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CONCEPT ESSENTIALS OF CHEMISTRY Some importantformulae, trends and termsfor a 'quick recap'. Class XII Organic
CONCEPT
ESSENTIALS OF CHEMISTRY
Some importantformulae, trends and termsfor a 'quick recap'.
Class XII
Organic Chemistry
Inorganic Chemistry
Physical Chemistry
The Solid State
General Principles and Processes of Isolation of Elements
Haloalkanes and Haloarenes
Z
M
3
d
g cm
Main steps involved in extraction of metals :
Reactivity order : RRI >
Br > RCl; 3° > 2° > 1°;
Density of unit cell :
3
a
N
Concentration of the ore : Hydraulic separation :
S
1
reaction
: 3° > 2° > 1°; S
2
reaction
: 1° > 2° > 3°
A
N
N
Total no. of atoms per unit cell :
for oxide ores; Froth floatation : for sulphide ores;
Electromagnetic separation : for magnetic
Dipole moments :
sc
fcc
CH Cl > CH F > CH Br > CH I
bcc
3
33
3
impurities/ores; Leaching : chemical method
CH Cl > CH Cl > CHCl > CCl (zero)
1
1
1
1
3
22
3
4
8
1
8
11
2
864
8
8
8
2
Relation between da,
and r
Conversion of ore to oxide : Calcination : for
carbonates and hydrated oxides; Roasting : for
sulphide ores.
Adsorption Isotherms
o-Dichlorobenzene
>
m-dichlorobenzene
~ chlorobenzene > p-dichlorobenzene (zero)
d
a
d
a
d
3 a
sc :
r
; fcc :
r
;
bcc :
Reduction of oxide into free metal : Smelting :
r
Alcohols, Phenols and Ethers
2
2
2
2
2
2
4
Reduction with carbon; Alumino-thermite process :
Acidity : Phenols > water > 1° alcohol > 2° alcohol >
Coordination number and packing efficiency
sc : CN = 6, PE = 52.4%; bcc : CN = 8, PE = 68%;
fcc : CN = 12, PE = 74%
Reduction with Al; Auto-reduction : for less
electropositive metals; Electrometallurgy :
3° alcohol
Distinction test of alcohols :
Electrolysis of fused oxide
Alcohol
Dichromate
Victor
Lucas
Size and no. of voids :
(Oxidation) test
Meyer’s test
test
Type
Size
No. of Voids
Acid
Blood red
No
Octahedral
0.414
R
N
(Orange solution
colour
turbidity
Tetrahedral
0.225
R
2
N
Refining of crude metal : Liquation : for metals
having low b.pts.; Distillation : for volatile metals;
Poling : for metals having own oxides as impurities;
Electrorefining : for Cu, Ag, Au, Ni, Cr, Al;
Zone refining : for Si, Ge, Ga.; van-Arkel method :
becomes green)
Ketone
Blue
for Ti, Zr; Chromatography : for elements available
(Orange solution
colour
Turbidity
in 5 minutes
Solutions
in
minute quantities.
becomes green)
Expression for concentration of a solution :
No reaction
Colourless
Turbidity
w
1000
w
1000
The p-Block Elements
2
2
immediately
M
;
N
M
V
2
E
V
(in mL)
2
(in mL)
Group 15 (Nitrogen family) :
Distinction test of phenol :
n
n
w
2
1
2
6
x
,
x
;
ppm
10
Bond angle, Thermal stability and Basic strength :
Test
Observation
2
1
nn
nn
12
12
M soln.
NH > PH > AsH > SbH > BiH
FeCl
3 test
Violet colour
33
3
3
3
On mixing solutions : NV + NV = N (V + V );
11
22
3
1
2
– B.Pt. : PH < AsH < NH < SbH < BiH
Br
– H O test
White ppt.
3
33
3
3
2
2
MV
+
MV
=
M
(+)
V
V
– M.Pt.: PH < AsH < SbH < NH
11
22
3
1
2
3
3
33
For liquid solutions : p
= x
× ppxp° ;
° ;
– Reducing nature : NH < PH < AsH < SbH < BiH
Liebermann's nitroso test
(NaNO + conc. H SO )
A
A
AB
B
B
33
3
3
3
2
24
p
– Bond angle : PF < PCl < PBr < PI
Deep green/blue
colour which changes
into red on dilution.
A
P
p
+
py
;
