to exist and discovered recently.
One of these (fou,th state) is called plasma state
which consists of a mixture of electrons and posi-
tively charged ions formed due to superheating of
the gaseous state e.g. in the sun or stars. Another
state (fifth state) consists of a supercooled solid in
which the atoms lose their individual identity and
condense to form a single super atom.
Whether a substa.nce will exist as a solid or a
liquid or a gas is the result ofcompetition between :
(i) intermolecular force.r
r'.e. the forces of inter-
action between the molecules of that substance
which try to bring the uolecules closer, and
due to temperature which results into the move-
ment of the molecules and herce tries to kep them
apart.
In gases, the iatcrmolecular forces of attrac-
tion are weakest while thermal energy is highest
(mainfested as random translatory motion of
molecules). In solids, intermolecular forces of at-
traction are strongest while thermal energy is min-
imum (onlydue to vibratorymotion aboutthe mean
position ofcoDstitueDt particles and no translatory
motion at all). In liquids, the two gpes of energies
are intermediate between those ofgases and solids.
Molecular Interaction Enerry
Solid ------- Liquid -------r Gas
ThernulEncr5r
Some of the properties of solids, liquids and
gases can be eryrlained on thc basis oftheir interac-
tion energy and thermal energy as follows :
(i) A solid has rigidity because thermal morion
is too weak to overpo\+,er the strong intermolecular
forces ol attractiotr. In a gas, thermal energy is so
high that the molecules ca-nnot come close
together. Hence there are large empty spaces be-
tween them. In a liquid, there is a reasonable
balance between the attractive intermolecular for-
 S'TATES OF MATTEF
213

ces and thermal etrergy. Hence molecules in a liq- volumes of liquids and solutions. These units are
uid exist together i.e. it is a condensed state of inter-related as follows :
matter but there is no rigidity. That is whytheyhave
no deFrnite shape. 1m3:1ddm3:
(ri) A solid melts on heatinq because on heat- 1ml:1cm3
ing, the thermal motion increase--s. llitre = 1d cm3 = 1dm3 :1O-3 m3
(ra) In both liquids and solid, their molecules (3) Measurrment of Pressure. Thc instru-
exist together i.e. both of them are con dansed state

atmospheric pressure at that place.

slic'IIo\-I Why is merrruy used as a barometric liquid ?
THE (;A*SI'OUS ST TIJ This is on account of the following two reasons :

.
rnv
barometer is
of the liquid.
As height of the
col tudy.
temperature of the gas. The aim of the present (ir) Mercury is non-volatile at room tempera-
section is, therefore, first to discuss the measure- ture. HeEce the vapour pressure due to mercury
ment of these properties of a gas and then to discuss vapours is negligible.
some of the gas laws obeyed by the gases.

2.3. Measurement of Mass, Volume,

Pressure and Tentperalure i:ii::,, :i'i:':: '1: ,

masses gives the mass ofthe gas. The amount oftbe

gas is usually expressed in terms of moles which can
be obtained by dividing the mass of the gas by its
molar mass t.e. ATM. PRESSURE
VACUUM 740mrh
Number of moles = YT:i" ot-t
Molar Eass
The moles can be converted into the number
of molpcules using the relationship
I mole : 6.022 x 104 molecules
(2) MeasureEctrt of Yolume. As a gas frlls the
whole of the vessel in which it is put, hence the
volume of the gas is equal to the volume of its
container which in turn can be calculated from the

oo
dimensions of the container.
The SI unit ofvolume is m3. But this is too big
a unit. Hence the units commonly employed ari
cm3 or dm3. However the units ri and lities also FIGiURE 2.1. (a) Barometer (b) Ctosd limb
contiuue to be used, genera-lly in expressing the manorneter (c) Open limb nEnometer.
 l'radc. t' " Net4 Course
2t4

The instrumeDt used for the measurement of However, the unit of pressure now commonly
used is 'bar'.

latm:1.01325bar
or 1bar : 0 987 atm
are : The SI utrit ofpressure is pasca.l (Pa) which is
, (i) Those in which the longer limb is closed dehned as the pressure exerted by a force of 1
(Fig. 2.1. b) nswtou on an area of 1 m2.
(it) ttrose in which the longer limb is open 1Pa = lNn-2 :7kgm-1s-2
(Ftg. 2.1. c)
Closed limb manometer is used only for gases The two units are related as

1 atm: 101, 325 Pa or Nm-2

= 1.0135 x td Pa or Nm-2
1 bar : 1d Pa or Nm-z

A bigger unit, called kilopascals (written as

kPa) is also sometimes used. Thus
pressure of the gas. '-'1
bar = 102 kPa
Aspressure isforceper unitarea' the pressurc
" lrx {tr ll'1,E. ,4 m anomter is connected to a gas
obtained in lerms of the height of the mercury
conlaining bulb. The open arm reads 43'7 cm
column can be converted into force per uait area as
wherees lhe arm conaecled to lhe bulb reads 15'6
follows :
cm. If lhe barometic pressure is 743 mm merxury'
Suppose height of the mercury column =h cm what is the pressure of gas in bar ? (N.C.E.R.T')
:
Area of cross-section of the tube A cm2 Solution. Difference of mercury levels in
. . Volume of the mercury column = A x ,r cm3 the 43'7 -15'6 cm = 28'1 cm
If density of mercury at room temp. As level in thc limb connected to the bulb is
= pgcIll " lower than that of the open limb, this means pres-
sure ofgas is more than the atmospheric pressure'
then mass of the mercurY column
.'. Pressure of the gas in the bulb
= Axhxpgtam
.'. Weight of the mercury column
= Barometric prssure
+ Difference of mercury levels
=(Axhxdxg +
= 74'3 cm 28'1 cm = 102'4 crn
where g is the acceleration due to gravity.
702'4
x
This weight ofthe mercury column is the [orce =|a'4 ^r^ -
1'o1325bar
acting on A cm2. Hence
76 --'-- 76
Force _Axhxpxg : 1 365 bar
Pressure (P) =
Area

The smatler unit commonly employed in ex- measured. These are

oressing the pressures of gas is mm or torr* (after
'Ibrricelli, who invented (i) Centigrade or Celsius scale (after the
ih" ni." of the
name ofAnders Celsius)
baromctcr). H_snce
(ii) Fahrenheit scale (after the name of Daniel
: Fahrenheit, a German instrument maker)
* The Intcmational committee of weights and Measurcs Iccommends that the usc of'tori should bc dropPcd
 STATES OF MATTER 2ls
(rr) Kelvia scale (after the aame of Loril Kel- GAS
vh) ATMOSPHERIC
PBESSURE
(Pa + h)
The Celsius scale is based upon taking the PRESSURE (PA )
freezilg poht of water as 0"C and thc bsiling poitrt
of water as 10ffC at normal atmospheric pressure
(r'.e. at sea level) and then dividing the range into
100 equal parts so that each part represents 1'C.
The Fahrenheit scale is based upon taking the
freezing point ofwater as 32'F and the boiling point
of water as 212 'F ald divi.ling the ratrge into 180
equal parts. Thus
100 Celsius degrees = 180 Fahrenheit
degrees
or 5 Celsius degrees = 9 Fa-hreoheit degreesr MERCURY

The Kelvio scale of temperatues has FIGURE 2.2. Boyle's apparah.rs for study of effect of
emerged as a result of study on gases. It is possible pressue on the volume of air at room temprature
to cool a substatrce below 0'C arrd thus we can have
negative temperatures. But experimentally it is The following generalization was observed
found that it is not
possible to cool a gas below which is known as Boyle's law :

- 273 .15"C as aftq that the gas ceases to exist. Thus Temperatute remaining constanl, lhe volumc o! a
this is the lowest temperature that can be attained given mass of a gos k inverscl! proportional to its
and hence is taken as 0 K on the Kelvin scale. Pfessure.
Negative Kelvin temperatures are as impossible as
negative volumes or negative lengths. Thus
Mathematically, Boyle's law may be stated as
I
- 273.15'C : 0K V c( for a given mass of a gas at constaDt
i
or 0'C = 273.15 K temperature
The size of Kelvin degree is same as that of _1
Celsius degree so that orV = t.F or PV =k
i.e. ,PV:constant at constant temperature
Kelvin is the SI unit of temperature ard ac- where P and Vrepresent theEessure and volume
cording to SI, it should be w ften without putting of the gas atrd t is a constatrt whose value depends
upon the mass of the gas and temperature.
the symbol ofdegree (') e.g. 10ffK should be written
Thus Boyle's Iaw mayalso be stated as follows:
as 100K.

The first quantitative relationship between Thrs if P, and V, are the initial pressure and
the volume a.nd pressure of a gas was studied ex- rclume- of a gas and keeping the temperature cotr-
perimentally by Robert Boyle in 1662. The studies stanl, if pressure ; cl'anged io Pr, t-hen volume will
were made with air at room temperature. He used change to V, (say) such that acf,ording to Boyle,s law
mercury and a simple U-tube of the R?e shown in
Fig. 2.2. The pressure was increased by puttiug Pr vr = P2 v2 at co_Dstanl_t!T1"l",Yi
i
more mercury into the open limb. The volume of I

the air enclosed in the space above mercury in the

shorter limb was noted each time. Similar experi-
. This form of Boyle,s law is very helpful in
solving nup-erical problems because linowihg any
ments were repeated with other gases. tfuee variables, the fowth can be calculated. '
. Thc conwEior mcthod wi[ bc cc = o.
; CF - 32) "n =
t 1"c; +:2.
216 Pra tl c e p's,N-i.ri/.|,1'G0.',:;:Ckem:lltty WIA
Experimental Verification of Boyle's law.
Boyle's iaw be verified using a simple method
"uo
as shown inFig.2.3.

P P

o o o
FTGURE 2.4. Graphical verification of Boyle's law.

the temperature (T). Hence for a given amount of

the gas faken, a different P - V curve is obtained at

such
E
E
o
o
t

, ,,,, fieune D.5: Giililffi 3t e".7ut U;. iiiri:ii

,i

We observe that if
constant temPerature,
half. Similarly if pressu
volume is reduced to U4 th and so on. P
Graphical Verilication of Boyle's law. Ac-
FIGI.IRE 2.5. Isotherms for a definite
cording to Boyle's law amount of the gas.

-v or
P*1 PV=constant
Significance of Boyle's Law. Boyle's law
Thus the law can be verified by plotting proves a very important fact that Jh9 gases are
1 compressible. The more it is pressed,-the denser it
(i) P vs when a straight line passing tbrough becomes. Hence it can be concluded that at con'
f stant temperature, lhe gas densi$ is directly propor-
the origin is obtained (Fig.2.4 a), or
tional to pressure.
(if) PV vs P when a straight line parallel to the as the atmospheric pressure is
At altitudes,
X-axis is obtained (Fig.2.4b),or dense. As a result, less oxygen is
low, the air is less
(rrr) V vs P when branch of hyperbola in the available for breathing. The person feels uneasi-
fust quadrant is obtained (Fig.2.ac). ness, headache etc. This is called altitude sickness.
It is interesting to note That is why the mountaineers have to carry orygen
: constant, thevalue of the cylinders with them.
the amount of the gas taken
,prrfg BOyLE,S LAW

I.:X,\NIPLE t. Atussel of 120m|cqacity cm- Vr : 120 ml, V, : 180 ml

fe. Pr:750mm Pr:?mm
it
Since the temperature remains constant,
therefore, by applYing BoYle's Law,
Solution. Since a gas completely frlls the
vess ch it is contained, therefore we P1 V1: P2V2
have:
STATES OF MAITER
217

Subcituting the corrcspouding values, ule have By applying Boyle's Law since temperature is
7fixlm=P2x180 constant,

or -gr= -7frxlzil = 500mm PzxV2= Pl xVl.

fm:
.'. Pressure of the gas= 5{X) mm Substituting the corresponding values, wc
l.lXAi\IPLlt Z. ml of cafion dioride were
103 have
collected at 2TC and 763 mm presswe. Wat will be x V2=
721 763 x lO3
ils volume if the pressure is chaiged to 721 mm a! the
same tempemfrfie ? -. 763 x 103
V"=-=I09ml
Solufion. Given Final ' 721
Conditions Conditiow
Vr = l(B ml .. Volume of carbon dioxide = 109ml.
Vz = ?ml
Pr = 763 mn Pz = 721am

A cnain mass of a gas occupies 39 rDl at 760 mm 5. Abulb)(' of unh.rci*nvolumecontaininga gasatone

pressure. What volumewould it oc{upyifthc pres- atmGpheric pressure is connected to aD evacualcd
sure is raised to 78O mm provided that temperature bulb of 0 5 litre capacity rhrough a stopqlck. C)x
remains constant ? [ 1n, 3t.0 ml] operdng the stop-coclq the pressure in the whole s',,1t-
2. 2OO ml of a gas are fouDd to havc a pressure of 750 tem affer some dme $,as aound to ha!,e a constanl
mm. What will be its volume f rhe prEssure is doubled lIuc of 570 mm at tbe same tcmprature. What is
at the Same temperature ? [.rrr. 100.0 mll the 'Dlume of rhe bulb X? [66. 1 5 litrel
3. A vessl is 120 mL capacity contaiDs a cenain 6. What will be tbe minimurE pressure requlrcd to
amount of gas at 35"C aDd 1.2 bar pressure. The compress 5OO dm3 of air ar I bar ro 200 dm3 a r 30. ?
gas is transferred to anothcr vessel of volume 1g0
(N.C.E.R.T.) [,1,. 2,5bar]
mL at 35qC. What Eould be its pressure ?
(N.C.E.R.7:.) [\D\. 0.r bar] 7. A gas occ'rrptes a volume of 2.5 L at
9 x ld Nm-2. Calculare tbe additional pressure
4. A balloon fiued with an ide3l gas is rakeD from rhe
required to decrease the volume of the gas to
surface of the sca deep to a depth of IOO m. What
1 5 L, keeping tbe temperaturc constant.
will be its volume in terms of its originalvolume ?
[\n.. 9. 3% of its voluEe at the $urfoce]

3. PrVr = P2V2 Le. 1 .2 x 12O = Pz x lB0 After coonecring to bulb ofo 5 L capacity, volumc
or P2 = 0 8bar = (v + 0.s L)
r:e. V2 = (V + 0.5) L, Pz = 570 mm =5jO/ :,60 atm
4. Pressure at the surfac = 76 cm ofHg
APply PrV, = P2V2, calculare V
= 76 x 13 .6 cm of H2O = 10.3 m of H2O
-- Pressure al 10o/ll depth 7.Vr-25L,Pr=9x ld Nm-2 ;
= 100 + 10.3m = 1tO.3m v2= l 5 L,P2 = ?
ApplynS PrVr PzYz,
(At sufacc) (Ar tOO rn deprh)
Apply Pr V2. Calcutate P2. We get
Vr = P2

10.3xV=tl0.3xV, P2 = 15 x ld Nm-2. Addrtrooal pressure re-

or V2=0098\/=9-3Eootv quired

5, Suppoce volume ofrhe bulb X = V = 15 x 106 Nm-2 - 9 x ld Nm-2

i.e. Vl=V and Pl=1a[m =6xlo5Nm-2.
 Pradeep's

I-AW
on the effect of temPerature on the 6 c!
volume of gas at constant pressure were f[st
a
cafiied out bylhe French scientist, Jacques Charles 4 =
in 178? and then extended byJoscph Gay Lussac in =
1802. The following generalization was observed 2 l=
T
which is known as Charles' law : o
-273. t'
- r'oo o 1

+ TEMPERATURE lNoC 4
FIGUBE 2.6. Vdume oI a gas a'Iunction of temperature
or fall in lemperalure. ln centgrade.

Mathematically,

v,=vo +
fixt
= vo (+-L) (ry) world so far.

sam
where V, is the volume of the gas at l'C and V6 is its
are
volume at 0'C. temperature axis at -27IC corresponditrg to zero
The volume of a certain mass of a gas at any volume as shown in Fig. 2.7 below :
temperature can be calculated by the application of
the above relation. Thus :
t
Volume at 10oC : ,o * +# r!
t
t
z
Votume at 1'C = V, * * ul
f
J/o
volume at - r"c = vo - n3 o

20 vo
Volume at -20'C = Vo - 2J3
FIGURE temperature
273V^ (in oC constant
volume at -zil3'C= vo - td=o
This implies that a gas at - 273'C will have Absolute z*ro and Absolute Scale of
,"ro o. oo uo-Ir.", i.e., it will cease to exist. Below lbmperature,
this tive which
Tlu lowat
is m traced the
lemperalun
rate gas uPto
to luve Ttro
at constant pressure. In actual practice,
-27TC More careful experiments have shown that the
all gases liqueffbefore this temperature is reached'
absolute zero of temperature is -273.15'C' How-
The same conclusion can also be reached ever, for most of the purposes, tho approximate
tain mass
value of - 273'C is used.
re (along
a now scale of
h consist-
temp as its zero' This
scal; Kelvin scale or
STATES OF MATTER 219

AbsoluteScale. The size ofthe degree on the Kelvin or V=tT

scale is the same as that on the centigrade scale. On Tte numerical value of the comtant k
this scale, the freezing point of water, i.e.,0'C is depends upon the amount of the gas talen and the
273' A. (Absolute) or 273 K (Kelvin). Thus, any Pressufe.
temperatu-re on the centigrade scale cal be con-
The above relation gines another definition of
verted to that on the Kelvin scalebyjust adding 273
Charles' law as follows :
to its yalue on the centigrade scale. Hence, the two
scales are contrected by the relation : Prwermuiaingursn , u volutw ol a givcn
Kelvin Temperature : Centigrade temperature nNta g4Jis dir*tf pWorttonal to ir tcmpcra-
+n3 tul[ indogtw Xelvir'-

TK=fC+273
I
The relation V .( T implies that
where T xe{n I = ao*r,o, constant pressure.
[e.
and the scale - -Y
This 1' "t
,

of temperature is als o cdled Thernodytanic scale

of tempemturc.
ffr*if q i, tt*olume of the gas at tempera_
ture T1 (in degrees Kelvin) and keeping the pres'
A comparison of celsius, Kelvin aud Fahren-
heit scales oitemperature is given in Fig. 2.8 below : surE consta.nt, temPerature is changed to T2, then
the volume will change to V2 such that

vl v2
Tr = ,t at constart Pressure

This form of Charles' law is very helpful in

solving numerical problems because knowing any
three variables the fourth can be calculated.
Thus a plot ofV us T at constalt pressure will
be a straight line passing through ths s gin (Fig.
2.e).

TIJ

FIGURE 2.8. Comparison of Celsius, Kelvin and

Fahrenheit scales of temperalure o
The advantage of kclvin scale lies in the fact
that the volume of a gas and its temperature on the
Kelvin scale are directlyproportional toeacb other.
TEMPERATURE (K)
This can be explained as follows :
Accordiog to Charles' law in the form already FIGURE 2.9. Plot o{ V vs T at
constant P.
defined
l'ttt - '\
,,_,o of Varia-
\ zT
Putting 273+t = 1
) Cotrstant
the corresponding
temperature on the Kelvin scale, we get ' ot r.a ut
.,-., T Constant Yolume (Anonton's law), The law which
',- 'o 2i3 governs the relationship between pressure and
As Vo and 273 are constart, henc temperature of a gas at constant volume is similar
Yq T or simply, V c< T to that betvr'een volume and temperature at con-
stant pressure, It states as u-Dder ;

1
2ho Neut Course Chemistrq

Vofure tt{,winiBg cot8turl, tJo prwure of a given

nosr ola p is iliroctb pnporthwl to ils tenWera-
twc tn dryr6 fzbin-
The generalisation, as given above, is referred
to as Prassur-lbEpratur Law or Amonton's
law
In 1703, G. Amonton constructed an air ther-
mometer based on the principle that the pressure
of a gas is a measure ofthe temperature of the gas.
The relation P a Timplies that
P-
FIGURE 2.1O. Apparatr.rs for the study of 'rarb0on T = Constaot at constart volume
volume with temperature at conslant prcss|lfe. which means that
lP' P^
Volutne rcmaining consta , lle presswe of a Eiven ut**t-tuo'
o-"
I fl= t'
]

mux ol a gas increasx or decrea$s b) 1n7i oI its

pressure at (fCfor etery 1'C rise orfzll ittetnpera- '

ture.
Experlmental Set up for the Study oflhrla-
tion of Pressurr wlth lbmpemturc at Constant
Mathematically, Yolume. This is shown in Fig. 2.11.

VARIABLE
(nl + t\ _-T
ir,= r. 1r
**)=r" \m -'0273
)
TEIUPERATURE
JACKET

where P, and P6 are the pressures of a certain

amount of a gas at fC aad ffC respectively.
As Po aad 273 are constants, hence
PreT
FIGURE 2.11. Apparatus for the stLldl, of variation
or simply PaT of pressure wilh temperah-ne at constant volume.
i.e. P=tT arles' Iaw.
The numerical valuc of the cofftatrt ft Air its densitY
depeuds upon the amount of the gas taken a[d the decr the atEos'
volurne. pheric air. This fact is made use of in filling hot air
Thus the above law may also be defrned as in the balloons which rise up for meteorological
follows : observations.
CHARLES' LAW ANt' .t,r,lONTON'S LAW

EXAIIPLE l. Z0 A of nydngen meosured at ?!_x308=

V-=
'2 288 21.38
15"C are heated to 35"C. Whdt iJ the new wlume al
the some pressurc ? Volume of hydrogen gas at 35'C

= 21 '3E ml.
Givencond,itions Finalconditions
Vr = 20 ml vz: ?ml :
l'l \.\\ I I'l - I', At what tempersfiye centigade
^t;:75+2i73=238 K T2=35 +273:t08K witl the volume of a gas at 0'C double itse$ pressure
remaining constant ?
By applying Charles' Law Solution.
v2 20 Let the volume o[ the gas at 0"C : V ml
308 = 288
STATES OF MATTER 2111

Thus, we have : Solutiotr. Suppose volume of vessel : V cml

Vz = 2Vml i.e. volume of air in thc llask at 27C : V cm3.
T1 = 0+273 :273K Tz=? VtVzVVz
vr_ Vz Tr 't2 "-' 300 75q
By applfing, Charles' Law,
Tr Tz or Y:=2 5V
Substituting the corresponding valueg we have .'. Volume expelled = 2 5V-V = 1'5 V
v2v .'. Fraction of air expelled = 2.5V= l5
2J3 T2
_ _2Y 273 546K><
=+ 200 mg
r l.\ -\\ ii'l.l,5.ln open vessel contains
12=-= of air at 17"C. What weiBht percent of air would be
: Tz = 546-273= 273"C etpelled iI the vessel is heated to 117"C ?
t..X_.\tIPl-f l -\. A i0.0litre container is filled, Solution. Suppose volume of 200 mg of air at
with a gas to a pressurc oI 2.00 ah at trC. At whal iTC = Vr
kmpemturc will the prcssure inside the container be As pressure remains constant (being an open
2' 50 alm ? vessel)
Solutlon. As volume of thc contfier remains Vt Vz. V Vz
constant, applying pressure - temperature law viz.
Pl P2
r, = T;**';o = 55orv, 1'34V
2atm 2 50 atm
:-
. . Volume of air expelled= 1.34 V V = 0. 34 V
n = uwecet z'tsK= T, Mass of 1 34 V air at 17TC 2N mg
or T2 = 14:lK:341-273"C : 6E C Mass of 0 34 V air at 117C
r i \\\ll'l,ll .1./ student set up tlg sryorana at
,ootfl temperutte Qrc). By mistake withart adding =ffi,0.*^"
he rcrclian mifrire he st@tcd l&atinghe tlask By the . . Mass 7o of air expelled
tittu hc rcalbed his mislalq dE Empeaue had shd
up to,t77C as reco edby a ppmete Whd fudion ZN x 0.34 1
q atw@Ahaw been qe cdant ? (N.C.E.R.T) = 1,.4 x 200 x 100 = 25'379o

?RO7LEM? FOR:,fu:RAg, ,[re:H t I

1. 300 ml of orygen gas at heated to 10'C. 5. A steel taDk containing ah at atm pressure at l5"C is
15
What is the new volume -10'Care
if pressure remains con- provi&d with willyield at a presure of
a safety \,ahE that
stant ? Ii\rs.3',12.E mll 30 atm :rb 14tat mioimum temprature must the air be
2, 25 dm3 of ammonia at 283 K are heated uDtil its bated to blow the safety \ElrE ? [ \ns.303oc]
volumc is 30 dm3. -Ib what temperature must it 6. It is desired to iDcrease of the volume of a gas by
have been raised to accomplish the change ?
?i atitho]ul changiDg the pressure. To wbat
temperature, the gas must be heated if the iDitial
I,\lrs.39.6 KI temprature of the gas $ 27' ? [.\'rs EToCl
3. What will be the lolume of bydrogen when 3 litres 7. A gas cylindcr mrtaioing cooking gas can withstand
of it are cooled from 15'C to at constant a pressure of 14 9 atmospheres. The pressure
pressure ?
-73'C
[,{ns 2.0t33 litFsl gauge of the cylinder iDdicates 12 atmosphere at
4. What volume of air will b expelled from a vessel
n'C. D\e to sudden fire iD the building, the
containing,l0O cm3 at 7"C when it is he3red to 27'C temperaiure star6 rising. Atwhat temperature ths
at the same pressure ? I dr s . 2t.6 cm3] crti,lder will explode ? [ \ns 99.5PCl

5
Vr Vz
q=E'". cm3
4. 400 V2 This is the voluDe after expansion.
@TT7!R=@r+-n x^ . . Volume cxpElled

or V,=ffix300cm3= 482 6cm3. = (42t .6 - 4oo)) cn3 = ?3.6 cm3.

2112 Neo Coursc Chemis

Pr Pz 15atm 30atm Now V, = V srn3, Tr = 300 K, Yz = I 2V,

t- C=E ,.?.
#iil =T o, rz=576K v- v-
= (s76-273)"c = 3o3'c
12= ? ArconstanrP,
+-;rx.=#
6. Suppose volumc ofgas at 27'C = V cm3
or T2 = 360K = 360 - 273"C - 87"C.

of 7. P, = 12 31rn,1l = 300 K, P2 = 14 9 atm, T2 = ?

Increase in volume desired = 20% V
=ffixv =0 2v As volume of the cylira". i,
| =
ft.
"oortrn,,
. Ftnalvolume=V+0.2V = l.zv

Boyle's law gives the effect of pressure on the Tt to T2 at constant pressure P2.
volume of a gas at constant temperature whereas uYz
Charles' law gives the effect of temperature on the '' Tr Tz
volume of a gas at constant pressure. However, it is
possible to derive an equation which gives the T.
simultaneous elfect of pressure and temperature or Y"= vx!lt
"
...(,,
on the volume of a gas. Substituting the value ofu ftom Eq. (i) in Eq.
The equorionvhbh givdstlu sir tlhn@us fia of (li), we have
pressure and tempontwe on tlv vohtme ol a gB is P. V. T^
ur=
huwn as ideal
uruiflg4,,.
gas eqwlionor eqtution oJ state{or
-I'i
Derlmtion. The gas equation may be derived
PrV, i
...(rr,)
from Boyle's and Charlcs' law as explained below : T"i
't
Let the volume of a certain mass of a gas
This is the most convcnient form of the ideal
change from V., to V, when the pressure is changed
gas equation for the purpose of calculations when
frorn P, to P, and temperature from T, to T2 in the any hve variables are given and 6th is to be calcu-
following two steps as shown in Fig. 2.12. lated.
Another popular form of the ideal gas equa-
tion can be obtained as follows :
PxV
\ / INDIRECT WAY\ Eqn. (iii) implies that -i = Constant
STEP.I\ { \,STEP.2
= r (say)
The value of the constant K
dcpends only
I Pr,"r, I upon the amount ofthe gas taken.Ifn is the number
of moles of the gas taken, then it is found that
FIGURE 2.12. Change of slate assumed to Kdn
be taldng PlacP in two sleps
or K: nR -.(iy)
Step 1. Frst supPose that the volume of a given where R is a constant of proportionality and is
mass ofagas changes from V, tou when the pressure found to be independent of the nature of the gas
is changed from P, to P2 at constant temperature Tl. and depends only on the amount of the gas taken.
Then according to Boyle's Law, For 1 mole of any gas, the value of R is the same.
Hence R is called 'uniee$ql gas constant'.
P2xu=PtxVl
Substituting the value of K in eqn (iii), we get
Pr vr
or ,=
T ...(') PV
T=/tK
 STATES OF MATTEB 2113

lpv =;Rrl
This is the most commo! form ofthe ideal gas
-.(v)
":, + ...(viii)

equation. This expression can be used for the calcula-

Altcrnatlve Derivatlon of Ideat Gas Equa. tion ofmolecular mass from a known value ofden-
tion. The ideal gas equation can be derived directly sity of the gas at a given temperature and pressure.
by combining Boyle's law, Charles' law and Alternatively, the expression (viri') can be used for
Avogadro's law as follows : the calculation of any one quautity from known
According to Boyle's law, values of the other quantities involved.
1 Deduction of Avogadro's Law from Ideal gas
V cr
fat constantT ...(yl) law. According to ideal gas law
According to Charles' law, PV : NRT
V cTatcoNtantP,..(yii)
Thus if two gases haye the same values of P
According to Avogadro's la\*,, and I then if their volumes V are equal, the values
V.. z at constant T and P ...(yrir) of n must be same. In other words, same volumss
where n is the number of molcs of the gas. (This is of different gases under same conditions of pres-
because according to Avqladro's law, cqual volumes sure and temperature must contain the sam num-
ofdifferent gases contain equal number ofmolecr es ber of moles which in turn will contain the same
under similar conditions of temperatue and pres- number of molecules (because 1 mole of any gas
sures. [n other words, vol"me is direcdy proportional contains the same number of molecules viz.
to the number of molecules which ia tum h dLedly 6.022 x LG3)
proportional to the number of noles of the gas) Standard or Normal Tbmperatur and Pres-
Combining (vi), (rzi) ard (rzri), we get surc (STP or NTP). It is obvious from the above
1
discussion that t
Vct ixTxn changes when
chaoged. Thus,
1 ments involving
V=RxFxTxz necessary to reduce the volume to certain standaid
or PV: nRT conditious oftemperature ard pressurc. Thc stand-
ard temperature is 0'C or 273 K while the standard
where, as before, R is molar gas constant. pressure is one atmosphere at sea level or 760 mm
For 1 mole of the gas, the ideal gas equation or 76 cm of mercury. These standard conditions arc
becomes known as Standard Tbmperature and Pressure i.e.
PV=RT STP or Normal Temperatue and Pressure i.e. NTp.
A gas that obeys ideal gas equation exactly is The standard pressure now commonly used is I bar
called at ideal gas . instead of I atm.'fhts
. An ideal gas equation is also called the equa-
tion of state because it defines the state of the'gas STP or NTP implies thot
completely when all the variables have been Tbmperaare = 0"C:273.15K- 273K
specified.
Ideal gas equation h terms of denslty. This
Pressure = I atm = 76 cm:760 mm = 760 ton
form of the ideal gas equation may be derived as = 101.i25 k Pa
follows : or Pressure =l bar = ]d pa = Id kpa
If rz is the mass of the
gas in grams and M is
the molecular mass of the gas, theo
m IMPORTANT
,t=M At STP i.e. 0"C and 1 atm prcssure, I mok o! any
gas hasa vofume equal to 22400 cmt. But a! I bdr
PV=nRT=
frnr pressure anl 0"C, lhe volume occupied hy 1 molc of
the is 22700 cm3 i.e. 22.7 dmt ir
":? #=,#
B4S
22.7 x ll-t m3,
2114
Ned Course

Nature and Yalues of the Gas Constant R. (iii) For ocpressing R in SI azi,r, put
From the gas equation, PV = n RX, we have
107ergs: l joule.
PxV = Pressure x Volume
R=--== * to'lor,"* degree-l mol-l
M.1". x 1b.pl""K HenceR: "foI
x :
ffi x 0-eogtnY ffi (Length)3 8'314joules degree-il mol-1
= E 314 JK-l mol-r
Moles x Degrees Moles x Degrees :
or directly taking P 101325 Nm-2 or Pa,
Force x Lensth Work
- Y = 0'0724m3, T = 2i73K
Moles x Degrees Moles x Degrees
weget R:8 314JK-l mol-r
= Work done pr dgree per mole or taking P = 101 325 kPa,
Thus R may be expressed in different units
depending upon the units of work.
!:22.4dm3,
Nurnerical Yalue of the Gas Constant (R) . T = 273 K
(i) At N.TP conditions, for I mok of the gas we get R = t'314kPadm3K-l mol-r
P: l atmosphere, Y =22'4 litres, (iv) To eqrex in terms of caloies, we know
't :2J3K n = l mole that 4 184joules = 1 calorie

PxV Iatmx22 4L rrer,ce R:ffi degree-l mol-l

'' ^- nxT - lmolx 273K "alories
= 0'0821 litre atmosphere degree-r mol-r :1'987 calories degree-r mol-r
If V:22400ctt3, To sum up
R : E2' I cmt atm deg-l -or-'
Units of P Units
or Taking P = 1 bar so that
ofv
Y =22 7 dm3,
lbar x 22'7 dm3 L atm K- 1 mol-
1
atmosphre litres 0 .
0821
^- lmolx273K or dlf or 0' 0821dm3atmK-lmol-1
= 0 083 bar dm3 K-r mol-r
1 1
atmosphere cm3 82 ' 1 cm3 atm K- mol-
(ii) ln the C.G.S. units, Ior 1 mole of the gas at dynes cm-2 cm3 8.31x 10? ergs K-l mol-1
N.T.P :1'987calK-l mot-l
P = 76 cm = 76 x 13'6 x 981 dYneVsq. cm
Y:224Cf m1, T = 273K, ,r = lmole N m-2 or Pa m3 8'314 J K-1 mol-l
8.314 kPa dm3 K-l mol-r
- -- PxV
. [,
''"-nx^f
(76x13'6 x98l)x22400
1x273
kPa dm3
0.0t3 bar dmr K-l rnol-l
= g.314 x 107 er3s deg1te-l mol-t
bar
l"-' | dE3
- l-
IDEALGAS.to-Yo'lo)
Nr B-+g

TYPE I. Based on the equstion By applying gas equation, we have

PrY, / Tr= P2\2/ "1, 760 x Y2 758 x 35

I--)({\ll'l-t- 1. jS mt of uBq collechd d

rB:2n
were
x 35x
6'C and758 mm pressut. &laiale its wtume al NTP .. v,=-fr. 758
fr; =34't6n.t
273

Volume of chlorine gas 34 16ml. :

Final conditions
Given conditioDs
vz=?ml ll\ \\ll'l 2
L At 27"C and one atnosPheic
Vr = 35ml
pressure, a gas has volume V Wat will be its volume
Pr = 758 mm Pz = 760 mrt -at
177'C and a Presswe of 1.5 atmosphere ?
Tf6+T!=n9K T2=0 +2n:273K
STATES OF MATTER
211s

Solution. Solutlon.
Given conditions Final conditions Let the volu-Ee of air in the tube be V ml.
? Given conditions New conditions
Pr = latm Pz= 1.5 atm Vr = Vml Vz = VmI
T| = 2:8+27 =!U K Tz= 273 + Ln P, = 760 mm = I atm. Pz = 3 atm.
450K ^ft :273+27 = 3O0K Tz: ?
Applying gas equation, we haJe
x By appllng gas equation, we have
t x V: 1.5 V2
3oo 450
VX1 VX3
.. 1xVx450 300 T2
'2- 3oox 1.5 ''' T2:300x3
.. Volume of the gas : V = $0K
.' A sealed tabe which cqn Thus the tcmperature above which the tube
wihsand a presure of 3 ofmosphere is ledwith ait will burst
f
at 2TC and 7& mm prcssurc. Find the Empetalurc = W-273
above which it will burst. : 627"C

FO
"RAfrL|,Ma
1. 50O ml ofnitrogen at 27o C are cooled ro
-5.C
the same pr6surs. Cflctllate the new volume.
ar 5. One litre flaskcontainiDgvapours of merhyl
(Molmass 32) ata pressureof 1atm. and 25.C was
alc_ohol

I '
I Lr
446.7 ttrll evacuated till the nnal pressure was l0-3 mm.
2. 400 ml of oxygen at 2fC were coolcd to _15.C How many molecules ofmethylalcoholwere left in
without the chaDge iD pressure. Calculate the mE_ the flask ?
1tuis.3.24 1 l0I5 moleculesl
traclion in volume. I s6.0 mU 6. 28.32 li!tres of chlorine wre liberated at nornal
3. A volume of bydrogen meisures one cubic conditioDs of temperature and pressure. Calc.lllate
decimctre at 2O.C and at a pressure of half an the \olume ofthe gas at l2oCaod 780 mm pressure.
atmosphere. What will be its\olume at leC and at
700 mm presure ? ..n. [ \n. 2E.to litres]
I
0.524 dDsl 7. 'Ibmperature at the foot ofa mountain is 3ffC and
4. 300 litres of ammonia gas at 2O"C aod 20 atmos- pressure is 760 mm whereas at the top of rhe
phere pressure are alloyed to expand in a spac of mounhin lese are 0.C and 710 m mparethe
600 litres capacity aDd to a pressure ofonc atmc_ densities ofthe air at the foot and top ol the
phere. Calculate the drop in temperature. mountain- 0.954: U
[ \"\ 263.7 KJ

FORDIFF
4' Prvr Pzvz, 20 armx3oo L
-71 _= -T;Le- ----z,n*- I atmx60o L ot V2= 1.2O5 x 10-3 c.m3
22lO0 cm3 at S.TP. 6 .02 x
ot T2=29 3K = 1023 motecutes

Drop iD temperarure = 293-29.3 = ?i3.'t K

:. 7.m5 x 10-3 cm3 at S.Tp
5' Pr = lo-3 mm,vr = looo cm3, T, = 298 K oiirif" *1 205 x 10-3 morecutes
=u
i
For mnverting this volume to volume at S.Tp-,
= 3 24 x lol5 molecules l

appry
+=ryxV) , r=#. ,",* +=+"8
. 10-3 x tffD 760
Le. ----B- mn . 273K 0.964
=--7I- - 760
3otK ^ 7l o;; = -l-
 Ne.a, Couyse
2116

'M, molecular masses

Solution. Suppose of A
and are-Mo and respectively. Then their
j Calculate the number of moles number of moles will bc
of hydrogen contqin
aa.
l2 ns =
and 70 cm Dressure. = Mf, M;
K-l mol-|. Funher Pa = 2 bar, Po + PB = 3 bar ie' Ps = lbar
above is found to be
App$ing the relation PV = nRT
mass of hydrogen.
P^V = no RT, P"V = nrRT
Solution' Here we are given
V = lS litres
PA nA l/M^ NIs
= ,W
?JM"=
T = ZTC = 27 +273K = 300K " % ^r=
P = 70 cm = iOl76 atm o,
-. 5=2x 3=
PB
zx?I = q or MB=4MA.
R = 0.0821 litre atm K-t mol-l MA
Using the ideal gas equation, 'iilil'i |
340'5 mL ofphosphorus vaPour
PV = zRT weigh 0 0625 g at 546"C and 0' 1 bar pressurl\h:1
is tie molar mass of phosphorus 2 (N'C'E'R'T')
pv _tzozzlllgl
RT = (on8rl) (3oq)
we have n= Solution. SteP 1. Calculation ol volume at
0"C and 1 bar Pressure
= 0'67 mole 1xV2
P,Vt PrYz 0.1x340 5
Further we know that : ie -i6int =6
n:
Mass : m n
Mola*lu, *uat M " or Vz = 11'35 mL
rt 1 350 1.1'35 mL ofvapour at 0"C and 1 bar pressure
... M:;=ffi=20r5u weigh : g'0625 t
10 g of Orwere introduced into
.'.znOO mL of vapour at 0'C and I bar
pressure will weigh
an evatuated vessel of 5 litre capacity maintained al
27'C. Calculate the presswe ol the 1as in almos' =yy.35 x227o0='t258
11
pheres in the containei
Solution. Since the volume of a gas is equal . . Molar mass = 125 g mol-l
to the volume of its container, therefore AltemativelY, lsiDig
V: 5 litres R = 0 083 bar dm3 K-1 mol-1
Further, molecular mass of O, = 32'0, there- PV
pV: nRT i.e. n=FT
fore the number of moles of O, gas are
10 : x (3'm'5 x l0-r d,n3)
0'l bar
n= moles
oogl uir a.3 r-r Mol-r x 819 K
-
We are also given =5x10-amol
T :2:TC = 2i7 +2il3K :300K
Thking R : 0'0821 litres atm K-l mol-l
... Massof I mote = = rzsg
ffig
and using the ideal gas equation' PV
: n RT Molar mass = 125 g mol-l
we havc i,\ ,i::'1 1 tlgof methane is placed in 5litre
o-f,M- t0/32\ O.082r\ (3N container at 27'C. Find Boyle constani
Solution. PV = Boyle constant
But PV:nRT: M
=
A-ol x 0 0821 LatmK-rmol-r x 300 K
16

= 12 315 L atm.
 STATES OF MATTER
2117

l. Clculate the number of moles ol hydrogen gas is then filled to a pressure of 735 mm at 31.C with
prescnt in 5@ cm3 of tbe gas taten at 3b0K ino i6O a gas of unkno\pn molecular mass aDd then
mm pressure. If this sample of hydrogeD is found rcweighed ; irs mass is 137.456 g. The flask is rhen
to have a mass equal to 4.09 x l0-2 g,calculatethe filled with waterandweighed again ;itsmass is now
molar mass of bydrogen. 1067.99. Assuming thar the gas is ideal, calculale
the molar mass ofthe gas.
I .1Ds2.03 x l0-2 Eole. 2.01 g mol-rl I EO.2S g mol_ll
2, 2.802 g of N2 gas is kepi in a lire flask at trC.
6. C-alculate the tempcrature of 4.0 moles of a gas
C.alqrlate the pressure exened ry thc gas. occupying 5 dm3 at 3.32 bar (R = 0.083 bar
[ \" '2.24 atEI dm3 K-r mol-l) .
N.C.E.R.T) I ,,.,s0 Kl
3. C-alculate the molar volume of 7. C.alculare the volume Gcupied by 8.8 g of CO2 at
a gas at ST?
[ .1ns22.4litrcrl 3i l'C and I bar pressure (R = 0.083 bar L
4. A 500 ml sample of a gas weighs 0.326 g ar 100"C K-lmol-r) (NC.E.R.T.) [ s.0s L)
and 0500 atm. What is the molecuhr mass of the t. 2 9 g ofa gas at 95oC occupied the same yolume as
8as ? [ 39.9 amul 0. 184 g of hydrogcn at l7.C at the same pressure.
5. A large flask fitted with a stop-cock is evacuared What is the molar mass of the gas ?
and weighed ; its mass is found to b 134.56j
E IL (N.C.E.R.T.) 1,rrrs40gmot-rl
-t I N -.- For-DtFFtc,uur ?RIrt:ava
t. Proceed as in sotued example L This gives z = 0.036 mol
2.8(D 8 of N2 = 2.80218 mol. Mass of 0 036 otol of the gas
Then apply PV = zRT = (13't 4s6-r34. 567) E = 2.889 E
3. At S.TP., P= atm,'l=273K Appty pv=n RT
1
. Mass of mot of rhe gas =
#f,:? = 80.2s
1
s
Dke4 = 1mol, R = 0.0821 Latm K-l mol-l.
6. PV = aRT
5 Mass of warer fitling rbe flask
= (1067 .9-134 567) C = 933.333 C or ,r=!Y=o${ffi=sox
.. Volume of flask = Volume of\rater lilling the 7. Appty PV = aRT
flask = 933.3- cm3
'"'1 '.' densiry of HzO = I g cm-3) t' As Pr = Pz and Vl = V2,
NorP = 735 mm, T = 31 + 273 K = 304I( . nrTl = n2T.-
V = 933.3 cm3
ff , <ss * zttl = lf , Oi + 273)
Appryins pv =,nr ;, (rff ",,") [ti3ot*i)
r x 0 0821 L atm K-l mol-l x
or u*=T##=4osmot-l
= 304 K

.. tut
dK 1.56x0.0821 x338
= P 745/760
The density of a gas is lound to
be 1.56 gllitre at 745 mn pressure ani 65.4. Catcu- = 44.2 u
lale the molecular mass of the gas.
_ _:
The density of a gas is 3.80 g
So_lution. Here we have d= 1.56glitrc-l L- ' at S:T.P. Cqlculste its density at 27,C and 70b
p=745mm=]9u,- torr pressure.
7fi
T : 65.C :65+273 = 338 K # a-
Solution. d = the same gas at two
R : 0.0821litre atm K-l mol-r different pressures aDd temperatures,
2118
l'ralr ty's Neut Course

d, P, T2 Solution. Using the solution, , = H,

da P2 Tl "
the same teEperature
dt = 3'80 8L-1,Pl = 76otor,,Tt = 273K MrPl = NQP, (as R is constant)
d, = 2,P, = 700 torr, Tz : 300 K (cascous oxide) (N,
, T =m*ffi o, dz=3 rtssL-1 .. Mr x 2=28x5
(Molecular mass of N, : 26
ti\A\l Pl,lr ' Ar 0"C, the density of a gaseous ';
oide at 2 b ar is sdme ds lhat of nitlogen at 5 bar l'yhst or Mr=70u
is the moleculu mass of the oxiile 2
(N'C'E'R'A)

l. The density of a 8as is found to be 3.43 gniue at pressure is equal to 1 bar). I 29.3I Eol-rl
30OK aod l-.00 atm Pressure. Calculate the rDolar 3.
ma,ss of the ga.s.
I E4.5 g mol-ll
2. If the deosity of a gas at the sea level at 0'C is 1 '29
kg m-3, what will be its molar mass (Assume that

dRT -3 x 8.314ljm K-1mol-'x273 K mol-r (1J=1 Nm)

2. M= -n-= =o.on{iir,",t-t =129.3 g

LAW OF PARTIAL PRES. ''.::!:!':!:::!: '

partial pressures :

IJ two or more gases wh, Pressures.

are enclosed in a vessel" t
Ps, : 50 mm, Po, = 1m mm'
lhz gsseous mi$ure is
partial
'presenl
press res ih P: Pr, + Por: 150mm
alone in ,hz
Applications of Dalton's I,aw of Partial Plts'
sures.

When the volume of the gas is measured after

careful levelling (so that the level iaside the measur-
 STATES OF MATTER 2119

Plrltospxem

FIGURE 2.14. PsB t P*ot",,o-,o = Pmst gE

each gas is considered to be an ideal gas, thon

applying PV : nRl
RT RT nciRT
pe, = ne_y ,pa = ns V,pc=
and so o[.
By Dalton's law of partial pressures,
pressure exerted by the gas and the water vapours Total pressure, P = pe, * pe * pc + .-.
is equal to the atmospheric pressure as shown in
Fig.2.14. RT-
=f(nl+xB+rlc+...)
If P and P' are the pressure of Qe dry gas aud
the moist gas respectively at t'C and p is the . Pe_ nA
:4Jn"+'rc+-
aqueous tension at that temprature, then by =-rA
Dolton's Law of Partial Pressures
f
(mole fraction of A)
P= p P'- or pA =JA x P.
Pary gr" = Pmoisr gF6
- Aqueous te$ion (at fC). SimilarlY,P" = x" x P and so on. Thtts
(ri) In the calculation of pa ial pressures. Partial pressure of A = Mole fraction of A
In a mi*ure of aon-reacting gases A, B, C etc., if x Tbtal pressure

N 9,@,..S* lavt or pARTIAL pBESSUc:s

r.\ \\tpLD 1. 38.U) ml of moist niiogen gas By applying the general gas equation :
were collected at 27C and 746.5 mm pressure. Cal- 7&xVz _ Tm x38
culale the volume of the gas at 0'C aad 7& mm
pressure. (Aq. tension at 2TC is 265 mm).
273 300
-. 'lm xS
Solutlon, :. Yr= -
3m.- * fr=22.rc^t
273

Given condilions Fhal conditions Volume of nitrogcn at ffC and 760 mm pres-
Vr : 38.0 ml Vz = ?ml sure : 32 .76 ml.
6y,q11p1 ,11 2. 25012I of nitrugen mointained, at
P t=746.5 -26.5:7m an Pz = 760 mm
720 mm pressare and j80 ml of orygen maintained
^ft=27 +273 =300K Tz= 0 + 2i73 at 6Y) mm Wssure arc put trythet in one litre flask.
IIthe temepmture is kcpt constanq what will be the
=Tl3K
fnd pressane of the minwe ?
 Neut Course Ch.mistrq
2120

Solution. By applying gas equation, we have

Step 1. 70 calculate the pqfiiql Prcsswe oI 760 x gug P2 x 1000
nilrogen n3 = 2f,8
Gieen conditions Final conditions
: Vz : 1000 ml
760x919x288 :
Volume Vr 250 mI P2 736'7 mm
lmox2:73
Pressure P1 :72Omm Pz:?mm
Slep 2. To Cslculate the vapour pressure of
Applying Boyle's Law since the temperature walet st 15'C.
remains constant Vapour pressure of water = Pressure of the
1000 x P2 : 1m x 250 moist gas - Pressure of the dry gas,

or Pz=
7m x 250
= 180 mm
: 750-736.7 : 13'3 mm
1000
Altemaliveb, ifp is the vapour pressure of
Thus thc partial pressure due to nitrogen
(Pu) = 180 mm.
water at 15oC, then take P, = (750 - p) mm. Sub-
stituting in the equation
Step 2. To calculate the pattial pressure o[
oxySen
P. V. _i_:,
__t_: =
P" V"
we get
Given conditions Final conditions It 12

Vr = 380 ml Vz = 1000 ml
760Z_9t9 _ (750 -?).x 1000.
Solve torp.
Pr = 650 mm Pz: ? mrn 2:t3 248
t. A 2-L .lask contains 1 6 g of
Applying Boyle's Law (since the temPetature
remains consta:rt) methaw and 0'5 g oI hydrogcn at 2TC. Calculate
x the poftial pressarc of each *as in the mintre and
1000 P2 = 380x650
hence calculate the lotal pressule,
380 x 650
P2
1000
= 247 mm Solutloo. 1.6pCH, = 19lnote = 0'1mole.
Ib
Thus, the partial pressure due to orygen (poz) Partial pressure of CHI @cHl)

= 247 mm. RT
Step 3. Tcr calculate the fnal prcssure of the =ncnlxT
gaseous miiule, x
If P is the final pressure of the gaseous mix- _01x0 0j821 300
= 1.23atm
ture, then accordi-og to Dalton's Law of Partial
Pressures, P=Pn, + Po, = 180 + 247 = 427 mm.
t
0.5sH, = f -ot=0 25 mote
t,xel,tt'l,E-r.A$venmassof a gas occupies
919.0 ml in dry sture 4t STP The same moss when
Pafiial pressure of Hz @uz) = rr, , Y
collected over v,latet 4t 15"C ond 750 mm pressure
occupies one litre volume. Cakulate lhe vaPour Prcs'
0.25 x 0 0821 x300
sure ol water at 15oC.
2
= 3'079 atm
s-slcEea-
S|ap l. Tb calculate the pressure of the dry gat Total pressure = Pcto+ Pu,
at 15"C and 750 mm pressure using the qas eEtation'
Given conditions at STP Final conditions = L'23 + 3'079 = 4 31atm
Vr : 919 ml Vz : 1000 ml l1\.\\lP 3.A gaseous mirtwe contains
g Nr, 44 g CO, and 16 g CHa- The total presswe
Pr : 760 mm Pz =? (DrY state)
56
of the mi*ure is 720 mm Hg Wat is the paftial
Tt =273 K. Tz=n3 +L5 =288K pressureofC,?
SIAIES OF MATTER 2121

it Partial pressure of CHo

Solulion. 56HNz -i = :.,'t".
44 'lcun _
_------_---t_ _ ! D
MgCO2=
Z =l mole, -
nl,r+ ncor+ nctlo
I
169CHn = =t 111ol" x 720 = lto mm
t6& = riin

1. 2C0 ml of hydrogen and 250 ml of nitrogen each
mcasurcd at l5'C and 760 mm pressure are pur
rogether in a 500 ml flask. What will be the final
pressure of the mixture at l5'C? [ \r\.6E4mm]
2. 400 ml of N2 at 700 mm and 300 ml of H2 gas
gas
at 800 mrn were iotroduced into a vesscl of 2 litres
at the saore tcDlperature. C-alculatc thc final pres-
surc of lhc gas mixture. I 260 mml
4. What will be the pressure exerted by a mixture of
3 2 g of merhane and 4.4 E of carbon dioxide
contained iD a 9 dm3 flask at 27'C ? (N.C.E.R.T.)
lArr O.tZ atml
5. Wbat will be rhe pressure of the gas mixture when
0.5 L ofH2 at 0.8 bar and 2 0 L ofoxygen ar 0.7
bar are introducd in a I L vessl at 27'C
(NC.E.R.1:.) [,$s.0 4 + l 4 = 1.E bsrl
?

3. Tlvo vessels of capacitics 1.5 litres and 2.0 litres

containing hydrogn at 750 mm pressure and 6 8 I of dygen and 4 g of hydrogen are confined in a

orygen at 10O mm pressure rcspeclively are con- vessiof l dm3at 27'C. Calculatc the totalpressure
nected to eacb othcr through a valve. What rvill be of the mixturc (R = 0 083 bar dm3 K-l mot-1)
the linal pressurc ofthc gasecus mixture assuming (N.c.E_R.7.)
lhat tempraturc remains coDstant ? 7. A minure of trydrcgen and oxyten at one barpres-
[,\,.. Prrz = 32L43 mm. Po2 = 57.14 mEL sure contains 20% by urcight of trydrogen. Calcu late

P,tlrrorn = 37E.57 mml

the panial pressurc of trydrogen. (N.C.E.R.T)
I";rs 0 t barl
H lNT5 FoRotFFtcut:r PRIetErv.a
l. As temperatulc is kepr constanr ar 15"C,
for calculatioD of panial pressure of Il2 gas,
a.r= f,ru =ff$
P1V1 = P2V2 Pcao

i.e. 2OO x '160 = P2 x 500 r|a p*, = 304 mrn 0.0821 dm3 atm K-1 mol-r x 300 K
9 dm3
For calculatioo of parlial prcssure of N2,
=0 55atm
Pr'V,' = Pr'17r' Pco.
rc. 76O x O = Pz' x 5N i.e. pN2 = 380 mm
14 4 \ 0 0821 dm3 atm K-l mol-l x 300 K
= (* ")
Finalprcssure of thc mixture ------ , dm3-
= 304 + 380 - 684 mm -O 27 atfi
3. Finalvolume = 15L+ 2.OL=3 5L pror.,=055+O27
For partial prcssure ofH2, PtVt = P"V2
= 0.82 atm
i.e.75O x 7.5 =Pzx3 5 5. Simriar to Problcm I and Problem 2.
orpHz = (750 x 1.5)/3 5 = 321 43mn nH"
7.Pur= i;!r- OxP
For partial pressure of Oz, Pt'V1, : pz,V2,
i.e. IOO x2 = P2' x 3.5 20a'/2
= fri7TT@i732 x 1 ba.
or poz = (100 x 2) / ?.5 = 57 .14 mm
10
' l',ni.,o," = 321 43 + 57 14 mm = 3?8 57 mm = raE= = 0.8 b".
 Net( Course

LAW OF DIFFUSION/EF- Thus knowing the relative rates of effusion of

the two gases and knowing the molecular mass of
When we enter irto kitchen, we get the smell ore of them, that of the other can bc calculated.
of food. Similarly, if a student in a class-room has
used perfume, everltody in the room gets the
fragrance of the perfumc. This is because the
molecules of the aroma of the food or the perfume
mix with the air. 7h e spreqding of the molecules of a
gas throughout the available space is called dif'
fusio_nj It differs form th
process in which d gas un
a tine hole or oifice in a
1:Pr\/E:P,
r, Pr'd, Pz
q
gas from a cyl or (ii) Compaison of volumes ol two different
escaping out he gases efusedldifused in lhe same time. Suppose ut
atomizer etc. is
is the volume ofgas 1 diffused in time r and u, is the
always followed by the process of diffusion.
volume oI gas 2 diftused in the same time r under
Thomas Graham studiedthe rates of diffusion
the same conditions ofteperature and pressure and
of different gases. He observed that the lighter
through the same orifice. Then
gascd diffuse faster than the denser gases. In 1831,
he put forward the following law :
Rate of diffusion of gas 1 1r.,1
a
= t

Ratc of diffusion o f gas 2 (rr1 = 2

t
lf d, ar,d d, are their resPoctive densities or
Ml and M2 are their respective molecular masses,

q
For two gases having densities dr and d, and
rates of diffusion r, and r, under similar conditions then
of temperature and pressure \='r"
r, ur/l =\=JL
u, dt
=
fl d2
f2 dl Thus volumes of two gases effusedldifrused in
the sdme time (hrough the same oifice) under
Here the term'Rate of effusion diffusion' im- similur conditions of temPemture and pressure are
plies as under : inversely proportional to the squorc rools of theit
densities-
Rate of effusiory'diffusion
(iii) Comporison of times taken fot elfusionldif'
_ Volume of the gas effrxed/diffused fusion of the sarne volume ol lwo dfurenl gases.
- Time taken
Suppose r, is the time taken for the gas 1 for dif-
The law may be modified for different types
fusion of volume u and,2 is the time taken for gas 2
of calculations as follows :
for diffusion of the same volume u under same
conditions of temperature and Pressure and

vapour dersities.
As mol. mass
also write l
:2 x vapour density, we can
through the same orifice. Then
r., u/1, t, tl
h v/tz lr
dz
dr

"fh\s times taken for efusionldifusion of same

q
1:JV
tz 'Mr
volume of two dfurcnt gases under the same condi-
tions ol lemperature and pressure (lhrough lhe sane
oifice) src diectly Propoftional to the square rools
where M1 and M2 are thc molecular masses of the of theit densilies.
two gases.
STATES OF MATTER
2123

seconds respectiveb). If the molar mass oI A is A0,

calculate the molar mass of B.
(N.C.E,R.T)
Solutlon. Suppose the volume of each gas fri
diffused : u cc. Then by Graham's law
' of dif-
fusion

rB
u/20
u

I -ffi-
/1O
q moniwn chloride will first aryea,
Solution.

*=ffi= \/
? (N.C.E.R.T)
By Graham's law of diffusion

1,' ={zTtr
or a= v80 = 1.465.
Thus NH, travels 1.465 timesfaster thanHCl.
or MB = 20 g mol-l
In other words, NH, will travel 1.465 cm in the
- 27 ml oI a cettain gas difuse in same time in which HCI travels 1 cm.
thes ml of chloine under the sunte Length o[ rhe rube = 200 cm.
cond,itions. Cakulale the molecular mass of lhe gas.
.'. Distance travelled in the tube bv
If , is the time taken for diffusion 1 465
of each gas, theu by Graham's law of diffusion NH: = x :
t.qfS + r 200 ll8'9cm
rx ln/t 7t Thus NH.CI will lirsr appear at a distance of

'.r, 700/t Mx 118.9 cm from NH, end or 81 . 1 cm from HCI end.

?.RO.BLEM3 FOR
1. Calculate the molar massofaD unknotrn gaswhrch What are thc relative rates ofdiffusion ofthese two
dimrss 1 117 times faster than o(ygen gas through molecules under ideal conditioDs ?
the same aperture utrder thc same conditions of
temperature and pressure. Itrr. 0 9957 : 1 0]
4. 50 mlof hydrogen takes 10 minures to diffuses our
[;\ns. 25 65 g mol-l] of a vessel. How long will 40 ml of orygen take to
2.1f 25 ml of CO2 diffuses out of a vessel in 75 diffusa out under similar conditions ?
seconds, wbat volume of SO2 would diffuse out in Itu.32minutes1
the same time under the same conditions ? 5. A small quantiry of gaseous NH3 and HBr are
ttrs. 20 73 EU in-lroduced simulraneously tnto rhe oppGi[e ends
3. Uranium isotopes haw been separated by raking ot an opn Iube which is one metre long. C_alculate
advantage of the differcnr rates of diftusion ofthi the distance ofthe white solid NH4B[ formed from
two fo-rms of u ranium hexafluoride, one contaming the aDd which was used to introduc NH3.
U-238 isotope and the other containing U_235:
I rrrs 6t 5t cm]
H lN rS FoRrlFFtcuLr ?RIrlLEv,I
1.rx-
,o, lE- 1111=\fF*
2' \ \/tl
12 v2/12
u*=nfiU=zs.65gmor
or r

- ti+=tE
 Neut Course

or +=l# oru2:20 73mr o. '^,

,o, =

5t
'#HB='ffi or
or
fr="
l=32min.
5. Similar to solved examPle 3.
ffiB# =',/$=o*,,,;
For morc numericals, see .c.B.s.E. (PM.T.) and I.I.T. (Maitrs)', at the end of this unit. Problems 11
and L2, page 2160 and Problems 10, 13 at'd 15, page 2'165,66'

:I volume coemcient (au). Al constaot pressure, the incre3se in volume of a 8as Pr degrce rise of temPerature
v, - \'o
per cc of the gas at 0"C is called the volumQ c.reflicicnt of the Sas Mathematically, %= -I5 x r
Vo = volume of thc 8as at 0'C
Vr = volumc of thc gas at r'C

For all Sases, velue ot auis 1D13.

rlse of
I PEssure coeflicient (ap). -At constant volumg, the incrsase in the pressure of a 8as per degree
temperature divided by its pressure at 0'C is called pressure cocfficient of the Sas Mathematically

".=H
For all gases, valuc oI cris 1213.
R g.:t4 JK-l mol-l
' Bottzmatrn constant (k) = Gas constant Per molecule = No 6.02 x 1023 rnoleculcs mol-
= r '3E x 1o-ts JK-1 molecule-1.
l: i .1 Gases baving lhe same molecular masses have same rates of diffusion e'g CO, Nr' CrHa' B2H5 (mol mass =
28).
;:|5.Atmo\sisTheprocessofseparationoftwogasesonthebasisoftheirdifferentratesofdiffusiondueto
I ' drfferince in their densities is;lled atmotpis. ir has been apptied with suc-clss for
the separatior of isotoPes
a[ld other gaseous ml\tures.

a large number of molecules which were in cease-

less iotion. For the same reason, it is also called a
'Dynamic particle model' of the gas Thc name
'Microscopicmodel' isalsousedbecausethemodel
 STATES OF i,,lATTER
assumes the gas to be made up of molecules which
cannot be seen.
Postulrtes or Assumptions ofKlnetlc Theorf,
of Gases fhe Microscoplc Model ofa Gas. Thc
- not have been possible ifstrong forces of attraction
main assumptions on which the kinetic theory of
gases is based are as follows : Posrulate (b) can be seen to be correct on the
made up ol a large number of
(i'1 Every gas is
extremely small paticles called molecules. All the
molecules of a panicular gas are identical in moss
and size and differ in these from gas to gas.
(ii) Tlu molecules of a gcs orc sepuated lrom
each other by larye distances so thst the actuul
volume of the ntolecules is negligible as compored to
the lohl volume oI the gas.
(iii) The distances of separution between thc
molecules are so larye that the forces oI attraction or
repukion between them are negl@ble.
(iv) torce ol gravitstion on lhe molecalcs is
The
also supposed to be negligible.
(v) lhe molecales are supposed to be nioving
conlinuously in dilferent dircctions with dilJerent
velocities. Hence they keep on collid,ing with one
anothet (called molecular collisions) as well as on
the walls of the conlaining vessel -
(vi) The pressure exe,led on the walts of lhe
containing vessel is due to the bombardment ol the
molecules on the v,,alls of the containing vessel.
(ii) The molecules are supposed to be perfectly
elaslic hard spheres so lhat no enc,W is u,lasted, when
the molecules collide with one another o ith the
w,alls oI the vessel. The energ) may, howeve; be
transferred from some molecules to the olher on
collision.
(viii) Since the molecules are moving with dif-
-
Jerent velocitie!, they possess different kiiaic enir-
il,#.,'l',fi
Justillcatlon ofthe abovc postulates :
2l2s
Posh.tlote (iii) is supported by a simple obser-
vation that even a highly compressed gas expands
when the pressure on it is decreased. This would
cxisted between thc molecules.
basis thatifa cylinder filled with air is invertedover
another cllinder containing a heavier gas (heavier
than air) like bromine, even such a heavier gas
travels up into the cylinder hllcd with air.
motion. When the molecules move, they will
naturally collide. The fact that a gas fills up a vessel
of any sizc in a very short time further supports this
postulatc.
Posfillate (i)is quite obvious. Since the
molecules are continuously moving. they can col-
lide not onlywith one anoth;r but al;o witir the walls
oI the container. Since a large number ofmolecules
aretitting the wall. they will exert some significant
push or an outward force on the wall. The force
cxcrtcd on a unit arca of thc wall is callcd the
pressure. This concept is further supported by the
inflation of a rubber balloon or a cvcle tube when
more and more air is pumped into ii.
Postulate (vii) statcs that the collisions are per-
lectly elastic. If it were not so, the lorces of friction
would havc slowcd down the molecules during every
collision. Ultimately, the gas should have scttlea down
after somc time. Since this, in fact, does not happer!
the posfulate must bc correct.
energy increases. On the contrary, when a gas is
cooled, the molecules slow down aod henci the
kinetic energy decreases. The Iiquefaction of gas
clearly supports this vicw.
,6 lstdbutlon o,
At a particular tempcrature, the different
molecules ofa gas posscss dilfcrcnt specds. F\rther
due to continuous collisions of the molecules
among themselves as well as against the walls ofthc
2126
Net4 Course Chem istrglfffil)
container, their speeds keep on changing. Maxwell For 1mole, mxn: massof l mole =M,
and Boltzmann, however, showed that as a result of
1
molar mas" in g. Hence PV = Mu2 or

e
collisions, though some molecules are speeded up, i
some otlers are slowed down and hence the frac-
tions of molecules possessing particular speed
remains constaEt at constant temperature. This is
,=\E=tr=
called Maxwetl-Boltzmaaa dist bution and is
rvhere d : M./V is density of the gas
shown by the curves in Fig. 2.15(a) for two differenr
tmperatures. Tlpes of speeds, It moy be tntcd that thcre are
lhree types of speeik ol gaseous molccules whirh are
z commonly used- These are
z
(i) Most probable sPeed (a). This is lhe sPeed
u,
fzrlt possessed by lha maximum traction of
)f
uJ
MOST
molecules.
o PBOBABLE
ul SPEEDS
o (ii) Root Mean Square (RMS) sped (u). 1, ts
the square root oI the mean ol tlu squares of the
o speeds ofthe molecuks. Thus iI u,uz,u3....u ndre
z lhe speeds oJ n molaules then
o
O Root Mean Square sPeed (u)
(!
IL
MOLECULAR SPEEDS ul+o!+ ... + v2,

FIGUBE 2.15(a). Maxwell's distribution of (ii) I, is tlu wemge oI the

speeds at two diflerent tempratures
Average speed (u).
difrerent speeds oI all lhc molaulc.s-
ut+uz+...,+un
POSS h'emge sryl (u) =
and
able Nole. Instetd o! symbols, a,o and u, symboh
rise uDp, udu qnd urn, are olten used.

Rclationship between dilTertnt tyres of

,f,::
speeds. As derived above, for root mean square
the fraction ofmolecules possessing most probable snecd
speed,decreases with increase in temPerature.

:il.'
a= r/y _i,l
IRT

th Similarly, for most probable speed (a) and

in the kinetic theory ofgases, a mathematical equa- average speed (u), we have
tion has been derived ftom which all the gas laws
can be deduced. This equation is known as'kinetic 8RT
gas equation.' It is usually written in the form
1-
"=y'E,,= nM
py _ Thus the three types of speeds are related to
iJ mnu, each other as
whcre P : Pressure exerted by the gas,
V = Volume of the gas u = 0'971u, a=0'816u
q:!:u = l: l'128: L'?24
J

rn = Mass of each molecule of the gas |

n = Total number of molecules present in These may be represented graphically in

volumc V
the Maxwell distribution curve for speeds as
u = Root Mean Square sPced of the gas follows:
 STATES OF MATTER 2127

to move about. Consequeotly, the number of

molecules striking the unit area of the walls of the
container in a given time will now become one half
f the original number. As a result, the pressure ofthe
o
-ct_ gas will be reduced to one half of its original value.
o u Thus it is obvious from the above discussion that
= pressure increases accordingly as the volume
o
z decreases or vice versa at constant temperature.
o
tr This sl.atement represents nothing else but Boyte's
o
q. Law.
Deduction from Klnetic Gas Equation. Ac-
cording to kinetic gas equation
MOLECULAR SPEE O .-------}

FIGURE 2.f 5O). Representation of rehtive

rv = ]mnu'?
values oI cr , u and u.
)
Explanalion/deduction ot Gas
aws f rom Kinetic Theory,.:,.:.i,::,r,;,1t:ii.,.,,..,,.,,.:r.-,i,,,,t|. 3' ]-n" = 1'*t*
(1) Boy'e's Law
(where rn xn : M is the total mass of the gas)

Explanation on the Basis of Kintic Theorf,. nut j rrau'? = Kinetic energy of the gas
According to Kinetic theory of gases, at constant
temperature, the average kinetic energy and hence )
the average speed of the molecules is constant. .. PV =
; K.E. ...('
Further, the number of molecules present in a given
Further, according to one of the postulates of
mass of a gas is also constant,
the kinetic theory of gases,
Let the volume of a given mass of a gas be
reduced to one half of its origina.l volume. The same K.E. c( Absolute 'Ibmperature (T)
number of molecules with their same average speed or K.E. = /<T ...(r,
will now have half the original space to move about. where & is a cosstant of proportionality.
As a result, the number of molecules striking the
unit area ofthe walls ofthe container in a given time Putting this value in equation (i), we get
.,
will get doubled and consequently the pressure is Pv =
also doubled. Conversely, if the volume of a given ;kr
mass of a gas is doubled at constart temprature ,2
As is a constant quantity, k is also a con-
(Fig.2.16) the same uumber ofmolecules with their i
same average speed will nowhave double the space stant, therefore, if T is kept constant, kT wilt be
3
constant. Hence PV: constant, ifT is kept
GAS constant, which is Boyle's law.
MOLECULES
IN MOTION
(2) Charles' Lav
ExplanatloD on the Basis of Kinetic

\ 1\ Theory. According to the kinetic theory of

gases, thc average kinetic energy and hence

\\tl the average speed of the gas molecules is

directly proportional to its absolute tempera-
LARGE VOLUIVIE SMALLVOLUME ture. Thus, it follows that when the tempera-
ture of a gas is inceased at constant volume,
FIGURE 2.f 5. Rate oI molecr..rlar cdltsions the average kinetic energy of its molecules
increases by decrease in volume.
increases and hence the molecules would

-.1
2128 Pradeep's

move faster (Fig. 2.17). As a result, the molecules numbcr of times per seccnd as ifno other molecules
ofthe gas *ill strike the unit area ofthe walls ofthe
container more frequently and vigolously. Conse-
quently, the pressure of the gas will increase ac-
cordingly. Thus, at constant volume, the Pressure
of a gas increases with rise in tcmperature. This
explains the Pressure Law.
vr'hen prcsent alone in that space. Hence the
Kinetic theorl,explains Dalton's Law of Partial
Pressures.
Deductlon from Kinetic Gas Equation. Let us
consider only two gas,?s. According to kinetic gas
\/ .
equation,
7 mnu2
w = \mnu2 or rP =:3 v
\"/, Now, if only the ffust gas is enclosed in the
vessel of volume V, the pressure exerted would be

LOWER TEMPERATURE HIGHER TEI/lPERATURE o - lmr\ul

SLOW I/lOVSMENT FAST MOVEMENT
't- 3 v
FIGURE 2.17. Again, ifoulythc second gas is enclosed in the
same vessel (so that V is constant), then the pres-
C)n the other hand, if the pressure of the gas 1 mzn2utr
is tobe maintained constant, the force per unit area sure exerted would be P, = i-:1-
on the walls of the coutainer in a given time must Lastly, ifboth the gases are enclosed iogether
be
in the same vessel then since the gases do not react
by
with each other, their molecules behave inde-
co pendent of each other. Hence, the total pressure
ga
exerted would be
explains Charles' Law.
Deductlon from Klnetlc Gas Equatlon. As o- 1^"'u1 * L mrnru!
de.luced in equation (ii) above from the kinetic gas
'3V3
equation, we have =Pr*Pz
w:!n Similarly, if more thatr two gases are present,
then can be proved that P = Pr * Pz + P3 + ...
it

This may be rewritten as

v 2k n Between Average Kinetic
T 3P and Absolute Temperaiure-
e"qlglIlrglUilejillhe_ory-._,: " ii:i:: nnii,r::,ir:
? i. .on.tunt, ft is also constant, hence if P is
3 According to Kinetic gas equation,
V
kept constant,
T = constant. which
is Charles' law' PY =lmruz
l
."(,
(3) Dalton's Law of Eartial Prtssures where P is the pressure, V is the volume ofthe gas,
Theory. m is the mass of each molecule, n is the number of
eattrac- molecules presnt and u is the root man squarg
same or speed of the molecules
different gases are very weak under ordinary con- If l mole of the gas is taken, then tho total mass
ditions of temperature and prcssure. Therefore, of the gas, m x ,t : M, the molar mass of the gas.
the molecules ofa gaseous mixture move complete- Hence eqn. (i) bccomes
ly independent of one anbther. As a result, each
molecule of the gaseous mixture would strike the Pv = (u)
+Mu2
unit area of the walls of the container the same
STATES OF MATTER 2129

It can be re-uritten as number, N i.e., the nunber ofmolecules present in

)1 one mole ofthe gas. Thus we have
ev : i.)uu'l
l-
aue,aee x.e. =
lftr
1
But
, Mur rcpreseDls the kinetic energy or 11s = jkr -.(v)
(K.E.) per mole
) where t = ft is called Boltzmanu cotrsta.nt
Heoce pV=;xK.E.
From eqn. (v), we observe that
? Average K.E. q Absolute temperature of the
or KE. =: PV for I mole of the gas ...(iii) gas irrespective of the nature of the gas. This is one
But for 1 mole of the gas, the ideal gas equa- of the postulates of kinetic theory of gases.
tion is Further, as l<.2. i.'e. K.E. ct z2 and
= zmua
PV=RT
Putting this value in eqn. (iii), we get
Thus, when T = 0 K, rr = 0 i.e. molecular motion
1
K.E. : RT tor 1 mole o[ the gas -.{ir) in a gas should become zero at absolute zero. In
; fact, the gas liquefies before this temperature is
To get average kinetic energy per molecule, attaincd. The motion of the gas molecules due to
divide both sides of eqn. (iu) by the Avogadro's temperature is called therpalEe$on.

(b) Aho calculate the root mean square speed

mo oI methane molecules qt 27"C.
mo
mo Solutiol. (a) Total K.E. = I? rrRT
late the sverage speeL rool meqn sEt$e speed and
most prcbable speed oI the gas at 2TC- =|"ft^ax 8 314JK-r mol-rx 3ooK
2 n,u,
Solution. Average spced (u.,) (Molar mass of CH4 = 16 g mol-l)
2n,
= 7482.6 I
10x4+20x5+,10x8 lQ 56.r-t
l0+20+q = =6 Average K.8.,
JK-l mol-l
Root mean square speed (ur.m.r.) ree.=|m =)" 6.02 8'314
x 10r molecules mol-l
a|ffi.ffi
' 2n, ' 10+4+40 = 6.21 x 10-2r J molecule-r
X3OOK

o, = ]nt *ot-r
160+500+2560
= 6 78 ms-I = I x 8.31a JK-l mol-r x 300 K
Most probable speed (u-) = 3741 3Jmol-r
= 0.916 x u,...,
= 0.816 x 6.78ms-l = 5.53 ms-r.
(D)u,,.,,.=tr
r i.\.1\lt,t.i.t I @) Colculate the totql qnd Using C.G.S. units, ptrt
average kinetic energ oI 32 g methane moleculcs at R = 8.314 x 107crgsK-lmol-l,
27'C (R : 8 3141K-1 mot-1) T:27+273=3C0K,
(Bihar C.E.E. 1997, N.C.E.R.T,) M (for CHo) = 16g mol-I, we get
430
l'radcay's Netq Course Chemi stryaifrlll

l-,
.,:v "t'16 *:r+, to' , eoo

=6'E39 x ld cm s-l
(i) For an ideal gas, as PV : nRl, Z : I
= 6t3 9 ms-l
1 (fi) For a real gas, as PV + nRL Z*1. Hence
using S.I. units, put R = 8'314 JK- mol-l,
two cases ari6e :
:
T 300 K M = 16 x 10-3 kg mol-l, we get (a) WhetZ < l, (e.g for CHo, CO2 etc.) the
3x8.314x300 gas k said lo show negative deviarion. This implies
16 x 10-3 that the gas is more compressible than expected
from ideal behaviour.
= 6E3'9 ms-r
This is also attributed to predominanc of at-
tractive forces among the molecules of these gases.

Boltzmann constanl. Also calculate the numbet of

(D) When Z > l,
the gas is said to show
positive deiatiot- This implies that the gas is /ess
molecules present in one mole of the Bas.
compressible tbar. etpected from ideal behaviour.
Solution. Average kinetic energy This is attributed to the predominance of the
1 strong respulsive forces among the molecules.
(K.E.) = itT
Z Greater the departue in the value of Z from
' L,:-\1
2 I(E unity, greater are the deviations from ideal behaviour.
3" T At the same temperature and pressure, the
-
2 5-62L x 10-21 J molecule-l extent of deviation depends upon the nature of the
=3' 273 K gas, as shown in Fig. 2.18 (a). Thus at intermediate

= 1.373 x 19-23;6-r molecule-l

No. of molecules in 1 mole of the gas
IE r.6

o
F
1.4
(Avogadro's No.) = o
f f; 1.2
8'314 JK-r mol-1
= 7.373 ,10-27 JK-l molecule-l ^E
E'J
r.o
ioteL ons
B ou

H 06
tL
^> 0.4
o
Ideal and Real Gases.,4 gaswhich obeys lhe
ideal gas eqtation, PV : nRT under all conditions of
lemperature and pressure is called m \deal gas'' Hr:w'
cver, there is no gas which obeys the ideal gas equation
9,.4 K
(I 273 K
under all conditions of temperature and pressure. o .".023 K
Hence the concpt of ideal gas is only theoretical or 5 r.z
hypothetical. The gases are found to obey the gas laws f-
fairly well if the pressure is low or the temperature is
high. Such gases are therefore krown a s 'Real gases.'
O=''o
d)
IDEAL GAS

AII gases are real gases. However it is found that gases 6

which are soluble in water or are easil, [q uefi able e.g ru 0.8
TE

CO2, SO2, NH, etc. show larger deviations thall the

c
like H, , O, , N, etc.
o
o
gases 200 4m 600 E00
Study of Deviations. The extent to which a PRESSURE (ATM) +
rcal gas deviates from ideal behaviour can be con-
veniently studicd in terms of a quantity 'Z' called FIGIIRE 2.1a. (a) Z us P for diflerent gases
(b) Z rs P for N2 gas at different temperahJes.
the compressibility factor, which is deFrned as
 STATES OF MATTER
pressures, CO2 shows much larger negative devia-
tion than H, or Nr.
For the same gas, at a particular pressure, the
extent of deviation depends upon temperature, as
shown irr Fig. 2.18 (b) for the case of N, gas.
Plots in Fig. (b) show that as the temperature
increases, the minimum in the curve shifts upwards.
Ultimately, a temperature is reached at which the
value of Z remains close to 1 over aa appreciable
range ofpressure, For example, in case ofN2, at 323
K, the value ofZ remains close to 1 uplo nearly 100
atmospheres..
Ilp tempcraan O whlch a r*l p bduva Eb an
idal gas owr ol aryrvioble prrvrr ranrye b
atld @etfst[Exllturar Boylc polnt.
Further from the plots shown in Fig. 2.18, it
may be seen that at ordinary pressures (1-10 atm),
Z rs very iear to 1 i.e. the deviatious from ideal
behaviour are so small that the ideal gas laws can
be applied.
Causes of Deviation from Ideal Behaviour. As
explained above, the real gases obeyidealgas equa-
tion (PV = zRT) only if the pressure is low or the
temperature is high. However, if the pressure is
high or the temperature is low, the real gases show
marked deviations from ideal behaviour. The
reasons for such a behaviour shown by the real
gases have been found to be as follows :
The derivation of the gas laws (and hence of
the ideal gas equation) is based upon the Kinetic
Theory of Gases which in turn is based upon certain
assumptions. Thus there must be something wrong
with certain assumptions. A careful study shows
that at high pressure or lou/ temperature, the fol-
lowing two assumptions of Kinetic Theory ofGases
are faulty :
(i) The volume occupied. by the gas molecutes
is negligible as compared to the total volume of the
qqs.
(ii)The forces of attraction or repulsion be-
tween the gas moleales are negligible.
The abovo two assu-Eptiors are trueonlyifthe
preisure is low or the te.Eperature is high so that
the distauce between the molecules is large. How-
ever, if the pressure is high or the temperature is
+It iiraybc
Pointed out that ior H2 and He. Z,
much below 273 K, Z < 1 elrn for these gases-
2131
low, the gas molecules come close together. Hence
under these conditions :
(!) The forces of attraction or repulsion be-
tween the molecules may not be negligible.
(ii) The volume occupied by the gas maybe so
small that the volume occupied by the molecules
may not be negligible.
Equation ofState for thc Real gases (yan dr
Waal's equation), To explain the behaviour of real
gases, J.D. van der Waal, in 1873, modified the ideal
gas equation by applying appropriate corrections
so as to take into accouDt
(r) the volume of the gas molecules, and
(r'i) the forces of attractiotr between the gas
molecules.
He put forward the modified equation, known
after him as yan der Waal's equatiou.This equation
for 1 mole ol the gas is
(r.#)ry-D)= Rr
andfor n moles of the gas, it is
e.#)
where'a'and'b' are constants, called van der
Waal's constants. Their values depend upon the
nature of the gas.
DerivatioD ofr,on der Waal,s equatio[. Van der
r*hal's equation has been obtaincd by modifylng the
ideal gas equation PV = ,I{T by applytng corrections
for the volume and pressure.
(i) Corrcctior for volume, Suppose the volume
occuprcd rythe gas molecules is r. When themolecules
are moviDg, their effective volume is four times the
actuaf volume ie. 4 u. Let us call it, ie. b = 4t(Callen
excluded yolume or co-volume). Thus the fteevolume
availablc to thc gas molcculqs for movement ie
Correcled volume = (V
- D) for one molc
or = (V - nr) for n moles
Qi) Correction for prcssurc. A moleculc (A)
lyiog within the vessel is atiracred equalty by other
molecules on all sides bur a molecule near the wall (B)
is aftracted (pulled back) by the molecules inside (Fig.
2.19). HencE it qens less pressure. In other vords,
observed prssure is less tban the idealpressure. Henc
Crrrected prcssure = P +p
> 1\r1e: T >
2?3 K and rncrcascs with inctcase in prEssure Al tempraturc
2132 Neut Course Chem istr1lm)
Unlts ofvcn der Waal's constatrts
WALL OF THE (i) Unlts of 'E'. As
VESSEL
an2
' v2'
... A=.
Dxv
1
n-
= atm L2 mol-' or bar dm6 mol-2
(ii) Units ofrb'. As volume correction
u = nb,
MOLECULE 'A' MOLECULE'B'
.'. b=9n = Lmol-l ordmtmol-l
FIGURE 2.19. Baclarard pull oIr moleculc
B by other molecules. Explanailon of the behaviour of Real gases by
van der Waal's equatlon
Evidcntly, the conection term p is proportional (r) At very lorr prtssurcs, V is very large.
to dcDsity ofthc gas ncar thewalland thc dcnsityofthe
Hehce the correction tcrm a/\P is so sDdl that it
gas insidc ie.
can be neglected. Similarly the correction term 'b'
p
" (densityf orp - d2
can also be neglected in cornparison to V. Thus van
[]ut d. Vforonemolc I
der Waal's equation reduces to the form PV :
RT.
This e:rplains why at very low pressures, the real
or d' Sfornmoles gases behave like ideal gases.
(ii) At moderate prssures, V decreases.
llence 2 d I for onc mole or p = a 161sns rn91s Hence a/V increases and cannot be neglected.
v2'v2 However V is still large enough in comparison to
'b' so that'D' can be neglected. Ttus van der Waal's
,r, o- trorn-olesor r= Siforn moles
v2'v2 equation becomes

.. Corrccted pressure = (y ,3) forone molc

'v (r.+)V=Rr or PV *+=o
or = \fr, - 4f fom moles.
v2/
ot PV=RT-+
where 4 is a constant depnding uPon the nature PV 1a
oI the gas. or RT= '-nrv
Substituting the corrected values ofvolume and _4
pressure in the ideal 8as equation, we get or Z= ' RTv
\tP+- v2 )
(v - ,) = RT for one mole Thus compressibility factor is less than 1. As
pressure is increased at constant temPerature, V
or \lP*onZ\ U - ,1b) = nRT for 4 moles. decreases so that the factor c/RTV increases. 'fhis
vzl cxplains why initially a dip in the plot of Z versus P
is observed.
Sigtrilicance ofvan der Waal's constants (riD At hlgh prcssurcs, V is so small that 'b'
(i) van der Whal's constant 'a'. Is value is a cannot be neglected in comparison to V. The factor
me a/\2 is no d6ubt large but as P is very high, a/V2
am can be ncglccted in comparison to P Thus van der
Waal's equation reduces to the form
(ii) van der lvaal's constant 'b'. Its value is a P(v-b)=Rr
moasure of the effective size of the gas molscules. or PV=RT+Pb
Its value is equal to four times the actual volurue of
the gas molecules. lt is called ucluded volume ot or PV Pb

co-volume.
RT=1*RT
 STATES OF MATTER 2/33

or z= 1+# Z is always greater thao 1 and increases with in-

crease ofpressure. This isbecause H, andHe being
Thus compressibility factor is grcatcr than 1. vcry small molecules, the intermolecular forces ,rf
As P is increased (at constant T), the factor PblRT attraction in thcm are negligible i.e. 'a' is very vcry
increases. This explains why after minima in the
curves, the compressibility lactor increases con- small so that is ncgligible. The van dcr Waal
fr
iinuously with pressure. equation, thcreforc, becomes
(iv) At high temperatures, V is very large (at P(v-b):Rr
a givn pressure) so that both thc correction factors
(a/V atd b) becomc negligible as in case (i). or PV=RT+Pb
Hence at high temperature, real gases behave l_ike or
PV Pb
idealgas. RT -' RT
Explanation of the xceptional behaviour of rhus i.e. Z> l and increascs with
hydrogen aod helium. From Fig. 2.18(a), it may be ff
seen that for H2 ard He, the compressibility factor increasc in thc value of P at constant T.

PROtsLEMS ON
l.\ \\l!,1_lj I Calculste the prcssurc excrled by
110 gof carbon dioide in a vessel of 2 L capscity at m
37"C. Given that the van der Waal's constants are at 10 bar pressure. Given that Ior SO2 gas, van der
a : 3. 59 L2 alm ntol-2 arul b = 0. 0427 L mol- t. Waol's constants ate : a : 6.7bar L2 mol-2 and,
Comparc thevaluewiththe cqlculatedvalue if the gas
b = 0.0564 L mol-l.
were considered as ideol.
. Solution. According to van der Waa-l,s equa-
. Solution. According to van der Waal,s equa-
tron
tron

b.4\ N -nb)=n.r
\ v,/' (r.#)(v-nr)=aRr
nRT
ot ^P=v-nb-nzsn2 _ (p + anztvz11v - nb1
nR
As pressurc is in bar, takins R = 0.08J L bar
n = 1.'9 =
Here,'44 ,'t molus. Substituring rhe
K-l mol- I and substituting thc frven values, wc gr-t
given values, we get
[10 bar + (6.7 bar L2 mot'z) (z mol)z / (5 L)2]
(0.0821 L atm K-l mol-1) (310 K
P= 2.5 mol) T= 5L-2molx0.0564Lmol-1
(2L - 2-5 mol x 0.0427 L mol-l) 2 mol x 0.083 L bar K- I mol- I

_ (3'59 L2 atm mol-2) (2.5 mol2) .072 bar) (5

_ (10 bar + 1 L - 0. 1128 L)
QL)2 2 x 0.083 L bar K-l
= 33.61 atm - 5.61 atm = 2E.0atm :326K
. .
If the gas were considered as ideal gas, apply- One mole of SOrgas occupies a
ing ideal gas equation volunrc oI 350 mL at 27.C qnd 50 atm pressure.
Cala ale tlrc coneressibility factor ol tlte gas. Cont_
PV=nRT m,ent o the type of deviation slrcwn by the gqs
Iomt
ideql belruviour
P=,IRT
V
Solution. Comprcssibility factor, Z = {
2.5 mol) (0.0821 L atm K-l mol-1) (310 K
2L Suhstiturin-g, n = I mol. p -
:31.Eatm _-
V=.1.50y10-rL=0.-l5L
5U atm,
2134
N ettt Course Chent istrtl

R = 0.0821L atm K-l mol-r,T = 27 + 2i73 = l'32 x 10-a cm3

= 300 K, we get Considering the moleculc to be spherical,
L)
(50 atm) (0.35
4nF=ir-32x10-E
Z:
(l mol) (0 0821 L atm K-1 mol-1) (300 K) 3

= 0'7ll or ,:1"*xL.32x10-73
For ideal gas, Z: lor thc given gas
1. As
Z < l, it shows negative deviation i.e. it is more
=315x10-24
compressible than elpected from ideal behaviour.
.ll\\\ll't,l! The van der Waal's constant'b'
.. 3logr = tog (3 15 x 10-z)
for orygen k 0 03
' 18 L mol- 1 . Calculate the diameter =-24+0'4983
o! the oqryen molecule.
= - 23'5017
Solutlon. b = 4u
or logr= - 7'8339 =S 166l
0 0318-
-
^, ,, =!-44 7.95 x Io-3 L mot I
.'. r = Altilog 8 1661

= 7.95 cm3 mol-l = 1 466 x 10-8 cm

. . Volumo occupied by one O, molecule
. . Diameter of orygen molecule

7.95
=2xr=2932x10-8cm
6.02 x 104 :2'%2 L

1. Calculate the pressure exerted by 10 2gofNH3in 2. 180 of steam is contained in a vessel of 25 L

I
capacity under a pressure of 50 atm Cilculate the
a 3 .
0 dm3 vesscl at 25"c (a) using ideal 88s equa- temperature of the steam. Given that for water
tion (6) using van der Uaal's equation The van der
vapour. a = 5.46bar l] mol-z and
vhal's constants arc i o = 4 17 daf atm mol-2, KI
b =0 031 Lmol-l. Ituls. 1531 7
6 = 0.0371 dm3 mol-1
[{lrs (a)4 9atE(r)4 Eatml
Dillerence between ldeal gas aorl Real gas. The main points ofdifference are summed up in the table
below :

Ideal gas Real gas

(i) It obq/s gas lau/s under all conditions of tempera- (i) It obels gas Iaws only under low pressure and high
ture and Pressure. temperature.
(ii) No gas is ideal. (ii) All gases are rcal.

(ri) Volume occupied by tbe molecules is negligible as (iii) Volume ocrupied by the molecules is not negliSible
compared to the toull volume occupied by the 8as. as compared to the totalvolume oc{uPied by the 8as.

(iv) The forces ofattraction among the molecules ofthe (iv) The forces ofattraction among the molecules cannot
gas are negligible. be ncglected at high Pressure and low temperature
(v) lt obeys van der rihal's cquation
(v) It obeys the idcal 8as equatior PV = nRT
(rr#)ry-rb)=nRr
 STATES OF MATTER 213s

2.1 1. Liquefaction of Gases and T"=31 '1oc,

Critical Temperature,i:'i:,:i:,:".1
P, = 73'9 atm,
The liquefaction of a gas takes place wheu the
intermolecular forces of attraction become so high V": 95'0 cm3 mol-l
that they bind the gas molecules together to form Critical constants of a few gases are given in
the liquid state. The intermolecular forces of at- TableZ.2below:
traction can be increased either by increasing the
pressure so that the molecules come close together TABLE 2.2. Crilical constants of some gases.
or by cooling the gas so that the kinetic energy of Gas T. (K) Pc (atm)
the molecules decreases and they become slower.
Henc,g a ga s c an b e li qu efi e d by c o ol in g or by app lica- He 5.3 2.29 57.7
tion of pressure or the combined effect of both.
H2 33.2 12.97 65.0
Gases like
ammonia, sulphur dioxide,
hydrogen chloride, carbon dioxide etc. could be N2 126.0 33.9 90.0
liquefied by any one of the modes mentioned above
i.e. either by application of pressure (at room CO 134.0 35.0
temperature) or by cooling (at atmospheric pres-
o2 154.3 50.4 71.4
sure). However, the effect of temperature on the
liquefaction of gases is found to be very important cHc 190.6 456 98.'t
as higher the temperature of the gas, more difficult
it is to liquefy it and higher is the pressure required. coz 304. 15 73.9 95.6
For example, pressures required to liquefy carbon
dioxide at different temperatures are given below : NHr 405 .5 113.0 72.3

Tbmp. ("C) 10 20 30 31.1 It is interesting to mention here that Andrews

-50 -30 -10
61 14. I 26.r
tTessure 44.4 )6 .5 7t.2 73.9 in 1861 was the first to study the critical phenomena
(atm) e4perimentallyusing CO, gas. He studied the effect
Further, it is observcd that gases like of pressure on the volume of CO, at different con-
hydrogen, helium, orygen nitrogen etc. could not be stant temperatures. Some of the isotherms thus
liquefied at room temperature by application of obtained are shown nFig.2.?-l.
pressure alone, howsoever high it maybe. Hence at
one time, thdse gases were called 'permanent
gases'. Now it is well known that each of these gases
could also be liquefied provided first it is cooled
down to or below a particular temperature. In other
words, for each gas, there is a particular tempera-
ture above which it cannot be liquefied, howsoever
high pressure may be applied on the gas. This
temperature is known as critical temperature. Thus
I
Crititql ol'a cat moy be it{rned
o_

as that
uJ
above vhich it cantnt be t
liquefuil lwwsuver higft pressure may be applied l
o
U)
on ehe gas. IJJ
E,
(L

VOLUME, V
-+
represented by T", P" and V". For example, critical FIGURE 2.20. Isotherns of CO2
(From Andrew's experiment)
constants of CO, are :
2136
At the lowest temperature employed
13 1"C, at low pressure CO2 exists as a gas, as
shown at the point A. As the pressure is increased,
thc volume ofthegas decrcases alongthe curve AB.
At B liqucfactiou of the gas starts. Hence volume
dccrcasis rapidly along BC because liquid has
much less volume than the gas. At the point C,
Iiquelaction is complete. Now the increase in pres-
sure has very little effect upon volume because
liquids are very little compressible. Hence a steep
ctrrvc CD is obtaincd. As thc temPerature is in-
creased, horizontal portion becomes smaller and
smaller and at 31 1'C, it is reduced at a point, P.
This means that above 31 1"C, the gas cauot be
liqucfied at maY be aP-
plied. Thus rature. The
correspond gas at the
criticai tem ure, P" (i.e.
73 9 atm). The volume occupied by 1 moie of the
gas under these conditions is its critical volume,
v. (i.e. 95'6 ml).
2.12. Methods tor Liquelaclion ol Gases ,,r:iii:i;
TWo methods most commonly used for li-
quefaction of gases are briefly described below :
1. By the adiabatic expansion of compressed
gas-Linde's Process. This process is based upon
joule-Thomson effect which states as follows :
llhen a gus undcr hilh pres.rure k
allowed lo ex'
pand adiubaticull! through atine orilice (hnle) into
a region o! ltw pressure, it is accompanfud b!
cooling.
The term 'adiabatically' implies that the ap-
paratus is perfectly insulated so that no heat is lost
to or gained frorn the surroundings.
An obvious reason for [he cooling is that when
the gas cxpands frorn a region of high pressure to
the iegion of low pressure, the intermolecular dis-
tanccs increases. Some work is done in seParating
the molecules apart. This is done at the cost of
kinetic energy ofthe gas. Thus the kinetic energy of
the gas decrcases and therefore the temPerature
falls.
(empcra-
sascs arc first cooled to some particular
iure and then allowcd to expand, thcy behave like
other gases. Thc tcmperaturc to which a gas should
Neut Course
i.e. thus be cooled is called thc invenion temperatwe.
The inversion temperatures for hydrogen and
helium are -80'C and - 24O'C respectively.
The process based uPon the above PinciPle is
known as Lit de's process. The apparatus used is in
shown in Fig. 2.21-. The chart showing the names of
the different parts is also given in the Fig. 2.21.
-.>
t
t
t
,,
air c
A = lnlet fo.
B = Compressor E = Copper sPiralwith a jet J
c F = Ouler chamber
= Condensing coils
D = Receiver lor water G = Outlet for liquefied air
F|GURE 2.21. Linde's process for liquefaction of air
The above apparatus was used by Linde for
the liquefaction of air. The procedurc adoptedis as
follows :
Thc air is first compressed to about 200 at-
mosphere in then Passed
through the c csult, the air
is cooled and condense to
form the liquidwhichis removed. The dry air is then
passed through the copper spiral E which ter-
minates iEto ajet J. The air expands through thejct
J into the chamber F where the pressure of the air
falls down to about 50 atmospheres. Thus as aresult
of JoulcrThomson effect, the air is cooled. As the
cooled air moves uP, it further cools the incoming
air. The cooled air is sent to the compressor again
and the process is repeatcd a number of times till
ultimately the air is cooled to such an extent that it
liquelies. The liquelied air collects at the bottom of
ihc chamber F and can be drawn off. Any uncon-
densed air is recirculatcd.
 STATES OF I\,4ATTER
2/37

--)
2.1 3. lnportance ol Critical Temperature
::+::j:,:r:ri.::ii;,:,i:r:

t:-:::-:::_:::::t

FIGUBE 2,22. Claude s process.

He H2 Nz co .q- NH,
\ (19 s.2 33.2 D62i4.o N4r-4os o
d @nLz O 0347 o.Ul t.Sg--t ag 3.5g 4.17

ADD KNOWLEDG| g'

,
UR
'"Jfi T": # i;rTd' rhe.most satisractory and
etc. vir.ial coeflicierts. At very
low pressure, first virial
I Van der al's constant ?, is r
ease ofliqueracrion of
the intermolecular ro'""' the
is in the order so2 , ", ";:]:::l^t:-th:
, ffi*,::"':'::ilffi';:: f,1'"fJffi":f;J::til**::1'::tr:
li.i;;
",, "il'jl
2138

APD TO YOUR KNOWLEDGE CONTP

in the Saseous state and liquid state are same and there
is
At the cntical poiot, the denslties ot the substance
no distinction between the two states substancs'
super citical fluids. They dissolve many orSanic
r 4. Fluids above the critical temperarure are called
of a mixture into ils comPonents'
ft ut"O fot qrick sepaiation
"y "r" a densltv of about]
and above 600 bar pressure has
co2 abo'Je 31 1'c
*u", * oinr,e
lj{^iltl"--i.1X:'::::::::
than chlorofluorocarbom which are h8rmtul for tbe
e'vironment.
;;;;;;;,, ou

SECTION_TI Based upon these postulates, the chalac-

t"ristic froperiies of the liquids can be explaiaed'
TTIE LIQUID STATE as discussed in the trext sectroo'
2.14. lntroduction

1. ShaPe.Liqu
take up theshaPe of
This is because the
state of co$tant raPid motion'
rne.This
action in
the gas
mpletelY
free to move.

pres
mol I

to; thet '

in a
(iii) The intemolecular lorces of anraction

rcmPeruture.
 STATES OF MATTER

kinetic theory of liquids, the molecules of the liquid Heoce

are constantly moving in different directions witir
different speeds. Thus as these molecules are

results related with the process of

given bclow :
(i) Cooling caused by evaporation. When a
Iiquid evaporates, the more energetic molecules
leave the liquid. As a result, the;verage kinetic
energyofthe remaining liquid decreases ind hence
the temperature falls.
(r'i) Factors afrecting yapour pressure. Tlvo
.rmporlaEt lactors on which the vapour pressure of
If the liquid is added into the evacuated vessel, a liquid depends are :

then initially, as there are no molecules of the (a) Naturr ofthe liquid. Ifthe intermolecular
Iorces o[ attraction in the liquid are weak, the
molecules can casily leave the liquid aIld come into
lhe.vapour phase and henc the vapour pressure is
highcr. For example, the vapour pressure of
acetone, benzene etc. is higher than thrt ofwater at
the same temperature (as shown in Fig. 2.25).
sation. also (Fig. Z.Zq- Ulrimately, a
_increases
stage is reached when rate o[ condensation be-

LIJ
I
(!
l
a
a
tu
d
(!
(!
l
o
I I
I I

.---+TEMPERATURE

_FIG[,RE 2.25. Vapour pressure

temparafure cruves for some liqujds
(6t ElTect of tempe
g of a liquid
is increased,
< liquid increases. This is
iE
Fig.2.25.

versus their corresponding kinetic

energies is as
This is bc@urc acco
E at tcrnFratuE
,nFraturE T is givcn
livcn by fu)ltnann
bv BottzrDann a.d
fact_., -
 Netl Course Chemistrg
2140

bubbles from below the surface start rising to the

surface and escape into the air. The temperatu-re at
*t i.tt tt it ttuppens is called the boiling point' Thus

attmspheric Prexure).
and so does the vaPour Pressure'
a
uJ
J fz, It
f
o
UJ
J
o
=
TL
o
z
o
F
o
ttL

Difference between Boiling and Evaporation'

Although boiling and evaporation -are. similar
pro.".J"., yet they differ in the following two
tu
increased till the vapour pressure De.cornes equar respects :

,ti".pfr"ti" pr".rri",
qtmosnheric Dressure. the vapour in the form of

EVAPORATION

Boiling takes Place at a particular temperature

1. Evaporation takes place sPontaneously at all
1.
where-vapour pressure becomes equal to atmos-
temperatures
pheric pressure.
t Boiling involves the formation of bubbles of the
2. Evaporation takes place only from the surface of *p"ri belorx the surface of the liquid (Ytg'2'27)'
the liquid

(iv) Heat of vaporisation (AI\)' When the

ATMOSPHERIC
PRESSUBE

uid changes into vaPour.

obof the
is callctl

forces
Obviously, greater the intermolecular
is the heat
of attraction pi"I""t in a liquid, greater
FIGUBE 2-27.Bolingof a liquid'
 STATES OF MATTER
2141
of point. For from position CD to position EE Thus some work
ex iling point has to be done against the force of surface tension.
of acetone'
be '
7. Surface tension. Surface tension is a char-
acteristic property of liquids which arises due to the
fact that the moleculcs of thc liquid at thc surfacc
are in different situation than those in the interior

FIGURE 2.29. Concept of

swlace energy.

TIE vok in e$s ,Wirrd to he itorv to irrcrqe or

Aod dttwfaaarw by l sq. cm is alwsudw
erwgL nE totib ol w{ou ercrg oe, tlurqfon,
ergs per q. cn (ot ioub per q. m*e ie.ln-z il
As a result-ofthis inward pull on all molecules lying SJ. sttum).
at the surface, the surface bebaves as if it wcri In terms of dimtnsions,
under tension (like
Surface energy = work per sq. cm.
this property of liq
inward attraction. =(Force x lengrh) per sq. cm.
liquids is called sur dvncs x cm
cm' = dyoes cm-I.
These units are the samc as those of surface
tension. Thus the surface eocrgy is same thing as
surface tcnsion. Hencc the definition of suriace
energy is sometimes taken as the definition of sur-
face tension.
S 5ome importanl.
results o[ surface tension
are bri
FIGURE 2.28. Surface tension oI a liquid.

FIGUBE 2.3O. Inward pull of surface

tmsion makes a drop spherical.
2142
pracleep's Ni ,,, ,",,',t, mii |.JfrtD
knc;wn as adhesive forces e.g- between water and
glass or mercury and glass etc- In case of water
CAPILLARY
TUBE
[aken in a glass tube, adhesive forces aro stronger
than cohesive forces whereas it is reverse for mer-
cury taken in a glass tube.
(iii) Effect of temperature on surface tension'
The surface tension of liquids generally decreases
with increase of temperature and becomes zero at
the critical temperaiure (where the meniscus be-
tween the liquid ancl the vapour disappears)' The
decrease in surface tension with increase of
temperature is obviously due to the fact that with
i.rcrease of temperature the kinetic energy of the
molecules (and hence the speeds of molecules)
increases and, therefore, the intermolecular attrac-
tion decreases.
8.Viscosity. It is well known that all liquids do
not flow with the same speed. Some liquids like
water, ether etc, flow rapidly while some other
liquids like glycerine, castor oil etc. flow quite slow-
ry. fnit i"ailates that
everyliquid has some internal
resistance to flow.

This internrrl rexirsttarce nlln*p*Eassd'y a lfuid

is calld its vMoif[y.

The liquids which flow slowly, obviously have

oonvex.
high internal resistance which is due to strong in-
:':::i':;::':':l:":l:: i:':::: ':i;l:': l i:":"::"'
' .i .:rl:':l::':r:i'::'l::

CAPILI.ARY
TUBE teimolecular forces and, therefore, are said to be
more viscous or are said to have high viscosity' On
the other hand, the liquids which flow rapidly have
low internal resistance which is due to weak
inter-
molecular forces and hence are said to be less

viscous or are said to have low viscosity'

To understand the nature of the internal
resistance or friction existing within a liquid, con-
(Fig'
sider a liquid flowing through a narrow tube
2.33).

u cm/sec
-FIGURE 2-32. (a) Water rises in the-capillary
-
- iUt l,,t"t.ury 'level
falls in the capillatv' u+du cm/sec

, FIG Flow throu$ a narro,rl tube'

,r.33. "i

Allparts of the
tube with the same
be made uP of a large
 STATES OF MATTER
2143
coaxial layers. The layer which is in contact with the Some Important Results. Some important
walls of the tube is almost stationary.
*ith the property of viscosity are as
results related
As we move from the walls towards the centre follonn :
of the tube, the velocity of the dindrical layers
keeps on increasing till it is maximum at the centre. (i) Uoits ofviscosity. As already described,
Conversely, we may say that as we move from the d1)
c lls, the velocity of the layers 4Ad*
k In other words, every layer
o or friction to thelayerimme_ f.tu _
d A. d1)

: dltes cm-z sec,

Thus the units of viscosity are dynes scc
cm-2. This quantity is called I poise (derived from
The flow of a liquid on a lxed horziontal the name of the pioneer worker, poiseuille, in the
surface may be represented in a similar manner as field oI viscosity).
follows :
As force = mass x acceleration
i-e. f = m X a,\ie can also write

-_mXsXdx gXcms-2Xcm
cm'X-i -sT
,l__..._._
T
A 'Aa

* =gcm ,s ,
* i.e. 1 poise = lgcrn-1s-l
u=0 like centipoise and
FIXED HORIZONTAL SURFACE
m ipoise = 10-2 poise,
FIGI.,RE 2.34. Representing florv ol thrae lavers 1
abovp lho fixpd horizontal surfacp

ln sr units. Id* =_l r -

t = Ad"
rcc of friction (fl - il, mln
area A sq. cn,,
having a velocity = Nrn -2s or pa s

v or in place ofg cm-ls-1, we have kg r2 - 15-l

. _dv or -
A .\*du 1
J " d, f= A I poisc =
I;rh ofSI unir.
where 7 is a constant known as coefficicnt of vis-
cosity. du,/d.x is called velocity gradient.

If dx=7 cm, A = 1sq. cm and ../r, = 1

cmlsec, then/ = 7. Hcncc
Coclftcitnt of viscosity may be delimd as thelorce
oI Jriction (in dlrlr;s) requirei to msintain e
u.elociE difltencc ol 1 cmlsec hetreeen tpo patal-
lel byers, 1 cm apart and each hzving an irea oy
I sq.cm
 Neqt Course Chem istrg
2144

its
:,lri l. Surfactalts. Soaps aod delergents which when added to water dcreas
'surfxctants' (surfacc activc cqcl'ls)
liouton'sRule.Forliquidswhicharenoo-assoc'Jledarldwhichdonothavetoohighboiliogpoints'theratio
of rhe heat ofvaporisation (o lhe boiling point is approximately
88JK-l ie
?-tt.I*-'
Guldberg's Rule. The boiling point of a liquid is nearly
two{hird of its critical temperaturc when both are

expressed on absolute scale Le. t o = trT

"

The reciprocalof the coefficieDt ofvlscosity of a liquid is called its fluidity e O=;
'
the effect of temperature on
Effcct of teEperature on surface tension (Eotvos equation)' Quantitatively'
surface tension (z) is given by Eotvos equation, viz

,=uu,_Dlk)r,,
temperature of the liquid '/< is a constant aDd I $
where p is density, M is molecular mass and;c is the critical
the temperature at which measurement is made'
: temprature' surfac tension of the hquid is zero Ai
Thus, when I = lc, / 0 This means that at the crltical
vapour disappears'
this point, the meniscus btween the liquid and the
The coefficient of viscosity of a liquid varies with
it*t 6 Elfect of temPerature or viscosity (Arrhenius equation)'
temperature acaording to the cquation 1 = A cEo/RT
-
called aoi'/adon energl for viscous flotn''
where A and Ea are constants for the Siven liquid and E, is

2.17. Classilication of Solids

SDC"TION_III
TIIE SOLTD STAIE The various solids are classified into the fol-
lowins two tvpes :
[fl Crvsiaffine solirts. All solid elements and
compounds
Am (2) glass, Pitch,
fused silica, r mass etc'
Points CrYstallin
solid and an AmorPhous solid.

(,) Risidity
(ii) A defrnite shape and a definite volume
(rii) IncomPressibilitY
(iv) Poor diffusability through them
(v) No fluiditY
 STATES OF MATTEB
2145

(rr) Melting points. The cr)ttalline substances

possess sharp melting points whereas the amorphous
substances melt gadually over a temperature ;ange.
(ii, Isotropy and Arisotropy, In case of anor-
phous substances, properties like electrical conduc-
tivity, etc. are
identi
riquid ffX,f
.O. a
O.o o
a

o a o
a o
a o
FIG
o I
ergoes
o o a

,.o.O
FIGUBE 2.35. Anisortopy o(hibired by Thus thc main points of diffcrence bctwecn a
crystalline substances. crystallinc solid and an amorphous solid may be
summcd up as follows :

(r) The coDstituenr parricles are arraDged in a rcgular (, Thc constituent particlcs are not arraDged iD aDy
fashion containing short range aswellas long ringe regular fashion ; there may be at the mostsomeshort
order. range ordcr only.
() They have sharp metriDg poinrs. (!r) They mslt ovcr a range of temperature.
(iii) They are anisotropic. (iii) They arc isotropic.
(iv) They uDdergo a clcan cleavagc. (-) They uDdergo an irregular cut.

In fact, only lhe crystalline solids are the true

solids wbereas arr orphous solid.s are considered to

Further it may be pointed out that due to short

range order possessed by amorphous solidg small
 Pratl.t:1t's Neut Coutsc C6"m iStrgSfrlD
2146

TARLL 2.3. Classiiication of crystulline solids into difterent tJpes

s. CRYSTAL CONSIITUENT MAIN BINDING PROPERTIES EXAMPLES

No. TYPE PARTICLES I'ORCES
1. Ionic Positive and nega- StroDg electrostatlc Brittle, high m.p., Sood con- Salts like NaCl,
tive ioDs arrangcd iD forces of attraction ductors in the aqueoussolu- KN03, LiE BaSOa
a definite order tion or fused siate, hiSh BaO, CaF2 etc.
heats of tusion

Molecular Small molecules van der Waal's for- Soft, lo$,r m.p., volatile, Solid CO2 (dry ict),
ces electrical insulators, Poor CHa, wax, iodine, ice,
thermal conductors, lor (Ss),
sulphur Phos-
heats of fusion
phorus (P1).

C-ovalent Aloms chemicaltY Covalent bond for- Very hard, tligh m.P., Poor Diamond, silicon
bound bgether in ces co[ductors of heat and carbide, silica, quartz.
the form of a net- electricity, high heats of
work fusion

4. Metallic Positive ions and Electrical attrac- All metals and some al-
mobile electrons tions (melallic loys-
bond)

iti:, l. Ionic solids do not conduct electricity in the solid state as ions are Dot free to move'
just a cluster (aggregate) of ions
Ionic solid is a rhree dimensional arrangement of cations and anions. It is
which on the whole is electrically neutral

Na+ lon

ion

FIGLJRE 2'37. Clustering of iorls to form an ionic solid, Iike NaCI

.lAcovalentsolidiSagiaDtmoleculehavingathrcedimeDsionalneiworkofcovalcntbondse'&struciureof
diamond is shoPn iD Fi8. 2.38 on the nexl page'
]Thevalenceclectronsofametalatomarcfreeelectrons(asiorceofaractiononthcmbythenucleusis
minimum;. Leuuing valence elecirons, the remaining portion isa Positve i n,called "kernel"'
The free mobile
electrons hold the kernels together.
The simultaneous airaction betweenthe ktmeb aml the mobile clectrons
,rhich hold the kernels logether c called
metallic bond.
STATES OF MATTER
2147

(FREE/

o"- o"- o"- o"- o MOBTLE)

ELECTRON

o"- o"- oe- oe- oe- KE RNEL

o"- o"- o- o"-

FIGUBE 2.39. Electron sea model ol
FIGUBE 2.38. Stnrcture of diamond metallic bond

Thus metgllic bond spreads over the whole crystal aod is Don- directional. Tbis model is called,,electron
sea
model" (Fig.2.39)
. 'Ihc order of melting poinrs ofdifferent rypes
of cr)dalline solids is as fouolrr:
Co!r'aleot > Ionrc > Metalic > Molecular
(_ 4000 K) (_ l0o0 K) (ss0-1000 K) (273-600 K)

''lf]emeltingPointofasubstancrs-ameasureofthemagnitudeofthebindiDgforceamonglheconstitucnt
particles. For example,
are given blo\r,
tbe order of melting points and hance that of lhc binding force for i few rrurt"n"",
:

oz <Nz < qHsoH < H2O < C6H6 < Na < NaCl
M.prs.(K) 55 63 l5e 273 21A 3'11 10'17
(__--.y-----J
t---____J
Molccular crvstflls Mcrallic Ionic

ual ,ue?tion?
(? | Airange solid, liquid and gas in
order of c,lerBi giving rcasoDs
Ans solid < Uquld < Gas. This is because a solid absorbs enerry ro chaoge iDro a liquid which furrher absorbs
enerry to change into a gas.
(l l ' A eas is lilled into a bulb connected to an opD
limb marometer. The diIlercnce irl the levels ofthe two limbs
is 2 1 cm. The atmospheric prcssure is 740 mm. What is the pressure
of the gas ?
Ans. 740 2l = 719 mm.
lJ t How-do you convert
(a) pressure in atmospheres into SI uDits ?
(6) tcmperature in oC to temperature in .F ?
Ans.
1a; 1 atm = 101, 325 pa or Nm -2 or I bar = ld pa
(r).c=;cF-32)
{J I What tyae of graph r+ill you get rvhen ryis plotted lgainst p
at co[statrt temperature.
Ans. A srraight line parallel ro pressure ards.
Q -i Hoy is the pressure ofa gss related to its density at s particular
temperstur ?
,MP
Ans. 4 =
RT
 Ncu,r Course Chem istrtl
a 8as iD a hixture relat'd to the total pressure of thc Etrseous mi'cur ?
Q. 6. How is the partial pressure of
'Ibtal Pressure'
An$ Partial prcssure ofa gas = Mole fraclion of that gas x
speed ond root Inean square sped on
Represent the rclative values of most probable sPed, avcrage
M;xweu's distribution curve for sPecd$
Ans. Refer to fig. 2.15 (b) Page 2D6.
ofa gas
1. r lvhat is the relationship bet*een svcrsge kinetic ener-A/ and the temPerature
?

nns. ffi = I tf where k is Boltzmann ."nu'"' =

lfr I
and 'h"! (N'C'E'R'T)
'.) 'j what is the significance ofthd van derWaal's co'nstanLs 'a'
,{ns.'4'isamcasureofthemagnitudeofthcintermolccularforccsolattractionwhileDisameasureoftheeffective
size of the 8as molecules.
is alwnys greeter than I and increases with
,.r lo Why in case ofhydrogen and helium' the comPresibility factor
increase of Pressure ?
and Hc' pagc 2/B 1'
Ans. Refer t^ 'Explanation of exceptional behaviou r of H2
i I ri The van der Waal's corstants for trdo Snscs ore as follows
:-
cas o (otm L2 mol-2) b (L E ol-1)
x 139 0 0391
y 359 o.M27
size ?
Whicl! o[them is more easily liqueliable aEd which has greoter molecular
gas is llqucfiablesimilatly' Srcatcr the value of '0"
greater is thc
'--' Greater lhe value of 'a', more easity the
Ans.
;;i;;i";;r". Hence gis y will grearer molecular
be more ;asily liquefiable and wllt havesize.

a5UF, 238UFa'
r-) rt Compare the rates ofdiffusion of "nd
Ans. Molecular massof E5UF6 =235+6x19=349

Molecutar ma;s of
ts8uF =239+6' 19=352

=,oon
H",ffi=ff=l/$
Thus r 1B5IJF51 :r1!8uFr; = t
ooltt'
rrr'Ataccrtainaltitude,thedensiBofairisl/lothofthedcnsityoftheearth'sstmosphereandtemperature
'.
;;:i;eil;;i"',il pr*"r;; it it orri,ua.r ,r"u.e rh;r air behrves like an ideal sas, hos urifo.tr
comPosition lrnd is at S.T.[ at the eerth's surface'

P,! .
tr=u, ttul,L.
o. ,. = lt Vz
""
,rn*. -f
T,
. P. Tz r"o , zor l-!,] z:
llfrrd. +.uencc Pz- -Tr [dz) - -- i- tr0r ='J
= z--.
""""'
lTrl-
r.i i l. lvhflt\ ould be the SI unit ror thl qrlantitypv2T2 'a ? <N'C'E'R'T')

tu" t*._1qL]-6f.
= Nm4 Kz mol-r
_273.C is the lowest temPemture. (,|[c.E.R.r)
, ) !iIn terms ot charles' law explain why
Ans. At volumc of the gas becomes equal to -cro i c the gas ceases to exist'
-273"C, stronger
(-) tr, Critical temperature for CO2 and CIla are 31 l'Card-tl 9PC respectiYely' Which of these has
(N'C'E'R'T).
intcrmolecular forces and lYhy ?
bc liqucficd-iJ glcatcr arc thc intcrmolecular forcas
-"'
'Ans, Highcr
lhc crilical temPcrature n)orc easlly lhc tcs c.1n
cb, has stronger intermolecr lar forcs than cHl'
oiiiiir",ion rrence
STATES OF I\,4ATTEB
2149
Q. I7. What is the ratio of average kinetic ener5/ oforygen rnolecules to that ofozotre molecules.t 27oC ?
Ans" Avrage kinetic erlerry of any 8as depends olly on temperarure aDd
not upon the nature of rhe gas. Hence
botb the tases will have same average kine tic erlerg aL ;.1.C i.e. the r rtio wlll
be 1 : I.
Q' lE what is thc dillcrene hctneeo toa.I tiretic eaergr and tratrslatioual kiletic energr ? For r,hat t!,pc of
]tlole(ulq the two orc equsl ?
Ars. al kineuc eDertics. The total kinetic
(He, Ne etc.) as they do not possqss

Q. l9.Out of N, End NH3, rrhlch orc rvill have grraaer volue of.a' ardrhich ore rvill hove greater r.alue of.b, ?
ADs' (0 As NH3 is more easily liquefiable (due to hydrogen bonding), itrtermotecular
forces of attracdon are
stronger than in N2. Hence NH3 will have greater\ralue for ,4,.
(ir) As NH3 molecule is larger in size thaD N2, henc NH3 will have greter
value for ,r,.
(For NH3, a = 4.lz L2 atln mol-z, D = 0.0371 L mot-r
For Nr, a - 1.39 L2 arm mot-2, b = 0.0319 L mol-l)
Q loyyhot f,ould hrve happered to the gas if the Eolecuhr colisiotrs r.re [ot erastic ?
Ar& On evry collision, there would hav been lo0s of enerry. As a result, the molecules would
have slowed Jown
and ultimately settle down in the vessel.
Q. 2 cor ls hcsvrcrthsr 02 rId N' goaes pEsertrn the air but itdoes Dotforo the rowerraycrofthc etmGphere.
Vihy ?
ADs' Gsses possess theproPeny ofdiffiJsion.which is indepeDdeni ofthe
force ofgmvitarion. Due ro diffusion, rhe
gases mix into cach other and remain almost uDiformly
distributed in the atlisphere.
Q 2'{ro ond co2 have ahc saEG rrt ofdifiusioD u,der ss,e coBditio,s ortEperature ond prcssur. why ?
Ahs. l- r). According to Graham,s law of diflusiotr, rates of diffusion of
to the square root of their molar masses under same conditions
of
Q. 2why llquids bsvG a ditroltc voluoc but m dc0rite shepe ?
Ans' This is because the intermorecurar forces arc_stroDt enough to bord
rhe molerules totether but not so
strong as to fix them into delinire posirions (as in iotids)llnstead,
they possss nriaity uro-t oo
definite shap. "o..
(J. 2At I portlculsr temFraturc, tf,hy
vslrour p'r6aurc ofocrioDc ls tcss thsr that olether ?
ADs' This becausc the intermoreruarr forces ofattraction m acetoDe are stronger
i6
than rh* preseot in ether.
Q 2f, rrqurd rs tra[sfcEed fro, o sDalrer v.sscr to o biggcr vcsser at the sar,G temlErature. whet
clfcct on the vapour pressure ? wiu be thc
AD& No effect as it depends only on the naturc of the liquid and
Emperature.
Q. y yegetsbles sre cokd rvith dimculty ot a hill stotion ?
A.trs. The atomopheric pressure is less and so ihe boiling point
is lo$red.
Q. y'tst
ls thc opproxi,atc rclotiotrahip betveer heat ofvoporisatiotr
aod boilitrg poi.,t ofs llquid ?
AD& A Hvsp. / Tb = 2l calK-l mol-l (frouton's rule).

Q at is the ellcct oltcEpcrrturc or

(.) SErfacr aeDsioE and (i0 Vlscosity ?
Ans. Bo{-b decreasc with increase of teEperaturc.
a- lalllng llquid drop are ephcrlcal ?
ADs' This is due to proPerty of surfac tension possessd by the
liquids. This makes the surface area minimum. For
a given volume, spherc has the minimum surfa@ area.
(,).Vlbst hrppeDs ifa tiquld is
hc{ted to the critical &El,erature ol lts vspours ?
Atrs. The meniscrs beteeen tbe liquid aDd Ue lrapour disappears
(surface teosion of the lhuid becomes zero).
2150
l' r a el c c p' s,t Ne t t 1;o' 7'xgs' :,:

Ch a m i sl tqi:@
(-). r I . Why liquids diffuse slowly as compared to gases?
Ans. In liquids, the molecules are less free than in a gas r.e. the intermolecular forces (van der waal's forces) in a

liquid are greater than in a gas.

liquids ?
J. -r2. Why amorphous solids are considered to be supercooled

Ans. (i) Like liquids, amorphous solids are isotropic

(ii) Like liquids, they possess/uidiry.
(,). .1-1. Why urea has a sharp melting point but glass does not ?
sharp melting points whereas
Ans. Urea is a crystalline solid whereas glass is amorphous. Crystatline solids have
amorphous solids do not possess sharp melting point'

CARRYING 1 MARK

Q.l.Whichstateofmatterhasadefinitevolumebutnodefiniteshape?
Ans Liquid.
Q. 2 . What is the equation of state of an ideal gas for z moles ?

Ans. PV = nRT
(). -1. What is the value of the gas constant in S'I' units?
Ans. 8'314JK-l mol-l'
Q J. What is compressibility factor ?

Ans. ,_PY
"-nRT
Q. _r. What is the equation of state for real gases ?

Ans. van der wbal equation, (t * (v--J) = RT

# )
the top of a mountain than at sea level ?
Q.6. why a liquid boils at a lower temperature at
Ans. This is because the pressure at the toP of a mountain is low'
Q.7. What are the S.I. units of surface tension ?
Ans Nm-1.
Q. n. What are the units of coeflicient of
viscosity ?

fuis Poise.
Q. e. vtrhat is sI unit of coeflicient of viscosity ? How is it related to poise ?

Ans SIunit=kgm's
-1 -1 ^

Poise=1gcm'.s'
-r -1

.'. 1 poise = #tn of SI unit.

;r i ,\ Why ice has a sharp melting point whereas glass melts over a range of temperature
? (N'C'E'R'T)

Ans Ice is a crystalline solid whereas glass is an amorphous solid'

r.' ! . What is the binding force between molecules, if a substance is a gas under ordinary-conditions of
temperature and pressure ? 1990) @'I'T Ranchi

Ans. van der Waal's forces

 STATES OF MATTEB
2ls1

5 A CARRYING 2 oT3 MARKS

Sec.2.l. What is the difference btween a baromerer and a maDomelcr ?
to 2.3.
On thc basis of intermolecular forcs and therrDal enerry, explaiD why
(r) a solid has rigidiry but liquids do not have rigrdity ?
(
) gases have high compressibility but tiquids and solids have poor mmpressibility ?
I
How is the pressure of a gas measured ?
Scc.2.4 4. Dcline Boyle's law. How is it represented mathemadcally ?
( What tlTre ofcurves are obtained when at constant temperature we
plot
P vs 1Al (,i) PV !s P (tu) v ir p
(l)
6. On the basis of Boyle's law explaiD why mountaineers carry orygeD
rylindeA with them.
DefiDe Charles'law. Give its mathematical formulae.
6. Defioe Absolute zero. Can this temperature be attaiDed in actual practice
? Give reason for your
answet.
9. Derive the value ofgas constant in S.I. units.
10. Definc Dalron's law of partial pressures. Using rhis law, hoB, is the pressure of dry gas determmed ?
11. Define Graham's law of ddfusion.
12, tweco pressurc, temperaturc and density ofa gas (re. M d RT/p).
Sec.2.5. 13. =
les ot kinelic lheory of gascs.
Scc.2.6. 14. ed, average speed;nd root mean square speed. Ho\f, are they related
to
to 2,t.
15. Write kine c gas equatioD. Ho\y does Boyle,s law follo\x from rt ?
16. Write kinetic gas equation. How does Charles, law fouow from it ?
Scc.2.9. ,, .!1r.1, or*" rhat rhe averase kineric encrsy of a
to 2.10- Ilonal Io l::ili:11..!T
:::.:iic^ tts absolute lempcrature. sas is direcrry propor.

1t' what is 'compressibility factor' ? what is its value for 'an ideal gas'
? How does it herp to understand
the extent ofdeviatioD ofa gas from ideal behaviour?
19. Why do rcal gases show deviation Irom ideal behaviour ? Wtite
van der Whal,s equation for ,, moles
ofa gas.
20. What are the unib of van der Waal,s constants ,4, and 6, ? What is rheir significance
?
Scc 2.1I 21' Why is rhe effect of temprature more important for trre ritueraction gases of ? Define critical
temperature and critical pressurg.
22. Detine Joute-Thomson effed- Why hydrogen and helium show
exceptioDal behaviour ?
23' Brietly descrjbe the rmportancr of criticar temperature. How
can it be correrared withvan dcr wbals
constant a' I
Sec.2.l,l. 24' Exprarn thc statemenl 'Llouid srate is intermediate between .he gaseous ,
state and thc solid statc
Io 2.15. 25.
26. Give reasons for lhe following:_
(i) Liquids have a definite volume bur no definite shape.
(ii) Liquids have higber density rhan gases.
(iii) Liquids are much less compressible ttlan gases.
(rv) Liquids possess fluidity.
27. DefiDe vapour pressure, boiliDg
[rcint and heat ofvaporisanon.
2t. What is differeDce beNeen BoiliDg aDd Evaporarion ?
29. Explain rhe effect of temperature on the follo ing:
(i) Surface rcnsion (,f) Viscosity
tiii) Vapour pressure (iv) Dcnsity
30. cive reasons for the following:
 Pradeep's

(i) Boiling point of a liquid rises on increasiog Pressure'

(ii) Drops of a liquid assume a sphlrical shaPe'
tube is
lrif me t*et ot m"rcury in a capillary tube is lower than the level outside when a capillary
ioserted in mercury-
it is qui* hot.
Sec.2.16. 31.
Scc.2.17. 32. solid 8Dd an amorPhous solid.
Scc.2.lE. 33. nt ryPes, Eiving reasons for your answer :

dry ice), BaSOa

and a 8as'
Sec.2,l. 1. List the main points of differencr between a solid, a liquid
explain why substances exist in ihre
Sec.2.2. i: il;; ffi;i iltermolecular forces ancl thermal energr,
different states.
Sec. 2.3" 3, How are the following measured ?
(i) atmospheric pressure (ri) pressure ofa 8as'
of this law
Scc.2.4. + 5ir" Boylct lii. How is the lai verifred graphicaly ? what is the sigoincanc
b the""o'*pr"lit
mountaineers?
zcro' ? How is this law
5. State aDd exPlain Charles'law. Hotr'does it lead !o tbe coocePt of'absolute
made use ofln the meteorological observations ?

6. Briefly explain Pressure-'IEmPcraturc law'

terms of density of the gas'
7. What is ideal 8as equation ? Hot^' can it be derived? Also sPress it in
t. Discuss the nature of the 8as mnstant 'R' Derive its Yalue in terms of different units' of
9. State and explain Daltol's law of Partial Presslres' How is this law apPlied in the delermination
presure of dry gas from that of tbe moist gas ?
10. Define Grabam's latY of diffusion. Give iE mathematicalformulation'
iVtrui u." rft" itp"rtant postulates of kinetic moleqrlar theory of
gases ?
Sec.2,5. 11. 1rj
iaj Wirc fin"tic gat equation. what do different symbols signify ?
or Brieflv exDlain the Dynamic Panicle Model or the Microsc'Pic model of a 8as'
i(. 2.6. 12, 1r; fr*ite a sfio.t note o; 'Mar$rell's distribution of
sPeds"
are thsy related
iaj O"no" p,ouable sPeed, aYerage sPeed and root mean square sped' How
,*t
to each other ?
Write kinetic I,as equation. Deduc follo\triog gas lav's tiom-it
:
Sec.2,1. 13.
-
to 2.t. ,,,, n^a-,"
(i) Boyle's r",,1
lari;;;\
(ii) ahrrles'law
charles'law (iii)
(t,0 Dalton's law of pa
partialPressures.
postulates' explain the
ra. i,rt portrtrtes ofKinetic-motecular theoryofgases On the basis ofthese
tf,"
following 8as laes:
(i) Boytc's law (ii) Charles' law (iit) Dalton's taw of Partial pressures
Scc.2.9. rS. Siirrln! frorn rinetic gas equation, derivi a'relatronship between average kinetic energy and absolute
tcmDralure o[ a gas
what is compressibiliry factor ? How does it helP in understanding
Sec.2,l0, t6. d[;;"-i;;i;tiJieal gases ?
thc deviation of real gases from ideal behaviour ?
gases (vaD der
17. why do rcal gases dcviatc from ideal behaviour ? Write the equation of state for real
Waal's equation).
of rcal gases undcr different conditions
lE. Starring from van der waal's equation cxplain, the bebaviour
of temperaiure and pressure-
behaviour of hydrogen and helium ?
19. How can van dcr Whal's equation explain the exceptional
sec 2.1I ,0. Briefly exptain Linde's ptocess for liquefaction ofgases'
to 2.13.
21. Briefly explain Claude's process for liquefac on of gases'
 STATES OF i,4ATTEH
2ls3
Sec.2.l4. 22. What are the main postula Kinetic Molecular Th"orym
to 2.15. ho$, can you qplain the fol properries of liquids ?
0) volume (ii) Density (rii) Compressibjliry (iv) Diffusion.
tie tetm 'lapour Pressure". what are the facrors on which rhc vapour pressure of a
" ill:li:flf[
u. teosioo ? What are irs unirs ? What is rhe effecr of remperature on surfa@
ITr:lfr*U"*
25. Define ,coefficieot ofviscosity,. What are its units
? What is the
ry of a tiquid ?
Sec,2.16. 26. cs ofsolids ? How do amorphous solids differ from crysta[ine
to 2.17.
Sec.2.l8. 27, Based upon the nature of the ccnstitutent particles
and tbe binding forces between them, ho are
the cr)Gtalline solids classified inro diff(lrent
ryPes ? Give thc important properfies and examples of
"uch
ryo".

t-

rl

I
 can:l?ltt:1"-1"-*lated to van der
iD terEs of Yan der Waal's corstatrts' The
1, Criticxl constants
uhal,s constants by the following efPressioN
Pc=4/2jtb2,.fc=8a/21Rb,Y,=3b.

they are related to each other as

PJ" = 3 RTc.
Funhr,
can be calollated' using the above
exPrs$ons'
Altunotivety,Baingcrithal corBtants' \ran der lvaal's coDstants
colstatrts f'=#-' Tt=fu
2. Boyle trEll. aEd crittcsl iGEP' iD terEs of vrn der waal's

Thus TB > Tc

r,=?1
nthemole$lesofaSascomeclostoeachother,astage@meswhenthe
when thev are clGest to e,ch
reDu di:il;;;;;-J;ntres of rhe molecules
diameter (o)'
tars uetween ttrem is called molecular
Li#

molecules

2lg
STATES OF MATTER
215s
ADDITIONAL UgEFUL INFORMATION

7. Expressions forcollisioh number (NC) and collision

frequercy (Z) Nc=.lZrrJn
wherer = average speed, o= molecular diameter
and ,| = no. of mole;ules/cc of the gas
C-ollisions among all the molecules
= Nc x ,
Na! n ,=
ru
As uoLx
each wxrlruD
collisioD rtwoNes trc molecules,
involves rl*! z _:i_
.v) ==_i n^ u;2
";,,n2
puuiDs ,=\F z 2,.n2#
increase in remperarure, o increases and with
*."r,)",rr""::::J,O increase in pressure n increases. So in borh
t'
Mean frEe patb. The distance travellei bya
molecule between arry rwo successive collisions
i$ called free
path. The average of rhes distaDces i5 calted + h +_\ + .....
rhe mean free par n I =lt
,
Marhemaricafly, ir is given by T =
G:Fn
where o = molecular diameter,
N= number of molccules of the tas per unrt
volume
Butforn molesofan ideal gas, .<=- 13 I
PV=}?RT ------J
or number of moles per unit volume, FIGL.,BE 2.41. Free paths.
$=ift
. . Number of molecutes per unit votume
= ff
Putring N = pNo,/RT, rbe above equarioD
becomes '
I= .-1_'
./r;aNRT

Thus 7. T and e 1,/p

9. IrgarithEic plots for Boyle,s law aDd Charles, law.
law,
According to Boyle,s pV
= mnshnt
... logp+logV=sonskrl or log p =_logV+ constant
Hence the plot of log p vs log V is as shonr
itmg. ZlO.

FIGURE 2.42. plor of log p rs log V. FICI.JRE 2.a3. iot of log V vs log T
Acrording ro Charles'taw,
{ =
"onr,.
Iog.V-log T = cqns1. s1 v = tog I. + consr.
-- plor of log V vs log
Hence
log
T will be as shown in Fig. 2.43.
 Pradeep's

I lrrs rdw D rr rnsr

volumes' rhi'
10. Amagat's raw partial vorumes'
law of partiar
of
11. "- :t*i:
i: P:':",,* :?Y#.q:l'lilffi"H'.: fffyJ:il:
tneii partiai votumes uhere Partial
rhis r"*,'"G;".;;i;ume of a mmure .""." i!1"11s^9Tl l'-*lll1.?1,^n and at ,n" ,
Dressure of
the pressure or the mnure.
rhe mixture."
i:i[:tJ[f13il:';#,","iffiT:[ dii"ie",;;?L,",emperature
Mathematically
VI=ul+tZ+D3+
trrixture'
ll. Average molecular mais of a gsseous
:,t M,
M-,=_r?=>,,Mr
M, is the molecular mass of comPonent
i (ri is mole ftaction of the
where lri is the number of moles and
comp heatins melt to 8'ive a turbid (milky)

riquid
is fou
il'"*";:'ff:"'Hi#:u1iJ:liH":
the
"*tull. *.u"u"".c.t called strlcmomcte. It is based uPon
of surface tension' The aPparatus usd. is falling from
orinciDle ihat rhe surrac" t.nsron oru iiiiii'ir
li,:"iii,ii"p".ional the mass Jf the spherical drop
to
(\ / h = mr / m2)
t4
I *piiru.y trbc

princiPle
rr"ro
'ertically
3"##il#J:ff:'H:ffilJ5i"x[
eir times of flow.
ofa liquidwith temperature The
" '1i"r.*ro"'"hPeyron equotiotr' It gives the variation ofvaPour Pressure
equatioD is

r.8p;
P,, ^IL rT2
- Tr)
= t.msE
I-TE-J
where aHr = enthalpy ofvaporisation of the liquid

flying at high altitude rs due to the solidificalion ,o.f

ic-e whictr is slowly reconverted
olrectry
rocryitallin;
 STATES OF MATTER
2ls7

c.B.s. E.- P. ',T, ({tiAlrys spEctAt"

A. SABJECTIW SUESTIONS (r,
e t. Prove that the excluded volumc.br ls four times ave
the
the actual volume of the gas Eolecules.
Ars, CoDsider two molecules fast
A and.B. Tbking the
molecules to be spherical, ifr is tbe radius oif the not kept Iow
molecules, then the distanc of closest approach pcrature, the
bet$Een the two molecutes = z r (as siriryn in the tyre may
Fi9.2.44).
e. .1. cive reason for the following :
(i) Sodium rDetal Is soft with low meltillg poiDt
whereas sodium chloride ls hard lrlth hig-h melt-

o
iDg poina.
(ii) Ditrmond has a yery high Eelting poinL
(iii) Copper is mallesble and ducdle but brass
is hard and briatle-

I
lz,

0i) DiamoDd is a coEleDt solid and is a giant

moleculc with three dimeDsiooal networ-k of
c{'valent bonds, Hence it has very high melting
Point.

e. 2. Draw the plot of

(i) Irg P vs Log V at constatrt tcEperature. Q.5. sh@that
(ii) Log V vs Log T at coDstant prcssure o gas ls
Atr& Refer io point 9, pag" Z|SS.
q, .r. Glve o rcacons for lte folloeila I (NC.E.R.T.)
ADs. Refer to page 2/13.
(i) The size of lratltr bolloon becotn.s
latger-ard larger os it asccnds into Hgh;;
altitudes.
(ii) lyrs of sutoEoblls arc lDnetcd to lesser
pressure lD aumEer thsr itr wlntcr.
 Ne.at Course
2lsa
Arronge the follo*ing in ordcr of iDcrcasinB --1.
=Rr
r /. ,)l
density, r+vr_Ef)l
the given form of the equation'
witi
Comparing
OxyBctr 8t 25'g 1 8tm ; OxyBen st ()"g 2 otm ;
Oxygn at 273'C' I atm B =D -R+
(LI.LN'R Albhahod 1992 )
l' l| For a real gas obeying von der Waal's equation'
Ans. d,+ and V=+ a graph is-plotted between
(x-axis) where
PV. (y-axis) and P
Vi is the Inolar volume' Find
V for 02 at 25'C, 1 atm (t.r.T 2oo4
y-interccpt of the graPh.
a *rrr, ,r, * For a real gas, the plot of Pv,l !s P caD be of the
= =
0
tvDe A or B but at the Point of intercPt, P =
v for oz at trC, 2 atm a'rio at any lolv presure'van der rJ*dal's equation

* * reducEs to ideal gas equation

= 1'' = ,ru.r
V for 02 at 273'C, 1 atm

=R'146=l+6R
Hence increasint order of dcnsity will be 02
at

273'C, I atfi; O, at 25'C, 1 atm; 02 at 0'C' 2

atm.
Q s Wby dry oir is heavier thrn Eoist oir ?
Ars. Average mol. mass of dry air
of Nzx?8 + % of Ozx 32 P
=- FTGURE 2.45.
Average mol. mass of moist air
otH2o:r18 PV=nRT or Pv,,, = RT
% of N2t+Eo ofo2x32+%
Henc y-intercept of graPh will be= RT
more () ll On which factors will the rate of diffusion of a
Evidentlv average mol. mass of dry air is ' fas rlepena t (Wet Beagalt E'E' 20041
and so iiits = M '/ v)'
dcnsity (l
(l I Oncrvay ofwriting the equatio! otstate for
rsl A-ns. Rate of diffusioD of a 8as dePends upon
Srscs is (i) density or molecular mass ofthe gas
(ii) pressure ofthe gas
(iii) temPerature of the gas

At consknt temPerature, t"f xfi'

B I' RO ltl.Lll\
An& Acmrding to van der \lhal's equation

l**4)
v'l rv-al
' =nr
\
- -RTa
v=y-:g- yZ

. rv=H-' fore, on" rolggglg = f "3

=lr!oso,. ro-rocmf
or rv=rr[/ -i;J
A\ '
-v = I .41 x to-B cm3
/ b\ a To camLte the emPty spac in 1 mole
of 02
=Rr
[
+V] -v e the volume occuPied bY 1

(Neglecting higher Po$ers of bfr') x lF molcclles' This will

t h a) x lo-a
+ PV=Rr l\, *V-gAfJ cul3) = E'49
"m3'
 STATES OF MATTER
2ls9
But volume occupied by I mole of molecules at . . Numbr of moles of 02 requircd to be rElessed
S.TP = 22400 cm3
. Empty space .49 cmJ =5-0.98=4.O2mol
.
= z24oo - E
or Mass of 02 required to be relcascd
= 22391 .S1 cm3
. gl,a$e of empty s!El(x,,
.
=4 02x32t=t2t.G1c
=
rrlrk;ir, too
= ee.e6*. 6. gt lih. ofdry N2 ir posscd rhmugh 36
S
HuO After thc porsogc ol thc 8r!, tL ErEs ol
__. _-t\fihn l. Thc hoilinS poiDt ol D_hcxrtre ls
*T rrdu.rd 1.&l & Crtculrrc rhc rqu.ous
6t 9"c. C{lculatr ,ts oppmximete criUca t"rp."rar.. :l!..
I -q
tDsioD ofyaaer oa 2fC
According to Guldbergk rule, for a liq_
V,hter carried a}?y by N2
uid ldLeter"-3rf,=|Ga.s * ztt;r gas
=36-34.80=1.208
= 512.85 K = 512.a5 _ Z7i"C As this water is carried aq/ay by 50 L of N2 gas,
this
= 239.rS.C. means that \rolume occupied by water \rapours
Thus nos, we bave = 50 L
I nthlen .t,ltsomlngcozto bcvrD d.rvlhol,s goE,
crlculstc lts Boylc t Epcrsturc. Givcn , = 1#=o.mozmol, v=
a = 3.59 L2 etm mol -2 arrd b = O.M27 L mol-r.
sol-, T = 3m rg
P=?
Bryle temperature iD terms of yaD der Applyitrg the ga3 equation, pV ,' RT
=
al's constanLs is TB = ffence
Ofo-. o_zRT
3 59 !2 atm-mot-2
Ts =(0 0821 _ 0 .0667 Eot x O.O82t LO.tm K- 1 mol-l x 300 K
L atm K- I mot-t) (0.U27 L mol-r)
= 1024 K.
= 0.03216atm = o.o32t6 x 760 mIn
= 2a.97 E,rn.
_-_ I'nhtun A 5-L v.f,scl contslDr I .4 g of nltrogcr.
7.
When heatcd to l6{Xt K, 30% ol mole,c;k!
crc ;b-
socjstcd iDto otoDr. C{lcl|lata thc prcrauE
of th. ga!
ar l600IC
Sotqdgu. l0Lat 200 atm Lar 1atm (rrmFEra_
= ?
N2
ture remaining consknt) 2N
P1 V1 =P2V2 Initial motes #,/n o
200x 10=1xV2 or yz=ML
Number of breaths = 0.05
Total volumc Moles afrer O.O5-ffix0.05 2x0.015
vorunc contumcd pcr brrath
2000 r- disso. -o ot5
=0.0S
= _-__::- -.*_ = 1t' a; = 0.030
= 0.035
... lbral number of moles
= 0.035 + 0.030
= 0.065
r?. a = 0.065 mol, V 5 L,
mber of moles of cygeD gas presnt =
T=1800KP=?
initial er= l6ot
-=smoles Applying PV = a RT we qer
mot-l 32 g
D- aRT
(Molar mass of Oz = 32gmol-l) ' --v-
Tb clc{rlate the Dumber of moles Dow presEot, wE hirve _ 0.665 mot x 0.0821 Latm K-l mol-1 x 1600K
P= l.2auD, T = 298K, V = 20.OL
Applying thc rclationr pV a pX *" 1r"r.
= = I .92.lm
7 2atmx20 0L agacundcr
cotrstatrt volumc ot
=0 9Emol -100.c
 Pradeep's
2160

creas
lume gxPansMty of a 8as means ln-
in volune per degree rise or fall in or 35
zg=
,1-+.
temPerature of its volumL rt0"C
,,. '2
V,=Vo+0 0037 xVox' or Mo.=?lx
lfi,) =4t 7't'
=vo(1 +0 00370 ch will dilfuse faster' ammonia or
Coz? relative rntes ofdilTusion ?
At 100'c,
x (BITRL'tchi1989)
V166'6=V6(1 +0 0037 100)
Mcoz = 44'
= 685 cm3 (Gi!en) NH3 = 17',

or vo = ,615, =
soo
"'3 .r. , . ' { fr , hence NH3 will dilfuse faster
At
-100'C, x (-
V-100'c = 500 [1 +
= 315 cm3
O 0O3? 100)l
'n*,-!E = \[4 =,.oon
Eo]-' MnH, ' tt
I'rorl. ,, 9 Calculate the temPeroture at which at 27oC is heste'l utrtil
Zt g oi N, t"itt o"""Py a volume of lo o litres et
2 46 nrrrt t"* I S -l,' op,en
"ess'l
atmosphere. (M L'N'R' All*luhad 19E7)

28 g N, = 1 mole of N2-

APPly'og PV=nRf
2'46 x 1O = 1x0 0821 x T- This gives
'l = 299 6K the vessel is oPen, Pressure and
volu staot. Thus ifnl moles are present ar
t,l)tot' 10. AtlE"C and 765 torr' I 299 L ofa
gas
moles are Present at T2, we can write
t,t 'l't
*.lnrr" liii e. cnl.ulate the sPProximste moleculEr and ,12

."ii-i .i,r," g"" <I's'M' Dhanbad 1987) PV=n,RT1 ; PV =nrRT,

solution' Pl = 765 torr'v' = 1 299L'Tr=zglK
Hence rl RTr = nzR'lzot \'f 1 = nzTz
converting to volum" tt M", += +' nt Tz
760 x v2 ot q= .tl
t.2g9 ---fr1-
8et :El-
i6a x.
we = ll
Suppose the no. of moles of air originally Present =
or Vu = 1 226'l L'
, .11 Afler heatinS, no of moles ot air cxPelled = t a

Mass of 22.4LarSTp =ffi"22.4E=4e sI . No of moles lcft after heating

Molar mass = 19 5gmol-t 3i
volutnes of ozone and chlorile
=n -3n= in
altre time sre 35 ml aril 29 ml
lecular weiSht of chlorine is 71' Thus n, = r' T, = 3oo K: rt2 =!n'rr= t
r wcight ol ozoEe'
(B'LT' Rotli 1988) ^TisTz ot
l--=mb 2=360
solution. Applying Graham's law of diftusioo' 5

=tT, =lF, or Tz = 750 K

V
Altemotively,stppce thevolume ofthe
vessel =
o'1/l
;v "i=lY, ie. Volume ofair initially al2'7'C = V

"q Volume of air exPelted = |v

n,
 STATES OF MATTER 2161

. Volume of air lefr at 27.C =

Ca6e (il) Pressure
;v
= 76 cm x 13.6 g / cm3 x 981 :m/.r2
Ho\ryever on heating to T'K it would bcome =V
As pressure remaiDs constant, (vesselbeing open), = 1 013 x cm-2 = I atm.
105 dyDes

vr Yz. 2t5Y v Problan 17.Eor lO aiDutes cach, et 27oC, from

- two idcDtical holeq nltrogen aDd on unkrowtr gas are
T=Ei.fm-K-qorrr=zsox lesked into o commorr vessel of 3 L cEpacity. The
I'robleDt I at is densityofSO2 gas at 27oC and resultiDg precsure ls 4.lE bar and ihc mixture cotr-
2 Etmospheric pressure ? (Al wts. S
taias 0.4 mole ofnitrogen. What is the molar masa
-- 32, O = 16, R = ofthe unknown gss ? (N.C.E.Rr.)
0 0t21 Latm K-l mol-l) (C.E.E. Dihar 1997)
sr!ggg!:
Solution. PV = nRT= (i)Cohndbnof runb* of rnoles inthe minue
total
#RT
2atm x 64gmol-l P = 4.lE bar, \/ = 3 L, T = 27C = 300 K
- d- _,e _ PM _
v Rl 0.0821 LarmK-l mot-l x 30o K
PV=zRrorn -fl+ -
= 5.t969 g L-l (ii) Cabdatbn of nunber"fufifu=o.somor
of molcs difrtsed ia thc
Problefi I 5.Tr*o tlasl$ of Gqu&l voluEe coDDected sgrnc tnv
by a narro!,v tube of nc8llSible volume arc lilled t{ith No. of moles of N2 prcsent iD the mixture
N2 gar. trYhen both ore iDEersed iD boillng water the
8as prlfsur lDsidc the syst m ls 0 5stE. Calculste tbe = 0.4 mol
pressure of ahe q/sterD t hen one of thc nasks is im- ..
mersed ln str ice-watcr Eixture keeping the other in
No. of moles of unknor,fl gas = 0 5--{.4
boiling order. (C.E.E. Bitwr 19981 =0.1mol
Solutior. Temp. ofthe gaswhen both the flasksare Thus in the same time (10 mioutcs),0.4 mol of
imme ling water = 100'C = 373 K. N2 and 0 . 1 mol of unkDos|n gas diffuse out.
Pressure=05atm (iii) Calclnafun ol molonasr. As volumes under
Average temp. of the gas wheD one flask is im- similar conditions are dirertty proportional to their trum-
mersed in ice and the other io boiling water ber of moles, applying Grahao's law of diffusion

=
o +r1oo

-p.p2
= 5s.6 = 323 K

+.I _E
*q**= G-
As volumtemains consEnt,
," 3-f=E * Mx=44E8mol-r
o 5 P2 problern I E.Calclllala the ioot EGan squarE slreed
311 - 321 (azs) of ozone kcpt iD a clo6d vesi!.| at 20.C aDd
1r1 pressure olEZ cm of IIg. (Bihot C.E.E. 2003)
or Pz=ffir 0 5=0 433 etm. Volume oc{upied by I mole of 03 at
I,r,,r'rrnr lr'.What is the dilference ih pressure 20oc and 82 cm pressure can be calculated as follows :

between the top and bottom of a vessel 76 cm deep at '16zUN 82xV

---z-=-Tx
27'C when filled with (, tmter (ii) mercury ? Density of
water at 27'C ls 0.990 gcm-3atrd that olmcrcury is
or Y = 22282 cm3
13 60 g cm-r. (C.E-O. Rihat 1998\
P = 82 x 13.6 x 981 dynes ./ cm2
Pressure = height x density x g
Casc (i). Pressure

/
,=v#
='76 cfii x o.gg E crn3 x 981 cm / s2

.3E x
1| 3 x82x 13.6x981 x 22282
- I ---
= ? 104 dynes cm-2 4a-
= 0.073atE (I atm = I.0t3 x t06 dynes cm-2; = i 90 x toa c[Vsec.
2162

I.I.T. (fiNAWS ) ST?ECIAL

I'roilat i Calcnlatethe critical colstants ofa gas lfr is the radius of the gas molccule, then
whose van der Waalts constlnts ane :
a = 0.751 L2 atm mol-2 and D = 0.0226 L mol-!. l,f = t-zes x 1o-z cm3

-1'7
n a 0 751 L2 alm mol-2 or P =ix;x 1.365 x lO-acm3
'"- nE-i;A.or%L^rrry
=54 5rtm = 3 251 x 10-24 cm3

8a r = (3 25T1/3 x10-8cm=1483x10-8cm
^
'c-27Rb f.4t3A or 14t.3 pm
=
r.. Iogr = 1

-ffi 8 x o 751 L2 atm mol-2 lPur x = O 25'l)" 3

1o93.257

= 120 K = x0 5128 = 0 1709 orr = 1 4831

Vc=3b=3 x0 0226 L mol-l l'rol,bDr .1. A mixture of CO aDd CO2 is found to
havc I deDsity of 1. 50 g L-l at 20"C and 740 Em pres-
=0 067ELmol-1. sure. Calculate the cornposition ofthe mixture.
I'rohlun 2. The critical constants of a gas are as
follows :
Sol tio Calculation ofaverage molecubr masr of
the minure
P. = 45 6 otrn, Vc = 0 09t7 L mol-l and ., dRT
T.=lm6IC
-l
Calculate the yar derWaal's constanfs ofthe Bas. _ 1 508L-l x 0.0821 Latm K mol-l x 293K
Also calculate the radius ofthe gas molecule assuming
- (740,/7&) atm
it to be sphericat. =37 06
Calculation of percentage composition. Supm,sf-
Solution. v.=36gives6=! mol 7, of CO in the mixture = t
Then molEo of Cozin the mixture = (100 - ,)
_ 0.0987 _L nol-l - 0.0329 L mol-r Average molecular mass

P, = = 27 P"bz
_rx28+(100-.r)x44
Eives a
,f* 100

. ar*a#-4, =zt oe
=zzr. (!)'=:r"v3
Le. a= 3P"v!
or 16.r = 4400 - 3706 = 694
or x=694/16= 43 38
= 3 (45 6 atm) (o 0987 L mol-l)2 .. Mol% of CO =43 3a
=I333L2atmmol-2 and Mol % ofCO2 = 100 - 43 38 = 56'62.
Calculation of radiut of the gos molecule J Assumilg that dry sir contains 7070
l'rrrl.?,
lue of b per molecule N2 and 2l% ()2 by volume, calculate the density ofdry
air at 25"C aDd I atmospheric pressure. A.lso calculate
b 0.0329 x ld cm3 mol-1 the density of the moist air under the same corditions
NA 6.022 x 104 mol-l ifit has a relstive humidity of407o. The vapourpnessure
ofwater at 25'C is 23 76 mm.
= 5 46 x lo-a cm3
Sotutio& Calculation of density of dry air, Den-
4\n :. tn- 4b = -----T-
5-46 x lO-B sity ofair means the mass ofair per litre.
But b = cIn-
First let us converr I L (1000 cm3) of air at 25'C,
1 atm pressure to the volume at S.TP
=1365 x 10-B cm3

\
STATES OF MATTER 2la3
Pr Vt PzYz No. of moles of N2 in the air (zN2)
-T.:-E-
cm3 atm x v2
=o3:#l?);r'-3 ,ex,o-2
I atm x 1000 1
29aK = Z'73K No. of molqs of 02 in thc air (zo2)

or V2 = 916 l cmj =uiid{r'f;#' =8 48 x,o-3

As air contains 79% N 2 arrd 21Eo o'2, . . lbtal mass of 1 L of air
. Volume of N2 at S.TP in tho air = 5.1 x 10-' x 18 + 3.19 x 1O-2 x 28
+ t,48 x 10 -3 x 32
= ffi " erc't cm3 = 723 72 cm3 = 0 .00918 + 0.8932 + 0.02114
= 1.174 t
Volume of 02 at S.TP in the air Hcnc! density of moist air = I .tlt g L-l.
Notr- Density of dry air cao also be calculated ry
= ft x eto.t cm3 = 193.38 cm3
this metbod.
Mass of 723.72 cm3 of N2 at S.TP Prublen 5 . N r.roa LElrcraturc aEEorlo gss at
I atm pEssure ard HCI gas at pEssure P attrt rre
= ffi rnt.n = o.eos e allowed to cllhse thrcugh ldctrtlcrl ptD holes from op-
pcit cnds of e Slass tube ol I Ecter lcngth ard of
Mass of 193 38 cm3 of02 at S.TP. uniform ares of cr6.ccctlon. NHaCI is first formGd at
r distsrcc of60 cItr froE the end through wh ich HCI gas
= iin " ts3 .18 = 0.276 t was seEt iD" Clculat thcyslucofn (I.T l9E2)
. Total mass of IL ofair at 25"C aod I atm Solutiotr. Acmrding to GrahaD's law of diffusion
for gases at different pressures,
= O.9OS +O 216t=1 1A1t
Hence density ofdry air = I .lEl
Calculation oldeNity of Eolst air
t to
'*-q,,
1&-
-
Pxo
MHo
% Relatirc humidity
Plrtiel prc.surc of H20 vaPours
rr'apour pressure of HzO at the same temp. x 100 #=+ v*i
.. Partial pressure of H2O vapours
or P= (.s),f+f
40 x 23.76 =1.5 x1.465 =2.19Eatm.
= ____fIE = ,,, ,. |'tu)l)L t 6 A spheicsl balloon of2l cEr diameter
As total pressure
is to be lilled with hydrogen at NTP frcm s c]rlinder
= 1 arm = 760 mm,
coDtsining the gas at 20 atrEosphere at 27'C If the
. . Pressure of N2 + 02 io the air cylilder can hold 2 E2 litrts of water, calculate the
=76O-9 5 =750.5 mm number of ballons thot cau be lilled up. (I.l.L l9E7)
As N2 alld 02 are present in the air in ihe rario of Solution. Volume of the balloon
79 : 21volume, 4 r 422 l2t\3
= T,r = i,
.. Partial pressure of N, x ;so s mrn = 7 " lT )
= ffi =,1851cm3
592.9 nm
and Partial pressure of Oz = 750 S - 529.9 = Volume of lhe cyliDdet = 2 &2lines = ?320 cm3
Pressure = 20 atm.,
157 6 mm lbmperature = 300 K
Apptying gas equation Pv = a RT ie. n = CoDverting this ro the volume at NTP
ff Pr Vt Pz Vz
No. of moles of H2O in thc air (r H2o)
-T, =-n-
_ (9 s/1&)armxlL mx282/J I xv2
0.0821 Latm K-l mol-t x 298 K we ger ---35_ = -773_
= 5.1 x 10-4 or Yz = 51324 ql .
2/64 Pradeep's
When the pressure in the cylinder is reduc-d to one No\r
atmosphere, no more H2willbe released and hence 2820 2NO + ..- Oz 2 NOz
of H2 will bc left in it Hence volume of H2 uscd in
Moles I .602 x 10-2 o.32 x 10 '
cm3
0
filling the balloons
before
= 51324--2820 cm3 = 485M cm3. reaction
Number of balloons lilled Moles I 602 x l0-2 0 o 32 x 10-2
= 48504/4851 = l0 after -2 xo.32x1o-2
The average velocity et T"t K and the reaction
most probable velocity at T"z K of CO2 ges is =0 429 x1O-2
9 0 x l0'cm sec-l. Calculstc the values ofT, and T2. Thus, molesof NO lefr = a 2q x to-3
(I.I.T 1990) Now T= 220K (Given),
Solution. Average velocity =0 9213 x R.M.S. v=2s9u*uJmr=o:sr
velocity
Applying gas equation, Pn6 V = n RT
=os2t3x .rNO---r
nRT
3xE.3x107xT, 0 0821 L atm K-l mol
'9xld=O.9213x
This on soMng gives
Tl = 1691 K

Mo6t probable velocity =

9x1d=
2x8.3x107xT,
tr = 0.227 alE,
Problen 9. A gra bulb of I lltre cspoclty coDtains
2.0 x ldr moleculcs ol nitrogeB ercrtttrg a prcsurt ol
1-57 xld
(r.m.s) speed,Dd
N rD-2, calculat the root mcan squarr
th.t
Il the rstlo ofthe DoEt proboblc
nper8turc oftbcmoleculeg
thc root meoD
EpGed to
8as

square speed is 0 .E2, cslculstc thc nost probablc sPced

This on soMng Sives Tz = 2147 K for thsr moleculcs et this temperature. <I.I.T 199i)
I't,,1,!, nI At rooE teEPersturc' thc follorring solutioE. volume of gas = 1 litre = 10-3 m3
reection Soes to coDpletion
.... N2O1 Pressure = 7.57 x 103 Nm-2
2NO+Or
-2NO2 No. of mols of the gas
Dimcr N2Oa .t 2.6t K ls solld' A 250 rzl llosk and
= (2.o x 7o2r) / (6.02 x 1#) = 0.fi332
a lfl) zrl 0ask ore separattd by a stoP- cock At 3(n K'
Appbting PV = nRT
ihc nitric oxide ln the lsrBer ltssk ex.rts Prcssure of
1.053 atm and the smoller one coEtalns 02 rt O 7t9 (?.57 x 101 x 10-3 = 0 00332 x 8'314 xT
atm, Thc Ssses sre mircd by oPenhS th stoP.cock and or T = 274'25K
alter ahe end of the reactiotr, the nosks 8rc coolcd to 220
K. NeSlectinS the vapour presturt ofdlEer' llDd out th. Root Mean square spc"o = \4f
plEsure and coErlro6itlon ol the gas FEaining at 220
K. Assume gss6 bohave ldeally <l.l.T 1992)
Solutiotr. ForNO: Y =EO mL=O E L'
T=3{nKP=1053atm
,tm
=|--------.--E--
PV=fffiffi='r'06exr0
1.053 x0 25 = 49426.5 cm r-l
.. ano=ftf '
ForOr rV = 1002L = 0 1 L,T = 300K, #ffiffiffiffi =o.82(Given)

P = 0.789 atm .. McBt Probable sPeed =0.t2 x R. M. S. SF!e..d

. 0789x01 - 32 xl0'-r'
,or=ffi=0 = o'82 x 49426'5 = 40529 7 cm s-r
STATES OF MATTER 2165

Pnrtlem 10. A 4 r I molar mixture ofHe artd CH. i.e. P = l atm,V = 41q).5rn3,T = 300 K
is contained ina vcssel at20 bar pressure. Due to a hole
R = 0 082 dm3 atm K- l mot-r 1{iivenl
in the vessel the gas mlxture le{ks out. Whst is tbe
composition ofthe rDixture effusing out initially ? PV = nRT
(I.I.T 1994) i.e. (1 atm) (4190.s ,,r3)
Applying Graham's law of eftusion, = r x (0 082 x 19-3-l *-' mol-l) x (300 K)
",rn
4190 5
fHc fhis givcs n =
rcH. o.o82x10-sx300
t 70345 .5 moles
r'.. He diffuss two times faster than CH1. Weight of 170345.5 moles He
.. Molar ratio of He : CHl effusing out initially
tg = ear 'r tg
= 1'1o345.5 x
fi
=t:1 Ttltal weighr of the balloon filled with He
Problem lI.
An LPiG (liquefied petrcleuD gas) = r00 + 681 4 kg = 7t1.4 kE
cylirder weighs 14 t kg when eEptF Whetr full, it
weighs 29.0 k8 aDd shows E prEssure of2.5 atm. ID the Maximum wEight ofthe air that caD be displaced by
course of use rt 27qC, tbc eelSht of lhe tull cllitrder balloon to go up = Volumc x Dcnsity
reduced to 23 . 2 kg. FiDd out the volumc of the gas in =4190.5x12=5028.6kg
cubic Detts used up st thc norEal usagc couditionq .. Pay-load ie extra load that can be attached to
ond the linol prssurc inElde the cflitrdeB AEsuEe LPG the balloon = 5028 6 - ?t1 .4 = 4247 2kg
to be n-butsne tf,lth normal bolliDg poiDt of (rC. I'atblut Ii The compcitlor ol tbe equilibriuE
(rJ.r 19%) mixture (Cl, ;+ 2Cl),which is athined at l20O'C is
!9!9!94, Decrease in the amourt of LPG determiDed by Eeesurlng ttc rate of efrusioE through
a piD-hole. It is obsrved that et 1.60 Dm Hg pressurc,
= 29.0 - 23.2 = 5.E kB
the mixture efnrss 1.16 tiEes ss fost 8s KryploE ef-
5800 fuscs under the samc cotrditiotrs. Colculatc thG fraction
= :;: motes = too motes of chlorire molccules di.ssociat d iEto otoms (Atomic
Volume of 10O moles at 1 atm and 300 K weight ofKr = E4) (I.I.T 1e95)

'lRT
P soEtien.ff =/H
1oo molc6 x 0 0821 L atm K-l mol-l x 300K

=
I Ulrn
x to-3 m = 2'463D't'
2463L = 2463
i.e. I 16= v#
Final pressure iNide the cylinder. As the or M.t, = 6f zfl
crlioder contains liquefied petroleum gas in equi- If.r moles of Cl2 dissociate at cquilibrium, theD
librium with its vapours, therefore so long as tempera-.
ture remains constant and some LPG is presenq Clz ir 2Cl
pressure will remaiD mostant. As the crlioder still con.
At. eqm. I -.r 2x
tains LPG = 23 2- 14.8 = 8 4 kg, pressure rnside the
cylinder will bo same ie. 2.5 stE. Average molecular mass of the mixture

Pnfilem 12. A balloon oldlamctcr20 m wcighr 1fi) _-i)x71 +2.tx35 5 _ 71

(1
k8. Cslculrte lts payJood lllt lE ll|led wlth Hc at I . 0 ctD
(1 -r)+zx I +r
11
aDd 27'C. DeDsity of tbe olr ls 1.2 lg cE-!. (R = Hence I +; = 62 43 which gves.r = 0 137.
0 0E2dml atm K-r mol-r) (Rurkee 1994)
Hencc fraction dissociatcd = 0 137
Solution. Radius of the ballmn = 10r, 1r',,r i! An iron cylinder contaiN helium at fl
. Volume ofthe balloon = 1z r' pressure of 250 kPo at 3OOK. ThG gdiDder cED
wlthstatrd a prcssure ofl x ld Pa. The room in which
= = cylinder is plactd cskhes lire. Predict *hether the
t "?" (10)3r'r3 41e0.5 m3
cylinder will blow up beforr it melts or troL
Volume of He filled at 7 atm aDdz7"C = 4190 5 m3 (M.P of the cyliEder = 1t00 K) (Itoorkee IDS)
 llrada a1t's Neqt Course Chemistra IMID
2166

Pr = 2JQ ( Px, Tr =300K Sotutlop. Volume of the liquld

K (14r _ 50)4
_
t2-' Tz = 1E00 = too ml
0 98I mol '
Applying pressure temperature law
Pr Pz
- = 0.1 titre
q=q This is the
volume of the gas.
volume of the vessel aDd henc the

P
or For ideal gas, Pv = n nf = ff nf or fr{ =
$
ffi=ffi P2 = l5o0 tPa
As the cylindor caIl withstaDd a pressure of ld Pa 0.5 c x o ot2 L alm K-l mol-l x 300 K
- latmxo.ll-
= 1d tla = 1o0O kPa, hencc tt w l blott uP.
Pnthlen 15.20 dm3 of SO2 difluec ttrough a = l23gmol-r
t'rohlen 18.llsingtan der Wsals equstion calcu.
porouE poilition ltr 60 s. I9hrt YoluEe ol Or eilt difilEe late the corstont t4'when fi{o moles ofa gas confrned in
undcr slmllrr c!trditions ln 3Ot? @oor*ce 1996) a four litre flask exerts s Pressure of 11 0 atmosphere
at a temperature of 30o K. The vatire of rD' is 0 05 lit
,-, = ?H+ =!0,',-r mol-l (I.LT, l99E)

,or=# =$a,n3s-l sorutio,,. [p

* e4l cr-*l =, *t
)
Applying Gmham'8 lsw of diffi$ion
or a= / zRT -\ V2
,o, \V
_rt- r )F
tq = -\ x-l mol-l-x30oK
- [z mot x o oezos Larm -tt r,r]
4l-2molx0 osl-mol-r
* +,+=G l\ )

ot 16= O or u=lr'14rlm3
I'roblrn 16. CotculatG thc total Plessue ln a 10 L
= 6 49 rtm L2 mol-2
clllnder whlch contalDa I'roblern 19. Aglwbulb contaiDs 2'24 LofH2 and
oud 1 .4I olnikogoD ot
I . 12 L of D2 st S.IiP It is conneclcd to a fully evacusted
pressur of helluD gsr
K-r mol-r). bulb by s stopcock sith a sDslt oPctrin8. Th EtoPcock
behoylour for goses. (R = 0 OE2 L stm
ls opened for eomcdDe and then dceil The llrst bulb
(R@*ce 199n
now cotrteirs 0'10 g of D2. Calculate the lrercertaSe
'Ibtal no. of moles of all the 8ass (z)
coEp6ldoD by weight of the Ssecs in the second bulb.
=)'ff*ff=o'z WeiSht of
(Roor*ce 199E)
2'Z Lof H2 at S.'fP. = 0 2I
volumc of the gaseous mixture (9 = 10 L
lbmp. (D = 27 + 273 = loolc = o. 1 mol (Mol. mass ot}Jz= 2)
wbight of 1 12 L of D2 at S.TE = 0 2 g
R = 0 082 L atm K-l mol-l
As gases have ideal behaviour,
= 0 05 mol (Mol mass of D2 = 4)
As number ofmoles of the tslo gass are different but
PV=nRT V and T are same, therforE, their Pa ial PrcssurEs will be
--. zRT 0'2 x 0'0&2 x 300 - O.4yZ atm
ort=-n-=--------fi- differeni i". in the ratio of their number ofmols. Thus
P\ n\ 0.1
.. Partial prcssure of helium
E-- nr=O.TS= "
=o i:ia 'o'+n=o 2'46 rta Nol{ D2 present in the first bulb = 0 1g (Givez)
I'robleu 17. Atcvrcnstcd oh<r vcs6.l rcighs 5{) 0 .. D2 diffirsed into the second bulb
g wheD eDpty 14E o g when n[cd wtth I liqui(i of = 0'2-0 l = g-:!JL= o s6 LatsTP
rlensttyo 9E g ml - r and 5O'5 g when [ltcd wlth an lde.al r*n Ps, rlMo,
8rs at 760 mu EB 8t 3OO IL DetlrDhc thG Dolccltllr
(1I.I199t,
Nou ,"=G", G
vclght olthc
""4
 STATES OF I\,iATTER 2167

*
uH. , = Pn. .fr-l or r'M; = 3 x r/U or Mx = 9 x28=252
,= ",% rr-;,. " "; Atomic mass of Xe = 131 a

T_
. . Mass of F atoms
= X2 - 131 = !2L tt
Aromic mass of F = 19 U

ot
]"oln=2"\ |
,H2=1584L=014tofH2 ... No. of F-atoms - 1?1 = u

.. WeiSht of the gases in 2nd bulb Henc the compound is Xct'5.

=0 10s(D2)+0 l4g(H)=o 2at Problem 22. Ttc prtsurc rxcrtcd by 12 g of an
Hence in the 2nd bulb, ideal gsc at tcEpcrsturc nC lu s vrascl olvoluBc V lltre
ls oDe ah!. VyhGD the tem!rcmaure ls increas.d by lO
qo of D2by wei1ht =
{fi , ,oo = nr.rrn degrecs rt tle s.Ee voluoq the prcssure incrcases by
% ofH2by weighl = 100 1096. Crlculote the teDpersture , aod volumc V
- 41 67 = 5a 33%.
(Molcculsr nclght ofthe gas = 120). (LI.T. 1999)
I'nhlon 20. lf the yolume occupied by CO2 Applying PV = ,t RT
molecules is D(Zligible, the! calculate the prrssune ex. Io the 1st case,
crted by one mole of CO2 gas at 273 K
(a = 3.592 atE lltrc-2 mol-2) <t.r.T. 2N0)
txV=.ifrxRx(n3+D
1a
...(,
In the 2nd case,
(v' 4 (v-D)=RT
Solution, Por 1 mote, i/r +
11
l.l xv=#xRx(283+0 ...(ir)
If b is ne:lisibre, (- - #; " = *, DMdint (,) by (ii\, t/t.t = (213 + t)/ (283 + t).
or -=+-# On soMnt it gives , = - l?3"c. Purting in (i)
V = 0.1 x 0.082 x I0O=0.E2litrt
or Pv2 RTV+a=0 I'roblqn 2i. Ihe comprcssion foctor (coEpres-
'lhis equation is quadrati ln V Flence sibility factor) for one mole ol a van der Waols grs at
0'C ard 100 stD prcssure is foutrd to be O.S. Assuming
*nr=Vn,r,-aop tbat thc yolumc olo gos molc<ule ls negligible, calculate
2P the van der Waals constaDt(] (I.I.T 2001)
As V can have oDly one value at P aDd T hencc wc
tlave R2T2-4aP=O Solutiorr, - PV t.e. u ) = lO0xV
L=iEr
must Tiomr;z-7r
or Rzt'=4ap * .=*;I' or V=01119L

_ (0.0821 L alm K-1 mot-l)2 (273 K)2 l\ 4)

v'l',r, -,, - RT ror l mol
l/r *
4 x 3.592 atm L-2 mol-2
Neptecrins a. /p * 4l v = nr
= 34.96 atm --\v'l
t'r, l.L Dt 2 1. One mole of nitrogen gas at
t{kes 3t s to dimtse thmugh a pio hole whereas one
mole ofan unknown compouDd ofXcnon with fluorioe
0.t atm
or rvr$=Rr or ffi-1fu=,
at 1.6 atm takes 57 s to dilnrse through the same hole.
Calculate the molecular forDula ofthe coErpourd.
o' o=(r-H)*'
('l'T 19991 =(l -0 5) 0.1119 x0.082x213
..-.*..-( i
sorurion. Rare ofdiffusion
= I 252 atm L2 r,ol-2
"fii-
tn, Px, I'n,hlur )J. Pay toad is detined as the dilference
rx
=-=-E-x \+; between the @ass of the displaced air and the mass of
the balloon. Calculste the pay load rryhen a balloon o[
radius 10 m, mass 100 kg is filled with helium at 1 66
Bur rno, = 1,/38molr-1and tx= 1/57 mols-1
bar at 27oC (Denslty of sir = 1 2 kg m-3 and R
=
. 'n, r/38 5i 3 1^; 0.8
0.083f, bar dm3 K-l hol-r) (N.C.E.R.T)
E=I7T|=N= Z= ln v B Proceed as in solved example 12,
Page [A-trs.36U l kg]
2168 Pradeep's
Problcm 25 Thc deElty of thc vapour of r BUE 1 atm x 50'25 L

"* *-t -o,-t

kgm-3. Thc 6 a321 1 x 500 K
= r.224
:: #i"1" (iv) As Z > 1, rePulsive forceswould dominate
(d) Determine (i) molecular weight (i, Etolsr
volume (iio cornprcssiotr factor (Z) of tbc vsPour and tbt E = ;kr
(iv) which forces aEoDg thc 8as Eolccules arc doEitrat'
ing, thc attractlYe or thc rePxlslac ? = x r .ss x 10-r JK-l molecule-1 x 1000 K
]
(b)l 10oo K, dctar'
miue the GtrerBl ol thc = 2 o? x 1o-2oJ pcr molecule
Eoleculc- <II.T 2002, ?rohlcn 26. The averoge velocity ofgas molecules
is 400 n/sec. Calculate its rns velocity at the saEre
. (a) (i) d = O 36 kg m-3. BY Graham's
tem
law of dimrsion, Ezootl
," 11q; . AveraSe speed, u = V#
tq=tq
Root mean square spe"o,, - \F
Le. 1$=\E or I\4=1t'0e
.. ;= ,.Fffi
V -T- x
FRf
(ii) 0.36 kg m-3 = 0 36I L-r
3 x3.143
ie. O 36t ofvaPour have volume = 1 L ----3- =1085
.. 1 molie. 18 09 9 of vaPour will have volume
. u= 1085xu= l O85 x400m.r-1
=5{3.*re.or =fi2sL = 4!4 ms-L
ot diectly,o = o g21ui.e.u=7 085 xo
(rii) ComPressibility factor (z) = #

1. The lemperature at which the volume of the 8as is 4. Amorphous solids

zero s (a) possess sbort range as well as long range order
(a) 0'C (b)rK (r) possess sharp meldng Points
(c) 0"F (d) nore of these. (c) are isotropic
(d) uDdergo a clean cleavage when cut with knife.
2, With increase of temPerature, the surfac tension
of a liquid 5. A bottle of dry ammonia and a bottle of dry
(a) increases (b) decreases hydrogen chloridc connected through a lo[g tub
(c) remains unaffected are opened simultaneousty a! both e[ds, the whire
ammoDium chloride ring first formed will be
(d) may increase or decrease
(a) at the csntre of the tube
3, Under identical experimental conditions, which
one ofthe following pairs of gases willbe most easy -lih)rear the hydroFn ctlloride bottle
to separate bY diffusion Process ? (c) near the ammonia bottle
(a) 02, N2 (D) 02, Fz
(d) througbout tbe length of the tube.
(c) Hz, Dz (d) 235u6,238uF6 tr.l.'t t98E)

t.b z,b 3,c 4,c 5.b

 STATES OF MATTER
2169
6. The rate of diftusion of methane at a givcn
(a)Dn=lDs.pa/pslt/z
temPerature is twice that of X. The molecular
weigFt ofX is
(b)Dn = lDs. pg/pA)t/2
lo{dq.o (b)32.o
(c) a0.0 (d) 80.0. 1flDo= D.1pot pr11/2
(l.I.T. 199o, ltIL.n'.R. Altahnbad I9eS,
qdD^= DBq,B/p^)t/2. (t.LT t99j\
Keraln E.E.E. )00I )

7. The densiry.-,
ofneon will bc tushe$ 13. A gas bhaves most like an ideal gas under coDdi-
ar
tiolN of
(a) sTP pfac,zatm f4) Iligh pressure aod low temperarure
(c) 273C,l atm (d) 273C,2 atm.
(r)iligh remperarure and high pressure
_l?).Low pressure and bigh temperarure
,,yy'furaing to *ineric theory of gases, # (d) I-ow pressure and low tempcreture.
molecule
(a) The pressure exened by tb gas is proportional
to the mean velocity of the molecule 14. Ifvapour dcnsiry of 02 and H2 are 16 and 1, then
(6) The pressure exertcd by rhe gas is proportional the ratio of rate of diffusion of H2 to that of dif_
to the root mean square vclocity of the molecule iusion of 02 is
(c) The rmt mean square velocity of the molecule
(a) t6 (b) U16
proponioDal to remperature
thversely
li,liThe mean ranslationat kinetic enerB/ of rhe J*$ (d) ll4- ,( ttrt t ro,t
' molecule is proportional to the aholute 15. Containers A B aDd C of equal volume contain
temperature. oxygcn, neon and methane respectively at the same
temperalure and pressure. The correcl. increasing
9. 1\t the sarDe tempcrature and pressure, which of
order of their masses is
lhe following gass will have the highest kinetic
energy per molc ? (a)A<B<C (r)B<c<A
(a) tr2 (D) oz (c)C<A<B 14yC.t. x
(c) CHa
.,16, Tcmpcrarure below which rhe gas does not obcy
Iy'rAll will havc equat vatue. tdealgas laws is
t \! t . lt \.r.t, tt, t, , '')l (a) Cnrical temperaturc
10. At constantvolume, for a fixed number ofmoles of (b) Inversion temperature
a gas, rhe pressure of the gas increases with rise of
(c)Boyletemperature (l)Reducd/temperarure.
lemperature due to
-(zffncrease in average molecular speed \7. The volume of 0.0168 mol of Oz obtamed by
(6) increased rate ofcollisions amongsr molecules
dccomposirioo of KCI03 and collecred bydisplace_
(c) increase in molecular altraction ment ofwarer is 428 mlat a pressure of754 mm Hg
(d) decrease in mean free patb. ;,: ar 25'C. Thc pressure ofwater vapour at 25"C is
(d) 18 mm Hg (6) 20 mm Ug
11. Equalwcights ofethane and hydrogen are mixed in
(c) 22 mm HB (d) 24 mm 119.,
an empry container at 25"C. The fraction of the
lotal pressure exerted by hydrogen is
(a) 1.2 (D)1:1 16. The vapour pressure of water at 3OO K in a closed
contaiocr is 0.4 arm. If the volume of rhe contaiDer
(c)1:16 ldf15:16. tttr. rsql is doubled, its vaFnur pressure at 3OO K\yill be
12. At constant volume and temperature conditioDs,
tbe rate3 ofdiffusion DA and DB of gass Aand B (b) O.2 atm

having dcDsities pA and pB are relatcd ry the sx_ (d) 0.6 atm.
pression
Itt D@n (.li.lr.'l: irt)t

6.a 7.b a.d 9. tl 70. a 13. c 14. c t5. d

16.c 17. d lE. c
2tz0

19. The ratio between the root mcan square velocity of (a) KEso = KF-N,
H2 at 50 K and that of02 at 800 K is
(D) KEco > reN2
(o) 4 (b)2
(d)114. \t.t t: te,6) (c) KE6e < KE1,
$r1
20. X ml oftl2 gas effuses through a bole in a mntainer (d) cannot be Fedicted unless the volumes of the
Sases are gNen.
(c.D.s.E. Mr.T 2oo0)
in 5 scconds. The time takeE for thc effusion of the
samc volume of the 8as spccif,ed bclow undcr iden' Dcnsiry ratio of 02 and H2 is 16 : 1. The ratio of
tical coDditioDs is their r.m.s. vrlocities will bc
(a) l0 sconds : He {d}6'sccoorts : O, (o)4:l (b)1:16
(c) 25 semnds: Co (d) 55 sconds: cO2' (c)1:4 (d) 16 : 1.

,. -/ ' l.l l'Jttt' tA.l l ,lL\ )t10(1t

ti(/-n *mpr*ibility factor for an ideal gas 27 . Pressurc of a mixture of 4I of 02 and 2 g ot H2

" s
(a)t .Pfn mDfined in a bulb of I litre at 0'C is
(c)zo tt t.t: I9e7t (a) 25 215 atm (6) 31.205 atm
@)-
22. The critical temperaru re ofwater ishigher than that (c) 45 215 atm (d) 15 210 atm.
of 02 because the H2O molecule has ill I:\l'S )(tt)''
(a) fe\xer electrons than 02 2f. Which of the folloying cxhibits rhe weakest inter-
molecular forces ?
(b) two covalent bonds (c) V-shaPe (D) Hcr
(a) NH3
.fd) diPole momenr.
(c) He (d) }{lo.
23. Ac.cording to Craham'slaw at a Siven temperature,
the ralio ofthe rates ofdiffusron ralrB of 8a!es A \'\ I-l ll S )ttt)tt
and B is Sivcn bY It30o mlofa gas at 27"C is cooled to ToCat constant
pressure, ils finalvolume will b
(a) 1rnlPs) (M6/Ms)l/2 (a) 135 ml (b) 540 ml
(b) (MA/MB) (PAl PBt/2 (c) 350 ml (d) ?3o
',lt.
t,t.l.I Jl.,s.2000t
1g(t 30. At oqc and one atm pressu re, a 8as oc{u Pies 10o cc'
^tt"11MstM,Jt/2
(d) (M^/MB) (PBlPar/2. If the pressure is increased to one and a half-time
and temperature is increased by one-third of ab-
(where P and M are tbe prqssurcs and molccular
solute temPerature, then final volume of tbe 8as
wi8hts of gases A and B respectvely)' ' /. i / " " will b
24. Which onc of the followint $atcmenlsts r4ong lot (a) 80 cc (6) 88.9 cc
gass ?
(c)66.1a, (d) 1m cc.
(a) Gass do not havc a definite shape and volume ( I).(' li.l; F: )t)0t)\
(6) Volume of the 8as is equal to tbe volumc of the
mnbiner confining the gas The deDsity of at ls 0 00130 8/ml. The vaPour
deDsity of air wi[ be
(c) Confined gas exens uniform Prsture on the
' ' wells of its contaiDer in all dire.ctions (a) 0 0006s (D) 0.65
uei8h' (c) 14 a816 (d) 14.s6.
-(/) Mass of the 8as canriot be determined by
ing a contaiDer in s'hich it b enclGed. il).(.E.D.E.2000|
t(' It \ i.: !'.\l I lt)I)lt\ 32. The retatioDshiP which desribes the variation of
vapour Pressure with temPerature is called
25.
(a) Hcss's law (r) Arrhenius equation
(c) Kirchoff's law
same temperature ? (D,Clausius-clapeyron equation. t 11. H. Li. 2 0 0 0 \

19. c 20. b 21. b 22. d 23. c 24. d 25. a 26, c 27, a 2t, c
29. d 30. D 31. d XZ,.l
STATES OF MATTER
'2n1
33. DeDsities of two gases are in thc ratio 1 :2 and tbeir (a)Vd> 22 4tilIes (D) V,n < 22.4 titres
temperatures are in the ratio 2 ; 1, then the ratio of
thcir respective prcssures is (c) V- = 22 4 litres (d) V,' = C4 31;1r"..
(d)1.1 (b) t:2 ,t l 't )i,,
.{)2: t (d) 4: t. 11 t'. )o0o 40. At 100'C and 1 atm, ifrhe densiry oftiquid weter is
?tr4as equation PV = ,r RT is obycd 1.0g cm-3 and that of water vapour is
(4) only isothermal process 0 m06g cm-3, then thevolume occupicd rywarcr
(r) only adiahatic process molcules in I litre ofsteam ai that temperature is
.@\6otn @) and (b) (a) 6 cm3 (6) 60 cm3
(d) None of these. (B.HU. 1000) (c) 0.6 crn3 (d) 0.06 CrI!3.
35. The rate of dimrsioD of a gas haviog molcc,rlar
t l.l l:2ht)tt
weightjustdoublc ofnilrogeD gas is 56 mlr-1. The 41. The root mean square wlocity of an ide3l g8s at
rate ofdiffirsion ofnirrogcD will bc constaDt prcssure \taries with dcnsity (d) as
(4) 79 l9 mlr-1 (b) 112 0 mls-l (o) d2 (b) d
(c) 56 mls-1 (d) 9O.O ml s-1. (c)'/t (d) 1 / ,td.
t(.1).1L1 J000 )

36. '[rc following graph illustrates 42. At whar tempe rarure will the RMS of SO2 be rhe
same as thar of 02 at 303 K ?

(a)273 K (r) 606 K

(c) 303 K (d) &3 K
tK.L.L,f.2t)ul
The ,irrl r. vclocity of CO2 at a temprature T (in
keMn) is-t cm.r- l. Ar wbat temperature (in keMn)
the rrru. r,elocity of nitrous oxide would be 4r cm
,-l ?

(a) Dalton's law

(a) 16 T (b) 2't
_.[t Charles 'law (c)aT
(c) Boyle's law (d) Gay-Lussac's law.
(d) 32't
I I.Lll11.E.R )t)t/t)t
I \\lt I I t

44. If the four tubes of a car are filled to thesame

37. 44 g of a gas at STp ocqrpies a volum e otZ.2A L,
pressure with N2, 02, H2 and Ne sparatcly, rhen
the gas can be
which one will be fi ed first ?
(a) oz (D) co (r) Nz (D) oz G)Hz (d) Ne
(c) NO2 (d) coz.
Ih^t
.;.:.
t n C.E,L.f 2t00) 45. Air at sea levelis dense. 'fhjs is practtcal applicat ion
of
The r-m.s. velociry of hydrogen is y'7 rimes the lrfioyt"'" t^n
r.m.s- velocity of nirrogen. If T is rhe temperature (b) Charles' Iaw
of the gas,
't (H2) = T (N/ (c) Avogadro's law
(a) (H,
(b) T > T (N2)
(d) Dalion's law
(c)T(rL)<T(N, (d)T(H, = \r/ T (N2). law t
^t:i.t t..i t:,
&) Gay-Lussac's
I I l. I t)ttt) | 46, Which of lhe follo\f,iDg has maximum rmt mean
Thc compressibility of a gas is less t ba n u niry at S-l? square velocity at the same temperaturc ?
Therefore (a) SO2 (6) co2

33..t 34. c 35. a X.b 37.d 3&c 40, c d

43. a 41. c 45. a
41. 42. b
2172 Ne.4 Course Chen istrtl
(c) oz ((i ) II2

47. Kinetic theory of gases Presumes the mllisiotrc be'

tween the moleculcs to be Perfectly elastic bccause
(z) the molecules are riSid
(D) the tmPerature remains coDstant irrcsPective
ofcollisions (a) T (K) (b) T (K)
(c) collisions will not sPlit the molec1rles
(K.C.E,T 2002\
(d) thc molecules are tiny.
The van der trlaal's cquation reducls itself to the
ideal gas equation at
(a) high prssure 8nd los, tcmPcrature
(b) lo$, pressure and lo EmPerature
(c) lolx pressure and hiSh temPerature T (n
(c) T(n (d) r (Kl

(d) high pressure and high temPerature.

(c l).s F:. PLLT 2002)
53. When the tempcraturc is increased, sur[ace lcnsion
49. For an ideal gas, Dumber of moles Per litre io terms ofwater
of is pressure i gas constant R and BmPerature T (a) increases (b) decreases
is
(c) remains consiant
(a) PT/R (,) PRT
(d) shows rrregular bhaviour
(c) P/RT (d) RT/P

54. Positive devratioo from ideal behaviour takes Plac

50. Among the solids, rhe highcr melting Oorr,, "*' bccause of
hibited by
(a) molecular nteraction between atoms and
(a) Covalent solids PV/n RT > 1

(b) Ionic solids (6) molecular intsractioo betweeo atoms and

PV/nRT < 1
(c) Pseudo solrds (c) finite size of the atoms and PV/,RT > 1

(d) Molecular solids (d) finite size of the atoms and PV/,RT < 1

(e) AmorPhous solids t!' 1't ''

55. 0 5 moleofeach of H2, SOz arid CHa are kept in a
51. When lhe temperature is raised, the viscosity of the
liquid decreases. This is because container. A hole was made in the container' Afler
3 hours, the order of partial pressurcs in the con-
(4) Volume of the solution decreases rainer will be
(b) i[crease in temPerature increases the average (o)Pso, >PcHo >PH, (b) PHz >
'Psoz PcHr
kinetic ener$/ oIthe moleculeswhicb overcom'
es the attracrive force between thcm (c)PcHa >Pso2 >PH. @)la" >Pcxr >Pso,
(c) covalent and hydrogeo bond forces decrease
(d) attraction betYeen the molecules increases 56. Ifrr7l-j speed of grr"or, ,ol""rl",
irx cm^ec at a
pressure ofp atm, thcD rm.J at a pressure of2p atm
(e) none ofthdabwe "."''\|t !
and constant temPcrature will be
52. Which of the following volume (V)-tcmperature (o), (b) 2x
('l) ptots rcprcscnls thc behaviour of one molc of (c)4x (d) xl4
an idcal gas at one atmosPheric presure ?

46. d 47, d 4E, c 49. c 50. d Sl. b 52. c 53. , 54' a 55. a
56. d
STATES OF MATTER 2173

57. In the equation PV = RT the value of R will Dor (c)1:4

depend on (one or more) 6' The pressure and temperature of 4 dm3 of carbon
(a) the narure of the gas dioxide gas are doubled. Then the volume of carb-
(b) the remPerature ofthe gas on dioxide gas would bc
(c) the pressure of lhe gas (a) 2dm3 (6) 3 dm3
(d) units of measurement.
(c) 4 dm3 1a; a om3
5E. Boyle's law may be expressed as (one or morc)
(a) (dP / dv)T = K/v (b) (dP / dvh = - K/V Hydrogen diffuses six times faster than gas A The
(c) (ctP / dv)r =-K/V molar mass of gas A is
l,al'|2 (b) 6
(d)v(i. 1

(c) 24 (d) 36
59. According to Charles' law (one or more)
(a) (dY /dT)p=K (b) (dv /d\p= -K What is the pressure of 2 mole of NH3 at
(c) (dv / d1)p = -K/T (d)v aT.
27'C when its volume is 5 litre in van der Whals
eguation ? (s = 4 77,b = 0.03711)
60. The root mean square velocity of one mole of a (a) 10.33 atm (6)9 33 arm
monoatomic gas having molar mass M is Ur.m,, .
(c) 9.74 atm (d) 9.2 ar.rr,
The relation between (he average kineric energy
(E) of the gas and U' is
The ratio of most probable velocity to the avcrags
velocity is
(o) u'...,. (a)tt2 (b) 2t t
(4 'li /2 (d)2/,ti
(D) u,.,,... l()rissa I.E Ir. 2l)0t
66. What is the kineric cnerry of 1g of Ozat 47.C?

.(4U,.^.". 614 u, tPt (b)224xrc7r

(d)u,,,,. = /+ (I.I.T 2004)
(c)1.2/x1dt (d)3 24 x te l

As the temperature is raisd from 20'C to 40'C, the Molar volume of CO2 is maimum at
average kinetic energy of neon atoms changes by a
factor ofwhich of the following ? (a) N.TP. (6) (rc 8trd 2 . 0 atm

(a) 12
(t+72Tcand 1 a.6 (d)273"Cand2atm
@'hB/293
JPrjt3ze3 (d)2 t.t.t.tr r. zLro,tt
iJeKc.L.r2l0t)
rtrhals equati .n of state of rhe gas law, Slope of tlte plot bctreen PV aod P at constaDt
6?. In yaD der
teEperature is
the mnstaDt , is a measure of
o (a) zerc (b) 1
(a) intermolecular repulsions
(c) tD (d) 1/,lz
(6) intcrmolerular attraction
tBtlLt. / .t; (, 1.: )t)011
,1relvolume occupied by the moleqrtes
(d) intermole{ular collisions per unit volume 7lJ The numeri@lvalue of N/a (where N is the nu mber
of molccules in a giln saDple of the gas and ,, is
(.t.t.t;.t:.E. )0ti4\ tbe number of moles ofthc gas) is
6e Containers A and B have same gas. pressure,
volume and temperature ofA are all twice tbat of -qtytla"rP
B. Then lbe ratio of the number of molecllles of A (d)166xlO-le
and B are
(a) 1 12 gfi'r I Kenla C.li.li. 200J i

A
57. a,b,c 5E. bd d,.I
59. 60. c 61, c 62. c 63. b 61. c 65. a 66, b
67. c 6E.c 69.c 10. a 71. b
2174 ),t;t. rt')s Neut Coutsc Chemlxrg llftfl
72. N2 is found iD a litre flask under 100 k Pa prEssure ar( 4+,lltnicn of the following statemcnl about amor-
02 is found in another 3 litre flask under 3m & Pa
L/ phous solids is incorrect ?

rcsultant (a) They melt over a range oftemperature

pressu re. If the tqD flasks arE conne{ted, the
(DfThcy are anisotropic
PrcssurE ls
(a) 310 k Pa (b) zto k Pa (c) There $ Do orderly arrangemeot of Particlcs
azo k Pa (d)365 kPa (d) They arc rigid and iDclmprcssible
G)
(e) 265 k Pa t turolo tLI..L.2001 Knnoruku ( l l. )t1t)l
I

?S. At a certain pressure, volume of the 8as at 27"C is

73. Tiiple poiot ofwater is
20 litre. If the pressure and temperature are
(a) 273 K (b) 3n K doubled, the volume will be
(c) 2o3 K (d) 1% K lirre --
(a) 40 -16J zotitre
(i.lt,rLC.2001 (c) l0.9litre (d) S.zlitre
(u.P ('.|,v.1: 2001

H INT5,/EXPLANATION9 tO M ullci pl e Ch oi c e @,u e sai o n s

rsr/ rf,,r- .1472 = ,/2 = t '414 Tbis is the med' Pressure of moist 8as = 754 rvn. Hence pressure
of water \.aPour = (754-13O) ntttt = 24 run
mum difference in the rate of diffusioo out of the
lltematively,volume of 0 0168 mol of O? at S'I P
gvcn pam.
r t i / .'/M. Molecular mass of HCI (36 5) is = o.0768 x 22400 = 376 3 rd
grcaier than that of NH3 (17), hence HCI will Thus Vr = 376 3ml,Pr=7@mm,T1=213K
diffusc slowly ie. the ring will be formed near the Yz = 428 ml, Pz = ?,'f, = 298ll.
HCI botrle.
C?lcr.llate P2.

"ir-..iE
rx : v McH.
;- ,:\/E
'- t 16 16. Vapour pressure of a liquid depends only on
temPcraturc and not on the volume of the con-
or Mx=64 0 tainer or the liquid.
HiShcr the pressure and iowcr the tempemture,
greater is the density
9. Kinetic eoeriy ofany gas per mole = ; RT. 1r.,,=f+r
11. ncaat= g uH,
'nt= ' 50 .. 32
:. n.,2= t+ / 2,nc2HG= w / 30 uo, 2^ 800

xllr=
w/2 l/2
i7TTi7fi - 177+;nfi 'H, ./_vf
r3030 ls '.=YM;,
21632 16

Pur= xttq x P,o,r1 - (15 / 16) x PtotoI * [Jx;=\E

12. DA
15.
/ D; = '1fi17
Undersimilar
sure, equal volumes
equal number of moles.
p^ Le.Dt= Dsllrls'
coDditioflE of temperature aDd pres-
of differeDt
P t^)t/2

Sases mntain
" +=E
'fhe equaluy holds good only for (b).
t
..Masses of 02, Ne and CH4willbe in the ratio Polar molecules (like H2O) have drpole mo-
32 i 201 16. meDt. As a result intermolecular forces of a!-
17, Prcssure of dry 8as, P = nRT
y'
traction are Sreatcr and so is the critical
= 0.016t x (0 0821 x 1000 760 rnlntm) t tcmpciature.
x 298 / 428 =130run

AAISLC'ERS
e 73.a 74.b 75. b
 2n5
STATES OF MATTER

23. rEPand d1/'ld or dl/'lPI. 37, Mass oI ?2 4 L of the gas at STP = Gram
Molecular mass.

Heme
+=+(#J"' u- A/3RT
v -Tr ,

24. Mass ot the gas rs determined by weiShiog the I (Hz) T (H:) M (Nz)
contaiDer containiDg the gas aDd theo the empty
conulner.
,rN;= M(q)ix'rNt'
ICE. ofa 8as depeDds only on temPerarure-

*+=+=q,=fr=,,0 Trtl^l
z=affix l+

or T(Nr-2T(H2)
nor=4/32= 1/8 mol,,H2 =2/zmol= ) rnol'
'lbtalz=9l8mol
ie. T(Nr>T(H2)
PV =nRTorP = zRTly'
or TGI, < T(Nz).
= (9,E) x (0 0821) (213)11 = 25 21s atm. z=ffi ie. ,ffi'.r
v1/ Tt =vz/'t2le.3oo / 3ffi = Yzt 2ao
or PV <nRT
or V2 = 280 ml or latmxv<lxO0E.21 x273
or V< 22'4lihca.
P
1Y 1 / -11= P 7Y2 / Tx
Mass of l L steam - 1000 x0 0006 =06t=
i.e. (1 xloq/213 =(1 sxv)/(2'13+91) Mass of liquid w8ter. Vol. of Pater = 0 6 cc. Same

or Vz = 88 9c.c. votume will be occ.udcd by w'ater molecules in

steam.
Mol. mass of air = Mas of 22400 cc at STP
= 0 00130 x22400 = 29 12.
,=\41
VD. = Mol. massz. When ,so, uor'
Clausius-ClaPeyrotr equation is Trq To,
P2
.rosq - rr'l Mr", M",
^tL [T2
= 2:30rn-L-rrl
Ttq m:
33. ry-rn*1 =Snr or -@-=g
- wRT dRT
or P=V-M-=-If or trq=**
ThusP-d,PaT.Hence
PrdrTrtz
E=4xT=2x7=
tt t.
43. .=\4r ffi=\ffi
Pv = ,rRT is obsyed by an idcal gas, the Process .x
Le. T44
may bc isothermalor adiabatic
47= aixf;
fFZ56
or Tnr6 = 16 T
35. tx/ t1'2= /Mx;7-Mi =
Lowr rhe densily of the gas, faster it will be filled.
=,/T72 = 1/ 'lZ-
As H2 has lolpest deDsity, it will b lilled first.
ot rN2=rxxrE=56xr/z=79 19 mls-l
45. A1 sa level, atmospheric pressure is hi8h. Hencr
air hashighdensity, This rsan application oftsoyle's
35. Ttle yariation of volume rMth temperature (at mn- law.
stant pressure) is go!'erned by Charles law.
2n6 N eut Co urs c Ch e m i strglftfi
, . 62,'6' is volume correctioo factor. Ir is a measureof the
oa. = \F Ar constant T 4 vrztrr. As H2
cffcctive volume occupied by the gas molgcules.
has least molecular mass, u will bE maximum for 63. For B, I'r = P, Vr =V, Tr =T For A, Pl = 2P,
r{2. y2=2P,T2=27
4e. PV=nRr * {,=fr Apptyin8 idcal gas equarion, PV = n R'll
l'r Vr PzYz
r'.e, no. of moles per litre = P/RT
-- t,V 2p x 2y
50. Some co\r'ateDi sotids like SiO2 (quarrz), SiC, ,,R-q -ttEq - arm-t;II"T
dEmond and graphite have wry high meltlDg n22
points ( - 4000 K). ot -:-
nt I
Pl,v, P.I 4_ (vz
rr -'-{l
Ta ," 1 - 2-r-
52. Volume of 1 mole ofan ideal gas at 273 K and l atm c,r.
is 22 4 L. Volume at 373 Kand I atm pressure will b

v-BI= o o82-x373
= 30.58 L - 30.6 L.

54. Deviations tom ideal bhaviour are cxpressed in

./fr;
Vi ar M^ - 72'

terms of compressibility factor, Z = ;H. nRT

From positive deviations, Z > 1.

55. Initially, partial pressures were equal, As or .- /t RI'

r =V=;6 _ or2
V,
r . '/iZ or ,/T7fr, thercfore amounts difhrsed
x 0.0821 x 300 _!:Jf ,22
out in the same dme will be Hz > ClI4 > SO2. '_ 2s=. r..13111 - -- ST-
Amounts left t ill br H2 < CHl < SO, or
SO2 > CHI , Hz,Hence psor, panou pyr.
= 10 - 0 66=9 33a[m.
vt-TffTTr ,/Ti \2i ,/i
"fRT/"M r'f 20- 2'
s6.,=\F=\F 6r. K.E -lnRr=3#n'
As temperature is consknt, PVis constant. Hence
,:nLJ. is constant even if pressure is doubled. =ir#"8 314 x32oJ = I 24 x r02J

5t. According to Boyle's law, PV = K at constant T 69. PV = RT or V = Greater rhe value of TE,
$.
.. P = KN or (dP/dv\ * -K/v7. greater ls thc volume.

Also Vc 1,t P. 70. Plot is a horizontal line, Hence slope = 0.

59,
v
AccordinS to Charle's lar , + = K al constanl P 71, Nh represents the no. ofmolecules per mole ofthc
gas r:e. Avogadro's no.
or V = KT or (dvldT)p - K. Also V c T.
72. PlVl+ P2 V2 = P3 (V1 + V2),
60. R.M.S. of one mole of a monoatotnic gas is
10ox 1+320x3=pr(1 +3)
,r..r.='F ot P3 - 265 kPa
1
Average K.E. is E-iRT or 2F=lRT 73. Tiiple point ofwater is the temperature at qhich all
the threc phases ic-water-vapour cocxist. ft is
T: 0.01"C = 273. 16 K at 4.58 mm prcssure.
Ur...t, = V ff 75. P1=P, Vl =20L, T1 =T
61. For monoatomi" n"nn E -] RT P2=2P, y2 -'t, Tz= 2'f
",orr,
E4o' Tm' 40 + 271 313 P,Vr PzYz p xZO 2PxV
40. I zo' 20 - 213 2o3
STATES OF IVATTER 2n7

ADDITIONAL UESTI
As se rti
o n - Re a e o n Ty p e Q.u e ons sli
rhe r"rroring q";ilons cotrEilt of t o stot",n*G p"r"u rr AlEcrdo' Etrd Resron, wbllc enuwcrlng
these questions you arc rlqulrld to cho(*. ary oDG ""*,
of thc follorlJlg llyc r6porr...
(a) If both Assertlon aDd RcaaoE orr truc sud thc Rlllor lE corrcct cxpl,rordon ol thc Arecrtlou
(r) If both AsrcrtioE aDd Rrsson rr! truc and the Rcr!'on is not thc coricct cxphnrdotr of ttc Alt rdott
(c) IfAssertlor ls true but thc Rroson b faka
(d) IfAs.sertion is falsc but th. Rcrsotr ls Eue.
(e) Il both AsrertloD ond Rcaaon arc fallc,

Assertion Reason
For a certain fxed amount ofgas, the producr PV Real gases deviate ftom ideal behaviour at lo pressure
is always constant. and high temperarures.
Different gases at the same conditions of tcmpera- AveraSe kinctic enerEr of a ta! is dirccly proportional to
ture and pressure have same root mcan square temperature h Ketvin scale.
velocity.
At zero degree KeMn the volume occupied by a gas All molecular motion cealcs at 0 trC
is negligible.

The pressure of real gass is less than the pressure Tbe intermolecular forcs of attraclion in real gass are
ofthe ideal Sas. greter than th6e of ideal gas.
The pressure of a fixed amount of an kleal gas is Frequericy of colloisions and 6eir iDpact botb iDcrcase
proportional to its temprature. in Proportion to the square root of the tcmperature.
Latent hear of fusion of solid carbon diodde is SiO2 exists a! a discreie molecule.
much less than that ofSiO2.
Liqucfaction of H2 and He is difficult. Critical tcmperarures of tI2 and He gases arc high.
t. The value of van der \lbals constant ,c, is higber Intermolec.ular t ldrogen bonding is prcscnt in ammoDia.
for ammonia tban for nitrogen. (I.LT t99t)
Effusion rate of mygen is smaller than nitrogen. Molecular size of nitrogen is smaltcr than dygen.
(a.r.r.M.s. 2000

True/Falge etatements
Wich of the Io owing stotemefis @e labe ? Revrite 7. A liquid which has high coefficicDt of yiscGity has
them cotectly. lo$, fluidity.
The graph between PV vs. P at constant tempera- E. Glass po$esses fluidity.
ture is linear parallel to the pressure axis. 9. Crlstallioe soli6 are isotropic.
Volume remaining constant, pressure is inversty 10. ID a 8as, intermolestlar forcB of anraction are
proporlional to temperature iD degrees keMn. weakest whilc thermal encrry is bighest-

Real gases shop deviation from ideal behaviour at 11. In the van der Vrbal's equation
Iow temperature aDd high pressures.

In the micrGcopic modol of the gas, all the

f -#l (v -zD) -2p1
molec-ules are luppored io rDovE witb tbe same tbe coortsnt ?' reFcrcotr th sctual \olumc of the
wlocities. gas moleculcs. (r.I.L 199i)
5. A liquid gcts heated up when it qrEporates. 12. A mixture of ideal gases is cooled upto liquid
6. Mercury rises in a capillary tubc. helium temperature (4 22 K) lo form aD ideal
solution. (r.I.T 1996)
2178 NesJ

Fill ln The ?lanke

l. 1 I- = ..... dm3.
t. Boiliog point is the temperature at which the
vapour pressure becomcs equal to .....
t I t-.ar = ..... N m-2. 9. Fluidity is ..... ofviscosity.
-fhc r.slr',,n,.eDi used lbr the measurernent oipres- 10. The crrsmlline parts of the amorphous solids arc
3.
surc ol, a gas is called ..... called.....
11. The SI unit ofviscosrty is-.,.....
4. The absolute scalg of tempcrature was Siven by .. 12. I poise = ......-.th of SI unrt.
A graph betweenvolume (in L)vs. temPerature (in 13. Solid Nacl s a .-... conduclor of electricity.
"C) at mnstant pressure on extrapolation cuts the (Ra*ec 1990\
temperalure ass at ..... . 14. The absolute temperature of aD ideal 8as is ..--..-
6. Aqueous terNion is the \ ,!nur Pressure of ... . and m/than the averagc kinetic eDergy of ttle gas
dcpends only upon .... . moleculcs. (l.I.T. 1997)
The model used to o(Plai[ the proPerties of gases 15. A liquid which is permaneotly supcrcooled is fte-
is callsd ..... quently called a.......... (l.I.T 1997)

Matchin7Ty?e Q.uesaiong
Lfatch thc cntrics of cohnu A with apopti* e*its ol cola,B B
columD A Column B

Rool mean square sPeei (ur.n.r.)

Average sped (!ay)
3. MGt probable sPced (r,,p) /H
4. Kmetic enerry pcr molc

ASSEHTION.REASON TYPE OUESTIONS

l,d 2.d 3.c 4.o 5.a 6.c 7. c Ia 9. c

TRUgFALSE STATEMENTS
2,4,5,6,9, 11, 12. (ideal gasca cannot be liqueficd above 0K)
FILL IN THE BLANKS

1.one2. ld3. manometer 4. Lord KeMn s. -213'C 6.watet vaPours, temPrature 7' Microscopic
model t. e.(ernal pressure (atmosPheric pressure) 9. reciProcal 10. crystallites 11.' Nm-2s
orPasorkgm-ls-1 rz.$rr. Poor 14' drrectly Proportionalto 15. glass.
MATCHING TYPE OUESTION S

1-z2-3,3-1,4-4.

H I Nf 9,/Ex PLA NATI O N I ao As s ertio n -Re a g o n Ty p e G.u e sli on s

z. a= /-j -L, M. so r depends not only ofl T but 9. Molecular size decreases from left to nght aloDg a
penod. Thus, molccular size of nitrogcn is Srealer
than oxygen.
3. \'ihratory motton cxists even at 0 K
7, Crrtical temperaturqi of Il2 and H gass 8r lo\x.
 [, NO UT

Atornic ?t?uctu?e
,,,.,,.'5-. -;E, ,., ;.,9,;:..,,.;

Fundamental particles, Rutherford's modcl of alom.

Nature of electro magnelic radiatio n, c missio n sp cclrum of hyd r o geir a ro r l, co nccf , i e ncrgy Icve/i
r

(orbitals), weaknesses of Bohr's model.

Modern concept of structure ol atom (elementary idea only), idea of shells, subshetts 'nd orbitals
the four quantum numbers, elecirurrir: conliguration of eierirents, Aui r prulciple (!-E ;ir exr: lusi,
principle and Hund's rule).

SECTION-I The charge and mass of these fundamental

particle are given in Thble 3.1 below:
EARLIER DB!'ELOPN{I INIS
ABOUT STRUCTUR.E OF AIOM TABLII 3.1, Clrarge and mass ol lrirrdarrrcrital
subatomic particlc.s
3.1. Subatiomic and Fundamenti-l Particles+:i
Particle Charge Mass
Although the credit for the first "atomic" u
kC
theory is usually given to ancient Greeks, a
landmark in the progress of chemistry took place Electron 1- 9.1(D39x10-31 0.000548596
with the advent of Dalton's atomic theory (dis- Proton 1+ 7.00727663
7-67262x1O-27
cussed in Unit 1).
Neutron 0 1.0086654
Dalton, a British school teacher, in 1808, 1.674/3xlo-27
proposed that matter was made up of extremely
small, indivisible particles called atoms (Greelg
One unit charge = 4.8fl298 x 10-10 e.s.u.
aloms meals'uncut-sble'). The concept continued or 1.6@10 x 10-le coulombs
to hold grounds for a number of years. However,
the researches done by various eminent scientists One u: lll}rhthe mass of 'l2C atom.
like J.J. Thomson, Goldstein, Rutherford, Chad- We shall now take up a systematic study of the
wick, Bohr and others in the later half of the 19th discovery of these fuudamental particles and other
century and in the beginning of the 20th century
have established, beyond doubt, that atom was not
related discoveries which have been made from
the smallest indivisible particle but had a complex time to time.
structure of its own and was made up of still smaller 3.2. Discovery of Electron-
particles like electrons, protons, neutrons etc. At Study of Calhodc Rays i
present, about 35 different subatomic particles are
known but the three particles namely electron, The electrical nature of matter had bcen indi-
proton and neutron are regarded as the fundamen- cated in very early experiments on the production
tal particles. of frictional electricity (i.e. rubbing of glass or

3^
 3t2

ebonite rods with silk or fur). This was further

confirmed by the experiments on the electrolysis of
substanccs by Davy, Stoney and Faraday in the first
half of the nineteenth ccntury. However, the dis-
covery of electron came as a result of the study of
conduction of electriciry through gases as ex-
plaincd bclow :

Mlliam Crookes, in 1879, studied the conduc-

tion of electricity through gases at lowpressure. For
this purpose, he took a discharge tube which is a
long glass tube, about 60 cm lon& sealed atboth the FIGURE 3.2. Production of a shadow of the
solid object by cathode rays
cnds and fitted with two metal electrodes. It has a
a stop-cock (Fig.3.1). This tube
side tube fitted with (ir) If a light paddle wheel (e.9. that of mica)
is connected to a vacuum pump and the pressure mounted on an a-rle is placcd in thcir path, thc
inside the discharge tube is reduced to as low as wheel begins to rotatc (Fig. 3.3.). This shows that
0.01 mm. Now wheu a high voltage (nearly 10,000 cathode rays are made up of nlqteiol pqrticles.
volts) is applied between the electrodes, it is found
that some invisible rays are emitted from the
cathodet. The presence of these rays is dctected
from the fact that the glass wall of the discharge
tube opposite to the cathode begins to glow with a
faint greenish lightt*. Obviously, this must be due
to the fromhardmetrt of the walls by some rays
emittedlrom the cathode. These rays were cathode
rays. LIGHT MICAWHEEL
MOUNTED ON
^xLE
GAS AT
LOW PRESSURE
CATHODE FIGURE 3.3. Rotation of light paddle wheelby
RAYS TO VACUUM cathode rays
PUMP
CATHODE ANODE
o (rii) When an electric field is applicd on thc
cathode rays, they are deflected towards the posi-
tive plate of the electric Freld (Fig. 3.4.). This shows
that cathode rays carry negative charye.
HIGH VOLTAGE
WALL COATED
l. l. WITH ZnS

FIGURE 3.1. Dlscharge tube experiment -

Production oI cathode rays.
LOW
Properties of Cathode Rays. From the VOLTAGE
various experiments carried out by J.J. Thomson (10 volr)
(1897) and others, the cathode rays have been HIGH
VOLTAGE ANOOE WITH
found to possess the following properties : - (10,000 voLTS) ELECTBIC
A HOLE
(i) They produce a sharp shadow of the solid FIELD
object placed in their path (Fig. 3.2.). This shows FIGURE 3.4. Deflection of cathode rays towards
that cathode rsys Eovel in straighl lines. positive plate of the ele.tric field

* lt may bc notcd lhat c,hcn thc gas prcssuE in thc tube is 1 arnosphcE, no clcctric currcnt flows rhrough the rubc. This is
bccause the grscs arc poor conduc-toi of clcctricity.

'.Thc tclcvision picturE tube ii s cathode ray tubc in$hich I picturc is prcduced due to fluorcscclce on thc telcvision screen
coated with stritablc material. Similarly, lluorcsccnt light tubcs arc also cathodc ra)6 tubes coated inside wilh suitable materials
which producevisiblc light on bcing hir with cathodc ray6
 ATOI.TIC STBUCTURE
3/3

_ Simi-larly, when a maguetie field is applied on

the cathode rays, these rays aredeflected in adirec-
Thus the mass of the electron may be calcu-
lated from the values of e/m and e as foilows :
tion which shows that they cary tregative charge.
e 1.60 x 10- re
rays strite a metal foil, the maSS=m=---:-=
ildicaaes
e/m 1.76 x ld
thaa csthode ru)E
gr g.Ll x 10-28

(v) They cause ionization Thc charge, 1.60 x 10-1e coulombs, is rhc
of the gas througlt smallest measurable quantity of charge, and is
which they pass.
callcd onc uait. The mass, 9,11 x 10-28 g, is ncarly
(vi)
They prcd,uce Xroys when they s,ike 7/1.837th ol that oI hydrogen atom. This can be
against the surface of hord metals like rungsten, easily calculated as follows :
molybdenum etc.
1 g atom of hydrogen
(vii)
They produce green fluorescence on the
glass x,alls ol the discharge albe as $,ell as on cetlain = 1.00ljg= 6 02x 1023 atoms
other substances such as zinc sulphide. i.e. 6-02 x 1023 atoms of hydrogcn weigh
(viii) They affect the photogq,hic ptstes. = 1.008 C
(o)rn"y rhey
.. One atom of hydrogeo wcighs
can easily pass Th"i I . 008
are stopped on hick- = 6 a2, 16z:..-
c = l' 67 \ 10' 24
I
ness.
Mass of H atom 1.6'7 x 1o-24 o
From the study of the various properties, as
Mass o[ clectron = ,;t, , ,-r{ = ls::
explained above, the two most importint results
are: Using morc accuratc values, the ratio comes
out to the nearly 1837.
(i) Cathode rays are made up of material
particles. ed as follows:
(r'i) Cathodc rays carry negative charge. rlicle which
The negalively charyed mateial panicles con_ hls a mass
stituting the cathode rays are called electrons. . ttwb eqa to I ll837th oJ tlwt of hydrogen anm.
Further experi.urenG were carried out to
determine the exact charge and mass of the _ Origin ofgatborie Rays. The carhode rays arc
first produccd from the material ofthe cathodi aod
electrons. Tllyo types of experiments were carried tube due to
out. These were by the high
cathode.'
Electron is a universal constituent of matter.

ferent mctals. He placed

He found every time tha
ofthe electrons was the s
to be
charge/mass = elm = 1.76 x 1d coulombVg
the material of the cathode and then procluced
on the from the gas inside the tube as a ,erult of th"
und by
il drop
bombardment high
speed electron **, it
is obvious that
charge : e = 1.60 x lO-leCoulombs st be
universal constitucnt of all matter. This is further
or 4.9 x 10-ro esu supported by the following expreriments in which
*'rhis is callcd Rcst mass of the electrcn
becausc it has bccn calculatcd assuming that lhe electron
much lcsi thin thc velociryof Iight. is movingwith a wclocrry
* No elcctric currcnt flows thrcugh vacuum.
314
Pratla c y's Nett Coursc Chu^i"trrr[frlD
the electroE emitted are fouad to have the same (ii) Thqt are made up of mateial particles -
charga and mass :
- (iii) They are positively charged, asidicatedby
(i) By strongly heating certain metal filaments. the direction of deflection of these rays in the
('i) By exposing highly active metals likc electric arrd magnetic fields. That is why they are
sodium and potassium to ultraviolet rap. callod'positive rays.'
(ai) By exposing any form of matter to X-rays. (iv) Unlike cathode rays, the ratio, chotgelmass
(i.e. elm) is found to be dilferenl for the particles
(lv) From radioacrivo substances in the form
constituting snode rsys when different gases are laken
ofB-rays.
inside the dischorge fube. In other words, the va.lue
I 3. Disco./ery o on-Study of Anode Rays :,r,, of e/m depends upon the nature of the gas taken
insido the discharge tube.
Since the atom as a whole is electrically neutral
and the presencc of negatively charged particles in it (v) The value ol the chaBe (e) on the particles
was established therefore it was thought that some constituting the otode ruys is ako Jound to depend
positirely charged particles must also be present in upon lhe nature of the gqs tsken inside the discharge
the atom. For this purpose, Goldstein in 1886, per- tube. }{ovevet, tle charge on these particles is
formed discharge tube experiments in which he took found to be a whole trumber multiple of the charge
perforated cathode and a gas at low pressure was kept presetrt on the electron. In other words, these Posi-
inside the tube, as bcfore (Fig. 3.5.).
tively charged particles may carry oue, two or thlec
units of positive charge, depending upon the num-
ber of electrons knocked out.
(i) The mass (m) of the paticles constituting
the anode roys is also found lo be different for
difrerent gases taken in lhe discharye tube- Howeve|
its vslue is found to be near$ equal to that oI lhe atonl
of the gas.
_ttz-94._!{91-Qe__ Further, experiments revealed that when
AT Low PRESSUBE
hydrogen gas is taken inside the discharge tube, the
particles present in the arode rays have ninirnum
FIGURE 3.5. Production of Anode rays mass i.e. lightest positively charged particles are
ot Positive raYs. produced. The charge onthese particles is found to
On passing high voltage between the be same as that on the electron i.e. 1.6 x 10-le
electrodcs, it was foutrd that some rayswere coming coulombs or one unit. The ratio, charge/mass, for
from the side of the anode which passed through each ot the particles is found to be 9.58 x 1d
the holes in the cathode and produced green coulombs per gram. Hence the mass of each of
fluorescence on the opposite glass wall coatedwith these narticles will be=
e'. l6x l0-t-9
zinc sulphide. Tbesc rays were called anode roys or e/m- 9.58 x ld
canal rays or positive rays (because theywere found : 1.67 x l}-2/ g
to carry positive charge). Ttis mass is nearly the same as that of the
Origin ofAnode Rays. These rays arebelieved hydrogen atom. These particles were termed as
to be produced as a result of the knock out o[ the protons. Hetrce
electrons from the gaseous atoms by the bombard-
ofthe cathode rays on
not emitted from the
he space between the
?nocle an<Ithe cathode.
It may be mentioned here that in case of any
Propertles of Atrode Rays. Using the samc other gas taken inside the discharge tube, the mass
expcrimental methods, as described earlier for of the positively charged particles was found to be
cathodc rays, the anode rays were found to possess
nearly a whole number multiple of the mass of the
the following main properties : -' proton. Hence it led to the belief that protons must
(i) They travel in straight lines. However their be fundamental particles present in all atoms and
speed is much less than that of the cathode rays.
 ATOMIC STRUCTURE
3t5
that the atoms of gases other than hydrogen con- 3.4. Thornson Model of Atom l:,ir4iir+r:,jii!j:.ti9jii,iiii1t!_l+1:rjiiii
tained some whole number ofprotons.
J.J. Thomson, in 1904, proposed that an atom
Aftcr h was a sphere of positive electricity in which were
electrons and
embedded number of etectrons, sufficient to
before the sci
were present within the atom. TUo models ofatom
neutralize the positive chargc (Fig. 3.7.). The
wcre proposed as discussed iu the next sections. stabilityofthe atom was explaioed as a result ofthe
balance between the repu.lsive forces between the
Rrdloefity. Aftcr thc di6aorrry of clc.fron and electrons aad their attraction towards the centre of
prDton, i t x,as wcll cstablishcd that atorn is divisiblc and is madc the positive sphere. This model is compared with a
up of charged particlcs. This v/as fufihcr confilrncd by thc
water melon in which seeds are embedded or with
phcnomcnon of radioactivity, dir.ovrrld by Bcaqucrrl in ig .
a cake or pudding in which raisins (dried
Radioactivi t b h. phcnoficnon oI sponrorEous anir-
riot of todiariorlt by cduin clcrr@tB Ua w@iyr't todiun cl(,. grapeykishmish) are embedded. That is why this
Thc clcrncntt anifrhg sltch radiatiot$ arc callcd radiooetivc model h sometimes called ralsin pudding model.
However, this model could not satisfactorily cx-
Thc phcnomcnon can bc obscrvcd by placmg thc plain the results of scatteriDg erperimeuts, carried
radioacli!,e clcmcnt in s c.vity rDsdc in a bloct(;f lc.d and
applyi[g clcctric o. magnctic ficld on thc radiarions being out by Rutherford in 1911 and was rejected.
emittcd and thcn allowing them to fa on rhc photographia
plate.
Three q'pes of ftdiations arc enittcd a6 crplaincd
bclova
(i) Tho6ewhic
ti\/e platc and hcncc
Thc paniclcs prcscn
a-paniclc has chargc
arc samc as helium nuclci and arc eprtscnrcd as f,Ic.

platc
callcd
Partic
of clcctrcn. Hencc it is rcp."""ntcd J1". FIGUBE 3.7. Thomson model
""
(rli) Thos. which rcrnain urdcflcctcd of atom.
arE callcd /-rsli.
Tltcy arE simply clcctromagnctic radialions.
I 5. Rdtherlorc s fllcdel (Nuclear t\4odel)
of Atorn-_Discovery ol Nucleus iiti:.i,:ii:::ijiii:it::tiii:.:i:i:,
Rutherfor4 h 1911, performed some scatter-
ing orperiments in which he bombarded thin foils

BLOCK

ligbt is giran out.

From these experiments, he made the follow-
FIGURE 3.6. Elfect ot electric field ing observations :
on lhe radlations emitted Irom a -
radloactive element, . (r) of the s-p3rticles (99.9 Vo) passed
Mo_st
though the foil without undcrgoitrg anydefliction.
.A, a-particlc ia r paniclc wh
othcr worG, thcsa pafticlcs arc nothi . ln
3/6
N e.!

MOST OF THE
c!-PARTICLES
C IRCU LAR STRIKE HERE
ZnS SCREEN
o

FIGURE 3.8. Ruthedord's scattering xperiments'

(ii) Few a-particles underwent deflection

though small angles.
(ifi) Very few (only ooe in 20,000) were def-
lccted bick i.d. through aa angle greater than 90'.
From these observations, Rutherford drew
the following conclusions :
- FIGURE 3.9. Scattering of o-particles b9
icles Passed tkough
(a) a single atom (b) a group o, atoms.
eflection, there must
the atom.
Since electrons have negligible mass, the mass

(ii) Extra-nuctar part i.e. space around the

close to this positive bodY. nucleus in which the electrons were distributed.
(fi| were deflected To exolain that the electrons do not fa.ll into
back and Particles, these the nucleu's as a result of al.traction, Rutherford
could be d theYstrike some
suggested that th
heavier body inside the atom. but were revolving
(iv cted circular orbits. As a
back is eavy into play which balances the force of attraction'
body pr verY Thus this model ofatom is similar to our solar
very small volume .* svstem where the nucleus is like thc sun and the
The small heavy positively charged body eiectrons are like the planets. That is why these
present within thc atom was called nucleus. electrons are also c a)led planetary clectrons .
ng 3 6. Oiscovety ot Neutron ri:i:: I i :l,:i:i:: : :i:i:: ;i: ::::,1:::,::l:i:ill:i:
::

oof
a
Thus, according to Rutherford's model of
atom, the atom consists of two Parts :
(i) Nucleus which is very small in size, carries
positivo charge and in which the entire mass of the
atom is concentrated.
th mdi us o[ th n uclcus
thectod fiediffercnce
isofth of about 5 km
in sizc
r.
No two clcmcnB hEvc thc 6ane atomic numbcl. Hcncc I proPeny of an clemcnt
chart
and is takcn as thc basis of classification of clcmcnts in thc Pcriodic
 ATOMIC STflUCTURE
3n

\__/:(J
G-'(/) \_,i
* o
o-particle Be-atom C-atom Nautron
Charge=+2 Alomic No.=4 Atomlc No.=6 Charge=0
than the actual mass of the atom. This Ied to the idea Mass=4u Mass=9u Mass=l2u Mals=1u
lhat therc must be somc other particlcs prescnt in the I|H" * lae ttc
-+ 3a
nucleus and that these particlei should be neutral but
should have considerable mass.
t( o
o-particle B-atom N{tom Neulron
Charge=+2 Atomic No.=s Atomic No.=7 Charge=O
Mass=4u Mass=11u Mass=l4u Mass=1u
t|H. . 'lB 'f r
* l,l
In view of the discovery of neutron,
Rutherford's model of atomwas modified. The only
modification was that the nucleus of the atom con-
tained not only protons but also neutrons.

MASS AND CHARGE OF FUNDAMENTAL PARTICLES

umber of elecbors .\. Find (a) the total numbet and

wh (N.C.E.R.T.) (b) th olptotons in 34mgo| Nasat S.T.p.
Solution. Mass of one electron (Assame he mass ofproton
= 1.6726 x l0-T kg)
=9 U x 10-31 kg W the answer change if Empcrafu& arrd pres-
i.e. 9.1,1, x 10-31 kg = 1 electron sure an changed ? (N.C.E.-II.T,)
:. 7 g i.e. 70-3 kg (a) 1 mol of NH, = 17 g NHr
1- x = 6 .U2Z
x 10?3 molecules of NH,
= t.lix 10:5 10-r electrons
= (6.022 x t0a3) x (7 + 3) protons
= 1 .09E x 1027 electrons.
late the mass and chage
= 6.U2Zx l0 protons
of on N.C.E.R.i)
.'. 34 mgi.e. 0 .034 g NH,
Mass of one elcctron 6.022 x 7e4
_x
= tl 0.034
= 9' 11 x 10-3r kg
.'. Mass of one mole of electrons
= 1.2044 x ld2 protons.
= (9. 11 x 10-31) x 16.022 x tgz:; (D) Mass of one proton
= S.4E6 x r0-7 kC
x 10-27 kg
Charge on one electron
= 1.67'26
.'. Mass of 1.2044
x 1022 protons
= 1.602 x 10-19 coulomb = (7.6726 x 10-27) x G.Z\M x
. . Charge on one mole of electrons 7021) kg

= (1.@2 x 70-1e) x (6.022 x = 2.0145 x 10-3 k.g

7023)
= 9.65 x 10. coulombs. There is no effect of temperature and pres-

. Actual mass of the neuilon = 1.6749 x 1O-u

E
Actual mass of (hc proton = 1.6t26 x 10-24 g
Thus the actual mass ofneutron is sligtlly larye!
than thar of proron.
3/8
Neut Course Chcn, istrrj

FO".-,P,,R.AC.1trlCE
lac (Assume that the mass of
1, Calculatc thg total number ofelectrons present ln neutrons in 7 mg of
one mole of methaoe, neutron = 1 .6?5 x 10-27 kg) N.c.E RT)
(N.C.E.R.T) [ \rs 6 02z x 102]
[turs. (a) 2.,109 x rdl (r) 4 035 x 10-6 ktl
2. Find (a) the totalnumber and (b) the totalmass of

T 9 FoRotFFtcuvr ?e.oeLr*v,g
l. 1 molecule of CH1 mntains lectrons z, 1 g atom cflaC - 14 g
=6+4=10 = 6 022 x 104 aioms
'. 1 mole ie. 6O22 x 1F moleculcs will coDtain =6 022tlOBx8neutrons.
electrons = 6.022 x 1024

3.7. Atomic Number and Mass Number rrll.li:i.i.:j:::r;:i:i::i MASS NUMBER

SYMBOL
Since the atom as a whole is electrically OFTHE
neutral, therefore the number of positively charged ELEMENT
AIOMICNUMBER
oarticles i.e. protons present in thc aton must be
eoual to the number oi negatively cbarged particles
i.e. electrons present in it. This number is called e.g. ,2fNa, ffcl and so on.
atomic trumber, Heace
3.8. Nuclear Slructure J!:::.,t,,,1,ii:,irhi'r__:1:_j,f::ff_'

tlu nucleus Knowing the atomic number aud mass num-

tha alom ber of an element, the number ofelectrons, Protons
and neutrons in the atoE of the element can be
Atomic number is also known as proton num- calculated. Hence the composition of the nucleus
bcr bccause the charge on the nucleus depends can be known.
upoa tic number of Prototrs.
For example, if'Z representsthe atomic num-
ber of an element and 'A represents its mass num-
ber (or atomic mass rounded off to the nearest
whole number), then
No. of electrons = No. of Protons
- Atomic number (Z)
and No. of Protons + No. of neutrons
atom. This is called mass number. Hence = Mass number (A)
Mos nuaficr d'endefrr a 'No' alFobrt .'. No. of neutrons : Mass number (A)
+ ilo' d'Eutmns'
- Atomic number (Z)
The mass number of ar element is nearly e.g. (i) For sodium'
atomi
equal to the ever'
:
thq main differen tuT Atomic number (Z) 11

number is alwaYs omlc

Mass Number (A) : 23
mass is usuallY not a whole number'
No. of protons = No. of electrons
: Z= ll
The atomic number (Z) and mass number (A)
and No. of neutrom: A-Z
of an element'X' ar" uso"ilyteptet"oted alongwith
the symbol of the element as =23-ll = 12
 ATOIVIC STRUCTUBE
3B
Thus the nucleus of sodium atom contains 11 special names. They arc repre,sented by simply in-
protons and 12 neutrons drcating I hc virluL,. r rIA t,rr thc svmlrrrl. For- cximple,
(ii) Forchloine, Atomic num[er (Z) = ]/ isolopcs , 'I chlo1in1. rrrc wr ilcn as ]5Cl and 37dl-
Mass number (A) : 35 2. Isobars. Some ;rtoms of different elements
. . No. of protons : No. of electrons =Z are tbund to havc samc mass rrumber,

=17 Such qtime ol differcn elemenrs which heve safil

and No.ofneutrons: A - Z:35-17
=18
Hence the nucleus of chlorine atom contains
17 protons and 18 neutrotrs.
Isotopes, Isobars, Isotones and
tronics.
1. Isotopes. In some cases, atoms of the same
clcment are lound to contfi thc same number of
lrotons hut dillerenl number of neutrons. As a
result, they have the same atomic trumber but dif_
fcrsnl mass numbets.
SrEh atoals of tlu saau ebte* lwiag sanw
alomic awrber bill difierart mN ,ut nhr-E are
callcd imtopa.
For example, there are three isotopes of
hydrogen having mass numbers, 1, 2 and 3 respec_
tively and each oi them having atomic number
equal to 1. They are represented as
]H. ]H and
lH and nan:ed as protium, deurerium (D) and
tritium (T) respoctively. Ordinary hydrogen is
protium. Isotopes of other elemerts do noi have
,nass.t umbe6 ( snd of coursa difiercnl atomic num-
ben) arc catld isoban
e.g.,lfufs, fipe.
..__
3. IsotoDes. It ma}, he noted that isotopes
Isoelec- differ in the numbcr of ueutrons only wherlas
isobars differ in thc numher o[ neutrons as wcll as
protons. However some atoms of diftcrent ele_
ments are found to havc tllc sano ntrmber of
neulrons.
4. Isoelctronics,
Thc
lluies (aloms or ions) cotusining thc samc
number oJ elcctrons are culled iJoel&tronie.
For example, o2-. F-, Na+, Mg2r, Al3+, Ne
all contain 10 clsctrons sach and hence they are
isoelectrtxic.

IO.,N N Uc LEAR sTR UCTU RE

. Wite the complete rymbol

for .. No. ofprotoos = 92
given atomic number (Z) and
and No. of electrons : 92

\i)z: lZA = 3s(ii)z = e2,A = 233 Further, No. ofneutrons : Mass number

(iii)z: 4n '- e (N.C.E.R.T,)

_ Atomic number

Solution. (,) ?;Cl (,r;r3u (ilr:Be. =A_Z=238_92=746.

Find out the atomic numbe4, mass
numb pmtons, elecnotls and neutons
present in the element with the notation U.
72E

Solutioq. Atomic number (Z) : !t The volume of a sphere

Mass number (A) _- 238 : 4r ;,4 wherc t is the radius of the sphere.
But we know that
.. Volume of the nlcleus : 4n F /3.
No. ofprotons : No. of electrons
= Atonic number (Z) = 41u (10-1)3nc#
3/10
Ne.4 Course Chemistrg

Similarly, volume of the atom But in the formation of calcium ion, two
elcctrous are lost from the extranuclear Part ac-
= k ln = AIt (lo-\3 n cmt cording to the equation Ca -r Ca2+ + 2e- but the
.. Fraction of the volume of atom occupied compoiition of the nucleus remains unchanged.
4 r7 110-13)3/3 cm3 _ .. No. ofelectrons in calcium ion
-- 20-2 : 18
by the oucleus 10_15

Mass number (A) = No. of Protons

tiX,i|-UPUt 4 ComP lete the follo$'inB lable :
+ No. of neutrons
Particle Mass Ato,llc Pro- Neu- Elec-
No. NG tons trons trors =21 +2.A=40'
Niuogen 7 7 For oxygen atom.
anm Mass number (A) = No of Protons
Calcium 2n m + No. of neutrons
ion = 16 (Given)
Orygen 16 8
Atomic No. (Z) : 8 (Given)
alom
45 36 No.ofProtons:Z=8,
Bromide
ion No.ofelectrons: Z = 8
qolu_!!g!. For nitrogen atom. No.of neutrons = A'Z = 16-8=8
For bromldc ion.In the formation ofbromide
No. of electrons = 7 (Given)
ion, one electron is added to the extranuclear part
No. ofneutrons :7 (Given)
of ihe bromine atom accorditrg to the equation
.'. No. of Protons =Z : 7 Br * e- -Br- but the composition ofthe nucleus
remains unchanged
('.' atom is electrically neutral)
Since the no. of electrons in bromide ion:36
Atomicnumber: Z:7
. (Given)
Mass No (A) = No of Protons
' No. of electrons in bromine atom
+No. of neutrons
:7 +7 --'36-1:35
=L4
Further since inthe above reaction, nucleus of
For calcium ion' the bromine atom remains unchanged'
No. ofneutrons = ?-0 (Given) ; ..
No. of protons in the bromide ion
Atomic No (z) = 2n (Given)
= No. of protons in the bromhe atom = 35'
.. No.of Protons=Z=2n\ Putting the values of the various vacant place
No. of electrons in calcium atom as calculated above, in the table, we have
=Z=20
Atomic No. No. of protons No. of electrons
hrticle Mass No'
(A) (z) (z') (z)
7 7
Nitrogen atom 7+7=74 7 7
20+fr = 4O m 2T m 2fr-2=78
Calcium ion
Orygen atom 16 8 8 16-8=8 8

Bromide ion 45+35 = 80 35 %- r=15 45 36

,lilx.1\1i'l,li 5.
Calculale the percentage of xx22+ (lW-x\?l - 2i.z
higher isotope of neon which hos atomic mass 20'2
100
oia tt itoiop"i nove the fiass numbet 20 aad 22' or22x+2100-2frx=2020
"
. SupPose zNe = xVo. or 2x=20
Then 2otle
= (100 - r) 70 ol x = lo i e. 22Ne = l07o
ATOMIC STRUCTURE
3111

PKO7LEMO FORiFiRA iE C"

1. Neutroos can be fouod in all atomic nuclei except in one case. Which is this atomic nucleus and wllat does it
coDsist of ?

Hon, many nuclcons are present in an atom of Nobelium, t How many electrons are presenr in the
ffiNo
atom? Hou, marry nuclmos may be considered ss neutrons ?
3. Crmplete the fo[oying uble :

Particlc Atomic No. Mass No. No. ofelGctrons No. of protons No, o[ neutrons
Sodiumatom l1 t2
Aluminium ioo 27 10
Chloride ion 18 18
Phosphorus atom 31 l5
Cuprous ion
-
28 ;
4. Complcte the follof,ing table :

Name ol the portlcle Moss No. Atomlc No. Piotons No, of Electrcns Neutrons
Oxygeo 8 8
Sodium ion
Bromine
23
l 35 45

5 Find the number of prorons, cledrom atrd neutrons itr

1ay f]af3+1ay |sOz=
6, How many ncutrons and protoDs are there in the foltosring nuclei ?

lrc, l.o, ?rMs, IfFe, !gsr. (N.C.E.R.T.)

1. The nucleus ofhydrogen atom does Dor contain any

neutrons. It consists of only one proton,
Cl- ion : e- = 18. Hetrc e- in Cl = 1?

2. Nucleons = 254, electrons = 102 aDd ncutrons Z=p=17

= n = 18., A=r,+p=18+17=35
254-1O2 = 152
3. Sodium atom: Z Patom : A = 31,p = 15.HenceZ = e- = 15
= tt,p = e- = lt,
A=p + n =11 + 12=2j n=A-Z=31-15=16
Al3+ ion : e- = 10. Hence e- in Al = 13, Cu* ion: e- = 28. Hence- in Cu = 29,
:. Z=p=13 Z=p=29
A=27,.. n=27_13=14 n=35 A=n+p=35+29=64
Particle Atomic No. Mass No. No. of clectrols No. of protons No. of neuttus
Sodium 11 2i 1l t1 12
Aluminium ioll l3 27 lo 13 t4
Chloride ion l',l 35 18 l7 l8
Phcphorous atom t5 3t 15 15 16
Cuprous ion 29 ?a 29 35
3112

Nome of the parti(le Msss No. Atomic No. Protons No. of Electrons Neutrons

16 8 8 8 8
Oxygen
sodium ion 11 11 10 12
80 35 35 35 45
Bromine
s. (a) P - 13,e- = 1O,n -- 14 (b)p =8,e- = lO, n ='1.
6. See HiDts belolr.

H lNT9 FoRDtFFtcut:r ?e.ooLEuo

s. rorllN,z = p = e- = t3, L = 2't' 6.
rc,,p = 6, n ='7 ;
.. n=A-Z=17-13=14,
A6C),P=8,t'=8;
e- in Al3+ = 13-3 = 10
1true' P=72, n--12,
ForfO,Z= P = "- = 8, A = 15 sffe, p 26, n 56-26 3O',
.. n=A-Z=15--4=7 = = =
e- inOz- = 8 + 2 = 10
!!sr,p = 36, z = 88-38 = 50.

{tr;p1p,;: iU,R,K'N,O,WL
It is helieved lhat fundatnenlal particles likc protons and neutrons are made uP
q combination ofelementary
ftactionalcharges and crtain
;;fti;;;r"d i;"[. it "i".i"r.nt"ry pahicles lquarks) are believed to have

ProPerties like colour and flavour.

lii:ii -1. The rest massofthe elecrron is 9.1095 x 10-31 kg. On the atomic scale, the rest mass of the elecron.=
0.0005486u.Itisthemasspossessedbytheelectronwhenit,ismovingwithavelocitymuchsmallerthanthe
p;: where c is
velocity of light. However, wheD it is moving with velocity l,, its mass is given bym = ,,/
I_ 1, r ciz
thevelociryofltsht.ThuswhentheeleclronismovingwiththevelocltyotliSht(sothaiU=c),itsma.ssisiofinite,
to the relation
r.rr.!r .l. The radius, r of the nucleus of an atom is related to its mass numbr, A, according
, = Ro o"' where Ih is a c.onstant having value = t 4* 10-15 m'

iii:ir {. .Ihe
rad:us of the nucleus isofrhe order of t0-15 ra while that of the atom is of
the order of 10-10 rz. Thus
nuclear radius is 1/l0O,0O0th ofthe atomic radius'
,iiil 5. The volume of the nucleus is of the order of 10-45 rz3 while that of the atom is 10-I rz3. Thus volume of the
to atom'
nuclcus is 10-15 of Lhat of the aiom ie. nucleus is very small in size as compared
i:;:ii 6. 'Ihe radiiof the nucleiare usually expressed in terms of Fermis (1 Fermi = 10-13
gm = 16-15 ,;
The nuclear radii lie in the range of I 5 to 5 5 Ferml'
Iili 7. 11.," nr.,"u, nas uery trigtr i.e. tora gtcml lor t0l7 kgzz3 or 10t tonnes/cm3; which is about 1012
oe;ii
times that of lead.
ti'
9. n.

10. Moselcy in 1913 He found that wtlen cathode rals hit the
6 aharacteiislic of the element bombarded'
,:.ll.Thomsonwasawarded1966NobelprizelnPhysicswhileRutherfordwasawardedl90SNobelprizeln
chemistry for studies on chemNtry of radioactive substaDces
 ATOMIC STHUCTURE
3/13

'
,-11L.,,,.
:r'lllll-lit()r
. \ I' tr
(rd) The radiations possess wave character
and travel with the velocity of light (i.e. nearly
1 r R.\ \ r ol )t.t,
-.Y1t1_!i ''"rjir'.- 3 x ld m/sec).
.- -::-: ': "' =''''"' ' " .,''
"'''''t' Because of the above characteristics, the
It is observed radiations are called Electromagnetic radiations
teristic line spectra or Electromagnetic warcs.
not be erplained
. _.(rr) equire any material
nuclear model of atom. Itr order to understatrd line medlu-Ilr example, rays from
spectrum it is essential to understand the nature of the suo ce which is'a non-
light (or radiant energy) which in turn was ex- material
SoEe imlnrtart ctaracErlsdcs of a mve.
The main characteristics of a wave are its
wavelength (l), frequency (rz) and velocity (c).
atom sullered from a serious drawback. Hence a These are defined as follows :
new model of atom, ca.llcd Bofu,s model of atom
was put forward. This model of atom was able to
explain the drawback of Rutherford,s model of CREST<-7r-+CREST
atom and the main lhes of the hy&ogen spectrum.
Now we shall ta-ke up a brief discussion of the
above developments one by one.
3.10. Nature ol Electrornagnetic Radiation
(Electromagnetic Wave Theory) Hfl_,iffiffi

This theory was put forward by James Clark

Maxwell in 1864. The main points of this theory are FIGURE 3.1 1 . Some characterrstics of a wave.
summed up as follows :
Wavelngth of a wave is delind os tlv ili an3e
bdveen ary two conscr;uive c?ests ot trouqhs. It is
reprcsented b! ), (lamhda) and is rrprused in or I
m or cm or nm (n4nofiEto) ot W biconater).
rudiant enetgt.
1 A = 10-8 cm = 10-10 m
ist ofelectricand mag_
netic ndicular to each othJr 1nm = 10-9 m, 1 pm : 19-12 p
and to the direction of Frequency a/a wave ir dcfined at tlu number of
propagation of the radiation (Fig. 3. t0) . wava past,l,g througft a polnt ifi ono second. It is
reptw ed by u (nu) and is *pressed in Hefiz (Itz)
Electric,leld or cyulzs/sec or simply srr- L s7 s-t .
component
1Hz = l cycle/sec
Yelcxlty of a vaw is defined as the lincar distance
traveltcd by lhc N,aye in onc second. It is reprc-
seucd by c ond k eqtressed in cmlscc ot
mlec (m s-t ).
Besides the above three characteristics, two
other characteristics of a wave are amplitude and
FIGURE. 3. 10. Radiaton colEidng of ekctic ard wavc number,
rnagn"tic flelds o-scilhting ln phnc. peryendi(llh,
lo each other and trolh perp.ndlcular to the dilPdlon
of propagDtlon. T}y have same warelenglh, lrcquency,
speed and amphude.
gl14 , Pradeep's

Electromagnetic spectrum. The different

types of electromagnotic radiations differ only
in- thcir wavelengths and hencc frcquencies.
thc reciprocal
'lhel;. wavelengths increase in the following
i (read as nu
order : -
_1
u:T Cosmlc rays < )r'-rays < X'rays < Ultnl-
If ,l is expressed in cm, 7 will have the units vlolct rays < Yisible < Infrared < Mlcro tvavs
cm '.
< Radlo wrves
Rclationship betten Yelocity, waYelength
and frequency ofa wave.
ber of waves passing thr
and,tr is the length ofeach
will givc the velocity of tbe wavc. Thus

.c=vx1
INCREASING WAVE LENGTHS

l016 lola rol2 1o1o 1or ld rd 1d2 100 102 1.oo

o
um)
;INFRA
i 'iEU'
ULTRA; MICRO M.qIq
r.RAys X.RAYS vjb'rti i_ iiAVdE wAvES
'Bi+g'
,(r'1) 106
1 lolE \1 1

ES.
,I(CREASI NG FREQUENCI

3AO .'430 450 490 550 590 650

l,(nm)

o
l,(nm)

FIGURE 3.12. (a) ComPlete electromagnetic sPectrum

(b) SPectrum of visible light

,la l. Carcu late (a) wcve number and (D) Calculation of the FrequencY
I,lX AI tPt
(b ) freEte.ncy ol ye tlow rudiation s hav ing wavele ngth
FrequencY z : f
ol 5800 A.
Solution' (a) Calc,ulation ofthewavc number Substituting c =3 x 108 nilsec
Wave number (7) = 1/l and l:5800x 10-1om
But i = 58004 (Given) we get
= 5800 x 10-10 m 3 x 108 nr./scc
i=
-L ' = ssm ,. 1o=o .
"' 58oillo:ril; = 5.172 x 10r' sec-r or cycles/sec or Hz.
= l'72 x 16 m'1
ATON,4IC STRUCTURE 3/15

EX I\IPLE 2:A particalatadio stationbroad- 3 x 1d ms-l

we have l. =
casts at alrcquency d 112! kHz (kilohe,fr). Anoher . 1t20 x 1d s-r
radio station bmadcasts at a lrequency of 98.7 MHz
(Megohea, Wat are the wavelenglhs o[ the radia- 267. t5 m. :
tions from each station ? (r) Calculation of wavelengtt corresponding
(a) Calculatlon of mvclength cor- to a frequency of 9t.7 MHa
responding to a frequcncy of 1120 kHz c
Wavelength, X
7)

Wavelength, X = i' Substituting c:3x1dms-l

Substituting c :3 x ldms-r and v = 98.7 MHz
and v = 112) kHz. (Given) = 98.7 x ld cycles s-l
(1 MHz = 1d cycles s-r)
= 7120 x ld rycles s-l
kHz :(1 ld cycles s-1)
we set- I. 3 x 108ms-l
98.7 x 1d s-r
= 1120 x 1d s-r = 3.0395 m.

F{.".': Ir,eE '.

"ROfiLEMg of
1' Calculatc the frequcncy ri
x tdnm- 1,,,. 10lrs-r1
havinS wavclength,3
infrared liatrons 5. Find rhe.frequency ofvisible light with wavelength
of5000A 1, 6x10t.sec:r1
2. Cllculate thc rangc^ of frequencies of visible light 6, Yello\p lighr emitted from a sodium lamp has a
from 3800 - 7600 A. waveleogth (r.) of580 nm- Calculate the frequency
Il (v) and the wave number (D of the yellow light.
[,\os. 3.95 x 10r' to 7.89 x l0l. s-
3, How long would it take a radiowave of fregueDcy, [ 517 x lorts-r, 172 x 1o5n-1]
6 x ld sec-l ro travel from Mars to thc Earth, 7. Calculate the wavelength, frequency and wave
a
distance of 8 km ? x 107
number of a light wave whosc period is

4, Calolate the qavc numbcr of radiations having a

2 0x 10-ros. (NC.E.R.I:.)
frequency of4 x 10la Hz.
1 \r:. 1 33 x 10a cm-r; [ 6 0 x 10-2ar,5.0 r 169r-1, 15.652-11

H lNl-5 FoR prFFr cuLT ?r.ort:-;wo

7' t 3, r^= x x l0-9n1
- 8 x 107 x 1d
(3
= ... .Ilmekken
106 106)

=3x70-3m 3x108
,=!=3xto8rru-r=lonr-l = 2.66 x lG sec
" 3 x l0-r rz = 4 min. 26 sec:
2' ). = zeoo A 3800 x 10-l0rz 3.8 x
= = 10-7rz 4. e = 4 x 1ot1 llz (i.e. s'1).
c a x 108rru-1 vevenumuerr=|=|
"- i = ;ffi+;= 7.8e x 1014s-r

l, = 7600A : ?600 x lo-to m = 7.6 x 10-7 m =###= t'33xt6m-l

, = Tc = --------------,-
a x 7oB ms-1
3.95 11 1614r-l ., *#==r.33xldcm-l
^ 7 6x1O-'m -
3. All radiations in vacuum ravel with rhe same 6. Similar to sotued erGmple l.
speed, !.e.,3 x 1d m sec-l
7. Frequency (v; =
Disbnc to b travelled from Mars to the Earth
=
U,ja, =
,o x+fir-t
8 x lo7km 8 x 107 x 1dm(l km = ldm)
= = S x 109s-1.
3/16

3.11. Limitaiions of Electrornagnetic Wave observing the amount ofcurrent flowing, the kinetic
Theory (Particle nalure ol electrornag energy oi the electrons can be determined.
radiation ; Planck's Ouanturn Theory)
Electromagnetic wave theory was successfirl in
explaiaing the properties of light such as interference,
diifractio-n etc. but it could not e':cplain the -J+
ohenomeua of 'Black body radiation', and
iPhotoelectric effee' which could be cxplaincd only if
e9
electromagtretic waves are supposed to harrc particle
nature. Each of thqse is briefly desoibed below :
(1) Black body rarlladon. If any substance
uli$ high 6slting point (e'g. an iron bar) is heated
it frrst Secomes ie4 tlen yellow and frnally besins FIGUHE 3.14. APParatue lor studying
to glow with white light' photoelectric elfect,
id However, the following three imPortant facts
tlu
are observed about the photoelectric effect :
(i) The electrons are ejected only iftheradia-
tion striking the surface of the metal has at least a
minimum fiequency (v6). If the frequency is less

than ro, no electrons are ejected. This value (vo) is

called Thrtsbold Frequency. The minimum enetgt
required to 4ect the elecffon (hv) is called wolk
functlon (l{o).
vary as the heating is continued. (ri
gy) of t
(2) Photoolectrlc efrffLwhen radiations with
quency
certain minimum [reTtenq (v) strike the sa(ace of
of its intensity.
a metdl, he eleclruns an ejected lrom the surface of (iii) The number of photoelectrons ejected is
the metal (Fig. 3.13). This phenomenon is called proportioual to the intenslty of incident radiation. .
photoelectic effect The elecfions emitted are called
photo-elecfions. The above observations cannot be explained
by the Electromagnetic wave theory' According to
ENEBGY OF this theory, since radiations are continuous, there-
ELECTRON = **" fore it should be possible to accumulate energy or
the surface of the metal, irrespective ofits frequen-
cy and thus radiations of all frequencies should be
INCIDENT able to eject electrons.
LIGHT - Similarly, actording to t-his theory the energy
of thc electrons ejected should depend upon lhc
intensity of the incident radiation.
Platrck's Quanturn Theory. To explain the
ohenomena ol 'Black body radiation' and
iPhotoelectric effect,' Max Planck in 1900, put for-
FTGURE 3.13. Photoelectdc eflect ward a theorv known after his name as Planck's
studying the ouantum theorv. This theory was further eKended
by Einstein in i905. The main points of this theory
ph
^of
3.14.It consists
al surface to be are as follows :
-

are ejected which move towards the detector. By

 ATOMIC STRUCTURE 3117

(ii) The eneryt ol each quantum is diectty (i) When lighr of somo particular frequency
propodionol to the frequency of the radiationr,i.e- falls on the surfac.e of metal, the photon gives its
Edv entire energy to the electron of the metal atom. The
electron will be dislodged or detachd from lhe
or
mstal atom only it the enerry of the photon is
where /r is a proportionality constant, called sufficient to overcome the force of attraction of the
Planck's constant. Its va.lue is approx equal to electron by
6'626xl0-u ergsec. or 6.626 x 10-sjoules sec. electrons are
(iii) The total anount of energ) emitted or ab- has a certain
sorbed by a body will be some whole numbet quanto. quency v).
Hence E: nhv (rI) If the frequency of the hcident tighr (v) is
where n is any integer. more than the threshold frequency(v), the excess
energy (hv -
ftvo) is imparted to the electron as
kinetic energy. i.e. K.E. of the ejected electron
= hv - hvoorlma, = h: - n o.

light of these views, Einstein in 1905 proposed that Hence greater is the frequency ofthe incident
ligit has dtal character light, grealer is the kinetic encrgy of the emitted
E phnedon of Black body radiadon and electron*'.
Photoelectric eltect
Explanation of Black Body Radiation. When
some solid substance is heated, ttre atoms of the
substance are set htooscillation and emit radiation

REMEMBER
acqu ed by an elxlron when it is s.-
vougfi a potcatial difrerene of onz volt
E_xplanauon of Phototectric efiect. plaack,s ebctnn-volt (1 eV)
quantum theory gives an explanation of the dif-
ferent poirts ofthe photoelectric effect asunder: leY =1.6V2 x 10-reJ

. . in thc visiblc light, atviolct radirtioos havc rhodmum frEqucncy and thc rcd radiatiois
-'Thus (he
havE rhinimum fraquenc1,
t.d lish r. simitarry, rrc urrraviotc rigur hal uishc; hcrE/ rha! thc violc. risht and rhc i;fra;?
f:l:r.g:1":lT -.::]ryllT
ngnr na5 lcs5 c'lcrgf uratr clcn Ihc ted light.
.rlf of
kinctic cncrgr
- (Fi&
ploticd egdn t rh! fEqucncy of thc abrorbcd phorons, a straigfir tinc
oJ slopc ,,r is obtaincd i photoc[ctronc is ptoitcd against intcnsity of tr," in"io"ri-?iuti*
(kceping frcquency constant as shc,!*n in t{& 3.d (r)

to

lrF
Ft I
os I

".E-,I
Er

FREOUENCY OF ABSOFBEDPHOTONS INTENSIIY OF INCIDENT RADIATION

FREoUENcY)
FIGURE 3.r5. plot of kinetic energy of
ph".""bl['"tll"?mJ3T
Ir]fr..|,rd.,..,ofah"ortre.jDt.^to,]r(b\'..^'..l.',.."til."i.l,r^;,.;d;;-.....=-.o'"
3/18 Neut Course Chemist !

|!.{i$}.&f,ERHflA:t '-9ilt,purucx's
GUANTUM THEOHY
AND PHOTOELECTRIC EFFECT

(i)E = hv,c =vl

where h=Planck's constant =6 625 x 10-34 joulgs scc.

v = frequency iD cycles/sec or sec-1, E = enerry in joules

c = velocity of liShtinmsec-1 = 3xlosrn sec-1
I = wavelength in metres (z) [1A = 10-10 ra]
I
(ii) KE. of the ejected electron, ! m u2 = hv - hvo

where lz = mass of the electron in kg,

u = velocrty of the ejected electron in,l1 sec-1
v0 threshold frequency in sec-
1, , = incidcnt ftequenry in sec- 1
=

.'. No. of photons emitted per sec

g oI 25 Js-l
=t#i,=nl=7'18x 10re'
Solution. (i) Frequency v =
f . EXAXII'l.ll 3. Calc'ulate the kinetic energt of
x ldrn sec-l
Substitutingc = 3 the electron eiected when yellow ligfit ol frequency
f=6000A=6000x10-rom 5.2 x l|ta sec-l falls on the surface ol potassium
3x ld metizl. Threshold {requency of Potassium is
wegetv= =5x101'ser-l 5 x 10t
a
sec-l.
6000 x 10-10 K.E. ofthe ejected electron is given
(ii) Energy of the Photon E = /tY by
Substituting lr = 6'625 x 10-3ajoules sec
v=5x10rasec-r l^r"=nu-hvo=h1r-uot
=6.625 x 10-x (5.2 x 1014 - 5.0 x 1011)
we get E = 6'6?5 x i:O-Y x 5 x 1011
= 6.625 x 10-x x o z x tora joules
=3 3125 x l0-l'Joules.
r IiXA,r\'ll'l,Ll 2. A 25 watt bulb emits = 1.325 x 10-20joules.
monochromalic yellow light of wavelengh of 0 57 EX.r$fPLlt r. A photon of wavelength
pm. Calculate lhe rate of emission ol quanta per .
x
4 10-7 m strikes on metol sutace, the wo* func-
second. (N.C.E.R.T)
Solutlon. Energy emitted by the bulb = 25
watt=25Js-l (... lwarr= tJs-r)
(i) EnergY of the Photon (E) : lrv
Encrry of one Pho roa (E) = hv = h * x (3x 1d)
hc. (6.6i26 x 10-34)
Here I = O'57 Pm = O'57 x 10-6 m ,{ 4x 10-'
(lPm=L0-6m) = 4'9? x 10-r' J
Putting c = 3 x ldms-1, 4.97 x lo-re -.
\,=3.l0eV
- 1.602 x 10-le " '
h = 6.62 x L0-31 J s, we gt
(ii) Kinetic energy of (] lzr')
(3 x 1d ms-r)
- _ (6 62 x 10-s xJs)70-6 "-i..ion \z)
O'57 m =hv_hvo
= 3 48 x 10-1eJ = 3' 10 - 2'13 = 0'97 eY
 ATOMIC STRUCTURE 3/19

Energ5r of a photon of radiation of

Qii+mu2 = o.s1 ev wavelength 300 nm will be
= 0'97 x 1 602 x 10-re J
l- r.=nv=hI
i.e.;x (9-Lt x r0-3rkg; x u2
(6.626 x lo-3'rJs) (3.0 x ldms-r)
=O'97x1.602x10-reJ (300 x 10-e rn )
or u2 =0'!47 x 1012 = 34.1x 1Ol0
= 6. 626 x ll-te !
or u=5.E4 x ldms-!. . . Energy of 1 mole ofphotons
' r.\-rll I't.t
Elcctrons are emi ed with zero
a.
= (6'626 x 10-re J)
velocity from-a metol surface when il is exposed to
radiation of wavelength 68(n i. Colculate the
x (6.022 x tF mol-l;
threshold frequency and work lunction (Wi oJ the = 3.99 x td J mol-l
metal. N.C.E.R.T)
as E = Eo + K.E. ofphotoelectrons emitted.
Solution. Threshold wavelength (,lr) .'. Minimum energy (E ) required to remove

= 6800 A= 6800 x 10-10 m 1 mole of electrons from sodium = E K.E. -

Asc=Y^ %=fc = 3.0 x ld ms-l - mol-l
= (3.99 1'68) 1d J
680010=16; = 2.31 x ld J mol-l
l0l's-r .'. Minimum energy required to remove one
= 4.41 x
Work function (Wo) = l,ro . 2'37 x 1d J mol-r
= (6.6i26 x 10-34 Js) (4.41 x l0t1r-1)
electroa=
ffiffifri=r=
3.84 x t0-reJ.
The wavelength corresponding to this energy
= 2.92 x lo-re J can be calculated as follows
' I\\\ll'l.l 6 Vt/hen electrumagnetic mdiation :

oI vravelength 300 nm falls on the surface of sodium, e=nv=hi

electons arc emitted with a kinetic energ of
1.68 x ld l mot-t. What is the minimum lnerg
needed to remove an elechon Ircm sodium ? What is
the maximum wavelength thqt teill cause a
photoelectron ta be emitted ?
(6'626x l0-v Js) (3.0 x ldms-r)
... t' = !!=
E 3'84x lg-teJ
= 5.17 x 70-1 m = 5L7 x 7O-e m: 5l7nm
(N.C.E.R.T.) which corresponds to the green light.

i:::kt#pL._Et\49 FCR,.FI ;fi. { i

1' whar !s the eoers/ of a more of phorons of radia- s, A 1oo watt bulb emib monochronratic light of
Iions whose frequency is 4 x 1014H2? ! 4OO nm. Calculare the num&r of
"velength
Photons emitted Per second by the bulb'
[\rr. 159,6kJmol-l]
2. whi liqhr
oroD of red N.C.E.R-T) ['\tr\' 2 01 x 10p]
wilh photon of gre-en 6, Find the energyofeach ofthe phorons whrch
liSht ? [ \.. crrenl (i) corresponds ro lithr offrequency 3 x 101i Hz
3. In rhc uttravioter region of rbe atomic sry3lT of '
6t,) frave wavetengtiof O.5O A. fNC.e n.il
hydrogen, a line is obtained ar 1026 A Calculare
the enerry of phoron of rhis wavelength (i) 1{EE x 10-ltJ(ri)3 9sxlo-tsJI
(h = 6-6i25 x 10-3a J-sec).
- 7' the nu^m-ber of photons of liSht with a

r\ \ 1e37xlo-rsJr
4. In the infrared region of rhe atomic specrrum of )i,:jffi;I*'ffi.:iJ;,".:;1";
e Light ofwaveiength 4 falls on the surface o?
bydrogen, a line is obtaiDed at 3802 cm - 1. clcu- cesium. cllculate the ener$r of the photo-electron
latc the enerry of rhis phoron (, = 6 .6 26 x l0 -34 J emitted. The crirical wavelength for photoelectric
sec). l,,i z.sO x to-aJl
etlect in casium is 6600 A.

[ \u" 1.95 x lo-r9joulel

3l2O

f,F.AQtlCE PROUL EVs C'-ri rl-i-)

9. What radia-
ratio berween rhe energies of-two
is the 11. Electromagnetic radiation ofwavelength 242 nm is
tioni, one with a waveleDgth of 6000 A and tne jusl sufficient to ionize the sodium atom. Calculate
othe;with 20oo A U [= 16-ro-1 r. t'' lr rhe ionizarion energy ofsodium in kJ mol-l-
' I ) mol-rl
' (N.C.E-R-T) l \',. 4e4 s kJ
10. The threshold eners/ for photo-electric emNsion of
electrons from a metal is 3 056 x 10-15 joule. If 12' Calculate the wavelenth ofa Photon in Angstrom
r,gii.i+iffi'f *i"il*itr, it rt"o, *itt ttt. units having energyofone electron volt'

electroos be ejecred or not ? (h = 6 63 x 1O-s t-\r" 12 40 x lf Al

Joule sec). lAns. Nol

OLEMS
1. E = Nltv =3 98x10 '-i.
101a v-l)
x 10-r Js) (4 x 7. 1 pm = 1O-17 m.Proced as in $lved exampls 2.
= (6 .023 x 1021 (6.626
10. Electrons will be ejected ooly if the energy of inci-
= 159 6 x 103Jmol-l = 159 6Umol-l dent light is greater than the threshold eoerg/.
.1
2. E =rtv = h;. Thus E ( i Energy otthe incidenilight = h v = hc1

3.E=hv=hl
(6' 626 x to-x ) (3 x ldms-
Js
l)
-
= --- (10'?5 ,. io=i6a- = 4 97 x 1o-1e !.
=193?x10-l8J rr. E=Nhv=Nhi
4., = 3802 cm-1, E =h" =h?-*t
= (6.626 x 1o-3'l Js) (3 x 1010 cm,r-1; r
mol-l
= 4.g45 x 105 J
(3t02 cn -1; = 7 56 x 10-20 J
= 494 5 kJ mol-l.
5, 1rua= lo-em 12.E=1eY= 1 609 x 10-1e J.
Proced as in solved examPle 2.
E=hv =hlorl =f
6 (i01= 0 50 x lo-lom,
(6 62 x 1o-s Js) Ox ld ms-l)
E=hv=hc7 - 1 602 x 10-1e J
16.626 x lo-31(3 x ld) , L
- = 72'40 x 1o-1 m = 12 40 x 703
0.50 x 10-lo

3.12. Study o, Emission and AbsorPtion Speclra the irBtrument is called a spectrograph and the
We have studied above that the electromag- P44ssaPh
record.ed on
of differcDt
a specuum
rumgnt used
icience dea
wavelengths
spectroscoPy.
a
The spectra are broadly classified into (i)
:: Emission spectra and (i) Absorption sPectra.
ns These are hriefly explained below : -
with the human eye. However, if in a spoctroscope, 1. Emission spectra. When the radiation
the telescope is replaced by a photographic hlm, emitted from some source e.g. from the sun or by
 ATOMIC STRUCTURE
passing electric discharge through a gas at low
pressure or by heating some substance to high
temperature etc. is passed directly through the
prism ard then received on the photographic
plate, the spectrum obtained is called 'Emission
spectrum'.
Depending upon the source ofradiation, the
emission spectra are mainly of two types :
(i)Continuous spectra WheE white Light
from any source such as sua, a bulb or any hot
glowiug body is analysed by pass-g through a
prism, it is observed that it splits up into sercn
different wide baads of colours from violet to rd
(tke rainbow), as showu in Fig. 3.16. These colours
are so continuous that each ofthem merges iato the
next. Henc the spectrum is called continuous spectroscope, it is found tlat no cotrthuous
spectrum.
o spectru-E k callcd'Line emission specfrum, or
R
Y sirrply Line specntm .
G
B
I
PHOTOGRAPHIC
PLATE
FIGURE 9.16. Continuous srrectrum of white light.
It may be noted that on passing though the
prism, red colour with the lougest wavelengtb is
deviated least while violet colour with shortest
wavelength is deviated the most.
(n) Lhe spectra When some volatile salt (e.g.,
sodium clrloride) is placed in lhe Bu$en llame
(Fig. 3.17a) or an electric discharge is passed
througb a gas at low pressdre (Frg. 3.17b), light is
PHOTOGRAPHIC
BURNER PLATE
LINES
FIGURE 3.17(a). Line spectrum produced frorn
a volatile salt placed in 6 flame.
rspcctroscoPic lncthods hal'E
hclpcd io thc diE ot Eryofa numbcr ofclcEcntE c.& hclium in thc ruo and Rb,
- in thcir tnincrel6.
lnd- Sc
3121
FIGURE 3.f7(b). Line spectrum produced from
light emitted by discharge tube.
mitted. The colour of light emitted depends upon
the nature ofsubstance. For example, sodium or its
salts emit yellow light while potassium or its salts
give out violet light. If this light is resolved in a
spectmm is obtained but some isolated coloured
lines are obtained on the photographic plate
separated from each other by dark spaces. This
Each line in the spectrum corresponds to a
particular wavelength. Further, it is observed that
each element gives its owtr characteristic
spctrum, differing fron those of all other ele-
ments. For example, sodium always gives two
yellow line-s (correspouding to wavelengths 5890
and 5896 A). Hence the spectra of the elements
are described as their finger pinrs differing
from each other like the frnger prints of the
human beingsr.
Further, it will be discussed later that the
line result ofabsorptiotr
and of energy by the
elec oms of the element.
Hencalhe line spectrum is also called atomic
spectrum.
. 2. Absorption spectra When white light from
any source is first passbd though the solution or
vapours of a chenical substance and then analped
by the spectroscope, it is obsenred that some dark
lines are obtained G the otherwise continuous
spectrum (Fig.3.18). These dark lines are sup-
posed to result from the fact that when white figlt
(cont,i"i"g radiations of many wavelenghsf is
passed through the chemical substance, radiations
cs, Tl, In, Ga
3122 Nev,t Course Chemistryfi[fl
charge tube and the light enitted on passing
DARK LINES IN YELLOW REGION
OF CONTINUOUS SPECTRUM

I
Vrl
G
B
NaCl I
The names of these series and the regions in which
SOLUT ION they are found to lie are given in the Fig. 3.18.
sLlr PHOTOGMPHIC The wavelengths of different lines in each of
PLAT E
these series are given in Thble 3.2.
FTGURE 9.18. Producilon of absorPtlon sPectrum ' 'i',Uii;t-'-i.t.'rl',i;i;iirltlii ii; ;ili ;i'
lirIir)us lines in thc different serics
, dependirg
same place
her it is ob- LYMAN
SERIES
BAL.
MER CHEN
PAS. -;rr
nnr.cx- I

I
PFI,]ND
SERIES
where coloured lines are obtained in the emission SERIES SERIES SERIES I

ancs. This shows that the 121.6 656.3 1875.1 4050.0 7451.O
re samo as were emitted 1u2.6 486. I 1281.8 2630.0 4652.O
The sPectrum thus ob-
91 .3 434.0 1093.8 2166.0 3'.140.o
tained is, therefore, cal7r,d'absorption spectrum'. .0
95 470.2 1005.0 1945.0
Dllfer.ence bctween emisslon sPectra and 8b-
sorptlon slrcctra. The mail points of difference
93.8 3n.o 954.6
between emission and absorption sPectra are 93.1 388.9
summed up in the table below : 92.6 383.5

EMISSION ABSORPIION 91.1

SPECTRUM SPECTRUM
Absorption spectrum
Ls obtained whon the
white light is first
passed through the
substance and thc The equationgives the calculation ofwave numbers
transmitrcd liSht is
@) of the lioes by the rormula 7= - (+ - + )
analysd
spectroscoPe.
in the ('i ni
)
It coDshts of bright It consists of dark where R is a constant, called Rydberg constanttt
coloured lines lines in the otherwise and has a value equal to 109,677 cm-l o.
sepsrated by dark conti[uous sPcctrum.
1 097 x 101 m-1, n, ard n2 are whole numbers
spaes.
Emission spectrum Absorptio[ sPecrrum and for a particular series z1 is constant and n2
cao bo continuous is al$,ays discon- varies. For example,
spectrum (ifsource tinuous sPectrum For Ll,rnanseries, nr = l,nz = 2,3,4....
emirs white light) consistilg of dark
or discontinuous lines. For Balmer series, n, = 2, n, = 3' 4' 5. ...
lioe spectrum if
r'.e.
For Pascheu series n1 = 3,n, = 4,5'6."--
sourc& emits somg
coloured radiatioD. For Brackett series n, -- 4,n, : 5'6"1.".."

Ernlsslon sDectrum of Hydrogen When For Pfund series, n, = S,ttr: 6,7,8...'-

ure- is taken--in the dis'
. minimum. As thc gr6c5 with highcr
Hydtogptr bcing thc lightcst clmclt, thc numbcr of linei produccd in thc spcctlum
i6

molcculai'luice arc titcn. thc s?cara bc mc rno'! and morc complcx'

.rlf thc formul. is writtcn for frcqucn(y i.e. v = a fl - -|'1,,n" *,"e of Rydberg constant, R = 3 29 x 1015 cycles/scc-
\^; ";) (...o=!=io,,=,o\
('. o=l=;,,'="")
 ATOMIC STRUCTURE
3123

S ERIES I LYM AN BALM ER PASCHEN BRACKETT PFUND

REGION I U LTRAVIOLET INFRARED

The above expressioo is called
mula.
For H-like particles, the formula is
t = * [+ - \) ,' when Z is rhe aromic num-
Rydberg !or- When n, = 2, the expression given above is
called Balmer's lormzlz as it was frst put forward
by Balmer in 1885 to erglain the seiies of lines
bearirg his name (i.e. lines in the visible region).

ri ";)
ber of the HJike particle.
Limitil
series in the
r, in the Ryd

l'.x {\l I'l.l'l 1. Calculste the ftequency and the oI the frnt line
Calculste the
limiting line in

rg's formula
(Rydbery constant = 109,677cm-1) _ 1 _(t ,.,
According ro Rydberg formula, v =T= R
lA-Al
, = * f+ - + ) For rhe Barmer ser;J., r, =lro6 for rhe lsr
n)
\ri ) Iine,n, = 3
HereR:709,677cm-1
nz=3
a1 : 1 (for ground state)
#=R R, (i-.,
/- = R ...(,
.'. n ='fie.6i7 11- I I For the second line, nt = nz
\1' 3') "--, 2, 4

= x I -r = j=n
'9
[+ a =. (i-+)
109,677 cm 9749O.i cm-l

"1r
A=; = 9.,4q, t
: 103 x 10-e
cm = 103

m = 103 nm
x t0-7 cm =*,*=1*
Dividing (i) by (ri), we get
. (,,

c
t=-=,{ 3 x 108ms-l
'--'-
103 x l0-e m --2.91 x l0lss-l *= *x f o,r : 485.e m

the For the limiting line, n., = Z, n, 6

ont
and i=*(;+ ,-')=t ...(iii)
 t1r<..ir.,'lr's Neut Coarse Chemis*g l&frlD
3124

Dividing (i) by (ili), we get Solving these equations, we get nr = 1,

7 nz=3
=5 x4 or l=364'4nm
6fiJ6
AltErradYety first calcualte R from (i) and
. ]=n (*- ,4),'
substitute in (ii) and (iii). For L?+ , Z
wovekn-gth..oJ the
frum ol Lt' ' ,on
etween two levels
whose swn is 1and. the difretence is z
Suppose the transition takes plac
be nl andnr. =l@677x8cm-r
Thenn, *n, = 4andnz- nt=2 or t = *fi , 1'14 x 10-5 cm.
rcn=

1. What is the waveleDgth of the liSht emitted Bhen 2. Calculate theuavelength from the Balmet formula
the electro[ in a hydrogen atom undergoes transi- when n = 3. [,rrs 656 nml
tion from aD ener$I level with a = 4 to an ener$/ 3. Calculate the wavelengtb of the spectral tine in
levelwithn = 2 ? What is the mlour mrrespo[ding Lyman series corresponding to n2 = 3-
to this wavelength (Rydbrg constant = 109,677
? nnl
lturs.102'6
cm-l ) (N.C.E.R.T) [,trrs 4E6 nm, Bluel

HINT,6
.,=. (;r-i-, ='o'u'"@-fi)" -' t- =L| = ---J------- . = 656 x lo-7cm
1s232 9 crlt''

2O564 4 cm-l = 656 x 1o-9 m = 656 nm

=
,_1_ I 3. ForLymanseries,r, =,,=" (i-+4
' 20564 4 cm -'
x l0-g m = 109611 x+ = 97490 7 cm-l
= 486 x 1o-7 cm = 486
= 486 nm
t =!v = ----l------------
,., --,*u,, (# - +,) .,-' 9i49o.7 crn-'
=
" (i - k) = 102 6 x 1O-7 cm
15232 9 cm-l = 1A2 6run

3.13- Dravrback of Rutherford's lilodel i,::i:l:i:i,ir:1,:ii:ri:i i:

i whereas the electrons and the nuclei are micro-
".nnicnertictes the nun and the olanets were big
Accororng to Kutnorloru s [lruul,r' au dtu'r
consists ofa small, heavy positively charged nucleus
in the centre and the ilectrons were revolving

i" go*.ra.,o, n"* branch ofphrsics' called Ouantum Mcchanics

 ATOMIC STRUCTURE
3125
the form of electromagnetic radiations. This is be- tionary does not mean that the electrons are sta-
cause when particle is revolving, it undergoos
I
acceleration due to change in direction even ilthc
tionary but it means that the eners/ ofthe electron
revolving in a particular orbit is fixed and does not
speed remains constant. Thus tne orbit of tbe change with time. The different energy levels are
r numbered as 1,2,3,4....etc. or designiied as Iq L,
a M, N, O, P....etc. starting from the shell closest to
3 the nucleus.
n_uclous. In other words, the atom should collapse.
Howevcr, this actually does not happen and thc
atom is quite stable.

FIGURE 3.21. CircuJar orbits (energy

lcvels/stationary stales)
around the nucleus.
ifferent stationary states
arr
its
3:Ix:
of thc
in
slon
ca are given by the expres-

cle * ?-n4ne'
3.14. Bohr's Model of Atom " n2h2

To overcome the drawback of Rutherford,s _ Substituting the values of rn (mass of the

electron), e (charge on the electron) and ft
model of
(Plarck's constart), we get
hydrogen
proposed
- 21 8x lo-le
quantum Ln = - -- 1- Jlatom
model of atom.
1. Postulatcs of Bohr's Model ofAtom. The
main postulates of Bohr's model of atom are as
follows :- 1eY = 7.6022 x
_ (i) An atorn consists ofa small, heavypositive_
ly charged nucleus in the centre arrd the electrons
revolve around it in circular orbits.
of circular orbits
the nucleus, the
rbits which have a
fued valte of enetgt Hence thesc orbits are called
energr levels or stationary stales. The word sta_

.","i*8,--Rx(#) *.0
2t.a
" to-191 For H-tike partictes, en= -2"'T,T"o i." u""i-2
 l'radeep's
3126

lst < 2nd < 3rd < 4th.........andsoon

or K < L < M < N........'.and so on'
For HJike particle e.g. }Je+ , Liz+ etc' (contfi-
ing one electron only), the expressioo for energy
is
7311*
o _ _Zn2m*ea = _ n7 w ^or,
1rz
where Z is the atomic number of the element
Z = 2; for Li2+ ,Z =3).
(For He+, -nz

RADIATION
OF FREQU ENCY

energy of an electron is quantiznd'

(iv) Like enerSr, the angular momentum of an
electron in an atom can have certain definite or
discrete values and not any value of its own' The
only permissible values of angular momentum are
given by the exPre r

Fnerav is absorbed when an electron lumps

i/orn% to""r. energy level to some hrgher energy
RADIATION
OF F REQU EN CY

3h/2rr .....etc. TLis meaqs enew the an'

t.}iat liLe
gular momentrtm of an elecfion in an atom is also

ground ststt. Fn.rsv rs emrtted when an electron lumps lrom a

(vi) Enersv is emitted or absorbed only when n'c;;'/ energy levet to some lower energy level
the e[jtons ji;p from one orbit to the other' For FIGURE 3.22. Energy changes during
example, when energy ls
examDle, supplied tu
is suPPucq atr dluru
to ax atom bY
uJ electronic iumPs'
t9mne11
--irl",-"
subje;tilg
',ii'J, it to electric discharge or high
in the atom irav jump from its Further, associated
,"riJ t"*l (ground state) to some higher withacertfi '
therefore'
"r.tgl,
level6i absorbing a dehnite amount ofcner- energy is alw in certain
eierqv
energy level bY

.Angulsl droncntum - MoEcnt of ilcrtie x An8;ular vElocity = I x (,'

Bt l=mc? and or = o/rshcrc u i5 tincatvclocity'

. Angular momcntu n1 =mr?xo/r=m"or'

 ATOI\,,IIC STRUCTURE
discrete quantities called quantas or photons and
not any value. This means that the cnergy of the
electron cannot change gradually and continuously
but changes abruptly as the electron jumps from
onc energy level to the other.
In other words, we c2m state that for a change
of electronic energy, the electron has to jump and
not to flow from o[e energy level to the other.
2. Electronic EnrE as Negative Energpr. In
the formula for the energy of the electron (8, =
- 7312/n2),we observe Lhat it has a negativevalue.
The concept ofnegative energy ofthe electron
may be explained as follows :
When the electron is at distance infrnity from
the nucleus, there is no force of attraction on ths
electron by the nucleus. Hetrce the energy of the
electron at distance infinity from the nucleus is
taken as zero.* As the electron moves towards the
nucleus, it experiences a forc of attraction by the
nucleus.Ai a risuh, some energy is given out. Since
its value was already zero, hence now it becomes
negative, Further, as the electron comes more and
more close to the Eucleus, the attractioo iocreases
and more energy is released. Hence the energy of
the electron becomes less and less. This explains
why the energy decreases as we move from the
outer to the inner levels.
Altematively, the energy of the aaom in the
ionized state is taken as zero. When electron is
addedup into theion, attraction takesplace, energy
it was abeady zerc, hence it be-
is released. Since
comes negative.
3. Quantization of Electronic EnerE/
Key Concept ofBohr's Theory. The most important
- The
postulate of Bohr's theory is the concept of quan-
tization of electronic energy. By quantization we
mean that a quantity cannot change gradually and
continuously to have any arbitrary value but chan-
ges only abruptly aod discontinuously to have cer-
tain definite or discrete values. To understand the
concept ofquantization, let us consider ar interest-
ing example. When we travel in a taxi, we find that
the pointer of the speedometer of the taxi moves
gradually and continuously since the speed of the
taxi can have any arbitrary value depending upon
the acceleration. On the other hand, the fare miter
only moves abruptly and discontinuously ia multi
ples ofone rupee. This is due to the rcason that thc
fare meter has been designed to have only certain
tAt inlinitc distancc, thc clcctto, is considcrcd ss a ffte electron at rcst, wherE
electron in an atom is lower than thc cncrry of flcc elcctrons at rest. Hcncc it is ncgativc.
327
specific values in multiples of one rupee. Thus, we
conclude that the fare of a taxi is quantized but the
speed is not. Similarly, in case of an atom, Bohr
postulated that electrons revolve around the
nucleus in certainfued circular orbits inwhich they
can continue revolving without gaining or losing
energy. This means that the energy of the electron
cannot change continuously but can have only
definite values. Thus, we car say that lhe energt of
an electron is quantizzd.
4. Usefulness of Bohr's Model. The main ad-
vantages of Bohr's model are as under :
(i) It explains the stability of th atom. Ac-
cording to Bohr's theory, an eleclron cannot lose
energt qs long as it stays in a pafticular otbit . There-
fore, the question oflosing energy continuously and
falling into the nucleus does not arise.
(ii) It explains the line spcctrum of hydrogen.
The most remarkable success of the Bohr's theory
is that it provides a satisfactory explanation for the
line spectrum of hydrogen.
According to Bohr's theory an electron
neither emits nor absorbs energy as long as it stays
in a particular orbit. However, when an atom is
subjected to electric discharge or high tempera-
ture, an electron in the atom may jump from the
normal energy level, i.e., gound, state to sorre higher
energy level, i.e., qcited state. Since the lifetime of
the electron in the excited state is short, it returns
to some lower energy level or even to the ground
state in one or more jumps. During each suchjump,
energy is emitted in the form ofa photon oflight of
a dcfinite wavelenglh or frequency.
The frequency (r,) of the photon of light thus
emitted depends upon the energy difference ofthe
two energy levels concerned and is given by the
expression, Q -E, = fiy s1 y =
E-Er
where E2 is the energy of higher energy level and
E1 is the energy of the lower energy level and h is
the Planck's constant.
Now, frequency is related to the wavelength
:
asv c/7 where c is the velocity of light.
E-Et
.hc
" %-E'
its cncrry is talcn as zero. The enerE/ of rhe
3128
Corresponding to the lrequcncy or wavc-
length of each p ine
in the spectrum ht)
of the spectral of
above equations are found to be in got)d agrcement
with the experimental values. Thus Bohr's theory
elegantly explains the line spectrum of hydrogen
and hydrogen like Particles (like
He+,Liz+,Be3+,etc.)
5. Simultaneous appearance of a large num-
ber oflines in the hydrogn spectrum. Although an
atom of hydrogen contai.ns only one electron, yet its
atomic spectrum consists ofa large nurnber of lines
which have been grouped into five series, i.c.,
Lyman, Balmer, Paschen, Brackett and Pfund. This
may be explained as follows :
Any given sample of hydrogen gas contains a
samplc is
ctric dis-
:''l;::l:
hydrogen atoms absorb different amounts of ener-
gies and arc excited to different enrg5r levels. For
example, the electrons insomc atoms are excited to
second energy level (L), while in others they may
be promoted to third (M), fourth (N), hfth (O)
energr levels and so on. Since the lifetimc of
electrons in these excited states is very small, they
return to some lower energy level or even to [he
ground state in one or more jumps. The various
possibilities by which the electronsjump back from
various excited states are showr in Fig. 3.23.
\=a
PASCH
S ERIES
( IN FRARED)
BALIV ER
SERIES
(vrsrBLE)
SERIES
(U LTRAVIO LET)
FIGURE 3,23. Dr{ferent series in the hgdrogen spectrum.
Thus different excited electrons adopt dif-
[erent routes to return to various lower energy
lcvels or thc ground state. As a result, they emit
dilfercnt amounts of energies and thus produce a
large number of lines in the atomic spcctrum oI
hydrogen.
For example, when the electron jumps from
encrgy levels higher than n = 7, i.e., n = 2, 3, 4, 5,
6.....etc. to n : I energy level, the group of lines
produced is called Lyman seies.These lines lic in
lhe u raviolet region,
Similarly, the group of lines produced whcn
elcctron jumps from 3rd, 4th, 5th or any highcr
energy level to 2nd energy level, is called Balmer
series. Tbese lines lie io the isible region.
In a similar way, Pasc,hen series is obtained by
the electronic jumps from 4th, 5th or any higher
energy level to the 3rd energy level. Similarly, z.
Brackett series results from electronic transitions
from 5th, 6th or any higher energy level to the 4th
energy level. Laslly, the Pfund seies originates by
electronicjumps from 6th, 7th or any higher energy
level to 5th energy level. The spectral lines of the
last three series lie it lhe infrared region.
To sum up
Lyman seies : Fromn = 2,3,4 ........ to n = |
Balmer seies : From n = 3, 4,5 ......... to n = 2
Paschen seires : From n : 4, 5, 6 ........ to tt = 3
Brackett seies : From n = 5,6,7 ........ ton : 4
Pfund seies : From n = 6, 7, 8 ........ to n : 5
B RACKETT
SERIES
 ATOMIC STRUCTURE 3i29

not only as a particle but also as a wavc. Bohr,

il,'; ;;;i";;;;*. r.o,,,r," ror-
however, considered electrons only as discrcte par-
ticles.
lowing wcaknesses or limitations.
(i) Inability to explain line (ii) Heitenbeds mcetlointy ptinciple. Accordlng
spectra oI multi-
electron atoms. Bohr's theory was successful in ex- to this pdnciple, the positiou ard momentum ofa small
plainiag the line spcctra of hydrogen atom and particle likc electron camot bc determined simul-
hydrogen like particles, containi-og single electron taneouslywith absolute accuracy. Howerer, according
only. However, it failcd to explain the line spectra to Bolu, the electron moves along a fixed circular path.
of multi-electron atoms. When spectroscopes with These will be studied in detail at the + 2 level.
better resolvingpowers were used, itwas found that
Ionizalion energr of hydrogen and hydrogen-
even in case of hydrogen spectrum, each line was
like particles. Ionization cnew is the enetg) re-
split up into a number of closely spaced lines (called
quircd to remove the electron completely from the
f,ne structure) which could not be explained by alom so as lo convefi it iflto a positive ion. Thls
Bohr's model of atom.
mcans that it is the energy absorbed by the
(ii) Inability to erploin splitting of lines in the electron in the ground state so as tojump ton =
magnetic field (Zeeman effect) and in lhe eleclic @. Thus for H-atom, as
field (Stark efrect). ln the production of line
spectrum, if the source emitting the radiation is - 21.8 x 10-le
placed in a magtetic field or in an elecric field, it En=-"'"'i'" Jatom'-l
is observed that each spectral line splits up into a
number of lines. The splittiag of spec[ral finls in the or -11]?g,no1-,
magnetic Eeld is called Zeeman efkct while the
splitthg of spectral lines in the electric field is .. I.E. = E- - Er
called Stark effect.Bohr's model of atomwas unable
to explain this splitting of spectral lines. = 0 - (- 21.8 x 10-leJarom-l)
(iii) Inability tc qlain the thrce dimorional = 21.8 X 10-le J atom-l
model of atom. Accordi.ug to Bohls model of atorn, or = 0 - (- 1312 kJ mol-r)= * 1312 kJ mol-r
the electrons move along certah circular paths in one For HJike particles,
plane. Thus r'l 6rves a llal mod4l of atom . But now it is
21.8 x 10-le -2.
well established that the atom is three dimensional }jn= - ----T::- Z. ) atom-1
and not flat, as had been suggested by Bohr.
(iu) Inabilityto e4lain the shapes olmoledes. or -!*zon^ort
Now it is well known that in covalent molecules, the
bonds have directional characteristics (i.e., atoms ..I.E. = E- - tr = o - (tEHZz)
= t x t.E+t
are linked to each other in particular directions)
and hence they possess definir: shapes. Bohr,s
model is unable to e4plain it. For example, for He+,2 = Z,
. (v) Inability lo explain de Broglie concept of ... LE. =4x I.E.H
dual charucter of matter and Heisenberg,s unceiai
ty pinctple. Bohr's model of atom is unable to ard, for L?+ ,Z = 3, LE. = 9 x I.E.H
explain the following :
In fact ionizution encrry of He+ is the second
(i) de Broglie concept of dual chuacter of mat- ionizatircn energr o
rer. According to this concept, an electron behaves of Li2+ is the third

l. Calculale the wavelength of the Solution. For hydrogen atom

radia when an electron in a hydrogen
21.8 x 10-re
alom undetgoes a tansition from 4th energt level to E,=- J atom-l
the 2nd energ level. In which pan ol the electomag- n2
netic spectrum does this line lie ? EEerry emitted when the electron jufips from
n : 4ton = 2 wilbe givcn by
3/30
!'t:,i1,,;, ' Neul Coutse Chemiswgfrffi
AE=Er-Ez = 2r.8 x 1o-', f+ - +'l
ni)
=zL.8x,r-,, (+_+,) l';
=2r.8x r._,,(+_*)
= 21.8 x 10-r' x * = 4 0875 x 10-1eJ
= E 72 x 10-20J
The wavelength corresponding to this energy z, = I, n2 =
For ionization from 1st orbit, @
can be calculated using the expression

E=hv=h.i (. c=vl) aE = 21.8, ,o-'n (;' - 1'l

\t' *)
.hc
so that "E = 21.8 x 10-1e J
li K.\l\ IPL E -r. Calc ulate the velocity of electron

1a 61375 v 16-tr r;
in rtr$ Bohr orbil of,hydrcgen atom. Given that
the
Bohr radius = 0' 529 A,
= 4.863 x 10-7 m = 4853 A (or 4E63 nm)
Planck's constant, h = 6'626 x t|-Y Is'
It lies in the visible region.
moss o! electron = 9' l1 \ 10-3t kg and
-. I.lxANlPLf'l 2.How much energ) is required to I = t kgm2s-Z.
t
ionise a hydrogen atom if the electrcn occupies ftfth
orbit ? Compare your answer with tlu ionisation
nh Or U:- nh
mVr='.-
energt of tryd.rogen atom i.e. lhe enetg) requied to 21t -' - Znmt
remove the electron frcm fr.'Il| orbit. (N.C.E'R.T,) (l) (6 626 x 10-14 Js)
x 10-rq Jatom-l
2l'8-lr'" - zrz.u, (9 11 x 10-3rkg) x 10 529 x 10-r0rz)
-
En=---
= 2. 188 x ld Js kg-t ,,l-r
For ionization from 5th orbit, n1 = J, n, =a
But 1J = lkgmz s-2'.
.. ae = E: - Er = - 21.8 x lo-re l+ - +)
rt
,,i) Hence u =2189x 106ms-l

?K:O7LEI,/ FOn: 'F [ \,.,-

1. If the enersv differeDce between two electronlc ' 4' Calculate the war nuDber for the longest
'' rLi* ir-ijalos iJ mJ:t, cal*late the frequ"nry of .tomic
wavelen$h transition in lhe Baln'rer serie's
Liiigtt, *ri,t"o *n"n an electron drops from thl hydroSgn (AIC.E.R.I) t r,rr r'523 x 105 nr-I1
hiSher to the lower state' Planck's constant, S. The electron energy in hydrogen aiom is giveo by
h=39]19 x 10-14 kJ sec mol-I. E" = 1- 2 18,
10-18;ztr2J.Crtcularerheanergy
[.rnr. 5 395 x 101'sec-rl required to remove the electron conpletely [ronl

2. rr hydroscn arom, an erecrron rumps ftom 3rd- [;,1i;:''*t]J:::",Jiff::ffi:",',*'"lHiX-"

orbit to the 2Dd orbit. Cllculate the wavelength ol
theradiationemitted (h=6 63",ltthr;
I \nL Al '".:ifi,',1,r"
o5D'l ";t#;i:;;';;,TJ.ii:;T:
electron of the hytrogin atom liom the lirsr Bohr
fifth Bohr orbit and what is the
- The eoerry associated with the first orbit in the
3.
whut
orbit to the
;;;;"*;;-z rz,ro-r8r,to,n-r
with the fifth orbil ?
H[fJt];:'!:J:tli:il',:"i;i:i":fff:',T.;
$ the energy electron energy is - z.t8 , lo-11 ergs.
associated

(N.C.E.R.T.) [.rrrr. -8.72 x l0 -20 JI

@.6.E.R.D hns. 2.09 x 1O-rr ergs, 951 At
.l J = Eorkdonc = Forcc x Distancc
= O,lass x Acceleration) x Distancc = (ligttu-21xm = kgmzs-z
ATOI\,,llC STRUCTURE 3/31

l' tE = h, r:e (214.68kJmol-l) 5i

i- cm
,
= 109,617 x
= (39 79 x1O -14 kJ sec mol-l;,
= 15232'9 cm-l = l'523 x 706 m-l.
or ,=5.395 x1914r-l 5.AE=E@-q
z. E, = -
21 8 Irlo-" J"to,,-, I 2. 18 x 10-18Jarom-l)

aE = E: - % =2r.s x,r-t, (+-+) l2')

=545xlo-l9Jatom-l
= 3.03 x lo-19J te=Ar=hI
,t =
^E=},,-hl
Or
;E
_ (6.63 x lo-34Js)(3 x ldn6-1)
(6.626 x to-r Js) xGx ld ms-l)
'',_nc
aE -
5.45 x '10-19 J
6.03 x lo-leJ)
= 3.647 x 1O-7 m
= 6-564 x 1O-1 m.= 6564 x tO-l0m= 6564 A
2 17 rrto 'o, = 3 647 x 10-5 cm.
3. En --
6.
^E=E<-Er
= 2.18 x ro-rr [4-+l
|'l'. s')
.. p. = - 2 17 x.lO-lE
= -8.72 x ro-zoJ.
= 2.rE x to-11 (*\ =, on x I o -rr ergs
4. For Balmer series, \z)./
When electron retuffis to grouDd state (i.e. to
i = tos.611 (l - -l) n=1), eners/ emitted = 2.09 x 10 -11 ergs.
\2' "') ".
l will be maximum orr is minimum = !) AsE= hv =hl ot ^=E
(r
for n = 3. The value will be _ (6 626 x 10-27 erg sec) (3 x 1010 cm J-1)
2 09 x 10-11ergs
I = ros.' rzz .m -r l/1 - 1)
\2' 3') = 9.51 x 10-6 cm = 951 x to-E cm = 951 A

I . Humphrey scries. This is another series of spectral lines which has ben reF,orted. It is produc.d when the
electron in rhe hydrogen arom jumps ftom outer shells to 6th shell re. for these lines

, = n f1 - f,) where n, = 7, s, e...

These lines lie iD the far infrared region.

l* ^i)
L The Dumbr of spectral lines producd when the electron from the nth shell jumps to thc ground state (due
("; . When aD elecrron returns from ,r2 to zr
='
ro all possible jumps )
" energy level, number of spectral

. (nz-nt)Vz-\ + l)
unes PrOOuCeq =

,l. --'T--.orbits was extended by Sommerteld by introduciDg tbe concpt of elliptical orbits.
Bohr's model ofqrcular
This belped to explain the fine lines ofthc atomic spectra.
I In any spectral series oftbe hydrogen specrrum, rhe intensity of line decreases as n2 increases.
 ,ttt L' Lt
t" s Neq, Course Chem istrttfiti[)
.\DD IO YOUR Kl'laJ!vLEDGE Col'{aD
iiiil s. The Edius of the nrst Boh/s orbii b 0 529A(52 9pm).
Theradiusof,thorbitofH-atomie.rr-0.529xn2(A).Puttiogn=l,2,3,4ald5theradiiofthefirstfive
orbits of H-atom are given beloq:
Orbit(n) 1 2 3 45
Radius (A) o 529 2.116 4.761 8 464 13.225

similarly, for H-like particles (e.& He+, Liz+ etc.), ,^=o 529-"2 A.

, r, VelGity of ao electroo in any orbit of the H-like particle is related to the radius of the orbit as

"='l* *."-i
Bafmer seriescontains four important lnes whGe wavelengths are 6563 A 'a 62 A,4341Aand 4102 A rhese
[From eqn. (r), page 3/61]

' 7
are rcspectively called Ha, Hp, H7 and Hd lines. They are obtained as a rcsult of jump ftom = 3, 4, 5 and 6
'l
resPectively to z= 2.

,,.r, L Bohr was awarded Nobel Prize in Physic.s in 1q22.

SI'CTION_IIT (1) de Broglie concept ofdual naturc of mat-

IVIODERN CONCI]I'I
STRUC]'URE oII ATONI
3.16. lntroduction:::l::i:ii:iii:r:i:r:1r::i:iii:t;i:-,:iii:i:ii:-li:iiiiir:iii::iii:r:!:r:,,:ii:ri:i:li
Though Bohr's model could explain the line
spectra of hydrogen and hydrogen like particles
and also the dra*back of Rutherford's model, it
suffered a scrious blow with the advent of de
Broglie concept of dual character of electrons and
Heisenberg's uncertainty principle. Hence a new
model of atom, called the 'Wave mechanical model'
or 'Ouarrtum mechanical model' has been put for-
ward. This model at present is considered to be the
most important. It gives a detailed arrangement of
the electrons around the nucleus. In other words, it
gives a clear picture of the 'electronic structure of
atoms'. This model could explain fully the line
spectrum of hydrogen as well as those of the other
elements. It is also able to explain the chemical
behaviour or characteristics of the atoms.
Just as Bohr model of atom was developed on
the basis of Planck's quantum theory, the wave-
mechanical model of atom has been developed on
the basis of a new branch of science called Quan-
-the
tum mechanics.* It takes into account de
Brcglie concept of dual characler bl ehctron (pfi
fbrward in 1924) and Heisenberg's uncenainty pin-
ciple (put forward in 197)
described below :
()[ tn Einstein in 1905 suggested that light has wave
character as well particle character r'.e. it has dual
nature. de Broglie in 1924 extended this idea to all
material particles (electrons, protons, atoms etc.)
and suggested lhat all mateial pafticles in motion
have duAl chsract He derived thai if any particle
of mass nr' is moving with a velocity u, the
wavelength associated with the moving particle is
grven by
.hh
muP
where h is Planck's constant un6 7n11 = p is the
momntum of the particle. This relation is known
as de Broglie relation.
(2) Heisenberg uncertainQ principlc. As a
consequence of tho dual nature of matter and
radiation, Werner Heisenberg in 1927 stated that t,
is impossible lo determine simultaneously lhe exqcl
position ond anct velocity of a miuoscopic Particle.
This is due to the fact that to locate the position of
the elcctron, we have to use light so that photon of
light hits the electron and the reflected photon is
seen in the microscope. However, as a result of
hittin& the position as well as velocity of the
electron are disturbed. If we attempt to measure
position with greater accuracy (by using lighl 61
which are briefly shorter wavelength), the uncertainty in velocity (or
momentum) increases and vice-versa. If Ax is the

i For mor details, rcad mattcr given in thc shadcd bsckground on pagE 3ly and 3135.
 ATOI\iIIC STRUCTURE
3/33
unccrtainty in position and A p is the uncertainty in
momontum, thcir product is always constant and
n.'fhus A-r x Lp =n/qn
cqual to h,/4
In the light of uncertainty principle, Bohr
model of atom lostulating that clectrons move
along definite circular paths and hence thcir posi-
tion and momcntum could be deterrnined with ab-
solutc accuracybccame unacceptable. Now we can
speak of only in terms of'probability' of finding thc
clcctron a[ any particular position about thc
nucleus at any instant of time,
Kceping in view the wave naturc of elcctron
and the uncertainty principle, the movement of the FIGURE 3.24. the ontg
clectron around the nucleus is likc that of a bee electron olthe undarv'
around the hive. Sometimes it may come close to surlace for m nsilV
thc nucleus and sometimes it may move away from
it. Further it does not move inone plare (as wrongly It is clear from the picture that most of the
postulated by Bohr) but moves iu all directions and dots lie at a certain distance from the nucleus on all
in all planes around the nucleus. sides. Since the probability offinding an electron is
directly proportional to the intensity ofdots, thcrc-
The concept of'probability' may be under-
fore, the electron spends most of its time in the
stood u/ith the help of the following simple ex-
amplos: volume ofsphere bounded by that distance an(l for
rest of the time, the elcctron can be found ouisidc
(i) Suppose on a particular day, there are
the rrolume of this sphere.
clouds in the sky. We predict that therc is achance
that it may rain. However, there is no certainty that . Tle rcgion ol spae aroand. thp nuclcus which
it would definitely rain because the clouds may d*riha thc probabihty qf fudiA cn elearon o!
rlisappear. This is expressed by salng that there is giwn ensg in kmt ol dals is called an elaclron
a probability of rainfall. clold,
(ii) In
a game of chess, a better player has a
Nowhere is the probability o[ finding an
chance to win but one cannot saywith certainty that
electron equal to zero. Even at vcry largc dis-
hc will definitely win. Thus a better player has a
probability to win. tance from the nucleus, there is a finite, though
small, probability of finding an elecrron of a
(ui) A brilliant studcnr has a chance to qualify given energy. This means that electron clouds
any entrance test but onc cannot say with ccrtainty
do not have sharp boundarics. However. [or
that he/she will definitely qualify. Thus a brilliant sake of pictorical clarity and for convcnicncc oI
student has a probability to quali[ the entrance representation, a boundary sur[ace mav bs
test.
drawn which connects points of cqtral prtrh-
Prohabilitl provides the bcsl possible d*cription ability and encloses a certaio volumc of thc
of a siluali.on tthich cannol be describctl with space around nucleus within which the prob-
cerlainty. ability of finding an electron of given cnergy is
maximum, say upto 90?b.'fhis is callccl an
To clari! the concept of electron probability,
atomic orbital.
it is helpful to do a h,?othetical
experiment in
which we take a set of pictures of a particular *t alonic orbital nay bc ilelittd qs tha three
clectron, say the only electron of hydrogen atom, at dimexional spwc aJound tlv nuclcus wirhin
very vcry short intervals oI time (say almost instan- which tlu pmbahiliE o!finding an electron oJgiven
taneously). If the electron in each picture is repre- erErg is n zximum 6q upta 90%).
scnted by a small dot and if all the pictures arc Differtncc betwn Orbit and Orbital. Some
supcr-imposed then the final picturc looks like the important points of difference between orbit and
one given in Fig.3.24. orbital are given below :
3134
Pratlt, t:1t's Neut Coutse Chemistr4lffi

ORRIT ORBITAL

t. An orbit is; wcn defined circular path around the T-E dECiE tlree 0rmensrional sPace around the
ttre
nucleus iD which the electrons revolve. nucleus within which the Probability of finding a[l
electroo is maximum QrPtogOEo).
2. It represents the planar motion of aD electroD 2. lt represeots the three dimensional modon of aD

arouDd the nucleus. elertron around thc nucleus.

3. -l}le concpl of aD orbit is not iD ac{ordance with 3, Thc concEpt of an orbital is in accorda[ce with the
the uave character of electrons and uncertainity wave cbaractcr of electrons and uncertainty prin'
principle. cipte.
4. Allorbits are circular and disc like. 4. Different orbitats havo different shapes. i.e. s'orbi-
tals are spherically symmetrical, p{rbitals are dum-
bell shaped and so on.
5. Orbits do not have any directional characteristics. 5. All orbitals except s{rbitals have directional cbarac-
teristics.
6. 'fhe maximum number of clectrons in any orbit is 6. The madmum number of electrons Present in any
given by 2a2 where z rs thc number of the orbit. I orbital is two.

In short, Schrodinger wave equation is writte n as

Quantum Mechanics. Classical mechanics'
based on NeMon's laws of motion, was suc- A V' = gV where Ii is a mathematical
operator, called Hamiltonian operator.
The solution of Schrodinger wave equation for an
electron in an atom gives the values ofE and9. The
ener-
. The
it did not take into account the concept ofdual
lunc-
naturc of matter and Heisenberg's uncrtainty
in an
principle. Hence a new branch of science
*hi"h take. dual nature of malter into con-
sidcration has been put forward. This is known
as'0uantum mcchanics'.
Quantum mcchanics, as developed by Erwin the square of the amplitude of thc clectron wavc
Schrodinger in 1926, is based on the wave mo- i.c. q2 at aay potllt Ei\Es the intensity of the electron
tion associated with the particles- For the wave vicw o[ Heisenberg's
motion of the electron in thc three dirnensional ProbabilitY of finding
Put forward the us4z at anY Poinl gives
ter his name as prcb
lhe elecl
which is con- eleclron oint.
m mechanics :
around repr
rt d7w azo 8n2m,. dcosity at different points is called an orbilal, that
"-tr+Y-I+++#(-v)v=o
a2
o, u)/
is why the wave fundon for an clcctron h an atom
is called orbital wave function or simply atomic
where rp is the amplitude of the wave where the orbital. Since an elcc&on can have many wavc
co- ordinates of the electroo are (.r, y z), E is the funcliong thereforc there are many atomic orbitals
total energy of the electron, V is its potcntial in an atom.
cncrgy, r is thc mass of thc electron and h is
Important Featurs of the Quantum lVlechani-
Planii;s constant. O7 tp/dxz represents second cal Model of Atom. The basis of this model of
dcrivative ofP w.r.t. x and so on. atom is Quantum mcchanics which iD turn is

#Ihe values of E and ty' are called .l8cn vrlu.s and.lgcr funcllons'
 ATOMIC STRUCTURE 3/35

based on Schrodinger wave equation. The im.
portant features of this model are as follows :
l. The electrons in an atom have only quantized
values of energy.
2. These quantizedvalues of energy are obtained
from tle solution ofSchrodinger wave equation.
The corresponding values of the wave function
rp are also obtatled from the solution of
Schrodinger wave equation.
3. The wave function g is simply a function of co-
ordinates of the electron and has no physical
significance as such. However, 92 gives the prob-
ability of finding the electron at that point i.e.
electron density at that point. The concept of
probability is justified in view of Heisenberg's
uncertainty principle.
4. By firding rlrz at. different points around the
nucleus in an atom, we can predict the region o[
space around the nucleus within which the prob-
ability offinding the electron with a definite valuc
of energy is maximum. ThLs space around the
nucleus is called orbital. That is wave function
V is callld orbitql wave lunction or simply atontic
orbital.
5. Since an electron can have many wave func-
tions, therefore, there are many atomic orbitals
in an atom,
g contains all the
6. Ttre orbital wave function
information about an electton in an atom and
quantum mechanics helps to extract this infor-
matlon.

Pr.'R l@--N trt,.BIt()(;t.IEEetl.{TI()N

Cala ate the wsycle gth oI an = 812 ms-l

e yelocity of 2.05 x ldms- t. By de Broglie equation
(N.cJ.R.T,) .h 6.6'25 x 70-u Is
Solution. By de Broglie equation mv (9. t x 10-:t kg) (St2 ms -r)
.h = 8.967 x 10-7 m : E967 A.
nn)
Calculale the mass of a plnlon
=@ 6.626 x 10-31Js with A.
Here,7 -- 3'6 A = 3'6 x lo-1o m'
(N.C.b.R.T,)

= 3.55 x 10-rl m As photon travels with the velocity of light,

(J = kgm2 s-21 u = 3'0 x 108 ms-l

By de Broglie equa tion, t=L

lste its wavelenglh. (N.C.E.R.T,)
or m=frh
Solution. v.e. =
),,u, 6.626 x 10-r Js
(3.6 x 70-to m) (3.0 x 108 ms-r)
.. u = tYl zKF, 2x3.0x10-25J
x
m 9.1 x 10-31 kg = 6. 135 10-2e kg.

FOR;F 0 \ iE-,,
l "RODLEMS l0-5Js). 1
a
What will be the wDvelngth of a ball of mass 0.1
kg moriDg with a velocity of l0 ms-l ?
electron =
ft -6.6 x
9.1-I lo-31 kg Planck's constant
. 7.2Sxl0-1 nl
I r\ns.6.626 x l0-rzr]
3, Calcllate de Brogiewawlength ofan electron rhat
2. A moving etectron has 4.55 x l0-5 Joules of bas ben accclerated ftom rest tbrough a poteorial
kinetic enerry. Calqrlate its wavelelgtb (msss of diffetnoe of I kV
[Ans 3.E7 x l0-rr nr]
3/36
' Net4 Course Chemistrallfi[)

H lNT$ FoRotFFtcuur ?e.or-LElas

3. K.E ofelectron = 1000 eV = : 000 x (1 .602 x 1O-19; J. Further pr ed as tn solved examPle 2 above.

I momenta' the elect'rons within the

A[ atom contaius a large nu
rhese are <listinguished from ea 'I.#'it:I;[?:ffi,i1"lffili"i
basis oftheirsrze, shape and oient fo[owing information :
in space. Thesc parameters of an
(i),Number
edpincipal, of sub-shells present within any
fr"J."J- *trn. "f three numbers, call
azimulhol ar,d mognetic quanfilm numbers -* F\r-
main shell
ther, to representtf,e spinlrotation) of the electron(tl) Contribution of energy due to an-gular
about its;wn axis, a fourth quantumnumber, called momentum towards the total
energy of thc
:d. Thus electron'
es ofthe sub-shells belong-
ing t
ubshells.
otbirllt t td lhe
(v) Orbital
momentum which is oqual

,"1 'ner+tt
ostal address of
a person. Toknowabout a particular person, Mr X, Note $at orbital angular momentum depends
wc shouki know about his country iJtown, hislane only on ttre value of ''' and uot z' Thus all
and housc number. J-orbitals (/ = 0),.e. 1s, 2s, 3s etc have orbital
rhe various quantum num ers are briefly 3l5iI;r,Iffi:1f1il,.(;i"51:?r!{r',.;r;ri
described below: -
reprc- have o.bit"l aogutai momentum
1. Principal Quantum Number. It is
=,tTTlT=I\ h/Ztt = [ih/ n and so on-
:,cntcd by )r'. It gircs thc following information :-
from This number helps to explain the linc lincs oI
(i) Approximate distance ofthe electron -''-
the s the presencc oI a largu
thc nucleus i.e. the sizc of the elec;;ffi.
(ii) Energy ur tr," p1";;;;, ",, l;iTn..u.pr. f"o""JJ:I[fih::'
shcll**, e.g. for hydrogen "t""t,oo
atom, For a given value ofn, / can have valucs [rom
gxl0-tqJarom-l=- l3l2 r,
g-= -2l ll*nt 0 to rt - l. Fir example.
nL nt Forn =1, / = Oic ontyonevalue
(,li) M"ximumrumber of electrons present tn For n Z, I = 0,1 i.c. two values
anyshcll (given by the formula 2r').
. Forn 3, /:0, l,2,i,e.threevalucs
This number helps to explain the main lines of
For n 4, I = 0,1,2,3,i.e. four valuos
thc spoctrum
Thus 1st,2nd,3rd,4th shells have 1, 2,3. and
It can have valucs n = 1, 2, 3, 4...... .etc. wltictt 4 ,"b:h;il;.j.p";iir"ly. tn gen"rut, ,th shell has ,r
aru callcd K. L, M, N.......etc. shells respcctivcly. irU"f,"ii..
2. Azimuthat (or Subsidi these sub-shclls are dcsignatedby thc
momentum) Quantum Number. ffort =0,7,2,a Jrcspectivetv
represented by'/'. It is found that he first letter o[ the words s6cr7r,
clectron calculated from the valu ed and furu)antental lincs of thc,
itsclf some contribution duc to an
*These lhrce quantum numbcrs follow from thc solution of Schrodinter I*avc cquation
.*As the elcctron clouds arc thrcc dimensional, the word'6hell'is now Prcfcrrcd over orbit or lcvcl'
 ATOMIC STRUCTURE 3137

Shell Sub-shells prcsnt Similarly, for d-sub-shelt, / : 2 so that /fl :

1st(K) 1s -2, -1, 0, +1, +2 i.e. d-sub-shcll contains livc
znd (L) 2s,2p orbitals. For f- sub-shell, / : 3 so that rlr : -3, - 2,
3rd (M) 3s, 3p, 3d -1,0, +1, +2, + 3 i.e. f-sub-shell has seven orbitals.
REMEMBER
4th (r.0 4s,4p,4d,4f
(The prefix before the symbol of sub-shell Uwlly m=0 is takan lor p, orbiul and
represents value ofn) m =! 1 for p,snd p, orbitals. Simtlarly, m = o
The number of sub-shells within the various for drzsld - 2 * + 2lor .1,2 _ 12 and d,y and
main shells are shown in Fig. 3.25. I *1lor
- or doand do
n =1 n=2 n=3 n=4 4. Spin Quantum Number. It is rcprescnrcd
\\ \\\ \\\\ by's'orrzrr. This number was introduccd to accounl
rt lll ll
tl t$ tttt for the fact that the electron in an atom not onlv
lt lll l t moves around the nucleus but also spins ahout ili
I tt t tt
I
t ovm axis (like the earth which not only revolves
I tr
n nt lt around the sun but also spins around its own irxis)
tt ttt nn (Fig.3.%). This number givcs lhc informarion
tt , lru about the direction of spinning of the clcctron
t!
s, t)
,rt trn present in any orbital. Since the electron in au
s s,p,d s,p,d,f
orbital can spin either in thc clockwise dircction or
FIGURE 3.25. Sub-shells present in the anti-clockwise dircclion, hencc lor a givcn
in the main shclls. value ofrn, s can have only twovalues i.c. + l/2 and
The energies of the different sub-shells - 1/2 or these are ver1, olten rcprosented hy lwo
present within the same main shell are found to be arrows pointing ir thc oppositc dircclion i.c
and
in the order s < p < d < f 1 ,1. .

Further, the electron cloud of's'is found to be

spherical while that of 'p' is found to be dumb-bcll
shaped. d and f have complex shapes.
3. Magtretlc Quatrtum Number. This number
is represented by 'm' or '2,'. This number is re-
quired to explain the fact that when the source

I
which take up different orientations utrder the in-
fluence of the external magnetic field. The mag- FIGURE 3.26. Spinning of etectrons.
netic quantum number tells the number 6f
orientat This quantum number holps to cxplain tho
Same su magnetic properties of the substances. A spinning
the num electron behaves like a micromagnet with a definitc
shell (as magnetic moment. If
an orbital contains two
For a given value of ( rn can have values from electrons, the two magnctic moments opposs and
-/to + / including'0'. Thus cancel each other.
_ For s-sub-shell, / : 0. Hence rn = 0 (only one
value) i.e. s-sub-shell has
Thus in an atom, if all thc orbitals are fullv
only one orieniation or hlled. net mag[etic momcnt is zcro.anrJ thc subi
has only one orbital. stance is diomugncric (i.e. repcllcd by the extcrnal
magneric field). However, if iomc hsif- fillcd orbi-
tals are present, the substance has a net magnotic
momenl atrd is paramagnetic (i.e. altractcd hy lhc
external magnetic field).
3/38
Neqr course chcm irtrgffri[
Idea ofstclls, subshells and orbitals. Tb sum up

(4 s,4 p,4 d,4fi.

second main she[ called L-shell and so on.

e sub-energY level oc-

(as main energY lerel is
a number ofsublevels of oue orientation wtich means s+ubshell consists of
energy). It is
ber (/). For a
for n - I, l
means that it
:
/ 0, 1 i.e. I has two values which means that it
has two subshells. Similarly, 3rd shell has three
subshelk, 4th has four and so on. The subshells orbitals present in different sukhells for ttre fust
corresponding to / = 0, 1, 2 and 3 are repre- three main shells may be reprcsented as shown
sented by s, p, d and/ respectively. Hence below :

(Five 3dorbitals)

-L-------
h- 3\ ,'
_::---:!-i----1 30 /.rhE! -t! orbiElsl
(MttllD \\
(One 3s orbital)

(Three 2p orbitals)

-4--------
. 2s _______ (One 2s olbiht)

(n = 1) ls /Ona I s
^rb'tal\
(K-shell) Subshells

IiX,C"MPI-E l. An ,lrrwn is in a 4l orbitat, For each value of rz, Oe spia quantun trum-
What possible vahtes Ior the Etantum numbe4, n' l, ber, s has two values, i.e', s = +I.f}aads= -U2'
. EIAtrIPLE 2. Wite down ahe Eta,tum nutn-
m atd s con it h@e ?
Since the electron is in a 4f orbital, bers n, I ond m for the following orbials :
the value of the principal quartum number,n = 4' i d? - rz (ii) 4 d S (iii) 3 d,, (iv) 4 d,,
(i)
For the f-orbital, the secondary quantum (v)2p"(i)sp,
number, I= 3. (i)n :3,1 = 2,m = -2 ot +2
The values of the magBetic quantum (m) are (iln:a,t:\m=0
.-l to +l including zero' Therefore, whelnl = 3,-m
has seven values i.J' -3, -2, -1,0, +1, +2and3'
(iii) n = t,l = \m = -2 or * 2
ATOI\.4IC STRUCTUBE
3/39

(iv) n = 4,1 :2,m = -1or + t (ii) This sct oIquantum numbers is permitted.
(v) n :2,1 : 7,m = 0 (li)
This sct of quantum numbers is aot per-
(vi) n = 3,1 : 7,m = - 1or -i- 1 mittcd bccause thc value of spin quantum number
EXA.I\IPLE 3. What dcsignation is iven to an canlot bc zcro.
orbital having (i) n = 2, l:1, (ii) n =.1,t = 0, (rv) This set of quanorm numbsrs is also not
(iii) n = l:3and(iv)n = 4, 1:2?
5, permitted since the value of ,rz, cannot be greater
(i) n : 2,1 : 1 means 2p-orbital than 1.

(ii) n = 3,1 : 0 means 3s-orbitat EXAMPLE 5. Which of the following orb:tats

(iii) n = 5,1 : 3 meafls 5f-orbital
(iv) n = 4,1 : 2 means 4d orbital.
EL1MPLE 4. Which oI the following sets
ol
quantum numbefi are not permitted 2
(i) n =2,1:2,m = -l,s = + 112
(ii)n : 2, l : \m = -1,s : - ll2
-(ir|":2,t=0,m=0,s:0
(tu)n = 2, 1- l,m = 2,s: + tl2
(i) This set of quantum numbers is
not permitted sir,ce the value of / cannot bc cqual
to n.
are not possible ?
lp, 2-s, 3l and 4d.
(i) The lust shell has only one sub-
shcll ich has only one orbital, i.e, 1s orbi-
tal. Therefore lp orbital is not possible.
(ri) The secondsub-shell has two subshells, i.e.
2s and 2p. Therefore 2s orbitals are possible.
(iii) The third subsbell has three subshells, i.e.
3s, 3p and 3d. Therefore, 3f-orbitals are not pos-
sible.
(iv) The fourth shell has four subshells, i.e.4s,
4p, 4d and 4f. Therefore, 4d-orbitals are possible.

1 AEzLIE,MISiF,OR 1P-ffiC, E
l. Ifn is equal to 3, what are the valucs of quantum (i)n - 1,1= O,m = O;(ii)n = 2,1= t,m =-1
numberslandm? ard(iii)n=3,1=2,m=+t
Ws. I = 0, t,2 n = +1, +2 lrns. (,) ls (rr) 2p (}, fil
-\ -1,O,
= + l/2 and - ll2 for each
and s value ofral
or zpr) (ni)
6. Grye the values of the quantum numbers for thc
2. If the quantum number ?' has a value of 2,what
electron with the highest energy in sodium atom.
are thc permitted values of the quantum number
[drs. n =3,I=0,m =0and.r= +l/2or-ll2l
7. Which ofthe following orbitals are nor possible?
ftns_ _2, _1. 0, +1, +21
3. List the quantum numbers (/ and n/) of clectrons 1p, 2s, 2p and 3i
for 3d orbiral ? (N.C.E.R.T.) Ans. lp and 3,
E, Which of thc follo\ring sers of quantum numbers
$rs, ,r = 3,, = 2,rr =_2,_1,O,+t,+z
are not possible ?
= + V2 atrd - l/2 for each value of,ll
aDd s
4. What are the values of n,l a1d m fot 2p-orbitals ? (i) n-3,1=2,n1 = 0,s = - l/2
F{s. For all 2p-clectmns, r = 2 and , = l, but zl can (ii) n = 3, 1 = 2,m = - Z,s = - 1,/2
lhave any oEe ofthree values i.e. atrd +ll (iii) n = 3, I = 3,m = - 3,s - + t,t2
-1,0
5. Vrtite the corre.ct orbital notations for each of the (iv) n = 3,1= 1,m -O,s = + 1/2
following sets ofquantum numbers:
[ns.(rrr1

6. Electronic configuration of IINa-ls2?-r24,63r1. 8. (,ii) is not possible because if

The electron wirh highesr enerry is 3sl for wttich rl n =3,1=O,1,2.
 Neur Course Chemistrq
3140

| :.::l:l:i it,:li:::i:i:a:: a:rl::i:i:i:ar; a,i:l : 0. Since

the spir
From a studY of the quantum numbers, erefore,
Wolfpanz Pauli, a German pbysicist in 1925 put h quan-
torwird"a principle known after his name as Pauli tumnumbers,n : 3,1 = 0,m : 0ands : + 12
exclusion principle. It states that : arrd the other with quantum numbers,n 3,1:0, :
m=0 s = Si-ilarty, any grven orbital
No two elcclrotls in an arom cin hLte tlu same sel
and UZ' -
olfow qwntutn numben. can have two and not more than two lectroDs' This
gives us another definition of Pauli's exclusion prin-
Ifone electron ir an atom has some particular ciple which states that
values for the four quartum numbers, then all the
other electrons in that atom are excluded from wr havc a maximurn
fui orbita! fiYo eMtans dnd
ihae nw lwe oPPin sPitts.
On the basis of a study of quantum numbers
and Pauli exclusion principle, the maximurn num-
ber of electrous tliat can be accommodated in
anv subshell or shell can be calculated' This is
brt the fourth must be different. illustrated in Table 3.3 for the 6rst four shells,
Now, any particular orbital is described by namely, I( L, M and N i.e. for n : 1,2,3,4'
three quantum numbers i.e., n, I and rn. For ex-

accoErmodated in a shell, its sub'shells and orbitals

Electrcns Total No.

