Reference Book

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About the Author
Ranveer Singh has an M.Sc. in Chemistry and has been mentoring and teaching Chemistry to JEE aspirants for more
than 15 years. He aims for perfection and has an enormous passion when it comes to applying new methods to create
solutions. These are the qualities that make him stand out from the crowd as a teacher and instructor.

Ranveer Singh
McGraw Hill Education (India) Private Limited

CHENNAI
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Physical Chemistry for JEE (Main & Advanced) Module-II
Copyright © 2017, McGraw Hill Education (India) Private Limited.
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ISBN (10): 93-5260-603-5
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Dedicated
to
Shri Amar Chand Ji Maharaj

Preface
Chemistry forms an important part of all entrance tests. In my teaching career, spanning over a decade and half, I have felt that a
chemistry book based on the changing perceptions, needs, feedback and the experiences of the students and educators is needed
by the engineering aspirants. It is with this vision that the present book has been written.
This book is not a textbook. It is a refresher text to help students revise their lessons in the quickest possible way and in the
most effective manner. It does not over emphasise theories, as has been done in several other competitive books available in the
market. However, every care has been taken to ensure that no important theory is left out. This book has several new features:
coverage of the syllabus of JEE (Main + Advanced); a great number of solved numerical examples to acquaint students with
the application of several theories, solution at the end of each exercise and two levels of questions at the end of the chapters to
give readers an opportunity to assess their understanding of the chapters. The use of easily understandable language is at the
core of the author’s efforts.
The exercises given at the end of every chapter is further categorised into three difficulty level of questions and their patterns
asked in JEE along with the previous year questions with solutions.
● Level-I has the questions mainly suitable for JEE Main exam.
● Level-II contains slightly difficult questions suitable for JEE Advanced.
● Level-III has the highest questions of various patterns asked in JEEAdvanced (such as more than one correct answer,
comprehension, match the column and single digit integer).

I hope this book will help in motivating and encouraging the students towards the preparation forthe Chemistry portion of
the examinations. Every care has been taken to make the book error-free. However, some mistakes may have been crept in inad-
vertently. Constructive suggestions and comments from students and teachers would encourage me to make the book more au-
thentic and acceptable in the next edition. We wish our young readers a great success at the engineering entrance examinations.
Ranveer Singh

Acknowledgements
I express my gratitude towards the publisher and the members of the editorial team. I would be failing in my duty if I don’t
express my thankfulness to Mr. Sanjay Agrawal for encouraging me to start writing this book and helping me step by step while
preparing the manuscript.

Contents
Preface vii
Acknowledgements ix
1. Chemical Kinetics 1.1–1.52
● Key Concepts 1.1
● Solved Examples 1.14
● Exercise 1.17
■ Level I 1.17
■ Level II 1.23
■ Level III 1.26
● Previous Years’ Questions of JEE (Main & Advanced) 1.33
● Answer Key 1.35
● Hints and Solutions 1.36
2. Electrochemistry 2.1–2.52
● Exercise 2.15
■ Level I 2.15
■ Level II 2.18
■ Level III 2.22
● Answer Key 2.29
3. Solution and Colligative Properties 3.1–3.39
● Exercise 3.16
■ Level I 3.16
■ Level II 3.19
■ Level III 3.20
● Answer Key 3.26

x Physical Chemistry-II for JEE (Main & Advanced)
4. Solid State 4.1–4.31

● Exercise 4.11
■ Level I 4.11
■ Level II 4.14
■ Level III 4.15
● Answer Key 4.20
5. Surface Chemistry 5.1–5.24
● Exercise 5.9
■ Level I 5.9
■ Level II 5.11
■ Level III 5.15
● Answer Key 5.19
6. Redox 6.1–6.44
● Exercise 6.15
■ Level I 6.15
■ Level II 6.18
■ Level III 6.19
● Answer Key 6.27
7. Thermodynamics and Thermochemistry 7.1–7.58
● Exercise 7.24
■ Level I 7.24
■ Level II 7.28
■ Level III 7.30
● Answer Key 7.38

Chapter
1
Chemical
Kinetics
Key Concepts
Moderate
INTRODUCTION TO KINETICS 2H2O2 h 2H2O + O2
Thermodynamics deals with the feasibility of the reaction but

kinetic deals with the rate of the reaction. [P]
Thermodynamics deals with the initial and final state of
the reactants and products but kinetics deal with the path by [R]
which reaction is taking place.
P.E.
? (kinetics)
Simple reaction P.E.
Complex reaction Those chemical reactions which
Simple reaction takes place in a single step are
R DH known as simple reaction.
P aA + bB Æ P R P
time
a b
r = K[A] [B] Reaction coordinate
CLASSIFICATION OF Complex
CHEMICAL REACTION Those chemical reactions which take in more than one step.
P.E.
Very fast Very Slow
I*
NaCl + AgNO3 Æ AgCl Ø+ NaNO3 1 25∞C
Fe + O 2 æææ Æ FeO
HCl + NaOH Æ NaCl + H2O 2 R P
Conc. [O]
Cellulose æææ
25∞C
Æ CO 2 + H 2O
[P] Reaction coordinate
Conc. aA + bB Æ P
r = k[A]m [B]n
[R]
[R] (m, n) π (a, b)
Time
Rate of reaction
[P] DC
(1) Average Rate:
Time Dt
IIT JEE PC-V2_01.indd 1 5/13/2017 10:25:42 AM

1.2 Physical Chemistry-II for JEE (Main & Advanced)
Conc. Rate Rate

[P] 98°F
[P] t2
[R] t1
[P] t1
[R] t2 [R] O
O temperature
t1 t2 temperature (K)
Time (Biological Enzyme)
DC È[ R]t2 - [ R]t1 ˘ [ P]t2 - [ P]t1 At T Æ ; maximum rate

= -Í ˙= For majority of the reaction; on increasing temperature
Dt Î t2 - t1 ˚ t2 - t1
by 10°C rate of the reaction increases two to three times.
–Ve sign indicate decrease in concentration of reactant (4) Catalyst
moles
Units of reaction rate: or M/sec–1 P.E. (–) ve catalyst
- sec
Without catalyst
Conc. (+) ve catalyst
C R
P
O
Reaction
R
t1 Time Catalyst increases the rate of reaction
O T
(5) Solvent
Ê dc ˆ OC Solvent
ÁË ˜¯ =
dt t = t1 OT
Polar Non-Polar
In general, rate of reaction changes with time C6H6
Protic Aprotic n-C6H14
Conc. Conc. SN1 SN2
H2 O CH3
T¢ H C N (DMF)
[P] O¢ Time EtOH
O CH3
t1 Time C (6) Surface area

O
For reaction involving solid surface area,
Ê dc ˆ CO¢ rate μ surface Area
ÁË ˜¯ =
dt t = t1 O¢T ¢ (7) Radiation
25∞C
CH4 + Cl2 æææ
hv
Æ CH3 – Cl + H – Cl
Factors affecting rate of the reaction:
25∞C
(1) Nature of reactants CH4 + Cl2 æææ
Dark
Æ NO reaction
700∞C Rate Constant (K)/Velocity constant/Specific reaction

C (graphite) + O 2 æææÆ CO 2 K1 > K 2 \ r1 > r2
K 1 rate
700∞C Rate constant is defined as the rate of the reaction. When con-
C (diamond) + O 2 æææ
K
Æ CO 2
2 centration of each reactant is unity.
(2) Concentration or volume or pressure aA + bB h P
n P
aA(g) + bB(g) Æ P [ A] = A = A rate = K[A]m [B]n
V RT
If [A] = 1 M
Rate = K [ A] [ B]
m n
and [B] = 1 M
K then rate = K
= ( PA ) m ( PB ) n
( RT ) m + n Characteristic of Rate constant (K)
(3) Temperature Rate constant for any particular reaction is constant at con-
Rate of the reaction generally increases with the in- stant temperature. It does not change with concentration vol-
creases in temperature. ume, pressure, time, etc.

Chemical Kinetics 1.3
Catalyst increases rate constant ‘k’. Molecularity

K depends on temperature. For a single step reaction: Molecularity is defined as number
Ea
- RT of reactant molecules participating in balanced chemical re-
K = Ae action. Molecularity of reaction is generally 1 or 2. For few
K reaction it is also observed to be 3.
Molecularity cannot be more than 3 because probability
A
of more than 3 molecules colliding at the same instance is
almost zero.
Molecularity cannot be –ve, zero, or fraction.
Time For complex reaction : each step has its own molecularity
RhP
KT +10 If mechanism R h P* + Q*
Temperature Coefficient (m) = = 2 to 3
KT P* + Q* h I*
Higher the value of rate constant; more will be the rate of I* h P
the reaction
but overall molecularity has no significance.
Higher value of rate constant; suggest reactant is kineti-
For elementary reaction; molecularity and order are same.
cally unstable.
Molecularity of a single step reaction can be obtained by
Graphite at 700°C is kinetically unstable than diamond
reaction stoichiometry.
Units of rate const. (K)
Example (1) A h B
RhP or
Rate = K[R]m Order of reaction(m) A h B + C Molecularity = 1
Moles Ê mole ˆ
m Example (2) 2A h P
= KÁ ˜¯ or
- sec Ë
A+BhP
1- m
Ê moles ˆ 1 M 1- m or
K =Á ˜¯ ◊ =
Ë sec sec A h 1/2 P Molecularity =2
Example (3) 3A h P
Rate Law or
aA + bB h cC + dD A h 1/3 P
1 Ê d [ A] ˆ 1 Ê d [ B ] ˆ 1 Ê d [C ] ˆ or
Rate = Á- ˜ = Á- ˜ = Á+ ˜ 2A + B h P Molecularity = 3
a Ë dt ¯ b Ë dt ¯ c Ë dt ¯
Unimolecular: N2O5 h N2O3 + O2
1 Ê d [ B]ˆ
= Á+ ˜ = k[ A] [ B]
m n
Bimolecular: H2 + Cl2 h 2HCl
d Ë dt ¯
Tri/ter molecular: 2H2 + O2 h 2H2O
d [ A]
- Æ rate of disappearance of A. Order of the reaction
dt In the expression of rate law, order is defined as (coefficient)
d [C ] of active mass.
+ Æ rate of formation of C.
dt aA + bB h P
m Æ order w.r.t. A. Rate = K[A]m [B]n
n Æ order w.r.t. B. m = Order w.r.t. A
m + n Æ overall order of the reaction. n = Order w.r.t. B
(m + n) = overall order of reaction
Relation between different rate constants Order of any reaction can be obtained only by experimen-
d [ A] tal methods.
- = K ◊ a[ A]m [ B]m = K A [ A]m [ B]n
dt Order of reaction may have –ve, +ve, zero or fractional
d [ B] value.
- = K ◊ b[ A]m [ B]m = K B [ A]m [ B]n
dt Order of reaction is related with reaction mechanism.
d [C ] reaction mechanism may change with experiment condi-
+ = K ◊ c[ A]m [ B]m = KC [ A]m [ B]n
dt tion order may also change with reaction condition:
d [ D] SN1
+ = K ◊ d [ A]m [ B]m = K D [ A]m [ B]n H2O R Nu + X \ Rate = K[R–X]
–
dt R X + Nu(–)
SN2 R Nu + X– \ Rate = K[R–X] [Nu–]
K K K K (2°)
K= A= B = C = D DMF
a b c d

Zero order reaction K [ A]

A Æ P If [A] >> K¢ then, Rate =
[ A]
t=0 a —
t (a – x) x (2) Half-life of zero order reaction
A Æ P
- d [ A] + d [ P] (i)
Rate = = = K [ A]∞ t=0 100 –
dt dt t = 10 min 50 50
- d [ A] + d [ P] t = 15 min 25 75
=K [or] =K t = 17.5 min 12.5 87.5
dt dt
a- x f x t Form the above information, reaction is zero order re-
Ú - d [ A] = K Ú dt Ú dx = K Ú dt action.
1
0 0 0 0
We know t1/2 μ n-1
(a – x) – a = –Kt x = Kt (ii) a
(a – x) = –Kt + a n -1
(t1/2 ) I Ê aII ˆ
[A]t = –Kt + [A]0 (iii) =
(t1/2 ) II ÁË aI ˜¯
Half-life of zero order reaction n -1
x = Kt 10 Ê 50 ˆ 1- n
fi =Á ˜ =2=2
at t = t½ = t50% = when x = a/2 5 Ë 100 ¯
a fi n = 0.
t1/2 = (iv) (3) Zero order reaction is 100% completed.
2K
(4) For zero order reaction in the same time interval, equal
Ê 1 ˆ amount of reactants are consumed and concentration
ln t1/2 = ln a + ln Á
Ë 2 K ˜¯
(v)
of reactants at the same time intervals are in A.P. with
Time of completion for zero order reaction. C.D. –Kt.
x = Kt AhP
t=0 a
a
= 2 ¥ t1/2 or 2 ¥ t50%
t100% = t a – Kt
K 2t a – K(2t)
Few graphs related to zero order reaction 3t a – K(3t)
Conc.
x = Kt
Conc.
[A]t [P] Examples:
[A]0
(1) Photochemical reaction
hv
H2 + Cl2 ææÆ 2HCl
Time (2) Reaction taking place at the solid catalyst surface.
Time
Ni
C2H2 + H2 ææÆ C2H6
Conc. Rate
AÆ P First order reaction
–K A h P
K t=0 aM —
K t (a – x) x
t50% t100% Time Time - d [ A] + d [ P]
Rate = = = K [ A]1 (i)
dt dt
a- x t
lnt1/2 - d [ A]
t1/2
45° Ú [ A]
= K Ú dt
Slop = ½ K a 0
fi ln(a – x) – ln a = –Kt
ln(1/2K)
fi ln(a – x) = –Kt + ln a (ii)
lna
a a-x
ln = - Kt fi a - x = a e - Kt
Characteristics of zero order reaction a
(1) Rate is independent of concentration and does not a
changes as the reaction progress. ln = Kt (iii)
a-x
K [ A]
Rate = 2.303 a
[ A] + K ¢ K= log10 (iv)
t a- x

Few graph related to first order reaction Half-life of first order reaction
Conc. [A]0 Conc. a = [A] 2.303 a
0 K= log
[P]t t a-x
[P]
2.303 a 2.303
K= log fiK= log 2
[A] t1/2 a - a /2 t1/2
Time Time 0.693 ln 2 1

fi t1/2 = = or t1/2 μ 1-1
K K a
(a – x) = ae–kt
x = a(1 – e–kt) t1/2
Degree of dissociation of first order reaction
A h P a
a — 1.0 0.693/K
a–x
a(1 – x/a)
x a
a= = 1 - e - kt A h P
a
t t=0 100 —
t = 10 min 50 50
ln[A] t = 20 min 25 75
Slope = –K t = 30 min 12.5 87.5
ln[A]0
Characteristic of first order reaction
(1) In first order reaction, in equal time interval, same frac-
time tion of reactants are consumed and concentration of re-
actants at same time interval are in GP with a common
log[A]t ratio e–Kt.
A h P
Slope = –K/2.303 t=0 a
log[A]0 t ae–Kt
2t ae–K(2t)
time 3t ae–K(3t)
Since [A]t = [A]0 e–Kt
ln a/a-x (2) Rate μ [A]t
1 0.693
Slope = K (3) t1/2 μ 1-1
and t1/2 =
a K
Examples of first order reaction
time H+
(1) CH3COOEt + H2O ææÆ CH3COOH + EtOH
log a/a-x (2) 2H2O2 h 2H2O + O2
(3) All nuclear reaction
Slope = K/2.303 (4) Decomposition of N2O5
Second order reaction
Case I: When concentration of both reactants are same
time
A h P
t=0 a –
Rate
t=1 a–x x
x
dx 1 È 1 1 ˘
(a - x) - n =
dt Ú0
or -
(n - 1) ÍÎ (a - x) n -1 a n -1 ˙˚
time x t
dx -2
Rate = K[A]t = K[A]0 e –[Kt]
dt
= K (a - x) 2 So Ú (a - x) dx = Ú K dt
0 0

1 1 1 1 Eq. (2) – (1) = Eq. (3) – (2)

fi Kt = - = -
a - x a [ A]t [ A]0 1 1
= Kt = -
Half-life of second order reaction [ A]2t [ A]t
1 Examples of second order reaction
t1/2 =
K ◊a (1) Hydrolysis of ester in basic medium
(2) Decomposition of actatdehyde
Graphical representation of second order reaction CH3CHO h CH4 + CO
Rate Rate = K[A]2 Case II: When concentration of both reactants are
Conc. AÆP different
A + B Æ P
t=0 a b –
t=t a–x b–x x
[A]
dx
Time Time = K (a - x)(b - x)
dt
x t
dx
Ú (a - x)(b - x) = K Ú dt
1/[A]t
Slope = K 0 0
t1/2 x
1 È (a - x) - (b - x) ˘
(a - b) Ú0 ÍÎ (a - x)(b - x) ˙˚
fi dx = K (t - 0)
Slope = 1/K
1/[A]0
1 È ˘
x x
1 1
time t 1/a fi ÍÚ dx - Ú dx ˙ = Kt
since a 1– x = Kt +
1 1 1
Since t1/2 = K ¥ a (a - b) ÍÎ 0 (b - x) 0
(a - x) ˙˚
a
1 È b a ˘
fi ln - ln = Kt
ln t1/2 (a - b) ÍÎ b - x a - x ˙˚
45°
1 È b (a - x) ˘
fi ln ◊ = Kt
(a - b) ÎÍ (b - x) a ˚˙
ln(1/K)
Special case
ln a
If concentration of A is too greater than B.
ln t1/2 = ln(1/K) + ln(1/a) [A] >> [B]
ln t1/2 = ln(1/K) – ln a a–x a
Characteristics of second order reaction: 1 b
K ¢ = ln 1st order w.r.t. [B]
A h P t b-x
(1) Rate = K[A]2
Rate = K[A]0[B]1
1
(2) t1/2 μ 2 -1 H+
a H2O + CH3COOC2H5 ææÆ EtOH + CH3COOH
A h P (excess) Rate = K¢[ester]1 (Pseudo unimolecular)
t=0 100 –
t = 10 50 50 Nth order
t = 30 25 75 A h P
t = 70 12.5 87.5 t=0 a –
(3) At equal time interval, concentration of reactants are in t=t a–x x
H.P. dx
1 1 = K (a - x) n
K (t ) = - (2) dt
[ A]t [ A]0 x
dx
t
1 1 Ú (a - x)n = K Ú dt
K (2t ) = - (1) 0 0
[ A]2t [ A]0 1 È 1 1 ˘
Kt = Í n -1
- n -1 ˙
K (3t ) =
1
-
1 (3) (n - 1) Î (a - x) a ˚
[ A]3t [ A]0

Half-life of nth order reaction (2) Using integrated rate equation (Hit and Trial)
1 È 1 1 ˘ A Æ P
Kt1/2 = -
(n - 1) ÍÎ (a - a /2) n -1 a n -1 ˙˚ t=0 a –
t1 a – x1 x1
1 2 n -1 - 1 C t2 a – x2 x2
t1/2 = = n -1
K (n - 1) a n -1 a : :
: :
2 n -1 1
C= for n π 1\ t1/2 μ n -1 Zero order reaction
K (n - 1) a x x x x
K= fiK= 1 = 2 = 3
Graph related to nth order reaction t t1 t2 t3
1 1 2.303 a
(i) n -1
= (n - 1) Kt + K= log if K1 = K2 = K3 … first order
[ A]t [ A]0n -1 t a-x
1 1È 1 1 ˘ if K = K = K … second order
K= Í -
t Î a - x a ˙˚
1 2 3
[A]tn–1 Slope = (n – 1)K
(3) Graphical method using concentration
1
[A0]n–1 [A] ln[A]
time
1
(ii) t1/2 = C ◊ n -1
a O I
t1/2 t t
1/[A]t 1/[A]n – 1
2n–1 – 1
Slope = C =
K(n – 1)
II nth order
1
an–1 t t
(iii) ln t1/2 = ln C – (n – 1) ln a
(4) Graphical method using half-life
ln t1/2
Slope = 1 – n ln t1/2
ln C Slope = 1 – n
ln a
ln a
Prediction of order of the reaction
(1) Initial rate method or different method (5) Half-life method
For nth order reaction:
A+BhP
dx C
Rate = = K [ A]m [ B]n t1/2 =
dt a n -1
n -1
Exp. No. [A]0 [B]0 Initial Rate (M sec–1) t1 Ê a2 ˆ
=
1. x y z t2 ÁË a1 ˜¯
2. 2x y 4z t1
ln
t2 ln t1 - ln t2
3. 2x 2y 8z = n -1fi n =1+
ln
a2 ln a2 - ln a1
4. p q x
a1
z = K(x)m (y)n (i)
Concentration terms replaced by other terms in first
m n
4z = K(2x) (y) (ii) order integrated equation.
8z = K(2x)m (2y)n (iii) A ææææ
ÆP
Ist order
m = 2, n = 1 t=0 aM –
Rate = K[A2][B] t=t a–x x

a [ A]0 (n A )0 (WA )0 (No. of A) at t = 0 V0 μ H+ (i)

= = = =
a - x [ A]t (n A )t (WA )t (No. of A)at t = t Vt μ H + + x (ii)
( PA )0 V μ H+ + a (iii)
= for gas since P μ n (If V and T const.)
( PA )t V – V0 μ a (iv)
V – Vt μ a – x (v)
(1) Concentration term replaced by partial pressure
2.303 È a V - V0 ˘
A(g) Æ B(g) + C(g) K= log Í =
t Î a - x V - Vt ˙˚
t=0 P0 – –
t=t P0 – p p p (4) Inversion of cone sugar
PT = (P0 – p) + p + p optical rot. (+ r10 ) + r20 - r30
PT = P0 + p
C12H22O11 + H2O h C6H12O6 + C6H12O6
p = PT – P0
(G) (F)
\ P° – p = P0 – (PT – P0) = 2P0 – PT
t=0 a – – –
P0 μ a and P0 – P μ (a – x)
t=t a–x – x x
2.303 P0 tÆ – – a a
K= log
t 2 P0 - PT | r20 | < | r30 |
a P0 P0 r 0 = ar10
= = (i)
a - x P0 - p 2 P0 - PT
r = (a -
t
x)r10 + xr20 - xr30 (ii)
(2) Concentration term replaced by volume of reagent
used in titration r = ar20 - ar30 (iii)
Stdandard KMnO4 From (i) and (ii); (i) and (iii)
V0 V0 μ a -r t t + r 0 r0 - r
Vt μ a – x = x and =a
r10 - r20 + r30 r10 - r20 + r30
rt - r
a-x=
r10 - r20+ r30
Vml sample
a r -r 0
H2O2 =
a - x rt - r
1st order
2H 2O 2 ææææ Æ 2H 2O + O 2
2.303 r0 - r
t=0 a – k= log t
t=t a–x x t r -r
2.303 V0
K= log Parallel Reaction
t Vt
K1 K1 B
A B
V0 Æ Vol. of KMnO4 used in titration against V ml
OR A K2
sample of Solution of H2O2 at t = 0. A
K2
C C
(3) Hydrolysis of ester in acidic medium
H+ - d [ A]
CH3COOC2H5 + H2O ææÆ CH3COOH + EtOH Rate of decomposition of ‘A’, = K1[A] + K2[A]
a – – – dt
= [K1 + K2][A]
a–x – x x
1 [ A]
– – a a K1 + K 2 = ln 0
t [ A]t
[ A]t = [ A]o ◊ e -[ K1 + K 2 ] ¥ t
d [ B]
Std. NaOH Rate of formation of ‘B’= = K1[ A]
V0 dt
d [C ]
Rate of formation of ‘C’= = K 2 [ A]
dt
d [ B ] K1 [ B ] K1
V m1 = = fi =
d [C ] K 2 [C ] K 2

K1 - K1[ A]0
% yield of B = ¥ 100 at t = 0, [B] = 0 fi C =
K1 + K 2 K 2 - K1
Concentration of [B] at any time
K2
% yield of C = ¥ 100 K1[ A]0 e( K 2 - K1 )t
K1 + K 2 e K2t [ B ] =
K [ A]
- 1 0
K 2 - K1 K 2 - K1
[A]0 = [A]t + [B]t + [C]t
K1[ A0 ] - K1t
eg: [ B] = [e - e - K2t ]
K1
K 2 - K1
K1 2B or A 2B
d [ B] K1[ A]0
A K2 A
K2
3C = [- K1e - K1t + K 2e - K 2t ] = 0
3C dt K 2 - K1
K1 and K2 are dissociation constants of A fi K1e- K1t = K 2 e- K 2t
K
-
d [ A]
= [ K1 + K 2 ][ A] e( K 2 - K1 )t = 2
dt K1
[ B]t [C ]t 1 K
[ A0 ] = [ A]t + + fi tmax = ln 2
2 3 K 2 - K1 K1
d [ B] If K2 >> K1, then concentration of [B] is very small and
= 2 K1[ A] = K B [ A]
dt practically becomes constant.
dC d [ B]
= 3K 2 [ A] = 0 fi K1[ A] - K 2 [ B] = 0
dt dt
[ B] 2 K1 2 K1 K
= and % B = ¥ 100 fi [ B] = 1 [ A]
[C ] 3K 2 2 K1 + 3K 2 K2
3K 2 Reversible reaction
%C = ¥ 100 Kf
2 K1 + 3K 2 H 2 + I2 2HI
Kb
Reaction in series
K K
r = K f [H 2 ][I 2 ] - Kb [HI]2
A ææ
1
Æ B ææÆ
2
C
1 d [HI]
- d [ A] r=
Rate of decomposition of A = = K1[ A] 2 dt
dt d [HI]
Rate of formation of B = K1[A] – K2[B] = 2[ K f [H 2 ][I 2 ] - Kb [HI]2 ]
dt
Rate of formation of C = K2[B]
d [H 2 ] d [I 2 ] d [HI]
r= = =
dt dt 2dt
[Conc]
C Kinetics for reversible reaction
When I order opposed by I order
Kf
B A B
A Kb
t
t=0 a –
dB dB
= K1[ A] - K 2 [ B] fi + K 2 [ B] = K1[ A]0 e- K1t t=t a–x x
dt dt
at equilibrium a – xe xe
On multiplying by e K2t on both sides d [ A] - d [a - x] dx
d [ B] - = =
e K2t ◊ + K 2e K2t [ B] = K1[ A]0 e( K2 - K1 )t dt dt dt
dt dx
= K f (a - x) - Kb ( x)
d [e K2t [ B]] dt
= K1[ A]0 e( K2 - K1 )t
dt dx
at equilibrium =0
d [e K 2t [ B]] = K1[ A]0 e( K 2 - K1 )t ◊ dt dt
On integration Kf(a – xe) = Kbxe
K1 ◊ [ A]0 ( K 2 - K1 )t K f (a - xe )
e K2t [ B] = e +C Kb = (i)
K 2 - K1 xe

Kbxe = Kfa – Kfxe Activation energy (Ea)

(Kf + Kb)xe = Kfa It is the extra amount of energy required by reactant mol-
ecules to reach up to the threshold energy.
Kf ◊a
K f + Kb = (ii) Activated complex
xe Ethres.
Ea
From Eq. (i), E
K f (a - xe ) ◊ x EP
dx DH
= K f (a - x) - ER
dt xe
dx K f Reaction Coordinate Æ
= [axe - xxe - ax + xxe ]
dt xe Ea = Ethreshold – ER
dx È K f ˘ = Eactivated complex – ER
=Í a ˙ ( xe - x)
dt Î xe ˚
(b) Orientation Barrier
dx In order to have effective collisions, the reactant molecules
= ( K f + Kb )( xe - x)
dt must collide in the proper direction.
On integration, Factor affecting rate of reaction
dx (i) Physical state
Ú ( xe - x) = ( K f + Kb )Ú dt Solid < Liquid < gas
(ii) Particle size
–ln(xe – x) = (Kf + kb)t + C
Smaller is the size if particle, more will be the rate of reaction
at t = 0; C = –ln xe because effective surface area increases.
–ln(xe – x) = (Kf + Kb) t –ln xe (iii) Temperature
1 xe For both endo- and exo-thermic reactions, rate of reaction
(K f + K b ) = ln increased on increasing the temperature.
t (xe - x )
On increasing the temperature by 10°C generally rate of
Arrhenius collision theory reaction becomes 2 to 3 times.
1. This theory is mainly applied to bimolecular collision. Rate = z ¥ e–Ea/RT
2. When reactant molecules collide among themselves zμ T
then, only they can convert themselves into product if
Effective collision occur. On increasing the temperature by 10°C, rate of reaction
3. Collision frequency is generally very high but number changes mainly because of fraction of effective collisions,
of effective collision or active molecules are compara- i.e., e–Ea/RT which becomes almost 2 to 3 times.
tively low. Temperature coefficient (m)
4. For any collision to be effective, there are two barriers. It is the ratio of two rates when temperature is increased by
(a) Energy barriers 10°C.
In order to have effective collisions, reactant molecules must R K
possess some minimum amount of energy known as thresh- m = t +10∞C = t +10∞C = 2 to 3.
Rt ∞C K t ∞C
old energy. DT
R2 K 2
= = ( m ) 10
Fraction R1 K1
of molecules
Effect of temperature on rate constant (K)
A/C to Arrhenius equation;
Ethreshold K = Ae–Ea/RT
Energy Æ
A Æ Arrhenius constant or pre-exponential factor or frequen-
Shaded area represents the fraction of active molecule cy factor.
which are having energy ≥ Ethreshold Ea
f = e–Ea/RT [fraction of active molecules] ln K = ln A -
RT
Ea Æ activation energy Ea
log K = log A -
R Æ Gas constant 2.303 RT
T Æ temperature

For example manufacture of NH3 by Haber’s process:

Fe(S)
+ve catalyst N2(g) + 3H2(g) æææ Æ 2NH3(g)
Energy Ea Ea > Ea¢ (3) Auto Catalysts:
Ea¢
In these reactions, one of the products formed act as a
catalyst during the reaction.
H + (aq)
Reaction Coordinate Æ
CH3COOC2H5(aq.) + H2O ææææ Æ
CH3COOH(aq.) + C2H5OH(aq.)
Ea (autocatalyst)
log K 2 = log A -
2.303 RT2 Photochemical reactions
Ea These are reactions which occur in presence of light and ra-
log K1 = log A - diation.
2.303 RT1
hv
For example H 2 + Cl2 ææÆ 2HCl
K2 Ea È 1 1˘
log = Í - ˙ These reactions follow zero order kinetics.
K1 2.303R Î T1 T2 ˚
rμI I = intensity of light
r=f◊I
Note: f = quantum efficiency or quantum yield.
1. As the activation energy of reaction increases, rate of Number of moles of reactant reacted
reaction decreases. f=
Number of moles of photon absorbed
2. For two different reactions:
Ea1 > Ea2 Reaction mechanism
DT fi identical (T1 = T2) In order to find the rate expression from the given reaction
mechanism, there are two methods:
Ê K2 ˆ Ê K2 ˆ
fi ÁË K ˜¯ > ÁË K ˜¯ (1) R.D.S. method (Rate determining step method)
1 1 1 2 (a) Select the R.D.S. from reaction mechanism which
is slowest step.
(b) Write the rate expression from the R.D.S. taking it
Catalyst
as elementary.
Positive catalyst speed up the reaction by providing alternat-
(c) If there is any intermediate then, remove it.
ing path of both for the reaction. In which energy of activated
For example,
complex is lesser, so activation energy is lesser. Hence, rate
Ex (1) Reaction: 2NO2 + F2 h 2NO2F
of reaction increases.
Mechanism:
K
+ve catalyst
NO2 + F2 ææ
1
Æ NO2F + F; (slow)
K
Energy Ea
Ea¢
Ea > Ea¢ F + NO2 ææÆ 2
NO2F; (fast)
r = K1[NO2][F2]
(2) Reaction: 2O3 h 3O2
Reaction Coordinate Æ Mechanism:
Negative catalyst or inhibitor decrease the rate of reaction O3 KC
O2 + O; (fast)
by providing an alternating path in which activation energy
K
increases. O3 + O ææÆ 2O 2 ; (slow)
Types of catalysis r = K[O3][O] (i)
(1) Homogenous catalysis: [O 2 ][O]
When reactants and catalysts are present in the same KC =
[O3 ]
phase.
here (O) is intermediate.
For example by lead chamber process
K [O ]
2SO2(g) + O2(g) æææÆ 2SO3(g)
NO(g) \ [O] = C 3
[O 2 ]
(2) Heterogeneous catalysis: From (i)
When reactants and catalyst are present in different phase.
For example Æ manufacture of H2SO4 by contact pro- [O3 ]2
r = K ◊ KC
cess [O 2 ]
V O (s)
2SO2(g) + O2(g) ææææ
2 5
Æ 2SO3(g) r = K ◊ KC [O3 ]2 [O 2 ]-1

(2) Steady state approximation method Velocity: a < b < g

This method is based on the fact that net rate of forma- Penetration power: a<b<g
tion of intermediate is zero. Ionisation power: a>b>g
1 - d [NO 2 ] Radioactive disintegration
r= ¥
2 dt All radioactive decay follow first order reaction:
- d [NO 2 ] Rate of disintegration or activity (A)
= K1[NO 2 ][F2 ] + K 2 [NO 2 ][F]
dt - dN
= μN
According to steady state approximation method. dt
d [F] Where N = (Number of radioactive nuclei left at given time)
= 0 = K1 ◊ [NO 2 ] ◊ [F2 ] - K 2 [NO 2 ] ◊ [F] - dN
dt = lN
fi K1 ◊ [NO2] ◊ [F2] = K2[NO2] ◊ [F] dt
N = N0e–lt
d [NO 2 ]
fi - = 2 K1[NO 2 ] ◊ [F2 ] N = Number of radioactive nuclei taken initially
dt
1 d [NO 2 ]
fi r= ¥ = K1[NO 2 ] ◊ [F2 ] N
2 dt
Reation of fractional order:
(i) H2 + Br2 h 2HBr Rate = K [H2] [Br2]1/2
(ii) COCl2 h CO + Cl2 Rate = K [COCl2]3/2 t
(iii) CO + Cl2 h COCl2 Rate = K [CO]2 [Cl2]1/2 1 N 1 A
l = ln 0 l = ln 0
(iv) Para H2 h Ortho H2 Rate = K [PH2 ] 3/2 t N t A
n
(v) Thermal decomposition of acetaldehyde 1 m Ê 1ˆ
l = ln 0 and Nt = N o Á ˜
Rate = K [CH3CHO]3/2 t m Ë 2¯
m0 : mass of nuclei initially n = Number of half-lite used
RADIOACTIVITY Nt m È1˘
n
\ = =
N 0 m0 ÍÎ 2 ˙˚
It is a spontaneous nuclear phenomena in which certain ra-
Half-life period (t1/2):
diations like a, b, g are emitted by the nuclei of radioactive
0.693
substances. t1/2 =
Radioactivity is independent of physical conditions like l
temperature, pressure etc. ttotal = n ¥ t1/2
a-rays Average Life: (tavg.)
These consist of helium nuclei (He+2). Due to each a-particle 1 t
decay, atomic mass number decreases by 4 whereas atomic tavg. = = 1/2
l 0.693
number decreases by 2. = 1.44 ¥ t1/2
A- 4
A
Z X ææ
Æ Y +a N = N 0 e - lt
Z -2
1
b-rays t = tavg =
These are composed of electrons. l
N0
–1e fi A = 0, Z = –1
0
at N= = 0.37 N 0
e
0 n ææ
Æ 1P1 + -1e0
1
It is time in which 37% of the initial radioactive nuclei
remain, i.e., 63% decay.
During the b-decay, there is no change in mass number but
atomic number increases by 1 due to the conversion of neu- Units of activity
tron into proton and electron. SI units: Disintegration per second (dps) or Becquerel (Bq)
g-rays Other units:
These are electro-magnetic radiation. Due to their emission, Curie (Ci) fi 1 Ci = 3.7 ¥ 1010 dps
there is no change in mass number and atomic number de- Rutherford (Rd) fi 1 Rd = 106 dps
creases the energy level in nucleus. Specific activity
It is the activity of 1 g radioactive substance.

Definitions (1) Up to Z = 20; n/p ratio is 1 for most stable nuclei but
(1) Isotopes : Same atomic number but different mass number above Z = 20, n/p ratio for stable nuclei increases because
(2) Isobars : Same mass number but different atomic number as the number of proton increases, electrostatic repulsion be-
(3) Isotopes : Same number of neutrons : [A – Z] Æ constant tween these increases. In order to overcome these repulsive
(4) Isodiaphers : (n – p) fi same OR forces, neutrons increase number.
Above Z = 83; there is no stable nuclei.
(A – 2Z) fi same
Among the stable nuclei, n/p ratio is maximum for Bi bis-
Radioactive disintegration series muith (1.5).
There are four natural disintegration series. Those nuclei which have number of neutron protons equal
Series Name Starting Stable End to magic number Æ 2, 8, 20, 28, 50, 82, 126 are more stable.
Element Product Maximum number of stable nuclei have even number of
neutrons and even number of protons whereas very few sta-
4n Thorium series Th – 232 Pb – 208 ble nuclei have odd noumber of neutron and proton.
4n + 1 Neptunium series Np – 237 Bi – 209 Favourable condition for disintegration
4n + 2 Uranium series U – 238 Pb – 206
Type of Favourable Effect
4n + 3 Actinium series U – 235 Pb – 207 decay condition
Application of radioactivity n
Age determination of minerals, rocks or the earth for age 1. a-decay Z > 83 ≠
p
determination, minerals or rock sample is analysed for the
amount of radioactive substance and its stable end product. for (heavy un-
92 U
238
ææ
Æ 90Th 234 + 24a
When age of the mineral can be obtained from the formula. stable nuclei
1 a n
l = ln 2. b-decay high n/p Ø
t a-x p
t = age of mineral 6C
14
h 7N14 + –1e0
a = initial amount of radioactive substance n n
Age determination of dead animals and plants or carbon = 1.33, = 1.0
p p
dating
3. g-decay high-energy decrease the energy level.
7N + 0n h 6C + 1P
14 1 14 1
level in nuclei
This method is based on ratioactive decay of 14C, which formed
in the upper part of atmosphere according to above reaction.
At the same time, C14 disintegrates so that ratio of radioactive Positron n n
4. low ratio ≠
carbon and non-radioactive carbon becomes constant. This decay p p
ratio is available in all living animals and plants. After the
(b+ decay) h 6C13 + 1e0
7N
13
death of animal or plant, this ratio changes due to disintegra-
n/p = 6/7 n/p = 7/6
tion of C14. The age can be determined from the formula:
5. k-capture 1P1 + –1e0 h 0n1
1 a
l = ln
t a-x It is the phenomena in which lighter unstable nuclei having
low n/p ratio capture the e– from the nearest shell (i.e., K-
Accuracy for this method is not good, when it is applied for n
very small or long time period. shell) in order to increase the ratio.
p
Cause of radioactivity
Those nuclei whose n/p ratio is in the range 1 to 1.5 are gen-
7
4 Be + -1e0 ææ
Æ 37 Li
erally stable. This range is called stability belt. n 3 n 4
For unstable nuclei, disintegrate in order to reach to the = =
p 4 p 3
stability best.
Nuclear reactions
Reactant nuclei + Bombarding particle Æ product nuclei
n + emitted particle
Representation
Reactant nucleus (bombarding particle, emitted particle)
product nucleus.
11Na + 1P h 12Mg + 0n
24 1 24 1
20 p 24
11Na (1P1, 0n1) 12Mg24

E = Dmc2
3 Li (a 2 , 2 He)3 Li
7 4 3 8
Example
1 amu = 931.5 MeV
Example 94 Be(g 0 n1 )84 Be
A1 - A2
During the nuclear fission and fusion, large amount of energy Number of a particle emitterd =
4
is released because of mass defect.
Dm = mass defect = mR – mP No of b particle emitted = 2a – [Z1 – Z2]
Solved Examples
1. At 10°C for any reaction rate constant = K, what will be

rate constant at 90°C (given temperature coefficient 2) [NH3] 0.6
R2 K 2 DT 0.4
Sol. = = ( m ) 10 = 28 K
R1 K1 0.2
5 10 20
2. (a) For the following reaction write down rate law: Time (sec) Æ
N2 + 3H2 h 2NH3
D[NH3 ] 0.2
12 g - = = 0.04 M/sec -1
(b) If rate of dissappearance H2 is . What is Dt 5
- sec
the rate of appearance of NH3. 1 0.2
r= ¥ = 0.01 M/sec -1
2 10
1 Ê - d [N 2 ] ˆ 1 Ê - d [H 2 ] ˆ
Sol. (a) Rate = Á ˜= Á ˜ 5. 2N2O5 h 4NO2 + O2, the variation of concentra-
1 Ë dt ¯ 3 Ë dt ¯ tion of N2O5 with time can be expressed by [N2O5] =
1 + [dNH3 ] [N2O5]0 e–Kt and K = 10–4 sec–1. If initially 1 mole of
= = K [N 2 ]m [H 2 ]n
2 dt N2O5 taken calculate.
(i) Rate of disappearance of N2O5 at t = 104 sec.
d [NH3 ] 2 Ê - d [H 2 ] ˆ 2 12 moles (ii) Rate of reaction during first 104 sec.
(b) = ÁË ˜¯ = ¥ =4 (iii) Variation of concentration of NO2 with time.
dt 3 dt 3 2 - sec
d [N 2O5 ]
= 4 ¥ 17 = 68 g
gram (i) Rate = - = K [N 2O5 ]0 e - Kt
- sec dt
-4
¥104
= K [N 2O5 ]0 e -10
3. For the reaction, 2A Æ 3B + 4C, the number of moles
of B increases by 6 ¥ 10–3 moles in 10 sec in a 10 L 1
= K [N 2O5 ]0 ¥
container. Calculate: e
(a) rate of appearance of B and C. 1
= 1 ¥ 10-4 [1] ¥
(b) rate of disappearance of A e
DConc. 6 ¥ 10-3 We know a =
x
= 1 - e - Kt for first order.
Sol. (a) rB = = = 6 ¥ 10-5 a
Dt 10 ¥ 10
1 - 1/e 1
rC rB 4 (ii) R = ¥
= fi rC = ¥ rB = 8 ¥ 10-3 104 2
4 3 3
(iii) 2N2O5 Æ 4NO2 + O2
rA rB 2 1 – –
(b) = fi rA = rB = 4 ¥ 10-5 1–a 2a a/2
2 3 3
2 mole
4. For the reaction; 2NH3 Æ N2 + 3H2, the curve is plot-
ting between concentration of NH3 v/s time. Calculate
(a) rate of decomposition of NH3 between 5 to 10
seconds. [NO2]
(b) rate of reaction between 10 to 20 seconds.
Time

6. For the given gaseous reaction A Æ 2B + C pressure 0.0453

after sufficient time was found to be 300 mm and after x= ¥ 238 = 0.05234
206
time 2.303 sec, it was found to be 200 mm calculate.
0.693 1 Ê 1.05234 ˆ
(i) rate constant (ii) half-life = ln Á ˜
A Æ 2B + C 4.5 ¥ 109 t Ë 1 ¯
t=0 P0 – – = 3.29 ¥ 106 yrs.
t=t P0 – x 2x x
t= – 2P0 P0 10. An old piece of wood have 25% of C14 as much as or-
P fi 300 = 3P0 fi P0 = 100 mm dinary wood today has. Find the age of wood given t1/2
P0 + 2x = 200 mm of C14 is 5760 yrs.
Ans. t = 2 ¥ t1/2 = 2 ¥ 5760y
x = 50 mm
11. For the elementary reaction 2A + B2 h 2AB. Calcu-
2.303 P late how much the rate of reaction will change if the
K= log 0
t P0 - x volume of the vessel is reduced to one third of its origi-
2.303 100 nal volume?
K= log = 0.3010
2.303 50 Ê dx ˆ
Sol. 2A + B2 h 2AB Á ˜ = K[A]2[B2]
Ë dt ¯ 1
0.6932 0.6932
(ii) t1/2 = = = 2.303
K 0.3010 V
if V is decrease to
234
disintegrates to gives 82pb206 as the final prod- 3
7. 20Th
uct. How many a and b particles emitted. fi Ê dx ˆ Ê dx ˆ Ê dx ˆ
ÁË ˜¯ = [3 A] [3B ] ÁË ˜¯ = 27 ÁË ˜¯
3
234
h 82Pb206 + x24a + y-01b dt 2 dt 2 dt 1
Sol. 20Th
reaction increases by 27 times.
A2 - A1 234 - 206
OR a= = =7 [OR] 12. In the reaction 2H2O2 h 2H2O + O2 rate of forma-
4 4 tion of O2 is 3.6 M min–1.
A fi 234 = 206 + 4x fi x = 7 b = 2 ¥ a – [Z1 – Z2]
(a) What is rate of formation of H2O?
Z fi 90 = 82 + 2x – y fi y = 6 = 2 ¥ 7 – [90 – 82]
(b) What is rate of disappearance of H2O2?
= 14 – 8 = 6 d O2
8. Activity of 1 g of Radium is found to be 0.5 Ci. Calcu- Sol. 2H2O2 h 2H2O + O2 = 3.6 M min–1
late the half-life period of radium and time required for dt
the decay of 2 g to 0.25 g. [A = 226] (a) Rate of formation of H2O
Sol. Activity = l ◊ N d H 2O
= l ¥ n ¥ NA = 2 ¥ 3.6 = 7.2 M min–1
dt
1 d H 2O 2
=l¥ ¥ 6.022 ¥ 1023
226 = 7.2 M min–1
1 dt
= 0.5 ¥ 3.7 ¥ 1010 = l ¥ 6.023 ¥ 1023 13. A certain organic compound A decomposes by two par-
226
allel first order mechanism
0.693
t1/2 = k1 B
l A
k2
l = 69.417 ¥ 10-13 C
= 9.9 ¥ 1010 sec. If k1 : k2 = 1 : 9 and k1 = 1.3 ¥ 10–5 s–1

Calculate the concentration ratio of C to A, if experi-
3
m 0.25 1 Ê 1 ˆ ment is started with only A and allowed to run for one
= = =Á ˜
m0 2 8 Ë 2¯ hour.
Sol. Given:
ttaken = 3 ¥ t1/2 = 3 ¥ 9.9 ¥ 1010 sec.
9. The final product of U238 is Pb206. A sample of pitch- k1 1
= , k1 = 1.3 ¥ 10–5
gland is 0.0453 g of Pb206 for every gram U238 present k2 9
in it, assuming that the pitch gland formed at the time k2 = 9k1
of formation of the earth didn’t contain any Pb206.
Calculate the age of earth, t1/2 for U238 = 4.5 ¥ 109 yrs. [ A] = [ A]0 e - ( k1 + k2 )t
ln 1.05234 = 0.051. k2 [ A]0
[C ] = [1 - e - ( k1 + k2 )t ]
Sol. a – x = 1 g fi mpb = 0.0453 g k1 + k2
a=1+x
[C ] k2 9k
0.0453 = [e( k1 + k2 )t - 1] = 1 [e10 k1t - 1] = 0.537
U238 h Pb206 [ A] k1 + k2 10k1
206

14. The reaction k1 k

k1
17. For the mechanism A + B C C ææ
3
ÆD
+ + k2
cis–Cr(en)2(OH)2 trans–Cr(en)2(OH)2
k2 Derive the rate law using the steady-state approxima-
is first order in both directions. At 25°C, the equilibri- tion to eliminate the concentration of C. Assuming that
um constant is 0.16 and the rate constant k1 is 3.3 ¥ 10–4 k3 << k2, express the pre-exponential factor A and Ea
s–1. In an experiment starting with the pure cis form, for the apparent second-order rate constant in terms of
how long would it take for half the equilibrium amount A1, A2 and A3 and Eal, Ea2 and Ea3 for the three steps.
of the trans isomer to be formed? k1 k
14. k = 0.16, k1 = 3.3 ¥ 10–4 Sol. A + B C , C ææ
3
ÆD
k2
so k2 = k1/k = 2.0625 ¥ 10–3 r = k1[A] [B] – k2[C]
k1 + k2 = 0.0023925
d [C ]
k k [ A] = k1[A] [B] – k2[C] – k3[C] = 0
[ B]eq. = 1 [ A]eq. = 1 0 dt
k2 k1 + k2
k [ A][ B ]
[ B]eq. k1[ A]0 [C ] = 1
Given [ B] = = k 2 + k3
2 2(k1 + k2 )
d [ D] k [ A][ B ]
k [ A] = r = k1[ A][ B ] - k2 ¥ 1
and [ B] = 1 0 [1 - e - ( k1 + k2 )t ] dt k 2 + k3
k1 + k2 k1k3[ A][ B ]
1 r=
so = 1 - e - ( k1 + k2 )t (k1 + k2)t = ln 2 k 2 + k3
2 since k2 >> k3
t = 289.71 sec. = 4.82 min.
k1k3
15. An optically active compound A upon acid catalysed knet =
hydrolysis yield two optically active compound B and k2
C by pseudo first order kinetics. The observed rotation A1 A3
of the mixture after 20 min was 5° while after comple- so Anet =
A2
tion of the reaction it was –20°. If optical rotation per
mole of A, B and C are 60°, 40° and –80°, calculate half (Ea)net = Ea1 + Ea3 – Ea2
life and average life of the reaction. 18. The decomposition of a compound P, at temperature T
Sol. A h B + C according to the equation 2P(g) h 4Q(g) + R(g) + S(l)
t=0 a – – is the first order reaction. After 30 minutes from the
t = 20 min. a–x x x start of decomposition in a closed vessel, the total pres-
t= – a a sure developed is found to be 317 mm Hg and after a
60(a – x) + 40x – 80x = 5 long period of time the total pressure is observed to be
and 40a – 80a = – 20 617 mm Hg. Calculate the total pressure of the vessel
on solving a = 0.5, x = 0.25 after 75 minute, if volume of liquid S is supposed to be
so t1/2 = 20 min. negligible. Also calculate the time fraction t7/8.
Average life = 1/K = 1.443 ¥ t1/2 = 28.86 min. Given : Vapour pressure of S(l) at temperature T = 32.5
mm Hg.
k1
16. For the reaction A P . Following data is pro- Sol. 2P(g) h 4Q(g) + R(g) + S(l)
k-1
duced: t=0 P0
Time/Hr. 0 1 2 3 4 t = 30 min. P0 – P 2P P/2
%A 100 72.5 56.8 45.6 39.5 30 t= – 2P0 P0/2
Find k1, k–1 and Keq. so P0 – P + 2P + P/2 = 317 – 32.5
Sol. At t = when equilibrium is established i.e., P0 + 1.5P = 284.5 (i)
[ P] 7 and 2.5P0 = 617 – 32.5 = 584.5
k= = = 2.33 so P0 = 233.8
[ A] 3
P = 33.8
k1 233.8
and = 2.33 fi k1 = 2.33 k–1 k ¥ 30 = ln fi k = 0.0052
k-1 200
k2 [ A]0 At t = 75 min
[ A] = [1 - e - ( k1 + k2 )t ] 233.8
k1 + k2 0.0052 ¥ 75 = ln
P0 - P
k–1 = 4.16 ¥ 10–5 sec–1
k1 = 2.33 k–1 = 9.7 ¥ 10–5 sec–1 P0 – P = 158.23 fi P = 75.57
PT = 32.5 + P0 + 1.5P = 347.155 + 32.5

PT = 379.65 mm Hg 67.7
(ii) 0.0052 ¥ t = ln 8 = ¥ 0.1 = 0.09575 mg
70.7
t = 399.89 min.
19. In a nature decay chain series starts with 90Th232 and 21. 84Po218 (t1/2 = 3.05 min) decay to 82Pb214 (t1/2 = 2.68
finally terminates at 82Pb208. A thorium ore sample was min) by a-emission, while Pb214 is a b-emitter. In an
found to contain 8 ¥ 10–5 mL of helium at STP and 5 experiment starting with 1 g atom of pure Po218, how
¥ 10–7 g of Th232. Find the age of ore sample assuming much time would be required for the number of nuclei
that source of He to be only due to decay of Th232. Also of 82Pb214 to reach maximum.
l l
assume complete retention of helium within the ore. Sol. 84 Po
218
ææ
1
Æ82 Pb 214 ææ
2
Æ 83Bi 214
(Half-life of Th232 = 1.39 ¥ 1010 Y)
Number of nuclei of Pb214 at time t are N2 =
Sol. 90Th232 h 82Pb208 + 6 2He4 + 4 –1b0
l1 N 0
t=0a [e - l1t - e - l2t ]
time t a – x 6x (l2 - l1 )
given: dN 2
For max. value of N2 =0
5 ¥ 10-7 dt
a–x= = 2.155 ¥ 10–9 mole
232 1 l
so t= ln 2
8 ¥ 10-5 (l2 - l1 ) l1
6x = fi x = 5.9523 ¥ 10–10 mole
22400 0.693 0.693
so a = 2.75 ¥ 10–9 when l2 = , l1 = ,
2.68 3.05
0.693
k= on putting these values
1.39×1010 3.05
a t = 31.87 ln = 4.12 min
k ¥ t = ln 2.68
a-x
22. A sample pitch blende is found to contain 50% Ura-
0.693 ¥ t 2.75 ¥ 10-9 nium (U238) and 2.425% Lead. Of this Lead only 93%
= ln = 0.2438
1.39 ¥ 1010
2.155 ¥ 10-9 was Pb206 isotope, if the disintegration constant is 1.52
¥ 10–10 yr–1. How old could be the pitch blende deposit?
t = 4.89 ¥ 109 year
Sol. Let the mass of sample in a g and initial mass of U238 is
20. A sample of 131 53 I , as iodine ion, was administered to w g, then
a patient in a carrier consisting of 0.10 mg of stable U238 h Pb206
iodide ion. After 4.00 days, 67.7% of the initial radio- t=0 w
activity was detected in the thyroid gland of the patient. 206
What mass of the stable iodide ion had migrated to the t w–x x
238
thyroid gland? (t1/2 = 8 days.) given w – x = 0.5a
0.693 206 x 2.425a
Sol. k = = ¥ 0.93 = 0.0225525a
8 238 100
A 0.693 A x = 0.026a
kt = ln 0 = ¥ 4 = ln 0
A 8 A so w = 0.526a
A
= 0.707 w
A0 lt = ln
w- x
Total activity is 70.7% of the original activity but only 0.526a
67.7% found in the thysoid so mass of stable iodide ion 1.52 ¥ 10–10 ¥ t = ln
0.5a
had migrated to the thyroid gland is t = 3.33 ¥ 108 year.
Exercise
tion was measured as = 2.5 ¥ 10–4 mol L–1 s–1. The rate
LEVEL I of change of concentration of H2 will be
(a) 1.25 ¥ 10–4 mol L–1 s–1
1. In a reaction involving the synthesis of ammonia by (b) 2.50 ¥ 10–4 mol L–1 s–1
Haber’s process, N2 + 3H2 m 2NH3, the rate of reac- (c) 7.5 ¥ 10–4 mol L–1 s–1
(d) 5.0 ¥ 10–4 mol L–1 s–1

2. In the formation of sulphur trioxide by contact process, k1

Y
2SO2 + O2 m 2SO3, the rate of reaction was mea- a
10. For a reaction (aX– x) , d[x] , is equal to
sured as = 2.5 ¥ 10–4 mol L–1 sec–1. the rate of reaction dt
k2
expressed in terms of SO3 will be Z
(a) –1.25 ¥ 10–4 mol L–2 sec–1 (a) k1(a – x) – k2(a – x) (b) k2(a – x) – k1(a – x)
(b) 50 ¥ 10–4 mol L–1 sec–1 (c) k1(a – x) + k2(a – x) (d) –k1(a – x) – k2(a – x)
(c) –3.75 ¥ 10–4 mol L–1 sec–1 11. The mechanism of the reaction : A + 2B + C Æ D is
(d) 5.00 ¥ 10–4 mol L–1 sec–1 (step 1) (fast) equilibrium A + B m X
3. The rate constant of a reaction is equal to rate of reac- (step 2) (slow) X + C Æ Y
tion: (step 3) (fast) Y + B Æ D
(a) When concentrations of reactants do not change Which rate law is correct?
with time. (a) r = k[C] (b) r = k[A] [B]2 [C]
(b) When concentrations of all reactants and products (c) r = k [A] [B] [C] (d) r = k [D]
are equal. 12. Mechanism of the reaction 2NO + Cl2 Æ 2NOCl may
(c) At time t = 0. be written as
(d) When concentrations of all reactants are unity. K
2NO (NO)2 …… (fast)
4. If the concentration of the reactants in the reaction 2A k
+ B Æ C + D is increased by three folds, the rate of the (NO)2 + Cl2 ææ Æ 2NOCl …… (slow)
reaction will be increased by Rate equation would be
(a) 27 times (b) 9 times (a) kK[(NO)2] [Cl2] (b) kK[NO]2 [Cl2]
(c) 64 times (d) 01 times (c) kK[Cl2] (d) kK[NO] ◊ [Cl2]
5. The rate of change in concentration of C in the reaction 13. The half-life of decomposition of N2O5 is a first order
2A + B Æ 2C + 3D was reported as 1.0 mol L–1 sec–1. reaction represented by?
Calculate the reaction rate: N2O5 Æ N2O4 + 1/2O2
(a) 0.05 mole L–1 sec–1 (b) 0.01 mol L–1 sec–1 After 15 minutes, the volume of O2 produced is 9 mL
(c) 0.5 mol L–1 sec–1 (d) None of these and at the end of the reaction 35 mL. The rate constant
6. In a first order reaction, the initial concentration of the is equal to
reactant was M/10. After 8 minutes 20 seconds the con- 1 35 1 44
centration becomes M/100. What is the rate constant? (a) log e (b) log e
15 26 15 26
(a) 5 ¥ 10–3 sec–1 (b) 2.303 ¥ 10–5 sec–1
(c) 2.303 ¥ 10 sec
–4 –1
(d) 4.606 ¥ 10–3 sec–1 (c)
1
log e
35
(d) None of the foregoing
7. Substance A reacts according to a first order rate law 15 36
with K = 5.0 ¥ 10–5 s–1. If the initial concentration of A 14. 99% at a first order reaction was completed in 32 min.
is 1.0 M, the initial rate is When will 99.9% of the reaction complete?
(a) 1 ¥ 10–5 Ms–1 (b) 5.0 ¥ 10–5 Ms–1 (a) 48 min (b) 46 min (c) 50 min (d) 45 min
(c) 1 ¥ 10 Ms
–4 –1
(d) 5.0 ¥ 10–4 Ms–1 15. T0.5 = constant, confirms the first order of the reaction
8. The mechanism of the reaction 2NO + O2 Æ 2NO2 is as one a2 T0.5 = constant confirms that the reaction is of
K K
NO + NO 1
N2O2 (fast) ; N2O2 + O2 ææÆ
2 (a) Zero order (b) First order
K -1
2NO2 (slow) (c) Second order (d) Third order
The rate constant of the reaction is 16. The half-life period for a reaction at initial concentra-
(a) K2 (b) K2K1 (K–1) tion of 0.5 and 1.0 moles L–1 are 200 sec and 100 sec
respectively. The order of the reaction is
Ê K ˆ
(c) K2K1 (d) K 2 Á 1 ˜ (a) 0 (b) 1 (c) 2 (d) 3
Ë K -1 ¯ 1
9. Dinitrogen pentaoxide decomposes as 2N2O5 Æ 4NO2 17. The slope of the line for the graph of log K versus
T
- d [N 2O5 ] 1
+ O2. The rate can be given in three ways = for the reaction, N2O5 Æ 2NO2 + O2 is – 5000. Cal-
dt 2
d [NO 2 ] d [NO 2 ] culate the energy of activation of the reaction – (KJ K–1
K1 [N2O5], = K2 [N2O5], = K3 [N2O5]
dt dt mol–1)
The relation between the rate constants K1, K2 and K3 is (a) 95.7 (b) 9.57 (c) 957 (d) None
(a) K2 = 2K1 and K3 = 1/2 K1 18. For a reaction, the rate constant is expressed as, k =
(b) K1 = 2K2 and K3 = 2K1 A.e–40000/T . The energy of the activation is
(c) K1 = K2 = K3 (a) 40000 cal (b) 88000 cal
(d) K1 = 2K2 = 3K3 (c) 80000 cal (d) 8000 cal

19. A reaction takes place in three steps. The rate constants 26. At 27°C it was observed during a reaction of hydroge-
kk nation that the pressure of H2 gas decreases from 2 atm
are k1, k2 and k3. The over all rate constant k = 1 3 . If to 1.1 atm in 75 minutes. The rate of reaction (molarity/
k2
sec) is: Given (R = 0.0821 litre atm K–1 mole–1)
(energy of activation) E1, E2 and E3 are 60, 30 and 10
(a) 8.12 ¥ 10–6 mol L–1 sec–1
kJ. The overall energy of activation is:
(b) 8.12 ¥ 10–6 mol L–1 min–1
(a) 40 (b) 30 (c) 400 (d) 60
(c) 4.87 ¥ 10–4 mol L–1 sec–1
20. For a chemical reaction A + 3B h Product
(d) 4.87 ¥ 10–4 mol L–1 min–1
It was observed that rate of reaction increases nine
27. The possible mechanism for the reaction : 2NO + Br2
times when concentration of B increased three times by
Æ 2 NOBr is
keeping concentration of A as constant. On doubling
NO + Br2 m NOBr2(fast);
concentration of both rate increases eight times. Dif-
NOBr2 + NO Æ 2NOBr (slow). Rate law is
ferential rate equation can be given as
(a) r = k [NO] [Br2] (b) r = k [NO]2 [Br2]–1
(a) r = k[A][B]3 (b) r = k [A] [B]2
2 (c) r = k [NOBr2] [NO] (d) r = k [NO]2 [Br2]
(c) r = k[A] [B] (d) r = k[A]2[B]1/3
28. The reaction 2A + B + C Æ D + 2E; is found to follow
21. A reaction is second order with respect to a reactant. If
the rate law as : r = k[A][B]2[C]0. If the concentration
concentration of reactant is doubled the rate of reaction
of A, B and C increases two times then rate of reaction
becomes
becomes
(a) doubled (b) halved
(a) same (b) doubled
(c) four times (d) remains same
(c) eight times (d) four times
22. The decomposition of NH3 is studied on platinum sur-
29. The following results have been obtained during the
face. The rate of production of N2 and H2 are respec-
kinetic studies of the reaction: 2A + B h C + D
tively (k = 2.5 ¥ 10–4 mol–1 L s–1):
(a) 5 ¥ 10–4 and 1.67 ¥ 10–4 Experiment [A] in [B] in initial rate of for-
(b) 1.67 ¥ 10–4 and 5 ¥ 10–4 mol L–1 mol L–1 mation of D in
(c) 1.25 ¥ 10–4 and 3.75 ¥ 10–4 mol L–1min–1
(d) 3.75 ¥ 10–4 and 1.25 ¥ 10–4 I 0.1 0.1 6 ¥ 10–3
23. In a reaction between A and B, initial rate of reaction
was measured for different initial concentration A and II 0.3 0.2 7.2 ¥ 10–2
B given as III 0.3 0.4 2.88 ¥ 10–1
[A] inmol L–1 [B] inmol L–1 Initial rate in mole L–1 s–1 IV 0.4 0.1 2.40 ¥ 10–2
0.2 0.3 5.07 ¥ 10–5
0.2 0.1 5.07 ¥ 10–5 The rate law and the rate constant for the reaction is
0.4 0.05 1.43 ¥ 10–4 (a) k[A]1[B]2; 6 M–1 min–1
Order of reaction with respect to A and B is (b) k[A][B]; 4 M–1 min–1
(a) 1, 0 (b) 1, 1 (c) 1.5, 0 (d) 1.5, 1 (c) k[A]1[B]2; 6 M–2 min–1
24. For the reaction R Æ P, the concentration of a reactant (d) k[A]2[B]; 4 M–2 min–1
changes from 0.03 M to 0.02 M in 25 minutes. The 30. From the following data for the reaction between A and
average rate in seconds is B,
(a) 4 ¥ 10–4M sec–1 (b) 4 ¥ 10–4M min–1 [A] in mol L–1 [B] in mol L–1 Initial rate in mole L–1 s–1
(c) 6.66 ¥ 10 M sec
–6 –1
(d) 6.66 ¥ 10–6 M min–1 2.5 ¥ 10–4 3.0 ¥ 10–5 5.0 ¥ 10–4
1 5.0 ¥ 10 –4
6.0 ¥ 10 –5
4.0 ¥ 10–3
25. N2O5 decomposes as follows: N2O5 Æ 2NO2 + O 2 1.0 ¥ 10 –3
6.0 ¥ 10 –5
1.6 ¥ 10–2
2
The order of the reaction with respect to A and with
- d [ N 2 O5 ] respect to B will be
If, = k1[N 2O5 ]; (a) 2, 1 (b) 1, 2 (c) 2, 0 (d) 1, 3/2
dt
d [NO 2 ] 31. A first order reaction takes 40 minute for 30% decom-
= k2 [N 2O5 ]; position t1/2 for the reaction is
dt
(a) 66.67 min (b) 80 min
d [O 2 ]
= k3[N 2O5 ] (c) 77.70 min (d) infinite time
dt 32. A carbon radio isotope ZXA (half life 10 days) decays to
Which one of the following is correct for k1, k2 and k3: give Z–2XA–4. If 1.00 g atom of ZXA is kept in a sealed
(a) k1 + k2 = k3 (b) k1 = k2 + K3 tube, how much helium will accumulate in 20 days in
(c) k1 = 2k2 + 1/2k3 (d) 2k1 = k2 = 4k3 STP:
(a) 22400 cc (b) 24400 cc
(c) 16800 cc (d) 17600 cc

1 39. A hypothetical reaction A2 + B2 h 2AB follows the

33. A gaseous reaction A2(g) h B(g) + C(g); shows mechanism as given below:
2
A2 h A + A (fast)
increase in pressure from 100 mm to 120 mm in 5 min- A + B2 h AB + B (slow)
utes. The rate of disappearance of A2 is A + B h AB (fast)
(a) 4 mm min–1 (b) 8 mm min–1 The order of the overall reaction is
–1
(c) 16 mm min (d) 2 mm min–1. (a) 2 (b) 1 (c) 3/2 (d) 0
34. For the reaction system 2NO (g) + O2 (g) h 2NO2
- d [NO 2 ]
(g); volume is suddenly reduced to half its value by 40. The rate law for the dimerisation of NO2 is
increasing the pressure on it. If the reaction is of first = k[NO ]2 dt
2
order with respect to O2 and second order with respect Which of the following changes will change the value
to NO, the rate of reaction will of the specific rate constant, k?
(a) Diminish to one fourth of its initial value (a) doubling the total pressure on the system.
(b) Diminish to one eighth of its initial value (b) doubling the temperature.
(c) Increase to eight times of its initial value (c) both.
(d) Increase to four times of its initial value (d) none of these.
35. The reaction : 2NO + 2H2 h N2 + 2H2O has been 41. The temperature coefficient of a reaction is
assigned to follow given mechanism: (a) ratio of rate constants at two temperatures differ-
I. NO + NO m N2O2 (fast) ing by 1°C.
II. N2O2 + H2 h N2O + H2O (slow) (b) ratio of rate constants at temperature 35°C and
III. N2O + H2 h N2 + H2O (fast) 25°C.
The rate constant of step II is 1.2 ¥ 10–4 mole–1 L min–1 (c) ratio of rate constants at temperature 30°C and
while equilibrium constant of step I is 1.4 ¥ 10–2. What 25°C.
is the rate of reaction when concentration of NO and H2 (d) specific reaction rate at 25°.
each is 0.5 mole L–1 42. The rate of a chemical reaction generally increases
(a) 2.1 ¥ 10–7 mole L–1 min–1 rapidly even for small temperature increase because of
(b) 3.2 ¥ 10–6 mole L–1 min–1 rapid increase in the
(c) 3.5 ¥ 10–4 mole L–1 min–1 (a) collision frequency
(d) None of these (b) fraction of molecules having activation energy
36. The decomposition of dimethyl ether leads to the for- (c) activation energy
mation of CH4, H2 and CO and the reaction rate is giv- (d) average kinetic energy of molecules
en by 43. The pre-exponential factor in the Arrhenius equation of
Rate = k[CH3OCH3]3/2 a second order reaction has the units
The rate of reaction is followed by increase in pressure (a) mol L–1 s–1 (b) L mol–1 s–1
–1
in a closed vessel, so the rate can also be expressed in (c) s (d) dimensionless
terms of the partial pressure of dimethyl ether, i.e., 44. A catalyst is a substance which
(a) increases the equilibrium concentration of the
Rate = k (PCH3OCH3 ) 3/2
product.
If the pressure is measured in bar and time in minutes, (b) changes the equilibrium constant of the reaction.
then the unit of rate constants is (c) shortens the time to reach equilibrium.
(a) bar1/2min (b) bar3/2min–1 (d) supplies energy to the reaction.
–1/2 –1
(c) bar min (d) bar min –1 45. Which reaction characteristics is/are changing by the
37. A reaction involving two different reactants addition of a catalyst to a reaction at constant tempera-
(a) Can never be a second order reaction ture
(b) Can never be a unimolecular reaction (a) Activation energy (b) Equilibrium constant
(c) Can never be a bimolecular reaction (c) Reaction entropy (d) Reaction enthalpy
(d) Can never be a first order reaction 46. A radioactive isotope having a half-life of three days
38. Which one of the following statement for order of reac- was received after 12 days. It was found that there were
tion is not correct? 3 g of isotope in the container. The initial weight of the
(a) Order can be determined experimentally. isotope when packed was
(b) Order of reaction is equal to sum of the powers of (a) 12 g (b) 24 g
concentration terms in differential rate law. (c) 36 g (d) 48 g
(c) It is not affected with the stoichiometric coeffi- 47. If uranium (mass number 238 and atomic number 92)
cient of the reactants. emits an a-particle, the product has mass number and
(d) Order cannot be fractional. atomic number:

(a) 236 and 92 (b) 234 and 90 (a) 20 min. (b) 33 min
(c) 238 and 90 (d) 236 and 90 (c) 15 min (d) 25 min.
48. Consider the chemical reaction, 55. In a first order reaction the concentration of reactant
N2(g) + 3H2(g) h 2NH3(g) decreases from 800 mol/dm3 to 50 mol/dm3 in 2 ¥ 102
The rate of this reaction can be expressed in terms of sec. The rate constant of reaction in sec–1 is
time derivatives of concentration of N2(g), H2(g) or (a) 2 ¥ 104 s–1 (b) 3.45 ¥ 105 s–1
NH3(g). Identify the correct relationship amongst the (c) 1.386 ¥ 10 s –2 –1
(d) 2 ¥ 10–4 s–1
rate expression: 56. Half-life period of a first order reaction is
d [N 2 ] 1 d [H 2 ] 1 d [NH3 ] (a) Inversely proportional to the concentration.
(a) Rate = - =- = (b) Independent of the concentration.
dt 3 dt 2 dt
(c) Directly proportional to the initial concentration.
d [N 2 ] d [H 2 ] d [NH3 ] (d) Directly proportional to the final concentration.
(b) Rate = - = -3 =2
dt dt dt 57. In the first order reaction, the concentration of the reac-
d [N 2 ] 1 d [H 2 ] 1 d [NH3 ] tant is reduced to 25% in one hour. The half life period
(c) Rate = = = of the reaction is
dt 3 dt 2 dt
(a) 2 hr (b) 4 hr (c) 1/2 hr (d) 1/4 hr
d [N 2 ] d [H 2 ] d [NH3 ]
(d) Rate = =- = 58. Under the same reaction conditions, initial concentra-
dt dt dt tion of 1.386 mol dm–3 of a substance becomes half
49. Rate law for the following reaction: in 40 seconds and 20 seconds through first order and
Ester + H+ m Acid + Alcohol; is (k )
zero order kinetics, respectively. Ratio 1 of the rate
dx ( k0 )
= k [ester]1 [H+]0. What would be the effect on the
dt constants for first order (k1) and zero order (k0) of the
rate if concentration of H+ ion is doubled? reaction is
(a) Same (b) doubled (a) 0.5 mol–1 dm3 (b) 1.0 mol–1 dm3
–1 3
(c) Half (d) Data insufficient (c) 1.5 mol dm (d) 2.0 mol–1 dm3
50. Consider a reaction aG + bH h Product. When con- 59. A radioactive element resembling iodine in properties
centration of both the reactants G and H is doubled, the is
rate increases by eight times. However, when concen- (a) Astatine (b) Lead
tration of G is doubled keeping the concentration of H (c) Radium (d) Thorium
constant, the rate is doubled. The overall order of the 60. Taking the reaction, A + 2B Æ Products, to be of sec-
reaction is ond order, which of the following may be the correct
(a) 0 (b) 1 (c) 2 (d) 3 rate law expressions?
51. What is the order of a reaction which has a rate expres- dx dx
sion rate = k[A]3/2 [B]–1 (a) = k[ A][ B] (b) = k[ A][ B]2
dt dt
(a) 3/2 (b) 1/2
(c) 0 (d) None of these dx dx
(c) = k[ A]2 [ B] (d) = k1[ A] + k2 [ B]2
52. The kinetic data for the reaction: 2A + B2 h 2AB are dt dt
as given below. 61. For a hypothetical reaction; A + B h Product, the
[A] mol L–1 [B2] mol L–1 Rate mol L–1 min–1 rate law is r = k[B] [A]0, the order of reaction is
0.5 1.0 2.5 ¥ 10–3 (a) 0 (b) 1 (c) 2 (d) 3
1.0 1.0 5.0 ¥ 10–3 62. The rate of the reaction A + B2 h AB + B; is directly
0.5 2.0 1 ¥ 10–2 proportional to the concentration of A and independent
Hence the order of reaction with respect to A and B2 of concentration of B2, hence, rate law is
are, respectively, (a) k[A][B2] (b) k[A]2[B2]
(a) 1 and 2 (b) 2 and 1 (c) k[A] (d) [B2]
(c) 1 and 1 (d) 2 and 2 63. Rate of a reaction; A + B h Products, is given below as
53. Units of rate constant of first and zero order reactions a function of different initial concentrations of A and B.
in terms of molarity unit are respectively
[A] mol L–1 [B] mol L–1 Initial rate mol
(a) sec–1, M sec–1 (b) sec–1, M
–1 –1 L–1 time–1
(c) M sec , sec (d) M, sec–1
54. For a reaction: X(g) Æ Y(g) + Z(g) 0.01 0.01 0.005
The half-life period is 10 min. In what period of time 0.02 0.01 0.010
would be concentration of X be reduced to 10% of orig- 0.01 0.02 0.005
inal concentration?

The half life of A in the reaction is 73. Identify the missing product in the given reaction
(a) 1.386 min (b) 1.386 time 235
92 U + 10 n ææ
Æ ? + 92
36 Kr + 30 n
1
(c) 0.01 min (d) 0.01 time
64. The reaction A(g) + 2B(g) h C(g) + D(g) is an el- (a) 141
56 Ba
(b) 139
56 Ba (c) 139
54 Ba (d) 141
54 Ba
ementary process. In an experiment, the initial partial 74. 99% of a first order reaction was completed in 32 min.
pressure of A and B are PA = 0.60 and PB = 0.80 atm. When will 50% of the reaction complete?
When PC = 0.2 atm the rate of reaction relative to the (a) 24 min (b) 8 min (c) 4 min (d) 4.8 min
initial rate is 75. In which of the following case, Ea of the backward re-
(a) 1/48 (b) 1/24 (c) 9/16 (d) 1/6 action is greater than that of the forward reaction?
65. Thermal decomposition of a compound is of first order. (a) A + 10 kcal h B, Ea = 50 kcal
If 50% of a sample of the compound is decomposed in (b) A + 20 kcal h B, Ea = 40 kcal
120 minute, show how long will it take for 90% of the (c) A + 40 kcal h B, Ea = 10 kcal
compound to decompose? (d) A – 40 kcal h B, Ea = 20 kcal
(a) 399 min (b) 410 min 76. A first order reaction : A h Products and a second
(c) 250 min (d) 120 min order reaction : 2R h Products; both have half - time
66. A reaction that is of the first order with respect to reactant of 20 minutes when they are carried out taking 4 mole
A has a rate constant 6 min–1. If we start with [A] = 0.5 L–1 of their respective reactants. Number of mole per
mol l–1, when would [A] reach the value 0.05 mol l–1? litre of A and R remaining unreacted after 60 minutes
(a) 0.384 min (b) 0.15 min from the start of the reaction, will be respectively.
(c) 3 min (d) 3.84 min (a) 1 and 0.5 (b) 0.5 and negligible
67. Calculate the half-life of the first-order reaction (c) 0.5 and 1 (d) 1 and 0.25
C2H4O(g) h CH4(g) + CO(g) 77. If ‘x’ is the fraction of molecules having energy greater
if the initial pressure of C2H4O(g) is 80 mm and the than Ea, it will be given by
total pressure at the end of 20 minutes is 120 mm.
Ea Ea
(a) 40 min (b) 120 min (a) x = - (b) ln x = -
(c) 20 min (d) 80 min RT RT
68. The half life period for catalytic decomposition of AB3 (c) x = e a
E /RT
(d) None of these
at 50 mm is found to be 4 hrs and at 100 mm it is 2.0
78. A photon of gamma radiation knocks out a proton from
hrs. The order of reaction is 24
(a) 3 (b) 1 (c) 2 (d) 0 12Mg nucleus to form
(a) The isotope of parent nucleus
69. The inactivation of a viral preparation in a chemical
(b) The isobar of parent nucleus
bath is found to be a first order reaction. The rate con-
(c) the nuclide 11Na23
stant for the viral inactivation if in the beginning 1.5 %
(d) The isobar of 11Na23
of the virus is inactivated per minute is
79. The decay constant of a radioactive sample is ‘l’. The
(a) 1.25 ¥ 10–4 sec–1 (b) 2.5 ¥ 10–4 sec–1
half-life and mean life of the sample are respectively
(c) 5 ¥ 10 sec
–4 –1
(d) 2.5 ¥ 10–4 min–1
70. In the reaction 2N2O5 Æ 4NO2 + O2, initial pressure is 1 ln 2 ln 2 1
(a) , (b) ,
500 atm and rate constant k is 3.38 ¥ 10–5 sec–1. After l l l l
10 minutes the final pressure of N2O5 is
1 l 1
(a) 490 atm (b) 250 atm (c) l ln 2, (d) ,
(c) 480 atm (d) 420 atm l ln 2 l
71. The decomposition of formic acid on a gold surface 80. Rate of the chemical reaction : nA h products, is
follows first order kinetics and specific rate constants doubled when the concentration of A is increased four
are 5.5 ¥ 10–4 s–1 and 9.2 ¥ 10–3 s–1 at 140°C and 185°C times. If the half time of the reaction at given tempera-
respectively. Energy of activation is ture is 16 min, then time required for 75% of the reac-
(a) 98.46 J mol–1 (b) 98.46 k J mol–1 tion to complete is
–1
(c) 23.7 J mol (d) 23.7 k J mol–1 (a) 24.0 min (b) 27.3 min
72. During a negative b-decay (c) 48 min (d) 49.4 min
(a) An atomic electron is ejected. 81. The rate constant of a reaction at 27°C is 2.3 ¥ 10–3
(b) An electron which is already present within the min–1 and at this temperature 0.001 % of the reactant
nucleus is ejected. molecules are able to cross over the energy barrier ex-
(c) A neutron in the nucleus decays emitting an elec- isting between the reactants and the products. What
tron. can be the maximum value of rate constant achieved
(d) A part of the binding energy of the nucleus is con- on raising the temperature?
verted into an electron. (a) 23.0 min–1 (b) 2.3 ¥ 10–2 min
–1
(c) 115.0 min (d) 230.0 min–1

82. The rate constant, the activation energy and the Arrhe- order with respect to A and B
nius parameter of a chemical reaction at 25°C are 3.0 ¥ (a) 1, 0 (b) 0, 1 (c) 1, 1 (d) 1, 2
10–4 s–1, 104.4 kJ mol–1 and 6.0 ¥ 1014s–1 respectively. 6. A drug is known to be ineffective after it has decom-
The value of the rate constant as T h is posed to the extent of 30%. The original concentra-
(a) 2.0 ¥ 1018 s–1 (b) 6.0 ¥ 1014s–1 tion of a sample was 500 units/mL. When analysed 20
(c) Infinity (d) 3.6 ¥ 1030s–1 months later, the concentration was found to be 420
83. If the rate of reaction grows 15.6 times on increasing units/mL. Assuming that the decomposition is of first
the temperature by 30 K, the temperature coefficient of order, what will be the expiration time of the drug sam-
the reaction will be approximately ple. What is the half life of the drug?
(a) 2 (b) 3 (c) 2.5 (d) 3.5 (a) 0.00872 month, 41 month
(b) 0.00872 month, 79.49 month
LEVEL II (c) 41 month, 79.49 month
(d) 79.49 month, 41 month
7. In an experiment to study hydrolysis of an ester 0.5
1. What will be the initial rate of a reaction if its rate con- M HCl at 300 K was used. 5 cm3 of the reaction mix-
stant is 10–3 min–1 and the concentration of reactant is ture was withdrawn after definite intervals and titrated
0.2 mol dm–3 also the amount of reactant converted against 0.2 M NaOH solution. Assuming pseudo first
into products in 200 minute is order kintics the rate constant at 300K from the follow-
(a) 2 ¥ 10–4 mol dm–3 min–1, 81.97%
ing data will be
(b) 2 ¥ 10–4 mol dm–3 min–1, 18.03%
t (sec) 0 600 1200 1800
(c) 2 ¥ 10–4 mol dm–3 min–1, 76%
V (cm3 of NaOH used) 11.5 12.0 12.5 13.0 25.5
(d) 2 ¥ 10–4 mol dm–3 min–1, 24%
(a) 6.061 ¥ 10–5 s–1 (b) 6.176 ¥ 10–5 s–1
2. The half time of first order decomposition of nitramide
(c) 6.296 ¥ 10 s –5 –1
(d) 6.177 ¥ 10–5 s–1
is 2.1 hour at 15°C.
8. The following rate data was obtained for the first order
NH2NO2(s) Æ N2O(g) + H2O(l)
thermal decomposition of SO2Cl2(g) at a constant vol-
If 6.2 g of NH2NO2 is allowed to decompose, then
ume.
time taken for NH2NO2 to decompose 99% and volume
SO2Cl2(g) Æ SO2(g) + Cl2(g)
of dry N2O produced at this point measured at STP will
Exp. Time (sec–1) Total pressure (atm)
be
1. 0 0.5
(a) 13.95 hrs, 22.4 L (b) 13.95 hrs, 2.217 L
(c) 2.1 hrs, 22.4 L (d) 2.1 hrs, 2.217 L 2. 100 0.6
3. The decomposition of N2O5 in CCl4 solution at 320 K The reaction rate when total pressure is 0.65 atmo-
takes place as sphere will be
2N2O5 Æ 4NO2 + O2; (a) 2.23 ¥ 10–3 sec–1 (b) 0.35 atm
On the bases of given data order and the rate constant (c) 7.8 ¥ 10–4 atm sec–1 (d) 2.33 ¥ 10–4 atm sec–1
of the reaction is 9. The gaseous reaction, A(g) Æ 2B(g) + C(g) is observed
Time in minutes 10 15 20 25 to be the first order. On starting with pure A, it is found
Volume of O2 6.30 8.95 11.40 13.50 34.75 that at the end of 10 min, the total pressure of the sys-
evolved (in mL) tem is 176 mm of Hg and after a long time, it is 270 mm
(a) 1, 0.198 min–1 (b) 3/2, 0.0198 M–1/2 min–1 of Hg. Which of the following is correct for the given
(c) 0, 0.198 M min –1
(d) 1, 0.0198 min–1 data?
4. From the following data estimate the order for decom- (a) The initial pressure A is 90 mm Hg.
position of an aqueous solution of hydrogen peroxide: (b) The partial pressure of A after 10 min. is 47 mm
Time (minutes) 0 10 20 30 Hg.
V (ml) 46.1 29.8 19.6 12.3 (c) The rate constant of the reaction is 0.0649 min–1.
where V is the volume of potassium permanganate so- (d) all are correct
lution in mL required to decompose a definite volume 10. For the reaction, 2NO + H2 Æ N2O + H2O the value
of the peroxide solution. of –dp/dt is found to be 1.50 Torr s–1 for a pressure of
(a) 0 (b) 1 (c) 2 (d) 1/2 359 Torr of NO and 0.25 Torr s–1 for a pressure of 152
5. Rate of reaction A + B Æ P is given as a function of Torr, the pressure of H2 being constant. On the other
different initial concentrations of A and B hand, when the pressure of NO is kept constant, –dp/
S.No. {A} {B} {Rate} dt is 1.60 Torr s–1 for a hydrogen pressure of 289 Torr
1. 0.01 0.01 0.005 and 0.79 Torr s–1 for a pressure of 147 Torr. The overall
2. 0.02 0.01 0.010 order of the reaction is:
3. 0.01 0.02 0.005 (a) 2 (b) 1 (c) 3/2 (d) 3

11. The optical rotation of sucrose in 0.5 N-hydrochloric (a) 699.31 dpm (b) 680.81 dpm
acid at 308 K and at various time intervals are given (c) 670 dpm (d) 500 dpm
below. The rate constant for the first order hydrolysis 19. For the first order reaction A(g) Æ 2B(g) + C(g), the
of sucrose will be initial pressure is PA = 90 mm Hg. The pressure after 10
Time (minutes) 0 10 20 30 60 minutes is found to be 180 mm Hg. The half-life period
Rotation (degrees) +32 25.5 20.0 15.5 5.0 –10.50 of the reaction is
(a) 0.0166 min–1 (b) 0.0164 min–1 (a) 1.15 ¥ 10–3 sec–1 (b) 600 sec
(c) 0.0168 min –1
(d) none of these (c) 3.45 ¥ 10–3 sec–1 (d) 200 sec
12. Bicyclohexane was found to undergo two parallel first 20. A(g) h B(g) + C(g)
order rearangemments. At 730 K, the first order rate - d [ A]
constant for the formation of cyclohexene was mea- = k[ A]
dt
sured as 1.26 ¥ 10–4s–1 and for the formation of methyl
cyclopentene the rate constant was 3.8 ¥ 10–5s–1. What At the start pressure is 100 mm and after 10 min, pres-
is the percentage of the methyl cyclopentene? sure is 120 mm. Hence rate constant (min–1) is
(a) 20% (b) 30% (c) 15% (d) 23% 2.303 120 2.303 100
13. 227Ac has a half-life of 22 years with respect to radio- (a) log (b) log
10 100 10 20
active decay. The decay follows two parallel paths,
2.303 100 2.303 100
on leading to 222Th and other to 223Fr. The percentage (c) log (d) log
yields of these two daughter nuclides are 2 and 98 re- 10 80 10 120
spectively. The decay constant for separate paths are: 21. Find out the % of the reactant molecule crossing over
(a) 0.693 y–1; 0.693 y–1 the energy barrier at 325 K given that DH325 = 0.12 kcal
(b) 0.387 y–1; 0.63 y–1 Ea(b) = +0.02 cal.
(c) 0.03087 y–1; 0.00063 y–1 (a) 41 (b) 81 (c) 71 (d) 91
(d) 2; 98 22. In a endothermic equilibrium reaction if k1 and k2 be
14. The decomposition of N2O5 is takes place as the rate constants of forward reaction and backward re-
action respectively at temperature t°C and k1¢ and k2¢ be
1 the respective rate constant at (t + 10° C) then
N2O5 m 2NO2 + O2
2 k¢ k¢ k¢ k¢
If the values of the rate constants are 3.45 ¥ 10–5 and (a) 1 = 2 (b) 1 < 2
6.9 ¥ 10–3 at 27°C and 67°C respectively then energy of k k2 k1 k2
activation will be k1¢ k2¢
(a) 222.5 kJ (b) 122.5 kJ (c) > (d) none of the above
k1 k2
(c) 112.5 kJ (d) 450 kJ
15. The decomposition of A into product has value of K 23. A first order gaseous decomposition of N2O4 Æ 2NO2
as 4.5 ¥ 103 sec–1 at 10°C and the energy of activation has k value of 4.5 ¥ 103 sec–1 at 1°C and energy of acti-
60 KJ mol–1. At what temperature would K be 1.5 ¥ vation of 58 kJ/mole at what temperature in kelvin rate
104 sec–1. constant would be 1.00 ¥ 104 sec–1
(a) 283 K (b) 293 K (a) 273 (b) 283 (c) 373 (d) 546
(c) 297.02 K (d) 293.8 K 24. A certain reaction A + B Æ C is first order w.r.t to each
16. For the decomposition of dimethyl ether, A in the Ar- of reactant with K = 10–2 L mol–1 sec–1 calculate the
rhenious equation k = Ae–Ea/RT has a value of 1.26 ¥ concentration of ‘A’ remaining after 100 sec if initial
1013 s–1 and Ea value of 58.5 kcal. The half-life period concentration of each reactant was 0.1 M
for first order decomposition at 527°C is (a) 1.11 M (b) 0.09 M
(a) 525 sec (b) 636 sec (c) 0.06 M (d) 0.07 M
(c) 800 sec (d) 425 sec 25. The rate constants for two parallel reactions were found
17. Two substances A and B are present such that [A0] = to be 1 ¥ 10–2 dm–3 mol–1 sec–1 and 3.0 ¥ 10–2 dm3
4[B0] and half-life of A is 5 min and that of B is 15 min. mol–1 sec–1. If the corresponding energies of activation
If they start decaying at the same time following first of parallel reaction are 60 kJ mol–1 and 70 kJ mol–1
order kinetics how much time later will the concentra- respectively. The apparent overall activation energy of
tion of both of them would be same. reaction is
(a) 30 min (b) 60 min (a) 130 kJ/mol (b) 135 kJ/mol
(c) 15 min (d) 10 min (c) 65 kJ/mol (d) 67.5 kJ/mol
18. A radioactive isotope has an initial activity of 2 ¥ 106 26. Number of natural lifes (Tav) required for a first order
disintegration/min. After 4 days its activity is 9 ¥ 105 reaction to achieve 99.9% level of completion is
dis/min. The activity after 40 days will be (a) 2.3 (b) 6.9 (c) 9.2 (d) 0.105
27. In zero-order reaction t75% = xt1/2. Then the value of x =

k k
(a) 2
3
(b) (c)
2
(d) 10 X ææ 1
Æ A + B and Y ææ 2
Æ C+D
2 3 If 50% of the reaction of X was completed when 96%
28. Graph between log k and 1/T (k = rate constant in sec–1 of the reaction of Y was completed, the ratio of their
and T is the temperature in k) is straight line rate constants (k2/k1) is
1 (a) 4.06 (b) 0.215 (c) 1.1 (d) 4.65
If OX = 5 and slope of line = - then Ea is 34. At certain temperature, the half-life period in the ther-
2.303
X mal decomposition of a gaseous substance as follows:
P(mm Hg) 500 250
log k t1/2 (in min.) 235 950
q
Find the order of reaction [Given: log (23.5) = 1.37; log
O (95) = 1.97]
1 (a) 1 (b) 2 (c) 2.5 (d) 3
T
35. A first order reaction is 50% completed in 20 min at
2 27°C and in 5 min at 47°C. The energy of activation of
(a) 2.303 ¥ 2 cal (b) cal the reaction is
2.303
(c) 2 cal (d) none (a) 43.85 kJ/mol (b) 55.14 kJ/mol
29. Inversion of sucrose (C12H22O11) is first order reaction (c) 11.97 kJ/mol (d) 6.65 kJ/mol
is studied by measuring angle of rotation at different 36. The rate constant, the activation energy and the Arrhe-
interval of time. nius parameter of a chemical reaction at 25°C are 3.0 ¥
H+ 10–4 s–1, 104.4 kJ mol–1 and 6.0 ¥ 1014 s–1 respectively.
C12 H 22O11 + H 2O æææ
Æ C6 H12O6 + C6 H12O6
glucose fructose The value of the rate constant at EA Æ 0 is
(a) 2.0 ¥ 1018 s–1 (b) 6.0 ¥ 1014 s–1
if (r – r0) = a and (r – rt) = a – x where r0, rt and r (c) Infinity (d) 3.6 ¥ 1030 s–1
are the angle of rotation at the start, at the time t, and 37. Given that for a reaction of order n, the integrated form
at the end of reaction respectively. Then there is 50% 1 È 1 1 ˘
inversion when of the rate equation is k = -
t (n - 1) ÍÎ C n -1 C0n -1 ˙˚
(a) r0 = 2rt – r (b) r0 = rt – r
(c) r0 = rt – 2r (d) r0 = rt + r where C0 and C are the values of the reactant concen-
30. For a reaction rate constant is given by tration at the start and after time t. What is the relation-
11067k ship between t3/4 and t1/2 where t3/4 is the time required
ln k(min–1) = - + 31.330 then what is the ef- for C to become 1/4 C0?
T
(a) t3/4= t1/2 [2n–1 + 1] (b) t3/4= t1/2 [2n–1 – 1]
fect on the rate of the reaction at 127°C if in presence n+1
(c) t3/4= t1/2 [2 – 1] (d) t3/4= t1/2 [2n+1 + 1]
of catalyst, energy of activation is lowered by 10 kJ
38. In a reaction involving one single reactant, the frac-
mol–1
tion of the reactant consumed may be defined as f =
(a) 10 times increases (b) 20 times increases
Ê Cˆ
ÁË1 - C ˜¯ where C0 and C are the concentrations of the
(c) 30 times increases (d) no change
31. The rate constant for the forward reaction A(g) m 2B 0
(g) is 1.5 ¥ 10–3 s–1 at 100 K. If 10–5 moles of A and 100 reactant at the start and after time t. For a first order
moles of B are present in a 10 L vessel at equilibrium reaction:
then rate constant for the backward reaction at this tem- df df
perature is (a) = K (1 - f ) (b) - = Kf
dt dt
(a) 1.50 ¥ 104 L mol–1 s–1
df df
(b) 1.5 ¥ 1011 L mol–1 s–1 (c) - = K (1 - f ) (d) = Kf
(c) 1.5 ¥ 1010 L mol–1 s–1 dt dt
(d) 1.5 ¥ 10–11 L mol–1 s–1 K
39. A reaction 2A + B ææÆ C + D is first order with
32. Reaction A + B h C + D follows following rate law respect to A and 2nd order with respect to B. Initial
1 1
rate = K ¥ [ A] 2 [ B] 2 . Starting with initial concentration concentration (t = 0) of A is C0 while B is 2C0. If at t
of one mole of A and B each, what is the time taken for as 30 minutes the concentration of C is C0/4 then rate
amount of A becomes 0.25 mole. Given: K = 2.31 ¥ expression at t = 30 minutes is:
10–3 sec–1. (a) R = 7C03 K/16 (b) R = 27 C03 K/32
3
(a) 300 sec (b) 600 sec (c) R = 247 C0 K/64 (d) R = 49 C03 K/32
(c) 900 sec (d) None of these 40. A Æ B 15 –2000/T
KA = 10 e
33. Consider the following first order competing reactions:

CÆD KC = 1014 e–1000/T (d) 60% B and 40% C

Temperature TK at which (KA = KC) is 47. A radioactive nuclide is produced at a constant rate of
(a) 1000 K (b) 2000 K a per second. Its decay constant is l. If N0 be the of
(c) (2000/2.303) K (d) (1000/2.303) K nuclei at time t = 0, then maximum number of nuclei
41. The rate of a reaction gets doubled when the tempera- possible are:
ture changes from 7°C to 17°C. By which factor will it (a) N0 (b) a/l
change for the temperature change from 17°C to 27°C? a l
(a) 1.81 (b) 1.71 (c) 1.91 (d) 1.76 (c) N0 + (d) + N0 s
l s
42. For the reaction A + 2B Æ products (started with con-
centrations taken in stoichiometric proportion), the ex- 48. A(aq) h B(aq) + C(aq) is a first order reaction:
perimentally determined rate law is Time t
moles of reagent n1 n2
d [ A]
- = K [ A] [ B] Reaction progress is measure with the help of titration
dt of reagent ‘R’. If all A, B and C reacted with reagent
The half life time of the reaction would be È mol. wt. ˘
and have ‘n’ factors Ín factors; eq. wt. = in
0.693 0.693 Î n ˙˚
(a) (b)
K 1/K the ratio of 1:2:3 with the reagent. The k in terms of t,
0.693 n1 and n2 is
(c) (d) not defined
2K 1 Ê n2 ˆ 1 Ê 2n2 ˆ
(a) K = ln Á (b) K = ln Á
43. For a reaction 2A + B Æ product, rate law is t Ë n2 - n1 ˜¯ t Ë n2 - n1 ˜¯
d [ A] 1 Ê 4n2 ˆ 1 Ê 4n2 ˆ
- = K [ A] (c) K = ln Á (d) K = ln Á
dt t Ë n2 - n1 ˜¯ t Ë 5(n2 - n1 ) ˜¯
1 49. A gaseous compound A reacts by three independent
At a time when t = , concentration of the reactant is
K first order processes (as shown in figure) with rate con-
(C0 = initial concentration) stant 2 ¥ 10–3, 3 ¥ 10–3 and 1.93 ¥ 10–3 sec–1 for prod-
ucts B, C and D respectively.
C C 1 k1
B(g)
(a) 0 (b) C0e (c) 20 (d) C If initially pure A was taken
e e k2
0 in a closed container with P = A(g) C(g)
44. A hypothetical reaction, A2 + B2 h 2AB follows the 8 atm, then the partial pres- k3
mechanism as given below sure of B (in atm) after 100 D(g)

A2 m A + A ...(fast) sec from start of experiment:
A + B2 h AB + B ... (slow) (a) 0.288 (b) 0.577
A + B h AB ...(fast) (c) 1.154 (d) None of these
The order of the overall reaction is:
1 LEVEL III
(a) 2 (b) 1 (c) 1 (d) zero
2
45. In the following first order competing reactions
A + Reagent h Product and 1. Match the following:
B + Reagent h Product Column I Column II
The ratio of K1/K2 if only 50% of B will have been 1
11Na + … h11 Na +
23 24
(A) … (p) 0n
reacted when 94% of A has been reacted is 1
(a) 4.06 (b) 0.246 (c) 2.06 (d) 0.06 (B) 21H3 h2 He4 + 2 … (q) 1H
4
46. A substance undergoes first order decomposition. The (C) 92U
238
h90 Th234 + … (r) 2He
decomposition follows two parallel first order reac- 0
29Cu h28 Ni + …
63 63
(D) (s) 1e
tions as 2
(t) 1H
K1 B
K1 = 1.26 ¥ 10–4 sec–1
A 2. Matching (For first-order reaction)
and K2 = 3.8 ¥ 10–5 sec–1
K2 C Column I Column II
The percentage distribution of B and C are: (A) t63/64 (p) 6t1/2
(a) 80% B and 20% C (B) t15/16 (q) 2t3/4
(b) 76.83% B and 23.17% C
(c) 90% B and 10% C

Passage 1
5
(C) t31/32 (r) t
3 7/8
Energy in KJ
30
(D) t255/256 (s) 2t15/16
10
3. Match Column I with Column II Products
Column I Column II Reaction coordinate
(A) Decomposi- (p) 10t1/2 The above graph represents the energy profile diagram for a
tion of H2O2 first order reaction taking place at a constant temperature of
47°C. The specific rate constant for the forward and back-
K308
(B) (q) first order ward reaction is 10–4 min–1 and 10–6 min–1 respectively.
K 298 6. The energy of activation for the backward reaction is
(C) Arrhenius (r) Temperature coefficient (a) 30 kJ mol–1 (b) 20 kJ mol–1
–1
equation (c) 10 kJ mol (d) 40 kJ mol–1
7. In overall reaction heat is
t99.9% for first K2 Ea Ê T2 - T1 ˆ (a) liberated (b) absorbed
log =
K1 2.303R ÁË T1T2 ˜¯
(D) (s)
order (c) no change in heat (d) cannot be predicted
8. The maximum rate constant for the forward reaction is
(t) 2 – 3 (a) 5.46 (b) 7.30 (c) 1.23 (d) 9.83
4. Match Column I with Column II Passage 2
A vessel contains gaseous dimethylether at initial pressure
Column I Column II
‘p0’ atm. Dimethyl ether decomposes on heating as per the
Order Rate Constant
reaction by first order kinetics.
1Ê 1 1ˆ D
(A) Zeroth K= - CH3 - O - CH3 (g) ææ
Æ CH 4 (g) + CO(g) + H 2 (g)
2t ÁË (a - x) 2 a 2 ˜¯
(p)
It is observed that the half-life period for this reaction is 0.2
1Ê 1 1ˆ hour. After a very long time, pressure in the vessel is ob-
K= Á -
t Ë (a - x) a ˜¯
(B) First (q) served to be 1.2 atm. Assume ideal behaviour of all gases
with constant V-T conditions.
9. What would be the approximate pressure in the vessel
x
(C) Second (r) K= at 0.6 hour? [log10 8 = 0.9]
t (a) 0.05 atm (b) 1.5 atm
(c) 2.303 atm (d) 1.1 atm
1 Ê a ˆ
K = ln Á 10. The initial rate of formation of CH4 gas is
t Ë (a - x) ˜¯
(D) Third (s)
(a) 1.386 atm h–1 (b) 0.7 atm h–1
–1
(c) 2.07 atm h (d) 1.4 atm h–1
5. Match Column I with Column II 11. For a first order sequential reaction,
k1 k2
Column I Column II A ææÆ B ææÆ C , k1 = 2.31 ¥ 10 s and k2 = 1.1
–3 –1
Order Rate Constant ¥ 102 s–1 and initial molar concentration of A is 2.0 M.
(A) First Order (p) t1/2 μ a The concentration of C at time t = 20 minutes is
(B) Second Order (q) (a) 0.75 M (b) 1.5 M
1
t1/2 μ (c) 1.75 M (d) 1.875 M
( a ) n -1
Passage 3
(C) Zero Order (r) 0.693 Dideuterocyclopropane (A) undergoes a first order decom-
t1/2 = position. The observed rate constant at a certain temperature,
K
measured in terms of the disappearance of A, was 1.52 ¥ 10–4
(D) nth Order (s) log(a – x) v/s time graph s–1. Analysis of the reaction products showed that the reac-
is straight line with –ve tion followed two parallel paths, one leading to dideutero-
slope propene (B) and the other to cis-1,2-dideuterocyclopropane
(t) (C). B was found to constitute 11.2% of the reaction product,
1
t1/2 μ independent of the extent of reaction.
a

12. The order of the pathways leading to the formation of 20. At the equilibrium state N2O5, NO2 and NO3 concen-
B and C respectively are trations are 0.2, 0.4 and 0.4 M respectively. k1 is
(a) 1 and 0 (b) 0 and 1 (a) 0.1 (b) 0.2 (c) 1 (d) 2
(c) 1 and 1 (d) 0 and 0
Assertion and Reasoning
13. Rate constant for the conversion of A to B is
(a) 1.7 ¥ 10–5 s–1 (b) 1.7 ¥ 10–5 mol L–1 s–1 (a) STATEMENT-1 is True, STATEMENT-2 is True,
(c) 1.52 ¥ 10 s
–4 –1
(d) 1.35 ¥ 10–4 mol L–1 s–1 STATEMENT-2 is correct explanation of STATE-
14. Rate constant for the conversion of A to C is MENT-1
(a) 1.35 ¥ 10–4 mol L–1 s–1 (b) STATEMENT-1 is True, STATEMENT-2 is True,
(b) 1.7 ¥ 10–5 s–1 STATEMENT-2 is NOT correct explanation of
(c) 1.52 ¥ 10–4 s–1 STATEMENT-1
(d) 1.35 ¥ 10–4 s–1 (c) STATEMENT-1 is True, STATEMENT-2 is False.
Passage 4 (d) STATEMENT-1 is False, STATEMENT-2 is True.
Ozone is prepared in laboratory by passing silent electric dis- 21. Statement 1: The rate of a chemical reaction increases
charge through pure and dry oxygen in an apparatus known with increase in temperature.
as ozoniser. This conversion from oxygen to ozone is a re- Statement 2: Increase in temperature increases the
versible and endothermic reaction. When oxygen is subjected number of effective collision.
to an ordinary electric discharge, most of the O3 produced 22. Statement 1: Generally, the activation energy of the
will get decomposed. When any insulating material such as molecule cannot be zero.
glass, is inserted in the space between the two electrodes and Statement 2: Because 100% reactant molecules can-
high current density is applied, silent electric discharge pass- not convert into the product.
es on between the two electrodes. By this process no spark is 23. Statement 1: Specific activity of the same radioactive
produced and much less heat is generated, and as a result the substance is same for 10 g radioactive substance as
decomposition of the produced ozone is much retarded. well as 50 g radioactive substance.
The decomposition of ozone is believed to occur by the Statement 2: Specific activity of a radioactive sub-
following mechanism: stance is its activity per g.
k1
24. Statement 1: In rate law, the exponents for concentra-
ææ
O3 ¨æ Æ O2 + O
æ (Fast step) tion do not necessarily match the stoichiometry coef-
k 2
ficients.
Kf Statement 2: In rate law expression, exponents for
O3 + O æææ Æ 2O2 (Slow)
concentration are determined by experiments not by
15. Order of the reaction is
balanced chemical reaction.
(a) 1 (b) 2 (c) 3 (d) 0
25. Statement 1: Half-life period of a first order reaction is
16. Molecularity of reaction is defined by
independent of initial concentration.
(a) slow step (b) reversible step
Statement 2: Half-life period for a first order reaction
(c) from overall reaction (d) not defined
2.303
17. When the concentration of O2 is increased, for the same is t1/2 = log 2 .
concentration of ozone, its rate K
(a) increases (b) decreases 26. Statement 1: The Arrhenius equation explains the
(c) remains the same (d) cannot be answered temperature dependence of rate of a chemical reaction.
Statement 2: Plots of log K versus 1/T are linear and
Passage 5 the energy of activation is obtained from such plots.
The rate law for the decomposition of gaseous N2O5 is 27. Statement 1: For a chemical reaction to occur, there
1 must be collision in between reactant species.
N2O5 h 2NO2 + O2. Reaction mechanism has been sug-
2 Statement 2: All such collisions necessarily convert
gested as follows themselves into product formation.
Keq 28. Statement 1: NO2 + CO h CO2 + NO r = k[NO2]
æææ
N2O5 ¨ææ æÆ NO2 + NO3 (fast equilibrium)
The rate of the above reaction is independent of the
k concentration of CO.
NO2 + NO3 ææ
1
Æ NO2 + NO + O2 (slow)
Statement 2: The rate does not depend upon [CO] be-
k
NO + NO3 ææ 2
Æ 2NO2 (fast) cause it is involved in fast step.
18. Order of the reaction is 29. Statement 1: For exothermic as well endothermic re-
(a) 0 (b) –1 (c) 1 (d) 3/2 actions; rate constant increases with increase of tem-
19. In 20 minutes 80% of N2O5 is decomposed. Rate con- perature.
stant is Statement 2: On increasing temperature activation en-
(a) 0.08 (b) 0.05 (c) 0.12 (d) 0.2 ergy of reaction decreases.