=
,
y
=1–
y
3
3
33
total =
A
BA
B
A
Azo dye test
Orange colour
p
– Lewis acid strength : PCl > AsCl > SbCl ;
p A
B
333
Colligative properties :
T
iK
m
PF
> PCl
> PBr
> PI
b
b
3
3
33
Aldehydes, Ketones and Carboxylic Acids
p
p
Group 16 (Oxygen family) : Bond angle and
T
iK
m ;
i
n RT
;
s
ix
f
f
2
V
p
Thermal stability : H O > H S > H Se > H Te
Reactivity order towards S
2
22
2
N
i
1
n
Volatility : H S > H Se > H Te > H O
RCHO > PhCHO > RCORR>
reactions : HCHO >
COPh > PhCOPh
;
(1 i
)
22
2
2
(disso.)
(asso.)
n
1
n
1
Acidic strength and Reducing nature :
Distinction test of aldehydes & ketones :
M
C
c
o
H
O < H S < H Se < H Te
i
or
(where
M
= molar mass,
2
22
2
Test
Aldehydes
Ketones
Adsorption Isotherms
M
o C
c
C = colligative property)
Stability : SF > SeF > TeF
666
Schiff 's reagent
Pink colour
No colour
Group 17 (Halogen family) :
Adsorption Isotherms
Fehling's solution
Red ppt.
No ppt.
Electrochemistry
Oxidizing power : F > Cl > Br > I
2
2
22
Tollens' reagent
Silver mirror
No ppt.
V
1
al
– B.Pt. and M.Pt. : HF > HCl < HBr < HI
RG
;;
R
;
G
– Dipole moment and Thermal stability :
IR
l
a
Acidity : Carboxylic acids > Phenols > Alcohols
Distinction test of carboxylic acids :
1000
1000
HF > HCl > HBr > HI
V
;
V
eq
m
Test
Adsorption Isotherms
Carboxylic acids
Phenols
N
M
– Bond length, Acidic strength and Reducing
nature : HF < HCl < HBr < HI
NaHCO
3 Brisk effervescence of
No reaction
c
bC
;
;
x
y
m
m
eq
c
a
m
c
a
– Acidic strength : HClO < HClO < HClO < HClO ;
CO gas
2
234
c
HOCl > HOBr > HOI; HClO > HBrO > HIO
FeCl
3 Buff coloured ppt.
Violet colour
4
44
m ;
G
nFE
RT
ln
K
cell
c
– Oxidizing power : HClO > HClO > HClO > HClO
m
234
E
W 1
1
Group 18 (Noble gases): M.Pt., B.Pt., Ease of
Amines
W
ZIt
;
;
E
E
E
cell
(cathode)
(anode)
W
E
liquefaction,
Solubility, Adsorption and
2
2
Basic nature : Aliphatic amine > NH
> aromatic
3
0.0591
1
0.0591
Polarizability : He < Ne < Ar < Kr < Xe
amine;
3° > 2° > 1° > NH
in gas phase/in non-aq.
EE
log
;
E
log
K
3 [
cell
cell
cell
c
n
n
n
Thermal conductivity : He > Ne > Ar > Kr > Xe
[
M
]
solvent
]; 2° > 1° > 3° > NH
in aq. phase, only —CH 3 subs.
3 [
amines
]; 2° > 3° > 1° > NH
in aq. phase, only —C 2 H 5
3 [
Chemical Kinetics
d- and f-Block Elements
subs. amines]
1–10
0–2
Distinction test (Hinsberg's test):
Expressions for different orders :
d-block elements : (n –1)d
ns
C
H
SO Cl
+ 1°, 2° or 3° amines
Rate law
Integrated rate law
Half-life
– Sc –
3d
series :
Zn
65
2
21
30
KOH
Rate =
k
[
A
]
0 [
A
] t =–
kt
+[
A
t
= [
A
] /2
k
– 4d
series :
Y –
Cd; 5d series :
La,
Hf –
Hg
] 0
Clear solution
Soluble salt [1° amine]
1/2
0
39
48
57
72
80
[0 order]
6d
series :
Ac,
Rf –
Cn
KOH
89
104
112
ppt.
No reaction [2° amine]
Rate =
k
[
A
]
1 A
ln[
] t = –
kt
+ ln[
A
]
= 0.693
k
0 t
1/2
Acidic character : MnO < Mn O < Mn O < MnO
34
23
2
No reaction [3° amine]
[1 st
order]
< Mn O ;
Ionic character
: MnO > Mn O
> Mn O
Rate =
k [
A
]
2 A
1/[
] t =
kt
+ 1/[
A
]
t
= k A
1/
[
]
27
34
23
+
+
– ArN
are more stable than
RX
N
.
0
1/2
0
2 X
> MnO > Mn O
2
[2 nd
order]
2
37
[
B
][ 0
A
]
– EDGs
stabilise
while
EWGs
destabilise
the
1–14
0–1
2
Rate =
kA
[
][
B
]
kt
1 ln
= kA
1/
[
]
f-block elements : (n –2)f
(n –1)d
ns
t 1/2
0
[
A
]
[
B
]
[
AB
][
]
00
0
diazonium salts.
[2 nd
order]
3+