Shell Principal AziEuthol Magnetic SpiE
preaent of electrons
Quantum No. Quantum No. Quantum No' Quontum No.
(subshelland (Orbitals)
its desigration)
(") (t) (m) (s)

l1
+2,-2
K 0 (1r)

1 1l .'
L 0 (2r)

t (2p) '2'
1
_,I
-1
0 '2'
1
-z 1

+1 *z' 1 1

1 rl )
M 0 (3o) '2', 2,-
| (3p)
-1
1
'2', 'l
0 +i, 1

+l 1
'2', iI
Conrd. on rrcrt Wge-..
ATOMIC STRUCTURE

--2 a- 11
'2' -- 2
11
-1 '2', 2
!- _-

11
0 '2' 2
+1 4- 1i _-
' 2' 2
+2 .1 I
'2' 2

N 0 (as) 11
'2' 2

| (1p) +- 11
-1 '2' -_ 2
11
'2' 2
+1 4- 11__
'z', 2

2(M) .l I
-2 '2' 2
11
-1
f
'2', -
_-
2

.1 1
'2' 2

+1 11
'2',
!- _-
2

+2 .1 1
'2' 2
11
3 (4f)
-3 'z', 2
11
-2 ' 2' 2
J- _-

11
-1 '2', 2
11
f
' 2' 2 -
__
32

+1 11
'2' 2
+2 11
'2' 2
+- 11_-
+3 'z', 2
3142
Pradeep's

ArDrt ' , Qiffi;K;N'O ,t.ErD'@iE I

ffi1. Quantum numbers were discovered by different scientists as follows :
Principal by Bohr, Azimuthal by Sommerfeld, Magnetic by Iltde aod Spin
by Uhlenbeck and Goudsmith'

PrinciDalo}arrtumnumber tells about the JEe ofthe orbita

shape
ffi2. about takes
;;;;';;j,rffiiG ;;tetic quaDtum number tells
uD in the magnetic fi eli oc thi number of orbtlalt present in a subshell'
PrinciDal quaotum number, ,, used by Bohr and azimuthal quantum numbr,
k used by Sommerfeld (by
ifr 3.
related to each other as
introd'ucing ttre conccpt of elliPtical orbits) are
n

Whent = n, the orbit becoffes circular. R.lrtherk canDot be zero becaus that means miDor axis iszerowhich
in turn implics linear motion of ttle elctron passing through the nucleus'
ifid 4. Theshapeofanorbitalistheboundaryorco[toursurfacrdiaSramobtainedbyjoiniDsthePointsofcqual
oD wbich the probability
protaOitity 1,72; ot tle electron around the nucleus. In other words, it is the surfac
that encloses the region within which the
deosiw r.i,lt is constant. Many such surfaces are possible but the one
pi"i"Li,ryG n"oi"gihe electron is very bigh, siy upto 907', gives the shaPe and size ofthe orbital'

ilil 5. The surface on which ?2 is coostant, ry' is also constant on that su rfac. Hence
boundary surfaces for 'p2 an<l
are identical.
'/

As already dfined, an orbitol is the region of

below ; ONE NODE

The ProbabilitY of frnd-
FIGURE S.27. Shapes of 1s,2s and 3s orbitals'
ing to s-orbital of anY main
shi cal in all directions at a
Alth g to different
given clistance from the nucleus. Hence s- orbital is
shells are in
theY differ
ipherical in shape which is symmetrical around the re
certain
nucleus (Fig. 3.27).
(i) The probability of ls electron is found to
Ahernatively, the shaPe of s-orbitals fol- be m#mum near the nucleus and decreases as the
lows from the concePt of quantum numbers as distance ftom the nucleus increases. In case of 2s
follows :
For s-orbital, azimuthal quantum number

in shape.
ATOMIC STRUCTURE
\rithin it. Similarly,3s has twonodes.In general, any
ns orb_lafbas (n- l) trodes.
/61 tne size and energy of the s-orbital in-
ofpases as the principal quantum numbcr n in-
cieascs i.e. the sizc and energy of s-orbital increases
in the order 1s < 2s < 3s....
Shapes of p-orbitals. Ou the basis of prob-
ability calculations, it is found that the probability
of finding the p-electrons is maximum in two lobes
on the opposite sides of the nucleus. This gives rise
to a dumb-bell shape for the p-orbital (Fig. 3.28).
FIGUIiE 3.28. Shapes of p-orbital.
However, it may be noted that the probabi.lity of
finding a particular p-electrou is equal in both the
lobes. Further, there is a plane passing through the
nucleus on which the probability of finding the
electron is almost zero. This is called a nodel plane.
Further, forp-orbital,l = l.Hencern = -1,
0, + 1. Thus p-orbitals have three different orien-
tations. These are designated as p,, pt a\d pz
depending upon whether the electron density is
maximum along the X-axis, Y-axis and Z-axis
respectively (Fig. 3.29).
I tals of hydmgen and lry&ogen likc panicles depend
Py
FIGIJRE 3.29. Ditrerent orientations of p--o6itals.
Thus unlike s-orbitals, p-orbitals have direc-
tional characteristics and hence are helpful in
predicting the shapes of molecules. Further it may
be mentioned that every energy level with,l greater
than t has three p-orbitals. As a increases, these
3143
p-orbitals become largcr in size and have higher
energies. However, the thres p-orbitals belonging
tg a p4rlicular ggg-rgaleveltrare.equal energies and
3rc called degenerate orbitals. Further whereas fu
orbital has no node, 3p has onc node, 4p has two
nodes aud so on. Thus, we may conclude that
Number of nodes in any_orbitql.= (n - /- 1).
Note.1. The formula given above is for finding
the number of sphericaVradial nodes only. It is
interesting to point out that whereas.r-orbitals have
spherical nodes only,p and d-orbitals have spheri-
cal as well as planar nodes. For examplc, @ orbital
has one nodal plane passing through the nucleus at
the origia. Similarly d-orbitals have two nodal
planes. The number of spherical nodes depends
upon th value ofn.
Thus tle above results may be generalized as
follows :
.lfrdfrb{ twd6 ir en!
"Ln-l
Nuntcl. o{ pfu*r aoda in aq orbinl = t
;. Ibrill tunifudlrtuLt W ?{!iP 4 n- * ti'
2. Positive and negative signs shown inside the
Iobes ofp-orbitals
have nothing to d
-charge. However,
always positive.
3.20. Energy Level Diagrams ot Hydrogen
Alom and Mullielectron Atoms,,r,,:,,;,,r'rii,,,:,,,'r,r,,i,:'i,
It has already been discussed that the dif-
ferent subshells of the same main shell have dif-
ferent energies. However this is true only h case of
multi-electron aronr as shown in Fig. 3.30(b). In
case of hydrogen or hydrogen-like particles (con-
taining one electrotr only), they have the same ener-
gy as shown in Fig.3.30(a). In othcr words, it rnay
be concluded that rvi eruas ene@es of difrerent orbi-
upon the value of principal qusntum numbet (n)
only, those oI multielecttun atoms dependbolh upon
principal quantum number (n) as well as azimuthal
quantum numbet (l).
3144 N e ut Co urse Ch c m i strgYYTl

4s 4P 4t

o
3s 3p 3d
(,
4s -9
E *
oz
E.

2s 29 OE
#
1s

1s

FIGURE 3.30. (a) Enegy leveldiagram for hydrogen abm.

(b) Energy level diagram for mullielectron abms.

Some important observations from energy The order in which the energies of the orbitals
level diagram of multielectron atoms maybe made increase and hence the order in which the orbitals
as follows : are filled is as follows :
(i) The subshells of a particular shell do not b ,% ,2p,* ,3p,4s ,M,41t,5s,
have equal energies e.g. ?-s atd2p have different
. M ,5p ,6s ,4{,il, @ ,7s ,5f ,U ,'7p.....
energres.
This order may be remembered by using the
(ii) In a particular shell, subshell with lower
method given in Fig. 3.31. Starting from the top,
value of I has lower energy. Thus in the second shell
:
N (l :0) has lower energythan2p (/ 1). Similarly the direction of the arrows gives the order of filling
in the 3rd shell, energies are in the order 3 s < 3p of orbitals.
< 3 d ard in the 4th shell they are in the order
4s<4p<4d<4f.
(irr) For the same value of n, the difference
between energies ofs andp-subshells is smallwhereas
betweenp and d-subshe\ it is large and so on.
(iv) As the value of n increases, the subshell of
lower shell may have higher energy than that of the
higher shell e.g. 3 d has higher energy than 4 s.
Note. In case of H-atom, the energies of the
orbitals are intheorderls < 2s :2p <3s:
3p :3d < 4s - 4p : 4d : 4f < ...

The filling of electrons into the orbitals of

different atoms takes place accordingto the follow-
ing three rules :
(1) Aulbau Principle. The word 'aufbau' in
German means 'building up'. The building up of
orbitals means the -filling up of orbials with
electrond The principle stales is follows : -
In tlu ground stale of tlu alon*, tlrc orbitals are
fillcd in order of tluir increashg mugies. In ollur
words, elmtrotu first oc,cupy tlw lowest-energt othL
nl avaiWle to lt en and enlq inlo hiirur eneigt
orhitok only wlun tlw hwer erurgt orbitals are
ftllcd.
FIGURE 3.31. Onderof fillingof orbitals.
Altematively, the order of increase of energy
of orbitals can be calculated from (z * I) rule.
The energy of an orbital depends upon the
values of principal quantum number, n and the
azimuthal quantum number / (in the absence of an
external magnetic field). The (n + l) rule states as
follows:
 ATOMIC STRUCTURE 3145

Lower tlu vahrc oJ @+l) lot qr. orbital thc lower sane (t + l) vdttc, the orbital with lower vabu o!
i; ils erargt Hence orbitah are Jilld in order oJ n has hver uurg and hcnu itfrlldJint.
increasing (n+l) yalues. If mo orbitab have thz The followingtable illustrates the (a + /) rule:

Orbital Value ofn Value of I Value oI (n + /)

lJ I 0
2s 0 2+O=2 -
2p 2 1 2+1=3 [ 4) @=2) has l@ter enerry than
3J 3 0 3+0=3 J 3t(n=3)
3p 3 I 3+ I =4
1 3p (n = 3) has lower enerry rhan
tu 4 0 4+0=4 J as (n =a)
M
a+1-sJ| tp(n= t).
3 2 3 + 2 = 5 3d (n 3) has lotler enerry than
4p 4 1
=

(2) Pauli Exclusion Principle. As alrcady ex-

Tlu pairing of elutmns in tlu orbitals behnging tn
plained, Pauli exclusion principle states as follows:
tlu satu sub-slull (p, d or fi dM not ,a*r plwe
An ortinl an hau ,iarilntm two e&f,irorts and until ath ortitalbebngi.ng to that sub-slullhat got
tlr* m$t luyc oppfire spi/flJ. oru cldron urh Lc. is sinfu utupicrl.

If an orbital is represented by a circle aad it Since there are three p, five d and seven f
contains two electrons, it is represented as orbitals, therefore the pairing ofelectrons will start
in the p, d and f orbitals with the entry of 4rh, 6th

@-@
i.e. the two arrows must point in the opposite direc-
tion. The electrons are said to bo paired or the
orbital is said to be fully hlled. It will be wrong to
represent it as
and 8th lectron respectively.
The reason for such a tendency is quite ob-
vious. The electrons are negatively charged and
repel each other. Hence they spread out and oc-
cupy the identical orbitals singly before they begin
to pair. As a result, the repulsions are minimuLm.
Hence the enerry is minimum and the stability is
maximum. Pairing occurs because less enerry is

oor@ needed to do so than the energy required to place

the electron in the next higher empty orbital.
Further, it is important to uote that whenever
orbitals are singly occupied as above, the electrons
If
an orbital contains only one electron, it is 'present
in them have the spin in the same direction
represented as i.e. either all clockwise or all anticlockwise. This is

oor o
and is said to be half-filled. Tbe electron is said to
because of the fact that such a state has lower
energy a.nd hence is more stable.

Tlu distribution ol clarmns iuo tliferent lzvels,

be in an unpaired state.
(3) Hund's Rule of Marimum Multiplictty.
sublzycb arrd ortids ol aa atom is csltcd i*
eletmnic @nfiguration.
This rule deals with the filling of electrons into the
orbitals belonging to the same sub- shell (i.e. orbi- Keepiag in view the above rules, arrd repre-
tals of equal energy, called. degenerate orbitals).lt senti.ng an orbital by a circle and an electron and
states as under the direction ofits sph by ar arrow, the electronic
:
- configuations of the first 12 elements may be rep-
resented as follows :
3146

ls Zr fp ls
Hydrogen 1

Helium
Lithium 3
o o
Beryllium 4
o @
Boron 5

6
E o
C-arbon

Nitrogen 1 o @
Orygen 8 E @
@
I
Fluorine 9

Neon 10 B
E
o
Sodium 11

Magnesium 1Z @
B @ @
The above method of writing thc electronic Chromium (Atomic numbcr = 24) :
configurations is quite cumbersome, Hencc, usual- Expected configuration :

ly the electronic configuration oI the atom of any Lsz 2sz 2?6 3s2 3p6 3d 4s2
clement is simply represented by the notation.
Actual configuration :
NUMBER OF
1:2 %2 2p6 3p6 f 4s1

Coppr (Atomic number = 29): .

Expected confi guration :
1sz 2sz 2p6 3s2 3p6 3d 4sz
Actual configuration :
1s2 'xz 2p6 :,s2 3p6 3d1o 4sl
8H'r',+f"'oo
Molybdenum (Atomic number = 42)
e.g. electrons are present in thc
1s2 means 2
Expected confi guration :
s-subshell of the 1st main shell.
1s2 xz 2p6 3s2 3p6 ldto 4tz 4pc 4fr Jsz
To get the complete configuration of an atom, a
number of such notations are written one after the Actual conhguration :

other in order of increasing energics of the orbitals, 1s2 2s2 2p6 3s2 3p6 3d10 4s2 4p6 4d5 5sr
starting alwals with thc orbital of lowest cnerryi.e. 1s. Palladium (Atomic number = 46)
Using the above method of representation,
- Expectedconhguration:
the electronic configurations of the various ele-
ments are listed in Table 3.4 on page 3148 to3149. h2 b2 2p6 k2 3p6 3d1o 4s2 4P6 4dB 5sz

Some exceptional electronic conligurations. Actua[ configuration :

Some elements such as chromium (At. No. 24), cop' Mto

lsz zsz 2p6 kz 3p5 3dto 4s2 4p6 5so
per (At. No. 29) etc. possess electronic mnfrgurations
different from those expected from the auJbau order' Thus generalty only one electron jumps from
This is because of the tendcncy ol the sub- shells to be lower erergy orbitat to higher energy orbital e.g.
acactly ha\-lilled or completety
filled -
from 4s to 3d. However in case of palladium, two
To ilustrate this point, a few examples are .electronsare involved (the only case with a dif-
given below :
- ferepce).
 ATOMIC STRUCTURE 3147

The reason for the tendency of the subshells to be completely filled or exactly half-filled is that it
lcads to grratr stability.
Cause qfgluter stdbillty of exactly half-lllled and completely lllled contlguradons. The greater
stabiFty of these configurations is due to the following two reasons :
(i) Syrnmetry, The half-filled and completely filled configurations are more symmetrical and syrn-
metry leads t.t gteater 'r,hilify
(ii) Exchang encrg/. The electrons prcsent inthedifferent orbitals ofthe same subshell can exchange
thei e results in release of energy, called exchange enerry and hence leads
to a
' aha r of exchanges that can tale place is maximum in the exactly half-frlled
ts (i.e. more in I than in / and more in dlo than in /j, therefore
exchange energr is maximum and hence the stability is maximum.
The number of exchanges that can take place in / configuration are as follows :
-

l
,K\
[rll] rL ]
3 EXCHANGES BY 2 EXCHANGES BY , l EXCHANGE BY
ELECTRON 1 ELECTRON 2 - ELECTRON 3
Ibtal number of exchanges = 3+2+ 7=6
The number of exchanges that can ta-ke place in d configuration are as follows : -

t t
<SI
1 1 1 t t t t
3

t I I I t
I

4EXCHANGESBY 3 EXCHANGES BY 2 EXCHAGES BY I EXCHANGE BY

ELECTRON I ELECTRON 2 ELECTRON 3 ELECTRON 4
Total number of exchatrges =4+3+2+1=10

Some lmportant polnts in writiEg
electronic conliguratlons. While writing the
electronic configurations, the following points
may also be noted:
(i)To avoid the writing of electronic con-
figurations in a lengthy way, usually the symbols
[He]2 [Ne]lo, [Ar]18 etc. are used as the first part
, conliguration.In the end, a student maybe curious
of the configuration. Such a sym.bol stands for the
elcctronic configuration of that inert gas and is
usually called the core of the inert gas.
(ri) Although the orbitals of lower energy are
filled Erst but the electronic configuration ae writ-
ten not in the order in which the orbitals were hlled
but in the order of principal quantum numbirs.
(rr) Unless otherwisc meutioned, electronic
configuration always meam the electronic con-
hguration in the ground state.
For elements with very high atomic numbers,
some deviations are observed other than on ac-
count of half-fi.[ed and fully filled subshells. How-
ever, for our purposes, such exceptioos are not
importart.
Uti I ityllmportatrce of studlng electronic
to know as to why we study electronic confrgura-
tions. It is importart to know that according to
modern approac\ the chemical behaviour of all
elements and compouads is explained on the basis
of their electronic configuration e.& why atoms
combine to form molecules, whysomeelements are
metals whereas others are non-metals or why some
elements Iike alkali metals and halogens are highly
reactive whereas noble gases like helium, neon,
argon etc. are not etc.
314A

ConllguratioD Number Conliguration

number

1 H 1sl 33 As lxlt*to *0,

, He lsz 34 Se lArle t'o *' oon
3 Li [Hel2 2rl
35 Br lxlz roro ot' n,
4 Be lljlelz 2?
36 Kr l*fe rlo *' On
5 B lPre)z xz 2p1 ot l.s2 ,2,sl2p6 * 3p6 3dro
6 C 1rte12 xz 2f
&af
7 N lPielz 2* ?f
37 Rb lkl36 5rl
Sr [k]36 5r2
8 o lli,Le1? xz
2pa 38

9 F 1Pre12 x2 tf 39 Y lxrPo t' t '

Ne x2 zp6 40 7-[ 1k136 d ssz
10 1we12
or t"2,2?,2p6 .41 Nb lKrl36 # sr1

11 Na 1Nelto 3sl ,*42 Mo [Krlre t' t"'

43 IC l(.Jl% 4d 5s2
72 Mg ltlelro 3s2

73 AI lNe]lo 3$2 3pl

+44 Ru [Kr1:o t' tr''
*45 [Kr]36 ndt 5rl
14 si 1Ne1lo :s2 :1 Rh

15 P 1Ne11o ss2 rf
. .46 Pd [IG]s ldlo 5ro

AS [Krl3a 4d1o 5rl

16 s [Ne]lo as2 :pa .-"41
:f 48 C{l [Kr]36 allo 5r2
17 cl 1Ne11o :s2

AI 3P5 49 In [Kr]36 4d1o 5s2 5p1

18 1l.te]lo:s2
or ts2 ,Nz ,zp6 ,Nz ,zf 50 Sn lrc)ts tn
*ro tt'
19 K [At]l8 4r1 51 sb [Kr]:cttot'"
20 Ca [Ar]18 4.r2
52 Ib Il{il$ Mlo 5s2 5P4
[arlla rr' *'
2l 53 I Uklx 4dto 5s2 5P5
II tArIs 3d2 4rz 54 Xe lKite *'o tt" to'
23 lerlte ,' *'
ot ts} ,2?2p6 ,k2 3p6 M1o,
rt *t 4s2 4p6 Mro ,ssz 5f
\Xz4 Cr larlts
25 Mn [Ar]18 3a5 +rz
55 Cs lxels4 tur
56 Ba 1xe1sa rs2
26 Fe [tu]18 31 4s2
n Co lArlte ar' *' .57 la 1xe15a sa1 er2
E
ed8 4r2
.58 Ce lxel54 4/ 5d1 tu2
28 Ni lArf
\-b1e Cu [arlte *t 59 Pr 1xe15a lf s/ es2

Ztt
'O''o
,to *' @ Nd f/'fil'4 4f 6s2
30 [Ar1ts
31 Ga lr'jl1l M1o *2 4P1 61 Pm 1xe15a tf *7
*' on 62 Sm lxels4 4f 612
32 Ge l*fe :,oto

-.Elements
with elerlroDic confisuratioDs.
 ATOIVIC STRUCTURE

aoDfiguration Ccnligura fion

63 Eu lxels4 4f $2 95 Am lRnle 5/ tu,

cd lXelsa tf 56t 6tz //96 cm lRnls 5f @1 lsz
65 Tb lxels' 4f &2 91 Bk [Rn]e s/ tuz
6 ry lXelsa nfo 6z 98 cf lRnls 5/o 7s2
67 Ho [xe]s 4f1 6s2 99 Es lRnls 5/r 7s2
68 Er lxels4 4f2 6s 100 Fm [RD]s 5/2 tu2
69 Tm lXe)sa tft 6oz 101 Md lRnle 5/3 tuz
70 Yb lXelsa tft 6tz 102 No lRole s/4 tu2
71 Lu tfa 54r 6tz 103 Lr
't)
[xelsa
lRnlu 514 1
1sz
Hf tla saz 6sz 104
[xe1sa Rfor Ku or Unq lRnl% 5f1 2
7r2
73 Ta nfa 54t 6tz Rutherfordium
[Xe]sa
orKurchatoviuh
74 w [xels1 4f1 5d 62 (UtrIlitquadium)
75 Re lHe1'a tfa sd 652 105 Ha or Db or Unp (P<nl6 sfa gt1"z
Hahnium
76 Os lXelsa +fa sd 6rz or Dubnium
77 lr lXelsa lla 54t 6tz (Unnilpcnrium)
r78 106
Pr [xe]sa +fa sd 6t Sg or Unh
lRnl% sl1 &f 't.tz

.Xls Au [Xe]sa +/a 57to 6ot

Seaborgium
(Unnithexium)
80 Hg lXelsa tfa 54ro 6z 107 Ns or Bh or Uns ds isz
[Rn]% 5114
[Xe15a tfa Sdto *z 6or
81 T'l Nilsbohrium
or Bohrium
82 Pb [Xe15a tfa saro 6tz 6op (Unnitscprium)
83 Bi [Xe15a tfa salo 6sz 6o' 108 Hs or Uno [Rn]% 5f4 ef h2
Hassnium
lXelsa tfe 54to 6z *e
84 Po
(Unniloctium)
85 AI [xe]sa tfa sato *z 6;5 109 Mt or Une
86 IRDIU 5f4 u7 7s2
Rn fXe)sa tfa 5d.1o 6sz 6oe , Mciherium
(Unnitennium)
ot 1s2 ,b2 2p5 , k2 3p6 3d1o
110 ' UuD lRnls 5/4 (,d8 7s2
4sz 4p6 Adto q14 ,ssz (Ununnilium)
5p6 sdlo ,6s2 6pc or Ekaplatinum
8',7 Fr [Rn]s 7.r1 111 Uuu [P.Dl6 5f1 d lsz
(Unununium)
88 Ra [Rn]s 7s2 or g('gold
#.as Ac ll2
[RD]s 6dl tu2 Uub 1Rn16 sla uto *
Th IRD)$ sf d is2
(Ununbium)
i'st Pa lF.:Dl* 5f ul is7
or Ekamcrcury

fi%
I 13 Uuo [Rn1% sla ulo l5z 7oz
U lRnls 5P 6dr tu2 lUnunqua'diuml
t|93 Np 5f dt ll4 Uuo
[Rn)% 7s2 lRnlu 5f4 6d1o 7s2 FF
(Ununpeh um)
94 Pu lRnls sf tuz

'Ecmcnt6 wlth cxceptioDrl c

*Thc na'lcs gNen in brackeis
ar.ILtpAC nafies. Rulcs tb- Deming r!.eI,1 Irc
dcscrir\,,, i1 tjn;t,{
3/50

O,N ELECTRONIC
l l i:;ii ,, ....,,,, .,,,,,
CONFIGURATION
(atomic No' 15) chromium
i I . \ '. r 1 . l.Find.lhe number ofurtPoircd electtons Prcsent in Phosphorus
(atomic No. and coPW (atomic No'29) alter witing theit orbital electmnic configtration'
Solution.
At. No. Etectronlc conliguratlon No. of unpaired electrons
Element
P 15 t* ,xz zp6 ,x2 yt,qtrlpt, 3

Cr 24 ts2 ,z,f zp6 ,x2lpu 3d , qt' 5+1=6

Cu 29 G ,a' zp5 ,x2 lpe 34ro , 4rr L

atonric numbers :
li', | .l.Wite the elec7onic configurations of the elements wilh the following
3, 8, 10, 14, 17, 25, 29' and 3E'
belong'
Also mention the gouPs of the peiod'ic table to which they
Solution.
Atomic No. Electronlc con[iguration Group ot pertodic T[ble

r,"N1 1
,5

8 t"'x'Ulzp)zpt, t6
10 t"'x'zplzptrU1 18

14 ti xz zp6 xz lp1,lp1, t4
lsz k2 3p11ptr3p1, r7
t7 zsz ?p6

1s2 z:2 2p6 lsz 3p6 3d 4s2 7

25
k2 3p6 3d1o 4'st 11
D b2 2s2 zp6
ts2 z! zp6 x2 lp6 zdlo 4s2 4p6 5s2 z
38

.'. Atomic number of the element : 21

Rules for linding the GrouP No'
(i) If the last shcll contains 1 or 2 electrons' Hence the element is Scandlum (Sc)
thcn ihe group nu-ber is I and 2 respectively' MAMPLE 4' A neutal alom of element hos
(ii) lf lhc last shell contains more than 2
clectrons thcn the group number is thc total num-
ber of electrons i-n the last shell plus 10'
(iii) Ilelectrons are presenl in (n - l) d orbital
in addition to thosc in the ru orbital' then the group Solution. The electronic confrguratiotr of the
number is equal to the total number of electrons elem 8L and 5M electrons will be
present in thi (n -1) d orbital and ns orbital' tP x, zfiz$fit* 3p',\P';Pt
' Whal qtoms arc indicatedbY tlte
(a) Total no. of electrons = 2 + 8 + 5 = 15
?
lollowing electronic conligurations ].' Atomic No. of the element = 15
0) 1s2 2s2 zpt
(ii) lArl4s2 3.11
(b) Tbtal no. of s-electroDs =2 +2+2=6
number of clectrons in
(c) lbtalno. of P-electrons : 6 + 3 = 9
Solution. (i) Total
bz 2sz 2p1 =2+2+l=5
(d) Since the atom is neutral,
.. Atomic number of the element : 5 ;. No. of protons = No. of electrons
Hence the element is Boron (B) = Atomic No' : 15
(ii) Total numbcr of electrons in (e) Since the element has onty three half-flled
M\ = 18 t- 2
lAr)4s2
t I = 21 atmi; fuitals. therefore, valency of the elernent = 3'
ATOMIC STRUCTURE
3/s 1

case should be completely fillcd before rhc

electrons go to higher energysubshell, i.e. 2p in the
(i) Cu2+ (ii) Cl+ 1ii) Fe2+ ottd Fsr+ present case.
(iv) H- (u) S'z-
the formation of cations,
elect in the formation of anions,
elect he valcnce shell. The num_
the
rs empty.
l"# (iv) This electronic confilruration is wrong
since after filling 2s-orbtial, the e'iectrons sbould gE
the
questlon. to 2p-orbital rather lhan 3s-orbital.
(l) Cu'?+ = 2sCu - k- 't .t :. Consider the follow,ing electronic
co J.'
= 1s2 bz 2p6 kz 3p6 3dto 4s1 _28- $) lsr zst 6i) 1s2 3st
= 1s2 2s2 2p6 k2 3p6 3de (a) Nsme lhe element coDesponding to (i)
(r'i) CF+ =
-Cr - 3e- . (b) Ddes (ii) cotdspondto the same ordifferent
= 1s2 22p6Xz3p6# 4st -k-"
(c) How can (ii) be obtained
= Lr2 bz 2?6 3s2 3p6 3d3 from (i) ?
(rii) Fe2+ = ruFe - 2e- (d) Is it easier to remove one electron
frum (ii)
or (i) ? Explain.
= 1s2 zs2 zp6 3sz q6 # 4] _ z.- (g) The elemeot corresponding ro
= 1sz 2p6 *1 3d6 3d ...
(i)
.
is
..Sgl.uJfon.
Lithium (Li).
pe3+=roFe_3e-
^2 (b) This electroaic con.figuration represents
.,
lhe samc elemetrt in the excited statc.
= 1s2 %2 2P6 3s2 3p6 \dt
' (iv) H-=lH+1e-=bl+kr (c) By suppllng energy to the elemenr when
=k2 theelectron jumps from the lower energy 2s_orbital
(v) 52- = 165 + 2e- to the higher energy 3s-orbital.

= 1s2 '2s2 zpg 3s2 3plQtrZp! + u_

l:'. I I I'l
29 electrons an
of protons and
element.

-S-o[u.!!qp.-For neutral atom, number of

protons = numberof electrons : 29
Thus atomic number of the element
= 29
Electronic configuration ofelement with Z=
29 will be
1 s2 2 s2 2 p6 3 sz 3 p6 3 dto 4 st
or[Arll8 sl r'.e. ,oCu.
3,.llo 4
Note. No. ofneutrons are needed onlv to find
mass number.
Mass number = Nol of prototrs + No. of
neutrons
=29 +35:64
 Pradeep's
3152

1. Give tbe electronic configurations of: (it) 1s2 2s2 zptr2p1"

(i) Scandium (At. No.21), aod (iiD b2 xz 2p6 3sz 3p6 3d5
(ii) Chrcmium ( (iv) tsz ?s2 2p61s2 3P6 3t 4s2
t '41 1,t"-, G z? tp! zp!, tp! #
1i7
4"lI
2. Write the electronic configorations and the names
1ii1I;*at.zp!,wl
of ths elemeDts having theatomic numbers 5,9, 10' @ir;:4,zp632b5&#
Q") G 2i 2?6 3? 3P6 # *tl
19 and 20.

I Alornic No. Ekctto'tic Ndme

9. The atomic mass ofaD element is double its atomic
co^figurolions
numbr. If there are four electrons in the 2+-orbi-
s G*a! Boron tal, then draw the mo'lel of the atom showing the
ariangement of protons, neutrons and elecffons'
s # b' A',4 zPl Flourine
Give itsvalency and name the element'
10 t"'zzi tfiz+1,fi Neou
1r's. Yl zi tfizpt ?], two, oweenl
19 lJJz?zP6*lP6*r Potassium
10. write the electronic configuration ,F19, ',uS32 of
zo 1? zs2 2p5 # 3P6 4? catciuEl
and ,rA.f8 and then point out the element with :
3. Givo thc elecronic configurations of the following
: (i) Maximum nuclear charge (ii) rDinimum number
elemcnts lgK, 25Mn , 2oca
Ji n.rttont (iii) highest mass number (iv) maxi-
[.\is. reK = G z] tpt * lp6 *r , mum number of uDPaired electrons

,rut = t? z? tPG t? b6 # 4? ' 1,\rrs. r['r, = * 2] r.p12P12pl,

,oca = G z? zPG * tP6 Gl ,0s32 = t'? z? zp6
ss' \P?Jef+'

4. Wrlte the electronicconfigurations ofthe elements: ,r;s = i? z's? 4e s? h6

Chlorile and PhosPhorus' (i) MatL rluclear chErge = lt in ,3Afl
1,{'rs.61'r1o"in" ( flcD = i' i2 2P6 3? 3e" lfi lpl in lFr9
' (ii) Minimum no. of neutrons = 10

Phcphorus ( rsD = G z? 2p5 33 3pSPFPll ulPaired electrons = 2 in ,oS'21

(iii) Maxiuum no. of
5. Give the electronic configurations of the following
11. What are the atomic numbers of clements whose
ions : (i) H- (,D Na+ (iv) N- ('v) N2+ outermost elecrons are represented by
1,r'.'. 14 rs: 1i4 # zl zps 1ir1 t ? tl zt_a
(D 301 (ii)2P3 and
@) G z? zptl
6. Writ; do\rn the elecironic confiSuration of an ele-
ment with atomic number 14 Which SrouP in the figurations ?
Periodic table does this
element b to ?

GrouP l4l (,) [He] 2rr (ii) [Ne] 32 3p3

(iii) [tu]3dr4s2 ' (i) Li (ii) P 0:t scl

7. Name the elements that correspond to each of the
1J. whi;h of'the follo\ i figurations rePresent
fotlowing electronic mnfisurations Write down
the element in the gro d which in tbe excited
their atomic numbem also'
state ? Name the elemeot in each case :

(i) tsz 2s2 2p2 (ii) lsz 2s2 2P6 k2 3P1

(i) 1s2 2\1 2p1 (iD 1? 2.t2 2p1
(iii) 1s2 252 2?6 k2 6
(iii) 1s2 xr 2pr,2P1j 2P1,
I s (r) 6C ('i) trAl (ir) 13Arl
Zal
t. Correct the follo$'ing electronic configurations
of 1it1tsz x2 zp6 x2 zpt, zpl, zp!
the elcments in the Sround state :
t!rs. (i) Be (i, B (iii) c (iv) s
(All are in excited state exctpl' (ii)l
(i) isz 2.s1 2p!, 2P2y2P13? 3Pt,
ATOMIC STRUCTURE
3/53

8,16f,: ..68:HRoE L'EM9. eo Nf I

14, Ap-subshellwhich consists ofprp) andp,orbitals
contains only ooe electron. In which one of these
(c) H+ (b) Na+ (c) 02- (d) F- (N.C.E.R.T)
three orbitals should the electron be located? Jus_ l, (a) rro (b) # 2l ?6 1c1r? z? zp6
tify your answer.
I In any one because they are degeneratel t7. whar aloms are indicated tr,r"til,H,,f 3:l
figurations ?
15. Which ofrhe following quaDtum numbers fororbi_
tals in hydrogcn atom has a greater enerry for
(a) [He] ]r (6) [Ne] 3r2 3p3 (c) [Ar] tu2 3d1
electroDs ? (N.c.E.R.T)
(i)n=3,1=za\dm=+1 I \rs.(a) 3Li (b) lsp (c) 2rScJ
(ii)n=3,1=2andm=-l It Give the numbr of electrons in the species
[ ' SaEe enerB/ but dilfcrcDt oriertatiotrsJ H2+, H2 and o2+. (N.C.E.R.T)
16. Write the electronic configurations of the following I rlls Hr+ =2- l=le-tHz=t+t=2e-,
loDs :
or+ = t 1g - 1= 1511

F OR DIF F ICUI:T ?RO?LEri/'S

6. E.C. of ,nX = kz 3f. as l.
1s2 2s2 2pG the last shcl I
1i; when tasr shell is 3rl. comptere E.C.
contains 4 electrons, group Dumber
= 10 + 4 =14. = bz 2s2 2p6 kl
7. (i)Z=6,Elemer.tisC(ii)Z= 13, Eemenr is At (r) When lasr she
(ii, Z = 18, EtemeDt is Ar. is !p3, comptere E.C-
= 1s2 v2 2r3
9. Valency = Number of half-flled orbitals.
(.ii) When last shell is 3/, complere E C.
= bz Z] 2p6 kz 3p6 t$2 M6.

The shapes of nve d-orbitals and tbeir desipations

are as follors :

The shape of the first four orbitals is called cloverJcafwhile

that ofthe last one is called dough_nut shap.
The shapes of sevenfurbitals are comphcated
but t leir desigoation, r, ,o,,rra,
"r"
13, , fl , fi , f,e2_y7 ,fy1t_,21 , f,1y2_?.1 , Ly,.
I:'or La (Z = 57), the expected electrodc, confguratioa is
[Xer5a 4/ 6 s2. But actuar electronic mnfiguration
is [Xe]s 5 dl 6 12 ie. ir belongs to d_blocl( aDd Dot/_block elemcot&
3154
Pradeep's Co ':,tefr.i;t
"N-C*

o_n-a*_a_PI
of the gas tEide the.discTTj:.:-:-::."'::
Q. Why cathode rsys are produced onlywheE the Pres6ure
l.
current lloqa through the tubc bcause gases
Lo e, iiglr", pr"oure (e.& at 1 atmosPheric pressure)' no eleatric
are Poor conductor of electricity'
q 2. Give two examples from evcryday life rYher cathode ray tubes are used_
tubs'
Ans. (i) Teleilsion picture tube (ri) fluoresceflt light
rays altd anode rays ?
Q l. What is the ililference in the origin ofcathodc
aDode rays are Dot prod"red from the anode They
arc
uhereas
**
Ans. Cathode rays originate from thqcathode
by hiSh speed cathode rals'
pt.ii"*oii", th"e gaseous atoms b'y knock out of tI e electroos
gas is taken ond in the other 02 gas is taken' will the
electrons and positive ions
Q. {. In one discharye tube.II2
diffcreDt ?
in the cathode rsys srd in thc anode rals be same or
same'
Ars. Electrons will be same but positive ions will not bo
foil of gold, very few a-particles are dellected bacL lvhat does
it prove ?
Q. 5. When a-rsys hit a thin
within the atom' called nucleus
Ans. There is a very small hea\y body present
atomic mass and ltrs'ss number ?
Q. 6. What is the differelrc! between
it the sum ofnumber oJ Protons and number ofncutrons whereas
Ans. Mass number is a whole number because is
aton]
mass of iis atoms as comPared with mass an
atomic mass is fractioout o"""rr" it i. tt average relative
"
of C isotoPe takeo as 12'
- 12exaEple
Q. 7 Give on. of each of the following :
(ii) Isobar of flAr (iii) Isotone of |ac
(i) Isotopc of i;cl
ans. 1iy llcr 14 f$r (i,,) A60

Name the elcmeDt itr each ofthe follo\*ilg cases

:
Q'8.
(i) A bivalent onion ofthe element having 10 electrons
(ii) A triva ation ofthe elernelt having 10 elcctrons'
What is th tionship between the two ions called?
Ans. (i) OxYgeD
(ii) Aluminium.
fhe two ions are called isoclcclronic' of
g aPproximate mass in kilograms of the nucleus
(). Calculate the aPProximate charge in coulombs and
x -1e coulombs
lltHT;'.iT[p,o', t ur : prfin. und 4 neutrons charge on one Proton = 1 60 10

^r.. x 1 60 x 10-19 c =4 80 x 10-19 c

''charge on 3 protons (i a charge on nucleus) = 3
Mass of proton mass ofneufion - 1 67 x 10-27 kg
=
. . Mass of nucleus ='7 x 1 61 x 70-21 kg = I1 69 x 10-27 kg
waYe theory ond Plarlcks quotrtum theory ?
Q. I (t Wh8t is the main difTereDce betrYeen electromagnetic
whereas according
the energy is emitted or absorbed continuously
ADs. According ro electromagnetlcwave lheory' in cerlain definite
l() l,lanck.s quantum ln*ry,.n"rgy ir;i,ied
orabsirbcd disconri0uousty i.e. Packelscalled

'quanta'
photon ?
Q l l what is the differnce betweeD a quantuE alld a
photon'
is allcd a quantum whereas that oflight'is called
Ans. The smallest packet of energy of any radiation
cach other ?
Q ll. Ilot sre flequency ond wave number related to

of light' v is l'requency and is wave number'

turs. c = , i =, ! o, , = c i, where c is velcxity '
-l accordiog to frequency'
Q- l Arronge X-rays, cosmic rays and radio\daYe's
 ATOMIC STRUCTURE 3/ss
Ars. Cosmic ra)4i > X-rays > Radiowaves
(.) lJ Whrt do you observe in the spectrum ofN&Cl ?
Ans, Two yellow lines with wavelengrhs 58m A and 5896 A.
(., I s Which series of lines of the hydrogen spectrum lie in the visible region ?
Ans. Balmer series.
. r.) I n Why are BohCs o.bits called stationary states ?
Ans. 'fhis is because rhe energies of the orbits in which the electrons revolve are fxed.
(-, , I What is the difference betrveen ground stat and excited state ?
Ans. Ground state means the lowest energy state. When the electrons absorb energy and jump to outer orbits,
" this state is called excited state.
() i s Why electroEic energ5r is legative ? Comment on the spacing between thc energr levels.
Ans. Refer to text (page 327). Tre spacing between the ener8y levels decreases as we move outwards from the
nucleus.
(.) I ')
What do you mean by saying that energy of ti:e ele.tron is quantized ?
Ans. 'Ihis means that the electrons in an atom have only definite values ofenergres.
r.\ l0 Why the numberoflines observed iD the hydrogen spectrum is very large ?
Ans. Refer to the lcxt (page 3PA).
(.) : I How much ener$/ is required for the removal of the only elcctron present in the hydrogn atoltr ?
Ans. aE = E6 - El = 0-(-21 8, 10-te J)

=21 8 x10-19J.
r.) -ll What is the maximum number of lines obtaioed when the excited electron of a H atom in,l = 6 drops to the
ground statc ? (N.C.E.R.T.)
tu$No.of a (a-:11 1)
lines produccd when electron fiom n th shelldrops to ground state - -6(6- -r,
[These are produced due ro following lransirioDs
6.+5 5-4 4.+3 342 2.+1
. 6-+4 5+3 4-2 3-l
6+3 5_2 4.l
6-2 5.+ 1
6.... 1
(5lines) (4lines) (3 lines) (2lines) (1 liDe)l
1.' : I lvhich transition betweeD Bohr orbils corresponds to third line in the Balmcr serics of the hydrogen
spectrum.
Ans. 5th orbit to 2nd orbit.
Q 2,f . Which ofthe folloying relate to waye mture oflight or partlcle DaturE or both ?
(a) IDterference (b) DifirsctioD (c) Pbotoelectric effcct
(d) Black body radiation (e) Planck,s equation E = hv
- (Q Einsteil equation E = zrl.
Ans. (4) tr\hve nalure (6) Wave nature (c) Particle nature (d) Pafticle nature () Both particle and wave nature
(/) Particle nature.
(.1 15 Which quantum number does rot follo\d from th solution of Schrodirger t7ovc cguotion ?
Ans. Spin quantum number.
l.) 'l(r What shell would be the lirst to have ag-subshell ? Horf, mony orbltols will bc polsiblc in og-subchcll ?
(N.C.E.R.T.)
Ans, For g-subshell, / = 4. As I = 0 to rr_1, henc 4 = 5 ie. 5th shell.
Fot I = 4, m = -4, _2, _1, 0, + t, +2, +3, + 4 ie. 9 values which means 9 orbitats.
rl l" How many electrons-3, are prcsetrt in ell subshells (fully.fillcd) with ,| + , 5 ?
=
3/56
N e ut Co ursc Chem isftgtrfrlD
An6. Subshells *ith,l +l=5are5s,4p,3d.HenctelectronsPresent=2 +6 +10 = 18.
(.) I s How many electrons in an atom have the following quantum numbers ?
I
()n =a,,,ls= - Z (ii)a =3,/=0. N.C.E.R.T)
AIrs. (i) lbtalelectro rsinn=4 are2n2 i.e.2 x 42 = 32.Half of them t..e 16 electrons twnen"= -).
(ii) n = 3,1 = O means 3$ orbitalwhich can have 2 electrons.
(l le What is the atrgular moEcntum of an electron in (i) 2 s orbitEl (ii) 4 f orbital ?
Ans, Angular momentum ofelectron in any orbital = * 'rnfA1,
.. For 2 r orbiral,I = O, .. angutar momentum = r'd@ + q =0.
-1
For 4fo6ital,, = 3, . . anguhr mornentum = AA-lf'!,= O!
(-) ! l,
If,'hat is the dillerErce between the rotstioBs , and L ?
Ans. 'l' represents azimuthal quantum number which can have values 0, 1, 2 etc. L represents second Bohr orbit
forwhichn = 2 always.
'.) ll
Do atomic orbitals have sharp bouldaries ? Erplain why or why not ?
or Why doD't wr draw a bouDdary surface diagi'am within ehich the pmbability oflinding thc electron is lfi)% ?
Ans. No, atomic orbitals do not have sharp bouDdaries bcause the probab ity of finding the electron even at large
distances may b very small but not equal to zero.
(l..ll what is the differenc! itr the angular momentum ofan electron prcsent in 3p and that pEscnt in + orbital ?
ADs. NodiffereDce becauseangula! mcrnentum = * 'ffr7=, ie it dePen6 only m the \.alue of land rlot a
(l l.l V/hy splititrg ofsp..tral lines taks placE wheE the source giviDg thc spectrum is placed in a EagEetic lleld ?
Ans. In the presence of magnetic field, the orbitals present in a sub-shell (which were degenerate) take up different
orientations.
(.) 1l How many electrons in sulphur (Z = 16)canhaYcz + r= 3?
Ars. 16s = 1122?2P53s23P4
For 1.r2,n +l= 1+0= I
For2s2,n+l=2+O=2
For2p6,n+l=2+1=3
For3sz,n+l=3+O=3
For3pa,n+/-3+1:4
Thus n + / = 3 for 2p6 and 3 s2 electrons t-e for 8 electrons.
ll .r5 The 4/subshell ofan atom cotrtains 10 electrotrs. What is the maximum nuErber of electrctrs having spin
in the same direction ?
Ans. SeveD.
ll .rt why Pauli exclusion principle is called exclusion principle ?

Ans. This is because acmrding to this principle, if one electroD in an atom has some particular values for the four
quantum numbrs, then all the other electrons in that atom are excluded from baving the same set ofvalues.
{.) tl Horr mary orbitals are presetrt in the M.shell ?
turs. shell (r) Sub-shells (0 orbitals (m)
3 0(3s) 0 = 1
1(3P) -1,0, +1 = 3
2(3 d) --:2'-1'O' +t' +2 = 5
Total = 9
Altcrnativetlt no. oforbitals = n2 = 32 = 9.
 ATOI\iIIC STRUCTURE 3157

Q -rs IIow many spherical Dodes are prcsclt itr 3p orbital ?

An6. No.of nodes = (n-l-1) = (3- 1-1) = I
Q l9 Why Hund's rule is called rule of rEaximum multiplicity ?
ADs. This is because out of thevarious possible electronicconfigurations, only that configurarion is mffect ior wbich
the total spin value is maximum.
(J. l(l-wbichoutotcu2+,
Fe2+ andCi3+ has highest paramagnetiso atrd why ?
Ans. Cu2+ has one, Fez+ has four and Cl+ has three unpaired electrons. Hence Fe2 + has highest paramagnelism.
QI I Which of the followiDg are isoelectroric speciqs ?

Na+, K+, Mf+, ca2+, s2-,Ar. (NC.E.R.T.)

tus. arc: Na+ = t1 - 1= 10,K+ = 19- I = 18, Mg2+ =
No. olelectrons t2-2-10,
C,az+ =2O- 2= 18,52- = 16+2= 18,Ar= 18.
Ilence isoelectronic species are Na+ and Mg2+ ; K+ , C.a2+ , 52- and Ar.
(.1 ll What src the atomic numberc ofelemeDtsphose outermost lcctrotrs are rcpresented by
(c)3sr (b)2p3and3F? (N.C.E.R.T.)
Atts.
G4ts22s2zp6ztl 1Z=11) (b)1szzs2zp3e=i) (c)ts22szzp63s23p6+s2zd1z=N1.
(.1 J-r' What is the maximuE DuEber ofelectrols that can be prseDt irl on atom io which thc highest priDcipal
quantum numbr is 4.
Ans. KeePing in view aufbau principle, the electronic conliguration of atom having highest !lue of n 4 will be
=
tsz 2s2 2p6 Ssz 3p6 4s2 Mlo 4p6 (y'J]tet 4p, fi
lling of 5s starrs)
Hence maximum number ofelecuons present = 36 (IG).

,?*kg-r-t-An?Y?l,,.qy'e-e!-:ip-te CARRYING I MARK

Q. 1. What are the dilfereDt isotopes of hydrcgen ?

Ans. Protium ( rH1), Deuterium ( lll2), Tiirium ( 1H3)
, Q,2. How maoy neutroDs are prcscnt in ,rU2s ?

Ans. 238 - 92 = 146

Q. 3. Wbat hsppens when s Eica whecl is pltced in the path olcathode rays ?
^ Ahs. It betins to rotate
Q. 4. YYrite down the actual value ofcharge and mass ofan electron ?
Ans. Charge = 1.60 x 10-19 coulombs,
mass = 9.11 x ro-31 kg
Q. 5. What tIPe of cathode lvas used by Goldstein iD his dxperimenls oD the study o[ anode 1.g]is ?
Ans. Perforated cathode
Q. 6. Which elernent does noa ha},e anv neutron iD it ?
^ Ans. Hydrogen
Q. 7. What is the value of PlanclCs cotrstaDt in S.t. unils?
AIrs. 6.62 x 1O-3aJs
- Q. t. What is Rilz combitration priDciple ?

Ans. ,=R f+ - + ) where R is calted Rydbrg constanr.

l"? n? I

Q. 9. Write the expression for the energ5r ofelectror ofhydrogetr atom in tbe rrth level.
4,,". 5- =
-lLl2umsl-r.
n'
 ltradet,lt's Neut Coursc Chemistrrf lfim
3/58

Q. 10. llhat is Bohr's postulate ofengular momentum ?

Ans. Angular mome ntom, m", = n L-

Q. 11, Which orbital dos not have directional characteristic ?

Ans. J-orbital.
Q. 12. Which quallttlm number deterEines the
(a) shapc (r) oricntation and (c) size ofthe orbital ?
Ans. (a) Azimuthal (D) magnetic (c) PriociPal
Q. 13. Which cnergy leycl does not hove ap'orbital ?

Ans. lst enerby level.

Q, 14. Which is the fitBt enerB/ level containing/-orbitals?
Ans. 4th
in the d'sub-shell ?
Q. 15. What is the maximum number of electrors that can be accoEoodated
Ans.'Ibn
Q. 16. Which element has olly one electron in thcd'orbital ?
Ans, Scandrum (Z = 21).
Q. 17. WhBt is the physical siSnilicancc o 1.l, atd,l'2 '!
Ans. as such has no physical significanc.
ry' ,y'z gives the probabitity of finding the electron at any point around the
nucleus.
Q.1t. Write Schrodinger waYG equation in the briefest possible form'
Ans. rI l, = E V where H is called Hamiltonian operato
sn orbital ?
Q. 19. Which quantuh Dumbcr tcnds to specify thc orientatior in sPace for
ADs. Magnetic quantum Dumber.

SWer eetio CARRYING 2 or3 MARKS

Sec.3.1. Ho\P are cathode rars oriSinated ?

to 3,2.
How can you say that electron is a universal constituent ofall atoms ?
3. Givc expenments to show that
(i) Cathode ra,s carry Degative chargc (ii) Cathode rq's consist of matcrial particles'
Scc.3J. 4. How was proton discovered ?
Scc.3.4. 5. What was Thomson modelofatom ?
to 3.5.
6. How can you say that nucleus is small in size but healy in mass ?

Scc.3.6. Who discavered oeutron and how ?

Sec.3.7. t. Define'AtomicDumber' and'Mass number'
to 3,8.
9, What are isotopes ? Ho'v are they represened ?
Sec.3.9. 10. Define wavelength, frequency, wave number and velocity of a wave. Ho$' are they inter-relatcd ?

to 3.10.
Scc.3.11. 11. What is Planck's QuaDtum Theory ?
Sec.3.12. t2. Hop is the aromic sperra of hldrogen obtained ? what are the differeDt series of lines presnt in it ? In
which regions do they lie ?
13. what is Rydberg formula ? How does it help to calculate the wave numbers ofdifferent serles oflines
of the hydrogen sPctra ?
14. what is the difference between Rydberg formula and Balmer formula ?
Scc.3.l3. 15. What was the drawback of Rutherford's model ofatom ?
Sec3.14. 16. What do you understand by statlonary states ?
to 3,15.
AIOI\,4IC STRUCTURE 3159

77. Whar do you mean by quantisation of electronic enerry aDd angular momentum ?
It. Holx dos Bohr model explain the linc spectrum of hydrogen ?
19. Hcw dos BohI model explain the simultaneousappe8ranc ofa large number oflines io the hydrogen
spectrum ?
20. Outlioe the wlnesss of Bofu's model of atom.
Sec,.l.l6. 2t. What happcDcd to Bohis model of atom in the light of uncertainty principle ? Explain rhe coDcpt
of 'probability'. Define 'atomic orbital'.
scc.3.t7. Ho are the quantum Dumbers related to each other ?
S cc. .l.l li. 23. DeEne Pauli crclusion pri[ciple. Why is it called exclusion principle ?
Scc.3.l9. 24. How do b, 2J and 3s-orbitals differ from each othcr ?
Scc.3.20. State and xplaiD 'aufbau principle.'
to 3.l, t.
26, State and explain'HuDd's rule of maximum multiplicity'.
'Why
do some atoms pcsess xccprional electronic configuration ? Fl(Plain with suitable ammples.

1. Ho[, was clcctron discoverd ?

z. How are cathode rays produced ? Briefly explain their important propcrties.
I What are Anode Rays ? How do they originate ? Ljst thcir important propcrties.
4. Briefly dscribe Rutberford's scatEring experimeDt about the discovery ofnucleus.
5. Hc,u, was tbe nucler model of atom discovered ?
6. Ho|l was neuuon discovcred ? Describe briefiy.
7. (4) Define the terms Aromic Number and Mass Number. (6) Holv dcs mass numbcr diffcr ftom
atomic mass? Ho\x do atomic number (Z) aDd mass oumber (A) help to calclllate the Dumber of
eleatrons, protooc and neutroDs iD an atom ?
E. What were the main poiDts of Electrc'nagnetic wave theory ? Wbst v/ere its limitations ? How have
these ben overcome ry Pianck's quantum theory ?
Bricfiy explain what do rou undersEnd by black body radiation and photolecrric effcct ? What is
work function ? How they led to the concept of panicle nature of electromagnetic wa\rcs ?
10. lrty'rite siort notes on thc followiDg :

(i) Solar spectrum or contiDuous spectrum

(ri) Atomic spectra or line spe.tra
11. What trras the drawback of Rutherford's model of atom ? Descfibe Bohr's model of atom and rplain
its usefulness over Rutherford's modcl.
What wre the wealnesscs or limitations of Bohr's model of atom? Briefly describ thc quantum
mechanical model of atom.
13. List tbe main poiots ofdifference bctwn orbit and orbital.
t4, List the main features of the "quantum mechanical model of atom,,.
Sec.3.l7. 15. What are 'quantum numbrs' ?
to 3.1t,
16. Briefly describe each of them.
(4) How thc study ofquanom numbrs led to Pauti exclusion priDciple ?
(r) U8ing tbe concpt of quan tum numbers, c{lcu late rhe distributioo of clecllon8 as well as maximum
number ofelecrrons iD rhe N-shell (4th shell).
Sec.3.l9. 17, Dscribe the shapes of,, aDdporbitsls.
Sec.3.20. 1t. St8te and erplain the follc'wing :
lo 3.21, (i) Aufbau principle (ti) Psuli xclusior principle
(iii) Hund's rule of maximum muttiplicity.
 I,OiNAl;U,s.E
l.canwescethcotoms?ForthelastDearty200years,theatomswerebelievedtoqistbuttherewasno
strow ttleir existence. It is only recntly that the-direct photographs of the atoms have
been taken
oirectlrooito
using i tcchnique called ScanEing Tlttrreling Micrmcopy (STM)'
in 1895 observed that when cathode rays hit the anode

ATOMIC MASS (A) ATOMTC No (Z)

AroMlc NO. (z)

FTGURE 3.32. Plot of JT vsAandJtr vsZ

3'BohrBurySchemeofdistributionofelcctrons.Todescribclhedistributio[ofelectronsindifferent
orbits around the nucleus, Bohr and Bury in 1926 put forward the follo\ irlg scheme :
(i) The maximum number of electrons in the,th orbit is givcn by the formula 2r2
(ii) The outermost orbit cannot have more thao 8 electrons and next to the outermost not more than 18
electrons-
(iii)Itisnotoecessaryforanorbittobecompletebeforcanotherstaltstobeformed.Infact,anewolbit
starb as sooo as the outermost orbit has got 8 electrons'
4. Calculation of radius of the orbil In a H-hke particle, for the electroo to coniiDue to move aloDg the
orbit of radiust,
electron
Force ofattraction on the electrcn by the nucleus = Ccntripetal force acting on the

:!/60
ATOMIC STRUCTURE 3/61

ADDITIONAL U9EFUL INFORMATION

.
Le. Zz2 mu2
._(r)

where ,?l is
==.+
f'
the mass and e is the charge on thc
electron, Z b atomic no. of the HJike particle (a& for
,Je+ ,z=2, for u2+ , Z=3 etc.) aDd u is the tangeDrial
wlocity. Also acmrding to Bohr's pctulale of angular
momeDtum.

mrr=n* h *(ii)
EliminatiDg u ftom eqos. (i) and (n) (by su bstitu ting
value ofr, ftom (ii) in (i) aod rearraDgiog), \xe get
n2 hz Bohr's Fltke atom.
...(rir)
4* m ZnL
For H-otoE, Z=I and fot lst orbit, n =I so that

,n= !' ;=os2-9A

u 4n2m"2 (called Bohr's radius)

Thus
o
For HJlke otomq ,o =
tt L
rn(,l-al,m)
and rr(H-tike atom) - - o szg n2
5. Calculatlotr of eEerB/ of the .lectroD. ^
Tbtal eners/ of the electron (E) = Kinetic eDer$/ + Potential ener$/.
t t ( 2.2\
=_n"-+\_ r )
Brlt from egn. 7i1,m,? = 4-

- 722
zf
722
f
7"2
,tf
Substituting thc value ofr ftom eqn. (ii), we ger
2.2 4r2m7z2 2 rz mz2 e4
-L= -2-x--An-= ----1"-
NotcthatKE. =4,r.r.= -4,-n,r^,"n rg.(\d= -+
... Erot.t,/KE. = (- Zz2 /2t),/ (7zz /2r) = - 1

Erotlf /PE. = (- Zez /2r)/ (- Zz2 t11= 172

KE./P.E. = (ZeL /2t)/ (- 7z2 try = - 1 72

6. Calculation ofthe ylo{ity of the elctron ir atry orbil Eliminating r from (i) and (ii) (by substituring
the value of r ftom (ii) in (i) and rerranging), we get
ForHJik atoms
""=+
rPotential enerry of the clcctrcn at distancct from thc nuclcus is thc Bork dotrc whcn thc clectron
moves from distancc
f
[ 2"2
6 to di6tancc r. Hcncc P.E. = I -+d,=--.z.cz
)r'
3t62 Pradeep's

ADDITIoNA_L-ueE-f qLlNEoR.!Y!AT!9!.1-c_ol1td
On substituting the values of the constants n,e and h,we get

108 cm s-l
2-lfs x ro8"rnr-1
o^=f; xx2.l8S, I

For H-stom, putting Z= 1

2*e2 2 188 x 108

t"= -ffi- = cmj '

Fhrther puttint n = 1, the velocity of electron in the first orbit of H-atom will be =2 lt8 x lotcmr-1
which is nesrly 1/137th of the veloclty of li8ht.
-7
AIso, from eqo. (i), it may be seen that ,2 =24 *61slr tho*s,l'tr, ""+
?, Cslculation of the number of rcvolutions of the electron in an orbit per sec
hnh ,;
By Bohr postu late. n ur = n i7 or = 1;;;
Number of revolutions per sec = -f49SU-9!!9-9'iss!!9!-

2ttt

2ltlrlf ,f=
= l< fon substituting the value ofu)
=4! lJtf
-. (ir)
1 it' nf

. . Time taken for one revolution =

4t?n?
---tr-
-.2
No. of revoluiions rer sec 'f
=4n'm * i
lo {.?'\
' ,'h'
\ )

+,?m7]ea
nJ hJ
Er
= --F 11\
l7)
where E1 = -'"'Y"n rrrr"eners/ of the tirst shell.

E, Calculction of numbcr of!,voves in any orbit

Circumfcrencc o[ that orbit= 2nt 2nt
No. ot waves rn any orDrt = ------T;;;i;;gG- = n7 mo
-
\ = J-
(t
tnu 6,. 6"
gro"lie relation)

2nrmo -tr-
- ---i- - 2 (tn
. u o"
2 nh -
- -i-
z; n
ATOIVIC STBUCTURE 3/63

C. B.S,E.- P.lt.T. ( /*,tA t N S ) S tzEC lA L

A. SU BJECTIVE QUESTIONS Protons inPOI- ion = 15 (in P) + 4 x 8 (in O)
Q. l. [Iow Eany Eodes are prlscEth qp.orhltal Rcp. =15+32=47
resent dlegrammstlcslly,
Neutrons rn POI- ion
Ars. Number of planar nodes = I (becaus forp-or-
biEl,, = 1 and [umber ofplanar nodes = value = (31 -rs) + 4 (16 - 8) = 16 + 32 = 4a
of, for that orbital) (in P) (in o)
Number of radiavsphorical nodes = n -, - 1 Q. .l Shold that the clrcuDfcrcncr ol the Bohr orblt
-3-7-1=1 for hydrogen otom ls sr htgral Eultlple ol thc
dc Brugltc vavclcugth eccodrtcd wlth the
Glcstrotr movhg srourd thc orblt (N.CER.I)
Ar& Arcoding to Bdlr pctulatc dangularmorrentum
m8-nT;h
PLANE PASSING
THROUGH NUCLEUS
^h - nh
or Zxr ...(r)

.'. Tbtal number of nodes in 3p-orbital

Accordhg to de Brogie cquation
en-1-3-l-2. ...0i)
Q. 2. If lhe enerE/ of a[ clcctrotr hr 3rd Bohr orblt ls
h (i) lst
^=!-
Substituting
mu
this value in eqo. (i), we get
-E, what ls the GrerSy olthe elcctron
Bohr o$lt (ii) znd Bohr orblt ? 2zr=nl
nns. E,
" 1... s " ]r". + " *,+ " ) Thus, the ciromferenc8 (2 zr) ofrhe Bohr orbit
for hydrogen atom is an integral mulriple of dc
Le-
l_
E2eT I BroSlie waveleogth.
\(r7, a. 5 (, AD atomtc orbltsl hss n = 3. mst are th.
E. pocclblc valuca ofl ond zr1 ?
.q=9.Er =eE;= -eE('.'q= -E) (ii) Ltst thc gosDtuD nuEbcrr (n, rnd 0 of
q4 cl.clrom for 3d-orbttsl.
q=E (iir) YVhlcI of the lollorhg orbltrk sr! pGtble ?
oo 1p, b afi 3!. (N.C.E.R.T)
...4=ier=_4E=_2.2sE. Ars. (,) When r =3,1=O,1,2-
Q -l. Calculate the total number ofel.ctrons, protons Whcn/ = O,rnr - 0. Wheal = 1,mt - - 1,0, +1.
and Deutrors in (i) NH.+ ior (i, PO:- ion. -
Wien I = 2,m = - 2, t,O, + 1, +z
hs. (iD For 3d-orbital, z = 3,1 = 2,
1i; Elecrrons in Nftf, ton = 7 (from N arom) + For I =Z,mr- -2.-1,0, + l, + Z
4 x I (fronl H atoms) - 1 (due ro presenc& of + 1
charSe)-7+4-1=10 (rtt) lp is mt possible because whcn z - t, / 0
=
only(forp,/=1)
Protons in NH4+ ion = 7 (in N) + 4 x I (in H) = 2r ir pGsiblc beaausc wicn n = 2, , = 0, 1 (for r,
'1 +4=ll t-0)
Neutrons in NH.+ ion = 04 - 7) + 4 (t - 1) ? i! pcsiblc bccausc wbcn n= 2, I= O, 1 (fot p,
(in N) in H ,=1)
=7 +0 =1 3/is not possible bcause wheo z =3,1 = 0,1,2
(ii) Electrons in POI- ioD = l5 (from P arom) + (totLl =3).
4 x 8 (from O arom) + 3 (due to presenc of- 3 Q. 6. Sho, thda groutrd ststc cEGrEt ol Glcctron ln
charge) hydrog!tr stoE lr cqual to the ,lr8t cxclted !tst!
ctrerDt oi clGcEo[ ln IIc+ lou, ascllDtDg thrt
=15+32+3=50 thelr Rydbcrg coDstsnts are equal.
3le Pradeep's

Ans. En = -Rr:!. Atrs. Refer to page 3/61.

Q. 10. The tlvo ext]a-nucles r electmDs In the ls orbital
lior H-atom, Z = 1 and for the ground state, of helium have ontiparallel spins (i J). Why
n='l not they haYe p0rrllel spiN ( t t)?
'tir=-RH (B.LT, Ronchi 1991)

For He+ rco,Z = 2and for the first excited state, ADs" they had parallel spins, tbe repulsion will in-
If
n crease. As a result, enerry will increase and the
=2 stability will decrease.
^2
%:-R,i=-R" Q. II. The eleEeDts P (Aton c ldcight 39) aDd Q
(Atomic $'eight tO) contalu 20 ard 45 oeutrotrs
Ilence the required result is pror'ed. respectively iD their Ducleus. Glve thclr
Q 7 @) Derive the relationship betwecn the electronlc arraDseDcnts Eeparat ly
waveletrgth associated with a moving Psrticle (I.S.M. Dhortud 1991)
ond its kinetic energs[ For elemeDt R A = 39,n =2O. As A =P + n,

or Derive the relationship therefore P:A -, = 3 9 -20 =19 . Ilerrcg e- = 19

^=L5^&Ej E.C. = 1"2 X
2P6 3s2 3f Asl
-- -2 4x1o''s!
(r) Horr is the frequency of the matter wave For element Q, A = 80,n = 45. Hence
related to the kinetic energ/ of the Particle ? p=A-n=8O-45=35. So no. ofe-=35. Hence
Ans. (4) According to de Broglie equation, t = a r.c- = t s2 z? 2p6 \s2 3p6 Mto 4s2 4p7 4t 4pt
Q. 12. Givc the name and stoEic number of the lEcrt
(, gos atoE iD whlch the totrl rumb.r of d-
2IcE. electrons is equal to the dlllerence bctEeen the
Further, KE. = ] m,2 or u = m 0i) trumbers of total p strd total s electroDs
Subshtuting in eqn. (i), we 8et (Wei Bengal t.EE. zlDi)
ADs. Electronic confiSuration of Krypton (Z = 36) is

^=*\/#-#
(6) Frequency ofthe matter wave,
36Kr = tsz z? zp6 3 ?
Tt tal number of
zoo roto o t' on

,r electrons = 8,

zK.E. 'Ibtal Dumber ofp- electrons = 18

' h/mt ^u2
l h h Differcnce = t0. Numberofdlectons isalso = 10.
'fhus frequency of the matter \l'ave is directly Q. l-1. what ore the total numbcr ol orbltels as-
proportional to the kineticenergy of the material socloted wlth the princiPsl quatrtuE DuEh.r,,l
particle. = 3 ? Brlelly cxPlatn ,
<Dirur C-8.8. 2003\
Q l{. For a hydrogenJike particle, derive the follor- Ans Number oforbitals in zth shell = n2. Hence for r
irg expression
= 3, number of orbitals = :2 = 9 (For explana-
tion, see 'Dble 3.3, page 3/40).
where zn is the velocity of the electrotr at dis- Q. I'1. A monoatomic atrloE ofunit charge contshs 45
tancc r, frcm the [ucleu$ Z is the etoEric num- neutrons and 36 electrons. Fintl thc stoElc
brofthe H.likc particle,z ard ere the charBe number, mass number of thc ioB with its idcn'
tilication. (West Ber,gal t.E.E. 2004)
and mass ofthe clectro[.
Ans. F-or H-like particle, force of attraction between .{ns. No. of electrons in the monoatomic anion
the electron and the nucleus = centrifugal force (x-r) =:o
. 7.2 mtf, . . No- of electrons in the monoatomic atom (X)
=35
,'^ Atomic No. = No. of protons = No. ofelertrons
" (zr'\1/' in neutral atom = 35
ot u;=-
" 722
- ".= l^r) Mass No. = No. of protons + No. of neutrons

Q 9 Calculate the ratio ofkineticenerBr to Potential =35+45=80

energt of any hydrogenJike Particle' Henc the ioD must beBr- (bromide ion)
 ATOMIC STHUCTUBE 3/6s
B. PROBI,/Lj,IIS problzm 4. When a crrtaln metal lras lrrodlsted
J,t |hL n 1. Calculate the distatrce of separation sith I light of ltequercy 3.2x1015H4 the
lretween the second snd third orbits ofhydrogen atom. photclechors had ttf,lcc the kiacdc cnerg5r os emitted
whrr thc same Eetrl was iFadlstcd l"tth ltght of It!-
Solution. For H-atom, the radius of ,th orbit is
qucDc] 2.0 x 1016 IIz Calculste ttrG thrcshol.l ftequer-
given =0 529xn2A cy (y0) of the ltrelsl
.. h - tz: O 529 (22 - t1 A Kinetic cnersr ,rf photoelegroDs
= 0.529 x5 - 2.645 A. emitt hvo-h1u-uo,
t'tobtLn 2 To which orbit the electron in the
hydroger atom will Jump aller absorbilg Io lst case, (K.E.)t = h Q.2 x lo16 - vo)
I .94 x 10-18 J ofenergr ? Ir 2rd cas, (K.E.)2 = i (2.0 x 1016 - vo;
Solution. Enerry of electron in the ntb orbit of
But (K.E.)r = 2 (KE.h (ciYen)
21 8 Iil0-le
H-arom is given by En -- J :. hA.2><1Or5-vs)-2h(2 0 x to16 - vo;

.. El = - 21.8 x 10-t9J ('.' n = I for ground or Yo=4 x 1016-3.2x 1Ol5

state of H-atom) = 0.8 x1o16=Ex10rlHz.
Afterabsorbing 1 94 x t0- t J ofcDers/, the cner- Froblcm S. The ravelcngth ol Ho IlEc ol Balner
S/ of the electron will be slrics ls 6gn ,tr" what is the rsyeletrgth of Hp llne of
= - 21.8 x 1O-le + 1 .94 x 10-ltJ Balncr sqies ?

2.4 x 10-19 Ha line of Balmer series is obtained

= - J
wlien\=\n2=1
- 2l'8 n
'Illus xrlo-Ig
=- 2 4 x lg-le Hp liDe of Balmer scries is obtained lltlen q = 2,
h=4
or nz =lf :e or n=3 rrusrx"=f =n,
Thus ttlc electron will jump to the ahird orbil [+-+, =", (+-+)
l'rublu l. An elec,ron in a hydrogeD atom itr the nr'f6 (0
grou[d state absorbs energ/ equal to I .5 tirEe the min. =
imum energr requlred to rcmove the clectron froDr the
hydrogen etom. Calculate the wavelenglh of the
elcctron emitted.
',, =
4 = ", (r' - +) = ", (,t- +)
Enerry required to remove electroo = n, fa
" ...0j)
from = 13.6eV
te of H-atom Dividing eqn. (i) by eqn. (iri), \r get
.. Enerry absorbed by the electron
= 1'5 x 13 5.V = 2O.4 cV
^rB s 16 20

After tbe remor'al of electron from the atom, extra

G-=B,T=27
coersr which is converted into kinetic eoerry ... t U-frx4o=ffxesoo A=,u14.Etr"
= 20.4 - 13.6 = 6.E cV
1- I\&km 6. Thc atomlc apectrum of hydrogen is
tirus jrn,z = 6 8 x l.6m x lo-leJ found to colttllD s sedes ofl ines at wavelengths 656 . 46,
4t6.27,4U.17 otrd 410.29 nm. Whot wtll be rhe
wavelength of the next line in the series ?
u= 1l
vi t
2x6.8 x 1.602x to-le
9 lI x l0-r' The given 'raveleDgths lie in the visible
regio they are expcred to belong to Balmer
='/14,10:r- = 1.55 x 106 ms-l series. Thus, zt = 2. [,et us calculale n2 for lhe shortest
wavelength viz. 410.29 nm
I /1 l\
r= ^""lv-al
\ '/
tO9.677 lJrn-l
x l0-'cm
410.29
t+ +l
3/66 Pradeep's

This on solving Sives /b = 6 =4x2.lEx10-ltJ

Thus the Dext line will be obtained for jump from - r.72 x to-ll J.
n2- 7 lo n\= 2, so that l'rohlun 9. Sodium ctrcet lsmP SlYec ol? r chsrsc'
_,(+_+) teristic yellov ll8ht ofttavclcDsth 56E nm. Calcuhtt tbc
+=n ,6n" energr per molc (ln kJ/mol) ol th6e Photons
(Bil,l, C.EE.2003)
=los,67j x (i_ir; ".-,
Solutlotr. I = st8 nm = 5tt x 1O-92r,
= ror,urr r#"^-1 =2s1Eo 9 "--l
c=3x10tms-l
or f = ----!---=. = 397 1 x 1o-7 cm e=Nohv=Nofti
25180 9 cm '

= 397 1 nuu (o.ozxtoa) x (6 63 x l0-3a) x (3 x 108),,,o,-r

l'r .l,ii rIl i Calculate the radius ofthc llrst orbit
- -------- 58S
ofelectron in on otom ofhydroge& "lO=!-
(LS.M- Dh4r6od l9ES) = 2.036 x 106 J mol-1
Solutiop. As derived on page 3/61, from eqn. (iii) = 2.036 x 103 kJ mol-1.

Rudir. ,' =
h' l't ol.h Di lt) Celculste the radius of Boht's lifth
12 . orbit for hydrogell atom, (N.C.E.R.T\
4*mZe'
For H-atom, /,, = o 529 x n2 A
t2 x (6 63 x 1o-27 erg sec)2
-
*ff)',<s 11x10-28g; x (4 8 x 1o-roesu)2
:.rs=O 52:9 x52 = 13. 4 = 1.3225!lm.
I'rohlu ll. Thc aDgular mometrtum of atr
= 0 53 x 1o-8cm - 0 531 elcctEtr itr Boh/s orblt of hydrogen atom is
/',.,r,,1, rr . CElculate the enerB/ requird for th. 4.22 x 1lo-v kgni s-l' catcul.t the wavelctrSth of
Processi thc spectrrl linc t?h.n thc GlcctroD fslls ftom thls lcYcl
to thc n.xt lof,Gr leY.l.
He+ G; Hs2+ G; .' .-
-
for the H-otom itr the
Angular momenlum (nor1 = n fi
The iotrizatioD etrer8o/
ground srate is 2 1t x 10-rt J atom-1. 1,V.Cf.f.f; 4 22 x 7o-Y klm1 s-7 (Given)
=
Sgbr-tlolL The energy of the electron in the llth
orbit of H- like Particles is ... n = 4.22x to-Y xT
u-= -'"'f:lth' =-x,{n'
n2
{x =.on,t"n,;
=-2\4.22xro-34x314
6.62i * ro-Y--
IEH=E--E,=o- ( fl -+K ..(i) When the electron jumps from z = 4 to n = 3, the
wavelength of the spectral line can be calculated as fol-
The enerry required for the Siven procss is I.E. of lows :
He+ for which Z = 2. 1- /1 1\
As He+ is hydrogen-like Particle
r=", l7-;l
\' ')
. I.E.H.+ = E- - El _, t1 1\
= loe,677 cm . _
t.r a,J
=o_[_*1r'l
r'] I =*ox ...(x)
= roe677 x f* - Jro,l = tosozz * fr-"--r
\v
. -.... lEn.*
From eqDs. (i) and (i), -f.ff =o
o, I = 15ffi7 rm = r.8t x 1o-'cm.
ie. I.E.H.+=4xLE.n
 ATOi,4IC STRUCTURE
3t67

l. l.T. {rtnAWS ) Sr,.ECIAL

l't,t,Lu I Find the quantum number .n, cor- . . 1 8 9 of hydrogen atoms coDtaio H-atoms
responding to the excited state o[He+ ion ifon traDsi.
tion to the ground state that iolt cmits two photons ir =6.O2xl0Bxl.8
succession with wavlengths 106.5 and 30.4 trm respec- = 10.84 x IOA
tively. Atoms present in 3rd energy level
Solutionr Suppose the electron in rhe excited state 27
= x 10.E4 x to4 = 292.68 x l02l
is present in the shell ,12. Firsr it falls from ,2 to rl
and =-
then from z1 to grouDd state (forwhich n = l).Thusthe Aloms present in 2nd energy levcl
two transitions involved and the corresponding
wavelengths emitted are =#o- x lo.8a x toE = 162 5 x lo2l
Atoms present in lst eners/ level
O nz+ \, \ = 108.5 nm = 108.s x 10-7cm
(ii)nr- 1,1, = 30 4nm = 30.4 x t0-7cm = #, x tlb = 62t.72 x tozr
tO.Sa

Applyiog Rydberg's formuta firsr ro case (r'i), wc ger Ionizarion potenrial ofH = 13.6 ?V meaDs thar
l?-6"v,
v=l=nz'11-11 = - 13 6eV,B = -
Er,"21
^ l* "i) g' = - 13.3"v
'3.
Energy released ftom all aioms when electrons
return from 3rd level to 1st level
= (B: - Er) x 292.68 x 1021
-1-0.75=025 / 136- tt \
= o) x zcz 68 x ro2rev
ot "1
ni=Oi=4 ot nt=2 [- i=
Applying Rydberg's formula no\y ro case (i), we get = 3 537 x 1024 eY
Energy released from all atoms when electrons
pzz(L 1\
lo-? "' lz2- "?l
return ftom 2nd level to 1st level
108 5 x
\ '/ = (82- Et) x 162.6 x tfr
=
l- tt.6 - 8.6)\ x 162.6 x to2t cv
[--fl
or -= 1
= 1.659 x loza ey
ni '. lbral enerry released
=0.25 -0 21 = 0.04
= (3.537 + 1 .659) x tou eV = 5 .tg6 x
.l t1z. eV
ot n;= Ofu=25 or tr=s. = (s 196 x t02a) x (1.602 x 10-le)J
l'ttklt! 2 1g hydrogen atorDs are exctted =8.3239x105J=E32.4U.
-.
radiatioDs. Thc study ofspcctntm indicrtG thstZT%;l
by
triply iotrized berylium
thc Etoms arc iD 3rd energgr level and 15% of otoEs arr
in 2nd enerB/ level and the rcsa in the ground stotc. ius as that ofthegmund
Ioniritiot! potItial of hl'drogE is 13 . 6 .V Cdculstc
- (a) number ofatoms ptrs.nt in cnerB/ lcvel lsg
2Dd atrd 3rd.
or. For HJike particles,r^ = O SZgx$
(r) total .ncrEy rrleascd injoules whcn all atons state of H-a(om. Z = l, n = l,
rctum to grouDd state. tr=0^For^ground
529 A

By mole concpt, I g of hydrogen atoms For Be3+ 12 = 4), ifzth orbit has rhe same radius,
conta x loa atoms
_.
then
3/68
I'rohlon T The ionizrtion energt of hydmgen
o 52gx+=o 52sornz = 4ie D=z atom is 13 6 eV What wtll be the ionization encrE/ of
He+ and Li2* ions ? (Roortce 1986)
+
Thus, second orbit of Be3 ion has same radius as
tbat of ground state (1st orbit) of H-atom' ^ 2r2 m 7]ea for hydrogen like
I'ril'lu l Nt elcctton iD a certain Bohr orbit has n2h2
particles
velocity U275 ofthc velo.ityofliShl In which orbit the
Glectron is revolving ? LE,=E--Er
Velociry of electroo
^ ( 2n2
='-[- ^zz
ea \ -L,1mzz ea

=fi"z"1olocms-l I )-----T
= 1 09 x 1oocms ' Fot H, z= 1 tz = 4!! = n a.u
VelNity of electron in nth orbit of Hlike particles ...(Given)
in C-G.S. units is given bY
For He+ ,2 = 2,1.E. = 13 6x7?
2nZz2
!r-_T =136x22=544eV
PrrltiD.gz = l for H and e = 4 80 x l0-l0eru (in For L?+ ,z=3,1.8 = 13 6 x 32 = l2z 4ev
C.c.S. units) andll = 6 626 x 10-27 erg sec, we get I'nthtut 8. Calculatc the velo.ity (crn/sec) of an
clectron placcd in the third orbitofhydrogenatom' Also
- z ts n to8
2 x.1 14 x (4 80 x l0-151 x
colculate the number ofrevolutions Per scond that this
,r x (o 626 x 10-27) electron Eakes around the [uclerts. (knrkee 1987)
2 18f< 108 As derived on Page 3/61
- 1'09 x 108 (calculated above)
24 z.ez 2x3.14x 1x14 8x 1o-ro;2
' n=2 "=--nE-= 3 \6A;1o=--
l\,,|'lut ; S laser emils moDochromatic radia-
10ti quanta per =7 27 xl cm/sec
powocr outPut of t
No. of revolutions Pe sec. = #
(Eqn- (,1,), page 3/61)
Energy ofone quantrm = hv = hcT
( nzhz \
'"lnl^a1
4*mtzez 2t mo zex
= 3 x lo-19 J 2, na hz n2 h2

EnerS/ emitted Per sec Per square metre = No' of

qr"nt, sq. metre Per sec x Energ/ of one
Per x
(3)2 x (6 63 lo-nf
".iit"d
quaDtum
=2 42xLIL
=1615x3'19-19;t-2t-l l'rohlen 9. Colculot the woyelcrgth and enerBr of
: 3 , 16-'; 6-2 s-r radistion emittcd lor the electronlc transitiotr from
1, , 1
l, ,n (, Calc]ulalE the frequency
ofthe spectral iDfiDity (.o) to station.ry st{te one of the h}drogetr atom
line emitted $,hen the clectron in rl = 3 in hydrogen (RydbcrB coDstrnt =1 0957E x 10' m-1,
atom alc-excites to the ground state (Rydber8 constant h = 6.62fi x lo-r Js). (Rarkee 1988)
cm-r) (Ru*oe 1985)
= 109,73?
,=R r!--L)
sor.rrio,,-, = - [+ - i] = ro,ru? (+ - +) \"i "i)
\"i "' )
(l - a) rn-r
= 97544 cn-l = r'ooe678 x ro?
\l' @- )
c
Y=T=cY = l 09618 x 107 m-l
I
= (3 x loro cm s-l) (97544 crr-'t) ^,:!=n l 09678 x to7 =9.11 x ro-sm
= 2 9263 x 1015 s-r
 ATOMIC STRUCTURE 3/69
Solution. Ener$, ofthe/rth orbit of H-like particle
E=hv=h.i=6.62s6x l0-ra x -9 11l,',91_u
x 10-E
=2179x10-ltJ 21.79 x to-19 x
z2!
nz
2 179 10-18 -. x
=;;1n=13-t''' .. Ener$/ of the 3rd orbit of He+ ion

2t .7g x to-tg
= 13.6eV (.. IeV = I.6 x 1o-leJ)
x 22 -
= - _-_-_ =-9.68x10-19J
I'rohlun 10. (a) Electromagoetic radiation of 3'-,
wavelength 242 Em is just sumcietrt to ionize the Enerry required to remo\,re the electron
sodium atom. Calculate the ionization energy of sod iuEt
in kJ mol-I. = 9.68 x 10-le J

(6) The ionizatio[ nerg/ of He+ is Now E=rrv-[i

19 6 x 10-18 J atom-I. Calculate the cnerp/ of the
lirst stationary state of Li2+. (Rnrkee 1989, 92) or r=f= 662x10-4x3x108
9 68 x l0-le
(a) We have to calculate enerryof radia_
lron with t = 2A2 Dm = 242 x 10-9 m. = 2.052 x l0-, m.

E=hv=hc - (6 6256 x lO-vJs)(3 x ldms-l) alculate thc frequelcy enertgr and

^ (242 x to-e m) wavel rsdiatioD corresponding to the
spectrsl liDG oflowest ftequetrcy in LyEan seiies iD the
= 0.0821 x 1o -17Jlatom spectra of hydrogen stoD. AIso cslculatc the frequency
for the corrcspotrding liDe in the spectra of Li2 + ion.
= (O 0821 x tO-17) x (6.023 x 104) J mot-l
(Rn = l 0!1678 x t07 m-r, c = 3 x l08 m s-1,
=0 494 x to6 J mol-l = 494 kJ mol-l
(6) As discussed on page 329
h=6.625x10-zJs) (Roorkee 1991 )
LE. of H-like particle =I.E.of H xt lr 1\
Solution. , =R
=ExZz l?- 4)
. I.E. (He+) =Ex* (ZtorHe=Z) For lowest frequensy in Lyman series,
nt=1,n2=2
I.E. (Liz+) = E x 32 (Z fot Li = 3)

... I.E.(He+)_ 4 . t= 10s677 x 107 fl|'r2- l l

e 22 )
I.E.(Li2+)
=O 82258 x 107 m-l
or I.E. 1li2+; = | x r.r. 1Hc+)
t="!= 1
I
= i x ts.e x 16-r8.; ulor-r
" o.Bzzs1 x to7 -
= 1.216 x l0-7 m
= 4.41 x to-17 J atorD-r
Pn,bh // Accordihg to BohrJs aheory the " =l = *o =3 x 108 x0.82258 x 107
- "
e rts' of hydrogen atoE in the Bohd; orbit
electroric
is given by = 2 47 x TOts s-r
21 79 x lo-19
E= hy=6.625 x10-34 x 2.47 x 1Ol5J
-
n- = 16 36 x lo-Ie J
Calculste the lowqst waveleugth oflight that vill I'nthlen l3_ Estimate thc difference in energy be_
be Dceded to Femove on clectron fmm the third Bohr tween the lst aDd 2rd Bohr orbit for a hyd.og", u-toln.
orbit ofHe+ ions. (r.r.T 1990) At what EiniEuE stoEic truDbcr, a transition from ,r
= Z to a = 1 eDerEO, level would rcsult in the emission
3170 Neut Co rse Cheru i strrl
I'robktn 15. Calculato the enerBy emitted rvhen
of X-rals *ith ,tr=3 0 x 10-t m ? Which hydrogen
electrons of1 0g atom olhydrogeD undergo transitlon
atom-likc species does this atomic number corresPond
(IT1993) giving the spectral line of lowest encr$/ itr the visible
to? regio[ of its otoEic spectrum
19 x fi-tg (Rx=I l x 10'm-l,c = 3xldnr-1,
solution. En - -21 .l

[ = 6.62 x 10-]' Js) (Roorkce l99j )

1)
. %_Er = _ 2t.7e x10',
-'o r '
\7_ 7) Solution: For lowest encrgy in the visible region of
atomic spectrum (Balmer series), /tt =/,nr=!.
= 16 34 x 10-1e J'

For ll-like parlicles, E n- -21

79 x L-o--tg xzz ! "-^t,l-Al
"=
(r-1] r.lx
n = roz f!-a'\
\z' *)
For a transirion from n = 2 Lo n= 1, =11x107(ra ;)=r uro,,S
LE = 21 1e x ro-le x z'(+ - +\ = 0. 1528 x 10? m-l
\l' 2')
f E=h"=ni=hct
= 16 34 x |O-le 7?

= 6 62 x lo-3a x 3 x 108 x 0 01528 x 107

^E=hv=hI
tr l=0ju
= 3 0346 x ro-19 J/g atom
. 11,.14 x l|-rs z7 = 6 62b x to-'o
' =3x 10-6 to-le; x 16 02 x l0a)
3 = (3.046 x J/atom

or 6 626 x 10-18 I o6o12=2. = 18 268 x ld J/g atom

z2 =i;?;; t+$ = = 182.6E kJ,/g atom.
H-atom like species that corresPonds toZ= 2isHe+' I'n'hh rn t(t Find out the number ofwaves made
I't,:i'tttn IJ What transition itr th hydrogen by a Bohr electron in its 3rd orbil (I.I-T. 1994)
spectrum would have the saEe wavelergth as the Bal' solution. No. of waves in any orbit
mer transition' z = 4toz = 2 of He+ sPectrum ?
Circumferencc of that orbit
(LI.T 1993, N.C'E-R.T) - Wavclcngth
Solution, For H-like particles in Seneral
_2nt _ 2nt -?lh,r\=+\h
l(h/mo)'hzr. =,
l\ l\
'=-ff 2n2mz2ea lt
F
--z(1
Al=^'' 14- 4) Thus, the number ofwaved in 3rd orbit = 3.
I'rohtur 17. Abutb eEits liSht ofyavelength 4500
. For Hc+ spectrum, for Balmer transitioD, tr- The bulb is rated ss l5{, rvatt snd 896 of thc ecrEy is
n = 4lo n =2. emittrd as light. Horv moDy PhotoDs ar. eEittcd by the
bulb per second. Q-I.T 1995\
r=!=tzz(; ;) Solutio!. Electrical enerry in joules = Poter in
watts x Tlme in seclnds
=n,4"rt=$ Thus 150 watt = 150 joules of ener$I emitted per
secoDd.
For hydrogen sPectru
... Ener$t emitted as light
,=|=n
113
[i ;)=;. e
=_;:xtso=t2J
or ni.--.=z
ni E=nhv=nhl
which can be so for n1 = 1 and nz = 2 .. n=-Exl
hxc
ie. the iransitioD is from ! = 2 to n = 1
 ATOMIC STRUCTURE 3n1

_ (12 J) x (4500 x 10-lo/n) .

EDerry required for excitation of0.0818 moles
- (6.46 ilo=s6 "O;lo5;-5 of H-atoms from ground state to first excited state

-27L7xLOl9. - (Ez - Er) x 0.0818 kJ

i'.,,hh rt j, Calculate thc wsvelength ofthcradia- l-lla- /-!p)lxo

= o8r8u
tion emittd producing a line in the Lymstr series when
aq electron lalls from fourth stltionarjr stste in
| ,' |' t'il
= 80.49 kJ
hydroScn atom. (RH - I I x 107 o-l) (Rorkce t99S) . Total enerry requircd = t?.83 +80.49 =9E.j2kl.
Solution. For Irman serics, r,1 = l,r2 = 4(Given) , | 't,,t _'i Calculate the ercrgy associated with
the first orbit ofHe+. A.lso calculate the radius ofthis
Applying Rydberg s formuta,, = R f+-+) orbiL
l"? ^i)
. r=1.1x107 lt1_ 1\ sofution. Ea - -21 8xl9r-re*,
\f q,)
15 _, zt Sxto-19x22
= 1.1 x 107 -- 87 2 x lo-19 J
'T6m'
_l 16 O 529xnz ,
r" = -----7:- A
1lx107x15
= 9.697 x 10-6 m =96.97aa1 - o s29-x tz - g 2n45 f,
lJr$lur lt) Calculate the wave number for the
shortest wavc lcngth transitior in the Balmer sEries of
atomic hydrogen, (I.r.T. 1996) of ll-atoms is 91 2 nm. Calculate the corresponding
Solutio_E For Balmer series,41 = 2_ Henc* wavelength ofIIe+ ion. <I.I.T. 200j)
Solutio_tr. For HJike paflicles,
- -11 l\
\22 nl )
'=r="ft-i)"'
, = i. Hence t will be shortest when r is largest ForHatom,Z=1
which in turn will be largesr if ,12 is bighest i.e. n, = a.
fr=n
Hence r = loe,6?7 fl
\22
- -L
*z )
l fr-+).r
For He+ ion, Z = 2. Henc for the same transition,
= 27419.25 clr,I.-l
l'rt,l)L n :4 Calculate the enertlr required to ex_
cite one litre ofhydrogetr gas at I atEr aDd 29t K to tbe
first excited stste of atomic hydrogen, The etrergJ, for
#=R (i-i)-.
the dissociatior of H-H bo[ds is 436 kJ Eol-1.
(I.r.T 2000)
.#=*=+*H=+
Pv
solution. No. of moles oI H^ !a a = ffi
-. ._s, ='i =2*= 22.E Dm.
^r.*
-^=l]-L:
= o 0821 x 29A = o uoo, Iiind th? wavelength of100g particle
.. Enerry required to dissociare them ioro atoms moviDg with yelocity 100 ms-1.
<r.r.T 2000
= 0 .0409 x 436 = 17.83 kI h _6.626 x 10-34 kgmz s-l
No.of moles of I{ atom = 2 x 0.0409 = o.0Et8 Solutioo. I = tno
o. t tg;loo;F-
r-=
'n' -1!l?sro1-r = 6.625 y 1n-SS ..
3172

1. The charge on the electron was found by 9. The ratio ofcDers/ of photon of,t = 2O0oAtothat
of I = /|om A is
(4) JJ. Thomson (6) Millikan
(c) hraday (d) Goldstein. .@\2 (b) r/4

2. The discovery of nucleus sas done by (")4 (d)i 1

\t t.t. tu\..
(a) JJ. Thomson (b) Chadwick
10. Anyp-orbital can ac{ommodate upto
(c) Rutherford (d) Moseley.
(a) four electrons
3. WheD.r-rays slrike a thh foil of gold (b) two eiectrons with parallel spin
(a) Most ofthe a-rays are deflected back
(b) All the @-rays Pass through the foil -{d6(clectrons
clectrons with anti-parallel spin.
(c) Most of the d-rays are deflected through cm3!l /Urytwo ,r t. r: r,t\tt
angle
11. lluthcrford'sscattering experiment is related to the
(d) Most of the a-rals pass thrcugh without any
deflection. E the
size

..ldfotcleus (r) atom

The series of lines prsent in the visible regio[ of
(c) electron (d) neutron. \l.l.T l9stt
the hdrogen sPecrum is
(d) Lyman (D) Balmer 12. WheD d-particles are sent through a thin metal foil,
most of them 8o straight through the foil because
(c) Paschen (d) Brackett.
(one or more)
Pascben series are Producrd \rhen electrons from (4) a-particles are much heavier than electrons
the outer orbitsjumP to
(b) a-par
(a) 2od orbit (6) 3rd orbit
(c) 4th orbit (d) 5tb orbit. ,tzfMost
(d) a-P tt ! i: tt)ttJ)
6. The elerEonic conligurarion of aD elemeot is

trz xa zf. The number of unpaired electrons in

lYAL correct st of quanlum numbers for lhe un-
this atom are " paired electron of Cl atom is
(a)3 (6) s (c)7 (d) 1.

which of the followiog is the correct electronic (a)2,o,o, + | 1O1Z,t,-t, * |

cooliSuration ofscandium (atomic Dumber = 21)?
(a) tsz 2:2 2P6 N2 3P6 3d3 )*7,1,\!+ @)z,o,o, tl.
(b) 1s2 ?s2 2p6 a? 3p5 3dr 4i tl.l.1:1t)39J
(c)1s2 2 2p6
k2 3P6 3& 4sl 14, The outer shell configuration of the most
electronegative element is
(d) 1s2 ?:2 2P6 X2 3p6 4s2 4P1.
1a1rcz npt (\ n* npa
Which of the following is the correct electronic
<c) nz nps @) ni np6. \t L't: teso\
configuradon of Fez+ ion (Z for Fe = 26) ? A r-orbital can accommodate
(a) 2? 3d 4s2
2p6 3s2 3p6
"t"crron" -ftl6
1s2
1oi + electrons
Q) b2 2p6 X2 3P6 3d (c) 2 electroN with Pardllel sPins
(c) 1sL
^2
* 2p6 r? 3p6 4s2 4P1 2 elertrons with opPosite spins
14
( M. L- N- R. AUa habdd I 99 0 )
(1) b2 b2 2p6 3s2 3P6 3d5 4sr.
r:i::iil:iir: jl, i:i:ril ir :, t: i i:.
:r :r
l, ii i i lrii ' :, i , l:i l: i l:i'i 'l

a.b 9.d to. d

l.b 2.c 3..1
1L a 12.4c 13. c
 ATOMIC STRUCTURE
3lz3
16. The principal quanrum number oian electroo rep- (D) It causes ZtrS to fluoresce
resco[s
(c) It is deflected by electric and magnetjc field
dsize of the ofiitat (d) They have wave letrtth strorter rhan ultra violet
(b) spin angular momentum rays. 1.t.7:1992)
(c) orbital angular momentum 23. The first use of quantum theory to erplain the
(d) spac orientaricn of the orbilal. structurc of atom was made by
i)1.1, \'. R. ,lllah(bdd let)0, (a) Heisenberg (6) Bohr
17. Electromagoetic radiation with maximum (c) Planck (.r) EiDstieD. t 1.t.1: tee)
waveleDgth is 24. Which ofthe following sratemeDts is not correct for
(a) Infrared p)dadio waves an electron that has the qua[tum numbers n 4 =
(c) X-rals (d) UlEaviolel andm=2?
lt. Which of the following represents a correct ser of (a) The elecrron may have the quantum number J
quantum numbers ofa4 d. elec'/.ro[ ? 1
=+,
(a) a, 3, 2, + lt2 (b) 4,2, r,o
(D) Thc electron may have the quantum number /
(cl4,3,-4 + ll2 l.ta,Z, t,-U2
t ,l L l . \t.lt. ,lllnhlthfld I990, B.t.'I Ra'.t,hi Itte) )
(c) The elcctron mayhave the quaDtum number/t1
19. Which of the folloving eleclronrc jump in a =-2
hydrogen atom will require the largqst amounr of
(.C)'Ibe elcctroD may have the quantum number,
eDerw ?
= o,I,2"3. (,V. 1,. N. R. Allalqbad 1 9 9.1
;lgfFrom n = lton =2 25. 'fhe set ofquanrum oumbers not applicable ro an
)

(D) F'rom n =zton=3 electron in an atom is :

(c)Fromn=@tor=1
(d) From n =3to4 =5.
(a) n = 1 ,l = 1,n = t,s = + )
(M.I-..\'.R. trllalnhad I9e2 t
(b)n = I .l = O ,O , n = O, = +
]
20. The or iDwhich both the Pauli,s ex- "
clusion Hund's rule are '/iolated is (c)n=l,l=O,m:O,s=+j
(o) 1t t (l)n =2,1=O,n = O,s: + j.
(lLL \'.R. /l ohohad tt)t)1i
.lbl' l+ TJ 26. Io what ratio should
flct ano ffct te present so
5Ct ?
(c)
as ro obrain
i;
J J I (a) t :2 (D)1:1
(c)r:3
(d) tt 1t t (d)3:1.
I tta^ttut (.I. L t 1,.t,).!
27' Bohr radius of hydrogen arom N
\ B.t l: Roru lti tt)s)
21. Whicb of the followiDg has maximum number of (a) O 529 x 10-8 m (6) 0.529 x t0-lo m
unpaired electrons
(c) 5 29 x ln-Bnr
?
(d)5.29x l1-rom
(a) ZD (D) Fc2+ tuanuttrt ( I..l: t. trrj
(c) Ni3 + (d) cu+. 2E. Which ot rhe followlng sels of quantum number
t81 t liittth! l,),t), rs/are not permilled ?

22. Which of the follot

rals?
iDg does Dot characrerise X_ (a)n=\l = 3,m = O,s = + j
(a) The radiation can ionise rhe gas (b)n=3,t=Z,n=+2,s=-L

a r&d a
/<s
76.
26. c
17. b
27. b
19. 2O. o 2tb 2Lc 2t. b Z4.d ZS. a
3n4
35. The orbital aDgular momeDtum of an electroD in
(c)n=3,1=t,n=-Z,s=-l 2 r orbital is
th
(l)n=3,1=O,m =0,s= +i
1

\q+r21' (b) zeto

I \.\t !)iu'nhad' 1991t .. h (d) 't2 2

lc) Zi \t.t.r. t,,tht
29. The electronic confiSuration of neon is '7'
36. l.'or a d eleckon, the orbital angular momentum is
@\ 1? (b) tsz 2.s2 2P4
(a) G E (b),ir E
t? zP zp6 @) 152 2s2 ?pt
1c1
(c)fr- (d) 2fi: tttr' teen
,,'.,";; ;";";' 37. If the eledron falls trom ,, = 3 to n - 2 in the
30. lhe i'troduction of a neutron
H-atom, thcn emittcd ener$r is
compositton of an atom would lead to a changc in
(a) 10 2eV (6) 12.09 ev
(a) The number ofelectrons also
(c) 1.9 cv (d) 0 65 ev
(D) The chemical nature of thc atom
(,1. li,rl.(. I'u nt. I t)!) 7 t

(c) Its atomic number

3E. The rctal number of orbitals io a sbell having Prin-
(d) Its atomrc wcr8ht r
cipal quaDtum number is
Jl. lte wavelengths of which sries lic towards thc
ultraviolet (s) 2n (b) nz
(a) Lymaon (D) Balmer (c) 2n2 (d) n + t
(c) Paschen (d) None ofthe above lt S. I997' Il'utam ( 1"'Ii l) )tt00t
''l-Lt
tt. J, (,. tt.J: tae6l with Co is
39. The ion that is isoelectronic
32. Which of the following statement does not form a
part of Bohr's model of t!/drogen atom ? (o) oz (6) N,
(4) Enrry of the elecron in the orbit is quanl ized (c) cN- (d) oz+
(D) Ttle elecron in the orbit Dearst to the oucleus t (. R.S. 1,. I!,1!.1: l r97
has tbe lotPer energY
(c) An8ular momeotum ofthc electron in the orbit 40. The Bohr orbit radius for the H----atom (r = 1) is
is quantisd apprqimately 0 530 A. The radius for the firsl
(d) The position and velocity of the electrons in the excited state (z = 2) orbit is (in A).
orbit cannot be determined simultaneously' (c)013 (D) 1 06
tI l, (, l:.F It)t)t,] (.1)2 12-
{c) 4.7't
tC.ilS.f t:,lt'1: t99ll lt'lut/ t ( l' ltti)J1
33. wbich of thc follor/iDg statement regardinS
sPectral series is corrcct ? 41. Among the folloxing which one is not ParamaS'
ra) The lines in thc Balmer series mrresPond to the netic ?
electronic transition from the enerry level lAtomic Dumber : Be = 4, Ne = 10,
As = 33, Cl
higher than n = 1eners/level = 171
(6) Paschen series apPer in the inftared regioD (a) cl- (D) Be-
(c) Tbe lines of Lyman sries apPear in the Yisible
regioo (c) Ne2+ (4 As+
( (:.8.5. L. Pll. 1: I 998)
(d) Ttansition ftom hi
S/ level Produces 42. The maximum number of electrons in aD orbit with
infrard region I =2,n =3 is
34. The number of nodal Plsnes '5d' orbital has
is (o)2 (b) 6
(o) zerc (D) one (c) 12 Ql) 10
t.tt MllLT !e98)
(c) two (d) three. is (are) mr'
43. lYhicb of the follos,ing statment(s)
, ttan tn:; (.ll D.?l I rect?

A
2E. a,c 29. c 3(Ld 31. l, 33., 34. c 35.b 36 a 37. c
3A. b X9. c 4o,4 .-* 4t- a
ATOI\4IC STRUCTURE 3ns
(4) Tbe electronic coofiguration of Cr is 51. Among the following groupings which reprcscnb
lr'trl t1 (Ar. no. of cr = z)
3 ds 4 the collectioD of isoelectronic speciqs ?

(6) The magne$c quantum numbr may have a (a) No+, q-, o2-, co
negative\lalue.
(c) ID sih/er alom,23 elcctroB hatr spin of ooe type (6) Nr, q-, co, No
aDd 24 of the opposite type (Al. no. ofAg = 47)
(c) co, No+, cN-, cr-
(d)'Ihe oxidation state of nitrogen in NHI is
-3.
( l.I.'t: t993.| (d) NO, CN-, N2, O;. i ti \ . tlt.t t ;,ti)t ,

44, The enerry of an eleclron in the fiIst Bohr orbit of Tbe energy of a photon is given as
H atom is .
6 eV The possible enersl l?lue (s)
-13
of the ciled state(s) for electrotr in Bohr orbits of AElatom = 3.03 x 10-19 J atom-1. TheD th
lrydrogen is(are) wavelength (t) of the photon is
(a)-3.4eV (b) -a zev (a) 65.6 nm (b) 656run
(c)-6.8eV (d) + 6.8eV tlr.'r. teest (c) 0.656 nm (d) 6.s6wn.
45. Who modilied Bohr's theory by introducing ellipti- t ( . It. \. L. L,t L'l: 20t)t) t

cal orbit! for elcctron peth ?

Principal, azimuthal and magnetc quantuD num-
(a) HuDd (D) Thomson
bers are respectively related to
(c) Rutberford (d) Sommerfeld.
(a) Size, orientation and sbapc
{ it\t tlt tt,rt., (D) Size, shape aDd orientatioo
46. Which is the correct statement about proton ?
(c) Shape, size aDd orientation
(4) Proton is nucleus ofdeuterium
(d) None of these. t.\.1 ) ll.s. )oait\
(b) Proton is a-particle
(c) Proton is ionized hydrogen molecule s4. For which of thc following spericq Bohr's theory is
not applicable ?
(d) Proton is ioDized hydroSen.
\i l, I r.,t i,,, (a) BC+ (D) U2+
47. Magnetic quantum number specifies (c) He2 + (d,) H. \ D. L. 11. i:. l'. : tt ()t )
)
(a) Size oforbitals (b) Shape oforbitals
Which of the follot ing b not possible ?
(c) Orientation of orbitals (d)n =3,1=O,,n =0 (t)n =3,1=l,m=-L
(d) Nuclear stability. \i l: t- I t. tr,)1 (c)n =2,1= o,m =- | (d)n=2.1=l,m=o.
The elecrons, identified by quaDtum numbers ,r Ilt.H.1..2t)t)o\
and I (i) n = 4,1= 1(ii)n = 4,1= O (iii) n = 3,1 =
2 (iv) n = 3, I = I can be pla@d in order of 56. The oumber of unpaircd electrons in
Mn2+ is
increasing enerry, ftom the lowest to the highqst as
(o) 1 (b)7
(a) (,v) < (ri) < (nD < (i)
(r) (ri) < (,v) < (i) < (rs)
(c) 3 (d)5. tC.l)M-T.2000J

(c) (0 < (,,,) < (rr) < (iv) 57. Which of rhe follotying atom has Do neutron in its
Ducleus ?
(d) (,rl) < (r) < (tv) < (rr) (I.I.T r 999)
(a) Helium (6) Uthium
49. The number of nodal planes iD apr orbiral is
(c) Protium (d) 'Ititium.
(a) ore (r) two
\< .f ii!.'l )t)00\
(c) three zero. t i.l T 20A0i
(d)
The electronic configuration of an element is Ifthe radiusofEIst Bohr orbit be 40, then the radius
l s2 2s2 zf 3 s2 3p6 3 d5 4 11. This represents irs ofthe third orbit would be
(a) excited state (r) Sround state (b)6xao
(c) ctionic form (d) anionic form. (d) 1/9 x ao.
!l.l. t: 2t1001
:

43. a,b,c 44. a 45. d 4.d 47.c 48. o 49.a 5(I, 51.e SLb
53. rt 54. c 55.c *..1 S1.c 5t. .
3176 Pradeep's
In Cu (Ar. No- 29) (a) Mn2+ (D) Fe2+
(a) 13 electrons have spin in one direction and i6 (") Ti'* @) cc+
electrons in other direction ('1 I l' L lt 20(t)
(6) 14 electrons havc sllin on, dircction ard 15 67. Which of thc following element outermost orbit's
electroDs in othel directio[ last elcctroD has magnetic quantum Dumber rn =0 ?
(c) one electron can have spin only in the clockwise (a) Na (D) o
directioD
(c) cl (d) N
(d) none ofthe above is correcl.
(Rqastlwt PM T 2002i
\HaDa rt L E II l:2t)0t)t
6& In hdrogeD atom, enerEr of the first exciEd state
The following quaotum Dumbrs are possible for is 3.4 e\l Thn find out the ICE. of the same
how maoy orbiials ? n = 3,1= 2,m = +2
-
orbit of H-atom
(a) | (b) 2 (a) + -? 4eV (6)+68eV
(c) 3 (d) 4 (c) 13.6 eV (d) + 13.6 eV
t( .lt..\ l;. l!,ll.l: )01)l t
- (c.ll.s. D. l:ll'l: 2002 )

electrons in In the Bohr's orbit, what is the ratio of total kinedc

In the ground state, an element has 13
enerry and the total enerry of the electron ?
ils M-shell. The elemeDt is
(a) Manganese (6) Chromium (a)-1 (b)-2 (c)+ 1 (d)+2
IR|iLstlm'1 l:,ll l: 2002)
(c) Nickel (d) lron
(E A.lI.C.E,7: 200I )
10. Rutherford's exPerimcot, wbjch established the
nucler hodel of the atom, used a beam of
62. Whiclr one of the folloqiDg paifs of ioos havE the
(4)p-panicles which impinged oo a metal foil and
same electmoic confiSuration ?
got absorbd.
(4) cP+, Fe3+ (6) Fe3+, Mn2+ (6) y-raF, which impinged on a metal foil and
+ ejected eleclrons
(c) Fc!+, Cd+ (4 sC+, cf
| 1,. \..11.( li l: :t)t) i I
(c) helium atoms, which imPinged on a metal foil
and 8ot scrttered
63. As the nuclear charge increases from neon to cal- (d)helium nuctei, which imPinged on il
cium, the orbitals energies aDd got scattered )

(a) increase (b) increase very rapidly lf the NitrogD atom bad ele,ctronic coo.figuration
(c) increase very slo tY lr?, it would ba1,e cner8y louer than that of the
(d) fall normal ground state configura on ts2 Nz zf ,oe'
(d) enerry remains constant caus the electrons would be clocer to the nucleus.
( kroln tll l: l; )()lD l Yet 1s7 is not observed because it violates
Chloride ion and potassium ion are isolectronic. (a) HeiseDbers's unc ainty PrinciPle
The. (6) Hund's rule
(c) Pauli exclusion princiPle
(d) their sizes are same (d) Bohr pctulate of sbtlmaryorbits (1 1.7: 2002)
(b) chloride ion is bigger lhan potassium ion 72. In Bobr series of lines of hydrogcn spectrum, tbe
(c) potassium ion is relatively biggr third line from the red end corresPoDds lo which
(d) depends upon the othcr cation or anion one of the following inter-orbit jumps of the
\ tr: ( l:"1: )t)tt) electron for Bohr orbits in an atom of hydroBen ?
oQected to be similar to that of
'
(a) s- 2 (b) 4- 1
The spectrum of He is

(t) Na
(c) 2- s (d) 13.- 2
(a) H (A IL I'' Ii )0011
(c) He+ @)u+ 73. The number of d-electrons retaiDed in Fe2+ 1At.
(lr.P. PM.T. 2002 No. of Fe = 26) ion is
Which of the follo ing ions has the maximum mag' (a) 4 (D) s
oetic moment ?

59. b 60, a 61. b 6.0 67.a 6.a

69. a 7O' .l 71. c
 ATOI\,,IIC STRUCTUBE 3177
(c) 6 (d)3 (A.r.E.E.E. 2003) Correct eDergy value order is
?4. The value of Planck's constaot
is 6.63 x lo-a Js. (o) ns np nd @ - t) I *_J/
The velocity of light is 3.0 x 1dm6-1. Which tPyt6 np 1n - 1) d@ - 4J ,/'-
t/'alue is closest lo tbe wavelength in nanometers of (c)n-rnp(n-1)d@-1)f
aquantumof light wrth liequencyof 8 x 1015 r-1 I {4 ns (n - 1)dnp (n - 7)l lorissa l.Ii.ti.2001)
(o) 2 x l}-b (D) 5 x ro-ts t3- Corect order ofradii is
(a)N<Be<B -..
-(6r-.O2-<N3-
(c) 4 x 10r (t)3 x 1O7
IC.B.S.E. PM,T 2OO.'\ (c)Na<U<K (d) Fe3+ < Fe2+ < Fe4+
(.1&K(:.FT1(10Jt
75. A spccies hayint oDly one clectron has ionizatioo
84. The corrcct sct of quantum numbers (4 I allld m
cnerry of I 1810 k, mol - I . The number of protons respecrivEly) for the unpaired electroD of clllorine
ln its trucleus will be atom is
(a) 1 (b)2 (d) 4
For principal quaotum numbr n = 4 the total
rlumber oforbitals having, = 3 is
85. The oDe electron speaies having ionization cner$/
of54 4 eV is

W
77. The ftequency of thc radiation emitted wheo the
(d)9 (A.I.I.M.S. 2oo4) (a) H (E) He+ (.) Ba+ ((rLiz+
(Kadla C.D.D. 2004\
efectron falls ftom n = 4aon = l iD a hydrogen @)B*+
atom will be (Given ionizatioo enerry of H 66; nme laken for an eleclroD to complete one tevolu -
tioD in the Bohr orbit of hydrogen alom is
- 2.lt x I -18 J atom-l aod
h - 6.68 x 1o-r Js)
O

o+ @)#,* @##
(a)154xlolsr-1
'!?f3'c8 x
(D)I03xtOlsJs-t @Th d# (rkrot.prv..t:zoott
rcts t-r (d)2Oxlorss-1 t7" If ltle ionizatioo encrsr of hydrogeo atom is 13.6
((:.B.S.L. L.lL7: 2(tl)J ) eY the enerry required to excite it from ground
7& The radius of which of the follot ing orbir is same state to the next higher state is nearly
as that ofthe first Bohr's orbit of hydrogen atom ? (a)3.4 cV 15ytd.zev
(a)He+ (n = 2) (b) Liz+ (n = 2) (c) 12.1 cY (d) 1.s ev
(e) 15 eV (Keruln il.L.li.20Alt
(c) U2+ (z = :; !/lsd+ 1n =21
t l.l l: 200J) AL fin =f,l =9,6 = 0, then atomic oumber is
79. Consider the gro (q) 12,13 (D) t3, 14
(Z = ).
The numberofel (c) 10, 11
tum numbersl = y
thal quan-
,gdn'n
lBilmr C.E.L.E. 2001)
(o) lzaBd 4 E9. whicn is the isotone of ]tce
(c) 16 and 4 (d) 16 and 5
?

.F l: )t)oJi @.\Tc,e l,tltse @Ak @)13ac

was discovered by ( Ha4tnn M,l. t! 2004)
i$,4roton
(a) Chadwick (r) Th 9l,. The number of d-elcctrons in Ni (at oo. = 2a)
equal to that ofthe
is

_llicoldstein (d)Bohr(;4.EL|.c. 2004)

tl. The number of ? electroos having spiD quantum (o) s aDdp electrons in F-
numberr -- 1,/2are (b)/ electroDs in Ar (at. Do. = 18)
(a)6 (b) 0
1zld<lectrons in Ni2+
(.)z W (d) 'Ibtal electrons in N (at. no. 7)
=
ktttateka
t L.I,.l: 2004\

,E
73. c 75. c 76. c 74. d 19. b E0. c 81, tl AL d
E3. E5. 15. a EE. d r9., 90. c
' '
3178
Ne@ Course chemistrgWA

c. E: hv: hl -rs. Orhrlatangular momcntum - "1T

- n*
tr iz For 2 J electron, l=0 Hence orbital angular
4oo0 A= z^ momentum = 0
F;= \= 2omT
36. For d-electron,I = 2. Orbital angular momeDtum
12. a-particles are heavier than clectrons nd, thcro- = vfil=-IJ,i = ,lrOilj ti = '/C fr
foie, cannot b stopped by eledrons Moreover 17. p - - -94"v
most part of the atom is emPty spac.
13. 'l}Ie u[paired electron in Cl
ll
is 3pl for which n = 3,
q- E,= 13 6 (+-i) "u=,., "
- (i-+)
l=t,m---1 or0or+1,r=+i ot -i.
= l-9 eV
HeDcE (c) is mrrect. 39. Electro[siDCO-6+8=14
14. as2
4f r"p.eseott halogen which is mmt 02- has e- = 8 + 8 + 1 = 17
eleclronegative,
Nr+hase- =7 +'7 =- l=13
n,=-1{2s661-t CN-hase- =6+'7 + 7=14
Or+ hase- = 8 + 8 - I = 15
En,_Er__""lhir)
40. rn=o53n7=o$x*=2lzA
41.
,.,ct- = tsz 2? 2p6 Zs2lfiZpjlpl (No unPaired
electron is prescnt)
n = 3,1 = 2meansld-subshell. Maxirnum number
ofelectrons present in it = 10.

Jump ftom,l = 6 ton = l will nol require ener$/.

Rather enerry t'ill be releasd' 43, 'fhe oddation stale of N in NH3 is +3.
2L. UnPoired electrorc
44, .- 11!,',r
n7'"
,ozn = tsz 2? 146 x2 3p6 3d1o 4i2 o
When 2,
3d ', =
,rFez+ = tsz 2s2 2pG 3s2 3p6 4
+
= lsz x2lp6 3P 3pc Y1 3
\= - "-ou = -t o"u
,"Nf ap(ii)+s (iii)3 d (ie) 3P. In ordcr of increasing
46. (i\
,ncu+ = t? N2 2p6 k? 3f ?urn o energies 3p <4s <1d <4Pi.e.(iv') < (ii) < (tii)
< (i).
X-rays are not defleded ry elecrric and maSnetic
50. 'Ite given E.C. is for ground state of chromium.
fields.
24. When m = 2, , cannot be 0 or 1, 51. In (c) electrons in cach sPecies arc equal.
25. when,r =-1,1 cannot be 1. so (4) is wronS CO=6+8=14,
26, Meanof37 8nd 35 comes ourtobe 35 5 only when Y6+=7+8-l=14,
they are in thc ratio 1 : 3.
CN--6+7+l=14,
28. WheD n = 3,, cannot be = 3.
So (a) is not Permitted.
4- -6+t+z=u
E=hv=hl
When I = ,', cannot b =
1,
-z
So (c) is not Permitted ^- , hc (6 63 x 1o-31Js)(3 x lo8n6-l)
orl=.:=--
E (i.03 x l0-,,.I)
30. As protons remaitr the same, iotroduction of
neutroD changes only the atomic weight. = 6'56 x 1o-1 m
34. Ad-orbital has two nodal planes. (Numbr ofradial = 656 nm
nodesrn5d- (n 1) = -f- 2 1) =2) (s -
ATOi,4IC STRUCTURE 3F9
54. lleT+ contain6 Do electroD. A]t others contain ooc 72. The lines at the red end hclong to Ralmcr scries.
electron each. These are obtair.ld forjumps to r = 2 trom outer
55. In (c), as 1 = 0, ,n cannbt be qualto-1. orbits(lsr line fromfl = 3, 2nd line trom r = 4, 3rd
56. ,rMn2+ = [tu]1t 3d5. No. of uDpaired clectrons
linefromz=5).
73. E.C of 26Fe = IAtlli 3 cl6 4sz
5& r, =ag un2ie.r^=aox32 =9al E.C. of Fc2+ = [Ar]18 36F
59. zecu = [Ar]r8 V1o 4s1 .. d-eleclrons = 6.

t c a x lo8 ms-l x tn' 1 m

AII elecftons are paLed excpt 4rl. Henc 14 e- 14. = i - ;.;t#= = o 3'15

have spin oDe direction and 15 e- in the other.

60. One setofquantum numbrs is oflly forone orbital,
= 37.5 x 1O-9 m - 37.5 nfrl = 4 0xl0nm.
In an atom, the trlo ffbital$ can have tbe &ame set 7s. LE. = t3!2 x z]
of quanturn nulnbers.
fior one electron species tfl thc grJund state,r? =I
61. 13e- ir M (3rd) shelt means 31313d5. Hencc
complete configuration \+,ill be .' 1312x7?
= 1181O
lsx 2s2 2p6 yz 3p6 4tt 34s or 7] =9orZ=3
r:e. rotale- - 24- Hence the elemem iscrrromium. 76. For a = 4, E.C. = t"a zr7 lp6 k7,
62. ,rMnz+ = 1er.1lE 3d.
,oFe3+ = [Ar],8 3d5, qf 3dto 4s2 4p6 Mlo 4f ..
63, Energies of ihe orbitals Z2.With ioci case in / = 3 means/subshell which hn( 7 orbirals.
"
nuclear charge, energies of the orbitals increase 77. 1.E.=F.@ Et =0-Er
vcry rapidly.
64. CI- prolons in the nucleusl,hile K+ ion
ioD has 17
=218x10*18Jatom-i.
bas 19 ptobns. Thus nuclear charge of K+ is Thus, E- = -
2 18 x-10 - 18 ., ,,o, - t
grcater and hencc its size is smaller. nl
65. I Ic has two ele.ctrons. Li+ also ha.s h+o electtons. aE = Ft- F, - - 2.1e lo,t il-*l
66. 25Mn = [tu]lt 3d5 4s2 ... Mnz+ = [tu]183d5
=2 044 x to-18Jatom-1
z6Fe = Ittrlt& 3# 4s2
'' Fe2+ = 1Ar.1t836e lo-18J
,;-Tt = tA4t9 3dx 4s2 :. TP+ = 1A4tB 3iz
aF = Au or h = ?{' t'25
'- 4E
!11 "
x lo-laJs
=3085x1015s-1
24cr = [Ar]t8 3d5 4r1 .- cr2+ = ttuf 3#
8
n. r^-L ..!D-!z-tr
Thus Mn2+ has maximum number of u[paired
clcctrons. . rrlni =9L\x f = o.s2eA
67. I I Na = tsz 2s2 2p6 Zsl i.e. tor last electron I = 0
.. rz =0, rr1Bc3+1=9iPJ!= o 52e A.
6& llnergy in rhc excited state h nothing bur KE. 79. TnCr = 1:t2 zJz 2p6 3s2 3p6 3ds 4s1
69. v.B. =)r^o2,r.8. = -+ I= 1 meansp-sub6hell and, 2meansd-subshell
=
I- 1 is fot 2p6 aftd 3p6 -.'Ibral eleclrons
= 12
But eleqrostaric force ,$t = d Gcntrifugal torel I= 2 is for 3d5 . .. 'Iblal clecrroos
= 5

. El. There are tbree 2p orbitab mntainint 3 electrons

P-E.= - m,] wiih spin + 12 and 3 wirh spin _ 12.
Tbraleners/ =t^u2-^u1 - - l^,, aZ. (l1 - I)/, minimum n = 5.
/, = 6. For (d)n = 5. .. E.C.
''. K.E.ffbtal enerry =
-1. lues are 5 + 0,4 + 2,5+ l.
70. ID Rutherfordt erperimcnr, a-rays wre used
rvhich are helium nuclei,
E3. F-, O2+, N3- are isoelectronic. Greater lhe
71. According to Pauli exclusion principlc, an orbilsl nuclear cbarge, greater is tbe attraction on the
canDot haye more than twoelecEons and thesc too electrons, smaller is rhe sizc.
witb opposire spin.
3/80 Neul t-aurse Chemistr4l
14. r7cl - ts2 x2 za6 x2lfizfi3p], For 3pl electron 47. 6 =-[9sY.a5=E,-5,
n =3,1= 1,m = -1,0 or + 1.
rc, t.e. = 13 !nz* ,v -- B 6 z] for oDe-eleciroD =. rr.n /*-l^) - r..ux1=ro zev
\L ')

speqes-
, = 3, 1 = 0 mcans last shell is 3r
'. E.C. will bc ,tz vz 2p6 Nr-2.
..13 67] = 54 4or7] =4orZ--2ie.He+ Atomic no. is 11 or 12.
hnh llumbcr of
t6. By Bohr Postulate, mu, = " f;ot " = ,h 89. lsotoncs arc atoms conlaining the same
neutrons (No. of n = A - Z). No. of nculrons in
No. of rvdutions Per sec
!!ce = x - zz = lt. !f;se has Deutrons
- Circumfelence of thc orbit
=7a-34-44.
rnhlnh
E.C. of 28Ni - B2 2s2 2p6 kz 3p6 1d8 4s2

2r.t 2fimr 2ttt 4/ml Ni2+ = rsz 2161r2 313dE

a"2m? 'l}tus .l-clectrons in Ni and Ni2+ are same.
. ]lme taken for one revolution = -:#-

ADDIT'ONAL 8$ESTTONS
As s erti o n-tr-e a e o n TY P e Q.u e eai on e
Thc foltowlng qucstloDs cotraist ol two st temetrls eech printEd as Assertion and Reason. lvhile ansrrering
thcs. qustioEq you src rqulrcd to choose any ore of the follo! ing llve responses'
(a) rboth AsstioD aDd Rcsao! or. true and the RGssoE 16 o corTect explanstion olttre AssertioD,
(D) If both Assentol and Rcrsotr ar truc but Rcason is not a corr.ct exPlaDatloD of tbc AssrtioD.
(c) IfAssertion 18 truc but the Resson is false. (d) If the Assertion is false but the Reason ls true.
(e) If both Assertiotr and Re,ason are false.
Assrtion Reason

l. An orbital cannot have more than two electrons. Two electrons in an orbitalcreate opPosite magnetic field.

The configuration ofBe atom cannot be 1t2 3 12. Hund's rule demaDds that the mnfiSuration should dis-
play maximum muhiPlicity.

1 p-orbrtal is dumb-bell shaPed. Electrons present in P-orbital can bave any one of the
three values of magnetic quaotum number t. e. + 1,0,
-l
4. Wave number of a spectral line for an electronic It is proportional to the velocity ofthe elcctron underSoiog
transition is quantised. the transition.

5, A spectral line will be scen forazpr - 2Py fiansi- Energy is released in the form of waves of light when the
eleclron drops lrom 2 /rllo2pyotbital
tioD.
U.I.I.M.S. 1996')
re are many ocited enerry levels aYailable.
(A.IJ.M.S. 199D

7. quantum number (z) is a measure of the

distanc of finding the eleciron around the'
(a.l.I.M.s. 199E'
+ l) rule is followed for determiniD8 the orbital of the
4J{rbital and Dot the 3 dorbital. enerry state (A'I'LM'S' 1999)
llowest
The free gaseous Cr atom has six unpaired r orbital has Srcater stability. tt4.I.I.M.S. 2004)
lHalf-fllled
electrons. I
 ATOMIC STRUCTUFIE
3/81

Tr u e / tr a Is e gt at e m nte p-
wich of the lo oteing sla,n,nrs ae true ? t.
Rutberford's model catr rplain the line specrum
1. No current flou{ through the discharge tub wben of hdrogen.
the pressu re of the gas iDside is one atmosphere. 9. The eners/ levels are called stationary states be_
The cherge on the parlicles coostituting the anode cause the ele1rons are stationary io these leveis.
rays does not depend uFrn tbe nature of the gas 10. The energies of different shells are in the order
takeD.
K>L>M>N......
3. Arode ra,s originate from the anode.
11. Eledmnic eDerEr is netati\ becaus electron bas
4, The magDitude of charge on an electron ard a negatiit charge.
proton is the same.
12. Bohr's model is not in accordaDce with de Broglie
The mass of proton is nearly same as that of concept and Heisnberg,s uncertainity priDciple.
hydrogen atom.
13. Tbe bouDdary of an atomic orbital canDot be
All elecromagnetic wavEs travel witb the velocity defined with abEolute accuracy.
oflight.
14, All orbitals have directional characteristics.
7. There is no diffcreDc between line spedrum and
atomlc spectrum.

Fill ln The Blanke

l. Cathode rals produce.......rals when strike agaiost
rhe surface of a hard metal like tungstetr. 16. For I =2,m

2. Carhode rara produce.......on s[iking a ZnS screeD. 17. The energr of a 4r orbital is....._than that of 3d
orbital.
3. Anode rays are deflected towards.......plate of the
electric field. 1E. r{rbiulls have.......shape whereas p{rbitals have
.....shape.
4, Proton was discovered by.......... . h.E the
5. The nucleus is nearly.......in size as compared ro the
; angular momentum of the electron in the
.......orbit of He+ (Roo*ce 1990)
totalsize ofthe atom.
The transition ofthe elertron in the hydrogen atom
6. Neutron was discovered by........ .
ftom founh to first erergl state emis a spectral linc
7. The arrangement of different electromagnetic
wbich falls in......series. (Rorkce 1990)
waves in order of their wavelengrhs is called.-.... . The light radiations with discrete quantitiesofeDer-
t. The quantum of lighr is called....... . S/ are called....... (r.r.T 1993)
22" tr\hve functions ofelecroDs
9. The lowest eDer$r state of an a bm is called......aDd iD atorns and molecules
after absorbing ener$/ it is said to be in.......... . are called.......
<1.1.T.199i)
10. The_splirring of lines in the magneric lietd 23. The 2p, ,2py and 2p. orbitals ofatoms have iden-
is ca ed
tical shapes but differ in their........ (IJ.I: lg93)

11. Bohr's model of atom is based upon--...-...whereas 24. The outermos! electronic configuration of Cr is
wav-e. mechanical model is based upon......... and (I.I.T. 19e4)

umbers n,I and /ll

12. The numbers which give complete lnformadon element having the
about the electron are called........ . 3 are......--.

13. 'fhc Dumber of sub-shells iD the nrh main shell (Bihu t99n
is.........and the number oforbirals is........ . The probabitty of finding the electroD at any poinr
14. The orbitals having the same ellergr are called.... . around the nucleus is found from the v;lues
of.......--. .
15. Forz = 3, / = ......, ....., ...... .
3182
Neu/ Course Chen istr,l Wil)

M atchinq Ty ? e Q.ue st'io ne

Mdrch the entries of colunn I with oppropriate entries of column lI'
ColuEIr I Column II
l.Orbitals are filted in order of increasint energy 1. Hund's rule
2.Degenerate orbitals are first singly occuPied 2. PauliexclusionPrinciPle
3.An orbital can have maximum t$o electrons 3. Aufbau priDciPle
4.Position and momentum ofa small Particle 4. HeisenbergprinciPle.
canDot be measured simultaneously with
absolute acauracy,

ASSERTION.REASON TYPE OUESTION S

l.b 2.b 3.b 4.c 5'e 6.a 7.a E.o 9.c
TRUE-FALSE STATEM EIITS
1, 4, 5, 6,'l , 12, 13.
FILL II'i THE-BLANKS
X-ra)T 2. green fluorescnc 3. neSative 4. Gol
rc
l
spectrum t. photon 9. ground state, excited state
de Broglie concrpt and Heisenberg's uDcertaiDty
14, deginerate oibitals. 15. 0, 1, 2 16. 0,
-2, -1'
orientation
20, Lyman 21. photons 22. orbitals 2Il.

YlI9ltY 1 {l!S!is IL9l' s

1-3,2-1,3-2,4-4.

HlNfS/ExPLANATloNSiLoAssertion-ReagonfypeG.ueet.iono
5. 2 p, and 2 P y arc degeneratc orbitals !.e har equal
o' o=* (4 - !"). Thus v depends only uPon tbe
l"i and"ili,2; b"tt*""n which the transiton 9.
encrSlcs.
[Ar]3d 4s1 r'.e. it has six unpaired
orbits ln, 21Cr =
takes placc and not on the velocity of the electroo' eledrons. Fully-6lleds- otbital has greater stability'
 [J hJ IT

Claeeificatto n of ElernenEs
and ?eriodiciV3r in ?ro?ertieo

,.',,',

The need for classification

(ir) Atomic number and periodic law
The signilicance of (r) Mendeleev's periodic taw,
The present form of the periodic table
The IUPAC nomenclatttre of the elernents with Z > 100
periodic table'
Electronic configuration of the elements and
Types of elements : s', P-, d'and f- blocks'
atlinity, atomic radii and valency'
Periodic trends in properties : ionization energy' electron i:

SECTION _ I
PEI{IODIC T.A'BLE

1.1. General lntroduction; N"1q

a periodic table. Thus

sepuruletl lrrtm one unolher-

of the Periodic Table ,i:i:iL+ ::r:l::ri:i:::::;::i:::::iil:iri:i:jii:iii:::;l:irl::i:::::i:::i::

In 1808,
Theory. Acco
element canb
basis of their
tempts on the ctassification of the elements were
b asi d up on their atomic weights'
1.. Doebereinet's Thiads. The first attempt
towards t'-f,e?Ia*itieafiOn of?fements was made by
I. DoebereinAr, a German chemist in 1817'

4t1
 412

He arrunged similar elemenlJ in groups o! three and shrwed lhtt lhs oromit ||eighlt qre eithar
nearl! the
same or tha atomic htei9fu of the midills element is (pproximalel! the urithmetic min
of the other two. ihesc
groups of three elemenls are called Doebereiner's Triadr ,

Some examples of thesc triads arc :

l. Triad Iron Cobalt Nickel

/t. wt 55.85 58.93 5a 71 Atomic weights are
nearly the same
2. Triad Lithiulrl SodiuIn Potossiurn Mesn of 16t and 3rd
ALt. '1
23 39 7+39 ^.
3. Triad ChloriDe Btomine Iodine
/1t. wt 35.5 80 ,t.tarr,
127 =r,..r,
4. 'IFiad Cnlcium Strontium Barirrm
/1t- trt 40 87.5 13',7
40+137_885

The major darwback of Doberciner's classilication was thaI the conccpt of triads coukl hc
applicd
only to the limited number of elements.
2. Iblluric periodic classihcation, in thc sensc in rvhich the term is
now uscd, was th sa<1b'1 de Chancourtols in 1g62. The unilcrlying concept
is, however, com this book.
3.-Newlands Law of octaves,. ln 1865-66, an English ahemist, lohn Newl,andr observecl that

are otrafiged in,order of tlteir i creqsing atomic weights, the properties of evcry
to lhe first one like the eighth note oI (1 tnusical scale. This generalizaiion wa.s
foctaves.
For e,rample, consider the following elements :

5r No. 1 ) 3 4 5 6 7
Elament Li Be B C N o F
Sr Na 8 9 l0 1l 12 13 l4
Elcttent Na Mg Aj si P s CI
St No- 15 16
Elzment K Ca

sodium,
Thus,
lithium andso is the
The same is true of
cium ; boron and aluminium and so on. In the
begrnnfug this idea was not widely accepted and
was actually ridiculed. However, his work was
recognized much laterby the Royal Society, Lon-
don by awarding him the Davy Medal in 1887.
ThLs generalization was alstr discarded since
it could not be applied to elements having atomic
weights greater thar that of calcium, i.e. /l{) a.m.u.
Furthermore, with the discovery ofnoble gases, the
to properties of the eighth element were no longer
m. similar to the first one.
al-
4. -Lother-Meyer arrangement. In 1869,
Lother Meyer, a German chemist, stridied the
physical properties such as atomic volume, melting
point and boilhg points of various clements.
He ph
(gon
dlomicveiglS of E elencnts and obsumed that thc
ehnens wiih similsr propertizs occupid similar
posiliorx on tlu cume (Fig. 4.1).
 CLASSIFICATION OF ELEMENTS AND PERIODiCITY IN PBOPERTIES
413

E
LIJ

l
J
o
o
o
F

ATOMIC WETGHTS
--+
FIGUBE 4.1. Loiher Meyer's atomic volume curves_
For example,
(i) The most sttongly elecb-oposiiye alkali nrctqls
(Li, Na, K, Rb ond Cs) occupy Arc peqks o the cune.
(ii) The less strongly electrcpositive alkaline these similarities, Mendeleev proposed his _ftri-
earth metals (Be, Mg Co, Sr an(l Ba) occupy the odic Law. It states that
descending positions on the auye.
(iii) The most elcctronegotive elaments i.e.,
halogens (E Cl, Br qnd t) occupy the ascending
positions on the cufle.
propcrtia an nputd $tr certain regk r ilrter-
vak.

t thc general pattern

o whcn atomic num_ tahly tbe first to fully recognize tbe significance of
atomic weights as a periodicity of properties of elements when ar-
ranged in increasing order of their atomic weights.
,13- Mendeleev's Periodic Law
4,4. Mendeleev's Periodic Table.isn:,;.+:lirri4r:i.:til+:r...,:::::r1:1:iL

_ lo
chemist,
1869, Dmitri Mencleleev, a
Russian Mendeleev arranged the then known ele-
used broader range of physical and cbemi_
ments.in order of their increasing atomic weights,
cal properties lo classifo lhe elemeots.
grouping together elements with similar propeities
 t)rntt a a y's Neut Coutse Chemisugl&frlD

and teaving out blank spaces wherever neces' .rty' .ulaDiuo were not
Ho also made the bold prediction that there r'ere proposed his peri
sonre uoknown elements whic[ ofcourse, wouldbe these elements as
discoverod in due course of time and would fill because he believe
thes(' l,lank spaces. Hc even predicted their alurninium and silicon resPectively. These ele-
propertiss in th; [ght ofthe properties ofthe other ments wcre discovered later and Mendeleev's
ect.
ilements in the sirme group. Later on, these uu-
as
known elements were discovered and were found
by
to possess exactly ihe same properties as predicted
by'Mcndelccv. For exa-mple, both gallium and ger-

as Predicted by
TABLE 4.1. Comparison of the properties of cka-atuminium and eka-silicorr
Mendeleev and those found experirnentally

PRoPERTY callirm lrkt-silicor (M)

(rbrnd) (Prcdicted)

70 '12.6
Atom:c mass 68

Density (g cm-3) 59 5 .94 55 5.36

Melting point (K) Irw 3U3.2, I Iigh 1237

Formula of oxide Mzor cEor Moz Ge02

Formula of chlorid MCt3 GaCl3 MCI4 &ol

4.4.1. Characteristics of Mendeleev's Peri-

orlic Table, Mendeleey's periodic table consists of:
Q) Eight veftica
are designated as I,
Except for group
divided into two sub
The elements which lie on the left hand side of each
group constitute sub aced ted the ProPeties of gallium
on the right hand s This germanium (eka-silicon)
that time. Later whenthese
sub-division is made ence
elements were discovered, their properl.ies were
in their properties. Group VIII contains nine ele-
fouad to be similar to those predicted by Men-
metrts in tfuee sets each containing three elements'
deleev (Table 4.1).
Group zero consists of inert gases-
3. Correction of doubtful atomic rYeights'
(ii) Six hoizontal tows called periods These
are aumbered from 1 to 6.
4.4r. Sig[iticance of Mendeleev's Periodic
thble. Some imPortant contributions of the
Mendeleet's periodic table are listed below :

can be easilY Predicted.

 l

MENDELEE\TS PERIODIC TABLD I

o
r
(;ROUI'S+ I II m ry v vI \,lI ,,rt a
a
Io
Formulac Rzo
of Oxides
RO Rzo: Roz Rzos RO: Rzo; Roq F
rn I
o
Forntulae RH RHz RH: RH+ RH: RHz RH
z
of Hydrides o
_n
m
I PERIODS B B rm
B B B B AB
m
1
rH zi
I 008 a
z
o
2
:Li lBe 5B 6c 7N ro eF !
6 919 9 012 m
10.8',1 12.01t 14.007 15.999 18.998 4
3
trNo tzMg r:Al ( 0
r+Si rsP irS ncl 6
2299 u.3t 26.9a 28.09 10.914 32.06 35 453 =
1 z
rqK zocu zts" zzTi uc, zsM, 26Fe 17Co 2gNi !
39.102 rl
40 08 44.9( 47 90 50 94 52.00 54.% 55.85 58.93 58.?1 o
-o
zlcu nZy ::A' vS" sBt m
I
63 54 us.:f, 14 92 78 96 79.9@ Im
o)
5 :rRb
85.47
:eS. :SY qoz' O'M ,rzMo ,:t *Ru .5Rh ouPd
a7.62 85 91 91 22 92 9t 95 91 (ee) 101.07 102.91 106.4
qtAg oacd aslo soS, srSb szt S:I
107.87 1't2.40 t14 82 118 69 121.75 12'7 60 126 90

6 ..Cs seBa
slLo
,zHf ltTu zw lsRe 76Os /r BPt
132.90 137.34
138 9
118 49 180 95 183 85 186.2 1 .2 t92.2 t95
lsAo aoHg gzPb s:Bi tlPo
196.97 - 200.59 arTl 201 19 208.98 (210)
2M.3',7

tAtomic Dumben of elements are gircn

on thg hft hand losEr comer of their syrnbols while atomic weights are giwn under tbeir symbob.
416
betwcen lithium (atomic weight 7) and boron
(atomic weight 11).
4.43. Defccts in the Mendeleev's Priodic
Thbl. In spite of many advantages, Mendeleev's
periodic table suffers from many serious defects.
Some oI these are discusscd below : This-led Mosetey to conclude that atomic number
l. Anomalous position of hydrogen.
Hydrogen is placed h group IA. Howcver it
resembles the elements ofbotlr the group IA (alkati
metals) and group VII A (halogens). Therefore, the
position of hydrogen in the periodic table
anomalous or controversia[.
2. Artomalous pairs of elemnls. Some ele-
ments with higher alomic weilht pre6ede the cle-
ments with lower atomic weight. For example, Ar
= 39.9) precedes potassium (at. weight
(at. weight
= 39'1) ; Co (at. weight = 58 9) precedes Ni (at.
weight = 58.7) and 'Ib (at. rveight = 127 6)
precedes I (at. weight = L26'9). No justification
has been provided for this ambiguity.
3. Posiiion ofisotopcs. lsotoPes arc tho atoms
of the same element having different atomic
weights. There[ore, according to Mendeleev's clus-
sificatioo, theseshouldbe placed at different places
in the periodic table according to their atomic
weights. For example, isotopes of hydrogen i.e.,
protium, deuterium and tritium with atomic
weights 1,2 and 3 should be placed at differeut
places.-flowever.-isotopqs of an element have not
been given differeot places in the periodic table.
4. Some dissimilar elements ar grouped
together whlle some similar elements are placedin
differcnt groups. For example, alkali metals such as
er wil.h
x,iil
same time, certain chemically similar elements likc
Cu furoup IB) and Hg (group II B) have becn
placed ia different groups.
5. -Position of elements of group YIII. No
proper pTac?Fas been allotted to nine elements of
group VIII which have been arranged in three tri-
ads without any justifi cation.
4.5. Atomic Number and Modern Periodic Law i
h 1912, Moseley, a young English physicist
measured the frequencies of X-rays emitted by a
metal when bombarded with high speed electrons.
He discovered that the square root ofthe frequcncy
(z) of the prominent X-rays emitted by a me[al was
proportional to thp atomic number and not to thc
atomic weight of the atom of that metal
Pradeep's
i"" ._9 =a(Z-b)
where 'a' is the proportionality constant and
'b' is a constant for all tbe lines in a given series of
X-rays.
Tlu plot of y'7 versus Z gave a str,'aie!.t_llng.
s, a
was a better fundamental property of an element
than its atomic weight. He, therefore, suggested
that atomic number (Z) instead of atomic weight
should be the basis ofclassification of the elements.
is This forms the basis of the modem peiodic law.
Thus,
odic Law. We know that an atom consists of a
nucleus (which contains protons and neutrons) sur-
rounded by electrons. Atomic mass is a nuclear
property and depends upon the number ofprotons
and neutrons in the nucleus whereas atomic num-
ber implies the number of electrons in the ex-
[ranuclear part or the number of protons in the
nucleus. Now, the chemical proporties of the ele-
ments depend, among other things, upon the inter-
actionbetween the atom and thereagent. Since the
nucleus is deep seated in an atom and is also
shielded by electrons in the extranuclear part so
atomic mass has little effect on the chemical
properties of elements. Electrons, however, are
exposed to the environnents and hence ca-u inter-
act with the reagent. As a rssult, the physiczrl and
chemical properties of the elements depend upon
their atomic numbers rather than atomic masses.
Further, it is understandable that the physical and
chemical properties ofelements could be different
depending upon the number of electrons and their
electronic con-figuration in any atom.
Let us now discussvihy the elementswith similar
properties recur after certain regular intervals.
:':i i:r';:i::r :'':
4.6' Cause ol Periodicity ' ':
:'
':i'i'r
i: :i i
'::i!r;;::
:: : :::l il:i
'i:
According to the Modern Periodic Law, the
properties of the elements are repeated aftet cer
tain regular intervals when these elements are ar-
ranged in order of their increasing atomic
numbers. Further, critical examination of the
electronic conhguration of the various elemenls
 CLASSIFICATION OF ELEMENTS AND PERIODICITY IN PBOPERTIES 4!7

(discusserl in Unit 3) clcarlv ;ndicates that wirh
gradual incrcase in atomic number thcrc occurs
rcpctition ol similar outer olcctronic conligurations
a[tcr cerlain rcgular intqrvals. By correlaling thcsc
t\\,o ()bscrvutions, we can say that
Tht caute oJ periodicily in propertics is tha repeli-
fitii of ,similar outer electronic conliguraliotL\ ul
ce rlui n regu lar inlem u ls.
a Consider the following examples for illtstra-
a tion.
All the elements of group IA (or 1) i.e. alkali
metals have the similar outer electronic configura-
tion, r'.e. nsl where n refers to the number oJ the
o[termost principal shell. These electronic con-
hgurations are given below in Table 4.2.

TABLE 4.2. Electronic configuration ofatkali metals

SYN{BOL ATOMIC NUMBER I'LIiCl'RONIC CONFIGUR TION

Li 3 l.tx z\t ot [Hef x1

Na ,1 1r2 2r2 ?p5 3r1 or [Ne] 3Jl
K t9 1t2 ztz 2p6 at2 3P6 ltl or [Ar] tu1
T Rb 37 tsz ztz 2p6 a\2 3p6 3d1o 4t2 4p6 5St or [I(I] 5r1
Cs 55 1.r2 x2 2p6 3sz 3p6 3r11o 4tz 4p6 4,110 5r2 spc 6rl or [Xe] 6,rl
Fr a7 kz 2t2 4,6 3sz 3p6 3(l1o 4<2 4p6 4dt0 4i4 ssz 5p6 5dto 612 6p6 7r1
or [Rn] 7,rl

Thus, it is because of similarity in clectronic configuration that all the elements have similar
properties.
In a similar manner all the halogens, i.e., elements ofgroup VII A (or 17) have similar outer electronic
configuration i. s- /rJz rtps and as such possess similar propirtiei. Thc eicctroiric configurations of halogens
arc given in Thble 4.3.

TARLD 4.3. Dlectronic configuration of halogens

I'I,I!MI]NT ATOMIC NUMBER ELECTRONIC CONFIGUMTION

F 9 7sz z\2 2p5

CI 7t2 ztz 2p6 3.\2 3ps
Br 35 b2 2t2 2P6 at2 3f 4s2 4f
I 53 l.t2 2t2 4)6 3,tz 3p6 3d1o 4tz 4p6 47to trz tS
At 85 1!t2 2t2 2p6 1t2 3p6 3d1o 4$2 4p6 Mlo 4J11 5sz 5p6 sdro e? 6pF

Again all the elemeuts of group 0 (or 18) i.e., 4.7.

inert gases_havc similar outer electronic confrgura-
tior,, i, . nsz np6 tnd also have sirnilar properties.
Now, it follows from thbles 4-Z arrd, 4.3 that
there is a repetitionin the electronic configurations
of alkali metals and halogens only after certain
regular intervals. fhese regular interyals being 2. 8,
8, 18, 18 and 32. Tbese numbers are alsosometimes
called magic numbers.
Ba-sed rrpon Modern Periodic Law, a number
of forms ofperiodic table have beenproposed from
time to time but the general plan of the table
remainedthe same as proposed byMendeleev. The
table which is most commonly used these days and
which i-s based upon the electrouic configuration of
elements is called the Present lirrm or the Long
418
-calkidBohr's
for the arran-
he nucleus.
Structural Featurs ofthe Present (or Long)
From ot the Feriodic Thble. The long form of the
periodic table consists ofeighteen vertical column-s
and seven horizontal rows. These have been ob-
tained by arranging the elements in order of iu-
creasing atomic numbers in such a way that the
elements with similar electronic configurations are
placed under each other in the same vertical
column. These veftica| columns are lotown as
groups or flaailies while the hoizontal rows are
called periods-These are discussed below :
1. Groups. (i) The present (long) form of the
periodic table consists of eighteen vertical columns
called groups. Each group consists of a number of
elements having the same electronic configuration
ofthe outermost shell (valency shelJ). These groups
are numbered from 1 to 18. Earlier in the modificd
Meudeleet's periodic table, these eighteen vertical
columns were divided into sixteen groups desig-
nated as IA, II A ... VII A ; IB, II B ..... VII B, vlII
and zero. Both these systems of numbering the
groups are shown in the long form of the periodic
table given on page 4/9.
(ii) The elements ofthe frrst two groups, i.c.,
1 and 2 on the extreme left involve the frlling of
s-orbitals whi-le those of the last six groups, i.e..
13 - 18 lying on the extreme right involve the filling
of electrons in thep-orbitals of the valence sheU.
The elements of these eight groups, i.e., L,2,
13, 14, 15, 16, 17 and 18 are collectively called
their valence shell electronic configuration
nsz np6.
(iii') The elements ol groups 3, 4' 5, 6' 7' 8' 9' 10,
1l and 12 are cslled trmrilion elements since lhei
properties lie beia,een the ProPetties of the reactive
metak (alkali and alkaline ea h metals) placed ott
the extreme left and non-metals (lfilogens and chal'
cogens :
rxygen fatnily) placed on the oLlreme iqht
of the peiodic table.
In these elements, both the outermost shell
aDd penultimate shell (next to the outermost) are
Neu/ Coursc Cheotistrg
incompletely filled but filling ofthe d-orbitals of the
penultimate shell occurs. As such their genera.l
buter electronic configuration is (n - 1)dl-10
nso-Z.
(iv) Tko series of elements each containing 14
elements are placed at the bottom of the periodic
table. The first series of elements with Z :
58 ao
Z 77 : *hich occur in the periodic table after
lanthanum are called lanthanides or bnthanoid-s
while the second series of elements withZ :
90 to
Z: 103 which occur in the periodic table after
actinium are called aclinida ot actbnids. These
elements are also called lnner transition elements.
In bcth these series of elements, the outer-
most shell and the penultimate shell are incom-
pletely filled but the filling of only/-orbitals of the
ante-penultimate shell occurs. .{s such their
general outer electronic configuration is
(n - - L) d-t ns2.
2\ lo-ra (n
2. Periods. As stated above, the long form of
the periodic table consists of seven horizontalrows
called periods. These are numbered as 1,2,3,4,5,
6 and 7 from top to bottom. Each period consists of
a seies of elements whose atoms have the same
pincipal quanrum number (n) of the outermost
sftell. In other words, each period begins with tho
filling of electrons in a new energy shell For ex-
ample,
The lirst priod corrcsponds to the filliog of
electrons in the first energy shell, i.e. n = 1. Since
this energy shell has only one orbital, i.e. 1s which
can accommodate oDly two electrol]s, therefore,
fint Deriod has onlv two elements.'lhese are
t ydrog.n (rr1) and h;lium (1-t2).
The seconrl period corresponds to the Iilling
of electrons in the 2nd energy shell, i.e. n :
2. Since
this shell has /our o,;bitals (one 2s and three p)
is
the second shell is comPlete.
The third period corresponds to the frlling of
electrons in the third shell, i.e. n = 3. This shell has
nine orbitals (one 3, three 3p and five 3d). How-
ever, we know tiom energy level diagram for mul-
tielectron atoms (Unit 3) that3d-orbitals have even
higher energy than 4s-orbital. Therefore 3d-orbi-
tals are filled only after r ing 'tr-orbitals' conse-
 |1 I
fl

o
F
@
U)
OLDGROUPNOS + B VB V8 VB \ IIB B B VIA VIIA 0 1'I
MODERNGROUPNOS + ,1
2 3 4 5 6 7 9 10 11 12 13 't4 15 16 17 '18
6
I
s-BLOCK (ns1-2; o
LONG FORM
P-BLOCK (nP1-6)
z
o
l'l
383ts8:1"?, OF THE PERIODIC TABLE @ m
+ 1
ns2 np6
r
m
2
E
(1s)
H
Hyd.ogon
1sl nsz
@@(E@o
npl) np2) np3
nsz ns2 1ns2 np4 ,s2 np5
H.
H.llum
'le2
m
z
--.1
3 4 5 6 7 I I 10 U)
a LI B! B c N o F N.
(2s 2p) L hium
2s1
B.rylllm
2s2 d.BLOCK (TRANSITION ELEMENTS) k2
B@
2p1
Carbon
zc2 zi
Nill*n
z"2io3
Oxre$
2s2 zg4
Fludim
2s2 2ps
N@n
2s2 2pG
zo
11 12 [(rl )dl-10 nso-2] 14 't5 16 17 18 -o
E N. M0 AI st P s cl Ar m
(3s 3p) Sodluh
3sl o o o o o o o @ @ (D
Slli@
L2 an2
Sulphur Chloire tu9oo
I
19
3s2
20 21 23 24 25 26 27 28 29 30
3s2 3p1
31 JZ
3s2 3p3
33
3s2 3p4
34
3s2 3p5
35
3s2 3p6
36
o
o
E K Ca Sc TI Cr J'N F. Co NI Cu Zn Ga Ge A! Sc Br Kr
(as 3d 4p) Pobsium CalciuD Sndium Iilanium Vanadium Chromrum lrcn Coball Nckel Copp. Zinc Gallium
12 ,^3
Selenrum BMire Krypton 6
4s1 6a2 ca1 t.2 3d2 4s2 3d3 4s2 3d5 4s1 3d5 4s2 3d6 4s2 N7 4s2 3d8 4s2 310 4"1 310 4s2 u2 a"1 k2 4s2 4p4 qs2 lp5 4s2 4pG
^n2
38 39 40 4',1 42 43 44 45 46 47 48 49 50 51 53 54
E
(ss 4d 5p)
Rb Sr
Ytu.ium
Zr Nb
Niobium
llo Tc Ru Rh Pd Ag
Silver
cd ln
lndium
Sn
Tin
Sb T I
ldine
Xe
Xercn
2
=
-u
q"0 4d10 5sl
5s2 4dl 5s- 4d2 5s2 4d4 ss'l 4d5 5sl 4a5 ss2 4d7 5s1 4d8 5s l 431 0 4d10 5s2 5s2 sp1 st2 sp2 ss2 sp3 5s2 sp5 ss2 sp6 a
E
55
C!
56
Ba
57
L.'
72
HI
73
T.
74
w R.
75 76
O.
77
lr
78
ft
79
Au
80
Hg
81
TI
82
Pb
83
BI
q
Po
E5
At
86
Rtr
o
1'
Csium Banuh Ianthenum Tanblum Tun96tff RlEnium
(6s (ar) sd 6p) H6fnlum Osmlum lddium Plollnum Gold Thallium Loed Bismulh Polonium Asbline Radon m
6s1 6s2 5d1 632 sa%s2 soa s* 5d5 6s2 5d6 6s2 5d7 6s2 5d9 631 56105s,| 310 5s2 6s2 6p1 6s2 6p2 os_ op" 6s2 6p4 6s2 6p5 6s2 6p6 I
8l 88 89 104 105 106 107 108 109 110 't 11 112 114 115
-t
a Ft R! Ac" Rf DI Sg Bh X! llr tun m
(7s (50 6d) Radium Ouhium
Uuu Uub uuq uup'
NOBLE
a
7s1 7P 6d'l 7s2 5y'4 6d2 7s: 6d3 7s2 6d ts2 6d5 7s2 6d6 7s2 6d7 7s2 6d8 7s2 56'lo 7"1 6d1 0 7s2 7s2 7p2 7s2 7p3

ELEMENTS I.BLOCIOINNER.TMNSITION ELEMENTS (RARE EARTHS)

{(r2)Pia (rl)dGr ns2l
-I,4ETALS

58 59 60 61 62 63 64 65 66 67 68 69 70 a1
'LANTHANOIDS (4f-series) Ce Pr Nd Pm Sm Eu Gd Ib Dy Ho Ef Tm Yb Lu
Cerium Tertium Erbium Thullium
1+tl-14 SOo-t Os2;
4fl 5d1 tu: 4F sdo 6s, 4F sdo 6s 4r7 fto 6s2 It7 sdl 6s: .P kP 83
90 91 92 93 94 95 96 97 98 99 100 101 102 103
-ACTINOIDS (sf-series) Th Pa U Np Pu Am Cm BK cf E3 Fm Md No Lt
Thorium Cudum
(5P-14 6do-1 7s2) Noblium
sP u2 7s2 t,:6dl 7s2 iP 6d1 7s, il{ 6dl 7s: 5F 6do zs2 sf 6do 7s2 it7 6d1 7si 5,9 6do 7s2 910 6do 7s, tf1 6do7s: <4: 6do 7si J13 tuo 7sj 5f{ 6d 7s tfla6d1 7sl

'Dis@ered rct rc@ntly by Ru$ian aDd US scbntist by hining arrcium (Z=95) with @ldum lZ=20) ?@teated in a cyclotron The calciurn nucleus simply tsed into the arrcium nuctous

5
@
 4110
quently, third period involves the filling sf only four
otbitols (o]ne3s and three 3p) and thus c ot.ltains eiSht
e/enrentri from sodium (Z :
11,3s1) to argot (Z =
18,3s2 3P6).
The fourth period corresponding to thefilling
of electrons in the fourth energy level, i.e. n = 4.lt
starts with the filling of,tu-orbital. However, after
filling4r-orbital, the hlling of hve 3d-orbitaLs begins
since the energy of 3d-orbital is lower than those of
9-orbitals but higher than that of 4s-orbital. Fur-
ther, the filling of ,ld and 4/-orbitals does rot occur
iu this period since their energies are higher than
that of even 5s- orbital. Therefore, in the fourth
period, the filling of only nine orbitals (one 4s, hve
3d and three 4p) occurs which can accommodate at
the maximum eighteen electrons. Therefore, ftitrth
peiod contoins eidteen elemenls from Potassium
(Z: 19) to krtpton (Z : 36).
The lifth period, Iike the fourth period also
contains eighteen elcments since only nine orbituls
(one 5s, five 4d and three 5p) are available for filling
witb electrons. It begins with rubidium (Z = 37) in
which one electron enters the 5s-orbital and euds
up with xenon (Z
=54) in which the filling of
5p-orbitals is complete.
The sixth period corresponds to the filling of
sixth energy level, i-e., n = 6. Since in this period,
-
or.ly six'teen oftitals (one 6s, seven 4/, five 5d and
three 62) are available for hlling with electrons,
lherefore, sixth period contains thirty-fivo elemeats -
It begins with cae.sium (Z : 55) in which one
electron enters the 6t-orbital and cnds up with
ratlon (Z = 86) in which the filling of6p-orbitals is
complete. of fu-orbi-
tal, the nff electron (i.e., enters the 5d*-
and thercafter,
f=156), the addition of ihc ncxt electton
(ia.5?th) shorld^occ!
tend ;o destabilize thc renon core (z = sq,lxrlUlo nf stz
electrofl preferc to entcrsd-olbitalwhich Iics outsidc the xenon
differcncc bctwEen 5/ and
,rsrabiti lectrons (i e 89th and mt h) a fte r thc filling of ?s-orbital prefcr tocntcr 6.r-orbitals bcfor
/ irliil ium (Pa : 91) and conlrnues till it is completewith lawEncium (Lr = 103)
..,1t . t' : Neu, Course t
the fillinsof seven 4f-orhitals begins with ceri.um (Z
= 5o-6i-anaends upwith lutetlum (Z = tl).'Thrsc
foirteen elements constit,'tc the flr!l,furi0ilqgr
transition series called lanthanides or lan-
thanoiils.These are separated frori the main fiiiic
of the periodic table and are placed at thc bottom
of the periodic table.
The seventh period corresponds to the filling
ofseventh energy shell,i.e. n = 7. Like sixth period,
it is also expected to contain thirty-two elements
corresponding to the fi)ltng of sixteen ofuitqb (one
7.r, seven 5/, five 6d and three 7p). However, this
period is still incomplete and only 28 elemcnts are
knowtr at present. In this period, after the hlling of
7s-orbital, the next two electrons (i.e., 89th and
90th) enter thc 6df * orbital against aulbau pincipk
and thereafter the filling of seven 5/-orbitals begins
with proactinium (Z = 9L) and ends up with
lawrencium (Z : 103). Although thorium (Z : 90)
does not have any electron in the 5/-orbital, yet it is
considered to be a /-block element. Since its
properties resemble more the /-block elements
than the d-block elements. These fourteen ele-
ments from thorium (Z : 90) to lawrencium (Z =
103).
These fourteen elements constitutc thc
seconrl (or5f) innertransition series which is com-
moily ialled as actinides or actinoids. lt mostly
includes man-made raalioacd\re-dlements. In order
to avoid the undue expansion of the periodic table
actinides like lanthanides, have also been placed
separately at the bottom of the periodic table
The number of elements in a period and the
tlpe of orbitals being tilled up is given in the
Table 4.4.
 CLASSIFICATION OF ELEMENTS AND PEBIODICIry IN PROPERTIES 4111

'fAIlLE 4.,1. Numbel of elemcnts in different periods

l'eriod No. ol the energy Orbrt:r Is ,einE Ii lerl No. ol clcctrons or elcmetrLs
level being Iilled ilr the period
I Lt )
2 n=2 Zt ,2p 2+6=8
3 n=3 at,3p 2+6=t:
4 4s ,3tl ,4p 2+10+6=18
5 n=5 5t -M,5p 2+10+6=18
6 6t ,4f , 5d ,6p 2+14+lO+6=32
7 1t ,51 , ,7p 2+74+70+6=32
(Out of these only 28
elenlcnls are kIlown
at present)

The frst three periods (1st,2nd and 3rd) ditficulties,thelUPACappointed aCommissionon

coutaining 2, 8, 8 elements respectively are known
as short priods while the next three periods (4th,
5th and 6th) containing 18, 18, 32 elemeqts respec-
tively are called long periods.
4.8. IUPAC Nomenclature
All the elemcnts withZ : 1o1-l72aulZ =
114 have bcen identihed. Some of these are known
since long while others have been discovered only
recently. Although names and slrnbols to many of
these clements have been assigned but these are
still not uriversally accepted. Also some of these
elements have been assigned two nameVsymbols.
For example, element vith Z = 104 is called either
Kurchatovium (Ku) or Rutherfordium (R) while
element with Z : 107 is called Neilsbohrium (Ns)
or simply Bohrium (Bh). To overcome all
Nomenclature of Inorganic Chemistry (CNIC) in
1994 to suggest a rational system of nomenclature
for clements with Z > 100 (also .^l t..tively c"lled
gs super heary elements). After having discussions
with chcmists around theworld, theIUPACin 1997,
approved the official names for elements with Z :
104 to Z = 109 (Table 4.5) and suggested a sys-
tematic nomenclature for naming other elements
with Z >
100 till their names are officially an-
nounced. The main points of this nomenclature
are :
(i) The names are derived directly from the
atomic numbers using numerical roots for 0 and
numbers from 1-9 and adding the suftix iran. A
strange mixture of Latin and Greek roots has been
chosen to ensurc that the symbols are all different.
The roots for the numbers 0-9 are :
thesc

TABLE 4.5. Roots for IUPAC nomenclature of elements

01234567E9
nil un l)i tri qund pent hex sept oct enn

nubtqphsoe

(ii) Iu certain cases, the names are shortened. 4.9. Eleclronic Configuration ol the
For example, bi iwn and tri ium are shortened to Elements and the Pedodic Table ::iii:ii:ii::iilrittiiitii::tit::

bium and. trium and enn n/ is short eted to ennil.

The present (long) form of the periodic table
(ur) The symbol of the element is then ob- is based upon electronic conliguration ofelements.
tained from the first letters of the roots of numbers With its help, it isveryeasyto find out theelectronic
which make up the atomic number of the element. configuration of any element. The outer electronic
The recommended and official names of some conhguration of all the elements along with their
super heavy elements are given in Thble 4.6 : symbols are given in the present form of the peri-
4112
Ner4 Course Chemistrq

IABLE 4.6. Recoruncnded and Olficial names of Glements with Z > 100

Z Ilecommended Ileme Svmbol IUPAC ollicllll Dam IUPAc syEllrol

l0l Uonilunium Unu Mendeleviun] Md

toz Unnilbium Unb Nobelium No
103 UDniltrium Unt Lawrencium Lr
104 Unnilquadium unq Ilutherlbrdiun'r Rf
105 UnDilpentiunl unP Dubnium Db
106 Unoilhsxium Unh Seaborsiunl Sg

107 Unnilseptium Uns Bohrium Bh

l0t UDniloctium Uno Hassoiun] Hs
109 Unnilen[ium Une Meitnerium Mt
110 UIlunnilium Uun
ltl Unununium Uuu
ttz UIrunbium Uub
113 Urluntrium Urlt
114 Ununquadiunr Uuq
115 UnuDpentium urP
116 Ununhexium Uuh
tt7 Ununseptium Uus
l1E Ununoctium Uuo
tL9 UnunenDium Uue
120 Unbinilium Ubn

odic table on page 419. However, comPlete
electronic configurations of all the elements along
with their names and symbols have already been
given in unit 3.
4.10. Division of Elemenls
Elemeots in the long form of the periodic
table have been divided into four blocks, i.e.,
s, p, d atdf. This division is based upon the name of
the orbital which receives the lasl elcctron. These are
briefl y discussed below.
1. s-Block Element s. Elements in which tlv last
electron enters the s-orbital of their respective out-
ermost shells are called s-block elements. Since
electron and this enters fu orbital. The rest of the
elemeats, i.. Li, Na, K Rb, Cs and Fr receive the
last electron in 2r, ls , rls , 5s , fu and 7J- orbitals
respectively. 'I'hese elements are, therefore,,said to
belong to s-block and have nsr as the general outer
shell electronic confi guration.
Now considcr He and the elements of group
2, i.e. Be, Mg, Ca, Sr, Ba and Ra. The last electron
in these elements also enters the r-orbitals, i..
fu,2r,3s ,,ls ,5s, (rs and fu-orbitals respectively.
Hence these elements also belong to s-block and
have ns2 as their general outer shell electronic
configuration.
Thus the elemens of groups I dnd 2' including
ch the s-orbitals arebeing
lled s-block elements' In
lements in the Periodic
table.
c,cfiBt$I AAls aefiguiltun { s'
blMkthirto,k

to be discoveled
"Elemcntsyct
 CLASSIFICATION OF ELEt\,4ENTS AND PEBIODIC|TY lN PHOPERTTES
,s
s-Block
d-Block El6ments
Elemenls
ns1 2 @-1)dt-l0 nso-'2
I
t-Block ElornEnts (rFz)P-ta 1n-t 1d-t
Division of periodic table into s, p, d- and f-blocks.
* ' Gencral characteristlcs of s.Block Elements
(i) They are soft metals with low melting and
boiling points.
(r'i) They have low ionization ethalpies (ener-
gies) and are highly electropositive.
(iii) They lose the valence (outermost)
electron(s) readily to form * 1 (in case of alkali
metals) and + 2 ions (in the case of alkaline earth
metals).
(iv) They are very reactive metals. The metal-
lic character and the reactivity increase as we move
down the group.
(v) The compounds of s-block elements with
the exceptioa of those of beryllium are
predominantly ionic.
(vi) Most of the metals of this block impart
cbaracteristic colours to the flame.
(ui) They are strong reducing agents.
(uu) All are good conductors of heat and
electricity.
2. p.Block Elemnts. Elements in which the
last electron enlers any one of the three p-orbitals oI
their respective outermost shells are called p.block
elements. Since ap- subshell has three degenerate
(same energy) p-orbitals, each one of which can
accommodate two electrons, thetfore, in all, there
In all these elements, the s-orbital of their
outermost shells is already complete but their
respective p-orbitals get progressively filled in by
the addition of one electron at a time as we move
from group 13 ao 14, 75,16, 17 and 18. Since these
elements contain one to six electrons in their
4113
respective outermost p-orbitals,
1s2
therefore, their outer shell
electronic confi surations varv from
o-Block nsz npt lo nsz nl6 a. *a -oua fro-
Elements
group 13 onwards upto group 18.
n*npl4
Thus, the elements of groups
13, 14, 15, 16, 17, lE (excluding
Irelium) in which p-orbitaLs are
n*
behg progressively filled in ate
c ol I e d p -block elementJ. Sio ce each
group has five elements, therefore,
in all, there are 3Op-block elements
in the periodic table.
General outer sheu
block elements : n?
The elements of group 18 are called noble
gases. Each period ends in a noble gas. Except
helium all the elements have closed shell nsz np6
electroDic configuration in the outermost shell.
Helium, however, has 1s2 clectronic configuration.
In these elements, all the energt levels which are
occupied are completely flled dnd this stable anan-
Eement of electrons cqnnot be eqsily altered by addi-
tion or rcmoval of eleclrons, As a result, these
elernents qrc highly stable and hence exhibit very lot ,
chemical reactivity.
. . The_elements.of group 17 are called hdegll
Gallprodteer.s) wbile those of group 16 are ia-liEd=-
chalcogens_(ore -fo tm i n g).
-hents have high iregafive
(or electronegativity) and
two electrons respectively to attain the stable noble
gas configuration.
General characteristics ofp-Block Elements
,.
(r)p-Block elements include both metals and
non- metals but the number ofnon-metals is much
higher than that of metals. F!fiher, the metallic
m top to bottomwithin a group
aracter increases from left to
this block.
.. _ (ii) Their ioni"ation energies are relatively
higher as compared to those ofs-block elements.
(iri) They mostly form covalent compounds.
4114
(iv) Some of them show more than one (uan'-
able) oidation states in their compounds.
(u) Their oxidising character increases from
left to right in a period and reducing character
increases from top to bottom in a group.
3. d-Btock Elements. Elements in which the
last electron enters any one of the ftve d-orbitals of
their respective penultimate shells are culled d'block
elements. Since a d-subshell has frve d-orbitals,
each one of hich can acco[rmodate two electrons,
w.
therefore, in all there are ten vertical columns com-
prising ten groups of d-block elements, namely 3, 4,
5, 6, 7,8, 9, 10, ll and L2.
The atoms of the elements belonging to these
groups usually have 1 or 2 (zero in some cases)
electrons in thes-orbital of the outermost shel7,i.e.,
ns-orbital while the electrons are being progres-
sively filled in, one at a time, in the d-orbitals of their
respective penultimate shells, r.e', (n - L) d-orbi-
tals. Thus,
Since the properties of these elements are
midway between those of .r-block andp-block ele-
ments, they are also called transition elements. All
thcse elements are further divided into four series
calledfirst, second, thirL and fotfih trawition seies.
The first transition series forms a part of the
tburth period of the long form of the periodic table.
It contains ten elements from scandium to zinc
( rrS" - ,oZn) h which 3d-orbitals are being
progressively filled in.
The second transition series which forms a
part of the hfth period also contains ten elements
from ytterium to cadmium (:sY - arCd) in which
4ri-orbitals are being progressively filled in.
The third transition series which forms a part
of the sixth period also contains ten elements, i'e.,
lanthanum ( srLo) and from hafnium to mercury
( rrHf - s.Hg) in which 5d-orbitals are being
progressively filled in.
The lburth transition series which forms a
part of the seventh period also contains ten ele-
ments, i.c., actinium (acA") and elements from,
rutherfordium (,*RI), to ekamercury or Unun-
bium (Z : Li}).In all these elements,6d-orbitals
are being successively hlled in.
Thus the etements of groups, 3, 4 5, 6, 7, 8, 9,
10, I1 and 12 belonging to fotuth, fifth' sirth and the
Pradeep's WD
incomplete seventh peiods in wlich tlrc lqst electron
enteni the d-orbitals of their respective- penultimate
shells are eollectively called d-block elements.
yffiineralcharacteristics of d-Block Elements.
' (i) 'l'hey are hard, malleable (i.e.. can be con-
verted into sheets) and ductile (i.e., car, be draum
into wires) metals with high melting and boiling
points.
(fi) They are good conductors of heat and
electricity.
(iii) Their ionization enthalpies are between
.s-andp-block elements.
(iv) They show variable oxidation states.
(v) They form both ionic and covalent com-
pounds.
(vi) Their compounds are generally coloured
and paramagnslis.
(rzl) They form coloured complexes.
(viii) Most of the transition metals such as !
Cr, Mn, Fe, Co, Ni, Cu etc. and tlreir compounds
are used as catalysts.
(u) Most of the transition metals form alloys'
(x) Zn, Cd and Hg which have the
0r - 1) dto rt*Z clectronic configuration, do not
show most of the properties of transition elements.
4. f-Block Elemelnts. Elements in which the lqst
electron enters any one of the seven f-orbitals of their
respective ante- penultirnate shells are colledf'block
elcmenls.In all these elements, the s-orbital of the
last shell (n) is completely filled, the d-orbitals of
the peuultimate (n - 1) shell invariably contains
zeto or one electron but the/-orbitals of the ante-
penultimate (" - 2) shell (being lower in energy
than d-orbitals of the penultimate shell) gets
progressively filled in. Hence
There are two series of/-block elements each
Threfore, in all there are 28
periodic table. These are
the periodic table.
Tlrc elements of the first series, i.e., cerium to
lutetium ( rrC" ,,Lu) which form a part of the
-
sixth period are collectively called as lanthanides
or lanthanoids since all these elements follow lan-
thanum in the periodic table and also closely
resemble lanthanum (La) in their properties. These
are also called rare earth elements since they occur
 CLASSIFICATION OF ELEIVENTS AND PERIODICITY IN PROPERTIES 4l'ls
scarcely in thc earth's crust. In lanthaoides, 4/-o.- Most of the non-metallic solids are brittle and are
bitals arc bcing progressively filled in. neithcr malleable nor ductile.
77tc eletner s of setics,l.c., thorium
rc secottd Thends in mtallic and non-metallic charac-
to lawrencium ( e6Th ln Lr) which forrns a part
- ter. 'llc-rnetallic character ilcreascs from top -t!
of tho incomplete scventh period arc collectively bottom within a group and non-metallic charaol.er
called actinides or actinoids since all these elc- _r4creases from left to This
ments follow actinium in the pcriodic tablc and also change lrom metallic t er is
closely rcsemblc actinium (Ac) in thcir propcrties. not abrupt as showu by long
In actinides, s/-orbitals arc being progrcssivcly - form of the periodic table given on page 4/9. The
fillcd in. elements silicon, germanium, arsenic, antitnony and
All the actinoids are radioactivc elenrents. tellwiunt (bo
Thc llrsl threc clements. i.L, thorium (Th). ly across the
protoactinium (Pa) and uranium (U) occur in na-- both metals
ture but the remaining 11 elements, i.e, from nep- callcd semi-metals cir mCGII6iili.
tunium to lawrencium ( rrNp - ,nrLr) have been 4.11. Advantages ol the Present (or Long)
prepared artificially through nuclear reactions. ,orm ol the Periodic Table i,,r.,,,
Tlrcsc eleven elemet s are cqlled transuranic or lrsn-
The present form of the periodic table has a
suranium elcments rince tlrcy follote urqnium in the
large number of advantages since it classifics [he
pctiodic tqblc oruL ulso haye been deived. from it
elements on the basis of electronic configurations
tltrough nucleat reoctions.
of their atoms. The important advantages are :
All the/-block elements, r.c., lanthanides and (i) It relates the position of an element in ths
actinides arc also called inner transition elements
table to its lectronic configuration more clearly.
sincc they form transition series within the transi-
tion clements ofd- block. (ri) It is easy to remember and reproduce. The
elements ca.n be teproduced more easily in se-
. General characteristics off-Rlock Elements
qucnce of atomic numbers.
'(i) Theyare hea\y mctals.
(ir'i) The elomeuts in the same group show
(ii) Theyhavc generally high melting andboil- marked similarities due to similar outer electronic
ing points. configurations. Thus, there is a logical classification
(ri) They show variable oxidation states. ot groups ro rt.
(ir) Their compounds are generally coloured. (iv) The elements are classified trrto tronrul
(u) They have a high tendcncy to form com 13- 17 groups and azn-
plexcs. to 3
- 12 groups on the
nic configurations.
(ui) Most ofthe elements of rhe actinide scries
(v) The elements are also classified as actiyc
are radioactive.
and 2, heavy metals
Metals, non-metals and metalloids. In addi- no,t-nletab placed in
tion to the division of the elements into r, p, d and ps 13- 18) of this pe-
/-block elements, all the elements can be broadly
divided into metals and non-metals.
_ (rz) Based on thei electronic configuration,
letals. Metals comprise 75% ofalt the known p, d arr'l l-
9fe1ent1,h9v9 been grouped into s,
clements and appear on the left hand side of the block. This has helped us to understand their
periodic table. With the exception ofmercury, gal- properties easily.
lium and francium which arc liquids, alt other me- ments of fourtb" fifth,
d sixth assigned properposi-
tiom
I (viii) A satisfactory position has been
s 8- 10 consist-
Non-metals. Non-metaLs may be gases, liquids (Group VIII of
or even solids with low meltiag and boiliog poinls.
4116
Since tong form of the periodic table corre-
lates the position ofelcments to the electronic con-
figuration of their atoms, it is, therefore, nearly an
ideal arrangement.
4.12. Dciecls ol the Present (or Long)
f orm o, the periodic Table : .:: :.r r.: :: .:: i ,:
Although the presetrt form of the periodic
table has removed most of the shortcomings of
Mendeleet's original and modified periodic table'
yet it suffers from the following defects :
.<:ff?osition of hydrogen is not scttled though
it fias been placed alongwilh alkali metals in
group 1 and halogens in group 17 since it shows
many properties similar to both alkali metals and
halogcus.
(ii) Lanthanides and Actinides have not been
accommodated in the main body of this periodic
tablc.
t.\ \\ ,t.tr 1,1. (s) Wite the electronic con-
of the elenwtls given below :
figtuotions
A (At. No. = 9), B (At. No. = I2)' C (At. No'
: 29), D (At. No' = 54), and E (At. No. = 58)
(b) Also prcdicl the peiod, group number and
block to which they belong.
9 ti
B
1t
C 29
D 54
E 58
(D) Element A receives the last electron in
orbital, therefore, it belongs to p-block elements
and its group numbcr : 10 + No. of electrons in
the valence shell = 10 +7 -- l7- Further the
period ofthe element = No. of the principal quan-
ium number of the valence shell = 2nd.
Element B receives the last electron in 3s-or-
hilal, thereforc, it belongs to s-block elements and
its group number = No. ofelectrons in the valence
rt iit = Z. Further the period of the element = No'
of the principal quantum number of the valence
shell = 3rd
Pradeep's
4.13. Prediction ol Period, GrouP
and Block ol a Given Element
The period, group and block of an element
can be easily predicted from its electronic con-
hguration as folows :
r: i :j .:i..:.:::..::rl (i) T'\rc peiod ol an elenrcnt conesponds to
tlrc pincipol Emnlrun ntunber of the valence shell.
(ii) The block of an elenrc t corespottds to the
ty?e ol oftitol wl'.ich rcceives the last eleclrun.
(iii) T'lu Sroup oI an elemeat is Predicted from the
number of electrons in the valence shell orland Penul'
timate shell (last bul one, i.e. n - 1) asfollows:
(a) For.s-block elemnt$ gtoup rutmber is
eEtal to the n,lumber ofvalence electrons.
(l) Forp-lrlockeleme 5 gntup number is eqrul
,o 10 + number of electrons in the Yalence shll.
(c) For d-btock elements, group number is
equal to the number of electrons in (n - l) d-su bshell
+ number ofelectrons ln valence shell (nth shell).
(c) Classify them as rcpresentqtive elements,
noble gases, transition ond, innet transition elements.
Solution. (a) Electronic conliguration of the
elenr B, C, D and E are as follows :
x2 zf
bz zs2 2p6 3s2
1'2 L\2 2p6 !t2 3p6 3dto 4t1
kz zt2 2p6 3s2 3p6 3d1n 4tz 406 47to 5<2 506
Ls2 Zf 2p6 3rz 3p6 3d1o 4r7 4p6 4dto 5.2 5p6 6sz 5d1 4f
]p- Element C receives the last electron in the
Element D receives its last electron in the
5o-orbital, lherefore, it belongs to p'block elements
uod it. g"oup nurrrber = l0 + No. of electrons in
the valJnce-shell : 10 + 8 : 18. Further, the
perlod ofthe element = No. oIthe principal quan-
ium numher o[ rhe valence shell = Sth.
 CLASSIFICATION OF ELEMENTS AND PERIODICITY IN PROPEBTIES 4117

Element E receives its last electron in the ([) (i) i.e. orygen, (iv) i.e. neon, (u) i.c. siticon
4/-orbitat therefore, it belongs to f-block elements. and (vi) i.e.nitrogen are2-block clements and
It may be noted here that the filling of 4f-orbital (i) Manganese i.e. (vii) is a transition elcment.
occurs only when oae electron has already entered
Sd-orbital. Therefore, element E belongs to f-block
L ,.' ii
.i !.Predict the positbn oJ thc clc-
elmnts and not to d-block cleneDts. Since it meti in the peiodic table sotisfying tltc clectronic
belongs to lanthanide series t-herefore as such it configuotion, (n - l) dt ns2 foru : 4.
does oot have atry group number. However, its (N.C.E.R.T)
period : No. of the principal qua-ntum number of Sulution. Forlt = 4. the elec(ronic configuru-
the valence shell = 5th. lion =-J4=l) 71 4s2 = 3d14s2. Thc elcmcnl- cor-
(c) Elements A atd, R arc representatiee ele- responding to this configuration is scortditun wlticlt
raezrs since their last electron entres p- and s-orbi- is a d- block element.
tal respectively. Group number = No. of electron in (a - l)
Element C is a transition element sincr it d subshell + No. of electrons in the nth hell
receives its last electron in the d-orbital. :7+2=3
Element D is ap-blo ck element
'.ith complele- Il\ \\ll'r.l 1.1. Elcments A, B, C, D ancl E
ly filled s- andp-orbitals of the valence shell. Such have the following electronic cottfigltto lhns.
a type ofp-block element is ca-lled a noble gas.
A: 1s2 2s22pt
Element E is an ,nn er transition element siace B: ls22s22p63P3pt
it receives its last electroa.it the f-o,bital.
c:1s22i2p63s2Jl
.The electronic configuraion of
some ven below :
D: I s2 2s2 2p6 3s2 3f
(i) 1s2 2s2 2p1 (i) ltz zsz zp6 3st E:1s22s22p63s23p64s2
(iii) W4tich among these will bclong to tlte sunrc
1s2 2s2 2p6 x2 3p6 *2 group in the periodic table ? (N.C.E.R.T)
(iv) ls? ?sz Zp6
. Soluggn. We know that elements having
(v) 1s2 ?sz 2p6 3sz 3p2 .-
similar valence electronic configuration belong t6
(vi) 1s2 kz 2pt
(vii) 1s2 2s2 2p6 3s2 3p6 $2 3d
(iii) lsz 2s2 2p6 x2 3p5
Natne these elements and indicate tyhich oI
them is (a) an alkali metal, (b) an alkatine eanjt
I,I\ANIPI_E {.5. ?7, e elements Z : I 17 and, Z
: 120 have not yet been discovered.
In what lamily
or group would you phce lhese elements qnd qlso
give the electronic configumtion in each csse.
Solutlon. Narnes of ihe elments : (N.C.E.R.T)

. . (i) Oryge" t,r) sodiun (ra) calcium (iv) neon

(v).siligon (ra) nitrogen (rzi) mauaganesi and
(nit) chlorine.
(a) (ii) r'./ sodium is an alkali metal
(b) (iii) ie. calcium is an alkaline earth metal
(c) (viii) ie. chlorine is a halogea
(a) (w) i.e. neon is a noble gas
(e) (vi) i.e. nitrogen belotrgs to group 15 Working on similar lines, the element with Z

. (f) (i) i.e. orygen, (iv) i.e. neon and (ra) i.e.
nitrogen belong to 2nd period
alkaline carth
configurution
) (ir) l.e. neon beirg a noble gas has lowest
7 p6 8sz or
reactrylty lement with z
= 118 is Uuo.
4118

l. Write the names and atoDlic numbcrs ofthe lollow- State to which blook of lhe periodlc table each of
lDg clements :
lhese elemerts belongs.

(i) The tburth alkali metal 3. An elemeDt 'X' with atomic nur,lber 112 has
recently been discovered. Predict its clectroniccoD-
(ii) The lhird alkaliDc earth metal figuration ancl suggest the SrouP in lvhrch this ele-
(,ii) The tifth element of the first transition series ment rvould be placed.
(iv) The tirsl lnner traDsitio[ elemeDt afld 4. Arrange the lbllowing eleD'lents il1 the incrcirsing
(v) 'l}le sixth uoble gas. order of nretallic character : B, At, M8, K
tN.C.E.n.r)
2. Ths outer electronic mnfiguration oi some ele-
lnents are given below : 5. W'ite the electro[ic configuration aDd tbe block to
which an element with Z = 90 bclongs.
(i) 3p3 (ii) 3(15 ,\t 1iii1zt2
3s2 3p6 +t2
6. How do the electronio configurations of the elements
(iv) 511 6e2 Q) 4f1 5dr (,,t1 with Z= 107 109 differ fiom onc arother'l
-

r. (,) Rb (Z = 3?), (i i) ca (z = 2o), (iii)Mn (Z = 25) 5. 1Rn1 6d2 2r2,1-utock

elements-
(,v) Cs (Z = 58), (r) Ro (Z = 86). 6. Elenrent with Z 1o'1 has five, Z
= =
103 has slx
2. (i) p, Qi) tt, (iii) s, (iv) d, (v) f while Z = 109 has seveD 5/-electrons.
r. 5/a ralo tr2, l2th group. Thus these elements differ in the number o[
1nn1
electroDs io the 5f-subshell.
4. B <A.l <M8<K

S EC-TION_II
AI'OMIC OR I'ERIODIC
PROPERTIES OF ELEMENTS
The various properties of elements may be
dividcd into the following two categories :

Clectronic confi gurations.

their atomic numbers, (i.e , get repeated after cer-

tain resular intervals) tberelore, these atomic
prop.rii". are also a periodic function of atomic
 CLASSIFICATION OF ELEMENTS AND PERIODICIry IN PROPERTIES
4119

. . I electron volt (eV) per atom

= 23.06 kcal mol-l
: 96.49 kJ mol- 1

For cxample, when hydrogon gas under Llr.

M(g) + encrgy ......_ M+k)
+fu)
whore M(g) and M rcpresent the gaseous atom
and the rcsultant gaseous cation (a positive ion),
Ionizstion enthalry it also known as ionizaion
potenlial since it is tlre minimnn poteltill dif-
lerence (ia a dischwge tabe) required to remove tite
most looxly hoanil ehctmn lmm an isohted
g$eout alom to lorm gsseouJ cation.
4.142. Units of I.E,/LP It ismeasured inunits
I electron volt (eV) per atom
: 3.83x l0 20 cal per atom
= 1.602 x 10-re J pcr atom (t cal : 4.184.1)
pressure is taken in the discharge tubo, a suclden
+ e- (g) very large increase in current flo\v occurs when the
voltage is 13.58 volts. Thus. ionization potentiat ot
hydrogen is 13.58 electron volts. Therefore, the
ionization enthllpy of hydrogen atom is 13.5g eV
or 13.58 x 96.49 : 1310.334 kJ mol-1
4.143. Successive Ionization Enthalpies. The
energy rcquired to remove the most loosely boLrnd
electron from lhe isolatcd gaseous atom is crllecl its
first ionizution enlhalpy and is dcnoterl by IE,
MG) + IEr ........_ M+(q') + r- G)
Similurly, the encrgies required tr) knock {)ul
second and third clcctrons arc called second rrnd
third ionization cnergics rcspectivclv c.g.
M+(q) + IEr..-......- NI,+(f) + c- k)
M'?+k) + IE3...._ M3+(g) + c- (g)
whcre IE, and IE, are thc seconcl and the
third ioniaton onthalpies respectively.

= .1.83 x It)-20 x 6.02.1 x 1021 cal mol- I

: rnol I
23.06 kcal
= 1.(r0 x 10-1e x 6 O23 x 1023 .1 mol-l The successive ionisation encrsies of somc
= 96.49 k.l mol-1 elcmcnls (in kJ mol- I 1 arc given in Tirhlc -1.7

TARLE 4.7. Successiye ionization enthalpies ofsome of clements (kJ mol- r)

H 1312
l,rl
He 112 2312 5250
Li lt2 zsl 520 7zvt 11810
Be 1r2 2r2 899 175't 14850 21000
B 7? z? 2p1 801 un 3638 250 3?l24
C 1.t2 2r2 2pz 1086 x52 4619 6220 3'1820 4',1280
N 1tr2 2t2 2oz t40z 2a58 4516 7413 9443 5325-5 6432u
o b2 zr2 zp1 t3t4 3388 5296 7468 10987 t3323 ri40-54
F lt' l68l
tsz 2.tz 33'15 6045 8408 1rc?n 15160 17564 92012
Ne \t2 2P 2p6 2080 3962 6226 9361 12186 t5236
4l2O
Neul Course

It maybe seen that,IE, is alwalt greater than which will hold its remaining electrons even more
energy required to remove
IE, and IE, is always greater than Iq, and so on
e gaseous atom should be
l' IE3>Iq>IEl required for the second
Explanation. This may be explained as follows: be greater than IQ. Thus,

When one electron has been removed from Iq>Iq>IEr.

the neutral gaseous atom, the + vely charged ion
-one
For example,
formed has electrotr less than the number of AIG) -e- AI+ G) ;
orotons in the nucleus. As a result, the electrostatic t"2 ztz 2p6 x2 3p1 1"? zsz 2p6 k2
Ittraction betweeo the nucleus and the remaini-og IEr = 579 kJ mol-l
electrons in the cation increases, i.e,, effective
Al* G) - e- el'* @) ;
u2 zsz 2p6 3tz 1s2 2s2 2p6 3s1

IEz : 179.5 kJ mol-1

alr* G) - " Alr* G) ;

the fust, i.e., Iq must be higher than IE1. 1.2 x.2 2p6 3"1 u'z? zpu

Further the removal of two electrons from the I4 = 2758 kJ mol-l

neutral atom gives a doubly +vely charged ion

Therelativestabilitiesofvariousoxidationstatesofanelementcanbeeasilypredictedonthebasisoftheir
successive ionization halpies.Il lhe dwfence in ionizalion entlnlpies of two succet\ive staleN is aPprc* eEul
e
ll or let, the lower oxjdation state ir hot ttable. conversely, if the
k) 10_15 eV pef otom (or 965-1150 kl mol-
diffetenceit'mofe thdn 15 eY the lower oidation slole is more stoble' Fot example' in case of Al'
te, = SZe U mot-1,I% = 1?95 kJ mot-l,IE3 = 2758 kJ mol-l and IEn = 11580 kJ mol-1'
Difference in successive io zation enthalPios.

IEz-IE1 = 1'795 -57g = 1216kJmol-r ; lEl - lF2 = 2'158 - 1795 =963kJmol-l

IE4 - Iq = 11580 - 2758 = 8822 kJ mol-
than 1450 kI n:ol - 1
and
Since the differenc' in succssiw ioniu tion energies bet reen IE2 - IE I and IE3 - IEz is less

rhat ofIEa _ IE3 is much more thaD 1450 kJ nrol-1, therclorc, + 3 oidation State ofAlitthemo stoble.

( l I,(ll()N ()1, l()}l/\1.I()\ l.N'l ll\|,l,ll,s

.F'''n-pip7,fiEa*ap.,|."I,,t.ttt:(.\I I ,:.:r:r i::::r '.:l

l.lx,ltr\ll{,E ;1.6 calculate the energ required . . Total amount of energy needed to convert

to convetl all the atoms ol magnesium to iagnisium Mg @) atom into Mgl+G) ion = IEr +IEz
ions present in 24 mg of magnesium vapours ? First
andiecond ionimtion enthalpies of Mg are 7i7 76
= 731 76+ 1450'73kJmol-r
urd 1450.7i kl mot-I respectivety. = 2188 49 kJ mol-1
)4U
ces
Accordi.trg to the defiaition of suc-
n energies.
24 mg ot Mg =
f.O t = 10ffi ^ot.
IEr ._
Mg+@)+e-@); = 10-3 mole
IEr = 737'76 kJ mol-l . . Amount of energy needed to ionize 10-3
Mc* G) + IE; ........ Me+ @) + e- (s) i mole of Mg vapours = 2188 49 x l0-3
IEl = 1450 ?3 kJ mol-l = 2.18t kI.
 CLASSIFICATION OF ELEMENTS AND PERIODICITY IN PROPEBTIES 4121

1. Calculate the eDer$/ in joules required to convert

all the atoms ofsodium to sodium ions presot iD
"RACTICE-
3. The first and second ionizatio[ potentials ofhelium
eV
atoms arc 24.58 aod 54.4 eV respectively.
2.3 mg of sodium lzpours ? Ionizatioo e[thalpy of Calculate the e[ergy in kJ required to produce 1
sodium is 495 kJ mol - I (Aromic mass of Na 23). mole of He2+ ions.
= [.1,D.. 7620 7t0 kI]
[.:tns. ll.s .1T; 4. The IEr aDd tE2 of Mg G) arc 740 and 1450 kJ
2. Thc ionizatioD potential of hydrogen is '13.60
eV
Calculate the enerry in kJ required to produce
n)ol-1. Calculate the percentage of Mg+ (f:) and
Mg2+ (g) if I I of Mg k) absorbs 50 kJ of ener$'.
0. I mole of H+ ioDs. civen, I eV = 96.49 kJ
mol-l; [.\lls 131.226|dl [,rr,.. Mg+ (g) = et.35% enrl Mg+ (g = 31.6s%l

H INlfS FoRDtFFtcuEr
No. of moles ofNa present is 2.3 mg ofNa
"RortElvs
= 0 0417 x 740 = 30.83 kJ
23xibi0
11xlf Ener!5/ feft unused = 50-30.83 =
= ro =1 x l0'mole 19.1'1 kJ
Nqw 19 17 kJ witl be used to ionize Mg+ G) to
..,Required eDergy = I x to-a x 495 x ld Mg'* G)
= 49.s J
2. Required energ)' = 0 1 x 13.60 x 96 49
.. No. of nroles of Mg+ G) mnverted iDto
l3l Mg2* G) = tg 1'.,11450 = o ot32
= 226 kJ
3. Required energy = t x (24 58 + 54.4) x 96.4g No. ofntoles of magnesiunl ions left as Mg+ G)
= 7620.1AO kl. = o.o4l?-4 0132 = O.t2A5
4. No. of Doles of Mg vapours present in 1 I = lZ4 .. %age otMg+ tg1= (0.028s,/0.0417) x 100
= 0 0417
Energy absorbed in the ionizatioD of 0 0417 nrole = 6a 35qa

of Mg
aIiEa a+eof M*+ G) = 100 - 68.3s = 3t.6Sjo.
k) ro M8+ k)

4'14.4.Factors Governing the Ionization Enthalpy. Ionization enthalpy depends upon thr:
-
factors:
following

(a) Nucleor charge

(b) Atomic size
(c) Penetration effect of the electrons
(d) Screening effect of inner electrons.
(e) Effect of a,angement ol erectrons, i.e. Effect of etactty half
Jified or completely ftlled orbitats.
to
he
he
ge

'IABLE4,8. First ionization enthalpies of

2nd r.o\1,elemelts in kJ mol I

Element Li BeB CNO FNe

Nuclear charge +3 +4 +5 +6 +'.l +8 +9 +10
Ionization enthalpy (kJ nrol-l) 520 899 801 1086 1402 1314 1681 2080
4122
Net Coutse Chent istrg

(fr) Atomic size or Raditts. lonizatkn energt

oI the outer electrons tiom the nucleus iocreases
thc ()uter elgctrons decreases. As a result, outer elcc
encrgy is required to knock them oul. Thus, ionizati
from
io, ionization enthalpy is found to decrease on moving down a group as is evident
'Iirhlc 4.9. "*o*pl",

"i all(xl: rrx lrrl- i)i i : '

l'AIll,E 4.9. liit \t ioniT.rtir)n crrlh'tiIi{ r I :

ffect of th effect ol lhe iruur electrons increase$, the ionimtion

as the Pen entlulpy decrcases.
is a well In mu-iilEGctron atoms, the electrons in the
iase-5f ;uiai--;Lciron atoms, the electrons of the
s-orbital has the maximum probability of being th
found near the nucleus and this probability goes on in
decreasiog in case ofp, d and/- orbitals ofthe same
shetl. In olher words, s-electrons of any shell are
more pe[etrating towards the nucleus than 2-
clectrons of the same shell. Thus, within the same
shell, thepgqqtlation effect decreases in the or{er :

" s>P>d>f
Obviously, if the pcnetration effect of the
is m!r!c, ifiEtrtt eloser to the nucleus and
charBe and the repulsive force felt by the valence
elqctron from the electrons presenl in the
Iflnce will be held more hrmly by the nucleus'
ih"ll-"l""trot.
inner shclls is called the shielding elf-ect q!'ggreen'
Cooscqucntlv, the ionization enthalpy will be high' charge
[ng etfect. Therefore, the eflective nuclear
ln ot hcr worJs. ionization enthalpy increases with (Z"y) is given bY the relation
the in
'fhus, 2., = Total nuclear charge (Z) - Screening
out g constart (d).
which where screening constant (d)i takes into ac-
tctnove a d-clcctron qnd so on. count the screening effect of the electrons present
For example, fitsl ionization enthalpy ol in the inner shelk. 6bviously greater the number of
alumitium is loier than that of magnesirm' This is electrons in the inner shells, larger will be the
due to the fact that in case of aluminium
(l;2 2\2 3\2 3p)), we have to pull out aP-electron to

tends to (lecrease the ionization enthalpy'

is lower than that of Be.

td)6hielding or Screening Glfect of the inner
*h"f dl""trrrns. As the shielding ot lhe suecning
the apptication of Sldr|
'ty'ct
 CLASSIFICATION OF ELEMENTS AND PERIOOICITY IN PHOPERTIES

enthalpies and hence dre highly reactive. In con-

trast, noble gases with stable zs2 np6 configuration
have highest ionization enthalpies and hence are
chemically inert. Similar trends are observed for
eachperiod a; maybe seen fromthe a graph plotted
betrveen the firstionization enthalpies along Y-axis
(iirrl_2",2pt,?!iubrr"Ts,":,l:l_:iH::Ti;d:frTi,,,l,:]il;f;,nf
and atomic number along X-o<is for the hrst 60
L".H::,1:
tion enthalpy than qryEs os2x22p12p1r2?1,). i;;;'i;r:i iil;.t;_r-"#;;;.;#:C;;?H;
This is because \contains exactly !4ll tilled p-or- most electropositive elemnt.
bitals. Such an arrangement gives extra stabilitytd
ff,iitom. As u r"*ritrr" i"ilou"r of electron be-

From thc above discrssion it follows thatzore 6 20 30 40 50

stsble the electronic confi,gurotion, grester is the
bnization enthqlpy.
Yariation of louiz:tion Enthalpy in the
4. 14.5.
Periodic Thble. The first ionization enthalpies of
the representative elements and noble gaies are
given in the Thble 4.10.
It can be readily noticed that the ionization
noble gases. Thus, alkali metals with one electron
in the outermost r-orbital have lowest ionization
AToMIC NUMBER (Z)
--+
(a) Variation along a period.ln general, as we
movc from teft to ight in a peiii!,-t-he ioiliiiion
enthalry itrcresses y)ilh increosint qtomic nunthers-
This is evident from the values of the first ionization
cnthalpies of the elements of second period as
given in Thble 4.8 or 4.10 and Fig. 4.3. The obscruetl
trend\ cqn be casily explained on the basis of in-
creased rutclear churge snd s,naller alomic rodii.

TABLE 4.10. First ionization enthalpiqs ofsome elements (kI mol- r)

TI I{e
1312
I-r Be B c N o F Ne
520 899 801 lm6 t4uz 1314 l68l 2080
Na Mg Aj si P S CI
496 73'1.6 517 786 1011 999 1255 1520
KCaca Ge As Se Br KI
119 590 579 760 946 941 1142 1350
Itb Sr In SIl Sb Ib I
,103 549 558 708 884 869 1009
Xe
1170
Cs Ba Tl Pb Bi Po At Rn
374 502 589 715 703 813 917 103',7
4124
Pradeep's

l**
i
Ne

o irrst ionization enthalpy ofB is lower than that of

= N (1402)
(1681) Be.
5 1500
o (1314)
B to c to N. As we move from B to C to N, the
5 keeps on
I (1086) g nuclear
F Be (E99)
zu., 't ooo
z, B (801)
o
E Li (s20) i,r
N
z soo
2 4 6 6 t0 o
o ATOMIC NUMBER (Z) + following reasons :

(i) Tbe electronic configuration of N

FIGURE 4.3. Variation oI Iirst ionization
with atomic number in second period'
"nt-halpy
(Ltz xi 2p1,2pty2pt") in which the ?-orbitals are
exactlv half-hlled is more stable than the elec-
irlri.' t ot o (7s2 bz 2piU'r2pt) i"
"orfigrrutio

simultaneous decrease in atomic radius, the o.

valence electrons are more and more tightly hcld
by right in .a
pe energy rs
rl9 ce lontza_
Li to Be, As we move from Li to Be, the
ionization enthalpy increases due to increased
nuclear charge and smaller atomic radius of Be
compared to that of Li.
mol
Bng
reasons.
(i) The outermost electron in B is present in
Z4- oiUita while in Be it is present in Zs-orbilal'
dince 2s-electrons are more penetrating towards
the nucleus than ?p-electrons, therefore, lesser
amount of energy is required to knock out a 2p-
electron than a fu- electron. Consequently, the first
ionisation enthatpy of B is lower than that of Be
(ii) The removat of an electron ftom O gives a
stable electronic configuration with exactly. half'
lrlled 2p- subshell, i.e. o+ $\2 zsz 2pt,2ptyzP:)
while this is not so in case of N, i e N+
(1t' 2"'2p1,2p)2pY). Since the removal of an elec-
tron from O gives
figuration than tha
the hrst ionization
of N.
O to F to Ne. The fust ionization euthalpy
increases from O to F to Ne because of the increas-
irg
as
has
the
is np6) electronic configuration.
(ns2
Similar variations iu the lrst ionization en-
thalpies of the elements of the third period have
been observed.
(b) Yadation down a group. The ionizalion
enthelpies keep on decreasing rugularl, as vtelnqe
down'a group fibm one element to the olfter' This is
evident from the values of the first ionization en-
thalpies of the elements of group 1 (alkali uretals)
as given in Thble 4.9 and Fig. 4.4.
 CLASSIFICATION OF ELEMENTS AND PEHIODICIry IN PBOPERTIES 4125

As a result, the distance of the valence electrons

tiom the mrleus increases. Consequeotly, the
Li (s20) force of attraction by the nucleus for the valence
electrons deceases and hence the ionization en-
1.* thalpy should, deoease .
(ir) Wrth the addition of new shells, the num-
-!
o
+so bcr ofinner electronshells whichshield the valence
= electrons from the nucleus increases. In other
g ,r'rctdsJhg sbieldilg ot the screening efrect increates.
_u 400 As a result, the force ofattraction ofthe nucleus fof
the valence electrons further decreases and hence
the ionization enthalpy should decrease .
5 15 25 35 45 55 (iii) Nucleor charye increases with increase in
ATOMIC NUMBER (Z) atomic oumber. As a result, the force of attraction
--+ hy the nucleus for the valence electrons should
FIGURE 4.4. The variation of first ionization increase and accordingly the ionization entha@
enthalpies with atomic number in should increase.
group I (alkali metals) ofthe periodic table
.'' Tlrc. combined elJect oI the increase in the
Ex;rlanatlon. The above tend can be easily ' -atorniisize and ihe screening fiecl more fhan com-
qlained on the bo$is oI inoeasfug atomic size and. pensates the efrect of the inoeased nucleor charge.
scrcening effect as follows : Consequently, thevalence elecfions becorne less and
(i) On moving d.own the goup, the atomic size less finnly held by the nucleus and hence the ioniza-
htueases gradrually due to the addition of onc new tion entlrulpies gaduolly decrease as we moye down
principal energy shell at each succeeding element. the goup.

l.). 1\ I l'!,1,. t.7 The electronic configtratiotr Since the M-shell is more distant from the
for the following neutral atoms are given for use in nucleus than L-shell, so lesser amount of energr is
Eteslion. required to remove an electron from M-shell than
(a) lsz , h2 ,2p6 ,3s2 ; (b) Is2 ,2sz , 2p6 , 3s1 ; from the L-shell. In other words, ionization enthal-
(c) lsz,h2,2p4: (d) ts2,2s2,2ps; py (IE) of atoms (a) and (b) shoutd be lower than
that of atoms (c), (d) and (e).
(e) 1s2,2s2,2p6.
Further, in case of atom (a), the electron is to
(i) Wich of tlrc electrcnic configuratiott givet
be removed from tbe more stable completely filled
above wouldyou expect for the noble gas ?
3s-orbital whereas in case of atom (b) it is not so.
(ii) Wticlt of lhe elecIonic confrgurotions given Therefore, the IE of atom (D) should be lower than
obove wortld you expect to ltote the lowest ionization that of atom (a).
enthalW.
The nuclear charge on atoms (c), (d) and (e)
(iii) List the above configurations in order of is +8, +9 and +10 respectively. Since the IE
i n cre o s ing ionization enthalpy. increases withincrease in nuclcar charge so theIEs
Solutlon. (i) Arrange the electronic con- of atoms (c), (d) and (e) follow the sequetrce:
hguralion o[7ll the atoms in order of increasing c < d < e.
atomic number in such a way that atoms containing From the above discussion, we conclude that
tho same outer energ5r shell are groupd together. the ionization enthalpies of the fivc atoms increase
Thus, we have in the following order :
1:7 zrz 2p4 l:2 2ps
2s2 b2 %2 2p6 b<a<c<d<e
(.) (d) (")
...L-shell i.e., Lr? 'b2 2p6 k1 < b2 2s2 2p6 3s2
L\2 'b2 zp6 k2 1s2 2
zp6 at1 ...M-shell . 1", b, Zp, . 1", 2"" d . 1", b, bo
(,) (6)
4126 Ner4 CouYse Chentist !
(ii) Evidently, atom (b) with elcctronic con- (d) a metqt lhatJotms a stable binary halide of
figuration, Ltz '2s2 2p6 k1 has the towest ionization the fonnul& AX2 (X = halogen). (N.C.E.R.T,)
enthalpy.
(ri) Since the outer electronic conhguration l;:tl"":
of ncble gases is ns2 np6, therefore, the electronic is fikely to
'!:2 2s2 2p6
conlrgura-tion, [atom ()l represents an
noble ga-s.
(b) Since the IE1 of element IV is very high
I,lx-All!'l.l- +.s nu fint (IE) qnd tlrc second
and its IF., is not so high (actually almost double),
(IE2) ioniz(ttio,t enthalpies (kJ mol-i) of a few ele'
it is likely to be a rec ctive non-metal (i.e., a halogen) .
men$ (lesigruted by Ronwn nwneruls ore sltown (c) Among the elements listed,IE, of element
bektw :
Element IEt lE, I is the highest and its IE, is also not so high,
therefore, it must be a noble gas.
I 2i72 5251
(d) The IE' of element III is higher than that
II 520 7i00
of element II, but unlike element II, its IQ is only
Irr 900 1760
it is likely that ele-
jiEq about twice its [El, therefore,
u t6t]0
ment III has two electrons in the valence shell (i.e.,
Whiclt of the above elements it likely to be
skaline earth metal). As such it will form a stable
(a) a rcsctive metdl (b) a reactive rtttn-metol binary halide of the fornula AX, where A is the
(c) a noble gas metal and X Ls the halogen.

l Arrange tbe following in the order of iocreasing 5. For each of tbe follclwing pairs, Predict which one
ionizatron enthalpy : bas lower first ionization enthalpy ?

(i) 1t22rz lsz

2p6 (ii) ls? 2 2p6 3sr (i) N or o (ii) Na or Na+ (iii) Be+ or M82+
(ii, h2 2t2 2p6 (v) B2 2\2 zpx (iv) I or I- l^ns. (i) O, (ii) Na, (r ) Be+ (lv) I I

1v1 tt2 2.r2 zp3 6. The first (IB1) and the second (IEz) ionization
[\r,,. (ii) < (i) < (iv) < (,) < (ii')l enthalpies (kJ mol-l) of tbree elements I, II, III
2.'fhe electronic configurations of some Deutral are given below :
atoms are giveo belo\, :
I II III
(i b2 ztz (ii)Ls2 2
2pr IEr 403 549 1742
(iii b2 2t2 2p4 1iv1 tP z? 2p3. tE2 2640 1060 2080
Which ot these electronic conliSuration would b
ldentifu the elemeDt which is likely to be (4) non-
expctcd to have the hiShest metal('6) an alkali metal (c) an atkaline earth metal.
(a) IEI (b) IEz (c) IE, (d)IEn?
(N.C.E.RT) [.415, (a) III (,) I (c) II]
rs. (a) (iv)' (r) (rir), (c) (r, (d) (i,)I
t/ 7. Predict which atom io each of the follo$'ing pairs
3. Among the eleDentsLi, K Ca, S and Kr, which one has the Sreater f,rst ionization enthalPy and exPlain
has the lowest first ioniztion enthalPy ? Which has your a Ner.
the highest first iooization enthalPy ? 0VC E R.I) (4) B ard C (D) N and O (c) F aDd Ne
fu1s. Lowest : K, Iltghcst : Krl (N.C.E.LT.) s. (c) c (D) N (c) Nel
4. Which of the follo[ing pairs of elements wou ld you
expect to have loerer first ioDization enthalPy ? t. From each set, choco the atom wtlich has the
Explain. (i) Cl or F (ii) Cl or S largest ionization enthalpyand exPlain your answer'

(iii) K or Ar (iv) Kr or Xe. (N.C.E.R.I:) (a) E o, N (b) Mg, P, Ar (c) B, Al, Ga

(N.C.E.R.T,) t (a) r (') Ar G) BI
I\,r. (0 cl (,0 s (ii') K (ir) Xel ',ts.
 CLASSIFICATION OF ELEIVIENTS AND PERIODICITY IN PHOPERTIES 4127

H;N:T9 FOR|;JIFFICULT ?F..ODLE|r',fj-

l. In a period, noble gas ,.e 1? ztz ?p6 (n, has the half-filled electronic coDliguratiol'l while in case ()1
highest IEl. Our of C, 1] 2]z 2p2 (.y) and N, N, an electroo has to be lost from a stable hall-filled
eleclronic configuration.
b2 2sz 2p3 (y), N has higber IE, due to higher
(ii) Na hB lotver IE1 thah Nl?+ because of the
nuclear cbange and stable qtscdy half-filled clectronic
configuration. Bcaus of bigger sizE both Mg, following two reasons :

t-tz 2t2 416 *2 (D and Na, b2 2f2 2p6 3rl (n) bave (a) In casr ofNa+, an electron ltas to be lost fron'l
loc/E{ IEI than q N, O. Out (, and (ii), (i) has higher a stable inefi gas coDfiguration but it't cilsc of Na,
IE, due 0o higher nuclearcharge and cornpletelyfiled loss ofan electron gives stable inert gas configura-
tion.
r.orbital. Thus, the overa[ order of inqeasiDg IEl is
(n) < (t) < (rv) < (y) < (rli,). (6) Na is neutral but Na+ is +!ely chargeci.
2. (aHrv) has highest IEI due to srable emcrly half- (iii\ Be+ hat lower I E', tlnn Mq2* hccitusc in case
filled electronic configuratioo. (DHi r) has highesr
of Be+, the loss of or]e eleclroD givcs a stablc iDert
IF2 since the second electron has to be remorr'ed
configuration but rn case ofMgz+, the electron
from the stable exactly half filled electronic con- -[as
has lo be lost fronl thc stable tnert gas contigura-
figuratio[ lefl after remo,/al of Ist electron, ie.,
tion
IE. IE
tr z? zpa t? lr2 d J (iv) I hat lowet IEr than 1- because in case of l-,
-i highest Iq since
(c){i) has the rhe rhird etecrroD an electroD has to be lost front a stablc inert gas
has to be remor'ed from the stable inefl gas con- configurahon.
IF. IF. IE,! 6. (a) IEr ot elenrcot III is rhc highest of rhc rhree
fiSuration, l?2? --; --: k"^ -,
B2 zst
elements listed, thereforc, il is a non-tnetaL.
(d)-(r'i) has the highesr IE1 sinc the fourtll
(6) SiDc IE ofelement I is very trigh Ns coorpared
electroo has to rcmoved from the stable inert gas
configuration, to rts IEt, therefore, it it an alkoli rnetal.
IE, IB IE. IE. (c) Since the IIll of etemen( II is higher than rhat
-: b2 xz -: b2 2rl -J 1rz
Llz 2rz 2pt
3. Among rhe elements Li, K Ca, S and -;.
of element I and lower thaD rhat of clcntent III,
Kr, thc therefore, it is an a/*aline eonlL tnelaL
elements K, Ca and Kr belong to 4th period. SiDce
itla period, alkalimetal has the lowest and inen gas 7. (a) C has hiBber IEI rhaD B because oI higher
has the highest IEl, therefore, K bas the lowesr Duclear charge.
IEt and Kr has thc highest IEl. (D) N has higherIEr thirn O becausc in cdsc ot N,
4. (, Because of the bigger sbe and stronger sbielding the electroD bas to be lost from a morc srablc
effect, Cl has lo er IEr thaD E exaclty half-fi lled eleutronlc conlidurctirr.t.
(c) Ne has higher IEt than F because ofsta btc inert
(r'i) Among S ard Cl, S ha6 tower IEI due to bigger
gas configurarion.
size and lower Duclear charge,
(ri) K has lower IEl tban Ar because K has one t. (.r) E O. N allbelong lo znd period. Antong lhcse,
F has the highest I Et because ( rfiLs solallesr size and
more electron than Ar and hence can easily 16 this
highest nuclear charge.
electron to aaquire stable Ar has mnfiguration.
(D) Mg, P, Ar all lie in the 3rd period_ AmoDg these.
(iv) Xr because of its bigger size aod stronger Ar has the highest IEI because it has stable xlert
shielding effect has lower IEI than Kr.
gas configuratioD.
5. (i) O has lower IE r rh4n N because iD case of O, loss (c) B, Al, ca all lie io group 13. B has rhe highesr
of an clectron gives O+ which bas stable exactly
IEt due ro its smallest size.

l. l5. Eleclron Gain Enthalpy. :ji:xj,tiii:ilsl,lliirj fiti

4.15.1. Delinition and Units. Just as energy
(called ionization enthalpy) is required to remoie
4l2B Neu) Course Cl,

Electron gain enthalpy oJ ot element mty be defmed second and higher electrongain enthalpies are also
os the energ relatwl when a ncufialisolded gltilttt possible. However, after the addition of one
dlom uccepl\ un elra elslron lo lorm lhe gascous electron, the atom becomes negatively charged and
negative ion, i.e., anion. Il is dcnoled b! L"s H. the second electron is to be added to a negatively
charged ion. But the addition of second electron is
This process may be represented as : opposed by electrostatic repulsion antl hence the
x (c) +e- ""--, X' (E) i enety hos to be supplied fot the addition of second
ncutml Saseous atom electron. lhus the
ariT'L., H . 1,y an element is po
electron is added
Evidently, greater the arnount of energy
energy is released. But when aqother electron is
released in the aboveprocess, higher is the electron
gain enthalpy of the element. added to O- ion to form C)2- ion, energy is ab-
ln oth er words, the electron gain enthalpy oI an sorbed to overcome the strong electrostatic repul-
elemmt is a meastre of the firmness or strength h)ilh sionbetween the negatively charged O- ion and the
which an extra electron is bound to it. Like ionization
new electron being added. Thus,
enthalpy, electron gain enthalpyis measured either First electron galn enthalpy,
in electron volts per atom or kJ per mole. o (s) +e- 1"1 '-"' (s);o-
Depending upon the nature of the elemenl the AH"' = 141kJ mol-l
- (EnaE/
process of adding an electron to the atom can be releatu,
is

eithier exothermic or endothermic. For majority of the Second electron gain enthalpy :
elements, energy is released when atr electron is o-(s)+e-G)+ o'?-G)'
AH"' = a 780 kJ mol-1
(Enet absotb.d)
is

Similarly, the second elecEon gain enthalpy of

S is also positive. Thus,
Flrst electron gain enthalpy,
ing an extra electron. s(6) + e- G) + s- G)
latge posilive elecion 6H.r = 200 kJ mol-r
oitra electron ha.s to - (Enct&/ is rcleasctr)
principal quantum enerry lewl thereby producing Second electron gain enthalpy,
highly unstable electronic configuration. S- (q) + e- (8) -'----'--- S'?- G) ;
4.15.2 Successive Electron gain enthalpies. AH". = a 590 kJ mol-r
Like second and higher ionization enthalpies, - lEnetR' is ahttbeA

ct(s) + e_ .,_
ftno -o,_,
is relessed when i'55 g of chloine is converted . .
Energy released when l mole ( : lJ.J g)
completely into Cl- ion in the gsseoLt stsle. of chlorine atoms change completely into Cl- k)
Sotutlon. According to the definition of
=3491rJ
elect nthalpY.
.In ma.iority of the text books, thc negativc of thc cnthalpy changp accomPanying thc addition of an clectrcn
to an isolatcd
g"""orr" i. o'.fin"d as .tccaron 6m ti(A"). Thc ctcctron irfinitfis said to be 'oslllv., il arcr&l is tclcoscd whcn dn isolat d
"to,i
gt,],cous otorn acccpi on ctectron dnd it is osighed a n gald,v. slg3rt if eneryl is to bc wPlied to odd an exlfa
dectort to the isolnlcd
i,ruseoreratom Thii is, hollrclrr, contrary to th; thermodynanlic con!ntion. Further, since electron affinity is de{incd at absolutc
;ero, thcrcforc, at any othcr temperaturc heat capacitics instead of elcctronaffinity of the rcactents and Produc6 should.bc
considercd. TherEforc, in vicrr o] thesc tso ncasons, the term clectron gain enlhalpy is used instead of
clcctron_affinity

Thc ts'o terms arc rclatcd to each other as

^H.s=-A.-;Rr !rluc of52 RTat 298 is
Thus numcrically clecrron gain cnthalpyis highcr than that of clcctrcfl affinity by52 RT. Sincc thc
l, uscd indistingpishably with thc only
iust 2.47/ kJ nrol- thercfore, this 6mall differEncc is oftcn ignord and thc two tcnns arc
;ifferancc lhat .t.clmn aeln cnthalPy b Jura th. nlEnllr'r ol'l'ctrcn smnlty'
 CLASSIFICATION OF ELEMENTS AND PERIODICITY IN PROPEBTIES
4129
Energ5r relased when 3 . 55 g of chlorine atoms
Cl @) + z---.-....- Cl- G) is 57.86 x 1o-r0 J.
change completely into CI- k)
. .'. The dectron gain enthalpy of .hlorine, i.e.,
= 9"3.5s
35.5 - -- = 34.err.I. the amount of energy released whea 1 mole
(6 023 x lG1 atoms of chlorine are converted
- The anount of energ into Cl- ions rccording to the above equation will
atoms of chloine in vapour be
Cl' ions according to tlrc -
57.86
-- ";
x 1o-ro
=_ x6.0Z3xtcE
Cl(g) + e- -----.....+ (g) is 57 .86
Ix 10ru
Ct- n-1o L x
Calculate the electron goin enthalpy o! chloine =- 348.49 x ld rmol= - 3llE.49*J/mol
alom in tems ol kJ mol-l
and eV per atom. Now l eVlatom = 96.49kJmol-l
The amount of energy released .'. Electmn gain enthalpy of chloine
when 1 x 1010 atoms ofchlorine invapourstate are w.49
converted to Cl- ions, accordirg to the equation. =- %4'g = - l'61eY/*om

1. The elerfion affiDity of bromioe is 3 . 36 eV Ho\, muci

encrsr in kcal is released \rten gg of bromiDe is com_
"RACTICE-
ions in the vapour state according to the e4uation,

pletely corFErted to Br- ioDs in the gasrous state ?

l(g)+c- I- (t)is4.9x t0-13J.
(1eV=23.66 1q'1 .o1-tr. -
Calculare thc ele.{ron af6nity of iodine in
I ADs.7.74t kcatl (t) k /mol and (n) in ev pcr arom.
2. The amount of erierry released wheo one million
I Ans . 295 hl/Eol rnd 3 .
06 cVlatoml
atoms of iodine are completely converted into I-

1. No. of moles ofBr = 8/80 = 0.I

Required enerry = 6.1 x 3.36 =29.5x1oix1O-3H
>< 21.06
= 295 k! mot-1
= 7.7{8 kcal
2. Elecrron afliniry = 295 /96.49 eV / atom
x = 3 06 eV / atom
= 6.023 1023 x 4.9 x 10-13 x 10-6

4'153' Factors on which the Erectron Gain Enrharpy

dpends, some important factors on which
electron affinities depend are discussed below :
a eases
which i As a
and the
the e
4.L7).
{t'i) Nuclear charye. As the nuclear charge increases, the force of
and the incoming electron iacre ases ara ruo""irr"'"i""t.oo attraction between the nucleus
gii" u""omes more negative.
"ltrrpy
exactly half_filled or completely hlled orbitals are
d an electron. Hence theii electron gai,
additional electron so easily. "rtlutr;""
n the periodic Thble. The electron gain
enthalpies of
 Neut Course Chentistry
4130

id#;.i;. ;i;il il;ffi;i;;i;i;; ;i ""-"'"i"-"ii"'ii r.i-"i'

Period 16 1'7 18
13 74 15
I GrouP - 1
He
1.H +rl8
-'73 Ne
C N o F
z. Li Be B
-122 +31 - l4l -324 + 116
-60 +66 -83
AI si P S cl
3. Na Mg
-119 -74 -200 -349 +96
-53 +67 -50
Ge As Se Br KI
K Ga +96
- ? -36 -116 -71 -195 -325
I Xe
5. Rb tj Irl Sn
-
Sn
101 -
1U
190 -295 +1'7
-47 -29 -7?t
At Rn
6 G Ba It Pb Bi Po
-n0 +68
-30 -101 - 110 -114
-46
and the electron
) is less negative
It may be noted
s the Eost trega-

.tive electron gain enthalPY.

geberul' elec'ron
ore negative Imm
be explained as
follows :

lows.

below :

bromine to iodine.
 CLASSIFICATION OF ELEMENTS AND PERIODICIry IN
PROPEHTIES 4131

I gso
I
z^
2i325
d>
z=
Y
F
soo
..(ri) enthalpy olnoble gases k
o
tr.l
r (-2es) pos ,vc. e fact that the atoms of
these ele letely fiJlcd subshelJs. As
9173553 a result, in their valence orbitals
ATOi C NUMBER (4 _______)
and the additbnal electron has to be placed in an
orbital of nexldgher shell. As a resuli energr has
FIGURE 4.5. Variation of electron to be supplied to add on additional electrl-n. In
gain enthalpies of halogens.
other words, lhe electron gain enthalpy of noble
gases is positive. Further, as we movi'down the
group, the size of the atom increases and hence
electron gain enthalpies have lower positive values.
For example, electron gain enthalpyof Ar ( I 96) is
lower than that of Ne ( + I l6).

.11. Which of he followhg ele-

negative electon gah enthalp! ?

(i) [Nel 3s2 3p3 (ii) [Nel 3s2 3p4 (iii) INel3? jps

resp . The element (chlorine) cor-

he electronic confisuration /iii\ \vi

(b) Cl has more negative electron gain enthal_

-
py than I.i
Reasoa. As explained in Example 4.11.
(c) S has more negative electroi gain enthalpy
,
thqn O.
of the following pain
negative electron gain

(i)NorO (N.C.E.R.T)
(ii) F or Cl (N.C.E.R.T)

. (d) C has more negotive elecnon gain enthalpy

that Si.
Reason.
thao Si-atom.
sions in these
contaiu ody4
 Neut Course Chent istrg
4132

Wich of the Jtllowing will

luve tlz most negative electron goin thalry ond
wllich the lcosl negqtive ?

ES,CI,F
(N.C.E.R.T.)
given a'oms into dif-
lere order of increasing
atomic nurnbers :
GrouP No. 15 76 1'7

2nd Period F
enthalP".
3rd Period P S Cl

has
3. Which ofle (atom/ion) in the followiDg Parrs
l.'- Arranre the elemenls wilh the folloxing eleclronic
higher electron gain enthalPY'l
.""it""u.ntiona in order oI lncreasing electron Eain
entha"lPy. (i) o-, s (ii) o, s- (tiD o- , s- (it') N- ' P
(i) b2 ztz 2p5 OD \2 ztz 2p4 Qii)82 2] 2p3
I .' - (DO- > S(i4s- > o (iii) o- > s-
(iv) N- > Pl
(tu) b2 2t2 2P6 3? 3P4

I (D < (i') < ('i) < (ii')l " The electron gainClenthalPies
4, of haloge[s dcorea'\e
2. Arranle the following elements in otder ofdecreas- inirr" oro", f:, > Bi > l. Conment upon the
rng ele-ctron gain enthalpy: B C, N' o' statement. I The statement>isl-lvronS' > Cll
The nctual orrler is I > Br
Ir' N' D' C' OI

FOROIFFICULT ?RObLE*N49
ffi"*rg -d;.f garo enthalpies is N' B'
t. out or F .s2 2\2 2p5), o osz zt2 2P4) c, o. "leotron
N (k2 2r2 2p3) arld s <|sz ztz .2p6.3t1 eledrons on
'/1t "lY^I 3. (i) Due to rePulsions between the
O- aDd the additional incoming eleclron' lhe
elecron Eain cnthalpy of O- is Positive while that
O a -ve.
(ii) On similar grounds, tbe electron Eain eDthalPy
of S- is +ve while that of O is -ve
(iii) Due to smallsize, repulsions between O- and
than in S-'
the incoolin8 electroD is much more
Therefore, electro[ gain enthalpy of
is n]ore
')-
+ve ihan that of S-
(iv) Due to repulsions bctwcen N- and the incom-
ing electron gain enthalPy ot N- is Pcsitive while
lhat P is -ve.

of atom is co'tsidered
i:i:ii:;:ii::iiilil:lit:riiii:iii:i::iiiiiiiili,Il:llgliixii:irliiji:iii:l:l:l:
to given bY the radius
4.16.1. size of an atom, i e'' the
Dcfinitton.The
'4 lonwn as atomlc
atomic.size is a vcry important property of an atom ra
since many other physical and chemical propemes
 CLASSIFICATION OF ELEMENTS AND PEBIODICITY
IN PROPERTIES 4133

The distance lrom the centrc of ,he nudctlt to thc For enmple, the internuclear distance be_
oukrmost shzA containing rht electmns.
Or
The distance trom the centre oJ the nutler$ ,o
thc
point upto which thz dewity o! the elqtron cloud
(i.e. prohability of finding the elqtron)
k mari-
mum.
(6) van der lVaals, rartius.
4.162. Difliculties in determining atomic
radius. Atomic radius cannot be delermined It is dqlitd as om-W thc .Iistarce betueen tlz
precisely due to the following reasons :
nucw o! tvo lderticsl twn-hondei! isolttd stot tt

(rr) It is not possible to isolate a single atom

- the
for
.
purpose of determination oI its rajus.

(ir) The atomic radius also changes whcn the

atom is present in different bonded stites.

(i) Covalent rudii (ii) van der Waols,radii

and (iii) Metottic rldii.
(a) Covalent radius.
is defrned as bdweqt thc
rurclei of tvo co of the same
elemgnt in a. mo
VAN DER WMLS'
Thus, for a homonuclear diatomic molecule, RADIUS = l!9 p61
1 COVALENT
/couatenr = RADTUS
; llnternuclear distance between = 99 pln

two bonded atomsl FIGURE 4.6. Covalent and yan der

. .Since the internuclear distance betweeu two
bondcd atoms is called the bond length. Thereforel
Waals radii of chlorine

and yan der

rco,alenr =
I
j Wa fanelemenr
[bond Ieugthl
isa s bccause ol
the
 Neu/ CouYse Chen' istnJ
4134
tracted bv a number of metal ions This simul'
,i-"ii io",
""tiiiniana ol attaction between the mobile
*"'posirive kemels k colled the melal'
lic bond.
: lt k iffitpi! as N,r.tt4{,hB inkrnuclzu dUgT z
;;,,;; i; *" ;dir-;, nctat io,,o in tt* "Ptnuic
lsltbe.

derWaals'radii.

o{ atomic
- -orbitolt 4.7 ' OverlaPping
FIGURE
to fotrn u tolalent bond

metallic radius > covalZnt radius'

van
Out of the threc typcs of atcmic radii(covalent'
and hente atomic radius ofan atonl s us
cleternrine
'fhe aiom rc usuallY exPress
number of
iil;;;; Dtry a
ius of xenon can
pr"pared.
covalenL radius.

Thbl'e
4.16.5. Variation of Atomic Radli in the Feriodic with i?u:!u i,?
ovalent or ean det Wsah' decrease
the atomic (covalent) raqr
ior example, consider
. 4.8).
 CLASSIFICATION OF ELEMENTS AND PEBIODICIry
IN PROPERTIS
4135

TNJLD 4.12,. Decreas in atomic ((o\alent) .raiiin tt p"rina

".".o.ra
Elemcnt Li BeBC N Ne
Nuclear chotge +3 +4 +5 +6 +7 +10
Outer ekctt onic 2v1 x2 2"r2p, 2r2 2oz '>"2 tJ b,2po zt, d 2t2 206
configtration
rudii (pn) 152 75 160+

u (152)
t '|

g
1 20
f Be (11r
o- )
(r '| 00

o B (EE)

I c (77)
N Os)
o
F (72)
(741
246a
AToMlc NUMBER (a--+

FIGURF 4.a. Variation of atomic radius with

atomic "'
number across the second perioJ.

From the above table, it is evident that_

. alkali metals b,hich are at the utreme
!),m"peiodic
lelt" tuble have the laryes size in i
-of_the radii also
period
a period.
(ii) The halogens which ue prcsent at rhe
ex- N, O and
trcnte ngl olthe peiodic table hqve the smollest
size. tively.

TAHLt,l ;1.1--t. Incr.(xse in xtonlic l, or alent) rarlii of tlre alkali mttals.

Elemenl U Na K Rb G Fr
+3 +t1 +19 +37
()t a ter electTonia +55 +a7
c onfg |olion

(:otllcnt todii (pm)

'2Jt
3l 4ol J,r' 6rl ,t:
152 186 B1 244 262

clear that the atomic r

metals. Similar trend is

+van der Waals,radius.

 Pradeep's
4136

300

2so
|
K (231)
zoo
E

f, rso
E
o 100
o--
=

0ffi6-;6-uo 60
ATOMIC NUMBER (Z) ------->

,, Lt;*ilt k'"lY:ll1'f t ;t;i:"'s';ii'ii:x:l'l

ttl
t.----+
'INTERNUcLEAR
DISTANCE

FIGUBE 4' 1 O' Internuclcar

distancP and ionic radius'

and 215 Pm resPectivelY'

4,i7, lonic Radii +Lriiililrt:iliii:

dii corresPond to the radii ofions

iont, i" iuto, are formed. when
 CLASSIFICATION OF ELEI\4ENTS AND PEBIODICITV IN PROPEBTIES 4137

from themeasured internuclear distturce in its com-

pound. For cxample, based upon Pauling's method,
the absolute value of the ionic radius of Na+ ion
has been determined to be 95 pm. Therefore, the
6)
\=/
6)
\--l
ATOM CATION
ionic radius ot Cl- ion = 2i76-95 = 181 pm.
Further , the radius of Na+ ion thus obtahed may 11 ELECTRONS 10
bc used to calculatc the radii of other anions, such +11 NUCLEAR CHARGE +11
as Br- and I- ions, by measuring the internuclear
157 pm S|ZE 95 pm
distances in NaBr and NaI. Sirnilarly, the radius of
the CI- ion may be used to calculare the radii of
FIGURE 4.1 I . Relative sizes of
other cations such as Li+, K+ etc. by measuring Na atom and Na+ ion
internuclcar tlistances in LiCl and KCI crvstals
respectively. rcsult. thc sizc o[ 1he cation is smallcr than the
4.17.1. Comparison of the ionic radii with parcnt atom lrom which it is lormcd. Fulther. due
corresponding atomic radii. A study of ionic radii to thc remoyll of elcctrons lrom thc parent atom,
o[ cations and anions reveals the following two the numbcr ol electrons in the cation dccreascs
generalizations : (Fig. .1.ll ) but its nuclear chargc rcmains thc same
(a) The radlus ofthe cation is always smaller as that of thc atom. As a result, the force of attrac-

than that ofits parnt atom. A cation is formed by tion hy the nuclcus on lhc clectrons increases (i.e.
cffecl it'c ttucleur ch trge increases) anrJhencc the sizc
loss of one or more electrons from the neutril
gaseous atom. This generally causes the removalof
oI the atom decreascs. Thus, in nutshcll,
the whole of the outermost (valence) shell of catitn is always smallzr lhun that oJ
The size oJ a
electrons, correwndinq slom due to (i) decrease in lhe
lh.e
e.8,, Na .-..-.....r Na+ + c- number o! shells (ii) increqse in lhe e[fective
1s2 2spz 2p6 3s1
x2 zp6 ts2 nuclear charge resuUing in geafer lorce oJ altrac-
Due to the removal of the valence shell, the tion by the nucleus on thc clectro$.
number of sbells in the cation decreases. ds a This is illustrated in Tablc 4.14.

TAIILE 4.14. Comparative sizes of atoms and their catioru

Atonl I.i Na K Be Mg Al Mn
Atotnic raclii (pm) I tSz 186 2i1 1 160 143 126
Crne:ponding cationt +
I Lr+ Na+ K+ Be2 Mg'* Al3+ Mn4+
l,,nt nt,lii llttttt j r,u 95 133 39 65 -50 16

Variation of ionic (cationic) radii within a decreases (i.e., effective nuclear .r).
Hetrce the elecoon cloud of the In
other words, the distance betwoe he
nuclcus and the last shell that contains electrons
increases thereby increasing the ionicradius. Thus,

^9, o
is 133 pm.
(D) The radius of the anion is always larger
than that of its parent aa(rm. An anion is fonned
when a neutral gaseous atom gains one or more ANION
electrons (Fig. 4.12). This increases the number ot
17 ELECTRONS lE
electrons in the anion while its nuclear charge +17 NUCLEAR CHARGE +17
iemains the same as that on the neutral atom. Sinie
the same nuclear charge now attracts greater num-
99 pm SIZE 181 pm

ber of electrons, therefore, the force of attraction

by the nucleus on the electrons of all the shells FIGURE 4,12. Relative sizes oI
Clatom and ct- ion
4l3A

The size oJ an anion is always brger than the corrcsponiling ulom mainly becausv of decreuse in lhe efrective
nucbar charge i.e. leser force of attmction by the nucltttr on lhe el$tror"\.
This is illustratetl in Tahlt 4.15.

IARLE 4.15. Comparative sizes ofatoms and their anions

Alom F CI Br I o s N
Atomic ndii (pn) 72 99 1"t4 133 74 102 75

Con'esponding anion F_ cl- Br- I- 02- s2- N3-

Ionic radij (ptn) 136 181 196 219 142 184 17t

Variation of ionic (anionic) radii lvithin in
group. Lik covaletll rudii, the ionic rudii of anions
also increase as we move down the group pimaily
due to an increase in the number of shells. For
example, the ionicradii ofF-, Cl-, Br- and I-
are 136, 181, L96 and 21.9 pm respectively.
4.172. lsoelectronic ions or species.
. Iis the difroent elnntnt J vhich hwe thp scrae
oJ
nanibt o! ewrons bw ilitsat
mognit& of fla
nucbr &arye w calld lsohlccftolrlc lons.
For example, sulphide ion (S2-), chloride ion
(Cl-) and potassium ion (K+) are isoelectronic
ions because each one of them has 18 electrons but
have different nuclear charges, i.e., +76, +17 ar.d
+ 19 respectively.
Besides ions, a neutral atom may also have
same number of electrons. For example, besides
S2-, Cl- and K+ ions, argon (Ar) has also 18
electrons. Therefore, Ar is also isoelectronic with
S2-, Cl- and K+ ions. In order to cover all thcse
species, the term isolectronic species is used. Thus,
lsoelctronic speci es may be delined as neutral
or ionic species which have tlrc sante number of
electrons but different ttucleat charges .
Thus, nitride ion (N3-), oxide ion (o2-),
fluoride ion (F-), neon (Ne), sodium ion (Na+),
magnesium ion (Mg3+) and aluminium ion (Al3+)
are all isoelectronic species since each one ofthem
ions contains 10 electrons but different nuclear charges
of + 7, + 8, + 9, + 10, +tl, + lZ aad * 13 respec-
tively.
Variation of ionic size among isoelectronic
ions. Within a series of isoelectronic ions, as the
nuclear charge increases, the force of attraction by
the nucleus on the electrons also increases. As a
result, ionic radii decrease.In other wotds,lhe ionic
rudii oI isoelectronic ions deueose with the increase
in the magnitude of the nucleqr chatge . For example,
ions: N3-, O2-, F-,
consider the isoelectronic
Na+, Mg3+ and Al3+. All these ions have 10
electrons but their nuclear charges vary i.e. these
are +7, +8, +9, + 11, + 12 and + 13 as showr in
Thble 4.8. Therefore, their ionicradiiincrease in the
order:
Al3+ < Mg+ <Na+ < F- < 02- < N3-.
This is illustrated in Table 4.16.

TABLE 4.16. Variation of ionic radii in an isoelectronic series

lonv I N'- 02- F_ Na+ Mf* Al3+

Nuckor chatge I *1 +8 +9 +11 +12 +13
lonic roditu (pmt | 171 140 136 95 65 50
 CTASSIFICATION OF ELEMENTS AND PERIODICIry IN PROPERTIES

The ionic size of isoelectrionic species can be easily conrpared on the basis of their atomic Dumber/number
of
electrons, r'.e. 7tre rutio. Sm4ller the val e of Zle, lorger the izz of the
ryecies. For example,
Ion Z zle lonic radlrrs (pm)
N3- 1 l0 o.'t 771
o2- 8 10 0.8 l,!0
F_ 9 l0 0.9 136
Ne 10 l0 l.o 112
Na+ 11 l0 1.1 95
Mg'* t2 10 12 65
Al3+ 13 l0 13 50

,p;.[$ r,t,.,- o I r t ; rs oELl,]c.t.R( )N l (,

SPECIES AND COI\IPARISION OF THEIR RELATI\IE RADII

IiXANIPt,tr 4.14. Nar?re the species that will be (iiil F (iv) M!+
isoelectronic with the {ollowing otonx or ions :
(v) Cl- (vi)AF+
(i) Ne (ii) ct- (vii) Ne.
(iii) Caz+ (iv) Rb+ Arrange them in decreasing order of their size.
(N.C.E.R.T,)
Solution. The number of electroDs in these
Solution. Isoelectronic species are those speciEi aid:
which have same number of electrons.
Atom or ion No. of electrons
- (i) Ne has 10 electrons. Therefore, the species
N3-, o2-, F-, Na+, Mg2+,AI3+ etc. each ofwhich 02- 8+2 = LO

ha-s also 10 electrons, are isoelectroaic with it. Na :11

(ii) Cl-
has 18 electrons. Therefore, the F
species P3- , S2-, Ar, K+ and Ca2+, each one of Me* t2-2:10
which contains 18 electrom are isoelectronic with cl-
it.
17+1:18
(ii)
Ca2+ has 18 electrons. Therefore, the
Al3+ 13-3:10
species P3-, S2-, Ar and K+, each of which also Ne :10
contains 18 electrons, are isoelectronic with it. Thus, O2-, Mg2+,
(iv) Rb+ has 36 electrons. Therefore, the which has 10 electrons)
Now nuclear charse on
species, Br-, Kr or Sl+ each of which also has 36
electrons, are isolectronic with it.
AP+ is + 13 and fre is
species decreases as the nuclear charge increases,
therefore, their size decreases in the order :
02- > Ne > Mg3+ > 4;:+.
0 oz- @) Na
4l40 Pradcep's Ney,t Course Chemistrg 1fifi

l. Which oneoftbe following pairswould havea large (D r, r+, r- (i,) c, N, si, P

size ? Explain.
(iii) 02- , N3- , s2-, F-
1i) K or K+ (ri) Br or Br-
lAns.(i)I+ < I < I- (ii) N < c < l'< si
(iii) 02- or F- (iv) Li+ or Na+
(iii) F- < 02- < N3- < s2-I
(v) P or ds (vi) Na+ or Mg2+ 3. Select froDr each group, the species which has the
(N.C.E.R.T) srnallest radrus stating appropriatg reasoD.
(t) K, (,r) Br-, (ii4 o2-, (iv) Na+, (a) o,o- ,o2- (r) K+ , sr2+ , Ar
t.r'tr
(r) As, (Yi) Na+l I
(c) si, cl. (N.C.E.R.T)

2. Arrange the following in order of increasing radii ? lADs.(4) o (r) Sl+ (c) cU

1. (i) Due to higher effective nuclear charge, K+ has deceas tom

left to right in a period due to higher
lower atomic size than K
nuclear charge, therefore, C has higher atomic
radius than N and Si has higher atomic radius thao
0D Due to lower effcctive nuclear charge, the size P Thus, the ovcrall order of increa.sing atonic radii
ofBr- is higher than that ofBr. is:N<C<P<Si.
(iii) 02- and F- are isoelectronic species. Since (ni) AmoDB Lsoelectronic ions, the size of anions
effective Duclear charge of 02- is lower than that increases as the nuclear charSe decrsases : F- <
of F-, therefore, 02- has higher atomic size than 02- < N3-. SiDcE S belongs to third pcriod while
F-. F; O, N all beloDg to thc semnd period, therefore,
(Ju) Li+ and Na+ both belong to Sroup 1. Bccause ioDic radius ot s2- is bigger than those of F-,
of greater number of shells (2 in case ofNa+ aDd 02- and N3- ions. Thus, the overail order of
1 in case of U+), Na+ has biggcr atomic size than i[creasing ionic radii is : F- < 02- < N3- < s2--
3. (a) AmoDg the different sPcies ofthe same atom,
Li+.
the size increases as the magnitude of negative
(v) As has four shellswhile P has three. Therefore,
atomic size ofAs is hiSher than that ofP. charge increass : Therefore, among O, O- and

(u) Na+ and Mg3+ are isoelectronic cations. 02-, O has the smallest radius.
Therefore, due to lower effective nuclear charge, (b) Although SP+ has I<I gas configuratioD (I.e.,
ionic radius of Na+ is higher than ihat of Mg2+. has four shells), but K+ has Ar gas coofiguration
2. (i) Size of a cation is always smaller while that of an (r'.e., has three shells), nevertheless ionic size of
anion is atwals bigger thaD the ncutral atom, t.e., Sf+ is smaller than that of K+ obviously due to
I+<I<I-. higher nuclear chargewhich outweiShs the effect of
an additional shell.
(O C and N lie in 2od period while Si and P lie belo$'
them in the 3rd priod. Since elements in the 3th
(c) Si, P and Cl all belong to 3rd period. Since
priod haw higher atomic size than tbce in the 2nd
atomic size decreases as the nuclear charge in-
creass. Therefore, Cl with the hiSbest nuclear
period, thercfore, aiomic radii of Si and P are higher
charge has the smallest radius.
than thce of C and N respecrivEly. Since atomic radii

The elcctmns present in the oulermost shEU of dn

4.18. Valency r:iii;:j:iiiri:ii1i;riili:ii::ili:lili:i::jii:ii!:iliiii;i:li:t'irr:ir:,:l:ili:iiillriili;::i:i:i:r utom dr6 ttlleil valence electrons and rlu number
of thesu electtons determine lhe valertrce or lhe
It has been observed that the chemical valency oJ the atom. It is becuuse of this reuton thal
properties of the elements depend upon the num- lhe ourermost shEll is ako calkd lhe valelAce shell
ber of electrons present in the outermost shell of ol the a,om anil the orbitals present in the vaknce
the atom. shcll the cullsd valerce orbitals.
CLASSIFICATION OF ELEMENTS AND PERIOOICIry IN PROPEHTIES 4141

Summary of the Tlends in the Periodic Properties of Elements in the periodic Thbl.

Alomic radiid6creas6

lonization enthalpy increasss

)
H

.q Non l\,4etals

I
.9
E -g

Transition metals z

lnner kansition elements

In case of representative elements, lhe valency Periodicity ofYalence

of an atom is generally equal to either the number
of valence electrons (s- and p-block elements) or
equal to eight mirus the number of valence
electron-s. In contrast, transition and inner transi-
tion elements, exhibit variebte vdencedtrdto iniol-
vement of not only valence elecirbiiSu -'64
/-electrons as well. However, their most com-Eon
valence are 2 and 3.
(c) Variatlon in a pcriod. As we move aqoss
a period from left to right, the number of valence
electrons increases from 1 to 8. But the valence of
elements, ha[t H or O 6rst increases from 1to 4and
then decreases to zero. This is illustrated in Table
4.17 .

TABI,E 4.17. Periodic trends in valence of elements slown by

the formulae oftheir hydrides and oxides.

Groups - 1213 14 15 16 17
J Periods
Iiormulae oI ) LiH cHr NH: Il2o HF
hydrides 3 J\AH siHl PHr HzS HCr
4 Ktl ftHl aHr H2Se HBr
5 RbH SnH. SbH3 Hzft HI
Formulae 2 LizO BeO BzO: COz
of oxides 3 NEo MgO AzO: SiOz
4 K2o CaO G%Ot ceoz
5 Rb2O SrO Itlzo3 SnO2
6 CEO Bao Pb02

(D) Variation in a group. When we move
down the group, the number of valency electrons
remains the same, therefore, all the elements in a
goup exhibit the same valency. For example, all the
elements of group 1 (alkali metals) have valency
one while all the elements ofgroup2 (alkaline earth
metals) exhibit a valetcy of two.
Noble gases present in group 18 are
zerovalent, i.e,, their valency is zero since these ele-
ments are chemically inert.
4142

F B-@-;E- LE-M,6,0,N r rt. t..ri c t,;

I,l\Al\lPLL l.16. Predict tlw fomrulae of the
stqble binsry compounds that wouldbe lormedby the
following pairs of elentenfi.
(a) silicon and orygen (b) ahtminium and
bromine (c) calcium and iotlitrc (d)element l l4and
fluoine (e) element 120 and oryge,t. (N.CJ.R.T,)
Solution. (a) Silicon belongs to group 14. It
has four valence electrons and hence its valence
oxygen belongs to group 16. It has six electrons in
the valence shell and hence its valence = 8-6 =2.
Therefore, the formula of silicon oxide = SiOz.
(b) Aluminium belongs to group 13. lt has
three electrons in the valence shell and hence its
valence:3.
Brominc belongs to group 17. It
electrons in the valence shell and hence its valence
= 8-7: 1.
Therefore, formula of aluminium
:AlBr:.
(c) Calcium belongs to group 2. lt has two
electrons in the valence shell and hence its valence
: 2. Iodine belongs to group 17. lt has seven
valence electrons and its valence = 8-7 = l.
Therefore, formula of calcium iodide = CaIz.
(d) In the 7th period, the 4th transition series
ends at element with Z : lLZ, aherefore, filling of
7p-subshell will begin with element Z
Hence, element wrth Z = 114 witl have two
= 113.
electrons in 7p-orbitals and two electrons in 7s-or-
bital. In other words, the element z: 114 will lie
in group 14 and hence its valence
= 4.
:4 Fluorine belongs to group 17 with seven
valence electrons and hence its valeqce
=8-7=1.
Tterefore, formula of compound formed by
element 114 and fluorine is MFn where M repre-
sents the element.
has seven (e) The 7th period will end at element with Z
= 118. Therefore,filling of 8th shell i.e. 8 s-orbital
will begin with elemell.Z = lL9 and consequently
bromide element with Z = 120 willbelong to group 2 and its
valence will be = 2.
Oxygen belongs to goup 16 with six valence
electronsandbenceitsvalence : 8 - 6 : 2.
Therefore, formula of compound formed by
element Z :
120 and orygen rvill be MO where M
represents the element.

1. Predict the formulae of the slable binary com- 2. Prcdict the formulae of the stable binary c-om-
pounds thatwould be formed lry the followinS pairs pounds formed by the following pairs ofelements :

of olements : (4) clcmeot with Z= 116 and hydrogen

(a) silicon and bromioe (N.C.E.R.Tl
(D) clemeDt with Z = 113 and fluorioe
(6) aluminium and sulpbur (N.C.E.R.T)
(c) Uup aDd sulphur (d)UueandUus.
(c) calcium aDd orygcn G1) aluminiuDr and carbon.

r. (a) SiBro (b) AlrS, (c) CaO (d) Alaq

2. (r) H2M (b) MF3 (c) MrS.whcreM (Z = 115) (d) MX where M (Z = 119)and X(Z = 117) are the elements.

1 Afulition offnt electron to a ne trdl alont ir at energic process whle tlut ofrccond elecfo, it rzz endorgic Procss.

). O,vnhun (Or) har the highe$ oidllion state (+ 8) ot valency (8).

t Among solid-t, osmiwn has irc higlAst den\ity of 22'6while anong Equids, mercury hat the highest den\ily of 13 6
i Among melalr, tuhgston (W) h.'it the highett melting point (j68j K) while anong non-melal:, cqbon han lhe
highe:i melting point (1000 K) Of all the ele,nenlt, heliun, however, ha.t the lowest boihngpoin @ 2K).
, ,l , i, ,' :, ,i:: :ri,r,:
CLASSIFICATION OF ELETiIENTS AND PEBIODICIry IN PROPERTIES 4143

Q LWor d yorr rgs,rd Zi <Z = $\Cd (Z = 4t)andIIC(z =t0) ss-s. ord-b:ock elements ? Cive reosors for
yo t answer.
Atrs. The la.st electron in Zr, Cd and Hg enleE the 4.r, 5r and tu-orbitals respectively. Tlrcreforc,on the batit of type
of orbital being fUed" Ese lhree elernenh sltould be rcgarded. as s-block elements. But thc properties of these
elemelts resemble more the d-block rather than J-block elemeoLs as listed below:
(i) Zn, Cd and Hg like other d-block elerDents form complexes but,r-block elcments usually do nor.
(r'i) Zn, Cd and HB like other d-block clemeots form maDy covalent compouDds whereas r-block elements
form ooly ionic compounds.
(iii) Like other d-block elements, the [i6t ionizalion eDergies of Zn, Crl aDd Hg are much higher than those
ofthes-block elements of the same period.
(iv) Like other d-block eleme[Ls, the atomic radii of Zn, Cd and Hg are much lower lhan those of ther-block
ele ments of the same period.
(v) Like otber d-block elements, the electrode potentials ofZn, Cd and Hg are much lEss negative rhan those
ofJ-block eleme[ts of the same period.
Fiom the above discu ssion, it is cleor that the properties of 'Zn, A and Hg resemble more the d-block elements
rather than the r-block elements-
Fhrther, to make the periodic classincation of clemenLs more rational, it is better to study tltem along with the
d-block elements.
Q 2How many elemenb caD he accoEDodated in ihe pEsent set up ofthe lotrg foru ofthe priodic talrle? BplalIL
An6. In the present set up of the long form of the periodic table, we have seleD periods (ie., principal quantum
Dumber, n = 7) and four blocks (r, p, d- andf-block elemeDts). Thereforc, the maximum number ofelements
which can be accommodated in tbe prescDt set up of the long form of the peri(dic tablc in ac.cordaDce with
Aufbau principlc is I s2 2 ? 2 p6 3 t2 3 p6 4 s2 j dro 4 p6 5 ? + d1o s p6 6 s2 4 f1 s dro 6 p6
'l sz 5 tta 6 dro 7 p6
=
118.
Q,3. Crn an element with atomic nurrber 12,6, ifdiscovered, ie accommodated in ttre pre6ent set up ofthe lorg
fortE of the pertodlc t{bel ?
Atrs. No. The maimum numbr of elemenb which cao be accommodated in the present set up of the long form
of the Periodic table is 118. Thereafter, filling of 8r{rbiEl shall begiD which will accommodaie ooly two
electroDs. After &-orbitals, the filling of sg-orbitals will begin. SiDce we do Dot havc any prcvisio[ for g-block
elements in the present set up of the long form ofthe periodic table, thercfore, ao element with 3tomic oumber
126, if disco\rered, cannot be accommodated in the prEsent ser up of the IoDg form of the periodic table.
Q. '1. What would be lhe rtomic nuEber ofthe rext (0 alk li lrelal (ii) alkaltne earth metsl (ii, hr.lo8en and (iy)
irert g8s, if dlscoYcrcd itr future ?
Ars. (i) The ocxt alkali metal, if discovered will, have to be placed io the eighth period and heoce its ouer electrcDic
coofi Suration will be &l - Therefore, its aromic numbr will be (1 t8 + 1) = I 19.

(r'i) Similarly, the next alkaline earth metal, if discovered, will havo &2 as its outer electroDic configuration and
hence its atomic number will be (118 + 2) = lm
(ai) The next haloSD, if discryered, willhave 7s2 7p5 as its outer eleatroDic configuration. Since the lilling of
7P-orbitals will begil after 6d- orbitals and up to 6d-orbitals, i[ ac{ordaDc with Aulbau principle, we can
actommodate oDly 1 12 elemeDts, t he refore, the atomic number of the next halogcD, if discovered, will be ( 1 12
+ 5) = 117.
caD easily sxplaiD, that the nxt inerr gas, if discovered, will have # 7p6 as its outer
(iv) Itr a similar way, we
electronic confisuratioD and its atomic number will be (l l2 + 6) = f 18.
Q. 5. What rrE super he{vy eleDents ?
Ars Elements with Z > 100 whici have high densities are callcd super hearT elements.
Q. 6. W'hat would be IUPAC rlame6 sDd syEbols lor elemelts vith otoDic truDber8 12a l?7r,.;l,ql4g andli0?
Ans. Ftom the Dble 4.5, the roots lot 2, 7 , 5 , 9 and 0 are bi, sepl pent, eru and ,n? respectivcty. Therefore, their
naDcs and symbols are :
4144 Pradeep's
z Nome Syurbol
Urbibium trbb
127 Unbiseptium Ubs
735 Untripentium UtP
149 Unquadennium uqc
150 Unpetnilium upD
Q 7. Arrange the follo*irg elements
(i) in the increaslng order of metallic chrracter : Si, Be, Mg' Na, P (NC.E.R.T. )
(r'i) in thc incrasing order oftron-metallic charncter : B, C, Si' N, [, (N.C.E-R.T)
Ahs. (i) ArrangiDg the elements into differeDt grouF and periods in order oftheir increasing atomic nuDlbers, we have,
1 213 14 15
Be
Na Mg Si P

We know that the mstallic character increases dot n a Sroup and decrerses along a period as we mo!r'e fron'l
left to rigbt. Therefore, Na is the most metallic element, followed by Mg and Si, while P is the least metallic
element. Among Be and Mg, Mg is more metallic thaD Be. Tberefore, the overall increasing order oimetallic
aharacter is P < Si < Be < Mg < Na.
(ii) Aranglng the elements into different groups and periods in order of their increasing a tomic numbers, we have,
13 14 15 16 1',7

BCN-F
si-
Sitrc the metallic charactcr iDcreases do\rn the group aDd noD-metallic character increases along a period
from left to right, therefore, Si h the mct metallic or the least non-mctallic element. The ovcrall i[creasing
order of non-metsllic character is: Si <B<C<N<E
e. E. The elGmcnt 119 hss not been discovered. Wh6t could be the IUPAC nome ard symbol for tlris elemelt ?
On the basis of ihe periodic trble, predict the clectronic configurstion of t}is eleme[t and also thc formula
of its rnost st^hle chloride and oxidc. (N.C.8.R.7:)
Ans. (i) The roots fot l andg arcun a ) erw respctively. Therefore, the name for the eleolent with Z = 119 is un
+ un + enn + ium = unuuennlurn and its symbol is Uue.
(ii) The mardmum number of clements wbich can be aclommodated iD the present set up ofthe long form of
itri perioAic taUte = 118 (For dehils refer to Q. 2 on page 4/43). Since this last elemeDt would be an inert 8as,
theiefore, the element with Z = 119 will be an alkalimetal and hence its outer electronic c.onfiguration will be
&l or its completc electronic configurationwrltbe Ls? 2t2 2p6 k2 3p6 Mto 4t2 4p6 M1o 4 f4
st2 sp6 sdto s f1 6"2 6rc 6aro *2lf 8,r.
(iri) Sinc the elemen twtrh Z = 119 witl be an alkali metal, therefore, fo.mula of its chloride will be MCI and
that of its sEble odde will be M2O where M is the alkali metal

Q.9. Why has the zcro group been placed at th extreme rlght ofthe perlodtc aable ?
Ans. Thisin ac{ordance with their electronic configurations because each Period starts with the fillig of i-subshell
is
and is completo after the filling ofp-subshell of the saDrc principal shell.
e. 10, Wblch ofthe elemcnts Na, Mg, St and P woulal hsve the grcatest dilference betwcel the lirst ond
the seco[d
- ionlzatiou enthalplc+ Brielly explaln your anatier' <N'C'E'R T-)
Ans. ADong Na, Mg, Si aDd P, Na is ao alkali metal. It has only oDe electroo in the valence sbell, therefore, its IEt
is very low. However, after removal of one electron, it acquircs neon 8as configuratioD, l e,
Na+ 1ts2 *2lpt. Therefore, ils Iq is expected to be very high. consequenrly, the difference in first and
seco[d ionization enthalpies would be Sreatest is ca,se ofNa
Howcver, it may be noted here that in case of Mg, si and P, although their IEI will be much bigher than that
ofNa but their IE will be much lower tban that ofNa. As a result, the difference in their respective IE1 alld
Iq would be much lower than that ofNa.
 CLASSIFICATION OF ELEMENTS AND PERIODICITY IN PHOPEBTIES
4145
Q ll Tlle lirst iohization enthnlPy ofmagnesirm is higher than that ofsodirlm. or
the other haDd, the sccotrd
iorizntion enthalpy ofsodium is much higher th; that ofmagnesium. Explain
Ans The first electroD in both the cises tlas to be remor'ed ftom the 2f
iN:C.;-i.f)
orbital but nuclear charge ofNa is less than
tioD of Na + is lp zrz 2p6 , Le ., that of Doble
isvery difficult. ln case of Mg, after the loss
tbe second electror. is to be remc,vcd from

Q. 12. Arrnngc the following ions in the order o[increasilg siz. ?

Be2+ , cl- , s2-. Na+ , Mg2+ , Br-.
(N.C.E.R.T.)
Ans. Affanging thc given ioDs iDto differenl
Sroups and periods in order of iocrcasing atomic Dumbers of their
rcsPcctivc clcmeDts. we havc.
Group No 1 2 16 t1
2nd period Bez+
3rd period Na+ Mg2* 52- Ct-
4th period
Br-
Clonsidcr rhe lollowirg poinrs :

(r) rhe sizcs of a,ions arc usuafly biggcr than those of the cations, !'. a, the sizes of sz -, cr- and Br - ions are
bigger rhaD those ol Bcz+, Mg2+ anri Na+ ions.
(ii) Witlrxr a group, thc iooic sjze increases from top to bollom
,tbercforc,ionic $ize of Mg!+ ion ir bigger tlon
tltot of Be2 r . Likc$,i\e, ioni(. size of Br- i.r bilger than tltat of
Cl- ion.
(iii) AnoDg isocrectronic roos, higher
the +ve charge, smaller rs rhe size. Thus, rbarc rize ofNa+
b biger thon
lm of M{+ Furthcr, anroDg isoereclronic ioDs, higher the
-ve chargc, bigger is the size. Thus, rbntc rize o/
52- 1* hi.q4r lmn tlnt ol Cl' ion.
Furthcr' thc incrcasc ln ionic sizc (luc to addition ol onc nrore shell
is usually greater thaD iDcreasing the
negativc charge by onc uDit. lhcretbre, //r c ionic .rize of Br- i e4tectett
to be higer thon 52_ ion.
combiling alr the above vie\rs, the ionic size of aI the risted ions increascs in the order :
Be2+ < u/+ < Nat < cl- < s2- < Rr- _

Q I-1. Among the elemenls B, Al, C anrl Si

(a) Which hrs the higlrest lirst iorlizarion enthalpy
?
(r) Which has the most negrtive electron gaiD enth{lpy
?
(c) WIlich has the larEest atomic rndirs ?
(d) Which has the mosr metallic chnracter ?
Ans' ArraDgiDg the given aloms iI diffcrent periods aDd groups @.C.E.R.l..)
in order of their increasing atomic numbrs, we

(;roup 13 14
2nd period B C
3rd period At Si
(o) since IEf iDcrcases arong a pedod but decreascs down grou
a p,Thereforc c htl, the highe
entlnlsty.
frfrt ionization
(r) Since electron gain eDrhalpres be(.omc more negarrye ak)ng a priod and less negativc down a group,
thctefore, C ho.\ thc mott negative electron gain entloipy.
(c) siDceatomic radiidecrease arong a pen*r bur incrcase down a gro rp,
therctorc,Ar rw he raryesl alomic rudhlt.
(d) since meollic characrer dccrc.rses arong a pcflod. but
iDcreases down a gfoup, th ercforc,Ar ho! rhe moNt
netollic charocter.

e, ll, Consider the elerDel|ts N. Ii O, S rrnrl armnge thetn in ord.r

of
(a) increasing first ittrization enthfllpy
 Neu,t
4146

(r) tDcrqshs ueZstive clcthon gain enthalPy (N C'E'R'I:')

(c) increasiag non'mctallic cherrctei
i[to different groups aDd priods io order of their increasingatomic numbers'
Atrs. arraoging altine Sivc[ elcments
we have,
OrouP 15 16

2nd poriod N O
3rd Period P s
(a) Since IEl decreases down a grouP, therefore' I
since N has more stable
difficult rc knock out an
has exactly half-filled ele
enthalPy of these clemeDts follo$'s the order :
Thus, the werall increasing order of first iooization
s<P<O<,.V

similarly,Nhase)(acttyhalf-filledetectronicconfigurationinthe?-subshellbutohashiEhernuclearchar8e'
to such an extenl' thai electJon gain enthalpy of N is
But thc addition of an efectron to'X causas repisions
alualty positive white that of o as sxPccted is Dega ivc'
enthalry of these eloments follou/s the order :
Combidug to abwe rsulls tie incf,easiDg order of ne8ative Sain
N<P<O<S.
alons a oeriod' therefore' O is the mGst
(c) Since tron-metallic character dertases down a SrouP but increases
f Thc actuaf oider oi increasing non-metallic
non-metaltic element wnire isiiJ ilsi,io-n-rrfitti"'.t"rn"nt.
ciaractet is: P<S<N<O
Q. t 5. Which of the following speciea will hav' thc
lrrB'st strd the smollest slze ?
At!+ N'C'E .-T)
Lr8, [r82+, Al,
period' atomic radii decrease due to i[cre'sed nuclear charge'
ADs. (i) Mr and Al beloog to the third pcriod' Acr6s a
'-- oro-ic ;ize ol Al is snouer thu thot ol t
\i.iZtor",
M{+ smaler than Mg and AP+ it
Parent atoms' Therefo rc'
i5
(ii) Further, cations are smaller than thcir
waller thstAl
liritMf,+andAl3+areisoelectroDicions.AmongisoelectroDicions,higherthe+vecharSe,smallerthesize,
\.r"ior",^o-n,riur of Al3+ it snoltzt than that of M{+'
smallast sia'
From the abc've discussion,it follo\rys that Mg has the lorycs whileAP+ hzc hc
1.,. fularge the lollorviDg loDs ir order ofdecrissing iontc radli I Ll2+, He+, Bel+.
'or*
Q.
decreass as lhe P6itilr
;;;, i,'i""d Bei+ are all isocleclronic ions. Among isoelectronicions' ionic radius
charge increases. Th"r"ro'", tri'JiiJ*oiiJ"o*tt i"o tn" oto"t: Het > Li2+ > Be3+
ilet Wazll radll: Cl' H' q N'
Q. 17. Arra-nsc the folloninS ln oritGr of dec recNiiltgvat
AD6.

Thuc, the ovemll dzneaskg ordo is :

cl>N>o>H.
 CLASSIFICATION OF ELEMENTS AND PEBIODICIry
IN PBOPEHTIES
4147

V ery .5 1t',.,q- 11" A 4 s we 1 Q u e?t;ipn?,, cARB'r N G r :MABK

Q. r. What are horizontat .-"" " ,
Ans. Horizontal rows are called "rra "".ti""i "oil;;;;;;;;#;"';ii;Lr*
peflods while vertical columns are call"O groupa.
'
Q. 2. What is the bssis ofclsssilicrtion ofelements in ahe
lolg form ofti" 1.foai" ,.lrt. f
Ans. Ph),sical and chemical properties of the elemeots
are a periodic n,n"tio, oittr"ir utolDic
numbers.
Q. 3. Nsme the groups of elemerts classified as J, p and
., blocks.
Als. ,-block = 1, 2,p-btock
= 13 to 18. d-btock = 3 ro 12.
Q. 4. What are the fltomic nurnbers ofelemeDts which constitute.lf.block
AIls, LaDthanoids = 58 to 71, Actinoids 90 ro 0srth{troids aDd actiDoids) ?
= 103.
Q. s. Compflre the size of (a) Na atom with Na+ ion (l) Cl
atom with Cl_ ioD.
Ans. (a) Na+ < Na (6) Ct- > cl
6. AI atom loses electrons successiyely to
Q. form Al + ,A12+ and AP+ ions lyh ich step
encrgy ? will havehigh.stionization
Ans. Al2+- p;,3+ +e-
Q. 7. Vt hy ioliz5tior
eDthalpy of nitrogen is greater tban that
oforygen ?
Nttrogen has exacrly half_fi lledZ_orbitals.
Q. E.
ive ?
Ans,
accept an addlional elcctron. Conseouenrh.
lo the much higher enersy p_orbitals of rhc
are posilive.
Q. e.
Ans. MeDdereev used rhe aron,ic masses orrhe^crem",,,
rohishw, I he propen ies of element5 are a periodic ,;'iUff;:ff:,il:ji:ffi#:,f,xl*re. Accordinr
funoion oi n.,, *.,Sf,o.
Q. 10. State the modern periodie law. ",ori"
Ans. that phrsical and chemicat properries
ff."f :H.fl"ffr::rsrares of rhe elemenh are a periodic tunction of
Q. 11. what wourtr rre the IUpAc Dame atrd syrnbor for the
eremelt with atohic rumber r20 ?
Ans. Unbinilium, Ubn
Q' 12 Which one amonE the fororving elemchls_has the
rowesr
- first ionisation entharpy and whicrr one hns the
highest lirst ionisntion enthalpy ? Li, K, Ca,
S and Kr.
K has the lowest lonlsntion enthalpy and I(r has
the highest ionisation enthalpy,
Q. lJ.
H[1"#t;,:it":",ii[il:;J* n'"' in separate rows at the bottom oi'tr,. p""ioai"
,nbre. Exprain rhe
Ans. These have been praced seDararelv at
the bottom of the periodic table for conveniencc.
rhc body ot lhe periodrc rabte. rheieriodrc rf they are placed in
,uor. *iri t.oir.Iilr.n#iy iln!"unu
Q. 14. Givc four exsmples ofspecies rvhich are isoelectronic "rro.^orr..
with Ca2+.
Ans. Ar, Kr, Cl-, 52- or p3- are isoelectronic
with Ca2+
Q. 1s.
:"T":f:H-"1;l;.'ir1'ilil'".;J,Yrlffi,l:tomi.veisht = 3e'e) has heen righrrv praced beforc potassium
Ans. This rs beouse argoo (Z
= 1g) has lower atomic number than potassiunr (Z = l9).
Q. 16. Which has a larger.adius ? (i) MgorCa (ii)SorCI-
Ans. (i) Ca (i,) S.
Q. 17. In terms ofelectronic configuration, what
the elements ofa giver period snd
ADs. o group hqve in commor ?
r.;
'i"J;J:ffiil:J:f.r&n# H:liiii;:'li*:i"q,ur""d
Q. It. Whict two elements ofthe followitrg beloog
";.;;;;,"n-"1,oup,,," n,,oerore,ec,rcns in

ro the same perlod ? AI, Sl, Ba

Aos. Al il[(r Si rnd O.
+

4l4a
gain enthalpy ? Fluorine' nitrogen' neon'
Q. 19.lvhich ofthe following elemenls has most positive electron
Ans. Bott niroser and neon havo Positive:r.'clri {iln:1t}.:lli::}:t:'l}l3L'l,li'l.l}[lfi:',1'ffif'J,'":i'811:
ffJf"lffi:H"'*H,!?,1;"';$:,}'ffi;""#;i"8ffi;6ffi;,h;o*,"r",,,tuur"d,",yharf-mrederectronic
configuration o[ l,litrogeo'
B and C, choose the element with higlrest
tirst ioDization enthalpy'
Q. ,0. U.oniu-on*"t Be,
charge and smaller size has the highest lE l amongst tne given elen-)enls
Ans. carbon because of its higher nuclear

?
wlrich are inner trnnsition elemenLs
Q. 21. Which rmorlg the following ere transition anil
58, Blq Er' fm' Fe' Pb' Cr, Co' Ar' Zr'
Ce

Ans, TiaDsition elen'leDts : Sg, Fe, Cr,

Zr
Inoer transition elenents : Bk, Er, Fm'
Ce
an'l lowest first ionization enlhalpies'
Q. 22. Name the elements
in the periolic table Yhich has the highest
Ans. Highest : Ilelium and lowest : Francium
more easily as compared
onrle'
23. ExPloin why chlorine can be convertcd ilto chloride ion
-L.".
Q.
than that of F
Etectron gain enthalPy of Cl is rnore negative
coitains 45 nerrtrons {rnd J6 Electrons' wh"t !rl,l'
monoatomic anior of unit charge
- 24. A.l"ment
e.
ond in which group of the Periodic tahlc
does it lie ?
anioll = 45
Ans. No. of neutrons of the nlonoatomic
No. oI electrons of the nolloaton]ic anlon =
36

. No. of electroos of the monoatomic atom = 36 - 1 = 35

to group 17'rc ;
' Atomic number or tne atonr il = 35) Therefbre' the atomis bromine aud it beloogs
haloBerl familY.
No. of Protons = No of eleotroDs = 35
. . Aiomic mass = No ol oeutrons
+ No of electrons = 45 + 35 = 80
(s, P, d or, does the element with
atomic nrmber 50 belong ?
Q. 25. Ib which block
3s2 3Pt 37to 4',2 4p6 4dto 5t2 5f
Plenceit a p-block elemert
Ans. E.C. o1 7=50 is 1? Bz 2p6

stion
I
Sec.4.1. 1. What was the Deed for classlflcation of elements
to 4.6.
justificailon'
2. Define Modern Periodia law Give its theoretical ? Explain with two exaolples
3. What is the cause of periodicity in properties of the elements
following elements
4. Predict the deDsity of Cs from the densrty of the
( 0 86 9cm3 Ca 1.548 g/cm3
.532 glcm3
Sc 2 gg1 llcrll3 Rb 1

sr 2 68 8,/cm3 Y l.zt glun3

3.51 9/cm3
Cs?Ba
La 6 16 g/cm3

IAns. Between I 532 and 2

6E g/cm3 nrotrnd I E x 2.0 g/cm3l
lorm of rhe table
Sec,4.7. 5. Describe the nlflin tcatures ot the long Periodlc
to 4.13. the periodic table ?
the maio teatures of the long form of
6. State modem Periodic lBw' What are in the lo[g form of the
7. ExPlain briefly'GrouPs' and
'Periods"Tiansition' and 'Normal' clements

thirdPriods contains 8 elements

E, conf,guradons' justiry that thc.scond-alld elemnents'
coot"tn i'd and the 6th Period contains 32
"r"li'"niieach
 CLASSIFICATION OF ELEMENTS AND PERIODICIry
IN PROPERTIES
4149
9. Account for the fact that 4th period has eigbteen
and not eight elements.
I0. Name the four blocks inro which the etemeDts ofthe periodic
named so ? Lisr rhc groups of periodic rabte Oelongng
to eactr Oi ;i..
-*" classified.
table have- beerl - Why are thsy
ll. doyou undcrstand by ,Representative
elcments, ? Name
_whaf
represenlative elemeDts.
the groups wh*o elemcnts arg called
12. what are transition eleme[ts ? why are they so clled ? Name the differeDt transitiod
serics.
t' called inner transi oD elements ? Name the different irner transition
#i';Hi"f"Tfl'ate seriqi. why
14. Describe the main ciaracteristics of ,, p d and/-block elemenls.
15' Namedifferent brocf,s oferements in rhe poriodic table. Give the generar @.C.E.R.T)
erectroDic coDfiguration of
16' Though coppcr, s ver a,,d gold atoms have completety fired sets
transition mekls. Wby ?
of d-orbitars yct tbey ae caled
17. The values for rhree of lhe quanrum numbers for the
what families ofthe periodic Lbh are these .t"m"nt"
tast electron
"' A
" -" iD '' and , ,*ll.'*;#:ll
pr"""rt:i "r"
A I +l +tD
83_2_lD
In. lAlrs. A= p.Btockel ntsl
19,29, and 36respect oDtc
c tabre each erement
Src. -l. r,l. 19. it vary along a period
20. sive iooization enthalpies ? Explain whysecond ionization

21. Define ionization enrhatpy. whar are ,o ,r,ll?inar

o ,0" principte of its measuremenr ?
22. Discuss briefly the various factors on whrch ionizatioo
enthatpy Oepends.
,, ionizarion enrhatpy increase as we go from teft to
rigbr acros.s a given period of lhe
#r"::?$: irsr
24. Explain why ioniarion e
25. The first live successive i
own a group of rhe periodic tabte ? 'il.t:;X?,
ofboronatonrare aOO, 2427, 3658, 25OU antJ32g24
kI mol-l. Explain these res.
26. Explain rhc Iollowing :
(i) IonrzatioD eDthalpy of Mg
more than rhat of Na and Al.
is
(ii) Ionizarion enthalpy ofDrtrogen
is more than that ofoxygen.
27. Why is rhe ionizahoo enrhalpy of Be ntorc than that of B ?
Lphin.
2t' If we coDsider ionizarion entharpies of erements in lhe second period
from Li ro Ne, rhev ordinarik
increase but Be and N have rrigher ionizat;;
endi;;;;;.'
them. Why is lt so ?
sre J.15. 29, Explain the term electron gain enthalpy ? How does it lEry
"il o;;$;;;J;il;iih":;,#"iJ
along a group and across a period.
30, Explain the terms jonization enthalpy and electron gain
e;thatpy ?
ean by successive electron
" Sain eoth;lpies? why is rhe second erectron eDtharpy ofan
"'r'i,itJoo..ffi:f
32. Flalogens have very high ncgative electroD gain
enrhalpies. ExplaiD.
33. Electron gain enthalpy oflluorinj
is less negative thanthat oichlorine.
Explain.
34, ble dases in positive. Explain.
35. , srate which atom/ion has higher ionization
entbalpy and more ncgative

(a) r, r- (D)Br,Br- (c)Li,Li+ (d)Br,r.

 Pradeep'st, rt,,i, it fiti-ii1-1a1lTfill
qlso

: Increasing order of ionic size

(N3- , N"* , F- ' 02- ' Mg'*)
36. Arrange the following as stated
lAns. Mg2t < N'r < F- <-o2- < N3-.lAll':T3*::t1t:::l:i
is the-size)]
the nuclear charg", smaller
tlor"" gr"at"r
properties of Jements ? Name any three such properttes'
Scc.4.l6. 37. What do you understand by periodic
to 4.lll.
3E. Howdoatomicsizesvaryinagroupanclinaperiod?Givereasonsforthevariations'
39. whatismeantbyatomicandionicradii?ExplaingivingreasonswhythesizeofCl_ionisgreater
thanthatofClatonrwhereassizeofNa+ionissmallerthanthatofNaaton:?
of its parent atom' Give reasons'
40. The size of an anion is larger than that
41. The size of a cation is smaller than
that of its parent atom' Give reasons'
electronic conftguratiot't'
than 02- ion although both have the sanre
42. Mg2+ ion is smaller
examples to illustrate your answer'
43. What are isoelectronic species ? Give
is either equal to the number of thevalence electrons or eight
44. Thevalence of representative elements
this rule ?
minus ttris number. What is the basis of
NIlSCltl.l. {]\'il'l()t js Qtllisl'I( )NS

el Periocl, Li to Ne' Pick

45. Anrong the
(i) with the hi nergy (ii) with the hi
(lii) with the (iv) that is the
I (ir) F and (u) Lil
(v) that is the most reactive nretal'
pick out the element
46. a*org the elements of the third period, Na to Ar'
(i) with the highest first ionization enthalPy
(,,) with the largest atomic radius
(rir) that is the most reactive non-metal
(N.C.E.R.T) tAns' (') Ar ('4 Ar (iii) cl (ir') Nal
(lv) that is the most reactive metal'
properties of the elements vary approxinrately
47. Fot the main group of the periodic table' the metallic
,

with their position as shown in the table'

I 2 1314 15 16 17 18
He
H
A B
C D
mo B' C or D ?
(r) Will the
at A' B' C or D ? tAns' (i) C ('i) Bl
(ii) Will the m
4E.A,B,Caretbreotherthanhelium.withthisinfornrationcomplete
the following table'
Also exPtain the following:
N-o.
or in the valeoce shell Group to which the elenlent belongs
Elenent AtomicNum5er "looons
A z-7
B Z
C Z+7
that of element C
(i) Electron affinity of element A is more than
less than that of element A
il4 tonization energy of element C is [Ans.A=[B=NeandC=Nn]
(iii) Electron affinity of B is zero'
 CLASSIFICATION OF ELEMENTS AND PERIOOICITY
IN PBOPERTIES
4151
t'' erenreots havins atomi@
Ii#:'*'.fli:T#: :i"1Til1,'*
[Ans E.C ofthe elemenawiti Z = ta is tJ Zl Zp6 32d. tt trelonss to
fl
group lt aod 3rd period. Its valency will he z!ro.
E C. of ahe element wi ah Z 26 is Lsz * g2 3re gt
tth group ard 4th period. lts most 4f
= 4r2. It helongs to
common
"nt"rr"l".
o"" Z urt- li
'Lqag r-RueE-tiens_.
Scc. 4.1. ,. of tbe tong form of the priodic rabte. In what
k) 4.13. il:s#ff:ff:rfearures respecr.ei" it .up".io. ,o

Src.l.lJ
1,, J.l ti

4' Define erectron gain entharpy. Describe the

factors which determiDe the magnitude
erecrron gain entharpy whatare the generar and sign of
trends ofvariation oi"il"i.l, guro in periodic
"ntrrurpies
5. Discuss thc trends in atomic sizes ofelements
iD the periodic table.
6. Explain what uodershDd bv c.y,/alent rcdius, van der Vrhal,s
radius, ionicradtus and atomic radius.
Holv do thsy 'ou
vary in a perioO anO in a group?
 ,4*
p-B,tTrt,ONA I- IUSE F UTL'IN:FO, lMAllilON

d.

l6.
(AB) io whjchlhe atoms A and B are linked by a single covalent
For a heteronuclear diatomic molecule
is given by the following relatiom'
t-o,ii" ut.il""sth aA-B)
(i)When thc aro,,sA o./t'l B lrcve nearly the sune eleclronegotivit!'
dA-B = tA+ rg
ofthe atoms A and B respectively'
whore rA and rB are the cwalent radii
elecn'onegaivitiet'
(ii\Whcn ,he atons A ond B have different
d^-s = ra + rB - 0'09 (rA -rB)
of the atoms A and B respectively'
whererA andrB are thc electronegativities
ond Stevenson'
This relation was given by Sboeiisker

1ls2
CLASSIFICATION OF ELEMENTS AND PERIODICIry
IN PROPERTIES
4ls3

c&s.r. -P.ll.T.
Q. ?, The tirst iotrization eDergy of carbou atom ls
Q. l. ArrEtrge tbe elcEeDte ofsroDd
lroriod ltr older
greater than that of boroh whcrss the reycrse
of ircrrasing scoril ionizatiou enthalpies. is true for the second iorization energy ExplalD.
Ans. The electronic configuration ofthe ions obt2iDed (u.T 1989)
after removal offirst electron ftom the elements

Tbe follou,ing cooclusioDs caD be drawn from the

above configuratioos :
(r) Li+ basroble,gas, viz, He gas coDfgurarion, s_more pnetrating and hence is more stroDgly
thetetorc, IE2 of Li is tlu highest in thi secon; attracted by the nuc.leus than a p-orbital, the;e:
petud fore, IE2 of B is higher than tbat of C.

(ii) Shoc iD B+, thc ele(troD Q.3. ArraDSg the foltowilg ious h order of ttreir
has to b Emoved
ftom a more stable tully filled 2 ,{rbilal while in bcEositrg iodc ndii I
Be+, it has to be lost from the less stable balf_
fillcd 2r.orbital and furthcrmore, tbe lcs of an AEs,

more stable Be2* ioo

on, theteforc, IE oI Be
2
y)^l!!: ?-,:
:b, ioDs and ?p6) ant a3+ 6i
2oe1
-hai
yz
(iri) SiDoe less ellerry is requircd to remove an.r_ are soetectrodc each one of these
clectron thaE a p_elestron of the same eners/
level, therefore, morc enerry is required 6
remove a 2r+ledroo rrom B+
ltfzf; tnan a
2p+t:d:!n from c+ 1e2i2pr). In orher
wor6,IE, of C is lowcr tlut that'of B. shells and Mg2+ and Al3* have two sbells each,
(iv) As rrye mo!r'e from C to N to O, the nuclear therefore, ioDic radius of K+ is the largest
fol_
cbarge_jncreases by one uoit at a dme, therefore, loned by Mg3+ and then Al3+.
their IE also increase accordingly. IIr othe;
words, IE 2 of O i.s higher thdL that of N which
ilt
turn, it Nghet thqn thar of C.
(v)_ ID case of o+ (1s2 zr2
?3) an electron is ro
be lost from an exac half-filled Zp_orbitat bul. in
y
case of F+ 17,s2 ?tz 2pa) this is not so.
However, due to an increase in charge ftom + I
irl Li+ to
lGs of atr eleclroD ftom F+ gives an exacly +3 in AJ3+, therefore ,the ionb rad u ofAl3+
half- is
filled (i.e., P+ 62 Nz Zp3;;, rher"_ lower han thot of Li+
.2p.orbirat
Iore, lE 2 of F should be lower thaa tiai of O. Thut, the ionic radii ol these
lour iol, increaec in
(vi) Lastlydue ro highesr nuclear charge in the
znd period, IE, ol Nc is qcckd. a Le much
*o*' * to.
htgher than thdt of LL
__
/. Classtry
ahe elements havirg
From rhe above discussion, it follows that
IEz of _.._.1:,1,:
EumDers as vetr balow iEto three seDarate pairsstomic
on the
the clements of2nd period increase in thc bf,6ls of sirDlhr cheuical propenies.
Be<C<B<N<F<O<Nc<Li ordcr :
erectmDlc explanatiotr : 9, 12, 16, 34,
cive brlef
53, 56.
(West Beryat I.EE. 2003,
4154
' ' Ne.4 Course Chemistqlfifr{A

clectrooic configuration is :

1szzs}2p63?3P6 3dro 4i2 4f .

12+8+18+18=5(r Ibtal number ofdlectrons = 10

16+18=34 Tbtal number ofP'electroDs = 6 + 6 + 6 = 18
'Ibtal number of r-elecfioDs = Z + 2 + z + 2
=8
.. Differeflce in total number ofP-aDd 'loctrons
= 18-8 = 10.
Thus, the inert 8as is kryPton'

i4UETT UES.Tr,0,

ooly
of 7. Which of the follov/iDg combinatioDs contains
1-
" ln loDffrom ofthe periodictablc the properties isoelectronicsPecies I
iii" ,r" , periodic funcli()n of lheir
"Lh"nt. (b) bnizntion enerry (4) N3-, O2-, cl-, Ne (b) F- Ar ' S2- , cl-
(d) atomic size '
(c) atomic mass (d) atooric number'
in the
2. Total number ot vertical columns (grouPs)
loDg form ofthc Periodic table is :
(a) 8 (D) 18

(c) lt ('/) 16
3rd period is
3. Number of elemcnts Present iD thr'
(a) 6 (b)32
tiofl ofenergY ?
(c) 18 (d) 8'
e- - Cl- (D)o- t c- - 02-
4. The number of periocls in thc Pcriodic table (.r) Cl +
is

(o) 6 (b)7 (c)O+e--O- (d)S+e--s-'

(c) 8 Gi) 10 10. Which of the fbllowing elements will have
bighest

5, The generaloutsr oleclronic conliguration of tran- electron affiDit), ?

sitioD nletals is

(a) CsI (b) LiI

(c) LiF (d) CsE
' (o) [Rn] s/4 6r,4 71 1t'; 1tn1 -s1ra oa5 l'1 12. Wbich of the follo ing rePresents mGt elcctro-
-
i"i inrt srtn r"f r'o ('l) lttnl s/14 611 7'2 7P3' P6itivc element ?

t tt 3d 6'd 7'c ll a 9'b 10' c

l.d 2.h 3I/
ll, tl
 CLASSIFICATION OF ELEMENTS AND PEHIODICIry IN
PROPERTIES
4ls5
(a) lHel2.tr (b) [}]lelzs2 22. ADongsl the following elemenis (whose electronic
(c) [Xe] 6sl (d) [xel 6". connguratrcns are given below), the one having the
13. The correct order ofelectron aflinities highest ionization ener$/ is ;
is
(a)O>S>Se (6)O<S<Se (4) [Nel313pr (r) [Ne] 3rz 3p3
(c)O<Se<S (d)S<Se<O. (c) [Nel 3r2 3p2 (rl) lArl uro 41 apt.
14. The five successive ionizatioD eoergies of afl ele_
ment are 800, UZ1, 3658, Zs(rU afi 32.5U kl 23. The sotemerr that
mol-1 respectively. The number of valence
is not correcl ror
sificatioo of elemeoB is
;ii,Jr::X:
electrons is (4) The properties ofelemeDls arc a periodic
ilDG
(a) 3 (D) 5 tion of their atomic numbers.
(c) 4 (,t)2. (6) Non-metallic elemenls are less iD number
thar
15. Which of the elemenh whose atomic numbers are metrllic elements.
givel below cannot be accommodated in the (c) The firsl ionizlion energies of elements
along
presert set-up of the long form of the priodic a period do not \,lary in a regular manner witi
lncreasc in atomic number.
(a) to't (D) 118 (d)
(c) 1 (d) tzo
16. An element of the 4th period which has maximunl
number ofuDpaired clectrons is 24. Which pair of atomic numbcrs represents r_block
clemenb ?
(o) zoh (b) zact
(a)7,1s O) 6,12
(c) ,oZn (d) :rtu (c)e,17 @)3,12
17. Which ot the following isolectronic ions has lhe (M. L. N-R.
lowest lirst ionization eners/ ? Alatnbad L 92)
25. fion of ahe elemert which
(o) K* (D ca2* with atomicDUmber43 in
(c) CI- (d) s2- is
It. Which among the following species has the same @)G*zpcaP 3pa3a1 4z
number o[ electrons in its outermost as well as
peDultimate shell
(b) 1s2 ztz 2pG rt2 3p6 3dto 4$z 4ps
?
(") M*+ (r) 02- @) G z? zp6 tP 3pa 3fi aot
(.) F- (q 13 2s2 2p6 X2 3pc Uto 4rr 4p6.
@) caz*
19. The towest fISt ionization enerEr would bc ' ()rL!,.r-.F, Artzhntud tt).)2t
as_
soqated with which of the folloudDg strudurcs 25. Whicb of rhe follou,ing traDsitions invokes maxi-
?
(a) 1i 2s2 zp6 xt mum amouDt ofeEerry ?
bz 2? 2ps
@)
(c11s22J2 2p6 (a)M-G)- M6) (D) MG)- M-6)
@) t-323 ?p6 313p2 (c)Mr6;- Yz+6) @)M2+@)- M3+@).
27, ion
(4) Booding bebaviour (r) EtectronegatMty be
(c) Iooization ener&r (d) Neutrodprotor
ratio. (a)G,Nzzpc,3sr e) tp ,xz zp6 ,z? 3pt
tD.l.T Randd tgso\
21. Tbe outerEct eledronic configuraaiotr oftbe mosr (q #,* ?p6, # 3p2 91 G, zi
4f,3.z.
etec.tronegative elemeDt is
t c.B. :i. E. Mt[.T. 1 e s3 )
(a1 nsz np3 (\ tG npa
2& The corred order of decresiog first ionisation
eDerry is
(c) ni nps (rt)*z ,p6. (LI.T tgsot (a)C>B>Be> U (r)C>Be>B>Li

12. c 13. c 14. a 15. c

22. b 23. d 24. d 23. a
16. b
26. d
17. d lE. d 19, a ZO. tt 21. c
27. cl
4156
36. Which of the follo$'ing element has thc maximum
(c) B > C>Be>Li (d)Be>Li >B>C electron affinity ?
(A l'I'M'S' 199i)
(a) cl (b) Br
29. Tick the correct order of second ionisation onerry (c) I (d) E
in lhe following: (c.R.s.l,. Pl,l.I: t 999)
(a)F>O>N>C (5)O>F>N>C ?
3?. Which of ttle following is most eleckoDegative
(c)O>N>F>C (d)c>N>O>F
(u.P c.E.E. 1996\ (a) CarboD (D) Silicon
(d)'fil t t'"1 !! )

30. Which of the following sPcies has the highest

(c) Lead
38. Which of the following remaios unchaDged orl des-
electron affinity ?
cendi[g a Sroup in the Periodic table
(4) F- (D) o
(d) valence electrons (b) Atonlic size
(.) o- (d) Na+
6\
(c) Density (d) Metallic char ter'
( Har.Yn ru C' L' li'X, I 99

(At' of
31. The electronic configuration of Gadolinium 39. The radii of E F-, o and 02- are in the order
No. 64) is
(o)02-, F- > F> o (b)F- > C)2- > F> O
(4) txol4f s/6f (b)
(c)02- > o > F- > F (d)02- >F- > o > F'
(c) [xe]4P sd5 tu2 (d)
tssn
40. Which of the folloMDg has maximum ionization
T]ne incorrect statement among the following
!s
32. - potential ?
ra) Tbe first iotrizaiion poiential of Al is less than
(a) Be (b) K
the first ionization potentialof Mg' (d) Ms
(c) Na
/b l The second ionization poieniialof Mg is Sreater t.l.!-l.M.S. l9e9 \
' ' ihao ttre second ionizaiion Poteniull of Na'
in which of ihe
r.\ Tbe first ionization porcntial of Na is less ihan 41. The ionic radius of 'Cr'is minimum
' ' the first ionization poteotial of ME followins comPounds 'l
(4) Krc;o4 (b) crF3
/l\ The third iodzation potential of Mg is geater
(c) cro2 (d) crcl3'
than the third ioDization PotentialofAl'
(I-I.T 19en illarytm( l l l i t't"
33. The lirst ionization poEntial (eV) of Be
and B 42' CN- ion is
The sPecies isoelectronic witb
resPectively are (a) Fz (b) oz
(a) 8'29,9 32 (b) e-32,8 2e
(c)9'32,9 32 (d)8.2e,8 2e (c) si @q-.
tc.lJ.s.E. LM.T 19981 (Hdr)\tt14 ( 'lt'lt 1: Il'9\
34, e following iooic com-
the maximum distance
and anions'

(a) CsF (b) CsI

(c)LiI (

'{"8 \E I'11T I &KC'E7:2001)

co[fiSuratioo rePreseots 44. The eteatron afiniues of halogoDs are :
35. following
--' Which of the element -having
the hiShest secord
oitt" F = $2" A = *9,8r = 324,1= 295 kI mol-l'
"i"rt
ioniu tion Potential ?
*fr" f- O as comPared to that of F is
m" t igft"t
(a)1122?2P4 (b)1s22?2p6 due to
(d)182232P63s2' (d) Higher atomic radius of F
G)1?2?2P6ss1
0h. ll .T 1e91t) (b) Smaller eEcrroDegatMty of F

37. a
b 29. b 30., 31. , 3Lb 33.b 34, b
2A.
40, c 41, s 42. c 13. b
3E, a 39. d
CLASSIFICATION OF ELEMENTS AND PEBIODICITY IN PROPERTIES 4ls7
(c) Wbaker electron-electron repulsion in Cl
(c)I+>I->I (d)I->I>I+
(d) more r?cantp-sub6hell in CI. t\D.C.l;. 199s.1
\.c.R.s.8. t!]t.T 19e7 lt|.p. (..L.t:.2at)0)
45. Among the following groupings, which represents 54. The ionic radii of N3-, O2-, F- and Na+ fo ow
the collection ofisoelectronic species ?
the order :
(a) No+, C;-, cot, co
(o) N3- , 02- > F- > Na+
(6) N2, q-, co, No
(b) N3- , Na+ > Ctz .l'
(c) CO, NO+, cN-, C;- (c) Na+ > 02- > N3- > F-
(d) NO, CN-, N2, Ot.
,(.Lt \ t::. ey.l: 2ot)/j) (d)C2-rF->Na+>N3-.
45. Electronic configuration of most electronegarive (,t7. I P :,1.'t: ! 9e tl, 2 0 00 )
element is 55. The first ioniatioD ener$/ of Na, Mg, A.land Si are
in the order
(o) 7 sz zsz zp6 3 s1 (b)tiz]zp63i3ps
(a)Na < M8 > Al < Si (b) Na > Mg > At < Si
(c) 1$2 2 12 2p5 (d) 1 s2 2 s2 2 p6 3 s2 3 p6 .
(c)Na> Mg>Al >Si (d)Na<Mg<At<Si.
LtI:;. B.H.U. 20A0t
47. The bond lengrh in LiFwillbe fiI.PPAr.r 20t)0\
56. What is the maximum number of electrons which
(4) Le&s than rhat of NaF
can be accommodated in an atom io which the
(b) Equal to thar ofKF highesi principal quantum number is 4 ?
(c) More thar thar of KF (?) lo (D) 18
(d) Equal to that ofNaE jC p.tll:200t)) (c)36 (d) 54. t1 1,1,11 1 1,1,1t1
4E. The correct seque[ce ofatomic radiiis 57. The frst ionization energy for Li is 5.4 eV and
(a)Na > Mg > AI > Si (r)At > Si>Na>Mg electroD affinity of Cl is 3.61 eV The AH (in
(c)Sr>Al >Mg>Na (d)Si> Al>Na>Mg. kJlmol) for the reaction,

t(.1!U.I:2000) Li (8) + cr G) + Li+ 1g1 + ct- 1g1,

49. The first ionization eners/ will be maximum for iftbe resulting ions do not combinewith each other
(a) Uranium (b) Hydrogen is1tcv-16xlo-leJ)
(c) Lithium (d) IroD- (a)'7o (r) 1m
(C.l!lI.T 2000; lV.PC.E.E. 2()001 (c) 170 @)no.
50. Whicb of the following has teasr electron affinity ? (M.PPM.7.2000
(4) Orygen (b) Argon 5t. Which of the follo\dng is the smallesl cation ?
(c) Nitrogen (d) Boron. (a) Na+ (qMf+
tA.IiM.C.200()t (r) C^2+ (4 At3+ .
51. Which ofthe follo\ving pairs is isoelectrooic ?
(a) Ar and Cl (D) Na+ and Ne ill.PI:M. [, 200t)\
59. T}ie conect stateme[t about d-block elemeDts is
(c) Na+ and Mg (d) Mg and Ne.
(a) they are all merals
(a.8M.C.2000) (D) tbey showvariabte yalency
52. The elements inwhich 4r{rbitals are pro$cssively
(c) they form coloured ions and complex salts
Iilled in are called as
(d) all the above statements are correcr.
(a) Actioides (D) TtaDsition elements
(c) Lanthanides (d) Hatogens. t \l.Pl!tl 1: )t!a|,
60. The conect order ofradiiis
lHarya a (;. E E.T.2000)
Which one of the following is correct order of rhe (a)N<Be<B (6) F- < 02- < N3-
size ?
(c)Na<Li<K (d) Fe3+ < Fe2+ < Fe4+

44. c 45. c 4Gc 47. a 4E. a 49. b 50. 51, b

54. d 55. a 56. c 57. c SA. d 59, t 60. ,'
 Neqt Coatse Chen' istr'!
4158

61. The set representing ihe correct order of first (4) caz+, cs+, Br (b) Na+, Ca2+, Mg2+
ionization Potential is (c) N3-, F-, Na+ (d) Be, Al3+, cl-
(b)Be > Mg > (l.l li.li.li. )'4)-l
(a)K> N,r > Li Ca

(c) B > C > N (d) Ge 70. 'l}lc rons o2-, F-, Na.l-, M82r 'ncl 'N3+ are
"' i,|,. .rr, , isoalectronlc. Their lonic radii show
among (a) l stgnilicant increase from 02- lo Al3+
62. The correct order of Ist ionization potential
following elements Be, B, C, N, O is 16) a signilicant decrease fronr
02- to Al3+
(a)B<Be<C<O<N (c) an increase from 02- to F- and then decrease

(b)B<Be<C<N<O from Na+ to Al3+

(c)Be<B<C<N<O (d) from 02- to F- and then rlcreasc
a decrease
rionr Na+ lo Al3+
71. The ioniu radii of isoelectronic species N3-' 02-
63. The atomic radius i[creases at w" move do$/n a
and F- in A are in the order :

group because (a)136, I40, 171 (b) I36, 171 140

(c) effectivo nuclear charge incf,easca (c) 1'71, 1 40, 1 36 (d) 1 71, 1 36' 1 40
(6) atomic mass itrcreass
(c) addidve electroDs are accommod8ted in new 72. The arrangement of decreasiog sizes of H+, H-
electron lwel al]dH$
(d) atomic Dumber incre (b)H>H->tl+
t'tilnadu C ET 2ltAI)
(d)H+>H>H-
64 The first ionization Potential of Mg, Al, P and
S (c)H->H+>H ta]u- >u1u+
folloqa the order :
(a)Mg<Al<P<S (6) AI s 73, Arrange the following in proper order of size
(c)Al<M8<s<P (d) M P (a)Mg < Si < Al < P (6)P > Al > Mg > Si
001) (c)Al < Mg <Si < P (d)Mg < Al > Si > P
65. Eka-aluminium and Eka{ilicon are known as
(a) Gallium and Scrmanium 74. The highly metalliceleorent willhave the configura-
tion of
(o)2,8,7 (r) 2, 8, 8, 5
(c) 2, 8, 8, 1 (d)2,8,2

6. 75. For electron affinity of halogeDs which of the fol-

block ? lowin! is correct ?
(d) l (b) p ra)B;> F (D)F>cl
(c)tt @)I i.j ar, ct (d) F > I
67. Identify ttre le6t stablc lon amon
(a)Lt- (b) Be- 76, Lanthanoids are
(c) B- Id) l4 elen'lelrls in the sixth period (atomic no =90
lo 103) thal are filling 4l-sublevel
6& According to Periodic
(6) 14 elements in rhe sevenlh period (atoolic no
tioD iD ProPerties of el
(a) nucler neuron-Proton number ratioc = 90lo 103) that are llllin8 5f-sublevcl
(c) (c) 14 elements in lhe sixlh period (alonlic no =58
to 7l ) that are fillinI 4/'sublevel
fr1) l4 etenlents in (he seventh period (atomic nt)'
6' srol
sPecl = 58 to 7l) thal are filling 4/-sublevel
Br = 35)
LUET<S
a 63, c 66. o 67.b 6A..1 69, c 10. b
61, b 62.
.l 13. .I 76. c
71. c 12.
 CLASSIFICATION OF ELEMENTS ANO PERIODICIry IN PROPEBTIES
4159
77. Ionic radii are 81, The clementswith atomic numbers 9, l?,35,53,g5
(a) inwrsely proponiooal to efieclive nuclear ciarge are all
(D) inversely propordooal ro square of effcctite (a) noble gases (D) halogens
nuclear charge (c) heary metats (d) Iight rnerals
(c) dircdly proportional to effective nuclear ciarge
(d)directty proportionat to square of 82. In a gi/cD
lruclear charge t.it\l-t\t.] effectiye
.-
shell, lhe order ofscieeoiDg effect is

7& Which of the follo*,ing has highest value of ionic

(o)s>p>d>f (b)f>d>p>s
radius ?
(c)p<d,<t<l (d)
(e)f>p>t>d .2001
(o) u+ (6) 83+ t3' Considrr rhc ions: K+, S2-, CI- and Ca2+. The
(") o,2- (d) F- raox ol these ionic species follo$, the ordcr:
79. The formatioD of the oxide ion 02- 19; requires (a) Ca2+ > K+ > Ct- > s2-
Iirst an exothermic and then an endothirmic step Cl- > Sz- > K+ > Ca2+
(6)
as shown below :
(.) Cu2+ , Cl- > K+ > 52-
o G) + r-* O- E); AH. = - 142kJrnol-r (,i) K+ > s2- > ct- > caz+
O- (g) + c- 02- 19;; aa" = + 844 kJ nrot-l (e) 52- > Cl- > K+ > Ca2+, i', r,, t ( t: r, )t)t,j
This is because - E4. Which of rhe follotring have Do u[it ?
(a) Oxygen is more electro[egative (a) clcctroncgarivity (b) elecrron
afhnity
(D) o)rygen has high electron afliDiry (c) ionisarion encrry (d, *"i",,:l
(") O- *itt tend to resisr rhe addirion of another f:irli::.
electron t5, The last ei(:crron of the
?_block, in the present
periodic labtc cin be represented by contiguratioD
(d)O- ion has comparatively larger size than where In] represents inen gas
orygen atom.
(a)ItnlTP 7p6 (b) Itnl7s2 5f 1 6dto
EO. Which-one of the follol ng sers otions represents ho
thc mllection ofisoelectronic species ? (c) Url 6i2 fl4 5d10 6p6 (.r) None of these
(4) K+, Caz+, SC+, Cl-
(D) Na+, Caz+, sC+, F- E6. Ha is an alphabetical slmbot for
(c) K+, ct-, M82+, sC+ (a) HafniuDr (D) Hassnium
(c) Hahniuor
(d) Na+, Mg2+, Aj3+, ct- di Hetium

i1 ii".i-i-::,. i:.:.
ole Choice Q.uesLions
6. In heavier elements, HuDd,s rule is not alwa)6 fol-
I5. Front z-= l2l s.138, rhe filtiog up of g.
lowed. orbitals
oetns Iorr\hrch lhcre is no provision in
t. Since lhe size of K is larger than K+ fl .34 A) and set-up of thc prriodic table.
he presnr
rhar of F is smalter than rhar of F- (l.t A), 17. Bigger rhe size, sma er rhc LE.
therefore, optioD (o) is conect.
9. The second electron aflinity of an element is nega- l& Ca2+ = 2,8, S.
trve, re, energy is absorbed. 22. B:th (h) irrr(l (l) have simitar fiacily half.filled
11. For ratio of anion size to catioD size to be lowest, elc(tronr r,.ntiSUratron, bul rhe slzi of
snlaller lhal rhirt of (d, 1af is
anion should be smallest (F-)
and catioo ro be
biggest (cs+), rd , option (d) is correct.
14. IE abruprty increases (ria IEo > > > I%) wben
an
electron is knocked out from the noble gas
core.

77. a 7t. c i9. c t0. a al, b ll2. a 3.!. r E4. a E5. c t6. c
 Ncr4 CouYse Chemistt4'
4l60

29. IEz of O is higher than that of F because in case of
(). the second clectron has lo he renloved from fl
more stable completely hrlf-filled electronic con-
frguration,ia, O+ 1t s2 2s2 2Ptr}ptyzPbwnnein
case of E this is lrot so, ie- F+
(1 !7 2? 2p?,2 Ply? lt.\
r
"ite^d removal o[
46. F O sa 2 t2 2 Ps ) is I hc n]ost electroDegativc clenlen t-
47. Due lo smaller size ol Li tban Na ot K, LiF has
smaller bond leogth than NaF and KE
4E, In a period, atomic radii decrease from Ieft to rigbt'
Beiog smallest, hrdrogen has thc maximum IE1'
49,
50. Inert gascs have zero clectron-affinity'

a[other electron from F+ giles a rnore stablc s1, Both Na+ and Ne have 10 electroos each-
conrptetely half filled electrooic cortfiSuration' ' a' p6' 36'
s6. I s2 2 rz 2 p6 3 sz 3 p6 3 4to 4 57 4
rt+ 0 ,2 2s2 2 P:Z Ptyz plr).
57. AH =(s.4 -3 6r) x (1 6 x lo-leJ)
--' Energy is released t hen an electron is added
30. to O
x (6 023 x roz3;x10-3 = 1?2 5 kJ rnol-1
Urt has to be spent when an electron is
"ln"tg, ftom top to httom'
added to o-, F- and Na+' 61. Witbin a grouP IEt decrease6

J1. The tilling of4 f-shellbegins onlywhen one elcctron 62. Because of sxtra sEbility of exacily half-filled
has alreaiy been added to 5 d-orhital' electroflic conf,Euration ofN, its IEr h higher than
32. lEz of Na in case
thnt of O. Furthet because of higher nuclear
ofNa, the d fronl charge, tE1 of C is higher thao that of Be and B'
(wal of
the noble Amongst Be and B, tbe IEr ofBe is hiSher than that
second electron gives a nobe gas corc' ot Be a 2 J-clectron is to
of
33. Be has higher IE, than B. re of B a 2P-electroD is to be
i. order is (a) ie , B < Be
Bi8ger the sizc of ions, larger is lhe distance
be-
]4. "ralt
t\I'eeo the ccntres of their nuclel' <c<c)<N.
elgctrons 63. As th Dumber of shells iocreases, atomic radius
3t, Each SrouP has a fDGd number of valence
accordiIlgly.
39. The size ofOz- > F--and lhat ofo > E Therefore' incl ea.ses

t}le o'r'erallorder is: Oz- > F- > o > F 64. Because of extra stability of exactly hau-filled
ioniza- electronic coofiguration of P ir IEt is hiShet thaD
40. Because of smalles! size, Be has the highest
tion Poterltial. that of s. Further the IEr of Mg is higher thaD that
41. Anrongst lqcroa, GF3, Cro2 and CrCl3, Cr has of Al because in case of Mg, electroo is to be
removcd from a 3 J{rbital while in case of Al, ihe
lhe maximum oxidation number of + 6 iD electron is to be removed from a 3P'orbital Thus'
*rcroo ano trence tras thc rtrinimum ionicmdius'
option P is conect'
42. CN- and Si both have 14 electrons' 67. Be has (2r2) and tberefore
43. In aoy period, r-block element has tbe largest size' shcnra I an extra elecfton to
45. Allthe specieJ have 14 electrons' lbffl Be-

ADDITIONAL ITfrSTT.

Aeaeracion-Reaeon Type Oleetione

Use the follovitlg
qucstions ertlotr' ln column I nnd thG'Resson'ln column 2'
T-he

coson ls tbe CORRECT GxPlsnation of the assertlon

t}!e assertion'
on is NOT the CORRECT explanadon of
cT.
ECT.
CLASSIFICATION OF ELEI\,iIENTS AND PERIODICIry IN PROPERTIES 4161

Assertion (colrm[ 1) Reosot! (colupr 2)

The iolizatioD ofr-electrons requires more enerry J-Electrons are closer lo the nucleus tbaDp-electroDs and
than that for the ionizatton ofp-electrons of rhe hellce are more strongly attracted by the nucleus.
same shell.
When traDsition n]etal ions ionize, the 4 .r-orbital The eoer$/ of 3 d-orbital clectron is lower than that of
electrons are ionized before the 3 d-orbilat electrorrs. 4r-orbital electrons.
Helium and beryllium have similar outc. electronic Both are chemically inert. (A.I.I.M.S. 1991)
contiguration of tbe typc , 12.
The element with electronic configuration The last electroD eters the l-orbital.
lxelsl 4f 5d1612 is a .r-btock etemenl.
The first ionization energy of aluo]inium is lower Ionic radius of aluminium is smaller thaD rhar of mag-
than that of ntagnesium. ncsium. (A.I.I.M.S. 1994)
6. Bolh N2 and NO+ are diamagnctic substances. NO+ is isoelectroDic with N2. (4.1.1.M.5. Igen
u.r.r.M.s. 1997)
7. ElectroD atfinity of orygen is less rhan rhat of IoDizarion porenrial is as foltows : *.
Iluorinc but greater tba[ thal of [itrogen. ?o.].].r.r. ,rrq
t. F atom has a less negative electron affinity than Cl Additional electrons are repelled Dtore effe ctively ty 3 p-
atom. electroDs in Cl than bv 2p-electrons in F atom.
(I.I.T 199E)
9. zn- ' rs dtamagnetlc. The electrons are lost from 4,r-orbital to form Znz+.
10. The first ionization energyofBe is greater than that 2p-orbital is lo$,er in energy than 2 J-orbital.
of B. (I.I.T 2001)

TruelFalse Statemente
An elenent with atontic number 47 is a transition 5. SecoDd electron affiDity is always negative.
element. 6. There are seven periods and eighteen groups in the
The second period contaios 8 and the third period periodic table-
contains l8 elen]eots. 7. The size of CI- ion is smaler (han that ofs2- ion.
1 The size decreases as Cu > Cu+ > Cu2+. t. The decreasiDg order of electron affioity of E Cl,
4. The Iirst ionization ener$/ of N is lower than that BrisF>Cl>Br.
of oxyge[.
(I.I.I 199i)
Fill ln The Dlanks
1. Ar, elementwith atomic nunrber 35 belongs ro..... t. valency of ap-block elen]ent is equal to eight.....
block. rhe nuntber ofetectrons prescot inthe -.... s[ell.
2. Each series ofd-block contains ..... elemeob. 9. Wben an elcclron is added to a uninegative ion,
3. The lirst ionization enersr of N is ..-.. than rhat of eDerry s ..... .

O while thesecond ionization eDer$/ of..... is higher 10. AD clementwhich lies right abde and belc, Cd in
than that of ..... the preiodic table are .... and .... respectively.
4. The radii of Fe, Fe3+ and Fe2+ decrea-se iD the 11. On thc Pauling electronegativity scate, the element
order. .... next to F is .... . (Roorkee 19E9)
5. In the second priod, the most lectroDegative and 12. Caz+ ion has a smaller radius that K+ because it
electropositive elements are........ and ...... respec- has (I.r.T. t9e3)
tively. 13. The radioactive series consisting of man-made ele-
6. The general outer 6hell electronic cooliguration of ments is called ..... elsments.
/-block elements is .... . (A.I.S.B. 1996)
7. Among the isoelectroDlc ioos, the ionic size io- 14. The clectrooic configuration of atoms and
creases as the ..... charge on the ion .... . ...........provide a basis foi periodic classification.
4162
Pradeep's

M atchinO Ty ? e Q.u estlons

Match tlrc item.g in cofumn I with those in columrr ll
Column I Column II
1. Horizontal rows (a) Ionization ener$/
2- Elements with electronic mnfiSuration a"^2 rPl-6 (b) valence electrons
3. M(g) + EnerB/......... M+ g; + e - (c) Blectron affinity
4.X(g) + s- X- G) + Eoergy (d)p-Block elemcDts
5. Electrons present in the outermost shell (e) Periods.
-

1. (a\ z. (a) 3. G) a. (e) s. (b) 6. (a) 7. (c) E. (c) r. (D) ro. (c)'
THUE,/FALSE STATEMENTS

l.Ttue2.False,bothcontain8olenrents,3.Ttue4.Fhlse,firstionizationenerslofNishiSherthao
that of O 5. Ttue 5. ltue 7. Ttue E False, Cl > F > Br.
FILL IN THE BLANKS

1.p- 2. ten 3. hiSher, oxySer, nitrogen, 4. Fe > Fe2+ > Fe3+ 5. Fluorine and lithiu m 6' 1n - ) f-ra
l0' zinc, meroury 11' qxygeo
6-y
|
a0- n?.7. negative, iocreases E. minus, valence 9. absorbed
i2. higher ouclear charge 13. transuranic 14. aufbau principle'
, MATCHING TYPE OUESTIONS
1 . (") z. (d) 3. (a) 4. (c) s. (b).

HINTS/EXPLANATION9 to
3. Coned ftawh : Nll,ough He and Be have siolilar
outer eiectrol]ic corEgulatiorl of thc type rr2, only
I{e (1$2) has inert 8as confiSuratioo afld henco is
chcmically irert bu t Be (l s2 2t2) does not have inert
gas configuration alld hEttceis l1ot ct]emic{lly inert
1. L:o\ect os.tcflion. Ba(OH)z is more ba$ic thar
NIg(OI I)2
Con'ect ftn\ort : Becaust of lower IEl of Ba than
that of M8, Ba(OH)2 ionises to a grester o.tent
rhan that o{ Mg(OH)z .nd heDce BB(OH)? is ol
stroogcr base thtrn Irlg(OI-I)2
 TJ N! OT

First Lavv of TherrrtodStnarr,ics

a rt d Ch e n-ti cal Er-r e rg eti c s

Some basic concepts-syatems, surrcundings, types of sysfems,

and extensive ptopertiea, slate lunctions, irre-versi6le process-
types ol processes, inlensive
Zeroth Law.
Firsl Law of Therr.dynamics-internal energy, e halpy, vyork, heat capacity, specific
capacily, molar heat capacity, enthalpy changeJludng pirii* rrun"iri"n". heat
Er halpy changes in chemicar reactions-srandard entharpy o, tormation, Hess,s raw
of consrant
heat. sumrnaiion, bond enthalpy, rneasurement ol enrhalili of re"citon",.n"rgy;t";;;;;ii.;
teactions-
Sources of energy--Sun as the prirnaly aource ol enetgy, Ahernalive goutcas
ol energy.
SEC'TION I
SOME BASIC CONCEPTS
USED IN TIIERMODYI{ANIICS

The lmportanccof thermodynamics Lies in the

following two facts :
-
_ (, ft helps us to predict whether any given
chemical reaction can occur under the given set of
conditions.
(u) It helps in predicting the extent of reac-
tion before the equilibrium is attained.
.Thc llafir.'therrEodydamics,'cIaE givcn byrn
-,
of h?at into nbchonical wo* lrha no mear6 heai an
briDg about this convE6io, is crllcd an ar&lra

5/r
512

The llmltatlons of thermodyuamics i.e. where

it fails to give any information are as follows :-
(i) lt helps to predict the letsibility of a
process but does not tell anything about the rate at
which the process takes place.
(r7) It deals onlywith
of a system but does not
mechotism of. the process
tho proccss) .

(iii) It deals with the

ture, pressure etc. of the m
tell anythiog about the
molecules.
A PIECE OF
MARBLE + HCI
f.:.) $or'.'F tri, tri :.:!i,-l a.rll.-eft5 ;i :iil:: :i I a:i: : i: :l::il:l:

FIGURE 5.1. Examples of open system :

Some basic terms and concepts commonly la) Watcr keDt in oDen vcssel
used in thermodynamics are briefly explained (h) Rear:tion taking'Pla.e ii-r an open vessel.
below :
1. System and Surroundings. The Parl of lhe reaction is allowed to take placc in an open
univene chosen lor thermodynanic considerution vessel (e.g. between a piece of marble and HCI)
(i.e. to study the decl oI temPerature, Pressurc etc.) (Fig. 5.1. b), exohange ofboth matter and energy
is called a system . takes place between the system and the surround-
ings.
The remaining pottion of the universe, exlud-
ing the systent is called surroundings. Animals and plants are open systems fiom the
thermodynamic point of view.
A system usually consists of a defrnite amount
of one or more substances and is separated ftom (D) Closed system. .I/ d system can ex-
the surroundings by a real or imaginary boundary change only energt with the surroundings but not
mattir; it is called o closed Eystem. For example,
through which matter ao.d energy can flow from the
system to the sutrounditgs or vice versa.
2. tlpes of systms (Otr cD' closed and iso'
latcal systeEs)
(c) Open system. I
system is said to be a
open system if it cu er.cho.nge both matter and energt
with ie surroundings. For example, if some water is vessel has conducting walls, exchange ofenergy
kept ia a:r open vessel (Fig. 5.1. a) or if some can take place between the system and the sur-
roundings.
If the reaction is exothermic, heat is given by
the system to the surroundings. If the reaction Ls
endothermic, heat is given by surroundings to the
systern. Further, if the reaction is accompanied by
a decrease in volume, mcchanical work is done by
the surroundings on the system and if the reaction
o is accompanied by increase in volume, the
mechanical work is done by the system on the sur-
I work is also a tYPe of
the Piston in or out also
of energY between the
HEAT
system and the surroundings.
SURROUNOINGS
FIRST I..AW OF THERMOOYNAMICS AND CHEMICAL ENEBGETICS s/3

Tea placed in an open cup is an example ofan

SURROUNDINGS
open system whereas tea placed in a closed steel
HEAT
tea-pot is an example of a closed system and tea
placed in thermos flask is an example ofan isolated
syste m. (Fig. 5.4)

o TEA IN STEEL KETTLE

SURROUNDINGS
OPEN SYSTEM

SURROUNDINGS
CLOSED SYSTEM

TEA IN
THERMOS FLASK

o ISOLATED SYSTEM

FIGURE 5.4. E<ample! b tllushate opeh,

chsed and boLbd slrstems,

SURROUNDINGS 3. Stat ofa systcm and State variables, I}e

system changes. That is wby these properties of a

system are called Jrare variables.
A process is said to occur when the state of
the sptem changes. The first and the last state of a
system are called the initial state a,,ld the
final state
respectively.