30. Statement 1: For a reaction A(gas) Æ B(gas) (c) When A is reduced to 0.06 mol L–1 then B will be
–rA = 2.5PA at 400 k 0.16 mol L–1.
–rA = 2.5PA at 600 k (d) All are correct.
Statement 2 : Activation energy is 4135 J/mole 37. Analyse the rate expression for the following reactions:
31. Statement 1: If the activation energy of a reaction is (i) 3NO(g) h N2O (g); Rate = k[NO]2
zero, temperature will have no effect on the rate con- (ii) H2O2 (aq) + 3I (aq) + 2H h 2H2O (l) + I3– ;
– +
stant. Rate = k[H2O2][I–]

Statement 2: Lower the activation energy, faster the (iii) CH3CHO (g) h CH4 (g) + CO(g);
reaction. Rate = k[CH3CHO]3/2
More than one correct (iv) C2H5Cl (g) h C2H4 (g) + HCl (g);
Rate = k[C2H5CI]
32. A reaction is catalysed by H+ ion. In presence of HA, Based on the above expressions, which of the follow-
rate constant is 2 ¥ 10–3 min–1 and in presence of HB ing is/are correct?
rate constant is 1 ¥ 10–3 min–1, HA and HB both being (a) Order of (i) reaction is two and unit of k is (con-
strong acids, we may conclude that centration)–1 sec–1
(a) equilibrium constant is 2. (b) Order of (ii) reaction is one and unit of k is sec–1
(b) HA is stronger acid than HB. (c) Order of (iii) reaction is three/two and unit of k is
(c) relative acidic strength of HA and HB is 2. (concentration)–1/2 sec–1
(d) HA is weaker acid than HB and relative strength (d) Order of (iv) reaction is one and unit of k is sec–1
is 0.5.
38. Zn + 2H+ h Zn2+ + H2
33. Rate constant k varies with temperature as given by
equation: Half-life period of the reaction is independent of con-
2000 K centration of zinc at constant pH. For the constant con-
log k (min–1) = 5 – . We can conclude centration of Zn, rate becomes 100 times when pH is
T
(a) pre-exponential factor A is 5 decreased from 3 to 2. Hence
(b) Ea is 2000 kcal dx
(c) pre-exponential factor A is 105 (a) = k[Zn]0 [H + ]2
dt
(d) Ea is 9.152 kcal
dx
34. For a first order reaction (b) = k[Zn][H + ]2
(a) The degree of dissociation is equal to 1 – e–kt. dt
(b) A plot of reciprocal of concentration of reactant (c) Rate is not affected if concentration of zinc is
vs. time gives a straight line. made four times and that of H+ ion is halved.
(c) The time taken for the completion of 75% of reac- (d) Rate becomes four times if concentration of H+
tion is thrice the t1/2 of the reaction. ion is doubled at constant Zn concentration.
(d) The pre-exponential factor in the Arrhenius equa- 39. The basic theory behind Arrhenius equation is that
tion has the dimensions of time. (a) the number of effective collisions is proportion-
35. The rate of change in concentration of C in the reaction al to the number of molecules above a certain
2A + B Æ 2C + 3D was observed as 1.0 mol L–1 sec–1.
threshold energy.
Which of the following is/are correct for the rate of re-
(b) as the temperature increases, so does the number
action?
(a) Rate of change of concentration of A is 1.0 mol of molecules with energies exceeding the thresh-
L–1 sec–1. old energy.
(b) Rate of change of concentration of B is 0.5 mol (c) the rate constant is a function of temperature.
L–1 sec–1. (d) the activation energy and pre-exponential factor
(c) Rate of change of concentration of D is 1.5 mol are always temperature-independent.
L–1 sec–1. 40. The calculation of the pre-exponential factor is based
(d) Rate of reaction is 0.5 mol L–1 sec–1. on the
36. For the reaction: 2A + B h A2B (a) idea that, for a reaction to take place, the reactant
The rate = k[A][B]2 with k = 2.0 ¥ 10–6 mol–2 L2 s–1. If species must come together.
the initial concentration of A and B are 0.1 mol L–1 and (b) calculation of the molecularity of the reaction.
0.2 mol L–1 respectively then which of the following is/ (c) idea that the reactant species must come together,
are correct? leading to the formation of the transition state
(a) Initial rate of reaction is 8 ¥ 10–9 mol L–1 sec–1.
which then transforms into the products.
(b) When A is reduced to 0.06 mol L–1 then rate be-
(d) calculation of the order of the reaction.
comes 3.89 ¥ 10–9 mol L–1 sec–1.

41. Which of the following factors affect the rate of reac- III 0.4 0.4 –
tion? –
(a) Nature of reactant
IV 0.2 2 ¥ 10–2
(b) Pressure Which of the following is/are correct for the above
(c) Volume of reaction vessel data?
(d) Radiation (a) Concentration of A in II experiment is 2 ¥ 10–1
42. Consider the following case of competing first order mol L–1.
reactions. C (b) Half life period of B is independent of initial con-
After the start of the reaction at t = 0 with k1
centration.
only A, the [C] is equal to [D] at all times. A
(c) Initial rate for experiment III is 3.2 ¥ 10–2 mol
The time in which all the three concentra- k2
D
tion will be equal is given by L–1 min–1.
(d) Concentration of A in experiment IV is 1¥ 10–1
1 1
(a) t = ln 3 (b) t = ln 3 mol L–1.
2k1 2k 2
47. Which of the following statements is/are correct?
1 1 (a) The rate of the reaction involving the conver-
(c) t = ln 2 (d) t = ln 2
3k1 3k2 sion of ortho-hydrogen to para-hydrogen is
d [H 2 ]
43. In which of the following, Ea for backward reaction is - = k[H 2 ]3/2 .
greater than Ea for forward reaction? dt
E
a = 50kcal (b) The rate of the reaction involving the thermal de-
(a) A æææææ Æ B; DH = - 10 kcal
composition of acetaldehyde is k[CH3CHO]3/2.
E
a = 50kcal (c) In the formation of phosgene gas from CO and
(b) A æææææ Æ B; DH = +10 kcal
Cl2, the rate of the reaction is k[CO][Cl2]1/2.
(c) A + 10 kcal Æ B; Ea = 50 kcal (d) In the decomposition of H2O2, the rate of the reac-
(d) A – 10 kcal Æ B; Ea = 50 kcal tion is k[H2O2].
44. Which of the following statements is (are) correct?
48. Which of the following reactions is/are of the first or-
1 der?
(a) A plot of log Kp vs is linear.
T (a) The decomposition of ammonium nitrate in an
(b) A plot of log[X] vs time is linear for a first order aqueous solution.
reaction, X Æ P. (b) The inversion of cane-sugar in the presence of an
1 acid.
(c) A plot of log P vs. is linear at constant vol-
T (c) The acidic hydrolysis of ethyl acetate.
ume.
(d) All radioactive decays.
1 49. Which of the following statements about zero-order re-
(d) A plot of log P vs is linear at constant temper-
ature. V action is/are not true?
45. The rate laws for the reaction: (a) Unit of rate constant is sec–1.
RCl + NaOH (aq.) h ROH + NaCl is given by, (b) The graph between log (reactant) versus time is a
Rate = k1[RCl]. The rate of the reaction will be straight line.
(a) doubled on doubling the concentration of sodium (c) The rate of reaction increases with the increase in
hydroxide. concentration of reactants.
(b) halved on reducing the concentration of alkyl ha- (d) Rate of reaction is independent of concentration
lide to one half. of reactants.
(c) increased on increasing the temperature of the re- 50. In a pseudo first order acid catalysed hydrolysis of es-
action. ter in water, the following results were obtained:
(d) unaffected by increasing the temperature of the t/s 0 30 60 90
reaction. [ester]/M 0.55 0.31 0.17 0.085
46. The reaction between A and B is first order with respect Which of the following is/are correct for the given re-
to A and zero order with respect to B. Analyse the given action?
data for the same reaction. (a) The average rate of reaction between time interval
30 to 60 seconds is 4.67 ¥ 10–3mol L–1 s–1.
Experiment [A] in [B] in Initial rate in
(b) Order of reaction is 2.
mol L–1 mol L–1 mole L–1 min–1
(c) Pseudo first order rate constant for the acid cata-
I 0.1 0.1 2 ¥ 10–2 lysed hydrolysis of ester is 1.92 ¥ 10–2 s–1.
II – 0.2 4 ¥ 10–2 (d) All are correct.

51. Which of the following statements are correct about 60. The rate constant for the reaction 2N2O5 Æ 4NO2 is 3
half-life period? ¥ 10–5 sec–1 if the rate 2.4 ¥ 10–5 mol L–1 sec–1 then the
(a) It is proportional to initial concentration for ze- concentration of N2O5 in mol L–1 is ......... ¥ 10–5.
roth order.
(b) Average life = 1.44 ¥ half-life; for first order reac- Subjective Type Question
tion. 61. In a catalytic experiment involving the Haber process,
(c) Time of 75% reaction is thrice of half-life period N2 + 3H2 h 2NH3, the rate of reaction was mea-
in first order reaction. sured as
(d) 99.9% reaction takes place in 100 minutes for the
D[NH3 ]
case when rate constant is 0.0693 min–1. Rate = = 2 ¥ 10–4 mol L–1 s–1.
52. Which of the following statements is/are correct? Dt
(a) The order of a reaction is the sum of the com- If there were no side reactions, what was the rate of
ponents of all the concentration terms in the rate reaction expressed in terms of (a) N2, (b) H2?
equation. 62. Dinitropentaoxide decomposes as follows:
(b) The order of a reaction with respect to one reactant 1
is the ratio of the change of logarithm of the rate of N2O5(g) h 2NO2(g) + O2(g)
2
the reaction to the change in the logarithm of the
Given that –d[N2O5]/dt = k1[N2O5]
concentration of the particular reactant, keeping
the concentrations of all other reactants constant. d[NO2]/dt = k2[N2O5]
(c) Orders of reactions can be whole numbers or frac- d[O2]/dt = k3[N2O5]
tional numbers. What is the relation between k1, k2 and k3?
(d) The order of a reaction can only be determined 63. The reaction 2A + B + C Æ D + E is found to be first
from the stoichiometric equation for the reaction. order in A second in B and zero order in C.
53. In Arrhenius equation, K = Ae - Ea /RT . A may be termed (i) Give the rate law for the reaction in the form of
as the rate constant at differential equation.
(a) very low temperature (ii) What is the effect in rate of increasing concentra-
(b) very high temperature tions of A, B and C two times?
(c) zero activation energy 64. In the following reaction, rate constant is 1.2 ¥ 10–2 M
s–1 A h B. What is concentration of B after 10 and
(d) the boiling temperature of the reaction mixture
20 min., if we start with 10 M of A?
Integer type Question 65. In gaseous reactions important for understanding the
54. Rate constant for a reaction H2 + I2 m 2HI is 0.2, then upper atmosphere, H2O and O react biomolecularly to
calculate rate constant for reaction 2HI m H2 + I2 form two OH radicals. DH for this reaction is 72 kJ at
55. A freshly prepared radioactive source of half-life 2 500 K and Ea = 77 kJ mol–1, then calculate Ea for the
hours emits radiations of intensity which is 64 times biomolecular recombination of 2OH radicals to form
the permissible safe level. Calculate the minimum H2O and O at 500 K.
number of half-lives after which it would be possible 66. The reaction 2NO + Br2 h 2NOBr, is supposed to
to work safely with this source. follow the following mechanism:
56. Two reactions proceed at 25°C at the same rate, the fast
(i) NO + Br2 NOBr2
temperature coefficient of the rate of the first reaction
slow
is 2.0 and of the second, 2.5. Find the approximate ratio (ii) NOBr2 + NO æææ Æ 2NOBr
of rates of these reactions at 95°C. Suggest the rate of law expression.
57. Calculate the number of neutrons accompanying the 67. A first order reaction, A Æ B, requires activation ener-
formation of 139 94
54 Xe and 38Sr from the absorption of a gy of 70 kJ mol–1. When a 20% solution of A was kept
235 at 25°C for 20 minutes, 25% decomposition took place.
slow neutron by 92 U, followed by nuclear fission.
What will be the percent decomposition in the same
58. The rate constant, the activation energy and the Arhe- time in a 30% solution maintained at 40°C? Assume
nius parameter (A) of a chemical reaction at 25°C are that activation energy remains constant in this range of
3.0 ¥ 10–4 sec–1, 104.4 kJ mol–1 and 6.0 ¥ 10–4 sec–1 temperature.
respectively the value of the rate constant T Æ is 68. Two reactions (i) A Æ products (ii) B Æ products, fol-
........ ¥ 10–4 sec–1. low first order kinetics. The rate of the reaction (i) is
B
k1 k1 doubled when the temperature is raised from 300 K to
59. For a first order parallel reaction A =8 310 K. The half-life for this reaction at 310 K is 30 min.
k2 k2
C At the same temperature B decomposes twice as fast as
(C )
then, at a time interval, the value of is given as A. If the energy of activation for the reaction (ii) is half
( A) of that of reaction (i), calculate the rate constant of the
e xa - 1
what is the value of x? reaction (ii) at 300 K.
x

69. Decomposition of H2O2 is a first order reaction. A so- oxide film at time t, a and b are constants. What is the
lution of H2O2 labelled as 20 volumes was left open. order of this reaction?
Due to this, some H2O2 decomposed. To determine the 75. The complex [Co(NH3)5F]2+ reacts with water accord-
new volume strength after 6 hrs, 10 mL of this solution ing to equation.
was diluted to 100 mL. 10 mL of this diluted solution [Co(NH3)5F]2+ + H2O Æ [Co(NH3)5(H2O)]3+ + F–
was titrated against 25 mL of 0.025 M KMnO4 solution The rate of the reaction = rate const. ¥ [complex]a ¥
under acidic conditions. Calculate the rate constant for [H+]b. The reaction is acid catalysed, i.e., [H+] does not
decomposition of H2O2. change during the reaction. Thus rate = k¢[Complex]
a
70. Isomerisation of cyclobutene into 1,3-butadine follows where k¢ = k[H+]b, calculate ‘a’ and ‘b’ given the fol-
first order kinetics as: lowing data at 25°C.
[Complex]M [H+]M T1/2hr T3/4hr
(g) — Æ (g) 0.1 0.01 1 2
0.2 0.02 0.5 1
The kinetic study was performed by taking same
76. At room temperature (20°C) orange juice gets spoilt in
amounts of cyclobutene in three sealed flasks. First
about 64 hrs. In a refrigerator at 3°C juice can be stored
flask was broken after 20 minute and the reaction mix-
three times as long before it gets spoilt. Estimate (a) the
ture was absorbed completely in bromine solution. 16.0
activation energy of the reaction that causes the spoil-
mL 1.0 M bromine solution was required. The second
ing of juice. (b) How long should it take for juice to get
flask was broken after a very long time and the reaction spoilt at 40°C?
mixture required 20 mL bromine solution of the same 77. A vessel contains dimethyl ether at a pressure of 0.4
strength. If the third flask was broken after 30 minute, atm. Dimethyl ether decomposes as CH3OCH3(g) h
what volume of bromine solution of same strength CH4(g) + CO(g) + H2(g). The rate constant of decom-
would have been required? position is 4.78 ¥ 10–3 min–1. Calculate the ratio of ini-
71. Decomposition of both A2(g) and B3(g) follows 1st or- tial rate of diffusion to rate of diffusion after 4.5 hr of
der kinetic as: initiation of decomposition. Assume the composition
K - 14000
A2(g) ææ
1
Æ 2A(g) K1(hr–1) = 102 e RT of gas present and composition of gas diffusing to be
same.
K - 20000 B
B3(g) ææÆ
2
3B(g) K2(hr–1) = 103 e RT 78. The reaction A proceeds in parallel channels A
C
.
If one mole of each A2(g) and B3(g) are taken in a 10 L Suppose the half-life values for the two branches are
evacuated flask and heated to some temperature so that 60 min and 90 min, what is the overall half-life value?
they start decomposing at the same rate, determine total 79. A certain reactant Bn+ is getting converted to B(n+4)+ in
pressure in the flask after 1.0 hr. solution. The rate constant of this reaction is measured
72. A first order chemical reaction was carried out for 1.0 by titrating a volume of the solution with a reducing
hour in absence of a catalyst and 20% reaction was reagent which only reacts with Bn+ and B(n+4)+. In this
complete. A catalyst was then added and reaction was process, it converts Bn+ to B(n–2)+ and B(n+4)+ to B(n–1)+.
allowed to continue for next 30 min when 60% reaction At t = 0, the volume of the reagent consumed is 25 mL
was complete. A second catalyst was then added at this and at t = 10 min, the volume used up is 32 mL. Calcu-
time and reaction was allowed to continue for further late the rate constant of the conversion of Bn+ to B(n+4)+
10 min when 90% reaction was complete. If activation assuming it to be a first order reaction.
energy of the original path was 80 kJ, determine acti- 80. The catalytic decomposition of formic acid may take
vation energy of catalysed pathways. Assume constant place in two ways:
temperature throughout to be 300 K. (a) HCOOH = H2O + CO
73. Derive an expression for the velocity of reaction: (b) HCOOH = H2 + CO2
2N2O5(g) h 4NO2(g) + O2(g) The rate constant and activation energy for reaction (a)
with the help of following mechanism: are 2.79 ¥ 10–3 min–1 at 236°C and 12.0 kcal mole–1
K respectively and for reaction (b) are 1.52 ¥ 10–4 min–1
N2O5 ææÆ
a
NO2 + NO3
at 237°C and 24.5 kcal mole–1 respectively. Find the
K
NO3 + NO2 æææ
-a
Æ N2O5 temperature which will give a product made up of equi-
K molar quantities of water vapour, carbon monoxide,
NO2 + NO3 ææÆ
b
NO2 + O2 + NO hydrogen and carbon dioxide.
K
NO + NO3 ææÆ c
2NO2 81. For the reaction A ææ
1 K
Æ B, 2 A ææ
1
ÆC
K
Find
74. The oxidation of certain metals is found to obey the - d [ A]
.
equation t2 = at + b where t is the thickness of the dt

(a) a-emission (b) b-emission

ÈÊ n ˆ Ê n ˆ ˘
V = V0 ÍÁ 2 ˜ - Á 2 - 1˜ exp(- n1kt ) ˙ ; (c) positron emission (d) proton emission
ÎË n1 ¯ Ë n1 ¯ ˚ 5. At 380°C, the half-life period for the first order decom-
È exp( - n kt ) ˘ position of H2O2 is 360 min. The energy of activation
[ A]t = [ A]0 Í 1
˙ of the reaction is 200 kJ mol–1. Calculate the time re-
( n
Î 2 1 / n ) - {( n /
2 1n ) - 1}exp( - n1 kt ) ˚
quired for 75% decomposition at 450°C.
82. Bicyclohexane was found to undergo two parallel first [IIT JEE, 1995]
order rearrangements. At 730 K, the first order rate con- 6. The rate constant for the first order decomposition of a
stant for the formation of cyclohexane was measured as certain reaction is given by the equation, log k(sec–1) =
1.26 ¥ 10–4 s–1, and for the formation of methyl cyclo-
1.25 ¥ 104
pentene the rate constant was 3.8 ¥ 10–5 s–1. What is the 14.34 – . Calculate [IIT JEE, 1997]
percentage distribution of Cyclohexane? T
83. At 380°C, the half-life period for the first order decom- (a) the energy of activation
position of H2O2 is 360 min. The energy of activation (b) the rate constant at 500 K.
of the reaction is 200 kJ mol–1. Calculate the time re- (c) At what temperature will its half-life period be
256 minute?
quired for 75% decomposition at 450°C.
7. The rate constant of a reaction is 1.5 ¥ 107 sec–1 at 50°C
84. The decomposition of Cl2O7 at 440K in the gas phase
and 4.5 ¥ 107 sec–1 at 100°C. Evaluate the Arrhenius
to Cl2 and O2 is a first order reaction.
parameters A and Ea. [IIT JEE, 1998]
(i) After 55 sec at 440 K the pressure of Cl2O7 falls
8. For a hypothetical elementary reaction
from 0.062 to 0.044 atm., calculate that rate con-
2B
stant.
k1
(ii) Calculate the pressure of Cl2O7 after 100 sec of k1 1
A where = . Initially only 2
decomposition at this temperature. k2 k2 2
2C
85. The first order reaction has K = 1.5 ¥ 10–6 per second
moles of ‘A’ is present. Then total number of moles A,
at 200°C. If the reaction is allowed to run for 10 hrs,
B and C at the end of 50% reaction is [IIT JEE, 1999]
what percentage of the initial concentration would have
9. The rate of decomposition for methyl nitrite and ethyl
changed in the product? What is the half-life period of nitrite can be given in terms of rate constant (in sec–1)
this reaction? k1 and k2 respectively. The energy of activation for the
two reactions are 152.30 kJ mol–1 and 157.7 kJ mol–1
PREVIOUS YEARS’ QUESTIONS as well as frequency factors are 1013 and 1014 respec-
OF JEE (MAIN & ADVANCED) tively for the decomposition of methyl and ethyl nitrite.
Calculate the temperature at which rate constant will be
1. A catalyst [IIT JEE, 1984] same for the two reactions. [IIT JEE, 1999]
(a) increases the average kinetic energy of reacting 10. The rate constant for an isomerisation reaction, A h
molecules. B is 4.5 ¥ 10–3 min–1. If the initial concentration of A is
(b) decreases the activation energy. 1 M, calculate the rate of the reaction after 1 hr.
(c) alters the reaction mechanism. [IIT JEE, 1999]
(d) increases the frequency of collisions of reacting 11. The rate constant for the reaction
species. 2N2O5 h 4NO2 + O2
2. The half-life period of a radioactive element is 140 is 3 ¥ 10–5 s–1. If the rate at a given time is 2.40 ¥ 10–5
days. After 560 days, 1 g of the element will reduced to mol L–1 s–1, then concentration of N2O5 at that time is
[IIT JEE, 1986] [IIT JEE, 2000]
1 1 1 1 (a) 1.4 mol L–1 (b) 1.2 mol L–1
(a) g (b) g (c) g (d) g (c) 0.04 mol L–1 (d) 0.8 mol L–1
2 4 8 16
12. 64
Cu (half-life = 12.8 h) decays by b– emission (38%),
3. A first order reaction A h B requires activation ener- b+ emission (19%) and electron capture (43%). Write
gy of 70 kJ mol–1. When a 20% solution of A was kept the decay products and calculate partial half-lives for
at 25°C for 20 min, 25% decomposition took place. each of the decay processes. [IIT JEE, 2001]
What will be the percent decomposition in the same 13. If I is the intensity of absorbed light and C is the con-
time in a 30% solution maintained at 40°C? Assume centration of AB for the photochemical process. AB
that activation energy remains constant in this range of hu
temperature. [IIT JEE, 1993] ææÆ AB*, the rate of formation of AB* is directly
4. 13Al27 is a stable isotope. 13Al29 is expected to disinte- proportional to [IIT JEE, 2001]
grate by [IIT JEE, 1994] (a) C (b) I (c) I2 (d) C.I

23
14. Na is the more stable isotope of Na. Find out the pro- (a) 2 (b) 3 (c) 0 (d) 1
24 22. The rate of a reaction doubles when its temperature
cess by which 11 Na can undergo radioactive decay
[IIT JEE, 2003] changes from 300 K to 310 K. Activation energy of
(a) b– emission (b) a emission such a reaction will be (R = 8.314 kJ–1 mol–1 and log 2
(c) b+ emission (d) K electron capture = 0.301) [2013 Main]
15. The reaction, X Æ Product, follows first order kinetics. (a) 53.6 kJ mol–1 (b) 48.6 kJ mol–1
In 40 minutes the concentration of X changes from 0.1 (c) 58.6 kJ mol–1 (d) 60.5 kJ mol–1
to 0.025 M. The rate of reaction, when concentration of 23. For the elementary reaction, M h N the rate of dis-
X is 0.01 M is [IIT JEE, 2004]
appearance of M increases by a factor of 8 upon dou-
(a) 1.73 ¥ 10–4 M min–1 (b) 3.47 ¥ –5 M min–1
bling the concentration of M. The order of the reaction
(c) 3.47 ¥ 10–4 M min–1 (d) 1.73 ¥ 10–5 M min–1
23 with respect to M is [2014 Adv.]
16. A positron is emitted from 11 Na . The ratio of the (a) 4 (b) 3 (c) 2 (d) 1
atomic mass and atomic number of the resulting nu-
24. For the non-stoichiometric reaction, 2A + B Æ C + D,
clide is [IIT JEE, 2007]
the following kinetic data were obtained in three sepa-
(a) 22/10 (b) 22/11 (c) 23/10 (d) 23/12
rate experiments, all at 298 K. [2014 Main]
17. Calculate total number of a and b particles emitted in
the nuclear reaction
Initial con- Initial Initial rate of
92U
238
h 82Pb214 [IIT JEE, 2009]
centration concentration formation of C
18. For a first order reaction A Æ P, the temperature (T)
[A] [B] [mol L–1s–1]
dependent rate constant (k) was found to follow the
1 (i) 0.1 M 0.1 M 1.2 ¥ 10–3
equation log k = –(2000) + 6.0 . The pre-exponential
T (ii) 0.1 M 0.2 M 1.2 ¥ 10–3
factor A and the activation energy Ea, respectively, are
[IIT JEE, 2009] (iii) 0.2 M 0.1 M 2.4 ¥ 10–3
(a) 1.0 ¥ 106 s–1 and 9.2 kJ mol–1
The rate law for the formation of C is
(b) 6.0 s–1 and 16.6 kJ mol–1
(c) 1.0 ¥ 106 s–1 and 16.6 kJ mol–1 (a)
dC
= k[ A][ B] (b)
dC
= k[ A]2 [ B]
(d) 1.0 ¥ 106 s–1 and 38.3 kJ mol–1 dt dt
19. An organic compound undergoes first order decomposi- dC dC
tion. The time taken for its decomposition to 1/8 and 1/10 (c) = k[ A][ B]2 (d) = k[ A]
dt dt
of its initial concentration are t1/8 and t1/10 respective-
Èt ˘ 25. Higher order (> 3) reactions are rare due to
ly. What is the value of Í 1/8 ˙ ¥ 10? (log102 = 0.3)? [2015 Main]
Î t1/10 ˚ [2012]
(a) low probability of simultaneous collision of all
20. The periodic table consists of 18 groups. An isotope of
the reacting species.
copper, on bombardment with protons, undergoes a nu-
(b) increase in entropy and activation energy as more
clear reaction yielding element X as shown below. To
molecules are involved.
which group, element X belongs in the periodic table?
[2012] (c) shifting of equilibrium towards reactants due to
elastic collisions.
29 Cu + 1H ææ Æ 60 n + 2a + 21 H + X
63 1 1 4 1
(d) loss of active species on collision.
21. In the reaction, P + Q h R + S, the time taken for 26. Two reactions R1 and R2 have identical pre-exponetial
75% reaction of P is twice the time taken for 50% reac- factors. Activation energy of R1 exceeds that of R2 by
tion of P. The concentration of Q varies with reaction 10 KJ mol–1. If K1 and K2 are rate constants for reac-
time as shown in the figure. The overall order of the tions R1 and R2 respectively at 300 K, then ln (K2/K1) is
reaction is [2013 Adv.] equal to
(R = 8.314 J mol–1 K–1) [2017 Main]
[Q]0 (a) 6 (b) 4
[Q] (c) 8 (d) 12
Time

Answer Key
LEVEL I
1. (c) 2. (d) 3. (d) 4. (a) 5. (c) 6. (d) 7. (b) 8. (d) 9. (a) 10. (c)
11. (c) 12. (b) 13. (a) 14. (a) 15. (d) 16. (c) 17. (a) 18. (c) 19. (a) 20. (b)
21. (c) 22. (a) 23. (c) 24. (c) 25. (d) 26. (a) 27. (d) 28. (c) 29. (c) 30. (a)
31. (c) 32. (c) 33. (b) 34. (c) 35. (a) 36. (c) 37. (b) 38. (d) 39. (c) 40. (b)
41. (b) 42. (b) 43. (b) 44. (c) 45. (a) 46. (d) 47. (b) 48. (a) 49. (a) 50. (d)
51. (b) 52. (a) 53. (a) 54. (b) 55. (c) 56. (b) 57. (c) 58. (a) 59. (a) 60. (a)
61. (b) 62. (c) 63. (b) 64. (d) 65. (a) 66. (a) 67. (c) 68. (c) 69. (b) 70. (a)
71. (b) 72. (c) 73. (a) 74. (d) 75. (d) 76. (c) 77. (b) 78. (c) 79. (b) 80. (b)
81. (d) 82. (b) 83. (c)
LEVEL II
1. (b) 2. (b) 3. (d) 4. (b) 5. (a) 6. (c) 7. (d) 8. (c) 9. (d) 10. (d)
11. (a) 12. (d) 13. (c) 14. (c) 15. (c) 16. (a) 17. (c) 18. (b) 19. (b) 20. (c)
21. (b) 22. (c) 23. (b) 24. (b) 25. (d) 26. (b) 27. (b) 28. (c) 29. (a) 30. (b)
31. (d) 32. (b) 33. (d) 34. (d) 35. (b) 36. (b) 37. (a) 38. (a) 39. (d) 40. (d)
41. (c) 42. (c) 43. (a) 44. (c) 45. (a) 46. (b) 47. (b) 48. (d) 49. (c)
LEVEL III
1. (A) Æ q, t; (B) Æ q; (C) Æ r; (D) Æ s 2. (A) Æ p; (B) Æ p; (C) Æ r; (D) Æ s
3. (A) Æ q; (B) Æ r, t; (C) Æ s; (D) Æ p 4. (A) Æ r; (B) Æ s; (C) Æ q; (D) Æ p
5. (A) Æ r, s; (B) Æ t; (C) Æ p; (D) Æ q
6. (d) 7. (a) 8. (b) 9. (d) 10. (a) 11. (d) 12. (c) 13. (a) 14. (d) 15. (a)
16. (d) 17. (b) 18. (c) 19. (a) 20. (a) 21. (a) 22. (a) 23. (a) 24. () 25. (a)
26. (a) 27. (c) 28. (a) 29. (c) 30. (a) 31. (b) 32. (b, c) 33. (c, d) 34. (a, d)
35. (a, b, c, d) 36. (a, b) 37. (a, c, d) 38. (b, c, d) 39. (a, b, c) 40. (a, c)
41. (a, b, c, d) 42. (a, b) 43. (a, d) 44. (a, b, d) 45. (b, c) 46. (a, d) 47. (a, b, c, d)
48. (a, b, c, d) 49. (a, c) 50. (a, b, d) 51. (a, b, c) 52. (a, b, c) 53. (b, c)
54. [5] 55. [6] 56. [5] 57. [3] 58. [6] 59. [9] 60. (80)
61. (i) [1 ¥ 10–4 mol L–1 Sec–1] (ii) [3 ¥ 10–4 Mol L–1 sec–1] 62. [2K1 = K2 = 4K3]
63. (i) [K1 [A] [B]2] (ii) [rate increases by 8 times] 64. [2.8 M, 0 M] 65. [Eab = 5 kJ]
66. [Rate = k1 [NO]2 [Br2]] 67. [67.17%] 68. [0.0327 min–1] 69. [K = 0.022 hr–1]
È –1 d [N 2O5 ] ka kb [N 2O5 ] ˘
70. [17.47 mL] 71. [8 atm] 72. [75.44 KJ, 70.975 KJ] 73. Ír = =
Î 2 dt k – a + 2kb ˙˚
74. [–1] 75. [1,1] 76. (a) (43.45 kJ) (b) (20.47 hr) 77. [0.26] 78. [36 min]
È - d [ A] ˘
79. [K = 0.02 min–1] 80. [397.6°C] 81. Í = K1[ A] + 2 K 2 [ A]2 ˙ 82. [76.8%] 83. [20.39]
Î dt ˚
84. (i) [6.23 ¥ 10–3 Sec–1] (ii) [0.033 atm] 85. [5.25% and 128.33 hr]
PREVIOUS YEARS’ QUESTIONS OF JEE (MAIN & ADVANCED)
1. (b, c) 2. (d) 3. [67.17%] 4. (b) 5. (20.358 min)

6. (a) [239.339 KJ mol–1] (b) [2.18 ¥ 10–11 sec–1] (c) [669K] 7. [A = 5.43 ¥ 1010, 22.01 KJ mol–1] 8. [3]
9. [282 K] 10. [3.435 ¥ 10–3 M min–1] 11. (d) 12. [30Zn64, 28Ni64, 28Ni64 33.70 hr, 67.41 hr, 29.28 hr]
13. (b) 14. (a) 15. (c) 16. (c) 17. (6) 18. (d) 19. (9) 20. (8) 21. (d) 22. (a)
23. (b) 24. (d) 25. (a) 26. (b)

Hints and Solutions
LEVEL I - d [a - x]
10. = K1[a - x] + K 2 [a - x]
dt
11. r = K[X][C]
-1 d [H 2 ]
1. r = [X ]
3 dt K¢ =
[ A][ B]
- d [H 2 ]
= 3 ¥ 2.5 ¥ 10–4 =7.5 ¥ 10–4 mol L–1 S–1 r = KK¢[A] [B] [C]
dt
= k[A] [B] [C]
- d [O 2 ] 1 d [SO3 ] 12. r = k[(NO)2][Cl2]
2. =
dt 2 dt [(NO) 2 ]
d [SO3 ] and K=
= 2 ¥ 2.5 ¥ 10–4 = 5 ¥ 10–4 mol L–1 S–1 [NO]2
dt
\ r = kK [NO]2 [Cl2 ]
3. aA + bB Æ P
1 D[ A] 1 D[ B] Ê 35 - 0 ˆ
Rate = =- = K [ A]m [ B]n 13. K ¥ 15 = ln Á
a Dt b Dt Ë 35 - 9 ˜¯
if [A] = 1 M and [B] = 1 M Ê 100 ˆ
14. K ¥ 32 = ln Á
Ë 1 ˜¯
Rate = K (i)
4. r = K[A]2 [B]
r = K[x]2 [y] Ê 100 ˆ
K ¥ t = ln Á (ii)
Ë 0.1 ˜¯
r¢ = K[3x]2 [3y]
r¢ = 27r eq. (ii)/(i)
t 3 ln 10
1 d [C ] 1 =
5. r = = ¥ 1 = 0.5 mol L–1 S–1 32 2 ln 10
2 dt 2
t = 48 min
2.303 Èa ˘
6. K = log Í 0 ˙ 1
t Îa˚ 15. Given t 1 μ 2
2 a
1
1
2.303 10 t 1 μ n -1
K= log 2 a
500 1
n–1=2
100
n=3
2.303
= log 10 = 4.606 ¥ 10- 3 sec-1 1 200 Ê 1 ˆ
n -1
500 16. t 1 μ =Á ˜
7. r = K[A] = 5 ¥ 10–5 [1] = 5 ¥ 10–5 M s–1 2 a n -1 100 Ë 0.5 ¯
8. r = K2[N2O2] [O2] (i) 2 = 2n–1 n – 1 = 1n = 2
17. K = Ae–Ea/RT
K1 [N 2O 2 ] K
= or [N 2O 2 ] = 1 [NO]2 from eq. (i) Ea
K -1 [NO]2 K -1 ln K = ln A –
RT
K1
r = K2 ¥ [NO]2 [O 2 ] Ea
K -1 2.303 log K = - + 2.303 log A
RT
Compare r = K[NO]2 [O2] Ea
K log K = - + log A
K = K 2 1 ¥ [NO]2[O2] 2.303RT
K -1 Ea
slope = 5000
1 d [N 2O5 ] 1 d [NO 2 ] d [O 2 ] 2.303R
9. r = - = = = K [N 2O5 ]
2 dt 4 dt dt Ea = 5000 ¥ 8.31 ¥ 2.303 = 95.7 kJ K–1 mol–1
K1 = 2K Ea
18. - = –40000
K2 = 4K = 2K1 R
K Ea = 40000 ¥ 2 = 8 ¥ 104 cal
K3 = K = 1
2

7.2 ¥ 10-2
- E1 - E3 + E2
[0.3]a [0.2]b
19. K = Ae–Ea/RT \ Ae–Ea/RT = Ae RT =
[0.3]a [0.4]b 2.88 ¥ 10-1
Ea = E1 + E3 – E2 = 60 + 10 – 30 = 40 kJ
20. (b) rate = k[A]n [B]m \ r = k[A][B]2 È1˘ È1 ˘
b 2
m=2 n=1 On solving Í ˙ = Í ˙ \ b=2

Î2˚ Î2˚
21. (c) r = K[A]2
r = K[A]2 = 4K[A]2 From experiments (I) and (IV)
22. (a) 2 NH3 m N3 + 3H2 [0.1]a [0.1]b 6 ¥ 10-3
=
d [N 2 ] 1 d [H 2 ] 1 d [NH3 ]
a
[0.4] [0.1] b
2.40 ¥ 10-2
+ =+ =-
dt 3 dt 2 dt On solving \ a=1
x
23. (c) r= k[A] [B] y rate law is ; rate = k[A]1[B]2
Change in concentration 0.01 Now rate = 6 ¥ 10–3
24. (c) Average= = = k[0.1]1[0.1]2
Time 25 ¥ 60
k = 6 M–2 min–1
= 6.66 ¥ 10–6 M sec–1 30. (a) Let the order with respect to A be ‘a’ and with re-
25. (d) For the given change spect to B be ‘b’. The rate law would then be repre-
- d [ N 2 O5 ] 1 d [ NO 2 ] d [O 2 ] sented as
=+ =2 Rate = K[A]a[B]b
dt 2 dt dt
Therefore by (i) and (ii),
On substituting values as given,
1 4.0 ¥ 10- 3 K [5.0 ¥ 10- 4 ]a [6.0 ¥ 10- 5 ]b
k1[N2O5] = k2[N2O5] = 2k3[N2O5] =
2 5.0 ¥ 10- 4 K [2.5 ¥ 10- 4 ]a [3.0 ¥ 10- 5 ]b
or 2k1 = k2 = 4k3 23 = [2]a + b
n DP \ a+b=3
26. (a) The change in molarity = =
V RT By (ii) and (iii),
=
0.9
= 0.0365 4.0 ¥ 10-3 K [5.0 ¥ 10- 4 ]a [6.0 ¥ 10-5 ]b
0.0821 ¥ 300 =
1.6 ¥ 10-2 K [1.0 ¥ 10- 3 ]a [6.0 ¥ 10-5 ]b
0.0365 a
Rate of reaction = = 8.12 ¥ 10–6 mol L–1 sec–1 1 Ê 1ˆ
75 ¥ 60 =Á ˜
4 Ë 2¯
27. (d) As the slowest step is the rate determining step, \ a = 2 and b = 1
therefore the rate law is , r = k[NOBr2] [NO]
Now since NOBr2 is an intermediate its concentration 0.693 2.303 100
31. (c) = log
can be calculated from Step 1 as follows: t1/2 40 70
[NOBr2 ] t1/2 = 77.70 min
Kc = ; [Kc = equilibrium constant] 32. (c) Initial concentration (N0) of radio-isotope is 1 g
[NO][Br2 ]
atom. Concentration remained after 20 days may be
or [NOBr2] = Kc[NO] [Br2]
calculated as
Substituting this value in above equation,
n
r = K ◊ Kc[NO]2[Br2] Ê 1ˆ
Nt = N 0 Á ˜
or rate = k [NO]2 [Br2] [k = K ◊ Kc] Ë 2¯
rate = k [NO]2 [Br2] where n = number of half-lives = 20/10 = 2
28. (c) 2
Ê 1ˆ 1
(i) The rate law according to given information may Nt = 1Á ˜ =
Ë 2¯ 4
dx 1 3
be given as, = k[A]1[B]2[C]0 Concentration decayed to a-particles = 1 – = g
dt 4 4
(ii) When concentration of A, B and C are doubled
atom. An a-particle takes 2 electron from air and from
dx
then rate will be = k[2A][2B]2[C]0 = 8k[A] helium gas. Thus,
2 2 dt 3 3
[B] [C]
Helium formed = g atom = ¥ 22400 cc = 16800
i.e., rate becomes 8 fold of the original rate. 4 4
cc
29. (c) Let rate = k[A]a[B]b
1
From experiments (II) and (III) 33. (b) A2 h B + C
2

d [C ] 120 - 100 2.303 800

Thus = = 4 mm min -1 55. (c) K = log = 1.386 ¥ 10-2 s -1
dt 5 2 ¥ 10 2
50
- d [ A2 ]
\ = 2 ¥ 4 = 8 mm min -1 1
dt 56. (b) t1/2 μ n -1
\n = 1
a
34. (c) Rate = K[NO]2 [O2]
Volume halved , concentration is doubled and the rate 57. (c) t1/2 = 0.5 hr
of reaction becomes eight times.
(a) Rate = kobs [NO]2 [H2] 0.693
35. 1
58. (a) t1/2 =
kobs = k ◊ Kc K1
36. (c) Unit of k = bar–1/2 min–1 a
0
t1/2 =
37. (b) Two reactant molecules are different. 2K0
38. (d) Order of a reaction can be fractional. 59. (a) Astatine as it belongs to halogen
39. (c) Overall order is 3/2 60. (a) rate = K[A][B]
40. (b) K depends only on temperature 61. (b) One
kT +10 62. (c) Rate = k[A]
41. (b) ª 2 to 3
kT 63. (b) Rate = [A]m[B]n
42. (b) Fraction of molecules with energy more than en- 64. (d) R1 = K[A][B]2 = K[0.6][0.80]2
ergy barrier increases After reaction A + 2B h C + D
0.6 – 0.2 0.8 – 0.4 0.2 0.2
43. (b) k = Ae - Ea / RT
0.4 0.4 0.2 0.2
At Ea = 0 R2 = K [0.4] [0.4]2
k=A
R2 K [0.4][0.4]2 1
44. (c) A catalyst decreases the activation energy. = =
45. (a) A catalyst decreases the activation energy. R1 K [0.6][0.8]2 6
12 0.6932
46. (d) n = =4 65. (a) K = (i)
3 120
È1˘
n 2.303 a
Nt = N 0 Í ˙ K= log
t 0.10a
Î2˚
2.303
È1˘
4 = log 10 (ii)
3 = N0 Í ˙ t
Î2˚ Equating (i) and (ii)
\ N0 = 48 gram 0.693 2.303
=
120 t
47. (b) 92 U
238
ææ
Æ 90Th 234 + 2 He 4 t = 399 min
48. (a) N2(g) + 3H2(r) Æ 2NH3(g) 66. (a) We know that for first order kinetics
2.303 a
-d [ N2 ] 1 d [H 2 ] 1 d [ NH3 ] K= log
=- = t a-x
dt 3 dt 2 dt
2.303 0.5 2.303
49. (a) Rate equation shows that it does not depend on the or t= log = = 0.384 min
6 0.05 6
concentration of (H+)
67. (c) a = 80 mm and a + x = 120 mm
50. (d) x = 1 y = 2 overall is 3
\ a – x = 40 mm
1
51. (b) Order = 3/2 -1 = 2.303 a
2 K= log
t a-x
52. (a) Rate = K[A]m[B2]n
2.303 80
53. (a) Rate =
Concentration = ¥ log
Time 20 40
2.303
a = a0 = 100 = ¥ 0.3010
54. (b) t1/2 = 10 min 20
and a - x = 10
0.693 0.693 ¥ 20
2.303 100 0.6932 t1/2 = = = 20 min
K= log = K 2.303 ¥ 3010
t 10 10

68. (c) t1/2 μ a1 – n 1

\ t1/2 = ln 2
4 μ (50) 1- n l
or 2 μ 2n -1
2 μ (100)1- n 80. (b) t1/2
1
μ n -1 \ t1/2 = k a (i)
a
\ n=2
16
69. (b) K =
2.303
log
100 = 2 (ii)
60 100 - 1.5 t1/2(II)
K = 2.5 ¥ 10–4 sec–1 16

t1/2(II) = = 11.3
70. (a) 2N2O5 Æ 4NO2 + O2, 2
p0 - -
16 + 11.3 = 27.3 min
2.303 p 81. (d) K = Ae–Ea/RT, for 0.001% K = 2.3 ¥ 10–3min–1
k= log10 0
t pt \ for 100% Kmax Kmax = 230 min–1
2.303 500 82. (b) K = Ae–Ea/RT
3.38 ¥ 10–5 = log ; pt = 490 atm As T h e(–Ea/RT) 1.
10 ¥ 60 pt
Hence, K = A = 6.0 ¥ 1014 s–1.
K2 Ea È 1 1˘ r2
= - ˙;
30
71. (b) log Í 83. (c) = ( m ) 10 or 15.6 = (m )3
K1 2.303R Î T1 T2 ˚ r1
9.2 ¥ 10- 3 Ea È 1 1 ˘ log 15.6 = 3 log m
log = -
5.5 ¥ 10 -4
2.303 ¥ 8.314 Î 413 458 ˙˚
Í On solving m = 2.5
Ea = 98.46 kJ mol–1.
72. (c) b-decay occurs by the nuclear change 0n1 Æ 1H1 + LEVEL II
0
–1e .
73. (a) 92 + 0 = Z + 36 + 0 fi Z = 56 ; 1. (b) Since K has unit min–1 and thus, given reaction is of
and 235 + 1 h A + 92 + 3 ; first order
Missing nuclide is 141
56 Ba Now, rate = K[reactant ]1
Initial rate = 10–3 ¥ [0.2]1
2.303 100
74. (d) K = ¥ log = 2 ¥ 10–4 mol dm–3 min–1
32 1
2.303 ¥ 2 0.6932 2.303 a
K= = Also K = log
32 t1/2 t (a - x)
t1/2 = 4.8 min 2.303 100
\ 10-3 = log
75. (d) A – 40 Kcal Æ B Ea = 20 Kcal 200 (100 - x)
\ x = 18.03%
76. (c) 4 mole L-1 æææ
20min
Æ 2 mole L-1 2.303 [ A]
2. (b) For a first order reaction, K = log 0
æææÆ1 mole L-1 æææÆ 0.5 mole L-1
20min 20min
t [ A]t
and for 2nd order t1/2 μ 1/a 6.2
- Ea /RT Initial moles of nitramide = = 0.1
77. (b) x = e 62
2.303 ¥ 2.1 0.1
\ ln x = -
Ea \ t= log = 13.95 hours
RT 0.693 0.001
Since, the decomposition is 99%, so 99% of the initial
78. (c) 24
12 Mg + g ææ
Æ 11
23
Na + 11H
moles of NH2NO2 would be converted to N2O.
79. (b) t =
1 A0
ln 0.1 ¥ 99
l At Moles of N2O =
100
A0 0.1 ¥ 99 ¥ 22.4
at t = t1/2 ; At = \ volume of N2O at STP = = 2.217 L .
2 100

3. (d) As discussed in the decomposition of N2O5

2.303 V
K= log
t V - Vt
2.303 V
Time Vt V – Vt K= log
t V - Vt
2.303 34.75
K= log = 0.0198
10 6.30 34.75 – 6.30 = 28.45 10 28.45
2.303 34.75
K= log = 0.0198
15 8.95 34.75 – 8.95 = 25.80 15 25.80
2.303 34.75
K= log = 0.0198
20 11.40 34.75 – 11.40 = 23.35 200 23.35
2.303 34.75
K= log = 0.0198
25 13.50 34.75 – 13.50 = 21.25 25 21.25
Since the value of K comes out to be constant, therefore, the reaction it is of first order.
The average value of rate constant is 0.0198 min–1.
2.303 V K = 0.00872 month–1

4. (b) K1 = log 0 , we get
2.303 500
t Vt expiry t = ¥ log = 41 time months
0.00872 350
2.303 46.1
(i) K1 = log = 4.364 ¥ 10-2 0.693
10 29.8 also t1/2 = = 79.49 months
2.303 46.1 0.00872
(ii) K1 = log = 4.276 ¥ 10- 2 7. (d) From the given data, V0 = 11.5 cm3; V = 25.5 cm3
20 19.6
\ a μ V – V0 = 25.5 – 11.5 = 14.0
2.303 46.1
(iii) K1 = log = 4.404 ¥ 10-2 and (a – x) μ V – Vt
30 12.3 r rt
Since K1 comes out to be nearly constant, the re- 0 r0
action is a first order one with K as the average 90 90
value of the three.
5. In first and second sets of experiments, [B] are same 180
whereas [A] is changing:
Let us suppose the rate law is R = K[A]m[B]n Putting the values of Vt = 12.0 at 600 sec; 12.5 at 1200
R1 = K[0.01]m[0.01]n = 0.005 sec and 13.0 at 1800 sec in the equation
R2 = K[0.02]m[0.01]n = 0.01 2.303 V - V0
K1 = log , we get
R1 1 Ê 0.01 ˆ
m
Ê 1ˆ
m t V - Vt
= =Á ˜¯ = ÁË ˜¯ fi m = 1
R2 2 Ë 0.02 2 2.303 14.0 2.303 14.0
(i) K1 = log = log
In first and third sets of experiment, [A] are same, [B] is 600 (25.5 - 12.0) 600 13.5
changing, therefore
= 6.061 ¥ 10-5 s -1
R1 = K[0.01]m[0.01]n = 0.005
R3 = K[0.01]m[0.02]n = 0.005 2.303 14.0 2.303 14.0
(ii) K1 = log = log
n n 1200 (25.5 - 12.5) 1200 13.0
R1 Ê 0.01 ˆ Ê 1 ˆ
=1= Á = fi n = 0,
R3 Ë 0.02 ˜¯ ÁË 2 ˜¯ = 6.176 ¥ 10-5 s -1
i.e., reaction is of first order with respect to A and of 2.303 14.0 2.303 14.0
(iii) K1 = log = log
zero order with respect to B. 1800 (25.5 - 13.0) 1800 12.5
2.303 a = 6.296 ¥ 10-5 s -1
6. (c) K = log
t a-x 8. (c) Let us say that the pressure of SO2Cl2 decreases by
2.303 Ê 500 ˆ x atm, then the increase of pressure of SO2 and Cl2 = x
= log Á
20 Ë 420 ˜¯ atm each.

[ 1 mole of SO2Cl2 decomposes to give 1 mole of SO2 0.25 = K[152]a (ii)

and 1 mole of Cl2]. Dividing (i) by (ii),
SO2Cl2(g) Æ SO2(g) + Cl2(g) a
1.50 Ê 359 ˆ
Pressure at t = 0 0.5 atm 0 0 =Á ˜
Pressure at t = t (0.5 – x atm) x atm x atm 0.25 Ë 152 ¯
Since total pressure (PT) = PSO2Cl2 + PSO2 + PCl2 Taking log of both sides,
359
= (0.5 – x) + x + x log 6 = a log \aª2
PT = 0.5 + x or x = PT – 0.5 152
Similarly, by keeping the pressure of NO constant, rate
Hence, PSO2Cl2 = 0.5 – (PT – 0.5) law is given by
= 0.5 – PT + 0.5 = 1.0 – PT 1.60 = K[PNO]a[289]b (iii)
Since, at t = 100 sec, PT = 0.6 atm 0.79 = K[PNO]a[147]b (iv)
\ PSO2 Cl2 = 1.0 – 0.6 = 0.4 atm Dividing (iii) by (iv)
(a) Evaluation of K b
1.60 Ê 289 ˆ
=Á ˜
2.303 initial pressure 0.79 Ë 147 ¯
K= log
t pressure at time t Taking log of both sides
2.303 0.5 Ê 1.60 ˆ Ê 289 ˆ
K= log log Á = b log Á
100 0.4 Ë 0.79 ˜¯ Ë 147 ˜¯
On solving K = 2.23 ¥ 10–3 sec–1 \ bª1
(b) Rate at PT = 0.65 atm \ overall order of the reaction = (a + b) = (2 + 1) = 3
PSO2Cl2 at total pressure of 0.65 atm = 1.0 – 0.65 11. (a)
= 0.35 atm (a) Here a, the initial concentration μ (r0 – r )
Rate = K PSO2Cl2 = 2.23 ¥ 10–3 ¥ 0.35 = 7.8 ¥ 10–4 x, the change in time t μ (r0 – rt)
atm sec–1 \ (a –x) μ (rt – r )
9. (d) Let the initial pressure of A be P0 mm of Hg and the Substituting these values for different (a – x) values
pressure of A decreases in 10 min be x unit. corresponding to time t from the data in the equation
A (g) Æ 2B (g) + C (g) for first order reaction
Initially P0 0 0 2.303 a 2.303 r -r
K= log = log 0 , we get
At time 10 min. P0 – x 2x x t a-x t rt - r
At time 0 2P0 P0
2.303 32 - (-10.5) 2.303 42.5
After long time interval, P = 2P0 + P0 = 3P0 (i) K1 = log = log
10 25.5 - (-10.5) 10 36.0
P
\ P0 = = 90 mm of Hg = 0.0166 min -1
3
After 10 min, Pt = P0 + 2x 2.303 32 - (-10.5) 2.303 42.5
(ii) K1 = log = log
176 = 90 +2x 20 20.0 - (-10.5) 20 30.5
\ x = 43 mm of Hg
= 0.0166 min -1
\ partial pressure of A after 10 min = P0 – x = 90 – 43
= 47 mm of Hg. 2.303 32 - (-10.5) 2.303 42.5
(iii) K1 = log = log
For a first order reaction, the rate constant expression 30 15.5 - (-10.5) 30 26.0
would be
= 0.0164 min -1
2.303 P
K= log 0 2.303 32 - (-10.5) 2.303 42.5
t P0 - x (iv) K1 = log = log
60 5.0 - (-10.5) 60 15.5
2.303 90
K= log = 0.0649 min -1 = 0.0168 min -1
10 47
10. (d) Rate law would be represented as Average value of K1 = 0.0166 min–1
K1
- dp Cyclohexene
= rate = K [PNO ]a [PH2 ]b 12. (d) Bicyclohexane
dt K2
Methylcyclopentene
Using the data given in the problem, keeping pressure
of H2 constant, we get K1
Percentage of cyclohexene = ¥ 100
1.50 = K[359]a (i) K1 + K 2

For Eqs. (i) and (ii)

1.26 ¥ 10-4
= ¥ 100 = 77% n1 = 3, n2 = 1
1.26 ¥ 10-4 + 3.8 ¥ 10-5 t = 3 ¥ 5 = 15 minute
\ Percentage of methylcyclopentane = 23% 18. (b) Initial activity a0 = 2 ¥ 106 dpm
0.693 0.693 Activity after four days at = 9 ¥ 105 dpm
13. (c) K = =
t1/2 22 2.303 2 ¥ 106
l= log = 0.19967 day -1
where K = K1 + K2, which are rate constant of separate 4 9 ¥ 105
paths
Activity after 40 days
Also K1/K2 = 2/98
On solving K2 = 0.03087 y–1 2.303 2 ¥ 106
0.19967 = log
K1 = 0.00063 y–1 40 at
K2 Ea È T2 - T1 ˘ at = 680.81 dpm
14. (c) log =
K1 2.303R ÍÎ T1T2 ˙˚ 2.303 p 2.303 90
-3 19. (b) K = log fi log
6.9 ¥ 10 Ea È 40 ˘ t p-x 10 90 - 45
log =
3.45 ¥ 10-5 2.303 ¥ 8.314 ÍÎ 300 ¥ 340 ˙˚ 2.303
Ea = 112.5 KJ fi log 2 = 1.1555 ¥ 10-3 s -1
10 ¥ 60
K Ea È T2 - T1 ˘
15. (c) log 2 =
K1 2.303R ÍÎ T1T2 ˙˚
0.693
\ t1/2 = 600 sec
K
1.5 ¥ 104 60 ¥ 103 È T2 - 283 ˘ 20. (c) Since P0 + x = 120
log =
4.5 ¥ 103
2.303 ¥ 8.314 ÍÎ 283 ¥ T2 ˙˚ 2.303 100
K= log
on solving T2 = 297.02 K 10 80
Ea 21. (b) DH = 0.12 ¥ 10 cal
3
16. (a) log k = log A – (i)
2.303RT DH = Eaf – Eab
Given A = 1.26 ¥ 1013 Eaf = 0.14 ¥ 103 cal
Ea = 58.5 kcal % of molecules crossing over the barrier
T = 527 + 273 = 800 K - Eaf /RT
= 100 ¥ e
Substituting these values in Eq. (i), we get
= 80.65 ª 81
58.5 ¥ 103
log k = log (1.26 ¥ 10 ) –13
22. (c) Ea > Ea1
2.303 ¥ 1.987 ¥ 800
= 13.1003 – 15.9799 = –2.8796 1 d (ln k ) E 1 d (ln k ) E
= a2 , = = a2
k = 1.3194 ¥ 10–3 sec–1 k1 dT RT1 k2 dT RT2
0.693 E¢ E
t1/2 = ¥ 103 sec = 525 sec 1 d (ln k )
= a2 ,
1 d (ln k )
= a2
1.3194 k1¢ dT RT1 k2 dT RT2
n
Ê 1ˆ 1 k2 k2¢ k¢ k¢
17. (c) Amount of A left in n1 halves = Á ˜ [ A0 ] fi > fi 1> 2
Ë 2¯ k1 k1¢ k1 k2
n
Ê 1ˆ 2 Alternate method
Amount of B left in n2 halves = Á ˜ [ B0 ]
Ë 2¯ k¢1 > k1 and k¢2 > k2 since Ea always + ve
At the end, according to the question For Endothermic reaction DH = + ve
[ A0 ] [ B0 ] 4 1 \ on increasing temperature keq ≠
= n fi n = n , [[A0 ] = 4[ B0 ]]
2n1 22 21 22 k1 k1¢
[ K eq ]1 < [ K eq ]2 \ <
2n1 k2 k2¢
\ = 4 fi 2n1 - n2 = (2) 2 \ n1 - n2 = 2
2n2 Ea
\ n2 = (n1 – 2) (i) 23. (b) log k = log A -
2.303RT
Also t = n2 ¥ t1/2(B) log A = 14.71
(Let concentration of both become equal after time t)
3031
n1 ¥ t1/2( A) n ¥5 n 4 = 14.71 -
\ =1fi 1 =1fi 1 = 3 (i) T
n2 ¥ t1/2( B ) n2 ¥ 15 n2

1 1 1 k1 log 2 0.3
24. (b) = Kt + = 1 ¥ 10- 2 ¥ 100 + = 11 = =
[ A] [ A0 ] 0.1 k2 2 log 10 - 2 log 2 1.4
[A] = 0.09M k2 1.4
= = 4.65
1 ¥ 10-2 k1 0.3
25. (d) Fraction of one product = = 0.25
1 ¥ 10 –2 + 3 ¥ 10-2 34. (d) P(mm Hg) 500 250
3 ¥ 10-2 t1/2 (in min.) 235 950
Fraction of another product = = 0.75
1 ¥ 10-2 + 3 ¥ 10-2 1
Overall activation energy is t1/2 μ n -1
a
0.25 ¥ 60 + 0.75 ¥ 70 n -1 n -1
= = 67.5 kJ/mol (t1/2 )1 Ê a2 ˆ 235 Ê 250 ˆ
0.25 + 0.75 = =Á ˜
(t1/2 ) 2 ÁË a1 ˜¯ 950 Ë 500 ¯
26. (b) Tav = 1 = 1.44 ¥ t1/2 n–1 = 2 fi n = 3
K 22 = (2)n–1
35. (b) t1K1 = t2K2 20 ¥ K1 = 5 ¥ K2
t99.9 = 10 ¥ t1/2 in case of first order reaction = 6.9 Tav
K1
27. (b) t1/2 μ a in case of zero order reaction \ -4
K2
- Ea 1
28. (c) Slope = =- \ Ea = R ÊK ˆ Ea Ê T2 – T1 ˆ
2.303R 2.303 log10 Á 2 ˜ =
29. (a) At 50% inversion Ë 1¯
K 2.30 ¥ R ÁË T1 ◊ T2 ˜¯
a Ea Ê 20 ˆ
x= log10 (4) =
2 8.314 ¥ 2.3 ÁË 300 ¥ 320 ˜¯
r - r0
r - rt = Ea = 55.332 KJ/mole
2 36. (b) K = 3.0 ¥ 10–4 s–1; Ea = 104.4 kJ mol–1
\ r0 = 2rt – r A = 6.0 ¥ 1014 s–1 K2= Ae–Ea/RT
30. (b) Conceptual But when Ea Æ 0
31. (d) A (g) m 2B (g) - Ea
-0
10–5 mole 100 mole K = Ae RT = Ae RT = A

Kf = 1.5 ¥ 10–3 s–1 \ K = A = 6 ¥ 1014 S–1
[100] 2Kf 1 È 1 1 ˘
K= = 37. (a) k = -
10 ¥ 10 K b
–5 t (n - 1) ÍÎ C n -1 C0n -1 ˙˚
1.5 ¥ 10-3 ¥ 10-7 1 È 2 n -1 1 ˘

Kb = t1/2 = Í n -1 - ˙ (i)
104 k (n - 1) Î Co Co n -1 ˚
Kb = 1.5 ¥ 10–11 L mol–1 s–1
1 È 4 n -1 1 ˘
32. (b) A + B h C + D t3/4 = Í n -1 - ˙ (ii)
rate = K[A]1/2[B]1/2 k (n - 1) Î Co Co n -1 ˚
dx Eq. (ii) ∏ Eq. (i)
= K (a - x)(a - x)
dt t3/4 È 4n -1 - 1˘ 22( n -1) - 1 (2n -1 + 1)(2n -1 - 1)
=Í ˙= =
dx t1/2 Î 2n -1 - 1˚ (2n -1 - 1) (2n -1 - 1)
= K (a - x)
dt
t3/4= t1/2 [2n–1 + 1]
2.303 Ê a ˆ Ê Cˆ
fi t= log10 Á 38. (a) Fraction of reactant consume f = Á1 - ˜
K Ë a - x ˜¯ Ë C0 ¯
2.303 Ê 1 ˆ df
t= log10 Á = K (1 - f ) (Remaining amount).
Ë 0.25 ˜¯
-3
for a reaction:
2.31 ¥ 10 dt
t = 600 sec 39. (d) 2A
K
+ B ææÆ C + D
k1
33. (d) X ææ k2 t=0 C0 2 C0
Æ A + B and Y ææ ÆC + D
C0 7C0
k1 log(2) t = 30 min,
= 2 4
k2 log(100/4)
Rate at that time = K[A] [B]2

2 3 K1
È C ˘ È 7C ˘ 49C0 ¥ 100 = 76.83%
Rate = K Í 0 ˙ Í 0 ˙ = 46. (b) % B =
K1 + K 2
Î 2 ˚Î 4 ˚ 32
40. (d) AÆB KA = 1015 e–2000/T % C = 100 – B% = 23.17%
CÆD KA = 1014 e–1000/T or %C=
K2
¥ 100
At T (KA = KC) K1 + K 2
1015e–2000/T = 1014 e–1000/T dt
47. (b) = a –lN,
10e–2000/T = e–1000/T dt
dN
10 = e1000/T For maximum number of nuclei =0
dt
1000 Ê 1000 ˆ a = lN fi N = a/l
T= T =Á
Ë 2.303 ˜¯
loge10 = 1000/T K
log e10 48. (d) Let n is the moles of reagent ‘R’ when R is reacted
K 2 2.303Ea Ê T2 - T1 ˆ with A at time t = 0
41. (c) log10 = ÁË T T ˜¯ A h B + C
K1 R 1 2
t=0 n 0 0
R log 2 ¥ 280 ¥ 290 at t n–x 2x 3x
= Ea
2.303 ¥ 10 at t Æ 0 2n 3n
K 4 2.303 ¥ R log 2 ¥ 280 ¥ 290 Ê 10 ˆ n2
log = \ 5n = n2 fi =
K3 2.303 ¥ 10 ¥ R ÁË 290 ¥ 300 ˜¯ 5
n1 - n
Ê K ˆ 280 n + 4x = n1 fi =
log10 Á 4 ˜ = log 2 4
Ë K3 ¯ 300
2.303 Ê n ˆ
K K= log Á
\ 4 = 1.91 t Ë n - x ˜¯
K3
1 Ê 4n2 ˆ
42. (c) so K = ln Á
A + 2B Æ products t Ë 5(n2 - n1 ) ˜¯
a–x 2a – 2x 49. (c) Overall rate constant = k = k1 + k2 + k3= 6.93 ¥ 10–3
d [ A] 0.693
- = K [ A] [ B] t1/2 = = 100 sec
dt 6.93 ¥ 10-3
Reactants are in their stoichiometric proportion
d (a - x) After half-life, PB + PC + PD = 4 atm
fi - = K (a - x) 2(a - x)
dt PB k1 200
= =
dx 0.693 PB + PC + PD k1 + k2 + k3 693
= 2 K (a - x) t1/2 =
dt 2K 200
PB = 4 ¥ = 1.154 atm
- d [ A] 693
43. (a) 2A + B Æ = K[A]
dt
A = A0e–Kt when t2 = 1/K
–1
LEVEL III
A = A0e A = A0/e = C0/e
44. (c) Rate = K[A][B2]
1. (A - q, t); (B - p); (C - r); (D - s)
[ A]2 (a) 11Na23 + 1H2 h 11Na24 + 1H1
K= fi [A] = {K[A2]}1/2
[ A2 ] (b) 21H3 h 2He4 + 20n1
1
r = K¢[A2]1/2 [B2] order = 1 (c) 92U238 h 90Th234 + 2He4
2
(d) 29Cu63 h 28Ni63 + 1e0
100
45. (a) For A K1 ¥ t = ln (i) 2. (A - p); (B - q); (C - r); (D - s)
100 - 94
2.303 A
100 k= log 0
For B K2 ¥ t = ln (ii) t At
100 - 50
Eqs. (i) and (ii) 3. (A - q); (B - r, t); (C - s); (D - p)
100 (A – q): Decomposition of H2O2 follows first order ki-
ln
K1 6 fi K1 = 4.058 netics.
=
K 2 ln 100 K2 (B – r, t): It is temperature coefficient and lies between
50 2-3.

k
K2 Ea Ê T2 - T1 ˆ A ææ 1Æ C
(C – s): log = is Arrhenius equa-
K1 2.303R ÁË T1T2 ˜¯ [A]0 = [A]t + [C]t
tion 0.6932
(D - p): t99.9% = 10t1/2 K1 = \ t1/2 = 300 sec. = 5 min.
t1/2
2.303 R0 half-life of the reaction is 5 min.
t99.9% = log
K 0.1 In four half-lives the amount of C formed is 1.875 M.
R0 ¥
100 12. (c) Formation of B is independent of initial concentra-
2.303 2.303 ¥ 3 6.909 tion it is first order, fraction of ‘c’ also does not change,
= ¥ log 1000 = = it is also first order
K K K
È 0.693 ˘ K1
t 99.0% = 10 ¥ Í = 10 ¥ t1/2 13. (a) = 0.112 fi K1 = 1.7 ¥ 10-5 s -1
Î K ˙˚ 1.52 ¥ 10- 4
4. A-r, B-s, C-q, D-p K2
14. (d) = 0.888 fi K 2 = 1.35 ¥ 10- 4 s -1
for nth order (n π 1) 1.52 ¥ 10- 4
1 È 1 1 ˘ 15. (a) Rate = kf[O3][O]
K= -
(n - 1)t ÍÎ (a - x) n -1 a n -1 ˙˚ K eq [O3 ]
[O 2 ][O]
K eq = ; [O] =
5. A-rs, B-t, C-p, D-q [O3 ] [O 2 ]
1 Rate = kf Keq[O3]2 [O2]–1
t1/2 of nth order =
( a ) n -1 \ order = 2 + (–1) = 1
6. (d) (Ea)b = 30 + 10 = 40 kJ/mole 16. (a) moleculatiry of complex reaction has no signifance
7. (a) DH = –10 KJ 17. (b) Rate = k¢[O3]2 [O2]–1
\ reaction is exothermic It means as concentration of O2 increases rate decreases.
Ea 18. (c) Rate = k1[NO2][NO3]
- RT
8. (b) K f = A f e [NO 2 ][NO3 ]
-4 -4 K eq =
Kf 10 10 [N 2O5 ]
Af = = 30 ¥ 1000
=
e -11.27
Ea
- RT - Keq[N2O5] = [NO2] [NO3]
e 8.314 ¥ 320
e \ Rate = k1 Keq [N2O5]
= 10-4 ¥ e11.27 \ order = 1
\ log Af = – 4 + 4.8614 = 0.8614 = log 7.3 19. (a) K =
2.303 A
log 0 =
2.303
log
100
\ Af = Kf = 7.3 t At 20 20
9. (d) 2.303
CH3OCH3(g) h CH4(g) + CO(g) + H2(g) = ¥ 0.6990 = 0.08
20
Initial p0 – – –
at time t p0 – x x x x 20. (a) N2O5 m NO2 + NO3
after long 0.4 ¥ 0.4
K eq = = 0.8
time – p0 p0 p0 0.2
given 3p0 = 1.2 \ p0 = 0.4 atm Since K = K1 ¥ Keq = 0.08
0.693 -1 \ k1 = 0.1
also K = h
0.2 21. (a) On increasing temperature number of effective col-
lision increases which increases rate of chemical reac-
2.303 p0
K= log tion.
t p0 - x 22. (a) Molecular collisions are random and hence it is not
\ x = 0.35 possible that 100% reactant molecule can convert into
\ PT = 0.4 – 0.35 + 0.35 + 0.35 + 0.35 = 1.1 atm product.
10. (a) Rate = K ¥ P o 23. (a) Specific activity is defined as decay per second per
gram of radioactive isotope.
0.693 24. (a) Order of reaction is an experimental quantity.
= ¥ 0.4
0.2 25. (a) Half-life is independent of initial concentration.
= 1.386 atm h -1 26. (a) Like y = mx + c
11. (d) Since k2 >> k1, therefore given sequential reaction 27. (c) When reactant molecules collide among themselves
converts as follows: then, only they can convert themselves in to product if

Effective collision occur for Effective collision Reac- \ rate = 2 ¥ 10–6 [0.06][0.18]2
tant must have minimum threshold Energy and mol- = 3.89 ¥ 10–9 mol–2 L–1sec–1
ecule should be properly oriented. 37. (a, c, d)
28. (a) (i) As Rate = k[NO]2 order = 2 and unit of k = (con-
NO2 æææ
Æ NO + O
slow centration)–1 sec–1
Fast
(ii) As Rate = k[H2O2][I–] overall order = 2 and unit
CO + O æææ Æ CO
2 of k = (concentration)–1 sec–1
29. (c) Activation energy does not depend on temperature. (iii) As Rate = k[CH3CHO]3/2 order = 3/2 and unit of k
30. (a) –rA = (2.5R(400))CA at 400 K = (concentration)–1/2 sec–1
–rA = (2.5R(600))CA at 600 K (iv) As Rate = k[C2H5CI] order = 1 and unit of k =
n P sec–1
Since [A] = CA = A = C A = A 38. (b, c, d) For first order, t1/2 is independent of initial
V RT
concentration.
Ê 6ˆ Ea Ê 1 1 ˆ
then log Á ˜ = -
Ë 4 ¯ 2.303R ÁË 400 600 ˜¯
2
dx È1 ˘
= k[4Zn] Í H + ˙ = K[Zn][H + ]
Ea = 4135 J dt Î2 ˚
- Ea dx
31. (b) K = Ae RT = k[Zn][2H + ]2 = 4K[Zn][H + ]2
dt
If Ea = 0 then K = A
39. (a, b, c) K = Ae–Ea/RJ
-3
2 ¥ 10 40. (a, c) Collisions are necessary to bring about the chem-
32. (b, c) =2
1 ¥ 10-3 ical reaction.
41. (a, b, c, d) Factors affecting the rate of reaction
Ea 2000
33. (c, d) log k = log A - =5- 42. (a, b) k1 = k2
2.303RT T
\ log A = 5 2
fi rd of A has reacted for [A] = [C] = [D]
A = 105 3
Ea = 9.152 kcal 1 [ A0 ]
k1 + k2 = ln
1 1 t 1/3[ A0 ]
34. (a, d) k = ln fi - kt = ln(1 - a )
t 1- a 1 1 1
fi t= ln 3 = ln 3 = ln 3
\ 1 – a = e–kt k1 + k2 2k1 2k 2
\ a = 1 – e–kt 43. (a, c) DH = Eaf – Eab if DH = – ve
- E / RT
also k = Ae a Eab > Eaf and If DH = + ve Eab < Eaf.
35. (a, b, c, d) 44. (a, b, d) use
1 d [ A] d [ B] 1 d [C ] 1 d [ D] PV = nRT
Rate of reaction = - =- = =
2 dt dt 2 dt 3 dt - DH
and KP = Ae RT
d [C ] 45. (b, c) R μ K
As = 1.0 mol L-1 sec-1
dt - Ea
d [ A] d [C ]
K = Ae RT
- = = 1.0 mol L-1 sec -1 \ on increasing temperature rate constant increases
dt dt
\ Rate increased.
d [ B] 1 d [C ]
- = = 0.5 mol L-1 sec -1 46. (a, d) Rate = K[A]1 [B]0
dt 2 dt For I 2 ¥ 10–2 = K[0.1] [0.1]0
d [ D] 3 d [C ] -1 -1 For II 4 ¥ 10–2 = K[x] [0.2]0
\ = = 1.5 mol L sec
dt 2 dt \ x = 0.2 M
1 d [C ] For IV 2 ¥ 10–2 = K [y] [0.2]0
Rate of reaction = = 0.5 mol L-1 sec-1 .
2 dt \ y = 0.1 M
36. (a, b) Rate = k[A][B]2 47. (a, b, c, d) See Example of fractional order in theory
Initial rate = 2 ¥ 10–6 [0.1][0.2]2 48. (a, b, c, d) See Example of first order in theory
= 8 ¥ 10–9 mol L–1 sec–1 49. (a, c) See zero order in theory.
Now as [A] is reduced to 0.06 mol L–1, i.e., 0.04 mol 2.303 a
50. (a, c) Use K = log –
L–1 of [A] is reacted t a-x
2 moles A reacts with 1 mole B.
\ 0.04 moles of A reacts with 0.02 moles of B 0.31 - 0.17
rate = = 4.67 ¥ 10–3
\ [B]left = 0.2 – 0.02 = 0.18 60 - 30

51. (a, b, d) 57. (3) The sum of mass number and atomic numbers of re-
actants = The sum of mass number and atomic number
1
(a) t 1 μ n -1 of product in a nuclear reaction.
2 a
Hence the given nuclear fission reaction is
1
(b) Tav = = 1.44 ¥ t1/2
235
92 U + 10 n ææ
Æ 139
54 Xe +
94
38Sr + 310 n
K
58. (6)
(c) t3/4 = 2 ¥ t1/2 for 1st order Ea
(d) t99.9 = 10 ¥ t1/2 for 1st order log K = log A -
2.303RT
52. (a, b, c) Order is experimental and determined by ex- (T )
periment only.
In the expression of rate law, order is defined as (coef- When log K = log A
ficient) of active mass. A0
aA + bB h P 59. (9) ln = (k1 + k2 )t
A
Rate = K[A]m [B]n
A+ B+C
m = Order w.r.t. A ln = 9a
n = Order w.r.t. B A
(m + n) = overall order of reaction A + 8C + C
ln = 9a
Order of any reaction can be obtained only by experi- A
ment methods. (C ) e9 a - 1
Order of reaction may have –ve, +ve, zero or fractional \ =
( A) 9
value
60. (80) Since it is a first order
53. (b, c) At Ea = 0, K = A
Also at very high temperature K = A \ rate = K[N2O5] = 3 ¥ 10–2 [N2O5]
= 2.4 ¥ 10–5
- Ea
Since K = Ae RT 2.4 ¥ 10-5
\ [N 2O5 ] = = 80 ¥ 10-5
54. (5) For reversible reaction rate constant is also reverse. 3 ¥ 10-2
1 1 61. (a) N2 + 3H2 h
Kr = = =5 3
K f 0.2 D[NH3 ]
Rate = = 2 ¥ 10–4 mol L–1 s–1
N0 N0 Dt
55. (6) N = = \n = 6
64 26 D[H 2 ] -1 D[H 2 ] 1 D[NH3 ]
- = =
Ê 1ˆ
n dt 3 dt 2 dt
We known Nt = N0 Á ˜ D[N 2 ]
Ë 2¯ = 1 ¥ 10 mol 1 sec -1
-4 -1
DT dt
7
(r ) Ê m ˆ 10 Ê 2.5 ˆ D[H 2 ]
56. (5) 2 95 = Á 2 ˜ = Á 3
(r1 )95 Ë m1 ¯ Ë 2.0 ˜¯ (b) - = - ¥ 2 ¥ 10-4 mol L-1s -1
dt 2
= 4.76 ª 5 = -13 ¥ 10- 4 Mol L-1S-1
OR
1
at temp rxn (I) rxn (II) 62. N2O5 (g) h 2NO2 (g) + O2 (g)
25°C r r 2
35°C 2r 2.5r –d[N2O5]/dt = k1[N2O5]
45°C (2)2r (2.5)2r d[NO2]/dt = k2[N2O5]
55°C (2)3r (2.5)3r d[O2]/dt = k3[N2O5]
65°C (2)4r (2.5)4r
(2)5r (2.5)5r d N 2O5 1 d NO 2 d O2
75°C - = =2
85°C (2)6r (2.5)6r dt 2 dt dt
95°C (2)7r (2.5)7r K2
K1 = = 2K 3
Rate of reaction (II) 2
Ratio of rates =
Rate of reaction (I) 2K1 = K2 = 4K3
63. 2A + B + C Æ D + E
(2.5)7 r
= = 4.77 ª 5
(2)7 r (i) dx = K1[ A][ B]2 [C ]0 = K1[ A][ B]2
dt

(ii) if concentration increases two times. \ k2 = 3.87 ¥ 0.01438 = 0.05571

dx
= K1[2A][2B]2[2C]0 = 8K1 [A][B]2 k2 = 0.05571 =
2.303
log
100
dt 20 100 - y
fi rate increases by 8 times
64. A h B K = 1.2 ¥ 10–2 M s–1 y = 67.17
Initially = 10 M 68. (i) A h
From the unit of rate constant, we find that reaction is (ii) B h
of zero order X1= kt. Êk ˆ Ea È 10 ˘
\ remaining = (10 – 1.2 ¥ 10–2 ¥ 10 ¥ 60) = (10 – 7.2) M log Á 2 ˜ = Í ˙
Ë 1¯
k 2.303 R Î 310 ¥ 300 ˚
[Remaining mole = 2.8 M]
If 10 = 1.2 ¥ 10–2 t log 2 ¥ 2.303 ¥ 8.314 ¥ 310 ¥ 300 = Ea
Ea = 53.6 kJ/mole
1000
\t= at t = 13.88 min reaction complete Ê 0.693 ˆ
60 ¥ 1.2 kA2 = Á min -1
Ë 30 ˜¯
\ after 20 min (13.88 min) contraction of reactant 0 M
Ê 0.693 ˆ
kB 2 = Á min -1
Ë 15 ˜¯
Ea
65. H2O + O 2HO° DH = 72 kJ
Eb
53.6
Ea = 26.8 kJ/mole =
Eab 2
Eaf k2 Ea È –10 ˘
log =
DH k B 2.303R ÍÎ 310 ¥ 300 ˙˚
Êk ˆ – 26.8 ¥ 1000
log Á 2 ˜ =
T = 500 K Ë k B ¯ 2.303 ¥ 8.314 ¥ 300 ¥ 310
Eaf = 77 kJ/mole fi DH = Eaf – Eab k2
72 = 77 – Eb log = – 0.151 = log (0.706)
kB
Eab = 77 – 72
Eab = 5 kJ Ê 0.706 ¥ .693 ˆ -1
\ k2 = Á sec
66. 2NO + Br2 h Ë 15 ¥ 60 ˜¯
(i) NO + Br2 m NOBr2 (Fast) k2 = 0.0327 min–1
(ii) NOBr2 + NO
Slow
2NOBr 69. 2H2O2 h 2O + O2
mili equivalent of H2O2 in 10 mL diluted solution
Rate is determined by the slowest step
= mili equivalent of KMnO4 titrated = 25 ¥ .025 ¥ 5 =
fi Rate = K[NOBr2][NO]
3.125
But NOBr2 here exist inform of intermediate.
mili equivalent in 100 mL solution = 31.25
[NOBr2 ] but 22400 mL O2 = 68 gm H2O2
\ KC = fi Rate = k1[NO]2[Br2]
[NO][Br2 ] 68
1 mL =
fi Rate = k1[NO]2 [Br2] and k1 = K ¥ KC 22400
fi 3rd order Reaction 68 ¥ 20
67. A h Ea = 70 kJ/mole t1/2 = 40 min 20 mL = ln 1 mL H 2O 2 solution
22400
K1 =
2.303 100
= 0.01438 min -1 68 ¥ 20 ¥ 10
log = in 10 mL H 2O 2
20 0.75 22400
k2 Ea Ê T2 - T1 ˆ Number of mili in 10 ml of 20 volume H2O2 solution
log10 =
k1 2.303R ÁË T1T2 ˜¯ Initially =
68 ¥ 20 ¥ 10 ¥ 1000
= 35.71
17 ¥ 22400
70 ¥ 103 È 15 ˘
=
2.303 ¥ 8.314 ÍÎ 298 ¥ 313 ˙˚ fi K=
2.303 Ê 35.71ˆ
log Á
6 Ë 31.25 ˜¯
k2
= 5.88 ¥ 10- 4 ¥ 103 = 100.588 K = 0.022 hr–1
k1
70. Initial m mol of cyclobutene = 10
k2 Let after 20 min, x m mol cyclobutene isomerised.
= 3.87
k1 m mol of cyclobutene left = 10 – x and m mol of diene
formed = x

No of millimoles of Br2 required ka

= No of millimoles of p bond in substance 73. N2O5 NO2 + NO3
k- a
m mol of Br2 required after 20 min = 10 – x + 2x = 10 k
NO2 + NO3 ææ
b
Æ NO2 + O2 + NO
+ x = 16 \ x = 6
k
fi 2a = 20 (only 1, 3 butadiene present) NO + NO3 ææ
c
Æ 2NO2
10 - d [N 2O5 ]
\ a = 10, 20 K = ln (i) dt
= ka [N2O5] – k–a [NO2][NO3] (i)
4
If y m mol of cyclobutene isomerized after 30 min. d [NO3 ]
= ka [N2O5] – k–a [NO2][NO3] – kb [NO2]
10 dt
30 K = ln (ii)
10 - y [NO3] – kc [NO][NO3] = 0 (ii)
From Eqs. (i) and (ii) y = 7.47 d [NO]
= kb[NO2][NO3] – kc[NO][NO3] = 0 (iii)
fi m mol of Br2 required = 10 + y = 17.47 dt
fi Volume of bromine solution required = 17.47 mL From Eq. (iii)
- 14000 - 20000 k
71. 102 e RT = 103 e RT Solving [NO] = b [NO 2 ]
kc
T = 313.42 K
Putting this in Eq. (ii)
fi Rate constant K1 = K2 = 0.464 hr–1
ka[N2O5] = [NO3]{ka[NO2] + 2ka[NO2]
n0 ( A2 )
fi K1t = ln fi n1 = 0.37 [NO3 ] =
ka [N 2O5 ]
n0 ( A2 ) - n1 k- a [NO 2 ] + 2kb [NO 2 ]
n0 ( B3 ) Putting this in equation (i)
K2t = ln fi n2 = 0.37
n0 ( B3 ) - n2 - d [N 2O5 ] k k [N O ]
= ka[N 2O5 ] - a - a 2 5
fi dt k - a + 2 kb
3.11 - d [N 2O5 ] 2ka kb [N 2O5 ]
n RT 3.11 ¥ 0.0821 ¥ 313.42 =
P= T = = 8 atm dt k - a + 2 kb
V 10 -1 d [N 2O5 ] ka kb [N 2O5 ]
72. Let rate constant in absence of catalyst is k1 r= =
2 dt k - a + 2 kb
Let rate constant in presence of first catalyst is k2
Let rate constant in presence of second catalyst is k3 74. t2 at + b
dt dt a a
k1 ¥ 1 = ln
100
fi k1 = 0.2231 hr–1 (i) 2t =a fi = = (t ) -1
80 dt dt 2t 2
80 order = –1
k2 ¥ 0.5 = ln fi k2 = 1.3862 (ii) 75. Given: r = k¢ [complex]a
40
and since t3/4 = 2t1/2
k3 ¥ 1 40 so a=1
= ln fi k3 = 8.317 (iii)
6 10 ln 2 ln 2
t1/2 = =
k1 = Ae–80,000/RT k¢ k[H + ]b
- E / RT On doubling concentration of [H+] ion t1/2 gets half so
k2 = Ae a1 Ea1 Æ Activation energy in presence of
b=1
First catalyst
76. Let at 20°C rate constant = K
k 80,000 - Ea1 1.3862
ln 2 = = ln Then at 3°C rate constant = K/3
k1 RT 0.2231
K E È 1 1 ˘
ln = aÍ - fi Ea = 43.45 kJ
Ea1 = 75443.8 J = 75.44 kJ K /3 R Î 276 293 ˙˚
- Ea / RT
k3 = Ae 2 Ea2 Æ Activation energy in presence of Let at 40°C rate constant is K1 then
Second catalyst K1 43.45 ¥ 103 È 1 1 ˘
ln = -
k 80,000 - Ea2 8.317 K 8.314 ÎÍ 293 313 ˚˙
ln 3 = = ln
k1 RT 0.2231 K1 = 3.125 k
64
Ea2 = 70974.9 J = 70.975 J So time required for juice to get spoil at 40°C =
3.125
= 20.47 hr.