La(OH)
to Lu(OH)
: Basicity decreases; La
1
1
n 1
2
1
3
3
Rate = k[A] n
(
n
1)
kt
3+
n
1
n
1
t 1/2
to
Lu
: Tendency to form complexes increases
[] A
[
A
n 1
0 ]
kn (
1)[
A
]
[n th
order]
0
Biomolecules
Coordination Compounds
Arrhenius equation :
E
TT
Ligand
E
a / RT
k 2
Central metal ion
a
21
k
Ae
; log
2.303 R
TT
K
[Fe(CN)
]
k 1
12
4
6
Counter ion
Reducing sugars : All monosaccharides
Non reducing sugars : All polysaccharides and
disaccharides like sucrose.
Fat soluble vitamins : A, D, E and K.
Coordination number
Coordination sphere/entity
Surface Chemistry
Water soluble vitamins : B , B , B , B
and C
1
2
6
12
–vely charged sols : Metals, sulphides, acidic dyes,
Spectrochemical series :
2–
2–
Polymers
starch, clay, silk.
+vely charged sols : Metal hydroxides, oxides,
basic dyes, haemoglobin.
Hardy–Schulze rule : Coagulation power for
I –
< Br
< SCN
< Cl
< S
< F
< OH
< C O
<
2
4
4–
H
O <
NCS < edta
< NH
<
en
< NO
< CN < CO
Addition homopolymers : Polythene, polystyrene
2
3
2
Condensation homopolymers : Nylon-6, PHB
n
(
n
2) B.M.;
4
;
t
9 o
Addition copolymers : Buna-S, Buna-N
3+
2+
+
CFSE = (– 0.4x + 0.6y) where, x = no. of e s in t
–vely charged sols : Al
> Ba
> Na
o
2 g
Condensation copolymers : Nylon-6, 6, Nylon-6, 10
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CHEMISTRY TODAY
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CHEMISTRY TODAY
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MAY '15
4–
3–
2–
+vely charged sols : [Fe(CN) ]
> PO
> SO
> Cl
orbitals, y = no. of ees in
orbitals.
Biodegradable copolymers : PHBV, Nylon 2- nylon 6.
g
6
4
4
CONCEPT ALCOHOLS, PHENOLS AND ETHERS Alcohols, phenols and ethers are the basic compounds of organic
CONCEPT
ALCOHOLS, PHENOLS
AND ETHERS
Alcohols, phenols and ethers are the basic
compounds of organic chemistry and they
find wide applications in industry as well as
in day-to-day life.
Chemical properties
l
Physical properties
B.pt. µ No. of C-atoms
Cleavage of O—H bond : Ease of reaction depends on stability
of alkoxide ion.
Acidity : Phenols > Water > 1° alcohol > 2° alcohol > 3° alcohol
l
Solubility
µ Branching
Cleavage of C—OH bond : Ease of reaction depends on stability of
carbocations.
Order of reactivity : 3° alcohol > 2° alcohol > 1° alcohol
ALCOHOLS
Reactions involving whole alcohol molecule :
l
443
K
(C
H
OH)
C
C
n
2n+1
413
K
Dehydration :
R—OH + conc. H SO
ROR
2
4
142 pm
96 pm
383
K
:
O
:
RO—SO OH
2
H
513
K
ROR
Preparation
C
108.9°
H
R—OH + Al O
2
3
633
K
3
H
sp
RX + KOH
® ROH + KX
C
C
l
(aq.)
H
[O]
[O]
conc. H SO /H O
2
4
2
Oxidation :
Alcohol
Aldehyde/Ketone
Carboxylic acid
(Markovnikov's addition)
Cu/273 K
ll
C
C
RCH OH
Dehydrogenation :
1° alcohol
Aldehyde
2
(i)
B
H
in THF
Alkene
2
6
Cu/273 K
Ketone
(ii)
H O , OH
2° alcohol
2
2
(Anti-Markovnikov's addition)
Cu/273 K
Dehydration : 3° alcohol
C
C
l
HCHO
H
/Pt or Pd or Ni
2
RCH OH
2
or
1° Alcohol
RCHO
or
Distinction tests
NaBH or LiAlH
4
4
or
R
CH
R
l
or Na/C H OH
R
2
5
C
O
OH
R
Dichromate test (oxidation) : 1° alcohol ® Acid with same
number of C-atoms; 2° alcohol ® Ketone with same number of
C-atoms; 3° alcohol ® No reaction under normal conditions.
2° Alcohol
Carbonyl
(i) RMgX/Dry ether
or
Victor Meyer’s test : 1° alcohol ® Blood red colour;
compounds
l
+