INSULATION

went by lift or by stairs. Hence work is not a state

function. Instead, it is sometimes called a,path
funaion'.
 Pradeep's
sl4

Atternatively, a Pftysical quontia! is said to be 6. lAes of thermodynamlc procsses../4 ,'ler-

5. Macroscopic system and Macroscopic as follows :

siv ProPertis).4 (,Isothcntral process. lVhen a process is

of chemical sPecies caried out in such a ma\tter thot the temperature
is called s macro' remains constanl throu?hout the process, it is cqlled
n such a
tem tothe
keep the
temperature of the systom cofftant.
ature, Pres- (ii) Adlabatic process.When a process is car'
oiling point ied out in such a manner thqt no hedt can tlow from
es or ther- lhe system to the sunoundings or vice vena i'e' the
modynamic properties. These are further classified system is comPletely insalated from the sttround'
into two types as follows : ings, it is called an adiabatic process.
(iii) Isochoric process.It is a Process duing
which the volume ol the system is kePt constant '
(iv) Isobaric process. It is a process duritg
which the pressure ol lhe system is kePl constont'
?. Reversible and Irreversible Processes' The
various types ofprocesses mentioned above maybe
carried out revenibly ot inevenibly. These terms
may be understood as follows :

In order to understand a reversible process,

(ii) InteEsivc properties. These are those imagine a gas confrned wi&in a cylinder provided
propeties which depend only uPon the nsture of the
'suistance with a frictionless piston upon which is piled some
and are in(kPendent ol lhe amount of the very frn sand
substance prcsent in lhe system. The common ex- exerted by the
combined pres
piston, the pile

PILE OF
SAND
PISTON

EXTERML
It is of interest to note that aD extensive PRESSURE

property may become

speci.ffing unit amount of
Thus mass and volume ar
density and specific volume (i.e. mass per unit
INTERNAL
volume and volume per unit mass respectively) are PRESSURE

FIGURE 5.5. Understanding ihe

Further, extensive proPerties are additive but concept of a reversible Process
intensive properties are not.
 FIRST LAW OF THERMODYNAMICS AND CHEI\,,IICAL ENEBGETICS
sure. Thus under these conditions, the piston
does not move at all and a state of equilibrium is
said to exist. Now if one particle of sand is
removed, the gas will expand very slightly but the
equilibrium will be restored almost immedialely.
Such a change is called, an infinitestimal change.
If the particle of sand is replaced, the gas will
return to its original volume. By the continued
removal of the particles of sand, the gas can be
allowed to undergo a finite expansion but each
step in this expansion is an infinitesimal one and
can be reversed by an infinitesimal chaoge in the
external conditions. At all times, the equilibrium
is restored immediately.
A process carried out in the above manner is
called a reversible process and may be defined as
follows :
ReYersible Froccss
1. The process is carned out infinitcsimally slowly r'_a
difference between the driviDg forc.e aod the opposrng
force is very very small.
2. Ar any srage during the pro@ss, equilibriunl is Dot
disturbed.
3. Ii takes infinite time for conrpletion.
4. It is oDly imaginary and cannot b achieved in actual
practice.
5, Work obtained in this process is maximum.
SECTION II
ZI'ROTH LAIY OF THERMODY\ATIICS
5.3. Definition ol Zercth Law ,' , "" - ' --::.'
_. As mentioDed iu the beginning of this unir,
this lawwas put forward much a_fter thi enunciation
ThLs leads to the following definitions for the
zeroth law of thermodynamics :
5/s
A reversibh procw is a Fuxs whkh i\ curriul ont
infinitutimally slovly n tha! ull dwryes rcurring
in lhc dirnt pftxms &n be ex ctb m,e^wl anrt the
slslem rcmaiw a[na$ in u iatt of equilihrium B,ilh
the surroutdings sr erery slage of the fot:c*r.
On thc other haruL a procesa which does not meel
the ubors requiramenls ir calletl un irrcversible
pnrcxs- In olher wordq an irrcversible procest i,r
defined u thd lrrocess h'hich i-\ no! cauied out
intinilesimally slowly (instead, it it Lwrricd out
rapidl so llml thc ltuccessive steps of rhe dirucl
process cannot he retfirced and an! chorge in lht
e$enal condilions d.isturbs lhe equilibriunt.
The main points of ffierence betu,een a re-
versible and an irreversible process may be
sumned up as follows :
Iueversibl6 Process
This process is not carried out infinitesimally slol ly
but is carried out rapidly r:e the difference between
the dri\ing force and the oppGing forc is quire large.
Equilibrium may exist only afler the completion of thc
PIOCe,ss,
Ittakes a finite time for mmpletioD.
These processs actually occur in Dature.
5. Work obtained in this procss is not maximum.
o
FIGURE 5.6. (a) Thermalpquilihrium I.(tweLn
bo,lies A anrl c
(b)-Thcrmal equilil'riun between hodi.s B an,l C
(c) lhermal .,quilibrium between hodi.s A and B.
Wlwn two bolies A and. B are separately in tlurtrru I
a lhi l hodJ C, they in turn arcin
um with each other
or
A and B havc cquality o!
When hoo botlies
lempcratare $'ith a third bodJ C, the! in lwn have
qunliE ol lcryreroture with each othcr
 s/6 Pradeep's
5-4. Application o, Zerorh Law in
SECTION III

- .The factstated aboveis sosimple and familiar.

that it does not Deed any further experimen ts for
its
support.
It rnay be pointed out that as thermometer is
 FIRST LAW OF THERMOOYNAMICS AND CHEMICAL ENERGETICS
slt
which contribute towards internal energy of the application of force is d.isplaced in the direction ol
a
system. But it does not matter, since we are not the force If
. R is the
magnitude of the force and d/ i.s
interested in knowing the absolute value ofinternal the displacement of the point of applicatiotr in the
energy of a substance. Rather, we are i[terested in direction in which the force acts, then the wotk
energy which accompanies a done is given by w:Fxdl
e determined. The change in
(or AU), Tte above type of work is called mechanical
accompaoy'ing a nork. However, there are many other forns ofwork
but in each of these forms
AE=%-Er llork done = IA generalized force ]
or AU=Uz-Ur
x lA generalized displacementJ
where E1 (or U,) is the internal energy of the Tlvo main types of work used in
system in the initial state and E, (or Ur) is the themodynamics are briefly described below :
internal energy in the frnal state. (i) Electrical \ ork The generalised force is
Since E, and E, are state functions, therefore, the E.M.F and the generalized displacement is the
A,E is olso a state quqntity of electrici4.' flowing through the circuit.
functiott (i.e- depends only on the
initial state and the fioal state of ihe system). Hence
ln case of a reaction, if E. (or U*) is the Electical work done
internal energy ofthe reactants ard Eo (or U) that : E-M.E x Ouantity of electiciy.
of the products, tle change in iaternal energ5r This type ofwork is involved in case ofreac-
ounng the reacttoD Ls grven by tions involving ions.
AE=Ep_En (ri) Work of expansion or Prrssure-volume
or AU=Up-Ur
TWo more importart points about the internal
energy are as follows :
(i) The iaternal energy depends upon the
q_uantity of the substance contained in the system.
Hence it is an erten sive propeny .
Consider a gas enclosed in a cylinder fitted
- (it) The internal energy of ideal gases is a with a frictionless piston (Fig. 5.7).
tunctlon of temperature only. Hence in isothermal
processes, as the temperature remairs constant,
there is oo changc in internal energy r'.e.
AE=0.
Sign of AE. Obviously, if E, >
e (or Eo >
E ), the extra enerry possessed by the system in the
initial state_(or the reactants) would be given out
and AE will be negative aciording to t[e above
equations.
if Er . E, (or E* < E/, energy
.__ _Similarly,
will be absorbed in the process and aE witt be
positive. Hence
AE @t La) is mg ive ilenrg is etolvd
and M (or L(l) is positiw i,fnqy k uhsortd FIGURE 5.7. Expansion of a gas.
Unlts of E or U. The units of energr are eryr Suppose
(in CGS units) orTbuies (in SI units)
Area of cross-section of cylinder = 4 sq. cm
l joule = 107 ergs.
(2) Worlc As learnt ftom lessons in pbpics,
Pressure on the piston =p
(whichis slightlyless than internal pressure of
wo* is stid to have been done whe:ttever *e point oy .
the gas so that the gas can expand)
s/8 Nerl Course
Distance through which gas expands : d/ cm Units ofw. The units of work are the same as
Then as pressure is force per uuit area, force those of energy viz. erys or ioules (1 J : 1 Nm
(f) acting on the piston will be/ : P x a = 1 kg m2 s-2)*
.. Work done by the gas (i.e. the system) Work done itr isothrmal reversible expan-
sion of an ideal gas.** The small amount of work
= Force x Distance=/Xdl=Pxaxdl.
done, dw, when the gas expands tbrough a small
B\t q x dl = dV, a small increase in the volume, dV, against the external pressure, P is given
volume of the gas. Hence the small amount ofwork by 6w= -PdY
(dw) done by the gas can be writtcn as
.. Total work done when the gas erpands
6w: PxdV from iuitial volume Vr to final volume V2, will be
If the gas expands from initial volume Vl to v2
lho final volume y2, then the total work done (w) t
will be given by
w=- I PdY
)
v2 v1
= nRT
,: I Pdv
For an ideal gas, PV
._rRT
i.e.

v2
If
the extcrnal prcssure P against which the
gas expands remains almost constant throughoxt Hence ,=- [l'iru
,rRT
ihc process (so thatitis ineversible apansion), tho )
above result may be written as v1
v2 For isothermal expansion, T = consta so that
( v?
w=P I dV = P (vz - V' ) = P. av
,y= -nRT
Ir
vl
J
)
I VdV
v1
whcre AV = (V2 - Vl) is thc total change in v,
volume of the gas (or the system). This is thq = - nRTln ;;Yl
cxpressioa for work of irreversible expansion.
If the external pressure (P) is slightly morc
than the pressure of thc gas, the gas will contract = - Z.:03 nRT log 3
i.e., the work will be done by the surroundings on
the syste rn, However, the same formula will apply = - 2.303 nRI log I
Pz
for the work done.
It may be mentione rJhere thatP is lhe extemol
(At const. temp., P,,r, = ,rr,
prcssure and hence is sometimes written as Prrr so ". f, = | )
that r? = P.rr x AV
The -ve sign indicates work of expansion.
Sign ofw. Accordinglo the lutest S.I- convetr (3) Heat. Just as work is a form of energy
lion, w is takerl as negtive i[ work is done by the which is exchanged between the systern and the
.ry.irem whereas it is taken as pasrlive if work ts done
on lhc slstem. Thus [or expansion, we wrilc
w = -P AV
and for contraction, we have
w = PAV churyed between the system and the surroundings as

+Work = Forcc x distance = N x t t =Nm= IJ

Force = mass x acceleratron. Hencework = kg x ms-2 x m = kg m: s-2
r+For reveNible expansion, externalpressur is not constant but is chanted continuouslyso as to bc infinitesimallysmaller
than the intemal prcssu re of the 8as
FIRST LAW OF THEBMODYNAMICS AND CHEI\4ICAL ENERGETICS 5/9

a fesult of tlv differcnce oI temPefature between oI some olherform oI met&) nust be produced. Fot
,lrem. It is usually represented by the lctter 'g'. example,
It maybe pointed olut ahat both heql and io* (o) In the operatioo of an electric fan, the
oppear onty at the bound.ary of the system. electrical energ5r which is consumed is converted
Sign of'q'. When heat is given by tJte system iato mechanical work which moves the blades.
to the surroundiDgs, it is given a negntlvc sign. (D) The electrical energ5r supplied to a heater
When heat is absorbed by the system from the is converted hto heat whereas electrical energy
surroundings, it is given a posttive sign. passing through the frlaraent of a bulb is converted
Units of 'q'. Heat is usually measured in terms into light.
of 'calories'.1 calorie is d6ned as the ryontity ol (c) Water can bc decomposed by an electric
heat required to rsise the tempemturc oI one gram of
currsnt into gaseous hydrogen and orygen. It is
water thrcugh ]"C (in the vicinity of I 5Y) .
formd that 286'2 kI of electrical energ5r is used to
In the S.I. slEtem, heat is expresscd in terms decompose 1 mole of water.
ofjoules. The two types of units are related to each
other as under : H2o(I) + 46. 2 w H, (c) + o, @)
: ---- +
I caloie 4' 184 ioules Eectricel
cncra/
which means the same thing as
This energy must have been stored in
1 joule = 0.2j90 calories
h/drogen aod orygen since same amount of energy
It may be noted that whereas internal energy ia the form of heat is released when 1 mole of water
is a state function, work and heat are not state (liquid) is obtained ftom gasoous hydrogen and
functions because their values do not dcpend mere- orygen.
ly on the initial and final states but depend upon
the path followed. I
Hz@) + G) H2o(t) + 2K' 2 W
Dilference between heat and work When heat ;o1 Heat cner8y
Ls supplied to a gas in a system, the molecules start -.
moving faster with greater randomness in different Thus 286' 2 kJ of electrical energy which was
directions. However, when work is done on the supplied to the slnten (rub*ance under obseNa-
system, then initially the molecules start movirg fibz) has been recovered later as heat energy i.a.
down in the direction of the piston. Thus phere4t
heat is a random Jorm of energ, wo* is an organised
Electrical energr supplied = Heat energy
produced
form of energt
Thus energy is consewed in one form or the
5.6. First Law ol Therrrrcdynamics . . r : .r:::: :rr. i+ .,:,:r::::.::.:
:
other though one form of energ;r may change into
Delinition. Tbe first law of thermodlnamics the other form.
is simply the law of conservation of energr which (ii) It is impossibk to consuuct s peryetual
states that nolion machine i.e. amachine which would.produce
wo* continuousty withoul consaming enetp
(Helm-holta 18a7).
(iii) There is at eruct equivalence between heat
and mechanical wo* i.e. for every 4. 184 jouks of
wo* done, 1 caloie of heat is produced and ice
vena (Joule 18,l()).
The above three observations are also some-
Justification for the First Law of Ther- times taken as alternate statements of the fust law
modynamics. This law is purely a result of ex- of thermodyranics.
perience. There is no theoretical proof for it. Mathematical fonnuladon of the llrst lav of
However, some of the following obseruations sup- thermodynamics (i .e. Relationship betweei intemal
port the validity of this law mergl wo* and heat).
(i) Whenever a certain quantity oI some fom The internal energy of a system caa be in-
of energt disoppears, an exsctlt equivalent amount creased in two ways (Fig. 5.8) :
5/10
Ned CouYse Chent istrg

+q

(HEAT (woRK
ABSOREEO) DONE ON THE
SYSTEM)

INITIAL STATE FINAL

STATE

FIGURE 5.8.lncreasing internal energy by

absorption oI heai and by doing work on the system.

(i) By supplying heat to the system conditions of temperature, Pressure and volume is
E^ (state A). Now suppose the conditions are
(li) By doing work on the system.
rhanged so that the internal energy is EB (state B)
Suppose the initial internal energy of the sys-
: (Fie. 5.9). Then if internal energy is a state functioo'
tem Er be
ih"-difl"r"nc" AE = Es - EA must same
If it absorbs heat 4, its internal energy will
become: Er *g
If further work w is done on the system, the
internal enerev will further increase and become =
-Let
E1 + q + w. us call this final internal energy as
E.Then Ez=Er+q+w
or E2-Et=q+w
or "'(' is a state function.

This equation is the mathematical fornula-

tion of the flrst law of thermodynamics.
If the work done is the work ofe)Qansion, then
w = - PAY where AV is the change in volume and
P is the external pressure. Eqn (i) can then be
written as 6g=q_pAV UJ
G,
f
or ,_g --tl! ' .'.(io UJ

E
Tlvo interesting results follow from th math-
ematical formulation of the hrst law of ther-
EodlDamics, as under : - VoLUME
-+
(i) Neither 4 nor w is a state function, yet.the FIGURE 5 9. Changes in internal
qunatiiy q +w ( = 69; is a state function (be- energY in direct andieverse Paths'
causc AE is a state functioa).
(rl) For an ideal gas undergoiag an isothermal Internal energr change ln terms of heat
Herce q= evolved or absorbed. From hrst law of ther-
change, AE = 0. -w modynamics, 4=AE+PAV
i.e. the heat absorbcd by the system is equal to
Ifthe process is carried out at constant volume
work donc by the slstem. AV = 0. The above equa-
(say in a closed vessel),
Itrternal enrcSr 18 I ststc furcdotr - A deduc' tion tben reduces to the form
don from the Flrsiiaw of Ttermodynamlcs. Sup-
pose tie internal cnergy of a system utrder some
dE = q, @ irdicating constant volume)

;oi using thc symbot U in placc of E fot intcmal cncrB/, wc c8n \vrite

AU={+$,ond4-AU+PAV
FIRST LAW OF THERN,IOOYNAMICS AND CHEMICAL ENERGETICS s/1'l

tt
PP
like internal energy, the work done during a
V+ V+
process does not depend merely on the initial and
the final states of the system but it depends upon
the oath followed. Hence work is not a state
funciion but a patb function. This may be made
clear as follows :

Suppose we wish to change the s1'stem from

A to B. This may be done by following different v-)
paths as shown in Fig. 5.10. Confining ourselves
to the work of expansion oaly, we know that the FIGURE 5.10. Dtfferent paths followed br
work done for a small change ia volume dV is gotng from state A to stale B.
PdV where P is the external pressure. Thus the
total work done is the sum of PdV terms and this That heat is not a state fitnction follows direct-
is equivalent to the area under the curve in the ly from the mathematical formulation of the first
P- V diagrams. law of thermodynamics viz.
From Fig. 5.10, it is obvious that areas under AE= q+n) $ q= LE-w
the curve are different and hence the work done is As AE is a state function but l, is not a state
different when different paths are followed. function, hence q is also not a state function.

AcrordiDg to first law of thermodynamics LE = q + w

q, AE and P are injoules
Heat absorbed by the srstem, q is + ve.
Heat given out by the srstem, q is
-ve.
Enerry absorbed by rhe system,
(,.e. intemal eners/ ofthe system inffeases), AE is +vc
Energy given out ry the system,
(ie. intemal ener$/ ofthe s)stem decrcases), AE is
Work done on the systeDr, r, is +ve.
-ve
Work doDe by the system, l9 is
-ve.
t..\ \\ll'l.tl L Calculate lhe intemsl enetry (ii) Here w: +5kJ
change in each oI lhe following cases : - q= -15k1
(i) A xystem absotbs 15 H of heat and does 5
kJ of wo* .'. 4s.olding to first law of thermodluamics.
. 0i) 5 A of work is done on the system and 15 LE=q+w=-15+(+S1 = - lgkJ
kJ of heat is given out by the system.
Solution. (i) Here q = +15k1 ie the hternal energr of the system dccreases
by 10 kJ.
w: -5kJ EX{NIPLE 2. Calculde the omount of wo*
.'. According to first law of thermodlnamics, done in each of hc following cara :-
LE=q+w:15+(-5):10kJ -
(i) One mole of anideal gas containcdh abulb
Thus the internal energy of the system in- of 10 lihe capaciE al I aon is allowed to cntet into
creases by 10 kJ an evaaukd bulb oI lN lifrz capaciay.
 5112

(ii ) One mole of a gas is allowed to expand from Putting n :

Vt = 15 L,
0.75 mol,
a volume of 1 litre to a volwne ol 5 litres against the
constont externol pressure of 1 atm (l lihe otnt :
Yz = 25L,T =27 + 273 =300K and
101.3 J) R : 8.314 J K-l mol-l,weget
Also cala.lole the inlemol enetgt charye (A,U) irt
eoclt case if tlrc ptxess weru conied, out adiabatically. w = -2.303x 0.75 x 8.31a x 3o0togff
Solution. (i) w = P.xtx LV
As expansion takes place into the evacuated
: -955 sJ
(
-ve sign represents work of expansion)
bulb, i.e. against vacuum, P.,, = 0.
For isothermal expansion of an ideal gas,
Hence w = 0. AU=0
For adiabatic process, q = 0 .. LU = q l = - w = + 955.5 J
w gives q
.'.AU=S+w=0+0=0 IaXAi\ll'l,E on monoxide is allowed to
,1. Curb
(,r) Av : v2 - Vr : 5-1 = 4litres expand isothermally attd, reversibly from l0 m3 kt
20 m3 qt 300 K and work obtained is 4. 754 H. Cal-
P:1atm
.'. w= -PAV culate the number of moles of carbon monoide.

= -1x 4litreatm = -4litre atm Solution, w = 2'303nO ,.*

= - 4 x 101.3J = - 4052J +
Altematively, tsing the SI units directly
P = latm:101325Pa
4754 = 2.3O3y n x 8.3t4 x .ro0 x togff.
AV=4L=4x10-3m3 This gives n = 2.75 moles.
.. w=-PxAV A 5-moles cylinder contained. 10
= -107325 x 4 x 10-3
J J= -405.3 m ot 27oC. Due to sudden leakage
The negative sign implies that thework is done through the lrcle, all the gos escaped into the etmor'-
by the system. phere and the cylindcr got empty. If the atmospluic
For adiabatic process pressure is 1 0 atmosphere, calculate tlrc wotk done
by the gas.
AU = q + w = 0 _ zl05.3J
= _ 405.3 J Solution. Y;,,,r1 = 5L,
Irt \,l.l,_ 3. Cqlculate the maximunr wo* T = ZTC : Z7 + 273K :300K
obtained tylrcn 0.75 mol of an ideal gas expands
isothennally and. rcversibly at 27'C from a volume of -- zRT 10x0.0821x300 :246.3
L
15 L to 25 L. Also calculate the value ofq and h,U
,
f^ot - p 1.0
ac c on tp any i n g the proces s.
AV = V1,,,r - Y^*, =v46 3-5=241 1L
Solution. For isothermal reversible expan-
sion oTTnIE gas. w",p: PAV = - lx24l.3Lntm
v, v,
w=-nRTln jvl = -2.303nRTlog.i
= - 24L.3 x 101.3 .I
vl : _2U43.7 J.

PRAbLEMS FOR
1. 500 joule of heat was supplied to a system at con- even when 2In joules of hcat is supplied to it ?
stantvolume. It resulted in the increaseof tempera-
ture ofthesystem from 20'C to 25'C. What is the
[415- rk dono by tho sltstcm = 300.1]
3. Calculate thc work done when 1 0 mol of water at
.
cha[ge in interDal eners/ of the system?
373 K!"porizes aSainst an atmcpheric pressure of
l'rr'" aE = 500 JI 1.0 atmosphere. Assume ideal gas behaviour.
2. What would be the work done on^,y the slstem if
[415.31fi1J]
the i[ternaleDerry of the s]stem falls by 100joules
 FIRST LAW OF THEBMODYNAMICS AND CHEMICAL ENERGETICS s/13

LI
l At constant volurre, Av = 0. Applylng _ 1x0 08?1 x 373 _
30.6 L
LB = q + w = I + PAYwegetAE = I = 500 J.
3. pv=rRrorv=n$ "-,:t":,,ff"jiT;.J;,:,rf :"J"r..,',
5.7. Enthalpy or Heat Conteni Thus if H, is the enthalpy of the system in the
If a process is carried out at con^stant pressure final state and H, is thevalue in the initialstate, then
(as is usually the case, because most of t he reactions Hr=Er+PV,
are studied in vessels open to the atmosphere or if
a system consists of a gas confined in a cylinder iind Hr = E1 + PVr
frtted with a piston, the external pressure acting on Putting these values in equation (vi), we get
the piston is the atmospheric pressure), the work of qp: Hz- Hl
exparsion is given by
ry= - PAV ...(r) ...(vii)
where AV is the increase in volume aad P i.s the where AH : Hz - Hr is the enthalpy change of the
constant pressure.
system.
Acording to frst law of thermodynamics, we
know that Hence enthalpy changc of a sysbm is eqsl to the
hcst absorbed or evolvcd b! the qstcm at corlttant
q=LE-w ..,(ii)
Prslflfe.
where 4 is the heat absorbed by the sptem, AE is
the increase in internal energ5r of the system and p It may be remembered that as most of the
is the work done by the system. reactions are carded out at constant pressure (i.e.
in the openvessels), the measured value of the heat
Under condition ofconstant pressure. putting
evolved or absorbed is the enthalpy change.
tv - FAV and representing the heat absorbed by
=
Further, putting the value of 4, from equation
qP'vte get
(vii) in equation (ur), we get
qP:AE+PAV -(r:rr)
AH = AE+PAV ...(viii)
Suppose when the system absorbs qrjoules of
heat, its internal energy increases from E, to E, and Hene tle entlwlpy change acconryarying a proes
the volume increases from V, to Vr. Then we have
AE=Ez-Er -.(iv)
and AV=Vz-Vr ...(v) Physical concept ofnthslpy or heat content
Putting thesevalues ia equation (rri) above, we In the above discussion, the enthalpy has been
get dehned by the mathematical expression,
qp=(E,-El)+P(V2-Vl) H=E+PV Let us try to understand what this
quantity really is.
o, Qt : (E; + PVr) - (Er + PVr) ...(vi) It has been described earlier that every sub-
Now as E, P and V are the functiors of state, stance or system has some dehnite energystored in
therefore the quantity E + PV must also be a state it, called the internal energy. This energy may be
function. Tfte thermodynumic quantity E + PV is of many kinds.
called the heat contc[t or ent}ldpy oI lhe system The merg slored within the substance or the systen
andis represented bythe symbol Hi.u. the enthalpy that is avaibblc for conyers n into htat
h4at is calted
calte.l
may be defined mathematically by the equation the h.sl con ent or enthalpy o! the subsmncc or the
qdlem.
5114

As H = E + PV and absolute value of E
cannot be determined, therefore, the absolute
value ofthe heat cotrtent or enthalpy ofa substance
or a system cannot be measured. FortuDately, this
is not required also. In the thermodynamic proces-
ses, we are concerned only with the changes in
enthalpy (AH) which can be easily measured ex-
perimentally. Further, it may be mentioned here
that as E and V are extensive properties, therefore
the enthalpy is also an eatensive propefiy.

l. Both intemal enerry and en(halPy are state furlc- 4. IDternal enerry change is tbe heat svolvcd or ab-
tions. sorbed at constantvolume while enthalPy change is
2. Both are exteDsive ProPerties. that at constant Pressure ie. AE = qu , AH = 4p.
3. The absolute t?lue of nei*lcr inEmal eDerry nor 5. In a cyclic process ie. when the q6tem returns to
enthalpy can be determined. origi[al state after a number of changes, AE or
AH=0.

5.8. Relationship Between Heat of AH=AE+AnsRT -.(vi)

Reaclion at Constanl Presaure
and lhst st Constant Volurne,llrrilEllrii+;i:1r,i:i:ir:l:j::':r: whereAnr: nz -
nr is the difference between the
riumber of moles ofthe gaseousproducts and those
It has already been discussed that of the gaseous reactants
Qo = LHatdq,: LE (,) Putting the values of AE from eqn. (i), eqn.
(vi) becomes
It has also been derived already that at con-
stant prcssure
qp=ql,+ NlrRt -.(rir)
AH=AE+PAV ...(r0

where AV is the change in volume Conditions under which (lp = (l'

Eqn. (ii) can be rewitten as
or AH=AE
AH=AE+P(Vz-v1) (i) When reaction is cqded out itt s closed
vesJel so that volume remains constant i.e. AV : 0
= AE + (Pvz - Pvr) ...(rr0
(ii) When rcaction involves ottly solids or
where V, is the initial volume and V2 is the hnal liquid: or solutions bttt no garieous reactdnt ot'
Yolume of the systom. product. This t-sbecause the volume changes of the
But for idealgases, PV = n RT so that we have solids alrd liquids during a chemical reaction are
negligible.
PV, = 1,PJ1' (iv)
(iii) Wen reuctiott itvolves Easeous reactunts
ondpruducls but theirrumber of moles are equol (i.a.
and PV, : rrRT (v)
no = nr) e.g. in the reactions
where n1 is the number of moles of the gaseous H2G) + CtzG) + z}{Ct G)
reactants and z, is the number of moles of the
gaseous products.
C(s) + Or@) .........-...- Co, G)
Substituting these values in eqn. (rid), we get Thus q, is different liom q" only in those
AH = AE + (t 2RT - nrRT) reactions which involve qaseous reactants aod
products and (n,
\' / SokoLt ) (^,\ *
\ t Sos.ottt
=AE+(nz-nr)RT
 FIHST LAW OF THEBMODYNAI\,IICS AND CHEMICAL ENERGETICS
s/15

NttrMiE"-BjieAiI-F ffi mr-..r.r'ro,**SHrprrl)rr\liDNq,ANDq,.

or aH =AU +d,,rRT
Here L E= (D-\\
_ t 8os.ou,

lf qparLd qu (ot LH and AE or AU ) are in calories,

R = I .987: 2 calldegree/mole.

If they are iD kcls,

R = 0.002 kca t/degree/mole.
IftheyareiDjoules,R=8.314JK-lmole-l and if they are in kJ,
R = 0.008314 kJ K-lmole-l.TistemperatureinK.

Also, we are given

LE (ot q,) = -3263.9H mol-1
T=25.C=298K
Solution. The reaction is R : 8.314 J K-1 mol-l
I
CuHu(t)+71o2@t 6cork) +3H2c)() =
8i# t-r r-, ..r-,
-
In this reaction, O, is the only gaseous reac- AH (or qr) : AE + d,r8 I{T
tant and COz is the only gaseous product.

'" Nts=nP-fi'
=-3263.e. l-:) l9#)/
\ 2/ ( 1000
,rrr
=- 3263.9 - 3.7
:(t-, _1 :
+ : - 3/2
l-= -3267 6 kJ mol-r.
2 -

1, The heat of comhustion of CHa k) ar coDslaDl atmcpheric pressure and 373 K is ---223.6 kJ
volume is measured in a bomb calorimeter at 29g.2 mol-l of NH. NOr(s) decomposed. What is the
K and found to be J/mol. Find rhe value
-885389
of enthalpy change. value of AU for the rection under the same condi-
,rns. _t90347
[ J mol -l ]
2, The enthalpy change (AH) for rhe reaction
tioDs ? (Civen R = 8.31 JK-l mol-l)
N2G) + 3H2G:)- 2NH3@) is (A.1.5-B- 1998) [ Ans. .9 mot -l I
-232 kI
,
38 kJ a r 298
K. Whar is AU ar 298K ?
-92 5. When 0.532 g of beDzene (c6H6), boiling point
(A.LS.B. 1991 S, 2@1, p5.8.95, N.C.E.P-T.) 353 K is bumt with excss of uygcD in a coDstant
volume srstem, 22.3 kI of heat i! given out. Calcu-
I Ans . ___r7 . 42 kJ] late AH for the combustion process (R
3. The internal energy change (aE) for the reaction = 8.31
cHa6) r 2O2G) ...._ CO:G) f 2H2O (l) is IK-1 mot-l) (A.I.S.B. 199e)

-885 kJ mol-l ar 298 K

what is aHar298 -3274 2 kJ mot-ll
I Ans.
K? @.PS.B. 1gg4) [Ans.-SE9.96 lrl mol-11
6. The heat of contbustion of naphthaleDe
(ctoHt (r)) at constant voluDte was found to be
4. WheD NHaNOz(s) decomposes at 373 K, it forDrs
N2 G) and H2O E). The aH for the reaction ar one - 5133 kJ mot-1. Cal te tbe \.alue ofenthalpy
change. s. _ sr2s.oa kJ mot-i]
 s/16

H INT$ FoR DrFFr cuLT ?RortElve

4. NH4NO, (r;...- NzG) + 2HzO (!), .. aE = - 6fifr7-u u,"r-r
c,,1.s=3-O=3
AE=AH-AnrRT = - 3269.8 kJ mol-l
Calculate AH as in solved example above.
= -223 6 -3 x(8 314,/1000) x373
6. qoHt (r) + 12 ozg)+ 10 CO2 e) + 4 H2O (l),
= - 232 9 kJ mol-1.
5.0 532 g CuHu = 0.532fi8 mole
AE = - 5133 kJ mol-1
6n=10-12=-2

l. lcal > ljoule> lerg.

2. WhcD a real gas is allorcd to crpaod adiaba c2lly from a region of high pressure to a region of low pressure
through a fine hole, it is accompanicd by cooling except H2 and He whicb get warmed up. This phercmenon
is knovm as Joule-Thomsotr effcct
During sdiabofc qpansion ofa realgas, enthalry (but trot intemal eners/) remaiDs constant. It is, therefore,
called tscrltrolplc pro..s.

ffi4. The iemperaturc at whici a real gas sho s Do cooling or heating effect on adiabatic expansion is called
Itrvelsior teDpcrrtuE Below this temperature i! shours cooling effect while above this temperaturc., it sho\^6
heating effecl
tI2 and He have very lo$, inrrsion tempc[atures- That is why they show hcating effect at rmm temperature
during adiabaric expansion.
, 6. During isothermal expansion ofan idealgas AE = 0, AT = o
. . H = E + PV or aH = aE + A (pv) = AE + PnRAT = 0 + 0 = 0. Henc enthalpy remains constaDr.

5.0. H.rat capacity, Specitic Heat c3f:ily Thus if dq is small amount of heat absorbed by a
and Molar Heat Capacity ,
!ii;i i: ::i: ,. , , :t: , ,':.:'.:.,,r'., r system whici iaises the temperature of the system
5.9.1. Delinitions. by a small amount dT (say from T to T + dT), then
the heat capacity of the system will be given by
Thc hcat capaciE of a ,\!stem is deJineil as the
amounl oJ heat requircd Ut rdire lhe tempersture oI c=# ...(,,)
the slslem througlt 1"C.

Thus if q is the amount of heat supplied to a

system and as a result, if the temperature of the
system rises from T, and Tr, then the heat capacity
(C) of the system is given by

c- = =-s _- =
Tz - Tr AT
_-s- . (i),"u""ll;:'l:#J,tlf;*,ili':,11ili;"',t:H:n;l
Thus
However since the
temperature, therefore
considered over a very n
 FIRST LAW OF THEFMODYNAMICS AND CHEMICAL ENERGETICS
5117

Example. To understand the difference be- Now, according to first

twcen icat capacity, specific heat capacity ard
law of ther-
modynamics, wc know that
molar heat capacity, let us take the tollowing ex-
ample :
dq=m+Pav ...(iii)
A piece of Al metal weighing 3 g requires ^ dE+ Pdv
...(ir)
-5 4 J of heat to raise the temperature from 29g K
trt
to 300 K. Then _ Wen lhe volume is kcpt constant, dV = 0 and,
Heat capacity of the piece of there[ore, equation (iv) becomes
Al
(.4 I
= ,'t =z.ttt1-, lc,= ffi)
Specific heat capacity of Al ,tl ...(,)

5.4 r orlor aa idcal&z,rr{,

= o.eJs-rK-r .De wnttcn
=
ffi
Molar heat capacity of Al
as
this equatiotr maysimply

\.4 .1 _ .rd.3
3x2"- J mol-t K-l ...(rr)

(. 1mol ofAl = 27 eof At) he

Bvidently, the amount ol heat, q required to
raise the temperature from T, toTrof masirn gram
i'h
emperqlure al cor$lan! volu4w.
of a sample and having specific heat C, can be
calculated from the expression _ Mlen the pressure k kept constant dnring the
absorption of heat, equation (iv) becomes
q=ruxcx(Tr-Tr)
=mXCXAT ',= (H),.'(#). (uii)
It is useful to remember that the specific heat
capacity. o[ water is 1 cal g-i K-l or Also, we know that the heat content or enthal-
_
py of a system is given by
4 18 Jg-t 1-t.
5.92. Tlpes of heat capacities or molar heat H=E+PV
capacities. Since'q' is not a state function and Differentiating w.r.t. T at constant R we get
depends upon I he pat h followed, therefore C is also
not a state fulction. Hence to know the value ofC,
/au')= i(.,/,
oe'\ *'
, -/av\ (viii)
tlre conditions, suchas constqnt volume or constant
Irr,], l-,/,
pressure have tobe specified which define the path. Combining equations (rti) and (vi ), we get
Thus there are two types of heat capacities, ;hich
are
(i) Heat capacity at constant volume (repre_ (r)
scnted by C,). 1..=
(ii) H_car capacity ar constant pressure (repre_
sented by (o). .be putor.for
in
ony ideol gas. this equation may simply
the form
The hcal supplittl ta
ture through loC
coNtunt it called vohtmc.
cr=F
^dH
G)
Similarly, thc hea
lemperatwc thro gh
surc constant is callcd heat cspacity at conslsnt
prafsure,

ts ls
.Fcranf.c.i.-,r<.it.a0bcsh^wn,hdltheint..,atencr./isindepcndentof\,olumcanddepcndsoilyonthe.Ercraturc
 Pradeep's
s/18

Alternatlwly, from equation (di), we can the system is to be raised through the same valuc as
directly say that at constant volume, then some extra heat is re-
(6q)" quired for doing the work of expansion Hence
"P_ dT
Cr, C,,.

But (6q)p = dH The difference between the heat capacities of

an ideal gas can be obtained by subtracting equa-
(according to def. of enthalpy change) tion (r.'i) from equation (x). So we have
... -"p-- dtl
df
dH dE
(._C = =::_- ...(xi)
'r dt dT
Note. Heat capacities C, and C, as defined
But H:E+PV (bY definition)
moleJhese are
above are the heat capacities per and PV = RT (for 1 mole an ideal gas)
of
therefore, sometimes rePresented by C, and C, .. H:E+RT.
Hence for n noles of the substance, we have Ditferentiating this equation w.r.t. I we get
c"=ne" and Cr=nQ dH dE (rii)
5.93' Relatlonshlp btwen Cp and Cu' If the dT dT
dH
or #'ffi=" dE ..(r,'i)

Combining equation (xr) and (xil'i), we get

for 1 mole of an ideal gas

Thus C, is greater than Cl bythe gas constant

R, i.e., approximately 2 calories or 8 314joules

USE OF SPECIFIC HEAT

Sotution. (a) EnergY needed (4)

=r?1 xCxAT
=10.0x045x(500-25)J
= 2137 .s J
(b)q=mxcxaT
2137'5=m x 0 13 x (500- 25)
or m :34 69
SECTION TV the energy required is greater than the energy
evolved, ifie nei result is the absorptiotr ol cnugt
ENERGYCHANCES and the process is called'endothermic' '
DURING CHEIVICAL REACTIONS Thus all chemicat reactions are usually ac-
5.1 o- General lntroductio n i:il:iiri:iiiii::r:

A chemical reaction involves rearrangement

ges manifest and the use to which they are Put are
given below :
 FIRST LAW OF THERMODYNAMICS AND CHEMICAL ENERGETICS
5/19
(i) Buming of coal ia air produces,hear. That surroundings is higher, the work is said to be done
is why it is used as a fuel o,l the system.
C (s) + O: G).-.* Co2 G) + heat. 5.1 1. Exolherrnic and Endothermic Reactions. .
(ii) Buming of naturalgcs (a mixture of lower
hydrocarbons) pro d\ces heot and lighr. Therefore, Exothermic Racllo[. Thesg are tl]}[jy. reacrio$
it is also used as a fuel. which ue auatrqoudd br the efolutiafl o! hoat.

+ 2ozq)-
CHo (g) Coz @) + z}{2o(t) The quanriry of heat produced is shown
Methane + hear + light alongwith the products with i.plus,sign. A few
2qH6 G) +7 ozk).......,4co2@) + 6Hzo(t) examples of exothermic reactioni are givin below :
Ethane +heat + light C (r) + or(s) .._ Co2 k) + 393.5 U
(iii) Combustion of petrol (CroHrr) in at
automobile engine produccs /r eat and rvechqnicql
Hz Gr ,i
1

Oz k)._..- Hr() (; + 295.s L1

work.It is, thercfore, used as a fuel for automobile Nr6; + r-Hr1s) .........- 2NH3Q| + gz.4kt
engines.
cH4k) + zoz@)...-, Co2G)
2 CloHz2 (t) + 31 orG) ....-._ zo CO2 @)
+ 2H2()@) + 890.4 k.l
+ 22 HzoG)
11
.. - (i.v).Slow combustion of carboltydrutes
biological systems produccs,/rcar
in C4Hrok) + +OrG)........*
which maintains
the body temperature. ttor lsl +5H, o G) + 2658 kJ
CuH,rOu(s) +6 Or(g)......+ f agz@) +6lH2O (l)
+ heat
(v) Bumingofcandle rn ari produces heat and
light. It k, therefore, used as source ot light.
i
Thking wax as C,rHr2, we have
C,r Hr, (s) + 2j Oz @) -........., t5CO2
@)
+ 16 H2O k)
_(ui) in a golvanic cell G) + 02 k)
N2 2No (s) - 180. 7 kJ
Produces maybi used to run
an electri c(r) + H2o(i)
beli, etc. -.....-
- k) + H2 k) _ 131.4 kJ
co
Zn (s) + Cu2+ (aq)...-...- Zr?+ (aq) + Cu(s) C(s) + 2s(r) -......* CS2k) e2. 0 kr
-
*dt H2@) + t2@).-,
zHr (s) _ sz.skJ
,@- 2 Hgo(s) .6
-....... 2l.tg (t) + or(s) - 181 kJ
Exothermic and Endothermlc mncfions ln
Modes of terms of AH. The enthalpy change (AH) accom-
sJAtem and the
panyng a reaction is given by
mon forms of e
tem and the sur AH = Heat content of proctucts
(r) Heat which is due to the difference
of - Heat contnt of reactants
temperature between the system and the surround- =Hp-Hn
rngs and flows from higher temperature A reactio_n is exothermici.e., heat is given oul
temperature.
to lower .
ur a reaction if tbe total heat content of t-he
reuc_
tants is more than that of the products,
r..e.,
Hn'Hr
But if it is so, then according [o the above
equation AH witl be negative. Hence
5120
Pratlecp's:i 7,,.: ttt:t t tslii|lfrlD)

MI is wptivefor emthcrmic reactions'

REACTANTS
Thus the exothermic reactions given above
I
may be written in terms of AH as 1
i I

C (s) + OzG)- Cozk), o; o-

J
A H=Hr-H*
ItttEGATIvEt
t'
AH = -393'5kJmol-1
-F I

HzG) +
1
zuJ
iorttl PRODUCTS

-Hzo0),
AH : -285'8 kJ mol-l PROGREES OF REACTION
Nzk) + 3HzG)- 2NHr(s),
LH : -92'4kJ mol-r
cHaG) + 2o2G)- Coz@) + zHzo(t),
AH: - 890'4kJmol-l o (L
J
c+Hro @ *+oz@)-4coz@) + sH2oG),
I
F
LH : mol-l zul
-2658 kJ
A reaction is endothermic i'e' heat is absorbed
PROGREES OF REACTION
in a reaction if the total heat content ofreactants is
less than that of the products, i'e', H* < H,
FIGURE S.11' (a) Exothermic rection
(b) Endothermic reaciton.
Then, according to the equation
AH: Hp Hn,AHwillbePositive'Hence 5.1 2. Thermochemical Equation i::: ::::::::::i::::::: ::::i:: ::::i:i:::: li:::i: i:::::::i:::::i::: i :

-
Whsn a balmceil chernicale4uul';ionnat only
indi-
LH is posilivefor enilothirmic rerc-tiorts'
cati the quanlilics of the differet reailants und
Thus the endothermic reactions given earlier proittut^t'bul obto indicates lh'e &tttount of hectl
may be written in terms of AH as 'evolved
ar absorbed (os in lhe above teucfiorui), il
+or(g)- 2NoG), is called a lhermochemical equutiow'
NrG)
: However, contraryto the usual practice about
AH + 180'7 kJ mol-r may
the balanced equations, fractional coel'l'icients
equation' For
c(s) + HroG)- CO (8) + H2k)' b" ,,r"d in writing a thermochemical
written
example, the formation of water is as
AH : * 1-31-'4 kJ mol-l 1

HzG) + Hzo(/)
C(s) + 2S(s).-..- CS2(/), irrrtd-
AH = +92'0kJmol-r + 285' 8 k.l mol-r

HrG)+Ir(g) ---zH.r(s), or HrG) + * ,lr(rl-

1
Hz() (i)'
LH : +52'5 kJ mol-r
AH : -28.5'fi kJ nrol-1
2Hgo(s) zHe(t) + o'G)' Thus 28-5'8 kI of heat is produced rvhen I
-'
AH : + 181'6 kJ mol-1 mole of hydrogen reacts with 0'5 mole of oxygen'
If the quantities of reactants are doublcd, tl're heat
Graphically' the exothermic and endother- produced will also be doubled' For examplc' in
thc
mic ,eaciions may be represented as shown in ibor" cute, we maY write
Fig. 5.11.
 FIBST LAW OF THERMODYNAMICS AND CHEMICAL ENEHGETICS
sl?1
2H2@) + or@) zHro(t) pletely with t mole of steam (i.e. l8g) l3l.4kJ of
.6 kJ heat is absorbed.
- + -571 mol-l
It is interesting to note that
or 2H2@) + OrG)- zH2O (t),
Heat of rcaction, AH : Heat contcnt of
AH : 571.6 kJ mol-r products - Heat content of reactallts.
If [he reaction is reversed, the sign of AH
Some Con'/entions about changes e.g.,
Thermochemical Equatlons 1
I'or
; o, G)-+
HzG) + HrO (i).
(i) For exothsrmic reactions, AH is negative
whereas for endothermic reactions, AH iiposi AH =
tive.
- 285.8 kJ mol-r
For HrO (/) ......._ H,
G) r j o, B).
(il) Unless otherwise mentioned, AH values are
for the standard state of the substatrces (i-e. Z9g AH = + 285.8 kI mol-r
K and 1 bar prcssure). Factors on which the heat o[ reaction
(rii) Thecoefficients of different substances rep- depentlsi The heat of a reaction depends upon a
resent the number of moles reacted and formed number of factors as explained below :
for the heat change reproseDted in the equation. (i) Quantities of the reactants involved. If the
quantities of the reactants are doubled. the heat of
(iv) The physical state (s, l, gerc.) ofthe difierent
reaction is also doubled. An example of this has
substances must be mentioned as the heat
already been given in section 5.12.
cvolved or absorbed dcpcnds upon the ph5ical
sl.ate (as discussed in the neK sectioo). (ii) Physical state of the rcactants and
Pr
(u) If the coelficienls of the susbtances are mul- of
tiplied or divided by some number, the value of an
AH is multiplied or divided by the same number. or
(vi) If the reaction is reversed, the sign of AH amlle. when hydrogen and orygen gases combire
to form Iiquid water. the heat o[ reaction is diflerent
changes but the magnitude remains thi same.
than when they combine to form water in thc
gaseous state i.e.,
I
H2 G) +; O, (6)..._ HrO (/),
The amount oJ heat evolved or ubmrbed in a "
chemical reaction whcn the number o! molct ol o" = -285.8 kr mol-r
Ihe rcactants as rcprevnted by the chemicil I
equttion have comptctcb reacted, ir cslbil the H2 B) + , (-)2
@)- HzO (il.
heat of reaclion.
A H = -248.8 kJ mol-r
Lct us consider the following two examples : Hence it is essential to write the symbols s, /,
C (r) + o, (g) ..._ cclz k), I ot oq. to indicate wheIher a particulai substance
is solid. liquid. gaseous or an aqueous solution.
AH = _ 393.5 kJ mol-r
C (s) + HrO k)..- Co G) + Hr(d,
AH : + 131 .rt kJ mot-l
C (diamond) + o, fu)
Co, 1,), ...._
A H = _395.4 kJ mol-l
C (graphite) + O, G) ---......r CO,
G),
A H = _393.5 kJ mol-l
5122
Pradeep's
5.14. Different TyPes ol Heats/Enthalpies
(iy) ConcentratloD of solutions. Heat o, Reaction or Phase Changes :i'i::!irr:i'i:::i rr:r'ir"''i:
change occuts when a soluto is dissolved in a
solve-nt to form a solutiou or wheu a solution is 'Heat of reaction' or 'Enthalpy of reaction' is
diluted. Therefore, if the solutions are involved
in a reaction, their concentrations affect the heat
of reaction.
(v)
depends
tants arld
reported at 298 K.
(vi) Conditions o[ constant pressure or con-
stant volume i.. whether the reaction takes place
at corstant pressure or at constant volume.
Stands(l enthalpy change. A substanc'e in its tions are as follows :
most stable form at 25'C or 298 K rutder apressure 1. Enthalpy ot combustion.
of one bar is said to be in its standard state.
The subslonce is
The enthalpy change of areaction when all the dejin ult! tlrc hedt
reactatrLs aad the products are in their standard avolv is comPletelY
states i.e. at 25' C oi 298 K and under a pressure of burnt or otidizetl in orygen.
one bar is known as the standard enthalpy change'
e.g. CHa @) + 2o2@)
It is usually represented by AH', or AH,2e8. -='co2 G) + zllzo G)'
AH = -890 4 kJ mol-r
This reaction shows that 890.4 kJ of heat is
nroduced when I mole o[ methane is completely
released when bonds are formed between the Lurnt. Hence enthalpy of combust ion oI methane is
atoms. Now as a chemical reaction involves break- 890.4 kJ mol-1.

two cases are different, viz.,

1

C (r) + * o, B)""""".. Co G),

we have '
Entholpy change of a reaction
o, = - 110.5 lJ mol-r

I Enerw reauireil to ) | Energ rekased u *e I C (s) + o, @) """""* Co2 G)'

=lareai*ebonas of l'lfotmation of bonds inl AH = - 393 5 kJ mol-l
Ithereactants )lthe Vodttcts I Complete oxidation means oxidation to CO,
If enercv required > energy releasfd, the net
and not to CO. Hence heat of combustion of carbon
result is theibsoiption of energ5r and thE reaction
is 393.5 kJ mol-l.
is endothetmic.

If energr released > energt rcquired, the net
result is thJebase of energy and the reaction is
erothermic.
The above point of view is further explained
with solved examples in section 5.18'
Standsrd hent of combustlon is the amaunf of
lpat evolved whzn one mole of the stbsance wtder
slmdard conititiar.s (298 X, I bar pressure) is
ionplaely bwnt lo form lhe producr also under
standari conttitians, h is representeil by 6If o
 FIRST LAW OF THEBMODYNAMICS AND CHEMICAL
ENERGETICS sl23
Note carefully rrrd, i, it not lhe combusliofi ths, i! tion under these conditions is called stamlard
tuking pltrce at 298 K, whkh, in luct" cunny hop- enthalpv of lbrmation.
pen, It is lhe totul heal chunge that occurs whan
the
initiul reockurts u.ttd I&aI produc* ur6 et 2:lg t
irnttpeclive ol tht lrct thrl durin{ c4n b&ion,
temperatuft is higiEr tfun 299 K.

For example, in tbe reaction

C (r) + oz G)- coz(O,
AHi = -393.59-o1-t
when I mole of CO, (g) is formed tiom its elements
viz C (s) and 02 G) Gll substanccs being taken in
(iuH,roo (r) + 6(), (q) thc standard stare), 393.-5 kl of beat is produced.
Hence standard enthalpy of tbrmation of gaseou"
6CO, (q) + 6HrO - + 284O kJ mol_r
G) CO, is 393.5 kJ mol-1.
Th is oxidaiion reaction is usually c alled,cotn_
-
btrstiort oJ J'o1tal'.
Similarly, in the reaction

Dillcrc-nt lucls and fo,rds produr.e rlillerent

2H2 @) + oz G) ...._..} 2H2O (t),
Jrnounls rrl hcJt ol (omhusli(,n. Thcsc arc usuellv AHi =
(\prcssl..d iIl rcrms (,I thcir (.rl,rrilit. v:rlues which ii -571.6 kJ mol-1
tlcfincd as lollos's : _ we observe that 577.6 kJ of heat is evolved
when 2 moles of H.t) (/) are formed from the ele_
unt
the
thl

2. Errthalpy ol formation.

The
,r'r,nditions r)l lctnpcrirlure Jnd presslrrc
trstr:rllyr'hoscn urc 2,)s K irnd I h r Drc\srrre Thi<
_ X AHi (Reactants)
*Aclually. A H"react.on Sum of enthalpics
= _ lSum
of enlhatpics
I ol racranr(
But if enthalpies of the ct"..-ne t"t"o
"." "s
r.,ol lh"n cnihalpy ;;;po]und = its cnrtralpy of fomsrior,
 Pradeep's
si24

Thus for a general reaction

NaOH + HCI '-""""-) NaCl + H2O,
aAl cC*dD
bB-- """> AH = -57'1kJ mol-l
A Ho."""ti,,n = [cAH'7 (C) 'r aAff7(D)l Hence enthalpy of neutralization of HCI with
NaOH or NaOH with HCI is 57.1 kJ.
- [a AH'1(A) + b Affl(B)] The enthalpY of neutralization of any strong
acid (HCl, HN'd3, Ff2So1) with a strotrg base
REMEMBER
For elementary substances in thc slandard state,
(AH/) is taken
the standard enthalpy of formation
as zero, The standard state of an elementary
substance means the mGst stable form of that sub-

Na++oH-+H++Cl--
Na+ + cl- + H2o , aH : -57'1 kJ mol-l
or H+ (aq) + oH- (44) ......._ Hzo O,
AH = --57 1 kJ mol-r
Thw ruufrulizalion is imply a rcaaion bawem
I,(s) whereas standard states for carbon and sul-
tlg H+ iortlt given b! tlu acid with tlu OH- ittns gitm
phur are C furaphite) and S, (rhombic) by ttu ba* ln lorm onc nwle of HrO* '
--6, we want to Predid the
enthalpy "*-p1",
"uppose
of methane' The reaction
of combustion
IS
CH4 G) + z)r(s)'C(), Ul) +2HzO o
''' AHo*r.tn'n
= [AH"rlor CO2 + 2 x A H'rforHr0]
- [A Hi Ior CHn + 2 x AHifororl
Putting the values of enthalpies oI formation
in the standard state
AHo."""tion= [- 393 5 + 2 x (- 285 8)]
-[-749+0l '*'
ionizes completelY
r,iEfi,iijou
ari
+ cH3coo-+H+
= -965 1+749= -890 2kJ
(ii) NaOH Na+ + OH-
[ .' A Hi for anY element like O, = 0l
-".
3, EntbalPY of Neutralization'

tion is 57.1- 1.9 = 55.ZtJ.

For example, when one gram equivalent of Similarly, in the neutralization of NH.OH
HCI is neutralized by NaOH or one gram with HCl. 5.6 kJ of heat is used up for the dissocia-
eourvalent of NaOH is neutralized hy HCL both tion of the weak base i.e. NH.OH Hence the
ioiutions being ditute and aqueous' 57'l kJ ot heat enthalpy of neutralization in this case is only
is produced. Thus we maY write s7.l - 5.6 = 51.5 kJ.

rmation of I molc ofH2O for thc ncutralisatlon of acid with basc'

.Thc units arc lJ mol
 FIHST LAW OF THEBMODYNAMICS AND CHEIuICAL ENERGETICS
5125

Nnte. Thc heat of neutralisation is takco for I S. Enth.rlpy ol Hydration.

gram equivalert of the acid and base This is
bccause neutralisation involves combination of 1
mol o[ H] ions with I mol of OH- ioos (as
explained abore) to form one mol of HrO. One
gram equivalent of any acid on complete dis-
sociation gives l mol of H+ ions. But I mol of an
acirl on dissociation may not givc I mul o[ tI+
ions e.& I mol HrSOn givcs 2 moles o[ H + ions For exanrplc. thc heat o[ hydrution of copper
-
srrlphate is -78.: kl mol-t. Thjs
on completc dissociation. Howevcr ons g11m -ay be relre_
sented as
equivalenl o[ HrSOr ( = 0.5 mol) gives t m-ol of
H+ ions. CuSOo (s) + .5HzO .....-...- CuSOo.5HrO (s),

4. Enthalpy of Solution.
AH = _ 78.2 kl mol-r
IMPORTANT

is bccause i[un erJuation is multiplied by a num_

hur, thc units do not change. For'cxample,
1
H, ({) + ; ()2
fi )-..- HrO 1/),
AH' = 28.5.8 kJ mol-l
-
KCI (r) + uq KCI (aq), The units oIAH" are kJ mol-1. If we mutiply thls
- AH = + 11i.6 kJ mol-r equatitu bv 2, we get
CuS( ),, (r ) + 2 H2 @) + <), (s) z Hro (t),
:rt1 )1 (a4),
-CuS( - AH. = -571.6 kI
- mol-r
AH = _66.5 kJ mol_r
-fhrrs The units olAH" are again kJ mol-1.
thc lirst case is endothermic and enthal_
py olsolLrtion : + 18.6 kJ mol-l 5.15- Meas rrement o, Enthalpy o, Heoctions ,.,,,,:,,,:,.,

Thc sccond casc is exothermic and enthalpy

ol solution = - 66.5kJmol-l

heat. For example,

C--uSO].5HrO * aq .- CtuSOJ (ar1).

AH = I t1.7k.l
,. Thus it can bc gcneralizod thar thc process oI
dissolution is Lrsually enclothermic [or
sults rvhich do not form hydrates ljko n-aCI.
_-__. _(r)
KCll, KNO, crc.
(/r) hydrared salrs like CuSO4.5HzO,
CaCl2 . 6H2O etc.
5126 Netu Course Chen istYq!
H:E+PV
.. AH= AE+ PAV+VAP
OXYGEN
FIRING
At constant pressure, AP = 0.
INLET
LEADS THERMOMETER Hence
AH:AE+PAV
STIRRER
At constant volums. AV = 0.
Hence AH = AE + VAP.
5.151. Measurement of Heat 0f
OUTER neutralisation. The heat of neutralisa-
INSULATED
VESSEL
t rn of an acid with a basc or vicc versa
can bc dctcrmined using a simplc
calorimeter consisting of a polythene
bottle* fitted with a cork having two
FILAMENT
holes, one [or the thermomctcr and the
,. other for the stirrer, as shorvn in Fig.
BOIMB
r:.1
(STEEL VESSEL) ofneutralisa-
5.13. Taking the examplc
tion o[ HCI with NaOH, the method
PLATINUM consists of the following steps :
CUP CONG.
KNOWN WT OF (i) A known volume oI HCI oI
SUASTANCE
known concentration (suy 100 cm3 of
0 5 N) is taken in one bcaker and an
cqual volume o[ NuOH rrl thc samc
concentrltion (i.c. l00 cmr rrl 0 5 N; is
FIGURE 5.12. Bomb calcrimeter. taken in anothcr bcaker.
in the compound. Combustion of the
immersed
compouad takes place. The increase in the THERMOMETER
temperature of water is noted. From this the heat STIR RER
capacity of the apparatus (i.e. heat absorbed per
degree rise of temperature) can be calculated.
(ii) Combustion ol known mass of the ex'
peimental compound. The experimnt is repeated
as in step (i)
In the above case, as the reaction is carried out
in a closed vessel, therefore heat evolved is the heat
of combustion at constant volume and hence is
equal to the internal energy change.
The value of AE can be calculated using the
formula
AE=QxArx14
m
FIGURE 5.13. Measurement of heat
Q = heat capacity of the calorimeter
where of neutralisation.
A r = rise in temperat re
hcukcrs urc kept in watcr huth till
m = mass ol rnc suos c
tain the samc Lempcrature'
ancl M = molecular maaa solution kept in the first bsaker is
Note. AH = AE + pAV.
cal0rimeter, aV = 0. Hence * ]i};,i:'[::::"t"j'l:,if;fft'r.,1".|J
AH = AE. However, this is not t hnt,l". Stirring is done to mix
relation AH = AE + PAV holds I."n"
The highest remieraruro attaincd
stant pressure. This may be seen a
.tn"t.uo ofpolyttr"n" u.i,f., f."r"o p"G,yr.*.rp *,if, i' sonreiimcs used.lt is callcd cofl'ee'lnPcalorlnreter.
" ","'"r "f.n
 FIRST LAW OF THERI\4ODYNAMICS AND CHEMICAL ENERGETICS
sl27

=fixroooxofJoules
5.153. Measurcment of heat of rractlon at .

constant prssuE (4p or AH). For any reaction oc-

follows -
Suppose the initial temperature of the acid
and the base tiC :
Final tempearature of the solution after
mixing = f'rC
. . : (t, - t,).C
Rise in tempemluls
Total mass of the solution : 100 + 100 = 200 g
tions, AH is negative whereas for endothermic
.'. Heat produced = x Specific hat
Mass reactions. AH is positive, as already explained.
x Rise in temp. Alternatively, for the measurem ett ol qo ot
:2O0 x 4.lU x (r2-rr)J =rJ(say). AH, the reaction may be carried out in a vesselwith
This is the heat produced by neulralisation of
100 cc of 0.5 N HCl. 3i""Trtfi,3l
. . Heat produced by neutralisation of 1000
cc
of1 N HC'l (containing one gram equivalent of tcmperature may be recorded ,.otT:tl:h1
calculated.
HCD
.F,."r$O"...-E".,,LE.ivl'-$...,,.ON t- rl,t:t, t..r't't ()\ o1 l,rN ,1'H.{r-r,l,oF so\.1rrrsrt()\
AND ENTHALPY OF NEUTRAI-ISATION

(ii ) 200- cmr oI 0.2M sulphuric acid is mixed

with 400 cmr ol0.5 M potassium hydroxide solutio,t.
heat of water is
qt absorbedby the
tyhat h,ould be the
ise is temperqdrre in each of the aboye cases ?
Solution. (i) 500 cm3 of 0. 1 M HCI
lgluiS". Rise in remperature
0.
:
300 78-294.05K = 6.73K = 1000
t
* 500 mole ot HCI
Heat transferred to the calorimeter = Heat
capacily of the calorimeter x Rise in temp. =0 0-5mole of HCI

= (8. e3 kJ K-r)
K) = 60. 1 kt
(6. 73
= 0.0-5 mole of H+ iom
200 cm3 ofO 2 M NaOH
Molar mass of CrHrt = 8 x 12 + 1g
: o.2
= 114 g mol-l I 200 mole of NaOH
.. Enthalpy of combustion 1000

60. I , = 0.04 mole of NaOH

= ,.Zm I 14 kJ mot-l = 0.M mole of OH- ions
: 54E1 .1 U mot-I
Thus 0.04 mole of H+ ions will combine with
0 04 mole o[ OH- ions to form 0.04 mole o[
HrO and 0 01 mole of H+ ions will remain un_
rcacted. Hcat evolved when l mole of H+ ions
ti) .500-rni o10.1 M hydrochloic acid is ruked
wilh 200 cnr ol0.2 M sodiuttt ltydnryide .rohtiott combine with 1 mole of OH- ions = 57.1 kJ.
 l)rndt: r'p's Neqt Course Chr-i"trqfiffi'
5l2A
Hencc hcat'rvolved :57 1x U 08
Heat evolved whcn 0 04 nolo ol H+ ions
..
combine with 0 04 mole of C)H- ions = 4'568 kl
In cqse (i). hcat Ptoduced : 2 284 kl
= 57.1 x0 04= 22E4N :22UJ
(ii) 2ffi cm3 ofO 2M H2So4 Total mass of tlte solution =-500+200:7(X)g
Spccilic hcat : 4 18 J K-I8 I

= !3
1000 "
200 mole ot HrSO.
xsxAJ
O= r?r
= 0 04 mole of HzSOc (l
= 0 H+ ions
08 mole of ,r XJ
)19L
-*.
,100 cm3 of 0' 5 M KOH _ 0.78.
05 700x418 =
= 1000
, ,100 mole of KoH
h case (ii),healProduced = 4 568 kJ
0'2 mole of KOH : 45(18 J
=
0'2 mole of OH- ions Total mass of the solution = 200 + ll01)
=
Thus 0 08 mole of H+ irrns will neutralizc = 6009

0'08 mole of OH- ions. (outof 0 2molcolOH- o 45rA

ions) to form 0 08moleof HrO ,fl x.! 600 x 4 l l'J

2. 2O.O g ol ammonium ritrate (NH4NO3) is dis-

20.7 kJ K-1, calculate the standard enthalPy ol

mmbustion of graPhite. J.\ls. 4 kl mol-rl (N.C.E.R.T) J'\ls -5 28 kJI
-393
FOROIFF|CULT ?R.ObLE-M.9
Z. d\ hcat capacity of water = hcal caPacily ol
calorinleler, lhc-heat gained by watcr = heat losl
by lhc calorimeter
x t2 8 r,:.ol = 125 x (2s6 5 - 286 4) x 4'184 J
= - 393 4 kJ mol-I. =52a2t=52aZkl.

5.16. EnthalPY Changes H2O (r) H2O o' AH = * 6 0 kJ mol-t

Ouring Phase Transiti Icc Water
2. Heat
- otlbPorisation.
1. Heat ofFusion.
lhe It is tlrc heut chtng accnmparqing lhc contersinn
nto oJ one mola ttf u liquid into its gxeotll sttle q' il:
hoiling ttoinl.

For examplc, the heat of fusion (AH1,,) ol ico For t]xample, thc heat ol vaporisatioll
(AH,.r,, ) ,rl rva(ir int,r its gascous:'lirte (steanl) ut
(m.p. :2'13 K) is 6 0 kl mol-r' It may he reprc-
rhe htiilirrrr l,oint r'l \tirlcr {373 K) is '10 kl'
7 lt mrrv
sented as ;
bc reprcscn'.ed as
 FIRST LAW OF THERMODYNAMICS AND CHEMICAL ENERGETICS

H2() (4 .....-...- H2O G), AH= +,t(),7kJmol-r

Watcr Slcam
3. Heat of Sublimation.
Suh[mation is r process in which a solid on
hcating changcs directly into gaseous s(ate below
its melting point.
Heat of sl
chaiw aq
solid rlireclly
ture bebv its

For cxample, thc heat ofsublimation ofiodine

is 62.39 kJ mol-I.
tz 6)........- 12 G), LH = +62.39kJ mol-l
Most solids that sublime readily are molecular
soli<[s, e.g, iodine, naphtbalene etc.
Itmay be poiated out that sublimation isnoth-
ing but fusion and vaporlsation carried out in one
step, i.e.,
C(;) + or@) .-.* Co2 k), AH= -393.5 kJ mot-l
AHsubtimation =AHfrson * AlLpo.i""tion Ifcarbon burns to [orm carbou monoxide first
Otberwise also, this equatiotr is true because which then burns to form carbon dioxide, the heats
enthalpy is a state property. evolved in the two steps are as follows : _
t
(i) c (r)+ {)2 G) -----+ Co ((),
;
AH= -110.5 kJ mol-r
I
07) coG)+; (), G) (q),
-,corAH=
-283.0 kJ mol-!

c(s) e-j-rJ
AH=-3s3sk.r

._.
Thus the total heat evolved in the two steps
= (-
_
will be AH + ( -283.0)
the statrdard s(ate conditiotrs, superscript e is
0.5)
kJ mol -r which is thc same whcn the reactioD takes
=- 39315
used with H, r'.e. we write,
place directly in one step.
A,He, A"Ho, ArHeetc. However, more (2) Sulphur (Rhombic) burns to form SO,
common way of representation is AH", AH7 etc.
or directly in one step as
AH"', AHr'etc.
s (R) + C)2 G)-....- so3 (s),
law ol Constant Heat Sumrmlion ;
G.H. H AH = _395.4 kJ mol_r
gave a law about Sulphur may change to SOt in two steps
as
of experimental
after his name as
(,) s (R) + oz k)- soz G),
AH = _ 297.5kJ mol_r
 Pvadecf 's Neut Course ChemistrgVffi
5/30
be
a number of times, a large amount of heat cun
crcatecl. This is, horvcver, against thc luw of cttnscr-
vation of cnergy. Hcncc Q nrust be equal to Q' i r'
Hcss's law must be correct.

S(R)

(,0 so2 G)+i 02 G).-* so3 G)'

consequence of Hess's law :
-
AH=-97 9 U mol-1 equutiotl4i can be lrcated us
Total heat evolved in lhe two sieps is w-hich can be uildcd' sub'
r ilivided.
LH = -297'5 + (-s7 9) = -395 4kJmol-r
This is the same as for the direct reaction in A few important applications o[ Hess's law

one step. are given below :

-
Theoretical Proof of Hess's Law' Considcr 1. Catculation of enthalpy of formation' Ths
cannoI
the general reaction A D
-""r
Suppose the heat evolved in this reaction
calou-
follorv-
directly is Q joules.
Now suppose the same reaction takes place in olJbrmu-
f l\.\\Il'1,t, l.C(\Iculqte lhe enllrulpy
three stePs as follows - :
tion of nrethane (CHo) frtnt thc followirtg tlotu :
A- B --+ c- D
SuPpose the heats evolved-in these three st eps (i) C (i) + o2G) Co, G) '
are 4r , q2 ' q3 joules resPectrvely'
-
L,H = -393'THntot-l
rhus rhe toral heat
""",""1f,11"1,i,,11; I
+ (l\
tii) H,lg) + ; O, (sl H ro .

"
= _2u5.6H rtnt-l
*
(iii) CH 4 @) +2o CO 2 G)+2H ro (t)'
2 @)
-'
LH=- l]90'4Hntol-l
Solution. We aim at
zG)- cHa (q) ; AH = ?

Multinlvinc equation (ii) with 2 adding to

(i)
FIGIJBE 5.14. Theoretical Proof of Hess's Law and then.ubirrJting equation (iii) from thc sum i c'

operating (i) + 2 x (ii) - (iii)' we gct

According to Hess's law, we must have Q = O'
If Hess's law were not correct, then either
e,<Q orQ'>Q LP^= - 393'7 + 2(- 285't')- (- 890 4)

=- 74 9 kJ mol-l
or C (s) + 2H, (q) -- CHo G) ;

AH = -74 9kJmol-l
Hence hcat oI formation oI mcthanc is
-1
Atl/ = - 74 9 kJ mol
 FIRST LAW OF THERI\,IODYNAMICS AND CHEi,4ICAL ENERGETICS 5t,,
laXAl\IPLD 2.Calculote the mthaw offonna- AH = -393 -5- (- 395.4)= a19L.I
tion of carbon monoxide (CO) lron lhe lollowinq or C(graphite) C(diamond);
dote :
(i) C(s)+ or(9- CozG); - aH = + 1.9kJ
3. Calculation of the nthalpy of hydration.
A,H=-3933klntol-l The experimental determination of the enthalpy of
I hydration is almost impossible. However, it can be
tii) Co \gt + ror(g\- Cor(gt; easily calculated using Hess's law as illustrated by
the following example :
LH = - 282.E kJ mol-1
Colcltlote the enthalpy of hydra-
Solution. Wc aim at
tion of anhydrous copper sulphate (CuSOr) into
1
C(s)+ 7orfu) ' co(c):AH=? lrydrated copper sulphate (CuSOo. SHrO). Given
tltut the entholpies of sohttions of anhydrous copper
Subtracting equation (ri) from (i), we get sulphate atrd )tydrated copper sulphate are 66. 5 -
I
+ rorG)-coG)-
C(t) 0r and * 11.7 kJ mol-l respectively
Solution. We are given
AH=- 393 3-(-2f,2'8) = - 110 5kJmol-' (i) CUSO, (s) + aq """""'r CuSOn (aq) ;
I
or C(s)+;OrG)........- COE); AH = - 66.5 kJ mol-r
as=-riosu. (ii) CuSOo . 5HrO (s) + aq-
. . Heat of formation o[ CO is CuSOo (aq) ; AH= + 11.7kJmol-1
AH, = 116 5 1t' to'-' We aim at
2. Calculation of enthalpy of allotropic trans- CuSOo (s) + 5HrO (/) .*
iormation. Elements like carbon and sulphur exist CuSOo . 5HrO (s) ; AH = ?
in different allotropic forms. The change of one
form to the other involves a very sma[ amount of Equation (i) can be written in two steps as
heat and is a very slow process. Hence the ex- (iil) CuSOn (s) + 5HrO (/) -----------+
perirental determination of heat changes for such CuSOn . 5HrO (s) ; AH = q, kJ mol-t
transformations is very difficult. These are calcu-
lated by the application of Hess's law as illustrated (iu) CuSOo . 5HrO (s) * 0q
by the example given below : - (aq);AH- = 4, kJ mol-1
CuSO.
l' \ ',\ll"l,1... Calculate the enthalry change ac-
companying the transfomation o! C (graphite) to According to Hess'slaw qiq2= -66.5 kJ mol-l
Co(diamond). Given that the enthalpies of combus- Further, equations (ii) and (iv) are same.
non of.graphite and.diamond arc 393.5 and 395.4
Rl mol ' respecdvely.
4z= l ll'7llJ mol-l
given
Putting this value above, we get
_S-o!gtlo_ll: We are
(i) C (graphite) + oz@) COz@) ;
qj+ ll.7 = -66.5
AH = -- 393.5 kJ mol-r
or 4r= - 66'5 - lL'1 YJ
(i) C (diamond) +O, G)-r CO, (g) ;
= - 78.2 kJ mol-r
Thus equation (iii) may be written as
AH =- 395.4 kJ mol-r CuSoo (s) + 5Hro (i)-----------r
We aim at
CuSOn . 5HrO (s) ; AH - 78.2kJmol-l
C(graphite) .......* C(diamond), AH = ?
Subtracting equation (ii) from (i), we get This is what we aimed at. Hence the required
C(graphite) - C(diamond) 9'
value of the enthalpy of hydration is AH
=- 78 2 kJ mol-r.
-
tlf may bc notcd thai thc hesl changc for lhc samc rcaction is sometimcs stightly diffcrcnt in difrcrcnt p-ro-uteis-astncsc
are thevalucs rcportcd try differcnt workcN and dcpcnd upon thc conditions oftcmperetuE ctc.
5132
Pradecp's Neut Course CheO i"trAWID
4. Prdicting the enthalpy change for any changes of certain other reactions. The numerical
reaction. Hess's law can be applied to predict the problems given below willillustrate the application
enthalpy change for any reaction from the enthalpy of Hess's law.

SOME ADDITIONAL NUMERICAL PROBLEMS ON HESS'S LAW

'fYI'li L OI thc calculatiou of hcats of fbrrtrrtion In order to get this thermochemical equation,
multiply Eq. (iii) by2 and add it to Eq. (ii) and then
subtract Eq. (i) from their sum. Wc get :
c+2H2- cH1 ,

enthalpies of fomwtion of COrand H2O arc 394 5 AH= -393 4 +2 (-285 7\-(-890 2) kJ mol-r
qnd 286'6 kJ mol-l respectively, calculate the en- = - 74'6 kJ mol-r
thqlpy o[ Iomtation of ethyl olcohol. Hence the heat of formation of methane is
We are given :
LHI = - 74 6kJmol-r
I.IXA\II'LIi -1. Calculate tlu heat ol fonnation
(0 qH5OH + 30, + lQ92 + 3HzO,
of KCI fronr the following dota :
AH = - 1380 7kJ mol-l (i) KoH (aq) + HCt (aq)
(rD C + Or-CO, AH= -394'5 kJ mol-r (l), --,57'3Hmol-1
, KCI (aq) + HrO LH -- -
I 1
(i,r) H, + * or.....-- Hro, AH=-2a6 6 kJ mol-r (ii) H2w) +
)Ortel- U.rO (t\,

w" ot LH= -286 2klmot-1

"i'- tl
1
* rO, iii) (gl + + q+
2C + 3H2 CzHs OH 1H, ,Ct2 G)
HCI (aq), LH = - 164'4Hmol-l
-
In order to get this thermochemical equation, ll
multiply Eq. @) by2 and Eq. (ir'i) by 3 and substract (iv) K(s) + !2o2 (E) * rH rte) * oq
Eq. (i) from their sum, i.e. operating 2 x Eqn. (ii)
+ 3 x Eqn (r'ii) - Eqn (i), we get KOH(aq), LH = - 487 4 k! -mol-l
(v) KCI (s) + oq KCI (oq),
2C + 3Hz*
1
qH5OH LH = t 18'4 kJ mot-l
iO, --- I
-
Soluton. We aim at
aH= (-3e4'5)+3 (-286 6)-(-1380.7)
2 I
= - 268 1 kJ mol-l K(r)+ Cl, (8)"""+KCl (s). AH=?...(t'i)
Z
Thus the heat of formation of ethyl alcohol is In order to get this thermochemical equation,
AH, = - 266 we follow the following two steps :
Il\ \)lPl ',O',tot-'
ll-1. Calculate the enthalp of fonna' Srep 1. Adding Eqns. (rii) and (ir') and sub-
tion of methane, given that the enthalPies of combus' tractiug Eq. (v), we have
tion of methane, grqphite and hydrogen are 890' 2 kJ' 1l
K(r)+ (s) + H2 G) + o,
i9j'4 H and 285'7 H mol-l respectively. ;Cl, i Gl.........-
We are given : KCI (s)+HCl (aq) + KoH (rq) - KCI (aq)
(,) CH4 + 2Or-"- COz + 2H2O, AH= - 487.4 + (- 164.4) - (18.4)
AH = - 890 2kJmol-1 = - 670 2 kJ mol-r ...(vii)
Step 2. To cancel out the terms ofthis equation
(rt) C + oz COz,
which do not appcar in the required equation (vi),
-' AH= -393'4 kJ mol-r add Eq. (i) to Eq. (uii) and srrbtract Eq. (ii) from
l their sum. This gives
(iiil H2+;O2 -'--- H2O
' 1
K (s) + Cl, G).-.......- KCI (r) :
AH=-285 7Umol-t ;
We aim at : LH= _ 6i o. z 51,1; j
C + Ztl, "'-------+ CHl AH : ? _+ l;T; :
'
FIHST LAW OF THERMODYNAMICS AND CHEMICAL ENEBGETICS s/33

l ltthylene on combustion gives carboD dioxide and 2SO2 G) + o2@) * 2SO3 G),
water. Its enthalpy ofcombustion is 1410.0 kJ/mol.
If rhe enthalpy of formatioD of COz aod I-I2O are AII " = -198 kJ nrol-l
393.3 kJ and 286.2 kJ re.spectively. Calculaie the kl mol-r]
col halpy of formation of ethylene.
[ "ns - '145'9
7. Calculatc the enthalpy oI formation of anhydrous
[turs. +51.0 kJ Erol-ll Aj2Cl6 from lhe follo\rying data :

2. Calculate the
enthalpy of formation of carbon
(i) 2Al (r) + 6lrct (aq) ......-
disulphide given that the enthalpyofcombusrion of AlrCl5 @q) + 3l1x@) + r 004.2 kJ. kJ nlol-r
carbon disulphide is ll0.2 kJ mol-l aDd tbos ot
sulphur and carbon are 29.4 kJ aod 394.5 k g (,,) H2 G)+cL (S) .+2HClE)+184.t kJmol-r
atoD'r rcspctively-
[,\ns. - t79.1 kJ mol-11 01i) IICI G) + aq l }ICl (oq) + 73.2 kJ mol-l
3. (hlculirtc the cnthalp) of formation o[ acetic acid (iv) FJ2CI66) + aq
lion] the fbllowlng dalr : -
Aj2 Cl6 (d4)+643. r kJ mol-r
(l) (l (r) + c)2 G) ......* CO2 G), AH =
-393.7};I I,\trs - 1352.6 kJ mol-ll
tii) II2 (s) * i o, (Xr .... H2O 1lr. E From the tollowiDg I hermochemical cquations, c{l-
culate the standard erthalpy oI formatioD of IICI (s).
aH = kJ (A) H, (B)
-2a5.8 2H (s),
(,iD cH3coolt (/) + 2o2G)
- all = +436.0 kl mol-l
zCOz G) + 2H2O (l),- = ---873.2 kJ
^H (B) clz (9)- 2cl(s), = +242.i kJ $ot-l
l\rs.-4t5.8klmol-rl ._ ^tl
(c) HCI (s) Il (s)+cr G),
4. Calculalc thc cnthalpy of ionnatioo of sucrose
(L rzl122 Ot l) tiom the lollowing data :-
AII = +431.8 kl nrot-l
(i) (lrz Ilz2 Orr + 12()2 I \ns kJ mol-lI
I2CO? + I lH2O, -92.45of
9. C-alculatc the eDthalpy of formalion r-hutanc
- =
All mol-l from the Ibllolring data :
(ti) C + 02 -..-.* (loz,
-5200.7IJ (i)zqHn@) + r3o2 G) ._
AH = kJ mol-l
-394.5
8CO2 G) + I oH2O (r), aH = - 5757.2 kJ nrot-l
+o, ....-llr(). atl = -285.8 kJ mot-l
1

{iii)ll, +
0i)c(.') + o2@) coq @),
I\Ds.- 2677.1 td Itrot-rl - AH = - 405.4 kJ mol-l
S. (hlculatc the eothalpy of formation of benzcoe, (iii) 2H2(8) + or(g) ?llr0 (1,
glvcn that enthalpies of combustion of benzcoe,
carhoo and hydrogcn are kJ, kJ -
AII = - 572.4 kJ mol-l
-3281.5
lD(l --286 I kJ/mol, respectively. -394.9 On lvhat law areyour c{lculations based ?

I Ahs +S3.t kJ mot-rl I,\ns.-174 kf mol-ll

10, Calculate the eDthalpy of tbrmation ofactic acrd if
6. ()rlculale the standard enthalpy of formarion of the enthalpy of crrmbustion ro CO2 G) and
SO3 ar 298 K using the following reactions and
H2O (D is --67.0 H mol-l aDd enthalpie$ of for-
cDthalpiqs-
ma(ion of CO2 G) aDd H2O (l) are respectively
s8 (r) + 8o2 G) 8so2 G),
- -393.5
and
-285.9
kJ mol-1.
dIl" =-2775 mol-l
[.\rs -491.t kJ mot-ll
5134
Pt trtit i.':tt's Ncut Coursc Ch"-ittrqlfrfrlp

l. Given 4. Aim : 12C(r) + 1r H2 (;) +

+02(s).-
(,) eH+ G) + o, z coz e) + z rt.o (I), CrzHrzOrr (r), AH ='r
| Gy
-
AH=-l4100kJmol-l 5. Aim: 6 C (.r) + 3 Hz G) * C6H6 (D, -?
^H
(,0 c (r) + 02 @) ... co2 G), Given: 1i) C5H5 rD
r<
+;02(B)-
AH=-3933kJmol-l 6 CO2 G) + 3 H2O,
(iii)Hz@) *lo.-o -... Hro (i), AH=-3281 5 kJ mol-l
AH=-2862kJmol-l 0i) c (r) + o2G)- Co2G),
Ainr:2c(r) +ZUrg) c2He(9 aH = ? AH--3949kJmol-1
- (i)
2 xE4n. (ii) + 2 x Eqn. (iii) gives the
required result.
-Eqn. (iii) H2@) +
t or@1- uro 1t),

2. Aim: C (,r) + 2 s (r)+ CS2 O, aH = ? AH =-286 1kJmol-l

civeD :
6 x Eqn. 0i) + 3 x Eqn. (lii)
(i) 6z (D + 1 o2g) + CO|G:) + 2 so2 E), (i)
-Eqn. ...-Sives lhe required result
6. Aim + : 58 (.r) +
] o, 6) So, 1g), 611 ="
AH=-I102kJnol-I
(it) s (r) + oz G) .- soz G), 7. Aim:2Al (r) + 3 cl2 G).* Al2Cl6 (r, AH - '1

AH=-2974kJmol-l EqD. (i) + 3 x Eqn. (io-Eqn. (iv) + 6 x Eqn. (iii)

(iii) C (r) + or(g)- COz@\, gives fie required result.
1r
AH=-3945kJmol-l E. Aim: i H2 (a) +;cr2 G,).- HCI G)
Eq. (iii) + 2 x Eqo. (ii)-Eqn. (i) Sives the required 9. Aim: 4 C (.r) + s H2 G) * C4H1o E), AH=?
result.
<1
3. Ainr:2C(,r) +2HzG)+ 02G)- CH3COotl, 4 x Eqn. (ii + i x Eqn. tiii) i x Eqn. (i) givcs

AH=? the required rcsult.

(iii) 10. Similar lo problem 3.

2 x Eqn. (D + 2 x Eqn. (ii) Sives the
required result.
-Eqn.

IYPE Il. On the calculaliort (irl) 2C (s) + 2H2@)'-, CrHo k),

oIenthalnles of combustiolr AH = + 52'3 kJ mol-1
1..XAi\ il't.tl. Calcurate the enthalpy of combus- We aim at :

tion ol ethylene (gas) to form CO, (gas) and HrO QHo G) + 302(0 --....--..,

(gas) at 298 K and 1 atmospheic pressure. The 2CO2 @) + 2H2O G), AH : ?

enthqlpies ol formation of CO, ,H2O and CfIo are
2 x Equation (i) +2 x Equation (ii)
- 393.7, -241.8 * 52.j kJ per mole respectively. Equation (iri) gives
Solution. We are given :
2c (s) + 2ozG) _.f - zCO2 @)
(,) c (s) + 02 G) --.........l coz G),
AH = -393 7Umol-r
+ oz?) + 2IJ2 G) + 2H2O G)

(i,) H, G) +
1
o, G) -._....' Hzo (8),
-2c - zHz@) - CzHq(c)
(s)
i 3o2@)-2coz@) + ZHzO (9 - CzHq(B)
AH = - 241'8 kJ mol-r or QHo @) + 3o2 @) @) +2H.2o G)

-zcoz
 FIRST LAW OF THERMODYNAMICS AND CHEMICAL ENEBGETICS 5/35

LH = 2(- 393'7) + 2 (- A1.8) - (s2.3\ AHR"""tion = (Sum of AH1'values of Products)

= - 1323.3 kJ mol-r - (Sum of AHr" values oI Reactants)
Alternative Method :
We aim at :
CzH4 G)+3O, (d....-zcoz @)+2}{2O G) -I*4"rra*"A'ftor)l
We are given : AH,r(co, = -393 .7 kJ mol-l
= Izx(-3e3. 7)+2x(-241.8)l-[(52. 3)+01
AH/(Hro)= - 241.8 kJ mol-t C. AHf for elementary substance=O)
AHf
fqs, = +52 3 kI mol-l = I-787 .4-4f6.61-52.3 = -1323.3 kI mol-r

1. Calculate the enthalpy of combustioo of beozene 3. Calculate the enthalpy ofreaction for
fronr the followiDg data :-
(i) 6C (, + 3H2 G)-C6H6 (0, CO(a)+Z02e)......* cO2G)
GivenC(r) + o2G)
AH =49.0 kJ mol-l
(r:HrGl* I or@;*Hzo (0,
-COzg}
AH = 5 kJ mol-1
-393
* ._
AH = -28i.8 kJ mol-l
c 1r; ] o, rg; Co G:)
^H
=-110.5 kJ mol-r

0,t) c (r)+o2 G) -- Co2 G), I r r,. kJ mot-rl

-2113
4. Find lhe enthalpy of combustion of carbon
alt =-389.3 kJ mol-l (graphite) to produce carboD monoflde G) on the
basis of data given belo\ :-
[ \,]: kJ mol-rl
-3242.2 C(graphite) + oz G)
2. The enlhalpies of formatiol of metbane, carbon
dioxide and water (liquid) are and
- COz (8) + 393.4 kJ mol-l
-74.8,
yJ respectivefy. Calculate the-393.5
eDthatpy of
-246.2 co()*lor@)
combustion ofmetbane at ordinary temperature. coz@) + 283 okJmol-l
[ \ns
-Egl.l kJ mot-l] -[ \rr. dH 110.4 kJ mol-11
= -
H lNT5 FoRDtFFlcuLT
r. Ainr : c6H6 (4 + AH nerction
"Rortr:vo
=
[^Hi(Co2) aHi(HzO)l +z
+ 02 G)
6 CO2@) + 3 H2O (/), arr = ? _ - l^Hi(CH4) + 2 ^Hi(02)l
-
6xEqn.(i)+3xEqn.(ii) 4. Aim : C (.r) * o, 1- CO (s.). 6H = ,
|
(i) givcs the required resutr. Eqn. (r)-Eqn. 0r) gives the required resutr.
-Eqn.
2. Aim I CHl e) + 2 o7@)- CO, (g) + 2 HzO (l)

rYPE III. On thc calculatior

(ii) S(ntonoclinic) + O2----, SO, (E),
of enthalpies of tiaositions

f
, \..\\ ll,Lla. Given rlr e followingthermochemi_
LH : - 300.0 kJ mot-\
cal cquations Cqlculqte LH for the
(i) S (rhombic) + O, (g) SO, (g), gtqm om o[ rhombic sulph
phur
AH : --.+
_ 297. 5 kl ntot-r
s/36 Pradeep's :r: a:i i!i/,i;t;lth'lsttglfi[)
Solution. We aim at : or S(rhombic) -.--.------ S(monoclinic),
S(rhombic)--' S(monoclinic), AH :? AH : +2.5 kJ mol-r
Equation (i) -Equation (ii) gives Thus for the transformation of one graul atom
of rhombic sulphur into monoclinic sulphtrr, 2'-5 k.l
S(rhombic) - S(monoclinic) -.-- 0,
mol- I of heat is absorbed.
LH = 297'5 - (- 300'0) : 2'5 kI mol-l
!lil

',?'', OttB:.E ,iM..,S',F--.@..RiiF iH

is red. The standard enthal-
l. The enthalpies of combustion of graphite and yellor and the other
diamond are 393.5 kJ an<l 395.4 kJ respectively. !:ies of formation of these two forms ate -217.3
Calculate the enthalPy change accompanlng the and kI per mole respectively. Calculate the
-219.0
enthalpy change for the solid-solid phase transition.
transformation of 1 mole of graphite into diamond-
PbO (Yeltow) PbO(red)
[.,tns. 1.9 kJ mol-l]
2. There are two crystalline forms of PbO ; one is - lAns.
-1.7
kI mol-r]

H li{Tg FoRotFFtcuLT ?r.orlEMe

(Ycllow)'
l' Given
3e3'5 kJ nror-r AH = - 217'3 kJ mol-1
(ii)c(di')+ 02 (8)* #r;; (ii) *
I
Pbo (Red),
Pb (s)
iorG)-
AH = - 395'4 kJ nrol-l
AFI : - 219.1) k.t nrot-l
Aim: C (gr)- C(dia), AH = ?
Eqn. Q))-Rqn. (i) gives the required rcsult.
Eqn. (i)-Eqn. (ii) gives the required result.

TYPE rVn the calculation

Equation (ii) may be written in two steps as

of enthalpies of hydration BaCl (.r) * ZHrO- BaClr.2HrO (s),

l.\ \\ll'l.l'. Enthalpy of solution (LH) for AH: AHr (say) ...(iy)
BuClr.2HrO and BaCl, are 8'8 snd - 20'6 kl BaCl, .2HrO (s) * uq BaClr(aq) ,
ntol- | respectively. Caladate the heat of hydration of AH = AHz (say) ...(v)
-
BaClrto BaClr.2H2O. Then according to Hess's law
_q[!g"r We arc given AHr+AHr=-20'6kJ
(i) BaCl, .zHzO (s)+ aq BaClz(aq), But AH, = 8'8 kJ mol-l
AH : 8'8 kl mol-1 ['.'Equation (i) : Equation (v) |
(ii) BaCl, (s) + aq -----_- BaClz@q), .'.AHr = -20'6-8'8= -29'4kJmol-l
AH : -20'6kJ mol-l But Equation (iii) : Equation (lu)
We aim at Hence the heat of hydration of BaC)I,
BaCl! (s) * 2H2O+ BaClr.2HrO ('s),

aH :? ...(rrr) = - 29'4kJ mol-l

? ;b: lLlE,.N/ ."9.. F'O .'R

"R'O
'l'hc enthalpy of solution of anhydrous copper sulphate (CuSOo) and hyclrated
coPper sulphate

(CuSOo.5H2O) are --{6'5 and +11'7 icJ mol-1 respectively. Calculate the enthalpy
of hydration ot

anhyrJrous copper sulphate to pentahydrate' 1 -78.2 kI mol-r]

 FIHST LAW OF THERMODYNAMICS AND CHEMICAL ENERGETICS 5137

H lNT$ FoRDtFFtcuvr ??ooLEuo

(iivcn : (i) CuSOa (, + aq + CuSO4l1,q), AH = - 66.s kJ mol-]
(li) CUSO4.5 H2O (t) + oq. + CnSOa@q), AH = + rl zrlmot-r
Aim: CUSOa (,r) + 5 H2O (/)- CuSOl .5 HzO (r), AH = ?

See solutron oD page 5/31

TYPE V On thc calculation What is LHo aa 25'C lor this reaction ? Given
ofcrtthalpy charge for any rcaction that the standard heats of Iomation of AlrO, and

py oI combustion of ethylene, hydrogen and Solution. We are given

athqne ore - 1410.0, -286.2 und - 1560-6 H
* lortgl .._
2
mol-1 respectively at 298 K. (N.C.E.R.T,) (r) 2 Al (s) Alzo3(r).
Solution. We are given
(i) 9Ha@) + 3o2@)-
AH = - 1675.7 kJ mol-l
1
(i0 2Fe (s) + FerO, (s),
2CO2 (d + 2H2O (r), ;O2G)
AH= - 1410 kJ mol-r AH:-' -828.4kJmol-r
I We aim at
(,,) H2B)*iOr(rl ------...... Hzo(0, 2Al (s)+FerO, (r) -----+ Al2O3 (s)+2Fc (s),
AH = -286.2 kJ mol-r AH: ?
I Equation (i) -Equation (r'i) gives
@i) qH6e)-r 31o (s) -........+
2Al (s)+ Fero. G) ...........+ Ato: (.r)+2Fe (s),
zco2 @) + 3Hzo (t), AH= - 1675.7 - ( -828.4)= -847 3 kJ mot-r.
AH = -1560.6 kJ mol-l Altemqtive Method
We aim at CrHo + H. (g)-.-,qH6 We aim at
G), AH = ? ........-
Equation (i) + Equation (ii)
2Al (s) +FerO, (.r) AtO: (s) +2Fe (s),
-Equation (rr) gives
HzG)- AH: ?
9Hl9 + QH6G), AHReaction = Sum of AHi of products
AH = - 1410.0 + (-286.2) - (1560.6)
- Sum of AH'/ of reactants
:- 135.6 kJ mol-l = x AH"r (Fe)l
[AH'r (Al2 03) + 2
f
,_XAi\lPI_f ,l 2. The thermite redction used
Iot - [z x AHi (a]) + AH., (Fero.)l
welding of ntetais inyolves the reactiol
2Al
=.1- 167s.7 + 0l - [0 + (-828 4)l
(s) + Fe ,D, (s) Al rO, (s) + 2Fe (s)
= - 847.3 kI mol-l
-

l. The enthalpies of formatioo of carbon moooxide C+HrO ....._ CO+H,

and steam are aod ---243.0 kJ mol-l
-110.5
respectively. Calculate the enrhalpy ofthe reaction L\I< +132.5 kl mol-l]
when steam is passed over coke t.e, for the reaction 2. Chloroform is prepared ftom metbane according
to the reaction
s/38
.,..,"i j Nert Course Chemistrglfiffi)
Vl: La i.ll l-l

cH4 g) + 3cr2 cr) ...* ana,rl,) t ,r., n, StaDdard enthalpies of formatioo (AH/) at 25' C

Calculate AH for the reaction Siven that enthalpies

for NH3 G), H2O G) and NO G) arc ---46.2,
and +90.4 kl/mole respeclively.
of tbrorarion of HCI (g), CH4 G) and cHCl3 (D are -241.8
-7
4.9 a1d
-134.3
kJ Per Dlole rcspectiYc- ["'' -904 4 kJ mot-11
-92.0, standard enthalpy of formation ofFe203 (r) ls
ly I kJ mol-rl 4. The
-335.4
Calculate the enthalpy ofreaction (aH') when am- - 824 2 kJ mol-l. Calculate the enthalpy chauge
monia is oddized : for the reaction
4NH3 G) + so2 G) 6Hzo (A) + 4No G) 4 Fe (r) + 3 o2G)- 2 Fe2O3 (r)
- [\''rs - 164t 4 kJl

FOR OIFFICUUT ?R.OELEM.S

l. aH Roactioo = [AHi(Co) + aHi(Hil =[(-134 3)+3(-e2 0)l -I(-74 e)+0]
- J^Hi(c) + = - 335 4 kJ mol-l
^Hi(Hzo)l 4. allt" = x aH7' (FezO:l
= J- 110.5 + 0l - J0 + (- 243 0)l 12

- + 132 5 kJ mol-l - I^H/. (Fe) + 3 H/. (O2)l

2. aHRcaction = [^Hi(CHC|3) + 3 = 12 (- 824'2)l - [0 + 0] = - 164E 4 k-I
^Hi(HCl)]

MISCELI"ANEOUS PROBLEMS ON THERMOCHEMISTRY

| \ \.rlf t,l i. The heat evolvedin the combus_ Hence O, used in the production of 44-5 15 kl
tion oI methane i; given by thc followitrg equotio,t : of heat = 22'4 litrts at STP
CH1@) + 2oz@) Cor(s) + 2H2o (t), i \{\tf'l-f ). Thc heat evolveditt the combus-
tion of glucose is shown in the followingcquation - :
- LH = - kt mol- 1
890 ' 3
(a) How many grams of methane would be CdI,rOo(s) + 5Or(d ---,
requied to produce 445' 15ld ol heat of combustion ? 6CO2 G) + 6H2O (O'
r
(b) How many grams of carbon dioide would L,H: -2840Hmot-r
be fonned when 445' 15 kJ of heat is evolved ?
Whot is lhe energt requiremenl Ior prodttction
t (c) Wat volume of ory4en at STP woukl be
of 0 36 g of glucose by the reverse reaclion ?
used in the combustion process (a) or (b) ?
Splgtlgq. The given equation is
Sol-r1!iq9. (c) From the given equation,
890 3 kJ of heat is produced from 1 mole of
Cd Hr2 06 + 6rJ2 @) """""'.
C}lIo i.e.,.L2+4 = 16gof CHr 6CO2 G) + 6HrO @) ;

. . ,145.15 kJ of heat is produced from 8 g of CHo AH : - 28,10 kJ mol-r

(b) From the given equation, Writing thc reverse reaction, we have
When 890.3 kJ of heat is evolved, CO, formed 6CO2 G) + 6HrO @) .........-
= lmole =,149 CuH,rO5 (s) + 6(), (g) ;
. . Whcn .145' 15 kJ of heat is evolved, COt
: AH : + 2840 kJ mol-l
formed 22 g
Thus for production of 1 mole of C6H,rO6
(c) From the equation, O, used in the produc-
(:72+12+96 = 180 g) heat required (absorhed)
tion of 890 3 kJ of heat = 2 moles = 2 x 22 4 :?A4O W.
litres at STP : ,14'8 litres at STP
 FIRST LAW OF THERMODYNAMICS
AND CHEMICAL ENEHGETICS
s/39
.'. For pr^odlction of 0.36 g of glucose,
heat (b) Wriring the reverse ofthe firsrreaction,
we
absorbed=#r0.36 = s.68 U have Alror(s) ......._ 2Al (s) + t
+or@) i
I:\,\\ll'1,L 3. Frum &e &ennochetnicol equotion
H = + 1667.8 kJ mol_l
cFa(D + ,lorUl O+6cor(O, _ .Thus
for the reaction given in part (D) of the
probtem, AH = + I667.El(.Jmot-i
-3H,o
Nt : _ 3264 .
64 kt mol_l
cqlculste the energ evolved when 39 g of
C6H6 are
bumt in qn open container Cqlculate the enthalpy of
fusion of naphthalene-
Solution. From the given equatioo,
When I mole of CuHo (78 g of CrH.) ,^ 9glglion. Molecular mass of naphthalene
is burat, (C,6 Hr) = 126
heat evolved = 3264.64kf g liquid naphrhale ne solidifie d,
. . When 39 g of Cu Hu is burnt, heat near -*i,:n ,,= 149
.^... evolved _of
joules.
evolved
I mote ie. t2B g ot napbrhatene
--,,,.Yb.:heat evolved
= _ ?8 x39=
3264.64 sordrtres,
1632.32 t<l : 19072 Joules
= 149 x l2gjoiles
. The thetmochemical equation .- ,Since,fusion
is_reverse of solidification, there_
forso rocket firc| ore givenbelow:_
:::: n."t for tusion of one mote of naph_
matene ="?:.9r_b^".d
19072joules
2At (s) + ,
) o, ,rl At, o, (s) ; i.e. Enthalpy of fusion (AH7)

-
LH: _ 1667.8H mot_1
: * 19fi72 joules/mole

nr@ + Hzo (t); hint

lo,@) ene,g/ in all fotms to a lo
- A,H = _ 285.9 k! mot_r is the change in intemal en
lost wqs stored. as sucrose
s of a lu minium and. hydrogen
..11 !,1 ",r:,!,.^^.te
-- ^ ulted,
orc many dqys should it take
which is q better rocket
fuel ? water loss.
(b) Determine NI the rcqction
for
Solution. Loss of energy per day
At, o, (s) 2At (s) +t 12000 _ 9500 :
I o, @) 2500 kJ

-
!g!Cqg.. (a) From the lust given equation
2 -g1." nf Al (i.e. 2 x 27 g
..- -. = 54 g) on com_
Dusrron grve heat = 1667.g kJ
. . 1 g ofAl on combustion gives heat
AE = _ 2500 U.
1667 .R
-'54-= o
30 9kJ ^ ,fo. Iost =ofl00
(Cr2H2zO1)
loss 1632 kJ of
g (given)
energy, sucrose

From the second given equation

For a loss of 2500 kJ of energy, sucrose Iost
1 mole ofH, ( = 2 g) on combustion gives heat 100
= 285.9 kJ = i632
r 2500 9 = 153.2*
.. 1g ofH, on combustion gives heat 153.2 g of loss ot weight takes
place in
I day
=
285 .
I . 1 kg (1000g) ofloss ofweight
= l42 95ld .
will take place
Thus, H, is a better rocket
'z 1
= f $. * 1000 days = 6.5days
fuel.
 PradeeP's
5/40
100 g beozene will require energY
'Standatd vaPoisation enthalPY
30 8
arhn ilig point is'30'8 H mol-t' For - '78
x 1oo kJ = 39 51J
i:^:.: tdti W electic hcqtet have to
second'
')iiro," i, ordrr,o ropoize a 100 gsample ofbenzene 100 W heater gives energy of 100 J per
39 kJ ofenergy
it**irs boiling tempera*e ? .'. Time required for getting 5

:
1poni, )n"'gt/time'
lw = lts-l) 39500 J
395 s
(N.C.E.RT.) =
100 J

Solution. 1 mole of benzene'

C6H6 (78 g) : 6 miE. 35 sec.

requi for vaPorization = 30 8 kJ

,i, rritrl uirrrpptv ofthe burner is insufficient (i s'

1, Grven tnat ll^1.'i".," il"tead of a blue flame), a Portion
" ""ri,ff . --r-.^,i^^ A..rrmi6o
Assuming
...CO2 G); hout combustion
(,) C(Eraphite) +O2G)
wasted due to tbis inefficien-
aH =- 393 7 kJ mol-l e cYlinder last ?
aPPror' 17 daYs aPProrl
(ii) C(diaDood) -- C(graPhite) ; Ys

AH = kJ mol-l
-2-1
to Co2
(a) Catculate AH for burning ofdiamond
th hite that rnust be
(b) Calculate
burnt to evolve [ fuls.620.7 g]
s kJ G) rs2'4 cI 2900 kJ mol-1
red phosphorus and liquid
by lhe
2. Crmpare the quantity of heat p-roducedwith thar "' Reaclion between
6. as
reaclion reptesented
'' ;;''ilil;;f l.o g g'tucose (c6Hr2o6) ir'Jti* it
"n.*olhermic
follows :

2P (s) r 3 Br2() ... 2PBr3GI)'

AH" = - 243 kJ nol-1'

Wha
Phos
_9.6 kJ g- ll Thke
alr for the sucrose =

is ,1() 79 kJ mol-l [turs. 1ltl 3 kJI

kJ mol-1
[,\ns. AH = + 2s40
LJ' '1g = + 2t4 kJl
 FIRST LAW OF THERMODYNAMICS
AND CHEMICAL ENERGETICS
5141

l. (a) Eqn.p))-Eqn.
1j; gives ttre re[uireO resutt.
(b) 393.7 kJ of heat is produced froDr
fh: l_ 9" of ,
graphite Eotc (lt(] g)"orr,urpy "r,rnfiGiffiuoion
of gtucce. Hence for 18 I gtucce,
= 12& AH=+2t4td
. . 500,0 kJ of hcar will b produced fiom graphite 4 (a) I Mole ClHto = 58g,
72
- 3!3? x s000 6 = 1s2.4 a ... Hear p.oducd from l12c{ g
2. C5H,rOa + 6 Or+ 6 CO2 + 6H2O 265A
=-5E- x r1200 = 513 8.9kJ.
& Rcacron = [6 AHi (CO, + AHi (fLO,
6 No. ofda)s for which it will tast
_
[^Hi(c6Hr2o5) + 6 Mifqli j
= 513268.9D.n,@O = 25. dara _ 26 days
(D) After wastage, heat avaitabte
= [6 (- 393.5) + 6 (- 28s .s)] _ (_ 1260) + 6 (0) 67
= - 2816.4 tJ mot- I = ;05- x 513268.9 = 343890 kJ
.. Heat produced from I g gucose No. of da)5 for which it will tast
2t16.4 = 34389020000 = 1? dals
= -116-= ts ou
5. Mot mass ofglucose (C6H12O6)
CtzHzzOtt +602-*6CO2 + 1l HzO 180. =
Glucse required per day
aHn."cr;,,n = [6 (_ 393.5) + t I (_
2s5.9)]
= (lE0 ,/ 2900) x 10.000l!.
- I- 2221 + Ol 6. RequLed AH =ff"z.utt J,o , *r.
= - 3284.9 tJ mol-l 7. For evaporarioo of I
.. fleat producd ftom I g suclse mol ot HzO ia 18 g. heal
requ[ed = 40.79 kJ
32A4.9
= 1;;- u = e.6 kI
.. For cyapomtion of 80 g of H2O,
heat required
3. Given: C6Hl206 (r) + 6 Oze)+ =
40.79
_lE_ x E0 = t8t.3 ["I.
6 COz@) + 6 HzO (0, t. AHvap for CO = 6.04 kJ mol-l
AH : _ 2t4O kJ mol_1 Le.6.O4kJ tor 28 g
Aint : Reversb Reaction for which . . Enthalpy change for vaporisation
of 2.38 g
aH = + 2840 kJ rnoJ-t = 181 ,r'ar*r=0.5134kr=(r1.2 r

For oolvatomic rL- L^-r -

.--,6, :-
th"r energy ^,,^r,.- r wheo
, 'rl^lF^rla.
. . We know tha[
rs rormed, and-energy
is evolved .
a bond
is required for the dissocia_
rroo ol a bond. Hence bond energy
is defined as
lbllows :
-

For diatomic molecules like H, Thus average C-H bond energy

, O, , N, ,
, HF erc., rhe bond energies are _ 42,7 + + 452 + 347 _ 7665
439
:,r.. T,
their dissociation energies.
equal to
4-4
= 416 kt mol-l
 Neal Course Chen, is tr4
5142

small difference and the two are used interchan-

geably.
An imPortant u sthat
it hclps to calculate on of
aloms. For example.

Enthalpy of formation of H-atom = ?

= 217'5 kJ mol-1
Calculation of bond nthalPy. For
Dilfercnce between bond cner5. and bond

enthalpies of sublimation, enthalpies of dis-

sociation etc.). Similarly, the bond enthalpies of
heteronuclear diatomic molecules like HCl, HF
etc. can be obtained directly from experiments
or may be calculated from the bond enthalpies
o[ homonuclear diatomic molecules These
calculations are illustrated in the examples
The corresponding bond energy (AU') for given on page 5143 and 5144.
this reaction is 430 8 kJ mol-r. Thus, there is very
TABLE 5.1. Bond energies ofsome common bonds
BOND EN'TTIALI'Y' ROND ENTIIAI,PY'*
BOND ITOND
(kJ mol-l) (kJ mol-11

H-H 436 C-H 414

H-F 565 o-H 463

H-CI 431 N-H 389

H-Br 364 C-C 347

H-I 291 C=C 619

F- F 155 C=C 412

CI- CI u2 C-CI 326

Br-Br 1q) c-o 335

C=O 'to7
I-I 149
O=O 494 C-N 293

N=N 941 C=N 616

C=N 879

(i) A H..r"tion = : - t aH/ (ReactaDts)

AH/ (Products)
(ri) a H."u"11on = 2 Bond Encrsiesor ED33lfffi:"::?,ntharpies
of products

=: B.E. (Reactants) - t B E (Products)

(iii) Hess's law treats thermochemical equations as alSebraic equations'

only one bond'

.Thc6c arE o(.ct vslucG bccausr ihcy itrvolvc dissocigtion of diatomic molcculc6' which contain
which contain mor than one bond'
.,These arc 6r,cragc valucs bccuasc thcy aIc obtaincd frcm molccules
 FIBST LAW OF THERMODYNAMICS AND CHEMICAL
ENERGETICS
5143

For the formation of HCI

l r, r, * ) ru ro......- r.r,rl, A H = A Hr
.'. AH =I B.E. (Reactants)
lolytron. First Method. By using the rclation I B.E. (products)
MReaction = 2 LI/., (producs)
_ E LIf (Reactonts) = j a.e. 6,y +
I n.E. 1cry - B.E. (HCr)
,
Here we are given
H, G) .-...} ZH(g),AH = +430Umol-r - ", = + , +to * lx 2a2 - B.E. (HCt)
. 8.E. (HCl) = 21.5 + 72t + 9t
ct,(g) '-+ zcl(g), AH : + 242 kJ -;;gl
= 427 kJ mol-r
,i
"'(")
we aim at of
Hcl G) ---.H G) + cl (s), AH = ? ...(nr) dissociqtion of H2arc -74.8, +7j9.6and435.4kJ
Evidently, for reaction (rrr) mol-1 respectively.
AH:>AH/' (products) - XAH/. (Reacrants) Solution. Here we are given
= [AH/'(H) + AH/" (ct)l - taH/. (HCl)l c(r) + 2H2
k).-......- CH1 k),
-'(iv)
AH : - 74.8 kJ ...(,
(,),
From equation^s (i) and cG)----------+ cG), AH = + 71s.6H ...(ii)

AH/' (H) = j{*+:ou) = 215kJ mol-l

H.(s)- 2H k), au : + 435.4H
... (ni')
A H/'(Cl)=
1
We aim at CH4 k) --.......r C (S) +
){+ztzuy= + t2r kJmot-r 4H(S)

Also we are given AH/ (HCl) .-(iv)

=- 91 kJ mol-t Eqn. Q;) + 2xBqt (iii) _ Eqn (r) gives
Putting these values in eqn. (iv), we get
c(., + 2Hrk).........-- cG) + 4Hk)
AH = [+ z7s + 7Z7l _ t_ 91]
: 427 kl mol-r -C -2H, @) - CHo k)
(s)

Second meihod. By using Hess's law 0= cG) + 4H(s) _cH4@),

We are given LH = 719.6 + 2(a3s. q _ G 74.8)
(,) HrG).+ zH(O, aP,: + 430 kJ mol-r or cHrG)..----.-ck) + 4Hk),
(rl) ClrG)- 2ClG), AH= +Z42kJ mot-1 AH = + 1665.2 kJ
This_gives the enthalpy of dissociation
Oi) ;H,@) * irr,t t.--* HC1G),
.
mole s ot C- H bonds
offour
Hence bond energy for C_H bond
AH = _ 91kl mol_l )
We aim at 76f.5.2
= 416.3 kJ mol-r
HCIG) --... HG) + cl G), aH = ?
ll
1x (i')+; x (,1) - 0t, cives the required result.
Third Method. By apptying the retation
A HReaction = X Bond Enthalpies of
Reactants
_ X Bond Enthalpies products
of
 Prade tt p's Neut Coutse Chem
5144

Calculate the enthallry chonge = tB.E.GIr) -

- 2B'E (HBr)
B'E. (Brr)l
l,t\.\]ill,l,l: l.
Ior the rcqctiotl =45+L92- Zx 4 =-101 J
+ Br2 G)
H2 G) zHBt (g) , lix t I,LI,I ?. PrcPane has tlrc stntcture
I

-
Given thot the bond enthalPies H-!1\ arc-'it -6n, )olcuiate rc change l enthalpy
'f
Br are 435, 192 and 364 kJ mol-' following reaction :
Br- Br and H - 'for theirnrtsl+5oz@)
re spectivelY.
Soluiion. Energy absorbed for dissociation i Co2 @) + 4 H.O (g)

of r -oGIiE-H bonds = 435 kJ avet bond enthalpies t re :

Given that
Energy absorbed for dissociation of I mole
of
C-C "ati' C=O
C-H O=O O-H
"i; 711 1e8 46t H not-7
Br-Br bonds = 192 kJ
Total energy absorb ed = 435 + 192
: 627 kJ ( r.c.E.R.T.)
Energy rcleased in the formation of 1 mole of
Solution. AH,..",an
H.-Br bonds = 364 kl --l-usn
of 2moles lrll
F. lH-c c-c-H
ofH rbed
I errergY.
.e.'to = =o)+
L\ ,I l
o-H)l
kl
= t2 B.E. (c - c) + 8 B.E. (c-H)
Energy released:728 kJ -627 kJ = 101

i.c. for the given reaction' AH = -101 kJ +sBE'({)=o)l

Allernatively, the problem may be solved.by
applying Hess's law or by applyitrg the
tollowng - [6 x B.E.(C = o) + 8B'E (o-H)l
= l2 (347) + 8 (414) + 5 (4e8)l
relation directlY
[6 (741) + 8 ('164)lkJ mol-l
A HR"r.uon = E B E' (Reactants)
=1694 +331 + 249n] - 14446 l7tzl
- XBE (Products)
= - 1662 kJ mol-r

bLEViSofFOR (ii) oz@)- ?-o (8), Allz = I13'l kcrl

l. Find the enlhalpy of formation Hydrogen
nuoride on the basis ot followinB data :
(i,D H2 g) + pze) uzo tsl
Bond eners/ of H-H bood = 434 kJ mol-l - AH3=-578kcal
Bond eners/ of F-F bond = 158 kJ
mol- I
l'\rs l10'6 kcall
Bond energy of H-F bond = 565 kJ mol-1 5. Calculate the enthalpy of hydrogQnation of
I t'u' kJ mol-ll C2H2 @) to QHr G)
-269
the reac on
2. Calculate the enthalpy change for lciven C-H = 4'14 0 kJ nol-l'
bond energies:
HzG) + rz3) zH.t G)
t = c = s2'7 0 kJ mol-r C = C = 606 o kJ
Given that the bond energies of- H-H' I-I arld
mol-I, H-H = 430.5 kJ mol-l;
H-] arc433,151 and 299 kJ mol-l pectively'
(A.I.S.B. 1gg7) [rl' -175 9 kJ mol-ll
[\ -r4 kJl
3. C-alculate the enlhalpry offormation
- il;i;b.;;;;;si;orH-H,o
sono are +f: u nior-1, 492
ofwater' tNen
= oando-H
kJ mol-1 arui 464 kJ
6. aH for the reaction

H-C =N (g.) + 2 H2 g)- H -c-

ri N -H G)
nlol-l respectivety [.rns. -249 kJ mol-ll ,!
data at 25" C' calculatc the bond
4. From the following kJ. Calculate the bood eoergy
of C = N
eDergY of o-H bord : is
-150
bond.
(;) il, rsl 2H (a), = 1M 2 kcal
^Hl
-
 FIRST LAW OF THEHMODY\AMICS ANO CHEMICAL
ENEHGETICS
5145

lcven bond energies of C-H = 414 kJ mol-l ;

(ii) C(graphile) CGt aH = 716.7 kJ
H-H = 435 kJ nrol-l ; C-N = 293 kJ mot-I, (utl H2@) 2H E), =435.9u
N-H = 396 kJ mot- t1 - ^H
1o.s.a. rcoas A.ssu me the -C-H bond enerry as 4 I 6 kJ

[.rns E39 kJ mol-r] lAns. 329.77 kJI

7. Calculale rhe enthalpy change for lhe follour'ing 9. Calculate AH. for the reaction
reaclion H2 G') + Ct2 (3) ......-- 2l ICI CH, = 6q, +302 -+ ZCO2 + ZH|O
G)
Given thar rhe average boDd energies ot rhe
GiveD that rhe bond dissociation energies of dit-
terent bonds are
II-H, Ct..-Ct and H_Ct arc 43.7 kJ:2 4 kJ arld
Bond C-H O=O C=O O_H C=C
433 kI mol-, respectivety. . kJI Bond 414 4gg 724 460 619
t. C-C bond ener!5/ rrom rhe fo owing
-lrs enert5/
3.lc'rl3l:lh:
data : (i) 2 c (Srapbite) + 3H2 G) -...* qH6
G): 1U mol-l; [,\Ds. kl mot-r] -964
AH = __{4.67 kJ

,. oio',,|u, * jrr.-s46g =, ucrs)

=[BE (c=c) +2x B.E. (c-H)
-E B.E. (products)
aH = >8.8. (Reacraotr)
+ B'E (H-H)i [B E (c = c)
=t n.e. 6rr; |n.e. 611- B.E. (HF)
* - (c-H)
'E
= ! r ue *! * ,,a- s5s = - 26e kr mor-r. = IBzi.6 + z x ttt o + tzi.!1

6'aH""ai"n =rBE (Reactants)

oru-u+ jo= o +H-o-HraH = ?
$3+!xne2 2x464 -rso=rBE (c_;li.liE:'$l
.
"-ffi Etr*t--
. r\er energy released q2g
mot-l
=
= 249kt
_ 679
E. Let us catcutare
-tr,"."
a,
(.-;)'z.BrE;(:"--?]
,o. ,n" ,"r*",1o1 "E
(N-H)J
Le. AH = - 249 kJ mol-l H H
Arternativety, aH = B.E. (H2) +
+ (o,B.E. qH6@) i.e.r_*_i_" O, .... 2c(s) + 6 H G)
_ 2 B.E. (o_H)
AH
*+x4s2 -2 x464 = - 24ekJmol-r. 2x Eqn. (r) +3 x Eqn. (rrD-Eqn. (i)
. :ot, gives
4. For reaction (iO AHReacfion
=?A25.,7j kl
AH = B.E. (H, * |zs.1or1- 2 B.E. (o -H) If, is the bond eners' of c--c bond, rben

-s1.a -",4.2 t!,rrr.o-2 xB.E (o_H)'t'"!lZnil.,==ffir]l,

or 2 x. B.E. (O-11)
= 221.2kcal
or x = 329.7j kJ
B.E. (o-Hi
^ AH,."ction
e'
tcai
= r 10.6 = [8.8. (C = C) + 4 B.E. (c-H)
H H +3B.8.(o = o)l _lzx2 xB.E,(c=o)
s' H-c =.-n * H-H...* I +2 x 2 x B.E. (o-tt)l
=.1 [619 + 4 (414)+3 (49C11-10
1tzo1*o ltoo11XS
=_964kJ
 PradeeP's
5146

ji::ir:i:i::;t::l:jti:t:till:lii::ji::iiii:i::.i::l::rji:iiii:i::'lil:ji:iijiii:lii:::i1:ii;iiliiiilil:;i:i1:;:ii:i:il;il::Ii:;i!:l:jr:1:i

AD.D TO Y U.R
comPounds wh e those
H1. rhe mmPounds whi:n nL" *qlllY-",:t5,1:[il:iilHnl"'":[rTJd,exothermic
with posiiNe enthalpies of formatron are
ca :::-..^,,^..
#2. VariationofheatofreactionwithtgmPeratureisEivenbyKirchoff,sequatiollviz.

l.!f;rl =o.o * {-fl=o.o

\ ,,, /T
(M)) = n.-u u, o1' -
I,
ar
*t'
L2-'1 = o, ;,
\ /v eDerry
at tenlperatures Tl and T2 and aE I aod AE2 are internal
where AH I aDd AHz are enthalpy chan8gs
changes at tenperatures Tt aDd
T2 respectively'

AC/ r cP of cP of reactaDts Products->

=
cu of readants
ac, = : c, or Prooucts-'
volume respectively-
at mnstant Pressure ald at coDstant
C" and C', rePresent tleat caPacities
(Le 1 / 2H2@) + oq
, t'"""*'", t",-ation of H+ ion in dilute aqueous solution is taken as zero -
value' the enthalPy of formation of any other ion ffi b*dt;l"t"d:
H+ 1o41 + e- , tn'= 0) Using this
*;i"'-
e.& Hcl13) :11 H* ('q) * cf sq) ^H = -
7s il1 kJ

7s 14 kr
,.r. au7{u+ (a{) + ^Hi(cl- (d4) - ^Hi(HCl G)) = -
get
But alri(HCl(8)) = -92 30 kJ' Putting the values'we

0+ AH'/(CI- @q))- (-s2'30) =-7s 14k'I

or (cl - (44)) = 44 YJ
AH
i -167 atomicmolecule
is nearly halfof th
ia, J EnthalPy of formadon of an aiom
e.g.H2@)'z]H(s)' AII'= 435 kJ mol-l

halPy of solution
quation (relating
tioD is

+-+l'l
q are solubilities at temPeratures
i' and T' respectively'
where Cl and
form
mation is takenaszero for the allotro-pic

ill;;;::x 1:';xili'x;,il'i"i"',fl lil'il'

oot change [es cusoa (r) + s Hzo
...
',lll"'JTillll;,"", the Phvsical state or the solid does
-rtOo.t rt charges'
UrO 1r;1. However durirg dissolution' is
oumber of moles of the solveni
wheo one mole of the solute is dissolved in a definitc
The enthalpy change
called lntegral heat of solution'
FIRST LAW OF THERI\,ItODYNAMICS AND CHEMICAL ENERGETICS sl47

,, Enrhalpy of ionization of a weak acid can be calculated by subtracting enthalpy of neutralisation of that acid
with a sirong base from 57 .7 kJ e.g. heatof ionization of CH3COOH:57.1 *55 2=I 9kJ
Likewise enthalpy of ioDization of a weak base can be calculated.
rr Enrhalpy of neutralisatiofl of HF is about 68 kJ i. e. n]ore than that of a stronS acid with a strong base viz 57. 1
kJ. This is due to very hiSh hydration eners/ of fluoride ions.
: AHm.uustion is always negative- Hou,ever, there are some reactions which involve combiDation with oxygen
leading to partial coDrbustion but AH is positive e.S Nz + Oz + 2 NO, AH = +ve
Further wheo F2 combines with 02 to form OF2, F2 is reduced and not o(idized and AH for the reaction is
positive

i.e. r, * lo, .... oFr. aH = +ve.

i { The neutralisation reaction ofa strong acid with a strong base is
tl+ (oq) + oH - (aq) -- H2O (D, AH = - 5?.1 kJ mol-l

SECTION-V etc.) provide the best source for means oftraaspor-

SOURCES OF ENtrRGY
5.19. Dilfereni Sources of Energy i.iji:i:i+:i,:ll:i."ii:i..r:ai.:i:::1ii:.:i:i::i:l
We need energy almost in every sphere of
life e.g. for lighting, cooking, Eansportation, com-
munication etc. Further every industry is depend-
ent upon energy. In fact, tbe progress of a country
is determined on the basis of the electrical energ5r
it consumes as it is an indication of the industrial
progress andthe progress ofliving standards ofthat '
country.
In this respect, India is still backward as the
electrical energy consumption per person is quite
low as compared to the developed countries. Afew
sources of energy are briefly explained below :
1. Fossil fuels. Coal and petroleum which are
believed to have been formed from animals and
plants that remained buried uader the surface of
the earth for millions of years where they were
subjected to high temperature a.nd pressure are
called fossil fuels. These are the most commonfuels
at the disposal of man and hence are call ed conven-
tional fuels. In India, nearly 907o of the total energy
requirement is met by these fuels. The various frac-
tions obtained by fractional distillation of crude
petroleum (e.g gasoline, diesel oil, kerosene oil
tation (i.e. scorters, cars, buses, trucks etc). Con-
densed Natural Gas (CNG) has been another
substitute for petroleum products. Similarly, the
heat energy produccd by burning of coal may be
used 'directly wherever required or may be used for
the production of steam which may then run the
turbine and produce electricity. This is the prin-
ciple of a thermal plant.
The sudden sharp rise in prices of crude
petroleum by oil producing countries in the mid
2000 and tbreat from global warming. rising sea
levels and climatic changes due to green house gas
emissions from fossil fuels forced the countries
across the world to think of alternatlve sourcts of
energy i,e. non- conventional all.d renewable. Afew
- of these are given below.
2. Dung and wooil. This is another very cheap
and easily available source of energy. Gobar gas
plants are becoming more and more popular in the
rural areas which make use of cow-duag and
decayed plants.
3. Water. Falling water has high kinetic energ5r
which can be used to run the turbine and produce
electricity. This is the principle of hyilro-electric
powet stations set up at Nangal and
Shivasamudram.
5148 Pradeep's,:!.t il11;,;,, 1,:,._Ai.Ai-i lAD
4. Radioactive elements. A small amount of a earth's interior in the form of hot springs. The heat
radioactive element such as uranium when under- of these springs can be utilized as a source of
goes nuclear fission produces a
tremendous eniergy. There are some places where people cook
amount of energy which is equivalent to the energy their dishes in thehot water springs.
produced by the burning of thousands of quintals 7. fidal waves and ocean currents which pos-
of coal. Hence every country of the world has been sess high kinetic energy can also be e4ploited as a
trying to harness energy from this source. The source of energy.
plants which work on this principle are called In India, coal has been the main source of
Nuclear power stations.In India, we have nuclear energy. It is only during the last few years that Oil
power stations at Thrapur (Maharashtra), Kota and Natural Gas Commi"ssion has made a break-
(Raiasthan) and Kalpakkam (Tamil Nadu). through in the field of petroleum. After inde-
5. Wind. This is a gift of nature. The use of pendence, considerable development has also
wind mills has been quite common but this source taken place in the field of hydroelectric power as a
has not been exploited fully yet. source of energy.
6. Geothermal sources. The interior of the The ffierent sources of energy consumption
earth is very hot. Hence, at a number of places, we in India and in the world, as they existed in 1,998,
find hot gases and hot steam rushing out of the are shown in Fig. 5.15 below :

INDIA WORLD
COAL (55'20/6)
orL (3s%) RENEWABLES
(2./")

HYDRO-
ELECTRIC
(2o/o)

NUCLEAR
NUCLEAR ENERGY (7%)
ENERGY (1%)

RENEWABLES
orL (31.s%) (3o/6) COAL (23o/o) BIOMASS
(100,6)
HYDROELECTRIC
NATURAL GAS (3o,6) NATURAL GAS
(7.s%) (21o/o)

FIGURE 5.15. Sources of energy consumption in Indh and World (1998).

5.20. The Sun as the Primary or
Ultimate Source of Energy :iti;r.;iil,
The various sources of energy such as fossil
fuels, wood, hydroelectric power, wind power,
nuclear power etc. are ultimately dependent upon
the sun, e.g.
(i) Plants grow by synthesising their food in
the presence of sunlight (photosynthesis).
(ii) The plants (forests) are then fossilized to
form coal or they are food for the animals which in
turn are a source of gobar gas or are fossilized to
form petroleum.
(iii) The heat of the sun causes rain and hence
:ii:ii::::i:
we have water-falls acting as a source of
hydroelectric power.
(fu) The heat of the sun causes winds, tides
and ocean waves.
(v) It is believed that all elements including
radioactive elements like uranium are synthesised
from hydrogen by the process of nuclear fusion
taking place in sun or other stars.
Efforts have also been made to explore the
solar energy for generating electriciry. However,
these efforts have not met with any appreciable
success so far.
 FIRST LAW OF THERMODYNAI\,IICS AND CHEMICAL ENERGETICS
The various processes are shown diagrammatically in Fig. 5.16.
NULCLEAR
GROWTH OF PLANTS
BY PHOTOSYNTHESIS
fog
FIGURE 5.16. The Sun as the ultirnale souce of energy.
5.21. Pollution Associated
with con su mption ol Fuels 1i:l{jiif.}i*?.in:.riftrirriii,irii
For the product.ion of electricity by the ther-
mal power plants and to meet the ever increasing
needs of trarsport in the cities and towns, the con-
sumption of fossil fuels (i.e. coal a.ud petroleum
products) is on the increase. The combustion of
these fuels produces carbon dioxide, carbon
monoxide, oxides of nitrogen and sulphur (by
oxidation of compounds of sulphur and nitrogen or
elcmental sulphur present as impurity in the fossil
fuels) and somo unburnt hydrocarbons. All of these
are the pollutants of the atmosphere as explained
below : the nuclear power stations, This sometimes causes
(i) Carbon dioxide. This is the main product
of combustion of the fossil fuels. If its percentage
in the atmosphere increases beyond a particu.lar
level, the climate of that place may ch aage e.g. ttLe
average temperature may increase+.
(ii) Carbon monoxide. It combines with the
haemoglobin of the blood forming carboryhaemo-
tThis cffc.t i6 csllcd '8rctnhoosc cftcct, (iis-cusscd in Unit 1E).
SOLAR ENERGY PRODUCTION
OF
(AN EFFORT IN ELECTRICIry
PROGRESS)
WNDS, TIDES
OCEAN WAVES
MARINE ANIMALS
FOSSILIZED TO
PETROLEUM
globin thereby making it incapable of transporting
oxygen to the different parts of the body.
(ili) Oxidcs ofnltrogen and sulphur. They are
corrosive and poisonous. They dissolve in the rain
water thereby making it acidic. This is called 'acid
rain'.It damages the stone buildings andforqsts and
also the metals.
(iv) Unburnt bydrmarbons. Some of these
hydrocarbons are a great health hazard and may
even cauie cancer.
Besides fossil fuels, another very important
sourc.e of energy is the 'nuclearfuel' being used in
even greater problems. A.lthough the release of
radioactivity into the atmosphere is strictly control-
led, yet disasters do occur sometimes. For example
in 1986, such a disaster took place in Russia (in
Chernobyl). A very large number of people are
affected when such a disaster occurs, The storage
of radioactive waste (produced by the nuclear
 s/50
power stations) which has still a very high radioac-
tive level poses a very serious problem.
Scientists all over the world are working to
control the pollution. Many advanced coutrtries
have already achieved a significant success. In
India, efforts are on to rninimize the pollution.
5.22. Why Energy Crisis-Alternativc Sources of
__!1"lgy- -I : " 1!l e 9I:9 !i"3!:"
o"rr"rgy
The various so*""s, as discussed
above; may be divided into two categories
(1) Renewable (Non-depletable)
(2) Non-renewable (Depletable)
Renewable sources include wood (plants),
wind, falling water, geothermal Power, ocan
waves, tidal waves, solar energy etc. These sources
are produccd coatinuously in aatue and are aLnost
inexhaustible, at least so long as the life exists on
this earth.
Crude oil (petroleum), natural gas, coal,
uranium etc, are non- renewable energy sourcs as
these have accumulated over ages and are not
quickly replaceable ufien they are exhausted.
The rate at which the non-renewable sources
of energy are beiag consumed, it is expected that
their stocks are likely to exhaust by the middle of
the 21st century. Hence there is a likelihood of
energy crisis.
It may be pointed out that the law of conser-
vation of energ5r does not fail here. The only prob-
lem is that the combustion of fuels is a one way
process i.e. either tho products of combustion are
not converted back into the original substances at
all or they are converted back at a rate much slower
than the rate of their consumption. For example,
coal burns to form CO2 but CO2 is converted back
into carbon by nature tlrough photosynthesis at a
much slower rate.
Foreseeing the problem of energl crisis,
scientists all over the world are trying to find ways
and means ofgetting all types of enerry &om altcr-
1 native squmu'i.e. renewable and non-convention-
al sources. A few of these are given below :
(1) Solar cEr1EI e.8 in the form of solar
' Lbokers, solar water pumps, solar photovoltaic
ce.lls, solar water heaaGgisystems etc.
(2) Blomass. It is thB waste material obtained
from animals and plants e.& cattle dung and dead
.To tap altcmati!'c sourtts,India has set uP Min
.all sou{tcs likc solar, xrind, biomass, hydro Projects etc
parts of plants and animals. When allowed torotten
in the absence of air, it decomposes to produca
biogas which like natural gas can be used as a
domestic fuel or to produce electricity. The residue
left contains a high percentage ofdtrogen and can
be used as a fertilizer.
(3) Coal. Coal as such has the problem of
transportation an The im-
purities of sulphu it is con-
verted into a gase c natural
: gas which can be easily transported in pipe lines.
The product contains a mixture of CO, [I, and
CHn all of which can be used as fuels.
(4) Hydrogen. It has high heat of combustion
and does not create any pollution problem. Its use
as a rocket fuel is well known. It can be obtained in
large amounts from water. It can be used as a good
fuel for production of electricity.
(5) Nuclear enerp. As already metrtioned,
radioactive elements such as uranium and
plutonium are a potential source of energy which
are being used to produce electricity.
(Q Other sources, These irclude geothermal,
wind and tidal waves and ocean currents.
However, we should also try to conserve ener-
gy as far as possible. A few practical suggestions
ior the consenation of energr are listed below :
(1) Use the fuel that is renewable.
(2) Use high gffiglsncy oil or gas stoves which
burn the fuelwith a blue flame and not with a yellow
flame (which is an incomplet combustion produc-
ing less heat).
(3) Keep ready the next item to be heated,
otherwise, put off the stove.
(4) Usethe vessels with flat bottom for heating
and not the vessels with round bottoms.
(5) Use energy-saving devices for cooking like
Pressrue cookers etc.
(6) Switch off the lights, fatrs etc. when not
required.
(7) In winter, better sit in the sun to warm
yourself in-stead of using heaters inside the rooms.
(8) Use casseroles for keeping the eatables
hot instead of heating them again.
(9) Thke bath with fresh running water instead
of using geysers.
(10) Plant trees ifyou have surplus land.
for Non-Crnvcntional Encrry Sources (MNES).It has tapped ncarly
 FIRST LAW OF THEHMODYNAMICS AND CHEMICAL ENEBGETICS 5/s1

, ) Classify the following into open, closed or isolated systems :

(i) Animals ond plants (ti) A refcrigerator or fl fridge (jii) A solar cooker:
Ans. (i) Open systenr (ii) Isolared systeD (xi) Closed slstcm.
il -l To what type ofsJrstem the following belong ?
(i) Tree (ii) Tea placed io a kettle.
Ans. (i) Open system (ii) closed s)stem.
r () -1. Which ofthc following are open, closed or nearly isolated systerns ?
(i) Human beings (ii) the earth (iii) ctrh oftohato soup (iv) lce-cube trny lilled with wrrer (y) A satellite ir
Irn orlrit (yi) Colfee in a therEros llask and (vii) llelium lilled balloon. (N.C.E-R.T.)
Ans. Open : Human beings, Earth, Ice cube tray
Close : Can oftomato soup, A satellite in an orbit
Isolated : Coffee in rhermos flask, Hetium filled balloon.
. {.1 -l Separate out the following inio extensive and intensive:
Volume, Ibrhpemtuie, Prssure, Boilihg point, Fre enerEsr
Ans. Volume aDd free energy are fitensive, others are intensive.
(J i What is the most important condition for a process to bc rcversible in Thermodynamics ?
Ans. The Process should be carned out infinitesimally slswly or the driving force should be infinitesimally greater
' or smaller ihan tbe oppGiog force.
Q 6 Which ofthe follo*ing sre state functiotrs ?
(i) Heightofa hill (ii) Distance trsyelled in climbing the hill (iii) Eneryy change iD cliEbing the hitl.
(N.C.E.RT)
Ans. (i) and (iii).
, Q. ?. Why'Kelvin scale of temPeraturd is called rAbsoluae scale of temperature' ? What are the reference poitrts
on this cqle.
Ans. On ihe Kelvin scale of temperaturc, zero point is tbe loweit p6sible temperature whereas on the celsius scale,
zero point is only with referenc to lce point. Hence the former is called absolute scale. The reference poilts
are absolute zero of temperature and the triple poiDt ofwater (0.01.C or 273. 16 K).
q) $ Ca[ the absolute volue of internfll energy be determined ? Why or why not ?
Ans. No, because it is the sum of different typs of energies some of wbich cannot be dctermlned.
(.) e One mole ofCO2 at 300 K aud I Atm pressure is heated
iD a closcd vessel so thot temp. is 500 K aDd prcssure
is S atm. Then it is cooled so that tcmp, is joo K ond pr:essure is I ath. Whotis the change in internnl encrgjr
ofthe gns ?
Ans. No chaoge because internalenerry is a state function.
(J Irr \lhter derDmPces by absorbing 256 2 ofelectri.fll etre45/
kl tEr Elole. When H2 and 02 conbi1e to form one
mole otHrO, 2E6 2 (l of he{t is produced. Which law is proved ? Whst statemeht o[ the lnw follot s from it ?
, Ars'Law of conservation of ener$/ or l st law of thermodynamics. Def, Energy can nelther bc created or destroyecl,
although it may be converted from orle form to another.
i., I L N.itherq nor'l, is:r state function. yet{ + l/ isa state function. Explsitr why.
ADs. .1 + r, = AE and aE is a state functioo.
{l ll Why heai is not a st{rte function ?
Ahs. According to first law of thermodynamics, AE =q +w otq = AE
-,r.AsAE is a state fuoction but l, is not
a state function, therefore q is also not a state function.
r., I 1 Why absolrte vahre of enthalpy c[nnot be determined ?
Ans. As H = E + PV and absolute value of internal eDergy, E nnot be determined, therefore
absolute value of
H caDnot be determined.
 Pradeay's Ncttt Courcc Chc-istrg@
sl52
t.t I J Whot is thc relation between AH atrd AU ? Undet what condition, the two ate equal ?
Ans. aII = aU + PAV = AU + A rr Kf For conditioDs see page 5/14.
-) I5 Explain why heat caPacity is not o st tc function'
Ans. Heat capacity (C) = As'4'is not a state fuoction, thcrefore C is also oot a state function
#.
(l Ic Derive thflt for an ideal gag C, =dE/t df,
^ndCp=dH/
AIls. Seo page 5/17.
(l ll Specific he{t ofl-i (s), Na (s), K (r), Rb (r)andCs (r) rt 39E K arc 3 57, 123,0 756,0 363 and0 242
J g-r 6-t r-espectivella Compute the holar heat capacities of these elehents oud identify any Periodic
i.ina. It tt i" t.en<I, use it to predict the molar hest copacity of Ft' (N'C'E'tr.T)
""" "
Ans. Molar heat caPacity = sPccific heal x Molar mass
1
Heoc for U, Na, K Rb aDd Cs, their values (JK- mol-1) will be rqspectively
3'57 x'l =25 0, 12ix23=2A 3, 0'756x39=29 5, 0 363 x85 =30 86,

0242x133=:z 2 JK-l mol-l.

Plotting and extrapotatiofl gives 33 5 JK-I mol-I for Fr2B.
(.1. ll{ ts {p atways greatcr than qr;? Explain why or why noL
Ans. qp is not greater thaD 4u always. It depends upon whether &rg is +ve or -ve Le nr>n,ot no<n,
(qp=qu+ N\RT)
(l I l). In what form the enerE/ is Produced vher Petrol is burnt in the engine of a csr or a scooter ?

Ans. Partly as mechanicalwork and partly as heat.

(J. l(1. What is the mo6a important rcoction thot tskes place in our body that mairtains body tampemture ?

A.trs. Slolv oddation of carbohydrates.

t
JI i
Why some reactions are exothermic while some others are erdothermic ?
Ans. lfthe total internal energ)i of the reactanls (ER) is greater than that ofthe producLs (Ep), the eners/ is released
and the reaction is exothermic. However if ER < Ep, then energy is absorbed and the reaction isendothermic.
(.). f: The resction
N2 G) + ()2 G) * 2 NO k) 7 Kl is...".'.. thermic ond AII = """"kJ
-r80
Atls. Endothermicand AH = + 180.7 kJ
1.). l-l will the heat volved he same in the followitrg two csse-s ?

(a) Hz@) ++o2@)- Hzo G) otH2Gt +

!o, G;..._ Irro 14

If not' ir !ryhich cas itwill be 8re&ter snd why ?

Atrs. No. It will b greater in case (D) because when H2O (8) condenses to folm Hzo (D' heat is released-
{). 2.1. Which of the followitrg ls/are exotherDic and thich igare endothcrmic ?
(i) ca ...- c"2+ g1 + z (ii) o G) + e- o- (S)
@) "-
(iii) N2- G) + ,- .....- Pr- g1 -
Ans Endothermic (ionizition energy
(i) is required)
(ii) Exothermic (first electron affinity is energy released)

(i ) Endothermic (higher electron affinities are energies required)

(.! l5 The prorlucts ofcombustion of6 g cabron contaitred 50% COrollrd SMo CO' The heat evolved'was 126 kJ'
calculate the enthalpy ofcombustion ofcarbon. Given that the enthalPy offormation of co is -110 5kJ
mol -1.
Ars. Heat evolved from the combustion ol one mole of C to form 50% CO, and 50% CO = 2 x l25 = 252kJ

Suppose heat evolved from conrbustion of 1 mole of C to COz = .r kI

FIBST LAW OF THERMODYNAMICS AND CHEMICAL ENERGETICS 5153

. I x.-
Heal ofevolved from mole = kI
Z A
Heat evolved from combustion of 1 mole of C to CO = 110 5 kJ
.. Ileal evolved
I llo 5
from mole = -i = 55 25
Z

;+ 55 25 =252 or r=393.5kJrnol-t.
Q. 26. The enthalpy ofcombustion of glucose (CfHl2Od is 2E40 kl mol-l.lYhat is i(s cslorific valuc ?

Ars. Molar mass of glucose (C6Ht206) = 180gnol-l

.. 2840 kJ mol .l = 15 78 kJ r,-l

Calorificvalue -
l80g mol-l
Q.27.HeotofdissociationofaceticacidisI9kJmol-r.Ilowmuchhc:rtwillheevolveCwhenonenroleofncetic
acid is neutralized by NaOII solution ?
Ans.57 1-1 9=55 2kJ
Q 28. Fill in the blanks.
(i) The dissolution of CuSO. is ,,,.,,. thermic while dissolution of CUSO4 . 5H2O is ........thermic.
(t'i) AH"*1*,1oo = AHr,,<oo + .....-......

(iii) The enthalpy of solutior of BoCl2 (r) and BnCl, . 2IIrO (s) a.e r and y kJ mol-l respectively. Then
enthslpy of hydration ofBaCl, will be.........
Ars' (i) exothermic, endotherD]ic (ii) AH,"porir"rion (iD) (r - r) kJ m ol - 1.

Q. 29.
t
hy boDd enerly is t{ken as an avcragc value ? ExplaiE with a suitable example.
ADs. The bond eners/ of the same boDd iII different polyatonric moleculcs is not sanle e.g. bond energy of C-Cl
boDd in CH3C|, CH3CHzCI etc. is nol same, Even in the same polyatonic molecule like CH4, the boDd
ener$/ of all the four C-Il bonds is not san]e. Hence an aYerage value is taken.
Q. 3(,. Give appropriate reasons for the following :
(i) lt is preferable to deterhine a chaDge in enthalpy than change in iDternal eoergy
(ii) It is necssary to delitre th'Staldsrd statd.
(iii) It is necessflry to speciS the phases ofthe resctarlts aDd products iE a thermochernicnl equation.
(NC.E.R.T)
Ans. (i) Change in enthalpy is the heat evolved or absorbed at constant pressurc. As most ofthe reactions are carried
out in open vessels ,.e. at clnstaDt pressure of olre atmosphere, henc change in enthalpy ts preferred.
(ir) This is ofa reaction depeods upon the conditions under which the reaction is carried out.
because the eDthalpy
(iti) The e[thalpy change of a reaction depeods upoo the physical state of the reactaDts aDd products e.&
standard e[thalpy offormatioD ofwater is nct saDte for H2O (g) and H2O (4.

Q -rl The enthalpy ofneutralisatior ofacetic acid by KOH is -55 tklmol-l while thst of hydrochloric ,rcid by
KOH is kJ mol -', Why are tley ditfereDt ard what does the dilTerence represent ? (N.C.D.R,T)
-57.3
Als. Heat of neutralisation of acetic acid $ less than that of HCI because acetic acid is a weak acid aod does not
ioDize completely. Some heat is used up for the ionization ofacetic acid. The difference represcnts the enthalpy
of ionlzation of acetic acid.
Q. -11 What is the basic difference between enthalpy of forEation ond enthalpy of reaction ? Ilhrstrflte with
suitnble examples. (N.C.E.R.T.)
Ans. (l) EnlhalPy of formation enthalpy change for the formation of I ltrole ofthe srbstrnce from its elemeltts.
is
For exaDrple, let us colNtder the following two thermochemjcal equatjoDs :

H2 G) +
1
(/1.
02 B) ...- llzO AH. = - mol-l
, 285 8 kJ

and 2l+(9 + oz@) +zHzO (4, AH" = - 571.6 kJ mol-l

5154 Netl Course Chemistrg
In the first case, AH" is enthalpy of tbrmation of HrO (/), while in the second case, it is enthalpy of reactioll.

(ii) Enthalpy of forrnation is for the formatioD of 1 mole of the substance from its elements only. For example,
we have
CaO (r) + Coz (8) .--_ CaCO3 (t), AH" : - 1?8,'3 kJ mol-l
As 1 nrole of CaCO, (,r) has bcen tbrmed from CaO (i) and COzG) and not fronr iLs elements, aH'is not
enthalpy of fornration. It is simply cr.;rhalpy of reaction.
Why in a reaction enthalpy chlnge is alwnys rvritten per mole even if two or more moles of a reactant or
prodrrct are present in the balanced equation ?
Ans. This is because if the units are multiplied by a number, the unils do not change.
One kg of graphite is burnt in a closed vessel. The same amount o[the same sample is brunt in an open
vessel. Will the heat evolved in the two cases be same ? If not in which case it would be greater ?
Ans. Same in both cases because Ms= 0.
Why standard heat of formation of diamond is not zero thorrgh it is an element ? (H.S.B. 1997)
Ans. The standard state chosen for carbon is graphite and not diamond because graphite is more common and
stabler form of carbon in the standard state.
' r. Is the bond energy of all the four C-H bonds in CHo molecule equal ? If not then why ? How is the C-H -1
bond energt then reported
'
Ans. No because after breaking of C-H bonds one by one, the electronic environments change. The reported value
is the average value of the bond dissociation energies of the four bonds. C-H
The enthalpy change for the reaction N2 G) + 3 Hz(9 .--- 2 NH, (g) is - 92.2kJ. What is the enthalpy of
formation of ammonia ?
Ans. Aim,l*, rrl **rrg)--_ NH: (s), = ?
^H/
Given : Nz G) + 3 H2@)+ 2 NH3 G), AHro = - 92.2W
o.r.')
.: AH,i(NHs) = - = -.16'l IrJ.

: '.. What is the basis of=Ilessts Law ?

Ans. Hess's law is based upon the fact that enthalpy is a state function r.e. enthalpy change depends only upon the
initialstate (r.e. enthalpyofthe reactants) and thefinal state (re. enthalpyoftheproducts) and does notdepend
upon the path followed.
', Write the standard state for each of the following in which AII/ is taken as zero : Carhon, Sulphur and
Bromine.
Ans. C (graphite), S, (Rhombic) and Br, (/).
r .r, Given that:
O G) + e- + O- - t42kJ nrol-l andO ft') * 2 e- + o'2- G),AH = + 712kJ mol-l
G),AH =
Whatwill be AH for O- (8) + ,- o.2- (g)?
Ans. The second reaction takes place in-two steps as :
O (g) + e- * O- (g), AH = AH1, O-- (C) + e- 02- (g), AH = AH2
-
Hence AHI + AHr= a 112 (/

But AHI -- - l42kJ nrol-l (Given)

.'. - l4Z + AHz = + 712 ot AH, : 354 kJ mol-l
/hernatively, subtract Ist eqn. from 2nd eqn.
: : Calculate the enthalpy of vaporisation of water at 25'C and 1 atm pressure. Given that the standard
enthalpies of formation of HrO (I) and HrO @) are - 2E5.E and - 24t.8 kJ mol-l respectively.
 FIRST LAW OF THERMODYNAMICS AND CHEMICAL ENERGETICS 5/s5
Ans. Aim : H2O O ..- H2O 1g;, aH" = r
AlI" = AH/ (H2O (s)) * (HrO (l)) = - 241 I - (- 28s.8) kJ nlot-l = 44 kJ mol-I.
^ri/
Q.l: AIIr.' for freo[, CHCIF, is
- 4t0.o kJ mol-r. Represcnt it hy thermochernicrl equatiotr.
Ans. C (r) **"r@> * + Fz G)-.. cHCtFz, - 480 0 U mot-r.
lClrg ^H/":
Q. J-t Why is AU = 0 for isotherEal cxpansion of an ideal gas ?
ADs' For an ideal gas, the interoal energ/ is a functron of temprature only. Duriog isothermal expansion, as
temperature remains constant, there is no chaDge in ioternal enertS/ t:e. AU = O.
e.,14. lvhy standard enthalpy of lormation o[elementory suhstances is token as zcro ?
Atrs- Enthalpy of formatioD is the heat chango iDvolved in thc formation of one mole of tbe substancE from its
elements. An element formed from itself means Do heat cbange ...e. AH./p = 0.

Q J5 ThesPecilic heot ofa gas is fouDd to bc 0 075 colorie at constant volume oDd its formuls rreight is 40. Whot
is the atomicity ofthe gas ?
Ans. Molar heat capacity. Cu = 0.075 x .10 calorie = 3 cal nrot-l
Co = C, + R = 3 + 2 cal nrol-l - 5 calmol-l
y= Cr/ C,, = 5,/ 3 = 1.66. Hence the gas is monoatomic.

v
Q, 1. Under whot conditioh, the heat evolved or f,hsorlred is cqual to the internal energr chnnge ?
Ans. When the volunte remaiDs coDlaDt
Q. 2. Under what conditioh, ah exteDsive property cltn become intensivc ?
Ans' An extensive property bccomes intensNe when unit an]ount of the substance is taken e.g. mass aDd volumc
are extcnsive but densily (nlass Per uDit volume) and specificvolunte (volume per unit nrlass) are intensive.
Q. 3. Why we rrsllally study enthalpy change and not internal energy change ?
Ans. Bccause Dtost of the processes (reactions) are carrjed out iD open vessels r:e. at constant pressure ( 1 irtnt)
=
Q. 4. Wlrat xre the.onditions for expressing stand.trd cnthalpy changc ?
tus. 25'C( 298 K) and one atmospheflc prcs.sure.
(:. 5. What is the sign of AH foi etrdothemic reactions and why
?
Ans. AH is positive because AH = H, - Hp and H^ < Hp
Q' 6. what is the relationship between standard enthalpy offormfltion and the entharpy ofa compound ?
Ahs. They are equal.
Q. 7, What is the vnlue of enthalDy of neutralizatio[ of { strong acid by a strong base ?
,,as.
-57.1kJ
Q. 8. lvhy erthalpy of neutralisfltio' is less ifeither the ocid or the base or both are weak ?
Ans' A part of the hcat is uscdup for the dissociation ofthe weak acid or the weak base or for bo(h rf rhcy are weak.
Q. 9. Why enthalpy of neutra lisntior ofHF is greater thar 57.l L.l mol-t t
Ans. This is due to high hydration energy of fluorjde i(n.rs.
Q. 10. Whflt are specilic he{rt capacity ubd molar hert cnpacity [or rrxter ?
Ans. Specific hcat capacily for HzO =4. 18 JK lmol-l
Mdilr hear capacrl),for H2o = 4. t8 x ls = 75.24 JK-t mot-1.
Q' 11' u4tat is the law c,rlled rYhich states that the totfll cDthalp) change in n cheorical re{ction is always
same
the sulrre tempemture ? ^t
Ans, IIcss s liw ol constilnt heal sunlmalioD
Q. 12. What are renervable sourccs ofenerlo.?
s/s6 Pradc.,p's Nert Course Chemist qlffifi
Ans. Those which are produced continuously in oature and aro inexhaustible e.g' wood, solar enersl etc.
Q. 13. What is SI delinition ofone KolYin ?
Ans. Ooe Kelvin is lZ73 16of the tiPle WiDt temPerature of watet (vizn3 16K).
1

thqr-t-#,nerY*?1.Rf;e,?P.i.o-ne,.,cARRvrNG2oi3n'ARKs
Sti il l. What do you undersEnd by open, clced and isolated slstens ? Illustrate with suitable oGmples.
1,, 5l
2. What are exteDsive aod i[tensive proPerties ? Give two examPles of each.
3. Classiry, giving reasor, the following into intensive and exteosive proPerties:
(i) Enropy (ii) Vsclsity (ir'i) Heat caPacity (rv) Surfac tension (v) VaPour Pressure
(vi) RefractNe i[dcx
4. How willyou distinguish between the two
(i) open and closed srstem
(r'i) extensive and intensive properties ?
r.,r i-r S. Define Zeroth Law of Thermodynamics. How hasit been useful in the measurement of temPera-
l, < .1 ture ?
\r( 5 5 6, Fxplain, giving reasons, which of the quantities out of internal energy, heat and work are state
r,' S 6 functions and which are not.
7. Derive an expression for tbe work ofexpaDsion ofa gas (le =
-
P A n.
t. (a) Sbow that the Pressure volume work, W =
-PAV
(D) List thc imPortaot sign conventions for beat and work.
9. What do you mean ry hw of conservation of eners/ ? Write a mathematical rolationshiP between
heat, intemal eDergy aDd work do[e by the s]stem.
10. State the law of cooservation of eners/ and give a mathematical expression for it. MeDtion also two
examples to supPort the law.
11. How can you justify that though q and are not state i'unctions, yet (q + w) is a state function ?
',
12. Discuss the significaoce of the mathematical expressioo in which the heat absorbed by a system is
related to interal energy and work done by the s)stem
13. Describe the 1st law of Thermodlnamics.
14. State tbe first law of thermodynamics aDd dcrive a mathematical expressio[ for it.
\, ( a: 15. What doyou undeIstand by'Etrthalpf and 'ErthalPy change' ?
16. Starring with the thermodynamic rclationships AB:4 - PAV and H = E+PY derive relationship
LH - qp
.r.i:\. 17. StaniniwiththethermodynamicrelationsipH=E+PV,derivethefollowingrelationshiP:
AH = AE + (Aa) RT
lE. Derive the relationship btween heat of reaction at coDstant pressure, qp and heat of reaction at
constant volume, 4u. or Derive the follo iog equation AH = AE + (4,l) RT.
\(( i 9 19. What is meant by Cp and Cu ? Derive the reaction Cp - C1, = R.
srf. a l0 20. What cicmical reaction ?
is the origin ofenthalpy change io a
21. Give some examples ro show that different t)?es of energies are evolved or absorbed in differelt
reactions.
. (. <I I 22. What are exothermic and endothermic reactions ? Explain with suitable examples'
23. Why enrhalpy change is negative for exothermic reactioos while it is Positive for endothermic
reactions?
:,..5.11 24. What doyou uDderstand by a thermochemicalequation ? Cao we use fractional coefficients in such
an equation ?
\,( . i-. 25. Define ,Enthalpy of reaction'. On what factors does it depend ? What hapPens to thevalueofthe
heat ofreaction if the reactio[ is reversed 'l
 FIBST LAW OF THERMODYNAMICS AND CHEMICAL ENERGETICS 5ls7
s!(. i.l.l. 26. Deline thc folowing:
(i) Enthalpy of combustion, (ri) Enthatpy of formatioD, (st) Enthatpy of neurralization,
(iy) Enthalpy of t?porisatioo.
27. Fill in the blanks:-
(D Hz E) + ck@) 2HCl (8) + 185 kJ
-
This reaction is ..... thermic (ero or endo), AH = ..... kJ

(,r) H2 E) * or@ ......- Hzo (0 , aH = -2a6

| kJ

2H2@) + o2g) 2H2O (r) .... kJ (t ?)

(iii) CH1 (g)+2o 2 (B)
--- CO, (8.) +2H2O (B), AH= __{09 kJ
The calorificwlue of 1 kg of CHa (8) is .... kJ/kg.
(rv) C(r) ..._ C (8), =,t16.1kJ, AH is the hear of .... ofgraphire
(v) H2O (g) .+ ILO^H(0, AH = __40.7 kJ, aH is rbe hcat of.... ofsream.
(,,)
Enthalpy ofneutralization ofH2so4 witb NaoH is the amouot ofheat cvolved wheo 1 more of
NaOH is neukatized by .... mole of tI2SOa.
EJplain why !h eDthalpy of neutralizatiol of a stroEg acid with a strong base is atyays same while it
is less if eitber thc acid is wEat or the base is weaL
Scc.5.l6. 29, Ho$, is enthalpy of su blimation relared to entbalpy of fusioo alld enthalpy of ydporisation ?
Scc. -5.17.30. Statc and erplah Hess's Law of constaot heat sum tioo"
Sr:c.5.1E. 31. Dfne 'bood eners/. Wbar b tbe origin ofcntba.lpy cbange
h a cbcmical reactioD ?
Sec.5.l9. 3L Briefv explaio thc various sources of eDerry,
b s.2t.
33. What are fNil tucls ?
34. Justify the stalemc that 'Sutr b the ultimate source of ener&r.
Scc.5.22. 35. Wbat arc reneerabl and non-rcDec.able sources of enerryi Why is there a likelihood of cnerry
cdsis ?

Ust some practical suggesdoDs for ihe coffcnration of ener$/.

Lq,*.q., _p,R I.
GARRYTNG s or;o'r uARr(s
Scc.5.l. 1 Define 'thermodynamics,. Briefly describe tho imponance aDd limitistions of therrDodynamics.
Scc.5.2. 2. Define the follo*,ing terms :
(i)s,,ste ropenies (v) Isothermal
Process
Scc 5.-1 3. State ao cs.
to 5.4.
4. Priefly explaio rhe terms btcmar cnerry, work a,,d hcat. How are they iDterrelated ? Justiry that
to 5.6 internal ener$/ is a state funclioo but work and heat are Dot.
5. State aDd explai[ the ,First law of rhcrmodynamics,.
6. Briefly explain the tcnns Enthalpy and Enthalpy change. Ho$, is it related to the internal energy
to 5.E. chaDge ? Derive the relationship.
7' Derilr the reratio$hip between heat of reaction at constant pressure aDd that at constaDt vorume.
Undcr what conditioos are the two equal to each other ?
Scc.5.9. & Pefine
the terms 'specific heat' aDd 'molar heat capacity. Name the tu/o
types of morar heat capacities.
Derive the relationship betweeD tbem.
sc! 510 9. Define 'Energetics'. Frplain with_suitable examples. wbat are the
different modes of transference of
enerry beMeeD the q/$em and tbe surroundings ?
\rc 5I r ' 10. what are horhermic aDd Endothcrmic reacti6ns ? Give three exampres
of each type. Explain the
sign of AH for these readioDs.
 s/s8 l'ralcap's
Scc. 5.1 3. 11. Explain the term 'Enthalpy of Reaction.' What are the factors on which the heat of reaction
depends ?

Sec. 5.14. 12. Define and exPlain the following terms:

(i) Enthalpy of combustion (ii) Enthalpy of formation (iii) Bnthalpy of neutralisation
(rv) Enthalpy of solution (v) Enthalpy of hydration
Scc 5.15. 13.ilriely expiain ho*, the follou,ing heats of reaction are measured elperitlentally :
(a) Heat of reaction at constant volume (or internat energy change) (b) Heat of neutralisation.
Scc.5.l6. Explain the following terms:
(i) Enthalpy of tusion (ri) Enthalpy of vaPorisation (iii) Enthalpy of sublimation.
Sce.5.l7. S[at"'geiSs hw of constant heat summation'. Ho does it help in the calculation of
(i) heat of allotropic transformation ? (rr) heat of hydration-?
,Bond energ5r'. FIow does it help in the calculation of enthalpy of reaction ?
Scc. -5.ltl. 16. iXno"
Scc.S.l9. 11. List the various sources of energy. Briefly explain each one of them. Brplain that suD is the ultitDate
to 5 21. source of enerry.How pollution is caused by the consumption of fuels ?
Scc. 5.22. 1E. *ty tt is eierry if is conserved in nature ? Give some Practical suggestions for the
I "t"
conservation of enerry. "tisit "o".51

I
I
 1. Entropy (S) snd cibbs I}ee EnerEr (c). Entop! 6) is a meuwe ofrandon nels of a syitem Tie change
in entroPy during a Process is equal to the heat absorbed isothermally aDd reversibly during a process divided 5y
the absolute temperature ar which heat is absorbed r'.e. N = qi!o. / T.hs units are JK-l mol-1.
/.v.
Gibbs free energy (G) is another lhermod]mamlc quantity related to the enthalpy and entropy ofthe system
according to r.he equation G = H-Ts. The change in irs value during an isothermal process is givin by
AG=AH-TAS.
2. SPontaneous process' A Process which can take place by itselfor by initiation indepDdent ofrate is called
a sponta[eous procss or a feasible procss. For a process to be spontaoeous, ac is _ve.
3. Applicotion of First lat/ of ThermodJ.namic-s to dilfercDt tJ4res of processes
(i) For an isocfutic proce.rr. As volume is kept coDstaDt, AV = 0. HeDce AE = q _ p LV becomes AE
= 4r,
(ii) For an ohaic proce.rr. As pressure is kept constant, AE =4p-pAV i e. 17r=66 a p1y =6].I
(iii) For an ircthermalProcer,t. AI constaDt tempEratu re, for ideal gas, aE = 0. As alrcady derived iD tbe text
under thrs condition. wctp = -2 3OJ n RT bt +: n nr !t2
-t = -2
.
30J rog

(iv) Fot an adiabatic Wcerr. .ds dq = 0,

. dE = 6q + dw gives dE = dp-
But ;i= Cu or dE=cudT.
Hence dw = C, dT for 1 mole or dl, = rcd dT fo r moles.
T2

.. t
Tbtalwork done, w = n CudT = ncuGz - Tr)
|
,t1

- C, or y-t=* -R
or U,,
* - =+
Furlher Cp C, = R. Dividing by ,
- = /- |
,,R (T2 _ T1) -r
Subsliluting this value. wc gel !, =
--r-
Thus if T, > T1, w = +ve ia work is done on the system
If T2< T1, w = ---+e Le. work is donc by the q/stem.

s/s9
s/60

ADDITIONAL UgEFUL INFORMATION cantr.l

z,Tha ratio Cp / Cl,tepresenEd ry / is as follows:

Nanre of the gas . Monalomic Datomic Tiiotomic

(He, Ar etc.) etc.)
(H2, 02, Co (CO2, H2S etc.)

v=co/C, | 16 1 .40 1 .30

4. Relationshlps betweeD B V otril T for adiabatic expansion of an ideal gas

PV/ = constant
or PrVI = P2VI I
uJ
-7 p(-t)tt = clostant
E
l
ot 'l1P\t -Y)/Y = TzPtt-r)/r ul
tII
TV/-l = constant
or Tr\-1 = Trvl-',
5. Grrphlcal rcprclctrt5don ollou boslc ticl[odrrrEic Proccsscs. voLUME+
6. Ilvolsler rnd L.ophc! hr. This is anotber law of thermocbemistry s,hich was put fosrard before Hess's
law. It states as follosrs :

The enthalpy ol decompsitia of a cdnqwd irto is elcrwru is equal ,o itr e halqy of fomation bu with
opposite sign e.g-,
C(r) + O2G) cozG),aH =- jel skJ a
- I
CO2G) .- C(r) + o2G), AII = + 393 5
'tJ ,!,
d
f
(r,
o
E
o,

the following four staSes :

I. Isothermal expansion
IL Adiabatic expaDsion
III. Isothermal oompression
Mdiabatic compression.
ie. A(Pl, \/t, Tr)* B (P2, V2, T1)- C (Pr, Vr, Tr)._ D (Pa, Va, T)* A(Pt, Vl, Tl)
It may be noted that the iDternal eners/ change or eDthalpy chan8e or entroPy chanSe in a cyclic procss is
zefo.
t. CoDversion ofhest into !f,ork-C{rtrot heat engiue. The fraction of the heat absorbed by a machine that
is converted into work is called the efticiency of the machiDe. It is Siven by
w Qr- Qr Tz-Tr
1= or=--er-=--r;
where Q, = heat absorbed ftom thc Jource at temP. T2
Ql = heat rejected to the rft,k at temp. Tl
FIRST LAW OF THEBMODYNAMICS AND CHEMICAL ENERGETICS s/61

c.B.s.E.-P.nn.T. (AnilNS) St ECIAL

/r. s u BJECT ItE QU I.:STIOIi,S
e I. Horv crn you justlly that
the tdork done in the
reverEible expensio! of A gas is the maxiEum
work obtalled ftom the system ?
Ars. Work done in the rcversiblc xpaDsion of
gven ry
W=-P..,AV
For the expansion of the gas, the sxtemal pres-
sure (Pcrr) has to bc less than the intemal pres-
sure of thc gas. Hou,ever, for reversible
expaBion, Pcrr should be iDnDitesimally smaller
than the intemal pressure. In other words, for
rcversible e,rpansion, Pcrr is the maimum value
of external pressurc. HeDce for a $ven chaDge
volume (Av), Pcn AV is the maximum value-
Thus,
W.o = W*"'
Q l. A s!6t I
is chaDBGd ftom state I to ststr II by
t-o dillcrent paths. IE the llrst path AE = 9.
CoEEent on the value of AE and q by the second
path. Clve rc{sorc for yolr onser.
Ans. AH by sccond path will be same as iD thefrstpath
because AH is a state fuoction. However, 4 will
not bc same by second path becuse it is not a
stete function.
Q.3. Whst is tte dltrcrlnc. b.hrcetr hord cD.rBr atrd
bond enttolpy ? Explatn takhg exaiDple of
E2(9.
AIts. Refer to paSe 5/42.
Q. J. Vghat is dillernce between hcst and work ? For
what tJ4,c of proccsss the two bccome equal ?
Ars DlficrEncr betv.[ hcst 8nd rorlc Refer to page
st9.
Condition urder which 4 = r. p1sm 6^,
thermodyDamics LE=q+w. Thus q=ry in
magnitude when AE = o. Tbis happeos during
the isothermal expanrion of aD idcal gas-
Q. 5. Why teDperature falls during ediabatic expan.
sion of a reol gas but remairs coDsteDt during
odiabatic cxlrarslo[ of oD ldcal g&s ?
Ans. In the adiabatic expansion of a real gas, some
work is doDe in overcoming tbe intermolecular
forcs of attraction. This work is done at the
cxpnse of internal enerry whici therefore falls.
As interoal eDer$r of a gas is a function of
temperaturc, hcoce the tempraturc falls.In case
ofideal ga6es, the forcs ofattraction betweeo the
Doleqlles are neSligible. HeEcc no work is done
to oi,ercome the iotermolec'ular forces of attrac
tiofr. As a result, intemal ener$/ remains constant
and so is thc tcmprature.
Q.6. Shoq' thst Ir the isothermrl .xpauslon of the
a gas is
ldeal gas' 6E = 0 and AH = 0.
Atrs. (i) For one mole ofan idealgas, C, =
ffi
ot dE=q,fr
For a finile change, AE = Cu AT
For isothermal process, T= constant so that
AT = 0. HcDce dE = 0.
(rr) H-E+PV .'. aH =AE + a(pv)
= AE + A(RT) -AE+RAT. But AE-o
(provcd aborrc) and AT = o (for isothermal -
of
process). .. aII =o.
Q.7. Itr what ri,8y ina.mal eDerg5/ ls dltrGrrtrt from
cnthalpy ? Erplain both the tentts slth suit8blc
examPles, (N.C.E.R.T.)
ADs. Intemal eDer$/ (U) is the eDer$r stored in a
subctaDc tbe chauge iD wh6e yalue during a
procss is equal to the ht flokcd or absorbed
if tbe process is carried out at coDstaDt volume or
is not accompanied by any change in volume ie.
6L1 = 4,,. Enihalpy (H) is the enerry storcd in a
subtanca iE the form of heat. That is why it is also
called he3t content of the suhtance or sy6tem.
The changc in its tralue duriDg a proccss ir equal
to the bcat evolvcd or absorbed if the process is
carricd out at or$tant pressure i. AH = 9r.
The two are related as H = U + PV or
AH = AU + Ars RT.
Thus if a z, = 0, 6g = 61-1.
ffAnris +ve ([a np > r,)rntco|E AH > AU.
It L n s = -ye (Lc. np < nrLG.o@ H < AU .
,.* at
For rEmple, for the reaction
N2G)+()2G)-2NOG),
Az, = O, thercfore, AH = AU. For the rcaction
CH4 ($ + 2 02 @) + CO2 @) + 2 HzO (l)
Az, = 1 - 3 = - 2.:e. therefore, AH < AU.
For tbc reaction,
CaCo3 (r) * cao (r) + co2 G)
Az, = 1 - 0 - I ie. itis +ve. HencAH > AU.
Q. t. Why should thcE he cn.rEr crislE rhcn hr of
conseraatlotr of erelEr hol& 3ood ?
sl62 l'radec y's Neur Course Chemistrg@
Ans. No dou bt, the law ofconservaaion of eDerg/ holds qglqtjg! St p I. CaLulation of rlondatd entholry
good but theoDly problcm is that the combustion of rcaction
of fuels is a one way process ie. either the M/" = !AH/'(Products) - rAH/o (Reactants)
products of combustion are not mnverted back
into the oriSinal sub6tancs at all or they are = I^H/. (o2) + 2 aH/ (HDJ
converted back at a rate much slower thaD the
rate of their consumPtion. For example, coal IAH/." (oF' + (HrO)l
^H/"
burns to from CO2 but CO2 is converted back
= t0 + 2 (- 270)l - l+ 20 + (- 2s0)l kJ m ol-r
into carbon by nature through Photosynthesis at
a much sloryer rate. = - 310 kJ mol-l.
fi. I'lt()BLDMt Step ll. Calculaion of tandord inlemal enetg/
l\,'l'1, ! kW heater take to lroil
How lotgwill s 2 change
2 L of water taken at 25'C ? Given thet the average For the given reaction,
specilic heat of woter in the range 25'C 100'C is - b,nr= (l +2) - (1 + 1) = 1
41E4JK-lg-1.
2 L of water =2000cm3=2000g AH"=AE'+All8RT
(dH2o = lScm ') or AE' = AH" - An, RT
'. Heat required Vy 2 L of water to raise its
temperature from 25'C to
'100'C = (- 310 kJmol-l) - (l)
1) (298
=rnXCxAT (8 .314 x 1o -3 kJ K-l mol- K)
= (2000 8) x (4.184 JK-l g-1) x (100 - 25) K
312 d8 kJ mol-|.
= -
= 62't60o I 1l.2Bof
l'tuhl?t,t 4. C.alclulatqtheworkdorewhetr
1
Heat supplied by 2 kW heater = 2000 Js- iron dissolves iD hydrochlortc acld ill (i) s closed vesscl
(ii) on oper beaket st 25"C (Atomlc mass ofFe = 56 /).
(, lW=1Js-l)
Iron reacts with HCI acid to Produee
.. 'Iime required to supply the required heat H2 gas as
621(,00 J :
= --'---'-'"1 5lq s
Fe (,r) + 2 Hcr (aq) Fecl2(4q) + Hz(8)
2000 Js '
-
= 5 Erln l4 r. Thus I mole of Fe ie. 569 Fe produce H2 gas = 1

l'n'blen 2. Gfie,l.that thc enthalPy offormntion of molg

H2O (r) is - 6s kcar mol-t' Calculate the enthnlpy of . . t 1 .29 Fe will produce H2 8as
formation of OH- (d4) ions.
1

SglqqgE For neutralization reaction, we know -s;x II 2 -- 0.2 mole.

that
H+ + OH-+ H2O,AH = - 13 Tkcar (i) If the reaction is carried out in a closed vessel,
Thus . AH Rcaction = [AH/ (HrO)]
-)l
.. rY= -PcxrAV=0
- l^H/' (H+) +
^H/'
(OH
(ii) If the reaction is carried out in open beaker
But AH/'(H+) = 0 (by c.onventioo) (external pressure being 1 atm)
- 13 .7 kcal = [- 68 kcal] - I0 + ^H/ (OH-)l
... Inhial volume = 0 (because no 8as is present)
Finalvolume occupied by 0 2 mole of H2 at 25'C
or AH/" (OH-) = - 68 + 13 7 kcal
and 1 atm pressure can be calculated as follows :

= - 5{ 3 kcol mol-l
l'rohlct .l Cnlcttrlat thestandard internnl energy
chaoge for the reoction OF2 (3) + H2O (8) -.
PV=zRr .. v=+
()2 G) + 2 HF G) at 29t K' Slven that the cnthnlpies of o 2 mol x 0 0821 L atm K-l mol-l x 298 K
lormotlon ofOf2 @)' II2O G) and EF G)sre + 20,-250
mol-l =4 89L
and - 270 kJ resPectively'
 FIHST LAW OF THERMODYNAMICS AND CHEMICAL ENEBGETICS 5/63
. . - \n;,;4 = 4.E9 L
AV = VfinEt I)roblen 7. T\c cnthdpy chaDgc lor thc r.{cdoE

w = - P.rtaV= - l atm x 4 89Latm Zn (s) + 2 H+ (aq) 1 ZIll+ (oq) + Hz @)

= -4 89Latm iB - 134.{f \t ool-r. Ttrc forErdotr of 2 I of

=-4 89 x 101 3J=-49S.4J hydrogen eryonrls ihc syEt m by 22.4 tltr6 ot I atD
b thc lEtcrtrsl GDGrE chauSe of the
/,rr,611,1 5 ColcuLEte 6U ard AH ttr caloriBllonc
mole of a llloiroAtolnlc ldeal gas is heated ot constont
m:rr*t
pressure of I atm from 25'C to 50"C. Dking thc initial volume as oegligible,
change in volume during expansion (AV) - 22.1L.tu.
Solution. For monoatomic ideatgas, C, = R tcmal Pr6sure (Pcx, = 1 atEl
]
AH=AE+PAv
^
Lp = ^FI
,rT or AE =AII -PAV
, . aH = cp aT mol-l (or n cp AT for n moles) PAV - 1 aim xn.4L-n.ALatra
s - 22.4 x 1o1.3 ! = 2307 I = 2-31lfJ
=i,l.se1 x25 =t24.2c"|
.. AE -- 154.4 -2.31 -- 156.71 LJ.
Work done, I'rublen 8. T\. hcal ol formrdo[ ol
ry=-PAV=-P(V2-Vt) (0 CO, 6) liom lts clqucnts ls +94.4 l(srl
(i0 CUO (r) fton lts elcnctrts Is 151.t kcal, snd
= - (pvz - PVI) = - (n RT2 -n RTr)
(n:r) Ttc hcst ol rcactloE hGtr..E CuO (r) otrd
=_"R(r2_Tr) cO2($la +4Z.25kcrl. Colculatr thc hcst offormotlon
of CuCO3 (s).
= - 1x1.987 (321 - 29A)cat (I.S.M Dhanbad 1987)
=-497.al Solutio& We are given

dE=q+w (i) C (r) + 02 6) * CO2 (8) , AH = kcal

-94.4
= 1U 2 - 49 .7 cal = 74.5 cal. t
0r) cu (r) + i 02 G).- CUO (r),
I'toh hn
froles (,. lO expardisother-
ofon idcal gas
mally and reversibly from a prc6cure of5 atE to I atm
at 300 K. Whst ls the largest mass that caD be llftcd
AH =-151 8 kcal
(r,f) CUO(j) + COz @) .+ CuCO3 (r)
through a height of I metre by this expauslon ?
Nl = -42.25 kcal
w.',=-Z3O3aRTtogI Wb aim at

Cu(r)+c(r)+ I o, 6 crrco, 1r1,

= -2.3O3 (10 mol) x
- | mor- I (3m K) log
-
(E 314 JK
+ Eqn. (, + Eqn. (rr) + F4n. (nD gives ,n" rilr;;
result. (all = .aS kcal)
=-40 15 x 103J -2EE
I'nblt'n 9. ThG Eolar hGot ol formatlotr of
If M is the mass that can be lifred by this worlq NE NOs ir --K1.54 E snd those of NrOG) and
through a height of t metre, then H2O(D src EI.46 \f -2t5.7t U
and r.rpcflvcly ot
work done = I{gfi 2fC ard I atE prBsurc. Cslculstr AII for thc rcaction
15xldJ=Mx9.81 ms-2x 1m
40 NII.NO3(') * N:O(t) + 2H2O(l)
<Dihzt C.E.E. 1997)
or, = +o=rl:< t{!rg42s-2 e = rg mz s-\ Solution. e'rcaaion - : AH'/(Producfs)
918ms-rxtrn
_ 4o9Z.i6 kA. - AH? (Rectanb)
5l Prarlaep's Neut Course Chemistrgllftfl
- {aHi(N2o) aHiGIro' - aHi(NH1No,
+2x l'nthlqt 1) Whcr 10 g of onhydmus Caclz is
dissolved in 200 g of water, the temPerature of the
= a7'46 + Z x (- 2Es 78) - (- 367's4)
solution rises by 7 7"C. Calculate the heat of hydration
= - 122.56lJ hol-t of CaCl2 to CaCt2 , 6 II20. Given that the he6t of dis-
I'robbn 10. Colcdrt thc hcat ol combustior of solution of CaCl2.6 H2O is 19 0E kJ mol-1. Assume
mctis[e at 29c. IhG Eotr bond Gncrgic6 for thc C-8,
OEO, C = O ard o-E are reaFc'tlvly 415,49t, t03 specilic heat ofthe solution to be same as that ofwater
and 463 kJ mol-1. (C.E.E. Bihar l99E) i.e.4.lt4Jg-r K-r. a
Stepl. Calculation of heat of dissolttlion
Solution. We aim at
of anhydrclw CaCl,
CIlaG,)+2 ozG)- CO2 @)+z IlrO (l), AH=? Molar mass of CaCl2
H
I
=40+2x35 5 = 1118 mo|-l
or H-C--H e)+2o=o(s)._ Heat evolved io dissolutioo of 108 CaCl2 in 200 g
I
H water=mxcxA,
o = c = oG) + 2H-O-H(f,.rH = ? = 20o x4 184 \7 7J
aHa..*1on = : B E. (Reactants) t B.E- (Products) .
- Heat ofdissolution per mole
= [4 xB.B.(C-H)+2 x B.E (o=O, _20ox4.1a4 Ill ,tlrJ
10 --
- [2 x B.E.(C = O) + 4 x B.E. (o-H)
= 71. 52 kl
- (4 x415 + 2 x 49a) - (2 x 803 + 4 x 463)
ie. AHdislo. (CaCl2) = - ?1 52 kJ mol-l
= 2n56-3458 = --a02 kI
Step ll. Cakulntion of heat of hydrorion
|'rriL * It A chemist while studyiDg the Proper'
tles of gaseous CCI2F2, I chlomfluorocarboh Aim: Caclz (r) + 6 HzO (0-ChCl2.6 H2O (,t)
rclllScrant coolcd a I 25 g sample at constant atmos- We have :
pberlc pr.cssure of 1 0 otm from 320 K to 293 K. During
cooli[gr the sample YoluEe decrcased from 274 to 24E aH6;..o. (cacl2) = - 71 52 kJ mol-1
mL Calculate AH 8nd AU for the chlorofluorocarbon (Calculated above)
lor this proceas. For CCI2F2, C, = E0 7 J/(mol K).
(N.C.E.R.T) Alldi.,o. (CaCI2.6 HzO) = t9 08 u mot-l
AH = qp and Cp is heat evolved or ab- (Given)
sorbed per mole for 1" fall or rise in temPrature llere, ie. (i) CaClr(r) + oq caA2@q),
fall in temperature = 320-293 = 21 K
-
AHI = - 71 52 kJ mol-t
Molar mass of ccl2F2 =12+2x15 5 +2x 19
4
(r0 CaCl2 . 6 H2O (,t) + aq Caclz@4),
I
= 121 8mol AHz = 19 08 kJ mol-l
. .
Heat wolved from 1 25 g of the samPlc on Reaction : (i) can be writteo in two steps as
being cooled from 320 K to 293 K at constant Pressure cacl2 (r) + 6 H2o (r) * cacl2 . 6 H2o (r)'

=8ffrt.zs t27 r = zz.st I AH = AH3

Caclz . 6 H2O (,r) + aq C'aCl2 (aq),
Rrrther AH = AU + PAv = ---22 51J -
All = AHa
pav = t arm, @ffi11)L = --o 026 Larnr '' AH3 + AHt = AI-l | = - 71 52 kJ mol-l

But aH4 = aHz = 19 08 kJ mol-r

= - 0.026 x 101 325J=--:263I
.'. -22'51 =LU-263 I . aH3 + 19 08 = - 71 52kJ mol-l
or AU=-22'51 +263J =-19 EtJ or AH, = - 90 5 kJ mol-r '
 FIRST LAW OF THEBMODYNAMICS AND CHEMICAL ENERGETICS s/65

,', l.T. utA tNS ) SpECtA L

12 g Le. O.O12 kg of carbon on coDbustion !o
ohtained by bacterial fermentation of ahimal refus. CO2 produce he3r = 394 kI
The main combrstible gas prcsent iE the gobar gos is
found to be methane (toqo by weight) whme heat of .. 4 8 kg of carboo oo combusrion to CO2 will
combustior is t09 kJ mol-1. How much gobar gas produce heat = x 4.8
would have to produced pr day for a villsgc of 100 a.-0!2*.
fnmilies ifthe average consuEptionole family ls 20,000 = 157600 kJ
kJ pcr dry to meet all ils enerEo/ r.quiremenls. 0 012 kg of carbon on oxidation to CO produce
Solution. Tbtal eDer$/ requiremeot for l0O hear = ll1kJ
fanrilies per day = 20,000 x 100 kJ = 2 x l06 kJ .. 3.2 kg ofcarbofl onoxidation to CO willproduce
Methane (CH4) uDdergoes combustion as follo$/s : t"at=ffirr'zr.r
CLt4 e) + 2 02 g)- Coz @) + 2 HzO (l),
= 29600 kJ

AH = - 809 kJ mol-l .. Ttral hcat produccd = 157600 + 296OO =

For 809 kJ of enerry, CHa required
r,v,20o l(J
= 16g If wen were 10O7o efncient, all carbon would have
(Molar mass of CHl = 168 mol-l) been co[yerted to CO2.

For 2 x l(F kJ of energy, CH1 required Heat produced ftom 8 kg carbon would have been
=ffi-xa = 2,67 kl
=ffirz >< 1o6g=3e.55*,
.'..k emaew = x
As gobar gas coDtains 80% by wcight ofmethane, ffi 1oo = n.r%.
thcrcfbre gobar gas required x 39.56 kg , ,, ,,,, r. Calculate the work of exporslon when
:
-'-
# 100 g ofwatr is clectrollEed st o constatrt pressurc of
= 49.45 kc. 1 atm and teEprsture ol25PC.
tl dtlt.m 2.It an oven, due to iDsumcietrt supply Solutlon. Ele4trolysis of water takes place as
of orygen, 6OVo ol lhe carbon is converbd to carbon- zHzO (t)
dioxide whereas the renrainiDg 4ll is coDyeded into 2H2@) + o2@)
-
cdrbon monoxide. If the heot of combustiotr of c{rbon Thus 2 moles of H2Oie.2 x
18 = 36gof H2O on
to C0, is 394 lql mol-l while that ofits oxidatior to CO electrolysis produe 2 mol6 of H2 gas and one mole of
is I l1 k f mol-r, calculate the total he.t produed in the 02 gas ie, total 3 moles of the gass
oven Dy burning 10 kg ofcoal containiug l()%.arbon by .. lmgof water will produce gases
weighL AIso calculat! tlle efliciency of the oven.
3
Solution The reactions raking placa in the wen = ae x 100 = 8.33 motes
are
Volume occupied by 8.33 moles of gases at 25oC
C (0 + 02 G) .- CO, (g) + 394 kJ mol-l aod I atm pressure is given by
-. ,,RT
v = --P-
C (r) +
; 02 G)- CO G) + 111 kJ mor-l
Carbon prese[t iD 10 kg coal _ (8 .33 mote) (O.O82l
L atm K-l mol- l) (298 K)
80
I atm
=i6b'x10k8=8k8 = 203 8L
thking the voluEre of liquid warer as negligible
Carboo conlrrted io COz (being l0O rnl = 0. I L), AV = 203 .8 L
60 .. W= - P",t AV
= 100 x80kg=4,8kt
= -1alm x203.EL= - 203.t L atm
Carbon convened ro CO = x a ks = j.2 tE - - 203.a x 101.3 J = - 20.6 u
ffi
5i66 . Ne.t cours. ch"-istrglGfrlD
Workdolte in the exponsion ofan ideal . Heat clange per u; = ffi
gas from 4 dm3 to 6 dm3 against a constant ext mal
pressrrre of2 5 atmrtas used io heat up 1mole ofvater = 3 939 kcal
xt 20'C. What rryill be the filtnt temPemture of wflter' , r,,/'r. /,r i give[ 100 g of glucose
AD athlete is
Given thnt the specillc heat of *ster (c5Hl206) of enerB' equiYalert to 1560 kI. He utilizes
| K-1, 50 percent of this gained energr in the event. In order
= 4.1s4 J8-
Solrtion.As work is betng done against coostant to avoid stotage of energy iD thc body, c^lculote the
exterDal pressure, the proccss is irreversible. Heoce weightofrvater hewould need to perspire. The enthfllPy
w=-p",tAV ofevspotation ofwater is 44 kJ/mol. (I.I.T 1989)

=-25atnrx(6-4)dm3 solution. Energy left unuliliTed = fU

=-5 0Latm (ldm3=1L; = 780 kJ
=-5.0x101 3J(1 Latm = 101 3J) For loslng 44 kJ ofenergy, water to bc evaPorated

=-5065J =1mole=l8g
For rsothermal expansion of ideal gas. AE = 0 so . . For losing 780 kJ of eDerry, water to bo evaporated
lhat11 =-11,=5065J. t8 ,
I = iix780E=3les
This heat is used uP to heat mole of water.
Applying thc relation , ' ,- The shndord enthrlpy ofcomhustion
q=mxcxLT at 25'C ot hydrogen, cyclohexene (C6llr0) and
5065=18x41tl4xAT cyclohexone (c6Hr2) ore snd
-241, -31100 -3920
or N =6125 kl/mol respectively C$lculate the heat of hldrogenn-
'. FinaltemPerature tion oIcyclohexere.
(I.LT. 1989,I.S.M. Dhonbod 1992 ; Bihot C.E.E. 2003)
=zO"C+6725=26'125'C
An intimate mixture of ferric oxide, .Solution. We are Siven
t
lerO3, and aluminium, Al,ls used in solid fuel rockets' (i)Hz+ iO2 .- H2O,aH =-241 kJ
Crlculate the fuel vrltre Per Bram End fuel value per cc.
!_7
ofthe mixture. Heats offormatioE and densities ar as (ii) c6H to + ; 02 -* 6co2 + 5H2o .

follows :-
AH = kJ
aIrT(Alz Or) = 399 kcaVmol -3800
(ii0 C6H12 + 90, 6CO2 + 6H2O ,
aIIl(FcrO:) = 199 kcal/Eol
AH =- -3920
kJ
Density of Fe2O3 = 5'2 Elcc ......-
we aim at C5Hlo + Hz CoHrz AH = ?

Density ofAl =2 7 glcc' (LI.T I98E)

Eqn. (i) + Eqn. (,r) (iii) gives the required
-S-olutiq!.
We aiD at
result. -Eqn. kJ]
[Ans. -12
Fe2o3 + 2Al zFe + Al2O3, AH = ? ,/ ,\
) ,,,1,1,Calculate the stnndflrd he.t offormation
AH rcaction = -12 x AHr (Fe) + AHf (Al2 Orl of csrbon disulphide (r). Given thot the standord ha{ts of
comhustion of carbon (s), slllphnr (x) and cnrlron disul-
- lHl(Fezo:) + 2 x aHy(Al)J phide (I) ore 3, --:293 72 and-110E 76 kJ
-393
= (0 + 399) - (199 + 0) = 200 kcll mol -l rrspectively
Thrs is the heat change that takes place when (Roorkee 1989)
I mole of Fe2O3 and 2 moles ofAl combine Solu.tion We are Siven
i.e.(2xs6 + 3 x16) +2 xng =214Eof the (D C (i) + 02 G) col?)'
mixture. Hcnce heat cbange per Eram
- AH = -393 3kJ
= :-
200
= 0.9346 kcal (i0 S (,r) + 02 G)) '- So2 G)
611 = 72 k)
Further 16ogFe2o3 = 112 = :rcncc (,i0 CS2 (D + 3o2 G) ....... -293
Co2 G)+2sozG)'
{r'.
and S4gN=ilu=zocr AH = - 1108 76 kJ
'Ibtalvolume ofthe mixture = 50 77 cc we aim at C (r) +2s (s) + CSz (I), AH = e
FIRST LAW OF THERMODYNAMICS AND CHEMICAL ENERGEIICS sl67
Eqn. (,) + 2 x Eqr. (ii) (iit) gives the Compound tt2f) cl\ G) C2lt6 G) C
requircd result -Eqn. 124.02 kJ]
[Ars. (graphite)
l'ttiilu 9.AE s fiir<ture of 3 6T litres ofethylene A" _1560.0
-2t5.t -E90 0
_393.5
and methane on complete combustiob flt 25oC produces
6 . I I Iitres of COr. Firld out the amount ofheat evolved (U/mol;
on huming one litre ofthe rnixture. The hcats ofcom- The st.lrndard heat of formatior of Ca IIs G) is
-103.t kl/rnol.
httstion ofethylenc snd methane are and (.1.T. 19921
-1423 -$91
k, mol-r at 25'C. Solution. We are giveo
(r.r.T. tegt) ,l
(r) H2G). t02g)-- HzO(0.
Solutior. Crmbustion reaction of ethyle[e and
methane are AII--2858kI
C2H4 + 3O2 ZCOz+ 2HrO , LH= kJ (ii) CIl4 @) +2o 2 G) + CO2 G) +2lr2o (D ,
-1423
CHa + 2Oz -...- COz + 2H2O , AH = kJ --890 kJ
-891 ^H =
Suppose volume of qfl4 in rhe mixture =r litres. (,iD qH6 G) *
ThcD volune of CH1 in the mifture = (3 .67 - r) litres
lor,r>
Fronr the above reactions :-
2CO2 @) + -
3H2O (l) . AH = k.l
-1560
I litre of qH4 Bives COz = 2litres (,v) c (r) + o2@) co, (s) .

. -t litres of qHa gives CO2 = 2r litres - dH = kJ

I litre of CHa -393.5
Sives COz = I litre (v) 3C (r) + 4Hz g) + qH8 G).
.. (3 6? - r) lirres of CHa gives CO2
= -103.tt kJ
= (3.67 _r) litres We aint at ^H
Total CO2 producad = r+ (3.67 -x)
qH8 G) + HzG) qH6 G) + cH4 G),
_ (3.62 +r) litres
' 3.6'1 +r = 6.tl
- AU=?
ot x=244 5 x Eqn. (i)
- Eqn. (v) - Eqn. (,i) - Eqn. (,,,)
.'. 1 litre of the ntixture willcontain qH4 + 3 x Eqo. (rv) gives the required result.

244 [Ans. kJ mot-l]

-55.7
i;7 = u 0o nrre
= In order to get maximum cfllorillc
output, a burner should hsve an optimum fitel volue to
aDd CHl= l-066= 0 34 litrc oxygen ratio which corrcsponds to 3 timcs as mrrch
22 4 litres of qH4 Sive hear = '1423 orygen as is required theoreticaly for completc combus.
U
tior ol the fuel. A burner which has been adjusted for
. . 0 66 litre of qHa wi give heat mcthane os tuet (with r litre,/hour of CIla cnd 6r
rl l .il litre/hour of O, is to be readjusted for butane, CaIIro.
=;frx0 66 kJ = 4r'e3 u In order to get the snme colorilic output, what sho[ld
lre the rate of supply of butane ond orygen ? Assume
22 4 trtre ol CHa give heat = 891 kJ that thc losses due to incomplete combustion etcarethe
. 0 34litre of CHa will give hear same for both the fuels and that the gascs behrve ideal.
ly, Ileats ofcombustion :
89 t
= ,2.4 x o.lt kJ = IJ 52 U CH. = t09 kl/mol,
. Tbtal heat producd = 41.93 + 13.52 CaHro = 2t7t kl/mol. (l.r.T 1993)
= 55.45 kJ Solution. Combustion reaction of CH4 aDd
tl)ldn I t) Determine the enthalpy ofthe reaction
l't CoH,o are
C3Hs (s)+II2 G) *C2H6 G)+cH. G) at 25"C
CHa + 2o2 .......- CO2 + 2H2O + 809 kJ
using the given heat of combustiotr values under
stI|ndard coDditions. cruro + for- 4co2 + 5H2o + 2878 kJ
 Pradeep's
5/68
We are given :
Calorific v-dlue of CH, = # = s0 s6 kJ g-l (i) c (r) + 02 G) co2 G),

Calorific value of Cr Hro =2-91! = a9 '6,

y1t-t - AH=-3935kJmol-l

C1Hl0 required to get the same czlorific value as @1*t, (9 * ! o, G) Hzo (D,

forr litres of CH4 = ffi"r= 10189.rlitres : - 285 8 kJ mol-l - AH

Tbeoretically oxygen required - f >< r'olsl* (d) 3C(r)+3H2G:).- qH6e),

= 6 623 i litres' AH = + 20 42 kJ mol-l

Actual oxygeo required = 6'627xx3 t.)Hzcr
......-QHe G)
= 19 869 r litres r--crL
cHz
Henc CaHl0 aod 02should besupPlied atthe rate AH=-330kJflrol-l
We aim at
of 1.0189, litre,ihour of c4Hlo and 19 869r litre/hour
of 02.
t', ,i,1,:r l-t The enthslpy chsnge involved itr the
H-C-CH.
'\/ '*lo,s)-
oxidstion of Slucose is u mol-r' lUertyfive tH, 3 Co2 rj) + 3 rr2o (/)
ofthii energi -28t0 for muscular work If
avsilable
oercent is Oprating (iv) (iii) + 3 x (r) + 3 x (ti),weget
ioo lJ of musculor work is needed to walk oDe
the required equation and
-
kilometer, what is th maximum distsrce that a Person
AII = 42 + 3 (--393'5) + 3(-245'8)
witl be able to wolk aner eating 1208 of glucos ? -33 -20
(I.I.T 199n = - 2091 32 kJ hol-l
,Sq!-uqo!!" Energ/ available for muscular work I'rot'lu lJ EstiDatethe average S-F bond cner-
S/ tn SFa. The standsrd heat of formatiotr Yal cs of
)\
kJ mol -l S G) and F @) are :- 1100, 275 rnd E0 kJ
= fib. x 28t0 SF6 k),
I
mol - rcspcctively. (r.I.T. teee)
= 720 kJ mol-l
Solutiop. We are Siven
Molar mass of gluclse = 180 g mol-l
. . Ener$/ available for muscular work from 120I } s3 {r) + : n2 rr) sF6 (a),
{D
-
glucose dH=-1100kJ
=ffi*tzou=aeou (,,)*ss(O --. sG), Nl = 275 kl

ln 10O kJ of muscular work, distance walked = 1

km @D+Fzer ---. F (s), AH =E0kJ

.. ID ,l80 kJ of muscular work, distanc! wa'lked I
I
we aimar f,lSFc18)-- sG)+6FG)l
= .i6o x 480
Eqn. (ti) + 6 (n:i)--(i) gives
-4 Elm sF6G)-sG)+6FG),
From the foltorvitrg data, cllculate the
eDthalpy chstrge for the combustioh of cycloPropanc at AH -275 +6 x80 -(- 1100) = 1855kl
29t K. The entholpy of formetion of CO2 G) ' HzO (l) .'. Average S-F bond ener$/
and propene (A) arc t 8nd 20 42 kJ
-393'5, -2t5 1855
mol-l respectively The enthalPy of isorDeilsation of 6
cycloproPane to Propeuc i6 - 33 0 u mot-l'
(IJ.t. 19eE) = 309 16 kl mol-l
FIHST LAW OF THERMODY\AMICS AND CHEMICAL ENERGEIICS 5/69

ANULT'PLE CHOICE uEsTtoMs

or
Competitive
Intemal energy ofa substaDce,hystem is of the following equations cofiectly repre-
(a) State tunction sents the staDdard hear of formarion (AHf) of
(6) Path function methane ?

(c) Neither state functiori nor path fuDction (o\ (l l(liamond) + 2Hr(g)- CHIG)
(d) Both srate function as well as path function :. agraphire) + zurgl-''''''- cHa (t)
The relarionship between enrhalpy aod internal (()C(graphirc) + 2Il2@)- CH1@)
enersr ciange is
(a)AE=^H+P Av (b)AH = +p
(d) C (graphite) + 4H+ CHa (g) tt.r..t: Ies2t
(c) d,H=-aE-P (d)PAV=^EdE+ ^v 9.'fhe enthalpi of vaporizrtion of liquid water using
^v ^I{
When a reaction is carried out in a clGed vessel the data
(a) qp < q" (b) qo , q"
ari6;l * lorgl Hzo (D ;
(c) qp = q, (d) q" = o.
- 6H = kJlmole
Thc boDd energies of H-H atrd Cl-{l are 430 kJ -285.'17
mol-l and Z2kJ mol-1 Nlrfor HCI
respectively.
tt, ts1 * lorg) Hzo E) ;
i6 91 kJ mol-|. The bond enerEr ofHcl wilt be -
AH = - 241 .84 kJ/mole is
4n kl
(a) (b) us Lt !.1+43.93kJlmot (6) - 43.93 k]lmot
(c) s tJ (d)'165tJ. (.) + 527 61 kJlmol (d) - s21.61kJtmot.
The relationship between free eners/ change ( l.l. l: 1991 )

(AG) and entropy change(AS) at constani rempera-

ture (T) is t/tl! tlraurhe same condirions how many mt of 1 M
KOH and 0.5M H2SO1 soturions, respecrivefy,
(a)AG = AH + T^s when mixed to form a total volume of l0O ml.
(6)AH = Ac + TAS produces the highest risc in temperature ?
(c) TAS = aG+ aH (a) 67,33 (b) 33,67
(d)Ac=-^H-TAs (c) 60
'2lo, lelso, so.
If hcat of dissolution of anhydrous CuSOa and t l.l.-t l99i ; Harya,-t ('.l .E.T 20t)(t)
CuSOa.5H2O are kcal aod + 2.80 kcal
-15.89 4re beatof neutralization of aqueous bydrociloric
respectivety, then the heat of hydratioD of CuSO4
acid by NaOH is.r kcal/mol of HO. Calculate tbe
io form CUSOa . 5H2O is hat of Deutralisation per rDol of aqueous acetic
(4)
-13.09
kcal (D) - 1t.6e kcat
(a) 0.5 r kcal
(c) + 13 .09 kcat (d) + 1r .d9 kcal. (6) r kcal
7. The differeocg btween heats of reaction at coD_ (c)bk(z,l
sta[t pressure and at constani volume for the reac- (d) cannot be calculated from the given data.
tion tl.\: ll l)lut"h d lettJ
2 C6H6 (D+1s oz@)- "tZ COz@)+6 H2o (l) 'IIe enthalpy chaDge for a given
reaction at 29g K
at 25'C in kJ is is -.r callmol. Ifthe reaction occurs spontaneousbr

lq--1 .43 (b) + 3.'12 at 293 K, lhe enlropy change at rhat iemperature

-3 72
(c) (d)+7.43. tr.t1: tse| (a) can be negative but numerically larger than
xt2gScalK-l

l.a
/3S
2.b 7.o &c 9.o
ll, .t l0.d
 ,. j-.r. ,.r,,r,'i Neut Course Chcmistrglfift[fi
call be negalive, but numerically smaller than coe)+ro2@)-coz@)?
x / 2gB c2lK-r
(d) aH =
(c) cannot be negative
(a) AH < ^E
AE
(d) cannot be positive. (1.'i,tl t)1 ,' ! i
(c) AH > AE
13. of CO2 G), CO G), N2O E) and No2 GI) in (d) AH is independent of the Physical state of the
^H'r

2NO2 ) + 3co G) N2O (8) + 3co2G) base is coostant and equals to

- (D) 1450 (a) 13.7 kcal (b) s't kJ
(a) 836
\{--asa (d) (c)57xldJ (/, All of the abc,ve.
-1460.
(I.5.rl Dlunbld, te9J) t.ll.l! (.ll.E. l')')q l
20. The following is (are) endothcrmic reaction (s)
14. GivcD C+02-* CO2, 611"=-r'tJ
that
(4) Combustion of methane
zCO + 02 ' 2 COz, ag' = -Y'tJ
{r) DecomPositioo of water
The e[thalpy of formation of carbon monoxide (clDehydrogenatio[of ethane to ethylene
will be (d) Conversion ofgraPhite to diamond.
.,.2x-v
(o)y - 2x \b ) --T'
21. lf aE is tbe heat of reaction for
kL# (d)Zx-y
t( R.\.1 Ir tl.l: Iae-\
qHjOHO + 7 oz@)+ 2 COz G) + 3 H2o
at constant volume, the AH (heat of reaction at
()

coostant pressure) at coostant temPerature ls

15. Standard molar enthalpy of formatioD of CO2 is
.lrfaH = an - nr (b) = - 2 RT
equalto +2RT ^H
(d) aH = Ae +RT.
^E
(c)AH =
(a) zero ^E 1( li..\ 1.. 1,.1t I )i)t) t

(b) the standard molar enthalPy ofcombustion /,ol include

22. Internal e[ergy does
(c) the sum of standard molar enthalpies of for-
(4) nuclear eners/ (b) vibratiooal eoergy
matioin of CO and 02
(c) rotational eDergy

-\dfeDerg
of $a.Jitational pull. )t)ttt) tr)l.rt\
23. Which of the following reactions is endothermic ?
(z,rtrrcity of water in equ ilibriu m wit h ice
\-Ny'lvlolat heat ..-znc)
- at constant pressure $ JdtrI2 + o,
(a) zerc (b)Hz + Clz- zHCl
(b) innnity (c) HrSOo + 2 NaOH Na2SO 4 + 2 HxO
(c) 40 45 kJ K- mol-lI -
(d) None of these. 6.EM.C. 2000)
(d) 75 48 JK-r mol-l. Q.l.T 1997 24. Amount of heat required to change 1 g ic at 0"C
to 1 I steam at 100'C is
17' ln thc reaction: s + 3202' so3 + 2x kcal
(a) 616 cal (D) 12 kcal
and soz + 1 / 2or- so' + / kcal' the heat of
(c) 7 71 cal (d) noDe of these.
formation of S02 is
IHl4aM'"IlET 2000)
(r -
(D) r) 25. The Arr/' for co2 (,:), co G) and H2O G) are
@{1zr - v1. and - 241 't kJ mol-l rcsPec-
i(ll\l l'tl I it'') -393
5,
- IlO 5
tivetv. The sulndard enthalpy change (in kJ) for the
lt. At constant T and R which one of the following reaition cor lg; + H2 G) co G) + H2o (g) is
statements is correct for the reactiol
-
RS
r2. b 13. c 14. c 15' d 16. b 71. d 18. 19. d 2O. b,cd 21. a
2r. d 23. a 24. c '
 FIRST LAW OF THERMODYNAMICS AND CHEI\,IICAL ENEFGETICS
5171
(a) 5u 1 qdu.z (a) + 172.5 lbt'-lto.s
(c) 262.s (.1)- 41.2. tl.I.T 2t)t)0t
- (c)
-1070
(d) --476.s
26. ID thermodynaDrics, a process is called reversible (e) + I10.5
when A',:ruh L L la 2t)01 :.i I li.ti ti 200.t)
(a)surrouDdings and sysrenr chango into each
32, Crmpounds wirh high heat of formatioo are less
othcr
stabic because
(b) there is no boundary bcrween system aDd sur-
(a) it is difficult to synrhesize rhem
roundiDgs
(l)/enerry rich srare leads ro insrabiliry
(r41iie surrouniJings are atwa,s in equitibrium with
the systenr (c) high temperature is requrred tosynthesize them
(d) the system changes into th() surrouDdirigs spon- (d) molecules ofsuch compounds are distorted
(aneously l.l.l. )tilt I
'.r0lWhich one of the tbllowing sraremcnts is false ? The heat required to raise the EDprature of a
J?lfork is a srate funcrion body by t K is calted
(6) lbDrperature is a state function (4) specific hear lbfihem,at CziBcity
(c) Chalge in the slate is completely defined when (c) water equivalent (d) molar heat capacity
the initial xnd final statcs are spcified \1.1.L.8.ti.2002)
(d) Work appears at lhe boundary of rhe system.
Io a reaction irrvoMng or y solids and liqu ids, whictl
ii: ) t)t: I ofthe follotPiDg is true ?
2t. Change in eDthalpy for the reacuon (4) dH < AE lpftu - tn
2H2O2(l)- 2H2O (l) + 02 G) (c) aH > AE (r/).\rr = At. r r{f .^

if hear of lbrmariotr of H2O2 (4 and H2O (/) arc

35. C (diamord) ...* C (graphire), AH = _vc. This
-188
kJ mol-l and kJ mol-l respectively,
ls
-286 shows that
_/
| ot- (b) + t 96 kJ nlot-l
J3}craphire is more stable than diamoDd
)r1-196 (b) Dianond is more stable than graphire
(c) + 948 kJ mol-1 (d) - 948 kJ mor-l (c) Both are equally srable
( It s 1.. I'v. t y)t)1 : (d) Slabiliry caDnot be predicted.

29. Enthalpy of CH n * CH3OH is Degative

!or-..- .

Ifcnthalpy ofcontbusrion of CH4 and CH3OH are

r aDdy respectively,theo which relatio[ is conecr ?
(a)x > y
(c)x
ft)x.v
= y (d)x z y (6)AE=w=q*0
tc.B.s.E. Mt.'I 2001\ (c)AE=0,W=4*0
30. If order to decompce 9 I water, 142.5 kI heat is (d)W=0,AE={ *o it'.8\.L. t!]t 1.204))
requirerl. Herce the enthalpy offorrDation ofwater is
(a) +285 H 37. An adiabatic expaDsion of an ideal gas alwals has
Itbl"--2gs kJ
(c) + 142.6 kJ (ayecrease in lemperature
(d)
-142.s
w
t A'.('.t.'t: 20t) 1) 16)q =o (c) w=0
31. 'l'he hears of combustion of graphire and carbon (d)^H =o
monoxide respecrively are
-393.5
kJ mol-l and \y. The arDount of eners/ released when 20 ml of
0 5 M NaOH are mixed with 100 mlof 0.1M HCI
-283 mol-1. Therelorc lhe heat ot formario[
kJ
ofcarbon monoxide in kJ nrol-l is is.r kJ. The hear of neu traliza on(iDkJmol-r)is

./7 fo', s
t.a 29.b 32. b 33. 34. b
'
 N e.4

(a) (r) the [ature ofintermediate reaction steps

-100r -s0, (c) the differe[ces in the initial and final temPera-
(c) + l00r (d) + 50.r
t llonial Pll'7: 2(tt)) t
rures of lhe invofued substances
(1) the physical state of the reactants and Products
J9. EnlhalDv of neutrilizalion of HCIwith NaOH is r' t.\ i I l' l' )t1tt t '
Tne hiat evotveo when 500 ml of 2 N HCI are
mixed wilh 250 n of 4 N NaOII will be 45. AIII of graPhite is 0 23 kJ/nrole and AH/ for
(a) 500r (6) 100r diamond is 1 896 kJ/mole . aH rnnsirion fron]
Pf" (d) 10x (A 8M t" 2002) graphite to diamond is

underSoes a changeof .7a>f1.66 kJ lrnole (b) 2 |YJ/fnole

) (4.0 arm, 5.0 L, (c) 2 33 kJlmole (d) 1 5 kJ/mole
- cnrgy, au = 30 0
rnal t 1l.l1 t ) t)1
(AI{ ) of the Procss
io L atm is
PY
46. The bond encrgies of C-C, C = C, H-H and

(a) a0 0 (b) 42 3 C-H linkage$ are 350, 600, 400 aDd 410 kJ per
mole respeclively. The hcat of hydrogenation of
(c) aa 0 ethylene is
(d) not defiDed because pressure is llot constant ,,,
(r) - mol-l
n)\ 1') - t?o kl nlol ' 260 kJ
/,/' (c) - 400 kJ mol-1 (d) - 4s0 kJ mol-l
f *li"t ot,l" follovinB reaction define (^.r.8.|i.|i.2003\
(a) C16;amo,a) + ()2 (q) .... Co2 G)
47, One gram otsamPle of NH4NO3 $ deconlposed iD
a bomb calorimcter- The teDlperature of the
Pfiurts* |nr 6;--- Hrg; calorimeter increases by 6 12 K The hcat caPacity
(c)N2G)+3Hz)-2NHrG) of the systenr is | 23 kJlgdeg. What is the molar
heat ofdecomPosition lbr NHaN03 ?
(d) Co qq) +;oz\8)-CozG) ,1.1.1.;0,,t (a) kJ/mol
-? 531 kJ/mol -398
(b) 1 kj/mol
(c)
42. For the reaction -16 -.\dl -sozxsl*ot
+ (l) tlll:ll'\ )/tttl
C3HB G) + s 02 @)-.. 3 Co2 G) 4 H2O
at coDstant temperature, AH - AE ls 4ll. How rDuch gner$r' is released wheD 6 moles of
octane is burnt in air ? Given AII/" fbr CO2 G),
(a) + RT 71,{-zw
(c) + 3RT (d) - Rr Hzo (8) and C8Hts (l) respectively are - 490, - z0
( (:.R.5.L. n M.'.l 200.i ) and + l60 kJ rDol-l

',ilro, which one of the followio8 equations s

(a) -6.2kJ 9l\ -zt.tw
- - 4H".",",,on to aHifor the Product ? (c) - 3s.5 kJ (d) - 20.0 kJ
"qual t'l'1 1' ll \- )ttr)Jt
(a) N2 G) + o3 G)...- NzO: (8)
49. lf thc bond energies of H-H, Br-Br aDd H-Br
(D) CH4 G) + 2 clzg)- {e 433, 192 and 364 kJ mol-l resPectivcly, the
cH2cL (D + 2 HCI G) aH'for rhe reaction H2 G)+B12 G)-2HBr (8) is
.',
6xe G) * z F2 G)..* xeFa G) (a) - 261 kJ (b) + 103 kJ

(d)z co (s) + o2G)- zco2@) (c) + 2;1 kJ (d) - 103 kJ

t( .11.\ l' l:ll l )t)ttt
t( B \'l': 11|'d )(t0fi
50. Thc work done during thc expanslon ol a gas fronl
44, The enthalPy chaoge for a rcaction does llot a volume of 4 dm3 to 6 dm3 a8aiost a constant
depnd uPon external pressure o[ 3 atm is ( 1 L atnr = l01 32kJ)
(a) use of different reactants for the sAme Products

39. c 40. c 41, b 42. b -1.1. . 44. l) '15. .r

46. a 41. d
3lt. a
4A. b 49- d
FIBST LAW OF THERMODYNAMICS AND CHEMICAL ENERGETICS
5lt3
(a) -.P J
The eDlhulpv of rhe rcasrion HzO (q) ++01G)
,pf-eott ....- II2O
(c) + 304l aHt and rhar of H2 @) *lorrf>
(C) is

(d) (c.B.s.E. Pti.T 2004) ...- II2O (l) is AH2. TtreD

- 304 J

51, Tivo moles of an ideal gas is cxpalded isotherrDally (4)aHl<AU2

nnd reversibly from I litre to 10 litre at 300 K. The (D) AHr + aH2 - 0
eothalpy change (in kJ) for (he process is
(c) AHr > AI.I2
(ll)11.4U
(h) - tt.4 kJ
(d) AI{ I = AHz Uhrnatalqt L.t.:. l: )/ )t:
(c) 0 kJ The enthalpy olcornbustion of methane at 25"C is
(d) 4.8 yJ (I.LT 2004) 89O kl. The heat liberated when 3 2g ofmethane
is burDt io air is
AD ideal gas expaDds iD
volume ftom (a) u5 kJ
1 x 10-3 m3 to I x 10-2 r# ar 30O K againsr a
(b)278N
constant pressure of I x ldNm-2- The work
(c) - 8m kJ
done is
(a)-$oJ (d) 178UJ (Korn akn (.tr,.l:2001)
(b) - em kJ 59, If for (i) C + 02 COz (il) C + 1/2 Ox'''- CO
(c) z'to kJ (iii) CO + 1/2Oz - * CO2 the heats of reaction
(/) 900 kJ A.l.E.F.-E. 200J) are Q, - 12 aod - 10 respectively. Then e=
During isothermal expaosion ofideal gas, its
(a) -2
(a) IDternal energy increases
(b)2
(c) - 22
(r) Enthalpy increases
(d) - t6 (Oissa J.E.E. 20041
(c) Enthalpy reduces to zero
(d) Enthalpy remains unchanged 60. 1 nrolc of H"SO4 is ntixed with 2 otoles of NaOH.
t t,. L(.. P. I t..t. )a0J \ The hear evolved will be
Internal energy is
(a)57 3kr @)2x57 3kJ
(a) parrly potential and partly kineric
(c) 57 312 (d) caonot be predictc(l
(D) totally kineric rIILK(.1,.1. llqlt
(c) totally potenrial 61,'Ihc enrhalpy of a monoaromic gas at T kelvin is
(d) Done of these (A.t M.C. 2004)
otl,w' laylnr
55. Anrong te following intensive property is
(4) nrass Gllnr g1|-"2
(b) volun're
(c) surfac. tension r")]nr \lhnmtaka C.lj.T 2()01t
G/) enthalpy ttt hV.( 2t)q{t 62. CH2 = CH2G).r -.-
H2 (q) CH3 - CH3 G)..fhe
56. when 50 cm3 of 0.2 N H2SO4 is mixed with heat oireaction is Ibond energyotC-C = g0 kcal,
50 cm3 of 1 N KO[I, the heat Iiberatod
C= C = 145 kc.rl. C-H = 98 kcal, H_g = tOj
is kcal
(a) 11.46 kr (d) - 14 kcal
(6).57.3 kJ
lh) - ?3 kcal
(c) 573 kJ
(c) - 42 kcul
(d)5'13J Uhnutdk1 C.E. [, 2004\ , (d) - 56 kcat (Bihar C.E.C.E. 200a)

,t).
60.
!
h
sr.
61.
.
e
52.a '..1 *
62. b
ro1
n'
, 56, d 57, a 5t. d 59. c
5174

HIN
4.

rl r 'l
el = l+.430+i zl12
L-
or B.E (l ICI) = (215 + '-21191 100 cal
= 245 kJ
at ffc
AG=AH -TAS or AH =AG+ATS i00"c.
6. Sec solved exanrPlc on Page 5/31
(,) CuSOa (r) + dq. -* CUSO{ (./4),
AII - -
15 89 kcal 2s, AH'Rcacrion = [^l]i(co) + ^Hi(l]2o)l
(li) Cu506 .51'1rO + aq.- Cusoa (a{),
AH=+280kcal
F4n (r)-Eq. (ri) direclly gives the rcquired rcsult

1'.
^- -t7-- -1{=-',1
-.c 2tl. allR.ac(ion = 12 AHi(or]
L}l't(ll"o +
aH - aE =An8R1' -z Atri(Hzoz)
=-3 x8 x29El --1 41kl
31.1 = 12 (- 286) + 0l - 2 (- 188) : - 1e6 k.I
9, Aim : HzO (r) * H2O @), AH - ? 29. (0 CII{ +2O2'''-COr+2HrO, AI-I - r
Eqn. (ii)-Eqn. (i) gNes the required resolt.
10. In the first three cases, an]ount neutralized is less lillcHrOH + ]or-. co2 + 2H2o, aLr -)
tha[ 50 nll and hence heat evolved is less. 0)--(li) gives rhe requirccl eqn. ie for the Siven
11. It will be less than -t because acttc ilcid ls a $eak reaction, AII = r- - -v
acid but cxact vrlue cannol be Preclictecl. ,\s AII = - !e,l < ,l'

aG .aH -TAs- - r - 296 x As For ac Lt)be J0' for deconrposilion of I mol H'zo (13 g) heat re-
as can be negatiu. rrrt as ,norroi"-r"t','ir,ii
-ve,
x/298 quired =2 x 142 5kJ =285 kl

13. auReacrion aH"y(co:)l

= I^Hi(Nzo + 3 ie H?o (l) -'-- II2G) * jo,G)'
- 12 AHi(NO2) + 3 aH";(CO)l ,\rl = + 285 kr
Hence forthe reverse rcaction' AH = 285 kJ
=[E) +3(-393)) -2(34)+3(-I10)]
= - 836 kJ Jl. Given : (i) C (gr) + oz (g) * Ct)2 G),
14. Aim:C+i ]o, -.- co,au =r AH=-3935k1

Eqn. (i)+ Eqn. (,,) gives tbe required rcsult (ij) Co (s) + ! orlsy- co, (sy,

6H=-2E3kJ
15. Aln:c{37)+ o2G)_.co2) AH"= ! 1
('()' all
of Ainr: cQ9) +io2Lc)-- ( ()
= l
This N sanre as nrolar enthalpy of combustion
graphite. F-qn. (i)-Eqn. (ri) giYes the rcquircd result

fi. Ce=# At equilibrium, as Nr = 0, 34. AH = aE + PAv. For solids and liquids,

Cp=- AV =0'
FIFTST LAW OF THERMODYNAMICS AND CHEMICAL ENERGETICS slz5

Graphrte will have lower energy and hence Breatgr ,16. Ainr i CHz = CH2 + Hz .. CII3 - CH3
stability-
}IHIIH
36. As (ontirner ii' ch)scd ilnd lnsuldlaJ. lhc nrocess
acliabatic so that 0. /\\
is t!t
ll L C ltrH ll 'tI-C- -ll
11 =
^F =.1 +W. Atj:W+0 ,\ ,l
37. Ibr l1(llaLratlc expansron, q= 0. AHreacr,oi :: B.E (Reaclants) -: B.E (Products)
36. l0 n'rlof 0 5M NaOH = 20 x 0 5 :[BE (4c-H)+BE (C = C) + B.E. (H H)
= 10 millinloles -lB.E (6c-rr)+BE (c - c)l
= milliequivalcnls
10 = B-E. (c = c) + B.E. (H - H)
100mlofo 1MHCI =100x0l -28.8 (C - r{) - B.B. (c - C)
=600+400-2x110 350 kJ
= 1000 - 1170 = - 170 kJ.
Heat cvolved trorD deoomposition of 1g
=123x612kJ
= 100-r U
la =123x6.12x80kJ
AIJn"o. = - 100r kJ
= 602 kJ.
39. 5tl0 nrl of 2 N HCI = 1000 nrl of I N HCI
4E. C8Hr8 + +C}2....-ACO2 -I H2O
250 ml of ,l N NaOH = 1000 ml oi I N NaOH
. B)' dcfinition, heat cvolved
Ar{'R*"ti.; = Is + e aH/ (H2o)l
='t kJ
^H/'(co2)
40. I]=I-I+PV - l^H/(c8Hr8, r -f aH/ro2)l
ns pressure is not conslant,
.\II=IIz-IIr
= (Uz + P2Vz) - (Ut + PlVl)

- z Il,L. (Products)
= (433 + 192) * 2 (364) = - 103 kJ,
g). Work done =-P".,rAV =-3(6-4)Latnr
not diamond
= - 6 I-arm = - 6 x 101.32 J = - 608 J.
42, L\ ng= np - nt= 1' 6 -- - 3 51. aH =A(E +PV)- AE + A(RT) = r\E + RAT

or ,\H AE=AngRT=-3RT. (. AE = Cu and AT = 0)

^"f
'.AII=0+0=0
52. W =
- pAV - _ 105 Nm-2 (10-2 _ l0-3; n13
=-t05x10*3(lo-1)Nnr
=-900x-m=-900J
53. Sce MCQ 51.
44, (b) b)' llcs\'s law.

Grrphilc * Dian'rond
56. 5(t cru3 ofo 2NHzSOl
45,
Afl.",uion = AII/ ((lian]oDd) - AH/(Braphite) = 50 x 0.2 \{eq = 10 \{eq
: 1.t196 - 0 23 = 1 666kJlnlol(). 50 cnr3 of t N KOH = 50 x t N{eq = s0 Mcq
5n6
'llus t0 Mcq oI H2SOI will neulralize 10 Meq of 59. EqD. (it) + EqD. (rii) givcs the required result.
KOH 60. I nrole ofH2SO4 = 2I eq. of H2SO4.
slo3oJJ 1
.'. He t tiberared = , lu 61, For nronoatomrc gas E =
t RT
= 0 573 kJ = 573.,. It=E+PV=E+R1'
WhcD fI2O (g) chaDges to H2O (/) i / coDdcDsc- 15
rron rakes nlacc. heal isrvohcdi.,' Allz rs grciiler
=|n'r +nr =]nr mor-l
than all I. 62. H Ractior = t B-E, (Reactants)
58. 169 Ctll pro(lucc beat = 890 kJ - E B.E- (Products)
. 3 2g CII4 will produce hcat c) + a B.E. (c - H) + B.E. (l{ - H)l
= IB.E. (c =
- (c - c) + 6 B.B. (c - H)l
[B.E.
=lix3.2=l78kJ =[45 +4 x98 +103] -{80+6x981 = - 28 kcal.

ADDITIONAL UESTIONS
As ee rlio n- Re a s o n Ty p e Q.u esii ons
The questions glvcr blow coDsist of an 'Assertlon' i! col umn I snd the'Reaaon' ln column 2. Use the folloui ng
key to chooce the appropriate onsroer.
(a) Ifboth ssscrtlotr and reason are CORRECT and reason ls the CORR.ECT cxplanatlon ofthe assertion
(r) If both assertion ard resson ore CORRECT but reason is not the CORR.ECT cxplanatloE of the assertion.
(c) Ifassertior is CORRECT but the rcsson ts INC0RRECL
(d) It assertion Is INCORRECT hut rcoson is CORRECr.
(e) Ifboth ossertion ond rcason arc INCORRECT'

AssertioD
1. Thc value of enthalpy of neutralization of a weak A]l the OH- ions furDished ty I g equivalent of a strong
acid and a strong base is numerically less thaD 57 1
base are not completely ncutralized by the H3O+ ions
kJ.
from the weak acid.
2. Standard enthalpy of graphite is lower than that ol Standard enthalpy of elements is taken to be zero ar-
diamood. bitrarily.
3. Enthalpy ofcombustion is negative. CoDlbustion reactioD can be exothermic or endothernric.
4. Ahsolute value of H canDot be deteflDined. Absolute value of E caunot be determined.
5. Endothermic compounds are more stable than the Endothermic reactions have positive eDthalpy of fornra-
cxothernric compounds. 1ioD.
6. Enthalpy ofvaporisatioD is alwa)B endothermis water is an exothermic compouod.
7. Enthalpy of neulralizatiou is always exolhermic- Neutralization involves reaction between an acid and a
hase.
& Enthalpy of neutralizatioD for both HNO, arrd HCI NaOII is a strong electrollte. (A.r.r.M.s. t997)
with NaOH is 57 1 kJ pe r mole.

True/Falee Staaemente
luhich of the following stalemenl$ arc not trTte ? 2. An extensii property depends upoD the anrouDt
Rewrite them cor7e c tly. of the substance.
l. An isolated q,stem is tha t which cao exchange ener- 3, In an isothennal procEss, tempcrature remains con-
ry but not Datter with the surrouDdings. slanl beaause ro heal caD enter or leaw the slatem.
FIRST LAW OF THERMODYNAMICS AND CHEMICAL ENERGETICS 5177

The work doDe on the slstem is positive whereas
the heat absorbed by the system is positive.
IDtemal eDer$/ change is the heat chaDge at con-
stant volume whereas the enthalpy chaDge is the
heat change at constaot Pressure.
lnternal eners/ is a state function but eothalPy is
not a slate functioD.
7. The standard state ofa substance is 0'C and 1 atm
pressute.
E. The S.I. unit of hcat is'calorie'.
9. The absolute value of intemal enersr of a sub-
stance cannot be determined.
10. W is positive when tbe aork is done on the system.
Enthalpy of combustion is the amouDt ofheat evofued
when the oulnber o[ n]oles rls representcd by the
balaDced equation have been completely oddized.
12. The total amount ofheat evolved or absorbed in a
reaction depcnds upon lhe Dun]ber of step.s in
which lhe rcaction rakes placc.
13. The e[thalpy ofcombustion ofcarbon (graphitc) is
nor equal to that ofcarbon (diamond)
l.l. Enthaltry ofsolution is alwars positive.
The totalamount ofheat cvolved or absorbd io a
15.
reactioo depeDds upon the number of step6 in
which the rectioD takes place.
16. The enthalpy of mmbustion of carboD (graphite) is
not equalto that ofcarboD (diamond).

Fill ln The Dlanke

1. A system which can exchange only eners/ but not 10. The part ofthc universe chosen for studyofeDerry
matter with the surroundings is called...... changes is called...........wbereas the rest of the
A thermodFamic property which depeDds ooly oD uoiverse is called ....
the nature of ttle substance is called ....... 11. The eners/ stored withio a substance is called iLs...
A proccss which is carried out ....... is called a revers- 12. A reaction in which heat is absort ed is called an ....
ible procrss. 13. The eDthalpy of any elemeDt iD the standard state
4. [-awofmnservationof enerryisalsokno oas........ iq taken as......
The heat change occurring at coDstaDt pressure is 14. Heat ofneutralizaUonofan aaid is theamouDtofheat
called...... svolved when ..-. of.,.- is neuiralized by.... oIthe....
The ditference belween molar heal capacityat coD- 15. AHsubtima(ion = ..-. + ..-.
staot pressure aDd that at constant volume for oDe
16. The enthaltry ofcombustion of benzeoe is
mole ofan ideal gas is equal to...... . -3264
kJ mol-l. The heat evotved in the combustion of
7. (4) A rystem is said to be .-... if it can neither
39 8 of beDzene will be ...-
exchange matter nor ener8ywith the surrouodings.
(D) The heat content of the products is more than
17. Coal and petroleum are called ..., tuels.

that ofthe reactaDts in an ....... teaction.
(r.r.T t9e3)
When Fe(,r) is dssolved in aqueous hydrochloric
acid in a closed vessel, the uork done is...,,.,....
Enthalpy is an.........-property.
It. The heat conteDt of the products is more than that
ofthe rcactants in an ..... reaction,
19. The enthalpy of neutralisatioo of a weak acid
is......--.- thaD that of a strong acid. The differenc
of the latter from the former is kDos,r as eothalpv
oi.........of the weak acrd. (Bihat C.E.E. 1998)

W atchin g Ty p e Q.u eeti ons

Match the entries ofcolumn Awith appropriate entries of c{,luDm B :

(o) A B
1. System can sxchanBe botb matter and eDerry with the surroundiogs. 1. Closed slstem
2. System can exchange neither matter nor ener$/ with the surroundings. 2. OpeD E6tem
3. Systcm can q(change eners/ with the surroundiogs but oot matter. 3. lsolared slstem
4. S,,stem can cxchange matter with the surrou[diDgs but not eoer!ry. 4. No such systgm exists.
(b) A B
1. A procss which is carried out infiDitesimaly sloA,ty. I Isochoric procss.
2. A process is carried out such that temperature remails constant. Isobaric process.
3, A process in which Do heat cnters or leaves the q6tem. 3. Isothermal process.
4. A process io which the volume is kept coDstant. 4. Re!'ersible procss.
5. A process io which presure is kept coDstant. 5. Adiabatic process-
5178 Pradct: St's Ne@ aourse Cltemistrqffiill

ASSERTION-REASON TYPE OUESTIONS

r.(a) 2.(b) 3. (c) 4.(a) s.(d) 6.(b) 7.(a) E. (D)
TR U E/FALS F, ;TA1 EM EN TS

1,3,6,8, 10, 11, 13, 14, 15.

FILL ]N THE BLANKS
1. Closed systen 2. Intensive property 3. Infinitesimally slowly 4. First law of thermodynanrics 5. Enthalpy
change 6. gas constant, R 7. (a) closed (D) endothermic E. zero 9. extensive 10. system, surroundings
1 l. internal energy 12. endothermic reaction 13. zero 14. one gram equ ivalent, the acid, excess base

15. AHgoslqn, Mvaporisation 16. 1632 kJ l7.'fossil. lE. endothermic 19. less, ionization.

MATCHING TYPE OUESTIONS

(rt) 1-2, 2-3. 3-1. 1-J (b) 1-1. 2-3, 3-5. 1-1. 5-2.

Ty?e Q.uegtions
5.

8.
 UN[]F

Cllernical Donding
and lvl olect)lar SErucb.)re
i
i ;ri
t:
:', i ,i:i ii

ia ':; 'U,
:---,
';--1 ,! ,'i:i' i,,

i Kossel-Lewis approach to bonding.

ii lonic bond-lattice enerEy, Born-Haber cycle. i
i covalent bond-Lewis structure of covalent bond, resonance structures. i
ii Geometry ol molecules, VSEPR model, Polarity of bond, Electro negativity, Valence bond approach, i
i concept of resonance, Direclional properties ol t ond. ::

i Hybridization (Qualitative treatrnent sp, sf , sp

6.1. General lntroduction-
M o le c u e s a n d C h e m ic a I Bo n d
I
1itr+iT.i.iili,ri:r:r.triiriiii::il:
Atoms are usually not capable of free exist-
ence but groups of atoms of the same or different
elements exisl" as one species e.g.
H2, (o7, Pa , S3 , HrO.
A group of atonr eristingtoplher as one species and
having characteristic propertia is called motaute.
Obviously, there must be some forcc which
holds these atoms together within the molecules.
Thisforce vhich hnhls the aloms together within a
mohcule is called a chemical bonil.
To look into the reasons for the answers to the
above questions, different theories have been put
forward from "-e to time. These are :
1. Kossel-Lewis approach
2. Yalence Shell Electron Pair Repulsion
(VSEPR) theory
3. Valence Bond Theory
4. Molecular Orbital Theory.
i
In this unit, the first three theories will be
b{:fty described while molecular orbital theory
willbe discussed at +2level
6.2. Why do Atoms Combine
:::::::::::::t:::::::::::::::;l::i::i::::::in

A number of questions now arise : A number of attemfis were made to explain

(i) Why do atoms combine ? the formation of chemical bonds in termi of
(ii) Why are only certain combinations pos_ electrons, but it was only in 1916 when Kossel and
sible, e.g., hydrogen exists as H, and not as
H, ? in grving a satisfac-
(iii) Why do some atoms combine while cer_ eory was based on
tain others do not, e.g. two H-atoms combine to so it is referred to
form H, but two helium atoms do not combine to as Kossel,s
form He, ? ganic gsrn-
ainly to or-
. (ir) Why do molecules possess definite
shapes, a.g., COris linear but HrO is tetrahedral
? The study ofnoble gases, earlier called inert
Similarly, BF, is planar but NH, is pyramidal. gases, (Group 18 elemenls) srrggests that neither

6tr
612 Neu/ Conrse Clrer istrq

they combine chemically with any other element 6.4. Lewis Symbols :.:i:+:::i:':ri.:ii:r::i::::::-"'-::ri:.r:':i:::ir:',:rr:;:i::i::i:i::'

nor among themselves. Their electronic configura- In the formation of a molecule, only the outer
tions are as follows : shell electrons are involved and they are known as
Noble gos Atomic No. Electronic valence electrons."fhe inner shell electrons are well
Confrguration protected and are generally not involved in the
Helium 2 2 combination process. It is, therefore, quite
Neon 10 2,8 reasonable to consider the outer shell electrons i.e.,
valence shell electrons while discussing chemical
Argon 18 2,8,8
bonds.
Krypton X 2, 8, 18, 8
G.N. Lewis introduced simple symbols to
Xenon 54 2, 8, 18, 18, 8 denote tle valence shell electrons irl an atom. The
Radon 86 2,8, 18,32, 18,8 outer shell electrons are shown as dots surrounding
the symbol of the atom. These symbols are known
From the study oI electronic configurations as Lcwis symbols or electron dot symbols. These
of thc noble gases, it is clear that thcy are chemi- symbols ignore the inner shell electrons. A few
cally inactivc because they havc 8 electrons in examples are given below :
thcir outermost orbit except in case of helium
which has 2. Hence, it was sttggcsted that they .Li .Be.B. .C.:N.:O
possess stable electronic configurations. In case
:F: :Ne:
o[ all other elements, the number of electrons in
their outermost shell is less than 8 and hence they Signlticance of Iaris symbols. The number
are chemically reactive. This led to the following of dots arouad the symbol gives the number of
conclusion: electrons present in the outermost shell' This num-
ber of electrons helps to calculate the common
The cloms of ddferent elemcn* combine with valency of the elment. That is why these electroLs
cach other in order to complzte their respective are called vqlence shell elecions -
octels (i.e. 8 elzclrons in their outzrmost shell) or
The common valency of the element is either
duplet (i.e., oulermosl shell luving 2 ekclrons)
equql to the number oI dots in the Lewis symbol (if
in case o! H, Li anil Be lo atlain slablg nedrest
these are 3 4) ot Sirinus the number oI dots (ifthese
noble gus confrguralion.
arc>4)
ri: tlL"! .lo Aio|l]s Cclllr,l.,i i
r i.lories r,;f Ci,,.micrl Llnrnbin::tiL-i'll
For example, Li, Be, B and C have valencies
to the number
1, 2, 3, and 4 respectively i.e. equal
As discussed above, atoms combine together of dots whereas valencies of N, O, F and Ne are 3,
in order to complete their respective octets so as to 2, 1 and 0 respectively i.e. 8 minus the number of
acquire the stable inert gas configuration. This can dots.
occur in two ways : Nowwe shall discuss each type ofbond one by
of one or ntore one.
,( By complete tralslercnce
qnolhet.This :' r : '
process is 6.5. Elecirovalent or lonic Bond
:. '. : : ' :r
elecions from one atom to
'. :1 '
..".:'.:.:.": "
.' '.:: .

referred to as lcctro-valcDcy and the chernical

bond or Wen a honil is Jormed by completc lransJerence
bond formed is termed as lctrovalent
of electrons Jrom one alorn lo anolher so us lo
ionic Bond.
complcte lhpit oulcrmost orbits by acquiring E
2. By shaing of etecrmns. This can occur in two elcctrons (i.e. octat) or 2 electrons (i.e- dupw) in
ways as follows: case ofhyilrogen, lithium elc. and hence acquire
bYWh* the shared electrons are confributed the slable nearest noble ga-s conliguration, the
by thitwo combining atoms eEtally hebondformed boruI formed is cullzil ionic bon.l or electrovale
is called covalent botd. bond.

X6 wn Explanation of the forna0on o[ ionic bond'

ty by iie of Atoms are electrically neutal Therefore, theypo-s-
jormed is ktt sess equal number of protons and electrons on
dative bond.
 CHEMICAL BONDING AND MOLECULAB STRUCTURE 6/3

Iosing an electron, an atom becomes positively (2) Formation of calcium fluoride. If cal-
charged since now the number of protons cium (atomic No : 20, electronic configuration :
exceeds
the number of electrons. 2, 8, 8,2) loses two electrons, it is converted into
A+ A+ + e,- calcium ion and attains the stable inert electronic
arrangement of argon. On the other hand, fluorine
(atomic.No. : 9, electroni-c conf,rguration : ;,7)
"
b comesnegative- on gaining one electron forms fluoride ion and
ly charged. acquires the stable confrguration ofneon.
B*e-+B- Here, calcium atom loses two electrons and
The oppositely charged particles formed of postive charge
forrn-s calcium ion with two units
above attract each other by electrostatic forces of and the two electrons are transferred to two
attraction. The bond thus formed is known as fluorine atoms, which are converted into fluoride
elecfiovqlent or ionic bond. ions, each with one unit charge. These oppositely
Such a type of bond is formed only when one of charge.d ions are then held together by strong
the atoms can easily lose electrons while the other can electrostatic forces of attraction.
gain electrons and thus each acquires the stable
electronic arrangement of the nearest noble gas. -
Examples
(1) Formation of sodium chloride. Sodium
[,i']
(atomic number : 11) has electronic configuration I cu l'*
2, 8, 1. By losing one electron of its outermost shell,
it acquires the inert gas configuration of neon and lz,a,s I
changes into ion.
Na- Na+ + e-
[,i,]_
2,8,1, 2,8 2,8
On the otherhand, chlorine (atomicnumber : or CaF,
17) having electronic configuration 2, 8, 7 accepts one
electron relea"sed by sodium to complete its octet by
attaining stable configuration of argon. In this Some More Examples of Formation of Ionic
process, chlorine is converted into chloride ion. Bonds
(1) Formation of magnesium oxide trom
:ai. *e--[t-.]r]- magnesium and oxygen.

(2,8 7)
Now we have rwo species, one is positively
(2 8,8)
Mc:l:i : _+ t yt l'. [,:i']'-
charged sodium ion and the other is negatively 2,8,2
charged chloride ion. As soon as they approacL
2.6 2.8
each other, they are held together by strong or MgO
electrostatic forces of attraction. Thus, formation
of sodium chloride takes place. (2) Formation of magnesium bromide from
magnesium and bromine.

[Na+l +
[, :: r
] -....-, tN"l*
[, :f
t]-
. Sr:
Ihe above steps may be represented directly
L'?:'l
as fbllows :

Naj,/-\"
]'.
+ .Clt Na+ :Cl:-
F
-
f_

--+ aa L' ?:'l

(2,8,7) 12,"5,11 (2,8) rr, ,, ,) (2,E,2) (2,8, 18, 7) 2,8, 18, 18
614
Prtrdecy's Ned Coutse Chemistrgl@[fi

(3) Formation ofcalcium sulphide. (ii) the formation of a negative ion hy gain of
electrons from another kind oI atom.
(,li) holding thc Positivc and ncgative ions by
cr:---S .. ! ....- Caz+ frl :s:.],- orcos electrostatic forces o[ attraction.
288
(2,8,8,2) (2.8, r) The formation of ionic bond depends upon
2'8'8 the following factors :
(4) Formation of sodium sulPhide. (i) Ionlsation Enthalpy (lonization Ener5/).

.. lNult+ - .. 12- or NurS ,J the anou of

2Na.* Si+ l:S:l
L" r
Iehott ftom thE
" 11v'11+ ouhr0url shz oJ ttt isol4leil alom in ga.suous

2'8 2' 8'8

pta-w fl at b corLf,rt il inlo d gaxtt^| posilfue iorL

It is clear that lescr [hq ionisation enerry, easicr

Whcn thc structures of atoms or ions arc writ'
will bc the rcmoval of an clcctroi, i a.,Tofmati on of a
tcn in such u way that the clectrons Presenl in thc oositive ion ard hencc lrcatcr the chanccs of lbtma-
l'ulcrmosl shcll (valence shell) are rcprcscntcd h1 hon of an ionic bond. I oiisati on e nergr (1.E.) of alliali
dots (.) around thc symbol ofthe element, as in the
cxarnpics above, these structures are called [,cwis
dot structur.gq.
The numbcr of ckcttons lost or gaincd duing lhe
lormation o! an elzttrowknt linlage is tenned ts
the elearovalency of lhe elgmenl-

For example, sodium and calcium lose 1 and

2 clectrons respcctivcly and so their valencies are 1
and 2. Similariy, chloiine and orygen gain 1 and 2
clcctrons respectively, so they posscss an of magnesium.
clcctrovalcncy of and 2. In other words,volency is
1 495 kJ mol-1
aqudl to the char4e on tlrc ion. Na (g) ............... Na+ G) + e-
743 lcl mol -I
Mg (g) .+ Mg+ (f) + e-

co-ordination number. Thus co-ordination number

o[ Na+ and Cl- iorus in NaCl is 6.
Co-ordinalion nufiber of an ion moy be ilelined as
thc number oI opposileb charged ions presenl ionic bond formation.
uround thql ion in an ionic crystaL
(,,) Electron Gain EnthalPy (Electron Af'
, rj i-. :.,: ,:,,.-i, li .l ihe
r , ..:t cr . . , -)r jr,-. Band! finlty)
Elntron @inity oJ
Thc formation of ionic bond involvcs endg w to
(i) the tormatiotr of a positive ion by loss of an ilp,,anfd alafi
'ebnseil a
clcctrons from one kind of atoms. fl,lseous negrli$e iort,
 CHEMICAL BONDING AND MOLECULAB STRUCTURE 6/s

ln the
itivcly
d ions

negatiye ions is very common, e.g, in
chlorioe, electron affinityis + 3zlti H/mole i.e.,
Cl @) + e-.- Cl- + 3zE kJ/mote
or E.A. : + 3rt8 U mol-l
Hence, the halogerrs can form negative ions
easily. On the other hand, elements ofgroup 16 form
divalent ncgative ion-s (by gaining two elections) but
not so ea-sily. This Ls becarxe the semnd electron
iLffrnity in case of these elements is much lcss and is
negative ,.e., energy Ls required to form divalent ions.
Let us discuss the case of orygen. Fifst, oxygen will
add up one electron to lorm monovaletrt ion which is
accomparried by release ofcertain amouot of energy.
But in tle process of addition of second electron io
the monovalent oxygen io4 energ5r is required to
overcome the forcc olrepulsion exerted by the nega-
tively charged monovalent ion to the incoming
clectron.
oG)+e- ...-o-(c),
A" + B-_......-A-B-
case of
..'1f4 energ, relcased when ItE rcqaisile nutnber tt!
gnsitive snd negoliye ions ambine to form orc molc
ofthe ion 'compound is calhtl lufrice energ.
of latticc cncrgv o[ the
ihe greator u,ill be tlrc
nd hencc grc.rtcr uill he
Ws know that the force of attraction bctwccn
ths oppositely charged ions is dircctly proportion-
al to the magnitudc of the charges (q,,qr) antl
inversely proportional to thc square o[ the tlis-
tancc (r/) betrvcen thcm. 1.c.,
iltxq)
Force of attraction cf, ---------)
d:
Hencc the value o[ lirttice encrgy dopcrrtls
upon the follorving rwo l:crors
I

(a) Charge on the ions. Thc highcr thc charrc

EA' : 1 142 ;t' -o'-' on ths ions, grcater is thc forcc ol attrirction irn(l
o- k) +s- + O'z- @), hence larger is thc umount ol cnergv r cl!ascd-
E& = -693 kJ mol-r $; Size of theions. As hirhlr chrrgecl.l'. r i.s
So electron a fhnity for thc overallprocess will ure raic, the other factor i.(,.. i-hc'intcrnrrelcal Llis
bc given by mes moro intporlitnt.Il
EA = + 142_693 , internuclcar distancr:
=- 551 kJ mol-l. altlrcti0n rvill hc lcss
while in case of small ions, intcrnuclcrr rlislancc is
less and so lbrce of attraction is (rcrrtcr.

-Net effect. lI Lut(icc cncrsy I El(ctr(,n .rl-

linity > loriization cnergy, thc nii eflcrIrvillbcrh..
release of energy and hencc an ionic honLl is
rare and trivalent are rarer. formed.
Nole C*rehrlly that the term ued ia ttc above Most ol the ionic compounds rc lil nr, .l l,e .
twccn cations from metals (brcaus r'I Iow ionizu-
discussion is Elearon amnity (e). However,
tion e ls (bccaL c
sometimes the term Electron Gfi EothalDv of hig rv cornrn n
(AH"r) is used in place of Electror afroity (ii eXCeP .. il C[tl ll
discussed in unit 4). The two are taken as equal in
made liom two non-metallic clemcrrts. A larsc
magnitude (as AH* is only slightly higt'er Ain.ar;
oumbcr o[ ionic compounds urc known in rrlrich
but opposite in sign. AH", has sarne sign as required NHo+ is the cation.
according to thermodytranics l'.e. if eucrgy is
ii-.;',) )i\tl
released, it is givc a -ve sign. A. has signs conliary
,rr I l!
to thermodynamic conventions.
It may be concluded from the above discus-
sionthat etween Mix Born and Fritz Habcr in l9l9 put lirr-
the atom and on
ward a method bascd on Hess's latv [or the ialcLllrr
the right tion oflattice encrgy (which could nor bc mcasur-r (l
6/6
l)ratle ap's Neut Course ChemistrgtffiU

directly) and hence for predicting the stability of series of steps indirectly may be represented by a

the ionic compound formed (h"cause Lrger.is the cyclic process as under :
negative t,alue for lattice energy' greater is the , al{'r
stiUitity of tbe compound formed)' The method is Na (s) + )wtr(g) -.------* NaCl(s)
known as Born-Haber cycle' It is briefly described
below taking the example of NaCl (s). +SJ *1o l
The heat of formation of NaCl (s) is found to Nu G) cl(s)
be -411kJ mol-l i.e.
+r.E. J/ -E.A.T
+ lclr($ --.*
1
Na (s) NaCl (s),
t
Nr+ G) cl- G)
----1-----_--J
AHi=-411kJmol-l
We canimagine that one mole of NaCl (s) can
be prepared by the following series of steps :
Applying Hess's law (according to which the
(i) Crystalline sodium metal is sublimed to
heat chinge is same whefher one mole of thc com-
form gaseous atoms
pound is formed directly or indirectly through a
Na (s)---'-* Na (8), number of steps), and using the ;ymbols withottt
AH=AHsoblimation:S proper signs, we have
(ii) One-half mole of gaseous Cl, molecules is 1
AHi=S+7D+I'E'+E'A'+U
dissociated to form 1 mole of gaseous atoms
Substituting the values with proper sigrtr (posi-
tive sign if energy is absorbecl and negative sign if
1
cl
i.rrg) - (8),
enetg1 is relased), we get for the case of NaC!

o^:+AHar,,o. =)o -4tL: + 109+ 2lrrO*+4s6-349+U

(iii) The gaseous Na atoms are ionized to form or U: -789kJ
gaseous sodium ions Thus lattice energy for NaCl (.r) has a large
negative value. This eiplains rvhy lhe compound
Nu (g) .----- Na+ (g) + NaCl (s) is highly stable.
"-'
AH = I.E. (Ionization energv) It may be pointed out that direct detcrmina-
tion of elettron nffinity is also very difficult. Ac-
(lv) The gaseous chlorine atoms are converted curate values have been obtained only fbr a few
into gaseous chloride ions by adding electrons elements. Hence Born-Haber cycle is used ftlr the
Cl (s) + e- + Cl- G), calculation of electron affinity also using the calcu-
AH : E.A. (ElectronAfhnitY) latecl values of lattice energy from crystal
parameters.
(v) The gaseous Na+ and Cl- ions combine to
Some Important Consequences of Lattice
form 1 mole of crystalliue sodium chloride
Enthalpies
No* (g) + Cl- (s) --- NaCl (s),
;frfGreater the lattice enthalpy, more stable is
AH=U(LatticeEnergy) the ionic compound.
The complete process involving the formation -"(!r)'Greater the lattice enthalpy of an ionic
of one mole of NaCl (s) directly and through a compound, less is its solubility in water.

lix \Ill'l.li. Calculote the lattice enthalpy of Ionizqtiort enargt of Mg : * 2IE7 kJ mol-1
Vupotisarion energt oJ'Br, (/) : + 3I kJ tnol-
|
MgBrr. Given that
Entlrulpy of formarion of MgBr, : - 524 kJ tttol-l Dissociation energt oJ' Bt, G) : + 193 k! mol-
|

enetgt of Mg : + 148 kJ mol-L Electrott gain enthalpy of Br : - 33 t kJ tttol-

|
Stblinration
 CHEMICAL BONDING AND MOLECULAB STRUCTURE 617

Born-Haber cycle for the founation of AHi: S + LE.

one mole of Mgtsr, may be represented as follows :
+AI{"p+D+2xE.A.+U
AFri
Mg (r) + Br, (l) -----_ MgBr, (s) or LJ = AH"r - (S + I.E. + AHvap

..J J ar\"r. +D+2xE'.A.)

BrrG) :-524-(148+2187+31
tvte (s) I*o + L93-2 x 331)
.,."J 2Br (s)
,[ z x n.a.
: -524-t897
, M8* @) zBr- (s) : -2421IrI mol-r

-a--u
?:,ft;;@lft, h E M,',9,,F,-,O,,Ri i

1. Calculate the lattice enthalpy of KCl. Given that gainof 1 mol of F (g) is kJ mot-l and (v)
AHsub of K = * 89 kJ mol-l, AHDi.r. for 1 mole -333
AHifor LiF (r) is 1 kJ n:ot-r. (N.C.E.R.T.)
-594.
of Cl, = + ?A.4 kJ n:ol-l, AHionization for K ft') =
[,\n' -1011 6 kI mol-l]
+ 425 kI mol-1, AHetectron gain for C| G) = 3. Calculate the lattice enthalpy of CaCl,, given that
-35S
kJ mo[-l, aH7 (KCl) = --438 kJ mol-l. the enthalpy of (i) sublimarion of Ca is
121 U mol-l (i) dissociation ol Cl, ro Cl is
[.\rrs. kI mol-11
-719 242.8kJ mot-l lirl; ionizarion of Ca to Ca2+ is
2. Calculate the lattice enthalpy of Lil given that the
enthalpy of (i) sublimation of Li is 155.2 kJ 2422kJ nrol-l 1iv; elecrron gain fbr Cl ro Cl- is
mot- 1 1i4 dissociation of half mole of F2 is 75. 3 kJ
-355 kJ mol-l and (v) ani for CaCl, 6r; is
(iii) ionization of Li is 520 kJ mol-1 (iv) electron -795 kJ mol-1.
(N.C.E.R.T.) [ \ns kJ mol-l]
-2tt70.tt
HiiilN,T$ FOR DIFFICULT ?R.OE-LEMs
7. * jo + I.E. + E.A. + U 2. v =^Hi- . ], + r.r. + e.a.]
^H"t=s [.
- 438 :w*! (244) + 4zs---3ss + u = -594. 1-(155 .2 + 75.3 + 520-333)
= -1011 .6 kJ mol-l
or lJ = J19 kJ nrol-l 3. U : - 795 - + 242.8 + 2422 - 2 x 355]
ll2l
= -2870.8 kJ nrol-l

:''?.{'' ':i chaFcterisl-.tjl. J.nq.u$

not as molecules. These ions arc arrangcd in a
The ionic compouncls possess the following - lggylg p3tlgrq qg&rm a latti.ce'
characteristics: The pattern of arrangement, however,
--I. physical State. These compounds usually depends upon the size and charges of the ions. For
-- --..J example, in case of sodium chloride, each sodium
exist in the solid state.
2. crvsta r structure. X-ray analysis or t_h1
ionic compounds shows that they exist as ions and
:itffi ff :#:"tolJ.'i;l'H',f -"?lir11* i:"1
iir"" il"lr.mal octahedral crystal strucutre. The
6/8 ))rttlat.y's Neut Courpe Chemi;p*fifiEl
formula of irn ionic compound merelyindicates the
relativc ngmber of ions present.
-[on-polar solvents like carbou tetrachloride,
benzcne etc. having lowdielcctric constants are not
-
,.,{rtigh meltingand boiling points. Ionic com- cap-able of dissolving ionic soli<h. Hei'iae-r6iic
pounds possess high melting and boiling points. solid-s are soluble io polar solvents and insoluble in
non-polar solvents.
flis !s _b,gcause ions are tightly held together by 5. Electrlcal couductivity. Ionic compounds
strong elsctrostatic forces of attraction and hence
are good conductors of electrici! in solutioiio-rin
a huge amount of energy is required to break the
the mollcn state. ln solution or molten statc, their
crystal lattice.
ions are free to move. As the ions are charged, they
4. Solubility. Electrovalent compounds are are attracted towards electrodes and thus act as
soluble in solvents like water which are polar in carriers of electric current.
nature and have high dielcctric constant. It is due 6. Ionic reactions. The reactions of the ionic
to the rea.son that the polar solvent interacts with compounds are, in fact, the reactions between thc
(he ions of the crystals and further thc high ions produced in solution. As the oppositely
dielectric constant of the solvent cuts off the force charged ions combine quickly, these reactions are.
of attraction between these ions. Furthermore, the therefore, quite fast.
ions may combine with the sotv;;t to liberate ener- [e.& Na+Cl- (a4) + Ag+NO3- (aq)-
gy called the hydration energt whichis sufficient to
AgCl (s) + NaNO. (a4)1.
overcome the attractive forces between the ions.

I 'l hc concept of ionic bond was put forward by Kossel.

: The dielectric constanr of DzO is greater than rh:rr of H2O.

1 variflble electrovalelcy. [o case of transistion n]etals, certain atoms cnn lose difl'ereDt numbr ofelectroDs 1o
acquire a stable configuration. I lence they show variable electrovalency. For example, Fe forms Fe2+ and Fe3+
ions and Cu forms Cu+ and Cuz+ ions. The more stable ioD is the one which has nrore stable core r.e. lhs
confiSuration obtained alter the loss of valence elcctroDs. For example. Fe3+ salts are ntorc stable than
Fe2+ strlts

26Fe = 2,8,14,2

Fe2+ = 2,8,1+ = 1tv.;lo 3 12 3p6.1d lrorrubt. '

"or")
Fe3+ = 2,8,13 - 1N"]10 3 ,2 3p6 3 d5 (stable core;
Cu2* salts are more stable than Cu+ salts.
2ecu = 2, 8, 18, 1
Cu+ = 2, 8, 18 = [Nelt0 3.jz 3p6 3 r1t0 lstabte core;
Cu2+ = 2, 8, 17 - [Ne]10 3 ,2 3p6 3 d9 (more slabte core)
Grcater stabdity of Cu2* than Cu + is due to the lact that rhe nuclear charge of Cu is Dot sutficienr enough to
hoiaT8EteCtroris of Cu+ ioo present in the outermost shell.
Similarly, rn case of heavier./r-block elements like Sn and Pb with the valence shell configuration ru'2 np2, all
the fou r electrons may be lost giving a valency of +,1 or oolyp-electrons may bc lost giving i valency of +) The
r-electrons rcmaiD attracted by lhe Ducleus due ro poor screening effect of the intervening r/ andl electrons
aod do not take part in bondlog. The effcct is callcd inert pair effect.
-1. For the lbrDlation of iooic bond betwecn two atonN, the electronegativity drfference between then1 should be
> t 9.
 CHEMICAL BONDING AND MOLECULAR STRUCTURE 6/9

6.9. Covalent Bond-Lewis-Langrnuir C o nc ept i:,ii:i,:

Some More Examples of Formation of
[,angmuir, in 1919 improved the Lewis con- Covaleut Bonds
cept by suggesting that when both the atoms taking
(1) Formatiou of Hydrogen molecule
part in a chemical combinatioo are short of H. + .H....-..-, u
electrons than the nearest noble gas configuration, 66Do, - H
they can share their electrons in order to complete (2) Formation of Orygen molecule
their octets. Each atom contributes thc same num- /a:K;\
_--Q(?i)o.
ber of electrons to form common pairs which are : ii : + :,;, ., ii = ii,
then shared by both atoms. (3) Formation of Nitrogen-molecule
Thc bondfornd betflfrn Ite fiw atorrs bt rwtual
stqh| aI eledtons betneea tlum n u O omphU :N! + !N:--,
thzir ocleE or duplcK h cw o! ehDQnlt h,'ying
onb one sfuA it calbd covalent borul or covdlmt
@.,:N=N:
(4) Formation of HrO molecule
linkage and the number ql ebctrons contrilud by
eqch atom is laown os cnvalcrw!, " . .I{
, . *.9. ^-)^
Example to illustrate the formation of
covalent bond. Let us examine the formation of -o0gQ9
chlorine molecule. In this case, two chlorine atoms
combine to produce chlorine molecule. Each
- H-O-H
chlorine atom is short of one electron to attain
stable configuration of argon. Each of them con- (5) Formation of NH, molecule
tributes one electron to form a common shared
pair. By doing so, both of them complete their
orbits and acquire argon structure, The completed
,...1...r_@
octets are generally represents by enclosing the
dots around the symbol by a circle or elipse. Thus

,/=-).':\ or H-N-H
:Cl . + .Ct 3 ........* f;g[\6t:'lor Cl-Cl
z.'i.t z.'i.t \#,
I

H
(6) Formation of Metbane (CHa) molecule

Similarly, in the formation of HCl, H and Cl H

contribute one electron each which is then shared
by both so as to complete duplet of hydrogen and +
octet of chlorhe H

H.+.C. +.H
I

H_C_H
H-cr
".-r.glr-@or +
I

H
Multiple covalent bonds. In the examples
c;ted above, each atom contributes one electron. H
Hence the coyalency ofchlorine and hydrogen is
1. The bond formed is called single covalnt bond
(7) Formation ofEthylene (CrHn) molecule
and is representedby single line ( ) between the
- H.+ +.H
two atoms. Covalent bond may also be formed by
the contribution of two or three electrons by
:c::c: .---.....'

each of two atoms. The bond then formed ii H.+ +.H

called double or triple bond and are represeuted H\ ..'H
by a_ double line ( = ) and a triple line (=) respec- or C=C
tively. g-z \g
6/10 17 r a d e r: p' s N ei tl Aa di r it it eh' c m: i stru|ffiI[)
"

Bond Pairs and Lone Pairs. The shared In this structure, duplet of H is complete but
pairs of electrons present between the atoms are octets of C and N are not complete. Hence multiple
called bond paris because they are responsible bonding is required between C and N. Octets of C
for the bonding between thc atoms. On the other and N will be complete if there Ls triple bond be-
hand, the valence electrons not in-volved in bond- tween C and N. Thus we have
ing'(i.a., sliaring) [re'shdWn as such and are
called non-6onilig-g I-ecJrons or lone pairs or
uilshaieil p:airs. H:C::N or H-C=N
5.10. Lewis Representation of Simple , l'.li {\11'l ,1r 2. Tb drsw the Lewis dot structure
Molecules and lons (the Lewis StructL!res) i:::::i of CO!- ion.
As e4plained later in reaction 6.13, Lewis Step 1. Total number of valence
structures have a number of limitations, yet they are electrons of CO, : 4 + 3 x 6 : 22
helpful in understanding the formation and proper- (oC :
2,4, BO :2,6)
ties of moleculs to a greater extent. Hence writing
of Lewis dot structures of molecules and ions is very Step 2. Total number of electrons to be dis-
useful. These structures can be written through the tributedinco3- : 22 + 2 : 24
following steps : Step 3. The skeletal structure of CO, is
Step 1. Calculate the total number of valence
electrons of the atoms present.
o
Step 2. If the species is an anion, add number oco
of electrons equal to the units of - ve charge and if Step 4. Putting one shared pair of electrons
the speciesis a cation, subtractnumber of electrons between each C and O and completing the octets
equal to the units of + ve charge. This gives the total of orygen, we have
number of electrons to be distributed.
Step 3. Select the central atom (which is :o:
generally the least electronegative atom) and draw
the skeletal structure by intelligent guess to indicate
which atom is linked to which other atom. -4b9-
renemb-qr-.tb*atEqqC*{-Usuqlly_^qgcJp_yterminal In this structure octet of C is not complete.
irosition. Hence multiple bonding is required between C and
--Stqi 4. Put one shared pair of electrons be- one of the O-atoms. Drawing a double bond be-
tween every two atoms to represent a single bond tween C and one O-atom serves the purpose

:o: I t,i, l'-

between them. Use the remainingpairs of electrons
either for multiple bonding or to show them as lone
pairs, keeping in mind that octet of each atom is ....1..1..1
completed. :o:: C ! o! or l9=c-9,.1
EX,tr\{PLE l. Tb draw the Lewis dot structure
of HCN moleaile.
Altematively, the structure may be obtained
through the following steps :

Step 1. Calculate the total number of valence

electrons (A) after subtracting for the cation or
adding for the anion.
the number of electrons (N)
for all the atoms.
shared pair of electrons (S)
by Ni.e. S : N-A.
Step 4. Draw the skeletal structure and repre-
H: C: N: sent the shared pairs.
 CHEMICAL BONDING AND MOLECULAR STRUCTURE 6111

Step 5. Complete the structure by repre- (ii) To dntw the Lewis struchlre of CN- ion
senting the unshared electrons (U = A S).
Stepl.A :
EXAMPLES. (, fo draw Lewis sttucture of CO, 1 x 4(forC) + 1 x 5(forN) + 1
(for negative charge) : 10 electrons.
Stepl.A = 1x 4(forC) + 2 x 6(forO)
Step2.N = I x 8 (forC) + 1 x 8(forN)
=4+12=16electrons. : 16 electrons.
Step2.N = t x 8(forC) + 2 x 8 (forO)
Stp3.S = N-A = 16 - 10 = 6 electrons
= 8 + 16 = 24 electrons.
Stp3.S = N - A = 24 - 16 =8electrons (shared).
Step 4. Drawing skeletalstructure with shared
(shared). .
parrs
Stcp 4. Drawing skeletal structure with
shared pairs C::N-
o:: c:: o Steps. U = A - S = I0 - 6=4
Step5.U:A-S=16-8=8.
. . Complete Lewis structure will he .'. Complete Lewi-s structure will be : C !! f.f i
'l Lewis structures of some typical molecules
:O=C=O: and ions are given in the Thble 6.1 below :

TABLE 6.1. LIyis structures ofsome t!?ical molecules and ions

Lerris Lepr6ertation

:C=O:
 Nerl Course Cheruistrg

(r,,) HNo2 H:O N o H-O-N =O :

(Nitro'rs acid)

o
.. -o,.
,/fuii)(Niric acid)
HNor H:O N H-4-Nz'/
,//
o 'o:

o II :iLH
O:H
..t..
H-O-P-O-H
(o) H3PO1
(Phosphoric acid)
H:O or
.'t..
:o:
:

(r) Not t: N o o =N-ol-)

(Mtdlc ion)

o-=N-ii:
(r) No:-
(Nitrate ion)
o
I o
t..
: '9'

o
(,0 sol-
(Sulphatc ior)
o s o

ol- o t'z- ot
(Peroidc ion)
t,g
I l+
(xre) HrO* i; ll
. (Hydrcnium ion) l"' H
t
CHEMICAL BONDING ANO MOLECULAH STRUCTURE 6/13

6.11. Formal Charge (EC.) on

an atom in a rnolecule/ion i.qi,slill+rii.-1#.i:.r,illr1lifffil':ir-i:.:

In a molecule, there is no charge on the ./--O--.---

molecule as a whole or in a polyatomic ion (e6. : o- ():
CO32- or NHo+ ion etc.) although the charge
p resent on the ion Ls the charge on the ion as a whole
and not on the individual atoms, yet for some pur-
t (.r.tll'f .1.. .:. Calculate the formal charye on
(i) S in HSO, ion (ii) Clin HCIOl
poses,it is useful to assign a formal charge to each
atom in a molecule or ion, Solution. (i) t ewis structure of HSO. ion is
' The charye on an atom in a molecule or
formal
ion is d$ned as the difference between the number :o:
of valence elecoons of thal alom in the ftee sttte and
the number of electons asigned lo lhol alom in the H: O: S: O:-
Lewk sfr1tcfrlte, assuming that h each shand pair of
elecions, the atom has one elecfuon of its own and :o:
the lone pair on it belongs to it completety- TbrJs tt
can be calculated as follows : Applying the formula for calculation offormal
I Formal charge (F.C.) on I charge.
I an atom in a molecule/ion .l Formal charge on S=6-0-;(8)
=6'4=+2
(ii) Lewis structure of HCIO. is

:o:
- I fr"trf no. of shared electronsl n: o: cr: o:
" L @onding electrons; l .\J.
Ii\,L\IPLI1 | Cahulate fomal chatge on each
O-atom of Ot mokcule.
nor-ul.Uu.g. on Cl = 7 - 0 - j tSi = *:
Solution. Lewis structure of O, is as follows :

2 atoms in (i) carbonate ion (ii) nitite ion

(N.C.E.R.T,)

,,\ ----6
t--
i, Solution. (i) Lewis structure of CO3- ion is

The atoms have been numbered as 1. 2 and 3.

Formal charge on end O-atom numbered 1
1

=6_4_r(4)=o
Formal charge on central O-atom numbered 2
I
=6_2_;(6)=+t Formal chargs on C atom
Formal charge on end O-atom numbered 3
I =4-o-i<rl=o
=6-6-j(z)=-t Formal charge on double bonded O atom
Hence ue represent O, alongwith formal
charges as follows ;
=6-4-lrol=n
6114 Pra tt r t: yt's Neut Co urse Chem i strgt lfrfil
Formal charge on single bonded O atom
1 : CI: ," t ! (Be has 4 electrons arouncl it)
=6-6-)(z):-t d]

(if) Lewis structure of NO! ion is F:B:F, CI:Af:CI

+
FCI
(B and Al have 6 electrons around them)
It6=,;-gt-] Thus octet rule is violated.
(iii) Formation of compounds like PCI'
Formal charge on N atom
SF. , IF, etc. In each of these molecules, the central
atom has more than 8 electrons (expanded octects)
=5-2-)rc1=o as shown below:
oa
Formal charge on double bonded O atom
:CI:
aa
=6-4-1r+l=o
2" :CI: P :
oa

CI:
F:
ao aa
Formal charge on single bonded O atom F:
3Cl;:Cl:
=6_6_|Q>=_' ( 10 e around P)
( L2 e- around S )
The main advantage of the calculation of for-
mal charges is that it helps to select the most stable
:F
structure i.e. the one with least energy out of the :F: F:
different possible--L_ewls StruQtures. The most I ": F:
stable is the one which has the smallest formal :F: F:
:l11s:_.
onthe at9m,s. .r
6.1 2. Exceptio ns to Octet Ru le i:i:::i:::iii'::iiiti:il:ii:ii:::;::::a:i::::ii:i:::.:::::::llli::..,

( 14 e- around I )
Although octet rule is able to explain
the formation of a large number of com- Again the octet rule is violated in thesc
pounds, there are some exceptions to this molecules.
rule as follows : (iv) Formation of compounds of noble
-/(iY' Formation of compounds involving gases. Noble gases which have already completed
hydiogen. As hydrogen atom has only one shell octets (or duplet in case of helium) should not
containing one electron, it needs one more electron form compounds. However, their compounds
to complete its shell i. e. to acquire the nearest noble like XeFr, XeF' XeF5, KrF, etc. have been ac-
gas configuraf,ion of helium. Hence hydrogen needs tuallv prepared.
to complete its duplet and not octet, as e:rplained (v) Odd electron bonds/Odd electron
in the examples above.
molecules. There are some molecules and ions
(rr) Formation of comPounds like in which the bonded atoms contain odd number
BeO2 , BF3 , Atcls etc.In each of these molecules, of electrons (usually 3) between them. Thc
the central atom (Be, B or Al) has less than 8 bonds thus present are called odd electron
electrons i.e. these are electron deficient com- bonds and the molecules are called odd
pounds as shown below : electron ftrolecules. Some common examples
are given below :
 CHEMICAL BONDING AND MOLECULAH STRUCTUBE
Molecule/Ion
., . (i) Nitric odde (No)
o
(ii) Nitrogen dioxide (N02) N N,7
o \
I ., (iii) Oxygeo molecule (O2)
, , (iv) Superoxide ion (ot)
A three elcctron bond is considcred to be
equivalent to half covalent bond.
Langmuir concept of covalent bood,
Lewis -
as explained in scc.6.!), has the following limita-
Lions:
(i) It could not explain how ths atoms are held
together in the molecules like Hr, Cl, etc. in which
there are no ions and hence thers are no electros-
tatic lorces of attractioni.e. it could not explain the
formation o[ a covalent bond.
(ii) It could not explain the shapcs o[
7 molecules containing covalent bonds.
(iil) It could not explain the release of cnergy
during the formation of a covalent bond.
To explain the above limitations, lwu impor-
tant theories called modern theories of covalent
bond formation have been put forward. Thcse are
based on quqntum nrcchonical pirtciples. -fhesc
arc :
(1) Valence Bond (VB) theory
(2) Molecular Orbital (MO) theor),
In the next section, we shall takc up a brief
discussion olValence Bond theoryonly and that too
in a simple manner without entering into the math-
ematical complexity involved. The discussion of
Molccular Orbital theory will be takcn up at t-2
level
6/15
Lewis Represcntalion
or .N:O.
o
e BonC Theory of
nt Bond (Orbital Concept) [,i:
This theory was put forward by Heitler an_d
London in 1927 and further developed by Pauling
and others. Ac.ording to this approach,
d.awlent hond is fonuil b tt& Wt'uil oveitnp ol
firohalf-fiUd omic ofiitah conlabtingeMrons
vith opposite spitl.c.
The 'partial overlap' means that a part of the
electron cloud of each of the two half-filled atomic
orbitals becomes common. As a result, the prob-
ability of finding the electrons in the region of
overlap is much more than at other places. Thus,
the two electrons (with opposite spins) although
keep on exchanging position between the two
atoms but are present for maximum time in the
region of overlap and hence are attracted to both
the nuclei simultaneously thereby forming a bond
between thg two atoms.
fhe strength of the bond depends upon the
extetrt of overlapping. Greater the overlapping,
stronger is the bond formed.
To understand the concept more clearly,let us
consider the following examples :
(i) Formation of Hydrogen Molecule :
When two hydrogen atoms having electrons
with opposite spins come close to each other,
their s-orbitals overlap with each other result-
ing in the union of two atoms to form a
molecule (Fig.6.1).
6/ 16 tlur dr r 7.'s Neut Course Chemistrgffi[l)
fluorine baving an electron of opposite spin in ?,
orbital, the half-filled orbitals overlap each other
resulting in the formation of a fluorine molecule as
shown in Fig. 6.3.

H-ATOM H-ATOM H2 MOLEC ULE

or in terms ot electron cloud pi.iure
Jl:ttarr,r
lffi&*. rr$Emfr*,i
i}ffii.'#ffij'
^rr:!idsr!i,

''?.ffifJ 'iB..ffiEiI'
''Lt,,-}''i " -)-i'
lg.ATOMtC 1s-ATOMtC OVERLAPPINGTAKES
oRBrrAL oBBrrAL tL6ft5
F.ATOM F,ATOM
""8.t#hEtst
FIGI.JRE 6,1. Fornntion oI hydrogen molecule.

(li) Iormation of Ilydrogen Fluoride

Molecule: In case of formation of hydrogen
fluoride molecule, when one atom of fluorine
(elecronic confrguration | 1s2 bz ?42ptr2p1)
having one unpaired electron in itsp-orbital comes
closer to hydrogen atom with electron of opposite
spin in its tu-orbital, then the two half- hlled orbi-
tals overlap each other and a chemical bond is
formed between the two atoms. Ttis is shown in
Fig.6.2
H'ATOM
HF IVOLECULE
FIGUBE 5.2. Formation of HF molecrle.
(lll) Formation of Fluorlne Molecule : Whcn
an atom of fluorine (electronic configuration :
1"'%'2p12ptr2p!) approaches another atom of
F2 MOLECULE
FIGURE 6.3. Formation of Fluorine Molecule.
Difference in the sfiugths o[ bonds in
H2, IIF and F2. As the orbitals involved in the over-
lap arc different, the extcnt of overlap is different
and hence the strength is different.
Existence of only H, and non-exlstence of
spcies like H, Il. etc. This can be easily explaiaed
on the basis of orbital concept. A hydrogen atom
contains only one half-filled atomic orbital (1s)
which can overlap with thehalf-filled atomic orbital
of another hydrogen atom only, forming Hr. No
more half- Frlled atomic orbital is available and so
no more bond can be formed.
Non-formation of Her. This can also be ex-
plained on the basis of orbital concept. A helium
atom contains fully-filled atomic orbital (fu'z) which
cannot overlap with the L orbital ofanother helium
atom because only half-hlled atomic orbitals can
overlap with each other. Thus He, is not formed.
Interpretatlon of orbital overlap ln terms (lf
enerXgr conslderatlon. Thking the example of the
formation of [I, molecule, when the two atoms are
far apart from each other, there is no interaction
between them. When they come clossr to each
other, the new forces come into operation, These
forces are of two tlpes :

rTheirbond strengths are in the order F-F < fI-11 < II-F
 CHEMICAL BONOING AND MOLECULAR STRUCTUBE
6117

thes
lhes
gy of the system.

-$r) The forces of attraction be )een the

nucleus of one atom and elect,bns d the othet afom.
These forces tend to decrease thl energy of the
system.

ITE DISTANC E
IN FIN

' NO INTERACT|oN -

H-Aror,,l (lt O H-ATOM (B)

cot\,tE
. CLOSER
.. INTERACTION
. STARTS Ile+l. I do= BoND LENGTH
E = BoND ENERGY
o o
FTGURE-6.4. (a) No interactions at large distances
+ff
(b) lnteractions start a< atoms im. closr,. I
lr,--r
l<
t>
UJ
F
t! POINT OF

INTERNUCLEAR OISTANCE (d)

FIGLJnE 6.5. Polential energy dia$-am showinq

vanation ol energ!, with internuclear
disbn.e behr,en tlvo H_atoms.

(i) Force of attraction between nucleus o[ A

and electrons of B.

_ (ii) Force of attraction between nucleus of B

and electrons of A.

. (ir'i) Force of repulsion between electrons of

Ihe atonrs-
(iv) Force of repulsion between nuclei of
thc
two atoms.
Thc diagrammalic representation o[ these
"
rorces
.
rs grven in Fig.6.5.

In
a certain
amourt to breat
the bon
have to
 Ne.4 CouYse Chen istY4
6/18

i
o
(l
l.tl
ztrJ

F
zul
F
o
0-

INTERNUCLEAR DISTANCE' d+

FIGURE 6.8. Variation of potential energy

whnn t,," hnlium .toms are_ brought closer'

6.15. fypes ol C
siqly .,,I1 :':trr- i-: '
Dependingupon the t)?e ofoverlapping, the
covalent bonds are mainly of two types ;

1. Sigma (o) bonil

. thc
He\ ler'
ATOM (A)r\ th4

NFW FORCES OF ATTRACTION

- sHowN av sol-to l-tNes The overlapping along the internuclear axis
ways
can take place in any one of the Iollowing
:

NFW FORCES OF REPULSION

'-siiowN aY sol-to utNes

FTGURE 6.7. New forces of attraction and repulsion

'riiJ.'"*"iti atorns approaching each other
r'r,"iirrn fluorine (Fig. 6.10).
 CHEMICAL BONDING ANO MOLECULAR STRUCTUBE
6/19

8?",fF+l1j l?",]:ie+H, o.3-nloolnf#'#,igpo* B?bi,?,..AF

AXIS H2 MOLECULE

FIGLJRE 6,9. Formation of H2 molecxje (sr owrlapping).

1S_ORBITAL 2Pz ORBTTAL s-p OVERLAPP|NG

oF H-AToM oF r-arou ALoNG |\4OLECULAR
'''-oh-s"n1j"
INTEBNUoLEAR Axts or rr uble-cure
FIGUBE 6,lO. Formation of HF mole.ule (s,p overlapping)
(iii) p-p overlapping: This type ofoverlap
.
p-grbital of the other is in case-of fluorinc
1", %,2p12prrzp! (i.e. it has a half-filled
[,
overlapping of Q, orbitals of the two fluorine atoms as shown in the Fig. 6.11.

2pz ORBTTAL 2pz OBBTTAL p-p OVEBLAPP|NG MOLECULAR

oF F-AroM oF F Aror.4 , ,r.*frt"ort?* *," .;nZTE:tL
FIGURE 6,1 I. Forrnation oI F, molecr.rle (p_p overlapping).
Similarly the formation of Cl Cl and Br Br can be explained.
Summing up, a sigma bond is formed by rwcrlapping of (i) s-s
orbitals (il) s-p orbitals (,i) p_p orbitals
along the internuclear a"ris as representeU in fig. fi'.i2. '

@ O> D@
s-s OVERLAP s-p OVERLAP p.p OVEBLAP

FlGt_rRE 6.12. Representation of s_s. s-p an.l po overlapping forming o bonds

Note. If Z-axis is chosen as thc ioternucle axis, n. overlapping can take place between s andp,
p, orbital orp, andp, or
orbitals r.e. there is zero overlap (Fig. O.f3j.

X
+
I

I I py
Pr Px

FIGURE 6-13. No ov.rl:phi:rr i. noss,hlp herrppn

l,\ r1,i .-- ' .'' ,,r\italc
 !,r,t,i: t.i,,1 Neu, Course Cheaistryfiffi)
6120

Fig. 6.16.

N.ATOM N-ATOiI

N2 MOLECULE
1t
(N=N)
1l
FIGURE 6.14. p-p overlapplng forming a pi bond

A z-bond is seldom formed between atoms FtGuRE 6.15. Formation o, nitogen molcule'
unless accompanied by a o-bond. For example' n
(iii) In
two carbon d
one /' bond

shown in Fig. 6.15.

case of the formation of a z-bond, sideways over-

lapping takes place which is only to a small exteot'
Hence, z-bond is a weak bond.
For the same reason, the strergth ofthe three
types of o-bonds is in the order
I
TWO HALF-FILLED
s-s>s-P>P-P
TWO HALF.FILLED
p-oRBITALS oF o'AToM Anoiher imfortant asPect about the o and
z-bonds is that whereas in case of o-bond, the
electron clo inter-
nuclear axis, etrical,
being more ow the
plane of the
O2 MOLECULE Note. Usingthe appropriate signs for thewave
,^ 7r
\\J__", ^. functions of theitomii orbitals, the overlap can be
positive or negative or zero as shown in Fig' 6 17 on
the next page.
FTGURE 5.15. Formation of oxygen molecule
 CHEMICAL BONDING A\,J MOLECULAR STRUCTURE
6121

FIGURE 6.17. Depiction ofFosilive, negative

and zero overlap.
ard pi Bonds. some importatrt poinrs of difference
o"r,llJil?ffliiifJsma beueen sigma andpi

SIGMA (o) BOND

Pi (,r) BOND
(i) Tbis bood
tbeir iDtern
(, P.i i: overtapping s6GfG
ro,m"o oy
lliilifiEiiiii
(lareral
6 }t^:.Llp"o q,overtapping betueen s.s, s_p or (r,
).
This is forned by rhe overlap
p-p orbttals. of p-p orbitals onty.
(A
3.:r]lry,o* p ruire largeaDd hence sigma bord is (i4 is to a smallextent. Hence
-Overlapping z-bondisa
weak bond.
lecrroD cloud in this cnse symmelrical about the
[ne Jotnlng the two Duclei-
is (iv) Electro[ cloud ofz-bbDd is unsyD]mekical.

!/3,:::.T:9^:l:i:T
slmmetncal aboul 9ronry ore eredron croud,
the intemuclear axis.
rotation about a o_boDd is p6sible.
+

Pradeep's','61!:gl',:', il;:. 'iii WID

6122
b. tt:l.

',.-;i

mean positions.

Thc averoge 'centres

of the
rurctei of llw calld its bond Factors affecting bond length
length The bond length in-
creas size of the atoms' For
exam are in the order
-X
HI>HBr>HCl>HF
bond. The bond length
6 iPlicitY of the bond'. Thus
6 bonds are in the
"arbon
C<C-C
o

In general, for a covalent molecule AB' the

bond lcngth (d) is given bY
d= re* t'y ,IP3c-lH,tP'c-H>sPC-H
The bond lengths of a few common bonds are
where r4 and rg represent covalent radii of
at'rms
given in Thble 6.3 below :
A and B resPectivelY

iAnlf 6.3. Rond length of some common bonds

Bond llond tength (Pm)

Ilond Bond length (Pm)
H_CI 127
H_H 74
CI_CI t99 H-Br 747

O=O 120 H_I 161

C_H 109
C_C 154
C_CI t77
C=C 134
C=C 120 o-H 96

( Bond enerry is usually expres-sed in kJ

-greater
(2) Bonil EnthalPY is the bond dissociation
mol-i. Further,
atoms come close together
energJ, stronger is the bond'
tion of bond between the
ConverselY, the energY is For diatomic molecules like H2, Cl2' 02' N2'
equal to
bond to get ttre seParated atoms' HCl, HBr, HI etc., the bond energies ar-e
and hince.have. fixed
Thc anwunl o{encrgt required to
break one mole oJ ln"ii ai..o"iation energies
slnce a
values. In case of polyatomic mole.c-ules'
so os lo sqarak lnem
mole-
band dissocislian ene r' ;;;;l.t typ" orui'"d present in different
 f.

CHEMICAL BONDING AND MOLECULAR STBUCTURE

6123
cules (e.&, O-H bond in H_O_H or
CHaO - H e tc.) or even in the same molecule (e.g,

,A
four C- H bonds in CH4) do not possess lhe same
bond energy (due to change in chemica_l environ_
ment), _therefore bond energies are usually the
average values.
The bond encrgies o[ some common boncls
have been given in Tablc -5.I ot Unir -5.
Fattors allecting bond energr
(i) Size of the ato,ns. Greatel the size of the
atoms, grealer.is the bond length and less is the Molecule: H-H O:O N=N C=O
Dond drssoctatron energy i.e. less is tbc bond
strength.
Bond order: 1 Z 3 3
(i,
Multiplicity of bonds. For thc bond be_ . For odd electron moleculos, as thc three
elcctron bond is considerecl as
tween the same two atoms, greater is fhe multi_ to hill
covalent bond, bond order can be"quivalent
fractional also.
plicity of the bond, greater is the bond dissociation
energy. This is fustly because atoms come closer
and secondly, the number of bonds to be broken is
For example, Lewis structure of NO is : N I O:
more. (See page b,l5). Hence its bond or,lcr = 2 ].
(iiil Nunber of lone ?uirs uI L.lectrons pru:jent.
2
^
Greatcr (he number o[ lone pairs of eiectrons . it is interesting to observe that isoelcctronic
present oD the_bonded aloms, greater is the repul_ species have the same bond order e.g.
sroo bctwecn thc utoms and hence less is thc bond (i) F, and Ol- have 18lectrons each and each
dissociation r:nergy. For examplc for a few single of them has a bond order = 1.
bonds. we have (ir) Nr, CO and NO+ have 14 elcctrons cach
C-C N-N O-O F-F
l-one pairs and each of them has a bond order : 3.
ofelectrons 1 0 Furthcr, it is also observed that
I 2 3
on cflch atom .,-(i) Greater the bond ordcr, grearcr is the
I stability ofthe bond rla greater is the B'ontl enthalpy.
ll(,hd ehcr$/ ] tJ8 Ir,3 I{r, lly Grcatcr the bond orrlcr,
fkJ nol ') .bond.(fi)
length.
shorter is thc
(3) Boud Angle. We know that a bond
11lll:1 ",e,,:.rii.r .. .
is
lbrmcd by lhe overlap uf atomic orbitals. Tbe direc- .-.
trrrn rrl overlap gives the direction of the bond.
The tnglz baween thc lirr6 rvFresenting thz direc-
lions of he bonds i.e. l,he otbitals contairrinE th2
bonding electrons Lt caltcd tlw bond anfu.
II isexpressed in degrees, minutes and It ionisation
):...""9: 19. exampte, H _C H bond angtc in
energy o atoms in
ClH4, H N- H bond angle in NU., H il _ their is
- - H
Proper
advity is a
bond angle iu HrO and F- B-F bond angle in
BF, are shown belorv :
 Pradcc y's
6124

+6 -6
H- cl

lxn-x, | =0 102 Vtr

'yherc h, = B.E. (A - B) values acrording to the equation
B.E. (A - A) + B.E. (B - B) il
2 r. = )9.e. + E.A.) = Z (1.E. - ^H,s)
and is expressed in kJ mol-1. (It may be recollected that EA-and tY,, ""
f the excess energY,
taken as equal in magnitude but opPosite in sign)
A, e electronegativities
Mulliken's values of electronegativity are
of given in brackets in the Thble 6.4
It is interesting to note that Mulliken's values
become equal io Paulins values if j 0.E' + E'A)
are given in Thble 6.4. values in aV are divided bY 3.17.

TAIILE 6.4. of reprtscnt.rtive (lcmcnls

GROUP GROUP GROUP GROUP GROUP GROUP
GROUP
1 t3 t4 15 16 11

H
2.20
(3.06)
Be B C N o F
Li 3.U 392
098 1 .51 2.04 255 304
(1 83) (2.6',1) (3.08) (3.22) (4.43)
(1 28) (1.e8)
si P s cl
Na Mg AT
3 16
0.93 I .31 1 .61 1 .90 219 2.58
(2.3e) (2.6s) (3.s4)
(1 21) (1 63) (1 .3?) (2 03)
Ga C,e As Se Br
K Ca
255 2.96
o.82 100 1.81 201 2.18
(1 30) (l .34) (1.e5) (2.26) (2 sl) (3 21)
(1.03)
In Sn Sb Te I
Rb Sr
196 2.05 2. 10 266
0.82 095 1.18
(1.83) (2.06) (2.34) (2 88)
(0.ee) (1 21) (1.30)
Ba TI Pb Bi
CJ
2.33 2.02
0.79
Values without the brackes are on Paulin8 scale
Values in brackcts are on MullikeD's sle'

scale -noD-evalualive
rMathematical calculation ot elerlrolleBalrvity bascd on MuUikcn
 CHEMICAL BONDING AND I\,4CLECULAB STRUCTURE
6125
How electrone{ativity is difrercnt from
electroE afliniry ?

(r) Electron affinity ca-n be measured ex_

pcrimentally whereas electronegativity is onlv a
relative number with respect to fluorine takeri as
4.O.
6.'18. Polar and Non-polai Covalent Bonds ::ir;r.Iti:,,;:,;

1. Non-polar Covalent Bonds. If two similar

atoms come close to each other and form a bond by
sharing their electrons, the shared electrons
ari
equally atuacted by the two atoms as tle

H 3 Cli or
l
I
MORE +d -6
ATTRACTED H_cl
tant bond is non-polar (Fig.6.18). TOWAROS Ct

.bond_The_ important characteristic of a non-polar

FIGURE 6.19. Polar coralent bond in HCI
is that the electron cloud is completetyiym_

H:H
l
I

EXACTLY IN H-H
THE CENTRE
:I 9j: ot
FIGURE 6.1a. Non-polar covalenr
bond between H-atoms.
t
MOBE ATTRACTEO
TOWARDS CI
metrical and there is no charge separation at all.
-The examples of some non_polar molecules FIGURE 6.20. Polar covalent bond in ICl.
are Cl, ,
O, , N, etc. Examples of some other molecules containing
more than one polar bond are shown in Fig. 6.21.

+
H

FIGUBE 6.21. Polar molecules containing

morp
than one polar pond.
 Ned Course Cltem i strtl
6128

Again, in case of symmetrical molecules (2) In the catculation of percentag ion'c

like
illustrated with the follow-
Uoroni".inuoria" (BF),tethane (CHnj unJ"utU- character. This may be
on tetrachloride (CCln), the molecular dipole mo- rng examPrcs :

of

ll
r case ofBFr, the
resultatrt of two bond moments' being equal rmd y:J
opposite to that of the third, cancels out'
-'
6 charactcr would be

: 6'12x 10-18esu'cm
-6lZD
ltottcwca =l 03 D (Given)
'. Eo ionic chatactet
il,
ll = 'r"b.'rnrd, t*
It ltionic

= 1'9: *^
-itz too = t6'837o

t-d LiH is , ,oo*,r1i"!,i!,'::,ii;:i,:,',:!

' ak,ttic (lislsnce befiveett Li atd H irt tltc
H*o cl txtlecule is I .596 A. Calculotc the percent
-
FIGLBE 5.25. Dipole moments of zero ,or symmelrical n)olv )e' io ic charactcr oJ lhe molecttlc'
Solution' If the molc ctic wcre 100'%
Applications of Dipole Moment : ionic,
lt ion;" =4xd
- (1 602 x 10-1e c) x (1 596 x 10-10,7r)

-- 2 557 Y. 10-2e Cm
llot'"n't = I 964 x 10-2e Cm (Givcn)

. . '% ionic charact ,' =t:B'L ' u'o

zero. This is because there is no charge separatlon
ri.rJ"il"., q : rr,r. al-pole mome nt 1 964 x 10-1e 9m x
rriir"."
urro u" o."a
o.
to diitinguish between polar and -- 2 557 x 10-2' cm 100

"u"
non-polar molecules. = 76.E1%.

?p.f1'f;1|El$},E; R
45 D aDd i(s boDd lenpth is 1 654 A late the
The obscrved diPolc momcnt for a molecule AB is 1
percrnage of ionic character in the bo;: @ihart E c'E' 20N) rs 3%I
 CHEMICAL BONDING AND MOLECULAH STRUCTURE
6129

held together less rigidly (by weak van der Waal's

forces), tban in case of ionic compounds.
. 4,__ Solubillty. Covalent compounds are
generally-soluble in organic (non-po[r or weakly
polar) solvents but insoluble in water anrl cther
not bc s),mmctrical iI it posscsscs somu molccular polar solvcnts.
clipolc momcnt as in casc of watcr (rz = 1 .g4 D)
and ammonia (! = | .49 D). But iI a moleculc Ele
5. there are no
contains a numbcr of similar atoms linked to thc
freeions to conduct
central atom and the overall dipole moment of thc
electricity, electricity.
molecule is found to be zero,lhis ryill implythat the . 6. Non-ionic reactions. Since these com-
'moleculc
_ pounds are molecular in nature aad not ionic, their
is symmetrical, e.g., in case oiBFl, CHn,
reactions are molecular and procced at a much
CCln etc. slower ral.e than those of ionic compounds.
6.2'l . Ch6r.rcteristics ol Covalent Compounds.r,:,,:,r, 7. Dlrectlonal characterlstics and
Isomerism. As the atoms in cor/alent compounds
1. Physical State. Unlike ionic compounds are held together by the shared electrons and not
(whlch gencrally exist as solds), the covalent com-
T pounds exist in allthe tbree states, viz., solid, liquid
by the electrostatic force, it i
Hetrce atoms in a molecule
and gaseous.
directionaI arrangements an
2. Crystal Structure. The crystal structure of and stereo-isomerism.
covalent compounds differs from that ofiooic com-
pounds. They usually consist o[ molecules rather
than ions. :]
5.'Meltlngand Boiling Points. Covalent com- The main points of difference between
podnds have low melting and boiling points be- electrovalent and covalent ocrnpounds are
cause the moleculcs in covalent compounds are summed up in Thble 6.5.

ELECTROVAI,ENT OR IONIC COMPOUNDS COYAI.ENT COMPOUNDS

(') Tley are lbrmed by shariDg ofelecrrons belween the

two atoms.

'1. * .]i,
_- :1: jr.:
(r'r) These conlpounds may be solids or liquids or gases.
(ii) Thcy are Dtadc up of nrolecules held together by
$'cak van der Wa.rl,s lbrces of attraction.
(r) They have generally low melting aDd boilitlg poinrs.

(v)

(u)

(r'ii)

0rr'i)
 Nerl Course Chent istrtl
6/30

,,1 t. is because Fe3

t ion has greater charge and sDaller size
FeCl, has greater c(rvalent character than Feclz. This
than Fe2+ ion. As a rqsult, Fe3+ ion has greater polarizing
pover (Refer to Fajan's rules discussed on page
6/68, 6e).
> > All3 This is because as the size of the
2 Solubility of alumiDium halides is in the order AlF3 > AlCl3 AlBr3
anionincreases,itSetsmoreandn]oreeasilyPolarizedandhenclcovalentcharacterofthen]oleculelncreases
(Refer to Fajan's rules on page 6/68, 69)
::r:a -1. Dipole moment also helps to
determine the tbllowlog :

.(i\Todistingtishhetweencisarullransiramerr..Ihisisbascdonthcfacllhalcisison]crusuilllvhushighcr
dipole mome nl than lrans-isomr '' g'
n-" I _cl
'-a-t' il 1, 2-Dichloroethene (+- shows

,-8.o
O) +
cis (,L
C)IC \H
trans ('r = 0)
directioD of diPole moment)

onho, meta and para itomers' This is based on the fact that the dipole nloment of
lii) To dislinguish between
p-iiomer = 0 and thal of ortho is Sreater than lhal ol meta e &
CI CI LI
lcl -t
ol
ortho-
54D
Q.,
p=148D
+ CI
Dichlorobenzene

P=2 Par'a-

orbitals' therefore if lhe

Vrriable and moximurn covalency. As covalencJ $ equal to lhe number ofhalf-filled
valence rhe paired elecrrons from , and/-orbil ls
;;;i;;i;;;i;;L"rr" t r, a-orbitals in rhi she ll,
"nipty du; ; excitation to emptv !'--orbi*ls As result'
a number or halr'-ril d
il;;;;i;;;h;[;"y be uoPai;d
a covalcnca
and so is the covalency. For example, sP = [Ne]10 3 ,2 Pl
3Pi 3P] Then it shows
orbitals iDcreases I

of3asinPCl3 Inthe excited state, we have l5P = INello311 3p13pi3p]:dl

Ttrus itwiltshow a covalcDcy
covalency is equal to the number of electront
of 5 as in ,PC-t5AfmfAy, we have SFo and SFu Tlte msimum
preseht in the s ahd P-orbitab of tlrc valence shell in the
ground state'
'l.or this comPound is
p-Oimettroxy Uenzene, # * 0. Tbis is because the structu re of
".-,._oJa _o/,CH,
CH"
\\-/,/
between two atoms is never greater than three'
The maximum number of covalgni bonds formed
#6. a o-bond'
A r-bood is Dever formed alone. It is formed alongwith
#7,
ffi{ E. H-atom always forms oDly one d-bond in the covalent compounds'

Theory Shell
6.23. Valence Shell Electrcn Palr Bespulslon
This
$ un- t940
able e lust esPie
simp in the

I
CHEMICAL BONDING AND MOLECULAR STRUCTURE
in 1957. The basic conccpt of this theory is
follows :
The central atom is linlted to other atoms by
covalent bonds which are formed by sharing of
electrons. Thus, the central atom is surrounded by
shared pairs (or bond pairs) of electrons and there
may be some lone pairs o[ electroDs also present
(which have not taken part in the formation of
bonds). The stabililv ofthe molecule demands that
it should have minimum energy. I[ the electron
pairs surrouading the central atom are nearer, they
will repel eachother, therebyincreasing the energy
of the molecule. But if the electron pairs are far
apart, the repulsions between them will be less and
so the energy of the molecule will be low. Thus the
main idea of the VSEPR theory is as under
:
Tlu elaron pain noarding thc centrul lbm
repel ow atwther aad move so far aparc lmm one
anolher hd there ore nolwther repulsitm between
tham. As a raull, thc moleculz
and ruximum stability.
Since after repulsions between them, the
electron pairs take up definite positions around the
central atom, hence the molecule has a dehnite
s'hdpe or geometry.
The above coricept leads to the following
results (called the basic assumpdons of the
VSEPR thcory) which help to hnd the shape of a
molecule :
(1) The shape of a molecule containing only
two atoms is always linear.
(2) For molecules containing 3 or more atoms,
one of the atoms is called the central atom to which
other atoms are linked.
(3) If the central atom is linked to simiLr
atoms and is surrounded bybond pairs of electrons
only, the repulsions between them are similar. As a
result, the shape of the molecule is sym metricql .and,
the molecule is said. to have a regular geometry.
(a) If the ceutral atom is lirked to different
atoms or is surrounded by bond pairs as well as lone
pairs of electrons, the repulsions between them are
different*. As a result, the molecule has aa.irregular
or distofied geornefiy. The order of repulsions be-
tween electron pairs is as follows :
Lone pair - Lone pair > Lone pair-Bond pair
> Bond pair-Bond
_._'Itwasthi6imPrc!'Ementwhichgla.sprrt-forrardbyNyholmandCiltespicinlgS?.Thcypointedoutthatthercisanimportant
differcrce bctq,recn lone Pairand bond Pair, Whcrcas the lone pair is locali;ed on the atom,_the bond pair is sharcd between t*n
ato.s. As a Esult, a lonc pair oc""rpias mo. s?acc and hence cau.cs gEatcr tcpursion, giving tbc otncr iplp > lp--+p > bp-np.
6/31
as (5) The exact shape of the molecule depends
upon the total number of electron pairs present
around the central atom.
Based on VSEPR theory, the shapes of
molecules containirg 2, 3, 4, 5 or 6 electron pairs
around the central atom, all of which may be bond
pairs only or some of these may be bond pairs and
the remaining may be lone pairs are given in Thble
6.6 on next page alongwith examples of each type.
The detailed discussion of the examples is given in
section 6.25.
6.24. Hybridisation (Valence Bond Approach) :,i:,,i:
No doubt VSEPR theory is able todplaiAth;e
shapes of simple molecules but is unable to predict
qaEx. Moreover -
_..1&E-efasf shape u-a_!C!Sbe.-9f
talking o[ the direclioa of electron pairs does nol
-G"6-o U" u..y ,"tional. lt was onlywith the advent
'of Valence liond Theory that the shapes of
molecules could be explained more preclsely. As
already explained, according to Valence Bond
thcory, a covalent bond is formed by the overlap of
half-filled atomic orbitals. The direction of overlap
gives the direction of the bond. However in apply-
ing this theory, a diffrculty was faced in a number of
cases as explain below :
As a covalent bond is formed by the overlap
of a half-filled atomic orbital, therefore the
covalency of the element should be equal to the
number ofhalf-ftlled orbitzrls present in an atom of
that element. However, on the basis of this concept,
the formation ofmany compounds such as those of
beryllium, boron and carbon could not be ex-
plained. Now let us have a look at this problem.
The electronic configurations of beryllium,
boron and carbon h the ground state are as follows :
Element Atomic Electronic
Number Conllguratlon..
'Bc 4 1"' ,2"'
B5 y2,x2,211, iti
C6 1"',%',2p:2pr,
On the basis of these configurations, we may
conclude that berflium, boron and carbon should
possess zero, one and two covalenceis respectively
.because beryllium has no half-filled aromic orbital,
boron has one and carbon has two. But actually
beryllium has a eovalency of two as in the case of
pair. CrnId. a page 6lj5
6132 N ettt Couyse Chem istrg

TABLE 6.6. Shapes (Gcometry) ofmolecules containing bond palrs onlyor bond paim and lone pairs.

Ibtal No. Geometry of the Bond Irne Geometry of the Exrmplcs

of electron poirs poirs Pairs molecule
electron
psirs

2 0 g=.=g
3e
Lincar a,.L

il
I

3 3 0 u

JY .l: :I
Triangular planar
Triangular planar

/\
: o: ,9,

l 4 0

Tetrahcdml

3 1

Trigonal prramidal
 \
6/33
CHEMICAL BONDING AND MOLECUI.AR STRUCTURE

TABLE CONTINUED

') 2

PCls
-5 0
5

Tligonal biPt'rar:liclal
Trigonal biPYramidal
sztd

sFn
4 l

J 2
ctF3

XeF,
2 3

(,
Linear
/
6134 Neut Couyse Chem istrr!

TABLE CONTINUEO

6 0 SFu

L
sfd
Octahedral

--t
sL'
d1

5 1 clF5

Square pyramidal

,-* ldi''
<)rt L_
4 2 XeFa
l'o
lt.,'
Square planar
x
Note. In predicting geometry of molecules containing double bond, the double bondis considered
as one electron pair. For example, in case of ozone, its two resonating structures are

'9-o=o -- 6=6-o,
In each structure, the central on" to* pui' two bond pairs (counting double bond
as one bond pair), n"o"" it rru, t"Xttof,l# "oa
"
 6/35
CHEMICAL BONDING AND MOLECULAR STRUCTURE

BeF2, boron has a covalencyof thrce as in BF, snall lobe opposite to a big lobe on the other side
of four, e.g, in as shown in Fig. 6.26.
whcreas carbon has a covalency
CHo, CClo, CO, etc.
To overcome the above problem, it was sug-
g OR
a
SIMPLY
e
case of carbon. Its atomic numbcr is 6 and so its
eonfiguration in the ground state Ls FIGURE 6.25. Representation oI a hybrid orbital

6c .......... tu' ,zsz Zpt,zpt' (Growd state)

I .,ftote carefully llra t the encrg requieil lor excita-
Thus, it has two unpaired electrons in the
ion of ebctrons becoma available when lhe com-
ground state. So it should form two bonds only. But beca*se energt
actually carbon shows a covalency of 4. To explain approach euch
this, it is suggested that an electron from 2s orbital other That Ls why hybrilkation never takcs place
iumps to !p orbital and so the configuration of in isol lcd alot Ls but occurs only al tha time of hontl
carbon in the excited state is
Iomdion.
(Excited state)
6c ........ tu2 ,zt' 2p',2p', ,2p: Some Important Points about Hybridisation :

Thus now carbon has four unpaired electrons
thereby explaining tetravalent nature of carbon. Its
one s and three p orbitals can overlap with the
half-filled orbitals of reactiug atoms, formiug four
covalent boods. But covalent bond formed by 2s
orbital of carbon should differ in energy from the
bonds obtained by the threep orbitals Houcwq'
experimental data clearly show tlnt all the four
bonds of iarbon are same in energy.,Moreover, the
three bonds formed by 2p orbitals should be at 90'
to each other and the fourth formed from 2r orbital
may have any direction. However, this is actually
not so. Hence a new concrpt was introduccd to
explain this abnormal behaviour of carbon. Ac-
cording to this concePt, all the four orbitals of
cubon having unpaired electrons ald possessing
slightly different energies mix up their energies aad
then redistribute it in four equal quantities thus
giving rise to four new orbitals each h aving the same
amount of energy. This new concept was referred
as hybridisation. Thus
Hybridisttian b dzlitd tt llv t tixirrg of ltg
utomic orbi.hls balonginE lo lhe ffimc attm bul
haing slipfuly tfifereat etwgir n lhol a
reilistribution of energ taha plarz behemt lham
tesulting in thE lot tuion of ncv orbit4ds o! qwl
othit/,ls tfuts
The shape of a hybrid orbital (made from s
ardp orbitals) is like that ofp orbital except that
the two lobes are unequal in size, i.e., there is one
(i) Only those orbitals which have ap-
proximately equal energies and belong to thc samc
atom or ion can undergo hybridisation
(ii) Number of hybrid orbitals produccd is
cqual to the number of atomic orbitals mixed
(iii) lt is not necessary that all the half:filled
orbitals must participate in hybridisation. Similarly,
i[ is no[ necessary that only half-filled orbitals
should participate in hybridisation. Even completc-
ly filleLl ,rrbitals with slightly diflercnt energies can
also participate.
(lr,) Hybridisation ncver takes place in iso-
latecl atoms but it occurs only at the time of bond
formation.
(r) flpe of hybridisation indicates the
geometry of molecules. One can tell thc shape of a
molecule b,'- knowing the kind of hybridisation in-
volved.
(,i) The bigger lobe of the h.vbrid orbital al-
ways has +ve sign while the smaller lobe on thc
oppositc side has a -ve sign.
fues of Hybridisation.
1. Diagonal or sp hybridisation.
When one s and one p orhital bebnging to tlD sdme
main shell of an aum mix lagelhzt to form fivo ftete
equivalenl orbitab, tln type ol hybridisation it
calM sp hybriilisation or diagonal hybridkation.
The new orbitrulsJormed are called sp hybid orbi-
,ro'ls.
6/35 Neu,t Coutsc Chemistr4

They arc collinear with an angle of ltl0' as

shown in Fig. (r.27.

o.
sp2 HYBBtDtsA.rtoN

Gsb
TWO sp HYB R lD OBB ITALS
rnae i sf Hvsnro onituLs
FIGURE 5.27' Diagonal or sp hybridization
FIGURE 6.2a. Trigonal or sp2 hybridization
Each ol thc hybrid orbitals formcd has 5017"

.r-charactcr arr.J 50'h 1t- chaructcr' Thc rcmaining
trr,, p-rrrhilirls rvhich Jrr nrrl particil'atr: irr
hvbriclisation remain as such. ll thcse arc hull-
lillccl, thcy nray lorm bonds with othcr atoms having
hall-llllcd atomic orbitals.
,/daupr,gs. A tcw compounds in rvhich.y.,
hylirldisation is involvetl are
(r) All compounds of beryllium likc BcFr,
BcH, ctc.
(ii) All compouuds ol carbon containing
C=C triplc hond Iike acetylene (CrHr).
Thcsc rvill be discussed later under 'Shapcs of
rnolccttles'.
2. Trigonat or sp2 hybridisati(,n.
(ii1 All compounds of carbon conl aininr.
C-Ctioublchond.
Thcsc arc discussetl latcr undcr 'Shalrcs r,l
mol, curcs.
-1. Tetrahetlral or sp3 hybridisation.
When one s and three Vorbittls halonging lo lhe
somc shell oI an alom mi-r togclher lo lorm four
ncw equivalenl orbilalt, the lypc oI hyhridisation
is tulktrl s1t! or lelrahcdrul hyhri isation. Tht
nex' orhilals arc culled sp3 or lclruhedral or-
b itu L\.
Thcsc arc clircctocl trrrvards the lirrtr corncrs
ol a regutar tctruhedrctn and mlkc an anqle ol l09'
lS' u,i(h one uno[hcr as rcltrcsentcd in Fig 6 29

l4hen one s and two p orbituls oI lhe sume sfull oI

an u,om mir lo lorm thrw new equivulenr orhitakt,
the qpe olhlhridisatlon is culled ry1 lrybridisalion
ur tiigtial fuhndintiot. The new orbitalsforrned
rc calltd sp2 hlhrid orbltdll,
All the threc hybrid orbitals remain in thc
sumc plunc making an anglc of 120' rvith onc
xnothcr irs rcprcscntcd in Fig. (r.2ll. sp3 t-rYB B tD tsarto t't
Each ol the hybrid orbitals tbrmcd has l/3rd
L-charactcr (33'Z) and 2,i3rdp'charactcr (fi %,). T nc
non-participating /.r-orbitnJ, if halt- trlled, can torm
honcl rvith othcr atorrrs having hzLlf-fillcd orbiturls.
EXAMPLES. A fcw compounds in rvhich FOUR SP3 HYBRID ORBITALS
\1r2 hybri(lisation takes placc are:
cg,, BFr' BH.
fi All contpott t ls r,[ boron. FIGURE 6.29. Tetmhedral or sp:l hybridiz:tion
clc
 CHEIVlICAL BONDING AND MOLECULAH STRUCTURE 637
Each.rpr hyhrid orbital has 25t/c s-charircrer A. SHAPES OT MOLECULES CONTAIN-
aad p- character.
7 Sc/o ING BOND PAIRS ONLY
EXAMPLES. A few compounds in rvhir:h .r23 (1) Shape of Beryllium lluoride (Bctr'2)
hybridisation occurs arc methanc (CHr), cthane moleculc:
(CrHo) etc., i.e., all compounds ofcarbon conlain- (a) On the basis of hltridlsation
Atomic number of Be = 4
ing C C singte bonds only. Thcsc are discusscd in
- Its electronic configuration in the ground
clctail in thc ncxt sectioo under thc'shupcs ol' statc is Lr2 2s2.
molecules'.
The elcctronic cotrfisuralion in the excited
It is interesting to mention here that thc size statc is tsz 2rl p].
of.rp-hyhrid orbital is smallcr than that ofrTr: ht brid One 2r a
orbital \\,hich in turn is smaller than th:rt ol .vr3 hybridisation to
hybrid orbital. bitals which are
c : _ :iir..cli.nel o-.,nndi6c .. irrnds overlap with the
atoms to give a linear shape as shown in Fig. 6.30.
and Geornetry or Shapes ol Molecules ;,.iri:ir:j!:iJl
(D) On tbe basis ofYSEPR theory, In BeFr,
As alrcady discussod, ionic bond is non-direc-
thc central atom is Be which has two valence
tional. Hence the structur-e_qf an ionic qomgound electrons. It shares these electrons with two
is dctormincd by the relative size of the ions. How- fluorine al.oms, r'.e. its Lewis structure is
cver a covalcnt bond is directional. This is becruse
a covalent bond is formed by the r-rverlap of half-
filled orbitals (hybridised or unhybridised). The :F : BC: F:
direction ofoverlapgives the direction ofthe b,,nd.
Furthor, it may be pointed out that a hyl.ridised
orhital has greater directional character thirn l)-or-
bital because p-orbital has equal sized lohcs rvith
equal electron dcnsity in both the lobes whercas a
hybridized orbital has greater electron dcnsitv on
one side. Thus, in case of molecules
containing three or more atoms, one o[
the atoms is the ceotral a(om and the
othcr atoms are linked to it in tlcfinite
directions.
A partieular Krar.gcncnt obtairud by
O.-%,,t'*i,"*db- sp
HYBRIO
ORB ITALS
bonding a numbet of atont in delinite
.liecliotlr to lhe central dtom of u 180o
molealt is called the geomclry or shape ---D F.-,r- Be-l- F
ofthe mol*ule.
LINEA R
The geometry or shapc o[ a
molecule (as found by experimental FIGURE 6.3O. Formation of sp hybrid orbitils and shape of BeF2
methods) can be explained on the basis
of either of the following : (2) Slape of Boron trilluoritte (B[.r)
(i) Volence Shell Electrcn pair Rcpulsion
molecule;
Theon, (VSEPR Tltcory) (a) On the basis ofhybridisati0n

(ii) Hybidisztion Atonric numbcr of B : 5

Its e-lcctronic configurulion in thc grrrunrl
The shapes of a few molecules on the hasis ol stxte is l.r2 lr2 ?,1
hvbridization as wcll as VSEpR thcory arc brrofly
dcscribcd below : Thc elcctronic etlnfiguration in the exeitr:tl
strtc isI r'2 :t'
],1 l,i
6/38 NeuJ CouYse Chentistrry

One 2s and two !p orbitals undergo sp2 hybridisation to form three haH-fill9d sP2-hybrid orbitals
which are planar and oiiented at an angle oi Lz}'to each other. These overlap with half-frlled orbitals of
three fluorine atoms to form BF, whic6, therefore, has triangular planar shape as shown in Fig.6.31.

sp2HYBRlD ORBITALS

FIGUBE 5.31. Formation of sp2 hybrid

orbitals and shape of BF3.

(D) On the basis ofVSEPRtheory. In BFr, the
central atom is B which has three valence electrons.
It shares these electrons with three fluorine atoms
i.e. its Lewis structure is
,f ,
F B: F:
Thus B atom is surrounded by three bond
pairs which according to VSEPR theory take up
positions at irn angle of 120'with respect to each
other thereby giving it a triangular planar shape as
shown in Fig. 6.31.
(3) Shape of Methane (CH) molecule:
(c) On the basis of hYbridisation.
Atomicnumber of C:6
Its electronic configuration in the ground
state is kz bz 2p'rU',
The electronic configuration in the excited
state is lsz bl zprrzpiui
One 2s and three 2p orbitals undergo sp3
hybridisation to form four sp3 hybrid orbitals which
aie arranged tetrahedrally nt il1 angls of 109" 28'
to each other.
The four sp3 hybrid orbitals overlap with the
half- filled fu orbitals of four'Il-atoms, tbrming
CHo as represented in Fig. 6.32' Thus CHn is a
tetrahedral molecule with each H-C- H angle
equal to L09' ?3' (= 109' 5").
(D) On the basis of VSEPR theory. Ceutral
atom in CHn is C. It has four valence electrons
vrhich are shared with four hydrogen atoms. Thus
there are four bond pairs of electrons present
around the central atom (carbon) as follows :
tI
H:C:H
H
Now according to VSEPR theory, these four
electron pairs will repel each other and thus move
so far apart that there are no further repulsions
between them. The only shape possible is
tetrahedral as shown inFig.6.32.
Some other examples of molecules/ions
having tetrahedral shapes are CCla, SiF4, SiH4,
NHo+, BQ- etc.
CHEMICAL BONDING AND MOLECULAR STRUCTURE 6/39

HH
H-AfoM

FIGURE 6.32. Formation oI CLI4 molecule.

(4) Shape ofEthane (CrH) molecule : In the

formation of ethane rnolecule, each carbon atom
uadergoes sy' hybridisation, thus forming four sp3
hybrid orbitals directed towards the corners of a
tetrahedron and inclined to each other at an atrgle
of 109'28' . one sf hybrid orbital of the Iirst carbon
atom undergoes overlappi.ng with one s1 hybrid
orbital of the sccoEd crrbon atom a-loEg the inter-
nuclear axis, thus forming a o bond between them.
H.ATOM
The remaining three sp3 hybrid orbitals of each H.
carbon atom urdergo overlapping with the half-
filled tu-orbitals of H-atoms, each along the inter- "
/'
nuclear axis and hence forming a o bond. Thus the
complete picturc may be represented as shown in /-.-
Fig.6.33
Obviously, the nolecule has a regular
geometry. \,
The various bond parameters are fouad to be
FIGURE6.33. Formation of elhane molecr.tle.
as follows :

(i) C-C bond length : 154 pm (5) Shape ofEthylene (C2H.) molecule : The
(ii) Each C-H bond length : 110 pm electronic configuration of C-atom in the excited
state is : uC : b2 2sl U:zp'r 2?:
(ii) Each H-C-C
In the formation- o[ ethyleoe molecule, each
or H-C-H bond angle = 109'28' C-atom undergoes spz hybridisation, thus leaving
ooe ?p, orbital in the original state, i.e., in the
(iv) C-C bond dissociatiotr etrergy
unhybridised state. The three{p2 bybrid orbitals of
: 3,18 kI mol-r. each C-atom are planar and are inclined to each
other at an angle o[ 120'. One spz hybrid orbital of
6140
the first C-atom ovorlaps with one spz hybrid
orbital ofthe second C-atom along the internuclear
axis thereby forming one sigma bood between
them. The other two spz hybrid orbitals of each
C-atom ove ap with the half-filled tu-orbitals of
H-atoms along their respective iaternuclear axis
forming o-bonds. The unhybridised !p, orbitat oI
the first C-atom undergoes sideways overlappiag
with the unhybridised 2p, orbital of the second
C-atom, thereby forming az bond between the two
C-atoms. So the formation of ethylene molecule
may be represented as shovm in Fig. 6.34.
FIGURE 6.34. Formation of ethene (C2H4) molecule
Thus the two C-atoms are linked to each other
by one abond and one z bond and each C-atom is
further linked to two H-atoms by o bonds. The
molecule is planar. The various bond parameters
are so follows :
(i) C :
C bond length = 134 pm
(ii) Each C-H bond length = 199 Oot
(iii) Each C-C-H or H-C-C bond angles
= 120"
(rv) Total C = C bond dissociation energy =
614 kJ mol-r.
Out of 614 kI, the bond dissociation energy
for obond is 3tB kJ (as alreadymentioned). There-
fore, the bond dissociatioa energy for z bond is
614- 3.18 : 6kJlmole. Hence z bond is a weaker
bond. This is the reason for high reactivity of com-
pounds containing z bonds.
(6) Shape of Acetylene (C2H2) molecule : In
the formation of acetfene molecule, each C-atom
Neqt Coutse Chemistrq
undergoes sp hybridisation leaving two 4, orbitals
in the original unhybridised state. The two sp
hybrid orbitals of each C-atom are linear, i.e., they
are 180' apart. One sp hybrid of the frrst C-atom
overlaps with one sp hgbid orbital of tbe second
C-atom along the internuclear a:ris thus forming o
bond bctwecn them (Fig. 6.35). Thc second sp
hybrid orbital of each C- atom overlaps with the
half-hlled 1s-orbital of H-atom again along the in-
ternuclear a.:ris and thus forming o bonds,
The un-hybridised 2p, orbital of the hrst C-
atom undergoes sideways overlapping with
the ?, orbital of the second C-atom, there-
by forming a z bond between the two C-
atoms. Similarly, the unhybridised fu.
orbitals overlap sideways forming another
z bond between the two C-atoms. Thus all
the carbon and hydrogen atoms are linear
and there is electron cloud above aadbelow,
in the front aad at theback ofthe C- C axis.
In other words, there is electron cloud all
around the internuclear axis thus giving a
calindrlcal shape as represented in Fig.
6.35.
,r-o N D
o
1l
g-6lIE6-s
L
FIGUBE 6.35. Formation of acetvlene (CeH.r)
molerr.rle (cylindrical shaf e).
The various bond paramcters of acetylene
molecule are as follows
:
(i) C = Cbond length = 120 pm
(i/) C-H bond length = 108 pm
( ) H-C-C bond angle - 180'
(iv) Total C=C bond dissociation encrgy
:811 kI mol-1
CHEMICAL BONOING AND MOLECULAH STRUCTURE 6141

(7) Shape of PF, molecule. In PFr, the that axial P-F bonds are slightly longer than
cenl.ral atom, phosphorus, has the ground stale P- F bonds (Bond
equatorial lengths : P- F axiatl
e lecrronic configur;ton lsz 2s2 2p6 atz qt,q) y! = L58 pm, P-F equatorial : 153 pm). However
NMR (Nuclear Magnetic Resonaoce) studies show
One of the 3 electron gets promoted to 3d orbital
that all the hve F atom-s are equivalent and can
giving the electronic conhguration 'ts2 2sz 2p6
exchange their positions* and hence all the five
kt 3p:3pjp: Ut. Thus it involves spJd hybridisa-
tion (rig. 3.ro).
P
- F bonds have the same length. The reason for
the difference in the two studies is on account r,i the
fact that electron diffraction gives instantaneous
F
picture of the molecule whereas NMR takes time
more than the time required for the interchange of
ixial and equatorial F atoms.
Otherexamples. Similar geometry is expected
for PCl, and SbCl, molecules. However in PClr,
axial P-Cl bonds (bond length : 219 pm) are
longer than equatorial P-Cl bonds (bond length
= 204 pm).
(E) Shape of sulphur hexalluoride (SF)' In
EouAloRtAL SF5, the central atom, sulphur, has the ground state
electronic confguration G 2;2 2p6 k2 3p13p1y3pt,
FIGURE 6.36. Trigonal bipyramiCal geometry of PF5 and F has 1"'2.? 2pizpiU:. One of the 3s

elecrtrons as well as 3p electron get promoted to 3d

Alteflrutiveb,, the central P-atom has 5 valcncc orbitals giving Ge electronic configuration
electrons. As a result, it is surrounded by five bond
'!s2 N2 2p6 kt
3pt,3pt"3p1,ut 3dr. Thus it involves
pairs of electrons. spry hybridisation. Aiternativety, it has 6 electrons in
the ralence shell. As a result, the cntral atom is
surrounded by six bond pairs of electrons in the
.F: valencr shell.
+5
.q
F .. 'i
:S:+6 .F: + F ..5 F:
According to VSEPR theory, for PF, to have
minimum energy, the bond pairs of electrons
i:"f .. F:
should be as far apart as possible from each other.
This is possible only if the molecule acquires a According to VSEPR theory, for SFu to have
trigonal bipyramidal shape. minimum enerry, the bond pairs of electrons
In this structure, three of the fluorine atoms should be as far apart as possible from each other.
lie in the same plane as phosphorus atom and are called ThLs is possible only if the molecule acquires a
equatorial fluorine atoms and the bonds formed are rtgular octahedral geometry (Fig. 6.37).
e led equatorial bonds, The other two fluorine atoms IfSFu, four S are in the same plane
lie at right angle to the plane of equatorial bonds and -Fbonds
are known :s axial fluorine atoms and the bonds at right angles to one another and are directed
formed by them are called axial bonds. towards the four corners of a square. The othr two
F atoms lie at right atrgle above and below the plane
Bond lengths anil Bond angles in PFr.
of F atoms.
Electron diffraction studies of PF, gas show that
SFu molecule is a symmetrical molecule and,
the equatorial bonds are at angle of 120" with each
other whereas axialbonds make an angle of 90'with therefore, is stable and far less reactive.
the equatorial bonds. Further, these studies show
?Thc interchange o[ axial and equatorial po6itions is called'pseudorotation'.
6142 Pradeer's Nett Coursc Chemisrg JIIDT
Its electronic configuration is
4 ts, N, zpt, 21, zlt"
,'i One 2s and three Q orbitals undergo qp3
hybridisation formiag four sp3 hybrid orbitals out
of which three contain one electron each and take
,,;\ part in bond formation and the fourth rp3 hybrid
,'i Y orbital contains a lone pair of electrors and hence
cannot participate itr the bond formation. The four
F Z--v .1p3 hybrid orbitals will obviously be directed
towards the corners ofa tetrahedron and hence the
bond angle between any two sp3 hybrid grbitals
would be 109' 28'. Now, when the three spr hybrid
orbitals, each containing one electron only, overlap
FIGIJRE 6.37. Octahedral geomety oI SF5. with the ls-orbitals of H-atoms to form NHr, the
expected H-N-H bond angle is 109' 28'. But ex-
Otherexamples. TeF 6 is also expected tohave
perimentally, the bond angle in NH, is found to be
a regular octehedral geometry.
107'. The obvious reason for the decrease in angle
B. SHAPES OF MOLECULES CONTAIN. is that the lone pair repels the bond pairs. Thus the
ING BOND PAIRS AS WELL AS LONE PAIRS formation of NH, molecule may be represented
(9) Shape of Ammonia (NHr) molecule :
diagrammatically as shown in Fig. 6.38.
Atomic number of N : 7

1s

7N =
@
N

BONDING
sp3.HYBRID ORBITALS

OR

HH
CHEMICAL BONDING AND MOLECULAR STAUCTURE
Such a shape is known as trigonal (or hian-
gularl pyramid in which thE three H-atoms form
the triangular base of the pyramid with N-atom at
the apex. The same applies to molecules like
PCl3, NF3 and HrO+.
(10) Shape of water (HrO) molecule : The
shape of HrO molecule can be explained exactly in
the same way as in case of NH, molecule.
Atomic number of Orygen : 8
Its electronic configuration is
1s2N2fi2p)zpr,
One 2s and three p orbitals undergo sp3
hybridisation forming four sp3 hybrid orbitals out
of which two contain one electron each and the
other two contain a pair of electrons (i.e., lone-
pair) each. As usual, the four sp3 hybrid orbitals
thus formed are directed towards the corners of a
tetrahedron and hence the bond ang.le between any
two sp3 hybrid orbitals would be 109"28'. Now when
the two sp3 hybrid orbitals containing one electron
each, overlap with the half-filled fu orbitals of
H-atoms to form HrO, the e4pected H-O-Hbond
go=
FIGURE 6.39. Forrnation of water (F{2o) molecule.
6143
angle is t09'28' . But e4perimentally the bond angle
isfound to be 104. 5". The reason for the still lesser
bond angle inH2O thaninNH, is that in thi5 snss
there are two lone pairs of electrons present which
repel the bond pairs. Thus in this case the repul-
sions are more than those in the case of NH,
molecule. The formation of HrO molecule maybe
represented as shown in Fig. 6.39. Thus water is
Y-shaped or bent molecule.
HF molecule is linear since it has only two
atoms though in this case also, four electron pairs
(one bond pair and three lone pairs) form
tetrahedral geometry.
Some other examples of molecules/ions
having shape similar to thatof HrO are SOr, FrO,
NH, , SCI etc.
(11) Shape of SF. molecule. This is an ex-
ample of a molecule in which the effect of lone pair
has a great significance in deciding the shape of the
molecule.
Atomicnumber of the central atom (S) : 16.
Its electronic configuration is
BONDING
sf-HYBRID oRBITALS
LONE PAIRS
OF ELECTRONS
6144 Pradeep's

1s2 2s2 2p6 3s2 3d 3Pry3pt"

F
or in the excited stat, it is
Lsz %2 A 3s2 3p1,3ppplY1
It undergoes sp3d hybridisation to form lle
TffI;
ectron
each which are shared with those of F-atoms.
In terms of VSEPR model, in SFa, S atom ha.s
5 electron pairs around it i.a. 4 bond pairs and one
o
lone pair. Hence their arrangement should be
trigonal hipyramidal.
Depending upon the position occupied by
lone pair, two possible structures of SFo are :

FF
Lone pair occupying Lone pair occupyhg
axial position equatonal Position
(Less slable) (More stable)

FIGURE 6.4O' Two possible structutes of SF4

repulsiorus at 90' LONE PAIRS
LONE PAIBS
wh IP-bP rePulsioas OF ELECTRONS
at e and hence the
correct strucfure* . lt is a distotted tetrahedron ol a
folded square or a see-sat4,.
(12) Sfrape of ClF, molecule. This is another
example in which the lone pairs decide the shape
of the molecule. It is isoelcctronic with SFo but it
has two lone pairs and three bond pairs The fol-
lowing three arrangements are possible :
on
Based lsions, it
is foundthat i.c. has Smaller distance {closgr
bond pairs), larger
minimum ener ence (a) repulsions.
is the correct struclwei.e. ithasT-shtpe.
Elfct oflectrotregativity ot the central atom FIGURE 5.42. Ilepulsion of bond pairs and lone pairs
on the bond angle of similar molecules. For cx-
rAl6o rmembcr that rcpulsion bclween electron paitE dccEascs with incrtisinE bond anglc betutcn thcm. ThcrcfoE
rcpulsioffi bciwecn clcctron Pairi at 120'and 180'rDaybe neglected in comParison to thosc at 9f'
..tn <a),lp - lp = 0, lp - bp = 4,bp - bp = 2
comPared with (b)' (a) has no'p - rePulsions' com-
tn (b),lp - tp = t,tp -bp = 3,bp - bp =1 with (c)' (a) has less {P - repulsioos'
'P
Pared
tn(.),lp - t? =o,lp - up = u,up - op =i 'p
CHEIiIICAL BONDING AND MOLECULAR STRUCTURE
Due to smaller size and high electronegativity
of O-atom, the bondpairs are closer to O-atom and
hence therepulsions between them are large. Aswe
move from orygen to tellurium, the size of the atom
increases and electronegativity decreases. As a
result, the bond pairs move away from the central
atom. Hence the repulsions between thebond pairs
decrease and so the bond angle also dccreases.
Similarly, in case of hydrides of group 15 (all
of which have pynamidal shape with one lone pair
of electrons on the central atom), the bond angles
decrease as follows :
NH, PH, AsH, BiHl
107.5'93.4" 91.5' 9t.2'
Conclusion. In similar molaub, as the
elearorugutivily of lhc ccrrtdlatom decre$, und
tlu she innerses,lhe borul anfu dffr?uff$'
Elfect of electronegativity oI the surrounding
atom on the bond angle of similar molecules. For
example, in the trihalides of phosphorus (all of
which have pyramidal shape), thc bond angles in-
crccse as follows :
PFt PCl3 PBT, PI,
9T 10ff 101.5' L02'
This is evidently due to the fact that due to
high electronegativity off,, bond pair ofelectrons is
more attracted towards F i.e. it lies away from the
central atom. As slectrotregativity decreases from
F to I, the bond pairs are closer to ths central atom
and the repulsions between the bond pairs increase
and so the bond angle also increases.
For the same reason, the bond angle in FrO is
smaller than that ir H2O.
Note, (i) For molecuJes or ions having regular
geometry, the change in the electronegativity of the
AICI, etc.
Similarly, CH4, CCl4, NH4+ etc. all have the same
bond angle viz. 1@?8'.
(ii) Bond angles may vary due to cqtain other
factors also e.g bond angle of NH, is greater than
that of NF, but bond angle of PH, is less than that
of PF, (See Page 6/67).
6145
6.26. Co-ordinate or Dative Bond t:::rrlij:iil::i;i,:i::!:i::i:ii;iii:::::::ir:::
Perkins in 1921, suggested a third possible
way by which atoms cao combine and form a
molecule to account for the sEuctures of certain
compounds such as sulphur trioxide, sulphuric
acid, nitric acid etc.
It was assumed that certain atoms which haye
complete octets can donate their valence electrons
which are not involved in thc bond formation, to
other atom/atoms which are short of electrons.
These donated electrons are, therefore, lone pairs
of electrons and arc shared by both the atoms.
Trm itt thz lottulhn oI d hond, fu ewftrn ,air
(b,e pair) b doaodry ortcdk,i bd *Edb! botk
lhE atoE,J fr ai lo @r,pki ilun odztg tlu botd
[ord it ald u*rdilutc hotil or dative botd
Thus whereas in case ofcovalency, the shared
pair of electrons has equal contribution from both
the combiningatoms, inthis case shared pair comes
from only one atom, and this atom is termed as
donor and the other atom tus acceptor. This bond is
represented by an arrow pointing from the donor
to thc acceptor. Compounds havingthis linkage are
known as co-ordinate compounds. Since this bond
has some polar character,it is also knorcafdative
ii semi-polarbond or co.ionic bond. Some illustra-
tions are given below :
(i) Combination of Ammonia and Boron tri-
fluoride : In case of ammonia, nitrogen has hve
valence electrons. C)ut of these, three electrons are
shared by three hydrogen atoms to form ammonia
molecule while the remaining two electrons form a
lone pair, which can be donated to any electron-
deficient atom or molecule. In BF, molecule,
boron is short of two electrons. So to complete its
octet, it shares the lone pair of nitrogen, forming a
dative bond as shown in Fig. 6.43.
HF
u +H-N+B-F
tt
lt
HF
FIGURE 5,43, Formation of a co-ordinate
hond between NH3 and BF3
 i rrtlrt,t,'s Nett Couvse Chemistrqlftfi[fi
(ii) Sulphur Dioxide : Sulphur as well as orygen atorns have six valence electrons and each is short
of two electrrons to complete its octet. In order to comPlete their octets, sulPhur atom and orygen atom,
share two electrons each thus forming a double bond berween them. Sulphur atom still has four unshared
electrons, i.e., two lone pairs to donate. Thus sulphur donates one lone pair to one orygen atom, forming
a co-ordiuate bond between sulphur and orygen and a molecule ofsulphur dioxide. By accepting this lone
pair, octet of oxygen is also completed, as represented in Fig. 6.44.