77. CH3OCH3 h CH4 + CO + H2 82. 76.8%

K1
t=0 0.4 Cyclohexane
t = 4.5hr. 0.11 0.29 0.29 0.29 Bicyclohexane
K2
P 0.4 Methylcyclopentene
kt = ln 0 fi ¥ 10–3 ¥ 4.5 ¥ 60 = ln
P P KAV = K1 + K2 = 1.26 ¥ 10–4 + 0.38 ¥ 10–4 = 1.64 ¥ 10–4
P = 0.11 atm K1 ¥ % of Cyclohexane = K
at t = 0 P0 = 0.4 K 1.26 ¥ 10- 4
M0 = 46 Fraction of cyclohexane = 1 = = 0.768
K 1.64 ¥ 10- 4
at t = 4.5 hr. P = 0.11 + 0.29 ¥ 3 = 0.98 atm
Fraction of methyl cyclopentene
0.11 ¥ 46 + 0.29(16 + 28 + 2)
M= = 18.77 K 2 0.38 ¥ 10- 4
0.98 = = = 0.232 .
K 1.64 ¥ 10- 4
R0 P0 M 0.4 18.77
= = = 0.26 83. 20.39
R P M 0 0.98 46
K2 Ea Ê T2 - T1 ˆ
log =
k1 B K1 2.303R ÁË T1T2 ˜¯
78. A k = k1 + k2
k2 C 84. (i) 6.23 ¥ 10–3 sec–1 (ii) 0.033 atm
0.693 0.693 0.693 2.303 0.062
= + \ K= log10
t1/2 60 90 55 0.044
t1/2 = 36 min. 2.303 0.062
K = 6.23 ¥ 10-3 sec -1 = log
79. Bn+ h B(n+4)+ 100 PCl2O 7
t=0 a – 85. 5.25% and 128.33 hr
t = 10 min. a – x x
0.693 0.693
v.f. of Bn+ = |(n – 2) – n| = 2 t1/2 = = = 462000 sec = 128.33 hr.
v.f. of B(n+4)+ = |(n + 4) – (n – 1)| = 5 K 1.5 ¥ 10- 6
Let normality of reducing agent = N
so 2a = 25N \ a = 12.5 N PREVIOUS YEARS’ QUESTIONS
2(a –x) + 5x = 32N
OF JEE (MAIN & ADVANCED)
7
2a + 3x = 32N N x= 1. (b, c) Characteristic of catalyst
3
n 4
a 12.5 N 1 Ê 1ˆ Ê 1ˆ
K ¥ 10 = ln = ln 2. (d) g or Nt = N 0 Á ˜ = 1 ¥ Á ˜
a-x 7 16 Ë 2¯ Ë 2¯
12.5 N - N
3 140 1 140 1 140 1 140 1
–1
1 ææÆ ææÆ ææÆ ææÆ
K = 0.02 min . 2 4 8 16
80. For reaction 1 3. A h B Ea = 70 kJ/mole
k2 = k1e
(
+ Ea / R T1 - T1
1 ) = 2.79 ¥ 10- 3 e6000( 1 -1
509 T ) K1 =
2.303
log
100
= 0.01438 min -1
20 75
For reaction 2 k Ea Ê T2 - T1 ˆ
log10 2 =
k2 = 1.52 ¥ 10- 4 e
(
12250 1 - T1
510 ) k1 2.303R ÁË T1T2 ˜¯
For given condition 70 ¥ 103 È 15 ˘

=
2.303 ¥ 8.314 Î 298 ¥ 313 ˙˚
Í
2.79 ¥ 10-3 e
(
6000 1 - T1
509 ) = 1.52 ¥ 10- 4 e12250( 5101 - T1 )
k2
= 5.88 ¥ 10-4 ¥ 103 = 100.588
18.355 = e
(
12250 510 T )
1 - 1 - 6000 1 - 1
509 T ( ) k1
k2
6250 = 3.87
ln 18.355 = 12.33 – = 2.9 k1
T
\ k2 = 3.87 ¥ 0.01438 = 0.05571
T = 670.6, K = 397.6°C
2.303 100
- d [ A] k2 = 0.05571 = log
81. = K1[ A] + 2 K 2 [ A]2 20 100 - y
dt
y = 67.17

4. (b) The species 13Al29 contains more neutrons than the

9. 282 K k = Ae - Ea /RT
stable isotope 13Al27
(means high n/p \ b decay) 157700 - 152300
2.303 log 10 =
0.6932 0.6932 8.314 ¥ T
5. At 380°C K1 = =
(t1/2 )1 360 \ T = 282 K
10. 3.4353 ¥ 10–3 M min–1
At 380°C K2 =
0.6932 k(a – x) = 4.5 ¥ 10–3 ¥ 0.7634
(t1/2 ) 2 = 3.4353 ¥ 10–3 M min–1
11. (d) As unit of k is sec–1, reaction is of the first order.
K2 Ea È 1 1˘
log = Í - ˙ 2.4 ¥ 10-5
K1 2.303R Î T1 T2 ˚ r = k[N2O5]; \ [N2O5] = -5
= 0.8 mol L-1
3 ¥ 10
K2 200 ¥ 1000 È 1 1 ˘ 12. 33.70 hr, 67.41 hr, 29.28 hr
log = ¥
0.6932 2.303 ¥ 8.314 ÍÎ 653 723 ˙˚ 64 64
30Zn , 28Ni , 28Ni
64
360 0.693
K 2 = 6.18 ¥ 10-2 min -1 t1/2 for b–-emission = = 33.70 hr
2.056 ¥ 10- 2
2.303 a 0.693
\ K2 = log t1/2 for b+-emission = = 67.41 hr
t 0.25a 1.028 ¥ 10- 2
t = 20.358 min 0.693
6. (a) Ea = 239.339 kJ mol–1 t1/2 for electron capture = = 29.28 hr
2.327 ¥ 10-2
(b) K = 2.18 ¥ 10–11 sec–1
13. (b) The rate of photochemical reaction μ intensity of
(c) T = 669 K
light.
(i) Ea = (1.25 ¥ 104 K)(2.303)(8.314 kJ–1 mol–1)
14. (a) 0n1 +1p1 + –1e0 or b–
= 239.339 KJ mol–1
Since n/p ≠
1.25 ¥ 104 \ b emission.
(ii) log K = 14.34 -
500 0.693 0.693
15. (c) Rate = K[X] = ¥ [X ] = ¥ 0.01
log K = –10.66 \ K = 2.18 ¥ 10–11 sec–1 t1/2 20
(iii) t1/2 =
0.693
fi K = 4.51 ¥ 10-5 s -1 = 3.47 ¥ 10–4 M min–1
K 0.1 M Æ 0.05 Æ 0.025 M
40 minute = 2 ¥ t1/2
1.25 ¥ 10-5 K
or –4.346 = 14.34 – , T = 669 K \ t1/2 = 20 min.
T
16. (c) 11 Na ææ
23
Æ 10
23
X + 10 b
7. Ea = 22.01 k mol–1 and A = 5.43 ¥ 1010 sec–1
17. (8) 92U238 h 82Pb214
K2 4.5 ¥ 10 7
Ea Ê 50 ˆ 238 - 214
log = log = Number of a particle =
2.303 ¥ 8.314 Ë 323 ¥ 373 ˜¯
Á = 6a
K1 1.5 ¥ 10 7
4
Number of b particle = 2 ¥ 6 – [92 – 82] = 2
\ Ea = 22.01 kJ mol–1
Total particles = 6 + 2 = 8
A = 5.43 ¥ 1010 sec–1
1
d [ B] 18. (d) Given log K = –2000 ¥ + 6.0
8. (3) = 2 K1[ A] T
dt Ea
2B
d [C ] K1 We know log K = - + log A
= 2 K 2 [ A] 2x 2.303RT
dt A K2 - Ea - 2000
[ B] K1 1 \ A = 106 and =
\ = = (2-x-y) 2C 2.303RT T
[C ] K 2 2 2y \ Ea = 2000 ¥ 2.303 ¥ 8.3 J = 38.3 KJ mol–1
\ [C]t = 2[B]t [ A]0
Total No of moles after 50% reaction 19. (9) For a first order process Kt = ln
[ A]
= [At] + [Bt] + [Ct] = (2 – x – y) + 2x + 2y
where [A]0 = initial concentration.
But x + y = 1
[A] = concentration of reactant remaining at time “t”.
\ 2x + 2y = 2
[ A]0
\ [At] + [Bt] + [Ct] = 1 + 2x + 2y = 3 fi Kt1/8 = ln = ln 8 (i)
[ A]0 /8

Kt1/10 = ln
[ A]0
= ln 10 Rate K [ M ]n
and (ii) =
[ A]0 /10 8 ¥ Rate K [2 M ]n
1 1
Therefore,
t1/8
=
ln 8
= log 8 = 3 log 2 =
t1/10 ln 10 8 [2]n
= 3 ¥ 0.3 = 0.9 fi [2]n = 8 = [2]3 fi n = 3

24. (d) This problem can be solved by determining the or-
fi t1/8 der of reaction w.r.t. each reactant and then writing rate
¥ 10 = 0.9 ¥ 10 = 9
t1/10 law equation of the given equation accordingly as
20. (8) Balancing the given nuclear reaction in terms of dC

R= = k[ A]x [ B] y
atomic number (charge) and mass number. dt
29Cu + 1H h 60n + 1He (a) + 21H + 26X
63 1 1 4 1 52 where, x = order of reaction w.r.t. A
y = order of reaction w.r.t. B
The atomic number 26 corresponds to transition metal
Fe which belongs to 8th group of modern periodic table. 1.2 ¥ 10–3 = k[0.1]x[0.1]y (i)
21. (d) Time of 75% reaction is twice the time taken for 1.2 ¥ 10–3 = k[0.1]x[0.2]y (ii)
50% reaction if it is first order reaction w.r.t. P. From 2.4 ¥ 10–3 = k[0.2]x[0.1]y (iii)
graph [Q], decreases linearly with time, thus it is zeroth y
(ii) Ê 2ˆ
order reaction w.r.t. Q. =1= Á ˜ \ y = 0
(i) Ë 1¯
dx
= K [ P]a [Q]b x
dt (iii) Ê 2ˆ
= 2 = Á ˜ \x =1
(i) Ë 1¯
Order w.r.t. P = a = 1
Order w.r.t. Q = b = 0 \ R = k[A]1[B]0
Thus, overall order of the reaction = 1 + 0 = 1. As shown above, rate of reaction remains constant as
22. (a) From Arrhenius equation, the concentration of reactant (B) changes from 0.1 M
K2 - Ea Ê 1 1ˆ to 0.2 M and becomes double when concentration of A
log = -
K1 2.303R ÁË T2 T1 ˜¯
change from 0.1 to 0.2. (i.e., doubled).
25. (a) The main conditions for the occurrence of a reac-
K2 tion is proper orientation and effective collision of the
Given, =2 reactants.
K1
Since, the chances of simultaneous collision with prop-
T2 = 310 K and T1 = 300 K er orientation between two species in high order reac-
On putting values, tions are very rare, so reaction with order greater than 3
- Ea Ê 1 1 ˆ are rare.
fi log 2 = Á - ˜
2.303 ¥ 8.314 Ë 310 300 ¯ R K
25. 2 = 1
fi Ea = 53598.6 KJ/mol = 53.6 KJ mol–1 R1 K 2
23. (b) For the elementary reaction, M h N È - Ea ˘
Rate law can be written as K2 Í Ae RT ˙
\ ln = ln
Rate μ [M]n K1 Í - EaRT+10 ˙
Î Ae ˚
Rate = K[M]n
K2 È - 10
˘
When we double the concentration of [M], ln = ln Îe RT ˚
Rate becomes 8 times, hence new rate law can be writ- K1
ten as -10 KJ -10 ¥ 1000
= = = 4.0093
8 ¥ Rate = K[2M]n RT 8.314 ¥ 300

Chapter
2
Electro-
chemistry
Key Concepts
This branch of chemistry deals with two types of conversion: Salt Bridge ______________________________
Conversion of chemical energy into electrical energy fi It is the U-tube filled with inert electrolytes like KNO3, KCl,
electrochemical cell NH4NO3, etc., mixed with gelatin or agar-agar.
Conversion of electrical energy into chemical fi electro-
Characteristics of electrolyte used in salt Bridge
lytic cell
1. Electrolyte should not be able to react with any ion in
Electrochemical cell/Galvanic cell/voltaic cell
either of the half-cell.
fi Electrical energy is produced from the chemical changes
2. Velocities of the cations and anions of the salt should
fi Maximum electrical work obtained from the electro-
be similar.
chemical cell = decrease in Gibb’s free energy.
Max. electrical work = –DG = nF Ecell Importance of salt-Bridge
n = Number of mole of e– involved in the transfer. 1. It completes the circuit by connecting two half cell.
F = Faraday constant 2. Maintain the electrical neutrality in two half cell.
3. It does not allow the intermixing of solution ion in the
= 96500 c
half cells.
Ecell = E.M.F. of the cell/cell-voltage
fi In Galvanic cell, spontaneous redox reaction takes place. Representation of Galvanic Cell
Daniel Cell: When Zn is anode and copper is cathode, electro 1. When metal electrode is dipped into its metal ion.
chemical cell is called Daniel cell. Metal/metal ion (C1) Metal ion (C2)/metal
Inert electrolyte
fi Oxidation occurs at anode, reduction occurs at cathode.
At anode: Zn Æ Zn+2 + 2e– oxidation half cell Salt bridge Reduction half cell
At cathode: Cu+2 + 2e– Æ Cu
Zn + Cu+2 Æ Zn+2 + Cu (cell reaction) Example Zn + Cu+2 Æ Zn+2 + Cu
fi Flow of e– from anode to cathode Zn/Zn+2 // Cu+2/Cu
fi Flow of i (current) from cathode to anode Example Zn + 2Ag+ Æ 2Ag + Zn+2
Zn/Zn+2//Ag+/Ag
2. When some gaseous species exist in the half cell reac-
tion then Pt electrode is used.
– + Example Cu+2 + H2 Æ 2H+ + Cu
Zn Salt bridge Cu Pt(H2)/H+//Cu+2/Cu
P1 atm
ZnSO4 CuSO4
Example 2H+ + 2e– Æ H2
H+/Pt(H2)
Anodic Half cell Cathodic Half cell Example 2Cl– Æ Cl2 + 2e–
Pt(Cl2)/Cl–

3. When only ions are present in the half-cell reaction Difference between E.M.F. of Cell and Potential Difference
then, use the Pt electrode.
Example Fe+2 Æ Fe+3 + 1e– E.M.F. Potential Difference
(Pt)/Fe+2/Fe+3 or Pt/Fe+2, Fe+3 (1) It is difference of two (1) It is difference of two
- electrode potentials of electrode potential,
MnO 4- æææ
Æ Mn +2
5e
Example
the galvanic cell when when there is current
MnO 4- /Mn +2 (Pt) there is no current flow flow in the circuit.
in the circuit, i.e., open
Electrode Potential (E) ____________________ circuit.
It is the Potential differ- (2) It is the maximum volt- (2) It is lesser than maxi-
ence between the metal and M
age obtained from the mum.
ions in the solution when cell.
a metal is dipped into its Mn+ + ne– M
metal ion. Mn+ (3) It is measured by poten- (3) It is measured by volt-
It is the measurement tiometer. meter.
of tendency of species for
oxidation or reduction. It can be of two types: E.M.F. of Cell or Cell Voltage
1. Reduction Potential (ER): E 0cell = (E A0 )oxidation potential + (E 0C)Reduction Potential
ER ≠ fi tendency for reduction≠ E 0cell = E (cathode)
0 0
– E (anode) if data in SRP
ER = –E0 0 0
= E (anode) – E (cathode) if data in SOP
2. Oxidation Potential (E0):
E0 ≠ fi tendency for oxidation≠ Electro-Chemical Series
ER = –E0 In this series, different species are arranged in the increasing
Standard Electrode Potential (E°): order of their standard reduction potential ( ERo ).
It is the electrode potential at S.T.P.
Li K Ba Ca Na MgAl Zn Fe Ni Sn Pb H Cu Mg Ag Au
T = 298 K
0 volt EoR = +ve
C=1M EoR = –ve
P = 1 atm or 1 bar
Note: Halogens
I Br Cl F
1. Electrode potential is intensive quantity: æææææææ
2
o
2 2 2
Æ
ER = increases
Ag+ + 1e– Æ Ag; o
EAg +
/Ag
= +0.80 volt
2Ag+ + 2e– Æ 2Ag; E° = +0.80 volt

APPLICATION OF
DG1 = –1 ¥ F ¥ 0.80 and DG2 = –2 ¥ F ¥ 0.80 ELECTRO-CHEMICAL SERIES
2. If direction of any cell reaction is reversed, mag-
nified of E remains same but sign will change: 1. Oxidising Power (μ ERo ):
Ag+1 + 1e– Æ Ag; E° = +0.80 V F2 > Cl2 > Br2 > I2 (order of oxidising power)
Ag Æ Ag+ + 1e–; E° = –0.80 V 2x– + Cl2 Æ 2Cl– + x2
3. Whenever two or more half-cell reactions are x = Br, 1
added. E is not additive in nature. So, it obtained 2. Reducing Power (μ E0o ) OR (μ 1/ ERo ) :
by DG:
HF < HCl < HBr < HI (order of reducing power)
Fe+3 + 1e– Æ Fe+2; E1o = +0.77 V 3. Displacement Reaction:
1
Fe+2 + 2e– Æ Fe; E2o = –0.44 V Generally, reactivity of metals μ o
ER
Fe+3 + 3e– Æ Fe; Eo = ?
(a) More reactive metal can displace lesser reactive
DG = DG1 + DG2
metal from its salt solution:
–nFE = –(n1FE1 + n2FE2) Zn + CuSO4 (Blue) Æ ZnSO4 + Cu
nE = n1E1 + n2E2 (Colour less)
fi 3 ¥ E = 1 ¥ 0.77 + 2 ¥ –0.44 Ag + CuSO4 Æ NO reaction
0.11 (b) Only those metals can displace the H from dilute
fi E=- V acids whose reactivity is more than H, i.e., having
3
- ERo .

Electro- chemistry 2.3
Zn + H2SO4 (dil) Æ ZnSO4 + H2 ≠ Half-Cell Reaction

Cu + H2SO4 (dil) Æ No reaction 2H+ + 2e– m H2
4. Feasibility or Spontaneity of Cell reaction:
H+/Pt(H2) or H+/H2/pt
For spontaneity DG = –ve = –nFEcell
fi Ecell = +ve 2. Calomel (Hg2Cl2) Electrode:
If Ecell = –ve fi non-spontaneous in the given direction Pt. wire
but spontaneous on opposite direction.
\ ERo lesser fi anode KCl
ERo more fi cathode Solution Paste of Hg2Cl2
If four elements w, x, y, z form diatomic molecule and
Hg
also form singly charged –ve ions. Following observa-
tions are made:
(a) 2x– + y2 Æ 2y– + x2 Half-Cell Reaction
(b) 2w– + y2 Æ no reaction 1
Hg 2 Cl2 (s) + 1e - Hg(l) + Cl- (aq.)
(c) 2z– + x2 Æ 2i– + z2 2
then the correct order of reduction potential and oxidis-
E.M.F. of this electrode depends on the concentration
ing power.
of KCl.
w>y>x>z
Representation
Whether under standard condition, following reaction are
possible or not: Cl–/Hg2Cl2/Hg/Pt When act as cathode
(i) Fe reduce Fe+3 to Fe+2 Factors Affecting Electrode Potential
Given:
fi Nature of electrode
ÏÔFe +3 + 1e - Æ Fe +2 ; E∞ = 0.77 V (cathode)
(i) Ì fi Temperature ˘
+2 -
ÔÓFe + 2e Æ Fe; E∞ = - 0.44 V (anode) fi Effect is given by Nernst equation
fi Concentration ˙˚
o
If Ecell = +ve fi Reaction Spontaneous
Nernst Equation
Fe+3 + Fe Æ Fe+2 + Fe+2
DG = DG° + 2.303 RT log Q
o
EFe +3
/Fe+2
+ E oFe/Fe+2
o
–nFEcell = – nFEcell + 2.303RT log Q
o
Ecell = [0.77] + [+ 0.44] = +1.21 V
2.303RT
(ii) MnO -4 ion literate O2 from H2O in presence of acid fi Ecell = Ecell
o
- log Q
nF
ÏÔMnO -4 + 8H + + 5e - Æ Mn +2 + 4H 2 O; E∞ = 1.51 V (Cathode) at 298 K
Ì + - R = 8.314, F = 96500 C
ÔÓ2H + 1/2 O 2 + 2e Æ H 2 O; E∞ = 1.223 V (anode)
0.0591
o
Ecell = EMnO
o
- +2 + EH 2O/O 2 = 1.51 + ( - 1.223) = 0.287 V
0 Ecell = Ecell
o
- log Q
4 /Mn n
Since Ecell o
= +ve fi Spontaneous For pure solids and pure liquids activity is taken as 1 and for
gas phase activity will be written in terms of partial pressure
REFERENCE ELECTRODE in atm or bar,
1. Zn + 2Ag+ h Zn+2 + 2Ag
0.0591 [Zn 2+ ]
Electrode potential of any electrode is measured with respect Ecell = Ecell
o
- log
to refrence electrode. 2 [Ag + ]2
1. Standard Hydrogen Electrode (SHE) or Normal = EZn/Zn +2 + E +
o o o
and Ecell Ag /Ag
Hydrogen Electrode (NHE):
2. Cu+2 + 2e– h Cu
H2 0.0591 1
1 atm or 1 bar Pt. wire E°
R=0 ECu 2 + /Cu = ECu
o
2+ - log
25°C
/Cu 2 [Cu +2 ]
3. Zn h Zn+2 + 2e–
0.0591
Acid sol. Pt. foil coated with EZn/Zn +2 = EZn/Zn
o
+2 - log[Zn +2 ]
[H+] = 1M pt block 2

Application of Nerst Equation Example (i) Zn/Zn+2(C1)//Zn+2(C2)/Zn

1. To find the equilibrium constant of cell reaction: Æ Zn + Zn+2 h Zn+2 + Zn
C2M C1M
Reduction half cell 0.0591
ER Ecell = Ecell
o
- log Q
n
State of equilibrium
- 0.0591 C 0.0591 C
Oxidation half cell
Ecell = log 1 = log 2
2 C2 2 C1
Progress of reaction 0.0591 [concentration] cathode
Ecell = log
at equilibrium: n [concentration] anode
fi DG = 0 fi Ecell = 0 C 2 > C1
fi No current flow in the circuit Example (ii) Pt/H2 1 atm/H+(C1)//H+(C2)/H2 1 atm/ Pt. fi
C2 > C1
0.0591
Ecell = E cell
o
- log Q Electrode Concentration Cell
n
0.0591 In these cells, driving force for the current flow is pressure
fi o
Ecell = log K eq. difference
n
Example Pt/H2 (P1 atm)/H+(1M)//H+(1M)/H2 (P2 atm)/Pt
2. To find PH of solution: H2 + 2H+ h 2H+ + H2
If the ECELL of following half-cell. P1 1M 1M P2
Pt(H2)1 atm/HCl; E = 0.25 V PH can be calculated as
- 0.0591 P 0.0591 P
H2 h 2H+ + 2e– Ecell = log 2 = log 1
n P1 2 P2
Since EHo + =0
2 /H P1 > P2
fi from Nenst equation
0.0591 [H + ] Metal-Metal sparingly (insoluble) soluble salt
Ecell = Ecell
o
- log electrode ________________________________
n PH 2
Example Silver-silver chloride electrode
0.0591 [H + ]2 In this electrode, silver wire is coated with AgCl
0.25 = 0 - log then, dipped into chloride ion solution.
2 1 atm
fi 0.25 = 0.0591 ¥ Ph Since Ph = –log[H+] Ag wire
0.25
fi Ph = = 4.23
0.0591
AgCl
CONCENTRATION CELLS
KCl Sol.
These are the galvanic cell in which both the two electrodes Reduction half-cell reaction: (when act as cathode)
are composed of same material so that always Ecell o
=0. AgCl(s) m Ag+ + Cl– ; DG1o
These can be of two types:
1. Electrolyte concentration cell Ag+ + 1e– m Ag ; DG2o
2. Electrode concentration cell
AgCl(s) + 1e– m Ag(s) + Cl– (aq.) ; DG3o
Electrolyte concentration cells
Representation
In these concentration cells, two identical electrodes are
Cl–/AgCl/Ag (when it acts as cathode)
dipped into metal ions of different concentration.
Ag/AgCl/Cl– (when acts as anode)
0.0591
ECl- / AgCl/Ag = ECl
o
- / AgCl/Ag - log[Cl- ] (1)
1
Electrode potential of this half-cell will depend only on con-
Zn Salt bridge Zn centration of KCl solution
DG3o = DG1o + DG2o
ZnSO4 CuSO4 fi -1 ¥ F ¥ ECl
o
- / AgCl/Ag = - 2.303 RT log KSP (AgCl)
C1M C2M
+ (-1 ¥ F ¥ EAg
o
+ / Ag )

2.303 RT Example Dry cell or leclanche cell

fi o
ECl - = EAg
o
+ + log K sp (AgCl) anode: Zn
/AgCl/Ag /Ag F
Cathode: graphite
0.0591 Electrolyte: ZnCl2 + NH4Cl + C + MnO2 (depolariser)
fi o
ECl -
/AgCl/Ag
= EAg
o
+
/Ag
+ log K sp (AgCl) (2)
1 Cell reaction
From (1) Anode: Zn h Zn+2 + 2e–
Cathode:
ECl- /AgCl/Ag = +4 +3
2 Mn O 2 (s) + 2NH 4+ + 2e Æ Mn 2 O3 (s) + 2NH3 + H 2 O
0.0591
o
EAg +
/Ag
+ log KSP (AgCl) - 0.0591 log (Cl - )] E.M.F. of cell = 1.5 V
1
0.0591 K [AgCl] 2. Secondary Cells:
fi ECl- /AgCl/Ag = EAg
o
+ / Ag + log SP - These are the cells which can be recharged and can be used
1 [Cl ]
again and again as their cell reaction are reversible in nature.
0.0591
= EAg
o
+
/Ag
+ log[Ag + ] Example, Lead storage battery
1 Anode: Pb
ECl- /AgCl/Ag = EAg + /Ag Cathode: PbO2
Electrolyte: Conc. H2SO4
If Ag+ ion concentration on both electrode are same.
E.M.F. depends on the concentration of H2SO4.
Ag+ + 1e– Æ Ag
Cell reaction
EAg + /Ag = EAg
o
+
/Ag
+ 0.0591 log [Ag + ] (a) Discharging
2- -
Heat of reaction (DH) in electrochemical cell Anode: Pb(s) + SO 4 (aq) Æ PbSO 4 (s) + 2e
DG = DH – TDS Cathode:
dG = V dP – SdT PbO 2 (s) + SO 24 - + 4H + + 2e - Æ PbSO 4 (s) + 2H 2 O
For chemical reaction: Net Cell Reaction
d(DG) = DV dP – DSdT Pb(s) + PbO2(s) + 2H2SO4(aq.) Æ 2PbSO4(s) + 2H2O(l)
At constant Pressure dP = 0 (b) Charging
d(DG) = –DSdT
During charging it act like electrolytic cell and all the
d
( DG ) = - ( DS ) cell reaction are reversed.
dT 2PbSO4 + 2H2O(l) Æ Pb(s) + PbO2(s) + 2H2SO4(aq.)
-d On passing IF charge, 1 mole of H2SO4 is produced
DS = (- nFE)
dT during the reaction.
Ê dE ˆ
DS = nF Á ˜ 3. Fuel Cell:
Ë dT ¯ P In this cell, heat of combution is converted into electrical en-
Entropy change in electrochemical cell: ergy.
Example H2 – O2 cell. (Bacon’s cell)
Ê dE ˆ
ÁË ˜¯ = Temperature coefficient of cell.
dT P
DG = DH – TDS
Ê dE ˆ
DG = DH - T ◊ nF Á ˜
Ë dT ¯ P H2 gas O2 gas
Ê dE ˆ
fi - nFE + TnF Á ˜ = DH
Ë dT ¯ P Anode Cathode
È Ê dE ˆ ˘ aq. NaOH + aq. KOH
\ DH = nF ÍT Á ˜ - E ˙
Î Ë dT ¯ P ˚ Anode: 2H2 + 4OH– Æ 4H2O(l) + 4e–
Battery Cathode: O2(g) + 2H2O(l) + 4e– Æ 4OH–(aq.)
These are the galvanic cells without salt bridge.
Net reaction: 2H2(g) + O2(g) Æ 2H2O(l)
Types of Battery
Fuel cells are used in aircraft because
1. Primary Cells: 1. These are lighter so, convenient to use.
These are the cells which cannot be recharged after using 2. No harmful product is formed.
once. Their cell reaction are irreversible in nature. 3. Efficiency is relatively high.

Efficiency of fuel cell 2. Electrolysis of aq. NaCl:

Electrical work produced At cathode
h= 1. Na+ + 1e– Æ Na;E° = –2.71 V
Heat of combustion
2. H2O + 2e– Æ H2≠ +2OH–; ER = –0.41 V
-DG nFE
= = Because of more reduction potential.
DH C DH C At anode
(i) 2Cl– Æ Cl2≠ + 2e–; Eo = –1.36 V
(ii) 2H2O Æ O2≠ + 4H+ + 4e–; Eo = –0.81 V
ELECTROLYTIC CELL Inspite of high oxidation potential (Eo) at anode, O2 is
not released because of its high over voltage.
1. It converts electrical energy into chemical energy. Over voltage = actual potential required – theoretical
2. In this cell, non-spontaneous cell reaction (DG = +ve) potential required
are carried out with the help of electric work. If solution is diluted then, O2 is released at anode.
+ – Note:
–
E e E ● In the aqueous solution if active metal ions like alkali
Inert electrondes metal ions, alkaline earth metal ions are present then,
Anode Cathode
H2O is reduced and produces H2 gas at cathode.
● If low reactive metal like Cu, Ag are present in the
Electrolyte (molten) solution then, these metal ions are reduced, not water.
● If halide ions (except F–) are present in the aqueous
solution then, halogen is produced at anode. But, if
at anode: oxidation occurs dilute solution of halide ions is there then, H2O is
2Cl– Æ Cl2≠ + 2e– oxidised to produce O2 at anode.
at cathode: reduction occurs ● If CO32 - , PO34- , NO3- , SO 42 - are present in the aque-
2Na+ + 2e– Æ 2Na ous solution then, H2O is oxidised and O2 is produced.
● Flow of electron from anode to cathode in outer circuit.
● Flow of current from anode of cathode through the so-

Example 1. Aq. CuSO4 solution:
lution. Anode: 2H2O Æ O2≠ + 4H+ + 4e–
● For the working of electrolytic cell, minimum voltage
Cathode: Cu+2 + 2e– Æ Cu
required is slightly more than the Ecell. 2. 1 M HCl solution:
Anode: 2Cl– Æ Cl2≠ + 2e–
PRODUCT OF ELECTROLYSIS Cathode: 2H+ + 2e– Æ H2≠
(USING INERT ELECTRODE) 3. Aq. H2SO4 solution
Anode: 2H2O Æ O2≠ + 4H+ + 4e–
1. Electrolysis of Water: Cathode: 2H+ + 2e– Æ H2≠
At Anode If highly concentrated solution of H2SO4 is
2H2O h O2≠ +4H+ + 4e– E0o = –1.23 V taken then, at anode following reaction takes
[H+] = [OH–] = 10–7 at ph = 7 place: 2SO 24 - Æ S2 O82 - + 2e -
0.0591
E o(at PH = 7) = - 1.23 - log[H + ]4
4 ELECTROLYSIS USING THE
= –1.23 + 0.42 REACTIVE ELECTRODE OR AT-
= –0.81 V TACKED ELECTRODE
At Cathode Whenever metal electrodes of electrolytic cell are dipped into
2H2O + 2e– Æ H2≠ + 2OH–; ERo = –0.8277 V their metal ion solution, metal is oxidised and metal is re-
0.0591 duced so that there will be not net reaction.
ER (at PH = 7) = - 0.8277 - log[OH - ]2 For example Electrolysis of CuSO4 solution using Cu
2
electrodes
= –0.41 V
At Anode:
Net cell reaction:
2H2O(l) m O2≠ + 2H2O≠ Cu h Cu+2 + 2e–
Ecell = –0.41 – 0.81 At Cathode:
= –1.22 V Cu+2 + 2e– Æ Cu
In this electrolysis, concentration of electrolyte remain un-
changed.

Faraday’s law of electrolysis l

Ist Law: Mass of the substance reacted on liberated at any Æ cell constant (cm–1) represented by G*
A
electrode is directly proportional to the charge passed. unit of ‘K’ = ohm–1, cm–1
wμQ
Note:
w = ZQ fi If l = 1 cm and A = 1 cm2 fi K = C
w = mass of substance in grams So, specific conductance is the conductance of all the ions
Q = charge passed in coulomb present in 1 cm3 of solution:
Z = electrochemical equivalent fi K is additive in nature.
E Ksolution = Ksolute + Ksolvent
=
96500
3. Molar conductance (lm) or Lm: It is the conductance
E = Equal weight of the substance. of all the ions produced by 1 mole of electrolyte present
Molecular weight Mwt in the given volume of solution.
E= = lm = (K)solute ¥ V
n-factor nf
1000 K
n-factor = Number of moles of e– transferred for 1 mole of lm = Ksolute ¥ Scm 2 Mole -1 =
the substance. M Concentration
1
w=
E
Q=
E
.i ¥ t lm = Ksolute ¥ Sm 2 Mole -1If K in Sm -1
96500 96500 1000M
w it Q V = volume (in cm3) of the solution containing 1 mole
Number of gm equivalent = = = of electrolyte
E 96500 96500
units = W–1 cm2/mole
= Number of Faraday 4. Equivalent conductance (leq.) or Leq:
= Number of moles of e– transferred It is the conductance of all the ions given by 1 gram
= moles of substance ¥ n factor equivalent of electrolyte in the given solution.
V leq = Ksolute ¥ V
=
Veq . 1000
Veq.= It is the volume occupied by 1 g equivalent of the gas. = Ksolute ¥
N
molar volume V-vol. (in cm3) of solution containing 1 gram equiva-
Veq = lent of electrolyte.
nf
Unit = ohm–1 cm2 g eq.–1
Volume of gas formed = gram Equivalent ¥ Veq Relation between lm amd leq.
2nd Law: Whenever two or more electrolytic cells are connected lm
leq =
in series then, mass of the substance reacted or produced at n- factor
any electrode is directly proportional to its equivalent weight.
n-factor = total +Ve charge or total –Ve charge in the
E
w= QfiwμE electrolyte.
96500 l
w1 w2 for Al2 (SO 4 )3 fi leq = m
= = ............ 6
E1 E2 l
for Na 3 PO 4 fi leq = m
3
ELECTROLYTIC
CONDUCTANCE Example The resistance of 0.01 N solution of electrolyte was
found to be 200 W at 298 K. If cell constant is 0.82/cm. Then,
1. Conductance (C): calculated eq. conductance.
1 K ¥ 1000
C= unit fi ohm–1 (W–1) or mho ( ) or Seimen leq or L eq =
R N
2. Specific conductance or Conductivity [K]:
1 l
1 1 l C ◊l K=
K= = ◊ = represented by Kork R A
r R A A 1 l 1000
l Æ distance between two electrodes in the cell. \ L eq = ¥
R A N
A Æ cross-sectional area of the electrodes

1 1000 Example Al2(SO4)3

Sol. leq = ¥ 0.82 ¥ = 410 ohm–1 cm2 eq.–1
200 0.01 lmo [Al2 (SO 4 )3 ] = 2 lmo (Al+3 ) + 3lmo (SO 24 - )
Factors affecting electrolytic conductance
leq.
o
[Al2 (SO 4 )3 ] = leq.
o
(Al+3 ) + leq.
o
(SO 42 - )
1. Nature of Electrolyte: Strong electrolytes provide
more ions so, their conductance is more compared to lmo (Al+3 ) lmo (SO 24 - )
weak electrolytes. = +
3 2
2. Nature of solvent: More the polarity of solvent; more lm
will be the conductance. nf = 6 \ leq =
6
3. Temperature: On in-
Example K2SO4 ◊ Al2(SO4)3 ◊ 24H2O
creasing the temperature,
interionic interaction de- l°m lm = 2 ◊ lm (K ) + 2lm (Al 3 ) + 4 ◊ lmo (SO 42 )
creased and average Ki-
netic Energy of ions in- lm lm
nf = 8 \ leq =
creases ≠ so, conductance 8
increases. 1 1 1
4. Concentration: With in- leq. = lm (K ) + lm (Al 3 ) + lmo (SO 24 )
C 4 4 2
crease in concentration
conductance decreases. Applications
(a) For strong electrolytes: 1. To find lm for weak electrolytes from strong electrolyte:
With increase in dilution incre in conductance for strong elec-
trolyte is very small. This effect is given by Debye Huckel On Example lmo (CH3COOH) = lm (CH3COO ) + lm (H )
sagar equation. = lm (CH3COONa) + lm (HCl) - lm (NaCl)
lmc = lmo -b c lmo or lm
Given that lm for Ba(OH)2, BaCl2 and NH4Cl are 523.28,
lmc Æ molar conductance at given concentration c 280, 129.8 ohm–1 cm2 mol–1 Molar conductance of NH4OH
can be calculated as
lmo molar conductance at 0 concentration.
lm (NH 4 OH) = lm (NH 4 ) + lm (OH )
lm molar conductance at dilution
1 1
b = constant = lm (NH 4 Cl) + lm [Ba(OH) 2 ] - lm (BaCl2 )
2 2
(b) For weak electrolytes = 251.44
There is rapid increment in the
conductance of weak electrolyte 2. To find degree of dissociation for weak electrolyte:
w.r.t. increase in dilution because 1000
degree of dissociation increases lm
lmc leq.
c K¥
a= = = M
appreciably.
lm leq. lm
fi lmo cannot be obtained graph-
C
ically for weak electrolytes. 3. To find solubility of sparingly soluble salts:
fi lm and leq increase with dilution but K decreases with For sparingly soluble salts, solution is always saturated so
dilution. their molar concentration = solubility
1000
lm lm = K solute ¥
SA or SB HCl or NaOH S
A 18°C, specific conductivity of saturated solution of AgCl is
Salt CH3COONa
1.19 ¥ 10–6 W–1 cm–1. If equivalent conductivity of Ag+ and
WA or WB NH4OH or CH3COOH Cl– at this temperature if 53.8 and 65.9 W–1 cm2 eq–1. Then,
Ksp of AgCl. can be calculated as
C
1000
1.19 ¥ 10-6 ¥ = lm = (53.8 + 65.9) = 119.1
Kohlraauch’s law S
At dilution, when dissociation is complete all the ions more
S = 10–5
independently and contributes towards molar or equivalent
conductance irrespective of the other ions present. KSP = S2 = 10–10

Ionic Mobility (U) + – H

H H H H H
Velocity of ion
U= O HO HH O H O O H O H
Potential gradient H H H + H H H
Potential applied O H O HO H O H O HO H
Potential gradient =
Distance b etween two electrodes + –
i.e., jumping of H or OH ions from one molecule of
2 –1 –1 water to another.
Unit of ‘U’ = m volt sec
leq = FU Æ experimental
Graph for titration of strong acid VS strong Base
Note:
● Conductance depends on both number of ions and
mobility of ion as ionic mobility. Conductance
● Ionic mobility of H+ and OH– ions, abnormally high
and so their conductance is too high. equivalence point
It is due to Grothus type of conductance for H+ and Base added
OH– ion.
HCl + NaOH Æ NaCl + H2O
Solved Examples
1. Calculate the maximum electrical work obtained from Sol. E ∞ = E o +3 +2 + E o +2 +4

the cell reaction in its S.T.P.: Fe /Fe Sn /Sn
Zn + 2Ag+ Æ 2Ag + Zn+2 = 0.77 + (–0.15) = 0.62
o
EZn +2 = - 0.76 V; EAg
o
+ = 0.80 V 0.0591
/ Zn /Ag 0.62 = log K eq.
Sol. W = –DG 2
Keq = 1021
o
= nFEcell o
and Ecell = EAg
o
+ + E oZn/Zn +2
/Ag 4. The standard reduction potential Cu+2/Cu is 0.34V cal-
= 2 ¥ 96500 ¥ (0.80 + 0.76) culate the reduction potential at PH = 14 for the above
= 2 ¥ 96500 ¥ 1.56 J couple. KSP (Cu(OH)2) = 1 ¥ 10-19.
2. Calculate the standard electrode potential of Ni+2/Ni Sol. Cu+2 + 2e– h Cu
if E.M.F. of the cell Ni/Ni+2(0.01M)//Cu+2(0.1M)/Cu;
Ecell = 0.59 V and ECu +2 /Cu = 0.34 V .
o 0.0591 1
E = 0.34 - log PH = 14 or POH = 0
2 [Cu +2 ]
+2 +2
Sol. Ni + Cu Æ Ni + Cu KSP = 1 ¥ 10–19 = [Cu+2][OH–]2
(0.1M) (0.01M)
0.0591 Since POH = 0 \ [OH–] = 1 M

Ecell = Ecell
o
- log Q \ Ksp = 1 ¥ 10–19 = [Cu+2] [OH–]2
n
fi [Cu+2] = 10–19 [OH–] = 1 M
0.0591 È 0.01˘
fi Ecell = 0.59 = Ecell
o
- log Í ˙
2 Î 0.1 ˚ 0.0591 1
E = 0.34 - log -19
o 2 10
Ecell = 0.59 volt – 0.03 = 0.56 V
0.0591
o
E° = 0.56 = 0.34 – ENi = 0.34 - ¥ 19 = - 0.22 volt.
+2
/ Ni 2
o = –0.22 V
ENi +2 5. E.M.F. of the cell given below is 0.767 V.
/ Ni
3. At 298 K; find equilibrium constant for the reaction Ag/AgI(s), 0.05 M KI//0.05 M AgNO3/Ag
2Fe+3 + Sn+2 h 2Fe+2 + Sn+4 Calculate solubility product of AgI.
Sol. KSP = [Ag+][I–] (1)
o
EFe +3
/Fe+2
= 0.77 V; ESn
o
+4
/Sn +2
= 0.15 V
= [Ag+]anode ¥ 0.05

+ + Fe2+ + 6CN– m [Fe(CN)6]4–; Kf = 1035;

Ag + Ag cathode h Ag anode + Ag
DG1o = –2.303RT log Kf = –199704.69 J
0.0591
Ecell = Ecell
o
- log Q Fe3+ + e– m Fe2+; E° = 0.77V;
n
DG2o = –96500 ¥ 0.77 = –74305 J
0.0591 [Ag + ]anode
fi 0.767 = 0 - log [Fe(CN)6]4– m [Fe(CN)6]3– + e–;
1 [Ag + ]cathode
E° = –0.36 V; DG3o = +96500 ¥ 0.36 = 34740 J
+
[Ag ] - 0.767
fi log = = - 13 Fe3+ + 6CN– m [Fe(CN)6]3–;
0.05 0.0591
DG4o = DG1o + DG2o + DG3o = – 239269.69 J
fi [Ag+]anode = 0.05 ¥ 10–13 M
From (1) KsP = [Ag+]Anode ¥ 0.05 = 25 ¥ 10–17 DG4o = –2.303 RT log K¢f
6. The standard reduction potential of Ag+/Ag electrode \ K¢f = 8.59 ¥ 1041
at 298 K is 0.8 V. 9. For the reaction, 4Al (s) + 3O2(g) + 6H2O + 4OH– h
Given that KspAgI = 10–16. Evaluate the o
4[Al(OH)4]– ; Ecell = 2.73 V. If DGfo (OH – ) = –157 kJ
(i) Potential of Ag+/Ag electrode in a saturated solu-
tion of AgI. mol–1 and DGfo (H 2O) = –237.2 kJ mol–1, determine
(ii) S.R.P. of I–/AgI/Ag electrode. DGfo (Al(OH) 4– ) .
Sol. (i) Ag+ + 1e– Æ Ag (a) 1.30103 kJ mol–1(b) –1.30103 kJ mol–1
E = 0.8 – 0.0591 log [Ag+] (c) 3.30103 kJ mol–1 (d) –3.30103 kJ mol–1
fi E = 0.32 V by putting [Ag+] = 10–8M Sol. (b)
AgI m Ag+ + I– o
The DG° and Ecell
o
are related by DG° = – nFEcell =
[Ag+]2 = KSP = 10–16 fi [Ag+] = 10–8 –12 ¥ 96500 ¥ 2.73 = –3.16 ¥ 103 kJ
(ii) EIo- /AgI/Ag = 0.8 + 0.0591 log 10–16 (since DGfo of Al(s) and O2 (g) are zero)
= 0.8 – 0.0591 ¥ 16 – 3.16 ¥ 103 + (6 ¥ – 237.2) + (4 ¥ –157)
= –0.16 V DGfo (Al(OH) 4– ) =
4
7. For a cell, Mg(s) + 2Ag+ (0.0001 M) h Mg2+ (0.130
= -1.30 ¥ 103 kJ mol-1
M) + 2Ag(s).
o
Calculate its Ecell if Ecell = 3.17 V 10. What is the equilibrium constant (Kc) of the reaction?
(a) 1.96 V (b) 2.96 V Cu(s) + 2Ag+(aq) h Cu+2(aq) + 2Ag(s); Ecello
= 0.46 V
(c) –2.96 V (d) 3.24 V
(a) 2.02 ¥ 1013 (b) 3.92 ¥ 1014
Sol. (b) The cell can be written as Mg | Mg2+ (0.130 M) ||
(c) 2.02 ¥ 1014 (d) 3.92 ¥ 1015
Ag+ (0.0001 M) | Ag
o 0.059 V
e RT [Mg 2+ ] Sol. (d) Ecell = log KC = 0.46 V or
E(cell) = E(cell) – ln 2
2F [Ag + ]2 0.46 V ¥ 2
log KC = = 15.6
0.059 V 0.130 0.059 V
= 3.17 V – log
2 (0.0001) 2
KC = 3.92 ¥ 1015
= 3.17 V - 0.21 V = 2.96 V 11. The standard electrode potential for Daniel cell is 1.1
8. Given the overall formation constant of the [Fe(CN)6]4– V. Find the standard Gibbs energy for the reaction
ion as 1035 and the standard potentials for the half reac- Zn(s) + Cu2+(aq) h Zn2+(aq) + Cu(s)
tions, (a) –212.3 kJ/mol (b) –2.123 kJ/mol
Fe3+ + e– m Fe2+ ; E° = 0.77 V (c) 21.23 kJ/mol (d) 21230 J/mol
[Fe(CN)6]3– + e– m [Fe(CN)6]4– ; E° = 0.36 V Sol. (a) D r G o = – nFE(cell)
o
Calculate the overall formation constant of the
[Fe(CN)6]3– ion. n in the above equation is 2, F = 96500 C mol–1 and
(a) 8.59 ¥ 1041 (b) 7.59 ¥ 1041 o
Ecell = 1.1 V
(c) 5.59 ¥ 10 41
(d) 9.59 ¥ 1041
Sol. (a) Therefore, DrGo = –2 ¥ 1.1 V ¥ 965000 C mol–1
Let Kf be the formation constant of [Fe(CN)6]3– ion. = –212300 J mol–1, = –212.3 kJ mol–1.

12. What is the potential of hydrogen electrode in contact Zn(s) + Ag2O(s) + H2O(l) h Zn2+(aq) + 2Ag(s) +
with a solution whose pH is 10 at 1 atm? 2OH–(aq)
(a) 0.581 (b) –0.591 V the DrG° and E° for the reaction is
(c) 0.059 V (d) 5.91 V Given Ag+ + e Æ AgEo = + 0.344 V
1 Zn+2 + 2e– Æ Zn Eo = –0.76 V
Sol. (b) For hydrogen electrode, H+ + e– h H 2 (a) –2.13 ¥ 105 J, 1.104 V
2
Applying Nernst equation, (b) –2.13 ¥ 105 J, –1.104 V
0.0591 1atm (c) 2.13 ¥ 105 J, 1.104 V
E H+ /H = E oH+ /H – log + (d) –1.13 ¥ 105 J, –2.104 V
2 2 n [H ]
Sol. (a)
=0–
0.0591 1
log –10 {pH = 10 means [H + ] = 10 –10 M} (a) Zn is oxidised and Ag2O is reduced (as Ag+ ions
1 10 change into Ag).
= –0.0591 ¥ 10 = –0.591 V o o o
(b) Ecell = EAg 2O/Ag (Red) + EZn / Zn 2+ (Ox)
13. The emf of the cell for the reaction
= 0.344 + 0.76 = 1.104 V
Ni(s) + 2Ag+(0.0002M) h Ni2+(0.160M) + 2Ag(s) o
o DG = – nFEcell = –2 ¥ 96500 ¥ 1.104 J
Given that Ecell = 1.05 V
= –2.13 ¥ 105 J
(a) 0.75 V (b) –0.45 V
16. Calculate the EMF of the electrode concentration cell
(c) 0.91 V (d) –0.82 V
Hg-Zn (c1 M) | Zn2+ (c M) | Hg-Zn (c2 M)
Sol. (c) Applying Nernst equation to the given cell reaction at 25°C, if the concentration of the zinc amalgam are 2
0.0591 [Ni 2+ ] g per 100 g of mercury and 1 g per 100 g of mercury in
o
Ecell = Ecell – log anode and cathode half-cell respectively.
n [Ag + ]2
(a) 6.8 ¥ 10–2 V (b) 8.8 ¥ 10–3 V
0.0591 0.160 (c) 5.7 ¥ 10 V–2
(d) 7.8 ¥ 10–3 V
= 1.05 V – log
2 (0.0002) 2 Sol. (b) The reactions at the two half-cells are
0.0591 1600 At cathode: Zn2+(c) + 2e– h Zn(c2)
1.05 - log ¥ 104 At anode: Zn(c1) h Zn2+(c) + 2e–
2 2¥2
Net cell reaction: Zn(c1) h Zn(c2)
0.0591
1.05 - log(4 ¥ 106 ) Applying Nernst equation to the net cell reaction gives
2
0.059 c 0.059 c
1.05 - 0.03[6 - 0.06] = 5.4 ¥ 0.03 o
Ecell = Ecell – log 2 = o
log 1 (since Ecell = 0)
2 c1 2 c2
1.05 - 0.162 = 0.888 V
0.059 Ê 2/65.4 ˆ
14. For reaction, 2Fe3+(aq) + 2I–(aq) h 2Fe2+(aq) + I2(s) Ecell = log Á = 8.8 ¥ 10 –3 V
o 2 Ë 1/65.4 ˜¯
has Ecell = 0.236 V at 298 K. The standard Gibbs en-
ergy and the equilibrium constant of the cell reaction 17. Calculate the EMF of the following galvanic cell
(a) 45.55 kJ/mol, 8.5 ¥ 108 Zn | Zn2+ (0.01 M) || Zn2+ (0.1 M) | Zn
(b) 50.12 kJ/mol, 7.2 ¥ 107 at 298 K.
(c) –50.12 kJ/mol, 8.5 ¥ 108 (a) 0.0395 V (b) –0.0395 V
(d) –45.55 kJ/mol, 9.6 ¥ 107 (c) 0.0295 V (d) 1.0345 V
Sol. (d) 2Fe3+ + 2e– h 2Fe2+ and 2I– h I2 + 2e– Sol. (c) The reactions at the two half-cells are
Hence, for the given cell reaction, n = 2. At cathode: Zn c2+ + 2e – h Zn
o
DrG° = – nFEcell = –2 ¥ 96500 ¥ 0.236 J At anode: Zn h Zn 2+
A + 2e
–
= –45.55 kJ mol–1
DrG° = –2.303RT log Kc Net cell reaction: Zn C2+ h Zn 2+
A
Applying Nernst equation to the net cell reaction gives
DrGo
or log K c =
2.303RT o 0.059 [Zn 2+
A ]
Ecell = Ecell – log
– 45.55 kJ mol –1 2 [Zn C2+ ]
=
2.303 ¥ 8.314 ¥ 10 –3 kJ K –1mol –1 ¥ 298 K [Zn 2+
0.059 A ] o
= 7.983 Ecell = log (since Ecell = 0)
2 [Zn C2+ ]
\ Kc = Antilog (7.983) = 9.616 107 0.059 0.1
15. In the bottom cells widely used in watches and other Ecell = log = 0.0295 V
2 0.01
decrease the following reaction take place.

18. The Ksp of CuI is 1.1 ¥ 10–12 M2. Determine EMF of (a) 0.31 Sm–1, 124 ¥ 10-4 Sm2 mol–1
the cell, represented as (b) 0.248 Sm–1, 124 ¥ 10–4 S m2 mol–1
Cu | CuI | I– (1 M) || Cu+ (1 M) | Cu.
(c) 1.12 Sm–1 , 221 ¥ 104 Sm2 mol–1
(a) 0.502 V (b) 1.203 V
(c) 0.705 V (d) 0.115 V (d) 0.196 Sm–1, 248 ¥ 10–4 S m2 mol–1
Sol. (c) The anode of the given cell is metal-insoluble metal Sol. (b) The cell constant is given by the equation
salt-anion type half-cell while cathode is of the type Cell constant = G* = conductivity ¥ resistance
metal-metal ion. The half-cell reactions at anode are = 1.29 S/m 100 W = 129 m–1 = 1.29 cm–1.
Cu(s) h Cu+ + e–; DG1 = - FECu|Cu
o Conductivity of 0.02 mol L–1 KCl solution = cell con-
+
stant/resistance
Cu+ + I– m CuI(s); DG2 = 0
Net anode reaction: Cu(s) + I– m CuI(s) + e–; DG3 = G * 129 m –1
= = = 0.248 Sm –1
- FECu|CuI|I- R 520 W
According to Hess’s law, we know Concentration = 0.02 mol L–1 = 1000 ¥ 0.02 mol m–3 =
DG1 + DG2 = DG3 20 mol m–3
\ DG1 = DG3 (as DG2 = 0) K
Molar conductivity = L m =
\ – FECu|Cu + = – FECu|CuI|I- Concentration
So, ECu|Cu + = ECu|CuI|I – 248 ¥ 10 –3 Sm –1

= = 124 ¥ 10 –4 Sm 2 mol –1
20 mol m –3
Since, the E value of Cu h Cu+ + e– and E value of
Cu + I– h CuI + e– are same, the representation of –1
anode can be changed from metal-insoluble metal salt- Alternatively, K = 1.29 cm = 0.248 ¥ 10 –2 S cm –1
520 W
anion half-cell to metal-metal ion half-cell, provided
the concentration of Cu+ in both the half-cells is same. and L m = K ¥ 1000 cm3 L–1 molarity –1
So, the complete cell can now be represented as
K ¥ 1000
Ê K sp ˆ Lm =
Cu |Cu + Á - ˜ ||Cu + (1M)|Cu M
Ë [I ] ¯
0.248 ¥ 10 –2 S cm –1 ¥ 1000 cm3 L–1
Reactions occurring at the two electrodes are =
0.02 mol L–1
At anode: Cu h Cu +A +e –
= 124 S cm2 mol–1
At cathode: Cu C+ + e – h Cu 20. The electrical resistance of a column of 0.05 mol L–1
NaOH solution of diameter 1 cm and length 50 cm is
Net cell reaction: Cu C+ h Cu A
+
5.55 ¥ 103 W. Its resistivity, conductivity and molar
Applying Nernst equation gives conductivity.
+ (a) 87.135 W, 0.1148 S cm–1, 229.6 S cm2 mol–1
RT [Cu A ]
= ECu
o
+
o
– ECu + – ln (b) 77.123 W, 0.241 S cm–1, 119.5 S cm2 mol–1
|Cu
C A|Cu F [Cu C+ ] (c) 92.29 W, 0.124 S cm–1, 272.3 S cm2 mol–1
o RT [Cu C+ ] (d) 83.92 W , 0.1192 S cm–1, 220.3 S cm2 mol–1
Ecell = Ecell + ln Sol. (a) A = pr2 = 3.14 ¥ 0.52 cm2 = 0.785 cm2 = 0.785 ¥
F [Cu +A ]
10–4 m2
RT [Cu C+ ] o l = 50 cm = 0.5 m
Ecell = ln (as Ecell = 0)
F [Cu +A ] rl RA 5.55 ¥ 103 W ¥ 0.785 cm 2
R= or r = =
RT [Cu C+ ] ¥ [I – ] 1¥1 A l 50 cm
Ecell = ln = 0.059 log
F KSP 1.1 ¥ 10 –12 = 87.135 W cm
Ecell = 0.70 l Ê 1 ˆ –1
Conductivity = K = =Á ˜ S cm
19. Resistance of a conductivity cell filled with 0.1 mol L –1 r Ë 87.135 ¯
KCl solution is 100 W. If the resistance of the same cell = 0.01148 S cm –1
when filled with 0.02 mol L–1 KCl solution is 520 W.
0.01148 S cm –1 ¥ 1000 cm3 L–1
The conductivity of 0.1 mol L–1 KCl solution is 1.29 Lm =
S/m. What is the conductivity and molar conductivity 0.05 mol L–1
of 0.02 mol L–1 KCl solution? = 229.6 S cm 2 mol-1

If we want to calculate the values of different quantities

K 4.95 ¥ 10 –5 S cm –1 1000 cm3
in terms of ‘m’ instead of ‘cm’. Sol. (c) L m = = ¥
C 0.001028 mol L–1 L
RA 5.55 ¥ 103 W ¥ 0.785 ¥ 10 –4 m 2 K ¥ 1000
r= = =
l 0.5 m M
-1
= 87.135 ¥ 10 –2 Wm If K in S cm
1 100 = 48.15 S cm3 mol –1
K= = Wm = 1.148 Sm –1
r 87.135
L m 48.15 S cm 2 mol –1
and a= = = 0.1233
L om 390.5 S cm 2 mol –1
Lm =
K 1.148 S m –1
= = 229.6 ¥ 10 –4 S m 2 mol –1 CH3COOH m CH3COO - + H +
C 50 mol m –3 C O O
21. The conductivity of 0.20 M solution of KCl at 298 K is C - Ca Ca Ca
0.0248 S cm–1. Its molar conductivity is: ca 2
(a) 120 S cm2 mol–1 (b) 115 S cm2/mol Ka =
2 –1 (1 – a )
(c) 124.0 S cm mol (d) 1105 cm2/mol
ca 2 0.001028 mol L–1 ¥ (0.1233) 2
k= =
K ¥ 1000 0.0248 S cm ¥ 1000 cm L
–1 3 –1
a (1 – a ) 1 – 0.1233
Sol. (c) L m = =
Molarity 0.20 mol L–1 = 1.78 ×10 –5 mol L–1
2 –1
= 124 S cm mol
25. The molar conductivity of 0.025 mol L–1 methanoic
22. The resistance of a conductivity cell containing 0.0001 acid is 46.1 S cm–1 mol–1. Its degree of dissociation (a)
M KCl solution at 298 K is 1500 W. What is the cell and dissociation constant. Given l°(H+) = 349.6 S cm2
constant if conductivity of 0.001 M KCl solution at 298 mol–1 and l°(HCOO–) = 54.6 S cm2 mol–1.
K is 0.146 ¥ 10-3 S cm-1. (a) Ka = 3.67 ¥ 104 a = 0.214
(a) 0.200 cm–1 (b) 0.219 cm–1 (b) Ka = 3.67 ¥ 10–4 a = 0.114
(c) 0.195 cm –1
(d) 0.190 cm–1 (c) Ka = 2.25 ¥ 10–4 a = 0.150
(d) Ka = 2.25 ¥ 10–2 a = 0.314
Conductivity
Sol. (b) Cell constant = Sol. (b) L om (HCOOH) = lo(H+) + lo(HCCO–) = 349.6 +
Conductance
54.6 S cm2 mol–1
= Conductivity ¥ Resistance
= 404.2 S cm2 mol–1
0.146 ¥ 10–3 S cm–1 ¥ 1500 W = 0.219 cm–1 L m = 46.1 S cm2 mol–1 (Given)
c
23. L om for NaCl, HCl and NaAc are 126.4, 425.9 and 91.0 L cm 46.1
S cm2 mol–1 respectively. What is the for L om (in S cm2 a= = = 0.114
L m 404.2
0
mol–1)
HCOOH m HCOO– + H+
(a) 426.9 (b) 390.5 (c) 517.9 (d) 552.2
Initial concentration C mol L–1
Sol. (b) L om(HAc) = l o + + l o - Conc. at eqm. C(1 – a) Ca Ca
H Ac
= lHo + + lCl Ca ◊ Ca Ca 2 0.025 ¥ (0.114) 2

– +l – +l – lCl – – l
o o o o o
Ac Na + Na + Ka = = = = 3.67 ¥ 10 –4
C(1 – a ) 1 – a 1 – 0.114
= L om(HCl) + L om(NaAc) – L om(NaCl)
26. Conductivity of 0.00241 M acetic acid is 7.896 10–5 S
= (425.9 + 91.0 – 126.4) S cm mol 2 –1
cm–1. It has L om is 390.5 S cm2 mol–1. What is its molar
= 390.5 S cm2 mol–1 conductivity and dissociation constant.
24. The conductivity of 0.001028 mol L–1 acetic acid is 4.95 (a) 1.85 ¥ 10–5 mol L–1 (b) 2.86 ¥ 10–4 mol L–1
¥ 10–5 S cm–1. Its dissociation constant is ________. if (c) 1.92 ¥ 10–4 mol L–1 (d) 3.52 ¥ 10–2 mol L–1
L om for acetic acid is 390.5 S dm2 mol–1. Sol. (a)
(a) 48.15 ¥ 10–3 mol L–1 K ¥ 1000 (7.896 ¥ 10 –5 S cm –1 ) ¥ 1000 cm3L–1
(b) 2.75 ¥ 10–5 mol/L L cm = =
Molarity 0.00241 mol L–1
(c) 1.78 ¥ 10–5 mol L–1
(d) 3.2 ¥ 10–3 mol/L = 32.76S cm 2 mol –1

L cm 32.76 OR
a= = = 8.4 ¥ 10 –2 E w i
L om 390.5 w= it fi =
96500 E 96500
Ca 2 0.00241 ¥ (8.4 ¥ 10 –2 ) 2 224 i
Ka = = = 1.86 ¥ 10 –5 fi ¥2= \ i = 1930 Amp.
1–a 1 – 0.084 22400 96500
27. A solution of CuSO4 is electrolysed for 10 min with a 31. Calculate the quantity of electricity in Faraday that will
current of 1.5 amp. The mass of copper deposited at the be required to liberate 710 g of gas by electrolysis of
cathode is concentration NaCl and also calculate the weight of
(a) 0.2938 g (b) 0.325 g NaOH produced during the process.
(c) 1.752 g (d) 0.92 c w 710
Sol. F= = ¥ 2 = 20 F
Sol. (a) t = 600 s charge = current ¥ time = 1.5 A ¥ 600 s = E 71
900 C 40
According to the reaction: wNaOH = 20 ¥ = 800 g
1
Cu2+ (aq) + 2e– = Cu(s)
We require 2F or 2 ¥ 96500 C to deposit 1 mol or 63 g NaCl Æ Na+ + Cl–
of Cu. 2Cl– Æ Cl2 + 2e–
For 900 C, the mass of Cu deposited for 1 mole Cl2 electricity required = 2F
= (63 g mol–1 ¥ 900 C)/(2 ¥ 96500 C mol–1) = \ for
710
= 10 mole Cl2 required = 2F ¥ 10 = 20F
0.2938 g. 71
28. Consider the reaction: \ Mole of NaCl used = 2 ¥ Moles of Cl2 evolved
Cr2O72– + 14H + + 6e – h 2Cr 3+ + 7H 2O = 20 mole
\ Moles of NaOH formed = 20 Mole
What is the quantity of electricity in coulombs needed
2–
= 20 ¥ 40 = 800 gram
to reduce 1 mol of Cr2O7 ? 32. An acidic solution of Cu(NO3)2 salt containing 0.4 g of
(a) 6 F (b) 5 F Cu+2 is electrolysed until all the Cu is deposited. The
(c) 4 F (d) 3 F electrolysis continues for 7 more minutes with volume
Sol. (a) 1 mole of Cr2O7–2 corresponds to 6 moles of elec- of solution kept at 100 ml and current at 1.2 A. Cal-
trons = 6 F of electricity culate the volume of gases evolved at NTP during the
as 1 mole of electron = 1 Faraday entire process.
29. If a current of 0.5 amp flows through a metallic wire for Sol. 1st electrolysis:
2 hrs, then how many electrons flow through the wire? At anode: 2H2O Æ O2≠ + 4H+ + 4e–
(a) 2.24 ¥ 1021 (b) 2.39 ¥ 1021 At cathode: Cu+2 + 2e– Æ Cu
(c) 2.246 ¥ 10 22
(d) 3.23 ¥ 1022 0.4
Sol. (c) Q (coulombs) = i(ampere) ¥ t (sec) = (0.5 ampere) g eq. of O2 = g of Cu = ¥2
63.5
¥ (2 ¥ 60 ¥ 60 s) = 3600 C.
A flow of 1 F, i.e., 96500 C is equivalent to flow of 1 0.4 22400
V1 = VO2 = ¥2¥ ml = 70.55 ml
mole of electrons, i.e., 6.02 ¥ 1023 electrons. 63.5 4
\ 3600 C is equivalent to flow of electrons = 2nd electrolysis:
6.02 ¥ 1023 Cathode: 2H2O + 2e– Æ H2≠ + 2OH–
¥ 3600 = 2.246 ¥ 1022 electrons. Anode: 2H2O Æ O2≠ +4H+ + 4e–
96500
1.2 ¥ 7 ¥ 60
30. How much current is necessary to produce H2 gas at the gm eq. of H2 = gm eq. of O2 =
96500
rate of 224 cm3/s at NTP?
Sol. 2H+ + 2e– Æ H2 V2 = VH2 = g eq. ¥ Veq.
2F charge required for deposition of 1 mole H2 1.2 ¥ 7 ¥ 60 22400
= 22400 ml H2 at STP = ¥ ml = 58.495 ml
96500 2
\ 22400 ml H2 liberated by 2 ¥ 96500 C 1.2 ¥ 7 ¥ 60 22400
2 ¥ 96500 V3 = VO2 = ¥ ml = 29.247 ml
\ 1 ml H2 liberated by 96500 4
22400
\ 224 ml liberated by \ Total volume of gases
= 70.55 + 58.495 + 29.247 = 159.292 ml
2 ¥ 96500
= ¥ 224 = i ¥ t = i ¥ 1 33. The molar conductivity of mono-basic acid at dilu-
22400 tion is 380 mho cm2 mol–1 and 0.01 M. acid specific
conductivity is 9.5 ¥ 10–4 mho cm–1.
i = 1930 Amp. Calculate

(i) degree of dissociation of monobasic acid. x = 1 ¥ 10–3

(ii) KA of acid. [Ba2+] = 1 ¥ 10–3 \ Ksp = S2
1000 = 1 ¥ 10–6
L Cm K ¥ M 35. An aquous solution containing one mole per litre of
Sol. (i) a = = each Cu(NO3)2 AgNO3, Hg(NO3)2 and Mg(NO3)2 is
Lm Lm
being electrolysed using inert electrodes. The values of
1000
9.5 ¥ 10-4 ¥ the standard electrolysed electrode potentials in volts
a= 0.01 = 0.25 (reduction potentials) are Ag |Ag+ = +0.80, Hg|Hg2+
380 = +0.79, Cu|Cu+2 = +0.34, Mg|Mg2+ = –2.37 With in-
(ii) HA H+ + A- creasing voltage ,the sequence of deposition of metals
on cathode will be
C - Ca Ca Ca
(a) Ag, Hg, Cu, Mg (b) Mg, Cu, Hg, Ag
a 2C 0.01 ¥ 225 ¥ 0.25 (c) Ag, Hg, Cu (d) Cu, Hg, Ag
Ka = = = 8.3 ¥ 10-4 (c) Higher the reduction potential, more will be the ten-
1- a 0.75 Sol.
34. The conductivity of a saturated solution of BaSO4 is dency of deposition (Mn+ + ne– h M) but Mg2+ ions
3.06 ¥10–6 ohm–1cm–1 and its equivalent conductance will not be deposited because H2O is reduced more eas-
is 1.53 ohm–1cm2 eq–1. The Ksp for BaSO4 will be ily than Mg2+ ions.
(a) 4 ¥ 10–6 (b) 2.5 ¥10–9 36. The resistance of N/10 solution is found to be 2.5 103
(c) 2.5 ¥ 10 –13
(d) 1 ¥ 10–6 ohms. The equivalent conductance of the solution is
Variation of conductivity and molar conductivity with (cell constant =1.25 cm–1)
concentration (a) 25 ohm–1 cm2 eq–1
Sol. (d) nf of BaSO4 = 2
(b) 5.0 ohm–1 cm2 eq–1
L
L eq = m (c) 2.5 ohm–1 cm2 eq–1
2
(d) 2.5 ohm–1 cm–2 eq–1
\ L m = 2 ¥ L eq
Sol. (b)
BaSO4 Ba 2+ + SO-42 1000
L eq = K ¥
K(BaSO4) = 3.06 ¥ 10–6 N
l(BaSO4) = 1.53 =
1
¥
1000
Let the aq. solution contain x moles of Ba+2 and x moles RA N
the of SO 4–2 and they are produced from x moles/L of 1 1000
= ¥ 1.25 ¥
BaSO4 2.5 ¥ 103 0.1
1000 = 5 Ohm -1cm 2eq -1
L m = 3.06 ¥ 10-6 ¥ = 1.53 ¥ 2
X
Exercise
0
LEVEL I 3. The EM 3+
/M 2 +
values for Cr, Mn, Fe and Co are –0.41,
+1.57, +0.77 and +1.97 V respectively. For which one
1. Electrolysis of a solution of SO–24 ions produces S2O8–2. of these metals the change in oxidation state from +2 to
Assuming 75% current efficiency, what current should +3 is easiest?
be employed to achieve a production rate of 1 mole (a) Co (b) Mn (c) Fe (d) Cr
S2O8 per hour? 4. For the redox change;
(a) 43.3 A (b) 71.5 A (c) 35.2 A (d) 58.3 A Zn(s) + Cu2+ h Zn2+ + Cu(s), taking place
2. How much will the potential of a hydrogen electrode
0.1 M 0.1 M
change when its solution initially at pH = 0 is neu- 0
tralised to pH = 7 In a cell Ecell is 1.10 volt. Ecell for the cell would
(a) increase by 0.0591 V (b) decrease by 0.0591 V be
(c) increase by 0.413 V (d) decrease by 0.413 V (a) 1.07 V (b) 0.82 V (c) 2.14 V (d) 180 V

5. An aqueous solution containing Na+, Sn2+, Cl– and 13. Cr2O72– + I– Æ I2 + Cr3+, E°cell = 0.79 V, E°Cr2
SO 2–
4 ions, all at unit concentration, is electrolysed O–2 +3 o
7 Cr = 1.33 V, EI |I- ?
2
between a silver anode and a platinum cathode. What
changes occur at the electrodes when current is passed (a) 0.54 (b) –0.054 (c) +0.18 V (d) –0.18 V
o 14. The standard emf of the cell Cd(s)|CdCl2(0.1M)||AgCl(s)
through the cell? Given: EAg + = 0.799 V
|Ag |Ag(s) in which the cell reaction is
o o Cd(s) + 2AgCl(s) Æ 2Ag(s) + Cd2+(aq) + 2Cl–(aq) is
ESn = – 0.14 V, ECl = 1.36 V,
0.6915 V at 0°C and 0.6753 V at 25° C. DH of the reac-
2+ –
|Sn 2 |Cl
ESo O2– |SO2– = 2V, ESn

o
4+ = 0.13 V tion is
|Sn 2+
2 8 4 (a) –176 kJ (b) –334.7 kJ
(a) Sn is reduced and Cl– is oxidised.
2+ (c) +123.5 kJ (d) –167 kJ
(b) Ag is oxidised and Sn2+ is reduced. 15. On the basis of information available from the reaction
(c) Sn2+ is reduced and Sn2+ is oxidised 4 2
(d) H+ is reduced and Sn2+ is oxidised. Al + O 2 h Al2O3 , DG = – 827 kJ
3 3
6. The limiting molar conductivities Lo for NaCl, KBr –1
mol of O2, the minimum emf required to carry out
and KCl are 126, 152 and 150 S cm2 mol–1 respective-
electrolysis of Al2O3 is
ly. The Lo for NaBr (S cm2 mol–1) is
(a) 2.14 V (b) 4.28 V (c) 6.42 V (d) 8.56 V
(a) 302 (b) 176 (c) 278 (d) 128
16. If half-cell reaction A + e– Æ A– has a large negative
7. In the electrolysis of CuCl2 solution using Cu elec-
reduction potential, it follows that
trodes, the weight of Cu anode increased by 2 g at cath-
(a) A is readily reduced
ode. In the anode
(b) A is readily oxidised
(a) 0.2 mole of Cu2+ will go into solution.
(c) A–1 is readily reduced
(b) 560 mL O2 liberate
(d) A–1 is readily oxidised
(c) No loss in weight
17. A standard hydrogen electrode has zero electrode po-
(d) 2 g of copper goes into solution as Cu2+
tential because
8. The density of Cu is 8.94 g cm–3. The quantity of elec-
(a) hydrogen is easier to oxidise.
tricity needed to plate an area 10 cm ¥ 10 cm to a thick-
(b) this electrode potential is assumed to be zero.
ness of 10–2 cm using CuSO4 solution would be
(c) hydrogen atom has only one electron.
(a) 13586 C (b) 27155 C
(d) hydrogen is the lightest element.
(c) 40758 C (d) 20348 C
18. What will be the emf of the given cell?
9. A current of 9.65 A is drawn from a Daniel cell for ex-
Pt|H2(P1)|H+(aq)|H2(P2)|Pt
actly 1 hr. The loss in mass at anode and gain in mass at
cathode, respectively are RT P1 RT P1
(a) ln (b) ln
(a) 11.43 g, 11.77 g (b) 11.77 g, 11.43 g F P2 2 F P2
(c) 22.86 g, 23.54 g (d) 23.54, 22.86 g
10. An electrochemical cell stops working after some time RT P2
(c) ln (d) None of these
because F P1
(a) one of the electrodes is eaten away. 19. Value of E H2O/H2(1atm)Pt at 298 K would be
(b) electrode potentials of both the electrodes become
equal in magnitude. (a) –0.207 V (b) +0.207 V
(c) electrode potentials of both electrodes go on de- (c) –0.414 V (d) +0.414 V
creasing. 20. Conductivity (units Siemen’s S) is directly proportion-
(d) electrode potentials of both the electrodes go on al to the area of the vessel and the concentration of the
increasing. solution in it and is inversely proportional to the length
11. Four alkali metals A, B, C and D are having respective- of the vessel, then the unit of constant of proportional-
ly standard electrode potentials as –3.05, –1.66, –0.40 ity is
and 0.80 V. Which one will be most reducing? (a) S m mol–1 (B) S m2 mol–1
–2 2
(a) A (b) B (c) C (d) D (c) S m mol (d) S2m2 mol–2
12. Zn(S) + Cl2 (1 atm) Æ Zn2+ + 2Cl– The E° of the cell is 21. For strong electrolytes, the plot of molar conductance
2.12 V. To increase E vs c is
(a) Zn2+ concentration should be increased. (a) parabolic (b) linear
(b) Zn2+ concentration should be decreased. (c) sinusoidal (d) circular
(c) Cl– concentration should be increased. 22. If the molar conductance values of Ca2+and Cl– at infi-
(d) partial pressure Cl2 should be decreased. nite dilution are respectively

118.88 ¥10–4 m2 mhosmol–1 and 77.33 ¥ 10–4 m2

[Zn 2 + ]
mhos mol–1,,then that of CaCl2 is (m2 mhosmol–1). Zn + Cu++ m Zn++ + Cu, K =
(a) 118.88 ¥ 10–4 (b) 154.66 ¥ 10–4 [Cu 2 + ]
(c) 273 ¥ 10 –4
(d) 196.21 ¥ 10–4 (a) 8.314 ¥ 1024 (b) 4.831 ¥ 10–31
23. Which of the following statements is true for the elec- (c) 8.314 ¥ 10 36
(d) 4.831 ¥ 1044
trochemical Daniell cell? 33. The standard electrode potential (reduction) of Ag+|Ag
(a) Electrons flow from copper electrode to zinc elec- is 0.800 V at 25°C. Its electrode potential in a solution
trode. containing 10–3 M ion of Ag+ ions is
(b) Current flows from zinc electrode to copper elec- (a) 0.623 V (b) –0.977 V
trode. (c) 0.892 V (d) 1.246 V
(c) Cations move towards copper electrode. 34. The number of Faradays required to produce one mole
(d) Cations move towards zinc electrode. of water from hydrogen-oxygen fuel cell containing
24. Best way to prevent rusting of iron is by aqueous alkali as electrolyte is
(a) making iron cathode. (a) 1 (b) 3 (c) 2 (d) 4
(b) putting it in saline water. 35. The solubility product of silver iodide is 8.3 ¥ 10–17
(c) Both of these and the standard potential (reduction) of Ag, Ag+ elec-
(d) None of these trode is +0.800 volts at 25°C. The standard potential of
25. Time required to deposit one millimole of aluminium Ag, AgI/I– electrode (reduction) from these data is
metal by the passage of 9.65 amp through aqueous so- (a) –0.30 V (b) +0.15 V
lution of aluminium ion is (c) +0.10 V (d) –0.15 V
(a) 30 s (b) 10 s (c) 30,000 s (d) 10,000 s 36. The standard electrode potentials (reduction) of
26. The cell Pt (H2) (1 atm) |H+ (pH = ?), I– (a = 1) AgI(s), Pt/Fe3+, Fe+2 and Pt/Sn4+, Sn+2 are +0.77 V and 0.15 V
Ag has emf, E298 = 0. The electrode potential for the respectively at 25°C. The standard EMF of the reaction
reaction AgI + e– Æ Ag + I is –0.151 volt. Calculate Sn4+ + 2Fe2+ Æ Sn2+ + 2Fe3+ is
the pH value:- (a) –0.62 V (b) –0.92 V (c) +0.31 V (d) +0.85 V
(a) 3.37 (b) 5.26 (c) 2.56 (d) 4.62 37. The emf of the following cell
27. The standard EMF of the cell in which the reaction Ni(s)/NiSO4 (1.0 M) || H+ (1.0 M)|H2 (1 atm), Pt at
MnO 4– + 5Fe2+ + 8H+ h Mn2+ + 5Fe3+ + 4H2O oc- 25°C is 0.236 V. The electrical energy which can be
curs is 0.59 V at 25°C. The equilibrium constant for the produced is
given reaction is approximately (a) 22.73 kJ (b) 45.55 kJ
(a) 50 (b) 10 (c) 1050 (d) 105 (c) 19.30 kJ (d) 23.60 kJ
28. If the pressure of H2 gas is increased from 1 atm to 38. The reduction potential of a half-cell consisting of a Pt
100 atm keeping H+ concentration constant at 1 M, the electrode immersed in 1.5 M Fe2+ and 0.015 M Fe3+
change in reduction potential of hydrogen half-cell at o
solution at 25°C is ( EFe3+
/Fe2+
= 0.770 V) :
25°C will be
(a) 0.652 V (b) 0.88 V
(a) 0.059 V (b) 0.59 V
(c) 0.710 V (d) 0.850 V
(c) 0.0295 V (d) 0.118 V
39. The specific conductance of a N/10 KCl solution at
29. During electrolysis of an aqueous solution of sodium
18°C is 1.12 ¥ 10–2 mho cm–1. The resistance of the
sulphate, 2.4 L of oxygen at STP was liberated at an-
solution contained in the cell is found to be 65 ohms.
ode. The volume of hydrogen at STP, liberated at cath-
Calculate the cell constant.
ode would be
(a) 0.912 cm–1 (b) 0.512 cm–1
(a) 1.2 L (b) 2.4 L (c) 2.6 L (d) 4.8 L –1
(c) 0.728 cm (d) 0.632 cm–1
30. Using the information in the preceding problem, cal-
40. Calculate the dissociation constant of water at 25°C
culate the solubility product of AgI in water at 25°C
from the following data:
[E o(Ag+, Ag) = +0.799 volt] :- given AgI + e– Æ Ag + I
Specific conductance of H2O = 5.8 ¥ 10–8 mho cm–1
E o = –0.151
(a) 1.97 ¥ 10–17 (b) 7.91 ¥ 10–17 l – = 198.0 mho cm2.
OH
(c) 1.79 ¥ 10 –17
(d) 9.17 ¥ 10–17 (a) 3.2 ¥ 10–15 mol L–1 (b) 4 ¥ 10–15 mol L–1
31. A current of 9.65 amp is passed through the aqueous (c) 1.62 ¥ 10–16 mol L–1 (d) data in sufficient
solution NaCl using suitable electrodes for 1000 s. The 41. Which of the following represents the reduction poten-
amount of NaOH formed during electrolysis is tial of silver wire dipped into 0.1 M AgNO3 solution at
(a) 2.0 g (b) 4.0 g (c) 6.0 g (d) 8.0 g 25°C:
32. Using the data EZno
+2
/Zn
= 0.76 V, ECu
o
+2
/Cu
= + 0.34 V (a) E°red (b) (E°red + 0.059)
calculate the equilibrium constant of the reaction at (c) (E°ox – 0.059) (d) (E°red – 0.059)
25°C.

42. If the solution of the CuSO4 in which copper rod is im- 52. Three moles of electrons are passed through three so-
mersed is diluted to 10 times, the electrode reduction lutions in succession containing AgNO3, CuSO4 and
potential (T = 298 K): AuCl3 respectively. The molar ratio of amounts of cat-
(a) increases by 0.030 V ions reduced at cathode will be
(b) decreases by 0.030 V (a) 1:2:3 (b) 2:1:3 (c) 3:2:1 (d) 6:3:2
(c) increases by 0.059 V 53. The emf of the cell involving the following reaction,
(d) decreases by 0.0059 V 2Ag+ + H2 h 2Ag + 2H+ is 0.80 V. The standard
43. The oxidation potential of a hydrogen electrode at pH = oxidation potential of silver electrode is
1 is (T = 298 K): (a) –0.80 V (b) 0.80 V
(a) 0.059 volt (b) 0 volt (c) 0.40 V (d) –0.40 V
(c) –0.059 volt (d) 0.59 volt 54. For the net cell reaction of the cell Zn(s)|Zn2+||Cd2+|Cd(s)
44. The electrode potential becomes equal to standard elec- DG° in kilo joules at 25°C is (E°cell = 0.360 V):
trode potential when reactants and products concentra- (a) 112.5 (b) 69.47 (c) –34.73 (d) –69.47
tion ratio is 55. How many faradays are required to reduce one mol of
(a) equal to 1 (b) greater than 1 MnO4– to Mn+2?
(c) less than 1 (d) None of the above (a) 1 (b) 2 (c) 3 (d) 5
45. Given standard electrode potentials: 56. Cu+ + e– h Cu, E° = X1 V;
Fe3+ + 3e– h Fe; E° = –0.036 V Cu2+ + 2e– h Cu, E° = X2 volt, then for
Fe2+ + 2e– h Fe; E° = –0.440 V
Cu2+ + e– h Cu+, E° (volt) will be
The standard electrode potential E° for
(a) X1 – 2X2 (b) X1 + 2X2
Fe3+ + e– h Fe2+ is
(c) X1 – X2 (d) 2X2 – X1
(a) –0.476 V (b) –0.404 V 57. M2+ + 2e h M. 0.275 g of metal M is deposited at
(c) 0.440 V (d) 0.772 V the cathode due to passage of 1 A of current for 965 s.
46. The reduction potential of a hydrogen electrode at pH Hence atomic weight of the metal M is
10 at 298 K is: (p = 1 atm) (a) 27.5 (b) 55.0 (c) 110.0 (d) 13.75
(a) 0.51 volt (b) 0 volt 58. A certain metal salt solution is electrolysed in series
(c) –0.591 volt (d) 0.059 volt with a silver coulometer. The weight of silver and the
47. The emf of the cell, Ni|Ni2+ (1.0 M)||Ag+ (1.0 M)|Ag[E° metal deposited are 0.5094 g and 0.2653 g. Calculate
for Ni2+/Ni = – 0.25 V, E° for Ag+/Ag = 0.80 V] is giv- the valency of the metal if its atomic weight is nearly
en by [E° for Ag+/Ag = 0.80 V] that of silver.
(a) –0.25 + 0.80 = 0.55 V (a) 1 (b) 2 (c) 3 (d) 4
(b) –0.25 – (+0.80) = –1.05 V
(c) 0 + 0.80 – (–0.25) = +1.05 V
(d) –0.80 – (+0.25) = –0.55 V
48. E° (Ni2+/Ni) = –0.25 V, E° (Au3+/Au) = 1.50 V. The LEVEL II
emf of the voltaic cell Ni|Ni2+ (1.0 M)||Au3+ (1.0 M)|
Au is 1. Consider the standard reduction potentials (in volts) as
(a) 1.25 V (b) –1.75 V shown in figure. Find E°.
(c) 1.75 V (d) 4.0 V –0.936 –0.576 1
SO2– SO2– S2O 2–
49. A chemist wants to produce Cl2(g) from molten NaCl. 4 3
2 3
How many grams could be produced if he uses a steady Eo = ?

current of 2 amp for 2.5 minutes?
(a) 0.326 V (b) 0.425 V (c) 0.756 V (d) 0.512 V
(a) 3.55 g (b) 1.775 g (c) 0.110 g (d) 0.1775 g
2. Calculate the electrode potential at 25°C of Cr3+,
50. Consider the reaction: (T = 298 K)
Cr2 O72 - electrode at pOH = 11 in a solution of 0.01 M
Cl2(g) + 2Br–(aq) h 2Cl–(aq) + Br2(aq) both in Cr3+ and Cr2O72–. E° value for the cell
The emf of the cell, when [Cl–] = [Br2] = [Br–] = 0.01
Cr2 O72 - + 14H+ + 6e h 2Cr3+ + 7H2O
M and Cl2 gas is at 1 atm pressure, will be (E° for the
above reaction is = 0.29 volt): E° = 1.33 V.
(a) 0.54 V (b) 0.35 V (a) 0.725 V (b) 0.936 V
(c) 0.24 V (d) –0.29 V (c) 0.652 V (d) 0.213 V
51. Three Faradays of electricity was passed through an 3. The standard oxidation potential for the half-cell
aqueous solution of iron (II) bromide. The mass of iron NO -2 (g) + H2O h NO3- (aq) + 2H+(aq) + 2e is
metal (atomic mass 56) deposited at the cathode is
–0.78 V.
(a) 56 g (b) 84 g (c) 112 g (d) 168 g

Calculate the reduction potential in 9 molar H+ assum- 11. The standard oxidation potential of Ni/Ni2+ electrode
ing all other species at unit concentration. is 0.236 V. If this is combined with a hydrogen elec-
(a) 0.235 V (b) –0.0142 V trode in acid solution, at what pH of the solution will
(c) 0.836 V (d) –0.0474 V the measured emf be zero at 25°C? Assume [Ni–2+] =
4. The emf of the cell M|Mn+ (0.02 M) || H+ (1 M) | H2 (g) 1 M.
(1 atm), Pt at 25°C is 0.81 V. The valency of the metal (a) 3 (b) 6.5 (c) 5.5 (d) 4
if the standard oxidation potential of the metal is 0.76 12. The equivalent conductance of silver nitrate solution
V? at 250°C for an infinite dilution was found to be 133.3
(a) 5 (b) 2 (c) 4 (d) 3 ohm–1 cm2eq–1. The transport number of Ag+ ions in
5. In two vessels each containing 500 mL water, 0.5 m very dilute solution of AgNO3 is 0.464. The equivalent
mol of aniline (Kb = 10–9) and 25 m mol of HCl are conductance of Ag+ at infinite dilution is
added separately. Two hydrogen electrodes are con- (a) 34.6 W–1 cm–1eq–1
structed using these solutions. Calculate the emf of cell (b) 61.9 W–1 cm–1eq–1
made by connecting them appropriately. (c) 52.7 W–1 cm–1eq–1
(a) 0.395 V (b) 0.792 V (c) 0.452 V (d) 0.312 V (d) 49.2 W–1 cm–1eq–1
6. The EMF of the standard weston cadmium cell 13. Same quantity of electricity is being used to liberate
Cd (12.5%) in Hg | 3 CdSO4, 8H2O (solid) | standard iodine (at anode) and a metal x (at cathode). The mass
solution of CdSO4 | Hg2SO4 (s) | Hg is 1.0180 volts at of x deposited is 0.617 g and the iodine is completely
25°C and the temperature coefficient of the cell emf, reduced by 46.3 cc of 0.124 M sodium thiosulphate.
Ê ∂E ˆ -5 -1 Find the equivalent mass of x.
ÁË ˜¯ = - 4.0 ¥ 10 V deg . Calculate DG, DH and (a) 213.5 (b) 108.2 (c) 111.2 (d) 310.6
∂T P
14. Dal lake has water 8.2 ¥ 1012 L approximately. A power
DS for the reaction in the cell when n = 2. reactor produces electricity at the rate of 1.5 ¥ 106 cou-
(a) DG = –196.5 kJ, DH = 198.8 kJ, DS = –7.72 J/deg lomb per second at an appropriate voltage. How many
(b) DG = 196.5 kJ, DH = 198.8 kJ, DS = –7.72 J/deg years would it take to electrolyse the lake?
(c) DG = 196.5 kJ, DH = 198.8 kJ, DS = –7.72 J/deg (a) 2.4 million years (b) 5.3 million years
(d) DG = –196.5 kJ, DH = 198.8 kJ, DS = 7.72 J/deg (c) 1.9 million years (d) 4.6 million years
7. The standard electromotive force of the cell: 15. Calculate the emf of the cell
Fe | Fe2+(aq) || Cd2+ | Cd is 0.0372 V Pt, H2 (1.0 atm) | CH3COOH (0.1 M) || NH3 (aq, 0.01
The temperature coefficient of emf is –0.125 V K–1. M) | H2 (1.0 atm), Pt,
Calculate the quantities DG°, DH° and DS° at 25°C. Ka (CH3COOH) = 1.8 ¥ 10–5, Kb (NH3) = 1.8 ¥ 10–5
(a) DG° = –7179.6 J, DH° = –7196.43 kJ, DS° = (a) –0.92 V (b) –0.46 V
–24.125 kJ/K (c) –0.35 V (d) –0.20 V
(b) DG° = 7179.6 J, DH° = –7196.43 kJ, DS° = 16. Calculate E° for the following reactions at 298 K:
–24.125 kJ/K
(c) DG° = 7179.6 J, DH° = 7196.43 kJ, DS° = 24.125 Ag(NH3 ) +2 + e – m Ag + 2NH3
kJ/K Ag(CN)2– + e - m Ag + 2CN -
(d) DG° = 7179.6 J, DH° = 7196.43 kJ, DS° = 24.125
kJ/K o
Given: EAg +
|Ag
= 0.7991 V, KIns[Ag(NH3)+2] = 6.02 ¥
8. A current of 0.193 amp is passed through 100 mL of
0.2M NaCl for an hour. Calculate pH of solution after 10–8 and KIns[Ag(CN)–2] = 1.995 ¥ 10–19
electrolysis. Assume no volume change. (a) 0.372 V, –0.307 V (b) 0.214 V, –0.21 V
(a) 11.9 (b) 12.82 (c) 12.0 (d) 11.5 (c) –0.21 V, 0.372 V (d) –4.12 V, 0.307 V
9. The emf of the cell is ________for this reaction 17. The equivalent conductance of 0.10 N solution of
Mg(s) | Mg2+ (0.1 M) || Ag+ (1 ¥ 10–4 M) | Ag MgCl2 is 97.1 mho cm2eq–1 at 25°C. A cell with elec-
trode that are 1.5 cm2 in surface area and 0.5 cm apart
o
EAg +
/Ag
= 0.8 V, EMg
o
2+
/Mg
= - 2.37 V is filled with 0.1 N MgCl2 solution. How much current
will flow when potential difference between the elec-
(a) 2.96 V (b) 3.2 V (c) 1.9 V (d) 4.4 V
trodes is 5 V?
10. Silver is electrodeposited on a metallic vessel of sur-
(a) 0.1432 amp (b) 0.214 amp
face area 800 cm2 by passing a current of 0.20 amp for
(c) 0.321 amp (d) 0.1456 amp
3.0 hrs. The thickness of silver deposited ___.
18. A solution of Ni(NO3)2 is electrolysed between plati-
Given its density is 10.47g/cc [Atomic weight of Ag =
num electrodes using a current of 5 amp for 20 min-
108]
utes. What mass of Ni is deposited at the cathode?
(a) 3.2 ¥ 10–4 cm (b) 1.29 ¥ 10–4 cm
(a) 2.2 g (b) 3.5 g (c) 1.6 g (d) 1.803 g
(c) 2.88 ¥ 10 cm
–4
(d) 4.2 ¥ 10–3 cm

19. Three electrolytic cells, A, B, C containing solutions of DH and DS of the reaction at 25°C.
ZnSO4, AgNO3 and CuSO4 respectively are connect-
Given: E o 3+ = 0.5 V, E o 3+ 2+ = –0.41 V
ed in series. A steady current of 1.5 amp was passed Cr ,Cr Cr ,Cr
through them until 1.45 g of silver deposited at the DG of the reaction at 35°C = –270.50 kJ
cathode of cell B. How long did the current flow? What (a) DH = –51.05 kJ, DS = 700 kJ K–1
mass of Cu and Zn were deposited? (b) DH = –31.05 kJ, DS = 700 kJ K–1
(a) 14.40 min, Cu = 0.427 g, Zn = 0.437 g (c) DH = –51.05 kJ, DS = 706 kJ K–1
(b) 15.2 min, Cu = 0.52 g, Zn = 0.247 g (d) DH = –53.05 kJ, DS = 706 kJ K–1
(c) 13.3 min, Cu = 0.437 g, Zn = 0.427 g 25. How many grams of silver could be plated out on a
(d) 12.5 min, Cu = 0.534 g, Zn = 0.232 g serving tray by electrolysis of a solution containing
20. In a fuel cell H2 and O2 react to produce electricity. In Ag(l) for a period of 8.0 hrs at a current of 8.46 amp?
the process H2 gas is oxidised at the anode and O2 is What is the area of the tray if the thickness of the silver
reduced at the cathode. If 67.2 L of H2 at NTP reacts platting is 0.00254 cm? Density of silver is 10.5 g/cm3.
in 15 min, what is the average current produced? If the (a) 124.18 g, 1.02 ¥ 10–5 cm2
entire current is used for electro-deposition of Cu from (b) 124.18 g, 1.02 ¥ 10–2 cm2
Cu2+, how many g of Cu are deposited? (c) 272.18 g, 1.02 ¥ 10–4 cm2
(a) I = 443.3 A , MCu = 190.5 g (d) 272.18 g, 1.02 ¥ 10–2 cm2
(b) I = 643.3 A , MCu = 190.5 g 26. The solubility product of Fe(OH)3 at 25°C is 10–36.4
(c) I = 643.3 A , MCu = 180.5 g mol4 dm–12 and E° (Fe3+/Fe) = –0.036 V. The standard
(d) I = 543.3 A, MCu = 190. 5 g emf of the reaction Fe(OH)3(s) h Fe3+ + 3OH–.
21. During the discharge of a lead storage battery, density (a) –0.586 V (b) –1.786 V
of H2SO4 fell from 1.294 to 1.139 g/mL. Sulphuric acid (c) –0.786 V (d) –0.286 V
of density 1.294 is 39% H2SO4 by weight and that of 27. The solubility product and solubility of AgCl in the fol-
density 1.139 g/mL is 20% H2SO4 by weight. The bat- lowing cell which has an emf of 0.455 V at 25°C is
tery holds 3.5 L of the acid and volume remains practi- Ag/AgCl in 0.1 M KCl | 0.1 M AgNO3 | Ag
cally constant during discharge. Calculate ampere-hour
(a) 1.95 ¥ 10–9, 1.396 ¥ 10–5 mol/L
of which the battery must have been used. The charging
(b) 1.95 ¥ 10–10, 1.396 ¥ 10–9 mol/L
and discharging reactions are:
(c) 1.95 ¥ 10–10, 1.396 ¥ 10–4 mol/L
Pb + SO 24 - h PbSO4 + 2e– (charging) (d) 1.95 ¥ 10–4, 1.396 ¥ 10–4 mol/L
PbO2 + 4H + +
SO 24 -
+ 2e h PbSO4 + 2H2O
– 28. For a saturated solution of AgCl at 25°C, specific con-
(discharging) ductance is 3.41 ¥ 10–6 ohm–1 cm–1 and that of water
(a) 245.04 A Hr (b) 255.04 A Hr used for preparing the solution was 1.60 ¥ 10–6 ohm–1
(c) 235.04 A Hr (d) 265.04 A Hr cm–1. What is the solubility product of AgCl? leq(AgCl)
22. By how much would the oxidising power of the = 138.3 ohm–1 cm–1 equiv–1.
(MnO -4 |Mn 2 + ) couple change if the H+ ions concen- (a) 2.51 ¥ 10–6 mol2/L2 (b) 1.21 ¥ 10–6 mol/L2
tration is decreased 100 times at 25ºC? (c) 2.71 ¥ 10–5 mol/L (d) 1.72 ¥ 10–10 mol2/L2
(a) Increases by 189 mV 29. A hydrogen electrode placed in a buffer solution of
(b) Decreases by 189 mV CH3COONa and acetic acid in the ratio’s x:y and y:x
(c) Will increase by 19 mV has oxidation potential values E1 volts and E2 volts
(d) Will decrease by 19 mV
respectively at 25° C. The pKa values of acetic acid
23. The useful work done during the reaction
would be (where pressure of H2 is 1 atm).
1
Ag(s) + Cl2(g) h AgCl(s)
2 E1 + E2 E2 – E1
Would be (a) (b)
0.118 0.118
(a) 110 kJ mol–1 (b) 220 kJ mol–1
(c) 55 kJ mol –1
(d) 100 kJ mol–1 E1 + E2 E1 – E2
(c) – (d)
Given: 0.118 0.118
0 0
ECl = 1.36V, EAgCl/Ag/Cl – = 0.220 V, PCl2 = 1 atm
/Cl –
2 30. EIo |I – = 0.6197 V and EI0– |I – = 0.5355 V
2 3
and T = 298 K
24. Construct the cell corresponding to the reaction: What is the equilibrium constant for the formation of
-
3Cr2+ (1M) h 2Cr3+ (1M) + Cr(s) triiodide ion I2 + I– m I 3 at 298 K?
and predict if the reaction is spontaneous. Also calcu- (a) 614.9 (b) 71.49 (c) 714.9 (d) 61.49
late the following:

31. A current was passed in series through a solution of

(c) A + A - A (d) A - A + A
1 2 3 1 2 3
a salt of a metal X and solution of ZnSO4 using zinc
electrodes. After a certain time, 0.348 g of X and 1.264 39. Salts of A (atomic weight = 7), B (atomic weight = 27)
g of zinc has been deposited. If the salt is represented and C (atomic weight = 48) were electrolysed under
as XCl, what is the molar mass of X? identical conditions using the same quantity of electric-
(a) 18 g mol–1 (b) 27 g mol–1 ity. It was found that when 2.1 g of A was deposited, the
–1
(c) 36 g mol (d) 9 g mol–1 weights of B and C deposited were 2.7 g and 7.2 g. The
32. Given, E° = –0.268 V for the Cl– | PbCl2 | Pb couple valencies of A, B and C respectively are:
and –0.126 V for the Pb2+ | Pb couple, determine Ksp (a) 3, 1 and 2 (b) 1, 3 and 2
for PbCl2 at 25°C? (c) 3, 1 and 3 (d) 2, 3 and 2
(a) 2.312 ¥ 105 M3 (b) 1.536 ¥ 10–5 M3 40. The cost at 5 paise/KWH of operating an electric motor
(c) 1.214 ¥ 10 M–4 3
(d) 2.416 ¥ 10–4 M3 for 8 hours which takes 15 amp at 110 V is
33. Consider the cell H 2 (Pt) H3O + (aq) Ag + Ag. The (a) `66 (b) 66 paise
1 atm pH = 5.5 xM (c) 37 paise (d) `6.60
41. A silver wire dipped in 0.1 M HCl solution saturated
measured emf of the cell is 1.023 V. What is the value with AgCl develops a potential of –0.25 V. If E°Ag/Ag+
0
of x? EAg +
, Ag
= +0.799 V. [T = 25°C] = –0.799 V, the Ksp of AgCl in pure water will be:
(a) 2.95 ¥ 10–11 (b) 5.1 ¥ 10–11
(a) 0.25 M (b) 2 ¥ 10–3 M
(c) 3.95 ¥ 10 –11
(d) 1.95 ¥ 10–11
(c) 1.5 ¥ 10 M–3
(d) 1.5 ¥ 10–2 M
42. Consider the reaction of extraction of gold from its ore
34. Hg2Cl2 is produced by the electrolytic reduction of
Au + 2CN–(aq.) + O2(g) + H2O h Au(CN)2– + OH–
Hg2+ ion in presence of Cl– ion is 2Hg2+ + 2Cl– + 2eQ
Use the following data to calculate DG° for the reaction
Æ Hg2Cl2. Calculate the current required to have a rate
Kf [Au(CN)2–] = X
production of 44 g per hour of Hg2Cl2 [Atomic weight
O2 + 2H2O + 4e– h 4OH– : E° = +0.41 V
of Hg = 200.6]:
Au3+ + 3e– h Au : E° = +1.5 V
(a) 5 amp (b) 4 amp
Au3+ + 2e– h Au+ : E° = +1.4 V
(c) 6.5 amp (d) 3.5 amp
35. The ionisation constant of a weak electrolyte is 25 ¥ (a) –RT ln X + 1.29 F (b) –RT ln X – 2.11 F
10–6 while the equivalent conductance of its 0.01 M so- (c) –RT ln + 2.11 F (d) –RT ln X – 1.29 F
lution is 19.6 S cm2 eq–1. The equivalent conductance 43. Consider the following Galvanic cell:
of the electrolyte at infinite dilution (in S cm2 eq–1) will Voltmeter
H2(g) Cl2(g)
be:
(a) 250 (b) 196 (c) 392 (d) 384 K NO–3
36. Which of the following curve represents the variation
of lM with C for AgNO3? Pt(s)
Anode Cathode
lM lM
(a) (b) By what value the cell voltage when concentration of
ions in anodic and cathodic compartments both in-
C C creased by factor of 10 at 298 K.
(a) +0.0591 (b) –0.0591
lM lM (c) –0.1182 (d) 0
(c) (d)
44. For the fuel cell reaction 2H2(g) + O2 (g) h 2H2O(l)
; DfH°298 (H2O, l) = –285.5 kJ/mol. What is DS°298 for
C C
the given fuel cell reaction? Given
37. Four moles of electrons were transferred from anode O2(g) + 4H+(aq) + 4e– h 2H2O(l ) E° = 1.23 V
to cathode in an experiment on electrolysis of water. (a) –0.322 J/K (b) –0.635 kJ/K
The total volume of the two gases (dry and at STP) (c) 3.51 kJ/K (d) –0.322 kJ/K
produced will be approximately (in litres):
45. The resistance of 0.5 M solution of an electrolyte in a
(a) 22.4 (b) 44.8 (c) 67.2 (d) 89.4
cell was found to be 50 W. If the electrodes in the cell
38. Equivalent conductance of BaCl2, H2SO4 and HCl
1 2 3
are 2.2 cm apart and have an area of 4.4 cm2 then the
at infinite dilution are A , A and A respectively. molar conductivity (in S m2 mol–1) of the solution is
Equivalent conductance of BaSO4 solution is (a) 0.2 (b) 0.02
(a) A + A - 2 A
1 2 3
(b) A + A + A
1 2 3 (c) 0.002 (d) None of these

46. The dissociation constant of n-butyric acid is 1.6 ¥ 10–5 4.

and the molar conductivity at infinite dilution is 380 ¥
Column I Column II
10–4 Sm2mol–1. The specific conductance of the 0.01 M
(Quantities) (Factors on which
acid solution is
dependency exist)
(a) 1.52 ¥ 10–5 Sm–1 (b) 1.52 ¥ 10–2 Sm–1
(c) 1.52 ¥ 10 Sm
–3 –1
(d) none (A) Molar conductance (p) Temperature
(B) emf of a cell in op- (q) Concentration of
eration species involved
LEVEL III (C) Electrode potential (r) Nature of sub-
stance involved
1. For the galvanic cell (D) Standard reduction (s) No. of electrons
+ 2+ potential lost or gained in
Ag|Ag (aq) (0.1M) || Cd (aq) (0.1M)|Cd the reaction
o
( EAg +
/Ag
= 0.80 V, ECd
o
2+
/Cd
= - 0.40 V), (t) Dilution
Column I Column II Comprehension I

(A) The cell reaction (p) –1.17 V The standard reduction potentials of some half-reactions are
(B) Reaction quotient (q) –1.20 V given as below:
(C) The cell potential (r) Non-spontaneous Cu2+ + e h Cu+; E1o = 0.15 V
(D) The standard cell po- (s) 1/10 Cu+ + e h Cu; E2o = 0.05 V
tential
Ag+ + e h Ag; E3o = 0.799 V
(t) E°cell = E°C – E°A
data in SRP The decrease in Gibbs energy (–DG) is responsible for the
production of equivalent amount of electrical work. Thus,
2. Consider the reduction reactions: DG = nFE
(i) Sn2+ + 2e– h Sn; E° = –0.14 V 5. The E° for Cu|Cu2+ in volt is
(ii) Sn4+ + 2e– h Sn2+; E° = 0.13 V (a) 0.35 (b) –0.35 (c) +0.325 (d) –0.066 V
o
Column I Column II 6. The Ecell for Cu|Cu2+ || Ag+|Ag in volt is
(a) +0.449 (b) 0.733 V (c) –0.339 (d) –0.474
o
(A) ESn 4+
/Sn
(p) –0.00 5 V 7. The E cell for Cu|Cu2+ (0.1 M) || (0.1 M) Ag+|Ag the
reaction is
(B) Standard oxidation (q) +0.005 V (a) 0.7034 V (b) 0.374 V
potential of Sn to Sn (c) –0.415 V (d) –0.10945 V
(+IV)
Comprehension II
(C) Disproportionation (r) Spontaneous
of Sn2+ o
ERP and their respective half-reactions for some change are
(D) Oxidation of Sn to (s) Non-spontaneous given below:
Sn4+ -
(i) MnO 4 (aq) + 8H+ + 5e h Mn+5(aq) + 4H2O(l);
x1E1o + x 2 E o2 E° = +1.52 V
(t) E∞ =
x3 (ii) MnO -4 (aq) + 4H+ + 2e h MnO2(s) + 2H2O(l);
E° = +2.26 V
3. (iii) MnO -4 (aq) + 2e h Mn+5(aq); E° = +0.56 V
Column I Column II (acid med.)
(A) Cathode (p) Primary cell (iv) Mn3+ + e h Mn2+; E° = +1.51 V (acid med.)
(B) 1 Coulomb (q) Secondary cell (v) Mn4+ + e h Mn3+; E° = +0.95 V (acid med.)
8. The most stable oxidation state of Mn is
(C) Dry cell (r) 6.24 ¥ 1018 elec- (a) Mn2+ (b) Mn4+ (c) Mn7+ (d) Mn6+
trons 9. Which is the least stable oxidation state of Mn?
(D) Lead storage cell (s) Concentration cell (a) Mn2+ (b) Mn4+ (c) Mn7+ (d) Mn6+
2+
(E) Zn | Zn (0.01 M) || (t) Positive terminal 10. The E° for, Mn + 2e h Mn ; is equal to
4+ 2+
Zn2+ (0.1 M) | Zn of electrochemical (a) 1.23 V (b) 2.46 V (c) 0.56 V (d) –0.56 V
cell

Comprehension III 14. Among the following, identify the correct statement.
(a) Chloride ion is oxidised by O2.
The potential of an electrode when each species involved in it
(b) Fe2+ is oxidised by chloride ion.
exists in the standard state is called its standard potential. The
(c) Iodide ion is oxidised by chlorine ion.
standard reduction potential of a couple is the measure of its
(d) Mn2+ is oxidised by chlorine.
tendency to get reduced. A series obtained by arranging the
15. While Fe3+ is stable, Mn3+ is not stable in acid solution
various couples in order of their decreasing standard poten-
because
tial is called electrochemical series. Any of the two couples
(a) O2 oxidises Mn2+ to Mn3+
of this series joined together gives an electrochemical cell
(b) O2 oxidises both Mn2+ and Fe2+
in which reduction occurs at the electrode which occupies
(c) Fe3+ oxidises H2O to O2
the higher position. The standard potential of hydrogen elec-
(d) Mn3+ oxidises H2O to O2
trode is taken to be zero by convention. Given below are the
sequence of half-reactions (acidic media) with relevant E0 Comprehension IV
values in volt at 298K.
The molar conductance of NaCl varies with the concentra-
0.560 2.26 0.95
MnO 4– æææ
Æ MnO 2–
4 æææ
Æ MnO 2 æææ
Æ tion as shown in the following table and all values follows
1.50 –1.18
Mn 3+ æææ
Æ Mn 2+ æææ
Æ Mn the equation
lmC = lm – b C Where lmC = molar specific conductance
Also given some more data are:
– 0.44
Fe 2+ æææÆ Fe(s) æææÆ Fe3+
+0.036 lm = molar specific conductance at infinite dilution
C = molar concentration
11. The E° for MnO 4- h Mn 2 + is equal to Molar Concentration of Molar Conductance in
(a) 1.054 V (b) 1.506 V NaCl ohm–1 cm2 mole–1
(c) 5.27 V (d) 7.53 V
4 ¥ 10–4 107
12. The value of E° for the reaction:
9 ¥ 10–4 97
MnO 4– + 5Fe 2+ + 8H + h Mn 2+ + 5Fe3+ + 4H 2 O,
16 ¥ 10–4 87
is equal to
When a certain conductivity cell was filled with 25 ¥ 10–4
(a) 0.734 V
(M) NaCl solution. The resistance of the cell was found to
(b) 0.284 V
be 1000 ohm. At infinite dilution, conductance of Cl– and
(c) 4.498 V
(d) Cannot be calculated as concentrations of species SO 4–2 are 80 ohm–1 cm2 mole–1 and 160 ohm–1 cm2 mole–1
are not given. respectively.
13. For the cell 16. What is the molar conductance of NaCl at infinite dilu-
Fe(s) | Fe2+ (0.1M) || 100 mL 0.3M HA (pKa =5.2) tion?
mixed with 50 mL 0.4M NaOH | H2 (1 atm), Pt (a) 147 ohm–1 cm2 mole–1
the Ecell at 298 is equal to (b) 107 ohm–1 cm2 mole–1
(a) –0.15 V (b) +0.185 V (c) 127 ohm–1 cm2 mole–1
(c) –0.44 V (d) +0.1623 V (d) 157 ohm–1 cm2 mole–1
17. What is the cell constant of the conductivity cell:
Comprehension IV (a) 0.385 cm–1 (b) 3.85 cm–1
–1
Redox reactions play a pivotal role in chemistry and biology. (c) 38.5 cm (d) 0.1925 cm–1
The values of standard redox potential (E°) of two half-cells 18. If the cell (C) is filled with 5 ¥ 10–3 (N) Na2SO4 the
reactions decide which way the reaction is expected to pro- observed resistance was 400 ohm. What is the molar
ceed. A simple example is a Daniell cell in which zinc goes conductance of Na2SO4.
into solution and copper gets deposited. Given below are a set (a) 19.25 ohm–1 cm2 mole–1
of half-cell reactions (acidic medium) along with their E° (V (b) 96.25 ohm–1 cm2 mole–1
with respect to normal hydrogen electrode) values. (c) 385 ohm–1 cm2 mole–1
(d) 192.5 ohm–1 cm2 mole–1
I2 + 2e– h 2I–; E° = 0.54
Cl2 + 2e– h 2Cl–; E° = 1.36 Comprehension VI
Mn3+ + e– h Mn2+; E° = 1.50 In a lead storage battery, Pb (anode) and PbO2 (cathode) are
used. Concentrated H2SO4 is used as electrolyte. The battery
Fe + e h Fe ;
3+ – 2+
E° = 0.77
holds 3.5 L acid with it. In the discharge process, the density
O2 + 4H + 4e h 2H2O;
+ –
E° = 1.23 of acid fell from 1.294 to 1.139 g/mL. The sulphuric acid
of density 1.294 g mL–1 is 39% by mass and that of density
1.139 g/mL is 20% by mass.