(ii) H O/H
2
R C—OH
3
2° alcohol ® Blue colour; 3° alcohol ® Colourless.
3° Alcohol
(i)
LiAlH
or B H /ether
Lucas test : 1° alcohol ® No turbidity; 2° alcohol ® Turbidity in
l
4
2
6
l
RCOOH
RCH OH
PHENOLS
2
+
5 minutes; 3° alcohol ® Turbidity appears immediately.
(ii)
H O
3
Carboxylic acids
(C
H OH)
6
5
109°
Some important alcohols
H
l
O
136 pm
Physical properties
2
sp
Methanol : Prepared by catalytic hydrogenation of carbon
monoxide or water gas. It is used as a solvent, preservative,
substitute for petrol, etc.
Pure phenols are colourless liquids or solids.
l
l
Form intermolecular hydrogen bonds hence, soluble in water.
l
Ethanol : Prepared by the hydration of ethene or by the fermentation
of molasses. It is used as an antiseptic, power alcohol, in beverages, etc.
Preparation
Chemical properties
NaOH
NaOH
dil. HCl
l C
H
SO H
C
H
SO Na
C H ONa
6
5
3
–H O
6
5
3
573-623 K,
6
5
–NaCl
2
Electrophilic substitution of phenols : Halogenation,
l
–Na SO
, –H
O
2
3
2
sulphonation, nitration, Friedel—Crafts alkylation, etc. occur at
dil. H SO , D
+
2
4
C
H
N Cl
– + H
6
5
2
2 O
C
H OH
o- and p- positions due to activating effect of —OH group.
–N , –HCl
6
5
2
Phenol
623 K, 320 atm
dil. HCl
C H Cl + NaOH
C H ONa
6
5
6
5
–NaCl, –H O
–NaCl
2
Tests to distinguish phenols from alcohols
1. O 2
C H CH(CH )
6
5
3
2
+
FeCl test : Gives violet colour
2. , H
H
l
3
2 O
Cumene
Br
– H O test : Gives white ppt.
l
2
2
ETHERS
l
(C
O
Liebermann’s nitroso test : Gives blue colour which turns red on
dilution
n H
2n + 2
Ammonia/Sodium hypochlorite test : Gives blue colour
where n > 1)
l
Azo dye test : Gives orange colour
141 pm
l
:
O :
Classification
H
H
l
Simple or symmetrical : Same alkyl groups are attached to
H
C 111.7°
C H
oxygen, ROR.
Physical properties
H
3 H
sp
l
Mixed or unsymmetrical : Different alkyl groups are
attached to oxygen, ROR¢.
Dipolar due to slightly polar C—O bonds.
l
l
l
Aliphatic ethers : R and R¢ both are alkyl groups.
B.pts. are lower than isomeric alcohols due to lack of hydrogen
bonding.
l
Aromatic ethers : Either one or both R and R¢ are aryl groups.
l
Solubility in water (soluble due to formation of
H–bonds with water)
Fairly soluble in organic solvents.
l
Chemical properties
Lighter than water.
l
l
Reaction of ethereal oxygen :
R
+
ROR + HCl(conc.)
O – H
Cl
Preparation
R
conc. H SO , 413 K
2
4
2ROH
l
Cleavage of C – O bond :
or Al O , 523 K
ROR
2
3
373 K
D Ether
R – OR + HX
R – OH + R – X
RX + RONa
– In case of alkyl aryl ethers, phenol and an alkyl halide are obtained.
–NaX
(Williamson synthesis)
dil. H SO
l
Williamson synthesis involves S
N 2 mechanism in case of 1° alkyl
2
4
ROR + H O
D 2R – OH
2
halides.
ROR + PCl
D 2R – Cl
l
In the case of 2° and 3° alkyl halides, elimination takes place.
5
l
Reactions involving alkyl group :
l
Dehydration of alcohols for the formation of ethers follows the order :
1° > 2° > 3°
– Formation of peroxides with air and light.
– Substitution products obtained on halogenation.
l
Electrophilic substitution reactions :
Uses
Aryl alkyl ethers give o- and p-substituted products due to +R effect of
alkoxy group (–OR).
Ethers are used as industrial solvents, heat transfer medium (diphenyl
ether), flavouring agents and in perfumes.
::
:
Grignard's
reagent
Reduction