J,.
FIGUBE 5.44. Formation oI sulphur dioxide molecule

(iii) Ammonium ion : In NHr, N atom has ooe lone pair of electrons. It can donate this lonc pair to
H+ ion thus forming a co-ordinate bond as represented in Fig.6.45.

H
H
(ii
H:N: +H+
w H
H
)r-! [":
H

FIGURE 6.45. Formation of ammonium (NHfl ion.

(ir,) Sulphuric acid : The Lewis structure of HrSOn is as follows :

:o:
H:O:S: O: H
X/ :o;

Evidently, S atom has two lone pairs of Co-orrlinate bond in terms ol

electrons which it can donate to fwo O-atoms Valence Bond Approach (Orbital concept).
forming co-ordinate bonds. Representing co-or-
dintae bouds by arrows, the above structure may
be drawn as under :
o
t This may be explained with the following ex-
H-O-S-O-H
I amples :
o
(i) Formation of ammonium (NHi) ion. As
Actording lo lhc moilern conccplt lhcre k no dis- already explained under the shape of NHa
tinction betien a cmalcnt bond and a cnardinstz
molecule, N atom in NH. still contaias one hybrid
orbital containing a lone pair of electrons. This
orbital overlaps with the emptys-orbital of H+ ion,
(as abesly distussed in Section 6.1I, page tbrming a co-ordinate bond as shown in Fig. 6.46.
a distittct fi is made.
 6147
CHEIVTICAL BONDING AND MOLECULAR STRUCTUBE

electrons. One of these orbitals overlaps with the

w IS
empty orbital of H+ ion, forming a co-ordinate
bond as shown in Fig. 6.4?.
PAIR

.o
CO-ORDINATE BOND
FORMED HERE

LONE PAIRS
EMPry

NH" MOLECULE
s-ORBITAL
OF H+ ION
NH ION
.o"'--
EMPTY
FIGUBE 6.45. Formation of NH{ion (orbital concept)' s-oR BITAL
OF H+ ION
H3O tON
(ii) Formation ofhydrotrium (H3O+) ion'As
already explained under the shape of HrO 5.47. Formation of H3O+ ion (odital concept)'
FIGLRE
molecule, the O-atom in HrO still contaios two
d hybrid orbitals, each containing a lone pair of

The dipole moment of ,CO molecule is greater than expected This is because
of the presenc of a dative
i
(co-ordinate) bond.
I H2O2 molcule is said to have an open- book t)? structure as shown iD the Fi8' below
:

95 pm
l\-r,'
- o-o-
G= 2.1 o)
,l47.5 pm

ir:: 3. The abi.t ryof the bybrid orbitals to overlap is in theorder tt:E.:lj" gcater is theP- character, Sreater
is tbe ability to overlaP.
iii:i a. The bond an8lcs formed by different hybrid orbita.ls are in the order rP (180) >sp2112/|--1','f lfm
Slie
ttle bond augle.
8reEr tbc J{haracler, Sleater is
The n -bond formed betwecn S aDd O atoms in SO2 molecule is due to overlaP betwecn thet P-orbihlr
or
i :ii 5 .
betwee[ p orbital of O-atom with d{rbital of S- atom (calledPz - d,r bonding)
p\rZ pt,
fis = 7 s2 z!2 2P6 3 t2 Z fiZ p,r-P,r
(Ground state configuration) b bonding
= 1 s2 2 s2 2 P6 3 tt 3 P1, 3 P)3 Pl, 3 d\
(Ercited srate confiSuration)

8o=1s2|sx2rtzP1y2Ptz
S-atom undergoes,rpz hybridlsation leaving one half-
Iilled 3pz orbitaland ooe d-orbitaluotrybridized. Out
of tro half-fllled orbitals of Otorn, oDe is invoh/ed in
formatioD of d-bond with S-atom and the other in
 6/4A

6.27. R
o-

,,.,.,/ \ \\
..-./ \
'P
"9' ,
This representation is somewhat mldeading be-
cause it suggests that the molecule has two forns, I
ard tr which oscillate back and forth between them.
One can arrive at a better representation of
the hybrid slructure by superimposing one struc-
For example, the structure of ozone can be
ture upon the other.
The result of this superimposition is shown
below :
ii
.'i ...-
:9 ..o..
oB
/"t,
where each orygen atom has an octet of
electrons. But this structure is unsatisfactory be-
cause it depicts the central O atom to be bonded
This representation indicates that (!) there is
to one O atom by a double bond and the other O
one stable hytrid form, (rt) this form is symmetrical,
atom by a single bond. Since double boud is
shorter than single bond, the two bond lengths in
(iii) the same length
this molecule should be unequal (O-O single (inb uble bond) and
bond length :lr8pm, O = O double bond (rr) rangement inter-
length : 121pm). But experimental evidence not mediate befween the two resonating structures
only shows that the bond lengths are equal but drawn earlier.
also shows that the bonds are intermediate be- Thus the structure of O, molecule may be
tween single and double bonds (equal to 128 pm). written a,s
Hence for molecule like Or, a single Lewis struc-
ture is unable lo explain the observed facts.
Hence an alternate Lewis structure can be writ-
ten in which the double and single bonds are ,/o\
interchangcd. ,/\
.../
..o.. \\...o.
6... oR

,/'\
Neither of the above two structures can ex-
plain all the properties of Or. Hence the actual
structure is intermediate between the two Lewis
structures and is said to be resonance hybrid.
The phenomenon is represented by drawing The resonance structures are arbitrary and
-- _
all the probable Lewis structure andputting doubl; imaginary and have no physical reality since neither
headed arrows between them*. The actuil struc-
of the two ozore structures, can be prepared in the
tures is intermediate between these. Thus O,
laboratory.
molecule is represented as
.Thc designation must be carefully distinguished from lhe dcsignation
teaction The double hcaded arrow does not have aDy ijFamic significance iit mercly implies that the molecule or ior
-
represcrtcd by both shrctures than byone of them alonc.
is better
 CHEMICAL BONDING AND MOLECULAR STHUCTURE
6149
Since there are matry molecures rike o, whose behaviour
cannot be explained by a single Lewis
structur' there is a need for this concept. The resonance
conceDt finds extensive use in expla'ining the
behaviour of unsaturated organic compounds,
structuns : tt is of interest here ro note that the different
",r"fi:"".U$:1ilrt
fiIHl:r resonaring

o-same poitions of atoms (ii\ sone number of shared an d unshared electrons (iii) almost
equal energt.
They differ only in the arrangement of electrons in different
resonating forms.
Examples of resonanc structures ofsome more molecules
and ions are given below:
(i) Carbon Dioxide (COr)*

!O=C=O: <+ !O=C_O: + lO-C=Oi

III
That the actual structure ofco, is a resonancc hybrid ofthe above tfuee structures is again supported
both the bond leogths is same (i.e. 115 pm) which
C = O triple bond (f10 pm).

:o: :o! : o':

il I

z
C C
I

C
-r"\-
:o: :o:
I :o: :o: \
I

o .-- s.--a
III

Dewar structures

:o: :o: :o:

il t t
S S
S
:o: ,9t ,:1,

..SrructuEs Page 6111.

llllo V put tofi,ard bv Dcqar and hcnce arc less stable i.c ha!'E hiSher
main contriburing
ontriburing structurEs fo;;6I";;i'").
Ir i""r f^;j::Eh:nelong6ond
structurei are I and II(put cner$r. Hcnce lhe
 Pratlc e p's Neqt: Cour,se Chemistr4frffi)
6/50

(v) Nitrate Ion (NOf)

:o: :o: :o:

ll
t
I
N N
N..._ \-
--'- \ -o:
:o- /
:o: tgt",,- ,9,-
{ii ) As a rcsult o[ resonancc, the bond lengths
in lr'molecule become cqual eg O-O bond
lengths in ozonc or C - O bond lengths in
COj -

ion.
(iil) The resonance hybrid has lowcr encrgv
ond hen.e grcuter slability than uny of the
con-
CONTRIBUTING
STRUCTURES tributing structures
(CANONICAL FORMS)
III (iv) Greater is the resonancc energy, greater
is the stabiliw of the molecule.
II
(v) Greater is the number of canonical forms
(, I
with nearly same energy' greater is the
(! "rp".iutty
UJ stability of the molecule.
zL! RESONANCE
ENERGY Clarilication about certain misconceptions
in Resonance
real existence
nesorueNcE XVAnto l'"'"hTi:iil:
presented bY a

energy sirgle Lewis structure.

FIGURE 6.48. Concept of resonance exist-
2. As canonical fofms do not have real
ence, it should be clear in mhd t-hat
The
(i) the molecule does not exisl in onc caloru-
and time and in other forms at dif-
lzust enagl| is cal@ rtsonance energf, ""r
fJ#io, tor.
ferent times.
(ii) there is no cquilibrium between dif-
f.renlcanonicut forms si;ilar to the one we have
i"'i'il-i""i"ritic forms (keto and enol) in
tautomerism.
existence.

or ions exhibiting resonance lt is calculated as follows:

.: l. The boDd order changes in case of moleculcs

Bondorder = gstructu.e"
o- o o-
ofcarbooaie ion,
I il
C_ t
e.g. (i) ln case /C\
\' ,/\ o- \
"/
 CHEMICAL BONDING AND MOLECULAR
STRUCTURE
6151

ADO TO YOUR KN OWLEDGE,CO N-rD.

Lookrng at bonds of c-arom wirh a narricurar oxygeD
atom (say rhe one Iinked on the retr) the bonds
and I respecriverv in rhe rhree srruciurcs aro nuiriu", are 2. t
or ioool,i"g
.. Bood order = ?j-l_1-.1 = 1=
"iir.i,iil. ,, l,
I .33

O ._ [3 ,
(/i) In case of benzene, uo'oo'661 =1i2=rs
The observed varue is, however, not exacfly
equar to r .5 due to some other conrributing
structures

C_O bond leDgths are differerlt but in formare

ion

nd lengths are equaldue to resoDance.

(ii)
Tlrc size olthe dectonegotiv( utont
.
be ynall. The smaller the size, the grcater
Jlt()4ld
is thu
erectrostaUc attraction.
Thus, only f; O and N
.hydrogen atoms can form
bonds, as tlese atoms are small in size
and have high electrooegativities.
Chlorine haviog the same electronegativitv as
+d -d +t -d +t -d ..
that. ol nitrogen does not
H- X -___ H_X _____ H_X to its large size.
form hydrogen iond duc

3. Examples ofhydrogen bonding:

,ing
rhc
Condltio,ns for hydrogen bondlns : In
2.. for
" the
rormalron ot hj/drogen bond, the followiig
condi-
hoDs must be fu.lfill;d :

-..t9,<-\ 1400 H-j ,,-,,..'\,*

gP',*
F-d
i-r
.Not incl
6152
oxygen atom linked to hydrogen
Water molecule contains highly electronegative
(ii) Water (HrO):
.' ' -^:-":'of
'J.'#,Pli:fl::'lfi1T-"--L
atom.rhusorysenatom :r":111t--::",T1tli'**:lt]:,*':.lTiJil.'til
ir"'"i'e""-t'*
"'a
ace as shown berow:
ot one mole"ule attracts the positive
;"d:'iil;;i;;;;Jry
+5 FE
IJ. ,H
\:0,/
.Lr.

"
+o ! lllDm
+b

'\ru/"
)Q ee Pm

the highly electonegative atom N linked

to H-atoms Hence'
(iii) Ammonia (NHr) : It contains
hydro'g;bonding takes piace as follows
'
H*6
\
:---------iij,':
,/ /-
H+o

Alc
(iv) acids In casc of HR H'?O' NH" ROH etc ' the
(RCO()H) highly hvdrogcn bondins causes the association of many
clecrronegati --oni il;;""i* hut in"carhorylic acids, the hydrogen
: bonding is limited to the association of
two
hence form a
molecules onlY
P R

1l
11 R
ALCOHOLS

-d +d -d

H.. Fbond dissociation energy is 41 8kJmol-t'

H . O bond dissociation energyis 29 3 kJ mol-1
N bond dissociation energyis 12 6
kJ mol-1
H.
u-n \r
Thc force \r'hich
l in a molcculat

- arc knolrrl
crlstal asva^d"t.*-11lll1*I""iJli;t";ffi>;ila.; on.l > r?n.rerwaal's forces
Eleatrostatlc lorce
 CHEMICAL BONDING AND MOLECULAR STRUCTURE
6153
,rn *n"" b"tween Hydrogen bond and Covalent bond. The
maia points of difference are given
b"lorj:
COVALENT BOND
(i) lt i[volve6 dipole-dipole attraitive interactions.- (4 It invohrs shariog of
(i4 It is formed btween a hydrogen arom and a highty "l"ct.o^.
(rr) It. is. formed between
electronegative atorn such as E O and N. -
two electronegativc atoms
wiich may be of the same elcmeor oi of differeDt
elemeDts.
(rii) The strcngth of this boDd is very smatt. e.g. boDd (iii) The bond strengh of this bond is sutficieotly high
streDgth cf H..........F bond is 41.8 kJ mof-r. e-&, bond strength of H-H bond is 433 kI mol-r.
6.. Elfects or Consequences ofhydrogen
bond-
ing.: Hydrogen
Hydrogen bond helps in explaioins tie abnor_
explaioing the alnoi_
mal physical
physrcal properLies in serveral cases. Some oI
nf
the properties affected by H-bond are given
below:

t50
I

lo I
a o-
: -50 F
F z
z o-
p -roo o-
o
Z -tso
z
tr
o
6l
LIJ

|
-200

rro
o
FIGURE 6.49, The abnormally hjgh m.p. and
b.p. of H2q NH3 End HF.*
 lrratleelt's Ne.4 Courie Chem ist,,rtrfrlD
6154
The enthalPics
same trend as
4e(")

q
HrS, HrSe and HrTe 5
(c) NH. has ligher boilirtg point thsn PH3 ' z
bonding in
I
This is again tecause there is hydrogen t2
NH3 hut d,

(,1) ling Point-jho.n o

diethyl et ogen b-onding,in
thc form nbonding in thc TL
o
latter. 0-

It is interestiflg to nole that a slronger H-bonl exists E

F
i-iii tt H2o, let watet boils at higJur zr!
"""in
thtn Hn fi is pmbsbb due to lhcldct
-iii
kmDeralure PERIOD
-} of vaporisation
iiu Jor^, t"o H-bonds as compared to one 'iii"A-"r6-49(c). Variation
FIGIIBE of enthalpies
urJl,va;des of elcments of periods 2 to 5'
in HF.

s
t
i
van dcr Waals forces also increase

BR
-l
+d
,,lo-...ri H
'--a6./
'o'
I

I.E H*6

Similarly, ammonia (NHr) is soluble in water

because of hydrogen bonding as represented
below :
I
+d
+6 -2n
H
-o. \g
(v) Yola lving
FIGIJBE 6.5O. Cage like stmcture oI
hyd.;;"il;; *T- HzO in the ice.
termolecular
 CHEMICAL BONDING AND MOLECULAR STRUCTUHE
6/ss

tbe importance of hydrogen bond lies ia

- -Tbusthat
the fact it can explain thi various abnormal
physical properties.
7. I}pos ofHydrogen bonding: There are two
typres of hydrogen bonding :

t
\

FIGUIF .51. group contains a H-

F-ach H2O molecule linked
to toor HzO moleculs tetrahedrally.
atom linked to an
electronegative atom and other group contains a
bighly electronegative alom lir*ed to a lesscr
Obviously, the m sely electronegative atom. The bond is formed be-
packcd as rhey are in ice group with the more
melts, this cage like s the e otber group. A few
molecules come closer the molecular hydrogen
same mass of water, the volume decreases and
hence density increases, Therefore ice has lower
density than watei at 273 K. That is whv ice floats
o OH
on water. lla -
i

t^\ar'
NotA thot each arygen dtom it liakeil ro H-
qbmt, two b! covalcnt bond.r and *o by lour :
H-boadr.
Eoth woter mobcuh it ti an h jo* *uo
ntu&1tks tet4fu&ally hl E-bodds" -r9,"tu -./i'*o
.)-Nitrophcnol Salirylic acid
hydrogen
be satisfied

(ii) The molecule should be planar.

- (iri) The hydrogen bonding shoultl lead to the

lormatron of a six membered ring including
the H
atom.

rhydrogen bonding.
bondiog prevents ai_
a contraction of sizc
 ijrrr C :' r l;'s N eul'Go utie, Chem.i qt'S,,WID
6/56

of the molecules and hence decreases its surface

;;t* Cu*equently, the effect cf intramole-cular
hrd.osen bonding'on physical properties of sub-
.'o"""?it to lower-their rnelting and boiling points'
.l""r"or" their solubility and increase their vapour
happens as a result
;;;;;, iuit oppotit"io what
tf iot"t*ol"culai hydrogen bonding'
:::::ill;ii:::::ii!:::ii:ii::i:::ii

A,H,V,' ' i :K iNi : L: Pl ,l;

\)
t.TheforcesofattractiorrthatexistamoDgthenon-potarmoleculeslikeH2,Cl2etc.oramongtheatomsofnoble
gaseswhichareduetoinstantaneouspolarisationofonemolecu[ean<ltheDinstantaneousinducedpolarization
are a typc of van der waa|s force s.
in the other are calred ionrlon forcei. These increasc in van der
points rronr n, to I, or fronr He to Xe is due to
2. The increase in n:elting Points t'lnd boiling
of which the potarisability
irr the size of the molecules as a result
waal,s forces which is turn are tjue to il'rcrease
of the molecules becomes easter'

Q'l.Writethel.ewisdotsymbolsandpredictthevalenciesyouexpectforthefollowingelements:
Nitrogen, Fluorine and Neon

.tns. :N.(valency =5or8-5 =3) ; :r:(valency =7or8-7 = 1) i 3iie3(valency=0;

Q. Z W.o Lewis rlot symbols for the following ions :

(I{C.E.R.T)
Li+,cl-, o2-, Md+ and N3-
.'. Lewissymbol = Li+
3Li =2,7,Li* =2,0
Atrs-

Cl- = 2,8,8 Lewis symbol = t t-

lrCl:2,8, 7,
"' :l

.'. Lewis sYmbol =!O12-

rO =2,6,02- =2,8

rzMg = 2,8,2,M{+ =)"$ .'. Lewis sYmbot = Mg2t

N3- = 2, B .'. Lewissvmbol=!N3'-

,
7N = 2,5, ..

of the two ? Justify'

Q 1 Is CaF, linear or bent or neither
CaFrisneitherlinearnorbentmoleculebecauseitisionicconrpoundandionicbondisnon-directional'
number of Na+ antl Cl- ions in NaCl
?
What is co-ordination
Eachhasaco-ordinationnumberof6i.e.eachiorrissurroundedbysixoppsitelychargedions.
 CHEMICAL BONDING AND MOLECULAF STRUCTURE 6157

'J ": OutofNaCl and trIgo, which has higher lattice cnersr and why ?
turs, MgO has higher lattlce ener6y because each ion carries two unit charge whereas in NaCl each ioa carries ooe
unit charge.
,1 ,
Why secood electron nmnity ofan elementis negative or second electron gai[ enthalpy is positive ?
Ans. AIter the additioD ofthe firsr electron, we gef a ne[,ative ioD which has, therefore, a Degative tendency to gain
anothcr electron ie. encrs/ is requircd for adding the second electroD.
. Why NaCl is o hxd (oDductor ofelectricity in the solid state ?
tus' In the solid state, Na+ and Cl- ions are riot free.
t ) s Why N6CI gives a rvhite precipitate with AgNO3 solution but CCla does not ?

Ans. NaCl is an ionio compound and henc gives Cl- ioDs iD the solutioD whicb combine with Ag+ ions giveo by
AgNOj to fornr a white precipitate ofAgCl but CCll is a covalent compound and does not give Cl- ions.
..,'r \yhy reaction l)etween NaCl a nd AgNO3 is very fast but reactior between H2 snd Clr is slow ?
Ans. NaCl and A8NO3 are ionic conlporrnds. In solutron, NaCl gives Na+ and Cl- ions and A8NO, gives Ag+

ilnd NOt ions. The oppositely charged Ag+ and Cl- ions combine immcdiately. The reaction between H2
ard Clz involves brcakiog otcovalent bonds which requires eners/.
! Q I o. Deline lstt How is it related to the stability o[ an ionic compound.
ce enthelpy. (N.C.E.R.T.)
Ans. Definjrion see page 6/5. Greater the lattice enthalpy ofan ionic compound, greaicr is the stability.
, ) , Drrw the Ler?is struct[res of the following molccules and ions and ions and tell in which case/cases the
octet rule is violated
CO2, SO2, BeCl2, NH3, AICI3, PCls, CO3-
tut' :6::c::o: ' :<i::s:o: :ii: e":di:
., t- .^' -12-
H:ii:H. :'cr :s:bl: 'ei.i.9p',b'i, l,u,J,al
L J
H :cr: :bi:bl:
The octet rule is violated in c{se of Beclz, AlCl3 aDd PC15-

(r -t trvhy two hydrogen atoms combine to form H2 but hYo helium atoms do notcombine to form He, ?
Ans, Refer to the text (oD the bass of (i) New forces of attraction aod rePulsion and (ii) orbital ooDcept).
(' , , why free rototion obout r r-bond is not possible?
Ans. The ovcrlapping vanishes arld the boDd break.
i) ll Ortofdand ir-bonds, rvhich one is stroDger ard why ?
Ans. o-bond is srronger. This is bccause o-boDd is formed by head-on overlappiDg ofaion:ic orbitals and therefore
the overlapping is large. JI-bord is formed by sideway overlapping which is small.
Q. I 5. C-II bond lengths do you expect in C2H5 , C2IIa atrd C2H2 nnd why ?
What order of
Ans. C-H (C2H6) > C-H (c2H4) > C-H (c2H2). This is bcause hybrid orbitals of carbon invotved in
overlapping wlth 1,r orbital of hy<lrogen are sp3, ,rpz and sp respectively and their sizcs are in the order
tp3rspz>sp.
,.) ri Arralge the following in order ofdecreosirg bolld sngles
(, cH{, NH3' H2O' BF3' C2H2 (ii) NH3' NH2-' NH{+
ans. (i) C2H2(180) > CH4 (109" 23') > BF3 (120') > NH3 (107") > H2O (104 5')
(it) NH4+ > NH3 > NHt
'llis is because atloftheor iDvolvelf hybndizatiol. The oumber of IoDe pair ofelectrons present on N-atom
are 0, 1and 2 respectively. Grealer the number of lone pairs, greater are the repulsions on the bond pairs aDd
heoce snaller lS the aDgle.
6/58 Pratlce y s Ne.l Coutse Chemistrglfiffi
() t r' Which of the follordng molecule/molecules will have zeto diPole mometrt ?
CO2, H2O' CCl4, cHCl3, BF3, BeF2, NH3.

ADs. COz , CCla , BF3 aDd BeF2.

Q. lx which bond do you expect to be strotrger iD each ofthe followiDg cases ond why?
(0 H H, cl-ci, (ii) 02 N2 (iir) F-4 cr-cl
- '
Ans. (,) H of smaller size of H-aloms.
-H is stronger because
(ii) N = N is stronger because it contains a triple bond while 02 contains a double bood (O = O).
(ir'i) Cl-Cl is stroDger because repulsions betweeD the two F-atoms in F2 are larger on accouot of Sreater
electron density around F-atom due to smaller size and helrce greater repulsions between thg iwo F-atoms.
Q I 9. Dellne electronegotivity. How dos it dilfer from electron allinity ? (N.C.E.R.T.)
tul!. DelinitioD--See paEe6123. DiffeteBce between EN and EA--See paBe 6125.
Q l(l- Arrange the follorving mol.cules in order of increasi[g io[ic character oftheir bonds
Li4 K2O, N2' SO2' ClF3 (N.C.E.f.T.)
Ans. N, < SO, < CIF3 < IqO < LiF
Q. 2 I tuTange the followiDg bords in the order of increasing ionic character :
C-H, F-H, Br-H, Na-I, K-F and Li-Cl (N.C.E.R.T)
An6. C-H < Br-H<F-H<Li--C|<Na-I<K-E
Q. 21. What is the total nurDber of sigma and pi bonds in the following molecules ?
HH
(a) c2H3cl (r) cH2cl, (") H3c-J = J-.
= (N.C.D.R.T.)
HH "-, H
,Lns. 1a;isHJ = J-Cr (5 o bonds, onez bond) (6) is H-Lcl (only 4 o bonds)

J,
HHH
(c) is H-C-C =
ttl C-C C,-H ( l0 o bonds, 3 z boncls)
=
I
H
Q. 2-1. Tokingr-sxis as ahe lnaemuclear axis, which out ofthe followirlg will form d-bond ?
(i)lsandls (ii) lsard2pr Qii) 2pra llp, (ir)lrand2s. (N.C.E.R.T)
Ans. Ailexcept (iii).
(., ll Whot is meant by (bord ordet' according to Lewis concept ? Calculate the bond order of
N2, 02 and CO.

(N.C.E.R.T\
Ans, Bond order-Definition se page 623.
Molecule: N=N O=O C=O
Bondorder: 3 2 3
Q 2i. Expfoin why dipole moment ofhydrogeD halides decreases ftom HF to Hl. (N.C.E.R.T)
Ans. This is because electronegativity ofhalogen atom dcreases from F to I- Henc the polar character decreases
aDd so is the dipole moment.

Q 16. Represe[t diagramaticslly the boDd moments atrd the rcsultlnt dipole moments ln
(i) SO2 (4) cis and tratts fomts ot C2H2CI2

*"t"-rli\-, +21 ts
(n) H-=c-o
+*
01,)H-c-cr
ll HResultant
(N.C.E.R.t)

cJ-n H-C_CI
Resultant F
aran -(/t = 0) cis-01 + 0)
Rcdultallt =0
 CHEMICAL BONDING AND MOLECULAR STBUCTURE
6/s9
(l ll. Predictwhich out ofthe following molecules will htrve hlgher dipole moment oEd why
?
CS2 and OCS
(Nc.E R.r.)
++..i-+-
Ans' s = c = s and o - C = s both are liDear molecules but bond momeDts iD cs2 caDcel out so that net dipole
momenr=0.ButirOCS,bond-.^T:nl9{C=Oisnorequat lo that of C S. Hence ir
= has a net dipote
moment- Thus dipole moment of OCS is higher.
Q 23 From eoch ofthe follolding pslrg select ahe Drolecul eith highcr value ofthe property mentiotred against
eoch pair :
(i) NIIJ. PI13 : bcnd angte (r, Nli, NH3 | dipole momeDt
(iii) IUpo. CllO: hxrdness (iv) HCl, HBr : ionic character
tus. (, NI{3 (,i) NH3 (,,r) MgO (,v) HCt
Q. 19 Write the stt[cture of an anion which is isostructural with BF3 ond the structure of a cAtion which is
isostructural with CH4
Ans. (i) NOr- (liiangular planar) (,i) NH{+ (tetrahedral)
(l {!. Dftrw
.r the shnpes of the following hybrid orbitals : sp, spz and sp3 (N.C.E.R.T)
Ans'
l,oo

109a 2g',

All the hybrid orbitals have same shape. However their sizes are in the order sp < spz < tf

OCa(}>-
sp sp2 sp3
(.) I I Expl[in how the valence bond theory accounts for
(i) a carbon-carbon double bond (C C) (j) a carbon_carbor
= triple botrd (C = C) (NC.E.R.T.)
Ans, Explain with examples ofethylene and acetyteDe (page 6/39 and
6/10).
Q -rl. Exploil why CHl has tetrahedml geoDetry and rotsquar planorwith car.bon
atom at the centre anal four
H atoms at the corners ofthe 6quare.
Ans' Thc hybridisation of csDtral c-alom
is s1 and not rlrp2 (as no rJ-orbital is available for perticipalion). Hence
square planar geometry is Dot possible.
i.r,'NnmethetypeofhybridisationofeachC.atomiramoleculeof(j)propylene(propene)(ii)propyne
Ilow mrtny a and r-bonds are preseDt iD each cflse?
t2J
Aus. (i) CFI3-CH = CH2 (C-1 is rp3, C-2 and C_3 arc rp2), ,_bonds = 8, z-bonds = 1.
123
(n) CHr-C = CH (C-1 is rp3, C-2 aDd C-3 are
ry), o-bonds = 6, -bonds = 2.
r_,,: Which hybrid orbitals are used by carbon atoEs
in the followitrg molecules ?
(i) cH3_cHo (i, CH!_COOH.
 Nc.4 Course Chent i stYtl
6/60
H..
\l 2./,H
Ans. (i)H-(l-c\. c-l is,rr3 hybridised
-
l7' o c-2 is,rf hybridised

H-o 2.//
\l
(ii) H C-l isrrr hyhridii'cd
H -C-41
'/ \o-n
,r rr ln SFa molccule, the lonc plirofelectrols occupies irn equttorial Positiol rother thltn oxilrl J'ositioo ill the
lvlly ? (N'C E'R T)
oversll trigonal bipyramidal arrsngenrent'
Ans.Thc/p_6PrePulsionsarolessifitoocuPiesequiltorialpositiol]thanifitoccuPiosaxialPositio[..4'saresult,
is l"ss and stability is more (sec pagc 6/44)'
"nerry
U r' Explain how VIt theory differs from Lewis concepl
hy muluul \h;rrin! oI clecltotls whereus accordil1g
Ans. (i) According lo Lewls concepl' il coYalcnl holld is l()rilleJ conlirlllilrg eleclrons u ilh
to VB theorY a covalenr hond ls lo;nlcll by thc t1\'crh11 ul hrrit'-llllc''l at'rntrc
'irhilills
opPosite sPin.
shaPes ofDrolecules whcreas Le$is concept cannot'
0i) VB theory can explain the
(iii) VB theory can exPlain tbe strength of bonds wheroas Lewis concePt cannot'
Q. -17. Dscribe the change in hybridisotion,
ifany
(4) oiAt otom ltr the raction AICL + Cl- -. Alclr ?
(r) olB ard N stoms in the reaction BF3+NH3 -.- F3B-NI!3? (N.C.E.R.T,)

Ans. (a) No chaoge (remains lP3;

(b) IrI BF3, B is rP2 hybridised and in NI]3' N is ?l hybridiscd AJior lhc rcaction' h]bridtsation o[B changes

to,rp3 but that of N remains unchaDged'

lr,.onthebasisofVSIIPRtheorypredictthesh,lPcsofthefollowingmolecules/ions?
(D SiF{ (ii) NHt (ii, NlI.+ (iv) c2u2 (v) II3O+ (v,P2O (zii) PCl3 (riii) PF5'

Ans.(i)TLtrahedral(i)v.shape(iii)Tetrahedral(iy)qllndrical(f).liigooalPyranridal(vi)v-shape(yii)Tiigonal
pyran]idal (riii) Tiigonal bipyranlrdal'

the following in order ofdecreasing bond {nglc, giYing reoson:

,.i 1rj tur'trge NO2'NO2+, NO2-
linear' No2 has one
Ans. Nor+ > NO2 > Not. This is becausc NOI has Do unshared electron and hence it is
unshared electron while NOt has one unsharcd elcctron Pair'

180' Ilond anglc = 132' UoDd a glc =

Bond angle = 115'

i,) l'r Why axial bonds ofPcls are lorger thnD cquatorinlbonds ?
pairs by the equatorldl bond pairs of electrolls-
Ahs. This is due to greater repulsion on the axial bood
, wlry NF3 is pyramidal h t BF3 is triangular plrnrrr?
hy lone pair of electroos bu t in BF3' B has the
Ars. In NF3, N has the hybridisatio[ d with one positiorr occuPled
hYbridisation.tf
'lriWhybordaugleinll2oisnearlyl045'hutthatinII2S'itisrcarly90'?
Ans. Refer to the text (PaEe 6144)-
 CHEIUICAL BONOING AND MOLECULAR STRUCTURE
6161
i Draw thc str cture ofll2SO4. wlrat is hytrridisation ofS.atom in it ?

o
I
Ans. Il-O-S-O-ll Hybridisarion of S-arru is ri-u3
J
o
Out ofp-orbitfll and sp.h)brid orhital ryhich has greflter directional charflcter and l"hy ?
ars' .tP-orbital has grcitcr dircctlolral character lhan
I,-orbital. 'lhis is bccause p-orbital has equal sized lobes with
equal electron dcnsitY in bo(h lhc lobes whcres .tp-hybrid orbiral has greaGr electron den:siry
on one side-
Expltin the important aspects ofresonahce r"ith reference to CO3- ion.
W,C.E.R.T,)
Ans. see resooating srructurcs on pagc 6/,19. ,,\[ the lhree bonds arc exactry idenrical in bond
st.cngth and bond
length.
. II3Po3 cnn be rePresented l)v thc strtlctn res I r nd ll shown belorv. Cnn these two structures
be taken os the
cnnonical forms ofthe reson:rnce hybrid ot I13pO3. If not. state reason for the sam.

H
II:O:P:O:II II:O:P:O:H
:o: :o:
llt
II

lN.cE"R-T)
A[s. No, these cannot be taken as coonical forms becausc the pcitions ofator's have ben clranged.
(1. ,17 Why HrO ls a liquld trhtle H2S is a gos ?

AnB. In ll2o, there is hydrogen bonding and heDce association of H2o moleqrlcs but in H2S there is no H-bonding.
(.,. .lb poirt then IICI ?
Vyhy HF hns hlSher boilitrg
Ans. In HF ttlere H-bonding and he[ce the molecules are assoc.iated together but in HCI therc is [o H-bonding.
is

Q 49 VVhy ethyl alcohol ls @hpletely Eis.ible !f,ith woter ?

An3. This is becausc ettryl alcohol forms H-boods with water.
Q io V/hy KHF2 exlsts but I(HCI2 does rot ?
AIls. Due to H.bonding ir HE wc havc H-F-----H_F.-___H_F___--,
This can dissociare to give HFz- ion and hence KHF2 exisrs but there is no H-bondiDg
in H--cl. so Hcr2- ion
dos not exist and hei Je KHCI2 also does Dot exist.
!J sr ' vyhen we .ooye fto'o HF to Hcr, the boirirg poi,'a dmp6 sharply but on movtng nrnher to HBr end HI tho

Ans" bolllng pornt l,cre{ses. \thy ? or out of Hrl HCr , HBi nnd til whtch has lowJt bo[r"8

[.JH:},,X#;itrH"*-H*,],r.'il1fl;'"HH':l{
e.r"t ;;;1; t--

oc.e HCI has the lowest boiling point.

V il
Ethstrol has hlgher boillDg point ttan dlethyl ther or ethylamlne. Why ?
Ars. ID ethanor, there is H-bonding but in diethyr ether, tbere is no H-bonding (because
o-atom is attached to
c-atom) and in case of ethyraminc rbe H-boods fom ed try N-atom are wcaler
than thme ro.meo ty o-atom.
Q. S-t Why lce hos lower dclrEity thsn woter orwhy ice lloats on the surfece o[voter ?
Ars. See rexl (page 6/54).

e St lvhy sater hos maxiEuEl density at 277 K ?

Ans. Refer to the texr (page 6/5a).
i5. Horv oany ll.bonds rre fomred by esch II2O molecule and
r.,'
hotr, Eanyrrat r Eolccul6 arc anrch.d to each
lroter molccule strd in rvhet directioD ?

-l
 NeqJ Coarse L lretu is lrq
6162

Ans. Each H2O molecule forms four H'bonds, two with o'atom and
two with H-atoms Further' each I'I2C)
molecule is linked to four HzO molecules through H-bonds tetrahedrally'
why ?
V 5 ('. Out of..,-nitrophenol ard p-nitroPhenol which hns higher boiling Point nnd
point because there is internolecular H-bondingwhile iD o-nitrophenol thcrc
.a.ns, p-nitrophenol has htgher boilinE
is rul ranlolecular I{-boDdinI
(J. 57 Though Cl h{s nerrly same electronegativity as N' yet there is no H-bonding in IICI'
r hy ?
Ans. Chlorine atom has a large size-
(J. 5E. why ghrcose, trnctose' sucrose etc' are soluble in water though they are covalent comporlnds ?
with water'
Ans. These conlpounds contain frolar -OH groups which can forfll fI-boods
l) 59. Jlenzene ring contEins alr4nste singlc and double l'ondq yet all the C-C honds are ofeq[allength' Why ?

Ans. This is due to resonance io benzene.

ofelectrolrs
r).61) Nitrogen has an atoEric nombcr of7 ond orygen h&s on atomic number ofE' The total n[mber
in hitrate ion (NO3- ) is ----' (B.I.T Ranchi 1990)

Ans. Electrons io No; =7 +3xa+1=32'

6I . The otomic number of nltroge[ is 7 atld thot of hydrogen is 1 ' IIov many elc'trcrs ore tbere in ammonium
Q.
ion, NHa+ ? (B.l.T Ranchi l99It
ADs' No' of electronsinNllo+ = ? + 4 - 1 = 10'
the vsPour wlll have diatomic molecules of sodium (Na2) \}'llrrt
Q. 62. Sodium metal vaporiscs on heating ond
(BITRdnchi 1991)
type of boniting is Prcsetrt in thc3' molecules ?
tuls. Covalent bonding.
(l honds, which bond is the least ioric ? (B.I.T Ranchi 19921
(,-1. ortt ot P-R F-[ S-t' and Cl-F
Ans. Ir-E
Q 6l. Why is water a liqnid whereos H2Se is a gas ? (I.S.M. Dhanbad l99il
Ans. 'lhcre is hyctrogen bonding in Hzo but no hydrogen bonding in H2Se-
Q. 65- t#hy an ionic bond is formed between tvo elements having large dilference in thGir electronegatiYi8 ?
(Bihdr 1997)
electrorrs to such a |arge exteDt thaD the othcr
Ans. 'fhe n,]ore electroDegative element will atrract the shared Pair of
that it will amouDt t6 transfer ofelcctron resulting in the formation of ioDs'
bond angle ?
Q. (16. Which ofthe following has maximum
H2O' CO2' NIr3' Ctl.. (Bihar 1997)

Ans. COr. 180" (due to lincar structure)

Q.67. wrst angles are associated with the follorving orbitals ?
(B.LT Rdnchi 2000',
,rp, .sp2 and sP3
tp = 180", ti2 = 120", qf = 1092a''
Write down thc I-ewis strrctures ofthe following : (i) CO2 (i, CN- (Bihar C.8.E.2003)

Ans Reler to sec. 6 10, Page 6/10.

Short inswer Queslions

formation?
Q. 1. lvhich electrons t{ke pErt ln bond
Ans. ValencE electroDs present io the outermost shell'
ploce when a molecule is formed froE its atoDs ?
Q. 2. Whot chonge in enerEr tskes
Ans. Lowcring of ellersl takes Plac!.
together in :rn ionic compound ?
Q. 3. Whot tJ?e of forces holit the atoms
 CHEMICAL BONDING AND MOLECULAR STRUCTURE
6/63
Ans. Elcctrostatic forces of attraction.
Q.4. In terDs o[ ionizatioir energy and electron alTDity. whnt tvpc of ntoms conrbine to form an ionic
compound ?
Ans. Metal atom with low LE and a non-metal aront with high E A.
Q. 5. choose the compo.nds conLrinihg ionic, covrlent and co-oralinate bohds out of the folrowing :

MgCl2, CH., CaO, HCt, NH.+, 03

Ans. Ionic = Mgclz, CaC);covalent = CHa, HCI; co-ordinare NH4+, OJ
=
Q.6. Whot E?e oforhitals c{ln overlap to form a covoleDt bond ?
Ars, Half-filled atomic orbitals containing electrons with opposire spin.
Q. 7. what orbitals car overlap to [onD a o-bord and which orbitars can ilo so to form a ,.,-bond ?
Ans. s-s, s-p, p-p for o-bond and only p-p for ,-bond.
Q.t. Nah. one cornpound each involvin g ry1 ,.rpz ani! ,tp hyl)ridisation.
ans. .l = CHo , tpz = q[a, sp = C2H2.
Q. 9, Name the shapes of the following molecules : CII4 , C2 H, , C02
Ans. CHa=tetrahedral, qHz =cylindrical COr=ling21.
Q' l0' Name the two co.ditions which must be satislied for hydrogen bonding to tske prace in a horecure.
Ans. (i) The molecule should conlain a highly electronegative aklm linkcd to H_atom.
(li) The size of the electroDegative arom should be small
Q. 11' Itr forhing a coEtPound xY atorns of x lose one electron each while the atoms o[ y acquire
one electron
each. Predict the Dature ofthe cornpound.
Ans. The compouDd XY is ionic in mrure
Q. 12. Predict the dipole morn.trt of a molecule of the type AXa *ith square plflnar armrgemcnt ofX atoms.
Ans. zero.
Q. 13. Identlfy the compound/compounds i[ the follorving in which S does not ohev the octet rule.
so2'sF2'sF1,sF6
Ans. SFn , SF5.
Q. 14. You are giveD the lectroDic conliguration of live neutra I atoms _ A, B, C, D and E.
A-rP * 3?
2p5 t-t?,zi,tq6tr, c_t?x?zo,
D
-# L? zpi
Write the empirical formula
E-ls2 L\2 zp'.
for the substance containinp (i) A and D (ii) B and D (rtj) only D
(ie) only E ?
Ans' (i) Empirical formula of the compound formed by A ancl D is AD2 as A has two valence
electroos and D has
seven. Atom A transfers iLs lwo electrons to two D atoD]s to complete their octets.
(ii) Empiricalfornrula ofthe comPound formed by B and D is BD as B rransfers rts one elecrron to D.
(r'ii) D2 as both the atoms ofD share one electron each to form a covalent bond.
(iv) Sinc it is a noble gas, no compound is formed.
Q. 15. Arrang the following in order of itrcreasing bor|d strehgths : f2,N21O2rClz ,ll.l t: ttu llti tt)9.)]
Ars, F2 < Cl2 < 02 < N2.
Q. 16. Arrange the followitrg ih order ofincr-casing strength ofhydrogen bonding Iq B S, Ct, N
(lv l"it'll' r99't1
Ans. cl <s <N < o < E 'rthluthal
Q. 17.what is valence bond approach for the formation ofcovarent bond ard a co-ordinate
bond ?
Ans. A co!r'aleot bond is formcd by the overlap of halffilled atooric orbitals
whereas a co{rdinate bond is formed
by the or'erlap of an entpry orbital with a tully-fillecl orbiral
 Pradt;t:p s Neut Course Chemistrqfiffi
6164
citlcutlrtion oflattice eherP] or electron a[Iinity
Q. 1ll, Name the method Senerntly used lbr the
Ans, Born-Habcr sycle.
Q. 19. Whtt are SI rrnils ofdiPole moment ?

Ars. Coulonb mcter (Cm).

Sec.6.l. What do you understand by a chemical bond I

to 6.8.
Bricfly explain Kosscl-Lewis aPproach ol chenrical bondinE'
exan]Ples Give the Lewis sl ructure of thesc
3. Illustrate the inadequacy of octet rule with two suitabte
nrolecules.
4. Why are the noble Bascs pQor chemical reactants?
'l
5. What happens when two hydrogcn atonls aPproach each othcr
ofchcmical colnbination bctwecn
6. OD the basis ofelectronic theory, brieflyexplain thediffcrent
modes
atoms.
1 Explain the term electrovalqncy.
ionic comPounds'
t.Briefly explain the factors which influence the formation of the
9. What are the important characteristics of iorlic compounds
?

of electricity irl a molten condition than in the solid state Explain'

10. NaCl is a better conductor
'l Explain its formation \vith two sultable examPles
11. What is an electrovalent bond (or ioDic bond)
12, An element A combines with elemcnt B. An atom of A contains two electrons io its outermost shell
,"t r, ot
tt g h"t six electrons in its outcrmost shell Tho electrons are transterred fiom the aton]
"i"""
A to the atom B.
(a) What is thc nature of bond between A and B ?
(b) What is the electronic structure of AB ?
(c) What is the electrovalencl otA and that of B ?
to forln ionic bond'
13. Name two conditions that are essenlial for two different atoms
it help to predict the stability of
Define Lattice enerry. On what factors does it clePeDd How
? cloes
14.
the ionic comPound formed ?
15. How caD the electron affidty ofchlorine be determined usiog Born'Haber rycle
? (rVC'Eft'I)
what are the condilions
Scc.6.9 ii, *t lr r*n, ty a covaleni boncl ? Explain with three suitable examples
nr 6.l5 for ",
the formation ofthis tyPc ofbood ?
qHz'
17. what are l,ewis structures ? Write the Lewis structures of Hz , F2, H2O, NH3 ' qH4 and

lt. ExPlain the term covalenry.

suitable examplcs'
19, Briefly dNcuss the orbitalconcePt ofcovalent bond formation takin8
'l taking the exaulple of
20. How is the formal charge olr an atom in ir Dolccule/ion calculated ExPIain
ozonc molecule
21. Differeotiate between d and J, bonds
Explain how the strength of a bond is relatecl ro (i) extent of overlapping
(ii) shape of the orbital
22,
dlagrammatlcally Which
23. What are sigma and pibonds ? Explain the different wals oftheir formation
one of them is stronger and why ?
Scr:.6.16. 24. Arrange the following according to bond len8th giving reasons :
(t) H-F, H-cl, H-Br, H-l
(ii) C-C, C=C, C=C
(iii) C-H bond lenglh in CH4, qH4 and qH2
lhe following single bonds in order of bond energy Siving reasons
:
25. Arrange
c-c, N-N, O-O, F-l-
CHEI\,4ICAL BONDING AND [,4OLECULAB STRUCTURE 6/65

src,, !;. 26. DeliDe the term Electronegativity. Explain itwith onesu(able example.I{ow does it helpin predicting
, (, l o
r whether a covalent bond ts polar or non-polar ? Explai[ each case with oDe example.
27. Define'ElcctroneEativity'. I{owisir calculated on (i) Pauling scale (ii) Mulliken scate
IIow are the two values rclatcd to each othcr ?

2E. Which of the following hydrogen halides has the most polar molecules and why 'l
HI, HBr, I{Cl, HE
29. HIr is nrcre polar than IIt. Explain why ?
30, What do you understand by partial ioDic character of covalent bonds?
.11. Define Dipole moment. Draw dipole diagrams of H2O aDd BF3.

32. Explaro : Each cirbon{)ry8en bond in COz nrolecule is polar but the molecule ilself is non-polar.
33. Explain thc ternr Dipole momenl. Name two molecules which have a dipole moment and two
molecules which do not have a dtpole ntontent. What is the sigDificance ofdipole moment ?

34, Explain giving rcasons. which of the follo\ ing molecules have elecrric dipoles
(d) CCta (b) CHCtr (c) CH2C|2 (d) CH3CI (e) CHn.
35. Give reason for tbc following:
(i) lonic conrpounds are soluble in waterNhercas covalent compounds are mostly insolublc in water.
(ii) Ionic compounds have higher rnelting points than the co\"lenr compouDds.
(iii) NaCl solution gives a white ppt with A8NOJ solution but CCl4 or chloroform does not.
s( ( /, l-r J6, What arc the nrain postulaics of Valcncc Shcll Illcctron Pair Rcpulsion (VSEPR) thcory ? What
r,, 6 .lI improvement was Dradc bv Nyholm aod Gillespie ?
37. What ts hybridisation ot orbitals 'l Dra!,, ourline sketches to show the formation of .rp ,y2 and sp3
hybrid orbitals.
3tl. What type of hybridisation is arisociated with thc central atom when the atoms attached to it lbrm
(d) an equrlatsral triangle (r) a regular tetrahedron ?
39, E\plain wh),carbol has a lalenry offour and not two and why are the four C.H bonds in methane
idenlical.
40. Explain thc lcrm Hybridisation taking the exan]ple of metbane.
41. Carbon has electronic configuratron I s2 Ztz 2p2 a\d.lhercforc, should be bivalent. Howwillyou justiry
its tgtravalency irl methane ?

42. DefiDe hybndisatroD. Describe the formation ofd

, rpz and sp hybrid orbitals ofcarbon atom. cive
one cxantplc of a molcculc in each case involving these different types of hybridisation.
43, What is valeDce bond approach of covalent bond ? Give two examples to illustrate it.
s.( 6 ti 44. Makrng use of the concept of hybridisattoo. prediot the shape of qH2 molecule.
45. Draw shapes of H2O and C2Ha-
46. Using the valency shell elcctron pair repulsion (VSEPR) model, predict the shapes of the following
nrolccules (i) BeCl2 (ti) BF3.
47. Sug8est the expcted shape of NH3,
4t. Draw welllabelled orbitaldiagrams for the followtDg molecules
(,) BeF2 (4) BF3 (x0 CH1 (iu) NH3 (,) QHe.
49. Predict the shapes of the following molecules using the wlence shell electroo pair repulsion model-
(i) BeCl2 (it) siFo (iii) BF, (iv) NH, (v) lJro.
50. Explain the shapes of SF4 and ClF3-
s".r'lr' 51. Whatis a coordinate bond I ExplalDwith two suitable examples. Flowisit diffsrent from a covalent
bond I
\cc o..li 52. What is resonanc ? Define ResoDance enerry.
53. Draw thg rcsonating structures o[ CO2 ?
6i66 lradcc 1t's Neur Course Chemistrrllfifr)
scL6.2t. 54. What is hydrogeD bonding ? Give three examples of molecules involving hydrogen bondinS. How is
hydrogen bond different from an ionic bond and a covalent bond ?
55. Accounl for lhe followin8:
(i) Water is a liquid while H2S is a gas. (ii) Nfl3 has higher boiling point than PH3.

(nt) Boiling point of HF is lower than that oiwater.

56. What is hydrogeD bonding ? Iri what respcts is it different from ionic and covalent bondiDg ?
57, Write a short l1ote on 'l [ydrogen bond'.
stl. tlxplain why ordinarily H2S is a gas while fI2O a liqurd even though both S and O are elements of the
same group in the periodic table and S has a higher atomic olass.
59. \rfttor is a liquid and hydrogen sulphide is a gas, although the molecular mass of hydrogeD sulphide
is almost double lhat ofwater. Explaill.
60. What requirement should a molecule fulfil for the formatioD ofa hydrogen bood I
61. Give one example of intramolecular hydrogcn bond.
62. The bothnE and melting points ofwater are abnormally higher than those of other hybrides ofBroup
16 of the periodic table. Give reasons,

,L qns :w 9" f gg.

-e"r,-e.,gig n
g
soc 6.l. 1. What do you mean by a chemical bond 'l I-Io\ry do aroms combine ? How maoy types of bonds are
to 6.tt. there ? ^:n
2. What arc essential coDdil ioDs for the fornation oI an ionic boDd t Explain the formation of an ionic
bond between aD atom of Na and Cl.
3. Describe various characteristics of clectrovalent conrpounds.
4. How can thc lattice enrhalpy of aD ionic compound like NaCI be determlend try using Born-Flaber
(rycle'l
Ste.6.9. 5. Explaio the forma(iol ofcovalent boDdon the basis of (i) l-ewis coocept (ii) Valenca Bond lheory,
to o.15. taking at least three surtable examples in each case.
6. Briefly describe Valence Bond Tbeory of covaleot boDd. How cao you iDterpret it in terms o[ enerry
considerations 'l
7. Whar arc sigma and pi bonds ? Explain the different wals of their formatioD diagrammatically. Which
one of them is stronger aDd why I
scc. 616. t. Explaio the terms bond length, bond energy and bond angle.
9. Briefly explain quantunr theory of covalent bond formation.
sr!.(,.i1 10. What do you u nderstand by partial ionic character of covalent bond ? How is it calculated I Explain
r,,r,.:o. rakingexampleol HCl,giventhatitsobserveddipolemonrentisI03Dandbondlengthis1275 A
t l. Define dipole moment. Discuss its important applications.
12. Why are some covalent bonds polar ? What is a dipole ? Ho\r, can a Drolecule that has polar bonds be
a non-polar molecule ? How do dipole moments of molecules of CO2, CHa, H2O and NH3 help iD
ascertaining their structure ?
Src.6.2l. 13. Listvanous characteristics ofcovalent conrpounds. DiffereDtiate between electrovalent aDd covalent
1,,6.:1. coD)pounds.
scc.n.2.1. 14. What is meant by hybridisation of atomic orbitals ? How dos lt explaiD the sbapes of molecules l
t,r 6.25. lllustrale your aDswer with suitable examples.
15. What is VSEPR theory 7 How does rt explain the bond angles observed in CHa, NH, and HrO
molecules?
srr (',-2(, 16. What js a co-ordinato bond ? Explain the formation of a co-ordioate bond. Describe it in orbital
overlap concept taking an exanrple.
sf,- 6.:7. 17. What is Rcsonance ? Explaio with a suitable example. Deline ResoDaDce enerry.
str'6.lli. lE. Whatisa hydrogen bond ? What requiremenl,s should a molecule fulfil for theformation ofhydrogeo
bond ) Explain the formatioo of hydrogen bond in HF and NHI molecules. Discuss intramolecular
hydrogen bond.
 ,U__9--E f,U tr I t-:,I,F,"eFMATIO N
'! 1' co,npuri"oo ofdipore DoEeDts of IyH3 ond NF3 - A typicar case.
Both NH3 aDd NF3 molecures have
oo N arom. As fluorine is bishry etectroDesarive, it appears that
R:fi.::ilH]Tl:1"_l.l:er-:!y*rons
N-F bond should be more polar and the net dipole momenr oixr, .r,rriJ"*-rr"-rr;;;;i;;#;:i#ir'iir:
However, actually the dipole moment of NF3 (0.24 D or o.8o x ro-s cm) is much sma[er than that of NHj
(vizI,{6Dor4.90xto-30Cm;.TtrisisexplainedoDtiebasisofthefollovingtworealons.
(i) The dipole formcd betwen the lone pair ard N atom has to be taketr
into coosidcration wbich is in ttre
direction oftho lone pair.
(r0 F is mote direction
.
electrooegative than -eleclronegative
than N, $ercfore N is more
H, tbe direction of thc bond is from H to N
between N and H ia 3.0 - 2.1 = 0.9 and betrun N antl Fie.?.
(It differcnce

F Resuftant
of 3 N-F
bonds
Th us Mereas resultaot moment of N_H boDds
parrly cancers the resulrant momert of rone pa,r.
adds up !o the bond moment of lone pair, that
ner"e tt nlt J[i"-,,oir,"iitr.rr,
of 3 N_F *"*
bonds
"
i. i"[ ol"-,iri ir NH,
.., 'i 2. Comparison of bond
dar io shapo with one rone
pl* o, N ;;;;;;;;;;
ivrr,.". ,t o"roprio
"
oi"r""i racted more towards F in

repursions between the boDd pairs in NF, is ress rban iD NH3.

Heo"",rr" ron" pui, #"^lfi
,nore thaD it does in NH3. As a result, the bond
aogle decreafo to lo2.4.wheress in NH3, '"fi'tlff:H,',i
it decreases to 107.3.
only.

6/67
6/68 Neut Course Chemistrq

ADDITIONAL U9EFUL INFORMATION

Note- PH3 and PF3 are atso pyramidal in shapewith one lone Pair on P. But PF3 has Sreater bond ange tban
pH3 (oppcite to NH3 and NF3). This is due to resonance in PF3 leading to Partialdouble bond character as showrr

belor, :

Asa result, repulsions berween P-Fbondsare largeand hence the boDd angle is large.There isno Possrbihty
for the formatioD ofdouble bonds lrl PH3-
Elfect ofthe type ofhybridisation on the directioll ofpolority ofs bond and magnitude ofdipole moment.
3.
For example, thedirection and Dtagnirude ofdipole moment of C-H bond in methaDe and ethylene are as follows :
H
I

c-r-H (in CH1) = i:*fr 1in crHal

1r = 0 30D p=0 40D
4. Sugden's concept ol stnglet llnksgc. Sugden put forward the view that octet rule is Dever violated. He
suggested tiat in case of moleqll; like PClj, SFa etc., some atoms are linked to the cntralatom by covalent bonds
wbile others arc linked by singlet bonds.,4 ringkt bond b fomed by one sided sharing of only one electton between
the r,)o o,torns atd is thirefore repesented, by half dnow ( ------t ) pointing from donor to accrptor. Thus we have
It can be sen that

cl FiF
\ t,/ S'

t\
I

FIF F
cl

No. ofsinglet bonds = Tbtal no. of bonds-No. ofelectrons required to complete the octet'
5. PolarlsiDg power and Pols ssblflty (Faien's Rules). Although irl an ionic comPound, the bond is
just as covalent bond has some ioDic
considered to be 1i6% ionic, actually it has some colralent character. Thus
character, ionic bonds have somc covalnt chamcter' This was exPlained by Fajan as follows
:
CHEMiCAL BONDING AND MOLECULAR STRUCTURE 6/69

4D_Drrlo,N4!:.!lqEFU!!ry_EqB!!4ILqN9_o_1id
When a cation appr@chcs an aDron, the eledrco cloud of the adm b attracted to$,ards the cation and hence gets
distorted. The effect is crued pol$isstion of the aDioD. The porver of the catioo to poladse tbe aDioD is called its
polarlshg polder and the leDdency ofthe anioo to 8et pohrisd is called iLs pnlarisabitity The greater is the polarisation
Producd, more is the neutralisatioo of the chargcs (ie. charge of the catioo by the clecilon cbud of th anion) and
hence the ionic character de.reass o. the covaleDt cbaracter incf,eiscs, Tho propertiGlikc melting poinq hat of
sublimatioq solubility in vater or oon-polar solvents change accordingly. The polarising porver of tha ca6on and ttle
polarisability of the aoion and hence the formation of cotr'alent botrd is hvoured by the following frctoN:
(i) shall size ofthe cltion Smaller the calio4 geaterb its plsititgpolrr. This sxplains why LiCl is more
co\r'alent than KCl.
(il) Irrge slze ol the anioa. l,arget ,he anio4 greoter is itt pobri.sabirry (because the hold on thc electron
cloud by the nucleus decreases). This xplaiDs why covalent characlcr of lithium halides is in the order
LiI > LiBr > LiCl > LiE
Ttrat is why their melling points are in the order
LiI < LiBr < LiCl < LiF
c) (s47 c) (513. g (&70'c)
(446"
(iii) l-arge charge ou the cation or anioo. Larger the chorye on the catio\ gredter is itt polori:ing power
(because the electron cloud of the anion is more easily and strongly attracted by the catioo). Hence covalent
chamcter iDcreases. That is why the covalent. character of rhe chlorides is in the order

Na+cl- < Mg2+cl, < Al3+ctr.

Similarly, grcater the charge oD thc aDion, more easily it gets polarised.
(iv) Elcctronlc corflguration ofthe crtior. If two cations have the samesize and chatge, thenthe one wirh
peudo noble gas configwotioa (with 18 electroDs in the outermGt shell)h os greaer polarising power than the other
withnobh gos configtration (with 8 electrons in the outermct shell). This explainswhy Cu+Cl- is more cotr'alent
than Na+cl-.
6. Applicrtion ofVSEPR ttrdory to cohplex holecules Le. Dot havltrg only otrc crltrsl atorr- Let us explain
ty takinS the emmple of acetic acid. lts Lewis structure is

HO

"_t_J_;,
I

H
The first C-atom on the left has 4 bond pairs only, therefore its gcometry is tetrahedml. Ttre second
C-atom (centralC-atom) has 3 bond pairs (countiDg double boDd as one bond pair). So itsgeometry is trigooal
planar. Tbe Dext atom viz o- atom has 2 bond pairs and 2loDe pairs. so ir has a beot geomltry. combining alt
tbese Eeometries, we get the overallgeometry ofac.etic acid as follo*s :

The above structure can also be written on the basis of hybridisatioo. Hybridisation involved will be :
C-atom, sf,2oa C-atom, ,l, Dext Otom, ,1 (with rwo orbitats containilg tone pairs of electrons).
6no N e u, courle Che m is t r7\fififi)

C. B. S. E.' P. lll.T. (,ll AI;US.1 ECIAt

Why is HCI predominsntlycovalent in the gaseous O O
state but ionic in the Aqueous soludon ? /:\ ll, ll.
- /;\ ^ "
cl and H ""'H-q.O)-N-o".'H-o-{(J \--'l}-N-(')"
Ans. Thc etectronegatMty difference between
atorDs is 30-2.r=os. H;"..'H;i-;
\:/
predominantly covalent io the Saseous slate. Hol '- pnltrophenol
6+ 3-
ever, being a polar moler1rle (H-O), when dis- As a re,sult, boiling point ofo-nitroPhenol is less
soh/ed in water, the polar H2O moleculs ioteract and hence is volatile in steam but boilirg Point of
with HO molecule as follo\ rs: p-nitrophenol is high and hence is not volatile in
steam.

Erplai! horr the valence bond theory exPlains

the existerce ol cia snd trans isomets.

According to valeoce bond theory, a co!,aleDt

bond is formed by c,verlap of half-filled atomic
orbitals. If overlap is along lhe intermolecular
axis, the bond formed is called o-bond aDd if the
As a result, the bolld betweeD Hand Cl is brokcn overlap is prpeodicular to the interDuclear axis,
aDd we get tlydrated H+ and Cl- ions in the the bond formed is called z-bond. In case of
molecules containing C = C double bond with
solutioo.
two different atoms or groups attached to each
doubly bonded C-atoms, they can exist in two
r,vhy PCls exists but Ncls does trot ? different spatial arralgements, called cit and
Electronic mnfiguration of toru (or geometrical isomers). For example, for
rsP is
the molelule CICH = CHCI (1, zdichloro
1 s2 Ztl 2p6 k2 3pl3pry3p:. Thus the 3d orbitals etbeDe), we have
of ihe valence shell are empty. Hence an electron
from Ir can jump to 3d, gMDS the configuratior
1s2 2:2 2p6 3sr 3p1pl3ptzul . Thus it can ex-
'\./"'
t\./"'
teDd its covaleosy to 5. In cas of?N, electronic
il il
configuration X 't? z! ZptrZptrzpl. As there is C C
oo 2d orbital, it cannot eflcnd its covalency to 5. s/ \c, crl \rr
cis-l, 2dichloro ethcrre trans-I, 2-dichloroethene
Why o-nitrcphenol is volatile in stlsl! butP'
nltrophelol is Eot ?
C = C double bolld consists of ooe d bond and
Ans. In o-nitrophenol, thcrc is intramolecular
one r bond, As ftee rotadon about a I bond and
hydrogen bonding and ttlerofore no further as-
hence aboul a double bond is oot possible, the
sociation among the molestles InP-nitroPhenol,
abor'c two molecules are comPletely different
there is intermoleqrlar hydmgen bonding and
and one canoot be changed into the other simPly
henco association amoDg the molecules.
by rotation. This explaiDs the existenca of cis aod
traDs-isomers.

lJ s NrE otrd rcprcseDt the types of bonds pEsent

ln CuSO4 . 5II2O.

Ans CuSO4.5H2O has ionic, coialent, coordinate

and hydrogen bonds as shorn below :
o-nitrophenol
CHEMICAL BONDING AND MOLECULAR STRUCTUBE 617 t

(r'i) H2O moleculc has a nel dipole montent

whereas dipole mon]cnt of CO2 is found to be
zero. A.lso central atom O in tlrO is .rp3
hybridzed whcreas central atom C in CO2 is
,p-hyrbidized.
(ir,) This is because each C-atom involves,rp2-
hybridisation.
Q.7. Taking carbo! (atomic numbcr 6) as an ex-
ample, explain the meaDing of valcDce
Note that four H2O molecules are liDked to electrons.
Cu2* cation by co-ordiDate bonds whereas fifth (B.LT. Ratchi 1991)
H2O molecule is linked by hydrogen bonds be- Ans. The electrons present in the outernlGt shell are
tween a coordinated H2O molecule aod sulphare called valence electrons because they tell about
the valenry of the atom e.& iu case of C-atont,
toD.
E.C. is 2,4. Hence its valency is 4.
Q.6 Give reasons for the followiug :-
Q.8. Frplain the followinS:
(i) Covalent bouds are called directioDal boDils
(i) AIF, is a high rnelting solid wheres SiFn is a
while ionic bonds are called non-directioual.
(i, Water molecules have beot structure gas.
whereas carboD dioxiile rlloleculca are liEesr. (ii) IlrS having high molecullr weight is a g,rs
(iii) Ethylene holecules ore planar, whereas II2O is a li(ltrid.
(I.S.M. Dhanbod 1990) (I.S.M. Dhanbad 1992)
(i) ln covaleot bond, rhe shared cledron paiN are ADs, (t) A1F3 is a[ ionic solid due to large drfference in
localized betu/een the tlro atoms or a coltlent bond
eleclroncgativties of ,/{ aDd F whereas SiF4 is a
is fomled by ttle overlap ofhalf-fillcd a tomic orbitats
which hale definite dircctions. Henc co lent co\ale nt cornpou nd aDd hen@ there arc only weak
bond i.s diircctional. In ionic compounG, each ion is van der Mal's forcqs anroDg their nrclecules-
su rrou nded by a Dumbor ofoppcitely charged ions (ii) Therc is hydrogen bondrng in II2O but no
and there is no defDite directioo. hydrogen boDding in H2S.

I. r-7. (ALA,AfSJ S FECTA L

I. S U B]ECT I VE QU ESTIONS e. i In each of the following pairs of compounds,
ryhich one is hore covalent strd why ?
Q. l Explaitr the lollowitrg oD the basis of yalence
(,) AgCl, AcI (r) BeCl2, MgCt2
bond theory
(i) Bf, is planar but NH3 is rot (iii) SnCl2, StrCla (iv) CuO, CuS

(ri) CCla atrd Sicla ore tetrahdral Ans. Applying FaJan's rules, tho result cin be obtaiDed
in each case, as follows :
(n'i) The HSE bord atrgle in H2S is closer to 90" (i) AtI is more covalcnt than AgCl. Thls is be-
thon HOH bond angle in II2O cause I-
ioD is larger in size than Cl- ion and
(i) Ir BF3, B-atom undergocs rp2 hybridisation. hence is more polarized thrn Cl- iLrn.
(ii) Beclz is more covalent rhan Mgclz. This is
Hence BFj is triaDgular planar. In NH3, N-atom
bccause Be2r ion is smallcr in,size than Mgz+ ion
undergoes ,rp3 hybridisation- Hence NH3 has
and hence has greater polarizing powcr.
pyramidal shap with one lonc pair oD N-atom.
(iii) Sncla is more co!-atenr rhaD SnCl2. lhis is
(.i) Both C in CCta and Si in SiCIa undcrgo.rp3
because Sn4+ ion has greater chargc aitd smaller
hybridisatioD. HencE they are tetrahcdral_
size than Sn2+ ion and hence has greater polariz-
(iii) Refer to pa8e 6/,14. rns power.
 t:, r'.t, .t,'-- Neur Course Chemistql&M)
6172

(iv) CuS is more colalent thaD CuO. This is i.) 'i) Account for the folloving: (Writc the ns\ver in
forrr sentences onlY.)
becauscs2- ion haslargcr size than 02- ion anJ
'fhe experimcntally determined N-l' hond
hence is more polarized than 02- iol'I.
length irr NF3 is gre:rter than the sum of the
Givitrg reasons in brief indicate whether the
sinple covalcnt rrtdii ot N .ind l: O.I.T 1995)
followilg statemenLs is TRUE or FALSE,
Ans,'Ihis is because bolh N aDd !- arc sn'lall aDd heDce
The presence of polar honds in o polyatomic
hxve high elcctrofl density. So lhey repel lhe
molccule suggests that the molecule hns holr-
(I.r.T tee0) bo[d pairs thereby n]akiDg the N--F boDd length
zero dipole moment.
larger.
Ans. False because in synmetrical polyatomic
orolecules like BF3, CII4, CCl4 clc, bonci mo- .j r (;ive renson for thc folloving :
The molecule of MgCl2 is linenr while tllat of
nle[ts cancel out aDd thc net dipole mor]cnt is
zeto. staIlhous chloride is aIlgular'
(M.L.N.R. Allahabad I 995)
Write trvo resonating structllres of N2O that
s tisfy the octet rule. Ant' E c. of l2Mg is Ltz 2tz 2p6 \'i2 in thc gr(lLlnd
(l.I.T 1990, M.L.N R. Alldrubad l99j) srate. lleDce in thc excitcd stale. iL is
ltz Ztz 2p6 3|t 3d. It ur:clergoes rP-hybriclisa-
Ans. 'tj = il = o : ** :N =N - ci :- tion.'lherafore lhe shaPe of Mgclzrs lincar ll.C.
of SD is IIkl 5r25p]5pj. It undcrgoes 72'
Q&ange tbe follorviDg in order of itrcressitrg hybridisation. l'he two hall-Iilled hybrid orbitals
strcngth of hyitrogen bonding (X......'.H-X). form bonds with Cl-atons whilc lhe third is oc-
o,4s,cl,N cupied try a loDe pair. Hcnce SnCl2 is bcnt or
(I.I.T. 1991, M.L.N-R. Allahabad 1993) V-shaped.
ADs. Cl<S<N<O<E rJ l1 Explnin why the diPole moment ofNfI3 is more
(l 6 Write two resonance structures ofozone which than thnt ofNF3? (ltoorkee 1995)
satisfy th octet rule' (I.I.T 1991)
Ans. Refer to page 6i'68.
Ans. See page 6/48.
lndicate t/hether the following st$tement is
() ll Explain why bond Ilngle of NlI3 is grcater tbflll
TRUE or FALSE. Justiry your answer in not thrt otNFa while hond nngle ofPl13 is less thxn
more than three lines : that of P[3.
The dipolemomeut ofCII3F isgreaterthan that Ans. Refer to page 6/68,6/69.
ofCH3Cl (r.I.I 1993) Q. r I Interpret the nonJiDear shapc of llrS and non-
ADs. False because Do doubt C--F boDd is more Polar planar shtpe ofPCl, usihg valencc shcll clectron
than C-Clbond due to greater electro[egativity pair repulsion (VSEPR) theory. GI.T 1996)
of F than Cl but C F boDd leDgth is much
smaller than C
-
bond lenglh. Ans. H2S
-Cl
{t ' Usirg the VSEPR theory idertify the tyPe ot No, of electroD Pairs around S

drow the structurc of OF2.

hybridisatiotr and 6+2 8 .
What are oxidation atates of O aDd tr ?
=--T=2="
(I.I.T, 19e4) So hybridisation = sp3
Ans. Electron dot structure of OF2 is

ii
,rt9x
i (v- shaPed or angular)
u -/,2' \.
FFFF y/
Thus the central atonr (O-atom) has 4 pairs of
electroDs (2 boird Pairs and 2lofle pairs) Herlce PC13

oxygen in OFz is.lf hybridiscd aDd the moleculc No. of electron pairs around P
is V-shaped. 5+3 8
Oxidalion state of F=- l, OxldatioD statc of O
=--z--1=4
CHEMICAL BONDING AND I\4OLECULAR STRUCTURE
6173

So hybridisation = sp3 Q. 16 Why HCI is polar while Clt molecule is non-

polar ? (B.I.T Ranchi 2000)
Ans Io Cl, (Cl-Cl) both atoms have same electro-
I
(Tii8onal f'yramidal shaPe) Degativity. Henc the shared pair of electrons is
ct,7P--- ct attracted e
ct/ the cntre.
charge. In
Q. 11. lvhich of thc follorf,irS has larger dipole mo- H. Hence
mellt Explain.
?
tracted towards Cl which, therEfore, acquires
l-Butyne or l-Butene (Roo*ee 1999) Degative charge while H acquires pGitive charge.
Ans. Their structures are (1. I 7. \trhich one of NF, and NH3 is Eore polar strd
why ? (llbst Benpl J.E.E. 20011
HrC-CHr-C=C-H Ahs. The electronegativity diffcrence between N aDd
I
-Butync H and that between N and F is oearly saore, yet
Each triply booded C-atom is,rp-trybridized NH3 is more polar thao NF3. Reason discussed
H3C-CHz on page 6/68.
\ -C=C _..-H It. Using VSEPR theory dpaw the shspes of pclj
Q.
H./ -\H
1-Butcne
and Br\. (I.I.T. 200i)
Each doubly C-atom is.'f-hybridized. Ans. (i) In PClr, number of electroDs m the vatence
1-Butyne has larger dipole moment b@ause tbe sbell of the central atom viz. p = 5. These are
electronegativity of .rp-C is more than that of shared with 5 Cl atoms. Thus there are 5 bond
pairs and no lone pair on the ceDtral atom-
fP2 - c.
Therefore, the bybridization is ry3d aDd the
Q. 15, Explein why o-hydroxybenzsldehyde is o liquid shape is tigonal biryamidaL
at room temperoturt while p.hydroxy benzal-
dehydc is o high EcltitrE 6olid. (I-I.T 1999) In BrF5, number of electroDs in the valence shell
Ars. In o-hydrory beDzrldehyde, there is iD_
ofthe ceDtralatom viz. Br = 7. Five out ofthese
tramolecular hydrogeD bondiog and hence there are shared with 5 Br atoms. Thus there are 5
is no further association amoDg the molecules r',. boDd pairs and otle lone pair. Hence, hybridiza_
they exist as siDgle molecules. In case ofp_hydro(y tion is rf I and the shaP is square
Womidat
beD?-aldehyde, there is intermolccular hydrogeD
bondiog and benc the molecules are associated ct
throu gh hydroge[ bondiDg

ct
I (, l') What is the S.I. unitofdipole homent ? Draw the
H LEwis dot diagEms of nitric acid. srlphuric acid,
o-hydrox] benzatdehyde phosphorous acid and hy,pophc;phomus acid,
IItrantolecular-bondiDg (West Bengot Jj.E. 2003)
No association Ars. TheS.L unitofdipole moment is C-oulombmetre
o ..{O}o-rr...o = c-@o-rr ... (Cm), 1 Debyc = 3 335 x t0-30 Cm. Lewis dot
\.:J
| \::-/ | structures ofthe given acrds are as follor{s
HH :

p-hydrory beDzaldehyde
r],
Intermolecutar H-bonding
H-O-N- O:
.. ' I
Association througb H_bonding
H-O-O-O_H
As a result. o-hydroxy beDzaldehyde rs a liquid
ll
O :O:
J-
while p-hydrory bnzatdehyde is a high nreliing Nilric acid
solid. Sutphnric acid
 Pradeep's
6174

:o: tI ,,=,q;7;z^*,*"
..t
H-O-P-O-H a-l-o-r,
"T urro ={to,,}o^*,,}o "^ *
-t ,

H 1.g4 = V1t .!2 + (1.5)2 + 2 (1 .5)2 cos *

PhosPhorousacid HyPoPhosPhorou6acid
Q. ill. g";rr* y5O* theory draw the molecular struc' or 34a56- 2'25 + 2 25 + 4 50 cos "
tures of OStr4 and Xetra indicating the locstion or cost=-02476
oflone palr (s) ofelectrons ond hybridisation of or c = 104'20'
certml atoms. ( I'T 2004)
Ans. lcos (180 - 0) = - cr.)s 0
F
!:e. cos (180 - 4)=O 24761
I'nthlur 2. Taking the HOH bond angle in HrO
molecule as 105", calculate the chorge on orygen atom'
Given thet the dipole moment of HrO molecule is
1.t4 D and O-H bon<l tlistance is 0 94 A-

F Solution.
l_-___--:--
TiigoDalliprramidal Squareplanar p,ro = ! pLn + af," + 2P$, cos lo5"
(rldhybridisation) (,ty'd2hybridisation)
(J 21 State with rcasons :. (1.84)2 -2pLH+zPbHx Q 2588)
(i) Which is Eore acidic-anhydrous HCI or
oqueous HCI ?
3 38s6 = zpbHo -0 2588)

(ii) Which is rDore polar or N2O ? - 751 = - 75'l

-CO2 [cos 105" = c.s (180 cos

(iii) Tlhlch is uore volatil'ortho nitroPhenol or = t.qazq (L,

para litroPheuol ? (West Beagdl l'E'E' 2004)
Alrs. (i) Aqueous HCI is more acidic For reasoD see or pzo' = 2 2839
Ans. to Q. 1,Pa86171.
(ri) NzO is morc polar than CO2 This is because or loH=151 D:151 x10-18esucm'
COz is linear aDd symmetrical. Its net diPole Butrro-H=CharSo(d)xd
moment is zero (O = C = O). NzO is linear but .. l 5l x l0-l8esucm =d x (0 94 x lo-8cm)
unslmmetrical. It is considered as a resoDance or d=1606 xlo-toesu
hybrid of the followirlg two structures As O atomacquires charSe = 2d (one d from each
O-ll bond) therefore cbarge on O-atom
:N=N=O:-,N=N-9,
=2\1606 x lo-lo esu
Ithas a net dipole moment of0 D'116
(iii) o-nitroPhenol is more volatile. For reason' = 3.2t2 x lo-10 esu.
see Ans. to Q. 3, Page 611. t'nfilt'n .l The dipole moment of KCI is
II. PROBI,I'IIS
3 336 x 10-29 coulomb metrcwhich indicates thflt it is
I'roblun 1 . The observed value of dipole moment a highly polarized molecule. The interatomic distance
of H2O rtrolecule is found to be l t4 D' Calculata the between K* and Cl- in this molecrtlc is

H-O-H botrd angle in HrO molecule, giver that the 2 6 x 10-10 m. Calculate the .liPole moment of KCI
molecule. if there were oPPosite charges of one fun'
bond momentof 0-H bond is 1 5 D'
dameltal ullit locoted Et each nucleus. Cnlculate the
. As diPole mo- percenisge ionic charocter ofKCl. (r.r.T 1993)
ment of H2O isthe resultalrtof
(o-H boDds), there wcre oPposite charges of one
If
thetwovectors
therefore, if a is the anSle be- fundamental unitic.4 =7'fi2x 10-le coulombs, then
tween the two vectors, then p_qxd
 CHFfuIICAL- BONDING AND MOLECULAR STBUCTURE
6n5
= (i sC2 x 10-19 coulombs; x 12.6 x l}-to m) = 64.2 kcat mol-l = 26E o kJ mol-l
-- 4 1652 x- lo-29 coulomb metre ,. lxu-xrl = o. t1z,/6i8.6 = 1.67
Fobscocd = 3 33r x t0 -29 columb metre Astp > XH, xF=7.61 +X,H
.. io[ic chafidet
7o = 1.67 + 2.1= 3 17 =3 E
3 336 I lo-11 x /?o6,lz11 5. fuihydrous AlCl3 is covalenL From the
l0o=E0.09%
i 1652 x l0-zY data given below, predictwhethcr itwould rcmain cora ent
or becolne ionic in aqueous sohltion (lonization eneq5/ for
AlCl, = 5137 ld mol-1, Alllya,"ti,n for Al3+ = -4665
lu-g = 1t)4 2 kcal rnol-1, kl nrol -1, AIInr^.! for Cl- = -3t1 klmol-I.
[. r=-r,i 6kr:al lnoi-I, (I.I.T t99n
Solution, AlCi3 {rt - aq A](l: r,r{t
li*.-, = 134 6 kcal mol-r ,M.L.N.R. tgg6)
- -
Sotution. Suppose thc electroncgativlties of[I aod
r'J3+ roql .lC| Oqt
'lbral energy releascd on hydrarioD of I mole of
F irr. .eDr.seoted rs IH and tF. Applying pauling's
iorD'lul,.r
Al3+ ions and 3 moles of Cl- ions

lx{ xrl = o loz \6 mot-l

when a is in kJ = 4665 + 1x 381 kJ = 5808 kJ mol-l
Energy required for ionizalron = 5137 kJ nrol-1
BE (H -H)-+ BE (F-F)
= BE {H _F) _ As energy released is greater than the eDergy re_
^ quired, hence the mmpound will ionize in aqueous solu-
t04 21-36
= t'.1 L - __f_
6 .
k(at rDol tion.

For CEs
LE CHOTCE atrsnoNs
and All Other Comp

A p,-.lrr covalent bond $ formed by (c) orbitals ofsane atom but with widely different
fr) lraosference ofone electron energies
(, ) iranrt?reoce ofoDe or ntore electrons (d) orbitals of different atorns with diffeient encr_
i./ ih.iring ofone electron ges
(.i) rh?riog ofoDe or nore electroft\. (e) orbitals of the same atom with exactly equal
energies.
Dip,ile rloDteot ofBeFz is
5. Which of the followiDg stateme[ts is wrong ?
(li) very iow (b) very higb (a) Covalent compounds are generally soluble in
(r) zcro (d) Dot definite. polar solvents
3. Cir5.r!'t u ethyiene involves the hybridisarion (b) CovaleDt compounds have low melting and
a) sp3 (b) tpz boiling poiDts
it,t )P (/) Done of these.
(.) Ionrc solids do nor conduct elecrricily
4. lL hiidisarion involves (d)Ionic conlpounds coDduct electricity in the
l// I ..rr-rrrals of same atoo] with sligh y different fused state.
{jIergtes \tr1o2 is isostructural with (one or more)
f/) I rrrl\itals ofdifferent atoms bu t wlth equal energies
Wne"\ (6) SnCIz

1.d 2.c 3.b Lu 5.a

6n6
glqH, (d) No2
0.r.7: ts86) 15. Which one of the following has zero diPole mo-
nrent ?
."/ Dipole moment is po6sessed by (one or more)
(a) CIF (b) PCl3
(a) l, 4-Dishlorobenzene
(")SF+ (d) cFCb. u.r.r. 1ee3)
Itf,lr 1, 2-Dichloroethene
(c),r.7r 1, 2-Dichloroethene 16. Two lone Pairs of electrons and two bond Pairs of
electroDs are present iD
(d{ffaltt-l,2,Dichloro-2-PeoteDe. Q'I'T I9E6\
(a) NH, (D) BF3
t. Which of the following contains both covalcnt and
ionic bonds ? (d) co2 G.PM.T t ee3)
(4) CCl4 (D) CaCI2
-+fdao
17, H2O has hiSher boiling point than H2S bcause
.I4 NH4cl (d)}{zo.
(a) H2o is a smaller molecule and hencE more
( Ll.l,-1\".R. A,llal,abad 1994)
closety packed.
9. Wbich of the following contains a coordinate
(D) the bond angte in H2O is more than iD H2S and
bond ?
henc! the former molecules are more l.iBhtly
lj'firu{ (b) Bacl2 packed.
(c) HCI (d) H2o. in liquid
intermolecular hydrogen bonding
,(pFfH,O
( M.l,.N'R' Alltlubad 1 990)
10. In which of the follo$dDg the central atom does oot (d) the latent heat of BPorisa on is hiSher for
use.d-hvbrid orbitals in its bondint. water than for H2S. U.S.M. Dlunbad, 1994)

_flrro; (6) oHr+ 1& The central atom assumes r/-hybridisation in

(c) NHt (d) NH3 {tC5 (D)so3
liil.L.N-/r'. 'l alubfld' I990) (c) BF, (d) Not
11. The molecule which does not exhibit diPolc mo- ( M. L. N. R' AllLhabdd I 994)
n.)ent is :

(a) NH3 (6) CHC|3 19. NH3 and BF3 fotm an adduct readily because they

gWct+ form
(c) Hro
(!I.L-N.R. Allahahad I99I I
(a) an ionic bond (6) a covalent bond
G)a mordioate bond (d) a hydrogen bond.
What is the maximuD number of hydroScn bonds (M. L.ll'R' Alhlubad l 994)
iD which a water molecule can Participate ?
(o) I (b)2 20. NH3 has a much higher boiling Point than PH3
(c) 3 4l+. because
iM.I^N.R. A ahahdd 1991,1.1.7. i992, (o) NH3 has larger molecular wsight
v.P. c.li P: Ieeg\
(6) N H3 under8oes umhrella inversi()n
'13. The linear structure is assuoled by (one or more)
forms hYdrogen bond
(a) SnCl2 Jgy'NH3
./p')Nco- (d) NH3 contaiDs ionic tronds whereas PH3 col]-
(c) NOr+ t4r6r. G.I.r. IeeI) tains covalent boIrds.
(M.L.N.R. Alldlwbad' I 994i
14. The molecules tbat will have dipole moment (one
or nlore)
21. Which of the followiDg has oet diPole moolent ?
(d) 2, 2-DimethYl ProPane
(a) CCln (b) BF3
p)kaos-2-Pentene
(9INH. (d) coz.
J?lcis-3 -Hexene
(d)2,2,3,3-tefiamethyl butane. (l l1: 1992) (Haryam C.E.E.T 1994)
i:i ili, iii:, i: :i;: ir, i:i:i :: ,:i:i i :i::i:,i:ii:iii:l:ii:iijitl

6. o,c 7. b'd E' 9, a 10, c l.l'. .l 13. bd 14. b,c 15. c

16. c 11. c lt. a
CHEMICAL BONDINGAND MOLECUI-AF STRUCTUBE 6M

g+Etharct (b) Diethyl ether 30. Wictr one of the followiug compounds has
(c) Ethyl chloride (d) 'Dicthyl amine. d
hybridrsatioD ?
61.L.N.R 1995) (a) coz
23. The Dumber and typ ofbonds betweeD two carbon
,p4'so,
atoms in Caq are (c) Nro (d) co. o.r.T 1es7)
(a) one sigma (o) and ooe pi (') bond 3I' Among Ko2, Alot , BaO2 and NOr+, unpaired
(6) oDe sigma (d) ard tro pi (z) bonds electron is presnt in
(c) oDe si8ma (a) and oDe and a half pi (rr) bond (a) NOr+ and BaO, (6) KO, and AIO'
, l!l) one sigma (o) bond (d) BaO2 onty.
'-ffini* of rhe following hydrogen halidc is mcr ;lclAorotrtY
volatile ? (1.1.L 199n
(a) HF Jh)1ict 32. The cylindrical sbape of aD alkyDe is due to
(c) HBr (4 ril. (c) three sigma C--C bonds
(HoD a,ra C. E. D.7: 1996 (6) three , C-C bonds
)
25. AmoDg the fo or,/iog specis, idendry thc isctruc- (c) two si8ma C-C bonds aod one ,r C-C bood
tural pairs NF3 , NO! , BF3 , H3+O , HN3
(4) One sigma C-C bond and two z C-{
bonds.
(C,B.S.E. PM.T I9g7,I
(a) [NF3 , NO3-] and [BF3 , H3+O]
33. Which one of the followiDg has highest dipole mo-
(6) [NF3 , HN3] and ment ?
[Not , BF3]

.(rlNF3 , H3+ol and [Not , BF3l

.6*n. (D) PH3
(c) SbH, (d) AsH3
(d) [NF3 , H3+o] and [HN3 ,
U.r.T rse6)BF3] t( B.S.E. IlM.l: 1997t
26. Arrange the following compounds in order of in- 34. In cqstals ofwhich ofthe following ioniccompound
creasing dipole moment would you expect maxinum distance between the
'Ibluene (I), ,n -dicilorobenzene cenres of cations and anion!,
0I), o-
dichlorobenzene (III), pdichlorobenzene (w) (a) GF ,.(b c"t
III ltfIv
(a) I < Iv < II < <l <II
<fi| (c) LiI (d)LiF
(c)IV< I < III < II (d)ry < II < I < IlI. i( 8..\ l:. l!l|'t 1993i
35, Which of the following statemeDt regarding
f/KF mmulnes wirh fIF ro form KH covalent bond is not true ?

poutrd contains the species (4) The electrons are shared between aloms
(a) K+ , F- .ind H+ (D) K+ , F- aDd HF (r) The bond is non-directional
(c) The srrength of the bond depends upon the
ana lP,Frl- (d) [KHFI + and F2.
;!p\A+ extent of orr'erlaPPing
(I.t.T. 1996) (d) The bond formed nray or may Dot be polar.
2t. Among tbe following compouDds, thc one that is (jl.ll Ptl '[ t998t
polar and has the central atom with sp2 hybridisa- 36, Hydrogen bonding is not presenr in
tioD is
(d) Glycerine (D) \lbter
,gfurco, (b) siFl
1q/Hyorogen sulpbide (d) Hydrogen fluorido.
(c) BF3 (d) Hcro2. i|.P PM.',f t998)
(LI.T 1 997, 2000)C. P-M-T, 37. The geometry and rhe r),p of bybrid orbitals
29. Which conrains both polar and non-polar bonds ? present about the cntral atom in BF3 is
)
(d) NHaCI (D) HcN (a ) linear, rp _lLfirgonal ptanar , q2

l2.a Z3.b 24.b 25.c ZG.b 2i. c ZE.d 29.c 3O.b 31. c
,2. d 33. d 34. b 35. b 36. c
 6l7A Newt Cotn st 4 {ir t;'t, -. '

(c) tetrahedral, rp3 (d) pyramirlal, ,sp3. 45. The correcl order of hybridisatioil oi i.ii! !.:r,tlri
atom in the iolloqing sPccics
(l.Lf, 1991 ; Ha4am C.t').t') Tl
38. The correct order of increasiDg C-O bond len8th NH3, IPtcl4l2-, PCI< and BCl3 is

of co, co3- , co2 is (a) dspz, dtp3 , spz and sp3

!2lsp3, d-tp2, dtp3, tpz

@)cc!-<co2<co
(c) dspz, spz, sp3 , rLtp3
(b) coz < co3- < co

(c) CO < cO32- < co2

-q4fco .co, < cozr- . (l.l.T. 19e9) gf*.r,,t ; (r) NH3, BF3
39. In a double bond connecting two atoms, there is a (c) co3'?-, so3- (d) PCrs, IO5
sharing of
(c.B.s.L. M|. l: )001\
(a) 2 electrons Jbf4 electrons
(c) 1 electron (d) All electrons. 47. In\rhich of thc following, bo[d angleis maximun'] I
(Ll.l! c.L.E. 1999) (o) NH: It'tr,rs[
40. Whicb one of the follqwiDg molecules will form a (c) PCls (d) scr2
linear potymeric structure duc to hydrogeD bood- (c.R.s.D, Pitl.T 2ool)
ing ?
(a) HCI
(c) Hro
ffin 4t. Which one of lhe
molecules is correct o[
fcllowing arlingcnrenls
the basis of their dipole
r)l'

QfNtt. moments ?
t(:. R.S 1,. Pll',L 2000\ (a) BF3 > NF3 > NH3 (b)NF3>Bt3>Nl[3
41. Which among the following has the largest dipolc (c) NH, > BF3 > NF3 lrNIJr :- Nl-3 > BI;1
moment ?
frro (e) NH, = NF, > BF. lKL th L L.1.. )001)
,I') NH,
(D)

(c) HI (d) so3. 49. Bond dissociation energies irf H , l{CI and Iltlr
follou the order
(A.l.l.M.s. 2000)
(a) HCI > HBr > HF (D) HF > HBi > HCi
42. Atomic orbitals of carboD in carbon dioldde are
{a) rp-hybridised (D) rp3d- hybridised
(c) ,p2-hybridised (d) rP3- hybridised.
(A.t.Liv.,l.2000t
cause
43. The values of electro[egatMty of atoms A and B (4) Covalent Dolecules have deflnite shape
. I\ are 80 and 4 0 respectively. The Prcentage of
1
(D) CcNalent bond is weaker than ioillc bond
ionic character ot A-B bond is
(c) Covalent bond is less exothermic
(a) so% (b)'72.24%
(c) 55 3% (d) 43%.
(D.C.D I; |i. 20(nt
51. Sulphuric acid provides a $imple exanii,irj of
,14. AmoDgst Hzo, Hzs, H2se and H2'Ib,lhe orewith
co'ordiante bonds
the_highest boiling Point is l[4)
(D) non-covalent comPouD(l
Lz1 H,o because of hydrogen bonding (c) covalent ion
(6) H2Te because ofhigher molecular weight (d) non-coir'aleDt ion
(c) HzS because of bydrogen bondiog (e) oone of these (Ibryla M.E.E. 2002\
52. In NOt ion, the number qf bond pairs airo lcne
(d) H2Se because oflo\ er molecular weiSht.
pairs ofelectrons on nitrogen irtonl are
0.t.'t 2000\

3a. d 39. b 40. d 41. b 42. a 43. b 44. a 45, b

4A. d 49. 50. d 51, a
 CHEMICAL BONDING AND MOLECULAB STRUCTURE 6179

(a)2,2 (b) 3,1 (o)No3-, coe- (b) so3, Not

(c) 1,3 k44,0
( ('.8.5.8. I!,v.T 2002) G) clot, co3- (d) co3-, so3
53. In OF2, number of bond pairs aDd lone pairs of (I.t.T 200.1)
electrons are respectively 61. Which of the following sktements is not correct for
sigma aDd pi bouds forDed between two carbon
(a) 2, o <tJzs atoms ?
(c) 2, 10 (d)19
@.P.r4T 2oo2)
(4) Sigma bond is stronger than pi bond
54. Which of the following has zero dipole moment ?
,(D') BoDd energies of sigma and pi boDds are of the
(a) CIF (D) PCr3
order of 264 kJlmol aDd 347 kymol
(d) cFct3 (c) Free rohtion of atoms about a sigma bond is
9)siF4
(M.P PM.T, 2OO2J allou'ed but noi iE case of a Pi-bond
55. In which of the following species is the underliDed
(d) Sigma bond determines the dircction berween
carbon atoms but a pi boDd has no primary
carbon having d-hybridisatioD ?
effecl in this regard. (C.B.S.D. PM.T 2003)
(4)cH3-cooH f)cH3cH2oH 62, Maximum bond angle is prqgnt in case of

(c) CHr-CO-CH, (d) CH2 = CH-CH3 !Q."rt 46; ncl,

Qrr, ({ same in all
(A.I.D.L,L. 2002t ( D. t!tL t 200.11

1)f. Wli"t of the following does Dot coDrain co-or- 63. Wbich of the followiDg pair of molecules will have
dinate boDd ? permanent dipole moment for both members ?

(r) BHr- (b) NHt (a) NO2 and COz (Ql NOz and 03
(c) Sifi and CO2 (d) SiF. and NO2
9"q- (d) H3o+
(F.ajastha n l! M.T. 2 0t)2)
(,r.r.8.t,.E.2003\

Shape of OzFz is similar to that of

57, Number ofr-boDds in Naphthalele is
(o) 6 (b) 3 (a) 9Fz ttln,o,
(") 4 $fr'
(Rojasrhan
G) H:Fz (d) 9Hz
P.M.T 2002) (A.l.I.LI.S.200J)
\ 5a. Which of the followiog hydrocarbons has the lowesr
dipole nloment ?
65. The ONO bond angle is maximum io
H:c (a) NO3- (r) No2-
(a\ \ Il=C -.-CHt
(c) NO2
H.../ ---H {d}Nor+
(A.I.l.ll.s.2001l
(b) CHrC = CCH,
(c) CHTCHTC = CH
., ifi The dioote moment is hichesr for

(d) CH, = CH_C = CH

rrans-2-butere
(4) (6) l,3dimetbyl benzene
U.r.l: 2002) actophenorie (d) ethanol
59. Among the following, the molecule with highest JD (A.LI.lIS.200J)
dipole moment is
4cfcarcr (b) cH2ct2 ofthe folloning is arranged iD the iocreasiog
order ofenthalpy of vaporisation ?
(c) cHcll (d) cctl g.r.T 200j) (a) NHr, PHr, AsH, (b)AsH3, PH3, NH3
60. Which of tbe following are isoeledronic and (c) NH3, dsH3, PH3 (dI?H3, AsH3, NH3
isostructural ? NO3-, CO3-, ClO3-, SOr t .l.l L,ll.S 20t).1t

52, d 53. b 54. c 55, , 56. c 57. d 54. h 59. a 60. a

62. d 63. b 64. b 65. d 66. c 67. d
61. b
 Pradeep's

qrllonrc raon are 73. The decreasing or.lcr of bond aD-tle is

- - (r, inveNely
Proponional to eEectivc nuc.lear charge (a) No" > No2+ > Not
(6) inversely proportional to the square of the et'-
lbctive nuclear charge (6) NOt > NOz > NO2+
(c) directly proportional to ellbctive nuclear charge
(f) NOzt > NOz > NO;
(d)directly proportioDal to the square of effcctive
nuclear char8e. l( .b \.1: !1,11 l: )t)itJ ' (d) No-+
/,r'\ No2+ > No-- No2
Not > No- \.1 & K c ti.l: )004)
69. In BrF3 nloleculc, the looe pairs oosuPy equatorial Which carbon is more electronegative 1)

position to miDinrize
(4) ,rp3 hybridized carboD
(a) lone pair bond pair repulsion only
(D) bond pair
- bond pair rcPulsion only (rf ;? hybridzed carboD
- pair repulsron ard lone pair-
(c) rp2 hybridizc(l carbon
(c) lone pair
- lone
bond pair repulsion (d) Always samo irrespective of iLs hybrld statc
lone pair lone Pair repulsion only (e) None of above llierah C.l':.li. 200J )
{d) - tL.lj.\.1: I: )ll l:,!i1t)11 The H O O bond an8le is [!2O2 is
- -
@) ln" 28' (6) 10e"28',
(c) 104 5" (d) 106'
(a) HzS < Silla < NH3 < BI-3 (f91' \rrala P\I.T 2c04\
(b) NtI3 < H2S < SiH4 < B[r3 If a molecule MX, has zcro dipole moment, thc
ferl{2s < NH3 < SiIJ4 < BF3 sigma bonding orbiials used by M are
(d) H2S < NH3 < BFj < S|II4 t,t I.L.E.E )0(tJt (o\ ip3 d-hyhrid (6) \p-hybrid
71. The state of hybridisatioD of boron and orygen hybrid
(c).r?3d2 k/) ?3- hybrid
{firyz-hyoria lKtnta Ptt.T 2004t
(a) sp2 atd ryz 1tfrpz ana ,p3 l. Which of the followiDg is lenst vol tile 'l
(c'S sp3 and sp2 (tl) sp3 ard ry3 J4HF (Dtflcl
(A.t.h:.E.8.2001\ (c) HBr (.1) III
l HiD^d n PlI.1: )004)
DcoreasinB order of C-C bond Iength is
78. Which ofthe following is not eleclron delicicnt 'l
t. qtt4 IL qH2 r1l, c6H6 Iv qFI6
{a)IV > III > I > II (b)I > II > IV > III {drNrr3 (D) BF3

(c) AlCl3
(c).ruul3 Drr,
Gl) BHr
(c)II > I > IV > III (d) tV > I > III > II \4)
(Otitsd J-D.8.2001) (Haryana PM.T 2004)

H I NT5/EXPLANATIO N 5 I,o M l.Jl1i-i le Choice @.ueel,ione

I. 2- Dichloro-2-pcntahe

CH"
l.t ' -C-Ct
Il Q.tA)
()-c-cH2cH3
Irans

6t. a 69. d 70. c

7t. a
 _f-

CHEM!CAL BONDING AND IVOLECULAB

STFUCTUBE
6/81

1
8.

(c
Y
=0
9. [(Nr]zNt12) .-.- Hl+ CI
I t,.
BcF; inlotves ry-hybridisariorr of Be- IV
t2. Each tI2O motecule can fbrnl lruo Hencc rhc ordcr is t\/ < I < Il < lll.
,r-*nd. ?7. KHF2- K+ + HF .
and_ lwo H-h)nds rhrough
$t:.ir-f 9--","1
l-t-aton]s (Sce Fig. 6
r$.o
2t. II2CO3 a-J
5l pflge 6/5-s). 2II+ r OOj_
lJ. IN=C^:.Ol- rnd S= (= Saretinear.
cllr
r4. cr t,-l'-CH-
"t (,, = 0)
CIII
cIIs_C_lI
(tt + 0)
H_c_cH2cl13
Jl. Flectrons prcsenr: NO2+. 7 + 1,_l=22,
cHlct t._c_t r
-il BaOr-56a16=72,
cI13-cH2_c_II AL t o).
?\tot=13+16+1=30
cII3 CH3 and KO2 = 19 + 16 =
il
('11.,-(:-1-11
3-5

-lr' 1
'Ihus only KO2
32. l orerantplc, H_C C_l
is odd clectron spcctes.
r.t13 a.jJl = I ( ilcarytcnc). [Jcl\een
Iwo ( '-aton]s, lhcrc is ouc o-hr)nd ancl two i -hr)n(i(
I S. SiFa is syulnerriml Dlolecule. flcrce its dipole
lno_ 33. Thc N-II
troncl is nosr polar. HeDce NH3
has
nteDt = 0_
highcst dipole moDtent.
lt ,rP = 1\z L2 2p6 31 3p:34 3p: 34" Cs+ ron is largesl cation and I-
is largest anioD
35. Colalent
- r (. 2_ .,y' hy.r,rirtrsrtron bonds are dircctioDal.
,J. (h" lll . so rl rnvoh.es one sigoru lnd t\\o
38. Thc slructurcs ofthe given specics arc
I /
i
pi nonds.
24, Most.vol tilc hydroge[ h{]lidc ts thc onc N.hlih has
Ieasl hollrng point vrz llCI c=o, , O=C=O.
2-5' NI-, auo
H:O* rr" pyramidal (rp3 hybrklscd)
whereas NOr- rnd BIr3 arc triaugllar
planar
Thus CO ontains kjpie bond, CO.
1.rp2 coarairrs
N is tincarl doublc bond $,hile C)O32- contaiDs
between single
]I d()ublc hond Hcnce C_O bonrl
:nd lengths \!.ill
C' De |l1 lhe order :
. , /
.CI V co<co2<co32_
r 41. tt (ttz0) = 1 84 D, ir (\Hr) -
11 sol
I .4,., D. I1 and
CI are less polar and heDce will
h ve less dipolo
cl moment.
",
= I 7r2ril.ls\oi 6( cs is 2.2, rhc
\y
uith sante
are calhd
6182

arolioearspctes
isGstrudural. BothXeFzandIF;

cHzcl: (Rl is cllcl3 (R2

s(xiatioD oner$/ O opposes R1)
lcss than R1
t
H-O-_S--O-II of CtIrCl Nct t.-1.03D
Il25()4 has tho struclure
rcs ltarrt is less)
t. = l'62D

(] _cl
(l
\
ctl",. 'ct
s3, : o: CC14 (synnnetrical)
(2 bond Pairs and S lone Pairs)
,,'\- :r: tt=0
:I': 60, No. of olectrons in NOt =? +24 +1=32
No- of elsctrons in C4- =n * 24 + 2 - 32

Hcnce lhey arc isoslectric l\'rlhcr

Total no. ofvalence elcctro[s in NOt

=5+6x3+l=24
otI
rl 'lotal no, oIvalencc electrons in COl-
cll,-C-cH3 cl{2 = C-cH3
-lLnx3+2=24
spz sP-
." Hybridization of central aton in both
cases rs

s6. co3- i, ,1f . Hencr: tlrey are isostructural

also'

o d is trc-1!cr thallthatfor
61.
"'' il;#'t1'-
Bond eDcrg-Y
6'j66 is
's = 264 kJ uol-r)-
11 = ra? kJ
i.,of -, ,o.r fo,
\aith a bord angle
62. A1l of thcnl arc lriangular planar
'fhere is l,lo co-ordinate bo[d' ot t20". .__ . .-F-
6J, nforO=(:=O lnd 1...-s,\1, tt
t No ofT-bonds=s-
@ NO, and Oa are beDl nloleculeii
uith perna[cDt
structure and therc-
5t.
- Ib ) is symmetrical wirh linear diPole rnoment
ioi., ritt hr," ,"ro diPole moment'
64. both have oPen book tYPe struc-
59.
/47) They howcver ciilter i[
bond
lengths'
"\/"
n.+.+'c'<+Rz
"\ */\,
H/
cH3Ct
ctla (Symmetrical) sruclu re.s
(Bond moments
C -H, C-Cl reinfor'e
rc giw rtsultatrt Rl 120'
Hencc ON
Res$ltaflt Rz further adds uP)
7r=186D
 CHEMICAL BOND!NG AND MOLECULAR
STRUCTUBE
6/83
NOz+ h s no uDshared elecrror and 71.
ry hybridisa-
tr('r) Ilulrceshapcisllnear{O
= N _ Ci; wrrtr bond
irn$le = lx0.
NOz hts onc unshared electron rr.hereas
NO, has
one unsharcd elecfon pair. I{cDce iD NO2-,
the
rcpulsx)n on thc bond pcirs are olore and
anglc is
Icss

Multiplicjty ofbord (or bood ordcr

I =2, II=3, III - rrL,W =t
rh." mutripticrty {bond or(tcr)
Sl::,.",
oo0d length.
tcss is lhc
132o
73- Refer ro e 65.
66. nc rs 3 Dcbye which 74, :tp orbital is sntallest in s it_e. Hence sp-
-hy,btidizcd
en compouDds. hybridizcd carboD has highesl elecrrooegativity.
67. __
75. H
- O - O hond flngle on I IzO: is ncarly 97".
B.pr.: NH3 > AEH3 > pH3
x
6E. Greater the e_ffeclive nuclear charge, greater I
pull un lhe eledron t y the nucleus, smaller
is the 76' . ,' = 0. Hybndizarron rrf M =.rp2
,rM\
radtus_
69. Similar roCtIi, discussed or page
is lhe
xx
6/44. 77, HF ts-lcilst voliltrlc duc ILJ sLrong hvdro-ten b( rochng
70. H2S < NH3 < siH4 < BFI 7& In NIlt. oclcr ol N is contplclc. Ilcn(c
rt is not
92.6" tor {w u, 12n"
electron deficicnt

ADDITIONAL AESTTONS
As s erti on-Re a s o n Ty p e e.u e sii,lio n s
Thequestiotrsgiven belotd coDsist
ofan .Assertion, in column
key to choose the sppropriaie otr6iur r. 2. Use the following
(a) Ifboth assertion and reason
sre coRRECT ard reasor is
(6) Ifboth assertion a,,d reason are C.RRECT the coRREcr expranalion ofthe assertion.
(c) If{ssertion is CORRECT
but reason is not ii" a"o**""ar.-rrratioD ofthe asscrtioh.
but the reason is INCORRECT.
(d) Ifboth assertion and reason are INCORRECT,

t.
e shared parrs of elect#epel
each olhcr wjlh eouat
ce so rhar al bonds are
equidisranr li._.;.;.;;;-",
randon)
nsofelectrons arouDd
nucleus electric dipolc. which
ces a rra
in lhe nearbJ,a(onts.
+

6184
Pradeep's

Assertion
3. The nearty tctrah lnice, each watsr molccu-le
lorms four hydrogen bonds as
about the q,rygen each nrolecule is fixed in spaca.
to form hydrogen
bourin! water molecules.
Ttere ire ten valence electrons on sulPhur aiom in The structure of SF4 molecule is a distorted trigonal
SF4 molecule. bitryramid.
BF3 molecule is planar whlle NF3 is pyramidal' N atom is sntaller than ll
occurs in p-Nitro-
6. o-Nitrophenol has a hiSher boiling poiot thaD P- Intramolecular hydroge[ bonding
N itroDhenol. phe[ol.
7. lonic'compounds tend to be non-volaiile' The intermolecular forces in these compounds arc weak'
(A.LI.M.S. 1994',)
polar mvalcnt molecule, the shared electrons sPend
The atoms in a covalent molecule are said to share tn a
electrons, yet some c{valent molecules are Polar' more time than average near one ofthc atoms-
(A.I.LM.S. 1996)
N in in NFI3 has,ty' hybridizatior'
NOt has ,'P2 and
NO3- is planDar while NHr is Plramidal'
(A.I.I.M.S. 1997)
t Electronegativity of phosphorus atom is less than that ot
10. Tbe bond angle of PBr 3 is Sreater than that of Pl-I3 bu
bond aogle of NBr3 is less than that of NH3
nitrogeo. 6.1'I'M'S' 1998)

11. Tbc diPole moment helF to Predict whether a The diPole n]onlent helps to Predicl the teoDletry of
molecules. Q4 LI M'S' 1999)
molecule is Polar or non-Polar.
'IIe lone pair-lone pair rePulsioD is weaker thaD boDd
,2. All F-S-F a;81s in SF4 8re Srester thar 9e bu t less
pair-bond pair repuliion. 6'I'I'M S' 2004)
thao l8(f.
True/False ?talements
Selecl lhe trae and fo!.se slatefients lrom the fouow' if it has less than eiSbt valence electroDs or to lose
ing slateme s :
all its outer electrons.
5. Mary Ph)'sical and chemcial Properties
are the
l. A group of amms having characteristic ProPerties
result ofthe shaP that a molecule has.
is known as a molecule.
2. The term chemical bond dos not exPress the exist-
7. The direction oi the bonds around an atom in a
enc of strong forces of attraction betwee[ the molecule does not depeud on the total number of
electron (bondiog as q/ell as non'bonding) in
Pairs
atorns.
the rleDce shell of the atom.
The attractive force resPonsible for molecule for- of a covaleot
mation is the electricalforce between electrons and
E. Ionic bond is not an e,rtreme case
bond.
nuclei. However, not all clectrons in an atom are
involved in molecule formation. 9. Molecule of H2O is angular itr sbape
4, Lewis symbols do not show inner shell electrons' 10. Molecule of methaDe is tetrahedral.
The mGt obvious way for ao atom io have aD octet 11. The presencr of polar boDds iD a Polyabmic
in itsvalence shellis to acquire additional electrons moleauE suSSests that the molecule has Don-zero
dipole momint. (LI'T 1990)

Fill ln The blanks

5. Ionic mmpounds are .--.......... in water arld have
Acaording to electronic theory, atoms combine
............. meltiog PoiDts.
with cach other to mmPlete their..........
6. A double boDd imPlies ....shared pair of clcctrons
An ionic bond is formed by ..... , of electroDs-
7. The two atomicorbitals that overlap to form a bond
3. A co.,6lent bond is formed try............' of electroN'
atoms, must have ....-........ electron/elcctrons each
4, For an ionic bord to be formed btween [wo
the metal atom should have "" ioDization t. The two electroos that ocriupy a bonding orbital
" " must have ........ ..
eDergr and Don-metal atoDl should have
elecfon affinitY. 9. The structures represented by electron dots are
oalled....... ...
 CHEMICAL BONDING AND MOLECULAH
STRUCTURE
6/85
10. overlapping of half_filled atomrc
.When orbilals 21. A double bond
raKes ptace along the internuclear axis, is atwals made of a ............. bond
rhe bo;;
axis- the hnn.t aDd a ............. boDd-
j:loo-,',. .... . oonJ. i r i'' rur",
I:.1::l-,: the pra""
srocways, bond formed is ca ed ............. boDd. 22, A co-ordinate bond is formed try.........ofelectrons.
11. nd-
SigDra boDd is..._....,.... than pi br 23. For
For hydrogen bonding to occur,
hydrolen atom
12. Elcclroncgalivity is ..,.
... lhc power, be li lkcd 1o.......-.... alont.
,r".,........L.,roi.. lo ur_ 24. The
'ust boiling
pomr o[waler is............. than rh
H,s because of ............. ol
t.]. Frecrr( )negariviry ,:f........... is rDarmum
and rs
zcro ror . ........... aJ' .r
2s. Hi oas
has ... -. . . boiling
;;;r;; poiDt
14. A covalent bond formed is nor ^^,^, lban lrcl because of
atoms have............. electronegal / of ice is ............ rhan that ofwal.erdue
Is. A bond is said to bc ioorc if th atlon of..,..........
differeDce bctweeo two atoms is vhich loses electrons acqurres
a ......,......
16. Dipole n.tontcDr of a diiltomic Dol
product of...........-. ,ond energy is around.-...........
17. Mixing ol orbirals ol a shell to lorm
equilulent29. rhe hybridisarion,tat (Roorkee l9il9t
r )rhrrals N called ............. e oforygen in*a,"ir.["ri!
llt' whcn2rl 2flanct2pjortitatsmix ro for
lhree new (Roorkee t9i0i
' ,,. I:..^;
"" ji:;:fl.:.:::,,;;:ffi:'.:,
iiis cailed ..... ... hybrrrrisa_ carboo in sirver
;:;*,*,,orbitars,
19. The hybridisatioD inlolved ir BeF2 (I.r.I re90)
is..-_-..... The
shape is ............. The bond angle 31. creater stability of an ionic compound indicates
is -............ .
20. Tbe hybridisatio, iouolueo ir'ff,
shape is ............. . The bond aDgle
i, ........:..:. . ft" ::^-1': "l:*
,r. AmongN2O,
is......-...... SO2. IJ+ and 13-, the linearspecres are
.
aDd (I.I.T 1997)

Matching Type Qlestions

Motch iteDs in column A tdth itcms in
column B. ColurDn A ColuEn B
Columl ,1 Columtr B
(iv) NH3(d) zero dipote momenr
(i) Me thane molecules (a) cG?lency
(ii) Sharing of eleclrons(r) letrahedrat (r) BeF2(e) potar molecute.
molecute
(ra) HzO(c) pyramidal molecule (vi) BF3 molecule(F) lioear molecute.

ASSERTION.REASON TYPE OUESTIONS

S.b 6.d 7.c &c 9.o t0.b tl.a ll-c

Tiue 5. ?ue 6. .Ilue 7. Fblse &
Rlse 9. ,Ilue 10. Itue ll. Fhlse.

2t.4.2{4 k.t Drof-1 29..tp3 30.tp 3l.targe

negarive.32. N2O andli
II4ATCHING TYPE OUESTIONS

(i)- (h), (ia- (,,i)_ (e) (ivF (.) (v)_ (b),

@), (i)_ (d).
 Pradeep'si iii ti WIE
onTy?eQ,uegtiong
HtNTg/ExPLANAT|oNgi-oAg.geri.lion-F.ea9

,trtls thc

iXiiiiiilr.iiil.:,
 AJN[T

Eq.rilibrir-l rn-!
(Equilibrium processes & phase
Equilibria)

Dynamic nature ol equilibrium, Equilibrium

processes' raw of chemical equiribrium, in .physical processes, Equilibrium in chemicat
Le-Chatelier's principle.
a.riv.tion
'rrvatron .i rne
or ir,! i"rlli
relationship between K, and K.,
ii..iiif :ii.:iiilf ]ilf i;a
7.1. lntrod
I-n general, a chemical equilibrium is repre-
problems based on chemical equa_ sented as
_, ^_ - ,rld,1:.r.rsing
tlorus rn Urut-l and thermochemi:al aA*bB S.rX+vY
equations in Unit
where A ana g ire tn"i"u"tari. uiix and y are
the products. The double urrr* b"t o"L-r-ih-"
."u"_
tants and products shows that the reaction
is taking
place in both the direction. .i-"ft*"o*1y.
reaction does not proceed
reacuon mlxture g6a[2rns reactanLs as well as Based on the extent of reaction before
equi_
products whose conceutrations ."-ui"
J*iorrt .o Yi,i* to
1rr3-"9, chemical,"aci-i-o*os ilri
s[reo mto tollowing three
U'"
categories : "ru._
$-Those reactions which proceed almost to
completion r.e. concentrations oi tfr" ,!u"tr"t.
is negfuible.
f"ft
t(d) Those reactions in which only a small
equili[du, may be define mis

Ii,:l
..
(ufThose reactions which proceed to
such aa
eKent that the concentrations of the,"u"tuit..
products at equilibrium are comparable.
_a
which
are in
es ofth

If tltc opponag prowsw io

In this ,nit, we shall discuss some imrrortant

aspects related to equilibrium in physical
antl
cnemlcal processes.

7t7
 PradeeP's
712

/.2. Equilibria
TO VACUUM
Thc dilfercnt typcs o[ equilibrir irrvolving PUMP
are
nrrr.i.ri .ttrng"t ulongvirh suillhlc cxamples
Lricfly described ['elow :
of
ir) solia-Liqula ,'(-
,."t. tt:.oi" i.".ub.. ulo n
VACUUM
,,n.t nntrnrt atmosPheric ,r leavc rhc
a

i;:il.;;i;;i;;,i'at no heat can eoter

to rcmuin
l"l.i";. ih;;"...;ii.. ond *or"' it tortnd prttcesses
H"**"r. the two opposing
"i,iiirt,. ui'.quitiu'io' u'" *ilting ol ie,. .nd
;:;iil;;
Ireezing ol water.
oi icc = Rate of frcszhg otuatff-
i.-nut" ot-"iini
ir* i't i"ptet"otetl ut
"q"liiu,i,n'
Hro(s) # Hrt)(0
At equilibrium,
'I'Irc tempetarure at which.the solid ontl liquitl
lonn of o puie substance ora in equilihtiwn-tt tlrt
'irrioi'rn",ii ,nutue i'; culletl tha nonnal lrtt ziny
poin ot melting poit of that substqttct'
(2) Liauid Gas cquilibrium {Eu ol'ot ution
ol
-
*riii r'r'i,*a u''rs'y'; considcr u closetl 'cs''cl o
to a manomcter and having arrangc-
"onnected
rn"* f". and addition of liquid into it'
.i""- ""**,i"n
i. Fig T l Supposc the vosscl is llrst
"t it"i*cl ol mcicury in both th': linrbs
""**i..r.
i ii. ,rnorn.r", *ill be samc' Norv supposc wul cr

,t,. apParirl us rs
and the wholc
l. oJa"U ;r,l'o
,if.*"a ,o stay at room temPeraturc (or at
"sscl thc

;.ii.J r.rn.ra,'rc hy placing it in a thermosldl )

i;t 'il;;ii;i ih" l.u"l oi"""v in the lelt

iliil;;;.";;;eteibegins to falt-and that in the
alter somc tro'Ic'
,",nUt iir.rU U"gi,a to rise' Howcvcr'
i;"" k*i;#;;";onsrant The sv'tem is thcn said
obsetvattonrn-
io huu" uttoined cquitibrium This
called

ffii:;
chanqes inlo vapours' lhc iamc
amount o[ wutcr
(u
il;:;; ;i;'s" b'ck into thu liquid wurur
Thus I ctiuilibrium
ni'o.".. *tt.aL"t""satiorr )
I rr" 9-1"1i1$1q"
: Rato of condcnsationl
as
The cquilibrium is rePresented
HrO o s -: HrO k)
in thc
Thc differenr:c in thc levels of rlercury
ttutl f ir'i.'gi".-tt'" cquilihritnt t'trltat ptts;tut ol
 EQUILIBRIUIV
- I

soluti.,rn aad the pressure corresponds to the con-

centration of the gas above the solution (in the
gaseous phase), we cao write
SATURATED
SOLUTION

UNDISSOLVED
SUGAR

FIGURE 7.2. Equillibrium betr,,,een undissolved (i.e. equilibrium pressure)

sugar and saturated solutiol
= Constant at constant temperature
and t-he concntration of sugar in the solution e.g for the equilibrium
remarn constant. COrG) ll COr(aq)
Thus in this case, at equilib,rium,
lcoz(pcl
= constant at constant l.emperature.
Rate of precipitation fCO, (SX
Thc cquilibrium is writlcn as
The reason why the gas fizes out (bubbles
out) when a soda water bottle is opened is as fol-
Sugar (Solid) .3 Sugar (in solution) lows :

Tie amounl o! lhe solitl in gmms thnt dissolyes in ln the sealed soda water bottle, the pressure
lW) g of lhc solvcnt to fonn a sotunrteil solution a! of the gas is very high above the liquid, so the mass
( Wrti{altr ofthe CO, gas dissolved is also high. As soon as the
that .roW in
bottle is opened the pressure tends to decrease to
(4) (ias-solution equilibriurn (Di.\.\olL ion atmospheric presslue, so the solubility decreases
oJ o gas in o liquid rur.lerprcs tcin u cktscdve:-sci). i.e. the dissolved gas escapes out..
Thc best example of this ty.p of equ ilih riunr is that
o[ a soda water bottle. The equilibrium that cxists . Xb sum up, the results discussed above aboul
'physical
equilibria arc reproduced below :
u ithin the bottlc is
ClO, (f) CO, (in solution)
(i) Solid + fiquid equilibrium exiss
a - i.e., the melting
Thc amount of the gas dissolvcd i governed such an equi-
by Henry's law which slates as lbllorvs :

The mt^at ol tt
go:t di\solved in a given nuss of a (i) In liquid <r gas equilibrium,lre
soltvnt ct ar! kmperqture is direoll! proporlional pressure oJ the vapoun above the liquid (i.e. vapour
to lhe plA$we of the glJs above the solvent. pressure) is conston! at constant temperature.
i,e mdp 0r m=kp (u) In solid <------s solution equilibrium,
t+h$c k is acon$unt ojpmportionuw qnd is culled lhe solubility ol the solid in the solution is constant
Iisnr!'s 6fltL\ltnl lts t ob.e depetdt awn thc nature at constant temperature.
oJ the y-s, rulure o! the liquid and tampcralure.
(rv) In gas
Altemdti,el), as the mass of thc gas clissolved
1=i solution equilibrium, dre
mass of the gas dissolved is constant fot constant
corresponds to the concentration ol the ttas in the equilibrium pressure at constant temperature.
PEYSICAL EQUILIBRIA

| 1. If
ol iod.ine is stined in
0.200 g
100 t
K till equilibnunt is reached,
298
what will be the mass of iod.ine found in solution and
the tnass that is lefi wrd,issolved. After equilibium is
reached, with 0.200 g of iodine atd 100 cm3 of wate4
ll, (aq)l at equilibium =0.0011 inot L-1 at 298 K
714
Pradecy's New Colrge

Solution. As the solubility of iodine (con- . ExAIlt'LE 3. Fill in the blsnl$ (a to i) in the
ccnlration et cquilihrium) is 00011 mol L-' lollowinE, table which contains the solubility thta of
(Cive o), Lhis mcans thf,l at equi!ibrium, oxygen in wotet o! 299 K.
1ffi0 cm3 of water dissolve I, :0.0011 mole EpL [o2@] Lo2 @q)lcq.
: 0,0011 x 254 g lnol L-l wd; ..1
(. Nlolar mass of Iz = 254gmol-l) I 106.4 a 0 0012 b
c 0.080 d 0 029
= 0.24 e
0.2i194 e = 0.li 0 029
333.3 e
. . 100 cm3 ofwater dissolve I, = 0.02E B
M 46.1 f 0 0a53
.. l, Ielt urrdissolved = 0.200-0.024 V 598.8 i o o28
_ o.til c (N.C.E.R.T.)
On adding 150 cm3 of water to the above Solution. Expt. I.
soluiion. total volume ofwater : 250 cm3. As total
solubilitr.rt iodine is 0.28 g L-1, therefore iodine PV : nRT or P=+Rr=cRr
that rvill disr,olve in 250 cm3 of water (
= ffi"250g= 0.076* o, C=+
106.4 kPa
.. I, lcft undissolved = 0.200-0.070 g - r;
(8 314 kPa L KjTlnol-l; 1zw
= 0.130 I = 0 043 mol L*r
Molar concentration of the solution
i.e. a=0 043mol L-l
0.130
'-- x 1 x lfi)O
= 'j254 250
^
. b_o.Wrz=ffi:oozr
- 0 0011mol L-r n
Ii\{\ll'1,1. 2. Duing bottlitlg, a cabonated Expt. Il. O"*...- =
0 029
bct'trage wts made by saturating Ilavourcd watet at
A" C with COz ql d pressure of 4.0 otu. Late\ the or d = 0'fi)23 mol L-l
bottle wqs opened qndthe soft dtink allowedto come P: CRT = 0 080 x8 314 x 299
to cquilihiunt at 25' C with dir containinq Cozat a : 198 9 kPa
prcssttrt: of 4'0 x t0-a utm. Find lhe concenlration i.e. c = 198'9 kh
of CO, in the freshly bottled soda ond in the soda
Exnt. IIl. = 0'02e
after it had stood open and come to equilibium. The ol5
Henry's constants Ior oqueous solution of COrare or e =00377 molL-r
At 0'C, k : 7.7 v 1g-2 o1^-1 P
^41-1 Expl.IVf=C=-
At 25'C, k = 3.2 x 1g-2 7-1 os,r-l
^o1 offi' |
Solution. By Henry's law, C = t1r where C is
gas concentration in solution,p is the partial pres-
= 8.3t4 x 299 = o l87 mol L-l
sure of that gas aod k is Henry's constant.
8=
o'?53=ffi =,,.04
(a) For the freshly bottled soft drint
C =kp
= (7.7vLO-2 rrlolL-r atm-1)x(4.0 atm) Expr.v. &=c=+=#*6q
:0 30E mol L-t
=0 241 mol L-l
(b) For opened soft drink at equiJibrium with
atmospheric CO2, 1= o.ox
h
C = (3.2x 10-2 mol L-r atm-1) x(4.0x 10-a atm)
= 1 2t x 10-s mol L-l .'. i=O'A)BxO'241 = 0 0067 molL-r
 FQUILIBRIUM
- I
715

Some of the inportaot characteristics of

physical equilibria are as follows.

, l-At equilibiut4 some obserutble propeny oJ

the,\ysten becomes constont (qs expluineaii secii<ti
? )l A+B i' C+D
g(Nes can be attained Tbe coocept of reversibility in a chenical
because iI the vessel is reactiotr may be explained witl the help of the
ard thore will be ro to[owing example :

If
pieces of gass
Equilibium is d)msmic in nafi.re i.e. there
3. tuDe heated from from
are two opposing processes taking plaCe at equal the other end (F ction
rates. takes place :
1. 4t equilibi,tm, the concentations ofthe dif_ 3 Fe (s) + 4 HrO G) - Fe:Or (s) + aH. (g)
- lnoo
f?ient subslqnces become constant qt constant Stc{m - Ircd odd. Hydrogen
tentpe.rarurc (asexplaioed in equilibria (ii), (iir)
aud
(iu) above) IBON
. .5. At eqdilibium, there eists an expression
--->
involving the concentrutions of the ,rubstancis which
ts constant at constant lempefature.
--+
STEAM
H2

(a)
e.B. for CO, G) -_ CO, (aq),
lcoz@s)l _>
= constant at mnstant te.mperature. HYDBOGEN
fCO, GX (b)
This constant is ealletl equilibiunr conswnt.
. 6- nle magnitude oI the eEtilibiun con,rtaut ----+
he process proceeds STEAM
For example, greater (")
e above case shows
water.
FIGURE 7,3. Reversible reaction occuring
7.4. Equilibria in Chemical processes ij.:.r:j:.1:.i::i+.i.r.:..i
in a dosed tube (c)-

Again if in place of iron, iron oxide (FerOn) is

ptayd iq the tube, heated from below and
nytuogetr K passed over it (Fig. 7.3b), the following
reactroE tales plac :
Feror G) + 4Hz G) ......- 3Fe (r) + 4HrO G)
IIE
Since in both the above ,r"*,irt'"l,lil'
"a..".,
open, hydrogea in the first case atrd water vapour

reversible. It may be represented as

3Fe (s) +aHrO @) i- Fe, Oa (s) + aH, k)
Obviously, whereas the first two reactions can
go to completio4 (r'.c. wbole of iron can be
con_
verted into iron oxide in the 6rst casc and
iron oxide
716
Pradeep's $diig frllt
In the beginning (i.e. at time , = 0), the con-
into iron in the second case), the last rcaction viz'
centratious of A and B are maximum and the con-
the reversible reaction does not go to completion'
In fact, ultimately, an equilibiunl ntixrure of the
various reactants and products is obtained io a
rcversible reactioa (as will be disc'ussed later)'
A ferv more common examples of reversible
reactions carried out in closed vessels arc givcn
below:
(i) CaCo, (s) + Cao (s) + co, (q) creasing.
eof
G)
(,,) N2()4 s -----\ 2NO, G) Ultimqtely
"rs ack-
forwaid reactionbe
(,t0 PCls G) + PCl3 k) + cl, (s) ward reaction. The in a

(iv) H, @) + I, (9) t' 2HI (g)

(r) N, (g) + 3Hz G) + 2NH3 k)

(vr) CH.CooH O + qH5oH (/) +

Acetic acid Ethyl alcohol shown in Fig. 7.4.*
cH3cooc2H5 O + HrO o
Ethyl acetate wste r

?.42. Irreversible Reactions

t
I
LIJ

a single arrow t
It is represented by puttirg
befween theieactants and the products, poioting
from reactants towards products i e' TtME__*
A+B-+ c+D
A few examples of irreversible reactions are
as follows :

(,) AgNO, (aq) + NaCl (4q) -'---'

AgCl (s) + NaNO, (aC) Examples. Tbe [r.rllowing examples illustrate
how the equilibrium is attuined :
(ii) BaC! (aq) + NarSOo (aq) ..-,...* (l I DecomDosilion ofCalcium carbonate in a
BaSOn (s) + NaCl (cq) closei vessel. If calcium carbonate is heated in a
u".."1, the reaction is reversible as shown
(iii) 2Mg (s) + oz G) '--"'' 2M8O (r) "io."A
below :
CaCO, (s) $ CaO (s) + CO2 (3)
ce is kept con-
s coonected to
st
a e (due to CO2

because hydrogen gas formed escapes out

keeps
gas) first telY be-
constant. the fact
7.43. Concept of Chemical Eqtrilibrium' comes
that now as muc CaCo3'
Consitler lhe general reversible reaction
the same amount o[ CO, reacts with CaO to
give
A+B + c+D
th i5 dilfcrent as discuss'cd inuni
.This is the gencral diagmm For the toPoration ofa l:o::;d rn a close'l '-'es.\el' 'r
2, undcr Vapout Prcssurc-
 EQUILIBHIUM I
- 717

from2fC when the broqn colour fades (indicating

combhation of NO, moleculcs to form ilrOn). -
(3) Combinatlon ofII, and I, to form HL It is
a reversible reaction as represented below :
Hz@) + 12 @) i------s' zIil (c\
(Colourless) (Purpte) (Colourlaa\)
If H, and I, (say in equimolar ratio) are
enclosed in the colour is deep
purple in th e time passes, thi
intensiry of and thtn no'liu_
i\.4ANoMETER ther change in colour is observed. This again ind!
cates that the reaction has attained istate of
eq uilibrium.
(4) Reaction potas-
sium thiocyanate ersible
reaction and may c form
as follows :

j:]*.(oq)+rsgm- s--: lFe(scN)lr+

(aq) (aq)
(Yellor) (Cotourless) (Deef rrd) ' "
The details of this reaction have been dis-
cussed later in Section 7.14.
MANOMETER

back CaCOr. In othcr words, the rate of forward

reaction and backward reaction have become
equal. Hence thc reaction has attained chemical cotrstant beciluse the colcentrations o[ H, I, and
,
equilibrium. HI become_constant. Similarly, in the decomposi_
(2) Decomposition ofNro. in a closed vessel. tron ol CaCO3 in a closed vessel at a particular
The decomposition of N2O! in a closed vessel is a temperature, the amount ofCO, becomes constant
reversible reaction as rcprescnted below; and in the dissociation of NrOo at a particular
NzOr G) 2NO2 k)
(Colourlcss)
i_
(Reddish browo)
NrC)n is almost stable at 0"C arrd is almost
colourless. Thus if NrOn is taken in a g;lass bulb

dynamic traturr of
Haber,s proceis,
of N, and H, and
carryrng out the__reaction at a particular tempera-
l.ure, whca equilibrium is a .ained, tbe concEtra_
718

tions o[Nr, H2 and NH3 becomo con-stant as shown

in Fis. 7.6. I[ the experiment is repeated by taking
deutJrium (Dr) in place of H2 but with the same
amounts ald exactly similar condition's as before, CRYSTAL OF
is attained containing D, and ND, in SULPHATE
"qotiU.ir-
placo of H, and NH3 but in tho same amounts' Now
CUS04SOL.
if thc two reaction mixtures are mixed, then after,
.li" ti-", it is found that the conceotrations of
CuSOa DUST
ammonia and hydrogen are same excpt that now
all forms oi ammonia (i.e. NHr' NHrD'

is dynamic in nature.

z
I
kd,
z SATURATED
o SUGAR SOL
o
(.) UNDISSOLVEO
d, RADIOACTIVE
SUGAR
o
FIGURE 7.t. ExPenmentsl Proof oI
dYnamic equilibtium'

FTGURE 7.5. Reprsenting the attainmPnt

oI equilibriun Iot the reaction
N2(9) + 3H2G)+ NH3(S)

Experiments to lllustrate ilynamic lature of

more clearlY :

ough the solution

the process of
from the CUSO4

senlzining undissolved
su e dissolved sugar in tbe
;; eakei is tilted so as to does not stoP.
 EQUILIBRIUM I
- 719

quifrbriam can be otmind lrom

eiths t i-e,lrom lhe illrection o! the resc-

. _ To undcrstand this characteristic, let us recon-

sider the rcaction
\o. G) s__ 2NO, G)
(Crlourlcss) (Rcddish broc,i)
Suppose two identical glass bulbs A and B are
filled with NO, gas at the same pressure. The bulb

whereas most of the molecules in bulb B have the

formula NOr. Now suppose both the bulbs are
placed in a 298 K. It is
observed th
7.45. Characteristics of Chemical Equi- whereas the
the reaction
t#:'Ji;
Iibrium. Some of the important characteristics of
chemical equilibrium are follows :
BOILING WATER

The. experiments sbowiDg the constancy of

pressure in tle evaporation of water ald decom_
position of calcium carbonate aad constancy ,;f
:91:our_ 9t equilibrium in the decomposition of
NrOo (already discussed in section 7.4.3-) prove the
Contains mostlv No"
above characteristic. (Reddlsh bro,;n) '
o
WATER AT 298K

Ha um
_ fhis is obvious because
lowed to escape
ifaay product is al- 2
out e.g. CO, gas in'cise of decom_
position of CaCOr, the reaction will no loager
remaia reversible. A chemical equilibrium has a
meaDrng only tor a reversible reaction.
Similarly, the reaction is irreversible if one of Nron
the products separates out as solid e.g., Noz
(Colourlci6) (R./di.h broDn)
AgNO3 + KCI ......- agCI +IOI{O3
I whereas the reaction taking place in bulb B
is
7110

2 NO2 Nzoo
(Rcddishbrown) (Colourless) a*I;nolesflitre
This is the active mass of the given NaOH
solution,
The activc mass of a substance is rsually rep-
rcscnted by putting the formula oI the substance in
Similarly, reconsider the reaction sqnare brackets, Thus in the above case, wc can
write
Ha@) + tz@) + 2HIG)
(colourlcss) (M stands for'Molar'
1c"r.rir"*) fPr.Prcl [NaOH] = aiV"
If 1 mole of H, and 1 mole of I, are taken in
concentration i.e. moleVlitre)
bulb A at 500'C and 2 moles of HI are taken in an
Mathematical exprtsslon. Consider the reac-
identical bulb B at 500" C, the inteD'sity of colour in tion
bulb A decreases while th A+B Products
and ultimatelY both hav '
According lo Law of Mass Action,
colour. This again Proves
be attained from either direction' Rate at which A reacts ( [A]
quitihrium Ratc at which B reacts c. [Bl
"(v't A cattbst ito6 not aUEt lltz state oI
. . Rate at which A and B react together

[Al [B] = k [A] [B]

c<

wherekis a constant ofproportionality and is called

'vebcilY constant' .
Again, consider the reaction
ZA + 38 --_--.--------+ products
It can be written as
A+A+B+B+B-Products
attained quiclCY--- Rate at which Frst A reacts o [Al
Actio n
Rate at which second A reacts d [Al
e two Norwegian . . Rate at which A reacts c. [Al [Al = [A]2
aw concerning the Similarly rate at which B reacts
action on the con- :
s law il known as "t lBl [Bl [B] tBl3
.'. Rate of reaction between A and B
Law of Mass Action. It states as follows :
c( [A], [Bl3

in a more general rvaY as follows :

The rale oIa rutclion ir ProPorlionulto lhe produrt

-r,t-. --ri,,.-...r, nftha reocrants, egch ra(ser/ lo
solution. Then we can saY :
Concentration of NaOH solution
= .r g in V litres

=4
4t)
moles in V Iitres

('. N'lolar mass of NaOH : '10

g mol-r)
EOUILIBHIUM 7111
- I

reversible reaction in equilibrium. For example,
consider the general reversible reaction
A+B <== C+D
At equilibrium, suppose the active masses of
A, B, C and D are represented as tal, tnl, [C] and
IDlrespectively. App$ing the Law of MassAction,
Rate at which A and B react together i.e. Rate
of the forward reaction c( [Al [B]
:
ki [A] [Bl
where'k; is a constant of proportionality and
called velocity constant for the forward reaction.
Similarty, Rate at which C and D
together i.e. Rate of the backward reaction
c( [c] [D]
= k6 [cl [Dl
where ki' represents the velocity co[stant for the
backward reaction.
At equilibrium,
Rate of forward reaction = Rate ofbackward
reaction
k/[A] [B] = e, [c] [Dl
Tlu product of the molot conc lrsti Ls of llE
products, earh raised to lha pover equal lo its
stoichiomplrb coeffteicnl dividtd hy the prod.acl oI
lhe molar concpnlralions oI lhc rcdclanlr, eqch
mised lo the power equtl to ils stoichirmelric coef-
fici.ent is coratunt ql consta lcmletolwe and is
caI&d Equilibrium constant.
It is customary to use K" for cquilibrium con-
stant expressed in tcrms of concentrations. Where
there is no doubt that K is in terms ofconcenlration,
c ls omittcd.
is
Concentration Quotient or Reaction Quotient
and Predicting the dlrcction ofractlorn.For the
react reaalion
aA + bB <-------\ il+/{
or an! slage of ht redcliot , o,hsr tfun the stage oI
chemical equilibrium, concentrqti.on ratio given on
the L.H.S. oI eqn. (i) Lt called conrentralion
quotient ot rctetion qlotienl. It Ls wually repre-
smted by Qor Q. Thus
g, =
IX' tnt
concentr*tion quotient,
V|'IBIb
(i) IJ Q = K thg reaclion is in eqvilibrium

tcltDl _ k/_ -
(ii) It Q > K, QwiA und to d*re6e so L\ la become

lal [Bl -k,-^

eq&l to K. As a raub, the reaction will proceed in
"' thz b ac ba'ord dir6t ion.
At constant temperature, as k, and k, are
bd b increase.
constant, therefore, k{k; = Kis also constant at
(iii) IJ 8 < K, I wiA A.s a resull,
lhe rea.clion wiU procce.l in tlu lorvard dirulfun.
constant temperature and is ca.lled 'Equilibrium
Thz three coses rnu! be represenled diagra -
constant'.
malicully osJolltws :
[Note : By convention, the actiye masses of the
products are written in the numerator and those of
the reaconts in the denominator].
Again, consider the more general reversible KO
reaction
aA + bB +..... <- ,X +)Y+....
Applying the Law of Mass Action, as before,
we gct
lxl' IYP ....
= K or IC (,)
tAT IBID,.., O"K
where K is equilibrium constant. It is constant at Ra.don ln
canstant temperature. aqu balrir
The alove mathematical equation is called
the Law of Chemical Equilibrium. Expressed in FIGUBE 7.11. Direction ofshift of raction depending
upon the value of Q as compared with K.
words. it may be dcfined as follows :
7112 tirattccp'slfii0' Ciiise,,,,ld.him JfrII)
For Gas-phase Reactions, (i.e. when the reac-
pY:nRT or p= t7
RT : CRT
tants and the products are gaseous), the equi- V
librium constant can be expressed either in terms rn
of concentrations in moles per litre or in terms of moles/litre
L" V:no'of
the partial pressures of the reactants and the
= C (molar concentration)]
products. If expressed in terrr^s of partial pressures,
.'. For the gases A, B, X and Y, we may wril.e
it is denoted by Kp. Thus if A, B, X and Y are
pn = CnRf, p": C"Rf
gaseous in the above general reaction, we can write
px: CxU and py: C"RT
Putting these values in equation (ii), we get
K), . (cY KX
(cx
KP:
wherep4, Pe, pxmdPy arethe partialpressures (ca K),. (c" K)D

_ ci. ci (RT)x
of A, B, X and Y respectively in the reaction mix- + v
ture at equilibrium. It may be noted that the pres-
sures in the above equation are taken in ci. cB (RT)"*o
abnospheres or ban or pascals (in SI units) .
Ci' C{'
- (a + b)
T.TT Relallonshlp between Kp and Kc t:tttii#:iitl:i::i:i:i:::::.i;.:.:.:i: - (RT)G+y)
co' c'"
Consider the general reversible reaction : Iq. (RT)^"
sA+bB =-l xX+yY
ci dt
If the equilibrium constant for this reaction is
expressed in terms of concentrations, $re may write
where K"
'- q.cg
accorcling to equation (i)

and Ln= @+y)- (a+b)

*. =
fil1# : No. of moles of products.
Ci.C} No. of moles of reactants
orsimplyas Kc = ...(r) : Change in the number of moles
ft
Hence
where C6, Cg , Cy and Cy represent the molar
concentrations of A, B, X and Y respectively. As the partial pressures are taken in atmos-
pheres, the value of R to be used in the above
If A, B, X and Y are gaseous, the equilibrium
constant for the above reaction may be expressecl
equation will be 0.0821 litre atmospheres/de-
greelmole. Temperature T will, of course, be in
in terms of pressures as
degree Kelvin ("K).
Further, as a.lready mentioned in unit 1 and

"r:m
If the gases are supposed to be ideal, then we
...(,, unit 2,
l pascal, Pa = 1Nm-2 and l- bar = td Pa.
If pressure is expressed in bars,
can apply the ideal gas equation, viz.
R = 0' 0831 litre bar K- I mol- 1.

SOLUED EXAATPLE

Il,}(,\t\ll'|,[. l. At 700 K, thc, equilibium con- Solution. Here no .= 3 moles, n, : 2 moles

st.ant Krfor lhe reactiort Ln:nO- flr:3-2:1mOle
xor@) -----s 2so2@) + or(c) Kp : 1'80 x 1o-3 kPa
is 1.80 x ru-3 k Pa. Wat is the numeical t'ulue of 1.80 pa
K" in moles per litre for this reaction at the same
= Stu,
1'80 x 10-s bar
lemperature ?
EQUILIBRIUM I 7113
-
R = 0'083L Lbar K-1 mol-r Note, With respect to staqdard state pressure
T :7OOK o[ 1 bar, K, = 1 80 i.e. dimensionless. Similarly
Using the relation5 uith rcspect to standard state cotrcentration of 1
Ko=\ Grr)^' mol L 1, I! = 3.09 x 10-7 i.e. dimensionless (as
K. discusscd later in sectionT.l2).
Kc=
x 10-5 bar
1.80
Ef= 0.0831 L bar K-r mol-r x 700 K ' EXAiIPLE 2.,, T Vj K, the equilibium con-
G\ + 3 H, G) i-
stqnt Kcfor the resction Nz
= 3 .09 x 10-7 mol L-l 2NH3 @) is 6.02 x l0-2 L2 mol-2. Calculqte the
Alterna tively,
value oJ Koat the some tempersilre.
q=*= (8.314
18Pa
JK-r mol-r) (700 K)
Solution. L,nr= 2 - !, =- 2

l'8 Nm-2 \ = t<.(nr)o'

(8.314 Nm K-hol-t) (700 K)
(. = 6-o2 x 10-2 L2 mol-2 (0.0821 L atm K-r
Pa = Nm-2,J = Nm)
mol-r x 773 K)-2
= 3 09 x 10-a mol m-3
.5
=3 09 x 10-7 mol dm-3 or mol L-l = 1 x 10-s atm-2

l. Kp tbr rhe reaction N2O1 (g) <=+ 2 NO2 G) is 3. Find out the value of I(c for each of the lbllowing
0. I57 atm at n"C and 7 atm prqssure. Calculate equrlibria from the value of I!
K for the reacti()n.
| ' . 6.J7 x lo-3 mol L-ll (a) 2 NoCl (s)
i-----j 2 No k) + cl2 G),
2. For tbe reaction AG) + B (,r) <- C G) + O (g), K, = l 8 x 10-2at500K
K" = 49 mol dm-3 at 127"C. CalvulateKp (6) CaCo3 (,') + cao (, + coz3),
KP = 167 at 1073 K.
I.\ns.l.5l x ld stml
[,!rs. (o) 4 33 x l0-. (r) I s?l

l. bt = no - nr = 2 - t = t, x" = Krz 1Rt)& 3. (4') =3 - 2 = l, h = Iq(RT)

^,ts
KD 18xlo-2
-(o .157 atn)(o.0821L atm K--1 mol-r x3ooK)l u, \=Rf =O:-ffitT?sm
= 6.3? x 1o-3 mol L-t.
(R = 0.0831 bar titrc mol-, K-1)
2. bt =nr-n,=2- 1= l,q = q (RT)&
=433x10-a
= (49 rnot dm -3) (0.0E21 dIo3 atm K-1 mol -1 (6)&'r=1-0=1,
x noo r;1 = i.61 :'. lo3 atnt I(-
q= RT = o*rf],.r. = r'az
7114 Pradeep's

A[}D TO' iu liKN@.. L:E,-@ E

\-,)
Law of chemical equllibrlum ln t rm ofo activities. Stricitly speaking, activities are uscd in Place of molalr
concentrations.
ActMty = ActMty coefficient x Molality (or molarity) i.e. 4 = v x m

For the reaction 4A + 68 t' cC+dD,we*rite \=ffi

Equilibrirrm coDstont in terms of mote fractions (Kt). Coosider the geoeral gasgous reaction
aA+ bB+cc+dD
-r -d
If at equilibrium, the mole lractions of A, B, C and D arerA,rB,xc and.rn respecrively then K' = {$'
fnfA
RelatioDship between K2 oDd Xr. C.onstdering the above geDeral gaseous reaction again, if P is the total
pressure of the reactioD mixture at eqrilibriufl], then partial Pressures ofA, B, C and D erill be
Pa,= xeP, Pa=xsP, PC=xcP, Po=xoP
nc^ nd^ r-r^ P)c. rx^ P)/ xc^ .A oc+tt
\ ='7ffi *, <n,*
Apprying Law of chemical Equitibrium =
#)\-;Ff ffi ** = =

where M = np_nt= G +d)_ (o +b).

, Ftom the relation

L = I! (RT )&, ,"" may coDclude that
(4Ir^,, =0,Ke= \ (,t) If lr, = +w (i-e. no > n,), K, > K" (ni)IfAlr: -vc(Le.nrcn,),Ko<K"

lg.clll'llt1qlcjjLElgllEgm constant',
Some of the important characteristic's of
equilibrium constant are as follows : For example, if the above reaction is writtcn
(i) The value of lhe equilibrium corafldrrJ Ior 2 in lhc reversc manner i.e :rs
purtirular readion is alwals consttnl depcruling cH3cooqH5 + H2o \-
only upon tho temryrulure of the rotaion and is cH3cooH + qH5oH
irulependent oJ thc conccntratior$ o! ltv resclanlt
rtith whieh we surt or thE ilireclionfromi,hich lhe the value of the equilibrium constant will be
equihb rium ir upproathzd- lcH3cooHl [qH5 oHl
K'," =
For example, for thc reaction bctween acolic lcHlcooqHsl [H2o]
acid ancl ethyl alcohol at 2-5"C, the value of thc | l.= o 25url-s(
cquilibrium constaut is found to be 4.0., i.c. for thc = Kcl=
rcaction
cH3cooH + qH{OH + (iii) If ,he equqtion (having eqnihbrium cotutilanl
Acctic acid Elhyl K) it tlieideil bf 2, the e4uitibium corutuntlor tlu
alcohol new equdi.oN is lhe squdlx rool al K (1.e. {K\.
cH3cooqHs + H2o Frrr examplc. if K is thc .(luilil)riunl (on..l.rnl
acctalc watel
Ethyl
for the reaction
lcH3cooc2 Hsl [Hrol N2 + 3H2 .-----\ 2NH3 ...(,
Kc at 25'C =
lcH3cooHl [qH5 oHl
4.0 then for the reaction
 EOUILIBRIUM I 7115
-
1a
;N2+;H' # uH, ...(,i) For rhis reaction, * =
IN02l,

the valuc of equilibrium constant, K' = y'K drl lti;F

Suppose the above reaction takes place in two
It is obvious because steps as

K= INH:12
(i)l N2+ o, <--------\ 2No
[For reaction
tNrl tHzl3' 2NO + C)2 <- 2NO,

*,_._ [M:l _ r.p For the lst step, *, -

[For reaction (ri)]
INz]4 [nr]r2 #%,
INO2l2
(iv) If lhe eqati.on (luviag equitibium constanl por rhe 2Dd step, K, =
K) is muhiplied b! 2, th.c equidbrium consant lor IftFlb;
I().
##
lhe neut equalion is lhp squsrc ol K (i.e.,
It can hc sccn in a manner simrlar io tho abovc.
.KxK2=dffi,
(v) f the e4udtian (huying cquitibrium conadd K) lNo,l'z
is written in fin sle4t (hrwing cquilibiam constanl
INrl [orl2 -^
K, urul K) thanKtxKl= K
Iaccording to equation (i)l
f-r,r crumplc. considcr thc rcacti,rrr The characteristics (ii) to (u) are summarized
N2 + 2O2 <- 2NO2 in the Thble below.

TARLE 7.1. Variation of equilibrium constant with variation of the reaction

(K = equilibrium constant for original reaction)

Wtlcn the equation is the neu equilibrium constant is

Reversed 1/K
Divided by 2 raK
Multiplied by 2 K2
DMded into 2 step6 K=Kr x&
(ri) Predi4tinn of the extnt ol reactjon. Thc (b) Intermediate value of K (10-3 to 103)
magnitude oJ e4uiubium conslant giyes at idea
the shows that the concenl.rations of the reactants and
ol c rekfiive dmounts ol the readants snd thc products are comparable e.g. for the reaction
producls. Fet+ (aq) + SCN- (aq) <-.-. [Fe(SCN)lr+ (aa),
(g) Large value of the equilibrium constant K" = 138 at 298 K
(> ld) shows that forward reaction isfavourerli.e. (c) Low value ofK (< 10-3) shows that back-
concentration of products is much larger than that ward reaction is favoured r. s. concentratiou ofreac-
ofthe reactants at equilibrium e.g. for the reactions
tanls is much larger than that of the products i.e.
H, (g) + Br, G) .-=) zHBr (g) the reaction proceeds to a very small ext ent e.g. for
4xtore the reaction
L=5
H, (8) + Cl, G) ZHCIG), + O,
N2 G) G) i------\ 2 No G),
KP=40x1dt
----------:
This shows that at equilibrium, concentration
Il = 4 8 x 10-3rat298 K
of the productsi.e. HBr and HClis veryhighi.e. the This shows that a1 equilibrium, the mixture
reactions go almost to completion. contains mainly N, and p, and very little of NO.
i
7lt6 t )ralta (
r's Neut Coutse Ch"-ittr4rJBII)
(vii) Thc vahr d lhl eqz,l,ilibitnt corrsldn b nnt (S)z : equilibrium constant at
affrteilby the aihlition oI a calalysl b tke ruulion. tempcrature T2

This is because the catalyst increi.scs the R : gas constant

speed of the forward reaction and the backward 7.10. Iypes ol Chen
reaction to the same extent.
' I'here are two types ofchemical eqrrilibria.
' ir_ai .rr icmDeralrjre on fhrse are
(i) Homogcneous Equilibria :
The nunerical value of the equilibrium con-
stant for a particular reaction is colstant as long as
Wn in an aquinbriam reactiolr, aU tlv rcsctunk
ani! tlle prodws an present in lhe sdrrv 1tfuxe (i.e.
the temperature is kept consta . It is a well knourr
9S Eascout or Equid), it is culld a homogeneous
equilibrium.
;; Exanrples of the rsactions in the gaseous
CI
1,hase are :

activation for the forfrard and backward reairtioiis I : rn which the number of m<rles of
Tlpe
are different, so a given hcroase i.n temper atur-e wiu ptuducts is cqual to the number of moles of rcactanlti
iucrease the rate of the forward and backward l7 +
}j.z+ zt{l
reactions to different edents. In other words, the
values of the velocity constants for forward and N"+Oz <.- 2NO
backward reactions i-e. kl ardk6 will change dif- CCI + HzO COz + Hz
ferently with a given rise or fall in temperaturc.
i--
hrrther since K = k/kt,therefore, the value of the [pe U : m which the number oI moles oI
pruducts is not equol to the number of moles oI
reacaorrts

N2 + 3H2 . ^ 2NH3
2soz + 02 2SO3
endothermic reaction increases (t, increases more . =----i ' PCI, + CL
PCls \-
than t5) and that of an exothermic reaction
decreases (k, increases more il!i" k/ with rise in
\or 2NO.

teEDerature. For reactions having zero heat of Two common examples of the reactions in the
reaition, temperature has no effect on the value of liquid phase arc
K. CH3COOH + CTHsOH \-=
Quattitatively, the effect of teEPerature on cH3cooqHs + HzO
the equilibrium constaot is given by van't HofI
equntlon, viz. Fe3+(aq)+(SCN) -(aq) <- [Fe(SCN)]2+ (aq)
dlnK,
_ AH. (ii) Heterogeneous Equilibria :
-A- - RT2 When in an equilibriumreacliory lhe rdrck nls ond
where AH' is the standard enthalpy change of the lht produt$ are presenl in ttPo or nnre than two
reactioE or in the lDtcgrrtcd form, it may be written phiros, it is caM a heterogeneous equilibrlum.
as (assuming AH' to be constant in the temperatu re
A ferv common examples are as follows :
range T1 to T,
CaC{\ (s) Cao (s) + Co2 G)
$
(&), aH' (r, - r' )
,be6i;=rmt 3Fc (s) + 4HrO (g) '- r FerO. (s) + 4H, G)

:
[-In ] C (.r) + Hro (8) + Co W) + H2 (s)
where (Ko)1 equilibrium constant at
temperature Tt Water gas
 EOUILIBBIUM I
- 7117
7.'11. Writing Expression tor Equilibrium
(lri) For the reaction

In Hiting
NrOr G) .- 2NO2 G)

coostant, the most i

in mind is that /re 1' = lNo, G)l'' .'a = do,
[NzOr k)l hroo
constsnti
is prcsent (iv) For the reaction
is also consldnt. In eilh* case, h)e pul their active PCl5 G) i- PC\G) + A2@)
mass equal to I (because their coostant values are
includedriltg.the equilibrium constaat) t.e. we put q= IPC\ k) tct, (s)l
. [Pure sotidl = 1, lPure liquid] = r. IPCI5 G)I
Ti" o^o, why molar concenhalion of a pure Pta., x Pa,
solid or a pwe liquidis taken qs constant is explained
below :
s= Pecr.
Molar coocentration of a substance means (v) For the reaction
moles L-l of the substance which is obtained by Fe3+ (d{)+(sCN)- (aq) (a4)
dividing the amount of the substa-nce in moles by
the volume of the substance in litres *' : _lle-lD'.&d.l_
[..,' {aa)]
=-r[Fe(SCN)12+
(aq)]
Moles of the substance [(SCN)-
i.e. Molar conc.
= Volume of the substance (vi) For the reaction

Converting moles hto mass, we cau unite

cH3cooHo+ qHs OH O. -
Molar conc. cH3cooq H5 o + HrO (/)
Mass of the substance/tlolecular nass Here no Iiquid is present in excess, hence
Volurne of the subctancc
,, : [cH3cooqH5l lHrol
_ Mass of the substaace ^ tc)rtr'orort{ IqHp[{l
Volume of the subEtanci
(uii) For the reaction

Molecular mass of the substarce

NH, (c4) + HrO (4 <_+
Density of the substance NHo+ (aq) + OH-(aq)
Molecular mass of the substance lNHl+ (a{)f loH- (aq)l
As density of a particular pure substance at a K=
particular temperature is coDstant (being an inten- [NH, (aq)l [Hro Ol
sive propetty depending ooly on the nature of the As H2O is present h excess (being the sol_
substance and not on the amount) a.nd molecular vent) therefore by convention, [HrO] is constant
mass of the substance is also constatrt, therefore, and put equal to 1. Hence we write
molar concentration is constant.
(oq)l toH- (aq)l
A few exmples are given below : K= lNHr*
(A) For Homogeneous Equilibrium INH: (aq)l
(i) For the reaction (B) For Heterogeneous Equllibrla
H2@) + 12@ zril (8) (i) For the reaction
-- CaCO. (s)'ir CaO (s) + CO2 G)
K" = __lEI3)r_,
pht
KP _ Applying the law of chemical equilibriqr, we
P\ " P\ have
(r'i) For tbe reaction
(s)l [coz
N2G)+ 3H2G) <- 2NHrG) K= [cao G)l
pfrx,
K"=
lM: G)l'?
IN, G)I tH, G)P
,s Px x fa, .
[CaCO,
But by convention, we put ICaO
(s) |

(s)l = t and
[CaCO, (s)] = I
7118
. Ne.4 Course
7.'l2. Unirs ol Equilibrium Constant ,rii:,,,i:i:j.i.iit :;:i::i','-i:.: ::
Hence K = [CO, G)l
Since the concentration of a gas is usually For the general reaction
expressed ia terms of partial pressures, hence we aA+bB # rX +yY
better write Y1= pco,
k - txf IYI: - tmot t-- I l'l'"
This explains why pressure of CO, becomes
constant when equilibrium is attained in the
decomposition of CaCO, in a closed vessel. = (mol L-1)(r+))-(a+6) = (mol L-r)^'r
(ii) For the reaction ,, f* P\ (atm)'+l or
-- lbar)'a/
Kr=
3Fe (s) + 4[LO G) + FerOa (s) + 4H2 G) foq=Gtn,f'-? i5;d.'r-6
Applying the law of chemical equilibrium, we = (atm or bar)(r+/)-(a+b) = (atm)& or (bar)&
have Evidently if &r = 0 i.e. number of moles of
[Fe, on (s)] [H, @)f products = number of moles of rcactants, \ or
-- -
^' [Fe (r)P tH,o G)]1 K, will have no units.
But by convention, we put [Fe3O4 (s)] = land For example, in case of reactions
[Fe (s)] = 1
Hz G) + Iz G) s--------r 2HI k)
lH, (s)ln
Hence K = or N, G) + 02 G) . ---' 2 NO (S)
lHpGil?
I! or K, will have no units (as n, = n,i.e. Ln = 0)
or in terms of presr*"*, 5 = P*ro
|fl' For the reaction
N, G) + 3 H, G) <----\ 2 NH3 G),
Thking the 4th root of both 0 e sides
as Nt=2-(L+3)= -z
P n" L-t1-z and K, has the
K,, = K" has the units (mol
p*o units atm-z or bar-2
(ni) For the equilibrium Similarly, for the reaction
HzO(0 : HzOG) PCL G) i""''
PCls G) + cl2 G)'
asAn = 2 - 1= I
..
,." =
[Hzo G)]
L-l
tHp (/I K" has the units mol and \ has the units
atm or bar.
But by convention, we Put [HrO (/)l = 1
Why or K, are taken as dimensionlss ?
\
Hence 4 = [HrO G)l Now a days, activities are used h place of molar
or in terms ofPressures, - PHzo (s) concentrations or pressures. These reprcsen[ con-
centration-s or pressures with respect a standard
This explains why vapour pressure ofwater is
state concentraiion (c6) of l mot L-1 or standard
constatrt at constant temPerature
state pressure (po) of 1bar. Thus a pressure of5 bar
(iv) For the reaction
with respect to a standard state pressure of 1 bar
Cu(s) + 2fu+ (aq) #
C'l2+ (qq)+zAs (s)
means jbar/l bar = 5, a dimensionless quantity.
* - ICu2+ (aa)l [Ag (s)l'z
Similarly, a concentration of 0 5 mot L-r with
' lcu ts)l lAe* @q\12 respect to standard state of 1 mol L-1 mcans 0 5
By convention, Ptltting [Ag (s)l = r, mol L-ll1 mol L-l : () 5, again a dimensionless
quantity, Hence Kc or K, are dimensionless.
and [Cu (s)] = 1, we have
lCu2+ (aq)'l However, the magnitude of the equilibrium
-^' -- constalt will depend upon the sta-odard state
1or* lrnr;' chosen.
 EQUILIBRIUi\,,l
- I
7119

;; :d;- "'-1"'"i*o,,r1 *. equiribrium ro

the concentration ol an equilibrium mixntrc "*13'#:,||:,'i,I$,"n","'";'

are N2O4
at 29g K t._ lHrlz _ (!.0/v\2
= 4.50 x l0-2 mote/litre and NO,
=.1-61 x 10-2 molellitre. Wat is rhe volue of equi_ (3.0|2
libium constant ?
= o+s , o-3, = sl:r
, t.\ \\ll,i I
J.Tivo moles of pclswerc heated
Solution. K: lNorl' to 327'C in a closed two litre vessel and
INro+] when equi_
libiunt wqs achieved, pcls was to be ab%
. Thking concentrations with respect to stand_ found
ard state conceqtration of I mol L-1, w" dissociated into pch and C!2. Calculale
h;;-- libium constonts Kpand K"Ior this reaction.
the equi-
.. (1.61x to-2\2
r\=?50;ln_i- s'76xlo-3 S_olution pCl, dissociates as
pcl, i- pcl3 + Cl,
Initial anount of pCI, : 2 moles (Givez)
7o age dissociation at equilibrium : .l{)%
.. PCl, dissociated ar equilibrium
Solution. Equilibrium constant K= tkb = q/700 x2= 0.8mole
.'. Amounts of pCIr, pCl, and Cl, at
-. equi-
= c,5 ,x ,o=
2.3810-a librium will be
= z'qz
PCl, = 2 -0.8= 1.2mole
PCl, = 96-o1"
Ct = 0'8 mole
[
.. 1 mole of pCl, on dissociation gives
1 mole of pCl, and I mole of Clrl
lo_lC!&n. The reactioa betweeu H, and I,
may be represented as
. Since the volumeofthe vessel is2litres, there-
lore, l.he molar concentrations at equilibrium wilJ
be
H2+ 12 . - 2H.1

*= o.6nort-t
Amounts of Hr, I, and HI at equilibrium are lPclsl =
given to be
H, = 0.45 mole, I, : 0.39 mole tPcl3l =T=0.4molL-l
and HI = 3.0 mole and
Suppose the volume of the vessel (i. e. reaction
fcLl = 9j=
2' o.4mol;--r
mixture) = V litres.
_ |pply,ng tne law of chemical equilibrium to
the dissociation equilibrium, we get
Then the molar concentrations at equilibrium
will be [Chl 0.4 x (].4
,. - -[PCI3]
"" tPal.l =1" = 0'267
tH,l= Y,r,,l = Y K, = r! (m)&
and [HIl = $ noteVlitre Here An:no_ nt=2_l=7
 j'rtt tla c t,' -< Nert Course Chemistr4frft[)
7l2O

s=
K"(Rr) or
0'1-x
But T = 327 + 273 = 600 K (Given)
or f+ 0'0414; - o'00414 = o
R : 0.0821 litre atmosphere/degee/mole
.. \ -- o%1 x 0.0821 x 600 = 13'15 l V16 o+l+12 -ax t tr1-!'m111
x = -0.0414
, l, \ \\ll'1.1. 5, For the reaction, 2_
b !!b2-4ac 1
the formula *= )
[Usin8
-0 0414 * y'6 --i-
mr-+-oT656-
-
-2
o'M14 + 0 0182b
Solution. The reaction is -2-
ffi+rHr61 .- 2NH3G)
=z-0 0414t 0 135

Wc arc given that at equilibrium

Px' = 0 80 atmosPhere = 0 0468 mol L-r
(The negative value olx is meaningless and
Pnu:040atmosPhere hence is reiected)
Par+ Pu, * PxHr = 2'80 atmosPhere Thus the concentralion o[ Cl, al equlibrium
L-t
= 280-(o8o + o4o)
.
''' Pxu3
ErhYl acetate (unestet) is [ormed
: 1'.60 atmospheres' etlianol snd acetic qcid lccord'
Aoolvinu the law of chemical equilibrium' we itl,oto tlrc reaclion
get (u-liiiig prissures with resPect to standard statc cH3cooH (t\ + cflsoH (/) +
pressure of 1 atm)
1H3COOCS{s(l) + HrO (t)
.. Pir, _ (I.60)2 SO.O
K, =
4I" E = oao ire:aY -= "" " (d) Starling with I 00
0' 180 mol of ethanol ot 29j
. l .\ t\ l l'l 1 . 6 0.1 mole ol PClr is vapoised' in fiue is found to contain 0 l
260oC Calculate the concentration o{ Caladate lhe cquilibium constanl'
a litre vessel at
Ciri i1 the equilibiutfl constant Ior the

dis
"q"iti\;"^,
sociation ol PCltis 0'0414'
of Clt at
$plullo". Suppose the concentration
equilibrium isx moles/litre. Then we will have Solution. (a)
PCls + PCl3 + clz
0 cH3cooH + ql{5oH <- C}{3COOC2IJ{ +HzO
conc. 0.1molo
Initial 0

Conc. at eqm. (0.1-r) x x Inirial 1.00 mol 0 180 mol

(moles/litre) nt eqm-
Applying the law of chemical equilibrium, we
l-0.171 0180-0 1'1-7 O'l'71mol 0171 mol
get = 0.829moI =0 009 mol
Molar coD(s.
..
..c lPcl3l lclrl o-829N 0.009 / 0'1'11N 0 171nl
IPCLI ICHICOOCTH5l lH2ol
Here K" = 0'0414 (Given) ^. - lcHrcooHllqHjoHl
... xxx _ (0.171/V\ (0.171/v) _
0.0414 = (o_1_r) - (o'sze/v) (o'Ng/v) 1.e2
 EQUILIBBIUM
- I
7121
(r) CHiCOOH+CzHsOH : CH3COOqH5+H2O , I \ \4,,,' t,r.AB2dissocidtcs qs
Initial I 000 n)ot 0.-500 mot
At eqn). ABr(s) i- AB (g + B (d.
l-r1.214 0.500_0.214 0 2I4 mot (J Zt4 mot .If the initiql prcssure is 500 mm of Hg and. the
tt,tal prcssut? qt equilihium is 700 mri
= ().786 mol
= 0.286 mot oiHg cat-
Reaction quotienr (ec) cUtote KpJor the feaction.

0.21.4/V\ (o.2t4/v , Sr!+igl

decrcase rn the pressure
Afrer dissociarion. suppose rhe
(0.786/Y) (0.236/V) = 0.204 ofAB, at equilibrium isp
mm. Then
As Q" - K", equilibrium has not beon attained.
\ll'1.1. s. Tlre quilibium (onstunt ut srG) <- ABG) + Bk)
27tJ pressure 500 mm
Initial 00
Cu (s) + 2 Ag+ (aq) <:: Pressures (5fi)-p) mrn 2mm pmm
at eqm.

..Totalpressure ar cquilibrium
= 500 -p + p + p = 500 +i, mm
500+p= 700 (Given) or p = 200mm
und,thc ..(utccntration ofAg+ ions is J.U Hence at equilibrium
x l0 -q ntol
L- 1.
ls this system ot
equitibiunr ? pas, = 500 - 2ff) = 3ff) mm,
Solrrti-on. Applying the law of chemical
,.,
lrhrtum to the given roactjon,
r:qui_ 2o, = 200 mm, Zs = 200 mm
we have
Po! tr& 2oo-x-2oo
Peo2-
C\2+ (aq\l lAs (silz K, =
K: ' 300 = r33.J mm
[cu(s)l [Ag+ (a4)1,
*r1". to stan(lcrd stare pressure
oI. ,I ,hilr t.s. Yf^I..nect
By convention, putting (s)l = 1
[Ag l).987 atm t.c. 750 mm,
and [cu (s)l = 1, .- = 133.3
rre
l5d_ = t). r7E.
*_ lCur+ (cq) I

lAe* @dlz t'qurntolurnttnure ofpCl,ond. Clrbe pluced

With respect to stan-dard stale conccntration at 250,C
or. I. mol L ', we put [Cuzrl = l.g x l0-2 in^otderto ohtain pclsqt I atm ? (K;for
tlissociation
and [Ag+l = 3.9 y 1g-r
olPClr= 1 761.

Suppose partial pressure of pCl,

,-.!l]tt!U, at
equilibrium = p atm
Then partial pressure of CI2 at equilibrium
= p atm
Purtial pressure of pCl, ar equilibrium
= I atm
For dissociation of pCl5
,
PCI.r + cl2
\_ PCls
Pect, \ po, xp
. . Solution.
state pressure of-With
refere_nce to the standard KP = 1.78 = P
-1 =P'
1 bat i.e. 7ff pa, Pto5
Ko= Pcor- 2 5xo1(FPa p={T'78=1.33atm
Total pressure = prc,r+ prc,r* pgt,
2.5 x l(f pa
= --Tm;- = o.rt = 1+ 1.33 + 1.33
= 3 .66 atm
 llradcat',- Neut Coutse Chemisttg ffim
7122
fi.2\z
448'C, the equilibium con-
f'lx,\i!lt'I-lt lz.At KP=
l:fiF x t =ffi=o o+rz
stant (K) for the rcactton
When dissociation is 50%t, i'e G = 0 5' sup-
H2@) + IzG) i- zHI (8)
pose total Pressure is P'. Then
Predict the dircclion itt which the reuclion will
is 50 5.
p,i""od to ,"o"h
'2.0
at 448'C' if we staft witlt
"quilibium
o.o4t7 =#d,y xY' =ffi"e'
x 10-2 mol if HI, 1 0 x 10-2 mol of H2and or P' = 0 125 atm
3'0 x l0-z mol o[ l2in a 2'0 L atntuirvt' ' Detemine
Solution. The initial concentrations are CO, be in
rolCOat
z-9+1! -' 2'5 1
E i= L-l = t 0 x 10-2 molL-1 Fe (s) + Co'(g)'
'ol Feo (s) + co G) ----s
=1
if!-' - 0 5 x l0-2molL-1 K'=5 o
1ur1 "rolL-1
lC().I s=rs,loa
lcorl
ILI = 1-9+9] "rol
L-1 = 1 s x 10-2 mol L-l Solution. K.=ffi i.e.
IHII, or [Cozl =5 x2'5\10-z
Reaction uotient,U=
tr,;11rt = 12 5 x 10-2 mol L-l
(1"0 x l0-z)2 At a certain temPerqfitte and a
= (o;, lo=x(r-'lr5 ' ' = Pa, iodine voPour contain 40Vt''
utoms F2G) = 2l (dl
Cllcu-
Q < K, the reaction will proceedin tht
Since
fo.war<t direction'to attain equilibrium so that O late Krfor the eluilibium' (N.C.E.R.T,)
becomes equal to K -, Solution. Partial pressure of I atoms
4 xrrPPa=o 4x105Pa
atmosPheic Pres' 100
stue is 0 2. Calculate the pressure at
which it will be
' Partial Pressure ot lz (plr)
QxrotP,
= fOO
half (50%t) dissociated at the same temPerod're'
Solution. Suppose a is the degree ofdissocia- =060xldPa
tion, then
PCls <------s PCls + cl2
Initial conc. l mole 0 0

At. eqm. l-a d a

. . Total number of moles at equilibrium
=l-czt('+a =l+q
then
If P is the total pressure at equilibrium'
partial Pressures will be

o..,r= Y'n'or=fiP 2HBr(g) +HrG)+Brr@)'

P*,r=fi;P'
r<=C6i,tr,
Pto..x Pcr,
, Kr= pr% Initiat 10 bar
AteqE. 10 -P plz Plz
('fo') '(,fo! - --Y- -2 p
x 1d
l-q2"
(i#") 1.6

W are givetr that at P

: 1 atm, a = 0 2' Hence
 EQUILIBBIUi.4
- I

7 /23
Thking square root of both sides, we get
. If total mass of the nixture of CO
P7 and g, then
,Od-pt=4xtd
or 4x702p=2(7O-p) CO = 90.55 g and CO, : 190_90.t5 : g.45 e
or .'. Number of moles of CC) = gO.55lZA :
4O2 p = 26 3.134
20
Number of moles of COz : g.45144 : O.Zt5
ot p=
m= 4.,)8 x l0-2 bar .
' ' Pco =
3.234
xI
Hence at equilibrium iajiTd7ia arm = 0. 938 arm

Ptr= Ptu,l = P/2 = 2'5 x 10-2 bar, 0.2r5

Pcor= l$laf,gj x I arm = 0.062 arm
Pru,=1b-P=l0bar
t. At j 12Z K dnd t atm pressurc, -2_ (0 938)r
v\.=--vco
o of CO anct COrin equilibium witi r Pco2 0'062 = 14,19.

solid.cqrbon has 90.5SVo CO bymass in the

rcaction Ntr=2-l=l
C (s) + Co, (g) <-\ 2 CO (g)
Calculqte K"
Kp\(m)
=
for this reoction at the above
tetnperature. o.K=Kr- l4'lg
N.C.E.R.T) - ^.- nr =brsrrrli, : o rs3.

CO G) + r ,/ 2 O" r!,) -------_r

co2 G)
Given rhat the-partial pressures ar equilibflum
in a
ve.sscl at 3O0O K are

Pco = 0.4 atm.p.o 0.6 atm arld p02= 0.2 atm

N, and of NH3 at cqui-
[ 1.|. K, 3.354, X. = 52.641
=
3. 1.5 moles of PCls are heated at constant
tempera_ -
t. 1':n"
How mu
(n) o.ro mor L-rl
to a one litre vessel
ture.in a closed vessel of 4 litrc capacity. 25f C in order to obtain a concentrahon of 0.1
Ar the at
eguilibrium poiDr, pct5 is 35% diisociared mole of.chlorine ? Equilibrium coostaDt
into ior tbe
PCIJ and Cl2. Calculate rhe cquiltbrium orssoqataon of pCI5 al 25OC is 0.04
constant. I 4.

4, The equilibrium corn*rn,on ,o, ,n" ,'"J ,oun ruJ"

PCl3+ Clz pCIs
0.20 0.10 i-' 0.40 motes./litre
Whal will be lhe equiltbrium concentratton
PClj o[
on adding 0.10 mole o[ Cl2 at the same CalqJlate the amounts of HI, H2 and
12 at equi-
librium.
- I,L)" 0
45 rnol L-ll
5. cid and I molc oferhyl alcohol lArIs. I = 1.6 oolo E,
= tL2 Dole I2 = 0j molel
action proceeds to equilibdum, I0. For the reactioD
of acetic acid and water are
cD O)+2 Ag+ (aq) ,:_ cu2+ 1a4;+u ag 1"y
7124
t't!t1!.t !, , Net( Course Chemisvglftftfi
, rl..al (-l r i.,-! i ir l,iJ C.]N rD
fill in rhc blanks in the following tablc for rhc three 16. Onc molc ol tl2O rnd one nrole of CO arc tlkell
solutions at equilibriun) io a 10 litro vesscl and heated nt 725 K. Al equi-
Solurion ICuz+1aq, [AS+(ag)] K,4itre mttl I librium 40 per cent ofwater (by mass) reacts with
CO according fo lhc cquatior')
lit-l
/nlol /mol lit-l
co (s) ltz coz (()
H2O (9) + 0{) +
1 (a) x lo-e 2.0 x lo15
l.o
l.c x 10-11
-
Calculate lhc equilibrium conslant for the reaclion.
2 20 x 1o-7 (b)
[.\n\ 0 4441
3 2.0 x lo-z (c) 2.0 x lols 17. At ?00 K, equilibrium coDstant fbr the reaction

I \ri. (a) = 2.0 x 10-3 mol lit-l (D)=2oxrot5 llz(9+tzg) + 2I{I(8)is5a 8. Ifo 5nrol
(c) = 3.t6 x 1o-e mol lit-li L-l of HI G) is present at equilibriuul at 700 K,
11. WheD PCl5 is heatcd rn a closed vcsselat 575 K,lbe
what are the cencentrutions of lI2 G) aDd I2 G)
rs found to be 1 alnr
assuming that wc lnitially started wilh Hl (8) and
tolal pressure at equilibrium
and partiai pressure of Cl2 is fourrd 1o thc 0 324 allowed it to reach equilibriunr at 700 K.

alm. Calculate the equilibrium constaot (Kp) for (N.C.E.R.T) [ r,r,i [H2l = [I2l = 0 068 mol L-ll
the dec{mposition rcactiou. [.rns.0 29t1 lll. 'lle equilibrium consiaot for the reaction
12. In lhe dissociaiion of Hl, 20% HI is dissociatcd at CH3COOH + qHjOH <-\
equilibrium at a certain terirperaturc. Calculate
CH3COoC2FI5 + Hzo
Kp for the reaction
is4 0 at 25"C. C-alculate the weiSht ot ethylacetatc
HI(s) <- lnr@*!rr@1. that will be obtained when 120 g oL acetic acid arc
[,\t'\ Kp=K.=01251 reacted with 928ofalcohol. [.\ll3 f17'048]

13, A reaction mixture containing N2 at 0 50 atnl. t9. A sample of pure PCI-5 was introduce.l into an

0 50 atnl is heated lo evacuated vessel at 473 K A-ftcr equil,brium wils

ll2 at 3 0 atm and NI{3 at
attaiDed, concentration of PCl5 was fouDd to bc
450'C. tn which direclion lhc rcaclion
N2 G)+3H2 G) .- 2 NI'I3 G) will go ir 05x l0-l n,]olL-l.lfvalueofI(cis8 3 x 10-3,
K, is 4.28 x 10-5 ? [ \,r. Ilrclo,vard direction] what are the concentrations of PCl3 aDd Cl, at
equrhbrium ? r)
(N.C.E.R.
14. Reaction betweeo nitrogen and oxygeD takes placc
as follows : I.\Ds lPcl3l = [Cl2] = 0.02 nlol L-ll
2N2tg) + o2@) + 2N2O G) 20. Bromine Donochloride (BrCl) dcconlPoscs into
If a mixturc of 0 482 mol ol N2 nd 0 933 nrol of bronrine and chlorine and attaiEs the equilibriunl
02 is placed m a reaction vesselofvolume 10 Land 2 BrCl ----------\ Br. (c) . Cl. {(l
l")
allowed to form N2O at a temperature fbr whlch tor which Kc = 32 at 500 K. If inilially pure BrCl is

K. = 2 0 x 10-37. Deternine the oomposition of prcsent at a conceDtratiorr of 3 30 x 10-3 nlol

the equilibrium mixture . (N.C.E.R.r.) L-1, what is its rDolar coDcentration in thc nll\ture
at equilibrium ? (N.C.L.ll.'t )
|.\rs. IN2l=0.04t2 mol L-r, lO2l=0 0933 mol l,-r,
\'r\ 3.tl x t0-a mol l, r]
[
INrOl = 6 6 x l0-21 mol L-ll 21. [-or the reacrion CHa g, + 2 IIzS Q{) <-
15. Nitric oxide reacts with bromine and gives nitrosyl 62 (g) + 4 H2 (s), a[ 1173 K, the magoitude of the
bromide as per reactioo Siven below:
equihbrium constant, Kc rs 3 6. For the iollo\tring
2 No (g) + Br2 G) + zNoBr(8)
conpositioD, decidewhether reactioD mixture is at
When 0 087 rDolof NO and 0 0.13? molofBr2are
equilihrium. If i! is not, dccide to whioh direction.
mixed in a closed contaioer at constant lempertr- the reaction should go
ture, 0 0518 mol of NOBr is obtained ar equi-
librium. Calculate equilibrium amount of [rtri{) [CHo] = 1 67 14, 1s2sl = 1 20 M'
oxrde and bromue. (N.C.E.R.T.) lcs2l = 0.90 M, [Hr] = 1 78 M. N.C.E.R.T)
IAns. NO = 0.0352 mol, Br2 = 0 0178 rnol] ['\rls Backward directionl
 EQUILIBRIUI\,4 I
- 7125

FOR DIFFICULT PROtsLEMS

H2 +lz i- 2Ht = 0 4 or 0.05 (0.{ is impossible because'r c,tnnot
Moles at eqm : 6.34 4.Oz 42.85 De greater than 0.2)
Molar @n(s..: 6.34N 4.U2ly 42.857-V mq1s5 1- 1 I{eoc [PCls] = 0.40 + 0.05
- 0.45 mor L-r
,,
\c = A2.a5 / V\2 5. cg1cooH + qHsoH
l6l-4G-:bTt = 70 042 ==clr3cooqHs + H2o
InitialImole lmole
2. co * *o, i- co At. eq. 1B mole 16 mote 2B mole mote
At. eqm.0.4 atm O.2atm Molar tB V 1BV zBV 2RV
O.6arm coD(s.
Pa" (mot L-t)
- 0.6
'>= ,."r4= t. ^ff7^ K"=#tr^#ffi=o
= 3,354
For the revease reaction
K, = I! (RT)& or K" = z (RT;&
$ cH3CooqH5 + H2o i- cH3cooH+qHsOH
= 3 354 / (0.0821 x 30Nt1- t/2
= 52.64 IDitial I mole 3 moles
At. eqm. (l -.r) (3 _ r) x x
Initial motes 1.5
.ir
at.esm.(r.s-#,,r) i] -r(3- = 4

I
or ai=l+3-4x
= 5---0.525 0.525 0.525 or 3l+4r-3=0
=0 975
Molar concs. 0.97514 o.5xt4 0.525/4 ^..._----_-zrT-
, -4!/-t6;4xf;-i
v _(o.525/g@.525/4\
'\--l[gB7ry-=o ozt
..
= 0.535 motc
Ester present at eqm.
+ q= of{fr-=zo = l__O,535
= 0.465 mole
New inirialconc. of Cl2 6. Suppose-we sta( with I
= 0.10 + O.l0 n]ole of HI and.r is the
oegrce ol d,ssocialion. Then at equilibrium,
= 0 .20 mol L-r lHIl = (1 -j)A4 tHrl -, / 2v.
New initialcoDcs. of pcl3 and pcl5 remain
thesame
[I2l = x./ 2V moles per lirre.
Supposing -r mole of pcl3 reacls, the
new equF Put thevalues in the equation
librium concs. wi be
[pcl3] = 0.20 _ r,
tHrl [Izl
[Cl2] = o 20 - j and lpctsl = 0.,t0 + x ti= -IHII-
Putting the vatues iD rq=
aDd calqJlate r.
di$, 7. z NU, ,_____. N2 3H2
Initial I mole
iD.to:r(o:i6=, = 20 Al. eqm- (1-{).2) mole
or (0 40 +r) = 20 (0.04 +r2 _ 0.40x) 0.1 mote 0.30 mole
= 0.8 mole
or 2Ol- 9r+0.40=0 Note that 2molesof NH3 dissociate
to form 1 mole
o,*-'t=Elf,i t.
ofN2 and 3 motes of H2.
pctj pCI3 +
t y'ET:ZT)olT:r
- -------2-x-Zn- =o-,
y
Initial -+ clz
a mole
40
At.egm. (a--{.1) I
0. 0.1 mot L-I
 PradeeY's
7126

On soMng, this givesr = 6 6 x 10-20

lPchl [cl2]
K. _ __TPeiJ_ x 10-21 molL-l 6
- [NzO]=01,=6
o l x01 15. 0 0518 mol of NOBr is fornled from 0
05'18 mol
Le. 0 0414 =;=T;f. of NO and 0 05182 = 0 0259 mol of Br2'
This gives a =0 3415mole .. At equilibrium,
I moles of Hz are formed at eqm Then
9. Supplse Amountof No = 0.08? - 0 0518 = 0 0352mol
concs. at equilibrium will be AmouDt ofBr2 = 0 0437-0 0259 =
0 0178 mol'
= (2 2 r) 10,
llltll - / [Hr] =r / 10
16. At equilibrium,
and =r/
Uzl 10 moles,4itre
1-#lg mol L-r = o o6 mol L-l
PCl5 + + cl2 tHrol =
11. PCl3

At eqm., Poz - Ppo, = 0 32,4 atm- Hence [COl = 0 06 mol t--l'

o 3U) = o 352 arrn lUrl = S mor L-l = 0 04 mol
L-1'
Peos= 1 - (O 321 +

Pror'Pa:. ro 32o [COr] = 0 04 mol L-l

,, =-7pc,, _o.32o = 0.298atm
\ 0 352
*=ffi=frffffi=oooo
12' HI + l.r, * l', 11.2Ftt(9 + Hz G) + 12 (8), K = U54 8

IDitial I mole At equilibrium, [HIl =0 5 mol.L-1'

1-0 20 0 10 mole 0.10 mole
At. eqm.
IHrl=tlzl=rmolL-r
= 0 80 mole
K"= = o. t25,
K=6+=fito*"'l'
Ke=q=0125 ThisSivesx = 0 068

13. Concertration quotient (Q) 1t. Initially, cH3co6H = s nrs1 = 2nrot

=ffi=";7'=o*'
H3 r,2r (0.50)2 crHroH =!|mol =2mor
- r)n/ mol L-l
At equilibrium ICH3COOHI = (2
As Kp < < Q, reactionwillSo iD the back'vard direc-
Y
lqHsOHl = Q' - x) / molL-1'
tion.
14. 2N2G) + o2G) + 2N2o (8)
lCH3COOqH5l = [Hro] =
t/V mol L-l
lDitial mol 0 933 mol
0 482
K= X*xr= 4(Given).
At eqm. O'482-I o'933-xn x x)'12 -
o 482 -x O933-x'2 x This givesx = 1 33 mol
Molar conc. l0 . . Mass of ethYl acetate = 1 33 x 88
111 o4E
0 x 10-37 is -m--
=
As K = 2-- very small' this means.that
urouot ot l'1, nod 02 reacted ('t) is veryiery (Molar mass of CH3COOQH5 = 88 n:ol-1;
g
,i"
small. Hence at equilibrium, we have 19. Similar to Problem.lT'
+ cl2 g)
[N2l = 0 0482 mol L-1' 20' G) <----\
2 Brcl Br2 GI)

lo2l =0 0933molL-r,1XrO1
=O t' Initial 3 30 x 10-3 molL-l
At eqm. (3 30 x 1o-3 -l)
xD xD
Iq= (x/2\U/2\
v.'c= ----)----------' = 32 (Given)
(3 30 x l0-r -r)'
- z.o x to-31 (Giten)
 EQUILIBRIUM
- I
7127

* .. At eqrD.
4 (3.30 x l0-r -r) lBrcll = (3.30 x lo-3 - 3 0 x 10-3)
= \/fr = 0 30 x 1o-3 = 3.0 x 10-a n:ol L-l
2 (3.30 x 10-3 -.q
=5 66
,,. o.
-c=,!T']J,T4:- o 2e' tr lg)1 =s.ao
,
= ll 32(3.30 x -r) '10-3 [cH4l lHrslz 1.07 x (l 20)'
ot -=JZ
12 32x = 11 32x3.30x 10-3 ,
tu Q" I(", equilibriunt will go in the backward
direction.
or x=30x10-3

EIIect of adding atr lErt gas to a rractlon

A system in equilibrium is affected by the mixturc in equilibrlum, Corsider the dissociation
following factors :
equilibrium
(1) Change of concetrtration of any reactant PCr5 G) <- PCl3 G) + Cl' G)
or product Applying the law of chemical equfibrium, we
(2) Change of temperature of the system get
(3) Change ofpressure on the system ..
..8 [PCr3] lctrl
(4) Addition of catalyst tPct"l
(5) Addition of some inert gas. (a) If the reaction takes place at corlslslllt
The effect of change of concentration, pres- volume (i.e. in a closed vessel), addition of an inert
sure and temperature is prcdicted with the help of gas (like nitrogen, helium, argon etc.) will not
a principle known as Le Chatelier's principle, change the molar concentrations of the reactants
described in the next section. The effect of adding and products. Henc the state of equitibrium will
a catalyst or an inert gas is explained below :
remain unaffected.
(b) II the reaction takerplace at constant pres-
EtTect of adaltng Catalyst on the cqulllbrlum.
surc, addition ofthe inert gas will increase tho total
It may be summed up as follows :
volume. Hence at equilibrium, the molar con-
Tle dn&ioi DI 0 @,&;u ifu tut nitur, itv centration of each of the reactatrts and products
qailibrisn Eifiiw@, it ,r/ps h tlu aa*iwr** o! will decrease. Since there are two concentration
qdhbrlurt quicr,b. term-s in the numerator and only one in the
For example, the following equilibrium exists :
denominator, therefore I!
should decrease. But
K., is constant at Constant temperature. Hence to
zHzG) + OzG) i- zH2O (B)
keep K" constant, either [PClrl should decrease or
But this equilibrium is never attained under
[PClr] and [Clrl should increase. This can happen
only if more of PCl, dissociates to give pCl, and
Cl". Hence the dissociation increases with the addi-
tion of an inei gas.
To sum up :
value of the equilibrium constatrt at 298 K is found
to be same i.e. 1.2 x tff
(which is quite large)
irrespective of the speed at which the equilibrium
is attained. This is obviously due to the fait th"t the
addition of catalpt increases the speeds of the
forward reaction arrd the backward reaction to the Note.
same extent. .In case of gaseous reactions of Tlpe I,
as no = n,i.e. there is no change in the numbir oi

?
7128 Pradeep's

moles, tlerefore there isno effect ofaddingan inert Fe3+ (aq) +

+ F- (oq) FeF?+ ktq)
gas on the state of equilibrium. Fc3+ (aq) + 2F- (uq)- FcFr+ (arl)
7.14. Le Chatelier's Principle :i
':i
r'r::r:i
:i; :r':i:i ::ii::
':
r::r':i: I :::
'
::r:::
Thus the conccntration ol Fc3+ ions
decreases. The intensity of the colour of the solu-
The elfect of concsntration, temperature
tion is found to decrease indicating that the cqui-
and pressure on a
librium shifts backward.
predicted with the
proposedby Frenc
a
The effect ofchangc ofconcentration can als<r
After his name, this be predicted by comparing thc reaction quotienL
Chatelier's principle. It statqs as follows : witi the equilibriurn constant. Lct us a considcr the
general rcaction
A+B <-------\ C+D
K- = -l!UP]
.-c ...(,
lAl IBI
Let us now discuss the effect of the various Suppose conccntration of the reactant [Al or
factors one by one. [Bl is inireased, so that now we writc Q" in place of
(t) EIIect of cbange of concntration. Con- Kc
sider the general reaction
A+B <- C+D vc=
o- l9l:lP-l
IAI tBl
...(,,)
I[to this reaction in equilibrium, more ofA or As [Al or [Bl has been incrcased, Q" will
B is added, then accordirg to Le Chatelier's prin-
ciple, the effect will be to decrease the concentra- become less than K". In order that cquilibrium is
tions of A zurd B . This is possible only if more of A re-estublished, O" witl tend to hcrease till it be-
and B react to form C and D, i.e. the equilibrium comes equal to K". This can happen only if [Al ancl
shifts in the forward direction' Similarly, the effect
of adding more of C and D to the reaction in lBl tlecrease aod lCl and lDl incrcase i.e. equi-
iibiium will shift in thc forward direction. Similarly,
cquilibrium will be to shift the equilibrium in the
it can be seen that the effect of rcmoval of product
backward direction.
reac-
tcl or [D] shifts the equilibrium in tbe lbrward
The effect of change of concentratiol on a
diriction. This has a great signihcance in the in-
tion in equilibrium can be very easily seen in the dustrial processes because i[ the product is
laboratory with the help of the following reaction reovered iide by side, the equilibrium will shift in
Fe3- (a4) + (scN)- (aq): [Fe(SCN)2+l (aq) the tbrward direction to form rnore product. Thc
(fate yeitoorl (Crlourl..ss) (Rcddish broq'r) removal of product is especially easy if it is a gas.
i.e. if to the solution ofa ferric salt e.g. ferric nitrate For example,
of sulPhocYanide (i) in the manufacture of NH. by Haber's
less) is added, a
proccss, NH, gas is liquehed and hcnce removed
due to the forma-
tion offerric sulphocyanide complex ion. Now if to side by side tiom thc reaction mixture.
t solution or Potas- (li) In the manufacture of quick lime (Cao),
s added, the colour by clecomposition of CaCO3, thc gaseous CO,
showing the forma- which is one of the products is allowed to escape.
Looking at eqn. (ii), it may be noticed that
continuous removal of the product kceps the value
rrf (). Iess than K.. As a rcsult, the rcaction con-
tinucs to move in the forward direct ion
Some examples from everyday life. If in a
system in couilibrium, the
part is disturbed. it no I
NaF mav bc added to the reaction mixture lt com- Iibrium and rcadiusts its
bioes wiih thc ferric ions as follows :
 EOUILIBRIUM
- I
7129

tablish the cquilihrium. This is illustrated with the

frrllorving cxamples
Il in a rcaAion in cquihbium, lhe conccntralion of
:
an! rcadad & increcsed, the equilibrium shi.Jts in
(i) Ckthes dry rytickcr wlvn tlrcre is q breeze or thc larwad dirqtion. On the otlrcr hund, d lhc
xc keelt ol shokitg it. This is because watcr vapour concent rlion ofun! producl it increused, the equi-
ofthe nearby air are renroved and cloth loses more libium shilts in the buckward diretrion. The
watcr vapour to re-establish equilibrium with the revene happens dthe concentration\ are decreusc(I.
surrounding air.
(ii) llb swcat nlore on a huntid dq! but it (2) Efiect of change of temperature. The
change temperature alters the itate of equi-
der the fan. Morc swe.ating -of
librium for only those reactions in *.hich eithcr hcar
srrrrounding air has large is evolvcd (cxothermic) or hcat is absorbccl (en-
and our skiu cannot losc dothermic). In fact. every such rcaction is ma,Je ufr
more to it. The fan removes the humid air and
ol trvo opposing reactions. lf thc lorward rcaction
evaporation starts from the skin. is exothermic, the backward reaction will bc en-
(iii) Tiqnspoft of otygen by h.oemoglobin in dothermic and vice-versa,
bhxttl. Orygen breathed in combines with the (i) Consider thc exothcrmic rcuction
hacmoglobin in the lungs according to the equi-
libriunr
N2 G)+3H2 G)
3 zrvH, (r). AH =
92.4k.I
Hb(s)+ orG) + Hbor(s) or it may be witten as
exo
When it reaches the tissues, the pressure of N, @)+3H, (C)
the equilibrium,
<=- 2NH, (q)+e2..1 1.1
endo
Whe[ it returns Obviously, the forward rcaction is exothcr,nic
gen is high, more whercas thc backward rcaction is cnclothcrnric
Now, i[ the temperature is increascd i.r, Irrr:L i.
(iv) Rentoval of CO, fiont tissues bv bktod. supplied to the systcm, thcn according trr I_r
The equilibrium is ('hatelicr's principle. thc cquililrriunr rviii rrr;r r .
co, G) + HzO (4 s I HrCO, (aq) thc side that absorhs hcat l.r,. in lhr. h.rckrval
tion. Similarly, decrcasc in lcmpL.raturc
tlir.i
rrlil .lrrrr
. - n+ @q) + HCo, (aq) thc equilibrium in the forwlrLl ,.lircttirrn.
As partial pressure of CO, is high in thc tis- (ii) .Again, consider thc cndothermic r cirction
sues, CO, dissolves in the blood. In the lungs, as N2 k)+o2 G) -- 2NO (q), AH= + 180.7 k.r
partial pressurc of CO, is low, it is released lrom or it may be written as
the blood.
cndo
(v) Tooth decayby slrseh. Our teeth are coated N, G) + o, (Jt) + 180.7 k.t s_ 2 NO k)
with an enamel of an insoluble substance known as
hvdrorypatite, Ca. (POo). (OH). It exists in equi- Ob\.iously, herc the fonvard reaction is cn-
librium with its ions as follows :- dothermic whcreas thq backtvard roaction is cx-
othermic. Arguing as beforc, thc incroase ol
Deftineralisation
temperaturc rvill favrrur the [orward reaction whilc
Ca. (Poo), (oH) (s) -- thc decrease ol temperar,ure \vill lavour the back-
Rannemlisation
ward reaction. Thus in gencral,
5 ca2+ + 3po:- + oH-
The forward reaction involving dissocation is
callcd demineralization and the backward reaction :tr:il;;
involving tbrrnation is called remineralization. If we
do not brush our teeth after eiiting sweets, the sugar (3) Effect of change of pressure, This fuctor
gets lcrmertcd or the tceth to produce H+ ions has u.signiliclrnt role to pluy only in r.asc ol guscous
rvhich combine with tbe OH- ions shifting the rcuctions .rnd thosc loo which procecd with r
equilibrium in the forward directiou therebyiaus_ change in thc number o[ moles.
iug tooth decay. (i) Consider the dissociation oI NrO, into
Thus in general, NO-;
 Pradeep's
7130

Nro4G) + 2NO, G) to Le Chatelier's principle, pressure will have no

1 molc 2 moles effect on this equilibrium. In general,
Here, the forward reaction occurs with in-
crease in sumber of moles. Therefore, the back-
ward reaction must Proceed with decrease in
number ofmoles.Ifnow the pressure onthe systcm

combination of NO, molecules to produce NrOo

i.e. suppresses the dissociation of NrOo into NO2.
NrG)+3H2G) +2NH3G)
ConverselY,
Suppose the reaction mixture is enclosed in a
decreased, the eq
direction which is
number of moles. In other words, decrease in pres-
sure favours the dissociation of NrOn i.nto NO2 i. ,
increases the dissociation of NrOo.
(ii) Now, consider another gaseous reaction
involvrng formation of ammonia. Now suppose the reaction mixture is com-
pressed to half the volune @g. 7.12) i.e. pressure
N, G) + 3H, G) <- 2M:G)
1 mole 3 molcs 2 molcs

4 moles reaction quotient is

{2 tr',{HJ}' 1 [NH3l2 t --
Q"= =?1N,1
{2 tNrl} {2 tHrl}3 1H7=;r'"
Thus Q" is tess than K,. To re-establish the
equilibrium Q"will increase till it becomes equal to
\. This can happen only if [NHrl increases and
place i.e., in tavour of formation of ammonia. Thus, shift in
'higher
the pressure, the better would be the yield [N2l and [Hrl decrease i.e. equilibrium will
of ammonia. the forward direction.
If,
system
that dir
moles occurs i.e., in the backward direction' In
other words, a decrease in pressure will favour the
dissociation of NH, hto N2 and H2. For example, for the reaction
(iii) Lastly, coosider the following equilibrium C(s)+ork) cl zcoG)'
reaction involving tbe formation of hydrogen
'""*.it" a"=ffii1
iodide.
H, (g) + I, (g) a.l zHr (g)
1 mole 1 mole
2 molcs ElIect ofchange in volume. If the volume of a
gaseous reaction is decreased, the pressure exerted
This reaction takes place in either dirsction
6v the molecules will increase Thus the effect of
without change in number of moles. So according
 EQUILIBBIUM _ I
7131

@@ o =N2
, & 88 @ =Hz

*lq
--#
Q =Hr.

GASES AT EOUILIBRIUM AFTER COMPRESSION- EOUILIBRIUM

DISTURBED EOUILIBRIUM RE-ESTAELISHED

w-ould be thc yield of ammonia. Usually a pressure

of 350 atmospheres is employed.

_. (iii) Effea ol Concmtration. According to Le

Chatelier's principle, an increase in the conientra_
tion ofreactants (N2 and Hr) would shift the equi-
librium in that direction in which the reactarts are
consumed i.e., in the forward direction. In other
715. Applications ol Le Chatelier,s principle i,;+-r.r: words, formation of NH, would be favoured.
(A) To Chemical Equilibrla, Le should be continuously
Chatelier's principle is very useful in predicting the
-con- so that oquilibrium shifts
conditions of temperature, pressure and
centration to get higher yields in certain industrial
reactions. A few examples ue given below :
l. Formation ofAmmonia (Eabefs proccss).
The chemical equilibrium takiag place in this
process rs
N2 G)+3H2 G)F- 2NH3 G), AH =-92.4t:r NrG)+o2G) .-2NoG), AH = +180.7kJ
(i) Effect ol Tempemrure. The forward reac_
tion resulting in the formation of NO is endother-

m state. Therefore,
make the process
rature of 750 K is
the leld of NHr, of
course, is less than that at a lower temperature. But
from indusrry poi.ot of view, it is rathei advisible to (ii) Efrect oI tuessure. In this equilibrium reac_
get a poorer yie.ld than to waste time unnecessarily. .
tion, no change in nunrber of moies takes place
Fhely divided iron since one mole of N, combines with one mdle of
achieve the equilibrium r 02 to produce 2 moles ofNO. Hence pressure has
(promoter) is used to incr
no effect on this equilibriuo reaction.
catalyst.
(ii) . (ii) Effeuof Conceatralion. Ahigfcancentra_
ol pressure. It has already been dis-
ffict
cussed above that higher the pressure, grater tion of N, and O, will favour thc formition ofnitric
odde.
7132
l'ra I t, a y's NeQ Couqle Ch'e',miiitrqlfrlD

3. Formatirrn of Sulphur Thioxide (Contact (iii) Efl'ect of Concentrafiort. Formation oI

Process). The equilibrirrm rcaction involving the CO, and Hl is favoured by high conccntration of
oxidation of sulphur clioxicle to srtlyhur trioxide water gas as well as steam'
may tre representetl as : S

2soz k) +()2 G) <------r 2So3 G) + 193'2 k'I princ a

(i) EfJ'ert oJ' TLmperttttu'e. The forward reac- asto c

tion lcacling trt thc formation of SO, being exother-

LeC e
discussed below :
rnic is lavourecl by lrlrv tempcrature in accordance -Water
rvith thr: L,e Clhatclier's principlc. Usually an op-
(i ) I ce Equ iI
Dlun-'{e]tluCtrUqg*
t i rn tr rn temperatu re ol 6'73 - 12-\ Kis used'
Further,
More volume Less Volume
Iinoll clil'icied platinum or vanadium pentoxide
(V2 i)s) is useci as a catalyst to attain the equi- The change of ice into water is an endother-
mic (a heat absorbing), reversible process' Thc
libtium state rapidlY.
reaction involves dccrease in volume i'c' whon icc
(ii) Elfect of Prcssure' The forward reaction melts into water, volume cleclcascs. Hence accord-
lovouii.,g [-he foimation of So, takes place with ing to Lc Chatelier's PrinciPlc,
dccrcasc in number tlf moles' If pressure on the (a) On increasing the pressrtre on this system
systcm is increased, the volume will clecrease cor- in equifibrium, the eguilibrium tends to shift in a
rLspondingly. Hcnce, the total number of moles per tlireition in which volume docrcases i'e' eqtri-
tunii voluml-rvill now be morc than before' Thcre- librium shifts to the right. Thus increasing pressure
lbre, accorcling to Lc Chatclior's principle, equi- l'avours change of icc into water i'c. n.rore of ice
litrrium will shift in that clirection in which decreasc melts.
in number crl rnolcs occurs i.c. in the forward direc- (b) into water is an
tion. Therelo rc,lhe Jonnation oJ' SO ris J'avowed 14' in
ondothcr temPerature
Itigh pre,rxre. Usually, a pressure of 1'5 to 1'7 at- tends to I,he right, i.e' on
rn<lsphere serves the Purposc. increa.sin e ice melts into
(iii) Effect o|Concenlratiott' Highcr. the con- watcr.
ccnLrition of SO, and 02, greator lvould be the (ii) Water'Vapour equilibrium -Vaporisa-
tion of water
-e
yiclcl ol SOr.
4. Brlsch Process lilr the Manulacture of \lhtcr * HeaL <-^ Water vaPour
Less volttnte Morc volunte
Hydrogen. In this pr()cess, H, is produced fiom
Thc change of water to rvater vapour is a
water gas and stcan according to thc following reversible endothermic (heat absorbing) process'
equilibrium reaction: The reaction involves increase in volume i'e' whcrl
H,k) +Cote) +H2ok) = ^ water vaporises into rvater vapour, "'olumc in-
---.-v--Water
Steanr
gas
creases. H"nc" according to Le Chatelier's prin-
ciple,
3 nroles (a) On increasing the pressure on this system
in cquiiibrium, the equilibrium tends to shift in a
: direition in which the volume decreases i'e' eqtli-
,2Hr(8) + Coz G),; AH + 42'0 k'l
librium shitts towards condensirtion of watcr
3 nroles vapour into water. In other words, the increase in
p.tt.t.tt" favours the condensation of water vapoul'
(i) Effcct of Tbnryerurure' The fr-rrward reac-
into u'ater and clccreasing prossure favottrs
tion Ueirig enclothermic is favoured by high vaporisation of rvater into water vapour'
tcmperatuie. Ustrally a tcmperatur e of' 67 3-7 23 K
(b
is used.
vapour
(ii) Efl'ect of Pre,ssure. Since thcre is no change
tcmPer
in tlrgtota"Lno.[',.. of moles in this revsrsible reac- on incr
tion,l.zz.r.stirz llus rut eJJ'cct ot this equilibrium reac-
into watet vapour.
Lion.
 EQUILIBRIUM _ I
7133
(iii) Solubility of Substances. Certain salts sure is
like solve with the absorp- piston,
tion The solubility of suih refore,
salts in temperature. means
On the other hand, certain salts like sodium that.increase of pressure increases the solubility of
hydroxide, calcium acetate etc. which dissolve with gas in liquids while decrease in pressure lowers it.
the evolution of heat, will have lower solubility at For example, an aerated soda water bottle like
higher temperatures. Campa, Thums up etc., on opening bubbles out
(iv) Gas-Solution System. Suppose there ex- dissolved carbon dioxide as pre.su.Jis decreased.
ists an equilibrium between a gas and its solution in

::l;:::::::r::::i:::::::::::::ii::::::::::::::j:ii;i:l::il:::l:::j:::::i::i:ri.i:::::::::::::::::rr:r::j::;:::::::j

A,P " :' , ::K,'N,.0W,L,EIDI@,.E I

iiri:i:l: L van't I{off equation is

dlnK, AIl"
7r- - *7
Assuming aH' to be coDstal)t over a smatl temperature range, integration of the above equation gives

10,,ry=l*B,,
)
on. I a-r
-"--J
," =

or lnKr:-#*,
where I is constant of integration. Thus a plot of ln K, versus 1/T gives a straight lirre with slope
= - AI{',2 R.
ii:;i:'i 2. From the van't Hoff equation,

, _Kz AH /Tz-Tr)
,oB
Rr Z:30tR we may conclude that

(r) rf
t-rtj,
= 0 r.e. no heat is evolved or absorbed in the rea tion,
^H log (K2lKt) : 0
i.e. K2/\ 1

or IQ=Kr
i.e. equilibium. conttant does not change wilh tem.perature

0i) IfAH = *ve i.e. heat is absorbed in rhe reaction, then

log (I!,2K,1 = +ve
or log K, > log K,
or I(2, Kr.
i-e. equilibtium conytant increayes with increase in temperahtre.
(rrr) If AH : -ve i.e. heat is evotued in the reaction, log (K,zK,;
= _vs
i.e. log Iq < log K, or & . Kl
i.e- equilibrium constont d.ecrcarcs with increase in tenpraate.
7134
Pradeep's

C'o
i , I::::t
N ue-str..iQna
:::ll::ll;i i:::l:ilitiiii:::::i::::::ll::::::l::li!lit::::ilii:i::::::::iii::il::ili::i:i::::::i

if any, do you
sugar is addetl into a saturated solution of sugar in a beaker- what process/processes
' L some
Q.
expect tJhappen with the passage of time? yghat is this state called ?
take place at equal rates. It is called a state
Ans. Ttro proceses namely dissolution and precipitation will continue to
of equilibrium.
1j - Why gas fizzes out when soda water bottle is opened ?
pressure' On opening the bottle, the pressure tends
Ans. The amount of the gas dissolved is very high due to high
to decrease to atmospheric pressure. Sb th1 solubility decreases i'e' the dissolved gas escapes out'
between acetic acid and ethyl alcohol attains a state of equilibrium in
an open vessel but
- -r, Reaction
e.
decomposition of CaCO, does nol T[h]?
and water are also liquids but one of
Ans. Acetic acid and ethyl alcohol are liquirls and their produ_cts ethJl acetate
the products of Oecomposition of iCO, is gaseous (COr) which escapes out and the reverse reaction cannot

occur.
and pr.oducG remains constatrL Does it mean that the
e. 4. At equilibrium, the mass of each of the r.eactants
reaction has stoPPed ? ExPlain.
wall as backrrard directions but at
Ans. No, the reaction does not stop. It continues to take place in the fonuard
as

equal sPeeds.
Q.5.Whathappenstoareversiblereactlonifocatalystisarldedtoit?
both the rate of forward and backward
Ans. The state of equilibrium is not disturbed but is attained quickly because
reaction increase to the same extent.

Q. 6. The value of equilibrlum constant

depends on what ? (B'I'T Ranchi 1990)
Ans. The value of equilibrium constant depends upon (i) nature of the
reaction (ii) temperature'
cylinder litted witn an air tight piston contains a small aDount of a liquirl at a fixed temperature' The
- 7. Apiston
e.
is moved out so that the volume increases'
(a) \ilhatwitl be the effect on the change ofvapour pressure initially
?

(D) Hor witl the ratcs of evaporation and condensation change initially ?

flnally anil what will be the hnal vapour pressrrre ?

(c) \ilhat will happen when equilibrium is restored
(N.c.D.R.T')

Ans. (a) Initially the vapour pressure will decrease'

vessel. (discussed in unit 2 under
(b) Thera Dritant temprature in a ctosed
,apour pr tion will d6crease because there are fewer molecules per unit
volume in r of collisions per unit time with the liquid surface decreases.
The final vapour pressure will
(c) when equilibrium is restored, rate of evaporation = rate of condensation-
be same as it was originallY.
expressions for the equiltbrium constant K for each of the followlng
reactions :
Q. ti. write
(r) 2Nocl (g) + 2 No (s) + cl2 G)

(ii) Narcor(s) + so3 @ +*o, G) + Narso.(s) + co2 (s)

(rr0 PbI2 (s) + aq <--r Pb2+ @q) + 2t- (aq) (N.C.D.R.T')

(s)12
Ans. (i)K= lNo lclz G)l
,r

lNocl G)'
[NqSoo (8)l ICo2 G)] lcoz G)l Pcoz
(,,) K
1N,pq 1r;1 tsoz G)l lo,itglr/z

,,,0 * = IlElffi{tti#tr = rpb2+ @s)nt- (aqf

 EQUILIBRIUM _ I
7135
(.J The concentrotio[ quotie[t ofa reversible reoction is Q, and the equilibrium constant is K. Wh{t do yon
' conclrde if (i)Q=K (irQ>K (rir)Q<K.
Ans. Refer 10 page 7/11.
1-r i i' Jf concentrfltiotrs are expressed in moles L- | and pressures
in otmospheres, whflt is the ratio of Kp to Kc
for the reaction 2SO2G)+02Gt) $ 2SOr@)at2fC?
Ans. Ara = ftp - nr= - 1.
Hence Kp=K6(RT)-l ot Kp/Kc= 1,/IrT=0rE;;2e8 =0.0a
i.) I i, The eqlilibriuh constsnt for thc reactioDs
Nz + ()2 2N0 and 2 NO + 02 -- 2NO2
are K, nnd K, respectiiely,
--r then what rvill bc the equilihrium constart for the rcaction
N2 + 2O2 <-------r 2NO2 ?
Ans, For the required reaction, K = Kt , &.
(J I I For the rcaction N2 G)+-r H2 G) : 2 NII] G), ar 400 K, Kp = 41. FiDd t}e vrhrc o[Kp for ench ofthe
follording resctio[s at the snme temperature :

(r2NH3G) N2G)+3rr2G)
<- (ii)
; N, G) +
] u, rsy .=,. NH,et
(iri) 2 N2 G) + 6 H2 G)
+ 4 NIt3 G) w.c.E.R.T.l
t-
Ans. (i) Ke = (x) tAT (iii) {a I )r.
41
(l I-1 What doqs the eqrilibrium constart K < I indicate ?
A[s, Thc reaction does Dot procecd n]uch in the forward direction.
Q l'l
For an exothermic reaction, what happehs to thc equilibrium constant iftempernture is increased ?
Ans. K = kl / kt.ln exothernlic reactlon, with iocrease of ten'rperarure li6 iocreases much nrore than lil. Hencc
K
decreases.
(.) I 5. Writc exprcssions for K, nnd K. for the retrction CaCO3 (r) i:. CuO (x) + CO2 G),

Ans. K" = lrtr*ffig, lirkint acrivc masscs of solids as uniry, q = lco, E)1. sjmi tady Kp = pcoz.

(J (,. The equiliDrium constart lNHsl'lorls

1
expression for a Eas rcaction .i"*-
--.-
lNol{ l1l2ol5
Write the bnlonced chemical equation corresponding to this expres-sion. (N.C.E.R.T.l
Ans. 4 NO (q) + 6 H2O G) ,l NH3 G)rs 02
E)
(l lT Whflthappers -)
to theequilihrium pcls (f) pcl3 G) + Ct2
-.= G), if nitrogen gns is added to it (i) at
constaDt voluhe (ri) at constaDt press re ? Give rensons.
Ans. (i) Tho state of equrlibriu nl rentains unalfectect
(ii) Dissocation increases (r'.e. equilibrium sbifLs tbrward) For reasoD, refer ro thc text (page 727).
l'' ls TI. .quilibrium constant ofa reaction is 2 x 10-3at2SoCanrl2 x l0-2 at 50"C.Is tle reaction exothernric
or endothermic ?
Ans' ds equilibrium constaDt has increased\,Jith ten]perature, the reactro[l ts endothern]ic(in the.fon\ard
(.) l" direction).
What two chnnges on the equilihrium Nr@)+3H2G) 2Ntf3G), All _ =_92.4U.
coD keep its strte urdisturbed ?
Alls' Increase o_f tenlperature alontwith suitable rncrcase of pressure or increase of pressLrre alongwith surtablc
increase of tcmperature.
7136 Pratlt'tl,'s Ncttt Course Ch"orittry lffi
Q.2t). some pnocesses ane given helop, what happens to the process if it sulriectcd to o changc given ln the
brackets ?
M. P(
(i) Ice rulhtet (Pressure is increased)
(ii) Dissolrtion ofNaOH in wat r (fernperature is increosed)
->
(ir4 N2 G) + 02 G) + 2 No G) lto 7 kJ (Pressure is increosed and temperotrr is dccreased)'
-
Ars. (i) Equilibrium willshlft in the forward drrectloD t'e. morc of ic will melt.
(ii) Solubilrty will decrease because it is an exothermrc process.
(ili) pressure has no effect. Decrease of teotperature will shift the equilibrium in the backward direction.

Q: I Explaitr why pure liquids ond sotids are ignored whilc writing the equilihrium colstant exPression.
(N.C.E.R.T)
\o of mols= Mass/nrol nrass
Ans. IPure liqurd]or IPure solrdl = ffi;;i t- --fiffi

Asdensiryorapurerio,,..,;,:ffi;,I,ll,,,T.,iln=.,llffH,atureandmolecularmassisarsocoosranr,
thersforc their molar conggntraticDs arc constant and included into the equilibrium constant.

e 22- Whot q nlitative ihformation cnn you obtein from thc msgritude ofequilibrium constoEt ? (N.C.E,R.T)

Ans, (i) Largc value of equilibrium constant (> 103) shows that foruard reaction is favoured t.a coDcentration of
produots is much larger than that of the reactants at equilibrium.
(ii) lnterDediate value of K (t0-3 to 103) shows that the co[centration of thc reaotants and products are
comparable.
(iii) Low value of K (< 10 - 3) shows that backward reaction is favoured ia crmcentration of reactants is much
larger lhan thal of the Products-

Q. l-1. The following reactiotr hos attained equilibrium

CO (g) + 2fl2f;) + CH3OII G), AH' = - 92 0 LJ uol-r
Whot will happtr if (i) Volume of the reaction vessel is sudde[ly rcduced to half?
(ii) the portiol prssure ofhydrcgetr Ls sudderly douhled ?

(iii) an ltrert gas is added to tbe system ? (N.C.E.R.T)

tcH,oHl Por.oH
\= p*i4
(i) when volume of the vesselis reduced to half, the conoentration ofeach reactantor Product becomes double
'llus
2 tcH.oHl
o"=
rrcorxffi;F=;K'
As Qc < Kc, equillbrium will shift in the forward direction, producing more of CII3OH to make Qc = Kc'

Por.ox - 1

(i0 op = pco x 1z p:H,f = 4 Ko.

Agaio Qp < Kp, equilibrium will shift ln the forward directioo to nlake Qp = Kp.
(iii) As volunrp remains constant, ntolar conceltrations will not chaDge. Hence there is no effect on the state
of equilibrium.
 EQUILIBHIUI\4 _ I
7137
Q l'l which oftbe following will be affected by increase of pressure ? Also mention whetherthe chflDge1rill cause
the reaction to go into right or left direction ?
(, cu4 (a) + 2 s2 G) -==
CS2 G) + 2 rr2s G)
(ii) co2(9 + c G) i=----r 2 co (s)
(iii) 4 NHj G)+s 02 G) s:= 4 NO (t)+6 H2O G)
(iv1 c2Ha@) + lr2 G) \-\ C2li6 (g)
(N.C.E.R.T)
ADs. N l except (i) will bc affccted by presswe (Fot (i) np = n. 3,
=
ln (ii), n, = l, np = Z i.e. tp > nr equilibrium will go to left.
lD (iii), nt = 9, np = l0 ia ,rp > ,,, cquilibrium will go ro teft.
ln (iv), n, = 2, n, = 1 L e. n p < h /. egutltbrlunt will go ro right.

Q 25 Hydrogen gos is obtoined fmm nfltnral gos by portial oxidation wiih stecm occordiDg to thc tbllowing
cndothermic reaction
CIt4 G) + Hzo G) Co G) +
+ -r H2 (3)
(@) Write lr expression for K, for the above reaction,
(rr) I{orv will thc value of Ko and composition of the cquilibrium mixhtre bc offected }y
(i) increasing the pressure ?
(ii) increflsing the tetnpemture ?
(iii) using a catalysl ?
tN.C.E.R.T)
Pco x P3y-
Ans. (a)xp =FA,l.r.r
(r) (i) By Le Chatetier,s principtc, equitibriuDr willshifr in rh backward direcrioD.
0'l) By Le Chatelier,s principle, cquitibrium willshifi in the backward directiorl
( l) Equiiibriunr conrpositioD wilr not be distu rbed bu t equirib.unr will be ar raincd quickry.
Q 2(r The following system is in cquilibriuh
so2cl2 + Heat
i_ SO2 + Cl2 ,
Whllt rvill h.PpeD to the temprnture ofthc systm ifsome Clz is odded into
it at corstant volume ? (; iYe reasorl
Ans.'ltn)pcrature of the slsteD will increase bcuse on adding cl2, equilibriuDwillsbift
iD the backwit rct direction
producing more heat.
(.). 27. ln which one of the follorying reactionln thc
)ield of thc prcdoct wi be maximum ?
2A+B + c,K= 10-5
c +2D <- E,K= los
D +38 \_J F,K=ld
r\ns' Higher lhc value olcquilihrium conslant K, greater is the yield ofproducts. Henceyield ofE will bc nranimunr.

Q lS Thc e(tuililriu. H2o (4 ---\

s H2o (r/) is athitred ir a cro.ed contailer ot 40oc. The aqueous reDsio[ of
watcr ltt 40o C is 23 mm. What is Kp for the sai.l equilihrium ?

Ans. Kp = pH2o = 23 ntnl

/
7138
Pra tl e e p's N ellt.;: Cinrre Chi,i m istr4 WD

, ,Llyg hg rt Angwer Quegliong cAhnlua'i :hrlARK

Q.l.Whichmeastrrablepropertybecomesconstantinwnter
temperature ?
Ans. Vapour Pressure.
Q. 2. Give one exnmple of everytlay life in which there is gas <- solution equilibrium'
furs. soda-water bottle.
Q. 3. Unrler whnt condition, a reversible Process becomes
irreversible ?
Ans. If one of the products (gaseous) is allowecl to escape out (i.a. in open vessel)

Q.4. What happens if ferric snlt is added to the equilibrium of the reaction between [e3* and SCN- ions ?
Ans. Red colour deePens.
Q. 5. Wrat is the effect on the value of equilibrium constant on adding cntalyst ?

Ans. No effect.
Q. 6. Write the expression for equilibrium constant
K, for the reaction
3 Fe (.s) +4 uzO G) + IerOn (s)+4 u2 G)
Ans. K, = pHr/ pH,o.

Q. 7. What is ttre effect of increasing Pressure on the equilibrium

N, + 3lI, a--.---l 2NII3 ?

Ans. EquilibriuDt will shift in the forward clirection fornriug more of ammonia'
Q. lt, lurat are the conditions for getting maximttm
yield of NfIr by Haber's process ?

Ans. lligh cot]centratiol'ls of N, and H2, low tenlperaturc, high pressure'

constant for the rcverse
e.9. If the equilibrium constant lor a reaction is 4'0, whut will be the equilihrium
reaction.
Ans. 1/4 =0'25.
into it nt the same
e. 10. lvhat happens to the dissociation ofPCl, in a closed vessel ifhelium
gas is introduced

temperature ?

Ans. No etf'ect.

5,-h,,o,,r,t,,fi n e w Ir Q u.9 st \?,n,?,,,,

c An nvt xc 2' o r 3
"M
AR KS

\ r.t l.l l. What clo you understancl by ternr 'Equilibrium' '? Explain physical equilibrium with one suitable
.
ro 7 -1. exan:ple.
2. Give one exanrple of each ol the following equilibria :

(i) Solid-Liquid Equilibira

(ii) Liquid-Gas Equilibrium
(iii) Solid-solution IJquilibrium
3. Deflne the terms'Vapour pressure ancl 'Solubility''
4. Define Henry Law. Why the gas lizzes out when a soda water bottle is opened ?

S.Unrjerwhatconciitioneachofthefollowingequilibriacanexist:
(i) Solid-Liquid equilibriunr
(ii) Liquid-gas equ ilibriu m
(lii)Solici-solution equilibriu m
(iu) Gas-solu tion equilibriutlr'
 7139
EOUILIBRIUM
- I

\cr ' 1 6. What do you u[dcrstand by Rerversible aDd Irrcversible reactions ? Iluskate your answer with two
examples. Under what conditions a revcrsible reaction becomes irreversible ?
7. What do you understand by chemrcal equilibrium? ExplaiD with orle suitablo example.
t. What do you understand by dynamic nature of chemical equilibriuD ? Give one experiment to provo
that equilibriunr is qnanrc in nature.
9. List any tbur important characteristiG of a chemical equihbrium.
\,i ri 10. State and explain the Law of Mass Action.
\,( l6 11. State aDd explain the'Law of Chemical Equilibnum.'
12. Derive a Seneral expression for the equilibrium coostant.
i!( r1. 13. Whatdoyou undcrstand try Kc and Kp I Derive a relationship between ihem.
14. Under what conditions Kc K, for a gaseous reaction 'l
=
s!r. 7.s 15. List the importa[t characterlstics ofequilib uD constant.
16. Hou does the magoitude of equilibrium constant give an idea oI the relative an]ounts ol the reactants
aDd products ?

17. The equilibrium constant for the reaction

N2 + 3I{2 + 2NH3
is K whar will be the equilibrium constant for the reaction
t1
jxr* jH, # NH3?
Srr tr, lt. Discuss the effect oftenrperarure on the equilibriumclnsra[t. Ho\xdoes it change for (a) exothermic
rcactioo (b) endothermic reaction (c) reaction having zero heat of reaction 'l
Sre 7l(i. 19. Define 'HomogeDeous Equilibria and }leterogeneous Equilibria'. Give lhree cxamples ofeach of
them.
Sr., l ll 20. Write lhc equilibrium coDstant expression for the following reactions:
(t) HCI (a4) + H* (oq) + Ct- (ott)
(,t) NHj (dq) + NHl+ @O + oH (a4)
(i'r) Ag2CrO4 (r) + (o9) Za!+ @4) + cfi1- @q)
=:f
(D Ar (r) + 3H+ (oq) A1'* (a9) + 3 / 2h2(E)
=-
(v) CH3 COCH3 (l) a-------r CHTCOCH3 G)
21. Applying the law of chcmical equilibriunr explarn whyvapour pressure ofwater is consrant at coDstaDt
temperature.
5r'c I ll 22. Why strictly speaking equilibrium coDstant has no uoits ?
5, ( .I.1 23, '[he cquilibriun] constant for the reaction.
rrr : ri. 2H2 G) + O2$) + 2H2O (g)

is 1.2 x 10o at 298 K,:a quite Iarge while H2 and 02 do not react under ordinary coDditions. IIow
do you explaio it ?

24. What is theeffect ofaddinga catallst or a reaction which is (a) io equilibrium (b) Dot in equ ilibrium ?
25. What is the cftbct ofaddrng I mole of He (g) to a flask containing SO2, 02 and SOJ iD equilibriunt ar
coDstaDt temperaturc ?

26, Name the factors which iofluenc the equilibriunl state. Explain iDflueocc of each tactor with the help
ofexamples.
27. State Le Chatelier's principle. Givc two examplcs of its applications in chemical industries,
2t, The follolving reprcsents a gaseous system at equilibrium.
2SO2 G) + oz G) + 2SO3g)+ Heat
IDdicate the direction in which the equilrbriuD will shift when rhe following changes are nradc :

(i) 'Ibmperature ofthe s) rtem is decreased

(ri) Total pressure is decreased
7140 Pra d e e i
p' s,iN iA,'.,,' i*;,,', C,ii,ir|I Siii:ryT,

Qii) Volume of the container is increased

(iv) A catalyst is added.
29. What is chemical equilibrium ? How does Le Chatelier's principle enable us to predict the effect of
change in external conditions on a systenl in equilibriunr ?
30. Consider the tollowing reaction
Nzo+(c) 2No2G) AH =58'6kJ
=+
What will be the effect of the following changes on the concentration of NrOo at equilibrium l
(i) Increasing the pressure
(ri) Increasing the temperature
(iii) Increasing the volume
(lv) Adding more NO, G) to the system without changing temperature and pressure
(v) Adding catalyst.
31. What will be the effect of increased pressure on the following equilibria ?

(,) H|G) + rz?) <----S z}lr(8)

(,,) Nz G) + 3Hz@) <- 2NH3 G)

(iu) 2ot@).^ 3ozg)

(v) Nz Or G) # ZNOr lg;
32. Using Le Chatelier's principle, predict the effect of
(i) decreasing the temperature and
(ii) increasing the pressure on each of the following equilibria :

A. Nz G) + 3Hz(6l) a---i 2NH3 G) + Heat

B. Nz G) + oz@) <- 2NO (S) + Heat

C. H2o (f,) + Heat $ HzG) + lorO,

D. zCO(9+oz@) ?CO1G) + Heat
==:
ifthe concentration ofC is increased ?
34. Mention at least three ways bywhich the concentration of SO, can be increased after the equilibrium
is established in the following reaction :

2SOz@) + o2G) <- 2SO, + Heat

35. What is Le Chatelier's principle ? Under what conditions is it applicable ? How does it cliffer from the
Law of Mass Action ?
36. Why does manufacture clf ammonia by Haber's process require higher pressure, low temperature,
use of catab/st and pure gases ?
37. State Le Chatelier-Braun principle. Discuss its application in the nranufacture of NFI, by llaber's
process.
3lt. With the help of Le Chatelier's principle, explain the following :

(i) Effect of temperature on the solubility of sugar in water, given that dissolution of sugar in water
is an endothern:ic process.
(ir) Effect of temperature and pressure on the solubility of gases in liquids.
(iii) Effect of pressure on the boiling point of a liquid.
(iv) Effect of pressure on the freezing point of liquid.
 EQUILIBRIUM I 7141
-
CARRYING 5 or more MARKS

srt.7.1. What do you understand by 'Equilibrium' ? Discuss one example of each of lhe followiDg physicnt
lo 7.3. equilibria:
(i)
(r)) Liquid-gas equilibrium
(iii) Solid-solutioo equilibrium
(rv) Gas-solu tion equilibrium
Give one importaot characteristic ofeach of the above equilibria.
Scc. 7.{. ,- Briefly explain the foll@ing :-
(i) Reversiblc and Irreversible reaction
(ii) Dynamic nature ot chemical equilibriuDr
3. Briefly explaio the important characteristics of chemical equilibrium.
S('c.7.5. 4, State and explain the Law of Mass Action. Derive the Law of chemicalequtllbflum and heoce define
1o1.6. equilibrium constant.
Scc.7.7. What are lq atrd ? Derirc a relationship bem,ern them.
\
Sec.7.E. 6. Erplain the effe{ of the following on the equilibrium constant.
to 7.9. (i) Concenhations of the reactaots are doubled
(ii) The reaction ls reversed
(rir) Catatyst is added to the rection
(rv) Tbmperature is iocreasd.
Scc.7.l0, 7. What are Horrogencous and Hetetogeneous equilibria ? Give three eEmples ofeach. rr\'trite expres-
lo 7.12. sions for their equilibrium constant and give its units in each cas.

Sec.7,l1 8. State and explain Le-Chatelier's principle. Discuss its application to the manufacture of
to 7.15. (i) NH3 by Haber's process
(ri) H2SO1 by contact procEss

t
 Cnlculntion of degree of dissociation from voPotlr density measurements
Degt eeof rlit,tociation of a fibrtance at a particular temperahie is defned ot lhe lraclion of the tolal numbet
of noleatler di.tsociated into impler molecules ol that Pshiculor lemPeruite i.e-
No. of moles dissocialed
l)e8ree ot dtssocratron (.) = ToGl-;;l;f;;ks r;I;;
Degree of dissociation caD be calculated fromvapour density measurements for ihose substances which are
accompanicd by cbange in the number of moles e.8.
PCl5 + PCb + Cl2 or
N2o4 <-
2 NO2 etc.
'fakiDg the example of dissociation of PCl5 , suppose we start with 1 mole of PCls and a is its degree of
dissociation at the exepenmental temPerature. Then we have
PCt5 G) PCl3 G) + cl2 G)
<_------r
No. of n]oles before dissociation I 0 0
No of moles after dissociatioD 1 'a
Suppose thevolume occupied try the vapout per mole = v litres. Then
Before dissociation, 'Ibtal no. of ntoles = - I lence total volume = V litres. If D is the vapour density of
'l

PCI( before dissociation (calle\l theoreticoI t oPour dentiily),lhen

D"+ ( 'oensrtr"c*,"" (!)

Alter dissociation. Totalno. ofmoles =(1 -.:)+.r+a=l +a

.. Totalvolume occupied by the reactioD mixture = (1 + r:) v litres
Now, if d is tbe density of the vapour (called obse1ed derltity), the|tr
a
,t
" ,1+,rlv "'lii)
Dividing eqr. (t) by eqn. (ii), we 8et

D+-D
7=-r= t +,t ot a=7- |

C+afV
D-d
o=--T- ...(ii )

7142
 EOUILIBRIUM
- I 7143

ADDITIONAL UgEFUL lNFORMATlONcont.d

As Mol. mass - 2 x Vapour density, eqn. (iii) can also be written as
M,-14
a= --Mo _.(iy)

where M, = theoretical (calculated) molecular mass

lv{o = obsrved (experimental) molecular mass

Al ternatively, observed molec,ular mass can be calculated from the mass of a definite volume ofthe vapour
at a particular temperature, using the relation
pv-#Rr or M"=iS ("", =#)
In case ofdissocistion ofN2Oa , we can write
N2O1(t) \-r 2NOz e)
No. of moles bcfore dissociation 1 0
No. ofmoles after dissociation l-.I 2a, Tota!=l+ d
Henc the same formulae will apply as for the dissociation of pCIs .

In genernl, ifone mole dissociares to give n moles of products

ie.A+nB
IDitialmoles 1 0
Moles after disso. l-a nd Tb[al = I -a+aa= I + (, - 1)a
rhen 3=r*r-t)a ot a=*(+)

"'
;";.;;;;;,,:,',,,,;;r
lound to be 70.2. Find the of
degree of dissociation PCls ar I olm weight 2'695^,;;,;",i,;.":,;;,)l),:,.,"0
g Colculatc the perceruage
PCls at this ,empratun. dirsociaion of pCl, at 523 K
Solution. -fheoretical vapour density of PCls is Solution, Applying the relation,
Mot. mass of pcls
5 x 35.5 pV _
^ 3r + RT
"=--------z-=------z_- #
2o8 s Mo=#=269sx9!q2lx523-,s.7
= --T- = toq zs
d=70.2 For PCl5 Mr =31 +5 x35'5=208'5
observed vapour density is, '
.. Degree ofdissociation (a) Mr- Iv{o ZOA.S - 115.7
tL.I-ru-rlo.2 " a=--E-=----ll3--r-=u ^ Eo
^^
= =o.ss = aO%

1. f! 3 celai! tempcrature, the vapour densiry of 2. I 588 g of N2O. givEs a total prdsure of 760 mm
.

N2o.is24.8. Calculale ils pcrcntage dissociation *l.n

finiatti oiooclated i|I I5OOmlvesselat 298.
at this temperaturc. K What is its degree of dirssiation at this
[,rn". E5.5%] tcmPeraturc ? l,{r)s. 0.1tgl
7144 l'radecp's Neut Course Chemistr4lfiffi

C, tl,S, 8,. P, A,l,T. ( ltl AIATSJ S PE C I A L

A. SUEIECTIW QUESTIONS 2AB2 g) + 2AB (8) + 82 E)

Q. I. Prove thatthe pressure necessEry toobtain S0 Initial 1 mole 0 0

dissociatlon of PCl5 at 500 K is nuEerlcolly Atcquilibrium ! -r 2x x
equol to thEe tlrDs the velue of the equlllbrlum Tttal numbr of moles at equilibrium
corctong Kp. = I - t + 2r + t = 1+ 2,
Ans. PCls <--s PCl3 + Ch 1-r
P At\ = t + 2x- x P
Initialmoles 1 0 0
05 05 2, --
Molesateqm. 1-0.5 ^ - I +2,r^,
rAB
'Ibtal = lsmoles
=0.5 xt'
If P is the total required pressure, theD Pnr= ;7
rr.,, = H " r = !, rrr, = S' n=
|, .. P-oox Pa,
.\=-._;-
ror=$'r =| " ABz
.. PPdrx Pct, t,/3\(P/3t P
" trl= ppo, =--lI71;=1
= (+#)'. (+++) (i;i,.)'
alp
or p=3Kp. or \ = ir=r6+ zo
Q. 2. Show that the degre. ofdissociatior (a) for the Neglectingr in comparison lo unity
dissociation of PCls into PCl3 atrd Cl2 ot pres'
Kp =
-
+Jp or ,= /lq )'"
surepis [oE
giyen by
"= Q l Glvin8 rcssons in brlef iDdicate whether the
,J

[#h)"' following statment is TRUE or FAIJE :

Ans. PCIs + PCl3 + Cl2
The rate of ar exothermlc raction increases
Initial moles 1 0 0 roith increasitrg temperature. (I.I.T 1990)
Moles after dilso. 1-d d a, Total =1+ c Arls. hlse because in an exothermic reaction, heat is
evohed. Increase of temperature will shift the
,. pro, - fi * v, p,., = # x P, lq= fi;, Y equilibrium in the backward direction ie. the
rate of reactioD decreases.

_-
rt=
ppor, po, (#,')(#"i ;P Q 5 Whst is the effectofreducinB thevolurDe on the
= p"o, l-a' srstem described below ?
2c(s)+ o2E) + 2CO(8)
or 1r -a215=azY (B.I.T Roachi 1990)

t _- ,t/2 Ans. On reducing the volume, tbe Pressure will in-

crease. By Le Chatelier's principle, equilibrium
or (p+Kp).2=qor"=t"e] will shift to the side accompaded by decrease of
pressure r'.e. decrease in the nuntber of Saseous
Q.l At tempereture 1 6 conrpound AB2 G) dis-
moles r'.e. backward direction.
socistes accordiDg to the reactlon 6
Q Nitrogen nnd hydrogen recct to form ammoniA
zAJz + 2ABG) + B2G)
as per the reaction
with a degree of dissoclation, r, whlch is small l/ZNrtjtzll, Nll3
compnred with unity. Deduce the expressloh for
When the mixture ofthe-three gases is in equl-
, in terms of the equilibrium const{nt' K, and lihrium, predict whether the arnottut of am-
the total pressure, P monia increases or decreases iI
(I.I.T Ie94) (i) the ptess[rc on the system is increased.
 EOUILIBRIUM I
- 7145
(r, th. tcmpqatur! ofth. E6t m ls rofu.d. As prqalure is kept constant, volume will in-
(iio thc corccnarotlotr of hydrogn I3 ltrcrcoscd. creasc. Hencc molar concentratoD of NHr, N,
(B.Ll. Rotdti t99t ) and H2 will decrcase. As there are two concentra-
ArLs. (D Wbcn pressurc is iDcrcasd, equi[brium siifrs
tion tcrms in numerator aDd four concentration
to that dhedioo in t}lliclr pres$re decrEses ia
terms in the denominator, to keep Kr constant,
number of mohs decre8s sfii:h is in thc ftrilard
direclion. HeDce tlrc amqlnt ofNH3 increalEs. decrease in NH3 shouu & morc ie. equihbrium
(u) As the fon\ard reactir b mlhqmiq iDcrease will shilt in thc baclaud ditection
of tem[Eraturewillshift lbe equilibrium in ]be bck- Q. I: At o pordculor trDrperatur, th number of
v.ard directim i. the armunt of NH, dcqEas. Dolcs of dlffercnt cotrsdtuctrts lor th. reactlon
(iii) On increasing the concntration of H2, N, + 3 Hr <::i 2 NH, {rc (r - a) for Nz,
3 (l - a) lor II2 &Dd 2 a for NIfr. Finrt out
equilibrium willshifr in the forward direrrion ie \ ln
the amount of NH3 iDcres!.s. t rDs ol a oDd th. totsl prcssurt- Show thot a
trlll lrcEeEG r'lth thc lDcrlnse of tb aotal pr6-
Q 7 Express XD ard K. for the rrsctlor surG- Assu[G thst a << 1.
N2 6) + 3H, G) i-------\ 2NHr G) (ttcd B6pt I.E.E. Z00t\
rrvhnt is thc Elstlon bctrv.er th6. cqulllbrlum Atr& Nz + 3 H2 \---.----r 2 NH3
constaDts for thc obovc rcsdlon ?
Moles at l-a 3(1 -a) 2o,
(1.5.t4. Dhqnd Dgt) eqm. T&[al=4-zd=2(Z-d)
Ans. u IM:P ,, rzrix3
hr- #52
^"-fNrlH;P'
"=
Ltt =2 - (1 +3)= -2
et j6' P*r, - zi\, ^r=ffi2
- x, = q lnryan = I(6 (RD-2 - Iq,/ (RD2 ,ft-,,
Q.8. A rcrcdor AG) + B 6) 2 Ce) k in L. hr.l4
=::f
cqulllbrluE ot f, c.rttltr tcEpcrrturc. C{B rr
lncreoao the emouot of Plodrcf! by (, oddlng ozto-otzlp2
co& yst (ii) hcccsiDg prrssnE ? l(t - a)t 2(z - a)lp x teTt -;f / Be --.yl
AIrs. (i) No, because cahlysi does noi disturb the state
_ t6 a212 - a)2 |
of equilibrium. (r'i) No, bccuse z, = nI
9. Thcrcoction N2Ot G)
l(t -;I-P
'Ihking a <<
Q. <-
2NO2 G) is belng t,
corried out ln a closed vcssel st 373 K. Af o 16a2 x (2\2 1
-Ap=------qj-^F,=tFr
64a2
particular insteug concentrotion ol NrOa os
well as NO2 ls I mol L- l. Itr Fhlch dlEcdon the If P is iDcreased, to kecp K? conshnt, a will increase.
reuctlon vill go to cs-tsbush thc Gqullibrlum ? t.r Mcntiotr two dillercnt rvoys ofdrawing the fol-
Tbecqulllbrlutn corstatrt for tb. ]!oction ot373 lowin8 equilibriurn torvsrds rlght
K is 0.36.
II'-
ADs. CrnccDtration quo0cnt, Q (at 3?3 K) CHTCOOH + CHTCH2OH +
tNo-t2 CH3COOC2H5 + H2O (aI are tiquids)
= itr;".1= l' But 4 = 0 36'
(West BenBal I.E_E. 200j\
ThuE to
establish the cquilibrium, e should Ans. (i) By adding more of CH3COOH
decreasc. This can happen if [NO2l decressee or or
cH3cHzoH.
[N2Oal increases ic. equilibrium shifts in the (ii) By remqving the ester or watcr formed.
bachpard direclion. , '' The equilihrium constant for the rractio]r i
Q. 10. ID ttr. FactioD N2 + 3 Hz ir 2NE, ot cqul. r{2 + B,
llbrtunr, gos ls lDJe.ted iDto thc yesscl vithout ==-
2AB is
\. Whet will be the equi-
librium constant for the ieflction, AB i:-
dtsturtlng tie overoll prtssul! ot the qa'tem.
Vyhat Flll b. tt. .trcct on th. cqdlibrlnm ? | +*!ur, [A, B onrl AB, aI are gases]
tNI{-t2 . llYest BeryalJ.E.E. 20041
Ans.K= ' "-
' INzl [Hr]' Ar& For A.2+82---2 AB, equtlibrium coostaot =Rp
7146 NeuJ CoaYse Cl;emistrq

Fi)r the reverse reaction, 2 AB <::.A2 + 82, concentmtion of CO to 0 6 mole by odding CO2 into the
equitibriuD constant = 1 ./ Kp vessel how maoy moles ofit must lre added into eqoi_
librium mixt[re ot conshnt temPernture in order to 8et
( )n drvr(trng b) 2. AB + ) nr - lur, this clrange.
Slrlution. Step l. 7o cakulate Kcofthe rc.Etion.
equrtihriurn (, rnsla,'ll I r'K;
.. ICO G)l lU2 (8)l 0.2 x 0 6
K. = =0 xrl 3-'
lco, Gtl luF)l 4
Ammonium carbamate decomPoses as
NII2COO NII4 (s) + 2 NH3 G) + co2 G) Step 2.To colctthle efrra Cozlo be ad.led

ln,r (losed vessel containing ammonium car- Suppose extra COz to be added = -r nlole Then
hnmxte in eqrtilibri[m, Nll, is added such that the writiDg the reverse reaction, we have
partinl pressure ofNIIS now eqrlals originarl tot[l pres_ COz + II2+CO + H2o
sure. Calculate the ratio of tohl pressure now to the 06 04 03
Initial nroles O2+x
originxl pressure.
after addition
Solution. Suppose the totalpre$sure ofthe mixture
lDuially is P This is due to NH3 and Co2which are Present
2+r-0 2) (0 5-0 2) 0 6 (0 3+0 2)
Moles (Molar (0
conc.)atnew =x =0 4 (Given) =0.5
rn rhc ralto o[2: l. Thus7"r., = i t ,ao, = ] O
equrlibriunr (V = lL)
1 0 ('x0 5
K. =it= Iorr=0 75mole
- K, = (PxH,)2 (Pco,,' = (?r)' (lr) = +r*
Alter adding NH3,pps, = P (Given) I t,)J,!, n 1
Thedegree ofdissociotior ofN2oa into

- a-L NO2 ot ore ntmosPheric pressure nnd 313 K is 0 310.

Pz x pcot=Ko= *P' ot Pco2=frP Cslculate Kp of the dissoclotion rerction nt this
' Total Pressure no\{ =PNHI + Pco2 temperature, Whot rvill be the degrec ofdissociation at
10 atmospheric pressure At the sahe temPerature ?

=P ' ' -- 3l o
+rlt Solution. For the dissociation reaction
27,
'. t{atio of total pressure now to the oriSlnal pres-
N2Oa G) t' 2 No2 G)

3l molcs I
lnilial 0
SUfe =, 2x0 310
Molesateqm. 1-0310
The equilibrium const[nt ofa reaction
(z=0 310,Given)
doubles on increosing the temperAture of the reaction
from 25"C to 35oC. Calcrtlnte enthslPy change of the =0 69 =0 62

retction, flssuming it tobe constontir thistemPerature 'lbtal =0 69+0 62=I3lllloles

rarrSe. At one atmosPheric Pressure,
Solution. Ac.cordin8 to integrated vanl Hoff 0.69 0.62
equati (pat'e ?/16) i"r,rroo = ffi x Iatm pNo!=l.JTx laln]
tK,)2 a Il" ITz - Tr )
rocG\ = r;o'rR fno,
tutting (Kr)22(I$)r = 2,Tt =
[-T-lTr-,J
25oC = 29a K,
*,=ffi (o.t 2/ t.3t attr,2
= o 42sarnl

T2 = 35oC = 308 K pr"rrrr", ,uppor" degree of

At10 atmospheric
It = 8 314JK-1 tnol-l,ue get dissociation = d. Then

rou z :
,^.., a H' (308 - 2e8) K N2O4 2 NO2
-,r8T 3o8T-
=
,Jo3;lil; rK:r;;F ' Initialmoles ----------r
01

or A H' = 52898 J nrot-1 =52 llgt kJ mol-l Moles at eqm. 1-a , 2d, Tbtal =1+d
Prubleh An equilibrium
mixture
x to atm
CO (g) + H2O (g) {r CO2 (g) + H2 (8) Present in nnroo= # 'lo atm' PNo2 = ?f;
:r vessel o[ one litre caPacity ot 1000 K wss found to ,, [20 at 1l + a1]2 4o az 4O az
contain 0 4 mole olCO,0 3 mole ofHrO,0 2 mole of tr? =
ili[=rd=;]=1r= dIT -
+a--7
CO2 .rnd 0 6 mole ofH2' Ifit is desircd to iDcrease the
 EQUILIBRIUM I
- ? 147

.. 4o
l-r,'"z- =o
tzs Zr.lH., x =\pHrs
p x (p + 0.5) = 0 11
NcglcctNe a2 in comparison to 1, 40 a2 = 0.42.5
or p2 + O S p = O 1I
or a=0103=lO37.
or
'' ,,/,, rr . Wlren d - D glucose is dissolved io /r2+ 0 -5p - 0.1I = 0
water, it undcrgocs m[tsrototioh to form tln equi- y'@.sf
libriuh mixture of a - D glrcose and p - D glucose -o s= -+t-n.rrl
conlflining 63.6qa of the latter. Colcrlflte K. for the
mutnrotation. - os t Vo.Zi=i:At
2
S!I]!iq!."- D Blucose s__ P - D glucGe
! Vo;g
At equilibrum 3(,.4Ec 63.6%
_ _ 0.5
2

r"=ffi= r tat = -0
5 !0 83
=
0 33
o trs
!" t,/.lt /,
--=
At77.Cand one atmospheric pressnre, . -i-
PHrs = 0 165 atm, pps. =0 665 atrn
NrO. is 707o dissociated into NO2. WlrBt will be the
volumc occupied by the rllixtrrr uDder thescconditions (Ncglectiug _vc valuo)
ifwe st{rt with l0 g ofNrO. ? / One mole of lI2 and three rnoles of lll
Sohttion. Molar mass ofN204 are injectad in a litrc flask Wtotwill be thc concentrr_
tion of H2,I2 flDd tll at eqrrili}ritlm at 490oC ? Tlrc
= 28 + ()4 = 92 8 not-1 equilibrium constrnt for tltc reaction at 490" C is 4S.9.
NzOl <------\ 2 No2 (M.L.N.R. Allalnhad 1 99 5 )

Initial moles *g 0
Sol[tion. IIu 12 + 2ljl +
9) Initialconc. 1 23
After di$sociation -#l< #
,,]! zxo oi6 moles f.--l
=0.109-0 076 =0.tsz Concs at eqm. O -.) (2-r) (3 ru)
=0 033 nrole L-l
Tbtal n'toles after dissociation
= 0.033 + 0.152 = 0.t85
K = :J+lr)'?
(t -x)(2-x) - e+4L+ l2.r- .lse
'f 2+i_3r
='l']'C ='11 + 273K = 35OK (Gite,t\
PV = 2t{1 o, V=+ . 9 + 4* + 12x =91.8 + 45.ge - :B7..7x
or 4'!.9l- t4g.7x+ 82.8-O
0 185 molc x 0 0821 t. atnr K-1 mol-l
'149.7 ! Y(49.7)2
-4x41.9x82.8
= 5.12 L.
l,tohl(h 7.Some soliil NHaHS ls plocd itr s
flosk - 11e.7 r ITI?lb-0-r=-T-8I7.?s
838
cortanlng 0.5 otm ofNII3. Whotlrorld be thc pItssure
= --li'8-
119 7 ! 92-4
of NH3 and HrS phcn equillbrluD is rcached ? = 2 8e and o 68
NH.HS (r) \-- NH3 6)+Hrs G) , Kr =0.r1 But i=2 89 is impossible. Ijenccr: = 0 6tj.l
.'. CoDcentrations at equiltbriuD.l \\iil be
(M.L.N.R" Albhotu 1994)
H3 arld H2S producd by the decom_ IHzl = t-r= t-0a,81 = 0.316nrot r.-r
position of NHiI{S will be same. Supp6 ar equitibrium
[Iz] = 2- y=Z-0.(,84 =I ;116moll-l
:1_+_!!sfressure = p atm due to decomposition of []lll =i+2t =3+2x0.684
NHaHS.Then p:HS =patm
= 4.36t mol L-t
PNH3 =P+0 5atm ' A hixture of H2 alld 12 (vapour) iD
Applying law of chemical equilibrium io the given holecular proportion of 2 : 3 was lteated tt 440oC till
thcresctiol H2 + 12
reactron <=:= 2[It reache<l equilihrium
7148
Neut Course

statc. Calculate the Percentage of iodine conveiled hto solutioD. +N2O4 G) 2 NO2 G)
III (K. ot 40-C is 0 02). (Bihat 1997) InitialamouDts 0lnrole 0
H2@) + tz (8) <-.------\ zHr G) At equilibrium (0.1 -r) 2x,
lnrtial 2 3 0 moles Tbtal=o l +rmoles
At eqm. 2-x 3-x 2x As P=latm,
2x 01-r b
Molar corcs + + v Pxroo = oiiai, PNor=tl-l +r-:atm'
-. (2t / v)2 pfr",
r{c=iE=t7vJf(3--_r-DlVJ v.? - ------1
pnroo
'-2
= lz-x)lr
---*.-----= = o 02 (Given)
-x) x\z 4]
This oo solvi[8 Sives-r = 0 1615
=ffiot/ 0.1 +
=?0-:1=lt?d +rt
. 7o of iodine converted into HI
'
4?
-o 3 1615xloo=53E7a 0.01 -,r
t\ thtt n ltt 0. 1 mole ol N2O. (g) was scaled in a
4P =0.14 or 4.14f =o.ool4
=
0.01-r2
tuhe under atmospheric conditions {t 25oC. Calculate or x=0018
the number of moles of NO2 (8) presetrt ll the cqui'
.,

.. No. of moles of NOz at equilibrium

librium N2O. (g) \-=r 2 NO2 (g) is reached after
=r(=2tO.O18 =0 036molc
somc time (K, = 0 14) (M.L.N.R. 1997)

INS ) SI?EC'AL
t'rol'htn I 'I\e dqrcc of dissocirtlon of HI ot a 1 (x/2f 4c
particular temlEmture 16 O t Calculsie th. voluEc ol ^c K:- lZ=ifTZ=d - @.4
=
'
t M Na2S2O3 colutlotr rcqulrGd to truhillr. thc iodire l--2-l (--2-l
presDt itr the equillbrluE mixture ol8 rc{ctlo! vhcr 2 4?t2xl2
-iot ,-=2or x=\
mote eoch ol H2 oud 12 ore hettd iu o clmed vessbl of 2 e:;f
litre clpacity,
l. Colculation ol Kc.
Srep
Thust2left=2-i=;mole
Step 3. Catculation of vohune of hypo wed.
Degrec ofdissociatioo ofHI (a) = o 8
zIJt+H2*Iz 2NazS2O3 + 12 ...- Na2S4O6 + 2NaI

Before dissociation 1 0 0 2 moles I olole

Moles after disso. I - a o/2 a/2 .. Moles of N2S2o3 r"3s1s6 = 2 x l nrole

,,-c _(a/2)(a/2) a2 - = (ot)2,-a 11

- 6_a1z - 4(t _e)z 4(l _o.Bf =5 mol"

stoe 2. Cdlculation of lrin equilibrium mimte. Volume of 2 M Na2S2OJ reacted

Hz+12-2HI
=ryr+=1600mL=r.6L
Initial moles 220 : tt":: ); At 627' c nnd one atmospher Prcs'
Moles after (2 -r) (2-x) 2x
sure, sO3 is psrtially dissociated into So2 aod O, os
reaction
Molar @Dc. (2-r)/2 Q-x)/Z bD so3 G) + so2 G) + ; 02 G).

.Thcse bcing originat prcblcms e5 askcd in thc compciitive examinations, ai many places units of \ and Iq havc bccn

includcd e6 pcr old convEntion.

 EQUILIBRIU|\,ll I
- 7149
Thedensltyoftheequilibriurnmixtureisfoundto No$, at 327"C aDd conslant volume,
be 0.925 g L-r. Calculnte the degree otdissociotion of Presure a No. of moles
S03 uEder the giveD cotrditio[s
:. 31 ta
mass caD be calculated 5OnasV
from :
. _d+b 50
or x=#,a
PV=4RT=#RT i =TT
% of NH3 dccompced
or M"b.=tF=dRr
4
_0.925sL-1x0 0821 L a_tm K-l mol-l x(627+273)K
=
.Prublem 4.Thc
x roo = z
^ ff *! rloo = 6r.3e6
l atnl , qtlllbrium coDBtaDt ol the reac-
tlol
= 68.35 g mol-l
Theoretical molar mN of SO: (14r,_.",i..t) 4@) + B2@) i-- 2AB G)
Et lfi,"c b gt If o oEe lltrc fiask coDtaltritrg one mole
= 32 + 48 = 80 g mot-l. of & ls cotrtrGcd to s two lltre ltosk contahtug tr*o
Ifa is the degree ofdissociation, Dolcs ol Br, hor tnstry nolcs ol AB wlll b fomed at
373K? (I.IX 198'
so, 1s; so2 G) + + o, e)
-- A2+ 82 <-----r 2AB
Initial moles I 0 0 Initial I mole 2 moles 0
At equilirbium 1-a I amounts:
Amounts 7-x 2-x u
mtat=t +7 at eqm:

Morar 1-t 2-x

--3- 2x
Theoreticat VD. (D) a
| (V = Motar volumc; coDcs at eqn,I.
5
Observed VD. (d) a
mol L-l
tABl2
K = tArl tBrl
D
., A=r+Zot a
or so =
r;qr=r
(r-l
t-3- J
On soking, we get x = 0 . 955 mole
Hence no. of mols of AB formcd at eqm.

/'ro6lei, .1, NE, is heated et 15 atu from 2?oC to -

2 x 0.9S5
347f keephg the voluEe constrrl Thc trr, prcssule I .91 nol.s
=
bctoEcs 50 aaE st equlllbriuD oftbe reacfion Prublem S.AE,it tutre ofsor, SO2 ard O, goses is
2NH3 i--i N2+3H2. moitrtsln d ot .qu lbrluu lr l0 litrr flosk at a aeEpero-
Cslculrtc ture at whlch I(r for thc rcsctioD, 2 SO2
% olmole of NE3 sctually decoupGd. G) + 02 G)
Solution, I
.-r 2 56, 6; is 100 mol - litre. At equilirbium.
2 NH3 Nz + 3 NHz
-:=
molcs
Initial a 00 (o) Lro. otDoles olsor rrd SOz h the Rosk are
Moles at e{m. o -b x k,'lotal=o+2x saltrg hort Drtr!, EoLs ol ()2 ore prracDt ?
Pressure of4 moles ofNH3 at 27"C = l5 atm. (b) lf tro. ollnoled olsOrlu tle flask are hf,lce the
Pressure ofo moles ofNH3 at 347.C aumber o[ ruoles of SOt, h mony Dolcs ol O, are
pl.lsert (Ro*tc
= p arm (rq,) I9E7)
SO2 G) + 02 (8) 2 So3
As votume remains consranr.
' lIr = !12 =+
15 P
or P=f1
,I="-|ffi- lu(Given)
tm'= r20' 21s1.

r)
7150

(a) As /'a)rrr, 3. tui equilibrium mixture at 300 K con-

[So3] = [so2],
1l hins N2Oa ond NO2 rt 0 2t and l 1 atm respectively.
.. ,* = f6i or lorl = fr1mot L-l Ifthe volume ofthe cont$iner ls douhled' calculate the
I new equilibrium Pressures ofthe two goses'
. . 02 presenl in 10 lilre = ltT x l0 = 0 l mol. (Roorkce 1991)
Iso.l Stelt l. Calculate of Kp
(/, ) tt lso3l - 2lsozl,
':e. iso;i = 2, then
N2O4+ 2 NO2

,*=1j;1 or [o2] =1f,nmol L-r Equilibrium pressures 0 28atln 1Iatnl

I J
PNoz ainf
.. 02 Present in l0litre = T06' x l0 - o 4 Brol' - (l I
-op=r,xq=t;f"trn -- 4.32 arm.
;' ,',i 'r /' The equilirbium constant Kp of the
renction 2SO2+02 + 2SOl of new e
pressurc
is 900 atm-l ot t00 K. A mixture containing SO3 and ift to the
Oz having ilitial Pressurc of I ottE and 2 atm resPec' f nloles ,:
tively is heated ot constant voluEe to equilibrate' Cal' Thismeans that pressure ofN2O4 will decrease while that
c$late the partiol prcssure of each gas st t00 K at of Noz wiu increase. SuPPose decrease in pressure of
cquilibrium, <I.I'T 1989) N2Oa =p. Then
Sohrtion. Considering the reverse reactioo, we +
N2O4 2 NO2
have
Initialpressures 0 28/2alrn 1 1/2atm
2 so3 +2 Soz + or, K, = qfu atn:
Dressures f0=28 -r'lrrn, {**zp) .) o,r't.
..,.. eonr.
\ 2 .)
New -r,...r._"_.__ \2
hitial pre$sure latm 0 2atm

x = (0'r4 -P)atm =(0 s5 +2P)atm

Pressure at eqm. 1-r Z+L,
,l'1 K,=ff 4 32 atm(catculatett dbove)
r,3o, x po., i x
. K,=-;6;=-7:;1= 1z I
#-
m 0 3025 + 4f +2 2P =o 6048 - 4 32P
,{s Kp for this reaction isvery small,, < < l.Thking 4p2 + 6 52p - 0 3023 = 0

+, - Z and (1 - r) : 1, we get -6 52 ! ,{425114 9

2 p =a=-=:ff = 0.045 atm.
^r,1
llZl=fr ot t'=]8ffi or r=0 0236
(minusvalue is Deglected)
Hence at equilibrium (For quadratiaequation d + bx + c = o
Pso, = 1 -t = 1 - 0 0236atm = 0 9764r1m
-t ='/F - ni
,=-------E-) .

Pso2=' = 0 0236 otm

Por=z+|=z+Lff= 2 or18 etm .. New equilibrium Prcssures
L r'r : wtetr
"/'l' sulPhur in the form of s3 is Puzo,=014-o o45-o o95 atm

heated ot 900 K' the initiol Pressrrre of I otm falls by

297. ot equilibrium. This is becrus of co[versiotr of Pxo,=0 55 + 2 x0 045 = 0 64xtm
58 to 52. Calculatc the equitibriuEt const{lt for the /'t,,/'i r,, 'J Kc for CO(g) + ll2g(g) +
reoction. (Roorkee 1990)
CO2G) + H2(c) Bt 9t6'c is 0 63. A mixture ofl mol
soruiou s3G) + 4 s26)
of UrO@; and 3 mol.s CO(g) is allowed to reoct to an
hitial I atm
equilibrium. 'Ihe equilibrium Pressnre is 2 0 atm
Ateqm. 1-0 29 4xO'29 atm
(d) How msny moles o[ Il, are Present at equi'
=O?1 atm =t 16atm librirrm ?
Pl (r) (r) Calculate partial Pressure ofeach Ens ot equi'
,'? : - ,,0 ,u)n = 2.ss atm! librium. $kn*ee 1992)
P,s (g) 71
 EOUILIBRIUM I
- 7151
CO (A) + H2O G)
-:
COz @) + Hze)
,, Pcurou r.sj
Initialmoles 3 1 0 0 \ =
4;iE =
0'+2;1 11p= o t:se
Moles at 3-x 1-x x x
eqn]. q= lcHsoHl
'Ibtal no. of moles at cquitibrium tcoxH;j,
= 3 -, t 1 - x + x + x = 4 o08/25
(o.o11 /2.rao.2487rif = 47a 2
K-. = ,. ',1I . r.a' o t3 - --j1-
(l-t)fl-r) J+r2-4x (r'i) No. of mots of H2 takeo iniria[y
On solving, ir givesr = 0.68'l =0.248+2x0.0E=0.308
( r'=^/F-; \ .
No. of moles of CO taken iDitially = 0. 15
Total no. of moles = 0.308 + 0 I5

.
l'=----2,,
Moles of H2 present-l 6tl = 0 4S8
at eqm. =0 rltole
ApplyiDg PV = ,RI
Total pressure at eqm. = 2 atm (Given) x2.5 = 0.458 x 0.0821 x 750
P
Total moles at eqnl. = 4 or P = ll.Ztotm
z.o=#x2=l 16etm I'n,hl|'n I I A ye-lisel at l0O0 K contains c{rboll
dioxide with a pressure of0.5 atm. Some ofthe csrbon
I- 0.681 dioxide is converted to carbon moDoxide oD addition of
PH2o = ----4- xZ=016atEr graphite. Calculote the value of K if the to&rl pressure
0.681 st equilibrium is 0 t ath, (Iloorkee 199j)
Pcor= PlH, = --Z--' Z = o J4atm.
Solutiop. The reactioD is
I'rohltnt 10. 0 15 mole of COtikenin2.5Illask CO2 E) + c (r) 2Co (s)
is mairtAincd {rt 750 K llongwith a catalvst so ihat the -=+
following rel|ctioD can Llrke place. Suppose decrease iD pressure of COz after reaction

co G) + =p atn'l
2H2 G) <- crr3oH G)
Then increase in pressure due tb CO 2p
HydrogeD is introduced until the total pressure of =
the system is t.5 atmosphere nt equilibiium and 0.0t
'.
= (0.5- +2p
Finalpressure
mole ofmethanol is formed. Calculatc =05+P=08atm (Given)
(i) I<}and Kcarld (ii) thelinal pressure ifthc sEme ''' p = 0.3 atm. He nce we have
nDourt of C0 and [I2 ns before are llsed but with rlo PCO\=0 5 -0 = 0 2 atn]
3
c{tslyst so that the rciction does not take place. and pco=Zxo.3=06atnl
(I.I.T 199j)
Sohtion. (i) CO + i-
rio
D7
ro er2
2Hz cH3oH
pco2 =E:=tt
lnitially : 0.15 Drolc
At eqm. : 0. 15-0.08 mole 0 08 ntole
= 0 017 mole
Totalvoluore, Y = 2.5 L, 1000 K. For the re.lctioD
'Ibtalpressurc P=8 5arm, T=750K. 2H2S G) + 2H2 G) + sG)
Applying PV = ,RT the value of K. is I 0x l0-5 (Roorkee 1994)
we get 8.5 x2.5= n x0.0821 x750
or Soluton. Molar conc. of H2S a-,
a = 0,345 mole -- ffi rno,
. No. ofmoles ofH2 at equilibriunt
= 0 25 mol L-l
= 0 34.5 - (0.017 + 0.08) = 0.248 mol Suppose degree ofdissociation ot H2S
,. = a. Then
rc" = 0 017 x8 5 atm o
o.ET = 42arnl
HzS (----...: 2H+ + 52-
^.p: - 0.248
O-as x8 5atm=6 llalm Iniialc!nc. 0.25 M
-rcH3oH = 008 Conc. at eqru.0.25 (1 - a) 2x0?5a 0.25a
n.3?5x8 5atm = I 97arm
= 0 5a
 llralaalr's Neur Coursc Che m i strgLJifrlll
7152
H2 + Br2 <- 2HBr
Iq= lnitial 0 6nlolc 02mole
(O .s a)210 25 a;
amouDll
.^-6
Ir, - = --ll)5-[l-;,
0'25 a2
-1 _" r) r) 2x
Amourts (0 6 - (0 2 -
Neglecting a in conparison to 1, we get at eqn]. moles

nz t)r n2 = 4x10-6 0.6--r o2-x

--T- 2x
1o-6 = 025 Molar concs --': T.
t)t a= 2xto-3= 0 fi)2 ut eqm'
molcs L-l
.. % agc dissociation = o 27o (V = volume ofreactio[ mixture)
I'rohlai It. Forthe rcectior Ag(CN)t + 0x/Y\2
--
Ag++2CN-, K. at 25'C is 4x10-19. Calcrtlote ''- ro6 -r\ n.2-x\
vv
lAg+l in solution which was oriSinelly 0 I M in KCN 4x2
ind 0 03 M in A8N()3. (I.I.T. Ie94l = It,.6 - rxo--=, =5xlOE
Originally on $ixing KCN aDd AgN03,
Or 4l =5x 108
thc reaction is 0.12-08,+.!.
2 KCN + AgNo3 --
or - 8x - 0 12) x 5 x tttE = 4l
(r2 o
Initialamounts 0 lM 003M x 10t1, we get
Neglecting 4.1 iD comParisoD to 5
AmouDts after (o l-o 06) 0
reaclioD =004M
l-o.tl-r-o'tz=o
- * V10.8;2-4x0.12
(cNt + KNo3 +K+A8
11.s
2
lnitialamounls 0 0
- o 8 I02
0 693
AmouDls after 0 03 M 0 03 M 0 03M - o ?465 and0 0535

rcactioD , = 0 7465 is imPossible. Hence, = 0 0535

Thus iD the solution, DoItr we havc . . Amounts at equlibrium will be
Ag (CN)t = 0 03 M, CN- = 0 04 M. Suppcc r is rhc -0
H2 = 0 6 0535 = 0 5465mol

aorount ofAg (CN)t dissociated at equilibrium. Then Brz =0 2-0 0535 = 0 146smolc

A8(CN)t+Ag++2CN- HBr=2x0 0535 = 01070nolc

t'rohlctn It At some temPniture and undet a
lnitilalamounts 0 03 0 004 pressurc of4 atm' PCl5 is 107o dissoeiated' Calculate
ADrounts at eqm (o'03 - r) x o.o4 + 2x the prcssnrc trt which PCls will tE ZO% dissociated'
,. l('N 12 -- r (l {lt + zrl'?
\ Ins'l tcl'lperature remaining samc. (Roorkee I 996)
(o 03 -'r)
tngtcN', 1 lst case. When PClrit lOVo dlrxrcioted

=lxto-19(Given) PCI( + PCl3 + Ctz

As I(. disociation of Ag(CN)t is!ry
is very small, Ateqm. I-01 0.1mole 01lllole
smirll i e. r,- is very small. tlenc! 0 04 + 2, - 0 04 and =0 9 mole
003-r=003. Tolalno. of moles = 0 9 + 0 l +01 - 1 1n.lole

or 1=?5x1o-r8 o.q 0.1

+-#=4x 1o-1e rno5 = ii x 4atm, PPo3 = x 4alm'

lhus al equilibrium, [Ag+|= 7 5 x l0-rl M 0.1

x4atm
!\ ohlt n lJ 4t700 K, hydrogel
brolriDereact
and Po2 = I.l
to form hydrogen bromide. The v{rlue of eqrtili[rium
consta[t for this reoction is 5 x l0t. Cslculate the
xPct2 04 04
xmount of the llr. Br, and IIRr at equilibrium il a
,, Ppcts I.lxl.T ' ='**
mixt[re of0 6 mole of II, anrl0 2 mole ofBrz is helted
i,i'
(Roorhee 1995)
to 7ll0 K.
 EQUILIBBIUM I
- 7153
2nil case. l[/]ten PCls i.t 2OVo ditociated_ S|p- l.t. Esiihrte thc initial conrposition ofthe air in molc
pose t(,tal prcssurc = atD. Thcn
P fraction ofN2 and ()2, (l.LT. 19971
PCls i- PCt3 + clz In the givcn re{clion, ihere is no change
lnitial I mole
in th of moles. Suppoee total no. of moles
initialty present iD the air = lm.Thenno.of molesafter
At cquilibrium I-02 02mole 0.2 mole attainment of equilibrium = l0O. We have
= 0 .8 lnolo N2G) + O2@) <- 2NO
lbtal no. olnrolcs = o 8 +o 2 + 0.2 Inirial o b 0
= I 2 Droles a+6=Iffi -.(i)
O.ll r. )
x Palnl.
At eqm. u-x b -t 2t
/oro, = 1.2' Patm. Ppoj = I.;
u. (b)2 4x2
0.2< _r i]tm \a-x)(b -r't (a -r)(b _r)
Pctr= 11 ID the questioD, we arc givcn 2r = 1 .8
0.2 P 0.2 P
.. l2 ^- l2 0.2 [.7 P {) 040.1
Kp = ----O:E-F- = -,i.2'
orx=09 and K.-2lxl0-3
=
1.2 -0+
(cahuktted abote\ .. z.t*,0-r="_##=o,r,
which givcs P = 0.97 atm
l'l,hleth 16. ZO% ol N2Oa tholecules nre di6-
ob - O.9 a - O.9 b + 0.8t = 1620

socinicd in fl snmple ofgns at 27.C and 760 torr. Calcu-

ob -O 9(a + r) + 0.81 = 1620
lnte the density ofthe equilihri[m mixturc.
ob-O9xl00+0.81 = 1620
qn*ee ot ob = l'l(D.19 = 17ff)
t996)
Solutioll. NrO4 6) <----: 2 NO2 G)
Now @-b)2 -(o+b12 -4ab
Initial I mole -0oo)2-4x1709=3164
At. eqm. I- (,.2 = 0 8 D]de () .l mote. or n -
b = \r.\164 = s(i.z ...(ii\
'li)tal Solung (i) and (ri), d - 78 I mote.s,
= 1.2moles
If V
11# = o zu
volunte of the vapour per mole, volulllc
is tbe Mote rracrion of N2 =
ofvapour beforc dNsooiation = V
Mole fraction ol ()2 = I- 0.781 - 0.219
llence derisity (D) * + i'rohltn 13. The Kp lor the reaction NrOl
But deDsiry betbre dissciiltion
;-
2NO, is 5rl0 mm ot 775 N. Calculate the perceDtage
Mol.t t._of NzOl dissocation olN2Oa at equilibriuB! pressure ofl60 mnr.
D= =r] = X At what prr*sure the dissociation Fill be 50% ?
(Theorericat deDsity) (kn*ee 1997)
Volune after dsy,ciation - 1 .2 V Suppose initialty N2O4 raken = I ntote
'. Densiry 1a) . ;]y and its degrec ofdissociation = .,
NrOo s_: 2NO,
?-+,. 1.zy=12 lnitial l mole
At eqm. l-a 2,t
o, a=S-S=st Total = t -a+2a-l +a
Ahematively, use (he formula direc y, If P is the total pressure at equilbriuDt, rhen

D-d t -r, 2.
'd Prroa = iTi r Pdr)d pNo2 =ff ^ P

I'rohhtn 17. A sahple ofair consisting ofN2 and

()2 was hented to !500 K l|Dtil the equilibrium -, 12"
Pio" ll+"' c)'
N2 G) + 02 G) + 2No (s) ? pr,o. 1-4 D
)+d
rvas established with an equllibrium constant
4a2 4r2
Kc = 2 l x l0-3. At equilibrium, the mote % of NO wes =at+")iI-")=l_7xP
 Pradeep's
7154

PuttiDg Kp = 640 nlm (Given) afnl equilibrium the solid decornposes into goseous nmmonia and
hydroEen
' 6nlPhide.
pressurc, P = 160mDl,weget 6ao:4x$o lil C.t.rtot. X. aDd Kp for the rcoction ot 27oC'
(ii) WhEt ttrottld hopPen to the equilil,riurr *hen
1 more solid NHaHS is introduced into the flnsk ?
o' Lr-o'=1 o' o2=l-J
(I.I.T 1999)
or 2,] - 1or"2 =O 5ota =o 1o'l =7[ 1qo (i) NHaHs (r) + NH3 (s)+H2s G)
For dissocatioo to be 5O%,a - o 50,Kp:640mn] IDitial 3 06 g
rconsranr) +t0,5'12. amouni =3 06/51mcle
- I (r 5r ^ e
ooo
= 0 06 Dole
- 1n
rJ At.eqDr.006-iffix006 0.018 0.018
rrr tr40=-r-TP=iP or P=4lt0mm
r-i =0 06-0 018
mole mole

The degree of dissociation is 0'4 at =0 042 nlole

400 K anrl 1 0 atm for the gsseorts reaction PCl5 t' Eq0r conc.s. 1 0.0182 0.0182

PCll+C12. Assuming ideal hehnvioor of nll the gases'

(being solid) =0.009 = 0.009
mol L-l
cnlculate the rlensity o[the equilibtium mixtute lrt 400
K nnd 1 0 ntmosPhere. (Atomic mrss ofP = 31 0 and -, [HzS] o .ooe x o.ooe
lNH3l
K.=JFIITFS| =T
Cl = 355) l.l.T 1998)
Solution. PCl5 <---r PCli + Cl2
= E.l x t0-5 ([NI{4HS (r)] = l)
At eqn). 06 04 0 4rnoles Ke = Kc (RT)eg
Average molccular mass of the mixture
=8 1 x lo-5 x (0 0ti2 x300)2
=o o49 (t','c=2Jr =z)
(lr) A,s K. = [NlI3] [H2S] trnd does Dot depend
_ 125 1+55 +12 6 _ t48 92
14 upon the alnount ofNH4IIS (r). HeDce thcrc will bc no
effect on equilibrium when more solid NH4l-IS is added-
For ideal gases, PV = rRT = # RT
I'robtun 22 The Kp value for the reoction
or PM=sRr=dRr Ilz + 12 + 2 Hl rrt 460"C is 49.

. PM l x 148')2- 4.5374gL-r If the initial pressure of H, snd 12 is 0 5 atm

'' 4 =nr=n 66205-vtrm respectlvely' determine the Partial pressurc ofcach gos
At540K'0 10 mol ofPCl3 are heated rtequilibrium. (Roorkee 1999)

in a t 0 L llosk Th. Pressure o[ the equilibriurn mix-

Hr+lr+zHl
ture is founal to hc 1 O atm. Calculate Kp and K. for the lDitial 05 05 0
resction. (Rmrkee 1998)
At. cqm. 0 5-, 0 5-x 2)c
solution. PCl5 + PCl3 + Clz

IDitial 0 l mol r,==!t"-=to

P (0.5 _.r)-
o, 6{f =I
At eqnl. 01-r x x or 2x=35-'7x or 9x=35
1,S
Total no. of ololes at eqm = 0 1+ x or x=:E1 =0.39
PV = nRT '. Pressure of H, and I2 at cqm. =0 5 0 39
. PV 1x8 -
i.e. ,,=hi=6:o6iirTAo=0 18 =011 atm
I'robl(t )3. A mixture in which the mol. mtio ol
.. Ol+r=018orr=008 H, nntl O, is2:1 is used to prePare water by the renction
(0 08/8)(0 08/8)
/ ='---o:027Tt
'' ^"
-0.04 2H2G) + o2@) 2llzo (8)

- contniner is 0 t atm at
Tte total pressure of lhe
Kp = K. (RT)^" = 0 04 (0 0821 x 540)1 = 1 77 Z0'C Defore the reaction' Dctermine thc final pressrtre
'
When 3 06 g ofsolid NIIaHS is irtro- at 120oC after rcaction assuming t07o yield ofwoter'
duced into a twoJitre evacuated flask at 27"C' 307o of
(Roortue 1999)
EOUILIBRIUI\,4 7155
- I

Solution. 2H2G) + oz(g- zHzO G)

Motar conc. of co2 =
Initial moles 2a a
.\s pressures are in the ratio of their moles
O
"*#+ra*
= O.Ol5 mol L-I
(b) When the gascootatns 5% COz by volume, this
.. 2a + d =O.8atmor3a = 0.8ora=Tarm meaDs that pressure exerted try CO2 is also sEo of the
Theorctically expeoted yield of H2O - 2,? (otal pressure. Thus if P is the totai pressurc, then at
an equilibriuur, p66, = 0 05 P and pco = 0 95 P
Aclualyield=2axffi=t 6a
. H2 reacted = I .6 a moles, t"o
s= pco2 til#=1oor 18o5P=ro
02 reacted = 0.8 a moles
ot P=0.554otm.
Molesalrer reaction : Hz = 2o - 1 6 a = O 4 a,
o2=o-O8a=O2a l'roblen 25. The value olK, is I x 1i-3 oqo-t n,
25oC for the Eaction | 2 NO + Cl2 + 2 NOCI. A
Tbtal oo. of moles
llask contalDs NO at 0.02 atm oDd at 25.C. Cslculste
=O.4o+0.2a+l6o=2'2a tbe mol of Cl, thot nrust bc oddcd if l% ofthe NO ls to
HeDce final pressure = 2 2 , !-9 - 0 s9ut- be convcrtcd to NOCI at equlllbdum. Thc volumeofthe
nosk is such thet 0.2 mol of the gos produc! I otE
l'^,hint )J. Al tI7oC, K, for the reaction btwecn preEsurc at 2SC.
CO2 (i:) and excess hot grsphite (s) is 10 arm (Iguore the probeble assoclation ofNO to N1O2)
(a) What are the cqrlilibrlum oonceDtrstions of (R@*ee 20Ol)
the gnses st E17'C and a totol pressure of5 atm ?
Suppose initial prcssurc of Cl2 added isp
(r) At rvhot total pressure, the 8os contains glTo atm. Then
CO2 by volume ? (Rnrtue 2000) 2NO + ctz <- 2 Nocl
(d)cox@) + c G) + 2coG)
Initial 0 02 atnt P Atm
Suppose at equilibrium, pressure of
CO (t co) = p atm *"c,.(ooz-ffi) (, H q#
Then pressure of Coz@cor)=5-parm =2 x 1o-z-2x11-t =p-to-l =zxto-4
.. Pco bz = 2xlo-1(loo-1) atm
rlp=pcor=6:p)=lo - 19t x 1O-4 atm
_2
orf + top-50=o ., PNoo
A- - --t-
-tr'/*-ao, ' PlNo x P<\

l0-l =
- 10 r y'T00-=?=Zo-0-f
=---,--=3.66atm (t98x1O-')2x(r-10-1
,4.
Thus ai eqm.,pco = 3 66 atm, or(P- lo ')=fiqlzx113=o 1

toz
Pco2= 5 -3 66 = 1 34atm or p=0102+00001 =01021 arrn
Applyrng PV = r, RT Volume ofthe vessel can be calculated as folloPs:

or nP PV =nRTorV - ff - o2 xo 9a2 x 213

L
v=RT ?1
p = 4.887 L
r?. motar conc. =
Ef To calculare the number of moles of Ch, agaiD
Molar conc. or CO = apply

"aE71+E+irr- PV = ,rf 61' .,i$?!:i#

L-l
= 0.04r mol
= H =
= 0 0204 mol
7156 Pradeep's

lUULTIPLE CHOICE Es'T/,ONS

For ,>E_ rNl I trrclll.llrrdr yr,
and All Other ComP

l. Reactioo between iron and steam is reversible if il 7, According to l-c Chatelicr's principle adding heat
is carried oul to a solid and liquid in cquilibriun'r will cause the
(d) at constaDt temperature ,{) amount ofsolid to decrease
(r) at constant pressure (6) anlount ofliquid to decreasc
(c) iD an open vessel (c) lemperature lo rise
(d) in a closcd vesscl. (d) temperature to fall.
2, The relatiooship bet*een Kp and Kc is iJl.l"N'R AlllJnbatl Ie90 )
t. In a reactioD 426) +4 BzQl)+ 2AB1g),
(aiK" = K,(Rr)^" 1tyt<.= 5lnrl-& AH < 0. The formatioo of AB4 G) will he fhvoured
= x. (nr)-&
,tdx, (.1) None or lhesc is correct' by

3, The equilibrium constant for the rcaction (4) lov le$perature aDd hiSh pres\urc
N2 + 3H2 <- 2NH3 is K. The equilibrium (6) high temperature aDd lo\x pressure
constant for (c) low temperature and low pressure
(d) hiSh temperaturc and hiSh Pressure.
lvrrlw, ;4 vH, w1169
(1.1.'I 1990)
(o)K / 2 (b)2K 9. The reaclion which proceeds in the forward direc-
pflK (d) K2 tion is
4 lf an inert gas is added to the equilibnum mixture (o) Fe3Oa + 6 HCI = 2 Fecll + 3 I-I2O
of the dissociation of PCls iD a closed vc'sel, (b) NH3 + Il2O + NaCl = NHacl + NaOH
(a) the concentration of Cl2 will incrcasc (c) Sncll + H82Cl2 = SnCl2 + 2 HSCI2
(b) thc concentration ofPCl3 will iDcreas
(d)2CuI+l,+4K+ = 2 Cu2+ + 4KI.
(c) thc coocentration of PClj will increase tl L'l: 1let )

(d) the cquilibriunr concaDtralions will remain un' 10. For which of the following reactioo, Kp = Kc ?
affecl ed.
(4) 2 NoL-l G) # z t'lo 1r1 + ct2g\
If pressurc iDcreased on the equilibrium
is
Nz + oz <=+ 2 NO, the equilibrium will <=--r 2 Ntl3 (c)
(b) N2 G) + 3 I12 G)
(a) shitt in the forward directioo (c) H2 G) + ch G) s- zHCl (8)
(r) shift in the backward directioD (d) 2 Nro4 ) <: 2 No2 Ui)
t
(c) renrain undisturbed
,1.1. L l99l)
(rJ) may shift in the lorward or backward drrectioD ,. ()z
. 11. ln u vesscl ,jnnlainlng S()3 . SOz and irl cQui-
For the reactioo
PCl3 E) + cl2 (S) PCls Cl)
'' librium somc heliuol sas is introduced so that lhc
+ total pressure increases while len'lperature and
the value of K. at 250"C is 26. 'lhe value of Kp at volunle remaiD coDstant Accordlng to Le
Chatelier's Prlnciple. Lhe dissociatroD oi S()3
this tcmperature \4ill bo
(?t) 0.61 (a) increases ,,@j c""r"^o
,lu1o-s'l
(c) 0 83 (d) 0 46. q;)remains unaltered bly.
(M. L.N. R- Allahabdd I 990 )
\ ( I'
iis
l. .l 2,b 3.c 4.d i.c 6.a 7. t E.d 9.d 10. c
ll. ,
 EQUILIBRIUM 7157
- I

12. lD a rcversible reacti()D: t\+'o substances are in equi- 17. ln 2lII Hz + Iz, thc ti)rward rcitction rs
librium. Ifthe concenlration ofcach oDe isdoubled. r,lccled =-
by change in
lhe equilibrium constant will be
(4) Catab6t (1,
) I'ressure
(d) Rcduc]ed to half its original value
(c) Volume (d)'lijnrperatoro
(D) Ilcduccd to onc lburlh of its original value
(c) Doutled (d) Coostant.
lll\Ofttut L"L.L l. It)ttJ
l& 64I of HI arc prcsent in a 2litre vcssel. '[}!c adivc
t,lI.L.N.Il. rlllalubad I9t)).lt.l.7: lt .hi l,t))) mass o[ I{I is
Ir. AD equilibrium mixture for lhe reactioD 5
(a) 0 <bTO.2s
2 HzS (B) s-:-: 2H2G) + sze)
.(t)l0 (d) Noneol the rhrce.
had I mole of HzS, 0.2 mole of H2 and 0 8 mole t Ih1^a,u (.1).L.1: lee:

of 52 io a 2 lilrc flask. Thc value of K" in mol L-l lt . The equilibnum consrant (Kp) for the roaction
ts POs G) + Pcl3 G) + cl2 g)
is 16. It lhc
(a) 0.fi)4 (r) 0.08 lolume of the oontainer is reducrd ro one-half of
(c)0 (l 16 (d)o.l(ff. ir r.T 1ee2) ils originalvolumo, the value ofKp for the reacrion
t*-ln what maDner will iDcrease ofpressure affect the at the same tempeEturc will be
" lbllo$'ing cquilibrrunl 'f Q1'tz .
(D) 64
C (r) + Il2O G) <=:+ CO E) + Hzo (f )
r<c) t6 ig)+.
(a) Shili in the forward direction l)t
-/..-t
(r) Shift iD the reverse direction ,4zlnarw;aion,A + of
(c) Increase in the yield of hydrogen A 3.0 mole of 'B'a in
a 2.0 L flask and the e4uilibrium concsntration of
(J7lio en-ect. (LLT. 1991i
'C'is 0.5 rflolc/L The equilibrium corshnt (K) for
15. 'I}le rcaction, SO2 + Cl2 i- SO2 Cl2 is ex.
othermic aDd rcversible, A mixrure of (D) 0.147
SO2 E) , cl2 E)
and SO2 Cl2 G) is atequilibrium in (d) o.026.
a closed contaioer. Now a ccrtain quantity of cxtra (Hda-dm C.E.E. [, 199(
SO2 is introduced i[to (he container, the volumc
gy'One mole of N2O1 G) at 3m K is ke?t in a ctosed
remaining the same. Whici of the follqlring is/are
truc ?
' co[taiDcr uDdcr one aunGphere. It is heated to
({n K s,hen 2070 by mass of N2O. (g) decompces
(a)The pressurc inside the container will llot
lo NO2 (t). The resultant pre.ssure is
change
(D) Thc lemperature will not change (a) 1 .2 (b)2 4 a.m
"tm
(c) The temperature will iDcrease (c) 2 0 atm (d) t.0 atm. I.I.T tss(
(d) The temperature willdccrease. 22. If the colcDtratioo ofthe reactaDis is lncreascd by
r, theo equilibrium constanl K becomes
I S ll l)tutlhLt.l. it)t):
16, The equilibrium coDstant for the reacrion, ... K
trtln- (r)+
x
N2G) + ozG) <- 2NO(a)is4 x l0-1ar
(c)K+r ldJx
2ffn K.
In prescnce ofa catalyst. equilibrium is attaiDed ten
A.Etl.C. I\tw 1997
23. In which case Kp is lqas than Kc ?
trmes faster. Tberefore, the equilibrium constant,
in presence of the catalyst, at 2000 K is: (rl)PCl5 + PCl3 + Cl2 .

165 t x ro-a
(a) 4O x lO-a (b) H2 + Cl2 + 2HCl
(c) 4 x 10-3 (.) 02 r=l
2SO2 + 2SO3
(d) difiicult to compute without more data. (d) All ofrhese it.E]I.C. I'tru 199i
IM.L.N.R. Alhtuhtd, 1994 t

A]VSLL'FRS
12. d 13. c 14. b 15. c 16, b 17. d llt. , t9. c 2lt. t 2t. b
22. d 2i.
758 N e.4

24. If Kl and Iq are the respective equilibrium con- 29. For the chemical reaction
staDts for the two reactions 3 XG) + Y(g) + X3Y (8), thc amouni of
affected tY
XeF6 G)+H2O 0I) + XeOFIG)+2HFG) X3Y at equilibrium is

Xeo4 G)+xe F6 G) + XeoFo (g)+Xeo3F2 (8) -(t/) tenrperature and pressure

(6) temperature only
the equilibrium conslanl of the reaction
(c) pressure only
Xeol G) + 2 HF G) + Xeo3Fz G) + Hzo (E)
(d) remperature , pressure. aDd catalyst
will be
30. For the reaction N2+3 H2 + 2 MI3 + Hoat.
@) Ktt$ (b)& Ic,
{d) Ke = K. (RT)-r (b ) Kp = Kc
(c)\/Ka )ulxa/ Kl
(c.B.s.E. Pm.T 1996) (c) K, = K" RT (d) Kp = K. (RT)-t.

23. For tbc homotencous 8a! reactiql

(D.C.E.E.li. 1999)
4NH3 + 5 Oz + 4NO+6H2O 31, What would happen to a reversible dissooialior
reaction at equilibrium when an inert 8as is addsd
the equilibrium constant, K! has the dimensions of
; $hile the pressuro renains unchanged f
(a1 conc+lo Q) con"+ | ' (4) Less ofthe product will be formed

(c) conc-1
-4'1 s)
,!81More of thc product will be tbrnled
(c) More of lhe reaotants will bo formed
(d) It remains unaffected. rl).c.l: Ii li. 1999)
Forn]atioD of SO3 takes plac acaordiDg to the
32. For the reaction !I2 G) + 12 [C) + 2 Hl (8),
reaction
the equilibrium coDstaot Kp challges with
2SO2+ Oz + 2SO3, arl = -45 2 kcal
(6) temperaturc (b) total pressure
Which of the following factors favoum the forma-
tion of SO3 ? (c) catalist (.1) amount ofH2 and I2.
(D.C.D.E,E. t999)
(a) Increase in temPerature
33, In thc gaseous reaction A+2B + C+heat'
_.pflncrease in pressure
the fonvard rcaction is favoured by
(c) Remol.al of orygen
(4) low temperature and low pressure
(d) Increase in volume (M'P PM'T' I99E)
(b) low pressure
27. Kp / K. for the reaclion
(c) high temPerature and hi8h Prcssure
co@)++o|@ + co2 G) is -{d)high pressure aDd low temPcrature
tD( IiLL le99)
(4) I (6) Rr
34. For a reversible reactioD, ii the concentratiolts of
141/,rrf (d) Gr)'/' the reactants are doutled, the equilibrium constant
uu.P PM.',t 199E, A.l E.E.E 2oo2) will be
For the reaction (a) halved (b) doubled
CO (A) + H2O G) + CO2G) + H2@) (rfthe same (d) oDe fourth.
(c.B.s.D. PM.T 2000)
at a given temprature, the equilibrium amount oi
Coz G) car be ircrea$ed by _/L' For the equilibrium
A
(.I) addinS a suitable catalyst MgCo3 (r) Mgo (x) + co2 G)
<-------\
(b) addrng an inert sas
which of the fouowing expressions is correct ?
(c) decreasinB the volume of the conlainer
Puso' Pco,
= P'sco, (h)- --
(d) increasrDg the amount of CO(8) [Mgo] lco2l
(t.1.7: t99E)
to) Kp 5 = JMgm;T-

74. .1 25. b 26. b 27, c 2E. d 29' a 31. b 32. a 33. d

34, c

,I
 EOUILIBRIUI\4 I 7lsg

PMso x Pco. 41. WheD two reactaDts A aod B are mixed to givc
(.) It = /r,rscq @) \ = pcoz. producls C and D, tbe reactioD quotie[t, Q, at lbe
initial shges ofrhe reactior
lc. lr.s. li. l!,t|.'l: )0t)t)) (4) is zero (lr) dccreases wil.h timc
36. What happens to the yield of this reaction whcn (c) is independent ot tin]e
tcmprature is incrcascd I (y') iocreases with tiorc. (1.1.7: 2ooo)
Nz+()2 # ZNO;+:.Zt<cat 42. At corlstant len]perature, the equilibrium coDstaDl
(4) increases (D) decreases (Kp) for thc deconrposrtion reaction
(c) remains samc (d) NoDe ofthese. N2O1 <- 2NOz Ls expressed by
\ 1 11 i - trl Ke= Ot \/( -l; where P = prcssure, r =
,, 500 mlvessel contaiDs I 5 M each of A. B, C and extent of dccomposition. Which one of tbe follow-
D at equilibrium. If 0.5 M each of C and D are ing statemeDts is true ?
. rakcD out. lhe \alue of K. lbr A+B # f;+O (.r) Kp incrcascs with iocreas of P
will be
(6) Kp iocreases with increase ofr
kr1 0 (b) lB
(c) Kp increases with decrease of.r
(c) 4/) (d) 8B
(D.('.1,.E.L: )0(1(1t -+Kp renrains constant with change in P andr.
3ll" Al 25'C the value of Kc for thc reaction . (! l.T 2t)01)
jI
x, + o, <-----r No2 is 2 x lty'. whar will he
23. 5 moles of SO2 irnd 5 moles of 02 arc allowed to

, react to form SO3 in a clGsed vessel. At the cqui-

the value of K.' for 2 NO2 <: N2 + 2 02
librium stage,60% SO2 is uscd up.'fhe total num-
(o),17 x ro2 kG:@ ber of moles of SO2, 02 and SO3 in the vessel now
ls
@)2xtd @) 1(f c.Piv.T 2oo0) . 6z.s (b) r0.5
39. Which oF the following is not affecled by increase (ff8.s (.1) 10 O (R.C.E.T 2001)
in pressure ?
-r4' A quantity of PClj was heatcd in a 10 drfl3 vesselat
(4) 2 NIL G) <r N2 E) + 3 H2 g)
250'C : PCls g) i- PCl3 E) + Cl2 E). At
(r)N2e)+3H2G) + 2NH3G)
equilibrium, the v6scl contaios 0.1 mole ot PCls
(.)N2E) +02e) + 2Nok) and 0.2 mole of Cl2. The equilibrium mostant of
(tl) ZSO.G) + 02 E) + 2SO3 G). the reaction is
t.l. I. Pll. I-, R. 2t)()0) (a) 0.M (D) 0 025
(c) 0.02 (d) 0.0s
(l)+l Hz ) ;-
,10, For the reversible reacrion, N2 (K.c.E.T 200t)
2NH3g) at 500'C, the value of Kp is 45. 9 2 grams ofN2O4 (g) is taken iD a closed oDe litre

1.44 x 10-5 when partial

pressure is measurcd in
vessel and heated till the following equilibriunr is
reached
atmospheres. The correspondiDg value of K.., wtth
N,O, 1g1 ---------s 2 116. n,
concnradoD in mole litre-1, is
At equ ilibriu nt, 507, N2O4 G) is dissociared. Whar
(a) 1.44 x 10-5,/(0.082 x 500) -2
is the equilibnum consrant (in mot lir-l)
(h) | 44 t< 1O-5 / (8.314 x 773)-2 (Molecular weight ofN2Oa = 92)
(c) .44'l
x 1O-s / (0.M2 x 773)7 (a) o.l libn.2
lLJ 1.44 x ll-s / (o.o82 x 713)-2. (c) 0.4 (d)2
(D.A.M.C.E.T 2001\

fS. .t 36, a 37. a 39. c 40, d 41..t 42..1 4!. c 44. .t

45, b

.l
7160 Netd Course
46. lf N2 + 3 H2 s---------r
2NH3-K then lNH.t2
is siven rry e=
2N?+6t12 4 NH3-X. ? INJE;p
=- 'lte reactioD
6x, (D) r'Ir (c)t/,/K glrt* (a)Q= K.
will proceed from riShl to left
0,)o.q (9Io > \ 1l)o=tt
if
(Roids nn llll.T 2t102)
47. In thecase ofa gaseous homogeneous reactioD, thc
i(.ll.s lt. Plt l: )0t)iI
active mass of the reactant is obtaind by the cx- 53. The following equilibria are given
Prcsslon
N2 + 3 FI2 <:l 2 NH3, Kr

- PV (a)RT
(.,)nT -,.P c)+ r\9o N2 +

H2+ioz <-
I
Oz i=:= 2 NO,

H2o, K3
Iq
\'tanil ,\'du L.l .'l: )olt)
4tl. In which ofthe folloBiDg equilibrium, change in the Thc equilibrium constant of the reaflion
volume ofthe system does Dot alter the nuDber of 2NH3+iO2 2NO+3ll2o
moles ?
+
in terms of Kt, Iq and Iq is
(d) N2 G) + 02 CI) i-s 2 No G)
(r) g) I! Iq
(a) Kr (6) Kr rqlrq
PCr5 E) <-PCt3 G) + ct2
(c) N2 G) + 3 H2 G) u-------s
2 NH3 G) G)\Rl/tq .\dIK2Y'.tr/ Kl
t(.8.\ li I!.11.7: )oo l
(d) so2cl2 (s) + so2 G) + cr2 G)
For the sfnthesis of ammonia by lhe reaction
trll l: l. :t)tl) "64.
' Nz +.1 H2 + 2 NH3 in lhe Haber's process,
49. I moleofN2 and 2molesofl{z are allowed to react
the attainment ofequilibrium is corrcctly predicted
ia a 1 dn| yessel.
At cquilibrium, 0 8 molc of hy the curve
NH3 is formed. The concentration of H? in the
z z
vessel is o I
Gr)O 6mole (r)0 8mole =
2i
(c)0 2mole (d)0 4 mole t2
, t.\liniDol l'\l l: )t)t)) '
zo =6z
'")O' Tt " rut" of fo*rrd reaction is two times that of thc
O
o o
rcverse reaction ai a Siven temperature and identF
cal concentration. K*ollitrium i.t

(o) 0.5 (6) 1.s z zo

(.KL.ll.l: 2ott) I
(c) 2.s W2.o E<
51. Considcr the follo$,iDg equilibrium in a closed con- <t
tainer: N2O1G) 2NO2G) A,
+ 2o =3z
At a lixed temperature, the volume of the reaction
zo o
container is halved. Fbr this chanBe, which of the o o
following statements, holds true regarding thc TIME
equilibrium constant (Kp) and dcgrec of dissocia- (c)
zo
tion (a) 'f
E
(d) Deithcr Kp nor a changcs
(e)
*a
(6) borh and a chan8e l,<uJ
5
(c) Kp changes but,, does nol change z
o
o
p)'k, does rrot change but 4 chariSes, /.1 i-ll,r/l
I IMI:
52. The reaclion quoticnt (Q) for the reactbn
N2ct) + 3 H2G) -- 2NH3E)

46. a 17. h {lt. a J9. h SU. ./ 51. I -(3. d 5.1. .t

EQUILIBRIUM I 7161
-
55. ln the reaction PCll(()+ClzG),
PCl5 (g) + (a) [cl2l > [PCL] (6) lcrrl > [P1]
thc cquilibrium concenirirtions of l'}Cl-5 and PCI3 (c) [Pa] > {cl2l (l) lPct3l > [P4]
arc 0 4 and 0.2 mole/litre resPectively. Ifthe value
of K. is 0 5, whal is the conccntratron o[ Cl2 ill u & KC.li.'l:200Jt
nloles/4itrc.'
62. ln Lhc gileD rcac ol 2 X G) + Y G)+2ZG)
+ 8() kcal, which conlbinahoD of pressure irnd
(o) 2 {t (D) 1.5 temperature will give the highest yield ofz at equi-
(c) I .0 (d) 0.5 libriurn ?
( E.A_ il t. c. l:.'l: 2 0 0.1 \ (4) lffn
atm and 200"C
56. Io a givcn s) item, wa(er and icc are in equilibrium. (6) 500 atm aod 500eC
If pressure is applied to the above $lstcm rhen (c) lmo atm aDd 20ffC
(.,) More of ice rs formed (d) 500 alm ard loO'C
(h) Amount of icc and water will remain same (e) 1000 atm and 50ffC tKtrala C.ti. | )|t)J t
(c) More of ice is meltcd 63, A mixturc ofNO2 and N2O1 has a vapour density
Gl) Either (o) or \lthto (
(c) l.:t)tt1 l( of 38 3 at 300 K. What is the numbr of moles of
57. Of tbe lollo#iDg which change wlU shifl the reaction NOz in 100 g of rhe mixlure ?

tovards lhe product ? (a) 0.043 (b) 4.4

12 G) I G), H', (298 K) =+ 150 kJ (c) 3.a (d) 3 86
^
(rr) increase in concentration iI I (c) o.a37 (K?rdln l!M.T 200J)
---------r2
(b) decrease in con0entration of12 64. Ammonium carbamate wheD hcated to 200'C
(c) increas in temperature giws a mixture of NH3 aod COz i|apours with a
(d) increase iD total pressure \ I I tl \ :ttt).]) density of 16.0. Whar is the dcgree of dissociarion
o[ammonium carbamate ?
5t. For the reaction CO G) + cr2 G.) i- Coclz G),
(o) 312 (b) 12
Kpl Kc equal to
(c) 2 (d) |
(a) 1/FtT (,) RT
(e)sD (IQrula PM.T 2004 )
(c) r'ET- (d) r.o
65. 2 mol of N2 is mixed with 6 mol of H2 iD a closed
t,tl l,.l: E 20t)l)
vessel of one litre capacity. If 50% of N2 is coD-
59. 56 g of nitrogeo and 8g of hydrogen gas are heatcd
in a closed vessel. At equilibrium, 349 of amnlonia vened iDto NH3 at equilibrium, the lralue of Kc lbr
are prescnt. The equilibrium oumber of moles ol the reaction N2 g) + 3 H2 6) + 2 NHI (a) is
nirogen, hydroen and amn]oDia are respectively (a) al2'7
(o) 1,2,2 (b)2,2,1 (b)nh
(c) t, t,2 (d)2,1,2
Un
(c)
tunntkd ( 11.1: )qi).li
60. Calculate the partial pressure
@)n
ofcarbon moDoxide
(r) e (Kerula Pll.l: 2tJo4)
from the lbllowinS data :
a56 Kp for the follqwing reaction will be equal to
GCo3(r)- CaO (r) + co2 t, K, = 8 x l0-2 (r) + 4 HzO G.)
COz G) + c (s)+ 2CO G).Kp = 2
Fe i==: Fe3Oa (s) + 4 H2G)
. ps^
(o) o.z W,4 (a)(Pn^)'@e..o.) (b);--1
(c) 1.6 (d) 4 r H20
\()ti\ut Il.l: 201)Jl (y'
s,) @ s-) @ p..o.)
61. The equilibriurn P4 (T) + 6 Cl2 g) 4 PCI3 G) (c)G;;F
is attaincd by mixing equalmolcs ofPl
=+ pp.
and Cl2 in
an evacuated vessel. Then at equilibrium (u.l c.t!M.T 200r

,r( _s
(t5. a
56. c 57. c 5t. a 61, c 62. c 63. e
66. c
7162 Netl Course Che ruisttg

H I NT9/EXPLANATI ON 5 t o W ul1i-i ?l e Ch oi c e Q.u e sti one

l. As othcrwrsL thc I{2 gas $ill cscirpe Applying PV = zKI] 1 x V - 1xRx3fi) ''(i)
2. Kr = Kc (RT)^' or Kc = K/ (RT)- ^n f
Whcn z = 1.2 mols, = 600 K,
PxV-l2xRx600 . (t/)
4. lu a closed vesscl, cor)ccntratloo$ of reactanls and
Dividing 0i) by (i), P = 2.,1 atnr.
products do nol chrDge ort addins inrt gEs.
6. (RT)A" = 26x(0 0821xs23)-l = 0 61'
22. Equilibrium constant is constallt at constal,lt
Kp = Kc
temPerature-
7. S()lrJ + l{eut # l-iquid. Adding heat wrll
shrll lhc cquilihriirm in lhc forward direclion. Kp - Kc (Rf )e. Kp is less thon l(" if aa = - uc i.e.
!t. 'l'hc given reirctioD is exotherffic (all < 0) and
lccomp nied try dccreas ir thc trun]ber of moles
IIcncc it will b,e fa\oured by low temperature and ,.
trr =
fxeoFollHFl'? ,, lxcot'al lxco3l zl
|\' =
high pressure JF4ITrJFI- lre-oJTxE4I-
9. FcCl3 alld I IzO do nol react to Eivc bsck FcaO4 and .. [XeO3F2]
Atm: -
Illrol Ka
HO. lxeo;l IHFIr Ri
11. Sec IliDt to Q.4.
12. Equilibrium constant ofa reactioo docs not depend
upon c([lrfcnlrations. [t is cotlrtant at cooslallt
x.=ffir=ffi'"'n"'
IH"ol6
tNol1 .^----.ro

t cll't pe ra Lu rc.
But with respect to stirndard stale concentration ol
14. ll)c for$'ard reaction is accompanied by the in-
crease in (he Dumber of gaseous moles. Hence 1 mol L-1, it is dimensionlc,ss.
incrcase of pressure will fflvour the reverse reac- _
r- /_ l\
tion.
&,s= I\I
*Z) =-Zt
t5. SO2 + Cl2 .- S(]161, + Ileat. OD adding xrz f. = 1nr;& = (RT)- 1/2
= t r r4{T'
SO2, thc cqurlihriurn will shitl fon ard is. nlor Back$ard reaction is dissociation reaction and
heat will be c1,olved. So tenrPerature will Increase, henct endothennic. The forward reactioD will.
16. Ilquilibriunr constaft of a rea0tion i! coDsunt Rt ilterefore, be exothermis. Fulther, it is accom-
cousfant tenlpcralure. paoied try decre&ie in the number of Saseous
17. Ir is an endothcrmic reaction. Hence equilibrium is moles. Hence its equilibrium will b affected try
tempErature and pressure.
affgcted by tcnrperature,
I{l = On addilU iDert 883 at coflsmnt prEssure, di$socia-
1E. Mol. mass of 130,
tion i[creases i.e, more of tho Produus will he
. Ilrrl =ffi"1=o zs. formed.
Equilibriunr coostant changes only with lcmpera-
19, Ki, docs not depeld upon voluD'lc or coDccDtra-
ture-
li(n)s. It is cor]slatlt ilt coosunt temperatute
3s. [Solidl =
20.u\*28+2C 1.
1.5 Y 1.(
lDitillconcs. 1molL-l 5motL-l 1 Imoll--l fl. X" = i# = l. ()n char)grng uoncenl rll iot1s.

/\t cqn]. (1 + 0'25) (1 5 + 0'.5) 0 5 cquilibriuff clDslsnl does not ohal1ge.

=l ls =:0 nrol I-l 3& The reactiol is rel,ersed alld nrulliplie(i try 2, thcro'
mol t.-l nrol L-l [or( equrlrhriun] conslr,tt -I K?

,, tu 5t2 = 1 ,, 12 x ltlalz =
'
N= 0't)5 -'1-
a toT
l15 \ edr = lo. X. = X, z1n'r1&
^
21. NrOl (- 2 NO2

lnitial 1 o]olc = 1 44 x'lo-s / 1o 082 x 113,-2

/\1 cqm. 1{ 20 0.40 mole,
lbtal = 1 2 n]ole
4r. A + B+ c + D, o =
{:tlBi
withrine, [c]
= 0.30 mole and [D] incrcasc ancl so does O.
I mole \apour ha\re pressure = 1 atm at 3(n I(

I
EQUILIBRIUM I
- 7163

HIN:T6 CONTD.
42. Kp is corsrant at constanl temperature.
Aim:K- lNolr llr,olr
''' K, Kj
4.3. 2SOz + Oz <===+ 2SO3 = _j-
Kr
lNHr12 Jo2]5/2
Irrtial molqs 5 5 54, (a) is ccrrect hecnuse coDcenlrations ol H2 il,td
nr cqnr. 5-TfrY5 5-1.5
r,0
1 N2 decreaso wi$l time while that o[ NII3 incrclses
wilh time ancinfter equilibriunt, irll olthem remiliD
=s-3=2 =3.5 constant_
'lbral=2+3-5 +3 =8 5
44. l(15 <_=+ PCll + Oz
5s. r\. =
lPClrllclrl
Molcs xt eqnt. 0 1 molc 0 2otole 0 2mole JpfXT_
Mohr coDcs. 0 1/10 O A:(t 0.2110 0.2 x lCl- l
r." o 5= rrr l( lzl - I (t nr,'r l r.
ntol dar-l --57-4
tr. Ice <=.J Whrcr.
x=!l${f14=o 61 Morevql. [,e$s vol-
45. lnitirl IN2Oa] =9 2/92moll,-l On apptying prss.\ure, equilibrium shifrs k) the si(lc
in *hrch volume is les.
=0.1nrolL-l 57- l'he givel rerclioll is endothcrn]ic.9l on increJs-
At. cqn]. (aftcr 50% drssociation),
rng temperaturc. it will shilt in the forward dirccti(nr
IN2O4] = 0 05 M, [NOzl = 0, I M 5ll.,trr=1-2=-1
I2
,, I't(,21
'r1,1 r0.1lr (R-l')^, = K.(t(f)-r=
K =
iNJIJ ='Ori- =u I Kp = I(" K..,lLI'
,17. 1\cllvc l'lilss = Molar conc =
or Kp,/K. - 1/RT
# 59. ,569 Nz = 5(',,28 = 2 motes,
Irrom pV=,,R'[+=# [i8 H2 - 8, 2 = .l molcs,
4t. (lhangc in voluDe changes the molar coDccDtra- 34gNfI, = 3,f ,' tl = I n1;1g\
tion. In (a),np = r,,- Change in volumewillnot alter
Nz + 3lt2 -.--+ 2NIJ3
rhe nuDtber ol n'loles in rhis case.
.{9. N2 + 3 tl2 \--+ 2 NII3
Initial 2 moles 4n]oles
At.(4D1,2- I nrolc 4-3 2 nrolLn
I:orotarion of 0.8 nrolc of NllJ means that
'I = I mole = lmole
r ( 0 li nrck' ol H2 hilvc reacterl. Hcncr con- 60. For reaclioo (i), Kp = pco, = 8 x tO-2 ((;ivn)

ccntrarron ofI12 = z-lxo.s =2-I.z=0.8mole F'or reaction (ii).

k, .,
", *=,
= (Given)
so. Kcqh =
i= i =,
51. Kp rs constant at constant temperatute, dslplume ,--rL-- tr.lrco=0..1
is hahed, prelsure wilt be doubled. I{ence equi-
libnunr will shill in rhe hacloxard direction i.e- de-
61. P4 (r) + 6 c,2 G) \,_r 4 PClr (s)
{rec of disst)ciation decreases. Initial lmole I nlole
52. 'l}le reaction proceeds fiont rigbt to left when At eqm. I -x 1- 6r .[x
Q, K. s,r lhrl Q tends to decrease to beq]me As (l - r) > (t - 6 r), heDce IP4l > [Ct2]
cquill to Kc.
62, 46 np < h..hi[hf.r I he pressure. greater will bc yicld
INI l l2 , r r^,2 of Z. As reaction is exofhermic iD thc tbrward
s-'. K, -
rNJfu'-, = did;I, yiekr
dirsc

IH.OI slot ,
,-#i:i#';
is used).
' lurl lo,l''' 61. Suptrce NO2 -.rg- Theo NrOo = (lur _.y).s
7164
Pr^lear's Net4 Course Chem istyqllft[)

64. NI ITCOONI{* 2NH3 + Co2

lvtolcs of Ntl, = ft, Moles ot Nrtl. = $jI -
lnitial l mole
x,4t ,\ller disso I - c 2e
Molc lruclloD ol N()2 --
x/. i I (100-:l)/(D- 'lbtal =l+2i
t )2 L\
'l})coretical dcnsity (D) t
46 t00+Y 100+(
1Y I
Mole trirctron olNzoo =t- ffu obscrved densrty (d)
" n -, ")A
100-Y
'
D^ t+2"
'I
00 + t I=
Molar mal\s of mixrurc .- lrD-d\ I I48-lqa) .ro
Lr
= ------- x .16 *
-.( , ,z^ = ,200
I00
166-ll
", "=Tl--T)=t \--!6r l-"'
roo;T 65 N2 + 3 }tz i=- 2 NH3

#=2x383:76.6 lnrlal 2mol 6mol

(w = 9200 At. eqm. 1 lnol 3 mol 2 nrol
or 76 - 7660 = t5a0
L-l
or r=20 109 MolarcoDo I J 2nrol
.- t2t2 4
K,=+=xlt
' Ix (3,' zt

ADD'T'ONAL uEsrloMs
Exarninati
Ae s erAi on -Re a s on T,
V V e Q.u e sAi o n s
The folloyilg questions consist oftwo st{tcmenLs, pritried as acseltion nnd Reasoh.
whilc a|rslverinI these
q{estions, you ort required to choose tlny one ofthe tollowibg follr responscs'
(a) Ifhoih A.ssertion and Reason are true nnd the Reason is the corrcct explanation of thc asscrtion.
(,)IfhothAlrserlionondReosonartttuebutreasonisnotacorEctexphDlrtioDofthe,Assertion,'
(c) If Asscrtion is true hrlt Reason is false.
(d) IfAssertion is tolse but Reason is trre'
(?) lf hoth Asscrtion ond Reoson sre fglse.

Assertion ReflsoD

The equrlibriuD coiffiifE fixerl and charac- The composition of the-firnlequilitrrium nlD(ture
ill a
teristic for any Siven chemica! reactlon at a paflicular temperaturc depeDds upoll thc starting
spcified temPerature- amount of reactants.
whe n a calarysl is added to a reaction mixturc in
'Ihe forward reaction becomes faster on adding the
equilibriunl, the amount of the products in' catalysl.
cteases.
Adding i[ert to dissociation equilibrium of Molar coDceDirations
SiLs
of the reac(anl5 ilDd Products
NrOn at consmnt Pressure itnd tenlpcralurc in- decrcasa-
creasqs the dissociatiotl.
4, Kp is lways Sreater than K". Ite efTcct of pressuro is greater oll thc ralc of reacliol'l
than the cffect of conce[tration.
5, Equilibrium constant of a reaction lncreases if l}Ic forward reaction bccomes taster with lncrease ol
temperature is increased. teD'rperature.
EQUILIBRIUM
- I

True/False 9tatemente
Whlch ofthe follorving statements flre false ? 4. The equilibrium constant of a reaction is in.lc-
Whe[ equillbriunl is attaiDed, tbe conceDtratioD of pendcnt of the concentratioDs oftbo reaclants.
e{ch of the reactants and products bcomes equal. 5. There is no effect on the equilibriunl conslaDt of
BurniDg of magoe$ium to forn] MgO tS an irre- H2+12
-=l2HI. if some inert gas is added to it.
versiblc process. 6.'fhere is Do effect of pressure on the dissociation or'
EquilibriuD is disrurbed ifcatatlst is added m it. Nzol'

Fill ln The blanks

When equilibrium is attained, the q)ncentration of ofthc diss$iation of PCl5 at constant pressure, the
each of the reactanb afld products bconles .... .
dissoqation of PCl5 will ..,.. .
2. Chemical cquilibrium is ..... in Dature.
1 Soll(l liquid equilbriunr exists onh al ....
9' tixothermic reactiorN arc
favourcd hy........
temperaiure.
4. The rate-ratwhich a subsiance reacts is proportioDal 10. For a giveD reactioD at a ltxed tempcraturc, equi-
to its.....
'Ihe value of equilibrium constant is constant ar librium constaots Kp and K. are relatcd as........ .

constant.._... (LI.T 19941

The value ofequilibriuot constant ofan endothcr- ll' A ten-fold increase iD pressure on the reaction
n)ic reaction ..... with ris in temperature. N2 E) + 3 rr2 G) =i 2 NH3 G)
___
7, 'lbnrperalure has no effecr on the equilibrium con- at equrlibrium results in....... in Kp. (.LT
tg96)
stant for readions for which AH is ..... . 12, For a Baseous re-aciion 2 B -..- A! the equilibrium
If an ioert gas rs added to the equilibflum mixture coostant is........ rolhao K6.
5 (t.I.T. 1997\

W atchi n S Ty p e Q.u eetio n s

l. Match ihe cntries of columD Awith approprEte eotries of column d
Column A Cohmr B (New eqm. corlst.)
(a) Reaction is reversed (a)'tK
(r) Reacnoo is divided by 2 ft) K2
(c) Reaction is multiplied by 2 (c)l/K
where K is the equilibrium consrant oftbe original reaction.
2. Match th entries of columD A with appropriate entries of columns B and C.
Cohrrnn A Column B ColurD[ C
(a) Nz + 3H2
+ 2NH3(a) Inqeasc ofpressurc shifts (a) lDcrcrse of temp. shifls the
AH =
-92.5
kJthe equitibrium in thc foru,ard equilibrium in the forq"rd direction.
direction.
(D) CII3COOH + qH5OH (b) Increzse of prcssure shifrs (D) IDcrease io temp. shifis rhe
.-J CII3 COOqH5 the equilibriunt in the backward equilibrium in the backward direction_
+ H2O,AII =0 dircclioD.
(c) N2Oa <=== 2NO2 (c) Increase of pressure has (c) Increase of temp. has Do effect
A H=+ 58.6 kJ no effect on equilibrium. on the equilibrium.
lrce i"^'t'.P's Neu't Co"rsc Chehliiiiytrfrln

ASSEBTION,REASON TYPE AUESTIONS

t. (n) 2. (e) 3. (a) a. (e) s. (e)
TBUUFALSE STATEMENTS
1,3,6.
FILL IN THE BLANKS
i]"oo.,"n, 2. dynamic 3, mclting point 4, active mass 5. temperature 6. iDcreass 7. zcro t. increasc
9. low 10. Kp = K. (tT)e 11. no change 12. less.

MATCHING TYPE OUESTIONS

(a) (c), (bHo), (c)--(b) 2. (4) (a) (D), (D) (c) (a), (c)-(,)-(c)'
1.
- - - - -

H I NT5 /EXPLANATIO N g Lo Ae6 e"tio n -R.e a 5 on Ty P e G.u e eaio n e

 L' hg OT

Equil,bri ur rn-l I
(tontc EquiltI)num tn Dotuuons,

Equilibria involving ions, various concepts o, acids and basee-Arrehenius, Btonsted-Lowry and
Lewis, dissociation of acids and bases, acid-base equilibria, ionization ol water, pH icale,
hydrolysis of salts, PH cElculation of salt solutlons, acid-base tilralion using indicator, solubility
equilibria-solubiity ot sparingly soluble salts, solubility equilibrium and solubility produci,
comrnon ion effect, elernenlary idea of bufler solulions.

8.1. Strong and Weak Electrolytes

1;;;;ffi ffi.*ffi
Faraday in 1824 classified all substances into two
categories viz electrolytes and non-electrolytes.
,4 strong electrolyte is defined as a sub*ancd,
which d(\sociutx qlrnast completeb into ions in:
a4ueous solution and hence is a very good conduc-
tor o! elrctriciE. e.g. NaOH, KOII,
H2SO., NICL KNO3 etc,
HCU.

..l,7 ffioll4o E tufrtrd B a wryoud vlw ,4 wcak electrollte ir delined us a sub$anre which
aqtwts dubr w ird udt* @. Oa ilu smauurenlin aqueo$ sohttion atd
diJlsoci.qtes tn a
ollw lwd, a unpndwlwrys slttion o n*& hcncc conduas elqTricily abo to a sttwll exletu. e.g:.
dM ttul @&d elffibity ucaihdanon*lecfiolyte. NHpH, CH3COOH etc.
For example, aqueous solutions ofsugar, urea As strong clectroly,tes are completely ionised
icity. Hence they are in the aqueous solution, therefore, thcir ionisation
olutions of inorganic is representcd hy putting a singlc arrow pointing
uct electricity. Hence. torvards right e.g
HCI H2O- HlO* + (.|-
Arrhenius in 1880 e:plained that the conductance
by an electrollte is due to the presence ofiors producrd NaOH + a4 -- Na+ (aq)+ OH- (aq) etc.
by the dissociation ofthe substance. Hower,er, different In casc o[weak electrolytes, as they are partly
electrolytes dissociate to differeot e*enLs. -
ionized, an equilibrium is'set up birwedn thl
Tlntmction oltlw tntal nurnber olmoblavhith ions and the unionized electrolyte. Hence their
dLts&ialx into ions is ullztl tht degres of dls- ionization is represented by putting double arrows
( <+ ) in betweeo e.g.
socittioa and is usuall! reprwilcn b a.
. No. of mohs dlssodeted CH3COOH + H2O
==:
CH3 COO- + H3O+
Total no, of moles takeu NH4OH + aq NH4+ @q, + OH- (oq) etc.
gree of dissociation, In - the ionisation
general, of a weak
eleckolytes into two elcctrollte, AB, is represented as follows:
ctlolytes, and ,weaL .. AB (s) + ,q i- A+ (oq) + B- (aq)

811
812 Net4 Course Chemi str4

Such an equilibrium is called ionic equl- cH3cooH + H2o + cH3c(x)-+H3o+

librium between the ions aad the undissociated Initial C 0 0
clcctrolyte. conc.
Applying the law of chemical equilibrium to Concs. C(l - a) Cd Ca
thc above equilibrium we get at eqnl.
lA+l lB- | = \ir Substituting the valucs of the equilibrium
- K. ualLu
ea ert inni(ation constant.
'|uu'Jo concentrations in cqua(ion (i), we get
lABl
Dilference btween'dlssoclation' and ,- C<, . C4 a2
C2 (-' a2
= :- ... (.r.,
'ionization'. WheD an ionic compound is dissolved C(l-a) C(l-a) l-a
in water, the ions which are already present in the In casc of weak electroll'tes, the value of a is
solid compound separate out. The process is called very small and can bc leglected in comparison to 1
dissociation. On the other hand, when a neutral i.e. I - a = l. Hence, we get
molecule like HCI (i.e. a polar covalent compound)
which does not contain ions but when dissolved in Ko = Ca2 0r " =\/ ? ...(iii\
water splits to produce ions in the solution, the The degree ofdissociation, a can therefore bc
process is called lonizatlon. However, generally the calculated at a given concentration, C if K, is
two terms are used without any difference. known. Further, if V is the volume of the solution
8.2. lonisation of Weak Eleclrolytes- in litres conlaining I mole of the electrolyte,
Ostwald's Dilution Law C: l/V. Hence wc haue a = IIRJ ...(jv)
Similarly, for a weak base likc NH.OH, we
Whon acetic acid (a weak electrollte) is dis- have a=/K;7e=/KaY -.(v)
solvecl in waler, it dissociates partly into H+ or Thc ahovc equationss lcad to the lbllowing
HrO+ and CHTCOC)- ions and the followingequi- rcstrlt:
librium is obtained : For u wuk elcclrolyle, lhe dcgree qf ionitulion i\
cH3c(x)H + I{2o <----\ cH3coo- + H3o+ inversvl! proportional to lhe square rool of molor
Apptying law of chcmical cquilibrium, concent ation or directl! ptoporlionul ao lhe square
root of volume conluining one mole o! lhc solatc.
ICH3COO-l x [HrO+l
K= This is called Oshvald's dilution law.
lCH3CooHl x lHrol
REMEMBER
In dilute solution, [HrOl is constant. Thc
product o[ K and constant [HrO] is denoted as K,, (i) The approximation 1 - q : lcanbeapplied
tlte ionization constant or dissocidtiott constant of only ifa < 5oZ. lf on solving a problem by apply'
tha acid. Thls ing the approximate formula, a comes out to be
COO-I x
lHsO+l > 5'%, lhe problem may be solved again by
K" = ICH1 IctrpooHl "'ir) upplying exact formula irnd a may be calculatcd
by appllng solution of a quadratic equation i c
ll 'C'represents the initial concentration o[
thc acid in moles L-1 anda, the degree ofdissociu- -u *,/F
2a
-tri
tion, then equilibrium concentration of the ions
(CH3COO- anil HrO+) is equal to C(I and that o[ (ii) Ostwald's dilution law is applicable only to
tho undissociated acetic acid = C (l - a) i.c. we weak electrolytes because for strong electrol}{es,
havc .! = li.e- Ka + @.

p,R.o.,. b,
EF_ M.8., 9i .11 .,,
1', 1,,), 1]1i.,u :l
*]:u,1
lr 1l:: : 1 1 "*111,,
Calculate the degree of-indissociu' Solution. Formic acid is weak electrolyte and
![on aru) concentrqliot of Hro+ ions 0.01 M ionizesinwater to give Hro+ ions accordingto the
sohLtion oJ'fomtic acid. Ka = 2.1 x 10-a tt 29E K. equation
 EQUILIBRIUM lt (ONtC EOUILTBRtUM rN SOLUTTONS) 813
-
HCOOH + H2O + H3C+ + HCOO-
Thus K, : 0.01@ x 0.01a
Let c be the degree of ionization. Then thc 0.0r
(1)nccntrution trI the vari0us species present al =001 xa2=2.7xlOa
cquilibrium would be as under: [K, = 2'r x 1o-4, givenl
HCOOH +H2O H3O+ + HCOO- . 2.1x l0-1
or dz=-;;=2lxr0-2
lnitial conc. 0.01 ---------\ 00
Conc. 0.01(r -a) 0.01a 0.01a
.. Degree ofionisation, a
at eqm. = 0.01 = '6.1x 10-z : 0.14
Concentration of H,O+ ions
[ .' c is very small and can be neglected
in comparison to 1l =C@=014x001
= 1.4 x 10-3mol L-l

l. Cnlqulale the degree of ionization and [fl3o+lof is the ionizntion coDstant ofacetic acid ?