19. Equivalent mass of sulphuric acid in lead storage bat- o

ENO - = + 0.79 volt ;
tery is 3 /NO2
(a) 49 (b) 98 RT
(c) 24.5 (d) None of these at 298 K(2.303) = 0.06 volt
F
20. Normalities of sulphuric acid before and after dis-
27. ECell for reduction of NO3– h
charge are
[HNO3] = 1 M is [At T = 298]
(a) 5.15, 2.32 (b) 2.32, 5.15
(a) = 0.61 (b) = 0.71 (c) = 0.51 (d) = 0.81
(c) 5.15, 5.15 (d) 2.32, 2.32
28. At what HNO3 concentration thermodynamic tendency
21. Number of ampere-hours for which the battery must
for reduction of NO3– into NO and NO2 by copper is
have been used is
same?
(a) 26504 amp-hrs (b) 2650.4 amp-hrs
(a) 101.23 M (b) 100.56 M (c) 100.66 M (d) 100.12 M
(c) 265.04 amp-hrs (d) 26.504 amp-hrs
22. The amount of charge which the battery must have (Assertion and Reason)
been used is (A) Statement 1 is True, Statement 2 is True; Statement 2 is
(a) 9.88 F (b) 8.98 F (c) 8.89 F (d) 7.88 F a correct explanation for Statement 1.
23. Which of the following takes place in discharge pro- (B) Statement 1 is True, Statement 2 is True; Statement 2 is
cess at anode? NOT a correct explanation for Statement 1.
(a) PbO2 + 4H+ + SO 4–2 + 2e– h PbSO4 + 2H2O (C) Statement 1 is True, Statement 2 is False.
(D) Statement 1 is False, Statement 2 is True.
(b) PbSO4 + 2H2O h PbO2 + 4H+ + SO 4–2 + 2e–
29. Statement 1: (E°)SRP value for the Mn3+/Mn2+ couple
(c) Pb + SO 4–2 h PbSO4 + 2e– is much more positive than that for Cr3+/Cr2+ or Fe3+/
(d) PbSO4 + 2e– h Pb + SO 4–2 Fe2+
Statement 2: The third ionisation energy of Mn is very
Comprehension VII high as it requires change from d5 to d4 configuration.
Chemical reaction involves interaction of atoms and mol- 30. Statement 1: Specific conductance decreases with di-
ecules. A large number of atoms/molecules (approximately lution whereas equivalent conductance increases.
6.023 ¥ 1023) are present in a few grams of any chemical Statement 2: On dilution, number of ions per millilitre
compound varying with their atomic/molecular masses. To decreases but total number of ions increases consider-
handle such large number conveniently, biochemistry, elec- ably.
trochemistry and radiochemistry. The following example il- 31. Statement 1: Calomel electrode especially saturated
lustrates a typical case, involving chemical/electrochemical with KCl solution is used as a reference electrode, i.e.,
reaction, which requires a clear understanding of the mole secondary standard electrode.
concept. A 4.0 molar aqueous solution of NaCl is prepared Statement 2: The potential of calomel electrode de-
and 500 mL of this solution is electrolysed. This leads to the pends upon the concentration of Cl– ions.
evolution of chlorine gas at one of the electrodes (atomic 32. Statement 1: The electrolytic cell during electrolysis
mass: Na = 23, Hg = 200; 1 Faraday = 96500 coulombs). of NaCl (aq.) on addition of little red litmus shows a
24. The total number of moles of chlorine gas evolved is blue colour.
(a) 0.5 (b) 1.0 (c) 2.0 (d) 3.0 Statement 2: At cathode: 2H+ + 2e h H2
25. If the cathode is Hg electrode, the maximum weight (g) The reaction at cathode gives rise to an increase in pH
ranging in alkaline medium.
of amalgam formed in this solution is
33. Statement 1: If an aqueous solution of NaCl is elec-
(a) 200 (b) 225 (c) 400 (d) 446
troysed, the product obtained at the cathode is H2 gas
26. The total charge (coulomb) required for complete elec-
and not Na.
trolysis is
Statement: Gases are liberated faster than the metals.
(a) 24125 (b) 48250 (c) 96500 (d) 193000
Multiple correct Question
Comprehension VIII
34. The electrolysis of aqueous solution of CuBr2 using
Copper reduces NO3- into NO and NO2 depending upon platinum electrode would lead to the evolving of
concentration of HNO3 in solution. Assuming [Cu2+] = 0.1 (a) Br2 gas at anode
M, and PNO = PNO2 = 10–3 atm and using given data answer (b) Br2 gas at anode and O2 gas at cathode
the following questions: (c) Copper(s) at cathode
o
ECu 2+
/Cu
= + 0.34 volt ; (d) H2 gas at cathode
35. Which of the following statements is (are) correct?
o
ENO -
/NO
= + 0.96 volt (a) The reactivity of metals decreases in going down
3
the electrochemical series.

(b) A metal can displace any other metal placed in which the cell reaction is 0.6195 V at 0°C and 0.6753
above it in the electrochemical series from its salt V at 25° C. The value of DH of the reaction at 25°C is
solution. (a) 167.26 kJ/mol (b) –1.961 kJ/mol
(c) The oxidising power of the substances decrease (c) 40 K/mol (d) –0.469 Kcal/mol
from the top to the bottom in the electrochemical 42. The standard electrode potentials, EIo /I- , EBr
o
and
-
series. 2 /Br
2
o
(d) A redox reaction is feasible when the substance EFe/Fe 2 + are respectively +0.54 V, –1.09 V and 0.44 V
having higher reduction potential gets reduced as the basis of given data which of the following is/are
and the one having lower reduction potential gets spontaneous?
oxidised. (a) Br2 + 2I– h 2Br– + I2
36. When a nickel spatula is used to stir an aqueous copper (b) Fe + Br2 h Fe2+ + 2Br–
sulphate solution
(c) Fe + I2 h Fe2+ + 2I–
(a) the solution is stirred well without any chemical
(d) I2 + 2Br– h 2I– + Br2
change.
43. Which of the following statements is (are) not correct?
(b) nickel spatula gets partly oxidized into Ni2+ ions.
(a) Metallic conduction is due to the movement of
(c) Cu2+ ions present in the solution get partly re-
electrons whereas the electrolytic conduction is
duced into Cu.
due to the movement of ions.
(d) copper gets deposited on the spatula.
(b) Both metallic and electrolytic conductions in-
37. Which among the following statement(s) is/are correct?
volve transfer of matter.
(a) If EA0 n + /A is negative, H+ will be reduced to H2 (c) Electrolytic conduction decreases with rise in
by the element ‘A’ temperature.
(b) Compounds of (Zn, Na, Mg) are reduced by hy- (d) Metallic conduction involves no chemical change.
drogen (H2) whereas those of noble metals (Cu, 44. Which of the following aqueous solution turn(s) alka-
Ag, Au) are not reducible. line after electrolysis?
(a) NaCl (b) CuCl2
(c) If EA0 n + /A is positive, An+ will be reduced to A by
(c) CH3COONa (d) K2SO4
H2 o
(d) M | Mn+ || H+ | H2 (Pt) will be spontaneous if 45. In which of the following cell(s): Ecell = Ecell ?
2+ +
EM0
n+ is negative (a) Cu(s) | Cu (0.01 M) || Ag (0.1 M) | Ag(s)
/M
(b) Pt(H2) | pH = 1 || Zn2+ (0.01 M) | Zn (s)
38. Electrode potential data are given below. (c) Pt(H2) | pH = 1 || Zn2+ (1 M) | Zn (s)
Fe3+(aq) + e– h Fe2+(aq); Eo = +0.77 V (d) Pt(H2) | H+ = 0.01 M || Zn2+ (0.01 M) | Zn(s)
Al3+(aq) + 3e– h Al(s); Eo = –1.66 V 46. Fuel cell involves following reaction(s):
(a) O2(g) + 2H2O(l) + 4e– h 4OH–(aq)
Br2(aq) + 2e h Br (aq); E = +1.08 V
– – o
(at cathode)
Based on the given data which statement/s is/are true? (b) O2(g) + 2H2O(l) + 4e– h 4OH–(aq)
(a) Fe2+ is stronger reducing agent than. Br–.
(at anode)
(b) Fe2+ is stronger reducing agent than Al.
(c) 2H2(g) + 4OH–(aq) h 4H2O(l) + 4e–
(c) Al is stronger reducing agent than Fe2+.
(at anode)
(d) Br– is stronger reducing agent than Al.
(d) 2H2(g) + 4OH–(aq) h 4H2O(l) + 4e–
39. We observe blue colour if
(a) Cu electrode is placed in the AgNO3 solution. (at cathode)
(b) Cu electrode is placed in the ZnSO4. 47. In lead storage battery, during discharging process.
(c) Cu electrode is placed in the dil HNO3. Which of the following is not the correct statement?
(d) Cu electrode is placed in the NiSO4. (a) PbO2 gets oxidised.
40. The emf of the following cell (b) H2SO4 is produced.
Fe(s) | Fe2+ (0.1M) || Cu2+ (0.01M) | Cu (c) density of H2SO4 solution decreases.
is found to be equal to 0.75V. The emf of the cell can be (d) density of H2SO4 solution increases.
increased by 48. 100 mL of a buffer of 1 M NH3 and 1 M NH +4 are
(a) diluting concentration Fe2+ solution. placed in two voltaic cells separately. A current of 1.5 A
(b) diluting Cu2+ solution. is passed through both cells for 20 min. If electrolysis
(c) increasing the concentration of Fe2+ ions. of water only takes place, what is not true regarding the
(d) increasing the concentration of Cu2+. pH of
41. The standard emf of the cell, 2H2O + O2 + 4e– h 4OH– (R.H.S.)
Cd(s)| CdCl2 (aq) || AgCl(s) | Ag(s) 2H2O h 4H+ + O2 + 4e– (L.H.S.)
0.1M

(a) half-cell on L.H.S. will increase. 58. In the cell,

(b) half-cell on R.H.S. will increase. Tl | Tl+ (0.1 M) || Sn+2 (0.01 M) | Sn
(c) Both the half-cells will increase.
(d) Both the half-cells will decrease. ETo /T +
= 0.34V, ESn
o
+2
/Sn
= - 0.14
49. A current of 2.68 A is passed for one hour through an
a current of 40 mA is flowing from tin to thallium elec-
aqueous solution of CuSO4 using copper electrodes.
trode. An external battery of 1.2 V emf is connected
Select the correct statement (s) from the following:
(a) Increase in mass of cathode = 3.174 g. to the cell so that its polarity is opposite to the natural
(b) Decrease in mass of anode = 3.174 g. polarity of the cell. If 0.38 g of thallium is deposited in
(c) No change in masses of electrodes. one hour at 25°C, determine % efficiency of thallium
(d) The ratio between the change of masses of cath- electrode. (Tl = 204).
ode and anode is 1:2. 59. The given cell,
50. Fe is reacted with 1.0 M HCl. E° for Fe/Fe2+ = +0.34 Ag | AgCl | HCl (0.1 M) | H2 (1 atm) | Pt || Pt | H2 (1
volt. The correct observation(s) regarding this reaction atm) | H+ (c M) | KCl (1 M) | Hg2Cl2 | Hg () is used to
is/are: measure pH of solution. Given E° = 0.2873 V for Cl- |
(a) Fe will be oxidised to Fe2+. AgCl | Ag couple and E° = 0.2415 V for Cl- | Hg2Cl2
(b) Fe2+ will be reduced to Fe. | Hg couple, determine the concentration of H+ in the
(c) since emf is positive, the reaction shall occur. right cell if the potential of the given cell is 0.1256 V.
(d) since emf is positive, the reaction shall not occur. 60. Determine the degree of hydrolysis and hydrolysis con-
stant of aniline hydrochloride in M/32 solution of salt
Integer and Subjective Type Question at 298 K from the following cell data at 298 K:
51. At equimolar concentration of Fe2+ and Fe3+, what must Pt | H2 (1 atm) | H+ (1 M) || M/32 C6H5NH3Cl | H2 (1
[Ag+] be so that the voltage of the galvanic cell made atm) | Pt ; Ecell = –0.188 V.
from Ag+/Ag and Fe3+/Fe2+ electrodes equals zero? The 61. Calculate E° for the following reactions at 298 K:
reaction is Fe2+ + Ag+ m Fe3+ + Ag. Determine the
Ag(NH3 ) +2 + e – m Ag + 2NH3
equilibrium constant at 25°C for the reaction. Given:
o Ag(CN)2– + e – m Ag + 2CN –
Eo + = 0.799 volt and EFe
Ag /Ag
+3
/Fe2+
= 0.771 V.
52. Calculate the volume of Cl2 at NTP produced dur- Given:
ing electrolysis of MgCl2 which produces 6.50 g Mg.
o
EAg +
/Ag
= 0.7991 V, K ln s [Ag(NH3 ) 2+ ] = 6.02 ¥ 10-8
At. wt. of Mg = 24.3.
53. An ammeter and copper volt meter are connected in and K lns [Ag(CN) 2– ] = 1.995 ¥ 10 –19.
series in an electric circuit through which a constant 62. The resistance of a N/10 KCl solution is 245 ohms.
direct current flows. The ammeter shows 0.525 amp. Calculate the specific conductance and the equivalent
If 0.6354 g of Cu is deposited in one hour, what is per- conductance of the solution if the electrodes in the cell
centage error of ammeter? [At. wt. of Cu = 63.54.] are 4 cm apart and each having an area of 7.0 sq. cm.
54. Cd amalgam is prepared by electrolysis of a solution of 63. The resistance of a solution ‘A’ is 50 ohms and that of
CdCl2 using a mercury cathode. How many minute long solution ‘B’ is 100 ohms, both solutions being taken in
should a current of 5 amp is passed in order to prepare the same conductivity cell. If equal volumes of solu-
12% Cd-Hg amalgam on a cathode of 2.56 g mercury? tion A and B are mixed, If the resistance of the mixture
[At.wt. of Cd = 112.40.] using the same cell is R find 3R. (Assume that there is
55. The standard oxidation potential of Ni/Ni2+ electrode no increase in the degree of dissociation of A and B on
is 0.236 V. If this is combined with a hydrogen elec- mixing.)
trode in acid solution, at what pH of the solution will 64. In a conductivity cell the two platinum electrodes, each
the measured emf be zero at 250C? Assume [Ni2+] = 1 of area 10 sq. cm. are fixed 1.5 cm apart. The cell con-
M and PH2 = 1 atm. tained 0.05 N solution of a salt. If the two electrodes
are just half-dipped into the solution which has a resis-
56. 3 amp current was passed through an aqueous solution
tance of 50 ohms, find equivalent conductance of the
of an unknown salt of Pdn+ for 1 hr. 2.977 g of Pd was
salt solution.
deposited at cathode. Find n. (At. wt. of Pd = 106.4)
65. A big irregular shaped vessel contained water, the sp.
57. An acidic solution of Cu2+ salt containing 0.4 g of Cu2+
conductance of which was 2.56 ¥ 10–5 mho cm–1. 500
is electrolysed until all the Cu is deposited. The elec-
g of NaCl was then added to the water and the specific
trolysis is continued for seven more minutes with the
conductance after the addition of NaCl, was found to
volume of solution kept at 100 mL and the current at
be 3.10 ¥ 10–5 mho cm–1. Find the capacity of the ves-
1.2 ampere. Calculate the volume of gases evolved at sel if it is fulfilled with water. (l NaCl = 149.9)
NTP during entire electrolysis.

66. The equivalent conductance of 0.10 N solution of 76. Kd for dissociation of [Ag(NH3)2]+ into Ag+ and NH3 is
MgCl2 is 97.1 mho cm2 eq–1. A cell with electrodes that 6 ¥ 10–8. Calculate E° for the following half reaction;
are 1.50 cm2 in surface are and 0.50 cm apart is filled Ag (NH3)2+ + e– h 3
with 0.1 N MgCl2 solution. How much current will Given Ag+ + e– h
flow when the potential difference between the elec- 77. The overall formation constant for the reaction of 6
trodes is 5 V? mole of CN– with cobalt (II) is 1 ¥ 1019. The standard
67. At 18°C the mobilities of NH+4 and ClO–4 ions are 6.6 ¥ reduction potential for the reaction [Co(CN)6]3– + e– Æ
10–4 and 5.7 ¥ 10–4 cm2 V–1 sec–1 at infinite dilution. [Co(CN)6]4– is –0.83 V. Calculate the formation con-
Calculate equivalent conductance of ammonium chlo- stant of [Co(CN)6]3–.
rate solution. Given Co3+ + e– Æ Co2+; E° = 1.82 V
68. For H+ and Na+ the values of l are 349.8 and 50.11. 78. The emf of cell: H2(g)|Buffer||Normal calomal elec-
Calculate the mobilities of these ions and their veloci- trode is 0.6885 V at 40°C when the barometric pres-
ties if they are in a cell in which the electrodes are 5 cm sure is 725 mm of Hg. What is the pH of the solution.
apart and to which a potential of 2 V is applied. E°calomal = 0.28?
69. The equivalent conductance of an infinitely dilute solu- 79. A direct current of 1.25 A was passed through 200
tion NH4Cl is 150 and the ionic conductances of OH– mL of 0.25 M Fe2(SO4)3 solution for a period of 1.1
and Cl– ions are 198 and 76 respectively. What will be hour. The resulting solution in cathode chamber was
the equivalent conductance of the solution of NH4OH analysed by titrating against acidic KMnO4 solution.
at infinite dilution. If the equivalent conductance of a 25 mL permaganate solution was required to reach the
0.01 N solution NH4OH is 9.6, what will be its degree end point. Determine molarity of KMnO4 solution. If
of dissociation? Eo for Fe+3 + e m Fe+2 is 0.77 Volt.
70. Calculate the dissociation constant of water at 25°C 80. An electrochemical cell is constructed with an open
from the following data: switch as shown below.
Specific conductance of H2O = 5.8 ¥ 10–8 mho cm–1,
V
lH+ = 350.0 and lOH- = 198.0 mho cm2
Sn X
71. Calculate Ka of acetic acid if its 0.05 N solution has Salt Bridge
equivalent conductance of 7.36 mho cm2 at 25°C.
( lCH 3 COOH = 390.70)
72. The specific conductance of a saturated solution
of AgCl at 25°C after substracting the specific con-
ductance of water is 2.28 ¥ 10–6 mho cm–1. Find the 0.5 M Sn2+ 0.1 M Xn+
solubility product of AgCl at 25°C. (l AgCl = 138.3
mho cm2) When the switch is closed, mass of tin-electrode in-
73. An excess of liquid Hg was added to 10–3 M acidified creases. If E° (Sn2+/Sn) = –0.14 V and for E° (Xn+/X) =
solution of Fe3+ ions. It was found that only 5% of the – 0.78 V and initial emf of the cell is 0.65 V, determine
ions remainded as Fe3+ at equilibrium at 25°C. Calcu- n and indicate the direction of electron flow in the ex-
o ternal circuit.
late EHg|Hg 2+ at 25°C. The equilibrium reaction is
2 81. 10 g fairly concentrated solution of CuSO4 is electro-
lyzed using 0.01 F of electricity. Calculate
2Hg + 2Fe3+ Hg 22+ + 2Fe2+ (a) the weight of resulting solution.
and E oFe2+ |Fe3+ = – 0.77 V (b) equivalents of acid or alkali in the solution.
82. One of the methods of preparation of per disulphuric
(a) 0.023 V (b) –0.793 V acid, H2S2O8, involve electrolytic oxidation of H2SO4
(c) –0.029 V (d) 7.93 V at anode (2H2SO4 h H2S2O8 + 2H+ + 2e–) with oxy-
74. Equinormal solution of two weak acids, HA (pKa = 3) gen and hydrogen as by-products. In such an electroly-
and HB (pKa = 5) are each placed in contact with stan- sis, 9.722 L of H2 and 2.35 L of O2 were generated at
dard hydrogen electrode at 25°C. When a cell is con- STP. What is the weight of H2S2O8 formed?
structed by interconnecting them through a salt bridge 83. Assume that impure copper contains only iron, sil-
find the emf of the cell. ver and a gold as impurities. After passage of 140 A,
75. Estimate the cell potential of a Daniel cell having 1.0 for 482.5 sec, of the mass of the anode decreased by
M Zn++ and originally having 1.0 M Cu++ after suf- 22.260 g and the cathode increased in mass by 22.011
ficient NH3 has been added to the cathode compart- g. Estimate the % iron and % copper originally present.
ment to make NH3 concentration 2.0 M. Given Kf for 84. For the galvanic cell: Ag|AgCl(s)|KCl(0.2
[Cu(NH3)4]2+ = 1 ¥ 1012, E° for the reaction, Zn + Cu2+ M)||KBr(0.001 M)|AgBr(s)|Ag,
h 2+ + Cu is 1.1 V.

Calculate the emf generated and assign correct polarity 92. A dilute aqueous solution of KCl was placed between
to each electrode for a spontaneous process after taking two electrodes 10 cm apart, across which a potential of
into account the cell reaction at 25°C. 6 V was applied. How far would the K+ ion move in
[Ksp(AgCl) = 2.8 ¥ 10–10 ; Ksp(AgBr) = 3.3 ¥ 10–13] 2 hrs at 25°C? Ionic conductance of K+ ion at infinite
85. An aqueous solution of NaCl on electrolysis gives dilution at 25°C is 73.52 ohm–1 cm2 mole–1?
H2(g), Cl2(g) and NaOH according to the reaction: 93. Calculate the equilibrium concentration of all ions
2Cl–(aq) + 2H2O m 2OH–(aq) + H2(g) + Cl2(g) in an ideal solution prepared by mixing 25.00 mL of
A direct current of 25 amperes with a current efficiency 0.100 M Tl+with 25.00 mL of 0.200 M Co3+.
of 62% is passed through 20 L of NaCl solution (20% E°(Tl+/Tl3+) = – 1.25 V, E° (Co3+/Co2+) = 1.84 V
by weight). Write down the reactions taking place at
the anode and the cathode. How long will it take to
produce 1 kg of Cl2? What will be the molarity of the PREVIOUS YEARS’ QUESTIONS
solution with respect to hydroxide ion? (Assume no OF JEE (MAIN & ADVANCED)
loss due to evaporation).
1. Find the equilibrium constant for the reaction, 2Fe3+ +
86. A sample of water from a large swimming pool has a
3I– m 2Fe2+ + I3–. The standard reduction potentials
resistance of 9200 W at 25°C when placed in a certain
in acidic conditions are 0.77 V and 0.54 V respectively
conductance cell. When filled with 0.02 M KCl solu-
for Fe3+ | Fe2+ and I3– | I–couples. [1998]
tion, the cell has a resistance of 85 W
(a) 5.2 ¥ 108 (b) 6.26 ¥ 107
NaCl were dissolved in the pool, which was throughly
(c) 3.8 ¥ 107 (d) 4.3 ¥ 107
stirred. A sample of this solution gave a resistance of
2. Find the solubility product of a saturated solution of
7600 W. Calculate the volume of water in the pool.
Ag2CrO4 in water at 298 K if the emf of the cell Ag
Given: Molar conductance of NaCl at that concentra-
| Ag+ (standard Ag2CrO4 soln.) || Ag+(0.1M) | Ag is
tions is 126.5 W–1cm2mol–1 and molar conductivity of
0.164 V at 298 K. [1998]
KCl at 0.02 M is 138 W–1 cm2mol–1.
(a) 1.45 ¥ 10–12 (b) 2.2 ¥ 10–11
87. In the refining of silver by electrolytic method what
(c) 3.2 ¥ 10–11 (d) 2.44¥ 10–12
will be the weight of 100 g Ag anode if 5 ampere cur-
3. Two students use same stock solution of ZnSO4 and a
rent is passed for 2 hrs? Purity of silver is 95% by
solution of CuSO4. The emf of one cell is 0.03 V higher
weight.
than the other. The concentration of CuSO4 in the cell
88. Hydrogen peroxide can be prepared by successive re-
with higher emf value is 0.5 M. Find out the concentra-
actions:
tion of CuSO4 in the other cell (2.203 RT/F = 0.06).
2NH4HSO4 Æ H2 + (NH4)2S2O8 [2003]
(NH4)2S2O8 + 2H2O Æ 2NH4HSO4 + H2O2 (a) 0.09 M (b) 0.2 M
The first reaction is an electrolytic reaction the second (c) 0.05 M (d) 0.3 M
is steam distillation. What amount of current would 4. Find the equilibrium constant for the reaction,
In2+ + Cu2+ h In3+ + Cu+ at 298 K
have to be used in first reaction to produce enough in-
o
termediate to yield 100 g pure H2O2 per hour? Assume Given: ECu 2+
/Cu +
= 0.15 V; EIno 2+ /In + = –0.40 V,
50% anode current efficiency.
EIno 3+ /In + = –0.42 V [2004]
89. Determine at 298 for cell:
Pt|Q, QH2, H+||1M KCl|Hg2Cl2|Hg(l)|Pt (a) 1011 (b) 1010 (c) 1012 (d) 108
(a) it’s emf when pH = 5.0 5. We have taken a saturated solution of AgBr. Ksp of
(b) the pH when Ecell = 0 AgBr is 12 ¥ 10–14. If 10–7 mole of AgNO3 are added
(c) the positive electrode when pH = 7.5 to 1 L of this solution find conductivity (specific con-
o
given ERP(RHS) = 0.28, EoRP(LHS) = 0.699 ductance) of this solution in terms of 10–7 S m–1 units.
90. Calculate the cell potential of a cell having reaction Given, molar conductance of Ag+, Br– and NO3– are 6
Ag2S + 2e– m 2 Ag + S2– in a solution buffered at ¥ 10–3 Sm2mol–1. 8 ¥10–3 Sm2 mol–1 and 7 ¥ 10–3 Sm2
pH = 3 and which is also saturated with 0.1 M H2S. mol–1. [2006]
For H2S : K1 = 10–8 and K2 = 1.1 ¥ 10–13, Ksp(Ag2S) = (a) 55 (b) 45 (c) 58 (d) 60
2 ¥ 10–49, EAg
o
+
|Ag
= 0.8. 6. Given, ECr o
3+
o
= –0.74 V; EMnO- /Mn 2+ = 1.51 V,
/Cr 4
91. At 25°C, DHf(H2O, l) = –56700 J/mol and energy of o
ECr
o
= 1.33 V, ECl/Cl – = 1.36 V
O2- /Cr3+
ionization of H2O(l) = 19050 J/mol. What will be the 2 7
reversible EMF at 25°C of the cell, Based on the data given above strongest oxidising
Pt|H2(g)(1 atm)|H+|| OH–|O2(g)(1 atm)|Pt, if at 26°C the agent will be [2013 Main]
3+ 2+ -
emf increase by 0.001158 V. (a) Cl (b) Cr (c) Mn (d) MnO 4

7. In a galvanic cell, the salt-bridge [2014 Adv.] 11. The standard reduction potential data at 25°C is given
(a) does not participate chemically in the cell reaction. below: [2013 Adv.]
(b) stops the diffusion of ions from one electrode to Eo(Fe3+/Fe2+) = +0.77 V; Eo(Fe+2/Fe) = –0.44 V;
another.
Eo(Cu2+/Cu) = +0.34 V; Eo(Cu2+/Cu) = +0.52 V;
(c) is necessary for the occurrence of the cell reaction.
(d) ensures mixing of the two electrolytic solutions. Eo(O2(g) + 4H+ + 4e–) h 2H2O) = +1.23 V;
8. Given below are the half-cell reactions. [2014 Main] Eo(O2(g) + 2H2O + 4e–) h 4OH–) = +0.40 V;
Mn2+ + 2e– h Mn; Eo = –1.18 eV 2(Mn3+ + e– h
Eo(Cr3+/Cr) = –0.74 V; Eo(Cr2+/Cr) = +0.91 V;
Mn2+); Eo = +1.51 eV
The E° for 3Mn2+ h Mn + 2Mn3+ will be Match E° of the rebox pair in Column I with the values
(a) –2.69 V; the reaction will not occur. given in Column II and select the correct answer using
(b) –2.69 V; the reaction will occur. the code given below the lists.
(c) –0.33 V; the reaction will not occur. Column I Column II
(d) –0.33 V; the reaction will occur.
P. Eo(Fe3+/Fe) 1. –0.18 V
9. The equivalent conductance of NaCl at concentration
C and at infinite dilution are lC and l , respectively. Q. Eo(4H2O m 4H+ + 4OH–) 2. –0.4 V
The correct relationship between lC and l is given as R. Eo(Cu2+ + Cu h 2Cu+) 3. –0.04 V
(where, the constant B is positive) [2014 Main] S. Eo(Cr3+, Cr2+) 4. –0.83 V
(a) lC = l + (B)C (b) lC = l – (B)C
Codes:
(c) lC = l – (B) C (d) lC = l + (B) C
P Q R S
10. Resistance of 0.2 M solution of an electrolyte is 50 W.
(a) 4 1 2 3
The specific conductance of the solution of 0.5 M solu-
(b) 2 3 4 1
tion of same electrolyte is 1.4 S m–1 and resistance of
(c) 1 2 3 4
same solution of the same electrolyte is 280 W. The
(d) 3 4 1 2
molar conductivity of 0.5 M solution of the electrolyte
12. Two Faraday of electricity is passed through a solution
in Sm2 mol–1 is [2014 Main]
of CuSO4. The mass of copper deposited at the cathode
(a) 5 ¥ 10–4 (b) 5 ¥ 10–3
is (atomic mass of Cu = 63.5u) [2015 Main]
(c) 5 ¥ 103 (d) 5 ¥ 102
(a) 0 g (b) 63.5 g (c) 2 g (d) 127 g
Answer Key
LEVEL I
1. (b) 2. (d) 3. (d) 4. (a) 5. (c) 6. (d) 7. (d) 8. (b) 9. (b) 10. (b)
11. (a) 12. (b) 13. (a) 14. (d) 15. (a) 16. (d) 17. (b) 18. (b) 19. (c) 20. (b)
21. (b) 22. (c) 23. (c) 24. (a) 25. (a) 26. (c) 27. (c) 28. (a) 29. (d) 30. (b)
31. (b) 32. (c) 33. (a) 34. (c) 35. (d) 36. (a) 37. (b) 38. (a) 39. (c) 40. (d)
41. (d) 42. (b) 43. (a) 44. (a) 45. (d) 46. (c) 47. (c) 48. (c) 49. (c) 50. (b)
51. (b) 52. (d) 53. (a) 54. (d) 55. (d) 56. (d) 57. (b) 58. (b)
LEVEL II
1. (c) 2. (b) 3. (d) 4. (b) 5. (a) 6. (a) 7. (a) 8. (b) 9. (a) 10. (c)
11. (d) 12. (b) 13. (b) 14. (c) 15. (b) 16. (a) 17. (d) 18. (d) 19. (a) 20. (b)
21. (d) 22. (b) 23. (a) 24. (d) 25. (c) 26. (c) 27. (b) 28. (d) 29. (a) 30. (c)
31. (d) 32. (b) 33. (a) 34. (a) 35. (c) 36. (a) 37. (c) 38. (c) 39. (b) 40. (b)
41. (b) 42. (a) 43. (c) 44. (d) 45. (c) 46. (b)

LEVEL III
1. (A) Æ r; (B) Æ s; (C) Æ p, t; (D) Æ q 2. (A) Æ p, t; (B) Æ q, t; (C) Æ s, t; (D) Æ r

3. (A) Æ t; (B) Æ r; (C) Æ p; (D) Æ q; (E) Æ s 4. (A) Æ p, q, r, t; (B) Æ p, q, r, s, t; (C) Æ p, q, r, s, t; (D) Æ r, s
5. (d) 6. (b) 7. (a) 8. (a) 9. (c) 10. (a) 11. (b) 12. (a) 13. (d) 14. (c)
15. (d) 16. (c) 17. (d) 18. (d) 19. (b) 20. (a) 21. (c) 22. (a) 23. (c) 24. (b)
25. (d) 26. (d) 27. ( ) 28. ( ) 29. (a) 30. (a) 31. (b) 32. (a) 33. (c) 34. (a, c)
35. (a, d) 36. (b, c, d) 37. (a, c, d) 38. (a, c) 39. (a, c) 40. (a, d) 41. (b, d) 42. (a, b, c)
43. (b, c) 44. (a, c) 45. (a, b) 46. (a, c) 47. (a, b, d) 48. (a, c, d) 49. (a, b) 50. (a, c)
51. [3] 52. [6] 53. [2] 54. [2] 55. [4] 56. [4] 57. 228.735 mL and 158.285 mL, 58. [25%]
59. 1.24 ¥ 10–5 M 60. 6.5 ¥ 10–4 M, 1.352 ¥ 10–5 M 61. – 0.301 V 62. 23.32 W–1cm2eq–1 63. [200]
64. 120 W cm eq
–1 2 –1
65. 2.37 ¥ 10 cc.
8
66. 0.1456 Amp. 67. [118.695 mho cm2]
68. [H = 1.45 ¥ 10 cms , Na = 2.08 ¥ 10 cms ]
+ –3 –1 + –4 –1
69. [0.0353] 70. (2 ¥ 10–16)
71. [1.76 ¥ 10 ]–5
72. [2.70 ¥ 10 (mole/L) ]
–10 2
73. (b) 74. [0.059] 75. [Ecell = 0.71 V]
76. [0.373 V] 77. 4.7 ¥ 1063 78. = 6.6 79. 0.41 M 80. [3]
81. (a) = 9.6025g, (b) = 0.01 82. 43.45 g 83. Cu = 98.88%, Fe = 0.847 %
84. – 0.037 V, 85. 48.74 hr., 1.408 M 86. 2.014 ¥ 105L 87. 57.58g 88. 315.36 Amp.
89. (a) – 0.1235 V (b) pH = 7.1 (c) Calomal electrode 90. – 0.1674V 91. 0.44137
92. 3.29 cm 93. [Tl+] = 10–8 M, [Co+3] = 2 ¥ 10–8 M, [Tl+3] = 0.0025 M, [Co+2 ] =0.005 M
1. (b) 2. (d) 3. (c) 4. (b) 5. (a) 6. (d) 7. (a, b) 8. (a) 9. (c) 10. (a)
11. (d) 12. (b)
Hints and Solutions
LEVEL I 0.059 [Cu 2+ ]

4. (a) E = Ecell
0
+ log
2 [Zn 2+ ]
1. (b) 2SO4– – Æ S2O8–2 + 2e– 0.0591 [Zn 2+ ]
For 1 mole of S2O8–2 Since Ecell = Ecell
o
- log
Electricity required = 2F
2 [Cu 2+ ]
75 0.059 0.1
= 2 ¥ 96500 = i ¥ t ¥ = 1.10 + log = 1.07 V
100 2 1
75 5. (c) At anode, either Ag can get oxidised to Ag+ or Sn2+
2 ¥ 96500 = i ¥ 3600 ¥ to Sn4+ or Cl– to Cl2 or SO 2– 2–
100 4 to S2 O8 . Their respec-
i = 71.48 Amp. tive oxidation potential values are –0.799 V, –0.13 V,
1 È 0.0591 ˘ –1.36 V and –2 V. From these values, it is evident that
2. (d) H+ + e– m H2(g), Í E = E 0 - log Q ˙ Sn2+ would be oxidised first, followed by Ag at anode.
2 Î n ˚
At cathode, either Na+ can get reduced to Na or Sn2+ to
0.0591 [PH2 ]
1/2
0.591 1 Sn or H+ to H2. The reduction potential value of Na+
= 0.0 - log = log -7 is highly negative while for Sn2+ | Sn is –0.14 V and
1 [H + ] 1 10
1 Ê 1 ˆ
= –0.0591 ¥ 7 ¥ log 10 = –0.413 V for H+ + e– h H 2 ÁË EH+ |H2 = – 0.059 log –7 ˜¯ is
0
2 10
3. (d) More the ERP , more is the tendency to get reduced
0 –0.41 V. Thus, Sn2+ will get reduced at cathode fol-
or lesser is tendency to get oxidised. ERP(Cr 3+
/Cr 2 + )
is
lowed by H+.
lowest or E 0 is maximum among all.
6. (d) L NaBr = L NaCl + L KBr - L KCl = 126 + 152 – 150 =
0 0 0 0
OP(Cr 2 + /Cr3+ )
128 S cm2 mol–1

7. (d) During electrolysis of CuSO4 solution using Cu \ DS = 2 ¥ 96500 ¥ (–6.48 ¥ 10–4)

electrodes, the cell reaction is –125.064 J mol–1
Anode: Cu(s) h Cu++ + 2e– DG = DH – TDS. Substituting the values, we get
Cathode: Cu++ (aq) + 2e– h Cu(s) DH = 167.6 kJ.
The loss in weight of anode is equal to gain in weight 2
of cathode. 15. (a) For 1 mole of O2, O2 h ¥ 3O2–
3
At cathode: Cu2+ + 2e– h Cu 2
8. (b) Weight of copper deposited = 10 ¥ 10 ¥ 10-2 ¥ 8.94 so that n = ¥ 6 = 4.
3
= 8.94 g
Hence, DG = –nFE given
8.94
Number of moles of copper deposited = DG – 827000
63.54 E= = = 2.14 volt.
– nF – 4 ¥ 96500
Cu2+ + 2e– h Cu
Number of Faradays needed to deposit 1 mole of Cu is 16. (d) Large negative reduction potential means large pos-
two. itive oxidation potential which implies that A– is easily
2 ¥ 8.94 2 ¥ 8.94 ¥ 96500 oxidised.
\ charge = F= C = 27155 C 17. (b) Just because of a convention.
63.54 63.54
9. (b) At anode Zn Æ Zn+2 + 2e– 18. (b)
At cathode Cu+2 + 2e Æ Cu At cathode: 2H+ + 2e– m H2 (P2)
2F required for 1 mole Zndisolution into Zn+2 At anode: H2(P1) m 2H+ + 2e–
(means weight loss) and 1 mole Cu deposite means Oveall reaction: H2(P1) m H2(P2)
weight Gain RT P2 RT P2 RT P1
E = Eo – ln =0– ln = ln
9.65 ¥ 60 ¥ 60 nF P1 2 F P1 2 F P2
\ = 0.36 F
96500 19. (c) For water at 298 K, [H+] = 10–7 M
1 1
fi ¥ 0.36 Mole Zn (Loss in wt.) = 11.77 gram Reduction reaction is H+ + e– h H2
2 2
1 PH1/2
fi ¥ 0.36 Mole Cu (Loss in wt.) = 11.43 gram RT PH1/2
2 \ E=– ln + = – 0.0591 log +2
F [H ] [H ]
10. (b) Ecell = Eox + Ered
= Eox – Eox 1
= - 0.0591 log
=0 10-7
11. (a) Best reducing agent is one which is itself oxidised = - 0.4137 - 0.414 V
most easily, viz, A. SinceAlkali metal have –ve SRP
Area ¥ Concentration
\ given data are in SRP. 20. (b) Conductivity μ
Length
RT [Zn 2 + ][Cl- ]2
12. (b) Ecell = Ecell
o
- in Area ¥ Concentration
nF PCl2 or Conductivity = K ¥
Length
13. (a) In the given reaction, I– has been oxidised to I2 and
+3 Conductivity ¥ Length
Cr2 O72– ions have been reduced to Cr or K=
Area ¥ Conc.
\ o
Ecell o
= ECr O2- /Cr +3
– EIo /I- S¥m
2 7 2
= 2 –3
= Sm 2 mol –1.
EIo /I- or EIo /I- = 0.54 V m × mol m
i.e., 0.79 = 1.33 – 2 2
14. (d) DG = –nFEcell 21. (b) The plot of Ÿ m vs c is linear according to Debye-
= –2 ¥ 96500 ¥ 0.6753 (at 25ºC) Huckel onsager equation.
= –130333 J 22. (c) Ÿ om (CaCl2 ) = lmo (Ca 2 + ) + 2lmo (Cl- )
È ∂E ˘ = 118.88 ¥ 10–4 + 2(77.33 ¥ 10–4)
Ê ∂E ˆ is called temperature ˙
DS = nF Á ˜ Í ∂T = 273.54 ¥ 10–4 m2 mho mol–1.
Ë ∂T ¯ Í ˙
Îcoefficient of cell ˚ 23. (c) Cu2+ ions gain electrons and are deposited on cop-
Ê ∂E ˆ E2 - E1 per.
ÁË ˜¯ = 24. (a) Iron loscs electrons to form Fe2+ only when it acts
∂T P T2 - T1
as anode.
0.6753 – 0.6915 25. (a) Al3+ + 3e– h Al
= = – 6.48 ¥ 10 –4
298 – 273

\ 1 millimole require 30. (b) AgI + e– h Ag + I– E° = –0.151 (i)

\ 3 ¥ 96.5 C = 9.6 A ¥ time in sec. Ag++ e– h Ag E° = 0.799 (ii)
3 ¥ 96.5 \ (i) – (ii)
Time = = 30 s AgI m Ag+ + I– E° = –0.151 – 0.799
9.65
0.0591
1 E° = –0.95 E = E° – log K sp
26. (c) H 2 + AgI h H + + Ag + I – E=0 1
2
–16.074 = log10 Ksp , \ Ksp = 7.91 ¥ 10–17
AgI + I–Æ Ag + I– E = –0.151
1 40
\ H 2 h H + + e – E = 0.151 31. (b) W = Zit = ¥ 9.65 ¥ 103 = 4 g
2 96500
0.0591
0.151 = -
0.059
log[H + ] = 0.059 ¥ pH 32. (c) E° = log K 1.1 ¥ 2 = 0.06 log K
2
1
0.151 36.22 = log K 1036.22 = Kf
pH = = 2.5 8.314 ¥ 1036 = K
0.059
0.0591 È 1 ˘
33. (a) Ecell = 0.80 – log Í –3 ˙ = 0.623 V
27. (c) For the given cell reaction, 1 Î10 ˚
DG o = – nFE ocell = – RT ln K eq 0 1 +1
34. (c) H 2 + O 2 h H 2 O –2 = 2F
2
–5 ¥ 96500 ¥ 0.59 = –2.303 ¥ 8.314 ¥ 298 log Keq
35. (d) See derivation of metal metal sparingly soluble
Keq = 7.8 ¥ 1049 ª 1050 electrode.
28. (a) The half-cell reaction for hydrogen half-cell acting When act as cathode (reduction half cell)
as cathode is (Result)
2H+ + 2e– h H2 0.0591
E I- /AgI/Ag = E oAg + /Ag + log[Ag + ] = E oAg + /Ag
0.059 PH 1
EH+ |H = EHo + |H – log +2 2
2 2 2 [H ] and
0.059 1 0.0591
\ EH+ |H = – log + 2 E oI- /AgI/Ag = E oAg + /Ag + log Ksp AgI
2 2 [H ] 1
= 0.80 + 0.0591 log [8.3 ¥ 10–17]
Now, when the pressure of H2 gas is changed to 100 + 0.80 – 0.95 = – 0.15 V
atm without changing [H+], the reduction potential be-
36. (a) 2Fe2+ + Sn+4 h 2Fe3+ + Sn+3
comes
E° = EC° – EA° = 0.15 – 0.77 = –0.62 V
0.059 100 37. (b) Ni(s) + 2H2 h NiSO4 + H2
\ E¢H+ |H = – log + 2
2 2 [H ] 0.0591 1
\ change in reduction potential = 0.236 = E° – log
1 1
0.059 100 [H + ]2 –nFE° = DG°
EH+ |H – EH¢ + |H = log + 2 ¥ = 0.059 V DG° = –2 ¥ 96500 ¥ 0.236 = 45.55 kJ
2 2 2 [H ] 1
38. (a) Fe3+ h Fe2+
29. (d) During electrolysis of an aqueous solution of
0.0591 1.5
Na2SO4, the following reactions occur at the electrodes. Ecell = 0.770 V – log
Anode: 4OH– h 2H2O + O2 + 4e– 1 0.015
= 0.770 – 0.059 ¥ 2 = 0.652 V
Cathode: 2H+ + 2e– h H2
39. (c) K = 1.12 ¥ 10–2 mho – cm–1
Number of Faradays needed to liberate 1 mole of O2 =
N/10 KCl solution
4.
2.4 ¥ 4 1 l
\ charge = F K= ◊
22.4 R A
1 l
1 1.12 ¥ 10-2 = ¥
Number of moles of H2 liberated by 1 F of charge = 65 A
2
2.4 ¥ 4 l/A = 0.728 cm–1
Number of mole of H2 = 40. (d) K (H2O) = 5.8 ¥ 10-8 mho - cm -1
2 ¥ 22.4
2.4 ¥ 4 ¥ 22.4 H 2O H + + OH -
Volume of H2 of STP = = 4.8 L
2 ¥ 22.4 C - Ca Ca Ca

Kd = Ca2 F
C = 55.55 M W = Zit = i¥t
F
L 71
a= m = ¥ 2 ¥ 2.5 ¥ 60 = 0.110 g
Lm 2 ¥ 96500
1000
K¥ 0.0591 [Cl – ]2 [Br2 ]
a= M 50. (b) Ecell = 0.29 - log
L mH+ + L m OH- 2 [Br – ]2 [Cl2 ]
0.0591 [10 –2 ]2 [10 –2 ]
Data insufficient = 0.29 - log
l (H+) must be given 2 [10 –2 ]2 [1]
41. (d) Ag+ + e– h Ag 0.0591
= 0.29 + ¥ 2 = 0.349 ª 0.35 V
Ecell = E° –
0.059 È 1 ˘ 2
log Í ˙
1 Î 0.1˚ 51. (b) Fe+2 + 2e– Æ Fe
= E°red – 0.059 2F charge = 1 mole Fe = 56 gram
42. (b) Cu2+ + 2e– h Cu
56
V1 = 1, C1 = 1 M \ 1 F charge = gram
V2 = 10, C2 = 0.1 M 2
0.0591 1 56 168
Ecell = E° – log Ecell = E° \ 3 F charge = ¥3= = 84 gram
2 1 2 2
0.0591 È 1 ˘ 52. (d) Ag+, Cu2+, Au3+
Ecell = E° – log Í ˙
2 Î 0.1˚ 1 1 1
: :
= E° – 0.059/2 = E° – 0.030 1 2 3
43. (a) H2 h 2H+ + 2e– =6 : 3 : 2
pH = 1, [H+] = 10–1 E° = 0 53. (a)
2
0.0591 [H ] 0.0591 È 1 ˘ o
Ecell = Ecathode
o
- Eanode 0.80 = EAg
o
- EHo 2 /H+
E= log +2 2 = log Í –1 ˙ +
/Ag
2 [H ] 2 Î10 ˚
0.80 = EAg
o
+ -0
0.0591 /Ag
= ¥ 2 = 0.0591 V
2 o
Eoxidation = - Ered
o
= - 0.80 V
0.0591 ÈP˘ ÈP˘ 54. (d) DG° = –nF E°cell
44. (a) E = Ecell
o
- log Í ˙ if Í ˙ = 1 then Ecell = Ecell
o ( 1 F = 96500 C)
n ÎR˚ ÎR˚ = –2 ¥ 0.360 ¥ 96500 = –69480J = –69.48 kJ
45. (d) Fe3+ + 3e– h Fe DG1 = –nF E°cell = –3F E°cell 55. (d) MnO4– + 8H+ + 5e– h Mn2+ + 4H2O = 5 F
Fe2+ + 2e– h Fe DG2 = –2F E°cell 56. (d) Cu+ + e– h Cu DG1 = –F E° = – FX1
Fe3+ + e– h Fe2+ DG3 = –F E°cell required Cu2+ + 2e– h Cu DG2 = –2F E° = –2FX2
Cu2+ + e– h Cu+ DG3 = –F E°
DG3 = DG1 – DG2
DG3 = DG2 – DG1 –FE° = –2FX2 + FX1
–F Ecell = –3F E°cell + 2F Ecell
E° = 2X2 – X1
–Ecell = –3 ¥ (–0.036) + 2 (–0.440)
E Atomic wt. ¥ i ¥ t
–Ecell = – 0.772 Ecell = + 0.772 V 57. (b) W = Zit = it =
F n¥F
46. (c) 2H+ + 2e– h H2 pH = 10, [H+] = 10–10
E° = 0 atomic wt. ¥ 14 ¥ 965
0.275 =
2 ¥ 96500
0.0591 [H + ]2 0.0591
Ered = log = ¥ 2 log[10 –10 ] Atomic wt. = 0.550 ¥ 100 = 55
2 PH (g) 2
2
0.0591 Ê atomic weight ˆ
= ¥ 2 ¥ [–10] = – 0.591 V ÁË valency factor ˜¯
2 w1 ( E1 ) Ag 0.5094 Ag
58. (b) = =
w2 ( E2 ) metal 0.2653 Ê atomic weight ˆ
o
47. (c) Ecell = Ecathode
o
- Eanode
o
= 0.80 – (–0.25) = 1.05 V ÁË valency factor ˜¯
metal
o
48. (c) Ecell = Ecathode
o
- Eanode
o
= 1.50 – (–0.25) = 1.75 V
0.5094 (valence factor) Metal
49. (c) 2Cl– h Cl2 + 2e– = valence factor 1.9 ª 2
0.2653 1

LEVEL II 0.0591
¥ 1.7 = 0.81 - 0.76
n
0.0591 ¥ 1.7
1. (c) n=
+6 +4
0.05
SO -4 2 + 2e ææ
Æ SO3-2 E1o = - 0.936 =2
+4 1 +2 o - 0.0591
SO -4 2 + 2e ææ
Æ S 2O3-2 E2o = - 0.576 5. (a) Ecell = Ecell log Q
2 n
1 o
Ecell =0
\ SO -4 2 + 4e ææ
Æ S2O3-2
2 At Anode: H2 – 2e h 2H+ (aq)
- 2 ¥ 0.936 - 2 ¥ 0.576 At Cathode: 2H+(aq) + 2e h H2(g)
nE ° = n1E1o + n2 E2o Eo =
4 0.0591 [H + ]2
= - 0.756 V Ecell = 0 - log + 2A
2 [H ]C
2. (b)
At cathode:
Cr2O7-2 + 14H + + 6e h 2 C r 3+ + 7H 2O E o = 1.33 V
10-3 25 ¥ 10- 3 25
[H + ] = = (5 ¥ 10-2 )
0.01
0.01 =
POH = 11 500 ¥ 10- 3 500
PH = 3 At Anode:
[H+] = 10–3
PhNH 2 + H 2 O PhNH3+ + OH -
0.0591 [Cr 3+ ]2
Ecell = E ocell - log
6 [Cr2O7-2 ][H + ]14 [OH - ] =
Kb
C
0.0591 [0.01]2
= 1.33 - log = 0.936 V 10-9
6 [0.01] ¥ [10-3 ]14 \ [OH - ]2 = = 10-6
0.5
3. (d) NO -2 (g) + H 2O h NO3- (aq) + 2H + (aq) + 2e 500
E o = 0.78 V \ [H+] = 10–8
Ecell = Ecell
o
-
0.0591 1
log + 2 0.0591 (5 ¥ 10-2 ) 2
\ Ecell = + log
2 [H ] 2 (10-8 ) 2
2
0.0591 Ê 1ˆ 0.0591
= 0.78 -
¥ log Á ˜ =+ log[5 ¥ 106 ]2
2 Ë 9¯ 2
0.0591 = + 0.0591[6 + 0.7]
= 0.78 - ¥ 2[- log 9]
2 = 0.0591 ¥ [6.7]
= 0.78 + 0.056 = 0.836 V = + 0.395 V
4. (b) A : M - ne h M n + E o = + 0.76
6. (a) ÊÁ ˆ˜ = - 4 ¥ 10-5 V/deg
(0.02 M ) dE
n Ë dT ¯ p
C : nH + + ne h H 2 (g) Eo = 0
(1m ) 2 n=2
n
M + nH + h M n + + H 2 (g). E o = + 0.76
o
Ecell = 1.0181 V
2
DGo = - 2FEcell
o
0.0591 [M n+ ]
Ecell = 0.81 = + 0.76 - log + n = –2 ¥ 96500 ¥ 1.018
n [H ] = –196474 J
0.0591 0.02 = –196.5 kJ
= + 0.76 - log
n 1 Ê dE ˆ
DS o = nF Á ˜ = - 2 ¥ 96500 ¥ 4 ¥ 10-5
0.0591 1 Ë dT ¯
= + 0.76 + log
n 0.02 = - 7.72 J/deg
0.0591
= + 0.76 + ¥ 1.7 Ê Ê dE ˆ o ˆ
n DH o = nF Á T Á ˜ - Ecell ˜ = 198.8 KJ
Ë Ë dT ¯ p ¯

Ê Ê dE ˆ E = 108.2
o ˆ
7. (a) Use the formula DH o = nF Á T Á ˜ - Ecell ˜ 14. (c) Volume = 8.2 ¥ 1012 L
Ë
Ë dT p ¯ ¯ Taking density app 1 g/c.c
n=1 Mass of H2O in the lake = 8.2 ¥ 1012 kg
dE = 8.2 ¥ 1015 g
= - 0.125 V/K H2O Æ H + OH
+ –
dT
At cathode: 2H+ + 2e– Æ H2(g)
o
Ecell = 0.0732 V
1
8. (b) Q = it At anode: 2OH– – 2e Æ H2O + O2(g)
2
i = 0.193 A, t = 1 hr = 60 ¥ 60 sec E
W = ¥i¥t
\ Q = 0.193 ¥ 3600 F
694.8 W¥F
= 694.8C = F \ t=
96500 E¥i
= 7.2 ¥ 10–3 F
8.2 ¥ 1015 ¥ 96500
= 7.2 ¥ 10–3 Mole Na+ t=
= 7.2 ¥ 10–3 Mole (NaOH) 1.5 ¥ 106 ¥ 9 ¥ 3600 ¥ 24 ¥ 365
7.2 ¥ 10-3 = 1.9 ¥ 106 years
[OH - ] = = 7.2 ¥ 10-2 M
0.1 = 1.9 million years
H
POH = 2 - log 7.2 ; p H = 14 - p O ; = 12 + log 7.2 = 12.82 15. (b) Pt, H2 (1 atm)/CH3COOH (0.1 M)//NH3 (aq, 0.01
M)/H2 (1 atm) Pt
0.059 (10-1 ) Ka(CH3COOH) = 1.8 ¥ 10–5
9. (a) Ecell = 3.17 - log -4 2
2 (10 ) Kb(NH3) = 1.8 ¥ 10–5
= 3.170 ¥ 0.02951 log 107 1
At anode: H2 - e h H+ Eo = 0
= 3.17 - 0.21 = 2.96 V 2
1
10. (c) Thickness of silver deposited = x cm At Cathode: H + + e h H 2 (g) o
Ecell =0
Weight of Ag deposited = density ¥ V = 10.47 ¥ 800x g 2
108 0.0591 [H + ]
Now 800 ¥ 10.47x = ¥ 0.2 ¥ 3 ¥ 3600 Ecell = Ecell
o
- log + A (1)
96500 1 [H ]C
x = 2.88 ¥ 10–4 cm
[OH–]2 = 0.01 ¥ 1.8 ¥ 10–5
+2
0.0591 [Ni ] [OH–] = 4.2 ¥ 10–4
11. (d) Ecell = Ecell
o
- log + 2
2 [H ] 10-14
[H + ]C =
0 = 0.236 + 0.0591log[H + ] 4.2 ¥ 10-4
0.236 = - 0.591log[H + ] Similarly,

[H+]2 = 1.8 ¥ 10–5 ¥ 0.1
= 0.0591 Ph
P H = 3.99 = 4.00
[H+]A = 1.8 ¥ 10-6
12. (b) Equivalent conductance at infinite From equation (1)

dilution for AgNO3 = 133.3 ohm–1cm2eq–1 Ecell = –0.0591 ¥ 7.78
= –0.46 V
tAg + = 0.464
16. (a) Ag(NH3 ) +2 + e Ag + 2NH3 E o = Xvolt
\ lAg + = 133.3 ¥ 0.464
Ag - e Ag + E o = - 0.7991
= 61.85
13. (b) Number of equivalent of I2 reduced Ag(NH3 ) 2+ Ag + + 2NH3 E o = X - 0.791
= 46.3 ¥ 10–3 ¥ 0.124 At Equilibrium
= 5.7 ¥ 10–3
Number of equivalent of I2 = Number of equivalent of Ecell = 0 K[Ag(NH + = 6.02 ¥ 10-8
3 )2 ]
metal 0.06
E o = X - 0.7991 = log K
0.617 1
5.7 ¥ 10-3 =
E

fi X = 0.7991 + 0.06 ¥ log(6 ¥ 10-8 ) 63.5 96500 ¥ 67.2

= ¥ = 190.5 g
= 0.372 V 2 ¥ 96500 22.4
Similar method applies to second question. 21. (d) Weight of solution before discharge
17. (d) l(aq) = 97.1 mho – cm2/eq. = 3500 ¥ 1.294 = 4529 g
Weight of H2SO4 before discharge
A = 1.5
l = 0.5 39
= ¥ 4529 = 1766.31 g
Normality = 0.1 N 100
K ¥ 1000 Weight of solution after discharge
leq = = 3500 ¥ 1.139 = 3986.5 g
N
1 l Weight of H2SO4 after discharge
¥ 1000
97.1 = AR 20
N = ¥ 3986.5 = 797.3 g
100
1 0.5 Loss in mass of H2SO4 during discharge = 1766.31 –
97.1 ¥ 0.1 = ¥ ¥ 1000
R 1.5 797.3 = 969.01 g
1000 Now from first law of electrolysis,
\ R= = 34.32 W Q¥E Q ¥ 98
9.71 ¥ 3 W= ; 969.01 = ;
96500 96500
V 5
\ i= = = 0.1456 Amp. Q = 954178.21 coulomb
R 34.32
Coulomb 954178.21
18. (d) Quantity of electricity passed = (5 A) ¥ (20 ¥ 60 s) Ampere-hour = =
= 6000 C; Ni2+ + 2e– h Ni 3600 3600
= 265.04 ampere-hour.
Thus, 2F, i.e., 2 ¥ 96500 C deposit Ni = 1 mol, i.e., 58.7
g 22. (b) MnO -4 + 5e– + 8H+ h Mn2+ + 4H2O
58.7 According to Nernst equation,
\ 6000 C will deposit Ni = ¥ 6000 g =
2 ¥ 96500
1.825 g 0.0591 È [Mn 2+ ] ˘
19. (a) Ag+ + e– h Ag, i.e., 108 g of Ag are deposited by Ered = Ered
o
- log Í - + 8˙
5 Î[MnO 4 ][H ] ˚
1 F = 96500 C
96500 Let [H+]initial = X
1.45 g of Ag will be deposited by ¥ 1.45 C =
1295.6 C 108 0.0591 È [Mn 2 + ] ˘
Q = i ¥ t or t = Q/i = 1295.6/1.50 = 863.7 s = 14.40 Min
o
Ered(initial) = Ered - log Í - 8˙
i.e., 2 ¥ 96500 C deposit Cu = 63.5 g
5 ÎÍ[MnO 4 ][X] ˚˙
63.5 X X
\ 1295.6 C will deposit Cu = ¥ 1295.6 [H+]final = = 2
2 ¥ 96500 100 10
= 0.426 g 0.0591 [Mn 2 + ] ¥ 1016
Ered(final) = Ered -
o
log
Zn2+ + e– h Zn 5 [MnO -4 ] ¥ [X]8
65.3 - 0.0591
\ Zn deposited = ¥ 1295.6 = 0.438 g E red(final) – E red(initial) = log 1016 = –0.1891 V
2 ¥ 96500 5
20. (b) Reaction at anode of fuel cell, This Ered decreases by 0.189 V. The tendency of the
H2(g) h 2H+ + 2e– half-cell to get reduced is its oxidising power. Hence
1 mole 2 mole the oxidising power decreases by 0.189 V.
22.4 L 2F 23. (a) For the cell reaction
2 ¥ 96500
67.2 L of H2 correspond = ¥ 67.2 coulomb 1
Ag(s) + Cl2(g) h AgCl(s)
22.4 2
Time = 15 ¥ 60 sec E0 = 1.36 – 0.22 = +1.14V
2 ¥ 96500 ¥ 67.2 0.0591 1
Average current = = 643.3 amp log
22.4 ¥ 15 ¥ 60 or E = E° – 1 (PCl2 )1/2
2 ¥ 96500 Under standard conditions PCl2 = 1 ,
Mass of copper deposited by ¥ 67.2 cou-
22.4 \ 1/2
log PCl =0
lomb 2

Useful work = –DG = +nFE 27. (b) Ag h Ag (a

+
+ e–
= 1 ¥ 96500 ¥ 1.14 ¥ 10–3 kJ = 110 kJ mol–1 1)
24. (d) The cell corresponding to the given reaction is as +

Ag (a 2)
+ e – ææ
Æ Ag
follows.
Cr2+(1 M) | Cr3+ (1 M) || Cr2+ (1 M) | Cr(s)
+
Ag (a 2)
ææ
Æ Ag (a
+
1)
I Cr3+ + 3e h Cr(s), DG oI = – 3FE oCr3+ ,Cr 0.0591 a

E=– log 1
1 a2
II Cr3+ + e h Cr2+, DG oII = – FE o 3+ 2+
Cr , Cr a2 0.1
= 0.0591 log = 0.059 log = 0.455
Eq. I - Eq. II: Cr + 2e h Cr(s), DG = –3 ¥ 0.5 F –
2+ o a1 a1
0.41 F = –1.91 F 0.1 0.455
DG o = - 2FE o 2+ = -1.91 F log = = 7.71
Cr ,Cr a1 0.059
1.91 0.1
\ E o 2+ = = 0.955 V = anti 7.71 = 5.129 ¥ 107
Cr ,Cr 2 a1
o o o
Ecell = ECr – ECr = 0.955 + 0.41 = 1.365 V 0.1
2+
, Cr 3+
,Cr 2+ a1 = [Ag + ] = = 1.95 ¥ 10 –9
5.129 ¥ 107
o
Ecell is +ve so DG° is –ve and hence the given reaction
[Cl–] = 10–1
is spontaneous
Solubility product of AgCl = [Ag+][Cl–] = 1.95 ¥ 10–9
\ DG° = –nF Ecell o
= –2 ¥ 96500 ¥ 1.365 J = –263.44 kJ ¥ 10–1 = 1.95 ¥ 10–10
From Gibb’s-Helmholtz equation
Solubility of AgCl = [Ag+] = [Cl–] = 1.95 ¥ 10 –10 =
È ∂( DG ) ˘ 1.396 ¥ 10–5 moles/L
DG = DH + T Í
Î ∂T ˙˚ P 28. (d) For AgCl, molarity = normality nf = 1
(– 270.50 + 263.44) actual specific conductance = (specific conductance of
– 263.44 = DH + 298 AgCl – specific conductance of water)
10
= (3.41 – 1.60) ¥ 10–6
= DH - 298 ¥ 0.706
= 1.81¥ 10–6 ohm–1 cm–1
\ DH = –53.05 kJ For saturated solution of sparingly soluble salt
DH – DG – 53.05 + 263.44 L eq = L eq , and solubility = concentration
DS = =
T 298
= 0.706 kJ K–1 = 706 kJ K–1. Ksolute ¥ 1000
L eq =
25. (c) S
E.i.t 107.8 ¥ 8.46 ¥ 8 ¥ 60 ¥ 60 1.81 ¥ 10 –6 ¥ 1000
wAg = = = 272.18g \ 138.3 =
96500 96500 S
272.18
Volume of Ag = = 25.92 mL 1000 ¥ 1.81 ¥ 10 –6
10.5 S (mol L–1 ) = = 1.31 ¥ 10 –5 mol L–1
138.3
25.92 AgCl(s) m Ag+(aq) + Cl–(aq)
Surface area = 1.02 ¥ 104 cm 2
0.00254 \ Ksp = [Ag+][Cl–] = S2 = (1.31 ¥ 10–5)2 = 1.72 ¥
26. (c) The cell can be formed as Fe|Fe3+; OH– || Fe(OH)3(s) 10 mol2 L–2
–10
| Fe 29. (a) CH3COOH m CH3COO– + H+
The electrode reactions can be written as
Fe(s) h Fe3+ + 3e– [CH3COO - ][H + ]
Ka =
Fe(OH)3(s) + 3e– h Fe(s) + 3OH– [CH3COOH]
Overall reaction is, i.e., by adding Ka[CH3COOH]
i.e., E 0 = E 0 – – E 0 3+ (i) \ [H + ] =
OH /Fe(OH)3 /Fe Fe /Fe [CH3COO - ]
o
EOH – can be calculated if we know E° and Ka ¥ y
/Fe(OH) 3 /Fe For the first cell, [H+] =
E° can be calculated as follows x
0.0591 0.0591 ¥ (– 36.4) 0.0591 Ê yK a ˆ
2
Eo = log 10 –36.4 = = 0.75 V log Á
Ë x ˜¯
3 3 E1 = EH + =–
2 |2H 2
From (i)
Ê yK ˆ
Eo – = – 0.75 – 0.036 = – 0.786 V From (i) = – 0.0591 log Á a ˜
OH /Fe(OH)3 /Fe Ë x ¯

xK a 1 1
For the second cell, [H+] = 0.6 = log , log 4 = log
y (X) X
2 1
0.0591 Ê xK a ˆ X= M
E2 = EH =– log Á
Ë y ˜¯ 4
+
2 |2H 2
= 0.25 M
Ê xK ˆ
= – 0.0591 log Á a ˜ E
Ë y ¯ 34. (a) w = Z i t w= ¥i¥t
96500
E1 + E2 = – 0.0591 log K a2
w 200.6 ¥ 2 + 71
E + E2 = ¥i
pK a = 1 t 2 ¥ 96500
0.118 44 236.1
30. (c) The standard emf of the cell in which the following = = ¥i
3600 96500
equilibrium is established
i = 5 amp.
I2 + I – I 3– 35. (c) Ka = 25 ¥ 10–6 LCeq. = 19.6 s cm2 eq–1
o o 0.059 K a L eq
C
is given by ( EI |I – – EI – |I – ) = log K c C = 0.01 M a= =
2 3 2 C L eq
Substituting the values of EIo |I – = 0.619 V, EIo- |I- =
0.5355 V
2 3 25 ¥ 10 –6 19.6 5 ¥ 10 –3 19.6
= fi =
0.059 0.01 L eq 0.1 L eq
(0.6197 – 0.5355) = log K c
2 19.6 ¥ 0.10
L eq =
On solving, Kc = 714.9 5 ¥ 10-3
31. (d) For the same charge,
1960
equivalents of X = equivalents of Zn = 392 Scm 2eq -1
5
0.348 1.264 ¥ 2
= , where E is equivalent weight of X.
E 65.4 36. (a) L M = L°M – b C LM
On solving, E = 9. y = C – mx
Since, n-factor of X in XCl is 1, the molar mass of X = slope = –ve
9 g mol–1. 1 C
32. (b) Given that E° = –0.268 V for Cl– |PbCl2| Pb and 37. (c) H2O h H2 + O 2 + 2e –
2
E° = –0.126 V for Pb2+ | Pb 2H2O h 2H2 + O2 + 4e–
The E° values of the two half-cells are related to each gases [H2 + O2] = 2 ¥ 22.4 + 22.4 = 67.2
other as 38. (c)
o o 0.0591 1
ECl –
|PbCl2 |Pb
= EPb 2+
|Pb
+ log K sp (PbCl2 ) A1 = L BaCl2 = L eq Ba 2 + + L eqCl- (i)
2 2
0.0591
– 0.268 = – 0.126 + log K sp (PbCl2 ) 1
2 A2 = L H 2SO4 = L eq H+ + L -2 (ii)
2 eqSO4
On solving, Ksp(PbCl2) = 1.536 ¥ 10 M . –5 3
33. (a) 2Ag+ + H2 h 2H+ + 2Ag A3 = L HCl = L H+ + L Cl- (iii)

0.0591 [H + ]2
1.023 = (ECo – EAo ) – log 1 1
2 PH2 [Ag + ]2 L =
L eq Ba 2+ + L SO2- (iv)
eq BaSO 42 2 eq 4
1.023 = (0.799 – 0) – 0.591 ¥ 2 log[H]+ + 0.591 ¥ 2 log[X]2
eq. (iv) = eq. (i) + eq. (ii) – eq. (iii)
2 2 = A1 + A2 - A3
0.06
0.294 = 0.06 ¥ 5.5 + log [X]2 39. (b) From 2nd Law W μ E
2
W1 W2 W3
0.06 = =
= - 0.036 = ¥ 2log X E1 E2 E3
2
= - 0.6 = log X 2.1 2.7 7.2
n1 ¥ = n2 ¥ = n3 ¥
7 27 48

3 44. (d)
0.3n1 = 0.1n2 and 0.1n2 = n3 2H2 + O2 Æ 2H2O DH = 2 ¥ (–285.5 kJ)
2
n2 = 3n1 and 2n2 = 3n3 O2 + 4H + 4e Æ 2H2O
+ –
E° = 1.23
2 2 2H2 Æ 4H + 4e + –
E° = 0
n3 = n2 = (3n1 ) = 2n1
3 3 for reaction:
n1 : n2 : n3 = 1: 3 : 2 O2 + 2H2 Æ 2H2O E° = 1.23
5 paise DG° = –nFE° = –4 ¥ 96500 ¥ 1.23 = –474780
40. (b) Cost = ¥ hour ¥ 15 amp ¥ 110
KWH DG° = DH° – TDS°
= 3
5
8 ¥ 15 ¥ 110 =
66000
= 66 paise – 474780 = –571000 – 298 DS°
10 ¥ WH 103 DS° = –322.8 J/K
41. (b) Ag + Cl– h AgCl + e– K ¥ 1000
E = E° + 0.0591 log [Cl–] 45. (c) lM =
M
–0.25 = E° + 0.0591 log 0.1 \ E° = –0.1909
1 Ê l ˆ 1 Ê 2.2 ˆ 1
Now for reaction K= Á ˜= Á ˜= = 0.01
Ag + Cl– h AgCl + e– R Ë a ¯ 50 Ë 4.4 ¯ 100
Ag+ + e– h Ag 0.01 ¥ 1000
Ag+ + Cl– h AgCl lM = = 20 S cm2 mole–1
0.5
= 20 ¥ 10–4 S m2 mole–1 = 0.002 S m2 mole–1
- + EAg + / Ag
o o
E = EAg/AgCl/Cl + 0.0591 log Ksp
46. (b) Ka = 1.69 ¥ 10–5 = Ca2 = 0.01 a2 = a = 0.04
since E = 0 at equilibrium and KSP = Keq
O = –0.1909 + 0.799 + 0.0591 log Ksp lM
a= fi lM = 0.04 ¥ 380
Ksp = 5.13 ¥ 10–11 lM
42. (a) Given: Au+3 + 3e– h Au m E1o = 1.5 K ¥ 1000
lM = 15.2 S cm2 mole–1 lM = M
Au + 2e h Au m
+3 – +
E2o
= 1.4
K ¥ 1000
so for reaction nE = n1E1 + n2E2 15.2 =
0.01
E° = 2 E2 - 3E1 fi E° = –1.7
o o
Au h Au+ + e–
K = 1.52 ¥ 10–4 S cm–1
Au + 2CN– h Au(CN)2– + e– E° = x
K = 1.52 ¥ 10–2 S m–1
Au + e h Au
+ –
E° = 1.7
RT
O = x + 1.7 – ln X
F LEVEL III
RT
x= ln X - 1.7
F (Match the Column)
For reaction
1. (A-r), (B-s), (C-p,t), (D-q)
O2 + H2O + 4e– h 4OH– E° = 0.41
Ag/Ag+ (0.1 M) || Cd2+ (0.1 M)/Cd
RT
Au + 2CN– h Au(CN)2– + e– E° = ln X - 1.7 0.1 M (0.1 M)
F
so for reaction At anode: 2Ag – 2e h 2Ag+ –0.8 V
1 1 At cathod: Cd + 2e h Cd
2+
–0.4 V
Au + 2CN– + O2 + H2O h Au(CN)2– + OH–
4 2 2Ag + Cd h 2Ag + Cd
2+ +
–1.2 V
RT RT
E° = 0.41 + lnX – 1.7 = –1.29 + lnX (0.1 M) (0.1 M)
F F
+ 2
DG° = –nFE° (n = 1) [Ag ] 1
Q= 2+
=
DG° = 1.29 F – RT lnX [Cd ] 10
43. (c) Due to –ve cell potential, reaction is non-spontaneous.
Anode: H2 Æ 2H+ + 2e– 0.0591 1
Ecell = - 1.2 - log
Cathode: Cl2 + 2e– Æ 2Cl– 2 10
E = E° – 0.0591 log [H+][Cl–] 0.0591
= - 1.2 +
on increasing concentration by 10 E will increase by a 2
factor of –0.0591 log 100 = –0.0591 ¥ 2 = –0.1182 V = - 1.17 V

2. (A-p,t), (B-q,t), (C-s,t), (D-r)

Æ Cu 2+
6. (b) Cu - 2e ææ E ocell = -0.066
Sn2+ + 2e h Sn E° = –0.14 V
2Ag + + 2e ææ
Æ 2Ag E ocell = +0.799
Sn4+ + 2e h Sn2+ E° = 0.13 V
Sn4+ + 4e h Sn 2Ag + + Cu ææ
Æ Cu +2 + 2Ag E ocell = +0.733V
Use nE° = n1E°1 + n2E°2 0.0591 0.1
7. (a) Ecell = Ecell
o
- log
- 2 ¥ 0.14 + 2 ¥ 0.13 -0.01 2 (0.1) 2
Eo = = 0.0591
4 2 = 0.733 - ¥1
2
o
ESn +4
/Sn
= -0.005V = 0.7034 V
∴ ESn
o
/Sn +4
= +0.005V Comprehension II
8. (a) The highest reduction potential for the formation of
Sn2+ + 2e h Sn E° = –0.14 V Mn2+ ions indicate, Mn++ is the most stable form.
Sn – 2e h Sn
+2 4+
E° = –0.13 V 9. (c) The three case Mn7+ dissociates to give Mn2+, Mn4+
and Mn5+ respectively. Thus it is least stable.
\ Sn + Sn h Sn + Sn
2+ 2+ 4+
E° = –0.27 V
10. (a) Mn4+ + e h Mn2+ E° = 1.51 V
If the potential of a cell is +ve, the cell reaction is spon- Mn4+ + 1e h Mn3+ E° = 0.95 V
taneous, otherwise non-spontaneous. use nE o = n1E1o + n 2 E o2
3. (A -t), (B-r), (C-p), (D-q), (E-s)
1.51 + 0.95
96500Coulomb = charge on NA e– Mn4+ + 2e h Mn2+ E° =
2
N A e− 6.022 × 1023 2.46
∴ 1coulomb = = = = 1.23V
96500 96500 2
6022 Comprehension III
= × 1018 11. (b)
965 +7
= 6.24 × 1018 e − M nO − 4 + e ⎯⎯
→ MnO −2 4 0.56
+6 +4
and see theory for cell M nO −2 4 + 2e ⎯⎯
→ M nO 2 2.26
4. (A - p,q,r,t), (B - p, q, r, s, t), (C - p, q, r, s, t), (D - r, s) MnO 2 + e ⎯⎯
→ Mn 3+
0.95
K × 1000 3+ 2+
(A) Λ m = Mn + e ⎯⎯
→ Mn 1.5
M − 2+
MnO 4 + 5e ⎯⎯
→ Mn
and M = Number of moles in one liter solution
0.56 + 2 × 2.26 + 0.95 + 1.5
1 E0 =
M∝ 5
V(dilution)
7.53
= = 1.506V
1 5
M∝
Temperature 12. (a)
and K depend on Nature of substance MnO 4 - + 5e ææ
Æ Mn 2+ 1.506 V
2+ -
2.303RT Fe ææ
Æ Fe + 2e - 0.44..... ..(i)
(B) and (C) E cell = E cell
o
− log Q
n Æ Fe3+ + 3e -
Fe ææ 0.036.......(ii)
(D) P, T and C constant at standard condition.
-------------------
Comprehension
Fe 2+ ææ
Æ Fe3+ + e - E∞ = ?
Comprehension I
use nE = o
n1E1o + n 2 E o2
Æ Cu +1 + e - E1o = -0.05 V
5. (d) Cu ææ
-2 ¥ 0.44 + 3 ¥ 0.036
+ +2 - = -0.772V = E oFe+2 /Fe+3
Cu ææ
Æ Cu +e E o2 = -0.15 V 1
Cu ææ
Æ Cu +2 -
+ 2e E∞ = ? \ E ocell = (1.506) + -(0.772) = 0.734V
2 ¥ E oCu/Cu +2 = 1 ¥ -0.05 + 1 ¥ -0.15 13. (d)
Fe|Fe 2+ (0.1M) || H + /H 2 , pt
0.20 (10-52 M )
\ E oCu/Cu +2 =- = -0.066 V
3 HA + NaOH h BA + H 2 O

m-moles 30 20 – – 1 l
10 0 10 – fi K = 77 ¥ 25 ¥ 10–7 = 1925 ¥ 10–7 =
R A
Acidic buffer,
Ph = PKa + log
[Salt ] ∴ = 1925 × 10 −7 × 1000 = 0.1925cm −1
A
[ Acid ]
18. (d) N = M ¥ 2
10
= 5.2 + log = 5.2 5 ¥ 10-3
10 fi M=
+ −5.2 2
∴ [H ] = 10 M
l
= 0.1925
At anode : Fe - 2e h Fe 2 + o
Ecell =x A
At Cathod : 2H + + 2e h H 2 (g) E ocell = 0 1000 ¥ 2
l = K ¥V = K ¥
+ 5 ¥ 10 -3
Fe + 2H (aq.) h Fe2 + + H 2 (g)
1 l 1000 ¥ 2
0.0591 0.1 = ◊ ◊
Ecell = Ecell
o
- log + 2 R A 5 ¥ 10 -3
2 [H ]
1 1000 ¥ 2
o
Ecell = x = + 0.44 V l= ¥ 0.1925 ¥
400 5 ¥ 10 -3
\ E cell = 0.44 -
0.0591
log
[0.1] = 192.5 W -1cm 2 mol -1
2
2 È10 -5.2 ˘
Î ˚ Comprehension VI
= 0.44 -
0.0591
log ÈÎ10+9.4 ˘˚ 19. (b) Pb + SO 4-2 Æ PbSO 4 + 2e -
2
PbO 2 + 4H + + SO -4 2 + 2e- Æ PbSO 4 + 2H 2O
= 0.44 – 0.277 = 0.1623V
Comprehension IV Pb + PbO 2 + 4H + + 2SO -4 2 Æ 2PbSO 4 + 2H 2O
14. (c) Species with greater reduction potential, oxidises During charging on passing 1F charge 1 mole of H2SO4
other with lower reduction potential. is produced
15. (d) Mn3+ oxidises H2O to O2 because the standard re- \ nf = 1
duction potential of (Mn3+ h Mn2+) is greater than 98
that of (O2 h H2O). EH2SO4 =
1
Write up V
20. (a) Weight of H2SO4 before discharging
16. (d) R = 1000 W
39
l (Cl - ) = 80 = 1.294 ¥ ¥ 3500
100
l (SO 4-2 ) = 160 = 1766.31 g
l = lm + b C Weight of H2SO4 after discharging
20
l = 107 + b 4 ¥ 10-4 (1) = 1.139 ¥ ¥ 3500
100
= 797.3 g
l = 97 + b 9 ¥ 10-4 (2)
Normality of H2SO4 before discharging
Eq (1) – Eq (2) 1766.31 1
0 = 10 + b(2 ¥ 10–2) – b ¥ (3 ¥ 10–2) = ¥ = 5.15
98 3.5
0 = 10 – b ¥ 10–2
10 = b ¥ 10–2 Normality of H2SO4 after discharging
b = 10+3 797.3 1
l = 107 + 103 ¥ 2 ¥ 10–2 = ¥ = 2.32
98 3.5
(NaCl) = 107 + 20 = 127
21. (c) D(NV) ¥ F = Total charge
1000
17. (d) λ m = K × Coulomb
M Ampere-hour =
-4 3600s
lm = l – b C = 127 – 10 25 ¥ 10
3
(5.15 - 2.32) ¥ 3.5 ¥ 96500
lm = 127 – 103 ¥ 5 ¥ 10–2 =
3600
1000 955832.5
= 77 = K ¥ V = K ¥ = = 265.5
25 ¥ 10-4 3600

22. (a) Assertion and Reasoning

Loss in mass of H2SO4 during discharge 29. (a) Assertion is correct (Can be checked from electro-
= 1766.31 – 797.3 = 969.01 g chemical series).
Moles of H2SO4 lost during discharge Reason B also the correct explanation.
969.01 30. (a) For specific conduction, the number of charge
= = 9.88786 carrying particles are less compared to the increases
98
During the discharge reaction, 4 moles of H+ ions, i.e., in Area. For equivalent conductance the increases in
2 moles of H2SO4 require 2F, 2 ¥ 96500 coulombs. volume is more comparable to the decrease in specific
\ 9.88786 moles will require conductance.
31. (b) Assertion is correct and Reason is correct but not
2 ¥ 96500 ¥ 9.88786
= = 954178 Coulombs the proper explanation . Assertion is convention based
2 but reason is related to Nernst equation.
Totalcharge =
954178
F = 9.9F 32. (a) Due to discharge of H+, the concentration of OH–
96500 ion increases and thus the solution become alkaline
23. (c) See lead storage battery discharge reaction. 33. (c) NaCl h Na+ + Cl–
H2O h H+ + OH–
Comprehension VII At Cathode: 2H+ + 2e h H2(g)
24. (b)
1
litre of 4 M NaCl is electrolysed. At Anode: 2Cl– – 2e h Cl2(g)
2 34. (a, c) CuBr2h Cu+2 + 2Br–
2Cl − ⎯⎯ → Cl2 + 2e − H2O h H+ + OH–
1 At Cathode Cu+2 + 2e– h Cu
× 4 = 2mole gives1moles Cl2 gas At Anode 2Br– h Br2 + 2e–
2
35. (a, d) Reduction potential means the means the abil-
OR
ity of the species to accept electrons. Metals are good
\ Number of equivalents of NaCl
contributor of electrons. That is why down the group
electrolysed = 2 eq
(which is arranged in order of increasing reduction po-
Amount of Cl2 produced = 2 eq = 1 mole
tential) reactivity decreases
25. (d) Amount of Na formed = 2 eqNa = 46 gNa
\ wt of amalgm (NaHg) = 2 mole ¥ [223] 36. (b, c, d) CuSO4 h Cu2+ + SO 4-2
= 446 gram H2O h H+ + OH–
26. (d) Total Charge = 2F = 193000C
At Cathod: Cu2+ + 2e h Cu(s)
Passage VIII At Anode: Ni – 2e h Ni2+(aq)
27. (b) (3e– + 4H+ + NO3– h NO + 2H2O) ¥ 2
37. (a, c, d) Hints: Top members in the electrochemical se-
(Cu h Cu+2 + 2e–) ¥ 3
ries are having the tendency to lose electrons I hence
8H+ + 2NO3– + 3Cu h 3Cu+2 + 2NO + 4H2O
oxidised. For a spontaneous cell reaction Ecell must be
0.06 P 2 [Cu +2 ]3 positive.
E = 0.96 – 0.34 – log NO (i)
6 [NO3- ]2 [H + ]8 38. (a, c) SRP – 1.66 < 0.77 < 1.08 for Al, Fe+2, Br–
\ Reducing power
since [HNO3] = 1 M so [H+] = [NO3–] = 1 Al > Fe+2 > Br–
E = 0.62 –
0.06
log (10–3)2 (0.1)3 = 0.71 V 39. (a, c) Due to formation of Cu2+ ions in the solution.
6 Hints: Refer electrochemical series and
28. (e– + 2H+ + NO3– h NO2 + H2O) ¥ 2 Cu + dil. HNO3 h Cu(NO3)2 + NO + H2O
Cu h Cu+2 + 2e– 40. (a, d) Fe(s) + Cu2+ (0.01 M) h Fe2+ (0.1 M) + Cu
4H + 2NO3 + Cu h Cu + 2NO2 + 2H2O
+ – +2 0.0591 [Fe 2 + ]
o
Ecell = Ecell
o
- log
[PNO2 ]2 [Cu +2 ]
2 [Cu 2 + ]
0.06
E = 0.79 – 0.34 – log (ii) 41. (b, d) T1 = 273 K
2 [NO3- ]2 [H + ]4 T2 = 298 K
Let [HNO3] = xM so [H+] = [NO3–] = x dE 0.6753 − 0.6195
equation (i) and (ii) =
dT 298 − 273
0.06 10 -9 0.06 10 -7 = 0.002232 V/K
0.62 - log 10 = 0.45 - log 6
2 x 2 x Ê Ê dE ˆ ˆ
DH = nF Á T Á ˜ - E ˜
0.06 0.06 Ë Ë dT ¯ ¯
0.17 = [ - 9 - 10 log x] - [ - 7 - 6 log x]
6 2 = 2 ¥ 96500(298 ¥ 0.002232 – 0.6753)
x = 100.56 M = –1961.6 J = –1.9616 KJ

42. (a, b, c) Refer electrochemical series.