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CHEMISTRY TODAY

JUNE '15

CHEMISTRY TODAY | JUNE '15 CHEMISTRY TODAY JUNE '15 CONCEPT SOMESOME BASICBASIC CONCEPTSCONCEPTS OFOF
CHEMISTRY TODAY | JUNE '15 CHEMISTRY TODAY JUNE '15 CONCEPT SOMESOME BASICBASIC CONCEPTSCONCEPTS OFOF

CONCEPT CHEMISTRY TODAY | JUNE '15 CHEMISTRY TODAY JUNE '15 SOMESOME BASICBASIC CONCEPTSCONCEPTS OFOF CHEMISTRYCHEMISTRY

SOMESOME BASICBASIC CONCEPTSCONCEPTS OFOF CHEMISTRYCHEMISTRY Introduction ofmostfundamental and important tools of
SOMESOME BASICBASIC CONCEPTSCONCEPTS OFOF CHEMISTRYCHEMISTRY
Introduction ofmostfundamental and important tools of chemistry which help in various calculations.
SI Units Law of Conservation of Mass M asses  SI system has seven base
SI Units
Law of Conservation of Mass
M asses
SI system has seven base units pertaining to
seven fundamental scientific quantities :
Matter can neither be created nor destroyed.
 Atom ic mass unit ( amu or u) : Mass exactly
th
equal to 1/12 of the mass of an atom of
C-12 isotope.
Physical quantity
SI unit
Law of Definite Propor tions
Length (l)
metre (m)
A given compound always contains exactly the
same proportion of elements by weight.
 Atom ic mass of an elemen t : Average
relative mass of its atoms as compared to an
atom of C-12.
Mass (m)
kilogram (kg)
 Aver age atom ic mass : Given for isotopes.
Time (t)
second (s)
 XA
where X =%abundance
i
i
i
Law of Multiple Proportions
Electric current (I)
ampere (A)
  X
i = atomic mass
i A
If two elements can combine to form more than
Thermodynamic
kelvin (K)
 Gr am atom ic mass : Atomic mass of an
element expressed in grams.
temperature (T)
Amount of substance (n)
mole (mol)
one compound, the masses of one element that
combine withafixed mass of the other element,
are in the ratio of small whole numbers.
 Molecula r mass : Sum of atomic masses of
all the elements present in a molecule.
Luminous intensity (I )
candela (cd)
v
Gay Lussac’s Law of Gaseous Volumes
Mo le Co n cep t
SI system allows the use of prefixes to
indicate the multiples or submultiples of a
unit :
When gases combine or are produced in a
chemical reaction they do so in a simple ratio
by volume provided all gases are at same
Mole : Collection of 6.022 × 10
In case of
atom ic substances :
23 particles
–1
1
deci - 10
deka - 10
1 mole=Gram atomic mass=1gram atom
temperature and pressure.
–2
2
= 6.022 × 10
23 atoms
centi - 10
hecto - 10
mole cula r substance s :
–3
3
milli - 10
kilo - 10
Avogadro's Law
–6
6
micro - 10
mega - 10
1 mole=Gram molecular mass
=1gram molecule
–9
9
Equal volumes of gases at the same temperature
nano - 10
giga - 10
= 6.022 × 10
23 molecules
–12
12
gase ou s substance s :
pico - 10
tera - 10
and pressure should contain equal number of
molecules.
1 mole = 22.4 L at STP
Scientific Notation
Dalton's Atomic The or y
Pe rc entage Co mp osition
A number is represented as x × 10 n
 Matter consists of indivisible atoms.
n is –ve if decimal is moved towards right
and n is +ve if it is moved towards left.
 All the atoms of a given element have
identical properties including identical
mass. Atoms of different elements differ in
mass.
It shows mass of a constituent in 100 parts of a
compound.
Mass % of an element
Mass of that element in the compound
 100
Molar mass of the compound
Significant Figures
 Compounds are formed when atoms of
different elements combine in a fixed ratio.
These are all certain digits with last digit
uncertain.
Em p iri ca l F ormu la
All non-zero digits are significant .
 Chemical reactions involve reorganisation
of atoms. These are neither created nor
destroyed inachemical reaction.
Zeros preceding to first non-zero digit are
not significant.
 It is the simplest whole number ratio of
different atoms present inacompound.
 Steps to obtain empirical formula :
Zeros between two non-zero digits are
significant.
Stoi chiomet ry
% age
Change to
Molar ratio 
Zeros on the right side of the decimal are
significant.
At. mass
 It deals with calculations based upon
chemical equations.
Molar ratio
 Various steps involved in calcul at ions are :
Simplest molar ratio 
Minimum molar ratio
– Write balanced chemical equation.
Dimensional Analysis
– Write the relative number of moles or
relative masses of reactants and products
involved below their formulae.
Change to
 Required unit=Given value×conversion
factor
Write the numbers below
the symbols of elements
 Some useful conversion factors :
Simplest whole
number ratio =
Simplest ratio × Integer
–8
–10
Length – 1Å=10
cm=10
m
– In case of gases write 22.4 L at STP in
place of1mole.
Empirical formula
–9
–12
1 nm = 10
m, 1 pm = 10
m
– Apply unitary method to make required
Volume – 1 L = 1000 mL
= 1000 cm =1dm = 10
Pressure – 1 atm = 760 mm or torr
= 101325 Pa
calculations.
3
3
–3
3
m
Mo lecula r F ormu la
L imiting Re agent
5
–2
5
1
bar=10 Nm
= 10
Pa
 It is the formula showing exact number of
atoms present inamolecule.
Energy – 1 calorie = 4.184 J
The reactant which gets consumed completely
 Molecular formula = n × empirical formula
–19
1 eV = 1.6022 × 10 J
and limits the amount of product formed is
1J=10
7 ergs
called limiting re agent.
Re action s in S o luti on s
w solute
 Mass percent (%) =
 100
HAVE A LOOK!
w solution
n
n
A
B
 Mole fraction (x ) =
, x B 
A
 Mass is the quantity of matter contained in the substance and is constant whereas weight varies
nn
nn
AB
AB
from
place to place.
w
 1000
2
 Molarity (M) =
 Exact numbers have an infinite number of significant figures.
V (in mL)
M 2
 Molar volume of a gas is 22.7 L at 1 bar and 0°C.
w
 1000
2
 Molality (m) =
 The number of molecules in 1 mL of a gas at STP is known as Loschmidt number.
 w
(in g)
M 2
1