0.01 M CH3COOH solutioD. The equllibnunl c.on- I.\n\ l.E0 x 10-61

stant ofacetic acid is 1.8 x lo-J 3. What will be the percnrage of dissociatioD in
1.0 M CH3 COOH at equilibrium having di$socia-
I,\ns 4.24 x rc-2,4.24 x l0-amolL-ll
tioD coDstaDt of 1.8 x 10-5 I
2. A 0.01 M soiutioD of actic acid is 1.3470 ioDised
(degree ofdissociation = 0.0134) at 298 K What [,llls.0.424]

2' cHrcooH <- cH3coo- + H+

="\i<3'8i*"-r 8xro-6
Cmoll-l
InitialcoDc. 0 0 3. ds in Problem 2,
At.eqm. C(l -a) Ca Ca n 2 t -- 2

.,
A"=
Ca.Ca CaZ 4=i+ l 8x to-5 ='i' T - "'
ie.
el'i=Zl = T:7
o, ,,=y'ill-ioT=,1 24x 1o-3
7(, dissoqation = (4 24 x ro-3) x 100 = 0 424

,, , t. Except HgCl2 aud CdBr2, all salts are strong electrolytes.

l , 2. If the concentration of common ions in the solutions of two electrolytes (e.g: OH- ion concentratioD in
Ca (OH)2 and Ba (OH)2 solulions) is same, lhen on mixing them there is no changc in thc dcgree of
dissociatioo of either of the electrolytes. Such sdutioos are called isohydric solutions.
Bt4 Pt a,lccr's lqerl coarse Che-isirlUIIU
An acid l.r
Throughout the history of chemistry, various
acid-base concepts have been proposed and used.
In this section, we shall bricfly discuss the different Examples. Substances like HCl, HNO, and
concepts put forth ftom time to time. Each of these
HrSOo, containing hydrogen, when dissolved irr
can be appliod with advantage in appropriate cir-
cumstances. In a given situation, the chemist uses water dissociate completety into H+ ions and the
the concept that suits his purpose best. negative ions as follows :
(1) Classlcal Concept of Aclds and Bases. HCI H+ + Cl-
The earliest classification of substances into acids Walcr
and bases was based upon the characterlstic HN03 H+ + Not
properties possessed by each one of them. For
Water
example, H2S04 2H+ + sol-
Acid was defrned as a substanc whose
aqueous solution possessed the following charac- Such acids are called strong acids.
teristic properties : Substances like acetic acid (CHTCOOH), car-
(i) conducts electricity, bonic acid (H2CO3), phosphoric acid (HrPOn),
(r'i) reacts with active metals like zinc, mag- etc., when dissolved in water dissociate into ions to
nesium etc. to give hydrogen, a small extent. Thus an equilibrium is set up be-
(iri) turns blue litmus red. tween the ions and the undissociated molecules as
follows :
(iv) has a sour taste. Water
(v) whose acidic properties disappear on cH3cooH + cH3coo- + H+
reaction with a base. Wate!
Base was defined as a substance whose HzCO3 <- 2H+ + COl'
aqueous solution possessed the following charac-
Water
terlstic properties :

(i) conducts electricity,

H3Po4 <.... 3H+ + Po?-
Such acids are called weak acids.
(ii) turns red litmus blue, In general, we can write
(rr") has a bitter taste,
(ir,) has a soapy (slippery) touch H++A-
(v) whose basic properties are destroyed on
reaction with an acid.
The above definitions of acids and bases are
called opemtional defnitions os they are based upon '
ce,Tain operutions (i.e. tests) to be performed on the
substancs. However, these have been replaccd by
conceptual definitions (put forvard by Arrhenius,
Bronsted-Lowry and Lewis) which go into the
causes of the observed behaviour, based upon
structure and composition of the substances.
(2) Arrhenlus Concept ofAclils and Bases. To
W6tcr
cxirlah thc obscrvcd propcrties ofelectrolytes, Ar- NaOH Na+ + oH-
rhcnius in 1884 put forward a theory popularly Watcr
knsrm as Anhenius theory o[ ionization'. The main KOH K+ + OH-
idea contained in this thcory was that when an These are called strong bases.
electrolyte is dissolved ia water, it dissociates into
positively and negatively charged ions' Substances like NH4OH, Ca(OH)r,
Based upon this theory, Arrhenius gave the Mg (OH), , el(OH), etc. dissociate to a small ex-
definitions of acids and bases as follows : tent as follows :
EQUTLTBBTUM [ (tONrC mltLrBRrUM rN SOLUTTONS) 815
-
Waler As a result of this process, the characteristic
NHIOH <- NH4+ + OH- properties of acids and bases are destroyed.
Water Utlllty and Llmltatlons of Arrhnius Con-
Ca (OH), + Caz+ + 2OH- cept The Arrheaius concept ofacids and bases was
Watcr able to explain a number of phenomena like
Al (oH)3 e--r AI3+ + 3OH- neutralization, salt hydrolysis, strength ofacids and
bases etc. However, itwas found to have the follow-
These are called weak bases. ing limitations :
Exlstence of H+ lon and OH- ion in aqueous (i) Nature oI H+ ions and OH- ions : Accord-
solution. H+ ion is simply a proton which is very ing to Arrhenius concept, acids and bases were
small in size (radius: 10-13 cm). lt has a strong defined as substances which gave H+ ions and
OH- ions respectively in aqueous solution. But as
discussed above, these ions cannot exist as such in
the aqueous solution but exist as hydrated ions,
written as H+ (aq) and O}{- (aq).
(ii) Inability to ocplain qcidic and basic charac-
tet oI ceftain substances : Arrhenius concept
demands that an acid must contain hydrogen and a
base must contain hydroryl (OH-) groups. How-
more of QO molecules (a procass called hydra- ever, a number of substances like NHr, Na2CO3 ,
tion) to form species like H5oz+ , H7O3+ and CaO etc. are known to be basic but do not contain
HrO.+. Hence we simply represent it as any hydroryl groups. Similarly, a number of sub-
staoces like COz , SO2 , SO3 etc. are known to be
HrO+ (ag). Similarly, OH- ions in aqueous solu-
acidic but do not contain any hydrogen.
tion can combine with one or more HzO molecules
This limitation is, however, overcome ifwater
to form species like HrOf , H5O3- , H?Oa- etc. is supposed to play an important role. This is clear
Hence we generally represent it as OH - (c4). Thus from the following reactions :
the dissociation of an acid in water m:.y be repre- NH3G)+H2O <- I.rHi @$+ OH- (aq)
sented as
Na2 CO3 (s) + H2O +
HCI + Water ...--. H+ (aq) + Ct- (a{)
CHlCOOH+Ubter + H+(4q)+cH3COO-(aq) IJCO; (aq) + OH- (aq) + zNa+ (aq)
or HCI + H2O H:O+ (aq) + Cl- CaO f H2O # Ca2+ (aq) + zOH- (aq)
CH3COOH+H2O +H3O+
- (aq) +CH3COO- (4q) Cx)2+ H2o --. Co3- @q) + 2H+ (aq)
Similarly, the dissoc"ation of a base may be
So3 + H2o + So?- @q) + 2H+ (aq)
represented as
NaOH*Water ------- Na+ (aq)+OH- (aq) (iii) Inability toqkin the reaction betu)een an
acid. and base in absence oI water '. TWo important
MI{OH+Water + I.rHi @Q+OH- (aq) examples are :

NH3 G) + HCI G) .------ NH. cl (s)

CaO (,r) + G) """""') CaSOn (s)

SO3

NaOH Na+ + OH- (3) Bronsted-Lowry Conccpt of Acl& and

Bases. To overcome the limitations of Arrhenius
HCI Hf + Cl-
concept, Bronsted (a Danish chemist) and Lowry
or Na+ + oH- + H+ + Cl-+ (an English chemist) independently and simul-
tatreously, in the year 1923, proposed a broader
Na+ + cl- + Hzo concept of acids and bases. According to this con-
or H+ + OH- HrO cept :
8/6 Necu Couvse Cfre m i strtl

An acid is deJined as a substunce which has the as$'ell as a basc and hence is callcd amphoteric or
lendenc! to give a prolon (fl+ ) md o base ir amphiprotic.+
deJined us a substance y'hfuh has a lzt denc! to (r,) The reaction (c) above indicatcs that
tocept a proton, In other words, afi ocid Ls a proton Bronsted- Lowry definitions o[ acids and bases are
donor vhercus s bqse it a proton acceplor. not restricted to aqueous solutions. In this reaction,
HCI is acid because it gives a proton and NH3 is a
The above definition may be explained with
thc help o[ the lollowing cxamples :
base because it accepts the proton.
(ul) The presence oI hydroryl (oH-) groups
(a) HCI + HrO . . H3O+ + Cl- is not essential lor [o act as a basc. Thc
a substancc
only requirement is that it should have a tenclency
(b) CH3COOH + HzO + Lo accept a proton.
H3O+ + CH3COO- (r,ii) The above reactions indlca[g that a sub-
(") stance acts as an acid i.e. gives a proton only when
NH3 + H2O <- NHl+ + oH-
unother substancc to accept the proton, i.e. a base,
(d) Co3- + H2o + HCot + oH- is prescnt. For example, acetic acid does not act as
an acid in benzene solution because tbe latter does
(r) HCI + NH3 + NH4+ + Cl-
not accept the proton.
Thc following important rcsults may be (viii) The reverse reactions arc also acid-base
derived from these equations: reactions. For example, in reaction (a), in the
(i) HCI and CH3COOH arc acids bccausc revcrse process, HrO+ cangive a proton and hence
they donate a proton to HrO. is an acid while Cl- can accept the proton and
(il) NH, and COI- are bases hence is a basc. Thts there are l.wo acid-base pairs
because they
in reaction (a). These ure HCI-Cl- and
acccpt a proton from water.
H3O+ -H2O. These acid-base pairs are called
(ii) Not only molecules but even the ions can co jugqte acid- bosepal)s. Obviously,
act asacicls orbasese.g, COrz- ion in the abovecasc
is acting as a base, I conlugate pair of rcid and a bare ilws b! d
proton onb i,e.
(ir,) In the first two reactions, water is accept-
ing a proton and hence is base. In the nelit two
Conjugate acid # Conjugate base * H*
rcactions, water is donating a proton and hcnce is The conjugate acid-base pairs in reactions (a)
acting ils an acid. Thus water acts both as an acid to (e) may be represented as follows :

Conjugate Pair I

Acid,
t
Basc,
Conjugate Pair II I

Acid, Base,

HCI + Huo \-- H.o* + cl-

cH3cooH + H,O \- Hlo+ + cH3coo-
----l
H2o + NHr NHo* + oH-
\-
HrO + coi- HCO; + oH-
\-
HCI + NH3 s-
---------.\ NHo* cl-

,.Note. According to this concept if t*o acids (rvhich are acids with resPect to water) are mLred, the
rveaker acid will act as a base with respect to the stronger acid c &
.Anrphotcric is a gcncml tcrm fo! a substance acting as an acid aswctl as a basc When a(id base behaviout is rcslrictcd to
protorr lransfer, it is caUcd amPhiFotic.
EQUtLTBRtUM [ 0ONlc EoUlLlBRluM lN soLUT|oNS)
-
HCIO4 + H2SO4 H3SO4+ + ClO4- ln acid ir defined os substsnce (ulom, ion or
Acidl Base2 Acid, Basel moleule) which is capubk ol acccpting a pair of
(Pcrchloric acid) eleclrons and a base is defued as a suhstance which
Thus HrSO. is a amphoteric or amphiprotic. is capoble ol doratiag an unshared pair of
ebttrons. In othcr word,t, un acid ir an electron pair
Adyantages of Bronsted-Lovvry concept oYer acceptor while u basc is an electron pair donotz
Arrhenius concept :
(i) Bron-sted-Lowry concept is not limited to Obviously, the reaction between an acid and
molecules but includes even the ionic spcies to act
a base, according to this concept, amountsto the
formation of a co-ordinate bond or dative bond
a.s acids or bases.
bctwcen them.
(ri) It can explain the basic character of the
Examples. (i) Reaction befiecett BF.' utttl NH., :
substances like NarCOr, NH, etc. (which do not
contain OH- group and hence were not bases
:F: H
accordingto Arrhenius defrnition) on thebasis that
.x .

they are protoo acceptors.

:f , B + :N xH .........-
.x .x
(iii) It can explain thc acid-base reactions in :F: H
the non-aqueous medium or even iD thc absence of
a solvent (e.g. between HL1 and NH).

Llmitations of Bronstcd-Lowr? concept. Al-

though Bronsted-Lowry cotrcpt has a widcr scope
than the Arrhenius concept but it has some limita-
tions e.9.,
(i) It cannot explain the reactions between
acidic oxides like COr, SO2, SOj etc. and thc while BF, (inwhich boron atomhas only 6 electrons
basic oxides like CaO , BaO, MgO etc. which take in the outermost orbit) can accept a pair of
place even in the absence of the solvent, e.g. electrons, NI{, is a base and BF, is an acid.
CaO + SO, '---- CaSOr (ii) Reoction betweert NHrand H+ ion
H
Obviously, there is no proton tratrsfer in-
H-N: + H+ .*
I
volved in this reaction.
(fi) Substances like BFr, AlCl, etc., do not I bwis acid

have any hydrogen and hence cannot give a proton H

but are known to behave a^s acids. lrwis bssc I H I' I H
(4) Lewis Concept of Aclds and Bases. Itlll
Bronsted-Lowry concept of acids and bases was
broader than Arrhenius concep in the seLse that it
could explain not only all the Arrhenius acids and
bases but included many more substances as bases.
However, it didnot much enlarge the scope ofacids
F
lH-N-Hl
L-r I t,l
(iii) Reoction between BF, and F- ion
or lH-N-H

as this concept also emphasized the presence of

I
hydrogen in an acid like the Arrhenius concept.
F-B +
G.N. Lewis (an American chemist) in the I

same year i.e. 1923, proposed a broader concept of F

acids andbases. This concept eliminated the neces- t wis acid
sity of the presence ofhydrogen in an acid and this
included manymore substanccs as acids and bases.
According to this concpt (also called electronic
concept) :
B/8

(iv) Reaction between CaO and SO, capable ofgiving an electron pair has the tendcncy
2- to accept a proton. For example, consider the reac-
tion

l ,- :o: o
Ca+ t): I + S: O :O:S:O:
l , O," -Ca2+ o:
l-Ewis acid

(v) Hydration of metal ions base. However Brcrnsted acid mqy not be o Lewi,t
acid. For example, in the above case, HrO is
,.H Bronsted acid because it is giving a proton but is
nlr+ + 6: O( -------
lAl (H2O)613+
kwis acid \H not a Lewis acid because it is electronically satis-
Irwis base hed.
TDes of Lewls Bases. Lewis bases can, ob- Usefulness and Limltatlons ofLewis concept
vioudy, be of two types. These are : No doubt, Lewis concept is the Eost general out of

-(i) Neutralmolecules like NH, , R - NH, ,

R - OH, H - - H etc., in which one of the
O
atoms has got at least one lone pair of electrons.
(r'i) All negative ions like F- , Cl- , Br-, not be explained
I-, OH-, CN- etc. it suffered from some serious drawbacks as fol-
ltlpes of Lewis Acids. Lewis acids can be of lows:
four types. These are : (i) Lewis concept is so general that it con-
(i) Molecules having a centrul atom with in- siders everyreaction forming a co-ordinate bond to
complete octet : be acid-base reaction. This however, may not be
F CI always true. [For example, according to this con-
cept, even some metals are acids e.6 nickel is acid
.X .x because it forms the co-ordination compound with
e.g. Fi B and Cl i Al
COi.e. Ni (: C = O: )n, called nickel tetracarbonyll.
x, .x
F CI (ri) The necessary requirement in Lewis con-
(BF3) (Alcl3) cept is the formation ofa co-ordinate bondbetween
the acid and base. However, the well known acids
(ii) Simple cations e.g., Ag+ , Cu2+ , Fe3+ like HCI and HrSOo do not form any co-ordinate
etc. These ions can accept pairs of electrons and
bond and, therefore, should not be acids according
hence are Lewis acids.
to this concept.
(jiif Molecules having central atoms with empty
d- ofritsls : The central atoms in these molecules -(ji) Aiid-base reactions are usually fast but
formation of co-ordination compound is slow.
call expand their outer octet by tahngup electrons
Hence it does not fit in the acid-base concept.
in their empty d- orbitals, e.g. SnClo, SiFa, PF, etc.
(iv) The catalytic activity of an acid is due to
have the central atoms containiug empty d-orbitals.
H+ (aq) ion. Since the presence of hydrogen is not
. (f) Molecules containing c ,nultiple bond be- an essential rcquirement for a Lewis acid, many
tween two atoms of diflerent electronegatiities e.g. Lewis acids will not have this property.
CO, contains double bonds between carbon and
-(v) +rrficniu+concopfarul Barnslgd
gqDcept
orygen (O = C = O). Since orygen is more can explain the strengths qf ir_c1d-q_ a_4d. [ases (as
electronegative than carbon, therefore carbon ac- discussed in the next section) but Lewis coacept
quires a slight positive charge and thus can accept cannot,
a pair ofelectrons. Hence CO2 acts as a Lewis acid.
It may be pointed out here that, no doubt,
It is interestitrg to obseruethal Lewis boses are Bronsted concept is more general than Arrhenius
olso Bmnsted Dases because a substance that is concept and the Lewis concept is the most general
 EQUTLTBRIUM
- I (ONtC EOUtLtBRtUM tN SOLUTTONS) 8/9

out of all but still Arrhenius concept continues to We put K [HrO] = It, called dissociation constant
be most important io explaining a number ol
phenomena. ofthe acid. Thus
lA-l IH3O+l
\ = tHA]
Diss<
Alternatively, we write
Acids like HCl, HNO3 and HrSOo when HA + aq <-- H* (aq) + A- (aq)
dissolved in water dissociate almost completely [H+ (aq)llA- (aqtl
thus producing a large number ofH+ ions. Hence 6=
these acids are called strong acr'ds. On the other
" IHAI
hand, acids like CHTCOOH, HF, I{2CO3 , Krowing the value of the dissociation con-
stant of the acid, \ and the concentration (C) of
HrPO. etc. dissociate only to a small extent in the
the weak acid HA taken, the concentration of
aqueous solution giving sriiall amount of H+ ions HrO+ or H+ (a4) in the solution can bc calculatcd
and hence are call ed,wesk acids. Similarly, bases
as follows :
like NaOH and KOH dissociate almost com-
pletely in the a HA + aq +H+ (qq) + A- (aq)
number of OH Initialconc. CnolL-l 0M 0M
whereas bases Corcs. at eqm. (C-r) M .rM xM
etc. dissociate only to a small extent in the ... * - lH+ (a(tl llA- (aqll _ x xx
aqueous solution and are, tberefore, called weok " tHAl C -x
bases. As usuallyx is very small as compared to thc
Thus the dissociation of weak acids or weak initial concentration C,r can be neglected in com-
basesinwatercanbereprcsented asan equilibrium parison to C. Hcnce the equation is simplihed to
process. For example, the form
HrO+ J
CHTCOOH +
NH3 + H2O
CIITCOO- (aq)+ HtO+ (oq)
K,=i o, x=,/qFe
<-------\ NH4t @q)+ OH- (sO erc.
However, it may be pointed outer that ifx is
ln general, if a weak acid is represented by more thara 5Vo of C,.r cannot be ncglected in com-
HA, its dissociation in water can be represented by parison to C and the equation has to be solvcd as a
the equilibriurr
quadratic equation to get the value of.r.
HA + H2O f- a- @q)+ HrO+ (aq) Similarly, the dissociation of a weak base in
Applying the law of chemical equilibrium, the water can be represented by the equilibrium
expression for equilibrium constant will be BOH + aq B+ @e + OH- (aq)
.- [A-l [H3o+l ==
The dissociation constant of the weak base,
" [HAl [HrOl represented by K6, will be given by

As HrO is solvent, its concntration is large K. _ lB+

(a4)lloH- (a4)l
and remains almost constant (= 55.5 mol L-l)r. " [BoHl

sot UED EXA,T,IPLE

;-:i----
------:-":..:_Tfi
= r.'.- Colculale lhe H+ ion concentra- CHTCOOH + aq
tion irt 0 M acetic acid solution. Given thot tlrc
10 =r
lissociution co .\tont of ucetic uci(l irt wttar is CH3CoO- (ail + H! @q)
/.,9 \ .lr-). IDitial 0.10M 0M 0M
coDc.
Solution. Suppose al equilibrium,
Concs. (0.10 -r)M rM rM
lH+ (oq)l : x mot L-1. Then at eqm.

1000 g. Thcnforc, numbcr of molcs in 1 L of H2O = 1OO0/18

= 55 5 molcs.
8/10
t-',
r,,'1.,1,1t's Ned Coutse Chemiitrqlfft[fi

ICH3CoO- (sq\l lH+ (aq)l = 1'8 x 10-6

lcHrcooHl r = V1.8; 10-6
. xxx t = 1.34 x 10-3 M
1 L1 ,,( rr, - 0.I0 _r - 0.I0 te [H+l = r'3a x 1o-3M
or ? = (1.8 x 10-5) x 0 10

H+ (aq)inO.2 M solution of HCN. Giveo that the dissociation constant of

Chlcutate rhe concentration of
llCN in water is 4.9 x t0-r0. l^ns. 9 9 x 10-'6 Ml

8.5, Strengths of Acids and Bases .+*x$irii,i{+tr.jri+}:ii{:.,:i

According to Arrhenius concePt, an acid is

clclinctl as a substance which when dissolved in
irtcr givcs H+ ions and a base is defined as a
rbstance rvhich when dissolved in water gives
OH- ions. Thus
Grealer lhe number of H+
io'/.s pmiluce.l in lhe HA + Water + H+ @fi+A- (aq)
uqueour the stronger is lle acid' Similar-
nhlion, Initial
ly,gre er the number of OH- ions pmduced in lhc 00
ul eo rs solulion, slronger is thc base.
conc. C
Conc. C - C4 Ca Cg
Now, as greater Ls the dissociation con-stant of ateqm. = C(1-4)
the weak acid (lK,),greater Ls the amount of Applying the law of chemical equilibrium, we
I{+ (a4) produced, therefore stronger is the acid. get
Thus Ko values give a measure of the relative lH+ (aq\l lA- (uq)l
, -
strengths of the weak acids. Similarly, Ko values give IHAI
a mea.sure of the relative strengths of the weak where K, is called the dissociation constant (or
bases. The lQ values of some common weak acids ionzation constant) of the acid.
urc given in Thble 8.1. Cs . C<t c'2 C

(K ) ofsome ueak rxrnol)asic acids at 29lll

A,s the degree of dissociation (a) of a weak
Acid Fo nulo Dissociation acid very small, we can take 1 - q =
is l.
constant (K.)
Fornric acid HCOOH 1.? x lO-a Kr=o2c .,' ': 141
Acetic acid cI{3cooII l8x10-5 Thus if two acids of equimolar concentration
Benzoic acid c6H5cooH 6.5 x 10-5 are taken (so that C is constant),
['henol c6H5oI-l I 3 x 10-lo
", -\/\
Ilydrofluoric acid }IF
HCN
6.8x 10-a 4- K,,
llydroclanic acid 4 9 x 10-10 But degree of dissociation is a measure of thc
Ilypochlorous acid HCIO 32x10-8 stren an say
llypobro[]ous acid
Hypoiodous acid
Nitrous acid
HBrO
HIO
HNO2
2 1x tO-e
2.3 x 10-ll
45x10-a
\l =q
 EQUTLTBRTUM [ (rONtC EQUtLtBRtUM tN SOLUTTONS)
- 8/11

Thus lhe relaliye strcngtht ol two acfuLs ol equi It must be remembered that since the ioniza-
moldr concenlration cfln be compared by t*ing tion of an acid or a base increases with dilution, the
squane flNl o! the rafio of lheir dis:sociation con. strength of the acid or the base increa-ses with
stanls. dilution.
Note that K, and Kb are taken as dimen-sion-
e.g K, for CHTCOOH = 1.8 x l0-5
less quantities (as already explained in unit 7) be-
K" for HCN = 4. 9 x 10- lo cause the standard state concentration of all the
species involved is taken as L mol L-1.
Strength of CH, COOH 1.8 x 1o-r
= Polyprotic acids and Polyacldic bases. Some
St.e,Uth.f t{CN 4.9 x 10-ro acids like sulphuric acid (HZSO.), carbonic acid
= t/3{ii " to, -- L.gz x tG = tEz (HrCOr), oxalic acid ((COOH).), phosnhoric acid
(H3POa) etc. contain more than one ionizable
Hence, CHTOOH r's neqrly 192 times sionger
than HCN.
proron. Such zctdB :trs-1qtreil polybasic or
For example,
Similarly, the relative strengtbs of two weak two steps as
bases of equimolar conccntrations can be com- -
foilb-ws':
pared by taking the square root ofthe ratio ofthcir
dissociation constants, i. e.,
., HrX (oq) + H* (aq) + HX- (aq)
ptrength of base (BOH), \A,/nx- lrqy + )r
w Strcngth of base (BOH), =\/tr
Ko,
H* (aq) +
Thcir ionization constants, K,r and I(o, called
@q)

where \, and IQ, are the dissociation c.nstants of (he first and the sccond ionization con^stant respec-
the two bases. tively, will be given by the equations
The dissociation constants of a few bases at
zcsr lre giyel rab]:.12 b:]:I K _ lH+llHx-l '-e2
K _ lH+llx2-l
in :.
'l'\lll,E It,2, I)issociation or krnization constirnts
't [HrXl lHx-l ',

(K6l ofsome \itJk l)ascs xt f,9sK The overall equilibrium may be btained by
adding the stepwise dissociation equilibria. Thus
Ilase lormrtla Dissociatiorl for the above process, the overall equilibrium will
coustllnt (Kr) bc
lnorSflDic Bases HrX (rrq) <:+ 2 H+ @e + X2- (aq)
lAflmonia NH: 1.77 x lO-5
I

nriDc NH2OH 1lxl0-8

lTJydroxyl
Ilydrazxte NHzNH2 17x10-6 Evidcntly, \ = \, "K,,
Organic Boses Similarly, a tribasic acid like HrPO. has three
Methyl anline cl13NH2 3.7 x 7O-a ionization constants. The overall ionization con-
stant (Kc) will be the product of the, ionization
Dimethylamine (cHr)2NH 5.4 x l0-a coBslants of the three steps r'.e.
Tiiethylantine (cHt)3N 6 45 x l0-5
ADiline c6H5NH2
L = IL, x &r, K,,
4 27 x lO- to
The ionization constants of some polyprotic
PyridiDe c5H5N x
7.7'1 10-e acids are given in Thble 8,3 below :
8112 Nett Course Chem istrgfiffi)
rmc rroltt acids at 29tK
I
Acid K., Ko., IL3

Sulphuric acid (rt2SO4) very high 1.2 x l0-2

Sulphurous scid (H2SO3) l7x10-2 6.4 x 10-8
Oxalic acid (co o g )2 5.9 x 10-z 6.4 x 10-5
CirboDic acid (HzCO3) 43x10-7 5 6 x 1o-11
Ph6phoric acid (H3PO4) 75xt0-3 6.2 x 10-8. 42x1o-t3
Arsenic acid (H3PO1) 5.0 x 10-3 83x10-8 6 x 10-lo
'7 4 x 1O-' I7x10-5 4.0 x lo-7
Citric ircid

It may be noted from the above table that strcng acid (H3O+) has the weak coniugate base
4,,K,,,K., (II2O). To sum up
Similarly, polyacidic bases also ionize il steps I stpng qcid has d wmk coniugate base md vbe
with ionization constsnts Krl Iqr , Kr3 etc. ,!ry4a.
'
According to Bromted'l,omf concePt, the Thus the relative strengths of some acids and
relative strengths of two acids are compared by their conjugate bases may be represented as fol-
comp to donate Protons. lows :
Simia hs of two bases are Stro[gest
comp tendencies to accept Acid : HIO, > HNO, > HF > HCOOH>HCN>H2O
protons.
Con- IO! < NOz- < F- <HCOO- <CN- <OH-
The relative streogths of the two acids or the jugate:
two bases involved in the two acid-base conjugate
Base :
pairs can be found out if we know whether forward
Strongest
ieaction is favoured or backwatd reaction is
favoured. For example, consider the reaction

Acidl **, Acidz Bascl

H favoured or the backward reactio n will be favoured '

to com
HCI is
stronger tendency to give prototr than H3O+)' An acid when dissolved in water gives H+
stronger base thatr Cl-. Thus t/re ions and the corresp otding anion. Similarly, when
Sirnilady, HrO is a
a base is dissolved in water, it gives OH- ions and
strong acid (HCI) has a weak coniugate base (Cl- )'
the correspouding carion. These anions or cations
Agairq consider the reaction further interact with water. The reaction of the ion
wrth water is calhd, !tStdr9fu!;-. The followirrg three
CHsQOOH + HrO + H3O+ + CH3COO- different possibilities arise :
Acidt Basc2 Acidz B"*r t hYdrated. The cations
Here, bachrard reaction is favoured. This of OH, KOH etc. alld the
shows that H3O+ is
stronger acid than an HCl, HNO3 etc simPlY
CH3COOH. Similarly, CH3COO- is a stronger undereo hvdration i.e. surrounded by water
moleiles aitracted by intermolecular forces. This
base than HrO. Thus we again observe that the
 EQUtLTBHtUM
- ll (tONrc EoutLtBRtuM tN SoLUTIONS) 8/13
is because these ions are such weak acids or bases co3-, HCo3-, s2-, HS-, CN-,
that they cannot react with water by splittitrg it into
H' and OH-
ions. Examples of some ions that CHTCOo-, pOl- etc.
simply undergo hydration in aqueous solution are 3. Positlve lons oft?cak bases rcsstvith water
cl-, Not, so?-, clo;, Na+, K+ etc. and
2. Negative ions ofweak acids react with $atr mple
molecules, setting up acid.base equilibria and base
giving alkaline solution. The general equation for NH.OH). Its hydrolysis may be represented as
anion hydrolysis may be written as NHl+ + Hzo + NH3+H3o+
x- + H2o +
Base
HX + OH- Acid Basc Bas Acid
Acid Acid Bas. As only the cations obtained from weak bases
e.g CN- + HrO HCN + OH- undergo hydrolysis as above, it can be said that
s2- + H2O
=- these are those cations that are stronger acids than
+ HS- + OH- etc. water. A few examples of such cations are
Anions that uudergo bydrolysis as above are NH1+, Be2+, znz+, Al3+, Fe3+ etc.
the anions of the weak acids.
are stronger bases than water Acid-base equilibria are also set up when salts
concept). Examples of some are dissolved in water. The reaction of salts with
are water is called .salt hydrolysls, and has been dls-
cussed in section 8.10.

i H+ ion (which rs barely

a proton) is so small rn size that it caDno! exist as such in the aqueous solution. lt
combines with four H2O molecules surrounded tcrrahedralty and exists as H9 Oa+ ion (H + + 4
H2O ...-
Hroo*)'
: Ltke fI2O, many other liquids also undergo auro_protolysis e.&

v^ NH3 + NH3 NHo+ + NH!

-r
H2SO4 + H2SO4 (r H3SOa+ + HSOa-.
ES 3. Clnssification of solvenLs

8.7. Dissoclation Constant

and lonic Product ol Water +*r+*trit*taxil+*r.+rltilt,
H2O + H2O i.----\ HrOr + oH- ...(t)
This ionization is czlled self-ionization ofwater.
_. . F " watcr is poor conductor of electricity.
This shows that water is a weat electroty,tc 1.e., it is , Applyrng_the law of chemical equilibrium ro
tbe above equilibrium, we get
ionized to a very small extent as
Hro i- H+ + oH- lH+l [oH-l _ _
or morq accurately, it may be written as
lHrol
 Pradeep's
all4
-] H30+) ions and OH- ions increasesand hence thc
lH3o+l [oH
or -- [HFF- : r\ ...(,,) toli-9 n19a19t {t9 ilcJg::::..
'I'AIILE 11.4.\blrres of q ut diftclcnt ((rnl)\'
where K is the dissociation constant of water'
Since water is ionized to a very snrall extent, femperenture ('C) K,,
this means that out of millions of water moleculcs,
only a few are dissociated into HrO+ ald Otl- 0 0.1 x lo-la
ions. Thus thc concentration of unionizcd rvatcr l0 0.3 x 10-la
molcculcs i.c. [HrO] remains almost ctrnstant 25 1.0 x t0-14
(being cqual to 1000/18 = 555 rnoles per litrc, 1.5 x 10-la
30
b".urr"." i litre of water = 10(X) cc = 1000 g and
molar mass o[ Hr() = l8 g mol-l) i e. 40 3.0 x 10-la

lH2ol : con'tant 50 5.5 x l0-la

60 9.6 x 10-la
Equation (ii) maY be rewritten as

lH3o+l[oH-] : KlHror- i HrO+ Ion and OH- ioD concentrations in

= constant X constant purc water at 298 K : Pure water ionizes as
= K.,' anotbcr constullt' H2O + HzO <------r H3Ot + OH-
callccl ionic product of water. Hence Obviously, for any degree of ionizatiou, we
will always have
Ionlc product of water rnoy be defrnd ns the
produc! oI tlta lrtoltt concentralion o! H!O+ ion\ lH3o+l : [oH-l
arut OII- iorts (or H+ iotts stul OII- ioz't), But at 298 K, we know that
The dissociation constaot ofwatcr, as givcl [ry 11,', = [HrO+l toH-] = 1.0 x 10-14
ctrn. Gi), cao be calculatod by subslituting th' .' [Hro+l [H3o+l = 1.0 x 10- r4
vuiucs ot [H.O1l,IOH ]afll lHzol. Thus, wc tsct
or lH3Orl2 = 10 x 1'0-14
lo-]=x=lo-? 1.8 x r{) 16
K=
55.)J = ot [H3O+l = VI 0x l0-r4
N,iG cariiuily- that dissociationr'ionizatiol =10xl0-7moles/litre
constanl of water (K) is diflerent from ionic Thus in pure water at 25oC,
product of water (K,). The two are related as x l0-7M
lH3O+l = toH-l = 10
K
*= 15; or K*=Kx55 55 8.8. H3O- ton and OH- lon Concentrations in
Aqueous Solutions ol Acids and Bases:'lr' 'r"
Further, it must be noted that ionic procltrct of
waler is constant oDly at conslant lempuraturu lt" As already explained above, for pure water at
vulue at 25'C (298 Kiis found to be 1 008 x l{)-r{ v)8 K
However, for simpliciry, the value of K- at 298 K is lHjo+l = [oH-l = 1s-r ]\4
usually taken as
Now, if some acid (say HCI) is added to the
K*= 1oox 10-u pure water, then
Effect of tmPerature on \' The ionic [H3O+l > 1o-7 M
However, experiments show that the equation
X* = [HrO+l IOH-I is still valid Thus the
[OH-l decreases and may be calculated
as
K_
[oH-l = ------ -
rnolecules dissociate into H+ (or HrO+) ions and
OH- ions. Thus the concentratiou of H+ (ol
 EaurLrBRluM (oNtc
- tr EQUILTBRTUM tN SOLUTTONS) 8115

Again, if some base (say NaOH) is added to method of expressing the H3O+ ion concentration
pur water, then
in terms of pH The symbol has been taken fiom rhc
loH-l > 10-7 M Danish word potea z de hydrcgen inn which nreans
But the equation Kl., :
[H]O+l [OH-] is still power of Hydrogen ions. The following diffcrent
found to hold good. Hence [HrO+l decreases and definitions of pH are used to exprcss the H1O+ ion
may be calculated as concentration.
K (i) pH oI d solutim is tl{rned us the magnitude o!
tH3orl =ffi tha negati"e pover to which lO trust be raired to
Eprsrs the hldtonium ion (H!O+ ) Lnnrzrtmtion*.
The increase or decrease of the H3O+ ion
conceotration in an aqueous solution of an acid or Thus ifin a solution
a base may be explained qualitatively on the basis
of Le Chatelier's principle (or common ion effect)
lHro+; = 16-' .'.(r)

as follows : pH=x
2H2O i- H3O+ + OH- However, this definition can bc used onlv
where the lHrO+l can be expressed as a powcr oi
Ifsome acid is added to pure water, HrO+ ion
10. In many cases, it may not be easy to do so, c.g ,
concentration increases, therefore the equilibrium a solution may have [H3O+l = 2.5 x 10-i N{.
shifts in the backward dkection (or ionization of
HrO is suppressed). Thus the OH- ion concntra-. A more general definition may be arrivecl ut
from equation (i) as follows :
tion decreases. Similarly, ifa base added, OH- ion
concentration incrcases. Again, the equilibrium Thkinglogarithm ofboth sides ofequation (i),
we get
shifts in the backward direction (or the ionization
of HrO is supprcssed) and hence the H3O+ ion log [H.0+] = log 10-'
conccntration decreases. = -.r log 10
e.9. pH-A Convenient ReDresentation or = -r (log 10 = l)
of H:O lon C c l] c e n I ratro n :::i:.i::,r::i:::ll,i,i:r:iil ::.: i: l: i : i:::i : or x= - log[H:o+l
It has already been discussed above that a i-e. pH = -log lH3()+l ..(i,)
solution may be neutral, acidic or alkaline, the
cq uation This is the most common form used in numcri-
K,, cal problems. Thus
= [H3O+] [OH-J
(ii) pII nay be deJined qs negdtive logarithn oI
= 1.0 x 10-ra at 298 K lEdmniwt io n conccarat ion.
always holds good. Thus if HrC)+ ion concentration
Equation (li) may be rewritren as
of a solution is known, OH-
ion concentration is
automatically fixed. Thus to express the acidity or pH : log [HrO+]-l
alkalinity ofa solution, it is sufficient to express only
the H.O+ ion concentration. Since the pioduct oi
or pH : log
tF1fr.
H"n"s

[H3O+] and [OH-] is always 1.0 x 10-14, the con- (iii) pII nay also be dcfined as logarithm oJ the
centration of H,C)+ ions mayvaryfrom 100i.s. 1M reciprocal ol H ,O+ ion concentration.

to 10-14 M. Thus a solution may have [HrO+l pH scale : Thcoretically, a solution m:ry lr.rr,
= 2.5 x 10-5 M or which may be writteD as any HrO+ ion conccntration and hcncc may ha\e
0.000025 M. Obviously, such a method of express- any pH value. Horvever, pructically, the solulionr
ing thc H.,O+ ion concentration is quite cumber- having HrO+ ion or OH- ion concenlration morc
sonre. Sorensen, in 1909, suggested a convenient than 100 ( = 1M) and hcnce OH- ron or HrO+
'srriclty scaking. iD ptacc of nrots. Goncrtrtrationr, acriviries of H+ ioru (rH+;";. I1.".;., r] l.*
the two arc cqual. "nr".nrrariorr.
8i 16
ion conc. less than 10-11 l'{ are not common. This
is because such solution's are not easy to obtain and
moreover as the concentration increases, the de-
gree of dissociation of the acid or the base
Netl Coutse Chenristrg
decreases enormously, Hence the pH range is
taken as 0 to 14 for most of the practical purposes.
The acidity or the alkalinity of a solution may bc
represented on the pH scale as follows :

lHso+l 11 1O-r2 i O-13 to-l{

1oo 1on 10-2 1o-3 1o-r o-5 I o-' l O-7 10- to-o 10-10
I tlll
ttll
ttll
ltll
rrll
gASIC CHARACTER INCREASES

NEUTRAL

0'l 910 11 12
pH

Relationship between pH and pOH. Just as -loglt - logK6= -logKp

- log [H+1, similarly, pOH
= -log [OH-l
pH =
Since [Hro+] IoH-l = K, = 10-r4 at 25' C
i.e. I pr., +p& =prv. lry-
. . log [HrO+] + log [OH-l = log K- Limitatlons of pIl scale.
(i) The pH values of the solutions do not give
= tog 10-14 - -14 the exact idea of their relative strength. For ex-
or -log [HrO+] -log [OH-l ample,
= -log K,, = 14 (a) A solution of pH = t has hydrogen ion
concentration 100 times than that of a solution of
pH =3, and not 3 times.
(D) A 4 x l0-5 N HCI solution Ls twice con-
Relationship betweenpKo andpK, values (i.c.
ceEtrated as compared to 2 x 10-s N HClsolution
balween ionization constant ol a teeak acid attd lhst but the pH values of these solutions are 4'4 and
ol it.r conjtgate bose). 4 7 respectively, and not double.
Consider the weak acid HF. Its conjugate basc (,r) pH = 0 is obtained in lN solution of a
is F-. They dissociate as follows : strong acid and lbr concentration 2N, 3N, 10N etc.
HF ;J 11+ 1P-, the value can be negative too. Similarly, for a con'
ccnhated solution of a strong base (> 1 M), pH
- - IH+l [F-l ..(D can be greater than 14.

F- + H2O <- og- +nr' (irr) A 10-8 M solutiotr of acid can not havo
pH = 8. The value will be close to but < 7 (see
- loH-l lHFl
^D -
(iD iolved example under'Tlpe VIII'page 8/26).
tF-l Messurement ofpH. Though accurate meas-
Multiplying eqns. (i) and (ii), we get urement of pH of a solution is done with the help
K, x Kb = tH+l toH-l =K? of an instrument, called pH-meter, approximate pH

v
(within the range of 0'5) can be determined with
I fr,xf.o=fv i
pll papers which show different colours
the help of
when dipped in solutions of different pH.
log Ko + log Kr = log K,
 EQUTLIBRtUM
- 0ONtC EQUtLIBRTUM tN soLUIoNs) 8117

?,R.@..;@.,rL_FM.-9-..@.N i r{L( t,r. \r'r()N olr rH.or l. roII- I & pH

IYPE I. Orl thc cslculatlo! of IHrO* ] and IOH- | 0 2 M sodium scetate. Givcn thqt the ionization
(K) lot acetb acid is I . I x 10-s,
constsnt
, I \ \\l!,1 \' 1 Calculate tlrc H3O+ and OH- Solution. Acetic acid ionizes to a small extent
ion concettrations at 25" C in wherEi-as
soclium acetate (being a salt) ionizes com-
(i) 0.02 N HCI solution pletely. Suppose acetic acid ionized at equilibrium
(ii) 0.005 N NaOH solution
: r moles. Then
CHICOOH+H2O ;:==l ggr699-agr6+
!4,1S1. (i) HCI completely ionizes as
Initial
HCI+HzO ,H3O+ + Cl- 0.02
moles
... [H3O+] : [HCU Moles 0.0?-x xx
: 0.02 N (Given) at eqm.
: 0.02 M cHrcooNa ...-r 9111699- .,r- 1r1u+
. HCl is monobasic)
( Inirial 0 z 00
= 2x10-2M moles
Now as [Hro+] [oH-l : Kr" = 1o-ra Moles 0 0.2 0.2
K l0- t{
at eqm.
' IoH-l = = Zx 10= Thus in the mixture solution
trptl ICH3COO-] = 0 2+ x =O.ZM
= 5 x 10-r3M
(il) NaOH completely ionizes as (CHJCOO- are obtained mainly from
NaOH Na+ + OH- CHTCOONa, therefotex < < 0.2)
. toH-l : [NaOH] = 0'005 N (G,ven) [cH]cooHl = o'02-x = 0'02M
(.. NaOH is monoacidic)
= 5x1o-3M Kr= lcH3coo-l [H3o+l
lcH3cooHl
Now as [Hro+] [oH-] = Iq = 10-ra
0.2 x [H3O+]
.'. lH:o*l =
. K, l0_r4 18x10-s=
lrr_| ,x ro= = 0.02

or 1.8 x 10-r x 0.02

=2x10-12M [HrO+; = 0.2
1.E x 10-6 M

T,ROBLEM9 FOR
lf hydrogen ion concentration iD a solurion is 1 x 10-5 moleMitre, calculate the concentration of oH - ion in
this solutior (K,y = 1O-l{ moles2 / titre2) [Ans. 10-9 mole-s/litrel

Note. Since the calculatioa of HrO+ iou concentration is tsually the first step towards the calculation
of pH, therefore the numericals of this type are automatically included in the various
rypes that follow.
8^8 N e.4

TYPE II. On the calculatlo[ of = 0.0005 M

pH ofcohpletely ionized aclds
lH3o+l = 2x [H2So1l
r li)(Atrll'l.ll, 1. Ca lculate the pH vqlue of = 2 x 0.0005M
(i) t|-z molar HNO, solution = 0.001 M = 10-3 M
(ii) 0.03 N HCI sohttion pH = - log[HrO+]
. (iii) 0.001 N HzSOlsolution. : _ Iog (10-3) : 3
(i) HNO, completely ionizes as
HNO3 -F HzO ......_ H:O+ + NOi
the pH of the coffee. Is this coffee acidic or alkaline ?
.. [H:O*l = [HNo3] = 7o-2]l..{ (Given) Solution. Here we are given that
pH = -log [H,O+l : -loC (10-'?) [H3O+] = 1.3 x 10-5
= - (- 2log10) = 2 pH = -log [H3O+l : -log (1.3 x 10-5)
(ir) HCI completely ionizes as
HCI + H2O -----------. H3O+ + Cl- = - (log 1.3 + log 10-5)
=-0.1139+5=4.8861
.'. [H:O*] : [HCl] : 0.03 N (Given)
= 4.t9
= 3 x 10-2N = 3 x 10-2M As pH is less than 7, the black coffee is acidic.
(HCl is monobasic) I.lXAl\{Pl,l.l 3. A solution is found to conta t
.. pH : -los [H:O+] 0.63 g of nitric acid per 100 ml of the solution. Wat
is the pH of tlu solution if lhe rcid is completely
(Eq. mass = Mol. mass)
dissocisled ?
=- Uog3 x 10-21
Concentration of HNO, solution
=- (log 3 + log 10-2)
= 0.63 g per 100 Irrl (Given)
=- (0.477L - 2) = 1.s229 K.?
(n'i) HrSOn completely ionizes as = 6.3 g per titre = motes/lirre
f;i
H2SO4 + ZHrO 2H3O++ SOi- : 1O-r M
( . Mol. mass of HNO, : 63;
lH3O+l- = 2x [H2SOal
Now, HNO, completely ionizes as
[ 1 molecule of HrSOn gives 2 HrO+ ions]
HNO3 + H2O ----.----' H:O+ * NO:-
But H2SOa = 0.001 N = 0.001 x 49 g,4itre
.'. [H3O+l = [HNO3]
(Eq. mass ofHrSOo = 49)
0.001 x 49
= to-r M
= -:j;- molcsnire .'. pH = -log [H:O+l
( .' Mol. mass of H2SO. : 96; : -log 10-1 : I

FOr< iF?.RA@1Ii:li6,E \
l. "ROBLF,lvi,I
Calculate the pH value of 0.001 N HNO3 solution 3. What is the pH of a sotution whose H+ ion con-
[.\ns. 3l cenkation is 2 x l0-5 g ions/litre ? I{ s. 4.699]
2. Calculate the pH value of lO-3 M HCI solurion 4. 0.049 g of H2SOa is dissolved Per litre of the giveD
nDs. 3l solution. Calculate the PH of the solution.
hns.3.01
 EAUtLtBRtUM I (ONtC EQUtLtBB|UM tN SOLUTTONS)
- 8/19

5. Calculatc tbe pH of a solution whicb is I x 10-3M 7. Cakllate the pH ydlue of a 4.9 x 1O-a N
with respct to sulphuric ac.id. monobasic acid solution assuming
JAns. 2.5tDl tioo.
6, 13.5 I of an acid HA, of rDolecular mass 135 was t. Calqrlate rhe pH ofa solution obr
dissolved in litres of aqueous solu tiorl Calculate
IO 25 rd of Nn 0O HCI ro 500 ml.
the pH of tbe solurioD, as miDg thc acid to b 9. I ml of 13.6 M HCI is dilured with give
completely dissociatcd. I.r.tts.2l 1 liue of thcsolution. Calcutaie pH o li.ing
solution. .Gjt

'Hi.lilN,T9
4, tll2so4l = o
qof,e n,or l-1 =5x
'lo-a M. E. NrVt = NzV2,25 x 1 / 100 = N2 x 500

As H2SO4 Ztt+ + SOl-, or N2 = 5 x 10-aN

- x lo-a;= 1s-3NI
[H+] =2" (5 tH+l = tHcrl = s x 1o-aM
e. Uat = i;l'Jm mor L-r = ro-2 M. pH=-tog(sx10-1)
=4 - log5 =4 -0.6990 = 3.301.
tH+l = IIIAI = lo-2 M.

TYPE IIL On lhe calculatlon of (i) Cdlculation of motarity :

pH of conrpletely lonlzed alkalies
Mass of NaOH dissolved 4.0 g/litre :
I,lx.\lll'I-ti L Calculate the pH of Nlt000 Mol. mass of NaOH : zl0
sodium hydmide solution- . assuming .omplete .. N'tolarity of the solution
ionizqtion (Kw: 1.0 x 10-14). _
qo!!!g& NaOH completely ionizes as
Strength in g/ litre
= --M"G;. 4.0 _
= _
=o ,
tv
+o
NaOH -------- Na+ + OH- (ii) Colculation of the OH- ion conc.
.. toH-l : tNaoHl = {1000
NaOH completely ionizes as
NaOH ...........+
Na+ + OH-
: 10-3 N = 10-3 M .. [oH-l =lNaoH] = 0.1 M = 10-r M
( . 8q. mass = Mol. mass in casc of NaOH)
Now as lHrO
tl 1OH-; = 1g-r'n (iii) Calculation of pH :
We know that
..[H:o*l =#=$=,0', [H3o+l [oH-l : Ky = 1.0 x 10-14
K.
.. pH : -log [H3O+lc = - log 10-11 = 1t ... IH,o+t
,--r- ' - I'o x lo-r4
LX\\lPL[]2. 4.0golNaOH are dissolvedper [OH-l - -- 10-=r--
.
litre. Find (i) molaity of the solution (ii) OH- ion = 10-13 M
concentration (iii)pH vahrc of the solution (At. mas_ .. pH : -log [H:O+l
ses..Nc = 23,O:16H = 1). = - log 10-13 = 13.

?R,ACTICE
l. Calculate the pH va MNaOH(6) 3. must be
0.01 M NaOH
' "c. and H soturion'ai iB N/10
D G) t2.6ol
2. Calculate th pH ofa solutbD contai gcaustic
soda/litrc of uater, D.69ryl
!rns. 4 g, 131
8120

4, C3lculate the PH of thc following solutions : aod hydroryl ions and the PH of the soluiion'
mnde (Atomic mass otsr = 87cdot6) (N C'E'R'T')
[ose Amourlt dissolved voiume ofsol.
(a) noH 2s 2L 1sl+; - o.rstt u, [oH-l = o'3152M'
". pE = 13.501
(b) ca(oH), 0 3I 5OO mL
6. If 0 .561
I KOH is dissolved in water to Sivc 200 mL
(c) NaOH 0 3I 2Il0 mL
ofsolution a]298 K calc'ulale the co[centration of
(Atomic masses : 1'l = 2O4, Ca = 40, Na = 23) potassium, hydrogen afld bydro]ry| ions. What is its
(N.C.E.R.7:.) [,r,.. (c) 11 70 (D) 12'21(c) 12 s7l inz (N.c.E.R.r.)
lenr. tK+l = toH-l = o'o5M'
solution. Calculate the concentratioos of strontiunl lE+I = z'o x 1o-r3 MI

HINTg FORDIFFICULT TROBLEM.g

4. (b) Molarity of Ca(OH)2 sol.
2. INaOH] =frmorl-r=5 x 10-2M
rle. [oH-] -5x10-2M =f y1999=s.11 x1s-3

[oH-l = 16'22x1o-3
= 2 x [ca(oH)2]
- [Hro*] = -19-11, =2* 16-r:.
.1 pOH - - log(16 22 x i0-3)
pH = - log 12 x 10-13; = 3 - 7'2101 = l'19
3. ForLof I N NaOH solution, NaOH dissolved =
1 :. pIJ= 14 -POH = 14-179=1227.
18eq. =408
.. For I L of N/10 NaOH sol., NaOH dissolved 6.tKoHI =+x#r=oor0M
KOH K+ + OH-,
=qo x#=rs As
-
... [K*)= {oH-]:0.05 M
{oH-l = 10-r M lH+l = Ky,/[oH-l
- [H:O+] = 10-13 M' = LO-11/0.05 = 10-r1l(5 x 10-2)
pH=-log10-13=13 = 2.0 x 10-13 M.

Ti?E Mn tle c.l4ulatlor ol OI lH3o+l = /K, tCH, CO'HI

H of aclds and hases lot completely lonized But IL= t'8 x to-s
Calculote the PH ol a 0.01 and [CH3COOHI = 0'01 M : 10-2 M
of scetic acid. K. for CHTCOOH is
solution
... lH3o+l = /(fi, 1o;, (lo-')
1.8 v 10-s at 25"C. "
Solution. CHTCOOH ionizes as = fi; >< 1o-' = fi8 r. 10*
= y'18 x 1o-a g ions/litre
cH3cooH+HzO 1* cHrcoo- +H3O+
Applying the law of chernical equilibrium, wc
= 4'242 x 10-a g ionMitre
:. pH -- -log [HrO+l
set K, = lcHpooHl =- log (4'242 x lo-4)
But [CHTCOO-] = = -Q.6n6-4) = 3.3727 = 3'37.
[H3O+]
, Colculate the PH of 0.1 M solu'
_ IHro*l' tk)n the degree ol dissociation ol the
- [cH3cooHl acid is 0.0132.

[. one molecule of CHTCOOH gives onc I Solution. Acetic acid dissociates as

IL' cHlcoo- ion and onc H+ ion or l-lrtl' ion j cH3cooH +H2O <--r cH3coo- +H!O+
 EOUTLTBBtUM
- (tONIC EOUtLtBHtUM tN SOLUTTONS) 8121

IfC moleVlitre is the initial concentration and Solution.

a is the degree of dissociatioD, we cao write C6H5NH2 + HzO C6H5NH3++OH-
cH3cooH+Hzo {r 6111969- agrg+ ==|
Initial C molL-l
Initial C After disso. C-x:C x x
conc. J
Conc. C - Ca Cq Co xu =t
at eqm.
Thus [HrO+] orx = y'&-xC = VArx 10T (to-3t
=QYa
=653x10-7
= 0.1 x 0.0132 i.e. [OH-] = 6'53 x 10-7 M
= 1.32 x 10-3 M .. [H+] = K,,,/[OH-I = to-t1/(6'53 x 1o-7)
.. pH = - log [HrO+] = 1.53 x 10-8M
pH=-loslH+l
=- log (1.32 x 10-r)
= loc (1 .53 x 10-8) = 7. El
-
=- log7.32 + log 10-r Degree of ionization (q) = r'qr-C
=- 0.72O6 - 3 = /(4 ,? 1o"r) - 10"
"
= 6.53 x 10-a
= 2.8794.
( .. . x 6.53x10-76.sax lo-aj\
3. Cqlculate the pH oJ l0-3 M
tlxANll'l,lt
qniline solulion. Given thqt its ionizotion constant,
directlya
(or =
a = ==ii.- =
Kr= 4 27 x 10-10. Also calanlate its degrec ofioni- Ko = Kl,,/Kb = Lo- 11
/ (4 27 x ]]o- to)
zalion and ionization constqnt oI its conjugote acid. = 2.34 x lo-s.

? ROBLE M I FO R rif?:RAe- ",,lili

l. Acetic acid has a dissociation consknt of 4. A sample of sour milk was fouDd to be 0.1 M
1.8 x 10-5. Calculate tbc pH\alue ofthe decjoor. solurioD of lacticacid CH3CH (OH) COOH. What
mal solution ofacctic acid. I Ans.z.t7J is the pII of the sample of milk ? I(, for lactic acid
2. A0.05 N solution ofaceticacid is found to be 1.97,
at 25"C is 1.37 x 10-4.
ionized ai 25'C. Calcutate (0 Iq for aceiicacid and
(r'i) thc pH ofthe solutioD. | ,. .2.431
5. Calculate the pH of 0.15 M solurion of hr?o-
I Ans.u) l.E x 10-l (ri) 3.02231
3. Calculatc the pH value of a solution of 0.1 M chlorous acid HCIO (Ku = 9.6 x l0-7).
NH, (K5 = 1.8 x lo-5) l2l I ars.1l I 3.421

2. Amount ofacetic acid dissociated

= 0.05 x 1.9,u 100 = 0.00095 Kb
.. Concs. at equilibrium :
ICH3COOHI = 0.05--{.00095 M. .. [oH-]
[cH3coo-] = [H+] = 0.00095 M
3. NH3 +H2O ar NHa+ +OH- lH+l
8122 Ned t

TYPE V OIl the calculatlon of , EXAIVIPLE z.Colculate the PH of a solution

pH of rnrrtures ol acldr and bases obtaineil by miing equal vohunes of the sofutions
with pH = j andPH = 5.
tl.lx.\\ll'1.1, l. What woLtl(l be tfu pH of a pH = 3means[H+l = 10-3 M and
solution obtoinedby tnlin| 100ln|o10.1 N HCI dnd pH [H+l = ro-5 u. On mixing equal
9.9 ml ol N NaOH solution ?
1.0
volumes, in the final solution,
Solutlon. Vol. of 0.1 N HCI taken : 100 ml fi-\/z
lH+l =(10-3 +
Vol. of NaOH mixed : 9.9 ml of 1.0 N
:99mlof 01N
. . Amount of HCI left unneutralizEd
= 0.505\xad-3 M = s otsx io-a lr.t
:
(100-99) ml of 1.0N = 1mlof0.1 N :. pH = - log (5 05 x 10-) = + -rO 76133
As the total volume of the solution aftcr
mixing : 100 + 9.9 ml = 109.9 ml = 110 ml, it means
I l\ \\ I l'Lla -l.Equal
vohtmes ol soltttions witlt
rhat 1 ml of 0.1 N HCI has been diluted 110 times pH :4 and pH = 10 ure m*ed. Calculate the pH
.'. Conc. of HCI in the solution after mixing ol the resulting soh.tion ?
: 0.1/110 = 9.09 x l0-4 M Solutlon. pH = 4 mean-s IH+l = l0-a M and
As HCI completely ionizes as pU = ro meani 1H+l = 10-ro'M
HCI + H2O +H3O+ + Cl- or [OH-l = 10-1 M. Thu-s they will exactly
neutralise each other andpH of the resulting solu-
.. [Hro*l = IHCII = 9.09 x 10-1M tion will be = 7.
pH = -log [HrO+l . EX Ai\ tI'I,I1Ca lculate lhe pH of the sohttion
.1.

: - log (9'09 x 10-a) obtained by miing 100 cmt of solution with pH = 3

with 4!N cm3 of solution with PH = 4.
= - [og9.09 + Iog 10-a] 100 cm3 of solutionwithPH =3con-
=- [0.es46 4l - H+ ,, ,,
= 3.0454 = 3.05
tains = ffi = 10-a mole

Altrnatlvely' 1m ml of 0' 1 N HCI 400 cm3 of solution withpH = 4 contains

= 100 x 0.1 milli eq. = 10 milli eq.
H.=#x400=4x10-5mole
9 9mlofINNaOH
Total H+ = 10-1 +4x 1o-5
= 9 9 x 1milliq. = 9 9millieq,
. . HCI left unncutralized =1o-1 (1 +o'4)=14x1d.
9'9 = 0'lmillieq. lbtal volume = 500 cm3
= 10 - :
Volume of solution = 100 + 9'9 109 9 ml .. [H*] =
,_1#,L x looo M
.'. Normality of HCI in resulting solution
0.1 0'l =2 8x 10-1 M
= 109.9= 110
= O.m x 10-1 N pH = - log(2.8 x 10-1)
=9 09x lo-4M = 4 - 0'4472 = 3'55

MS FCR \; :

1. Calqrlate the PH of a solution obtained by mixing 3. Calc-ulaic thc PH vsluc of I mixture cf,rtoinlnS 50
50 ml of 0.2 M Ho with 49.9 ml of 0.2 M NaOH ml of I N HOand 30 ml of 1 N NaOH solutioD'
solution assuming both to be completely dissociated.
Ans. 0.602U
[ tu,s.3.699] I

2. Clculate the PH of a solution obtained by mixing

( A 50 rnl lolution of ?H = 1 is mixed with 50 ml
equal volumes ofN/10 NaOH and N20 HCl. solution of pH = 2. What will be of the the
[,i ns 12.39E] mixrurc ? I .1 261
 EOUTUBRIUM [ 0ONrC EQUTUBRTUM tN SOLUTTONS) 8123
-
FORDIFFICULT TR.OOLENr',S
1.49 9 Drlof0 2M NaOII will neutralise 49 9 mlof 0 05 I eq. of HCI vrill neutralise 0.05 g eq. of
0 2 M HCI. Hence HCI left uoneutralised = 0.1 NaOH.
ml of 0.2 M. volume after mHing = 99.9 ml ... NaOH left uDneuiratised = 0.05 g eq.
- loo ml. Hence
applying N1V1 = N2Vr,
Volume of solutioo = 2 L
0.1x0 2=Nzx 100 or N2=2x 10-4. In the . . CoDceotration of NaOH in lhe final solurion
finalsolution, [HCl] -2 x lo-1M - l-r
r:e. =2x 10-aM.
$, ", = 0.025 N
[H3o+]
lNaOHl =[OH-] = 6.625 Y = 2.5 x 10-2
2. Suppoce I L of N/10 NaOH is mixed wirh I L of
N20 HCt. .. [H:O+] - 1o-ra t (2'5 x lo-2)
I L of N/10 NaOH contains NaOH
I
-4 x10-13M
=mgeq.=0 t Seq. 4. In the mixturc, [H+l = 1tg-t + 1O-2) / 2
I L of NZI) HCI coDtains HCI
-ol'-o.orr=5.j x ro-2
=;seq.=0.059eq. pH = - log(5.5 x 10-2) = 2 - o.14 - 1.

TYPD YI. On the calculatlon of i.e. [H3O+12 = 9.55 x 10-r{

pH ofrrater frolrr lts ionic product
or [H3O+l = Vr.55 10-"
. l.lX.\i\ I t,l,l,l. fhe valueoJK*is 9.55 x i0-14 at "
= [H3o+] [oH-l
s certain temperafiirc. Cslculate the pH oI water at
thk temperorure. = [H3O+l [H3O+I=[H3O+F
Solutlon. Here we are given = 3.09 x 10-7 M
K*,=9'55x10-u pH = -log [HrO+]
Now, as for water [H3o+] = [oH-]
= - los (3.09 x 10-7)
. K, = [H3O+] [OH-l = - uog3.09 + log 10-71
= [H3O+l [H3O+l = [H3O+12 = - [0.4e _ 7l: 6.s1.

l. The i?lue of K* at a ccrtilin temperature is 2. Thc ionic producl of sater at 310 K is

6.25 x 10-14. Calculate the pH ofwater. 2.7 x lo-ra. what is the pH of neutral vater at
I r.ns 6.6021]
this temperature I (NC.E.R.T) [ Ans.6.7t]

TYPE ML On the otlculation of H+ loD conc. = - 6.58 {pH = 6.58, given}

or OH- ion conc. or lonizstion constant .'. [H3o+l = antiloc (-6.58)
(X" or K6) from given value ofpH.
= a\tilogl.4z
Calculste the HrO+ ion con- = 2.63 x 10-7 g ions/ltre
cefltrqtion oI a solution haing pH 6.58. Calculste the mass of HCI to be
Solution. pH = - log [H3O+]
disso the solution so lhat is pH value
is 1.3
.. log [H]O+l :
-pH pH = _ log [HrO+]
8124 Nerl Course Chenr i strg

.'. log [H3O+l = -PH : - 1301 NaoH Na+ + oH-

------------'

lH3o+l = antilog (- 1 301)

.'. [oH-] = [NaoH] = 10-2 M
Mo. mass of NaOH = tl{)
= antiloc (r.699) . . Amount of NaOH dissolved per litre
= 5.0 x 10-2 g ions/litre
But [H3O+l ions are obtained from HCI by its
= 10-2 x +0 :0.4g
. I,-\ \1tt'1.1. ) The pH of a solution obtdined
complete ionization as by dissolvirtg 0.1 mole of an acid IIA in 100 ml oI the
HCI + H2O H3O+ + Cl- qqueous solution was lound to be i.0. Co.lculate the
.'. -, = 5.0 x 10-2 M dissociotion constant of the acid
HCI = [HjO+l
S,S!tt!!9-tr. pH
= -log [H3O+l
Molar mass of HCI + 36.5gmol-l
..5.0x10-2MHCI .. log [HrO+] = -PH
= (5.0 x 10-2) x 36.5gof HCI/lire = -3.0 [PH : 3 0, givenl
= 1.825 s/lifte or [H3O+] = antilog (-3)
l,:X\XIPt.l'l 3. How many grams of NaOH = 10-3 g ionslitre
must be dissolved in one litre oI the solution to give
= 0.001g ion4itre
it a pH value of 12 ?
Original conc. of the acid HA : 0.1 mole in
pU = -log [HrO+] 100 ml. = l mole/litre
.'. log [H3O+l = -PH = -tZ HA dissociates as
''' [H:o*l = antilog ( - 12) HA +H2O <"r H3o+ + A-
= antitog (12) Initial conc.: 1M 0 0

= 10-12 g ions/litre Conc. at

equilibrium: 1-O.001M 0.001M 0.00lM
But we know that
.'. Dissociation constant (K) will be given by
lH3o+l [oH-] = K,, = lo-u
K,10- 11
v: lHlo+l lA-l
toH-l =t"p=l =,=t .. -:----=-------,
[HAI
0.001 0.001 10-6
x
= 10-2 g ions/litre
0.001 =-=t0-5
Since NaOH is a strong electrolyte, it under'
1 - 1

goes complete ionization as

(Neglecting 0 001 in comparison to 1)

?RO?LE'M I F,C R iFiRA6,lilil,.6',8

"
1. Calelate the H3O+ ion concentration ofa solution 5. Lmon juice has a pH = 2.1. lf aU the acid in lemon

hsvlng a pH of 10.6. citric acid (H Cit. <---\ H+ + Cit-l) 8nd X!

[Ans. zS12 x 1011 Ml
is

2. The pH of blood serum is 7.4. What is the hydrogen fur citric acid b 8.4 x tO-' mole/itre, lYhat is thc
ion concentration of blood Eerum ? conctntration of citric acid in lemoniuice ?

[['rs.4 x 10-t Ml [.\lls.7.! x 10-2 MI

3. Urlne has a pH of 6.0. If a paticnt ellminates 1300 6. Calculate the dissociation constatrt of an acid, I M
ml of urine per day, how many gram equivalents of solution of whicb has a pH vslue of 4.
the acid he eliminates Per day ? [.rrrs tO-ll
IAnr. 1.3 x 10-'8 'qulvrlcn6] 7. The pH of 0.1 M solution ofsn organic add ls 3.0.
4. A ssmple of ftesh apPle juice has a PH of 3.76. Calculate thc dissocistton coNtant of thc acid.
calculate [H+]. Ians,1.74 x l0-'l l.tus. 10-'1
EOUTLTBRTUM [ 0ONtC EQUtLrBHtUi.,! rN SOLUTTONS) 8l2s
-

t. 0.01 M solution of an organicacid is found to have and its dcgrce of ionization in rhe solution.
a pH of 4.15. Calc.ulate the concntratior of the (N.C.E.R.T.)
anion, the ionizrtioo constant of the acid and its
I u,s K, = 2.09 x 10-4,.z - 0 0{s7l
PK.' I n!ls. [A-l = 7.0E x 10-3 M,
11, Calculate the hldrogen ion concenration in the fol-
IL = 5.0E x to-1, pKo = 6.29l whce pH are g rn below
lowing biological fluids :
9. The pH ofo.005 M codeine (ctsH21NO3) solution (4) HumaD muscle-fluid, 6 83
is 9.95. Calculate its ionization caNtant aodpKD. (b) HumaD stomach fluid, 1 2
(c.) H-uman blood,7 38
[ \,,..K, = l
s.tl 6 x 10-6,pK, =
(d) Humansaliva'6 4 (N'cER'7:)
10. ThepHof 0.1Msolurionof cyanic acia lucNo;
is 2.j4. Calcutate the iooization constanr ofrhe acid | \r',.(a) t 46 x t0-7M(r)0.063(c)4.17 x t0-8M
(d)398x10-71

3. pH - 6 0 means [Hro+1 - 19-6 Y or [H+] = 7.08 x 10-5 M

ie. IAcidl = 1s-6 Y = 1g-6 P HA + H+ +A-
Thus 1000 ml of lhe urine coDtain acid Hence al equilibrium
.8
= 10 eq. IH+l = tA-l = 7.08 x lo-5 M
. . 1300 ml of the urine will contain acid -= 7.1 x 10-5 M
= 1.3 x 10-6 g eq.
IIIAI = (0 01 - 7.1 x l0-5)
5. pH = 2.1ie. - Ios [H +] = 2.1
= (0.01 -0 000071)M =0 009929M
or log [H+] = - 2.1 -1.9
q = IH+l IA-l
or [H+] = 7.943 v 16-:
HCit + H+ + Cit-l _ (7.1 x lo-5): _ 5.08 x l0-7
9 Y29 x lo-r
K. = r"ilE:ii_,r
PK, = .-loBK,= -log(5 oE x:o-7)=6 29.
(7.943 x 101(7_.943 x 10-1
8.4 x 10-4 _ 9. Codeine + water codenium ion + OH-
=:=+
From given pH, [H+] = r.12 x 1o-10 M
or [HCit] =? s x1o-2M
5. pH = 4 mcals [H*] = 1o-o M .. tOH-l = K-l[H+] = r.e3 x 10-5 M

HA+H++A- K, = rBiJSoJf_r
Ar eqm 1- 10-a - 1M t0-1M 10-4M
(8 93 x -5)2
lO
to-ax1o-a=ro-a 1.6 x 10-6.
O_
r0. HCNO i.l H+ + CNO-
7. RCOOH <=- RCOO- + H+ pH = 2.34means - tos IH+l = 2.34
lH+l - [Rcoo-] - ,o-, M
1... ,u = ry or log[H+] = - z
=a.66?,4

lRcooHl - 0.1 - 1o-3 - 0.1 M or [H+] = Artilog 3.66 - 4.5? x 10-3 M

K, = rR?RoCo#rfl.| = 1o-3 x-10-3 - ,o-s. lCNo-l = [H+] = a,57 v 1e-r Y

(4.5? x l0-3d.(4 57 x l0-3)
t. pH = 4.15 means
- Iog [H+1 = 4.15 q - * z.oe x to-1
or log[H+]= -4.15=5 85
=,/z-ii][:ii -o.ust.
8126
I
)tzt t{ t t'
;,' 5 N etO Coursc Chem i str4 fifi[fl
YPE vul. pH = 1o-7 (10-3 + 1) = 1.001 x 10-7 M
acld or alkali
.'.pOH= -log(1.001 x 10-')
LX,\-\1lr.l Calculate the pH of 10-t M acid
solution. = 7 - log 1'001 = 7 - 0'0004 = 6'9986
!qlu-tiq+. Note. At the lirst instance, it ap- or pH = 14 - 6.996 = 7'0ffi4
pears that asIH+l = 10-8, therefore pH should be 'lYI'll IX pll or dilrtlion
8. But pH cannot be 8 but should be less than 7
because the solution is acidic. The reason is that
'. I An acid having pH = 6 is
Irom Hro, [H+l = 10-7 l'I
which cannot be es. What will be the pH of the final
solution ?
neglected in compa son to 1O-8 M. The pH can bc
calculated as follows :- pH = 6 means [HrO+] = 10-6.
From acid, IH+l = 10-8 M After diluting 1000 times,

From HrO, [H+] = 10-7 M [H3O+l = 10-611000 M = 10-eM.

.. Total [H+l = 10-8 + 1O-7 .. [H:O*l ftom HrO cannot be neglected.

= 10-t (1 + 10) Total [HrO+] = 10-e + 10-7

= 11 x 10-E M = 10-7 (10-, + 1) = r0-7 (1 .01)
.. pH = - [H+l = - log (11 x 10-8)
log :. pH= - log(1.01 xt0-7)=7-0 0043

= -[og 11 + Iog 10-t] = 6 9957.

=-[1.M14-8] .
1..\ \\l l'l-l,l l.,l cnt3 of 0. 0 1 N HCI is added to
one litre oI sodium chloide solution. Wat will be
= 6'9586 = 6'96 pH of the resulting solution ?
the
Calculate he pH of 10-ro M Solution. As NaCl solutionis neutral, itsimp-
NaOH solution- ly dilutes the HCI solution from L cc to 1000 cc.
Solution. [OH-l from NaOH = 10-10 M
Now [H+l = 0'01/1000 - 10-5 M
IOH-lfrom HrO = 10-7 M .'. pH = 5.
Total [oH-] = 10- ro + 1o-7

1. 1o-6 M NaoH solution is diluted 1000 times cal- 3. The pH of a solution is 5. Its hydrogen ion c.D'
cntratioD is increasd 100 times. What is the PI{
culatc thepH ofthe dilutcd base.
of the resultifl8 solutiou ? [/\ns. 3.01
I,\u\ 7.04541
2. Whatwill be thePH ofthe resulting solution if to a
100 ml of HCI solution ofPH = 1 0, 900 ml of
distilled water is added 'l 201I
HINTg FOROIFFICUUT ?ROOLEM-9
.. pH=2
1. After dilutioD,
[oH-l - 1g-a y. HeDcp [oH-]
3.
fiom H2O cannof be ncglccted. pH = [H+] = 10-5 M. on iocreasing
5 means 100

2. l0O mlba! bccn dilutcd to lfi)O mt. Hencc dilution tinres, new [H+l = 1o-3 M. soPft = 3'

10 timcs. Now [H+1 = 16-t 7 19 = 16-z

y
=
 EQUILtBRtUM [ 0ONIC EOUtLtBHtUM lN SOLUTIONS)
- 8127

i. For a neutralsolution,pH = 7 at 298 K (25'c). With increase in temprature, as dLssxiation of HzO molccules
incteasesie. [H + ] and Iotl - ] increa,se, so the ionic product iocreases with increase of remperature. Fur(bcr,
as IH+] increases, pH decreases with increase of temperature.
A few interesting results are given beloff :

(i)Ar273K(0"C),K,=10-l5sothaipHofneurratsotutionarthrsremperarure=T.5andpHscaleis0to
15.

(ir) At 333 K (60"C), Kl/ = 10-13,pH of neutral solution = 6 5 andpHrangeis0to 13.

(rr) At the temperature of the human body which is nearly 37.C,pH of neurral solution = 6.8.
i pH values of a few clmmon subsEncEs are given bclolv :

Saturated NaOH sol. - 15 Black coffee 5.0

0lMNaOHsol- 13 Tbmato juic - 4.2
Lime water, Ca(OH)2 10.5 Vinegar and Soft driDks -3
Milk of magnesia, Mg(OHh l0 Lcmonjuice - 2.2
Sea water and white of egg 7.8 Gastricjuice - 1.2
Human blood and'Ibars 7.4 1 M HClsol. -0
Mrlk 6.8 Croc. HCI - - 1.0
Humao saliva 6.4
, .r. pH is invcrsely related to the acidity ofa solutioD..4r acidiry incrcascs,pH decreasqs.
i L PH of the solution of a weak acid or a weak base depends upon its degree of ionizrtion (a). The relatiooship
may be derived as follov.s taking the example ofweak acid IIA
HA ._r H++A
Initialconc. C
Conc. at eqm. C(l -a) Ca Ca
lH+l=c" :. pH= -togtH+l = -rogCo. Bur Iq= aoz o, g=I\taz
pH = - tog (Ko/ a)

8.'l 0. Sa lt Hydro lysi s tl;st:tii,is.I,#?:,11l*,i+;ir,!rrii&!::+iiil:r:ir;;:]

All salts are strong electrolytes andthusionize
g.10.1. Delinitlon and ExamDles completely in rhe aqueous solution. If the acid
s atr
sab rM
ffiatssk ts dgacd a rhe
tcllh vabr ta gire ba* lle
prow in.whieh,
ulil atd th
$sL::"lT:l-ijlTffi1#:r:i:1$,t:l
i.
bme.
B+ +A- + H2O --. H+ +A- + BOH
+ Water ---r Acid + Base
Salt
. or BA + H2O HA + BOH
or B+ + H2O ------+ H+ + BOH
Salr Watcr- Acid Basc Thus, in this case the cation reacts with water
Thus salt hydrolysis mqt be considered as to give an acidic solution. This is called cationic
re vers e of n eutalization. hydrolysls.
 8128
Neu) Coqrsc Cheruistrg
Again, if_the acid produced is weak and
,oase produced the lll. Salls of strong aclds and weak bases
ts strong, we can write -
b,xamples are :
:

. B+ + A- + H2O ..._.. HA + B+ + oH.- NHaCl, CuSOa, NHaNO3, AICI3,

CaCI2 ctc.
'-,"" ot A- + H2O ....-| HA + OH- an illustration, the hydrolysis of NH.CI
H:r:, the_aniotr reaits with warer to give -As
.trasrc
.-, sotution. the may be representcd as follows :
This is called anlontc hydro-lysis,
NHaCI + H2O i.-----\ NHIOH + HCI
or NHo+ + Cl- + H.o ,
NH4OH+H++cl_
or NHo+ + H2O .._ NH4OH + H+
As it produces H+ ions, the solution
,_ . ofsuch a
salL ls actotc ln character.
[Y Salts ofweak acids and weak bases : Ex-
_ L Salts ofstrong acids and strong bases :
Exanlples are
.
amples are :
:
CH3COONHI, (NHa)2CO3, Alpoa etc.
NaCI, NaNO3, NqSO4, KCl, KNO3, IqSO4
As an illustration, let us discuss the hydrolysls .As an illustration, the hydrolysis of
monrum acetatc may bc represcntcd
am-
.
of- -NaCI. We may write : a.s follows :
cHlcooNH, + H.o -_---...\
NaCl + HrO_-r NaOH + HCI
cH3cooH + NHIOH
or Na+ + Cl- + H2O-...- or CHTCOO- + NH4+ + H2O ....-
Na++oH_+H++Cl_ CH3COOH + NHIOH
or H2O ----- H+ + OH- Thus it involvcs both anionic and cationic
hydrolysis.

... Thc resul(ing solution may bc neutral or

dightly acidic or bisic depending upon
the relativc
ocgrees ot tonization ofthe rveak
acid and thc weak
Dasc produced. In thc prescnt
example, thc acid
(CHTCOOH) and the bisc (NH4OH)
formed ar.
_ ll. Salfs of weak acids and strong bases ;
almost c_qually wcak. Hence the resulting
solution
Examples are : rs ahost neutral-

CHTCOONa, NqCOr, KrCOr, NarpO, Hydrolysis constanr. Thc general

etc. -_. .qrr*.
equarron tor the hydrolysis of a salt (BA) -may
As. bc
_illustration, the hydrolysis of sodium
a-n
_ wrrtten as
acetate (CHTCOONa) may be represeoted
lows :
as fol_ BA+ O n---\ HA + BoH
CH3COONa + H2O
-==-\ CH,COOII + NaOH . Applying thc law of chemical equilibrium, we
get
or CH.COO- + Na+ + HzO F_ lHAj [BoHl
IBA[Hrol = K. the equilibrium constant.
CH3COOH+Na++OH_
Since wate is present in very large
or CH,CC)O* * HrO -------r -, excess in
tne aqueous solution, its concentritiorilHrol
may
be regarded as constant so that we have
cH3cooH + oH_
As it produces OH - ions, the solution of such
[HAl[BoHl
.
a salt is alkaline in nature.
--lBAl-=KlH2ol=K'
where K6 is called the hydrolysis constant.
 EOUIL|BR|UM [ 0ONIC EQUtLtBRtUt\,t tN SOLUTTONS)
- al29

8.103. Degrs of Eyrlrolysls. The degree of

hytuolysis oI a salt is defined at he fraction (or ...(iv)
percentage) oI the totql salt which is hydrolysed.
(D) Degree of Hydrolysls. Suppose the
i.e. h = original concentration of the salt in the solution is
8.1 1. Calculatlon ot Hydrolyelr Constant, 01916.
c i
moles,{itre and is its degrec of hydrolysis at this
concentration. Then we have
ol Hydrolysis and pH o, Sah Solutlonr x,,,1,,ri A-+HzO+OH-+HA
As already explaincd, salts oI strong acid and Origioal
strong base do not undergo hydrolysis, therefore to molar conc. c 0 0
talk of K, or h of such salts is meaningless. The Molar conc.
cases of the other three types of salts are discussed
at equilibrium c (l - h) ch ch
below :

I. Salts of lyeak acid and strong base ; The hydrolysis constant (Kr) witl, therefore,
(a) Hydrolysis constant. Representing the be given by
salt by BA as usual, the hydrolysis may be repre-
sented as follows :
,, toH-llHAl ch .ch chz
" tA-l c(l -/r) t-h
BA + HzO . - BOH + HA IfI is very small as compared to 1, we can take
salt srrong weak
J t- 1 - /r = 1 so that the above expression becomes

or B+ + A- * HrO.-rg+ + OH- + HA chz = Kh or tr2 =t!c

i.c. it is a casc of anion hydrolysis.
The hydrolysis constant Kn for the above rcac-
tion will be given by
Substitutiag the value of K, from equation
Kr, =
toH-llHAl (rv), we get
G)
tA-l
For the weak acid HA, the dissociation equi-
librium is
/,=lF
(c) pH. In the present case, we have
.-(v)

HA + H++A- A- + H2O s-) OH-+HA

.'. The dissociation constant I of the acid Originalconc.: c 0 0
HA will be given by Cooc. at eqm.: c (1 - r) ch ch
lH+l tA-l i-e., [OH-l = cl
K' = --lllAl "'(ti) K" K*
.. tH+l -
Further the ionic product ofwater, q is given tOH-l- ch
by Substituting the value oft from equation (v),
we get
K- = [H+l [oH-l ...(r,,

.by (iii),
_ .Multipllng
equation (i) wirh (,r) and dividing
rH.t=?q
we get
Kr, L IoH-l tHAl [H*] lA-l lH*l =
K* tA-l " lHAl ( \'. pH= -log[H+] = -log
1,
X-:l
tHrl IoH-1 = -r"* (55)'"
 Pradeep's

(D) Degree of Hydrolysis. Proceeding as in

,u = - ] itocrv + logKo - togcl the earlier case, we get the same relationship vJz
This equation may be rewritten as

p" = lI- log \ - log K, + log cl Substitutiug the value of Kr, from equation (r),
we get
pH = pKa + los cl
+bK- +
...(rr)
At 298I!pK. = 14.Hence at298 K, we have
I (c) pH. ln this case we have
pH =7 + i [pK" + logc]
B+ + H2o <----s BOH + H+
Thus knowing the molar concentration c of
origiDal conc: c 00
the solution and the dissociation constant K, ofthe Conc. at eqm: r (1 - l,) ch ch

weak acid involved, the pH of the solution can be i.e., [H+l = ct

calculated. Substituting the value of I from equation (.8') ,

we get
Il. Salts of strong acid and weak base :
(a) Hydrolysis constant. For the salt BA, thc
hydrolysis may be represented as
BA + H2O + BOH + HA
,H.'=c =rs=(Yj)',,
sak Wcak Slrong
Ji '"
or B+ + A- + Hzo i-----r BoH + H+ + A- :. pH=-log[H+l
'l *',l
=-,"rf5t:'l
or B+ +H2o + BoH +Ht
i.e., it is a case of cation hydrotysis.
The hydrolysis constant K, will be given by eu = - lloev*- log K, + log cl ..,(.r'r)

lBoHl lH+l
|] - :__------:-:----!
Nn ...(yii)
[B+l As before, this equation can be rewritten as
For the weak base BOH, the dissociation
equilibrium is eH::bK*IpK6 + loscl
BOH i.------: B+ + OH-
At KPI!" = 14. Hence at 298 K, we have
..
The dissociation coostant K, of the weak 298

base BOH will be given bY

pH=1-)@rr+toe"l
r.D' lB+l [oH-] ...(viii)
III. Salts ofweak acld and urak base
IBOHI
The ionic product ofwater, K*, is given by (a) Hydrolysls constart. Representing the
salt by BA as before, we have
KY = [H+] [oH-l ...(ir)
BA + HzO <.---\ BOH + HA
Multiplying equation (vii) with (vr'ii) and Salt

dividing by (u), we get

I
K, Kr B++A-+H2o 1r noH + ua
*- =' i.e., it involves both an on hybolyis as well es
cttion hy&otysis. Witing the various equatioEs as
G) before, we have
 - [
EQUTLIBRtUM (tONIC EQUtLtBRtUM tN SOLUTIONS) 8/31

__
.,,, _
[BoHl [HAl
...@ii)
Kt=h2
[B+l [A_]
For the weak acid, n=.&,= (ru)
HA i- H+ + A-,sothat
(c) pH. For the weak acid HA,
-.(nv) HA H++A-
For the weak base, -rlH*llA-l
BOH <- n* + OH-, so that

- [B+lloH-l
,.b _ ...(:v)
or [H+]=,..#l- =K";T*6
IBOHI
Also, we know that t
=r.1-h
Kl, = [H+] [OH-] ...(rvO
Multiplyi'rg equations (rii), (.riv), (xv) and But from equation (xviii),
dividing by equation (rvi), we get
f7 = r'( to tr'at we have
Kr, & Ka
=1
K,/
tH*l=K,/q =x,/Rk
...(xyri)
-.ffi
-Y-K-
(b) Degree ofHydrol;nis.In this case, we have
B+ + A- + HrO <-------\ BOH + HA
pH=-log[H+l =-l"s\ry
Original cc 00 , , t/2
. lK"K-l
@nc.
Cono.
:

at. eqln.
c(1-lD c(l-r)
:
ch ch
=_,*l , ,l

__ tBoHl [HAl
or
.y - [B+][A_]
pH = -j tr"c r" + log re - log Kol

ch.ch * or this equation may be written as

= cTl : h\.;0 - D = 6r;5 -'1"''r
Here, the relationship between K, and i does
not involve c. Thus rhe degee of hydmtysis of uch o
ralt is indgpendent oI the concentralion of the solution. "';,2e8K;i;"
If /z is very small in comapri-son to 1, we can p.J=7+)Wx"-IiK,l
takeL-h = 1so that equation (.rvr'ii) becomes

f \ \\ll,t.t.t .t. Calculate the hydrolysis con- Degree of hydrolpis,

stant, degree of lrydrolysis and pH of 0. l0 M KCN
solution at 25'C. For HCN, Ko = 6.2 x t0-10.
As KCN is a salt of strong base and The hydrolysis reaction will be
weak
Hydrolysis constant,
CN- + I{rO i=:= HCN + OH-
Initial cM 0 0
-- K* 1O-1. Ar eqIIL c---+ x x
6,'-fd=1a = 1.6 x t0-.
IC = =
d (r = No. of moles of CN- reacted)
8132
Pradcep's

IHCNIIOH-l rxr
K,,=-,6fi=t * =, - *- tog (1 6 x 1o-5) + log o 1l
-=,_,=;
nr, = & x i = v(r.6 x r0-5) (o.l) =t -)Us- o.o2o41) - 1l
=126x10-3
i.e. [oH-l = t'?5 x 10-3 =510
c l.\\\ll'{ I ''. Calculate the pH ol 0'01 M
K- 10-14
. tH'l = toH-l = t r6x lo-3 solution of NHaCN. Given that the dissociation con'
x KrIor
stonts are: Ko for HCN = 6'2 10-10 and
=1'94x10-12 NH, = 1'6 Y P-s.
pH = - log [H+] = - log (7 94 x 10-1'z) and
!o-!utrglr-. As NH.CN is a salt of we ak acid
= 12-0'90=11 1 weak ba-se
l,l\,{i\ I I't.|.. 2. Calculate the pH of 0 }0 M
sotution olNHoCl. Tlrc dissociation constant (K) ol = 1'0
NHris 1'6 x 10-s.
As NHoClis a salt of weakbase and
strong acid,
K*
*,=il=#=625xr0-ro
10-14
6"2 y 16-ro;66-rr
1.6 x 10-5
The hydrolysis reaction will be
+ H2o <----r NHi + H3o+
NH4+ = /t{?5 'r lo-r'g
ot NH4+ + NH3 + H+ x lO-to
-- 6'22
Initialconc. c M :. pH = - log [H+l = - log (6 22 x 10-ro)
At eqm. c-x x x =7O-O79=9'21
lNHrl lH+l xxx * Alternatlvety, applying the formula directly

prr=1+lan-o*ol
or, = q;; = v(6.25,,s-roy x o.t
= 7'9 x 10-6 M ++l-log\ + logK6l
=7
,.e. [H+l = 7 9 x 10-6M
:. pH= -log[H+] = - log (7'9 x 10-6)
x
=7+ los (6'2 1o-ro)
=6-0 90=5'10 +F
Alternatively, applying the form.ula directly + los (1 6 x 10-s)l
1
pH=7-ib\+toecl =7+ +(fi - o'7s2A) + (- 5 + 0 2041)l
1

=, -;l- log K5 + Iogcl = 9'21

1. Whatwould be thePH of 0 1 molar sodium ace tate hvdrol,rsis of aniline hvdrocbloride in I 0N solution
solutioD, EiveD that the dissociatioD oonstant of a[ 25'6. Aso calculaictherH of the solution.
aceticacidis18x1O-5 gns. t tTl [rrs.0 415%' 2 3El
3. At 25'C, the ionisatio[ coNtant of anilinium
2. The dissociation constant ofaniline (C5H5NH2) as
hydroxide is 4 6 x 10-10.'Ihking ionic Product of
a base is 5.93 x 10-10.The ionic product of watcr
water as Ir 10-11, catculate (a) hydrolysis con-
ar25"Cis 1 g2 x 10-14 Calculate the Percntage
EQUTLTBHtUM fl 0ONtC EQUtLtBRtUM tN SOLUTTONS)
- 8/33

stant of irniliDium chloride (D) the degree ot 6, Tho ioDization coostant of chloroacctic acid is
hydrolysis aDd (c)pH vatuc of0 2 nrolar solution
of the salt. I 35 x l0-3. What will he rhepII of 0.1 I\,t acid
[,\rs (a) 2.17 x l0-s 0.1 M sodium salt solutioD.l (N.C.E.R.,I)
aod irs
(b) 3.29 x tO-2 1c; l.tS;
[.\ur 1 94, 7 94]
4. The iooizatioD ooDstaDt of Dirfous acid is 7, C.alcularc thepH of0.05 M sodiunt acerate solu-
4.5 x tO-4. Calculate rhepH ofO.M M sodium tion rfrhepK, ofaccric acjd is 4.74.
l..\!rj t.721
nitrite soluiion and also its degree of hydrolysis. t. The pK.a of aceric acid and pKb of aD]moDiunr
(N.C.E.R.T.) hydroxHe are 4.76 and 4.75 respcclivcly. Catculal(
lAns.pIJ=7.h,a = z.:e x ro-!I the hydrob6is constant oi amntoniurrr acelare ar
S. A 0.fi2 M solution ofpyridine hldrochloric haspH 298K and also the degree ol h)ctrol).sis an(lpl I ot
= 3.214. Calculate the ionization constant of (a) 0.01 M and (r) 0.04 M sotutrors.
Pyridine. N.C.E.R.T.) [,\ns. I .5 x 10-rl l.\us Ki = 3.25 x 10-5,1 = S.7 x 10-3
sndpH = 7.00S (s6me in hcth coscs)l

H lNTg FoRotFFtcuvr rr.oeuevs

K,,
,. xr=d=;ffi=s
to-I1
s6 x ro-ro tt=tKli =,/;2r-l1_rr 1ni
fi " 16-lo = 36 x l0-5
=
CH3COO- +H2O (r CH3COOHrOH- '
toH-l = ,f;, c x
1ou-1 = 'rqr- = {-i" rotl lon+;
d
=r's 88"10 =e 42x1o-1
=C;;=q,.", ='t.46x 10-6- *"=;tlill,l?::'"1,
1u*r=ffi"=r34xK-e
pH- -ros(r.34 x r0-e;-e-6
= 8 8?3 : E.87
127 ,.,r,,ll,l",ilJ?'i.;l';l,oi,=*.1,11",",,,,0
strong acid, Hence

2. Anilire hydrocbloririe lcrHriUrCt-) is a salr of

pu = - j tros x- - tos KD + tog cl.
weak base (c6H5NFI2) and strong acid (HCl).
Kr,
i.e. 1.44 = - it- ,o - log KD + tog (2 x t0-2)J
', 1.02 x 10-la or 6.88 = t4 + tog K6 + 1 .7(l
^r=X;=rOffi=t72xto-s or log K, = - 8.82 = 9.t8
CuHrNHr+ + H2O=- C6H5NH2 + H3O+
or or K6 = 1.5 x 10-e.
CaHTNI Ir+ ;=::i CHTNH, + H+
6'
tH+l = vR; x c
=V1.[, 10-, " 01 = 1.16 x l0-z
or 4.15 x tO-3 x1N% = O.4t5To pll = - log (t. 16 x l0-2)
= v1, x c =Y
=2-006=1.94
[H'f t.72x l0-5 x 1.0
Sodium salt of chloroacetic acid is a salt. of strong
= 4.15 x 10-3 M base and weak acid. HoDce
pH = - log(4 15x 10-3; = 3 - 9.616
pn = - x,, + log Ke -
= 2.382 - 2.38 | lroU los cl.
4' *, x-tx" 8. First calculate Ks and K6. Then
= = to-14,/(4.5 x 10-4)
= 2.22 x 10-ll K6 = Kpl(Ka.Kr) ardh = tK;.
 Pradeep's
al34
8.12. Acid-base Tilration Using lndicetor tion), prccipitation titrations (e & Nacl vs AgNO3),
nvolving formation of
8.12.L. Delinitions take uP abriefdiscus-
Tltrallor is the measurement ol the volume of in aqueous solutions
t
only.
;
f
volume of ono solution that must be added to
another solution till the reaction is complete, lftts t.122. Theory of Acid-Base Inallcators
(Ostwatd's theora). According to this theory

so concentration
of aratus used is
sh of the solution
is the helP o[ a
Dinelte) and the other solution is tukun in [h':
Lr.irette'which is graduated in cc's and has a stop- (2) They dissociate in aqueous solution as

clock at the bottom to control the amount of flow follows :

into the flask. The solution to be titrated (taken in H+ + Ph- ...(i)

the flask) is called titrate and the solution with (Color.tlesr) (Pink)
which the titration is to be done (taken in the Me+ + oH- _.(ii)
burette) (Red) (colourlas)
required The unionized form has one colour and the
the other ions have differeot colour. For example, HPh is
two is ca colourlesswhile Ph ions have pink colour. Similarly
MeoH has yellow colour while Me+ ions have red
colour.

BURETTE

STOPCOCK
TITRATION
FLASK

SOLUTION A red.
Phenolnhlhulein cqnnot ba us?d us indicator il
the buse is weak e.g NH.OH. This is because the

FIGURE 8'2. Apparatus for titration
Thcrc arc many t,?cs oI Iitrations such
rcdox titrations (involving tlxidation and reduc-
tion), acid-base iittrations (involving ncutraisa-
oH- iom produced from the weak base are in'suf-
ficient to ihift the equilibrium (i) towards right
as
substantially. Similarly, nrcthyl orange is .not .a-
iuitable indicator if thi ucid is wesk\ke acetic acid
EQUILIBRIUM II (|ONIC EQUILIBHIUM IN SOLUTIONS)
- 8/35
(CHTCOOH). This is because the H+ ions
produced are irxufficient to combine with the
OH- ions and shift the equilibrium (ri) towards
right significantly.
8.123. pE at the End-Point of Acid-Bas
Tltrations. One often assumes that the pH at the litration curves of strong acid against strong basc
end point ofan acid-base titration must b;7. How- (e.9. HCI versus NaOH), weat acid against itrong
cver, we must remember that what we have at the base (e.g CH3COOH versus NaOH), weak basE
end point is an aqueous solution ofa salt formed as
against strong acid (e.g. NH.OH versus HCI) and
weak acid against a weak base (e.g CH3COOH
versus NH.OH) arc shown in Fig. 8.3(a), (D), (c)
and (d) respectively. The point at which there is a
sudden chalge inpH when a very small amount of
the titranr is added to the titrate is called point of
lnllection.

pH
t
I I

o o

Volume of NaOH added in mt Volume of NaOH added in mt

i METHYL RED COLOUR

CMNGE MNGE
pH

o
Volume ot HCI add6d in mt
Volume of0.1N NH4OH added in mt
 Neut Course Cfrcnt i stru
8i 36

howpH changes during acid- When 50 ml of 0' 1 N NaOH solutioo has becn
To understaod
ation of 50 0 adde AII
solution.The the a aCl
lutionmaybe only. has
sudd
Further addition of oven a very soall amount
Initiallv. as the solution taken in the flask is 0'1ml) increasos thepH of
of NaOH solution (say
0.1MHCiiH+l = 10-r, pH = 1 0. After l0 mt the solution very rapidly. This may be seen as fol-
of 0.1 N NaOH has been added, it will neutralize
lows : -
10 ml of O'1 N HCI so that HCI left in the solution
60 Now, volume of the solution
= rl0 ml of 0' I N and total volume of solution =
ml. To calculate normality of HCI in the final solu- = 50 + 50'1= 100'1ml
tion, apply Nrxvr=N2xv2 i'e 0'1x40=N2x60 0' N NaOH solution left unneutralized
1

or N2 = 0 '0667 N or 0' 0667 M = 0'1 ml

To calculate normality of NaOH in the final
i.e. [H+l = 6'OZ x 10-2 M'
solution, applY
Hence PH=118. N,Vr = frlrYrl.r.0'1 x 0'1= N2 X 100'1
Similarly, when 20, 30 or zl0 ml otc. of NaOH or N2 = 10-4 N or 10-4 M
solurion have been added, the corresponding pH i.e. [OH-l = 10-1 M.
values can be calculated as given in Table 8 5' Upto
Hence [H+l = 10-10 orpH = 10'0' Similar-
the addition of 49'9 ml of 0'1 N NaOH solution,
ly, [OH-] and hencc [H+l orpH can be calculated
the following general formula can be used to calcu-
wirLn noie of NaOH solution is addcd' In general,
late normalitY of HCI or [H+l can
normality of NaOH solution and henco [OH-l
Normalityol HCl=
/so - ,\ xo l=lHrI be calculated by applying the formula
iffil /,, - sq) x o.r M
rvhere u is the volume of 0 1 N NaOH solution lNaoHl = loH-l =
added.
lsoTrl
8.5. Thus it maY
tAitl,E $.5. titration 50 0mIof0' lNHCI .9 ml of NaOH
sith0INNaOHsolution geby three units,
ange of six units.
VolumeofO l NNaOH PII
solution sdded
0.0 1 .00

10.0 118
20 .0 137
300 1.60

,IC,0 1 .96

490 300
4 .00
49.9
700 solution is added from thc buette.
500
E.12,,1. Selectlon of a sultsble lndlcator' The
50.1 10.00
indicator used should be such that it shows change
51 0 11 .00 in colour in the same pH range as required around
1196 the equivalence point. A number of indicators are
60,0
avaihLb for the entire pH range. These are given
700 t2 22 in Thble 8.6. below.
EQUtLtBBtUtvt (ON|C EOUILIBRIUI\,4 rN SOLUTTONS) Bl37
-
T.A.RLE 8,6. Common acid-base indicators arrd ?.
,\ln _ lH+llln-l
_
their coloul. changes lHLrl
Indicator pII.range Acidic Alkallne The exact point of the colour changc will be at
colotlr colour thepH when lHDrl = [In-1. Substituting thisvalue,
we get
Methyl violet o-2 Ycllow Violet
Methyl yellow 12-2.3 Red Yellow Krn = JH+l or - Iog K,n = - loe [H+l
Methyl oran8e 3. 1--4.5 Red Yellow i.e. pKr" = ?H
Bromocresol 3.8-4.6 Yellow Blue
Thus for a particular, tittration, the indicator
greeD
selected should be such for whichpKrn = pH ofthe
Methyl red 42-42 Red Yellow
solution at the equivalence point. For example, in
Litmus 4.5--.3 Red Blue the titration of HF with Naotl, pl{
at the
Bromotbymol 6 0-7.5 Orange Blue equivalence point is 8.1, pKr,, for cresol red is 8.1.
blue Hence cresol red should be uscd as indicator in this
Phellol red 6.4---4.2 Ycllo Red titration.
Cresol red 7 .2-8 8 Yellow Red E.12.6. Explanation ofthe pH range of2 units
of indicators. From Table 8.6, it may be seen that
Thymol blue 80-96 Yellow Blue
most of the indicators have a useful colour change
Phenolphthalein 8 3-10.0 (hlourless Red over apH range of 2 units. For example, the most
Thymolphthalein 9 ,3-10.5 Crlourless Blue common indicator, phenolphthalein, changes from
colourless to pink in thepH range from 8.3 to 10.0.
Aliza rin yello$, 10 1-12 0 Yello$/ rfiobt
This solves the problem for the fact that we maynof
Tlinitrobcnzene 12 0-14.O C.olourlcss Orange have an indicator for whichpK,n is exactly equal to

From the titration curves, it rnay be observed the pH at the equivalence point. Thc cxplanation
that for thepH range of 2 units is as follows :
(i) For titration of a strong acid against a For the indicator HIn,
strong base, any indicator out of methyl orange, HIn (44) <- H+ (aq) + ln- (aq)
methyl red and phenolphthalein can be used to
determine the end point. HIn and In- have dilfcrent colours. The equi-
(ri) For titration of weak acid like acetic acid librium constant is

- lH+llln-l
against a strong base like NaOH solution, only ,,
K'' ='
pheoolphthalein is a suitable iodicator.
(iii) For titration of weak base like NH.OH
tiinl- "'(')
Our eye can detect the change in colour if the
again-st strong acid like HCl, onlymethyl rcd canbe concentration of one ofthe colourcd form is at least
used as an indicator. 10 times greater than the concentration of the
E,12.5. To prove that for the colour change other. Thus (o see lhe acidic colour
pKrrrror. = pH at thc equlvalcnce polnt
lln-l _ 1
As already meotioned, acid-base indicators [HInl l0
are weak orgalic acids or weak organic bases. Sup-
and to sce the alkaline colour
pose we consider an indicator which is a weak
organic acid. Let it be represented by HIz. In lln-l _ 10
aqueous solution,it dissociates as [HIn] - 1

HIz (aq) <-: H+ (aq) + h- (aq) Rearranging eqn. (i), we get

HIn and In- have different colours. The equi-
rH+l = Kr"
librium constant for the above reaction is ffiT
8/38
p7a/eep's

.. For acidic colour to be visible 8.12J. Formula for calculatlon of volumetrlc

ana$rls. The basic principle is that the reactatrts
lH+l = 10 ..<r.
reac* with each other in equivalent aEounls.
or - log [H+] = - log 10 - log K1n
Suppose the two reactants involyed arc A and
i.e. pH = p\r - L B. Fbrther suppose V1 cc of the solution ofreactant
For alkaline colour to be visible A having normality N, react exactly with V, cc of
.t the solution of reactant B having normality N2.
Is.l = ra K,,
Number of gram equivalents of A reacted
or - log [Htl = log 10 - log Kr" N.
= -":-': X Vt
i.a. PH = P\, + 1
Number of gram equivalents of B reacted
Thus for colour change of an indicator
N2
pH=pKrn!l =Im* u,
i.e. pH runge for colour change is from
As the reactants react in equivalent amounts,
pKr" - l topKr. * li.e. aprl rarge of 2 units.
Nt xVl N2 xVz
E.12.7. Calculation ofp\ or pI( values from
1000 1000
pH of equiyalence point. ThepK of a weak acid or
weak base can be determined from the measure- NlxVr=N2XV2 (,)
ment ofpH at the equivalence point from the titra-
tion curve. For example, for a weak acid, HA This is called normality quation.
In terms of molarities, as
HA + H++A-
Normality of an acid (\)
_ _ lH+l lA-l = Molarity (MJ x Basicity of the acid (n,)

or rH.l=1X+K,
and Normality of a base (Nr)

= Molarity (Ma) x Acidity of the base (n 6)

or - Iog [H+] = - toC K, - l"g the equation \xVa = NlxVo can be written as
tH
I!41 noMoYo = n5MoY5 (,,)
i.e, pH = pKo- Iog
tA-l Thus ifboth acid and base have same basicity
The half-equivalence point is the point in the and acidity i.e. na = ,rr, we can write
neutralisation at which one half of HA has been
neutralised in the reaction
M"V,=M5V5 ...(I1r)

HA + OH- # HrO +A- Equation (ii) and (iii) are called molarity
At this point, tHAl = IA-l equations. These equations may also be uritten
:. pH = pKo - log 1 =pK,. as

Thus at the half-equivalence point (half- n, M, V, = nrMrY,

neutralisation)
and MtV, = M2Vr.
pH = pK,
 EQUtLtBHTUM (lONtC EQUtLtBRtUM tN SOLUTTONS) 8/39
-

, l_ IDdicators used iD different titrations

Type oftitrotion lndicatot uted
(D Strong acid vs strong base Phenolphthalein or Mcthyl oraDgc or Methylred,
Bromothymol and thynolphrhalein
(iD Weak acrd vs slrong base Phenolphthalein and 'l'hymotphthaleio
0ir) Strong acid vs weak basa Mcthyl orange or Methyl red and Bromocre,lol green
,,i2. U[iversal indiclton Il is irn]D(tureofa nun'rber ofindicators which shows colour changes over diffcreot pI-I
ranges
pH:246 810 12
Colour : Red OraDge Yellow GreeD Blue Purple

8.13. Solubilhy Equilibrium and Solubility Produci Similarly, the solubility products of BaSO4,
If a sparingly soluble salt like AgCl is stirred Al (OH), and Car(PO)n may be represented as
rvith water, only a small amount of it gocs into
solution (and makes the solution saturated) while BaSt\ (s) <J Bo'* + SO?- ;
most of the salt remains undissolved. But \yhatever
little amount of thc salt dissolves, it gcts completely
(o = [na'z+1 1srlo2-;
dissociated into ions. In other words, when a spar- Al(oH)3 (s) + Al3+ + 3OH-;
ingly soluble salt is added to water, there cxists a
dynqmic eEtilibitut between the undissolved solid \p = [Al3+l [oH-13
salt and the ions which it furnishes in solution.
At equilibrium thc solid AgCI continues to Ca, (POo), (.r) .* 3Ca2+ + 2PO3o- ;

dissolve at the same rate at which the opposite

process ofprecipitation takes placc. Th us, thc eqr,i-
\o = [ca'?+13 lnol-12
librium can be rcprcsented by a reversible equation In general, for any electrollte,\ By, the equi-
as shown belorv : librium may be represcnted as
Dissolution
AgCI(s) \-J AgCl (aq) \= A, B, + -rAI+ + /Br-
Precipira(ion
Thus the solubility product for A, B, may be
Ag+ (qq) + Ct- (aq)
written as lto = [er+y x [Br-],
or we may write directly as
Ag Cl (s) ;-r ee* kq) + Cl- (aq) where.r and y represent the number of ions in the
Appllng law of chemical equilibrium, we have formula of the elcctrollte. Thus

._ [As+l lct-l SolubiuE product oJ an elearolytc

tAgcll
Since concenlration of the undissoiiated solid
remains almost constant, wc may wr;te
lAs+l [cl-l : K x [Agcl] : Ks,
The values ofsolubilityproducts ofsome com-
where \, is callcd solubility product and is equal
mon sparingly soluble salts are listed in the follow-
toionicproduct [Ag+l [Cl-] tbrasatxraredsolu- ing table :
tion.
8l40 Neul Course Cltemistrg
'lAItt,D 1t.7. Soiubility products ofsome com- of Solubitity Product. The
mon sparingly solutrle salts at 29t K product of a sparingly soluble salt at a
temperature can be calculated from a
Salt ri.p is"rr I K* of the solubility of the salt in water at
that icular temperature. This is illustratedwith
AgCl l 8 x 10-lo SrSOa 3.2 x 10-1
the i of the following examples :
/\gBr 5,0 x 10-13 SrF2 2.5 x 10-e
7'1rc solubility of AgCl in water
AgI B 3 x 10-17 SrCO3 t I x 10-10 be 1.06 x 10-s motes per litre.
Ag2CrO4 l.l x 10-12 cds 8 0 x 10-27 the sohtbility product of AgCl at this
A!"SO. 1.4 x 10-5 CUS 6.3 x 10-36 . AgCl ionizes completely in the
A82CO.r 8lx 10-12 Hgs 4 0 x t0-53
BaSOa l 1x 10- 10 MrS 2 5 x 10-13 AgCl ----------- Ag+ + Cl-
mole of AgCl in the solution gives I mole
r'.e. 1
BaCrOa 1.2 x l0- lo Nis 4.7 x 10-5
of Ag+ ions and 1 mole of Cl- ions.
IJaF2 1.0 x 10-6 Pbs 8.0 x 1o-28 Now, as the solubility of AgCI
CaS04 9.1 x 10-6 SDS 1.(lx l0- 25 :
1.06 x 10-s moles per litre
CaqC)4 4.0 x l0-e Zus 1.6 x 10-24 ,1 [AC+l = 1.06 x 10-5 moles/litre
CaF2 5.3 x 10-e Fes 6.3 x 10-18
and [Cl-] = 1.96 x 10-5 moleVlitre
CuCl
r'. K.o for AgCl = lAg+l [Cl-]
CaCO3 2 8 x l0-9 1.7 x 10-6
Oa(Orl)2 55x10-6 H82Cl2 l 3 x 10-18
Pbctz
= 1.1 x 10-lo
Cu(OU)2 2 2 x 7O-7o 16x10-s .Er,rrtt'1.t.- :. I'he sohtbility oJ Mg(oH)2 is
.,u(oH)3 13 x 10-33 PbF2 77x10-8 835) x 10-3 gllitre at 290"c. Find out its K,pat this
lre(OtI)3 10 x 10-38 PbB12 4.0 x 10-5 temryrafi$e.
MS(oH)2 I 8 x lo-ll PbI2 ?1xl0-e Sotutlon. Mg (OH), ionizes completely in
Pb(()t l)2 Pbs04 the {olution as
1.2 x l0-lJ 1.6 x 10-B
(OH), -""""'- Mg*' + 2OH-
Mg
Dillerence Detween Solubllity Product anil
Iouic Product. Both ionic product and solubility
.' [Md+l = ltvtg (oH)rl
product represent the product of the concentrations and IoH-l = 2 x [Ms(oH)21
o[ the ion-s in the solutioq each raised to the power But Molar mass of Mg(OH), = 58gmol-l
equal to the numbcr of ions as represented by the
dissociation of oue moleole of thc substance. How-
ever, they differ in the following two aspecLs :
.'. [Ms(oH),I= *##P
(i) The term ionicproiluct has a broad meaning 8'352 x 10-2
since it is applicable to all t),pes of solutio\s, may be -58
utlsohrated or safiuated. C)n the othcr hand, the = l'44 lO-holes/litre
Y.
solubility produc't h:di\ reslrictcd memhg since il ap- .'. tMd*l = 7 44 x lo-a moles/litre
plie\ o,tly to a satlqqted sohttioninwhidl there qists a
dynarnic eEiDbr tm between he undis;qJ-u3d salfand
and [OH-] = 2x1.44x70-1
tle ions prcsat in sotrfi'on. Thus the solubility product = 2.88 x 10-a moles/litre
is in fact t[E.ro-nicTnsduct for a saturated solution. .. \rforMg(oH), = tMg'?+l IoH-12
(ii) The solubility product of a salt is constanl (BY dehnition)
at constant temPerature whereas ionic product = G.44 x 10-1) x (2.88 x 10-4)2
depends upon the concentrations of ions in the
solution. = 1.194 x l0-rr
EQUtLTBRIUM ll (ONIC EOUILIBRIUM lN SOLUTIONS) 8141
-

l. Clculate the solubility product ofsilver bromidc if the solubility product coosiant at roonr tempera-
the solubiliiy of the salt iD saturated solution is ture. (At. wt. : Pb = 20'l, Cl = 35.5)
x tO-7 noles,4itre. l,rr. 3,25 x 1o-13;
.5.? [\rs 3.09 x 10-a]
A saturated solution of sparingly soluble lead 3. The solubility of lead iodide in water is 0.63 Mitre.
chloride on analysis was found to coDtaiD 11.84 Calculate the solubility product of lcad iodirle. (At
Mitre of the salt at room temperature. Calculate massofPb = 207,I = 127) [.tDs, 1o-81

2. Solubility of Pbclz K? = [Pb2+] [O-]2

rnott--l = (4.zss x 1O-2) x 4.259 x
= rurjl$rr3 <2 lO-2)2

x l0 'nrol L '
= 4.259
=309xl0'
PbCl2...- P5z+ 12 61-,

providcs thc common Cl- ions, the solubility o[

I! m un ionic equilibrium',{A i- l++B-, AgCl decreases.
a salt Lwlaining s common ion (e.8. AC ot BD) is
ailded, the equilibrium shifts in the bdckt+ ard direc- AgCl (s) <.----l Ae* @q) + Cl- (aq)
tion. Thit k cnllul commofi iot efect, NaCl ------+ Na+ + Cll-
Ths results can be easily explained on thc This is again because by Le Chatelicr's prin-
basis oI Lc Chatelier's principle. ciple, increase in the concentration of Cll- ions
shifts the equilibrium in thc backward direction i.e.
Examples. (i) Acetic acid, being a wcak acid,
some solid AgCl separates out. Similarty, solubility
ionizes lo a small eKent as [ollows:
of lead iodide (Pblr) in rvater decreases if Kl is
CH3COOH <--------\ CH3COO- + H*...(i)
added to it.
To this solution suppose the salt of this woak Thus'common ion etlect'may also be defined
acid with a strong base (e.& CH3COONa) is added. as follorvs:
It ionizes almost completely in the solution as fol-
lows and provides thc common acelale ions Il to the soltttion of a b,eflk electrubte (e.9. &cetic
CHTCOONa .......; CH:COO- + Na+ acid or ammonia) , whi.h ionizd la a sn4U &enl,
a strong eledrotllc hr. a common ion k added
As a result, the concentration of CHTCOO- which ionizes alnust the ionizattun ol
ions increases and by Le Chatelier's principle, the lhg$e\k rased. Similorty,
dissociation equilibrium (i) shifts backwards i.e. if to the solution of a solthle salt (like
dissociation of acetic acid is further suppressed. AgCl, PbI2etc.), iI a common
(li) To the solution of the rvcak base, ion ir ailded, tfu sotubiliry of lhe sparingly tohtble
NH4OH, if NH.CI is added which providcs the sal further decreues.
commoo NHo+ ions, dissociation of NH,OH is sup-
Remembcring that the solubility product of a
pressed
salt is constant irrcspective of the source ofthe ions,
NH4OH + NH4+ + OH- thc solubility of a sparingly soluble salt in the
NH4CI + Cl- prescnce of a soluhle sall having common ion can
-NH4+
(iii) To the solution ofsilver chloride in water,
be calculated. (See solved example 3 on page of
8t44).
(being a saturated solution because solubilitv of
8142 Prldeep's .;i

'?-R9:?"t.1;.:E|V.9,., @r!s;t trlnuRNclt ot,'c'ot\tNloN r()N rirt.'t,tc'r' ()N

DDGREE OI,- IONISATION oI.' ACII)S AND I]idS IiS

phenate ion in 0.05 M solution olphenol ? Whqtwill

. - [H+l [x- |
bc its degree oI ionization if the solution is also 0.01
tHxl
M in sodium phenute ? (N.C.E.R.'r.)
is constant at constant temperature irrespectivc of
tho source ofH+ or X- ions. The degree o[ioniza- Solution.
tion is given by C.H.oH C6H5o- + H+
d= tnitial d oi pr
'f(rt (Refer to page 8t10)
rvhcrc c is the molar concentration of HX. How- After disso. 0.05-r - xx
cvcr, degree oI ionization is affected iI extra H+ or
X- (liom any other source) are present.
K"=::x
' (,.o5 x=
r.o x ro-ro (civ(n)
-
_1
Similarly, for a base MC)H (MOH <-
N{+ + OH-) the ionization constant Kb is constant
ut =1-=10x
u.05
l0-lo
aI constant temperature irrespcctivc o[ the source (Taking 0.05 -r: 0.05)
o[ M+ or C)H- ions. The degree of ionization is
given by or l=5x10-12 or x=2.2xlO-5.l,{
a = 'IRJV In presence of 0.01 CuHrC)Na, suppose y is
However, degree of ionization is affected if the amount of phenol dissociated, then at equi-
extra M+ or OH- (from any other source) are also librium
present. [C6H5OHI = -, :0 05,
0 05

lC6HsO-l = 0.01 +) - 0.01 M,[H+] =yM

oJ iotrization if its solution is 0.05 M. Wst will be its
degea of ionizution if the solution is 0.01 M in HCI K. = qT050 = 1'o x to-lo (Given)
&lso ? (N.C.E.R.T,)
or Y=5X10-10
Sglllgl. As already discussed on pagc 8/10
o = ,IK.Jc .'. q =Lv = 5"="
x 10-lo
i" =- = 111-r.
f--------------'
c Jxl(,'
=Y (1.32 x I0-5) x 0.05 = t.62 x t0-2
( HICH?COOH . CHTCHzCOO- + H+
In presence of HCl, equilibriun will shift in IIS- iotrs in its 0.1 M solution and how tyill this
-
the backward direction i.e. concentration of concentration be affected if the solution is 0. 1 M in
CH3CH2COOH will decrease. If c is the initial I{Cl qlso ? If the second dissociation constant ol
concentration andr is the amount now dissociated, i
HS is 1.2 t0-t3, calculate the concenrration if
thcn at equilibrium 52- under both conditions. (N.C.E.R.T.)
Solution. To calculate IHS-]
[CH3CH2COOHI = c -:, HrS i- H+ + HS-
ICH3CH2COO-I =x,[H+l =0 01 +-r Initial 0.1M
. k. _x(0 01 +-r) -x(0 01) After disso. 0.1 - -r x x
" (-x c :0.1
, L 1.32 x 1o-5 9.1x 1o-E
- c 001 l0-r =132xl0-r " =',x'=
K-
0.1
a=l32xl0-'- or f=97x10-e or r=9.54 x l0-5.
EOUTLTBRTUM
- [ 0ON|C EOUTLIBHtUM tN SOLUTTONS) 8143

In prescnce of 0 1 M HCl, suppose HrS dis- ln the abssnce of 0.1 M HCl,

sociatcd isy. Then at equilibrium [H+] = 2ls'?-l
[HrS] =g'1-y:O t, Hcnceif lS2-l =.r, [H+l = 2r
lH+l = 0.r +y:0.1,[Hs-l =],M r.oszx
o'u',f
tr+= Lo-2o

K,= x (Giyen) 1O-8 or 4f = 1.192v 16-zr

or
'''
Y=9'1x10-tM
'= or I =0.273 x 10-21 = Z73x 70-21
3logx = logTl3 - 24 = 2 4362- 24
To calculate [S2-]
logx = 0'8127 -8=8.872:7
K
or .r = Antilog 8.8127
HrS . - H++HS-
= 6.497 x 10-8 = 6.5 x 10-8 M.
K
\ In prcsence of 0. I M HCl,
HS- =-r H+ + 52- suppose [S2-] = y, then
For the overall reaction, lHrsl = 0 -y :0 1M,
1
H2S .-r 2H+ + 52-
lH+l = 0.r +y:0.1M
& = K,, x &, = s't x 1o-8 x l'2 x 1o-r3
K, = fo = 1.oe x
=7 092 x"10-20 lli'Y 10-20

,, _ lH + 12 ls2-l y=109x10-reM.
lH,Sl

P-Rpib.L.EM5 FOR
1. The pKa value of acetic acid is 4.74. Calculate 2. Calculate lhe de8ree of ionization of 0.02 M
degree ofionization of 0 05 M acetic acid solution. dimethyl amine solution. GiveD that its ionization
How is the degree of ionizatioD affected if iLs solu- coDsiant is 5.4 x l0-4. What percentage of
tioD is also (u) 0.01 M (6) 0.1 M in HCI ? dimettryl amine is ionized if the solution is also 0.1
[.lrrs. 0.019, (a) 0 001E (D) 0 flX)lE i.e. each case, M in NaOH ? [.\ns 0 164,0 00541
It decreases by o factor of10l

1. pKo = 4.74 eals-togKa=4.74 In presenc! of0.1 M NaOH, ifr is rhe amount of

dimethyl amine disseiated.
ot log Ka = 5.26
lMoHl = 0 ()2 -rs0.02M,
or &=18xtO-5. [oH-; =g 1+r:0.l,lM+l-rM
,a =,tRJc =/l
" to-s?o{5 = 5 .4 x 1o-1 (Given)
=19xl0-2=0.019.
Further proced as in solvcd example 1. r=108xl0-aM
2'
. =,tfrZZ ='lS+rto-rro.tn =o.rc1
"=i=to?-tio-o=ooos+.
8.15. Applications ot Solubility (1) Calculatlon of solubllity of sparingly
Produd and Conrnon lon Eflect soluble salts. Knowing the solubility product of a
Some of the inportant applicaiions are dis- spaingly soluble salt a( any given temperature, we
cussed below :
cau very easily calculate its solubility.
8144 Praltaep's Ncu Course Chemis
Thc relationship botween solubility (r) in Let the solubility of PbCl, be s moles/litre.
nrol L- 1 and solubility product (\r) depends upon Then the solution will contains moles of Pb2+ ions
lhc rlrrlure of the salt. For example, and a' molcs of Cl- ions respectively per litre.
(i) For salts of the type AB (e.g. AgCl, Hence, the solubility product, Ilo of PbCl2, would
BaSOo, PbSOo, AIPO. etc.) be giveo by the expression,
AB $4+ a 3- K,e = [Pbr+l [Cl-F
JJS
=s x (2s)2 = 4s3
Kre=[A+] [B-] =5 v5 =52 of
But the vlaue Kp=1.7x 10-5 (Given)
(il) For salts of the type ABz (e.8.
4t'= 1.7 x 10-s
PbCIr, CaF, etc.) x
2+ or e" ='';'" 1.7
= o 425x10-s
10-s

AB, <--l A+28- or r= (0.425 xtl-s)t/3

sr?5
K,, = [A+] [B-12 =, x (2 s)z = 453 = (4.25 x to-\vl
Similarly for salts of the type A2B (e.9.
Let x = (4.2rr4
.. log.r = l/31oe4.25 - LB (0.6284)
AgrCrO., AgrSO. etc.) also, I!, = zls3.
= 0.2095
(lii) For sal(s o[ the type AB, (e.g
r = Antilog0.2095 = 1.620
I'c(()H)r, Al(OH)3 etc.) Hence s = 1.620 x 10-2 mol L-l
K,, = s x ($)3 = 27sa and so on' ir\ \ill'l i.. 17'1rc solubility product oIAgCl in

I;\.\!IPLIj t . Tlrc solubility product for silver wqter is 1.5 x 10-10. Calculate its solubitity in
chlotide is 1.2 x tl-to s! 29E K. Calculote the 0 01 M NaCl aqueous solution. (Roorkee 1995)
.t(rlubility ol r-illYr "hloidc ot 298 K. Solutlon. As NaCl dissociates completely,
Solution. Silver chloride dissociates accord- therefoie-in d-.01 M NaCl solution, [Cl-] 0.01 M :
ing to-ihe-e[iration lf solubility of AgCl in 0.01 M NaCl solution
AgCl (s) + AgCI (aq) + Ag+ (oq)+Cl- (aq) is s mol L-1, then from AgCl that dissolves,
Let s bc the solubility of AgCl in moles per [AC*] = [Cl-l = .1 pol 1-t
litre.
.. Total [Cl-] =0 01 +s=0'01 M
Consequently, the molar concentration of
Ag+ and Cl- will also be.t each. Substitutiogin the \o for egcl
= IAs+l [Cl-l
oxpression for solubility product ofAgCl
=rx0 01 = 0'01s
rqP = [As+l [cl-] .. 0'01s = 1'5 x 10-ro
= sxs= s2 or i=l5x10-tM
Btrt \p = 1.2 x 10-to (Giten) , ' \ !! i
Whol is tl& minimunt volunrc of
'1
wdter reEtired to dissolve I g o[calcium sulphatc ot
'" * = 12x10-ro 298K. For calciunt sulphate, Krp = 9' I x l0-o.
y'l r; 10-rt
or r= (N.C.E.R.r.)
Solution.
= l 1x l0-jmolL-l (s) +
. IIXAI\IPII, 2. Lead. cltloide has a solubility
CaSOa <J Ca2+ (aq) SOf,- (aq)
pto(htct of 1.7 x l}-s 298 K. Calculate its If s is the solubility of CaSO, in moles L-t,
:ohtbilily ol tltis temperatltre. thbn
Solution. The solubility equilibrium for x lsol-l =r'?
PbC irepresented as: 4r= 1ca'?+l

PbCl, (s) .r Pbz+ (aq)+2Cl- (aq) or ,=r'K;=/t1 ,10*

 EOUtLIBRTUt\/| (lONlC EOUtLtBRtUM lN SOLUTTONS)
- 8145

= 3-OZ x 10-3 mol L-l Thus for dissolving0.411 g, water requirccl =

= 3.02 x 10-3 x 136 g L-l 7L
= 0.411g L-r .. For dissolving 1g, water requircd
(Molar mass of CaSOn = 136r111or-1, I
= 0.4,' L = 2.43 L.

!-g:.M5 FOR. e E..t ... ., '

"RAe?
calculate the solu bility of silver chloride ir
if the solubility
room temperature
waterat
producr or
4.5 x lo-ze respccrivel),. Also calculillc
molarltles orttiir in,tivldual ioos.
rhc

Agclis16x10-10
[,\ns sohrbility ofAg2cron = 6.5 r 1,,-sn,
L-ll
[.\]rs l'26xlo-5mol
MolarityofAg+=1.30xr0*4M
If solu bility product for CaF2 is 1.7 x 10-10at298
Motarity;fcr;:_ = e.s x to_sNl
K calculatc the solubility in mol L-1. solubility ofHgrl, = 2 2{ x l0-r0lV
I rn' 35x10-a] Motarity of Hgl+ =2.2{ xl0-r0N,l
How many moles of AgBr (\p = 5 x tri-t:
Molarity of I- = 4.4s x l0_roMl
mol-2 L-2; will rlissolve in 0.01 M NaBr solution? 5. The solu bility ofproduct consra nr\ of AS2croa and
I r'r..5 x l0- mol L-ll AgBr are 1.1x 10-12 and 5.0 x 11-13 rcspcc-
Csl@late the solubilities of siker chromate and tively. Calculate thc ratio of n]olirrilics ot rhcir
mercurous iodide in water at 298K Giveo that their sarurated solutions. W.C,E.R.TI
solubility products are l.1x 10-12 and I.\i\.9.151
FO R D IF F IC U LT PRO E} L E I.",{

3. Suppose solubility of AgBr in 0 0r M NaBr 4.H3r, <- "r:- -T

= s mot L-1. Then as
AgBr*Ag++Br- K"o=t x (2s)2 =4l3or,r3=45x 10-29,21
lAg+l = r mol I--l and or 3log.r = log 4.5 - 29 - tog 4 = - 28.9489
'Ibtal [Br-] = o.ol +r-o.olM or logr = - 9.6496 = m.3504
Ilp - tAs+l tBr-l or r = Antilog m.3504 =2 24 x tl-to.
rla5x10-13=sx0.01 5. Clculate thcir solubilities separatcly atld then c l-
culate the ratio.
or s=5x10-llmolL-l

recipitatlonraction. ecipitale out or not wircl t\v()

sents the upper limit known conccntration ol.its
ated solution of any er. This is illuslratcd bt,the:
r words,

centration oI ians itt th rulatbn wwds the value

!;Wf,trf,,#:0,,,,1|)urf,.,,oy j,nl,";i,!!ri,l!;,;,',;,,r,;r;,,;;;
(ii1 Equul rohunes of 2 x t\-E Al Bd(
Thus, having a of solubility
knowledgc lt.,t,hr.
prod uct o[ any sparingly soluble salt, we can predict tionond 2 x l0-3 lt Naz so1.\oltttiou
,tr( /4ir,tl:,
8146

Solution. (i) BaCl, ionizes complotely in thc volunrcs, there is no precipitatiott of -iron sulphide ?
solution as
For iron n phide, K", = 3'l x lO-18. 11,1.g.e.n.f)
BaCl' Ba2+ + 2Cl- Pose the concentration of each
-' ofFe isr mol L-1. Then after mixing
[Ba2+1 = [Baclrl =2x10-3M (Given)
cqual volumes, [FeSOa] = tNarsl = ] rrl
NqSOo ionizes completely in the soluticrn as

NqSOn ._ 2 Na+ +SOl- i.e. IFe'z+l = ts'?-l =;M

. . tSOi-l : tNa, SOrl=2 x r0-4 M (Given)
K,, for Ps5 = [Fe2+] [S2-]
Since equal volumes of the two solutions are
nrixed togethir, therefore, the concentrations of
Ba2+ ions and Sol- ions after mixing will be
i.e. 6'3 x rn-" --l"i
or *=25'2x10-tg
2x10-3
IBaz+l= = 1o'-rM or r=5'02xlo-eM.
t IiXAllI'l-E 3. The concentrution of rulphidc
anrr tsol-l = ?t#: = 1o-{ tu ktn it 0 t M HCI solution saiuated with hybogen
sulphide is 1'0 \ 10-1eM. IIt0mLof this solution
.'. lonic product ofBaSo4=lBaz+l [SO?-] is odtled to 5 ntL ol 0'04 M solution of
FISO o, MnCl2, ZnCl, and CaCl, in which solu'
= 10-3 x 10-a = 10-7
tidns precipitation will take place ? Given K,o for
which is greatcr than the solubility product FeS = 6.3 x 10-18, MnS = 2.5 x 10-t3,
1t x to-101 of BaSoo. Hence a precipitate of ZnS = 1'6 x IT-a ond CdS = 8'0 x t0-?.
BaSO4 will be forrned. (N.C.E.R.T.)

(il) Here, the concentrations bcfore mixing Precipitation will take place in the
are :
solut hich ionic product is greater than
2x 10-8M (Given) solubility product. As 10 mL of solution containing
IBa'?+l=[BaCl2]= 51- ion ii mixed with 5 mL of metal salt solution,
tso!-l=tNqsoal= 2x 10-3 M (Given) after mixing

.. Concentrations after mixing equal volumcs ls,-l = 1.0 x lo-le x 13 = 6 oz,. lo-',
will bc -, = 2' x^ :"
l0-8
= l0-8 M
lBaz+ | lFe2+l = [Mn2+l = Iz*+l = [Cd2+]
2 x to-3 =fxoo+=l'33x'10-2M
and [Sol-l = = 10-3 M

.. Ionic product ofBaSO4 =[Baz+] [SO?-l .. Ionic product for each of these will be

x 10-3 = 10-11 = [Mr+] [Sr-l

= 10-8
= (1.33 x 1g-z;16 12 x 10-20)
which is less than the solubility product
(1 x 10-t0). Hence no ppt. will be Iormed in this =887x10-22
case. As this is greater than the solubility product
!\1\ll'1.1. 2. Whqt is tlv maxinutm cutt' of zns and CdS, th ereforc, ZrtCl, ar,d, CdCl, solu-
cenlrqtion of equimolar sohttions of fenous sulphate. tions wil be precipitated.
snd sodium sulphide so that when mixed in equal
 EQUTLTBRTUM [ (ONtC EQUTLtBRtUM tN SOLUTTONS)
- 8147

?,B,O,gy,EM,B,,F_O.R
l. Predict whether a precipitato will be formed or Dot 4. PbCt has a solubility product of 1.7 x lO-8.Witl
on mixing 20 ml of 0.001 N NaCl soluiion with 80 a precipitate of PbCt form, when 0.010 mole of
nrl of 0.01 N AgNO3 solution. Itp for AgCl
lead [litrate aod 0.0'10 mole of porassium
= 1.5 x l0-lo [_ L tyill be forEed] chloride are mixed aDd water added upto
2. ll 20 ml oI2 x l0-r tion is mixed wirh I litre ?
20 nrl of 1 x 10-5 M NE SO4 solution, willa ppt. I .lns.yesl
rorm ? (\.p. Ibr Baso4 is l.o x t0-101 ; '.Nol 5. Fquat votume s of 0.002 M solulions of sor.iruur
J. Ca" ions is added to a lilre o .0l M
0.03 nrolc of iorjareandcopperchlorateilrentixedlogclhcr.
SO?- solurion. Will it cause precipiration ot Will it lead to precipitatioo ofcopper iriiate ?

For copPer iodatc' Krp=? 4 x l0-8'

caso4 ? Ilp for casor =2.4 x 10-5
[ .\r) \.precipitatiotr of casoa will occurl @'C'E'R'T') I turs No precipitationl

H INTO FoRrlFFtcuLT PRor.LEMo

1. Alter Drxin8, total volume of the solution = 100 Dtl 4. ds final volu orc of the solu troll = 1 I_, rhcrc ft)rc
20nrlof 10-3MNactsot = l00mlof?M [Pbz+] =001 M=10-2M
IUolariry of NaCl solution in the finalsolution [Cl-] =0.01 M= lO-2M.
=tiulfl-'=2x10-4M Ionic producr of PbCt, - 1tt2+1 1Ct-12

or ICI-I =2x10-4M = (10-2) (10-2)2 = 10-6

which is greater than Krp. Hence ppt. of PbCl2 will
80 nll of l0-2 M AgNOI sol = 100 ml of ? M be formcd.
Molarity of AgN03 solution in the final solurioD 5.2NaIO3 + CuCrOo..- NECTOa + Cu(IO3)2

=80iorrfl-'=s*ro-'rtr Alter mixing, [NaIOr] = [lor-]

2 x l0 "
or [Ag+] =8x10-3 ----Z- = 10-3 M
.. Ionic product = 1eg+; 1Ct-; = 16 x l0-?
= 1.6 x l0-8
whlch is greater thaD thc solubility lcucroal = 1c"'z+; = ?-If1= 16-: y
product. Hence ppr. will be formed.
Ionic producr of Cu(I03L = [Cu2+] [IO3-F
3. In the final solution, [Ca2+] = 0 03 M and
O.Ot M. Henoe ionic producr of casoa = 1ro-31116-:;z = 16-e
lSOl-1 =
As ioniu product is lcss than Krp. no precipitalion
= (0.03 (0.01) = 3 x t0-4 which is greater than willoccur.
Ilp. Henc precipitatioD will occur.

j(i) In explaining salting out or precipitation stirring with sodium chloride. The process is calletl
oflsoluble sal(s. For example, on passing ,salting out,.
hydrochloric acid gas tfuough a saturated solution
of sodium chloride, the concentration of chloride
ions will be increased. This increases the ionic
product of NaCl and the solid salt will be
precipitated.
_ Similarly, soap (which is sodium salt ofhigher
fatty acids)is precipitated out from its solution by
solutions, tJre concentration of ions are disturbed
 Ne4l

and in place of K"r, we use the sl,rnbol Qr, fiust as the ca-
are not
we use O.in ptacc oIK"). The concept is applicable
se their
even to soluble salts like NaCl exccpt that we use
activities in place of molar concentratious (due to
(ii) Prccipitation of the hydroxides of group
bigh concentration of their ions). Thus in case of
Na('1.
NaCl(s) sr Na+ (rg) + Cl- (0q)
K,, = [Na+ (oq)l lcl- (oq)l
It tlCl gas is passed through the saturated flightly ionised, whereas NHoCl, being a strong
solution oI NaCl, Cl- ion concentration will in- hectrotye, ionizes almost completely to give a
cl cirslj so that Q,, > Krr, In order that Ory may large concentration of NHn+ ions.
bccoure equal to K,r, cquilibrium will shift in the
NH4 OH s- NH1+ + OH-
backwarcl direction i.e. pure solid NaCl rvill
precipitatc orlt. NHoCt NH4+ + Cl-
(.1) ln Qualitative Analysis. The separation D\e lo
-.... ion elecl,
to ahe common aon the qcgrgg
effect, tno of
degree or
ancl iclcntilication ofvarious basic radicals into dil dissociatiou of NH.C)H gets suppressed and hence
Icrcnt groups is hased upon th(r concentration of OH- ions in solution
(u) Soiubility ptoduct ptittciple, according to decreases appreciably. But even with thislow conc.
rvhich 'a prccipitate is formcd if ionic prodlrct is o[ OH- ions, the ionic products of the cations of
gr eatcr than the solubility produc('. group III and OH- ions excecd the low values of
(h) Connton ion effccr, according to which'il' the solubilityproducts of their correspondingmetal
to thc sohrtion oI a rveak electrol)tc (like NHoOH), hydroxides. As a result, the cations ofgroup III get
r strong clcctrol)'tc having a common ion (like precipitated as their insoluble hydroxides.
NHo (ll) is addcd, the ionization o[ the rveak On the other hand, cations ofgroups I! Vand
clcctroly'tc is further suppressed. Mg which require a large cooc. of OH- ions due
A brief description of the separation of basic
to their high solubility products will not be
precipitated.
radicals into different groups is given below :
(iit) Prcipltation of sulphldes of Sroup IV
Precipitation of sulphides of grottp II'
(i)
Sulphides of group II arc precipitated by passing
The sulphides ofgroup IV are precipitated by pass-
HrS gas through the solution of thesc cations in ing HrS through ammoniacal solution of these ca-

prcsence of dil HCl. tions.

HrS heing a weak electrol)'te ionizes only Both H2S and NH4OH, being weak

slightly, while HCI being a strong electrolrte is electroll,tes; ionize only slightly as :

almost completely ionized. H^s

.s- 2H+ + s2-
HrS.-2H++S2- NH4OH NH4+ + OH-
HCI ,H++cl- =-----\
The H+ ions and OH- ions combine to
Thus the common ion effect takes place. As a produce practically unioniscd molecules of water
result, tho degree ol tlissociation of lIrS dccreases H++OH--HzO
su[[icicntly and the concentration of52- ions irr the As arcsult, the above dissociation equilibrium
solution bccomes very small. But with this lorv con- reactions get shifted in thc forward direction, so
centration of S2- ions' the ionic product of rhe that the cotrcEtration of52- ions goes on increas-
cul.iqns of second group and the sulphide ions ex' ing:Ultima cations of
ceeds the very low solubility products of their cor- group IV solubility
responcling sulplrides. Therefore, the cations o[ products o sulPhides
group Il get precipitated as their insolt:ble sul- and hence get precipitated.
phidcs.
EOUtLTBBTUM [ (rONlC EQUILTBHTUT\,r rN SOLUTIONS) 8149
-
(iv) Prtcipltatlon of Carbonates of Group V K,o for BaCrOa =12x 10-10
The carbonates of group V are precipitated by
adding (NHo), CO, solution to the solution ofthese K,, for SrCrOo = 3 5 x 10-5
cations ia the presence of NH4CI and NH.OH. Assuming volume change ofthe solution to be
(NH4)rCO3, being a weak electrolyte ionises only negligible due to addition of concentrated
slightly to give a sma[ coocen[atioo of CO!- ions. KrCrOn solution, [CrOl-l required to start
(NH4),CO3 2NH1+ + CO3- precipitation of 0. 1 M Ba2+ may be calculated as
<- follows :

On the other hand, NH.CI being a strong

clectro$e, ionises almost completely to give alarge lBa'?+l [CrO?-l = (, for BaCrOa
concentrationof NH1+ ions. Due to the commonion (0 =12x
1) tclo?-l 10-10
effect, the dissociation of (NHo)rCO, is suppressed
aud hencc the coocentration of CO]- ions in the or [crooz-l - 1 2I 10-'0 = 1.2 x to-e M
solution decreases corsiderably. But even with this
low concentration ofCOl- ions, the ionicproducts Similarly [CrO]-l required ro start precipita-
of these cations and CO!-ions exceed the low tioo of0 1 M Sr2+ can be calculated as follows:

valuesof the solubility products of their cor- lsl+l [Cr(X-l = K,, for SrCrOo
responding metal carbonates and thus get
precipitated. (0'1)[Crol-] =3 5 x 10-s
However, under these conditions, Mg salts do
not get precipitated as MgCO, since its solubility or [cro]-l - 3'5] -10-5 = 3.5 x 1o-4 M
product is comparatively high and thus requires a
Thus BaCrOo starts precipitating first be-
high concentration of Col- ions for precipitation.
cause CrOl- concentration required to precipitate
The carbonates of Na+, K+ and NHl+ ions are also
BaCrC). is much smaller than that required for the
not precipitated because they are quite soluble.
precipitation of SrCrOo.
The necessity of addingNH.OH arises due to
the fact that (NH1)zCO3 solution usually contains 8.16. Bufler Solutions and Buffer Action :l:i:j,:I,,ij:r,.,,

a large amount of NH.HCOT. Thus the cations of It is sometimes necessary that a solution of
group V will form not onlyinsoluble carbonates but definite pH be prepared and stored. The preserva-
soluble bicarbonates as well. As a result, the tion ofsuch a solutionis even more difficult than its
precipitation will not be complete. In order to con- preparation. If the solution comes in contact with
vert NHaHCCT3 to (NHl)z CO3 , NHIOH is always air, it will absorb carbon dioxide (an acidic au-
added. hydride) and becomes more acidic. If the solution
NH4HCO3 + NH4OH -.--""r (NH4)2 CO3 + H2O is stored in a glass bottle, the alkaline impurities
present in glass may dissolve iato the solution and
(5) In fractional prccipitation. Fractional
may alter its pH.
precipitation is a technique of separating two or
more ions from a solution by adding a suitable
rcactant that precipitates first oneion, then another
and so on. For example, suppose we have a solution
which is 0. 1 M in Baz+ and 0'1 M in Sr2+. When
a concentrated KrCrOn solution is added (o it slow-
Tlpes ot BulIer solutlors. There are two t)?es
outirst. Wlren most of the
ly, Ba2+ ions pre cipitate of buffer solution-s. These are :
Ba2+ ions (almost whole of it) have precipitated
(l) Solutlons of single substances. The solu-
out, Sr2+ ions start precipitating out. The reason
for this may be orplained on the basis of their tion of thc salt of a weak acid and a weak base c.g.
solubility products as follows :
ammonium acetate (CHTCOONH, acts as a
buffer.
8is0 ;i'! a' Cottsc Chc tu i stt'q

(ii) Soludons of Mixtures. These are further Bufler Action

of two qpes : lJt us consider theb
(a) Acidic Bufier. It Ls the solution ofa mixture cdntaining CH,CO
of a weak acid and a salt of this weak acid with a
strong base (2.9. CH3COOH +CHTCOONa).
(6) Baslc Bufrer. It is the solution of a mixture
of a weak base and a salt of this weak base with a
stmng acid. (e.9. NHIOH + NHICI).

BulTer Action. frrc prow ! of a bufrer sol.ttion lo CHTCOONa .......- CH:COO- + Na+
resist any change in itr.t pH valte evea when smull ...(r,
urutunls o! lhe acid or ,hz base are oddel lo it L\ By'comrnon ion efrect', the ionization of
called 'Buffer action'. H3COOH is further suppressed. Thus in the solu-
The buffer action of different types of buffers D, there are excess of acetate (CHTCOO-) ions
may be orplained as follows :
d a small amount of HrO+ ions.
Bufier Actlon of Ammonlum Actste Solu-
tlon, AmEoEiuE actate like all other salts, is al- When a few drops of an acid are added to the
Eost completely dissociated in the aqueous above mixture solution, the H3C)+ ions given by the
solution as follows : apid combine with the CH3COO- ions to form
CH3COONH4 , CH3COO- + NH4+ eakly ionized molecules of CHTCOOH.
Thus in the solution there is excess of
CH3COO- ions and NH.+ ions.
Thus the HrO+ ion concentration and hence
Whcn a few drops of an acid (say HCI) are pH of the solution remaiD^s almost constant.
added to the above solution, the HrO+ ions given
Similarly, when a few drops of a base are
by the acid combfue with the CHTCOO- ions to added, the OH- ions given by the base combine
form weakly ionized molecules of CH3COOH.
CH3COO- *H3O+ .------ CH3COOH+H2O idnized molecutes of HrO.

Thus the H3O+ ion concentration ofthe solu- H.o+ + OH- 2H2O
tion does not change practically and hence the pH lFro (r)l IGivcn bY the bascl
-
of the solution remains alrnost constant. Similarly, As the HrO+ ions are consumed, the equi-
when a few drops of a base (say NaOH) are added llbriurn (i) shifts towards right (according to Le
to the above solution, the OH- ions given by the Chatelier's principle). Thus more of CHTCOOH
ba*se combine with the NH.+ ions to form weakly dissociates to make up the loss of HrC)+ ions.
ionized molecules of NH4OH. Hence the H3O+ ion concontration or the pH of
NHf, + OH- NH4OH thc solution does not change.
--- Buller Action of Basic BuIIer: The buffer ac-
Thus the OH- ion conccntration aud hence
the HrO+ ion concentration or the pH ofthe solu- tion of a basic buffer e.g NH.OH * NH.CI may
tion remains alrnost consant. he explained as follows :

On thc contrary, the solution of a substance NHoOH dissociates to a small extent whereas
like NaCl cannot act as a buffer because NaCl NH.CI dissociates completely in the aqueous solu-
dissociates completely to give Na+ and Cl- ions. tion as follows :
These may combine with the base or the acid added
to forrnNaOH or HCl. But these ionize comple tely
NH4OH a----\ NH4+ + oH- ...(r)
to give back the OH- ions or HrO+ ions. Thus the NH4CI NH4+ + Cl- ...(r'r)
HrO+ ions crncntration of the solution changes By common ion effect, the ionization of
and hence the pH of the solution changes. NHa OH is further suppressed. Thus in the solu-
EQUTLTBRTUM 0ONIC EQUtLTBRtUM rN SOLUTTONS) 8/51
-
tion, there are excess of NHi ions and a small But [A-l = [BA], therefore
amount of OH- ions, lHAl
When a few drops of a base are added, Lhe lH3o+l =
K"
ffi: rq lAcidl
lsrl,l
OH- ions given by it immediately combine with . (,,)
NH{+ iols to form the weakly ionized NH4OH.
.. pH = - tog [HrO+l ...(n:r)
NH4+ + OH- .+ NH{ OH
Thus the HrO+ ion concentration or the pH
oI the solution remains unaffected.
= _ rog{ro
#itt lAcidl
Similarly, when a small amount of an acid is =- loS I( - tog
added, the HrO+ ions given by it combine with the [Suttl
OH- ions already produced by NH.OH in equi-
or ...(rv)
librium (i).
Hro* + OH- --, ?H2O or substituting the value of [HrO+] from eqn.
Icivcn acidl [Giv bY (i)l
by thc (i) in eqo. (ni), we get
As the OH- ioos are consumed, the equi-
librium (i) shifts itr the forward direction. Thus pH=-logxr-bclH
more of NH.OH dissociates to produce more of
OH- ions which makes up the loss of OH- ions. or pH=p\+rog$J
Hence the OH- ion concentratiotr and therefore,
the HrO+ ion concentration or the pH ofthe solu-
tion rcmains fairly constant.
-lr::r".*t@..r,
Note. (i) From titration curves given in Fig. It is iateresting to observe that if [Salrl/[Acid]
8.3, it may be seen that some portions of the titra- : 10,pH = plq + 1 and if [Acidl/[Sal{ = 10, pH
tion curves are flat. i.e. the pH of the titration = p( - 1. Thus if the ratio of the conjugate acid-
mixtures changes very little even on adding acid or
ba-se pair is changed by 10 times, pH changes by
base. These portions are generally mixtues of acid
and salt or base and salt. Tbus they correspond to =1.
buffer mixtures. (r) For basic bu[fer mlxturr like
(i) A solution ol a strong acid (e.g. HCI) ol Bou + na,
illin!11nanne1
reasonable concenaation ( - 0. I M) also acts as a tSaltl
Dujl'er The acid is completelydissociated and allthe poH = pKb + losffi ...(rr)
H+ ions are present in the free form. From the
titration curve, it may be sen that initial pH in- As pH + pOH :
14, pH can be calculated.
creases only by 0.3 even after half of the acid is Altematively, the above equation can be ex-
neutralized. pressed in a different form as follows :
Calculation of pH of a buflr mixture
pH+pOH=L4
(a) For acldic buffer mixturc (Henderson-
Ilasselbalch equatlon) or pOH=14-pH
If the weak acid is HA and its salt is BA, then Also pK, + pKb = 74
HA + H2O <-r + A- H3O+
or pKt = 14 - pK"
BA -----.. B+ + A-
Substituting these values in eqn. (vi), we get
K"= lH3o+l [A-]
IHA] 1.4-pH=:a-pK.+togf4q-
' [Basel
: -,
lH3o+l
lH (D
or pH= pK"-,"tffi
8152 ),,r."r,
Buffer capacity
pH=pK"+ bcm ...(vii) No. of moles of the acid or bas
added to 1 litre of the buffer dn
where K, is the ionization corLstant ofthe conjugate Change in pH d pH'
acid of the base (e.g, io the buffer Buffer capacityof abufferis maximum wfn the
NH4oH + NH4CI, NH4+ is the conjugate acid oI coocentration of the weak acid and its salt or weak
the base NH3 and I! represents the ionization base and its salt are equal i.e. when pH = pl(o or
constant of the reaction pOH = pKu. (Refer to Henderson equation).
NH4+ (u4) + Hro O <- Importance of BulIer Solutlons :
(1) In blologlcal processes. The pH of our
NHr (as) + H+ (aq) blood is maintained constant (at about 7'4) inspite
Thus for this basic buffer, the above equation of various acid and base-producing reactioos going
implies that on in our body. In the absence of its buffer nature,
we could not eat a variety offoods and spices.
pn=p\* l"gffi (2) In Indusfial
pa
procsses. The use ofbuffers is
an important ofmany industria.l processes, e.&,
(i) In electroplating ;

i.e.l pH = pY1+togiA#ml ...r,o (ii) in the manufacture of leather, photo-

gtaphic matcrials and dyes ;
(iii) in analltical chemistry ;
Buffer capecl$ or BulTr lndex. It is defined (iv) to calibrate the pH metres ;
as the number of moles o[ an acid or abase required (v) in bacteriological research-culture media
lo be added to one life oI the bulfet solution so as to are generally buffered to maintain the pH rcquired
chmge its pH by one urir. Thus for the growth of the bacteria being studied.

PtR-@^i ,9,N ttt ttt..R sot.uiroNs

By Heoderson equation,pH of aD acid buffer is SiveD by

pH =pK, + logffi
Similarly, for a basic buffer

PoH =PK, + ro8#s

pl{ r pOH = 14 Le. pH = 14 - pOH.

1. Calculate the pH of a buffer

' l:xr*lPLE
1 M in acetic dcid gnd 0'15 M in sodium
=(5-0.2430)+o1761
wlrich is 0' =4 757 +01761=4'933.
acetate- Gieen thita lhe ionization constsnts o[ acetic (i) 1 cc of 1 M NaOH contains NaOH
acidk 1'75 x 10'5, Also catcllate he chanie in pH 10-3 mol. This will convert 10-3 mol of acetic
=
of the buffer if to 1 litrebflhe bulfet acid into the salt so that salt formed = 10-3 mol
(i) I cc of I M NaOH\ore odded Now [Acid] = 0' 10 0'001 = 0'099 M
(ii) 1 cc ol I M HA ore added
-
Assame that the change in volume is negligible. [salt] = 9 15 + o ool = o'151 M

$slutton. pH = pK" + log '!u!L pH=4.757+rosffi

fncidl
= - los (1.75 x ro-j) + louo*E = 4 757 + 0.183 = 4.9110
EQUTLIBRTUM ll (loNlc EQUILIBBIUM lN SOLUTIONS) 8/53
-
.'. Increase inpH = 4'94O - 4 933 = 0'00'l 250 mL of0 1M NHaCI
which is negligible. = 250 x 0 l millimole = 25millimoles
(ii) I cc- of 1 M HCI cootains HCI Total volume ofsolution after mixing = 255 rnl-
= 10:3 mol. This will convert 10-3 mol
){
CHTCOONa into CHsCOOH. .. lsaltl = lNH4cll = ii; M
.. Now[Acid] =010+0 001 =0101 M n.<
[Saltl =015-0 001 =0'149M [Basel =[NHooHl =#M
... pH = 4.757 + rosfr1#
pol = pKu+ r"e#H
=4 757 +0169=4'926
..DecreaseinpH = 4' 933 - 4 926 : 0' 007 + bc##*
= - rog(1.8 x 1o-5)
which is again negligible.
t t,l\ \\ll't )
i. Culculate the PH of s soll ion = (5 - 0 2553) + 1 6990 = 6 443'7

obtained by miing 5 mL ol0 1MNHooHtaith250 pH = 14-6.4437 =7 5563

nrL of 0'1 M NH4CI solttion. Kb lor NH,OH Note. For more solved examples, see problem
= 1'8 x 10-5. 5, page 8/66 and problems 70, 14,24 ar.d 31,
S-ohltion.5 mLof 0 1MNHIOH=5x01 pages8170,7l,74 and 75, given under CBSE-PMT
millimole : 0 5mil.limole (Mains) Special and IIT (Mains) Special.

?RACTICE
1 How muchvolume ofo 1 M HAc sbould b added monium chloride to give a buffer solu tion ofpH 10.
to 50 mL of 0 2 M NaAc solutioD if wc waDt to civen pK! for NHaOH is 4.75. [,\r,,,. ll2.SIDLI
prepare a buffer solution ofpH 4 91. GivenPIq
3. The ionization constant of formic acid is
for acetic acid is 4 76. [rrns. 70 92 nll 1.8 x 10-4. Calculate the ratio of sodium formate
2, Ho,x much of0.3 M aornronium hydroxide should and iormic acid in a buffer of pH 4.25. [.rns.3.24t
be mixed witb 30 mL of 0 2 M solutioD ot aDt-

1. pH = pKo+ roUffi pot=pKb+ bs#H

i.e. 4.s1= a.z6 + tosffi 4 = 4.1s + t.c
IB"ES

o,rosffi=o ts
or rogffi= - o.1s =T.2s
1s=1
o, ffi=0.177s
", fir4$=Antiloso
Moles of Salt
41
.
re. Moles of salt
u.l //d
M6tes;IAcid- = l 4l
M6E6TT- =
0.2
o.2
lTfri x )u o.o * g':l =01778 orv=rr2.5mr
r.e -or--= = r'4r ot o.mTtlv = I 4l v
mm'u mr''
3. pK.= - log(1 8xt0-1)=3.74
or V = 100.u 1 41
= 70 92 mL, Iogffi=pU - pK!= 4 2s -3.74 =0.s1.
2.pOH=14-pH=14-10=4
or lsalt]/[Acid] = Artilos 0.s1 = 3.24.
8154 I Newr Course

A,D,iP I iUiiR,.K,,N,'O L-i . iE t

I

t pH of a buffer solution does not change on dilution or on keeping for long time or on adding small amounts
ofan acid or a base.
: pH of a buffer changes with temperature because K* changes.pH decreases with increase of tenrperature.
, Buffer solutions can also be obtained by mixing an acid salt and a normal salt of a polybasic acid e.g.
NarHPOo + NarPOo.

How does the degree ofionization ofa weak electrolyte vary with concentration ? Give exnct relationship.
What is this law called ?
Ans a : '/KV-C. It is calted Ostwald's dilution law (K, is ionization constant and C is nrolar concentration of the
electrolyte).
: Classify ench of the following substances into nn ncid or bnse or both and mention the concepVconcepts
on the hasis ofwhich you can do so.
(i) Hcl (aq) (ir) NH3 (iii) Na,G) co3@O
(ir,) CHTCooII (as)

(y) Co, (g) (ri) BF3 (rir') Ag+ (r,iii) cN-

(lr) Hzo (.v) H2So. (d) Hcot (rt| siF;

Ans. (i) HCI (aq) Acid (Arrhenius conc.ept and Bronsted Lowry concept)
(rr) NH3 (g)
- Base (Bronsted concept and Lewis concept)
-
-
(iii) NqCO, (oq) Base (Bronsted concept)
-
(iv) CHTCOOH (aq) Acid (Arrhenius concept and Bronsted concept)
-
(v) Co, (g) Acid (Bronsted concept and Lewis concept)
-
(vi) BF, Acicl (Lewis concept)
-
(vii) Ag+ Acid (Lervis concept)
-
(viii) CN- Base (Lewis concept)
(rr) H2O
-Both acid and base l.e. an:photerric (Bronsted concept)
-
(Bronsted concept)
(x) HrSOo
- Both acid and trase r.e. amphoterric
(ri) HCOI
- Both acid ancl base ie. anrphoteric
(Bronstcd concePt)
(rD SiF4 Acid (Lewis concept)
-
; r Write down the conjugate aciil and conjugate bnse of
(i) Hzo (i, Hso; (rri) NH3 (ir,) HS-
Ans. (i) H3O-F , OFI- (i') FI2SO4
'
SOl- ('ii) NH4+
'
NHt (iv) HrS 52-
'

Q. 4 ecles:
IrNO2' cN-' HCIO4' F-' OH-' C()3-' 52- (N.C.E.R.T)

,t-
EQUTLTBRTUM (tONtC EQUTLTBRTUTV rN SOLUTTONS) 8/5s
-
Ans. NO! , HCN , ClOa , HF, H2O , HCO3- , HS-.

Q. 5. Which of the following nre Lelvis acids ? tI2O , BF3 , H+ , NH.+. W.C.E.R.T:)
Ans. BF3, H+ and NHf (Remenrber that all catioos are Lewis acids).

Q.6 Classify the following into l,ewis acids and [,ewis bases, oll- , F- , It+ , BCl3.
Ans. OH- and F- are Levr'is bases bccause thcy can dooate a pair oI electroDs while H + and BCb are Lewis acids
because they can accpt a lone pair of electrons (lo BCl3, B is electron delicient).

Q.7. lvhich cohcept c6n justify that CaO + SO3 ........- CaSOa is an [cid-lrase reactlon ?
Ans. Lewis concept.
Q. r{. Ionization constants Ko for formic acid trnd acetic acid flrc 17.7 x '10-5 and I 77 x 10-5. Whlch acid ls
stronger flnd how many times the other if equimolar concentrations ofthe two are trkcn ?
Ans, Ko for HCOOH > K. for CH3COOH. HeDce forDic acld is stronger.

Kltcoott
Further
Strenlth of HCOOH
Strength of CH3COoH
--.:: = y'IU = 3.16 rimcs.
Kcttacoou
(J.9. Fill in the blanke:
A strong acid has a wealc..,....and a weak base has a strong........
Ans. Conjugate base, conjugale acid.
Q.llr. Out of CH3COO- and OH- which is stronger base flnd why ?

Ans, OH- ions can combine with H+ ions nore rea<jily rhan CH3COO- ions can do. Hence OH- is a srollger
base.
(1. ll What will be thepH ofl M N0NO3 solution at 25'C ?

Ars. NaNO3 is a salt ofstrong acid and strong base. Ilencc its solurion will be neutral. At 25'C, irspH will be = 7.

Q. I 2 IIow ls the degre of dissociation of a weak b^se related to its molarity ?

A"".
" = fi;/ C= z M where M = nrolariry
Q. 13. What is the elfect of temperature oD ionic product of water and why ?
-Ko
Ahs. Ionic product of watcr (Iqd) increases with increase of temprature because Iq = [H3O+] [OH-] aDd
dissociatioo of FIzO to Eivc lt3O+ and OI"I- increases with increase of tempemture-

Q. l.l What happens to the idnic product ofwrter i[some acid is added into ttrEter ?

Ans. If remaiDs unchanged.

Q. I5. What ispK, ? What is its value at 25'C ?

Ans'
P\e = - los K,, = - log 1o 1a= 14

Q. l6. Whflt are pH ond pOH vnhes o[ a neutral solution flt r temp.rrt[re at which K, = 16-rJ i
Ans. pKl" = pH + pOH- But/Iq = 13. Also, for neutralsolution,pH =pOH. Hence pH = pOH = 6.5.

Q. 17. The ionization constants of IIF is 6.E x 10-'. Calculrt. the ionizatlon consttrnt of the corrcspondllg
conjugate hose. (N.C.E.R.T)
Ans. Kb=Kr,/q= rc-14/(6.8x 10-a; = 1.47 x t0-rl :1 5 x l0-1r

Q. 18. Whst pH do you expect for 10-t M soluti.rn ofan ncid ?

Ans. Clos to 7 but < 7. (Refer to solved example on page 826).
8/56 Pradeep's
Q. 19. Predlct the ncidic, boslc or ncutral nature of the solutions of the followlng Eolts :
NoCl, KBn NaCN, NH.NO3, NnNO2, KE (N.C.E.P.r)
Ans. NaCN, NaNOz, KF solutions arc basic
NaCl, KBr solutions are neutral
NH4N03 solution is acidic.
(.) lt)
Whot is the differencc Detween ionic prodrct nnd sohtbility product ?
Ans. Solubility product rs the product of the molar conccntrations of the ioDs in a snturnted solution but ionic
product is for any soluiion.
r.r : I When is n precipitote formed whcn solutions of BaCl2 nnd Nn2SOa ore mixed ?
Ans. wher in the fiDalsolution after nrixing, the ioDic product [Ba2+] [So?-] > I(o for Basoo.
i.) -tl lvill A8CI l)e Inore soluhle in oqueous solution or NaCl solrrtion and why ?
Ahs. Agct . - Ag+ + cl-
In NaCI solution, [Cl-]rvill incrcasc. As IAg+l [Cl-] = K5, remains constant, [Ag+] will decrease ie. the
solubility will be lqss in NaCl solutioD than iD warer.
rJ -t-r. Why solid NnCl starts separrting out from ft satunrted soltttion of NnCl if IlCl gas is pEssed through it ?
tus. HCI iD the solurioD provides Cl- ions. This increases the ioDic product of NaCl and so the solid NaCl starts
seParating out.
tJ ll wlry cornmorl salt is sdded to precipitBte otit soap from the solution dttring its man[fficture ?
hs. Soap sodiun salt ofhigher fattyacids (RCOONa). OD adding common salt, Nat ion concentration increases.
is

Heoce the equilibrium RCOONa (r) <- RCoo- + Na+ sbtfts in the backward direction r|e soap
precipitatcs out.
(l -.:! Through n solution contnining Cu2+ nnd Ni2+, [IrS gasispnssed after adding dil HCl, which lvill precipltote
out nnd why ?
Ans, Cu2+ will precipiiate out because in thc acidic medium, only ior:ic proriuct ICuz+ I [S2- ] exceeds the solubility
product of CuS.
r., tii why in Group V of qualitative nnnlysis, sullicient NlloOH solutioa should be added hefore adding
(NH.)2CO3 solution ?
Ans. This is done to convert NHaHCO3 usually present in Iargc amounts alontr ith (NHr2CO3 to (NH1)2CO3
NHlHCO3+NI14OH+ (N IIa)2CO3 + H2O
(2 17. Whnt is pll of our hlood ? lvhy does it remnin dlmost constflrrt inspite the yariety of foods oltd sPices

Ans. pH ofour blood is about 7 4- It remails constaDt because it is a buffer.

(l lU. ThepH ofon enzyme catalysed renction hns io be maintaiDed between 7 flnd E, Whnt indicator sho[ld be
used to monitorond control thepll ? (N.C.E.R.T)
Ahs. Bromothymol blue or Phenol red or Cresol rcd (see'Ihble 8.6 Page 8,47).
(l lr. ThepKIr ofan indicntoris 10 5. Forwhichpll trnrsitionrange is the indicator most suitsble ? @.C,E.R.I:)
turs. pKrn r 1 r:e. 9.5 ro l1 .5.

e 10. Benzoicocidisamonobnsicocid,When122gofitspuresampleoredissolvedinwaterandtitratedagainst
base,50mlofo 2 (N.C.E.R.T)
M NaOII are uscd Up. Cfllculate the molst mnss of benzoic acid.
Ans. 1000 nrlof t M NaoH will neurralize acid = ij# " 1ooo = t22 s
But 1000 ml of 1 M NaOH contarrr 1 mole of NaOll and will neutralize I nrole of mooobasic acid. Hence
nrolar mass ofbenzoic acicl = t22I mol-1.
(J. -t I A solutioh gives yellow colourryith methyl orange, methyl redcnd phenbl red. What is thcPHof the
solution ?
 EQUTLTBHtUM (tONlC EQUtLtBRtUM tN SOLUTTONS)
- 8ls7
Ans, Yellow colour with Dethylorange meanspH > 4.5
Yellow colour with methyl red meanspH > 6.2
Yellow colourwith pbenol rcd meanspH < 6.4. Henc the lolution haspH bchpEe n 6.Lao 6.4.
Q.32,ThelonlzstloncolsirDtoflormlcacldlsItxl0-'.Arou[dwhatpEl" lltsmtlturrtrlthlodlumforIlstr
give huffer solution olhlShest capacity ?
Ans. Buffer solution of highcst capacity is formed at whicbpH - plq - _ log (f .8 x l0-l _ 3.74.

CARRYING ,I MARK
Q'1'whotlsthelsvcall.dwhlch8lvrchdoDsblpbctrccrd.grGcofdlmtodo!ofrr..kclet,lyt.Ddlt
concentratloD in thc solution ?
Ars, Ostwald's dilurion law.
Q. 2. Whot ls the dillerence btnccD a coqlugqt ocld ard o coEJugsaG borc ?
tus A coniugate acid and base differ by a proton (Conjugalc acid q=* ConjugaE bolc + H+)
Q. 3. Wtitc the cxPressioD for comParison of relative strengths of two mat acids in tcrlllr of thalr ionizrtlon
coDsialrts.

*-ff*!{ffi =\
Q. 4. Whnt is the flctive mass ofwater ?
Ans. 55.5 mol L-l
Q. 5. How can we predict whether a precipitate wlll be forDcd or not on mixing two Golutiotrs ?
Ans. A precipitate will be formed if ionic product > solubility product
Q. 6. Whnt happels when HCI gos is passed through saturated NaCl solution ?
Ans. NaClwill be precipitarcd our.
Q. 7, Whnt is the f[nctior ofaddihg NH.OII in group V ?
Ans. Ir conyerrs any NHatlCO3 preseDt into NH1)2 CO3.
Q, tl. Whar hrpl,ens to the ptl if ! few drops of rcid are added ro CII3COONHa solutlo! ?
Ans. pll will rentain
almost comtant (beinga butfer solurion).
Q.9 which ihdicotor shourd preferably be used for titration ofNHaoH with Hcr sorutton ?
Ans. MethyloraDge.
Q. 10. Whot is the relationship betweenpKh aDdpH ot thc equivalence poilt ?
turs, /,I!n = pH ar the equivalence point.
Q' 1l' At half-neutrolisation ofn weok acid with o strong bflse, what ls the relfltloNhlp betwc.rplf ord dlssockrtlor
constont (q) of the rryesk ocld ?
Ans. Al halt-neulralisation.pH - pKs,
Q. 12. lvhnt is the rrnge ofarH indicator in terms ofits dissoclodon constrnt (Kh) ?
Ans. pH =pK,n t 1.

Q. 13. Whrt hflppens to the solubility ofAgCl in nater lfNnCl solutlon ls added to lt ?
Ans. Solubrlity ofAgCl decreases due to common ion effect.
Q I4' *'rnt is thc rerationship between pl(o and pKo varues nhere Kn and Ka reprs.nt ionrzaron constaDb or
the scid nrd its corJugote hase reslectively ?
Ans. pq + /rK, = pK* = A.
Q. 15. lryhat is the relationship hetryeen pH {nd pOII ?
Ans. pH + pOH = pl<w 14. -
8/s8
,) r.t.i('t'i,'s Neqt Course Ch.mistrq@

CARRYING2oT3MARKS
the deSree of
Sec.lt.l. l. What are strong and weak electrolytes ? Derive ao expression for the calculation of
ro lt..:. ionization ofa weak electrolYte.
2. Derive and defioe Ostwald's Dilution l-aw'
Scc. tt.-1. 3. DeIiDe tho follo\.t'ing giving xamples :

(i) Bronsted-Loery acid (ri) Bronsted-Lowry base (iii) Conjugate acid (iv) CoDjugale base
(v) Lewis acid (vi) lrrvis base
Disqrss lhe Proton tramfer theory (Bronsted Lo\T thcory) of acids
8nd bases'
4.
5. What is meanl q the conjugatc acid'base pair ?
the Bronsied definition ?
6. Discus Lewis delinition ofacids aDd bases. How is it more useful tban
Deline the tcrms 'acid' and 'base' ac.cording to each ofthe follo 'ing conceP$
:

(i) turhenius (ii) Bronsted-Lsrry (ir'i) Lewis

gleak bass'
t. Derive expression for dissociation constants of weak acids and
Sec. E.4 9. io" o"yi, thc strengths ot acids aod bass oo tbe basis of Arrhenius theory ?

to 8.5 "rpf"in
or ionization consunts'
10, Discuss the strengths of acids and bases in terms of their diss@iation
and strong base has a weak
ll. Justiry the slatement that a strong acid has a weak conjugaie ba'sc

Scc. t.6 12, the ions of weak or sttong acid or base are allowed to iDteract with water ?
useful in
Src.ll.7. il: tand by the term'ionic Pr-oduct ofwater'? Hqw has this concept beeD
to t.li. nd basicity ofa solution I
t4, ExplaiD the term 'ionic Product of w'ter'
lS. F-xplain the significance of K-.

t6. IJow does iQvary with temPerature and wby ?

Scc. t.9. l?. Bricfly exPlain the term'PH'.

'l
rs. whaido iou undersrand by ,pH sc2le, ? cao a solul ion have pH tess rhan 0 or more than l4 Explain
your answer, Siving suitable reasons.
Sr:c 8.10. u. beriue expreision-for the calculation of pH of a solutioo of a salt ofweak acid with a stronS base or
to 8,1l. weak base with a strong acid.
with a weak base (e8
-20, I'rove that the de8ree of hydrolysis of the solution ofa salt of weak acid
-rrrcoot,tttn; is independLnt of the coDceotration of the solulion'
21. Derive Lhat for the solution of a salt of sirong acid with a $/Eak base (hlwing concentration =cmolL-l)
pH= - | tros x, - log K6 r log cl

Sec. t.12. 22. Brietly explain why PheDophthalein is oot suitable indicator wheo the base is weak acrd why methyl
a

rlrangL is not suitable when lhe actd is weak'

'l Explaio why or why not'
23. Is pH of the end Poinl of acid'base titration a /als equal to 7
equivaleoce point'
24. Prove that for the colour chaogeP&ndicaior = PH at the

25. Why most of the indicators have a useful colour change over a PH range of 2 units ? Prove
mathematicallY.
result
26. Hou, is pK of a weak acid or a weak base determined from the titration curve ? Derive the
matbenlaticallY.
equation' ryM1Y = n.-M2Y'
2?. Derive norrnality equation, NrVr = N2v2 and the nolarity '
acidity and basicity of the base and the acid resPectively'
where n
I and n2 arc the
2ll. ExPlain thc terms
ion elfect
1ij solutritity proouct (ii) Common
 EOutLlBRtuM [ (oNtc EoutLtBHtuM tN soLUT|ONS)
- 8/s9
29. How.does solubility producl differ fro, iooic product ? Discuss two important applications of
solubility product
30. Give rcasoDs for the following :

(i) zDc sulPhide is PreciPirated by hydrogen sulphide ftom an amD.loniacal $olution but not fiom
stroDg hydrochloric acjd solutioo. ir

(ri) The PrcciPitatioo of M8 (oH)2 is preventcd by the addition

of NH.cl prior ro the addirion of
NHaOH but its precipitatio, ty NaOH is not preveDied by the prior
addirion of NaCl.
(rii) ID quatitative anabsis, NHaCI is addcd before adding NHaOH solurion for tqstint
Fe3+, Cf+ and Al3 +
or Discuss rhe use ofamoronium chloride in group III of the
inorganic analysis.
31. Define the term ,sotubiliiy producr,. How would you use this
uoncept lo separate rhe sulphidcs ol.
copper from rbat ofziDc ?
32. H_ow is concept ofsolubility producr urilized in qualitarive
analysts ?
\(r r r6 33' what is the Buffer sorutionl Give an cxampte iran aciuic uufocrand
exprain its buffer action.
34. Derive Henderson-Hasslbalch equation.

CARRYING 5 or more MARKS

Sec.lt.l. l. what arc slrong and naak eledrolytes l Define rhe term ,degree
of ionization, and deriyc hol the
to t.2, degree of ionization is related to the concentration ofthc solu-tion
of rhe etcctrollte.
Src.ll.3, 2. What are acids and bascs accordiDg to
(r) Arrhenius concept (,:i) Bronstea-Lowy coocept ?
In wha( rcspcc,ts (ri) h supcrior to (i) ?
3. Wbat is Lewis coocept of Acids and Ba.ss ? Classify the follo\yi,t
into Lewis acids or l_6rris bass
gMDgreasons: IlzO, BFJ, NH3,SiF1,Ag+, O-, CO2
What are the advaDtages aod limitations of this co[ccpt c,ver the
Sec. {.l,4.
.
4. Derive_ expression relariDg the stleDgrhs of m )nob;t u"ior'li.or"
earlicr mncepts ?
ro t1,5. ionizntion constants of thc acidr.
iorar concentration to the
Scc. E.6. 5. Bricfly explain Aid-Base equilibria taking suirable e)omplc.s.
Sec. E.7. 6. txplain the tcr,,, ,lonic producr of \rhter, and ,pH'vatue,, How
does the former cba[ge with
lo ti.9. temperaturc ? Whal is pH sc{lc ?
Scc tt.l0. 7. Briefly explain the tcrDs-Sall ll1dro[sis, hydrobfsis constant and
degree ot hldrolysis. Derivc
t0 E.l l. opressions for thc calculation otpH of' '
(a) salt ofstroog acid with crat base (r) satt ofweak acid
with weak base-
Scc,lt.l2, t. D6cribc Ostwald,s theory of Acid-Bsse illdicators.
9. Brprain the diffrena types of acid-base tirration curves.
How is a suitabrc indicator serecled for a
particular tirration ?
Sec.8.lJ. 10. B-riefly cxplain the term ,solubility produrl., Disc.uss its aDDhcarion
to 8.15. (r) ill calc.tllatio ofsolubility ofa sparingty solubtc salt (ri1 in quatitative anarysir.
11. Frplain 'Common Ion Effe{t,.
Stc. li.l 6. 12. What ir a 'Bufier solution, ? What are difierc[t types of buffers
? Dhcuss their buffcr actio[. Wbat
k the importaocc of buffers iD biological prcess;'?
Derive expressions for thc pH of (a) aD acidic buffer mixture (D) a basic buffJr ntixture
 2.,

ONiALSI E
solvents' As already explained' acids like HCI' HNO3'
1. tevelling elfect of water and dilferentiatiDg
in water dissociate alnosi completely r"e
their dissociation equilibrium is almost
H2SO4 etc. wtrci ttissolved
H3O+ + Cl- or may be uritten simply as HCI +
H'O --
completely to the right (e.& HCI + H2O <-
all acids stronger than
I{rO+ + Cl-). These acids behave a's equally stroDg in water' In fact' in aqueous solutioD'

is apoor Proton aouePlor. It accepts prolons lo different

which mly be represented in Seneral as
HA (d4) + cH3cooH (44) + A- (aO + ct\cooHl @q)

(4{)
p.g. Haoa (uD+ cH3cooH (d4) <----\ clo4- ('9) + cH3cooHz+
I{No3 (.!q) + cH3cooH (aq) + Not ('I4) + cH3cooHf (44)l
.rheireorrilibriumconstantscanbedeternrinedaodhenctheirrelativestrengthcanbefound.ForexanPle'
ti und to be in the order
," *J;;,h"1*.-h';;;rion.i uu*", tt'" 't'"ngths are
HCIOI > H2SO4 > III > HBr > HCI > HNO3
completely'
strong acids and strong bases dissociate almost
Lastly, it may be mentioned lhat in water' as
K, or KD has no meanlng.
Another solution'
2. on change ln PII on dilution or mixlng i{ith
Ar lnterestlng ol'serYatlon
volttme becomes double' the pH of the diluted rclution
If o solution of PH = 2 b dihued with woter so that the
: PH = 2 nreans [H3o*] =
t0-2 M
can be calcululed ar follows
r
r'r = 5 x l0-3 M
After dilution to double the volume, [H3o*, = 5'
PH = - log(5 x 10-3) = 3 - log5 = 3 - 0 69e - 2 3

2 is mixed with an equal vohune of

a rclution ol pH = 5' tlrc pH of the linal solution con
II o t;olurion of pH =
he calculated ar followt :

r/60
 EQUTLtBRtUM 0oNlc EQUtLtBRIUM
- tN SOLUTTONS)
8/61
ADDITIONAL UgEFUL TNFORMATTON 6ohrd

After mixiDg, for soturion wilhpH = 2, ,5'

[H]O+ j = = S , tO-, t,t

and for solurioD wirh pH = 5, [H3O+] =

,5' = S ,. tO-u t.t
Total [H3O+] = 5 x 10-3 + 5 x 10-6
=5xlo-3(1 +0.001)=5x1001 x l0-3
= 5.005 x tO-3
pH = - log (5.005 x 10-3) =: - tog s.oo5 - 2.J
Thu6 we observe that the sotu-tioo-ofpH 2 when diluted with waler to
=
2 3 Again when the sorurion of rH = 2 is mixed double the volume, pH changes ro
with equat votume o'f-sJru tron ofpH 5, pH agaiD changes
2.3. It means rhar the soturion ofpH 2 b.ir;.;r;;;.;;il']#ti,#ir'o,r,,on, = to
= ot pH = J s7 pt1= 7 r:e warer
havc Do role to Play. Holvever when the acid is diluted so that
ir.s concenlration of I{ro+ ions fatLs b.f*
rO-i,
then it is the [H3o+] ofwater which retains thepH below
7. similarly io czse ot a very dilute solution ofa base
e.& 10-10 M NaOH sorution, it isthe
lolr-] from H20 which herps ro retain thepHof rhe sorution above 7.
(Refer to solved examples of'Iype VIU and X on page
S2O;
3' Double lndicotoE ln the acid.-base litrations, generally
rhe indicators used are phenolphthalein and merhvl
oraDge. As thcy give end point ar differentpH rangii
nence'it is irponun, ,o r.r.riu;;i;;;;ri"*;;r- "*"r'
(i) For tiiratioD ofa base such as Nqco, against a strong acid iHcr), ifphenorphrharein is used as indicaror,
the end point is iDdicated only for half neutralization of NECO3
(ie. upto NaHCO3), NECO3 + H+ .*
NaHco3+Na+ Ifmethylorange isused, the eod point is indicaledwhen
aI the alkaliis comptetety neurralized.
(,j) For titration ofa mixture of Na2CO3 + NaOH vs HCl,
there are rwo wars to c:rrry out ths tirration :
(e) Phenolplrthalein moy be ured
fu sr rc get first end point fo owed hy metlryl (nonge to get .tecond end Doint
Then Acid used upto 1sr eDd poinr C_omplete neutralization
= ofNaOH + j. neu tralization of NarCO,

Acid used from 1st end poiDt to 2nd end point

= ncutralization ofNa2CO3
i
*t be catiied out frrut t$ing Phenolphthalein and then with
rame voh.tme of fre.rh
.",n \\ffrltin" 'antpk
tLting

Acid used wirh phenotphtharein as iodicaror

= comprete neutrarization of NaoH + neutratization of
NazCO3 !
Acid used with methvloranoe as incricator complete
= neutrarization ofNaoH + comprete neutrarization
of Na2CC)3. See solved exanrple 4-0, page ufl9.

;T:t'l'j'r[:iHf ,'"i*f ::il

K2HPOa are ac;dic salLs while
are acidic salts while N%SOa, Na2CO3 etc. are
Dornal
Boslc salts are salts that contair
ro rhe usuar aDions. Basic sar.. may
te mnsiaereaa. ttre ;ffi;#;;:il?|,::
pb(OH)NO3
::*:',:#i#""lrr'",trddition
from pb(OH)2 + HNO3
Irad hydrory nit.atc
or as thc products of the loss ofwater ftom satts
contaiDing hydroxide ion egr
 Net4 Course Chen' i str'!
8162

I NFoRMATToN
ao.lld
-^9SLISNAL U9EFUL
BiOCI from Bi(oH)zCl bY loss of H2O'
ll$m h oxYEhloride
-Ite solubility ofa salt of weak acid i[creases if the solutioo i6 made more acidic
Effect ofPH on solubility,
5.
pH n- a""i""JJl ioi exurnir", ctre sorubility equilibrium of CaF2 Dmy be represoted as
<ir.
CaFz (1) -: t:az+ qaql+zr- 1oq1

I{+ ions wil! combiDe with the F- ioDs As a result' equilibrium will
oo makiogthe solution more acidic,
shifl forward i.e. solubility will increase'

T.Bs;E-r JllT. ffttArnlsl sPEctAL

(J 5 Give reason for the follorritrS:
(i) Zirc is not Precipitrted ss Z1(OE)2 oD ad-
(.1 I What are the conjrrgate bases ofthe follor7ing ?
dirg NHaOH to q zinc salt solution contalnilg
Ctl3oH, HNr, lAl(H1o;ot3
f'
NH.Cl.
Ans. cll3o-' Nt, [A(H2O)5OH]2+ (ii) BaSOa Precipitate is rvashed wlth water con-
methoxidc ion aade ion tailing a small amourlt ofH2SOa in gravirDetric
(.' Why is ammonia termed as n hase thorrgh itdoes
I analysis.
Irot contain OH- ions ? (iii) CO2 is more soluble in aqueous NaOH
Ans. : NH3 $ termed as a base orl the basis of LeNis solutioh than itr water.
coDcept bcausc it can ciooale a lone pair of (iv) A brovn PreciPit8te iD o bottle cotrtaining
electrons- aqueous FeCl, solution aPPcars on standing'
.) 1 Glycine is ar a-amino scial which exists in the Ans. (i) NHaCI suPPresscs the iorization ofNH4OH
+
form of Zwittr iotr as NII3CH2COo- ' Write due to common ion effect. Hence concEfltration
OH- decreases such that the ionic Product
the formule ofits coniugate acid and coltiugate of
base. + I7-o2+llOH-12 does l1ot exceed solubility
Ars. Conjugare acid = nttrCHrCOO- + H* proouiti u.nci znloH)2 is nol precipitalcd
t
= NH:C}IzCOoH (ii) BaSOI {s) $
dissociates as naSoo
+ Aa2+ 1aq; + sol- (aq) Additiotr of H2SOa
Conjugate base = NH3CH2Coo--H+
Eives con]mon sol-
ioos which supPresses the
= NIIzCHzCOo- dissociation ofBaSOl and thus helPs io the com-
(1. .l Write reactio[ for autoProtolysis ol water' plere PreciPitation.
Hov is ionic Product of water related to (iti) Inwater, CO2 dissor'cs to form carboDicacid
ioDization conitaut of water ? Derive thc
(H2Co3)
relotionshiP.
Ans. AutoPrototlsis of HzO takes place a's folloEs :
CO2 G) + H2o (/) <- H2CO3 (4{)

H2O + H2O 5J H3o+ + OH- As the reaction is reversible, the solubility

is low

reacts to form sodiuD

For ionizatioD of H2O, Io aqueous NaOH, CO2
carbonate
HzO <------r H+ + OH-
2 NaOH (aq) + coz G)
*. L,=,
.\ -lH+lloH-l
=- - = s5 5s mol L-' NarCO3 (c4) + H2O (l)
lEol tHrol - is more
As De reaclion is ine!'Ersible, the solubility
or q=Kix55 55
 EQUtLIBHtUM _ (ONtC EQUtLtBRtUM tN SOLUTTONS)
8/63
(ir,) Feclj u[dergoes hydrolysis forming a brown
(0 co3- , r{2co3
precipitate of ferric hydroxide
FeCl3 + 3HzO Fe(OH)l + 3HCl 0i) HPO4- , H3PO4

(., ,' -
- Brown ppt. (sr) NHt , NH4+
Why Po3 ion is rot arnphiprotic ?
(iv) s2-, H2s.
18.I.T Ratchi, t990)
Ans. Ar1 rmphiprotic ion is one which can donaLe r.' I NaCl solution is added to s saturated solution
ofPbCIz, rffhat will happeD to the concertration
protoo as well as acccpr proton. poi- ion can
accept proton(s) but cannot donate any proton. ofPb2t ioas ?
Ans. Pt2+ ion concentration will
Hcnce POi- is Dor amphiprotic. decrease to kecp
!, - In the reaction hetweeh BF3 and CrHrOCrH5
\, constant.
,.
v ',,- Mich is astrongerbase in each olthefollowing
which oDe of ahem will act a6 an ccid ? Justiry
pairs and why ?
your ansver. (I.S.M, Dhanbad 1990)
Ans. The reactioD ber\reen BF3 aDd qH5OqHj is
(i) H2O , Ct -
(ii) cH3coo-, oH-
QHs.. i
qn,io'* f -t (D Hzo
F 0i) oH-.
Refer to Bronsred-Lowry concept for retattve
strengths
QHr\ .._ Bi F th
-o
9H,- -

As Blj
i
accepts a pair ofelectrons, herice BF3 is
s,h
s

the Lewis acid.

(l lt Anhydrous AlCl3 is covaletrL From the data
(.r \ Give reason in ore or two sertences for the giver below, predict whether it would remain
followitrg I covaleht or become ionic in aqueous solutioD
(Ionization enerE/ for AI
Ammonium chloride isocidic in liquid arnmonia = Sl3? ltl mol-t,
solvent (I.T 1991) aHtya*uon for Al3+ = - 4665 kf mq;-r,
Ans, In solutioD of NHaClin liquid NH3 , the followiog AHhydrsuor for Cl- _- _ 3tl kJ lnol-t).
reactioo takes plac
(I.I.T r997)
NHo + + NH, (.S NH. + NHo + AIls. 'Ibtal enerS, released due ro hydration of ions
Thus NHaClgives proton. Henc it is acidic. =-466s-3 x 38I = _ 5808 kJ mol-I. Thrs
enerE/ is greater than the ionisatioo enerty ofAI
(.) 9 Arrange the follotyirg in order ol their ircreas_
iDg bssicity whtch is 5137 U mol-l Hence it would be ionic
in lhe solution.
II2O , OH- , CII3OII, CH3O- e lr Classifly the followirg species os I_ewis acirls
(t.I.T.1992) and Lryis hoses
&". Hro < cH3oH < oH- < cH3o- NlI3, BF3, SrlCta, C5H5N, CO, Ni2+
(1. lr) The followiDg can actas both Brolsted acid and (Bihu 1997)
Bronsted base. lfite
the formula in eoch cese Ans, Lewis acids: BFr, SnCln, Ni2+
(of the product)
Lervis bases ; NlIr, CrIIrN, CO.
(4 HCO3- (ri) H2PO.-
e t6. Give reasons for the tolloMrrg !
(rrr) NH3 (ir) HS- ocetate decreflses
(I.S.M. Dhanbod I99Z) aseswilh ircrease
 Pradeey's
8164
( ) 10. classlfv the fotlowlng os ecid or bsse according
(ir) MsSnGsluE lr not PrcctPllstlil ftoE r solu- cor'
to Bronsterl-l,owry theory aud rsme their
i'r* oitt" sslt by NH.OH ln the Presercc of re.sPorillng conjugate base or acid
Ngicl. (Roor*ee 2000\
(D NHr (ii) cH3coo-
elicr
AD& (i) Thh i8 cn- (ID II,O+ (iv) H-
|iinclPtc. s ex-
bottrc-rmi (vi) sro!-.
othcrmlc i.?. (v) HOO-
(NO3t + aS (We st B engal J'E' E' 2004)
Pb <r ha
Pb (NO3)2 (4q) - Hc't Ars.
'--- Acrording to Bronsted-Lowry theory' an acid
suustandwnich can donate a proton while base
CsAca+ zHao ' is a subshnce which c2D accePt a
proton'
Cs(OHb+2CH3cOoH (t) NH: is a Bronsted base
Ca (OHh + ,{ i- Ca (OH)2 (44) + Hcat' (NH3 + H+ NHf ) Its conjugate acid is
-
(ii) The solubility Product of M8 (oH)2 is higtr' NHn*'
NH.CI supPresscs thc dissociation of
Prescnce of
(iD CH3COO- is a BroDsted base
NHaOH due to common ion cffcct thus Siving
(CH3COO- + H+ CH3COOH) lts con-
[OH-l Tho ionic Product'
low canccntration of -
it iriiott, *ono, o.i"d thc solubility product' iugate acid is CH3CoOH'
(t. li Explsln thY Pg ol0' (rrr) Hro* is a Bronsled acid
rcld ttll b. hl8h* th
HrO + H+;. Its conjugato base is
dor olHcl ? (HrO+
Hzo'
-
Arr
(iv) H- is a BroNted base (H- + H+ H, in
-+ OH-)'
As tho reaction H- + H2O <------s H2
ionlzcd SMng morc H+ lon concsnEEdon
will be Its c.njugate acid is H2'
pU - - iog gl+1 ; rcss tbc [H+1, Srcstcr
(v) HOO- is a Bronsted acid (HOO-
.-
Ol- + H+ in the reaction HOo- + H2O
...
01- + H3o+) Its conjugale acid is 01-
(peroxide ion).

(vi) Srofr- is a Bronsted base (Sro!- + 2 H+

* 2 HSO' in the reaction S2oA- + 2 H2O

!t ill bc morc than at 25"C'
roltc arc NerHPo, and NaES ? z ttsol- + oH-) Its conjugate acid is
e it. whot tyPG of a-
lwct Beisalt'E'E 200i) HSo;.
by reac$on btween ofa r eak
An& Ns2HPOi is obtai[ed ( )tl Prove that the degree of dissociatlon
ocid is give[ bY
NaoH end HsPoJ (a dibssic acid) monoProtic
t
o a=
i | +;J'E;fr
D
n/i\on
I
where Ko isthe <lissoclfltion constant ofthe
we start wilh C mol
acid'
L-l
of the weak
ans. suDDose
OH HA Then
monoProtic acid
Na'
Both disDlaesblc hldrogcnr arc rePlasd by H++A-
io rtya-g"o'is lc-ft' Hcncc Na2HPO3 is a HA <-
""ioiisalt NaHS
is obtain?d by rcplacement.of Initial molar conc.
normol
onc acidlc hydrogen of tI2S ry Na (on reaction
wtn Molar canc. C-Ca Ca Ca
N8OH). Hcncc NaH S i8 an acidic sol'' after dissociation =c(t-a)
 EQUTLTBRTUM
- [ 0ONIC EOUtLtBH|UM tN SOLL'T|ONS) 8/6s

rhus
",=3t:;=
g (0
I'rohleDt
cortsining
2. CaLld.lit the ratlo of pH ofa solution
I mole ofCHTCOONa + I Eole ofHCl per
./!so IH+l = Ca litre to that of o solutiol contoirirg 1 mole of
0i) CH3COONa + I mole of CH3COOH per litre.
Substiruting rhc value of C from eqn. (i), we gct
K rl -ar K.(1 -a) . Case l. Calculation of pH of solution
[H+] = -ij-z---: or a-- containingl mole of CHTCOONL+ I molz oIHCI per litre
CH3COONa + HCI
,.* ,, *, = - ,a, O + rog 1r -
CH3COOH + NaCt
- "y"-
rog,l -
lnitial l mole lmole 0 0
or pH =pL - log(l - a) + loga
moles
1_- Moles00l1
or log :;-: = pKo - pH
after reactiorl
or li'=tctr"-N r.e. [CHTCOOH] - I mol L-r
or ]- I = rrr*"-rH CH:COOH ;S CH3COO- + H+

o, Initial C mol L-l

:= 1* 11YK.-PH
After C - Cd Cc, Ca
or a= I
dissocratton
r +l;r;q=;n
ll
r.) (a) For o,l aqueous solution NHaCI prove that

lll3o+l = r'qT'
.'. [H+l -c@Bu!d "tr
(c.B.s.E. PM.T 2004) '' lH+l =.8
-*==y1.-=K1/2
Ans. Refer to page 8/30.
(.) l-l Arrange the followi[g ( C= lmol t-l;
compounds in the
decreosing order of basicity on the basis of . -toslH+l= -*,o**,
!l roIlsted -Ir!vD' concept
BaO, CO2, SO3, B2O3, Cl2O7. i.e. (r'H)r = - + ros K, .(,)
(r.t.T. 2004) C^se lI. Calculotion of pH of solution coruaining 1
Ars. BaO r H2O <=:=
.
mole of CHTCOONa + I rnle oI CHJCOOH per lirri
Ba(OH)2 (Basic)

;=J UrCO, lWeakly acidic)

CO2 + H2O ApplyiDg Henderson equarion
SO3 + H2O 5) UrSOo lStrongly acidic) (pH)z = pKo* rog
B2O3 + 3 H2O # Z H:SOs (v"ry weakly acidic)
ffi
=pK. = - tog K, 0,)
ctzOz + HzO <r Z UCtOr 1very srrongly acidic)
Hence iD the decreaslng order ofbasicity,we have [[Salt] = lAcid] = I nrolL-rl
From equations (i) all,d (ii), Q,H)t/ Qt}lh = t /2.
BaO > B2O3 > CO2 > SO3 > ChO7.
t , ,t ', ,\ r O TMCHTCOOH (pII 3) ts titrated
R I'IIoIII L,\15 =
rvith 0.05 IU NaOH solu on. Calculate the pH when
Problem L Cslculate the de?ree ofdisso.iotior ot (i) I/4th ofthe acid has becn neuttBllzed.
0 5 M NH' ol25'C in s solutlon ofpH = 12.
(ii) 3/4th ofthe acid has heen neutralized.
NH4OH <----5 NHo+ + OH- Calculation of dittociuiott con tont oI
the
lnitialconc. C mol L-l 00
disso. C-Ca CHJCOOH Qfl.QQQ- 1fl+
After Ca Ca --r
pI{ = As pH = 3, - [H+1 = 1g-: y,
12 means [tl+] = 10-12 or [OH-] = l0-2
ICH3CoO-l = [H+] = lo-3 M
..torr-t ca=10'2
=
"'"=+=# ICH3COO-l[H+] lo-i x l0-3
, -leErZbOHf = ---T:l-- - ru "
=2 x 1o-2 or ZEa. ^'
8/66

(i) Whzn I l4lh of the acid hlu been neu,l't lized .. o'1vx 1 -3.oxro-3
CHTCOOH + NaOH- CH:COONa + H2o 136 V'
or V'- olV -=0245v
lnitial 0 1M
136x3x10-r
conc. . . Volune ofwater evaPorated
0.1x
?l 0lxi =V -V,=V -o.Z45v = 0.755 V
Afrer l/4rh i Le. ofwater should be evaporated off.
75 57o
neutra- 5
A butfer solution with pH 9 is to be
)'rohltn
lization = 0.075 M 0.025 M prepared by mixing NH{Cl ond NHaOH. Colculote the
numher ofmoles ofNHaCl thatshould he addcd to one
.. PH =PK, + ros##+
litreofl 0MNH.OH (Iq=I E x 10-s)
=_togl0-.- + logo:d6
0.025
(M.L.N.R. AIl4l abad I99I )

= 5 - O'4711 =4 5229 solution. For a basic buffer

(ii) Wen il4th of neutalized
the acid ltos been
Po:H = PKb + los -[!3!!L
CHTCOOH + NaOH+ CH:COONa + HzO IBase]
IDrtial 0.1M Further pH + pOH = 14
conc. so thar POH = 14--?H = 14-9 = 5

PKa = Kt
Afrer 3/4th o.t x f Ivf o.r x Irvr -log
= -log (l 8 x rc-\ = 4'744'1
ncutralization
=0.025M =0075M [Base] = [NH.OII] = I nrolL-l
,. pH = - loc lo-5 + Ios &3# '. 5=a7aa7+losEq
=5 +0'4711 =S'1111 or log lsalil = 0 2553 or [salt] = l's mol L-l
Prohlen 1. A saEple of hnrd water contoins 100 t'rohlrm ('. c.alculslte the amounl. of (N IIa)2SOa in
ppm ofCaSOl,What Elinimum fraction ofwnter should
g which must be sdded to 500 mL of0 2MNH3toyield
be evRpomted olfso thstsolid CnS04 begi[s to seParate
a solutior of pH = 9 35' K, for NH3 = 1 ?E x 10-5.
out ? K, for CaSO4 is 9 0 x 10-6.
(M.L.N.R tee2)
MaxiDum solubility of CaSO4 irl water Solution. As it is a basic buffer,
can be calculated from its Krp value as f'ollows :
pol=pK6+ l.c1$#l
S='.q =V9Oxl0-o IN H4+ l
=3ox1o-3molL-1. = - ros KD + loc
I-NHFEI
SuPPose the volume ofwater taken = V litre
,ds pH =9.35, .. pOH = 14 - 9 35 = 4 65
As CaSOl present is 100 ppn rle. 1008per 1068 of Milli moles of NHaOH in solution
water, therefore, CaSO4 present in V litres (V x lo38) = 0.2 x 500 = 100
ofwater suppose milli moles of NHn+ to be added = x

= **
10" "
v x rrPg = 6.; vs = !{}motes . 4 65 = - log(1 78 x 10-5; +.r#i%
(Molar mass of CaSO4 = 13r,8 nrol-l ) = (5 - 0.250a) + logiloo

V'litre
After evaporation, suppose volume o[water left = or tog
1fu = -0
0996 =i oooa - o'r
or logx=2l or x=125 9
ThusV o[waterwillnow contain n:oles '. Milli moles of (NH4)2SO4 to be added
lrtre !f
125 9
of CaS04. = ---'- = u''"'
This should be equal to the ma\inlum solubility ilr
moles L-1.
( 1 nlilliDrolc of (NHa)2SO?=2 millimoles of NHf)
 EQUTLTBBtUM
- I 0ONrC EOUtLtBRtUM tN SOLUTTONS) al67
. . Mass of (NH{)2SO4 ro be added
Kp for AgBr = 1ag+1 1rr-1
= (62.sS t r O -3 moles) (132 t mot-l) =@+ y= 5.0x10-13 (clven) ...(i,
= 8.i094 g. Dividing 01) by (i),
I'n*lin 7 Givcrl that the solubility product of
radium sulphate (Rosoa) is 4 x 10-lI. Cslculate the I=u, or | = O 5x
solubility in (a) pure wster (r) 0.10 M Na2SOa. Putting in (i),
(I.SJU Dhofiul 1992) (r + 0.5.r).r = l0-12 or l.5l = 10-12
ot l-9.667r1q-tz
(a) Suppose the solubility of RaSOI in
or x = 0 82 x 10-6 mol L-l
water = -r mol L-l.Tbeo
.. y- Q.J;=o 4l x10-6mot L-l
Raso4-Ra2++sol-
imolL-1 Solubility of ABSCN = 0 62 x t0-6 mot L-r
r mol L-l r mol L-l
Solubility of AgBr = 0,4t x 10-6molL-l M
\, = 1na2+1 lsol-; l'rohlotr 9. Colculate the hydrolysis constant of
= rxx= ? the salt cont$ining NOr- ions (Given q for
or l= 4Y 16-11 HNO2=45x10-lo (M.L.N.R. 1996)
or x= 6.66 x,l0-6 mol L-r For the salt containing NO; ion G.a salt
(D) NEso4 .._ 2Na+ + sol- ofweak acid)
As INE So4] = 0 10 M, -, K- lo -4
Kr=d=*i.=-u-2zyto-s.
.. ISo;-l from NE so+ = 0.10 M
l'nthlut 1a. Calculate the degree of hydrolysis of
.. 'It tal [SO?-] = x+o rM a 0.01M solution ofKCN,I(, for HCN is 6.2 x 10-10.
= 6.66 x '10-6 + 0.1 = 0.I (Bih4, C.EE. l99t)
Hence \p = [Ra2+] [sO?-] SolutioD. l,
K_
- R;7
4 x 10-11= [Ra2+] [0.1]
ot [Ra2+] = 4x t6-lomolL-l
. . Sulubility of RaSOI in 0.1 M Na2SOl
6.2x10-t0xl0-2

- 4 x lo-lo mol L-l = 0.04 = 4qo,

l'r!,hlq,t 8, Cslculate tbe simultoncous solubility t'r oblon t t. Ka ofAI (OH)3 st 25"C is 5 x 10-33.
of AgSCN and AgBri Ka for AgSCN and AgBr are Calculate tbe solubility of AI (OH)3 irl moles/litre at
1 0 x 10-12 and 5.0 x l0-13 respectivcly. 2YC. (Bihor C.8.8.2000)
(M.LN.R. Allahabad I D 5 ) Suppose the solubitiry of At (OH)3
. Suppose the simultaneous solubilities of I
= s moles litre-
A8SCN and AgBr arer andy moles L-1. Then as
+ao
AgSCN+Ag++SCN- Al (OH)r ...-' A.lJ+ + 3 OH-
and AgBr -- Ag+ + Br- r 3r
'. Total [A8+l - r +y moles L-1, K,p-s x(3t)3 =21ra =5 x lO-33
[SCN-] =a n1s;$ 1-t, or sa=fixrc-zt
[Br-] =ymotes L-l
for Ag sCN = [Ag+]
or 4logr = log 5 - log 27 - 33
\p [scN-]
= @+ y)x = "t.o x fi-12 (Given) ...(,
= 0.6990 - 1.43t4 - 33 -33.ii24
8/68 Pradeep's
or logr=-8.4331 -9 5669 IHCO3-I Kr
or r = .3 6E9 x 10-e M. Irreq-f =tH;i
I'n,LtLn t2. pH = 7 40, Kr of H2CO3
pH =7 40meaDs - log[H+] =?.1
= {.5 x l0-7. what Mll be the rarlo of tHco3l to
or rog [H+] = - 7.1 -9.6
lH2cosl ? G.B.S.E. EM.T 2004) , to-s
or , [H+] =:sst
H2Co3 <------r H+ + HCo3-
lHco;l=;;5lx16=.=tt
4.5 x t0-7
,, [H+] [HCO3-] Ifrp;{f ''
^t =lEeqf-

l. l.T, {^nArAtsJ strEc IAL

I'tu'hlol 1
What rolume of 0'10 M sodium for'
of0 05M formic
mate solution should be oddcd to 50 Itrl
acid to produce a huller solution of PH 4 0 ? PIq for
tion of H2O into H+ and OH- ions
formic acid is 3 t0' (Roorkee )990)
Solutio_n. The reaciion is ' solutiotr The pH i?lue ofan acid buffer is given
HrO iJ H+ + OH- by

pl=pY\+.c a=3 8+
At?'C, pH = 7 means [H+] = 10-7 M
.. *", = 10-to
ffi" loc
ffiS
At 35'C,pH = 6 n:eans [H+1 = 10-5 M
or ros
ffi=o.z
or
ffi: 1 584e

= 10-12
Krr, o, ffi$ffiffi=r'ssre
As cquilibrium constanls for the dissociation of
HzO are in thc same ratio as ionic Products ofwater, wc ( . Volume is same for both)

can aPPly the relation No. of moles of acid P1s5sn1 = ffixso

. R",,- aH (1 - 1\ = 25x10-3
q:
ros
,:365E rrJ
[r, .. No. ofmoles ofsalt = 1 5849 x2 5 x 10-3
- lo-!2 aH
"'oc ro=1r - rT6t;Elt4iFrr;rr = 3.962 x to-3
/ I _ __.!_) Hence volume of0 l M sodium fornlate required
(2e8 K 308 K/
or AtI - 52t9t J mol-l = 52 t9E u mol-!. = f;f ,:.rez , to-3
I'ntblcn 2. Colcul.tc tbo sPPE)dmste PII of I
0.10o M squeous E2S colutlon. Kr rrl K2 lor II2S art -39 62ml

1.fl) x 10-? ond 1'30 x l0-rt rtspocttvely st 2yc. /'ri,li|ra J Colculate the PH at equivolence Point
when a solution of 0 10 M acetic acid is titrated with o
(Roorkee l9EQ
solution of 0.10 M NnOH solutlo!. Kr for ocetic acid
I! << \. Hence H+ ions are maiDly
-qg!CE-o!. = l.9xlo ' (Roorkee 1990)
from lst dissociation H2S <-----\ . At the equivale[t point, CH3COONa is
-- tH+l IHS-I formed and its conceotration = !_l M = 0.05 M.
' IHusl
It is a salt ofweakacidand stroDg base. The formula
or rr+1 = {, grpl for finding the pH of such a salt is
... [H*] = 40-\ 10" = 10-a pH --+ IlosKq,+ loglq-logcl
Hence pII = 4
EOUtLTBBTUM
- 0ONrC EQUtLtBRtUM tN SOLUTTONS) 8/69

- PH= l'roblttn t A 40 mL solution ofa weak bose BOH

is titroted with 0.1 N HCI sohrtion, The pH of the
-t ['og to-" + log (1.9 x 10-5) - log (5 x 10-2)] solutioI| is forlnd tobe 10.04and 9.14 afterthe additior
of 5 0 mL and 20 0 rnl- of ocid respectively. Find out
=- ltro + (-5 +0.2?88) - (-z +o.6seo)l K, for the rdeak hase. (I.I.T t991)
Suppose inirialty 40 mL of weak base
= loo * t - o.ziBB - z + o.eteol -11:9 = BOH containsr milli ntoles of the base.
".r,
l,roblun 5. Calclum loctst ls 8 salt of s r.ak Cnse I. After adding 5.0 mL of 0. I N HCt,
organlc ocld sDd represeDt d ss Co (Ilc)2. A saturoted pH = 10.04
solution ol Ca(Lsc)2 cortalns 0.13 molc of ihis salt ln .. pOH = 14 - 10.04 = 3.96
0 . 50 lltr solutiotr. The pOH of this solutlon ls 5 60. .
5 mL of 0.1 N HCI = S x o.l milli moles = 0.5
AsguEhrg complet dlasoclstiotr ol thc srlt, calculate milli mole
Kr of lactic acid. (funrkee 1991) BoH + HCt .._ BCt + H2o
Solutio_Irj. In solution, Ca (Lac)2 is hydrolysed as
Inirialmilli r 0.5
follows: n]oles
C-a (Lac)z +2H2O <-------\ Ca (OH)2 -
rT.t"T. Millimolcs .t - 0.5 0 0.5 0.5
(weak) after reactioD
C,az+ + 2Lac- + 2HzO <-r pou =pKo + logffi
C-az+ + zOIj- + Zl{l-ac o.(
ot 2Lac- + 2H2O q:) 2OH- + 2HLac - 3.96 = - to8 KD + to8;+ ...(i)
Case Il. Afler adding 20.0 mL of 0.1N HCt,
or Lac- + H2O OH- + HLac pH = 9.14
Hyd10l)6is constant, =- ..pOH=10-9.14=486
[oH-l lHlacl 20 mL of 0.1 N HCI 20 x
= 0 1 mitli moles =2
'. =-
'c' "'(o nrilli moles

But -Fi'-molL-l
[Ca (Lac)21 = 0 26 so rhat
Initiaf milli
BOH + HCI
x 2
_ BCt + Hzo
0 0
[Lac-l = 6 52 -o11-t moles
and pOH = 5.60 so that Millimoles x-2 0 2 ,,

afier reaction
lo8 [OH-] = 5 60
- a
or .. 4.86 = - tog Kb + log (...x)
[OH-] = sD11qr 1-, ,, r--:--
Subtracting eqn. (i) from cqn. (ii), we get
= 2 51 x l0 -6 M
4 86-3.%=toEi4- rog,#T
Iq= or 0.9=log2-togtr-2)
= 1 21 x l0 " - log 0.5 + Iog (r - 0 ,S)

FUrther HLac <J H+ + Lac- orlogl:$=6 9-log2+ log0 5

+l =0 9-0.3010-0 3010
... K - lH ll-ac-l (r0
' [HLac] -0 298

Also Kw = tH+l IOH-I ...(iit) or r;-# = 1.986

From (,), (,,) and (,1,), or x-0.5 = -1.986t -3.972
. K* 10-11
or 0.986r= 3.472 or x-3.52
^" - x; - 121 xlo=lr Substituting in eqn. (ii), we ger
,,
10-' 4.86=_logK6+loET:S;_
= 8.26 x
817O
Pratlec y's Neii Coursi Chemistrg fi[fr
or ll, Calculation of the alnottnl of Ca (OH)z in
logKr= -4 86+0 301 -0-1818 Stcp
toh.lion afrq mli\g. L\ equal volumes ot (h (OH)z
=-4140E=5 2592
solution and (l 4M NaOH solution bave been nrixed
j Ka=I ElTx10-5'
Cooc. of NaOH iD the mixture - )=o zU
I'rohhtn 7. A certaiD weak acld has
K'c = f 0 x I0-'. Calculate the equilibrlum conststrt loH-l = [NaoH] = 02M
for its renctioD with o strcng base. (I.I.T I99I)
Ile for Ca (OH)2 = [Ca'?+) [oH-]2
HA+BoH+BA+H2o
weak strong ''' IC"2+l -''1;:Ui!
ot HA+ B++OH-+ B++A-+H2O = 1 105 x to-3 molL-l
ot HA + OH- <- A- + H2O Tbtalvolume oflhe solulion after mixing
'1000
= 500 + 500 = ml
K (, '. Amount of Ca (OH)2 in the mixture solulion

Further for the weak acid, = 1.105 x 10-3 x ?4g = 0 0818t = 81 8m9
HA # H++e- .. Amouoi of Ca (OH)2 precipitaled

,.. = Eafir ...(,,) = 823.9

l'rt)blt
- 81 8 =742'1rng
t ') Calctulate the pH at which Mg(OH)2
nrso Kw = IH+l JOH-I ...(,ri) begins to prccipitEte from a solutiotr containing 0 10 M

From cqns. (i), (ii) and (rri), Mg2r ions. K, of Mg(OH)2 = 1 x 10-rr.
solution. Minimum [OH-l after which
x=ft-ffi=ro" Mg (OHh begiDs to prccipitate caD be calculated from
(Ka) of
Problen E. The solublllty proiluct lMg2+l [oH-]2 = K,p orMg (oH)2
cs(oEL st z?C is 4'4Zx 10-5. A 500 Dl of I
(0.10) toH -12 = 1o-ll
sEturattd solutlon ol Co (OIl)2 ls mlrcd wtth 'qusl
yolume ol 0 4 M NaOH. IIov much Ca(oH)z lD mll' or [OH-]2 = 10-lo or [OH-] = 1g-s
ligr8ms is precipitated ? (l.I.T 1992)
or [H+] = 1o-e
Step l. oI omoun of
Cdlculslon
or
Ca(oH)z in 50O ml of soasoled lokllio\ SrPpcF'e PH=9
i'r"t,it It 1o The pH ofblood streem is maintained
solubility of Ca (OHh= x mol L-r by a proper balance ofHrCO, and NalICO3 corcehtrn-

Ca (OHt .....- Ca2+ + 2OH- tions. What volume of5M NaHCo, solution should be
mixed with a 10 ml sample of l)lood which is 2M in
.r Ksp -- tca2+l toH-F IITCO3 in order to maintain a PH of 7 4 ? q for
= xx(2t)2= 4l HrCOrinbloodisT.t x 10-7. (I.I.T l99i)
. 41 = 4 42x 10-s
or .t' = l.lo5 x lo-5 -sdc@. pH =pK" + rou ffi
3 lo8! = log (1 105 x 1o-5) - [NaHCOll
7'4- - log (7 8 x l0-') + log
ffi
= 0.M34 - 5 =-4.9566

01
logx =- = 2 347A
1'6522
x=2227 x Lo-znolL-r
,"rffffi =7 4+ (-7+o'8Y21)
. . Amount of Ca (OH)2 Present in 500 ml = 1 2921
x lo-z x'l49
=2
- --
Z--
221
or sffi = Antilons 1.2s21= ls ss

= 82'39 x10-2g=323 9r,

 EQUtLtBHtUM (lONtC EOUtLtBRtUM tN SOLUTTONS) glt
- 1

H2CO3 pre.senr in 10 ml ot blood (2M H2CO3)

HNIC \-:: H+ + NiC-
= mi6- x
2
l0 = 0 02 mole Inilialanlounl 0 1 mole
Amount 0.1-0la O.1a 0.1a
.. NaHCO3 that should be present eqm
at = 0.1 (1 - a)
=19 59 x0.02 = 0 3918 mole Molar conc. =0.1 (1 -a)tZ O.la/2 0.7a/2
Volume of 5 M NaHCOI required at eqm.
ltm r o.:lts 7t.i6 mt K +]
= = .-a: IH INiC_]
[HNicl
l'tu)t,tt! lj An aqueous solution of a metal
bromide MBr2 (0 .05 M) is saturated with H2S. lvhat is or r.4 x ro-5 = @
i?i, (?):T;i2)
the minimum pII at phich MS will be prccipihted ? Ifa<<1,then
(Kp for MS = 6.0 x l0-2r, concentratior ofsetlrr.rted
r ,r x 1o-5 = ,## = o.o5a2
H2S =0l M, Kl =10-7 and Kr=1.3x10-13 for H2S)
(I.I.T r99i) or a2 = 2.8 x 10-a
solr'!!!E. [M2+l = [MBr2] = 0 05 M
or a- 5.29xto-2= 0.053
% dissociatioD = 0.053 x 1oo = s.3Vo
For the precipitation of MS, minimum I52-]can be frubb t l3.ThepEof 0.05 M aqueoG solution of
calculated from
diethylamiue is I2.0. Calculatc its KD.
ls2-l [M2+] = Iqe r:e. I0 051 [s2-] = 6.0 x r0-2r (Roorkec 1993)
or[S2-] = 1 2 x 10-le (c2H5)2 NH + HzO +
S2- ioos are obtained from the foltowing dissociations (c2 H5)2 NH2+ + OH-
K.
H,S As plj = 12,... [H+] = t0-t2
------.: H+ + HS
or
K2
[OH- | = l0-2, 16r11r;rY11
HS- <- H+ + s2- = 0.05 - 0.01 = 0.04

,, l(c2Hsh NH2+lloH-l ro-z x lo-2

rsr = tH+llHs-l ,, = lrr+lls2-l \- = -_lGH;tNEr-
ffi;-,Kl lHs l -T:r4-
=25x10-3
'' Kr 19 l'rohlen l1- O.15 rnole of plTidinium chloride has
been fldded into 500 cm3 of 0.2 M pl,ridine solutlon.
IH+12 Jl:2-x 10-lel Colculate pH and hydroxyl ioll concentmtion in the
10-7 x 1.3 x l0-13 = (0 1) resulting solution dssuming no chonge ln yolume (I(n
or for pyridine = 1.5 x l0-1e M) (Roorkee 1995)
l.3x10-20x10-l 1.083 x For basic buffer,
lH*12= = 10-2
7.2 x lO-19
poH=pKb+ bsffi
or [H+l = l o41 x1o-1 = 0.1041 M Here base is pyridine and salt is pyridinium
.. pH = (o.1o4l ) = 0.9t26. chloride.
-log
,'. ,, , r/ 11. Nicotinic acid (K. 1.4 x l0-5) Conc. ofpyridine = 0.2 M
= is
C-ooc. of pFidinium chloride
represerted by the forirlulo HNiC. Cnlculate its per-
centage dissociation in o solution which contains 0.10 = 0 15 mol iD 500 cm3 = o.30 M
mole of nicotinic acid per 2.0 litre ofsollltion.
PIq =-log(1 5 x ro-e)
(Roorkce l99j)
Solution. Suppose degree of dissociatioD of = - [0.1761 -91= B.t23s
nic!tinic acid = a : pOH = 8.E23e + log#;3
e
8n2 Pradeep's

= 8 8239 + logl5 or pH = - ttros( + losKs - losKbl

= 8 8239+01761 = 9'0
=iPq*PK\-Pr\l
-log[oH-] =9
LC. 0

or logloH-l - -e = |t:s* 14-481 =6s

IoH-l = 10-e /l ,/,irr, /7. What is thepH ofa 0 50 M aqueous

froD Hzo = t0-7 M ofCN- is 4 70. U.LT. 1996)

NaCN solution ? pK,
[oH-]
solution. NacN + H,O ---------r, NaOH + HCN
''. Total [OH-] = 1o-7 + 10-e M oH- + HCN
or CN- + Hzo
- ro-e (102 + l) 4
=l0lxt0-7M K. = loH-l IHCNI - [oH-12
K, " [cN-] lcN-l
.... t.,
IH+lt -=
1oH-l= ---ln-'o
r.or;ali=7 ''. pKD = - lo8Kb = -z tog [oH-] + loglcN-l
=990x1o-EM or 4 70 = - 2 log loH-l + Iog (0 5)

.. pH = log [H+] = (e 90 x lo-8) t\ lcN-l = [NacN]l

- -log7 0044 or 2loglOH-l =-500
=- I0 9956-81 =
l'rohltn l5 Ar aqueous solution contglns 107o or lo8[OH-]= -2 5
nmmortie by mass and hos a density of 0 99g cm-3'
- log [oH-] - 2 5
Calculnte hydroryl and hydrogen ion concentration in poa- 2.5
thls solution.I(, for NH.+ = 5 g x 10-10 M
(Roorkee 19951
pH=14-?5-tt s
i'rdtttm l iiThe lonization constant of NHf ln
Solutlo[ 107, ammonia by mass means 10 I
NFI, aiE t in 10og of the solution rynter is 5 6 x 10-10 at 25"C. The rnte constant for
.. MolaritY of the solution renction of NHa+ and OH- to form NH3 artd H2O nt

= 1+ , *rr-fOTU
, 1000 = 5 82 M 25"C is3.4 x l0l0litre mol-l sec-1. Calculate the rate
constant for proton transfer from woter to NH3.
NH, + Hro- NH4oH + NHi + oH- (I.I.T t9e6)

Iritial C mol L-l s-otution. NHo+ + H2o + NHaoH + H+,

conc,
Aftr d issociation C-Ca Ca Ca &=56xto-to
kr
-c(1 -d) NHj + H2O OH-,
.. c.q-i <+ NHn+ +
IoH-l = c" = ='tTF k
_,r<K;IE;c ka=34xl0lo
lo '- *5.82 =l'o79xlo-2M Aim. Ib lind k,
'=
5 0 x 10-ru We know that for a conjugate acid-base pair
K,/ 10-l' x K6*, = K* ie. K., Kr = K.
Ko",1
loH-l 1(I79x l0-'
K' 10-11
26s x 1o-tl M ''' '.
-0,9268x1o-12M-9 ^r=4-=5 6 rroiu
rh|,n l1.Cr,l(]ulrte the pE olon oquaous solu'
I' k,
tion of 1.0 M 8mBotrlum formotc assumlng comPlcie
dissoclatton (PK., of foErtc gqld = 3't ond p\ of
But Y.b=
i
ammonia = 4 E) (I.LT 1995)
he salt of weak acid and wEk base,
tr=ro,t6=;ffix3 4x 1010

,= =0607x106=60?x105
 EQUTLtBRTUM (ONIC EOUtLtBRtUM tN SOLUTTONS)
- 8173
lrohlut l9 Calculste the pcrcertage of +
hydrolysis ir 0 003 M aqueous solutiol of NaOCN ,, [c6HrNH3]JOH-l
(K" for HOCN = 3.33 x r0-4 M) (Roorkee 1996)
Nr'=-TQENET- ".(4
Solution.NaOCN + H,O =---r NaOH + IIOCN Further, we arc given
+
or OCN- + HzO + OU- + HOCN c6ll5NH3 cofIrNH, + H+
Initialconc. c -) +l
Conc. at eqm. c ('l-1,) ch ch
,. lc6H5NHrl lH
^.=_-----_i-...(Il)
=C lc6H5NH3I
where h is the degree ofhydrolysis Arso IH+l IOH-I = Kr? ...(r,,
.. Hydrollsis constant, Combining eqns. (i), 0?) and ( )
K, = ch ;ch =r1,2 or h={yj, ,, K* lo-t1 to-8
^,=4=r;;ro-=z.a-
gr1 K. = IOH-l IHOCNI
- IocN-l
SubstitutiDg rhe values in eqn. (i), we get,
10-8 l0-8 xr
K,=rH+l5oeR'r-l tHocN + H++ocN-l i=T =tr which gives r=to-2M
Problen 2l.l sa6ple of hard water contelns 96
K. = tH+l IoH-l ppm ofSO!- ond tt3 ppm of IICOJ- with Ca2+ as the
Combining these equations, onlycntion. How mary moles ofCaO will he required to
,. K,, 10-14 remove HCOt ltom 1000 l(8 otthts wsrer ? If l0O0 kg
^r=x;=a:5:,ro= of this water is trested wlth the amount of CaO calcu.
laied above, whet will be the concentrotior (in ppm) of
lo-10 I
{l:r'= 16-o
T5r'r;lo-3 = residuat Co2+ ions ? (Assume CACO3 to be cornpletely

..%age hydrollBis = l0-a x lfi) - 0.01

insoluhle in water), Ifthe Co2+ ions in one litre ofthe
completely exchangcd with hydrogen
Pntbkn )0. An aqueous solufion of anlllne ol its pll ? (Onc lpm rhcans ore part of
corcentration 0 24 M is prepared. Whst conccntrstior
of sodlum hydmxlde is Deeded ln thls solution so that
in one miuior ,^*
snilitrlum ion concertratlon remains at I x l0-t M ? O1!.r\)i.1,
(K., for C6H5NH3 + =2.4xrc-5[)
SOn2- present in 10Oo kg ofwarer
(Rbo*ce tgg6)
Sohrtion. In aqueous solution, aoiline is = 3$ x t00okg = 96 g = I
hydroD^ied as
#= mote.

HCO3- present in l0O0 kg ofwarer

C6H5NH2 + Hzo + cuHrilH, + oH-
=l{-" tmo rg = l83g=ff=3ms1es
When NaOH is added, hydroDsis wi be sup-
pressed so thai in the finalsolutoiD, Ca2+ presenr atongwirh SO?- ions
= 1 mole
+
lo-t M (Given) Ca2+ present atongwirb HCO; as Ca 1HCO3)z
{c6H5NH3l =
3
If co[c. of NaOH added is .r rnol L-t , then ar = t mole
equilibrium
.. Tbtal Ca2+ present in l00O kg ofwater
lc6HjNII2l = 0.24 - 1o-8 = o.z4
=l+i=25moles
+
[C6H5NH3] = l0-8 M (ciren) CaO added will react wrrh Ca (HCO3)2 as follows :

Ca(HCO3)2 + CaO- 2 CaCO3 l +H2O

[OH-l - 1O-t+r= rM
.. Hydrolysis consknr, But Ca (HCO3b prcs e* = mole (calculared above)
|
an4 l'ratlcty's Neur Course Chemistig |!ffi)
t'ntl,hn )t. CtllNhte the rmolnt of NH3 and
;. CaO rcquired =imole = l 5 moles NII4CI required to PreParc a bulTer solution ofPII9 0
Alter treatment with CaO ie. remc'val of when totall concentr$tion of bttfTerlng reagenls is 0 6
Ca (HCOr2, amouni of Ca2+ Ieft (due to caSoa only) mol L-1. pK5 for NHJ = 4 7, log 2 = 0 30.
in 1000 kg ofuater = 1 6e1e = 40 ! (Roorkee 1997)
.. Concertration of residual Ca2+ (in PPm) Solrrtiop. pH = 9 0. l{eoce pOH = 14 -9 = S

= /() ppm poH = pKb+ q##

Now lffn kg ofwater conuitl Ca2+ = 1 molc
lsaltl lsaltl
sel or logiBaaET-
.'. lfl)O g of water tt/ilt contaio Ca2+ = 10-3 mole s = 4.? + lociE 0.3
No. ofmolesofH+ sxchanged - 2 x 10-3 mole ISaltl
:. pH= -lo8@x 1O-3)-27'
o' iB#T = Anrilogo 3=2
t'roblzn 2). A sample of AgCt wss trc8ted wlth i.e. lsalt] =2xlBase]
5.lXl ml of 1'5 M Na2 COt solution to SiYc A*2CO3' The Also we are Siven :

remoining solutlon cotrtstucd 0 0026 g ot Cl- per lltrc' lsaltl + [Base] =0 6molL-l
CatculatJ the solobtltty prodoct ol fuCl (Kr lor 0 2 mol L-l
This on solviDg gives [Basel =
A82CO3=t z x ro-2; (I.I.T teen 4motl-r
and [Sflltl = 0
1 .5 M Na2co3 gives ICoS-l = l 5 M t'n,l'ltn )5. K, for ascorbic acid (HAsc) is
Ile for As2co3 = lAs+F tco3-l

.1 [Ag+] =
K* for

tco3-1
A&cOr _ ,/+
=2'34xlo-6M
5 x 10-5. Colcrlate th. hydroger iorl concentration
snd percentage ofhydrolysis in on aqueous solution in
which the conc.[tmtion ofAsc- ions is 0 02 M'

Solution. As ascorbic acid is a

(kn*ee
weak acid, aqueous
1997)

solutioD of ,{.sc- meaos the solution ofa salt ofwsakacid

Ktp for AgCl = tAg+l tq-l with strong base. For such a salt, degre of hydrolysis is
giveo by
=(2.34x10-5(#)
Pa,httu 21.
=171 xt0-lo
At acidtlIp lrdl@tor, HIn dilfers lu
,=\T-Vr;im=
= r0-4 = l0-a x tOO% = O.Olqo
colour ftom lta coqjuSstc bose (In-). Tte humon eye is
seEttive to c{lour differ.nces only wher the ratlo Asc- +H2O + HAsc + OH-
lltr-I/tgbl ls 8Ert r thatr 10 or smollcr thsr 0 1'
i{hai shoul! bc ihe mhltEum chanSc ltr the pH of the L-l
c mol

solutlon to obs.ra. a cuPletr colour chatrge' c-ch ch ch

(K.=t o x 16-5; r (l.I.T teeT) 02 x1o-1 = 2 x to-6 mol L-1

[OH-l =slt =O
<- H+ + In-,
K ,"-t4
Solution.- H In ..IH+l = ---+ = -r:- ?
lH+luD-l
&=--Ttrni-- :5 x l0-9 mol L-r
IHIDI I'rtl'ltt 26. The solubility product ol SrF, in
or tll+l = K,
waterlst x I0-10. calculate its sotubllity in 0'1M NaF
ttnT (Roorkee 19971
nqueous solution.
when [In-]{HInl = 10,
Solution. As NaF is a strong electrolyte, it ionizes
lH+l=10-r,fr=ro-u, PH=6 completely. Hence[F-] = 0 1 M
\o for srF, = ts*+l tF-12
when Un-l4HInl =01,
IH+l = tO-s 1 lQ = lQ-4, pH = 4 ... Bx 1o-lo=[srz+] (0.1)2
.:. Minimum chaoge in PH = 2
 EOUTLTBRtUM 0ON|C EOUTUBRTUM tN SOLUTTONS)
- an5
or [Sr2+1 =3x t0-8molL-1 = (1 .2 x 10-17) x (.1 x l0!e;
. Solubiliry of SrFz in 0.1 M NaFsol.
= 8.52 x 1O2
=axl0-tmolL-r '. --l-
-2
i t t,/,i, ,tj :- = 8.52 x 102
Z0{} ml of nn oqu (t - 2x)
hixed lYith 300 ml or
=12 0)? -J77=Zn.Z
sohrtion. pH = 2 meaos [H+] = l0-2 M
or x=29.2-58.4t
ot r=O.49mole
PH=12meansJH+l = l0-12
l't,,hlult )9.O.16 got NrHa ore dissolved inwater
or [oll-] = l0-2 M
alld the total volumc Esde upto gxt ml. Colculate ahe
Ttrus, 2fi) ml of 10-2 M HCt are mi\ed wirh 300 perccntage of N2lfa thst has reocted ryith water in this
nrl of l0-2 M NaOH. After neutralisation NaOH left
= solutior. The K, for NzHa ls 4.0 x l0-5 M.
100 ml of '10-2 M
Tbtalvolume after mixing = 566 r1 (Roorkee l99E)
. In the linalsolution, after mixing N2H4 + H2O i:r N2Hj+ + OH-
lo;'= 2 x lo-3M
IoH-l -
Conc. of N2Ha = O. t6 g iD 500 ml.

oriz
rn-14 = 0.32 s L-l = mor l-r
or 'lH+l= rv -=5xt0-12
2xl0-' =0 01 M = l0-2M
'. PH=-log[H+l =-tog(S,. ro-12) I(, for N2H{ = 4.0 x 10-6 M (civco)
= l2 - 0.69 = 1r.39
l'n $lr ) D I \ Determi\e the rumber of Eoles ofAgl 10-1.
which may lre dissolved in 1.0 litre of 1.0 M CN- ^-./*- 4xl0-5xlO-2
solution. Kry for AgI olld K. tor Ag(CN)2- are = | " 16-: = n.. x l0-3 = 0.1sq,
l 2 x lO-1 M2 7.l x l0I911-2respectivety. The solubility of pb(OII), in water is
^nd
(Roorhee I 99E) 6 7 x 10-5 ltl. Calculate the solubility ofpb(OH)2 in a
Solutior, Suppose number or molcs ofAgl which bulfer solution ofpH
= t. (.1.I t9ee)
Dray be dissolved in I .0 litre of I .0 M CN-solurion = r. sotutior. pb(OH)2
Then i-l pbz+ + 2 OH-

AgI (r) + 2 cN -(44) <-[A8(CN)2]- + I- - \e = [Pb2+] [oH-]2

Intial x =s x (2 s)2 -4F -a x (6.7 x to-6;3
moles =120x10-15
Moles 0 l-zx x x
In a solution with pH
and [oH]- = l0-6
= S, [H+] - l0-8
after reaction
. 1.2 x 10-15 = [Pbz+] x (10-6)2
,, [As(cN)rl- [r-l .] 15=l.2xlo-JM
^'q=--tcr.r-F -= iZf (') or lpu2+1- l2x1,0.
(10-6)2
Further, AgI (r) i- AB+(a9)+r-(,rq) !. t.:, ,/Tlrobullers(X)andfy)otpH4.0and
6.0- respectively areprcparcd from acid
_
I(,p - tAg+l II-l = 1.2 x lo-t7(civen) ...(ii) HAand the salt
NaA. Both the burfers are 0.S0 M ln tIA. What would
Ag+ 1aq1 + 2 cN - (aq) [Ag (CN)21- be the pH of the solufion obtained by mixing equal
== volumes ofthe two bullers? (KHA = 1.0 x lo-J)
IAEI CNLI-
It =,^ffi = 7.1 x lore(cryen) ...(,iD (Roorkee 1999)
Solutiorl For bufer X,
From eqn. (0, (n) and (rt)
L' = \r'4 pH =p K" + tog
ffiie. 4 = 5 + ros I3:$

,
8n6 t)rt(.7p.e p's Netl Coutse Chem istrLfiffi
NeglectiDg this cotrc. in eqn. (i), we 8et
rog+ll- - r
lAg(NH3)z+l - o'1.

SS- 1s-' Putting tbcse values in eqn. (ii), we 8et

lsalt] = 0.05 M
For bufier'{ ---9j...._:=r.o*to'
l0-e x [NH3]!

pH=px"+logffi or tNH3l2 = ----'=-ia-----:-=

i.e. 6=s+logffi =re_

I
l!=
"
or togff+= I or rNH,l = ----l---"- = 2 5M
' '' 4x10-'
or $$= ro Also O 2 M NH3 is needd to dissolve 0'01 M

or lsalt]=5M Ag+ ions. Thus

when equalvolumes ofboth the buffers are mixed, [NH3] = 2 5 +O'2=2 7M'
.l'r.)rlr, -J.i. The averoge concentratlon olSO2 ln
lAcidl = 0 '5'
the atmosphere over o city on a certah day ls 10 Pprn
1sattl =IJ-9-91 =z sozs when the avernge temPeroture ls 29t K. Giver that the
solubtlity of SO, In nater at 29t K is 1'3553 moles
pH =p Ka + rosffi,I+ litre-l and thcPKd ofH2SOS ls 1 92' estimste thePH

2.5025
ofrr|n on that dry. GI'I2000\
=s+rog_otj_ Solution. SO2 + H2O -- HrSO3

=5+1o85'05=57 litre-l
[HrSO3l = lSO2l = 1 J653 moles
I)1,t,ic .l2 Determine the concentrstion of NH,
sohtion whose one litr6 gsn dlssqlve 0 10 mole AgCl ' H2so3 i+ 2H+ + Sol-
Klp of Agcl and K, of fu(NH3)f ore I 0 x 10-10 M2 Supp6e at equilibrium, [H+] =r mol L-l
anrl 1 6 x 107 M-2 resPectiYely. (Rn*ee 1999)
Then lH.so,l = h:osr -4'1,
Solution. AgCl- Ag+ + Cl- \.i
' 0 1 moleAgclondissolutionwill giveo 1 mole
tsoS-l = ; morL-1
Ag+ aDd 0 1 mole Cl- ioDs. A8+ ions willcombioewith
NH3 as follows : ,. tH+F tso3-
n,=1ffi{f- |

Ag+ + 2NH, + Ag (NHa)z*

x2 xx/2 - .^-r'92
Henc.e [Ag+] + [Ag(NH3)z+] =o l mole ...(i) = (1T65T=777i tt'
givcn
Also for the above formation reaction, we are ( " PK, = 1 92meaDs - logKo = 1 92

r.e
.
, 10,= ttu(NH3h*l (rr) or log K.d = - 1'g2or'Ka= 10-1
e2)
b= lAf I1NHF
Neglectingrz in comparison to 1 3653, we get
F\rrther [A8+] [cl-l = K"p = 1o-lo y' ,,.,-r.ez
-
2xT:36tJ-'"
or [Ag+] (0 1) = 1o-ro
or
or f =z noe ,1 16-1 92
[A8+l = 1O-e'
 EQUTLTBBtUM (tONtC EOUILtBBtUM tN SOLUTTONS)
- 8n7
or 3 logr = toE2.73O6 - 1.92 A8NO3 left = 0.01---0.005
= 0.005 mot. Whotc
= 0.4348 - 1..92 - - t.4t5Z of it will react completely with N%CrO1 (as it is presenl
or -logr=0.485 in larger amounr).Na2CrO4 reacted
= 0.0052 = 0 OOX
i.e. pH = 0.4t5. mol. Hence NECTO4 teft = 0.1---0.0025 0.0975 mot
=
lrntbk'n .1J. What lIJ,rO +l hust be maintained in
AgzCrOa (ppr.) formed = 0.0025 mot.

n satumted H2S solution to precipltate pb2+ lrut not Total [CrO:-] = 0.0975 mot + CrOl- obrained
Zn2+ from a solution in which each ion is preselrt at a from Ag2CrOa (negtigibte)
concentration of0.01 M ?
IK,? H2S = I .I x 10-22 anrt K, ZnS = I .0 x l0-2rl - 0.0975 mot = 9.7S x l0-2 M
(Rarkte 2000) AgzCrO4 + CrO;-
-2Ag+
Kry for ZnS = to-2r K,p (A82CrO1) = [A8+ j2 ICrOl-]
and [Zn2+1= o.U M - l0-2 M I 1g-2; = 16-8
IAB+]2x(9.75
But KrP (ZnS) = [zn2+] [s-2] or [Ag+]2 = 0.1 x 10-6
i.e. 10_2r = [10_2] [S2_] or [ng+] = 0.32 x 10-3 M
or [S2-] - lo-le M = 3.2 x lo-4 M
Thus to preveni precipitation of Znz+ ions, Total precipitate formed = 0.005 + 0.0025
lS2-]
must be less than l0-19 M. Further
= 0.0075 rDol
2 H^O This is the rotat [Ag+] preseDr in the solution (ob-
HzS ---:* 2 HrO+ + 52- tained from A&CrOa and AgIO3).

; K,p (Hzs) = [H3o+]2 [s2-l AgIO3-Ag++lOt

l 1 x 10-22 = [H3O+]2 x 10-te KrP (A8IO3) = lAc+l tlotj
or [H3O+]2 = 1 1 x 10-3 = l l x l0-a 1g-13 = 13.2 x 1o-4) IIo3-l
or [HrO+; = 3 32 r. 1n-z t. or [IO3-] = 0.3125 x 10-e
l'thh nr ti. 0.01 rnol of AgNO3 is 6dded to ore
litre ofn solrtion which is 0. 1 M in Nfl2CrOn and 0 005 = 3.125 x l0-lo M
M in NaIOr. Calculote the mol ofprecipitote formed flt
equilibrium nDd the concentration of Ag+,IOt trnd
(i) Colculate the degree of dissociatlon of acefic
Crol - (Kry values otAg2Croa ard AgIO, ore l0-t and acid in the rcsulting solution and pH ofthe solutioD.
10-r3 respectively). (ii) If6 g ofNaOH is ndded to the obove solutioh,
(Roo*ee 2001 )
determine the linal pII JAssume therc is no change in
Solution. 2A!NO, + Na-CrO, volume on mixing: Krofaceticacid is 1 .75 x 10-f mol
0.1 mol
...- L-rl u.I.T,2oo2)
AgzCrOq + 2NaNO3
(i) Miltimotes of CH3COOH
A8NO3 + NaIO3 * AgIO3 + NaNO3
= 500 x 0.2 = 100
0.005 mol
Millimotes of HCt = 500 x 0.2 = l0O
AgNO3 rhat will reacr with NaIO3 0.fft5 mol
=
Finalvolume after mixing = 596 1 5gg
AglO3 (ppt.) formed = 0.0O5 mol
= 1000 nrl-
8lt8
r'rndt' t,t,'s Nett Course Chemistryl$[)
Solution. C6H5COOA8* Cunr()OO- * Or*
,. lcHicooH}=ffi=o rru,
Solubility ir water. SuPPose solubility in water
tHol -ffi=o 1M
= r nrol L-1. Then

cH3cooH + cH3coo- + H+ JC6H5COO-I = [Ag+] =r mol L-1'

Before O1M 0 01M .. P =K,oor, =",q = Vz s x to-13
dissociation (from HCI)
After (0 1-r) 't (0 1+') - 5 x to-7 mol L-l
Solubility tn buffer of PH = 3 19
dissociation
pH -3 19meaDs - loglH+l =319
or log[H+]=-319=481
Presence of HCl, dissociation
As in tbe of
CII3COOH will be very small (due to coormon ion ef-
or [H+] =6 45?xlo-a
fect), -r is very very sn]all. Hence C6H5COO- ions oow combine with the H+ ions
- rr0
Ka =-ii.f1) =r to form benzoic acid but [H+] remairis almost constant
bcause we have buffer solutio[. Now
= I 75 x lo-5 mol L-t lcivenl C6H5COOH <- CeHsCOo- + H+
UHgj
... Degiee of dissociation = # =
_ -- [c5Hscoo-] [l{+l
=175xl0-' ^,=_rqs_Foosl-
1g+1 6.4s7 x 1f|-4

Further
= O'O01157o
[H+l=01+r-01
- IC5H5COOH]
ofiffi=tr=:--::+::='
- ro "'(')

pH - - log0 1- 1 SuPpose solubility in the buffer solution is y

mol L-1. Then as mosl of the beozoate ioDs are con-
(ii) 6g of NaOH = fr mole
verted into benzoic acid molecules (whicb remain alnlost
= o 15 mole iooized), we have
Hencc now the equilbrium will be y = [Ag+] = [c6H5coo-l + Ic5HscooH]
cH3cooH + HCI + NaoH
Initial 0'l o1 0.15 = IC5H5COO-I + l0 [c6H5coo-]
Ar eqm. 0 05 00 = l l [C6H5COO-] (usiDg eqn. (i))
cHrcooNa + NaCl + H2O
000 ... tc6H5coo-l =+
0.05 0 o

Thus the solution will now be 0'05 M in

'. K,e = [C6HsCoO-] [A8+]
CH3COOH aod 0 05 M iD CHJCOONa i' it is acidic
i.e. z.s x 1o-3 =+ xy
buffcr.

pH=-rosKd+b8#i:l ot f =215 x 10-12 or y=166x10-6

v 1.66 x 10-6 - .^
= -loc(1 '75 x 1o-5) + lo8oq8; r 5 x l0-'
= 4'7s1 Note lh8t in case of salt of weak acids, the solubility
ti is more in tbe acidic solutios than in watcr. The reasoD,
i'r ,hlttn The ioDizotlon constsnt of benzoic
in general, may be explained as [ollows :
acid is 5 46 x l0-5 ond K? for sllver benzoate is
Taking ermmPle of C6HlCooAg, we have
2 5 x 10-rl. How mhny timc6 is sllver betrzoate more
soluhle in a buffer ofPH 3 19 comPared to its solubility c6HjcooAg # cerlscoo- + lg*
in pure water ? w c'E'R'r)
 EQUILtBRtUM (ONtC EQUtLtBRtUM tN SOLUTTONS)
- 8n9
ln acidic solution, the a[ions (C6H5COO- in the 1

presenr case) undergo protoDation lo presence of acid.

= 7 + r16 - 0 6990 +0.6990 - 2l

Thus, C6HTCOO- ions are remo!,ed. Hence equilibrium =9

shifts forward prGlucing more Ag+ ions. AlterDatively, 1,, t J/r Assmple of hixed alkalis contairlng
-- -_i't.,,!
NaOH and Na2CO, is tirrated
as C6FI5COO- ions are remowd, Orp dccreases. IR in the following two
order to nraintain solubility product equilibriunl schemes:

(Orp = K"p), Ag+ ion concentration musr increase.

(it l0 ml ofabove mixture requircs t ml of0.l N
HCI by using phenolphthatein.
Hencc solubility is more,
(ii) l0 ml ofahove mixrure requires l0 ml of 0.1
t'tihtu, .lS. Cslculate the solubility ofAgCN in a N HCI hy using methyl orsnge,
bulTer solution of pH 3.00. K,p for AgCN is Calculate the ratio of the weight of NaOII ard
2 2 x 10-16 anrl t! for HCN is 6 2 x l0-r2. NarCO, in the sample mixture,
Solutioh. SiDlilar to problem 37. We shalt get (Wcst Beng I l.E. E. 2 0041
SolutioL Basic principle iDvolved is as follows :
_lrisy=qf=,0-,
[CN-l K, 62xl0-l o=
r.6x ro6 Acid used with phenolphthalein as indicator.

= Complete Deutralization of NaOH

sorubirity. r = JAs+l = [cN-] +[lIcN]:[HcNi I
+ i neulralization ot NazCO3
(as [CN-] = [IICN],/(I 6 x 106; is negligible in
conrparison ro HCN) Acid used with methyloraDge as iDdicator
[HCN] x
... rcN-t - I6xl0o = l.tr x 106
= Complete neutralizatioD of NaOH
+ Completc neutralization of NECOJ
KrP = [Ag+] ICN-] M eq of HCI used for l0 ml of mixlure usinB
phenolphthalein

l.6Xt00 =22x1O-t6
-' =8 x0.t = 0.E
ot .t = 1.9 x 10-5 mol L-r. . . M eq of NaOH + M eq of Na2CO3 = 0.8
+
I !..., t, /t ttt 0.1 M HA is titrated agsinst 0 IM
NaOH. Find the pH nt the cnd point. Dissociation con_ ...(,)
stant for the acid HA is 5 x l0-5 oncl the degree of . . M eq of HCI used for l0 n)l of mixture using
hydrolysis, /r < 1. methylorange
0.1.i 2004)
Solution. HA + NaOH-NaA + HzO = 10 x0.1 =l
(weak) . , M eq of NaOH + M eq of NazCO3 = 1 ...(ri)
At the end point, their equir"alent amounts react Fronl eqns (i) and 0i),
together
M eq of Na2CO3 = (1 - 0.S) x 2 = 0.4
. . In ihe final solutioD, tNaAl = = 0.05 M
+ M cq ofNaOH = I- 0.4 =0.6
As NaA is a salt of weak acid and strong base, it Eq. wt of Na2CO3
hydrolyses as = tO6/Z - 53

Eq.wtofNaOH=40
A- +H2O ga+OH
=+ .. 0.4 M eq ofN%Co: =
For sucb a salt, 1ffi x 0.+ = o.o2t\g
pH=7 +
+lpKo+ togcl
0 6MeqofNaoH = ffi , o.c = o.rzr

Ratio of weight of NaOH and NECO3

=t +l.be6 x lo-5 + togo.o5l
= o'02a / O.0212 = 1.132
8/80

MS, AFMC, DPMT, CPMT, BHI

lations
l. Mcral ions like Ag+, Cuz+etc-aclas t, The following equilibrium is established when
bydrogen chloride is dissolved in acetic acid.
(a) Bronsted aqd (D) Bronsted bases
(c) Lewis acids (d) Lewis bases' Hcl+cH3cooH qJ 61-.'6tI1699I]r+
2. With increase iD temperature, ionic product of The sst that charactcrises the conjugate acid base
\!ater pair is
(glncreases (r) decreases
(a) (Hcl, cH3cooH) and (cH3cooHi' cl-)
(c) remaiDs umffocted
(b) (HCt, CU3cooH2+) and (cH3cooH cl-)
(d) may increaso or decleale '
3, In the titration ofaweak acid agailrst a strong base, (c) (cH3coOH2+, HCD and (cl-, CH3COOH)
at the half-equivaleDce Point (half-neuualisation)
.
(d) (HCr, cl-) and (ctr3cooH2+' CH3COOH)
@pH=+pK, (07pH = pK"
(1.1.7:199))
(c) pH = 2P\ (d) Nonc is correct. '9.' Which of fte followinS solutions willhave pH clGse
' to10'l
4. ThepHof a lo-sMsolutionof IlClin water is
+ 100 Drl of (M/10)
(o) 100 ml of (M/10) HCI
(D)
(c) 8
-8 NaOH
(c) between 7 and 8 (4betwccn6 and 7'
(D) 55 nrlof (M/10) HCI + 45 n,llof (M/10) NaOH
' (M.L.N.IL Nrahabad 1990, M'P PM'T 1996'
(c) 10 n of (M/10) HCI + 90 mlof (M/10) NaOH
Haryarn C'D'E'T 2000)
_(d) 75 nrl
of Gv!s) HCI + 25 ml of (M/5) NaOH
5. At 90"C purewater has [H3O+l = 1o-5 M what t l.l. l. !t)gL:

is the value ofKl, at this teDlPeraNre ? 10. Which of thc following will occur ifa 0 1Msolutioo
of a weak acid is diluted to 0 01 M at collstaot
(a) 10-5 .6ro-" temPerature ?

(c) 10-13 (4 10-14

(d) [H+]will decrease to 0-01 M
(M. L.N. R All4h4bd.t I 9 9 0 ) (b)pII will decrease
6. GNen that lhe dissociatioD coosiant for H2O is ]rlpercentage
iooizatioowill increase
(d) will increase.
Kp = 1 x lo-14 mol2 litre-2, whal is the PI-l ofa
Ka

0 001 M KOH solutioD I . (Ji'1- lt)t))

'\:Il '1|'llvtl'kl
(a) 10-1r (b) 10-3 11. The ptl ofa 10-t0 M NaOH solutioD is Dearest to
(")3 kf1t. (o) l0 (b)7
(M.L.N.k AllLltdbdd 1990) W
(d)
-10.
(M.L.N.R. Allthabdd 1992
i. Among the following hydroxides, the one which has
)

the lowest value of Ksp at ordinary temPerature 12. The prccipitate of CaF2 (\, = l 7 x 10-10) is
(about 25'C) is oblained when equal volumcs of tho following aro
(4) MS (oHh (b) ca (oHh mixed:
(c) Ba (OH)2 FlBe (oH)z. (4) 10-4 M ca2+ + F-10-4 M
(I.LT l99o M Ca2+ + lo-3 M F-
.llb) to-2

1.c 2.a 3.b 4.d 5.b 6'd 7'd E'd e'd 10' c
11. ,
 EQUILTBBTUM
- I (ONIC EQUtLtBBtUM tN SOLUTTONS) 8/81

(c) 1o-5 M caz+ + 1o-3 M F- moles of HCN in water aDd lDaking upto total
volume to 500 ml is
(d) 10-3 M ca2+ + l0-5 IUF-.
<tq 9.3o (b)'7 30
. (c) 10 30 (l)8.30. it ,

Acerrarn buffer solutioD contalns equal coDcentra-

tion ot X- aDd HX. The Ka for HX is l0-8. 'l}le
19. The solubility otAgI rn NaI solution is les.s than that
in pure water becausc :
pH of tbe bufler is
(.r) AgI forms coDplex wirh NaI
(a) 3 -(r) 8
(b) otcontn)on ion effect
(c) 1r (d) 14.
(c) solubiliry producr ofAgI is tess rhan thar ofNaI
(d) lhc remperaturc of the solution decreases.
14. Which of lhc followiug is not a Lewis basc ?

lsfas* (D) H2O 20. Whal is thc percentagc hydrolysis of NaCN in N/80
(c) cN- (d) NH3. slutioD $'hen thc dissociation conslaol for HCN is
I 3 x 10-e and Kx/ = 1.0 x lQ-la
15. Which anion is the weakest base ? @)2.a8 (b)s.26
(,) QHso- (d) Not 2
(.) 8 (d) e.6
t' : | 1 l
(c) F- (d) cH3coo- \
'.?t. Thepll indicators are
(4) ofstrong acids and srrong bases
salts
16. The correct order of increasing [H3O+l in the (D) salts ofweak acids and weak bases
following aqueous solutions ts .. (c) eitber weak acids or weak bases
(.r) 0 01 M HzS < 0.01 M H2 SO4 (r/) cither strong acids or strong bases
< 0.01 llt Nact < 0.01 M NaNO2
(6)0 01 MNaCl <00lMNaNO2<0.01 M 22. -Ihe solubilily producr of AgCI is 4.0 x 10-10 ar
298 K. The solubiliry of AgCt in 0.04 m C2Cl2 wi
II2S < 0.01 M H2SO4
be
(c) 0,01 M NaNOz < 0.01 M NaCl < 0.01 M
m
(a) 2.0 x l0-5 (b) 1.0 x 10-am
H2S<001 M H2SO4
(c) 5 0 x 10-em (d) 2.2x1O-am.
(l) 0.01 M H2S < 0.01 M NaNO2 < 0.01 M
NaCl<0.0tMIlzSO4. 23. How ntuch sodiunt acetate should be added to
0 I m solution of CH3COOH to give a solution of
'llre best explamrioo for rhe solubitityof MnS in dil pl I 5.5 (?K! of CH3COOH=a.5).
Uir.
lIClis that (a) 0.1 m (b) 0.2 m
(.r) solubility product of MnCl2 is less rhan rhat of +)F1.0m (d) r0.0 m
MnS ,llttr\!. tr( t ! i ,

(D) concentration of Mn2+ .14. The srrondest base of lhe tollowing species is
is Iowercd by the forma-
tion of complex ioDs with chloride tons (a) Nrr2- (6) OH-
(c) concentration of sulphide ions is lowered b_v (.) o. (d) s,-
oxidation to tree sulp-hur
(l) conceDtration ofsulphide ions is lowered by the 25. Which of rhe following sutphides has rhe lowesr
lbrmation of lhe weak H2S. solubility product ?
(4) Fes (b) Mns
It. The pKa of HCN is 9.30- The pH of a solurion
) (c) Pbs (d) ZDS
prepared by nri\ing 2.5 moles of KCN and 2 5

12. b 13. b 14. o 15. b 16. c 17. d 18. a 19. h 20. a 2t. c
22, c 23. c 24. a 25. c
8182 Net4 Course Chemistrg
26. The pH ofa solution obtained by mixing 50 ml of pfAutoprotolrsis constant of water increases with
0.4 N HCI and 50 mlof 0 2 N NaOH is temperature
(a) (r) 0.2 (d)Wheo a solution of a weak monoprotic acid is
-lo9z
(c) 1.0 (d) 2.o.
-log titrated against a strong base at halfneutraliza-
fion Poioi, PH = (12)PK.a. IIT t992
i,.
The concentration of [H+] and IOH-] of0 1 M
27. lD a mixture of a weak and its sall, lhc ratio o[ thc
aqueous solutron of2oZ ionized weak acid is (ionic
conccntration of acid to salt is incrcased tenJold
'[tepH ot the solulion product ofwater = t x 10-1a.1

(a) decreases by one (r) decreases by one tenth (a)0 02 x l0-3Mand5 x 10-11 M
(c) increases by oDe (d) iDcreases ten-fold. (b) I x 10-3Mand3 x lO-11 M
(c)2 x 10-3M and5 x lo-12 M
2t lfa neutralsolutron hasPKv = 13 36at50"C (heD
(d)3 x 1O-2Mand4 x 10-13 M.
plI of the solution is
(A 6.68 (b)1
The strongest conjugate base is
(c)7.63 (d) None of these
r.4.li,1I (. l\tnt 1997, K ttla l: l: I -""' i (a) Nol (b) cr-
LrlThe solubiliry product of CuS, A82S and HgS and (c) sol- . (d) cH3coo-
10-31,10-44 and 10-51 resPectivcly. The
solubilitiss of these sulPhides are is the order
36. The solubility of a saturated solution of clcium
(.l) Ag2S > CuS > HgS (6),{825>HgS>CuS
fluoride is 2 x 10-4 moles Per litre lls solubility
(c) HgS > A&S > CuS (d) CUS > A&S > HgS. product is
t( ll\t l)\l t t j')- (a) 12 x 1o-2 (t) 14 x 1o-'
30. If for flouride ion at 25'C is 10 83, the iooisa-
pKD
(c)22 x lo-11 (4Zz x 1o-rz
tion constant of hydrofluoric acid at this tempera- t('.lt ,\ l, l:)11.1 )9YY)
ture is
01 M solutioD ioniss to
(a) 1.74 x 10-5 (6) 3.52 x 10-3 v{ A monoprotic acid in a 0
0.001%. Its ionization constallt is
(c) 6.75 x t0-' (d) 5.38 x 10-2 x l0-3
(a) 1.0 (6) 1.0 x 10-6
(c)10x10-8 (y'; 1.0 x t0-r2
31. 'lhe solubility of ArX, is y mol dln-3. Its solubility
product is 3t. What is the correct rePresentation for the solubility
(a\ 6 (D 6av' product ofSnS2 ?
va
(c):61 <affiats. tt.t.t: teeT (c) [sn2+l ls2-]2 Irflsn4+l [s2-12
+l
+2. Which of the followi[g can act both as Bronsted (c) [sn2+l [2 s2-12 0dls [2s2-F.
acid and Bronsted base ?

(a) Na2CO3 (D) oH- 39. The solubility of CaCo3 in water is 3 05 x lo-a
(c) HCO3- (d) NH3 molesritre. Its solubility Product will be
(trl.P Pltl l: l9t (a)6.1x 10-' (D) e.3

q3. Which of the following statement(s) is (are) cor- (c) 3.05 x l0-' (d) 9.3 x 10-8
rscl ?

(a) The pH of t 0 x 10-8 M solution of HCI is 8 40. pH of water is 7. When a substance Y is dissolved
in water, thepH becomcs 13. The substance Y is a
(6) The conjugate ba.se of HrPO! is HPOI- salt of

,r{Rs
25. c d
27. 2E, a 31..1 3L c 33. b'c 34, c 35, d
f6. cl 37..1 38. ,
EQUTLTBBTUM fl (ONrC EQUTLTBRTUM rN SOLUTIONS) 8/83
-
(d) weak acid and weak base (c) Weak acid and its salt with stroDg base
(b) strong acid and strong ba,se (d) Weak acid and irs salt with weak base.
(c) strong acid and weak base Ii.ll t :,11,
(/) weak acid and strong base. ' {A Which solurion wlll be strongly acidic ?

4I. The pH 0 1 M solutron of the following salrs in- (a) wheD pOH=4 5 (6) whenpH = 0
creascs iu the order (c) when poH = 14 .(d) Borh (b) and (c).
(d) NaCl < NHaCI < NaCN < HCI
\(' I)ll T. )tttt,,
(b) HCI < NH4CI < NaCl < NaCN 4t. The?H ofan aqueous sotution ofCH3COONa will
(t) NacN < NH4ct < Nact < HCI be
(a) 7 (b)3
(d) HCI < NaCl < NaCN < NHaCl.
J"T9 (d) 14. tc.PM.T. 20001
49. Which of the followiDg is no, a buffer ?
'42. Which one of the following is true for aly Orproti"
acid, HzX ? (a) HrCOrt HCOI
(a) &z t K,r Ff*r'xo (6) CH3COOH/ CH3COONa
(c) NHaOH/NHaCI
(.) K,, = (d) \"2 = K,r.
* .1afNH.ouzcnrcoon. t r.r.prr.ri.R. 2i)00t
t( B S.Ii. I!.v.'|- 2000\ 50. For a buffer with equal amouots of the salt and rhs
43. The conjugate acid of NHz- is acid with K, = to-t, thcpH is
(o) o (D) 13
(a) NHo+ (6) NH2OH

lrlirHj (d) N2H.:

tir (d)8-log2.
Ha4dru C.E.L.T 2000)
(

("
li. I!,r1.T. 2000) 5.
t R. 51. Iorisation onstant of CH3COOH is 1.? x lO-5
44, Which of the following statements aboutpH and and conccntration of H+ ions is 3.4 x 1O-a. Then
H+ ioo concntration is incorrect ? initial cooclntratioD of CHsCOOH molecules is
. (d) Asolution ofthe mixture ofoneequivalent each x 10-a
of CH3COOH and NaOH has apH of 7
(c) 3.4 (D)3 4x to-r
(6)pH ofpure neutral water x 10-3 (d)1.7x10-3
is Dot zero -(9!5-B
t (. B s.L. P,tl't: 2()0 I \
(c) A cold and concentrated H2SO{ has lower
H+ 52. In HS-,I-, R-NH2, NH3, order of proto[ ac-
ioD coDcentration than a dilute solution of
cepting tendency will be
H2S04
(d) Additioo of one drop of concDrrared HCI in
(a) I- > NH3 > R-NH2 > HS-
NH4OH solution decreasespH of the solution. (D) NH3 I-
> R-NH2 > HS- >
,i,\: 1',t - )it
(c) R-NH, > NH3 > HS- > I-
45. Which of the followiDg has lowesrpH valuc I
(a) I M Hcl (b) 1 M NaoH (d) HS- > R-NH2 , NH3 > I-
{.r1 M H2so1 (d) r M qHsoH. t(. B \.t.: It11,t: 200t\
53. HydrogeD ion concentration of aD aqueous solu-
Which solutions are mixed to form a buffer solu. tion is I x t0-4 M. The solution is dituted with
lioD ? equal volume of warer. Hydroxyl ioo concDtration
(a) Strong acid and ils salt with strong base of the resultant solutio[ irl terms of mol dm-3 is
(6) Strong acjd and its salt wiih g,Eak bas (c) 0.5 x l0-to dzxrc-to

40.d 4t.b 4Lb 43, c 45. c 46. c 41,.1 4t. c 49. tt

c
50. 51,c 52. c
ala4 Neqt Course Chem i strrl
(d) NazS > ZnS > CUS
(c)1x t0-6 (d) 1x 10-6
.. 6L Whioh ofthe following has highestplj ?

54. pH ofa solutlon produced when aqueous solu-

aD (o) CHrCooK (D) NEco3
tion ofpH 6 is nrlxed with an equal volume of an (c) NHaCI (d) NaNO3 .
aqueous solution ofpH 3 is about
@)a s (6)4 0
(c)a.3 (d)33,' 62. Which of the following is the buffer solutioo of
strong acidic nature'l
55. ThepKo of a weak acid ii 4 8. what should be the
ratio ol [Acid]/[Salt] of a buffer if pH = 5 8 is (a) HCooH + rlcoo-
required ? (b) CH3COOH + CH3Coo-
(4) 0.1 (D) 10
(c) 1 (d)2 (c) H2qo4 + qoi-
lL.A.M.C.L.T 20()l ) (d) H3Bo3 + Bo!-
Which of the folloling would Produce a buffer 63, Wa(cr is a
solutio[ when mixed in equalvolumes ?
(4) protophobic solvsot (r) protophilic solvent
(a) 1 M CH3COOH and 0 5MNaOH
(c) anrphiprotic solvent (d) aprotio solvent
(D) 1 M CH3COOH and 0 5MHCI
(c) I MNH.OHand0 5MNaOH 64. Among lhe lollowing, the weakest base is
(d) 1 M NH.O and 0'5 M HCI (a) H- (b) cHt
(li.A.u.c.E.T 2001) (c) cH3O- (t) ct-
ThepH of8 0.1 M squeoussolution ofa wesk acid
(HA) is 3. What i! its degrce of dissociation ? 65. ln the reaction 12 + l- -..- I3-, which is the Lewis

(b) lovo base ?

(a) 1%
(c) sovo (d) 2s% (a) lz (6) r-
\ l: \.ll ( .1: l: )ttt)i :
G)13- (d) None of these
5t. ThepH range ofmethyl red indicator is
(lktjdstltt LlL'f :0(): )

(o) 4.2 to 6.3 (D) 8.3 aod 10.0

How do vou differentiate between Fe3* and
(c) 8.0 to 9.6 (d) 6.8 to 8.4
cf + in group tII t
(a) By taking excess of NHaOH
59. For a sparingly soluble salt Ap Bq, the relationship
(b) By increasing NHo+ ion concentration
of its solubility product (Ls) with its solubility (S) is
(c) By decreasing OH- ion concentration
(a)4-sP+c.f.C (d) Borh (b) and (c) (A.I.E.E.D. 2002)
(q4-s/,+c.Pc.4P at l. Solubility of atr MX2 tyPe elcctrolyte is

(c) ls = sr, ./ .C 0.5 x 10-{ mol L-t, then I(+ of tbe electrolyte is

(t)\= sPc (pqf+c. (a) 5 x l0-12 (b) 25 x lo-10

60. Idcrtiry thc correct order of solubility of (c) 1 x 1o-13 (l) 5 x 10-13
( (,8.,\.8 I',,ll.I:
Na2S, C\s and ZnS io aqucous medium 2002 )

(a) CUS > ZrS > NES In which of the followiDg acid-base titration, pH is
greater than 8 at the equi!lencr point ?
(b) ZnS > Na2S > CUS
(4) Actic acid versus ammonia
(c) Na2S > CuS > ZnS

s3. b g. .l 55. c 56. a 57. a 5E. @ 59. a 60. d 61. b 62. a

63. c 64. il 65. b 66. d 67, d
 fl (ONrC EOUrLrBRlUL4 lN SOLUTTONS) 8/85
EQUTLTBRTUT\,r
-
(D) Acetic asid versus sodium hydroxide (c) 6.1 (d)7.2
(c) Hydrochloric acid vcrsus ammoDia The rapid change of pH near the stoichiometric
(d) Hydrochloric acid veNus sodium hydrdide point of an acid-base titration is the basis of iD-
i?l i /. ll sl -'r1l.r l
dicator detectioD. pH of the solution is related to
ratio of concentration of conjugate acid. (HI^ ) and
Whcn rain is accompatried by a thunderstorm, the
the base [1r-) forms ofthe indicator by the expres-
collected rain watcr will have pH value
ston
(a) slightlyhighor than thatwhen the tbunderstorm
is not thcre
(D) uDinfluenced by the thunder storm
@)rrgffi-pK,,-pH
(c) which depeDds on the amount of dust in air rogl+ql
(D) =pK,, -pH
(d) sligbtly lower than that of raio vater witbout lr/r I
thunder storm \ t.t. r. :|t):
1c; togllP =pu -pr,,
70, In the hydrobsis of a sslt of wcak acid and weak
base, the bydrolysis constant Kr, is equal to
(a)KN/Kb (b) K*/ K" @)rcsffi=fi-tx,^
(c) Ki,/It K6 (d) Ka K,
A weak acid HX has the dissociation constant
I x 10-5 M. It forms a salt NaX on reaction with
Tbc solubility prduct of AgI at 25'C is
alkali. The degree of hydroB6is of 0.1 M solution
1.9 , 19-16In62 1-2. The solubility of AgI in of NaX is
10-1 N solufion of KI at 25.c b apprdimately (in (a)o.ffil% (b) 0.o1%
mol L-1) (c) o.7% (d) o.15vo
(a) 1.0 x 10-t6 (D)1.0x10-12 ??. The molar sotubility (in mol L-l) of a sparingly
soluble salt MX1 is r. The mnesponCing solubility
(c) 1.0 x 10-lo (d) 1.0 x 10-8
product is given ry Ilp. r is gwen in terms of I$ try
the relation
Solubility of PbIz is 0.0013 M. Then solubility
product of PbI2 is (a)s = 1l\ot DAlt/' 1t)s =(?6KQt/a
(a)2.2 x 1o-e (6) 8.8 x 10-e 1c;.r = 12s6 \r)r/5 yfs - (K,p/ 256rt/5
(c) 6 8 x 10-6 (d) s.8 x 10-6
t I). t: li.l. )t10.i )
Whici one of lhe follo$,ing is not atr amphoteric
subctatrce ?
A solution which is 10-3 M each in Mn2+, Fe2+, (a) HNO3 (D) Hcot
Zn2+ ana H{+ is trea ed with 10-16 M sulphide
(c) rIzO (d) NH3
ion. If Iqp of MDS, FeS, ZDS aDd HgS are 10-15,

10-23, 10-20 and 10-54 respectively, which one .,9. The mixture ofacetic acid and sodium acehte, the
\rill precipitate Iirst ?
ratio of concentrations of the salt to the acid is
(a) FeS (6) Mss inqeased ten timcs. TheopH ofthe lolution
(c) Hgs (d) Zns (4) increases by one (6) decreases by one
14, What is tbcpH of 0.01 M glycine solution ? For (c) decreascs ten fold (d) increases ten fold
gb'Eine

K,r=4 5 x 10-3anoK,,= 17x l0-'0at298K E0' Select thepKa value ofrbe strongest acid ftom the
follo ing :
(a) 3.0 (b) 10 0
orl.o (6) 3.0

6E. , 69..1 70. c 71. b 72. b 73. c 74, c 15. d 76.b 77..1
7t. a 79. a
 8/86
t' :.,l!.t,': Nct4 Course ChemistrgWlll
(c) 2.0 t/)1s (,) 1 (b) 5
(c) 8 (d)e
' .p! me pX" of acetic acid is 4 74. The concentration (e) 13 (Keruld C.|a.E.200-l

or CH3COOH is 0 01 M. ThepH of CI{3COOH t4. The principal buffer present in human blood is
(c) NaH2POa + NazHPO4
(b) 4.31 (6) fl3PO4 + NaH2POa
(d) o.414
(c) CH3COOH + CH3COONa
@riss.t _l.L.E. 2t)01
(d) Na2HPo. + Na3Por
tz 50 HCI and 50 mlofo 2MNaOHare
mlof0.1 M
mixed. ThepH of the resultiDg solutioo is
(b) 4.2
l/fircorrucol Ketdln I:M.'l: 2004
65. De8ree of dissociatioD of NHaOH in water is
(d) 11.7o
(.1 & K L.lr.1:201 I .8 x 10-1, then hydrollsis constant of NHlcl is

\41' (c)1.8x10-5 (D) 1.8 x 10-ro

o :rs s or HCI gas was passed through 100 cnr3 of
0.2 M NaOH solution. The PH of the resulting (c) 5.55 x l0-5 ldfi.55 x lo-ro
solutioD would be (llilur C.Ii.(.Il. )00

HINT5/EXPLANATION9 t o Wult iple Choi Q.uesaione

3. At half-equ iEleDcc Point, 11. See sotued example on Page 826.
PH - PKd 12. ln (b), ionic product = lca+l [F-]2
4. Sec soh,cd cxample on Page 826. = 1 25 x l0-9 which is greater tllaD lqp,
s. K,r = IH+l toH-1 = 1to-6; 116-e; = 16-tz 13. pH*p(d+bsf#:l
6 0 001 M KOH means [OH-l = 10-3.
ll =-los1o-t+IogI-8
Heuce [Hro+] = 10- .. PH = 11. 14. Ag+ ion is a Lewis acid- CH4 is neither Lcu'is acid
7. The solubility incrtases down the Sroup due to nor Lewis base,
inc[oase iD sizc of the ioD and deqease in lattice 15. weak No3-
base has a strong conju8ate acid. has
eDer$/. Lolrer the solubility, louer is the Krp.
ihe stroflUest co[jugate acid HNO3.
e. (a)pH - 7.
(D) IvV10 HG lcfl uDneutralized = 10 [l)l of M/l0 16. FI2S = weak acid, H2SOa = strong acid, NaCl =
Ttrlalvolume = 100 nll. neuEal, NaNO2 = basic. Hence [H3O+1witl be in

''' 10x#=l0ox?M the order : NaNO2 < NaCl < HzS < H2SOa.

.. lHcll = -]- = to-2 t''t. pH = z 17, MnS + 2Hcl* Mncl2 + H2s. As H2s i5 a weak
electrolrte, it ionises very lcss. Heoce coocentration
pll will be > 7.
(c) solutioD is basis,
ofS2- ions is lowered-
(d) 75 ml M/5 HCI = 15 milliDloles,25 mlof M/5
NaOH = 5 millimoles- HCI left unneutralised = 10 1& pH-pKd+t*i#S
nillrmoles. Volume = 100 ml.
=e 30+loC#=e 30
.. tHcrl -ffi=o rru
19. AgI (r) + a4 ;* Ag+
1aq1+t- 1aq1,
PH=-lo8(0 1)=I ryn1 Na+ + I-. Due to common ion effect,
10. On dilutioD of a weak aoid soiution, percentage -
equilibrium shifts backward.
io8isation iDcrease&
'lls
E0, a t1. a 1t2. c ltJ. I ll'l e E5. d
EQUtLtBRIUM (tONlC EOUtLtBRtUM tN SOLUTTONS) 8187
-
20. NaCN is a salt ofweak acid (HCN) and strong base 29. .r (Cus) = r'-K, = y'ro=f = lo-ts s,
(NaoH).
AgrS ...- 2Ag+ + S2-,
Hence
Kro = 1z s;2 x r- 4,r3
,r=\E =
l0- 14
(1.3 x lo-e) x 1,/ 80
or ,= lt -- \r/3
= 2'48 x 1D-2 [a \nJ
. . %age hydrollsis L ^-41\t/3
= (2.48 x l0-2) x lfi) * 2.48.
= l!,-l
t-t = 12 5;r/3 x lo-r5,
22. If-r is the solubility ofAgCl in 0.04 ,'| CaCl2, then r'R;
.r (Hgs) = = v10-54 = 10-27
[Ag+] =: rn L-1, 30. The dislociation mnstants of a weak acid and irs
"t conjuBate base are rclated as
[Cl-] = (0.04 xZ) +x-0.08 pK"+pKb=pK-
.. t(0 ft])=4x 10-lo . plL + 10.83 = 14
or -t = 5.0 x 10-9 m
or PIq = 3.17
ICH.COONaI
23. pH = pKo + log -torKe=317
lc-Ee-Oo_Hi or logK,- -3.17=483
ICH.COONaI
5.5=4.5+ros-_lo-j1-: or x to-4. &=6 7a

=4 5 + loc [cH3COoNal +1 31. A2X3- 243+ + 3 X-2,

or log [CH3COONaI = o K,p- (2y)2 x (3i,)i = lo8f.
- [CH3COONa] = lz 32. I ICOt caD accept a proton as well as Bive a proton.
24, Due to highest eloctron density on N in NH2-, ir 34. HA # H++A-
can ac{ept protons mosl casily and heDc is the
c
stroDgest base.
25. Sulphides of Group II (PbS) haw low solu\ility
c(1 -a) ca ca,
product. ... [H+] =Ca=0.1 x0.02-2x l0-3.
26. 50 mt ofo.4 N Hc, = *-1 xso =0 02geq.
Hence loH-l
- - lo-14. = 5 x lo-12
2 x l0-r
x so = o.0l
50 ml of 0.2 N NaOH =
ffi g eq.
J5. Strong conjugate base has a wak conjugate acid.
0.01 g eq. of NaOH will neutralisc 0 01 g eq. of Weakest conjugate acid is CH3COOH.
HCr
..- HCI left uDneutralised = 0.01 g eq. 36. CaFz C-a2+ +2F-,
Volume ofsolution = 50 + 50 = 100 ml
-
K,p = r (2s)2
.. tHol =
oi6oJ
xloooN =o.tN
=ls3-4x(2x'10-a)3
or [H+] =o 1M =32x10 ''
.. pH - log (0.1) = 10. 37. HA + H++A-
pH=p\+rogffi c
c(l-a)
=px. + log fr:pR, - 1. .. CdXC.,
l\.=--ca_
c (l -a)
24. pl<v=pH+pOH.
c = 70-2 M,
As [H+l = [oH-], 0 001
a = -iTD- = l0 -,
PK.,=2xP}t
or pH-13.36/2-668 ... K= 10-2 x (10-5)2 = t0-12
8/88 Netd Course Chemistrg
40. pH = 13 meaDs the solution is basic. ... Isarrl{Acidl = 10
41. NaCl = neutral(pH = 7);NHaCl = Slightlyacidic or lAcid]4saltl = 1/10 = 0.1
@H < 7); NaCN - basic(pH > ?); HCI = strongly Vc.c. of 0.5 M Naofl will neutralise VD c.c. of 1
acidic(pH << 7). M CII3COOH to form sodiunr acetate. VZ c.c. of
. . order will be HCI < NH4CI < NaCI < NaCN. I M actic acid will be preseDi alon8with sodiunl
acetate.
42. For diprotie acid Ko, . Ko,.
IIA + II+ + A-,
43. NH2- + H+ = NHr.
lH+l -c"-ro-: (.'PH=3)
44. pH = 7 at the end poini is only for strong acid with
strong base, rle.0.lxa=10-3
45. Higher lhe [H+]. lon'er is the pH. or a=lo-z=77o
I M H2SO4 has hi8hest [H+ 1. 59. AoB, = pf.r+ + qB-
47. Pon= 14 meansPlI = 0. Less thepH, morc acidic SpSqS
is the solution. K* it. L, = (pSF ({S)q = 9+s f f
4E. As the solution is basic (not very strongly basic),PH Sulphides of alkali metals are soluble in water.
=9. Sulphidcs of group II have lower solubility than
50. See Q. 13. those ofgroup IV radicals.
s1' cHrcooH
+ cH3coo- + It+ 61. NH4CI solutiol is acidic, itspH < 7. NaNO3 solu-
tion is neutral, its pH = 7. CH3COOK and
Initial a
NECO3 solutions are basic, lheir pH > 7. But
At. eqm. 1r-a axto-a; 3.4 x 10-' 3 4 x 10-a N%CO3 solution is more basic, its pH > pH of
(3.4 x roll.1I_10-4) t..7 x to-i (Given) CHJCOOK solution,
=
(4-3.4x10-') 62, Out of the given acids, HCOOH is lhe stronSest.
(3.4 x lo-12 63. \4hter is an amphiprotic solveot asit can ac{pt
or h 3.4r _ ro-11 =
1.7 x l0-' protons as well as given protons.

=68x10-3 64. Cl- is the weakest base because it has lhestroDgest

conjugate acid viz. HCl.
or d =6.8 x 10-3 +3,4x IO-a=6 8 x 10-3
52. In R-NH2, electroo pair otr N is mosl easilyavail- 65. ln the rcaction 12 + l- I:-, I- is the electroo
-
pair doDor and hence is a Lcwis base.
able for protoDatioD besause R iselectron releasiDg
grouP. 66. In group III of aDalysis, addition of NHaCI iD-
s. After dilutlo[, [H*l = lo-o t 2. creases NHo+ ion concentration aod decreascs

OH- ion concntration produced from NHaOH

Hence r"H-]=
i*;i due to common ioD effect.

_ to-ta
10-4
l2 _2 x l0-ro M ''Y + M2+
sZs
+ 2X'
ln the final solution, I<le = (r) (2 s)2 = 4't3
lH+l - (10-6 + 1o-3)/2 =4x(o.5xto-4)3
t0 "
-...--z-
r.001 x
- 5 Y 16-13.
68. pH > 8 at the equivalcDcc poinl means that thc sali
= O.5oo5 x 10-3 - 5 005 x 1o-4 formed oB hydrolysis sbould give basic solulion r'.e.
whell acetic acid reacts with NaOH.
pH = - log [H+1 - log (5 005 x 10-1)
=
=4 -0 6994 -3'3 69, Due to thunder storm, temperature increases ie,
pu =pr! + rogffi IH+l increases which meanspH decreases.
70. For salh ofweak acid aDd wEak base,
o, rosffi=s8-4'8=10 q = K_/rt Kb_
 EQUILtBBtUM (tONtC EQUtLtBRtUM tN SOLUTTONS)
- 8/89
71. Total [I-] = lo-4 + t0-6- 10-1M 7e. Isr crse. ?H =/rq + tos#ffi =,/,Ka + k)c
lAs+l II -l = I(p
2nd case. pH =fK, + fog1p
.. [Ag+l I10-4J - 1.0 x 10-16
or [Ag+l = t0-12. =pKa + logf + tog10=pK, + togf + r

72. Pbl2 P*+ +21- t0. tligher the I(s r"lue or lowcr the pK, value,
- stroDger is thc acid.
..[Pb2+]=l3xl0-3M Itl' cHrcooH :-' cll:cro- + H+
Il-l=2x 1.3 x 10-3M =2.6 x 10-3 M
c00
&P = tPb'z+l [-F a
c---< ca cu
= (l 3 x 1o-3) (2-6 x 10-3)2 K,=.ffi= ;:;-c":."=,TV
.. ca.c4 ctz
= 8.8 x 10-9.
lrr+l=ca =, "T7; ="Tj
73. The one with lowest value of qp ie. HgS wi
prccipitate out first. irll - IoglH+l = - Iog(K,c)r'2
74. Gtycine H3N+CH2COO- is morc acidic than = x. - tog.1
| I-r,,s
basic, IDstead of K, !"lue, the second giveo Ka
value Is mrrEsponding to the K6 value 1r". - togc; =f
= 1l ,z,r - ros ro-21
(. I! x Kr = 10-la;. Hence overatl ionizarion
mnstant,
=!*a.t+ = t.tt
tZ 50mlof 0.1MllCl =S0 x 0.1 uri[imotes = 5 o]it_
K- xK- =4.5x 10-3 limoles. 50mlof0.ZNaOII = 50 x 0.2 millinl(rcs
x17xto-lo=765xl0-I3 = 10 miltimoles Millinloles ot NaOl I lcfl rfler
nculralization = 5. Volunte of rctution
y'265;-10-15; = 1Jr1y s.,1.
H+ = /Kc'= grt . Molar conc. of NaO11 = J-
. sx -2 M
100 =
1o
= /0-%5 ,. td=rT = 0.87 x t0-7 M
pOI{--tog(5x10-2)
- pH = - log (0.87 x l0-7) = 7 - 0.93 =6.07
7s. pH = p\
* bc Iggqffd-I@ (see pase 8/51) :--1-
= rog
5 x t0-;'
= IoS 20 - I 301
pH=14- t.301 = 12.699 = t2.10
:.pH-pKrn=t"ci#t
ll3. 0.365 g HCt = !-! mote = o.o I motc
76. Hydrollsis reaction is X- + H2O
HX + OH- =:+strong
For a salt of weak acid with
100 cm3 of 0.2 M Naoll _
*# x loo = 0.02 r.rotc
base, NaOH left unDeutralized = 0.01 molc
.. K_
r\b=K-=ca'
Volume of solution = 100 ml
.- Molarity of NaOH in the soturton
t0-14 0 0r
. j-_-?=0.1 xotoroz__ l0-8616 = 16-l =ffix1ooo=o tM=10-rtu

% hydrolysis = 10-4 x
. IH.l -#i;= 10-rrM
100 = l0-2 = 0.Ol
77. MX1 (D \-= M4+ (aq) + tx .. pH=13
@q)
, 4.t K* l0-t4
K,p =.r x (4.r4 = 256ss qs = 1K,ot 61t/5

= 5.55 x 10-10
8/90
Neu) Course Chenistrq

ADDITIONAL
As e erLi on -F.,e as on Typ e Q.u e sti ons
n. rvhile onswerlng these
oDe of th
(d) If both AEertloD atrd Rosou are truc lnd the u of the Aaslrtiott'

(ri If both Assrrtlon rnd Reoson sr. true but reason is not a corr'tt cxPlanetlon of the 'Assertlol''

(c) Il Asscrrtol i8 true hut RGasoD is fslse'

(d) If Assertion is falsr but Rc[sotr is true'
(e) Il botb Asscrtlon nDd Rcason sre false'

Assertion Reason

uPon the dielectric

\rhter effective in screening lhe elec' The forcD of ioDic intcraction dePnds
is sDeciallv
trostatic i;teractions betwecn t.i|c dissolved ions' constani of the solvent.

molar concenration of water

The de$cc of ioDization of water is small at ln pure water at 25'C the
-
25"C, only about one of every l0' molecules in
is essentially mrsEnt.
pure urater is ionized at aDy instant.
aod protoD
ThepKo of a sat scid bcroms equal toPH of The molar coDcentrations ofProton accePtor
donor become equal at mid Point of a weak acid'
the solution at the mid-poinl of its tilration'

4. pH of Hdsolution is less than that of acctic scid In equimolar solutions, (he number of titrable Protons
presint in HCI is less thao that Present in actic acid'
of the same concentratioo.

Acetic acid is I wesk acid. It has a weak conjugate base.

6. pH valueof HCN solution decrEases when NaCN NacN provides a common ion cN- to HcN'
is added to it.

pH of e,arcr increass with increasc in temPera- Iq/ ofwater increases with iDcrease in tenPrature'
ture.
buffer solution resists the changc in
when a small amount of stroog acid is added to Buffer action ofthe
added ro it.
a buffer solution, it! PH value docs not cianSc pH when
some acid is

significantv.
I to resist the An aqueous solution of ammoniurn acetate can act as
A buffer solutions has caPaciry
change inPHvalue oD additionofa smallamount buffer.
ofacid or base to it.

10. Sb (III) is not preciPitated assulPhide when in its Tbo coocentration of 52- ion in atkaline medium is

alkalina solution, H2S is Passed. iDadequate for PrcciPitation. lA.I IJL,1S' 2004)

11. AdditioD of sitver ioDs to a mixtur of aqueous Ilp of Agcl < Iqp of AgBr. Q4.I I'M'S' 200')
sodium cbloride and sodium bromide solution
will first preciPitate AgBr rather than ASCI'
EQUtLtBHtUM (toNtc EQU|L|BB|UM lN SOLUTTONS)
- 8/91

True/False Otatemenis
Whic h oI lhe folloh'ing bremeny
s ore fahe ? Ret+,rite 5. A_ solulion with pH less thaD zcro or greater than
rhem conectly.
14 cannot be prepared.
l. The degree of ioDization ofa salt is directlypropor-
6. More_acidic is the solutioD, grca(er is itslH.
tional to its molar concntration
7. ThepH of lo-E M HcI sol;rion is 8.
2. A Lewis baseisa substaDcewhich carldonate a pair t. Ionic product of watcr is ah,ays cqual ro l0-14.
of electroos. 9. PhenolphthaleiD is not a suitale iDditor for ritru_
3. CO2 is a Lewis basc. lion of HCI solution wiih Na2CO3 solutioD.
4. The ionic product of warer 10. Tbe solubility of pblz in watcr dccreases if KI
changes if a few drops is
ofacid or base are added to ir. added to it.

Fill ln The Blanks

1. A compound whose aqueous solution or melt con_ 4, A strong acid ha! a wrak ..... base.
ducts electricity is called ..... .
5. The sum ofpH aDd ..... is equat ro 14.
2. The dcgree of dissociation of a salt is ...-. propor-
tional to ..... .
6. Tbe loqlEr thepH, more..... is the solution.
3. According to Bronsted-LG,ry concept, an acid 7. Solubility Foducr is the producl of thc concenrra-
is a
suhstance which can ..... whereas a base is a sub_ rlon oI rc m a..... colution.
stance which caD ..... . - t. In thc readioD I- + I2r I3-, the Lewis acid is
(I.LT t99Z ; A.I.I.M.S. l99I)

Matching Ty?e Q.uestions

l. Match the entries of columnAwith appropriate cntriesof
column B.
Columr A columr B
(4) fitration ofacetic acid with NaOH solurion
(u) No suitabte indicator
(r)'I'itrarion of NECO3 solurion wirh HCI (6) Pbenolphrhatein
(c) Titration ofNHaOH with aceuc acid
(c) Methyl orange
2. Match rhe enkies ofcolumD Awith appropdate entries ofcolumns
B.
Column A
Columtr B
(a) Copper sutphare soturion
(o)pH >.t
(r) Sodium actare soturioD (b)pH<7
(c) Potassium nitrate solution
(c)pH = 0

AS SERTION-REASON TYPE OUESTIONS

AAISWET<S

1,3,4,6,7,8.
FILL IN THE BLANKS

l. an electrotyte 2. inversety, squarc rmt of molar coDccntratioD J. donate a proton, accpt a proron
4. conjugate s.pOH 6. acidic 7. saturared. t. 12

MATCHING TYPE QUESTIONS

t. (a)
- (b), (b)-(c), (c)--{a) 2. (a) _ (b), (b) _ (a), (c) _ (c).
sle2
Neut Course

HINTg/ExPLANATtoNgtoAe9,ert,ion-Reagonrvp"9:"=!iong
of HrO is smatl because 7. p]Hofwater decreases with increase in tenrpera-
,. ,"*r"" .f ionization
Hro is1*'y*t?5"1'rictrolvte' 10. sb (III) is precipirared (in Group IIB) by HrS in
j. pH = pKo + log
3' fridT'
il{cidT' acidic medium (dil. HCI). In acidic medium, s2-
At nrid point [Satt] = [Acidl. concentration decreases so that radicals of Group
4. Numberof fitrataUtepiotonsinHCl isgreaterthan IV are,ot precipitated. In alkaline medium, 52-
present in acetic acid. ion concentration increases and not decreascs.
5. weak acid has a strong conjugate base' rr. I(, of Agcl > Kro of AgBr. For precipitation to
6. gCN + H+ + CN-. NaCN gives common oc'cur, ionic proOuct should exceed solubility
CN- ions. Equitibriunr shifts backward, [H-] Product.
decreases so thatPH increases'
 R-edoxReactione

1d ion-electr

,., :
.-j1!_.1_!1,9l_!a:1,,,:1,1i:,:'',|:.i]ii,':li:l1i,jo+j,,-,Ii

In the previous uni! wehave sitdiednantmliza-

tion reactiots in which H+ ions ftom an acid (HC[
H2SO4, CH3COOH etc.) combinewithOH- ions of ol ltydntgen or any oher electmpositive eleme4t.
a base (NaOH, Ca(OH)2, NH4OH etc.) to form a For example,
salt ard weakly iodzed moleculas of water. In this (i) 2Mg(s) + 016) ----------.' 2Mso(r)
Q4ddition of orygen)
(ir) Mg (s) + Ct G)......- rvrecrz (s)
(Addition of electnnegative element, chloine)
(,,r 2n S
G) + 016)......+ zs(s) + 2Hroo
(Removal of hydrogen)
(t)4@d+Hro(O+orG)-
zKoH(aq) + I2(r) +or@)
(Removal of electmpositive element, potassiunt)
-. _In all these reactiotrs, the compound under-
lined has undergone oxidation.
. 922. . Oxidising agent or oxidanL According
to the classical concept,
examples of redox reactions, Before we discuss these Ar oddlsiDB agrrl or of,ila[lit a srt'/la*euhtch
redox reactions in detail we must be familiar with the ot arr! oth?r elaroiwgtitc eb-
concepts of oxi&tion and reduction.
fj_!:!i""-R".1,,,.,, -. a 1.r.. j Con..pf
-' _ rar ,,,::,r::l

92.1. Orddation. According to the classical

concept,
For example, orygen, chlorine and ozone in
reactions(i) to (iv) listed above in Sec. 92.1. are
9t7
912

Mg (s) + F, @) "'-"' 2MgF2 G)

4HCl(\q) + MnO2(s) -"-"'
Cuo (s) + C(s) .......-. CoG) + zn(r)
Mnclr(4q) + Cl2G) +2I[2O(I)
Fe2or(r) + 3coG) ""'-"'2Fe(s)+3co2G)
+
Hror(aq) zKr@Q """-'.' 2KoH(44) + I2(s)
Fero3(s) +Zal(s) ...-._.. 2FeQ) + Alror(s)
zKMrlOa@q) + 10 FeSO4(cq)+ 8H2SOa(aq)
2KMnO.(ag) + 3HrSO.(aq) + 5HNO,( 4q)
-""'-'' 2MDSo1(4g) + Krso.(aq)
-
K2SO{(49)+ 2Mnso{(uq)+5 HN or(4q) +3H20(')
+ 5Fe"(So.)3@q) + 8H2O(0
925. Orklaflon'reductio[ rtactlons art
K2Cr2o7@q) + 3So2G) + H2soa(aq) -"""'+
Crr(SOa)r(aq) + KrSOa(cq) + H2O(0
lOHNOr(aq) + Iz(s) ....-
10NO2G) + zlIlor(aq) + 4H2o(0
923. Rerluction. According to the classical
concept, the following examPles :
,:;#, (i) Resction betwcen ltydngen salphiilc and
chlorbrc
or dnY H2sG) + a&) 2HCl@) + s (s)
othet ebeionegatiy e element'
For examPle,
-
Herc, HrS is oxidised to S while Cl2k nduced

2I{BrG) + s(r) bHA.

(D&G) + H2sG) -""'4 (ii) Reaaion betn'cen sta$otts chMde and
(Addition of hYdrogen) mercwic chWde.
Q)aHsct|(ad
+ SnClr(aq) --- stC::@q) + 2Hgpl"(aq)-"'sncl.(a4) + Hgrclr(s)
Hcrct G) + Sncl(aq) Here, SnCl2 rs ondrs ed to StCl, while HgCl"
(Addition ol elecnopositiw element me'u'y) is redtced to HgrCl"
(ui) cuo (.r) + Hr@) "'-'-''cu(r) + Hro(0 (iii) Reaction between manganese dioxide and
(Rsnovol ol ocleen) hydtochWic acid
MnOr(s) + 4IlCJ(aq)
Gfl aFecto 1n1 + So2G) + 2}r2o(t)
zRe3l2@$ + HzSOI(4q) + zHCJ./oq) - M"Ar@q)-+ Cl2G) + 2HrO(D
(Remova! ol clcctonegttive. Herc, HA is uiilised to Cl, while MnOris
clcnenl chloinc) ,ehrced lo Mttch.
In alt these reactions, thc compound under' 9.3. Oxidation and Heduclion-
lined has undergone reduction'
92.4' Rrdiclng agprt or rcduclrrL Ac'ord'
ing to the classiel concePt,
A reducing agent or EductsDt Eay ddhed-as
ot aT olh2t
a nbstanti i*icn supptla lEilmgclt '?
elcctropositite
other eleclron
dter curyiLg,
chembal reaclinn.
 FIEDOX HEACTIONS
e13

Oxidation may be deJined as a process in which an

stom or an ion loses one or more ebctront. Thd is

This loss of electrons either iacreases the

positive charge or decreases the negative charge of
the atom or the ion. For example,
other words, oxidation-reduction reactions are
(i)
Loss of electtons resufis in increase
-
tive charge
in posi- complementary ie. , they always go side by side or
'.
hand in hand.This may be iUustraied by th; follow_
Na........* Na+ + e- rng reacttons :

Mg.-. M* + u- 2Mg(s) + oz@) 2Mso(s)

Fe2+ Fe3+ + e- Mg(s) + Fr(g) ...---.- MgFz(s)
.......-
-..
-
Sn2+ Sn4+ + 2e- Mg(s) + CIr@) Mect(s)
Qi) Loss ofelectrons results in decreaseinnega- -...-
tive charge :

MnOo2- """""* MnOa- + e-

[Fe(CN)5f - -----------r [Fe(CN)5]3- + e-
zcl- + cl2+ 2c-
Mg * M* + u-
""-----r (oxidation)

S2- ...........+ S+2e-

lol + b- -....- IoF- Qedttction)
or 02 + 4c- .----- 2trO12-
The overall reaction may be written as follon6:

zMs: + | ii : L -------- 2 [Ms2+: 2-]

ii :

ot 2Me+O2-

Fe3+ + e- ---.-_ Fe2+

2H{+ + 2e- .--. Hd+
sn4+ + 2e- "'- snz+
Mg: + [ ' Cl :1, ----...r Mgl+ [: Cl :-.1,
S+ Ze- _.-...-) Sb3+
(ii) Gain of elecffons
.
tive choqe :
results in ircaose in nega-
Ina
are trans
Cl2 zcl-
+ 2e- other, i.e.
MnO.- * e- -....
.......r MnOl- redox-nactions may be regarded as electron-tansfer
rcactions in which the elec|orc an transfemd
S + 2e- ...- , 52- one reaclant to the orier The substance which loses
[im
[Fc(cN)6f - + e- ..+ tne(o!5f- electron is called a reducing agent while the other
kldation-rcductlotr as an electron.hansfer which accpts the electrons k called an oridking
process. We have discussed above that oxidation agenl T)lns
involves loss of electrons and reduction involves

I
914 NetX Course Chemistrq
Further since, reducing agents donate electons Here, Al rcduces F%()3 to Fe while itself gcts
to other substnacs while oxidising agents accpt oxidised to A[1C)J. Conversely, FerO, oxidises Al
eledrons from other substancqs, lherefore, ruducing
ggents are ele{,,ron donors whik oxidising apt*an toAlrO, whilc itselfgets reduced to Fe. Therefore,
electron accrptors. ln other words, reducing agents Al acls os a reducing agent while FerO, acts os a,t
Xter reducing other substancqs thenselves get oxidising ogent.
oxidised while oxidising agents after oxidising other
substanccs thernselves get rcduced ia the process.
From thc above discussion, we conclude:-
Let us now reconsider the two reactions (be-
tween Mg & O, and Clr) discussed above in the Oxidalion iJ a process in whith one or more
light of reducing and oxidising agenrc. elcctrons ore losl.
In the reaction of Mg with Or, Mg gives Reduction Lr a process in which one or more
electrons qre gainad.
electrons to orygen which gets reduced to 02- ion
while Mg gets oxidised to Mg3+ ion. Conversely, Oxlda[t rJ a substsnce which can sccepl one or
more electrons,
02 accepts electrons from Mg and gets reduced to
Reducant rs d sursrazce which can donale onc or
()2- ion while Mg gets oxidised to Mg3+. There- more elcclrons.
forc, Mg is a reducing agent while O, is an oxidising
agent. Sitnilarty in the reaction of Mg with F, or In a redox reaction, oxidant is reduced by ac-
ceptinq electrcns and rcductant is oidised by losing
Cl2,Mg acts as a reducing agenl while F, or Cl, elcclrot$.
behaves as at oxidising sgent. For further illustra-
tion, consider the following reactions :
Using electrcn trqnsfet idetiily
Oxidised ---------I the oidant snd reductant fu the following redox
(D HzS + 2FeCl3--.-+ 2FeCl2+2HCl+S rcqchon.
(Rctt\cing (Ondising A
agent) a#N) Zn(s) + 1/2 Or(g) --"""'- ZnO (t)
I
I R"du."dJ (N.C.E.R.T.)
Here, HrS reducrs FeCl, to FeCL while itself Solution. Each atom of zinc loses two
gets oxidised to S. Conversely, FeCl, oxidises IlrS electrons to from Zn2+ while each atom of orygen
to S while itself gcts reduced to FeCl2. Therefore, accepts these two electrons to form oxide ion
HrS acts as a reducing agenl while FeC\ acts os sn (O2-) as shown below :

oxidising agent .
[-oxidised--l zr,: +ll:o: ], .-----_ ,r'* [,9,'-]
(ii) Al + F%o3 ......., Al2O3 + 2Fe
(Red!/cin9 (oidisins Thus, Zn acts as reductant (ot reducing agent)
agcnt) n ond orygen scts as an oxidant (oxidising agent).
ogent) |
I p"4u".6____J

Using electron-transfer concept, identiS/ the oddant aDd reductant iD the following redo( reactions.
(o) zn(s) + zlj+(aq) Znz+(aq) + uz@) (N.c.E.R.T.)
-
(6) 2{Fe(CN)6la- (a4 ) + H2O/r,q + 2H+ (oq) EFc(CN)613-(zq) + 2Hz)(dq)
-
(c) 2[Fe(CN)6]3-(44) + 2oH-(4q) + H2o2@q1 2[Fe(CN)6]{-(4q) + 2HzO(O
-
(d) Bto; (aq) + F;,g) + zou- (aq) Bro;(as) + zF-(aq) + H2o(t)
(e) 2NaClO. 1ag) + tz@4) I -
2NaIO3(aq) + cl2G)
REDOX REACTIONS 9/s

oxirlants: (a) H+ (b) H2o2 (c) [Fe(CN)5]3- (0 F, (e) Iz

Reductanls r (a) zn (b) [Fe(cN)614- (c) H2O2 (d) Brot (e) Naclo3

9.4. classilication ol Bedox Reactions':+;irr;:'iil'::i':ii;:i'ii ln this reaction zinc acts a reducing agent and
reduces Cu2+ to Cu metal by transferring two
All the redox reactious may be divided into
electrons.
the following two tyPes :
Thus. durins this redox reaction, zinc gets
oxidiscd to znz+ ions while Cuz+ ions get reduced
,f#:,f,#;;# to coDDer metal. On the basis ofthis redox reaction,
rcactions' For ex-
-- all the'above observations can be easily explained :
'anple, -
(i) Since zinc is being oxidised to Zn2+ ions
(i) Displacement ofcopper from CuSOo solu-
which go into solution, therefore, zinc rod starts
tion when a zinc rod is diPPed in it. dissolving.
(fi) Reduction of HgCl, to HgrCl, by SnClr' (ii) Since each Cu2+ ion accepts two electrons
(b) Inrlirect redox reactlots. Redox reactions lost bv zinc. therefore, Cu2+ ions are reduccd to
in whiih oidation and. reduction take Place in dif' copper metal which, in turn, settles down at the
ferent vesseh sre called indirtct redox rcactions' bottom of the beaker'
hhese hdirect rertox reactions form the basis of MathematicallY,
clectrochemical cells' Loss in wt. of zinc rod Eq. wt. 9f zinc
Wt. of copper deposited
- Eq. wt' of copper
9.5. Direcl Redox Reactions-Oxidation'
Reduclion Reactions in I Beaker "i:iir'+r:iiir'il:;ii1'iriilili 325
31.75
'fake a zinc rod and clean it well with a sand
(ir'i) Since the Cu2+ ions are reduced to cop-
paper.Now sulPhate
inibeaker A sPon- ner metil. the blue colour of the solution which is
taneous rea changes iue to Cu2+ ions slowly starts fading.
would be observed. sofits own,
(i) Zinc rod grailually stuns dissoling' is
it and hence
(ii\ Copper metal either sta,ls setlling st the AG therwords,
a certain amount of energy must be released in the
bouom of thi beaker or deposilinSon lhe zinc rod'
reaction which appears asheat and hence the solu-
(iii) The blue colow oI lhe solution star.tt lading' tion becomes hot.
(iv) The reaction is *othermic s,td the solution
(v) Since each Zn atom loses two electrons and
becomes hol. ea"h du2* ion accepts two electrons, therefore, the
(v) The solution remains electricolly neutral number of eleclrons lost in the oxidation half reaction
througJlout. i-s equal to the number of electrons gained in the
Let us try to explain these observations : reduciion half reaction. As a result, the solution
In aqueous solution, CuSOn dissociates to remains electrically neutral throughout

form Cu2+(aq) and SO!-(aq). When zinc rod is Simitarly, when a copper rod is placed in a
solution ofsilver nitrate in abeaker, we observe that
dipped in CuSOo solution, the following redox the solution againDeco
reaction occurs :
dissolving. This is apP
oxidation (loss of 2z-) solution which was
f 1 chansins to blue due to thc oxidation of Cu to
zi1s1 + cuz* 1aq1 --- Zn2+ 1a,.)+Ctt1s1 Cu2+"io;. At the same time, Ag+ ions get reduced
t' to silver metal which in turn, settles down at the
LR"ao"tion (sainof?z-) _J bottom of the beaker [Fig. 9.1 (b)1. The overall
redox reaction may be written as follows :
 9/6 Neq' Conrse Chenr istrq
Oxidation (loss of tu-)1 than rut ol Cuwhile electron donating ability of Cu
;- is mole ths.n lhat o[ Ag.
Cu(;) + 2Ag+(aq) ......._ Cu2+(aq) + Ag(s)
I R",lu"tio, (sain of k-) J "(i')
A large numbcr of redox reactions occur in

cu2* toNS Ag+ toNs

IN WATER IN WATEB

sum of two half rea ctiols one involving oxidation

-
called oxidationhalfrEscflon and the other involv_
ing reduclion usually called rcductionhalf rcacdon.
To explain these half reactions, Iet us consider the
oxidation of aqueous potassium iodide byhydrogen
--! peroxide. This reaction can be divided into'lhe
lollowing two half reactions :

FINE PARTICLES FINE PARTICLES

2t' (aq) .----+ ze- @xidation)
t2 (s) +
OF COPPER MEIAL OF SILVER METAL HrO, (aq) + 2 e- ......- Z OH- (aq) (reduction)

FIGUBF;9.I.
'|,,
(a) Znc dirsolves to form Zn2r iors
wh.ite Cuz+ ions geI reduced to copf,er metal lrfiich
setflrs down in torm of finc padides at the hottom
of the heaker.
(b) Copper dissdves to form Cu2+ ions while Ao+
iors get reduced to silver mptal whicn sc-tties ao',in
tn lorm ol ,ine particles at the bottom of the beakpr.
tions arc simply added if
. In this reaction. copper acts as a reduces agenl
and reduces Ag+ l.o Ag mel.al by transferring-two
ost during oxidation are
electrons gained dluring
electrons-
2r- (aq) .-----t l2(s) + ze- @xidation)
HrO. (aq) + 2e- ......., 2 OH- eeduction)

Ovemll redor reaclion :

2 I- (aq) + HrO, (aq) .......' Iz (s) + Z OIl,- (aq)
This represents the net balanced ionic egua-
Thus, we conclude that oidation-reduction -
tion.
arc conplementary processes, i-e., one cannot occur
Suppllog the required number of spectator
occurs simu oneously. In oher -
ions, the balanced redox equation is
t i; oidised ot the expense of the :

ced. zKl (aq) + H7O2 @q) ------+ I, g) + ZKOH (aq)

It
may be mentioned here that the role of a
substance to act as an electron donor or an electron but
n oxidant spe
donating K+
in Eq. (i), (ir) If the number of electrons lost during
reversed. .
oxidation halfreaction are different from the numf
duction half reac-
re multiplied by
two equations are
of the final redox
AEDOX HEACTIONS 9n

equation. For example, cossider the oxidation of Overall redox equation :

aqueous lerrous sulphate to ferric sulphate by crro2l- @q) + 3 so2 G) + 2 H+ (aq) '------
aqueous acidified KMnOa solution.
(aq) + 3 SOl- @q) +Hro (t)
2cf+
MnOo- (ag) + 8H+ (4q) + 5e-
Supplying the required sPectator ions, wc
t'/:n2+ (aq) + 4 HrO (/) (reductio ) have
Fez+ (aq) Fe3+ (aq) + e-l x 5 KzCrzOl @q) + 3 SO2 G) + H2SOa (aq)
-- (oidatiou) -
KrSOo (aq) + Crr(SO), (aq) + H2O o
(v\ Reduction of nrcrcuic chloide to mer-
Overall redu reaction: curous chloide by slannous chloide.
l/lrtoa @Q + 5 Fe2+ (sq) + 8 H+ (4q) Sn2+ (aq)------- Sna+ (aq) + 2e- (oidotion)
. Mn2+ (aq) + 5 Fe3+ (oq + aHzo (q Ht* @q) + e- I Hg+ (oq)l x z
Supplying the required spectator iotrs, the Qcduction)
complete balanced redox equation is
KMnoa (aq)+5 FeSOa (aq)+4 H2SOa (ag) --'- Overoll rcdox reaction :

MnSO4 (4q) + 5/2Fer(SO), (aq) + 4 H2SO. (l) Sn2+ (a41 + zHe+ @d--,
Sna+ (aq) + zIJg+ (aq)
To eliminate fractional numberg multiply the
entire equation by 2. We have, Suppllng the required spectator ions, we
have
2 KMnOa(aq)+ 10 FcSO4(aq) +8 H2SO{aq)
+ 5 Fe2(SO.), (aq) + - (0
H2o
SnCl2 (aq) + ZHgCl2 @d
2 MnSOn (o4) 8
-
SnCIo (aq) + Hg2Cl2 (r)
For further illustration, consider the following
equations :
(vi) Self oxidation redl.ction oI Clzin prcsence

Qii) Ondafion of sodium thiosulPhate to of alkali

sodiun letrathionste by aqueous iodine Cl2 @) + Ze- , 2 Cl- (aq)l x 5
2 sroS- (a{) ""'- s .cl|' @q) + 2 e- (reduction)
(oxidation) Clz @) + tZ OH- (aq)
l, (aq) + 2 e- '------t 2l- (oq) Qeduction)
-
2 ClO, (aq) + 6 HrO (l) + 10 e -
(oxidation)
Overqll red(N rcactio,t I

2Srol- @fl+r2@q) -..-. sro?- @q)+?r- (aq) eqution :

Overall redox
Supplying the required number of sPectator 6Ct2@Q + 12 oH- (uq)
ions, the balanced redox equatio is -,
ro Ct' (aq) + 2 CIO; (aq) + 6 Hro (t)
z NarS2O3 (a4) + lz@q)
- NarSoO, (aq) + 2 Nal (aq)
To remove the common factor, divide the en-
tire equation by 2. We have,
(iv) Reduction of acidified potassium
3 Cl, G) + 6 oH- (aq)
dichronrule by sulphur dioxide.
-
Crrol- @q) + t4 H+ (qq) + 6 e- '------, Cl- (aq) + ClO, (aq) + 3 HrO (/)
5

2 CS+ (aq) + 7 },,zo (t) (oidation) Supplying the required spectator ions, we
have,
so2 G) + 2ld2o (t) ---) 3cl2@) + KoH (aq) ....t
6
Sol- (aq) + 4H+ + Ze-lx3 (reduction)
s Kcl (aq) + Kclot (aq) + 3 Hro (t)
 9/8 Neur Course Che nt i stry

FORiP.KA,efflep r,:
following redox 2. Split the tollowing redox reactions irl the oxidarion
and rcduction half reaclions.
(a) Fez+ (aq)+2t- (oq)- 2Fe2+ (otD+tz@q) (a) 2K (r) + ctz@) ......- 2Kcr (r)
(b) Zn (r) + 2H+ (04)- Znz+ (aq) + HzG!) (b) 2N (t) + 3Cu2+ 1aq1

(c) Al (r) + 3eg+ 1ag1- AP + 1a4; + :ag 1r;

- 2Al3+ (aq) + 3Cu (j)
(NC.E.R.T) (NC.E.R.T.)

l. 1o1Zt- 1oq1-12@q)+zc- Al (,r) + 3As+ (aq) Al3+ @O + 3^EO)

...oxidation
Fe3+ 1aq; + Fe?+ 1aq1[x z ,.Reduction - ...Overa ll realox rcac t ion
"- 2' K
- 1r) .......- K+ 19; + e- [x z ...oxidqtion
2Fe3+ 1aq1 + 2l- (aq) 2]r.:e2+ 1aq1 + trlaqy Clz@)+2e- + zct- (g ..Reduction
- ...Overo ll re drx teac tion K+ (g) + cl- (g) Kcl (,t) [x 2
(h) Ztt (t) Ztt2+ (aq) + 2 e- ...(Xidotion -
- +
2H+ (aq) 2 c- .+ Hz (g) ..Reduction
2K (r) + ct2 G) 2KCl (r)
- ...Overa U redox re a c lion
(D) Al (r) .- A3+ c- Ix 2...Oridation
z^(s)+zH+ (04) + tu?+@ + HzG; @q) + 1

...Overull redta re ac t ion

Cu7+ 1aq1+ 2e-+ Cu (r)[ x 3 ..Reduction

(c) Al (r) ..* 1.tt+ 1oq1 + t ...Oxidation

"- 2Al (.r) + 3cu2+ (aq) 2N3+ G) + 3Cu (r)
Ag+ (aq'1+ c- '-Ag(r)lx3 ..Reduction
- ...O verall redox re ac ti on

9.7. Oxidalion Number

chlorine atom. Yet in HCI molecule, Cl atom has
As already discussed, oxidation-reduction us there is a partial
reactions involve the transfer ofelectrons from one from hydrogen to
atom or ion to the other. In case ofionic reactions, can easily say that
it is very easy to determine the total rumber of lorine is an oxidant.
electrons trausferred from one atom or ion to the Similarly, in the reaction,
other. However, in many redox reactions involving cH4 G) + 4F2 @)--+ CF4 G) + 4HF G)
covalent compounds, it is not so easy to determine
CH. acts as a reducing agent and F2 acts as an
(r) direction of transfer ofelectrons and (r'i) number
oxidising agent. With a view to identiry oxidant and
of electrons transferred from one reactant to the
reductant by keeping track of number of electrons
other simply by looking at the chemical equations.
transferred from ono reactart to the other both in
For example, in the following redox reaction,
ionic and covalent compounds, and to help in
H, G) + ct G)*zHctG) balaacing of equations, the concept of oxidation
both the reactants and thc products are covalent number was introduced. Thus,
compounds. From our knowledge of chemical
bonding, we know that during the formation ofHCl
molecule, an electron pair is shared between
hydrogen and chlorine atoms and that electron is
not completely transferred from hydrogen to
 REDOX REACTIONS
9.7.1. Rules for asslgning Oxidation Num-
bers.
The following rules are applied to determine
the oxidation number of an atom in an ion or
molecule.
l, The dcidalion number of all lhe atoms of
dfurent elenVnts in thei respective eiementary slales
and allotropic forms is taken to be zero. For example,
in Nr, Clr, Hr, He, Pa,56, 02, 03, C (diamond
or graphite), Br, , Na , Fe , Ag etc., the oxidation
number of each atom is zero.
2. The oidation rumber oI a nnnootomic ion
is the sa,ne ds lhe clntge on it. For example, oxida-
tion numbers of Na+, Mg3+ and Al3+ ions are * 1,
+2 and +3 respectively while those of Cl-, S2-
and N3- ions are -1, -2ar,d -3 respectively.
3. The oxidation number ol htdngea is -+ I
when conbined with on-melols snd is I when - or an ion. Metals invariably have positive oxidation
cbnibined wiih active mitaE calted mefiffri,ilrides
nat as Lin, KH,Wgryr; eary'e-tc.
" 4. The oidation number of otygen is -2 in
most of ils compounds, ercept in peraxides like
' HrO, BtiOretc. where it is L .Another interest-
, -
ing'exception is found in the compound OF,
(orygen difluonde) where the oxidation number of
orygen is +2. This is due to the fact that fluorine
being the most electronegative element known ha-s
always an oxidation number of - I.
5. In compounds Iormed by union oI metak
with non-metals, lhe metol atoms will have positive
oidalion numben and the non-metals will have
negolive oidation nurzbers. For example,
(a) The oxidotion number of alkali metals (Li,
N4 K etc.) is always + 1 ar 7 those of alkaline eaah
ntetals (Be, M& Ca etc) is + 2.
(b) The oxidation number of hologens (f;, Cl,
Bt; I) k ulways - I in metat halides such as KE
AlCl, MgBr, Cdlr. etc.
6. In compounds formed by the union of dif-
ferent elemenls, lhe more elecEonegative otom will
have negalive oidation rutmber whereas the less
electronegotive qnm will have poitive oxidation
numben For exzmple,
(a) N is given an oddation number of -3
when it is bonded to less electronegative atomasin
NH, ard NIr, but is givcn an oxidation number of
+3 when it is bonded to more electronegative
atoms as in NCl3.
9i9
(D) Since fluorine is the most electronegative
element known so its oxidation number is always
- L in its compounds i.e. oxides, interhalogen com-
a pounds etc.
(c) In interhalogen compounds of I Cl, Br,
and I ; themore electronegative ofthe two halogens
gets the oxidation number of 1. For example, in
-
IF7, the oxidation number of F is 1 while that of
-
Iis + 7. Similarly, in BrClr, the oxidation number
of Cl is - 1 while that of Br is + 3.
7. In neutral compoun^, the sum olthe Nida-
lion numben of all lhe aloms is zem.
E. In comples ions, the sum of tlrc oidation
numbe$ of qll the atoms in the ion is equal to the
cho,ge on the ion.
With the help of above rules, we can lind out
the oxidation number ofany elenent in a molccule
numbers while non-metals may have positive or
negative oxidation numbers. Tlalsition metals
usually display several oxidation numbers. The
highest positive oxidation number for s-block ele-
ments is equal to its group number but forp-block
elements it is equal to group number min*s l0
(except for noble gases). However, the highest
negative oxidation number forp-block elements is
equal to eight nrinzs the number ofelectrons in the
valence shell. In other words, the highest positive
oxidation state increases across a period in the
periodic table. For example, in the third period, the
highest positive oxidation number increases from
+ I to + 7 as shown below :
Na+ (+1), Mg2+ (+2), Al3+ (+3), si (+4 as
in SiCl., SiO, etc.), P ( + 5 as in PF5 , PaO,o etc.), S
( + 6 as in SF6, SO3 etc.) and Cl ( + 7 as in ClO, or
CIO.- ion).
As stated above oxidation numbers are also
called oxidation states. For example, in HrO, the
oxidation number and oxidation state of hydrogen
is + l while that of oxygen is -2.
We shall now illustrate the use of above rules
in determining the oxidation numbers and also for
identi$ing the reductants and oxidants in redox
reactions.
l,lx-{i\l PLtt 9.2. Calculs,e the uidation num-
ber of (i) S in HrS, (ii) C in CO, (iii) C in CHzClz,
(iv) N in (NH).SO|, ft) Pb in PbrOrand (vi) P in
NarPOo.
L
9/10 : ,., . Neto Coursc Chemistrqlft[)
Solutio!, (i) S in HrS. Lct the oxidation /r+r\ -z
numbcr of S in H2S be x. Writing the oxidation (N n. J, so.
number of each atom abovc its symbol, (. Oxidation numbe r of SOI- is -2)
+l .r . . Sum of oxidation numbcrs of all thc atoms
Hzs in (NHo), SOo
(.
Oxidation number of H is +1)
= 2x+2(+ I x4)+(-2)= 2x+O
Sum ofoxidation numbers ofvarious atoms in But the sum of oxidation numbers of all thc
H,S atoms in (NHa)rSO n (neutral) is zero (Rule 7).
= 2(+1)+x= 2+x .. 2x+ 6= 0or.r= -3.
But the sum of the oxidation numbers of Thus the oidation nunber of nittogerr irt
various atoms in H 25 (neutol) is zero (Rule 7). (NHo), SOo is -3
-'. 2+x = 0 or .t= -2 , (v) Pb ln Pb3O.. Let the oxidation number of
Thus tlrc oidotion ttumber of S in HrS is -2. Pb in PbrOo be .r. Writing the oxidation number of
n (il) C in CO2. Let the oxidation number of C each atom above its symbol
in CO, be .r. Writing the oxidation number of each x-2
atom above its symbol, Pb: 04
x -2 ( . oxidation
number of O is - 2)
coz .'. Sum of the oxidation numbers of all thc
( .' Oxidation number of O is 2) atoms in PbrOo
-
.'. Sum of the oxidation numbers o[ various . = (3).r+ ae4= 3v-s
atomsin CO2 =x+2(-Z)= x-+ But the sum of oxidation numbers of all the
But the sum of oxidation numbers oi various atoms in PbrO, (neutral) is zero (Rule7).
atoms in CO, (neural) is zero (Rul 7). .. 3-r-8=0or -r=8/3
:. x-4= 0 or r= + 4 Thus the oxidotion number ol Pb itt PbsOo :
ThL.s the oxidqlion number ol C in Cozis + 4 E t3.

r (iii) C in CH2CI2.Let the oxidationnumber of (vi) P in NarPOo. Let the oxidation number of
C in CHrCl, bex. Writing the oxidation number of P in NarPO. be.r. Writing the oxidation number of
cach atom above its symbol, each atom above its symbol,
r +l -l +1 r -2
c H2 cl2 Na, P On

(. Oxidation number of H is +1and ( . Oxidation number of Na is + 1 and that of ()

that of Cl is - 1) is -2)
..
Sum of the oxidation numbers of various Sum of the oxidation numbers of various
atoms in Na3POa
atoms in CHrCl, = x + 2(+ 1) + 2(- 1) = r
But the sum of the oxidation numbers of = 3(+1)+r+4(-2)=*-s
But the sum of oxidation numbers of all the
va r io u s atoms in CHrCl, (neutra l) rs zero (Ru le 7) . atoms in NarPO. (neutral) in zero (Rule 7).
.. -r=0 .. -r- 5=0or r= +5
Thus, the oxidatton rumber of C in CH2CI2 is Tllus the oxidation tumber of P in NarPO. t-t

zer(t +5
r (iv) N in (NH.)2SO.. Let the oxidation num- ) \i 1t\u,!.1' ,t t. Calculate the oxidation num-
ber of nitrogen in (NHo)rSOo be x. Writing the o!
ber
oxidation number ofhydrogen above its symbol and (i) N itt NOt ; (ir) P in H3P2O; (iii) C i,t
that of SOI- ion above its formula. Col-, @) Cl in Ctoo antl (v) Crin C4ol-.
 REDOX HEACTIONS 9/1 1

(i) N in NOl. Let the oxidation t-2

number of N in NOI be.r. Writing the oxidation
cl o1

number of each atom above its symbol.

.'. Sum of oidation number o[ all the atoms
r-2 in (ilr), ion : r + 4(- 2) = ,r - g
Nor But the sum of oxidation numbers of all the
.'. Sum of the oxidation number of all the atoms in ClOo ion is equal to the charge present
atoms in NOr- ion = .r * 3(- Z) = x - 6 on it, i.e., I (Rule ll)
-
But the sum of oxidation numbers of all the
..x-8=-1 or x-+7
atoos in NOr- ion is equal (o the charge present on Thus the oxidation number of Cl in ClOo is
it, r'.e.
- 1 (Rule E) +7
.'. r-6= -lorx= *5 , (y) Cr in Crrof-. Let the
oxidation number
Thus he oxidation number of N inNOl is +5 of Cr in CrrOl- bex. Writing the oxidation number
(lI) P ln HrPrOr- . Let the oxidation number of of each atom above its syrnbol.
,_2
P in HrPrOr- be.t. Writing the oxidation number of cr.- o,
each atom above its symbol.
+l ,-2 .. Sum of the oxidation numbcrs of all the
H3 P2 ()7 atoms in CrrOl-ion = 2(x)+7(-2)=la- 14

(. Oxidation number ofH is + 1 and But the sum of oxidation numbers of all the
that of O is atoms in CrrO]- is equal to the charge on it, i.e.,
-2) 2 (Rule E)
Sum ofthe oxidation numbcrs ofall the atoms -
in HrPrOr- .. 2x-74= 2 or x= 6
nus he oxidation,rumber of Crin CrrOl- ion
=+1 x 3 + 2(x.) +7(-z)or 2x-17
But the sum of oxidation numbers of all thc i.v *6
atoms in H3Pz 07- is equal to the charge present on
* tlXANfi'Lll9.1. Whatis the the oxidqtion num-
b;et bf nrctals in (i) lFe(cll)5la- ond (ii) Mno; ?
it i.e. - 1 (Rule 8)
-. 2x- 11 =-1 orx= +5 (i)
Fe in [Fe(CN)6]'-. Let the
Tltus tlrc oxidqtiort number of P in H3P2O7 ,s oxidation number of Fe in [Fe(CN)ula- bex. Writ-
+5 ing the oxidation number of each atom above its
(iii) C in COI-. Let the oxidation number of synnbol and that of cyanide ion above its formula,

C in COI- be.r. Writing the oxidation number of

we get
r -1 , eL'l'
each atom above its symbol, Fe (CN)6
t-2
c()3 .'. Sum of oxidation numbers of all the atoms

..
in [Fe(CN)5la- = .r + 6(- L) = x e -
Sum of the oxidation numbers of all thc
atomsinCO]- ion = r+ 3(-Z)= x-6 But the sum of oxidation numbers of all the
tl atoms in Fe(CN).la- is equal to -4. (Rulc E)

luu
lal
atoms in
But the sum of oxidation numbers of all the
COI- ion is -2 (Rule 8)
:. x-6: -4
Thus the oidation number
or x=12
ol Fe in
l-+ .'. x- 6: -2
IFe(CN)51'- r:r + 2.
or x= * 4 (ii) Mn in MnOt. Let the oxidation number
nrus he oxidotion stqte of Cin COrz- rl +4
of Mn in MnOn- be r. Writing oxidation number of
t (lv) Cl in ClOa. Let thc oxidation number ol'
each atom above its symbol, we get
Cl irr CIO; ber. Writing he oxidation numbers o[
each atom above its syrnbol, Mn o4
 9112 Ner4 Couyse Chemistrq
.'. Sum of the oxidation numbers of all the .. x-8 = -l
atoms in MnOo- = x+4(- 2)=x-8 or x= +7
But the sum of oxidation numbers of all the nlus, the oidqtion number ol Mrt inMnOo is
atoms in MnOl- is - 1 (Rule t) +7

iir,1E l.tri,$f#rs*sf",Ei,ti+8",*+tlii4s,,I0.J1i.-+sEHf.*.+.rt1ij1rt++ils1.,+;i:,ifl1:.1itijiti,+ili:i:ilti:i:i:il i:tJ\.t .