0.0591 [Fe3+ ]
SRP + 1.09 > + 0.54 > – 0.44 for Br2/Br–, I2/I– and Fe+2/ o
0 = Ecell – log
Fe 1 [Fe2+ ][Ag + ]
\ Fe can reduced Br2 and I2 into Br– and I– and 1
I– can reduce Br2 into Br–
o
Ecell = 0.0591 log = 0.028
[Ag + ]
43. (b, c) Electrolytic conduction increases with rise in
temperature because due to formation of more ions. 1
log = 0.4737 = log 3
Also check Nernst esn. [Ag + ]
44. (a, c) In first case, H+ and Cl– discharges, which in- 1
creases the amount of OH–. \ = 3 and
In second case, CH3COO– hydrolyses with water giv- [Ag + ]
ing a solution of PH > 7. [Ag+] = 0.34
45. (a, b)
nE o
0.059 [Cu +2 ] log K = = 0.4737 = log 3
(a) Ecell = Ecell
o
- log 0.0591
2 [Ag + ]2
K = 3.0
0.059 0.01 52. (6) At cathode: Mg2+ + 2e– h Mg
= Ecell
o
- log
2 (0.1) 2 at anode: 2Cl– h Cl2 + 2e
\ Ecell = Ecell
o equivalent of Mg at cathode = Equivalent of Cl2 at
anode
0.059 0.01
o
(b) Ecell = Ecell - log 6.5 wCl2
2 (0.1) 2 \ =
24.3/2 35.5
at Ph = 1 and [H+] = 0.1
46. (a, c) See theory fuel cell \ wCl2 = 18.99 g
47. (a, b, d) The following reactions take place in a lead
weight
storage battery during discharging process: At NTP PV = nRT = RT
molarmass
At Anode: Pb + SO 24- h PbSO4 + 2e–
18.99
At Cathode: 1¥V = ¥ 0.0821 ¥ 273
71
PbO2 + 4H+ + SO 24- + 2e– h PbSO4 + 2H2O Volume of Cl2 = 6.0 L
\ net cell reaction 53. (2) Current flown = 0.525 amp as shown by ammeter
Pb + PbO2 + 4H2SO4 h 2PbSO4 + 2H2O Actual current flown
In the overall reaction H2SO4 is consumed and water
w 0.6354 ¥ 96500
is formed. (Pb, PbSO4 and PbO2 are solids). Therefore, (i) = ¥ 96500 =
the density of H2SO4 solution decreases. E¥t (63.54/2) ¥ 60 ¥ 60
48. (a, c, d) Since OH– is produced in R.H.S., hence the \ i = 0536 ampere
pH of R.H.S. increases, whereas H+ is produced in the Thus error in (i) = 0.536 – 0.525 = 0.011
L.H.S, hence the pH of L.H.S. decreases. 0.011 ¥ 100
\ % error in ammeter = = 2.05% =
49. (a, b) 0.536
2.0% approx.
Oxidation at anode∴mass ↓
54. (2) 88 g Hg has 12 g Cd
12 ¥ 2.56
Cu+2 + Cu Cu + Cu+2 \ 2.56 g Hg require = = 0.349 gram Cd
88
Cd = 0.349
Reduction at cathode ∴ mass ↑ È 112.40 ˘
since Cd2+ + 2e h Cd Í\ ECd =
E 63.5 ¥ 2.68 ¥ 3600 Î 2 ˙˚
W= ¥i¥t= = 3.174 g
96500 2 ¥ 96500 Now, w =
E.i.t
96500
50. (a, c) 2H+ + Fe h Fe2+ + H2
E°cell = E°cathode – E°anode = 0 – (–0.34) = 0.34 V 112.4 ¥ 5 ¥ t
0.349 = = 120 sec = 2 min
Fe will oxidised emf is +ve, the reaction shall occur. 2 ¥ 96500
o
51. (3) Ecell = EFe
o
2+ + EAg
o 55. (4) Ni h Ni2+ + 2e o
EOP = 0.236 V
/Fe3+ +
/Ag
= –0.771 + 0.799 = 0.028 volt 2H+ + 2e h H2 o

ERP =0
At equilibrium, Ecell = 0 Ecell = 0

Volume of O2 at STP released at anode

0.059 [H + ]2
\ Ecell = Ecell
o
+ log10 1.2 ¥ 7 ¥ 60
2 [Ni 2+ ] = ¥ 22400 = 29.245 mL
96500 ¥ 4
0.059
0 = 0.236 + log10 [H + ]2 Total of gases (Cl2 + O2 + H2) liberated at STP during
2
entire electrolysis
0.059
fi +0.236 = × 2 ⎡ − log ⎡⎣ H + ⎤⎦ ⎤ = 141 + 58.49 + 29.245 = 228.735 mL
2 ⎣ ⎦ Second, let us assume that the that of CuSO4
4 = –log[H+] = Ph In first part of electrolysis, the ions discharged at cath-
\ pH = 4 ode and anode are Cu2+ and OH– respectively.
56. (4) Since Pdn+ + ne h Pd At cathode: Cu2+ + 2e+ h Cu
w i¥t 1
For Pd, = At anode: 2OH - h H 2O + O 2 + 2e -
E 96500 2
2.977 3 ¥ 1 ¥ 60 ¥ 60 2 ¥ 0.4 0.4
= \ mole of O2 liberated at anode = =
106.4/n 96500 63.5 ¥ 4 63.5 ¥ 2
n=4 \ volume of O2 at STP liberated at anode
57. The problem does not mention about the acidic salt 0.4
of Cu2+, i.e., what kind of acidic salt is this? Does the = ¥ 22400 = 70.55 mL
63.5 ¥ 2
acidic salt have chloride, sulphate or nitrate as anion In second part of electrolysis, the H+ and OH– ions are
against the cation Cu2+ and the answer will solely discharged at cathode and anode respectively.
depend on the assumption we make in the beginning At cathode: 2H+ + 2e– h H2
about the acidic salt. First, let us assume that the salt is
1
of cupric chloride (CuCl2). At anode: 2OH - h H 2O + O 2 + 2e -
In the first part of electrolysis, the reaction occurring at 2
the two electrodes are Volume of H2 at STP released at cathode
At cathode: Cu2+ + 2e– h Cu 1.2 ¥ 7 ¥ 60
= ¥ 22400 = 58.49 mL
At anode: 2Cl– h Cl2 + 2e– 96500 ¥ 2
[The reaction occurring at anode is the oxidation of Volume of O2 at STP released at anode
Cl– in preference to OH– since the standard oxidation
1.2 ¥ 7 ¥ 60
potential of Cl– > OH–]. = ¥ 22400 = 29.245 mL
96500 ¥ 4
0.4
Mole of Cu2+ reduced at cathode = \ total of gases (H2 + O2) liberated at STP during en-
63.5
2 ¥ 0.4 tire electrolysis
Mole of electrons required at cathode = = = 70.55 + 58.49 + 29.245 = 158.285 mL
63.5
Mole of electrons released at anode [Note: If we assume the salt to be Cu(NO3)2, the vol-
2 ¥ 0.4 ¥ 1 0.4 ume of gases liberated (at STP) still remains same as in
\ mole of Cl2 liberated at anode = =
the case of CuSO4 (158.235 mL) as NO3- is also resis-
63.5 ¥ 2 63.5
Volume of Cl2 liberated at STP at anode tant to oxidation (just like SO 24- ) and OH- oxidises in
0.4 preference to NO3- ].
= ¥ 22400 =141 mL 58. (25%) For reversible cells, if an external voltage of op-
63.5
In second part of electrolysis, when current is passed posing polarity is attached to the cell, a current flowing
for 7 more minutes, the H+ will be reduced at cathode from thallium to tin electrode is given as
since Cu2+ ions are discharged completely and OH– I=
E – Eb
(i)
ions are oxidised at anode since Cl– is also completely R
oxidised. The reactions occurring are: where E = Applied voltage = 1.2 V, Eb = Back emf (i.e.,
At cathode: 2H+ + 2e– h H2 reversible emf of cell) and R = cell resistance.
1 Calculation of R:
At anode: 2OH - h H 2O + O 2 + 2e – For cell: Tl | Tl+ (0.1 M) || Sn+2 (0.01 M) | Sn
2
1.2 ¥ 7 ¥ 60 o 0.0591 [Tl+ ]
Mole of electrons passed = Eb = Ecell = Ecell – log
96500 1 [Sn +2 ]1/2
Volume of H2 at STP released at cathode 0.1
= (0.340 – 0.140) – 0.059 log fi Eb = 0.2 V
1.2 ¥ 7 ¥ 60 (0.01)1/2
= ¥ 22400 = 58.49 mL
96500 ¥ 2

Ecell Ecell 0.2 The cathode half-cell is a hydrogen electrode is which

+
I= fi R= = ; R = 5W C6H5NH3 on hydrolysis gives H+
R I 40 ¥ 10 –3
(Cationic hydrolysis)
1.2 – 0.2 +
Using the value in equation (i), I = = 0.2 A
5 C6 H5 N H3 + H 2O h C6 H5 NH 2 + H3O +
Charge passed for 1 hour = 0.2¥ 3600 C = 720 Cou- C(1 - h) Ch Ch
lomb Ch = 6.5 ¥ 10–4

720
Equivalent of thallium deposited = \ h = 6.5 ¥ 10 –4 ¥ 32 = 2.08 ¥ 10 –2
96500
Ch 2 (2.08 ¥ 10 –2 )2
Weight of thallium deposited =
720
¥ 204 = 1.52 g Kh = ; Ch 2 = = 1.352 ¥ 10 –5 M
96500 1- h 32
0.38 61. The instability constant of
Efficiency of thallium electrode = ¥ 100 = 25% Ag(NH3) +2 Ag + + 2NH3 (i); K1 = 6.02 ¥ 10–5
1.52
59. In the given cell \ DG1o = – RT ln 6.02 ¥ 10 –8 = 0.426 F
Ag | AgCl | HCl (0.1 M) | H2 (1 atm) | Pt || Pt | H2 Ag+ + e– h Agm(ii); E° = 0.799 V
(1 atm) | H+ (c M) | KCl (1 M) | Hg2Cl2 | Hg
Ecell = 0.1256 V \ DG2o = –F(0.799)
E°= 0.2873 V for Cl– | AgCl | Ag, and E° = 0.2415 Adding (i) and (ii), Ag(NH3 ) +2 + e - m Ag + 2NH3
V for Cl– | Hg2Cl2 | Hg (iii)
Let E1 and E2 be the emf of the LHS cell and RHS cell The standard free energy change of (iii) is given by
respectively, then Ecell = E1 + E2 DG3o = DG1o + DG2o ;
The overall cell reaction of the LHS cell is –FE° = 0.426 F – 0.799 F; E° = 0.373 V
1 Similarly, Ag(CN) -2 m Ag + + 2CN - ; K2 = 1.995 ¥
Ag + HCl h AgCl + H 10–19
2 2
( PH2 )1/2 DG4o = – RT ln 1.995 ¥ 10 –19 = 1.1 F
\ E1 = ( EHo + |H - ECl
o
- ) - 0.059 log Ag(CN) -2 + e - m Ag + 2CN -
2 \AgCl|Ag [H + ][Cl- ]
= 0 - 0.2873 - 0.059 log

1
= - 0.4053 V DG5o = DG2o + DG4o ; – FE° = –0.799 F + 1.1 F
(0.1) 2 E° = –0.301 V
E2 = Ecell – E1 = 0.1256 + 0.4053 = 0.5309 V. l 4 -1
The overall cell reaction of the RHS cell is 62. Cell constant = = cm
a 7
Hg2Cl2 + H2 h 2Hg + 2H+ + 2Cl– specific conductance = conductance ¥ cell constant
0.059 [H + ]2 [Cl – ]2 1 l 1 4
\ E2 = ( E o – – EHo + |H ) – log = ¥ = ¥ = 2.332 ¥ 10 -3 mhocm -1
Cl |Hg 2Cl2 |Hg 2 2 PH2 resis tan ce a 245 7
0.059 1000 2.32 ¥ 10 -3 ¥ 1000
0.5309 = (0.2415 – 0) – log [H + ]2 ; = leq = K ¥ =
2 N 0.1
On solving, [H+] = 1.24 ¥ 10–5 M. -1
= 23.32 W cm eq 2 -1
60. The given cell is

Pt | H2 (1 atm) | H+ (1 M) || (M/32) C6H5NH3Cl | H2 (1 63. (200) Let K1 and K2 be the specific conductances of the
atm) | Pt Ecell = –0.188 V. solutions A and B respectively and the constant of the
The cell reactions are cell be l/A.
\ For solution A:
1 Specific conductance = conductance ¥ cell constant
Anode: H 2 h H + + e-
2 1
1 K1 = ¥x (i)
Cathode: H + + e- h H2 50
2 For solution B: specific conductance
(H+)c h (H+)a 1
+
K2 = ¥x (ii)
[H ]a 1 100
\ Ecell = 0 – 0.059 log ; – 0.188 = – 0.059 log +
[H + ]c [H ]c When equal volumes of A and B are mixed, both the
solutions get doubly diluted; hence their individual
On solving [H+]c = 6.5 ¥ 10–4 M
contribution towards specific conductance of the mix-

K1 K 1000
ture will be and 2 respectively and the specific Λ eq = K ×
2 2 1 N
conductance of the mixture will be (K1 + K2). 1 1000
2 ∴ Λ eq = ×
RA N
1⎡ 1 1⎤l 1 l (iii)
= ⎢ + ⎥ = 1 1 1000
2 ⎣ R1 R2 ⎦ A R A 97.1 = × ×
R 3 0.1
1
+
1
=
2 ∴ R = 34.328Ω
50 100 R V
3 2 ∴ i = = 0.1456 Amp.
= R
100 R 67. We know leq = F ¥ U
200
R= Ω l NH
o
= l NH
o
+ + l
o
= F ¥ u oNH+ + F ¥ u ClO
o
-
3 4 ClO 4 4ClO – 4 4 4
∴ 3R = 200 = F(u oNH+ + u oClO- ) = 96500(6.6 ¥ 10 -4

+ 5.7 ¥ 10 -4 )
4 4
64. Since the electrodes of the cell are just half-dipped, the
effective area will be 5 sq. cm. = 118.695 mho cm 2
l 1.5 68. We know leq = F ¥ U

Cell constant = = = 0.3 cm -1
a 5 l o + 349.8
Specific conductance = Conductance ¥ Cell constant uHo + = Ç = = 3.62 ¥ 10 –3 cm 2 volt –1s –1
F 96500
1 o
= ¥ cell constant l Na
50.11
+
resistance o
u Na + = = = 5.20 ¥ 10-4 cm 2 volt -1s -1
1 3 F 96500
= ¥ 0.3 = mho cm -1 Further, we know that
50 500
1000 Ionic velocity (cm/s)
leq = K ¥ uo =
N potential gradient volt/cm
3 1000
= ¥ = 120W -1cm 2 eq -1 2
500 0.05 \ velocity of H+=3.62 ¥ 10–3 ¥ =1.45 ¥ 10–3 cms–1
5
65. Let the volume of the vessel be V cc.
2
weight in grams Velocity of Na+ = 5.20 ¥ 10–4 ¥ = 2.08 ¥ 10–4 cms–1
Number of equivalent of NaCl = 5
equivalent weight
69. l NH4Cl = l NH+ + lCl-
o o o
500
= = 8.547 4
58.5
\ l NH
o
+ = L oNH4Cl - lCl
o
- = 150 – 76 = 74
\ volume of water (cc) containing 1 equivalent of 4
V \ l NH
o
= l NH
o
+ + l
o
= 74 + 198 = 272
NaCl = 4 OH OH -
4
8.547
lc 9.6
The specific conductance of the NaCl solution (only Further, degree of dissociation = = = 0.0353
due to presence of Na+ and Cl– ions) l ∞ 272
= 3.10 ¥ 10–5 – 2.56 ¥ 10–5 = 0.54 ¥ 10–5 K × 1000 5.8 × 10 −8 × 1000
70. λ cm = = = 1.044 × 10 −6
V M 55.55
\ LNaCl = 0.54 ¥ 10–5 ¥ λ c 1.044 × 10 −6 1044
8.547 α = ∞m = = × 10 −9 = 1.9 × 10 −9
since the vessel is big, the resulting solution may be λm 350 + 198 548
supposed to be dilute. H2O H + + OH −
\ L NaCl = L oNaCl = 149.9 C − Cα Cα Cα
V Kd = Cα = 55.55 × (1.9 × 10 −9 ) 2
2
0.54 ¥ 10–5 ¥ = 149.9
8.547 201.6 × 10 −18
V = 2.37 ¥ 108 cc. 2 × 10 −16
0.50 1 l ⎛ 1000 ⎞
66. Cell constant = = = ⎜⎝ [H 2 O] = C = = 55.5 mole / L⎟
1.50 3 A 18 ⎠

Lc 7.36 Ph calculation of weak acid (Ionic equilibrium)

71. Degree of dissociation a = = = 0.0188
L 0 390.7 \ (pH)1 = 12 pK a1 - 12 log10 C
(for CH3COOH, 0.05 N = 0.05 M)
CH3COOH m CH3COO– + H+ 1 1
Similarly, (pH)2 = pK a 2 - log10 C ( C are same)
0.05 2 2
0.05(1 – a) 0.05a 0.05a \ E cell = E OPH+ / H + E RPH+ / H
0.05a ¥ 0.05a = 0.059(PH) 2 + (-0.059(PH)1 )
Ka =
0.05(1 – a ) From (i) and (ii)
since a is very small, \ Ka = Ca 2
È1 1 ˘ 0.059
= 0.059 Í pK a 2 - pK a1 ˙ = [5 - 3]
Ka = 0.05a2 = 0.05 ¥ (0.0188)2 = 1.76 ¥ 10–5 mole/L Î2 2 ˚ 2
72. AgC Ag + + C −
= +0.059
aq
(S) aq
75. Cu2+ + 4NH3 m [Cu(NH3)4]+2
If the solubility of AgCl in water S moles/liter
K SP = [Ag + ][C − ] = S × S = S2 [Cu(NH3 ) 4 ]+2 1.0
\ Kf = 1 ¥ 1012 = +2 4
=
K × 1000 K × 1000 [Cu ][NH3 ] x(2.0) 4
and λ m = = at saturation M = S
M S \ x = 6.25 ¥ 10–14 M
Since AgCl is sparingly soluble in water, Note that due to high value of Kf almost all of the Cu+2
L AgCl = L oAgCl =138.3 ions are converted to [Cu(NH3)4]2+ ion
1000 0.059 [Cu 2 + ]
\ ¥ 10 ¥ –6
= 138.3 Now Ecell = Ecell
o
+ log10
S 2 [Zn +2 ]
or S = 1.644 ¥ 10–5 eq./L or mole/L 0.059 [Cu 2 + ]
Ksp = S2 = (1.644 ¥ 10–5)–2 = 1.1 + log10
2 [Zn +2 ]
= 2.70 ¥ 10–10 (mole/L)2
0.059 6.25 ¥ 10 -14
73. 2Hg( ) + 2Fe3+ Hg 22 + + 2Fe 2 + 1.1 + log
2 1
t=0 excess 10 −3 M – –
1.1 - 0.3894 = 0.71V
−5 −4 −4
Equilib. excess 5 × 10 4.75 × 10 9.5 × 10 Ecell = 0.71V
at equilibrium Ecell = 0 76. Ag h Ag+ + e– ERP = 0.799 V
−4 −4 2
0.059 4.75 × 10 × (9.5 × 10 ) [Ag(NH3 ) +2 ] + e h Ag + 2NH3
E ocell = log ERP = ?
2 (5 × 10 −5 ) 2
[Ag(NH3 ) +2 ] m Ag+ + 2NH3
0.059 4.75 × 9.5 × 9.5
= log × 10 −2 0.0591 [Ag(NH3 ) +2 ]
2 25 o
Ecell = Ecell + log10
1 [Ag + ][NH3 ]2
E ocell =
0.059
2
(
log 0.17 = –0.023 = E oC − E oA data in SRP ) 0.0591
0 = Ecell
o
+ log(6 ¥ 10 -8 ) fi Ecell
o
= - 0.426
E oFe3+ |Fe2+ − E oHg2+ |Hg = –0.023; 0.77 + 0.023 = 0.793 1
2
o
Ecell = ECo - E Ao
E oHg|Hg2+ = –0.793V
- 0.426 = ECo - 0.799 fi ECo = 0.373 V
2
74. The cell is,

Pt H2(1atm)|HA2| |HA1|H2(1atm) Pt 77. Use [Co(CN)6 ]4 - h [Co(CN)6 ]3- + e;
0.059 o
EOP = + 0.83 V
At L.H.S.: EH/H+ = E°OPH/H+ + ¥ log10[H+]2
1
Co3+ + e h 2+
; o
ERP = 1.82 V
–log H+ = pH \ EH/H+ = E°OPH/H+ + 0.059 (pH)2
(i) [Co(CN 6 )]4- + Co3+ m Co 2+ + [Co(CN 6 )]3-
0.059
At R.H.S.: EH+/H = E°RPH+/H + ¥ log10[H ]1
+
0.059 [Co3+ ][Co(CN)64- ]
1 and Ecell = Ecell
o
+ log10
\ EH+/H = E°RPH+/H – 0.059 (pH)1 (ii) 1 [Co 2+ ][Co(CN)36- ]
For Acid HA1 HA1 m H+ + A1– or
0.059 [Co3+ ][Co(CN)64- ][CN - ]6
[H+] = C ◊ a = Ka ◊ C Ecell = Ecell
o
+ log10
1 [Co 2+ ][Co(CN)36- ][CN - ]6

Also 6 CN - + Co 2 + m [CO(CN)6 ]4 - 81. (A) At cathode:

2e– + Cu+2 h Cu
[Co(CN)64- ] At anode:
and K f1 =
[Co 2+ ][CN - ]6 2H2O h 4H+ + O2 + 4e–
Equivalent of O2 evolved = Equivalent of Cu
and 6 CN - + Co3+ m [CO(CN)6 ]3-
formed = 0.01
[Co(CN)36- ] 0.01 ¥ 63.5
and K f2 = Total loss in weight = 0.01 ¥ 8 +
[Co3+ ][CN - ]6 = 0.3975 2
0.059 Kf Weight of resulting solution = 10 – 0.03975=
\ o
Ecell = Ecell + log10 1 9.6025 g
1 K f2
(B) Equivalent of H+ = 0.01
0.059 Kf 82. In beginning (Concentrate H2SO4 present) So
0 = 0.83 + 1.82 + log10 1
1 K f2 At anode:
2H2SO4 h H2S2O8 + 2H+ + 2e–
(At equilibrium Ecell = 0) At cathode:
K f2 2H2O + 2e– h H2 + 2OH–
\ = 1044.67 = 4.7 ¥ 1044 After some time
1019
(When concentration of H2SO4 decrease)
\ K f 2 = 4.7 ¥ 1063
At anode:
RT [H + ]2 2H2O h 4H+ + O2 + 4e–
78. E = Ecalomal
o
+ EHo + - ln
2 /H nF PH2 At cathode:
2H2O + 2e– h H2 + 2OH–
8.314 ¥ 313 [H + ]2
0.6885 = 0.28 – ln ¥ 760 2.35
2 ¥ 96500 725 Moles of O2 evolved =
22.4
[H+] = 2.57 ¥ 10–7 2 ¥ 2.35
During this time moles of H2 evolved =
pH = 6.6 22.4
79. For Fe+3 + e– h Fe+2 E° = 0.77 2 ¥ 2.35
so Fe+3 will reduce to Fe+3 Volume of H2 evolved with O2 = ¥ 22.4 =
22.4
Faraday of current passed 4.7 L
1.25 ¥ 1.1 ¥ 3600 Volume of H2 evolved with H2S2O8 = 9.722 – 4.7 =
= = 0.0513 F 5.022 L
96500
+2
gram equivalent of Fe = gram equivalent of KMnO4 5.022
Moles of H2 evolved =
required 22.4
25 5.022
0.0513 = M ¥ 5 ¥ Moles of H2S2O8 formed =
1000 22.4
M = 0.41
5.022
80. (3) At cathode: Weight of H2S2O8 formed = ¥ 194 = 43.45 g
22.4
Sn+2 + 2e– h Sn
83. At cathode only pure copper is deposited so % of Cu =
At anode:
22.011
X h X+n + ne– ¥ 100 = 98.88%
22.26
Cell reaction:
Since Cu is getting deposited, iron will also get reduced
n Sn+2 + 2X h 2X+n + nSn
because its SRP value is lesser than Cu.
E° = –0.14 + 0.78 = 0.64
Charge passed
0.0591 [ X + n ]2 = 140 ¥ 482.5 = 67550 Coloumb
E = Eo - ¥ log +2 n
2n [S ] 67550
= = 0.7 Faraday
0.0591 96500
0.65 = 0.64 – [log 0.01 – log (0.5)n] 22.011 ¥ 2
2n Faraday used for reduction of Cu = =
63.5
0.0591 0.69326
0.01 = - [–2 + n log 2] so Faraday used for iron = 0.7 – 69326 = 0.00674 F
2n
0.03384n = 2 – 0.3010n 0.00674 ¥ 56
mass of iron = = 0.1887 g
0.6394n = 2 2
n = 3.12 3 0.1887
% of Fe = ¥ 100 = 0.847%
22.26

84. At anode: 1Êlˆ 1 Êlˆ

Ag + Cl– h AgCl + e– K = 2.76 ¥ 10–3 = Á ˜= Á ˜
R Ë a ¯ 85 Ë a ¯
At cathode:
AgBr + e– h Ag + Br– (l/a) = 0.2346
1 l
[Br - ] For H2O : K H2O = ¥
E= o
EAg/AgCl/Cl - + o
EBr - - 0.0591 log (i) 9200 a
/AgBr/Ag [Cl- ]
Ksolute ¥ 1000
For reaction: For NaCl solution: KNaCl= lM =
M
Ag + Cl– h AgCl + e–
( K NaCl - K H2O ) ¥ 1000
Ag+ + e– h Ag lM =
M
E = O = EAg/AgCl/Cl
o
– + E +
o
Ag /Ag Ê 1 1 ˆ
ÁË - ˜¯ ¥ 0.2346 ¥ 1000
1 7600 9200
- 0.0591 log 126.5 =
[Ag + ][Cl - ] M
M = 4.2438 ¥ 10–5
- = E
o o
EAg/AgCl/Cl Ag/Ag +
– 0.0591 log Ksp (AgCl) (ii) 500
M= =4.2438 ¥ 10–5
for reaction 58.5 ¥ V
AgBr + e– h Ag + Br– V = 201400 L
Ag h Ag + e + – V = 2.014 ¥ 105 L
Total volume of H2 = 58.464 mL
o
E = 0 = EBr - + EAg/Ag
o
+
/AgBr/Ag 108 ¥ 5 ¥ 2 ¥ 3600
– 0.0591 log [Ag+][Br–] 87. W = = 40.29
96500
o
EBr = EAg
o
+ 0.0591 log Ksp (AgBr) But since anode is 95% pure with Ag so along with
- +
/AgBr/Ag /Ag silver some impurities will also come out so actual.
(iii)
40.29
From Equations (i), (ii) and (iii) Weight coming out of anode is = 42.41 g
0.95
Ksp (AgBr) [Br - ] Weight of anode now = 100 – 42.41 = 57.58 g
E = 0.0591 log – 0.0591 log
Ksp (AgCl) [Cl- ] 100
88. Moles of H2O2 = moles of H2 =
34
3.3 ¥ 10 -13 ¥ 0.2
E = 0.0591 log = –0.037 V 100 100 50
2.8 ¥ 10 -10 ¥ 0.001 Weight of H2 = ¥2= = Z it ¥
34 17 100
85. 2NaCl m 2Na+ + 2Cl–
100 1 ¥ i ¥ 0.5 ¥ 3600
2H2O m 2H+ + 2OH– =
At anode: 17 96500
2Cl– h Cl2 + 2e– i = 315.36 Amp.
At cathode: 89. At anode: H2 h 2H+ + 2e–
2H+ + 2e– h H2 E° = – 0.699
Net reaction: At cathode: Hg2Cl2 + 2e– h 2Hg + 2Cl–
2NaCl + 2H2O m 2OH– + H2 + Cl2 + 2Na+ E° = 0.28
0.0591
35.5 62 Ecell = – 0.699 + 0.28 – log [H+]2 [Cl–]2
WCl2 = 1000 = ¥ 25 ¥ ¥t 2
96500 100
Ecell = – 0.419 + 0.0591 pH
t = 175374.83 sec = 48.74 hr.
(a) Ecell = –0.419 + 0.0591 ¥ 5
1000 = – 0.1235 V
Moles of OH– = ¥2
71 (b) O = – 0.419 + 0.0591 pH
Volume = 20 L pH = 7.1
2000 (c) Ecell = –0.419 + 0.0591 ¥ 7.5 = 0.2425 is Ecell >
[OH–] = = 1.408 M
71 ¥ 20 0 cell is spontaneous & Calomal electrode with it
86. For KCl work as cathode i.e. positive electrode.
(Ecell = –0.419 + 0.0591 ¥ 7.5= 0.2425 Ecell > 0
K ¥ 1000 K ¥ 1000
lM = = 138 = 90. Ag2S + 2e– 2Ag + S–2 E° = x ....(i)
M 0.02 + –
2Ag 2Ag + 2e E° = –0.8

Ag2S 2Ag+ + S–2 E° = x – 0.8 For K+ ion v.f. = 1 so

0.0591 leq = lM = 73.52
E = x – 0.8 – log [Ag+]2 [S–2] Ionic mobility
2
at saturation E = 0 73.52 speed
= =
and Q = Ksp 96500 potential gradient
0.0591
0 = x – 0.8 – log Ksp 73.52 6
2 \ speed (m) = ¥ = 0.000457 cm/sec
0.0591 96500 10
x = 0.8 + log 2 ¥ 10–49 = –0.639 Distance = m ¥ t = 0.000457 ¥ 7200 = 3.29 cm
2
so for equation (i) 93. moles of Tl+1 initially = 0.0025
moles of Co+3 initially = 0.005
0.0591 Tl+1 2Co+3 h 2Co+2 + Tl+3
E = E° – log[S–2] ...(ii) +
2 0.0025 Mole 0.005 Mole – –
H2S 2H+ + S–2 K = K1 ¥ K 2 x 2x 0.005–2x 0.0025–x
[H ] [S ] (10-3 ) 2 ( S -2 )
+ 2 -2 0.0591
1.1 ¥ 10–21 = = E°cell = 1.84 – 1.25 = 0.59 = log Keq
[H 2S] (0.1) 2
\ Keq = 1020
[S–2] = 1.1 ¥ 10–16
since Keq value is very high almost all Tl+ & Co+3 will
putting this in equation (ii)
convert into Tl+3 & Co+2 respectively.
0.0591 \ 0.005 – 2x = 0.005
E = –0.639 – log 1.1 ¥ 10–16 = – 0.1674V
2 0.0025 – x = 0.0025
1 (0.005) 2 (0.0025)
91. H2 + O 2 h H2O DH1 = –56700 J/mole ...(i) 1020 =
2 4x3
2H2O h 2H+ + 2OH– DH2 = 2 ¥ 19050 ...(ii) x = 5.386 ¥ 10–10 mole
cell reaction: total volume = 50 mL = 0.05 L
at anode: H2 h 2H+ + 2e– 2 ¥ 5.386 ¥ 10-10
1 [Co+3] = = 2 ¥ 10–8
at cathode: 2e– + H2O + O 2 h 2OH– 0.05
2 [Tl+] = 10–8
1
net reaction: H2 + H2O + O 2 h 2H+ + 2OH–
2
...(iii) PREVIOUS YEARS’ QUESTIONS
equation (i) + (ii) = (iii) OF JEE (MAIN & ADVANCED)
DG1 + DG2 = DG3
DH1 –TDS1 +DH2 – TDS2 = – nFE 1. (b) For the given reaction.
(DH1 + DH2) – T (DS1 +DS2) = – 2 FE 0.0591
ECell = Ecell
o
- log K eq
(DH1 + DH2) – T (DSnet) = – 2 FE 2
dE At equilibrium, = Ecell = 0
DS = nF so
dT \ 0.0591
o
Ecell = log K eq
(See heat of reaction in electrochemical cell) 2
we know 0.0591
0.23 = log K eq
È Ê dE ˆ ˘ 2
DH = nF ÍT Á ˜ - E ˙ \
Î Ë dT ¯ ˚
log Keq = 7.78
\ Keq = 6.26 ¥ 107
DH = –56700 + 38100 = –18600 J/mole
2. (d) Concentration of Ag+ in LHE = C1 = xM
È dE ˘ Concentration of Ag+ in RHE = C2 = 0.1M
T ¥ Í ˙ = 0.001158 ¥ 298 = 0.345
Î dT ˚ For the given cell
DH -18600 0.059 C
\ = = [0.345 – E] Ecell = Ecell
o
+ log 2
nF 2 ¥ 96500 1 C1
E = +0.09637 + 0.345 = 0.44137 0.059 0.1
0.164 = log
92. leq = Ionic mobility ¥ 96500 1 x
lM = leq ¥ (v.f.) [since Ecell = 0 for concentration cell]
o

0.1 Total conductivity = K Ag + + K Br - + K NO- = 55 ¥ 10-7

log = 2.8 3
x
6. (d) Higher the standard reduction potential, better is
0.1
= 6.26 ¥ 102 o
oxidising agent. Among the given EMnO - is high-
x /Mn 2+
4
x = 1.6 ¥ 10–4 = [Ag+] est, hence MnO -4 is the strongest oxidising agent.
1 7. (a, b) Hint: This problem is based on characteristics of
[CrO-4 2 ] = [Ag + ] = 0.8 ¥ 10- 4 salt-bridge.
2
Functions of salt-bridge are
Ksp (Ag 2CrO 4 ) = [Ag + ]2 [CrO 4-2 ] (i) It connects the two half-cells and completes the
cell circuit.
= 2.44 ¥ 10–12
(ii) It keeps the solutions of two half-cells and com-
3. (c) Let ‘E’ be the emf of a cell I (With lower EMF)
plete the cell circuit but does not participate
According to the given value,
chemically in the cell reaction.
0.06 [Zn +2 ] (iii) It maintains the diffusion of ions from one elec-
E = Eo - log for cell-I (1)
2 [Cu +2 ] trode to another electrode.
(iv) A cell reaction may also occur in the absence of
0.06 [Zn +2 ] salt-bridge. Sometimes, both the electrodes dip in
E + 0.03 = E o - log for cell-II (2)
2 0.5 the same electrolyte solution and in such cases we
Eq. (2) – Eq. (1) do not require a salt-bridge. So, option (c) is in-
correct.
0.06 0.5
0.03 = log (v) This prevent mixing of two electrolytic solutions
2 [Cu +2 ] hence, option (d) is incorrect choice.
0.5 Hence, correct choices are (a), (b).
fi log = log10
[Cu +2 ] Oxidation
or [Cu+2] = 0.05M
4. (b) In + e– h In+, DG0 = –1 ¥ F(–0.4)
+2
8. (a) Mn+2 + 2Mn+2 Mn + Mn+3
In+ h In+3 + 2e– DG0 = –2F(0.42)
In+2 h In+3 + e– (Oxidation) Reduction
Use nE° = n1E°1 + n2E°2 ∞ = ( E∞ )
A OP + ( EC ) R.P
Ecell ∞
–1 ¥ FE0 = 0.4F – 0.84F
\ °
EIn = 0.44V
∞
EMn +2
/Mn +3
+ EMn
∞
+2
/Mn
= - 1.51 + [ - 1.18] = - 2.69
+2
/In +3
\ ∞
EIn +3 = - 0.44 V Since E° = –Ve
/In +2
\ Non spontaneous at standard condition.
Now Ecell = EC - E A
o o o
9. (c) According to Debye Huckel Onasager equation,
= 0.15 – (–0.44) = 0.59V lC = l - B C
∞ = 0.59 =
0.059 where, lC = limiting equivalent conductivity at concen-
At equilibrium, Ecell log K eq
1 tration C
Keq = 1010 l = limiting equivalent conductivity at infinite dilu-
5. (a) Ksp(AgBr) = [Ag+][Br–] = 12 ¥ 10–14 tion
+ C = concentration
[Ag+] = [Ag+]AgBr + [Ag ]AgNo3 = x + 10–7
10. (a) K = 1.4 Sm–1, R = 50 W, M = 0.2
\ (x + 10–7)(x) = 12 ¥ 10–14
On solving, x = 3 ¥ 10–7 (K ) =
1 l
¥
\ [Ag+] = 3 ¥ 10–7 + 10–7 = 4 ¥ 10–7 ¥ 10–3 R A
= 4 ¥ 10–4 mole/m3 l
Similarly, [Br ] = 3 ¥ 10
– –4 fi = 50 ¥ 1.4 m–1
A
[NO3- ] = 10-4 l
For second solution, R = 280, = 50 ¥ 1.4 m -1
-3 -4 -7
K Ag + = l c = 6 ¥ 10 ¥ 4 ¥ 10 = 24 ¥ 10 A
1 1
K Br - = 8 ¥ 10-3 ¥ 3 ¥ 10-4 = 24 ¥ 10-7 K= ¥ 1.4 ¥ 50 =
280 4
K NO- = 7 ¥ 10-3 ¥ 10-4 = 7 ¥ 10-7
3

Now, molar conductivity (R) Cu2+ + Cu h Cu+ + Cu+

K 1/4 1 For thus E° of Cu2+ h Cu+ is also required.
lm = = = Cu2+ + 2e– h Cu
1000 ¥ M 1000 ¥ 0.5 2000
Cu h Cu+ + e–
= 5 ¥ 10-4 S m 2mol -1 Cu2+ + e– h Cu+
11. (d)
Hint: When different number of electrons are involved n1 E1o + n2 E2o
E3o =
in a redox reaction n3
Use n3 E3 = n1E1 + n2 E2
o o o
2 ¥ 0.34 + 1 ¥ (- 0.52)
= = 0.16 V
n1E1o + n2 E2o 1
\ n3 =
n3 Also,
Æ Cu + + e -
Cu ææ
(P) E3o 3+
Fe / Fe
Cu 2 + + e - ææ
Æ Cu +
Net reaction Fe3+ h Fe
is obtained from both given reaction Cu 2 + + Cu ææ
Æ Cu + + Cu +
Fe3+ + e– h Fe3+ E° = –0.52 + 0.16 = –0.36 V
n1 = 1 E1o = 0.77 V \ (R) — (1)
(S)Cr3+ h Cr2+
Fe + 2e h Fe
2+ –
is obtained from
n2 = 2 E2o = –0.44 V
Cr 3+ + 3e - ææ
Æ Cr
Fe3+ + 3e– h Fe n3 = 3 E3o =?
Æ Cr 2 + + 2e -
Cr ææ
n1E1o + n2 E2o 0.77 + 2(- 0.44)
E3o = = Cr 3+ + e - ææ
Æ Cr 2 +
n3 3
- 0.11 - 0.74 ¥ 3 + 2 ¥ 0.91
= = - 0.04 V E3o = = - 0.4 V
3 1
\ P – (3) Thus, S = (2)
Net reaction P — (3), Q – (4), R — (1), S – (2)
4H2O m 4H+ + 4OH– 12. (b) Given, Q = 2F
is obtained from both given reaction Atomic mass of Cu = 63.5 u
2H2O h O2 + 4H+ + 4e– Valency of the metal Z = 2
We have, CuSO4 h Cu2+ + SO 24-
2H2O + O2 + 4e– h 4OH–
4H2O h 4H+ + 4e– Cu 2+ + 2e- h Cu
1mol 2mol 1mol=63.5g
n1E1o + n2 E2o 2F
E3o = = E1o + E2o = 1.23 + 0.40
n3 Alternatively,
= - 0.83 V E 2 ¥ 63.5
W = ZQ = ◊ 2F = 2E = = 63.5
\ Q — (4) F 2

Solution and
Chapter
3
Colligative
Properties
Key Concepts
Solute (Solid/Liquid/Gas) + Liquid solvent h DH vap.
Liquid solution (Homogeneous Mixture) DS =
T
Vapour Pressure of Pure Liquid RT DH
At equilibrium dP = dT
P T
Rate of evaporation = Rate of condensation P2 T2
dP DH dT ln P
Evaporation Condensation Ú P
=
R Ú T2
P1 T1
P2 DH È 1 1˘
ln = -
R ÍÎ T1 T2 ˙˚
1/T
It is the equilibrium pressure exerted by the vapours of the P1
liquid on the liquid surface. -DH
or lnP = + C from indefinite integration
Factors affecting vapour pressure of pure liquid RT
d DH
(1) Nature of liquid or (ln P) = differential form for pure liquid at a
Intermolecular forces Ø fi volatility≠ or B.P. Ø fi V.P. ≠ dT RT 2
(2) Temperature effect given temperature its vapour pressure is fixed it is indepen-
Temperature ≠ Æ more vapour pressure ≠ dent of size or shape of the vessel.
Variation of Vapour Pressure with temperature is given by
classius – Clapeyron’s equation Boiling Point ____________________________
P DH vap. È 1 1˘ It is the temperature at
ln 2 = ÍT - T ˙ which vapour pressure of 1 atm
P1 R Î 1 2˚ l V
liquid becomes equal to P
H 2O(l) H 2O(g) external pressure. When ex-
∂( DG) = DV ∂P - DS ∂T ternal pressure is 1 atm it is
called normal boiling point.
At equilibrium DG = 0
fi It is difficult to cook
DV = Vg – Vl Vg food on mountains or hilly BP T
Since Vg >>> Vl areas because boiling point
RT decreases as external pressure is less.
= (for 1 mole) fi It is convenient to cook the food in pressure cooker be-
P
cause boiling point increases as external pressure is high.
nRT
= for n mole
P

Raoult’s Law ____________________________

For two miscible and volatile liquids 1
PB°
PA μ x A fi PA = PAo ◊ x A P = PA + PB 1
P 1
PB μ xB fi PB = PBo ◊ xB PA°
m
at a given temperature PA and
yA = 0 ¨ mole fraction Æ yA = 1
PB are the partial pressure of the
A+B yB = 1 yB = 0
vapours of A and B respectively.
yA 1 - yA 1
PAo and PBo
vapour pressure of + =
pure liquid A and B respectively. PAo PBo P
xA and xB mole fraction of A and B in solution or in liquid 1 Ê 1 1 ˆ 1
= – yA + o
phase. P ÁË PAo PBo ˜¯ PB
Total vapour pressure of solution
P = PA + PB PAo – PBo 1 ( PBo - PAo ) y A + PAo
P= =
P = PAo x A + PBo xB (i) ( PBo – PAo ) y A + PAo P PAo - PBo
P vs yA graph will be a curve definitely.
P= PAo x A + PBo (1 - xA )
P= ( PAo - PBo ) x A + PBo P P°
A
If xA = 1 – xB from (i)
P°
P = ( PBo - PAo ) xB + PAo B
o o yA = 0 yA = 1
Example, If P = 90 + 120xB find PA and PB if PAo = 90 mm Hg
yB = 1 yB = 0
If xB = 1; x A = 0 \ P = PBo = 210 mmHg
Graphical Representation of Compositions in Liquid
xB = 0; x A = 1\ P = PAo = 90 mmHg phase, Vapour phase and Effect of Pressures
Graphical Representation of Raoult’s Law ___ Pmax P°
A
P Liquid
Pressure
ia
ilibr
+ PB°
xB P°
B (P) Equ Pmin
°x A L V
P = PA P°B
Vapour phase
P P°A
P° PA xA
B
PA=
xA = 0 Malefaction xA = 1
PB PB =
PA PB°x xB = 1 xB = 0
B
xA = 0 xA = 1 fi If Psystem > Pmax fi only liquid phase will exist there.
xB = 1 Composition xB = 0
fi If Psystem < Pmax > Pmin fi L m V will exist.
(mole fraction)
fi If Psystem < Pmin fi only vapour phase will exist.
Relationship between mole fraction in liquid phase (xA) and Case 1
mole fraction in vapour phase in distillate (yA) When for vapour mixture of A and B pressure is increased.
PA = PAo x A = y A P by gaseous state Dalton’s law Effect:
If (nA = 1 and nB = 1)
PA = mole fraction in gas phase (yA) ¥ total Pressure (P)
Condition (a)
PB = PBo xB = yB P At P = Pmin fi first drop of liquid is formed, so it is called
Dew Point.
1 1
TOTAL V. PRESSURE OF yA = yB =
SOLUTION IN TERMS OF yA 2 2
Condition (b)
xA + xB = 1
at P = Pmax. fi last bubble of vapour remains
P ◊ y A P ◊ yB
+ =1 xA =
1
xB =
1
PAo PBo 2 2

Solution and Colligative Properties 3.3
Case 2 nB No of moles of solute

For liquid mixture of A and B pressure is decreased. Molality m = ¥ 1000 =
wA weight of solvent in kg
If (nA = 2; nB = 1)
nB nB
Condition (a) = ¥ m A (mol wt. of solvent)
at P = Pmax fi first bubble of vapour is formed, so it is called n A wA
Bubble Point. nB m P 0 - PS
fi = ¥ mA = A
2 1 n A 1000 PS
x A = ; xB =
3 3
PAo - PS 1000
Condition (b) \ ¥ =m
PS mA
at P = Pmin fi Last drop of liquid remains
2 1 Mixture of two immiscible liquid
yA = yB = They will behave like two separate liquids.
3 3
Raoult’s Law When non-volatile solute (B) is added to PA = PAo and PB = PBo
pure solvent (A). Total vapour pressure of mixture
Total pressure of solution P or PS P = PAo + PBo P = PA° + PB°
B is non-volatile so no vapour will be there but xB π 0. \ xA < 1,
Two immiscible liquid behave like
i.e., vapour pressure will decrease.
separate pure liquids so that partial
A+B
PS = PAo x A + PBo xB ( PBo = 0) pressure will be equal to their pure
form.
PS = PAo (1 - xB )
PS = PAo - PAo xB Note:
As vapour pressure of the mixture is greater than both the
PAo - PS two components in pure form, so boiling point becomes
xB =
PAo lesser than both the two components in pure form.
xB = mole fraction of non-volatile solute
T < TAo ; T < TBo
PAo - PS = DP = Lowering in vapour pressure
PA = P \ y A = PAo ; PB = P \ yB = PBo
DP
= relative lowering in vapour pressure. PAo y A n A wA /m A
PAo So = = =
PBo yB nB wB /mB
Note:
nA, nB are moles of A and B in vapour phase.
On adding non-volatile solute vapour, pressure decreases
and according to Raoult’s Law, mole fraction of non-vol- Ideal solutions
atile solute becomes equal to relative lowering in vapour 1. These solutions obey the Raoult’s Law.
pressure. i.e., PA = PAo x A ; PB = PBo xB
PAo - PS nB P = PAo x A + PBo xB

=
PAo n A + nB 2. Strength of intermolecular forces remain unchanged,
before and after the mixing.
PAo n +n n
= A B = A +1 FA–B = FA–A = FB–B
PAo - PS nB nB 3. DHmix = 0 ( no changes in intermolecular forces)
PAo P n hence no change in interaction.
-1fi o S = A 4. DVmix = 0 Vf = VA + VB
PAo - PS PA - PS nB
No change in intermolecular forces.
PAo – PS nB 5. DSmix = +ve (for both ideal and non-ideal solution)
= always correct for any solution di- 6. DGmix = –ve (has spontaneity for both ideal and non-
PS n A lute or concentrate solution.
ideal solution)
PAo - PS nB DGmix = DHmix – TDSmix
= for dilute solution only
PAo nA Since DHmix = 0
Since If nB << nA \ DG = –TDSmix = –ve
nA + nB = nA

Since 3. DHmix = –ve (heat releases)

PA = xAPA° 4. DVmix = –ve; Vf < (VA + VB)
PB = xB PB°
Examples:
P°x B P°A 1. Acid + Water (form more stronger H bond)
Pressure
°x A + B
P = PA 2. CH3COCH3 + CHCl3 (accetone + Chloroform)
P°B PA°x A
Ø Ø Ø
PB°xB Form H-bond with Polar-polar Van der
xA = 0 xA = 1 chloroform due to Waal forces
xB = 1 xB = 0 which volatility decreases
Øes > C = 0 .............. H.
Examples:
fi Benzene + Toluene Graphical Representation
fi Methanol + Ethonal (Homologues)
fi Ethyl chloride + Ethyle bromide
PB°x B P°A
fi Clorobenzene + Bromo benzene P
PA°xA +
fi Very dilute solution P°
B PA°xA PA < xAPA°
PA PB
Non-Ideal solution PB < xBPB°
PB°xB
They do not obey the Rault’s law.
xA = 0 xA = 1
PA π PAo x A ; PB π PBo xB ; P π PAo x A + PBo xB xB = 1 xB = 0
Non-ideal solution can be of two types:
Showing positive deviation from Rault’s law. Azeotropic Mixture OR Constant Boiling
Showing negative deviation from Rault’s law. Mixture_________________________________
* Showing positive deviation from Rault’s law: These are the liquid mixtures which distill off without change
1. Volatility more compare than the ideal solution, i.e., in their composition.
PA > PAo x A ; PB > PBo xB ; P > PAo x A + PBo xB . Azeotropism observed in non-ideal solution at a given
pressure for the fixed composition.
2. Strength of intermolecular forces decreases At this condition separation of two liquids is not possible.
3. DHmix = +ve (heat absorbed) Azeotropic mixtures can be of two types.
4. DVmix = +ve, Vf > (VA + VB) (bond formed is weak so
distance between the particle increases) Minimum Boiling Azeotrops
1. B.P. of azeotropic mixture is less than both the two
Example:
components.
Alcohol + Water
2. It is formed by the solution which shows +ve deviation
{Intermolecular H bonding comparatively weaker than pure
from R Law.
water)
CH3COCH3 + CCl4 or CS2 (Interaction weaker) Graphical Representation
Ø Ø (high pressure)
Polar Nature Non-Polar Liquid phase
Vapour Pressure
Graphical Representation
Temperature
Vapour phase P°A

T°
B
(higher temp.)
T° P°B Vapour Phase
P > PA + PB A
P°A
Pressure
Liquid phase
PA > xAPA°
P°B PA°xA Azeotrope Azeotrope
PB > xBPB° xA = 0 Mole xA = 1 xA = 0 Mole xA = 1
PA PB xB = 1 xB = 0 xB = 1 xB = 0
PB°xB fracion fraction
in liq. phase
xA = 0 xA = 1
xB = 1 xB = 0
Example:
Showing Negations Deviation From Raoult’s Law: Boiling point of C2H5OH + H2O
1. Volatility decreases compare to the ideal solution, i.e., (96%) (4%) By weight
Mixture 78°C and Bolling Point of H2O = 100°C Bolling
PA < PA x A ; PB < PB xB ; P < PA x A + PB xB
o o o o
point of ethenol = 78.6°C which is less than BP of ethanol
2. Strength of intermolecular forces increases is or water.
FA - B > FA - A , FB - B

Maximum Boiling Areotrope:

PAo - PS Decrease in mass of solvent
1. Bolling point of the mixture is more than both the two o
=
components. PA Increase in mass of the dehydrating agent
2. It is observed in those solution which show –ve devia- PAo - PS Decrease in mass of solvent
tion. =
PS Decrease in mass of solution
Graphical Representation
Elevation in Boiling Point:
Vapour
On adding non-volatile solute vapour pressure decreases so
Vapour Pressure
Boiling Points
T°A T°B boiling point increases. Then elevation in boiling point DTb
Liquid T°A
T°B Liquid DTb = Tb - Tbo
Vapour phase Tb OR (Tb)s – boiling point of solution
xA = 0 Mole xA = 1 xA = 0 Mole xA = 1 Tbo – boiling point of pure solvent
xB = 1 fraction xB = 0 xB = 1 fraction xB = 0
DTb μ DP Lowering is vapour pressure
in liquid phase
DP nB m ¥ m A
Example: = =
PS n A 1000
HNO3 + H2O
(68%) (32%) by weight at 1 atm. pressure mA = Molarmass of solvent
B.P. (mixture) = 120.6°C, Which is greater than Boiling Point m = molality
of water (100°C) and Boiling Point of HNO3 (80°C) Solvent
Solution-1
Solution-2
COLLIGATIVE PROPERTIES Vapour pressure
These are the properties of dilute solutions which depends

only on the number of particles of the solute but independent
of its nature. DTb
There are four colligative properties:
T°
b Tb Temperature
DP
1. Relative lowering of vapour pressure o = xB
(x = mole fraction of solute). PA DP μ m
B
2. Elevation in boling point. DTb μ m
3. Depression in freezing point. DTb = Kbm
4. Osmotic pressure
Osmotic pressure are mainly used to find molar mass Kb Molal elevation constant
of unknown solute. DTb = Kbm
Measurement of Relative Lowering of Vapour Pressure wB ¥ 1000
by Ostwald and Walker Method: DTb = K b ¥
mB ¥ wA
Since PAo > PS
mB = molarmass of solute.
PS P°
A Here solute is neither associating nor dissociating.
moist
dryair air Dehydrating
dryair Molal elevation constant (Kb):
agent
It is the characteristic property of the solvent.
Solution Pure R(Tbo ) 2 ¥ m A

Kb =
(wt. decrease) solvent (wt. increase) 1000 ¥ DH vap.
(wt. decrease)
DHvap. molar heat of vapourisation (should in per mole)
Decrease in mass of solution μ PS
Kb for water = 0.52 K kg Mol–1
Decrease in mass of pure solvent μ PAo - PS
Unit of Kb = K molal–1 or K kg mol–1
Increase in mass of dehydrating agent = Decrease in mass of
Depression in freezing point:
(solution + solvent) μ PAo
Freezing point is the temperature at which vapour pressure of
solution and liquid phase becomes equal.

Solvent Osmotic Pressure (p):

Solution-1
Solution-2 h fi height
l h raised due
(More, non volatile
solute) to osmosis
Pressure
Solution
S V Pure
Solvent
DTf
TF T°
F Temperature SPM
At Freezing Point p = hdg
Liquid Solvent in Solution m Solid Solvent It is the hydrostatic pressure developed on the solution
So, at Freezing Point only solvent solidify, so that amount of
which stops the osmosis.
solvent remains unchanged in the solution and concentration
It is the external pressure applied on the solution that just
of solution increases.
stops the osmosis.
or
On adding non-volatile solute vapour pressure decreases so 1. If Pext = p no osmosis
Freezing Point also decreases depression in Freezing Point. 2. If Pext < p osmosis will occur
3. If Pext > p reverse osmosis
DTF = TFo - TF
(Solvent particles moves in reverse direction)
TFo = Freezing Point of pure solvent or towards dilute solution
TF = Freezing Point of solutions. Reverse Osmosis:
DTF μ DP μ m Solvent particles move in the reverse direction, i.e., from so-
DTF μ m lution to the solvent.
DTF = KF ¥ m This method is used in purification of sea water.
KF = Molal depression constant or Cryoscopic con- Vant-Hoff’s Equation for Dilute Solution:
stant p = CST
w ¥ 1000 p = CRT
DTF = K F B
mB ¥ wA p = osmotic pressure
Molal depression constant (KF) n
It is the characteristic property of the solvent. C= [C - concentration of solution (Mol L–1)]
V
R(TFo ) 2 ¥ m A
KF = Solution constant S = R = 0.0821 atm L K–1 mol–1
1000 ¥ DH fusions
n
KF for water = 1.86 K molal–1 or K. kg mol–1 p= RT
V
For dilute aqueous solutions molality molarity
m M pV = nRT
Osmosis: n-moles of solute
It is the spontaneous phenomena in which solvent particles
move from lesser concentrated solution to higher concen- Note:
trated solution through a semi-permeable membrane. (SPM) 1. For two different solution if p1 = p2 isotonic solution
2. If p1 π p2
Solution with higher osmotic pressure forms hyper-
tonic solution.
Dilute Higher Where solution is with lower osmotic pressure
solution Solvent concentration known as hypotonic solution.
● The solvent particle moves from hypotonic to
SPM hypertonic
● To just stop the osmosis external pressure
should be applied on more concentrate solution

egg and Pext. = p2 – p1
Size of egg Size of egg
increases due Size decreases due
to exsosmosis H2 O of egg HCl to endosmosis

Vant Hoff’s factor (i): 1. 0.1 M glucose, 0.1 M NaCl, 0.1 M BaCl2
Number of particles of solute finally Colligative Property μi ¥ C
i=
Number of particles of solute initially if C.P ≠ fi V.P of Solution decreases
Observed value of colligative properties C.P ≠ fi F.P of Solution decreases
=
Normal value of colligative properties C.P ≠ fi B.P of Solution increases
Normal molecular weight of solute C.P ≠ fi p (Osmotic pressure) increases
=
Observed molecular weight of solute 2. 0.1 % glucose, 0.1% urea, 0.1% sucrose. if i same then
(i) if i > 1 fi dissociation 1
(ii) if i < 1 fi association C.P μ
Molar mass
(iii) if i = 1 fi neither dissociation nor association
\ C.Pmax for urea \ V.P. and F.P. fi minimum
Examples:
BP and p fi maximum
(i) BaCl2 h Ba+2 + 2Cl– i = 3/1
(ii) K3[Fe(CN)6] h 3K+ + [Fe(CN)6]– i = 4 Concentration Term:-
(iii) thimerisation fi i = 1/3 Precent Strength
(iv) dimerisation fi i = 1/2
w weight solute
Relationship Between Degree of Dissociation (a) and i. %= ¥ 100
A m nB w weight of solution
Initially 1 – w
= B ¥ 100
Finally (1 – a) na w
(1 - a ) + na w weight of solute (in gram)
i= %= ¥ 100
1 V volume of solution (in ml)
i = 1 + (n – 1)a w w
% = B ¥ 100
i -1 V v
a= v volume of solute
n -1 %= ¥ 100
v volume of solution
Relationship between degree of association (a) and Vant- V V
Huff factor (i): % = B ¥ 100
V V
nA m An
1 – weight of solution w = (v ¥ d) of solution.
a Molarity (M ) No of moles of solute in one Liter Solution
1–a
n nB
M=
a V (Liter)
1- a +
i= n fi i = 1 + Ê 1 - 1ˆ a
ÁË ˜ If V in ml
1 n ¯
nB n
i -1 1- i M= = B ¥ 1000
a= ¥n a = ¥n V (ml) V ml
1- n n -1
1000
Modified Forms of Colligative Properties: w
Since, V=
DP d
= ixB = i ¥ (mole fraction of solute)
PAo wB 1000 wB 10 w 10
\ M= ¥ = ¥ 100 ¥ = %¥
mB V (ml) V mB V mB
DTb = iKbm
w 10d
DTf = iKfm M= %¥
w mB
p = iCRT
Normality N:- No of gram equivalent in 1 Liter solution.
Isotonic Solutions:
wB 1000 w 1000
p1 = p2 Condition for isotonic N= ¥ = nf ◊ B ¥ = n f [M ]
Eq. wt. V (ml) mB V (ml)
at a given temperature T
È w 10d ˘
i1C1RT = i2C2RT \ N = nf Í % ˙
Î w mB ˚
i1C1 = i2C2 Concentration should be mole based.

È w 10 ˘ 2 Temperature:
\ N = nf Í % ˙ Gas + Liquid fi Solution + heat (exothermic)
ÎV mB ˚
As dissolution of gas in liquid is exothermic process.
Molarmass So on increasing the temperature solubility decreases.
Equivalent weight =
n - factor 3. Pressure:
On increasing the pressure solubility of gases in liquid
Molefraction:- ratio of number of moles of one component
increases. This effect is given by Henry’s Law.
to the total Number of moles of solution
nB Henry’s Law:
Mole fraction of solute xB = for binary solution. fi At a given temperature mass of the gas dissolve in the
n A + nB
given amount of the solvent is directly proportional to
nB
\ xB = …(i) partial pressure of gas.
Sn
mμP
nA
xA = = mole fraction of solvent m
n A + nB = constant
P
xA + xB = 1 from (i)
\ nB = xB ¥ Sn fi At constant temperature, mole fraction of the gas dis-
wB solve in liquid is directly proportional to partial pres-
= x B ¥ Sn sure of the gas.
mB
xg μ P
\ wB = xB ¥ Sn ¥ mB …(ii)
and wA = xA ¥ Sn ¥ mA …(iii) P = KHxg KH: Henry constant
we know molality m = No of moles of solute in one kg sol- Unit Æ Pressure units.
vent Value of KH depends on temperature and nature of gas
w 1000 and liquid.
\ m= B ¥
mB wA
ng
From (i) and (ii) P = KH ng – moles of gas dissolved
ng + nl
x Sn mB 1000 x 1000
m= B ¥ = B ¥ =m nl - moles of the liquid
mB x A Sn m A x A mA
but
mA = molar mass of solvent.
ng << nl
Relation between molality (m) and Molarity (M) :- ng + nl nl
fi
If molarity of solution (M) means M moles solute dissolve in
1000 ml solution, if density of solution d gm/ml ng
P = KH use this
weight of solution = V ¥ d = 1000 ¥ d nl
weight of solvent = weight of solution – weight solute
According to Henry’s law, at a constant temperature
wA = 1000 d – MmB
volume of gas dissolve in the given amount of solvent
wB 1000 is independent of the pressure.
\ Molality m = ¥
mB wA Applying ideal gas equation for dissolved gas,
M ¥ 1000 PV = nRT
m=
1000d - MmB PV =
Mass
RT
Mwt
w
Since, nB = B = M = No. of moles of solute in 1 liter solu- Ê M ˆ RT
mB V =Á ˜
tion. Ë P ¯ Mwt
Factors Affecting Solubility of Gases, in Liquid: V = Constant
1. Nature of gas and liquid:
In polar solvents like water polar gases are more solu- Limitations of Henry’ Law _________________
ble whereas, solubility of non-polar gases is lesser (like
1. Solubility of gases in liquid should not be too much.
dissolves like). Gases which can be liquefied easily are
2. Henry’ law is applicable at high temperature and low
comparatively more soluble in water.
pressure concentration.

Solved Examples
1. If 0.4 g of NaOH is present in 40 mL of solution. What Sol. Weight of solution = 3.65 + 25.08 = 28.73 g
is the molarity and normality [M.wt. of NaOH = 40] 3.65
Sol. We know that Weight fraction = = 0.127
28.73
Given wB = 0.4 gram Weight percent = 0.127 ¥ 100 = 12.7%
V = 40 ml 8. A solution was prepared by adding 125 cm3 of isopro-
mB = 40 pyl alcohol to water until the volume of the solution
\
wB 1000 was 175 cm3. Find the volume fraction and volume per-
M= ¥
mB V (ml) cent of isopropyl alcohol in the solution.
0.4 1000 Sol. Volume of solute = 125 cm3
= ¥ = 0.25 M Volume of solution = 175 cm3
40 40
N = nf ¥ M 125
\ volume fraction = = 0.714
= 1 ¥ 0.25 175
= 0.25 N 125
2. The normality of 1.5M H3PO4 is and volume percent = ¥ 100 = 71.4%
175
Sol. Basicity of H3PO4 is 3 9. The density of a solution containing 13% by mass of
We know that N = nf ¥ M sulphuric acid is 1.09 g/mL. Calculate the molarity and
N = 1.5 ¥ 3 = 4.5 normality of the solution.
3. How much volume of 10 M HCl should be diluted with
w 10d
water to prepare 2.00 L of 5M HCl? Sol. M = %¥
Sol. In dilution the following equation is applicable: w mB
M1V1 = M2V2 13 ¥ 10 ¥ 1.09
=
10M HCl = 5M HCl 98
10 ¥ V1 = 5 ¥ 2.00 = 1.445 M
5 ¥ 2.00 10. Vapour pressure of solution containing 3 and 1 mol re-
V1 = = 1.00 L spectively of x and y is 550 mm at the same tempera-
10
N ture another solution (containing 4 and 1 mol x and y
4. Find out the weight of H2SO4 in 150 mL, H2SO4. respectively). The vapour pressure becomes 560 mm at
7
this temperature calculate vapour pressure of x and y in
Weight in gram pure form.
Sol. N =
Equivalent weight ¥ Volume 3 1
Sol. xx = xy = P = 550
Weight in gram = Equivalent weight ¥ N ¥ volume 4 4
1 150 21 4 1
= 49 ¥ ¥ = = 1.05 g yx = xy = P = 560
7 1000 20 5 5
5. Find out the molarity of 1 L of 93% H2SO4 and its den- P = xx Pxo + x y Pyo
sity is 1.84.
3 o 1 o
Sol. Molatrity 550 = Px + Py
4 4
w 10d 93 ¥ 1.84 ¥ 10
M= %¥ = 4 o 1 o
w mB 98 560 = Px + Py
5 5
= 78.68 M 2200 = 3Pxo + Pyo
6. A 100 cm3 solution is prepared by dissolving 2 g of
NaOH in water. Calculate the normality of the solution. 2800 = 4 Pxo + Pyo
wB 1000 – – –
Sol. N = ¥ –600 = –Pxo
Equivalent weight V (ml)
2200 = 1800 + Pyo
2.0 1000 N
= ¥ = Pxo = 600 Pyo = 400
40 100 2
11. Two liquids A and B are miscible over the whole range
7. Find the percentage by weight and weight fraction of of composition obeying the Raoults law at 350 K. The
aspirin in the solution prepared by dissolving 3.65 g of vapour pressure of pure A is 24 KPa and B is 12 KPa.
aspirin in 25.08 g of water.

A mixture of 60% A and 40% B is distilled at this tem- 4

perature. A small amount of the distillate is collected \ yBo =
5
and read distill at 350 K. What is the composition of
second distillate. 1
(c) y A = yB =
2
Sol. PAo = 24 KPa PBo = 12 KPa
1 Ê 1 1 ˆ 1
60 40 = - yA + o
xA = xB = P ÁË PAo PBo ˜¯ PB
60 + 40 60 + 40
60 40 \ P = 240 torr
= =
100 100 4 1
(d) x A = xB = i.e., liquid phase composition
24K 12K 5 5
= PAo PBo = is asked.
0.6 0.4
Py A 240 ¥ 1/2 4
40K = PAo PBo = 30 K xA = = =
PAo 150 5
yA & yB yA¢ and yB¢ = yA≤ and yB≤
13. What mass of non-volatile solute is to be dissolved in
100 g of water to decrease the vapour pressure of water
by 25%.
DP nB
1st distillate 2nd distillate Sol. =
PS n A
xA = 0.6 x¢A = yA = 3/4
xB = 0.4 x¢B = yB = 1/4 PAo – PS nB 25 wB ¥ 18
= = =
PAo x A 24 ¥ 0.6 3 PS n A 75 60 ¥ 100
yA = = =
P 24 ¥ 0.6 + 12 ¥ 0.4 4 25 ¥ 60 ¥ 100
= wB
1 75 ¥ 18
yB =
4 10
¥ 100 = wB
3 9
24 ¥ 6
4
A = y ¢A =
x ¢¢ = 111 g = wB
3 1 7
24 ¥ + 12 ¥ 14. 1000 g of 0.6 molal sucrose solution in water cooled to
4 4 –3.2°C. What weight of ice would be separated out at
1 this temperature. Molar mass of sucrose = 342.
xB¢¢ =
7 Sol. Weight of ice = Weight of H2O initially – Weight of
12. A liquid mixture of A and B is composed of 1 mol of A H2O finally.
and 1 and of B. If the pressure over the mixture at 300 K 1000 g H2O have 0.6 mol sucrose.
is reduced, at what pressure does the first bubble of va- wsol. = 1000 + 0.6 ¥ 342 = 1205.2 g
pour is formed. What is the composition of first bubble 0.6
of vapour formed. If the pressure is reduced further. At Moles of sucrose in 1000 g solution = ¥ 1000
1205.2
what pressure does last drop of liquid disappear. What = 0.5
is the composition of last drop of liquid given. wH2O initially = 1000 – 0.5 ¥ 342 = 829 g
PAo = 150 torr and PBo = 600 torr
1.86 ¥ 0.5 ¥ 1000
DTf = 3.2 =
PAo- PBo WH2O finally
Sol. (a) P =
( PBo - PA ) y oA +
o
yBo ( wH2O )finally = 290.6
1 Weight of ice = 829 – 290.6 = 538.4 g
x A = xB =
2 15. Calculate the osmotic pressure of solution containing
1 1 0.4% urea and 3.42% sucrose at 27°C.
P = PAo xB + PBo xB 150 ¥
+ 600 ¥
2 2 Sol. Molecular Mass urea = 60
= 375 torr 75 + 300 fi 375 Molecular Mass sucrose = 342
(b) Composition of vapour phase is required. We know p = CRT
n
PAo x A 150 ¥ 1/2 1 = RT
So = yA fi = V
P 375 5

Ê w 10 ˆ 19. A substance x Mwt = 94 associates in water to form

Ê w 10 ˆ
p = p1 + p2 = Á % RT + Á % RT dimer. A solution of 1.25 g of x in 50 g of water lower
Ë V mB ¯ urea Ë V mB ˜¯ sucrose
˜
the freezing point by 0.3°C calculate degree of associa-
Ê 0.4 ¥ 10 3.42 ¥ 10 ˆ tion of x. Kf = 1.86.
=Á + ˜ 0.082 ¥ 300
Ë 60 342 ¯ Sol. DTf = iKf m
p = 4.1 atm 1.86 ¥ 1.25 ¥ 1000
16. 100 mL aq. solution of glucose with osmotic pressure 0.3 = i
94 ¥ 50
1.2 atm at 25°C is mixed with 300 mL of aqueous solu-
0.3 ¥ 94 ¥ 50
tion of urea at 2.4 atm, at 25°C. Calculate the osmotic i=
pressure of the mixture. 1.86 ¥ 1.25 ¥ 1000
Sol. Must U = 60 Must 60 = Constant temperature i = 0.6
p1 = 1.2; T1 = 298 Ê1 ˆ
p2 = 2.4; T2 = 298 i = 1 + Á - 1˜ a
Ën ¯
At constant temperature
p V + p 2V2 Ê1 ˆ
0.6 = 1 + Á - 1˜ a
p mix = 1 1 Ën ¯
V1 + V2
1.2 ¥ 100 + 2.4 ¥ 300 Ê -1ˆ
0.6 = 1 + Á ˜ a
= Ë 2¯
400
1.2 + (2.4 ¥ 3) 1
= 0.6 = 1 - a
4 2
1.2(1 + 6) 1
= a = 0.4
4 2
8.4 a = 0.8 = 80%
fi 2.1 atm
4 20. At 20°C and 0.02 atm pressure. Calculate the solubility
17. The Van’ hoff factor for 0.1 M barium nitrate solution of oxygen in 1 L of water. Given KH for oxygen is 4.6
is 2.74. What is the degree of dissociation? ¥ 104 atm.
i = 2.74 C = 0.1 M Ba(NO3)2 Æ Ba +2 + 2NO3- Sol. KH = 4.6 ¥ 104
\n = 3 P = 0.02
i - 1 2.74 - 1 1.74 T = 293 K
Sol. a = = fi fi 0.87
n -1 3 -1 2 ng
P = KH ¥
18. The vapour pressure of 0.1 M solution of urea at 20°C nl
is 0.311 mm less than that of water and vapour pressure ng
of 0.1 M KCl solution is 0.574 mm less than that of 0.02 = 4.6 ¥ 104 ¥
nl
water. Calculate the apparent degree of dissociation of
KCl at this dilution. 0.02 ¥ nl
= ng
Sol. For urea 4.6 ¥ 104
DP nl = No. of moles of water in one liter
= i xB
PAo 1000
= = 55.55
0.311 18
= (i = 1) xB (1)
PAo 0.02 ¥ 55.5
\ ng =
fi since equal molal 4.6 ¥ 104
For KCl
Ê 0.02 ¥ 55.5 ˆ
0.574
= i xB (2) ÁË 4.6 ¥ 104 ˜¯ ¥ 32 = mass of O 2 per litre
PAo
(2) 0.574 7.7 ¥ 10–3 g/L
= = i = 1.845 21. 1 mole heptane (V.P. = 92 mm of Hg) is mixed with 4
(1) 0.311
mole Octane (V.P. = 31 mm of Hg), form an ideal solu-
i = 1 + (n – 1)a
tion. Find out the vapour pressure of solution.
1.845 – 1 = a
Sol. Total mole = 1 + 4 = 5
0.845 = a
Mole fraction of heptane = xA = 1/5
a = 84.5%
Mole fraction of octane = xB = 4/5

PS = x A PAo + xB PBo DTb =

w
¥ 1000 ¥ Kb
1 4 m¥W
= ¥ 92 + ¥ 31
5 5 0.15
0.216 = ¥ 1000 ¥ 2.16
= 43.2 mm of Hg. mB ¥ 15
22. At 88°C benzene has a vapour pressure of 900 torr and 0.15 ¥ 1000 ¥ 2.16
mB = = 100
toluene has a vapour pressure of 360 torr. What is the 0.216 ¥ 15
mole fraction of benzene in the mixture with toluene 26. The rise in boiling point of a solution containing 1.8 g
that will be boil at 88°C at 1 atm pressure, benzene – glucose in 100 g of a solvent is 0.1°C. The molal eleva-
toluene form an ideal solution. tion constant of the liquid is
Sol. PS = 760 torr, because solution boils at 88°C. Sol. DTb = Kb ¥ m
Now 760 = 900 ¥ mole fraction of C6H6 + 360 ¥ [1 – wB
mole fraction of C6H6] DTb = Kb ¥ ¥ 1000
mB ¥ wA
\ 760 = 900a + 360 – 360a
DTb ¥ mB ¥ wA
a = 0.74 where ‘a’ is mole fraction C6H6. \ Kb =
23. The vapour pressure of benzene at 90°C is 1020 torr. A 1000 ¥ wB
solution of 5 g of a solute in 58.5 g benzene has vapour DTb = 0.1°C
pressure 990 torr. What is the molecular weight of the mB = 180
solute? wA = 100
wB = 1.8
P 0 – PS nB wB m A
Sol. = = ¥ 180 ¥ 0.1 ¥ 100
PS n A mB wA Kb = = 1.0
1000 ¥ 1.8
1020 – 990 5 ¥ 78 27. If freezing point of a solution prepared from 1.25 g of a
=
990 mB ¥ 58.5 non-electrolyte and 20 g of water is 271.9 K, the molar
mass of the solute will be
mB = 220 Sol. Given = Tf = 271.9 K
24. Calculate the vapour pressure lowering caused by ad- wB = 1.25 g wA = 20 g Kf = 1.86
dition of 50 g of sucrose (molecular mass = 342) to 500 DTf = T0 – Tf
g of water if the vapour pressure of pure water at 25°C = 273 – 271.9
is 23.8 mm Hg. DTf = 1.1
Sol. According to Raoult’s law, DTf = molality ¥ Kf
DP nB wB
= xB = DT f = ¥1000 ¥ K f
P o
n A + nB mB ¥ wA
n wB ¥ 1000 ¥ K f
or DP = B ¥ P o mB =
nA DT f ¥ wA
50 500 1.25 ¥ 1000 ¥ 1.86
Given: nB = = 0.146; nA = = 27.78 and mB =
342 18 1.1 ¥ 20
Po = 23.8 mm Hg mB = 105.68
Substituting the values in the above equation, 28. Molal depression constant for water is 1.86°C. What
0.146 is the freezing point of a 0.05 molal solution of a non-
DP = ¥ 23.8 = 0.124 mm Hg electrolyte in water?
0.146 + 27.78
Sol. DTf = molality ¥ Kf
25. 0.15 g of a substance dissolved in 15 g of solvent boiled
= 0.05 ¥ 1.86 = 0.093°C
at a temperature higher by 0.216°C than that of the pure
solvent. What is the molecular weight of the substance. Tf = T o – 0.093 = 0 – 0.093
[Kb for solvent = 2.16°C] Tf = – 0.093 = Freezing point of solution
Sol. Given: Kb = 2.16°C 29. A cane sugar solution has an osmotic pressure of 2.46
wB = 0.15 g atm at 300 K. What is the strength of the solution?
DTb = 0.216°C Sol. p V = nST
wA = 15 g n
DTb = molality ¥ Kb or p = ST = CST
V

p 2.46 here n = 3
or C= = = 0.1 M a = 0.2433 or 24.33%
ST 300 ¥ 0.0821
33. A solution containing 30 g of a non-volatile solute in
30. A solution containing 8.6 g urea in 1 L was found to exactly 90 g water has a vapour pressure of 21.85 mm
be isotonic with 0.5% (wt./vol.) solution of an organic, Hg at 25°C. Further 18 g of water is then added to the
non-volatile solute. What is the molecular weight of or- solution. The resulting solution has vapour pressure of
ganic solute? 22.15 mm Hg at 25°C. Calculate (a) molar mass of the
Sol. Solutions are isotonic solute, and (b) vapour pressure of water at 25°C.
so p1 = p2
P 0 – 21.85 30 ¥ 18
n1 n Sol. = for I case......I (i)
ST = 2 ST {S and T are constant} 21.85 90 ¥ mB
V1 V2
Now weight of solvent = 90 +18 =108 g
n1 n2
so, = P 0 – 22.15 30 ¥ 18
V1 V2 = for II case.......II (ii)
22.15 108 ¥ m
Ê w1 ˆ Ê w2 ˆ \ By eq. (i) P°mB – 21.85 mB = 21.85 ¥ 6 = 131.1
or ÁË m ¥ V ¯˜ =Á ˜
1 1 urea Ë m2 ¥ V2 ¯ organic By eq. (ii) P°mB – 22.15 mB = 22.15 ¥ 5 = 110.75
0.30 mB = 20.35
8.6 0.5
or = 20.35
60 ¥ 1000 m2 ¥ 100 \ mB = = 67.83
0.30
m2 = 34.89
On substituting in Eq. (i),
31. A very dilute saturated solution of a sparingly soluble
salt A3B4 has a vapour pressure of 20 mm of Hg at P 0 – 21.85 30 ¥ 18
=
temperature T, while pure water exerts a pressure of 21.85 90 ¥ 67.83
20.0126 mm Hg at the same temperature. Calculate the \ P° = 23.78 mm
solubility product constant of A3B4 at the same tem- 34. The freezing point of ether was lowered by 0.60°C on
perature. dissolving 2.0 g of phenol in 100 g of ether. Calculate
Sol. Ps = 20 P° = 20.0126 the molar mass of phenol and comment on the result.
P° – Ps 0.0126 nB wB m A Given: Kf (ether) = 5.12 K kg mol–1.
= = = ¥
Ps 20 n A mB wA wB 1000
Sol. DT f = K f ◊ m = K f ¥
moles of solute mB wA
= 0.00063
moles of H 2O 2 1000
0.6 = 5.12 ¥ ¥
1 mole H2O = 18 g = 18 mL mB 100
18 mL solution = 0.00063 mole 5.12 ¥ 2 ¥ 10
0.00063 mB = = 170.6
1 L solution = ¥ 1000 = 0.035 mole/L 0.6
18 = observed molar mass
Let solubility of salt A3B4 is S then Actual molar mass of phenol C6H5OH
7S = 0.035 72 + 6 + 16 = 94
S = 0.005 mole/L It means phenol dimerise in solution.
Ksp = 33 ¥ 44 ¥ (S)7 = 27 ¥ 256 ¥ (0.005)7 35. To 500 cm3 of water 3.0 ¥ 10–3 kg of acetic acid is
Ksp = 5.4 ¥ 10–13 added. If 23% of acetic acid is dissociated, what will be
32. A 5% solution of anhydrous CaCl2 at 0°C developed 15 the depression of freezing point? Kf and density of wa-
atm osmotic pressure. What is the degree of dissocia- ter are 1.86 K kg mol–1 and 0.997 g cm–3, respectively?
tion of CaCl2? Sol. DT = Kf ¥ molality ¥ (1 + a)
Sol. p = iCST For acetic acid: CH3COOH m CH3COO–+H+
È w 10 ˘ 1 0 0
15 = i Í % ˙ ST 1–a a a
ÎV mB ˚
Given, a = 0.23; Also,
È 5 ¥ 10 ˘
=i¥Í ¥ .0821 ¥ 273 Mole of acetic acid
Î 111 ˙˚ molality (m) =
Weight of water in kg
i = 1.4857
3 ¥ 10 –3 ¥ 103
i – 1 1.487 - 1 = = 0.10
a= = 500 ¥ 0.997
and
n –1 3 -1 60 ¥
103

DT = Kf ¥ molality (1 + a) 105.3
DT = 1.86 ¥ 0.1 ¥ 1.23 = 0.229 p= atm
760
36. A 0.01 m aqueous solution of K3[Fe(CN)6] freezes at
105.3 (ii)
–0.062°C. What is the apparent percentage of dissocia- ¥ V2 = n ¥ S ¥ 298
tion? [Kf for water = 1.86] 760
Sol. DTf = i Kfm 0.062 = i ¥ 1.86 ¥ 0.01 \ by Eqs. (i) and (ii), we get
i -1 V1 283 105.3 V1 1
i = 3.33 and a= = ¥ =
n -1 V2 298 500 V2 5
3.33 – 1
afi a fi 0.777 \ 77.77%
4 –1 \ V2 = 5V1
37. A solution containing 0.011 kg of barium nitrate in 0.1 i.e., solution was diluted five times.
kg of water boils at 100.46°C. Calculate the degree of 40. A 0.1 M solution of potassium ferrocyanide is 46% dis-
ionisation of the salt. Kb (water) = 0.52 K kg mol–1. sociated at 18°C. What will be its osmotic pressure?
0.011 ¥ 10 –3 i –1
Sol. DTb = i Kbm 0.46 = i ¥ 0.52 ¥ Sol. p = i CST a =
0.1 ¥ 261 n –1
i –1 K4[Fe(CN)6] h 4K+ + [Fe(CN)6]–4
i = 2.098 a= \ n=5
n –1
2.098 – 1 i –1
fi a fi 0.55 0.46 =
5 –1
i = 2.84
3 –1
38. At 300 K, two solutions of glucose in water of con- p = 2.84 ¥ 0.1 ¥ 0.082 ¥ 291
centration 0.01 M and 0.001 M are separated by semi- p = 6.785 atm
permeable membrane. Pressure needs to be applied on 41. A 1 L solution is prepared by dissolving some solid
which solution, to prevent osmosis? Calculate the mag- lead-nitrate in water. The solution was found to boil at
nitude of this applied pressure? 100.15°C. To the resulting solution 0.2 mole NaCl was
Sol. added. The resulting solution was found to freeze at
–0.83°C. Determine solubility product of PbCl2. Given
For 0.01 M solution, For 0.001 M solution, Kb= 0.5 and Kf = 1.86. Assume molality to be equal to
n1 /V1 = 0.01 n1 /V2 = 0.001 molarity in all cases.
T = 300 K T = 300 K Sol. Pb[NO3]2 Æ Pb+2 + 2NO–3
Strong electrolyte completely ionise.
p1V1 = n1ST1 p2V2 = n2ST2 \ n=3
\ p1 = 0.01 ¥ 0.0821 \ p2 = 0.001 ¥ 0.0821 DTb = iKbm
¥ 300 ¥ 300 0.15 = 3 ¥ 0.5 ¥ m fi m = 0.1
= 0.2463 atm = 0.02463 atm Now, Pb(NO3)2 + 2NaCl h PbCl2 + 2NaNO3
The movement of solvent particles occurs from dilute 0.1 0.2 — —
to concentrate solution, i.e., 0.001 M to 0.01 M solu- — — 0.1 0.2
tion. Thus, pressure should be applied on concentrated Now, this solution contains two salts
NaNO3 strong Electrolyte \ Completely ionise
solution, i.e., on 0.01 M solution to prevent osmosis.
and PbCl2 partially ionise
Also, magnitude of external pressure = 0.2463 – 0.0246
= 0.2217 atm pressure on 0.01 M solution. PbCl2 h PbCl2 h Pb +2 + 2Cl-
Solid (aq) S 2S
39. At 10°C, the osmotic pressure of urea solution is 500
mmHg. The solution is diluted and the temperature is 0.446 = 0.4 + 3S
raised to 25°C, when the osmotic pressure is found to S = 1.54 ¥ 10–2
be 105.3 mmHg. Determine extent of dilution. \ KSP = [Pb+2] [Cl–]2
Sol. For initial solution, = 4S 3 = 1.46 ¥ 10–5
42. A protein has been isolated as sodium salt with their
500 molecular formula NaxP (this notation means that xNa+
p= atm , T = 283 K
760 ions are associated with a negatively charged protein
500 P–x). A solution of this salt was prepared by dissolving
¥ V1 = n ¥ S ¥ 283 (i) 0.25 g of this sodium salt of protein in 10 g of water
760
and ebulliscopic analysis revealed that solution boils at
After dilution, let volume becomes V2 and temperature
temperature 5.93 ¥ 10–3 °C higher than the normal boil-
is raised to 25°C, i.e., 298 K

ing point of pure water. Kb of water 0.52 kg mol–1. Also 44. Two beakers A and B present in a closed vessel. Beaker
elemental analysis revealed that the salt contain 1% so- A contains 152.4 g aqueous solution of urea, contain-
dium metal by weight. Deduce molecular formula and ing 12 g of urea. Beaker B contains 196.2 g glucose
determine molecular weight of acidic form of protein solution, containing 18 g of glucose. Both solutions al-
HxP. lowed to attain the equilibrium. Determine weight % of
Sol. DTb = i ¥ Kb ¥ m Molar mass of NaxP = M glucose in its solution at equilibrium:
( x + 1) ¥ 0.52 ¥ 0.25 ¥ 1000 Sol. Beaker A:
5.93 ¥ 10–3 = wt. of water = (152.4 – 12) gram
M ¥ 10
= 140.4 gram
( x + 1) Mole fraction of urea
= 4.56 ¥ 10–4 (i)
M
12
M 0.2
= 23x (ii) = 60 = = 0.025
100 12 140.4 0.2 + 7.8
\ M = 2300 x +
60 18
\ x + 1 = 2300x ¥ 4.56 ¥ 10–4
x + 1 = 1.0488x Beaker B:
x = 20.34 20 wt. of water = 196.2 – 18
From Eqs. (i) and (ii) = 178.2 gram
Formula of protein = H20P 18
M = 2300 ¥ 20 – 20 ¥ 23 + 20 = 45560 amu Mole fraction of glucose =
180
fi 0.01
43. The vapour pressure of two miscible liquids (A) and 18 178.2
+
(B) are 300 and 500 mm of Hg respectively. In a flask 180 18
10 mole of (A) is mixed with 12 mole of (B). However, Mole fraction of glucose is less so vapour pressure
as soon as (B) is added, (A) starts polymerising into above the glucose solution will be higher than the pres-
a completely insoluble solid. The polymerisation fol- sure above urea solution, so some H2O molecules will
lows first-order kinetics. After 100 min, 0.525 mole of transfer from glucose to urea side in order to make the
a solute is dissolved which arrests the polymerisation solutions of equal mole fraction to attain equilibrium.
completely. The final vapour pressure of the solution is Let x mole of H2O transferred
400 mm of Hg. Estimate the rate constant of the poly-
merisation reaction. Assume negligible volume change 0.2 0.1
= fix=4
on mixing and polymerisation, and ideal behaviour for 0.2 + 7.8 + x 0.1 + 9.9 – x
the final solution.
Sol. A + B h An + B now mass of glucose solution = 196.2 – 18 ¥ 4 = 124.2
PS = PT = PM = Vapour pressure of solution. 18
weight % of glucose = ¥ 100 ¥ 100 fi 14.49 %
124.2
PM = PAo x A + PBo xB
45. The addition of 3 g of substance to 100 g CCl4 (M =
Let a mole of A are left due to polymerisation after 100 154 g mol–1) raises the boiling point of CCl4 by 0.60°C
min. of Kb (CCl4) is 5.03 kg mol–1 K. Calculate
Ê a ˆ Ê 12 ˆ (a) the freezing point depression.
PM = 300 Á ˜ + 500 Á (i)
Ë 12 + a ¯ Ë 12 + a ˜¯ (b) the relative lowering of vapour pressure.
(c) the osmotic pressure at 298 K.
2.303 10 (d) the molar mass of the substance.
K= log (ii)
100 a Given: Kf(CCl4) = 31.8 kg mol–1 K and r (density) of
in 2nd Case solution = 1.64 g/cm3.
After 100 minute solute is added and final vapour pres- DT f Kf 0.6 ¥ 31.8
sure is 400 mm Hg, i.e., Ps = 400 Sol. (a) = = DT f = = 3.793∞C
DTb Kb 5.03
PM – 400 0.525
= (iii) (b) Relative lowering of vapour pressure
400 (a + 12)
3
from Eqs. (i) and (iii) a = 9.9 n
= 251.5
2.303 10 = = 0.018
n+N 3 100
Putting this in eq. (ii) K = log = 1.0 ¥ 10–4 +
100 9.9 251.5 154

n Sol. P = 179XB + 92
(c) p = CRT = RT PB = 271, PT = 92
V
n=
3
= 0.012 PBo = 271, PTo = 92
251.5 936 736
103 nB = = 12, nT = =8
V= = 62.8 mL 78 92
1.64 12
0.012 XB = = 0.6, X T = 0.4
p= ¥ 0.0821 ¥ 298 = 4.65 atm 20
0.0628 PT = 271 ¥ 0.6 + 92 ¥ 0.4 = 199.4
5.03 ¥ 3 ¥ 1000 271 ¥ 0.6
(d) 0.6 = fi mB = 251.5 YB = = 0.815
mB ¥ 100 199.4
46. If 20 mL of ethanol (density = 0.7893 g/mL) is mixed YT = 0.185
with 40 mL water (density = 0.9971 g/mL) at 25°C, On further condensation
the final solution has density of 0.9571 g/mL. Calculate XB = 0.815, XT = 0.185
the percentage change in total volume of mixing. Also PT = 271 ¥ 0.815 + 92 ¥ 0.185 = 237.844
calculate the molality of alcohol in the final solution.
271 ¥ 0.815
Sol. C2H5OH h V1 = 20 mL, d1 = 0.7893 g/mL YB = = 0.9286
237.844
m1 = 15.786 g = wB 48. The vapour pressure of a certain liquid is given by the
H2O Æ V2 = 40 mL, d2 = 0.9971 g/mL equation:
m2 = 39.884 g = wA 313.7
Log10P = 3.54595 – + 1.40655 log10T where P
T
Total mass = 55.65 g is the vapour pressure in mm and T = Kelvin Tempera-
dsol. = 0.9571 g/mL ture. Determine the molar latent heat of vaporisation as
Total mass of solution a function of temperature. Calculate its value at 80 K.
Vsol. = 58.14 mL =
density of solution d ln P DH
Sol. = …(i)
60 – 58.14 dT RT 2
% change = ¥ 100 = 3.1%
60 313.7
log P = 3.54595 – + 1.40655 log T
wB 1000 15.766 ¥ 1000 T
m= ¥ = = 8.6
mB wA 46 ¥ 39.884 313.7
ln P =3.54595 ¥ 2.303 – ¥ 2.303 + 1.40655 ln T
T
47. Vapour pressure of C6H6 and C7H8 mixture at 50°C is
given by P (mm Hg) = 179 XB + 92, where XB is the d ln P 313.7 ¥ 2.303 1.40655
= + …(ii)
mole fraction of C6H6. A solution is prepared by mix- dT T2 T
ing 936 g benzene and 736 g toluene and if the vapours Comparing Eqs. (i) and (ii)
over this solution are removed and condensed into liq- DH = R[313.7 ¥ 2.303 + 1.40655 T]
uid and again brought to the temperature of 50°C, what
at T = 80 K
would be mole fraction of C6H6 in the vapour state?
DH = 1659.9 Cal.
Exercise
LEVEL I x
PA0 (1 - x) 0
(c) (d) PA
(1 - x) x
1. If PA0 is the vapour pressure of a pure liquid A and the 2. In a mixture of A and B if the mole fraction of the com-
mole fraction of A in the mixture of two liquids A and ponent A in vapour phase is x1 and mole fraction of
B is x, the partial vapour pressure of A is component A in liquid mixture is x2 ( PA0 = vapour pres-
(a) (1 - x) PA0 (b) xPA0 sure of pure A; PB0 = vapour pressure of pure B), then
total vapour pressure of the liquid mixture is

12. Arrange the following compounds in order of de-

PA0 x2 PA0 x1 PB0 x1 PB0 x2
(a) (b) (c) (d) creasing the depression in freezing point of aqueous
x1 x2 x2 x1 solution.
3. At 40°C, the vapour pressure in torr of methanol and (i) Acetic acid
ethanol solution is P = 119x + 135, where x is the mol. (ii) Trichloroacetic acid
fraction of methanol. Hence (iii) Trifluoroacetic acid
(a) vapour pressure of pure methanol is 119 torr. (a) i > ii > iii (b) ii > iii > i
(b) vapour pressure of pure ethanol is 135 torr. (c) iii > i > ii (d) iii > ii > i
(c) vapour pressure of equimolar mixture of each is 13. During depression of freezing point in a solution,
127 mm. which of the following are in equilibrium?
(d) mixture is completely immiscible. (a) liquid solvent, solid solvent
4. A solution that obeys Raoult’s law is (b) liquid solvent, solid solute
(a) non-ideal (b) colloid (c) liquid solute, solid solute
(c) ideal (d) saturated (d) liquid solute, solid solvent
5. In a mixture A and B components show negative devia- 14. Nitrobenzene freezes at 278.98°C. 0.25 molal solution
tion as of a solute in nitrobenzene causes freezing point de-
(a) DVmix = +ve pression of 2°C. Kf for nitrobenzene is
(b) DHmix = –ve (a) 2 K m–1 (b) 4 K m–1
–1
(c) A–B interaction is weaker than A–A and B–B in- (c) 8 K m (d) 12 K m–1
teraction. 15. 0.15 g of a substance dissolved in 15 g of a solvent is
(d) None of the above. boiled at a temperature higher by 0.216°C than that of
6. 100 mL of liquid A was mixed with 25 mL of liquid B the pure solvent. Find out the molecular weight of the
to give a non-ideal solution of A–B mixture. The vol- substance. (Kf for solvent is 2.16 k.kg. m–1).
ume of this mixture would be (a) 1.01 (b) 10.1 (c) 100 (d) 10.0
(a) 75 mL 16. The freezing point of equimolal aqueous solution will
(b) Either less or more than 125 mL. be highest for
(c) Close to 125 mL but not exceeding 125 mL. (a) C6H5NH3Cl (aniline hydrochloride)
(d) Just more than 125 mL. (b) Ca(NO3)2
7. Which of the following liquid pairs shows a positive (c) La(NO3)3
deviation from Raoult’s law? (d) C6H12O6 (glucose)
(a) Water-nitric acid 17. When mercuric iodide is added to the aqueous solution
(b) Benzene-methanol of potassium iodide, the
(c) Water-hydrochloric acid (a) freezing point is raised.
(d) Acetone-chloroform (b) freezing point is lowered.
8. Liquids A and B form an ideal solution. (c) freezing point does not change.
(a) The enthalpy of mixing is zero. (d) boiling point does not change.
(b) The entropy of mixing is zero. 18. Which of the following is not a colligative property?
(c) The free energy of mixing is zero. (a) Osmotic pressure
(d) The free energy as well as the entropy of mixing (b) Elevation in B.P.
(c) Vapour pressure
are each zero.
(d) Depression in freezing point
9. Which of the following solution (in H2O) has the high-
19. Arrange the following in order of decreasing solubility
est boiling point elevation?
in H2O.
(a) 0.2 m urea (b) 0.1 m K4[Fe(CN)6]
Phenol (i), Toluene (ii), Chloroform (iii)
(c) 0.2 m K2SO4 (d) 0.3 m Glucose (a) (i) > (ii) > (iii) (b) (iii) > (ii) > (i)
10. When mango is placed in dilute aqueous solution of (c) (i) > (iii) > (ii) (d) (iii) > (i) > (ii)
hydrochloric acid, it 20. A X molal solution of a compound in benzene has mole
(a) shrinks (b) swells fraction of solute equal to 0.2. The value of X is
(c) brusts (d) Nothing happens (a) 14 (b) 3.2 (c) 1.4 (d) 2.0
11. If 32 g of an unknown molecule (assumed to be union- 21. What will be the mass percentage of aspirin (C9H8O4)
ised in solution) dissolved in 200 g of H2O of, then in acetonitrile (CH3CN) when 6.5 g of C9H8O4 is dis-
elevation in boiling point is found to be 1.04°C . Find solved in 450 g of CH3CN?
out the molar mass of the unknown molecule (given Kb (a) 2.848% (b) 1.424%
for H2O = 0.52 kg mol–1) (c) 14.24% (d) 28.48%
(a) 160 g/mole (b) 80 g/mole 22. The vapour pressure of a solvent decreased by 10 mm
(c) 40 g/mole (d) 320 g/mole Hg when a non-volatile solute was added to the sol-

vent. The mole fraction of solute in solution is 0.2. 32. The values of observed and calculated molecular
What would be mole fraction of the the solvent if de- weights of silver nitrate are 92.64 and 170 respectively.
crease in vapour pressure is 20 mm of Hg? The degrees of dissociation of silver nitrate is
(a) 0.8 (b) 0.6 (c) 0.4 (d) 0.2 (a) 60% (b) 83.5% (c) 46.7% (d) 60.23%
23. What is the mole fraction of toluene in vapour which is 33. For a dilute solution, Raoult’s law states that
in equilibrium at 30°C with a benzene-toluene solution (a) the lowering of vapour pressure is equal to the
with a mole fraction of benzene of 0.400? mole fraction of the solute.
( PBo = 119 torr and PTo = 37.0 torr) (b) the relative lowering of vapour pressure is equal
(a) 0.0237 (b) 0.337 (c) 0.437 (d) 0.237 to the mole fraction of the solute.
24. At a given temperature, total vapour pressure in torr of (c) the relative lowering of vapour pressure is propor-
a mixture of volatile components A and B is given by tional to the amount of the solute in solution.
(d) the vapour pressure of the solution is equal to the
PTotal = 120 – 75XB hence, vapour pressure of pure A
mole fraction of the solvent.
and B respectively (in torr) are
34. Benzene and toluene form ideal solution over the en-
(a) 120, 75 (b) 120, 195
tire range of composition. The vapour pressure of pure
(c) 120, 45 (d) 75, 45
benzene and naphthalene at 300 K are 50.71 mm Hg
25. Liquids A and B form an ideal solution and the former and 32.06 mm Hg respectively. What will be the mole
has stronger intermolecular forces. If XA and X A¢ are fraction of benzene in vapour phase if 80 g of benzene
the mole fractions of A in the solution and vapour phase is mixed with 100 g of naphthalene?
in equilibrium, then (a) 0.0675 (b) 0.675 (c) 0.35 (d) 0.5
X A¢ X A¢ 35. Benzene and toluene form nearly ideal solutions. At
(a) =1 (b) >1
XA XA 20°C, the vapour pressure of benzene is 75 torr and
that of toluene is 22 torr. The partial vapour pressure (in
X A¢
(c) <1 (d) X A¢ + X A = 1 torr) of benzene, at 20°C for a solution containing 78 g
XA of benzene and 46 g of toulene, is
26. What will be the mass of a non-volatile solute (molar (a) 50 (b) 25 (c) 37.5 (d) 53.5
mass 40 g mo1–1) which should be dissolved in 114 g 36. The vapour pressure of pure liquid A is 0.80 atm. On
octane to reduce its vapour pressure to 80%? mixing a non-volatile B to A, its vapour pressure be-
(a) 10 g (b) 4 g (c) 2 g (d) 16 g comes 0.6 atm. The mole fraction of B in the solution is
27. Vapour pressure of water at 293 K is 17.535 mm Hg. (a) 0.150 (b) 0.25 (c) 0.50 (d) 0.75
What will be the vapour pressure of water at 293 K 37. 100 g of liquid A (molar mass 140 g mo1–1) was dis-
when 25 g of glucose is dissolved in 450 g of water? solved in 1000 g of liquid B (molar mass 180 g mol–1).
(a) 17.44 mm Hg (b) 174.4 mm Hg The vapour pressure of pure liquid B was found to be
(c) 34.88 mm Hg (d) 8.72 mm Hg 500 torr. What will be the vapour pressure of pure liquid
28. The modal elevation constant is the ratio of the eleva- A and its vapour pressure in the solution respectively if
tion in B.P. to the total vapour pressure of the solution is 475 torr?
(a) molarity (a) 28.7 torr and 32 torr (b) 280.7 torr and 32 torr
(b) molality (c) 28.7 torr and 3.2 torr (d) 280.7 torr and 3.2 torr
(c) mole fraction of solute 38. 3.0 molal NaOH solution has a density of 1.110 g/mL.
(d) mole fraction of solvent The molarity of the solution is
29. The boiling point of an aqueous solution of a non-vola- (a) 2.9732 (b) 3.05
tile solute is 100.15°C. What is the freezing point of an
(c) 3.64 (d) 3.0504
aqueous solution obtained by diluting the above solu-
39. When 5.0 g of BaCl2 is dissolved in water to have 106
tion with an equal volume of water? The values of Kb
g of solution. The concentration of solution is
and Kf for water are 0.512°C and 1.86°C molality–1.
(a) 2.5 ppm (b) 5 ppm
(a) –0.544°C (b) –0.512°C
(c) –0.272°C (d) –1.86°C (c) 5M (d) 5 g L–1
30. Which of the following 0.1 M aqueous solution will 40. At a certain hill station pure water boils at 99.725°C. If
have the lowest freezing point? Kb for water is 0.513°C kg mol–1, the boiling point of
(a) Potassium sulphate (b) Sodium chloride 0.69 m solution of urea will be
(c) Urea (d) Glucose (a) 100.079°C (b) 103°C
31. What will be the osmotic pressure of a solution pre- (c) 100. 359°C (d) unpredictable
pared by dissolving 25 mg of K2SO4 in 2 L of water at 41. The freezing point of 1 molal NaCl solution assuming
25°C, assuming that it is completely dissociated? NaCl to be 100% dissociated in water is
(a) 5.27 ¥ 10–3 atm (b) 52.7 ¥ 10–3 atm (a) –1.86°C (b) –3.72°C
(c) 26.3 ¥ 10 atm
–3
(d) 2.63 ¥ 10–3 atm (c) +1.86°C (d) +3.72°C

42. 10 g of solute with molecular mass 100 g mol–1 is dis- 2. 0.2 molal acid HX is 20% ionised in solution. Kf = 1.86
solved in 100 g solvent to show 0.3°C elevation in boil- K molality-1 the freezing point of the solution is
ing point. The value of molal ebullioscopic constant (a) –0.45°C (b) –0.90°C
will be (c) –0.31°C (d) –0.53°C
(a) 10 (b) 3 3. How much the amount of CaCl2 (i = 2.47) dissolved in
(c) 0.3 (d) unpredictable 2.5 L of water such that its osmotic pressure is 0.75 atm
43. If the observed and theoretical molecular mass of NaCl at 27°C?
is found to be 31.80 and 58.50, then the degree of dis- (a) 0.3 mole (b) 0.03 mole
sociation of NaCl is (c) 3 mole (d) 0.003 mole
(a) 83.96% (b) 8.39% 4. Boiling point of pure H2O is 373.15 K. If 32.5 g of
(c) 90% (d) 100% KCN is dissolved in 100 mL of H2O, what will be the
44. The substance A when dissolved in solvent B shows the boiling point of solution? (Given Kb for H2O = 0.52 K.
molecular mass corresponding to A3. The Vant Hoffs kg mol–1 and molar mass of KCN= 65 g/mole)
factor will be (a) 105.28°C (b) 100.52°C
(a) 1 (b) 2 (c) 3 (d) 1/3 (c) 373.67 K (d) 373.75 K
45. A 5% solution of cane sugar is isotonic with 0.877 % of 5. The freezing point of a solution of acetic acid (mole
X. The molecular weight of substance X is fraction is 0.02) in benzene is 277.4 K. Acetic acid ex-
(a) 59.98 (b) 119.96 (c) 95.58 (d) 126.98 ists partly as a dimer 2A m A2. Determine the equi-
46. The osmotic pressure of equimolar solutions of urea, librium constant for dimerisation. Freezing point of
BaCI2 and AlCI3 will be in which order? benzene is 278.4 K and (Kf for benzene is 5).
(a) AlCl3 > BaCl2 > Urea (a) 3.39 kg mol–1 (b) 33.9 kg mol–1
–1
(b) BaCl2 > AlCl3 > Urea (c) 1.68 kg mol (d) 16.8 kg mol–1
(c) Urea > BaCl2 > AlCl3 6. Which one of the following pairs of solution can we
(d) BaCl2 > Urea > AlCl3 expect to be isotonic at the same temperature?
47. A certain substance ‘A’ tetramerises in water to the ex- (a) 0.1 M urea and 0.1 M NaCl
tent of 80%. A solution of 2.5 g of A in 100 g of water (b) 0.1 M urea and 0.2 M MgCl2
lowers the freezing point by 0.3°C. The molar mass of (c) 0.1 M NaCl and 0.1 M Na2SO4
A is (d) 0.1M Ca(NO3)2 and 0.1 M Na2SO4
(a) 122 (b) 31 (c) 244 (d) 62 7. The osmotic pressure of a 5% aqueous solution of cane
48. Which of the following solutions will exhibit highest sugar at 150°C is (Mol. Wt. of cane sugar = 342)
boiling point? (a) 4 atm (b) 3.4 atm
(a) 0.01 M Na2SO4 (b) 0.01 M KNO3 (c) 5.07 atm (d) 2.45 atm
(c) 0.015 M urea (d) 0.015 M glucose 8. If the solution of mercuric cyanide of strength 3 g/L
49. What is the osmotic pressure of 12% solution of can has an osmotic pressure 0.3092 ¥ 105 Nm–2 at 298 K,
sugar (mol. wt. 342) at 17°C? what is the apparent molecular weight and degree of
(a) 8.35 atm (b) 9.35 atm dissociation of Hg(CN)2 respectively? (Hg = 200.61, C
(c) 5.36 atm (d) 7.35 atm = 12, N = 14)
50. Mixture of volatile components A and B has total va- (a) 240.2, 2.45% (b) 480.4, 2.45%
pour pressure (in torr): (c) 480.4, 24.5% (d) 240.2, 24.5%
P = 254 – 119xA, where xA is mole fraction of A in mix- 9. Concentrated nitric acid used in laboratory work is 68%
ture. nitric acid by mass in aqueous solution. What should be
Hence PAo and PBo are (in torr) the molarity of such a sample of the acid if the density
of the solution is 1.504 g mL–1?
(a) 254, 119 (b) 119, 254
(a) 1.623 M (b) 16.23 M
(c) 135, 254 (d) 154, 119
(c) 162.3 M (d) 0.1623 M
10. Heptane and octane form an ideal solution. At 373 K,
the vapour pressures of the two liquid components are
LEVEL II 105.2 kPa and 46.8 kPa respectively, what will be the
vapour pressure of a mixture of 26.0 g of heptane and
1. A solution is obtained by mixing 300 g of 25% solu- 35 g of octane?
tion and 400 g of 40% solution by mass. What will be (a) 7.308 kPa (b) 73.08 kPa
the mass percentage of the solute and solvent resulting (c) 730.8 kPa (d) 7308 kPa
solution? 11. The vapour pressure of water is 12.3 k pa at 300 K.
(a) 23% and 77% (b) 12.5% and 87.5% What will be the vapour pressure of 1 molal solution of
(c) 33.6% and 66.4% (d) 50% and 50% a non-volatile solute in it?