| 4746

CHEMISTRY TODAY

JULY '15

CHEMISTRY TODAY

|

JULY'15

CHEMISTRY TODAY JULY '15 CHEMISTRY TODAY | JULY'15 CONCEPT PHYPHYSICALSICAL CHEMISTRYCHEMISTRY (Part-I)(Part-I)
CHEMISTRY TODAY JULY '15 CHEMISTRY TODAY | JULY'15 CONCEPT PHYPHYSICALSICAL CHEMISTRYCHEMISTRY (Part-I)(Part-I)
CONCEPT
CONCEPT
PHYPHYSICALSICAL CHEMISTRYCHEMISTRY (Part-I)(Part-I) Solutions, Electrochemistry and Chemical Kinetics form the basis of
PHYPHYSICALSICAL CHEMISTRYCHEMISTRY (Part-I)(Part-I)
Solutions, Electrochemistry and Chemical Kinetics form the basis of physical chemistry and give an idea about the nature of
solutions, relationship between chemical energyand electrical energy in redox reactions and also the rates of reactions.
SOLUTIONS Expressing Concentration of Solutions  Mass percentage : Grams of solute in 100 g
SOLUTIONS
Expressing Concentration of Solutions
 Mass percentage : Grams of solute in 100 g of
solution.
 Strength : Grams of solute in 1 L of solution.
 Molarity: Moles of solute in 1 L of solution.
 Normality : Gram equivalents of solute in 1 L
of solution.
 Molality : Moles of solute in 1 kg of solvent.
 Mole fraction : Moles of the component/ total
no. ofmoles of all components.
 Parts per million : Mass of solute in one
million (10 ) parts by mass of solution.
6
Laws
 Henry’s law : m = K  p or p = K  x
H
where K is Henry’s constant hav ing units of
H
pressure
.
 Raoult’s law :
p

p
n
s
For non-volatil e s olute :
2  x
2
p 
n
n
1
2
For volatile c ompone nt s :
= x p ° ; p = x p ° and p
= p + p
p A
A A
B
B B
tota l
A
B
Types of Solutions
 Ideal solutions : A–B interactions are of same
magnitude as A– A and B–B interactions,
V
=0and
 H
= 0.
mix
mix
 Non-ideal solutions : A– B interactions are of
different magnitude than A– A and B–B
interactions,  V
 0 and  H
 0.
mix
mix
– Non-ideal solutions showing +ve
deviations : A– B interactions are weaker
than A– A and B –B interactions,  V mix
= +ve,  H = +ve and resulting vapour
mix
pressure is higher than that expected.
– Non-ideal
solutions
showing
–ve
deviations : A–B interactions are stronger
than A– A and B–B interactions,  V =
mix
–ve,  H = –ve and resulting
vapour
mix
pressure is lower than that expected.
 Azeotropes: Constant boiling mixtures.
Colligative Properties
 Colligative properties depend only on the
number of particles of solute dissolved in a
definite amount of solvent. These are :
– Elevation in boiling point : Boiling point
of solution is higher than that of pure
solvent.  T = T – T °
= K
m
b
b
b
b
– Depression in freezing point : Freezing
point of solution is lower than that of pure
solvent.  T = T
°
=
K m
f
f
T f
f
– Relative lowering of vapour pressure :
p

p
n
s 
x
2 (for dilute solutions,
2 
p 
n
1 n
<<<
n
)
2
1
p

p
s for dilute as well as
n
2
 concentrated solutions
p
 
 
s n
1
– Osmotic pressure :  = CRT
van’t Hoff Factor ( i ) and its Significance
i 
Observed value of colligative property
Normal value of colligative property
Calculated molecular mass
Observed molecular mass
 For solute undergoing association :
n
(1
i
)
;
i
1
(Degree of association)
n  1
 For solute undergoing dissociation :
i
 1
;
i 
1
(Degree of dissociation)
n
 1
 Modified colligative properties :
p

p
s  ix
2 ;  T
= iK
m , T = i K m ;
p 
b
b
f
f
 = iCRT
ELECTROCHEMISTRY CHEMICAL KINETICS Basic Terms Rate of Reaction  Conductance : Reciprocal of resistance. 
ELECTROCHEMISTRY
CHEMICAL KINETICS
Basic Terms
Rate of Reaction
 Conductance : Reciprocal of resistance.
 Forareaction, aA + bB  xX + yY
1
1
d A
[
]
1
d B
[
]
1
d X
[
]
1
d Y
[
]
1
C
; Unit :
or S
Rate 



R
a d t
b dt
x d t
y dt
 Conductivity : Conductance of 1 cm
3 of the
 Greater the concentration of reactants, faster is the
reaction.
conductor.
 Rate becomes double for every 10° rise in
l
1
1
1
 