;h. D.,-'"T,:.Q' ,IJ."..R.K'N t

l. The o.N. of c in its \rarious compounds containing only H and o atoms cn be qsily-calculated by the
application of thc following formula : ,H ( l) + noe 2) + n. (O.N. of C) =0 or O.N. of C =
no(2) - nHO)
nc
where rH , n0 and zc are the number of H, O and C atoms in the given compound. For emmplo,

Compound ,IH ,to r,C (2) -'x (l)

6.tr1o1g - "o nc
cHl 4 0 1 o(2)-4(1)/1=-4
9Ho 6 0 oQ)-6(1)/2=-3
QHr 4 c ) o(2)-4(1)/2*-2
cH3oH 4 1 1 1(2)-4(1)/1--2
9Hz 1 0 , o (2) - 2(7)/2 = - 1
cH2o ) I I t(2)-2(1)/1=O
HCOOH ) ,,
I 2 Q\ - 2(1't/1= + 2
r:i l. Ifa comPouDd cootains two or more atoms ofthe same element, the O.N. determined by the application of
the ab@e rules is oDly an average of the o.N. ofall the aroms present io the molecule. f6r exaniite, o.N. of
Fe iD F%oa (magnetic qide of iron) is 3x+ 4x -z-o or x= +8/3. similarry, in ferrifirrocyanide,
Fe4 [Fe(CN)6]3 molccule tho average O.N. ofFe is 7r+l8x-l=0 o( x=18/.1.
The aclual c0ddation numbers of indMdual atoms crn, horet/er, be determiDed if the stoich iometry or the structu re
of the compound is kno$m as disqrsed uDder Additional Useful Infonnation
for Cornptitive Ex;nination.

FaRiP- I],CE
l. "RA?LEMS
Find the o(idatim number of the elemcnt in bold
iD the follo$dng species :
5, Find out the cxidation number of sulphur in the
following species :

O SiHl, BH3, BF3, SrO!- BrO.- and HrOo2- (NH4hsol, H2so1, s2o42-, szo?-, Hso3- and
(N.C.E.R.T.)
r{so;. (N.c.E.R.T.)
(u) Pbso4, u2or-, B.o?-, crol-, rqMno..
2. Determine lhc midation numberof 6. Dctermine the oddation number of all the atoms
C in the fo ow-
ing :
in thc following well known Gidants
KMnO., KrCrrO, and KClOn.
qH6, ClHlo, CO, CO2 and HCOt. (N C.E R.I; N-C.E.f.T.)
7. DetormiDe the change in the oddation Dumber of
3. Detetmine the oddatioo number of O in the fol- S in H2S and SO2 in the following industrial reac-
lo iog :
tion :
oF2, Na2o2 and CH3cooH. (N.C.E.R.T.)
4. Find out the crddationoumber of CIio HCl, HCIO,
2H2S G) + so2 G)- 35 (s) + 2HzO (J)
(N.C.E.P.T.)
CIO;, CaOCl2 aDd Cl02. (N.C.E.R.T.)
 REDOX REACTIONS
9113

EI<S
1. (,) si = - 4 insiHo, n = - : in n{ I *1,,* 4. O.N. of CI =-linHCt,+linHCIO+7in
BF3,S = a 2inS2O3-, Br = + 7in BrO; and ClOt in CaOCt2 and + 4 in CIOz.
p=+5inHpo?-,
5. O.N. of S = + 6 in (N I I4)2SO4, I,I2SO4 and
0i)S = + 6inPbSOa, U = + 5ioU2Or-, B = + HSoo and SrO?-, + 4 in HSO3- and + 3 in
3 iD B4O?-, Cr = + 6 in CrO?- and MD
= + 6 ir szol-.
K2MnOa.
2. O.N. of C = - 3 in
eHe, -2.5 in C4Hr0, + 2in 6. K= + 1,Mn = + 1,O = -Z;K= + l,Cr=+ 6,
CO, + 4 iD CO2 and + 4 in HCO'.
O= -Z;X= '1,
+ Ct = + 7,O = -2.
3. O.N. of O = + Z io OF2, - 1 iD NEO2 aod _ 2 7. O.N. of S changes from - 2 in II2S and + 4 in
in CI{rCOOH. SO2 to zcro in elentental sulphur.

e.u Hedox Heactions in Terms Here, the oxidation number of iodine in-
creases from _ 1 to 0, es
from 0 to _l while tha n_
changed. Therefore,Ill is
In terms of oxidation number, teduced to Cl- ions.
C)xidatio
in which
1-Oxidised--1
+4-200+3
(l)3Mn Or+4Al -2
number of an a,om or alom^s while reduction mo, .-..........,3 Mn + 2AIz o3
be defined as a chemicsl chtnge in vhich theie I R.du""d 1
occurs a decrease in thc oxidstion number o! at
altm or stons. A redox reflclion mcy then he
dgfined as a reoction in which the oxilutiin nunher
oJatomt undergox a change.
For cxample, considcr the rcaction bctwecn AlzoT
zinc and hydrochloric acid. Writing the oxidation
numbcr o[ all the atoms above thcir respcctive f-Reduced ------f
sl.rnbols, we have,
Oxidise -----l (iii)2ilo21*rogl * r#-z ri'n*s 3q*s Hr-o'
f- d
I
0 +1 -l 2+ -1 0 o*iai""a_J'
Zn(s) + 2H Cl ---+ Zn Cl2 +Hz In this reaction, thc oxidation number ofman_
LReduced +' ganese dec +2 in
Mn2+ ions, _l in
Cl- ion to n and
hydrogen remain unchanged . Therefore, MnOl is
Cl- is oxidised.
reduced while

For further illustration, consider the following _ 93?: O:ddising and Reduclng agents in
examples. terms of Oddatlon Number

+'t -1
,-- Oxidisedl
0 0 +l _l
(i) 2H I+Cl2-Ir(s)+2H Ci
I R"do"".t t
 Pradeep's
9114

F-o.N. increases ---J

ox
An Dt maY be
dejnbd as number of -2+5+20
HzS +HNO3 N^O + S +H2O
wlrcse atom
examPles, i'e , (i) to
' L u^. a""."rr".J
(irr), chlorine decrcases Here, the oxidation number of S increases
i.; that ofmanaganese from -2 in H2S to 0 in elemental sulphur, while that
decreases from +4 in MnO2 to O in Mn ; that
of
of N decreases from +5 in HNO, to +2 in NO,
manganese decreases from +TinMnOato
+2in lheref.ore,HrS is a reducing agent while HNOrin on
Mnz+ ion. Therefore, oll the lhree, Le" Cl2 ' oxidising a4ent .
MnOratd MnOl are oidising agents or oidsnts ' . l,lx.Al\ I Pl-I, 9.5. 1de ntify th e oxi dant and re duc'
Similarlv. the oxidation number of N decreases tant in the followin9 reactions :
rr;. ij in KNo, to +3 in KNo2, therefore, (a) 10H+ (oq) + 4Zn (s) + No; (aq)-'
KNO, is an oxidising agent. 4Zn1+ (aq) + NHI @d + 3H2o (t)
(b) Ir(s) + HS @)"""'> zHI (s) + s (s).
decrea.". a. (N.C.E.R.T,)
*f-O.N. (a) Writing the o.N of all the
2KNO3 zKN 02
atoms above their sYmbols, we have
+t 0 +5
Likewisc, KCIO3 is an oridising agent since 10H+ (aq) + 4Zn (s) + No. (cq)
-*
the oxidation of Cl decreascs from + 5 in KCIO3 to +2 -3 +t -2
- 1 in Cl- ion. 4Z*+ (oq) + NHl+ (4q) + 3HrO o
Thus, there is no change in the O N' ofH and
r o.N. decreases --1 O-atoms. O.N. of Zn changes lrom zero in Zn to
+2hZr]+ awl,therefore, it is oxidised and hence
2KClOr 2KCl + 3O2 Zn tcts ss a reductanl.
The O.N. of N decreases from + 5 in NOt to
Therefore, KCIO, ako ocs on oxidising agent -3 in NHf, and, therefore, it is reduccd and hence
Reduclng agcDts or
NO; acts as lhe oxidqnl.

ing agents are electron (b) Writing the O.N. of all thc atoms above
electrons causes a corre their symbols, wc havc,
oxidation number, therefore, according to the 0 +l-2 +l-1 0

12 G) + H2S (9 zHt (g) + S (s)

oxidation number coocePt' -'
Here O.N. of H does not change' The O N of
I, decreases from zero in I, to - 1 in HI, therefore,
I, is reduced atd lrcnce it acls os an oxidant 'fhe
O.N. of S increases from -2 in HrS to zero in S,
qcts qs tlrc
therefore, HzS is oxidiscd and hence it
rcductsnt,
At to +3 in A!O, and that of chlorine increases
9.9. Disiinction between Valency
from - 1 in Cl- ion to 0 in Clr' Therefore, all the and Oxidation Number
three, i.e., HI, Al and Cl- ion are reducing agents '
The term oxidation number and valency
F\rttrer consider the following redox reaction be- meanings as discussed below :
have different
tween HzS and HNO3.
 REDOX REACTIONS
9/1 5

Valency Oxidation Number

l. Valency is the combining capacity of an elemcnt. l. Oxidation num&r is the charge which an atom has or
It iS defined as the number of hydrogen atoms or appears to have when present in the combined state.
double the number of orygen atoms with which
an atom of the element conrbines.
, Valency is only a nunrber. As such it does Dot have ,
attached to it. For example, in
of oxy,gen is two and that of,
I

3. ent caDDnot bezero. I

I

3.

4. 4.

6. 6.

9.10. Oxidation Number ar

oxidation number of of copper is + 1 while that in
The compounds of metals which show more CuO, it is *2. Therefore, these two oxi<Ies are
distinguished as Cq(I)O and Cu(II)O oxide
respectively. This system of nomenclature was in-
troduced byStock and is commonlyknown as Stock
notation after his name. As an illustration, consider
the stock notations for the following compounds :

Formula and chemicnl nnme o[the compounrl

CurClr, Cuprous chloride Cur(I)Cl,

CuClr, Cupric chloride
Cu(II)Cl,
FeSOo, Ferrous sulphate
FeIII;SOo
FerlS04)3, Ferric sulphate
Fe2(III)(SOd3
CrrOr, Chron:iuin trioxide
C12(III)03
NarCrOo, Soclium chromate
NarCr(VI)Oo
VrO, Vanacliun: pentoxirle
v2(v)os
IlCr rO r, Potassiu m dichromate IQCr(vrl)o,
MnrOr, Man ganese heptoxicle
Mn(VII)O,
9/16
,. t, r's Nes, Course Chemist'Cfiiil)
Step 7. Ia ca-se of ionlc rcactions,
(a) For acidic medhtm. First balance O aloms
by adiing HrO molecules to whotever side deficienl
in O atoms nnd then balonce H atoms by odding
of +3 and +5 respec-
ohorous in oxidation state H+ ions to whatever side defrcient in H atoms'
iluitv ut" by names only, ie',
distinguished (D) For baslc medllum. Fint balance O aton$
phoiphorus trichoride and phosphorus pen- by adding HrO molecules to h'hateeer side deftcient
lachloride resPectivelY' in O atoms The H amms are then balanced by
adding HrO molecules equdl in number to the
deficienq of H atoms and an equal nyyUel 9l
OA- iins are added lo the opposile side oI the
equation. Remove the iluPlication' iI arty'
These rules are illustrated by the following
examples.
Fl IPLE 9.6' Balance the equstion,
Ms(aq)+ HNot@q) *
(i) Hit and Tnal Method
Ms(Not)r(aq)+ NrO @)+ H2o (t)
(ii) Partial Equation Method
l. Find out the elements which
However
oxidation and tot oxidation number (O'N')
more easilybe
ing two methods \ /,/ O.N. increases bY 2 Per Mg atom
l. Oxidation bhmber Method t-------------l
b +t+s-z +i +s-z +l-2 +l-2
tJ{rlon-Electron Method or Half EEtation
Me tod Mg + HNO, ...* Mg(N Os)z + N2O + H2O
l. Oxldatlon Number Method (')
The various steps involved in the balancing of
rerlox equations by oxidation number method are : Per N atom
O.N' decreases bY 4
Step l. Wite the skeletal equation ol all the Here, O.N. of Mg increases from 0 in Mg
reactanls and products ol the reaction' metal to +2 in Mg(NO3)2 and that of N decreases
Step 2. Indicate the oxid
from + 5 in HNO3 to + 1 in NzO.
element above its symbol and
which undergo a change in t Saep2, Find out the to,al incrcase and detease
(o.N). in o'N'
either side
of N' of Mg is
2. in NrO on
R.H.S. and onty one in HNOron L'H'S' of Eq' (i),
therefore, multiply HNO, on L.H.S. of Eq (i) by 2

undergoing that change.

and thus the total decrease in O N' of N is
2x4=8.
e formuloe ol the uidising
bY suitable intwn so as to Step 3. Bolance in
se ot decrease in oxidalion Since the total increase in
stP 3. 8, therefore, multiPlY Mg
lha H and O' and 3, we have,
Step 5. Balance all atoms other
4 Mg (s) + 2 HNo3 (aq) "-"'
Step 6. Frnal/y bolance H dnd O atoms by
adding Ii ,O moleciles uing hit arul trial method' Mg(No), (aa) + N2o G) + H2o O "('D
 REDOX REACTIONS
9l't7
other than O and H. Step 3. Calculate the totsl irrcreaseldecresse i,t
of Eq. (i), mulriply O.ll Since there is only one Fe atom on either side
of Eq. (i), therefore, total increase in O.N. of Fe is
4 Mg (s) + 2 HNo3 (aq)......- 1. Further since there are two Cr atorl's h CrrOl-

4 Mg(NOr), (ag) + NrO G) + HrO (D ..(r,, on L.H.S. of Eq. (i) but onlyone in Ct'+, the refore,
mulriply CP+ on R.H.S. ofEq. (r) by 2 an<l thus the
oms on R.H.S. total decrease in O.N. of Cr is 2 x 3 = 6
, therefore, to Step 4. Balance increqseldecrease in O.N.
cient of HNO3
Since total increase in O.N. is 1 and decrease
of Eq. (ir), we is 6, therefore, multiply Fe2+ by6. Combining sreps
have, 2 and 3, we have,
4 Mg (.r) + 10 HNo3 (aq) ......- crzo4- @q) + 6Fe2+ 1aq1..-
4 Mg(Nor), (aq) + Nro G) + Hro (f .. (iv) zcp+ @q) + Fet+ (aq) ...(ii)
Step 5. Balance O ond H atoms by hit and frial Sttpi.Balan H andO.
mellrcd. To balance Fe on , multiply
30 orygen atoms on L.H.S. but Fe3+ on R.H.S. of
gnly s on R.H.S. of Eq. (iy), rherc- crrol- @q) + 6 Fez+ 1aq1+ H+ .....*
fore, omq change tbe coillicient of
Hzo have, z0f+ @q) + 6Fe3 (aq) ...(iii)
a Mg (s) + 10 HNo3 (a4) ......- Step 6. Balonce O otoms by adding HyO
molecules. Sincn tberc are 7 O atoms in CrrO] - but
a Mg(Nor), (aq) + N2o
G) + s Hro (f ...(v) only one in HrO, therefore, to balance O atoms,
The II atoms get automatically balanced.
Thus, Eq. (v) represenls the corecl balanced equa_ multiply HrO by 7 on R.H.S. of Eq. (ur), wc have,
tron- crrol- @q) + 6Fe2+ (aq) + H+ (aq1 -....-
2 Cl+ @q) + 6 Fe3+ (aq) + 7 HrO (t) ...(iv)

Saep 1. Write the skeletal equation

of th ction,
Crr0l,- (aq) + Fez+ 1aq1.--
cf* Crrol- @q) + + t4 H+ (aq)
Fe2+ (aq)
-..+
@O + Fe3+ (aq)
S|ap I-dentify the atoms which underyo a ZCF+ @q) + 6Fer+ (aq) + 7 HrO (f ...(u)
.
change in O.N.
!.
Thus, Eq. (v) represents the correct balancd
equaEon.
O.N. increases by 1 per Fe atom

+6 -2 +z 3+ i+
I Cr, o7 f2- (qq)+Fe (qq) + Cr (oq)+Fe taq)
|l,u
C).N. decreases by 3 per Cr atom
The
Stcp l. Wite the skeleul equstion.
uation for the given reaction is :
mor- (oS) + Br- (aq).......t
Total decrease =2x3 =6
Here O.N. of Fe increases from + 2 in Fe2r MnO, (s) + BrO3- (aq)
to + 3 in Fe3+ while that of Cr decreases from + 6
in CqOl- to + 3 in Cf +. . St p 2, Find out he elements which tutdergo a
change h oriilafion number (O.N.)
9/18

o.N. iDcreases bY 6 Per Br atom Thus, Eq. (v) reprcscnl.s the correct balanccd

+'7 -l
!---------1,
+4 +5
equation.
1 \ \\ il'i l 'J ' Bulu ce the oxidation reduc-

(s)+BrOl tion rcsction,

Mnof (aq)+Br- (44)-MnO2 (aq)
...(D
FeSz+02-FczOs* SOz

his is an examPlc o[ a reaction

O.N. decrcascs b}, 3 Per Mn atom of acids and bases and
abscnce
Herc, ().N. o[ Br increases from Br- to
- 1in of () atoms cannot be done bY
+ 5 in BrO;, thereforc, Br- ocls u rcductanl' F\tt' molccnles but has to be done on
ther, 0.N. of Mn decreases from + 7 ir MnOt to
the basis of gain or loss of electrons To balance
+4 in MDO2, therctore,MnOf, acts os oxidant' such reaction"s, following steps are followed :
Stef,3' Fi,td oltt tolal increaseldccreose in O N' Slep l. Identifu oton; who:ie oxidotion t tn'
bers undiryo a ctra;gt'. writing the oxidation num-
side,
ther, ber of eac-h atom above its symbol, we havc,
side, +2-1 0 +3 -2 +4-2
FeS,* O, ....- FezOr *SOz
Steo 4. Bulurce increaseldecrease iu O'N'
Since thl total increase io O.N. is 6 and dccrease in
O.N. is 3, therefore, muttiply MnOo- by2 Combin-
ing steps 2 and 3, we have,
zn/inoa @q) + Br- (dq)'-""''
Mno, (s) + Brol (aq) "(ii)
togetJrcr
Sten 5' Balance all oton$ other lhan O ond H' llrc lotal increqse ottd
Eq (ii), multiply Step 2, Detcnninc
tobolunce Mn on either side of
decrease in oxidalion nurubers'
MnO2 bY 2, we have,
Indicating thc increase ancl decrease in oxida-
zMnof, (uq) + Br- (oq) ' tion numbers in each case, we have,
2Mno, (s) + Brot (4q) (i") +2 +3
Fe ,Fe l1l
Step 6, Balonce O dtoms bY adding HrO -r +r I=111 "'('i)
rttttlccules. Since there are 8 orygen atoms on Sz--..'2s l0tJ
L.H.S. of Eq. (iii) and only 7 on the R H'S , there- 2-
f"r", oti"'ff rO to the R.H'S of Eq (iii), we .i^ oz...* 20 4l...(rri)
"aa
have,
Step3.Balonce lhe total increosc ond decrease
zMnOf (a4) + Br- @q)' it oxidation nurnbers.
2Mno, (s) + BrO! (a4) + HrO (/) "(iv) To balance the total increasc in oxidation
number of Fe and S and decrease in oxidation
Slep 7, Balance H atoms by adiing HrO and
number of O, multiply Eq. (ii) bv a and Eq (iii) by
OH- since llft rcaction occurs in basic mediunr' 11, and adding, we have,
Sioce Lhere are two H atoms on R H S and nonc +2 -1 +3 +4 -2
on L.H.S. of Eq. (iv), therefore, add 2HrO to L'H
S'
4[Fe + Srl + 1l o, -'--+4Fe + 8S + 22o
anrl 2OH- to R.H.S. of Eq. (ir), wc have,
'-(ir)
2Mnt)a- (44)+ Br- (oq) + 2H2O (l) -> 2-
2Mno, (s)+BrO! (aq)+HrrJ (l) +zort- (aq) Since 6 <loes not occur independently so the

or Mnof (,q) + Br- (aq) + H2O (/)----"') 226 must be faciorized in such a mlnner that thcy
2N'tno2 (s) + Brof (aq) + zoH- (aq) "'(v)
b"co.e purts of ferO, and SC)r' Rearranging, Eq'
(iu), we have
 REDOX REACTIONS
9/19
+2 -1 +3 2_ +4 2_ TIE tn)o half reactions are then aclded ap. These
4 [Fe +S2l+ 11 02 [4 Fe +6 ol+[8 s + 16 Ol
--.] rules are illustrated by the following cxamplas.
or 4 FeSz + 11 Cl2...-2FerOr+gSO, Pemantonqte ion reacts with
medium to give Fe3+ and
. This represenls the required balanced equa_ ced chemical equalion for lhe
tron. (N.C.E.R.T.)
II. Ion Electron Method or Half-Reactioo l. Write the skeletsl equation
Method lot th
MnOa (aq) * Fe2+ (aqy--...t
}./.nz* (oq) + Fe3+ (aq) ...@
equal to he electrons gained duing reduction hatf Step2. Wite the O.N. of alllhe elcments ubove
rcaction. The vaious steps involved in this method lheir respective symbols.
are :

+7-2 +2 2+ 3+
(Mno4)-t + Fe Mn+Fe
Step 2. Frnd out lhe species which orc uidked
and which are reduced.
O.N. increases by I per Fe atom
stcp ha| Step 3. Fnd out the species which have been
,eactions, tion oidised aad reduced ond split lhe given skelcton
haf reaction .
equslion into two haf reactions,
Saep 4. Bdlance thc tn o ha[ reaction eEntions
Since the O.N. of Mn decreases from +7 in
separately by the rules descibed below :
MnOa- to + 2 in Mn2+ while that of Fe increases
(i) ln each halfreactioq firstbalancethe atoms
of the elements which have unde,gone a change in
from +2 in Fe2+ to +3 in Fe3+. Thercfore.
MnOa- gets reduced while Fe3+ gers oxidised.
oxidation number
(ii) Add electrons to whalever side is neccssam Thus, the above skeletal Eq. (i) can be divided into
to mske up the dwrcnce in oxidaion numbet in thc tbllowing two half reaction equations :
each half reaction. Oxidation holf equation :

H+ ions if the Fez+ (aq) --.--- Fel+ (oq) ...(rr)

and by adding Redrction hav eErstioa :
in the basic Mnoi @O
-. Mr,z+ (aq) ...(ni)
(ii)
.(iv) Balance orygen atoms by addilg tequired
number of HrO motecules to the ;ide defr;ie; in O nol
atams.
ne
- (b) Balaace the oxidation number by adding
elect oN. T\e O.N. of Fe on L,H.S. of Eq.
14 ii
Fer* is +2 while on the R.H.S. in fe3+'is'i3.
Therefore, addonee- to R.H.S. ofEq. (i), we have,

numb Fe2+ (aq) ----r Fe3+ (aq) + e- ...(iv)

numb
of the ionr. Not

f"liTlli:
_.... Slap 5, To balatcc thc tzhrction ha{ eq.ation
(iii)
 (u\ Balsnce qll the atoms othet thqn H and O' +3 -z +5
As, 53 (s) + No! (aq) + H+ (aq)
N.,t r,eeded since Mn is already balanced -
+5 0 +2
MnOo- (44).-........r M*+ (aq) .'.(rrr)'
Asol- (aq) + S G) + No, G) + H2o (0
b\ Balonce lrc oxidation rutmber by adding Here. the oxidation number of As has in-
electini..t. Thc oxidation numtrer of Mn in MnOn- creased from + 3 to + 5 and that o[S has increased
on L.H.S. of Eq. (iii) is *7and +2ontheRHS'
ftom -2 to 0 while that of N has decreased from
+ 5 to + 2.In other words, both As and S havebeen
Thercforo, addis- to L.H.S. of Eq. (iii), we have,
oxidised while NOr- has been reduced' Since 'es
MnO; (a{) + 5e- + Mnz+ (cq) "'(r') j
and S must maintain their ,tomic ratio ol 2 : (as in
As therefore, the chonge in oidation numbers of
)
arye bY addirtgH ,S
tvo cidic nrctliunt ' T these rwo atoms must be considered together Keep-
oo . (v) is -6 and ins in view these points, the above redox reaction
ca"n Ue sptit up i"t6 the followingtwo halfreacl'ions
:
ir e, add 8H+ to
have, Oxklation :
Mnoa (aa) +8H+ (aq) +3-2 +5 0
As2s3 (s) """', AsOl- (aq) + S (s) ..'(i)
Mn2+ (aq) "'(r'i)
+5 +2
(d) Balance O atoms by adding HrO mole' Reduction : Noi (oq) "-' NO G) "'(n)
cales. Since there are four O-atoms on the L H'S'
Step 2. Tb baloace the oxidation half Eq' (i)
oi Eo. (vi) but no O-atom on the R.H S', therefore'
adtl d Arb to the n.H.S. ot Eq. (vi), we have, h\ Balsnce all the atoms olher thon H dnd O'
frlultipfy esOl- by 2 and S by 3 on R.H'S' of Eq'
MnOa (arl) + 8H+ (4q) * 5e- a
(i), we have,
Mn2+ (arJ) +4H2O (aq) "'(vii\ +3-2 +5 0
AsrS3 (s) 2 Aso34- @q) + 3S (s) ...(iv)
The H-atoms get automatically balanced'
-
Thus, Eq. (vii) repreients the balanced reduction
half equation.
Step 6.Tb balance the etectrons lost in Eq (iv)
andgainidin Eq. (vii), ntultiply Eq' (iv)by 5 andodd
to Eq. (vii), we have,

5Fe (oq) 5Fe3+ (aq) + 5 e-

-
(4q) + 5 e-
MnOa @$ + 8H+ '
Mn2+ (a4) + 4H?o o """o o1- @q) + 3 S (s) + 10 e-
Aqs3 (s) 2 As
t
Mnoa- 1a4) +5Fe2 (4g)+8H+ (aq)' -.(iv)
}./lrl+ (aq) + 5Fe3+ (aq) + 4H2o o (c\ Batance charge by odding H+ ions' The
This gives the final balanced redox equation' total i(arge on R.H.S. of Eq. (iv) is - 16 and zero
oo tn" I-.ir.s., therefore, adi 16 H+ to R'H'S' of
. I
!"\ \1'll'l ').ll.Balancelhe equalion'
(iv) have, . .
Eq. we
.asr.S., (s) + NO, (aq) + H+ (aq) Aq$ (s) -"- 2 Asol- (aq) + 3 S (s)
-
Asdn- @q) + s (i) + No (9 + Hro (t) + l6H+ (oq) + 10e- "'(v)
(N.C.E.R.T.) (O Balance O ltoms bY ailding HrO
Solution SteP 1' Io i rlhose molectles. Sinct there are e8',' O-atoms on the
otidalion nttmbers-huve tut
Writ- n.U.S. of eq. (v) but none on the L'H S', therefore
i.., 8IIro to the L'H'S' of Eq'
ing the oxidation number tutr"""
ovc its io O^-ui add
symbol, we have, (v). We have,
 REDOX REACTIONS

+ 8 H2o (/)
As2S3 (s) 2 A sof,- @q) Step 2.Witc he O,N, of all the elements above
-
+ 3 S (s) 16 H+ + 10 e- ...(vi\
theb rcspective sylb ols.
O.N. of Cl increascs by 5 per Cl atom
The H-atoms get automutically biilanced. v
Thus Eq. (vi) rcprescnts the balanccC oxidation ol -1 +5
half equation. Cr2 G) + oH- (aq) ct- (aq) + CJlol @q)
Step 3. To balance the reduction half Eq. (ii) -
(a) Balanca oidatiot nuntber by addirtg O.N. of Cl decrcases by 1 per Cl aiom
elecoons. Oi,Jation of N is + 5 on L.H.S. whilc it is
+ 2 on R.H.S., therefore, add 3 e - to L.H.S. of Eq.
Total increase =2x5=10
(il). We have, Total decrease =2x- I=- 2
NO, (aq) + 3e- 'No G) ...(,ir) Stcp 3. Fitd out the oidant and the ,edrctana
and splil lhe skeletol Eq. (i) into two half reaaions.
(b) Balance charge by odding H+ ior6. Thc
Here, O.N. of Cl decreases from 0 in Cl, to
total charge on L.H.S. is - 4 while it is zero on
R.H.S., therefore, add 4 H+ to L.H.S. of Eq. (uii). - 1 in Cl-, therefore, Cl2 dcts ss on midotl Frr-
Wc havc, thcr, the O.N. of Cl increises from 0 in Cl, to +5
NOr- (aq) + 4}]+ (oq) + 3 e- + NO G) in ClOr-, therefore, Cl2 acts os a reductant.ln othet
...(viii) words, Cl acts both as an oxidant as well as a
(c) Balance O atoms by addingHrO ntolecules. reductant. Therefore, the two half reactions are :

Since there ue three O-atoms of the L.H.S. of Eq. Reduction half : CL, (il- Cl- (sS) ...(,i)
(viii) but only one on the R.H.S., thcrcfore, add
2 HrO to thc R.H.S. of Eq. (vfri). Wc have,
OidLtion ha[ : Cl2 G) .._ ClOi @il ...(iii)
Step 4.T o bolance the reduction ha{ equation
NOI (aa) + 4H+ (oq) + 3 e-
(ii).
No @)
-+ 2 Hro (/) ...(u) (o) Balance nll aroms other that O ond H.
The H-atoms are automatically balanced. Since there are 2 Cl atoms. On L.H.S. of Eq. (ii)
Thus, Eq. (ir) represents the balanccd reduction and only one on the R.H.S., therefore, multiply
half equatiou. Cl- ion by 2, we have,
Step 4.To bolance the electrons lost in Eq. (vi) c\(oq) '--'' act- (aq) ...(i,)
and gained in Eq (ix), multiply Eq. (ix) by l0 und (b) Balance oxidotion number by adding
Eq. (vi) by i and add. We have, elecfionr. The O.N. of Clin Cl, on L.H.S. of Eq. (iv)
3 As2S3 (s) + 24 H2O 11; .._ 6 a ,6:- 1or.1 is 0 while on the R.H.S. it is -1. Thus each Cl
+9S(s) + 48H+ (qq) + accepts one electron. Since there are two Cl atoms
on the R.H.S., therefore, add.Z e- to L.H.S. of Eq.
l0No3 (aa) +tfiH+ (aq) +30c-- ^Oe-
(iu), we have,
10NoG) +20H2oo
Clz (d + 2e- -----.- zcl- (aq) -.(r)
3 A9S3 (s) + 10 Not (afl + aHro (t) (c) Balance charye. Not needed sinct charge
6 Asoi- (aq) + 9 S (s) + 10 No G) + 8H+ (sq) - on either side of Eq. (v) is balanced. Thus, Eq. (v)
represents the balanced reduction half reaction.
This gives the final balanced redox equation.
Step 5.'Io bolance the oxidttion half equation
. liX.Ar\{PI.lt t).12. In passing chloine gar (iii)
through a concentrated solution of alkali, we get (a) Bdance all atoms othet than O and H,
chloidc and chlorate ions. Obttin balqnced, chemi-
cal equation for tlii rcsction. (NCE.R.r) Since there are 2 Cl atoms on L.H.S. of Eq.
(r'rr) a.nd only one on the R.H.S., therefore, multiply
-Sdu!l.gn. Step l. Wa'l e the skeletsl equationfor
the g,]',cn rcaction ClOr- ion by 2, we have,
Cl, G)+OH- (aq)+cl- (aq)+Cto, (oq)...(i) c\(0 zctot (aq) ."(v,
-
9122 , Ned Course Chcmistrg !;eil)
(b) Balance oidation number by adding cl2 (9 + tzoH- (aq)
electons. The O.N. of Cl in Cl, on L.H.S. of eq. (vi) zclo, (oq)-+ 6HzO (0 + 10 e- ...(i:)
is zero while in the R.H.S. i.n ClO3-, it is + 5. Thus,
By doing so, H atoms are automatically
each Cl atom loses five clectrons. Since there are balanced, therefore, Eq. (rr) represents the
two Cl atoms on R.H.S., therefore, add 10e- to balanced oxidation half equation.
R.H.S. of Eq. (vi), we have, Step 6. Tb balance the electrons gained in Eq.
70e- (v) and lostin Eq. (ix), mulriply Eq. (v) by 5 and add
Ctz G) aclot (aq) + ...(vr,
-
(c) Balonce charye by adding OH- ions since
to Eq. (ix), we have,
+ lO e- .-.-+ l0Cl-
5Cl, G) (aq)
the reaction occws in the bask medium. Tbe total ct2 @) + 72oH- (aq)
chargc on the R.H.S. of Eq. (vr'i) is 12 and zcro - zclo, - + 6Hro (/)
(aq) + 10 e-
on the R.H.S. Therefore, add 12 OH- ions to the
L.H.S., we have, 6clz @) + lzoH- (oq) """'t
clzB) + taoH- (aq) "'--'.2clq @q) + I:oe' L}Cl- (aq) + 2clot (aq) + 6Hro ({)
...(viii)
(d) Balance O atoms. The R.H.S. of Eq. (vnt)
or 3Cl2 @)+ 6oH- (aq) -""+
contains six O atoms but on the L.H.S., there are 5Cl- (oq) + Clo, (aq) + 3H2o (0
12. Therefore, add 6HrO to the R.H.S., we have, This represents the firral balanced redox
cquation.

l. Balance the following equations in acidic medium (Pni) H2S G) + Fc3+ 1a41
by both oxidation number aod ioll electron
methods and ideotiry the oxidanB and lhe reduc- -
Fe2+ 1a41 + s 1s; + H+ (oq)
tants :
(ix) l- (a4 + to; (oID + H+ 1oq1
(,) MnO; (a4) + czHzoa @q)- -
lz@q) + HzO (l)
Mnz+ 1aq1+ co2 G) + H2O (r)
(r) Bi (r) + NOt (a{) +H + (4q)
(N.C.E.R.T.)
Bi!+ 1aq1
-
+ No2 E) +Hzo (r)
00 H2S (aq) + cl2 G)- S (r) + cl- (44)

) @) r- (oS) + 02 G) + H2o (D

(iir) Mnot (oq) + cz'so,^(aq) -

lt@ + oH-Qq)
-(N'.'E'R'T
Mnz+ 1aql+ cH3COoH (44) (ri) Cu + Au+ Au + Cu2+
(N.C.E.R.T) - (oq) + H+ (q)+
(rii) sn (r) + Not
(iv) Bi (r) + Not (4q;.- 313+ (dq) + Noz G) Sn2+ 1a4; +NH.+ 144) +H20 (r)

(v) CrrO]- @q) + czH'/o (aq)- (rv) cu (.r) + Not (aq) + H+ (aq)._
CF+ 1a4; + czl{41zll,q) Crz+ (oq) + No G) + H2O (r)

(v,) MnO; (oq) + Br- (oq) + (rv) zD (r) + Nol (a4 +H+ @4)-
Mr:2+ 1aq; + Bt2 @q) Zoz' <oq) +N2o E) + H2o (4

(v,i) cu (44)+Not 1*'1- coz+ (oq)+Noz?) (xrr) Sr (aS) + Not (oq) + H+ (4q)
(N.C.E.R.T.) - + H2o
snoS- (a{) +No2 G) (r)
REDOX BEACTIONS 9123

(rvii) As (.r) + N of (aq) + H + (4q) ._ (Jyii) As (s) + s Not (aq) + 2 H + @4+

esol- ta91 + r.ro, G) + HrO g1 Asoi- (aq) + 5 Noz Gr) + H2O (I)l

I\ (t 2MnOi- 1q1 + eU+ @q) + sczHz}4 @q) 2. Balance the follotping equarioos in basic medium by
both cfiidation numbcr and ion eleclron merhods aDd
2ynz+ pqy l l oco2 GI) + 8H2o (r) idcDdry the reductants aDd the crddants.
-
(ri) H2S (aq) + ctzg)+ (0 P (r) + oH- (4s)- PH3 G) + urPOl (a4)
s (r) + 2Cl- (4g) + 2H+ (o1) (N.C.E.R.T.)
(iii) 4MDOa- (a{) + sczHsOH (o{) + 12H+ @q) 0D N2H4 G) + clot (aq)- NO (g) + ct- (aq)
* 4Mn2+ + 5CH3COOH (aq) + l1HzO (0 (Nc.E.R.T.)
(tr) Cl2O7 G) + HzOz@q)*
(iv) Bi(s) + 3No3- (4q) + 6H+ (oq)-
cto; (aq) + o2@) (N.C.E.R.T.)
Bi3+ (4q) + 3No2 G) + 3HzO (I)
(iu) C(OH)a pq) + HzOz(pO-
(v) c;zolt- @q) + 3czH1o (oq) + BH+ @q)
c/.Ol- @q) + H2o (t)
2g1s+ @q) + 3c2H1O2@!t) + 4H2O (r)
- (v) Zo (r)+No3- (4q)- 7n2+ @q+NH[ @4)
(vi) 2MnOo- @q) + loBr- (aq) + ]6H+ @q)
(!r) At (r) + N of (a{) --
2YDz+ @q1 + sBtz@q) + 8H2O (4
- N(OH); (aq) + NH3 G)
(r,r'i) Cu (r) + 2No3- (4q) + 4lg^+ @q)

.* (vri) PbO2 (r) + ct' (dq)+

Cu2+ (a4) + znoz (g) -r 2HzO (l)
Pb(oH)t (aq) + cto- (aql
(r,iii) HrS @) + 2Fc3+ 1aq1
(vr'ii) Fe(OH)2 (aq)+HzOz (c4) * 2Fb(OH): (r)
-
2Fe2+ 1aq1+ s (r) + 2H + (aq)
(.r) Bi(OH)3 (r) + snol- (a4) ..-
(ir) 5l- (aq) + tol (uD + 6H+ (oq)
Bi (r) + snot2_ (a{)
312 (!q) + -3H2O (h
(r) Bi (r) + 3Not (oq) + 6H+ (aq)- (r) Cr (r) + cto; (oq)
-
BP+ + :NO, 19; + 3H20 (I)
Cr(oH)3 (.r) + ctot (oq)
1ag1

@) 4I- (aq) + oz@) + zHzO (4

I\x,. (i) 4P (r) + 3oH- (aq) + 3H2O (l)+
212@q) - + 4oH- (aq) PH3 (g + 3HzPo; (aq)

(di) Cu (r)+2Au + (aq) 2Au (s)+cu2+ (a4)

(ri) 3N2H{ (g) + naol @rt)-
(rrii) 4 Sn (r) + No! - + 10 H + (aq)-
(a9) 4ct- (aq) + 6H2O (l)
6NO G) +
(nr) ct2o7 G) + 4H2o2(uD + 2C. - (aq)
4 Sn2+ 1c4; + NH.+ I4q) + 3 H2O (r)
zC],O; @q) + 4o2e) + 5H2o (/)
(riy) 3 Cu (r) + 2 Not (a{) + 8 H+ 1aq;..* -
(iv) 2c(oII); (oq) + 2oH- (a4) + iHzoz<oq)
Z C!2+ 1aq1+ 2 No G) + 4 H2O ()
zjq @O + 8t12o (t)
(xv) 4Zn (r) + 2 Not (a4) + to u+ 1aq;- -
(v) azn 6) + Not (a4) + TH2O (,)
t Znz+ 1aq1 + N2O G) + i H2O (r) + 4tuP+ (4q) + NH4+ @q) + loo - laq)
(.tr,, Sn (-r) + 4 Not (4q) + 2 H+ (oq)- (vi) 8Al (r)+3No3- (4q)+18H2O (D+soH - (ag)
sno3- (aq) + 4 No z@) + H2O (t) 8Al(oH)a (a4) + 3NH3 G)
-
9124 Pradcep's

(vii) PbO2 (r) + ct- (aq) + HzO (D + oH- (a{) (v) lt + HNO3
- Fe(No3)2+NH4No3+H2o
Pb(OH)3- @q) + cto- (aq)
- (vi) Sb - HNO3 HrSbO. + NO2 + H2O
(tiii) ZFu(OH)2 @q) + u2o7 @9)
- (vii) Hg + -
IINOr- Hg"(NO3)z + NO + I-I2O
t"
l.\nr. (i) SnO2 + 2C+ Sn + 2CO
(&) 2 B(oH)3 (r) + 3 snol- ,*, l"to" (ii) Fe3Oa + 4C- 3Fe + 4CO
2 Bi (r) + 3 sno3- @q) + 3 H2o (l) (iii) 12+10 HNO3 ._ 2 HIO3+ 10 NO2+4 H2O
(x) 2 Cr (r) + 3 cto; (aq) + 3 H2O * (iv) 6 FeSOa +2HNO, + 3 H2SOa
2 C(OH)3 ('i) + 3 ctot (arl)l 3 Fe2(SOa)3 + 2NO + 4 H2O
3. BalaDce the following redox reactions : (v) 4 Fe + 10 HNO3

(i) SnO2 + C+ Sn + CO -
4 Fe(NO3)2 + NHaNO3 + 3 H2O
(ii) F%Oa + C- Fe + CO (vi) sb + 5 HNo3- Hjsbo4+5 No,+Hzo
(iii) I, + HNO3 HIO, + NOz + H2O (rii)6Hg+8HNO......-
- + H2SOa
(iv) FeSOn + HNO, .._ 3H82(NO3)2+2No+4H2Ol
Fer(Soa)3+No+I'I.o

It is evident from balanced equation that

1 CrrOl- = 6 molcs of Fc2+
rnotc of
Stolchlometry of redor resctions means csl' or 1 mole KrCrrOr = 6 moles FeSOo
culation ol the quantities oI the oxidising and rcduc-
ing agents atd theit producls in Gidation+eduction ot 2x39 +2x52+ 16x7 g=
reactions. 6x(56+32+16x4)
Stoichiometric calculations can be done or gYlCrrO, =6 x 1529 FeSOu
294
either by using mole concept or by redox titrations
Now 6 x 1529 of FeSOo are oxdiscd bY
using normality or molarity equation.
Y:rCr2O, : 294 g
9.12.1. Determinatlon of stoichiometry using
mol concept, For carrying out stoichiometric cal- . . 15 2 of FcSOo will rcquire K2CrrOT
culation-s, we need a balanced redox equation for 294 x t5.2
the reaction since the stoichiometric coefficients in -- = A,qo
the balanced equation tell us thc ratio by moles in
6x152
which the reactants combine and the products are
, .,i''f i 2'68x 10-3 ntoles ol o
formed. The following examples will illustrate the solution contoiting an ion A"+ rcquirc )'6lxt0-3
method. moles MnOf, for the oxidation oI An+ to AO; ilt
. \ r' \\1f'! ,' Ho$l many grams of potas-
| t\ acid mcdium. lVhot is the vahrc of n ?
sium dichromste are required to oidise 15'2 g of Snlution. Step L Tb write tlrc reduction and
FeSO oin acidic ntedium. atidati on ho lf rea c ti orts.
.solutiotr, Stp 1. Io tvite balatced chemicul Reduction:M\O; + 8H+ + 5e--'
equation of the redox reaclion Mn2++4FIro...(r)
crzo?- + ]4H+ + 6e- -----+ 2 CP+ + 7 H2o
Oidation : N+ + 3 HzO"""''
Fe2+ ------- Fe3+ + e- | x 6
+s
AO3- + 6 H+ + (5 - n) e- ...(ii)
crro2r- + 6Fe2+ + 14H+._2gf+ a 6 Pg:+
Step 2. Tb ft td our lhe value of n.
Slep 2. To calculatc the amount of K.CtrO, Since ina rcdoxreaction, numbcr ofelcctrons
required. lost - number of electrons gained, thcreforc, mul-
REDOX HEACTIONS

tiply oxidant of Eq, (i) i.e. MnOo- by (5-+r) and (i) Oidation of fenous salts :
reductant of Eq. (r'!) ie. An+ by 5 and equate, we 6Fe2+ + Crro|- + 14 H+ -----'
haic, 2CF+ + 6Fe3+ + 7H2O
(5-n)MnOo-=54"+
A'+ (ii) Oxidation of Mohr's salt :
i.e., (5-+l) moles of MnOa- will oxidise =
Mohr's salt is a double salt of (NHn)rSOo and
5 moles
or 1.61 x 10-3 moles of MnO.- will oxidisc FeSOo r'.e. (NH1),SO1.FeSO1.6HrO. Out of thesc
two salts, CrrO|- oxidises FeSOo to Fer(SOn), as
5 per the equation shorm under oxidation of ferrous
=Fi;" 1 6 x l0-3moles ...(iri)
salts.
But the number of moles of An+ actually 3, Ceric sulphate tttmflons. In these titra-
oxidised tioDs, the reducing agents such as Fe2+ salts, Cu+
= 2.8 x 10-3 moles
...(ir) salts, nitrites, arsenites, oxalates etc, are directly
Equating the values of Eq. (rrr) and (iv), we titrated against ceric sulphate, Ce(SOo), as the
have, oxidising agent. For ercample,
5 x t.61 x 1o-3 = 2.68 x 10-3 (i\ Oidation of fenour salts :
5-n
=
Fe2+ + Ce.+-aFe3+ + CC+
or 5 x 1.61 -(5-n)x2.68 Fcrousion Cric ion FeEic ion Ccrcus ion
or 2.68n = 5 (Z'68 - l'67) (r) Oxidation of aresinites (AsO3-) to ar-
-5xl.Ul=5.35 senatcs (AsO!-).
or n =ra=5'35
z
A"o3- + 2Ce'++Hzo-
9,122. Detrmlnotlotr of stolchlomettf uslng Ars.nitc ion Ccric ion
Redox tltratlons. These titrations involve the reac- Asol- + cd+ +2H+
ticn between cxidising and reducing agents in A*enatc ion Ccrcus ion
acidic medium. Depending upon the nature of the
oxidising agent, these are divided into the following (iii) Oidation of oxalic acid :
categories : (COOH), +ZCea++
Potassiumpet anganate titmtions. In these
1. Oxalic acid
tiEations, reducing agents like FeSOo, Mohr's salt 2co2+ zcf+ + 2H+
[(NHa)2SOa . FeSO4 .6 H2O], H2O2, AEO3, 4. Iodimetric titrations. These titrations in-
oxalic acid (COOH), and oxalates (COONa), etc. volve the direct use of iod.ine as the oxidising aryt
are directly titrated against KMnO. as the oxidising (h neutral or slightly acidic medium) using starch
agent in acidic rnedium. Fo. orample, as an indicator. The various reducing agents used
(i) Oxidation oflenous salts. in these titrations arc thiosulphates, sulphites, at-
s enites and ontimonites.
5 Fe2+ Mno4- + + 8 H' ' Iz *
Fefous ion permaganatc S.o3- --+ 2l- + S4O3-
ioll ion
Thi6ulphate Tctrathionatc ion
5Fe3++Mn2++4Hro 12 + so3- + Hzo ----. zl- + so?- + 2 H+
Fcrric ion Sulphite ion
(ii) Oidation of aralatcs : I, + AsO!- + HrO + 2l- + AsOi- + 2H+
coo- Alscnitc ion Ardrnatc lon
5 | +2MnO; + 16H+ ""'-.
+ SbOi- + H2O- 2I- + SbOi- + 2H+
coo- 12

oxatatc ion Mnz+ + 10 CO2 +

2 8 H2O Antimonite ion Antimonate ion
2. Potasslum dichroEstc titrations 5. Iodometric tltratlons. These titrations are
In these titratiorx, the above listed rcducing carried out in two steps. In the first step, oxidis.ing
agents are directly titrated agaiDstIqCrrO, as the agents such as KMnO., KrCrrOT, CuSO4,
oidising agent in acidic medium. for exanplc, peloxides etc. are treatedwith an excess ofKI when
9126 Neg Course Chem istrg
I, is liberated quickly and quantitatively. For ex- Mol. M. of KMnO4
or Eq. wt. of KMnOo =
ample,
2 MnOn- * 16 H+ + 10 I-
zMr2+ +
-'
512 + 8H2O
=rr*rf*uo=rr.u
(b) In neutral or alkaline medium
ctrol- + 14 H+ + 6I- -+
MnO; + 2H2O + 3 e- MnO, + 4 OH-
?cF+ +312+7Hzo - gained : 3
Total number of electrons
2Cl2+ + 4I- + CurI, + I, Total change in O.N. of Mn = 7 - 4 = 3
In the second step, the liberated iodhe is
. . Eq. wt. of MnOf
Mol. wt. 55 + 64
titrated against a standard solution of sodium 33
thiosulphate using starch as an indicatot. All such
titrotions in which iodine libemnd ftom potaseium = 39'66
iodide with the help oI an oxidising Agent is titmhd
against a standatd sofution of sodium thiosulphate
Eq.wt. ofKMnO. ="*l*uo =tr.UU
are called lodometrlc tltrations. (ii) Equivalent welght of I!CrrO,
Before we solve problems on stoichiometry of Crrol- + 74 H+ + 6e--ZCf+ +7HzO
tedox reactions we must be familiar with the follow-
ing three concepts : Total number of electrons gained : 6
(i) Equivalent weiglrts ol oxidising and reducing Total change in 0.N. of Cr
ogents. =2x6-2x3=6
(i i) N orm ality e qu ation Mol. wt. of CrrO]-
(iii) M ol ui ty e quation. .. Eq. wt. of CrrOl- =
(i) Equlvalcnt welgbb ofoddlslngand Educ- 2x52+7xL6
lng agnts. 'Ite equivaletrt weights of oxidising and =36
reducing agenls can be calculated by the number of
electrons gained or lost. Thus, rrre equivalcnl weighl
Mol. *t. of IQCr2OT
crr Eq. wt. of lQCrzOl = ----'i:
of an acidising agent is equol to the moleculu weight
of the substance diided by the numbo of elecuors 2x39+2x52+7x16
gqined as rcprcsentedin the balanced chemical equa- =---------;:--=.,
tion.
Likewise, the equivalent weigltt of a reducirg
Further, we know that the total number of agent is equalto its molecular weigltt divided. by the
electrons gained or lost in any balanced orida- nunber of electrons lost as rcpresenled in the
tiory'reduction half reaction is equal to the total balanced clrcmkal equation. For example,
change in the O.N. of a particular atom of the (i) Equivalent wetght of HrO, :
oxidising/reducing agent. Therefore, eEtivolent
weigits car also be determined simply by diving the H2O, ---+ 211+ + gz + 2e-
molecularwcight oI the substancelspecies by the total
chsnge in the O.N. of a pafticular atom. For example, (acidic ntediunr)
(i) Equivalent welght of I(MnO.
H2O2 + 2 OH- ...-ZHLO + Oz+2e-
(a) In acldic medium,
(basic medium)
MnO; +8H+ + 5- -------| Mn2+ +4tto
Total number of electrons lost = 2
No. of electrons gained =5
Total change in O.N. of Mn = 7 - 2 = 5 Total change in O.N. ofO = 0 - (- Z) = Z
Mol. wt. of MnOf Mol. wt. of H2O2
;. Eq. wt. of MnOo- = Eq. wt. of HrO, =

=
s5 lre = zt't =2+r9 =n
REDOX HEACTIONS

(ii) Equivalent weight of (COOH), : (i ) Equimlcnt rrclght of FeSO. :

QHzOo 2co2+2H+ +2e-
Oxali. acid - Fesol +
+
H2sol .-.-.- jrerlso.)' + e-
Total no. of elcctrons lost = 2
Total aumber of electrons lost = 1
Total change in O.N. of C= 2x4-2x3=2 'Ibtal change in O.N. of Fe = 3 2 1
.'. Eq. *t. of oxalic acid - =
Mol. wt. of FeSO4
Mol. *t. of . . Eq. rrt. of FeSOo =
QH,O.
2
56+32+4x76
24+2+& = 152
-2

equivalcot weight of the underlined (d)3C12+6NaOH

species io tcrms of its molecular weight M in each 5NaCl +NaClO3+3H2O
of the folloring rcdo( reactioos.
(e) 4Fe2+ + 2 NH2OH
142CuSOr I 4 61 Cu2I2 + 12 + 2&SOa -
- 4Fe2++Nro+4H+
(iD 2 Narsro, * r, .- Nazsror + 2Na IO3- + 3 tlso3- t- + 3H+ + 3SO1-
0)
1ur;
ffiQor + MnO. .- M16, .. 2 63, G)
Mnoz * I gCt *- MnClz + Cl2 + 4 H2O
(iv; FeSz + o, ...- Fezo: + Soz (r) slr + 4 HNo3 (conc.)
-
H2SnO3+4NO2+2H2O
1v;
Aszsr + H+ + Nof
- (i; 3 ng + a HNo: lrrrf ...*
NO+HrO+AsOl-+SOn2-
3AgNO3+NO+2HzO
[ turs.(i) M (ii) M (iri) W2 (it) Wta O) l\AzEl
g1 + zn + lo lxo: 1a,4
2. Determine the equivalent weighl ofthe underlined
specie,s/compounds in the following equatioDs : zl
-
Zn (No3)2 + NHaNo3 + 3 H2o
(4) s2o3- + 5 H2o + 4ch- I \n\ (a) 14; (r) HS- = t.25, HSOr- = 40.5;
2SO1-+8Cl-+10H+ (c) Mho2 - 43 S, KclOs= 20.4 ' <d) 2r'3

(D)2HS- + 4 HSOt 3sro3- + 3 H2O (?) 16 s (D Io3- = t7.5, HSOs- = 40.5;

(c) 3 MpO2 + 6 KOH + KCIO:
- -* G) 43.s (rt) sn = 29.7, HNor = 63;
3IqMnOa + KCI +3H2O () 21 i A) 7 .ttl

(iv) Calculate the total chaDge in O.N. of one Total increase iD O.N. = 2 + t2 = t4
molecule of FeS2 Hence, Eq. wt. = M/14
FeSz=Fe2++252- (y) Calculate the rotal change in O.N. of one
molecule of AtS3
2+ O.N. incrcsses +3
2Fe FerO, AhSr=2As3+ +352-
WZxl=2
+4 _. O.N. incrca6es +5 -
2S
O.N. incrcascs
2 SO2
2 Asr. 2 AsOi-
W2x6,12 by2x2=4

-+
 9128 i t " ,, . Nett Coursc Chemistrglftffi

2- O.N. incrcases +6 . Naclo- 2 x Mol wl'

35 3 (SO1f-
Eo. wt. of - 10
bv3x8=24
'Ibtal increasd in o.N. 4 + 24 28
2(23+3s.s+4R\
= = l0 -
fi. = M28.
Henc, Eq. -l +1
2. +z 2- +6 z- (e)2NHrOH-...N2O
(a) 52 03 *2S or
TttalchaDge in O.N. = 2 x 1 - z (- t) = 4
lbtalchange in O.N. of S - 2 x6 -zxz=8 .. Eq. wt- of NH-oH 2 x Mol wl'
.. Eq.wt.of szo3- = Mol. wr./8 - 4

= 712/8 = 14
2x13
=-4_=16.s
-2 ._ +2 2-
(6) (0 2 [H s]- s2 03 o(0rot-r-
Tbtal change in O.N. ofS Total change in O.N. of I=+5- (- t) = 6
=2x(+2)- (2 x -2)=8 .. Eq. *r. of lor- = Moli wr 12? 48
qi' 62 = -+ - 17 .
s
,.. Eo.wt.of
,8 Hs- - 2 x Mol +4 +6
(i0 Hsoi sol-
=2133=r.zs Tbtal change- iD O.N. of HSOJ = +6-4=z
+4+2-
(ii) 2 HSO3- 52 Ol-
.. Eq. Et. of Hso3- - M'l *t - $ = lo .s
- +4 +2
Ibtalchange iD O.N. ofs - 2 x4 -2x2=4 G) MnO2 * MnCl2
2 x l\'!ol wt M'l*t =f
.. Eq. wt. of Hso3- - Eq. .*r. orMno2 = = n..t
2 x 8l
=--?-=lo s
(r) (l) sn ..- lt2sDo3
+4
+4 +6
(c) (i) Mno, IQMnon .. Eq.wr.of sn = At-wt =11!7-rr.,
- O.N. of Mn = 6
'Iblal change in
- 4=2 +5 +4
.. Eq.wt.of Mno2= Mo! wt (i0 HNo3 No2
=55;32 =a3.s -
Eq.wt. = 1r4q1.wt. = 1 + 14 + 4E = 63
+5 -1
(it) KCro3 * KCr +5 +2
(i) HNO, p6
Tbtalchange in O.N. of CI = 5 - (- t) = 6
-
Eq. wr. = 11461.1y1.;3 = 638 = 2l
.. Eq.wt.of Kcloi = Moliwl - 12? 5
- 20.a +5
6o 0) HNo3 -*
-3
0+5 [NH4]+
(d) Clz Tbtalchange in O.N. ofN - 5 - (- 3) = 8
-2NaClO3
Tbtalchange in O.N. ofcl = 2 x 5 .. Eq. wt. = Mol. 1l1.E = 63/8 = 7.8A
- O = r0

,based(i)upon
Normallty. equatlon. This equation is .'. V, cm3 of N, KMnOn contains KMnC)o
the law of chemical equivalints which
N.
states that substances react in the ratio of their , V, gram equivalents
equivalent weights. To derive this equation, let us = 1000
consider the volumetric titration between acidified and V, cm3 of NrFeSOo contain FeSOo
KMnOo and FeSOn solutions. Let N, and N, be the
N,
normalities of KMnOo and FeSOo solutions respec-
1000
= , V, gram equivalents
tively. Suppose V, cm3 of N, KMnOo solution react Since substances react in ratio of their gram
completely with V2 cm3 of FeSOo solution. equivalent weights, therefore,
tNormalityis dcfined as thc number of gmm eq u i!"lcn: 1', cigh ts of a substancc dissoh'ed pcr litrc of the sotulion.
 REDOX BEACTIONS
9/29
NrVt/1000 = NzVz/1000 coefficients, we can derive the molarity equation.
Consider for example, the vol,rmetric titrat'ion be-
or N,xV,=N2xV2 trveen KMnOo and FeSOo solutions. The balanced
This is called normality equation. With the chemical equation for this reaction is
help of this equation, we can easily determine the 2KMnO. * .f SH2SOn....-r
10FeSO.
normality (N,) of anyunknovm solution if we know IQSO. + 2MnSOo + 5Fe(SO1)3 + 8H2O
thc yolume (Vr) of this solution which rcacts com-
pletely with another solution of normality (Nr) and Suppose V, cm3 of Ml fUnO. solution rea9
volume (Vr). Having determined be normality of completely with V2 cm3 of M, FeSO. solution.
the desired solution, its strength can then be calcu- .'. V, cm3 of M, KMnOn contains KMnOn
lated by the relation,
M.
Strength = NormaLity of the solution =mxV,moles
x Eq. wt. of the solute and V, cm3 of M, FeSOa cortain FeSOa

The above method of determining the stoichio- M.

re
metry oI owledge of
=ffixVrmotes
equivalent determine - But.according to batanced redox Eq. (r), the
as discuss ke atomic molar ratio inwhichKMnO. and FeSO.,eic't com-
rveightand molecular vreight, equivalent rvcight is pletely Ls 2 : 10. Therefore,
not a fxed quantity ; it varies from reaction to Vll1000 2
Ml MrVr M,V,
reaction. In view of these difficulties, it is easier to
express the concentration of a solution in terms of M:y'tr/tm = ld or -r-=-ff (i')
moleVlitre) rather than u,here 2 and l0 are the stoichiometric coefficienLs in
e days, morality cquation the balanced chemical equation (l). If we now repre-
sent these stoichiometric coellicients by n, ani n,
(i) Molarlty equation. In order to derive respectively, therefue, Eq. (g) can be rewritten as
molarity equation, we must know what are Mrvr M2v2
slolchiometric coeflicients. For this purpose, con- _
sider the following general balanied- chemical nt n2
equation for a redox reaction, This is called morallty cquation and can be
oA+b8.......>cC+dD used to determine any unknown quantity if the
Here A and B are the reactants while C and otber tbree quantities are koown.
D are the products. The coefficients a, b, c .and d Jn gcneral for any rolumctric titration inrohing
are called stolchlometric coefiicients. These coef- rcaction be turcen A and B, the molarity equation is
"
ficients indicate the number of moles of the reac- Molarity of sol. A x Vol. ofsol.A
No. of moles ofA in balanced Eq.
_ Molaritv of sol. B x Vol. of sol. B
- No. of .otoEE-iiT iiEZEll

Io all rypes of titradons, N,V, = NrV, bur MtVl * M2V2

Ilowever,
titrations,
equation a
ofelectroo
 9/30 ; - Ne.4 Course Cltentistrg

?n P-.'.o...i[* l)( )\ l'l rlt rl lo\i

'''
I.l\.\XIPi,la 9.I5.A potticalat acid rain water 5 qo'?4- + 2 MoO; + t6 H+
contoins sulphite (Sq-) ions. II a 25 . 0 cmt sample 10cO2+2Mn2+- +8HrO
oI this water reqies i5.0 on' of 0.02 M KMIOI
solution for titruti what is the amount of SO!-
5 FeCrOo + 3 MrO; a, 2411+ --->
ions per litre in rain wakr 7
Slcp,..Tb write the balonced eEta- 5 Fe3+ + 10 Co2 * 3 Mnz+ + tzHzo
tionlor the rudu rcaction. Step 2. fo determine lhe molaity of FeCrOa
MnOa- + 8 H+ + 5e--+ Mn2+ + 4HrOl x 2 solution
so3- + H2o +2H++ze-lx5 Mol. wt. of FeCrO.
-sol =56+2x72+4x76=1449
2Mno; + 5SOl- + 6g+ Wt. of FeC2O4 dissolved = 1 ,14 9
-r
2Mn2+ + 5 So?- +3H2o Volume = 100 cm3

:tolulion.
Step 2. To determine the moloity of SQ- ion
- Molaritv=I&!E!L,
*--1ffi
.
Let M, be the molarity of SOI- ions in acid =1,f lN = 0., t
t44" 19
rain water. Applying molarity equation, Step 3. To calculate lhe volume of 0 01 M
M,V. M.V. KMIO. solution
---= (So3-) = ---:--1 (Mno;) Applying molarity equation tobalanced redox
' equation,
we have,
Mr x 25 M.V, M,V^
or5=z 35 x 0.02
,j tn"c'o') = ,'2' '(KMno,)
Mr= 35x0.02x5
') ,! )< =0 07 or5 0 1x 100 0.01 x V2
3
Thus, the molarity of SOr2- ions in acid rain
water = 0.07 M.
or _. 3 x 0.1x lm
Vr=ffi=600cm3
Mol. wt. of Sol- ions = 32 + 48 = 80 Thus, volume ol 0.01 M KMnOn solution re-

.'. Amount of SO!- ions in rain water quired = 600 cmt.

IaXA.I\IPLII 9.17.25.0 crrf oI a solution con-
=0.07x8=0'56gI-r. taining 15'0 g oI a panially ctxidisied sample of green
i._\ '\:li' )
l.44goIpure FeCrOo was
1..
vitriol (FeSO o .7 HrO) per libe requircd 20.0 cm3
dissolved in dil. HSO| snd lhe solution diluted ml of 0 01 M potassium dichromate sofution for
b 100 cnf. Colculate the volume of 0.01 M oidotion in acidic medium. Find out the pertentage
KMrtO, reqtired to oidise FeCrO. sohttion com- purity of the given sample of green vitiol.
pletely. Sllution. Step |ro wite balanced equarion
S..qfqtlort. Step l. To write the balanced equa- lor the redox reaction
tion Ior the redox reaction. IqCr2O? + 4HrSO.-----*
Both the cationic and anionic components of IQSO, + Crr(SOn)3 + 4HzO + 3 O
FeCrOo (ferrous oxalate), i.e., Fe2+ and QOI- are
2 FeSOa + H2SO4 +O
oxidised by KMnO. to Fe3+ and CO, respective ly.
-
Fer(SOo), + H2O Ix 3
the complete balanced redox equation is
5 Fe2+ + MnOr- + 8 H+ """'> IqCr2O? + 6 FeSOa + 7 HrSOo--+
5Fe3++Mn2++4H2o Iqso4 + cr2(so4)' + 3 Fer(Soo)' + THro
 REDOX BEACTIONS
9t31
From the above cquation 2 KI + H2SO. + HzO2 +
1 mole of KrCrrO, = 6 moles of FeSOo
K.SOI +Iz+HzO
Step 2. Tb find percentage puity of geen vitriol. 2 NarSrO, + I, NqSoO. + 2 NaI
Let M, be the molarity of the oxidised sarnple -+
of grcen vitriol. Appllng molarity cquation, we 2 KI + H2SO4 * 2 NarSrO, + H2O2 .*
have,
ItSOn + NqSoO6 + 2NaI + 2H2O
M,x25
rfJJ {r*so.) = 4fg t,.,.tr.,1 From the above equation,

20 x 0.01 x6 1 mole of HrO, = 1 mole of lz

or M, = = 0.048 M
25 : 2 moles of NarSrO,
Mol. wt. of FeSOn.T HrO Step 2. Tb lnd
out the concentration ol H
20 Z
= 56 + 32+ 4 x 16 + 7 x 18 = 2it8 Let the molarity of HrO, solution = M,
Wt. of pure FeSOa.T H2O Applying molarity equation,
= 278 x 0.048 = ti.344gL-1 M,V, M-V-
'% purity ofgreen vitriol -"-::(H2O2) = (NurSrOr)
13.444 f
= 15 x 100 = EE.96
M1 x25
or1=z 10x0.1

in acidic medium and lhe liberuted iodine required or M, = 19-I!-1 = o.o2 M

10.0 cru3 of0.) M thiosulphate sohttiott. Fiid our
the concaimtion olHrOrin Mol. wt. of H2O2 = 2 x I + 2
grams per litre ? x 16 = A
S_S!!ISL Stepl.Tb wite the boluncett chemi- .'. Concentration of HrO,
cal equotion of the redor rcoclion.
= 0.OZ y.34 = 0.6Eg L-I.

I. Calculatc the volume of 0.05 M KMoOa solution

required to uidise completcly 2.
(H2qO, iD acidic medium.
2. How maDy grams of I(2G2O7 Deutralization of fcrrous calate solu iD acidic
cidise Fe2+ present 15.ZgofItSOa to Fe3+
medium. I .f S0 trlU
iD if
thc rection is carricd out in aD acidic medium.
6. Metallrc rin in presnce of HCI is oxidised by
IqCr2OT to stannic cbloride. What volume of

3. ls .0 cm3 of 0. t z M rrrlno. solurioo

Ia decinonnaldichromate solutioD will be reduced ty
ijl l g of rio ? At. 1+t- of Sn I18.?)
=
to qidise m.0 ml of FCSO. solurion in acidic
medium. What is themncntration of FeSOa solu- [ 336.9 cm3l
7. tlow many millimoles of potassiu chromate is
requ
solut
4,2.48
of rhe solution. 2I) cm3 of thb solutioo rquired
l0
cml of0.0l M iodioc solutioo. F.lnd out
rhe value
l,\nsst.67%l or-t I ,5l

i
 Netu CouYse Che i stru
9132

9. 0.2gof asampleof H2O2 reduced20 ml cf " t

li{ decimolar KIor for comPlete sridaticn oi I- icns

KMno4 solution in acidic medium' What is the to ICI. Find out the lalue of V [ .\us. 20 cm3l
pcrcrntage purity of the samPle of H2O2 ? 1r. Both cr2ol- (4q) and Mno4- (44) csn bc uscd to
[ \ns t57o] titrate Fe2+ (4q). lf in a given titration, z'50 cm3
10. 16.6 g was dissolved iD
of0 1 M Crzol- were used, then what volume of
wate; uPto one litre' V
cm3 of with 20 cm3 of2 0. 1 M MnO; solution lvould haYe been used for
M HCI quired l0 cm3 of the same titration ? I At's. 29.4 cm3l

FORDIFFICULT r2R.O
20 I
l. Balanced equation for the redo'x reaction is: 15 12
truror) - tn"so,)
2KMnOa + 5 (COOH), + 3 HrSOo-
to i.,M

Iqso4 + 2Moso4 + 10 co2 + 8H2o or ru, = 1lffirJ9 - 6 a5 v

No. of moles of oxalic acid = 2 70/90 = 0 03 mole 4. Balaoced chemical equation for the redox reaction
From tbe balanccd cquation, is:
5 moles of (cooH)2 = 2 moles of KMnor 2 MnO4- + 16 H+ + 5 qol-
to ol -
.. 0.03 moleof (cooE)z=215 2 Mn2+ + 10 co2 + 8 tl2o
=0 0'12 mole of KMnOa ApPtYing molaritY equation'
Now 0 05 mole of KMnOI is present in solution Mr 10 o cl,"8tunor-)
= 1fi)0 cm3
i rcroi-) =

. . 0 0'12 mole of KMnOI is Present in solu(ioD

or Mr =0 02M

_ 1000 x 0 012 Mol. wt. of qol- = e

0.05 - 240 cm3
Conc. of qO;-ingL-l =ea xo 02-I 768
2. The balanced chemical equation for theredoxreac-
tion is : % qol- =L:!! J)oo =ss'67.
K2Cr2o7 + 6FcSOa + ? HrSOr....
5. MolaritY of Ieqol solulior
+ Cr2(so1)3 + cr2(Sod3 + 7 H2o
Iqsoi
From the balanc.e(r ,'quaiion, ii is clear that
6 moles of Feso4 = 1 mole of lc2cr2o?

or6 x 152I of FeSOa are orddised bY =#=o.ortro

l,tct|O1 = 294 g The balancd chemical equaiion for the tedox reac-
tion is :
or 15 2I of FeSOl are oxidised by IqCr2OT
5 FeqOl + 3 MnO4- * 2411+ *
- 6 x ls2 " '-
--2!-,,<.'t - 5 Fe3+ + 3 lr{n2+ ' 10 Coz + 12 Hzo

=4.98 AppllDg molaritY equation, we have,

reac-
3. The balanced chemical equation for the redox 0 013x v (lvlno4-) = 0 025-x 100 lpec2oa)
tion is :
KMnO4 + l0 FaSOo + HtSOo 0025x100x3
or --v - --3-i-6TT-
2 8
-
IqSo4 + 2MnSO4 + 5 Fe2(Sod3 + 8 H2o
molarity equatioo to the above redox = 150 cm3
APplyiog
reacticn,
FIEDCX HEACTIONS
9/33

coi.j'iD.
6. Balanccd chemical equatioD is:
= 158 + l8.r
ZK^CrzO7 + 3Sn+28HCt .. Amouflt of Na2S2O3 .rH2O prescnt per litre
2(: x39+2 x5:+7x l{,) 3x356.t
116 7 -
=2x294 - g - (1s8 + 18.r) x 0.Or 8
=5E8s But the adual amount dissotved 2.48 g
4KCl + 4 C[CI3 + 3 Sncta + l4H2O =
EquatiDg these values, we have,
Now 356.1 g Sn react wi r IqCr2OT = 588t (15t + 18r) xo.O1 =2.48 orr=s
9. No. of moles ofKMDO4 prcsent in 20 mlof0.1 M
.. l gSn wil reacr with IqGrO? = ;:qig
KMnO{ solurion = -?9- " 9.1 = 2 x l0-3
= I .6519
Eq. *t. orK2cr2o7 = t'of* =?=0, The balaoced equaron for the redox reaction is :
2KMnOa+5H2O2+3H2SO1--
Decinormal K2C[2O7 solutio[ means l00O cm3
solurior-r coritaiiis 1.9 g y\Crzol, i.e. 1.9 g K2SOa + 2MoSOa + 8 H2O + 5 02
From the equation,
IqCr2O? are present iD l00O cm3 solution
2 moles of KMnO4
.. l = 5 moles of H2O2
65t I K2CtzO:. wil be present in
1000
.. 2 x 7O-3 moles of KMDO4 will react with
{f x l 65l cnrr = 336.9 crn3
arOr=|xz xro-3=5 x to-3 rroles
7. No. of mittimoles of IqCrzOT presenr in 24 cnt3 of
0 5 Msolution = 24 x 0.5 = t2 Mol. w1. of H2O2 = 34
The balanccd chemicalequation for rhe redox reac_ .. Amount ofH2O2 actually preseot
tion is :
K2CI2O7 + 6 (NUa)2SOa. FcSOa. 6 H2O + 7 H2SOa =34x5xtO-3=O.l7g
IqSO4 + 6 (NH4)2SO4 + 3 Fe2(SOd3 :. %agepuityotH,O, =ffi x roo = rs
-
r cr"(So4)j + 43 H2O 10. The ctremical equation for the redox reaction is :
Fiom rhe balaDced equation,
IO3- +2I- +6HCt+3ICt +3Cl- +3H2O
6 moles Mohr's satt are oddised by IqCr2OT

- 1 Drole Molarity of KI soturioo = 1it;u o I frl

=
.. 12 n'tillimoles of Mohr's salt will be oxidisd by
Applying Dolariry equaUon,
K.Cr-O-=lxrr
..t 6

= 2 millimolcs $Jror=!i!1,oo,,
t. The balaDced equatioD for the redox reactioo is : or V=20cm3
2 Na2S2OJ + Iz ...-,Na2SaO6+?NaI 11. Suppose V, cm3 of M, Fe2+ is ritrated agaiost
Lct thc nlolarity of NES2O3 .x H2O solution Ml
= 2 50 cm3 o.r M Crrol- and V, cm3 of 0.1 M
Applying molarity equatioD to rhe above redox
rcaction, we have, Mn04- solutions, then,
M, x20
_--_ ('! .2u3) = (I2)
?1{-!11c,,q-) -',,v, ir",*y
i (,
.. Mt=oolM Vr x0.l M^V-
cnd ---- (MnOo-) = -i-:1Fe2+)
Mol. wt. of Na2S2O3 .-rH2O ...0.r)

- 2 x 23 + 2 x 32 + 3 x 16 +.r x 18
Equating (i) ard (ii), Vr = 29.4 cm3
 i. lndirect Redox Reactions-
Electrochemical Ce[ls

coll. Thus,
cell
,4n electrochemical celt or simply a chemlcal

bridge.
When the switch is in the off position' no
no
reaction takes place in either ofthe beakers and

9.13.1. Construction ELECTRON

FLOW
of an Electrochemical
Cell

the above redox reaction

indirectly, Place zinc rod I'(uso.'- l"-
in 1M ZnSOn solution in zSol l@
the lefl beaker and a coP-
per rod in a lMCuSOo CATHODE
solution in the
COP P ER
zrN c ROO
ROD
CUSO4
ZnSo4 SOL.
SOL,
salt solution in each
UULIr the reduced
DCaKCT both
bcaker
anri oxidized forms of the 9.2. An electrochemical or galvanic cell
rRF s
FIGURE
same sPecies are Ptesent'
',Gr
--ten-i*n in the rcdox reacti do not tcsct wilh lhc solutioN of thc
a."-,r"frt" is onc whotc ioo6 do not tslc part thc is silvEr containirgAgNo3
clcctrolytcs takcn ln th" tcur"ts' not "-tfr""jxE
tTiti'Iiii''Jtjiri "* "i 'tccttodc
white PPt of AgCl
u.**" XO ,"acts with AgNO3 6olutioo to form
"olurion
 REDOX REACTIONS
9/35
current flows through the metallic wire. As soon as
the switch is in the on position, the voltmeter shoqrs
a deflection thereby indicating the flow of current
through the circuit.
Let us investigate as to why this current flows.
This currcnt is due to chemical reactioa taking
place in two beakers. COPPER
VESSEL

POROUS POT

soL.'
zrNc Roo
ZnSO!
soL.

FIGUBE 9.3. A popular form of DanleX ce[.

Zil (s) Znz+ (aq) +2e- ...(r)
ectrons flow in the outer
- r cLcuit is completed by
olution to the other and

(ri) It helps to maintain the electrical

oeutrality of the solutions in the two half cells due
to flow of ions (e.g. SOI- ions may shift and com_
bine with the Zn2+ ions in the hrst half cell).
d* (oq) + 2e- --.+ Cu (r) ...(O , ,lf the salt btidge is not cmployed the flow o[
etecuTc cunent will not occur as e>rplained below '
The overall reaction taking place in rwo :
beakers is The moment the two rods are connected by a
Zn (s) + C\2+ (aq).-...- Z.*+ (a4) + Cu (s) copper wire, the flow of electrons from zinc to

migrate from CuSOo solution to the ZnSO. solu- As Zn2+- ions are produced near tbe zinc rod,
tion. an equal number of SO!- ions will mou"
fronr i#
. 9.132. Salt bridge and its funcflons. The two
main functions of the salt bridge are as follows :
. .(i) It a[ows the movement of ions from one
solutron lo the other without mixing of
the two
 Net4 Coarse Chemlstrglffi
om the negativcPole
a result. the solutions in the two beakers remain circuit However'
electically neutral and lhus allow lhe electic
cwrent to nal
;; suid ro flow itr' tltc
to llow.
9.133. Salient featurcs ofan Electrochemical
cett. Som" important foatures of an electrochemi-
cal ccll are sumarized below :
(i) Thc zinc ro occurs
the anode
which
is caliid
iieietluction take" d"'
current falls with the passage of time'
(ir) As a result of rcdox rcaction' lhe weight
,'r .Jn.i"i rod increuscs whilc thut uf zinc roJ
J..r.'ri.t rr,lI' g"in and loss in wcights oIthc nrcti'l
.,,,t. i. ln ttt. raio of thcir equiYalcnt wcights For
example,
l-oss in wcil,ht ol Tinc rod E(l' \\4 o[ Ztr
GffiGshGf .qrP.**t - Eq 'r1 of cu
-3250
31.75
Somc imporatnt gcneralizi'tiorts atrout an
ctrochemical'cell maybc summed up aslollows
:
ele

Oxidation occurs at lhe anodc whilc reduction

-oi..ru's at the cathode
A.node aca us a negativ Pole Pl'i& calhode
scls

half cell reactions' unode lo ctthoile in the eier-

(v) The two half reactions always take place urrent lows from calhode lo
tokc
simulianeously, i.e., ha[ cell retctions cannot unode.
m
Chtmical energ ol lhe redox rtsclion occutnng
the galvanic cell is converted inlo electrlcal energ'
The two main functions ol the salt bridge are
as follorvs:-
(,) r
onc soluti
solutions.
(rvhcreas
wirc).
posltlYe Polc or electrode'

the sone ionic mabilitier

(i'e' dirlance trovellzd
Onlv forwhich in the sah briclge' Tltus
pot ) orc wed os electrolftet
by in nder a
"riil od Nuox acl' NaNo3 and Na2soa'
mobility'
among anioru' OH- hat tlrc highesl ionic
Among corions, H+ ion lws the hig!rcst ionic nobiliry and
ordcr
common cations and anions follous lhe
:
:n
i i&i"
".oiri,y.rsome , cr'*
c"tion", rr+ > NHf, = 6+ t Ag* < NIg2t, Na+ > Lr+
REDOX REACTIONS 9137

ADb To'lci0h kNowrcocr coi\'tD.

Anions: OH- > SO;- > cl- > NOt > CO3- > F- > CH3CoO-.
iiii -r. Agrr-ugor is a seaweed coUoid. Ilb a mbowe of two polysacchorides, i.e. agarose (main) ond agorcpectirl lt.
dissolves in hot water and sets, on cooliDg, to a jelly at concentratioo as low as 0.57o. Its chief uscs arc as a
solid medium for cultivating micro-organisms, as a thiikner, as aD eorulsioo stabilizer in food industry and as
a laxativs.

9.13.4.ReprtsenlatlonofanElectrochemical flE
Cell
An electrochemical cell is ropresented in a electode potantial
manner as illustrated below for the Daniell cell :

Zr I hl+ (cr) llcu'?+(cr) | Cu

By convention, the electrode on which oxida-
iion occursis written on the left hand side and the
electrode on which reduction occurs is written on
represent the concentratiou of Zn2+ (aq) ions and
Cuzt (a4) ions respectively.
-
In a similar manner Cu AgNO, cell may be
represented as Cu lCu2+(q) llAC*(.J IAC
Instcad of writing siugle vertical liaes, some-
times semicolons are used. Thus, the above cells
may be represented as
Zn iZnz+ (c) llcu2+(cJ;
cu; cu2+(q) llAc*(%) ; Ac
Further, when the ions are in direct contact
e.g. for Daniell cell using a porous pot, a single
vertical line instead ofa double vertical line
Thus, in such a case, we have :
Zr;Z*+ (cr) I Cuz+(q) ; Cu
9.14. Electrodc Potenlialij,. :, .:r,: : ,:
Further, the electrode potential is termed as
oxidatloD potenual if the electrode loses electroas
and is called the reduction potentlsl if the
electrode gains electrons. Oxidation and reduction
potentials are just reverse of each other. For ex-
ample, if the oxidation potential of an electrode is
.r voltr then its reduction potential is - .r volrJ.
9.141. Effect of Concentratlon (or mtal
ions) and Temperature on the Electrod Potentlal
- Standard Electrode Potntial,
When an electrode say zhc rod is dipped in
the solution of its own ions, the following two op-
posing tendencies may occur :
(i) The zinc atoms of the rod may lose electrons
to lorm Zi+ iom which pass into the solution and
the electrons thus released accumulate on the rod
(Ftg.9.a a).
zt (s)""-' znz+ (aq) + 2 e- (oxidation)
(ri) These accumulated electrons may attract
the Znz+ ions from the solution to form atoms of
Cu zinc metal which get deposited on the zinc rod.
is used.
:j,: :i,: . r,.:' ':. ., r.. ' :. '. :
i',: ': : :: :: : r.

9.14.1. Delinitlon.
It has been discused above that each
electrochemical cell consists of two electrodes or
half cells. Each electrode, in turn, consists of a
metal dipped in the solution ofits own ions. At ore
of these electrodes, oxidation occurs while at the
other, reduction takes place. In other words, one
oo
OXIDATIONTENOENCY REDUCTIONTENDENCY

FIGURE 9.4. Development of a

electrode has a tendency to lose electronswhile the Dotential difiercncc between'la\ Zn and Zn2+
'
other has a tendency to gain electroN. ions and (b) Cu and Cu2+ iorB.
 9i 38
Z*+ (aq) + 2c- + Zn (s) Qcduction)
These two opposing tendcncies will continuc
ancl evcntually thc tbllowing cquilibrium is
reached.
Zn (,r) Zn2+ (aq) + Zc-
==l
Now if thc motal has a higher tcndcncy to get
oxidised, then at equilibrium the metal rod will
acquire a net negalivr, charge h).rt. thc solution. Il
however, the metal ions have a highcr tendency to
get reduced (Fig. 9.4 b), a net positive charge will
develop on the rod nzrr. the solution. This separa-
tion of chargcs, in turo, creates a potential dif-
tcrence betrveen the metal rod and the solution.
?-ltis potential diffcrence whiclt is set up betwacn the
trlctol atd. its own ioh- iit the sohttion is colled the
electrode potential, Tho magnitude ofthis potential
diffcrcncc, however clepcnds upon thc following
lactors.
(i) the ndturc oI the nrtql and its ions
(ii) the concentrarion of the ions in solution
(iii) teruperaturc
Thus, we conclu<le that clectrode potentials
dcpcnd upon the concentration ofthe mctalions in
solutioo and the tcmperature. Therefore, electrode
poleltials are gcnerally measured undcr standard
conditions i.e. 7 molar concentrulion of ntetal ions
(1 nnl L-t) ond a tempcratute of 29ti K and arc
colled staodard clectrode potcntials ancl are
tlenotcd by E".
Thus, to definc a standard clectrode potentiaLl
for a half cell or an clcctrode, wc writc
Cu2+( l mol I--1, aq) + 2d-
--"- Cu(s)
Thc equation tbr the lulf cell is rvritten as a
red ction reaction and rhc electrode potential is
callc d,rt au do rd rcdr tc lion potanl a l.
9.14.3. Measurement of Standard Electrode
Potcntial.
'I'hs absolute value of potcntial for a single
clcctrodc cannot be mcasurcd directlv because of
the following Lwo rcasons :
(i) A holf ccll reaction cannot take ploce inde-
Pendently.
(ii) It is a rclative tentlency b lose or gqin
electrons.
(iii) For puryose of nuqsurcnrcn4 as )-oon as
otlolhct melul conductot i,t prtt into thc tolution, it
will sct up its own pote tiol.
_'The_activiticsofpurEsolidsandliquidsorlakclasunityandindilutcaqucoussolutions,thcactivityofagiv.nsolutionis
nearly equal to its ftolarity. For gaseous spccies, thc activityis nearlyequal to its pafiisl prcssurc cxprcsscd in
pressure, thc activity of thc (ascous species is ncarlyone.
l'radtcy's Neu, Coatse themistr4 &Il1I!
In view of thesc diffrculties, the electrode
potential has to be mcasured against some rcfer.
ence electrode. The reference electrode u.sed is the
standard or normal hydrogen electrode (NHE).
It consists of a platinized platinum electrode
(platinum electrode having a coating of black
platinum) dipped in 1 M* (more precisely unit
activity) solution of H+ ions (1 M HCt) at 298 K
and pure hydrogen gas maintained at a pressure of
1 bar* is bubbled through thc solution containing
platinized platinum electrode (Fig. 9.5).
H2 GAS AT
1 BAR PRESSURE
COPPER WRE
BUBBLES Hg
OF H2 GAS
lrcl soL.
PLATINUM FOIL
COATED WTH
Pt BLACK
FIGUPE 9.5. Standard Hydrogen Elechode.
The finely dividedblack plathum coated over
plaiinum absorbs H2 and thus herlps to establish a
rapid equilibrium betvr'een Ii2 and H+ iorls :
When in a ccll, this electrode acts as theaaoda
i.e. oidation takes place, the tbllowing rcaction
occurs, i.e., some hydrogen gas changes into H+
ions which go into the solution.
Hrk) 2H+(aq) + 2e-
When this electrode
- acts as the cathode, i.e.
reduclion takes place, the lollowing reaction oc-
curs:
zH+(sq) + 2e- + H2k)
i.e. some H+ ions from the solution change
into H, gas. Thus, tie electrode it rcverrible witlt
rcspect to H+ ions, This electrode is usually rcpre-
sented as:Pt, H2G, l bar), H+ (aq,cotc:c)
nrc ekctrode potcntiql of tlrc standard
Itydtogen electrode is tuken ss zero.
bi. Thus at 1 bar
 REDOX REACTIONS 9/39

To determine the electrode potential of any
electrode, a cell is set up using this electrode as ons
of the electrodes and the second slectrodu is the
standard hydrogen electrode. The EMF of the cell
is measured. As the EMF of the cell is thc dif-
ference in the electrode potentials of the two half
cells and since the eloctrode potential of the staod-
ard hydrogen electrode is taken to be zero, there-
fore the EMF of such a cell will directly give the
electrode poteotial of the cell under investigation.
The direction of flow of current further indi
at
to
vent o.iti;"
sign oxida-
tion gation
with
The determination ofelectrode potential may
be further illustrated with the help ofihe following
two simple examples :
(i)Determination of slandard electrode
potential of Zn2+ / Za ele&rode. A cell compris-
ing of zinc electrode, i.e-, Zn rod immersed in
1 M ZnSOn solution is on the left and thc standard
hydrogen electrode on the right is set up as shown
in Fig. 9.6.
Here, the reading ofthe voltmeter is 0.76 volts
and the direction of flow of electrons is from zinc
electrode to the hydrogen elcctrode. Since oxida-
tion occurs at thc zinc clectrode, therefore, the
standard electrode potcntialfor Z*+ /Znhalf cell
is - 0.76 volt.
The two halfreactions taking place in this cell
are :
Zn(s) Zna+ (aq) + Zc- (oxidation)
-> +
zE+(aq) 2c---.-..-,}{,6) (reduction)
(u) Delemrlnation of tbc standard electrode
potential of Cul +,/Cu electrode. A cell comprising
of standard hydrogen elcctrode on the let and
copper electrode , ,'.e., Cu rod immersed in
lM CUSO. solution on the right is set up as shown
in Fig. 9.7.
Here, the EMFof the cell comcs out to be 0.34
volt and the direction of flow of electrons is from
the hydrogen electrode to the copper electrode r'.e.
reduction occurs at the copper electrode. Since
reduclion occurs at the coppcr electrode, there-
fore, the staodard electrode potential for Cu2+/Cu
half cell is + 0-14.
The two half reactioru taking ptace in this cell
:ue :
ttzG) ?lt+(aq\ + 2n- (xidation)
- + 2,- ---.....r Cu(.r) (reduction)
Cl2+ (oq)
Similarly, we can determine the electrode
potential for non- nrelals which givc ncgative ioDs

VOLTMETER

SALT BRIDGE

H2 GAS AT
18AR
PR E SSUR E

,I
M HCI
sot
Pt FO'L

FIGURE 9.6. Measurcrnent of stan dard ele ctode rritenial o[ Zn2+ / Zn

elec1rode rBing cbndand hydrogen as lhe re[e;n.; '
;tb";;. -
9140
H. GAS AT
'tB,tn
PRESSURE
lMHCI
soL.
R FOIL
FIGURE 9.7. Measurement of standard electode poiential ofCu2+/Cu
electode LLsing standard hydrogen as the reference electrode.
in aqueous solution. For example, the standard
electrode poteDtial of chlorino can be determined
by using an electrode con"sisting of Cla gas at one
bar pressure in equilibrium with t molar concentra-
tion of ch.loride ions. The half reaction for such an
electrode is
cl2@)+2e- '.""- zct- (aq)
Further, by using standard
electrode, we can determine the electrode poten-
tial for metal ions involving variable oxidation
states. For example, the electrode potentialfor the
system, Fe3+(a4) /Fe2+(aq) is obtained bymeasur-
ing the EMF of the cell given below using Pt as the
inert electrodes,
Pt lHrG) lH3O+(aq) llFe3+ (aq) ;Fez+ (aq)l Pt.
From the above discussion, it follows that a
metal in contact with its own ions constitutes a half
cell and if we join two half cells together yia a salt
bridge, we get an electrochemical cell. For ex-
ample, Daniell cell can be made by joinitrg the two
half cells i.e., Zn (s)l Znz+ (aq) and Cu (s)/Cu2+
(aq) by a IQSO. salt bridge or tho two half cells are
separated by a porous pot.
'l: 1 ,r,c,r
lhe stalrdard electfode oolentrals ol a
--- - bJeln;;;;#.;
larse number of erect.odes have --'...--*:----*
reference -':"-:;'
usinc standard hvdroscn electrode as the
elecirode, for rihich the electrode potentiat
Neu
been arbitrarily taken as zero. By convention,
slandatd electrode potentials refer to reduction reac-
lions. It is because of this reason thot earlier they
were refernd lo as standard reduction electrode
potentiols. If, however, reactions are written in the
opposite way i.e. as an oxidation reaction, the
electrode potentials are referred ao as standard
oxidstion electrode potentials. Since reduction half
hydrogen reaction is just the reverse of oxidation half reac-
tion, the oxidation potential of any electrode is
obtained from the reduction potential just by
sfinnging the sign. For example, the Jran dard reduc-
tion potential of the electrode Znz+ /Zt (aq) for the
reaction,
Zn2+ (aq) + 2z- Zn(s) is - 0.76 \
----.-----,
then the standsrd oxidation potentiol of lhe
elecftode Z,a./Zrl+ (aq) for the reaction,
Zn(s)- Z*+ (aq) + k- is + 0.76Y.
According to the latest convention adoptedby
IUPAC, the terms standard oxidation electrode
potential and standard reduction electrode poten-
tial are not used but only the term standard
electrode potential is used and the half cell reac-
tioos are always written as reduction reactio[s.
Furthcr,
Standard electrode potential is given a posl.
ttve sl8,r.if rcduction occtt* otthat eleclrode L''rt' lhe
stq,tdard hydrosen electrode and is giverr a negative
!|:.4
srgn u o*qalron occurs 4I Ine etectroae w'iL tne
has
HEDOX REACTIONS 9141

standa hydmgen electode. Futhq the mognitude table, the reducing agents are written in decreasing
ol lhe slandard elecEode potential is a measure oI the order of their strength i.e., the tendency of the
tendency of the haff reaclion to occur in the torward oxidation half reaction goes on decreasing as we
direcion i.e., in lhe direction of reduction. move from top to bottom. Such a llst of reducing
The standard electrode potntials of a num- agents amnged in deoeasing order of thei strength
ber of electrodes at 1 M concentration of the dis- is cdlled the actiity or lectromotlve or
solved ions at 298 K are given in Thble 9.1. In this electrochemlcal serles.

t'ABLE 9.1. Standard electrode potentials at 29E K

Electrode Reoction

Lt', (4q) + L(') 05

e
-3
K+ @q) + c- K(r)
-2.93
Ba2+ 1oq'1 + zr' Ba (r)
-2.90
Caz+ (aq) + 2e- caG) 47
-2
Na+1aq; + Na(r)
"- -2.'71
u{+ 1aq1 + ze- Ms(r)
-2.31
AJl+ 1aq1 + zc' Al(r)
-1.66
zEzo(t) + 2e- H2(g + 2oH- (oq) --{ 83
7n2+ (aq) + 2e- zn(t) {).76
cf+ pq1 + t"- CrG)
-0 74

Fez+ (aq) + 2e- Fc(r) ---0.40

Cd.+ (oq) + 2e' G(r) --4.40
PbSOa(r) + 2e- Pb(') + sol-(aq) {).31
c&+ @q) + zc- co(r) -4.28
Niz+ (oq) + 2e - N(r) -4.25
sn''(aq)+2e Sn(r) --4.14
Pb2+ (oq) + 2c- Pb(r) {).13
Fe3+ 1aq1 + le' FeG) ---0.036
2H+ 1a41 + ze- H2(g) (standard clctrode) 0.00

AgBr(r) + -e Ag(8) + Rr- + 0.'10

Agcl(r) + .- Ag(r) + ct- + O.22
Cuz+ 1a41 + c- cr*(oq) + 0 18

Crl+ 1aq1 + zc- Cu(r) + 0.34

Cu+ 1aq1 + e- Cu(s) + 0.52
126) + 2c' 2l- (aq) + 0.54

ozg) +2:g^+ +2e- HzOz(I) + 0.68

e-
Fe3+ 1oq'; + F"'* (oq) +O7'l
tt$+ @q) + zc- 2Hs(I) + 0.79
 9142 Pradeep's
TABLE 9.1. Contd.-.-..

Ag+ , + ......- Ag(r) +080

1aq
"'
llgz+ 1aqy + ze- .......- IIg(l) + 0.85
Not(aq)+4H+ + 3d- NoG) + 2H2o (I) + o.97
Br2(g) + 2e- -+ 2Bt-(oq) + I .08

)oyg * zarot lo, t z.- 3H20(l) + 1.23

crro|-1oq1+ 4Ir+ + 6e- - ZCf +
@q) + 1H2O (s) +I33
ClzQ) + 2e- - 2ct-(4q) + 1.36
Mnoa-(oq) + 8H3O+(a{) + 5e- - Ynz+ 1aq'1 a 1211r91q + 1.49
nu3+(oq) + 3e- - Au(r) + 1.50
H2o2r'q) + 2t1+ +2c- _
- 2H2O(t\ + I .78
Co3+1ary; + coz+ (aq) + I .81
"-
F2G) + 2e- +
- 2F- (aq) + 2.A',1

9.15.1. Applications of the Electromotlve electrode potential, therefore, Li metal is the

Series
Some of the important applications are given
below : crease in the order Li < K < Na therefore, their
' f. To comparr th reducing and oxldlslng
capability of elemnts. II lhe standard electrode
potentiol is great$ thon zero, then re&tced lorm is
more stoble than hydrogen gas. Similarly if the smnd-
atd elecfiode potential is negative, then hy&ogen gos
is ntore stoble llrun llv rcduced Iorm oI species. ln
other words, a negative Eo means that the redox
couple is q stronger rcducing agenl than the H+ /H2
couple ond a positive E" means thst lhe .redu couple
is u wcaker reducing agenl lhan lhe H' /H2 couplc.
The standard electrode potential of fluorioe is the
maximum in the Table 9.1, therefrrre, F, is the
strongest oxidising agent and F- ion is a very poor
reducing agent. Since the standard electrode
potentials of halogens decreases in the order
F2 > Cl2 > Br, > Ir, therefore, their oxidising
power decreases in the same order, i.e.,
F2 > Clz > Br, > [r. Conversely, the standard
electrode poteutials for halide ions decreases in the
order : I- (- 0.53 V) > Br- (- r'08 V)
Cl- (- 1 36 V) > F- (- 2'87 V), therefore,
reducing powers of the halides decrcases in the
same order, i.e., I- > Br- > Cl- > F-
Among alkali motlls, l.i (- 3 05 V) has the
lowest while Li+ ( r' 3 0-5 V) has the higlrcst
strongest reducing agent while Li+ is the weakest
oxidising agent. Since the electrode potentials in-
reducing power decreases in the opposite, i.e.,
Li >K>Na.
Besides the above applicationq electrochemi-
cal cells are exten"sively used for determining the
activity coefFrcient of electrolytes, pH of solutions,
solubility product and for potentiometric titrations.
Electrode potentials can also be used to determine
the stability of inorganic and organic species.
From the above discussion, it folloux that a
rnetal which lies higher up in the series is a better
reducingagent in the aqueous solution thanthe one
which liesbelowit. Ttrs, whereas zinc can displace
tin, lead, copper and other metals lying below it
from the aqueous solutions of their salts but copper
cannot displace lead, tin, zinc and other metals
lfng above it from the aqueous solutions of their
salts. Similary, copper can displace silver from its
salts but the reverse does not happen
2. To prodlct whther a metal wlll liberate
hydrogen from the aquous solutions of acids or
not. AII metals with negative electrode potentials
are stronger reducing agents than hydrogen and
hcncc would liberate hydrogen from the aqueous
solutitrns of acids. Conversely, all metals with posi-
tivc values of electrode potentials ore tt."U"t

4
 FIEDOX REACTIONS 9143

reducing agents than hydrogen and hence will not will libcrate hydrogcn but metals like Cu, Hg Ag
liberate hydrogen from the the aqueous solutions etc. do not liberatc hydrogen from the aquoorls
of acids. Thus, metals like Mg, Al, Zn, Fe, Sn etc. solutions of acids.

,S$$ nlt.crnourorlvE SERIES

f)\,\lll'l,I.l t).19. The standatd elecffode
potentiql corresponding to the
rqctiott
Au3+ (aq)+3 e-'-"'-Au (s) Ls I '50 V Predict iI Bold
can be dissolved in lM HCI solution and on passing
hydrogen gas through gold salt solutio4 metallic gold
willbe precipitqted or not.
Solution. Consider the half reactions,
zIJ' (aq) + 2e- .--"'+ H, (3) ; E"
Since E (1.50 V) for Au3+/Au is higher than
tnat n+lln, (0.0 v), therefore, Au3+ can be
more easi.lyreducedthan H+ ions. This implias that
Au3+ ions can be reduced to metallic gold by H,
(N.C.E.R.T,)
gas but H+ ions cannot oxidise metallic gold to
Au3+ ions. In other words, metallic gold does not
: 0'0 V ilissolve in 1 M HCl. lnstead H, gas caa rcduce gold

Au3+ (a4) +3e--, Au(s);E = 1'50V salt to metallic gold.

PO:R ,EJE;
2. With the help oftablo 9.1 select lhe reducing ageIlt
can oJddisc oxidise which can reducethe followingions totheir metallic

(a) Ct- (oq)ro Ct2@) staie (a) Ag+ (aq), (D N+ @q) and
(c) Ni2+ (ry). (N.C.E.R.T.)
(6) Fe (.r) to Fe2+ (aq) and
IdeDtiry the strongest and weakest reducing aSents
(c) l- (oq) Lo 12@q) (N.C.E.R.T.) from ihe following metals : Zn, Cu, Ag, Na, Sn.
(N.C.E.R.T,)

1.
1a; ejl species having E higher than Cl-./Cl2 2'1a.1 Alt mctals having E" lower lhan Ag+/Ag
electrode, r.-e., Mg, Al, Zn, t'c, Ni, Sn ctc.
electrode, ie., Fr, Mnoo , Au3+, acidified
(6) All nlerals having l!' Iower lhan Al3+/Al
IIrOr, c-o3+ etc. clecrrodc, i.d.. Li. K, G1. Na, MU clc.
(b) AII species baving E" higher than Fez+./Fe (c) AII nretals having E lower lhan Ni2+/Ni
electrode, i.e., Ni2+, snz+, cuz+,12, electrode, r'.e., Fe, Cr, Zn, Al, Mg, Na, Ca, K, I-i
etc.
02, Ag+, Hgz+' NO3-' Br2' Cr2O]- and all other 3. Among the elements listed, Na has the most neSa-
oxidants listed under Ans. I (a). tive F," and heoce it is the strongcst reduciDs agent
(c) All spccies having E hiSher than I-,/I2 whilc Ag has rhe hiShcst E and hence it is the
weakest reducing ageDt.
elccrrode, r'.e. tlr2, G2o?-, Cl, and other oxidants
listecl under Ans. 1 (a).

9.16. EMF ol an Eleclrochemical Cell
It is a well known tact that whenever a cur-
rent flows through two points, a potential dif-
ference is said to exist between them.The potential
difference generated by a cell when the circuit
draws no current (under conditions of zcro
electron flow) is called electromotiYe force (EMF)
or the cell potentlal.
ri'.'r':':r',+.;e,.+::ii:ri Ws know that an electrochemical c.ell consists
of two half cells, i.c., clcctrodes. C)ne of lhese
electrodes ltust havc a higher electrode potential
(higher tendcncy to lose electrons) than the othcr
electrods. A.s u result of this potential difference,
the electrons flow t'rom thc electrode at a higher
potcntial to thc elsctrodc at a lorver potentiul, i.e.,
irom nerlativc electrodc to lsss nsgative or positive

r\
9144

electrode or from less positive elecl.rode to more / lrx-{luI'f,li 9.2{t. A cell is prcpared by dipping
positive electrode. However, current flow is in a a chromium rod in I M Crr(SO.), solution and an
direction opposite to the electron flow. Thus, iron rod in I M FeSO , solution. fie standard reduc-
EMF of a cell mry be tion potentiqls of chromium and iron electrodes are
the elocltoilc pstentlols -0.75 V and -0 45 V respectively.
efl is @ wndincc.wryrt thmvdt tlrc sirait. (q) What wi be the cell ,caction ?
The standard EMF of the cell (E may be (b) Whqt will be the standard EMF of the cell ?
".r)
obtained by subtracting the standard electrode (c) lhich electrode will act qs anode ?
potential of the anode from that of the cathode, i.e., (d) l4hich electrode will acl as cathode ?
Solution. The two half cell reduction equa-
tionsf, I
Fez+ (oq) + 2 e- ' Fe (r) :
E"=-0.45v...(r)
or Eo.",, = Eocathode - Eo"nod" ...(rr) CF+ (oq) + 3 e-'--, Cr (r) ;
Further by convention, the anode is placed on E.=_0.75V...(rr)
the left and cathode is placed on the right while Since Cf +/Cr electrode has lower reduction
representing an electrochemical cell, therefore, the potential, therefore, it acts as the anode whlle
EMF of the cell is given by the e)eression Fe2+/Fe electrode with higher electrode potential
E : Eop - Eo1 "'("') acts as the cathode .
""n
where E\ and Eo" refer to the standard To equalise the number of electrons, multiply
electrode potentials of the cathode and anode Eq. (i) by 3 and Eq. (ii) by 2. But do not multiply
respectively. their E values. Thus,
In order to determine the reaction taking 3Fe2+ (oq) +6e- '3Fe(s);
place in the cell, the following steps are followed. E.=_0.45v...(",
(i) Wite reduction equations Iot both lhe zCF+ (aq) + 6d- ,2Cr (s);
eleclrodes olong with lheir electode potentisk, one E.=-0.75V...(,v)
ofter the other To obtain equation for the cell reaction, sub-
(ii) Balance the electrical charges and the num- tract Eq. (rv) from Eq. (rii), we have,
ber of atoms of each element on eitlrcr side of each 2 Cr (s) + 3Fe2+ (aq\ --'-
oI the above two rcduction equations.
ZCf+ (aq\ + 3 Fe (s) ;
Qii) Multiply each reduction equation by a
suitable integer so thqt the number of elecfions in-
E
"ar
=-045-(-075V)= + 0'30 V
volved in both the half reactions are equal. Thus, the EMF of thecell: + 0.30 Y
e EX]\r!IPI-E 9.21. The half cell reactions with
their oxidation potentiqls are
Pb (s) ""+ Pb2+ (aq) + 2 c- :
E'*i= +0'13V
(iv) Subttqct the equqtion with lowu electrode AsG) Ag (aq) + e- ;E o,,= - 0.80Y
Qeduction) potential from the one hoving higher - cell reaction and calculqte its EME
Wite the
electrode potential. This difference gives the EMF of
the cell. Rewrite the two equations in the
reuction form. Thus,
fie electrode with higier reduction potential
pb (s) ;
Pb2+ (aq\ + 2e-
has a strong tendenqt to gain elecEons and hence acts
as the calhode while lhe electmde wilh lower reduc-
-. E.=-0.13V...(')
tion has a strong tendenqt to get oxitlised potential Ag+ (aq) + e- ..-- Ae 6) ;
octs as tlrc atode. E.=+0.80v...(fi)
REDOX REACTIONS
9145

To obtain the equation for the cell reaction, Pb (s) + 2 Ag+ (aq)-------
multiply Eq. (,i) with 2 and subtract from Eq. (i),
from Eq. (di), we have, Pbz+ (oq) + 2 Ag (s) ;
E"..rr = +0 80- (-0 13) = a 6 93Y

l Calculate the standard e.m.f. ofthe cells formed by

differeDt combiDations of the followiDg halfcells :
[Given E cu2+/Cu (E.rcJ = * 0.34 volr
E"es+ze, (E","6; = +o 80voltl
Zn (r) | Znz+ (aq), Cu (r) | cuz+ (a{),
(A.I.S.B. 1986, PS.B. 1988, t9B9) [\,,, 0.46voltl
Ni (r),/ Ni2+ (a4), and AE (r) I As+ (d{)
4. Write the cell reaction and calculate the sraDdard
(N.C.E.ET) E of the cell :
(i) Zn (s) | zn2+ 1aq1l I cu2+ (aq) | cu G) ; kll znz+ O M) ll cd2+ (t M) | cJ
Ecctt = +0'34 - (-0 76) = + l 1v Given E z,r, znz+ = 0.'763 volt
(ii) Zn (s) | znz+ 1aq1 I I N i (aq) I Ni (r) ;
E 6o, *z+ = 0 403 vott
E = -0 44-(- 0'76)= +o z2v
[,\rs 0 360 volt, Zn * Cd2+.+ Zaz+
".rr ..66;
(iii) Zo (s) | znz+ 1aq1l I As+ (aq) I As (r) ;
5. Thc standard EMF of the cetl
E'cctr = + 0 80 - (- 0 76) = 11 56Y Ni lNi2+ llcu2++cu
(iy) Ni (r) | Ni2+ 1a4; 1 1 cu2+ 1aq; I cu 1,y; is 0.59 volt. The staDdard electrode potential
(reductioo potential) of copper electroda is 0.34
E = + 0 3+O - (- 0 44) = + 0 7tV volt. Caiculate ihe dard electrode potential of
".rr
(v) Ni (.r) | Ni2+ 1aq; 1 I As+ (aq) | As (r); nickel electrode. Btrz+, m = _{.25 voltl
I
Eccn = + 0 80 - (- O 44) = 1 1 24Y 6. The e.m.t (E) ofthe fo ot ing cells are

(yi) Cu (.r) | ctz+ 1oq1 I I As+ (aq) | As (r) ;

fu I A8+ (1 M; ll Cu2+ (l M) Cu;
E ccrr = + o 8o - (- 0 34; = 16 46Y. E'=J) 46V
2. A cell is prepared by dipping copper rod in 7n I znz+ (t M) | | cu2+ (l M) | cu:
lM
copper sulphate solution and zinc rod in lM E = + l.l0V
ZDSOa solutioD. The standard rcductioD poteDtials Calculate the e.m.l of the cll
of oopperandzincare0,34aod -.T6Vrespective-
zn I Zn2+ 1tM) | | Ag+ (t M) l Ag
ty.
(i) What is the cc reacrioD ?
(A.I.S.B_ 1989) | . r.s6!,I
7. Tixo halfcrlls are
(rl) What will be the standard electromotive force
(EMF) of the cell ? et3+ laqy t X ana Mg2+ 1aq1 t Mg
(rli) Wbich electrode will be posirive ? The reductioo potentials of these half cells are
(iv) How will rhe cll be represented ? V and V respcctively. Calculate rhe
-1.66
cell -2.36the cll reaction
potential. Write also.
[,rns (r) Zn (s) + CuSO. (a4)- ZnSOI (a{) + Cu
(s)(ii)E.",=f I V (rir) Cu electrode (PS.B. 1ee7) I
0.70 Y
(iy) zn I znso. (t M) ll cuso. (t M) cu] 3Mg+2A13+*3Mg2++2All
|
E. Calculate E. for the cell
3. Following cell is st up belwcen copper and situer
electrodes: Cu I Cuz+ (,,q) ll AE+ @q) | Ag Al Ar3 + (1
I ll
M) Cu2+ (1 M) | Cu.
If its two halfcells work under standard conditions, Given : EoAtr+/,At and E.cu2+/.cu as .66 v and _l
calculate the e.m.f. of the cell 0.34 V respecrivety. (H.P-S.B- 1997) 1, 2.0Vl -
 NeuJ Co ntse Clteat istrtl
9i 46

9.16.1. To prealict the SPontaneity ofa Redox

Reactlon
The EMF of a cell is an important ProPerty.It
can be used to predict the spontaneity of a redox
does not ocaur ; instead, the reverse reaction oc-
reaction as discossed below. will illustrate this
curs. The following examples
To predict whether a given redox reaction is point :
teasible or not, the EMF ofthe cell based upon the

@ l,lKAltPl-ti 9.22. Predict whether zinc and sil- Thus the EMFof the supposed cell comes out
eer reuct with 1 M sulphuic acid to give ont hydrogen to be negative. Hence this reaction docs not take
or not. Givert thal the stqndqrd potentials of zinc ond place.
silver are - 0.76volt and t 0.80 volt respectively' /
lix.\l\l ['t,la 9.2-1. Can a solution of I M copper
(q) To predict rcaction of zittc with sulphate be stored in a vessel made of nickel nwtql ?
sulltlruic acid : Given that E.y; ,y12+ :
+ 0.25 volt,
If Zn reacts, the following reaction should Ecu ,crr*: -0.34 volt.
take place ot Is itpossible to store copper sulphate solution
Zn * HrSOa ...* ZnSOr*Hz in a nickel iessel ? (N.C'E'R'T')
i.e., Zn*Z}l+- Znz+ + H, In this Problem, we want to see
whether the following reaction takes place or not
By convention, the cell will be represented as
Ni+ cuso4 + Niso4+cu
Ztl Z*+ llH+ lHz +
i.e. Ni + Cu2+ Ni2+ Cu
Stanrlard EMF of the cell ----
8y convention, the cellmay be represented as
E"""tt = (E ;gnt) - Bt"r, Ni I Ni'z+ llCu2+ | cu
:0-(-0.76) = * 0'76 volt We are given that tbe oxidation potentials as
Thus the EMF of the cell comes out to be
E r.*i . Ni2+ :
+ 0'25 volt
positive. Hence the reaction takes place.
and E :
-0.34 volt
cu2+
(b\ To predict the reoction of silver with sul' cu ,

ptudc acid . Hence the reduction potentials will be

If Ag reacts, the tollowing reaction should BUi2+,Ni : - ffr.ti, Niz+
take place :
= - 0.25 volt
2Ag + H2SO4-----' AgrSOa * H,
and E arz+,* = - E c,,cu2r
i.e. 2Ag+ ZP.+ '-"' tu\g+ + Hz
= + 0.34 volt
By convention, the cell may be represented as Now 8".1 = Eo;r6, - E"1.6,
Ag I Ag+ llH+ lH, + 0.3a -(- 0.25) =
''' Erefi : Eog+.trr - E"eg*.ag = + 0 59volt
Thus EMF comcs out to bc positive. 'Ihis
=0-0ttO implies that CuSOo rcacts with nickel. Hencc
= -0.80 volt culttot be $torcd it u ttickel vcrscl
CuSOo solution
REDOX BEACTIONS
sl47

,P,-,RAC-TICIE- '
3. Is it safe ro stir I M AgNO3 solutioo with a copFr
lowing metals :
(i) copper (n) tead (ir'i) iron
sPoon? GiirD E'Ag+AS
= o.Eorolt E Cu2+
,
Given E Crr2+ Cu = 0.34 volt ; E.pb2+ pb =--O.34 \Dl!. Frplain Not
rr .
. 4. Can we use a copper vcssel to store
,
I M A8NO3
= --{.13 vok ; and E"Fc2+ Fc = -{1.,t4 votr
, solutio, ? ciwn thal Eocu2+/cu
= +0.34 V
t (r) No (rr) yes Gii) yesl
and Ehs+/As = + 0.80 V
2. Cao a solution of I M ZnSO4 be stored iD a vessl l.rns Nol
5. Why bluerotour of copper sulphsic lolutbn gcB
Dade of copper ? GiventbatEzl
,h?+ = + 0.76 discharged wheD zioc rod b dippcd in it ?
volt, aod EoCu2+ 0.34 volt
, Cu = (Giveo E"o,2+/ot 0.34 V and
=
I Yesl
Y7y7nz+ = 0.76 1r)

Q. I. Whst rrc the ttroJdmum oDd Dhlm![ qrldotlon ruD]6 olN, S snd Cl ?
Ars (i) The high*t qidsti, numbcf (o.N.) of N b
+5 since it ha frrrc erec'troos in the larcncc rrrcl (2 ,2 2p3)
and it! mlnimum o.N. b -3 lrince it cari accept thrce
conngatim.
chctrom to aquirc the ncarEst
'oorE
i;'g* afi"i
(lir-simihrt' thc highcst o.N. of s b +6 sinca it has sk crcctron! in the varncc
!he[ (3 ,2 3 pi ano iu ninimum
o'N. h -2 slnce it ncdr tx.o morc etcdrq'' ro acauirc the nearcsi incn gas
1ar; connguration.
(rt ) Ut,wisc the mdmum O.N. of O b +Z sinc it has sclro
clect.* io ,frl ,,rt"oo it1, ,, apr; uoO io
miDimum O.N. b -l sitrcE it rEds ooly onc morc to i-he nearest (Ar) ga!"[confguratioo.
Q2 "t.rf-nrcrd "cqr;c
Nrtrrc scrd rcts orry o6 s! odd."rrg sgc''t whirG nl'o* octs bott os otr o drfit o! rs r rcduchg
ogcnt VYhy ? 'crr
Ans (i) HNO, : Oxidarion numbr of N is HNO, aJ
=
M imum Gidation numbcr of N = + 5
Minimum qidation numbcr of N = -3
Sincc ,lE didorion rumbcr of N & HNO, ir ncintm (+5),
thereforc, it con only dcctcatc, Hcttcc HNOS acr,
only u ot cidising agent
(r'i) HNO2 : Oddation rumber of N in HNO2
= +3
Muimum qidation number of N = + 5
Minimum qidation number of N = _ 3
Tlutt, thc uidation nutbcr of N c.oa
Thatfwe, HNOroca both ar oi aidkiag .irrctcase by loiag cbctront or con
' dccrearc by tcqdng chctoru.
u
""i^;;;A;;;;'
Q 3. crtr thc rcccdor' crro;-+H:o:2 cro!-+z lt+ tc rtgarraea ar a rtaox rt cdon ?
Ar& Oridation number of Cr iD Cr2Ol- + 6
=
Oridatio6 number of Cr in CIOI-
=+6
shcc huing his rcactio4 thc axidaion nlorbct of
rtoction canaol bc regardcd an o redq rcqtion
o has ncitfur dccrcosed rur incrcorcd, thafu thc abovc

e, 4_ ldcrtlfy tbc oddants sDd reductatts lD the foltowhg reoctlotls I

(@) cH.
G) + 4ct2 G)+ cct. G) + 4HCt G)
(b) Crll2Or(aq) + 2II + (o{) + MrO2
$)- Mo2+ (aq)+zco2 @)+2H2O (D
(c)lz@ + 2s2o3- @q) 2t- (oq + s.o16- @c)
-
(d) cl2 G) + 2Br- (oq) + 2CI- (oq) + Br2@O.
(N.C.E.R.I)
9l4A
Ars. Wtiting the O.N. of atl the atoms above their symbols, we have,
-4+1(g + 4 ctz?) o +4 -1 -1
(a) c H4 c cl1 6)+4H cl G)
O.N. of C incrases ftom -- 4 in CH1 to +4 in CCll and that of Cl decreases from 0 in Cl2 to - I in CCla or
HCl, therefore, Cr2 a crs ai the oxidont ond CH 4acts 4t the reduclant'

-3 +l -2 +4 +2 +4
(b) c, H; oi @q1 + z H + (d4) + Mn oz (r) .-
MD (aq) + 2 co2 G) + 2 H2o (0
O.N. of C increass from - 3 in qH2O4 to +4 in Co2 aDd lhat of Mn dccreases ftom +4 in MoO2 to +2 in

Mn2+, therefore, Mz O2acls 4, lhe oxidonl while CzHzo 4 acls at lhe rcduclani
o +2 2- +2'5 2-
G1lrlaq1 + z s, o3@q1 zt- (dq) + s. o6@q)
- of S increases from +2 in S2O3- to +2 5 in
Here, O.N. of I decreases from 0 in 12 to - I in I- aDd that

s4o? -, therefore, 12 octs qi ,he oxidsnl tehile SrO!- acu as the reductont'

o-1 -1 o
(d) clz?) + 2 Br- (c'q) 2cl- (oq) + Btz@q)
-
Hereo.N.ofcl2decreasesfrom0inclzto-1incl-ionwhilelhatofBrincreasesftom-]inBr-ionto0
in Br2, therefore, Cr2 acts 4t the Nidait while Br- ion ocls at lhe rcduc'anl
(,),5 The electrode Pot.Dtlol of four metsllic etemenk (A, B, CondD) sr.e + 0't0' -'0 76' +0 12 8rld +0 34 V
lo$Er is the
Ans.
in the sane
order : B, C, D A.
q n ir ria n"r"* added to a solutlon contninlng Br- ohd I- lons what reactlon wlll occur lt
lr+2e-'------21' iE = +0 54Vatrd Rtz+2e- 2Br-;Eo= + 109V ?
tendency to ac4pt electrons that 12'
Ans. Since E of Br, is hiSher than that of 12, therefore, Br2-has a hiSher
c,nverscly,I.ionhasahighertendeDcytoloseelectroosthanBr-ion.Therefore,tbefollowingreactionwill
occut:
zl- 4 12+ 2e-
Brr+2e--2Br-
2l'+Bt2-l2+2Br-
In other wordt I- ion will be oxidised lo I ,white Br, will be re&rced m Br- ions'

Q.7. Is lt poesible to stort :

(i) Copper sulphnte solutior ln o zlnc ves$el ? (il) Copper sulphnte hr 6 nls[6] vqssel ?
"o;n1161
(iil) Copper sulphate solution in o silvrr vessel ? (iv) Copper sulphate sotutlor in a Sold vessel ?
(rVC.E.X.?)

Ans. (i) We caonot Placr CuSO4 solutioD in a zioc vessel, ii the followiog redox reaction occurs :

zn + cusoa + znsoa + cu 6u2* * Zr]+ o' 7n + C't

"
By conveotion, the cell may be rePresente d asZn | 7n2+ ll cu2+ lcu
.. E.c[ = E cuz+, co - E:znl+, z]t = O'14 - <- 0 76) = + r'10 v
In other words' Cr SO sohuion camol
Sincc EMF comes out be pqsitive, thercfore, CuSO4 reacts with zinc'
'
be stored in a zinc vessel
(b) Same as solved in examPle 9.23 on Page 9/46'
redo'( reaction occurs
(c) We cannot store CuSOl solution iD a silvcr ve'asel if lhe folloPins
:

2Ag + Cu2+ + /4g+ a Cu

 REOOX REACTIONS
9149
By coovention, thc cell ofthe above redq reaction may be rcprBcntcd as
AglAg+ llGr2+ lCt
and Ecccl - Eo62+, Brr+, or- -o.Bo-_0.s6v
sinc thc EMF of rhe cs[ is -ve, rhcrefore , cuso. ooo ooir*,t ffitr'sifrer.^r-0.34
In ottrer woro , cusoa sorution
catuot bc ctoted h a ilvct vcsscl
(d) Wb catrnot store, CtlSOa solution in a gold vesscl if tbe follorriDg redq reacdon
occurs :
2Au+3Cu2+ 24u3++3Cu
The cll mnEspondbt to tbc abotlc rcds rractioll msy bc repracntcd ar -
Au lAu3+ llcu2+ lcr aod E-- = B:a21, a- E Ar-0.34 _r.50 __r.2lv
since the BMF of tbe abovE reactbn is -{.c, therefore, ^or*,
cuso. sorutioo om not rcsa with gold. In other words,
Cusoasoulrion cot bc stoed h a gold trstcl

CARRYING 1 MARK
Q.1. Dellne oxidaalon srd Fducdon i]r tcr[rs ofelcctron&
ADs Odda ion i[rtolves gain ofelectrons.
Q. 2, What e enuple_
Ars Oxida e called rcdcxoreasions' Mg + F2 + M82+ (F-L'
e. 3. Derire ox
Ars. oxidisiDg educiDg ageob are electron donors.
Q. 4. Ivhat is I
Ars. Refer to the tcxt on p6ge 968.
Q. 5. The stardard elccEode potetrtials of c lev trleaals are giveD belov :
Al (-f .669, Cu(+O.gV), U(-3.0s9, Ag (+ 0.sov) oDd Ztl ({.76V),
\f,hlch of tbe$e wr[ behrve as the strotrgcst oxrdisrrg sgetrt snd phich aa the
Btrorgcat Fducrtrg ogetrt ?
Ans. Li is the slrongest reducirg ageDl white Ag+is ttre srr6ng-cst qidiSns a;enr.
Q. 6. Itr the reoctlon, MrO, + 4HCl + MnCl2 + Cl;+ 2H2O w;k; spccte6ls oxlsted ?

(B.I.I R rqhi 1990)

Ars. HCI is oxidised to Ct2.

Q, 7. What is th oxldation nuEber of

(i) C in CH2O
(M.LNR. Alldh4hn t99O)
(,r) ft tr [Pt(CzHa)cljl -
(M-LNR Allalsb&l 199i)
Ans. (i) zero Gt) 2.
Q. E. What is the oxidatior state ofNi in N(CO). ?
ll.I.s.B. 1995)
Alrs. ZEto.
Q. 9. Why is it not possible to measure the voltage ofan isolsted reduction holfreactior ? (HS.D. 1ee5)
Ars. Consult sec. 9.14.3 on page 9/38.
Q. 10. Whatb s rcdoxcouplc? W.C.E,RT)
Ans. A redq couprc comisrr of cidi.sed and rcduced form of :he same
subtancc taking prt in an qidation or
reduction half reaction. For mmpte, Zn2+ (aq)/Z^, A2 / cac" @) A- @q)
Q. 11, On the basis of stoichloDetry dcterDhc thc orddsdor truEbcr ol
(t) F h Fc!O.8rd Fea [Fc(CN)5I (A) cl ttr caocl2.
(N.C.D./!*Tl
Ans" (0 Thc compsirion of F%Oa is FeO.F%O3.
.. The O.N. of Fe iD FeO is + 2 white in Fe2O3, ir is + 3.
In Fe4 [Fe(cN)5], the o.N. ofFe inside thecoordinatioD sphere
is + 2white thar ofpe outside the coordinarion
sphere is + 3.
(fi) The composirioD of CaOCt2 is Ca(OCl)Ct. Hence, O.N.
of Ct in OO- is + t white io Ct_ ioD. ir is _ l.
 itr,.d.c1,'s Neur Course Ch.m ittrgl&ElD
9/so

A CARRYING 2 OT 3 MARKS

in each case'
Scc.9.l. Explain the terms : oxidation and rcduction iD terms ofelectrons' Give oDe examPle
to 9.-1.
ageDts according to the elect ronic concept Givoone
I)efine the terrns: oxidising agent and reducing
example in each case.
3. Comment upon thc statement : oxidation and reduction reactioos 8o side by side'
reactioo ? Give one
Scc.9.4. 4. Wtrut O" yo,i ,o,f"r.tnad by the torrDs : direct redox reactioD aDd indirect redox
to 9.6. example in each case.
to illustrate rour ansrrer.
5. Frrlain o<idatir:o_reduction readiom occurring in a beaker. Give two er(amples
6. dplain what happens when a zinc rod is dipPed io Cuso4 solulion ?

7. What are halfcells and half c.ll reactioDs ? ExPlain with examPlcs'
E. Writc the following redox reactioDs usinE halfequations-

(,) zn(r) + pbcr2(44)- Pb(r) + zrclz@q (i 2Fe3+ (aq)+21- (aq)- l2(q+2Fe2+ @4)

(iii) 2Na(r) + crzc) + 2 Nacl(r) (iv) M8(r) + ct2G) i-....- Mgcl2(r)

(v) '/r(s) + 211+ (aq)- Zn2+ (aq)+ttzg)

In each ofthe reactions given above, meDtioo
(i) whicb reactaDt is didized ? To what 'l (r') which reactant is the oxidher I

ii;4 *t i"t ,"a"runt is reduced ? 'Ib what I (iv) which reaciant is the reducr ?

[Ans. (i) ZD(,r) Zt]+ + ?t- (oxidation), Pbz+ (oq) + 2e- Ptt(s) Q"duction\
- and Zn is the reducer'
- ZD2+, Pbz+ is reduced to Pb; Pbz+ is the oxidisr
Zn is oxidised to
(ii) 2Fe3+ + 2e- zFez+ (redtction), 2l- lz + 2r- (uidotion)
-
Fc3+ is rcducEd to Fc2+, I- is oxitliscd to I2; I-
-
is the reduc'er and Fel+ is the oxidiser'

(d) 2Na 2Na+ + 2z- (atidation) , Cl, + 2e- ZCl- (teduction)

- -
NaisoxidisedtoNa+andCl2isreduccdtoCl-;NaisthereducerandCl2L\theoxidiser'
(rr) Mg-y*z+ + 2t- (ox,lation), Clz + 2e- 4 2 Cl- (redttction)

Mg is oxidised to M82+ while Cl, is reduced to Cl-; Mg is the reducer

alld Clz is the oxldiser'

(,) zna Zrf+ + 2e- (oxidation), 2H+ + 2z- Hz (teduction)

-
oddised to Zn2+ while H+ is reduced to I-I2 ; ZD is the reducer and H+ is
the oxidiser']
Zn is
case to illustrate
Sec.9 .7. 9. Define o\idation and reduction in terns oroxidatioo number. GiYe exaDlples in each
to 9. l0 your flnswer.
10. b#ne oxidising and reducing agenls il] tern]s ofoxidation number'
cite two examPles in each case
to support Your aNwer.
11. i[tt oity u t"ductant whercas SOz acls oxidant and reduclant both' Why'
irS
^
12. H2O2 acls as reductaDt as well as oxidant. Explain'
13. Explain the differeoce btween valency and oddation nuDlbr'
14. Staie and explain tbe 'Stoc* Dotation'used to name inorgaric compounds
iNoMnt different cDddatioD states'
;;;;;;il:h;;;"trectly balaDced half reactions, ;;ite theoverallnet ionic reaction in lhe following
15.
chaoges :

(i) Chloride ion is oxidised to Ch by ![4O; (in acid solutioD)

(ii) Nitrous acid (HNo2) reduces Mno4- (in acid solution)

(ii) Nitrous acid (HNOz) oxidises I- to 12 (in acid solution)

 REDOX REACTIONS
915'l
(iv) Chlorate ion (CtOt) oxidises Mn2+ ro MnO2 (r) (in acid soturion)
(p) Chromitc ion (CrOt) is oxidised by H2O? (in srroogty basic medium)
Also find out the chaDgc in the oxidatioD number of the underlined atoms.
IAns" (i) 2MnOa- + l6H+ + locl- + 2Mn2+ + 8HrO
Oxidation number of Mn changes froDr-5C12
+7 in MDO4- to +2 in Mn2+
(iD 2Moo; +6H+ +5Not + 3ItO+2Mr?+
Oxidarion Dumber of N changes-5NOt
from +3 in NOt ioD ro +5 in NOr- ion
(iii)21- + 411+ +2NO2--.....- I2 + 2NO+2H2O
Oxidatiotr number oI N changes from +3 is NOz- to +2 in NO

(iv) 3Mn2+ + ClOt + 6H+ .-- 3Mna+ + Cl- + 3HrO

Oxidation [un]ber of Cl changqs from + 5 in CIOi to _ I in Cl-
(v) 2 CrOr- + H2O2+2OH- ..- 2GO1- +2HzO
C)xidatioD numbcr
ofCr changes from +5 in CrO; to +6 in CrO?-l
16. What do you mean by iodomciric and iodimetric titraiions. Give one
example ofeach typ.
11. Drflw a lahelled diagram for rhc DaDiel cell. Discuss
its working

l& Discuss bnefly tho functtoo of the salt bridge iD aD electrochemical cell.
19. Give the conslruction of S.H.E. What is its standard reducrion potcntial ?
How does it help ro
delcrntinc thc standrrd elcclrode potentials ofolher clements ?
20, Write ir note an slandard hydrogeD electrqte_
21. What is an electrochemical serics ? HowcaD rhis bc used toexplaiD rhe
oddisingand reducing abilitics
ofelements ?
Why docs the blue colour oI copper sulphate solution ger discharged when
ao iron rod is dipped inlo
it ? Given : ECJ+ ,Co = 0.34VantjE.rt2+
/Fe = _0.44y
23, Arra,gc the lorkrwing nretars in increasiDg order of rcactMty. which
one wi be thestrongest reduciDg
agent and which is the wcakest ? Mg, Na, Ag, Cu, Fe, Zo

t-o..n4ld;np",,.Wf ti.-o."n*e*, caBnylN,g:frijinio.iu1iAnBs:

"R11,g-p.
Scc.9.1. l. Explain rhe terms : (r) oddatioo, (a) rcducrion, (iro midisint agent
to 9.6. of electrons. cive two example,s in ech cas to jriti'tr, you ---- (iy)
' and
'-
rEduci[g agcnl in rerms

2. Briefly cliscuss some redox readioos occurring io aqueous"o"dr.

solutioDs.
Scc.9.7. 3' Detine oxidarion number. H'^, does il diffe;from rarDcy z utiie
ttre generar rures of assigniDg
to 9.10. oxidation Dumbem to \rarious alonB in ions and molecules-'
4. Explain the rernN : (i) oxidarion, (i!) reduction,-(r, uidising ageo!
and (iy) rcducirg agcoa in tcrms
of oxidation numbe r. Give two enmples in eactr cjse to iflus-trai" yo,
5. GMog oDe example in each case discuss (i) oxidatioo number method "rilr"r.
alld (O ionlcclron method
for balancing redq reactions.
Scc.9.l2 6, Discuss briefly sloichiometry of redo( reactions in aqueous solutions.
Scc 9.13. 7. What is an electrochemical cell ? Bdefly discuss its co'nstruction
ani *orfirg. Uo*
to9.l6. is it represented ?

- hydrogen electrode ? How can it be used ro derermiDe sraDdard elcdrode potentiat

#:l rT::::::rd
9. What is electrocbemical series ? How does ir help us (i)
conlpariDg the oxidising and rcducing potvEr
ofdiftbreDr ctements and (O predicring wbett i _"iit*itt
gas or not ?
iiaJJi i rrnjrr.ur *io ,o give hydrogen
"r
 Ap,p.lT,lCI,N:Al-,,LJ,.,5E-Fuil-,'INiFoKM l,ON
ion Number
(o N.) or
cases the

el(amPle,
F
(a) Oxidation number of Cr in CrO5
x -Z or x= + lO(wrong)
(i) By convenlional method: 6r O", ot '**5x(-2)=0
be nrore than +6 siDce it has 5 electrons in
But this is wroDg because the n]a(imum O N ol Cr cannot in it are
five oxygen atonrs
3l-orbitals aod oneetectron in 4s'oruirfi' ;ilil';il;;;; because four of the

prescDt as two peroxide bonds:

O-.: _O
(ii) I T:ne strlcture of CrO5 is
By chemica! bond.ing method l):i<l
o
.. o.N. of Cr in CrO5 cao be calculated as follows:
4x(-1)=0 or x-2-4=O or
x + 1\(-Z) + (for o-o)
'=+6
(for Cr) (one=o)
= +6
Thru, the O.N. of Cr in CrOs
aci'l or pentronosulphuric acid)
(6) Oxidation number of S ir H2SOs (Caro's

ir1, i a" or 2x(+l)+r+5x(-2)=a 61 x= +tlwrongl

+ 6 since it has only six
oxidation number of S cannot be more thao
But oi O'N fo' S it Ou" to the reason that the two
of the orygen atoms
etecl rons "
in H2SO5
O

(ii) By chemical bonding merhod T:ne sttuctu re of H2SO5

is n-o--J--o-o-n
I
The O.N of S can be calculated as iollows
:
. .
2+x-6-2=O s1 a=*6
2x(+1) + .r + 3x(-2) + 2x(-1) =0
(forll) (for S) (for othcr (for O-O)
O ttomt)
Tlau, hc O.N. of S in H2SO5 is =+6
9t52
REDOX REACTIONS 9153

CaEe IL When thc corrwuryl co aiw covabnt ond coqdinde covolenl bondr. Tb calculate tho oddation
number ofatoms in such molecules, the folloring ruls are generally used.
(a) For eoch covalertbnd between two dbtimils atoms, auign ot uitlotbn ruonbet d +1 to lhe less
elecffonegalive Ltorn qid electonegolive elemenl.
-l to the more
O.N. of the two carboo atoms in CH3COOH may bc calgllated 8s follows :
For cxample,
HO
n-Ll--o-,
#'
q is attached io three H-atoms (less electronegative than carbon) and oDe -COOH
group (more
electroocgative than carboD), therefore, O N of Qis 3 x(+ 1)+x+ 1x(- l)=0 ot x= -z
Ct is, however, attached to one oxygen atom by a double bood, one OH (O.N. = -1) and one CHr (O N'
= + I ) grouP, therefore, O.N. of Ct is + r +r x(-2) + I x (-1)=0 ot x= +2
lf, however, the covalent borld is berween two similar atoms or betwecn two similar atorDswhich are further
attacbed to similar species, eacb atom is given an O.N. ofzero. For sxample, the cEntral Catom in carbon suboxide
(c3Oz) has aD O.N. of zero while each terminal carbon has an oxidation state of +2-

o =tC= 3 =B= o
Similarty in terrarhionare ion (SlOt-), O.N. ofeacb of the S-atoms linked with cach otber in the middle is
zero while that ofeach ofthe reamining two S-atoms is +5.
oo
-o-.rJ-3-3-*5J-o-
JJ
(r) ln case ofcoordinote covslent hoDdsr two cole! arlJe'.
(i) If a coordinate bond is formed between sane atoms or dissimilar atoms bul lhe donor alom is less elecio'
negafi)i ion the acceplor atofi, assign on oidotion number of + 2 to the donor atom ond -2 lo lhe otot L
^ccePlor
(ii) Conversety, il the donor atom is more elzcffonegotive tlun the occePlor alot\ neglect he contribution of
the coordinate bond.
The folloering examPles will illustrate the above rules :

(c) Oridottor numberof Cin H-C=NandH -N?C

(i) By conventionat nulho.r. since there are no staDdard rules for determiniog th oddalion numbrs
of c
uno Xl it Jr"fot", *nventional method caDnot used lo calculate tbe O N of C in HCN or HNC'
(ii)Bychemicalbondingmethod.SinceNismoreelectronegativethaoC,lberefore'eachcovaleDtbond
gives inb.i,{. or_t to N. N& since there are three covatent bonds, lherefore, the o.N. of N is HCN is -3.
+1 x-3
Now, tl C N +1+r-3=0 or r=+2
Thut, lhe oidation nufiber of C in IICN = + 2'

oxidation number ol c in H-N 2 C. Herc rhe contribution of coordiDatc bood is neSlected because

the donor atom, I..e' N is more electrorregative than the acceptor atom, |..e., c. Thus' the
o.N. of N in H-N c
since it has three covalent bonds. Thus,
'
remains to be
-3 +l-3+r=0 or x=+2
1x(+l) + 1x(-3) + x =0 or
(for H) (forN) (for C)
Thus, lhe oxidalion number of C in HNC =+ 2,
 \

9154 !,ratlt, , :' Neut Course Chemistrglfifi

ADOITIONAL UgEFUL INFORMATION contd.
Cinse lll. l*hen the compound contains two or more olornt of the wtu elencnt in d.iffereru oidalion slates.
For example
(a) Oxidation Dumhers ofS atoms in NarSrO,
+1 \_2
(i) By conventional method : Na252 03 or 2x(+1)+Zx+3 x(-2)=0 ot x- +Z(wrong\
But this lvrong because both the sulphur atoms caDnot be in the same qidatio! state as is evideot fiom
is
the fact thalwhen NES2o3 is trcated with dil. H2S01 , oDe S atom gets precipihted wbile the other gets coNrrted
into SO2 . The oxidatioo oumbers of these two S atonN can, howevcr, be determined by the chemical boDding
rnel hod.

s
(ii) By chemical bondirgmethod. The strucrure of NES2O3 is Na+ -O - $ - O-nu*
A
Since there is a coordiMte bond between ihe two S atoDs, therefore, the acceptor S atom has an O.N. of
The O-N. of the other S atom can be calculatcd as follows :
-2. 2x(+1) + 3t(-2)
+, + 1x(-2) =0 or +2-i+x-2=0 or ,=+6
(for Na) (for O atoms) (forcoordinatc S)
Thut, the tE/o S otomt in NarSrOrhave oxid.ation number! of and +6.
-2
(r) Oxldation trumber oflron atoEs in magretic oxide (p.3Oa).

(i) BJ conyentional method. ierO4nor3x - 2 x 4 = Oorx - + B/3.

(ii) By ttoichiometry. Fe3Oi is knowD to be a mixture of FeO aDd Fe2O3 having the composition j
FeO.Fe2C)3. Therefore, O.N. of Fe in FeO is +2while in Fe2O3 it is +3.
The value of 8/3 for the O.N. of Fe as obtained by conventional method is infact the average ofthe actual
O.N. of afl the Fe atoms io the formula, e.g.,(7 x Z + 2 x 3)/3 = 8/3.
(c) Oxidatior runber ofiron in Fea[Fe(CN)513
.xx_l
(i) By conventionol method Fea [Fe (CN)5]3 or 4.r+3x[r+6x - ll=O ot x=tB,/1
(ii)
By ttoichiometry. From our knowledge ofcoordinate compounds, we koo*, that Fe4 is the +ve part while
the complex ion,,.e. [Fe(cN)6]3 is -ve part- Therefore, iotal +ve charge on 4 Fe atoms outside the coordination
sphere rs balanced by total -ve charge on the complex ion. sinc Fe has two oxidatioD states, ie. +2 and
+3,
therefore,-Fe in the comPlex ion has an O.N. of +2 while the Fe atoms outside the coordination sphere
have an
o.N.of +3 and the average value of o.N.of the Fe atonls in the molecule = (4 x3 +3 x2)/,7 lg/7.
=
(/) Oxidation Dumber ofchloriue in bleaching po*der, CeOCl,

2tut
Average o.N. orClinCaoct2is 6tro, z, , z- 2 = o or x =0
(ii) By stoichiometry. The composition of breaching powder is ca2+1oct-;cr-. Here o.N. of cr in ocr-l
is +l whilethatinCl- is-1 and the average of two oxidation oumbrs = I x + I + I x _ I = O.

\\
REDOX REACTIONS 9/ss

c. B.s.E. - p,ii.T, ( r4A I N S SPECTAL

A. SUBJECTIW QUESTIONS (Common fith I.I.T) Equ i v ole n I we i n Ni d ati o n -re d uc ti o n re a c t i o n
W
is the weight of the su bsta[ce which gains or loses
Q, l. Copper dissolves h dilutc trlHc acid but Eot ir one mole of electrons.
dllutr HCl. BpLlE
Q.J. FiDd out the rstio of equivolent weiSht of
Ars' 51nge E of Cu2+zCu electrode (+ 0 34 v) i8 H2C2Oa. 2 HtO os an ecid ond its equivolent
highcr than that of H+/H2 electrode (0'O V), rveight ss f, reduciatrl
E. 2004)(West B eng4l,l.E.
lhercfore, H+ Gidis Cu to Gr2+
ioDs canDot
ions and hence C\r does not dissohiE in dil. HCl. Ans. (i) Mol. wt. of HzqO4-zHzO (oxalic acid) =
ID contrast, the clectrcde Potential ofNOt ioo, 126

r:-, NOt/NO, electrode (+ 0'97 9 is hiSher .. bo- wl. oI aClO =

. Mol- wt. of acid
' l,esrclly
thaD that of coPPer electrode atrd hence it can
r26
Gidis Cu to Cu2+ ions artd heDce Cu dissolvEs =-T-=bJ
in dil. HNO3. fraA, Ca disrolves ia diL HNOrdue
(ii) Oxidation of omlic acid involves 2 e-
to oxidarion ol Cu by NOI iorc a not by H+ change, i.., -
ions- coo-
Q. 2. Arrange A, B, C' D, E strd E iD order oflDctcas- 2CO2 + 2e'
ilg clertEde Pot Dttsl in thG Glechochemicql coo-
scrles lf Thus, Eq. M. of Hzqo1.2H2O
A + HrSO. ASO.+H,
Mol. wt.
AClr+C-
- CClr+A No. of clcctrons lost
ECl2+C.....- No rr.cdoD 126
=-t=0"
zBCt+D _ Dc.t2+ ZB
. Ratio of Eq. wL of oxalic acid as aD acid to its
II2SOa + D +
.
No tt ctlotr
Eq. wt. as a reductant is 63/63 = t.
AD& (i) A rects with tl2SO1 to libcrate H2 but
Since r.j : Hory does Cu2O act os both oxidaot and reduc-
D does not, thercfore,,4 lics abwe otd D lbs tsnt ? Exphln rvith proPr rtactions showing
below H it th chccqlunicd *ria the chrrge of oxidation nuEbrs in each ex'
(ri) Fbrther 6ince D displscs B trom BCl, therc- ampfe. BenBalI3.E.2o04) (Wen
fore, E of D is lou/er than that of B, ic., D lies Ans" Cb2O uodergG disproportionation to form
abovc B in thc clectrocbemical serks.
C1.r2+ and Cu.
From (i) and (ii), the order of inqeasbS E" of tbc
four elcmoDts ie., A H, D, B. 2cr+ (oq q4 cuz+ (aq) + cu (s)
(ui) Since C displaces A tom ACl2 but not E Tluu, Cu+ or CurO acts bolh as an oidont a.\ r'ell
hom EC12, therefore, E" of C is louer than that os a rcduclanl
of A and that of E is lo$/er than that of C. (i) Wbeo hcatcd in air, Cu2O is oxidisd to CUO
From (D, (n) and (iii), it is evidcnt that thc owo, +1 +2
ordcr of increasing elcctode potcttials ol thcse CUO+1/202-2CuO
five elemotr is : E, C, A, H, D B. and Cu2O ocls os o teduclont and reduces o2lo
3. Wbot ls ttre diflcrctrc! iD the defiriilotr of ![
Q.
equivalc[t i[ alr oclil-bosc re{ctlo[ rnd oD d-.
equivalctrt itr an orddstlon-Educdor r.sctloD ? (fi) When heated with CurS, r7 oxidises 52- to
(DJ.I Roldn leeol SO2 qld hence Cu2O acrs ss an oxidan,
A$. EquivaLnl tnigfu in acid-batc Eacti@t is, llre +1 +1 0
weight in grams which suppliG or accpts one 2Cu2O + C!2S 6Cu+SO2
mole of H+ ions.
-
9/s6 Pradeep's
r.! n Bolance the following equations by oxidation Step 1.'Ib determirre unreacted Mohr's salt.
number mcthod ; 50 cm3 of diluted Mohr's salt
(i) S + IINOs... SO2 + NO2 + H2O
= 10 cm3 ofO 1 N K2Cr2O?
(ii) P{ + NaOH + HrO-* PH, + NaH2PO2.
(We* Bensal l.E.E. 200O .. Normality of diluted solutioD = 0 02 N
Ans. (i)S + 4HNO3 +SO2 + 4NO2 + 2H2O Mol. wt. of Mohr's salt = 392
.. Amount of uDreacted Mohr's salt present in
(ii) P1 +3NaOH+3H2O .....* 250 cm3 solution
PH3 + 3 NaH2PO2
O.O2 x 392
i; I'tit ) Bt rll\
|\fiLm L 6.70 g of an alkall metsl oxalat was Amount of Mohr's salt used = 10 -I 96=804g
dlssolvcd per litrc ofthe solution. l0 cml ofthb solution From balanced equation,
requlrtd 20 cm3 ol 0'01 M Potasslum pcnnanganate 2 Moles of Mohr's salt (i.r. 2 x 392 8) react with
solutloE iu acidlc medluD What k thc atoBlcweight of one mole of MnO2 = 87 g
the alkali metal .. 8 049 of Mohr's salt will react with MnO2
The balanced chemical cquation for the
redo( rcaction is R7
=2'3g2-x804E=o'8s:8
2 KMnO4 + 5 (COOMb + 8 H2SO4-
Now 0 892gofpure MnO2 are Present in 1 5Iof
IqSOa + 2 M[SO{ + 5 M2SOa + 10COz+8H2O pyrolusite
wbere M is the alkali metal
.. %age of Mno2 in pyrolusite = TP x 100
Let Ml be the molarity of the alkali metal omlate
solution. Apptying molarity equadon, we have, = 59 4wo
M1 xl0 29r6.61 .
-+-=T or Ml =0.05M Itrohten.l. ZS cm3 of a solution contairling ferrous
sulphate and ferric sulphate acidified with H2SOa is
Let A be the atomic Eeight of the alkali metal. reduced by metallic zinc. The solution required 34 25
.. Mol. wt. of (CoOMt=2A+S8 cm3 ofO l N \CrrO7 solution for oxidation. Ilowever,
Thus, amounl of metsl c,Elate present Per litre of
rhe solutioE = (2A + 88) x 0.05 r hefore rEductionwith zinc,25 cm3 ofthe same solution
But the amount of alkali metal oGlate solutior required 22 45 cm3 ofthe sameK2Cr2OT solution. Cal-
- 6.7 eL-l (Srren) culate the amount of feEous sulphate flnd ferric sul'
.. (2A+88)xo 05 -6 7 orA=Xl phote preseni, per litre ofthe solution.
I'r oblem 2 . l .S g olpyrolusllr oll werE trEated with
'Iltration before reductioD Sives only
10 g ofMoht's salt and dllute E2sO+ After the readion, FeSO4. After reduction, Fe2(SO4)3 is also reduced to
FeSO4 and titration Sives total concentration of FeSO4
the solutiotr tras itlluatit to 29) ct!r'. 5() cm3 of diluted
and Fe2(SOa)3.
solutlon rEqulred 10 cml of 0'1 N IqcrtoT solutiotr-
FlEd out percentrge of pure MnO2 h p!rcluslte. Milliequivalents of IqCr2OT used after reductioo

Pure Mno2 present in Pyrolusite oxidises = voluore x Dormality = 34,25 x o 1

Fe2+ of Mohr's salt (NH4)2so1 . Feso4 .6 H2O) to = 3.425

Fe3+. Unreactcd Fez+ of Mohr's salt is determined by Milliequivalents of IqCr2OT used before reduction
YlCtrOr.
=2245xO'l=2245
Chemical equatioDs are :

MnO, + 2 Fe2+ .' 4 g+ .. Milliequivale nts of FeSoo in a5 cm3 = 2 245

- and nilliequivalents ofFez(so4)3 in 25 cn3
Mn2++2Fe3++2Hro
Crrol- + 6 Fe2+ + H+ -...
14 = 3 425--:2.245 = 1, 180
Now Eq. wt. of FeSO 4 = 15211 = 152
2Cf++6Fc3++7HrO
REDOX REACTIONS slsT

Eq. wt. of Fe2(SOa)3 = 4002 = 200 2.55

= :-- mtlltmoles
(4 -.r)
Ilence FeSOn g L-r, = i#, rsz , tf But SeO2 actually reducrd = 0.64 millimoles
Equating these two values, we have,
=13 65
).s5
ffi=0 64 or r=6
Fez(so.)3 g L- r) = * {q9
ffi ,. zoo
l,n,hiLut 5 l-1 g of a somple of copper orc is
=9 44. dissolved ard Cu2f (cq) is treoted wlth KI. The iodine

t'rohitttt J. 12.53 cm3 of 0 051 M SeO2 rescts thrs liberated requlred 12.12 cm3 of 0.1 M NarSrO,
solutiotr for titratlon. Whst is the perccntage ofcopper
exactly with 25.5 cm3 ofO.1 M CrSO. *hich is oxidised
in the ore ?
to Cr2(SOa)3. To what oxidation state ls the selenium Solution. The complete balaoced equation for the
colvert d during the reaction ? redox reacdffi is
Solutior. Let O.N. ofSe in the new compouDd =r 2 Ct2+ + 4l- + 2S2O3-* Cu2I, + SrOfi- + ZI-
duced-
J No- of moles of s2O3- ussg = 11:14 )< 6 1
..- SC+ + Cf+
= 1.212 x lO-3 moles
O*,O,r.OJ Fronl the balancEd equation,
Now 12.53 cm3 of0.05l M SeOz
2 moles of SrOr2- reduce Cu2* = 2 moles
=12.53x0051 . . 1 .212 x 1O-3 moles of S2O3- will reduce
= 0.64 millirDoles of SeO2
Cttz+ = 1.2t2 x l0-3 moles
and 25.5 cm3 of 0.1 M CrSOo = 25 .5 v 6 .1
.. Wt. of pure Cu present in thc ore
= 2.55 millimoles of CrSOI
= 1.212 x tO-3 x 63.5 = 0.0?7g
But acmrding to balanced redot equation,
(4 - r) moles of CrSOa reduce I mole of SeO2 Thus, %age of cu in 11," or" =
tf , too
.. 2.55 millimoles of CrSOlwill reduce SeO2
= 7?.

,-7. {rt\Arl-tf-SJ SP.frCIA {

e. l.5.0 I of a semple of bross werc dissolved in I hypo solution. The complcrc balanced e4uation
litre dll. H2SOa. 20 cnl of this solution were for the rcdq rcactions is
mixed wlth KI and liberated lodlne required 2 CISO. + 4 KI- 2 &SO. + 2 CuI2
20 cml of0.0327 M hlpo solutlon for tihatlon. 2CuIz '-Cu2Ii+12
Calculate the perceDtrge of copper i[ the olloy,
12 + 2Na2S2O3 NqSaO5 + 2 NaI
Ans. Brass is an alloy of Cu and Zn. When brass is -
treated with dil. H2so1 in presenc of air, 2 C\SO. + 4KI + 2 Na2S2O3 .-
CUSOa and ZnSOa are obtained acEording to the C%I2 + IqSO. + Na2SaO6 + 2N8I
follorpiDg equations :
sa.p l. Tofrid @t rhc noloity of CuSOasohuion
2Cu + 2H2SOa + Or-2CuSOo +2HrO
Lst thc molarity of CISOa loltl. - Ml
Zo + H2SOa- ZDSO{ + H2
Applying molarity equation,
Out of CUSO{ and ZnSO1, only CuSOa reacts
M,V, M.V"
witb KI to form 12 which can be titrated against (c\'so{)
---: - -i-: (Na2sro,
9/58 l'tr:ttey's Neut Course Chemist.g jm
or Mr x 20 = 0.0327 xmot Mr-O.UfTl . Amouot of Sn2+ oxidised = 118.7 x 0 00051
Slcp 2. To fittd od tlu prccnoge of coppq it the = 0.06I
alloy
.. 7,age ofsn in the ore =
frff x100=15
Volume ofalloy solution = 1000 c'rn3
(.) r. A sample ofhydrazine sulphate (N2ll5SO.) was
Molarity of alloy soluti:n urr Ctr2+
dissolvcd ln 250 ml ofvatcr. l0 rlll ofthis solu-
=o.BnM tion rvas reacted with exccss o[ ferric chloride
But Al. wL ofcu = 63.5 solution arrd Eormed to complet. the reaction.
.'. Amoutrt of Grz+ f6mcd Ferrous ioE formed was estimsted nnd it re-
quird l0 ml of ll/l/25 potassiuh perrnangflnate
- o.032? x 63.5 =2'0lt6g solutiotr. Estimste the aElount ofhydmzinc sul-
But thc amouDt of Cu2+ ior! in lolution is egual phate dissolved itr 250 ml ofthis solution
to thc aEcrnt of C! io thc 8[oy.
4Fe3+ + NrH.- N2 +4Fe2+ + 4 H+
.'. Amount of coPPer in tt c aflcty = 2 '076 t
But the amounr ofalloy (brsss) lakcD = 5'09 Mno!+5Fe2++EH+-.-
.'. % of copper in thc alloy Mn2+ +5Fe3+ +4Hro
2'376 ,. roo 4r.szrh i)
= = (M.L-N.R. Allahabad 1 99

Tlau, h. Frtqragc ol copa ia tfu alloy Ans. Step l.

Tb derermine the number of moles of
KMnOrwed.
= 41.52%
We are gi\D 10 ml of N2H6SOa sol.
Q. 2. IB sn orG, thc only oxldhoblc urtcrlel lr Sn'+.
Thls ort is titratcd wlth s dlchromst solutlon
= l0 ml of MA5 KMnOa sol.
coDtrlDlng 2 . 5 I of IqCrrO, lD 0'5(, Utrr, Tbe
.. 250 ml of N2 H6SOa sol
0.40 lsmplc oi thG orc rcqulrrd l0'0 cml of
t
tltrrDt to rerch G{ltrrlGtrt pollt C{lcuht OC = 250 ml of M25 KMnOa
pcrrcDtrgc oftlE ln thG oI! (K-3,'I'Cr=5a
Sn = Ilt.7) (Roo @.1993') = 2f , ,fu , zso rnotes of KMnol
Ans. wi. of lqcr2oT present i[ 500 qn3 = 2'5 g
= 0.01 mole of KMnOa
.. Wt. of IqCr2Oz preseDl in 10 cm3 Step 2. Tb find out rhe amouttt ol Ny'tCOr
,.<
_ffix10s Multiplying nrst Eq. Siven in tbe questioD with 5
and secoDd Eq. with 4 to caDcEl Fe2+ aDd then
Mol. wt. of lqCr2OT = 294 on adding, wc 8et,

.. No. of mohs of IqCr2O? Present in l0 cm3 4 MnOa- + 5 NzHa + 12 H+ ...- Protlucts

solulisn = i-!-Ilq = o.ooo17

Thus 4 moles of KMnO4 react with 5 nroles of
N2H6S01
The balancfd chemical equation for lhe redox
reaction is :
.. o.0l mole KMDO4 will react with N2H6SO1

ct"ol- + 14 H+ + 3 Sn2+ =ix0.01 molc -0 0125mole

-
2CF++3Sna++?Hro = 0.0125 x 130t(Mol.wt.of NzH6SOo = 130)
From lhe above balanced equatioll, = r.G2S g
CrrO|- =K"CrrOr=3Sn2+ (J I 0 5 g ssmple .'oDtaltring Mno2 is treated with
HCI liberating CI2, The chlorhe is passed into
ie.,1molell2Cr2O]- cidises Sn2+ = 3 moles
a solutior of KI atrd 30 0 cm3 of 0 01 M
.. 0.00017 mole IqCrrOT will oxidise Sn2+ Na2S2O3 ore required to titrate the libcrated

- 3 x 0.0001? = 0 00051 mole iodin.. Calculate the percentage ofMnO2 ill the
srrDple (At wt of Mn = 5t. (Rn*ee 199O
BEDOX REACTIONS 9/59

Ans. Step l.'Io write the complete equalion for the 2 Na2S2O3 + 12 -- NES1O6 + 2 NaI
redox reoalioru
SuppG sreight of IqCr2OT in the mixture = rg
MnO2 + 4 HCI -.MnClr+Cl2+2H2O
Then weight of KMnOI in tbe lllixture
zKl+Clz 12KCI +\
= (0.s _r)t
Iz + 2 Na2SzO3 NES.O6 + 2Nal
- Iodine producrd from x S Y.2Cr2O, = xxg
ffi
Mnoz + 4HCl + 2KI + 2 Na2S2O3 ...- Iodine produccd fmm (0.s - r)t XMno.
MoCl2 + 2KCl + N%SaO6 + 2NaI + 2 H2O
-ff'10's-'1r
Stcp 2. Tb calculate lh. prcentogc of MnO 2in the Tbtsl iodinc produced
sanple x -r\ -
No. of moles of Na2S2O3 prescDt in 30 crn3 of 0 . I 291Ll27O(0.5
-762 316

M Na2S2O3 solution lm ocof0.15 N N%S2O3

= 100 cc ofo'15 N solurioD
-ffixo.r = o.oo3 mole
12

From the balanced equalioD, it is svident that,

- r27iI.t 15
x roo s - r .ro5 6

2 moles of N%S2O3 = I mole of MnO: -- '162x 1no(o.5 - a

Hcnce
7'4- + - l 'eos
.0 .fiI3 mole of Na2S2O3
.
-fE-
which on solving givcs x = O.tl3 t
. . % a$e of Y\Cr2Ot in lhe mixture
= x 0.003 = 0.0015 mole MnO2
i
No$, Mol. wt. of MDOI = 55 + 2 x 16 = 87 - %3, roo - 1..6i
. . Wt. of MnO2 reacred = Moles x Mol. wr. aDd % ate of KMnOa h thc mixturc

= 0.001s x 87 = 0.1305 I - 100 - lit .6 = t5.,tt

Trage of MnO2 in the sample
Q 6 A 3.0 8 ssEplc colt lnhrg Fcroa, F.rO! rlld r]t
hcrt hp[It .uhstrtrcg lr Ec.ttd sttt cxc.sc of
= S;# no =26.1%. XI coludon In prtscnct ol dilute HrSO.. The
"
Q 5. 0.5 g mlxturc of KrCrrO, and KMDOa wos endtc lroo ls clnycrtcd lnto Fe'+ alotrgwitb
llbcrodoD of lodlnc. Thc rcluldDg solutlotr Ig
trst d l{ith
KI in acidic medium. Iodine
excess
d trtrd to lm r[L A 2,0 nl olttG dllut dEoludon
liberated requird lfi) cm3 of 0.15 N sodium Equlr.s 11.0 El of0.5 M Ns2StOr solutlon to
thlosulphste solution for ti aratioD. Fird the per-
rcducr thc lodlnc prcsclt A 50 El of thc dllutld
cert amount ofeach in the mixture (AL wtsr K
6oludo! rfbr coDplct crtrrcdoD ol lhc lodioc
= 39,Cr = 52,Mn = 55,Na = 23S = 32) rtqulrrs 12 t0 ml of 0.25 M KMtrO. solutlon
(Rtu*ee 1995)
in dilut! HrSOa Ecdl[m for th. oddadon of
Ans. Tbe reactions involved are:
IqCr2OT+7H2SOa+6Kl- Fcl+. Calcubtc thc pontlta3ca ol Fc1Ol ond
rcro. h ahc ortStnd !.Eptc- GI.T 1996)
294 E
Atr& FcaO. is aD equlrdar mLturl of RO and Fe2O3
4 IqSOI + Cr2(SO4)3 + 7 HzO + 312 ...(0
The rcactions invoh,red arc :
7x254 (r) FeO + HrSO. FGSO. + H2O
(n) F%O3 + 2 H2SO.
-
2 KMnOa + 3 H2SO. * ,n O i'u" -2FeSO.+2H2O+(O)
2x158
=3168 2KI+H2SO.-IqSO.+2HI
IqSO4 + 2 MnSO4 + 8 H2O + 5I2 ...(ri)

5x254 FcrO, + 3 HrSO. + 2 KI-

=l2mg 2 FeSO. + IqSOI + 3 H2O + 12
9/60

( ) 2 Na2S2O3 + 12+ NqSaO6 + 2NaI = 0.00925 mote

(iv)2KMnOa+3H2SO..- Thus in the mixture
Fe3Oo = 9 9045 ,.le 232 x 0'm45 = 1 O'l4 t
Iqsoa + 2MnSOa + 3 H2O + 5 (O)
2 FeSOa + H2soa + (O) + Fe2O3 = 0.00925 mole 160 x0 ffi = l',188
.. % agc of Feroa in the mixture
Fe2(SOa)3 + H2Ol x5
-I 944 x fio-,.4.E%
2 KMDOa + 8 H2SOa + l0 FeSOn 7, age of FezO3 ifl the mixture
K2So4 + 2MnSo4 + Fc2(so1)l + 8 H2O
-
- 1:1! 1 1e9 , 4e.33*
Resulting solution contaiDing I, + Fez+ after
dilution = 100 ml Q.7. On. Iltrc ol. Elxturc of ()2 ard 03 ot NTP
!r8s allotred to rcsct rtlth on excess of
20 ml of diluted solution = 1r'o fll of 0 5 M
scidilicd solutlon of KI. The iodlne llberated
Naz5203 rcqulrcd 40 ml ol W10 sodlum tblosulPhate
.. 1fi) ml of diluted solution solutlotl lor tltratlon. Whot ls th.wclght per-
ofo 5 M N&2S2O3 cctrt of ozotre h the mixture ? Ultravtolet
= 55 0 ml
radlstloss ol woecleugth 300 nrtr con dccom-
, poae ozone. AssumlnS thst one photon con
= ffi ss = 0.0275 mote N%Szo:
dccompose onc ozore moleculg how mony
o 0-275 photoDs would havc bcen required for the
- - 0.01375 moles l. coEplctc dccomposltlon of ozotre ltr the
original mixture ? (r.r.T 1e97)
= 0.01375 mole Fe2O3
Again, 50 mlof diluted solution
turs. 03.- 02+O
= 12.80 ml of 0.5 M KMnOa 2 KI + H2SOa + (o) .* IqSOa+H2o+12
.. 100 mlof diluted solution 2 NESO3 + 12 N%SaO6 + 2 NaI

x zS.oo = o.0064 moleKMDO4 -

= ffi
2 N%S2o3 + 2 KI + 03 + H2SOa
= 5 x 0.0064 - 0.032 mole FeSO4
Thus 0.032 mole FeS04 has been obtained ftom
- + 2NaI
oz + Iqsoa + H2o + NEs1o6
0.01375 mole Fe2O3 and the rcmaining ftom 2 moles ofNa2s2o3 react witb one ntole of 03
Feo.
No. of moles of NEs2o3 in 40 mlof S Na2szol
As 1 mole Fe2o3 = 2 moles FeSol
.. 0 01375 mole Fe2O3 = 2 x 0 013?5 moles =frrffi>.no=4xto-3mote
FeSOa - 0.0275 mole FeSOa
.. 03 reacted (present) = 2 x 10-3 ntole
.'. FeSOa formed from
(. 2 mole Na2S2O3 = I mole 03)
FeO = 0.032- 0.0275
=0 0045 mole Volume of 03 = 2 x 10-3 x 22 4L
But I mole FeSO4 = I mole FeO - 0 0448 l,
.. 0.0045 mole FeSOa = 0 0045 mole FeO .. Volume of O, = I - 0 0t148 = 0 9552 L
As Fe3O. contains equal moles of Feo and WeiSht of 03 = 2 x l0-3 x 48 = 0 096 I
Fe203
x
. . Fe2o3 present in Fesor = 0 0045 ntole
weigtrt of 02 =
ffi 32 = 1.3646 E

. . Free Fe2O3 preseflt in the mixlure

.. WeiSht of mixture
=0 096+13646=l4tt06 I
= 0 01375 - 0.0045 mole

t
REDOX REACTIONS 9/61
., % of 03 by rveight
10 I- .--.---.+ 5 12 + 10 r-
-ffi*rc0 =e .stt*
2IO; + 12H+ + l0I-......- 6 12 + 6IizO
No. of moleculer in 2 x 10-3 mole of O,
2 S2O3- + Iz SlO2- + 2l-l x6
-2 x 10-l x6.U22xlP -
=12044x1021 2lo; + nH+ + 12 S2o3- .._
., No. ofphotoos required = I .20{4 x l02l
6SaO?-+2I-+6H2O
Q.E An aqueous solution of 0.10 g KIO3 (formula
wGlgtt = 214.0) was trcat d witb an excess of No. of moles of KIO, =
KI solutlon. Thc 6olutlo! sos acldlllcd with f;]
HCl, The liberat d I, consumd 4S.0 ml of No. of moles of Na2S2O3 ,"6g1s6 = x e,
thlGulphrtc soludotr to dccolourise the blue 2lq+
which are present in 45 0 ml.
sarrch lodltre complcE Colculatc tie Eolsilty of
sodlum thlosulphste soludor. (IJ.T l99E) Hence molariry of Na2S2O3 sol.
Ans. The readions involved are : 0.1 6 1000
x
= --r-i1- x -73-
2IO; + 12H+ +10c-+6H2O+12
= 0.0623 M.

Oxidation oumber of sodium in sodium amalgam (D)

is
G) 5162
(4) +1 (r) 0
(c) -1 (d) + 2.
2. For thc reactioD,
Mr+ + MnO!- MOr- + Mn2+ + 7 / 2O2 (a) A is easily reduced .
(b) A is readily cxidised
if one mole of MnO; oxidises 1 .67 moles of Mr+
(c) A- is readily reduced
to MO3-, then the value of-t in the reaction is
(d) A- is readily oxidised.
(a) s (b) 3
(") 2
(M. L N. E Alhhabd.t I 99 2)
(d) 1.
6. Tbe oxidation stare of chromium in Cr(CO)d is
3, The oxidatioD number of phosphorus iD
Ba(H2P02L is sr6 (b) +2
(a)+3 (b)+2 (c) -2 (d) +6.
w+1 (d)-r. u.I.T teso) (A.t.t.M,s. r993)
4. For thc redox rcaction, 7. Which of the follo\f,iDg ir zo, a redox reaction ?

MnOo- +CrOl- +H+ Mn2++COr+H:O

(4 CaCo3 - Cho + Co2

-
the correct coefficienls of the reactaots for the
(b) 02 + 2H2 - 2HzO
balancd reaction are : (c) Na + H2O - NaOH + 1 ,/ 2H2
Mnoa- qo?- H+ (d) MrC\ - MnCl2+ | / 2 C\
-<6) 2 s 16 (A-I.LM.S. 1993)

t,b J.c .a 5. 11 6.u 7.o

 Neul Coutse
electroDs to (d) hydrogeD is easiest to oxidize
A mole of N2Ha lcrses ten moles of
that all the (f)'ihis electrode potential is assumed to be zero

,what is the (c) hydrogen atom has only one electron

there is no (d) hydrogeo is the lighest elemeDt il'l l: lt)t)7)
change in the midatioo number of hydrogen) 15. Which of the following is a rdox reaction ?
(a) -r (b)-3 (4) H2SO4 with NaOH
(c) +3 (d) +5.
|R.H.U. leer)
(b) In atmosPhere ,O3 froD 02 by lightninB
9. When copper is trcated with a certain concrntra-
rion ofniiric acid, nitric qide and oitrogen dioxide -6) Nitrogen oxides fron] Ditrogen aDd oxygen by
lishtniDg
are liberated in cqual volumes according to the
eouatioo. (d) EvaporatioD of H2O.
, bu+y irNo, H2o' (('-lt \'1" l''ll '1 1')1)7 )

-cu(No3h+No+No2+
The cofncients of.r and I are 16. The oddatioD Poteotials of A and B arc +2 37 V
(o)2aDd3 g[7 afi 6 and + t 66 V respcctively. In a chemical reaction,
(c) I and 3 (d) 3 afld 8. (o) Awill be rcPlac.ed bY B
("fi s ): lt\I l: lt)')tl - (r) Awlll replace B
10. ln which of the following Pairs, there is Sreatest (c) A will not replac B
differenc in ihe oxidation number of the under- (d) A and B will oot replac each other.
lined elements ? tt).t!\ tl..l.'l: 1996: l'h (.1 'l: 19971
(a) NO, and NzOa (6) f2O5 and & Olo 17. Which among the follo$'ing is the strongest reduc'
(c) N2o aDd No -/tqo2 and SO3' ing agent ?

ll).(.1; 1991) Given, Fe2+ + 2e- + Fe (-0'44V) '

11. In the reac on, Ni2+ + 2 e- .+ Ni (_ 0.25 V);

2FeCl3 + H2S ...- 2FeClr+2HCl+S * 2 r- ......-
tnz So (- 0.14 9 and
qidizing
(r) FeCl3 acts as an aSeDt
Fe3+ + e_ _ Fe2+ (_ 0.77 V)
(b) Both H2S aDd FeCl3 are oxidized' (a) Fe lDYTez+
(c) FeCl3 is oddised while H2S is reduced (c) Ni (d) sn ( IJ.l1.U, l99li)

(d) II2S acrs as rn crddizing agent' lE. Y'lithout losinS its concentration, ZnCl2 solution
tU P S l;A I:19t)('| cannot be kePt in mntact with

of KMnO4 required to oxidise

(a) Au liA
\/ I{..'Number ofof moles
Fe(qoa) io acidic medium is
(c) Pb (d) As.
onc mole t( lt.\.1' i:.\l !: l'')t;
(a) 0.6 (b) 1.67 19, The standard reduction potential values of three
(c) o z (d) 0'4 metalliccations, X, Y, Zare 0 52, -3 03 aIld -1 18
(Haryam C.L.E.1l 1996) V resPecivcly. The order of reducing power of the
corresponding nletal is
13. ln the reactioo,
IrO ...-5Br- t BrO; +6HCOt
447 rzrx (b)x>Y >z
lBr. +6CO1- +31
(c)Z>Y >X (d)Z>*'
(td Bromine is oxidised and carb6ndte is reduced ,, ,,,r,
(b) BromiDe is reducd and water is oxidised 20, The oxidation numbr of sulphur iD

(c) Bromine is neilher reduced nor oxidised s8 , S2F2 , Hzs resPeativelY, are

-@ Bionlino is both r",t,""u u''o o''u't11 .1afo,+tarda (b) + 2, +1and I

, ,,,, (c) 0, +l and + 2 (O) a'* ru",1
. 14. A staDdard hydroBeo electrode has zero electrode ,,;, ,rry
potential because
AA'S ii' i' l< s
E.c 9. b lO. tt ll. a 12. a 1X. d 14. b 15. . 16' b 17. b

lt.,
REDOX REACTIONS
9/63
21. A gas at I
8tm is bubblcd through a solution 2t, In the givcD re3dion,
containing a mixture of 1 M Y- aDd I M Z- at
&Cr2O7 + XH2SOa + YSO2
25oc. If the rcduction porntial of Z > y > X, -
ihen IqSO4+Cr2(SOr3+ZH2O
(a) Y will Gidize X and not Z X"Y,Zarc
(6) Y will Gidbc Z ard Dor X (a) l, 3, 1 (b) 4, t,4
(c) Y will cnidize both X aDd Z (c)3,2,3 (d) 2, t,2.
(d) Ywillreduce both Xand Z (t.t7: tsse) lR.H.U. 1991.20t)01
2L A ion M3+ lces 3 clcdrons, its qidatio[
mf,aal 29. The oddation DumbcrofiroD is Fe3O{ is
number will b
(o)+2 (D)+3
(a) +3 (D)+6 (c) 8B (d)28.
(.) o (d)'-3 tc'.tt,tt.t tccct (C.B.S.E. l!n[.T 1999 ; HoD,ana C.E.D.T.2000)
23. 'Ib an acid solution of an anion, a fcw drops of
3lL Which will bc ihc proper altcrnative in pl8cc of A
KMnO4 solution are added. Whih of the foitcm,-
in thc fo[oying cqua[on.
iDg, if prescnt, will not decolourisc the KMnO4
solution ?
2#+ 1aq1 + saz+ 1aq1+ 2Fe2+ @qt + A
(a) Sna+ (D) Sn3 +
(d) co3- (6) NO2-
(c) Sn2+ (d) sn.
(") s2- (d)Cl-. tD L:.t:. teee) (1t.PC.8.8.2000)
The pa ial ionic equaiion, 31. Numbcr of mol6 of Iqq2O, rcdued B , mol
C.x2O4- + 14 H+ a6s--2G3+ +71\O ofsnz+ is
suggests that rhe equivalent urcight of Cr2O?- will (a) 116 (b) 18
be equal to it! formula sreight divided by G)a3 (d) 1.
(a) 3 (6) 6 (Haryam C.E.D.T 1996, 2000j
(c) 1 (d) 14. 32. Which ofthe follotring is nor a reducing ageDt I
i D.(. t,. 19q9) (a) so2 (b)H2o2
25. Oddation state of osmium (Os) in OsOa is (c) Co, (d)NOz. 0 (:.t:,.2o0ot
(a)+7 (b)+6 33. Equiralent mass of cidising agent in the reaction,
(c)+4 SOr+2HrS-3S+2HzOis
Jfr+8.
t l t t.11.\. ttrl.tl
(o) 32 (b) 64
FluoriDe is the best oxidisir,g agent because ir has
(a) higbest elecrron affinity
(c) 16 (d)8. (D.c.E.2ooo)
The cddation state of c$romium ill
(D) highest E ,cducrion
lc(PPh3)3(co)31 is
(c) hiShest E"oridlrion (a)+3 (6)+E
(d) lowest elecrron aflinity. (c)zfito (d) + 5. (D.c.ti.2ooo\
i Iln^ntlr ( l..l:.t: totgt 35. Thc !.alues ofr and / in the follo$ring redox reac.
A compound contains atorns of tbree elemenb _
A, B aod C. Ifthe oxidarioD number ofA is + 2, B r Cl2 + 6 OH- CtO3- +y CI- + 3 H2O are
is + 5 and that of C is - 2, tbe possible formula of
the qrmpound is (o)x-2,y=4 - (b)r=s,y-3
(4)q(Bcrz (D) .\(Brc): (c)x-3,y=s @)x.=a,y=L
(") eBQ (c.t!M. [ 2000)
(d)A3(Bqh
J6. Arnongsr the follo$,iDg, idcntify the species with an
\ c.B.s. D. I!.tt.T 2000) atom in +6 qidation state

ANgWE
2-l.g ??.b 23. a 24. b 2s. d
31. b 32. c 33. c 34. c 35. c
26. b 27, a
9/64

(a) MnO.- (r) cr(cN)e- MoO; (aq) + 8H+ (44) + 6 e- a

(c) NiF!- (qcIozclz Mn2+ 1aq; + luro 1l) E = 1 5t V

u.l.'l:2000) C;.zolt- @q) + 14H+ (aq) t 6 c-
lM+ llx- lX,
37. For the electrochemical cell, M
-
2ci+ 1aq1+ 7H2o () ; Eo = 1 38 v
EM+/M=0 44VandEx,,;- =0 33V'
From these data one can deduce that Fe3+ (aq1 + e- Fsz+ 1aq1;E' = O'tl V
(a) 1- 14+ + x- is the sPonhneous reac-
- zcl-
1r4 1 Clz@)+2c- @q)iEo=14Ol/
tion -incorrect statement regardio8 the
the oDly
Identlry
(6) M+ + x- + M+x is the sPonmneous reac- quantitative estimatiion of aqueous Fe(N03)2
tion
(a) MnOa- can be used in aqueous Hcl
(c) Ec.r - 0 77 V
GrO]- HCI
(d) E""n - - 6'7 Y (l.l.T 2000) (b) can be used in aqueous

3E. In the standardiztioo of NES2o3 usin BY\ct2ol (c) MnOa- can be used in aqueous H2SO4
by iodometry, the equivalent weiSht of IqCr2OT is
(d) CrzO?- can be used in aqueous H2SO4
(a) (moleculsr weiSht)z
t I.l 1: :ltt) ) \

(b) (molecular weighD/6 ul'

43. WheD KMDO4 acts as aD oxidising agent and
(c) (molecular wi8ht)R
(r.I.T 2oot) timately forms Mno4-2, Mno2, Mnzo3 and
(d) same as molecxlar wciSht.
(oq)' Mn+2, then the number ofelectrons traDsferred irl
39. The raction,3 CIO- each case resPectively is
clo; (aq) + 2 cl- (44) is an examPle of (a) 4,3,7,5 (b) r, s,3,7
(rI) Oxidation reaction (c) 1,3, 4, 5 (d) 3, s,'1,1
(b) Reduction reaction lAl ltEL 200)t
(c) DisProPortionation reactio[ Which of the following is a redo( reaction ?
(d) DcmmPosition reactioD. (1 1.t 2001) (c) NaCl + KNor- NaNo3 + Kcl
40. Standard electrode potentials are (D) CaqO4 + 2HCl CaClz + HzCzO+
FeE = -0,14v,Fe+3zFe+zEo-o71y
-
Fe2+ .t (c) Mg(OH)z + 2NHoCl- MgCl, + 2NH4OH
Fe+2, Fe+3 and Fe blocks are kept together, ihen (d) Zn + 2AgCN 2Ag + Zn(CN)2
(a) Fe+3 increases
- (A'lEElt'2t)02)
(D) Fe+3 decreases A smuSSler could not carry gold by depositing iron
oll the gold surfac sinc
(c; Fe+2 z Fe+3 remains unchanged
(o) Gold is densr
(d) Fe+2 decreases (b) Iro[ rusts
(c.B.s l. P.'tlr200I) (c) Gold has hiSher electrode Potential than iron
41, The reductioD Potentials of Zn, Cu' Fe and Ag are
(d) Gold has lovrcr electrode potential than iron
in the order :
(Kanutk*a C'Ii '1: 20t2 )

(a) Ag, cu, Fe, Zn

(b) Cu, A8, Fe' ZD
46. The oddation states of sulPhur in the aoions
(c) izD, Cu, Fe, Ag
(d) Fe, Zn, cu, Ag
so3-, s2o1- and szol- follou'the order :
(N.5.1!.20ol)
42. Standard electrode potential data arc useful for (c) sro!- < so3- < s2o3-
understandiDg the suitability of an oxidaot in a < s2o?-
re<tox titratioi. Some half cell reactions and their
(b) so3- < s2o1-
shndard potentials are given belou' :

39.c 42. a .13. c 44. d '15. c

36. / 37.b 3E., 4/0.h 41. a
REDOX REACTIONS
9/65
(c) sro!- < s2o?- < so3- (a) Evolved 12 is reducd

(d) s2o3- < s2o?- < so3- -{.tfcu[2 is formed

(L:. B. S. E. P Lt.'t: 2 003) (c) Na2SzO3 is oxidised

47, Which of the tollowing is acrually t ossible if oxjda_
- (d) Cu2F2 is formed
\A.t.ti.l:.1.).200j\
tion potentials o_f ZD = + 0.76 V aDd
53. The oxidatioD number of carbon iD CH2C|2 is
A8=-o80v?
(aro (b) 2
-@'Zn +2AE+ -Znz+
+ 2Ag
(c) 3 (d)5 (A.cM.C'. 2004)
(b) Znz+ + 2 Ag- V, t, Ot* lf,* flhat b th cquivalent mass of IOi- when it con-
(c)27n+2AE-Znz+ + 2 Ag+ wrtcd into 12 in acid medium ?
(d) Znz+ + Ag+ eE (o)W6
-Zn+( lh rd tta .I.G.t. lU.S. 200.j ) &rfrw
(c) W5 (d)Mt4
For decolourizarion of I mole of KMnO., ihe (c) Done of thesc (krala IrLD.li.2004)
nroles ofH2O2 rcquired is 5i q
\Crzol + b KCI + c H2SOa CrOzClz *.r
@) W (b) 3/Z +) KHsoa +z li2o
.lc)512 (d)712 The above equation balaDces wheD
,.r I L,!LS.200Jt (a)o=2,b =4,c =6attdx=2,!, =6,2=3
49, The pair of compounds having metats in rheir
highest oxidation state is
@)o =a,b =2,c=6andx=6,y=Z,z=3

1,jrrno,, necr, flp, ="r:,i=^;,'"==2T:r,,==t;,rr==rul,,"==1

-(r) MnO;, CrO2Cl2 (e)o=l,b =6,c =4and.t=6,y=Z,z=3
(c)lFe(cN)613-,[co(cN)]l i6 Aruminium ooo,"." orororfr"ir!k';r!;r;'il!,
(d) [NiCl4F- tcocll]- whereas silver does not. The E.M.Ii of rhe cell
, \t.t 7: 2001)
g). Consider lhe following E"ralues prepaJed by combining AlzAl3+ aod A8,/A8+ is
E Fca+/Fe2+ = o z7v, E.snz+zs,:_.,:
Under srandard condirions, rhe porenrial for :1-y-
the
3 i.."u;v{i111.flffirs#,1i":xi:,:fffflx:
i"
reaction, "l".tio;"
sn (r) + 2 Fe3+ (aq) 2Fc2+ r,oq1 + sn2+ 1aq1 ':;: :rY"
," - 'lr-'r::r:,
Kornntnkn (.t.: l: /t)0.1
(
(d)o63v (b) 1.40v s?. which of rhe rollo$r'ing starements is rrue for rhe
14i 91V (d) 1.68 V etecrrochemicat Daniel ce I

-0 41, + I 57, + o.7'.- and + I ,97 V resDectivelv. -ftCurrent flows from zinc eleclrode to coDDer
For which one ofthesc metals, the change in oxid;- electrode
tion state front + 2 to + 3 is easiesr ? {}&tions move towards copper electrode
(a) ft (D) Mn (d) Carions molr'e ro$rrds zinc elecrrode

Na2S203 solution added to it. Which ofthe state-

is

ments is iacorec, for the rcaction ? H2O + Br2 .- HOBr + HBr

A^JSWERi
it.I il:i 4E. c 4e. b 50. c sr. tt s2. b 53. o s4. b ss. d
9/66
1r 's Nc.t Coursc ChemistrAWII)
L'
t'

(a) Proton accePtor only 1g1g+ tHg- + O.79, Cr2+/Cu = +O'34V,

(D) Both oxidised and reduced M*+ twg- -z'tt.
(c) Oxidised only With increasing voltage, tbe scquenc of dePositioD
(d) Reduced only (c.D.s.E. PM-T. 2004) of metals on cathode will be
59. In a galvanic cell, the electrons flow ftom (a) A8, Hg, Or, Mg (D) Mg, c\t, H8' Ag
(a) anode lo cathode through lhe solution (c) Ag, H8, Cu (d) cu, Hg, Ag
(6) cathode to anode ihrough the solution (e) cu, Hg, A8, Mg
(clanodc to cathode through thc extemal circuit tt.t'l: 1931 ;litt(1 ,11.11 L 2o01)
U+
(d) cathode to anode rhrough the c,(emalcircuit
Crrol- + xl- cf + + H2o + o:ddised producl
ofX, X in the above reaction caDnot be
l@ An ,qu"out tolution conl
of each Cu(NO3)2, @94' (D) Fe2+

M8(NO3h is beiDg electrolysed using inert (c) sol- (d)*- rc.nv.r zoo,tt
electrodes. The values ofstandard electrode Poten-
tial (reduction are Ag+'/Ag + 0 80
Potential) -

HINTg/EXPLANATION9 to
1. Sodium amalgam is a homogenous Dixture ofNa
o.N. of two N aloors in Y inqcases by 10,'e thc
tolal O.N. of two N atoms in
and HE and a\ such Na exists in thc elementalstate
aod hence ils O,N. is zero Y=-4+10=+6.
+1 ..
O.N.of eaohNis\ = + 6[2 = +3.
2. MnO4-*5"--Mnz'
9, Balanced cquations for producing NO and NO?
Sinc I mol of MnOa- acapts 5 moles of resPectively are :

electroos, therefofe, 5 molesofelctrons are lost by 3Cu+8HNO3 .-

1.67 moles of M'+ 3 Cu(NO3)2 + 2NO + 4l{2O (i)
.'. 1 mole of Mr+ will lote elctrons = 5/1 67
Cu + 4 HNO, -...- Qu(NO3)2 t 2NOz + 2 IIzo
= 3 molfs (awox) ...(,,)
Since Mr+ changes to Mof (where o N' of M = Adding Eqns. (t) aDd (ii), we havc
+ 5) by sccePing 3 clectrons 4Cu + 12HNO3
.. oxid8 on stste of M,l"e,, 4 cu(No3)2 +- 2No2 + 2 No t 6 I{2o
x=+5-3=*2
or 2Cu +6tlNO3 -......-
4. The balanced redox equatiotr h
g+ 2 Cu (NO3)2 + NOz + NO i 3 I{2O
2 MnO.- + 5 CrOl- * 16
ccflicientsr and/ of Cu and HN03 resPec-
2Mf2+ +- loco2+8H2o
Thus
tiwty are 2 aod 6.

Thus, the cooffickrnts of MnOf , CrO!- and H+

12. MnOa- * 3H+ +5 g-- Mnz+ +'1Hrt)
respcctivcty are 2, 5 and I 6.
FeCrOo__fe2trC-zOl-
5. LorBe ngath Potenthl for the reaction, A + e-
A- imdics thal thc reverse reactioo oc{:u$, Fs2r Fe3* +e-

-rle., A- is readilY oxidised- qol- - lCOz + 2e'

7- 'fhe O.N. of Ca, C and O rsmaio the 6ame Since ons- nlole of FeC2O4 lcses 3 Dloles o[
E. TotalO,N. of2 nitrogen atoms in N?H1is --4' SiDce
eleclrons while one nlole of KMnO4 ilcccPts five
it lcs 10 moles of eletrons, thereforc, the total
tE:\,Rir.s
!!tt'11Tri:!\tnr..s!":
u
5E. D 59. c 60. c 61. c
REDOX REACTIONS
9167
moles of electrons, therefore, number of KMnO4 32. C in COz has the ntaximum O.N. of + 4 aDd betrcc
requtued to cDddise one mole of FeqO4
= 3/5 it cannot acr as ir reducing agenl.
= 0 6 molc. 33. In rhis reaction SO2 oxidises HzS ro S. therslore,
16. A metol wirh hither O.p. (r... A) replaces a metal Sa)2 acts irs rhe oxidisiDg agent. During oxidation,
wirh lower O.P (r:e. B) from its aqueous solution.
four elec{rons are lost, !.e,
17. The species wilh the lowest electrde potential is
the strongest reducing agcnt i.e. Fe2+,
SOrr4e-.*S+202-
']hus, Eq. wr ot SO,
lll Onty Al (E = .66 V) has lower electrode = Ir,,169. s,1-74
poteDtialthanZD -l(E" = -{).76V) aM henco irwill
= 64/4 = 16.
rcduoe Znz+ lo ZD while all others have higher 34. Sinc both rhc tigaDds, ie., pph3 (rriphcnytphos_
electrode potentiab than Zrl.
phinc) and CO are neutral aDd the complcx does
19. Lowt the reduction potential, strooger the reduc_ not carry anv charBe, therefore, O.N. of Cr is zcro
ing ageDr. Y (- 3.03 V) > Z F I.66 g >
x (+ 0.52 v.) J5. The balanced chemicalequation is:
21. Since the reductioo potential of y h greater than 6OlI-+
3Cl2 + CtOt + 5 CI- + 3IlzO
lhat of X but l$rcr thaD that of Z, tberefore, ywll
37. M++e-...-14. E.= +0.44V ...(r)
oxidize X bur rct Z.
X+e-*a-; E.= + 0.33V...(ii)
22. M3+ M6+ + 3e-.
- Subtracing EqD. (ii) from EqD. (i), wc have
23. In CO3-, C ha6 highcsr o,(idarion stare of + 4, M+-x...tM-x-' E =+o.llv
rherefore, it cannot act asa reducing ageot while all
othcrs aet as reducing agents and hebce will not o, M*+X--*M*X ; E.=+0.llV
decolourisE KMnOr srolurion. / ie., M++X--..-M+X
2{. Six electron changc, is ihe spo{rtaDeous reactioD.
. . Eq. ,rt. 3E. Since K2Cr2O7 accepts 6 elcctrons for its reduction
= nrol. wt,/6.
27. 3 x (+ 2) + 2 x (+ 5 + 4 x - Z) to Cl+ ioos. ... F4. wl. IUot, wr./6
=
-+6+2(_3)=0. 40. SiDce E"Fc?+/,po is therefore, Fe has a high
2t. The balanccd equation is -ve,
tendenc, to
pass into Fe?+ ioDs. As il rcsult,
KzCr2OT + HzSOa +3SO2
- 1Fc2+l incrcases and hence thar of [Fc3+]
IqSOa+Cr2(SOa)r+HzO. decreases. Alternariwly, Since Fc3+zFe2r is +ve.
Therefore, X Y aod Z, the comcieDt.s of lherefore, Fel+ has a stroDg tendenc) to pass iDto
I{rSOo, SO, aud HrO relpecrivety are l, 3, t.
Fez+ and hence [Fe2+l increases i]nd rhat oi
30. The balancd equatton is; 1Fe3+] decreases.
2Fej+ 1aq1+ sn2+ 1aq; -* 41. E"\ralues decrease in the order :
Ag(+ 0 8{}V), Cu (+ 0.34 9, Fe (_0.4J V),
2 Fe2+ 1aq'1+ sna+ (o4)
Zn (-4 'l6v).
Thus Ais Sn4+.
42. MnO; wiltoxidise Ct- ior according to rhc equa-
31. Gzolt.- + 14 H+ + 6e- l,gf + a711rg tion,
-
Sn2+ 5n1+ + ze-l x3 2KMDO; + l6H+ + t0cl- *
-
2Mn?++8H2O+SCI2
0rO|- + 14 H+ + 3 Sn2+ -* The rell correspondinu lo lhis rca(lit.,x is
3Sna++2CF++7Hro Pr, Cl2 (lbar) | CI- | | Mnoo-, Mn2+,II+ 1 pr
From the above EqD., it is svident that 3 moles of Ec = 1.51 - 1.40=0.1t!,
Sn2+ reducc 1 mole of CrrOf- As Et[ is +ve, thr abcrtp reaction Ls feasible aud
.. 1 rnole ofSn2+ will reduce lB mole ofCr2O?-. MnO; wil uidise nor only Fe2+ ioD bur Cl- ion
also.
 Neut Course Chenr i strg
9i 68
+5 (ii) 2 Na2S2O3 + 12..... NES2O6 + 2Nal
lo + e- (M nOa)-z.
- Cu[2 is only ilcorrect statemeDt.

54. 2IO1- + 16 l2+81-l2o

+3
1/2 MD?Ol Eq.*r.of Io1-='" Y;'*t = *ru
+2 55. IqCrzOT + 2 Flzsoa *
Mn 2 KHSoo + 2Cro3 + Hzo
Red
7n7+ + 2e- ; Ag+ + e- Il' 4g 2KCI + H2SOa* 2KHSOa + 2HCl x 2
45. Gold ha.r higher li" (+ l 50V)thanFe(-0 44v) Cro3 + 2IlCl * CrOzClz + H2O x 2
and hence q.ln oxidisc I"e to ['-e2+
+6
IqCrzOT + 4 KCI
46. szo12- (r 3) < so3- (+ 1) < s2o;- (+ 5). 2CrozcL+6KHSO4+3H2O
s6. Al lA.r3+ ll Ac+ lAc
E-1 - Eo^r+7^, - ff rrr'* / ot
or 2.46 = 0-80 - E"Al3+urr
or E AP+/AI = - 1'66 V
60. Hirher lhe reduction potenlial more easily it is
reiuccd. Since the reduction polential (-2 37
Vt of Md+ is much lo$er lhan ihat of s'ater
t-o s: V), therefore, H2o EErs reducd in
Dreference to Mgl+ ions. ln other words, Mg
iannot be oblainad by electrolylic rcduction of
M92+ ions in aqueous solution. Thus, the actual
sequence of dePosition is Ag, Hg, Cu'

61. SOl- is not a reducing agertt and henc does Dot

reduce Crro]-.

Lg
2' Use the lolloring
Thequesools
key to choGe the sPPrcPrhte oNwer'
Utf assertiou and reason ore CORRECT aDd reoson ls thc CORRECT cxphnotlon ofthe
acsertion'
laif exPlslstlon ofthe assertlon'
iolttoo,t rnd reasol are CORRECT but reasor ls not the CORRECT
"""."Oor
(c) IfossertioD is CORRECT but thc resson ls TNCORREC'I'
(d) Ifboth ssscrtioD and reason ore INCoRRECT'
Assertior (Columr l) Reoson (Column 2)

1. Blue colour of CuSO4 solution fades away whcn Cuz+ ion is oxidised by Fe
iroD plate is Placd in it.

Copper liberates hydrogen from a dilute solution HydroSen is below copper iD the electrochemical sries'
of bydrochloric acid.
u.I.I.M.S' l99s)

Zinc displaces copper from copPer sulphate solu- E of Znis-0 76 V aDd that of Cu is + 0 34V
(A.I.I-M.S. 1999)
tion.
BEDOX REACTIONS
9/69

Tru e, / Falee 5t atement s

lhbh ol ,lE lollowitg srolements a,c tuc orld ti,hich 6. Stck notation is used to Damc compounds of me-
ore folte ? Rcl,4|ire lE lobe rtateriqrt cdTectty. tals which iovolve variable cidation staEs.
1. Oxidation is a process \rhich i6/olt rs ic6s ofelectroos.
Reducing agents are electron accsptors.
7. The oxidation numbr ofN in Np3 is +3.
3. Copper mel,al can be Gidised by Zo2+ ions. t. Metals whose electrode potendals are lower than
that of sta[dard hydrogen elcctrode react with
4, Cl2 caD criidise Br- iosn to Br2. aqumus mineral acids to evohr [I2 gas.
Copper sulphate solution can be placed iD a vqssel
made of ziDc.
9. HgCl2 aDd Snclz caonot exist as such if presnt
together in an aqueous solution.

Fill ln The Blank.s

OxidisiDg ageDts are.............. wbile reducing agenls
4te.................,..
In oxidation, the oxidation Dumber of ao elemcDt
................. while in reduction, it .............--..
A substanc which increases the cxidatio[ number
of some other substanc in a chemical reaction is
called an ................. .
4. The oxidation number of N iD NI3 is
5. The teDdency of an electrode to gain or
electroN is cnlled
6. Standard electrode potentials are measured uDder
................. conceotration of metal ions and a
tempcrature of .....,........... .
.
7. The standard electrode potentials of siDgle elec-
Irodcs arc measured with referenc to ,.,............., ,
E, In the electrochemical series, the clements are ar-
rangcd iD order oftheir incrcasing ................. .
9. The compouDd YbBa2C\rO7 whici shorrs super.
conductivity, has copper in midation state
......-.......... Assume that the rare eartb element yt.
lose
terbium is in the usual +3 midation state,
(rJ.x 1ee4)

M atchin O Typ e e.u estio ns

Match thc apropiate enoics h coh.trn B X anlt y
x
l. Ruorine (a) Liberates Ct2 from Cl- ions
2. Znc, magnesium, iron etc. react with (6) Reduces HgCl2 to Hg2Ct2
dil. H2SOa to evoke
3. Stamous chloride (c) Hydrogen tas

1. Elcctm[ acccptors, clectroo doDors A iD6essca, dccreases J. qidising agent 4 _3, 5.

eledrcde
urogeo etectrode & electode poteotials 9. 76.

r. (a) a (c) 3. (r)

Ht NT9/EXPLANATIONg to AsserAion'Reason Ty?e Q,uest',ione
 QJ N! OfT

?rinciple= and ?roceeseo

of E><tractiort of Elen-tenEs

)i
I
i Concentration ol orcs,
Concenttation ores, reductiory' oxidation (eleclronation/
(eleclronation/de- electro- nalion), refining ot metals. i
t*.. -. _ - _.*.* **
,"--,""., ".'",,,.-.,'*,*,"'"..,..;

variety of nuclear
Elemerts are the basic units of all types of
matter in this universe. How were these ellments
eutroos emitted b
originally formed and how are they distributed on ffNe + lue .....- fiwg + Ut
earth ? What are their modes of occurrence in the
earth's crust and how are they obtained iu the pure llt'to + ln ..-.* lrMo + /-ra)6 +neutrino
hrm ? These are some of the interestiog qu..iion. ,l
which come upin our minds and in this uiii we shall
W+ -?p
The daughter ouclide such as !!Mo and
!!Tc may capture more neutrons giving rise to
elements with higher atomic numbers. Besides
10.2. Origin of Elements :!:rrr:.:r::.:,:::j:i;::,:j,:,:ir:i:r::.:::.:.::;::::,::i::::i,::.,!,:,:,:: neutroacapture, cleE
impact of cosmic rays
accepted views, within phere. For example, I
two of the universe, there
was rature and most of the l.N+ [, -- l1c+ lH
matter at that time still consisted of hydrogen
(89Vo) and treli,um (llo/.). The condensation-of _ This reaction still continues andis responsible
for asteady concentration of l.C in the living world.
some of the clouds of H and He resulted in the
10.3. Oistribution of Elements on Earth
influence
and den-
to merge
rred. The

.In flualcar Eactions, thc numbcron

_
thc bottom lcft dcnotc6 thc atomic numbcr.
thc top lcft ofthc symbol oft

utlt
1o12

Volatile elements : C, halogens, Hg, Pb' Zn (i) Based upon the stsbilities of tha nuclei,
elements with even atomic numben are more abwt
Non-volatile elemenls ; Fe, Co' Ni, Si, Be, Ca
dont than those wilh odd atomic numbers.
It is, therefore, reasonable to believe that ter-
(ii) Thehig! abundance ol iron h due to its ltigh
restial distribution of non-volatile or less volatile
nuc\ear binding energt
elemenG would be somewhat similar to the overall
cosmic (i.e. in the universe) distribution. On the (iii) The low ligl er elements
abundsnces oI
other haad, volatile elements are greatlyless abun- ruch as Li aft
Be and B due lo thei ability to rcact
dant on eatth due to their loss during the high wih more 4- Particles Ioming other elements' For
temperature periods accompanying the formation qMPlq
of the earth.
lne + lue ""'.' l'zc
Cosmic abutrdances of elements.t The cos-
mic abundances of elements are shown in Fig 10'1' 103.1. Condensatlon Processes
These data are only approximate because of the The non-volatile elements becauso of their
following reasons : higb melting points underweot condensation
without any loss at relatively high temperatures
and thus appeared as minerals in high abundances.
The moderitely volatile elements such as Ag, Zn,
1',. Ge, Sn and F, however, condensed in lower abun'
$a
z
dances while volatile elements such as Cd, Hg, Pb
and halogens (other than F) condensed in rather
o-
zo relatively low abundances. Thus, the early conden-
dl sates inilude metallic iron (with 12'5% Ni) and
u4 diopsidz (Ca Mg Si, 05) aad anofihite
t-
5^ (Ca Al, Si, Or).
e_ In this way, Fe, O, Mg and Si account for about
o0 mVo ot ahe earth, the elements S, Ni, Al and Ca

Th account for anothe t 6 -7 Vowhtle allother elemenLs

I
l-a accotnl for 3-4Vo of the earth.
.U
1032. Zonal DlsHbutlotr
ATOMIC NUMBER ---+ The earth mainly consists of the following hvc
zones :
-
1. The atmosPhere

2. The hydrosPhere

3. The crust or The lithosPhere

fi\ Elemensore not unilonnly distibuted' i'e' 4. The mantle

rhere on higher concentrations oI ce,tain elements in 5, The core
different rugions ol he eqnh.
(ii) Eanh is not uniform from he core to the
cntst.
(iii) Compotilion of othet ploncts is not the
same as that oJ the ea h'
In view of the above facts, terrestial abundan-
ces have little or no relation with cosmic abundan-
ces. However, there is a broad concensus on the photosynthesis.
following conclusions :
tNon-evaluative
PRINCIPLES AND PROCESSES OF EXTHACTION OF ELEi,,IENTS
The three inner zones, i.e.,lithosphere, mantle
and core are studied by seismography. These are
distinguished on the basis of properties which
depend upon density and elasticity.
Let us now briefly dlscuss the comPosition ol
these zones.
1. The atmosphere. The gascous mixture sur'
rcunding lhe earth is called the atmosPhere. It col-
tains mainly nitrogen (78'W%), orygen Q0'957o)
and other gases such as COr, He, Ne, Ar, Kr and
't0 - 50 km
2900 km
2100 km
650 km
FIGURE 1O.2. Main zones in the earth's interior.
(l) Igneous rocks. It is believed that the
temperature deep down the earth is very high. The
ertre,nely hol mateial present inside the eulh is
called magma.D\e to earthquakes, some Yents are
created in the upper layer of the earth. The high
temperature inside the earth sometimes forces the
magma out of the earth',. surface through these
vents in form of volcanic eruptions. ThLs magma
gets spread ovcr the surface of the earth. With
gradual cooling, over the years, it gets solidilied in
the form of rocks. Thtts, igneous rockt are formed by
gradual cooling and solidification (i.e. Iructional
crystallization) over billions of yean of the molten
moteiql coming out oI the eatTh's surface duing
volcanic eruplions. The word igneous implies
formed by fire. These are mainly made up of
aluminosilicates along with certain other ions such
as Fe2+, Mg2+, ca2+, Na+ and K+. These rocks
cover about 4/5th of the earth's crust. Some impor-
tant examples of igneous rocks are : grazite, basalt,
gabbru, etc.
10/3
Xe (< l%). The atmosphere extends not more
than 60 km above the surface of the earth.
2. The hydrosphere. The liquid phase oI the
edrth (oceans,lokes etc.) is called the lrydrosplure.lt
covers about 807a of the earth's surface. There are
a large number of elements present in sea water.
3. Th crust or the lithosphere. The upper
solid phase of the earth is called the crust or the
lithosphere. Its thickness various from 10-50 km
(Fig. 10.2). It consists of three tlpes of rock.
CRUST (LITHOSPHERE) : lgnous rocka-shale,
aandstong, llmodone
MANTLE : Solid layor olmagnesium and iton
sllhai.!.nd lome rulPhldq!.nd oxldc!
OUTER CORE : Llquld Fo-Nl alloy
INNER CORE : Solld Fe-Nlalloy
(ii) Scdimentary or Strattlied rocks. The
weathering (selective extraction) of igneous rocks
by water, carbon dioxide and humic acid (organic
acid formed when water passes slowly through a
mass of decaying vegetation) dissolves
Na+,Mgl+, caz+,Fe2+ etc. leaving behind in-
soluble residues consisting of TiOr, Fe2O3 and
SiOr. These insoluble residues are ultimately
broken into fine pieces called sediments. These
sediments are then carried awaay by water to river
banks and sea beds where they get deposited. With
the passage of time new layers are deposited over
the old ones. The bottom layers are ultimately con-
verted into rocks by the pressure of overlying layers
and presence ofcementing material like lime. Thus,
sedimentary rocks are composed mainly of
minerals such as dolomite, limestone, silica, iron
oxide, clay etc. The sedimentary rocks are also
called stratified roc&s since they occur in form of
layers. Limestone, sandstone, dolomite, shale etc.
are some important examples of sedimentary rocks.
1014
(iii) Mtamorphic rocks. These rocki ure
fotmed by the structlrrul modilicalions of the igneous
and sedimenlary rocl<s due to hiSh lemperait c
4. The mantle. The portion of the earth lying
immediately below the crust is called the mantle. Its
thickness is about 2900 km. It mainly consists of
silicates of Mg2+ and Fe2+ along with some sul-
phides and oxides.
5. The core, On the basis of type of phase, the
core has been divided into two parts, viz, the outer
core and the inner core. Whereas the inner core is
a solid of about 650 km depth, the outer core is a
liquid of 2100 km depth. Both these ParG maidy
consist ofFe-Ni alloy.Apart from Fe and N| other
elements alloyed with iron in the core are Co, Pd
and Rh. Seismic studies also suggest the presence
of some orygen or more probably sulphur in the
core.
Goldschmtdt Classificatlon' According to
GoldschrEidt classification, earth consists of the
following four zones :
1. Slderophtl. The innermost Poftion of the
eorth is called the iron core or the metallic core or
siderophil (sideros it Greek means iron). This
covers both inncr and outer cores as meutioned
above. The elements present in siderophil are
called iderophiles.
2. Chalcophtl. Thz loyer ol the eotlh sutround'
ing lhe iron corc (i.e. mantle as mentioned above) li
called chalcophil. Since this layer mainly contains
sulphides of Cu, Zn, As and Pb, therefore, tbe
elements present in this layer are called chal'
cophiles (/<iral&os in Greek means copper and
brass).
S.Lithophil,The outermost po,Tion of the earth
is caltedlithophll (,lit&os in Greek means stone) and
the lements present iD this layer are called
lithophiles.
4. Atmopbll. The gaseous mirture sunounding
E crust or the lithosPhere is called the atmophll.
The distribution of the elements in these four
different zones is different as shown in'Ihble 10.1.
Ne.a,
1'AIILD 10.1. Distribution of
elcments in dilTcrent zones.
Constitnents
Zoae
Sidcrophil Mn, Fe, Co, Ni, Cu, Ru, Rh, Pd, Ag,
Re, Os, lr, Pt, Au
Chalcophil B S, Zn, Ga, Ge, As, Se, Cd, In, Sn,
Sb,'Ib, Hg,1l, Pb, Bi
Lrthophil Chlorides, sulphates aod carbonates
of metals like
U, Na, I( Rb, G, Mg, Ca, Sr, Ba
Silicates aDd oddes of metals like
Be, Al, Si, Y, l-a, Ac,'fi, Zt, Hf , T-tr,
Y Nb,'Ih, Cr, Mo, \Y U
Atnrophil F, Cl, Br, I, B, C, Si, N, O, He, Ne, Ar,
IK, XE
From the above table, it is evident that an
element may be prominent in more than one
geochemical category. For example, orygen can
be regarded both as a lithophile and as an at-
mophile.
10.4. Abundances of Elemenls
in The Earth's Crusl
Earth's crust is made up of light clements
such as orygen, silicon and aluminium. Oceanic
crust is mainly basalt (which also contains mag-
nesium and iron). Continental crust is mainly made
up of t*o types ofigreous rocks :
(i) Light tockr, i.e., granite and related types
containing 707o SiO2 together with AlrOr.
(ii) Heavy roclg i.e., basalt containing40'50Vo
silica togetber with MgO.
Aluminium is the second most abundant elc-
ment in the light rocks andmagnesium is the second
most abundant element in the heavy rocks.
112 elements are knowlr at Present time. Out
of these, 88 have been found in nature and the
remaining have been synthesized. Orygen con'
stitutes nearly half (a9'5) and silicon one'quarter
of the total mass of elements in the earth's crust.
The sixteen most abundant elements in the earth's
crust and their percentages by weight are listed in
Table 10.2.
 PRINCIPLES AND PBOCESSES OF EXTMCTION OF ELEMENTS 10/s

'lABl,E 10.2. Sixteen most abun(lant elements in the Darih's Crust.

Atomlc number Elelnent Percentogc Atolrtic nurnlrer ElGmeot Prcentage
(by wri8ht) (lryweight)
8 O)rygen 49.5 I Hydrogen 0.9
t4 Silicon 25.7 n 'fitanium 0.6
13 Aluminium 7.5 l7 Chlorine o.z
Iron 4.7 t5 PhGphorus o.l
m Calcium 3.4 25 Manganese 0.09
ll Sodium 26 6 Carbon 0.0E
19 Potassium 2.4 16 Sulphur 0.06
t2 Magnesium 1.9 56 Barium 0.M
Ctbtal prcntage weigbt of rhese elements = 99.?7)

T\vo poins which emerge from the about table '10.6. Oceans as a Source ol Elements r"rftirg*;,++irr',i
are :
Oceans are a rich source of many useful
(i) Elemens with low atomic numbers con- substances, nutrients and minerak;. For example,
stitute a major porion of the earth's crust.
(i) Oll and natural gas octur in continental
(li) Elements with evco atomic numbers are shelf sedimentes.
generally more abuldant than elements with odd
atomic numbers, There are, hoq/ever some excp- (ri) Gold and manganese are present as sedi-
ments on the ocean floor.
tions. For example gases (with even atomic num-
bers) occur only to a small extent because they
probably escaped into the atmosphere during the
condensation period.
i 0.5. Llernents in Biological Wo rlcl f:ir,i+.:rjii li.iii.ii:i.,ii:,,i,:

Many elements are accumulated in living or- (i) Igneous rocks consist ofaluminosilicates of
ganisms. For example, sodium, pota-ssium, calcium etc. Rain water con-
(r) Iodlne rs sea weeds, (li) vanadium in sea taining dissolved CO, dissolves these elements as
cucumbers (ilr) Magnesium in chlorophyll, the thei.r bicafionates wlich go ioto sea water leaving
green colouring pigment of planLs. (iv) Potassium behind clay and sa nd (called detrias cloy) .
and iron also present in plant life. (v) Carbon and Igneous rock
hydrogen are major comtituents of all organic
CaAtStos
molecules (Dimoleczles) present in our body in one
Co I c itgn o lumin dtili c atc
form or the other. Besides, these living organisms
contain different elements in different parts. For + KAIS3O8 * Rain water
example, (i) lron in haemoglobin (blood). (PoL olumhatilica,c) (H2o + co,
(i) Zlnc in eyes of some animals and the + NaAlSi3Ot
enz,,rne carbonic anhydrase present in cells. (Sod" oluminNidcotc)
(iii) Tiaces of Mn, Fe, C\ ln abe chloroplqsts. Stream ofwater + Detritus clay
It may be noted that very little is ktrown as to (ca2+, K+, Na+, HCot) (claY + Sio)
why a particular elernent is present in a specific (ri) Marine organisms convert Ca2+ and
region of the living organisn. However, it is known HCOI ions to form CaCO, (shells) which form
that their deficiency causes many disorders in the sediments,
body. For example, deficiency of iron causes
anaemia while lhat of iodine causes goirre. _ _ Irarinc organisms

F\trther, except iodine, no other element has

beer isolated from these biological sources. caco3+H2o+c()2
10/6
Neut CouYse Chemistrut

(rrr) HCI injected by undersea volcanoes the air occur in the native state. For example, gold,
reacts with HCO; to form chlorides of Na, K and platinum, noble gases etc.
(ii ich are
Ca in sea water
HCI+HCO| CI-+H2O+CO2 readily carbon
dioxide state in
-
The relative abundance of elements in sea form of their compounds called minerals.In the
water is shown in Fig' 10.3. combined state non-metals are found in the
reduced form while metals are found in the
oxidised form such as elements are generally
10 present as oxideg carbonates, sulphides, silicates
etc. as shown in Thble 10'3.
1-.Ult lt !U.-l' llrrpot'tant'l\pes ot ()l'es
Ore type ExamPles
I
o) Natlve
Y
J
O ta-2
Oxides
O
zo
o

104

Carbonates

CI NaMgS CA K C BT B ST Si N Li AI Rb
MAJOR ELEMENTS MINOR ELEMENTS

FIGURE 10.3' Elements in sea+'

Although sea water contains many elements Sulphides

but only four ,i.e., sodhtm, nlogtesiunt, chloine und
bromine are commercially recovered from it'
Besides these, some rare metals are recovered
from manganese nodules which are occasionally
found in sea beds.
Huge amounts of metallic and non-metallic
elements are present in sea water. Some important
ones are Na+, Mg3+, Ca2+, K+, sr2+, cl-, soi-,
HCO3-, F-, Br-, I- etc. In future, sea water may
become an important source of many metals such
as uranium and gold.
.::.::: :: '::::. : t

Elements may occur either in the native (ot Phosphates

free) state or in the combined state.This is mainly

due to the reason that different elements possess
different chemical reactivities'
(i) Natlve state. Elements which are not at- A variety of minerals are found in India. For
tacked by moisture, orygen and carbon dioxide of example,

'Non-evaluative
PRINCIPLES AND PROCESSES OF EXTRACTION OF ELEMENTS
(i) ffssa and Blhar have the largest deposits
of ores otiron, manganese, chromium in addition to
coal, mica and phosphates.
(ri) Madhn Pradesh and Maharashtra have
sizeable reserves oI maganese, chromium and
bauxite.
(ra) R4lasthan is rich is non-ferrous metals
like copper; zinc atd lead
(rv) Thmll Nadu has large deposits of iro4
manganese, mkq limestone a\d lignite.
A number of industries are producing iron,
aluminium, zinc, gold etc. The Steel Authority of
India (SAIL) is producing over 10 million tones of
steel through a number of steel plants.
1o i)- Occurrence o, Metals-Minerals and Ores,,r,r
Majority of the metals occur in the crust of
the earth in the combined state in form of com-
pounds called mluerals. Thus,
The nafitral materidls or the chemical com-
pounds in which the melals occur in the eqrth are
called minerals.
In other words, metals are extracted from
minerals. But every mineral is not suitable for the
extraction of the metal.
llu mincraltmm *hich the melal ts conventg l!
arul econonicel$ *acal is slltil an one. Ihzs,
aU org5 are mlnsok ba all mtnemb on t* ors.
For example, iron is found in the crust of the
earth as oxides, carbonates and sulphides. Out of
these minerals ofiron, oxides of iron are employed
for extraction of th e metal. Thus, oxides of iron are
called ores o/ iron. Similarly, aluminium occurs in
earth's crust in form of two minerals, i.e., bauxite
(AlrOr.2HrO) and clay (AlrOr. 2SiOr. 2HrO). Out
of these two minerals, aluminium can be con-
veniently and economically extracted from bauxite
while no easy and cheap method is so far available
for extraction of aluminium from clay. Therefore,
the ore of aluminium is bauxite. Further, the main
minerals ofcopper are copper glance (CuS), cupnk
(Cu2OL copper pyitet (CuFeS), malschite
(CuCOr.Cu(OH)r) etc. but copper can be con-
veniently extracted from copper pyrites.Thus, cop-
perWite is the orc of copper
10.10. Exiraction o
As stated above, only a few elements occur ilr
the native state in nature while majority of them
lOlt
occur in the combiled state.In the contbined state,
metals usually occw in the oxidised form, (e.9.,
FerO, AlrO j, SnO, MnOr) while non-metals
occur in lhe reduced fotm such as X- (X = Cl, Br,
I). Silce the modes of occurrence of metals and
non-metals are different, therefore, their methods
of extraction or isolation from their natural sources
arc differett. Metals orc usudlly oblained from their
oidised forms by reduction while non-melals are
obtained from lhet reduced lotms by oidqtion.
Whereas reduction is btought about by eleclton,a-
tiot, i.e. ; addition of electons dinctly ot indirectly,
oidation is canied ou, b) dc-clcctronation, i.e., by
removal oI ekctrons dircctly ot indirectly.
10.10.1. Extractlon of Non-metalllc elements
Non-metals occur in the combined state in the
reduced form. Therefore, they are generally ex-
tracted or isolated by oxidation of their com-
pounds. Consider, for example, the oxidation of
chloride ion in water.
2 ct- (aq) + zHrO (t) --.---+
zoH- (aq) + H, G) + Ct G)
Since this oxidation cannot be carried out by
ordinary chemical methods. Therefore, it is ac-
complished by electrolysis. The minimum potential
difference required for the oxidation 'ts 2,2 y.
Similarly, fluorine is extracted by electrolysis of
their fluorides. Elements like oxygen, nitrogen and
noble gases are directly obtained from this. In con-
trast, carbon, sulphur and phosphorus are ex-
tracted either from native ores or by oxidation of
their compounds occurring in nature. From the
above discussion, it follows that there are no
general methods available for extraction of non-
metals. Therefore, the individual methods of their
extraction will be discussed while dealing with the
chemistry of these elements in uDit 13.
10.1 1. Melallurgical Processes
The procrns o! dtacting mcrd\r Jrom their ores Ls
called metalfurg.
The process actually employed for the extrac-
tion of a metal depends upon its physical and
chemical properties and the impurities associated
with it. Sioce differeot metals have different physi-
cal and chemical properties, they have different
methods of Theref or e, a s in gl e, univ ers a I
tnethod csnnot be sppliedfor the efiruction of oll the
/zerab. Still there are some procedures and proces-
ses which are common to the metallurgies of
various metals. These are termed as metallu,Eical
opemtions.
10/8 I't <t,i, , 1.': Neut Coursc Chemistrglffi[l)

Eveo l6{D yes6 ago, Indians had a high level ofskill io metallurry. This is evidenl &om the Delhl IroD plllar
Near Kutab Mioar. It is essntially made up of wrough iron (99 .72Eo), carbon (0.08%), silicoo (O.M6%),
sulphur (0.006%), phGphorus (0 1l4%)and margaoese nil. Since40OdD., it has been existio8 without any
rust or siSDs of decay.
Thi! s pdmarily due to the reason that during linishiDg treatment gitn to the pillar, a ihin Alm of magnetic
oxide (FcaO, $as applied on its surfacc.

Some important metallurgical operations are : 2. Hyilraullc Washlng or Levlgatlon or

I . Crushing and. grinding of the ore
ll, Concentmtion and bendaction of tlu ore.
lll, EJdmctiot, of crude metal lrom the con-
cenfiated orc.
lV. Refinint ol ahe crude metal.
These are briefly described below :
l. Crushlng and grlodlng of the ort.
Tte ores usually, occur in nature in forrn of big
lumps. These lumps are broken into small pieces
rvith help of crushen or grindErs. This process is
called crushlng. These small pieces are then
reduced to a fine powder with the help ofball mill'
or stamp milP.This process is called Pulyerlsatlon.
ll. Concutraton or Benefaction of the ore
(Ort-dresslng).
Oras as they are obtained from earth's crust are
never pure. They are usually asociated with earthy
and silicious impurities (in addition to the impurities
of other minerals) called gangue or matrlx. These
impuritics har,re to be remowd from the orcbefore the
extraction of the metal is actually done.
The finely ground ore is concentrated by the
following mcthods :
1. Hand plcklng. In case the impurities are
quite distinci from the ore so that these may be
differentiated by naked eye, these may be separated
by hand picking.
Grsyity scparatlon. The process by which lighter
eqilry pa,ticles aw freed from the heavier ore par-
ticles by washing with water is called levlgatl on. For
this purpose, the ore Ls either agitated with water
or wtshedwith an upward stream ofrunningwater.
The lighter impurities are washed away while
heavier ore particles settle down.
This mahod is used when the ore particles ore
lrcavier than the earthy or roclq gangue patticles. The
oxrZe ores such as those of itroo (hoematite), tin (tin
stone) and native ores of Au, Ag etc. are usually
concentrated by this method. The process is carried
out in specially desigrcd tables called Wilfi ey tab les.
3. Electromagnetlc separation. This method
oI concentration is employed when either the ore or
tlrc impuities associated with it are magnelic in nq-
ture. Fot example, chromite, (FeO'CrrO, =
FeCrrO.) - an ore of chromium, maguetite
(FerOo) - an ore of iron and pyrolusite (MnO2) -
an ore ofmanganese being magnetic are separated
from non-magnetic silicious gangue by this method.
Similarly, a'nstore o r cassiteite (SnOr), an ore of tin
being non-magnetic can be separated from mag-
netic impurities like those of tungstates of iron and
manganese which are generally associated with it,
by this method.
In this method, the powdered ore is dropped
over a travelling belt moving around two rollers -
one of which has an electromagnet in it. As the ore
particles rol[ over the belt, the magnetic particles
are attracted by the magneticroller. As a result, two
heaps are formed separately. The hcap collected
below the magnetic roller contains the magnetic
particles while the heap formed away from the

'A strmp mlll ir r hcsiystrmp or boltwhich riJas and falls on a die bclof,onwlrich c 6hcd orc is fcd from onc sidc. A t nll
mlll, on thc othcr hand, consists ofa bigstccl tank containing a fe* stecl balls ora fcw picccr ofhard stonc likc flint in it. Thc steel
tank is fed with crushcd orc and w'etcr, and rciatcd. Stcl balls fal! on thc crushcd orc and rcducc it to powdcr.

, F
 10/9
PRINCIPLES AND PROCESSES OF E)fiBACTION OF ELEI\'IENTS

magnetic roller contains the non-magnetic im- The suspension is violently agitatcd by the
purities (Fig. 10.4). In case of tinstone. thc rotating paddiewhich draws in air causing frothing'
iunqstates biing magnetic fall in a heap under thc During this process, the ore particles which
mafoe tic roller while the ore particles i.e. SnO, fall are preferentially wetted by the oil become lighter
in a separate heap away from the magnetic roller. and thus rise to the surface abng with the froth
while the ganguc particles which are preferentially
wetted by water become heavier and thu-s settle
ELEcTfi oI\,lAGNErlc poFJ,,lBEeLJeo down at the bottom of the tank. The froth is
ORE skimmed off. It is allowed to collapse and finally
dried to get the concentrated ore.
If the mineral to be concentrated consists of
NON.
MAGNETIC
PARTICLES

MAGNETIC
PARTICLES
,i..ic
FTGUBE 1O.4. Electornagnedc separatisr.
4. Ftoth tlotatlon. This method is widely used
for the concntration of sulphide ores such as zinc
blende (ZnS), copper pyrites (CuFeS), galena
watet,
The ore is crushed into a frne powder and
mixed with watcr to form a suspension in a tank
stabilize the froth.
sodium cTanide is used as a dePressant to separate
lead sulphide (PbS) ore from zinc sulphide (ZnS)
ore. This is due to the reason that NaCN forms a
zinc complor, Nq [Zn(CN).1 on the surfacr ofZnS
thereby preventing it from the formation of froth.
Under tlese conditions only PbS forms froth and
hence can be separated from ZnS ore.
4 NaCN + ZnS ""'- Nar[Zn(CN).] + NarS
Sod. tctraq/anozincatc (II)
5. lrachlng. This prucess consists in lreoting
lhe powdered ore with a suiloblc reqgettt (such qs
acitls, bases or other chemicals ) n)hkh can selective ly
dissotve lhe ore bul not the imPuilies.
In the Baeycr Procss, pure aluminium oxide
(AtOJ) is obtained from the bauxite ore (which
contains impuities ofFerO, and silicates) by trcat-
ing the powdered ore with a strong (457") solution

ROTATING PADOLE
ORE FROTH

.:a:::::::::::::::::::::
::::::::::::::::::::::::
:;:;:r1g:-:-!::::::
:_:_:1{.[$:;:_:_:
:::::::1..I:::::=+::
.- ""J#:',sllo'
PADOLE ORAWS IN AIR
AND STIRS THE SUSPENSION
10/ 10 Pradeep's

of NaOH when alumina (Al2O) dissolves forming (ii) For gold, 4Au + 8KCN + C)2 + 2H2O
sodium meta-aluminate leaving behind impurities aK [Au(CN)rl + 4KOH
which are Iiltered off. Pot. dicranoauratc (l)
AlrO, . 2 H2O (s) + 2 NaOH (aq) + I{.O (f """'r (Solubk compla)

Alurninn III. Extraction of Crude Metals - Reduc-

2 Na[Al(OH).1 (aq) or 2 NaAlO2 (aq) + tioni Oxidation
sod' mcta-tlumi*tc
4H2o (r)
The solution of sodium aluminate is filtered, Since many metals can be easilyobtained from
cooled and irs pH adjusted downward either by their respective oxides by reduction (electrona-
dilution or by neutralization with CO, when tion), therefore, the extraction of metals acutally
aluminium hydroxide gets Precipitated ; sceding involves the following two chemical processes :
with a littli freshly precipitated aluminium
l.Convenion o{ the ore into metallic oide, i.e.,
hydroxide quickens the process.
Dilution de- electronotion oI ores.
Na[AI(oH).1 (aO 2, Reduction ot elect,onaaion of the metallic
or CO2 oxide to the Iree metal.
- (s) J + NaoH (aq)
Al(oH), 1. Converslon ofthe ore into mctallic oxide or
de-electronation of oras. Metals are usually present
Aluminium hydroxide, obtained as above, is
in ores as hydrated oxides (hydroxides), carbonates
filtered, washed and finally heated to about 1473 K
(AlO3). and sulphides. Depending upon the nature of the
to get pure alumiaa
rninerals present in the ores, the following two
1413 K
Al2O3 + 3H2O methods are used for conversion of orcs into their
2 At(OH)s
-""+ respective oxides.
Leaching is also used for stracting pacious (a) Calclnation.
nrctqls like silver and gold by convetting these metak
or aheir o,es into their sofuble conplaes.
In this process, the finely powdered argentite
or the native silver or gold is treated with a dilute
solution (0.5 %) of sodium or Potassium cyanide This method is commonly used to convert
while a current of air is continuously passed' As a
metal carbonates and hydroxides to their respec'
result, silver and gold pass into solution forming
their rcspective soluble comptex cyanides while the tive oxides. During the process of calcination, the
impuritiis remain unaffected which are filtered off. following chemical changes occur :

Thus : (i) Moisture is diven o*.

4M + 8CN- + 2H2O + 02 """''
(air) Qi) Volatile impuities of S, As und P arc
4 M(Cr.{)2- + 4OH- removed as thei volatile oxides.
Solublc complcx (iii) Water is rmrcvedfrom hydraterL oxides ond
(i) For silvu, hyd,roide ores.

4Ag + 8NaCN + o,2+ zHzO- Al2Os.ZHzO

Heat
------. Alzor + 2H2O
cNa[fu(CN)r] + 4NaoH Bauxite Alumina
Hat
or Ag2S+4NaCN -----..l 2Na[Ag(CN)r] +Na2S FerOr.3HrO ...........r FezOr *3HzO
Sod. diqaroaBcntatc (I) Linronilc Fcrric oxide
(Soh/bh con9la)
NqS thus formed is largely oxidised to
(i) Cabonate ores are converTed inlo their
respective oides by loss of carbon dioxide .
NarSOn by the air current.
Heat
4NqS + 2HrO + 5Or(air)"""""* CaCO, CaC) + CO2
Linestone Calcium oxide
2NarSOo+4NaOH+25
PFIINCIPLES AND PFTOCESSES OF EXTRACTION OF ELEI,4ENTS 10/r 1

Heat 2Zlr$ + 3O2.- ZZIO + 2SO, I

CaCOr.MgCO3 CaO+MgO+2CO, Zincsulphide Zi nc oxide
Dolonlirc 2 PbS + 3O2 -----------' 2 PbO + 2 SO' 1
Heat L6d sulphidc Irad oxide
CuCOr.Cu(OH)2 ....._ 2 CtrO + H2O + CO2
(v) It mokes the ore porous ond hence easily
Malachitc workable in subsequent stsges.
Hcat Like calcination, roxting Ls al,so carried out in
ZICO, ZnO + COz
Calaminc
a reve,beratoryfumace (Fig. 10.6). During roasting
- air vents are kept open while during calcination, air
(v) It makes the ore porcus and hence easily vents are either partially or completely closed.
wo*able in subsequent stages . Calo.aaaion is usually 2. Reduction or elcctronation of the oxide to
caried out it a revetberatory fumace (Fig. 10.6). the free metal. The roasted or the calcined ore is
The concentrated ore is placed on the hearth then converted into the [ree metalby reduction with
ofthe furnacc and heated by flames deflected from a suitable reducing agent. The choice of the reduc-
the roof. ing agent, however, depends upon how difficult the
(b) Roasdng It is the process of converting an reduction process is. If the metal to be extracted is
ore into ils metallic oxide by heating stongly ot very reactive like the alkali metals or the alkaline
temperature insufricient to melt in ucess of air.This earth metals, thenthe reduction ofthe oxide can be
process is com.monly rsed for sulphide ores. The done only by the electrolytic method. The oxides of
following changes occur during roastitrg : less reactive metals like those of copper, lead, tin
(i) Moisuue is removed. etc., can be reduced by a number of reducing
agents. The frnal choice of the reducing agent is
(ii) Oryanic maner is destnryed.
decided by the energetics and economic.s of the
(iii) Non-metafiic impurities Eke thal oI sul- reduction procss.
phur; phospho s and anenic sn Nidlted snd are
The various reduction processes have been
removed es volatile gases-
divided into the following four categories :
s8+8o2 ,
| (Sulphur dionde)
8SOz
(a) Chemical reduction
P4 + 502 | (Phosphorus pentoride) (b) Auto-reduction
"-""-' 2 AaO3 i (Arcenious oxide)
4 As + 3 Or-P4Or0 (c) Displacement method
(iv) Ores are genemlty convefted into metuAic (d) Electrolytic reduction
oxides. (a) Chemlcal Reductlon

CHARGE HOOPER (i) Carbon as a reducing

U Smelting
agent -
o
Lr,.l
l
.\-,.

In this process, the roasted or

the calcined ore is mixed with a
calculated quantity of carbon (coal
or coke) and heated to a high
temperature above its melting
point in a reverberal.ory furnace
when carbon reduces the metal
oxide to the free metal. For ex-
ample,
FIGURE I 0.6. Reverberatory furnace.
10112 N e.r/ I

ZDO+C. + Zn+CO I FeO + SiO2 FeSiO,

1173-1573 K
(Daic impwitks) fitLr)
(Acidic (Fusible sto.)
SnO, + 2C Sn + 2C0 t
(ii) Basic fluxes. For acidic impuities like
Pbo + c ----------, Pb+ co I silica (SiOr), phosphorus pentoide (Paorc ) etc.
2 Fe + 3 CO I
present fa the ore, basic lluxes /ike limestone
FerO3 + 3C
---r (CoCo3), mqgesite (Mgco), haematite (FerOo)
i
Th" monoxide thus evolved or etc., arc used.
produced by"orbo.r
incomplete combustion ofcarbon can SiOz + CaCO3 CaSiO3 + CO2 t
also bring about the reduction of metal oxides to
free metals as shown below : sioz + Mgco3 - MgSiO, + COz t
(Acidic (Baiic !hs) (Fuiblc slot)
1600 K
Zt + COzl inpuities) -
ZnO+CO
- 823 K Production of Iron from the oxide or
Fe2O3+CO ' 2FtO +COz I
Iron is the most important industrial metal.Its
1123 K extraction is carried out in a blast furnace (Fig.
Feo+Co ._ Fe+CO2 1 10.7). It is a tall cyclindrical furnacc madc of steel
lined with fre clay refractory bricks. It is narrow at
The mctal thus produced is in themolten state
the top andhas a double cup and c.ne arrangement
and is tapped out from the furnace. Sometimes
for introduction of charge and outlet for waste
metals may be obtained in the vapour s tate, e-9.,21.
gases. The charge consisting of calcined iron oxide
In such cases, smelting cannot be carried out in an (haematite, FerO, and magnetite, FerOo), coke
open furnace.
and limestone is fed into the toP of the furnace. A
[lux. lf the calcined or the roasted ore still blast of air pre-hcated to about 1000 K is blown in
cootains non-fusible impurities ofearthy matter, an
by means of uarrow pipes (called tuyeres) at the
additional substance called the fluxisusually added
base of the furnace.
during the rcduction process. Thus,
F\tx is a substance whiclt chemically combines Reactions taLing Place ln the furnace'
with gangrc (eanhy intputitia:t) wltich moy still he The following reactions occur in the blast fur-
present i,t lhc )asled or the calcined ore lo fomt an tace.
easily fitsible nrutcial cdlled the slag.
(i) Zone of combustlon. Near the tuyeres,
Flux + Gangue- Slag coke bums to form carbon dioxide.
The slag formed melts at the temperature of C + 02 ---t CO, ; AH = -393'3kl
the furnace. It is insoluble in the molten metal and
also being lighter floats over t-he surface of the Since the reaction is exothermic, lot of heat
molten metal from where it can be skimmed off produced and the temperature here is around
from time 1o time. 1800 K.

I}pes oflluxes. Depending upon the nature of
the impurities present in the ore, fluxes are clas-
sified into the following two tyPes :
(i) Acidic lluxes' For basic impuities like lime
or metallic oides (FeQ MnO etc.) yesent in the ore'
acidic lluxes &,te sr?lc a (SiO) and boru (NarBoOr.
l0HrO) ac. are used
Cao SiO2
(ii) Zone ofheatabsorption.ThLs is lower part
of the furnace and the temperature here is between
74.23-1673 K. As the CO, formed near tuyeres
moves up, it meets the descending charge. The coke
present h the charge reduces CO2 to CO.
co2 + c--.+ 2co ;AH = + 163 2kJ
Since this reaction is endotherrnic, therefore,
CaSiO,
the temperature gradually falls to 1423 K.
 PHINCIPLES AND PROCESSES OF EXTRACTION OF ELEMENTS 10/13

Furmce Double
charg! cuP
(ore + coke) and cone
+ limestone arran9ement

Oro lose3 Fumace gases

molsture and containing 25% CO
becom6s more used lo heat
porous incomrhg air blast
523 K. Fire bricks

Slag tormailon sholl Redudion bogins

CaCO3rCaO+CO2 E23 K Fe2O3 + CO rr 2FeO + CO2
Fe3O1 + CO r.3FeO + CO2
CaO + SiO2 -.) CaSlO3(Slag) l1Z3 K
Melting ofslag Reduclion compl6tcd
and iron 1423 K FeO + CO -, Fe + CO2

Fluid slag and 673 K

liquid Fe trickle
'r
Coke bums to fonn co"
down lnto hearth t&x, K which on passing up '
fumace through more
hot coke is reducad to CO
C+O.-'Co"
Tuyeres
+t -+ c6
co2

//
Mollen pig iron

FIGURE 1O.7, Blast lumace for the manulacturc of pig or c.rst iron.

But the further reduction ofFeO to Fe by CC)

(iii) Zone ofslag formatlon.It is the middle occurs around 1123 K
part of the furnace. The temperature here is
rln K
1123 K. In this region, Iimestone decom- FeO + CO --.---..r Fe * CO,
to form CaO and COr. The CaO thus
However, diect reduction of iron ores, i.e.
acts as a flux and combines with silica magnetite etc., which might have es-
as an impurity) to form fusible calcium reduction around 823 K gets completely
silicate slag d to iron by carbon above 1123 K.
CaCO, (s) CaO (s) + CO, fu) > 1123 K
Fe2O3 + 3C -------- 2Fe + 3CO
CaO + SiO2 -"""""- CaSiO,
(v) Zone offuslon.Thisis the lower part ofthe
Calcium srlicatc (dag)
furnace. Temperature here is in betwee niqZ3-rcll
(lv) Zone o[ reduction. This is tbe upper K. In this region, spougy iron melLs and dissolves
of the furnace. The temperature here is some C, S, I SiO, etc. CaSiO, slag also melts in this
around 823 K. Her the ores are reducd to FeO
region. Both themolten slagand molten iron trickle
co. down ilto hearth where i-hey form two separate
823 K The molten CaSiO, slag being lighteiforms
Fero, * CO 2 FeO + COz upper layer while molt
--=r
823 X r.sthe lower layer. The
Fe3O1 + CO -------r 3 FeO + COz allytapped off. The iron
is called pig lron or cast lron.
10114
l'rarlt t l's Neut Course ChemistrgWID

(ii) Reductlon or electronation by hydrogen. separated from the other products ofthe reaction.
Hydrogenis alsoused for reducingoxides of metals A few examples are :

but this is more expe.sive than using carbon. Fur- 2Al + Cr2O3 N2O3+ zct
ther, because of its inllammable nature, it is used
only in those cases where carbon does not work. 8Al + 3MqOl - 4AlO, + 9Mn
The oxide of the ore is placed in a tray and heated
in a current ofhydrogen. For example, -r be reduced to metaUic
Likewisc Fero, can
Ilcat iron.
WO3 + 3Hz ........+ + 3H2O w
'fungsten Tungstcn 2Al * FcrO, '---------' Alzo,r + zFe
trioxide
Hcat The molten iroa produced as a result of ther-
Nio + H2 Ni + HrO mite process can be used to weld broken parts of
Ilcat heavy machinery of all kinds, such as girders, rails
MozO3 + 3Hz--------- 2Mo +3H2O etc, This pmcess is calred tbcrmltt weldin8.
olltide nu Molytrdenum
M Dr (lv) Other metals as rcduclng agents. Like
trioxide
aluminium, other electropositive metals can be also
(iii) Aluminlum as a rducing agent. Many be used as usually agents. For example,
oxides like CrrOr, Mn3C)a , Fe2O3 etc. are not easi-
ly or satisfactorily reduced by carbon or carbon BrOr+3Mg-'3MgO+28
monoxide. These oxides are, however, easily TiO2 + 2Mg- Ti + 2M8O
reduced by aluminium.
Thc process oJ TiO, + 4Na-r Ti + 2 NabO
metal vilh llg ,
Instead ofusirg oxides of metals, their halides
can also be used. For example, titanium can be
obtained hom titaniun tetrachloride by reduction
In this process, a nt ixnte ol aluminitm powder with nagnesium ((roll's process).
and the metollic oide (say CrrO.,MnrOo etc.)
TiCln + 2Mg """"".. fi + 2MSCI2
called thermi'E is ignited in a closed crucible by
inserting a burning magnesium ribbon into the ig- O) Auto-rtrluc'llon or Self reducdon or Self
nition mixture consisting of magnesium powder electronsdon,
and barium peroxide (Fig. 10.8). This process is
Somc metal sulphidcs can be used for the
called thermite process or the slumlnothermlc
reduction of their own oxides. Thus, when the sul-
process. Metals like maaganese and chromium are
phide oras of the less active metals (whose oxides
obtained by this process.
are unstable towards heat like Hg, Cu, Pb etc.) are
roasted in an excess of air, a part of these sulphide.s
are oxidiscd to their oxides which further react with
more of the sulphide ore to yield the metal. 77ir
Mo POWDER
+ Bao2 process is c4rJed sclf-rcductlon or a[to.rcductlou.
For example,
AI POWDEH (l) ues (s) + o, G) -'-"'r
+ Cr2O3
Hg(8) + So2 G)
or 2 HgS (s)+3 Oz(0
2 -Hgo (s) + 2 So2 G)
FTGURE 1o.8. Alunrinothermic process. 2 Hgo (s) "'-' Hg G) + oz G)
The ignition powder burns to produce a large also 2 HgO (s) + HgS (r)
amount ofheat. As aresult, the metals are obtained
in the molten state and hence can be easily
-)
3 Hg (8) + So2 G)
 PFIINCIPLES AND PROCESSES OF EXTRACTION OF ELEMENTS 1O/15

(ii) zPbs + 3o2 ...........+ 2PbO + 2SO2 (NaCl solution) using mercury cathodes, the Na+
Galcna is discharged atcathode and forms an amalgam. On
2PbO + PbS 3Pb + SO2 the basis of electrochemical series, the liberation of
H, should have occurred at the cathode. However,
-,
Sometimes the sulphide ore may be oxidised
to sulphate which is thetr reduced to the free metal due to high H, overvoltage at the Hg cathode,
by the excess of the sulphide ore. liberation of Na occurs in preference to H, gas.
PbS+2O2....._PbSOa NaCl -----------r Na+ + Cl- (Ionization)
PbSOI + + 2SOz
PbS -----......r 2Pb (Mohat)

(m) 2CurS + 3o', - --+ lQtrzo + 2SO2 At cathode: Na+ + e- ----.-r Na (deposited)
Copper At anode: Cl- - e- , Cl
pyrites Cl+ Cl ......._ Cl, t
ZCt}rO + Cu2S 6Cu + SO2 (il) Electrolysis of alumlna. Metals other than
The roasting of the--sulphides are discussed s-block elements can also be extracted by
above is usually carried out in a reverberatory elecirolysis of fused compounds. For example, in
furance (Fig. 10.6). Hall and Heroult process, alurrinium is obtained
(c) Displscement method, by electrolysis of a fused mixture of purified
alumina (AlrOr) and cryolite (Na3AlF5) at 1150-
Some metals are reduced by displacement by
1173 K, when molten aluminium collects at the
a more reactive metalfrom their soluble complexes.
cathode.
For example, silver and gold are obtained from
their complex cyanides (obtained during leaching) IV Re{ining or Puriflcation of Metals.
by addition of more electropositive zinc metal. The metals obtained by any of the methods
Na[Ag(CN)r]+Zn- discussed above are still impure and hence are
2 Naz [zn(CH) al+z Ag L called crude metals. The impurities generally
2 K[Au(CN)rl + zt- \ [zn(cN)nl + 2 Au I present io the crude metals are :
(d) Electrolyttc mthod. (i) Othet metah -produced by simultaneous
Active metals such as alkali netals, alkaline reduction of their respective oxides originatly
earth metals, alumi!,ium etc. cannot be obtained by present in the ore.
reduction of their respective oxides with carbon. (ii) Non-metah -like silicon and phosphorus
This is due to the reason that the oxides of these formed by reduction in the furnace.
metals are very stable and thus have to be heated (irl) Unreacted oxides and sulphides of the
very strongly with carbon in order to reduce them metals, and
to the metallicstate. Further, at such high tempera- (iv) Substances taken up in the furnacr, e.g.,
tures, metals liberated combine with carbon form- residual slag, flux etc.
ing their respective carbides. Thus, such metals are
extractcd by the electrolysis oftheir molten or fused The crude motals are, therefore, purified or
refined. The method actually used for purification
oxides, hydroxides or chlorides. The metal is
liberated at the cathode. depends upon the nafure of thc metal and the
nature of the impurities to be removed.
The process of exlraclion oJ melqlr b, electrollsis of
their fkted sa s is called elcaromaallurg. In thlt
process, eleclrons seme &r the reducin? aqent.
Some common methods used for refining of
metals are discussed below:
(i) Electrolysis of NaCl. The s-block ele-
ments, i.e., alkali (group 1) and alkaline earth 1. Distillatlon Process, This method is
employed for purtification of volatile metals like
materials (group 2) which occur as chlorides or
trxosalts are converted into their chlorides. When
electric current is passcd through a fused chloride,
metal (M't+) ions are discharged at cathode and
deposited. Similarly during the electrolysis ofbrinc
'10/16
it used for
2. Liquation Ptocess. This mcthod
puifrcstion of such metal,' as corttoin nPuities
which are less fusible lhan thc,ncldls tlrcmselves, i.e.,
lhe meltingpoinls those
ol tlrc impwities. in ao
inert atmosphere sloP-
FIGUBE 10,9. Liquation process.
3. Oxidation Process' Iftis Process of metal
molten metal thus obtained is brought in contact
with air. The impurities are oxidised and form a
scum on the surface ofthe molten metal ftomwhere
it is skimmed off. Sometimes the oxide of the metal
itself is added which supplies the necessary orygen
to the impurities for oxidation. For example, iron
oxide is added to molteu steel and copper oxide to
molten copper. The various oxidation Processes
employed for different metals are briefly described
below :
(i) Bessemerisation. This process is carried
out in a specially designed furnace called a be-
ssemer converter (Fig. 10.10). The impure metal is
Pratlea p's Net4 Course ChemistrqtrfrlD
ing hearth of a reverberatory furnace (Fig. 10.9)
when the metal melts and flows down into the
receiver leaving the infusible impurities on the
hearth. Metals like tin atd lead are pttrified by this
method.
melted and a hot blast of air is passed through it
when impurities are oxidised. Pig iron and copper
are purified by this method.
Another converter vrhich has been used is
called the Pierce-Smith convrter. It consists of a
large horizootal steel drum resting upoa rollers. Air
is forced into the molten crude metal through
tuyeres. During the process oxidation of impurities
occurs and the heat thus evolved raises the
temperature to about 2673 K.
(ii)Cupellation. This method is aPPlied
when the impure metal contsins imPuitiesololher
metals which form volstile oxides. For example,
last traces of Iead are removed from silver by this
process.
A cupel is an oval shaped pan with shallow
hearth and made up of bone ash or cement. The
impure metal is heated in a cupel in presence of
a blast of air or orygen. The impurities are con-
verted into their volatile oxides which escape
along with the blast of air or orygen while the
pure metal is left behind. Thus, when impure
silver containing lead as impurity is heated in a
cupel along with a blast of air, lead is oxidised to
litharge (PbO) which being volatile escapes
alongwith the blast while the shining mass of
silver remains in the cupel.
(iii) Politg.This method is employed when the
crude metal contains impuities ol the oxide of lhe
metal itself. For example, impure copper contains
 PRINCIPLES ANO PROCESSES OF EXTRACTION OF ELEI\,4ENTS 10117

crrzo and impure tin contaiqs stannic oxide The net result is the transfer of pure metal
(SnOr). from the anode to the cathode. The voltage applied

.Air is brown through crudemorren metar

which a suitable flux may be added-.As a result,
to :i:;['J::lf,:;:ti3,J*"fl[f;iffi;
impurities get oxidised and escape either as ga-ses
*i.r""ll.p"rr,r", of the less electroposirive me_
such as COr, SOz etc. or pass into slag. The surface
,rf r-#"i""r""l.rired and settle down under the
-^".;;';;^;O"
or anode sludge. Thus in the
of molten metal is then covcred with-low sulphur electrolytic refining ^"dof copper,
coke,_.i.e , anthracite (to prevent oxidation of the like zini remain in -the solutionas
-"r'" u".i"."t"r.
cations, whereas
metal) and stirred withgreen wooden poles. At this ress basic metals rike au, eg, Te io; ir," r""a"
high temperature of the molten metal, the wood mud. "tc.
liberates gases such as methane which reduce any
oxide present in the metal (.e. CqO ir blister
copper) to copper metal.
3 Cr2O+ CHa ---'-'---r f qg + 2H2O + CO
4. Electro-relining. A large number of me- nis method is bqsed upon tlrc pinciple that
taf,s such as copper, silver, gold lead, nickel, when q mollen solution of lhe impure menl is al-
chromium zinc, aluminium etc. are rehned by thls lowed to cool, the puremetal crystallises outwhile the
method. impuities remain in the melt.
In this method, the impure metal is corverted In this method, the impure metal is converted
into a block which forms the anode while cathode into a bar which is heated at one end with a moving
is made up of a pure strip of the samc metal (Fig. circular heater (Fig. 10.12) so that this enrl melts
10.11). These electrodes are suspended in an and forms amolten zone or the melt. As the heater
electrolyte which is the solution of a soluble salt of is slowlymoved alongthe lengthoftherod, thepure
the metal usually a double salt of the rnetal. Wheo metal crytstallises out of the melt whereas the im-
electric curreut is passed, metal ions from the purities pass into the adjaceDt molten zone. This
electrolyte are deposited at the cathodein the form process is repeated several times till the impurities
of pure oetal while ar equivalent arnount of metal are completely driven to one end of the rod which
dissolves from the anode and goes into the is then cut off and d kcarded. The pmcess is usaally
electrolyte solution as metal ions. The process takes canied out in an inen atmosphete to prevent tie
place as under :

Arodc: M ---.. M"+ + ne-

Cathode : M'+ + -----.* M
1c-
BATTERY purities.
6. Vapour.phase refining. In this method,
the crude metsl is freed from impuities by
ftrst
con
hea
twe and, then decomposing the volatile compound
ot some higher temperqnlre to give the pl[e nrctal.
This method is illustrated by the foflowing two
processes :

. (i) Mond process. It is used for rcfining of

nickel. Whenimpure nickel is heated in u
"uoi"nt
of CO at 330-350 K, it forms volatile nickel car-
bonyl leaving behind the impurities. The nickel
carbonyl thus obtained is then heated to a higher
10/18 Pradeep's

MOLTEN ZONE

PURE METAL ?,3$,]Ailll"" TMPURE MErAL

t----- I ---+---------->--------.------->--------.>
DIRECTION OF MOVEMENT
t OF I'OLTEN ZONE
MOVING AND IMPURITIES
CIRCULAR
HEATER

temperature (450-470 K) when it undergoes ther- mixture to be separated or purified is dissolved in

mal decomposition giving pure nickel. a suitable solvent and applied to the top of the
columr. Depending upon their polarity, the com-
330-350 K
4CO N(CO). ponents of the mixture are adsorbed to different
Ni +
Inlpulc Nickcl c.6onYl extents on the column. When the column is ex'
tracted (or eluted) with a solvent (eluent), the
450-4m K
N(CO)I Ni + 4CO weakly adsorbed component is eluted hrst followed
PUIc by the more strongly adsorbed and so on. ftts
technique k especiolly suitable Iu such elemenls
is method is used
which are available onbt in minute quantilies and lhe
for metals such as
impuities are not very much dwrent from the ele-
titra are used in sPace
ment to be puifed.
technology. In this method, zirconium is heatsd
in iodine vapours at about 870 K to form volatile A flow-sheet diagram of the metallurgical
processes dlscussed above is given in Fig. 10'13.
zirconium tetraiodide which when heated over a
tungsten filament at 2075 K decomposes to give 1 0.1 2, Thermodynamics of Melallurgy rri':::i:'i'i:i::::i:l;::rri::,::l

pure zirconium.
Thermodynamic aspects ofthe reactions uscd
K t7o
'Zr (s) + 2lr(g)--' hlq G)
m15K in metallurgical operations are very important.
These canhelp in decidingthe temperature and the
(l^p*) e2rap-o) Tungstcn filamcnt choice of the reducing agents in the reduction
Z.r (s) + zlr(g) processes. An important thermodynamic functior
(Pw.\ is the standard Gibb's energy change (AG'). lt is
related to cnthalpy and entropy of the system by the
Similarly, - relation,
523K 1700 K AG=AH+AS.
r(s)+zr2(s) ----+ rillG) ------' !(s) +zIzG)
(Inpoe') (P&) For determining the feasibility of aay process'
AG should be negative. Therefore, AG decides the
7. Chromatographlc method. This method is direction of the process at constant temperature
based upon the principle that vadous comPonenls and pressure. We shall learn more about AG and
of a mirture are adsolbed to difrerunt dents on an its applications in class XII.
iborbert. In column chromatograPhy, an adsor-
bent such as AlrO, is packed ia a glass colurm. The
PBINCIPLES AND PHOCESSES OF EXTBACTION OF ELEMENTS 10/19

Step 1

CRUSHING AND GRINDING

Slep 2

PULVERISATION OF THE ORE c Lavlg.tton

e Froth lloi.tbn
ts El.ctsonrgn tlc aaparation
Step
e Lalchhg
3

CONCENTRATION OF THE ORE

(Separalion of othsr minrals)
+- Crldnellon"l Convcrrlon
e Ro!.Une J lnb mctrt ortd.
es
eR Conversion ol
eE metal oxldc
Step 4 eD to metal

EXTRACTION OF THE METAL

(Rernoval ot olher gl.Yl.nts to
obtain lho doskod nlet D

e Lhu.ton
r- Pollng
c- El.cEo-I.fnlng
Step 5 G Zone rolining
\Apour ph63e rafnhg
PURIFICATION OF THE METAL
(Rmoval of impuritie3 ol
e Chronrtogr.phlc nFthod
olh6r lem6nts)

FIGURE 10.13. Flow-sheet diagram for general mutallurgical operations. In the above diagram,
functions oI the proce-sse-s are given on the left wfiite the methods used are written on the right

Summary of the methods oI extraction of some common metals

lvetels Occutrence &tractio! method Remnrk
1. Lithium SpodumeDe LiAlSi2O5 Electrol)sis of fuscd LiCl/KCl Because of high reacrMty these
Lepidolite, (U, Na, K)2 are extracted under anhydrous
conditioos
Ar2(sio3)3 Fe(oH)
2. Sodium Rock salt, NaCl ; Feldspar, Electrolysis of fused
Na3AlSi3Og NaCl/CaCl2,"
3. Magnesium Camallite, KO.M8O2 . 6 H2O ; Electrolrsis of tused MgO or C.arbon reduction is not possible
Magnesite, M8CO3 MECI:./ C)Ch with alkaline earths since a car-
bide is formed with them.
4, Calcium Umestone, CaCO3 ; Dolomite Electrolysis of fused
Caclz / cj.F2
M8CO3. CaCO3 ; q/p6um,
CaSOI . 2 H2O
5. Copper Copper pyrites, CtrFeS2 ; Roasting of sulphide. Initialty It is an example of auio-reduc-
Cuprite, Cu2O ; Malachite, formed Cu2O reducs Cu2S to tion. Sulphuric acid leaching is
Cu also employed.
CUCOs . CI(OH)2
 Pradeep's

6. Aluminrlm Bauxite, y'Jzo3 .2 HzOElecrol)Eis of Al2O3 dissotved

;
cheap source of electricity is
Deeded in the extraction of Al.
Cryolite, Na3A1F6 ; AluminGsili- in fused Na3AlF5 or Na3AlCl6
catcs
7. Zinc Zinc blendeor Spharelite, ZnS ; Roasting follovrcd by reduction metal Day be purilied by
CalamiDe ZnCO3 vith crboo fractional distillation.

t. Lead Galena, PbS Roasting followed by reduction

with carbon.
9, Tin Cassiterile, SnO2 reduction of the oxide Magnetic seParation
employed as the imPurities
this case are ma8[etic.
10. Silver Ag2S Hom silver, rlaDide leaching of the
and fiDally displace-
ment of Ag by Zo.
11. Gold occurs in smallamounts Clanide leaching, same as in
ores of Cu, Ag eto. case of Ag.

12. ChroEi m Cbromite, Feo . cr2o3 Si or Al reduction of the qxide

rare ?
Q. I . \4,hy ls Fe an abundrtrt element on earth and why sre the elemerts with high stornlc numhers increosingly
(N.C.E.R.T.)

Ans. Fe bcause ofits high nuclear bindinS ener$/ is very stable and henc is an abundant element on the earth. As
thc atomic numbei increases, the niutron/proton, ie., n/p ratio increases. As a result, the Duclear binding
enersr decreases aod hence the abundaoc of elemeots with high atomic numbers decreases.
Q. 2. Give e'omples oflgncous rnd sedimrtary rcck& What l9 rhe origin ollgneous rocks oDd
what is the origitr of
scdiEentary rods ?
Ans. Ignco[s rocks : Sranite, baMlt, Sabbro ctc,
sedlmenlory rocl(s : limestone, sandstoDe, shale, dolomite etc.
orlgln. Igneous rocks are formed by Sradual cooling and solidificatioo of magma'
ScdimeoLs are obtaiDed byweathering of igneous rocks. These are brought by rain water, wiDd, CO2 aDd humic
acid to river banks, sea and lake beds where they 8et dePosited to form sedimentary rocks.
Q. 3. M.tels ltl{! cu, A& Z,lr' IIg ad Pb occnr ln naturc &s sulPhides rEther tllan odd6 ? Why ?
hA The cations of these metals, t.e, Cu
+
,Z*+ , AE+ aod H{+ tpseudo itrert gos confrgwatio4 1n -tl s7 f dtol
axrd Pb2+ (inen pair configuratio4 1n -t1 s2 p6 d1o ntz) have high Polarizing Power and henc car easily
potarize thi oiggcr sulphide ion than the smaller cxido ion. As a result, sulphides of these metals are more
;table thaD the oddes;nd hence thesc metals occur i'l naturc in form oftheir sulphides rather than oxides.
Q.4. In general whlch metals do you t:xpect to occur lD the native stst ln n8tur! ? Glw cr(8mples. (N'CERI)
Ars. Metals such as C\, Ag, Au, Pt etc. which lie below trydrogetr in the eleclrocbemical series are not readily
attacked by orygen, moisture and CO2 ofthe atmosphere and hence occur in the native state in nature.

Q. 5. Copper and sllverlie below ln the electrochemical serics and yet they sr found in the combined state 8s sulphides
ln nsturq comment (N'c'EJ.n
Ans. As exptai[ed in Q. 3, due to high polarising power of their cstions, their sulphidcs arc eveD more s]able than
the metals.
Q.6. Metal,s usuolly do notoctur ln n turt rs nltrst4s. why ?

Ans. Nitrates of all metals are solublc in wBter. Thcreforc, if metal dirates were Present in the crust of earth, ihes
would be slowly and graduallywashed by rain wster into thesea. It is becauseofthis reason tbat metals usually
do not occur iD nature as nitrates.
PBINCIPLES AND PHOCESSES OF EXTRACTION OF ELEMENTS 1O121

Q. 7 . How does NoCN oct as a depEssont h prcventing ZrS ltoE folmiDg the ftoth ? (N-C-E.R,T)
Ars. NaCN combineswith ZnS to form a complex, Na2 [Zn(CN)4|on the surface of ZnS aDd thus prevenls it tiom
forming tbe froth.
ZnS +4NaCN .+ NE[ZD(CN)4] + NazS
Sod. tclracranozimarc (lI)
Q. 8. Wby b ltadvontogeous to rEst $llphlde orc no ttie dide befotr rEduction ?
a (N.C.E.R.T)
Ans' The standard free energies (Ac') of formatioo of most of the sulphides are greater than those of CS2 and
H2S (CS2 is, iD fact, is an endothermic mmpound). Therefore, neither carbon nor hydrogen can reduce Detal
sulPhidcs to metal. Io coDtrast, the staDdard free energies of formation of oxides are much lower than ihose
ofS02 and heDcr csidation of metal sulphides to metal oddes is thermodrramically favourable. Therefore, it
is the mmmon practice to roasr sulphide ore to the oxide before reduction.
Q. 9. !,r/het is ahe themod5mamic consideration in the choice ofo rcduclng [gent in met{llurfs/ ? (N.C.E.R.T\
Ars. For aoy spontaneous reaction, the free enerry change (AG) must be negative
Ac =AH -TAS
AH is thc enthalpychangc, during rhe reactioD, T
is the ab6olute tempcrature and AS is rhe change
in entropy duriDg the reacrion.
Let us investigalc the AG during lhe conversioD
of a metal i[to its oxide
M+02 MO2
In this reaction,
-
dimygen---a gas
L
is usd up, and E
metal oxide-a solid is formed. Since gases have f
higher entropy than liquidsand solids, therefore,
o
during this reaction, As becomes negative. Thus,
if temprature is raised, the[ TAS becomes more
ncgative. SiDc TAS issubrracted in theequation,
iherefore, AC becomes less ne$atiye. Thus, ,he
lrcc cnzrg change increascs trith an infieore i, ,E
temperonre.
Consider the Ellingbam diagram (Fig. 10.14) tbr
E
some mctaloxides. o
From the diagram ir is evident that Detals for
which free eDer$/ of formation of their oxides is
more negative can reducr those metaloxides for
which the free enerry of formation of their
respective oxides is less negative. In otherwords,
any metal will reduce the odde of orher metals
which lie above it iD the Ellingham diagram be-
cause the free energy changc will becoDe more
negative by aD amount equal to the difference
between the two graphs a! that particular FIGURE 1O,14. Ellingham dhgram showing the
temperature. Thus Al reduces FeO, CrO aDd change in free energy (AG) with temperature
NiO in Thermite reaction but Aj will not reduce for oxides (hased upon 1 mole o{
MgO at rempcrature belo^, 1773 K From the dioxygen in p,ach case)
above discussioo, it is clear that thermodyDamic
coNiderations help us in choosing a suitable reduciDg agent in metallurgy.
Ql0 Carbon monoxide ls o more effective rtd ucing agent thsn carbon below 9ti3 K btlt I bo].e this tempcmturE rcveNe
is true. Horv will you explair this ? @.C.E.R.T)
Ans. When carbon reacts wlth diqygen two reactions are possible :
C+02 + 2CO2
2C+Oz 2Co
-
1O122
Pradeep's

ln thc first reactiol'I. the volunle of COz produced is

the same as that of 02 used, therefore, as is very -200
small and aG does oot change with tenlPerature. L C+ O2') Coz
a
Thus, the SraPh ofAG against T is almost horizontal E -4oo
(Fig. 10.1s).
The second reaction produces twovolumes ofCO for o
everyone volumeof O z!sed.n%\ L-s is Potiitive and >. -00
hence LG become:r increasingty negalive 4s lhe
tcmDetaate iacreaner Consequently its line on lhe
Ellingham rJiagram slopes dou'nwards (Fi8 l0.15)
3 -aoo
The two lines for the reactioDs, C ...- COz and C
+ CO cross at 983 K. Belo$' this temperature, the -1000 ;
E
reactioo leading to the formation ofCO2 is energeli-
o
cally more favourable
ofCO is preterred. In
C and CO can act as 773 3 1273 1773 2273 2773

can be more easily oxidised to CO2 than C to Co2, TEMPERATURE (KD

ducing

:t-:: HGUBE lo.l5. Ellnsham diagnm for carbon'

]ll'-:
983 K,
(The composite cun is the solid line).

carbon is a better reduciDg ageDt tban CO.

Q'll.whichmetolssrtscnerallyextrac,edbyelectrolytcpIo(lss.s?WhichPcltionsthcsem.talssenerallyoccupyln
(N'C'E
i R'T')
the periodic tabte
Ans. Electrolytic Process is used for the extraction ofactiv me ere allother method's
fail. Except Al and few other metals, tbese metals belong

- 12. tlou are prcvidedrvlth

Q. asample ofsome impurc metals such Whlchmethodswould
yo,, r.-rrr-"ntfor tbe puri-flcation of eacir of these metals (N'C'E'R'T)

Ans.

zinc metal iD tbe distillatoD flask.

as explaiocd on Page 10/17'
0i) The metalzinc may be further purfied by electrolytic refining
(rii) The metat copper is relined by Poling.
(ie) The metal Sermanium may be Purified by zone refining as exPlaind on Page 10/17-10/18'
Q.13.Whlchmethodwouldyousuggeslforthesporatlonolthemetalsinthefollotf,iDgmlxtues?
(i) Zn ftom iron (ii) coPPer from magnesium (t'ii) Rarc eorths'
cive rasons for your choice-
(/VC'E R'I)
Ans (i) Zn (b.p. 1180 K) cn be easily seParated from iron (b P 3273 K) by distillation'
(ri) A mixture of cu and Mg metals is trcated with dil. Hcl when Mg di.ssoh'Es formin8 Mgcl2 while coPPer
rema ns

pu rified by electrolytic refu:in8' The M8O2 obtaiDed above is made

uDreacted. The imPu re cDPper thus obtained is

anbdrousbyheztinsinacurrentofHclge6.Theanh}drousMgcl2thusobtaiDedisaddedtoamirureofmolten
NaO aDd CaCl2 (93-1025 K) and electrobsed when pure Mg gets dePosited on the caihode
(iii) Rare earth metals (ie., lanthanides abbrwiated as Ln) can of
ch
it tiiirimpl" tuttt tr"h ai niirates, sulphates, bromales, Prchlora
r.lg(No3)2 . 2a H2ct because they crystallize we
to
in 1lbr1, . :
"t a numbcr
Lu, therefore, salts at the Lu eDd of the Series will crystallize first. The Procss has to be rePated
to good separations. Non-aqueous solventssuch as diethylether have Jeenused to seParate
ofiimes o6tain
Nd (No3)3 and Pr (No3)3.
 PHINCIPLES ANO PROCESSES OF EXTRACTION OF
ELEMENTS 10123

Q. 1. Whot is a
mineral ? How doqs it dilfer from an ore?
Ans. The natural materials or the chemical compouDds iD
wbich the metals ocur iD the earth are callcd mioerals.
The minerar from which the me."r is convdnientry ano economicaif,liiieo
are minerals bw all minerols ore nol ores.
i" *,ea ,n_o rc. -fht)s, alr orer

Q. 2. Whnt tl4rcs of ores ore mssted ?

Ans Sulphide ores arc roasted to conven them into their oddes.
Q. 3.Metal sulphides occur Eaitrly ltr rocks anrl metal hsUdes ln lakcs
srd scos. Explaln.
Ars. Mctar harides being sorubre in water,.get dissolved in
rain water and are carried to rskes and sar durinc
weathering ot roc*s. on the orher hand, meralsutptrides being irisorror" lii u"l,ri iril,;ffi#;il,:
Q. 4. What arc fluxes ? How trre they useful ? "i"
Ars. Frux is a substaoce which c,mbines with ganguc which rnay sti,
bc prcsenr in the roasted or calciDed ore to
form an easily tusible materialcalled lhe slag.
Q. 5.Whst is o slsg ?
Ans. A slag is an c
fl_gangue still preseDt in the roasted or the calcjned
combines wit of iron' cao (flux) combiDes with silica
ore
easity tusible 8angr" to roinl

CaCO3 * CaO+CO2 ; CaO + SiO, .- 6aSio3

(ios)
Q. 6. Why do come metcls occur in the rative state ?
Ans. Mctals like Au and pt, which are not reactive, ie., are
no! atracfed by 02, moisture and CO2 of tbe air occur
in the native state.
Q, 7, What do you mean by berefaction process ?
Ans. The process used to concentrate an ore N called the benefaction
proccss.
Q. 6, What is gangue ?
Ans. The earthy aDd silicious impurities associated rvith
the ores is called gangue.
Q. 9, Deline aluminothermy,
Ans, The reduction of oxides of metals like CrrOr, Fe2Ol,
MDtOa etc. to rheir me.ols by alun,niunt is called
aluntinothermy.
Q. 10. WhEt is cupellatlon ?
Ans' cupellation is a method used for relining ofsuch nretals which
coDtain impurities otother metals which rorm
volatile oxides. For example removal oflast traces of
lt from e!.
Q. I l What is potirg ?
Ans' PoliDS is a method used for refininS ofsuch meials which
contain impurity of the oxidc of the nretal rtseI. For
example, CUO in crude Cu.
Q. 12. WhEt is th principle ofzone reliring ?
Ars. When the molten solution o[ ito In]pure rDetal is allowed to cool, thc purc melal cr]stallizes
impuri es remain i,, solrtion. out whilc the
Q. 13. What is Vnn Arkel method ofobtaining ultrapure metals ?
Ans' The impure metal('Il or zo is first converted inro irs volalile
iodide by hearingwith 12 at some low temperature
and then decomposing the voratirc iodide at a suilabre
high tcmperature to give the pure metar. For exampre.
870K _- 2075K
(Inpurc) w ril"n.nr 1rr).i - ''
Q. 14. Glye ihe chemical formula ofdolomite and cornalllte.
Ans" CaCOr.MgCO3 and KCt.MgCt2.6H?O.
 P ratl e a lr's N eut Coiise Chemist,AifrlD)
tol24
Q. 15. GiYc one imPoitsnt ore ofal$miniunr'
Ans. tJauxite (Al2O3 . 2H2O).

Ans'
Q. 16.
iaB':[iH:flf:'lliffiill;f,"",*3,)"li
elrts it fron] formin8 the froth'

rrvhat is the role of a sturhilizer in froth-floistiotr Process ?

Q. t 7.
1 \'( / ii /
Ans.Chetl]]icalcon]poulrdslikecresolsandaniliDewhichtendtostabilizethefrotbarecalledfrothstabilizers'
nt 9t3 K (or 710'C)' carbon or carhon monoxiile ?
Q. 18. \Yhich is n better rducing oEent does'
does nol act as a good reduciog ageDt but carbotl
Ans, CO. Above 983, CO being more siable \(] /r'
atwhich cnrbon can he useil ns a reducing aPent for FeO' I

Q. 19. Indic[te the temperatrrre

,\ns. Above 1123 K, carbon can reduce FeO to Fc'
certsin cooditlons Mg con re'luce SiO' anrl Si can
reduce MgO? \ ( / /i l
Q. 20. ls it true that under
1773 K Si can reduce M8'
Ans. Below 1773 K, Mg can reduce SiOz but above
l4C ohtained in the atmosPhere ?
Q. 21. Ilow is ..
rays and atmosPheric nitrogen' ie + pt + lft
Ans. I)ue to nuclear reaction between imic ' |af'f |ac

22. Why is the cosDic abundance of Fe very hl8h

?
Q.
A[s. Duc to its vcry high nuclear bindiog energy ?

Question
is different'
Sec. 10.1. 1. Explain uhy terrcstiat aDd cosnic abundance ofelemeots
to 10.6.
why are the elements with higher atomic Dumbers
Why iron is an abundant element on earth and
increasingly rare ?
3. write shon notes on : (i) HydrosPhere,
(ii) LithosPhere (iii) AtmosPhere and (iv) Biosphere
organFm
4. Name a few elements present in lhe livtng
of tbe various elements present in ihe sea- water'
5. Givg a brief accouDt
6. Ocean is a storehouse of the clements Colnment 'l
yet only a few elements are recoveted from it
Although sea water contains almost all thc elements'
E. How d6 the elements ocrur in nature
?
Sec. I0,7'
to 10.10. 9. fi;;;;-r;;i;"r""ts occur in the Dative state whilc others do oot ?
10. Differentiate betweeD mineral and
ores'

11. ence oflhc followi[g in the earlh's crust :

lead (N'C'E'R'?')
(c) sodium (d)
(ar leasr rhree), exptain how the reacriviry of a metat
ls r:/;5.i.?.fi
12.

predict the mode of occurreoce o[ the following three types of metals : (i) Highly
reactt-: q'j']:)
13.
i,iftloo";,;,y;;;,iliie.,i:e) (iii) noure nritarlr:e,eu; N'c'D'R'r)
t4, Howdonon-metalsoccurinnature?Howaretheyextracted/isolatedfromtheirDaturalsources?
(N.C.E.R.T)

Sec.l0.l0. DiscusssomeofthefactorswhichncedconsidcrationbeforedecidingoDthemethodofgxtractionof
(N'C'E'RT)
to 10,12. metal fronr its ore
What is the role of a stabilizer and of a depressant ?
16. Describe the principle of froth flotation Process (IVCE R'I)
Give oDe examPle each. ?
by froth flotation procss wbat is meant by a dePressaDt
17. Name three ores which are concentrated (N.C.E.R.Tl
 PFIINCIPLES AND PBOCESSES OF EXTRACTION
OF ELEMENTS
10125
18. Differentiate betweeo the followin!: fi\ calcinatioD .., .^^.ll-l_.ll]-
*r.t.,,ri^" and roastiDg' (ri) gaDgue aod flux'
r9. whar is meanr by *r""rorrion J8;":)
20. What is the purpose ofroastiDg and calclnation
ln meEllurgical operations I
21. What do you mcan by leaching ? Fxplain with
an cxaD.rple.
22. Explain rhe difference between leaching and levigation.
23. Silver ores and native gold have to be leached with metalcyanides.
Suggesr a reasoD for this.
24. Giviog ooe example in each caje, dittereniiate between
(i) Hydrometa urgy and (ii) Etecrromera urtl/
25. What is a flux ? Discuss its types and uses in ntetallurgical
oprations.
26. is aluntinothermy ? Explain wth one example-
27. _What
What do you uoderstand by lhe following terms
?
(i) Roasring (ri) Catcination (ir) Snrelting.
2t' Naore rhe nretars which are associated wirh rhe
forowing rerms in their exrracur, ,r.,, ,$l;"';X
(r) Bessenter,s converter (ti) Blast furnace l'
(ru) A.luntiriothermic process (iv) MagDetic
separation

,r. I:.!1* gl" leducing agent rDa prlicular case depcnds upon rhe the
you agree with this statement ? rmodyoam- r",$.?'J;11
I
30. rscarboDasarisro"to.y,.ou"r,,g'ffii#l;Hffi'::;Hi',?;," (N.c.E.R.r)
3L Describe rhe principrcofeach olr the follo\ring
rns (N'C-E.R.T')

(a) MoDd,s process (6) ZoDe refining (c)

?
processes in det,ir
Elecrrolyric refiDing.
,. *, nrean by vapour phase refining. DescriOe ,ran"ertet
(N.C.E.R.T)
Ni:ira,i me[hod used for purificztio' of
33. Describe the principle of extraction of each
of the followiDg :

34. ucr. wrrar wi, happe, ,r$lrtf;ll

,r"0 r.,,n. .,tl*lflXi3i
36. ^ WC.E.R.T)
J7.
Sreet Aulhoriry of India. W.C.E.R.T)
Cupeltation.
3t. d clcination ?
39. and poting ?

werQueeti
Sec. 10.I. L Discus the origin of elementr iE rhis unryerse.
to 10.t. Dtsclss briefly ttrc distribution ofclemcnts
on eanh.
3. Wtite the zones of the e3rth and discuss the
distributioo of clerEat! iD thcse zoncs.
4.
tioll of thc earth.
Scc 10.9. were they formcd duriog formation oferth
6. ?
to 10.12. ores,. Dscribe bricny the various methods
used for
Giye a bdef account of tbe various methods
used for obtaining mefals from tbc
r@$ed or calcjtred
? Describe bricrlv thevariousrErhods empgrcd
YJHt,f#:1'iifl.?:fl:rry turisohtionormctars
9. Give an appraisal of the methods uscd for
rcduclion of mctallic qidcs to mctals.
10. Discuss briefly the various methods usd for
refioing of crude metals.
 ,.."l.J.....i,r...'.,Jt.i.i,.rr,.,,

The principle ofelect

1. Electrostatic -dc PrhciPI
corcentration'
nds uion the differenc in the
ly wneD brought into ao electrostattc ---'
ectrode carrying the charge'

inc su fed uPon tt roller in a

thin
easi
i,[il
e to tho roller'
rJJsffi::?il::l
not

chemical reatent followed by cxlraction

Hvdrometollurgy lhe Process of dissotving lhe ore in a.suitable
is Ag and Au are
meiat sv a more etectroposiiiue melal
2.
ot rhe meial either by
lhis Process'
electrolvsis
"' ;;;'i;tiilir'i;t
extracted bY

4Ag + SNaCN + O, + 2HrO 4Na[Ag(cNLl + 4NaOH

-

2 NatAg(cNhl + zn Na2[zn(cN)rl + 2Ag I

-

ng behi'ld the metsl'

ro/26
 PR!NCIPLES AND PBOCESSES OF EXTRACTION
OF ELEMENTS 'tol27

Q I Delire amalgamatio[ ? Discuss its nse in the

purllicatioD of gold and silver. CoD Fe be
purllied by this method ?
Ans. Iron nnot be purified by this mclhod siDce Fe
not form as amalgam.
dc,es

Q 2. Cinnabsr (HgS) sDd galena (pbs) on roasting

often give thcir respective metals but zilc
hlende (ZtrS) does Dot. Explain. Al, Zn, Fe, Pb (West Behpl l.E.E. 2003\
AIls. OD roastiDg all-these sulphide ores are partly Anr. AlumiDium caDnot be extraeted by the smelting
converted into (heir respective oxides. Since th; process because of the following reasons
:
oxtoes ol mercury and lcad are unstable while (i) Ai is a highly etecrropGttive
very srong affinily for mvs
AlrO, is a very stabli *rporij
rct be rcduccd by carbon.
(n) Ahos wheo heated with carbon forms
Hgs + 2Hgo a sHg+soz alumiDium carbide.
(uistoblc) 2AhO3+6C A.t+e + 6CO
-
lUALTI I,LE CH UEisTTONS
and rve Exsminations
Durirlg smeliing, an addirional substaDce is added
which contbines with impurities to form a fusible
6. In the uluminothcrn)ilc proccss, illuntiniunr acts
us
mass. The additional substanc is called (4) atr qidising agcnt (r) a flux
(a) FIux (c) a reducing agent (d) a sotder. (t.t..t
(D) slag te|.t)
(c) can8ue (d)Ore. 7. Inwhich ofrhe followirg minerah, aluminiumis
nol
prEsent ?
-' he
by
(a) Crlotite (6) Mica
(c) Fledspar (4 Ffucspar.
(l l'T 199 t )
(4) Electrometallurs/ (D) Hydrometa & An important orc of magnesium
(c)Electro-relining
u rS, is
(d)ZnDe_rcfinin|. (a) Matachire (D) Cassiterire
3. Smelting involves reduction of metal oxide with (c) Carnatlite (d) calena.
(c) Carbon (b) Carbon moooxide I D.lll! t 't
(c) Magnesium 'l
(d) AlumiDium. 9. The salt which is least likely to be found in
minerals is
has been emptoycd for prepariDs
3::::l1T
urrrapure samples of
(a) Chtoride (6) Sulpbare
(c) Sutphide (d) Nitrate.
(o) cE (b) zn
(") ce tl).L \1. /. !rr.t
(d) Ac. 10. The ex&actioD of which of the following
5. Which of the followiDg is an ore of aluminium
? involws bcss"meri.gtion.
metals
(a) NajAlF5 (b) r'J2O3.2Il2O (s) Fe (r) A8
(c) Al2O3 (d) ?+o3.H2O (c) Al (d) Or. @.H.u. teet)
 l'rtrt!r:,:1,'s Ne.l Cou$e Chem istrylft[p
1Ol2A
20. ln the equation, 4 M + 8 CN- + 2H7o + oz
11. Which of the folloEng metals is obtained by leach'
iog the ore with dilute c,anidc solution ? ...- 4 [M(CN)r]- + 4 0H-, the metal M is
(4) Silver (b) TtaDium
(a) Copper
(c) Vaoadium (d) Znc.
(A-l.l l'l.s l99l) (b) IroD
(c) Gold
12. Which method ofPurification is represented ry the
eouatioos.
smK
.It +2LlTitr 1675 K
,'Il + 212
(lmoure) ' (Pure)
Process
(4) As (6) Na
ta) iupeitation (b) Poling
(c) Al (d) cu
(c) Van Arkel (d)'/-ane rcfioin9. (1.1.1,.E 1,.2002\
(/r'l-l.n'1.5 199J)
22, Pyrolusitc is a/an
13, Which of the following benelaction processes
ls
(a) Oxide ore (b) Sulphide ore
used tbr the miDeral Al zolz}lzo ! (d) Not aD ore
(c) Carbide orc
rd)Froth-floatation (D)
(D.Ml.1:2002)
@\ aration
i.ji.iqrurion
Io thc extraction of coPPer ftom its sulPhide ore'
ihe metal is formed by iaduction of Cuzo
witb
14. Thc process of concentrating Au and Ag
orcs ls

based uPon their solubillty lD (a) FeS (b) co

(a) NH, (b) HNO3 (c) CurS (d) so2

(c) Hcl (d) KcN. tlllllIS 200l)

lC. .5.8. l!M.7: 1991) 24. In the Process of extraction
of 8old,
15. Malachite is an ore of o"
(a) Iron (b) Tinc Roasted gold ore + cN - + H2O --; lxl + oH-
(c) CoPPer (d) MerorrY lxl + Zn- [Y] + Au
(M.lPM.T 1998)
IdeDtiry rhe comPlexes [Xl and [Yl
found
16, Which of the follottr'iog meials is sometimes (a) x = [Au(cN)2]-, Y = [ZD(CN)4]2-
native in nature ?
(a) A.luminium (r) Copper (b) x = tAu(cN)4r2-, Y = [zn(cN)a]2-
(c) Iron (d) Magnesium.
(;t1.PC-E.l:. 1999) (c)x = [Au(cN)2]-, Y = [Zn(cN)6]1-
17. Which of the follo 'ing metals is n]ost abundaflt in (d)x = {Au(cN)al-, Y = lzD(cN)412-
'l
the earth's crust i.l T.2l)0.1)
(a) Me (b) Na
25. The olethod of zone refining of metals is based on
(c) Aj (d) Fe ( teee)
the PrinciPle of
(a) ireater mobility of the Pure metal than
that of
Hearing Pyrites to remove sulphur
is
l&
(a) Smelting (D) Calcination the imPuritY.
lhat
(c) Uquarioo (d) Roasting. (b) higher melling Point ot thc imPurity than
t itl.l: llil. l: 200t) ) of the Pure metal.
tban
c,lrPel- (c) Ereater noble character of the solid metal
19. In the metaltursr ofwhich of the fottoxinS' that of the imPuritY'
lation Process is usd ?
molten
(ll rrcaler solubility of the imPurily in the
(a) CrPPer ;late rhan in the s( lid.
(c) Iror t(R \ t' l!rl.'l:2A01)

l(h 11 t: tlt. rJ 19. b 20. c

13. b
27. a
 PFIINCIPLES ANO PROCESSES OF EXTRACTION
OF ELEMENTS
10129
26. The Dlethods chiely uscd for the extractioD ol lead 3I. During the exrraction ofiron, slag produccd is
and tin from their ores are respectively
(a) cO (D) FeSiO3
(a) Selfreduorion aDd CarboD reduction
(D) SclfreductioD and Electrolytic redocrion (c) MgSio, (d) casio3
(c) Carbon reductioo and Self reduction
\.1 t K L:.tt t: 1001)
(d) C)anlde pr@ess and Carbon reducrion 32. Silver contaiDtng lead as an impurity is purilicd by
(.r) PoliDg (b) cupelarion
27. vapour phase refining ofnicketis carr,:l: 'JL;; (c) LevigatioD (d distillation
(q) rz (b) ct2 (J & KC.Ii.',l:2(t04)
(c) Hcl (d) co 33. Out of the followiDg melals that caDnol be obtained
(e) No b),electrobsis of ihe aqueoussolution of their
(It tdle E.Ii.f:. 200Jt salts is
28. Thomas slag is (4) As (r) cr
(a) CalciuDsilicate (D) Calcium phosphate (c) Cu (d) Mg
(c) Barium phosphare (d) Strontium siticarc u& KC.F:.',t:2004\
(e) Bariun silicate 34. ln the fiolh-floatalion prooess for bencfircti n ,\J
lK(ratn I;.L.ta 2tjtlJ )
lhe ores, the ore parttcles floal because
Silver is obtained fronr Na
[A8(CN)2J by reaction (4) they are tight
with
(r) their surface is not easily wetted by water
(a) Fe (6) Na
(c) they bear electrostatic charge
(c) ZD (d) ht tc.c1t.r zoot (d) they are insotubte.
Wbich onc of the followiDg ores is bqst con-
cntratcd by froth- flotatioo method ?
(a) Malacbite (6) Cassirerite
(c) Galena (a) Ni (D) At
(d) Magoerite
\.1 tL.h:.L.200J
(c) Fe (d) Cu Ouittt.c. zoot:

HlNT5./EXPLANATIONS to M uliiple Ch oice @.u eetion s

7. Fluorspar is CaF2.
:8. Calcium phosphate is calicd Tho-as stag.
9. All nitrates are soluble iD water. J3. Since the reduclion potetrlial of Mg2+ (_2.3-t
V)
ll- much tower than rhar ofI{rO
1_1t.6i yy,16s1"1
rs
Silver dissolves in NaCN solution.
16. Copper Iore, H2O gets reducerl inprefereneof Mgz+ ions.
is very slowly a
acked by air, ntoisture and
COz and henc. sometimes occurs in nalive state. J4. Ore particles float because lheir surfacc it wctted
by oil.

ADDITIONAL UESTIONS
The lollorlng
key to choosJ 2' U3 atle fotloryin8
(a) Ifboth assertion ard resson are CORR-ECI
and reasou is the CORRECT explanation ofahc
assertion.
(b) If hoth o.sertioD and ,"asor orc coRREq but
rcasor ls Nor the coRREcr exptsnatron of the assertion,
(c) If assertior is CORR.ECI, but reason is INCORRECT
(d) Ifassertion is INCORREC,I; bur reason is
CORRECT,

L.LI E R .S
26. a 27. tl 2a. b 31.d 32. b 33. d 34. b 35. o
10/30

l) Reflson (Cohtmn 2)
Assertion (Column
1. 'Il can be Purified by van Arkel Process' lll1is a rolarile coln=-und
whhhdcq]nrpces at a high lemprature
has a high nleltiDg Polnt'
2. Aluminothermy is used for exkaction of Alumina
chromium from chromiun] oxide'
associated with these ores dissolve io NaCN
A! aod Au are extracted by leaching thier I$purities
o; with a dilutc solulion of NaCN' ln fro(h-floatation process Pine oil is used because
it preferentially
C.arboDates and hydroxide ores are con'
wets the ore
centrated by froth lloatatioD process' Particles-

TruelFalee ?tatemente
o'td 4. The process emPloyed lo conceotrate an ore is
Which of ,he Jollo,iing stalefienl\ are true called (he
-
s. ieactring Particular mioeral
1.
io un orj ivelY bY using cer'
taiD acids, bases or other reagcnts'
e. freiim&al orirnpurities ftom an ore by forming
salts is called slaSSing oPeratio['
,l ieactive cannot be obtained
z. ia"iar. tntria
",Jiigfily
by elecrolYtic rcduction.
called an ore.
FilllnThe Olanks metals are
exkacted Highty eleotroPositive metals like alkali
1. AD orc is a . . .. from which the metal ca n be

ies 5.
2.
6.
'io ;;
3. its ores.
orrvert it into ....

Vatchin7TY?e Q.uesAions
4. concentration ofsulPhide ore (d) Firc
extioguishers
Match rtctns give n in Column Aagainst those given
5. concentatioD of ore
rn Colun]n B. od
6. Sodium chloride
Column A Column B is used in
7. Sodium bicarbonate
l. Bauxite (a) Flame to.st
8. Alkali metals aro
(b) r-Block elements (i) An ore ofsodium
2. Galena 9 Atka[ne earlh metals are
AlkaliDetals are extraoted bY (c) Frolh-floalalion 10. Magnesium does nor give (/) Pbs
3.

ASSERTION.REASON TYPE OUESTIONS

:iii
MENTS
'Iiue 7' Blse'
, mineral 4' Tiuc 5' 'Iiue 6'
FILL IN THE BLANKS

LA NATI O N5 to As 3 ertio n-Rea e on'fy ? e Au estio n 5

H I NT9 /EX P

cnncct etDlonalion. Al is a Sood reducing auent'

4, Care a\.tertiott Sulphide orcs are
in NacN solu- by froth- floatrtior Procs*'
3. ii,ril"r r"loroo Ag and Au drssolvc
tion to form tieir soluble coDlplexes'
 H>/d?ogen
:lXii
'iEi ' ,.lJ,.*
Unique position in the periodic table, occurrence, isotopes.
i Dihydrogen-preparation (including commercial preparation), properties, reactions and uses.
ii Hydrides-molecular,salineand interstitial.
i: Water : structure and aggregation of water molecules, physical and chemieal properties, hard and r:

ii soft wate4 water softener. Heavy water, hydrogen peroxide. hydrogen economy, use of liquid i
i1 hydrogen as a fuel.

11.2. Unique Position of

Hr.Thatiswhyitisalsoialted,dihydrogen.Itwashrst_ Hydrogen in the Periodic Table:::::::::r:::::::::::::::::::::::::::i:::::::::::::::::

Itiscoveredb$/errry_Q_g-v:f4l1nnLl(fi. Heprepareql Hydrogen is the fust element in the periorlic

it by the acfldn- of ilil. H2SO4 on iron. Its name could not be
eet's periodic
ble because of

The various forms 'isotopes, allotropes, (i) In some properties, it resembles alkali me-
molecular and ionic forms are hydrogen are given tak. as such, it b" placed in group 1 of the
in the box below : "unwith alkali m--e1[l-s:
periodic table along

Erectronic
Lrvvrrvtrtw : lsr
lf ,i -"lij1):,::.:ilil
g oup 17 along with -:i.^::::'
" wq' uv
halogens.
configuration
L(ltllSul dLlull
Isotopes : prorium, IFI r...
(irr) fn:oT"y,:tanotherprop,erties,hydrogen
ditfercfrom-both a]kali m-elals and [alqgggg.
Deuterium, 2H or D I position of hydrogen in theperiodic
Ttirium, 3H or T I ., is controveglg!3r orygll$ous, The main
lhus'th.1
: a_Lr
orthohvdrogen'o-H, I -table
iAltotropes
:
rrrrhnhrnrrnoen
I
Parahydrogen,p-H, p"ir",..r"r#r#ffihffith"".rffi*
iril;;Ji;l;;;;;;;;t;;fr'y di,Z;.;J betow :

lA]so o-u2,p-Dr, o- I r, p- IrJ 1. Resemblance with Alkali Metals. Hydrogen

Molecular fornls , Hr, zH, 1or Dr;, resembles alkali metals, i.e.,Li, Na, K Rb, cs and
3H, T,). HD. HT erc. Fr of group I of the periodic table in the following
1or
rcspects:

tur
 11/2 Pradeep's

l. Electronic configurati(,n. Likc alkuli me- and thus have one eledron le.ss than the stable
tals. hydiogen also conlains one elcclron in its out- configuration of the nearest inert gas. Hydrogen, on
ermost (ualence) shell : the other han( has one electron in the outermost
Hydrogen, H Lithium, Li shell and thus has one electron less than the stable
1sl "ll
zst configuration of the nearest inert gas, l'.e., He.
Sodium, Na Potassium, K H One elcctron less than Hc
Lt2 zt2 2po 3st L\2 L2 476 7.\2 3p6 4st Lyl b2
2. Electropositive character. Like alkali mc- F ()nc electron less than Ne
tals. hydrogcn also loses its only clectron to lorm
hydrogen ion, i.c., H+ Qrroton). 1s2 z\2 2ps t"2 %' zpo
H+H++r Cl One electron less than Ar
lrl Iro 1s2 zsz 2p6 kz 3ps ltz N2 2p6 k2 3p6.
Na Na+ + s- 2. Electronegatiye character. Halogers have a
ls' 2sz 2p6 !s1 1s2 2$2 zp5
strong tendeocy to gain one electr'on to form halide
Tltus, hydrogen like alkqli metals Lltltibitli
ions. In a similar way, hydrogen shows some tendency
c le c t rcpos i tiye cha rq cter.
to gain one electron to form hydride (H-) ion.
l-.Oxidation slate- Like alhali metals, hydrogen
exhibits an oxidation state of + [ in its compounds. H + r- ------------) H-
H+ cl- Na+ Cl- K+ Br- h'l 1.r2
Hydrogen chloridc Sodium chlodde Potassium broDide (He gas conliguration)
4. Combination with electmngative elements cl +c- +
ornon-meia.ls. Like alkali metats, hydrogen combines
cl-
with electronegative elements (non-rncrals) such zr^s Lt2 zr2 2p6 k2 3ps ts2 zt2 2p6 3s2 3p6
orygen, halogens and sulphur forming their oxides, (Ar gas cortfiguatiort)
halides .rnd sulphides raspectively. For example,
3. Ionization enthalpy. The ionization enthalpy
Oide : HrO likc NarO , KrO etc. of hydrogen is quite comparable with those o[
Halid.es :HCI like NaCl, KCI etc. halogens but much higher than those ol alkali metuls.

Sulphide :
HrS like NqS , IlS etc. ElcDlcnt lonizqtion enew

5, Liberatlon at th cathode. When an H 1312 k.l mol-1

aqueo[s solution of HCI is electrolysed, H, is F 1681kJ mol-r
liberated at the cathode in the samc way as alkali Cl 12-55 kJ mol-l
metals are liberated at the cathode during tho Li 520 kJ mol-r
electrolysis of their fused halides.
Atcqthode At anode
Na 496 kl mol-r
Electrol,sis K 419 kJ mol-l
ZHCl(aqt H2G) + ctz@) 4. Oxidation saate..Iust likc halogen-s, hydrogen
shows an oxidation state of 1. For exarnple,
2NaCl(/)
Electroh,sis
--------:-
2Na(/) +
-
ctz?) llith soditutt: Na+ H- likc Na+ CI-
6. Reducing character. Like alkali metals, With calciton :
hydrogen afso acts as a strong reducing ogent. For
Ca2+ 1H-), like Ca2+(Cl-)2
example, 5. Liberation at the anode. When fused alkali
Hcat rnetal hydridcs such as lithium or sodium hydride is
Fe3O1 + 4H2 .+ 3Fe+ 4HzO subiected to electrolysis, hydrogen is liberated at thc
Heat anodc. Similarly, halogcns are liberated at the arods
B2O3+6K ........- 28 + 3IgO when fuscd alkali metal halides are electrolysed.

II.
Resemblance with Halogens. Hydrogen At utrcde At cathode
resembles halogens, r'.e. f;, Cl, Br and I ofgroup 17 Electrolvsis
of the periodic table in the following respects :
2NaH(/) ..................- HzG) + 2Na(/)
1. Elcdonic configuration : All the halogens Elcctrolysis
haw seltn electrons in their respedive outcrmost shells
2\l('l(/) .+ Cl2G) + 2Na(/)
HYDBOGEN 1113

6. Atomicity and non-metallic character. Just rutcleus and only one electron in tlu extravcleor
likc halogens, hydrogen also exists as a diatomic Paft.
nrolecule : Hz,F2 , C\, Br2 etc. Furthcr, like 3. Nature of oxides. The oature of oxides of
halogens, hydrogen Ls also a tlpical non-ruetal. alkali metals, halogens and hydrogen is quite dif-
7. Combination with metals. Hydrogen com- ferenl. The oxides of alkali metalt qre basic while
bines with highly electropositive alkali trnd alkalirc those of halogens are a.ci.lic but the ox(,lc of
carth metals to form metallic hydrides. In a similar nyarogei, i.e., Ft ,o is neutral. Thus,
way, halogens combine with these metals to form HzO ,
LirO , NarO . K2( ) etc , Cl2( )7
metallic halides. Na&al --v- Acidic
Bosic
Wth alkali metals
zNa + t! -._ 2NaH 4. Absence of unshared pairs of elc,Ltrons.
---
The hydrogen atoms in hydrogen molecule do not
2Na + Clz + 2NaCl possess ary unshared pairs of electrons whereas
With qlkaline earth metals halogen atoms in halogen molecule possess three
unshared pairs of electrons as shown below :
Ca + H2 CaI{2
+ Cl2 -+
Ca CaCL HH CI CI
ll. Formation --r
of covalnt compounds. Lile
halogens, hydrogen readily combhes with non-mo- 5. Nature of compounds. The compounds oI
tals such as carbon, silicon, nitrogen etc. to form hydrogen with halogans, i.e. hydrogen halides (Hf,
covalent compounds. HCl, HBr, Hl) arc low boilirtg covqlent cotnounds
With hydrogen : CH4 siH4 NH: whereas alkati metal halidcs (Lif; NaCl, KBr, CsI)
Methane Silane Ammonia arc high melting ionic soli^.
With halogens : CCl4 SiCl4 NCl3 6. Size of ions. The size of H+ ions
( - 1 -5 x lO-3 pm) is much smallor than those of
Ca6on Silicon Nitrogen
letrachloide tetrachlondc trichloridc alkali metals. Similarly, thc sizc o[ H- ions (220
9, Replacement or Substitution reactions. ln pm) is much smaller as compared to halide ions.
many compounds of carbon, hydrogen can bc 7. Structure of hydrates, H+ ion sxists in
rcplaced by halogens and halogens can be replaced aqueous solution as hydraled pruton having the
by hydrogen. For example, formula. IHe( )ol+ in which four Hr( ) molecules are
Diffuscd sunlight
cHl + cl2 ---------------- cH3cl + HCI tetrahedrally arrangcd around the H+ ion. How-
ever, it is generally rvritten as [H.o+l and called
Mcthane Mcth,l
chloride hydronium ion. Alkali metal cations also exist as
Sn/HCl hydrates but the extent of hydration decreatses as
cH3cl + 2[Hl ....._ cHl + HCI the size of alkali metal cation increases. Thus
Methyl or Z^/HCI Merhane
chloride
H
lII. Difference from Alkali Metals and
o ._Ht
H
Halogens. Hydrogen differs from both alkali metals
irnd halogens in the following respects :
t. Hydrogen is comparatively less electropo:;i-
tive thqn qlkqli ,netals and less electronegative thdn lL(Hro)61+
f,ilhium hcxahldrate catlofl
hologens.For example, hydrogen has less tendsncy
to form H+ ions as compare dto alkali metalswhich Halide ion-s, also exist in aqueous solutions as
rcadily fbrm monovalent cations. Similarly, hydrated ions but their structures are not well es-
hydrogen has less tendency to form H- ions as tablished. That is why, they are usually represented
compared to halogens which readily form halide as X-(ag) where X =F,Cl,Brorl.
(X-) ions. Conclusion. From the above discussion, it fol
2. Unlike lulogens attd alkali metals, lrydrogen lows that hydrogen is unique in its bchaviour be-
contains otb) one proton (bfi no rtetLtrons) in its cause it
not only resembles alkali metals and
1114 Neta Course Chent i strg
halogens in certain properties but at the same time Tiitium being unstable because of its radioactive
it differs from both of themin certain other proper- nature occurs only in traces (one in l0l8 parts) i.e.
ties. Therefore, it is not justified to include the natural abundanccs of lH, lH.andfH arc in the
hydrogen either along with alkali metals ol Wup I ot ratio of1:1.56 x 10-2: I x 10-18.
halogens of group 17 In other words, /r e position ol
hydrogen in the peiodic table is qnomalous or con-
Some importalt characteristics of thesc
isotopes are giveD io Table 11.1.
fioversiol. That is why hydrogen is sometimes
referred to as a 'ro8u e element'. TAIILE 1Lf. Atomic I)toperties
')f lsotr)prs
rrl H.r,rlrogen
1 1 3. Occurrence of Hydrogen :':r:.": :::1:. :

Property II I) I
Hydrogen is the most abundant elementin the .007825
Relative 1 2.014l(D 3 016049
univerce (70Vo of the total mass of the universe). atomic mass
The giant planets such as Jupiter and Saturn con-
Nuclear spin 1 1t2
tain mostly hydrogen. Hydrogetr mnstitutes about
quantum
half of the mass of the sun and stars.
number
The extremely high temperature of the sun NoD-radio-
Radioactive NoD-radio- Iladioactive,
brings about fusion of hydrogen atoms liberating stability active stable active stable emits low
large amount of energy energyP-
4 ------*
lH lHe + z\e + Energy particlcs,
Helium Positon tr,tz= 12 33Y
It is the third most abundant element on the Electronic structure.All the three isotopes of
surface of the globe. In the combined form, it con- hydrogen have the same atomic number (Z = 1),
stitutes 15 47o of the earth's crust and the oceans. therefore, all have only one electron in thcir only
However, on the earth, it, is the Dinth element in shell (i.e., K-shell) and one proton in the nucleus.
order of abundarce and forms 0.97o of the earth's Since the mass numbers of the three isotopcs are
crust by weight. In the crustal rocks, it is 10th in different, therefore, they differ from one another in
order of abundance approx. 0 l1Vo by wei$i. the number of neutrons in the nucleus as shown in
Hydrogen is also the essential constituent ofwatcr, Fig. 11.1.
coal, petroleum, clay and all animal and vegetable
matter.
Earth does not possess enough gravitational
pull to retain the light H, molecules, therefore, it is
not found in our atmosphere.
1 1.4. lsotopes of Hydrogen iiii::ri:i::i:i:i:,i1i::::.,,:i:!rri:r:: i:,:, i

ure sdfie ele- HYDROGEN

OR PROTIUM DEUTERIUM TRITIUM
number bul
d i,ffe r ent m.as s n umb e r s.
(lxl (fx or o1 (fH or 1

Hydrogen has three isotopes. These are called FIGURE I l.l. Isotopes of Hydrogen
protium, duterium and tritium.
Represenlation. The isotopes of an clement (i) Protium or ordinary hydrogn [lH]. This
are usually represented byputting the atomic num- is the most abundant isotope ofhydrogen. Since its
ber as the subscript and their mass number as the atomic number is 1a-nd mass number is also 1, its
superscript on the symbol ofthe element. Thus, the nucleus has only one prolon (but no ,rcutron) a\d
three isotopes of hydrogen are reprcsented as one electron is revolving around the nucleus in its
lu, ]u or o and fH or T, only shell, i.e. K-shell.
Occurrence. The most abundant isotope of (ii) Deuterium or heavy hydrogen t fH or Dl,
hydrogeu is protium. This occurs in natural Its natural abundance is 0.O756% . It is usually
hydrogen to an extert of99 9844Vo;the remaining prepared by the electrolysis of heary water (DrO).
0.0156% being deuterium mostly in form of HD. Since its atomic number is 1 and its mass number is
HYDROGEN 1 1/5

2, therefore, its nucleus has one ptoton snd one Properties- lsotope Elfect. Since the thrce
neutron w[)le on,e electron is present in the K-shell. isotopes ofhydrogen have the same atomic number
It is generally denoted by the symbol D. and electronic configuration (Lrl), they have
Qii) Thitium tfH or q.
It is the least abun- similar chemical properties. But owing to their dif-
dart (Lo-167o) of all the isotopes of hydrogen and lerent masses, the rates or equilibrium constants of
is forrned in the upper atmosphere by reactions thesc reactions aie different, For example, reaction
induced by cosmic rays.ltisrodioactive with a short between protium and chlorine is 13.4 times faster
halfJife of 12.33years.It decays byB-emission with lhcn bclween deuterium and chlorinc : protium is
no 7-radiations adsorbed more rapidlythan deuterium on activated
+ charcoal. Similarly, electrolysis of ordinary water
?H ------ lHe _[e
(HrO) occurs more rapidly than thaI ofheary water
It is prepared artificially by the bombardment
(Dzo).
of nitrogen or an isotope oflithium with neutrons:
]aN + ln
_.....- lrc + iH Thit ttpeolilifrerenceifiprary h dw todlfferenra
jI-i + &, -----------
lne + fn in atomic mds.scs is cal*d lsotope tffect.

Since its mass number is 3 and atomicnumber
is l, its nucleus has one proton ond two neutrons
while one electron is present in the K-shell. It is
usually represented by the symbol T.
nMs, the tlvee isotopes of hydrogen differfrom
one another only in the numbet of neutrons i,t the
nucleus.
Further, due to different masses, the physical
propertics of these isotopes are quite different.
Some common physical properties of H,
(dihydrogcn), D, (dideuterium) and T2 (ditritium)
are given in Table 11.2.

TABLI

PRO PI'R'fY IIz Dz T2

Molecular mass (a.m.u.) 2 016 4.028 603

Me ltiDg point (K) 11.957 18.73 20.63
Boiling point (K) ?i.39 23.67 25 .00

llnthalpy of fusion (kJ mol-1) 0 ll7 o.197 0 250

Enthalpy of vaporization (kJ lnol - r) 0 904 1.226 1 393
Enthalpy ofdissociation (kJ nrol-t at 298 2 K) 435 88 443.35 446.9
Inlernuclear distance (!.D) 14.14 74.14

Uses of Thitium. Tiitium is used to make ther- I. From water. Dihydrogen may be obtained
monuclear devices and fbr carrying out researches from water by any of the following method.s :
in lusion reactions as a means ofproducing energy. 1. By the action ofwater on metals
Tritium gas is usually stored by making UTr, which (i) Cold water Very active metaLs, l'.e., alkali
on heating to 673 K releases Tr. and certain alkaline earth metals like Na, K Ca etc.
671K react with water at room temperature evolving
zuT, 2u +3'f2 dihydrogon.
It -
widely used as a radioactive tacer si\ce
is ia 2Na + 2H2O ......._ 2NaOH * H,
is relatively cheap and easy to work with. 2K + 2HrO -----------+ 2KOH + H2
i1 t n!^Drralron or Dihydroggn
Ca * 2HrO ......._ Ca(OH)z + Hz
The important sources of dihydrogen are The reaction with alkali metals is so vigorous
water, alkalies arrd acids. and exothermic that the hydrogen evolved catches
1 1/6 Pradeep's

llrc. I n ordcr to slow down the reaction, amalgams Ilcat

(alloys with mercury) of these metals are generrlly Zn + 2NaOlt Na2ZnO2 + H2
usctl. In thcse rmalgams, orrly a small surfacc area Sod. zincale

oI ths mctal comes in contact with water and, there- FIcat

fore, the reaction is slowed down.

Sn + 2NaOH ----------- NazSnO: * H,
Sod. stanritc
With calcium, thc rcaction is not so vigorous
and hcnce cun he casily controlled. 2Al + 2NaOH * 2H1O 2NaAlO" +3H2
Sod
(ii) Boilitrg woter Less active metals like Zn, - nreta-alunrinate
Mg, Al ctc. rleconrpose boiling water liberating
clihydrogcn.
Ill, I-rom Acids. Mctals which ars rnorc
IIcat
elcctropositive than hydrogen i.c., lio above
Zt* HrO ZIO+H2 hydrogcn in the electrochemical series) such as
zinc, iron, magnesium etc. reuct with dilute mineral
Mg + Hr() -tleat
-----------+ MgO + Hz acids (dil HCI anrl HrSOo) to liberate clihydrogen
gus.
Heat
2Al+3H2() ...........+ AlzOr + 3Hz Zn + H2SO1 ZnSO4 + H2

(iii) Steom. Still less reactive metals likc Fc, Fe + 2HCl -----------+
- FeCl, * H2
Sn, Ni etc. dccompose steam at high temperatures Mg + 2HCl ----------- MgCl, + H,
evolving dihydrogcn.
3Fe+ 4H2() .....-.-.- FerOo * 4H, Metals like copper, silver, mercury etc. which
are less electropmitive than hydrogen (i.e., lie
(Stea,n) Magnetic oxide
below hydrogen in the electrochemical series) do
2. Byelectrolysis ofwater, Dihydrogen of high not liberate dihydrogen from acids.
purity is usually obtaincd by the electrolysis of
watcr in presencc o[ small amount of an acid or a
115.1. Laboratory PreParation of
Dihydrogen
hasc. f)uring electrolysis, dihydrogen is collected at
cathode while diorygen is liberated at anodc as In the laboratory, dihydrogen is prepared by
shorvn bslow: action ofdil. H2SO1 on graDulated zinc.
Electrol!{is Zn * HrSO. (dil.) """""- ZnSOn * H,
2 HrO(t) J 2H2@) + OzG)
Granulated pieces of zinc are placed in a
Pure water is only weakly ionized (i.e. is a bad Woulfe's bottle and are covered with water. The
conductor oI elcctricity) but in presence of an acid bottle is fitted with a thisde funnel and a delivery
or u base, the degrec of ionization increases. tube as shown in Fig. 11.2.
H2t)(/) ---------"r H+ (aq) + OH- (aq)
Atcothode: H+(aq) + c- H
FI, + .H - HZG)
Atanode: OH @q) + - OH+e
2H2O(t) + O2@)

Although dihydrogen prepared by this

mcthod is of bigh purity, yet this method is not
commercially viable since it is quite expensive.
However, where elcctricity is cheap, this method
can be used.
lI. From Alkalies. Metals like beryllium, zinc,
tin and aluminium etc. roact with boiling alkali
solutions liberating dihydrogen. FIGURE 1 1,2, Preparation of dihydrog"n
gac in thP laboratory
Hcal
Bc * 2NaOH ..........- NarBeC), +H, Conc. HrSOo is poured slorvlv through thc
Sod L)eryllute tlrislle funnel. As thc acid falls in thq Wbulte's
HYDROGEN 1117

bottle, it gets diluted and then reacts with zinc l2',t,K

evolving dihydrogen gas. It is
collected by
downward displacemetrt of water.
It has been observed that sometimes the bub-
blas of dihydrogen produced stick to the surface of
the zinc metal preventing the further reaction ofthe
acid on the metal. Such a situation car, however, be
avoided by adding a few crystals ofcopper sulphate
to the reaction mixture.
Notes, The following points must be noted
wbile preparing dihydrogen gas in the laboratory.
l. Pure zinc is not used tot the preparation of
gas becouse it reads very owly with dil- HrSO o. The
presotce of impuities, howeve4 increases the rdte oI
reaction due to tlu fomution ol electrochemical
couples.
t coG) + H2G) + H2OG)
2. Conceniated sulphuic acid is not used for
.
the pepamtion ol dihydrogen gas becouse zinc reacts
wilh concentrated acid lo Iom SO, gos instead of
Hzgas.
7i + 2H2SO1--"- ZnSOr+SO2+2H2O
(conc)
Preparatlon of pure dibydrogen gas. In case
pure dihydrogen (> V) 95Vo) gas Ls required it
very
may be obtained as follows :
(i) By the action of pure dilute sulphuric acid
on magnesium ribbon.
Mg + HrSOn (dil.) ......._ MgSOn + H,
(ii) By the electronlysis of a warm solution cf
barium hydroxide using platinum or nickel
electrodes.
(lii) Bythe action ofwater on sodiumhydride.
c(, + HroG) -""""'- coG) + HrG) -t2t'3u
Water gas
Dihydrogen is removed from water gas hy any
one of the following two methods :
(i) Liquefaction Pmcess. Carbon monoxide li-
quefies at 83 K while dihydrogen at 42 K. Thus,
when water gas is cooled under pressure, CO li-
quefies while H, passes out.
(ii) By Bosch Process,ln this precess, water
gas is mixed with twic its volume of steam. The
mixture is then passed over a heated catzrlyst (con-
tainiag oxidas of iron, chromiun and cob alt) at773
K when a mixture ofcarbon dioxide and dihydrogen
is produced.
FczOy'c'rlOl
v ---J ",3 K
Watcr gas
COz@) + 2H2(E)
Carbon dioxide is removed by dissolving it in
water under pressure (20-25 atmospheres) and the
dihydrogen left behind is collected.
2. From steam and uDtr gas - Lane's
Prrxcss. Dihydrogsn is manufactured by passing
alternate currents of steam and water gas over red
hot iron. The method, in fact, consisls of two stages.
(i) Ondation sra8e. Super heated steam is
- IO73
passed over iron filings heated to aboua 1:02i
K when hydrogen is formed and magnetic oxide of
iron is left behind (Fig. r1.3).
STEAM OIHYDBOGEN GAS

NaH + HzO -'-'- NaC)H * Hz I POBOUS IRON t

(iv) By the action of KOH on scrap aluminium I

(Uyeno's method),

This method is used for military purposes.

2 Al + 2KOH + ZH|O --+ 2KAIO2+3H2
1152. Commerclal preparation or Manu- i- t llryl -i
facturc of Dlhydrogen t @2 + H2O
WATER GAS
Dihydrogen can be prepared on a commercial
scale by the following methods :
(l) From ratcr grs. When supcr heated steam
is passed ovcr red hot cok at 1270 K a mixture of
carbon monoxide (CO) and dihydrogen (Hr) called
water gas is produced.
 '1118
Netl Course Chemistrg
(ii) Reduction rrsge. When the whole of iron tlihytlrr:gen involves cither partial oxidation of
has been oxidised, the steam supply is cut off and a hydrocarbons obtained from petroleum or thermal
stream ofwater gas (H, * CO) is passed to reduce cracking of natural gas.
FerOo back to iron. (i) Partial oxidation nfhydrocarbons or coke.
Fe3Oa+ 4H2-3Fe*4HzO A_mixture of hydrocarbons (say irude naphtha) is
mixed with steam and pa.ssed over a heated Ni-Cr
FerOo + 4CO -..........r 3Fe + 4COz catalyst at 1270 K.
Thus by pa-ssing steam and watcr gas alter- Ni-Cr
nately over heated iron, dihydrogen gas can be
C^Hzn*z + nH2O
manufactured from a small quantity of iron. Naphtha Steanr 12'70 K

3. By the electroysls ofwaten This is rhe best

nCO + (2n + 1)H,
ln this process, instead of crude naphtha,
natural gas may also be used.
Ni_Cr
CH4 G) + Hr() (q)' -......_ Co G) + 3H, G)
Natumlgas Stam tz70 K

Similarly,
Ni- Cr
QH, G) + 3 H2o G) -.........- 3 co (s) + 7 itr(S)
DIOXYGEN<- .---} DIHYDROGEN 1270K
trI C(s) + HrO
127C K
C(s) + H,@)
CO is converted to CO, by passing the gases
and steam over an iron oxide or cobalt oxide
catalyst at 673 K resulting in the generation of more
20% NaOH
SOLUTION
:lt ASBESTOS
DIAPHRAGIV
H2.
FcrO, or CrrO,
=-_ co + H2o . co2+H2
673 K
FIGURE 11.4. Eectrolysis of water for commerciat This is called the water gas shlft rraction.
prcparation of dihydrogen.
small amounts of dihydrogen (l
ln this cell, iron sheet is used as a cathode -Relatively
l7 m3h-r) are obtained by passing a 1 :-1 molar
-
while nickel plated iron sheet acts as anode. mixture of vapourised methanol and water over a
base-metal chromite q.pe catsl',st at 673 K. Thc
mixture of hydrogen aud carbon monoxide thus
obtained is made to react with steam to give CO,
and more dihydrogen
673 K
NaOH solutionis used for electrolysis, the decom- CH3OH--.............* CO + H2
position of water takes place as follows : Catallst
H2O -.........- H+ + OH- 673K
CO + H2O ....-........r COz+Hz
At cathode, Catatyst
H+* e- ........-.- H. 5. As ! by-product. Large quaotities.of
dihydrogen are obtained as a by-product in various
H2
industries. For example,
At anode, O From petroleum cracking planls,
4OH- + 4OH + 4e- (ii) Manufacture of sodium hydroxide by brine
4OH + electrolysis, (iri) From coke oven gas.
2 HzO + 02 (u) Ttermal cracking of natural gas.
4. From hydrocarbons. One of the most Dihydrogen mayalsobe obtained by thermal crrck-
recent methods developed for manufacture of ing of natural gas.
 HYDROGEN 1l19
lnoK 2. It is the lighest substarre known. For ex-
CH1 """""""'- C+ zHz
ample, one litre of dihydrogen at N.TP weighs
catallst
0'0899 g. Its densityis approx. U14 th ofthat ofair.
Presently above 77Va of the industrial
hydrogen is produced from petrochernicals, 187o 3. It is slightly soluble in water since its
from coal, 4Vo from electtolysis of aqueous solu- molecules are non- polar.
tions and l7o from other sources. 4. It can be liquefied uDder low temperature
and high pressure.
1 1.6. Properties ot Dihydrogen
Some important physical constants of
(d) Physical propertles. l. lt k a colour- dihydrogen alongwith dideuterium aud ditritium
less, tosteless and odourless gas are given in Thble 11.2.

ortho ard Para Hydrogen, Dihydrogen has two nuclear spin isomers called onho and paiOitryorogen.
when two hydrogen atoms combine to form a molecule ofdihydrogeD, the two electrons arways spin
in the
opposite d irections (Part li \ uclution principle) as orhenrise the moteiute wrri not ue sta6e. How&er, the
spins
of the protoDs (nuclei) may either be in the same direction or in the opposite direction.
Wen the spiw of the nuclei are in
the same direction (pnallel spiru),
dilEdrogen it called ortho
hydtogen and when the spins ore
in rc oppoite dircctioru (at-
tipdrallal ipiw), difudrogen it
cal/ed psra hydrogen.
'lle two forms ofdihydrogcn are ORTHO HYOROGEN PARA HYDROGEN
(Patallel nucleat spins i lolal
sho$,n in Fig. 11.5. lAnt i parcl I el nucl e at spi ns ; lolal
nuclearspin = + + 1= nuclarspn'++-
Conversion of one isomer into the f 11
+=0)
other is a slow process. Para
isomer with lo$i/ ener$/ is
favoured at low temperatures.
At room temperature, ordinary dihydrogen contains
d, rhe percentage of
at about 20K i( is
o 400 K or abovc, ah
7). Thus, it b postible ,o obtoin Ftre Wa hyboge bu,
The phlrical-p_roprties ofdihydrogen are llot greatly affected by nuclcar spin isomcrism, Howcver,
some of
the Dotable differences are :
(i) Thermalconducruty of p-Hzts 50% Erearer ihan rhat ofo-FI2 and
(fi) The meldDg point ofp-Hz.is O. 15 K tower than thar of hydroge n @naaining,tsVo o-H2.

(D) Chemlcal propertles. Some important nzg) + or{g)-.-+ za"O(t)

chemical properties of dihydrogen are dlscussed
o its high bond dis-
below :
socia mol-l), dihydrogen
1.Neutral character, It is neutral to litmus. is qui mposition of H2 into
2. Combustlblllty. It s aht$ly combus tibk gas its atoms occurs only above 2n00 K (0. 081% which
and burns in air or dio4tgen with a pale blue flame increases to 95. 57o at 5000 K)
to form water. However, it is not a supporter of 5000 K
combustion. H2@) '--------r zH(E)
%.5%
11/10
lleat
Action vlth metals. Dihydrogen reacts with
4,
+
PbO + H, --.-.---..' Pb H2O
strongly electropositive metals like sodium, potas-
sium, calcium etc. to form salt-like (e/ectrovalent or IIeat
Fe3Oa + 4Hz r 3Fe + 4H2O
rozrc) metal hydrides, in which the oxidation state
of hydrogen is - 1. For examPle, The uides ol strongly electroPoitive metals
573K such as those of alkdli and alkol E es,th metsls are
2Na + H2 -""""'' 2 Na+H- not reduced by lhis method.
Sod. hydride
573 K
Dihydrogen also reduces some metal ions in
Ca + Hi """""'' Ca2+1H-;, aqueous solutions. For cxamPle,
cal. l4idridc P&+ (aq) + Hz G) Pd (,s) + 2 H+ (4q)
5. Actlon with non.metats. Because of iLs high -
?. Ilydrogenation of unsaturated hydrocar'
bonJ dissociation energy (435'88 kJ mol-r), bons, Unsaturated hydrocarbons such as alkenes
and alkynes add dihydrogen in presence of a
i: catalyst to form saturated hydrocarbons.
Et Ni or Pt or Pd
or motecular hydridcs. For example, CH, = gg, * H, CH3-CH]
Ethcnc 413K
--------:+ Ethanc
@ lmth diorygen,llrforms HrO. The reaction
Ni or Pt ot Pd
is strongly exothermic
K
HC = CH + 2Hz CH3 - CH3
9?0
Accqdene 473K Ethanc
2H2@) + O2@) 2H2O(r)
or Elcciric discharge Hydrogenation of uDsaturated organic com-
(ii) With halogem. Dihydrogen ombineswith poundi irpresence of heterogenou's and
halogens ()lr) to form halogen halid s Lomogeneous iatab'sts is used in many industrial
processes. For example,
H: (.c) + &G) -'--r2HX(8) (i) Hydroformylatlon of olefins. Olefins react
(x: !'Cl,Br,t) with carbon monoxide and dihydrogen in presence
The reactivity of halogens towards dihydro- of octacarbonyl dicobalt as catalyst under high
gen decrea es in the order: temperature and Pressure to form aldehydes.
Fz> Cl2> Br, > Ir. ICo (Co)412
RCH=CHz+H2+Co
in dark, chlorine in
Thus, flourine re. cts High temp., plessurc
of diffused sunlight, while the reaction
presence RCH2CH2CHO
with bromine and iodine occurs on heating in AldehYdc
presence of a catalyst.
(vi) Wittt ditttrcgen, it forms ammonia. This reaction is called hyrlroformylation or
673K 200 atm. the oxo-process. The aldehydes thus obtained on
NrG) + 3HrG)- 2NH3G); subsequent catalytic reduction give alcohols.
Mo Ammonia
Ft, RCH2CH2CHO + H2 ----) RCH2CH2CH2OH
AH = - 92'6 kJ mol-r Aldehydc Alcohol

This eaction is u ed for the anufacture o[

ammonia.
Reduction of meial oxides and ions'
6.
DihydroRen octs as s reducing ag t and hcncc
rctluces oxides otcertain less elecl.roposil.ive metals
such as those of Cu, Zn, Pb, Fe etc. to the cor'
responding metals. For examPle,
Heat avoid this, double bonds are reduced. For this pur-
CuO + H2 Cu + HzC) pose, dihydrogen is bubbled through edible oils in
Heat presence of finely divided nickel oI473 K when the
ZtO t H, Zt I{rO oils are converted into solid fats
 HYDROGEN '1r/11

Ni.473 K (iv) in the manufacturc hydrogen chloride

Edible oil + Hz .............* Edible fat
(,iqtiA gohd) hv
This process is called hydrogenation or har- H, G) + cl, G) 2HCt(8)
dening of oils and is used in the manufacture of -
(v) in the manufacture
vegetable ghee likc Dalda, Gagan, Rath etc. from of meta.l hvdrides
vegelahle oils. It may, howevcr, be noted that (refer to scc 11.7).
h,yd.rogenation reduces the number of double bontls (vi) in metallurg to reduc heavy metal
but does not completely eliminale then. oxides to metals.
1 1.7. Uses of Dihydrogen ,,:.r
(vri) in the atomic hydngen (produces
Dihydrogen is usecl temperatures around 4000 K) ad ory-hydmgen
(i) in the lorcier (producqs temperature betwe en 2270-2770
Habcr's process) K) for cutting and welding. Dihydrogen is dis-
oIvarious Iertilize sociatcd with the help of an electric arc and the
calcium ammoniu hydrogen thus obtai-oed are allowed to recombine
(l) in the hydrogenation of vegetable oils to on the surface to be welded. ds a temperature of
lbrm solid fats, i.c., Vanaspati Ghce. around ,1000 K is generated.
(ir'i) in the manufacturc o[ bulk chemicals such (uii) Liquid hydrogen (mixed wirh liquid
as methanol orygen) is used as a rocket fuel in space research.
700 K 200 atm. It is also uscd in fuel cells and in bubble chambers
co G) + 2H2@) cH3oH (/) for study of high encrg5r particles.
Coball calalvsl

S; l. Hydrogen unde r very high pressure is expcted to behavc like a melal.

ff,g z. Tlc Dame dibydrogen is commonly used tor H2 molecule, but while referring to the isolopic mixture with

Depcnding upon the physical and chemical

Dihydrogen combines with a number o[ ele-
ments to fornr binary compounds called hydides.
Their general formula being MI{, wherc M repre-
seots the elemnt and .r the number of hydrogen
atons. The yarious elements which form hydrides
are :
properties, the hydrides have been divided into the
following thrce broad categories :
l. Ionic or Salrlikc or Saline hydride,s
2. Metallic or lnterstitial hydndet
3. Molecular or Covalent hydrides

_ (D All the main group elements except those

of noble gases and probably indium and th-allium.
(ri) All lanthanides and actinides.
(iri) Tiansition metafs-Sc, Y, La, Ac, Tc, Zr,
Hf, Pd and to a lesser erent Y Nb, Th, Cr, Cu and
Zn.
polymeric structures.
11112
Net4 Course

Properties' Some important ProPerties of SiClo + 4NaH --"- SiHr + 4 NaCl

ionic hydrides are listed below :
PbSOa + 2CaH, + PbS + Ca(OH),
(, Howeve4 their reactivity towards HzO limits
fiot t th their usefulness as reducing ogents in aqtteous solu'
contqin
hydtide, lions,
(i:t) They fortn comples:es fltcll ss litliunt
(ii) T'hese are white crystalline solids and their'
oluntinium hydide (LiAlH 4\ and sodiunt
cryStal strucfiires consisl of ions.
borotrydide (NaBH) which are widely used us

rcduc ing agents in orgonic synthesis.