(a) 24.16 k pa (b) 1.208 k pa (a) 1 (b) NA/20 (c) 2 (d) 0.1 NA
(c) 2.416 k pa (d) 12.08 k pa 20. 1.0 molal aqueous solution of an electrolyte X3Y2 is
12. The boiling point elevation constant for toluene is 25% ionised. The boiling point of the solution is (Kb for
3.32 K kg mol-1, the normal boiling point of toluene H2O = 0.52 K kg/mol):
is 110.7°C. The enthalpy of vaporisation of toluene (a) 375.5 K (b) 374.04 K
would by nearly (c) 377.12 K (d) 373.25 K
(a) 17.0 k Jmol–1 (b) 34.0 kJ mol–1 21. The molal boiling point constant of water is 0.573°C
(c) 51.0 kJ mol –1
(d) 68.0 kJ mol–1 kg mole–1. When 0.1 mole of glucose is dissolved in
13. A 5% solution (by mass) of cane sugar in water has 1000 g of water, the solution boils under atmospheric
freezing point of 271 K. What will be the freezing point pressure at
of 5% glucose in water if freezing point of pure water is (a) 100.513°C (b) 100.0573°C
273.15 K? (c) 100.256°C (d) 101.025°C
(a) 273.15 K (b) 279.07 K 22. The boiling point of an aqueous solution of a non-vola-
tile solute is 100.15°C. What is the freezing point of an
(c) 269.07 K (d) 293.07 K
aqueous solution obtained by diluting the above solu-
14. At 300 K 36 g of glucose present in a litre of its solu-
tion with an equal volume of water. The values of Kb
tion has osmotic pressure of 4.98 bar. lf the osmotic
and Kf for water are 0.512 and 1.86°C mol–1:
pressure of the solution is 1.52 bars at the same tem-
(a) –0.544°C (b) –0.512°C
perature, what would be its concentration? (c) –0.272°C (d) –1.86°C
(a) 0.061 M (b) 0.61 M 23. An aqueous solution of acetone, CH3COCH3, is 10%
(c) 0.0061 M (d) 6.1 M acetone by weight. What is the mole percentage of ac-
15. The ratio of the value of any colligative property for etone in this solution:
KCl solution to that for sugar is nearly ____ times (a) 3.332% (b) 5.000%
(a) 1 (b) 0.5 (c) 2 (d) 2.5 (c) 10.00% (d) 11.11%
16. When 0.6 g of urea dissolved in 100 g of water, the 24. The freezing point of an aqueous solution of a non-
water will boil at (Kb for water = 0.52 kJ. mol–1 and electrolyte is –0.14°C. The molality of this solution is
normal boiling point of water = 100°C): [Kf (H2O) = 1.86 K kg mol–1]:
(a) 373.052 K (b) 273.52 K (a) 1.86 m (b) 1.00 m (c) 0.15 m (d) 0.075 m
(c) 372.48 K (d) 273.052 K 25. Dry air was passed successively through a solution of
17. A solution prepared by dissolving a 2.50 g sample of 5 g of a solute in 180 g of water and then through pure
an unknown compound dissolved in 34.0 g of benzene, water. The loss in weight of solution was 2.5 g and that
C6H6 boils at 1.38°C higher than pure benzene. Which of pure solvent 0.04 g. The molecular weight of the sol-
expression gives the molar mass of the unknown com- ute is
pound? (a) 31.25 (b) 3.125
Compound Kb (c) 312.5 (d) None of these
C6H6 2.53°C.m–1
2.50
(a) 2.53 ¥
1.38 LEVEL III
34.0
(b) 1.38 ¥ ¥ 2.50
2.53 1. Match the columns:
2.53 1
(c) 2.50 ¥ 103 ¥ ¥ Column I Column II
34.0 1.38
1.38 (a) CH3COOH in H2O (p) Neither association
(d) 2.50 ¥ 103 ¥ ¥ 2.53 nor dissociation
34.0
18. When 1.20 g of sulphur is melted with 15.00 g of naph- (b) CH3COOH in benzene (q) When a non-vola-
thalene, the solution freezes at 77.2° C. What is the mo- tile solute is added.
lar mass of this from of sulphur. Data for Napthalene (c) Polymer in water (r) Molecular mass
Melting point, m.p 80°C Freezing point, depression observed greater
constant, Kf = 6.80°C m–1 than molecular
(a) 180 g mol–1 (b) 194 g mol–1 mass actual.
–1
(c) 260 g mol (d) 450 g mol–1
19. 12.2 g benzoic acid (M = 122) in 100 g H2O has eleva- (d) Vapour pressure of a (s) DTb(obs) > DTb(calc.)
tion of boiling point of 0.27°C, Kb = 0.54 K kg/mole. If liquid decreases
there is 100% dimerisation, the number of molecules of (t) van’t Hoff factor,
benzoic acid in associated state is i>1

2. Match the columns: Comprehension I

Column I Column II According to Raoult’s law (which is applicable for a mixture
(a) Azeotropes (p) Molality of volatile liquids) the partial vapour pressure of a liquid is
directly proportional to the mole fraction of that component.
(b) A mixture of CHCl3 (q) Intermolecular at-
Further assuming ideal behaviour for vapours and applying
and benzene shows traction negative
Dalton’s law we can write different equations as follows:
deviation from
ideal behaviour. PA = PAo x A , PB = PBo xB
(c) The ratio of observed (r) van’t Hoff factor PTotal = PA + PB = PAo x A + PBo xB = PBo + ( PAo - PBo ) x A
molecular mass to
theoretical molecu- Further mole fraction of a component in vapour phase is
lar mass equal to the ratio of partial vapour pressure to total vapour
pressure of mixture.
(d) The number of moles (s) Solutions with
The vapour pressure of two pure liquids A and B which
of solute dissolved in same composition
form an ideal solution are 300 and 500 torr respectively at
1000 g of solvent in vapour and liq-
temperature T. A mixture of the vapours of A and B for which
uid phase.
the mol fraction of A is 0.25 is slowly compressed at tem-
(t) Constant boiling perature T.
mixtures. 5. The total pressure when first drop of condensate is
3. Match the columns: formed will be
(a) 428 torr (b) 400 torr
Column I Column II
(c) 388 torr (d) 358 torr
(a) CCl4 + CHCl3 (p) Raoult’s law 6. The pressure when only the last bubble of vapour re-
mains will be
(b) + H2 O (q) Nearly ideal solution (a) 350 torr (b) 375 torr
(c) 525 torr (d) 450 torr
(c) PA μ xA (r) Non-ideal solution 7. The mole fraction of B in the last bubble of vapour will
with –ve deviation be
(a) 0.16 (b) 0.84 (c) 0.20 (d) 0.80
(d) CHCl3 + acetone (s) Non-ideal solution
with +ve deviation Comprehension II
(t) Hydrogen bonding A solution of sucrose (molar mass = 342) has been prepared
4. Match the columns: by dissolving 68.4 g of sucrose in one kg of water. Kf for
DHf = Molar heat of fusion of ice; Lf = Latent heat of water is 1.86 K kg mol–1 and vapour pressure of water at 298
fusion of ice (g–1) K is 0.024 atm.
DHv = Molar heat of vaporisation of water; Lv = Latent 8. The vapour pressure of the solution at 298 K will be
heat of vaporisation of water (g–1) (a) 0.230 atm (b) 0.235 atm
(c) 0.236 atm (d) 0.0235 atm
Column I Column II 9. The osmotic pressure of the solution at 298 K will be
(a) Molal depression (p) (a) 4.29 atm (b) 4.49 atm
18 ¥ 373 ¥ 373 ¥ R
constant of water (c) 4.69 atm (d) 4.89 atm
1000 DH v 10. The freezing point of the solution will be
(b) Molal elevation (q) (a) –0.684°C (b) –0.342°C
373 ¥ 373 ¥ R
constant of water (c) –0.372°C (d) –0.186°C
1000 Lv
Comprehension III
(c) DTf of solution (r) 18 ¥ 273 ¥ 273 ¥ R A system of greater disorder of molecules is more probable.
containing 9.0 g of 1000 DH f The disorder of molecules is reflected by the entropy of the
glucose in 50 g of system. A liquid vaporises to form a more disordered gas.
water When a solute is present, there is additional contribution to
(d) DTb of solution (s) 273 ¥ 273 ¥ R the entropy of the liquid due to increased randomness. As the
containing 3.0 g entropy of solution is higher then that of pure liquid, there
1000 L f
of urea in 50 g of is weaker tendency of it to form the gas. Thus, a solute (non
water volatile) lowers the vapour pressure of a liquid, and hence a
(t) Kf higher boiling point of the solution.

Similarly, the greater randomness of the solution opposes (c) Statement 1 is True, Statement 2, is False
the tendency to freeze. In consequence, a lower temperature (d) Statement 1 is False, Statement 2 is True
must be reached for achieving the equilibrium between the 14. Statement 1: If a solution is heated such that keeping
solid (frozen solvent) and the solution. rest of all things unchanged, volume is changed, then
Elevation of boiling point (DTb) and depression of freezing it also brings changes to colligative properties related
point (DTf) of a solution are the colligative properties which with it.
depend only on the concentration of particles of the solute, Statement 2: The molarity of solution changes on
not their identity. For dilute solutions, DTb and DTf are pro- changing the volume of solution for same amount of
portional to the molality of the solute in the solution. solute.
2
RTbo M 15. Statement 1: The vapour pressure of a liquid is the
DTb = Kbm Kb = Ebulliscopic cons tan t = equilibrium pressure of liquid-vapour equilibrium at
1000 DH vap
and DTf = Kf m; the given temperature.
2 Statement 2: The ratio of the lowering of vapour pres-
RT fo M sure of a solvent upon dissolution of a non-volatile sol-
K f = Cryoscopic constant =
1000 DH fus ute, to the vapour pressure of pure solvent increases
(M = molecular mass of the solvent) with temperature.
The values of Kb and Kf do depend on the properties of the 16. Statement 1: Reverse osmosis is used to purify saline
water.
DH vap
solvent. For liquids, is almost constant. For solutes Statement 2: Solvent molecules pass from concentrat-
Tbo ed to dilute solution through semipermeable membrane
undergoing change of molecular state is solution (ionisation if high pressure is applied on solution.
or association), the observed DT values differ from the calcu- 17. Statement 1: The boiling point of 0.1 M urea solution
lated ones using the above relations. In such situations, the is less than that of 0.1 M KCl solution because
relationships are modified as DTb = iKbm; DTf = iKfm where Statement 2: Elevation of boiling point is directly pro-
i = Van’t-Hoff factor, greater than unity for ionisation and portional to the number of species present in the solu-
smaller than unity for association of the solute molecules in tion.
solutions. 18. Statement 1: Gases always tend to be less soluble in
11. Depression of freezing point of which of the follow- liquids as the temperature is raised.
ing solutions does represent the cryoscopic constant of Statement 2: Vapour pressure of liquids increase with
water? increase in temperature.
(a) 6% by mass of urea in aqueous solution. 19. Statement 1: Azeotropic mixtures are formed only by
(b) 100 g of aqueous solution containing 18 g of glu- non-ideal solutions.
cose. Statement 2: Boiling point of an azeotrope is either
(c) 59 g of aqueous solution containing 9 g of glucose. higher than both the components or lower than both the
(d) 1 M KCl solution in water. components.
12. Dissolution of a non-volatile solute into a liquid leads 20. Statement 1: The vapour pressure of 0.1 M sugar solu-
to the? tion is more than 0.1 M KCl solution because
(a) Decrease of entropy. Statement 2: Lowering of vapour pressure is directly
(b) Increase in tendency of the liquid to freeze. proportional to the number of species present in the so-
(c) Increases in tendency to pass into the vapour lution.
phase. 21. Statement 1: One molar solution is always more con-
(d) Decrease in tendency of the liquid to freeze. centrated than one molal solution because
13. To aqueous solution of NaI, increasing amounts of sol- Statement 2: The amount of solvent in 1 M and 1 m
id HgI2 is added. The vapor pressure of the solution aqueous solution is not equal.
(a) decreases to a constant value 22. Statement 1: Out of various colligative properties, os-
(b) increases to a constant value motic pressure is used for determination of molecular
(c) increases first and then decreases masses of polymers because
(d) remains constant because HgI2 is sparingly solu- Statement 2: Polymer solutions do not possess con-
ble in water stant boiling point or freezing point.
23. Statement 1: If a liquid solute more volatile than the
Assertion and Reasoning Code
solvent is added to the solvent, then the vapour pres-
(a) Statement 1, is True, Statement 2 is True; Statement 2 sure may increase i.e., Ps > Po because
is a correct explanation for Statement 1 Statement 2: In the presence of a more volatile liquid
(b) Statement 1 is True, Statement 2 is True; Statement 2, solute, only solute will form the vapours and solvent
is NOT a correct explanation for Statement 1 will not.

24. Statement 1: van’t Hoff factor is equal to unity if the 30. The colligative properties of a solution are
elecrolytic solute undergoes 100% dissociation be- (a) μ molality
cause 1
Statement 2: van’t Hoff factor for sucrose solution is (b) μ
molecular mass of the solute
unity.
(c) Proportional to each other.
Multiple Correct Type (d) Independent of the nature of the solute, i.e., elec-
25. When a solute is added to a pure solvent, the trolyte or non-electrolyte.
(a) vapour pressure of the solution becomes lower 31. Identify the correct statements.
than that of the pure solvent. (a) The solution formed by mixing equal volumes of
(b) rate of evaporation of the pure solvent is reduced. 0.1 M urea and 0.1 M glucose will have the same
(c) solute does not affect the rate of condensation. osmotic pressure.
(d) rate of evaporation of the solution is equal to the (b) 0.1 M K4[Fe(CN)6] and 0.1 M Al2(SO4)3 are iso-
rate of condensation of the solution at a lower tonic solutions.
vapour pressure than that in the case of the pure (c) For association of a solute in a solution, i > 1.
solvent. (d) The ratio of van’t Hoff factors for 0.2 M glucose
26. Which is/are correct statement(s)? and 0.1 M sucrose is 2: 1.
(a) When mixture is less volatile, there is positive de-
0
32. 1 mole benzene ( Pbenzene = 42 mm) and 2 mole toluene
viation from Raoult’s law. ( Ptoulene = 36 mm) will have
0
(b) When mixture is more volatile, there is negative (a) total vapour pressure 38 mm
deviation from Raoult’s law. (b) mole fraction of vapours of benzene above liquid
(c) When mixture is less volatile, there is negative mixture is 7/19.
deviation from Raoult’s law. (c) positive deviation from Raoult’s law.
(d) When mixture is more volatile, there is positive (d) negative deviation from Raoult’s law.
devation from Raoult’s law. 33. A binary liquid (AB) shows positive deviation from
27. According to Raoult’s law, the relative decrease in the Raoult’s law when
solvent vapour pressure over the solution is equal to 0 liq 0 liq
(a) the mole fraction of the solvent. (a) p A > p A X A and p A > pB X B
(b) the mole fraction of the solute if solute does not (b) Intermolecular forces: A-A, B-B > A-B
undergo association or dissociation. (c) DVmix > 0
(c) the number of moles of the solute. (d) DHmix > 0
(d) i times the mole fraction of the solute which un- 34. The azeotropic solutions of two miscible liquids
dergoes dissociation or association in the solvent (a) can be separated by simple distillation.
(i = van’t Hoff factor). (b) may show positive or negative deviation from
28. Which of the following statements are correct for a Raoult’ law.
binary solution which shows negative deviation from (c) are supersaturated solutions.
Raoult’s law? (d) behave like a single component and boil at a con-
(a) The negative deviation from linearity diminishes stant temperature.
and tends to zero as the concentration of the solu- 35. If P0 and Ps are the vapour pressures of the solvent and
tion component approaches unity. its solution respectively and N1 and N2 are the mole
(b) When solutions form, their volumes are smaller fractions of the solvent and solute respectively, then
than the sum of the volumes of their components.
(c) Heat is released during the formation of the solu- (a) PS = P0N2
tion. (b) P0 – PS = P0N2
(d) Heat is absorbed during the formation of the solu- (c) PS = P0N1
tion. (d) (P0 – PS)/PS = N1/(N1 + N2)
29. In the depression of freezing point experiment, it is 36. Which of the following form ideal solution?
found that the
(a) C6H5Cl and C6H5Br (b) C6H6 and C6H5CH3
(a) vapour pressure of the solution is less than that of
pure solvent. (c) Hexane and Heptane (d) Ethanol + Cyclohexane
(b) vapour pressure of the solution is more than that 37. At constant temperature, the osmotic pressure of a so-
of pure solvent. lution is
(c) only solute molecules solidify at the freezing (a) directly proportional to the concentration.
point. (b) inversely proportional to the molecular weight of
(d) only solvent molecules solidify at the freezing the solute.
point.

(c) directly proportional to the square of the concen- ing point is 0.112°C lower than that of pure benzene.
tration. Deduce the value of x. (Atomic mass of Se = 78.8 g
(d) directly proportional to the square root of the con- mol–1).
centration. 46. The vapour pressure of pure benzene at a certain tem-
38. Ideal solution is formed when its components perature is 640 mm Hg. A non-volatile solid weighing
(a) have zero heat of mixing. 2.175 g is added to 39.0 g of benzene. The vapour pres-
(b) have zero volume change. sure of the solution is 600 mm Hg. What is the molar
(c) obey Raoult’s law. mass of the solid substance in nearest integer?
(d) can be converted into gases. 47. Addition of 0.643 g of a compound to 50 mL of ben-
39. In the depression of freezing point experiment, it is zene (density: 0.879 g mL–1) lower the freezing point
found that from 5.51°C to 5.03°C. If Kf for benzene is 5.12 K kg
(a) the vapour pressure of the solution is less than that mol–1, calculate the molar mass of the compound in
of pure solvent. nearest integer.
(b) Freezing point of 1 m sucrose solution greater 48. The vapour pressure of two pure liquids A and B, that
than 1 m NaCl solution at same temperature. form an ideal solution are 100 and 900 mm Hg respec-
(c) only solute molecules solidify at the freezing tively at temperature T. This liquid solution of A and B
point. is composed of 1 mole of A and 1 mole of B. What will
(d) only solvent molecules solidify at the freezing be the pressure, in mm Hg when 1 mole of mixture has
point. been vaporised?
Integer and Subjective Question 49. Mixture of two liquids A and B is placed in cylinder
containing piston. Piston is pulled out isothermally so
40. At 20°C, the osmotic pressure of urea solution is 400 that volume of liquid decreases but that of vapour in-
mm. The solution is diluted and the temperature is creases. When negligibly small amount of liquid was
raised to 35°C, when the osmotic pressure is found to remaining, the mole fraction of A in vapour is 0.4. Giv-
V en P°A = 0.4 atm and P°B = 1.2 atm at the experimental
be 105.3 mm. Find final
Vinitial temperature. Calculate the total pressure at which the
41. An aqueous solution containing 5% by weight of urea liquid has almost evaporated. (Assume ideal behav-
and 10% by weight of glucose. What will be the DTf of iour)
solution? Kf¢ for H2O is 1.86° mol–1 kg? 50. 1.5 g of monobasic acid when dissolved in 150 g of
42. A certain mass of a substance when dissolved in 100 water lowers the freezing point by 0.165°C. 0.5 g of the
g C6H6 lowers the freezing point by 1.28°C. The same same acid when titrated, after dissolution in water, re-
mass of solute dissoved in 100 g of water lowers the quires 37.5 mL of N/10 alkali. Calculate the degree of
freezing point by 1.40°C. If the substance has normal dissociation of the acid (Kf for water = 1.86° C mol–1).
molecular weight in benzene and is completely disso- 51. The molar volume of liquid benzene (density = 0.877
cated in water, into how many ions does it dissociate in g mL–1) increase by a factor of 2750 as it vaporises
water? Kf of H2O and C6H6 are 1.86 and 5.12 K mol–1 at 20°C and that of liquid toluene (density = 0.867 g
respectively. mL–1) increases by a factor of 7720 at 20°C solution
43. A complex is represented as COCl3. xNH3. Its 0.1 mol- has a vapour pressure of 46.0 torr. Find the mole frac-
al solution in aqueous solution shows DTf = 0.558°. Kf tion of benzene in the vapour above the solution.
for H2O is 1.86 K molality–1. Assuming 100% ionisa- 52. Calculate the boiling point of a solution containing 0.61
tion of complex and coordination number of Co as six, g of benzoic acid in 50 g of carbon disulphide assuming
find the value of x. 84% dimerisation of the acid. The boiling point and Kb
44. A very small amount of a non-volatile solute (that does of CS2 are 46.2°C and 2.3 K kg mol–1, respectively.
not dissociate) is dissolved in 56.8 cm3 of benzene 53. At 25°C, 1 mol of A having a vapour pressure of 100
torr and 1 mol of B having a vapour pressure of 300
(density 0.89g cm–3). At room temperature, vapour
torr were mixed. The vapour at equilibrium is removed,
pressure of this solution is 98.88 mm Hg while that of
condensed and the condensate is heated back to 25°C.
benzene is 100 mm Hg. If the freezing temperature of
The vapour now formed are again removed, recon-
this solution. If the freezing temperature of this solu-
densed and analysed. What is the mole fraction of A in
tion is 0.73 degree lower than that of benzene, what
this condensate?
is the value of molal freezing depression constant of
54. 30 mL of CH3OH (d = 0.7980 g cm–3) and 70 mL of
benzene in nearest integer?
H2O (d = 0.9984 g cm–3) are mixed at 25°C to form a
45. The molal freezing point depression constant for ben- solution of density 0.9575 g cm–3. Calculate the freez-
zene (C6H6) is 4.90 K kg mol–1. Selenium exists as ing point of the solution. Kf(H2O) is 1.86 kg mol–1 K.
a polymer of the type Sex. When 3.26 g of selenium Also calculate its molarity.
is dissolved in 226 g of benzene, the observed freez-

55. When the mixture of two immiscible liquids (water 0.1 M KI solution dissolves 12.5 g/L of I2. Calculate
and nitrobenzene) boils at 372 K and the vapour pres- the equilibrium constant Kc for the above equilibrium.
sure at this temperature are 97.7 kPa (H2O) and 3.6 kPa Also calculate the freezing point of the resulting so-
(C6H5NO2). Calculate the weight % of nitrobenzene in lution. Assume molarity to be equal to molality and
the vapour. also assume that conc. of I2 in all saturated solutions is
56. The molar volume of liquid benzene (density = 0.877 same. [Kf for water = 1.86 K kg mol–1].
g mL–1) increases by a factor of 2750 as it vaporises 63. Two solutions of non-volatile solutes A and B are pre-
at 20°C while in equilibrium with liquid benzene. At MA 1
27°C when a non-volatile solute (that does not dissoci- pared. The molar mass ratio, = . Both are pre-
MB 3
ate) is dissolved in 54.6 cm3 of benzene vapour pres-
sure of this solution, is found to be 98.88 mm Hg. Cal- pared as 5% solutions by weight in water. Calculate the
culate the freezing point of the solution. ( DT f ) A
ratio of the freezing point depressions, of the
Given: Enthalpy of vaporization of benzene (l) = ( DT f ) B
394.57 J/g. solutions. If the two solutions are mixed to prepared
Molal depression constant for benzene = 5.12 K kg. two new solutions, S1 and S2, the mixing ratio being
mol–1. 2:3 and 3:2 by volume for S1 and S2 respectively what
Freezing point of benzene = 278.5 K. ( DT f ) S1
57. An ideal solution was prepared by dissolving some would be the ratio ?
( DT f ) S2
amount of cane sugar (non-volatile) in 0.9 moles of wa-
ter. The solution was then cooled just below its freezing 64. The vapour pressures of two pure liquids A and B that
temperature (271 K), where some ice get separated out. form an ideal solution are 300 and 800 torr, respectively,
The remaining aqueous solution registered a vapour at temperature T. A mixture of the vapours of A and B
pressure of 700 torr at 373 K. Calculate the mass of ice for which the mole-fraction of A is 0.25 is slowly com-
separated out, if the molar heat of fusion of water is 96 kJ. pressed at temperature T. Calculate
58. The freezing point depression of a 0.109 M aqueous (a) the composition of the first drop of the conden-
solution of formic acid is –0.21°C. Calculate the equi- sate.
librium constant for the reaction, (b) the total pressure when this drop is formed.
HCOOH (aq) m H+ (aq) + HCOOQ (aq) (c) the composition of the solution whose normal
Kf for water = 1.86 kg mol–1 K boiling points is T.
59. 10 g of NH4Cl (mol. weight = 53.5) when dissolved in (d) the pressure when only the last bubble of vapour
1000 g of water lowered the freezing point by 0.637°C. remains.
Calculate the degree of hydrolysis of the salt if its de- (e) composition of the last bubble.
gree of dissociation is 0.75. The molal depression con- 65. At solution containing 12.5 g of non-electrolyte sub-
stant of water is 1.86 kg mol–1 K. stance in 175 gram of water gave boiling point eleva-
60. The freezing point of 0.02 mol fraction solution of ace- tion of 0.70 K. Calculate the molar mass of the sub-
tic acid (A) in benzene (B) is 277.4 K. Acetic acid ex- stance. Molal elevation constant (Kb) for water 0.52 K
ists partly as a dimer 2A = A2. Calculate equilibrium kg mol–1.
constant for the dimerisation. Freezing point of ben- 66. What weight of the non-volatile solute, urea (NH2 –
zene is 278.4 K and its heat of fusion DHf is 10.042 kJ CO – NH2) need to be dissolved in 100 g of water, in
mol–1. order to decrease the vapour pressure of water by 25%?
61. Tritium, T (an isotope of H) combines with fluorine to What will be the molality of the solution?
form weak acid TF, which ionises to give T+. Tritium is 67. Ethylene dibromide (C2H4Br2) and 1,2-dibromo pro-
radioactive and is a b-emitter. A freshly prepared aque- pane (C3H6Br2) form a series of ideal solution over the
ous solution of TF has pT (equivalent of pH) of 1.5 whole range of composition. At 85°C, the vapour pres-
and freezes at –0.372°C. If 600 mL of freshly prepared sures of these pure liquids are 173 mm Hg and 127 mm
solution were allowed to stand for 24.8 years, calculate Hg respectively.
(i) ionisation constant of TF. (ii) Number of b-particles (a) If 10 g of ethylene dibromide is dissolved in 80
emitted. g of 1, 2-dibromo propane. Calculate the partial
(Given: Kf for water = 1.86 kg mol K–1, t1/2 for tritium pressures of each components and the total pres-
= 12.4 years.) sure of the solution at 85°C.
62. The freezing point of an aqueous saturated solution of (b) Calculate the composition of the vapour in equi-
I2 is –0.0024°C. More than this can dissolve in a KI librium with the above solution and express as
solution because of the following equilibrium: mole fraction of ethylene dibromide.
-
(c) What would be the mole fraction of 1,2-dirbomo
I 2(aq) + I aq I 3- (aq) propane in solution at 85°C equilibriated with
50:50 mole mixture in the vapour?

68. A dilute solution contains m mol of solute A in 1 kg of 3. A solution of non-volatile solute in water freezes at
a solvent with molal elevation constant Kb. The solute –0.30°C. The vapour pressure of pure water at 298 K
dimerises in solution as 2A m A2. Show that equilib- is 23.51 mm Hg and Kf for water is 1.86 degree/molal.
rium constant for the dimer formation is Calculate the vapour pressure of this solution at 298 K.
K ( K m – DTb ) [IIT-JEE, 1998]
K= b b 4. To 500 cm3 of water, 3 ¥ 10–3 kg of acetic acid is added.
(2 DTb – K b m) 2
If 23% of acetic acid is dissociated, what will be the
Where DTb is the elevation of the boiling point for the depression in freezing point? Kf and density of water
given solution. Assume molarity = molality. are 1.86 K kg mol–1 and 0.997 g cm–3 respectively.
69. Distribution coefficient of an organic acid between wa- [IIT-JEE, 2000]
ter and benzene is 4.1 in favour of C6H6. If 5 g of acid 5. 1.22 g of benzoic acid is dissolved in 100 g of acetone
is distributed in between 50 mL of benzene and 100 and 100 g of benzene separately. Boiling point of the
mL of water, calculate the concentration of acid in two solution in acetone increases by 0.17°C, while that in
solvents. the benzene increases by 0.13°C; kb for acetone and
70. Heptane and octane form ideal solution. At 373 K, the benzene is 1.7 K kg mol–1 and 2.6 K kg mol–1. Find
vapour pressures of the two liquids are 105.2 kPa and molecular weight of benzoic acid in two cases and jus-
46.8 kPa respectively. What will be the vapour pres- tify your answer. [IIT-JEE, 2004]
sure, in bar, of a mixture of 25g of heptane and 35 g of 6. For a dilute solution containing 2.5 g of a non-volatile
octane? non-electrolyte solute in 100 g of water, the elevation
71. The freezing point depression of 0.001 m Kx[Fe(CN)6] in boiling point at 1 atm pressure is 2°C. Assuming
is 7.10 ¥ 10–3 K. Determine the value of x. Given, Kf = concentration of solute is much lower than the concen-
1.86 K kg mol–1 for water. tration of solvent, the vapour pressure (mm of Hg) of
72. The composition of vapour over a binary ideal solu- the solution is (take Kb = 0.76 K kg mol–1).
tion is determined by the composition of the liquid. If [IIT-JEE, 2012]
xA and yA are the mole fractions of A in the liquid and (a) 724 (b) 740 (c) 736 (d) 718
vapour, respectively find the value of xA for which (yA 7. Consider separate solution of 0.500 M C2H5OH (aq),
– xA) has maximum. What is the value of the pressure 0.100 M Mg3(PO4)2 (aq), 0.250 M KBr (aq) and 0.125
at this composition? M Na3PO4 (aq) at 25°C. Which statement is true about
these solution, assuming all salts to be strong electro-
lytes? [2014 Main]
PREVIOUS YEARS’ QUESTIONS (a) They all have the same osmotic pressure.
OF JEE (MAIN & ADVANCED) (b) 0.100 M Mg3(PO4)2 (aq) has the highest osmotic
pressure.
1. The degree of dissociation of Ca(NO3)2 in a dilute (c) 0.125 M Na3PO4 (aq) has the highest osmotic
aqueous solution, containing 7.0 g of the salt per 100 g pressure.
water at 100°C is 70 per cent. If the vapour pressure of (d) 0.500 M C2H5OH (aq) has the highest osmotic
water at 100°C is 760 mm, calculate vapour pressure of pressure.
the solution. [IIT-JEE, 1991] 8. The vapour pressure of acetone at 20°C is 185 torr.
2. Addition of 0.643 g of a compound to 50 mL of ben- [2015 Main]
zene (density 0.879 g/mL) lowers the freezing point When 1.2 g of a non-volatile substance was dissolved
from 5.51°C to 5.03°C. If K¢f for benzene is 5.12 k m–1. in 100 g of acetone at 20°C, its vapour pressure was
Calculate the molecular weight of the compound. 183 Torr. The molar mass of the substance is
[IIT-JEE, 1992] (a) 32 (b) 64 (c) 128 (d) 488
Answer Key
LEVEL I
1. (b) 2. (a) 3. (b) 4. (c) 5. (b) 6. (b) 7. (b) 8. (a) 9. (c) 10. (a)
11. (b) 12. (d) 13. (a) 14. (c) 15. (c) 16. (d) 17. (a) 18. (c) 19. (c) 20. (b)
21. (b) 22. (b) 23. (d) 24. (c) 25. (c) 26. (a) 27. (a) 28. (b) 29. (c) 30. (a)
31. (a) 32. (b) 33. (b) 34. (b) 35. (a) 36. (b) 37. (b) 38. (a) 39. (b) 40. (a)
41. (b) 42. (c) 43. (a) 44. (d) 45. (a) 46. (a) 47. (d) 48. (a) 49. (a) 50. (c)

LEVEL II
1. (c) 2. (a) 3. (b) 4. (a) 5. (a) 6. (d) 7. (c) 8. (a) 9. (b) 10. (b)
11. (d) 12. (b) 13. (c) 14. (a) 15. (c) 16. (a) 17. (c) 18. (b) 19. (b) 20. (b)
21. (b) 22. (c) 23. (a) 24. (d) 25. (a)
LEVEL III
1. (A) Æ s, t; (B) Æ r; (C) Æ p; (D) Æ q 2. (A) Æ s, t; (B) Æ q; (C) Æ r; (D) Æ p

3. (A) Æ p, q; (B) Æ s, t; (C) Æ p, q; (D) Æ r 4. (A) Æ r, t; (B) Æ p; (C) Æ r, s, t; (D) Æ p, q
5. (a) 6. (d) 7. (b) 8. (d) 9. (d) 10. (c) 11. (c) 12. (d) 13. (b) 14. (b)
15. (c) 16. (a) 17. (a) 18. (b) 19. (b) 20. (a) 21. (d) 22. (c) 23. (c) 24. (d)
25. (a, b, c, d) 26. (c, d) 27. (b, d) 28. (a, b, c) 29. (a, d) 30. (a, b, c)
31. (a, b) 32. (a, b) 33. (a, b, c, d) 34. (b, d) 35. (b, c) 36. (a, b, c) 37. (a, b)
38. (a, b, c) 39. (a,b,d) 40. (4) 41. (3) 42. (3) 43. (5) 44. (5) 45. (8)
46. (65) 47. (156) 48. (300) 49. (0.66 atm) 50. (18.27%) 51. (0.732) 52. (46.31°C)
53. (0.1 and 0.9) 54. (–19.91°C, 7.63 M) 55. (20.11%) 56. (277.51 K)
57. (12.54 gram) 58. (1.44 ¥ 10–4) 59. (h = 0.109) 60. (3.225)
61. (Ka = 7.3 ¥ 10–3, 3.7 ¥ 1022 b-particle) 62. (707.2 and 272.62 K) 63. 9/11
64. (a) XA = 0.47 (b) 565 torr (c) XA = 0.08 (d) 675 torr (e) XA≤ = 0.11 65. (53) 66. (111.118 gram) and (18.52 m)
67. (a) PA = 20.42 mm Hg; PB = 112.04 mm Hg (b) 0.154 (c) 0.5 and 0.5 68. Derivation
69. 67.22 gram/litre and 16.39 gram/litre 70. (73.08 kPa) 71. (3) 72. PAo PBo
1. (746.24 mmHg) 2. (156.06) 3. (23.44 mmHg) 4. (0.229) 5. (122 and 244) 6. (a)
7. (a) 8. (b)
Hints and Solutions

7. (b) mixture of polar CH3OH and non polar benzene
LEVEL I show +ve deviation.
8. (a) For an ideal solution DHmix = 0; DSmix > 0; DGmix <
1. (b) PA = x PAo 0.
2. (a) Mole fraction of A in vapour 9. (c) DTb μ i ¥ m: Higher the value of i ¥ m. more will be
DTb order of DTb b > c > d > a.
PA P0 x 10. (a) The H+ ion concentration in the medium is lower
= = A 2 = x1 = y A
Ptotal P than that of H+ concentration present in the mango
PA x2 juice, therefore osmotic pressure inside the mango is
\ Ptotal = Ps = higher than that of aqueous hydrochloric acid. There-
x1
fore, H2O will be passes out from the mango into aque-
3. (b) PT = PA + PB, for pure ethanol, x = 0 ous hydrochloric acid. Therefore mango shrinks,
\ 0
Pethanol = (119 ¥ 0 + 135) torr w 1000
11. (b) DTb = iKb ◊ m = iK b B ¥
\ vapour pressure of pure ethanol = 135 torr mB wA
4. (c) Ideal solution obey Roult’s law. i=1
5. (b) For a non-ideal solution with negative deviation, 1 ¥ 0.52 ¥ 32 ¥ 1000
DHmix = –ve \ DTb = = 1.04
mB ¥ 200
DVmix = –ve
6. (b) Either less than or more than 125 mL because \ mB = 80 g/mole
DVmixing = 0 for ideal solution. 12. (d) ‘i’ value of CF3COOH > CCl3COOH > CH3COOH
Since, i μ acidic strength

13. (a) On freezing a solution, only solvent freeze, but not wB = 10 gram.
solute. P0 - PS 17.5 - PS nB 25/180
DT f 2 27. (a) = = =
14. (c) K f = = = 8 Km -1 P0 17.5 nB + n A 25
+
450
m 0.25 180 18
1000 ¥ K f ¥ wB 1000 ¥ 2.16 ¥ 0.15 Relative lowering of vapour pressure
15. (c) DT f = fi 0.216 =
wA ¥ mB 15 ¥ mB
P o - Psolution
\ mB = 100 = xsolute ;
Po
16. (d) Higher the value of ‘i’ less will be freezing point. 25 25
17. (a) 2KI + HgI2 Æ K2[HgI4] 17.535 - Ps
= 180 ª 180 ;
18. (c) Relative lowering of vapour pressure is a colligative 450 25 450
17.535 +
property.
18 180 18
19. (c) Solubility of phenol > chloroform > toluene due to
\ Ps = 17.44 mm Hg
H-bonding.
xB ¥ 1000 0.2 ¥ 1000 DTb
20. (b) m = = = 3.2 28. (b) K b =
(1 - xB ) ¥ m A 0.8 ¥ 78 m
Since, DTb = Kb ◊ m
21. (b) Mass percentage of solute 29. (c) DTb = Kb ◊ m and DTf = Kf ◊ m
Weight of solute ¥ 100 DTb = 0.15°C; 0.15 = Kb ¥ m
=
Weight of [solute + solvent] On diluting the above solution with equal volume of
Mass percentage of aspirin in acetonitrile water molality becomes approximately half.
6.5 DT f K f 1 DT1 1.86 1
= ¥ 100 = 1.424% = ¥ ; = ¥ ; DT f = 0.272°C
(450 + 6.5) DTb Kb 2 0.15 0.512 2
Dp 10 30. (a) DTf = i ¥ Kf ¥ m ; i value of K2SO4 is maximum, so

22. (b) = = 0.2 fi P o = 50 the freezing point is least.
Po Po
31. (a) p = iCST; K2SO4 h 2K+ + SO 24- ; Van’t Hoff
DP 20
= = 0.4 Factor, i = 3
Po Po n
\ xsolvent = 0.6 osmotic Pressure, p = i RT ;
V
23. (d) Total pressure of the solution is given by
25 ¥ 10 –3
PTotal = X B PBo + X T PTo p =3¥ ¥ 0.0821 ¥ 298 ; p = 5.27 ¥ 10–3 atm
174 ¥ 2.0
= 0.4 ¥ 119 + 0.6 ¥ 37 = 47.6 + 22.2
Observed molecular weight
= 69.8 torr 32. (b) i = ;
Applying Dalton’s law for mole fraction in vapour Calculated molecular weight
phase Normal molecular weight
i for AgNO3 = =1+a
PB 47.6 Observed molecular weight
yB = = = 0.763
PTotal 62.4 170
a= - 1 = 0.835 = 83.5%
yT = 1 – 0.763 = 0.237 92.64
24. (c) Given PTotal = 120 – 75 xB 33. (b) Roult’s Law states that the relative lowering of va-
pour pressure is equal to mole fraction of solute.
P = x A PA0 + xB PB0 0 0
34. (b) PT = x A PA + xB PB
For pure A, XB = 0; PAo = 120 torr
P P
y A = A or yB = B
For pure B, XB = 1; PBo = 120 – (75 ¥ 1) = 45 torr PT PT
PA PAo x A x¢ Po P0 - PS nA
25. (c) x ¢A = = fi A = A <1 35. (a) =
PS PS xA P P0 n A + nB
78 46
(Since the liquid A is less volatile, PAo < PS) n A + nB = + = 1 + 0.5
DP nB wB m A 78 92
26. (a) = = ¥ 1
PS n A mB wA PB = PBo ¥ = 75 ¥ 0.66 = 50
1.5
20 wB 114
fi = ¥
80 40 114

P0 - PS i = 1 – a + a/3 a = 100%
36. (d) = xB 1 1
P0 =1–1+ =
3 3
0.8 - 0.6 0.2
= = = 0.25 45. (a) 5% solution means 100 mL solution contain 5 g
0.8 0.8 cane sugar.
37. (b) P = x A PA0 + xB PB0 0.877% means 100 mL solution contain 0.877 g X iso-
tonic solution C1 = C2
PT = PA + PB = PA0 x A + PB0 xB = PB0 (1 - x A )
p1 = p 2
100
140 \ C1ST = C2 ST
xA = = 0.11
1000 100 C1 = C2
+
180 140 5 0.877
=
\
0
4.75 = PA ¥ 0.11 + 500(1 – 0.11) 342 ¥ 100 M wt. ¥ 100
0.877
PA0 =
31.0
= 280.7 torr Mwt = ¥ 342 = 59.98
0.11 5
PA = PA0 ¥ x A = 280.7 ¥ 0.11 = 32 torr 46. (a) Osmotic pressure μ Colligative properties
OP = iCRT
M ¥ 1000
38. (a) m = AlCl3 (i = 4), BaCl2 (i = 3), Urea (i = 1)
d ¥ 1000 – M ¥ Molar mass of solute
1– i Ê 1- i ˆ
M ¥ 1000 47. (d) a= = n
3= 1 ÁË 1 - n ˜¯
1110 – M ¥ 40 1–
n
3330 – 120M = M ¥ 1000 1– i
3330 0.8 = ; i = 0.4
3330 = M(1120) \ M= 1
1120 1–
M = 2.97 n
39 (b) The concentration of solution (ppm) DT = iKf ¥ m
Weight of solute 5 wB ¥ 1000
= ¥ 106 = 6 ¥ 106 = 5 ppm 0.3 = 0.4 ¥ 1.86 ¥
Weight of solvent 10 mB ¥ wA
40. (a) DTb = m ¥ Kb
2.5 ¥ 1000
DTb = 0.69 ¥ 0.513°C 0.3 = 0.4 ¥ 1.86 ¥
mB ¥ 100
DTb = 0.69 ¥ 0.513°C mB = 62
Tsolution – Tsolvent = 0.3597 48. (a) DT = i ¥ Kb ¥ m
Tsolution – 99.725°C = 0.3597 i ¥ m of Na2SO4 is highest, hence its boiling point will
Tsolution = 100.0789°C also be highest
41. (b) DTf = i ¥ m ¥ Kf [NaCl = Na+ + Cl–] Na2SO4 i ¥ m = 3 ¥ 0.01 = 0.03
KNO3 i ¥ m = 2 ¥ 0.01 = 0.02
DTf = 2 ¥ 1 ¥ 1 ¥ 1.86 Since, i = 2
Urea i ¥ m = 1 ¥ 0.015 = 0.015
DTf = 3.72
Glucose i ¥ m = 1 ¥ 0.015 = 0.015
Tsolvent – Tsolution = 3.72
n
0° – Tsolution = 3.72 49. (a) p = ST
V
Tsolution = – 3.72°C 12 1
42. (c) DTb = m ¥ Kb = ¥ ¥ 0.0821 ¥ 290
342 0.1
10 ¥ 1000 = 8.35 atm
0.3 = ¥ Kb
100 ¥ 100
50. (c) When xA = 0, xB = 1
Kb = 0.3
\ P = PBo
M – M 0 58.50 – 31.80
43. (a) a = T = = 0.8396 = 83.96%
M0 31.80 \ PBo = 254,
44. (d) 3A h A3 when xA = 1, xB = 0
1– a a/3 \ PAo = P = 254 – 119 = 135

Hence the molality of A after dimer is formed = (1 – a)

LEVEL II ¥ Initial molality = (1 – 0.48) ¥ initial molality = 0.52 ¥
0.262
300 ¥ 25 a
1. (c) Weight of solute in 300 g solution =
100
= 75 g Molality of A2 after dimer is formed = ¥ molality =
2
400 ¥ 40 0.48
Weight of solute in 400 g solution = = 160 g = 0.24 ¥ 0.26 = 0.06288
100 2
\ Total weight of solute in resultant solution = 75 + The equilibrium constant
160 = 235 g [ A2 ] 0.06288
Keq = = = 3.39 kg mol–1
Total weight of solution = 300 + 400 = 700 g [ A]2
(0.13624) 2
Mass percentage of solute in resulting solution
\ mA = 100
235 6. (d) Number of ions in solution of NaCl = 2
= ¥ 100 = 33.6%
700 MgCl2 = 3; Urea = 1; Na2SO4 = 3; Ca(NO3)2 = 3
Mass percentage of solvent in resulting solution
= (100 – 33.6)% = 66.4% \ iC = 3 ¥ 0.1 = 0.3 for both Ca(NO3)2 and Na2SO4
2. (a) DTf = i ¥ Kf ¥ m n
7. (c) p = CRT = RT
0 – Tf = (1 + 0.2) ¥ 1.86 ¥ 0.2 = 0.4464 V
\ Tf = –0.4464°C Êw 10 ˆ
3. (b) p = iCST; Osmotic Pressure; p = iCRT =Á %¥ ¥ RT
ËV mB ˜¯
n
or p = i RT 10
V =5¥ ¥ 0.0821 ¥ [150 + 273]
n 342
\ 0.75 = ¥ 0.0821 ¥ 300 ¥ 2.47 = 5.07 atm
2.5
0.75 ¥ 2.5 8. (a) Let the apparent molecular weight = mo
n= ; \ n = 0.03 mole
0.0821 ¥ 300 ¥ 2.47 n w 1
Osmotic pressure = p = ¥ RT = ¥ ¥ RT
w B 1000 V mo V
4. (a) DTb = iKb ¥
mB wA 3 ¥ 10-3 1
or 0.3092 ¥ 105 = ¥ -3 m3 ¥ 8.314 ¥ 298
32.5 1000 mo 10
= 2 ¥ 0.52 ¥ ¥
64 100 \ mo = 240.2 ¥ 10 kg
–3
= 240.2 gram/mole
DTb = 5.28 Since,
\ Tf = 100 + 5.28 = 105.28°C
Number of particles after dissociation
5. (a) Let acetic acid = A; Benzene = B i=
Assume, a part of A forms dimer Number of particles before dissociation
2A m A2 N ormal molecular weight
=
1 0 Initially moles Observed molecular weight
1–a a/2 Moles after dimer is formed
\ Hg(CN)2 m Hg++ + 2CN–
(1 - a ) + a /2 1–a a
\ i= = 1 - a /2 2a
1 \ Number of particles after dissociation
Molecular fraction of A = xA = 0.02; = (1 – a) + a + 2a = 1 + 2a
= mole fraction of solute
1 + 2a 252.61 ¥ 10-3
Molecular fraction of B = xB = 0.98 \ i= = ;
= mole fraction of solvent 1 240.2 ¥ 10-3
0.02 1000 a = 0.02457 or 2.4567%
Molality of A in B = ¥
78 0.98 w
= 0.262 mol kg–1 of Benzene 9. (b) Given % = 68%
w
Since, DTf = Kf ¥ i ¥ molality mB = 63 and d = 1.504 gmL–1
278.4 – 277.4 = 5 ¥ i 0.262 or, 1 = 5 ¥ i ¥ 0.262
w 10d 68 ¥ 10 ¥ 1.504
1 M= % = = 16.23 M
i= = 0.763; 1 – a/2 = 0.763 fi a = 0.48 w mB 63
5 ¥ 0.262
10. (b) P = x A PAo + xB PBo

o
PHeptane = 105.2 kPa 1000 Kb wB 1000 ¥ 0.52 ¥ 0.6
16. (a) DTb = Tb - Tbo = =
o mB wA 60 ¥ 100
POctane = 46.8 kPa
Tb – 373 = 0.052 Tb = 373.052
Ê 26 ˆ Ê 35 ˆ
Á 100 ˜ Á 114 ˜ 1000 ¥ Kb ¥ w2 1000 ¥ 2.53 ¥ 2.5
PS = 105.2 ¥ Á + 46.8 ¥ Á 17. (c) mB = mB =
26 35 ˜ 26 35 ˜ DTb w1 1.38 ¥ 34
ÁË + ˜¯ ÁË + ˜
100 114 100 114 ¯ 1000 K f wB
= 73.08 kPA 18. (b) DT f =
mB wA
PAo - PS 1000 1000 ¥ 6.8 ¥ 1.2
11. (d) ¥ =m mB = \ mB = 194.2 g/mole
PS mA 2.8 ¥ 15
12.3 - PS 1000 1000 Kb wB 0.27 ¥ 122 ¥ 100
¥ =1 19. (b) DTb = i ¥ i=
PS 18 mB wA 1000 ¥ 0.54 ¥ 12.2
1018 ¥ PS = 12300 a
i = 0.5 i=1–a+
12300 n
\ PS = = 12.082 KPa
1018 weight 12.2
No. of moles = = = 0.1 mole
RTb2¥ mA Molar mass 122
12. (b) K b = 2C6H5COOH (C6H5COOH)2
1000 ¥ DHV
0.1 0
R(Tbo ) 2 m A 0.1
DHV = 0 mole
1000 ¥ K b 2
= 33919 J ª 34 KJ 0.1 0.1 N
mole = NA = A
13. (c) Let the mass of solution = 100 g 2 2 20
20. (b) 1–a 3a 2a
( DT f )1
273 - 271
( DT f )1 = K f m1 fi K f = = DTb = i Kbm x3y2 h 3x+2 + 2y+3
m1 5 1000
¥ i = 1– a + 3a + 2a i = 0.75 + 1.25
342 95
i=2 Tb – T bo = 2 ¥ 1 ¥ 0.52
For glucose (DTf)2 = Kf m2 and (Tf)2 = T f – DTf
0
Tb = 373 + 1.04 Tb = 374.04
273.15 – Tf = Kf ¥ m2 21. (b) DTb = Kbm Tb – T bo = 0.573 ¥ 0.1
273 - 271 5 1000 Tb = 373.0573 K
= ¥ ¥
5 1000 180 95 22. (c) DTb = Kbm 0.15 = 0.512 ¥ m
¥
342 95 m = 0.292 DTf = Kfm¢
Tf(glucose) = 269.07 K 0.292
14. (a) p = CRT m¢ = m/2 Tf – T fo = 1.86 ¥
T = –0.27°C 2
We know that f
p1V1 = C1RT1 and p2V2 = C2RT2 23. (a) Acetone = 10 gm Water = 90 gm
Since, (V1 = V2, T1 = T2) 10/58
mole % of acetone = ¥ 100 = 3.33%
10/58 + 90/18
p1 p 2
\ = 0.14
C1 C2 24. (d) DTf = Kfm m= = 0.075 molal
1.86
p 2C1 1.52 ¥ 36 P° – PS Loss in weight of solvent
\ C2 = = = 0.061 M 25. (a) = (i)
p1 4.98 ¥ 180 PS Loss in weight of solution
(C.P)1 i1 Exp. colligative property P° – PS wB m A
15. (c) = ; iKCl = = ¥ (ii)
(C.P) 2 i2 Normal colligative property PS mB wA
from eq. (i) and (ii)
Number of particle furnished by KCl
= =2 0.04 5 ¥ 18
Number of particles before dissociation =
2.5 180 ¥ mB
For an ideal solution of sugar isugar = 1
mB = 31.25

LEVEL III 7. (b) P = x A PAo + xB PBo

PA
yA = , yB = 1 - y A
1. (A - s, t), (B - r), (C - p), (D - q) PT
1. CH3COOH in H2O undergoes dissociation.
P o - PS 1000 w 1000
2. CH3COOH in C6H6 undergoes dimerisation 8. (d) ¥ =m= B ¥
3. Polymer in water undergoes neither association PS mA mB wA
nor dissociation. 0.024 - PS 1000 68.4 1000
¥ = ¥
2. (A – s, t) (B – q) (C – r) (D – p) PS 18 342 1000
(a) Azeotropes or constant boiling mixtures with
PS = 0.0239 atm
equal composition in both vapour phase and liq-
uid phase. 9. (d) p = CST ; p = C ¥ R ¥ T;
(b) CHCl3 in benzene shows negative deviation be- 68.4
= ¥ 0.0821 ¥ 298; p = 4.89 atm
cause of increase in molecular interactions. 342
Observed molecular mass 1L
(c) i =
Theoritical molecular mass 10. (c) DTf = i ¥ Kf ¥ m; T f0 - T f = i ¥ K f ¥ m
Weight of solute 1000
(d) m = ¥ 0 – Tf = 1 ¥ 11.86 k kg mol–1 ¥
68.4
mol/kg
Molar mass of solute Weight of solvent 342
3. (A - p,q), (B - s,t), (C -p, q), (D - r) = 0.372°C 1
(a) CCl4 and CHCl3 are similar in structure and pos- Tf = –0.372°C
sess similar interaction so they are nearly ideal
11. (c) DTf = Kf.m for a solution with m = 1, DTf = Kf
solution and obeys Roult’s law.
Cryoscopic constant Kf = DTf of solution having unit
(b) C6H6 in H2O, weakness the hydrogen bonding in
molality of normal solutes (means i = 1)
H2O and exhibit positive deviation.
9 ¥ 1000
(c) In ideal solution, PA μ XA Molality of glucose solution in m = =1
(d) For non-ideal solution with negative deviation (59 - 9) ¥ 180
P < x A PAo 12. (d) Since the solution has greater entropy (disorder)
4. (A - r,t), (B - p), (C - r, s, t), (D - p,q) than the pure liquid, so former has lesser tendency to
freeze, i.e., the temperature has to be lowered to freeze
(Match the Column) the solution. It has lesser tendency to pass into the va-
2 2 pour phase.
RT fo RT fo m A
+ - + 2-
(a) K f = = ; 13. (b) 2Na (aq) + 2I(aq) + HgI2(s) h 2Na (aq) + HgI4(aq)
1000 L f 1000 DH f
The number of mole particles decreases from 4 = (2Na+
T fo (water) = 273 K, mA = 18
+ 2i–) to 3 = (2Na+ + HgI 24- ). Hence, the colligative
2 2
RT fo RT fo m A property will decrease or, the vapour pressure will in-
(b) K f = = ; crease to a constant value until NaI is completely con-
1000 L f 1000 DH f sumed
T fo (water) = 373 K, mA = 18 14. (b) On heating a solution, volume decreases and mo-
larity increases. Therefore, colligative property also
9 ¥ 1000 changes
(c) DT f = K f ¥ m = K f ¥ = Kf
180 ¥ 50 P DH È 1 1˘
15. (c) ln 2 = ¥Í - ˙
3 ¥ 1000 P1 R Î T1 T2 ˚
(d) DTb = K b ¥ m = K b ¥ = Kb
60 ¥ 50 16. (a) In the process of reverse osmosis, solvent flows
from concentrated side to dilute side of the so saline
5. (a) P = x A PA + xB PB
o o
water can be purified.
P
y A = A , yB = 1 - y A 17. (a) DTb = iKb ◊ m
PT i for urea < KCl
18. (b) Follow Henry’s Law
6. (d) P = x A PAo + xB PBo 19. (b) Azeotropes the boiling point of solution is either
= 300 ¥ 0.25 + 500 ¥ 0.75 = 450 torr lower (+ve deviation to R-Law) or higher (–ve devia-
P tion to R-Law) than that pure components.
y A = A , yB = 1 - y A
PT

DP 34. (b, d) In azeotrofric mixture, both components will boil

20. (a) = i ¥ xA at same temperature.
Po
i for KCl > urea P o - PS
35. (b, c) = 1 - xsolvent
n n Po
21. (d) M = solute ; m = solute Po – Poxsolvent = Po – PS
V(solution) W(solvent)
–Poxsolvent = –PS
22. (c) Since molecular weight of polymers is very high,
DTf and DTb will be very small so that accurate values PS
\ = xsolvent = N1
cannot be obtained. But osmotic pressure of polymer Po
solution can be measured accurately. \ PS = PoN1
23. (c) Vapours formed above a solution in composed of P o - PS
both volatile solute and solvent. = xsolute = N 2
24. (d) For 100% ionisation, i is equal to number of ions Po
produced from one mole of solute. e.g., For 100% ioni- \ Po – PS = PoN2
sation of NaCl, i = 2 36. (a, b, c) Components with similar molecular structure
25. (a, b, c, d) When a non-volatile solute is added to a and similar molecular interaction will form an ideal so-
pure solvent, the solution vapour pressure is less than lution.
that of pure solvent. e.g. C6H5Cl and C6H5Br, C6H6 and C6H5CH3;
26. (c, d) If a mixture is less volatile then the solution ex- 37. (a, b) p = iCST
hibits negative deviation and if the mixture is more vol- 38. (a, b, c) Ideal solution: Obeys Roult’s law
atile then the solution exhibits positive deviation from DHmix = DVmix = 0
Roult’s Law. 39. (a, b, d) When a non-volatile solute is added to a pure
P0 - Ps solvent to form a solution vapour pressure of solution
27. (b, d) = X solute decreased compared to that of a solution. At freezing
P0
point, only solvent freezes in a solution DTf = iKf m.
28. (a, b, c) For a solution with negative deviation, DHmix < 0; p C
DVmix < 0. 40. (4) p1 = C1ST; p2 = C2ST; 1 = 1
p 2 C2
29. (a, d) When a non-volatile solute is added to a pure
solvent to form a solution vapour pressure of solution 400
For initial solution, p = atm, T = 293 K
decreased compared to that of a solution. At freezing 760
point, only solvent freezes in a solution. 400
30. (a, b, c) Colligative property μ molality ¥ V1 = n ¥ S ¥ 293 (i)
760
1 After dilution, let volume becomes V2 and temperature
μ
Molecular mass 105.3
is raised to 35°C, i.e., 308 K. p = atm
31. (a, b) 760
1. For both urea and glucose i = 1 105.3
¥ V2 = n ¥ S ¥ 308 (ii)
2. For both K4[Fe(CN)6] and Al2(SO4)3, i = 1 + 4a 760
3. For association of a solute in a solution i < 1 V 293 105.3
4. Glucose and sucrose do not undergo either asso- By Eqs. (i) and (ii) we get 1 = ¥
V2 308 400
ciation or dissociation
V1 1
32. (a, b) PT = Pbenzero
o
xbenzene + Ptoulene
o
X toulene =
V2 4
Pbenzene 14 7
ybenzene = = = V2 = 4V1
PT 38 19 i.e., solution was diluted to four times.
1 2 41. (3) DTf = (1.86)[(narea + nglucose)10]
PT = 42 ¥+ 36 ¥ = 38 mm
3 3 solution has 5% by weight urea and 10% by weight
33. (a, b, c, d) In case of non-ideal solution with positive glucose
deviation from Roult’s law. Weight of solute
% by weight = ¥ 100
Weight of solution
1. Ps > x A PA0 + xB PB0
\ Weight of water = 85 g; Weight of urea = 5 g; Weight
2. DHmix > 0 of glucose = 10 g
3. DVmix > 0 DTf = DTurea + DTGlucose
4. A-A and B-B later actions are more than of A-B
interaction 1000 ¥ 1.86 ¥ 5 1000 ¥ 1.86 ¥ 10
DT = + = 3.04
60 ¥ 85 180 ¥ 85

42. (3) We know,

P o – Ps wB m A
1000 K f ¥ wB = ¥
DT f = Ps mB wA
mB ¥ wA
640 – 600 2.175 ¥ 78
1000 ¥ 5.12 ¥ w \ =
In C6H6: 1.28 = (i) 600 mB ¥ 59
mN ¥ 100
\ m = 65.25
1000 ¥ 1.86 ¥ w 47. Given
In H2O: 1.40 = (ii)
mexp ¥ 100 wB = 0.643 gram, Kf = 5.12 Kmol–1 kg
(Since given that solute behaves as normal in C6H6 and DTf = 5.51 – 5.03 = 0.48
dissociates in water.) By Eqs. (i) and (ii) wA = wt. of benzene = V ¥ d = 50 ¥ 0.879 g
1000 ¥ 5.12 ¥ 0.643
mN 1.40 5.12
= ¥ = 3.01 \ 0.48 =
mexp 1.28 1.86 mB ¥ 50 ¥ 0.879
wB 1000
mn (Normal molar mass) = DT f = K f ¥ ¥
Since, i = mB wA
mexp. (experimental molar mass)
\ mB = 156.06
i = 3.01 ª 3.0 48. Let nB mole of B present in 1 mole of mixture that has
43. (5) DTf = i ¥ Kf ¥ m been vaporised.
CoCl3. xNH3 h CoCl. xNH3 + nCl– Thus, yB = nB
1 3–n 0 xB =1 – nB
1–a a na P = PA°xA + PB°xB = PA° + xB(PB° – PA°)
Let n ions of Cl– are attached with Co. through prima-
ry valencies which undergo dissociation. All the NH3 P – PAo
xB = = 1 - nB
molecules are attached through secondary valencies. PBo – PAo
(NH3 behave as neutral ligand)
DTf = (1 – a + a + na) ¥ Kf ¥ molality PBo xB P o (1 - nB )
yB = fi nB = B
0.558 = (1 – 1 + 1 + n) ¥ 1.86 ¥ 1 ( a = 1) P P
\ n=2 nB P = PB - nB PB
o o (i)
Thus complex is [CoCl.xNH3].Cl2. PBo
Since coordination number of Co is six, thus x + 1 = 6 nB = (ii)
or x = 5. PBo + P
From Eqs. (i) and (ii)
P o - PS 1000 DT f
44. (5) ¥ =m= PBo P - Po P P - Po
PS mA Kf 1- = o Ao fi o = o Ao
PBo + P PB – PA PB + P PB - PA
100 - 98.88 1000
\ m= ¥ = 0.1452 On solving
98.88 78
DT f P = PAo PBo = 100 ¥ 900 fi 300 mm Hg
0.73
now K f = = = 5.027
49. PT = PA x A + PB xB = PA x A + PB (1 - x A )
o o o o
m 0.1452
100 - 98.88 1000 PT = PBo + x A = ( PAo – PBo )
\ m= ¥ = 0.1452
98.88 78
PAo x A PAo x A
45. (8) Given Kf = 4.9 yA = = o
PT PB + x A ( PAo - PBo )
wB = 3.26 wA = 226
0.4 x A
DTf = 0.112°C mB = x ¥ 78.8 0.4 =
1.2 - 0.8 x A
wB 1000
DT f = K f ¥ ¥ 1.2 = 1.8 ¥ xA
mB wA
2
4.9 ¥ 3.26 1000 xA =
0.112 = ¥ 3
x ¥ 78.8 226 1
so xB =
46. Given that, 3
P° = 640 mm, Ps = 600 mm, 2 1 2
wB = 2.175 g, wA = 39.0 g, mB = 78 PT = 0.4 ¥ + 1.2 ¥ = = 0.66 atm
3 3 3

0.5 Tf = –19.91°C
50. = 3.75 ¥ 10–3 fi mB = 133.33 23.94
mB M= = 7.63 M
1.86 ¥ 1.5 ¥ 1000 32 ¥ 0.98
0.165 = (1 + a) ¥
133.33 ¥ 150 wt of Nitrobenzene
55. ¥ 100
1 + a = 1.1827 wt of Nitrobenzene + wt of water
a = 0.1827 = 18.27% 3.6 ¥ 123
= ¥ 100
78 3.6 ¥ 123 + 97.7 ¥ 18
51. VB = ¥ 2750 mL = 244.583 L
0.877 = 20.11%
92
VT = ¥ 7720 mL = 819.192 L 56. At 20°C:
0.867
78
1 ¥ 0.0821 ¥ 293 ¥ 760 For C6H6 Æ V = ¥ 2750 mL
PB = = 74.74 torr 0.877
244.583
PV = 1 ¥ 0.0821 ¥ 293
1 ¥ 0.0821 ¥ 293 ¥ 760 P = 74.74 mm Hg
PT = = 22.317
819.192 If vapour pressure of benzene at 27°C is P1 then
46 = 74.74 xB + 23.317(1 – xB) P1 DHV È 1 1 ˘
52.423xB = 23.683 ln = –
P R ÍÎ T T1 ˙˚
xB = 0.451
P1 394.57 ¥ 78 È 1 1 ˘
P o ¥ xB 74.74 ¥ 0.451 ln = –
yB = B = = 0.732 74.74 8.314 Î 293 300 ˙˚
Í
PT 46
P1 = 100.364 mm Hg
a 0.84
52. i = 1 – =1– = 0.48 P° – Ps 1000
2 2 m= ¥
0.48 ¥ 2.3 ¥ 0.61 ¥ 1000 Ps mA
DTb = = 0.1104 100.364 – 98.88 1000
122 ¥ 50 m= ¥ = 0.1924
Tb = 46.2 + 0.1104 = 46.31°C 98.88 78
1 DTf = Kf ¥ m = 5.12 ¥ 0.1924 = 0.985°C
53. PA° = 100, PB° = 300, xA = xB = Tf = 278.5 – 0.985 = 277.51 K
2
1 1 57. Initial moles of H2O = 0.9
PT = 100 ¥ + 300 ¥ = 200 torr DHf = 6 kJ
2 2
1 RT f2 M 8.314 ¥ (273) 2 ¥ 18
100 ¥ Kf = = = 1.86
yA = 2=1 1000DH f 1000 ¥ 6000
200 4
DTf = Kf ¥ m
1 3
On condensation x ¢A = , xB¢ = 2
4 4 m= = 1.075
1 3 1.86
PT¢ = 100 ¥ + 300 ¥ = 250 so in 1000 g H2O Æ 1.075 mole solute
4 4
25 1.075
y ¢A = = 0.1 in 1 g H2O Æ mole solute
250 1000
On further condensation 1.075
in 0.9 ¥ 18 g H2O Æ ¥ 0.9 ¥ 18 mole solute
A = 0.1
x ¢¢ 1000
Mole of solute (nB) = 0.0174.15
xB¢¢ = 0.9 means composition of 2nd distillate
P° – Ps nB 760 – 700
54. CH3OH Æ V1 = 30 mL, d1 = 0.798 g/mL = fi = 0.0857
Ps nA 700
m1 = 23.94 g = mass of CH3OH
H2O Æ V2 = 70 mL, d2 = 0.9984 g/mL 0.017415
m2 = 69.888 g = mass of water Moles of H2O (nA) = = 0.2032
0.0857
mT = 93.828 g = Total mass of solution Moles of Ice separate out = 0.9 – 0.2032 = 0.6968
dsolution = 0.9575 g/mL Mass of Ice separate out = 0.6968 ¥ 18 = 12.54 g
Vsolution = 98 mL 58. DTf = (1 + a) Kf ¥ m
1.86 ¥ 23.94 ¥ 1000 0.21 = (1 + a) ¥ 1.86 ¥ 0.109
DTf = = 19.91 1 + a = 1.0358
32 ¥ 69.888

a = 0.0358 Moles of b-particle emitted = 0.06156

Ca 2
0.109(0.0358) 2 Number of b-particle emitted = 0.06156 ¥ 6.023 ¥ 1023
Ka = = = 1.44 ¥ 10-4 = 3.7 ¥ 1022
1–a 1 – 0.0358
62. 272.6256 K
59. NH4Cl h NH4+ + Cl–, NH4++H2OhNH4OH+H+
[ I 3- ]
C Ca Kc =
C–Ca Ca Ca Ca – Cah Cah Cah [ I 2 ][ I - ]
C – Ca + Ca + Ca – Ca h + Ca h + Ca h DTf = i ¥ Kf ¥ M(M = m)
i= DTr = Kfm
C
= (1 + a + ah) m=
0.0024
= 0.0013 mole/kg
DTf = i ¥ Kf ¥ m 1.86
-
(1 + a + a h) ¥ 1.86 ¥ 10 I2(aq) + I (aq) m I 3- (aq)
0.637 =
53.5 0.0492 0.1 0 Initial
1 + a + ah = 1.832 and (0.0492 – x) (0.1x) x Equilibrium
since a = 0.75, h = 0.109 Now, 0.0492 – x = 0.0013, because of conc. of I2 in all
8.314 ¥ (278.4) 2 ¥ 78 saturated solutions is same
60. Kf = =5
1000 ¥ 10042 x = 0.0479
0.02 ¥ 1000 [ I 3- ]
m= = 0.2614 Kc =
0.98 ¥ 78 [ I 2 ][ I - ]
DTf = i ¥ Kf ¥ m (0.0479)
Kc =
a (0.0013) (0.0521)
i=1– = 0.7643
2 Kc = 707.2 I –3 + I2 + I – + K+
a = 0.4713 DTf = 1.86(0.0479 + 0.0013 + 0.0521 + 0.1)
2A m A2 \ freezing point of the resulting solution = 272.6256 K
C 63. 9/11
C–Ca Ca/2 ( DT f )1 M 2
Ca /2 a =
K eq = = ( DT f ) 2 M1
(C – Ca ) 2
2C (1 – a ) 2 5
0.4713 ( DT f ) = K f ¥ ¥ 1000;
K eq = = 3.225 95M A
2 ¥ 0.2614(1 – 0.4713) 2 5
( DT f ) = K r ¥ ¥ 1000
61. TF h T+ + F– 95M B
C–Ca Ca Ca ( DT f ) A
\ MB 3
C - Ca + Ca + Ca = =
i= =1+ a ( DT f ) B MA 1
C
for dilute solution C = M = m (molality) Further for solution S1, molality
\ DTf = iKf ◊ m = iKf ◊ C = È 5 ¥ 1000 ˘ ¥ 2 + È 5 ¥ 1000 ˘ ¥ 3
PT = 1.5 fi [T+] = 0.0316 = Ca Í 95M ˙ 5 Í 95M ˙ 5
(i) Î A ˚ Î B ˚
0.372 = 1.86 ¥ C (1 + a) For solution S2, molality
C + Ca = 0.2 (ii)
È 5 ¥ 1000 ˘ 3 È 5 ¥ 1000 ˘ 2
from Eqs. (i) and (ii) = Í ˙¥ +Í ˙¥
C = 0.1684, a = 0.1876 Î 95M A ˚ 5 Î 95M B ˚ 5
Ca 2 0.1684(0.1876) 2 ( DT f ) S1 molality of S1
Ka = = = 7.3 ¥ 10–3 =
1–a (1 – 0.1876) ( DT f ) S2 molality of S2
In 600 mL solution [TF] = C–Ca = 0.1368 mole/L 3 ˘ È 3 2 ˘
È 2
So moles = 0.1368 ¥ 0.6 = 0.08208 =Í + ˙ /Í + ˙
Since, 24.8y = 2t1/2 ÎM A MB ˚ ÎM A MB ˚
0.08208 MA 1
Moles left after 24.8 years = = 0.02052 2+3 2+3¥
4 MB 3= 3 = 9
Moles disintegrated =
MA 1 2 11
= 0.08208 – 0.02052 = 0.06156 3+3 3+2¥ 3
MB 3 3

64. (a) XA = 0.47 (b) 565 torr (c) XA = 0.08 (d) 675 torr (e) 0.25 wB 18
XA≤ = 0.11 fi = ¥ \ wB = 111.118
0.75 60 100
x A p oA xB pBo 111.11 1000
x ¢A = and xB¢ = \ molality = ¥ = 18.52
p p 60 100
xA po ¥ xA 67. (a) PA = 20.42 mm Hg, PB = 112.014 mm Hg
= oA
xB pB (1 - x A ) (b) yA = 0.154
(c) yA = 0.5
Given
PA0 = 300 torr, PB0 = 800 torr We know PT = x A PA0 + xB PB0
X A¢ = 0.25, X B¢ = 1 - 0.25 = 0.75 nA

xA = , xB = 1 - x A
n A + nB
(a) By the condensation of only one drop, we can as-
PA
sume that composition of the vapour remains the yA = , yB = 1 - y A
same PT
PA0 X A P0 X Let C2H4Br2 = A, mA = 24 + 4 + 160, where mA = mo-
X A¢ = and X B¢ = B B lecular weight of A
P P
mB = molecular weight of B and B is C3H6Br2 = mB =
X A¢ 0
P X
or = 0 A A 36 + 6 + 160 = 202 Moles of A,
X B¢ PB (1 - X A )
wA 10
Putting various known values, we get nA = = = 0.053 Moles of B,
m A 188
XA = 0.47 and XB = 0.53
(b) P = 300 ¥ 0.47 + 800 ¥ 0.53 = 565 torr wB 80
(c) 760 = 300 XA + 800 XB nB = = = 0.396
mB 202
XA = 0.08 and XB = 0.92
(d) When only the last bubble of vapour remains, nB 0.396
\ xB = = = 0.882
we can assume composition of vapour is now the n A + nB 0.053 + 0.396
composition of the condensate. \ xA + xB = 1
Hence, P = 0.25 ¥ 300 + 0.75 ¥ 800 = 675 torr \ xA = 1 – 0.882 = 0.118
(e) Composition of the last bubble; (a) We know, total pressure
PAo X A 0.25 ¥ 300 PT = PA + PB Where PA, PB are partial pressures of
X A¢¢ = = = 0.11 A and B respectively.
P 675
X B¢¢ = 0.89 = PA0 ◊ x A + PB0 ◊ xB , where PA0 , PB0 are partial
pressures of pure component of A and B.
wB 1000 PT = 173 ¥ 0.118 + 127 ¥ 0.882 = 20.42 + 112.014
65. DTb = Kb ¥ ¥
mB wA = 132.43 mm Hg
Kb ¥ wB ¥ 1000 Here partial pressure of A, PA = 20.42 mm Hg
\ mB = Here partial pressure of B, PB = 112.014 mm Hg.
DTb ¥ wA
(b) Mole fraction of ethylene dibromide in the vapour
According to available data
Partical Pressure of A 20.42
Mass of solute (wB) = 12.5 g yA = = = 0.154
Total pressure 132.43
Mass of water (wA) = 1.75 g
Molal elevation constant (Kb) = 0.52 K kg mol–1 (c) In vapour phase nA : nB = 50:50 yA = 0.5, yB = 0.5
Elevation in boiling point temperature (DTb) = 0.70 K nB
=
n A + mB
(0.052 K kg mol-1 ) ¥ (12.5 g) ¥ 1000
\ mB = 68. 2A m A2
(0.70 K) ¥ (175 g)
m 0 initially
= 53 g mol-1 ma
(m – ma) after dimerisation
P 0 - Ps wB m A 2
66. = ¥
P0 mB wA ma
m(1 – a)
75 2
Po - Po ¥ where a is the degree of dimerisation and m is molal-
fi 100 = w ¥ 18
75 ity which is also molarity (given for dilute solution)).
Po ¥ 60 100
Hence due to dimerisation, final molality = m
100

ma Ê aˆ 70. (a) Heptane C7H16 mA = 100

m(1 – a) + = m ÁË1 - ˜¯ (b) Octane C8H18 mB = 114
2 2
i = 1 + (n – 1)a wA 25 35
nA = = = 0.25 ; nB = = 0.3
Ê1 ˆ m A 100 114
i = 1 + Á - 1˜ a
Ë2 ¯
0.25 0.3
Ê aˆ xA = = 0.45 xB = = 0.55
= Á1 - ˜ 0.25 + 0.30 0.25 + 0.30
Ë 2¯
= 0.45
Ê aˆ
DTb = Kb ¥ m ¥ i = Kb ¥ m Á1 - ˜ P = PA0 x A + PB0 xB
Ë 2¯
= 105.2 ¥ 0.45 + 46.8 ¥ 0.55
2( Kb m - DTb )
\ a= = 47.34 + 25.74 = 73.08 kPa
Kb m 71. DTf = i ¥ Kf ¥ m
Equilibrium constant K for the dimer formation is 7.10 ¥ 10–3 = i ¥ 1.86 ¥ 0.001
ma i = 3.817
[ A2 ] a i –1
K= = 2 2 = from Eq. (i) a=
[ A]2
m (1 – a ) 2
2m(1 – a ) 2 n –1
2 3.817 – 1
È K m – DTb ˘ È 2( Kb m – DTb ) ˘ a=
K = 2Í b ˙ 2m Í1 – ˙ ( x + 1) – 1
Î Kb m ˚ Î Kb m ˚
x = 2.817 ª 3
Kb ( K b m – DTb ) \ molecular formula of the compound is K3[Fe(CN)6].
K=
( K b m – 2 K b m + 2DTb ) 2 72. Since
K b ( K b m – DTb ) x A PAo
K= Proved yA =
(2 DTb – K b m) 2 PBo + ( PAo – PBo ) x A
69. Let the amount of organic acid in Subtracting xA from both the sides, we get
C6H6 layer = a g
x A PAo
Volume of C6H6 = 50 mL y A - xA = – xA
a PBo + ( PAo – PBo ) x A
\ concentration of acid in C6H6 = g mL–1
50 Differentiating this with respect to xA, we get
Since total amount of acid = 5 g d ( y A – xA ) PAo
\ amount of acid in H2O layer = (5 – a) g = o
and volume of H2O = 100 mL
dx A PA + ( PAo – PBo ) x A
Ê 5 – aˆ g x A PAo ( PAo – PBo )

\ Concentration of acid in H2O = ÁË ˜ - –1
100 ¯ mL {PBo + ( PAo – PBo ) x A }2
Concentration of acid in C6 H 6 The value of xA at which yA – xA has a maximum value
Now, K = can be obtained by setting the above differential equal
Concentration of acid in H 2O
to zero. Thus, we have
a 100
= ¥
50 (5 – a ) PAo
-
(
x A PAo PAo – PBo ) –1
a 100 PAo + ( PAo – PBo ) x A {PBo + ( PAo – PBo ) x A }2
\ 4.1 = ¥
50 (5 – a )
PAo PBo – PBo
or a = 3.361 g. Solving for xA, we get x A =
\ Amount of acid in 50 mL PAo – PBo
C6H6 = 3.361 g The value of P at this composition is
3.361 or P = x A PAo + xB PBo
\ acid concentration in C6H6 = ¥ 1000
50
P = PBo + ( PAo - PBo ) x A
= 67.22 g/L
Also, amount of acid in 100 mL H2O = 5 – a = 5 – 3.361 Ê Po Po - Po ˆ
= 1.639 g. or P = PBo + ( PAo - PBo ) Á Ao B o B ˜
1.639 Ë PA - PB ¯
\ acid concentration in H2O = ¥ 1000
100 or P = PAo PBo
= 16.39 g/L

PREVIOUS YEARS’ QUESTIONS 5. Since, DTb = K b

wB 1000
¥
OF JEE (MAIN & ADVANCED) mB wA
Kb ¥ wB ¥ 1000
1. Ca(NO3)2 m Ca2+ + 2NO3- \ mB =
Before dissociation 1 0 0 DTb ¥ wA
After dissociation 1–a a 2a
\ total mole at equilibrium = (1 + 2a) ( a = 0.7) For acetone solution:
= (1 + 2 ¥ 0.7) = 2.4 1000 ¥ 1.7 ¥ 1000
For Ca(NO3)2: mB = = 122
0.17 ¥ 100
P o - PS n For benzene solution:
=i B
PS nA 1000 ¥ 2.6 ¥ 1.22 ¥ 1000
mB = = 244
760 - PS 7 18 0.13 ¥ 100
= 2.4 ¥ ¥ = 0.01844
PS 164 100 Molecular weight of C6H5COOH is 122 and thus it is
evident that benzoic acid remains as normal molecu-
760
PS = = 746.24 mm Hg lar species in acetone but shows 100% dimerisation in
1.01844 C6H6, i.e., in C6H6 it exists as (C6H5COOH)2.
2. Given wB = 0.643 gram, Kf = 5.12 Kmol–1 kg wB 1000
6. (a) DTb = K b ¥
DTf = 5.51 – 5.03 = 0.48 mB wA
wA = Weight of benzene = V ¥ d = 50 ¥ 0.879 g wB DTb ¥ wA
= nB =
1000 ¥ 5.12 ¥ 0.643 mB K b ¥ 1000
\ 0.48 =
mB ¥ 50 ¥ 0.879 2 ¥ 100 5
= =
wB 1000 0.76 ¥ 1000 19
= DT f = K f ¥ ¥
mB wA [For very dilute solution (nA + nB = nA)]
\ mB = 156.06 P o - PS nB n w m
3. DTf = Kf ¥ m = xB = = B = B ¥ A
P o
n A + nB n A mB wA
DT f P o - PS 1000 760 - PS 5 18
\ m= = ¥ = ¥
Kf PS mA 760 19 100
760 - PS 9
0.30 23.51 - PS 1000 =
= ¥ 760 190
1.86 PS 18
760 - PS = 36
1002.9 PS = 23510
PS = 760 - 36 = 724 mmHg
\ PS = 23.44 mmHg
7. (a) Given Salts are completely ionise
4. DTf = i ¥ Kf ¥ M, i = (1 + a) Since, colligative properties μ i ¥ M
DTf = Kf ¥ molality ¥ (1 + a) and i ¥ M for C2H5OH = 1 ¥ 0.5 = 0.5
For acetic acid: CH3COOH m CH3COO– + H+ For Mg3(PO4)2 = 5 ¥ 0.1 = 0.5
C 0 0 For KBr = 2 ¥ 0.25 = 0.5
(1 – a) Ca Ca For Na3PO4 = 4 ¥ 0.125 = 0.5
Given, a = 0.23; \ all have same osmotic pressure because (i ¥ M
same) p = [i ¥ M]RT
Mole of acetic acid
Also, molality = P∞- Ps wB m A
Weight of water in kg 8. (b) = ¥
Ps mB wA
3 ¥ 10-3 ¥ 103
=
500 ¥ 0.997 185 - 183 1.2 58
60 ¥ = ¥
103 183 mB 100
C = 0.10 1 1.2 ¥ 58
DTf = Kf ¥ molality (1 + a) =
183 mB ¥ 100
DTf = 1.86 ¥ 0.1 ¥ 1.23
= 0.229 mB = 63.68

Chapter
4
Solid State
Key Concepts
1. Crystalline
2. Amorphous
1. In these solids, constituent particles are arranged in fixed pattern. 1. Constituent particles are arranged randomly.
2. Having sharp melting point 2. No sharp melting point. They melt over a range.
l
M.P. Cooling curve
S Temp.
Temp.
Time
Time
3. These are anisotropic in nature (different physical properties in 3. These are isotropic in nature (having similar
the different direction). physical properties in different direction).
4. These are called true solid. 4. These are called pseudo-solids or super cooled
For example, NaCl, diamond, i.e., quartz. liquids.
For example, rubber, glass, plastic.
Based on the type of binding forces among the constituent particles they are classified into four types.
1. Molecular solid Molecules Van der waals force and hydrogen bonding Solid Ar, dry ice
2. Ionic solid Ions, i.e., cations and anions Electrovalent bond NaCl, ZnS
or ionic bond
3. Covalent solid Atoms or molecules Covalent bond Diamond, quartz, SiC
4. Metallic solids Metal atoms and free valance electron Metallic bond Cu, Zn, Fe

UNIT CELL
It is the smallest repeating unit in the crystal lattice.

Geometry of the unit cell depends on the intercept made
on the 3 crystallographic axis, i.e., a, b, c and angle between
these, i.e., a, b, g.
zc
Atom is present on each corner as well as at body centre.
b
a
x
a
g
b
y
if, a = b = c and a = b = c
cubic unit cell Atom is present on each corner as well as at only one set of
opposite face centre.
Seven crystal systems are possible.
1. Cubic P, F, B a = b = c a = b = g = 90°
2. Orthorhombic P, F, B, E a π b π c a = b = g = 90°
3. Rhombohedral P a = b = c a = b = g π 90°
Note:
4. Monoclinic P, E a π b π c a = g = 90 b π 90° 1. There are 14 Bravais Lattice.
5. Triclinic P a π b π c a π b π g π 90° 2. In cubic system, there are only three types of unit
cell, i.e., simple, face centred and body centered.
6. Tetragonal P, B a = b π c a = b = g = 90°
7. Hexagonal P a = b π c a = b = 90° g = 120
These are of four types.

1. Body centered 1 1 {Fully
One atom is present on each corner of the cell. enclosed}
2. Face centered 6 1/2
3. Edge center 12 1/4
4. Corner 8 1/8
5. Body diagonal 4 1
1. Simple Cubic
1
Atom is present on each corner as well as on each face centre. z= ¥ 8 =1
8

Solid State 4.3
2. Face-centered cubic (FCC)

1
Z=
1
¥8+ ¥6=4 PACKING FRACTION (P.F.)
8 2
3. Body-centered cubic (BCC) Volume occupied by the spheres
P.F. =
1 Volume of the unit cell
z =8¥ +1¥1= 2 4
8 p ¥ p r3
P.F. = 3
Volume of unit cell
It is half of the distance between the two nearest neighbour

atom.
a
2r = a
r = a/2
Atom touch each other along the edge length.
4 3
pr ¥1
a 2 = 4r 4/3p r 3 ¥ 1
P.F. = 3 3 =
a a 2 ¥ 2 ¥ 2 ¥ r3
r= p
2 2 = = 0.52%
6
52% packed; 48% voids.
2a
a
Atoms touch each other along the face diagonal.
3a = 4r
3a
r=
4
3a
4 3
pr ¥ 4
4/3p r 3 ¥ 4 p
P.F. = 3 3 = 3
= = 0.74
a (2 2r ) 3 2
i.e., 74% packed; 26% voids.
Atoms touch each other along the body diagonal.

fi In this packing, each row of spheres is identical.

fi Each sphere is surrounded by four voids.
fi All the voids can be occupied by the second layer
sphere.
4 3 4 3 fi This is more closely packed compare to the square lattice.

pr ¥ 2 pr ¥ 2
3 3 3p fi Alternate rows of spheres are identical.
P.F. = = = = 68%
a3 (4r / 3)3 8 fi Each sphere is surrounded by 6 voids and out of these
60% packed; voids are 32%. only three alternate voids can be occupied by the second
layer sphere.
Mass of unit cell Total mass

d= =
Volume of unit cell Total volume
Z ¥ Atomic mass or M mass
= g/cm3
N A ◊ a3
1 Å = 10–9 cm 1 nm = 10–7 cm
1 Pm = 10–10 cm
It is the number of nearest neighbour atom for the given atom

in the crystal lattice.
(a) Simple Cubic
Based on the arrangement of third layer sphere packing in
CN = 6 (1 atom is surrounded by 6 atoms)
3-D. This can be of two types:
(b) fcc
CN = 12 (a) Hexagonal closed packing (hcp)
(c) bcc (b) Cubic closed packing (ccp)
CN = 8
1. Here third layer sphere is kept on the newly formed
First layer of the spheres can be formed in 2 ways: square void in the second layer, so that first and third become
lattice and hexagonal lattice. identical. Hence it is also called ABAB......... type
packing.
(A)

Solid State 4.5
(B)
(A) 1. In this packing, third layer spheres are kept on the old
voids. So that first and fourth layer become identical.
Hence it is called as ABC ABC ........ type packing.
Coordination number of each sphere is 12.
(a)
h = height
of hexagon
(b)
(c)
a = 2r
Effective number of atoms in unit cell (Z)

È 1 1˘
= Í1 ¥ + 6 ¥ ˙ ¥ 2 + 3 ¥ 1 = 6
Î 2 6˚
\ Z=6 (a)
3 2
Volume of hexagonal unit cell = 6 ¥ a ¥h
4
h
2
Since 2 =
a 3
2
\ h = 4r
3 VOIDS OR INTERSTITIAL
HOLES
3 2
and V =6¥ ¥ (2r ) 2 ¥ 4r = 24 2r 3
4 3
Triangular void is enclosed between
\ packing Fraction
the three spheres on joining their cen-
6 ¥ 4/3p r 3 p tres an equilateral triangle is formed.
= 3
= = 0.74
24 2r 3 2
When a sphere kept on the trian-
gular void is enclosed between
the 4 spheres. So that on joining Tetrahedral
Second layer colour change. their centres a regular tetrahe- voids
dron is formed.

rVoid a 2
= 0.225 R+r= (1)
RSphere 2
2R = a (2)
From (1) and (2)
Tetrahedral void r
= 0.414
R
fi
Tetrahedral Void
This void is formed in the square closed packing at the
3
R+r= a (i) body centre of a cube when atom is present on each
2 corner.
2R = a 2 (ii) r
= 0.414
r R
\ = 0.225 3a
R R+r=
Number of tetrahedral voids = 2 ¥ effective number of 2 (1)
atoms 2R = r (2)
Position of tetrahedral void = 2 at each body diagonal
See Li2O Crystal
O
––
ion in face centred cubic Cubical
void
Li+ ion in each tetrahedral void
Octrahedral
voids
r
(1)/(2) = 0.732
R
Order of size of void
This void is formed by the overlapping of two trian- Cubical > Octahedral > Tetrahedral > Triangular
gular voids in different layers. So that void is enclosed
between the 6 spheres on joining their centres regular
octahedron is formed. r + Radius of cation
Number of octahedral voids = Effective number of atoms =
In fcc unit cell, octahedral void are produced at edge r - Radius of anion
centre and body centre. Radius ratio determines the coordination number and shape
in ionic compound.
Cl– r+
If ≠ fi CN ≠
Na+ r-
1. – – rcation = rvoid
Na+ Present in
Octahedral voids Cation
–
Stable for coordination number = 3
2. – – rcation > rvoid

rvoid +
= 0.414
Rsphere –

Solid State 4.7
C.N.≠ here. So stable for higher C.N. (c) C.N of both Na+ and Cl– is 6. So it is called 6: 6 coor-
dination.
3. – – rcation < rvoid (d) Number of NaCl formulae unit/unit cell
– 1
Na + = 12 ¥ + 1 ¥ 1 = 4
4
This system does not exist because of anion-anion re-
- 1 1
pulsion. Cl = 8 ¥ + 6 ¥ = 4
No close packing is possible. 8 2
Z = 4 means 4 NaCl per unit cell
(e) 2(r+ + r–) = a a = edge length
– –
4r– = a 2 only for ideal crystal, i.e., anion-anion con-
tact.
– Actual volume occupied
(f) Packing fraction =
Volume of unit cell
r-
cos 30∞ = 4 4
r+ + r- 4 ¥ p ( r + )3 + 4 ¥ p ( r - )3
P.F. = 3 3
r+ (2 2r - )3
= 0.155
r-
p ÈÍÊ r + ˆ ˘È
3
˙ r+ ˘
= Á -˜
+ 1 Í here -
= 0.414˙
S.No. Radius ratio C.N. Shape 3 2 ÍÎË r ¯ ˙˚ Î r ˚
1. < 0.155 2 Linear
2. [0.155 to 0.225) 3 Triagonal planner
3. [0.225 to 0.414) 4 Tetrahedral Cl–
Cs+
4. [0.414 to 0.732) 6 Octahedral
5. [0.732 to 1) 8 bcc
AB type
AB2 types or A2B type
(a) Cl– is present on each corner while Cs+ is present at the
Here C.N. of both cations and anion are equal. AB-type sol- body center of the cube or vice versa.
ids can be of three types. (b) Cs+ is present in the cubical void.
1. NaCl type or Rock salt type (c) (Number of both Cl– and Cs+ is 8 so it is also called
2. CsCl type 8 : 8 coordination.
3. ZnS type or Zinc blend type
1
(d) Cl- = 8 ¥ =1 Cs+ = 1 ¥ 1 = 1
8
CsCl unit/unit cell, i.e., Z = 1
Cl–
(e) 2(r + + r - ) = 3 a
Na+
2r– = a only for ideal crystal.
(f) Packing fraction
4 4
1 ¥ p ( r + )3 + 1 ¥ p ( r - )3
P.F. = 3 3
(2r - )3
p È ÈÊ r + ˆ ˘
3˘
– = ÍÍ ˙ + 1˙
6 Í ÍÁË r - ˜¯
(a) Cl is present at each corner and on each face centre
ÎÎ ˙˚ ˙˚
whereas Na+ is present on edge center and body center
or vice versa.
(b) Cl– is present in fcc lattice while Na+ occupy all the r+
= 0.732
octahedral holes. r-

A2 2
1 1. Anion forms the fcc lattice and cations occupy all the
(a) S2– are present in fcc lattice while Zn+2 occupy of
2 tetrahedral voids.
the tetrahedral voids.
2. C.N. of cation is 4 whereas that of anion is 8. So it is
(b) CN of both Zn+2 and S– – ion is 4, so it is called 4: 4
called 4: 8 coordination.
coordination.
(c) Number of ZnS units per unit cell = 4
S–2 = 4(fcc) O– –
1 Li+
Zn +2 = 8 ¥ = 4
2
a
3◊
+ -
(d) (r + r ) = 2 = 3a
2 4
S– –
3. No. of A2B units per unit cell i.e. Z = 4 for ideal crystal
Zn++
r+
= 0.225
r-
Electronic defect Atomic defect or point defect

(due to excitation and (it is due to dislocation of
removal of e–from the atom) atom from its regular site)
4r - = a 2 only for ideal crystal. Atomics defect can be of three types:
(e) Packing fraction 1. Stoichiometeric defect
4 4 2. Non-stoichiometric defect
4 ¥ p ( r + )3 + ¥ 4 ¥ p ( r - )3 3. Impurity defect
P.F. = 3 3
(2 2r - )3 Because of atomic defects there is no change in electrical
neutrality.
p ÈÍÊ r + ˆ ˘
3
= ÁË - ˜¯ + 1˙ This can be of two types

3 2 ÎÍ r ˚˙
(A) Shottky defect (b) Frenkel defect
Ê r+ ˆ
here Á - = 0.225˜
Ër ¯ + – + – + – + –
– – + – + – +
AB2 2 +
1. AB2 type on CaF2 type or fluorite structure. + – + + – + –
2. Ca+2 is present in fcc lattice whereas F– occupy all the – + – + – + – +
tetrahedral holes.
3. CN of Ca+2 is 8 while that of F– is 4. (1) Equal number of (1) Cation is missing from
So, it is called 8: 4 coordination. cations and anions are its regular lattice site by
4. Number of CaF2 units/unit cell (Z) = 4 missing from their occupying the void in
lattice sites. the crystal.
3a
(r + + r - ) = (2) Density will decrease. (2) No change in density.
4
5. For ideal crystal 4r + = a 2 Lattice will be cation. (3) This defect is ob- (3) This defect is observed
6. Packing fraction served in the ionic in ionic solids hav-
solids having similar ing dissimilar sizes of
4 4
4 ¥ p ( r + )3 + 8 ¥ p ( r - )3 sizes of cation and cation and anion, i.e.
= 3 3 anion, i.e., having having the low
(2 2r + )3 high CN. coordination number.
p ÈÍ Ê r- ˆ ˘Ê
3
r- ˆ
= 1 + 2 Á + ˜ ˙ Á here + = 0.225˜
3 2ÎÍ Ë r ¯ ˙
˚ Ë r ¯

Solid State 4.9
This can be of two types: S. No. Solids Conductivity

1. Metals 108W–1 cm–1
It can happen in two ways: 2. Insulators 10–12W–1 cm–1
fi When anion is missing from its lattice site and e– in en-
3. Semiconductors 10–5 to 106W–1cm–1
trapped in place of it called F-centre (forbe means colour)
Metals oxides and sulphites have metallic to insulator behav-
+ – + –
F-centre iour at different temperatures.
– + e– + For example, NaCl LiCl KCl
+ – + – Ø Ø Ø
– + – + Yellow Pink Violet These substance are weakly attracted
by magnetic field. These substances possess permanent
Presence of F-centre ≠ the conductivity and impart the color magnetic dipoles due to the presence of unpaired elec-
to the crystal. trons. For example, TiO2, CuO, O2, etc.
fi When extra cation and extra e– are entrapped into the These substances are strongly attract-
ed by magnetic field. These substances possess more
voids of the crystal.
unpaired electrons than ordinary paramagnetic sub-
+ – + – For example, ZnO (white colour) stances. For example, Fe, Co, Ni, etc.
+ This arises when net dipole
– + – + but when use heat yellow colour
e–
alignment is zero due to equal and opposite alignment,
+ – + – MnO, MnO2, Cr2O3, etc.
1
– + – + ZnO h Zn +2 + O 2 ≠ + 2e - This arises when there is net dipole
2
moment non-zero. For example, Fe3O4, ferrities.
The substances which are feebly re-
pelled by the magnetic fields. These substances have
+ – + – all their electrons paired, For example, V2O5, NaCl,
– +2 – + C6H6, etc.
+ – + –
– + – +
It is electricity which is produced by
This defect is observed in the compounds of transition metal, applying mechanical stress on solid crystal, e. g., PbZ-
because they can show the variable oxidation state. rO3 (lead zirconate)
Density will decrease. It is electricity which is produced by
For example, wustite Fe0.94O heating solid crystal.
Cationic vacancy is 6%. Here some Fe+3 is there. Sometimes in a piezo-electric crys-
tal, the dipoles are polarised even when no electricity
When any foreign or external atom occupies the lattice site in flows through them. When electric field is applied to
the crystal, it is called impurity defect. them, the direction of polarisation changes. This is
called ferro-electricity.
Example 1 Formation of P type of N type semiconductors
by adding the impurities in the pure semicon- For example, Sodium potassium tartarate.
ductor lattice. Bi and Ge. When dipoles of a crystal align
Example 2 Impurity of SrCl2 in NaCl. in such a way that they do not have any net dipole mo-
ment, the phenomenon is called antiferroelectricity.
P type impurity due to presence of IIIA (Al),
For example, PbZrO3.
element N type impurity due to presence of ele-
ment of VA(As) The structure of crystal is determined by
X–ray analysis.
nl = 2d sin q
where, d = diffraction order [1, 2, 3, …]
Solids are classified into following classes depending on the l = wavelength of incident X–ray
extent of conducting nature: q = angle of diffraction

Solved Examples
A solid has a cubic structure in which x atoms are locat- 1

ed at the corner of cube and y atoms are at cube center cations B occupy of the octahedral voids. What is
2
and O atoms are at edge centres. What is the formula of the formulae of the compound?
the compound? Oxides ions are forming the lattice reference
1 \ Number of oxide ion = 4 (CCP)
x=8¥ =1 \ Tetrahedral void = 2 ¥ 4 = 8
8
y=1¥1=1 1
and Number of A atom = ¥ 8 = 1
1 8
O = 12 ¥ = 3 Number of octahedral void = 4
4
XYO3 1
\ Number of B atom = ¥ 4 = 1
Potassium crystallises in a bcc lattice. What is the num- 2
ber of unit cells in 3.9 g of K. Atomic weight of K = 39. \ molecular formula AB2O4
What is the simplest formula of a solid whose unit cell
3.9 NA
(Number of atoms) K = ¥ NA = has the atom A at each corner, the atom B at each face
39 10 centre and a C atom at the body centre?
in bcc = Z = 2
2 atom = 1 unit cell (a) A2BC (b) AB2C (c) AB3C (d) ABC2
An atom at the corner of a cube is shared among 8 unit
1
Number of unit cell = Number of atoms cells. As there are 8 corners in a cube, number of corner
i.e., 2
1
atom (A) per unit cell = 8 ¥ = 1.
NA 8
\ Number of unit cells =
20 Face-centred atom in a cube is shared by two unit cells.
Calculate the number of atoms in a cubic-based unit As there are 6 faces in a cube, number of face-centred
cell having one atom on each corner and 2 atoms on or 1
atoms (B) per unit cell = 6 ¥ = 3.
each body diagonal. 2
Number of corner = 8 Number of body diagonal = 4 in An atom in the body of the cube is not shared by other
each cubic crystal cells.
1 \ Number of atoms (C) at the body centre per unit
Number of atoms present at corner = 8 ¥ = 1
8 cell = 1.
Number of atoms present body diagonal = 4 ¥ 2 = 8 hence, the formula of the solid is AB3C.
\ z=9 Analysis show that nickel oxide consist of nickel ion
Silver crystallises in is fcc unit cell. Density of silver is with 96% ions having d8 configuration and 4% having
10.8 g/cm3. Calculate the edge length of the unit cell in d7 configuration. Which amongst the following best
Picometers. represents the formula of the oxide.
(a) Ni1.02O1.00 (b) Ni0.96O1.00
z ¥ Atomic Mass
d= (c) Ni0.98O0.98 (d) Ni0.98O1.00
N A ¥ a3
d8 Æ Ni+2 d7 Æ Ni+3
4 ¥ 108
a =
3
Total charge of nickel
6.023 ¥ 1023 ¥ 10.8 (0.96 ¥ 2) + (0.04 ¥ 3) = 2.04
4
= ¥ 10-22 Number of O–2 ion =
2.04
= 1.02
6 2
a3 = 0.66 ¥ 10–22 Formula of solid = NiO1.02 = Ni0.98O1.00
Ferric oxide crystallises in a hexagonal close packed
= 6.6 ¥ 10–21 array of oxide ions with two out of every three. Octa-
= 10–7 (6.6)1/3 cm hedral holes occupied by ferric ions. The formula of the
ª 400 pm ferric oxide is
(a) FeO (b) Fe3O4
In a compound oxide ions have ccp arrangement, cat-
(c) Fe2O3 (d) None of these
1
ions A are present in of the tetrahedral voids and Suppose the number of oxide ions (O2–) in the packing
8 = N.