C
; Unit :
cm
or S cm
temperature.
a
 Equivalent conductivity : Conductance of a
 Greater the surface area of reactants, faster is the
reaction.
solution containing 1 g-equivalent of an
electrolyte dissolved in V cm of the solution.
3
 1000
Order and Molecularity
2
 1
; Unit : S cm
eq
eq
Normality
a
b
 Molar conductivity : Conductance of a solution
 Forarate law equation, rate = k[ A] [B ]
Order of reaction = a + b .
containing1mole of an electrolyte dissolved in
 Molecularity is
the number of atoms, ions or
V cm of the solution.
3
molecules that must collide simultaneously with
 1000
one another to result intoachemical reaction.
2
 1
; Unit : S cm
mol
m
Molarity
 Electrod e p otential : Tendency of an elec trode to
Integrated Rate Equation and Half-Life
lose or gain electrons when it is in contact with
solution of its own ions.
Order
Integrated
Half-life
 Cell potential or EMF of the cell : The difference
between electrode potentials of two half-cells.
t
=
rate equation
1/2
0 [
A
] =–
kt
+[
A
]
[
A
] 0 /2
k
t
0
1 ln[
A
] = –
kt
+ ln[A]
0.693/ k
Types of Cells
t
0
2 1/[
A
] =
kt
+ 1/[
A
]
1/
k A
[
]
t
0
0
 Electrochemical cell : Device used to convert
chemical energy of a redox reaction into
electrical energy.
[
B
]
A
]
0 [
2 kt 
1 ln
[
A
]
 [
B
]
[
A B
]
[
]
0
0
0
 Electrolytic cell : Device which uses electricity
to bring aboutanon-spontaneous redox
reaction.
n  1
1
1
2
1
n (
n
1)
kt
n
1
n
1
n  1
[
A
]
[
A
0 ]
k n
(
 1)[
A
]
0
 Relationship between time for different fractions of
a first order reaction to complete,
Laws
t
or
t
= 2
t
3/4
75%
1/2
 Faraday’s first law : W = Zit
3
 t
3
t
t 87.5%
1/2
2 75%
W
E
 Faraday’s second law :
1
 1
=4
t
=2
t
W
E
t 93.75%
1/2
75%
2
2
=5
t
t 96.87%
1/2
 Kohlrausch’s law : For an electrolyte A B ,
x y
=10
t
t 99.9%
1/2
° = ° + ° or ° =°+° 
x
y
m
+
eq
+
Nernst Equation and Electrochemical Series
Temperature Dependence of Rate of
Reaction and Effect of Catalyst
 Nernst equation : For the reaction :
 Arrhenius equation : k = Ae –E a / RT
n +
M
+
ne
M
,
k
E a  T T 
2
2
1
RT
M
or log
E
 E

ln
or
k 1 R
2.303
T T
 
1
2
 
n
nF
[
M
]
 Activation energy
0.0591
1
E
 E

log
at 298 K
n
= Threshold energy–Average kinetic
energy of reactants
n [
M
]
 Collision theory : k = P Ze –E a / RT
 For concentration cell :
where P is steric factor and Z is collision
0.0591 log
C
2
;
E
+ve if
C
C
E ce ll
ce ll
2
1
frequency.
n
C
1
 increases the rate ofareaction
Ca talyst
 For a reaction in equilibrium :
without itself undergoing any permanent chemical
0.0591 log
E
K
at 298 K
change.
ce ll
n
 Electrochemical series : It is the arrangement of
electrodes in order of increasing standard
reduction potentials.
– This series helps in comparing the relative
oxidizing or reducing powers, relative
activities of metals and to predict spontaneity
of the redox reaction.
HAVE A LOOK!
 Different solutions having same vapour pressure
are called is opiestic solution s .
Commercial Cells/Batteries
 Deliques ce nt substances absorb moisture because
vapour pressure of their saturated solutions is less
than that of water vapours in air at that
temperature.

Primary cells cannot be recharged e.g. , dry cell,

mercury cell.

Secondary cells can be recharged e.g . , lead storage battery, Ni–Cd storage cell.

Fuel cells convert the energy produced during

combustion of fuels into electrical energy directly e.g. , H –O fuel cell.