4LiH + Alclr 'LiAlH4 + 3 Licl
4 NaH + B(OCH)I* NaBHr + 3 CHTONa
thcse hydrides decrease progressively as the-size oI
the meial cation increases from Li+ to Cs+. In a 2. Metallic or lntentitial hydrides. d-Block
similar way, the stabilities of hydrides of alkaline La,
earth metals decrease in the order : and
CaH2>SrH2>BaH2. eat-
oul)

those
isbec
ol lhe metal without disto ing ahe metal lqttice'
(iv) Tlrcy hne high melting snd boiling Points
atd conduct ekctricity in the rttsed state' libersling
dihydtogen at he anode.
LaH3,TiH2,Z.rHz, HfH2, vH, VH2, NbH, NbH2,
At anode :2H- (l) '------> HzG) + 2e-
TaH. T have ProPerties
At cqthode:Na+ O + e- ""-'' Na (l) t
similar als and hence are
(v) They have high heats of fotmation and are called these hYdrides,
always stoichionetric.
(vi) Except LiH, they bum in air o', strong #iii:
called
heuting (675-775 K) rfue to heir decomposttion
into hydmgen which is inllammable lnterstitial hydrldes.
615_TEK These interstitial hydrides rnay also be
CalI, """""""" 91 a 1q olid solu-
(vil) rmthe it is trot
ol in the in-
correspon tion
ions with
dihydroge
NaH (s) + HzO (/) ...- NaOH (aq) + H2 G)
delocalized electrons.
Propcrties. Somo imPortant Properties of
CaH2 (s) + 2H2o (l) "+ these hydrides are listed below :
Ca(OH), (aq) + ZHz@) (i) They are hard, hove a metallic lustre, cott'
&rct etectricity and have magnetic properties.
Because 6f the exothsrmic nature of the reac-
tion,(he evolved H, catches fire. The frres so The
(ii) thon
those of mela e the
produccd cannot be extinguished by CO, because crystal lottice
it gets reduced by the hot metal hydride- However,
(r,r)These hYdrides are often nll
sand is useful since it 3 fiighly stable solid.
stolchiometrlc (ZrH, where X : 1 30- 1'7-5,
(iii) Thq arc powerful reducing agenls, espe'
cidlly at high temPemtwes TiH, where X = 18-2 0, ZrH,.o, Pdll6.7,
2CO + NaH I HCOONa + C VHr.6, LaH2.sz, YbHr'55, CeH2.z) Further the
 HYDI]OGEN
11/13
rotio of H-atoms tothe metal atoms in these hvdides 713 K
is not frxed but vuies with the temperature ;nd the Hr(g)+S(/) HrS (g)
Ptefsure. Dark,little moisture
Uses. Due to interstitial hydride formation, H2G) + F2@) - HF(0
these metals absorb large volumis of hydrogen ori 23K
their suytace- This propeny of adsorption of igas by (ii) By reduction of a suitable halide with
u tnetol ir known as occlusion. LiAlHoin dry ether
occluded depends 4 BCl3 +
LiAlHl -....t 2BrHu + 3 AlCl3+3 LiCl
3
te of the metal, r..e.,
SiCla + LiAlHa------- SiH4 + AlCl3 + LiCl
nt > plalinunt >
(iii) By action of acids on suitable binary com_
If red hot Pd is cooled in Hr, it
absorbs or poun^.
occludes about 935 times its own volume ofH, gas. 2 MgrB2 + 4 H3PO. .......;

This may be used to separate H, or D, from He and Mag. boride + 2 Mgr(POo), + H,

BoH,o
olher gases, However, on strong heating, the oc- ALq + 12HCt......- 3 CH4 + 4 AtCl3
cluded hydrogen is liberated. Further meials which Aluminium
can clissolve varying amounts of hydrogen in this carbide
way can acl us catalysls for hydrogenal.ion reac_ FeS+HrSOo._HrS+FeSOn
lions. Metallic hydrides can also be used as Ca3Pz + 3 H2SO4 ----- 2 pH3 + 3CaSOa
hydrogen storage media.
Cal. phosphide
3.lVlolecular or Covalent hydrides. These are
mainly formed byp-block elements and some r- (iv) By reduction of an oxoucid with NaBHnin
block eloments (Be and Mg) primarily due to the aqueous solution
reason that the electronogativity difference be_ 4 HrAsO, + 3 NaBH, ------->
tweeo these elements and the hydrogen atom is
quite small. Their general formuia is-either XH, 4 AsH3 + 3 H3BO3 + 3 NaOH
(for s-block elements) or XHr_, (forp-block ele- _ _
Classilication. Depending upoa the number
ol electron-s and bon& preseot in their Lewis struc_
ments) where n is the number of electrons in
tures, molecular hydrides have been classified as
valence shell.
elecfon-dqcient, elecffon-exact and electron ich
crete covqlent
hy*ides.
wcak van der
are cqlled covalent or molecular hydrldes. _Properties, Some important properties
- of
covalent hydrides are discussed below :
Nomnclaturc. The systematic names of
molecular hydrides are usually derived from the (r) ually volatile com-
name of the element and the suflu-ane. For ex- pounds ioiiing points and
ample, phosphane for PHr, oxidane for HrO and also do
azane for NHr. However, common names like (ii) Hydrides of gruup lj (i.e. BH,,AW, etc.).
phosphinc, water and ammonia are more common_ do ,tot have sufrcient number of ekclrons to Iomt
ly used. normsl covalent bonds and hence are cslled
electron-defi cient hydrides. They geoerally exist io
_ Preparation. These are preparcd bya number
polyneric forms such as Brtlu, noH,o, 1ntfury, e tc.
ot ditterent methods:
(i) By direct combin&tion of elements with _ (.i0 Hybides tl group t4
CHn, SiHn, GeHo, SnH4, PbHi have exa{t number
0.e.
th lty drogen. For example,
673 K 200 alm of electrons to lonn nonlal covalent bonds and
N2k)+3HzB) ......................-2NH3
k) cise hydrides. All th ese
Fe, Mo shapes. Their bond
Electric discharye to PbH, as the size of
zH2@) + ozE) ---------------,--........- zHzo (s) the element increases from C to pb.
11114

(iv\ Hydndes ol goup 15, 16 ond 17 (i'c '

NH3,'PH3, HzO, HzS, HE HCI etc') have
ntote

elechons lhutt requircd to foml nomnl coyolenl

borrds ond hence ire called electron'rich hydrides'

Gronp l5 Groutr l6 Group 17

,lv- l).t, Irv" b-p. tlv- b.p.

dridc (K) dride (K) dridc o()
associated molecules as shown below :
HF 2v2.4
NIr3 2i8.5 Hzo 373

PH: 185 5 HzS 213 HCI 188.0

l,z[ii
\H-
RrIi:
\H-
R=[i:
-H--
AH: 210 6
254 6
Hrse
HrTe
23'l

270 8
HBr
HI
205.9
?31.5
sbI-I3

'. ?i- E* '. d- 6* \ i,- 6*

.........:o-i.........:o-H......... io--.H.. ... ..
ot(- o.( ^'(.
6* 6- 6+ 6- 6* 6- etc.), followe<l by nitrogen (N.Ho, NHr), orygen
..,......H-F H-F H-F "
(Hror, Hror) and sulphru (HrS, whetex = 2-6)'

iooic rtain hydrides are better kDowD

Bcsides three main cateSories ofhldrides, i e ,
as potymeric hydrides and comPlsx hydrides For
e
in rhe range I . 40 _ 2 . 0. Thsse
held together io two or tbres
ples are :

(siHa), etc'
@cH)o, (AlH3)6' (InH3)n, (GaH3),,,
evolve H2
These arc amorphous solids whicb dcaomP6e above 523 K to 8a-s'

three-ceDtre-two electron bonds as sbown

Shucture- Bery'lium hldride exists in the Polymeric form invoM[g
below :
 HYDFIOGEN
1111s

LONE PAIRS
OccurrEnce. Water is essential to all forms
of life but distribution of water over the carth,s
surface Ls not uniform. Whereas deserts have oo
permaDent surface water, oceans cover vast areas c6-
(l .61 x 108 kmz), i.e.,78Vo oI the earth's surface.
Of the lotal-eslimated global supply of about
1.4 x 10e km3, the oceani and the lniand saline HH */\*
water bodies hold 97.3Vo and the fresh water
amounts to less thar.2.TVo.Most of the freshwater
oo
(2.5-2'9 x 107 km3) is locked up in Antartica ^ P=' too
and Artica glaciers. Fresh watcr lakes contain I
I .25 x 105 km3 of water, more than half of which
is in the.,tbur largest-lakes : Baikal (26000 km3),
Tirnganlka (2IlC0 km3), Nayassa ( 13000 km3; aod
/,\
HO-H
Superior (12000 km3). Other major sourceso[lresh
water are : ground water, springs and rivers. Tbc FI ga. Fha"a
fraction of fresh water readily available for human
use is only 0.0067" ofthe totalglobal water supply. ec.tre.

In nature, water is found is all the three (2.1) and hence the shared pairs of electrons in the
phases, r'.e. solid, liquid and gas.
11.9.1. Structurc of \f,hter Molecute and its
Aggregates
In HrO molecule, the orygen is sp3-
hybridized and hencehas four s1y'-hybridized orbi-
tals. T\yo of these sd-orbitals are half-Iilled antl
hence with fu-orbitals of hydrogen to firm polar molecule. Its actual dipole moment is l.g4 D
-overlap
two.rp3-s, O (Fig. 11.6(c).
-H, o-bonds while the othJ, to,o con-
Lain a lone-pair of electrons each. Since the oxgyen Hyrlrogeo bonding in water and ice. In the
atom is s23-hybridized, therefore, the geometfi of liquid state, tbe HzO molecules are held together by
HrO molecule should be tetrahedAl and the
ZHOH bond angle should be 109.-5.. But ex-
perimentally, it hasbeen determined that theactual
LHOH bond angle is 104.-5.. This maybe explained
follows :
a.s molecufes as shown in Fig. 11.7(a). Thus in the
In HrO, the oxgyen atom is surroundedbytwo liquid state, H2O exists as an associated liquid.
shared pairs, and two Ione pairs of clectrons. But
according to VSEPR (Valence Shell Electron pair

tn8-
Ice, the solid form of water. can exist in nine
O
-H bond has a bond len6h of 95.? pm.
In the crete
molecules HrO
molecule in asrn
Fis tl.idt. tures, it conde$es to cubic form. In the nornral
The elecrronegativity oforygen (3.5) is much hexagonal
,. . !9e,9ach or(ygen atom is terahetiraifi
trBtrer (uext only to fluorine) thaa thal ofhydrogen surounded by four other oxygen atoms,..s.. rhere
11/16

words, the density of liquid water at 273 K is higher

----./ than that ofice and hetceicelloau over liquidwater'
As the temPeratur
.,/I
.H 273 I( more and more
quently more and more
ltzzp-

VACANT SPACES
277 K.

,\ .t
H/
even during sevcre cold weather.
11.92. ProPerties of Water
(a) Phlsical Pr
properties of water
H-bonding between
physical constants o
deuterium analogue, i.e., heat'y water (D2O) are
listed in Table 11.4.
Some ofthe important physical properties are
FIGUBE 11 er in the
liquid state ement
ol

intemolect at hydrogen bonding in HrO molecules

which is, howevet absent afiiottg tlrc molecules of
HzS , H2Se, HzTe etc'

(iii) Waterbec constant

Q|'3b)'hr.s the ab
the inor-
gonic ('ionic) comP rcSatded
 HYDBOGEN
11117

TABLE 11.4. Some ph,sical constants ofII2O and D2O.

PROPI]ITTY IltO D20

Molecular r]ass (g mol-l) 18.015 20.0276

Meltnrg poiDt (K) 273.0 2't6.8
Boiling point (K) 3'73.O 374 4
'len]perirture of ma,xintum density (g/cm3)
216.9a 2f'4.2
Ma\rnrun] densiry (293 K) (g/cm3) 1.ffto 1106
DeDsity (298 K) G/cm3) 1 .0000 1.10-59
Enthalpy oI fbrD]arrol.1, AfI/" (kJ mot- I)
-2A5 9 -294.6
Enthalpy ofvaporisarion (373 K) (kJ mot-r) 40 66 41.6t
EDthalpy of fusion (kJ nrot-l) 6.0 t 62A
Specific heat (Jg-1 K-r) 4 17',1

lonisarion coDsrant [H+ j IoH-] (molz L-1 I 00tl x lO-la .9-5 x l0-l-5
Diclectric constant '7A.39 78.06
Viscosit)'at 293 K (rn centipoise) 0.8903 1.107
Electrical coDductivity (293 K/obm-l cm-l) 5.7 x 10-8

aJ a universal solvent. Whereas solubiliN of ionic Electric current

compounds takes place due to ion- dlpoie lntera- 2H2o(t) 2H2G) + o2@)
tions. (i-e. solvation of ions), ahe solubility of cathode) (At o ode)
(At
covalent compounds such as alcohols, amines, 2. Acid.base character Amphoteric charac-
urea, glucose, sugar etc. takes place due to the -
ter. Water is a weak electroll,te, i.e., it undergoes
tendency of these molecules to form hydrogen ionizatiol to a small extent to givc HrO+ (aq) aoci
bonds with water.
OH-(aq) ions. As a result,pure wster lrus very low
Qii) Heavy warer (DzO) has slightly higher e I ec ti c o I c on du ctiv i ty.
values of physical constants because of its higher HrOO + Hro(/) H3()+ (qq) + OH- (aq) |
molecular mass as compared to that of ordiiary -.
water (HrO). K- = 1.0 x 10-14 mol2 L-2 at 298 K.
nu$, wqter qcts both as an acid qnd as a base
wide und hctlce is liaid to be omphoteic in character Fot
base, examplc, it can ac[ as an acid towards NH, and as
ions. Some ofthese properties are discussed below: a base torvards HrS :

f. Stabillty. Due to high oegarive heat of for-

mation (AH/ = 245.9 kl rnol-l), water is quite
HrO O + NH3 (arl) --' NHo+ (ar!) + OH- (aq)
Acid Basc Acid Base
decomposes H2o (1) + HrS (aq) ..* H{)+ (aq) + HS- (aq)
erature. The Base Acrd .\cid Base
not appreci-
In general, wqler cqn act a5 u base towards
qcidt slronger lhsn self and as an acid lowards a
1500 K bqse sltonger than it. 'fhns, in
zHzo(s) zHz(d + o2@)
terrn_s of its am_
photcric nalurc, auto-protolysis of water may be
-
->
Water also decomposes into its elements, rcpresented as follows :

wheu HrO (i) + HrO + OH- (aq)

_electricity is pa-ssed through it in -pr".erc" oi O == H.O+ (aq)
a small amount of an acid or an alkali. Acid Basc Acid2 Basc2
11/18
Pradeep

3. Oxidation-reduction or Rcdox rtactions. PoO,o (s) + 6 HrO (/).* 4HrP()o(aq)

Besides, acid-ba-se reactions, water also undergoes PhosPhoric acid

oxidation-reduction reactions. CaHr(s) + 2HrO(t) .........- Ca(OH)r(aq)

(i) As an oxldistng agent. Water reacts with hydddc
carciunr + 2Hr(g)
number of active metals like Na, Ca etc. whose SiCt4(/) + 4H2O(/) .......- SiOr.2 HrO(s)
electrode potential is less than -0.83 V liberating
di\drogen gas. or Si(OH)a + aHCl (aq)
[2H2O(l) + 2e- '-"""'.zOH- (aq) + Hz@) i AlCl3 (.r) + 6 H2o (/) ....-
' E : -0
83V1 lA(oHr)5f+ @Q +3ct- (aq)
zNa(.r) + 2Hro(D -""""' 2NaoH(aq) +H2(a) cacr(s) + 2H2oO ca(oH)z@q)
(Redtcta ) @xid@tt)
Sirrilarly, when steam is Passed over red hot
coke (1273 K), water gas is formed.
Calcium carbidc
- * ":;,fi*G)
.-+K
1273
+ n@) Alocj(l) + tzHz()U)
C(s) + Hrtxg) co@)
Aluminium carbidc
(Rcdtaonr) 66tron11
Water Bas aAl(OH)r(aq) + 3CH40i)
Merhanc
ln all these reaction s,water acts ar an oidisittg
agent ond lrcnce ilself Sels raducedto dihydrogen 8a\. Ca3N2(s) + 6H2O(/)
(ii) As a reducing agent. Water reacts with Calcil'nl nitride
-
highly electronegative eleme nts like fluorine whosc 3ca({'tH)r(aq) + 2NH3G)
el;ctrode poteotial is higher than + I '23 V liberat- Anrmonra
ing dioxygen and triorygen. AIN(s) + 3H2o(/) -"""""' Al(OH)r(aq)
lOzG) + 4H+ (aq) * 4e- a zHro(t); Alunrinium nitidc
Eo= + 1 23Vl NH'G)
2F2@) + zHro(t) carPr(.r) + 6Hro(/) '+
(Ondait) (Redl/ctant) -> Calciunr phosphide
or(g) +
4}{+ (aq) + 4E- (oq) 3Ca(OH)r(uq) + 2PH3G)
Pho{sPhir
or 3Fr(g) + 3H2O0) O3k) + 6F- (oq)
-+ + 6H+ (aq)
NarCt\(s) + z}.zo(l)
2NaOH(a4)
- + HzCO3@q)
ht these rcactions, wqter acts as areducingsgenl
urttl hence ilself gets oxidised to cither O, or Or' Since the hydrolysis of NarCC). produces a
Similarly, during photosyntbesis, water is oxidised strong base (NaOH) and a weak acid (H2C()3),
to diorygen. therefore, an uqueous solution oJ NarCO. is
Sunlight
ulkoline in nature.
rCO, + yHrO q(HrO)) + xO2
ChhroPhyll In contrast, the hydrolysis o{ CuSOo produces
4. Hydrollic reactions. Water can hydrolyse a weak base i.c., Cu(OH)2 and a strong acid
many oxides (metallic and non-metallic), hydrides, (HrSOo), therefore, an uqueous soltrtion of CUSO o
carbides, niLrides, phosphides and other salts. In
is acidic in nahue.
these reactions, H+ and C)H- ions ofwater interact
with thc anions and cations of the compouotl CuSOo(s) + 2H2OO =_ Cu(t)H)r(a4)
rcspcctively leading to the formatioD of an acid or + HrSO.(ari)
a hrsc or both as shown below :
5. Hydrate formation' Many ionic compounds
Cao(s) + Hro(/) ...-..-.- Ca(oH)r(aq) crystallise from water with one or more molecules
SOrG) + Hr{)(l) .....* H2SO3(44) oi water associated with them. For example,
SulphuroLrs acid BaClr.?HrO, CuSOo.5HrO, FeSOa.7H2O,
 HYDROGEN 'I
1/19
NarSOr.l0HrO etc. nis w(!tct ut contbinatk)tl witll react with the anions of fatty acids prescnt in soaps
ionic ,\olts i.t cdlled water of cD,stalli,tatiort (lnd su.clt to form curdy white precipitates. As a result, haid
ctystuh arc called h\rdruted soht ot.sitttply hydrstes. watcr does not produce lal.hor with soap immedi-
Thcse hydrates can be classified into the following ately.
threo categories ; 2C,rH..rCOO- Na+ + CaCl2
(i)
Water ntolea es ore coordiwted to the Sodhrm stearalc
ccn|'.!l nrcta I ion lo Iot|tt compl.x ions. For example, (soa (C,.rH35COO)rCa J + 2NaCl
in nickel nitrate hexahydrate, and lithium chloride Calciunr steamte
hexahydrate, the six water molecules are Iinked to (culdt ppi)
vthirc
the central ion Ni2+, Fe3+ or Cd+ ion by coor- 2Cr7H3,C()O- Na+ + MgS()o -.*
dinate bonds. Sodium stcarate
lNi(oHr612+(NOt)2, + 3 Cl-, (\oop)
IFe(OHr)6f
ICr(OHr)6]3+ 3 Cl-
(C,,HrrCOO)rMg J + NazSO4
Magnesiunl s!earate
(ii) ll'ater nrclacules are lirkad to sonu o4,gen (Cu b, whiu ppt.)
contaii q ankttr by hydrogen bonding. For ex_ However, rvhen all the Ca2+ ancl Mg2+ ions
amplc, in copper sulpbate pentahydrate,
CLrSOo.-5HrO, four HrO molecnles are linked to the
central Cu2+ iou by coor.dinate bonds while the
Iifth H2O molccule is linked to thc sulphate
(S{)02-) ion by H-bon<ling.
(iii) W'(tter nnlecules dt.{ prese t itl interstitial woter.
:;ilq or wtitls irt the crystal lafiicc. For example, in
bariun chloride dihydrate, BaClr.2HrO, the two U.I{).1. Thes nf Hardness of Water
HrO molecules occupy the voids in thc crystal Ilardness ofwater is oI two types :
la!
tice.
(a) Tentpornry hardnesl and
(b) Petnrunent hadnes:-
11.10. Hard and Soft Water
(a) Temporary hardness. Temporary harl-
Natural water contains dissolved salts. ncss ofwater is due to the presence of l)icarbonatcs
Dcpentling upon its behaviour towards soap solu- of calcium and magnesium, Le. Ca(HCOr), ancl
tion rrrl. llther lornlation, water may be classified Mg(HCOr)r. It is called temporary hardness sinco
,):,.ttlt t J,nd lk)t'd h otct.
h)olt
it can be easily removed by simply hoiling anrJ
S oftw aer, Wate I th a t producc s I a tlrcr wit It soLp Iillcring the water. Termporary hardncss
rcudilf is called solt palsr: Examples of soft water
ii also
called carbonate hardness.
arc : rair. wator, distilled watcr and demineralised
(b) Permanent hardness, Permanent hard-
water.
ness of water is due to the l)resence of soluble
Hard water. V/qtet whicll does not produca chlorides and sulphates oIcalciunr anrl magncsiunr,
ha wqtir A feyt
lotlter witll soap rcttdtb, i.t called i.e., CaCl, , CaSO. , MgCl, and MgSO4. This rypc
oxamples ofhard water are : sea water, river water,
of hardness is called permancnt hardncss since it
spring rvater, lake rvater.and well water.
cannot be removed simply by boiling the water.
Cause of Hardness of Water. It has been es_ Permanent hardness is also called non-carbonate
tablished that hardnes.s of water is (lue to tl.rc hardness.
presarce oJ bicarbonotes, cltlorides and.\ulpltotes ol
11.102. Methods of Removing Hardness of
calututt artd ntagusiun fu it. }Ja:lJ. water does noi
prodrrcr lirther rvith soap readily. This may hc ex_ Water- Softening of Hard Water
plainetl us under:
Soirp is rodirrm or lotassiunt salt ol cerluin
highe r frt t; acids s uth rsstruic .t, id. pdlmitic qcid,
oleic acid ctc.When hard water is tre ated with soap
solution, Ca2+ and Mg2 + ions present in hard water
1112O

I. For temporary hard water. The temporary 1. Lime-soda process. This method is
hardness of water is due to the presence of bicar- employed for
bonates of calcium and magnesium. It can be contains both t
removed by any one of the following methods : In this method,
W
1. By boiling. r is Ca(OH), and sodium carbonate are used. Where-
boiled, bicarbonates um as, slaked lime removes temporary hardness,
decompose to form ag- sodium carbonate removes permanent hardness.
nesium carbonates resPectivelY. Ca(HCO3)2 + Ca(oH)z-ZCaCot I +2H2o
A
Ca(HCOr), """'-"' CaCo3 I + CO2 + H2O CaCl2 + Na2CO3 CaCO: J + 2NaCl
(Tixnponryhadrrcss) Cal.carbonate MgSOa
----
+ Na2CO3 +MgCO3tr * Na2SO4
A
Mg(HCO3)2 """"".r MgCO: I + CO2 +H2O 2. Ion exchange method. Tbis is the most
(Tempotury ha n $) Mag. carbonatc modem method for softening ofhard water. In this
method, the Caz+ and Mg2+ions present in hard
These insoluble carbonates are removed by
water are exchanged by those present in complex
hltration and the water is rendered soft.
inorganic and organic compounds called ion ex-
2, By Clark's Process. This process is used on changers.lon exchangers are mainly of two types :
a commircial scale. In this process, calculated
(a) Inorganic ion exchangers - Fermutit
quantity The bicarbonates
methoil. Compelx inorganic salts like hydrated
presenti terreact withl.ime
sodium aluminium silicates, NarAlrSlO*. xHro
io form magnesium car-
bonates which can be easi.ly filtered off. have the interesting proPerty of exchanging Ca2+
CaO(s) +HrO ...........r Ca(OH),
Quick lime Slaked linre

Ca(HCOr), Ca(OH), .....-

+
2CaCOrI + ZH..O

Mg(HCOr), + Ca(OH), .....- silica (Sior). The fused mass is washed with water
the Porous mass
CaCo3 J + Mgco3l + 2Hzo Both zeolite and
Howeve,4, if excess of lime is added, watet will for-
again become hard dte to absorption of COrfum 't'h;e;neral
the atmosphere by unused slaketl lime lo form The zeolite or permutit is loosely packed over
s olub le calciwn bicatbonate. layers of gravel and sand in a big tank (Fig. 11.8).
Ca(OH), + 2CO2 """-'r Ca(HCOr),
NaCl
II. For permanent hard water. The following SOLUTION
methods are used for the removal of permanent
hardness ofwater. HARD
WATER
Washlng soda prmess. In this process, hard
water is treated with a calculated amount of wash-
ing soda (NarCOr) when chlorides and sulphates
ZEOLITE
of calcium and magnsium prosent in hard water
get precipitated as insoluble calcium and mag-
-nesium
cirbonates which can be easily filtered off GRAVEL
The water thus becomes soft.
Cacl, I NqCo3 --"""' J + zNacl
Caco3
MgSOo + Na2CO3 ...........r MgCO3l + NqSOo
III. For both temporarJ and ptmannthard
waters. The foltowing methods are used.
 HYDROGEN 11121

Hard water introduced from the top into the base

is are even superior to zeolites since they can remove
of the tank. From the bottom, water dses up not only all types of catiotrs but also anions present
through the gavel and sand layers and finally per- in hard water. The resulting rvater is called
colates through the bed ofthe permutit. During the demineralised water or deionised rater and is as
process, the Ca2+ and Mg2+ ions are exchanged by good as distilled water.
sodium ions in the permutit. Ion exchange resins are giant organic
Na2Z + CaCl2 molecules of high molecular masses. These are
Sodiumzeolite (Frcm hord woter) essentially of two f,?es :
CaZ + 2NaCl (i) Catlon exchange resins. These resins con-
Calcium zcolite sist of giant hydrocarbon framework attached to
(lelt in ,hc tar*) acidic groups such as - COOH (carboryl) or
where z = Al2SrrOE .rtI2O. -SO,OH (sulplrcnic ocid) groups. They may be
Similarly, represented by the general formula R COOH or
N'arZ + MgCt MgZ R- SO2OH where R represents- the giant
sod. zeorite (Fion hotdwatet) hydrocarbon framework.
Wnfr:ili"
+ 2 NaCl Since these resins can exchange H+ ions with
cations such as Caz+ and Mf+ ions present in hard,
.{s a result, Ca2+ and Mgz+ ions get attached
to the zeolite and the water which rises above the
wttei they are called cation exchange resins or
simply cation exchangers.
permutit layer is reasonably soft. The softened
water still contains sodium salts. But these sodium ( ) Anion exchange resins. These resins con-
salts do not precipitate soap and hence do not sist of giant hydrocarbon framework attached to
prevent the lather formation. basic groups such as OH- (hydroxide) ions usually
After some time, the whole of permutit gets
in form of substituted amoonium hvdroxides.
These may be reprsented by thc generai formula,
exchausted due to the conversion ofsodium zeolite +
into calcium and magnesium zeolite. It can, how-
ever, be regenerated by passing a 107o solution of
R - NHTOH- where R denotes the giant
hydrocarbon [ramework- Since these resins can ex-
NaCl through it.
chonge OH- ions with anions such os Cl- and
CaZ +2NaCI ........- NurZ + CaCr2 SOf,- ion^t ptesent in hard water, lhey qre called
(Exhaurle! (Repzratcd
Pa?nuttt) pemuttit)
anion exchang resins or timpl), anion exchangers.
MeZ + 2NaCl ...........+ NazZ + MgCl2
Let u-s nowexplain the working ofthese resins
(Exchausted (Regfierated
in demineralization of hard water.
pctmuut I ponutit) First ofall, hard water is passed though a tank
The soluble calcium and magnesiumsalts thus packed with cation exchange resins supported over
formed are rvashed away by water and the gravel (Fig. 10.13). All the cations present in hard
regenerated permutit can be used again. water will exchange with H+ ions furnished by
resins as shown below :
Advantages of th Permutit Process
(i) It is an efhcient process. 2 R-COO-H+ + CaCl,
resin)
(Cation exchar.ge (From hard water)
(i) This is a very cheap process since during
the process only sodium chloride is consumed -----------' (RCOO)2Ca + 2}{+ + ZCt-
which is quite cheap. (Exchoustcd rcsin)

(rii) It can be used to remove both temporary 2R-COO-H+ + MgSO4

and permanent hardness completely. resin)
(Cation cx.hange (hom hord wat r)
(b) Organic ion exchangers. One ofthe major -----------' (RCOO)2M! + zH+ + SO?-
drawbar:ks of the inorganic ion exchangers (per- (Exlousted rcsin)
mutit process) is that these can remove only Ca2+ Thus, the water which comes out from the
and Mg2+ ions present in hard water. However, bottom of the first tank is richer in H+ ions. This
recently it has been found that certain synthetic water is then passed through a second tank which
organic exchangers also called lon exchange resins is packed with anion exchange resins supported

)
11122 Pradeep's

ovor gravel (Fig. 11.9). Here, the Cl- and SOo2- Similarly, the exchausted resin in the second
ions present in hard water exchange with OH- ions tank is rcgenerated by treatment with moderately
strong NaOH solution.
of the esins.
+
+
R-NH3OH- + Cl- R-NH3CI- + Na+ oH- ..........*
(E.rchausted rcsin)
(A ion ercharqc resin) An water) +
+
R-NH3CI- + oH- R-NH3oH- + Na+ + Cl-
(Exhoustcd tctin)
(Rcqenera4.t ftlitt)
+ Thus, the cation and anion cxchangers can be
zR-NHTOH- +
SO?- used over again and again. lt makes this proccss
(A io dchangercsii) (in wato) both efficient and cheap.
+ 3. Calgon process (reqttcsrrurion). In this
(R-NH3)2So?- + z(JH- process, Ca2 + and Mg3+ ions present in hard water
(Ethausted rcsit) are rendered ineffective (sequestrated) by treat-
Simultaneously, the Ht ioos coming from the ment $/ith sodium polymetaphosphate, (NaPOr),
hrst tank combine with OH- ions liberated in the where x is as high as 100, or more commonly with
sccond tank to form water. sodium hexametaphosphate. Nar[Na.(Pt\)61. Thc
Hr+ OH- + HrO trade name lor sodium hexametaphosphate is cal'
gon (which means calcium gone).
Thus, the water obtained by this method is
frce lrom all types of cations as well as anions. When calgon is added to hard water, the
Therefore, this method is particularly useful for Caz+ and Mg3r ions present in it combinc with
obtaining drinking water from sea water and also sodium hoxametaphosphate to form soluble com-
for obtaining pure water for laboratory Purposes. plex of calcium and magnesium salts.
Regeneralion of rcsins. The exhausterl resin in zCaCl.- + Na2[Na4(PO3)6]
the iirst tank is regenerated by treatment with (Ftonhadwoler) Sod.hcxanlelaphosphatc
noderately concentrated HrSOo or HCl. Nar[Car(POr)61 + 4NaCl
ComPlcx salt(.roIublc)
ca(oocR), + 2H+ Cl-
2MgSOo + NarlNao(POr)61
(Dxhausted. resin)
(Fromhatdwalet) Sod.hexaoletaphosphale
zRcoo-H+ + Caz+ + 2Cl- NarIMgr(POr)o] + 2NarSOo
(Regenenrcd ru\in)
Complcx salt(rotuble)

HARD WATER

DIL. HCIOR DlL. NaOH

H2 SOa--.-- FOR
FOR REGEN ERATION
REGENERATION

CATION ,/ANloN
EXCHANGE EXCHANGE
RESIN RESIN
GRAVEL

FIGURE 11.9. Ion exchange process involvingorganic resins

 HYDROGEN 11123

The complex calcium and magnesium ions do not form any precipitate with soap and hence reaclily
_
produce lather with soap solution.
ess can be used for laundry and household washing purposes
n is also used in rynthetic detergents to check the wistige of
rcmoing boiler scoles.

rEil r. Degre of hardtwis defined ar he mwber of parts of cokium catbonate or equivolant to voriour calcium and
magnesiwn sahs preseht in a nihon Frtt of wuer by mast. It ir eqressetl in ppn
ExtdMPLE. one liffe oI o ro,nple of hlnd baler conroin\ I mg of coct, aad t mg of Mgcl, Find oul the totol
hordness in terms of parts of CaCO , pr I d partt of troter by marr.
Solution. (i) Mol. ntass of Caclz = I 1l
Now, lllgof CaCl2 = lffigof CaCO:
.. I mg of CaCt2 = jf; x r mg of CaCO: = 0.9 mg of CaCO:

(ii) Mol. mass of MgCl2 = 95

Now 95I of MgCl2 = l0og of CaCOt

.r t mg ot MgC[ = xI mg oi CaCO] = r .0s mg of CaCO:

S
Thus, I litreofhardwatercontaios =0 90 + I 05 = t.95 mgoICaCo3
ODe litre of watcr = I 03 g = 166 ,.r.r,
.. Degree ofhardDess = I .95 ppnr.
liill 2. Estimntion of to Ca2+ and Mg2+ ion
volumetrically. solutionofpH tbis tilra
solution of ED salt) using'Eriochrome
under these conditions, ca2+ and Mg2+ rons form complexes with EDTA. when allthe ca2 + and Mg2+ ions
are cor$umed. The next drop of EDTA chaDges the colour of the i[dicator tiom wine red ro blue.

1 I .1 1 , Heavy Water i:ii:t.:r:iti:i:i:,:lii::.:-liir:t::r:i:::::i::i.::.ii.;r:tl::;itiili:iii::li:it:

(i) Being smaller in size, H+ ions have gruater
Chemically heavy water is deuterium oxide mobility (or speed) as compared to D+ ions.
(DrO). It was discovered by Urey, an American (ii) Becarce oI lowu dischage potenlial, H+
iorc on dischatged at thc cahode more easity than
Chemist in 1932. He showed that ordinary water
contaiEs traces (1 part in 6000 parts) of DrO.
D+ ions.
(iii) Hydmgen atoms combine much more
11.11.1. Preparatlon of Heavy llhter rqpidly to form moleculor hydrogen thoa do
Heavywater is rnainly prepared from ordinary deuteium atoms to Iom D7.
water either by exhaustive electrolysis or by frac-
tional distillation.
l. By exhaustive electrolJrcis. This method is
hased upon the principle that when ordinarywater
is electrolysed, protium (or hydrogen) is liberated
much morereadily than deuterium (Dr) because of 29,000 litres of nrater must be electrolysed to get
the following reasons :
one litre of 97o pure DzO.
11124
The electrollic cell designed by Brown, Deg-
get and Urey for the preparation of heary water is
shown in Fig. 11.10.
It consists of a steel cell (45 cm. long and L0
cm. in diameter) which acts as a cathode. Thc
anode is a cylindrical sheet ofnickel with a number
of holes punched in it. In actual practice a large
number of such celts are employed for electrolSis
of water in a number of stages. The gases obtained
from each stage areburnt separately and water thus
produced is returned to the previous stage. As a
result, the concentration of heary water goes on
increasing slowly in the residual water' Generally,
the whole process is carried out in five stages as
described below :
iscarried out for nearlyT2 hours. Thegases evolved
(protium and orygen) in this stage are discarded.
After the fust stage, the charge is reduc.d to about
15 litres and contains about 2 5 per cnt heavy
water.
Second Stage. In this stage, the residue ftom
the hrst stage is electrolysed in a battery of six cells.
The electrolpis is continued till heavy water con-
tent trcreases to about 12 per cent. The gases ob-
tained areburnt and returned to the cells inthefirst
stage.
Third Stage- The residue obtaioed in the
second stage is further electrolysed to raise the
heavy water content in it to about 60 Per cent. The
gases evolved are burnt and returned to the cells in
the second stage.
Fourth Stuge.'fhe tesidue from the third stage
is electrolysed again in order to increase its heavy
water content to about 99 per cent. The gases
evolved are burnt as usual and sent to cells in the
third stage.
Fifth Stage. ^fhe heavy water obtaincd as above
is contaminated with impurities of alkali and ordi-
oary water. It
is subjected to distillation and the
distillate Ls electrolysed when pure deuterium is
obtained. This is burnt separatelywith orygenwhen
100 per cent pure D2o is obtained.
A flow sheet diagram for the preparation of
heavy water by this method is given inFig 11.U.
ORDINARY
SECOND STAGE
(6 CELLS)
FIGURE 1 I .l l. Flow sheet diagram for the
oreoaration of heaw water hv continuous
' ind prolonged efectrolysls'of wat"r.
In India, hearywater is manulhctured at Nan-
gal in
Punjab and at Bhabha Atomic Research
Centre (BARC), TrombaY in
BombaY
(Maharashtra) by electrolysis of ordinary water.
2. Byfractlonal
pheric pressure, the
heavy water are 373
This small differenc
the basis of preparation of hearywater byfractional
distllation of ordinary water. In actual practice,
fractionating columns of the order of about 12
metres height are employed.
HYDBOGEN 11125

11.112. Properties of lleavy Water CUQ +ZDrO Ca(OD)2

(a) Physical Properties. It is a colourless, Calcium carbide -
odourless and tasteless mobile Iquid heavier than + DC=CD
water. Because of higher molecular ma^ss, there is a Deuteroacetylene
marked difference in physical properties of ordi- 6.Action with,netsllic nitrides, phosphides and
nary water and heavy water as shown in Thble 11.4. arsenides. Heavy water reacts with metallic nitrides,
Further since dielectric constant of DrO is phosphides and arsenides liberating deuteroam-
lower than that of HrO, therefore, ionic com-
monia, deuterophosphine and deuteroarsino
respectively.
pounds are less soluble iu DrO than in HrO.
Mg3N2 + 6DrO -------r 3 Mg(OD),
(b) Chemical Properfies. the chemical C.l. tritride
properdes of healywater are quite similar to those + 2 ND3
of ordinary water. However, the reactions ofheavy
Deuteroammonia
water with most of the substances proceed at a
much slower rate as compared to ordinary water. CarP, + 6D2O -------r 3 Ca(OD)z
Some important chemical properties of heary Cal. phosphide

water are described below : + 2PD3

7. Electrclysis. When heavy water is Der.rterophosphine
electrolysed, deuterium is obtained at the cathode. NarAs +3DrO.._3NaOD+ AsD,
zDrO ZDz +Oz arsenide
Sod. Deuteroarsine

- Deuterium 7. Formation of deuterates. Like ordinary

2.Action with alkali and alkaline eatth metak. water, heavy water also combines with many com-
Heary water reacts slowly with alkali and alkaline pounds as heavy water of crystallization. The heavy
earth metals producing deuterium. hydrates thus obtained are called, d,euterates. For
2 Na + 2 DrO -.--- 2 NaOD + Dz example, CuSOo . 5 DrO ; NqSOo . 10 DrO ;
Sodium dcutcroxide
MgSOn. 7 DrO, NiCl, . 6 DrO, Coclr. 6 D2O etc.
Ca*2DrO .......' Ca(OD), +Dz
Calcium dcutcroxidc
t. Exchange reqctions. When treated with
heavy water, many compounds exchange Lheir ac-
3. Action *,ith metallic oides. The oxides of
tive hydrogen atoms either partially or completely
active metals like sodium and calcium react slowly with deuterium. Some of these exchange reactions
with heavy water to
form their respective are given below :
deuteroxides.
NqO + DrO -------' 2 NaOD
HCI + DzO + DCI + HOD
CaO + DrO ------.r Ca(OH)z NaOH + D2O i-- NaOD + HOD
4.Action with non-metalic oides. Non-metal- cHCl3 + DzO : CDCI3 + HOD
Iic oides such as phosphorus peotoxide (P2O5), Chloroform Deuterochloroform

sulphur troxide (SOr) etc. readily dissolve in heavy NHICI + D2O + NH3DCI.+ HOD
water forming their corresponding deuteroacids. NH3DCI + D2O +- + HODNH2D2CI
P2O5 + 3 D2O D3PO1 NH2D2CI + DzO i-' NHD3CI + HOD
-* Deutercpho+horic acid
NHD3CI + D2O i- ND4CI + HOD
SO3 + D2O -* D2SO4
Deutercsulphuric acid
9. Biological propefties. Heary water is in-
jurous to human beings, plants and animals since it
5. Action with metallic caftides. Heavy water
slows down the rates ofreactions occurring in them.
reacts with metallic carbides forming Thu-s heavy water does not support life sowell as
deuterohydrocarbons.
does ordinary water.
AloQ + lzDzo------.
Aluminium Carbide 11.113. Uses of Heayy Watr
4 A(oD)i * 1. As a moderator. Heary water is extensively
,.,,.SRi,n"n. used a.s a moderator in nuclear reactiorx since it
 Pradeep's i;i,t, lttii*i; qll
,vs down the fast moving neutrons a-nd thus helps deuterium. ThLs suggests that H3PO, has only one
:, rrnlrolling thc nuclear rcactions. ionizable H-atom ar.<lhence it is a ntonobqsic acid-
tracecompound. Heavy water is widely .
2. As a 3. For thc preparatlon of deuterium. Heavy
,ic<l rrs a tracer compound for studfng the hydrogen or deuterium is produced by the
rcihanism of many reactions, For example, when electrolysis of heavy water or by its decomposition
r,,n1-phosphorus acid (H,PO) is heated with by Na metal.
, o. only one H-atom is found to exchange with

iU L l)euterium peroxide is prePared by the action of D2SO4 dissolved in HzO on BaOz

BaO2 + D2SOa .- BaSOr + DzOz

ir, 2. I)eutcrium chloride may be preParcd by any oDe of the following methods :

2AgCl +D2 +2AE+2DCl

2 NaCl + DzSOa 1'IarSOa + 2DCl
SoCl2 + 2Dzo - D2SO3 +2DCl
-
11.12. Hydrogen Peroxide . Ba{)2.8H2O (.r) + H2SO4 @d
Hydrogen peroxide was discovered by Danumpcroxroe-- -
li.'neh chemist !.L. Thenqrd in 1818, Irs "^ilt:"]::-,,-
-" BaSoo (s) + Hro, (aq) + 8H2o o
,r, . ular lbrmula is HrC)r.
Hyd rogen peroxide
! l.l2.l. Prcparation of Hydrogen Peroxide The white precipitate ofBaSoo is removed by
i. l.rom sodium peroxide (Merck's method). liltration leaving behind a dilute solution (5%) of
L- rl:rtcd tmount ofsodium peroxide (NarOr) is HrOr. In dais metho4 utthydrour barium peroxide
, .rrrllv added to an icc-cold solution of 207, cannot be used since the precipitated BaSO oforms a
..s)I protective layer oround unredcted boiurn peroxide
Nr2o, + H2Soa ...........t NarSOo + Hro, thereby prcventing the firdter reaction .

S, drum Hydrogen Llmltatlon. Hydrogen peroxide Prepared by

r.roridc Pcroxide this method contains appreciable quantities of
r pLrn cooling, crystals of NarSOo.l0HrO Ba2+ ions (ia the form of dissolved barium persul-
phate) which catalyse the decomposition of HrOr.
. ,,:,Lrtc orr[ and the'resulting solution contains
: '.,r \Otli, HrOr. The solution also contains some Therefore, [IrO, prepared by this method cannot
-. , ivcrl NarSOo but it does oot interfere with the
r
be stored for a loag time.
.,.,r ,ns o[ HrOr. A pure sample of HrO, may, Further, HrSOo also acts as a catalyst for de-
. . r, bc prcpared by vacuum distillation. composition of HrO, therefore, the use of weaker
2. [r'om barium peroxide- Laboratory acids such as COr( or HrCOr) and HrPOo are
, .!troJ of preparation. Hvdrogcn peroxide is preferred to H,SO..
,,,. i, rrcd from barium peroxide by the following
(b) By the action of carbon dioxide or carbonic
, t irrrils :
acid. When a rapid stream of CO, is bubbled
(tt ) By tlte ctction of d,ilute sulpltuic acid. A thin
through a thin paste of BaO, in ice-cold water,
,irsl'r oI hydrated barium peroxide (BaO2.8HrO) is
HrO, and BaCO, are produced :
l,r.prLled in ice-cold water and then added slowly
,l icc-oold solution of 2096 HzSOr. BaO2 + H2O + CO, """'r BaCO, J *H2O2
 HYDBOGEN 11127

The insoluble bariunr carhrrnrrl c is r tnrovcd bv 2NH1HSO1 2H+ + 2NH1SO4-

liltration leaving behind a dilute solulion ol I-l,Or.
(c) By the action ofpltoslthoric trcirl Hl,clrogen
At cathode - + 2c--
:2H+ }J,zi

peroxide can also be prepared hy thc action of At anode : 2NHoSOt ------+ (NH4)2S2Os + 2z -
phosphoric acid on barium peroxiclo : Amln. per6ulphate
3BaO2 + 2H3PO4 Ammoniuni persulphate formed around
anode is withdrawn and distilled with water to give
- Bur(POo), J + 3HzO2 Hzoz'
This method has thc advuntilgs over (NH1)2S2O' + ZH'O .----------+
BaO, -HrSOo mcthod sincs almost all thc hcary
netal (s.& Pb ctc.) impuritics prescnt iu BaO, and
2NH1HSO4 + H2O2

which catalyse the clecon.rposition oI H,O, are This process is now used only for the
laboratory preparation of D2O2, i.e. ;
removed as insoluble phosphates. As a rcsult, thc
resulting solution of H2O2 has good keeping IqS2O8 + 2 DrO-+ 2 KDSO4 + D2()2
properties. 2. By autoxidatlon of 2.ethylanthraqulnol.
11.12.2. Manufacture of Hydrogen Peroxide This is a new method and is widely used in U.S.A.
I. By electrolysis of 507o. HrSOa. Hydrogen In this process, air is bubbled through a lOVo solt-
peroxide is manufactured by the elcctrolysis o[ a tion of2-ethylanthraquinol in
benzene and
col<l 50'k solution of H2SO4 in an electrolyic cell cyclohexane when z-ethylanthraquinol is oxidised
to 2-ethylanthraquinone and HrO, is formed ac-
using platinum as anode and graphitu us cathode.
Thc reactions taking placc arc : cording to the following equation.
2HrSOo 2H+ + 2HSO;
C.H.
Atcotlutde'.2H+
- + 22- + Hzt o2

At unode i ZHSO; H.S2O8 + 24- HlPd

Pcruxodisrlphuric
acrd
Peroxvdisulphuric acid formed around anode
is withdrawn and then distilled with rvatcr under
reduccd pressure. The low boiling HrO, clistils over
along with water leaving bchincl high hoiling
HrSOo which is recovered and recl,cled.
+ H2O2
H2S2Os + H2O --...* H2SO5
Pcroxod isu phu ric
I Pc rorio nKnrcs u lph u ric
acid ,ri{l o
+ H-SO4 2- Eth,'lanthraquinonc
The HrO, thus formed (about t%) is ex-
H2SO5 * HrO.+ H2SO4 + HzO2
Peroxonronosulphuric
tracted with water and the aqueous solution is con-
acid centrated by distillation under reduced pressure to
Modificatio[. Recently, it has bcen observed glve 3OVo (by weight) HrO, solution.
that if instead oI HrSOo, an equirnolar mixture
-504lo 2-Ethylanthraquinone formed in the process
of H2SOa and ammonium sulphate is elcctrolysed, is reduced with H, in presence ofPd catal),st to give
a more concentrated solution of H"O, is obtained. back 2-ethylanthraquinol which is used again.
The reactions taking place are :
Thus, in this process, onlyatmospheric orygen and
(NII4)2SO4 * H2SO. hydrogen are used up which are ioexpensive.
2NH4HS01
---+ Therefore, this method is quite cheap and is widely
Anini hldrogcrr
sulDbate used for the manufacture of H2O2.
1't128
11.123. Concentration of Hydrogen hroxide
solution
Hydrogen peroxide prepared by any of the
above methods is in the form of di.lute aqueous
solution. Quite often for a large number of reac-
tions, we need a concentrated solution of HrOr. It
cannot be concentrated simply by distillation since
it decomposes much below its boiling point to give
HrO and O,
2HrO2 2H2o + 02
-""t
Further, the process of decomposition is
catalysed by presence ofheary metalion impurities,
dust rurd rough surfaces. In view of thcse difficul-
ties, concentration of HrO, is carried out carefully
in a number of stages as follows :
(r) Evaporation on a water bath. The dilute
aqueous solution of hydrogen peroxide is taken in
a large shallow evaporating dish and is heated on a
water bath. Slow evaporation of water continues
until the solutioa contains about 5OVo hydrogerr
peroxide. Further concentration of hydrogen
peroxide by this method Ls not possible since it
tends to decompose.
(ii) Dehydratlon ln a vacuum desiccator.50Ta
solution of HrO2 as obtained above is taken in a
dish and placed in a vacuum desiccator containing
conc. HrSOo as shown in Fig. 11.12.
TO VACUUM
P UMP
VACUUM
DESICCATOH
CONC.llasO.
FtGLriE If.12. Vacuum Deslccator.
Pres(irre inside the desiccator is reduced by
connecting it to a vacuum pump. As a result of low
pressure, water'readily evaporates and the water
vapours thus produced are absorbed by conc.
HrSOo. In this way, hydrogen Peroxide of about
9070 concentration is Produced.
+A negative catallst retards or decreascs thc ratc of
Netl Course Chcn, isttu
(tll) Dlstlllation under reduced pressurt. The
907" solution of hydrogen peroxide as obtained
above Ls subjected to distillation under reduced
pressure (10- 15 mm). During this proces-s, water
distils over between 303-313 K leaving behind
almost pure (99%) hydrogen peroxide.
(ly) Removal of last tracs (,fwater. The last
traces of water in hydrogen peroxide are removed
by freezing it in a lreezing mixture consisting ofdy
ice (solid carbon dioxide) and ether when crystals
of hydrogen peroxide separate out. These crystals
are removed, dried and melted to give pure
hydrogen peroxide.
Storage of hydrogn peroxide. The following
precautions are taken while storing hydrogen
peroxide solution.
(i) Hydrogen peroxide cannot be stored in
glass bottles since the rough surface of glass, alkali
oxides present in it, and exposure to light catalyse
its decomposition. Therefore, Hro, Ls usually
stored in coloured paffin wax coated plostic or
tellon boules.
(ii) To further check the decomposition of
HrOr, some stabilizer or negative catalyst* such as
glycerine, acetanilide, phosphoric acid etc. must
also be added.
11.12.4, Strength of Hydrogen Peroxide solu-
tion
The strength of an aqueous solution of
hydrogen peroxide is usually expressed in the fol-
lowing two ways :
It
(a) Percentage strength. expresses the
amount of HrO, by weight present in 100 ml of the
solution. For example, a 307o aqueous solution
(Vv) of H.O, implies that 30 grams of H2O2 are
present in 100 ml of the solution.
(b) Volume strength. The most common
method of expressing the strength of an aqueous
solution of hydrogen peroxide is in terns of the
volume (tu ml) ol orygen liberated at N.TP by the
decomposition ol I ml of that sample of hydrogen
penxiile. Thts, the aqueous solutions of hydrogen
peroxide sold in the market are labelled as /0
volume, 20 volume, i0 volume, 100 volume etc. A
solution ol hydrogen peroxide labelled as 10 volume
actually means that 1 ml of such a solulion of
hydrogen peruxide on decomPosition by heat
produces 10 ml of orygen ol N-TIP
a chcmical leaction.
 HYDROGEN 11129

Sinriarly, 1ml of20 volume, i|volume and 100 . . 10 ml of C)2 at N.TP will be obtained from
volume HrO, solutions produce Z) ml, 30 ml and 6R
10sof Hro2
100 trll of oxygen at N.TR respectively. ffix
Let us now calculate the percentage stlength But 10 ml of 02 at N.T.P are produced from
of a 10 volume H.O, solution.
7 ml of l0 volume HrO, solution
Hydrogen peroxide decomposes on heating
Thus, 1 ml of 10 volume HrO, solution con-
according to the equation :
2HrOr"""+2HrO + 02 tuio. x 10gof HrO,
2 x 34 g 22.4li!Igs ar N,T.p.
ffi
or 24{D crn3 at N.T,p.
. 100 ml of l0 volume HrO, solution
. will
From the equation, .68 x 10 x I00
contarn
22.4 \tres of O, at N.TP are obtained from fffi i = 3.035c
2 x 34 or 68 g of tI2O2. Thts, a l|volume H,O, solution is approx. 37a

N t-.-FRQE_U..n\i,,9r9il* rrcsrnr,\u(;rH()r..
H.lI)t,t( )(;tr\ l,t,_tioXIDL SOLUTIONS

t..\t\tpll,tIl.l. Calculate the nomolity ol20 ... Eq.Et.of H2O2 = 17

volume hydrogen peroxide solution.
ate the nomatirv of 20 votume
step t. Tb catculate the strcngth t, ,ro)]ifrl;*.catc
Bll e H2ozsolution.
strength
By definition, 1 litre of 20 volume HrO, solu- ''
Nowwe knowthat, Normalitv - Eq. *n.
tion on decomposition gives 20 Iitres of orygen at
N,T,P
Consider the chemical equation,
=i=t'st
60;7

Hence the normality of 20 volume HrO, solu-

zHzOz "--------- 2HzO * Oz
tion
2xy=6EE 22.4lkres at N.T.P. = 3.57 N
Now 22.4 litres of 02 at N.TP will be obtained
from H2O, = 69 * Solution. We know that strength
.'. 20 litres of 01 at N.T.P. will be obtaircd from
=-N-rilaliry x Eq. wt.
s"or= 9# E= Go.7c and Eq. wt. of H2O2 = 17

Thus, the strength of Z) volume HrO, solution .. Strength of 1.6 N HrC), solution
cl
= @.7 =l.6xL7C
_ Step 2, To cakulak the equivalent wciglt ol Now 68 g of HrO, gives 22,100 ml O, at N.Tp
H,O,
.'. 1.6 x 17 g of H2O, will give
Consider the chernical equation,
2241n
2H2Oz '-----'- ZH2O * Oz
68 x 1.6 x 17 =8960 ml of O, at N.T.p
6E parrs by Eight 32 porir b, srighr
From the above equation, But 1.6 x 17 gof HrO, are pre sent in 1000 ml
32 parts by wt. of oxygeE rre obtained from 6g of HrO, solution.
parts by wt. of IIrO. Hence 1000 ml of HrO, solution gives 8960 ml
.. 8 parts by wt. of orygen will be of 02 at N'TP
obtained
from
.. 1 ml of HrO, solution will give = 99
1000
lTpartsbywt. of HrO,
#rt= =8 96 ml of Oz at N.Tp
1 1/30
Pradeep's

Hence the volume strength of 1'6 N H2O2 Step 2. Tb culculste the volwne of Ozliberated

solution :E 96 volume ot STP fiom 100 nn! of 2M solution.

Irf{Nl PLIt 1 1.-3. Calculate the volume strength 1 titre of 2M HrO, solution contaios H2O2
of s 3Eo solution of HzO2. = 689
SteP 1. Io cdlculate the omount of . . l(X) cm3 of 2M HrO2 solution will contain
HrOrpresent in one litre ol 3o/o soltuion. Hzoz
100 mt of HrO, solution contain HzO2
=**"100=6.88
1000
=3c
. . 1000 ml of HrO, solution will contairr The cquation rcpresenting thc decomposition
? of HrO, is
HrOr=ffix1000=309 zH.Oz ZH|O * Oz
Step 2. To calculate the volume strength 2 x = 3.1 6ti g 22400 cml ar STP
-
Consider the chemical equation, Now 68 g of HrO, at STP give O,
2I{2o, / llr1l I 02 : 22400 cml
2xy=6Ag-"+ 22 4litrc. at N.T.P.
. . 6.8 g of HrO, at STP will evolve O,
Now 68 g of HrO, give 02 at N.TP
z24oo
= 22'4litues - x 6.8 -- 2z4o cm3
6u
. . 30 g of HrO2 will give 02 at N.TP = Z24litres
21.4 ml o[ a H rO rsolution ofter
= ,30 : 9'88 titres
EXAMPLE 11'5' 30
68 acidifcatnn required 30 ml ol NII0 KMnO4solution
= 9880 ml.
Iot conlplctc o.\idation- Colculate tlu percentage a,td
But 30 g of HrO, are present in 1ff)0 ml of voluruc sttungth ol H20, solution.
Hzor' Solution. SteP l. Tb determine the non tolity
Heuce 1000 m[ of HrO, solutioin gives 0, at tf n. Fronr the given data,
N.T.P = 9880 ml H"C)., Vr = 30 ml,
For Nr = ?

.. L ml of HrO, solution will give O, at Fctr li|tnOo,Y, = lQ 1| = N/10 Nz

p1p=2!!9=e.88rnl. Applyirg normality equation, N1V1 = NrV,
1000
i.c.,30x Nr = 30 x 1/10
Hence the volume slrength of 3Vo HrO, soht'
tion : 9 88 ''' Nr=o lN
II)LAXIPI-E 11.4. What is the mass of hydrogert Thus, thc normality of HrO, solution = 0' 1 N'
on ? Calculqte SaeD 2 . To detennine lhe Percentage strengtlt oI
upon complete HzOzsolulbn,
ve solution.
calculste the moss of Wo know that, Hro z- 2H+ + oz + 2 e-
Solution. SteP 1. fo
H2 of 2M solution. .. Eq $t. of HrOz = 34/2 = 17
Molecular mass of H2O2 = 2 x 1+ 2 x 16 Hcncc strength of HrO, solution
:34amu = Normality x Eq. Et.
By definitiotr, 1 litre of 1M HrO, contains 34 =01xL7=l'7g1itre
g of HrO,
.. H2O,
Strength of
l 7x 100
"/o = ffi
.'. 1 litre of 2M H2O, will contain HrC),

:34x2=68C = ll lflo.
 HYDROGEN

Step 3. 1"o detcmtine tl& volunrc strcngth oI But 1.7 g of HrO, are present in t00() rri
HzO2;ohttion. HrO, solution.
Consider the chemical equation, Hence Lff)0 ml of HrO, solution give :. -ir,it
2 H2O, -"+ lltr1l I O, of O, at N.TP
689 22400 nl a! N.T.P

Now 68 g of HrO, give O, at N.TP

. . I ml of HrO, solution will give
:
. . 1 7 g of
22400 ml
HrO, will give O, =ffi=o s6ml ofo' at NTP
. . Volume strength of HrO, solution
=T"1.7 = 560mt
= 0.56.

-r -'j
Problems oD perccntage strength, norDality, molariry and volume srrengrh of Hro, canE easily sotrL .t 1..
the applicalion of the following relations.

l. volrme strensth = s.6 x Normlrfiy = s.r, uHHHiffi*, * ro

FOR.,P,RAC,. I.CE r' '

"RO7LEM7
1. Calculate thc concentration in gram/4itre of a 20
v(rume II2O2 solution.
| 60 Tpltl
3. Calculate the Dormality of a solutioD o[
hydrogeo proxide labelled 30 voluores.
I tr ,.

2. Find the volunte strcngth of 2N H2O2 solution. I S i:.

4. C-alculate the antount per litre of I0 ntlolr sr,
[ 11.2 volumel
of hydrogen peroxide labellcd 20 volull]cs.
I 60-- j

11.12.5. Properties of Hydrogen kroxide 6. The dipole moment of HrO, is littlc rl

(a) Physical properties. (2. l D) than rhat of Hro (l .84 D).
.. .1. i!." hydrogen peroxide is a thick syrupy
liquid with pale blue colour. TABLE 11.5. Some Phlsical
2. It has a bitter taste. Characteristics of HrOr.

1. Hydrogen peroxide is more deose (L.rl4 Melting poiDt 2',12.4 Density (Lquid
g/cmr) and more viscous than water. This is due to (K) ar 298 K)
the reason that the molecules of HrO, are even (8 cnr ')
more highly associated through H-bonds than Boiling poiDt 42i Viscosity at
HrO molecules. (cxtrapolared) 294 K
(K) (Centipoire)
1.9 Dielectric con-
Pr9SSUre at stant of 298 K ,

298 K(nm Hg)

Density (solid t.6434 Electrical coD-
ar268.5) 15.'l x l()
5. It is completely miscible with water, alcohol ducriviry ar 298'
and ether in all proportions. (gcm ") K (a-l cm-t;
11132 Pradeep's

(b) Chemical properties. 1. Decomposition. In basic mediwn,

Pure hydrogen peroxide is an unstable liquid and H2O2+ OH- + 2c- ....- 3oH-
decomposes into water and orygen on long stand-
ing or hcating. Some important reactions in which hydrogen
peroxide acts as anoxidising agcnt are givcn bclow:
2l120r- 2H2O + Oz;AH=-196.0kJ
l. Oxidising action in acidic medium.
It is an example of quto-oxidotiotl ar,cl outo-
(i) It oxidises acidifi ed fetolts s lphqte tofenic
tcduclion.
,tulplurte
The decomposition is further accelerated by
the presence of cerlain metalions (e.6 Fe2+), metal
H2O, ---------r H2O [Oi+
powdurs (Co, Au, Ag, Pt etc), and metal oxides (c.g 2FeSOo +HrSOu +[O] + Fe,(SO{)r + H2o
MnOr). Evcn carbon, rough surfaces and light also
catalyse its deconrposition. 2FeSOo +HrSOo +H2O2 *Fe2(SO4)3 +2H2o
2. Acidic nature. Pure hydrogcn peroxide
tlJrnshhtc litmusrel,, but its dilute solution\sneutral or 2Fe2+ + H2o2 + 2H+ 2Fe3+ + zHzo
k) /irrxrr. I t thus hehaves as aweak acid Its dissocia- (ii) It oxidises -
acidihed potassiunt fer-
tion constant is 1 .55 x 10-l2at2g3Kwhichisonly rocyonide to poto ssium feqicyanide
slightlv highcr than that of water (1.0 x 10-11). HzOz-H2O+[Ol
Tlurs, lrydrogatr pcroxide is or y a .ilightly rtonger
ucid tltotl leoter. Since hydrogen peroxide has two 2Ko[Fe(CN).] + + [O] ----'----+
H2SO.
ktrti:ubic H- olotn.r, it forms two serics of salts, i,e., 2Kr[Fe(CN)o] + K2SO4 + H2O
I\rltrtltcroxidcs (qcidic ta :i) anclpenxides (nonttal
t0lts ).
H2O2 .- H+ + HOt (hydroperoide ion) 2Ko[Fe(CN). + H2So4 + H2o2 -------'
I-12o, ...,' 2I'l+ + ()3- Qteroxide ion) 2K.[Fe(CN)5] + K,SO4 + 2H2O

Thc acidic nature of hydrogcn peroxide is or 2[Fe(CN)6]a- + H2oz+ 2}l+

shorvn by il.s neutralization reactions with 2Fe(CN):- +- 2H2O
hydroxidcs ancl carbonates.
NUOH + H2Oz ..._ NaHO, + H2O
(iii) It tiberates iodinc from ocidified potas-
situtr iodide solutiott
Sod lrydroperoxide
HzOz .-_....rH2O + [OI
2NaOH + H2O-r"--'+ NarO2 + z}1zo
Sod peroxidc 2KI+H2SO4 +[O] K2SO4 + 12 + H2O
Ba(OH), + H2O2 ----------+ BaO, * 2HrO -
3. Oxidising and reducing character. 2KI + H2SO4 *H1(), "-""+ K,SO1 +1, +2H2o
Hydrogcn peroxide bshaves as an oxidising as well or 2I- + H.rO2 + 2H+ -------.Iz + 2H2O
as a reducing agent in both acidic and alkaline
solutions. Thc oxidation state of oxygen in (iv) Hydrogen peroxitle oxidi.tes icc-cold
hydrogen peroide is - 1. It can be oxidised to O, o cidif ed potas s ium di c ltorno t e s o h li ot t ( c ont q ini try
r

ether) to chromium pentoide which dissolves in

(zero oxidation state) or reduced to H2O or OH-
etlter producing a blue colowalion.
(-2 oidation state for orygen). However, HzOz HrO + [O] x4
It.yrlrrryart peroxide is a powerful oxidisingagent bul a
tftak rcducin? sgenl. tlCrro' +- H,SO4 + 4[O] -------i
(a) Oxidising character. Hydrogen peroxide I!SO. + 2CrO, * Hro
acts irs an oxidising agent both in acidic as well as
in alkaline medium. ...._
IqCr2OT + H2SO. * 4H2O2
Itt ucitlic ntcd un,
K2SO4 + 2CtO5 +5H2o
HzOz+2|J+*2e- ZHzO Chlonriu pentoxidc
-
 HYDFIOGEN 1 1/33

Chromium pentoxide is actually a peroxide or Mn2+ + H2O2 + 2 OH- -----------r

o-- .,o Mrr0z + 2H2O
having the structure I )Cr(
o'' ll \o (iii) It oxidises cftro mium salts kt chroinates in
o alkaline medium.
(u) Hydrogen peroitle oidises leud sulphidc Crr(SOn), + 3H2O2 + 1ONaOH
b lectd sltlplute Chromiunr sulphate
Hz()z HrO + [O] x 4 __ 2 NECTOI + 3Na2SOa +8H2O
Pbs + 4[ol ------------' PbSoa Sod. chromatc
or 2Ct'+ +3Hzo+ looH-
Pbs + 4H2O2 PbSOn + 4HrO 2CrO?- + 8H2O
bad^sulPhide -------rt ad sutphare (iv) It oxidises/ozfl aldehyde
(Black) lwhiicl
to formic acid
HCHO + HzOz HCOOH + H2O
This reaction is used in restoring the white Formaldehydc F_onnic acid
colour of lead paintings which have blackened due -
(v) It oxidises benzene to phenol bt alkaline
to ths formation of lead sulphide by the action of medium
HrS present in the air. On treatment with H2O2,
C6H6 + H2o2 C6H5OH + H2O
lead sulphide (black) changes into lead sulphate
Benzene -.-.-' phenol
(white) a.od thus the colour of lead paintings is
(b) Reduclng char8ctn In presence ofstrong
restored,
oxidising agenLs, hydrogen peroxide behaves as a
(vi) Hydrogen percide oidises HzS to sul- reducing agent both in acidic as well as alkaline
phw dnd sltlphurous acid lo ntlphuic acid. medium. In all these reactions, molecular orygeo is
H2S + H2O2 """"-- 2 H2O + S always produced by the combination of HzO2 with
H2SO3 G) + H2O2 @O -----r the orygen atom released by the strong oxidising
agent :
HrSOo (aq) + H2O o +
H2O2 IOI --------.--r HrO +O,
(vir) It oxidises mercwy to mercuic oide in fmm oxidising
acidic medium agent

Dil. It2so4 Acidic medium,

Hg * HrO, HgO + H.O HzOz ..........- ZH+ + or+ 2e-
2. Orddising actlon in alkaline medlum Alkaline medium
(i) It oxidises rulpt ites, nitrites and srsenites to HzOz +2OH- .+ZHzO +Oz +2e-
sulphates, nitrstes and a.,renates respectively in
Some important reactions in which hydrogen
alkaline medium.
peroxide behaves as a reducing agent are given
NarSO, +HrO, --- Na2SO4 +H2O below :
Sod. sulphite Sod. sulphatc
1. Reduclng action lo acidic medium
KNO2 + H2O2 ----------- KNO3 + H2O (i\ It reduces .ocidified potassium perrnon-
Pot. nitrite Pot. nitiatc ganate solution. As a result of this reaclu,on, the pink
NarAsO, +HrO2 + Na3AsOa +H2O colour of KMnO n solution is discharyed
Sod. arsenite Sod. aEenate
2 KMnOo * 3 HrSOo
(ii) lt oidises manganese salts to mqngqnese
dioxide irt alkaline medium. + 2 MnSO4
K2SO4
- + 3 H2O + 5[Ol
MnSOa + HzOz + 2NaOH H2O2 + [Ol ......--. HzO + 02] x5
Mangauese sulphate

........_ NarSOo + MnO2 + 2H2O 2KMnOn + 3 H2SO4 + 5H2O2

Manganese dioxide IISO. + 2 MnSOo
--'
+ 8H2O + 5C)2
11134
, !,'. Ne.1., Course Chem istrCltifrlD

or 2MnOf, + 6H+ + 5Hr0, ----"'' (ii) It ruduces fenic salts to lenous solts in
olkaline medim't
zMrf+ + 8H2o+502
2Fe3+ (aq) + HrO, (ar) + 2 OH- (aq)
(ii) It reduces acidified potassium dichromate -
2Fe2+ (aq) + ozG) + 2H2O (t)
solution. As a result of this reaction, the orange
colour of KrCrrO, changes to green due to the |ormu' (iii) It reducer alkaline potassium fenicyanide
tiotl ol chrotnium salt. to p ot o s sium feno cyanide
IlCrrO7 + 4 H2SOa .-...._ 2 Kr[Fe(CN)r] + 2 KOH -----""'+

IqSO4 + +4HrO+3[0]
Crr(SOo), + H2O + [o]
2 Kr[Fe(CN)u]

Hro2 + [Ol '--------- H2o + 02] x 3 H2O2+ [O] +

H2O + Oz

IlCrrO7 * 4 H2SO2 + 3HrO, 2 \[Fe(CN)61 + 2KoH + Hzo2

Pot. ferricyanidc
I!SO. + Crr(SOo)3 + TH2O+3Oz
- ----, + + O'
2 rqlFe(cN)61 2H2O
or CrrO]- + 8H+ + 3H2O2 Pot. ferrocyanid
-*
zcf+ +7H2o+3,.J2 or 2 [Fg(CN)5]3- + 2 oH- * H2O2
------'
Qii) It
reduces monganese dioxide to rnan' 2 [Fe(CN)uf - + 2H2o + {)2 4s
ganese sulphqte in presence of dil H2SOo.
(iv) lt r edtces meta I oxides to metals, i.e., silver
MnO2+ H2SO1 ......-MnS()n + H2O + [O] oside to silverin the alkqline medium. Howeve4 leud
dioxide is reduced to lead monoxide.
H2O2+[Ol
AgrO * HrO, + H2O + Oz
* -H2O*02
+ HzO2 ......._ ----2Ag
MnO, HrSOo PbOz + HzOz ._ PbO
MnSOn * 2H2O+ 02 Lead dioxide lJad monodde

(iv) It reduces ozone to diorygen + H2O + 02

O: ...........' Or+ [O] (v) lt red,uces hypohalites to halides in alksline
Hro2+ [Ol .-.-- Hzo * oz nrediunt
NaOBr +H2O2 + NaBr + H2O + C)2
H2C)2 + ()3 HzO + 2O2 Sod h,?obromite
---
(v) Chloine and bromine arc reduced to HCI CaOCl2 + H2O2 CaCl2 +H2O+O2
and HBr respectivel). This property is called An- Illcaching powder -+
tichkrr. 4. Bleaching action. The bleaching action of
Cl2 + H2o + zHCl + [O] hydrogen peroxide is due to the noscent orygen
which it liberates on decomposition.
HrO, + [O] ---""""' HzO + Oz HzOz ' [O] H2O +
HrO2 + Clr._ 2 HCI + 02 The nasceut oxygen combines with colouring
matrer which, in turn, gets oxidised. Thus, rhe
and LIrO2 * Br, ..-..._ 2HBr + O, bleaching oction ol HrO, is due to the oidation of
(vi) It reduces hypoholorts dcid to hqlide ioa itl colouingmattet by nqscent ollgen.It is used for the
ucidic medirm bleaching of delicate materials like ivory, feather,
HOCI (aq) + HrO, (aq) silk, wool etc.
HrO+ (aq) +-Cl- (aq) + <)r@) Colouring matter + tOl ....".......- Colourless matter
2. Reducing action in alkaline medium 5. Addition reactions, Hydrogen peroide
rcacts with olkenes to form glycols.
(i) It reduces potassium permangsnqte to ntqn'
ganelte dioxide in alkalitrc medium. cH, cH2oH
2 KMnOo + 3HrO, (rq) .......' 2 MnO2 (r) ll +Hro, I
@q)
+ 2KoH (aq) + 3or(g) + 2H2o
cHz - cH2oH
o Ethylene Ethyle nc glyml
HYDROGEN 1 1/3s

11.12.6. Uscs of Hydrogen Peroxide
(i) The most important irdustrial use of
HrC), is as a bleaching agent for delicate materials
like textiles (silk, wool), paper pulp, straw, leather,
ivory, oils and fats.
(r'i) Domestically, it is used as a hair bleach
and as a mild disinfectant.
(rr) It is extensively used to manufacture iaor-
ganic chemicals like sodium perborate andpercar-
bonate which are important constituents of good
quality detergeDts.
(iv) It is used in the production of epoxides,
proplyene oxide and polyurethanes.
(v) HrO, is also used in the synthesis of hydro-
quinone, pharmaceuticals like cephalosoporin and
food producs like tartaric acid.
(vi) HrO, is increasiagly being used in en-
vironmental cheElstry to control pollution by
(i) treatment of domestic and industrial effluents
(ii) oxidation of cyanides and restoration ofaerobic
ca[ditioD.s to sewage wastes.
(ur) It is used as an antiseptic under the name
perhydrol for washing wounds, teeth and ears.
(vi ) It is used for restoring the colour of lead
paintings which have blackened due to the action
of HrS present in the air oo lead paints.
(rr) It is used io the laboratory for detecting
the presencr of ckomiun, titaoium and vanadium
salts with which it yields peroxides of characteristic
colours.
(x) 93Vo HrO, so\ttion is used as an oxidant
for rocket fuel and as a propellant for torpedoes
and submarines.
(xr) It is used as antichlor (to remove Clr) in
texti-le industry to remove cxcess of chlorine after
bleaching operations.
U.12.7. Tbsts of Hydrogen hroxldc
(i) H2Oz on treatnent with atr acidifed solu-
tion of titanium salt gives a yellow or organc colour
due to the formation of pertitanic acid (H2TiO4)
Ti(SO4)2 + H2O2 + 2 HzO ------ HzTiOl
+ 2 H2SO1
(li) It liberates iodine from KI solutionwhich,
in turn, gives blue colour with starch solution,
(r'ii) When an ethereal solution of HrO, is
shaken with acidified solution of IQCrrOr, blue
colour appears in the ethereal layer due to the
formation of chromium pentoxide (CrOr)
(iv) When brought ir contact with H2O2 solu-
tion, afilter paper with black stain of PbS turns white.
(v) It decolourizes acidified KMnOo solution.

1 Peroxides. Melallic 6ides which on reatment with dihue acid|; prod,uce hydrogen peroide are called peroider.
For fiample, NEO2and Ba02. lD lhese peroxides, the two oxygen atoms are linked hy a single bond and each
oxygen atom has aD oxidation state of-1. In other words, all peroxides crl)tain a peroxide ion ( O3-) haviDg

the structure -: O-O :-. In lhis structure, all the electrons are paired and hence all peroxides are diam{rP.

netic
'fhere are certaiD other oxides like PbO2 and MD02 which may be mistaken as peroxides. These con'tpouDds,
however, do not Sive H2O2 on treatment wilh dilute acids. As such these contpounds do Dot clDtain a peroride
ion (o1-) and hence they cannot be called as peroxides. Actually in these compouDds the rwo oxygen aroms
are linked to the metal atom by a double bond and henc are called dioxides, i.e., O = Pb = O (lead dioxide)
and O = Mo = O (mangenses dioxide). In dioxides, rhe oxidation state ofeach oxygen atont is -2.
: Superoxides, Bcsides peroxides, alkah metals also form higher oxides callcd supcroxides. For example,
Potassium superoxide (Ko2), rubidium supcroxide (Rbo2), c.esium supero(ide (csoz) etc. All rhese supcr-

oxi(les mnl ain a suPeroxide ion, l. e. Ot havrng rhe structure, , O-O -.

, Thus all supe roxides contai[ an ocld

numbr of eEctrons (ia 13) and hence are paramagrctic.

1
'1136 Pradeep's

apPlTp:v@lr&KNowuEe6-E{C-ONilip.
lil 3 o the tbllowing types :
mber of tbe elemcnt (M) can be deduced fronl the
orygeo as-2 aro callcd normaloxides For cxaDrPle,

HzO, NazO, MgO Al2O3, CO2 etc. All these oxides contairr M-O bonds'
number ortbe
(iD poly;xues. .Ihese oxides colrtai|r morc oxygen than \pould be expecred from thc oxidation
ilcmeni ltrl;. mese trave becn further classifierl into Peroxides, aDd superoxides'

ll.l23.StructurofHydrogenhroxirle.Thereareseveraladvantagesofhydrogen

nitrogen that are responsible for acid rain, -nor

COr Ihat is responsible for the green house effect,
nor carcinogenic hydrocarbon's, nor lead com-
Pounds.
H oweve
achievins the
peroxide in the gas pha.se and the crystalline state is to find"out a
are shown in Fig. 11.13. tionof H2.TW
are : electrolysis of water and
the thermochemical reaction
cvcle. The first method is not
90 2"
ect.rnomicallv viable since the
cost of proiuction of H, bY

H
----:i----l:---
\
i01.5. electrolysis of H2O is so high
that almost all H, is obtained
from natural gas which itself is
o o in short supplY. The other
method involves series of ther-
mochemical reactions in which
the only things consumed are
water and heat and the onlY
nroducts are hvdrogcn and orygcn while all other
,pccies are recycled. Clne such thermochemical
The coal and oetroleum reserves ofthe world
reaction cycle is
arc limited and ari fast dwindling. Therefore, the 175 K
3 FcCl2+4 H2O-Fe3O4 +6HCl + Hzll< Z
475 K
2 Fcaoa + 12 HCI + 3 Cl2
6FeClr+6H2O+Oz
-
7L5 K
2 FeCl, .-..._ zFsclz+Clzl x3

2112() zHz+ Oz
economy. -
HYDROGEN 11137

Whether any of the methods listed above can
produce H2 cheaply enough to make its use prac-
ticable is a most distant possibili(y. The other prob-
lem is to hnd out an effective means of stroring
Hr. The gaseous H2, because of its bulk, is difficult
to store, but liquid H2 can be stored relatively easily
and safely in cryogenic tanks (already in use for
space programme in U.S.A.). It is also feasible to
transport liquid H, by road or rail tankers of20,000
US gallons capacity. It can also be stored in under-
ground tanks and transported by pipelines. How-
fuel cells are rountinely used as power source on
spacecraft. A 4 5 megawatt fuel cell power plant
(with conversion efficiency of 70-85%) has been
established in Tokyo. Unfortunately such fuel cells
are too expensive to be used in consumer oriented
applications in developing countries like India.
The combination of all these potential uses of
hydrogen could bring a fundamental change in our
way of life, giving rise to what is called hydrogen
economy.
11 .'14. Use of Liquid Hydrogen as a Fuel ::l:, :i: I
,
ii i ,:i r i::i

ever, it may not be convenient to store liquid H, in Use of hydrogen as an automobile fuel has
a home or a car since the boiling point of H, is very many advantages :

low (20.4 K) In either case (gaseous orliquid form)
H, must be kept out of contact with o4gen or air
with which it forms explosive mixtures. The only
alternative left is to store H, in a metal or in an alloy
(such as iron-titanium alloy, LaNir, Mg-MgHr,
Ti-TiH, etc.) as interstitial hydride.
The gas can then be released on mild heatinq.
ln an automobile, for example, this storage system
would replace the gasoline tank. The heat required
to release H, from the metal hydride could come
hom the exhaust gases from the engine.
Ifthe problems discussed above can be solved,
not only can H, be used to substitute gasoline as a
fuel for transportation, but it could also replace
natural gas for space heating. Moreover, because
H, is a good reducing agent, it could replace carbon
(as coal or coke) in many metallurgical processes.
And, ofcourse, itwouldbe abundantly available for
reaction with N, to produce NH, for fertilizer
manufacture and other use'. Hydrogen can also be
used as a direct substitute for electricity which can
be generated by wide spread use of fi.rel cells. The
(i) First the heat of combustion of H2 is by far
the largest, i.e., 115 megajoules per kilogram
(MJ/kg) as against 43 MJ/kg for a typical unleaded
gasoline, 39 MJ/kg for ethanol and Z) MJ/kg for
methanol. Thus, an automobile engine is ?5 - 50Vo
more efficient when it uses H2 rather than gasoline.
(i) The exhaust is free from pollutants like
CO, CO2, Nq, SO2, hydrocarbons, aldehydes and
lead compounds.
(iii) Combustion product is water with some
traces of 'ritrogen oxides.
(iv) Internal combustion engine can be easily
modihed for use of hydrogen as fuel.
The most cffective means ofstoring hydrogcn
is in the liquid form. The liquid H, is widely used
as a rocket fuel since it gives higher thursts than
most of the other frrels.
The range of supersonic aircraft could be in-
creased if the aircraft used liquid H, as a fuel.
Further hlpersonic aircrafts would also become
pqssible if liquid H, is used as a fuel.

c'?*ne,entaa,|*Aue.-q*i,p,ns.,
t.r I lVhich isotope o[hydrogen is used as a tracer in orpxnic renctions.
Ans. H)'drogen has three isotopes, qz. H, D and T Due to dittereDce in masses, the rate constants ofthqse isolopes
with the saore substratc are differeDl. ln orher worcls, both D andT shw irotope effecl But since T is not only
raclioactive but is also least ahundant hydrogeD isotope, therefore, D is used as a tracer to study the mechanism
oforganic reactions.
1.; I Name one examPle of a reaction in which dihydropen xcts (i) rls nn oxidising agent nnd (il) os a reduclng
agent.
Ans. (i) In rhe reaction ofdihydrogen with merals ro forD] n.tcral hydrides, it acts as an oxidisiDg agent.

2 Na (,) + H, r<,Ia 2 Na+ H - rrl

 1 1/38 Pra c! e e y's N e ut:',,,C o urs e, Ch e n iiiig,JfrlD
Ilere, Na has been oxidised to Na+ while <JihyrJrogen has been reduced to hydride (H-) ion.
(ii) In the reaction of heated cupric oxide with dihydrogen to form Hro antl copper n:etal, dihydrogen acts as
a reducing agent.

cuo (.r) + H2 ('r) '"ul au (r) + H2o E)

Here, CuO is reduced to Cu while dihydrogen is oxidised to HrO
Q'-1' Hydrogen forms three types of bonds in its compounds. Describe each type of bonrling using suitnble
examples. -
W.C.E.R.T.)
Ans. Hydrogen forms compounds in three different ways:
(i) by loss of electront as in the reactions of tI2 with metal oxides, le., heated CuO and FerOo.

cuo +H2G) '"ul

(s) (r) + rr2o (g) ;
H"':
",
.HzO
FerOo (s) + 4 HzG) 3 Fe trr; + 4 (g)
(ii) by goin of elech.ons as in the reactioDs of H, with metals.

Heat
Na 1s1 + Hz@) :::- 2 Na+H- 1.r; ;

Ca (r) + Hz@ Y ca2+ (H- )z

(iii) by .rhaing of electrow as in the reactions of H2 with halogens :

HzG) + F2G) -IIL 2H-F(/) ;

23K

Hz@) +",, G; ry*l zH-ct G)

sunlight
Q. 4. Conc. H2SO4 cannot be used tor drying IIr, Why ?
Ans. Conc. H2SO4 on absorbing HrO from moist I{, produces so much heat that hydrogen catches fire.
Q. 5. Why is diorygen paramagnetic ?
Ans. M.O. diagranr shows that O, has two unpaired elecfirtny and thus shows paramagnetism.
Q. (r. Can marine species live in distilled wnter ?
Ans. No, because distilled HrO does not contain dissolvecl Or.
Q. 7. A sample of hard water is allowed to pass through an anion exchanger, WII it produce lather will soap
eaSily ?
*t' and Mg2+ ions are still prese nt and these will react with soap to form curdy white ppt. Therefore,
Io.._9'+
it will
not produce lather with soap easily.
Q. tt. Can dlstilled water he called as deionised water ?
Ans. Yes. Distilled water does not contain any cations and anions and hence can be called as deionized water.
Q. 9. Explain why oxide ion is called a hard ion ?
Ans' Oxide ion is very small in size and thus cannot be easity polarized and hence it is called a hard ion.
{). I{1. Anhydrous BaO, is not used for preparing HrOr. \ilhy ?
Ans. Anhydrous BaO, is not used because the BaSO4 formed during the reaction forms a protective layer around
unreacted BaO, and the reaction stops after sonte tlnte.

fr
 HYDBOGEN 1 1/39

Ve"1y.,,Q*l1oyr.A1,swg.5,Qu,9_2ti.o-1,?, CARRYING ,I MARK

Q. l. Which isotopc of hydrogen (i) does not contflin neutrons, (ii) contslns equol number of pmtons end
Deutrons, (ii) is radioactive.
Ahs. (i) proliunr Gl) deuterium (iii) tritiuD.
- Q. 2. Why is dlhydrog.n Dot prefered in hatloons these days ?
Ahs. Dihydrogen is highly combustible and hence rs likely to cstch fire in presence of exce$s ofair
Q. 3. Name one compound each in which hydrogen exists in (i) +I and (ii) -1 oxidation stote.
ADs. (i) HClor H2O or NH3 ( )NaHorCaH

Q, 4. What is the importahce ofheflr] wat.r ]yith reg.rd to nuclear power generation ?
Ans. It is used as a moderator to slow down the neutrons produced as a result of fission and thus belps to coDtrol
the nuclear reactioos.
Q. 5. How is heaq vater produced from ordinary wnter ?
Ans, lr is obtained by repeated elecrrolysis of ordlnary warer contaiDing 3% NaOH.
Q. 6. WhAt do you mean by 15 yolume HzO2 solution ?

' Ans. 1cm3 ofa 15 volume HzOz solutioo gives 15 n)lofOz ar NTP.
Q. 7. Namc two compounds which rettrrd the decomposition ofH2O2 solution.
Ans, Actanilide, glycerol.
Q. E. Colculste the smount ofH2O2 present in l0 ml of25 yolume H2O2 solution.
Ans. 10 ml of 25 volunre H2O2 liberate O2 = to x 25 = 250 nrl at NTP

2H2O2 zHzO+ 1;2

6Eg - 22400 ml at NTP

. . Anrount of Hzo2 lhat ,.!lll hberate 250 nrl of oz at NTP =

\ff = o lsl z
Q.9. Hydrogen peroxide is used to restore the colour ofold oilpaiIltings contoining leod oxlde. Write a balarced
equotiotr ofthe resction that tokes plnce in this proc;ss.
Ans. Refer to Ans. to Q. 2. of C.B.S.E.-PM.T (MAINS) SPECTA! on pa8e l1l4?.
Q. 10. 10 ml ofa given solution ofH2O2 contains 0 9l g ofHrOr, Express its strength ln volume.
- Ans. 689 of H2O2 produce 02 = 2200 mlai NTP

- 22400.,\ 0 et
''. 0 91gof H2O2will produce 02 =300nrlatNTP
. volume strength = 199 = ro

Q. 11. What is the cherDicol composition ofzeolite ?

\
Ansr Hydrated sodium alumiDium silicate, NqAIrSirO, .xllrO. .
. it prcpered ?
Q. 12. Whot is water gos ? How is
Ans. An equimolar nlixture of CO aDd II2 is called water gfls. Itisprepared by passing steam over red hot coke,
1215
c(') + Hro (s) co 6; + n2 e)
Q. 13. Name one example ofa reoction in lyhich dihydrogen acts (i) asan oxidising agent (ii) asa reducihgsgenL
Ars. OxidisiDg ageDt : 2Na + H2 -....... 2Na+ Il-
Heat
Reducing agent : CuO + II, Cu + HzO.
Q. 14. What happeDs !f,hen heavJ - is added to calcium carbide
wster ?

ar
 11140 Neul Coutse Clrent i strq
Ans, Deuleroace9ene is formed, (hq + 2D2O Ca(OD)z t DC = CD
-
Q. 15. Whnt is deminerolized wnter ? IIow is it obt.nillcd ?

Ans. Water which docs not contirio cations and anions is called den'rineralized waler. 11 is obtained by PassiDg
ordinary water through ion exchange reslns.
Q. 16. The hoil ing point of H2O is higher thfln that of fI2S. ExPlain.
Ans. Due to extensive iDternlolccLr lirr i I -bondiDS irl I l2 o, I hc b.p, of H2c) is ntuch hiSher thaD that of H2s.

Q. 17. Whnt is hydrolith ? Hotd is it prePared ?

A
Ans. C-a + Hz ...* CaHz (hydrolith).
Write the structures of trvo complex metot hydrides \rhich nre rlsed ns reducing agent
t. tu organic synthesls.
e. I
Ans, LiAjHa and NaBHa.
Q, 19. Whet type ofelements form interstitisl hydrides ?

Ans. d- and/-block elelneDts,

Q. 20. Writc tr?o uses ofibterstitial hydrides'
Ans. (i) Storing H2 aDd (ii) catalysts for hydrogenation reactions
Q. 21.
rrYhrt happens when chloroforD is trerted with hexry water ir Presence of$n slklli ?

Ans, Deuterochloroforn (cDCl3) is fornled. CFICI3 + D2o-....- cDcl3 + DoH'

Q. 22. Why is sodiurD chloride less sol hle in heary water than in ordinary\vater
?

Ans. Due to lower dielectric constant of D2O over I'12O, NaCl is less soluble in DzO thao iD H2O'

Q, 23. Explain why heryllium forms a covalent hydride while calcium forms sll ionic hydride'
Ars. Because of higher electronegativity (E N = I 5), Be forms covirlent hydride while due to lower
electronegativity (E.N. = I 0) Ca lbrDrs ionic hydride.
Q, 24. Give two ndvantages ofusibg hydrogen ns a ftlel over Snsoline'
Ans. High heat ofcon]bustioo and no Pollutants Iike S02' NO2,COrelc'
Q, 25, Explnin why electrolysis of ordinrtry water occnrs fnster
thnn hear? wnter ?
Ans. Due to lower bond dissociarion ene rgy of protium bonds in H-o-I{
thaD dsuterium bonds iD D-o-D,
electrolysis of Hzo occurs much tilster lhan that of D2o

Q.26. What is rneant by autoprotolysis ofwater ?

(\:( /tk /l)
Ans, Autoprotol,,sis of water means that two molecules of water react with each other t hrough Proton transfer ie.
one acts as the acid whrle the other dcts as the base. Thc molecule which accePts a Proton is coDverted into
H3O+ while that which loses a protou is convcrted tnto OH- ion'
Thus, H2O (l) + HzO (l) HrOt 1aq1 + OH- (aq)
acidl base, acid2 basel

Q. 27. tYhot is understood lry hydrogenfltion ? /'\ r''l- /(' 11)

Ans. Hydrogenation means addition otH2 in Presence ofa catalyst to multiPle bonds to tbrm saturated compounds.
\ior Pr orPd
For example, CH, = gg, + Hz ........-..-................. CH3 - CH3
Ethene 473 K Ethane
to say thot hydrogen can l)chave rs a metal ? stlte the conditions under which such hehaviour
Q, 2t, Is it correct
can bc possible ? \:( / li /
Ans. Yes, H2 can act as a metalunder very vcry high pressures'
Q.29.Ionichydridesorcfrequentlyusedtolemovetrlrcesof\YnterfromorgllniccomPouhds.whatisrtnderlyin8 /
hrsls oithis process ? \1(''Ir- I /l '

is a strong Bronsted base and hencc reacts $'ith I 12O readily liberatin8
H- H2 gas
Ans,

\
al
 HYDROGEN 11141

H2O (I) + H - (r) -* Hz G) + oH- (aq)

Q. 30, Although D2O re{arDbles H2O, chemiqlly yet lt is o toxic subctance. ExplsiD.
(N.C.E.R.T)
Ans. D2o is toxic siocc, D + reacts ar a much slower rare as comparcd to H+ in en4mc-catallze d reactions.
Q. 31, Give an exomple eBch ofan ionic hydride ond a covaleDt hydrlde. (t;.('.1: R I:)
Ans. IoDtc: NaH or CaH2.
CovaleDr: H2O. BrHu, CIIo etc.
Q. 32. Whnt is the dilference hetween hydrolysis and hydrotion ? r \ r ., /t .r r

Ans. lDteractlon ofH+ and OH- ioos of H2o wth the inrioD and the carion ofa sall respeclively to give the original
acid ard the origiDal base is called hydrolysis. For exan]ple
Na2COl+2HrO _2NaOH + HrCO,
sart Basc Acid
r: . Hydrslion, olthe other hand, nleans addition of H2O lo rons or molecules to form hydrated ioDs or hydratcd
salts, For example,
Na+cl- + Hro * Na+ (oq) + ct- (oq)
Sslt
CUSOa+5H2O- CUSOa . 5 H2O
<Colourle$) (BIuc)

5 A cARRytNG 2 or3 MARKS

Scc. I l.l Discuss the characteristics in which hydrogen resembles halogens.
to 11,2
2, Discuss two characteristics in which hydrogen rescmbles alkali mctab.
1 Explain w-hy hydrogen is besi placd separatety in thc periodic rable ofelemcnts.
(N.C.E,R.T)
S!c. lll 4. i
flow is dihydrogen prepared (i) from warer by using reducing agen! (id) in rhe laboraiory in pure
till.1. form and (iii) hldrocarboDs ? W.b.E.t.f)
5. wbat is meant by \mter gas shifr reactio''? Describe its use for the preparation ofdrhydrogcn.
(N.c.B.R.T.)
Describe the industrial applicaiions of hydrogeD depndcnt oo :
(i) the heat liberated when the aloms arE made to combinc on thJ iurfacr of a metal.
(ri) its effect on unsaturated organic slstcms in presence ofa cataly*t.
.
(ir'i) its abiliry ro combine wirh nitrogen uoder specific cooditioDs (N.C.E.n.T)
1. Explain the correct context in which the lbllo\ving terms are uscd.
(i) diprotium (r'i) dihydro8en (i!i) protoo aDd (iy) hydron.
N.C.E-L-T/
t. Name rhe i'otopes ofhydrogen. What is the imponancc of the heavicr isotopcs of
hydrogen ?
(N.c.E.R.r)
9.How will you prepare healy hydrogen is lhe laboratory ?
10. How many allotropes ofdihydrogeo are known ? What is their importance
? (N.C.E.R.T)
11. Cornplete the following reactio,rs :
(i) Cuo (r) + H2 G)..* (i,) co G) + H2@)+ (N.CE.R.T)
icc.l !.3. 12. How is dihydrogen obtarned from
to 11.1. (i) water (r'i) dilute acids (ir]) atkalies ?
13. How does dihydrogen react with
(i) Blue litnrus soturion (ri) chtorine (ai) flourine (iv) nitrogen (y) sutphur (yi) (arbor
(vii) sodium (vxr) ferric-ferro oxide (mag[etic odde) (E) carbon mooGide ?
11142
Pradeep's

14. Horv is dihydrogen obtained ftom

(4) dilute sulphuric acid (D) sodium hydroxide (c) watcr ? Givc oDc cquation in each case'
15. Give one method (other than electrolysis) for large scale Preparation of dihydroSen'
16. Name the different vmys in which hydrogen forms comPounds ? Give oxanlPles
Src. I l.tt. 17. What arc metallidintcritltiat tryOtUi f U*' do t ,y differ from moleorlar hydrides ? (N'C'E'RT')
1t. Hvdrolen forms compounds with elemcDts haYing atomic numbers: 9, 11,12and l7 Whatare their
ctiemi&t rormuue r i)omparc the ir cheorical behiviour. N'C'E'R'T)
lHlnL Hq NaH, MgHz and HCII
19. Namc the class of hydrides to which H2O, BzH6, NaH and LaH3 belons What is understood t'y
hydride gap ?
(N'C'E'RT)
20. Distioguish between salt like and covaleDt hydrides'
21. Disruss bricfty thevariatioo in boiling Poinls amoog the hydrides otSroups 15, l6 and 1'7.

What are intersdiial hydrides ? Discuss their iDportant uscs.

Discuss briefly the characteristics ofsalt likc hydridcs.
Sec, I1.9. 24. Explaio whywater has high boiling and melling points as comPared to H2S' (N.C.E.R.T)
to 11.11.
(N.C.E.R.T)
25. kplain the structure of ttle common form of ic.e.
26. HydrogeD fornls three tyPes of boods in ils compounds. Describe each tyPe of bonding usiDg suitable
e*ampies. @'C'E'R'T)
27. Explain the amphoteric nature ofwater. (N'C'E'RT)
2ll, Describe sonre unusual ProPerties of water. (N C'E'R'T')
29. Whar is the difference btween hydrolysis and hydration @'C'E'R'T')
30. Why do lakes freeze from toP towards bottom 'l (N'C'E'RT)
31. why is ice less deNe than water aDd what kind ofattractive fotces must be overcome to olelt ice ?
(N.C.E.R.T)

32. Complcte lhe following reaclions:

(r) CJo (r) + H2o (f .... (,,) Na2o (r) + H2o (D- (iii) Fe ('') + Hzo (s)' (N.C.E.RT.)

33.
- Elcmeots witb atomic numbrs 17 and 20 form comPounds with hydrogen Write the formulae!f
ttr"r" rompounOs aDd coolpare their chemical behaviour in water'
q'C'E'R'T')

lIIinL HCl, CaH2l

34, Distinguish bet\ryeen (i) hard and soft water and (ii) temPorary ard permanent hardness'
(N.C.E.R.T.)

35. Discuss the Principle and method of sotlening of hard watcr by organic ion cxchaDge resins'
(N.C.E.R.T)

36. Discuss the importanc! of heavy waier iD nucleat reactors d'C E R T)

3?. Explain : (i) water has maximum density at 277 K (ii) ice tloats over water'
3ll. Describe Permutit procEss for softening of hard water'
39. Discuss brie$y demi[eralisation and deionisation of water by ion excban8e resins'
40. Describe the principle ofsequestration for softeDing ofhard watcr'
41. Calculate the hardnes ofa water sample whioh coDtaiDs 0 OOl mole of MgSOa dissolved per litre of
lAns. = 100 pPmI
lhe solutio[.
watcr oo (i) Calcium carbide (ii) Calcium PhcPhidc (iri) Magnesium nitride ?
42- Whai is Lbe action of
to form hydrate'
43. What are the $ts)a in which water molecules are boDded to the anhydrous salt
44. Wtry is water an o(ccllent solvent for ionic or polar comPounds ?

45. How is heavy water

PrePared
?
from normal water
(N'C'E R T')

46. Discuss the imPorta[ce of heavy water is nuclear reactors

(N'CE'R'T')
water'
47, How is heavy water Preparcd ? Compare its phlsical ProPerties with that of ordinary
HYDROGEN 11143
4t. What is thc action of heaty water on
(i) sodium (ri) sodium hydrqide (rii) ammonium chtoride and (iy) sulphur rriqidc ?
49. NT: tle follo ingcotpounds and wlite down howcaD $ey bc prepared frorD hesry yatct:1.
(0 cDCl3 GD DCI (rii) D2 (iy) qD2 and (y) CDa.
50. whitc the structures of six varieries of heavy water difteriDg in atomic mass of cfrygen alom and thcir
molecular masss.
Scc I L| 2 Sl. Comparc the structures of HzO and H2O2.
(N.C.E.R.I)
5a Compare the chemicl propertie.s of H2O and tlrOr. (NC.E.R.t)
53. sho' by propcr chemicar reaqions ho, hydrogen Fr idc can tu[ction boo u an qidiling 8trd I
reducing agent. N.C:E.&O
54. Complete the following equatioos :

(i) PbS (r) + H2Oz@q- (ii) MnO; (aq) + H2O2@q+ (N.C.E.kT)

What happens when H2O2 is lreated with
(.t) acidified potassium pannangaDare
(b) lead sulphide
(c) alkaline potassiu nt ferriryanide
(d) aciditied ferrous sulphare
(?) sulphurous acid ?
(f) sodium arsenire ?
56. What bappens wheo
(r,) Barium peroxide is treated with cold dilute sulphuric acid.
(6) Sodium peroxide is lreated with cold dilute sulphuric acid and the rsulting mixturc is cmled below
n3K
(c) Barium pcrodde is treted with pbosphoric acid
(d) Hydrogen peroxide is treated with sodium carbonate
(e) Hydrogen iodide is added ro hydrogcn peroxide?
57. Write equations for the following rcactions :
(4) A solution of 2."thylanthraquiDol in a nti*ure of benzene and cyclohemnel
h ffiidiscd
(b) Ttre organicproduct obrained in (4) is treatedwirh hydrogen in the prescnce ofpaladium
cararyst.
(c) Perqydisulphuric acid is hydrollsed
(d) Chlorine ts passed through hydrogen peroxide solution
(d) Sodium hydroxide is treared wirh hydrogen pro(idc.
5E, Give ion elcctron equations for the following reactions :_
(a) Oxidation offerrous ions to ferric ions try bydrogeo perqide
(6) Oxidation of iodide ron ro iodiDe by hydrogen proxide
(c) Oxidation ofacidified permanganate ion by hydrogen percide
(d) ReductioD ofalkaline ferricJanide ions to ferrocyanidc ions
(e) Oxidation of tbrrocyanrde ions to ferricyanide tons In acidic medium.
59. "HydrogeD peroxide is a strong o\idising agenr borh in acid
and alkaline medium.,,Justiry gMng
suitable reactions.
60. How is a solutioD of H2O2 prepared by electrol,,sis of an aqueous solution of ammonium
sulphate
and H2so4 ?

61' Ho', is a sorution of H202 concer)rrated ? why cannot ir be concDtrated by disiirario[ a[ ordinary
Pressure ?
62. Justify the statemeDt ,An aqueous solution of h,drogeo percfiide
is weakly acidic,,.
11144
Pradeey's tli;Nii4

63. In the preparation of hyclrogen peroxicle, the use of PhosPhoric acid has atl aclvantage over dilute
sulphuric acid. ExPIain.
64. Name the conrpound of hydrogen ancl orygen which acts both as an oxidising as well as a rcducing
agent. Give one n:ethod for its preparation.
65. How does HrO, act as a bleaching agent ?

66. . Give three uses of hydrogen peroxide.

67. Explain :
(r) H2O has a higher boiling point than water.
(ii) H2O2 cannot for Prolonged pcriods'
be stored
Write
Hydrogen peroxide is used to restore the colour of old oil paintings containing lead oxide.
a
6lt.
tratanceo equation for the reaction which takes place in this process.
Scc, ll.l3 eS. Whrt it unierstood by hydrogen econorrly '! (N'C'E'R'T')
to I 1.14
70. what are advantages of using hydrogen as a fuel over gasoline or ooal ? (N.C.E.R'T)
of water.
71. Give one thermochen:ical cycle of chemical reactiolts depicting the decomPosition
72. Discuss two nrethods tbr storing hydrogen.
73. Discuss the use of liquid hydrogen as a fuel.

Sec. I l.l. 1. Discuss the position of hydrogen in the periodio table'

to I1.4.
2, What are isotopes ? Discuss briefly the structure, properties and uses of isotopes of hydrogen'
Scc. 11.5: 3. How is dihydrogen PrePared fronr :
tc I 1.7. (i) water (ii) acids and (iii) alkaties. Discuss its vartous uses'
How is dihydrogen prepared oD a commercial scale ? Give one convenient method for
preparing
4.
dihydrogen in the laboratorY'
5. Give equations to show the reactions of dihydrogen with : Na, Ca, CO, N, S' Cl and CuO.
Scc" i l.tt, 6. What aie hydrides ? Discuss their various types. Ho$'are they formed ?
7. Discuss briefly the nt types of hYdrides'
what doyou mean diffeient methods used for softening of hard water ?
S cc. 1 i.9. E.
to ll.l2. Briefly otplain the
the structure of (a) water in the gaseous and liquid states (D) ice. Explain why water
exPands
9. Discuss
on freezing ?
is the process
Give the equation for the auto-oxidation of 2-ethylanthraquinol to produce HrOr. Why
I ().
called auto-oxidation ? What is the advantage of this prooess ? Give one example of a reaction
with
stronger
equation in which ozone acts as an oxidant but no oxySen is produceQ. Which element is a
o*iOant than ozone ? (West BmgalJ.E,E' 2001)

11. Horry is hydrogen peroride prepared in the laboratory and on a commercial scale ? Giving four
6f .udn gie
iiactions starement that hydrogen peroxide acts both as an o:<idising as well
lustiryifre
as a reducing agent.
t2. Write notes on:
to II.l4 (a) Hydrogen economy and (D) Liquid hydrogen as a tuel of the future'
 AD'D,|,T :IONAL iU 5,EFU'L I N:f. 6 RVlAf I ON
Aionlc hJdrogi-lt is Produced wheu molecrrlar hydrogen is passd through
-tungsteo
.l'
elccrrodes (377U2i3 K).
an electric arc struck betwecn

Ele.tic ar.,3n3 - 42TjK

2H; AH = 435.9 kJ mol-l
The life time of atomic lrJdrogcn is 0.3 scc.
and hence it immediately gels converted into tbemolec1llarform
for welding pur[nss in form ofstomic hydroSen torch FIg. --- -a large
Iiberating
- aEount ofencr&r which is used
If.f+

BROKEN IRON PIECE

FIGURE 11.14. Atomic Hydrogen Torch.

Alomic hydrogen isvery reactive and hence it acrsas a powerfur

reduciDg agent. lt reducs, dides, chrorides,
sulphides and surphares or heavy merars and many alkari
miral salrs orhcr th; ;hrorioes ano srirftrarei. '- '
CuO+2H- Cu+HzO ; AgCt +H_ Ag+HCl
CuzS + 2 H * 2 Cu + H2S ; BaSO4 +8H * BaS+4HzO
It also reduces oddes ofnon-metals. For example,
CO2 + 2H- HCOOH
CO + 2H- HCHO
Paolo+32H 4pH3+ l0H2O
-
77t45
 Pra tl ee p' s, N e' u 6 q s v s 9i',',:, e hE' mi i s;t ygW[D
1'.t148

ADDrriuNAtu_QEr-u-L-!Nr-qBUAf!9|!'--':":',
Oz, Ag and Hg at tow temperatures to tbrrn their respective
hydrides'
It combines with
Or+2H-HzOz ; Ag*g.--AgH
nract wilh the substance to be reduced Ls called nascenl

chromic and chloride ions respectively'

'/1$Qo 1 /fl (na''cent hydrogen)
Zn + HrSOn
-
2MnO! + 6H+ + 10H' 2Mnz+ + 8HrO
Fe3++11 --- F"2++H+
Crrozr- + 8I{+ +6H 2Cr3+ + 7 HrO
-
ClOl+6H--* CI-+3H2O
of zinc and dil. H2so4, (ii) a mixture of tit't
Some common sources of nascent hydrogerr are : (i) a urixture
and (iv) ZiDc-copper couple and HrO or alcohol'
and conc. HCl, (ii) metallic sodium and absotute alcohol
The activity of nascent hydrogen may be due to :
ha association with a Part of
(0 it s liberation in form of tiny
chemical se satisfactory to explain the
bubbles
behaviour of nascent hYdrogen.
3.ComparisonhetweenAtomicandNascenthytlrogen.Mainpointsofdifferenceare:
atomic hydrogen is produced at
hydrogen can be produced cven at roon'l tentPerature but
(i) Nascent
elevated temPeratures.
(ii)Nascenthydrogencanneverbeisolateclbutatomichydrogencanbeisolated.
(iii)Reducingpowerofaton:ichydrogenismuchgreaterthanthatofnascenthydrogen.
Ingeneral,thereactivityofthethreeformsofhydrogenincreasesintheorder:
Molecutw lrydrogen (H2) < Narcen! hydrogen < Atomic lrydrogen
temperatures to
4. ained by subjecting a stream of molecular hydrogen at o-rdinary
in natu.re (half life = 0'33 sec) and conrbines
silcnt el 30,fi)0 volts' It is'very reactive
directlywithPbandStbrmingtheirrespectivehydrides. a little of HrSoo or
of heavy water containlng
5. Heavy hydrogen. It is manufactured by the electrolysis
NaOH to make it a good conductor of electricity'

zDz}(l) E""'o'tr',' ZDzG) + oz9)

Heavywater (Atcathode) (Aranode)
water on sodium nreta|.
ID the laboratory, it can be prepared by the action of heavy
zDz}(l)+2Na(s) + 2NaoD(ag) +D2G)
 HYDROGEN
11147

.P, SPECTAL
!1. SuD.llta'11l'li QUES7'10NS (Lot motwith LI.'t:)
Here, Cf + gets midircd to Cr6+.
Q. l. The proceds 12 H2@) + c- H- (B) ls en- ReduciDg lgent I
dotherElc (AII = + t5l kJ Eol-l),
- yetsalr like 2 K3lFe(cN)61 + 2 KoH + Hzo2 ..*
hydrides are krowD. Hop do you accourt for
this? 2& [FC(CN)5] + 2H2O + c}2
An& It is true thar formarioD ofhydride (H-) ioD is an Herc Fe3+ gets reduced to Fe2+.
endothermic process, yet alkaliand alkaline earth
mctals form salt like hydrides. This is due to the e. 5. A rvhite solld Is elthcr Nr2O or Ns2Or. A plect
reason lhat high latdcr enersr released (eDerry of red lituus pspcr tunr6 rvhite wheo it is dlpped
releasd duri[g tbe formatioo of solid meGl into I frshly mode aqueous solution ol the
hy whit solid.
M (i) Identtly ahe substoncr ond explsln wltlr
DC balanced cqustion
gas. (ir) ExplaiD rhatrould hrppeD to thc rcd titErs
Statues costed withwhitelead or long.xpo6ure if thc whitc solid ver thc other coDpoutrd.
Q.2.
to atmosphere turr black altd the origiDal (LI.T 1999)
colour con be restored on treatDentwith H2O2. tu& (r) NEO2 + 2H2O 2NaOH + H2O2
whv ? (Roo*ee 1987) -
H2Oz thus produced turns rcd litmus paperwhite
Ahs. On long exposure to atntosphere, $hite lead is
due to its bleaching astion.
converted into black pbs due ro the adion of
HzS present in the atmosphere. As a result, 0i) Na2O + H2O 2NaOH
statues turn black.
-
NaOH thus producd will tum red litmus blue.
PbO2 + 2ll2s _* PbS + 2H2O e. 6. Atr eleDent h86 its tDarlEum sDd EiDimum
On treatntent of these blackened stalues with + n s\il -m respccdvely
H2O2, the black pbs gets oxidised ro white the possibllity of uDdeBo_
on lu sny of ias coEpolld&
PbSOa and the colour is restored. ,n?
PbS + 4 H2Oz .+ PbSOr +,1 IIzO (We Benrat t.E-E. ZN3)
(.r A mixture of hydrazine and IlrO2 \yith Cu (II) Ars. Hydrogeo hasm imumaod miDimumqidation
-r states as + I and 1 respcrtively. Eement! of
catalyst is used as r rocket propellarlt. \yhy ? -
goup 14, ie., C, Si, Oc, Sn & pb caD also have
ADs. 'Ihe reactioD between hydrazine and H2O2 ts m$dmum and mioimum qidaaiotr slates of + 4
btghly exothermic and is acrompaned by a larte aDd -4 rEspcctilrly. But all these elements u Dder_
tncrease ln lhe volunle olthe productsand hencc go disproportionation reactions in some of their
thts ntl{ture is Lised ari a rocket propllant. compounds. For eEmple,
o
.NH2-NH2 (/)
Cu (ll)
il
- 2 H20, 111......._ 2H---C-H + NaOH *
N2G)t+4H2oG),l (o.N.ofC=0)
,.1 I Ilydrogen peroxide octs both as an oxidising CH3OH + HCOONa
agent ilDd as a reducing agent in alkaline solu_ - 2) (oN'ofC= + 2)
(O.Norc =
tion towards cerlsin lirst rorv traDsition metsl Therefore, the value ofn is l.
ions, llllEtrnte both these properties ofH2O2
Q. 7. (8) Is it pGible to rlEove complcrely by hoilhS
using chemicnl equotiolls. (l.I.T. 1998) the temporary hsrd[ess due ao Mg(HCOr2 ? -
ADs, Oxidising ag.[t: (b) Cstculrte thG molarity strergth of II2O2
2Cr(OH)l + 4 NaOH + 3 H2Oz..--- solutlor mrrLed j30 volumd.
2NazCrOa+8H2O (tyed Bengat t.E.E. 2004)
11148

Ans. (c) Tbmporary hardness of HzO due to

<ixVl=2x200
Mg(HCO3)2 can be clmPlatcly renloved by l)oil- 2x200x56
or -.
Vr= ----10-
inB because soluble M8(HCOI)2 is c]onverted
into insoluble M8CO3 which can be ren)oved by = 124 cmt,
filtration t'nhlLn ) The degree of hardness of n given
Boil somple of hnrcl wnter is 40 PPm. If the entire hardness
uglHCo3)z ll Mgco: I + coz t + Hzo in due to MgSoa, how much ofMgS()4 is present per kg
(Solrble) (I soluhle) o[ water ?
(b) Molarity = Volume strength/l1 2 solutton. Degree of hardness of H2O is 40 ppm
= _19-
tlz = z.er u. r'-e., 106 g of water coDtain CaCO3 = 40 g
D PR( )B1 t':ltls Since 1 mole of C-aCo3 = 1 mole of MgSOa

j'rr,/,lra, I Calculote thc volume of l0 volume .. 100 g of CaCO, = 120IofMgSOa

II2O2 solution thnt will resct with 200 IIll of 2 N 1!+*?9
KMnOl in acidic nedium :
. . 106I of water contain Mgso4 =

Solution. Normality of 10 volunlc H2O2 = 488

10x68 l0 ^'
=D4xrt=Sh^
or 103 g otwat r will co[tain MgSOa

Applying DormalitY equation, = 1!I-ld , 1d m,r

100
N1V1 - N2V2
or 1 kg of water willcootaro M8SO4 = 48 mE
<H zO) (KM no .)

,ATSJ SPECTAL
Q L A5 0 cm! solutlon ofH2or lib'rates 0 50tgof .. I 0 r.,m3 of I{2Oz solution will give
iodine ftom sn scldltled Kl solutlon' Calculate
02 =22s4 = '1 48cnr3atNTP
the strength of H2O2 solution in terms of
Yolumc stEngth at STP (I.I.T 199s) Thus, volume strength ofBiven HzOz solution
Ars. (4) 2KI + H2SO4 + H2O = 4.4t.
-_ KzSOa + 2H2O + 12 (l I To a 25 ml II2O2 solution, ex'ess of acidified

From the above equatioD, tIzO2 = 12 solution of potassium iodiile rvas added 'Ihe
ioiline liberated required 20 ml of0 3 N sodium
34 g of HrO, e 254 g of I, thiosulphate solutioD' Colculote the volume
., 0 508 of 12 willbe liberated from strength of H2O2 solution. (l.I.T 1997)
B
Ans. Step L To (letemine the notmality of Hror:tolu-
Hror=i*x0 s08=o 068 I lrcn.
(6) The deomPcition of H2O2 oc{urs as Let the normality of the H2O2 solution be Nl
2H7O2 2H2O + Oz Acrording !o tho question,
25 nrl of Nr Hzoz = 20 nl of 0 3 N Na2s2o3 solution
2x34-68I 22100 cm3 at NT?
.. 0.068 of H2Oz uPoo decomPositionwill Sivc
or 25xNl =20x0 3

o,=ffxo068=224 I or N,=20iro3=uzlrn
Thut, tlrc normaLity ol the given Hzoztolulion
(c) Now 5 0 cm3 of H2O2 solution gives
=0 24N
Oz = 22 4 cm3 at NT?
HYDROGEN
11149
Step 2. To detetmine the omount of I!2O2in 25 ml
2MoO;+5HrOr+6H+...-
.tolution
1000 nrl of I N H2O2 solutioo contain H2O2 2Mnz++502+8H2o
=178 (i, Itr neutral medium,MnOf, cxidiset MnI+ to
. 25 ml of 0 2,1 N H2O2 solutioo willcontain MnOr.

H,o,=%t{i#=u rozc MnO; + 2H2O + 3 e- MnO? + 4 OH-l x 2

-
Step 3. 7a deteniine the vofune strengh of Mn2+ +4OH- + ZHzO + Ze-l x j
I{rO, tolution -MnOz
Consider the chentical equation,
2MnOo +3Mn2++4OH-
ZHrO, 21116 a g,
2><34=689
- MnO2 + 2 H2O
22 4 litres at N.TP.
689 of lI2O2 give Oz (u) Ir acidic medinm, MnOz oidisel ,todium
- 22.4 tjlres a[ N.Tp
qalale lo CO2
0 1029 of H2O2 wrlt give
22.4 x x MnO, + 4 H+ +Ze-.-Mn+ +ZHrO
^"2 - ---------88-0.102
1000

9o1- z+ze-
= 33.6 nrl at N.TP
Now, 25 ml of H2O2 solurion give
-2c
MnOr+CrOo2-+4H+ *
02 = 33 6 ml at N.TP
. 1 ml of H2O2 solution will give 02
Mn2+ +2COr+2HrO
336 or 5MnO2 *5qq- +20H+
=-i-= t.sqt -
5 Mn2+ + l0 CO, + l0 HrO ...(iv)
n the vohune ltrengh of the given HaOr,rolu-
t,t,
Fronr the above three balaDcd equalions, it fol-
tion = 1.344
lo\rs that
,., , Hydrogen peroride solution (20 ml) reacts
quantitfltivelywith a solution ofKMnOa (20 ml) (iv) 5 qo?- =2 Mno; = 5 H2o2
acidilied with dilute H2SOa. The same volume Saep 'fo determine the numbet
-2. of nales oJ.
ofKMnO{ sohrtioh isjust decolourised by l0 ml CrOf,- present in 10 tnl oJ 0.2 M lotlitm oxalate.
of MnSOo in neutrnl medium simultaneously No. of nloles ofsodium oxalate
forming a dork hrown precipitate of hydrated
= Molarity x volume tn litres
Mn02, The browh precipitat; is dissolvcd in t0
ml of 0.2 M sodiuh oxalate uhder boiling con. =o zrffi =2 xlo-3mote
dition in the presence ofdilute HrSOa, Write the
Step 3. To calculale the molatity of HzOz
balflnced equations involved in the reactions
and calcnlate the Inolflrity ofll2Oz. From Eq. (iy), it fo ows rhat 5 qO?- = 5 H2O2
(I.I.T. 2001) or 2 x 10-3 mole of CrOo2- 2 x l0-3 mole
Ans. Stcp =
1. To rrite balonced equatioru for tlrc reac- ofH202
Itons inyolved.
(r) In acidic medium Now2 x l0-3moleof H2Oz is present iD 10 ml
, MnO; oxidises Hzozto 02.
ofH2O2

H2O2 ...- Or+211+ +2e-lx5 .. Motarity HzO2 - 2 tll-' >< rooo

=0.2M
1 1/s0
Ned CouYse Chentisttg

UfrT"LE ;UE9TI,ON9
(a) CaCO, (6) Ca(OH),
l. whiob of the followll]g statemenL\ is nlost ap-
plicable to hydrogen 'l It cao act (c) Caclz (d) Hcl.
(c) as a reducing agent
In the calgon process of softeniDg ofwater, \r'hich
(D) as an oxidsing agent of the following is used 'l
(c) both as oxidisirg aDd reducrng agents (.r) Sodium polymetaPhosPhate
(d) Deither as ao oxidising Dor as a reducing agent' (b) Hydrated sodium aluminium silicate
Hydrogen contbiDes with other clements by (c) Cation exchaDge resins
(a) losin8 an electroo (d) Anion exohaoge resins.
(b) gaining an electroD 10. Hydrogen will Dot reduce
(c) sharing an electron (d) heated cupic oxide (b) heatcd ferric oxide
(d) l6inB, gaining aod sharing ofan electroo' (c) heated slannic oxide
l. Ttrs tirst ionization ener$/ (kJ mol-l) for H, Li, E (d) beated alunrinium oxide.
Na has one of ihe followirgvalues: 1681' 520, 1312,
I t. Thc oxidation states exhibited by hydrogen in its
495. Which of these values mrresPonds to that of
various c!n]pounds are
hydrogen ?
(4) -l only (6) zero only
(a) 1681 (b) t3tz
(c) 52o (d) 4es. (c) + 1, -l and zero (d) + 1 oDlY

4. The correct increasing order of the acidity of CO2'

The oxidation stirtes of the most electrooe8ative
I{2O and H2O2 is element in the products of the reaction, Ba02 with
< II2O2 < HzO
(n) CO, dil. H2soa are
(Ir) H2o < H2O2 < CO2 (4) 0 aDd
-10
(b)
-l ard -2
ard + l.
(c) HzO < HzOz > COz (c) and (d)
-2
-2
(d) H2o2 > coz > H2O
solution that 13. 30 volumcs HzO2 meaDs
5. The volumc of 10 voluole H2O2
(o) 3oVo HrO2
decolourises 200 ml of 2N KMDoa solution in
acidic Dredium is : (b) 30 cn]3 of the solulion cootains lg of H2O2
(a) 112 ml (6) 336 ml
(c) I cm3 of the solution hberatcs 30 cm3 of oz at
(c) 200 ml (d)zu mt.
STP
which of the followinS meials csnnot be used for
(d)3(t cnr3 of the solution contain one mole of
liberating dihydrogen from dilute hydrochloric
acid? Hzor'
(o) Zinc (b) Copper 14. An oxide worch gNes fl2oz on treatment with
(c) Iroo (d) Magresium. dilute acid is
7. Which of the folloering is used as a modctator in G,) l,boz (b) Na2oz
-IlO2.
nuclear reacbrs ? (c) MnO, (,1)
(.r) Hard water (b) Heary waler
(c) Deionizd water (d) Mineralwater' 15, Nascent hydrogeo consists of
E. The lemporary hardness ofwater due to calcium (d) Hydrogen atonls with excess encrS/
bicarbonate can be removed by adding

wL-:r<s 9,a
l.c 2.d 3.b 6.b 7.b E.' 10. d
11. c tz. b 13. c
 'I 1/5'1
HYDROGEN

(b) Hydro8en molcules with excess energy (c) H203

(c) Hydrogen ions in the excited state 24.'ft e hiBh density of waler as corrlparcd to icc is due
(d) Solvated protons. tA.l.l.M.s. l99Jl to
16. The oxidation nuntberofO io H2O2 is: (4) Hydrogen bonding intcraclrons
(D) (b) Dipoledipole ioteractions
(a)
-2 -l (c) Dipole-induced dipole inleracl ions
(c) +l (d) +2.
\\t I \,.R ttht,,ltul t,),,t (d) Inducd dipole induced dipole interactions
,,i <I /,1;:
17. The O-o-H bond angle in tl2oz is
25. The volume strength of 1 5N ll2o2 solutioD is
(a) 106" (b) lw 28',
(a) 4.8 (b) s.2
(c) 120" (4 e4.r.
I t;\i t\ ) : (c) 8.8 (d) 8.4
i' .t ,,,.1 i'\: I
It. Hydrolysis of one mole of peroxodisulphuric acid
produces 26. The hydride ion H- is a stronger basc than
hydroxide ion. Which ofthe tollowiug reactions will
(,?) t$o moles of sulPhuric acid (Natl) is dissolved
occur if sodiunr hydride iD
(/r) two moles of peroxomonosulPhuric acid $ater'l
(u) oDe olole of sulphuric acid and one mole of ..--
peroxomonosulPhu ric acid
(a)H-(nq + H2O(D ttrO+ 1oq1

(./)ooe nrole of sulphuric acid, one n]ole of (b)H-(@t) + tl2O(D oH-(.,rJ) + rl2G)
peroxomoDosulphurlc acid and one mole of -
hydrogen Peroxide- lt l "' (c) H- + H2O -..- No reactior'l
Which cootains both polar and non-polar bonds ?
(d) None ofthese. "; :.:
(a) NHaCI (D) HCN 27. When a substance A reacts with water, it Ptoduces
(c) Hro, (d) CH4 ttrt t,/- a conbustible gas B and 4 solution ofsubstance C
in water. Wben another subslance D reacts with
The critical lenlperature ofwater is higher than that this solution oI C, it Produces the sanle gas B on
of ()2 because lhe H2O Dolecule has warming but D can producc gas B oo reaclion wlth
(d) F'ewer electrons than oxYgerl dilute sulphuric acid at rooDl teDlperature. A io]-
parts a dseP golden yellow colour to a snlokeless
(b) Two covalent bonds (c) V-shaPe
flanre ofBunseo burner. A, B, C and D resPectively
(rJ) Dipole momoot ate :
Anrong KOz, AlOt, BaO2 aDd NOr+, unpaired (d) Na, H2, NaoH, zll
elect ron is prcsent iD (b) K, H2, KOH, Al
Bao,
(a) Nor+ and (D) Koz aDd Aloz- (.) Ca, H2, Ca(OH)2, Sn
(c) KOz only (d) BaO2 oDlY @) Caq, qHz, C.a(oH)2, Fe.

Which of the follo\viog stalements is correc, 'f 2t. Whlch of the following pairs of su bstaDces on rcilc-
(n) Hydrogen has saDe ionization Potential as tion will not evolve II? gas I
alkali metals (a) Fe and H2SOa (aqueous)
(D) H- has saore electrooegativity as halogeDs (r) Copper and HCI (aqueous)
(c) H- has oxidation number of-l (c) Sodiunr and ethyl alcohol
(d) tl- will Dot be lberated at anode (d) lron aDd steam. c-B.s.D. nM.'1: 1re8
' \ I i ',r': 29. Acidifled solutioD of chromic acid on treatment
with H2O2 yields
What is hea\) water 'l
HlEo (b) Hl6o (a) cro3 + I-I2o + Oz (D) Crzo3 + H2o + ()2
(,? )

,Ar s wEr<-< d
ts. b 16. b 11. .l It. c 19, c 20. t 21. c 22. c 23, 24. a
25..1 26. b 27, a 2A. b
111s2
Neut Course Chem istrrl
(c) CrOs + H2o (d) HzCtzOl + H2OtOz. (e) Dz (Ibrula M.E.E. 2002
:r1 P( r.I; l99tt which oDe of the following processqs will produca
pernlaDent hard water I
30, Anroogst H2O, HzS, HzSe and H2Tb , the one wih
(4) Addition of Na2S()4 to water
the highest boilioS Point is
(a) H2O because of hydrogen bonding (b) Saturation ofwaterwith CilCO3

(b) H21b because of higber molecular weighr (c) Saturation of water with MgCO3

(c) H2S because of hydroscD booding (d) Saturation ofwater with CaSOa

(d) HzSe because of lower molecular weight

31. Pora and orlho bydrogen differ in
(a) atomic itumber
(c) spins of protons
(b) atomic mass
(d) number of [eutrons
t 1 l. :1'1.( :ttl) I
36. The reagent commonly used to detern'line hard'
ness ofwater titrimetricilly is
(a) Oxalic acid (b) Disodrum salt of EDTA
(c) Sodium citrate (r.i) sodiunl thiosulphate
)

37. The structure of H2Oz is

32. Heavy water is obtained bY
(4) planar (b) non-planar
(4) boiling water
(b) fractional dislillation of H2O (c) spherical (d) linear.
(c) prolonged clectrolYsis of H2O
(d) heanog Hzo2 r.EM.C.2ooI) H2O2 acts as an oxidising agent iD
33. Polyphosphates are used as water softening agents (a) Ncutral medium (b) Acidic medium
because they (c) Alkaline mediunl
(4) form soluble complexes witb anionic species (d) Alkaline ard neutral n'ledium
(b) precipitate anionic sPecies (e) Acidic and alkaline D)ediuDl
(c) torm soluble comPlexcs wilh calionic species
(d) precipirare cationic species 39. Comnrercial 1l'2 volunle H2Oz solution has a
tt r t. .!):j..
molarity of
34. Action ofwater or dilute mineral acids on metals
(d) 1 0 (b) 0's
caD gNe
(c) ll 2 (d) l tz
(4) Monohydrogen (b) Tiitium
(e) 0 75
(c) Dihydrogen (d) TiihYdrogen

NT 5 / EX" LANATIO N 5'co M ul+ci 7l e, Ch oi

ofalkali metals but lt. HO-SO2-O-O-SO?-OH + HrO ....-*
3. IE of H is n]ore than that less
rhan that of E PeroxodisulPhuric acid
4. A stronger acid disPlaces a weaker acid from its salts. Hoso2oH + HooSo2oH
BaOz+H2O+CO, BaCO3 + H?Oz SulPhuric Permono-
Weaker acid acid sulPhudc acid
Strongcl acid - 19. H bond is non-polar while O-H bonds are
5, Retbr to Problem 1 on Page 1U48 for arN'xcr' polar.
10. Al-O bond is very strong -2 -1 K+1-:ij_g:l
12. BaO2 + H2SO4 SaSOa t fI2O2

15. Hydrogen molecules with excess eDer$/. 25. Multiply normality by 5.6. ie. 5'6 x I 5=8 4
-
A
29, c 30. 4 31, c 32. c J3.. -1J. r 35. d 36. b 37. b 3t. e
39. a
HYDROGEN
1 1/s3
27.2Na+2H2O-H2+2NaOH 2 Ca2+ + Na2 [Naa (PO3)6] .-
ABC
a]Jd Zn+ 2NaOH 4 Na+ + Naz [(Ca2 (pO3)6]
DcB- complcx (solublc)
-NEZnOz+Hz
Sodiun hexameraphosphare-a polyphosphate, 35. Saturation of warerwilh CaSOa produces hardness

conbines with cations (ie., Ca2+, Mgz+) to form 39. Molarity = Volunre strength/l I .2
soluble complexes. =lt A1l 2-r'O

ADDTTTONAE gUEST|ONS
Aa se rt;i o n - Re a e on Ty p e e.u e sli o n s
.fhe foUowltrg quectto;;corJit oi t-. stat"tlerk n. Whllc anst erlng
these qustions, you arc requlred to choose ony one o
(a) lf both Assertlotr and Rcason sar hue aDd ahe Re{son ls o correct explanaflon
of the AssartloD.
(r) If both as.sertion alld Ressotr ore true but ReasoD is Dot a corrcct explanatiotr
of the Asserdor"
(c) IfAssertion is true but the Reosor b fclse. (d) fboth Assertior
and Ileason are false.
A.sscrtlon Reason
rrlhter is a gmd s6ive-Ef-nt
for ionic clmpouDds but Hydration e cient enerry to
poor for coyalent compounds. overcome la rogen bondi in
water while nds interact so
wcakly that even in der Uhals,forces between molecules
oIcovalent compounds nnot be brokeD.
H2O2 liberates 02 when it reacts with aciditied KMnOa oxidises H2Oz to 02.
KM0O4 solution.
H2O2 has higher boiling point tha[ r,!rter. The dipole moment of H2O2 is lirtle more than that of
Hzo'
The eleclronegativity differcoce betweel Be and H is very
high.
5. Its degree ofdissociarioD is high.
6. H2O2 on ioniccompound.
is (A.1.1.M.5.2003t

fr ue/ Falee Statemente

Which of the follo\*'iDg statemenb are true aDd 5. When tretcd with H2O2, lead dicxide is reduced
which are falsc ?
rilAter can act as an to lead metal.
cxidising as well as a reducing 6. ID copper sulphare penrabydrate, all the water
ageot. molccules arc athched to the C!2+ ion by coor.
Sequestration of Caz+ and Mg2+ ions presnt in dinatc cotalent bonds.
hard $ater is cnrried out by using zeolites. 7. Znc hydrqide dissolvcs iD excss of NaOH solu_
Completc hydrob6is of onc mole of perfiydisul_ tion !o 6,olvc dihr/drogen gas.
phuric acid gives one molc of H2O2 and two moles t. trad dicidc on readion with dil. H2SOa givcs
of H2SO{. Huor'
During electrolysis of aqueous hydrochloric acid, 9. Deutcrium ir an isomer of protium.
dihydrogen is liberated at the anodc.
10. \l6ter cannot bc usd to extinguish petrol f,re.
11154 Neut Coursc Chemixr{fiffi
-l-'Pr
F ii i l ri c: r;'' i..: r-l k,z
l. Dihydrogen acts a reducing agent in iis rcaction 6' The chemical formula of permutit is
wrth .................... while it acts as aD oxidisiDg a8eot 7. Hydrogen gas is liberated by the aciion of
in its reaction with ... aluminium with a coDcentrated solution of ...... ... .
2. In rhe reaction of F2 with Hzo' Bater acls as a (I.l-T 1987)
E' The electrolvsis ofmolteD sodium hydride liberaies
3. The bleaching action of hydrogen Pero)dde isdue ....................-. gasat rhe anode. (t.I.T. l9S9)
to.................,...... 9' cal8on is the t'ade name of" " """
4. 'Ibmporary hardDess or water is due ro
i. rfiJlog"; p".*ide rurns siarch-pottssium iodide l0' Hydrogen has"""'isotoP! and"""nuclear isomers'
papr blue due to the liberatio[ of............ ......... .

Vlat chinq TY?e G'uestiong

Match iteEs ofcolumn I rvtth aPproprlate items ofcolumn II
Col mn-l Column.lI
1. Deuterates are salts wilh (d) Dihydrogen
2. (htion exchange resios cootain (6) Nuclear reactors
3. Palladium hydride (c) DzO as waler of crystallizllion
4. Zn dissolves in NaOH (d) Sod. polymetaPhosPhate
5 Calgon fe) Non stochiometric.
6. Hea\y water ifl acirJic group such as - CooH and - So3H

AlVSOUEI<S
ASS ERTION.REASON iYPE OUESTIONS

t. (a) 2. (a) 3. (D a. (c) s. (d) 6 (d)

l_194I4!?! llltylll9
4. E at the c2thode 5' q PbO 6' R four are bonded to Cu2+
by c
f. T 2. F; sod. polyrnetaPhosPhate 3. T
one is bolrde<l to SOI- ion by H-boDds 7. E Zn(OH), + 2NaOH -....-
oordinate bords while the fifth
-O - o- ion and hence it docs
N% ZnO2 + 2H2O E. E PbO2 is [tot a Peroxide since it does not mntain
of protium lo' Being ligher'
noi""otu"- UrOrto treatment \f,ith dil. H,SO4, 9. E deuterium is an isolope
Petrol floats over water.

c\oor Fe3o1 ; Na or Ca' 2. reduciDg agent, 3. nascent orygen. 4. blcarbonatcs of caz+

& M82+
1. heated
l0' three
s. I, e. NarAfrslo, . rH2O 7. sodium hydrodde & dihydrogen 9' sodium hmmeEPhosPhate
(H, D, T), two (ortho and Para).

r. (c) 2. (f) 3. () 4. (a) s. (d) 6 (b).

H I NT5/EX LANATIO Ne t o Aes ert-io n-Rea eon

P Q.ues'ciong
3. tonirr etplanation, tre eiteni of H'uoriding in Conect avsertion r The O-O bond len8th in
H2O2 is higher thar that in H2O. lo[8er than that ofO2F2.
H2O2 is nruch

4. Con'ccl reoton r The electroflggativity dilfcrencs
betr{cen Bc (1 5) and H (2 1) issmall.
t Coftect ossetlion : D2O is called heary water'
Correctreaton: DDe to strooger D-O bonds, ttle
degree ofdissociation of D2O is lower lhan that of
H2O.
6, Coftecl rea.\on : The lone Pairs of electroos olt thc
O atoms are strongly attracted by ihc electronega-
tive Fatoms. As a re-sult,lone Pair-lone pair rePul-
sion ofthe two ory8en atoms is far less iD.O2F2 tban
in H2O2. As a result, O-O) bond length is O2F2
(1 22A) is nruch shorter than in H2o2 (I 48A)
 r

e-Alock Elerr.er,ts
ol the
General inttoduction to sblock elernents-abundance, occurrcnce' anonElous ProPedbs
lirst elements in each gro.lp, diagonal relationship'
Alkali metals----occutrence, eleclronic conligurltion nd Physical. properties
(including lE, reactiiity and ]eactions with oryqen'
hydrogen, hal la. Basii natu roxides' halides' Li and
Na-otcurren and uses, NarCOa.
in atomic and Physical
proP
The
non-
Bi[lHl,E1":':j""Xilj
f alkaline earth metals-
Mag ,
strlal uses ol lirne, lirne stonB' coment'
CaO
l,: :,r i, , r
12.1.1. Occur:tncc and Abunilance.
,,:
:, , , . r: ,,1], , ]:
,
:,': j r: ,, :., , ,:
,:,
: r:, : j r:1

Both alkali and alkaline earth metals are high-

Dependiug upon the type of the orbital wbich
ly reactive and hence do not occv in the free stote
receives'the lasi eicctron, the element in the long
but are widelydistributed in nature in the combined
state. Whereas alkali metals rnostly occur as halides
oxides, silicates, borates and nitrates, alkaline earth
metals mainly occur as silicates, carbonates, sul-
phates and phosphates.
Atthough alkali metals have similar chemical
properties yet they do not occur together mainly
ErouDs contain one or two electrons in their outer- Leciuse thiir ions are of different sizes. Similarly,
i,.r.d s-orbital while all the inner shells are com- alkaline earth metals usually do not occur together
except dolomite which is a double carbonate of
calcium and magnesium [MgCO, . CaCOr].
Likewise some double salts of alkali and alkaline
earth metals such as carnallite
(KCl.MgC! .6 H2O) are also known to occur in
nature.
Some alkali and alkaline earth metals occur
abundantly in nature. For example, calciutll is the
frllln, mognesium is tlre slxah, sodiunt is rrre sevcnth
and potassium is the eigllth, baiunt is the fotur'
alkaline earth rnetals on!y.
tenth and srror iurz is rhe lifteenth most abundant

tzll
 1212 Neul Course
element by weight in the earth,s crust. Sodium and 12.13. Diagonal r:latlonshlp.
magnesium are also present in relativety large
amounts in sea water, brine wells and a few silt . ofcertair groups in the second
Some elements
period resemble with the certain elements of the
Iakes. Calcium and potassium also occur in sea
water but to smaller extents.

It is intcrcsting to note that although soatium and

potassium are almost cqually abundant (2.837o Na and
2 59qo K) in thc eaflh's crusl, ylt sca ozlci conrains 2.87a Group 1. Group 2 Group 13 Group 14
NaO butonly0 E7o KO. Thi6 is duc to thc Eason trat mucb peiod: Li.-
2nd Be... B\ C
of potassium appcaring in ground watcr from di&sotlcd
minc16ls ifl takcn up pr.fcrEntialtybyptants whilc sodium ion
gocs to thc 6cs watcr. 3rdpeiod: N" \M, \4 \S,
Thus Iithium resembles magnesiurq beryllium
resembles aluminium and boron r-esembles silicon.,It
The remaining elements are much less abun-
may, howeve4, be noted that lhese similaities are much
datt, i.e., rubidium rJ ,he twenty.thlrd , caesium is
rlre for8-slxth and beryllium
ri ,lre fiIty.llrst most
weokg lhan The
main reason
abundant element by weight in the earth,s crust
(i) Sim

radiotherapy treatment of cancer at one time but

now &Co is used. Marie Curie was awarded the
Nobel Prize for chemistry in 1911 for isolating and
studying radium and polonium.
The element francium was discovered later in
1939 by Pierre at the Curie Institute, paris. Its
longest lived isotope 223Fr has a half-life period of
21 minutes. As a result, not much is known about
it; chemistry. Nevertheless, whatever little ajor.Tic and ionic radii (Fig. 12.1) and hence have
element clearly srmllar propertres.
mical properties, Electronegativity increases, Atomtc and ionic
sizes decrease, Polarlzing power increases
12.1r. Anomalous bhavlour offlrst element 'Dam
of a group. *
nor6
=.9

E5S.
I e.q
frHfi
frr-fi
Slmllar electronegatlviv Similar atomic and
lonic radii, Similar potadzing power
metals (Mg Ca, Sr and Ba).
FIGURE 12.1. llustration of diagonal rclationship.

chargc)(ionic 6izc). Polari6ilg parPlr h aldo 6omctimc6 hcs6urEd in tcrm6 of charge pcr u n it arEa, i.c
:z
J
(ioni. radius)'
S.BLOCK ELEI\,4ENTS 1213

(iii) Similarity in polaising powel On moving (i) spodumene, LiA(SiO3)2, ald (ii)
lcpidolite,
across a period, the charge on thc ions increases LirAlr(SiOJ (FOH),. Sodium aad potassium are
and size decreases, causing the polarizing power to
the sevanth aI[id eighth most abundant elements by
increase. On moving down a group, the size in-
weight in the earth's crust. IiaCl and KCI occur in
creases and the polarizing power decreases. On
large amounts in sea water. The largest source of
moving diagonally, these two trends partly cancel
out. As a result, diagonally related elemcnts have
sodium is rock salt (NaCl). Other important
minerals of sodiumare: NarBoO, . L0 HrO (borax),
similar polarizing power and bence have similar
propertics. NarCOr. NaHCO3.z}{z0 (tona), NaNO, (clu7e
sl,l("il()\-l sdlt petre) and sodium sulphate (mimbilite) .

AI,KAI,I NII'TALS Potassium mainly occurs as KCI (sylule), a

The group 1 of the periodic table contairs six
elements, namely lithium (Li), sodium (Na), potas-
sium (K), rubidum (Rb), caesium (Cs) and fran-
cicium (Fr). All these elements are tlpical metals.
These are usually refe(red to as alkali metals since
their hydroxides from strong bases or alkalies.
Alkali metals are highly reactive and
hence do not occur n the free state blut are widely
distributed in natute in lhe combined state iD. f.orm
of halides, oxides, silicates, borates and nitrates.
Lithium is the rlrir)y'y'tft most abundance ele-
ment by weight in the earth's crust (lithosphere)
and mainly occurs in form of silicate minerals, i.e.
l'AllLE 12.1. Electronic configuration ofalkali mtals
mixture of KCI and NaCl (sylrznife) and tho double
sak, KCI.MNL . 6HrO (camallite) and as
IqO . ALO3 . 6 Sio, (felspar) .
12.3. Electronic Conllgurallon i:::r:r:r:::....::::.:r;...j.r;..:.:...::
Alkali metals are .r-block elements, bc-
cause last electron in them enters the s-orbital.
They contain only one s-electron outside the noble
gas core. Therefore, their general electronic con-
hguration is [noble gaslnsl where n = 2 to 7. Since
all these elements have similar valence shell or
outer electronic configuration, they have similar
physical and chemical properties. The electronic
configurations of alkali metals are given in Thble
t2.t.

EIcrncIlts Atomic Electrollic CohfiSuratjoo

Number (jomplete Wiih Inert tirs core

Lithium (Li) 3 7:\z zt1 []tel 2rr

Sodium (Na) 11 1s2 2t2 2p6 3sl [Ne] 3.rl
Potassium (K) 19 tiz xz 2p6 3? 3p6 4s1 [Ar] 411

Rubidium (Rb) 31 7sz z\2 ?f 3s2 3p5 3dro [Itul5,rr

Ajz 4p6 5rr
Caesium (Cs) 55 1s2 zt2 2p6 x2 3p6 3d1o [Xe] 6rr
4sz 4p6 4d1o sP 5p6 &1
Francium (Fr) 87 lP z'z 2f Nz 3p6 3dto [Rnl 7rl
4s2 4p6 4dto 4f4 5"2 5p6
5d1o 6t2 6f itr

Some important physical properties by alkali metals are given in Table 12.2.
1214 llradc cyt's Neut Course Chem istt4l$[f
TARLE 12.2. Some phlsical properties r.rf gloup 1 elements (alkali metals)
Elements
I'roperty l,i Nn K Rb Cs l.r
(Radioxctive)

1\tomic number 3 ll t9 31 55 a'l

Aromic mass 694 22 99 39 10 a5 .4't 132.91 223
Metallic radius (pm) 152 186 248 265 375

Io0ic radius (M+/pm) 76 102 138 152 16'.7 180

lcDization enthalpy I 520 496 419 403 376
(kJ mol-l) II 7298 4562 3051 2633 2230

I llct roncgativity
(PaulinE scale) 0.98 0.93 0.82 0.82 o.'19

Density/g cm-3 (at 293 K) 0.53 0.97 0.86 1.53 l90

Meltrng point/K 454 37'l 336 312 302
lloiliDg poiDVK l6l5 r 156 1032 961 944
Il'(V) at 298 K for
M+(4q)+e--M(r) -3.04 -2.114 -2.925 -2.930 -2 92',1
occurrence iD Lithcpherc 18. 227" I .84'' 78.12' 2.6'.

These proprties are briefly discussed below
l. Inrge atomlc t dll. The anmic radii of
u largestin the respeclivepeiods.
l\<ali tnetals ore tlrc
,]7rcSe increase os we lravel down the group fum Li
to Cs as shorvn in Table 12.2
Explanation. This is due to the reason that as
hc atomic number increases, the number of energy
shells increases by one with each succeeding ele-
nrcnt. As a result, the screening effect of the inner
lilled shells on the valence s-electron increases and
lhc electron cloud tends to expand.In other words,
ths distance betweeeo the nucleus and the last shell
increases and thus the atomic radius increasEs with
increase in atomic number. It may, however, be
stilted herc that asthe atomic number increases, the
rrrrclcar charge alsogoes up. This ten& to deqease
rhc atomic radii by attracting the electron cloud
inrvarrl more forcibly. But the screening effect is so
li!r ge that it ovcrcomes the cotrtractiv effect of the
irrcrcirscd nuclear charge. Hencc. the increase in
,t ontic t tdius os we move down thc gtoup
from Li to
s is primaily due to the predaminstt soeening
, il,'ct (addition of anew meryt shell ) of innerfrlled
tltclls on lhe valence s- electon.
2. Iarge ionic radll. The ionic mdii ol the
, tttions fonned by them are smaller in ske than the
: conesponding atoms. However like atomic radii,
these are the largest in their respective periods.
Explanation. When the valence s-electron is
lost from the alkali metal atom, the monovalent
cation formed has one shell less than the cor-
responding metal atom. Further,with the loss ofone
electron, the effective nuclear charge increases and
thus the remaining electrons are pulled closer to
the nucleus thereby decreasing the size of each
individual energlshell. Hence, it can be concluded
lhat &te to contractive efrect oI lhe inueased nuclear
chatge and lesser number of energ shells, the radii ol
cations are much smaller thon the conesponding
atoms.
Thend ln the group. Like atomic radii, rfte
ionic radii increase we move down the group from Li
ro G primarily due to the addition of a new energy
shell with each succeeding element as shown in
Table 10.1.
3. Low ionization enthalpies. 7-1rc ionizalion
enthalpies of the alkuli melals are the lowest a,\ com-
pared to the elements in the othet groups.
Explanation, This is mainly because of the
fact that noble gas core shields the lone s-electron
in the valence shell from the direct attraction ofthe

'pf'm (parts pcr million "pcrccnt.gc byvciSht.

1
 S.BLOCK ELEMENTS
positive charge on the atomic nucleus. As a result,
the valence s-electron is loosely held bythe nucleus
and can be easily knocked off by supplying only a
small amount of energy.
Thend ln the group. The ionbatian enthalpies
ol alkali metals decrease progressiely os we move
down the group from Li to Cs.
Explanatlon. This is due to th fact that the
s-electron to be removed becomes farther and far-
ther away from the nucleus because oftbe addition
of a new shell with each succeedhg element (Li,
2rl ; Na,3rl ; I( 4sl ;Rb,5r1 ; Cs,6sl and Fr,7sl).
Due to an increase in tbe number of inner shells,
the screening effect also increases. As a result, the
attraction of the nucleus for the valence s-electron
decreases and hence the ionization enthalpies
decrease as we travel down the group from Li to Cs.
4. +1 Oxidation state- Uniposldve lons.
The alkali metals uhibit oxidation state of + I in
their compounds and are strongly elect opositive in
charactei The electopositive chaructet increases
from lithium down lo caesium in lhe gtoup.
Explanation. As the alkali metals have low
ioaization energies, they have a strong tendetrcl to
lose the single valence s- electron to form the
unipositive ions. Thus they show an oxidation state
of + 1 and are strongly electropositive.
M ---------- M+ + e-
The second ionization energies of these ele-
ments are fairly high and thus the loss of second
electron Ls quite difficult. This is due to the fact that
the second electron has to be lost ftom the most
stable noble gas core, i.e. ni np6. Thuq we may
conclude that the cft emistry of alkali metals k essen-
tially lhe chemistty ofunipositive ions.
As we go dowtr the group, the atomic size
increases and the ionisation energy ofthe elements
decreases, i.e. the tendency of the elements to lose
electrons increases. Consequently the electroposi-
tive characler increases.
5. Metalllc chaEcter. The elements of this
Wup aw typical maah and are soft. Ttese can be
easily cut with a knife. When freshly cut, they are
silvery whitc and on exposure to air they are tar-
nished (i.e. become dull.) The metallic character
increases down the group.
Explanatlon. The tendency of an element to
lose valence electrons to from positive ions deter-
mines its metallic character. As alkali metals have
low ionization energies, they have high tendencl to
lose valence electrons and are, therefore, typical
1215
metals, The metallic character increases down the
group because ionization energ5r decreases down
the group.
The bigger the kernel or smaller the number
of valence electrons, the weaker is the metallic
bond.
Since the atoms of alkali metals have bigger
kernels and smallcr number of valence electroDs,
the metallic bonds in them are very weak. Hence
they are soft and can be cut with a knife.
6. Meltlng and bolllngpoinls.The melting and
boiling Wints of atkali metab are very low and
decrease with inucase in atomic numbeti
Explanatlon, As alkali metals have large size,
the intermetallic bonds in them are quite weak.
Hence they have low melting and boiling points
which decrease down the group with the iocrease
in the atomic size.
7. Naturc of bonds tormed. AU ,he alkali me-
tals Iom ionic (electovalent) compounds. The ionic
character increases from Li lo Cs as we move down
in thc group.
Explanation. This is because alkali metals
have low ionization energies which decrease down
tho group.
E.Denslty,The densiay oI alkali metals are Etite
low as compared to othet metals. Li, Na and K are
even lighter than waat These den:ities increase from
Li to Cs.
Explanation. Because oftheir large size, their
atoms are less closely packed. Consequently they
have low densities. Rlther as we move down the
goup from LitoG, both the atomicsize and atomic
mass increase. But the increase in atomic mass
more than compensates the bigger atomic size. As
a result, the densities ofalkali metals increase from
Li to Cs. Potossium is, howevet lititer than sodium.
This is probably due to an abnormal increase in
atomic size of potassium.
9. Flame colouratlon. AU lhe alkali metols
imparl a chorockristic colour to the tlatne.
Ll
Metal Na K Rb Cs
Colour Crim- Yellow Pale Red Blue
son violet violci
llnm 670.8 589.2 766.5 780.0 455.5
Explanatlon. On heating an alkali metal or its
salt especially chloride due to its more volatile
nature in a flame, the electrons are cxcited easily to
higher energy levels because of absorption ofener-
1216
gy. When these excitsd electrons returD to their
ground states, they emit extra energy in form of
electromagnetic radiations which fall in the visible
region thereby imparting a characteristic colour to
the flame.
The colour actually arises from electronic
transition-s in short lived species which are formed
momentarily in theflame. The flame is a rich source
of electrons, and in case of sodium, the ions are
temporarily reduced to atoms
Na+ + e-- Na
The yellow flame of sodium commonly called
sodium D-llne (actually consists of a doublet
centred at 589.0 nm 539.6 "-) arises from the
"o6
electronic transitio rr3 s1 3 pt in sodium atoms
formed in the flame. It may - be noted here ahat the
colours lrom differenl elements do not all arise from
the sqme transition, or from the same species. For
example, crimson colour of lithium arises from a
short lived LiOH species formed in the flame.
10. Photoelectrlc e[Iect. Alkali metals (escept
Li) exhibit photoelecffic effect. Photoelectic elfect
is the phenomenon of ejection or emission of
eleclrons from the melal suiaces when eleclromag-
netic rodiations sre made lo strike against them.
Explanation. Due to low ionization energies,
alkali metals, specially potassium and caseium,
eject electrons when elposed to light. It may be
noted that lithium which has the highest ionization
cnergy amongst the alkali metals cannot be used in
photoelectric cells because it does not release
electrons when exposed to light.
12.5. Chemical Properties
Somo important chemical properties of
alkali metals are discussed below:
12.5.1. Reactiyity and Elctrode Potcntial.
All the alkali metals are highly reactive ele-
ments since they have a strong tendency to lose the
single valence .r-electron to form unipositive ions
havinginert gas configuration. This reactivity arises
due to their low ionization enthalpies and high
negative values of their standard electrode poten-
tials (Table 12.2). Ftr tlher dlue to lheh strong tenden-
qt lo lose electron, alkali metals ako &ct as slrong
reducing agents. In other words, reactiity oI on ele-
ment is nteasured in tems oI its rcduclag character.
Reducing character. Ionization enthalpy is a
measure of the tendency of an atom to lose
electrons in the gaseous state. Thus, lower the
ionization enthalpy, greater is the tendency of an
Pradeep's
element to lose electrons and hence stronger is the
reducing character or higher is the reactivity of the
elemsnt. Since the ionization cnthalpies of alkali
metals decrease down the group, therefore, dreir
reducing character ot reactiviEt in the gaseous state
increases from Li to Cs, i.e., Li < Na < K < Rb <
Cs.
However, in aqueous solutions, it has been
observed that the reducing character of alkali me-
tals follows the sequence : Na < K < Rb < Cs <
Li. In other words, Li is the strongest while sodium
is the least poweful rcdrcing agent in aqueous solu'
,ion. This may be explained in terms of electrode
potentials (E) of alkali metals.
Electrode potential is a measure of the ten-
dency of an element to lose electronsi[ the aqueous
solution. Thus, rnore negative is the electrode poten-
tial, highu is the tendenc! oI the elemenl to lose
eleclmns and hence stronger is the rcducinB ogent-
Siace tbe standard electrode potentials (E)
of alkali metalsbecome more and more negative as
we move down the group from Na to Cs, therefore,
reducing character of these elements increases in
the same order, i.e., Na to Cs. However, standard
electrode potential of lithium, is the lowest, i.e.,
- 3. 04 volts. In othet wotds,lithium is the strongest
reducing agent in the aqueous solution This may be
explained as follows.
Electrode potential, among other things,
depends upon : (i) enthalp of sttblimatkn,
(ii) ionization entholry and (iii) enthalpy ol hydra-
,ion as shown below :
Sublimation cnthalpy
(D Li G) Li(c)
loniza tion enthalDv
(,i) Li G) -------------5 Li+ G)
(,,,) Li+ G) + aq """- Li+ (aq)
+
enthalpy of hydration
The sublimation enthalpies of alkali metals
are almost similar. Since lithium has the smallest
ionicsize among alkali metals, its enthalpyofhydra-
tion is the highest. Although ionization enthalpy of
lithium is the highest among alkali metals, it is nore
thatr compensated by the large hydration enthalpy
released in step (iii). Thus, among alkali metals,
lithium has the most negative standard eleckode
potential (E :
-3.MY) andhence is the strongest
reducing a4ent in the oqueous solution. Sircn, it
general, stronger reducing agents have higher rcac-
tivity, therefore, Li should also bc most reactivc in
aqueous solution. This is, however, not correct as
discussed below :
 S.BLOCK ELEN,4ENTS
12.52. Reaction wlth uater.
Alkali metals react with water, Iiberating H, and
forming their hydroxid es- The reaction becomes morc
qnd more iolent as we move down the gruup, Tltr:s,
lithium reacts gently, sodium melts on the surface of
water and the molten metal moves around vigorously
and may sometimes catch fue, potassium melts and
alwap catches fue and so are Rb aad Cs.
zLi + 2H2O .------.2 LiOH + H2
2Na*2HrO --+2NaOH+Hz
2K+ zHzO '--.--r 2KOH + H,
Because of their large negative reduction
potentials alkali metals are better reducing agents
than hydrogen. Hence they react with compounds
containing acidic hydrogen atoms such as water,
alcohol and acetylene liberating hydrogen gas.
2M +2 HrO -----------+ 2MOH +H2
(Alkalimerals) Atkali metal
hydroxidc
2 M + 2qH5OH---------- 2 qH,OM
Alkali metal
cthoxidc
M + HC = CH -C C- M+ +H2
--.....r M+
2
=
Alkati metal acct,,tide
Thns, lithium is the least reactive while the
reactivity of othet alkali metals towards water and
other acidic hydrogen contoining compounds in-
creases on moving dow'n the group fom Ns to Cs.
Cause for low rcactivity of lithium. The low
reactivity of lithium may be explahed as follows :
Standard electrode potential (E ) and Gibbs
free energy (AG') are related by the equation,
AG'= - nFE'
wheren is the number of electrons lost by the
metal and F is the faraday constant.
Since E for the reaction, Li+ (aq) + s-
U (s) has the lowest negative value, r'.e. - 3.04- {
therefore, AG'ofthe reaction has the largest posi-
tive value. In olher words, this reaction does not
occur However, the reverse reaction, Li (r) -------'
Li+ (aq) + e - has a large negative value of AG', so
Li liberates more enerry than any other alkali metal
whenit reactswithHrO. Inview of this, atft st sight,
it appears surprising why Li reacts with HrO gently,
whereas Na, which liberates less energy, reacts
more vigorously and the hydrogen produced
catches fire. The e:<planation for this observation
lies in the kinetics (i.e., the rate at which the reac-
tion procceds) and not in the thermodynamics (i.e.,
the total amount of energy liberated) .
1217
Sodium has a low melting point, and the heat
of the reactioD is sufficient to make it melt or even
vaporize. The molten metal thus spreads out there-
by exposing a larger su ace to water. As a result, it
reacts even faster, gets evenhotter and catches fire.
Lithium, o! the other hand, has high melting point.
Although the heat of the reaction is high, it is still
Dot sufEcietrt to melt the metal and the hence the
reactioa proceeds gently. Other metals of thls
group with lower melting points react explosively
with water.
Rom the above discussion, we learn that ws
should be cautious while predicting the chemical
behaviour of elements on the basis of one single
fundamental property ofatoms since in many cases
it rnay depend upon many other factors.
1253. Reaction with olrygen,
The alkali metals tarnish in air due to the
formation of an oxide or hydroxide on the surface.
When heated in excess of air, alkali metals form
different types ofoxides depending upon the nature
+ H2
of the metal, e.9.,
Lithium whenheated in orygen forms lithium
monoxide (and some lithium peroxide).
4Lt+O2 """""'- zLhO
Sodium when heated with oxygen at about
575 K forms mainly sodium peroxide (and some
sodium oxide).
575 K
2 Na * O, NuzOz
--r Sodium peroxide
Olher alkali mecals, i.e.,I( Rb and Cs react
with orygen to form superoxides of the general
formula, MO, whelg N4 : K, Rb and Cs, e.g.
K+ 02 -----------. Koz
Potassium supeloxide
Thus the reartivily oI alkali metals with orygen
increases down the group. Furthe4 the increasing
stability of peroxide or superoxide, as the size of the
metal ion increases, is due to the stabilkation of
latger anions by lar4 cations through higJter lattice
eneryies.
u
Na
K
Rb
Ca
1218 Ned Couvse

Explanatioo. Because of the small size, Li+ The order ol reoctivity of the olkali ttrctal;
has a soont positive freld arovrd it which attracts towards hydrogen decreases as we ntove down the
gtoup ftom Li to Cs. This is due to the reasott thqt the
lattice energies of thcse hydides <lecrease progres'
sively as the size o[ lhe ntelal cation inTesses and
thlts tlrc stobility ol these hydides decreases from
hand, Na+ ion because of its larger size than Li+
positive field around
LiH to CsH.
ion to combine with 1073 K
peroxide ion, Ol-.
ZLi+Hz 2 LiH
Lithiuor hFride
The larger, K+, Rb+ and Cs+ ions have still - 613 K
wcaker positive fields around them which cannot
2Na+H2 .._ 2NaH
Sodium hydride
preveni even peroxide ion, O!- to combine with
Alt the alkali metal hydrides are ionic solids
atrother orygen atom to form suPeroxide, Ot. with high melting points.
7/202 02 Since these hydrides contain the hydride ion
02- .-.---.--------- 20; (H-), therefore, they liberate hydrogen at the
oxidc Pcrqidc supcaoxide anode on electrolysis.
It may be pointed out here that superoxide ion All these hydrides react with proton donors
such as water, alcohols, gaseous ammonia and
J:O
r O :)- has a thrce elecion bon4 i.e., it hos alkynes liberating H, gas.
one unpaired elecfron which makes it coloured
(LiO2, NaO, are yellow, KO, is orange, RbO, is LiH (s) + Hzo (0 ......._ LioH (aq) + H2@)
browrr and CsO, is orangc) and Parumagnetic- NaH (s) + ROH O --"""'r RoNa (s) + H2 @)
Sodium peroxide is ycllow in colour probably due Hcat
to the presence of a small amount of superoxide in NaH (s) + NH, @) ..........* NaNHI (s) + H2 @)
it. The normal oxides of alkali metals are however, Hcat
c olourles s and dianagnetic. 2KH (s)+HC=CH G)+ KC=CK (r)+2H2 @)
12.5.4. Ac'tion ot alr and moisturt. Lithium hydride is used as a source of
AII the alkali metals on expcure to atmosPhere hydrogen for military purposes and for filling
o oxides, metrological balloons since it has a low molecular
alkali me- weight and on reacting with HrO, it evolves highest
moisture. percentage of hydrogen by weight.
4M+02 """' ZMrO 12.5.6. Reaction with halogens.
Alkali metals react vigorously with halogens
M2O+H2O ' 2MOH to form metal halides of the general formula,
2 MOH + CO2 """+ M2CO3 + HzO M+X- wbere M stands for the metal and X for the
halogen.
It is because of tbese reactions that alkali 2 M+ X2 """"".r 2 M+X-
metals arc stored in ineft hydrocubon solwnts likc
petroleum ether and kerosene oil which prevent where M = Li, Na, K, Rb or Cs and
them from c.ming in contact with air a[d moisture. X: E Cl, Br or l.
1255. R@cfion rYith hydrogen. The reactivity of alkali metals towards a par-
All the alkali meta.ls react with hydrogen at ticular halogcn increases as we move dovm the
673 K (Lithium at 1073 K) to form colourless crys- group from Li to Cs. For example, potassium reacts
talline lonic hydrtrles of the general formula, with chlorine more vigorously than sodium.
M+H- where M stands for the alkali metals On the other hand, reactivity of halogens
Heat towards a particular alkali metal decreases form
2M+Ht """""r 2M+H- Frlolr, i.e.,

where M : Li, Na, K, Rb or Cs Fr>Clr>Brr>1,

 S.BLOCK ELEI\,4ENTS 1zls
12.5.7. Solulrility in liquid ammonia. 2 M+ (NH3)r + 2 e- (NH3)r-
F2
2 M+ NH2- + H, + (r +,y - 2) NH..
U I!
tI clz
However, under anhydrous contlitions anrl in
Na IF u2 the absence of catalytic impurities such as tran:ii
K tr or! Brz tion metal ions, these solutions can be stored for
d several days.
Rb
l2 '12.6. General Characteristics of lhe
Ca
Compounds ol the Alkali Metals i:ti:r:: :i:i ,t:, ,:r,,r

All alkali metals dissolve in liquid aounonia AII the compounds of alkali metals are
(solubiliry may be as high as 5 M) giing higlty predomirantly ionic. Some of the general charac-
conducting deep blue solutions. teristics of these compounds are discussed below :
Eryrlanatlon. These solutions contain am- 12,5.1. Oxidcs and Hydroxldes
moniated cations aod ammoniated electrons as All the alkali metals, their oxides, peroxides
shown below : and superoxides readily dissolve in water to
1 M+(.r +),) NH3-----.r M+(NH3), +e-(NHr), produc corresponding bydroxides which are
strong alkalles, e.9.,
When ordinary light falls on ttrese am-
moniated electrorx, they get excited to higher levels
2 Na+ 2 HzO-.-....| 2 NaOH + H2
by absorbing energy corresponding to red region of NqO + HrO .----------r 2 NaOH
the visible light. As a result, trarsmitted light is blue
which imparts blue colour to the solution. Some
NarO,+2HrO -.-.....r 2NaOH * HzOz
important properties of blue solutions of alkali 2KO2+2H7O 12KOH + H2O2 + ()2
metals in liquid ammonia are as under :
Thug peroxides and supcroxides also act as
(i) Dilute solutions of alkali metals in liquid axidbing agent since they react with HrO forming
ammonia are dark blue in colour but as the con-
HrO, and C), respectively.
centration increases above 3 M, the colour changes
to copper-bronze and the solutions acquire metal- The hydroxides of all the alkali metals arc
lic lustre due to formation of metal ion clusters. white crystalline solids. Thcy are strongest of all
(ri) The blue coloured solutions areparurzca" bases and readily dissohe in water with the evolu-
netic due to the presence of large number of un- tion of much heat. A number of hydrates of the
paired electrons but bronze solutions are heavicr alkali metal hydroxidas e.g., NaOH, Hz()
diamagnetic due to formation of electron clusters (where n = 1,2,3,4,5 and )
have been preparcd
in which ammoniated electrons witb opposite spin from their aqueous solutions but little is known
group together, r'.., about their structures.
2e- (NHr)r-------r I I e- (NH:)rl I J e- (NHr)rl (i) Basic swngh. The basic strength of thosc
(iri) The solutions of alkali metals in liquid hydroxides increases as we movc down thc group
from Li to G. Thus, NaOH is a stronger alkali than
ammonia are good conductors of electricity due to
the presence of ammoniated cations and am- LiOH ; I(OH is a stronger alkali than NaOH ancl
moniated electrons. However, the conductivity so oD.
decreases as the concentration increases sincc the
ammoniated metol cations are bornd by he fue UOH
unpaired electrolos $)hich have been descrbetl as \,laot
extr andd metals.
(lv) These solutions are stronger reducing
KOH 2i,6
agents than hydrogen and hence will reacf with bz
water to liberate hydrogen.
(v) In preseace of inpurities or catal)6t such
Explanation. The hydroxides of alkali metals
as Fe, the blue coloured solutions dccompose to
behave as strong bases due to their low ionizqtion
form metal amides with the liberation of Hr.
ner8r'er. Due to low ionization energies, the M O
-
 12110
atse ChcmiswsfrBlD
bond in M
()H - ions.
- O - H can easily break giving M+ and
MOH ....- M+ + OH- (basic narure)

, . Qi.) _ Sotubitiity ond stobility. All

hydroxidcs are highlysoluble in water and thermal-
rhese

ly stablc cxcept lithium hydroxide.

A
2 LiOH ._ Li2O + H2O
(ii.i). F()-rmation
,nycroHdes
. oI salts with acids. Alkali metal
being strongly basic react with all acids
Iorming salts.
NaOH + HCI NaCl + H2O
-+
2 NaOH + HrSOo -"-- Na2SO4 + 2 H2O
D

. _ The salts are colourless ionic solids which are

soluble in water.
12.6.2. Halides

M+ x-

MrO + 2 HX._....>
MOH + HX
lMx + H2O
o6)
I
llr +'---',
-.-) MX + HzO PoLARrzrNc poLABzED I
M2CO3 + 2 HX---r ZMX + CO2 + H2O CATION ANION gpp61aqg2E9
ANION
(where M = Li, Na, I( Rb or Cs and X
^. Br
Cl, ^ or I) = F,
The_covalent character of any compound, in
general, depends upon the following factlrs. ' c

_._.!icl > NsCt > KCI > RbCt > CsCl Thus,
LiCl is more covalent than KCl.
ilnip iz.i.'S
(in kl mo
;i;; (7) Slze o-fthe arllor
_,_s potarizability.
ts !-arycr the at on, greqter
This explains why coval eni char_
acter oflithium halides is in the order

Li 4tz LiI>LiBr>UCl>LiF
-398 -350 -2'11
Na ,_ _F9r
tle samc reason, dipole moment of LiI
-569 -400 -360 -2A8 -
(o.25 D).is much less than the theoretically ex_
K -563 424 -392 pected value of 11.5 D ifit were l\OVa ioltc.
-3U
Rb -549 423
Cs -531 4U
-389 -329 . (rr) Charge on the ton. Greater the chop on
the catio4 Water is its poloizing power
-395 -337 and .lience
S-BLOCK ELEMENTS 12/11

larger is the covalent character. That is why the (c) Hydration cnthalpy. It is the amount of
covalcnt character ofsome of l.he halides increases enthalpy released when one mole of gaseous ions
in the order Na+Cl- < Mg3+Cl2 .
Alr*Clr. combine with water to form hydrated ions.

Similarly, greater the charge otr the adon, M* G) + aq M+ (aq) + hydration enthaipy
morc easily it gets polarized thereby irnparting x- (g) + aq --'-'+ x- (aq) + hydration enthalpy
morc covalent character to the compound formed. Higfier the hydrolion enthalp, of the ions",
For example, covalent character increases ia the greotcr is tle solubilily oI the enthalry in water
order : NaCl < NarSOo < NarPO. as the size of Further, the odeDt of hydration depends upon
the aniou increases and hence larger is the covalent the size of the ion. Smaller the fie of the ion, more
characler Thus, the covalent characlet decreases es higbly it is hydrated and hence greater is its hydrated
the size oI the anion decreases- ionic radius and less is ils ionic mobility (conduc-
tance) . Thus the order of their radii and mobility are
(iv) Electronic configuration ofthe cation. If
two cations have the same charge and size, the one Ionic radius : Li+ < Na+ < K+ < Rb+ < Cs+
with apseudo noble gas configumtion, i.e., having 18 (in pm) 76 r38 152 167
electrons in the outermost shell has greater polariz- Hyd.ration
ing power than a cation with noble gas configura-
tion, r'.e., having 8 electrons itr the outermost shell.
rrumberar' 25'3 16.6 10.5 10.0 9.9
For this reaction, CuCl is more coralent that NaCl Hydroted
(although Na+ and Cu+ have same charge uiz +L rochus: Lr' >Na+>K+>Rb+>cs+
and nearly the same size ra'z Na+ (1'02 A) and (inprn) 3q n6 2i2 2U Z2A
cu+ (0.96 A).
Ionic mobility : Li+ <Na+<K+<Rb+<cs+
(D) latfice nthslples. Latticr etrthalpy is
defined as the amount of enerry required to
(ar ntfnite 33 5 43.5 64.5 67.5 68
separate one mole ofsolid ionic compound into its dilution)
gaseous ions. Er4zenlly greater lhe lattice enthalpy, In the light of above argumentE let us now
higher is the melting point oI the alkali metal halide explain the melting points of alkali metal halides and
and lower is iu (Tbble 12.4) sohtbiliE in wateE their solubility in water or organic solvents. Thug
r\BLE l.ai(i.:..nri'iipi-i. t'f,ir,,ii ,i' .'-'
12.4. (i) A delicate balance between lattice enthal-
thalpies (in kl mol- r). (sohrhilitie\ (in /l{)0 g xf
H.())) and melting Points (in X) of sornt alk;rli ieh
metal halides.
lotlice enew ?1005 A mofl) n hercas the low
Com- Lrttice Hydrationr Solu. MeltirE solubility of Csl (44 g1100 g HrO) is due to smallet
polIEd enthalpy eothalpy bitiE DoiIIt hydration enet&t ol the two ions (-670 kl mol-l).
LiCI -445 -a76 63.',l 887
NaCl J'to J76 35.7 1084
KCt -:703 -700 34.7 1039
Rbcl -6'14 -680 17.0 988
CsCl -444 -646 162 925
NaF -493 -919 4.22 1261
NaCl -,70 -1'16 35.7 1084

NaBr -145 116 1028 soluble in HrO lhan NaCl'

-730
Nal -685 -685 184 944 (,i,) B
LiF -1005 -1019 0.n 1115 electronega
470 44.O
predominon
CsI -582
cnthalPics of cation6 and snions'
'Sum of thc hydraliot!
..Thc hldration entlalpy ol thc alkrli mctal cations and halides (in ld mol-l) rcspcctiwty arc :
Li+ (-506), Na+ G.406), K+ (-330), Rb+ (-310), Cs+ (-276) and F- (-513), Ct- (-370)' Br-
(-339)' I- (-39a)'
..rThc h,'dration number i5 thc avciagp number ofwatcr moleflrles associatcd with thc mctal ion'
 12112
ortanic sotvenls sach as alcohol, acetone, eW
ocetate ; LiCl is ako soluble in Widine. ln contrast,
NaCl being ionic is insoluble in organic solvents.
(iy) Due to highhydration enthalpyofLi+ ion,
lith tm halides are soluble in watet scept LiF which
is spaingly soluble due to its high lattice entlrulpy.
However, as we move dor*n the group, the solubility
of a.lkali metal fluorides increases regularly as we
move from LiF to CsF since the decrease in lattice
eathalpy more than compensates the decrease in
hydration enthalpy.
(v) For the same alkalt metal, the melting
points deoeo:e in the order : fluoide > chloide >
bromide > iodide.
Explanation. For the same alkali metal ion,
the lattice energies decrease as the size ofthe halide
ion increases. For example, lattice enthalpies of
Naf,, NaCl, NaBr andNal are919,776,745 and 685
kJ mol-r. As the ldttke enthalpies decrease, enew
reE.ired to break the lattice (meltingpoint) decreoses
dnd hence the melting points of sodium halides
decrease lrom NaF (1261 K) -------+ NaCl (1084 K)
"-.+ NaBr ( 1028 K) ----.- NaI (944 K).
(w) For the same h alldeion, the meltingpoins
of lithium hqlides are lower than those of the cor-
responding sodiwn halides and thereafier they
decrease as we move dowtt the goup ltom Na to Cs.
Explanation. The low meltitg pnint d LiCl
(887 K) as compored to that of NaCl is prubably
because LiCl is covalent in nature while N aCl is ionic
(because Li atom is smaller in size than Na atom).
Thereafter, the meltingpoints decrease as we movo
from NaCl (1084 K) .._ KCI (1039 K) + RbCl
(988 K) -"- CsCl (925 K) because the lattice en-
thalpies decrease as thesizeofthe alkali metal atom
rncreases.
12.63. Salts of Oxoacids
electroposi-
tive, vory strotrg
base all oxoacids
(H2CO3, H3PO1, H2SO4, HNO,, HNO, etc.).
They are generally soluble in water aad stable
towards heat. Here, we shall discuss only car-
bonates and bicarbonates.
The carbonates (MrCOr) of alkali metals are
rem
first
oxid
and decomposes readily.
Neur Course Chemistry
A
Li2CO3 """'' Lizo + co2
Being strongly basic, alkali metals also form
solid bicarbonates. No other metals form solid
bicarbonates, though NH.HCO, also exists as a
solid. Lithium, however, does not form solid bicar-
bonate though it does exist in solution. All the
bicarbonates on gentle heatiag undergo decom-
position to form carbonates with the evolution of
coz.
A
2MHCO, """'r M,CO3 + CO2 + H2O
As the electropositive character iacreascs
down the group, the stability of carbonates and
bicarbonates increases.
All the carbonates and bicarbonates are
soluble in water and their solubilities increase
rapidly on descending the group. This is due to the
reasotr that their lattice energies decrea.se more
rapidly than their hydration eaergies on moving
down the group.
1 2.7. Anomalous behaviout of Lithium,,r,+iir:iiii,,:i.i,
Lithium - the first element of group
I (alkali metals) differs from rest ofthe elemcnts of
this group in many rcspects cotrtrary to the expec-
tations. Thb anmlous bchavina.o{Iithhqi*drc -
to the following reasoru :
(i) vcry suaE eine of lithium atom aad its im.
(r)
higher polarizing power of Li+ (i.e.
chargelsizn ratio) resulting in increased covalent
character ofits compounds which is responsible for
their solubility h
organic solvents.
(rr) comparatively high ionization energ and
low electropositive character of lithium as com-
pared to other alkali metals.
(rv) non-availability ofd-orbitals in its valence
shell.
(v) stroDg intermetallic bonding.
Some of the properties in which lithium difrers
its
.illustrating
(r) Uthiun is harder while all other alkali
metals are soft.
(ii) The melting and boiling points of lithium
are comparitively high.
. (d Uthium forms monoxide with orygen
while other alkali metals form peroxides (t"t Ori as
well as superoxides (MOr).
S-BLOCK ELEMENTS 12113

(iv) Lithium combines with nitrogen to form
nitride while other alkali metals do not
6Li+N2 -* 2Li:N
(v) LiOH is a weak base *hile the hydroxides
of other alkali metats are strong bases.
(yi) Lithium hydroxide on heating
poses to form lithium oxide while othc.r alkalimetal
hydroxides do rot
2 LiOH ---------* Li2O + H2o
(wi) Lithium carbonate* on heating dccom-
poses to give CO, while other alkali metal car'-
(ry) Lithium ion, being very small in size, is
very strongly hydrated in aqueous solution than
other alkali metals ions that is whv effective size of
Li+ ion in aqueous solution is thjlargest.
12.8. Diagonal relationship ol
Lithium with Magnesium ii:i-:r::iiii+,1irr+:ri:i.r:.i:riiir:::":
dccom-
Lithium resembles magnesium mainly
due to the similarity in sizes of the ir atoms (Li :
152 pm, Mg : 160 pm) and ions (Li+ = 76 pm,
Md+ = 72 pm). The main points of similarity are :
(i) Both LiOH and Mg(OH), are weak bases.

bonates do not ( ) Both form ionic nitrides whn heated in an

Li2CO3 """""'' Li2O + CO2 atmosphere o[ nitrogen.
A
(viu) Lithium bicarbooate does not fo:n a 6Li+N2-2Li:N
solid though it exists in solution while all other r,lkali A
metals form solid bicarbonates. 3 Mg + N, Mg3N2
(ir) Lithium does not react u'ith cthyne (ar.:cty- (iii) The hydroxidcs and carbonates ofboth Li
lene) to form lithium acetylide while all other alkali -
and Mg decompose upon heating.
metals react to form the corresponding acctylides. A
l-iq. NIII 2 LIOI{ -.....--.t LLO + H2O
zNa+HC=CH ' A
196 K Mg(OH)r-MgO+HrO
Na+ -C = C- Nil* + H2 A
LirCO, ........_ Li2O + CO2
Disodium acetvlide
However, when Li is heated with carboo, it A
forms lithium acetylide (or lithium carbidc) while
MgCO, .........- MgO + CO,
other alkalimetals do notreactwith carbon directly (iu) Both Lithium and magnesium do not form
A solid bicarbonates.
ZLi+ZC + Li+ -C = C- Li+ (v) LirO and MgO do not combine withexcess
Dililhium acctylide
(x) Lithium nitrate on heating decomposes to of orygen to give a peroxide or a superoxide.
give LirO, NO, and O, while other alkali metal (ur) Both lithium and magnesium nitrates
nitrates decompose to give the corrcsponding decomposc on heating producing nitrogen dioxide.
A
nitrite and orygen 4 LiNO, '------r / li2o + 4 NO2 + ()2
4 LiNO3 """""'r 2 Li2O + 4 NOz + O2 A
2 NaNO, ...._ 2 NaNO, * O, 2 Mg(NOr),
---+ 2MgO + 4 NO, + O,
(ri) The oxide, hydroxide, carbonate, phos- (vii) The hydroxides, carbonates and fluorides
phate and fluoride of lithium are sparingly solublc of both lithium and magnesium are sparingly
in water whereas the corresponding salts ol other soluble in wa.er.
alkali metals are soluble in water (vrii) Because of covalent character LiCl and
MgC[, are soluble in ethanol.
(xi) Because of covalent character, halidcs of
lithium (like LiCl) are soluble in organic solvents (u) Both lithium perchlorate and magnesium
while those of other alkali metals are i-nsoluble. perchlorate are highly soluble in ethanol.
(.rn'i) LiCl is deliqucscent and crystallizes as a (-r) LiCI and MgCl, are deliquescent and crys-
hydrate, LiCl.2HrO, whereas other alkali metal tallise from aqueous solution as hydrates,
chlorides do not form hydratcs. LiCl.2 HrO and MgCL.6 H2O.
Li-o\
.Strucrure of Li2CO3 is C
li-o,/
12114
llrtttit'r rt's Neut Coprse ChemistrqWID

-' t.
l:ili MonoxtdGq peroxirlcs and suPcrodds of alkali metat& All the flve alkali mctals can be induced to form
normat cidis (r'.. moncddes), permides aod superoxides by dissoMng the mctal in liquid ammonia and
bubbling in the approPriate amount of o)(ygen.
:jii 2. Ctl6td;tructurti olmonoddcs olalkall mctals ExcePl Cs2O which has anti-Cdcl2laycr structure, all other
monoxides, ie., Li2O, Na2O, K2O and Rb2O have anti-fluorite structures.
,ri -1. FotrsshE supctordde (Kor) isusd asa sourEc ofoxygen in subElarincs, sPacEshuttlcs and inemergcDcy breathing
appamtus suci s @O,B?l ,narb. Such rDast6 are used in resqre work in miDs aod in other areas wbere the air is so
Aihcient in ulrgcn that 8n artifcial atmosphere must be generated. The moisture of the &eath reacts with
superside to liberate Gygeq and at tbe same time the potasium h)drcldde formed remo\s carboo diodde as it
is odaled thereby alo ing the atmccphere io lhe mask !o be continuousy regenerated.
4KO, (s) + 2 H2O 6) 4KOH (4q\ + 3 o2gt i KOH (44) + coz G)+ KHCO3 (s)
-
with Co2 forming lqco3 and with co2 and the moisture forming KHco3.
KO2 also combines directly
4Y'o2+ 2co2 a2l$Co3+3oz; 4Koz+4co2+2H2o 4KHco3+3o2
,.ii' :l Potssslum ozoDlde (Ko3) is formed when ozone is Passed tbrough KOH.
-
2KOH + 503 2KO: + 5 o, + H2o
-
It is an orange coloured solid and contaiDs the paramagnctic Ot ion.
::,:r !i. Uthlum hldroide (UOII) bused to remc've CO2 from exhaled air in contined quaflerslike submarines and
sPac vehicles.
,,r,i 6. fbe alkali m etals rcact uritb, halogens and inlerhologen CI,mpounds formi[S lonlc polyhalide compounds.
KI+ Iz KlI3l
-
KBr + ICI * KlBrICll
KF+BrF, K[BrFll
-
solutio[ of alkali metals such as Li, Na or K in
' ? The
r:iii; on of ethylenic double
bonds, acetylenic triple bonds to double bonds and me Birch reductlon.
r,,i 8 Lithium is lhe li8hlcst knol n metal, having deDsity be, stored i[l keroseDe
oil becausc it floats otl the surfac, It is kePl wrapped in Parafhfl wax.
,i!ti 9. C.s is the mc! electroPositive elcment due to its lowest ioniztion enerry.
,,i | ,r Uthium canDot bc used in makiDg photoelectric crlls bcause out of all the alkali metals, it has highest
ionization enersr and canDot emit elcctroDs when exposed to light.
,il IIThe compounds ofalkali metals are mlourless (unless the anion is coloured like permangaDate or dichromate)
.
and diamagnetic. Thls is because they have noble gas coDfiguraton with no unPaired electroD.
t;i:t 12. The pcrfiides ofalkali metab arc colourless and diamagneticwhilesuper idcs are paramagnetic aod colouM.
iiiir l-1. All alkali meta.ls exist as body-cntred cubic lattice with a coordinatioD number of8.
,ti l.{. Due to small size, lithium does not form alums.
:,,l ti. Alkali metals combiDe $rth mercllry to form compouDds kno n as AmalSams. This readiolr is hiShly oothermic.
1;1.9. Lithium i!:..lliit;i:;r,iii:i:;ir:iii:i:!t:jri:ii:j:iin:i:i:rj:t:.:.:iL.iii,tiir.:iiiii:ij:j mineral is alWays small and thUS extraCtiOn of the
so easv' some importa minerals of
Lithirun is the tust member of alkali m" illilXltJ::
tals. It is the lightest metal known. Mhcrals of.,thtum
12.9.1. Occurrence. (i) Spodumene, LiAl(SiO3)z containing 4-
67o lithium'
Lithium is the thirty-frfth most abundant ele-
ment by weight in the earih,s crust. It mainly occurs Qi) Triphylite, (Li, Na)rPOn.(Fe, Mn)r(POo),
as silicate minerals but the amount present in any containing upto 47o lithium.
S-BLOCK ELEI\,4ENTS 12115

(iii) Petalite, LiA(Si2O5)1 containing 2.7- (SiOr). The ftltrate thus obtained is treated with a
3'7Vo lithilum. calculated amount of NqCO, to precipitate
(iv) Lepidolite, (Li, Na, K), (SiO3)3 OH)2 aluminium and iron as carbonates which are fil-
containing 1. 57o lithium. tered off. Excess of NarCO, is then added to the
(v) A mbtygonitc, LiA(PO1)F. ftltrate to precipitate LirCOr. This is filtered and
dissolved in HCI to obtain LiCl which is purihed by
Lithium also occurs in certain spring waters
and insome plantssuch as tobacro, beat and sugar- cxtraction with alcohol.
cane. In India, Iithium is mainly found as lepidolite (ii) Fuslon method. The powdered silicate
in Bihar, Rajasthan, Karnatka and Kashmir. mineral is fused with CaCO, and the fused mass is
12.92. Dilliculties encountrd during ex- extracted with HCI and filtered. The filtrate con-
traction of alkali metals. tains chlorides of Li, Al, Ca, Na and K whereas
Alkali metals, cannot be extracted from their silicon is removed as insoluble residue. The filtrate
ores by the usual methods of extraction of metals is evaporated to dryness and the residue is ex-
becausc of thc following difhculties :
tracted with pyddine in which only LiCl dissolves.
Pyridine is distilled offwhite LiCl is leftbehind. The
(i) Alkali metals are strong reducing qgents and
method discussed above may be summed up in the
hence can tot be &rocted, by reduction of their oides following flow-sheet.
or chloides.
(ii) Alkali metals being higltly electropositive Lithium ore (Spod,rmene or l,epidolite)
cannot be displaced from the aqueous solutions of Flrse with CaCO3,
tluir sahs by otlrct rnetals.
and enract with Hcl and filter
(iii) Alkali metals csnnot be isolated by
electt olyis oftlrc aqueous solution oI their salts since
hydrogen is liberated ot the csthode instead ol the
alkali metalbecausethe discharye potentiols oI alkqli (sio2) (Chlorides of Li, Al, Ca, Na, K)
nwtals are much higlwr than that of tlrc lrydmg*. Evaporate to dryness aod
However, by using mercury as cathode, the alkali
extract with pyridine
metals can be deposited at the cathode but the
alkali metal so deposited readily combines with IDs-oluble
mercury to form an amalgam from which its (LiCD
rccovery is very difficult. flacl, KCl, CaCl2, AICI3)

Therefore, in view ofthe above difficulties, rh ofllthlum chlotkle. A mixture

only ruccesslul method is the elecnolysis of their
molten (fused) sqlts usudlly chloides.
But the melting point.. of these chlorides are
vcry high which are normally difficult to attain. This
difficulty can, however, be overcome to some extent
by lowering the melting points of these chlorides by
the addition of suitable salts such as CaClr, l(F etc.
12.93. Extraction of Lithlum,
It involves the following steps : tions take place
2. Electrolysis
of dry lithium chloride (557o) and potassium
chloride (457o) is fused and electrolysed in an
electrolytic cell shown in Fig. 12.2.
Potassium chloride is added to increase the
condtctiity of lithium chloride a.od to lower the
fusion temperaure. The cell is operated at a
temperature of about 723 K and voltage of 8-9 volts
is applied.
As a result of electrolysis, the following reac-
:

1. Preparation of lithlum chloride. The Licl + Li+ + cl-

minerals are fust of all converted into lithium
chloride by any one of the following methods :
(i) Acid fieatment method. The finely pow-
dered silicate ore is first heated to about 1373 K to
make it more friable and then with HrSOa at 523 K.
The LirSOo.HrO thus formed is cooled, leached
with water and then filtered to remove silica
At cathode : Ll+ + e- -------'Li
+ C\
At anode : 2 C'l- - 2e-
Chlorine gas, a valuable by product, liberated
at the anode leaves the cell through the exist while
molten lithium rises to the surface of the fir-sed
electrolytc and collects in the cast iron cnclosure
surrounding the cathode. The metal thus obtained
12116 Pradeep's

MOLTEN LITH IUM

INLET FOR
REFRACTORY clz FRESH CHARGE
LINING
1 I
CAST IRON
ENCLOSURE
FUSED
LiCl+ KCI

GRAPHITE
ANODE
BRICK I /ORK
STEEL
CATHODE

FIGURE 12.2. Electrol9,tic cell for exkaction of lithium.

is 9970 pure and is preserved bykeeping it wrapped in air or orygen at about 375 K, it burns with a
in paraffin wax. It may be noted here thal lithiunt brilliant white light forming lithium monoxide,
being the lighest metal known (cknsity :
g' 5j4 t Li2o
cm-3) cannot be stored in kerosene oil since il llodls 4Li + Oz '------' zLiko
on the surface.
Llthium. (ii) Action of water Lithium reacts slowlywith
12,9,4. Propertles of
water evolviug H, gas, However, the reaction is
(a) Physlcal properties.
much less vigorous than in case of Na or K.
(i) Lithium is a silvery white metal.
LLi + 2H2O -'-- + zLiOH + Hz
(ii) It is the hardest alkali metal but still is soft
enough to be cut with a knife. (iii) Action of acids. Lilhium.being a strongly
(rrr) Atomic and ionic radii of lithium are the electropositive metal, readily reacts with dilute
lowest aootrgst alkali metals. acids evolving Hr gas.
(iv) It is the lighest element known (density 2 Li + H2SO4 ----'' LizSOl + H2
5'34g cm-3). 2Li + 2HNO3 ...-2LiNO3+H2
(v) Being the first member of alkali metals, it
has the highest elec(ronegativity (0'98), highest (iv) Reuction with non-metdls. Lithium on
ionization enthalpy (520 kJ mol-l), highest melting hea[ing combines readily with number of non-me-
point (453 5 K) and highest heat of atomization tals forming their corresponding compounds.
(1603 K). A
2 Li + Hz -------> 2 LiH (Lithium hydide)
(vi) When voltatilized, it imparts a crimson
red colour to the flame. A
(b) Chemidal propertles. Lithium like other 6Li + N2 Z LitN (Lithitrm nitride)
alkali metals, is a monovalent electropositive ele-
-A
ment. It a highly reactive element. However, 2 Li + Clz " -'- 2 LiCl (Lithium cltloide)
amongst alkali metals, it is the least reactive. Some
important chemical properties of lithium are : 16 Li + Ss .*A 8 Lr2S (Lithium sulphide)
(i) Action of air Lrthium tarnishes slowly in A
moist air while dry air has no effect. When heated 12 Li + P4 4 L1p (Lithirtnt phospltide)
-
 12117
S.BLOCK ELEMENTS

In fa ali metal which (viii) Lithium hydride is used as sourcc of

combines o form lithium hydrogen for meterological purposes aod for filling
nitride. Li is rubY red. Ou of balloons.
heating to a high temperature, it decompose's to its fu\ Liihium hvdroxide is used for removing
constiiutent elementi. lt also reacts with water cO, ion exhaled an in closed quarters like sub-
evolving ammonia marines and space vehicles.
A 's
UrN """r 6 Li + N,
2 (x) Lithtum sluminium hytuide (Li.AJIl.)
used as a reducing agent itr sytrthetic orgatric
Li3N + 3H2O -""'3LiOH +NH3 chemistry.
(, ffie other alkali 12.10. Sodium
metaG, ammonia to form
a deep formation of am' Sodium is the sevcnth most abundatrt
moniated electrons. elerne.at by weight fouod in the earth's crust.
1%-200I( Mlnerals of sodlum
Li + (.t + y) NH,
(i) Atbite or sotu leldspu Na2O.Al2O3.6SiO2
Li (NH3), + e- (NH3),
or NaAlSirO,
Howcver, when NH, gas is passed over mol- chloide NaCl
(ii) Rock salt or sodioa
ten lithium, lithium amide is iormed. nioate
A (iil Aile salt pene ot sodium NaNO3
2 Li + 2 NH3 --'r 2 LiNHz * Hz (iv) Glanbels salt or sodium svlPhate
12.95. Uses of Llthlum. Na2SO..10[O
(r) (a)
(v) Boru or soilium borate
lithium- for
Na2[B.OdOH)a]. 8HrO or NarB.Or'10HrO
making es'

(b) eat tcnsile Out of these minerals only NaCl has been used
strength steel lt is econoEically to exEact thc metal and /rence NaCl
used for is the ore oJ sodium.

(c) Lithium is 12.102. Extraction of Sodium

extremely tough rs Sodium is extracted by the electrolpis of
used for armour ts' fused sodium chloride by a process called Down's
(rI) It is used for producing thermonuclear Proccss,
energr iequired for propelling rockets and guided Dllliculties encountered Although sodium
missiles. chloride is very cheap and h abundantly available
or scavcnger vet the derclopme tt of Down's process for the ex'
since and nitrogen' iraction of sodium ftom fused sodium chloride was
Thus ces of orygen delayed because of the following reasons :
and nitrogen during refining of metals such as cop- (i) Sodium chloide melts o. Im4 K ad it is
per and nickel. difrcufi to afrain and maintain this high lempemture'
Gv\ Lithium corbonate is used in making a (ii\ Sodiwn boih at about I 156 K and hence at
speciil variety of glass which is very strong and is rhe temperanre of electrolysis, the melal liberuted
weather proof. will vaporise.
(v\ Lithium chtoidz s used iu air-condition' (iii) Molten sodiwn fotms a metallic fog (col'
ing ptants to regulate the humidity. lt is also used io loidal sohttion) with fitsed sodium chloide'
Ni-Fe accumulators. $v\ The pruducas of eleclrolysis, sodium and
(i) Lithium bimide is used in medicine as chloiii, corride the mateial of the cell at this high
sedative. temPerufrua.
Mi'l Lithiun bkaftonote and lithium salicy In 194, J.C. Down overcane all these diffrcul-
,ate havi been used for treatment of rheumatism ties. He observed that the addition of calcium
since the resulting lithium urate is soluble in water'

v
 12118 Pradeep,s
chloride and potassium fluoride lower the
melting
point of sodium chloride to g50_E75 K. CH LORiN E

INLET TOR FRESH SALT

FIGLTRE 12.3. Down's cllfor exkaction ofSodium.

At cathode: Na+ +s_ _+ Na

At qnode -.

Cl- "'-.----+ Cl + e-
CI + Cl ..........- Cl2
Adyantages of Donn,s procss.
(i) Sodium metal obtained is of high purity
(abo* 99 5%) .
,, .(ii) The starting material, rle., sodium
cnrorr(lc rs yery cheap.

.
(lii) Chlorine is obtained as a valuable by
product.
The chemicat reac(ions taking
_,^_-l::j,,on:.
placedunng electrolysis are
(iv). This process is cheaper
than Costner,s
: prorcss rnvolving electrolysis of fused
Dissociation sodium
Nacl .....-...- Na+ + cl-
hydroxide.

A'KN,@, irE
:;l;l: ii::;:iil i:lii::i,tr :,:i

Extratron ofpotolsdunl since K mctaris more

sorubre-io t(cr (tha[ Na metar is
soruble inrNacr;, porassium
flrfio#:
obrained b' eredrorr^is ora rused.orrtion
oJ iliii"In, iio**'Ji,'i..',",r.d by the rorrowins rwo
1. By electrolysis otfused KOH

KOH--g+1gq-
Aa cathode :
K++e-*11
At orode :
4OH-- C,2+2HzO+4e-
2. Reductlon ofKCI with so.liunr.
Potassium can arso be obtained by reduction
ofKCrlvith Na vapoun at about I125I( in a large f.ctiona ng corumn.
KCI +Na _ NaCl +K
Potsssium thus obtai[ed is about 99.5%
pure
 S.BLOCK ELEMENTS
12119

12.103. Propertles of Sodium 2 Na + 2 HCI ---..+ 2 NaCI + Hz

(a) Physlcal properfles
(vi) Action ol hydrogen. When hcared with
(i) Sodium is a soft, silvery white metal. hydrogen, it forms sodium hydridc.
(r, It is lighter than water, irs density being A
0'97 g cra-t .
2Na + H2 2Na+H-
(iii) lt is sufficiently malleable and ductile. - non-ntetah.
(vii) Action of other It conrbincs
(iu) It imparts golden yellow flame when in- readily with chlorine, sulphur and phosphorus
troduced into bunsen flame. Iorming sodium chloride, sirlphitle anj phosphide
(v) Like other metals, it is a good conductor respectrvely.
of heat and electricity. A
2 Na + Cl, ------+ 2 NaCl
(b) Chemical propertles. Sodium is
more A
reactive than lithium. Some important chemical 16 Na * S, --- 8 NazS
properties of sodium are :
A
(i) Action ol air and moirrrre. Sodium is a 12Na + Po --__r 4 Narp
highly reactive metal. It is tamished rapidly on (viii) Action of ammonia. Sodium dissolves in
exposure to moist air. At first a thin filT ofsodium
liquid ammonia to form a blue solution which is a
monoxide, NarO is formed which changes readily
good conductor of electricity.
into sodium hydroxide by the action of moisture The blue colour of the solution is due to the
and finally into sodium carbonate by the action of formation of ammoniated electrons.
carbon dioxide present in air.
196 K
4 Na + Or """+ 2 |.I2rQ Na + (-r +y) NH, ...-.r Na+(NH3)"
NarO * HrO .......r 2 NaOH Ammoniated sodium

NaOH + CO, ------- Na2CO3

+ e- (NHr),
2 + H2O
Afi moniatcd clecirons (rlre)
or NqO * CO, Nqgo, However, when ammonia is passed through
-r
(ii) Action of orygen When heated in a current molten sodium, it yields sodamide ivolving H, gis.
of air or oxygen, it burns formiag a uixture of 475 K
sodium monoxide and sodium peroxide. 2 Na * 2 NH, ----+ 2 NaNH, * H,
4 Na * 02 """- 2 NEO . (ix) Reducingacabrr. Sodium is a strongreduc-
2Na2O + Oz *2N%Oz ing agent. It reduces many chlorides and oxides.
A
(ili) Action of watez It reacts with water more BeCl + 2Na ..--.r Be + 2NaCl
vigorously than lithium producing H2 gas. A
2 Na + II,O ......- 2 NaOH AlClr+3Na.....r Al + 3 NaCl
2 + tlz
A
Since ionization enerry of Na is lower than Al2O3+6Na ----. 2Al + 3NqO
that of Li, therefore, NaOH is a stronger base than
12.10.4. Uses of Sodium.
LiOH.
(i) Sodium is :used as a reducing agent a the
(iv) Actibn of alcohol. It reacts slowly with
extraction ofboron and silicon.
alcohol evolving H, gas.
mployed as a reduc_
2 qHjOH + 2 Na -..-r 2 C:H5ONa * H, amalgam and as a
Sod. ethoxide in the synthesis of
This reaction is widely used for removing ex-
cess of sodium from various reactions involving Q)i) It is also used in Lassaigne,s test for the
sodium. detection of N, S and halogens in organic com-
, (v) Action o/ acidr. Sodium being more pounds.
electropositive than lithium reacts with dilute acids (rr,) About 60Vo of world production of
and liberates H, gas. sodium is used to nake tetiaethyl lead,
 Pradeep's
12120

Pb(CrHr)n whiclr is used as an anti-kttocking sqent heated to give pure sodium carbonate. Recrystal-
lization fr-om water produces washing soda,
for gasoline. Na2CO3.10 HrO.
@ Liquid Na or its alloy with potassium is NECO3 + CO2 + HzO ---"'r 2 NaHCOT
usetl as a coolant in nuclear reactors.
(r'i) lt is used in lhe manufacture ofnumber ol' 2 NaHCo, '-""+ NazCor + H2o + CO2
chemicals such as Na2or, NaCN and NaNHr' Function of ammonla. COz is only slightly
(uii) Sodium is used in sodium vapour lamps' soluble in water. ds a result, the conccntration of
is largcly used in industry for the
(viii) Sodium HrCO, is very low. Further since H2CO3 is a very
protlucrior: oI artiFrcial rubber, dyes, drugs etc' weak acid, the concentration of HCO3- in the reac-
(r-r) Because o[ its lightness and high thermal
tion mixture is extremelY low.
concluctivity, it is used for filling exhaust valves of :. H2CO3 ...(r)
co2 + H2O
aeropiane engines.
a9ii!9 1..l:: :'i1 1" h' Na2c o:' H2CO3 : H+ + HCO; ...(r,
1
i:l i:-s'- 9 ::l
:

Sodium carbonate commonly known as To shift the equilibrium in the forward direc-
wqr;hing soda is manufactured by Solvoy amnronio tion, a base such ai NH, is used which combines
process.
with H+ to form NH.+ ion.
H+ + NH3 ----' NHr
Thus the function of NH3 is to Produce a
solution.
sufficient amount of HCO! ion which enables
Na+ NHi , cl and HCol sparingly solubleNaHCO, to precipitate out ofthe
,
reaction mixture.
Out oI the various compounds possible, (c) Dtalls of the process. The manufacturing
sodium bicarbonate being sparingly soluble crystal-
lizes out. This is finally calcined to form sodium details of the Solvay ammonia Procss are
carbonate. described below :

(b) Thory When carbon dioxide is passed

brine solution salurated with ammonia,
'r.rough
sodium bicarbonate is formed:
NH3 + HzC) NH:.Hzo- NH1+ + OH-
- ammonia while impurities of cal'
with
Na+ + cl- + NH4+ + oH- + co2""'+ saturated
cium and magnesium present as impurities in coT-
Na++HCo3-+NH1++cl- mercial sodiirn chloride get PreciPitated as their
\a+ + HCot -...- NaHCo3 (as PrecrPitate) corresponding insoluble carbonates.
, NHrCI (in solution) .. (0 2 NH3+CO2+H2O """'-- (NII|rCO3
NHi + Cl-
CaCl2+(NHa)2CO3 """'-'- 2 NH4CI + CaCO3 I
Becau-se of the common ion effect due to the
orcsencc of Na+ ions oI sodium chloride' sodium MgCl2+ (NH)2CO3 ......- 2 NH4CI+ MgCO3 I
Licrrbonate precipitates out. It is filtered and then The ammoniated brinc thus obtained is
ignited to get sodium carbonate. pzssed through ftlters to remove precipitatcd cal-
heat
H2O cium and magnesium carbonates and then passed
2 NaHCO3 ---- NazCO: + CO2 + '('D
through the carbonation tower.
Sodium carbonate as obtained above is con- s made uP of iron
tamirated with ammonium salts. It is puritied by forated horimntal
passing CO, through its aqneous solution' The d brine solution is
soclium bicarbonate thus fornred is filtered and top of the tower

'Non-ev.rluatiw.
 S-BLOCK ELEMENTS
12/21

AMMONIA + LITTLE CARBON D|OXtDE This recovered ammonia mixed

with little carbon dioxide is used lor
saturation ofbrine in the ammoniation
tower as discussed above. Calcium
chloride is obtained as a by product.
Hl AEI--,,EjjJ''"*''" (vi) Lime kiln. Here,
dioxide is generated by heating lime-
carbun

stone to about 1273 K

1273 K
CaCO3 -'-'-' CaO + COz ...(r,)
The carbon dioxide is broucht to
STEAM the carbonation tower whilc liire is
NH.rCl + A LITTLE NHTHCOo slaked with water in a tank known as
slaker to form milk of lime which is
pumped to the ammonia recovery
tower.
FIGURE 12.4. Sofuay.Arnmonia plocess for the Raw Materials. Ttc solvav-am-
manulacfu re of sodium carbonate_ monia process is very economica[since
except NaCl and CaCO, all olher raw
while carbon dioxide
liom the bottom at a p materials used are not consumed in the process.
Carbon dioxide rises For exarnple,
reacts tyith ammoniated brine (a) Quick line (CaO) left in the lime kiln and
to form sodium
bicarbonate. ammonium chloride (NH.CI) left in the mother
NaCl + NH-1 + CO2 + HzO .-._ Iiquor after removal of NaHCO, are reactecl to
produce NHr. Therefore, except for small losses,
NaHCO,(s) + NHoCt (ag)
no additional NH, is required.
Throughout the process, a temperature of
- 310 K is maintaincd.
300- (b) CO, produced during conversion of
(iii) Filtration. The solution flowing out of the NaHCO3 to NarCO, acmrding to reaction (iri) is
carbona(ion lowcr contains tiny crystals of sodium reintroduced in the carbonation lower.
bicarbonate. These are fiItered by passing through Thus, NaCI and CaCO3 are rhe only raw
vacuum ttlters.
materiallused which are quite cheap. At the same
(iv) Calcination ofsodium bicarbonates. The time CaCl2 is produced asa bye product which, of
sodium bicarbonate obtained above is heated
course, has no large scale
strongly or calcined in a kiln when sodium car_ Thus, solay ammonia oroc
bonate is formcd. tiuuous and self-contained
2 + CO2 + H2O
NaHCO, -------+ NarCg,
(v) Ammonia recovery tower. The filtrate
from the carbonation tower contains ammonium
chloride and a little ammonium bicarbonate It is
made to flow down the ammonia recovery tower
while a current of steam is matlc [o go up. Vilk of
lime is introduced at a point little above Ge middle
of the tower. Ammonium bicarbonate is decom-
posccl by steam anrl ammonium chloritle by milk of
limc as lollorvs :

Hcat
NH4HCOT -------. NH3 + CO2 + HzO

2NIloCl+ Ca(t)H)2 .- 2NH3 *CaCt, *2HrO FIGUBE 12.5. Flow-sheet for

SolvayAmmonia process
12122
Net{ Course

(fi) It is used iD the manufacture of soap,

soluble in water, potassium bicarbonate (KHCO)
is fairly soluble in water. Thus, when CO2 is passed
through ammoniated brine, NaHCO3 gets
precipitated while KHCO, does not get
precipitated when CO2 is passed througb an am-
um chloridc. Hcnce,
be PrePared bY the
glass,'borax, caustic soda, sodium phosphate etc'
(rv) A mi:cure of Na2CO, and I!Co, is used
as a lusion mbaure.
(v) It is used in paper and textile industry and
also in ietroleum refining and metal refining'
(u) It is used as a reagent in the laboratory'
SI]CTION_II
,\t,Ku.l)il': I'lAl{ l I{ Irl-liNIIIN',IS

Propertles. (i) Sodium carbonate is a white

crystallini solid which crystallizes as decahydrate
(NqCOr.10H2O).
(r1) It is readily soluble in water.
(iii) Action of h
it loses 9 molecules
lorm monohYdratc elenents of grouP 2.
above 373 K, the monohydrate changes to an an-
hydrous white powder called soda ash but does not
decompose further'
Blow 37J K are
NarCOr.lOH2O """"'-" Na2CO3'H2O+9H2O the
Ab.,vt 37J K the
Na2CO3.H2O Na2CO3 + H2O
(iv) Hvrlrolvsls. Being a salt of a strong base
NaO'gj ana weaf acid (H2CO3), when dissolved
i n water, sodium carbonate undergoes
hydrolysis to
lorm at alkaline solution.
Na2CO1 * ZH2O'----'H2CO3 + 2NaOH
:
(frLakt $io"Q
itt*d) iotti"tr) t
(v) Actlon of acftls. It reacts with dil' mincral
elernent bY
acids evolving CO, gas.
inly occurs
Na2CO3 +2 HCl """'+ 2 NaCl + H2O + CO2 t and chalk.

(vi) Reactloo wlth mltk of llme. With hot milk

Other important mineraLs of calcium are
of lime, Ca(OH)2, it reacts to form sodium lluoropatite [3 (Cq(PO)) . CaFJ' Wntm
CaSO. . 2 HrO and anhYilrite CaSOn
hydroxide.
Strontium and barium are much less abun'
Ca(OH)2 *Na2CO3 -"""+ ChCO3 J +2NaOH dant. Whereas strontium is mined irs'celestite
SrSOa and.t mntiarlire SrCO, and harium is mined
Uses. (i) It is used for softening ofhardwater,
laundry and cleaning. as barl'tes, BaSOo. Radium is extremely scrare and
is radioactive.
(li) It is used in Paints and dYes.
.MaBncsia (MgO ;trontia (SrO) and baryta (BaO).
 S.BLOCK ELEMENTS
12123
12.13. Electronic Configuration
the atkaline earth Eerars have two s-electrons in their
outermost shel (ns2) as shorvn
a *#";1r".'" "tall

TABLE 12.5. ELectronic configuration of alkaline carth metuls

Elcctronic

Bcryllium (Be) 4 b2 ztz

[Hel2t2
Magne,sium (Mg) l2 G x2 2p6k2
[Nel 3r2
Calcium (Ca) 20 1s2 2sz 2p6 xz 3p5 4] [Arl 4r2
Strortium (Sr) 38 k2
1t2 2s2 2p6 tsz 3p6 34to 4p6 *2 I Kr] 5l2
Barium (Ba) 56 hz X2 2p6at23p63dto*2 4p6 4dro *2 Sp6 &2 [Xe] tu2
Radium (Ra) 88 7s2 ztz 2p6 a? 3pG Sdto 4sz 4pF 4rto 4ft [Rnl 7.r2
ssz 5p6 sdto 6tz 6p6 iiz
As these elemcnts have similar varence.h"rt
chemical properties. "t"tio@
some important physical properties of arkaline earth meta.ls
are given in Thbre 12.6.

TABLE 12.6. Phlsical properties ofgroup 2 elements (alkali

Sr Ba Ra

Atomic number 4t220

Atomic mass 9.01 24.3't ,().08
Metallic radius/pm 112 160 197
Ionic radiuvpm
IoDisation eDthalpy I
51
899
72
't3'7
100
5m
i*
509
(U mot-r) [ 1'157 1450 1146 9't9
Enthalpy of hydratioo of -u94 _1577
-1921
M2+ iors (kJ mol-l)
ElcdmocgatMry
(Pauling scalc )
Density/g mol - I at 293 K
Melting point /K
Boiling poinr /K

B (9at 298 Kfor

M2+ 1aq1 +zc- -1.97 -2.37 -2.81
-y1s1
Occurence io lithGphcre

rppm (pans per million) percentage byxEighr

'r
 Pra,lcc l"s Ner4 Course Chemist4llffi
alkaline earthmetals (e.g. Mg), the second electron
i" to be t"mou"d from"a citioo (unipositive ion)
l. Atomic radii The atomic rudii ol alkaline able noble gas con-
the
eafth metqls are foirly tarye though smaller than I of second electron
<:orresponding aikali metals qnd lhey inoeose dotett s requires much less
llrc gtoup.
due to higher nuclear
c tends toPullthe orbital
e ds the nucleus'
on movins down the group, atomic radii in-
crease primaritidue to addition ofan extra shell of
electrons in each succeeding element'
2. Ionic radii. The atoms oJ lhese elements
fotttt divalent ions which show the sane trend ot
-increase
in lheir size down the group.

follows :
(i) The divalent cations of alkaline earth me-
tals ac(uire stable inert gas configuration'

nuclear charge than those of alkali mctals'

MgCl2 is - 642 kJ mol-l. Thus, the enthalpy of
disproportionation reaction,
2 MgCl MgCl, + Mg
-+
is - 642 - 2 (- 125) = - 392 kI mol-r
charge. This imolies that anv method used to prepare
Il is of interest to note lhdt the second ionizotion MX would iways result-ia the formation of MX,
L'nllnlpies I E2 ol the elements of group I are higher compounds. Similarly, we can show that in case of
thqn lhose of the elemenls ol grouP 2' The 'IEt and alkaiine earth metals. MX, compounds are not
18, values ofsodium (alkalimctal) and magnesium formed. In other words, alkaline eqtlh metals
(alkaline earth metals ) are given below : unifurmally lomr diPositive ions.

[.)lenrcnt IEI (kI mol-l) IEr (kJ lEol-r)

Na (Group 1 ) 496 4562

Mg (Group 2) 737 1450

cctron in case of those of alkali metal ions of comparable size [e g',

a removed from a AHvd for Li+ (size 76 pm) = 506 kJ mol-',I-
c alreadYacquired -
anyU fot Vg3*'Gize7} pm) = 1921 kJ mol- I
a reas in case of
 S-BLOCK ELEI\,,IENTS
12125
while thosc ofmonovalent alkaline earth metals are
lower [e.g AHyd for Mg+ =
- 365 kJ mol-rlthan
the corresponding alkali metal ions. Larger hydra_
tion enthalpy is due to the fact that thi alkaline
energy change accompanfng the formation of
MgCl, (ag) is uruch htgler (i.e. 774 H mol -r) than
that of MgCl (aq) i.e. 74 kJ mol-r as calculared
As a resull the enthalgry of hydration of MgCl. is below. Thereforc, atkaline eafth metols preler to
much higher I- tg?f, (Me\ - z. x 370 (zct-) lorm divalent ions rather lhan monovalent ions.

C.mpaLis.n nf .t,rng", i" ,n" n,.-rrr,,, nr*li ,",r l,r,i ir*ii, tr.,l
"n..gy "i
MgCl (aq) aH(tiJrnot-l) MgcL (.rr) A H (kJ nlot--l)

Mg (s).....- Mg G) 150 Mg (r) ...._

Ms G) 150
Mg(s) .....* tvtg+1g;+c- i37 .-
Mg 1s) Mgz+ 91 + z c- 218't
I
ictze) ct (a 122 c\(9 2ct(O 244
-
Cl (g) + c- Cl- (g _348 -
zcl(g)+2e- I _696
Z Ct- G)
Mg* G) * ct-- (E) + aq Mg2* (g) + z ct- (g) + aq
-735 -2661
Mc+ @q) + ct- (oq) Mcz+ (aq) + z ct- (aq)
- Net eDergy changc =
-74 - Net energy change =
-7?4
5. Elec-tropositive or Metaltic character The

. On
rncrease
p, the atomic radii
s decrease. Conse_
quently, metallic character
mcreases.

rnels and greater

etallic bonding in
as compared to
 Pradeep's
12126

tion enersv decreases. Beryllium forms covalent
compoun;s because iL has smaller size and high
ionization energY.
alkali metals, therefore, alkqlifle earth metals ate
lcss reactive thon coresponding alkuli metals'
12.15.1, Realucing character.
The alksline earth metals are weaker reducing
aeents than the alkali metels. Like alkali metsls'
tieir reducing chdracter also increases down the

crcases fro,n Ca to Ba.

lattice.
9. Flame colouration Akaline earth metals
intpafl a characterislic colour to the llame'
Calcium Strontium Barium Radium
Brick red Cimson Apple gzen Cimson'
Be to Ba.

12.152. Reactton with water-Formatlon of

colour to the flame.

r'.'; ieactivrty a n_ci_l: lectrcCe
. steam even at red heat.
All the alkaline earth metals are highly
reactive elements sinc they have a strong tendency
i.-i"." in" two valetrce i-electrons to form the yet
gas con-
corresponding dipositive ions having inert and
reacts with boiling water or steam'
Mg + H2O MgO + H2
-+
or Mg + 2 HzO """'D Mg(OH)2 + 2 H2'

is the most reactive elemenl'

Further since the ionization energies of
electrode
atk"lirJeurth metals are higher and their
;i;;i. [.. negative than the corresponding
 S.BLOCK ELEMENTS
12127
ing vigour even with cold water, liberating H, and A
lbrming the corresponding metal hydroxides 3M+N2 ._ M:Nz
Ca+2HrO-Ca(OH)r+H, BerN, being covalent is volatile while the
Tbis means that reactivity of alkaline earth nitrites of all other elements are cr)ttalline solids.
metals increases as we move down the group. How_ Allthese nitrides decompose on heating and
ever, the reaction of alkaline earth metals is less react with water liberating NHj
vigorous as compared to alkali metals. A
B%N2 """'' 3 Be + N2
Bs CarN, + 6HrO ......+ 3Ca(OH)r + 2NH,
Mg larger ca-
=s
Ca
E- Hili;
(BaOr) is
?3"
Sr formed by passing air over heated BaO at 773 K but
n3K
Ba 2 BaO + 02 .-------+ 2 BaO2

7nK
2 SrO + O, SrO2
12.153. Reaction with air (uitrogrn anrl high prEssurc
nrlgen) SrO, b prepared in a similar way but under

lium
--
highpressure aod temperature. CaO2 isnot formed

form lhk yry^blr_ 9"1 be prepared as rhe hydrale by

treating Ca(OH), witb HrO, and then deLydratin!
ever, powdered and
burns brilliantly e of
the product.
beryllium oxide ride Ca(OH), + HrO, .......r CaOr.2HrO
(B%Nr)
Crude MgO, has been made using HrO, but
A peroxide of beryllium is not known.
ZBe * 02 (air) ......- 2 3"9
A
All peroxides are white crystalline ionicsolids
3 Be + N2 (air) ----. 3%IV, cortaining the peroxide ion, Ol-.
Treatment of
peroxides with acids liberates hydrogen peroxide.
than
ance BaO, + 2 HCI -....+ BaC! + HrO,
and 12,15.4. Reaction with hydrogcn _ Forma-
lion of hydrides.
A
Mg + air ...-" MCO + Mg3N2 pt berryllium
ating to form
even
form
Hca!
es. M+ H, """""'r MH,
Metal b.dridc
The hydride of beryllium caa also be obtaiaed
by the re duction of BeCl, with LiAltfn
zBeclz + LiAlHa -....+ I f,e112 +LiCI+AICI3
(D) Formatton of nitrldes. All the alkaline Both beryllium hydride (BeHr) and mag-
earth metals burn in dinitrogen to form ionic
nesium hydride (Mgtl.) are cnvalena compounds
nitrides of the formula, MrNr. Tbis is in coDtrast to
hoving polymedc soucaues in which H-atoms be-
alkali metals where only Li forms LirN.
tween beryllium itoms are held together by tbree
 i'r'azlca1,': Nety' Coarse Qlla:m istryfififl
12128
1375 K
cntre-two electrotr (3c - 2e) bonds as showD caq + N. -""""rCalcaNCN +c
below : cr'nsrnidc
Tho mixture of calcium cyanamide and carb'
on is called zifolim and is used as a slow acting
>"()'"<)'"(-)'"< nitrogenous fertilizer as it hydrolysis slowly over a
period of months evolving NH3 gas
The hvdrides of other elemenls ofthis group, CaNCN + 3tI2O """r CaCO3 + 2NH3
!.e., CaHr, SrH2 aod BaH, are iontc and contain 12.15.6. Reactlon with ackls.
'he
f1- ions. the hydrides of alkaline earth metals
All All alkaline earth metals react with acid's
react with water fberating H, gas and thus act as liberating Hr.
re:lucine aents
" -trlH,
+ zHzO 'M(OH)2 + 2 H2 M+ 2HCl'-'- Mcl2 + H2
(M=Bc, M& Ca' sr' Ba)
CaH, is called hyrlrolith and is used for
Be being amphoteric also dissolves is alkali
production of H, by action ofwater on it' liberating Hr'
- Formatlon of
12.155. Reactlon with carbon Be * 2NaOH + 2 H2O-NarlBe(OH)al + H,
carbldes. Sod' bcty'late
When bervllium oxide is heated with carbon 12.15.7. Reactlon with Liquid Ammonia
at 2175-2215 i( a brick red coloured carbide of
Like alkali metals, all alkaline earth metals
the formulu, BerC is formed.
2115-7275 K ;l?
eto
It is an iozic compound and reacts with water the formation of metal clusters.
forming methane Thqse solutions decompose very slowly form-
BerC+4HrO ' 2Be(OH)z + CH+ ing amidas and evolving Ur, but ttre reaction is
accelerated by many traDsition metals and their
Sr compounds.
M M + (.r + 2Y) NH, "-'->
in t{2+ G'IH3), + 2e- (NH3)v
heated with carbon.
1
K
"'-"'- CaQ
C; +ZC
1375
e- (NHr)r-'+ NHI + iHr+ 0/ - 1) NH3

UEK Whereas evaporation of ammonia from solu'

CaO+3C , Caq+CO tions of alkali metals gives the metal, evaporation
AII these carbides react with water producing of ammonia from solutions of alkaline earth metals
acetylene gas. eives he)(asmoniatcs which slowly decompose to
"give
"-"r the corresponding metal amides.
CaQ + 2 rlO HC = CH + Ca(OH)2
cal. carbidc A'ttylcnc M(NHS)G "--
M(NHJz + 4 NH3 + H2
here that MgQ on heating
It may be noted 12.'16. General Characteristics ol Compounds
gives MgCr. This carbide contains Q- units and ol the Alkaline Earth Metals p':illtlil;s:1'Yitji:'i;ir't'i'
reacs with watcr to form propyle (i'e'
As discusscd above, due to higher enthal-
methylacetylene) py of formation in the sotd state and due to higher
MAQ + 4HrO""- CH3C = CH + 2 Mg(OH)2 Lidtutio" enthalpy in the aqueous solution'
PrcPYnc aikaline earth ureials unformally form dipositive
Calcium carbide is an important chemical in- ions.
termediatc. When CaC, is hiated in an electric Firrther due to increased auclear charge and
furnacc with atrrosphcric dinitrogen at lii75 It it soaller size, alkaline earth metals form compounds
forms calcium cyaaamide, CaNCN
 S.BLOCK ELEI\,4ENTS 12129

which are less ionic than the corresponding com- BeCI, + 2NaOH-r Be(OH), [ +2NaCl
pounds of the alkali metals. Usually tbe cxides and
other salts of Be and Mg are rnore covalent than MgSOa +2NaOH +
Mg(OH), J + NahSO4
those formed by the heavier and larger members Properties of hydroxides. (i) Basic chuackr.
(Ca, Sr, Ba). A general survey of some of their Due to small size and high ionization enthalpy,
compounds is presented below. Be(OH), is amphoteric. It, therefore, dissoGs
12.16.1. O)ddes and Hy&oxides both in acids and bases.
Oxides. The oxides of alkaliae earth metaLs Be(OH), + 2HCl r BeCt + 2HzO
MO, are obtained either by heating the meta.ts itr
diorygen or by thermal decomposition of their car- Be(OH), + 2 NaOH......+ NarBeO2 + 2 H2O
bonates. Sod. beryllatc
A or Be(OH), + 2 OH- + [Be(OH)a]z-
2M+02 r2MO (M =Be,MgCa) Bcryllatc ion
A The hydroxides of Mg, Ca, Sr and Ba are
MCO3 ""'* MO + CO2
basic. Their basic strength increases as we move
(M : Be, Mg C4 Sr, Ba) down the group. This is because increase in their
Except BeO, all the oxides have rock-sa-lt sizes and decrease of their ionization energies
structures. Rrther, the enthalpies of formation of weaken the strength of M-O bonds in trlOH
these oxides are quite high and consequently they which ultimately breaks to give OH- ions and thus
are very stable. increase the basic strength.
Metal o(ide However, these hydroxides are less basic than
BcO Mso C.ao SrO BaO
hydroxides because
A/ I I' (kJ nrol -l) 550 590 62i 5m 5,15
smaller ionic sizes
These have high melting poiots, have very low
vapour pressures, are verygood conductors ofheat, (ii) Solubilily in watert. Alkali.urc earth metal
are chemicallyinert and act as electrical insulators. hydroxides are less soluble in watsr as compared to
Because of these properties, these oxides aro used the alkali metal hydroxides.
for lining furnances and hence are used as refrac- The solubility of tbe alkaline earth metal
tory materials. Due to small size of beryllium ion, hydroxidesin water increases with i.ncrease in
BeO is covalent but still has high melring poiat
because of its po|,m eic rlLaaure. Each Be itom is
tetrahedrally coordinated to four other orygen
atoms. Therefore, like other metal oxides, BeO is
also used as a refractory.
Hydroxides. The hydroxides of Ca, Sr and Ba
are obtained either by treating the metal with cold
water or by reacting the correspondhg oxides with Be(OH)z
6
L!
water. The reaction of these oxides with HrO is also
IU
sometimes called as slaking. trs(oH)e ar d,
(.) z
M + 2H2O U(, Eo
o
I
-'M(OH)2+H2 Ca(oH)z 1o
(M = Ca, Sr, Ba) o: o
Mo+H2o._M(OH), o5 LzI
s(ot0e oz @ Lll z
(M = Ca, Sr, Ba -I LIJ
I
o
Be(OH)2 and Mg(OH), being insoluble are s4oH)2 E
obtained from suitable Eetal ion solutions by
precipitation with OH- ions.
'l]lc solubility of a 6alt in wate. dcpcnds upon : (i) Iltticc
crlergf and (ii) Hydration cncrE.
In gcneEl, If hrdration cncrB, > Ltticc cocrBr, soh di$ott.|J,.
If hydration cnerB, < lattice cnctE , sar, doar noa d.i,il,ohv.
12130
Pradeep's

12,162. Halides Be + 2NH3 + 4HF -"' (NHa)2[BeFal

A
The alkalhe earth metals combhe directly
with halogens at apProPriate temperatures forming -BeF2+2NH4F
873 K
halides , MX2.
BeO+C+Cl2 ..._ BeCl2+CO
These halides can also be prepared by the v73K
action of halogen acids (HX) on metals, metal 2 Beo + CCln '-"""'' 2BeC\ + COz
oxides. hvdroxides and carbonates.
M+2Hx + H2 5. BeF, is very soluble in water due to the high
'M&
MO + 2 HX"-""'* MX2 + HzO hvdration enerqv of the small Be2+ ion' The other
fl'uorides (Mgir, caFr, SrF, and BaFr) are almost
M(OH)2 + zHx-4MX2+z}IzO
MCO3 + 2HX """'-+ M& + COz + H2O
Properties of halldes
1.
covalent down the group.
are hydr
On hydr
BeCt2 + 2H2O- Be(OH)2 + 2 HCI'
2. The halides of all other alkaline earth me-
tals are ionic. Their ionic character, however, in- 6. Except BeCl, and MgCl2, the other
creases as the size of the metal ion increases'
2 chlorides of alkaline earth metals impart charac-
3. Excpt BeCl2, a[ other chlorides ofgroup
teristic colours to flame.
form hvdrates but their tendency to form hydrates CaCl, SrCl, BaCl,
decreases. For examPle, MgClr'6 H2O, colour Gmssy gEcn colour
Brick rrd colour Crimso[
CaClr.6 HrO, SrClr.6 HrO and BaClr'2 HrO' In the solid phase, BeCl2
Sot.cture ol Becla.

below :

Uses. Calcium fluoride or fluorospar

(i)
In the vapour phase it tends to form a chloro
bridged dimei which dissociates into the linear
(CaF) is by'far the most importaot of all the
iiiutErt" -oro*"r at high temperatures (at nearly fluorides of the alkaline earth metals since it is the
1200 K). orly large scale source of fluorine.
al (ii) CaC! is widely used for melting ice on
.' - o./-'\
--\Ct,/ B" - cl cl - Be - cl roads. oarticularly in very cold countries because
30% eutectic mixture of CaClr/ice freezes at 21 8 K
Mooomer
(Dimcr)
 S.BLOCK ELEI\,4ENTS 't2131

compated to NaCUice at 255 IC It is also used as a ever the hydration encrry decrcases from
desiccant (drying agent in the laboratory). Bez+ to Ba2+ appreciably as the size ofthe cation
(iii) Anhydrous MgCl, is used in the iucreases down the grottp. Hence, the sohrbilities oI
electrolyte extraction of magnesium. sulphates ol alkaline eafth metab deoease down the
gmup nzinly &te to
12.17. Solubility and Therrnal
Stability o, Oxo Salts lrom B*+ toBaz+.
MgSOois due to he high hydration mergies due to
The salts containing one or more atoms of smaller Bd+ and Mf+ ions.
oxygensuch carbonates, (iii) Stability. The sulphates of alkaline earth
bicarbonates, tes oxalates metaf,s decompose on heating giving the oxides and
and phosphat Let us now
discuss the solubility and thermal stability of some
sor.
of the oxo salts of alkaline earth metals. A
MSOa """- MO + SO3
12.17.1. Sulphates.
The sulphates of alkaline earth The temperature of decomposition of these
metals
(MSO.) are prepared by the action of sulphuric sulphates increases as the basicity of the hydroxide
of the corresponding metal inireases d-own the
acid on metals, metal oxides, hydroxides and car- group. For example,
bonates.
M + H2SOI """"'- MSOr + Hz Compunds: BeSOI MgSOa CaSOr SrSO.
MO + H2SO1 ..-.---. MSO. + H2O Temp. of

M(OH)2 + H2SO. ---------- MSO. + 2 H2O

decomposition: 773 K 1168K I4ZZK 1647 K

MCO3 + H2SO1
-------+
MSO. + COz + H2O Uses. (i) The almost negligible solubility of
Propertles of sulphates. BaSO. in water is used h the detection and estima-
(i) The sulphates of alkaline earth metals are tion ofSO!- ions.
all white solids. Berylliuq magnesium and callium (rr) BaSOoii both insoluble in HrO and opa-
sulphates crystallise in the hydratert form, i.e.,
BeSO..4HrO, MgSO1.7H2O, CaSOo.2HrO but que to X-rays. Thereforc,,baium meal is used to
obtair a shadow of the stomach on an X-ray film
sulphates of stronium zrnd barium crystallise which is useful in diagnosing stomach ulcers.
without water of crysta llization.
12.172. Cartonates and BicarboDates.
BeSO4 Alkaline earth metal carbonates are obtained

MgS04
=6
z2
as white precipitates when
(i) calculated amount of carbon dioxide is
CaSOa 6 a0 passed through the solution of the alkaline metal
l!o hydroxides
Q>
SrSOa
M(oH)r(aq)+Coz (8).......' MCor(s) + H2o(4
;!c
BaSO. 3ur and (ii) sodium or ammonium carbonate is
added to the solution of the alkaline earthmetal salt
(ii) Solubility. The solubiliry ofrhe sulphares such as CaC!
in water decreases down the group, i.e. Be'> Mg
Caclz @4 + NarCO, (cq)
> > Ca > Sr > Ba. Thus, BeSOo and MgSOn are
highly soluble, CaSOo is sparingly soluble but the -......-. CaCOr (s) + 2 NaCl (aq)
sulphates of Sr, Ba and Ra are virtually insoluble.
Explanatlon. The magnitude of the lattice
energy remains almost constant as the sulphate is
are
ltYd
,fll.TlJfJT;
hydraied ion
so big that small increase in the size of the cations [B" and hencc is
from Be to Ba does not make any difference. How- precipitated only in an atmosphere of COr.
 prn41' 1' 7r'5 Ne.4 Coulse thcmistqlifrlD
12132
BeCO3 MECO3 CaCO3 SrCO3 BaCO3
B6CO3 <373K 813 K 1171K 1563 K 1633 K
MgCos k*
oaE
BeCO, is thus unstablo and can be kept onty
CacO3 IUJ
ir, o in an atmosphere of COr'
srCo3
o iil Bicarbonates. The bicarbonates of alkaline
gE earth metats are prepared by passing CO2 tbrough
BaCO3
a suspension of metal carbonates in water'

Ab,scncc of CO2 M2CO3 + HzO + COz """.l M(HCOr)2

(soluble)
BeCO3 + 4HzO : (h$olublc)
PEscncc of COz All the bicarbonatcs of alkaline earth metals
arc stable only in solution aIrd have not been iso'
lBe(H2o)112+ + co3- lated in the pure state.
Uses' The extremely low solubility of alkaline
earth carbonates itr watei is made use ofin qualita-
tive analysis. For examPle,

slightly soluble in water but BaCO, is alrnost in'

soluble.

NH4OH.
of
(r'i) The solublo carbonates, i e', carbonates
alkali metals and NH.+ ion are detected by
precipitation insoluble magnesium carbonate'
as
(rr, CaCO3 is used in
solvaY-ammonia
process for manufacture of NarCor, in glass

making and in cement manufacture.

Bez+ to Baz+ . 12.173. Nltrates
Alkalin ared in
All
are, how solution aad saltsby
CO, due the action of nd car-

bonates. For example, bonates.

caco, (s) . .o, *, * Mo+2HNo3-M(No:)z+H:o

lro"rljr"or, M(OH), + 2 HNO, '-+ fvt(|{Orh + 2H2O
MCo3 + 2 HNos -"-' M(Nor)z + Co2 + HzO
fii:, Stobiliy. The carbonates of all alkaline "r,
earth'metals decompose on heating to form the (M = Be, Mg, Ca, Sr or Ba)
corresponding metal oxide and COr' Macnesium nitrate cq'stallizcs as
MgNoj2.6H2o whil eBa(llor)rcrysmllises as an-
A
MCo3 """.. Mo + Co2 trydJali sall
Bervllium nitrate is unusual because it forms
basic nitiate, i.e., [Be.o(No)5l in addition to the
norrnal salt.
All nitrates on heating give the corresponding
oxides.
 S.BLOCK ELEMENTS
12t33
2 M(NO3)2 '2MO+4NO2+02 other members arc iorrtc e.g., CaC, is
(M : Be, Mg Ca, Sr or Ba) Ca2+ 1C
=
q;z-
Strontium and barium nitrates are used in (rzi) Beryllium carbide reacts with water to
pyrotechaics for giving red and green flames producc methane gas whereas carbidcs of other
respectively. alkaline earth metals give acetylene gas. Thus
From the abov-e discussion, il follows that cal- BezC+4H2O -.....- 2Be(OH)z + CH+
cium, strontium and barium are the tfuee elemenls
CaC. + ZHrO .......--+ Ca(OH)2 + qH2
ofgroup 2 whosep rdes
are closelyrelated with (xu) Beryllium does not exhibit coordination
increasing atomic are
highly electropositive, have high negative electrode
potentials (.e. E ) and show systematic l.reods in
the solubility oftheir oxo sa-lts. by making use of d-orbitals in additioa to s- and
'12.18. Anomalous behaviour ol p-orbitals.
Beryllium forms fluoro complex anion
Beryllium, the first member of alkaliae -(rr)
(BeF!-) whereas other members of thi group do
not form fluoro complex anions.

(a) exceptionally small atomic and ionic size

(D) high ionization energy Just as lithium shows resemblance with
(c) absence ofd-orbitals in its valence shell. ils diagonally opposite element magnesium, in a
similar way bery'lium shows resembjance with its
,_-- Someinpo
differs from thi
beryllium diagonally opposite elcment aluniniurn. This is due
its group to the reason that these two elements have the same
(especially the n follJws :'
(i) Beryllium and the
is harder than other members of
its group.
Be2+:
of lheir
(ri) It has higher melting and boiling points
than the other members. Some points o[ similarity are given below :
( ) Beryllium does not react with water evn ve a tendeucy to form
at high temperatures while othcr mctals do, c.g.,
the cblorides ofboth (i.e.
Mg + H2O MgO + Hz cova-lent are soluble in
(Boilins)
(rv)
-' organic solvents.
(ri) Both BeCl and A.lCt, act as strong Lewis
(because
acids.
poladzin
ionic compounds. (ur) Both BeCl, and AICI, have bridged
Because of covalent character, salts of beryl- chloride structures in the vapour phase.
Iium are easily hydrolysed. For example, CI. CI .CI CI
_. _/ \- \./
BeCO, *
HrO.---r [B(HrO).|2+ + CO3-
4
Cl-Be- Be-Cl Al \./'-Al
(v) Beryllium oxide and hydroxide are am- \",/ ,/\,/\
photeric whereas oxides of other alkaline earth CI CI CI
metals are basic.
BeO + 2 HCI ..........- BeClz + HzO
BeO + 2NaOH ---+ Na2BeO2 + HzO
Sod. bcrr atc
(vr) Carbides of Be(BqC and BeCr) are
covalent (e.g, Be = C = Be) whereas carbides of
 Net4 Cttttrse Chenr istr4
12134

(vi) The oxides and hydroxides ofboth Be and Be2C 4H2O ' 2 Bo(OH)z + CHr
+
Al aie amnhoteric and dissolve sodium in ALq + uH2O ,4AI(OH)3 + 3CH4
iua.nxide soiution as well as in hydrochloric acid' (eiii) Salts of both these elements lorm
BeO + 2 HCt ----"* BeClz * HzO t ydrui"d' ions e.8., [Be(OHr)nlz+
and

BeO+2NaOH --.....- NarBeO2 * HzO [Al(OHr)6P+ in aqueous solutions'

AtO3 + 6HCl 2AlCl3+3HzO

AlzO3 + 2NaOH -+ 2NeAlO2+HzO
Sod mela-aluminale

(vii) Carbides of both the metals react with

water liberating methane gas. lA(9o.)r13-'

iii:ti:lii.r:i::iil.:ij:l::iii:lii::iilIil:i;ii::l(:liii:i'ii;ii'6i:-iiiii:i;::.:i:i':;'jliiii'iiiJ:iII;''ii':iii3r1,li:lli:iiiijiii:i:i';

APD R,K
::l.Thecon]poundsofalkalineearlhmelalsinwhichrhemetalisdittslentarcdiamaSneticandcolourlessunless
' with no unpaired electrons'
,rr. #rrii. Thls is tecausc itrey trave notle gas configuration
""toured. most ofthe barium compounds are made from
ili;'i 2. Reduction ofsulPhateswith carboo givessulphides Therefore'
barium sulPhate.
Basoa+4c auur*oao
.:i:j3'MaSnesiumpercblorate(Mgclo4)isusedasadryingageotcalledanhydrone.

12.20. Mag Besides these minerals, magnesium is the es-

sential constituent of chlorophyll, the geen colour-
12r0.1. Minerals of Magnesium' ing matter of the Platrts.
Masnesium is the srxrll most abundant ele- 12202. Extraction of Magneslum
ment by" weight in thc earth's crust lls chiel l. trlom Magneslte or Dotomlte' The ore is
minerals are : calcined to form the oxide.
A
(i) Comollite, KCl. Mgclz 6 HrO MNO: MgO+CO,
(ii) Mognesite, MgCO3
-A
MgCOr.CaCO, MgO'CaO + 2 COz
-"r
(iii) Dolornte, cacor. MgCO, The mineral is obtained ftom the oxide or the
(iv) EPsomite, MgSOo.T HrO' mixed oxides as follows :
(v) LangPeinite, IISO4 2 MgSOo
(c) ftom MgO. The oxide is mixed with carb'
on and heated in a current of Cl, gas.
(vi) Talc, HrMgSiO,
MgO+C+Ct .-.... MgCl, + CO
(vii)Asbestos, CarMgSitOrr(OH), The anhydrous MgCL thus obtained is sub-
Masnesium is also present in sea water up to
an eneni of 0 l3Vo as MgC! and MgSO. from emixed
which it is being extracted on an increasing scale' osilicon
India has a sood reserve (approx. 250 million ton- under reduced pressure above 1273 K.
nes of magn'esite ore, mostly in U.P, Tamil Nadu >l?73K
ud Rajasthan. 2 MgO.CaO+FeSi 'ZME + Fe
+ Ca2SiOa
S.BLOCK ELEN/ENTS 12135

2. Flom sea water. The sea water cotrtainitrg At anode: Cl- Cl+e-
magnesium chloride and magnesium sulphate. is -""'
Cl + Cl ---.-.r Cl2.
concentrated under the sun and is treated with
slaked lime, ca(oH)2. chlorine liberated at the anode passes o.ut
ftom the exist Drovided in the porcelain tube while
MgCl, + Ca(OH)2 """'r Mg(OH), + CaCl, the magnesiurir liberated at the cathode is in the
Magnesium hydroxide being almost insoluble molten_statc (T p %4 K) It being lighter rises to
thus pre;lpitated ii filtered and f,eated to give the the surface- o-f the molten electrolyte from whre it
oxide. is removed from time to time by meaas of per-
a forated laddles. Magnesium thus obtained is about
Mg(OH), """'r MgO * HzO 99Vo ptrc.It is refined further by subliming at 873
K under a Dressure of 1 mm mercury.
lhe onde so oDtarneo ls converteo lnto
MsCl2 as described under I then
(a) above and 3. trlom camalllte' 2 xcl.Mgclr.6Hro. car-

subjected to electrolysis as described below: nallite is hfated to 625 K itr an atmosphere of

Electrolysls of anhydrou ' hvdrosen chloride gas to make it anhydrous Etcess
the hvdmtvsis oJ magnesium
rhe anhydr"* r'aecr,
chrorrde. '1,15]-t::,!:1*L
added to a norten mixture or
"u,"i""i1[Xill
-;;i;;il 'o''""Ir:;i'::{!3'"J,lif?rr.,
is -
(973
- ltlli K) and electrolysed. The electrol6is :
iarried out in an iron vesiel which serues is the The anhydrous carnallite thus obtained is
cathode (Fig. 12.6). A graphite rod which dips 1, fused with anhydrous cacl2 and Nacl. The
the molten electrolyte (MgCl2+NaCl+CaCIr) electrolysis of the fused mixture is then carried out
acts as the anode. Thc anode is surrounded by a as described above'
porcelain tube which prevents the intermixing of 12203. ProPerties ofMagnesium
the products of electrolysis (Mg and Clr). The (a) Pl,ysical propertls. (i) Magnesium is a
electrolytic tank Ls heated to 923- 10Zi K to melt silvery white metal which soon becomes dull in air
the electrolyte. A stream of some inert gas such as (ri) It is a light metal with a density of
coal gas is passed through the tank to epel air in l.74gcm-3.
order to protect the moltenmagnesiumfrorn oxida- (rii) It is fairly malleable and ductile.
tion. On passing electric current, fused McCL un-
-----o-2 -'-
dergoeselectrolysisasrouows: ,,
"",fJtJIl'T,1il:X;"ff#,Xt?:[;""1;:';
calcium, strontium and barium. Some inrportrnt
PORCELAIN i--z -GRApH;TE chemical properties ofmagnesium are :

iJiE-":' -4-
f /.. ANooE OAction of orygen orarr Magnesium does not
react with dry air but slowly gets tarnished in moist
cHLoRtNE GAs
air due to the formation of a thin lllm o[ thc oxidc,
3!3t
-;-I_J I lJ-*coAL GAS Mgo. It burns in orygen or air with a rlazzling light.
A
2Mc+O,
CATHODE
-2MgO
of cafton diuide ond
FU'ED Qi) Action sulphur
:fiE dioxide. Because of its great affinity for orygen,
ffiELtA,rrE::=::::E-+::=.=l H%}t"'' magnesium keeps on burning even in co, or So,'

lRoN 2Mg+CO, .......) 2MgO+C

vEssEL a
2 Mg + SO, """'r 2 MgO + S
FIGURE 12-6. Extraction of Magnesium Uii) Actbn ol nilrcgen. on heating, mag-
.""'n"'." *irh nirr.gcn ro lrrm nragncsiunr
Mgcr, ------- Mgr+ + 2cr- :i;lj:l
At cathocle : Mf+ + 2 c- ) MS .l Mg + Nz * MgrNz
 )\,,dcc p's Neur Coirsc Chr*trwglfrm
12136

Thus whco magncsium burns in air both thc
oxide and the nitride are formed.
(iv)Action ofhologenr. Magnesium on heating
with halogens rcadily tbrms the halides, e.9.,
A used in the extraction of boron and silicon from
Mg + CI2 ....- MgCl,
(v) Action of water Maglesium does not
decompose wrter in cold but decomposes boiling
water or steam.
Mg + HrO (steam) --- MgO + H2
Magnesium amalgam, however, liberates H,
from cold water.
(vi) Action of acids. Difute acids including
nitric acid react with magnesium
dihydrogen.
Mg + 2HCl MgCl + H,
.......r
Mg + Dil..HrSOa ....-MgSOolH,
Mg + 2HNO3 *Mg(NO:)z+Hu
However with conc. HrSOo, SO, is produced
Mg + HrSOo -->MgSOa + SO2 + 2 H2O
(conc.)
(vii) Reaction with allql and aryl halides. Mag-
nesium reacts with alkyl and aryl halides in dry
ether to form covalent compounds called Gignard
reaBenls.
Dryether
Mg + C2H5I CrH5MgI
Ethylmag iodide
Dryethcr
Mg * C5H5Br C6H5MgBr
Pheflylmag. bromidc
-
1210.4. Uses of Magnesium.
(i) Magnesium is the lightest structural metal
having density two-thirds of aluminium. It is there-
fore, widelyused in the preparation ofalloys, Some
ofthe magnesium alloys contain more that9lVoMg
togethet rith 2-9Vo Al alJd 7Vo Zn. Duralumit (Al
= 95Vo, Cr.r:AVo, Mn, = 0.5Vo and Mg = 0.5%)
being light tough and resistant to corrosion is used
for the manufacture of airplanes and automobilc
parts.Magnalium (Al=NVo andMg = tj%)beiry
light, tough and hard is uscd for making balance
beam.s.
(ii) Magnesium burns with an intense light.
Therefore, magnesium (as powder or ribbon)
used in flash bulbs for photography, fireworks and
signal fires,
(iii) Magnesium is also used in cathodic
protection of metals and as an orygen scavenger in
rnetallurgy.
(iv) Being a reducing agent, magnesium is
their respective oxides.
BrOr+3Mg-'+3MgO+2B
SiOr+2Mg p2MSO +Si
It is also used in the extraction of other metals
such as Ti, Zr and Hf.
(v) Magnesium is used in the preparation of
Gignard rcagentr whtch are widely used in organic
synthesis.
to produce (ra) Magnesium is used for ignition of ther-
mite cbarge in aluminothermy.
(ui) A suspensioa of magnesium hydroxide
knowt as milk of ma6reslc is used as an antacid for
patients suffering from acidity.
(rzii) Magnesium carbonate is one of the com-
ponents of tooth paste.
sticTl()N-IIt
12.21. Compounds ol Alkaline Earth Metals
Alkaline earth Eetals form many com-
opounds. Some of these are discussed below :
1211.1. Magneslum sulphat, Epsom salt,
MgSO..7ErO.
Magnesium sulphate ocrurs as Kieseile,
MgSO..2 HrO in Stassfurt (Germany) deposits or
as Epsomite, MgSOo.T HrO in the mineral waters
of the Epsom springs in England. It is prepared
from these minerals by ftactional crystallization.
Prtparation (l) Flom dolomlte.The dolomite
ore is boiled with dil. H2SO4.
CaCO3.MgCO3 + 2H2SO4
Dolomitc
-,
caSo. J + MgSOa + 2H2O +2CO2
The precipitates of sparingly soluble calcium
sulphate are filtered off and the two sulphates from
the resultingsolution can be separated byfractional
crystallization.
(li) From magneslte. The magnesite ore is
powdered and dissolved in dil. HrSoo. The result-
ing solution is concentrated and crystallized in the
is temperature ratge 275-32i K when crystals of
MgSOo.T HrO separate out.
MgCO3 + H2SOa
--'--'MgSO 4 + CO2+ H2O
S-BLOCK ELEI\4ENTS 12t37

(ili) trlom ldeserite. The mioeral kieserite (v) Anhydrous magnesium sulphate is used as
(MgSOa.H2O) is powdered and dissolved in water. a drying agent in Organic Chemistry.
The resulting solution upon conccntration and 1221.2. Calclum oxide.., Quick llme, CaO
crystallization is the temperature range 2il5-320 K Preparatlon, Calcium oxide is called quick
gives crystals of MgSOa.7H2O. lime. It is prepared by heathg limestone in a
(iv) Iaboratory prtparation, In the rotatory kiln at 1273 K.
laboratory magnesium sulphate is prepared bydis- 1273K
solving magnesium metal or magnesium oxide or CaCO, <- CaO + COz;
magnesium carbonate with dil. H2SO4. a H -- + 179'9 kJ
Mg+ H2SOa .--........ MgSO+ + Hz It is only above 1100 Kthat CO2 escapes freely
MgO + H2SO4 """""'r MgSOa + H2O and hence a temperature of 1273 is mahtained.
The necessary conditions for obtaining a good
MgC03 +H2SO. MgSOa + CO2 + H2O
yield of quick lime are :
The resulting- solution upon concentration (i) Since the reaction is rcversible, cotbon
and cooling (275-3m K) gives crptals of dkxide should be removed as soon as il is formed in
MgSOn.T HrO. order to shift the equilibrium in the forward direc-
Properties. (i) Magnesium sulphate is a col- tion in accordance wilh Le Aadiels Principle.
ourless efforoscent (loses water of crystallization (ii) The tempeiature should not be allowed to
slowly) crystalline solid highly soluble in water. rise above 1273 K otherwise silica present as im-
Its extract formula is [Mg(HrO)5lSO..tI2O. purity in lime will combine with calcium oxide to
form infusible calcium silicate.
(ii) Isomorphisma. MgSOn.THrO shows
Abo!,e 12?3 K
isomorphism since it exists in two crystalline forms CaO+SiO, CaSiO, (calcium sili-
; one isomorphous with ZnSC)o.7HrO and the other cote)
isomorphous with FeSO4. 7H2O. Propcrties. (i) It is a white amorphous solid
(ni) It forms double salts with alkali metal with a m.p. of 2?i73 K.
sulphates. The double salt, KrSOo.MgSO1.6H2O is (r'i) It is usually obtained itr form of hard
sold as a fertilizer un der the laame potash magnesis. lumps. When heated is oryhydrogen flame, it emits
brilliant white light called limelight,
(iv) Action of heat. When heated to 423 I( it
loses six molecules of water of crystallisation and (iii) When exposed to atmosphere, it absorbs
charges into magnesium sulphate monohydrate. moisture and carbon dioxide forming slakcd lime
The monohydrate becomes anhydrous when and calcium carbonate respectivoly.
heated to 503 K and on further strong heating, it CaO + H2O ----------- Ca(OH)z
decomposes to give MgO and SO, gas. (moisture) Galciumiilicotc)
423K CaO + CO, CaCOt (calcium caftonate)
MgSOa.T H2O MgSOr.HzO
-6H20 (iv) On adding water, it produces a hissing
-
503 K - Strong sound and a large amount of heat is evolved which
MgSOo ...-- MgO+ SO, conve s water into steam. This process is called
-HzO heating slaking of lime and the fine powder thus obtained is
called slaked lime.
Uses. Magnesium sulphate is used :

(i) in weigbtirg, sizing and fue-proofing of

CaO +H2O ---. Ca(OH)z ;

Paper and cloth. AH = -64 mol-r 5 kJ

(ii) as a mordant for dyeing and tanning. (v) Action of acids and acidic oxides. It is a
(iri) in the preparation of paints and soaps. basic oxide and hence combines with acids and
(n ) as a purgativc in medicine. acidic oxides forming salts.

'Compounds having same crFtal stluctulc arE called lsoErotphous and the Phenomcnon is callcd lsomorPhbm.
" Non -valuative.
121s8 Neq, Course Cl

CaO + 2HCl """""+ CaCl, + H2O (ra) Rcactlon with chlorlne. Slaked lime
reacts with chlorine to form calcium hypochlorite,
CaO + SiO, .........- CaSiO, a con-stituent ofbleaching powder
6 CaO * PaO16"""""'r 2 Car(PO.), 2 Ca(OH)2 + 2 Cl2 """',
CaO + SO, '--""- CaSOs CaCl, + Ca(OCl), +2H2O'
(vi) Reactton ryith coke. When heated with (iv) Reaction with carbon dioxide. Whsn
coke in an electric futnace at2Tl3-3273lt it forms carbon dioxide is passed through lime water, it
calcium carbide. turns milky due to the formation of insoluble cal-
22T3-3273K cium carbonate,
CaO + 3C CaC2 + CO
Ca(OH)2 + CO2 """""'' CaCO3 I + H2O
(vii) Rcacdon wlth amnonlum salts. On heat- (Milkinets)
ing with ammonium salts, it liberates ammonia gas. on
passing excess of carbon dioxide, the
CaO + 2 NHaCI """'-+ CaCl2 + 2 NH3 + H2O precipitates of calcium carbonate dissolve to form
Uses. (i) As a constituent of mortar, it is used
soluble calcium bicarbonate and hence tlrc nilki'
ness disappeors.
on very large scale in building constructions.
a
(ri) In the preparation of cement, glass, cal- CaCO3 + CO2 + H2O '--'--- Ca(HCO:)z
(Soluhle)
cium carbide and sodium carbonate (from caustic
soda). If this clear solution of calcium hicarbonate is
(iv) It is used in the preParation of ammonia heated, the solution again turns milky due to the
and sodalime (CaO + NaOH). decomposition of calcium bicarbonate back to cal-
cium carbonate.
(u) It is used for drying alcohols and non'
Heat
acidic gases. Ca(HCO)r(aa) -..."....- CaCo3(s) + Cozftl)
(r,i) It is used as a basic lining in furnaces. + H2Oo
12213. Calclum hydroxide'' Slalred llme'
CB(oH)2 (v) Reaction with acids. Slaked lime being a
strongbase reacts with acids and acidicgases form-
Pr.eparatlon. (i) Ftom qulck lime. Calcium ing salts.
hydroxide is prcpared on a commercial scale by
adding water to quick lime. This process is called
Ca(OH), + 2 HCI --'---""- Caclz + H2O
shking of lime. Ca(Ofl), * SO, """'r CaSOo + HrO
CaO + H2O """""'. Ca(OH)2 However, Ca(OH)2 does not dissolvc in dil.
HrSC)n because the calcium sulphate formed is
During the prccess of slaking, lumps of quick
lime crumble to a finc powder. sparingly soluble in water.
(tl) triom calclurn chloride.It is also obtained Uses. (i) Calcium hydroxide is used
by treating calcium chloride with caustic soda. (r) for absorbing acidic gases such as

CaCl2 + 2 NaOH ......... Ca(OH)2
Properttes, (i) It is a white amorPhous powder
sparingly soluble in water, the solubility decreasing
further with rise in temperatlutre. An aEteous sofu-
tion is known as Ettu vsbr and a susPension ol
slaked lime in wwer is colled mllk of llme '
(ti) Action of heat. On hcating, slaked lime
loseswater odyat temperatures greater than 7fi) K
?00 K
Ca(OH), """'r CaO * Hzg.
* 2NaCl cor, Nor, SOr, SO, erc.
(ii) lor preparing ammonia from ammonium
salts.
(iii) in the production of mortar which i-s used
as a building material.
(iv) in white washing due to its disinfectant
properties.
(v) for softening of hard watcr.
(vi) in the manufacture of bleaching powder.
(vii) in the laboratory, as linte watar for delec-
tion of carbon dioxide,
S-BLOCK ELEI\,'IENTS
(r,iri) It is also used in making glass, in tanning
industry, as a cbeap alkali for neutralising acids and
in the purifrcation of sugar and coal gas.
1221.4. Plastr of Paris*, CaSO.. l/2 H2O
or (CaSO.)r,HrO.
Plaster of Paris is calcium sulphate hemihy-
dratc Casoa. 1./2 H2O.
Prcparation.It is prepared by heatingglpsum
to 393.
393 K
2 CaSOo.2 HrO ............_ 2 CaSO + 1/2H2O
Gr?6um Plastcr of Pans
+3H2O
The following conditions are necrssary :
(i) The temperatue should not be allowed to
rise above 393 K because above this temperature
the whole of water of crystallisation is lost. The
resulting anhydrous CaSOa is called dead bumt
p/arler because it loses the properties of settiog with
water.
(ii) The gypsum should not be allowed to
come in contact with carbon containing fuel other-
wise some ofit will be reduced to calcium sulphite.
Propertics, (i) It is a white powder.
(ii) On mixing with one-third its weight of
water, it forms a plastic mass which sets into a hard
mass ofinterlocking crystals of gypsum within 5 to
15 minutes. It is due to this reason that it is called
plaster. The addition of common salt accelerates
the rate of setting, while a little borax or alum
reduces it. The setting ofPlaster ofParisis believed
to be due to rehydration and its reconversion into
gypsum.
2 CaSO+ 1/2H2O *3 HrO-----------r2 CaSO4.2 H2O
PlasterofPairs cr?sum
During the process of setting, slight expansion
(l%) in volume occurs. As a rEsult, it cnn take the
shape and impression of the mould in which it is
put.
Uses. (i) Plaster ofParis is used for producing
moulds for pottery and ceramics and casts of
statues and busts.
(ii) It is used for makng statues, models and
other decorative materials.
(iii) It is used in surgical bandages used for
plastering brokea or ftactured bones of the body
and for preparing black board chalks.
'Non-e\,? luativc.
12139
(ir,) lt is alstr used in dcntistry.
Uses of lime. Calcium oide is called lime or
quicklime. Its main industrial uses are :
(i) It is used in steel industry to remove phos-
phates and silicates as s/cg
(if) It is used to make cement by mixing it with
silica, alumina or clay.
(iri) It is used in making glass.
(rv) In chlor alkali industry (includes the
production of three main chemicals : NaOH, Cl2,
NECO3), it is used in thc lime-soda process for the
conversion of NarCO3 to NaOH and vice-versa.
(r) It is used for softening water, for making
slaked lime, Ca(OH)2 by treatment with water and
calcium carbide.
Uses of slaked lime. Calcium hydroxide is
called slaked lime. Its main industrial uses are :
(i) Slaked lime is used as a building material
in form of mortar. It is prepared by mixing slaked
lime with 3-4 times its weight of sand. The mixture
is made into a thick pastc with gradual addition of
water. The paste is called mofiar and is used in
building construction. It sets into a hard mass by
loss of HrO and gradual absorption of CO, from
the air. Sometimes coal ash is mixed with lime
instead of sand.
(ii) It is used in the manufacture of bleaching
powder by passing Cl, gas.
(iii) It is used in making glass and in the
purification of sugar and coal gas.
(iv) It is used in softening of hard water.
Uses oflimestone. Limestone rock is the com-
mon form ofcalcium carbonate.It occurs as chalk,
marble, corals, calcite, aragonite etc. Mixed
',lith
magnesium carbonate, it occurs as dolomite. Its
main uses are :
(i) It is used as a building material in form of
marble.
(r'i) lt is used in the manufacture of quicklime.
(iii) It is also used in the man facture ofquick
lime .
(iv) It h used as a r*w amterial for the
manufacture of sodium carbonate is Solvay-am-
monia process,
12140

(v) Commercial limestone contai-qs iron amounts of magnesia (MgO) and iron oxide
oxide, alrmina, magnesi4 silica and sulphur, with a (FerOr) are also required for imparting suitable
CaO content of 22-56Vo. and MgO content upto colour to csment.
217o. It is used as such as a fertilizer. 12233. Manufactur of Cment
Portland cement is chiefly manufactured by
the following two processes :
(i) Wet Process (ii) Dry Process.
The wet process is preferred wheo the raw
materialsi.e. lime stonc and clay arc soft, climate is
humid and the fuel is cheap. The dry process is
preferred when the raw materials are hard.
The main raw mate rials are lime slone andclqt
building stone in England those days. He, whereas the former supplies lime while the latter is
therefore, named it as portland cement. a source of silica, alumina and iron oxide. The raw
materials are hrst crushed separately in a suitable
machine. They are then mixed in the required
proportions (3 parts lime stone + one part cla,
and ground togcther finely. This grinding is done
either by the dry process or by the wet Process -
The chief components of cement are trical- In the wet process, the clay is washed with
cium silicate, 3CaO.SiO2, dicalcium silicate, water in a wash mill to removo flint and other
2CaO.SiO, and tricalcium aluminate 3CaO. foreign substaaces-
ALO3. Out of all these, tricalcium silicate is the quantity of limesto
mi.ll. The resulting
homogenised to get 'raw slurr/ containing about
4OVo watq.
Inthe dry process, theraw materials are dried
1j!23.1. ComPosltlon of Portland Cement
and mixed h desired proportiors. The mixture is
The average composition of portland cement then finelypowdered and passed through3fi) mesh
is sieves and hornogenised with the help of com-
Line (CaO) 50 - 6n% pressed air. The homogcneous mass is called 'raw
Magnesium oxide (MgO) 2 -3% meal'.
Silica (SiOr) 2l - 25Vo The slurry or the raw meal is introduced into
the upper end of a rotary kiln (Fig. 12.7) by means
Ferric oxide (FerOr) L-2% of screw conveyer. The kiln consists of al inclined
filrrrnina (AtOr) 5-10% steel rotating cylinder, 150-200 ft long and about
10 ft in diametor lined inside with firebricks. The
Sulphur trioxide (SOr) 1-2% charge trarcls downwards slowly due to tbe
For a good quality cment, the ratio of rotatorymotiong given to the kiln and is heatcd by
alumina (A1.Or) to silica (SiOr) should lie between burning coal dust which is blown in from the lower
* end. The charge takes about 2- 3 hours to cover
2.5 and 4 while that of lime (CaO) to silica
the entire journey in the kiln.In thekiln, the follow-
alumina + ferric oxide should be as close to 2 as
ing changes occur :
possible.
(i) In the upper patt of rie tirn, the temPerature
2r3a..Rrfr Materlels
is around 1000- l1fi) K. Here, the charge loses all
The ossentiaf raw materials required for the its water due to evaporation by hot gases.
manufacture of cemetrt are : (i) limestone CaCOt'
(ii) In the middle of,rre kilrr, the temperature
(ii) c/av which orovidesboth silica and alumina and
is around 11m-U!0 K. Here, linestone decom-
iii g'p*^, baSOo.2HrO. Besides these, smalt poses to form calcium oxide and carbon dioxide.

'Non-c!eluatilc.
 S,BLOCK ELEMENTS 1441

RAW MATERIAL

COAL DUST
HOPPEB

DUST
CHAMBER

@LD CLINKER OISCHARGE

FIGURE 12.7. Manufacture of Portland Cement.

(iii) The lower pan of the kiln, f romwherc usal 4 CaO +AlrO, +FezO: + 4 (}O. AlrOr.FerO,
dust is blo*n in is the hottest with the temperature Tckacalcium aluminofcrdlc
ranging betwecn l7'7O -1870 K. As the chargc Due to very high temperature in this zone,
reachcs here, chemical combination takes placc
about 20 - 3070 mirss melts and combines with solid
bctween lime, alumina and silica to form calcium mass to form grey coloured balls (ranging in size
silicates and aluminates : from a pea to that of an egg) called cement clinkers.
2CaO + SiO, 2CaO.SiO, The hot clinkers are coolcd by cold air and are
Dicalcium silicate mixed with 7-3Vo gypstm (to slow down the
3 CaO * SiO, - 3 CaO.SiO, process ofsetting of cement and thereby imparting
l ricalcium silicate greater strength to it) and finely powdered to 325
3 CaO * AlrO, 3 CaO.AlrO. mesh size in grinding machines. The hne powder
Tricalcium alu inate called the 'Potland cement'is sieved and packed in
bug..
2 CaO + AlrO, 2 CaO.AlO,
The flow sheet diagram ofthe entire manufac-
Dicalcium alumtnatc
turing process is given below :

Calcium silicates
Bumt at (2CaO.SiO2, 3CaO.SiO2)
17m - l8m K Addition of
powdered and mixed * Calciuim aluminates Porlland ccnlent
in a Iot tory Liln (3CaO.AlrOr, 2CaO.Al2O3) gPsum
(Cement Clinker)

1223.4. Settlng of Cemcnt sional net work structure involving

The important constituents present
Portland crment ar dicalcium silicate (Ca2SiO.),
2.6Vo, triczlcitdm stlicate (CarSiO5), 517o and trical-
cium aluminate (C arAl,rO r), ll%o.
When water is adde dto cemen,a, arlexothermic
reactior. occvs. During this process, thc cment
reacts with water to form a gelatinous mass which
slowly sets into a hard mass having three-dimen-
-Si - O-Si-
in and -Si- O-Al- chains.
Out of the various constituents of cement, the
most important is tricalcium silicate. It.sets quicLly
and develops considerable strength within a few
days. Dicalcium silicate sets slowly and devolops
appreciable strength after a month or so. Thical-
cium aluminate sets instantaneously in prescnce of
water. The intcrnal strength acquired by cement is
primarily due to the setting oftricalcium aluminate.
12142
Neu) Course Chent is trY

Tetracalcium aluminoferrite also sets rapidly but 1223.6. Cement industrY in India
not as quickly as tricalcium aluminate. India is one of the major cement producing
12.23.5. Cment Substitutes countries in the world. At present more than 60
units, both in prirate as well as public sectors, are
engaged in the manufacture of cement. Their com-
ceme
bined annual production of cement is about 21
creas
million tons. Of these, Associated Cement Com-
some
which is a waste Product from steel industry and
mainly consists of calcium silicate (CaSio3). This
can be added to cement to reduce its cost without
groups.
affecting the quality. In many countries, rice husk
with hith siliia content has been used to make In Haryana, there are two cement factories,
Dadi .
one at Surajpur and the othet at Charkhi
cement,

inalQn5
Q. l.sodlumflrcinthelsboratoryshouldDotbeextlnguishedbyPortritrgreater'Why?
rather
Ars. sodium reacts violentty with vatcr Producing H2 8as which also calches fire. As a result, the fire sPreads
itran Uelng extinguishid. Thereforl, HrO shou-ld not be used for cxtinguishing sodium fire. IDstead Pyrene
(CCL) should b used.
Q. 2. why doe-s tsble salt get wet in raitry ses.son ?

AIls. p'.rre Nacl but rable salt is impure NaCl clDtaining impurities of N%soa ' casoa, M8cl2
is not hygroscopic
aDd Caclz. All of these biog hygrqscoPic absorb moisture from air in rainy
season' As a re'sult' table sall gets

wet.
Q. 3. Alkolt Eetals
are paramagnetlc but their salts sre diaEastretic' EJrplsiD'
during salt formation'
ADS Alkali metals coDtain onc upaired electron (,u1) aod hence are ParamagDetis' However,
*-
th; [o;-metallic forming i$ anion. As a rsult, salt has paired
ifiii ,"p"irio is transferred to ato61
in the cation as well as in the anion and hence alkali metal salts are diamagnetic in nature.
;lecEo;s both"rcctron
Q.4. r,vhich out ol6odium or Potasslum hss blSher Delting potDt ?
weZkens. In other words
ars. on going from Na to K the size of the atom inqeases and hence the meEllic bondi[8
sodi-um f,as higrer melting point than Potassium because ofstronger metallic bonding'
Q 5' Why ceslum can be used h photoclectric cell while lithium canuot be ?
lithium has the highest ioDization cnthalPy. Hcnce Cs can lGc electrons very casily
AN. cesium has the lowest while
while lithium caonot.
Q 6' Why alkali mctals lmPart colour to the llame ?
the flamc and are
A|!s. Alkali metrls have lotr ionization cnthatPics Their valencc elcdfons easily atEorb eners/ ftorn
'-'exlteoiorrignerencrgllcr,rls.Whenth&ebctroDsretumlothegroundstatgttleenerryisemiitedinformofliEttt.

Q 7' Why alkali metals are DorDally kept in k rosenc oil ?

-An6. This is because iD the

8ir they are easily uidized to oxides which may dissoke in the Dloisture ofthe air to form
---tryOro:riaes or they also mmtine directly with water vapours present in moisturc to form
hydroxides.
Q 8' Among alkali metals ln aqueous solutlon, Li+ iou has the lowc6t moblltty' why ?
ans. Because of smallest size among alkali meials' Li+
a

resuli, among alkali metals, mass of hydrated lithiu

rp?
tential.

iiJr":Hf,:"ffi l:'s,ti:'"
Ans (i) Duo to smaller size, Li+ is more polarising than Na+ and hcncc LiCl is more covalent than NaCl.
S.BLOCK ELEMENTS

(ii) Due to bigger size, I- is more polarizablc than F- and hence LiI is more covalent thar LiE
(iii) Due to higher charge, Mg2 is more polarising thaD Na+ and hcocc MgCl2 more corr'alent than NaCI.
(rv) Due to pseudo inert gasconfiguratioo, Cu + is more polarising than Na+ and hence CuCl is more covalent
thaD NaCl.
Q. I l. What mokcs lithium to show properties uncorninon to the iest ofthe olkali metals ? (N.C.E.R.T)
Ans. The unusual propertics of lithium as comparcd to other alkali meta.ls is due to (i) the excptionally small size
ofits atom and ion aDd (ii) hi8h polarising powr (charge/size ratio).
Q. 12. When ls o catton hlghly polarlslng ? Whlch olksll meaal ho6 the hl8h6t polorlsltrg power ? (N.C.E.R.I)
tut A cation is highty polarising if its chargeAize ratio is very high. Li+ ion has the highest polarising pol er among
the alkali metal ions.
Q. 13. The enthslpy offormation of hypothetlcal Cocl(s) ls theoretically fould to be - l8E kJ ool-r ond A/H'
lor Cocl2(r) ls - 795 LJ mol-1. Colculote ArE forthe disproportlorrtlo[ reactlon.
2 Cacl(s) * Caclr(s) + ca(r) (N.C.E.R.T.)
Ans. A/ H'for the above reaction = A/H'(products) A/H'(reaclanls)
-
- A./.H'(CaCl2) + d/ H'(Ca) - 2 Ar.H'(CaCD

= -795 +O - 2 x - 188kJmol-l = -419 kJmol-l

Q. 11. why docs the reactiou )C-Cl+Mf + >C-F + MCI procccd bctter wtth NF thsn wlth NaF ?
(N,C.E,RT)
Ans. The standard e[thalpies of formation of alkali mctal chlorides bcome more and more negative as we move
dot n thc group, ie. a/H'of I(Cl is morc negative (- 42t kJ mot-l) than rhat of NaCl (- 4oo kJ mol-1).
Tberefore, the absve reac on procds better with KF thaD with NaE
It Rb sld Cs fontr supcroddcs ltr preferenc:r to oxldcs
Q. 15, Why is tt that on b.lDg hrated ltr Gxcrss supply ofair,
nnd peroxides ? (N.C.E.R.T,)

ADs. K+ , Rb+ and Cs+ are large cations and superoxide (o;) is larger than cide (o2-) and perqide (ol-) ion.
SiDcc a larSc 6tion stabllizcs a largc aDion, thereforc, these metals form supercidc! in prcfcrence 1o didcs
and perqide.s.
Q. 16. Vghy soludoEs oldksll mctrls ln llquld amuonlo are coaduciug parauagnctlc ond blue la colour ?
<PS.D. twt s)
Ans. Refer to Scc. 12.5.7 on B.gD 1219.
Q. 17, MsgnesluD metal bums ltr sir to givr I tbltc osh. WheD ahls ash ls trcatd wtth tystcr, the odour olsmEonlo
can bc dct ct!d. ExplalD
AtE, Mg bums io afu to form MgO and Mg3Nz.
2ME+Oz +2M8O ; 3Mg+N2-Mg3N2
Magnesium nitride on hydrobGis with H2O gives NH3.
Mg3N2 + 6 HrO.+ 3 M8(OH)2 + 2NH3
Q. lE. Why is crlcluE prclerrcd over EodluE to rcDove lost trrces olDolsture ftoD alcohol ?
Ars. Both Na and Ca reast with water to form thcir respeciive hydrcide!. But Na readily reacts with alcohol to
form sodium ethodde but Ca reac6 only very slowly.
zqHjOH + 2Na._ 2qHjONa + H2
Therefore, Ca is prefcrred over Na !o removc the last traces of moisture ftom alcohol.
Q. f9. Whst k thc dlllcrcncc bctrrccu mllk of llDG and llEG nlter ?
Ars. A sulpension of slakcd lime, i r., Ca(OHt in water is called milk of limc bu I I clear decaoted solutioD of slaked
limc itr watcr is called limc water.
Q. 20. A plcce ol burmlDs Erg[.rtuE rlbboD coDtluue to bun lD rulphur dldde &phlr.
12144 Pradeep's
Atr6. A piece of magDcsium ribbon contioues to bum in SO2 since it reacts to form MgO aad S.

2M8+SO2 "ul *
'*rO '
that heat cvotved keeps the magnesium ribbon burninS.
This reacrion is so much exothermic
Q.21. Alkaline earth metals olr/alrs forlr dlvalcDt catlotrs eve[ though their secoEd ionlzstloE GntbolPi6 rre
olmost dooblc thrtr their llrst lonlzotlon crthrlpi.. Exploir.
Ars. The highcr enthatpy of lattice formation by M2+ ions more tban comPcDsats the tlighq second loniztion
enthalpies of metals.
orgsrlc solvcnta vtlle thosG of Bo do not. Why l]3 lt .o ?
Q. 22. Eelides oI Bc dlssolYc lt!
Atrs Halides of Be are co\raleot because of high IE of Be while those of Ba are ionic due to low IE of Ba.
Q. 23. E $laln vhy handcs ofberyllluo fuEc lr! molst alr but other al]aliDe eorth |Deiol hslld.s do nol
(PS.B. 19e2t

Ans. Beclz being a salt of a wk baac, Bo(OHh aod a strong acid, HCI uodcrgoe6 hydrobsis by watcr to form HCI
wbich fumes in air. BaCl2, oD the other hand, being a salt ofa strorg base, Ba(OHh and stroDg acid, HO dos
Dot undcr8o hydrol,'sis by water to form HCI aod hence does [lot fume in air'
BeCl2 + 2H2O Be(OH)z + 2 HCI ; BaCl2 + H2O *t Ba(OHh + 2HCl
-
24. Itrhy Be and Mg do not glve charact ristic colour to the ltame vhcreoa otbcr alkDllnc earth metal6 do 8lYG.
e.
(IIIS.B. 1993)
Ans. Be and Mg hsve high ionization enthalpis and henc their \.alence electmns are not easiv excitcd.
Q. 25. Why superoxldes ot stksli Detsts sre poromagnetic while nornrsl oxldes art diamagnctlc ?

Ar& Superoxides contain thc ion 02- which has tbe strucEre (: O : O :)- co[taining a thrcc eleclron bond, ia,
it has one u[paired elec-tron and hence is paramagnctic. Normal mids containing the ion 02- do not have
any uDpaird dectmN aDd hcncc are diamagnetic.

,,rv,gi1?Il,Anp,wgr, Q"u.e,s,,*,lgnz aaREVrlI. r MAB*

lNsme thc alksu trrct&ls which form 6upGloxidcs ldben heated ln exc6s of air ? (NC.E.R.T)
Q,
ADs. K, Rb and Cs.
(NC.E.R.T)
Q. 2. Nsmc the Ectal rvhich lloats on xrtlr without ary aPPoraDt rexctlon
vlth iL
Ans. Li.
Q. 3. Nsme the chlel lsctor EspoDEible fo! the anomalous behariour of lithluh' (N.C.D.R. r)
Ans. Small size, high elecrooegatMty and high ioDization enthalPy.
Q. 4. Name the leEcnt which ls Invarlably biYslent ord wh6e odde is soluble lE ercr6s ol Nf,OH rrtd lts
dipositivc ion bas noble 8ss core. (N.C.E.R.T.)

An6. Be ; BeO dissolves io alkali to form beryllates.

(NC.E.RT)
Q. 5. Mention tbe msln corstituctrts ol Foilsnd cement ?
Ans. Dicalcium silicatc, tricalcium silicatc and tricalcium aluminate.
Q. 5. Dr$d the structure ol (, Becl, (vapout) (i0 Beclt (s). (N.C.E.RT)
A-os. Refer to the text.
Q. 7. What happns when Ko2 rcacts with water ? write the balance chemical cquation for th reactloD
l ,!.4. /t.1i 7:)

Ans. 2KO2 + 2H2O+ 2 KOH + H2O2+ o'2.

Q. t. PFdlct glvlDS rrslon the outcomc oltiG rEsdon,

LII + KF- (N.C.E.RT,)
Atrs LiI + IC: + LiF + KI ; lar8er cation smbilizcs larger anio.
S-BLOCK ELEI\,'!ENTS 12145

Q. 9. Name ore reagent or one opemtion to distinguish between

(i) BeSO. and BaSO.t (fi) Be(OH)2 and Ba(OH)2 t \( t.. k t:
Ans. (i) B9SO4 is soluble in H2O while BaSOa is ror (ir) Be(OH)2 dissolves in alkali but Ba(OH)z does not.

Q, 10. Why does bcrylllum shory similarities with aluminiurn ? I \' a / /i 1l

Ans. Due to same electronegativity (l .5) and very sinrilar polarizing power (Bez +=0 064 and Al3 + = 0.060) of
their ions.
Q. 11. Arrsngc the followiDg ilr order ofthc incressi[g covaletrt chsracter : MCl, MBr, Mn, MI (wherc M = alkAli
metsl). I \i( /.' /i 1i,
Ans. As the size ol tbe aDion increa-ses, coralent character increases aod beoce the order is MF < M CI < MBr < ML
Q, 12, What is the geneml llAme for elements ofgroup I ?
Ans. A.lkali metals.
Q. 13. Which olksli metal i6 radioactive ? Give its trtomic rumber also. iI\l,:ttil
Ans. Fr, Z = 87.
Q. 14. Name the alkali rnetalwhich shows diagonol rclationship with magnesium.
Ans. Li.
Q. 15. Which alkali metal acts as the strorgest reducinp agent irt aqueous solution ?
Ans. Li.
Q. 16. Name the alkaline earth hetal which forms covalent compounds.
Ans. Be-
Q. 17. Which alkaline earth metal is radioactive ?
Ans. Ra-
Q. 1E. Narne the alkalire earth Eetsl hydroxide which is amphoteric.
Ahs. Be(OHt.
Q. 19. Why the eleEents ofsecold rorr (lirst short period) show s number ofdilferences in properties from othcr
members of their respcctive familis.
Ans. The difference in tbe properties of the first Drember of a group from thGe of the other meDbers is due [o
(i) smaller size of the atom (ii) presence ofoDe inner shellof only two electrons and (ii) absence ofd-orbitals.
Q. 20. Whflt is diagoEsl rlotionship duc to ?
Ans. Similar size ofatoms or ions, similar electroDegativity or similar polarising power.
Q. 2!. Why alk liDe earth metals have a greater tendency to form coDplexs thatr the alkali metals.
Ans. Due to higher ouclear charge.
Q. 22. Alkali and alkaline earth metals cannot be obtained by chemical reduction method. Explain.
Ahs. Since they are themsekes stroDger reducing ageDts thaD Dajority of the mmmoo reducing agents.
Q. 23. Why does table salt get wet in raiDy serson ?
Ans. Titbld salt contains impurities of CaCl2 and Mgclz which beiog deliquesc&Di compounds absorb moisture from
the air in rainy season.
Q, 24. Why is sodirm metal kept under keroseue oil ?
Ans. Na nretal is highly reacri!,E aDd combines with moisture, 02 and COz of the air forming NaOH, NazO and
Na2COJ etc. Therefore, to protect Na from moisture and air, it is kept under keroseDe oil.

Q. 25. What are the raw mnterials used fo. the manulocture ofwashi[g soda by Solvay pnocess ?
Ans, NaCl, CaCO3 and NH!.
Q. 26. Why is calcium preferred ovcr
sodiuE to remove last traces ofmoisture from alcohol ?
Ans' Both Na and Ca react with water forming their respective hydroxides. In contrast, Na reacts with alcohot ro
form sodium alkodde but Ca does not-
Q. 27. Boncs contain calcium ions. What do you think would be the anion associated with them ?
Ans. PO;- ioD.
12146 Pradcap's
Q,2t, Give one irnportont orc ofeach o[sodiuh ond pottrssiurn.
ADs. Na : NaCl and K: KCl.
Q.29. Give two ores ofmngnesium.
Ars. ClrDallite (Kcl.Mgct2-6H2O) and magnesium chloride (Mgclr.
Q. 30. Thc second ionizfftion enthalpy of calclrm is more than that of the lirst ond yet calcium forms CaCl, nnd
Ilot CaCl, Why? (NC,E,RT)
Ars. The higher cDth6lpy oflattice formation ry Ca2+ ioDs mL,e than compnsates the higher ionization enthalpy
of calcium.
lorEula of dolomitc rrd csrnrllltc.
Q. 31. Glve the chemlcsl
Ars. CaCO3.MgCO3 and KC1.MgC|2.6H2O.
Q, 32"lvhst ls the forEula ol SlPsum ? Whst hsppetrs wher it ls hesterl ?
Ars. CaSO..2HrO. Wben heated to 393 K it gives Plaster of Paris (CaSOa.12H2O) but at 473 K it gives dead
burnr plaster (CgSO4).

Q. 33. What ls qulck llme ? what happeDs whar we sdd wstcr to lt ?

Ars. CsO, slakcd limc, Ca(OH)2 is formed.

Q. 34. Whst ls the forltruh ol Plsster of PorlE ?

I
Ans CaSO..jHrO.
Q, 35.What ts desd burBt plsster ?
Ans. Anhydrous CaSO4 which has Do tendcncy to absorb HzO is called dead bumt plsster.
Q. 36, What 16 Epsom sslt ? Vyhat ls thG scdotr olheot otr it ?
4?3K 573K Hcat
Ars. MgSO..7 HzO; MgSOa.T H2O MgSO.. HrO - MgSO.- MgO+SO3.
-6H2O -tLO
-
Q. 37. Vvty ls lt ueccssarf to rdd gpcuur ltr the llnal 6ta8e ol prepsratlon ol ceElcDt ?
Ars. Gypcum is added to slo$, dowlr the process of setting of ccme[t and thus impartitrg gr3ter strcngth to it.
Q.3t, Wbut ls ,ly osh ?
Ans, It is a waste product from steel industry and has properties similar to that of cment. It mainly consists of
calcium silicatc.
Q. 39. Whyc{lnot sodftlln rnd potssslum bc prparEd by the elc.Eol}5ls ol thclr squcous EolualoDs ?
Ans. The electrode potential i.c. rcduction potential of Na (- 2 .71 v) or K (- 2.92) is much lower than that of
H2O (- 0.83 V), iherefore, upon eleclrolysis, water gets reduced in prcferenca oo Na+ or K+ ions. In other
words, sodium and potassium cannot bc obtained by electrolytic rcduction of Na+ or K+ ions in aqueous
solution.
Q. ,(). Amongst olksu Eetsls, why ls ltthlum rgrrded as tnct spt rcduciEg sSent ln aqueous solutlons ?
(D.S.B.2o0t)
An6. Amongst alkali metals, Li+ has the smallest size and hencr has the highest hdration enerry. In other words,
it has the lo!rcst electKde potential (Eo = V), ie-, it has the maximum tendency to lose electrons and
-3.M
hen(p is lhc t'2ntest (mcf,t aPt) ruducing agent amongst alkali metals.
Q, 41. Strte sny orc resson tor alkallnc earti lltetals having a grEcter tcndency to forD mmplcxct thon elkali
Eetols. (D.5.8.2001)
An& Because ofsmaller size and higher charge on alkaline earth metal cations as compareq to the corresPotrding
alkali metal cations, alkaline earth metal cations have a Sreater tendency to fonn comphxes.
 12147
S-BLOCK ELEMENTS

Scc. 12.1. 1. What are ,r-block elements ?

2. Comment on the statemeDl, "The first element of a grouP shoPs anomalous behaviour with resPct
to the rest of the members of the grouP."
3, What is meant by diaSonal relationshiP io thc Periodic table ? What is it due to ?
(N.C.E.R T)

4, What is thc cause ofdiaSooal siDrilality ?

(A.L'.8.1992)
sec. 12.2. 5. Why are the elements of SrouP 1 called the alkali metals ?
to 12.t.
6. Name the alkali metab in order of infieasinS atomic masses and wrlte their elecronic confiSurations.
The altsli mctals follow the noblc gass in their atomlc structure. what Properties of these metals
can bc predicted from this iDformation ? (MJI f)
& Account for thc follo$,ing :

(0 Alkali mctals show only +1 didation slate.

(ir) Thc hydrqides of alkali metals are strong bases. (P.S.B. 2000\

(iii) Na and K impart colour to the flame but Mg does [ot.

(iv) Li is the be$ reducing agent in aqueous solution. (8.5.8.2004)
9. Discuss the diagonal relationshiP of lithium with magnesium.
t0. List threc properties of lithium in which it diffcrs ftom rest of the alkali metals.
(/vc.E.R.I)
11. Discuss thc anomalou3 behaviour of lithiu m in its 8rouP. compare the Proprties of lithiu m with those
of maSnesiurD- (H.S.B. 2004 C)

12. Alkali mctals have lo 'ionizaiio[ energies. Why is it so ? (a.I.S.B.I9e3)

13. Account for the following
(r) There is a striking similarity betc/n Li and M8. u.I.s.B. 1994)
(i) Alkalimetals are difficult to rcduce. (H.PS.B. 1994)
14. wlry alkEli metah and their salts 8ii charactetistic mlour to the flame ?
(H.S.B. 2001\

15. when ao alkali metal dissotves in liquid aormooia, the solution acquires different colours. Explain the
reasoN for this tyPe ofcolour change. (N.C.E.R.T)
16. What happen. whcn
(i) sodium metal is dropped in water ?

(ii) sodium metal is heatcd in a free suPPly of air ?

(tii) sodium perodde dissolves in waler (N.C.E.R.T\

t1, Explain what happens when
(i) sodium hydrogen carbonate is heated
(i0 sodium amalgam reacts with water
(iii) fused sodium metal reacts with ammonia. (N.C.E.R.T)
Write balanced equatioN for reactions betwcen
(a) NEO2 and water
(D) Ko2 ard waier
(c) Na2O ard CO2. (N.c.E.R.T)
Comment on each ofthc follol,ing observations:
(a) The mobilities of alkali metal ioDs in aqueous solutioD at : Li+ . Na* . K+ . Rb+ < G+
 Pradeep's
(r) I-ithium is rhe only alkali metat ro fo.m a nitride directly
(c) LiF is leasi soluble among the fluorides ofalkali metals
(d) LiF is nrore soluble thao KF in ethanot.
(?) Ljl is rDore soluble than KI in ethanol. (N.C.E.R.T)
20. State as to why
(a) lithium on beiog hered iD air llainly forms rhe monoxide and Dot the peroxide
<N.C.E.RT)
(r) sodium is stored
in kercene oil.
scc. I2.9. 21. List somc importan! mioerals of lithium and sodium.
lr) l2 ll
EDumerate the main diffic'uhies encounBred io the extrac{ion ofalkali metals by usual methods.
23, Sodium metal cannot be obtained by the electrolysis ofaqucous sodium chloride solution. Why ?
u. Dcscrib the Gxtracfion of sodium by DoPn's proces. What precautioDs are takeo for collecting
sodium ?
25. Enlist some important uss ofsodium and potasrium metals.
26. VJhitc equations for thc rections involved in making sodium bicarbooate from sodium chloride.
27. Discrss briefly the funclion of ammonia in sotvay- ammonia process for manufacture of sodium
carbo[ate,
24. Staning with sodium chloride hol will you proceed to prepare (state thc steF onty)
(i) sodium Detal
(ii) sodium hydroxide
(ir'i) sodium peroxide
(iv) sodium carbonate- (N.C.E.R.T)
29. State as to why
(4) A solution of Na2CO3 is alkaline
(6) Alkali meials are prepared by clectrollsis of rheir fused chlorides
(c) Sodium is fouod more useful than porassium.
Give reasons for the follorYing :
(i) Sodium carbonate is prepared iDdirectly through sodium bicarbonatc in Sokay-ammonia process.
(ii) Potassium carbonate cannot be prepared b,, Solvay- ammonia process. (N.C.E.R.T)
What happns when :
(t) Carbon diodde is passed through ammoniacal briDe solution.
( ) Carbon dioxide is passed rhrough aD aqueous solution of sodiun carbonate.
(iii) Sodium hydrogen carboDate is hcated
sec ll t2. 32. Why are elemeots ofgroup 2 kno\Mn as alkaline earth metals ?
to 12.22.
33. Name the alkaline earth metals and give rheir electronic coofigurations.
34. Why are alkaliDe earth metals good reducing agents ?

35. Alkaline eartb metals form ionic salts having bivalent ctioDs. Justify the statemenr by giving reasons
iD favour of),our answer. (lLS.B. Sanple Paper 1991)
36. In what respects does BeC'12 differ ftom the halides ofother group 2 elemeots ?
31. What is diagonal relationship ? Discuss the diagonal relationship between Be and AI. cive the points
of resemblanc between Be and Al. tt. & K. 1997; H.S.B. 20041
3t. Explaio the trend ofsolubility ofcarbonates, sulphates and hydroxides ofalkaline earth metals down
tbe group. (PS.B. 1992\
39, The second ionization energy ofan alkaline earth metal is higher thao its first ioDization eners'. Why
isitso? (A.I.S.B. 199i)
S-BLOCK ELEMENTS 12149

40. Why do alkalinc earth metals not (rccur in the ftee state ? Name some important minerals of
magnesrum.
41. Holr does magDesium occur in nature ? Hor is lhe magnesium metal obtaincd by the electrol,6is
method ?
42, Why alkaline earth metals cannol. be obtained by reduction oftheir dides with carbon ?
43. Give reasons for thc following ?

(0 Alkaline earth mctals do not occrr free in nature.

(ir) Magnesium doe6 not impart colour to the flame whilc calcium does.
(iri) Alkalioe earth metals always form dirralent catioDs cveD though the second ionization etrergies of
thesc metals are almct doublc their first ionization energiet
(iv) A piece of buming magnesium ribbon contiouc-s to burD in SO2.
(v) Be and Mg do not impart mlour ro the flame. (H.S.B.200tt)
44. The hydrdides and carbonates of sodium and potassium are essity soluble in water while the
corresponding salB of rnagnesium aod clcium are sparingly soluble irl E?ter. Frplain.
45. Give three important uses of eacb ofcalcium and magnesium.
46. What happens when
(i) nagnesium is bumt in air
(fi) quicklime is heated with silica
(rii) chlorine reacls with slaked lime
(iD calcium nilrate is heated. (N.C.E.R.T)
47. Commercialaluminium alt*a)6 contains somemagnesium. Name two such allojls ofalumilium. What
properties are imparted by tbe additioD of magnesium to these allq6 ?
(N.C.E.R X)
Beryllium qhibits some similarities with aluminium. Poi[t out tbree such propertics.
(N.C.E.R.T')
Like lithium in Group l,
beryllium shows aDomalous behaviour in Group 2. Yy'rite three such
properties of bcryllium which make il anomalous io the group. (N.C.E.R.T)
Complete the following equations for the reaction betwecD
(i) C + Hzo
0i) BeOH + NaOII
('lr) C(oHh + Cl2
(iv) BaO2 + H2SOa. (N.C.E.R.T.)
Cootrast the action ofheat on the following and explaio your aDswer:
(i) Na2CO3 and CaCo3

0i) MgCl2.6H2O and CaCl2-6H2O

(ni) Ca(NO3)2 and NaNOj (NC.E.RT)
s2. Ho$, will you explain ?

(i) BeO is iosoluble but BeSOI is soluble in water

(x) BaO is soluble but BaSO4 E iDsoluble in warer

(iri) E for M2+ (oq) +2 e- (where M = Ca, SrorBa) is nearly constant.

-M(s)
(iy) NaHCO3 is knotm in solid state bur Ca(HCO3h is oot isolated in solid state.
@.C-E.R.T)
53. Give one method of preparing quick lime. What happcDs when raiD water falls oo it ?
54. What is Epsom sali ? How is ir prepared ? EDIist its important uses.
55. How is Plaster of Paris prepared ? Describe its chief property due to },hich it is widely used.
(NC.E.R.T.)
12150 Pradeep's
56. Differentiatebetween
(d) quick linre
(b) lime water
(c) slaked liole. (N.C.E.R.X)
57. Describe two imPortant uses of each of the following :

(i) quicklime
(i,) gypsum
(iii) calcium carbide
(iv) magnesium sulphate.
5E. Describe the importance of the following :

(i) limestone
(ii) cemeDt
Paris.
(iii) Plaster of (N.C.ER-TI
ste I.2.52.59. Listthe raw materials required for the manufacture ofPortland cmcnt ? Whatisthe role of$PsuDl
in it (N'C'E'R'T"'
60. Whar is the effecr of hear on the followiDg compounds ? (Write equatioDs for the reactions).
(i) Calciunr carbonate
(ii) Magnesium chloride hexahydrate ?

(,,t) G}?sum
(iv) Magnesium sulphate heptahydrate.

L CARRYING 5 or rnor6 MARKS

Sec. 12,1. 1. Discuss the position of lithium in the Periodic table. How does it differ from other members of the
to 12.20. famity ? Ib what other elemelts iD the Periodic table does it resemble t Justiry your answer with
suitable oramples. @.1.5.8. 1990 C)
2, Give general characteristics of alkali metals. Discuss thc anomalous bebaviour of lithium. Mention
similaiitics sho n bylithium towards magncsium ? (A-I.S.B. 1992')
3. List some imponanc ores of lithium. Discuss the various difficulties encountered in the extraction
ofalkali metals. Describe briefly the extraction of lithium ftom a silicate ore.
4. How is sodium obtained ry the Down's process ? Write equations for the reactiom involved. Why
sodium cannot be obtained L'y electrolysis of aD aqueous soluiion of sodium chloride ?
Describe iD detail manufacture of sodium carbomte by the solvay process. State the PriDciPles
iovolved in rhis procss . (N.C.E.R.T'
Why is it thatJ-block elements Dever occur free io nature I What are thgir usual modcs of occu rreDc
andhow are they generally prePared ? (N.C.E-R.I)
1 write three general characteristics of the elements ofJ.block of the Periodic table which disrinSuish
them ftom the elemcnis of the other blocks. <N.C.E.R.T)
Crmpare the solubility and thermal stability of the following mmPounds of the alkali metals with
those of the alkaline earth metals.
(4) nitrates (c) carbonates (c) sulPhates (N.C.E.R.T\
9. MeDtion the geDeral treDds in Group 1 and Group 2 with increasing atomic number with respect to
(i) deNity (ri) melting point (i.i) atomic size (iv) ionization erthalPy. (N.C.E.R.")
How do the following proPeriies change on moving froD Group I to Group 2 in the Periodic table ?
(i) Atomic size
(ii) Ionization eothalPy
(iii) Density
(iv) Meldng points. (N.C.E.R.T)
S.BLOCK ELEMENTS 12!51

11' ComParc and contrafi the cicmistry of Group 1 mctals with thcc of Group 2 mctab Mth respcct to
(r) natur ofcddcr
(ir) lolubility and thcrmal stability of carbonatB
(sr) polarizing pof,.cr of cations
(rv) reactiviry 8nd rdudtrg pcnEr. (N,C,E-R"T)
12, Tbc chcmfutry of bcrylliuE ir mt esseoually ionic. Justlry tbc lurtcEcnt brr meki[g a rcfsrsBcc to the
nsturc of cidc, d oride, fluodde of bcryllium. W,CA.R.D .
13. Give any.thrce Point! ofsimilarity between beryllium and sluminium and mo points ofdbslmilarity. '
_

bett*En bryllium ard bariuD"

. f4 DE*cribc threc iDdwtrial uscs of caultic soda. D6cdbc orc Ecthod of manufteurc of rodluE
trydrcdde. Whst happeDs $tcn sodium ,rjdr(ddc rescls wilh (r) atuminium mctd (n) COz
(tOsio2? w.c-B-rcn)
Sec. 12.21 13 Name chlf forms ofoccurrcnce of m8gneslum h nature. Howb magDcrium e of
ractcd irom one
to t2 .23 . ?
its ores -
N.CE.R.L)
16 Dcscribc thc manuhctur of podand cemctrt., Wbat b itr spprGiDstc cGlpoaltim ?
 Sodium Peroxide
1.
Manufacture. It is manufacturcd by heating sodium metal oD aluminium trals in CO2 free air'
2 Na + 02 (air) -.... Naroz
peroxide is due to
Properties. (i) Pure NEO2 is colourless. The faiDt yello\r'colour of the ordinary sodium
ycllow colour' however'
the presence of a small amount of sodium suPeroxide (Nao2) as an imPurity' The
disappears when it comes in contact with moist air due to the formation of NaOH and NqCO3 Thus'
4NaO2 + 2Co2
-2NECo:+3oz
zNa2oz + zHzo .- 4 NaOH + 02
2 NaoH + CO, -.- NarC6, .' 11rg
(r'i) Sodiun] perodde is a po$'crtul oxidising agent' It oxidises
iii chromium (III) hydroxide to chromale ion
Ol- +2HrO+2e--4OH- lx3
Cr(OH)3+5OH-- Crof,- +4H2O+3e- lx2

2 C(oH)3 +2ol- 297of,- +2oH- + 2H2o

-
(ii) Manganese atlphale to sodium manganole
Mnsoa + 2 Na2o2 .. NazMnor + NazSol
(iii) Sulphidet to ;ulPhates

S2-+3Ol- +2H2O _ Sol- +aOH-

Uses(i)ItisusedtorthepurificatiooofairincoDfinedspacessuchasubmarinessinceitcombineswith
CO2 to form sodium carbonate and oxygen.
2N\O2 + 2COz -- 2 NazCO: + Oz

(Ii) Because of its oxidising ProPerty, it is used as a bleachinS ageDt'

and many che-licals such as benzoyl peroxide' sodiuD
il;;; NarO, is wiOety used in the manufacture of dyes
perborate ctc.
2. Sodium hydroxlde, Caustic soda, NaOH
CausticsodaisnaDufacturedtrytheelectrolysisofanaqucoussolutionofsodiumchloride'ThgfollowinS
two types of cells are used.
12152

a
S.BLOCK ELEMENTS 12153

ADDITIONAL U9EFUL INFORMATION

(.,) The mercury csthode cell-(Castner-Kell[er cell), It consists of a large rectaDgular iron tank iD which
mercury flors at the bottom of the cll and is made the cathode. The brine solution flo\+s in the same direction.
The anode consists of a number ofgraphite blocks. When electricity is passed. electrolysis of briDe occurs. Since
bydrogen has a hi8h over voltage at mercury cathode, sodium is prelerentially discharged at the cathode which
forms amalgam with mercury.
The sodium amalgam flows out and is reacled with watcr ro give NaOH.
2Na.Hg + 2H2O 2NaOH + 2Hg + H2
Hydrogen and chlorine are the two bye-products
-
of this process.
(D) Dinphragm cell-Nelson Cell. In this cett, NaOH aDd Cl2 are kept separate by the use ofa diaphragm. It
consists of a U-shaPed perforatcd steel cthode lined on the inside with asbestG diaphragm and is suspeoded in
a rectangular iron ta[k. The anode coDsists ofa Sraphite rGl and issuspeDded in thesolution. On passing electricity,
electrol,,sis begiDs ; Cl2 is libratcd at the graphiie anode and NaOH is formed at the outside edges ofthe cathode.
(c) UsingNaflon Mmbrane Cell. The naturalbril)e is now clectrollsed io a membrane cellinwhich cathode
and aDode are seParated by NAFION membrane. Nafion is a copotymer of tetralluoroethyleoe altd perfluoro-
sulphonylethory ether. Tbe copotlmer is supporred on a tefloD mesh. plastic membraDes (at NafioD) are
increasingly being used in diaphragm crlls thcsc da)6 because of rheir lower resistance than asbestos.
Properties. (i) Sodium hydrqide is a deliquescent solid and absorbs moisture and csrbon dicide forming
a hldrated solid carbonate.
2NaOH+CO2+9HzO ..- NazCOr.t0 HzO

(ii) ILs aqueous solution contains a high concentratioD of oH- ions and thus precipiEtes insoluble metal
hydroxrdes ftom their aqueous solutioos contaiDing these catioos :

fg3+ llet{- .... Fc(oH)l I ;

Fcrric hydroxidc
(Ikddi:h btotqt ppl)
Cl+ + 3oH- ...* c(oH)3 I
'n'u:H#i"'."
The hydroxides ofAl, Zn, Pb and SD being ampboteric dissolve in excess of NaOH giviDg clar solutions.
Za(oHh + 2oH- [Zn(oHL]2-
- Zncatc ion
or Zn + zOH- + 2H7O [Z1(OH)4]2- + H2
-
AI(OH)3 +3oH- ..- [AI(OH)6]3-
Aluminatc ion
or 2Al +6OH- +6H2O 2 [Aj(OH)6P- +3Hz
These metals also dissoke in NaOH liberatiog H2 gas.
-
U:o NaOH is widely used ir (a) soap, paper, textitc afld petroleum industry (b) thc preparatioo of pure
fats and oils and artificialsilk.
12154

(T,IAIJTISJ SI2ECIAL
' Hotd ls snhydrous mognrsluttr chlorldc pre' Q. 3, It ls necessry to add S4lsum ln the llnal Etsgc6
psred ftlm ms8tresium chloride hQxshydrote ? ofpreParotlon ofcemenl B(ptstn why ?
Ans. Cypsum (CaSO12[I2O) is added in thc Enalstages
Ans Adlrdrous MgCl2 caDrot be PrePared by simPly
oi preparation ofcement since when Hzo is added
heting MgCl2 . 6 H2O bccausc it gets
to cement it slo\ s do\r,n tbe PrGess of setting of
hvdrotvsed bv irs otrn u,ater of cr)Etallization' cemeot so that it Sets sufficie[tly hardened thcreby
rrigCh. o ILO- MgO + 2 HCI + 5 HzO
imparting Sreater stength to it.
mchlorid is hcatcd Q. I . Whqt is fly 8sh ?
650 K it cltd!8 the Ans. It is a waste Product from iron industry and has
the tDdrated ma8' proPerties similar to that of cement. It mainty
r ofcrystallizatbn to consists calcium silicate (casio3).
form anh)dr$s magnesium chlffi'e Give brtefly the lsolatlon of mogneslum ffom
Q.5
-'
Hcl -'
ca6
MgCh+6H2O seo wster lry the Dow Proces& Give cquotions for
MgClz.6H2O
- lneolved. (I.I.T 1993)
630 K the steps
(). 2. Account for thc followltr8 : AJls. See pages 1230.
(i) Be(OE)2 ls lnsotuble but Ba(oH)2 ls fairly Q 6. MgrN, *h"o reacted with wster gives ofl NH3
soluble ln w.ter. butHCl ls trot obtrlned ftom M8Cl2 oD rcactlon
(ii) Be(OH)2 is smPhoterlc whlle Mg(OH)2 ts
ivith woter at rooE temP.rature. (l'I'T' 199t
hasic.
Ans. Mg3N2 is a salt of a strong base, M8(OH)2 and a
Ans
weak acid (NH3) aod heDce gets hydrolyscd to
give NH3 . In contrast, M8CI2 is a salt of a stroog
base,Mg(OH)2and a strongacid, HCland hence
than that of M8, the M-OH bo[d can break lcss does noi undergo hydroDsis to give HCI'
easily iD Be{OH)2 than in M8(OHL. In other Q 7 The cq'stalline salts of all@line e,rth mctsls cotr'
wot&, Be (o Hh ocls ot a weak boY even weaker taln more rflater of crystalllsstion than the cor'
respording alkEll Eetal sslts. Why ? (I'I'T 1997)
thott Mg<oHtz.
Ans. Due to smaller size aod hiSher nuc,ear charge,
Fbrther be@use of smaller size and higher alkaline earth memls have a higher tende[cy tha[
electronegativity than that of M8, Be(OHt can alkali metals to attracl H2O molecules and thus
acccPt OH- ions from alkalies to form beryllate contrain more water of cr)Gtallization than alkali
ion but M8(OHh dos rot. metals. For eEmPle, UO.2H2O aod MgCh 6H2O'
Q.li, Chlorinatlon of calclum hydroxlde proiluces
BC(OH)2 + 2oH-.. Be(oH)l- bleachitrg Powder. Vltite lts chelrlcal equatiou'
-
Beotr- + 2H2o (I.I.T, 1998)
Bcty'latc ion Ans, Bleaching PoPder is obtained by Passing Cl2into
Ms(oHt + 2oH- i(' M8(oHf- Ca(OH)2. Though bleaching Powder is ofteD
Thus, Be(oH)z acE ta a $'eak scid bu MitteD as Ca(OCl)2, it is actually a mixture'
Mg(o[)z does nol combining both the focu' we 3C,a1OH)1+2C\-
coacbde tlat Be(oth it @nPhotetic but ca(ocl)z. ca (oH)z. c,aclz -2H2O
Mg(OH)2 ir Da,tic. BlcachingPosdcr

t. I,T, (ATA/iMq) SPECIAL

Q. 1. Calcium burrs in nitrogen to produce a whlte
Dorryder whlch dissolves in sulllclent t?ater to
produce a gns (A) and nn alksline solution' The
S-BLOCK ELEIUENTS '12155
Ans. (h burns in air to form CaO and Ca3N2. IdeDtify A5 B, C, D ond E.
2Ca+Or+2CaO (r.r.T t99e)
3 Ca + N, CarN, Ans. (i) CaO + H2O-- Ca(OHh
- hydrolrsis with fI2O gives
Calcium nitride on (A)
ammonia (A)
Ca3N2 + 6HrO* 3 Ca(OH)2 + 2NH3
0i) NH3 + H2O + COz * NH4HCO3
(B)
The alkaline soturion of Ca(OH)2 rfrus flrmea
reacts with CO2 present in thC air to form
CaCO3(B). (nr) 2 NaHCO3 NECO3 + CO2 + H2O
Ca(OH)z + CO2- CaCO3 + H2O
- (c)
B
Thus, A=NH, and B=CaCO: l(white pol der) (rv) NHIHCO3 + NaCt- NaHCO, + NH4CI
Q2 The Hober-process cln be reprccerted by the (D)
followlng scheme.

CaCO3
(v)2NH1CI+Ca(OHt-
+
2NH3+2HzO+ G0z
H^O (E)
Thtts, A = Ca (OH)2,
1A B = NH iHCO3,
C=NarCOj,
D - NHpt
and E = CaCtz.

CHOTCE ItfrsTtoMs
^,tllLTlPLE CPMT, BHU

1. The raw matcrials used in the maaufacture of 4. Whicb of the following is not prese[t in cement ?
sodium csrboMte by Solva /s proccss are :
(c) Gypsum (6) clay
(a) Ammonia and carbon diffide
(c) Alumim (d) Alum.
(D) Sodium chloride and carbon diqide 5. Which of the fo[orring bas the lourcst mctting
(c) Sodium chloride, limestone and carboD dimjde point?
(d) Sodium chloride, limcslotre and ammonia. (a) Ucl (r) Nact
Glauber's salt is (c) KCI (d) Rbct.
(a)FeSOa.7H2O (6) MgSO..7H.O 6. Whici of the folloring alkaline arrh metal sul_
(c) NECo,.1oH2O (d) NqSO..t0rLO. phates is least soluble in water ?
(a) BaSOa (D) Mgsoa
Plaster of Paris is
(c) SrSOo (d) CaSO1.
(a)(crsoah.H2o (D) c8so1.2Il2o
7. The basic character of thc oddes, MgO, SrO, K2O,
(c)Casoa.tl2o (d)C8sO1.
NiO and Cs2O increases in the order :

1,.1 2,d 3,a 4. .l 5.a 6.4

 Pradeev's
12156

(a) M8o > sro > Iqo > NIO > Gzo (c) excitaiio[ of frec electrons
(d) existence of body ccntred cubic lallice'
(r) Cqo < K2O < MSO < SrO < Nio tI I. l: 1939)
(c) Nio < MgO < Sro < IqO < CqO
< MBO < Sro < cszo' 16. GyDsum on heaiing to 390 K gives
(d)Y.zo.Nio (.t'caso1.2H2o (6) caso4
& Which of thc following are arranged in hcreasiDg (c)CaSOa.l /zHzO (d) SO3 aod CaO'
order of solubilities ?
\C ItM'l: 1t)9i\
(o) CaCO3 < KHCo3 < NaHCO3
17. The by-product of Solv
(6) NaHCo3 < KHCOT < CsCoJ (d) Carboo dioxide
(c) KHCO3 < N8HCo3 < CaCO3 (c) Calcium chloride
(d) caco3 < NaHcO3 < KHco3 i,
9. The thermal stability of atkaline csrth metal car- 1E. Thedrying agentwhicb absorbscarboo dioxide and
booates decrcascs in tho order ;
reacts violeotly with water is
(4) BacO3 > srCO3 > caco3 > MgCO3 (4) Sodium carbonate (b) Almhol
(c) Conc. H2SO1 (d) Calci'rm oxide
(D) BaCO3 > S[CO3 > MgCO3 > CaCO3
t B. H. t',. 1991\

(c) Cacos > srco3 > Mgco3 > Baco3

19. Metallic calciuD is prePared by
(d) M8CO3 > CaCO3 > SrCOr > BaCO3' (4) Displacemeot of calciunr by iron from calciunr
10. Which of the follo ing alkali metal halides has the sulphate solution
lo$est lattice cnerry ? (b) Electrolysis of molten calcium chloride
(a) LiF (D) NaCl (c) Reduction of limc bY coke
(c) KBr (d) csl.
11. A solution of sodium metal in liquid ammonia is

strongty reducing due to the Presence of 20, The follswing compounds havc beeo arranged in
ldeDtiry
(a) sodium atoms (D) sodium hydride orderof theirlncreasingthermalstabilities
(d) solvated electrorls- the correct order :
(c) sodium amide
(l.l.T. 1981) Iqco3 0), Msco3 (Il)' caco3 0ll)' Beco3 0v)
12. Sodium reacts with water more vigorously than
{atl<II<llt<Iv (b)lv< II <lll<I
lithium because, it i"j tv. tt. r. ttt (d)ll < w< III < I
t I.l.T. 1996\
(a) has higher atomic weight
(lr) is a metal 21. Among Ko2, AlOt , Bao2 and Nor+, unpaired
clectron is Prescflt in
Bao,
(a) Nor+ and (D) Ko2 and Alot
(c) KOz oDlY (d) BaOz only'
of t L I.',l. lt)97t

(r) Al3 t 1a; la+ 22. Property ofalkalille earth metals lhat increaseswith
(t.t.r' tesl) their atomic Dumber is
(c) Be2+ (4 Mf+
(a) ionization ener$/
14. The comPound insoluble in acetic acid is
(b) solubility of their hydroxides
(4) calcium oxide (D) calcium carboDate
(c) solubility of their sulPhates
(c) catcium oxalate (d) *1"luo, (I I T le97t
Y;?Iil;,, (,J) electronegativity
23. C.alcium is obtaiDed bY the
15. The metalliclustrc cxhibited by sodium isexPlained
by (d) Roasting of limcstonc
(a) diftusioD of sodium ions (6) Electrolysis of a solution ofczlcium chloride in
HrO
(b) Gcillation of loosc electrons
ERS
 S.BLOCK ELEMENTS
12ts7
(c) Reducrion of catcium chloride with carbol (c) SOr, ClrOr, Mp, AlrO.
(d) Elcdrolysis of molteD anhydrous catcium
chloride. (C.B.S.E. nM.T t997)
(d) MgO, AI2O3, SO3, Ct2O7. @.C.8. rgss)
24. For trrD 32. Which one is uscd ar an air puriEer in spacr craft ?
ionic Golids CaO aod KI, ideo tily tie wrong
shtement amoDg the follo ing ? (d) Quick lime (r) Staked time
(c) Porassium superffide
(a) Latticc energ of CaO is much higher tban that (d) ADhydrous CaCt2.
Of KI (D.C.8.2000\
(6) KI is soluble in bonzcne 33. The active constituent of bleaching por,\der is
(4) ca(oCl)2 (6) Ca(ocl)Cl
(c) CaO has hig! m.p.
(c) Ca(ClO2)2 (d) ca(clorct.
(d) KI has higlr E p. (c.B.s.E. pM.T rssn
25. The compouDds of alkalioe earth metals have ttle 6.nM,C.2000t
follou,ing magnetic nature 34. Bleaching po$der lces its power on keeping for a
(4) Diamagneric (D) Paramagnetic loog timc because
(c)Ferromagnetic (l,) ir changes iDto calcium bypochlorate
(d)Antiferromagnetic
(.lt l!P.u.T 199t) (b)it changes ioto calcium chloride and catciun]
hydroxide
26. The stability of the followiog alkali metal chtorides
follorrys the order : (c) it absorbs moisture
(a) UCI > KCt > NaCt > CSCI (d)it
changes into calcium chloride aod calciun)
(r) CsCl > KCI > NaCt > LiCl
chforate. lKanv ko ( l . t: 2000t
35. The correct order of increasing ionic characrer is
(c) Nacl > KCI > LiCl > CsCt
(a) BeCl2 < MgCl2 < CaCI2 < Bactz
(d) KCI > GCI > NaCt > LiCt tv.t!t!.tt.t: ts%)
(6) BeCl2 < MgCt2 < BaCt2 < CaCt2
27. Which of thc followiDg substaDces can be used for
(c) BeCl2 < BaCl2 < MgCl2 < CaCl2
drying gases ?
(a) Calcium carboDate (6) Sodium carbonatc (.r) Baclz < CaCl2 < Mgctz < Bectz
(c) Sodium bicarbonate (d) Catcium oxide.
llr.LlI.C.20t)0t
t_\L LC. L. E. 1999) 36. KOz (pota.ssium superoride) is used in oxygen
28. Epsom salt is cylinders iD space and submarines because
(a) MgSoo.T HrO (6) CaSo4.HzO
it
(6) absorbs CO2 and increases 02 mntent
(c) MgSOa.z H2O (d) BaSO1.2 H2o.
(D) eliminatcs moisture
.'t.t:c.L.r. t99et (c) absorbs CO,
29. Among the alkaline earth metals, thc eleDent
formiDg prcdomiDaDtly covalent coDpound is (d) produces ozone (A.I.E.E.E. 2002\
(a) Barium (D) Strootium 37. M readity forms water soluble sulphate
A- metal
(c) Calcium MSO4, water insotubte hydrcxide M(OH); and
(d) Bcrylium.
(M.PC.E.E. t999\ oxid MO which becomes inert on heatio!. The
hydroxide is solubte in NaOH. The metal M"is
30. The solubility in warer of sutpharcs dolr,n the Be
group is : Be > Mg > C > Sr > Ba. This is duc to (a) Be (6) Ms
(a) Increase in mclting point (") Ca (d)Sr (A.t.E.E.E. 2002 t
(D) High ionizatior erergy 3E Which oflhe following process is used in the extrac_
tive metallur$r of magnesium ?
(c) Higher coordioatioo numbcr
(a) fused salt etecirolysis
(d) Allof these. (LLI.M.S. 1999)
(6) selfreduction
31. Which of thc following is the correcl order of
g'adually desearing basic naturc of thc oxides ? (c) aqueous solution elec{ rolysis
(a) AI2O3, MgO, Cl2O7, SOj (d) thermite reducriotr it.l.T )no2 )

39. Ide[tify the correct order ot acidic strengths of

(D) Ct Or, SOr, At Or, MgO COr, CuO, CaO, HrO

AAISWERS
23. d u.d ?1," 26. d 21. d Zt. a Zg. tt 30. c 31. d 32. c
33. b 34. .l 35. a 36. a 37. a 38. a
 Net4 Course
1A58
(d) hydrating sand and Eravel mixed with clment
(d) cao < Cuo < Hzori Coz
(A.I.E ll.Il 2003)
(b) HzO < Cuo < C-aO < Co2
45. ME and Liare similar in their propcrti; due to
(c) Cao < H2O < Cub < CO2 (aisame c/m ratio (D) same electron afiinity
(d)H2O<COrcCaOcCuO i' i"j *m" group (d) same ionic PoteDtial
(A.Elll.c.2004)
40, The paramagnetic sPecies is
(a) Koz (b) sio2
Photoelectric effect is maximum in
(c) Tio2 (d) Bao2 (4) G (b) Na
(4 1'1 111's 2003) (c) K (d)b (A.t M.c 2oo1)

47, Which of the follo\Ping metal has stable carbonates ?

41. On dirsoMng moderatc amount of sdium metal (a) Na (D) Mg
in liquid NH; at lo tcmPeraturc, which onc of the
(c) Al (d) si 6.tiM C',. 2oo1\
follouring does llot occur ? 4$. A sodium salt of unknowo anioD wben treated with
(a) Bluc colourcd solution is obtaincd MgCl2 gives white preciPitate onty or boiling' The
1r) Na+ io are formed iD the solution anion is
of
icj Uquio ammonia bccomd g@d conductor (a) sol- (D) Hcot
electricitY
(d) Liquid ammonis remains dia (c) col- (d) NOt
u L r. 2oo4)
200j\ 49. Asolid comPound'x on heating Sives CO2 gas a[ld
4e Thc aubsEncc not likely to contain CaCO3 is a residue. The residue mir(ed with watcr forms'Y''
On passing an a(crss ofCOz through'Y inwater'
(a) dolomiE (D) a m
(c) calciDcd EEsum (d) sea a clear solution'Z is obtained. Oo boilinS '2"
)oo.tt corDDound 'X' is reformed. The comPound'X'is

dol n tbe mag-

(4) Ca(HCO3)2 (b) CaCOJ
43. Solubilities of carbomt6s dcrease
(d) Y\co3
(c) Na2CO3
ncaium SrouP due to desease in
(c B.s.D. Prl T 2oo4)
(o) cntroPY of sotution formation
!O One molc of maglesium nitride on reaction with afl
(E) lattlcc encrgica of solids

(a) co rtbg lood into siliclc scid 51. Which of the follor,/ing is not a Mg ore ?
(a) GyPsum (D) Magnesite
(D) krPing it cool
(c) Dolomite (d) Carnallite
(c) devcloping interlocting necdlc like caystals of (c.PM.'l:2001)
hydratcd silicates

H I NT9/EXP LA NATIO N I r,o M ult'i?l e Ch oic e Qu e e'cio n g

10. Bigger lhe sizc of the ions, lar8cr is the distance (r)
be-frcen thelr centres and lower is ihe lattic cDcrgy
@rqtt ?)'
13. Na+ h8s + l unit charge, Mg2+ and Be2* have +2
unit charge while Mgl+ and AP+ have +3 unit
is more basic tban MsO. Thereforc, the overall charge, thcrefore, br'dration eners/ of All+ and
order is NiO < MgO < SrO qO ' CqO' Mg3+ is e4ectet to be biShr than those of
'
t. The solubility of bicarbonates o[ alkali metals in- Mgz+ and Be2+, which in turn, 8re cxPcted to b
crcases down the grouP. But alkaline eanh metal higher than that of Na+. Furtber the hydralion
carboDates are insoluble in H2O

I ,1' ' (('El<s

42. c 43. c c 45' d 46' a 47' a 4t' b
t9, s 4.a 4l.d 44.

!0,!- !L :\
-
S.BLOCK ELEMENTS 121s9

eDer$' of Be2+ is higher thad thar orMg2+ due to
its smaller size. Inotierwords, hydration etlerby o(
Mgz+ is expected ro be higher than that ofNa+.
14. CaO, CaCO3 and Ca(OH)z are allbasessnd hsnce
mu6l dis$oh,e iIIacctrcacid to form calcium ace(ate,
Onty calcium oxalate docs oot. dissolve in
cH3cooII.
21. ODry KO? bas an unpsired clectron,
J6. 4 KO2 + 2 CO2 * 2 K2CO3 + j 02
Although KO2 ako rcacts wath moisture of the
breath but dos not completely eliminate it.
4ROz+zHzO*4KOH+302
For furrher eplaoafion, refer to page l?14.
37. BeO being ampholeric dissolvqs in NaOI I.
39. H2O is a neurral oxidc. Non-metallic oxjdes, (i.e.
COz) arc acidic white metallic oxides (i,.. CaO and

K+ -,il-o'. CUO) are basic. IIowever, (xides of alkaline earth

metals are ntore basic than oxides of transilion
metals Thus, the ol.erall acid strength docreases i11
24, Due to lc|vcr latticc cner$/ of KI as coflrparqj 1o that thc ordcr: CaO < CUO < H2O < COz
of CaO, them.p. ofKl is much lou'er than rhat ofclo.
26. The stabiliiy ofa compound depends uporl its en-
45. I-i+ and Mgz+ ions have similar polarisiflg power
thalpyof fbrmation,AH'/ Evideutlymore negative or ioDic porential,
thc !"lue of AH", moro stable is lhe compouod. 4E, Bicarbonates on heatingform iDsoluble carbonates

(Reter to Thble 12.3 on page 1?10). Thus, option Mgclz+2NaHCO3 ..- NaCl t Mg(HCO3)2
(d) is corrEct, r.e., KCI (--428) > C-sCl (---424) >
NaCl (--a00) > LiCl (-399). The values given in Mg(HCo3)2 Mgco3l +co2 + H2o
mol-I. A -
pareDtheses are in kJ
49, CaCOs * CO2 + CaO
30. As the size inrcases, the extcnr of hydrarioD, ie., (x)
coordiDatio Dumber decreass and hence the
CaO+HzO (}r(Ofl)2
solubility dccIeases accordingly.
-
Jr. MgO is basio, A.lzol is amphoteric SOj aDd Cl2O7 tY)
both are acidic but ClzO? is otore acidic thao SO3.
Ci(OU)2 2COz * Ca(HCOJz
Therefore, optioD (d) is correct.
(exces6) Z
A
35. As the sizeofthe cation increasos, elecrronegarivity Ca(HCOt)2 ...- CaCOr + CO2 + HzO
defieases and heDce the slectrotregativity dif-
fcrence increases and heoce ionic characrer in.
ZX
creases acaordingly.
50. M83II2 + 3 H2O * 3 Mg(CH)2 + 2 NH3

ADD'TIONAL 9UESTIONS
ornpe e E)<arn ifrr ofts
Ass erti on -Re a s o n Ty p e e.u e stio n s
The following questions corslst ofor iAssertiort In column I and the rReasor, in colum[ 2. Use the following
k.y to choose the appmpriate srtsxer.
(a) Ifboth assrtion and reason are coRRECf and reason ls the GoRRECT explanation ofthe assertion.
(r) If both ossertlon and reasotr arc CoRREgf but rason is NoT the coRREcT explanatioD of the a-sserdon.
(c) If assertion ls CORRECI| but reason is INCORRECX,
(d) Ifassertlor ts INCORRECr, but resson is CORRECI.
12160 l'radcap's NeU Cortr1e Cfrcmistrq WIll
Aasertion (Column 1) ReasoB (Column 2)
Magnesium can be obtained by the electrol),sis of -Ihe reduc',ion potential of Mg2+ is far lower thao that
aqueous MgCI2.
ofH+.
2. Common salt becomes damp after some tirl]e oD Comnron salt ir NaClwhich is hygroscopic iD nature.
keepiDg in air.
3. MagDesium keeps on burniog iD CO2. Magnesium reduoes CO2 to C.
4, Calcium and magnesium qides are oot reduced by Calcium and magnesium oxides react with carboo to
carboo. tbrm their respective carbides.
5' Li+ 1o4; has larger ionic radius than that of Li+ (4q) is relatively more exlensively hydrated as com-
N.+ (r{). Dosed to Na+ (oq).
6. Potassium can be obtained by the electrolysis of Metallic potassium is soluble in melt (molteD Caclr.
tused KCI io molten Caclz. Thus, the cll for electrolysis gets short circuited.
7. The alkali metals are strong reduciDg ageuts. They have only one eleclron to be lost from theirvalence
shells.
E. Potissium erbonate cannot be rnanuhctured ry a Potassium hydrogen carbonate is less soluble in water
p.oass similar to the Solvq/s soda ammonia proce.s$ fiarl sodium hydrogen carboDate.
9. r-i resembles Mg.
U+ has same size as Mgz+ (A.r.r.M.s. 1994
10.. NazSOa issolublein waterwhileBaSOa is insoluble. Lattic eDer$/ ofbarium sulphate exceeds its hydration
energy. u.I.I.M.S. 1997)
11. The alkali metals can form iooic hydridcs whicb The alkali Drelals have low elec(roDegatMty ; their
qrDtair the hydride ion, H-. hydrides conduct electricity when fused and liberate
hydrogen at the anode. (I.I.T 199s\
12. Sodium ioos are dischargcd in prelereDce to The nature ofcathode caD affect the order ofdischarqe
hvdrogen ions at a mercury cathode. of catioos. (A.I.I.L4S. 1996)
13. Alkalimetals impart colour to the flame. Their ionizaton cDergicsarc lcir.
(AJ.I-L(S. l99E)
14. Sulphur is estimated as BaSO4 and not as MgSOa. The ionic radius of Mgl+ is smauer than that of Ba2+.
(IJ.r, 199E)
15. LiCI is predominantly covalent compound. Electronegativity differcnco bctwEeo U 8nd Cl h too
small. (It.t l99E)
16. Al{OH)3 is ampholeric in nalurc. Al-O and O-H bonds can be broken with equal ease
in Al(oH)3. (LI.T. l99El
!7. Barium is not required for nornlal biological Barium dcs not shotv variable qidation state.
function in buman. (aJ.I.M.S.2o0j)
lt. Barium carbonate is more soluble in HNO3 than in Carbonate is a wcak base and reacts with thc H+ ftom
plain water. the strong acid causing tbc barium salt to dissociate.
(A.LI.M.S.2003)
19. Mg is Dot present in enamel olhuman teth. Mg is an essential element for biologi@l fuDdi,ls of huma[.
(AJI-MS.2ln4l

True/False StatemenAs
Whbh ol the tollowilg staternents qe m4 qld Desd bumt plaster can be used as a dcsiccanl
which are falte ?
6. Calcium is prdcnt in the bones of snimah and
1. Elements found in the combinEd state arc often huma[ bcirgr a8 phcphates.
presetlt as dids, carbo[ats, sulpbides and silicats.
Mg and Ca form dipGitive ions duc to tbeir high
All alkali metal bdrqidcs are strotr8 bass.
hydratio[ encrges.
3. Sodium carbonate is called soda ash. Solvaymmonia procss is used for the manufac-
4. Magnesium imparts pink colour to the flame.
ture ofcaustic soda.
S-BLOCK ELEMENTS 12161

9. Lithium rqlembles magrlesiuDl since their 14. Magnesium is aE essentia! mnstitueDt of

e lectmDegatMtics are alm6t the same. chlorcphy , thc glecD mlouring Eatter of Dlants.
10. Uthium burns iD nilrogen to gi\ litbium nitride.
15. Sodium whcn buror- in excms ot' GygeD gives
11, Beryllium is rnore electroFsitivc thaD Eagnesium. sodium.Jxide. (r.r.T, 1e87)
12. Alkalioe earth meials are befter reducing agents
than alkali metals. 16, ID group l ofatkali metals, the icnizatioD po[ential
decreases dollltr the group. Therefore, Lithium is a
13, Beryllium rsembles aluminium clcety in its po$edul reduciDg agenE.
propenies though it belo[gs !o a differeot group.