Solid State 4.11
Number of octahedral voids = N Z ¥ atomic mass

As 2/3rd of the octahedral voids are occupied by ferric d=
a3 ¥ N A
ions, therefore, number of ferric ions present
For fcc lattice of copper, Z = 4
2 2N
= ¥N= Atomic mass of copper, = 63.5 g mol–1
3 3
4 ¥ 63.5 g mol –1
2N d=
Therefore, ratio of Fe3+: O2– = :N=2:3 (3.61 ¥ 10 –8 cm)3 ¥ (6.022 ¥ 1023 mol –1 )
3
Hence, the formula of ferric oxide is Fe2O3. = 8.97 g cm –3
Iron crystallises in a body centred cubic structure. The The number of unit cells in 58.5 g of NaCl is approxi-
radius of Fe atom (if edge length of unit cell is 286 pm) mately
is. (a) 6 ¥ 1020 (b) 1.5 ¥ 1023
(a) 120.9 pm (b) 123.8 pm (c) 6 ¥ 10 23
(d) 0.5 ¥ 1024
(c) 23.8 pm (d) 223.8 pm Molar mass of NaCl = 23 + 35.5 = 58.5 g
Edge length, a = 286 pm \ moles of Na+ = moles of Cl– = Moles of NaCl =
3 3 58.5
For BCC, radius of atom, r = a= ¥ 286 =1
4 4 58.5
1.732 ¥ 286 In a unit cell of NaCl fi
= = 123.8 pm
4 Number of Na+ ion = 4
The limiting radius ratio of the complex [Ni(CN)4]2– is Number of Cl– ion = 4
(a) 0.225 – 0.414 (b) 0.414 – 0.732 1
(c) 0.155 – 0.225 (d) None \ Total Number unit cell = ¥ Number of NaCl
4
The complex [Ni(CN)4]–2 is square planar Since 1 6.02 ¥ 1023
Since CN– strong field ligand \ hybridisation dsp2. So, Total number of unit cell ¥ NA = = 1.5
4 4
it has limiting radius ratio as octahedral structure, i.e., ¥ 1023
0.414 – 0.732. In fluorite structure (CaF2)
In closest packing of A type of atoms (radius, rA), the ra- (a) Ca++ ions are ccp and F– ions are present in all the
dius of atom B that can be fitted into octahedral void is tetrahedral voids.
(a) 0.155 rA (b) 0.125 rA (b) Ca++ ions are ccp and ions are present in all the
(c) 0.414 rA (d) 0.732 rA octahedral voids.
For octahedral void (c) Ca++ ions are ccp and ions are present in all the
octahedral voids and half of ions are.
rB (d) F– ions are in fcc and Ca++ are present in all the
= 0.414
rA tetrahedral voids.
or rB = 0.414 rA. Ca2+ ions are ccp and F– ions are present in the tet-
Copper crystallises into a fcc lattice with edge length rahedral voids. So, the number of Ca2+ ions is 4 and
3.61 ¥ 10–8 cm. The calculated density is number of F– ions is 8.So, the formula of the calcium
(a) 8.97 g/cc (b) 10.9 g/cc fluoride Ca4F8 or, the simplest formula of calcium fluo-
(c) 5.45 g/cc (d) 6.02 g/cc ride is CaF2.
Exercise
of each of the cube faces. What is the formula of this
LEVEL I compound?
(a) AuCu6 (b) AuCu
A cubic solid is made up of two elements A and B. At- (c) AuCu3 (d) None of these
oms B are at the corners of the cube and A at the body KF crystallises in the NaCl type structure. If the radius
centre. What is the formula of compound? of K+ ions 132 pm and that of F– ion is 135 pm, what is
the closet K–K distance?
(a) AB (b) AB2 (c) A2B (d) None
(a) Cannot say (b) 534 pm
A compound alloy of gold and copper crystallises in a (c) 755 pm (d) 378 pm
cubic lattice in which gold occupy that lattice point at AgCl has the same structure as that of NaOH. The edge
corners of the cube and copper atom occupy the centres length of unit cell of AgCl is found to be 555 pm and

the density of AgCl is 5.561 g cm–3. Find the percent- An element crystallises in a structure having fcc unit
age of sites that are unoccupied. cell of an edge 200 pm. Calculate the density, if 200 g
(a) 0.24% (b) 2.4% (c) 24% (d) None of this element contains 5 ¥ 1024 atoms.
The effective radius of the iron atom is 1.42 Å. It has (a) 5 m/cm3 (b) 30 g/cm3
fcc structure. Calculate its density (Fe = 56 amu). (c) 10 g/cm 3
(d) 20 g/cm3
(a) 2.87 g/cm3 (b) 11.48 g/cm3 If the length of the body diagonal for CsCl which cryst-
3
(c) 1.435 g/cm (d) 5.74 g/cm3 allises into a cubic structure with Cl– ions at the corners
The density of CaF2 (fluorite structure) is 3.18 g/cm3. and Cs+ ions at the centre of the unit cells is 7 Å and
The length of the side of the unit cell is
the radius of the Cs+ ion is 1.69 Å. What is the radii for
(a) 253 pm (b) 344 pm (c) 546 pm (d) 273 pm
Cl– ion?
If the anions (A) form hexagonal closest packing and
cations (C) occupy only 2/3 octahedral voids in it, then (a) 1.81 Å (b) 5.31 Å (c) 3.62 Å (d) None
the general formula of the compound is Which of the following formulas is consistent with the
(a) CA (b) CA2 (c) C2A3 (d) C3A2 unit cell of the rhenium oxide compound shown be-
A solid is formed and it has three types of atoms X, Y, low?
Z. X forms a FCC lattice with Y atoms occupying all
the tetrahedral voids and Z atoms occupying half the
octrahedral voids. The formula of the solid is Oxygen
(a) X2Y4Z (b) XY2Z4 (c) X4Y2Z (d) X4YZ2
A compound XY crystallises in BCC lattice with unit Rhenium
cell edge length of 480 pm. If the radius of Y– is 225
pm, then the radius of X+ is:
(a) 127.5 pm (b) 190.68 pm
(c) 225 pm (d) 255 pm (a) Re2O6 (b) Re2O3 (c) ReO6 (d) ReO
An ionic compound AB has ZnS type structure. If the The figure below shows a unit cell of the mineral
radius A+ is 22.5 pm, then the ideal radius of B– would Perovskite (the titanium atom is at the centre of the
be cube). Which of the following is a correct chemical
(a) 54.35 pm (b) 100 pm. formula for this mineral?
(c) 145.16 pm (d) None of these
NH4Cl crystallises in a body centred cubic type lattice
Calcium
with a unit cell edge length of 387 pm. The distance
between the oppositely charged ions in the lattice is Oxygen
(a) 335.1 pm (b) 83.77 pm
Titanium
(c) 274.46 pm (d) 137.23 pm
A cubic solid is made by atoms A forming close pack
arrangement, B occupying one/fourth of tetrahedral
void and C occupying half of the octahedral voids.
What is the formula of compound?
(a) A4B4C2 (b) A4B2C4 (a) Ca8TiO6 (b) CaTiO
(c) A4BC (d) A4B2C2 (c) Ca2TiO3 (d) CaTiO3
An element crystallises into a structure which may be An atomic solid has hexagonal arrangement of unit
described by a cubic type of unit cell having one atom cell with height of hexagonal (in close packed arrange-
on each corner of the cube and two atoms on one of its ment) as “h”. The radius of atom in terms of height is
body diagonals. If the volume of this unit cell is 24 ¥
10–24 cm3 and density of element is 7.2 g cm–3, calcu- 2 h 2 h 3 h 3
(a) 4 h (b) (c) (d)
late the number of atoms present in 200 g of element. 3 4 3 4 2 4 2
(a) 1.1513 ¥ 1024 (b) 3.472 ¥ 1024 What is the formula of a compound of niobium and
(c) 10.416 ¥ 10 24
(d) None of these nitrogen that crystallises in a hexagonal closest packed
Xenon crystallises in the face centred cubic lattice and array of nitrogen atoms with niobium atoms in half of
the edge of the unit cell is 620 pm. What is the next the tetrahedral holes?
nearest neighbour distance? (a) Nb4N (b) Nb2N (c) NbN (d) NbN2
(a) 738.5 pm (b) 620 pm Select the incorrect statement for CsCl crystal.
(c) 438.5 pm (d) 310 pm (a) Coordination number for Cs+ and Cl– is 6

Solid State 4.13
rCs+ (a) 0º, 90º (b) 90º, 0º (c) 30º, 90º (d) 90º, 30º
(b) = 0.732 A crystal is made of particles A and B. A forms fcc
rCl – packing and B occupies all the octahedral voids. If all
(c) The structure changes to NaCl at 760 K the particles along the plane as shown in figure are re-
(d) Cl– ions are present at cubic sites moved, then, the formula of the crystal would be
The radius of an atom of an element is 80 pm. If it crys- A
tallises as a body centred cubic lattice, what is the edge B
of its unit cell?
(a) 140 pm (b) 184.7 pm
(c) 209.2 pm (d) 147.5 pm
A solid XY has NaCl structure. If radius of X+ is 100
pm. What is the radius of Y– ion?
(a) 120 pm (b) 136.6 to 241.6 pm (a) AB (b) A5B7 (c) A7B5 (d) A2B3
(c) 136.6 pm (d) 241.6 pm The number of atoms on HCP unit cell is
A solid is made of two elements P and Q. Atoms P are (a) 4 (b) 6 (c) 12 (d) 17
in CCP arrangement and atoms Q occupy all the octa- The volume of HCP unit cell is
hedral voids and half of the tetrahedral voids, then the
(a) 24 2r 3 (b) 16 2r 3
simplest formula of the compound is
(a) PQ2 (b) P2Q (c) PQ (d) P2Q2 64r 3
(c) 12 2r 3 (d)
Fraction of total volume occupied by atoms in a simple 3 3
cubic cell is In a ccp lattice of X and Y, X atoms are present at the
p 3p 2p p corners while Y atoms are at face centres. Then the for-
(a) (b) (c) (d)
2 8 6 6 mula of the compound would be if one of the X atoms
The number of atoms in 100 g of an fcc crystal with from a corner is replaced by Z atoms (also monova-
density d = 10 g/cm3 and cell edges as 200 pm is equal to lent)?
(a) 3 ¥ 1025 (b) 5 ¥ 1024 (a) X7Y24Z2 (b) X7Y24Z
(c) 1 ¥ 10 25
(d) 5.96 ¥ 10–3 (c) X24Y7Z (d) XY24Z
The correct statement regarding defects in solids is The density of solid argon (Ar = 40 g/mol) is 1.68 g/mL
(a) Frenkal defect is favoured by a very small differ- at 40 K. If the argon atom is assumed to be a sphere of
ence in the size of cation and anion. radius = 1.50 ¥ 10–8 cm, what % of solid Ar is appar-
(b) Frenkal defect is not a dislocation defect. ently empty space?
(c) trapping of e– in lattice leads to the formation of (a) 35.64 (b) 64.36
F–centre. (c) 74% (d) None of these
(d) Schottky defects have no effect on the physical A body centered cubic lattice is made up of hollow
properties of solid. spheres of B. Spheres of solid A are present in hollow
‘C’ represent the height of the hcp unit cell and ‘a’ rep- spheres of B. Radius A is half of radius of B. What is
resent edge length of the hexagonal surface of the hcp the ratio of total volume of spheres of B unoccupied by
unit cell. What is the value of C/a? A in a unit cell and volume of unit cell?
2 8 32 3 7 3p 7 3p
(a) (b) (c) (d) (a) (b)
3 3 3 2 64 128
Antifluorite structure is derived from fluorite structure 7p 7p
by (c) (d)
24 64 3
(a) heating fluorite crystal lattice.
A compound formed by elements A and B crystallises
(b) subjecting fluorite structure to high pressure.
in a cubic structure where A atoms are at the corners of
(c) interchanging the positions of positive and nega-
a cube and B atoms are at the face centre. The formula
tive ions in the lattice.
of the compound is
(d) introducing the impurities to the lattice.
(a) AB3 (b) AB2
The anions (A) form hexagonal closest packing and the
(c) AB4 (d) None of these
cations (C) occupy only 2/3 of octahedral holes. The
A binary solid has rocksalt structure. The edge length is
simplest formula of the ionic compound is
400 pm and the radius of cation is 75 pm, the radius of
(a) CA (b) C3A2 (c) C4A3 (d) C2A3
anion is
At what angles for the first order diffraction, spacing
(a) 100 pm (b) 125 pm
l
between two planes respectively are l and ? (c) 250 pm (d) 325 pm
2

Total volume of all atoms present in face centred cubic voids are occupied by divalent (X++) ions, while one-
unit cell of metal is (r = edge length) half of the octahedral voids are occupied by trivalent
p r3 24 3 12 3 16 3 ions (Y3+), then the formula of the oxide is
(a) (b) p r (c) pr (d) pr (a) XY2O4 (b) X2YO4 (c) X4Y5O10 (d) X5Y4O10
3 2 3 3 3
Xenon crystallises in face centre cubic lattice and the
edge of the unit cell is 620 pm, then the radius of xe-
LEVEL II non-atom is
(a) 438.5 pm (b) 219.20 pm
1. Niobium crystallises in a body centred cubic structure. (c) 536.94 pm (d) 265.5 pm
If density is 8.55 g cm–3. The atomic radius of niobium, Calculate the ionic radius of a Cs+ion assuming the cell
(given that its atomic mass is 93 u) is edge length for CsCl is 0.4123 nm and that the ionic
(a) 49.8 pm (b) 150.1 pm radius of a Cl– ion is 0.181 nm.
(c) 143.1 Å (d) 143.1 pm (a) 0.176 nm (b) 0.231 nm
In a hypothetical solid C atoms are found to form cubi- (c) 0.358 nm (d) 0.116 nm
cal close packed lattice. A atoms occupy all tetrahedral An alloy of two metals Q and R has a cubic structure.
voids and B atoms occupy all octahedral voids. A and B The unit cell maybe described as cubic close packed
atoms are of appropriate size, so that there is no distor- with respect to metal atoms Q. The R atoms are in the
tion in ccp lattice of C atoms. Now if a plane as shown body centres of alternate minicubes made by partition-
in the following figure is cut. Then the cross section of ing the main cube into 8 equal parts as
this plane will look like. shown in the diagram.
On the basis of above description, iden-
C B C tify the incorrect conclusion.
(a) The number of nearest neighbours
A
B B B of R is 4.
(a)
A (b) The radius of R atom is less than that of Q atoms.
(c) The angle made by the line connecting any R
C B C
atom with two of its nearest neighbours (Q atoms)
is 109°28¢.
(d) The number of nearest neighbours of Q is 8.
C C C X+Y– crystallises in a bcc lattice in which the radius of
X+ = 0.4A. If all the X+ ions are removed and another
(b) B B B cation z+ is inserted, what should be the maximum ra-
dius of the cation z+ to crystallise in a fcc lattice with
y–?
C C C
(a) 0.548 Å (b) 0.010 Å
(c) 0.400 Å (d) 0.226 Å
When heated at 916°C , iron changes its bcc crystalline
C C C form to fcc. The ratio of density of the crystal before
A A heating and after heating is
(c) B B B (a) 1.069 (b) 0.918 (c) 0.725 (d) 1.23
A A A metal M crystallised in both fcc lattice and in bcc lat-
tice. If the densities of these forms are in 2:1 ratio the
C C C
corresponding cubic edges are in the ratio
(a) 1: 2 (b) 2: 1 (c) 1: 4 (d) 1: 1
A metal of atomic mass = 75 forms a cubic lattice of
C C C edge length 5 Å and density 2 g cm–3. Calculate the
radius of the atom (given Avogadro’s number, NA = 6 ¥
A A 1023.)
(d) B B B
A A (a) 261.5 pm (b) 523 pm
(c) 145 pm (d) 130.5 pm
C C C
Ionic compound AB has NaCl type of structure. The
radius of A+ ion is 41.4 pm. If the radius of A+ ion de-
In a cubic packed structure of mixed oxides, the lat- creases and becomes equal to 30 pm, then in what type
of structure would AB crystallise and what would be
tice is made up of oxide ions, one fifth of tetrahedral
coordination number of A+ ion?

Solid State 4.15
(a) ZnS-4 (b) CsCl-8 X-ray analysis Mn–Si alloy with 75% by atoms of Mn
(c) MgO-6 (d) BeO-8 and 25% by atoms of Si, showed that the unit cell is
A metal crystallises into a lattice containing a sequence cubic and lattice parameter is 2.86 Å. The density of
of layers of ABC ABC. If the radius of metal atoms is alloy = 6850 kg/m3. How many number of atoms are
174 pm, then the distance between the two successive present in the unit cell?
layers (i.e., A and B) is Mn: 55 and Si: 28
(a) 348 pm (b) 174 pm (a) 2 (b) 4 (c) 6 (d) 8
(c) 284. 2 pm (d) 492. 2 pm Regarding graphite the following information is avail-
A metallic element exists in simple cubic structure. able:
Each edge of the unit cell is 3 Å. The density of metal
is 10 g cm–3. How many unit cells will be there in 16.2 Top view
g of the metal?
(a) 6 ¥ 1022 (b) 16 ¥ 1031 3.35 Å
(c) 2.8 ¥10 23
(d) 4.2¥1021
The percentage vacant space in one layer of square
packing of spheres touching each other having 4
spheres is
3 Ê pˆ The density of graphite = 2.25 g/cm3. What is C–C
(a) p ¥ 100 (b) Á100 - ˜ 100 bond distance in graphite?
8 Ë 6¯
(a) 1.68 Å (b) 1.545 Å
3 p (c) 2.852 Å (d) 1.426 Å
(c) p (d) 100 - ¥ 100
8 6 A CCP of n spheres of radius r, n spheres of radius
In a face centered cubic cell, the atom at the face centre 0.414r and 2n spheres of radius 0.225r are introduced
is supposed to touch adjacent corner atoms. In this cu- in the octahedral and tetrahedral void respectively.
bic close packing of identical atoms, some vacant space Therefore packing fraction of the lattice.
is left in the crystal. The layers are arranged parallel to (a) 0.74 (b) 0.81 (c) 0.68 (d) 0.79
the body diagonal. Copper metal crystallises in fcc with What is the diameter of the largest sphere that will fit in
an edge length of 3.61 Å. Calculate the size of largest the void at the centre of the cube edge of a bcc crystal
atom which could fit into the interstices of copper lat- of edge length a?
tice without distorting it is nearly (a) 0.134a (b) 0.76a
(a) 0.212 Å (b) 0.421 Å (c) 0.05548a (d) 0.098a
(c) 0.525 Å (d) 0.640 Å
The height of a hcp unit cell is 5.715 Å. What is the
volume of the unit cell in (Å)3? LEVEL III
(a) 91 (b) 182 (c) 273 (d) 82.5
A crystal is made up of particles X, Y and Z. X forms
1. Match the columns:
fcc packing, Y occupies all octahedral voids of X and
Z occupies all tetrahedral voids of X. If all the particles
along one body diagonal are removed, then the formula
of crystal would be (A) Cubic (P) Simple or primitive
(a) XYZ2 (b) X2YZ2 (c) X8Y4Z5 (d) X5Y4Z8
(B) Tetragonal (Q) Body Centred
KCl crystallises in the same type of latice as does NaCl.
r + r + (C) Orthorhombic (R) Face Centred
Given that Na = 0.55 and K = 0.74 . Calculate the (D) Monoclinic (S) End Centred
rCl- rCl-
ratio of the side of the unit cell for KCl to that of NaCl. 2. Match the columns:
(a) 1.123 (b) 0.891 (c) 1.414 (d) 0.414
In cubic ZnS, the radii of the Zn and S atoms are 0.83
Å and 1.74 Å respectively. What is the edge length of
the unit cell of ZnS?
(a) 2.57 Å (b) 3.64 Å (c) 2.97 Å (d) 5.935 Å
An elemental crystal has a density of 8570 kg/m3. The
packing efficiency is 0.68. The closest distance of ap- (A) (P)
proach between neighbouring atom is 2.86 Å. What is
the mass of one atom approximately?
(a) 29 amu (b) 39 amu (c) 63 amu (d) 93 amu

Perovskite, a mineral containing calcium, oxygen and tita-

(B) (Q) nium crystallises in the given unit cell.
Calcium
Oxygen
Titanium
(C) (R)
Total number of atom present in a unit cell is
(a) 3 (b) 4 (c) 5 (d) 6
The oxidation number of titanium in the perovskite is
(a) 5 (b) 4 (c) 3 (d) 2
(D) (S) If oxygen atom is removed from alternate position then
the formula of perovskite is
(a) CaTiO (b) CaTi2O
(c) CaTiO2 (d) Ca3Ti2O
3. Match the columns:
(A) ZnS crystal (P) fcc There are solids which are difficult to prepare in the stoichio-
metric composition, e.g., pure FeO is difficult to obtain and
(B) CaF2 crystal (Q) hcp normally we get a composition of Fe0.95O but it may range
(C) NaCl crystal (R) Distance between from Fe0.93O to Fe0.96O. Zinc oxide loses oxygen reversibly
closest particles is at high temperatures and turns yellow in colour. The excess
3 metal is accommodated interstitially, giving rise to electrons
a trapped in the neighbourhood. One of the common methods
4
of introducing defects in ionic solids is by adding impurity
(D) Diamond crystal (S) Only one type of ions having different charge than host ions.
voids are occupied Fe0.95O can be due to presence of iron in +2 and +3
4. Match the columns: oxidation numbers. Then iron present in +3 oxidation
state will be
(a) 15% (b) 13.5% (c) 10.5% (d) 8.85%
(A) Schottky defect (P) In NaCl defect Assertion/Reason
produced by
heating NaCl in (a) Both Assertion and Reason are correct and Reason is
SrCl2 the correct explanation of Assertion.
(b) Both Assertion and Reason are correct but Reason is
(B) Frenkel defect (Q) Defect produced by not the correct explanation of Assertion.
heating NaCl. (c) Assertion is correct but Reason is incorrect.
(C) F-centres (R) NaCl (d) Both Assertion and Reason are incorrect.
(D) Metal deficiency (S) AgCl r+
As increase coordination number is also
Match the columns: r-
increases because
r
(A) Cubic close pack- (P) Empty space = 48% When + = 1 the C No. tend to 12.
r-
ing
The square close packing is not possible in
(B) Body centred (Q) Empty space = 26% closest packing but hexagonal close packing is possible
cubic in the closest packing.
(C) Hexagonal close (R) Coordination num- In the closest packing three spheres of same
packing ber = 12 radius are mutually touching each other.
(D) Simple cubic (S) Coordination num- There is a large difference between the
ber = 8 melting points of NaF and MgO.
Cations and anions are both the salts are iso-
electronic.

Solid State 4.17
In NaCl structure, Na+ ions occupy octahe- Silver has a cubic unit cell with a cell edge of 408 pm.
dral holes and Cl– ions occupy ccp. Its density is 10.6 g cm–3. How many atoms of silver
The distance of the nearest neighbours in are there in the unit cell?
NaCl structure is a/2 where a is the edge length of the A compound AB has a rock salt-type structure with A:B
cube. = 1:1. The formula weight of AB is 6.023 y amu and the
closest A – B distance is y1/3 nm. Calculate the density
Multiple Answer Type Questions of lattice.
The ionic radii of Cs+ and Cl– are 0.165 nm and 0.181 At room temperature, sodium crystallises in a body-
nm respectively. Their atomic weights are 133 and centered cubic lattice with a = 4.24 Å. Calculate theo-
35.5. Then, retical density of sodium (Atomic weight of Na = 23).
(a) The lattice parameter is 0.4 nm Copper has the fcc crystal structure. Assuming an
(b) Inter ionic distance is 0.4nm. atomic radius of 130 pm for copper atom (Cu = 63.54):
(c) The density of Cs Cl is 4.37 ¥ 103 kg/m3. (a) What is the length of unit cell of Cu?
(b) What is the volume of the unit cell?
(d) The Cs Cl structure has a bcc structure
(c) How many atoms belong to the unit cell?
The data given below is used to find the type of cubic
(d) Find the density of Cu.
lattice to which the crystal belong.
Compute the percentage void space per unit volume of
Ag Al Cu Na unit cell in zinc sulphide structure.
In a close packed structure of mixed oxides, the lattice
a (pm) 407.7 405 361 424
is composed of oxide ions, one eighth of tetrahedral
r (g cm–3) 10.5 2.7 8.92 1.002 voids are occupied by divalent cations while one half
At. mass (gm) 108 27 63.5 23 of octahedral voids are occupied by trivalent cations.
What is the formula of the oxide?
Which of the above crystallizes in FCC unit cell A compound formed by elements A and B crystallises
(a) Ag (b) Al (c) Cu (d) Na in cubic structure where A atoms are at the corners of
The coordination number of FCC structure for metals a cube and B atoms are at the face centre. What is the
is 12, since formula of the compound?
(a) each atom touches 4 others in same layer, 3 in NH4Cl crystallises in a body centred cubic lattice,
layer above and 3 in layer below. with a unit cell distance of 387 pm. Calculate (a) the
(b) each atom touches 4 others in same layer, 4 in distance between the oppositely charged ions in the
layer above and 4 in layer below. lattice, and (b) the radius of the NH4+ ion if the radius
(c) each atom touches 6 others in same layer, 3 in of the Cl– ion is 181 pm.
layer above and 3 in layer below. Iron occurs as bcc as well as fcc unit cell. If the effec-
(d) each atom touches 3 others in same layer, 6 in tive radius of an atom of iron is 124 pm, compute the
layer above and 6 in layer below. density of iron in both these structures.
Which of the following is/are true? A solid A+ B– has NaCl type close packed structure. If
(a) Piezoelectricity is due to net dipole moment. the anion has a radius of 250 pm, what should be the
(b) Some electric current is produced on heating po- ideal radius of the cation? Can a cation C+ having a
lar crystals, this is pyroelectricity. radius of 180 pm be slipped into the tetrahedral site of
(c) Ferro-electricity is due to alignment of dipole in the crystal A+ B–? Give reason for your answer.
the same direction. Calculate the void space in a primitive unit cell and
(d) Ferri-electricity is due to the alignment of dipole also the fraction of the total volume occupied.
in the same direction. The density of solid argon is 1.65 g/mL at –233°C. If
Which of the following is/are correct? the argon atom is assumed to be sphere of radius 1.54 ¥
(a) Crystalline solids are anisotropic. 10–8 cm, what percentage of solid argon has apparently
empty space? (Atomic weight of Ar = 40).
(b) Amorphous solids are isotropic.
An element crystallises as body centred cubic lattice.
(c) Crystalline solids have sharp melting points.
Its density is 7.12 g cm–3 and the length of the side of
(d) Amorphous solids also have sharp melting points.
the unit cell is 2.88 Å. Calculate the number of atoms
Integer and Subjective present in 288 g of the element.
An ionic solid A+ B– crystallises as a body centred cu-
KF has NaCl structure. What is the distance between bic structure. The distance between cation and anion in
K+ and F– in KF, if the density is 2.48 g cm–3? the lattice is 338 pm. Calculate the edge length of the
The density of CaO is 3.35 g/cm3. The oxide crystal- unit cell.
lises in one of the cubic systems with an edge of 4.80 The edges length of unit cell of a metal having molecu-
Å. How many Ca++ ions and O–2 ions belong to each lar weight 75 g/mol is 5 Å which crystallises in cubic
unit cell, and which type of cubic system is present? lattice. If the density is 2 g/cc then find the radius of
metal atom (NA = 6 ¥ 1023). Give the answer in pm.

In face centred cubic (fcc) crystal lattice, edge length A unit cell of sodium chloride has four formula units.
is 400 pm. Find the diameter of greatest sphere which The edge of length of the unit cell is 0.564 nm. What is
can be fit into the interstitial void without distortion of the density of sodium chloride?
lattice. The composition of a sample of wustite is Fe0.93O1.0.
A metal crystallises into two cubic phases, face cen- What percentage of iron is present in the form of Fe(II)?
trered cubic (fcc) and body centred cubic (bcc), whose If NaCl is dopped with 10–3 mol % SrCl2, what is the
unit cell lengths are 3.5 and 3.0 Å, respectively. Calcu- number of cation vacancies?
late the ratio of densities of fcc and bcc. Ice crystallises in a hexagonal
The density of mercury is 13.6 g/mL. Calculate volume lattice. At the low temperature
at which the structure was deter- b
of mercury atom assuming that each atom is occupying a
cube of edge length equal to the diameter of mercury atom. mined, the lattice constants were
a
An element (atomic mass = 60) having face centred a = 4.53Å, and b = 7.60Å (see
figure). How many molecules are contained in a given
cubic crystal has a density of 6.23 g cm–3. What is the
unit cell? [density (ice) = 0.92 g/cm3]
edge length of the unit cell (Avogadro constant, NA =
A compound formed by elements X and Y. Crystallises
6.02 ¥ 1023 mol–1) in a cubic structure, where X is at corners of the cube
The density of KBr is 2.75 g cm–3. The length of the and Y is at six face centres. What is the formula of the
edge of the unit cell is 654 pm. Find number of KBr in compound? If side length is 5 Å, estimate the density of
one unit cell. the solid assuming atomic weight of X and Y as 60 and
An element crystallises in a structure having fcc unit 90 respectively.
cell of an edge 200 pm. Calculate its density, if 200 g The element chromium exists as a bcc lattice whose
of this element contains 24 ¥ 1023 atoms. unit cell edge is 2.88 Å. The density of chromium is
An element crystallises into a structure which may be 7.20 g/cc. How many atom does 52.0 g of chromium
described by a cubic type of unit cell having one atom contain?
on each corner of the cube and two atoms on one of its The edge length of the unit cell of MCl (NaCl like
structure; fcc) is 6.28 Å. Assuming anion-cation con-
diagonals. If volume of this unit cell is 24 ¥ 10–24 cm3
tact along the cell edge, calculate the radius of the M+
and density of the element is 7.2 g cm–3. Calculate the
ion. ( rCl- = 1.8173 Å).
number of atoms present in 200 g of the element.
Element A is every element of FCC, atom B is present A cubic unit cell contains manganese ions at the cor-
at every octahedral void, atom C is present at 25% of ners and fluoride ions at the centre of each edge.
(a) What is the empirical formula?
tetrahedral void. Find out the possible molecular for-
(b) What is the C.N. of the Mn ion?
mula of the compound?
(c) Calculate the edge length of the unit cell if the
Thallium chloride, TiCl (240 g mol–1) crystallises in radius of a Mn ions is 0.65 Å and that of F– ion is
either a simple cubic lattice or a face centered cubic 1.36 Å.
lattice Cl– ions with Ti+ ions in the holes. If the density (d) Calculate the density of the compound (Mn = 55,
of the solid is 9.00 g cm–3 and edge of the unit cell is F = 19).
3.85 ¥ 10–8 cm, what is the unit geometry ?
A crystal of lead (II) sulphide has NaCl structure. In
this crystal the shortest distance between Pb+2 ion and
PREVIOUS YEARS’ QUESTIONS
S2– ions is 297 pm. What is the volume of unit cell.
The length of the side of the unit cell is 412 pm and Cl– ion 1. The number of atoms per unit cell in bcc and fcc is
has a radius of 181 pm. Calculate the radius of Cs+ ion. respectively
If the radius of Mg2+ ion, Cs+ ion, O2– ion, S2– ion and (a) 8, 10 (b) 2, 4 (c) 1, 2 (d) 1, 3
Cl– ion are 0.65 Å, 1.69 Å, 1.40 Å, 1.84 Å, and 1.81Å How many unit cells are present in a cube-shaped ideal
respectively. Calculate the coordination numbers of the crystal of NaCl of mass 1.00 g?
cations in the crystals of MgS, MgO and CsCl. (a) 1.28 ¥ 1021 unit cells
Formula mass of NaCl is 58.45 g mol–1 and density of (b) 1.71 ¥ 1021 unit cells
its pure form is 2.167 g cm–3. The average distance be- (c) 2.57 ¥ 1021 unit cells
tween adjacent sodium and chloride ions in the crystal (d) 5.14 ¥ 1021 unit cells
(i) AB crystallises in a rock salt structure with A:B
is 2.814 ¥ 10–8 cm. Calculate Avogadros constant.
= 1:1. The shortest distance between A and B is
An element A (Atomic weight = 100) having bcc struc-
Y1/3 nm. The formula mass of AB is 6.023 Y amu
ture has unit cell edge length 400 pm. Calculate the
where Y is any arbitrary constant. Find the density
density of A and number of unit cells and number of
in kg m–3.
atoms in 10 g of A.

Solid State 4.19
(ii) If measured density is 20 kg m–3. Identify the type (a) 39.27% (b) 68.02% (c) 74.05% (d) 78.54%
of point defect. Copper crystallises in fcc lattice with a unit cell edge of
What type of crystal defect is indicated in the diagram 361 pm. The radius of copper atom is
below? (a) 181 pm (b) 108 pm (c) 128 pm (d) 157 pm
Na+ Cl– Na+ Cl– Na+ Cl– A compound MpXq has cubic close packing (ccp) ar-
– – +
Cl Cl Na Na+ rangement of X. Its unit cell structure is shown below.
Na+ Cl– Cl– Na+ Cl– The empirical formula of the compound is
Cl– Na+ Cl– Na+ Na+
(a) Frenkel defect
(b) Schottky defect
(c) Interstitial defect
M=
(d) Frenkel and Schottky defects X=
The edge length of unit cell of a metals having atomic
weight 75 g/mol is 5 Å which crystallises in cubic lat-
tice. If the density is 2 g/cc then find the radius of metal
atom (NA = 6 ¥ 1023). Give the answer in pm.
Total volume of atoms present in a face centred cubic

unit cell of a metal is (r is atomic radius) (a) MX (b) MX2 (c) M2X (d) M5X14
The arrangement of X– ions around A+ ion in solid AX
is given in the figure (not drawn to scale). If the radius
24 3 12 3 16 3 20 3 of X– is 250 pm, the radius of A+ is
(a) p r (b) p r (c) p r (d) pr
3 3 3 3
In a compound, atoms of element Y form ccp lattice X–
and those of element X occupy 2/3rd of tetrahedral A+
voids. The formula of the compound will be
(a) X4Y3 (b) X2Y3 (c) X2Y (d) X3Y4
In hexagonal systems of crystals, a frequently encountered (a) 104 pm (b) 125 pm (c) 183 pm (d) 57 pm
arrangement of atoms is described as a hexagonal prism. Experimentally it was found that a metal oxide has for-
Here, the top and bottom of the cell are regular hexagons and mula M0.98O. Metal M, present as M2+ and M3+ in its
three atoms are sandwiched between them. A space-filling oxide. Fraction of the metal which exists as M3+ would
model of this structure, called hexagonal close-packed (hcp), be
is constituted of a sphere on a flat surface surrounded in the (a) 7.01% (b) 4.08%
same plane by six identical spheres as closely as possible. (c) 6.05% (d) 5.08%
Three spheres are then placed over the first layer so that they Which of the following exists as covalent crystals in
touch each other and represent the second layer. Each one of the solid state?
these three spheres touches three spheres of the bottom layer. (a) Iodine (b) Silicon
Finally, the second layer is covered with a third layer that (c) Sulphur (d) Phosphorus
is identical to the bottom layer in relative position. Assume CsCl crystallises in body centred cubic lattice. If ‘a’ its
radius of every sphere to be ‘r’. edge length, then which of the following expressions is
The volume of this hcp unit cell is correct?
(a) 24 2r 3 (b) 16 2 r 3 3a
(a) rCs+ + rCl- = 3a (b) rCs+ + rCl- =
64 3 2
(c) 12 2 r 3 (d) r
3 3 3
(c) rCs+ + rCl- = a (d) rCs+ + rCl- = 3a
The empty space in this hcp unit cell is 2
(a) 74% (b) 47.6 % (c) 32% (d) 26% Sodium metal crystallises in a body centred cubic lat-
The packing efficiency of the two-dimensional square tice with a unit cell edge of 4.29 Å. The radius of so-
unit cell shown below is dium atom is approximately
(a) 1.86 Å (b) 3.22 Å
(c) 5.72 Å (d) 0.93 Å
L

Answer Key
LEVEL I
1. (a) 2. (c) 3. (d) 4. (a) 5. (d) 6. (b) 7. (c) 8. (a) 9. (b) 10. (b)
11. (a) 12. (d) 13. (b) 14. (b) 15. (d) 16. (a) 17. (a) 18. (d) 19. (d) 20. (c)
21. (a) 22. (b) 23. (b) 24. (a) 25. (d) 26. (b) 27. (c) 28. (b) 29. (c) 30. (d)
31. (c) 32. (a) 33. (a) 34. (a) 35. (b) 36. (b) 37. (d) 38. (a) 39. (b) 40. (a)
LEVEL II
1. (d) 2. (c) 3. (c) 4. (b) 5. (a) 6. (d) 7. (d) 8. (b) 9. (d) 10. (a)
11. (a) 12. (c) 13. (a) 14. (d) 15. (c) 16. (b) 17. (d) 18. (a) 19. (d) 20. (d)
21. (a) 22. (d) 23. (b) 24. (a)
LEVEL III
1. (A) Æ P, Q, R, (B) Æ P, Q; (C) Æ P, Q, R, S; (D) Æ P, S 2. (A) Æ S; (B) Æ R; (C) Æ P; (D) Æ Q

3. (A) Æ P, Q, R, S; (B) Æ P, R, S; (C) Æ P, S; (D) Æ P, R, S 4. (A) Æ R; (B) Æ S; (C) Æ Q; (D) Æ P
5. (A) Æ Q, R; (B) Æ S; (C) Æ Q, R; (D) Æ P
6. (c) 7. (b) 8. (a) 9. (c) 10. (b) 11. (a) 12. (b) 13. (a) 14. (a, c, d)
15. (a, c) 16. (b, c) 17. (a, b, c) 18. (a, b, c) 19. (269 pm) 20. (fcc)
21. (4) 22. (5.0 kg m–3) 23. (1.002 g cm–3) 24. (a) [367.64] (b) [4.94 ¥ 10–23 cm3] (c) 4 (d) 8.54 g cm–3
25. (25.16%) 26. (AB2O4) 27. (AB3) 28. (a) [335.15 pm] (b) [154.15 pm]
29. (7.886 g/cc in bcc and 8.89 g/cc in fcc) 30. (103.4 pm and cannot slipped) 31. (0.48 and 0.52)
32. (62%) 33. (3.386 ¥ 1024) 34. (390.3 pm) 35. (216.5 pm) 36. (117.2 pm) 37. (1.259)
38. (2.44 ¥ 10–23 cc) 39. (4 ¥ 10–8 cm) 40. (4) 41. (41.7 g/cc) 42. (3.472 ¥ 1024)
43. (A2 B2C) 44. (scc) 45. (2.096 ¥ 10–22 cc) 46. (175.8 pm) 47. (4, 6, 8)
48. (6.05 ¥ 10 )
23
49. (5.188 g/cc, 3.0115 ¥ 1024, 6.022 ¥ 1022) 50. (2.169 g/cc) 51. (15.053%)
52. (6.023 ¥ 1018) 53. (4) 54. (XY3, 4.38 g/cc) 55. (6.05 ¥ 1023) 56. (1.3227 Å)
57. (a - MnF3, b - 6, c - 4.02 Å d - 1)
1. (b) 2. (c) 3. (i) 5 kg/m3 (ii) non stoichiometric defect 4. (b) 5. (216.5 nm) 6. (c)
7. (a) 8. (a) 9. (d) 10. (d) 11. (c) 12. (b) 13. (a) 14. (b) 15. (b) 16. (c)
17. (a)
Hints and Solutions

LEVEL I Au = 8 ¥
1
=1
8
1
B=8¥
1
=1 A=1¥1 Cu = 6 ¥ = 3
8 2
\ MF = AB \ formula AuCu3

Solid State 4.21
[3 ¥ M ]
7.2 =
F F 6.023 ¥ 1023 ¥ 24 ¥ 10-24
F K
F F 2.67
Ê 200 ˆ
F fi Number of atoms in 200 g = ÁË ¥ NA˜
F F
K M ¯
F F fi a= 2
F
F 2.67 = 3.472 ¥ 1024 atoms
F F
a = 620 pm
(distance) fi 267 2 fi 377.6 pm a
r1 = nearest neighbour =
z ¥ Molar mass 2
d=
N A ¥ a3 r2 = next nearest neighbours = a = 620
200 M Ê 200 ˆ
4 ¥ 143.5 ¥ N A = 5 ¥ 1024 ◊ =
a3 = V = M N A ÁË 5 ¥ 1024 ˜¯
6.023 ¥ 1023 ¥ 5.561
M
170.954 ¥ 10-24 ¥ 100 4¥
V = 17.137 ¥ 10–23 = NA
17.137 ¥ 10-23 d= = 20 g cm3
(200 ¥ 10 –10 )3
(5.55 ¥ 10 –8 )3 a 3 = 2rCs+ + 2rCl– ◊ rCl– = 1.81 Å
% occupied = ¥ 100 = 99.75
Volume
% unoccupied fi 0.245 Effective number of Rhenium =
1
¥8=1
For fcc 8
Z¥M total mass 1
Use d = = Effective number of oxygen = 12 ¥ =3
N A ¥ a 3 Total volume 4
\ formula = ReO3 or Re2O6
È 40 + 2 ¥ 19 ˘
4¥Í 23 ˙
1
Effective number of Ca = 8 ¥ = 1
Î 6.023 ¥ 10 ˚ 8
d = 3.18 = fi a = 344 pm
(a ¥ 10 –10 )3 Effective number of Ti = 1 ¥ 1 = 1
1
2 Effective number of O = 6 ¥ =3
A=6 C=6¥ =4 2
3 \ formula = CaTiO3
A 6C4 fi A3C2 or C2A3 a r
X=4 h /2 h
2 2
1 = fi =
Y=8 =2 Z=4¥ a 3 4r 3
2
\ formula X4Y8Z2 OR X2Y4Z h 3
\ r=
a = 480 pm 4 2
a 3 = 2rx+ + 2ry – Volume of hexagonal = 24 2 r3

3
480 ◊ 3 = 2rx+ + 2 ¥ 225 fi rx+ = 190.68 pm Cross-section area of hexagonal = 6 ¥ ¥ 4r2
4
rA+1 22.5 = 6 3r 2
= 0.225 =
rB –1 rB – Volume = Height ¥ Area = 24 2 r3
rB –1 = 100 pm Effective number of N = 6
1
a = 387 pm Effective number of Nb = 6 ¥ 2 ¥ = 6
2
a 3 \ formula = Nb6N6
d NH+ -Cl – = = 335.1 pm
4 2 or = NbN
1 The Coordination Number of CsCl is 8
A=4 B=8¥ =2 4
4 22. For bcc edge length (a) = r
1 3
C=4¥ \ formula A4B2C2 4
2 = ¥ 80
1.732
1
Z=8¥ +2=3 = 184.7 pm
8

For NaCl like structure. The radius ratio should be l

(Since C.N = 6) In second case, 1 ¥ l = 2 ¥ ¥ sin q
or sin q = 1 = sin 90º 2
fi 0.414 to 0.732
or q = 90º
r + 100 100
= – = 0.414 , – = 0.732 A4 4 B 2
r - rmax rmin. +
8 2
4–1–
4
100 A2.5 B2.5 or AB

\ –
rmax = = 241.6 pm
0.414 Total number of atoms in 1 hcp unit cell =
100 12 2 3
\ –
rmin = = 136.6 pm + +
0.732 6 2 1
Since, P atoms are forming the lattice reference \ [(12 corner, 2 face centered, 3 body centers)] = 2 + 1 +
No. of P atom 4(ccp) and 4 atoms (Q) from the half of 3=6
the tetrahedral void contributes one unit cell. So, for-
mula of solid is P4Q8 so, the simplest formula of the h 4r 2 12r 2 - 4r 2 2
= 4r 2 - = = 4r
solid is PQ2. 2 3 3 3
In simple cubic arrangement, number of atoms = 1, Area of base = area of 6 equilateral Dle
a = 2r 3
Volume occupied by one atom =6¥ (2r ) 2
\ packing fraction = 4
Volume of unit cell 3
\ volume = area of base ¥ height = 24 2r
4 3 4 3
pr pr X 7 Y3 Z 1 fi \ X7Y24Z
3 3 p
= 3
= 3
= 8 8
a (2r ) 6 Volume of all atoms in 1.68 gm Argon

d ¥ a3 ¥ N A 1.68 4
M= = ¥ NA ¥ ¥ p ¥ (1.5 ¥ 10–8)3 = 0.3564
Z 40 3
Volume of solid argon = 1 cm3 = Volume of unit cell
10 ¥ (200 ¥ 10 –3 )3 ¥ (6.02 ¥ 1023 ) % empty space = (1 – 0.3564) ¥ 100 = 64.36
4 Number of atoms of B in unit cell = 2
= 12.04 g Total volume of B unoccupied by A
6.02 ¥ 1023 4 7p R3
Number of atoms in 100 g = ¥ 100 In a unit cell = 2 ¥ ( R3 – r 3 ) ¥ p =
12.04 3 3
= 5 ¥ 1024 64 3
It is the characteristic fact. Volume of unit cell = a3 = R
3 3
In hcp unit cell
For bcc 3a = 4R
2
= C = 4r 7p R3 /3 7p
3 \ rratio = =
64 3 64 3
a = 2r R
3 3
C 2 8 1
\ =2 = Number of atoms of ‘A’ in a unit cell ¥8=1
a 3 3 8
Since the C.N. of fluorite and antifluorite structure are 1
Number of atoms of ‘B’ in a unit cell ¥6=3
same, hence by interchanging the positions of cation 2
and anions lattice can be interchanged. \ formula of the compound = AB3
Since, A forming the lattice reference. a = 2[r+ + r–] = 400
2 2r+ = 400 – 2 ¥ 75
The number of C in one unit cell = ¥ 6 = 4 2r+ = 250
3
\ m.f is C4A6 ∫ C2A3 \ r+ = 125
n ¥ l = 2d sin q a 2 = 4r
In first case, 1 ¥ l = 2l sin q
a 2 a
1 \ r= =
or sin q = = sin 30º 4 2 2
2
or q = 30º 4 3
\ Total volume of 4 atoms = 4 ¥ p r
3

Solid State 4.23
3 It is a typical zinc blende (ZnS) structure

4 È a ˘ p a3
=4¥ pÍ = but in question symbol Q atoms are cubic close packed, R atoms are situated in
3 Î 2 2 ˙˚ 3 2 alternate tetrahedral voids.
of edge length given r –QRQ = 109°28 (tetrahedral)
p r3 Coordination number
\ Total volume = With respect to Q = 4
3 2
With respect to R = 4
For a bcc lattice
LEVEL II
x+ 0.4
-
= 0.732 fi y– = = 0.546 Å
y 0.732
M ¥Z
a3 = pm3
d ¥ N A ¥ 10 –30 z+
Now for fcc lattice = 0.414
y-
93 g mol –1 ¥ 2
= pm3 fi z+ = 0.544 ¥ 0.414 = 0.226 Å
8.55 g cm –3 ¥ 6.02 ¥ 1023 mol –1 ¥ 10 –30
2 ¥ 56
a3 = 3.61 ¥ 107 = 36.1 ¥ 106 pm3 d1 = g/cc
3
a = (36.1)1/3 ¥ 102 pm = 3.304 ¥ 102 pm = 330.4 pm Ê 4r ˆ
ÁË ˜¯ ¥ N A ¥ 10
–30
For body centred cubic, 3
3 4 ¥ 56
r= a = 0.433a = 0.433 ¥ 330.4 pm = 143.1 pm. d2 = g/cc
4 (2 2 ◊ r )3 ¥ N A ¥ 10 –30
Atoms occupying at tetrahedral holes and octahe- d1
dral holes do not touch with each other if touches dis- = 0.918
d2
tortion in ccp seen.
3
In CCP anions oxide ion are forming the lattice ref- Z d FCC Ê Z FCC ˆ Ê aBCC ˆ
dμ \ =
erence and cations occupied voids. In ccp there are two a 3 d BCC ÁË Z BCC ˜¯ ÁË aFCC ˜¯
tetrahedral voids and one octahedral hole.
3
For one oxygen atom there are two tetrahedral holes 2 4 È aBCC ˘
fi = fi 1:1
and one octahedral hole. 1 2 ÍÎ aFCC ˙˚
Since one fifth of the tetrahedral voids are occupied
by divalent cations (X2+). Z¥M
d=
\ number of divalent cations in tetrahedral voids = N A ¥ a3
1
2¥ d ¥ N A ¥ a 3 2 ¥ 6 ¥ 1023 ¥ 5 ¥ 5 ¥ 5 ¥ 10-24
5 Z= =
M 75
Since half of the octahedral voids are occupied by tri-
= 20 ¥ 10–1 = 2
valent cations (Y3+)
1 Therefore, the cubic lattice will be body centered.
\ number of trivalent cations = 1 ¥ For bcc lattice: 3a = 4r
2
So the formula of the compound is X2/5Y1/2O or X4Y5O10 3
For fcc lattice \ r= a , since a = 5 Å = 5 ¥ 102 pm
4
4r = 2a where a = 620 pm 1.732 ¥ 5 ¥ 102
1 = = 2.165 ¥ 102 = 216.5 pm
r= ¥a 4
2 2 rA = rNa + , rB = rCl-
1
¥ 620 m = 219.20 pm rA
2 2 (i) = 0.414 is the ideal radius ratio for NaCl
rB
Cs Cl has bcc structure and for it
structure.
3¥a 3 ¥ 0.4123 r ¢+
rCs+ + rCl- = = r 41.4 30
2 2 (ii) rB = A = pm = 100pm A = = 0.3
0.414 0.414 rB - 100
0.7141
= = 0.3571 nm Radius ratio is in 0.225 – 0.414 range which is for
2
rCs+ = 0.3571 - 0.181 = 0.176 nm tetrahedral. It crystallises in ZnS type of structure.
Coordination number of A+ ion changes from 6
(in NaCl) to 4 (in ZnS) type of structure

ABCABC… pattern gives rise to face centred cubic rNa + rK +

lattice. The layers (ABCA) are present perpendicular to = 0.55, = 0.74
the body diagonal of the unit cell. rCl- rCl-
\ the distance between two successive layers = rNa +
Ê Length of body diagonal ˆ + 1 = 1.55 ...(1),
ÁË ˜¯ and a = 2 2r rCl-
3
for FCC or CCP rK +
+ 1 = 1.74 ...(2)
rCl-
3a 3 2
= = 2 2r = 2r
3 3 3 Dividing (ii) by (i)
1 unit cell volume (a ) = 27 ¥ 10 cm
3 –24 3
1.74 rK + + rCl- rCl-
= ¥ = 1.123
1024 1.55 rCl- rNa + + rCl-
1 cm3 volume contains = unit cells
27
density given 10 g/ml S2–
a/2
1024
10 g of metal of 1 ml of metal contains unit cells a/2
27
\ 16.2 g metal contains S2– a/2
16.2 10 24 Zn 2+
= ¥ = 6 ¥ 1022 (unit cell)
10 27 S2–
Volume of cuboid box = 4R ¥ 4R ¥ 2R = 32R3
16 3
Volume of 4 sphere = pR S2–
3
16 3 Let edge length of the unit cell = a
pR
Volume occupied by spheres 3 p a 1
P.F. = = 3
= 3¥ ¥ = r 2+ + r 2-
Total volume 32 R 6 2 2 Zn S
Ê pˆ a
= 0.83 + 1.74 = 2.57
Percentage vacant space = 100 Á1 - ˜ or 3
Ë 6¯ 4
3.61 4
4r = 2 a r = = 1.28 Å or a = 2.57 ¥ = 5.935 Å
2 2 3
We have to find the radius of dark circle in the figure. The packing efficiency = 0.68, means the given lat-
tice is bcc.
The closest distance of approach = 2r
3a 2 ¥ 2.86
3.61 - 2.56 2r = 2.86 Å = or a = = 3.30 Å
Radius = = 0.525 Å 2 3
2
2 Let atomic weight of the element = M
The height of the hcp unit cell = 4 ¥ r = 5.715
3 2¥M
\ = 8.57
5.715 ¥ 3 6 ¥ 10 ¥ (3.3)3 ¥ 10 –24
23
\ r= = 1.75 Å
2¥4 M = 8.57 ¥ 3 ¥ (3.3)3 ¥ 0.1 = 92.39 93
The base area of the unit cell = 6 3 r 2
Let total number of atoms present in the unit cell =
The volume of the unit cell = Base area ¥ Height
n
= 24 2 r 3 = 181.8 Å3 3 n
\ number of Mn atoms = n; number of Si atoms =
When all particles along one body diagonal are 4 4
removed, 2X particle from corner are removed, one Y Ê3 n ˆ
particle is removed and 2Z particle is removed. ÁË n ¥ 55 + ¥ 28˜¯
4 4
\ = 6.85
X particle =
1 1
¥6+ ¥6=
15 6 ¥ 1023 ¥ (2.86)3 ¥ 10-24
8 2 4 n[41.25 + 7]
(Y particle = 3, Z particle = 6) or = 6.85
6 ¥ 23.39 ¥ 0.1
\ X 15 Y3 Z 6 = X 5Y4 Z 3 6.85 ¥ 6 ¥ 2.339
4
or n= = 1.99 2
48.25

Solid State 4.25
Let C–C bond distance in graphite is a Å

LEVEL III
3
\ surface area = 6 ¥ ¥ a2
4
3 1. (A) Æ P, Q, R, (B) Æ P, Q; (C) Æ P, Q, R, S; (D) Æ P, S
=6¥ ¥ a2 ¥ 10–16 cm2 2. (A) Æ S; (B) Æ R; (C) Æ P; (D) Æ Q
4
3. (A) Æ P, Q, R, S; (B) Æ P, R, S; (C) Æ P, S; (D) Æ P, R, S
\ volume of the unit cell
4. (A) Æ R; (B) Æ S; (C) Æ Q; (D) Æ P
3 5. (A) Æ Q, R; (B) Æ S; (C) Æ Q, R; (D) Æ P
=6¥ ¥ a2 ¥ 10–16 ¥ 3.35 ¥ 10–8 cm3
4 Cubic close packing is fcc both ccp and hcp have a
\ mass of the unit cell packing fraction = 0.74. They both have a coordination
number of 12.
3
=6¥ ¥ 3.35 ¥ a2 ¥ 2.25 ¥ 10–24 g.
4
1
\ 6¥
3
¥ 3.35 ¥ 2.25 ¥ 10–24 ¥ a2 Number of Ca atoms = 8 ¥ =1
4 8
1
10 Number of O–atoms = 6 ¥ =3
= 12 ¥ ¥ 10–24 ¥ 2 2
6 Number of Ti–atoms = 1 ¥ 1 = 1
10 1¥ 2 Total number of atoms = 5
\ a2 = ¥4 = 2.04265
3 3 ¥ 3.35 ¥ 2.25 CaTiO3
or a = 1.429 Å 2+x–6=0
CCP means Z = 4 and a = 2 2r x=4
If no O–atom is removed from alternate position
4 4 4
4 ¥ p r 3 + 4 ¥ p ¥ (0.414r )3 + 8 ¥ p ¥ (0.225r )3 (face)
P.F. = 3 3 3 1
(2 2r )3 Number of O–atom remain = ¥ 2 = 1
2
4 Hence formula of perovskite is CaTiO.
4 ¥ p r 3[1 + (0.414)3 + 2 ¥ (0.225)3 ]
P.F. = 3
16 2r 3
Let iron present in +3 oxidation state is x, then
p
P.F. = [1 + (0.414)3 + 2 ¥ (0.225)3 3x + 2(0.95 – x) = 2, x = 0.1
3 2 0.1
p % of Fe in +3 oxidation state = ¥ 100 = 10.5%
= (1 + 0.070958 + 0.022781) 0.95
3 2 As cation size increase more number of anion can
or P.F. = 0.8096 0.81 attached with it hence C. No increase.
a/2
a/ 2 x
void a/2
Square close packing Hexagonal close packing and
a/2 Not possible in closest triangular close packing are
packing possible
In MgO electrostatic attraction between Mg2+ and
2–
O is much greater than the electrostatic attraction be-
a2 a2 a2 a tween Na+ and F–.
x= + = =
4 4 2 2 NaCl or Rock Salt Type
The atom present in the void will touch the atom at the
corner at first Cl–
3a Na+
\ rx + r = a/2; 4r = 3a or r =
4
a 3a 2a 3a a
\ rx = - = - = (2 - 3)
2 4 4 4 4
= 0.067a
\ 2rx = 2 ¥ 0.067a = 0.134a.

1. Cl– is present at each corner and on each face Length of the edge of unit cell = 408 pm
centre whereas Na+ is present on edge center and Volume of unit cell = (408 pm)3 = 67.92 ¥ 10–24 cm3
body center or vice versa. Mass of unit cell = Density ¥ Volume
2. Cl– is present in FCC lattice while Na+ occupy all = 10.6 g cm–3 ¥ 67.92 ¥ 10–24 cm3 = 7.20 ¥ 10–24g
the octahedral holes.
Mass of unit cell = Number of atoms in unit cell ¥ Mass
2(r+ + r–) = a = edge length
of each atom
4r– = a 2 Only for ideal crystal, i.e. anion-anion Now, mass of each atom
contact.
Atomic mass 108
Cs Cl packed in bcc unit cell = = = 1.79 ¥ 10–22g
r+ = 0.165 nm, r– = 0.181 nm Avogadro number 6.023 ¥ 1023
3a = 2r + + 2r – Let the unit cell contain ‘Z’ atoms, so that
Mass of unit cell = Z ¥ 1.79 ¥ 10–22 = 7.20 ¥ 10–22
(2 ¥ 0.165) + (2 ¥ 0.181)
a= = 0.399526 = 0.4 nm 7.20 ¥ 10-22
3 Z= = 4.02
Z ¥ M (kg) 1.79 ¥ 10-22
1 ¥ 168.5 ¥ 10 –3
Density = =
N A ¥ a(meter)
3
6.02 ¥ 1023 ¥ (0.4 ¥ 10 –9 )3 \ number of atoms present in a unit cell = 4
AB has rock salt (A:B::1:1) structure, i.e., fcc structure
= 437 ¥ 10–26 ¥ 1027 = 4.37 ¥ 103 kg/m3 (n = 4) and formula weight of BB is 6.023 y amu having
closest distance A – B y1/3 nm. Therefore edge length of
d ◊ a 3 N A 10.5 ¥ (4.07 ¥ 10-8 )3 ¥ 6.023 ¥ 1023 unit cell = 2(A+ + B–) = 2 ¥ y1/3 ¥ 10–9 m
Z Ag = = =4
M 108 Z¥M
\ Density of AB =
(4.05 ¥ 10-8 )3 ¥ 2.7 ¥ 6.023 ¥ 1023 N A ¥ a3
Z Al = =4
27
4 ¥ 6.023 ¥ y ¥ 10-3
(3.61 ¥ 10-8 )3 ¥ 8.92 ¥ 6.023 ¥ 1023 =
Z cu = =4 6.023 ¥ 1023 ¥ (2y1/3 ¥ 10-9 )3
63.5
Hence all crystallises in FCC unit cell. (molecular weight in kg)
= 5.0 kg m–3
See HCP Diagram and FCC diagram in theory. 1
The total number of atoms per unit cell = 8 ¥ +1= 2
2
See dielectric properties of solid in theory. Z¥M 2 ¥ 23
Density = =
NA ¥ a 3
6.023 ¥ 10 ¥ (4.24 ¥ 10-8 )3
23
See Classification of solid in theory.
Due to NaCl type structure, Z = 4 = 1.002 g cm–3 approx. 1g/cc
Z¥M Z¥M
\ d= As we know d = ,
a3 N A N A ¥ a3
Z¥M 4 ¥ 58 (a) For fcc structure 4r = 2a , a = 2 2 r
\ a3 = =
d ¥ N A 2.48 ¥ 6.02 ¥ 1023 = 2 2 ¥ 130 pm = 367.64 pm
a = 5.3762 ¥ 10-8 cm (b) Volume of unit cell = a3 (3.67 ¥ 10–8 cm)3
= 4.94 ¥ 10–23 cm3
\ 2(r+ + r–) = a (c) Z = 4
a (d) density = 8.54 g/cm3
\ (r + + r - ) =
2 Given data show ZnS type crystal
= 2.688 ¥ 10–8 cm = 269 pm
p ÈÍÊ r + ˆ ˘
3
\ ÁË - ˜¯ + 1˙
(ans :- fcc) PF =
From equation 3 2 ÎÍ r ˚˙
d(density) = 3.35 gm/cm3 3.14 r+
= [(0.225)3 + 1] Since - = 0.225
Z¥M Z ¥ 56 3 2 r
d= =
a 3 ¥ N A (4.8 ¥ 10-8 )3 ¥ 6 ¥ 1023 3.14 ¥ 1.0114
= = 0.7486
\ Z=4 3 ¥ 1.414
So, cubic system is fcc type. % of void = 100 – 74.86 = 25.16%

Solid State 4.27
Since oxide ion forming the lattice reference a = 2r Volume of the cube = a3 = (2r)3 = 8r3
\ Number of oxide ion = 4 r r
Number of tetrahedral voids in lattice = 2 ¥ 4 = 8
1
Number of divalent cation (A) = ¥8=1
8
Number of octahedral voids in lattice = 1 ¥ 4 = 4
a
1
Number of trivalent cations (B) = ¥ 4 = 2
2 Volume of one atom
\ Formula = AB2O4 Packing fraction =
Volume of the cube
A atom are eight corners of the cube.
Therefore, the number of A atoms in the unit cell = 8 ¥ Ê 4 3ˆ
ÁË p r ˜¯ p
1/8 = 1 3
= = = 0.52
B atoms are at the face centre of six faces = 6 ¥ 1/2 = 3 8r 3 6
The formula is AB3. \ void fraction = 1 – 0.52 = 0.48 \Void space = 48%
In a body centred cubic lattice, oppositely charged 4
ions touch each other along the body-diagonal of the Volume of one atom of Ar = p r 3
3
cube. So, we can write,
1.65
2r+ + 2r– = 3a Also, number of atoms in 1.65 g = ¥ 6.023 ¥ 1023
40
3 3 \ total volume of all atoms of Ar in solid state
r + + r– = a= (387 pm) = 335.15 pm 4 1.65
2 2 = p r3 ¥ ¥ 6.023 ¥ 1023
Now, since r– = 181 pm 3 40
We have, r+= (335.15 – 181) pm = 154.15 pm 4 22 1.65
= ¥ ¥ (1.54 ¥ 10 –8 )3 ¥ ¥ 6.023 ¥ 1023
In a body centred unit cell, atoms touch each other 3 7 40
along the body-diagonal. = 0.380 cm3
Hence, 4r = 3a Volume of solid argon = 1 cm3
4 4 [1 – 0.380]
a= r= (124 pm) = 286.4 pm \ % empty space = ¥ 100 = 62%
3 3 1
for bcc lattice, Z = 2, Hence, Volume of unit cell = a3 = (2.88 Å)3 = (2.88 ¥ 10–8 cm)3
= 23.887 ¥ 10–24 cm3
ZM 2 ¥ 55.8
r= = -12 3
Volume of 288 g of the element
a N A (286.4 ¥ 10 ) ¥ 6.023 ¥ 1023
3
Mass 288 g
= 7.887 ¥ 106 g–3 = 7.886 g/cc = = = 40.499 cm3
Density 7.12 g cm –3
In a face centred unit cell, atoms touch each other along Number of unit cells in the given volume of the ele-
the face diagonals. ment
Hence, 4r = 2a Volume of the element 40.449
= =
4 Volume of the unit cell 23.887 ¥ 10 –24
a= r = (124 pm) = 350.7 pm
2 = 1.693 ¥ 1024
For fcc lattice, Z = 4, hence, each unit cell of bcc lattice contains 2 atoms
= 8.89 ¥ 106 g m–3 = 8.89 g cm–3 \ number of atoms in 288 g of element
As A B has NaCl structure, A+ ions will be present in
+ –
= Number of unit cells ¥ number of atoms per unit cell
the octahedral voids. Ideal radius of the cation will be = 1.693 ¥ 1024 ¥ 2 = 3.386 ¥ 1024
equal to the radius of the octahedral void because in In a body centred cubic unit cell, the distance between
that case it will touch the anions and the arrangement the cation and anion (r+ + r–) is related to the edge
will be closely packed. Hence, length (a) by
Radius of the octahedral void = rA+ = 0.414 ¥ rB -
= 0.414 ¥ 250 = 103.4 pm r+ + r– = 3 ¥
a
Radius of the tetrahedral site = 0.225 ¥ rB - 2
= 0.225 ¥ 250 pm = 56.25 pm 2 +
As the radius of the cation C+ (180 pm) is larger than the \ a= (r + r - )
3
size of the tetrahedral site, it cannot be slipped into it.

It is given that (r+ + r–) = 338 pm 1 g atomic weight of Hg = 200 g = weight of 6.023 ¥
1023 atoms
2 676
\ a= ¥ 338 pm = = 390.3 pm 6.023 ¥ 1023
3 1.732 Number of atoms present in 1 g of Hg =
200
Edge length of unit cell = 5 ¥ 10–8 cm = 3.0115 ¥ 1021
Volume of 1 atom of Hg or unit cell =
Density = 2.0 g/cc, molecular mass = 75
NA = Avogadro number = 6 ¥ 1023 1 g of Hg
Number of atoms ¥ density
Z¥M Z ¥ 75
d= = 2.0 = -8 3 1
a ¥ NA (5 ¥ 10 ) ¥ 6.0 ¥ 1023 = 2.44 ¥ 10-23 cm3
3
=
13.6 ¥ 3.0115 ¥ 1021
125 ¥ 10-24 ¥ 6.0 ¥ 1023
Z =2¥ =2 Since element has fcc structure hence there are 4 atoms
75 in a unit cell (or Z = 4), Atomic mass is 60 (or M = 60),
Hence, it is a body centred cubic structure NA = 6.02 ¥ 1023 and d = 6.23 g cm–3.
Z¥M Z¥M
3 3 d= \ a3 =
r= ¥a= ¥ 5Å = 2.165 Å = 216.5 pm a ¥ NA
3
d ¥ NA
4 4
For a face centred cubic crystal (4) (60 g mol –1 )
=
(6.23 g cm –3 )(6.02 ¥ 1023 mol –1 )
a 2 = 4r , r = radius of sphere
240 ¥ 10-23
2 a = = 6.4 ¥ 10-23 cm3
r= a= 37.5046
4 2 2 a3 = 64 ¥ 10–24 cm3
400 ¥ 2 \ a = 4 ¥ 10–8 cm
= = 100 ¥ 1.414
4 Length of the edge of the unit cell
= 141.4 pm. a = 654 pm = 6.54 ¥ 10–8 cm
\ volume (V) of the unit cell = (6.54 ¥ 10–8 cm)3
For an octahedral void
Molecular mass of KBr = 39 + 80 = 119 g mol–1
a = 2(r + R)
Density of KBr = 2.75 g cm–3
Diameter of sphere = 2R = a – 2r = 400 – 2 ¥ 141.4
Diameter = 2R = 400 – 282.8 = 117.2 pm Z¥M d ¥ a3 ¥ N A
Length of edge of fcc = 3.5 Å, noumber of atoms in fcc d= \ Z =
a3 ¥ N A M
(Z1) = 4
length of edge of bcc = 3.0 Å, number of atoms in bcc (2.75 g cm –3 )(6.54 ¥ 10 –8 cm)3 (6.023 ¥ 1023 mol –1 )
=
(Z2) = 2 119 g mol –1
Z1 ¥ M 2.75 ¥ (6.54)3 ¥ (6.023)(10 –1 )
Density of fcc = dfcc = , N = Avogadro number = =4
V1 ¥ N A A 119
Atomic weight of metal = M, V1 = (3.5 ¥ 10–8)3 = a13 Z¥M Total Mass
Use d = =
4¥M a ¥ N A Total volume
3
d fcc = (i)
(3.5 ¥ 10-8 )3 ¥ N A a3 = 24 ¥ 10–24 cm3 and d = 7.2 g cm–3
Mass of the element (M) = 200 g
V2 = (3.0 ¥ 10–8)3 volume of bcc unit cell
Number of the atoms (Z) per unit cell
2¥M = (1/8) ¥ 8 + 1 ¥ 2 = 3 atom
dbcc = (ii)
(3 ¥ 10-8 )3 ¥ N A Z¥M Total Mass
d= 3 =
Divide Eq. (i) by (ii) a ¥ N Total volume
d fcc 4¥M (3 ¥ 10-8 )3 ¥ N A N=
(3) (200 g)
= ¥
-8 3
dbcc (3.5 ¥ 10 ) ¥ N A 2¥M (24 ¥ 10 cm3 )(7.2 g cm -3 )
–24
d fcc 4 ¥ 27 N = 3.472 ¥ 1024 atoms

= = 1.259
dbcc 2 ¥ (3.5)3 Atom A is every element of fcc = 4 atoms of A
Atom B is present at every octahedral void = 4 atoms of B
d = 13.6 g/mL
25
Atomic mass of Hg = 200 = M Atom C is present at 25% of tetrahedral void = 8 ¥
= 2 atoms of C 100

Solid State 4.29
So, the possible molecular formula is A4B4C2 = A2B2C. Ê 10 ˆ

(Ans:- scc) VTotal = ÁË ˜ = 1.9275 cm3
5.188 ¯
Z¥M
d= 1.9275
a3 N A fi Number of unit cells =
(400 ¥ 10 –10 )
da 3 N A = 3.0115 ¥ 1022 unit cells
\ Z=
M Ê 58.5 ˆ
4¥Á
9.00 ¥ (3.85 ¥ 10 –8 )3 ¥ 6.02 ¥ 1023 Ë N A ˜¯
= d= = 2.16 gm/cm3
240 (0.564 ¥ 10 –7 )3
= 1.3(= 1) being whole number Fe0.93O
Thus simple cubic lattice. fi x¥3+y¥2=2 (i)
x + y = 0.93 (ii)
rPb+2 + rS-2 = 297 pm
y
a = 2 ¥ 297 pm = 5.94 ¥ 10–8 cm % Fe+2 = ¥ 100 = 15.053%
0.93
V = a3 = 2.096 ¥ 10–22 cm3
Since one Sr+2 can replace two Na+ So each doping will
a 3 = 2rCl – + 2rCS+ create vacancy so total vacancy per mole
412 3 = 2 ¥ 181 + 2rCS+ 10 –3
= 6.023 ¥ 1023 ¥ = 6.023 ¥ 1018
100
rCS+ = 175.8 pm È ˘
3
V = Ía 2 ¥ 2˙ ¥ b
Î 4 ˚
S.No. Radius ratio C.N. Shape M 18
Z¥ Z¥
1. < 0.155 2 Linear NA 6.023 ¥ 1023
d= =
2. [0.155 to 0.225) 3 triagonal planner. V È 3 ˘
Í ¥ (4.53)3 ¥ (10 –8 ) 2 ¥ (7.6 ¥ 10 –8 ) ˙
3. [0.225 to 0.414) 4 Tetrahedral Î 2 ˚
4. [0.414 to 0.732) 6 Octahedral Z =4
5. [0.732 to 1) 8 BCC x y
1 1
rMg +2 0.65 8¥ 6¥ fi XY3
MgS fi = = 0.35 8 2
rS–2 1.84 1 ¥ [60 + 3 ¥ 90]
CN = 4 Mass of unit cell 6.023 ¥ 1023
rMg +2 d= =
0.65 a3 (5 ¥ 10 –8 cm)3
MgO fi = = 0.464
rO –2 1.40 = 4.38 gm/cm3
CN = 6
Z¥M
rCs+ 1.69 Density d =
CsCl fi = = 0.933 a3 N A
rCl – 1.81
CN = 8 7.2 ¥ 6.02 ¥ 1023 ¥ (2.88 ¥ 10 –8 )3
Z¥M = = 51.77 g mol–1
d= 3 2
a NA 52.0 52 N A
Z¥M \ 52.0 g = mol = = 6.05 ¥ 1023 atoms
\ NA = 3 51.77 51.77
a ¥d For fcc structure,
4 ¥ 58.45 a
= Edge length r(M+) + r(Cl–) =
(2 ¥ 2.184 ¥ 10 –8 )3 ¥ 2.167 2
6.28
= 6.05 ¥ 1023 mol-1 r(M+) + r(Cl–) = =3.14 Å
2
10
No. of atoms = ¥ NA = 0.1 NA r(M+) = 3.14 – 1.8173 = 1.3227 Å
100 1
(a) Number of Mn atoms at corners = 8 ¥ =1
Ê 10 ˆ 8
ÁË 2 ¥ N ˜¯ 6
d=
A
= 5.188 g/cm3 Number of F atoms at faces = = 3
(400 ¥ 10 –10 ) 2

Empirical formula = MnF3 Number of tetrahedral voids = 2 ¥ 4 = 8

(b) C.N. = 6 structure being fcc type \ Number of X atom per unit cell
(c) a = 2(r+ + r–) = 2(0.65 + 1.36) = 4.02 Å 2 16
(d) Total atoms in the unit cell = 4 [one Mn and three F] = ¥8=
3 3
\ z=1
\ Formula = X 16 Y4 = X16Y12 = X 4Y3
Z¥M 3 1
d= 3 = 2.86 g/cm3
a NA
PREVIOUS YEARS’ QUESTIONS

Number of per atom unit cell in bcc and fcc are 2
and 4 respectively.
h = height
One unit cell of NaCl contains of hexagon
4 NaCl units which has
4 ¥ 58.5
Mass = g
6.02 ¥ 1023
\ number of unit cells in
6.02 ¥ 1023
1g = = 2.57 ¥ 1021
4 ¥ 58.5
a = 2r
Z¥M
(i) d = 3 Effective no. of atoms in unit cell (Z)
a ¥ NA
È 1 1˘
a = 2Y1/3 ¥ 10–9 m = Í1 ¥ + 6 ¥ ¥ 2 + 3 ¥1= 6
Î 2 6 ˙˚
6.023
M = 6.023 Y = Y kg. = 6.023 ¥ 10–3 Y kg \ Z=6
1000
Total atoms = 6
4 ¥ 6.023 ¥ 10 –3 ¥ Y 3 3
d= Volume of hexagonal unit cell = 6 ¥ a ¥h
6.023 ¥ 1023 ¥ (2Y 1/3 ¥ 10 –9 )3 4
4 ¥ 6.023 ¥ 10 ¥ Y h
=
6.023 ¥ 8 ¥ Y 2
Since 2 =
d = 5kg/m3 a 3
(ii) Observed density is higher – non-stoichiometric 2

\ h = 4r
defect. 3
As equal number of Na+ and Cl– ions are missing
3 2
from their lattice site so it is Schottky defect. and V =6¥ ¥ (2r ) 2 ¥ 4r = 24 2 r 3
4 3
Z¥M
d= 3 \ Packing fraction
a ¥ NA
6 ¥ 4/3p r 3 p
Z ¥ 75 = = = 0.74.
2= fi Z = 2(bcc) 24 2r 3
3 2
(5 ¥ 10 –8 )3 ¥ 6 ¥ 1023
Vacant space = 100 – 74 = 26%
3 3
For bcc: r = ¥a= ¥5 Diagonal = 4r = 2 ¥L
4 4
r = 216.5 nm 4r
L=
Total number of atoms in fcc = Z = 4 2
4 Area = L2 = 8r2
Assuming atom to be spherical, its volume = p r 3
Total volume of all atoms present in fcc 3 1
Number of spheres = 1 + 4 ¥ = 2
4 ¥ 4p r 3 4
=
16
= p r3 Area of each = pr2
3 3 2 ¥ pr2 p
Since element Y form lattice reference Packing fraction = = = 0.785
\ Number of Y atom in one unit cell = 4 8r 2 4

Solid State 4.31
For fcc: Total M3+ present in one molecule of

2a = 4r MO = 2 ¥ 0.02 = 0.04
\ total M2+ and M3+ = 0.98
2
r= ¥ 361 = 127.6 0.04 ¥ 100
4 Thus, % of M 3+ = = 4.08%
0.98
1
Number of M = ¥ 4 + 1 = 2 OR
4
1 1 2x + (0.98 – x) ¥ 3 = 1 ¥ 2
Number of X = ¥ 6 + ¥8=4
2 8 0.98 - x
% of M+3 = ¥ 100 = 4.08%
M2X4 = MX2 0.98
Given arrangement represents octahedral void and Silicon exists as covalent crystal in solid state.
for this (Network like structure, as seen in diamond.)
r+ (cation) In CsCl, Cl– lies at corners of simple cube and Cs+
= 0.414
r- (anion) at the body centre. Hence, along the body diagonal, Cs+
r ( A+ ) and Cl– touch each other so
= 0.414
r( X - ) 2(rCs+ + rCl- ) = 3a
r(A ) = 0.414 ¥ r(X ) = 0.414 ¥ 250 pm
+ –
= 103.5 pm = 104 pm 3
Hence, \ rCs+ + rCl- = a
From the valency of M2+ and M3+, it is clear that 2
three M2+ ions will be replaced by two M+3 causing a
For bcc unit cell, 3a = 4r
loss of one M3+ ion. Total loss of them from one mol-
ecule of MO = 1 – 0.98 = 0.02 3 3
r= a= ¥ 4.29 Å = 1.86 Å
4 4

Chapter
5
Surface
Chemistry
Key Concepts
Surface chemistry is the branch of chemistry that deals with Water vapour
the properties and processes occurring at the surface or inter-
face that is the boundary separating two bulk phases.
A B
ADSORPTION
A fi Silica Gel (Adsorption)
B fi Anhydrous CaCl2 (Absorption)
The phenomenon of attracting and retaining the particles of
a substance on the surface of a solid or a liquid resulting in If the process of adsorption and absorption both occur si-
a higher concentration at the surface rather than the bulk is multaneously then the process is known as sorption.
known as adsorption. For example, Chalk dipped in Ink.
Æ The substance of the surface of which the process of
adsorption takes place is known as adsorbent (s/l). Mechanism of Adsorption _________________
Æ The substance which is gating adsorbed on the surface The particles present in the bulk and at the surface of a sub-
is known as adsorbate (s/l/g). stance are under different conditions. The forces acting on the
Æ The removal of adsorbate from the surface of adsorbent bulk particles are mutually balanced as they are surrounded
is known as desorption. by the same type of particles from all sides but the particles
Æ The adsorption of gases on the surface of a metal is on the surface have unbalanced or residual attractive forces
known as occlusion. as they are not surrounded by same type of particle from all
sides as a result they have a tendency to attract and retain the
Adsorption Absorption
particles of other substance on their surface.
Æ In the process of adsorp- Æ In the process of absorption
tion the concentration of the concentration of the Adsorbate S/L/G
Surface particle Adsorbent
the substances increases substances is uniformly
only at the surface of ad- distributed throughout the Fnet π 0 solid or liquid
sorbent. bulk of the solid or liquid.
Bulk particle
Æ It is a surface phenom- Æ It is a bulk phenomenon. Fnet = 0
enon.
Thermodynamic approach for Adsorption
Æ The rate of adsorption de- Æ The rate of absorption is
DH adsorption = –ve [Due to decrease in surface energy]
creases with time. uniform through out the
DS adsorption = –ve [Due to decrease in degree of move-
process.
ment]
For example, NH3 on charcoal For example, NH3 in water
IIT JEE PC-V2_05.indd 1 5/12/2017 6:30:11 PM

As we know, Note: I
DG = DH – TDS The process of physical adsorption occuring at a low tem-
= –DH + TDS perature can be converted to chemical adsorption at a high-
\ DGadsorption = –DH + TDS er temperature.
(i) At low temperature
For example, adsorption of Hydrogen on the surface of Ni
DH > TDS
to form metal hydride.
\ DG = –ve
Adsorption is spontaneous
(ii) At high Temperature FACTORS EFFECTING
DH < TDS ADSORPTION
DG = +ve
Adsorption is non-spontaneous 1. Surface Area of Adsorbent
Surface area μ Extent of Adsorption
DH
(iii) When T = 2. Nature of Adsorbate
DS (i) In chemical adsorption, the particles of the adsor-
then TDS = DH bate adsorb on the surface of adsorbent only if they
\ DG = 0 are able to make chemical bonds.
Hence, equilibrium is attained in between adsorption For example, Oxygen is adsorbed on the surface of
and desorption. metals to form metal oxides.
Adsorption For example, Hydrogen is adsorbed on the surface
Adsorbate + Adsorbent Adsorbed
Desorption of transition metals to form metal hydrides.
Types of Adsorption (ii) In physical adsorption critical temperature (Tc)
1. Physical Adsorption Æ Also called physisorption. Tc μ Ease of Liquification μ Extent of Adsorption
For example, H2 N2 CO CH4 CO2 HCl NH3 SO2
Æ When the particle of adsorbate are held to the sur-
If Tc increases, Ease of liquification increases Ex-
face of adsorbent by the weak Van der Waal forces.
tent of adsorption increases.
Then, the process is called physical adsorption.
3. Effect of Temperature
2. Chemical Adsorption Æ Also called Chemisorption.
Æ When the particles of the adsorbate held to the sur- Ê xˆ
fi Extent of Adsorption Æ Á ˜
face of adsorbent due to the formation of strong Ë m¯
chemical bonds then, the process is called chemi- It is defined as the mass of adsorbate adsorbed per unit
cal adsorption. mass of adsorbent.
Æ The bond may be covalent or ionic and it requires x fi Mass of adsorbate
activation energy. Hence, it is also known as acti- m fi Mass of adsorbent
vated adsorption. At constant Pressure At constant Pressure
x
Physical Adsorption Chemical Adsorption m x
m
Æ Not specific in nature Æ Specific
Æ Activation energy is not Æ Activation energy is
required required Temperature fi Temperature fi
Æ It arises due to weak Van Æ It arises due to formation (A) Physisorption (B) Chemisorption
der Waal forces of strong chemical bonds
Æ These curves are called adsorption of isobars.
Æ Heat of adsorption is low, Æ Heat of adsorption is high,
(A) fi The extent of physical adsorption decreases
i.e., from –20 to –40 kJ i.e., from –80 to –240 kJ
with increase of temperature because the strength
mol–1 mol–1
of Van der Waal forces decreases with increase in
Æ Reversible in nature Æ Generally irreversible in temperature and also as the process is exothermic.
nature (B) fi The extent of chemical adsorption firstly in-
Æ Multi layer of adsorbate Æ Mono layer is formed on creases with temperature because it requires acti-
are formed on the surface the surface of adsorbent vation energy for the bond formation and after that
of adsorbent on increasing the temperature the extent of chemi-
cal adsorption decreases because the process is
Æ Low temperature is fa- Æ Favourable at high tem-
exothermic.
vourable for adsorption perature and extent of
4. Effect of Pressure
and extent of adsorption adsorption decreases with
The variation in extent of adsorption with change in
decreases with the in- increase in temperature
pressure at constant temperature can be explained with
crease in temperature
the help of some graphs called adsorption isotherms.

Surface Chemistry 5.3
(A) Freundlich adsorption isotherm: For physisorption (B) Langmuir Adsorption Isotherm: For chemical adsorp-
Æ He explained the variation in adsorption due the tion
change in pressure graphically and mathematically Postulate–1 He postulated that, the particles of adsorbate
as follows. can only form a single layer in depth on the
Æ Adsorbate – Gas surface of adsorbent.
Æ Adsorbent – Solid Postulate–2 There is no interaction in between the adjacent
adsorbed particles.
C D Postulate–3 There is a dynamic equilibrium in between the
x
m process of adsorption and desorption.
B
Postulate–4 All surface sides have equal tendency to at-
tract and retain the particles of adsorbate.
A x aP
P = where, a and b are Langmuir
m 1 + bP
Case-I At low pressure (A Æ B)
constant.
x
μP (i) At low P,
m
1 + bP 1
Case-II At high pressure (C Æ D)
x
x So, = aP
μ P∞ m
m
Case-III At intermediate pressure (B Æ C) Èx ˘
\ Í μ P˙
x Îm ˚
μ P1/n [where n = 1 to ] (ii) At high P,
m
1 + bP bP
x
The resultant condition = KP1/ n x aP a
At low P fi n = 1 m So, = =
m bP b
At high P fi n =
At intermediate P fi 1 < n < \ Èx ˘
ÍÎ m μ P∞ (constant) ˙˚
\ the value of (1/n) ranges from 0 to 1.
Here x fi Mass of adsorbate * As we know,
m fi Mass of adsorbent x aP
=
P fi Pressure of adsorbate gas m 1 + bP
K and n fi Constants that depends on the nature of ad- It can be written as
sorbate and adsorbent. 1 1 + bP 1 b
= = +
Note: 1 ( x /m ) aP aP a
For adsorption of solute in the solution, the expression for 1 1 1 b
Freundlich adsorption isotherm can be given as: \ = ¥ +
x /m a P a
x ∫ y = mx + C
= KC1/ n where, C fi Concentration of solution.
m
Slope = 1
a
Logarithmic form of Freundlich adsorption Isotherm
1
x/m
Slope = 1
n q
x
log m b
q Intercept = a
Intercept = log K 1/P
log P fi Note: 2
As we know Exception,
H2 + Glass (Endothermic)
x
= KP1/ n
m (II) Colloids Æ Colloids are heterogeneous system in
Taking log on both sides which a substance (dispersed phase) is dispersed as
x 1 very fine particles in dispersion medium.
log = log K + log P
m n

Æ Colloid have two parts: 7. Ex- NaCl, KCl in Starch, Gum, Sand Iron
(i) Dispersed phase fi The substance which is pres- H2O Protein in hails in H2O
ent in lesser amount just like solute in true solution H2O
is known as dispersed phase.
(ii) Dispersion medium fi The substance which is * Classification of Colloids:
present in greater amounts just like solvent in true (A) On the basis of physical state of dispersed phase and
solution is known as dispersion medium. dispersion medium.
* Classification of solution on the basis of size of
particles. Dispersed Dispersion Colloids Examples
Phase medium
Properties True Solution Colloids Suspension
Solid Solid Solid Sol Gem Stones
1. Size of Less than 1 between Greater then
Solid Liquid Sol Paints
particle nm 1-1000 nm 1000 nm
Solid Gas Aerosol Dust
2. Nature Homogenous Heterog- Heterog- Liquid Solid Gel Cheese, Jellies
enous enous Liquid Liquid Emulsion Milk, Hair Cream
3. Visibility Not visible Visible under Visible with Liquid Gas Aerosol Fog, Cloud
microscope naked eye Gas Solid Solid Sol Pumice Stone
4. Separation Gas Liquid Foam Froth
(i) Filter paper ¥ ¥ ÷
(B) On the basis of Dispersion Medium
(ii) Membrane ¥ ÷ ÷
5. Tyndall Do not show Shows May or may Dispersion Medium Colloid
effect not show
H2O Hydrosol OR Aquasol
6. Settling Do not settle Does not set- Settles
Benzene Benzosol
down of tles but under down
Air Aerosol
particles ultra centrif-
Alcohol Alcosol
ugation they
can settle
(C) On the basis of Interaction in between dispersed phase and dispersion medium
Lyophilic (Solvent loving) Lyophobic (Solvent lating)
(Hydrophilic)
(i) When the particles of Dispresedphase have a greater (i) When the particles of Dispresedphase have a lesser
the colloids are known as Lyophilic. colloids are known as hyophobic.

(ii) Easily prepared just by mixing the dispersed phase (ii) It requires special methods for preparation.
with dispersion medium.
(iii) More stable (iii) Less stable (requires, stabilising agent)
(iv) Reversible in nature (iv) Irreversible in nature
(v) Coagulation is not so easy. (v) Easily coagulated
(vi) Higher degree of solvation or hydration (vi) Lower degree of hydration or solvation
(vii) Viscosity is more and surface tension is less as com- (vii) Viscosity and surface tension are nearly the same as
pared to that of dispersion medium that of dispersion medium.
For example, generally of organic nature like sols of protein, For example, generally of inorganic nature like sols of met-
starch, etc. als metal sulphides, etc.
(D) On the basic of type of particles of dispersed phase size lies in the colloidal range such type of systems are
(i) Multi-molecular colloids known as multi-molecular colloids.
On dissolution a large number of atoms or smaller For Example,
An (gold) sol and sulphur solution in sulphur sol
molecules aggregate together to form particles whose 1 Dispresed phase particle = 1000 or more S8 molecules

(ii) Macro-molecular colloids Methods of Preparation

Macro-molecules (having higher molecular mass) in a 1. Lyophilic colloids
suitable solvent forms solution in which their size lies They are easily prepared just by mixing the particles of
in the colloidal range such systems are known as mac- dispersed phase with the dispersion medium.
ro-molecular colloids. 2. Lyophobic Colloids (intrinsic colloid)
For example, Starch, protein (Natural macro-molecules) These colloids are prepared by the following methods:
Nylon, polyethene (Man made macro-molecules) (A) Dispersion method
(B) Condensation method
(iii) Associated colloids
Æ There are some substances which behave as strong
electrolytes at lower concentration but at higher (A) Dispersion Method
concentration they exhibit colloidal behaviour due In these methods larger particles are broken into smaller par-
ticles.
to formation of aggregates. The aggregate thus
(i) Mechanical Dispersion
formed are known as micelles and the system is
Inlet (Suspension)
known as associated colloids.
Æ The temperature and the concentration above Metal
which the formation of micelles occurs is known plates
as craft temperature and Critical Micelle Concen-
tration (CMC). Outlet Outlet
For example, Surface acting agents (Surfactant’s) like
soap and detergent. Colloidal Mill
(A) Anionic Surfactants In this method, the particles of the suspension are grind-
Sodium stearate fi C17H35COO–Na+ (Soap) sodium lauryl ed to colloidal sized particles by placing it in between
sulphate two metal plates that rotates in opposite direction in a
Colloidal mill. This method is used for preparing the
CH 3 (CH 2 )11SO 4- Na + (Detergent) colloids of paints, varnises, dies, etc.
(B) Cationic surfactants (ii) Electrical dispersion Bridics Arc Method
Catyl Trimethyl ammonium Chloride fi C16H33(CH3)3N+Cl–
Octadecyl ammonium chloride fi C18 H37 NH3+ Cl- Metal electrodes
fi Associated colloids have both lyophilic and hyophobic H2O (Dispersion Medium)
part. A micelle may contain 100 or more ions. +
KOH
Mechanism of micelle formation (stabilising agent)
C17H35COONa Æ C17H35COO– (stearate) + Na+ Ice Bath
or RCOONa and RCOO– and Na+ Æ In this method, on striking an electric arc in be-
Head tween the metal electrodes result in the vapouri-
(Hydrophilic) sation of metal which is then condensed by the
polar effect of ice bath. This metal disperses in water
Tail and hence forms a colloid. This method is used for
(Non polar) preparing colloids of metal like Au, Ag, Pt, etc.
(iii) Peptisation
Fe(OH)3 + FeCl3 h Fe(OH)3|Fe3+
Precipitate Electrolyte Colloid
Precipitate + Dispersion Medium + Electrolyte (Small
amount) fi Sol.
ÈPeptidising agent ˘
Electrolyte used as ÍÍ i.e.,stabilising ˙˙
(a) Arrangement of stearate (b) Micelle formation on ÍÎ agent ˙˚
ions on the surface of at CMC. (Non-polar tails
water before CMC. towards centre. Polar on Æ The process of converting a freshly prepared
surface of sphere. Precipitate into a colloidal solution by adding elec-
trolyte is known as peptisation.