2

2

 Ef fl ores ce nt substances lose their water of crystallisation because their hydrated
 Ef fl ores ce nt substances lose their water of
crystallisation because their hydrated crystals have
vapour pressure larger than that of water vapours in
air.
 Association generally occurs in non-aqueous
solvents (non-polar) because high dielectric
constant of water helps in the dissociation of the
associated molecules.
CONCEPT STATES OF MATTER States of matter are distinguished by the strength of the bonds
CONCEPT STATES OF MATTER States of matter are distinguished by the strength of the bonds
CONCEPT
STATES OF
MATTER
States of matter are distinguished by the strength of the bonds holding the
molecules of the matter together. Gases, liquids and solids are all made up
of microscopic particles, but the behaviour of these particles differs in the
three phases.
Crystal Lattice and
Unit Cell
lCrystal lattice : The regular arrangement of
constituent particles in a three dimensional space.
lUnit cell : The smallest repeating unit of space lattice.
lTypes of unit cells :
d
a
Classification
– Simple cubic : Particles at the corners only,
r
,
2
2
lAmorphous solids : Constituent
Z = 1, efficiency = 52%, C.No. = 6.
particles are not arranged
in regular
– Body centred : Particles at the corners as well as body centre,
pattern.
d
3 a
Z = 2,
r
,
efficiency = 68%, C.No. = 8
– short range order and isotropic in nature.
2
4
– supercooled liquids or pseudo solids.
– Face centred : Particles at the corners as well as face centres,
lCrystalline solids : Constituent particles are
arranged in definite geometric pattern.
d
a
Z = 4,
r
,
efficiency = 74%, C.No. = 12
2
2
2
– long range order and anisotropic in nature.
– true solids.
lCrystalline solids can be molecular solids,
ionic solids, metallic solids or covalent
solids depending upon the nature
of intermolecular forces.
lIf N is no. of spheres in ccp then tetrahedral voids = 2N,
having radius = 0.225 R and octahedral voids = N,
having radius = 0.414 R.
SOLID STATE
Imperfections in Solids
lDefects in stoichiometric crystals :
– Schottky defect : Arises when equal number of
cations and anions are missing from the lattice sites and
results in decrease in density of the crystal.
– Frenkel defect : Arises due to dislocation of smaller ion from its
normal site to interstitial site and does not affect the density.
lDefects in non-stoichiometric crystals :
Metal excess defect :
Magnetic
Arises when a negative ion is missing from its lattice site, leaving
Properties
a
lDiamagnetic substances : Weakly repelled
by external magnetic field. e.g., N , NaCl, Zn,
TiO , etc.
lParamagnetic substances : Weakly attracted by
hole which is occupied by an electron (F-centre).
When an extra cation is at interstitial site and electrical neutrality
is maintained by electron present in another interstitial site.
2
Electrical
2
Properties
– Metal deficiency defect :
Arises when metal shows variable valency and is characterised
lConductors : Conductivity range,
7
–1
–1
2+
3+
3+
external magnetic field. e.g., O , Cu
, Fe
, Cr
, etc.
10
4 to 10
ohm
m
2
–20
by missing of a cation from its lattice site and the presence of a
cation having higher charge in the adjacent site.
lInsulators : Conductivity range, 10
to
lFerromagnetic
substances
:
Show
permanent
–10
–1
–1
When extra anion is at interstitial
site and
10
magnetism even in the absence of external magnetic field.
m
lSemiconductors : Conductivity range, 10
ohm
–6
electrical neutrality is maintained by extra
e.g., Ni, Fe, Co, etc.
lAntiferromagnetic
4
–1
–1
charge on adjacent metal ion.
substances :
Have
zero net
dipole moment due to presence of equal number of
domains in the opposite directions. e.g., MnO.
lFerrimagnetic substances : Possess very
small net magnetic moment due to
unequal number of domains in
the opposite directions.
e.g., Fe O .
to 10 ohm m
– n-type semiconductors : Group 14 elements
doped with group 15 elements, free electrons
increase conductivity.
– p-type semiconductors : Group 14
elements doped with group 13
elements, holes increase
conductivity.
GASEOUS
3
4
STATE
lA substance exists in gaseous state
if the thermal energy of molecules pre-
dominates over the intermolecular forces.
lGas laws :
1
Boyle’s law :
P
(at constant T and n)
V
– Charles’ law : V
T
(at constant P and n)
– Gay Lussac’s law : P
T (at constant V and n)
LIQUID
– Avogadro’s law : V
n (at constant P and T)
STATE
– Dalton’s law of partial pressures : P
= p + p +
+ p (at constant V and T)
total
l
2
n
lA substance exists in liquid
= P
– aq. tension
P dry gas
moist gas
state if the intermolecular forces lie
between gaseous and solid states.
lProperties of liquids :
r M
d
2
2
– Graham’s law of diffusion :
1
r
d 1 M
2
1
lIdeal gases : Follow gas laws in all conditions of temperature and pressure.
– Vapour pressure : Pressure exerted by vapours in
equilibrium with the liquid at a particular temperature.
– Boiling point : Temperature at which the vapour pressure of a
liquid becomes equal to the atmospheric pressure.
– Surface tension : Tangential force acting along the surface of a liquid
at right angle to a line of one unit length drawn on the surface of
the liquid.
– Viscosity : Measure of resistance to flow.
lEotvos equation : Relates surface tension (
temperature (T) and critical temperature
(T ) of liquid to its density (d) and
– Follow ideal gas equation; PV = nRT
lReal gases : Follow gas laws only at high temperature and low
pressure.
– Follow van der Waals equation;
2
an
P
(
V
nb
)
nRT
2
V
),
lCritical constants and van der
Waals constants :
a
3
b
,
P
V c
c
2 ,
27 b
c
8
a
molarmass (M),
T c
2/3
d
27 Rb
k T
(
T
)
c
M

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