Fill ln'fhe Alanks

l. Highly electropcitive Derals like alkali metals arg 10, Calcium cfride is mmmonly knowD ..... y.,hile cal-
obrained bv.... . cium hydroxide is called ..... .
2. Magne.sium hurEs io air fo give . . aR.l !1. 'Ile.. .....of Be is highcst anlong the atkalirnetals.
3. Lithium resernbles ntcre with......tbanwith sodium. 12. Tbe alkali metal hydroddes are......and tbe basici!y
of the hydroxide with increaso io slze of thc
4. Be(OHh is.... . .aDd thus di,jsolves i:rslkalies asltell catioo-
as acrds.
13. Among alkaline earth Dtctals, ... salts impart red
5. Lithium nitr3te oD heating gives.......,arld........ . colour while ..... salts do not impar! any colour to
the flame.
6, Na2CO3 is........in weter but BaCO3 is........ .

14. Ca is extracted by the electrolysis ofa fuscd [rixture

7. In Solvay process, excess cl.......is passe.l th:ough of..... and .... .
sodium chloridesolutionwhich has bn previo'rsry
saturated with........ . t 5. Ca2+ has a smaller ionlc radius than K+ bec{use i!
has (I.I.T. 1993\
8. Sodium is obtai[ed by the electrolFis of.... a! wel!
as .:.. in their molteE slate. 16. Or hearing, Rb(ICl, wiu decompose 9iving..........
and......... (I.I.T t997)
9. During electrolvtic extrrctioD of Mg fiom MgCl,
.... i$ added to lowcr !!:e meltlDg point of the 17. -4 solulioD of srjdium in liould ammonia at -33.C
electrolyte. colducls electricity. On cooli[g, the co[du ctivity of
this solutio[l....-...

M atchin O Ty? e Q.u estio ns

Match items giwrl in C-olumn A against thse give n in Column B.
Column A Column B
L Alkali metals are eKracfed by (a) Flame tcst
2 Sodium chloride (D)r-Block elemeoB
3. Sodium bicarbonate is used iD (c) Fire extinguishcrs
4. Alkali metals are (d) Re{tucirg agetrrs
5. Alkaline earth metals are (e) Electolytic method
6. MagDesium does not ive (f An ore ofsodium
12162 llradee p's Ne@ Course Ch'"m iitrg.Wlil

t. (d)2. (c)3. (a) a. @) s. (a) s. (d)7. (a) E. (c) e. (a) 10. (a) 11. (a) 12. (a) 13. (a) M. (D) ls. (c) le. (a)
17. (b) 18. (a) o. (b).
TRUUT-ALSE STATEMENTS

1. Tiue 2. Tiue 3. Ttue 4. False, does not impart any colour 5. Fhlse 6. Tfue 7. Tlue t. Fhlse, washing soda
9. Ttue 10. Tiue 11. Fhlse, Mg is more electropositive than Be 12. Fblse, alkali metals because of their
more electronegative standard electrode potentials are better reducing agents than alkaline earth metals.
13. Thue, diagonal relationship. 14. Ttue 15. Fhlse, NarO, 16. False, electrode potential of Li in the most
negative amongst the alkali metals and hence it is the strongest reducing agent.
FILL IN THE BLANKS

1. electrolytic reduction 2. MgO, MgrN, 3. maguesium 4. amphoteric 5. NO2, LirO and O, 6. soluble,
insoluble 7. carbon dioxide, ammonia E. sodium chloride, sodium hydroride 9. NaCl and CaCl,
10. quick lime, slaked lime 11. ionization energy or electronegatMty. 12. strong bases, increases.
13. d+ , Mg2+ u. C-2tclz, C,2F215. higher effective nuclear charge 16. RbCl and ICI 17. increases.

MATCHIN G TYPE OUESTIONS

l, Con'ect assertioiT r Mg can be obtained by the Con'ect realion : KHCO3 is more soluble in HrO
electrolysis of tused MgClr. than NaHCOr.
2. Cot'r'ect reoson :
NaCl contains impurities of 14. Correct *planation. BaSOo is insoluble while
MgClz,CaClr, MgSol, CaSoo etc. which are MgSOn is soluble.
hygroscopic.
rs. Cot'rect rea.tolL Because of small size Li prefers to
6. Con'ect as,tertion .' K cannot be obtained by the
share rather than donating electrons.
electrolysis of fused KCI in molten CaClr.
 GJ N! [TT

3orne p-Dlock El ernertEs

,
,,:,,,,,, , ,1,,; : ,, : :l:, , i ,1: ,1:: ,1,,, .
,,,:.,, i
' '.,,,

Boron-occurrence, isolation, physicaland chemical properties, borax, boric acid, boron hydrides,
halides (elementary idea of boranes, diborane, borates)- Uees of boron and its compounds.
Carbon-terrestrial abundance and dislTibution, allolropes (graPhiie, dianpnd, elemenlary idea of
tullerenes). Alomic and physical properties, chemical properties, oxides, carbides, halides,
sulphides, uses oJ carbon.
Nitrogen-terrestial abundance and dislribution, dinhrogen-isolallon, alomlc and physical
properties, chemical reaciivity, fixation ol nitrogen-industrial and biological.
Ammonia-induslrial preparation, Haber's process only, lnpoIlanl properlies and reactions.
Oxides of nitrogen---prcparalion, stnrq(ure (skeletalonly), prl - pr bonding. Nilric acid-industrial
production (ostwald process). Uses ol nilrogen and its corrPounds.
Orygen-lerrestrial abundance and distribution. Diorygen-atomlc and physical properties.
chemical reaclivity. Oxides-acidic, basic and amphoteric.
)aralion, structure and sorne oxidising properties
Ozone-preparalion, properties
.',','' "..".'.,." .,""", ...::i
'13.1. General lntlodUclion i,EfiEl:ltitrlr!.::...iti:ilrf-i.i11(ir.L:i,ij:i:i+i:l
In general,
What are p-Blmk clemnts ? Elements in (i) Non-metals have higher ionization enthal-
which the last electron ente.s any of the threcp-or- pies and higher electronegativities than those of
bitals of their respective outermost shells are called metals. Therefore, in contrast to metals which
p-block elements. Since a p-subshell has three readi$ form cations, non-metals readily form
degenerate (same energy) p-orbitals, each of which amons.
can accommodate two electrons, therefore, in all, (ri) The compounds formed by the union of
there aresixgroups ofp-block elements, i.e., groups metals with non-Detals are generally ionic because
13, 14,15,16, 17 and 18 (excluding helium). The of large differences in their electronegativities. Ob-
atoms of elements ofthese groups receive their last viously, compounds resulting from the uuion of
electrons in 2p, 3p, 4p, 5p and 6p-orbitals. non-metals generally tend to be molecular in na-
General chemlcal behavlour. The elements in ture,
the periodic table have been divided into four Dilfertnce in chemlcal behaviour offirst ele-
groups,i.e., s-, p-, d- and/-. Out ofthese four blocks meot of each group. It is interesting to note that fus(
of elements,p-block is the only one, of course with member of each of the groups 13-17 of thep-block
few exceptions, which contain non-metallic ele- elements differs in many respects from other mcm-
ments. These elements display diverse chemistry bers of their respective groups. These differences
depending on the group to which they belong. are quite striking in goups 1i}-16. But, the elements

7?t7
13i2 t)ra,te ap's Neu Course themistr5fft[)
r,i group i7, i.e., halogens show much more aeeds awo mor: clectrons to complete it$ octet.
sii,iiarity in thei chemical behaviour tha! the ele- CoDsequently, boron compoundg espcciaily thc
mcnts ofany other group. The main reasorx for the hydridcs, arc usually rcferred lo as electon-defi-
dilierent chemical behaviour of thefust member ol cient coitlpoiinds. Ftrtther, trec-".use thcir of
a paiticular group of elements in thep-block com- electrol-defi cient nature, boron coinpounds readi-
pared to other members of the same group are ly accept electrons from other molecules capable
presumably its small size, high electronegativity of donating a pair of electrons. Boron compounds,
and absence of d-orbitals. For example, thus behave as Zeryis acr'ds. For example, BF, com-
(i) First member of each group has only four bines with Lewis base NH, to form
valence orbitals (one fu- and there Q-orbitals)
available for bonding and hence at the maximum
H3N : -- BFr.
can accommodate four pairs or 8 electrons. In 132,1. Occrrrtcncc of Boroo
other words, thes elements can-not expand their Boron occurs in two isotopic forms, !0B
valence shell and hence seldom form-compounds
in which the coordination number exceeds four. (19%) ad ltn 1er%;. ts abundance in the earth's
(ii) Because of smaller size and higher crust is very low (0 . 0(I)1% by mass) . Boron mainly
electronegativity, first member ofeach group shows oclurs a.s borates and orthoboric acid. Some im-
greater ability to form pz -pz multiple bonds portant minerak ofboron are :
either with itself (z.g,C : C, C = C, N = N) or (i) Orth ob oic oc i d, H rBO,
with other mcmbers of the second row of elements
(e.g., C : O, C : N, C : (ii) Borc, Nq[B.oj(oH).1 . EH2O
= N, N O) ascompared
to the subsequent members of thc same group. ln or NarB.O, . 10HrO
other words, elements of third and subsequent rows
of the periodic table do not exhibit any strong (iii) Ke mit e, N arlBlo5 (OH)41
tendency for this q?e of multiplc z-bonding. or NqB.O, . 2HrO
In this unit, we shall study the chemistry of
(ie) Colemaaite, Ca2[83O1(OH)312 . 2H2O
boron, catbon, nitrogen atd a1gm, the first mem-
bers ofgroups 13- 16. Among these, carbon forms or Ca.BuOrr.5tlO
the basis of all forms of life on this planet since all,
biotnolccules (i.e., molecules of life) are essentially Boroa in form of borates is chiefly found in
made up of carbon, nitrogen and o4/gen. California (U.SA.) ard T[rrkey. In India, boron
ocrurs as borax in Puga Valley of Ladakh region of
13.2. Boron Kasbmir and Sambhar Lake in Rajasthan.
Boron is the first member of group ll} of the 132J. Isoladon ofBoron
perodic table. It is the only non-metal of this group. Elemental boron is obtained by aay one of the
Therefore, the chemistry of boron is quite different following methods :
from rest of the members ofthis group. The elechonic (i) By rcdtction of boric oxide wi t hiihty
configuration of boron (Z = 51 is fu2 2s2 p] and electmpositive metdk likc potasrium and mag-
thus has three valence electrons. Because of its nes an in absence of ah
sma.ll size (80 pm) and high ionization energy. HGtt
(IE, = ggo kI mol-l, IE2 = 24n H mol-l Md BrO, (s) + 6K(s) -"'-'* 2B(s) + 3KrO(s)
I4 = 3658 kI mol-l; it carnot lose all its three H.{t
valence electrons to form 83+ ions. Irstead, be-
Bror(s) + 3Mg(s) ---* zB(s) + 3MgO(s)
causc of its small size, high ionization cnthalpy and Thc product thus obtaincd is boiled with
high electronegativitv, boron caa form three hydrochloric acid and fiftered whcn IQO or MgO
covalent bond.s by sharing iLs three v"alence dis<olves lcaving bchiad clemcntal boron. The
electroirs. In this respcct, boron resembles carbon powdered boron thus obtahed is thoroughly
and silicon of group 14 and differs from other washed with water to free it from hydrochloric acid
mcmbers of its own group, i.e., group 13. and is fmally dried.
Since boron forms three covalent bonds, (ii) By mhrction of volatile borut halides with
iherefore, in the compounds of boron, tlc cenrral dihydtogen at niPt tunperanre ( 1270 K) ot abealed
boron atom has only a sextet of electrons and thus tantalum frlament
SOME p-BLOCK ELEMENTS 13/3

r2?0 K
2BCl1@) + 3Hr(g) -----------+ 2fl'6) + 6HCIG)
r2m K
2BBrr@) + 3Hr(g)--'-+ 2B(s) + 6HBr(g)
Boroa of high purity (- 99'9Vo) czt'oe
prepared by this method.
(iii) By electrotytic reduction oIfiLsed borutes ot
other compounds ruch as KBF, (potassium
tetrafluoroborate) in molten KCVKF at 1073 K.
(iv) By thermal ilecompoition ol boron ti'
iodide over ftd hot nngsten frlomen, (van Arkel
mcthod)
w
zB\(g) '-'------'- 2B(s) + 3lr@)
7173 K

(v) By themal decomPosition of boron (rrl) Being a non-metal, boron has low electri-
hydrides cal condu ctivity which, however, increasc's with rise
1173 K in temperature.
........... 28 (r) + 3H, k) 132.4. Chemical Proprtles of Boron
EHo@)
Diborrrc Chcmlcal inerhess. The chemical reactivity
1323. Physlcal Propcrties of Boron of boron depends markedly on the state of sub-
(i) Boron is an cxtremely hard solid with melt- division and temperature. At ordinary tempera-
grcater thar 745O K. Its boiling point is tures, it is relative$ chemically i en. However, at
ing point
cts with all notr-metals
2825 K. gases, all metals excePt
(ri) Elemcntal boron erists in several diffcrent Cd, Hg, Sn, Pb, Sb and
allotropict forms. At lcast four allotropes of boron Bi. Some important reactions of boron are
may be obtaincd under different conditions. How- described below :
ever, transition between diffcrent forms is an ex' (t) Action of alr Amorphous boron burns in
trcmely slow proccss. All the four allotropic forms ai at 973 K forming boron trioxide (BrOr) and
contaitr Bl2 icosahedral units.. (Fig. 13.1) with
boron nitride (BN).
boron atoms at all the 12 corners. The different vnK
allotropic forms differ from one another in the way 4B(s) + 3Or@) """""- 2 B2O3(s)
the icosahedra are bonded together. yf3K
2B(r) + NrG) """""'' 2 BN(r)

t:l:ii L Boron nltnoe (BN)

l,orolr nltrlde (EN, caD alro Dc prepared
aLYJ bc prePareo by neaung boron
oy heating !n a curreDt ofammonia.
ooroD in oI ammoDla.

2B + 2NH3 * 2BN+3tI2
It b a white (.yslaliDc posrdc{ with I E of 3273 K The structur of BN b similar io ltrat of graphite with the only
p.
difrrcncE ttrat ficrle.troB io graphite 8re cdllpletelydcluliEd ovcr a[ thc ]hr atsrB of the lattice bui the
zlectrqB in BN arE o y plw deleoliad o!'er boroo atoms lcadi gtoueryal B-N bond lcttgtla.
Rccently, a crlslalline form of boroD nitride called borazotr has been synthesized by application of high
temperature and pressure. This form is eve, hat'det th,an dianond Ntd is usad as ol abrulive

tThc phcnomcnon of exiatcnae ofon clemcnl in two or morc for,ns *'hich ha!,E differcnt phFical propcrtics but identical
chcmical prcp.rtics is callcd allolropy and the diff.rcnt fol'rns arc callcd ollot.op.s.
.rPolyhcdron with 20 faces.
1314 l)rt;dta;t s Nett Course ChemistrgnfrD

ADD TO YOUR KNOlV -E]DGE CONTtr)

, I Boron carbide (B4C) is obtaiDed by reducing B2Oj Nith c-ilrbon at 1873 K
1873 K
2BzO3 + 7 C+ B1C+6CO
Boron carbide is eveo harder than diamoud and is increasiDgly being used as an abrasive ior polishiDg. It is
uscd for brake lining for cars. Fibres of B4C havc aD cDormous LeDsile strength and arc usad to makc
bu efproof clothing. These fibres are made as follows :

c (fibre) + 4 Bc\ + 6H2 ...* B4c (fibre) + 12 Hcl

(li) Actlon of non-meials. Boron combines HrSOn and HNO3 (2 : 1) forming boric acid
with 02 and N, when heated in air giving boron (H3BO3)
trioxide and boron nitride rcspectively as shown
Ileat
abovc. B(s) + 3HNOr(ag)
It also combines with halogens at high -.r
temperatures to feld covalent trihalides. H3Bo3 @q) + 3NorG)
Heat Boric acid
2B(s) + 3Fr@) "".- zBF3@) lleat
2B(s) + 3HrSOr(ad
IIeat
2B(s) + 3clr(6) zBCljG) -
HrBOr(aq) + 3SO2G)
(iy) Action of alkalies. Boron resists the ac-
2B(r) + 3Br2(0
-Hcat 2BBrr(g) tion o[ alkalies (NaOH or KOH) upto 773 K but
above this tempcrature, it reacts forming borates
2B(s) .+ 3lr(s)
-Heot
-----------+ zB\(E) and liberating dihydrogen gas.
> 113K
Boron trifluoride (BFr) can also be prepared 2B(s) + 6KOH(s) .......- 2KrBo.(s) + 3H2G)
Pot.borate
indnecdy by heating boron trio:ride with calcium
flu.ide and conc. tIzSOl. It also dissolves in fused NarCOr/NaNO, mix-
ture at 1123 K
B2o3(s) + 3 CaF2(s) + 3H2SO4(D
g 2B(s) + 3NarCO3 (s) + 3 NaNO, (s)'---.
2 BFr@) + 3 CaSO.(s) + 3HrO(0 2 NarBO, (s) + 3 NaNO, (s) + 3 CO, @)
All the trihalides of boron are
electron-defi- (v) Action of mtals. Boron combines with
cient compounds and act as Lcwis acids. For ex- many metals except group 1 and heaiy metals (c.g.
ample, Ag, Au, Cd, Hg, Sn, Pb, Sb, Bi) to form their
BF: + : NH, -""""'+ F:B * NHr corresponding borides which are generally very
hard and high melting solids.
kwis acid [rwis basc
Heat
3Mg(s) + 2B(s) -----'r MgrBr(s)
BF, + :F:- BFa- Mag boride
Tctra fluorcbo!-atc ion
IJwis acid
Irc.is basc Heat
The relative acid shength of boron trihalides
B(s) + Cr(s) """""'r CrB(s)
Chromium boridc
follows the order : (vl) Action of water. Boron is inert towards
BIr> BBr, > BCl3 > BF,
water. It Ls not even attacked by steam.
(ili) Action ofactals. Boron does not react with
(vii) Reduclng character. Boron is a powerful
non-oxidising acids such as hydrochloric acid.
reducing agent and thus reduces CO, to C and
However, it is attacked at high tempcratures by
strong oxidising acids such as a mixture ofhot conc. SiO2 to Si.
 SON4E p.BLOCK ELEMENTS 1315

Heat CarB6Olr + 2NarCO, ..........., NazBrOz

48 (r) + 3CO, G) 2BrO. (r) + 3C (s)
Colmanite Borax
Heat
48 (s) + 3SiO, (s) -------> 28203 (s) + 3Si (s) + 2NaB0, + 2CaCO3 'tr

Sod. flctabomte
132.5. Uses of Boron The precipitate of calcium carbonate thus
(i) Metal borides are used in atomic reactors formed is removed by filtratioo. The filtrate is con-
as protective shields and control rods because of
centrated and cooled when crystals of borax
the high ability of B-10 GoB) isotope to absorb separate out. Sodium metaborate present in the
mother liquor can be converted into borax bypass-
neutrons. This special property of l0B isotope to ing a current of carbon dioxide throught it.
absorb neutrons is also of current interest in tbe
possible use of boron compounds it cancer 4NaBO, + CO, ...........- NarBoOT
chemothempy. Sod. mctaborate Sod. tetmborarc
(ri) Boron fibres are used in naking light, I, NazCOl
composite materials for aircrafts.
3. From boric acid. Borax can also bc
(r'z) It is used as a semi-conductor for making prepared in small amounts by neutralising boric
electronic devices.
acid with sodium carbonate.
(rv) It is used in steel industry for increasing
the hardness of steel. Boron has virtually rcplaced 4 H3BO3 + NarCO3 ....._ NarB.O,
o(petrsive metals like Mo, Cr and W in the r- 6H2O + CO2
manufacture of special steels.
(v) Boron compounds are becoming increas- On coolin& crystals of borax, r'.e.,
ingly important as rocket fuels because oftheir high NarBnOr.loHrO separate out.
enerrylweight ratio. Prope les. (i) It is a white crystallinc solid,
(r,r) Boron is an essential elemcnt in plant in cold water but morc soluble in hot
less soluble
metabolism. water.
(rai) Boron carbide fibres are very hard but (ri) The aqueous sohttion of borax is alkaline
lighl 6d hence are used for making buUet-proof due to hydrolysis. Borax is, therefore, used as a
vests. water softner and cleauing agent.
13.3. Compounds ol Boron ir,*+ir:ri,:+r;r,ir.,i:,1:r.r,,.+rrjii::itrr:j!:i
NqBoO, + 2H2O 2 NaOH + HrBoO,
(stone atkal) (ibak ncid,)
133,1. Borax, Nar[B1Os(OH)al .8HrO or -,
H2B1O7 + 5H2O -......| 4H3BO3
NarB.O, . 10HrO
Tctraboric.cid Eoric acid
Borax or sodiurn tetraborate decahydrate is
the most important compound of boron. I[ occurs
(ni) Actlon of heat-Borax bead test, On
naturally as rulcal (Suhaga) in dried up lakes of heating, borax loses its water of crystallisation
Notheren India, Tibet, Ceylon and California and swells up to form a puffy mzss. On further
(u.s.A.). heating it melts into a clear liquid which
sotdilies lo a transparent Elass like bead which
Preparation (i) From tincal. Tincal ob- consists of sodium metoborute (NaBO) snd boric
tained from dried up lakes contains about 507o
borax. It is boiled with rvater and filtered to anhydride (B2O).
remove insoluble impurities ofclay, sand etc. The Hcat
filtrate is concentrated when crystals of borax Na.BoO, . l0HrO Na2BaO, + 10H2O
separate out. Heat -+
(iD From colemanlte. The mincral
NarBrO, 2NaBO, + Bror
colemanite, (CqBuO,,) is finely powdered and is Sod. metabor1re Boric.nhrdride
-
boiled with sodium carbonatc solution.
Tmnsparcnl gassy bead
13/6 Pradeep's

The Nu,B4O7 + H2SC)4 + 5H2O --- '

bead arad NarS(). + 4H,tsO,
detection
Ni2+, co2+, cl+,
cu2+, MnZ+ etc. Whenever a H3B()3 + 3ClzH.OH -.-+ B(OC2H5)3 r-3H2O
coloured salt containitrg these cations is heated Ethyl alcohol Triethylborate
This reaction is used as a test for borate ion in
qualitative analysis.
Uses of Borax. Bora.x is used
to form coloured metaboratss. This test is called
bomx bad test. Thus, (i) in the manufacture of enamels and glazes
Hcat for earthen wares i.e., tiles, pottory etc. The glazed
CoSOn """"'- CoO + SO3
surface is resistant to heat, stains and scratches,
Hcat
Coo + B2o3 -"""' Co(Bo), (ii) as a flux in soldering.
Cob.tt oxidc Cobalt nctabor.tc("!?) (lr) in thepreparation of medicinal soaps due
Hcal to its antiseptic properties
Nio +rlo:........... N(BO,2 (iv) in the manufacture of heat resistant (i.e
Nickcl oxidc Nickcl mctaboratc(roha) very low coefficient ofthermal expansion) borosili
' Hcat cate glass (pyrex).
Cr2O3 + 3 BrO, """""' 2 Cr@Or),
Cltromiurn trioxidc Olromium mctaboratccttan) (v) to make peroxoborate li.e.,
Heat Nar[(OH)rB(O - O)zB(OH)r1.6 H2Ol- an impor-
MnO + BzO: .-- Mn(BOr), tant cleansingand bleachingagent present in wash-
Mangancsc oEde Mangancse mctabomte
ing powders. They also act as bightnen since they
@;nk viol.t)
absorb UV light and emit visible light.
CUO + BzO: Cu(BO2)2
(vi) as astiffening agent for candle wicks
Cupric oxidc CuPric metaborate(dalt bfu e)
-
Certah metaborates are reduced to the free
(vii) to produce a good finish in laundary
(viii) in the laboratory for borax bead test
metal by the carbon present in the reducing flame
of the burner. For examPle, (ir) in softening of water.
2Cu(BO2)2 + C "'-"""r
2CuBO2 Structurt of Borax and olher borates. Boron
CuProus meteborEtc(co'oYr'Gs) forms strong bonds with orygen. This is supported
+ B2O3 + CO by the fact thatboron invariably occurs in nature as
borates. In borates, the basic structural unit may
2CuBO, + C -"""-. Cu +B2O3 + CO have one or more boron atoms linked together by
Mctal('rd)
intervening orygen atoms in form ofchains or rings'
(iv) Actlon with sodlum hydroxlde. On addiog Borax itself contains the tetranuclear units, i.c,
acalculated quantity of sodium hydroxide to borax' its
[BoO.(OH)n]2-as shown in Fig.13.2. Therefore,
sodium metaborate is formed. 8HrO.
correct formula is Na2[BaO5(OH)a] .
Na.B.O, 2NaOH "-"""+ 4NaBO2 + H2O
*
(v) Actlon Mth sulDhuric acld. On adding a OH
calcutled ouantitv of concentrated sulphuric acid I

to a hot conientraied solution of borax, boric acid

Ls produced.
NarBoO, * HrSO. -* NqSOI + H2B1O7

H2B4O7 + 5HrO ----""'t 4H3BO3'

-l
OH
 SOME p.BLOCK ELEMET\iTS
1317

13.3.::. Ortlioboiic riciri ,,Boir acid/, H.90. (iv) Action of heat. Boric acid, on heating,
:;r E(OIt), loses water in three different stages at different
:n. . .-:/ . .ilL i-r.hll al1e Ci at.; oL().t: temperatures ultimately giving boron trioxide.
ocld. 3?0 K
Preparation (i) f'rom borax. Boric acid is H3BO,
-.-. HBO, + H?O
obtained by treating a hot concentrated solution of Boric acid Mctaboric acid
borurvith hydrochloric acid or sulphuric acid. The 410 K
resulting solution on conceDtration and cooliug 4 HBO2 ----------.) H2B4O7
gives crystals of boric acid. Metaboric acid -HzO 'l!traboric acid
Rcd hcat
Na2BaOT + 2HCl + 5HrO ----......r 2B2O3 + H2O
Boron trioxide
4HrBO, + 2NaCl (v) Rcaction wlth ethyl alcohol. Orthoboric
NarBoO, * H2SO4 + 5H2O ........* acid reacts with ethyl alcohol in presence of conc.
H}SO/- to torm tiehylborste.
4H3BO3 + NaZSO4
Conc. H2SOa
(ii) By hydrolysis of boron compounds. B(OH)3 + 3qH5OH
Boric acid can also be prepared by the hydrolysis Orthoboric acid Erhyl alcohol
of boron compounds such as halides, hydrides B(OqH5)3 +3H2O
and nitrides. Tric thly'bordtc
BCL + 3H20 -------- H3BO3 + 3HCl The vapours of triethylborate when ignited
BzH6 + 6H2O .+ 2HrBOr+ 6H, burn wi th a green- e dged llame . Thrs forms the basis
for detecting borates and boric acid in qualitative
BN + 3H2O .----+ H3BO, * NH, analysis.
(iii) From colemanite. Boric acid is obtained by
Uses. Boric acid is used :
passing sulphur dio:ride through the solution of the
(i) in the manufacture of heat resistant
borosilicate glass.
(r'i) as a preservative for milk and food stuffs

(r'r) in the manufacture of enamels and glazes

carBuo,, + 4so2 + 11H2O -+ in pottery.
Colemanite
(iv) The aqueous solution ofboric acid is used
ZCa(HSOr), + 6HrBO3 as a m ild antiseptic especially as eye wash under I he
Cat. bisulphite Boric acid boric lotlon-
. Properties. (i) It is a whitc crystallinc solitl Structure of Borlc acld. The ground state
with solt soap), touch.
a outer electronic configuration of boron is 2s2
( ) It is sparingly soluble in coid water but
el.
ID the excited state, one of the 2s-electrons geLs
fairly soluble in hot water. promoted to the vacant ?/-orbital. The three h-alf_
(iii) Acidic nature. Boric acid behaves as a
weak (K" : 1 x 10 e) monobasic aci<l. It does not
act as a pmton-dono, i.e., proionic ucid but behaves
aLewis acid i.e.,'ti a(:cepis a pai of clecrrols from
OH-
i
io,r.

,..--.\ Therefore, BO!- (borate) ion has trigonal

H:oH -i B(oH)r [B(oH)rl- + H+ planar structure as shosm in Fig. 13.3.

-
13/8 Pratle,,.1:'s Neut Coursc Chem istr4fiffi
2p, 2py 2pz
B
(Ground date)

SP2.HYBRIOIZATION
B
(Excited state)
illl lt lt li I

,/ o
FORMS THREE B- O 6- BONOS

FIGURE 13,3. Trigonal planar sbucture of BO!'unit'

Inboric acid, planar BOI- units are joined by Notc, It may be noted that wherever two or
more boranes with the samc number of B-atoms
hydrogen bonds to give alayer structure as shown in
but different number of H-atoms are known (for
Fig. 13.4. rancs, octaboranes
of hYdrogen atoms
the name so as to
distiuguish them from onc another.
Prtparatlon ofDlborane. It riray bc prepared
by the following methods :

(i) By reduction oI boron tritluoide etherate

with lithium aluminium hydride (LiAlH) in diethyl
elhe,l
Dicthyl
4BF3.Et2O+3LiAlH.
cthcr
Boton rrifluoridc
cthcratc
2B2Hs+ 3LiF + 3 AlF3 + 4 Et2O

(r'i) Laboratory
FIGURE 13.4. Stnrcture of boric acld Diborane is prepared
(dotted lines represent hydrogen borids).
oxidation of sodium b
1333. Boron HYilrldes iodine in diglyme
(CH3OCHPH2OCHTCHTOCHT) as solvent
Didvrne
2 NaBH. + !L B2H6 + 2NaI + H2
( i) Inrlustrlal prtparadon. On the industrial
scale,'diborane is obtaincd by the reduction of
BF3 with sodium hyddde.
(r) B.H,+. (called nido'boranes) such as
450 K
BrH, (diborane), BsHe Qrentaborane-9)' B6Hto 2 BF3 + 6--' B2H6 + 6 NaIi
NaH
(hexaborane- 10), BgHr2 (octabomne',2), BloHt4
Preparation of hlgher boranes' Higher
(decaborane) etc. B5H, and BroHrn) are ob-
boranes (-BnH,o, BrH11,
(ii) B,H,*. (called cracftno-boranes) such as K
tained when BrH, is heated at 373-523
BoHrn (telraborane), BrH,, Qtentaborcne- l1),
Properfles. (i) Physlcaf stste. Diborane is a
B5Hr., (hettborane' t 2), B"Hr, (ocmborane- 14),
colourlesi, highly toxic gas with a b'p. of 180 K'
BoJJr, (nonabomne or enneoborone) elc'
 SOIVIE P.BLOCK ELEMENTS
13/9

n:p,-
3n
Brlfo -:-: .- .*
- 523K n-[
BaH16, C5H1, 86H,, etc. I
S.olcd tube H
temperature, pressure Borazine
an iudividual boranes can H
be

2BrHu
353_363
;;;---11-
K
B4Hro + Hz
'\fizJ--...-il"
200 atm,S ht

. (l'it) Combustibility. It catches fire spon_

l.aneously upoo exposure to air. It burns in oxvqen
evolving an enormous amount ofheat. '- "z'\i_zr\,, I
B2H6+302 ....*BzO:+3H2O; H
Borazinc
aJf = - 1976 kJ mol-r H
Like- diborane, higher boranes also spon_ H-..,.o:[-"--.-,,
taneously burn in air.
(iv) Hydrollsis. Boranes are
hydrolysed by water to form boric acid
BzH6 G)+6 H2o (/).....- 2 H:BO: (aO+AHn@)
readilv
,---l \ "--J--n
I
With methanol, trimethylborate is formed H
Bcnzene
B2H5 * 6CHrOH.......r 2B(OCH3)3 + 6H,
Because of its similarity with benzene,
.borazine is also called inorganic benzene,
(vii) Formation of complex borohydrides.
^
Several metal hydrides react with diborur" to fo.rn
telrahydridoborutes commonly known as
BrH. * 2 NMe,
-.r2BHr.NMq
.--..r
borohydrides. AII these contain the tetrahedral
B2H6 + 2CO 2 BHr. CO [BHol- ion. For example,

+ B'zH5
.i fr}." {3 2Na+[BH1l-
Sod. borohydride

to give a volatile compound called borazine (or ..a)H + B2H6

.uthiuhhydride - -
l:g 2Li+[BH4l-
erhcr Lirhiumborchydridc
borazole).
lrw tenrD. .Bojl sodium borohydride and lithium
.Dorohydnde
3 B2H6+6 NH3 ---i 3 lBHz (NH3)21+[BH4l- are used as reducingageDLs in organic
slmthesis. Ttey also serve as stiti-ng materiil
413 K for
--_.-----, 2 B3N3H6 + 12 H2 many other borohydrides.

Bor.azine - (vll) Rmction with alkalies, Diborane dis_

(NaoHor
1i::ii'q"rertl.{:s KoH) to p,oau..
metaborates and dihydrogen gas.
82I{6+2KOH+2H2O
2KBO2 + 6H2
pot. metaborate
 Ne.a
13/10

(er) Actlon of halogen acids. Diborane reacts IIH

with hiogsn acids to give halodiboranes evolving
H, gas. T[e reactivity of halogen acids follows the
H:C :C:H
H;
X-Diffraction studies have shown that the
structure of diborane is as shown in Fig 13'5
halides as catalYst.
323K
BrHu + HI '-""""+ B2H5t + H2
Dibonnc lododiboranc
AlBrl D"'
B2Ho + HBr B2H5BI + H, q:
Dibolanc lihomodiborane

aor
B2H6 + HCI B2H5CI + H2
Dibomne o orcdiboraflc
FIGIIRE 13.5. Slrucrure of a diborane molerule'

In this structure, therc are two tyPes cf

Thus Cl, reacrs explosively at roorr tempera-

ture, Br2 reacts rapidly at 373 K whilc I, reacts

slowly at still higher tcmPeratures.

29E K

ExPloivE Chlorcdibo.nc molecules.

(i)
Structure of dlborane (BrH)' The struc- covulent
ture of bond is
diborane, tween B
centre elcc'tron palr bonds or two centre two'
electrons
boron for etectron bond (2c
-2e).
hvdrocen atoms, then there are no elcctrons
lJft wlth boron atom for sharing with other

ethane as shown below :

bonds.
HH
n:i t i:n
HH
No elcctron6 for B-B bond formatior
 SOME p-BLOCK ELEMENTS
13/11
whereas the third half-filled hybrid orbital of one (l) By heating a mixture of boron oxide or
boron atom ard the vacant hybrid orbital of tlre bor:u with calcium fluoride and conc. HrSOn
second boron atom (showo by dottedlines) overlap
simultaaeously with the half-hlled orbital of H- BrO, * 3CaF, + 3 H2SO4 Gonc.'1!
atom. Thus the electron cloud contains only two Boron oxide
electrons but spreads over ttree atonls (trvo B
atoms and one H-atom). That is why this bond is 2BF. * 3 CaSOo + 3HrO
called three cnlre electroo pair bond, Because of
the shape of the electron cloud formed, it is also
Na2BaC)7 + 6 CaF, * 8 HrSOo (conc.) -1
called banana bond. Borax
4 BF3 + 2 NaHSOa + 6 CaSOn + THrO
b
In the abovc reactioD-s, HF may be used in-
5B
(Grcund Slatc) E stead of CaF, i.e.

B?O3 + 6HF + 3H2SO4

d

sB
\Excitcd Statc) tI Boron oxide

Na2BaOT + lZHn +
2BF3

ZHTSO.
-
+ 3H2SO4.H2O

.a
,p3 - Hpriai""tion Borax
2NaHSOo+4BF3+7H2O
(ii) By heating a mixture of bomn oride ond
,11 antmon iun
\,.&",,/ (iii) B2O3
t, le trafluorob ora le

* 6 NHoBFo .-.----r
.\ \H 8BF3+6NH3+3H2o
-JH Pure BF, can, however, be prepared in the
3c-2e B
Iaboratory by thermal decomposition of ben-
Molecules tike BrII5 which do oot have suff- zenediazonium tetrafl uoroborate.
cient number ofelectrons to form normal covalent A
honds (two ceotre-electron pair bonds) are callcd C6H5N2BF. ....- CoHrF* N2 + BFj
electron defi cieni molecules.
The structures of boranes were studied in (D) BCl, and BBr, are obtained by passing
detailby William Lipsocomb who was awarde<t the Cl2 orB12 on a heated
mixture ofboron trioxide and
1976 Nobel Prize in Chemistry. porvdered chiucoal.
'l3.4. Boto n Ha Iides ;.t i!:,ti:irl:iir:;i:r,:iiir::rliii;1,j:iii::iij,iir:r|']lti,::: i::ir. I
TBK
B2O3 + 3C + 3Ct .+ 2BCl3+3CO
Due to small size and hieh electronesativitv
boron forns covalent trihafides of the g"enerai T73K
forms, BX, (where X = i Cl, Br or I) B2O3 + 3C * 3Br, 2BBr. + 3CO
The covalent character of these trihalides is
---r
BCl, can also be prepared by heating boron
supported by the following facts
trioxidc rvitb phosphorus pentachlorirle in a sealcd
(i) They do not condtd elcciicity in the liEtid tube.
state.

,o
m
'il?#f !;ii; BzO3 + 3PClj ......-
A

(c) BI, can be prcpared by reduction of

?BC\+
BCl,
3 pOCl3

Pnparaflon. (a) BF, is prepared by eithcr of wirh HI

the following three rnethods BCL +3HI
-rBIr+3HCl
13112
Structurt. The trihalide of boron are plarar
pounds.
' i' ptcung 13.6. Stucture oI boron trthalldes
' ']::,.: :.;' : :]l
Retative acid strngth of boron trlhalides'
The boron atom in all the boron trihalides has only
six electrons in its valence shell and hence need's
two more electroas to comPlete its octet' There-
fore, all the boron trihalides behave aslen'is acids'
The relative strength of the various boron
trihalides increases in the order :
BF3<BCl3<BBrr<BIr.
This order canbe easily explained on &e baru
ol the tendency ol the hqlogen atom lo bock don0te
iis pai oi electrons to the empty p-otbital
lont
b;;;" A;^ ihroush p,t - pn- boidins (Fig'
Since the size of the vacant ?-orbital of B and the
2r-orbital of F containing a lone pair of electrons
a're atmost identical, therefore, the lone pair of
electrons on F is donated towards the B atom'
Further, due to back donation by three F atoms,
BF, can be represented as a resonance hltrid of
the following three structures (Fig' li} 8)'
l),-. .--* )"-,.*')'-'
FIGURE 1g.8. Resonance stuctures of BF3
molecule invofuing back bonding'
As a result of ptt-ptt back donation and
resonance, the electron deficiency of B decreases
and thus BF, is the weakest Lewis acid' As the size
to BBr, to BIr. 7rl s, the relative acid stenglh of the
borcn tihalides Iollows the sequence :
BFi<BCl3<BBrr<BIr.
(a) Physical properties. (i) All the boron
tihalides exist ss monomeic covolenl species' They
do nol ilimeize like BH, s tce lhe lone pairs on the
halogens can interact with the vacant p'otbiaal ia
pn : pn back-borrding as discussed above.
(ii) BF3 (m.p. 145 9 I! b.p. 172 K) and BCl,
(m.o. 166 K b.o. 285'5 K) are colourless gases at
ioo, t"-p"rrtut.. BBr, is a colourless liquid (m p'
227 K"h.p.364 K) while BI, is a white solid (m'p'
422.9K).
(rD BF3 is extremely soluble in water and is,
therefcre, collected over mercury.
(iii) BF, forms two hydrates, BF, . HrO and
oI the
BF3 . 2 H2O.
13'7)'
(D) Chemical ProPrties. (i) Hydrolysis' All
the boron trihalides are hydrolysed by water'
B\ is tlydrolysed slot ly and incomPletely to
lonnlhtoboic acitl This is because HF Frst
formed
reacts with H3B03.
BF3 + 3H2O H:BOr+3HFlx 4
-
4 HF + H3Bo3 ""'- HBFr + 3 H2ol x 3
4BP3 + 3HzO HrBOr + 3 HBF4
- Fluoboric acid
The other tihalides ue hydtolysed completely
to give boic acid ond the corresponding halogen acid
BX3+3 H2O """'' H3BOr+3 HX (X:Cl, Br or I)
Due to formatioo of hydrogen halides as a
result of hydrolysis , boron trihalides lttme in sir
 SON/E p-BLOCK ELEMENTS 13/13

Bx3 + NR3 ---- xjB .-NR3 Naturally occurring carbon has two stable
structures. Some of these complexes of BF, are isotopes: rzc (98.9Vo) and r3C (t'lVo) in addition
to traces of radioactivc laC isotope with a half life
shown below :
of 570 years. It is used in radlocarbon datlng to
F. OEt2 F M: determine the age of archaeological samples of
\u/ \"r, organic origin i.e., fallen trees, dead animals etc.
The l2C isotope is assigned a mass number of
o,,'\o \o 12' 00000 units and is used as an international unit
for atomic mass instruments.
trifluoridc
Borc,l
cthctatc
"/
Boron taifluoridc-
ammonia complex 135.1. Tbrrcstrial Abundance and Distrlbu.
tion

or TbtoJlaorcboruc
ion mqlachite
( r) Reactlon wlth Grlgnard rcagrnts and or.
ganolithlum reagcnts, Boron halides react with
Grignard reageats and other organolithium
reagents to form trialkyl or triarylboranes.
BF3 + 3qHjMgBr ......} B(9Hs)r + 3MgBrF
Tricthrtboraac
Uses,(i) Due to greater resistance of BF, to
hydrolpis as compared to BClr, BBr, and BIr,
BF, is *tensively useil os cstalyst in fuied.l-&afis
allElalion and aqlotion re actions.
BFr
C6H6 + CHICH2F -- C.H5 - CHTCH3 + HF
Eth}'lbcnzcnc
BFr 13.52. Allotropic forms of Carbon
C6I++CH3CH2OH.-.........)C6H,CH2CH3 + HzO
(ir) BF, is also used as a catalyst ia esterili-
BFr
RCOOH + R'OH -.--+ RCOOR'+ H2O
cation and polymerization reactions used to
prepare polyisobutylenc and butadiene-styrcne
polymrers.
(ur) Bclris used in production of clemental I. Crystalline, and II. Amorphous
boron by its reduction with Mg. I. Crystalline allotropic forms of carbon.
13.5. Carbon Tfuee allotropes of caibon having well dehned
.crystal structures are :
-
Carbon is the seventeenth most abundant ele-
ment by weight found in the earth,s crust. Never- 1. Diamond, 2, Graphite and 3. Fullerenes.
theless, it forms more compounds than any other Due to different structures, they have dif-
element except hydrogen. ferent properties.
13114 Pradeep's

1. Dlamond (iv) Diamond is also used for making dies for

It occurs in nature. It can also be prepared drawing thin wires from metals.
artificially but because of the high cost and poor 2. Graphite
quality, diamonds are seldom made artifrcially. It occurs in nature and can also be manufac-
Structure. In diamond, carbon is sy'- tured artihcially by heating coke to 3273 - 3300 K
hybridized. Each ca in an elecric furnace.
four neighbouring Structur.. In graphite, carbon is sp2-
strong C - C, s1 - hybndized. Each carbon is thus linked to three
tends in three dimensions (Fig. 13.9) and is very other carbon atoms forming hexagonal rings a-s
rigid. shown in Fig. 13.10a. Thus, unlike diamond,
graphite has a rwo-dimensional sheet like (layered)
slmcture crrrsrsting of a number of benzene rings
fused together (Fig. 13.10b). The various sheets or
layers are held together by weak van der Waals'
forces of attraction. The distance between any two
successive layers is f.rlO A (lO pm).

142 pm
<.+

FIGURE 13.9. Sttuctue of dlamond

Propertles. (l) Purity. Dianond is the purest

form of cafion .
(li) Bond length. Because of #-hybridiza-
tion, C- Cbond lengths indiamond are 1.54A (154
pm). o
(tll) Hardness. Sinc e diamond sists as 4lhrce'
dimensional neflvork solid it is lhe ho esl substance
lorown with higfi density and melting point
(lv) Conducdvlty. Since all lhe elecoons an
firmly held in C-C, o-botds, there are no free
electrons in a diamond crystal. Therefore, diamond
is a bad conductor of clectricity.
(v) Thansparrncy. Becoure ol its higfi rcfrac-
tive inilu (2.5), dianond con rcIlect dnd relract light.
It is, lherelorc, a tmnsparent fltbstsnce.
Uses. (r) Because of its hardness, diamond is
used for cufting glass, making borers for rock drill-
ing and for making abrasives.
(ri) When diamond is cut and polished, bril- o
liant light is refracted from its surfaces. That is whyl
diamond is used for making precious gers aod
jewellery.
(iri) It is used for grinding and polishing of
FIGIJRE 13.10. Shucture of graPhlte
hard materials.
 SOME p-BLOCK ELEMENTS
Propertles, (i) Pttrlty. Like diamond, graphite
is olso the purest fomt of carbon.
(ii atiotl
the c- ( 142
pm).
(lii) Softness. Srzce any two successive ldyers
are held. togelher by weak lorces of attmctio,t, one
layer can slip over the other This makes graphite soft
and, a good htbicoling agenl.
(iv) Conductivity. Srzce only tluee electrons oI
each cdtbon are used in making hetagonal ings in
graphite, foutth ydlence electron of each carbon ;s
hee to move. This makes graphite a good contluctor
of hest and electricity .
(v) Opaqueness. Un like diamon+ gaphite is a
black substonce snd possesses a metallic luslre.
Uses. (i) It is used as a reducing agent it steel
manufacturing.
(ri) It is also used in high-strength composite
materials.
(rii) Graphite is used for making electrodes
for dry cells.
(iu) Graphite marks papcr black and is, there-
fore, calJed black lead. Mixed with desired quan-
tities of wax or clay, graphite is used for making
cores of lead pencils.
(v) lt is used in the manufacture of crucibles
which car with.stand high temperature.
(vi) Graphite is also used as a moderator for
fast moving neutrors itr atomic reactors.
(vri) It is used as a solid lubicaat for heavy
machinery.
3, Fullerrnes
Discovery. B
allotropes of carb
were known. But
lotrope of carbon
entists namely R.E. Smal/ey
University, Houston, Texas
,o of the University of Sus_
sex, Brighton (U.K.). For this discovery, these
scientists shared rhe 1996 Nobel prize in chemistry.
Preparafion and separation. lcu llerenes con-
tion ofgraphite using a powerful laser. However, a
more practicalmethod for production of fullerenes
in macroscopic quantities, involves heating of
13/15
graphite in an electric arc in an inert gas such as
helium or argon when a sootymaterial is formed by
the condensation of C, small molecules. The sooty
material so formed mainly con-sists of C* fullerene
with sma.Uer quantity of Qo and traces o[ other
fiIlerenes consisting of even number of carbon
atoms upto 350 or above. The C* and Cro ful-
lerenes can be readily separated from the fullerene
sootby extractionwith benzene or toluene followed
by chromatography oyer alumina.
The complete process of formation and
separation of C, and Cr6 fullerenes from graphite
may be sketched as follows :
Electric arc
Graphite -------------.-- Vapourisedcarbon
He or Ar
Condensatiorl
Fullerene soot
(C6o + tit e C7d
Chromatography
Ceo+go
oveaAl2O3 Fullercne Fulterene
It is interosting to note that unlike graphite or
diamond, the fullerenes dissolve in organic sol-
venls. Asolution ofCa6 in tolueneis purple whereas
that of Cro is orange rcd,.ln fact,Iullerenes are the
ottly pure form of cafton becsuse thE do not hove
daagling edge or surface bonds which attract other
dtorns as is lhe cose of graphite or dianond.
Structurr. Of all the fullerenes, C.o allotrope
is most stable. It looks like a soccer ball and is
sometimes called as bulky ball. It contains 20 six
membered ings and 12 five membered nhgs. Six-
membqred rin&s are fused both to other six-mem-
bered rings and five-membered rines, but the
five-membered rings are connected only to six-
mernbered rings (Fig. 13.11).
This molecule has spherical shape having 60
vertices with a carbon atom at each vertex. Noting
the similarity of this molecule to the geodesii
domes (having hexagou al and pentagonal patterns)
designed and built by the American architect,
Robert Buckminster Fuller, it was named as buck-
minster fullerrrne or sirhply fullerene.
Because all the caibon atoms are equivalent,
the strain caused by the distortion of the bonds
from coplanarity is equally distributed among all
the carboo atoms. ConsequeDtly the molecul-e is
quite stable.
13/16
Ft rene (Crd.
ent ard
afe
It contains both singte and doublebonds with
C-C distances of 145'3 and 138'3 pm respec-
tively.
Q9 fullerene, on the other hand, resembles a
rugby ball. /r consis s of 12 five-membercd rings md
2i six- membered rin6s. As in Co6 fullerene, the
pentagons are isolated from each other.
Propcrtls. (i) Fullercnes being cova.lent
soluble in organic solvents.
ft;) fhey can be reduced electrochemically
and react with group 1 alkali metals, forming solids
such as IqC6o. This compound behaves as a suPer-
conductor below 18 K which means that it carries
electric current with zrro resistance.
(ri) It reacts with OsOn which adds across one
of the double bonds in the cage.
(iv) It also forms platinum complexes'
At
Uses. have anY
practicaluses
ierenes may fi I aPPlica-
tions.
II. AmorPhous allotroplc forms o[ carbon
T'ho important amPhorphous allotropic forms
of carbon are :
1. Coke 2. Charcoal 3. Carbon black. These
are all impure forms of graphite or fullerenes.
---G"i'"out ir,.ubjcctpd to dcsttuctivl dirtillstioD for the ma.lufactu& of oil 8at, cokc is lcft 8s Gsiduc
samr timc, a thick dcPo6it i5 obiaiocd on thc roof
Neul Coarse Chent istr4
1. Coke,It is a greyish black hard solid and is
obtained by destructive distillation* (strong heat-
ing in absence of air).
2. Charcoal. It is obtained in the following
four forms, i.e.,
(i) Wood charcoal. It is obtained by strong
heating of wood in a limited supply of air.
(ll) Anlmal charcoal. It is also known as bone
black ar.tl is obtained by destructive distillation of
bones. It consists of approximately 10Vo carbotrest
being calcium phosphate.
(iii) SugBr charcoal' It Ls tho purest form of
amorphous carbon and is obtained by the action of
conc. HrSOo on sucrose or cane sugar.
Conc. H2SOa
.........._
Cr2H22Olr (r) 12 C (s) + 11 H2o (0
sugar charcoal
(lv) Activatd charcoal. All forms of char-
coal are highly porous substances and can adsorb
of gases. Their
her increased bY
current of super
removes the im-
purities such as residual hydrocarbons, orygen
etc. sticking on the surface and thus blocking the
capillary pores. CharcoaI thus prepared is called
are activated charcoal.
(v) Carbon black or lamp black. It is an
petroleum, turpentine oil, acetylene etc. aro
burnt in alimited suppty ofair. The soot obtained
is made to stick on wet blankets hung in a cham-
ber. After drying, the soot is removed from the
blankets. The soot thus collected is called the
lsmp black or carbon black.
that ful-
cH4 + 02
A
c + 2H2O
Limited supply of air Carbon black
All the allotropic forms of carborq whether
crystalline or amorphous, burn in excess of orygen
at diftbrent temperatures to form carbon dioxide.
This shows that all the above forms are allotropes
of carbon.
in tbc rEtort' At the
and sid'x of thc trtort' It i' callcd ti gts cttbo[
 SON,IE p-BLOCK ELEMENTS 13117

, i, I Of all tbe crlstalline allotropic forms of cnrbon, graphite is thermodyDamically rhe most ;ble allotrope. Its
standard enthalpy of formation (qf{) is assigncd a value of zero. The standard enrhalpy of formation
(A/H) of rliamond and C6o fullcrene are 1.98 aDd 38.1 U mol- l respcctively.

iii:t : Graphlte is thermodynamically more stable than diamond since ils free eners/ of formation is 1 .9 kJ mol-l
losrcr al rmm temperature and atmGpheric pressure. Although the conversion of diamoDd into graphite is
thermodynamically favourable, yet is Dormally does not @cur because of high enerry of activation for the
Proccss.
Ifthe enersr of actiration is made available, the cooversion ofdiamond into graphite can occur.
The rwerse process, r'.e., conversion ofgraphite into diamond is thcrmodlnamically not pcsible but can be
done only under forcing co[ditions. Thus, graphite can be corrverted iDto diamond at 1873 K under a prqssure
of 50,000--50,000 atmGphercs.
i::: 3. Dl.mond has the highesl lhermal conduclMty of any known substance (about fiw times that ofC\) although
it is a bad conductor ofelectricity. It is becaur of its high lhermal cooductMty, diamond tipped tools do not
over heat aDd hence are odeDsively used for drilling and cuttiDg purpces.
iJ,, .1. Kohlnoor dieDord. The valuc of diamDo[d is exprcssed in tenru of its wcight and purity. The weighr of
diamond is cxpressed in terms ofcarats (l cardt = 200 mg). The famous Kohlnoor diamond which decorates
the cro n of England's queen at present weighs 108.93 carals, Horever, wheo it was takcD from lndia to
Eogland, it wcighed 181 carats. Tb restore its brillialce and lustre,43 ot its on6nal weight was shed.
, 5 Corbon nanotube6. A nanotube is a structure which looks as though it were formed ry rolling a sbeet of
Braphite like carboo (a flat Detwork of fused benzene rings resemb[flg chickeo wire) ioto the shape of a
cylindrical tube and capping each end with halfofa buckyball (or tullerene like hemispheres). These are also
produced by elcctric arc svaporatioD ofgrapbite.
The discovery of carbon nanotubs has trig8ered worldwide interest in studyiog the ph),sical propenies of
carbon naDotubes and their potcntial applic-tions in catallsir, nanotechoolosr and electronics.
Nanotubes are very tough-aboul. 100 times as stroog as steel. Besides their poteltial as strengthcners for new
comPcite materials, some nanotubes havc been shown to act as electrical conductors or semiconductors
dependiDg upon their precise size. They are also bing used as rips for anab,sisof DNA and proreins by atomic
force microscopy (AFM) or as molecular size test tubes or caFsules for drug delivery.

13.53, Atornlc anrl Physlcal Propertles. TABLE 13.1. Atomic and Phl,.sical
(i) Carbon
exists in various allotropic forms of Properties of Carbon
which diomond, gmphite and fullerene are cr]atal- Den- Mel. Cova- EIe!-
line while coaf h)oo4 charcoal, oimal charcoal ; sity ting lent fro-
G
lamp black, coke and gas carbon are amorphous. point Ilo8a.
cm-3)
The X-ray anal)'sis has revealed that so called at 293 (K) (Pl,,) tivity
amorphous carbons also have extrcmely fine crys- K
tals. Therefore, these allotropes are called I II III IV
mi c roc rys ta I I ine c atb on s. .51 'l't
3 4373 25 to86 2352 4620 6220
Some atomic and physical properties of carb-
on are listed in Thble 13.1.
13/18

13.5.4. Chemlcal Proprtles (ii) It is oxidised by conc. HNO, to give

graphitic acid, C,,HaO5 which is an insoluble yel-
lowish green substance.
(r,r) With alkaline KMnOa, it is oxidised to
oxalic acid and me llitic acid, C5(COOH)5.
'13.6. Oxides ol Carbon
one another to Iomt covalent bonds lo form long or
branched chains and ings ol different.rlzes This Carbon forms many oxides. T\vo of these
oxides, vrz. carbon monaxide (CO) ar.<l cabon
dioxide (COr) are extremely stable and important.
The three less stable oxides are '. corbon suboxide
However, as we (C,OJ, C5O2 and C,rOr. Others which are even
t-element bond lcss stable include graphite oxides,
(355 kJ mol - t), QO and QOr.
? kI mol-l and 1. Carbon monoxide
Sn-Sn (155 kJ mol-1), therefore, the tendency for Preparation. (i) It is formed by incomplete
catenation decreases in the order : combustion of carbon and carbon containing fuels.
C>Si > Ge>Sn. 2C + Oz ---'-'
zCO
(ii) Multiple bondiag. Due to its small six and
higher electronegatiity, carbon has a strongtendency This type of incomplete combustion occurs
to Iorm W - pt muLiple bonds eitht with iBeU during burning of petrol or diesel in automobiles
(C -- C, C = C) ot with othu atoms of similar size and, therefore, CO is always present in automobile
ntch ar orygen (C: O) and nitrogen (C = N C=N). oxhausts, It is also present in volcanic gases and
gases coming out of furnaces.
In viw of these two properties, carbon forms
several millions of compounds both naturally oc- (ii) Carbon monoxide can also be prepared by
curring and man made. reduction of oxides of heavy metals with carbon.
Some important chemical Propcrties of three ZIO + C """""'. Ztr + CO
important forms of carbon are described below : and FerO, + 3C ' zFe + 3CO
(a) Charcoal. (i) Of all the allotropic fgrmn
(iii) In the Iaboratory,pure carbon monoxide
ciarcoal is the most reactive. It readily burns in air
to form COr. It reduces conc. HrSOa and conc. is obtainedby dehydration offormicacid with conc.
HrSOo at 373 K.
HNO, to SO, and NO, respectivelY.
H2SO4
(ii) It combines with many metals to form the HCOOH co + H2o
corresponding carbides, e.g, CaC2, AlaQ etc. acid 371K Cafton llonoxidc
Irormic
(iii) When heated with sulphur, it forms carb- Carbon monoide can also be prepared in the
on disulphide (CSr). laboratory by the action of conc. H2SOa on Potas-
(i) Dlamond. Chemically, diamond is mmt sium ferrocyanide.
resistant towards most of the chemical reagetrts. lt Ko [Fe(CN)rl + 3 H2SO4
burns in air at 1173 K to form COz.
2 K2SO1 +- FeSOI + 6HCN
(rI) It is slowly oxidised by a mixture of
IQCrrO, + conc. HrSOo at 473 K to give COr. HCN + 2 HzO +HCOOH+NH3l x6
(iii) It is stable in vacuum upto 1773 K brt HCOoH '----* H2o + CO I x 6
changis into graphite at ?!73 K and more rapidly 2 NH3 + H2SOa- (NH1)2SO1I x 3
at 2/73 K.
(c) Graphlte. (i) Graphite, Iike diamond, is
not atiacked 6y dilutC acids. It is slowly oxidised by \[Fe(CN)6] + 6H2So4 * 6H2o
-----'r
chromic acid (HrCrOn i.e IlCrrO, , *
conc. Pot. fcrrocrEDidc
2K.SO4 +' FeSO, + 3 (NH.)rSO4 + 6CO
HrSOn) to CO2.
SOIVE P-BLOCK ELEMENTS 13/19

Commercial preparation. (i) It is mmmer- ++

cially produced bypassing steam over red hot cokc.
-:C:::O: or -:C=O: or:CSO:
This reaction also produces hydrogen. IIa IIb IIc
413-1273 K However, CO is best represented as a
C(s) + HrO COG) + HrG) resonance hybrid of the following two structures.

-'c=J,
A mixture of CC) and H,
Water
is called watergas
g'as

or '.4i'.-*
The presence of a triple bond between C and
synthesis gas. O is supported by the following evidences :
(r'i) When air is used instead of steam, a mix- (i) The carbon-orygen bond length isjust 113
ture of CO and N2 are prdouced. This mixure is pm which corresponds to a carbon-orygen triple
called producer gas. bond.
7273K (i) The dipole momentof CO is very low due
2C(s)+02G)+4N2G)............- to back donation of a pair of electrons from the
more electronegative O to the less electronegative
Air C-atom.
2COG)+4NrG) Properties. Some physical properties of CO
are given in Table 13.2.
Producrr gas
(i) It s a neutml axide.
CO present in water gas or producer gas can
(ii) It is a colourless and odourless gas which
further undergo combustion forming CO, with
is only slightly soluble in water.
evolution of heat. (rii) Poisonous naturc. Carbon monoxide is
zco G) + o,(g) """.zco,(s); highly poisonous (toxic) in nature. Its toxic nature
al{' = - 566 kJ mol-r Ls due to its abilig to form a stable complexwiththe

haemoglobin present in the red blood cells to form

Thus, water gas and producer gas are two cafioxyhoemoglobin as discussed below :
industrially important fuel gases.
Haemoglobin + CO Carboryhaemoglobin
Structure. In CO molecule, both C and O --r
atoms are sp- hybridized. One sp-hybrid orbital In the lungs, haemoglobin combines with
each of C and O overlap to form a C-O, o-boni molecular orygen loosely and reversibly to form
whilc the othersp-orbital on eachatom contairsthe oryhaemoglobin.
lone pair of electrons. The two unhybridized p-or-
bitals ofc and O formtvtop -pttbotds. Thus, CO
Oryhaemoglobin thus formed in the lungs
is a linear molecule.
then travels to all parts of the body through blood
_+ stream aud delivers 02 to the various tissues ofthe
lonepair ----- : C = O : .- lone pairin
body. However, CO combines with haemoglobin
in sp hybrid orbital sp-hybrid oribital. irreversiby (i.e. forms stronger bonds than O).
Due to the presence ofa lotre pair ofelectrons
on the carbor atom ,CO aicts alewis base or a ligond
Therefore, if CO is present, it will form stable
and can form a coordinate bond with metals complex with haemoglobin (i.e. car-
+ boryhaemoglobin) which destroys the orygen car-
(M <-C = O) to form metal carbonyls. rying capacity of haemoglobin. As a
result,
The electron dot structure for CO may be haernoglobin does not take up orygen easily there-
represented either by formula I or Ia. by causing suffocation and ultimately death.
(lv) Reduclng proprties. Since CO can be
: C:: (i: or :C = ii: easily oxidised to COz,ia acts a as powe4ul refurcing
IIa a8nt. As such it reduces many metal oxides to their
In these structures, C has 6 while O has 8 respective metals.
electrons in the valence shell. To complete the octet ZnO + CO .---------- Zt * COz
arourd C, O donates a pair of electrons as shown
in structure (IIa or IIb or IIc). CUO + CO -........+ Cu * COz
13120 Neut Course C(temistrq
Crrbon dloxldc
FerO, * 3CO 41273 K 2Fe + 3COz
2.
Prrparaflon. (i) It is prepared by burnirg
It also reduces PdClz to Pd ard I2O5 to I2. carbon, fossil fuels and other organic comPound.s
in excess of air or oxygen.
PdCl2 + CO + HzO- Pd + CO2 + 2HCl
c (s) + 02 @)
-------. @) coz
I2O5 + 5 CO'------ Iz + 5COz
CsHrz G) + 8 02 @)--"+ 5 CO2 (8) + 6 Hzo G)
(v) Formatlon of metal carbonyls. It com-
bines with many transition metals such as iron,
(ii) In the laboratory it is prepared by the
action of acids on carbonates.
cobalt, nickel etc. forming metal carbonyls. For
example, CaCO3 + 2HCl CaCl2 ' + CO2+HrO
330-350 K (iii) Commercially, Co, is produced as a by-
Ni + 4CO N(co)4
product during manufacture of ammonia. The
Nickcl carbonyl
hydrogen needed for the purpose is obtained by
473 K 100 atm. prcssurt
passing steam over heated CO or CHn.
Fe + 5Co Fe(CO)5
Iilcn crrtonyl A
co G) + Hro @)- co, (9 + Hz(s)
Nickel carbonyl is volatile. When heated to A
,{4O
- 450 K, it decomposes to form pure nickel. CHl G) + 2Hzo (g)- coz (9 + 4 Hz(g)
450-470 K
Ni(CO)o .................- Ni + 4CO It is also formed during manufacture of lime
or ethyl alcohol by fermentation of glucose or fruc'
Therefore, nickel carbonyl is used for tose.
purification of nickelby Mond's process.
1600 K
(vi) Formation of phosgene. It readily com- CaCO, CaO + CO,
bines with Cl, in presence of sunlight to give car- Lirnc6tonc Linc
bonyl chloride or phosgene which is an extremely z-fiie
poisonous gas. C6HI2O6 4 ?9HsoH + 2Co2
hs Gluco6. orFructosc Ethy' alcohol
Co G) + ctz G) ..._ CoCl, G) Structurc. In CO, nolecule, C is sP'
Phosgene
hybridized, it fonns two a-bonds with two o4lgen
(vii) Absorption. Carbon monoxide is readily atoms and twopz-p, multiple boads. As a result,
absorbed by a solution of CuCl in conc. HCI or COr's a linear, monomeic covalott compound.
NH, due to the formation olsoluble complexcs. For
example,
The electron dot structure for CO, may be
CO._ represented by either formula I or Ia
CuCl + NH, + [Cu(CO)NH3]+ CI-
(Soluble comPlet)

C.Cl + HCI .,- 69 ....* 11+1Cu(CO)Cl2l- :ii,,C:,ii' o,,ci=c=ti:

(Sohtble
Uses, (i) it is an important constituent of two
industrial fuels !.e., water qas and producet gas.
(ii) It is used in Mortdtprocess for purification
of nickel via its nickel carbonYl.
(iii) It is used in the manufacturc of methyl
alcohol, acetic acid, synthetic petrol, sodium for-
mate etc.
lIa
compla)
This structue predicts that both the carbon-
orygen bond lengths in CO, should bc equal and
should hare a typical bond leagh of 122 pm. How'
ever, operimcntally, it has been found that carbon-
orygen bond length in CO, is only 115 pm' This can
be explained, if COz is considered tobe aresonance
hybrid of the following struclures :

agent.
(iv) In the metallurgy ofrlron as a reducing
-,5\ .4, *, ,fl .41, --
+
(v) Iron carbonyl is used in the mandlacture :O=C- O:-
of maletic tapes foiuid"oe, and tupe ,ei6rders.
SOME p.BLOCK ELEMENTS 13121

Due to resonatrce, carbon oxygen bond length Proprtles. The phpical properties of CO,
acquires some triple bond character and hence the are quite different from those of CO. Some impor-
bond length decreases from 122 pm to 115 pm. tant physical properties of CO and CO, are given
in table Ij|.2.

TABI.E 13.2. Physical properties of CO and CO,

co cor
Melting point (K) 68 216 4 at 5.2 atm.
BoiliDg poiDt (K) 81 5 $a.5 $ubl aes)
Deosity (8L-l) at 273 K 1.250 1.977
C-O bond length (pm) r12 115

Heat of formation r'.e. Hf (kJ mol-l) 10.5

-1 -393.5
(i) lt is a colourless and odourless gas about COr2-. These equilibria are very important itr
1 5 times heavier than air. HrCOr/HCOI buffer qistem which helps to main-
(ll) Unlike CO, CO2 is not poisonous. How- tain the pH of the human blood between 7.26-
ever, it does not support life in animals and human 7.42. Rrrthermore, the rate at which CO, comes in
beings. However, it can cause soffocation and even- equilibrium with H2CO3 is slow and this is also
tually death due to lack of oxygen.
important iu the physiology of COr.
(lll) Non.combusdble nature. Ordinarily
CO, is neither combustible nor a supporter of com- (vl) Reactlon wlth llme nater. When CO, is
bustion. However, certain active meta.ls such asNa, passe d through lime water, it turns lime water millry
K Mg etc. continue burning in it. due to the formation of insoluble cakium car-
ZMg+ CO, --'t 2MgO + C bonale.

(tv) Solubility.It is slightly soluble in water.Its

Ca(OH), I CO2 '--+ CaCO, + HrO
solubility in water, however, increases with increase
Limcsetcr (Insolablc)

in pressure. Soda water and other aelated soft However, if CO, is passedfor a longer period,
drinks are, in fact, solutions of carbon dioxide in the turbidity disappears due to the formation of
water (containing sugar, somc flavouring and s oluble calcium b ic arb on nte.
colouring agents) under prcssure. caco3 + H2o + coz Ca(HCOr),
(v) Acftllc nature. When CO, dissolves in (Sol!!blc)
water, only some of the molecules react with water or Ca(OH), + 2CO,
-
-..- ca(HCOr)z
to form carbonic acid (HrCOr) while most of the (vil) Photosyothesls, Carbon dioxide is ab-
dissolved CO, remains loosely hydrated. Carbonic sorbed by plants. In presetce of chlorophyll (the
acrd is a weak dibasic acid. It forms two series of green colouring pipent of the leaves) and sun-
salts, i.e., the hydrogen carbonates and carbonates light, the absorbed CO, combines with HrO to form
derived from the anions HCOt and CO!-. Thus, glucose and starch (carbohyd.ratcs) which are used
COris the anhydride of cafionic acid. as food by the plants. This process is called
photosynlhesis.
CO2 G) + HrO (f """+ HrCO, (aq)
c,rloroohvll
Cr6onic acid 6CO2 + 6H2O ----i; c6Hr2o6 + 602
H"Co, (oq)+ H+ @fi + Hco, (aq) sunlighi Cluclsc
HCof (aq) + H+ (aq) + col- @q)
(viii) Actlon of arnmonla, When CO, is
rcacted with liquid ammonia at 453
Thus, a sohrtion of CO2 in water is actually atr -473 K under
a pressure of 220 atnospheres, it first forms am-
equilibrium mixturc of CO2, H2CO3, HCO3- and monium canbamate which subsequently decom-
poses to give urea.
13122

453 - 473 K (iv) Solid carbon dioxide is used as a

2 NH3 + CO2
220 atfi
-------' NH2CONH2 + H20
Uses. Carbon dioxide is used
.(i) in the preparation of aerated waters.
(ii) as a lire ertinguisher because it is a non-
supporter of combustion.
(fi) in the manufacture of washing soda by
Solvay ammonia process.
[NHTCOONHI] refrigerant under the commercial naae dri kold
Amm. ca.tJamate (see under dry ice).
(v) Supercritical COr* is used as a solvent to
Urea
extract organic compounds from their natural sout-
: ces such as caffEine from coffee bean^s and per-
fumes from flowers.
(vi) lor anifcial respr'ratioz (for victims of CO
poisoning) as a mixture of 95Vo 02 and 5Vo CO2
under the name cariogvn
(vi) for purification of sugar in sugar industry.

,,i t The suboxide, Cr2O9 is also somewhat stable. It is a white solid and is an anhydride of mellitic acid,
c6(cooH)6.
, :,, L Nickel carbonyl, Ni(CO)1 has tetrahedral while iron carbonyl, Fe(CO)i has trigonal bipyramid geometry.

13,6.1. Dry lce Carbonates and bicarbonates of many metals

Dry ice is the name given to solid carbon are known but the bicarbonates of ony alkali metals
dioxide.lt is also called cardlce,Itis obtainedwhen exist in the solid state.
CO, is cooled under Fessure (50-60 atm.). When In aqueous solutions, both carbonates and
solid carbon dioxide is allowed to evaPorate in uir bicarbonates undergo hydrolysis producing OH-
ly ions.
a HCO| + H2O ---'-'- OH- + H2CO3
r-
e. co3-+Hro-oH-+HCO3-
Tltus, aqueow solutiow ol both bkarbonates
and cqrbonates are basic in nailre.
Imporlance. Many carbonates such as
NqCOr.l0HrO (washing soda),
KrCOr, CaCO3, NaHCO3 (baking soda) arc
widely used in industry and for domestic Purposes.
articles in food industry. Dry ice is also used for F\rther, it is interestingto mention here that bicar-
curing local burns and in hospitals for surgical bonates of calcium and magnesium are responsible
oPeration of sores. for temporary hardness of water.
13,62. Carbonates and blcarbonetes Structure. The central carbon atom of
Being an acidic oxide, CO, readily reacts with HrCO3, HCO3- and COI- ion is spz-hybridized. It
alkalies forming carbonates and bicarbonates forms three a-bonds with three orygen atoms. The
NaOHf COz NaHCO3 unhybridizedp-orbital on the carbon atom is delo-
NaHCO3 + NaOH .-..Na2CO3+ HzO calized over the p-orbitals of the three olq/gen
- atoms to form z-bonds (for details refer to unit 6).
2NaOH + CO, "-"+ 1rl6rq93 + H2o
g". .- u" iiq[n"a uilpplyirg prcssurr it ir is bcto\r, its crilical tcmpciaturc. For co2, thc criticat Prcssurc and
-.a
tcmperture are ?3 x 1 ,013 x 1d Pa (approx. 72.9 atm) and 3& K rcspecti!'Ely. A substancc abovc its criticll prcssurE is
callcd
yrt il is very dense and hence can hehave as a solvenl'
ip*ctiticol lluid- elnough at this Press;rc, CO2 is a gas,
 SOt!4E p-BLOCK ELEt\4ENTS 13123
'13.7. Carbides
ln these mmpounds, the carboo atoms occupy
Compounds o! arbon with elemerts of low* or interstitial voids in the close packed lattice of metal
about equal elrtronegativity are ullcrl carbidx. atoms. Carbides of this t)?e are extremelyhard and
electrically conducting.
Some important examples arc CaCr, Preparation. Carbidcs are usually prepared
AloC, , BerC , SiC etc. Thesc are further classified by heating the clement or its oxide with carbon at a
according to the t)?e of bonding involved in thcm. very high temperature. For example,
1. Ionic or salt like carbides. These are thc (r) Silimn carbide is prepared by hcating
compounds of carbon with strongly electropositive either silicon or silica with carbon.
elements such as Mg, Ca, Al etc. Salt-like carbides 2500 K
are further classified according to the typc of hy- Si+C SiC
drocarbon they give on hydrolysis as shown below: Silicon Silicon carbide
2273K
(l) Methanldes. The carbidcs which give sio, + 3c SiC + zCO
methane on hydrolysis are called methanides. For Silimn carbide
Silica
example, beryllium carbide (BcrC) and aluminium
(ii) Calcium carbide is prepared by hcating
carbide (AlnCr). CaO with carbon at 2273 K
Be2C + 4H2O ----------- 2 Be(OH)z + CHr 2n3 K
CaO + 3C -------. CrQ + CO
ALC3+ 12H2O ........- 4Al(0H)' + 3CHn Lime calciunr carbide
These carbides contain C- ions. (rii) Aluminium carbide is prepared by heat-
(i) Acetylides. The carbides which on ing Al and C in an electric furnace
hydrolysis give acetylene are called acetylides. For Electric furnac
example, magnesium carbide (MgCr), calcium car-
4Al + 3C ALq
Aluminium cartride
bide (CaCr), barium carbide (BaCr) etc
(iv) Beryllium carbide is prepared by heating
Mgq + 2H2O -----------+ Mg(OH), + HC = CH BeO with carbon atzzW-?iN K.
These carbides contain g- or (C= C)2- 2200-23i)0 K
2BeO+3C BerC + zCO
ions.
Beryllium carbidc
Some other carbides having similar structurcs Ho\ ever, BeC, is prepared by heating Be
are CyC" , AgrCaetc. Howcver, these carbidcs on
with ethyne
hydrolysis do not give acetylene anrl hence are not
(v) Magnesium carbide (MgCr) is obtained by
regarded as true carbides.
(iii) heating magnesium oxide with carbon.
Allytides. The carbides which on
hydrolysis give allylene or propyne arc called al- 2273K
lylides. For example, magnesium carbide (lragrCr).
MgO + 3C -_ Msq + Co
MgQ, however, changes to MgrC, onheating.
Mg,C.+4}{rO --+zMg(OH)2 + CH3C= CH
Ally'cne or propyne Uses. Carbides find extensive applications in
indrrstry.
These carbidcs contain Q'- ions.
(i) Calcium carbide is the chief sourcc lbr
2. Covalent carbides. These are the com- acetylene gas.
pounds of carbon with elerncnts having
electronegativity slightly less than rhat of carbon, CaC, + 2HrO --.......- Ca(OH)z + CH = CH
i.e., silicon and boron. For example, SiC, B4C, Cal. carbide Acelylenc

84C3 etc. Acetylene is the raw metcrial for a number oI

3. Interstitial carbides, these are the com-
pounds ofcarbon with transition elements. e.6. TiC.
WC, ZrC, VC, VrC, VnC" , FerC (ceraentite) etc.
industrially important compounds such as vinyl
plastics, ethyl alcohol acetic acid etc. It is also
employed in uy-acegime llome for welding pur-
p0ses.
13124
Pradeep's

(ii) Silicon carbide (SiC) is very hard and is
used as an abrasive under the name ccrborundum.
(iii) Ttrngsten carbide (WC) is also very hard.
It is used for polishing, drilling and cutting tools.
(i) BoC (boron carbide) which is even harder
than silicon carbide is now increasingly being used
as an abrasive. It is also used as a shield for radioac-
tive radiations and for making bullet'proof
('.e., clothing).
'13.8. Halides ot Carbon
Carbon combines with halogens to form both
simple and mixed halides. All the four simple
hulides of carbon, i.e., CFa, CClr, CBra and CI.
are known. The stabitity of these tetrahalides
decreases as the size of the halogen increases, i.e,
CF4 >
CCll > CBro > CIo. This is due to the
reason that the bond energies of the carbon-
halogen bonds decrease in order ; C-F > C- Cl
> C-Br > C-I. Amongest the mixed halides,
CFCI3, CF2CI2, CClrBr etc. are quite common.
Preparation. (i) Tetrafluoromethane or carb-
on tetrafluoride (CFo) is prepared as follows :
CO2+SF4 ' CF1 +SO2
SiC + 2 F2 ------ CFr + SiFr
...-
CF2CI2 + F2 CFa + Clz
Freon
(ii) Carbon tetrachloride is prepared
action of Cl, on CS, in presence of ferric chloride
as a catalyst.
FeClr,303 K
csz + 3cl2 ccl4 + s2cl2
Feclr,333 K
csz+2s?cl2 ccll +6s
(iii) Freon (CClrFr) is prepared as follows
Howevcr, if sufEcient energy is provided by
using superheated steam thenCClo is hydrolysed to
form a poisonous gas called phosgene or carbonyl
chloride
suDcrhcalcd
ccll + H2o cocl2 + 2HCl
stcam Phosgene
Uses. (i) Carbon tetrachloride is a common
vests
solvent. It is also used as a fire e><tinguisher under
the name Wrene . Carbon tetrachloride is also used
in medicines as anti hook-worm in intestines'
(ri) Mixed halides of flourinc and chlorine are
especially important as coolants or refrigerants be-
cause oI being easily liquefiable go.ses having lot')
b.p.'s and low specifrc heats. For example, CFrCl,
(dichlorodifluoromethane) is widely used as a
refrigerant under the tameireon.
13.9. Sulphides of carbon
Carbon forms three sulPhides, i.e., CS, (carb-
on monosulphide), CS, (Carbon disulphide) and
CrS, (carbon subsulphide) correspondiog to three
oxides, i.a, CO, CO2 and QO2. CS is produced
when CS, is subjected to sunlight. It is also
produced when CS2 is subjected to high frequency
electric charge. CS is unlike CO, and is a highly
reactire radical even at tie temperature of liquid
air.
by the Howevcr, when electric arc is passed through
CSr, it giws CrSr. Its strudure is
s=c=c=c=S.
Itis ared liquid.Like QOr, it also polyrnerises
slowly.
Of thesc three sulphides, carbon disulphide
(CSr) is the most important and is discussed below :
:

sbclt
Pteparatlotr. @ It is prepared directly by
, heating sulphur and coke in iron retorts at 1023-
CCl4 + 2HF CCI2F2 + 2HCl
12nI(.
sbcl{
3CCll+2SbF3 ....-.-_ CClzFz + 2SbCl3 c+2s l0n-1273K cs2
Properties. (i),41l the tetrahalides arc covalent (ii) Now a days, S
contpounds hdving tetralrcdrul shapes- phase reactioa betwe ln
(ii) T'hey are chenicslly inen, non-Jlammable presence of AlrO, or
c <tntpoLuttls. 8%K
(iii) 71rcy orc not hydrolyscd by water under cH. + 45 cs2 + 2H2o
Al2o3 or Silicr 8cl
nomnl conditions since carbon cannot uPand ils
coordinaliot nunrber beyond lour because ol the Structurt. C$ is a linear molecule, S =C :S
ohsence ol d-oftilals. like CO, in which carbon is sp- hybridized.
 SOi,,E p-BLOCK ELEMENTS 13125

Physical Properties : (i) Pure carbon disul- MgO, SO, and HSOTCI (chlorosulphonic
phide is a colourless, volatile liquid b .p.319.2 K. acid) all react in a similar manaer to form COS.
(,i) It freezs at 161 .4 K.
MgO + CS2 -.---r COS + MgS
_ (iii) It is iufl"-mable. It has a low flash point
(3O3 K) and it;gnites spontaneously ar 373 K. COS+MgO ._ CO, + MgS
(iv) Its vapours are toxic affecting braia and (vi) Reactlon vlth ethanol and celtulose.
CS,
central nervous system. reacts with ethanol in presence of alkalies to give
Chemical Properties. (r) Highly Inllammable. xalthates.
CS, is highly inflammable and burns in air to give
CO, and SOr.
cS, + NaOH + qH5oH ......-

+302
CS2 ------ CO2+2SO2
,="IoQ''
\s-N"t
*",,,
Sunlight changes CS, to CS. That is why CS,
Sod. x3nthate
is stored is dark coloured bottles.
(S od. etb,l di, hi oe a rb ona te)
(ii) Reactlor yith meaal sulphides. It com- Ifin the above reaction, ethanolis replaced by
bines with metal sulphides to give thiocarbonates.
cellulose, celulose xanthate is formed which dissol-
MS + CSz """'e MCS: ves in aqueous alkali to form a viscous solution
called vlscose. When viscose is acidified. cellulose
where M is a divalent metal. isregeneraled eitberin form offibres called viscose
(ur) Reaction with NaOH. It reacts with rayon (artificial silk) or as a thin film callcd cel-
NaOH to give a mixture of NarCO, aad NarCS, lophane.
(sodium trithiocarbonate or simplysodium thiocar- (vri) Reac,tion wlth chlorluc. GS, reacts with
bonate) Cl, in preseace of ferric chloride or aluminium
3 CS2 + 6 NaOH ----.* chloride as catalyst to form carbon tetrachloride.
CS2+3CIz ..._CClo + SrCl,
NaL2COr+2NqCSr+3H2O
(iv) Rcacfion wlth ammonla and smlnes, It Cq + ECl, ------- CCL + 6 S
reacts with ammonia, primary and secondary (rzit) Reactlon wlth sulphur trloxlde. CS2
amines to form dithiocarbamates. combines with SO3 to form thiocarbon dioxide
(or carbonyl sulphide)
NH3 + CSz + NH2-C IS Cq + 3So3 ---' COS +
AnlmoDia \ s-NHo* Thiocarbon dioxide
4SO2

([t) Actlon with phosphorus pentachloride.

(qHs)rNH +
qt';*-.zt
Amm. dithiocarbamate
CS, reacs with PCl, to form thiocarbonyl chloride.
CSr.......r
\ CS, + PCl.- CSCI, + pSCl3
Dl'ethylafiiIe C=Hr/ s-Nr* Thiocarbonyl Thiophosphonyl
Sod. satt ofN, N_ chloridc chloride
diethy'dithiocarbarDate (-r) Actlon with nltric oxide. It forms an ex-
(v) Reaction with water. CS, reacts with water plosive nixtue with nitric oxide.
to give thiocarbon dioxide (COS) and HrS at 473 K
2CS2 + 10NO......- 2CO + 4SO2 + 5N2 .
and CO, and HrS at higher temperatures.
(.r) Formatlon of complexcs. CS, is an effr-
473 K
CS2 + HrO ----.......r COS + H2S cient complexing ageql,and forms complexes more
Throcarbon dioxide readily than COr. I t rcts as a biitend ; ligand with
>473 K one C atom and one S atom bonded to the metal,
COS + H2O CO, + HrS and CS, molecule is bent. For example,
--.r
13i26
l'ralet f 's Ned Course

Pt(PPh3)2C12 + CS ing from - 3 to + 5. Thc common oxidation statcs

ar; -3 (r.&, NH3, MgrNr), +3 (c.g NaNo2) and
Bis (triphenylphosP ine)
Pt (Il) chloride + 5(e.g NrOr , HNO).
ph3p.:._
_,,_q = s 13.11.1. Terrestrial Abundance and Dis'
PL-
.-"-i'I 2 Cl' tribution
o
Y lY'
"-/ -J
Dinitrogen occursbothin the freestatc aswell
13.'10 Uses ol Ca bon :,j:!ii!:r;i., :::l:iii:la:i :::::a:l'r:ri+lvJi8{i*+ili as in the combined state.
(a) In the fre state. Dinitrogen occurs in the
(i) Uoalcncosively used a^s a luel in boilcrs,
is
atmospherc to an e*Ler.L otlgVoby volu me. lt is also
cngincs. lurnaccs ctc. lt is also uscd in thc manufac- presenl in volcanic gases and gascs evolved by thc
turo ol coalgas(CO+H, + CH4 + CO2)producer
burning of coal.
gi\s, tvtlet 8a\ or i)?rftrerb go-t (CO + H,) and syn-
(b) ln combined state. Nitrogen is present in
thetic Dctrol. Anthracitc is used as a rcducing agent manycompounds such as potassium n ifi (hdiat
in mctallurgical processes antl for the manufuclutc ^te
salt ?ene ot sitttply nilreT, sodium nitrate (chile solt
of graphite. peoi) arrd many ammonium salts (e.g NH.CI
(ii) Cokc is used as a fucl and as a reducing (NH4)2SO4 etc.). Nitrogen is an important con-
agent in mctallurgical opcrations.
stituent ol proteins in plants and animals. Its total
(iii.) Cl.arcoal.,4clivatcd chucoal is tse(l x an
abundance in earth including the atmosPhere is
cxccllcnt absorhcnt in gus masks and for removing
oflcnsive odour from the air used in air-condition-
0 017o by weight.

ing proccsses. ll sing 13.112. Isolation from air - Commercial

ag'ont in sugar ind and preparatlon of dinitrogen.
other chcmicals 3 also rom air
as a catalysl. lt has also been used in the treatment When
o[ drinking rvatcr after chloriuation to adsorb cx- having
ccss ol chlorine. Sugar charcoal is used to colour leaving
winc and rvhisties. behind liquid diorygen (b.p. 90 K). Thc dinitrogen
(n,) Lamp black. lt
is used lor making black obtaincd irom air contains traces of diorygen and
inks. nainrs and shoe-polishcs. black pigments clc' some of thc noble gases as impurities. World rvide
It is widely uscd as r liller for rubber tyres to mukts production of dinitrogen lrom liquid air is morc
them hard and strong. than 50 million tonnes Per Year'
lr') Gas cJrbon is a good conductor o[ 13.113. Preparation o[ Dinitrogen
clcctricitv. lt is used [or making eleclrodes,
The main source of dinitrogen is ammonia
(vi) For uses of diamond and graphite refer to and its compounds as discussed below :
sec. t3.5.2.
(a) From ammonia. Dinitrogen can bc ob-
tained from ammonia by the following methods :
(i) By heating with copper oxide. When am-
monia is passed over heated copper oxide,
dinitrogen is obtained.
Heat
3cuo + 2NH3 ----"- Nz + 3cu + 3H2o
of tbur covalent bonds (e.g. NHn+) because of the (ii) By action on bleaching powder.
abscnce of d-orbitals in the valence shell Like 3CaOCl, +2NH, ._ 3CaClz + 3H2O +Nz
hvclro(cn and orygen, nitrogen also exisls in its Bleaching
.i.rn""ntol to.rn ut idiatomic mole cule (N2) Therc- poeder
tbre, it also called dinitrogn.lt is a typical non-
ii (iii) By action on chlorine' Ammonia reacts
meral with a high electronegativity (3 0) next only vigorously with chlorinc evolving dinitrogen'
to fluorinc (4'd) and orygen (3'5) Ninogen forms 2NH3 + 3Cl2 --' 6HCl + N2
a variety ofcompounds in all oxidation states rang-
 SOME p-BLOCK ELEMENTS 13127

(b) From amrronium compounds. A

Dinitrogen is obtained from ammonium com- Bu(Nr), Ba+3N2
pounds a-s follows: Barium azidc
(i) By heating ammotrium nitrite- 13.11,4. Chemical volcano
l,aboratory method of prtparation. ln the When a heap of ammonium dichrorrate is
laboratory, dinitrogen is obtained by heating anr- ignited, a spontaneous reaction occurs. Tbe N,
monium uitrite. Since ammonium nitrite is aE un- produced quickly rushes out of the heap splashing
stable compound, an aqueous solution containing green ash of Cr2O, arouad. This phenomenon G
an equivalent amount of ammonium chloride aud
sodiumnitrite is heated gently in a round-bottomed called chemical volcano.
flask (Fig. 13.12). Ammonium nitrite is first formed 13.115. tuomic and Physlcal Properdes
by double decomposition which subsequently (a) Physical propertles. (i) Dinitrogen is a
decomposes to form dinitrogen. coloutless, odourless and tasteless gas. It has two
stable isotopes : l'N and lsN.
(i) It is slighUy lighter than air ;
its vapour denrity being 14.
(ur) Dinitrogen gas is not
DINITROGEN
poisonous (i.e. non- toxic) but
BEEHIVE animals die in its atmosphere for
SH ELF
want of diorygea.
(iy) It is very slightly soluble in
Hzo watet (23-Z cm3 per litre of water at
273 K under one atmosphere or l bar
pressure).
FIGUBE 13.12. Laboratorv preparation of dinifogen. (u) It is adsorbed by charcoal.
NHoCI(aq) + NaNOr(aq) s of atornic
NHnNOT(ag) + NaCt(aq) and le 13.3.
Heat '1 .-\Ilt.l.l l I. ,\tomic and l\Iolecular
NH4NOT(aq) .._ NrG) +zHroo
-'1.

i'r'r):)(t ties ol nitr-ogen

Since dinitrogen is insoluble in water, it is A'I'OMIC MOLECUI-AR
collected by downward displacement of water. PROPERTIES PROPERTIES
During this reaction, small amounts of NO and IoDizatioDenthal- 1402 Melting pomt (K) 63.2
HNO, are also formed. Thesc impurities can be py (kJ rnol-l)
easily removed by passing thc gas through aqueous Electron gaiD en- 'l BoiliDg point (K) 77.2
sulphuric acid containing a small amount of potas- mol-l)
thalpy (kJ
sium dicbromate.
ElectronegatMry 3.0 Density CglL) at 1 .L5
(ii) By heating ammonium dichromate. Pure (Pruling scale) S.TP,
dinitrogen gas can also be prepared iu the Atomic radius 10 Bond length (p,r?) 109.8
laboratory by heating ammonium dichromate. (pn)
(NHa)2Cr2O7 """', CrrO, + N2 + 4H2O Ionic radius 177 Bond enerry 916
Chromium oxide (N' ) (pn ) (kJ mol-1)
(NHo)rCrrO, may be prepared in situ by heat-
1.6. Chemical Reactivity
13.1
ing an equimolar mixture ofpotassium dichromate
and ammonium chloride. Dinitrogen is chemi c"lly inen orunreactive.ln
its molecule, the two nitrogen atoms aro linked by
(c) From barium azide. Very pure nitrogen
a triple bond (N=N) with a bond length of 109 8
can be obtained by the thermal decomposition of
pm and bond dissociation enerry of 946 kJ mol-l.
sodium or barium azide.
The loh, reactiity oI dinitrogen is due to its smsll size
13128
13?3K
and hig! borut ilissociation ene,&t.However, at high CaQ f N, ""-r CaCN2 + C
tempe-ratures, dinitrogen reacts with many active Cal. cstbidc C.st. c,anmidc
metals and non- metals.
Calcium cyanamide reacts with water to form
Some important chcmical propertics of ammonia,
dinitrogea are discussed below :
CaCN2 +3tI2O CaCO3 + 2NH3
"""'
1, Action ofllhlus.It is neurral towards litmus'
Cal. cyanamidc
2. Actlon of metals. Dinitrogen in neither
Thirefore, it is used as a fertilizer under the
combustibl
mme nidolim (CaCN2 + C).
ever, many
on burning 13.11.7. Uscs of Dlnltrogn
their respective nitrides. Inspite is an inert
Hcat gas and does withmanY
6 Li + N, """"+ 2Li3N
elements, yet :
Lithium nitridc
(i) It is used in the maiufacture of nilric acid,
Hcst
3Mg + Nz- MgrNz ammoni4 calcium cYananide etc.
Ma& nitridc (ri) Dinitrogen Provides an inert atnosphere
Hcat in many uetallurgical operations.
3Ca * N2 carN, (r'r') Dinitrogen is used in frlling electric bulbs
-+ cal. nitridc to reducc the rati of volatilisation of the tungsten
Hcal filament.
2Al * N2 """-'+ 2AlN (iv) Dinitrogen gas-filled thermometers are
Aluminium niiridc
used for measuring high temperatues
3. Action o[non-metals. Dinitrogen also com- is used as a refrigerant
bines with non- metals such as dihydrogen,
to erials, in freezing food
diorygen etc. as discussed below :
ar
(i) Acdon of iUhyrlrogen. When a mi:(ure of ::i:1;!:i:tEi::+ni:ti.t+l:*lr',ii:r4+ri:t+ilir
dinitrogen and dihydrogen is heated to about 673 13.12. Fixation of Nitrogen
K undei a pressure of20o atmospheres, inpresence Nitroccn is vital to life. Although we live in an
of iron as catalyst and molybdenun as promoter, atmospberE which cnnlans 79Vo of N, by volume
ammonia is formed.
vet it cannot be used by plants until it is fned, i e',
N2@) + 3H2G) 1r zNHr@); 'convcrted into biologicilly useful forms such as
aF = - 92'2}Jmol-l ammonia.

This reaction forms the basis of Hsbels

method for lhe manufacture of amnonia.
(il) Actlon of dlorygen. Dinitrogen and
artificial.
dioxvsen combine to form nitric oxide when the (r) Natural or Blologlcal llxadon. A large
mixtirie is heated to about 3300 Kin aa electric arc.
amourit of atmospheric dinitrogen is brought to the
N2+02 (.l 2NO ; soil by the following two processes
Nitric oxidc
(a) During lightining N2 and 02 of the atmos-
AfH'=+135Umol-r
ohere mmbine to form NO whidr then combines
This reaction forms the basis of manufacture ivith more O, to form NO2. NO2 thus formed com-
of nitric acid by and Eyde process. bines with more O, in presenc.e of HrO to form
4. Actlon of nitride is
IINC)3
formed.
3300 K
2013 K N2 + 02 """""""'' 2 NO
Al2o3 + 3c + Nz '".+ zAlN +3CO
5. Actlotr of calcium carbide. Calcium zNO+02 2NO'
ryanamidc is formed.
-
4NO2 + 02 + 2H2O- 4 HNO3
 SOME p-BLOCK ELEMENTS
13129
Nitric acid is carried by rain water to the soil (iv) Hydrazine (Rar chig process)
whereit combines with CaCO, aod MgCO3 present Ao. atkati
in the soil to forrn their respective nitrates which 2 NH3 + NaOCI--------.......r NrH. + NaCl + tlO
serve as ferti-lizers. gclatln

These nitrates are converted into ammonia by NrHn is used as a rocket fuel and for removing
deultri.fylng bactria probably through the follow- dissolved O, (which causes corrosion) from tI.O
lng stages. used in boi-lers.
Nitrates,------r Nitrites.......r NOz* N2 ------. NH3 Calcium carbide (Cae) can also be used to
roduced is utilized by plants lx the N, of thc atmosphere in form of calcium
tei[s aud other nitrogenous ryanamide which is exensively used as a fertilizer.
for their growth and other 1373 K
coQ + N,
----------r . CaNCN + C
(D) Organisms such as blue.green algae and Cal. carbidc
Nirrolinr
symbiotic bacteria present in the roots of
13,13. AmrnoniE

It is the most important compound ofnitrogen

13.13.1. Preparatlon of Ammonlat
Ammonia may be prepared by the following
.
methods :

(ii) Artificial or Industrial fixatlon. A large (l) By beating ammonium salts. When the
amount of atmospheric dinitrogen is lxed in foir salts of non- volatile acids such as ammonium sul-
ofNH, in industry by Haber,s process. phate, a-urmonium sodium hydrogen phosphate or
650-E00 ammonium phosphate are heated, ammonia
K 200-350 arom Ls
N2+3Hz 2 NH3 produced.
Fe catal,st, Mo prcmotcr A
Ammonia thus produced can be converted (i{H4)2s01 2NH3 + H2SOI
into number of useful compounds such as nitric Amm. sulphate
acid, urea,tydrazine, ammonium nitrate by chemi- A
cal methods :
NH4NaHPOT + NapO3 +H2O
Amm. sod. Sod.
(i) Nitric acid (Oslwald process) hldrogco pho6phrt. mctapho6phatc
Pt, 1100 K A
4NHr+502 4NO+6H2O (NH4)3PO4 .--------r 3NH3 + HpO3 + H2O
NC) thus produced is converted into Amm. phosphate McEpho6phoric
HNO, by
acid
the reactions listed above.
(2) By headDgammonlum salts wlth a strong
(ii) Urca -base such as sodium hydroxide, potassiui
453_473 K hydroxide or calcium hydroxide either in the solid
2 NHj+COz [NH2COONH4I state or dissolved in water.
220 atm
---. Amm. carboDate

-r
NHTCONH, + HrO (NH.),SO. + 2NaOH -j* UqSOn
Urea
(iii) Amm. nitrate + 2H2O + 2NH3
NH3+HNO3 NH.NO, A
NH4CI + KOH -...+ KCI + H2O + NH3
Bothuraand -
NHaNO, areused as fertilizers. Laboratory
A mixture of NH.NO, and frrel oil is used as an monia is prepare
explosive in miaing operations. mixture of slaked
rNot included in rhe New
C.B.S.E syllabus.
13/30 Netl Course Chemistrq
A 13.132. Manufacturle of Ammonia
2NH1CI + Ca(OH), HabeCs Process (slEthcsis of ammonla)' It
Cacll2 + 2NH3 + 2H2o involves direct combination of dinitrogen and
dihydrogen as shown below :
A mixture of
ammonium chloride and
N2G)+3H2G) + 2NH3G)
slaked lime (1 : 3) is heated in a round bottomed
flask. Ammonia thus produced is collected by AF = -92 2 kI mol-r
downward displacement of air since it is lighter This reaction is reversible, exotlermic and
than air. occurs with decrease involume. Therefore, accord-
(3) By the action ofwater on metal nitrides ing to Le Chalelier\ pinciple , the favourable con'
MgrN, +6HrO ._ 3Mg(OH), + 2NH3 ditions for the manufacture of ammonia are :
(i) Low temperaturt' Since the forward reac-
Mag. nitride
tion exothermic, low temPerature will favour the
is
AIN + 3H2O ---""""'' A(OH)3 + NH3 formation of ammonia. However, at low tempera-
Alumioiun tures, the rate of the reaction will be slow. The
nitride
optimum temperature for the reaction has been
e moisture Present found to be around 7fi) IC
in passing it through
(r'f) Iligb prcssurc. Shce the forward reaction
at CaO. It cannot be
occurs with decrease in volume, high pressure will
dried by :
favour the formation of ammonia. The reaction is
(i) Conc. HrSOo since it reacts with it forming usually carried out at a pressure of 200 x 1d Pa
ammollium sulphate. (about 200 atm).
(n'i) Catalyst. The rate of reaction is fairly low
2NH3 + H2SO4 --""""r (NHo)rSOa
around 700 K.It is increased by using finely divided
(ii) Anhydrous calcium chloide sir.cc it iorms iron as catalYst ter
a complex having the composition, CaCl2.8NH3. (which increases In-

it stead of iron, ir of
Phosphorus pentoide
(iii) sjd(rce reacts to
Ibrm ammonium phosphate.
IlO and AlrO3 can also be used.
Detalls of the process. The plant commonly
PzOs --"""'* 2HrPOr
+ 3HzO
used for the manufacture of ammonia Ls shown in
3NH3 + H3PO4 -"""""r (NH4)3PO1 Fig. li|.13.

H2+-

", ,-l
RATIO 3 : 'l
PURE ANO ORY
H2:N2
3:'l

N2+H2+NH3 Liquid NH3

FIGLRE 13.13. Flow chart Ior the manufacture oI ammonla'

 SOME p.BLOCK ELEMENTS
1 3/3'1

A mixture of N, and H2 in the ratio 1 : 3 by bond angle decreases tiom 109'- 28, to _t07.8.. As
volume _is compressed under a pressure NII, nrclecule hqs plramidal geometry
a result,
200 x lot Pa (abo-ut 200 atm). The compressed withN-Hbondlength of l0 t .7 pm untl bond angle
gases are passed through soda Iime tower (not o[ 107 5". (Fig. B.r4).
shom in the Fig.) to remove moisture and traces of
carbon dioxide.
The compressed gases are then passed into a
catalyst chamber where the gascs are heated
electrically to about 700 K in preience ofiron oxide
as catalyst alongwith small amounts of KzO and
AtO3 to increase the rate of attainmeot of equi-
librium. The reaction being exothermic ; the heat
evolved maintains the desired temperature and fu r-
ther heating is not required.
The gases which leave the catalyst chamber
containNH, andunreacled N, and Hr. These gases
are cooled by passing through condensing pipes FIGURE 13.14. Sbuchm of ammonia.
where NH, gets liquefied and is collected- in ihe (b) Chemical properties :
to 1. Basic nature. Ammonia is highly soluble in
water. Its aqueous solution is rveakly basic due to
it the formation of OH- ions.
NH3G) +HrOO <=:= NH1+(a{) + OlH- (qq)
The annual world production of amraonia
now exceeds 1fi) million tonnes. Being basic. it turns moist red littttus blue and
13.133. Propcrtles of Ammonla
neutralises acids in the dry statc as well as in
aq.ueous solutions forming their correspondiog
I. Physical propertis I salts-
I . Ammonia is a colourless gos with a charac_ NH3+HCl-NHoCl
teristic pungent smell called the ammoniacal smell.
It causes tears in the eyes. ZNH4OH * H2SO. ...--...- (NH4)rSO4 + 2HrO
2. It is lighter thau air (density = 0.68 gcm3) 2. Reaction with heavy metal salt solutions.
3. It is extremely soluble in water ;one volume Ammonium hydroxide reacts with nraoy metallic
ofwater can dissolve about I000 volumes ofthe gas salts and precipitates them as hydroxiriei.
at273 K. FeCl3 +3NH4OH-_ Fe(OH)3 J + 3NH1CI
. 4. Ammonia caa.be easily Iiquefied bycooling
under pressure. Liquid ammouia boils at 239.7 Ii -_
Brown ppt.
AlCl3 +3NH4OH AI(OH), I +3NH1CI
and freezes at 198.4K. In the solid and the liquid
Whire ppt.
states, it undergoes densive intetmolecular H_
CrCl. +3NH.OH.-----+ Cr(OH)3 i +3NH4CI
bonding (ust as in case of HrO) which accounts for
creen ppr.
its higb melting and boiling points.
. This property is made use of in precipitating
. 5. When vapourized, Iiquid ammonia causes these metals as their hydroxides in the group UI oi
urten-se cooliog. qualitative analysis.
Stru-cturc of ammonla. The nitrol]en atom in 3_. Oxidation. (a) // is oxidisedto nilrogen
when
NHj isd-hybridised, therefore, NH, ihoula have possed oyet lrcsted copper oide.
tetrahedral geometry. The tbee of thc four sp3-or_
bitals form three N-H o-bonds while the iourth 2NH, * 3Cu0 ._Heal 3Cu+3HzO+N2
cotrtaiDs a lone pair of eledrons. Since the lone
iq, mixed with qn ejcess of uia,
pay-pon{ pair repulsions are stronger than bond
latinunt gauze st I 100 K, it is
pair-bond pair repulsions, therefore,'ihe H-N_ H
13132
Pradeep's

Pt, 1100 K With I,:

4NH3 + 5O2 '"-""- 4 {o + 6H2o
2NH, *3I, """""* NH,.NI3 + 3HI
This reaction forms the basis for manufacture Nitrogen tri-iodide
of nitric acid by OstwolC's process anrmoniate (brown PPt )
4. As a t ew s base. Due to the presence of a When NHr.NIr, in the dry state, is either
lone pair of electrons ou the nitrogen atom, ant' rubbed or struck against a surface, it explodcs with
monia acts as a Lewis base. Consequently, it can noise liberating vapours of iodine.
easily donate its electron pair to form co-ordinatr.: + 5N2 + 9I2 + 6NH4I
8 NH3.NI3
boni with electron-deficient moleculcs (such rs
BFr) or transitionmetal cations havingvacant d-or- Thus, it is a mild and harmless exPlosive.
bitals to form complexes. For example, 6. Reaction with carbon dioxid. When
NH3 + BF3 + NH. ul 45t -
H3N +BF3 gaseous CO, is reacted with liquid 473

eg+ @q) + 2 NH, (ag) K under a pressure of 220 atmaspheres, it first

forms ammonium ciubamate which subsequently
[Ag(NH)J+ (oq) decomposes to give urea.
Cuz+ (aq) + 4NH, (a4) 453 - 473K
2 NH3 + CO2 [NH2COONH4]
ICu(NHr)ol2+ (a4) 220 atm. Amm. carbamatc

(ry)
_-' NHzCONH2 + H2C)
Cd2+ (aq) + 4NH3
Urca
[Cd(NHr)ol'?+ (aa) Urea is widely used as a fertilizer since it
Due to the formation of complex ions, white slowly decomposes in soil to give NH, and COr.
oot. of silver ct loride dissolves in excess of am- * HrO -""""'r 2 NH3 + CO2
NH2CONH2
moniu to form a comPlex comPound
tAg(NH)rlCl, diamrninesilver (I) chloride' It has a very high nitrogen content (467o)
Similarly, copper sulphate dissolves in excess of 7. Action of metats. Ammonia when passed
ammonia to form soluble deep blue coloured com- over molten sodium or potassium metal at 575 K
p'lex tetrammine copper (lI) sul-
[Cu(NH3)a]Soa, form correspon<Iing amides with the liberation of
phate. dihydrogen.
5?5 K
AgCl +2NHaOH
-' [ag(NH)2]Cl + ?HzO
2Na*2NH, + 2NaNH2+H2
Diamnrinesih"er (I) Sodamide
chlori e
575 K
CuSo4 * 4NH4OH [Cu(NH)al SOa 2K+ 2NH3 ..........- 2 KNH2 * H2
-+ ,:.[T#'&::rffiii) Pot. aflide

+4H2O
8. Reaction with Nessler's reagent. with
Nessler's reagent (an alkaline solution of KrHgI,)'
These reactions are used s tests for these ammonia or ammonium slats givc a brown
cations in qualitative analYsis. precipitate due to the formation of iodide of
5. Action of halogens. Halogens react with Millon's base.
ammonia as follows : ZK"rHgln + NH3 + 3KOH ...._
With excess NH, : N_esslc/s rcagent

8NH3 + 3Cl2 + 6NH4CI + N2 HrN - Hg- O - Hg -I + 7Kl + 2H2O

lodide of Millon's base
Wrth excess Cl : (btowt PPt.)
NH3 + 3C12 ' NCl3 + 3HCl 9. Raction with sodium hypochlorite' When

With Br,
a largeexcess treated with
:
sodirim hypo of glue or
8NH, * 3Br, + 6NH1Br + N2 gelatine, it get
 SOME p-BLOCK ELEMENTS 13/33

2 NH, + NaOCI-- NI{2.NH2+NaCI+H2O (ri) In the manufacture of nitric acid by the

Hydrszinc Ostwald's process and in the manufacture ofsodium
Actually thc reaction proceeds in two steps : carbonate by the So lvqls process .
(ra) Liquid ammonia is used ris a refrigerant
(r) NH: + NaOCI--------------' NaOH + NHrCI
in ice-faclories and cold storages.
Chloraninc . (iv) As a cleansing agent for removing grease
(Fast reaction)
etc.
(ri) NHrCI + 2 NHj NH2.NH2 + NH4CI (v) As a laboratory reagent.
--- (Slow reaction) 13,135. Tbsts of Ammonla
Glue or gclatine catalyses the slow reaction (i) It turns moist red litmus paper blue and
and inhibits the secondary reactioq i.a, moist turmeric paper brown.
(ri) It gives brown precipitate with Nessler,s
NzH4 + 2 NH,CI ----------.-.-- Nz + 2 NH.CI reagent.
10. Llquld ammonla as a solvent Just like (,,r) With a drop of HCl, it produces dense
watei, ammonia also undergoes selfianisation n white fumes of ammonium chloride.
liquid state. (iv) With copper sulphate solution, it gives a
deep blue solution.
2 NH3 + NH1+ + NHt
(v) It gives a yellow precipitate with chloro-
(ci. 2HrO-: H3O+ + OH-) platinic acid.
Therefore,liquid ammonia is used for dissolv- H2PtCI6 +2 NH! -.-r (NH)rPtClo
ing many polar compounds and also for carrying Chloroplstinic Amm, chloropletinarc
out many reactions in rte non- aqueous medium. .cid ppl)
OEllo*,
13,13.4. Uses ot Ammonia 13.14. Oxides of Nitrogen
Some important uses of ammonia are :
Nitrogen forms a number of oxides in which
(r) ln the formation of various dtrogenous
the oxidation state of nitrogen varies from + I to
fertilizers such as urea, ammonium nitrate, am- +5.
monium sulphatg ammonium phosphate, calcium
Some important characteristics of the oxides
ammonium nitrate (CAN) etc.
ofnitrogen are given in Table 13.4.

TABLE 13.4. Ondes of nitrogen

Formula Name Oxidation Properties
State ofN
1 NzO Dinitrogen nronoxide or Nitrous oxide +l Colourless gas, rather unreactive
2. NO Nitrogen monoxide or Nitric odde +2 Colourless gas, rective, paramagDetic
3. N2O3 DinitrogeD trioxide +3 Dark blue in the liquid or the solid
state, unstable in the gas phasc.
4. (a) No, Nitrogen dioxidc +4 Brown gas
(b) N2O4 Dinitrogen tetroxide +4 Colourless, qists in equilibrium with
NO2 both iD rhe gaseous and liquid
state.
5. N2O5 DinitrogeD pentoride UDstable as gas, io the solid state qists
as [NO2l+ [No3]-

1. Dinitrogen monoxiile or Nitrous oxide Hcat

(NrO) is prepared by heating ammonium nitrate or NHaNO,
--...r N2O + 2H2O
by the action ofnitrous acid on hydroxylamine. NH2OH + HONO N2O + 2H2O
---+
13/34
Ne...' Coltrsc Chedristrq

It is also calted /aag,ftirtggas because it catrses Structutr. Nitric oxide is regarded as a

resonance hybrid of the following two structures, I
hvsterical Iaughtcr or euphoria. ln small amr:unts,
it also acts aian anacslhetic agcnt particularly in ANd II
dentistrv. However, its largest use is as a propcllant + -+
ror whipped icc cream because it has no taste and N O-. ' :N::O:= :N = O:
115 Pm
is non-toxic.
I It Resonance h)'b d
It is a neutral oxide and reacts with sodamide
to form sodium azidc (NaN) Thus the resooance hybrid contains a double
._ bond as well as a three electron bond betweelr
N2o + 2NaNHz NaNl*NH.+NaoH nitroplen and orygen atoms.
N2O does not burn itselfbut decomposes on heat-
ing to producc O2 which supports combustion
8?3 K
2N2O --"""") 2N2 + ()2
A
S + 2N2O SOr+2N, 2NO ---------- o=N-N=O
SYmmctrical dimcr
A
-
Mg+NrO....-..r MgO + Nz The asvrnmetrical dimer (Fig' 13.5) has been
observed to'beformed as a redsolid in thepresence
Structure. The simplest electronic structure
of HCI or Lewis acids.
of NrO in which both nitrogen and orygen atoms
have complete octets is shown below :
*- - - -2!8!t - - - 6
N::: N: O; or
Itt9 le

113
:

Pm 1'19 Pm
ll=
A- - - - -DIMER
- - LOOSE - --- N

N-N --------+O or :N-N-O:-

Thus NrO is linear molecule and is expected
a FIGURE 13.15. Sbucture of nitric
oxide in liquid and solid states'
to have a large dipole moment. However, its dipole
momenl is iety 1ow, i.e., 0'17D, therefore, it is Properties. (i) Since odd electron molecules
regarded as a resonance hybrid olthefollowing two
ur" ,.roliy highly teactive, therefore, NO instantly
structures: reacts witl O, to give NO, and Cl, to give nitrosyl
,ni-4: ........ :N=N=O: chloride (NOCI)
2NO+C)2-_2NO,
2. Nltric oxiite (NO). PreParation' It is
2NO + Clz '--+ 2 NOCI
prepared by catalytic oxidation of ammonia at 1100
K in presence of Pt as catalyst.
Pt wirh
4NHj + 5O2 ' 4No + 6Hzo with
1100 K
rvhich is responsible for the colour in thebrown-ing
In thelaboratory, NO is prepared eitherby.the
test for nitrates (refer co page 13142).
action of dil. HNO, on copper metal or by reduc-
tion of HNO, bY I- ions, (iii) It is thermodynamically unstable and
decomposes irrto its elements at high temperatures
3 Cu + 8 HNO3 (dil.) ------
(1373 - 1.413 K).
3 Cu(NOr), + 2NO + 4H2O 1373 - 1413K
2HNO2 + I
21- 211+ "-""> 2NoG)----------------_NrG)+orG)
2NO+12+2H2O Therefore, it suPports combustion at high
Like NrO, NO is also aneutral oide' tcmperatures,
 SON4E p-BLOCK ELEMENTS 13/3s

1373 - 1413 K Propertles. (i) NrO, condenses to a blue

Mg + 2NO MgO + N, coloured liquid below 243 K.
In spite of its reactive and harmful nature, (ii) It is an acidic oxide and dissolves in water
NO occurs in biological systems iu traces. It acts to form nitrous acid.
as a neurotraDsmitter and plays a sigoificant role
NzO3 + H2O --.-.. 2HNO2
in controlling blood pressure by relaxing blood
vessels. It also provides protection from bacterial Therefore, it is regarded as an anhydride of
infections. nitrous acid.
3, Dinltrogen trioxide (N2O) is prepared by (rrr) It reacts with alkalies forming cor-
cooling an equimolar mixture of nitric oxide and responding nitrites.
nitrogen dioxide below 253 K 2NaOH + N2O3 """.) 2NaNO2 + ItrO
< 53K Sod. oitritc
NoG)+Noz@) Nzork)
(iy) It reacts with c.ocentrated acids forming
-
Structurr. This oxide exists in two different nitrosyl salts.
forms which can be interconverted by iradiation
with ligbt of appropriate wavelength
N2O3 + HOO. ".-.- 2NO[ClOol + HrO
Pcrchloricrcid Nirrosylpcrchlorate
N2O3 + I{2Sq ------- 2NO[HSorl + Hzo
Nirrc6rl hydrogcn sulphate
4, Nltrogen dloxide (NOr) is prepared either
by heating nitrates of heavy metals such as
Pb(NO), or by the action of conc. HNO3 on cop-
per, silver, lead etc.
Heat
2Pb(NO3)2 2PbO + 4NO2 + C)2
o=*\orr*=o Cu + 4HNO3(coxc
"j5 Symmodcal brm
Cu(NOr), + 2HzO + 2NO2
Str[cture. The NO, molecule is angular with
The asr/mmetrical form may also be regarded a bond angle of 134'and N- O bond length of 120
as a resonance hybrid of the following two canoDi- pm.
cal structures.

\ /
<--
d
N+

-N NO2, BROWN GAS (PARAMAGNETIC)

rO' 'iz
/" ov,-
N '-,1:
/ - 07 l34o ro
..o..
RESONANCE HYERID
13/36

Because of the presence of an unpaired 2NO, + 2NaOH '-r

electron on N atom, NO, undergoes dimerization NaNOrfNaNOr*HrO
at low temperature to form NrOo. (v) The NO2 N2Oa system is a strong oxidis-
-
X-ray diffraction on solid NzOa suggests that ing agent. NO, reacts with F2 and Cl2 forming nitryl
it is planar. The N-N bond length is abnormally flouride and nitryl chloride respectively
long (175 pm). 2NO2 + F2 '-""'
2NO2F
Nitrrl fluoridc
2NO2 + Clz """'' 2NO2CI
Nitryt chloridc
It also oxidises HCI to Ct and CO to CO2
4HCl + 2No2 """' 2NoCl + clz + zt{zo
NO2 + CO I NO+COz
o
#
\*-d,.."
-i
Uses. Liquid NrOo is used as an oxidiser for
NI rocket fuels in missiles and space vehiclos.
\ Both nitric oxide and nitrogen dioxide are
o o used in the manufacture of nitric acid and nitrate
ll201, coLouRLEss, fertilizers. However, oxides of nitrogen (NO and
OIAMAGNETIC NOr) are emitted into the atmosphere during the
(RESONANCE HYBRIO)

Properdes. (r) NO2 is a reddish brown

poisonous gas. On cooling (294 K), it turns into a
liquid and a solid at 261 '8 K.
(ri) It is an odd electron molecule (23
electrons) and isparanr sgnelic aadwt'!rcacli'te. At smog (for details, refer to unit 18).
low temperaturei, it dimerises to form NrOo which 5. Dinltrogen pentotdde (NrO) is prepared
is colourless and dianagn elic. by dehydration ofnitric acid with phosphorus pen-
Thus NO, exists in equilibrium with N2O1 and toxide (PoO,o)
thc equilibrium is temPerature dePendent. 4HNo3 +P1oro """- 2 N2o5 + 4HPo3
N2O1 2NO2 MctaphcPhoric
<---r
(Colowlas) (R .Uish btoet)
Thus, NrO, is regarded x an anhYdide of
In thc solid statc, i( consists of only N2O4 nolecules
ninic acid-
Propr'tl$. (i) Below 273 I( NzO5 exists a's a
colourless solid. X'ray dillraction shows that solid
N2oj is ionic (No2+ No3-)
the gas aonsists of only NOz molcculG.
K the
colo decom-
(iii) It dissolves in water forming a mixture of posi
nitrous acid and nitric acid.
2NrO, """-' 4 NO2 + 02
2l.IO2 + HzO ""+ HNO2 + HNO3
as a mixed anhydride At 303 K crystals melt giving a yellow liquid
Therefore, it is reg arded
and HNO3'
which decomposes at 313 K giving brown NOr'
of HNO2
(iv) It reacts with alkalies to form a mixture of (ii) It acts as a Jrrozg oxitlislng agent and oides
nitrites and dtrates. I, to Ir0, and Na to NaNO3
 SOME p.BLOCK ELEN,lENTS
13137

I2+5N2O5.+IzOs+10NO2 um at a tempera-
Na+N2O5....-NaNOr+NO, (9 bar) pressure
ic oxide.
(rr) Italso reacts with H2SC)4 to form pr. Rll
nitronium ion and NaCl to form niryl chloride. 4NH3 G) + so, @) ..._ aNo @)+6Hro @);
N2o5 + 3H2SO4 ....- lr00x
AH= -90.0 kJ
2NO2++H3O++3HSO; Since the reaction is exothermic, the heat of
NrO, * NaCl ------- NaNO: + NO2CI perature of the
Structure. NrO, is considered to bc a
required. About
resonance hybrid ofthe following two Lewis struc-
tures: (ii) Oxidatlon chamber, The gases coming out
of the catalyst tower are cooled below 420 K when
.:di o .li- the utrreacted oxygen in air reacts with NO to give
"-\t/" Noz.

\.o,* ,o/ < 4mK

2NOG)+OzG).....--......' 2NO2G)
(ili) Absorption tower. Nitrogen dioxidc from
oxidation chamber is introduced at the bottom of
an absorption tower packed with acid- proof flint

>",h,-ti._ or- quartz picces. Water is sprayed from the top of

this tower. Nitrogen dioxide dissolves in watci to
give nitric acid and NO which is recycled.
RESONANCE HYBRID
3 NO2 G) + HrO (/)------r 2 HNor (rq) + NO (S)

Nitric acid (HNO3) is the most stable and (iv) Conceutration of tbe acid. Dilute nitric
most important oxy-acid of nitrogen. Another im-
portant ory-acid is nitrous acid (HNOr). It is, how-
ever, quite unstable and exists only in wry dilute tion to about 9896 is achievd by dehydration with
solutions.
corc. HrSOn. Fnrz ing nitric acid is obtained by dis_
13.15.1. Manufacturc of Nitrlc acld solving an excess of NO, in conc. HNOa . It is biown
- - Nitric acid
clusively bv the
is prepared commercially
catalrtic
ex- in colour.
'
oxidation of ammo'nia "[Xt]]Eu OXIOATION
(Ostrrald process). The flow-
sheet diagram of the plant
employed is given in Fig.
13.16.
The process involves the 2NO + o. FOR
ECYC LING
following steps : I R

2NO2
(i) Converter. Ammonia
obtained by Haber's process
is mixed with dust free air in
the ratio 1 : 10 by volume and
the mixture is passed through
a converter made up of steel (1 10)
and packed with a
metal
gauze made of pure platinum
FIGURE 13. f 5. Manufacture of HNO3 l_.y Ost.rald s process.
 Neqt '
13/38

I-aboratory prtparatlon of nlHc acid' Nitric nitric acid itself is reduced to nitrogen dioxide'
acitl is oreparid in Lhe laboratory by heating For example,
sodium or potassium nitrate with conc' H2SC)4 at (i) torbon is oxidised to carbonic acid
(H2CO).
423 - 473 K in a glass retort.
NaNo3 + H2So4 "'--'.. NaHSon + HNo'
2HNo3 --""'* H2o + 2No2 + [ol x 2
C + 2[O] + H2O-----"' H2CO3_
Anlrydrous nitic ocid is obtained by distilla-
tion of conc. HNO3 with PlOlo C + 4HNO3 ...._ H2CO3 + H2O + 4NO2 I
13.152. Physlcal Propertlcs of Nitrlc acld (ii) Sulphur is oxidised to sulphuic ocid
(H2SOi.
Pure nitric acid is a colourless/zrzizg liquid
1.
with ounc;nt odour. However, impure acid is yel- 2HNO3 .-.......... H2O + 2NO2+[o] x24
low iue-to the presence of dissolved oxides of + 24[Ol + 8H2O
s8
nitrogen in it.
58 + /8HNo3 """"'-' 8H2So4 +'ENo2 +16H2o
2. It forms a constant boiling (393'5 K) mix-
ture i.e, azeotrope with water containing about (iii) Iodine is oidized to iodic acid (HIO,)'
68.5% of nitric acid. 2HNO, "---""'r H2O + 2Noz + lol x 5
3. It has a corrosive action on skin and
produces painfu I blisters.
I, + 5[ol ....-'.-lzOs
4.It boils at355.6 K and freezes to a white solid
at 231.4 K. Its density at 298 K is 1 504 g cm-3' 12+ 10HNO3 .....--_2HIO3 + 10NO2+4H2O
13.153. Chemlcal Propertles of Nitrlc acld* phosphoric acid
(iv) Phosphorus is oidised to
1. Decomposltlon. It decomposes on heating (H3PO4)
giving nitrogen peroxide, o:rygen and water'
hcat 2HNO, =-'r H2O + 2NO2 + [o] x 10
4 HNO3 (aq) -; 4NO, G)+O, G)+2 H2O o P4 + 10[Ol ....-} PrOro
2. Acftllc nature. Nitric acid is a strong
monobasic acid. ln aqueous solution, it ionizes as :
+20HNO3 ....._ 4H3PO4 + 20NO2 +4H2O
HNo3(aq) +H2o(D ' H:o+(aq) +Nol(aq) Pa

monobasic acid, it reacls with metallic

(v) Arsenic is oidised to arscnic acid
Being a
(H rAsO o)
oxides, hydroxides, carbonates and bicarbonates
giving only one series of salts called nirra'es' 2HNO3 H2O + 2NO2+[o] x 5

CaO + 2HNO3 ........... Ca(NO:)z + HzO +- s[O]

2As ._ AsrOs
NaHCO3 +HNO3- NaNO3 +CO2 +H2O AszOs + 3HzO 2H3AsO4
Na2Co3 +2HNO3"""'-'' 2NaNo3 +Co2 +H2o za.+ ro UNO, - 2H:AsOq +2H2O+10 NO2
3. O)ddlsing agcnt. Nitric acid is a very strong
-' H3Aso4 + H2o+5No2
or As+5 HNO, ---"'r
oxidising agent since it readily gives nasent orygen Arsenic acid
both in ihe conctntrated as well as in the dilute form SimilarlY,
2HNO, (cozc.)- + 2NO2 + [OI
H2O Sb+5HNOr- H3SbOl + H2O+ 5NO2
2HNO3 (drr.) """'-' HrO + 2NO + 3[o] Antimonic acid

Therefore, nitric acid oxidises many non-me- B. Oxidation ofcompounrls. Dilute as well as
concentrated nitric acid oxidiscs a number of com-
tals and comPounds.
pounds. For example,
A. Oxidadon ofnon'metsls. Dilute nihic acid
nitric (i) Hydrogen sulphide is oidised to sulphur
has no action onnon-metals. However, conc
acid oxidiscs many noa-metals such os catbon, (a) With conc. HNO, :
sulohttr iodine aod metalloids like arsenic, un' 2HNO, -.'......- HrO + 2NO2+[OI
tittiozy etc.to their corresponding oxy-acids while
 SOME p.BLOCK ELEMENTs
13/39
HrS + [ol .........- H20+s
csse, nasce hydmgm is libe,zted which
H2S + 2HNo3 ---..' 2H2O+2NO2+sl ,educes nitric
ludhet
(b) wirh dir. HNo, :
Metal + HNO3 .---...r Metal nitrate +H
2HNOr-------+ H2O + 2NO + 3[Ol HNO3 + H -...- Reduction product + H2O
+ [OJ .......* acid giing a variety of reduction products such
H2S HzO+Slx3 as
, NO, NH3, NH4NO3 and N2O as
3H2S + 2HNO3 ----.-..- 4HzO + 2NO + 35
I
ryO2
shown below :
..
(ii) Sulphur dioxide is oidised to sulphuic +H +2H +ju
acid [INo3 Nq -= No -i;
(a) With conc. HNO, : -*
-Hro -Hro -Hzo
2HNO, ----.......r H2O + 2NO2 + HNOI a
[Ol NHINO3 -.....+ N2O
SO2+H2O+[Ol ........- HzSOr -2H2O
so2 +2HNO, .._-...r H2SO4 + 2NO2
(b) with dil. HNO, :
2HNO3 .._ H2O+2N()+3[Ol
SO2 + H2O + lOl --| (l) Yery dllute nltrlc acld. Magnesium ond
H2SO1 ] x 3
3SO2 + 2HNO3 + ZH2O'- 3H2SO4 + ?slwesc .are the only metals which produc
2NO hydrogcn with very diute (t_2%) nitric acid.
(iii\ Fenous sulplrute is oidised to Mg + 2HNO3 -...+ Mg (NOr), + H,
,
l'llol.'
fenic sul_
Mn + 2HNO, ..-..+ Mn (NOr), + H,
(a) With conc. HNO, ;
(ll) Cold dllute nltric scld. More active
2HNO, -----) H2O + 2NO2 + [Ol ...
like
metals
lagnesium, zing tin and ircn react with cold
2FeSO. *HrSOo +tol ......"..- Fer(SOo), + HrO dil. HNO, to form ao.monium nitrate.
2FeSOa + 2HNO3 + H2SOa .- zn + 2HNO3 zn(NO3)2 + zlPtl x 4
Fer(SOo), + 2H2O + IINOs + 8H-. NH, + 3HrO
2NO2 --+
(b) wth
dit. HNO. : NH3 + HNO3 NHlNO3
-...*
2HNO3 .......-.- H2O + 2NO + 3[Ol 4Zn + r0 HNO3 -..-..-4 h(Nd-)-
2FeSO4+H2SOa +[O] +H2Olx3
Fer(SOa)3 + 3H2O + NH4NO3
-+
6FeSOa + 2HNO3 + 3HrSOo.._ Amm nitiate

3 Fer(SOo), + 4H2O + zNO

simirarry, 4 Sn + l0HNo, ,

_ _ Nitric oxide evolved combincs with ferrous Sn(NOr), + 3H2O + NH4NOJ

4
sulFhate to form a darkbrown addition
FeSOa.NO, nitroso-ferrous sulphate. This
"ornporia,
4Fe + 10HNO,
-......r
reaction
fbrrns the basis of the nag /est for nitrates. 4Fe(NOr)2 + 3H2O+ NH4NO3
Leod, under similat conditions gives nitic
u:ide instead of amnnnium nitrute.
Pb + 2HNO3 pb(NO3)2 + 2HI x
-..- 3

Itro:- T No+2Hrolx2
3Pb + 8rrNo3 -..-..* r ru6or;,
- A. Ractiotr with metals which ar more
electroDositlye.th{n hydrogen (Na. X, Ca, fvfg.
Mn, Zn, Cr, Cd,.Fe, Co,Ni,Sn,pb,Sb etc). inis
ai +4H2O + 2NO
Nitricdidc
13/40
l)r,t da r, l,'s Neur Course Chemistryl@fi
nitric acid. with hot For example, in case of iron, a protective layer
m nitrate thus formed of ierrosoferrii oxide, FeO.Fero, is formed on the
dilu
und to form nitrous oxide surface of iron
(Nzo)' Rescdon wlth metals whlch are less
B,
zn + 2HNo3 _-' Zn(No:)z + 2}{l Y 4 electroposltlw than hydrogsn (Cu, Ag, Hg etc')'

HNO3+8H + 3HzO+ NH3

NH3 + -* NHrNO:
HNO3
NHINO, + NzO+ 2H2O
4 Zn + 10 HNO3 -'-----'
Metal + HNo, """a 14ghl 6xids { No'
+ or NO + H2O
4 Zn(NOr), + 5H2O N2O
Nitrous oxide Metal oxide + HNo3'-"' Metal nirate + Hzo
similarty, 4Mg + 10 HNO, The metal oxide thus formed reacls further
4Mg(NO3), + 5H2O + N2O with cxcess ofniric acid to form the corresponding
metal nitrate and water. Fot example,
(iy) With conc. nitric aciil' with conc' HNOr'
(i) Wth conc. HNO,, niffogen diaxide (NO)
metals like zinc, magnesium, bismuth, lead etc'
is fomed.
form nitrogen dioxide (NO). ..-..... H2O+2NO2+[Ol
2HNO3
Zn+ 2HNO, Zn(NO3)2+ 2H
' Cu + [O] "-"""] Cuo
HNO3+ H+ HzO+NO2l x2
CuO + 2HNO, -""{ Cu(NO3)2 + H2O
Zn + 4HNO3 Cu +4HNO3- Cu(NOr)z + 2H2O + 2NO2

Zn(NOr)r+2H2O+2NO2 SimilarlY,
Nitroscn dioride Ag + 2HNO3-"-'AgNO3 + H2O + NO2
Simirarry, Mg + 4HNt\ Hg+4HNO3 -""'+ Hg(NO3)2 + 2H2O + 2NO2
+ 2H2O+ 2NO2
Mg(NOr), , nittic oide is evolved'
( ,) ,ltrrr dil HNO3
Bi + 6HNO3 B(NO3)3 + 3H2O + 3No2 2HNO3 .......-* H2O+2NO+3[Ol
-'
Pb+ 4 HNo3---""' Pb(No3)2 + 2H2o + 2No2 Cu + [ol '-""'+ Cuo lx3
Exception. Tin, however, reacts with conc' CuO+2HNO3- Cu(NO3)2 + H2Ol x3
HNO3 to form meta-stannc acid (HrSnOr) and
nitrogen dioxide. 3 cu+8HNo3 ""'- I cu(Nor)z +4H2o+2No
2HNO3 .......-- H2O + 2NO2 + Olx2
SimilarlY,
Sn + 2[Ol * HrO--"r HrSnO,
3Ag + 4HNO3"'-) 3AgNO3 + 2H2O + NO
Sn+ 4HNO, ..-.+ HrSnO3 6Hg + 8HNo3'--r3 Hg2(No3)2 +4H2o+2No
Meta stannic acid
C. Reactlon wlth noble mctals' Noble metals
+ 4NO2 + HzO like sold atrd platinum do not react with conc'
uUdr. However, these metals dissolve in a4ua
Passivity. When dipped in conc' HNO3, me-
/"grd (3 pa s of mnc. HCI + 1 part conc' HNO3)
forming their respective chlorides'
HCI first reacts with HNO3 to produce nas-
cent chlorine which then reacts vith noble metals
formiag their respective chlorides'..
 SOME P.BLOCK ELEMENTS
13141
3HCl + HNO3.-...., NOCI + 2H2O + zcl
Nitroryl Nascent
Aqua regia chloride chlorine
AuCl3
Auric chloridc
Pr+4cl- PtCl4
PlatiDic cbloride
T}ese chlorides subsequentJy dissolve ia ex_
+ 3Hro
cess of HCI forming their corresponding soluble Similarly phenol reacts with
a mixture ofconc.
complexes. Thus, HNO3 +
conc. HrSOo to form 2, 4, 6- trinitro_

. AuCl3 + HCI H[AuClnl pherol Qticic acid), albeit in low

feld.
Auric chloridc Aurtrhloric acid
_ ftgt,
.
+ 2HCl -----r HrtPtcl6l
chloridc
Platinic
ctbroplatiric acid
5. Action of organic compounds
(i).Oxidation. Many organic compounds are
. -. of glyceryl tinitrate and glyceryl dinitrute absorbed
oxidised by conc. HNOr. Foi example,tane sugar
over kieselguhr (a kind of porous earth).
on oxidation gives oxalic acid.
Nitric acid also reacts with proteins giving a
COOH yellow compound called xonthoprorein It is be-
C12H22O +_18[o] ...-+ 6I +5HrO cause of this reason that ntiric acid turns the skin as
Crne sugar from nitric COOH
acid oElic acid
well as wool yellow.
(ll) Nltratlon. A mixture of conc. HNO, and 13.15.4. Uses ofNitrlc acld
conc. H2SO. (ako called nitrating rn irrnre) is used
The important uses of nitric acid are :
for introducing one or more NO, (nitro) groups
- (i) In the manufacture of ammonium nitrate
into the benzene ring. This process is called nitra. and basic calcium nitrate [CaO.Ca(NOr)rl which
tion. For example,

o.
are used as fertilizers.
Conc. H2 SOa
HN()3
(ii) In the manufacture of explosives such as
guu cotton, nitroglycerine, triaitrotoluene (TN.T),
(conc.) 330 K
picric acid etc.
NO:
. . -(l,r)
Io the preparation of nitro compounds
which are used as perfumes, dyes and mediiines.
+ H2O (iu) In the manufacture of artificial silk.
Nitrobenzene
(v) For purification of gold and silver.
(rr) For pickling ofskmless steel trul etching
-
of metals.
Conc. HrSOn
+ 3HNO3 (vii) As an o:<idiser in rocket fuels.
(conc.) (vr'il) As a reagent in the laboratory.

13.155. Structurc of Nitrlc acid

Spectroscopic studies have shown that in the
gaseous state, nitric acid has a planar structure
as
+ 3H2O shown in Fig. 13.17.
The above structure ofnitric acid is, in fact, a
resonance hybrid of the following two structures.
 Neut Coarse Chcmisttg {?r!,D
13142
13.15.7. Rlng lbst for Nltrate ion
In oualitative analysis, the presence oI nitrate
ion is detected bv inr 'Jt.ln this test, a freshly
oreoared solution of firrous sulphate is added to
ih"'uor"out solution of a nitrate. Pure conc'
HrSOn is then added carefully dropwise along the
walls of the test tube. The aPpearsnce of a dark
brown ring at lhe junction ol lhe two ltyen indicates
the presence oI a nitrate ion .

The brown ring is due to the formation of a

brovor comDlcx befween nitric oxide (formed as a
FIGUnE 13.17. Shuclwe of nitrlc acld In result of re-<luction of the nitrate ion by the Fe'-
the gascotE state.
ions) and Fe2+ ions.

n o:
2 HNOr'-""'r FIzO + 2NO + O

NO!(cq) + 3Pe2+ (aq) + 4I{+ (aq) -""""'+

*/'
HO_N
+
>?
Y1
.---- ro-*\o, NOG) +
Nirric otidc
3Fe3+(a4) + 2H2o(11

\ Fez+ (aq) + NOG) + 5H2O(r) -------'-

IFe(HrO)rNo+]2+(aq)
13.15.6. Structure of Nltratc lon
(l)
Pcntaquanitrosoniumiron
(Btowi cofiPld)
Like nitric acid' nitrate ion also has a planar
structurc. The nitrogen atom is spz'hybridized and The colour of the complex, is actually due to
hiice the O - N - O-bond angle is 12Oo as shown in chorye tmndu i.e., an electron is transferred from
Fig. 13.18. NO"to Fe2i' As a result, this complex formally
cootains iron in the +1 state and NO+' Conse'
q comPlexshould be
D and not Pentaa'
q NOF*'
ii:,::::,:lilxi:i::ili:i:'iiii:i'ii:;1i'.il:liii:ilxir:i::i:::!lli:ii:::iii:Iiii;i.i:

KtrlScheele, the Swedish chemist, was the

FIGURE 13.18. Stmchne of nlFale lon
Itr fact, nitrate ion (NO3-) is a
hytrid of three structures (Fig' 13 19) :
As a result of resonance, all the tbree N -
bond lengths arc equal and are 218 pm [ong'
first to prepare orygen by heating mercuric oxide
in t72. He recogniied it as one of the major con-
stituents of air and naned il as frre air or vital air'
loseoh Ptiestlev,the English che mist, also prepared
oryien in tTi by focussing the sun's rays with the
resonance
heii of a lens on mercuric oxide' lls elemental
natlre was, however, established by the French
C)
chemkt, Lavoisier.

T:6:s
II n:i.T .ll
/*\a
j:i.' RESONANCE HYBBID

FIGI BE 13.f 9. Resonatir'g stmctures of NO3- ion

 SON/E p-BLOCK ELEMENTS
13143
The electronic-conhguration of orygen in the 13.162. Prcparatlon of Dloxygen
ground state is 1s2 2sz Ut2pt, ?p]. Orygen has
l. By decomposluon of o:r5gen-rich . com-
three naturally occurring isotopes, i.e. 1610 pounds, Certain compounds containing large
(99.762Vo), t78o (0.038%) arl,J 1t8o (o,zoovo). amounts of orygen such as KClOr, KMnOo,
Out of these three isotopes, l8.C) is radi oactiye and KNO, etc. give dioxygen on strong heating.
hence is widely used in studlng the mechanlsm of Hcat
organic reactions and in other tracer techniques. 2 KMnOo ----------r IQMnOa + MnO, *O,
Like hydrogen, orygen also exists in the elemeatal Pot. Pemangana(c Pot. msnganatc
form as a diatomic molecule (Or) and is, therefore, Hcat
referred to dioxygen. An itrteresting point about
as 2KClO3 zKCl + 3O2
diorygen is that although itsmolecule contains even Pot. cNoratc Pot. chloride

number of electrons (16), it has two unpaired Hcat

electrons and hence s paramagnetic io, nattie. 2KN03 ---.. 2KNO2 + ()2
Pot- riitratc Pot. nitrite
,^. Ory, gerr has two allotropes, r'.e., diorygen
(Or) and triorygen or ozone (Or). Hcst
ZBaO, 2BaO * Oz
13.16.1. Ibrrestlal Abundsnce and Dlsh:Ibu_ Barium pcExidc Badum oridc
tion
Laboratorl method of prtparatlon (a) Ther.
Just as hydrogenis the most abundant element mal decomposltion of potasslum chtorate. ln the
in the cosmos, diorygen is the most abundant ele_ is produced by heating a mix_
ment on the surface of the earth. It occurs both in
orate and manganese dioxide
the free as well as in the combined state. It con-
4 : I in a hard glass test tube
stitutes about 507o byweight ofthe earth, bodies of
wateraEdatmosphere.In
in alr ao an efte\a of ZlVa Mno2
weight. In the combined s 2KCIor(s) -11 2KC(s) + 3oz@)
4nK
ight. In the earth,s crust,
of silicates, aluminates, The gas is collected by downward tlisplace_
metals. Almost all the metrt ol water as shown in Fig. lii.2O.
is believed to have been In the absence of MnO2, the thermal decom_
produced by photosynlhesis taking place in green position of KCIO, occurs slowly
plants in the presence of chlorophyll at 670-7m K.
lrenritize4 Therelore, MnOracts as a catal1st. It nol only lota,en
and sunlight
Suolicht
the tempemture of decomposition of KCIO,
fronr
.rCO, + .rHrO :l= (CHTOL + rork)
chlorophyll csrbohydratc
670
- 720 K to 420 K but also accelerates the rute of
decomposition .

KCI-Or + MnOz

FIGURE 13.2O. preparation of dioxygen in the laboratory.

 Pradeep's
13144
Heai
(b) B oxide'
2 Ag2O 4Ag + O,
Diorygen orY bY
Silvcr oxidc
Silvet
the action
Heat
2Naro2(s) + 2HroO -""""' NaoH(aq) + or(g)
4 3Mn02 Mn3Oa * Oz

For thispurpose, sodium peroxide is placed in Manganese dioxide Trimanganic

tetroxide
a flat-bottomi<l flask fitted with a dropping funnel
13.163. Pur Dioxrgen from Barlum
hydroxide
Pure diorygen canbe prepared by electrolysis
of a solution oi Ba(oH), using nickel or platinurn
electrodes.
BEEHIVE 13.16.4. Isolatlon of Dlo:rYgen
SHE LF
The main sources for large scale preparation
of diorygen are (i) air and (ii) water'

aving
K) in

(ii) trtom be
prepared by the ng a
Diorygen can also be prepared by the action small amount of
of acidifieJ potassium permanganate on sodium
peroxide. zIJrO({) :ElcctrolvEis 2H2@)+ O2@,)

2 KMnOa + 3 H2SO4 --"""-'' Diorygen is collected at the anode while

IISO4 + 2 MnSOo + 3 H2O + 5 [O] dihyrtrogen is liberated at the cathode'

Na2O2 + H'SO4
......* NqSOo + H2O2 lx5 The world's total production of diorygen is
over 100 million tonnes Per Year.
H2O2 + [O] + H2O+02 lx5 13.165. Atomic and Physical Properties
I. Physical proPerttes (i) Diorygen is a

colourless, odourless atd tasteless gas '

2KMnOa * + 8H2SO4 """""''
5Na2O2

IQSO. + 2MnSOo * 5 NarSOn + 8H2O + 5O2

2. Bv thermal decomposition ofmetal oxides'
The oxides of certain healy metals such as Hg, Pb,
Ag etc. onheating decompose to liberate diorygen'
ganic wastes in water bodies.
lleat
2HgO zHg * Oz (iii) tt cau be liquefied to a pale blue liquid at
Mcrcuric oxide l\{ercury qo z k.'When cool;d with liquid dihydrogen, it
freezes to a buish white solid melting at 54'4
K'
Heat
2 Pb3o4 6PbO + 02
The important phlnical proPerties of atomic
Lthatge 'Ihble lll'5'
Red lead and molecular o:rygen aie given in
SON,4E p-BLOCK ELEI,4ENTS 13145

I'ABLE 13,5. Atomlc and molccular propertlcs of oxlgcn

ATOMIC PROPERTIES MOLECUT"\R PROPERTIFS

Ionisation enthalpy (kJ mol-l) 1310 Meltirg point (K) 54 4

Electron gcirr enthalpy (kJ nrol-l) 140 Boilin8 piDt (K) 90 2
Electronegativity 3 50 Density (9,/L) at S.TP 1.129
Atomic radius (pnr) 73 Bond length (pm) l2o 1

lonic radius (o2-) (pm) 140 BoorJ eoergy (kJ mol-l) 493 4

13,13.6. Chemlcal Rcactlvlty Heat

aAl(s)+3or@) 2 AlrO, (s)
The bond dissociation enerry of diorygen is
high and hence the reactions of diorygen require Hcat
4 Fe (s) + 3 O, (8) ----.-.. 2 FerO, (s)
initiation by exernf [s3ting. However, when the
reaction starts, it continues of its owD- This is due (iv) Less active metak like gold ond platinunt
to the reason that the chemical reactions of do not rcact with diorygen.
diorygen are exothermic atrd the heat liberated (b) Re{cdon wltt Don-metals. Diorygen com-
during the reaction is sufhcient to carry on the bines with many tron-metals except noble gases
reactions. forming their corresponding oxides. For example,
Some important chemical properties arc dis- (i) With tlihylmgen :
cussed below : 1073 K
l. Actlon of lltmus. Diorygen is nantol to zHz@) + oz (s)
orElEctric dischar8e
2 Hzo (B)
litmus. water
2. Supporter of combustion. DioDEen k nol (ii) With dinibogen I

conbustible bul is a supporter oI combustion.When

a glowing wooden splinter is brought in an atmos- N2 0r) + 02 G) ...-
3300 K
zNo G)
phere of diorygen, it burss out into a flame. Nilric oxide
3. Oxldatlon, Dio:rygen is a powerful oxidising (iii) With sulphur :

agent andhence can oxidise metals, non-meta.ls and Hcat

other compouads to their respective oxidcs. S(s)+or@) soz G)
Sulphur dioxide
(a) Reaction wlth metals. Diorygen directly
combines with most of the metals (except some of (iv) With cafton :

the less reactive metals such as gold and platinum) Heat

to form their respective oxides. For example, 2C(s) + or@) zco G)
(limited) Carbon monoxid
(i) Active metals li*e sodium, calcium etc.
react at room temperature forming theirrespective Ileat
oxides.
C(s)+ o.@) co' G)
...........r 2 NarO (s) (*er') Carbon dioxide
4Na (r) + Oz G)
(v) Wtlt phosphorus :
2Ca(s) + OzG) 2CaO(s) IIeat

-
However, sodiun also reacts with dio:rygen at
Pa (s) + 5 O, @) """""'+ PaOr. (.t)
575 K to form sodium peroxide.
(aice$) Phosphorus pcntoxide

575 K (c) Reactioo with compounds

2 Na (s) + Oz@) Na.O, (s) (i) With sulphur dloxlde. Dioxygen reacts with
sulphur dioxide at 723 K under a pressure of2 atom-
- in diorygen to form
(ii) Magnesiunt burns
spheres ernd in prescnce of platinum or vanadium
magnesium oxide.
Heat fientoxide as catal)st to form sulphur trioxide
2Mg(s) + OzG) ._ 2MgO (s) 723 K.2 atnl
(iii) Aluminium and uoz. When heated in air 2SO2@) + OrG) sOrG)
form their respective oxides. Pl or V2O5
 13146
NeuJ Couyse Cheru istrg
'Ihis reaction forms the basis of Contact gets converted into ozone which is an allotropic
prccess for the fianulacture of sulphuric
acid. torm oI oxygcn.
(ri) Wth ammonia. Diorygen oxidises am_ Silclt clectric dischaagE
monia to nitric-oxide in presence 5f plat;num gauz. 30, 20t
as catalyst at 5fi) K. Dior(ygcn Ozone
K 500 t\
4NH3G) + 5or0t) -__-__)
4NOk) + 6Hro(s)
This reaction forms the bdsis of Ostwqld
prucess for the manutacture of nitric acid.

. (lll) chloride
,hydrogen Hydrogen chloride. Diorygen oxidises
chlorine in preseice o[cupric
to
13.16.7. Uses ol Dlo:rygen
chloride as catalysr at 700 K.
(i) Diorygen is use d n ory-hydrosen and oh)-
?00 K. CuCl,
acety.tene aot&es which are uleci for"cutting aid
4 HCIG) + oz@) + Ctr(s) weldiug of metals.
This reaction forms the basis of Dzcort,s (i).lt.is used n metallu@cal processe; to
-*"'zHroG)
process for the manufacturc of chlorine. remove t-he impurities of those metals and non_me_
(r'r,) Wth carbon disulphide. Carbon tals which form volatile oxides.
.._ rlisul_
phidc burns in diorygen to form carbon dioxide and
sulphur dioxide.
Hcar
Cq(8)+ 3or@) ..-.---- c'or6)+2sor6)
0) wl
phides such
high temper
dioxide.
[Icar (yi).lt is also used in large scale production
zZnS (s) + 3O2 g) + _.^ and synthcsis of
@) zZnO 2SO, (g) TiO, gas (CO + Hr).

3(), G) -'-
IIcat
2HgS (s) + 2Hgr) (s) + 2So2 k) 13.17. Oxides i{i..:.r1ii1rl:ij:ririii:tt::;iil!!itii::iiir:ini;rti:rriii:1:itii:t:i:ilit:i:L:tir:i::ii:,.,ii

(vi) With hydrocarbons. Both saturated and

unsaturated hydrocarbons burn in excess of air or
diorygen to form carbon dioxide and rvater.
CHo G) + 2Or(g)- Co2
G) + Hzo G) ;
Methane

A.H" : _ 890 kJ mol-r

CH, = 911, @1 * roz @)
Ethyrcnc @) ?HrO 2CO2 + (g)
- ;

A"H" = - 1411 kJ mol-r

2CH=CHG)+50,G)-'
Accry'cnc 4c(rz k) + 2HzO G) i
-\
AcHo =- 13fi) kJ mol-l
These reactions arc called combustion reac.
tlons and are highly exothermic in natrre. That is
why hydrocarbons are userl as fuels.

. 4. Acllon of silent electric discharge. Under

the adion ofsilent electric dlscharge, d.iai"*yg..
 SOME p-BLOCK ELEMENTS 13147

NEo(r) Hro(/)+ 2NaOH(aS) (ir) Neutral oxides . Oxides which neither react
MgO(s) + Hro(/) Ms(OH)r(aq) wilh ocidr nor with bases are called neutral acides.
- For example, HrO , NzO , NO , CO etc.
FerO.(s) + 3HrO(t)-.' zFe(OH)r(aq)
Tiflds ln Acid-base behavlour of oxldes ln
The basic oxides react with acids to form salts
and water.
- lhe Periodtc table.
a given
Nazo(.r) + zHcl(aq) -----------+
e oxides
zNaCt(aq) + H2O(/) throu&
FerOr(s) 4 3 H2SOo(a4) ---.......-
NarO MgO AIzOr SiO2
Fer(SOo)r(ar1) + 3H2O(t) slrcngly basic tsasic erpiotJ;" wcakty acidic
(ii) Acidic oxlds..4a rxide which combines PlOro soz clzot
teith water toIomt an acid ir called an acid.ic oxide. Stronglyacidic Strcngvacidic VcryEtronglyacidic
The oxides ofnon- metals are acidic in nature, For (ii) Amon4st .r-block elcments, on moving
example. down a group, the basic chdracter of the oxides in-
COz@) + Hro(/) -------* Hzco3?q) creases. For example
Carbonic acid LtTO NuzO X;O
So3G) + HrO(/) ...* HrSO.(aq) Weakly basic Basic Morc stmngly bs6ic
PnO,o(s) + 6H2O(/) ._ 4H.POn@q) RbrO, CEO
Vcry strcngly basic
Phosphonc acid
N2o5 (/) + HrO (/) 2 HNO3 (aq)
(iii)
down lhe
Cl2o1G) + HrO(/) --.._ zHClOo@q) decreases
Perchloric acrd example, in group 13, the acidic character of oxides
These acidic oxides react with bases to form decreases as :
salts and water. For example, Bzo: Al2o3 Garo,
SOrG) + 2NaOH(aq) ........_ Acidic Amphoteiic Weaklybasic

NarSOr(aq) + HrOo In O, TLO,

Basic Strongtybasic
PnO,o(s) + 12 NaOH(a4) ------.----
(iv) Amongst non-metallic oides, the acid,ic
4NarPO.(aq) + 6H2O(/) choracler incleases os the oidation stale oI the non-
(n)Amphoteric oxides. Oxrdes whiclt teact ntetal i creoses. For example,
with bolh acids and bases are cdlled qmptntetic +1 +2 +3
oides.These are generallyformed by elements that NrO NO Nzo:
are on theborder line between metals and non-me- Ncutml Neutrdl Acidic
tals, i.e., elements (Al, Zn, Sn, Pb etc.) which lie in +4 +5
the centre of the periodic table. For example, NrOo NrO,
Al2o3(r) + 6Hcl(o(i Stmngty acidic Very 6trongly acidi.
(Basic) Mixed Oxides.
-
zAtc\(aq) + 3H2o(/) two simple metal oxi
oxid,ation states are
A!Or(s) + 6NaOH(aq) + 3HrO(/) mixed oxides show the properties of both the metal
(Acidic) oxides simultaneously. For example,
_----_-_+ 2Nar[Al(oH).l(a4) Pb3O1 + 4 HNO3 Pbo2
Sod. hcxaaquaalunlinalc Red lead --* crom djoxid.)
tcad.
C)ther examples of ampboteric oxirles arc : + 2Pb (NO3)2 + 2H2O
ZnO, PbO, SnO. (tdn Ld Nid.)
13148
Pradeop's

Thus, red lead is cons'dered to be a mixture
of two oxides - lead dioxide (PbOr) and lead oxidc
(PbO) and is givcn the formula, PbO, . 2 PbO.
Similarly, magnetic oxide
oxide (FerOo) is considered tobe a mixture offerric
oxide (FerOr) and ferrous oxide (FeO) and is given
the formula, FerO, . FeO. Consequently, it gives a
mixture of ferric and ferrous salts on treatment with
acids,
Fe.O, . FeO+8HCl+ 2 FeCl3+FeClz+ 4 HzO
Likewise, trimatrganese tetroxide, Mn3Oa
(2 MnO . MnOr) is coosidered to be a mixed oxide
of manganous oxide (MnO) and
dioxide (MnOr).
EXAMPLE 13.1. Classily the following into
ucidic, basic or
equations for th
acids or akalies. SO, ZnO, BaO.
Solution. (i) SO, is an acidic oxide since
reaction with water produces sulphurous acid.
(0
, 2H+ @fl + sQ' @q)
soz G) + Hzo
(r'r) ZnO is an anphoteric oxide since it dis-
solvcs in an acid to iorm Zn2+ ions aad in a-o alkali
to form IZI(OH)1]2+ ion.
ZnO (s) + 2Il+ (aq) ' Ztz+ (aq) + HrO (l)
ZnO (s) + zoH- (aq) + H2O (/)
lzn(oH).1?+ (aq)
(ni) Bao is a basic oxide since it reacts with
watcr to form an alkaline solution of Ba(OH),
Bao (s) + Hro (0
1 3. l 8, Ozone :i:lii:;::i::!:iii;i:,:rllili:ij:ilii+:a;l:i::l:l:iiiri:ilr:i;rll:l:il'l:i1i+ili:;lii:;i:ii:
Elemental orygen exists in two molecular al-
lotropic forms, i.e., O, and Or. The triatomic
molecule, i.e., O, is called oioxygen or ozone.
tions on dio:<ygen.
UV ligit
"""'------'
3Oa@)
Ozone absorbs ultraviolet radiations (220 -
290 ru7.\ aruJ thus protects the earth and its in-
habitants from the harmfut radiations ofthe sun.If
there werc no ozone layer, more ultraviolet radia-
tions will reach the surfac-e of the earth causing
much damage to plant and animal life.
Ozone layer in the stratosphere is depleted by
or ferrosoferric (a) nitric oxide, (b) atomic orygen and (c) reactive
hydroryl radicals which are also present in the
atmosphere due to bio-mass burning.
(a) or G) + No G)-'-+ Noz G) + o, G)
(b) 03 G) + o (s)-.--+ o, (s) + o, (B)
(c) or G) + Ho G) "'-". o. (6) + Hoo @);
Hoo o G)"""- Ho G) + oz G)
G) +
Flights of supersonic aeroplanes and nuclear
manganese
explosions and lightningrelease NO into the atmos-
phere.
Ozone layer is also depleted by man-made
chlorofluorocarbons (CFC's) which have been
used since long as aerosol propellants and as
refrigerants (CFrClr, freon). Chlorofluorocarbons
its are long lived molccules and diffuse into the strato-
sphere where they undergo photochemical dis-
sociation to produce chlorine atoms. These
chlorhe atomsreact with ozone thereby decreasing
the concentration of ozone at a rate much faster
thatr its formatior from 02.
ht
ClrCF, G)
-- 'Cl G) + 'CCIF, G)
.cl G) + 03
G) ' clo. (9 + oz@)
- clo. G) + 'o G) * 'cl G) + 02 G)
Volcanic eruptions also release chlorine
atoms into the atmospbere' Due to the hazardorls
effecs of CFC's on the ozone layer, U.S.A' has
<------\ Ba(oH)2 banned the use of CFC's in spray cans.
Three scientists namely P.J. Crutzen, MJ.
Molina and F.S. Rowland recived 1995 Nobel
Prize in Chemistry for their pioneering work ia this
area. As a result oftheir wor\ there is a world'wide
concern about the depletion of the ozone layer in
the uPPer atmosPhere the stratosphere and serious efforts are being made
face of the earth) where to hnd alternatives for CFC's and to liadl ths smis-
f ultraviolet (UU radia- sions of oxides of nitrogen (NO), into the strato-
sphere.
2O3(g) 13.18.1. Prparatlon of Ozone (IHo)r)?n)
Ozone is prepared by pass*g silent elecfiic
dischorye thrott{t pure, cold and dry dicxygen in a
specially designed apparatus called the ozoniser.
SOME p-BLOCK ELEMENTS
Silcnt eleclric dischargE
30z@) zotk);
aH,,, = * 142'7 kJ mol-r
The reaction is thus endothermic awJ 742.7
kJ ofenergy is absorbed when one mole ofozone is
formed from diorygen.
A silent electric discharge (spa*less electric
discharye) is used since it produces less heat. This
prevents the local rise in temperat'Jre which may
decompose ozone back to diorygen.
Ozone is prepared in the laboratory by the
following two types of ozonizers : (i) Siemen's
Onnizer and (ii) Brodie's Ozonizer.The description
of Siemen's ozonizer is givcn in Fig. 13.22.
T*-
ozoNtsEo
OXYGEN
INDUCTION
FIGURE 13.22. Seimm's Ozoniser.
It consists of two co-axial glass tubes sealed at
one end. The inner surface of the inner tube and
the outer surface ofthe outer tube are covereri with
tin foils. The inner and outer coatings oftin foil are
connected to the terminals of an induction coil.
One end of the coaxial tubes has an inlet for pure
and dry diorygen and the other end has an outlet
for the ozonised orygen.
A slow stream of purc, dry and cold diorygen
is passed through the annular space between the
concentric tubes and subjected to the silent electric
discharge when some of the diorygen gets con-
verted into ozone. The product which actually
comes out of the outlet is a mixure of O, and Or.
JCTURES
13149
It is called ozonis e d orryen and conlqins sbout 10-
157o ozone.
The leld of ozonised orygen can be increased
by rrsing (i) pure and dry diorygen, (ii) dry ozoniser
(iii) avoidingspa*ingand (iv) main ainingfoi ylow
tempemturc (about 273 K)
Prcp[ration of pure ozone. In order to
prepare purc omne, the ozonlsed orygen is cooled
with liquid airwhen ozone (b.p. 161.2K) condenses
in preference to oxygen (b.p. m.2 K). The liquid
ozone thus formed still contains some dissolved
dioxygen which can be easily rernoved by lractional
distillation.
13.182. Structurc of Ozone
The central orygen atom in ozone is sp2-
hybridized. Thus, it has an angular structure as
shown in Fig. 13.2j. The O - O - O bond angle is
116.8' and both the orygen-o4tgen bond lengths
are equal i.e. 127.8 pm. This bond length lies in
between O - O single bond length of 1rB pm and
o = O double bond length of 110 pm.
FIGURE 13.23. Structure of ozonc.
In order to explain the oxygen-orygen bond
length in ozone, it is considered to be a resonance
hytrid of the follorving two resonating structures
(Fig. 13.2a).
Because of resonance, both the orygen-
orygen bonds have partial double bond character.
In other words, both tho orygen-orygen bonds are
equal (127.8 pm) and lie in between those of
orygen-orygen double bond len6h of 110 pm and
orygen-orygen single bond length of 148 pm.
AESONANCE HYBRID
13/50 l'raIt,i,t, . Neu, Coursc Chemistrglf;fi[fl

13.1E3. Properties of Ozone cus (r) +4o3 G) cuSOr (j) + 4(t2 @)

(a) Physlcal properties. (i) Ozonc is a pale ZnS (.r) + +tl: G) .....---} ZnSor (s) + 4Oz q)
blue gas having a strong characteristic smell.
-
(ri) When cooled i
liquid air, thc ozone
Cds (r) + 4O3 G) ----""' Cdsoa (s) + 4o2 U)
present in ozonized o:rygen condelses to a deep (ii) Ozone oxidiser halogen ocids lo cor'
blue liquid ft.p. 161'2K) and thon (o aviolet-black rcsponding lrulogens
solid (m.p. 80 6 K). o:G) ----_ orG) +oG)
(iii) lt is about 1 67 times heavier than air 2Hcl(aq)+o (g) Cl, @ + HrO (0
bccause its vapour density (VD.) is Z while that of
air is 14.4. - k) + Hzo (t) + OzG)
zHCl (a(i+o3G\ ---.C12
(iv) It is slightly soluble in water but readily Similarly, HBr is oxidised to Br2 and HI to 12.

dissolves in organic solvcnts such as turPenthe oil, (iii) Ozone o-ridkes ,tilites to nilrotes
cinnamon oil, cerbon tetrachloride, glacial acetic
acid etc. OrG).--......* o2@)+o(B)
(v) Ozone is diamagnetic whilc dioxygen is KNO, (a4) + O G) """""'r KNO, (aq)
paramagnetic.
KNO, (aq) + 0r G) ......_ KNO, (c4) + Oz G)
(b) Chcmlcal properlles l. Neutral character.
Ozone (trio:r1gen) is ncutral to litmus.
(iv) Ozone aridises moi:t potassitttrt iodide to
iodinc
2. Decomposltion, Ozone is not a very stable
compound. Even at ordinary temperature, it orG)- ()2G)+oG)
decomposes slowly to give diorygen. Horvever, 2K (oq)+H2o (t)+O G)"-"'.zKOH (aq)+12$)
when heated to 473 K or in thc presence of a cat al)'st
such as manganasc dioxide, platinum black or cop-
zKt (oq) + Hzo (0 + O, G)
per oxide, the decomposition takes place very 2KoH (a{) + 12 (,r) + o, G)
rapidly. ---'
This reaction is used for quantitive estimation
473 K ot c3tal,6t
aot(B) 3oz(s) of ozone,
Oronc Diox)tscn (v) Ozone axidises acidified ferrotts solts to
3. Oxldlslng agurt, Ozone is a poweful atidk- lenic sal*.
ing agent much stmnger thon ilioxygen. This is due to orG)+ oG)
o:G)
-
the rcason that ozone has higher energy content
than diorygen and hence decomposes to give
- @4 + o
2FeSOa (ag) + H2SO4

dioxygcn and atomic oxlgen. Fer(SOn), (aq) + HrO (/)

orG)- ozB) + oG)
ozonc DitxYgcn Atomic oryBcn 2FeSOa (aq) + H2SOa (dq) + ()3 G) .....-.....'

Th atomir Aygen thus liberated brings about Fer(Soo), @q) + Hro O + Oz G)

the oxidatioa drhile molecular otf/gen is set free.
(vi) Ozone oxidises potossiunt ferrogrunide lo
Some important oxidation reactions of ozonc arc
discussed below : f
p o I fl s s i un t c rri q'sni de
(a) Oxldation of conrpounds orG)- ozb)+o(8)
(i) Ozone axidises block lead sulphide to ririte 2K,1[Fe(cr.!61 @q) + }{2o (l) + t) @) -...-.".-
lead sttlphale. 2Kr[Fe (CN)61 @q) + ZKOH (aq)
o:(c)-o.G)+ o G)l x4
Pbs (s)-r 40 @) Pbson (s)
2\[rc(CN).1 (aq) + H2o (/) + or G)-
2K, (CN)ol (aq) + 2 KoH (aq) + o, (s)
PbS (s) + 2K)3 @)
- PbSOo (s)r'4O, @) [Fe

-' sulplrides of Cu, Ztr

Similarly, ozone oxidises
(vii) Ozone otidises potassium mangonate
and Cd to their rspective sulphates. Gteat) to potsssimt pennongonate (pink)
 SOME p.BLOCK ELEMENTS 13/51

osG)------- or(B)+oG) (ii) Ozone oidiseti moist anti,nony to an-

2K2lt{n()a @d +H2o O + o G)'---------+ titnonic ocid (H rSbOo)

?_\Y:9,_\,9 !L\9!1!!)
o,k)- o,G)+oG)l x5
zKrMnOo @Q +
Hzo (/) + 03 G) -----' 2Sb (s) + 5t) G) '-----+ SbrO, (s)
ZKNtnOn @q) + zKoH (aq) + O, (g) SbrO, (s) +3H2O O ----------- 2H:SbOr (aq)
(b) Oxldatton of non-mtals. Ozone oxidises 2Sb (s) + 5o3 G) + 3H,o O -----,
non-metals like iodine, sulphur and phosphorus to zH3SbOa (aq) + 5O2 G)
their corresponding oryacids. For example,
(d) Oxidatton of metals. Ozone also oxidises
(i) Ozone oxidises moist iodine to iodic acid certain metals like silvcr, mercury, copper etc. to
(Hro) their corrcsponding oxidcs. For example,
()3G)------_orG)+oG)lx5 (i) Silver is oitlised to silver oxide (AgrO)
12 (r) + 50 G) .._ Izos (r) o:G) ._-...* or@)+oG)
2Ag (r) + o G) --------' AgrO (s)
I, (s) + 50, (g) + HrO (0 ......._ 2As (r) + oj G) ---------' A&o G) ;-o, G)
zHlO.' (aq) + 5i), G) (i) Mercury h oidised lo mercumus oxide
(ii) Ozone oidises moist sulphur to sulphuic (Hgzo)
acid (HrSO). ()3 @) oz8) + o (s)
-----'--+
orG) ._ o,G)+oG)l x3 2HgO+ok)...*Hg,o(s)
58 (r) + 24o G) ...._ E So3 k) zHs (t) + o: G)
...........r Hg,o (s) + o, (6)
SO3 k) + HrO (/) '----"' H2So1 (aq)l x 8 The mercurous oxide thus formed dissolr,s in
S, (s) + 24O3 @) + 8I{rO (0 meranry. As a result, mercury loses its menisos and

---- starts stickirg to the gless. This is cdled tdllry d

8HrSO. (aq) + 2e, (S) memny. The menhcus carq however, be restorcd by
(iii) Ozone oxidises moist phosphorlls to plos- shaking it with water which dissohas merctmus cride.
phoric acid (HfO). (e) Exceptlonal bchaviour. In all the oxidation
orG)-orG)+oG)lxt0 reactions discusse is brought

P. (s) + 10 O @) P.O,o (s)

aboxt by the atom nis always
-- evolved. Howevet; of SO, to
__PlO,. (r)- SO, and ocidifed SnClrto SnAothe ozone is utitized
Pa (s) + 1003 G) + 6H2o (/) as a whole and dioxygen is not evolved. Thtlrs,
--+ (,) 3sorG) +o:G)
4HrPOa@fi+ 10orG)
(c) ffidadon olmetolloftls. Uke non-metals,
dioxide
Sulphur
-_l Sltphursor(oc)
ttiqidc
ozone also oxidises metalloids like arsenic and an- (,r) 3 SnCl, (s) + 6HCl (aq) + Or G)
timony to their corresponding ory acids. For ex- Stannous chloride
ample, SnCl (oq) + 3HzO
(i) Ozone oxidises moist ssenic to onotic acid
o
Stannic chloridc
(HrAsOr) (Q Bleaching actioln, Because of its axidisiag
or@)-------.ozG)+oG)l x5 action, omne octs as o mild bleuching agent and
bleaches veget oble colouing matter.
2As (s) + 50 G) --------, Asros (s)
Vegetable colouring matter + 01 -----.--+
ot (aq)
2As (s) + 5O3 G) + 3H2O
JH2u (4
(r)
Colourlcss oxidised matter + 02
--..-. _ As such ozone blcaches indigo, ivory litmuq
2HrAsO. (aq) +5O2@)
delicate fabrics like silk, wool etc.
131s2 Pradeep's

4. Reduclng agcnt. Although ozone is an ex- 13.1E.4, Uses ol Ozone (IHo:qgen)

tremely powerful oxidising agent yet in some reac- (i) Because of its oxidising nature, it is used as
tions, it acts as a weak reducing agent. For example, a disinfectant and as a germicide for sterilizing
it reduces peroxides such as hydrogen peroidc, water.
bariurn peroxide etc. liberating diorygen. (ii) It is used for bleaching delicate fabrics,
HrO, (ur) + ()3 @) H2O (l) + zoz @) oils, starch, ivory etc.
BaO2 (s)
--r
+ O, G) ._-..' BaO (s) + 2O, @) (nr) It is used for purifying air in crowded
places such as cinema halls, underground railway
-addltlon rcactlon
5. Formation ofozonides
stations, tunnels, mincs, slaughter houses etc,
When ozone is bubbed through the solution of
(fv) It is used in industryduring the manufac-
an alkene in an inert solvent such as ture of artificial silk, synthetic camphor, Potassium
CH2Ct , CHCI3 , CCll etc. at 196 K it adds across
permanganate etc.
the double bond forming an ozonide'
(r,) It is used as a reagent in Organic Chemistry
c)
CH, 116 K //,CH2- for carrying out ozonollsls and other oxidation
ll +os t'--..-a*r-f, reactions.
CHz ccl4
Ethylene
- Ethy'cnc ozonide
13.185, Tbsts of Ozone

196 K
(i) If turtrs alcoholic solution of benzidine
CHr-CH=CH, *os brown.
ProPylene
cctl (ii) In presence of Or, mercury loses meniscus
and starts sticking t o f,ass (tailing of mercury)
,'-o\ (rit) It turns moist starch-iodide paper blue.
cH3 - cH CH, (rv) Omne does not reduce acidilied solution
tl
o-o of KMn0. and IQCrrOr.
Propylcnc ozonidc

Q. t. why doc! rot bor form Bl+ lons?

Ars. Boron tra! threc clcctrons lD the valcDce shell. Bec.use of itll $rsll rizc 8od high 3um of thc first thre! ionizs tion
enthalpiq (ir., IEI + tq + Iq), boron doeE not locc all it! wlenc! electronr to form Bl+ lons'

e.2.Although borlc acld B(OH!, cmtalns tlu-c hydruryl grutpd )t! ft Msvt3 sr s monobadc odd. Eqlsltr t?ty ?
An& Becaure of tlle small slzc of boron atom and presnce of onty six ?lcctroB in its valcnce shell in B(OH)r, it
accDpts a lone psir of clertrons from the oxygen atom of the H2O mole,cule to form a hydrated rPcier'

,,o,,fio<X * *.,,u-QX B(oH)r-+H+

Hydiatcd rpccic. -
Thc +vc chargc on thc o-atom, iD tum, pulls the olc4lroDs,of thc o-H bond lou,ards itlclf, threby
facilitating the ;?kssc of a proton. A.e a resuit, B1o ny aca a wcak molI,o|Fsic Lswit acd and thur rcacb with
NqOH rolution to form rodium metaborate.
B(OH)3 + NaoH Y2+F1oH1.1 or Na+Bot + 2H2o

- Sod. mctaboBtc

e. 3. Dlarnond k covllctrg Ft lt'br r

hlSh m.ltlng PolnL vyhy ?
Ans Diamond har three-dimensional Det-work structure invoMng rtrong C-{ bond!. Hcncr dlamond hr6 hlSh
melting polnt insPite of ils cor,Elcnl nature.
SOME p.BLOCK ELEMENTS 13/53

Q. 4. Whlch oddC of crrbo! ls en lrhydrftlc of cartonlc acld ?

Ans. SiDcc carbonic acid decompcs to Sivc CO2 and HzO, thercffic, CO2 ir rcgardcd as an ontt dridc ofcarbonic
acid H2CO3 r
H2O + CO2
Q. 5. Carbotr moEoddc b rcadlly atcorbcd by rtEDonhcd cuprour chlorld. lohaloE but ctrboE dloddc k not
ExphlD.
Ar& Due to tlre prcactrcc of a lo,te palr oF cleclron! on carbon in CO, aqs a! I La9L, bNc (q ligand) and ahrs
formr a lolublc compl. with ammooiacal cupros cllbrldc solutlon.
CuCt +NHr+CO * [Cu(CO)NH3l+Ct-
Solublc conplcx
On the other hand, CO2 do6 not act. ar a lrei,
Darc siDc it dG harc a lonc pafu of clcclrons oo thc carboD
atom and hcncc does not dissoly in ammoniacal cuprous chloride loluton.
Q. 6. Slls[c. rrc lcr' lE [umb.r vhcEar alkrtr.s ar! lo]gG lD rumbcr. Erplaln
h Carbon has the m4imum tcodeocy fff carenation due to stroogcr C--{ (355 kJ mol-l; bonds. Ar a result,
It form! I Iargc numbcr ofallaner.
Sllicon, on the othcr hand, duc io wakct sl-Si (200 t I mol - t
) bonds has much lerscr tcndcncy for catcnstion
and henc formr only I fa[, rilaDc..
Q. 7 , Ctr!f,lly thG lollowlDg hto (D lonlg c@lbDt rrd lltlrttltlal cartldcg :
(r) slc (ir) vc (rr) wc (ry) Al.g

ADA (i) co/alcnt, (ii) and (iu) interstitial and (iv) ionic.
QE $tltr balanccd cqurtlon lor th. hydrolFb ofHcot and co3- to!6.
AIt'. HCOs- + H2O il H2CO3 + OH-
ol- + Hro <-r Hco3- + oH-
Q. 9. Glvc onc ErctloD lD t'hlch oDlloEh octs 6s I rcduclng ogctrL
A!s, When NH3 is passcd over heated cupric Gidc, metallic mpper is formed

3 CrO + 2NH3 I1l gCu+Nz*gHzO

In this reaclion, NH3 acts a reducing agent and thur redu@s CuO tometallic copper, whilc it itsctf b ddircd
to N2 gas.

Q. 10. Corc. HNO, turn. ycllorv ln sor llghL Wty ?

An& ln prc&ncc of aun li8ht, HNO, Partislly decomposes to produce NO2 wiic,l thcD dissohg in HNO! to imp6n
ycllow colour to it.
s'n li6l
4 HNo, 4 No2 + 02 + 2 rLo
Q. I l AluDlnluE coEtrlDcr! can bG us.d for ctorhg conc. HNO,. Erplsll.
Arr. In prclcnce of conc. HNO3, Al bccomcspar,l,vc, ia , a thh protecriv? lErcr of 1l, ddc (Al2O, ir formcd on
iE surface which Prc,vcntt the further adion bctwEcn the mctal 8nd thc acid. Thcrcforc Al co[taincn cgn bc
uscd for storing cono. [INO3.

e. 12. BurnlDg m8g[c.lum contlDua to bom vhllc bur.ttlng ulph[' i.lr ddDgELi.d rt r dropEod hto irrrol
nltrtc oddc. Erphln
Ara Hcat votvcd durlng bumlng of M! l, qultc cnough to deroorporc No !o N2 and 02. Thc 02 thus produccd
supporb comburtion of M& In molrasq thQ hcat Foduccd orlng bumiag, d s b lor quitc rufficirnt to
demmpce NO. Ar a r6ult, rulphur rtop6 bumlng.
e l-1 N8DG str loE whlch lr bo.l.ctrotrlc rlth DltrEtr I n,WLrtL rhrf ?
Arr. Not im ir hchdlonbwlrh co3- ion sirr borh conEin 32 cbcrm!. r.& No3- h, coi- kx lr arro plaoar.
13154
Pradeep's

Q.14. llorv will you prepure u sample of ND, ?

Ans. Bv the action of heavy water on nlagnesium nitride.

2 MgrN, + 6 D2O + 3Mg(OD)2 + 2ND, (N.C.E.R.T)

:,; ry thort-'Answer Quesliong iri6^ - --i;;r:;---

e. 1 What happens when a bornx solutlon is acidlfleil ? !\bite a halanced equation for the reaction.
(,\.('.1r. R.'l:t

Ans. Boric acicl is fornred, NarBoO, + 2HCl + 5HrO .......- 2NaCl + 4I{rBO,
Q. 2. Ry means of a halanced equation show how B(oH)3 hehaves as nn acid in water. w.c.ta.R.'f,)
Ar.. B16H;, + 2 Holi+ [B(oH)4]- + Hro+
(N.C,I!,R.7:)
Q. 3. \Yhut happens when boric ncid is heated ?
3?0 K 410 K Red heat
Ans. 4l{rBO, ' 4HBO2 ------ I-I2B4O7 2BrO, + HrO
-4H2O -HzO
e ('\l( '' 1:' 1( ll ;

Q. 4, Why do boron halides form addition compounds -with amines

Ans. Boron hali<tes are Lewis acids and hence accept a pair of electrons ftom amines to form addition compounds.
Q. 5. \{rite the structtrre ofdiborane.
Ans. Ilefer to Fig. 13.5 on page 13/10.
Q, 6. Why do boron halides behave as l,elvis acids ?
Ans. Boron halides behave as Lewis acids since the boron atom in them has only six electrons in the valence shell
and needs two more electrons to ccmplete its octet.
Q. 7. What are boranes ?

Ans. Stable covalent boron hydrides like BrHu , B4fIl0 , BrH, etc. on analogy with alkanes are called boranes.
Q. ll. How is diborane prepnred ?
Drv ether
Ans. Bl', + 3LiBHo 2BrHu + 3LiF
Q, 9. Wrat is the correct structurnl formula of borax (NarBaO7.10Il2O)
Ans. Na, [B4O5(OH)4] .8H2O'
Q. 10, Why does horon not form 83+ ions ?
Ans. Because of very high lirst three ionization energies.
(N.C:D.R7l)
Q. 11. What is dry icc ? Why is itso called ?
Ans. Solid CO, ; it does not wet the surface when it melLs.
Q. 12. What is carborundum ? V[hat is its common use ?
rtns. Silicon carbide (SC). It is used as an abrasive.
Q. 13, Whnt is the chemical name of freon ?
Ans, Dichlorodifl uoromethane.
Q, 14. What is catenation ?
Ans. Property of selfJinking of atoms to form chains is called catenation.
Q, 15. What is water gas ? How is it prepared ?
Ans. An equinrolar mixture of CO with H, is called water gas. It is obtained by passing steam ovet red hot coke.
1273K
C (r) + HzO (g) + CO (8) + H2 G)

the above reaction.

Ans. C-aCO3 + CO, + H2O -* Ca(HCO3)2
 SOME p-BLOoK ELEMENTS 13/55

Q. 17. What ls the oxldrtior stat ofcnrbotr in each of the follorvign compouEds ?
(a) CO (r) IICN (c) H2Co, (d) C:rC2.
@.cE.nr,)
Ans (a) + 2(h) + (c) + 4 (d)
2
lt. -1.
Wrlte resolsrce structures of CO3- and IICO!
Q. ion.
(N.C.E.EI)

- A.os.
9"
H-O-C:-'- -o
Yot --- o
Resonance struotures of HCO' ion.

&"?T- -.-.4 --o

--o_c \o
ResonaDce structures of Cojz- ion.
Q. 19. What is the state ofhybridization olcartron in
(a) CO!- (r) HCN (c) diahord (d) ersphite,
(N.c.E.ET,)
Ans- (a) spz (b)spG1sp3 1d1ryz.
Q. 20. DeterEitre the oxidstlo[ number ofrltrogeD in
(@) N2O (r) No2 (c) HNo3 (d) NII3.
(N.C.E.R T)
A.rs. (a) + I (b) + 4 (c) + 5 (d)
wtite
-3.
Q.2l ' balol,ccd equatlon for the preparotion ofelcmcDtrl boror by r.drcttoD ofBBt,tth. tydroglD.
A.rls, 2 BBr3 G) +3H7@)+28(t)+6HBrG)
Q. 22. Hot" dlnltrogen pFpared in the laboretory
iB ? (N.C.E.RT.)
A.Ds. By heating a solution of NH.CI + NaNOr.

Q. 23. cile exsmples ofcompounds in which Ditrogen exhibits oxidstiotr stats of (i) --J, (i, + 3 oDd (ni) + s.
t \,.t .1.:.It ! i
Ans. (i) NH, (i) NF, (iii) N2Or.
Q.24. Glv-e one cxample ofa rcactior itr rdhich dinitrogen acts an oxldising agent
0 0 ...- +2 -3
Ans. 3 Mg + N, Mg, Nr.
ln this reactioD, N2 oxidises Mg to Mgz+ and is it.sclf reduced lo Nt.
Q. 25. Give otle example ofindustrial fixation ofnitrogen.
673 K
Ans. Nz + 3 H2 2 NIl3 (Haber's process).
-+ 200 atnl
Q. 26, What is Nessler,s reagellt ? What is its use ?
tu* An alkaline solutioo of K2tIgIa is called Nessler's reagenr. It is used for dercction of NHJ and NHa+ MlLs.
Q. 27. Why dos nitroger fail to forh pDt{halide ?
Ans. Due to abseDce of d'orbilals rn the valence shcll and also due ro high encrsr required for promotioo
of
2.r-electron to 3 r{rbital.
Q.2t. ExPIair why reddish hrown niirogen peroxide on cooling undcrgoec dlmerftndon to glve colourlc6s
dlnltrcgetr tetroxidag
Ans. Because of the presence of ao unpaired electron on N, NO2 utrdergcs dimerization oD cooling to form

colourless NzO4. Z NO, -...- OzN-NO2

Q.29. Name the oxide ofniirogen which is parnmagnetic in the gsseorE 6tate ord diamsgredc i|l thc liquid or the
solid state.
13/s6 Neu' Course Che nt istrg

AIls. Nitric oxidc (NO).

Q, 30,lvhat ls laughlog gas ? llorY is it PrePared ?

Ars. NzO. It is preparcd try heating NllaNO3

Nll4Nor a N2or2rlzo
Q. 31. Name a [itrogen contoining ion which is isoelectronic with ctrhonote ion' ! hot is its shaPe ?

Ans, NO! is isoelectronic with CO3- since both coDtain 32 electrons. Like CO32-, NOt is also Planar'

Q, 32, Whot hoppe[s when concentrflted ritric ocid rcscts with cane sugar ?

Ans. Oxalic acid is formed.

CrzHzzO + 36 HNO3 * 6 (COOH)2 + 36 NO2 + 23 H2O
oxalic acid

Q, 33, Wrlte the formrtla ofthe brown comPlex formed during rlng test ofnltrntes'
Ans. IFe(H2O)5NO+]2+ pentaaquanitrosoniumiron (l).

Q. 34. NAme n nitrogen containing lon whlch is isoelectronlc wlth CO2 ? lvhat ls its shaPe ?

Ans. C.vanamide ion (cN 1-) is isoelccrronic with CO2 sincc both contain 22 electrons. Like CO2, CN; - is also linear.

Q. 35. lvhot happens wher lroD ls dipPed ln concentrated nitric scld.

Ans. Iron is rendered passive due to thc formation of a thin protectivc layer of ferrosoferric oxide, FeO . Fe2C)3, on
its surface whicb preven6 further action.

Q. 36, Give ttvo reoctlons ofozo[e in whlch dioryEen is llot libereted ?

Ans. (i)3soz + o:....3So: 0j) 3 sncl? + 6Hcl + 03-3sDcla + 3H2o

Q. 3?. Whst ls totling ofmercury ? Horv can it he remorcd ?

Ans, 03 oxirlises Hg to Hg2O. The tlg2o thus tormed dissolves in mercury. ds a result, H8 lGes its meniscus aDd
startssticking to theglass. This is called tsillng ofmercury The meDiscuscan, however, be restored bysbakinS
it with H2O which dissolves [1g2O

Q. 3lt. Writc the resontrnce structures ol N2O thot will sstisfy the octet rulr/ , 1l I 9s i , .1r. /.. !.11. ,1/ tn hfit rl i )91 :

*.. ,rt fi4, -*;" = fi = o'

e. 39. Wtot hnppers wheD nqueoos ornmorla ls Ildded drop*lse to a solutlon ofcopPer sulphntc until lt ls ir
excess ?

Ans. 'Ib begin with a bluish white ppt. of Cu(OH)2 is obtained which di$solves in excess of ammonia to form a deep
blue solurion due to tbe formation ofa deeP blue ccrDplex, [cu(NH3).lso1. itt.l te,\-
Q. ,m. Gold ls dlssolved ln squo rr8ln. Glv! cqustlon.
Ars. Au +3HNO3 +4HCI* HAuCll +3NOz+ 3H2O tlJt.t. ttutnhi t99rt
Q. 41. Write the reactlon oforonised ox,?Gn wlth cthylenc'
ADs. Ethylene ozonide is formed. Coosult the text for rcaction'
Q. 42. What are ftlllerenes ? How inony Pentasonll trrld
hexagolal rings are present ln C6o molecule ?

Ans. Fullerenes constitutea new familyofcarbon allotropes consisting oflarge spheroidal nlolecules of compGsition
'12
qr (where'l z 3O). C6o fullerene contains 20 hexagonal aDd PentaSoDal rings
SOME p-BLOcK ELEIVlENTS 131s7

MARKS
Src l-l I 1. How does boroD oc{ur ? How is it extracted ?
t(, l-1 l.
2. Describe briefly how elemenhl boroD can be obtained ?
@,C,E.R.X)
3. Why does boron rescmble more with silicon than with aluminium I
4. Why are boron haridcs and diborane referred to as electro[ deticicnt compouods ? (N.c.D.R.r)
5. Write balanccd equattons for thc reactio[ of elemental borcr with etementai chlorine, oxygen aDd
ritrogen at high temperatures. @.CE.R.T)
6. Explain the chemistry of borax bead !est.
7. Write thc structure of diborane and explain the flature of bolldillg in it. (N.C.E,R.T)
t. How are boron tnhahdes prepared ?
9. Discuss the structure of boro[ trihalides.
10. Why do boron trihalides behave as Ler*,is acid.s ? Discuss their rclative acid strengih.
l1'DescribethesbapsofBF3andBH4-.whattypeofhybridizationcanweassigntoboronineachof
these compounds ? @.C.E.R-T)
12. Lisr some uses o[ boron and its mmpounds.
srr I-t 5 t3. What is allotropy ? Name two elements which exhibit allotropy.
14. ExplaiD the differencs in the properties of diamoDd and graphite oD the basis of their structures.
(NC.E.R.T)
15. Account for rhe following:
(, Dtamond is hard bur graphite is soft.
(r'i) Graphite is a good conduclor ofelectricity bur diuntond is nor.
(irr) Diamond is used in jeweltery
(iv) Graphite is usedas a lubricant but diaDond is used as an abrasive.
16. What are fullerenes ? I{ow are they prepared ? Discuss their structure.
W,C.E.R,I)
17. What is catenation ? How does it exptairl huge numbcr otcarbon compounds.
sr( l-r o. lt. What is dry ice ? Why is it so called ? Give tts one use.

19, Account for the todc Dature o[carbon mo[(xide.

20. Write equations for the production of water gas and producet g8s fiom coke.
21. ExPlain the following : (i) Carbon dioxide turns lime waier milky. Bur if it passed for a long time, the
solution becomes clear again.
(r'l) CCla is resisranr to hydrol)sis. (ifi) Frcofl is used as a refrigeraDt.

22" Give equations for the follo\ying :

(i) Preparation of carbon dicxide (r'j) Basic properties of Eodium carbooate solution
(iri) Formation of aceryleoe.
23. Why carboDates and bicarbonatcs ofalkali metals bhave as weak bases in their aqueous solutions ?
24. What are carbides ? Name the different typcs of carbides. cive one o.ample oreach typ.
25. Give equations for the PreParation ofacttytene ftom calcium carbidc and methane from aluminium
carbide.
26. Ho\P is carbon disulphide prepared from naturalgas I How is cellulose converted iDto (i)viscse rayon
(ii) cllophane ?

27. Discuss the structures of CO and CO2.

2t. Write equadoDs for the following :
(i) Carbon disulphide reacts with qH5OH in prescnc of NaOH.
't
3/s8 Pradccst's NeV Courrse Chemlsirg@
0i) CsrboD disulphide reacts with Cl2 in prcsence oiierric clllondc as catalyst.

(iri) Malonic acid is trested with P1olo.

29. Wtite balancd equations for the following reaclions.
(4) Combustion of CaHlo in a limited supply of rxygen to form carboo monoxide.

iltint. 2 CaH10 G) + e oz G)+4 CO (g) + l0 HzO (f ;

(A) The reaction otcalcium carbide \rlth water to form acatylene.
(c) Tbe preparation ofcalqum clananricle from caloiunr carbide and nitrogen.
(d) Formation of hydrogcn clanide fron] methone and ammonia. (N.C.E.R.T\

lHinr. cH4 G) + NHr (g) L'1"8t hcN (q) + 3 lr2 G)l

1500 K
30. What is freon ? How is it prepared froDr CCl4 ? Writc its impoflant uses.
s!c.ll.ll 3l, Hon,willyou prepare diniirogen in ihc laboratory ? Why is dinitrogen someNhat inert in nature'l
lr, l-1.12.
32. Discxss ooe method each for biological and industrial fixation of dinilrogen.
scc.l-1.1-1. 33. Briefly discuss the manufacture of ammonia by Haber's procss. Explain clearly the effect of
tmperature and pressure on the process
34. Discuss thc coDditions required in thc Haber process for the lnanufacture of ammonia. (i{CE..R.I)
35, Explain
(i) Ammonia is a gmd complcxing a8ent (ii) Shape of ammonia molccule.
src ll.lJ. !(. List the odde,s ofnitrogen and give oddation numbcr ofnitro8en rn each oxide- Give their structures
l(, 13.15. and uss.
37. Illustrate hot Ditrogen compounds provide g(x)d examples of multiple boDdiDg aod resoDance.
(N.C.E.R.T)
3& r'kitc tbe resonaDc Lewis srructures for N2O, NO2 and NOt. N.C.E.R-T\
39. HoI is nitric acid manufacturod ftom ammonia ?
40. Wtite balancd equation(s) for tbe manufacturc of nitric acid by the oxi(lation of ammonia.
(N.C.E.R.T,)
41, Oive three reactions to show lhat nitric acid acts as an oxidising a8ont.
42. What is the actioD of coDc. nitric acid on :
(a) acidified ferrous sulphate solution (D) PhNphorus (c) coppr'l
43. What happcns when dilute Ditric acid reacB with coppr ?
44. What happcDs when ammolia gas mixcd with oxygen is passed over heatcd platinum catallNl I what
is the utility of this reaction in iDdustry ?
45. What is ihe structurc of oitric acid ?
46 Illustrate how a metallikecoppcr csn give different productswith nitric acid. Give balanced equations.
47. Desaf,ibe the u6es of ammonia and nitricacid. (rt{Cr'.R?)
,18. Identify the products of lhe following reactiom. Give balaDced equatioDs :
(i) MB3N2 + H2O (ii) 12 + HNO3 (conc.; .- (iii) Cu + HNo3 (conc.)
(iv) Li + N2 + -(v) HNO3 + PoO16..- - (N.C.E.R.T)
scc l.r.l6. 49. (o) Give one laboratory method for the preparation of dioxygen 8as.
t,) ll.l7.
(6) Why is MnO2 added to potassium chlorate for getting diorygen ?

(c) What is tbe action ofwater on sodium peroxide?

50. Ho is dioxygen obtained fiom liquid air I
51. How does diqygen react with sulphur dior(ide, anmoDia, hydrGhloric acid and nitric oxide ? Staie
the conditioDs uDder which thesc reactioDs take Plac-
 SOME p.BLOCK ELEMENTS
13/s9
52. cive at least four uses ofdioxygen.
53. Classify differcnt oxides on ihe basis of their acid.base character.
54. Classi$, the follo ing q.,mpounds into acidic, basic and amphotcric oxictes :
SrO, Si02, Al2Oj, N2O5, SO2, P1O6, Ct2O7
\*tite balanced equations for the reactioo ofcach of these compounds with watsr, a base or thc acid
as the case may bc. d.C.E.R.T.)
[Ans. Basic: SrO, Amphoteric: AlzO3 ; AcirJic : N2O5, SO2, p4O6. C12O7]
55. How would rou convert diGygen into ozonisd qygen ?
56. what is the shape of ozone morqrre ? write Lewis dot structure(s) for ozone morecure and exprain
why O-O distancs iD ozone are equal. W.C.E.R.T.)
57' Give an account of the struc.ture of ozone ? Give reasons for rhe folrowing. IJ.)th o-() bonds in
03 have same length.
5E. Hor/ does ozone react with KI and lead sulphide?
59. Give at least two uscs ofozoDe.
60. What is the importance of ozone for plaDt and animal life on earrh ?
d.C.E.R.T)
61. Give two chemicar properries of ozone whish show that it is a more powerfur oxidising ageDt
than
ory8en.

CARRYING 5 oi moro MARKS

t. Ho'p does boroo occur io Dature ? How is it xtraclcd from boric uide and boron harides ? Give
its
r',clioDs with air, halogeDs, concentmted nitric ac.id, coflcentrated sulphuric acid and fused alkali.
MeDtion a few important uses of boron and its mmpounds.
Giye thc preparatbo of borfi ftom thc mincral colcrnanite. Briefly describe its properties aDd uss,
Sec.l3.6 I Explain thc differcnces in propertiEs ofdiamond and graphite
ba;d upon rheir structures.
to 13.10
4. Name tlvo ides ofcarbon. Disc.uss briefly their preparation, properties and uscs.
5. What are carbides ? Ho aro they chssified ? Discuss one metbod ofpreparation, two propcrtics
and
two uscs of eaci tyPe
6. Discuss the methods of prcparation, properties aDd uses of halides of carboD,
Hof, is carboa disulphide prepared ? Discuss its importaDt proprties and uses.
Scc.l3. t I t. Holtr, is dinitrogen prepared ? Dsqibe irs propcrtii anO uies.'
to l -1.15

9. Ho$, is ammonia obtained by Habcr,s process ? Whar are the optimum condilioDs to obtain
its
muimum yield ? Give bahncEd clEmical eguations for its reactioos with halogens and orygen.
10. Describe ostwald procers ior tb rDaDufBcture of nirric acid. Descrite its
action on metals with rhe
help of balanced chemical cquatims.
11. Name the various oxid6 of nitrogen. Give thcir oxidation states and draw thetr strucrures.
Sc(-13.I6. 12. Dis-trss briefly the methods of prEparatjon, proppniEs and uses of dioxygen_
lo 13.17.
13. Hof,, are the didcs ctassified ? Give two eEmples of eact type.
14, H-ow h done prepared ? Disanss bric0y its qidising propcnies. Also comment upon
the structure
of szooe moleqrle.
 IONAl-"U9,E FULlN.FO,Rh/
1. sodium borohydrtrte, Na[BHa] is obtained by heatin8 sodium hydride with diborane'

NaH + B2H6
j' Z NuSHo
2
of aldehydes and
NaBHa mild reducing agent and is extensii'Ely used io organic chemistry for the reduction
is a

ketones to the corresponding alcohoh and also for the reduction

ofcyaDides (R-{
= N) to 1'amiDes
(R-NH2)'

2. Carbon suboxlde
with P4Ol0
Carbon subodde (ca02) is preParcd by dehydratioo of malonic acid
Pooto
HO-CO-CH2-CO-OH o-c=c=c-o+2H2O
Carbon subo{dc
Malonic acid
Properttes' (i) Carbon subsxide
-
is a linear molecule
yellow solid' and at
(ii) it is a foul smelling 8as, b.p. 279 K At roonl temPerature, the 8as Polymerises to a
higher len]pertures to red and purPle solids'
and with NH3 to forn]
(ir.j) Ii rcacts with H2o to rorm malonic acid, with Hcl ro form malonyl chloride
maloDamide.
qO2+H2O .- CHr(COOH)z
Malonic scid
qoz+2HCl * CH:(COCI)z
Malonyl chloridc
qo2+2NH3 .- CHz(CONH2)2
Malonamide

3. Carbon-nltrogeD cotEpounds. (i) CalciuE cyan-am-ide' Ore of

the most important:T,!3:l1t^t-:Ht::E
cilcium cyaDamidc, CaCN2 [t is obtained by the reaction ot calclum catDloe wltn
both carbon and nitroigen is
nitrogen at 1373 K

caq (r) + N2 G) '3"{ cuNCN(')*c(')

CalciumcySnamideisusedasalertilizer.ItisalsousedforthemanufactuleofmelamingplasticDeededfor
makinS rron- breakable olbckery.
and sodium
[i; Soaiuur cya ad., Sodium syanide is formed when calcium cyanan]ide is fused with carboo
carbonate.

l3/60
SOME P.BLOCK ELEMENTS -t3161

ADDtnONAL USEFUL TNFORMATTON c o n19a.

Crciq+C+N%CO3
*,
-^O, * rn"Oa
Sodium cl'aaire b usd fu lhc crtrdi)tr of
td ad sih/er from thcir o.Es.
(lli) HydrocFoic acftL HG{ B.produced vbcn sslum c}.ar*lc b rrEaaed q,iah stIoog
cohurlss gas altd bebaris as arEat rid in aquous solutim (px.'_ 9.o)-
scirs HCN b a
Idufihly. HcN b".brabJt;i.,
olamDodia m r tatre ar high tcDpcrafur.

cH.6) + NH3e) ++
lJflI K
HcNG) + 3s2c)

- 'I}letr ingqstlon or inhata]ioo (:an

tead polymers and adiponitrile which Ls
used rial for rrylon{5.
tion of HCN by 02 io the prcsence of silver as a catal)lst or
by the oxidation of CN by Cr2*
A
4tlCN +()2 ...- 2(CN)2 + 2
2()
2Cuz+ +4CN- < 2CuCN + (CN)2
. lt b a linear molecule- Cyatrogen resembles halogeos in
r'p For example. in basicmedium,likc halogeDs,ir undirgoes
disp

(cN)2 + 2OH- + CN- + OCN- + H2O

(v) cl''rtrmide, H2N.N. liea.,ent or caNCN with warer giles cyanamide which b a sorid with
m.p. 3 r8 K.
CaNCN + H2O ...- CeO + II2NCN
It b ussd iD tbe prepar?tion d guaiidirE ar,)d ,hi.a.no-
4' Nitrous acid (HNo2) a{rs as a srroot Gidbing ageDt sioce it can
bc easiry reduced to qides of Ditrogen.
lD cootrast, Ititrous acid (H Noz) call be ei6er reduced to nitric
olide (No) or otrdlsed to nitric acid and hence it
acls both as an oxidising os wcll as a rEdtrciDg sgcnt
2 HNO2 2NO+H2O+[Ol
-
...-
HNO2 + Iol HNO:
(!) misirg proprtis. It qidiss tl2s to s, H2so3 ro H2so+ sncr2
in HCI to sacl., ac.idi-6ed Fesoa to
Fe2(SOdr3 aod md$ KI ro Iz.

H2S + 2 HNO2 S+2H2O+2NO e

H2SO3 + 2HNO2
-
-+ HrSOr+H2O+2NO
SnC! + 2HO + 2HNO2 -.- SDCta + 2HzO + 2NO
2 FCSO. + H2So. + 2 HNO2 ...- Fe2(soth+2H2O+2NO
2KI + 2HNO2 2KOH+12+2NO
(b) Reduci[* proFrties. It reduces acidified -
KMno., acidified t<2cr207, barogens to harogen acrds and
H2O2 ro H2O.

2 KMDor + 3 .* Iqsoa + 2 Mnsor + 3 lt2o + i HNo3

H2soa + 5 HNo2
l9Ct2O7 + 4 H2SOI + 3 HNO2 ..- IqSOI + Cr2(SO1t + 4H2O
+ 3HNO3
Cl2 + HzO+ HNO2 2HCl + HNO3
H2O2 + HNO2
-
_H2O+ [INO,
 Pradeep's

c.g*s.f- * F*l,l.T- { fuI Al N S ) S llE C l A L

Q. l. Boric ocid crn be titrated ogritrst sodiuE
hydroxide uslng methyl orong. ss lndlcrtor oEly
:F A
-_\u_.tlt, ,r?- n
ln the presence of polyhydrcry comPounds like
catechol, msn[itol et.. ErQlain. _ )B:r;
B(OH)3 reacts t'ith NaOH to form sodium ,i/ ,i/ -
metaborate.
B(OH)3 + NaOII .- Na+BO; + 2H2O
+lA
The end point during the titration ofH3BO3 with
NaoH is oot sharP si[c'e NaBoz undergoes ex-
.. H ,ii..- _
)-B-F'
..
\ "
lo Eive backH3BOrand NaOH
cessive hydrobdis ?'l
..1
-F: :i//
+
NaBO2 + 2 H2O <+ B(OH)3 + NaoH
However, wben certain Potyhydrory compouDds Duc to ahenc of lotre pair of electrolr3 on H'
such as catechol, glycarol, mannitol or sugaB are atom, this comPensation does not occxr in BH3'
added to the titratioD solutioD, the metaborate
ID otber words, electron deficiency of B stays and
ion combiDes with Polyhydrory comPouDd to
hence to reduce its electron deficiency, BH!
form a comPlex.
OH dimerises tq form B2116.
z (All- + Bo'-
' (D) Beaus of double boDd charactr of B-F
\l\oH -2H,o bonds in BFr, it has a thortcr E-F bond leD8h
Catechol
than in BF;.

[@:>"<:r@] Q.4. Nttrous o de suPpods combustloD Eore

Atrs
rously thsr olr. DQlsln
N2O dicomPoss to produce 02 which is about
YiEo-

Due to ttle formatiol of this comPlex, BOt ion

Hcat
does not u[dergo hdrolysis. As a rqsult, boric 2NrO-2Nr+O,
acid beha\,ts as a stroog monobasic acid and the
end PoiDt can thus be easily detected' lR of the volume of gases Produced
(2N2 + 02) while air cootains 02 which is about
Q.2. Commcrd.et nitro,Son is pass.d through coPPer
driF k.pt ln artmonla to remore oxygem' Bplaln' U5 of its volume. Due to this greater uygen
ADs. Copper dissolves in ammonia in Presenco ofo2
content, N2O suPPorts combustion more
to form blue cotourcd tetrammine coPPr (II) vigorously than air.
hydroxide. - frlt
Q,5. thc cheEtlcal rerctions sssociatcd with
rbrc". rltrg tcst,. (I.I 2000t
2Cu + 8NH3 + O2+ZHrO-
2 [Cu(NH3)a] (oHh Ars. Refcr to PaSc 13/42.

Q. 6. ? Glve cheEi-
orar
As a result, commerical nitroge[ is freed from condltioD$ ltHte
traces of 02 Presnt in it. roctlon wtth HCL

Q.3. (4) lM|rby BFr tdsts thcncs BH3 doct nof (II.T 2002'
(r) CorDPore the B-F bood length ln BF, and Ans Na2BlOz- 10tI2O + H2SO. (cotrc.)-
Bonx
Bra. Na2SOr + H2B.O? + 10 HzO
Ans. - p, bck bondinS, the lone Pat of
l'a) Due lo rrn Tetraboric acid
efia,ont o-f F b denoied io the B{tom' Tbb + 4 H3BO3
th deficiency of eledmo's oD
H2B.O7+5H2O
deloelizdon reduccs
Boric aci''
B thereby iDqeasing the $ability ofBF3 moleule'
SoME p-BLoCK ELEMENTS
13/53
Rcd h.lr wben oraDge solution turns green due to reduc.
2 H,BO, B2O3 + 6H2O
tioo of Cr2O? - ion to Cd+ ionswhite CO, passes
Boric didc
A out unreacted.
B2O3 + 3 -
ttlg * 28+3MgO Why BBrJ is o stronger Ijwis acld as corhpaEd
For strudurc of ll2tl6, rcfcr ro page l3llo. With ao BFf though lluorine is Eore clechDeg.tive
dry HO, B2H6 cryohs H2 gas than chloriDe. (c.8.s.E. PM.t 2004)
qH5o + [r, AIts. The B atom in BF3 and BBr3 has oDly six
\H6+ HC/,11tn
-
7. (l) D6crtbG nlth cqustlior ele{lroDs in its yalence shell and hcnce can ac-
Q. rhsthappcrs vhe! oept a pair of electrons to mmplete its octct.
carton ls heoted wlih coac ErSOa i
Therefore, both BF3 aDd BBb act as Lewis
(Ued BqgoUEE. 2O0J) acids. But in BF3, tbe sizes of empty
(ll) Stste hoti' rvil you cepsratc CO, ard SOz
hrbitat
flom thelr lrixtttr ?
AJrs. (0 H2SO1 oxidises C to CO2 aod itself is reducd
to so2
tlrc electon.defrciency of boron decreoses- ln
+4 +4 contrast itl BBr3, the size of sporbiral of Br
C + 2 H2SO. * CO, +2Se + 2HrO containing the lone pair of ekrtrons is much
(n) Sincc the O.N. of C is CO2 is + 4 whiclr is rhe biggcr rhan the empty 2p-orbilat of B and hencf
doDation oflone pair ofeleckons ofBr to B does
ent. As a result,
much higher in
ence BBr3 is a
strooger Lewis acid than BF!

I.I.T, UfiAI
A
GnJ:GzOu crro,
Afim. dichrcmatc Grccn rcsidue,
a
+ N2 + 2H2O
Ars. (i) Since the gas E formed dens white tumcs with Colourlcss
ga6, C
HCl, it nay be NHr-
A
(r, Since gas E is producd whcn a whit solid D 3Mg+N2 Mg3N2
mntaining Mg reacts witb HzO, tbcrefore, D - Ma& nit idc, D
mutl be magnesium ninide. MgrN2 +6H2O 3Mg(OHt + 2NH3
(4r) Since white solid D i?. magDcsium nirride, is
prod ucd wteo a colourless gas C reacs wittr
-
.._
Ammonia, E
Mg, NH3 + HCI NH.O
lhercIorc, C ,flr/-tt be N2- (Dcn6c whitc tuo6)
(iv) Sinc a colourless gas C ie. N2 along wirh a Q. l. ColciuE burDs lD Dltrogc! to p.oduce o *hlte
pordcr rtlch dlEsolv.s iD surnclent water to
T
chronic oxi.le (C.zO"). All the reactioos invo#
in thc qucstion are :
',1,
13/at Pradeep's
Ca(OH)2+ CO2 * @Oi + UzO
A
Ar.r 3Cs + N2 .* (4Nz (M'l6t'tt)
D

Q. 5. CoEIould X oD lductitlt
sith LtAlHa givcs e
C5l'nitlilc
(jriiElda')
CtN2 + 6H2O + 3Ch(OH)2 +2NH3
@*fte ed ) (A)
+ CO2 + Cacoi I tl2o
C5(OH)Z brD.tir dY otd irs rc.ctioo tlth rir' Drorr the
(u,aa@) (o,i[rt.) stnrctuE ofY. [I.I.I 2N1\
Ail* Sr.p l.Ib.t ramirv tc t futinnlllo utd
tcllrtozd.ryrrd\
I Sitrcs the hdride Y rEaca with air formiDts
Li-, t i"ao",it r+- ,Y ,nufl bc a" N'id' oI
bdc,.
(ii) %H -- 2t "r2% rcivat)
:. %B = l@-21'72 = 7a A%
tiors' H= ?!72 = 7'12 21'72 = 1 1 3
1+q,
25(rC ... EF. of Y = DHr
AE (t) NILNO, + N2O + ZHzO
(A l Nrtt@ Irlqttnl sirlcE Eu fuB tfltD tFes of h!,+idst ic',
cidc (B) Gie (c) Brur+a Filrdq@s) aad BiH'+6 (0ac,F
(t:i) l0N2O + P4 drtaan t) thcfue, Y mulr b I nilobordDc
Nitrut. (ri& (B) sitb n=2 TbB, }fE ofY = 82[16. IfY is B2H6
+ lONt + P4Oro (dihmc)' thca 13 dtttclurE mrsr E a hlbws :
tto+hott' Fntcidc . Brid[Es E-....H
= 133 Pm
(WabsW't\ Turmimt F-H = 119 lrn

,'^'--{'
-..rr,,'\x
er. (i) Sincr clmcat A boms b
iini: cmPoud B' thaefct
nfuid. W2.To fudrE tfu ttruz o{ tlu cott'
'#ffiffi @L
fu cmpurd Y ia, Bztl6 b lirEcd by rcduc-
fin dcryrdxrfrh LiAlH., $Grefac' X
(iir) Sioce C EG milky dr hrslbs Coz'
musr cithcr BC! r BF3.
c6cr
(ivl tf C b cahiuE tyotoOOc, ltco A mud be 4BF3+ 3tiAtH. ;- 282H6 + 3 LiAlF.
irfi*um aod B mutt u ('hiutrt Ditrilc (ctN, xY
A[ the rEacti$ imlt/Ed itr tbe Srcstbl can ocv TE cgrralim rcPrEsGotiDE tb raion of Y$ilh
E.4hitcdEflbx|l: q m, bcYin a6f&]l:
A 2\O3 + 3tl2o
3(h+N, C.bNz qH6+3O2
(A) - fliDore,Y - Bod t iai'.
c.r.'nEi& (B)
CtNz + 6H2O * C8(OHL + anHs ThusX=BPrandY-rfe.
(B) (g (D)
 SOME P-BLOCK ELEMENTS
13/6s

/I,TULTIPLE CHOICE UESilOA'S

l. An aqueous solution of bord is (3) N?Os (r) N203
(a) basic (b) acidic
(c) NrO (d)No.
(c) neutral (4 ampno(cric.
lZ Wbct of lte tu[onht mE dE h!&oE! wirh
a Oftbohoric acid when heated to red heat givcs dil HNq ?
(4) inctaboric acid
(c) boroD trifiide
(b) reiraboric acid (c) Mt @lzr
(d) bore (.) Al (d) sn-
3. CarboruDdum is Thc cfiipuDihhht givrs offGJtrn dt [rodcfale
(c) Boron carbide (6) Silimn carude lreatio! b
(c) Aluminium cart*re (d) Catcium carffie. (s) qrFic circ (6) mcrrrrtu cide
_ 4. Dia[xrod aDd graphite are (c)zinc'ib ar***r;Tl?rrr.,
(a) HqDotogucs A[orropes
(D)
G) hoE crs (d) None of the sbotE. 14 Tbe boDG prcsqt in N2O5 are_
5. Whict of rhe folbwing is rhe hardest SlBtancc (a ) only ionic (6) orraleDt ard c@rdinate
hwn ?
(c) only covalnr (d) cotalot aDd iqic.
(4) Graphite (r) CarhtruDdum
(c)DbrDood ll.t.T leE6)
(d) Coke.
Which of Ur ffirring b thc rncr ccrnlm , f s. TlE brwn rbt co4a comportrd b formutarcd
used
refriFf,ant ? I [t(HrO)rNO+Fo.. Thc qitatbn srele ot
(4) cFq (r) ccl3Br iroll N
(c) CFro (4 szct. (o) 1 (b\ 2
1 Whii of thc folowing b the h6r $abb caftm (.) 3 (d)4. t I.L'l: t9u7)
halide ? 16. Which of the fooolving Gides of nitrogen b a
(a) COa (D) CF. colourcd gas ?
(a) Nro (b) No
(c) CBr. ct+
(d)
& Caibon torms a hrge nuDk of mIulnds (c) Nzoa (d) Noz- U.t.L ts87)
bc_
cau6c it has 17. A,lqltsr te trihalides of niarogen, whirl one is
(a) t6riable valeoc, (D) I-ov elcrtql afriry least lEsic ?
(c) High bizaaiD eocrg/ (a)M: (D) Noj
(d) Propcrty of catcnatiorl (c) NBr3 (d) NIr. \t.t..t: 1s8T)
9. 'I}lling of me{qrry b duc to the tuDatir d ft. Th light litrt bolts iD the atnGphere cause the
(a) Mcrorric qirc (D) Merqlrqrs qilc formation of
chlorid,c (d) Merqlrqls dtloride.
(c) Merorriq (a) No (D) Mr3
ro. The qilc whit b smpltorqic b (c) NHaOH (4 NII2oH.
(a) H2o (D) cao
U.t.'t: 198E)
(.) Alzor (d) ct o"_ lt CoDceotratcd HNO! reads sith iodiDe ao gii/E
ll. The qide of oitrogeo obtainql by desratin of (a) HI (6) rror
oitric aci, bt Clqhqus pcnmide t ('c) HOIO2 (d) HoIo3. (1.r.1: leEe)

l.a Lc 3.0 6t 7. t d ,.b

ll. d lL a r3,, 1t I0. c
16. d 17. o l&r 19.c
13/66 Pradeep's

acid is PolYmeric due to 2t. When formic acid is treated with conc. H2SO4, the
20, Boric
gas evolved is :
(s) lts acidic oature
(a) H2s (6) So2
(b) The prcsenca ofhydrogen bonds
(c) Its nlo[obasic nature (c) Co (d) co2.
(d) Its geometry. ( (;.E.RT 1990) t,ll L,\'R Atlalnbnd i99nt
21. Which will quickly ab'sorb o,(ygen the moststabb form ofcarbon
29. Thermodynamically
((,) Alkaline solution of Pyrogallol s
(b) Cooc. H2SOa (c) Lime water (a) Diamond (b) Graphite
(d) Altaline solution of CuSOo. (c) Peat (d) coal
(C.B.S E. Mcd. 1992) (,rl l"N'k it)')ot
' 'llht1nh!1d

22. When ammooia is passed otr'er heated Cu, it is

30. The metal which reacts with HNO3 to give five
oxidised to different products dePending uPon the concentra-
(o) Nz (D) NO2 tioD ofthe acid is:
(c) Nro (d) HNOz (.,) Cu (b) Fe
( Roorkee 1992) (c) Zn (d) Ar.

Pure nitrogen can be PrePared from

t'lI I"l'lt ttlltltthtd lt)e('t
23.
(a) NHaoH (D) caiN2 31. Which of the followin8 dides is neutml ?
(c) NH.NO, (d) Ba(NO2)2. (a) co (D) Soo2

(A.FM.C. )993) (c) ZrrO (d) SiO2. t:.t.T te')6

24. All ihe follorving decompose easily on heatinS to 32, The test of ozone can be done bY
Sive oxygen as tbe
onty gaseous Product cT ePt (a) As (r) He
(a) Lead nitrate (D) Potassium chlorate (d) None of these.
(c) Au
(c) Mercuric oride (d) MaDgaDse dicride'
(D.C.D.E. 1991)
resPect to 33. Whicb one of the followins has the highest dipole
25. Identiry the incorrect statement wilh
ozone moment ?
(a) Ozone is formed in the upper atmcphere by a (a) NH, (D) PH3

photochemical reaction involving dicfiy8en' (c) sbH3 (d) AsHs

. (r) Ozone is more rcactive than diGygen l('.ll s.li 1997
ic) ozone is diamagnetic while diqygen
is
34. Among the followiDg species, identify the isostruc'
ParamagDctic
turalpairs.
NF3, NOt H3O+ HN3
26, ' BF3 ' '
is false ? (a) [NF3, Notl aDd [BF3, H3o+]
(4) It scls as a moDobasic acid
(D) IMr, HN3l and [No3- , BF3]
(6) It is formed by the hydrolysis of boroo halides
(c) [NF3, H3o+l and [Not , BF3]
(d) [NF3 , H3o+lard {uN, , BF3}. , ,

35. AmmoDium dichromate is used in some fireworks'

cPt
(6) B2(cH!)4t12 The greeD coloured Powder blo$'n in the air is
(a) HrBOr
(a) CrO, (6) Cr2O3
(c) B2(CH3)5 (d) NaBH4.
(c) Cr (d) Cro(o2)
t(:.8.5 D. P.J[.T. 199J)

.,AERS
25,.1 26..t 27. c 2t c 2.9.b
35. D
 SOME p-BLOCK ELEMENTS
13167
36. In graphite, elecrroDs are 02 molecule is
(a) Localized on every third carbon
(4) paramagDetic (D) diamagneric
(r) Preseni in anribonding orbirals
(c) Localizcd on eacb carbon atom
(c) feromagnctic (d) none of these.
(c.PM.T. 1999)
(d) Spread out belwceo the structure
4. Io thc OstraEt frcss for the manufacturc of
t (..8 S,E. t!,tLT 1997)
HNO3, rhe catabsa used is
37. Sodium Ditrate decomposes above g0O"C to givc
- (d) Mo (D) Fe
(c) Nz (D) oz (c) Ni (d) P..(M. P. C.E. E. r e99)
(c) Noz (d) N%O tessJ 41. Which is detecied by Nessler's reagent
U.r.T ?
3t. Which of the following does not shou, electrical (a) NHo+
conduction ?
(D) Moo.-
(a) Potassium (6) craphite (.)P4- @oq-.
(c) Diamond (d) Sodium. (M.P C.E.E. 19ee\
(c.B.s.E. P.M.T t99e) .l& Conc. HNO3 is stored in containers made up of
39. Percenrage of tead in lead pencit is
(o) cx (b)tu
(a) zerc (b)N
(c) Al (d) sn.
(.) 80 (d)7o.
(HaOana C.E.ll.T 1999)
(c.B.s.D. PM.T 199e\
The correcl struclurc of Fc(CO)s is 49. Which of the following leairs lto residue on hea!-
in8 ?
(a) Octahedral (r) Tftrahcdral (a) Cu(Nojh (6) NaN03
(c) Square ptanar (d) Tigooat pfamidat.
(c) Pb(No3h (d) NH.NO3.
(c.B.sE. PM.T.2000\
41. Thegeometryand the type ofhybrid orbital presenr (B.H.U. 1994 ; Haryatu C.E.D.T 2000t
about the cnrralatom in BF3 is S0. bond lensth (deqsins) in
(a) liliear, sp (D) trigonat ptanar, ,p2 ryrffi.ffi
(c) tctrahedrat, rp3 (d) gSamidat, sp3.
(a) 02 > H2O2 > 03 (6) Or > 02 > Hio2
(c) H2O2 > 03 > 02 (d) H2O2 > 02 > 03.
42. The mrrect order of incrcasing c--o [lj',:ili; (D.C.8.2000)
ofco, cO3-, CO2 i. sl. A metal X on hcating in nitmgen gas gives y. y on
(c) cor2- < co2 < co (D) co2 < co32- < co treatmenr with fLO giv6 a colourlss gas which
when posscd through G\SOa solution givE! a bluc
(c) co < col- < co2 (d) co < co2 < co3- c{lour. Y is
tl.l.7: I s99 )
(4) Ms(Nor2 (r) Mg3N2
43. In compounds of rhe rl,pe ECb, where E B,
= BAs
or Bi, theangle Ct-E--Clfordifferenr Eare inthe G)Mr (tr) MgO. @.c.n. zooot
order 52. Ammonia can be dried by
(a) B > P =As = Bi (a) Conc. H2SOa
(D)B > p > As > Bi (D) PlOro
(c)B < P =..\s = Bi (d)B < p < As < Bi (c) CaO (d) anhydrous CCt2

44. on hearing ammonium o,"o.ro,r,::';"";;] s3. The hybridizrtion of

evolved is "r"ri.
Nor+, Nor- and NHo+ are
".bi,"b "rlil:;Jl;;
(a) oxygen (D) ammonia
(c) nitrous odde (a) rp, sp3 and.rpz respectivety
(d) niljoger.. t LL t: lg99)
(b) sp,.rp2 and sp3 respectively

36. d 37. b 3t. c

t?s
39. a 4tb
46. d 47. d ,lE. c 49. d 50. c 51. b
42. a
5Lc
4.d 45. a
13/68 Pradeep ;

1c; rp2, rp and sp3 rcsPeaivetY (c) N : pyramidal, rp3 ; B : ptanar,.rp2

(d).rp2, spl anrl.rp rcspccrivrly

(l.l.T 2000) (.1) N : ryramidal, ryl ; B : tetrahedral, rp3
54. Among thc follrsiog the elcdrmdcfcicnt corn- iI I T: 11!5t 20021
pound is 62. Which orle of the folloviDg is atr amPhoteric qide ?

(a) Co.o (D) PcI5 (a) RzO3 (b)7-ro

(c) BcCl" (r) !,( rj (c) Nazo (d) soz
(c.B.s.h:. Pnr.T 2ooo\ (A.I.E.E.E. )003)
55. whicll of thc folbwiog alb6oPic fGrtrs of carboo Wbicfi of the folbs,ing molccular sPeci6 has uo-
is isomorPhous with crr6tallinc silicon ? Fird clectron(s) ?
(?) (;raphite (6) c,@l (a) Nz (6) Fz
(c) Coke (d) Diamood
(D.A.M.C.D.T 2001)
(.) oi @) o?z-
(IlT lest 2002)
The t ?c of trytridizetim of ho in dibtr8[c1s
a. Gmphite b a sofr solid lubricant cxtrEmely diffiqrlt
(a)rpbybridiztioD (6)sp2-hybn-dizatin to melt. The rEmo for thb anomabus beiaviour
b that graphile
(c).rpr-@idbatbf kDtfdz+lybadD5irjg.t
(c.B,s.E. PM.T 1999) (c) has carboD atofls arrall8gd in large Plats of
rings of stmngly bouDd carbo[ aroEls vrith PEak
s7. Whrt is lbc prduct fGmod shen @nerdswiih interplate bonds
rDcrqry ?
(D) is a noD-crystalline substanc
(r) Hto (D) Hho2
(c) b an albtrwic torrn of carkro
(c) Hg2o (d) Hgo2 (d) has molerrrles ofvariable molctular massEs like
(E.A.M.C.D.T 2001) polyme rs (A.LE.E.E.2ooi)
Wbq! amErmia b pM orcr bated coPPEt Ammonia fqms thc compk ioo |C\(NH3LF+
qlle, metallic mpper b obtaincd. Ttle reactb with coppet iolls in alkaline solutioN but oot in
sbors that ammonia b acitic s.rutims. lvhat is reasoo for it ?
(a) DefrJdrating a8Bnt (D) AD qidilint 88snt (a) Crpper hrdrcdde is ao amPhoteric s.rbstancr
(c) A reducint agE rt (d) A nilrati4 stcDt (')to acloic solutbos, hdration protects Cu2+
(M.P PE.T 2oo2) lons
(c) In acidic solutio$, proiots coordiDate witb am-
h Nor- ioo, the numbr of hd Pair atrd lme pair mooia moleorlcs formiog NHa+ ions and NH3
of clrcalG cr nitrogca atom arc molecules arc not available
(a)22 (6) 3, 1 (d) ID rlk llne solutid\ solublc Cu(OHL is
(c) 1,3 (d) 4, 0 prccidtated whidl is sofublc in cxcess of any
(c.B.s.E. P.LLT. 2002) alkali Q1.1.11 F,1, 200.))
A mixture of dlccntratcd HCI aDd HNO3 mad Whici of thc fo[o$,int b ttot 8 Protooic acid ?

in3: I ratio cortairB (a) B(oH)3 (6) Po(oHt

(a) ClOz (b) Noo (c) so(oHh (d) so2(oH)z
(c) NCl3 (d) Nzor (c.B.s.L. M.T 2003)
67. H3BO3 is
5r. sFiry rho oqrtmtin (a) MqEhicdld Irwb il
trjdririiath of N ard B atoos
of BF3 and NH3
"*.Stffi'#
in a : I co.nd6
1
(6) MomBis Eak BrqBted Ecit
eod
(c) Mo0oh.et ad lroog t th id
(o) N: tetraicdral, rp' ; B : terralrdd, sy' (d) Tiibsic rd rcaf Brctod [(i, Q.I.T 2003)
(D) N : gyrarnithl,sf ; B : PYramiihlf

K S.
stc 59. d A.h 6l.d 6Lb
6ac Aa 65c 6.d e,.t
SOME p-BLOCK ELEMENTS 13i69

6& Which of the tollo$,iDg are isoelectroDic and (a) R(oMe).r (D) NaOMc
isostructural?
(c) Al(oPOl (d) sn(oHt
NO3-, CO3-, OO3-, SO3
(A.l.l.M.s.2oo1
(a) No!,col- (D) so3, No3- 71. Shape of O2F2 is similar to rhat of

(c) ctoi, c03- @)9Fz (6) H2O2

(d) co3-, so3
G) HzFz (d)ciHz
tl l7 )l0l l

(.4.1.1.il5.200J)
6r. 'fhe element which forn$ cfiids is a cidation 75. Mcral rtict dG d form amfird um nitrarc by
sratcs +l ro +v is rtactbr with dilutc ritric ei, b
(r) P (o) Al (')e
(d) Sb t.,t. 1. 1..t 1. 5. 2ott1, (c) Pb (d) Mc
follmring qidc.s of nitrogeD is a (Knrrnlaklr ('.F-.7 :
76. Amoug the halogens, the one whici is oxidised by
(D) N2O nitric acil b
(o) fluorine (D) iodinc
(d) Nzos
(c) chlorin (d) brcmioe
A.ELt.S. 2004) 77. Which of the following is respoosible for depletion
of the ozone layer io the upper strata of the atmos-
71, The ONO aogle is maximum in pberE ?
(a) No3- (6) NO2-
(a) fotytatogcG (6) Ferrcne
+ (c) FIrIcIlns
(c) NO2 (d) No, (d) FrEoos
rc.B s.l:. I11.1: 2
\'l !.1..r1.\.20trlt
7t. Ozone (O3) dl\solvs in
72* (NHttCr2OT on heating gives a gas E'hich b also (a) turpentine oil (b) acctone
FwD by (c) borh (a) and (6) (d) None of th6e
(o) Heating NH4NO2 (D) Heating NH.NO3
I ll (; I ,l \ \tr:- !i-|
(c) Mg3N2 + HzO (d) Na (comp.) + II2O2
79. OzoDe in stratcphere is depleted by
I.l. l) 201)1t r (a)cFzrl.z (6) QHro
73. Which of the follovring imp8rts green cobur to the G)c6l+q (d) QFe
burner flame ?

H I NT9,/EXPLANATIOI.I9 to M ulAlpl e Ch oi c e @.u eeti on s

13, IIeaW metal oxides otr hdiEg giw O, gaw, ie- 29. Graphite k thIomdrramiDdly morc ataHe tban
6 diamond ad its free energy of formatiotr is I ,9 kJ
z2 Ilgo 4 z2 Hg
nE + u7'
02. m.r-I t,:s,er *i
md-l Io$Er at ,* temperatue ,n.t
r@m rFmernrn.F and ordinary
'rBr' - ^r.tin,ru
17. DUE to high elecrmnegativity, F trills the hoe pair prcssurc-
ofeleclroos on N towardi it.self- A.s a rsllt, itis Dor 3it. Zncor rEadioordth FINO] under different coodi-
alEilat ls for plorobation.
siiEs rnE diftrcnt Plodudq ia,
ricErs
24 2 PqNqh ...- 2 Pbo + 4 Nq + 02. N2o, No, Nor, NH! aod NH.Nq.
25. ozotre abEorts {rv radiatiom but not gamma 31, co is Deurral snoz, zrio and sio2 are am-
radislions' obo{.ic.
27. CH3 SrouP bcing t i8 @nnot fcrEl a hrid te hetcrem
r*o smau sEed bo{or atoms, " 3?' 'IhiliEg or H8:

J< _c'
6&a 69.o 74. b 75. d 76. d 77. d
1t-c 79.o

{
13nO Pradeep's Netl Course Chemistrq

As we move fion NH3 + Pl{3 + Asll3 + }{z0z (l)' O3 ( 5), 02 (2), ie.

SbH3, electronegatiyity of the element decreases H2O2 (148 pm) > o: (127.8 pm) > oz (120 7

arld hence the metal- hydrogen bond becomes less Pm). a

and lcsr polar, thereby lo*ering thc dipole moment. 51. 3 Mg + N2 * Mg3N2 ;
'Ihus NI13 has th highest dipole moment. (x)
Mg3Nt + 6HzO* 3 M8(OH)2 + 2NH3
INFI ard H3O+l are pyramidal while [NO; aod
BF3lare planar.
C\rSo. + 4 NH, j)al soa (6[ie)
-*lcu(NH
Itr NO2+, ie. O = N = O, N is.rp-hybridized. in
39. Lead pncils mntain gaphite mixed fl/ith clay or
wax but no lead. No3- it is .rp2-hybridize{t while in NH.+ it is .rp3-
42" The bond order iD co3- is 1.5, in coz it is2while hybridized.

in CO it is 2.5. Therefore, higher the boDd order,
somllerthe C-O bond length, r|e. CO3- < Co2 <
co.
43. ln BC13, B
is rpz hybridized and henc has aD angle
of 120"while in PCL, AsCl3 and BiCL, the elenrents
B As and Bi are ry'-hybridized. Futher, as the
electronegadvity of the element decreases ftom P
to Bi, the bord pairs nro!,c away frolll tbe central
fltom aIId heDce th bond angle decreases from P
ro Bi. Thus, optioo (b) h correct.
4E. Al is rendrcd passive by formarion of a thin im-
prvious layer of A.l2O3 on ilssurfacewhen brought
in contacl. with conc. HN03.
50. Bofld dislances decrcases as bond order increases.
No{, bond order decreases in the order
Each silicon atom in crystalline structure olsilicon
is terahdrally suffouDded by four other silicon
atoms. This struclure issimilar to that ofdiamond.
61, OriBi[alty in NH3, N is p]ramidal (rp3) bu( ro BFr3,
B is plaDar (rp2). But after the bond lorDation, r'.c.,
in thecomplexH3N -
B F3, both N aDd B have Iou r
shsred Dairs of electroDs and heDc both havc
tctrabedral Gp3) geomctry, ie., option (a) is LUr-
rest.
No. of elcctrons iD NOr- = 7 + 8 x3 + 1=32
Both NO3- anrJ CO!- have saore number of
electrqrs aDd hence arc isostructural (triSoral
planar).

Ah*tTtoNA{, guEST/oN
)t1:
The followirg qucstlons consist of two steteErents eoch, pdnted os Assrtion and Reason. While onswering
thes. questlotrg you arc rquiEd to choose any one of the follovlng four responses.
(d) Ifhoth Assrtlor sod ReosoE are arue md the Reason is a correct explanatlon ofthe Assertio[.
(r) lf botb Ass.rtiotr ond Reoson are true but Reosor is not a ctrrcct exPl.nation of the Assertion.
(c) If Aseniotr ls truc but the Rcason ls false.
(d) Ilboth Asertlon and RessoE ere fals.-

Assertlon Resson

t. Although PFs, PClj and PBr3 aro knotm, the pen- Phosphorus has lowr electronegativity thaD nitrogen.
tahalides of nitroSen havc not beetr obscrved.
(I.r.T 1995)
Thc bond angle of PBr3 is Sreater than that of The size of bromine is less than that of hydrogcrl.
PH3 but the botld angle of NBr3 is lss than ihat 6.r.r.M.s. r997)
of NH3.
3. Diamond does Dot retlect or rcfract li8ht. Diamond has low refractive index.
4. Gmphite is a good mDductor of heat and Graphite has all the electrons firmly held in C-C, o-
ehctridty. bonds.
SOME p.BLOCK ELEi.4ENTS 13171

Assertion
5, Carbon moDodde is highly tor:ic (porsonous) in (lirrboD moDoridg forms a stable complex \rith
nature. hflclnt': \'lrrn prr'sL.nl in rec blood cells.
6' Carbides containinj tj- u,r,,,, l.r u.l.lr(l { tl,(.2 ruli,..9?() tre not trug acetylides bcause these
acctylides. on li\'(lrolyjis dc no( pr(xiuc acetylene.
7. Amoronium nitrite on heatiD.( rlives NL-) NO is aD acidic oxide.
& Allthe N-O bnnds in NOt are equat. NOi is i! icsoriancc h\hrid ofthree equivalent resonat-
ln8 sttuclurcs-
9. Nitrogen is uoreaclive at roont tcmpcrillure but In nitrogcn ntolccule there is exlensive delocalization of
becomes reactive at clcvrtcd tcll)pcrittutcs rrr ill electro s. (A.LI.M.S. 1996)
presnce of a catalyst.
10. Ozone is a polar moleculc itlthourh tt is It contains a coordinate bond and has a beitt structure.
homoatomic.
11. Nitrous acid (HNO2) ntay act as iln oJi(lisrng uri 'Ihe oxidnlion nuBtber cf nitrogeD remains same in all
wdl as a reducing agent. the contpounds.
12. Uquid ammonia is used for refrigeration. It vapourises quickly. (A.I.I.M.S. 1997)
13' NOi is ptanar while NH3 is pyramidal. N in i\la)t ,., rpz- hybridized bur in NH3 it is q.p-
hybridized. (A.I.r.M.S. 199n
l{. [INO3 is a stronger acid than HNO2. In HNO, therc are two nirrogenffygen in
-fgds'white
- (t.Lt
HNO2 there is only one. lggE)
+
o
15. The electronic structure of ()3 is
//-\
O': O:- ./o\
oo slruciure is not allowed bcause octet
around O cannot be expanded. (r.r.T I99E)
16. Dinitrogen is chemically unreactive at or(liDarv 'fhe
temperature and is very stablc.
bond dissociation energy is 946 U mol-l

@.J.1.M.5. r99E
17. lriliDg of mercury occurs on p.ssing O, throuL:h I),-rs 1o oxiclition ofntercurv_ (A.I.I.M.S. teee)
it.

True/Falee Statementg
Schcr rhc fii/ arl Iokc atementt iro,n the iollow- 7, Dinitrogen is almost chemicalty unreactiw beqiuse
a8i cf jts high bond dissociation eDerE.
l. A[ clements give bor bad test. iJ, During ring tesr lor Ditrate ions, fenous ions reduc.e
Silicol diamond like structure.
has NOt ro NiJ.
3. The tendenc, for catenation is much higher for C 9. [n coppcr sulphale [Entahydrale, all the water
than for Si. (I.lll !9931 n't' ):eculcs trc attach xl to the Cu2 + ion by mor-
dtilatc covaleot bonds.
4, A aqueous solution of N%CO3 is acidic lL' litmu:J.
Iii. Chlorofluorocitrboos deplete the ozone layer in the
5. Carbon diqide combines with haernogr )bi!.r ,Ji iltnlcsPhcie.
blood to form carboxyhaemoglobin. 11 . a)xi(le ion is consi(lered as bard too sincc ii canoot
6. Diamond is barder than graphitc. U.i.i i99ji be e;1iil! trolaflze.;t
i2. Nztl and NO arc ncuiraloddes cf oitrogeD.

Fill ln The Olanks

1. Of all the boron trihalides, the u,eakesl Lc,!,ls ].iil 3. The t$'o t Tes of bonds prcsent in Brllo arc
is..... .
(I.I.T. t994\
,. A cqDpound of fluorine knqvn us .... . .. i. ,l ( ,..)- llN(E,(m dctlvdralron \rirh p4or0 gives
widely used in refrigeratron and aeros<,rs.
(Roorkee I 999)
13F2 Pradeep's
ozorle b ...-............ q,tile -............. b paralBgDctic- Nitric acid coDtaiDing .................-....-. is called
6. b ao acidic qiie wbib SiO2 b aD fuming dtric acid-
...-.-..-.............. cidc. 10. l-aughing gas is obtained when .....,-..-..,.-., is hcated.

7. Aqua rcgia is a mixturc of .......,.-............. .

lt. Tbe tailin8 of mercury is due to lhe formatbn of
& In gaseous stat, Ditric Glre b --....-.-...--....-... wl le
IL 02 is ahorbd by ....... O,
-. aod is ab6orbed by
in lhe lhuid or $olk, state it b ...-...-..-........ .

,3. Ttle formula of acidic litrogcn hydride is

Watchin7 Ty? G.ueslions

atchinO Ty?e
a
Matdr itcrns of colum[ I with appropriate alom6 of (.olumo II. G
col[En-l Colomo.Il
:r
l. DiDitrosen tetrcdde (a) Flllererle and diamoDd
2. Arnmonia (D) Diamond structurc
3. Carborundum (c) Boric acid
,L Colemanite (d) Complqing agDt
5. Alotmpes io Krket fuels- {

ASSERTION-REASON TYPE OUESTIONS

l.(6) z(d) 3.(4 a. (c) s.(o) 6.(a) 7. (d) t.(a) e. (c) r0. (a) 11.(c) 12.(D)
ra (a) r{ (c) ls. (a) 16. (a) 17. (o).
TRUE/FALSE STATEMENTS

l. Fh&c 2. 'Itue 3. 'Iluc a. BEc, hiq 5' Rlc' @ cqnttin6 Eirh tamoSlotin of bld to torm

dfb $c 6frh @c b omocO to sol- im by l{.bond. lll'Ituc ll.'Ituc duc to slEll dp of Gitc im and

t DcE d- bo b a bard im. l/t'Ituc.

FILL IN THE BLAI'IKS

1. BF3 a frem a @ogtn Hle a tm clcdrqE N2Oi

thrcE ccotrc boods. ( t dhmagntic, 02 ',

6 NO2 tr CtOT ampboaqb 7. HNOs + 3 HO t. Paramagrtic' diirDstdic t Gib. of dtrofn

lo amrtrooiEm oitsatc 11, mqluls qirc lZ an alkaliDe solutirl of PyroEatbl, turPcotiDc oil
ra N3H (bldruic aid).
MATCHIN G TYPE OUESTIONS

r. (c) a (4 3. (D). (c) s. (a).

,,:,,::,,,,.
 ru h! [1r

Organic Cherrtiot'.ryr
5 orrt e Aasic ?rin c,ipleo

Telracovalency-ot calbon, hybridization, (p and s) bonds, shapes of simple nrclecules, lunctional

groups : -C = C-, -C = C-, tunctlonal grcups containing halogen, orygen, nitrogen and sulphur.
Honrologous series
lsornerism
General inttoduclion lo naming organic compounds-lrivial and IUPAC nomenclature. lllustration
with simple examples.
Electronic displacerEnt in a covalent bond : induclive efiecl, electrome c eftecl reEonance and
hyperconlugation.
Fission ol a covalent bond : free radicals, elecrrophires, nucleophiles, carbocarion! and calbEnlon6.
common iypes oJ organic reactions : substitution, eadition, erimination and rearangemont
reacliona. lllustraiions with examples.

14.1. lntroduction
It has been knoum since times immemorial that
minerals. plants and animals are the ihree major
sources of oaturally Bur it was
on! in eighteeth century that thesc compomds nrere
divided into tc/o classes, viz Organic and Inorganic
compunds mainly on the basis of the ir ytwe,. Cqn-
ptunds lke we4 sagot\ oib, ldt dtes, Weinr,
eitamins dc, *ltich wae bolated diraly u iadinaly
Imrn livingdgotbns such os otimals qd plotE wut
calkd Organia Cmpuads nd tlv bruieh oI
chembby dtich dcolt with he sudy ol these cottt-
potuds was callcd Orgfiic Ctcnistry. On the dur
hon4 cotttputds like conmant sa\ msble, uhans,
nioe blue od gxen vitiols elc. b4tich twe itolated
lrun run-living sam+ sud as ruks otd minault
werz colled ltugmic. Compnmdg and rhe brutch ol
chenbt! which dcal with 0u sttdy of ihese unr-
pounds was called lnorgltric Chemistr}
14.1.1. Vital Fortc Thcory
Until early oineteenth celtury, it was
believed that organic compounds cannot be
prepared io the laboratorybut cao only be isolated
from animals and platrts. On thebasisofthisbelief,
Benelius, a leading Swedish chemist in 1E15,
propouruled Vital Forcc Thorf,. According to
this theory, argarlic compounds an produced onty
unds thc infiuCicc of somc mysteians lorce erist-
ing in the liing ugonisms. This nysteious lorce
was called the Yilal Force. Since such a
Eysterious force cannot be created artifrcially, it
is inpossible to synthesize organic cornpounds in
the laboratory. This thcory reigned suprene for
a number of years.
Hovrever ,'m 1828, Wohle4 a German chemist,
made an interestirg discovery. fle accidentatly ob-
tatned uea, a well tnowr organic compound,
presenl in the urine of man and oihcr mammals by
cvapogating an aqueous solution of amnodum
{al,ate, a typical inorgadc compound (obtahcd
by double decomposition of ammonium chloride
and potassium cyanatd :
NH.CI + KCNO ----------- NHICNO + KCI
Arlrn. cfanatc

t4ll
 Pradeep's
1412

..)

Ilcat ll
t'..,:,. tt,, t iitrliwr.
NH4CNO NH-, -(-l-'iii.i-
(horganic co tpo:1n,!) llcan'rli8s \)\ea ;,o]'gattic (.ottt.)dttnl) 14,2. Tetravalency o{ Carbon :i i,i. ,
, ': : :: ::,:i , : :'i :,i::,,:, !:i,;:.:::

This tleath biorv to I'irl1 r1'rcc

synthesis ga'.'e a
th t/lr:t rti.t ii :ir.t: L:
. L'urbon is lhe essentlal elcment of all organic
Theory aul clearly demonstrated
L:rrircules lts olectronic configuratiou is 2, 4. In
ot}rcr words, sarbon has four electrons in the
valcnct' shell and thus needs four more electrons to
.()mp!e te its octet. Therefore, carbon is tetravelent.
Frirtirrr, it is very difticult for carbon to either gain
,'r l.;:rr iour eleetrons [o achieve the nearest inert
11.is curfigurrtion. Con-sequently, carbon
always
l)il.II. so_
Elcctric iombines u,iLh oihcr atoms by mutual sharing of
2C+H2 HC=CH cilatrons and thus lorms covalent bonds. Slnce all
atc Acctylcne HgSCa
1it,) otydtltc colnlLittnds conlain carbon as the essen-

-CII,CHOorliatlo;+ ( il1cl )1 r!] riril cleneai, chemical bond-

ttrS itt otgutri covalent, Thrus'
Acelal(tchlde ,\1 r;t ' l ., it forms four
t:ahon is al
Thertufter thousartds anci tircrttsLt:<ls rl 'rr- covalent bcrnds with othcr atoms as showl below :
ganic compounds have been s].nthcsized in illr H CI
hboratory thereby showing condusivclv (\rrl rii'-
I
inorganic compouods, organic cr.rmpoun'i'; c:tn D:
I
H_C-H CI-C-CI
easily sy,nthesized in the laboratori'.
I I
14.12' Moilern definitiorr o[ Orgrrnic {)r' r'- H CI
pounds Methanc Czrbon tclrachloride
With the downfall of l4tttl Fotic i-hc't't' ;i" I'I H
lil tl
H_C_C_H
il ii I-I
,t
H
few other elements such as oxygen, nitrog';n sl'l- lrthanc
phur, halogens and phosphoms 'fhtts. orgotrit [iowcvor, thcse slructures do not reveal a-s to
ifternistry is now defined us the chemistN of cu'bot1' rri,.r is lh;. sp,itial oricntation of these four bonds
compounds containing usualty ltydroge,t itttd o'rc ot'
more additional elemenls like oryget4 nitoget4 'siri
phu4, halogens, phospltonts elc. lrtoruii;,, r'l' 'i' i'ri
on the,t rr hoad, is ,lelinL'd u.i tl;t rtt"ttt't 't ';l'
elenrcnts otltct tha catbot lltd (lt(tt t o;1iilt)ttt :!\
tt should be nrentioned herc []ra[ solrL !']nr- e:irl'on atcm are directed towards the four corners
pounds of carbon such as CO, COr, HrCO., notal of t rcgilar klruhedron, i.e, the angle betwoen any
carbonates, carbides, cyanides etc., which sLo'.rld Lwo ailiacoot bonds is 109" - 28' (tetrahedral angle)
otherwise have been included in orglnic chentisl I1 .rr ..i,o'r'n in lrig. 14.1.
are stilI studied under inorganic chenistry bclrtttr'c l'his tetrahedral concept of carbon has been
of their greater. resemblance with inorganic corn- esl,rblishcd heyond any doubt by electron diffrac-
pounds. tion. X-ray diffraction and spectroscopic studies.
Further.,'orgnnic compound" madc up ol o''1" 'l'h:. tctriihcdral arrangement of fourbonds of
carbon and hydrogen atoms arc culled /r' lr' r"' ,:ru bon Iaid the foundation of the present day fas-
i6i onI?iott .i organic- < om1'rruntls rnrtr r" crnrrlirrg tiold of 'slcrcochemistry'. It is because of
rt'6i?ded to havc beenclcriYed ftom lhrse- tlils rcasorl that van't -Hoff was aw-arded tbe-fust
hy-drocarbons by replaccment o['one or ttri:'rc trf lJobcl Prjze in Chcmistry in 1901..He is also some-
their hydrogen atoms by othsr atoms c'r trouPs riLrr.s cirllcd 'Thc lalhat ol Oryanic Chemistry'-
 ORGANIC CHEMISTRY _ SOME BASIC PRINCIPLES 1413

1s

tz
# ll\ Re) (") \
ffi
'1s

\,&

t .H
PART I (b)

HYI}RIDIZATION ANI)
STI,API'S OIT NIOI,ECUI-ES FIGURE 14.2. (a)Orbital picture of methane.
(b) Bond angles and bond llngths tn methane.
14.3. shad; ,::1.+:.i:

One of the most important aspects of H ATON'

organic chemistryis to understaod the fundarntntal
concepLs of molecular structure since on thc basis
of these structures, we catr easily predict the
properties of organic molccules. To explain the
structures of organic molecules, Ge eleclronic
theory oI valeocy aad tbe concept ofhybridization
was introduced in unit 6. On'the basis of sp3-
hybridizatiou of carbon, the structures of methane
(Fig. 1a.2) and erhane (Fig. ta.3) molecules were
predicted to be tetra-hedral.
Similarly, structure of ethenc (CH2 = CH2)
was explained_ to be planar on the basis of sp2-
hybridization (Fig. la.a) and thar of ethyne (HC
= HC) to be linear on the basis ofsp-hyUriaizaiion H..
as shown ir FIg. 14.5.

! 090-280

Thus, in terms of o- and z-bon&, a carbon- FIGURE I4.3. (a) Orbttal pkhre of ethane.
carbon double bond consists of one strong o_bond tD) Lrond lengths and bond angles ln ethane
1414
lratle e p's NeU aaursc Ct e*i$rrl:@

H.AToM SP, SPZ H'ATOI'

I-bond

o-bond

?r-bond
p
o 154 pm
>
l,lE
C (sp) - c (sp)
138F
Further sincc, the sideways overlap of two
p-orbitals (to forrn z-bonds) brings the two carbon
itoms clcser to have an optimum degree of overlap,
therefore, a siagle bond Ls longer than a double
bond which, is turn, is longer than a triple bond.
o Thus,
_c_c_ >c=c< _c=c-
FIGUFE 14.4. (a) Orbilal picture ol ethene-
154pm 13,l Fn l2o Prn

\ 1) p-eleclrcn cioud consists ot two equal

halvos; one lying above and other bolow the
plane ot carbon and hydrogen atoms'

decrease accordingly.
c(r1)-H, c ("1)-H > c(sp)-H
lor) Pm 10? 6 Pm loi Pn-

tion energr). For exarrPle,

(i) c(.sp)-H > c(sp)-H
5o7 lcl mol-l ,143 IJ mol-1
> C (sp3) H -
45 U mol-l
tD c Gp)-c (sP) > C (rp2) - C(tp')
43U mol-r 383 Ll mol-l
, c(#) - c(ry')
- |
347 til mol

Itr contrast, a z-bood is formed by the

and onc weak z-bond. Similarly, a carbon-carbon

triple bood consists of one strbng o-bond and two
weak n-bondi.
ond ooger
and bond
size weak
triple
 OFIGANIC CHEMISTFIY SOME BASIC PRINCIPLES
- 1415

bond is still stronger (803 kJ mol-r) than a carbon groups attached to an atom by a subscript. For
carbon double bond. example,
(rii) Electronegativity. The type of hybridiza- CH,CH, H,C = CH, HC=CH CH3-OH
tion also affects the electronegativity of the atom,
of the hybrid orbitals
or C2H6 or CzHq or C2H2 or CH3OH
e atom. Thus, a sp- Ethane Ethene Elhrnc Methanol
ng hybrid orbitals with Such sttuch$ol rcpresentations orc called con-
50Vo s-character is more electronegative than a densed structural formulae.
sp2-hybridized carbon with 33. 334 s-char acter Sometimes these structural formulae can be
and sp3-hybridized carbon with 25Vo s-charccter. further condensed by enclosing the repititive struc-
electronegativity are tural unit within a brackets and placing an inleger
d chemical properties as a subscript indicating the number of times the
structural unit gets repeated. For example,
I 4,4. Structural Representalion of CH3CH2CH2CH2CH,CH2CH2COOH can be fur-
Organic Compounds ther condensed to CH3(CHT6COOH.
14.4.1. Complte and Condensd Formulae 14.42. Bond-line Structural Formulae,
The structures of organic compourds can be It is a simple, short and convenieat method of
represented in several different ways, The most representing organic molecules. In this method,
important of these is the Lewis structures. But carbon-carbon bonds are shown bv lines drawn in
a zig-zag fashion and carbon atomsty liqe ends and
single by a
doubl lines
bond (=).
dashes (=) to represent a triple bond. The lone
atoms toms
other than carbon and hydrogen atons are shorrn
toms (e.g, orygen,
on the zig-zag line. Further, it is assumed that each
may or maynot be
carbon on the line end or intersection is attached
erhene (qHa),
to requirednumber of hydrogen atoms, r'.e., termini
ethyre (CrHr) and methanol may be represented
denote CH3 groups and an unsubstituted intersec-
by the following structural formulae.
tion a CH, group. For example,
HH
lt
H-C-C_H
H\
C=C
..H
CH3CH2CH,CH2CH2CHTCHTCOOH can by rep-
resented by the following bondJine structural for-
lt
HH
H'/ \H mulae.

Ethanc
Ethene o
H-C = C-H
Eth,,i ,^r^rV(o"
HH
.t..1 14.43. PollBon Formulae
H-C-O-H or H_C-O_H The re are memy organic compounds, in which

t'l
HH
the carbon atoms are not joined in a chain but are

- Methanol
Suchstruciral representations arc called com-
plte structural formulae or graphic or displayerl
formulae. of a polygon denote a carbon-carbon bond. If an
Those structural formulae can be further ab_ atom or a groupof is
breviated by omitting some or all the covalent attached to carbon, of
bonds and by indicating thc name of identical atoms is showtr in th
1416 Pradeep's

(c) HOCHTCHTCHTT, -r, ('Ot

I
CH,
cHt
e
OH
I

(d) N =C-CH -C = N (N.C.E.R.T.)

S0lution. Condensed Formulae
(a) (CH3)2CHCHTOH
chl
(b) CH3(CH2)5CHBTCHTCHO
E)(AMPLIi 14.1. E4 and each ol following
the (c) Ho(CHr)rCH(CH3)CH(CH3),
condensed formulae into theit comPlete structurul
(N.C.E.R.T,) (d) HocH(cN),
fotmulae
(a) HOCHTCHy''tH2 Bond-line Formulae
(b) cH3(cH)3oH (a)
/ \oH
(c) CHTCHTCOCHTCH, /i Br
(d) CH jCH = CH(CH).CH,

' HH
(a)
tl
H-o-C-C-N-N
rtl
HHH (c)

HHHH
(b)
llll
H-c-c-c-c-o-H (d)

rlll
HHHH
f,l\.\\rl'1.1,r11.1. Eryland each of the fouowing
HHOHH bond-line Io,nulae to show a.ll the atoms including
(c)
tlllll
H-C-c-C-C-C-H carbon and hydrogen. (N.C.E.R.T,)

llll HH
HH ,",G @\/\/\,/\\/
HH HHHHH
H-C-c
tllllll C-c-C-C-C-H l)t
(d) =
llll
at z/\( ot
,\/clu
I
u
H HHHH
I
li\ANlt{,I, 11.2. For each of the following
compounds, wite a more condetsed tormula ond oP
also theirbond line fomulae. H
!
(a) 1H31HCH2OH I
I
CH,
BrH
tl
t-

H
$(i-'
r'-?-'-'
tb) CH3CH2CHzCHTCH2CH2CHCH2C =O
H
 OEGANIC CHEMISTRY SOME BASIC PRTNCIPLES AN
-
HH No. ofz. = 6bonds = t x 2 (double bonds)
lt
(r)H-c- -c-H I'.XAXIPLE 1.1.5. t4hot is the type of ltybitliza_
tt
HH
tion of each carbon in the following compourtds ?
(a) CH.CI (b) (CH)2Co (c) CH.CN :
(d) HCONHT(e) CHrCH = CHCN
(c) H-c = (N.C.E.R.T,)
Wrire Lhc partly condensed fbr-
mulae of the above compounds and indicate the
(d) type of hybridization on each carbon. u1,
spt ttp'
"p1
(a) CH,
- Cl (b) cH3-c-cH3
tl ,..1
o
spl sp spz

-C = N
c (c) CH, (d) H-C-NH,
il

sp! spz spz sp

(e) CHr-CH CH-C = N
IIKAI\ IPl,la 14.6. What is the shape of
following
l--\Alll,l,li 11.1. How many o_ and n-bonds compoundt ?
qrc prcsent in eoch of the
following molecules ! (a) H2C = O (b) CH3F (c) HC = N
(a) HC= CCH = CHCHT (N.(_-.E.R.T,)
(b) CHr= C = CHCH: (N.C.E.R.T) (a) ln HrC = O, C is .rp2-
Solutio4. Write the complete structural for- hybridized, hence formal<lehyd.e is tigonal plunox
mulae and count the number of carbon-carbon, (D) In CH,-F, C is.rp3- hybridized, hence
carbon-hydrogen srSma-bonds and carbon-carbon me thyl fluoride is tetruhedral.
pi-bonds :
(c) Io H-C=\, C is sp-hybridized, hence
H HCN is a linear molecule.

@1a!clc!cic!!
ol ' "--n CLASSIFICATION
P{R'T II
d\D NOMEN-
//'tt
oHHH lo 'l
CLATURE OF ORGANIC CON{POUNDS
No. of o"-- = 4 ; No. of o-_,
=6
Totalno. ofo-bonds : 4 + 6 = 10
Total no. ofz.
= 6 bonds
= 2 (triple bond) + 1 (double bond) =l
H
t"
@)H!c3s3696=H
"1 " " l" lo"
HHH
No. ofo"_- = 3 ; No. ofo"_, = 6
Total no.ofo-bonds:3 + 6 = 9
1418
Pradeep's

nounds have been broadly divided into two are [urther divided into the following two sub-clas-
categoriesdependinguponthenatureoftheircarb- ses.
on skeleton. These are : (a) Alicyclic comPounds.
I:Acyclic ot open chain comPounds.
'/-I{. cwytund.s which raemhle aliphatit
Qctic or closed chdin comPounds. i mon of theit propercies are called
ll:'f
either For example,
straight chains or branched chains. For example,
Stralght chafu compounds :

CH3-CH,-CH2-CH, CH,-CH=CH-CH,
,-Butanc But-2-ene cHz-
(forme Y 2-butarc)
o cH^-cH"
CHr- CHr-C=CH cH3-cHz-c- cH2-cH3
Bul-1-Ync Pentan-3_one
tl
l'l'oR
cH;- c{z
(fodndly I -burtne) (fome Y3 -Pcntanone)
Branched chain comPounds :

CH,
I

cH3-cH-cH3 cH3-C-CH3
I I

CH, CH:
kohutane Ncopcntane

cHr cHr
I I

CHr-C = CH, CH3-CH-C = CH

Isobutylenc 3-Mcthylbut-1-Ync

\-'.;'
Nu-h.trDEldsrolDattomPantdsTherearecertanarornaticctrnpoundwhidl.donotcontainbenzDneringeThsc
ue Mrstfutzonid M,e "-'P;d* T@leamples of ordr ccnpound a|p uopok|I|e ard anlem'
 ORGANIC CHEI\,IISTRY SOME BASIC PRINCIPLES 1419
-
ADD.TO YOUR KNOWLEDGE CONTD.

Hc\- cH

H H
Tropolon Azulah.

The name aromatic for this class of cyclic The heteroatorns cornrnonly found in these com-
unsaturated compounds has been derived from the pounds are o{/ger\ nitrogen and sulphur tiut oc-
sincs casionally phosphorus, boron, silicon and some metal
vered atorls like tin, selenium etc. may also be present.
term Depending upon the chemical behaviour, they are fir-
aromatic has now lost its original signfficance be- ther classfied into the following two categor;es :
cause many aromatic compounds are now known (i) Aticyclic heterocyclic compounds :
to poss-ess unpleasant odours. Aliplrutic cyclic compounds containing one or mo,u
'- Some important examples of monocyclic, heteroatoms in their ings are culled alicyclic
bicyclic and tricyclic aromatic compounds are : lrcterocyclic compouzds. For example,
(i) Monocyclic aromatic compounds :
,r-"\ CH,- CH.
CH, CH2 tt
CH.
o
Oxirane CH^
'
O
Benzene Tolucnc
-CH2
(Ehylcnc o.id.)
\./
Tet rahydaofu ran
CTHF)

cH.-cH- cH.-cH-
l' t'
CH. CH^
l'
CH.
t'
CH^
'
\n,,/ \",/'
H Tetrahydrothiophcne
ry'rrolidine

Anthiacenc hetrocyclic compounds. For example.

(llicrtut\
CH---{H
ilil
CH CH
\o/
Fumn
.In organic chcmistry, atoms othcr than Cand H ato
1411O
P ra tie t p's Neut Co urse Caem i strg fiffi
CH---{H ClHH
il ltlt
CH

H
ll
CH
U CH CH
\,/
fiiophcne
Ii-il
\sz'
ryTrole

The above classification may be summarised as follows :

Organic Compounds

f-
Acyclic or open chain

Alicvclic Alicyclic

B*nr"looid Non.henzlnoid

From the above discussion, it follows that the

':
4.6. Functional or Characleristic G ro up s ,':r'r:i:,i'ir:,rr

Asalready the
parent organic co unds
ire considered to mbY
replacing one or more of their hydrogen atoms by (CH3)'CHOH etc. all produce hydrogen when
some otfer more reactive atom or group (G) treated with sodium metal.

R-H
-H
R_G 2R-O-H + 2Na + 2R-O-Na+ + H,
HldrocaiboD + G Alcohol Sod. alkoxidc

where R : -,
CHr CH:CH2 -,
Thus, each organic molecule consists of two
parts i.c., R and G. The hrst part i.e.,'R'denotes (CH3)zCH - etc.
ihe ca,bon- hydrogen fi amework of the molccule The reason for this similar chemical bc-
while the second pa rti.e.,'G' iscalled the functionol
haviour is that C-C and C- H lronds are very
gottP
strong and hence do not break casily. In contrast,
anElom the O - H bond isweaker aod hence reactivc. Thus,
h vhbh we conclude thatarty organic compound will behave
in llrc same manner as qny olher otgqnic compowtd
hoving the same Ittnctional group no matter whdt the
The rcmaining part of the molecule (e'g R) rcst of the molecule is. However, exceptrons are
mainly rrflccts thc phvsical properties such as melt- known when the molecule is very large (e g group
ine point, boiling pcinl, tlensity, solubility, refrac-
tirlc indcx etc. For example. - OH (.hydroryl) isthe
lirnctional group o[ alcoh ls since in almost all the
chcmical rcactions of alc hols, it is the OH group
that undergocs a change while the rest of the functional group.
molctulc 1cg. 11) rcnrlinr ttnchanged ln a similar Somc of the common lunctional groups
rvay, (:OOH is thc li:nc:tional group of carborylic
- present in various organic compounds are listed
acids. below :
 ORGANIC CHEMISTRY SOME BASIC PBINCIPLES
- 14111

Class of organic compounds Nohc ofthe ftrnction^l group Sirlrcture of the [unctional group
Alkenes Double bond
Alkynes
)c=ca
Ttiple bond -C=C-
Halogen deriyatives Halogen - x (F, Cl, Br, I)
Ajcohols Hydro!ry
Thioalcohol Thiol or Sulphhydryl
-oH
or Mercaptan or Mercapro -slI
Ethers Dii?lenl. orygen
Thioether or Sulphides DivaleDt sulphur
-o-
-s-
o
lt
Aldehydes Aldehydic (formyl) -c-H
Thioketones Thione >c=s
Ketones Ketonic ((1.!o) >c=o
Th ioaldehydes Thial
-CH=S
o
ll
Carboxylic acids Carboryl -c-oH
o
SulphoDic acids I
Sulphonic acid
-s-oH
i
o
Primary amines Amioo - NHz
Secondary amines Imino
'IErtiary amines )${H
Tbrtiary N-arom >\N-
Alkyl cranides or qroo or nitrile -C=N
Alkyl isocyanides or isonitriles lsonitrile or'isoclano -N-c
./P
NitroalkaDes Nitro
'lo
or -i'.o
\o-
Alkyl nitrites Nitrite -O-N=O

Aldehldc
CHO NHz

t''9o'"I
(D)
d Srtut!-gl(a)

OH
o Ao.*,rr,*rrr,,,
tJ

o\
c-NHCH3
CHr+
iCHr-N(';cn;
(c)
I
CH3CH2CH(CHr2CoCI (d)o I 'QHri
i

T l',{mino group 3' Afiino Foup

CH= CHNO2 l,lronntic) (Aliphatb)
 14112

j -ij- --- ---- -- -:2.-- z' e*io. CH3CH2CH,CHTOH Butan-1-ol

\-c-utt;-cu.
i'---"'t--"'--' (font r e rlY l -b rttort o I )

Some other homologous series are alkenes,

(c) cH3- cH2 - cH - cH2- cH2-i _99_9_tj alkynes, alkyi halides, cthers, aldehydes, ketones,
Acid chloride amines, esters and carboxylic acids etc.

(d) (a))-i CH = cH i-: N04.1xi,'o g.oup

Characteristics of a Homologous Series
' \\2,/ r-----------J r---..' (l) Each homologous series cqttbe rcPrcsented
Ilthylenic by a generol fttnnula. For examPle,
doublc bond C,,H2,+l COOH is thc general formula of car-
borylic acids.
To simplify and to systematize the study of
organic chemistry, all the organic compounds have
been divided into different families or groups
depending upon their structure and chemical
properties. Each such family or a group is called a
hontologous series. ketonic group, i.e., >C= O.
(3) The successive members of a lrcmologous
seies differ by a CH, group orby 12+2 x I : 14
tnass uttits.
@\The indjuj-@1al rnembers o[ a homologorts
seies cotr be prepared by the Eenerql methoh ol
develoPed for that seies.
_prcpqrutio
density,
t enofa
I witlt ise
itt molecular mass.
(6) The chemical prcpefties of lhe memben of
futnolcigous series ore sintilarthough theftrstmem'
' QHr qH8 C4Hto C5Ht2
a
cLIl C6Hl4
ber may vary coniiderably from rest of the members'
Mcthafle Ethanc Propanc Butane Pcntanc Hcrdnc
These hydrocarbons can be represented by
the same general formula, CoHr*2 whe'e z is the One of the most important characteristics of
number ofcarbon atoms. Flrther, any two adjacent organic compounds is their abiliry show to
members of this class differ by a CH, group' isomerism.
Two

properticr are callcd isot

is known us isomerism,
this series can be represented by the general for- It is of two types :
mula CnHr,rl OH. The first four members of this
1. Structural isomerism and
series are :
2. Stcreoisomerism
Formula IUPAC names 14.8.1. Structural lsomerism
cH3oH Methanol
cH3CH2OH Ethanol
cH3cH2cH2oH Propan-1-ol
fformerly |-proPanol) isomerism.
 OFGANIC CHEMISTRY SOME BASIC PRINCIPLES 14113
-
Tt is of thc following slx types : 321
(i) Chain or nuclear isomerism. CH, = qg-gLr., CH, = C11-9-ar,
PIop-2-cn-1-ol Mctho{Ethcnc
Compounds h.aving thc same molecular tormula (A yl olcohoD (Mchyl vitryl cthcr)
but tlifferent urrangement. of carbon chain within
lhe moletuk are called chain or nuclcar komen FurtherexaErples of Functional Isomerish
und the phenommon k cslkd chain or nuclear The following classes of organic compounds show
isomerism. fu nctioDal isonterism amoDg themselves.
(d) Alcohols rnd Ethers
For example, butare and 2-methylpropane
are chain isomers. qH6O represents :
CH,
: zl I CH3- CH2-OH and CH3-O-CH3
cH3-cH2-cHz - cHr cH3-cH-cH3 Ethanol
(EthylolcohoD
Mthoxymclhanc
(Dim.thvl ethet)
B].ltane(n-Butatle) 2-Methylpropane(/(,blrane)
(r) Carboxyllc acids and steN
(ii) Position isomerism.
qHaOz represents:
Compoundc whhh have the satne slructure of the
carbon chain but tlifrer onb in the position oI the
oo
mabiple (double or triple) horul or the fimctiontl cHr-J-ou ana H-l-ocn,
group dre callcd position isomen and the Ethanoic acld Mcthyl mcthanoatc
pherutmenon * called posirion isomerism. (c) Aldehldes aDd ketons
For example, but-l-ene and but-2-cne are q[I6O represeDts:
position isomers.
4321
oo
4321 ll I
CH3-CH2-CH=CH, CH3-CH=CH-CH3 CH3- C-CH3 and CH3CH2- C- ll
But-1-cne But-2-ene Propanone Propanal
Simiiarly, propan-1-ol and propan-2-ol are (d) Dienes, ollenes ond alkynes
position isomers. oH C4H6 represents :
3 2 I 3 2l I cHr= 611 - CH = CHz, CHz = C= CH - CH3
cH3 - cH' - cH2 - oH cH3-cH-cH3 Bura- l, 3-diene BDta-7,2- diene (An allmc)
Propan -I -ol Propan-2-ol and CH3CH2C = CH or CHrC CCH,
=
(n-Proh,l olcohoD Usopro t alcohot) But-l -yne But-2-vnc
(iii) Functional isomerism. (e) Nitroalksrlcs and alk!'l nltrites
Compounds lruving thc same molecular lormukt qH5NO2 represeDts :

b ul differerl lunntional groupt are calhd

Juntlinn- CH3CH2-NO2 aod CH3CH2-ONO
al itomers andthe phzaomenon ir cdldltmctional i_itroethanc Ethyl nitrite
isomerism. (RI', 2'and 3"-Amines
For cxample, the molecular formula, CrHuo qHgN represeDts :
represents the tbllowing two functional isomers: cH3cH2cH2NH2, CH3CH2-NH-CH3
cH3-cHz-oH cH3-o-cH3 Propan - I -anlinc N- Mcthylthanamine
Ethanol McthoxrrEcthanc
(l'Anine) (2" Aminc)
(Eth)'l olcohof) (Dindryl cthct)
9Hc
Similarly, the molecular formuta CrHoO rep-
resents the following four functional isomers.
and CH3-N -CH3
I

N, N- Dimcthytmcthanaminc
o o (3aAmine)
il il (g) Cyanides end lsoclanldes
cH3-c-cH3 cH3-cH2 - c-H qHjN represenb :
Propanonc prcpanal
(Acebnc) (Propionoldthfde) N and CH3 - N: C
CI{3-C =
Erhanenirrile Me thylisoryanide
 Neql Course Che nt isttu
14114

(ir) Arcnrrtic ,rlcolols, phenols snd cthers o

(iHrO represcnts: ll
(d) cH3cH2-c-cHrcH3
OCTI
A cHr
Pcntan-3-one
(Dietbt keto e)
()r is a metametamer oI
o
Bcn4lalcohol Anisolc o-Cresol ll
cH3 - c -cH2cH2cHl
A OI.I

()1.,,,
uo@cH,
Pentan-2-onc
(Methyl n-Propyl ketoDc)
o
ll -.cHt
,z-Cresol /-Cresol or CHr-C-CHi
- CH,
(iv) Metamerism. 3-Mcthylbutan-2-one
(Isopropr*lmcthylketonc)
Cnrnpounds h@ing the same molecular formuh
hul l{farunl numhor ol carhon ulomr (or albyl It may be noted here that metamers may also
grotps) on cither side oflhe functional group (Le" be position isomers. For example, pentan-2-one
and -CO-) are c.olled rnetamers and pentan-3-one may be regarded as position
-O-, -S-, -NH-
tnd the phenotnenon is cnlhil meta erism. isomers as well as metamers.
Met(meriw uccurs among lhe memhers of fin (r,) Thutomerism.
some homo loprl-s fomilY.
It aris{s il e lo l, j-migration ol a hydrogen atom
For example, lron onc polytabnt atom to the olhzr within the
samg molecule. Isomed ,htts obtained which erlst
(a) CHTCH2 -O-CH2CH3 is a metamer of
in tlyrumb eqvilihrium wiih each ollrat sre utllad
Ethoryethane
(Diethylethet)
liutomax anl lhE phanomenon is ctlled
tuulomerirm.
-/CH.' There are several types of tautomcrism but
cH3 -o-cH2cH2CH3 or CHr-OCH..- keto-enol taulonleism is thc most imPorlant. In
l-Mclhoiypropanc -CH,
this type of tautomerism one form (tautomer) con-
(Methyl n-ptopyl chcr) 2-'MelhoryProPanc
(t!'optory' I fiethYl ethet)
taios the keto group ()C =()) while the othcr
I

(b) CH3CH2-S-CHrCH, is a metamer of contains the enolic (>C = C OH) group. TWo -
Diethyl thioether simplest examples of keto-enol lautomerism are
acetaldehyde and acetone.
.zcHt 3O OH
( Hl-S-CH,CH2CH, or CH, -S - CHI
Methyl r-proFyl thioether
\ CH, zll
rcH3-c-H CHr=g-11
I

IsoProPYl mcthl thiocthcr +

Accraldchydc (k to fonn) Yii'Jl (cnolic forn)
^lcohol amount)
(c) CHTCHT-NH- CHTCH, is a metamer of e tnoTo) (Negligible

Diethylaminc 3ct

cH3 -NH-CH2CHzCH3
Methyl ,t+roPylamine
""lt
rcH3-'c-cH3
Acetone (k lo forrn)
OH
./cHt (ee'77o)
.rr CFl,
' - NH -CHl\crI. I

3
CHr=q-gg,
lsopropylmethylaminc Ptop- 1- .I.-2-al (cnolic fom)
(NcgliEible drnourr)
 ORGANIC CHEMISTRY SOME BASIC PHINCIPLES
- 14115

o OH oo
ll
d
fl
I
CC
O cry' \cH,/'\.,.,,
Ace\ lacctone (keb form, UVa)
Cyclohexanone Cyclohex- l-en- l-ol
(e8.gco)
In all thcmonocarbonyl compouads llstcd
(1.2%)
4'"'i'-o
o-)
t,
{-'.r
above, the greater stability ofthe keto-fo rmwlt. Lh--
enol form is due to lbe greater strength of the
carbon-orygen .r-bond (364 kJ mol-l) as com-
pared to carbon-carbon.z-bond (254 kJ mol-l).
(Enol fon\ 76%)

Ectofi Fectl trs-iEeE;iiie o-..-,.H \o

nnd enol forhs in keto-ehol toutomerism.
a mofi G-6iTeto
It
CC
The following three factors affect the position of -,,/
CH:- \ 'CH'/./z- \ 'CH,
equilibrium in keto,enol tautomerism.
lD coDtrasr, the compouDd cyclohexa-2, 4<lien-1-
(i) Stability ofthe eDol form, As stated above in
simple aldehydes and ketones (;a acetatdehyde, one exists totally in its eool form.
OH

is much greater than in acetaldehyde or actons. For

exanrple, in acetoacetic esler, the amount of enolic
fu*;+ d
Cyclohexa - 2.
(kzto
4 -dien - 1-o[e Phenol (otol form)
-form\
lot11 is 7 E" Thi reasbn baing that the enol form is aromalic
and is, theretbre, stabilized by the resonance energy o[
o
ll il
the benzene ring ( 151 kJ mol-1;.
C l-rrom lhe above discussion it follows. ,ra, ,tlidrer
ar,./ arrlt \ooHs <- the \Mbility oI the enol fonn, greatet b the enot ciniint.
(ri) Steric hiDdronce. Anothcr factor which
Acetoacetic ester
(1, 3 -Dicafionyl conpouatr) de(erntines thc enol content is the steric facior.'Ib
(keb fom\ 93%) illustrarc this, let us consider the enol coDtent of
acetvlacetone aod a- methylacetylactone.

()'.-H... ".o
lrr
CC
cnr/ \tcul 'crt,
(Etot Ionn 77.) Acetylacetone
(9 I -93Vo in gos phose)

t-l-.....H.\o o/H""o
lt lil ," C.
C.
,.CC\ z1r, \ ct\. ,,, \ ,,, \ 'cr.rl
cl\/ 'cH/" 'nqr, 'l
cHr
SiDtilarly, acetylacetone (,-r a l,3diketone) also a-Melhylacetylacetone
cxhibits kcto-enol tautomerisn but the antount of
cnolic fornr here is much hilhet (16%) rhan even iD
reetoacetic esler.'fhis is due to the reason thar keto
groop is a mttch bettet electron-wilhdran)ing group than
llkeslet group.
14/16
Pradeep's

44 5%) as comPared to that of acctylaceione

(el.e3%).
(iii) ElTect of polorlty ol solveEL Polar Prolic
solvens such as uater, mctbanol, acetic acid eic.which
form H-bonds Mth thc carboltyl SrouP of the kelo-
fofi daoease he enol conr L On thc other hand,
aDrotic solvenls such as hc,Gne, benzeDe etc. (or even whch arc in?-chain isomers.
tlie ahence ofsolvent) increase thc enol content. For Similarly, but-2-ene or 2-methylproP'1-ene
example, cnol form of acetylacetone is 76% in othaool are ring chain isomers of cyclobutane and methyl-
but is 92% in hcmnc. cycloproPane.
Es6entlol coDdltlors. For an aldchyde or a (c) CrHo represents :
ketoDe to cxhibit kcto-cnol tautomerism' it is cssential
that it nust have at le{st one a'lrydrogen atom. Thus, CH.C = CH and
aseaophenone, butaD-2{nc 8nd Propionaldehydc all ProPync
contain a-hydrogen atoms afld hence shco, keto-nol
which are also ring-chain
tautomerism.
oo
ldalo
14.E2. Stroisomerlsm

-H, - C- ctlrcH, Isomers which have the same structuralIor'

c6Hs- C- 6H3 mula but have different rclative arqnge,nent oI
Acctophcnonc Butan-2-onc O
utoms rS
o (Greek the
al phenom ex-
cH3-cH2-C-H ample, of
ProPioDaldchYdc
stereoisomerism.
In contrast, bcnzaldehyde, beMophenone etc' do
nol show ketonol tautomerism because they do Dot
CH3\ .z CHt
C=C-
CH, --.- _
C=C-
contain a-hydroSen atoms. - -\H H.,''
oo H.r/
.ir-But-2-ene
-CH.
@r-, @J"o lrans- B$t-2- cne
Due to n-bonding between the two carbon
atoms, the rotation around carbon-carbon double
Benzaldehyde
Bcnzophenone bond is prohibited and hence the geometry of the
atoms or grouPs attached to the carbon atoms gets-
simitarly, nitroomPounds also show tauto'
mersm.
fxcd in- spice. That is why this rype of
3
stereoisomeiism is also called geomcticdl
3
isomeism. Other t)?es of stereoisomerism are op-
cII3 -
+
N zo
-\o- \- 12
+
cHr=y .,,-oH \o- tical and geometrical isomerism' We will learn
72 more about stereoisomerisrn in unit 15.
Nitromcthane (l{iro -/ota) Q4ci-Ionn) 14.83. Steric hindrance
If two non-bonded atoms or groups in an
(vi) Rlng-chain isomerism

(a) CrH5 reprcsents :

which are ,qnJ-but-2-ene which has no steric hindrance.
ing-chain
CH3CH = CH2 and
Futher as the size of the atom-VgrouPs
isoners around a bulky atom increases, the sterichindrance
PtoFcnc increases accordingly. For example, as we move
 ORGANIC CHEMISTBY _ SOME BASIC PHINCIPLES 141't7

No stcric CH., stcric

H 7 TLiltlc
STERIC NO STERIC
' -/ rinana." , ' -/ hindrance
HINORANCE HINDRANCE
n-[4e, . H-[4,
tt
HH
Bromomcthane Bromoclhanc

H H

cls-gut-2-ene irareBul-2-ene

from bromomethane to bromoethane to 2- These steric effects are very important in Or-
bromopropane to re[-butyl bromide, steric ganic Chemistry since they influence the structure
hindrance increases as shown below : and reactivity of many organic molecules.

\- e Problems on structural isomerism and structure dererminarion of orgaDic

by lhe concept otdouhlc hond equivalerts (D.B,E) which inplies rhe stin of
in the molecule,lt is given by rhe relalron,
p.g.p. Ir (u - 2) * ,
= z'
where n is lhe number of differeot kinds of atoms present iD the molecule and u
is the valency of each arom.
For exampte, D.B.E. of M.E
j(4_2)+6(t_Z\+t(Z_Z\-r+l=0+l=l
CrHrO =:' -' "1'- -t''t'
Thb mcaw that voriot u tmcrurul isomen of C'H6O will conrain either one double bond (C
= C or C = O) or one
ing (lamoqtlb or futeruclclic) ar disctused betaw unda e2.
+ ona ing.
ond o hrce

isom
acyclic and cyrlic
uh, CrHrO.'
(r,,) CUr=Cg-61rrO, ,.. CH, = C11- ggt.
Prop-2-cn-l-ol Methoxycthenc
Solution. D.B.E.= (b) Clclic isomers are: HOH
)OO-zl+6(t-2)
Since D.B.E.
+t(2-2)l+t=t
= 1, therefore, CrHuO may con_
(y)
I t"
r-O
,,,2l
tainaC = CorC = O double bond or a ring. The Oxetanc Mcthylo.iranc Cyctopmpanol
following seven isomers are possible.
(a) Acyclic isomers are : Thus, CaHrO has seven isoners :
oo
illt s for
a-(e
(r) CHr - -
C CH3 (,r) CH3CH, - i - ff
Acriorc propioraldch)dc
14118
l'ratlca 1,'' Nest Course Ch"-ittriltrfrlD

FOR:,F.RA,ffi\.i'
l. "K:AE-LE-\\A9
Draw slructures ofall lsoDleric cthers corrcsPood-
iog to the molccular forn]ula C5H120.
2. Write condeNed and bond line strucl ural lbrmu lac
tor all the possiblc isomers of molccular torDula
c4H6'
(N.C.E.R-'f.)
3. Draw allthe possible isomeric polygoD tbrmulae for
lhe Dolocular fonnula CsHto.

AlV5-(L', Et<s-
1. D.B.E.= rZ [5 (4-2)+ t2(1-2\+1(2-2)] + 1=0' (i) CHz = Crl-CH = CH, or
Since D.B,E. = 0, theretbre, C'51{l2O rePreseDts Buta-1.3-diene
only saturated elhers. The follotriDt six isonrers ilrc
(ii) CH3CH2-C = CH or
possible. But- I -yne /\/
CH: (iii) CHr-C = C-CI{3 or
I But-2-yne
(0 cH3ocH2cH2cH2CH3 (ii) ctl3o-cHCHzCI ll (iv) CH2=C=CHCH3
l-Methorybutanc 2-Methorybutane Rula-1,2-dicnc

?', $r
(ni) cH3-o--cH2-cH-cH3
I mcthYIProPanc cyclobut6n6
>>-cH3
1-M6thykYcloPIoP6n
-Methoxy-2-
CH.
(ir)
'
cH,--o-c-ctl.
t- ,,,,
D(ln,
3.MethylcycloproF -n
,,,, f--"n,
M6thylsnocycloProPan
ln,
(ix)+
1

2-Mthqy-2- mcthYlProPane
(r') CHTCHT-O-CH,CH2CII3 Bicyclo[1 .1 .01 bdan.
I - EthoxyProPane
3. By polygon formulae, we mean Lyclic iornrulae.

o J A-
CH: C5H10 has the following six PotySon formulae :
I
(vi) CHTCHT-O-CH-CH3
2-EthoxYProPane

2. D.B.E. =rF (4 - 2) + 6 (1 - 2)l r | =2 cyclopentene MelhylcldobuEne ElhylcvcloProPan

Since D.B.E. = 2, (herefore, C4H6 has either two
double boDds or one triPle bood or one double
YA
bond and a ring or two rings.
The following nine isomers are Possible : /\/\
1 . 1 -DimetlrylcycloFop.nc 1 , 2-Dirlethylcyclopro pane

14.9. Nomenclature ol Organic CornPounds

The term nomenclature meals the system of

naming of orgauic compounds. ln case ofaliphatic
-two systenr-s o[ nomenclature arc
compJunds,
lentirully wed : (i) Tiviol or common q'stent and
lii) IUPAC sY*enr.

Thase namas of organic compounds are called trlvial

 ORGANIC CHEMISTRY SOME BASIC PRINCIPLES
- 14119

names or common nams, Originaly thc.se names
were given without any s)ntematic basis but later on
certain rule
compounds
rules have a
used to name all orgamic compounds.
(rr) IU"AC system. Because of the unique
property of catenation arrd isomerisrq carbon
Even
mber
hat it
com-
1947. These rules underwent modfications from
time to time and the most exhaustic rules for
IUPAC nomenclature of organic compouuds.
14.'10. General Rules of IUPAC System ror
Naming Organic Compounds .,.....
The IUPAC system is the nost rutional and
widely used system of nomenclaturc in organic
chemtstry.The most impottsttfedtltrc ol tltis systenr
is that dny given moleculor stnrcture has onlv one
IUPAC nome and ony given IIJPAC nu,:,t d,l nt,rcj
onbt otrc moleculor struclure.
The IUPAC namc of any organic compound
esscntially consists ofthrec pJrts. i.(.
l. Word root ?. Suffu and 3. PrcJix.
l. Word root. /f r'J rlebasic nttit of the nanrc. It
denotes the rutmber ol corbon otoms prcsent in thc
principal c\ah (the longest possiblc contitutour
chain of catbon utoms including the Iunctional group
and tlrc multiple bonds) of the oryanic ntolecule.For
chains from one to lbur carbon atoms, special wcrd
roots (based upon the common names of alkanes)
are usedbut forchains offiye or more curbon atoms
Greek number roots arc usetl as giverr boktu, :

CIIAIN LENGTH WORD ROOT CHAIN LEN(TtI \YORD ROol'

ct Meth- q Uept (/r-
q Eth- q Oct (.r)-
q Prop (aF q Non (zF
c4 But (4F 9o Dec (a)-
c5 Pert (aF 9r Uodec (r)-
c6 Hex (aF 9z Dodec (n)-

.Extra-'a'given in parenthesis is used only if the primary suflx (explained larer) (o be rrdLlctl rti thL
word root begins with a consonant. ln general, the woid rooifor any carbon
chain is alk.
2. SuIIIx. There are two t1ryes of suffixes :
(i) Primary sufifix.A pimoty sufix is always addetl to the word root to indicate
, $ saa$akd
cnon or unsaturated" T three basic primary suffixes are given below
wlrcther thc carbon
:
TYPE OF CARBON CHAIN PRIMARY SUFFIX
(a) Saturated (conraining sirgle bonds oDly)
-ane AlkaDe
(6) Unsaturated with one double bond --eDe A.lkene
(c) Unsaturated with one triple bond
-yne AlkTnc

_
Ifthe parent carbon chain co tains two, three,
such as di (for two), tri (for three), tetra (for fourj etc. are added to
TYPE O[ CARBON CHAIN

(.r) Unsaturated wirh two doubte bondc

-diene Alkadiene
(b) Urisaturated with two Eiph bondr
-dyre Alkadiync
14120

suflxes in naming organic

The following examples illustrate the use of word roots and primary
compounds :

WORD ROOT PRIMARY SUFFIX IUPAC NAME

ORGANIC COMPOTIND

But ane Butane

cH3cH2cH2CH3
Prop ene Propene
CH3CH=CH2
Erh re Ethyne
CH=CH ,T

Buta. diene Buirdiene

cH2=cH-cH=cI{2
Butadiyne
HC=C-C=CH Buta. , diyne

*Extra,a,hasbeenaddedtothewordrootsincetheprimarysuf6xi.e.,dieneordiynebegiDswitha
consonant i.e., 'd' instead of a vowel as is the case in the last two examples'
(li) Secondarf, suflix .A secondary s1tfrx is then added to the-pimy *try b *!:':t:-:!:.::!:*
suffxes ofsome important tunctronal groups
lu"cdiii gr"up pisentin the oryanic compound' Secotdary
are given below :

Alcobols -oH
_CHO
Aldehydes
Ketones >C=O
Carbo,(ylic acids -cooH
Acid amides -coNH2
Acid chlorides -coct
Esters
_COOR
Nitriles -cN
Thiol --sH
Amines -NHz
It mov be noted lhat while imary sufrix' the terminal 'e' of the pimory
besiis itn a vowet but is rctained iI the
',ffi;i{::;;;';;;';;;;;;;
secondary suffa begins with a consonanl
Thefollowingexamplesillustratetheuseofwordroot,primarysufExandsecondarysuffixinnaming
organic compounds.
PRIMARY
SUFIlIX

Erh an (.). ol Ethanol

cH3cll2oH
an (e). amine PropaDamine
clllclr2cE2NH2 Prop
an (r). oic acid Butanoic acid
cH3CH2OH2COOH But
aoe nitrile Propanenitrile
cH3cH2cN Prop
en (.). al Prop-2-en-1-al
CH2=CHCHO Prop
yn (?)' oic acid Prop-2-yn-l-oic acid
HC=CCOoH Prop
 ORGANIC CHEMISTRY _ SOME BASIC PBII'CIPLES 14121

*The terminal 'e' from the primary suflx has

been dropped because the secondary suflx begins 321
with a vowel. HC = C- CO2H
Prop-2-yn- I -oii: acrd
It may be noted that according to 1993 reconr. (Iotl c )' 2 - ptop)l t oi c ac i,l)
mendatlous o[IUPAC nonnclature of Organlc
Compounds,
3. Prelix. There are two types of pretixes :
(i) locauts (numticals and/or lette6) are placed (i) P mary prelix. A primary prefix is used
irumediateb before the patl of the name to which simply to distinguish cyclic from acyclic com-
tlrcy relate. For example, pounds. For example, in case ol corbocyclic com-
pounds, u pintaty prefix, cyclo is used immediotely
But-z-ere Propan-2-ol
bcfore tlre word root.Thts,
(formerly2-butene) (formerly2-propanol)
CH,, Cyclo + pent
{ii) the locant } (uniq) is oftcn omi edwhen there ,/\ preiix Word root
Primary
is no afihiguity. For example, CH, CH.
l' | ' + ane : Cyclopeutane
1 CH2- CH2 Primary suflx IUPAC name
CH,CH3CH,NH2 Propsn-l-alnine is often
rrunted as Propanamine
If the prefix cyclo is not used, it simply indi-
CICH2CH2OH cates that the compound is aqrclic or open chain.
2-Chloroethan- 1-ol is often
trutned as 2-Chlorcetlwnol
(ii) Secondary prcllx, In IUPAC sptem of
nomenclature, certain groups are not considered as
t
CH3CH2CHZCHO Buton-|-al is often wrium functional groups but instead are treated as rzr-
as
stifittents. These ore called secoIodary prefixes and
B tanal
are odded immediately before the wod rool (or rc
pinttry prefu in case oI corboctulic contpounds) in
Howeve4 ir this book, the nunruicol locant I ir tlphabetical order to denote lhe side chains or rub-
always included wlren onotlut nlu,tcticql loca ap- stitutenl groups. The secondary prefxes for some
peqrs in lhe sanrc tranre. For example, groups which are always treated a*s substitutent
321 groups (regardless of the fact whether the organic
CH, = 911-gg. compound is monofunctional or polyfunctional)
Prop-2-en- I-al are given below :
U)moly 2-propenaD

SECONDARY SUBSTITUENT SECONDARY

PREFIX GROUP PREFIX

-F Fluoro OCH3 (OMc) Methoxy

-ct Chlom -oc2H5 (-oEt) Ethoxy

Bromo
-Br
_I Iodo - cHl (-Mo) Methyl

-Noz Nitro -c2H5 (-Eq Erhyl

-NO Nit160 -CtlzCHzCHj (z-Pr) l,-Propyl

+
-N =N Diam -cH(cH3)2 (-iPr) Isopropyl
Alkuy _c(c H3)3
-oR tert.-Butyl
14122
Net4 Course Che istr,!

Besides these, other functional groups are Secondary prefu + Pimary Prefa + Word
also treated as substitutent groups in case of root + Pimary suffir + Secondary tafrx
polyfunctional compounds as discussed later in this The following examples illustrate the use of
unit. word root, primary and secondary prefxes and
Thus, the complete IUPAC name of an or- suffixes in namiug organic compourds :

ganic compound consists of the following Patts :

ORGANIC SECONDARY WORD PRIMARY IT'PAC NAME

COMPOUNI)S PREflX ROOT sul-Flx

CHJCH2BT Bromo eth aDe Bromoethane

cH3N02 Nitro meth aDe Nitromethane

qH5oqI{5 Etho.y eth ane Etho(yetharle

In case of carbocyclic compounds, primary 1. Saturated hydrocarbons - Alkanes

prehxes are also used. For example,
Br 4-Bromo + cyclo + hx

General fonnula: C,H-*2wherc n = L,2,3,

I addingthe suffxane to the word root indicating the
OH
The comrnon ald IUPAC names of some im-
portant classes of organic compounds are given
below :
1 4.1 1. Nomenclature of dirlerent classes
Compouruls ol carbon and hydrogen are
called hydrocarbons. These are further divided
into two classes '. sdturated and unsdturated
hydrocarbons.
Primary suflu : ane.
The IUPAC names ofalkanes are obtained by
number of carbon atoms.
For example, names ofalkanes containing five
or more carbon atoms are obtained by adding
prefxes such aspezt (five),
oct (eight) etc. indicating
atoms in the molecule to th
the first four alkanes (CH4 to ClH,o) have their
sDecial names i.e. methsne, elhqne, ProPane and
bitane. The tame of an individual alkane is always
written as one word. The molecular formulae,
IUPAC and cornmon names of some alkanes are
given below :

n FORMUI"A COMMON NAME IUPAC NAME

.t. Methane
cHl Methane
Etbane EthaDe
cH3cH3
cll3cII2cH3 Propane Propanc
3.

cHrcH2CH2CHr ,!-Butaoe ButaDe

4.
,r-qentane PeDtane
5. crI3cH2cH2cH2CH3
CH3(CH2)aCHr n !Hexaoe Hemoe
6.
 ORGANIC CHEMISTRY SOME BASIC PRINCIPT-ES 't4123
-
7. cH3(cHz)5cH3 n.Heptare Hepune
8. cH3(cHz)6cH3 /'-OctaDe Octaae
9. cH3(cH2)7cHr a-Nonane Nonane
10. cH3(cHrtcH3 n-Decane Dene
11. cH3(cH2)t8cHl IcGane
12. cH3(cH2)28cH3 ?iamotaEc

I}pes of allanes. Dcpending upon the struc-

ture ofthe carbon chain, alkanes are of the fotlow- 9H,
I
ing two types :
cH3 - c-cH2cH3
(l) Stralght chain alkanes. As the name I
suggests, these alkanes contain straight chains of cH.
carbou atoms in their molecules. In other words, 2. 2-Dinre!hyjburanc
alkanes in which no carbon stom is linked to more (Ncohevne)
than lwo other carbon atoms are called slraight To distinguish the straight chain alkanes from
chain olkanes branched chain alkanes of the same molecrrlar for-
mula, the prefixes l,ro and neo are used in thc
common system. Tho prelx rio is used when the
cHr-cH2-cHz-CH3 second carbon ofthe brauched chain alkane cerries
B\ltane (n-Butahe)
onc methyl group while the prela neo is used for
those branched chain alkanes which contain a
quutetlwry catbon at the end of the chain.
cH3 - cH2-cH2- cHz- cH2 -' cH3
Hcxanc (nJlqane) Types of Carbon and llydrogen atoms in
Alkaues
The common names oI straight chain alkanes The carlton atoms in an alkanc molecule may
are tbe same as their IUPAC names except that the be classified inro folur tgpes as pimqry (1.), secon-
prel\x n-(normal) is used in lhe common names dary (2'), kniary F ) andquatemury (4) as follows :
(given within brackets). (i) A cohon atom attached to one other (or no
other) cqrbon dtom i,r called a primary carbon atom
(ii) Branchedchain alkanes.In these alkanes,
und is designated ss 1o carbon.
all the carbon atoms are not presont in a linear
sequence. In other words, a/kar es in which at least (ii) A calbon atom ofloched to tno other carbo,l
otte catbon atom is linked to three or slortts is called a secondar? carbon atom and is
fou otlrcr
designated as 2o carbon-
cud)on atomt ore calledbranched chain alkone s. For
example, (iii) A cubon qlom attached to three othcr
.cH3-cH-cH3 carbon atoms is called o tefliary carboa atom ond
cH3-cH-cHzcH3 is designated as 3" carbot
I
cHr (iv) A cafion atom ottaclrcd to four othercorb-
CH:
on aloms iscolleda quaternary carbon atom andis
2-Methylprcpanc z-Methylbutanc
(Iwbut@re) (hopewanc)
designated qs 4o carbon. .

cH3 -cH - cH2cH2cH3 cHl_( -CHl

i',
rl
CH: CH,
2-Mcrhylpcnlarc 2, 2-Dimdhy'proparc
(lsohaarc) (Ncoryttort)
14124
Pradc cp's Neut Coarsc Chcmistrg ftft[p
1' miral 'ane' of the corresponding alkaue by the
CH, suffx!'.
r12"3'1' Alkane - qne + ),, = AlkYl
cH3-4'c-cH2-cH-cH3 In case of propane and higher alkanes, the
tt
cHt
position of tbe carbon atom from which the
Lydrogen is removed is also prefixed to the name of
rcHs the alkyl group.
The IUPAC narnes and structural formulae of
AIM SFoups. The remova.l of one hydrogeo some ofthe alkanes and their alkylgroups are given
atom from the molecule of an alkane gives an allcyl below :
group. Thus, alkyl groups have the general formula,
Gneral Fomrula, qHr, * 1 wherc n= 1, 2,3,
QHr,,*r. These are often represented by the letter
R. Their names are derived by replacing the ter- 4.... etc.

Name Brd structural formuls CorredPondihg nlkyl grorp IUPAC name

ofthe rlknne (commo[ name)

MethaDe CH4 cHr- Methyl (Merlryl)

Ethane, CH3 - CH3 clt3 - cH2 - Ethyt (E tyl)

Renroval of l"H 321
cII3-CH2-CH2- 1-Ptopyl (n-Prcpyl)

1" 2" 1'

cH3-cH2-cH3
RerDoval of2"H 2
cH3-CH-CH3 2-Propyl (lsopropyl).

Removal of 1'fI 472t

cH3cHlcH2cH2- l-Butyl(r-Barl)

cH3cH2-CH-{H3 z-Blutyl (tec-Btttyq

CH
Removal of 1"H
3n.-'J*, dn,- z-Methyl - 1 -pt oryl (h o b u ry D
l'
CH,.

3rr-'',lr-5r, CH,
3n,-'tr-ir,, 2-Methylz-ptoryl (te - Butyl)

CH: CH:

,I
CH._C-CH,
I
crr,-l-cu.-
' Neopentyl

cH3 [n,
Ncopcntanc
I
dlr(clt2)scHz r-Daql (n-Decl)
cH3(cH2)8cl.I3 -
Decane
ORGANIC CHEMISTRY SOME BASIC PRINCIPLES 14125
-
2. Unsaturated hydrocarbons. Open chain z = 2,3,4....
Genemllormula: CoHr. where
hydrocarbons which conlain carbo,r{arbon double etc. Pimary stfix: = enc
( >C=C <) or triple (-
C= C -)
bonds i,t ttteit
C0mmon names: Alksne-qnc + ylene
rnolecules oru called unsaturated hydrocarbons.
These are further classified into two types'. olkanes
: Alkylene
and allqnes. IUPAC names : Alkane-ane+ene :Alkene
(l) A]kenes. Unsatwsted aliphotic hydrocor- The positions of the double bonds are indi-
bons containing a ca,bon-carbon double bond are cated by the Greek letters o ,F ,y ... etc. in the
colled alkenes.They are also called olelins (Greek : common system while arabic numerals, r'.e. 1, 2,
olefiant : oil forming) since the lower members of 3, 4 etc. are used in the IUPAC system. For ex-
this class react with chlorine to form oily products. ample,
Their general formula and suffix are given below :

D FORMUT.A COMMON NAIUE IUPAC NAME

,,
CHr-Cg, Ethylcnc Ethene
3 CH,CH=CH, Propylene Propcne
fd
4 CH3CH2 CH=CH, a-Butylcne But-1-ene
2t
pa
4 cHlcH=cHcHl p-ButyleDe But-2-ene

(ii) Alkynes. Unsqturqted oliplrutic hydrocar- Common names i Acetylelte sd iE allEl

bons containing a carbon-catbon liple bond. otc derivotives
culled alkynes: In the common system, they are
called acetylenes after the name ofthe first mcmbcr
IUPAC names :.,{/kane
- ane + )me = Allryne
The position ofthe triple bond on the parent
of this family, i.e. acetylene. chain is designated by lowest possible arabic
General formula : CnHrn-, numerals-
where r = 2,3,4, .... elc. The common aod IUPAC names of a few
Pimary suffa = yne simple alkpcs are given below :

n FORIIIUI-A COIITMON NAME IUPAC NA.[IE

, CH=CH Acetylene Ethyne

3 CHr-C=CH Melhylacetylene or Allylcne Proprne
zt
4 CHTCHT-C=CH Ethylacetylene But-l -yne
2l
CH,-C=C-CH. Dimethylacetylene But-2-yne

3. Haloalkanes..i?alogen deivatives of olkanes or R-X where R is any alkyl group

are called haloalkanes. They are further classified
Functional group : X(halogen)
as ntono-, di, tri- and telrahaloalkanes etc. accord-
ing as they contain one, two, three, four etc. halogen Secondary prefu = Halo
atoms respectively in their molecules. Common names. Add the word halide
(a) Monohaloalkanes. The monohalogen (fluoride, chloride, hromide, iodide) to the name of
deiyatives oI alkanes are called alBlhalldes. the alkyl group,
Geneml formula: C,IIr.*, Xwheren = 1,2, i.e., Allql + lrulide : Alkyl hallde
3 .... etc. and X : R Cl, Br or I.
14126
IUPAC namcs. Add thc secondary prefixha/o
to the name of the corresponding aiitaae.
i.e., Halo+ alkane = Haloalkane
i t.ta.t'1,'s Neut Coursc Chemistrglfifi
In case of dihalogen derivatives, the positiofts
of both the halogen atoms are indicated.
The IUPAC and common names of some im-
portant haloalkanes are given below :

FORMULA COMMON NAME IUPAC NAME

cH3-ct Methylchloride Chloromethane

cHrcHr-Br Ethyl bromide
321
cH3cH2cH2-I n-Propyl iodide
321
cH3 -cH-cH3 Isopropyl iodide
I
I
(b) Dihaloalkanes. Alknes containing two
halogen atoms per molecule oJe called
dilwloalkanes.
Gcneral formula: C.H2nXzwhercn : 1,2,
3....etc.
Common names. For purpose of naming,
dihalogen derivatives of alkanes, these are divided
into three categories :
(i) Al|rylidene dlhalldes. Dihalogen deriva-
tives of alkanes in which the two halogcn atoms are
attached to the same carbon atom are called
allrylidene dihalides or sinply allrylldcne halldes.
Further since the positions on the same carb-
on atom are called geminal posrfrbns, therefore,
alkylidene dihalides are also called gemlnal
dihalides or simply gemdlhalldes.
(ii) Alkylene dihalldes. Dihalogen deriratives
of alkanes in which the two halogen atoms are
FORMULA COMMONNAME
Bromoethane
1-Iodopropane
2-lodopropaoe
attached to adjacent carbon atoms of the chain are
called allqlene dihalides or simply allrylene
halides. Further since position-s on the adjacent
carbon atoms are c alled vicitrol positionS therefore,
alkylene dihalides are also called vicinal rllhalldes
or simply vic- dihalides.
(iri) Polymethy'ene dlhalidcs. Dihalogen
derivatives of alkanes (containing three or more
carbon atoms) in which tbe two halogen derivatives
are present on the termiral carbon atotr.1i.e.,a,w-
positions of the carbon chain are called
polymethylene dihalldes.
IUPAC names. In the IUPAC system, all types
ofdihalides are called dihaloalkanes, the positions
of the halogen atoms being indicated by lowest
possible arabic numerals.
The common and IUPAC names of some
dihaloalkanes are given below :
IUPAC NAME

c}fzct:. Methylene chloride Dichlorometharle

CH3-CHBrz Ethylidene dibromide 1, l-Dibromocthane
BrCH2-{H,Br EthyleDe dibronlide 1, 2-Dibromoethane
cH3cH2cHCr2 Propylidene dichloride l, l-DicbloropropaDe

-tl-
CH,--CH-CH, Propylene dichloride 1, 2-Dichloropropaoe

ci cl

a,rlf', 21
Isopropylidene dichloride 2, 2-Dichloropropanc

CI CI
321
ctcH2cH2cHzcl liimerhyleoe dichloride 1,3- Dichloropropane
 OBGANIC CHEMISTRY SOME EASIC PRINCIPLES
-
(c) Ihi. atrd tetrabaloalkanes.The generul for-
,zur4 of trihaloalkancs is Co Hr,-1 X, while that of
tetrahaloalkanes is C, Hr,-2 X. where n : 1, 2,
3.....etc. and X :
g Cl, Br, i.
IUPAC names. In the IUPAC system, these
are called trlhaloalkanes and tctt'shaloalkares.
The positions of the halogen atoms on the carbon
chain being indicated by arabic numerals.
14127
Common or Tlivial names. There are no sys-
[ematiccommon names for tri- and tetrahaloalkanes.
However, triha-lomethancs are bcst known by their
trivial namcs r'.e,, hakrforms, tctrahzrlogen derivatives
of methane are qrlled carbon tetrahalides. While
symmetrical tetrahalogen derivatives of ethane are
called aety'ene ttrahalides. The trivial and IUPAC
names of some tri- and tetrahaloalkanes are given
below :

FORMUI,A TRMAL NAIIIE IUPAC NAME

clIF3 FluoroforD Ttifluoromethane

cHCt3 Chlorotbrm 'Itichloromethane
CHBrI Bromoform TtibromomethaDe
cHIs Iodoform ThiiodomerhaDe
cH3-cct3 l, 1, 1- 'IiichlorocthaDe
ctcll2-cHCl2 1, l, 2- Thichloroethane
cctl CarboD tetrachloride 'IEtrachlorometbane
B12CH-CHB12 Actylene tetrabromidc 1, 1, 2, 2jfetrabromoethane
ctcH2-ccl3 1, l, 1, 2- 'IbtrachlorGrhane

4, Alcohols or Alkanols Functional goup :- OH (hydtoxyl)

Almhols are classified as manohydrig Secondory saffa : ol
dihydric, oihydric and pofuydric z6asrling as their
Common namcs. Add the word alcohol to the
molecules contain one, two, lhree al,,dmanyhydroryl
namE of the altyl group,
groups respectively. Since presence of two or r.:ore
hydroryl groups on thesame carbon atommakesthe Le., AlSl + akohol = AIM alcohol
moleculc unstable, therefore, in di ad an dpolyhydric
alcohols, each hydroryl group is present on a dif- IIJPAC namcs. Replace thc terminal 'e, from
ferent carbga atom. the name of the corresponding alkane by the suffix
alcohols. 'ol'.
!g46onohxdrtc i.e., Alkane - e + o/ : Alkanol
Generalformula: C"Hr,*, OH (wherer = 1,
2,3 ...) or R-OH (where R is any alkyl group) SoEe imporant eramples are :

FORMUI-A COMMON NAME IUPAC NAME

cH3-oH Mcthyl alcohol Methanol

cH3cH2-oH Erhyl alcohol Ethanol
321
cH3cH2cH2-oH n -Propyl alcohol Propan-l -ol
321
CH1-CH-CHT
-l lsopropyl alcohol Propan-2d
OH

(ii) Dihydric alcohols :

General formula : Cn H1 (OH), where n : 2,
3,4....etc.
14128 Neur Cottse Cltem istrq
glycols etc. Thus, a-glycol is 1, 2-glycol, B-glycol is IUPAC names. Add the suffix 'diol' to the
1, 3-glycol and ro-glycol is one in which the two OH namc ofthe alkane containing the same number of
groups arc attached to the tcrminal carbon atoms carbon atoms as the diol.
of the chain.
Alktne + diol = Alkanediol
Common names. In the common system, q-
g/ycols (also called vic-glycols) arc named byadding The position o[ the two hydroxyl group is
the word 6/ycol to the common name of the alkene indicatecl by urabic nunrerals.
from which they have been prepared by direct The common and IUPAC namcs of some
hydrorylation. In contrast, B-,y- and ru-glycols are glycols are given below :
named as the corresponditg polymethylene glycols.

F'()RIUUI-A COI\,IMON NAME IUP-,I,C NAME

21
HOCIJ2-CH2OH Ethylcne glycol EthaDe-1, 2-diol

21
cH3-cHoH-cHzoH Propylene glycol Propane-1, 2-diol

321
HOCH2-CU2-CH2OH Tiinrethylene glyml PropaDc- 1, 3-diol

(iil) TFihydric alcohols IUPAC name. Add the suf{ix'rlior to thename

ofthe alkane containing the same numbcr ofcarbon
General formulo : C, Hr,-l (OH), atoms as the triol.
Alkane + lriol = Alkanetriol
Common namcs. Therc is no gcneral rulc for
The positior. of the hydroryl groups is indi-
naming these alcohols.
catcd by arabic numerals.

FORIUUIN COMMON NAME IUPAC NAME

32r
cH--cH-cH- Glyccrol or Glvcerine Propaoc-1,2,3- triol
l'|
OH OH OH
t'
- '
.5. Ethers or Alkoryalkanes ethers, the numericalprefxdi is added to the name
Geneml fotmula : R-O-R' where R and of the alkyl group followed by the word ether.
R' are same or different alkyl groups. If R : R', IUPAC names. In the IUPAC system, ethers
ethers are called rr'rnp le ethen atd if R * R',then are called alkoryalkanes. The smaller alkyl group
ethers are called m ixed ethen. forms a part of the alkory group while the bigger
alkyl group forms a part of the alkane. The names
Functional Wup i- O- of the ethers are then derived by adding the suffix
Seconday prefa: Nkox! alkory to the r.arne of the alkane,
Common names. Itr case of mixed ethers, add i.e., Alkory + alkane = Alkoxyalkane
the word ether to lhe names of the alkyl groups
arranged in alphabctical order. In case of simple Some important examples are :

IIORIlIUT,A COMMON NAME IUPAC NAME

cH3-o-cH3 Dimethylether Meiho)rymelhane

Ethyl methyl ether MethoxyetLane
$ti-4-cH2CH3
cH3cH2-HH2CH3 Diethylether Ethoryethane
 ORGANIC CHEMISTRY _ SOME BASIC PRINCIPLES 14129

6. Monocarboxylic acids or Alkanoic acids Common names. These are derived from the
Gcnerul formula: C,II,,*1COOH where z = name of the platrt or animal Iiom which they were
0,7,2,3..... etc. or R-COOHwhere R = H or first isolated.
any alkyl group. I(JPAC names. Replace terminal ,e, from the
o name ofthe corresponding alkane by the suffix orc
ucid
ll
Functional goup : -C-OH (carboryt) i.e., Alkane -e + oic acid =Alksnolc acid
Secondary suffa : oic aeld Some important examples are :

FORMUI.A COMMON NAME IUPAC NAII'ID

_ n-6oon Formic acid Metbanoic acid

cH3-cooH Acetic acid Ethaooic acid
cH3cH2-cooH Propionic acid Propanoic acid
cH3cHzcHz-cooH z-Butyric acid Butanoic acid

7. Aldehydes or A.lkanals Common uames. Replacc lc acid from thc com-

Generalformula: CnHrnll CHO where n = mon name of the corrasponding acid which they give
0, 7,2,3..... etc. or R-CHO upotr oxidation by th e word oldelyde . po, example,
where R = H or any alkyl group. Acetic acid - ic ocid + aldehyde :
Acetaklehyde
o IIIPAC names. Replacc the terminal .e , from thc
name of the corresponding alkane by the sulfx al
il
Functional group: - C-H (aldehyde) Le., Alkane -e + a/ = Alkanat
Secondary suffa : al Some cxarnples are :

IIORMUI,A COMMON NAME IUPAC NAJIII'

h-LHU Formaldehyde Mcthanal
cH3-cHo Acetaldehyde Erhanat
cH3cH2-cHo Propionaldehyde Propaoal
cH3CH2CH2-CHO a-Butyraldehyde Butanal

t, Ketones or Alkanones Common names, In casc of mixed ketones,

Genem$ormuh : C rHar*1COCrHr,*1 where name the alJcyl groups in alphabeticat order and
n= RandR,, then add the word ketone. In case of simple
may If R=R" kctones, the numerical prefix di is used before ihe
keto if R*R,, name of the alkyl group,
keto IUPAC names. Replace terminal ,e, from the
name ofthe corresponding alkane by the suflxoze
Functional group : >C = O (Ketonic)
i.e. Alkune -e + one = Alkanone
Secondory suffu : ollre
Some ex4grples are :
l4130
iiralc.tll's Netl Course Chemiqtrq@

IIORMUIi COMMON NAME

Dimethyl ketone or Acetonc Propanone

cH3-co-cH3
Ethyl orethyl ketone ButaD-2-one
CH3-CO-CH2CH3 or Butanone
12145 Methyln-ProPYl ketoDe PeotaD-2-one
/'f-H3-CO-CH2C[12CH3
't2345
Diethyl ketone Pentan-3-one
cH3cH2-CO-CHzCIl3

. 9. Acitt chlorides or Acyl chlorides or Acetic scid - ic acid + yl chloride = Acetyl

Alkanoyl chlorides chloride
General lormulo: RCOCI where R = H or IUPAC names : Replace terminal 'e'from the
any alkyl grouP name of the corresponding alkane by the suffix oyl
o chloide,
ll i.e., Alkane -e I oyl chloide = Alkanoyl
Functiottul gtouP : -C-Cl chloride
Sccondary sulfu : oYl chloride
Common names : Replace ic acid' from thc Some important examPles are :

common name of the corresponding acid by y/

chloride For examPle,
COMMON NAME IUPAC NAME
T.ORMUIN

Formyl chloride MethaDoyl chloride

H-1OCI(trnstobb)
Aclyl chloride EthaDoyl chloride
cH3-{ocl
PropioDyl chloride Propanoyl chloride
cH3cH2-COCI
Butanoyl chloride
tirrcnrbnr-coct ,,-Butyryl chloride

'. 10. Acld anhYdrtdes Common or IUPAC names: Replacetheword

-General scid ftom the common or IUPAC name o[ the
lotmual : R- CO - O - CO -
R' or
corresponding acid by the word anlrydride '
(RCO)rO where R or R' may be same or different
alkyl groups.
oo
llll
Functional grouP : - C- O - C-
Secondary suffx : anhYdride ' Sonie imPortant.examPles are :

COMNION NAME IUPAC NAME

FORMIIIA

Acetic anhydride Etbanoic anhydride

(cHsc.oLo
Propanoic anhydride
ltHrcn co;ro Propionic anhydride
Bis(chloroacetic anhYdride) Bis(chlorocthaDoic anhydride)
(crcurco;ro
Acltic formic anhYdride EthaDoic metbanoic anhydride
4co-o-cocH!
 ORGANIC CHEMISTRY _ SOME BASIC PRINCIPLES
14131
11. Esters Common or IUPAC n rmes : Write the name
(ieneral formula r R-COOR'where R=H of the alkyl group before the common or IUpAC
or any alkyl group while group R, is always an alkyl name of the parcnt acid with its tcrminal rc acrd
grouP. replacrd by oate.
o
il
Functional group : - C- OR, (esfer)
Some important examples are :
Secondary prefa : alkyl
Secondary sufa : oate

IUPAC NAME

H-COOCH3 Mctry formaE Methyl mcthanoate

H-cooqH5 Ethy' formate Ethylmethanoate
cH3-coocH3 Metbyl acetate Methylethanoate
cH3- cooqHs Ethyl acEtate Ethyl ethanoatc

12, Acid amides or Nkanamides

Common names : Replacc ic acid, ftom lhe
Generolformula: RCONH, where R = Hor common nartre of the corresponding acid by the
any alkyl group secondary sufEx azride.

o
il
th
arnide,
.tJffi
Ft.nclional Wup : - C
- NH, (omide)
i.e., Alkane - e + amide = dkanamide
Secondary suffa : amide Some important exaanplcs are :

IUPAC NAME

H-CONHz Formamide Methanamide

cH3-coNH2 Acetamide Ethanamide
cH3-cH2-coNH2 PropioDamide Propanamide

13. Primary Amines (i) Altach the prefixamrno to the name ofthe
General formula r R-NII, where R is corresponding alkane,
any
alkyl group ie., Amino + alkane = Aminoalkarre
nurctional goup : -NH, (amino) IUPAC names. Replace the terminal ,e, from
tbe nam-e of the corresponding alkane by the secon-
Seconda,l- suffa : amine dary suffix anine,
Common names : (i) Add the wotd amine to
the name of the alkyl group, i.e., Alkane -e * amine = Alkanamine
ie., Allcyl I amine = Allcylamine Some importaDt examples are :
 llrad a,, 1,'s Nett Course Cheoristtrlfiffi

COMMON NAME

Methylamine or Arninomcthane Methsnamine

cH3-NH2
Ethylamine or Amiloethane E(hanamine
cH3cH2-NH2
121 ,l.Propylamine or I -AminoProPane Propan-lmine
clt3cII2CH2-NH2
or PropaDamioe

\{{. SecondatJ amlnes numerical prefx di is used before the name of the
alkyl group.
General fotmula: R-NH R'where R and
-
groups' the name of
R' may be same or different alkyl
Functional grouP: > NH (rrn ino) the ouP forms a

N-Nlql
par larger alkYl
Secondary Prefa : gro
Secoruhry sufft: amllrc IUPAC names : Add the prefix N-a'Ikyl to the
ups name of the alkanamine corresponding to the
in in"' larger alkyl grouP,
ln the
i.e., N-All<yl * alkanamine =N'Alkylalkanamlne
Some ImPortant examPles are : s

COMMON NAME ITIPAC NAMD

FORMULA

N-MethylmethaDamine
Cl-I3Nl ICH3 or (cH3)2NH Dimc rylamine or N-Mcthylaminomethane
Eth,'lmetlrylamine or N'Methylaminoethane N-Mctlrylethanaminc
cH3cII2NHCH3
Diettrylamine or N'EtbylamiDothaDe N-Ethylethanamine
(cH3cl-12)2NH

' 15. Tertisry amines

R'
I
General fonnula: R-N-R" where R, R"
R" mav be same or different alkylgroups or two of
group.
them may be same while the third may be dilferent'
IUPAC
' Secondary Prefu : N-allrYl' N-alkYl
N-allcyl (sma
I
alkanamine
Functional poup : -N - (tertiqry ni'rogen
gouP.
atont) Secondary sufu: amine
Some important examPles are :
Common names. (i) Name the alkyl groups in
alphabetical order u"dj!9i!9.'ffi* ot" Ifj*'
COMMON NAI\{E IUPAC NAME
NORMULA
N, N-DimethYlmethaMmine
(cH3)3N fimetlrylamine or N, N'DimethylamiDomethane
N, N-Dimeihylethanamirle
cHrcH2N(CH3)2 Ethyldimcthylaminc or N, N'Dime thylaminoe thane
N-Ethyl-N-methylethanamine
(ci3cHr2NCH3 Diethylmethyldiiine or
. N-Ethyl-N-mttlirlaminoethane
N, N-DiethyletbaoamiDc
(cH3cH2)3N Ttiethylamine or N, N-Diethylaminoethane
 ORGANIC CHEMISTRY _ SOME BASIC PBINCIPLES
14133
16. Nltrt,alkanes Common names. There are rro common
Geteral fonrutla .. R-NO2 where R is any names for nitroalkans.
alkyl group. IUPAC names. Add the secondary prefxn ra
Functionol group : to the name of the alkane,

_N z'
\o -i4\()- <,u-,
i.e., Nitro + alkone = Nitroalkane
Some important examples are:
Secondary prefx : nitro

Noz
cHr-NO2 Nitrome thane cu,1JH-[H, 2-Nitropropane

cH3cH2-N02 I
Nitrothane cH3CH2CH2CH2-NO2 l- Nitrobutane
Noz
cH3cH2cH2-NO2 l- Nitropropane lH,3Jr-.n,.r, 2- Nitrobutaue

17. Alkyl nitrits Common names : Add the secondarv suffix

Generol formula : R-O-N = O where R is nitrite to the name of the alkyl group
any alkyl group
Le., Allql + nitite = Alkyl nitrite
Futrctional group : -O-N = O (nifite)
IUPAC names. There are no IUpAC names
Secondsry sufix i nitlile for alkyl nitrites.

FORMULA
FORI\{ULA COMMON NAME

cll3--o-N = o Methyl nitriie cH3cH2cH2-o-N = o r-Propylnitrite

O-N=O
cll3ct-I2-o-N =O Ethyl nirrire cur-Ju-cn, Isopropyl nitrite

\*t(
Alkyl cyruldes or AlkanenlHles Acelic dcid - ic acid + onitile = Acetonitrile
-_ -General formula I R-C = N where R is any However,
alkyl group . J.eplacEd.by
$
in case of propionic acirJ. onic acid
Functionql goup: onifiile.For example, propionic acid
-C=N (clano or nitrite) onrc sctd + onitrile = proplonitdle.
Secondor sufu : nll,Jfile
Comlo-n names : (i) Add the suffu cyonide to suffix n /a7e to the
..
the name of the alkyl group, naT the same number of
carb ide,
i.e., AllEl + qtanide = Alkyl qanldc
i.e., Alkene + nitrile = Alkanenltrlle
_ (u) Replace lb acrd from the common name of
the conesponding Some ingertant examples are :
acid by the suffix orlarZe. ior
example,
14134
Pradee lt's Neur Coirse Chem istiq WII)
COMMON NAME IUPAC NAME
I]ORMUT-A

cH3-cN Methyl cyanide or Acetonitrile Ethanenitrile

Ethyl cyanide or ProPioDitrile Propanenitrile

cH3CH2-CN
cH3cH2cH2-cN n -Propyl cyanide or n -Butyronitrile Butanenitrile

19. IsocYanides or Isonitriles Common names. Add the sufltxisocyanide or

curbylamine to the name of the alkyl group.
General formulc .' R-N C where R is any
alkyl group
= IUPAC nams. There are no IUPAC names
for isocyanides or isonitriles.
Furtctionol group : -N ) C (isocyanide or
isonitile) Some imPortant examPles are:

Secondary suffuc.' isocyanide or isonitrile

FORMUI.A COMMON NAME

cH3-N = C Methyl isocyanide or Methyl carbylamine or Methyl isonitrile

cH3cH2-N = C Ethyl isocyanide or Ethyl carbylamine or Ethyl isonitrile

l4.ll.l.Rules for IUPAC Nomenclature for Branched chain Alkanes

The following rules are used for naming branched chain alkanes.
1. Longest chain rule. Select the longest con
atom& This is called the parent