Æ The electrolyte used in this process are known as 2. Electrodialysis: This method is used when the impuri-
peptising agents. ties are electrolytes.
Æ This process involves the adsorption of suitable 3. Ultrafiltration:
ion (common ion) on the surface of Precipitate Ultra filter paper = Filter paper + Collodion solution
provided by the added electrolyte. As, a result the [4% Nitro – Cellulose is a mixture of alcohol and ether]
charged particles repell each other and thus forms
a colloid. Impure Colloidal
Ultrafiltres
paper Solution
(B) Condensation Method
In these methods smaller particle are aggregated together to
the colloidal size.
(i) Chemical Method after some time
double
Æ As 2O3 + 3H 2S æææææÆ
decomposition
As 2S3 (sol) + 3H 2O
Oxidation Pure
Æ H 2S + Br2 ææææÆ 2HBr + S(sol)
Colloidal
Reduction
Æ 2AuCl3 + 3SnCl2 ææææÆ 2Au(sol) + 3SnCl4 particle
Hydrolysis
Æ FeCl3 + 3H 2O ææææÆ Fe(OH)3 (sol) + 3HCl Impurities
Æ In chemical reactions the molecules form aggre-

gate together to form particles that lie in the col- 4. Ultra centrifugation: In this method, the tube is ro-
loidal range. tated at a very high speed as a result of which pure col-
(ii) Physical Methods loidal particles settle down and the impurities remain
(a) By exchange of solvent: In this method, a true so- in the solution. These pure colloidal particles are col-
lution is mixed with an excess of solvent in which lected and mixed with the dispersion medium to form
the solute is less soluble and the solvent is com- colloidal solutions.
pletely miscible.
ÈSulphur in C2 H 5OH ˘ ÈSulphur in Alcoholic H 2O ˘ PROPERTIES OF COLLOIDAL
Í True solution ˙ + H 2O = Í ˙ SOLUTIONS
Î ˚ Î Colloidal ˚
(b) By excessive cooling: In this method on excessive 1. Heterogeneous nature:
cooling, the molecules of a substance condense to- 2. Visibility: Colloidal particles are too small to be seen
gether to form particles of the colloidal range. with naked eye, but they become visible as bright spots
against dark background when viewed through an ultra
On excessive
H 2O + CHCl3 æææææ
Cooling
Æ ice + CHCl3 fi Colloidal microscope due to scattering of light caused by them.
3. Filterability: The size of solute particles is smaller
(c) By condensing vapors: In this method the vapour than the pore size of filter paper, and therefore, they
of sulphur or Hg are passed through cold water can readily pass through ultra filters, parchment paper,
containing ammonium nitrate.
or animal membrane.
4. Surface tension and viscosity: The surface tension and
PURIFICATION OF COLLOIDS viscosity of lyophobic sols are not very different from
those of the dospersion medium. On the other hand,
1. Dialysis: lyophilic sols show higher viscosity and lower sur-
face tension in comparison to the dispersion medium.
H2 O + 5. Colligative properties: very low due to high molar
Dialysing dissolved mass.
membrane Impure Impurities
Colloidal 6. Brownian movement: The colloidal particles of a col-
solution
loidal solution when viewed through an ultramicroscope
Inlet
Dialyser show a constant zig – zag motion. This type of motion
was first observed by robert brown and is known as
Æ This process involves the diffusion of dissolved
brownian movement. This motion is independent of the
impurities through the membrane and leaving be-
hind a pure colloidal solution. nature of the colloid but depends on the size of the par-

ticles and the viscosity of solution. Smaller the size and The direction of the flow of water (dispresion
lesser the viscosity, faster is the motion. The Brownian medium)depends on the charge of the colloid. For
movement is due to the unbalanced bombardment of the positively charged sols, the medium is negatively
particles by the molecules of the dispersion medium. charged, and hence the flow will take place from
7. Optical Properties: Tyndall effect: The scattering of one side to other. On the other hand, for negative-
ly charged sols, the reverse will occur.
light by the colloidal particles in a colloidal solution
9. Coagulation or precipitation or floculation of col-
is known as tyndall effect as it was first observed by
loids:-
Faraday and later studied in detail by Tyndall. Tyndall
The process of settling of colloidal particles is called
effect is caused by the scattering of blue part of light by
coagulation or Precipitation of the sol. The coagu-
the colloidal particles. lation of the lyophobic sols can be carried out in the
Tyndall effect is observed only when the following following ways.
two conditions are satified: (a) By electrophoresis
The diameter of the dispersed particles is not much (b) By mixing two oppositely charged sols
smaller than the wavelength of the light used. The re- (c) By boiling
fractive indices of the dispersed phase and the disper- (d) By persistent dialysis
sion medium must differ greatly in magnitude. (e) By addition of electrolytes
Zsigmondy:- Tyndall effect to set up an apparatus Colloids Around US
known as ultramicroscope. (a) Blue colour of the sky
8. The electrical properties of colloidal solutions are re- (b) Fog, mist and rain
lated with two phenomena: (c) Food articles :- Milk, butter, halwa
Reservoir (d) Blood :- It is a colloidal solution of an albuminoid sub-
stance.
(e) Soils :-
Cathode
(f) Formation of delta:-
Anode
Application of colloids
(a) Electrical precipitation of smoke
(b) Purification of drinking water
(c) Medicines
Initial level (d) Tanning
(e) Cleasing action of soaps and dettergents
Water Colloidal (f) Photographic plates and films
(dispersion solution
medium) (g) Rubber industry
(h) Industrial products
Zeta potential:
The potential difference between the fixed layer and the dif-
Stop cock fused layer of opposite charges is called electro kinetic poten-
tial or zeta potential.
(i) Electrophoresis: The existance of charge on col- AgI I– K+

loidal particles is determined by electrophoresis. – +
AgI I K
The phenomenon of the movement of col- Mobile layer
AgI I– K+
loidal particles under an applied electric field is
called electrophoresis. The positive charged par- AgI I– K+
ticles move towards the cathode while negatively Fixed layer
charged particles move toward the anode.
(ii) Electro – osmosis: Electro – osmosis may be de- Hordy sulzi rule: Greater the valency of the active ions or
fined as a phenomenon in which the molecules of flocculating ion greater will be its flocculating power
the dispersion medium are allowed to move under For example,
the influence of an electric field whereas colloidal (i) Al+3 > Mg+2 > Na+ for –ve sol.
particles are not allowed to move.
(ii) [Fe(CN)6 ]-4 > PO 4-3 > SO 4-2 > Cl- for + ve sol

Gold Number: The protective power is measured in terms Positively charged colloid Negatively charged colloid
of gold number. It is defined as the number of milligrams of Hydrated metallic oxide Metals Cu, Ag, Au, Sol
a lyophilic colloid that will just prevent the precipitation of Al2O3. xH2O, CrO3. xH2O, Metalic sulphides As2S3,
10 mL of a gold sol on the addition of 1 mL of 10% NaCl Fe2O3. xH2O Sb2S3, CdS sol
solution Basic dye stuffs methylene Acid dye stuff eosin, congo
1 blue sol, red
Protective Power μ Haemoglobin (blood)
Gold Number
Oxide TiO2 Sol Sols of starch, gum gelatin,
clay
Solved Examples
1. For a linear plot of log (x/m) versus log P in a Freun- x 1 =1

dlich adsorption isotherm, which of the following Sol. (d) log = log K + log P n
m n x
statements is correct? (k and n are constants) log m
(a) 1/n appears as the intercept. y = +c + mx
tan 45 = 1 log K
(b) Only 1/n appears as the slope.
(c) log (1/n) appears as the intercept x
log = log 10 + 1 log (0.5) log P
(d) Both k and 1/n appear in the slope term. 1
Sol. (b) log x = log 10 + 1 ¥ log [5 ¥ 10–1]
x log x
1 log x = 1 + (–1) + .6990 = .6990 = log 5
= Kp n m
m \ x = 5 gram
1
x 1 n 4. Gold number is a measure of
log = log K + log P (a) stability of colloidal system.
m n
(b) coagulating power of a colloid.
y = + C + mx log P
(c) size of colloidal particles.
2. The coagulation values in mil- (d) efficiency of the protective colloid.
limoles per litre of the electrolytes used for the coagu- Sol. (d) Smaller is the gold number, higher is its protecting
lation of As2S3 are given below: power.
I. (NaCl) = 52 II. (BaCl2) = 0.69 Gelatin – .005 to .01
III. (MgSO4) = 0.22 Haemoglobin – 0.03
The correct order of their coagulating power is Gum – 0.15
(a) III > I > II (b) I > II > III Egg albumin – .08–.10
(c) II > I > III (d) III > II > I Starch – 25–40
Sol. (d) Gold No. The minimum amount in milligram of pro-
1 tective colloid which must be added to 10 mL gold sol
Coagulation value μ
Coagulating power in order to prevent its coagulation against 1 mL 10%
NaCl (52) BaCl2(0.69) MgSO4(0.22) NaCl solution.
(I) (II) (III) Ê xˆ
5. Graph between log Á ˜ vs log P is provided for ad-
\ coagulating power for As2S3 Ë m¯
MgSO4 > BaCl2 > NaCl sorption of NH3 gas on metal surface.
III > II > I Calculate weight of NH3 gas adsorbed by 50 g of metal
3. Plot of log ÊÁ ˆ˜ against log P is a straight line inclined
x surface at 2 atm pressure.
Ë m¯
at an angle of 45°. When the pressure is 0.5 atm and
Freundlich parameter (K) is 10, then the amount of sol-
ute adsorbed per gram of adsorbent will be (log 5 = 45°
log (x/m)
0.699): A
(a) 1 g (b) 6.99 g 0.3
(c) 3 g (d) 5 g
log P

(a) 100 g (b) 75 g DS = –ve

(c) 200 g (d) 50 g DG = –ve
1 DSurr. = 0
Sol. (c) slope = = tan 45∞ = 1 7. Fe (SCN)n3–n absorb colour because of the complex
n
Fe(SCN)n3–n only, whereas Fe3+ and SCN– both are co-
slope = 1
n = tan 45° = 1 lourless. In the given table, the equilibrium concentra-
tion of Fe3+ and SCN– and corresponding absorbance
45° are given–
x
log m
log K = 0.3 = log 2 Exp. No. [Fe3+] [SCN–] Absorbance
1 3 ¥ 10 (M)
–3
(10 M) 3
log P
2 3 ¥ 10–3(M) (10)2/3(M) 0.3
Considering absorbance proportional to concentration
x 1 of the complex, the value of n is
= KP n (a) 3 (b) 6 (c) 4 (d) 2
m
3+ – ææ Æ 3–n
x 1 Sol. (a) Fe + nSCN ¨æ æ Fe(SCN)n
log = log K + log p
m n
[Complex]
1
= log 2 + log 2 K form =
n [Fe3+ ][SCN - ]n
x { [complex] = Kform [Fe3+][SCN–]n
log = log 2 + (1) log 2
m
\ log [complex] = log Kform + log [Fe3+] + n log [SCN–]
x
=2¥2 [Fe3+] is constant, hence
m
x [Complex]1 [SCN – ]1
=4 log = n log
50 [Complex]2 [SCN – ]2
x = 200 g
10
6. Which of the following parameter is correct regarding \ log 3/0.3 = n log
adsorption of gases over solid? (10) 2/3
(a) DSsystem> 0 (b) DSsurrounding> 0 1
(c) DG > 0 (d) DH > 0 1= n ¥
3
Sol. (b) Adsorption
DH = –ve or n=3
Exercise
x
LEVEL I m
C
B
1. The formation of micelles (Associated colloids) takes A

place P
(a) above CMC and at kraft temperature.
(b) at CMC and above kraft temperature. x x 1
(a) = kP (b) = kP n
(c) at CMC and at kraft temperature. m m
(d) above CMC and above kraft temperature. x x
2. Which of the following is an example of positively (c) = kP1 (d) = kP n
m m
charged sols?
(a) As2S3 (b) Gold sol 4. Gelatin is added in manufacture of icecream in order to
(c) Congo red sol (d) Haemoglobin (a) prevent formation of a colloid.
3. When a graph is plotted between x/m versus pressure at (b) stabilise the colloid and prevent crystallisation.
constant temperature. The Freundlich equation at ‘B’ is (c) cause the mixture to solidify easily.
(if n > 1) (d) improve flavour.

5. Which of the following statement is incorrect? 14. Which one of the following characteristics is not cor-
(a) Lyophilic sols are reversible. rect for physical adsorption?
(b) Lyophilic sols are more stable than lyophobic (a) Adsorption on solids is reversible.
sols. (b) Adsorption increases with increase in tempera-
(c) Lyophobic sols require stabilising agent for their ture.
preservation. (c) Adsorption is spontaneous.
(d) Lyophobic sols can be formed by direct mixing of (d) Both enthalpy and entropy of adsorption are nega-
dispersed phase and dispersion medium. tive.
6. Which of the following graph represents the variation 15. Identify the gas which is readily adsorbed by activated
of amount of chemisorptions of a gas by a solid with charcoal.
temperature under constant pressure? (a) N2 (b) SO2 (c) H2 (d) O2
16. The concentration of electrolyte required to coagulate a
(a) (b)
given amount of As2S3 sol is minimum in case of
(a) K2SO4 (b) Al(NO3)3
x/m
x/m
(c) Mg(NO3)2 (d) KNO3

17. Plot of log x/m against log p is a straight line inclined at
T T an angle of 45°. When the pressure is 4 atm and Freun-
(c) (d) dlich parameter, k is 10, the amount of solute adsorbed
per gram of adsorbent will be (log 5 = 0.6990)
(a) 2 g (b) 4 g (c) 16 g (d) 40 g
x/m
x/m
18. Which one of the following is an example for homoge-

neous catalysis?
T T
(a) Manufacture of sulphuric acid by contact process.
7. The colloidal sols are purified by (b) Manufacture of ammonia by Haber’s process.
(a) Peptisation (b) Coagulation (c) Hydrolysis of sucrose in presence of dilute hydro-
(c) Dialysis (d) None of these chloric acid.
8. Which of the following is not heterogeneous? (d) Hydrogenation of oil.
(a) Emulsion (b) True solution 19. The efficiency of enzyme catalysis is due to its capacity
(c) Suspension (d) Colloidal solution to
9. In multimolecular colloidal sols, atoms or molecules (a) form a strong enzyme-substrate complex.
are held together by (b) change the shape of the substrate.
(a) H-bonding (b) van der Waals forces (c) lower the activation energy of the reaction.
(c) ionic bonding (d) polar covalent bonding (d) form a colloidal solution in water.
10. Colloidal solution of gold prepared by different meth- 20. Which of the following reaction is an example for ho-
ods are of different colours because of
mogeneous catalysis?
(a) variable valency of gold.
MnO (s)
(b) different concentrations of gold particles. (a) 2H2O2(l) ææææ
2
Æ 2H2O(l) + O2(g)
(c) impurities produced by different methods. V O5(s)
(b) 2SO2(g) + O2(g) ææææ
2
Æ 2SO3(g)
(d) different diameters of colloidal gold particles.
NO(g)
11. Cod liver oil is (c) 2CO(g) + O2(g) æææÆ 2CO2(g)
(a) fat dispersed in fat (b) fat dispersed in water Ni(s)
(d) H2(g) + C2H4(g) æææ
Æ C2H6(g)
(c) water dispersed in fat (d) water dispersed in oil
12. Cellulose dispersed in ethanol is called 21. Which of the following electrolytes is least effective in
(a) emulsion (b) micelle coagulating ferric hydroxide solution?
(c) collodion (d) hydrophilic solution (a) KNO3 (b) K2SO4
13. According to the adsorption theory of catalysis, the (c) K2Cr2O7 (d) K4[Fe(CN)6]
speed of reaction increases because 22. Example of intrinsic colloid is
(a) adsorption lowers the activation energy of the re- (a) glue (b) sulplur (c) Fe (d) As2S3
action. 23. Match the following colloids (in Column 1) with their
(b) the concentration of reactant molecules at the ac- specific name (in Column II) and choose the correct
tive centres of the catalyst becomes high due to codes given below.
adsorption. Column-I Column-II
(c) in the process of adsorption, the activation energy
of the molecules becomes large. A. Smoke 1. Foam
(d) adsorption produces heat which increases the B. Alloys 2. Aerosol
speed of the reaction. C. Froths 3. Gel
D. Cheese 4. Solid sol

Codes
A B C D LEVEL II
(a) 4 3 1 2
(b) 2 3 4 1 1. Colloids are purified by
(c) 2 4 1 3 (a) Brownian motion (b) Precipitation
(d) 3 2 4 1 (c) Dialysis (d) Filtration
24. In Freundlich adsorption isotherm, the value of 1/n is 2. Which of the following substance give a positively
(a) between 0 and 1 in all cases. charged sol?
(b) between 2 and 4 in all cases. (a) Gold (b) Arsenious sulphide
(c) Starch (d) Ferric hydroxide
(c) 1 in case of physical adsorption.
3. When excess of electrolyte is added to a colloid it
(d) 1 in case of chemisorption.
(a) Coagulates (b) Gets diluted
25. Which one of the following characteristics is associ-
(c) Dissolved (d) Does not change
ated with adsorption? 4. Gold number is a measure of the
(a) DG is negative but DH and DS are positive. (a) protective action by a lyophilic colloid on lyopho-
(b) DG, DH and DS all are negative. bic colloid.
(c) DG and DH are negative but DS is positive. (b) protective action by a lyophobic colloid on lyo-
(d) DG and DS are negative but DH is positive. philic colloid.
26. The addition of catalyst during a chemical reaction al- (c) number of mg of gold in a standard red gold sol.
ters which of the following quantities? (d) None of the above
(a) Entropy (b) Internal energy 5. A liquid is found to scatter a beam of light but leaves no
(c) Enthalpy (d) Activation energy residue when passed through the filter paper. The liquid
27. Fog is a colloidal solution of can be described as
(a) Liquid in gas (b) Gas in liquid (a) A suspension (b) Oil
(c) Solid in gas (d) Gas in gas (c) A colloidal sol (d) True solution
28. Substances whose solutions can readily diffuse through 6. A catalyst is a substance which
animal membranes are called (a) Increases the equilibrium concentration of the
(a) Colloids (b) Crystalloids product.
(c) Electrolytes (d) Non-electrolytes (b) Change the equilibrium constant of the reaction.
29. The size of the colloidal particles is in between (c) Shortens the time to reach equilibrium.
(d) Supplies energy to the reaction.
(a) 10–7 – 109 cm (b) 10–9 – 10–11 cm
7. A catalyst
(c) 10–5 – 10–7 cm (d) 10–2 – 10–3 cm
(a) Increases the free energy change in the reaction.
30. The size of a colloidal particle is
(b) Decreases the free energy change in the reaction.
(a) > 0.1m (b) 1 mm to 0.1 m (c) Does not increases and decreases the free energy
(c) < 0.1 mm (d) More than 3000 mm change in the reaction.
31. If dispersed phase is liquid and the dispersion medium (d) Can either decreases or increases the free energy
is solid, the colloid is known as change depending on what catalyst we use.
(a) A sol (b) A gel 8. A catalytic poison renders the catalyst ineffective be-
(c) An emulsion (d) A foam cause
32. An emulsion is a colloidal solution consisting of (a) It is preferentially adsorbed on the catalyst.
(a) Two solids (b) It adsorbs the molecules of the reactants.
(b) Two liquids (c) It combines chemically with the catalyst.
(c) Two gases (d) It combines with one of the reactant.
(d) One solid and one liquid 9. Regarding criteria of catalysis which one of the follow-
33. The colloidal solution of gelatin is known as ing statements is not true?
(a) Solvent loving (b) Reversible (a) The catalyst is unchanged chemically during the
(c) Hydrophilic (d) All of the above reaction.
(b) A small quantity of catalyst is often sufficient to
34. Peptization is a process of
bring about a considerable amount of the reaction.
(a) precipitating the colloidal particles.
(c) In reversible reaction, the catalyst alters the equi-
(b) purifying the colloidal sol.
librium position.
(c) dispersing the precipitate in to colloidal sol. (d) The catalyst accelerates the rate of reaction.
(d) movement of colloidal particles towards the op- 10. Which of the following is lyophobic in nature?
posite charged electrodes. (a) Gelatin (b) Phosphorus
(c) Starch (d) Agar-Agar

11. Gelatin is mostly used in making ice creams in order to 22. Position of non-polar and polar part in micelles:
(a) prevent making of colloid. (a) Polar at outer surface but non polar at inner sur-
(b) stabilise the colloid and prevent crystalisation. face.
(c) stabilise the mixture. (b) Polar at inner surface but non polar at outer sur-
(d) enrich the aroma. face.
12. Blood may be purified by (c) Distributed over all the surface.
(a) dialysis (b) electro osmosis (d) Are present in the surface only.
(c) coagulation (d) filtration 23. Milk is a colloidal
13. The slope of the straight line graph between log x/m (a) liquid is dispersed in a liquid.
and log P for the adsorption of a gas on solid is (b) solid is dispersed in a liquid.
(a) k (b) log k (c) n (d) l/n (c) gas is dispersed in a liquid.
14. The work of enzymes in living system is (d) sugar is dispersed in a liquid.
(a) oxygen transfer. 24. Adsorbed acetic acid on activated charcoal is
(b) to provide immunity. (a) adsorbed (b) absorber
(c) to catalyse bio’ chemical reactions. (c) adsorbent (d) adsorbate
(d) to provide energy. 25. Who was Awarded Noble Prize for the study of cata-
15. A chemical reaction is catalysed by catalyst X. So X lytic reactions?
(a) increases the activation energy of reaction. (a) Ostwald (b) Berzelius
(b) does not affect equilibrium constant of reaction. (c) Vanthoff (d) Werner
(c) decreases the rate constant of reaction. 26. Colloidal particles carry charge. This can be shown by
(d) decreases enthalpy of reaction. (a) Tyndall effect (b) electrophoresis
16. When some special substances like protein particles. (c) Brownian movement (d) dialysis
Blood corpuscles, etc., are separated by a permeable 27. Which forms a colloidal solution in water?
membrane, the process is called (a) NaCl (b) glucose
(a) dialysis (b) diffusion (c) strach (d) barium nitrate
(c) exosmosis (d) endosmosis 28. Hydrophilic gels, when placed in water, absorb liquid
17. Which is not the characteristic of hydrophobic sols? resulting in an increase of their volume. This process of
(a) They are highly susceptible to coagulation by swelling of gels takes place with
addition of electrolytes. (a) no change in volume
(b) They have nearly the same surface tensions and (b) net increase in volume
viscosity as that of dispersion medium. (c) net decrease in volume
(c) Their stability is due to both electric charge and (d) large reduction in volume
salvation of the particles. 29. When dilute aqueous solution of AgNO3 excess is
(d) Sol particles can be seen under ultramicroscope. added to KI solution, which of the following positively
18. According to Hardy Schultz law the order of coagula- charged sol particles of AgI are formed due to adsorp-
tion power of cations will be tion of ion?
(a) Na+ > Ba+2 > Al+3 (b) Al+3 > Ba+2 > Na+ (a) KI+ (b) Ag+ (c) I– (d) NO3–
(c) Ba+2 > AI+3 > Na+ (d) AI+3 > Na+ > Ba+2 30. The process which is catalysed by one of the products
19. Which one of the following method is commonly used is called
for destruction of colloid? (a) acid-base catalysis (b) autocatalysis
(a) Dialysis (c) negative catalysis (d) None of these
(b) Condensation 31. Which of the following statements about a catalyst is
(c) Filtration by animal membrane true?
(d) By adding electrolyte (a) It lowers the energy of activation.
20. How enzymes increase the rate of reactions? (b) The catalyst altered during the reaction is regener-
(a) By lowering activation energy. ated.
(b) By increasing activation energy. (c) It does not alter the equilibrium.
(c) By changing equilibrium constant. (d) All of the above
(d) By forming enzyme substrate complex. 32. Colour of colloidal solution is due to
21. Which is not correct regarding the adsorption of a gas (a) different size of colloidal particles.
on surface of solid? (b) due to formation of complex.
(a) On increasing temperature adsorption increases (c) due to formation of hydrated crystal.
continuously. (d) none of the above
(b) Enthalpy and entropy change is negative. 33. Which of the following is a property of colloid?
(c) Adsorption is more for some specific substance. (a) Scattering of light (b) They show attraction
(d) Reversible (c) Dialysis (d) Emulsion

34. The size of particles in suspension, true solution and 45. Surface tension of lyophilic sols is
colloidal solution varies in the order? (a) lower than that of H2O
(a) Suspension > Colloidal > True solution (b) more than that of H2O
(b) Suspension > (Colloidal + True solution) (c) equal to that of H2O
(c) True solution > Suspension > Colloidal (d) None of these
(d) None of these 46. The catalyst used in the manufacture of methanol from
35. At the critical micelle concentration, the surfactant water gas is
molecules (a) V2O5 (b) Ni + Mo
(a) decompose (c) ZnO + Cr2O3 (d) Pt + W
(b) dissociate 47. Which one of the following is an incorrect statement
(c) associate for physisorption?
(d) become completely soluble (a) It is a reversible process.
36. The adsorption of a gas on a solid surface varies with (b) It requires less heat of adsorption.
pressure of the gas in which of the following manner? (c) It requires activation energy.
(a) Fast Æ slow Æ independent of the pressure (d) It takes place at low temperature.
(b) Slow Æ fast Æ independent of the pressure 48. The colligative property of a sol compared to the aque-
(c) Independent of the pressure Æ fast Æ slow ous solution of glucose of same concentration will be
(a) Much smaller (b) Much higher
(d) Independent of the pressure Æ slow Æ fast
(c) The same (d) Slightly lower
37. If gold number of A, B, C and D are 0.005, 0.05, 0.5
49. Sodium lauryl sulphate is
and 5 respectively, then which of the following will
(a) cationic sol (b) anionic sol
have the greatest protective power?
(c) neutral sol (d) None of these
(a) A (b) B (c) C (d) D
50. Which of the following does not form sol?
38. Which of the following colloids are formed when hy-
(a) Electrophoresis
drogen sulphide gas is passed through a cold solution (b) Peptisation
of arsenious oxide? (c) Electrical disintegration
(a) As2S3 (b) As2O3 (c) As2S (d) As2H2 (d) Solvent exchange
39. The movement of colloidal particles towards the 51. Which of the following is not an emulsion?
oppsitely charged electrodes on passing electricity is (a) Butter (b) Ice cream
known as (c) Milk (d) Cloud
(a) cataphoresis (b) Tyndall effect 52. Which of the following reaction is catalysed by en-
(c) Brownian movement (d) None of these zyme maltase?
40. Which of the following is used for the destruction of (a) Starch Æ Maltose
colloids? (b) Maltose Æ Glucose
(a) Dialysis (b) Condensation (c) Lactose Æ Maltose
(c) By ultrafiltration (d) By adding electrolyte (d) Maltose Æ Glucose + Fructose
41. Brownian movement is 53. Which of the following factors affects the adsorption of
(a) Zig-zag motion of the colloidal particles. a gas on solid?
(b) Migration of colloidal particles under the influ- (a) Tc (critical temperature)
ence of electric field. (b) Temperature of gas
(c) Scattering of light by colloidal particles. (c) Pressure of gas
(d) None of these (d) All of these
42. Enzymes with two sites are called 54. The volume of gases NH3, CO2 and CH4 adsorbed by
(a) apoenzyme (b) holoenzyme one gram of charcoal at 298 K are in
(c) allosteric enzyme (d) conjugate enzyem (a) CH4 > CO2 > NH3 (b) NH3 > CH4 > CO2
43. Wood charcoal is used to decolourise sugar because it (c) NH3 > CO2 > CH4 (d) CO2 > NH3 > CH4
(a) adsorbs coloured material 55. The heat of physisorption lie in the range of
(b) absorbs decolorised material (a) 1 to 10 kJ mol–1 (b) 20 to 40 kJ mol–1
–1
(c) reduces coloured material (c) 40 to 200 kJ mol (d) 200 to 400 kJ mol–1
(d) None of these 56. Which of the following is not a gel?
44. A catalyst can effect reversible reaction by (a) Cheese (b) Jellies
(a) changing equilibrium (c) Curd (d) Milk
(b) slowing forward reaction 57. Which of the following is used to adsorb water?
(c) attaining equilibrium in both direction (a) Silica gel (b) Calcium acetate
(d) None of these (c) Hair gel (d) Cheese

58. An emulsion is a colloidal system of 69. Under the influence of an electric field, the particles in
(a) two solids a sol migrate towards cathode. The coagulation of the
(b) two liquids same sol is studied using NaCl, Na2SO4, and Na3PO4
(c) one gas and one solid solutions. Their coagulating values will be in the order
(d) one gas and one liquid (a) NaCl > Na2SO4 > Na3PO4
59. Which of the following is a lyophobic colloid? (b) Na2SO4 > Na3PO4 > NaCl
(a) Gelatin (b) Sulphur (c) Na3PO4 > Na2SO4 > NaCl
(c) Starch (d) Gum arabic
(d) Na2SO4 > NaCl > Na3PO4
60. The nature of bonding forces in adsorption is
70. Tyndall effect would be observed in a
(a) purely physical such as Van der Waal’s forces.
(b) purely chemical. (a) solution (b) solvent
(c) both chemical and physical always. (c) precipitate (d) colloidal solution
(d) None of these 71. Adsorption is multilayer in case of
61. The Tyndall effect associated with colloidal particles is (a) physical adsorption (b) chemisorption
due to (c) both (d) None of these
(a) presence of electrical charges. 72. A liquid is found to scatter a beam of light but leaves no
(b) scattering of light. residue when passed through the filter paper. The liquid
(c) adsorption of light. can be described as
(d) reflection of light. (a) a suspension (b) oil
62. Which one of the following is not applicable to chemi- (c) a colloidal sol (d) a true solution
sorption? 73. The ability of an ion to bring about coagulation of a
(a) Its heat of adsorption is high. given colloid depends upon
(b) It takes place at high temperature. (a) its charge.
(c) It is reversible.
(b) the sign of the charge alone.
(d) It forms mono-molecular layers.
(c) the magnitude of the charge.
63. In the colloidal state the particle size ranges
(a) below 1 nm. (d) both magnitude and sign of charge.
(b) between 1 nm to 100 nm. 74. Which of the following ionic substances will be most
(c) more than 100 nm. effective in precipitating the sulphursol ?
(d) None of the above. (a) KCl (b) BaCl2
64. All colloids (c) Fe2 (SO4)3 (d) Na3PO4
(a) are suspensions of one phase in another. 75. Which gas will be adsorbed on a solid to greater extent?
(b) are two phase systems. (a) A gas having non polar molecule.
(c) contain only water soluble particles. (b) A gas having highest critical temperature (Tc).
(d) are true solutions. (c) A gas having lowest critical temperature.
65. When a colloidal solution is observed under ultrami- (d) A gas having highest critical pressure.
76. Colloidal particles in a solution can be coagulated by
croscope, we can see
(a) heating.
(a) light scattered by colloidal particle.
(b) adding an electrolyte.
(b) size of the colloidal particle. (c) adding oppositely charged sol.
(c) shape of the colloidal particle. (d) all of these
(d) relative size of the colloidal particle. 77. Emulsifier is an agent which
66. Colloidal solutions are classified on the basis of (a) accelerates the dispersion.
(a) molecular size. (b) homogenises an emulsion.
(b) organic or inorganic. (c) stabilizes an emulsion.
(c) surface tension value. (d) aids the flocculation of an emulsion.
(d) pH value. 78. Given below are a few electrolytes, indicate which one
67. The electrical charge on a colloidal particle is indicated among them will bring about the coagulation of a gold
by solution quickest and in the least of concentration?
(a) Brownian movement (b) electrophoresis (a) NaCl (b) MgSO4
(c) ultra microscope (d) molecular sieves (c) Al2(SO4)3 (d) K4[Fe(CN)6]
68. Crystalloids differ from colloids mainly in respect of 79. The minimum concentration of an electrolyte required
to cause coagulation of a sol is called
(a) electrical behaviour (b) particle nature
(a) flocculation value (b) gold number
(c) particle size (d) solubility
(c) protective value (d) None of these

80. Smoke precipitator works on the principle of 3. Match the columns.

(a) distribution law. Column I Column II
(b) neutralisation of charge on colloids.
(A) Protective colloids (P) Gold number
(c) Le-Chaterlier’s principle.
(d) addition of electrolytes. (B) Example of lyophilic (Q) Gelatin Colloids
81. Which one of following statements is not correct in re- (C) Dialysis (R) Purification of sols
spect of lyophilic sols? (D) As2S3 sol (S) Negatively charged
(a) There is a considerable interaction between the sols
dispersed phase and dispersion medium. 4. Match the columns.
(b) These are quite stable and are not easily coagu-
Column I Column II
lated.
(c) They carry charge. (A) Fog (P) Gel
(d) The particle are hydrated. (B) Milk (Q) Foam
82. As2S3 sol is (C) Cheese (R) Emulsion
(a) positive colloid (b) negative colloid (D) Soap lather (S) Aerosol
(c) neutral colloid (d) None of these 5. Match the columns.
83. Which of the following electrolyte will be most effec-
Column I Column II
tive in coagulation of gold sol?
(a) NaNO3 (b) K4[Fe(CN)6] (A) Electrophoresis (P) Movement of mol-
ecules of dispersion
(c) Na3PO4 (d) MgCl2
medium
84. During electro – osmosis of Fe (OH)3 Sol
(a) Sol particles move towards anode (B) Electro-osmosis (Q) Mechanical property
(b) Sol particles move towards cathode (C) Tyndall effect (R) Optical property
(c) The dispersion medium move towards anode (D) Brownian motion (S) Determination of
(d) The sol particles do not move in either direction charge on colloidal
85. Alums purify muddy water by particles
(a) dialysis (b) absorption Comprehension 1 (Q. 6 to 8)
(c) coagulation (d) forming true solution
There are certain colloids which behave as normal strong
electrolytes at low concentrations, but exhibit colloidal prop-
erties at higher concentrations due to the formation of aggre-
LEVEL III gated particles. These are known as micelles or associated
colloids. Surface active agents like soaps and synthetic deter-
1. Match the columns. gents belong to this class.
● Critical micelle concentration (CMC) is the lowest
Column I Column II
concentration at which micelle formation appears.
(A) Gas dispersed in liquid (P) Emulsion CMC increases with the total surfactant concentration.
At concentration higher than CMC, they form extend-
(B) Liquid dispersed in gas (Q) Foam
ed parallel sheets known as lamellar micelles which
(C) Liquid dispersed in solid (R) Gel resemble biological membranes. With two molecules
(D) Liquid dispersed in liquid (S) Aerosol thick, the individual molecule is perpendicular to the
sheets such that hydrophilic groups are on the outside
2. Match the columns. in aqueous solution and on the inside is a non-polar
medium.
Column I Column II ● In concentrated solution, micelles take the form of long
(A) Example of (P) Scattering of light cylinders packed in hexagonal arrays and are called ly-
Coagulation totropic mesomorphs.
● In an aqueous solution (polar medium), the polar
(B) Dialysis (Q) Converting precipitate groups point towards the periphery and the hydropho-
into colloidal solution bic hydrocarbon chains point towards the centre form-
(C) Peptization (R) Purification of colloids ing the core of the micelle.
● Micelles from the ionic surfactants can be formed only
(D) Tyndall effect (S) Formation of deltas above a certain temperature called the kraft tempera-
ture.

● They are capable of forming ions. 12. Electrical chimneys are made on the principle of
● Molecules of soaps and detergents consist of lyophilic (a) Electroosmosis (b) Electrophoresis
as well as lyophobic parts which associate together to (c) Coagulation (d) All of these
form micelles.
Comprehension 3
● Micelles may contain as many as 100 molecules or
Question No. 13 to 14 (2 Questions)
more.
6. Select the incorrect statements (s). The protective power of the lyophilic colloids is expressed in
(a) Surface active agents like soaps and synthetic de- terms of gold number a term introduced by Zsigmondy. Gold
tergents are micelles. number is the number of milligram of the protective colloid
(b) Soaps are emulsifying agents. which prevent the coagulation of 10 mL of red gold sol. when
(c) C17H35 (hydrocarbon part) and –COO (carboxyl- 1 mL of a 10 percent solution of sodium chloride is added
ate) part of stearate ion (C17H35 COO–) both are to it. Thus, smaller the gold number of lyophilic colloid, the
hydrophobic. greater is the protective power.
(d) All are incorrect statements. 13. On addition of one mL of solution of 10% NaCl to 10
7. In multimolecular colloidal sols, atoms or molecules mL of red gold sol in presence of 0.025 g of starch,
are held together by the coagulation is just prevented. The gold number of
(a) H-bonding starch is
(b) van der Waal’s forces (a) 0.025 (b) 0.25 (c) 2.5 (d) 25
(c) ionic bonding 14. Gold number gives an indication of
(d) polar covalent bonding (a) protective nature of colloids
8. Cleansing action of soap occurs because (b) purity of gold in suspension
(a) oil and grease can be absorbed into the hydropho- (c) the charge on a colloidal solution of gold
bic centres of soap micelles and washed away. (d) g-mole of gold per litre
(b) oil and grease can be absorbed into hydrophilic
Assertion/Reason
centres of soap micelles acid washed away.
(c) oil and grease can be absorbed into both hydro- These questions contains, Statement I (assertion) and State-
philic and hydrophobic centres but not washed ment II (reason).
away. (a) Statement I is true, Statement II is true; Statement II is
(d) cleansing action is not related to micelles. correct explanation for Statement I.
(b) Statement I is true, Statement II is true; Statement II is
Comprehension 2
NOT a correct explanation for statement I
Question No. 9 to 12
(c) Statement I is true, Statement II is false
The clouds consist of charged particles of water dispersed in (d) Statement I is false, Statement II is true
air. Some of them are positively charged, others are negative- 15. Statement I: For adsorption DG, DH, DS all have –ve
ly charged. When positively charged clouds come closer they values.
have cause lightening and thundering whereas when positive Statement II: Adsorption is a exothermic process in
and negative charged colloids come closer they cause heavy which randomness decreases due to force of attraction
rain by aggregation of minute particles. It is possible to cause between adsorbent and adsorbate.
artificial rain by throwing electrified sand or silver iodide 16. Statement: IMore heat evolved in physisorption than
from an aeroplane and thus coagulation the mist hanging in in chemisorption.
air. Statement II: Molecules of adsorbate and adsorbent
9. When excess of AgNO3 is treated with KI solution, AgI are held by van der Waals' forces in physisorption and
forms by chemical bonds in chemisorption.
(a) positively charged sol 17. Statement I: Protein, starch are lyophilic colloids.
(b) negatively charged sol Statement II: They have strong interaction with the
(c) neutral sol dispersion medium.
(d) true solution 18. Statement I: Isoelectric point is pH at which colloidal
10. Clouds are colloidol solution of can move towards either of electrode.
(a) liquid in gas (b) gas in liquid Because
(c) liquid in liquid (d) solid in liquid Statement II: At isoelectric point, colloidal particles
11. AgI helps in artificial rain because become electrically neutral.
(a) It helps in coagulation 19. Statement I: When AgNO3 is treated with excess of
(b) It helps in dispersion process potassium iodide, colloidal particles gets attracted to-
(c) Both of these wards anode.
(d) None of these Because

Statement II: Precipitate adsorb common ions (ex- 28. Which of the following are multimolecular colloids?
cess) and thus become charged. (a) Sulphur sol (b) Egg albumin in water
20. Statement I: For adsorption DG, DH, all have –ve (c) Gold sol (d) Soap solution
values 29. Which of the following colloidal solutions contain neg-
Statement II: Adsorption is a spontaneous exothermic atively charged colloidal particles?
process in which randomness decreases due to force of (a) Fe(OH)3sol (b) As2S3 sol
repulsion between adsorbent and adsorbate. (c) Congored (d) Gold. sol.
21. Statement I: A gas with higher critical temperature 30. Lyophilic sols among the following are
gets adsorbed to more extent than a gas with lower (a) Gelatin (b) Gold sol
critical temperature. (c) Starch (d) Sulphur
Because 31. Which of the following statements are true?
Statement II: The easily liquifiable gases get adsorbed (a) Soap solution contains ionic micelles as the col-
to more extent due to high value of (a) Vander Waal loidal particles.
constant. (b) Physisorption reversible in nature
22. Statement I: Micelles are formed by surfactant mol- (c) Chemisorption is highly specific.
ecules above the critical micelle concentration (CMC). (d) Chemisorption needs high activation energy.
Because 32. Which of the following statements are true for physi-
Statement II: The conductivity of a solution having sorption?
surfactant molecules decreases sharply at the CMC. (a) Extent of adsorption increases with increase in
23. Which among the following statement are correct with pressure.
(b) It needs activation energy.
respect to adsorption of gases on a solid?
(c) It can be reversed easily.
(a) The extent of adsorption is equal to kpn according
(d) It occurs at high temperature.
to Freundiich isotherm.
33. A lyophobic colloidal solution can be precipitated by
(b) The extent of adsorption is equal to kp1/n accord-
(a) adding lyophilic colloid.
ing to Freundlich isotherm.
(b) heating.
(c) The extent of adsorption is equal to (1 + bp)/ap
(c) adding electrolyte.
according to Langmuir isotherm.
(d) adding same charged colloid.
(d) The extent of adsorption is equal to ap/(1 + ap)
34. For physical adsorption of a gas on solid adsorbent
according to Langmuir isotherm. (a) DH is positive (b) DS is negative
24. Select the incorrect statement(s): (c) DG is negative (d) DE is positive
(a) Surface active agent like soaps and synthetic de- 35. Which of the following statements is/are correct?
tergents are micelles. (a) In adsorption, the concentration of the adsorbate
(b) Soaps are emulsifying agents. increases only at the surface of the adsorbent.
(c) C17H35 (hydrocarbon part) and –COO–(carboxyl- (b) In absorption, the concentration is uniform
ate part) of stearate ion (C17H35COO–) both are throughout the bulk of the solid.
hydrophobic. (c) Adsorption is instantaneous, thus fast.
(d) Micelles form above critical tempreture. (d) Absorption is slow.
25. Which of the following statement(s) is/are correct? 36. When negatively charged colloids like As2S3 sol is
(a) Higher the gold number, more protective power added to positively charged Fe(OH)3 sol in suitable
of colloid. amounts
(b) Lower the gold number, more the protective pow- (a) Both the sols are precipitated simultaneously.
er. (b) This process is called mutual coagulation.
(c) Higher the coagulation value, more the coagula- (c) They becomes positively charged colloids.
tion power. (d) They becomes negatively charged colloids.
(d) Lower the coagulation value, higher the coagula- 37. Which of the following are colloids?
tion power. (a) Milk (b) Ice cream
26. The charge on the colloidal particles is due to (c) Urea solution (d) Blood
(a) self-dissociation. 38. Which of the following is/are correct statements?
(b) electron capture during Bredig’s arc method. (a) Hardy Schulz rule is related to coagulation.
(c) selective adsorption of ion on their surface. (b) Brownian movement and Tyndall effect are
(d) addition of protective colloids. shown by colloids.
27. Which of the following aqueous solution is most effec- (c) When liquid is dispersed in liquid, it is called gel.
tive in the coagulation of an arsenious sulphide sol? (d) Gold number is a measure of protective power of
(a) KCl (b) MgCl2 (c) AlCl3 (d) FeCl3 lyophillic colloid.

39. Which statement is/are correct? (a) 1.9 ¥ 1012 (b) 6.3 ¥ 1014
(a) Physical adsorption is multilayer non-directional (c) 6.3 ¥ 1010 (d) 2.4 ¥ 106
and non-specific.
(b) Chemical adsorption is generally monolayer and
specific in nature. PREVIOUS YEARS’ QUESTIONS
(c) Physical adsorption is due to free e– OF JEE (MAIN AND ADVANCED)
(d) Chemical adsorption is stronger than physical ad- 1. The volume of a colloidal particle, VC as compared to
sorption. the volume of a solute particle in a true solution VS,
40. Which is the following is/are correct for lyophillic could be [AIEEE, 2005]
sols?
VC VC
(a) Its surface tension is lower than that of H2O. (a) 1 (b) 1023
(b) Its viscosity is higher than that of water. VS VS
(c) Its surface tension is higher than that of water. VC VC
(d) Its viscosity is equal to that of water. (c) 10 –3 (d) 103
VS VS
41. Which statement(s) is/are correct?
(a) A solution is prepared by addition of excess of 2. The disperse phase in colloidal iron (III) hydroxide and
AgNO3 solution in KI solution. The charge likely colloidal gold is positively and negatively charged, re-
to develop on colloidal particle is positive. spectively. Which of the following statement is NOT
(b) The effects of pressure on physical adsorption is correct? [AIEEE, 2005]
high if temperature is low. (a) Magnesium chloride solution coagulates, the gold
(c) Ultracentrifugation process is used for prepara- sol more readily than the iron (III) hydroxide sol.
tion of lyophobic colloids. (b) Sodium sulphate solution cause coagulation in
(d) Gold number is the index for extent of gold plat- both sols.
ing done. (c) Mixing the sols has no effect.
42. Colloidal solution can be purified by (d) Coagulation in both sols can be brought about by
(a) dialysis (b) electrodialysis
electrophoresis.
(c) electrophoresis (d) ultrafiltration
3. Among the following, the surfactant that will form mi-
43. Coagulation of colloids can be achieved by
(a) centrifugation (b) adding electrolyte celles in aqueous solution at the lowest molar concen-
(c) change in pH (d) adding water tration at ambient conditions is [JEE, 2008]
44. Which are the properties of sols. (a) CH3(CH2)15N+(CH3)3Br¯
(a) Adsorption (b) Tyndall effect (b) CH3(CH2)11OSO3¯Na+
(c) Flocculation (d) Paramagnetism (c) CH3(CH2)6COO¯Na+
45. Which of the following is not lyophillic? (d) CH3(CH2)11N+(CH3)3Br¯
(a) gelatin sol (b) silver sol 4. Which of the following statements is incorrect regard-
(c) sulphur sol (d) As2S3 sol ing physissorptions? [AIEEE, 2009]
46. Colloidal Gold can be prepared by (a) Under high pressure it results into multi molecu-
(a) Bredig’s are method (b) reduction of AuCl3 lar layer on adsorbent surface.
(c) hydrolysis (d) peptisation (b) Enthalpy of adsorption (DH adsorption) is low
47. The coagulation of sol particles may be brought about and positive.
by (c) It occurs because of Van der Waal’s forces.
(a) heating. (d) More easily liquefiable gases are adsorbed readily.
(b) addition oppositely charged sol. 5. Among the electrolytes Na2SO4, CaCl2, Al2(SO4)3 and
(c) addition electrolyte.
NH4Cl, the most effective coagulation agent for Sb2S3
(d) persistent dialysis.
sol is [JEE, 2009]
48. Which one is not lyophobic in nature?
(a) Gelatin (b) Sulphur (a) Na2SO4 (b) CaCl2
(c) Starch (d) Protein (c) Al2(SO4)3 (d) NH4Cl
49. On adding 1 mL of solution of 10% NaCl to 10 mL of 6. The correct statement(s) pertaining to the adsorption of
gold sol in the presence of 0.25 g of starch, the coagula- a gas on a solid surface is (are)
tion is just prevented. The gold number of starch is (a) Adsorption is always exothermic. [JEE, 2011]
(1) 0.25 (2) 0.025 (3) 25 (4) 250 (b) Physisorption may transform into chemisorption
50. The density of gold is 19 g/cm3. If 1.9 ¥ 10–4 g of gold at high temperature.
is dispersed in 1 L of water to give a sol having spheri- (c) Physisorption increases with increasing tempera-
cal gold particles of radius 10 nm, then the number of ture but chemisorption decreases with increasing
gold particles per mm3 of the sol will be temperature.

(d) Chemisorption is more exothermic than physi- (IV)
Potential energy
sorption, however it is very slow due to higher
Eads
energy of activation. 0 Distance of molecule
7. According to Freundlich adsorption isotherm, which of from the surface
DHads = 150 kJ mol
the following is correct? [AIEEE, 2012]
x
(a) μ p0 (a) I is physisorption and II is chemisorption
m (b) I is physisorption and III is chemisorption
x (c) IV is chemisorption and II is chemisorption
(b) μ p1
m (d) IV is chemisorption and III is chemisorption
x 9. Choose the correct reason(s) for the stability of the lyo-
(c) μ p1/n phobic colloidal particle. [JEE, 2012]
m
(a) Preferential adsorption of ions on their surface
(d) All the above are correct for different ranges of
pressure. from the solution
8. The given graphs/data I, II, III and IV represent general (b) Preferential adsorption of solvent on their surface
trends observed for different physisorption and chemi- from the solution
sorption processes under mild conditions of tempera- (c) Attraction between different particles having op-
ture and pressure. Which of the following choice(s) posite charges on their surface
about I, II, III and IV is (are) correct? [JEE, 2012] (d) Potential difference between the fixed layer and
(I) the diffused layer of opposite charges around the
P constant
gas adsorbed
Amount of
colloidal particles
10. Methylene blue, from its aqueous solution, is adsorbed
on activated charcoal at 25°C. For this process, the cor-
rect statement is [2013 Adv.]
T
(a) the adsorption requires activation at 25°C.
(II) P constant
gas absorbed
(b) the adsorption is accompanied by a decreases in

Amount of
enthalpy.
(c) the adsorption increases with increase of tempera-
ture.
T (d) the adsorption is irreversible.
(III) 11. The coagulating power of electrolytes having ions Na+,
gas adsorbed
200 K
Amount of
250 K Al3+ and Ba2+ for arsenic sulphide sol increases in the
order [2013 Adv.]
(a) Al3+ < Ba2+ < Na+ (b) Na+ < Ba2+ < Al3+
P
(c) Ba2+ < Na2+ < Al3+ (d) Al3+ < Na+ < Ba2+
Answer Key
LEVEL I
1. (d) 2. (d) 3. (b) 4. (b) 5. (d) 6. (c) 7. (c) 8. (b) 9. (b) 10. (d)
11. (d) 12. (c) 13. (a) 14. (b) 15. (b) 16. (b) 17. (d) 18. (c) 19. (c) 20. (c)
21. (a) 22. (a) 23. (c) 24. (a) 25. (b) 26. (d) 27. (a) 28. (b) 29. (c) 30. (b)
31. (b) 32. (b) 33. (d) 34. (c)
LEVEL II
1. (c) 2. (d) 3. (a) 4. (a) 5. (c) 6. (c) 7. (c) 8. (a) 9. (c) 10. (b)
11. (c) 12. (a) 13. (d) 14. (c) 15. (b) 16. (a) 17. (c) 18. (b) 19. (d) 20. (a)
21. (a) 22. (a) 23. (a) 24. (d) 25. (b) 26. (b) 27. (c) 28. (c) 29. (b) 30. (b)

31. (d) 32. (a) 33. (a) 34. (a) 35. (c) 36. (a) 37. (a) 38. (a) 39. (a) 40. (d)
41. (a) 42. (c) 43. (a) 44. (c) 45. (a) 46. (c) 47. (c) 48. (a) 49. (a) 50. (a)
51. (d) 52. (b) 53. (d) 54. (c) 55. (b) 56. (d) 57. (a) 58. (b) 59. (b) 60. (c)
61. (b) 62. (c) 63. (b) 64. (b) 65. (a) 66. (a) 67. (b) 68. (c) 69. (a) 70. (d)
71. (a) 72. (c) 73. (d) 74. (c) 75. (b) 76. (d) 77. (c) 78. (c) 79. (a) 80. (b)
81. (c) 82. (b) 83. (d) 84. (c, d) 85. (c)
LEVEL III
1. (A) Æ q; (B) Æ s; (C) Æ r; (D) Æ p 2. (A) Æ s; (B) Æ r; (C) Æ q; (D) Æ p

3. (A) Æ p, q; (B) Æ q; (C) Æ r; (D) Æ s 4. (A) Æ s; (B) Æ r; (C) Æ p; (D) Æ q
5. (A) Æ s; (B) Æ p; (C) Æ r; (D) Æ q
6. (c) 7. (b) 8. (a) 9. (a) 10. (a) 11. (c) 12. (b) 13. (d) 14. (a) 15. (a)
16. (d) 17. (a) 18. (b) 19. (c) 20. (d) 21. (a) 22. (b) 23. (b, d) 24. (c, d) 25. (b, d)
26. (a, b, c) 27. (c, d) 28. (a, c) 29. (b, c, b) 30. (a, c) 31. (a, b, c, d) 32. (a, c)
33. (b, c) 34. (b, c) 35. (a, b, c, d) 36. (a, b) 37. (a, b, d) 38. (a, b, d) 39. (a, b, d)
40. (a, b) 41. (a, b) 42. (a, b, d) 43. (a, b, c) 44. (a, b, c) 45. (b, c, d)
46. (a, b) 47. (a, b, c, d) 48. (a, c, d) 49. (d) 50. (d)
PREVIOUS YEARS’ QUESTIONS OF JEE (MAIN AND ADVANCED)
1. (d) 2. (c) 3. (a) 4. (b) 5. (c) 6. (a, b, d) 7. (d) 8. (a, c) 9. (a, d) 10. (b)
11. (b)
Hints and Solutions

etc. may be prepared by just shaking them with water
LEVEL I but Special Methods are needed to prepare lyophobic
sols and the methods used are
1. (d) Micelles formation takes place only above CMC Æ mechanical method
and above kraft temperature. Æ electrical method
2. (d) positively charged sol. Æ ultrasonic dispersion
Æ Sols of metal hydroxide (Fe, Al, Cr) Peptisation and condensation method
Æ Sols of basic dyes (methylene blue, methyl violet)
Æ Haemoglobin, protein in acidic medium
Physical Chemical
Æ Oxides TiO2
Æ Some metal sols like Bi, Pb, Fe, etc. Æ By exchange of solvent Æ Double decomposition
–vely sols Æ Super cooling method Æ Hydrolysis
Metal sols Au, Ag, Pt, Cu metal sulphide AS2S3, CdS Æ Vapour condensation Æ Oxidation
Starch, mud, charcoal, congored Eusin, Acidic dye, si- Æ Reduction
licicacid Blood, Smoke, Soapmicelles 6. (c)
Neutral colloid
Tween-20 polyoxyethylene glycol derivative.
3. (b) At intermediate pressure in freundlich adsorption x
x m
isotherm = kp1/n
m
4. (b) Theory based
5. (d) Lyophilic Colloids needs no special method and the T
Physical adsorption
sol is easily prepared by bringing the dispersed phase
in the contact with dispersion medium example col- Ea = 0
loids of gum, gelatin starch, agar-agar, protein starch DH = –ve

So, according to Le Chatlier principle x

x 1 \ = antilog 1.6020
μ m
m temperature
x
\ = 40 gram
m
x
m 18. (c) Reactant and catalyst occur in same phase
NO(g)
2CO + O2 2CO2
T (g) (g) (g)
Chemical adsorption
Same Phase fi Gas Phase
Extent of adsorption first increases up to certain tem-
perature and then desorption is favoured at high tem- +
C12H22O11(l) + H2O(l) H Glucose + Fructose
perature initial increase in the extent of chemisorption
with temperature is because some Ea is required to
cross energy barrier. Solution Phase catalysis
7. (c) Theory based
8. (b) True solution is a homogeneous mixture 19. (c) Catalyst change the path of reaction positive cata-
9. (b) Theory based lyst EaØ Enzyme act as positive catalyst.
10. (d) Colour due to size of disperesed phase particle if 20. (c)
size of Au different then colour different. 21. (a) Coagulating power μ charge
11. (d) Water in oil emulsion cod liver oil. NO3- < SO 4- Cr2O7- < [Fe (CN)6 ]-4
12. (c) Cellulose dispersed in ethanol called collodion.
22. (a) Intrinsic colloid or Lyophilic colloid, e.g., strach,
13. (a) Threshold energy of intermediate adsorbed com-
rubber, protein, glue.
pound is less than unadsorbed intermediate.
23. (c) Theory based
x 1
x
Uncatalysed (Ea ) 24. (a) In Freundlich adsorption isotherm = K ¥ pn
m Catalysed activated m
Complex (EaØ) \ n = 1 to
1
T \ = 0 to 1
Chemical adsorption n
14. (b) Extent of adsorption decreases with increase in 25. (b) Adsorption is a spontaneous process so
temperature. DG = –ve
15. (b) Adsorption μ Polarity or M mass DS = –ve
16. (b) According to Hardy Schulze rule, higher the va- Since bond formed so DH = –ve.
lency of the active ion greater will be its power to pre- 26. (d) Catalyst change the path of reaction
cipitate the solution and reciprocal of coagulation value or
(or amount of electrolyte). Activation energy Ø (+ve catalyst)
For As2S3 sol (–vely charged sol) amount of cation Activation energy ≠ (–ve catalyst)
used for coagulation. 27. (a) Fog fi Liquid in gas
K+ > Mg+2 > Al+3 Dispersed Dispersion
Phase Medium
x 1
17. (d) = KP n 28. (b)
m
29. (c) 1 nm to 1000 nm
x 1
log = log k + log p fi 10–9m to 10–6m
m n 10–7cm to 10–5cm
1 30. (b) 1 nm to 1000 nm
= log 10 + log 4
n fi 10–9m to 10–6m
1
slop = = tan q = tan 45∞ = 1 10-9 10-6
n -6
m to -6
m fi 10-3 m to 1m
10 10
x 1
log = 1 + log 4 fi 1 millim to 1m
m 1
31. (b) Characterties of lyophilic calloid
x
log = 1 + 0.6020 = 1.6020 32. (b)
m

33. (d) Gelatin when dissolve in water, is a calloid because 42. (c)
the protein molecules dispersed through the water gela- 43. (a)
tin remains in liquid when warm becoming a gel (an- 44. (c)
other colliod) when cooled. 45. (a)
34. (c) 46. (c)
47. (c)
48. (a) Molar concentration of a sol is much smaller than
LEVEL II that in a true solution of same strength (g L–1) due to
much larger particles.
49. (a)
1. (c) Colloids are purified by dialysis, ultrafiltration.
2. (d) Gold, strach AS2S3 – vely charged colloid 50. (a)
3. (a) Coagulation is a process which involves coming to- 51. (d)
gether of colliodal particles by neutralising the charge 52. (b)
of dispersed phase particle. 53. (d)
4. (a) 54. (c)
5. (c) 55. (b)
6. (c) 56. (d)
7. (c) 57. (a)
8. (a) 58. (b)
9. (c) 59. (b)
10. (b) 60. (c)
11. (c) 61. (b)
12. (a) 62. (c)
13. (d) 63. (b)
14. (c) 64. (b)
15. (b) 65. (a)
16. (a) 66. (a)
17. (c) The stability is attributed to electric charge on the 67. (b)
sol particles. 68. (c)
18. (b) 69. (a) Since the sol particles migrate towards cathode,
19. (d) they are positively charged. Hence, anions would be
20. (a) effective in coagulation. Greater is the valence of effec-
21. (a) tive ion, smaller will be its coagulation value.
22. (a) 70. (d)
23. (a) 71. (a)
24. (d) 72. (c)
25. (b) 73. (d)
26. (b) 74. (a) The sulphur sol is negatively charged and would be
27. (c) coagulated most effectively by Al3+.
28. (c) There will be net decrease in volume. 75. (b)
29. (b) 76. (d)
30. (b) 77. (c)
31. (d) 78. (c)
32. (a) 79. (a)
33. (a) 80. (b)
34. (a) 81. (c)
35. (c) 82. (b)
36. (a) 83. (d)
37. (a) 84. (c, d) In electro – osmosis, the sol particle are pre-
38. (a) vented from migration where as the dispersion medium
39. (a) migrates in the direction opposite to those of particles.
40. (d) Here the medium is negatively charged.
41. (a) 85. (c)

LEVEL III (iii) More stable (iii) Less stable (Requires,

stabilizing agent)
(iv) Reversible in nature (iv) Irreversible in nature
1. (A Æ Q, B Æ S, C Æ R, D Æ P)
2. (A Æ S; B Æ R; C Æ Q; D Æ P) (v) Coagulation is not so (v) Easily Coagulated
3. (A Æ P, Q; B Æ Q; C Æ R; D Æ S) easy.
4. (A Æ S; B Æ R; C Æ P; D Æ Q) (vi) Higher degree of sol- (vi) Lower degree of hy-
5. (A Æ S; B Æ P; C Æ R; D Æ Q) vation or Hydration dration or Solvation
(vii) Viscosity is more and (vii) Viscosity and surface
Comprehension 1 surface tension is less tension are nearly the
6. (c) as compared to that of same as that of disper-
7. (b) dispersion medium sion medium.
8. (a) Ex. Generally of organic Ex. Generally of in organic
nature like sols of protein, nature like sols of metals
Comprehension 2 starch etc. metal sulphides, etc.
9. (a) 18. (b)
10. (a) 19. (c)
11. (c) 20. (d)
12. (b) 21. (a)
22. (b)
Comprehension 3 23. (b, d) According to Freundlich isotherm
13. (d) x 1
μ pn
14. (a) m
x 1
Assertion and Reason Kp n n 1
m
15. (a) x
16. (d) = extent of adsorption
m
Physical Adsorption Chemical adsorption x 1
log = log K + log p
Æ It arises due to weak Æ It arises due to formation m n
Vanderwall forces of strong chemical bonds. Following equilibrium is established:
Adsorption
Æ Heat of adsorption is low Æ Heat of adsorption is high A (g) + M (S) AM (s)
Desorption
i.e., from –20 to –40 kJ i.e., from –80 to –240 kJ
mol–1 mol–1 Ra μ P ¥ [n(1 – q)] = Pressure ¥ Number of sites avail-
able.
Æ Reversible in Nature Æ Generally irreversible in
Ra = KaPn (1 – q)
nature
Rd = Kdnq
17. (a) At equilibrium
Rate of adsorb = Rate of desorption
Lyophilic (Solvent living) Lyophobic Ka ¥ P ¥ n(1 – q) = Kd ¥ nq
(Hydrophilic) (Solvent lating)
Ka
Greater affinity (Hydrophobic Lesser ¥ p (1 - q ) = q
affinity) Kd
a ¥ p(1 – q) = q
(i). When the particles of (i) When the particles of
Dp have a greater af- Dp have a lesser af- 1-q 1
=
finity for the particles finity for the particles q a.p.
of dispersion medium, of dispersion medium 1 1
then the colloids is then the colloids is -1=
q a.p.
known as Lyophilic. known as hyophobic
ap
(ii) Easily prepared just by (ii) It require special meth- q=
1 + ap
mixing the dispersed ods for preparation
phase with dispersion Number of adsorption site occupied
q=
medium Number of adsorption available

24. (c, d)
2.38 ¥ 1012
25. (b, d) \ Number of gold particle in 1 mm3 =
26. (a, b, c) 106
27. (c, d) = 2.38 ¥ 106
28. (a, c)
29. (b, c, d) PREVIOUS YEARS’ QUESTIONS
30. (a, c) OF JEE (MAIN AND ADVANCED)
31. (a, b, c, d)
32. (a, c) 1. (d)
33. (b, c) 2. (c)
34. (b, c) 3. (a)
4. (b)
35. (a, b, c, d)
5. (c)
36. (a, b)
6. (a, b, d)
37. (a, b, d) 7. (d)
38. (a, b, d) 8. (a, c) Graph-I represent physisorption as in physisor-
39. (a, b, d) ption, absorbents are bonded to adsorbate through weak
40. (a, b) van der Waal's force. Increasing temperature increases
41. (a, b) kinetic energy of adsorbed particles increasing the rate
42. (a, b, d) of desorption, hence amount of adsorption decreases.
43. (a, b, c) Graph-III also represents physical adsorption as ex-
44. (a, b, c) tent of adsorption increasing with pressure.
45. (b, c, d) Graph-II represents chemisorption as it is simple acti-
46. (a, b) vation energy diagram of a chemical reaction.
47. (a, b, c, d) Graph-IV represents chemisorption as it represents the
48. (a, c, d) potential energy diagram for the formation of a typical
49. (d) Minimum amount of protective colloid in milli covalent bond.
grams which prevents a color change from red to violet 9. (a, d)
of 10 ml gold sol by the addition of 1 ml of 10% NaCl 10. (b)
solution. Æ Physical adsorption takes place with decrease in
Here protective colloid 0.25 gram starch = 0.25 ¥ 1000 enthalpy thus exothermic change. It is physical ad-
= 250 mg sorption and does not require activation. Thus, (A)
is incorrect.
\ Gold No. = 250
Æ Being physical adsorption DH < 0 thus, (B) is cor-
50. (d) Volume of the gold dispersed in 1 L water =
rect.
m 1.9 ¥ 10-4 Æ Exothermic reaction is favoured at low tempera-
= = 1 ¥ 10-5
d 19 g/cm3 ture thus (c) is incorrect.
Radius of gold particle = 10 nm = 10–6 cm Æ Physical adsorption is always reversible, thus (D)
is incorrect.
4 4 22
\ volume = p r 3 = ¥ ¥ (10-6 )3 = 4.19 ¥10-18 cm3 11. (b) According to Hardy Schulze rule, greater the charge
3 3 7 on oppositely charged ion, greater is its coagulating
1 ¥ 10-5 power. Since arsenic sulphide is a negatively charged
Number of particles in 1 ¥ 10–5 cm3 = sol, thus, the order of coagulating power is Na+ < Ba2+
4.19 ¥ 10-18 < Al3+.
= 2.38 ¥ 1012

Chapter
6
Redox
Key Concepts
Here copper acts as non-reducing agent means as an oxidis-
OXIDATION AND REDUCTION ing agent.
Oxidation is the process of de-electronation during which Rules for Assigning Oxidation Numbers
oxidation number increases. (i) Sum of oxidation numbers of all atoms present in a
Oxidation reaction can also be defined as follows. neutral compound is equal to zero.
(i) Loss of hydrogen (ii) Sum of oxidation number of all atoms present in an ion
(ii) Gain of oxygen is equal to charge on the ion.
(iii) Loss of electron (iii) The oxidation number of an atom in elementary state is
Reduction: It is the process of electronation during which zero.
oxidation number decreases. (iv) The oxidation number of a mono-atomic ion is equal to
Reduction reaction can also be defined as follows. charge on it.
(i) Gain of hydrogen (v) The oxidation number of oxygen in most of the com-
(ii) Loss of oxygen pounds is –2. But in peroxides, it is –1 and in OF2, It is +2.
(iii) Gain of electron (vi) The oxidation number of hydrogen is +1 in most of the
Oxidising Agent or Oxidant: It is the substance which compounds but in active metal hydrides (hydrides of
undergoes reduction, and oxidises other substance. It gains group 1 and 2) it is –1.
electrons and its oxidation number decreases. (vii) The oxidation number of alkali metals in all the com-
e.g. O2, O3, X2, KMnO4, K2Cr2O7, H2SO4, HNO3, etc., and pounds is +1.
oxides of metals and non metal (in heighest oxidation state) (viii) The oxidation number of alkali metals in all the com-
pounds is +2.
Reducing Agent or Reductant: It is the substance, which (ix) The oxidation number of fluorine in all the compounds
undergoes oxidation and reduces other substance. It shows is –1.
loss of electron during the process and its oxidation number (x) The oxidation number of all halogens is -1 except when
increases. All the metals are reducing agents. the other atom present in the compound is oxygen.
Reducing agent: [H], C, CO, H2S, SO2, SnCl2, Na2S2O3, Al, (xi) The oxidation number of metals in amalgams is zero.
Na, CaH2, LiAlH4, NaBH4 (xii) Maximum oxidation state of any element = Valance
Alkali metals and alkaline earth metals in general are very electron
strong reducing agents. Q. State which of the following changes are oxidation, re-
In general metals behave as reducing agent while non- duction, both or none:
metals behave as oxidising agents but it is not always true. Na h NaOH
( +1)
For example, CuSO4 + Zn h ZnSO4 + Cu (0)

Since ON of sodium increases means oxidation. Reduction of Cl

( +6) ( +6)
(+5) (–2) (–1) (0)
and K 2CrO 4 ææ Æ K 2Cr2O7 KClO3 KCl + O2
e.g.
None since ON of chromium remains same
Reduction Oxidation of O
Q. Identify the examples of intermolecular disproportion
0 –1 +5
Cl2 Cl– + Cl1O–3 and intermolecular redox reaction.
Oxidation
Oxidation (–1) (–2)
1 (0)
One chlorine oxidises and other one reduces 1. H2O2 H2O + O
2 2
( +5) ( +5)
P2O5 h H 4 P2O7 Reduction
Disproportionation reaction:
Since ON of phosphorus remains same in both cases
here no process takes place. Reduction
Q. Find oxidising agent (OA) and reducing agent (RA): (–3) (+3) (0) (–2)
(0) (+1)(+1) (+1) (+4) (0) 2. NH4 NO2 N2 + 2H2O

(A) Si + 2KOH + H2O K2SiO3 + 2H2
(+1) Oxidation
R.A O.A \ Intramolecular reaction
Hydrogen (Oxidising Agent) and Hydrogen Present in (N) Reduced
KOH and H2O and Si Reducing agent
+2 +5 –2 +2 +4 0
( +2) ( -1) ( +1)
+2 -
(0) 3. 2Pb (NO3)2 2Pb + 4NO2 + O2
(B) 2Cu + 4I h 2CuI + I 2
Reducing agent = I– (O) Oxidised
Oxidising agent = Cu+2 Intramolecular redox reaction
( -1) ( -1) ( -2) (0) 0 -1 +5
(C) 2I -2
+ H 2O 2 h 2OH - + I 2 4. 3Cl2 + 6NaOH h Na Cl + NaClO3 + 3H 2 O
R.A O.A Disproportionation reaction
( +1) ( -3) ( +1) ( -3) 0 +1 -3
(D) Ag (NH3 ) +2 + 2H + h Ag + 2NH +4 None +
5. P4 + 3NaOH + 3H 2O h 3NaH 2 PO 2 + PH3
Disproportionation reaction
TYPES OF REDOX REACTIONS 6.
( + 2) + (4)( -2)
CaCO3 h CaO + CO 2
( +2) ( -2) ( +4)( -2)
None (not a redox reaction)

Inter molecular redox reaction: If oxidation and reduction
0 +1 -1 -
takes place in different substances then the reaction are called
7. Cl2 + 2OH - h ClO - + Cl + H 2 O
intermolecular redox reaction example.
Si + 2KOH + H 2O h K 2SiO3 + 2H 2 Disproportion reaction
RA OA +7-2 +6 (0)
8. Mn O 4- h MnO 4-2 + O 2
Disproportionation Reaction _______________
Intramolecular
If oxidation and reduction take place within same compound
and of same element then the reaction are disproportionation Balancing of Redox Reaction: Total no of e– accepted by
reaction oxidising agent = total number of e– given by reducing agent
Oxidation 1. Oxidation number method
0 –1 +5
Following rules are used to balance redox reaction by oxida-
–
For example, Cl2 Cl– + ClO3 tion number method:
(i) Assign oxidation number to the atoms in the reaction
Reduction and identify the atoms, which are undergoing oxidation
Intramolecular redox reaction: If the oxidation and and reduction.
reduction take place with same compound and the elements (ii) Divide the redox reaction in two half-reaction; one rep-
involved are different or if same then in different oxidation resenting oxidation and other reduction.
number. (iii) Find the change in oxidation number per atom in both
half-reactions. Make equal changes in each half-reac-
tion by multiplying them with suitable integers.

Redox 6.3
(iv) Balance all the atoms except hydrogen and oxygen at-
MnO 4- + 5Fe +2 + 8H + h Mn +2 + 5Fe+3 + 4H 2 O
oms.
(v) In acidic medium, balance hydrogen atom by H+ ions This is the balanced equation.
and oxygen atom by H2O molecule. For example, (iii)
(vi) In basic medium, balance hydrogen atom by OH- ions Reduction
and oxygen atom by H2O molecule. 8
+3 –1 +2 –1 0 –2
(vii) Balance the charge on each side of half-reaction by Pb3O4 + HCl PbCl2 + Cl2 + H2O
adding suitable number of electrons to the side defi-
Oxidation
cient in it.
(viii) Add the two half–reaction to get balanced redox reac- Oxidation Reduction
tion. 2Cl Cl2 + 2e– 2e– + Pb3 3Pb
Ex. (i) Balance the following reaction by the oxidation
Net Reaction:
number method:
2Cl + Pb3 h 3Pb + Cl2
Cu + HNO3 h Cu(NO3)2 + NO2 + H2O
6HCl + 2HCl + Pb3O4 h 3PbCl2 + Cl2 + H2O
Sol. Write the oxidation number of all the atoms.
Balanced Reaction:
0 +1+5–2 +2+5–2 +4 –2 +1 –2 8HCl + Pb3O4 h Cl2 + 3PbCl2 + 4H2O
Cu + HNO3 h Cu(NO3)2 + NO2 + H2O
There is change in oxidation number of Cu and N. For example, (iv)
Reduction
0 +2
Cu h Cu(NO3)2 ....(1) (–2) (–3) (–1/2)
(Oxidation no. is increased by 2) P2H4 PH3 + P4H2
+5 +4 Oxidation
HNO3 h NO2 .....(2) Oxidation Reduction
(Oxidation no. is decreased by 1)
2P2 P4 + 6e– [P2 + 2e– 2P]3
To make increase and decrease equal, equation (2) is multi-
plied by 2. Net Reaction:
Cu + 2HNO3 h Cu(NO3)2 + 2NO2 + H2O 2P2 + 3P2 h P4 + 6P
Balancing nitrates ions, hydrogen and oxygen, the following 5P2 h P4 + 6P
equation is obtained.
5P2H4 h P4H2 + 6PH3 (Balanced)
Cu + 4HNO3 h Cu(NO3)2 + 2NO2 + 2H2O
For example, (v)
This is the balanced equation.
+3 -2 +5 +5 +6 +2
Ex. (ii) Balance the following reaction by the oxidation As 2S3 + HNO3 ææ
Æ H3 As O 4 + H 2SO 4 + NO
number method :
Oxidation Reduction
MnO 4- + Fe +2 h Mn +2 + Fe+3
As2 h 2As + 4e –
(N + 3e– Æ N) ¥ 28
Sol. Write the oxidation number of all the atoms. S3 h 3S + 24e–
+7 - 2
As2S3 h 2As + 3S + 28e–
MnO 4- + Fe +2 h Mn +2 + Fe+3
Net Reaction:
change in oxidation number has occurred in Mn and Fe. 3As2S3 + 28N h 6As + 9(S) + 28N
+7 +2
MnO 4- h Mn (1) 3As2S3 + 28HNO3 h 6H3AsO4 + 9H2SO4 + 28NO
(Decrement in oxidation no. by 5) +2 -1 0 +3 -2 +4 -2
For example, (vi) FeS2 + O 2 h Fe 2 O3 + SO 2
Fe+2 h Fe+3 (2)
(Increment in oxidation no. by 1) Oxidation Reduction
To make increase and decrease equal, equation (2) is multi-
1 [O2 + 4e– h 2O]11
plied by 5. 2Fe h Fe2 + e-
2
MnO -4 + 5Fe +2 h Mn +2 + 5Fe+3
S2 h 2S + 10e–
To balance oxygen, 4H2O are added to R.H.S. and to balance
hydrogen, 8H+ are added to L.H.S. È 1 -˘
ÍÎFeS2 h 2 Fe 2 + 2S + 11e ˙˚

Net Reaction: Balanced reaction:

4FeS2 + 11O2 h 2Fe2 + 8(S) + 22O 2ClO 2 + SbO 2- + 2OH - + 2H 2O h 2ClO -2 + Sb(OH)6-
4FeS2 + 11O2 h 2Fe2O3 + 8SO2 For example, (iii)
For example, (vii) Oxidation
+4 +6 +6 +3 (+7) (–3) +(5) +(4)
SO 2 + Na 2 CrO 4 + H 2 SO 4 h H 2O + Cr 2 (SO 4 )3 + Na 2SO 4 KMnO4 + NH3 KNO3 + MnO2 + KOH (Neutral)
Oxidation Reduction
3[S h S + 2e–] 6e– + 2Cr h Cr2 Reduction
Oxidation Reduction
Net Reaction
[NH3 h KNO3 + 8e ] ¥ 3 –
[3e– + 3KMnO4 h MnO2]8
3S + 2Cr h 3S + Cr2
3NH3 + 8KMnO4 h 3KNO3 + 8MnO2 + 5KOH + 3H2O
3SO2 + 2Na2CrO4 h Cr2(SO4)3 + 2Na2SO4
0 -1 +5
Balanced Reaction: For example, (iv) Cl2 h Cl- + ClO3- (Basic)
3SO2 + 2Na2CrO4 + 2H2SO4 h Oxidation Reduction
Cr2(SO4)3 + 2Na2SO4 + 2H2O 1 È 1 - -˘
Cl2 + 6OH - h ClO3- + 5e - ÍÎ 2 Cl2 + e h Cl ˙˚ 5
2. Ion electron method 2
Following rules are used to balance redox reaction by ion Balanced reaction
electron method: 3Cl2 + 6OH - h ClO3- + 5Cl- + 3H 2O
(i) Divide the redox reaction in two half-reactions; one
representing oxidation and other reduction. For example, (v)
(ii) Balance all the atoms except hydrogen and oxygen Oxidation
atom. (+3) (+7) (+5) (+4)
(iii) In acidic medium, balance hydrogen atom by H+ ions AsO–3 –
3 + MnO4 AsO4–3 + MnO2 (Basic)
and oxygen atom by H2O molecule.
(iv) In basic medium, balance hydrogen atom by OH– ions Reduction
and oxygen atom by H2O molecule. Oxidation
(v) Balance the charge on each side of half-reaction by [2OH - + AsO3-3 Æ AsO 4-3 + 2e - ] ¥ 3
adding suitable number of electrons to the side defi- Reduction
cient in it.
(vi) Multiply one or both the half-reactions with such a [3e- + MnO -4 Æ MnO 2 + 4OH - ] ¥ 2
number so that total number of electrons lost and 6OH - + 3AsO3-3 + 2MnO -4 h
gained are equal.
(vii) Add the two half-reactions to get balanced redox reac- 3AsO 4-3 + 2MnO 2 + 8OH -
tion. Balanced Reaction:
( +7) ( +3) ( +4) ( +2)
For example, (i) MnO 4- + C2 O 4-- h CO 2 + Mn +2 6OH - + 3AsO3-3 + 2MnO -4 + 2H 2O h
(Acidic medium) 3AsO -4 3 + 2MnO 2 + 8OH -

Oxidation Reduction Calculation of n-factor
5[C2O 4-- -
h 2CO 2 + 2e ] [MnO -4 + 5e- + 8H + ææ
Æ Mn +2 ] ¥ 2 For the calculation of n-factors reaction can be divided into
three parts:
Net Reaction: Acid-Base neutralisation reaction. Redox reaction and
5C2O 4-2 + 2MnO -4 + 16H + h 10CO 2 + 2Mn +2 + 8H 2O Substitution or exchange reaction.
Acid Base Neutralisation: For acid the number of H+ ions
+4 +3 +3 +5
For example, (ii) ClO 2 + SbO -2 h ClO -2 + Sb(OH)6- donated or OH– ions accepted or number of lone pair accepted
by one molecule of acid is called its n-factor (Basicity of Acid).
(Basic)
For Base: Number of H+ ions accepted or OH– ions released
Reduction Oxidation
or lone pair donated by a molecule of a base in reaction is
[ClO 2 + e - ææ
Æ ClO -2 ] ¥ 2 SbO -2 + 2OH - ææ
Æ Sb(OH)6- + 2e - called n-factor (Acidity of Base)
For example, (i) 1H2SO4 + 2NaOH h Na2SO4 + 2H2O
2ClO 2 + SbO 2- + 2OH - + 2H 2O h 2ClO -2 + Sb(OH)6-
n-factor of H2SO4 = 2
n-factor of NaOH = 1

Redox 6.5
For example, (ii) H2SO4 + NaOH h NaHSO4 + H2O p q

n-factor of H2SO4 = 1 and nf of NaOH = 1 Case-I Ax1 By1 h Ax2 By2 _______________
For example, (iii) 1 Fe+2 + 6CN– [Fe(CN)6]–4 Æ n-factor for Ax1By1 = x1|p – q|
In the above case, there is no change in ON of B.
Æ n-factor for Ax2By2 = x2|q – p|
n-factor 6 1
Important Reaction:
For example, (iv) 2H3PO4 + 3Ca(OH)2 Ca3(PO4)2 + H2O
Permanganate ion
+7
n-factor 3 2 1. MnO 4- h Mn +2 (Acidic medium)
2H3PO4 + 3Ca(OH)2 h Ca3(PO4)2 + 6H2O (5) = n-factor
By observation we have balanced other elements in reaction. +7 +4
2. MnO -4 h Mn O 2 (Neutral medium) or weak basic
Acid-Base Titration by using double indicators
For the titration of acids and bases, we use indicators which (3) = n-factor
changes its colour in a particular PH range and indicate +7 +6
equivalence points in titration. 3. MnO 4- h Mn O 4-2 (Basic medium)
PH range Colour (1) = n-factor
Methyl orange (MeOH) 3.1–4.4 pink–yellow +6
phenolphthalein (HPH) 8.3–10 colourless–pink 4. Cr2 O7-- h Cr +3 (Acidic/Basic)
For the titration of strong acid and strong bases we can use 2|6 – 3| = 6 = n-factor
any indicator but for other titrations we used that indicator +3 +4
which has its pH range close to its equivalence point. 5. C2O -4 2 h CO 2 (Any medium)
In case of polytrophic acid (H more than 1) and polyhy-
2|3 – 4| = n-factor = 2
droxy bases (OH more than 1) we get more than 1 equiv- +2 2.5
alence point so depending upon the choice of equivalence 6. S2 O3-2 h S4 O6-2
point we need a suitable indicator. Thiosulphate
(i) H3PO4 + NaOH h NaH2PO4 + H2O 2|2 – 2.5| = 1 = n-factor
first equivalence point Some times its also called as hypo. (Na2S2O3. 2H2O)
0 -1
(ii) NaH2PO4 + NaOH h Na2HPO4 + H2O 7. I 2 h I - (Any medium)
second equivalence point n-factor = 2|0 + 1| = 2
(iii) Na2HPO4 + NaOH h Na3PO4 + H2O 8. Fe+2 h Fe+3
third equivalence point n-factor = |3 – 2| = 1
fi In the titration of H3PO4 by NaOH in presence of methyl Concentrated nitric acid behaves as strong oxidising
orange indicator the colour of solution changes at first equiv- agent and reduces itself into NO2.
alence point so n-factors in this case of H3PO4 is 1. +5 +4
fi If we use phenolphthalein indicator in the same titration Concentrate HNO3 h NO 2
separately then change of colour occur at second equivalence n-factor = |5 – 4| = 1
point. In this case the n-factor of H3PO4 is 2.
Acidity of third acidic hydrogen is negligible. Case-II _________________________________
Na2CO3 + HCl h NaHCO3 + NaCl p r q s
first equivalence point Ax1 By1 h Ax2 By2
NaHCO3 + HCl h H2CO3 + NaCl n-factor of Ax1By1 = x1 |p – q| + y1 |r – s|
second equivalence point Condition: In the above case either both A and B are oxidising
or A and B are reducing.
n-factor in Redox reaction = Total change in oxidation +3 –2 +5 +5 +6 +2
number per molecule either by oxidation or by reduction 4H2O + 3As2S3 + 28HNO3 6H3AsO4 + 9H2SAO4 + NO
change in oxidation number per molecule during a reaction is
called n-factor (in case of Redox reaction only)
n-factor 28 3

n-factor of AS2S3 = 2|3 – 5| + 3|–2 – 6| = 28 1

n-factor of HNO3 = 1|5 – 2| = 3 [3Cu + 8HNO3 ]
4
All other remaining are balanced by observation.
3
+2 –1 0 +3 –2 +4 Cu + 2HNO3
4FeS2 + 11O2 2Fe2 O3 + 8SO2 4
3
n1 = 2 \ n2 =
11 4 4
3
n-factor of FeS2 = |2 – 3| + 2|–1 – 4| \ n-factor of HNO3 =
4
= 1 + 2(5) = 11
n-factor of O2 = 2|0 + 2| = 4 For example,
0 +2
\ balanced reaction (ii) 4 Zn + 10HNO3 h 4 Zn(NO3 )2 + NH 4 NO3 + 3H 2 O
4FeS2 + 11O2 h 2Fe2O3 + 8SO2 2 n
1
[4 Zn + 10HNO3 ]
Case-III Disproportionation Reaction _______ 5
n1 = 2 = n-factor for reduction 4
Zn + 2HNO3
n2 = 10 = n-factor for oxidation 5
4
n2 = 10 n-factor of HNO3 =
Ex. 1 Cl2 h Cl– + ClO3– 5
For example,
n1 = 2 0 +5
(iii) P4 + 10HNO3 + H 2O h 4H3 PO 4 + 5NO + 5NO 2
1 1 1 Ê nn ˆ
= + or n = Á 1 2 ˜ 20 x
n n1 n2 Ë n1 + n2 ¯
2[P4 + 10HNO3]
|2 ¥ 10| n2 = 2
fi n= 2P4 + 20HNO3
10 + 2 –1 –2
1 0
H2O2 H2O + O2 n-factor of HNO3 is 2
20 2
= p q r
12 n1 = 2
5 Case-V Ax1 By1 h Ax2 By2 + Ax3 By3 ______
n=
3 In the above case either the oxidation of A is taking place or
reduction of A is taking place in product side.
3Cl2 + 6OH - h 5Cl- + ClO3- + 3H 2O
If x1 = x2 + x3
n1n2
n= n-factor of Ax1By1 = |x1p – x2q – x3r|
n1 + n2
= |x2(p – q) + x3(p – r)|
2¥2
n= If x1 π x2 + x3
2+2
n =1 aAx1By1 h bAx2By2 + cAx3By3
fi ax1 = bx2 + cx3
Case-IV Complex Reaction occur in more than | ax1 p - bx2 q - cx3r |
n-factor of Ax1By1 =
one step a
| bx2 ( p - q ) + cx3 ( p - r )|
For example, =
a
0 +5 +2 +5 +2
(i) 3Cu + 8HNO3 h 3Cu (NO3 ) 2 + 2NO + 4H 2O For example,
+5 +2 +4
(i) H 2O + P4 + 10HNO3 ææ
Æ 4H3PO 4 + 5NO + 5NO 2
Redox È3Cu + 2HNO3 h 3CuO + 2NO + H 2O ˘
Í ˙
Acid-Base Í3CuO + 6HNO h 3Cu(NO ) + 3H O ˙
Î 3 3 2 2 ˚
n-factor of HNO3 = |10 ¥ 5 - 5 ¥ 2 - 5 ¥ 4|
10
ÏCu + HNO3 For example,
Ô +2 +3 +4
nfactor Ìn1 n2 n1 = n f of Cu = 2 0
(ii) 4Fe (CrO 2 ) 2 + 8Na 2 C O3 + 7O 2 h
Ô
Ó fl n2 = ?
+3 -2 +6 +4 -2
n2Cu + n1HNO3 2Fe 2 O3 + 8Na 2 Cr O 4 + 8CO 2

Redox 6.7
n-factor of Fe(CrO2)2 = 1|2 – 3| + 2|3 – 6| = 7 Case-II: When substance forming solution are in same state
nfactor of O2 = 2[0 – (–2)] = 4 then the solvent is one which is present in large amount.
Amount compared should be in mass and mole. Some
hints are given in the question like A in B. Then A is solute
Case-VI and B is solvent.
Reduction All the conc. Terms defined are applicable only for ho-
n2 = 3 mogenous mixture not for heterogeneous mixture.
–3 +3 0
For example, NH4NO2 N2 + 2H2O Weight of solute
n1 = 3 1. Density =
Volume of solution
Oxidation
In this case, we will calculate either the n-factor for oxidation Unit gm/ml or gm/L
or the n-factor for reduction. The value of both is same and is It is temperature dependent because Mass independent
equal to n-factor of the compound. of temperature but volume depend upon temperature.
n-factor for NH4NO2 (T μ V)
= n-factor for oxidation (n1) \ T inversily proportional to density
= n-factor for reduction (n2) Weight of solute
=3 (density) except water
Volume of solution
Reduction
W
+7 –2 +4 –2 –2 2. Mass percentage or percentage mass %
For example, Mn2O7 MnO2 + O2 W
W Weight of Solute
Oxidation %= ¥ 100
W Weight of solution
n-factor of Mn2O7 = n-factor for reduction
= 2|7 – 4| Temperature independent
=6 Eg.:- 20% mass of NaOH solution means 100 gm of
n-factor of Mn2O7 calculated by Mn not by oxygen because solution contain 20 gm of NaOH and mass of solvent is
few oxygen present in – 2 oxidation state also in MnO2 means 80 gm.
No change in oxidation state. W
3. % Weight by volume or % or % by volume :-
\ n-factor of Mn2O7 = n-factor for oxidation V
= 2|–2 – 0| W Weight of Solute
= 14 (wrong) %= ¥ 100
V Volume of solution
3
Mn 2O7 h 2MnO 2 + O 2 V
2 4. % Volume by volume or % or % by volume
\ n-factor of Mn2O7 = 3 |–2 – 0| V
= 6 correct V Volume of Solute
%= ¥ 100
V Volume of solution
Substitution or Exchange Reaction __________
Moles of solute
In these type of reaction exchange of cations and anions oc- Molarity :- M =
cur between salts during the reaction and products may be Volume in liter
some precipitate. Temperature dependent
n-factor of the salt = (Number of metal ions) ¥ (their charge) Eg. 2 M NaCl solution means 1 Litre solution contains
For example, (i) 2AgNO3 + 1CaCl2 2AgCl + Ca(NO3)2 2 moles of NaCl.
(ppt)
1 2
For example, (ii) 2(NH4)2SO4 + 2BaCl2 2BaSO4 + 4NH4Cl
MOLARITY OF PURE
(ppt) SUBSTANCE
2 2
Solution is defined at a homogenous mixture of more than 1 ml contain = 1 gm
one substance in which one is solvent and rest other solute. 1000 ml = 1000 gm = 55.56 moles
Whatever the substance is solute or solvent is slightly con- \ moles in 1 L pure solution
troversial and should be concluded in following case. Weight
Case-I: When substances forming solution are in diff. states Molar mass 55.56 mole
= = = Molarity = 55.56 M
the final state of solution will be solvent irrespective of Volume in liter 1 liter
substances.

MOLALITY [m] SOME TYPICAL

CONCENTRATION TERMS
Number of moles of solute in one kg solvent. These conc. terms are typical in the sence that they are de-
So temperature independent. fined exclusively for the substance concerned depending
Eg. 2 m solution of NaCl means 2 mole of NaCl present in upon for what purpose substances are used.
1000 gram of solvent. (i) Concentration of H2O2: - H2O2 is used as a source of
oxygen gas and hence the typical conc. of H2O2 gives the
MOLE FRACTION value of oxygen obtained from the given solution. Since it
decomposes according to following reaction.
2H2O2 Æ 2H2O + O2
Ratio of moles of one component to the total number of
moles of solution Definition of concentration term of H2O2:- “x volume
A B C H2O2” means 1 Litre of H2O2 gives x litre of O2 gas at STP.
nA nB nC number of moles Eg. 20 volume H2O2 means 1 Litre of H2O2 gives 20 Litre
xA xB xC mole fraction of O2 at STP. It can be converted to normal concentration.
nA “V volume H2O2” means 1 Litre of H2O2 gives V litre of
xA = O2 gas at STP.
n A + nB + nC
2H2O2 Æ 2H2O + O2
and Sx = 1 V
or xA + xB + xC = 1 nO2 =
22.4
For binary solution xA + xB = 1
\ nH2O2 = 2 ¥ nO2
xB = 1 – xA
log10[xA + xB + xC] = log101 = 0 V V
=2¥ = mole
If Sn = 1 22.4 11.2
Number of moles V/11.2
xA = nA Molarity M = =
It means mole fraction of A = mole of A. Volume in L 1L
V
PPM and PPB (Parts per million and Parts per billion) \ Molarity = M
Parts of solute 11.2
PPM = ¥ 106 V Ê W ˆ 10
Parts of solution = Á %˜ ¥
Parts of solute 11.2 Ë V ¯ 34
PPB = ¥ 109
Parts of solution V Ê W ˆ 10d
= Á %˜ ¥
11.2 Ë W ¯ 34
(i) For gases
n f of H 2O 2 = 2
Volume of solute
PPM = ¥ 106 N = nf ◊ M
Volume of solution
Moles of solute V V
PPB = ¥ 109 \ N =2¥ =
Moles of solution 11.2 5.6
and H2O2 in gm/Liter = N ¥ 17 = strength in gm/L
Æ For gases parts = volume = moles V
Æ For solid/liquid parts = weight = ¥ 17 gm/L
5.6
(ii) For solid/liquid
Molar mass of H2O2 = 34
Weight of solute
PPM = ¥ 106 34
Weight of solution and equivalent weight of H2O2 = = 17
2
Weight of solute
PPB = ¥ 109
Weight of solution
CONCENTRATION OF OLEUM
Æ For dilute solution
(Weight of Solute Weight of Solution) Oleum is considered as a solution of SO3 gas dissolved in
Weight of solute H2SO4. H2S2O7 is type of oleum of 1 mole of SO3 and 1 mole
PPM = ¥ 106
Weight of solvent of H2SO4.

Redox 6.9
H2SO4 + SO3 h H2S2O7 weight of substance

Equivalent or gram equivalent =
Liq. Gas equivalent weight
Solvent solute solution Molar Mass(M)
Concentration of oleum is defined in such a way that it gives fi Equivalent weight =
n-factor
an idea of amount of H2SO4 it can give. M
Concentration of oleum is given by x % oleum. It means E=
n-factor
100 gm of this sample of oleum can maxima give x gm of
H2SO4 by the addition of (x – 100) gm of water. where M is molecular mass or molecular weight
For e.g. 109% oleum means 100 gm oleum is capable of weight of substance
Equivalent =
giving 109 gm H2SO4 by adding 9 gm of H2O in 100 gm of M /n-factor
oleum. w
An oleum sample labelled as x% implies the (x – 100) gm Equivalent = ¥ n-factor
M
of H2O will be required to react with all the SO3 present in
Equivalent = moles ¥ n-factor
100 gm of oleum according to the following reaction
where w Æ weight of substance
H2O + SO3 Æ H2SO4 in 100 gm oleum
Unbalanced Reaction
So, number of mole of water required = number of moles of
SO3 gas present in Oleum A + B C + D
G E
x% Max. W nH2O WSO3 WH2 SO4 H F
H 2O
Oleum H2SO4
= nSO3 Equivalents of A reacted = equivalent of B reacted
= equivalent of C produced
104.5% 104.5 4.5 0.25 0.25 ¥ 80 100 – 20 = equivalent of G reacted
= 20 = 80 = equivalent of H produced
109% 109 9 0.5 0.5 ¥ 80 60 = equivalent of D produced
= 40 = equivalent of E reacted
118% 118 18 1 1 ¥ 80 20 = equivalent of F produced
= 80
NORMALITY
Relation between concentration term
This is defined as the number of equivalent or gram equiva-
1000M
Molality (m) = lent of any substances dissolved in one litre of solution.
1000d - ( M ¥ Molar Mass of Solute)
Equivalent
ÊW ˆ 10 N=
Molarity (M) = Á %˜ ¥ Volume (in litre)
Ë V ¯ Molar Mass of Solute
Moles ¥ n-factor
N=
ÊW ˆ 10 ¥ d Volume (in litre)
Molarity (M) = Á %˜
Ë W ¯ Molar Mass of Solute
* Normality = Molarity ¥ n-factor
Molality (m) =
Mole Fraction of Solute * Equivalent = Volume (in litre) ¥ N
Mole Fraction of Solvent * Milli-equivalent = volume (in mL) ¥ N
1000 On dilution moles and equivalent will not change or equiva-
¥ lent of substance will not change on dilution.
Molar Mass of Solvent
BACK TITRATION
LAW OF EQUIVALENCE
Back titration is mainly used to calculate amount of agent
In any chemical reaction, one equivalent of any substances used in excess or to find out percentage purity of any sample.
will react with one equivalent of other substances and will In this method, for the excess of agent we use some other
produced one equivalent of products. agent and with the help of this we can find out the agent used
or initially for the reaction mixture and with this we can find out
In any chemical reaction, the equivalents of substance re- the initial composition.
act or the equivalent of product produced will always be same.

Results
IODOMERTRIC TITRATION 1. Remaining equivalent of HCl = equivalent of Ca(OH)2
2. Equivalent of NaOH = [given equivalent of HCl]
– [Remaining equivalent of HCl]
In iodomeric titration we use potassium iodide in solution
which has some oxidising agent. 3. Equivalent of NaOH = [given equivalent of HCl]
This oxidising agent oxidises iodide to iodine (I2). The io- – [equivalent of Ca(OH)2]
dine librated can be measured by following ways:
Oxadising agent + KI (excess) h Reduced form + I2(solid) Hardness of Water
I2 react with any of the reducing agent. Hard water is that which does not gives foam with soap.
1. I2 + 2Na2S2O3 h 2NaI + Na2S4O6 Classification of Hardness of Water
1. Permanent hardness
2. I 2 + I - h I3- (dark brown) 2. Temporary hardness
3. I 2 + AsO3-3 h I - + AsO 4-3 Temporary Hardness
Some important reactions This type of hardness easily removed by heating of water
-1 +5 sample.
(i) KI + MnO -4 h IO3- + Mn+2 D
Ca(HCO3)2 (soluble) ææ
Æ CaCO3 Ø + CO2 + H2O
x eq = x eq = x eq = x eq
(According to law of equivalence) It is generated by bicarbonate of calcium and magnesium.
(nf)6 5 6 5
Permanent Hardness
+5 +4 +6 0
(ii) IO3- +
SO 2 h + I2 SO 4-2 It is removed by suitable chemical process. It is generated by
chloride, sulphate of calcium and magnesium.
(nf)5 2 2 10
(iii) I– + Cu+2 h Cu+ + I2 Degree of Hardness
(nf)1 1 1 2 weight of solute
(Parts per million) PPM = ¥ 106
(iv) I2 + Na2S2O3 h Na2S4O6 + NaI weight of solvent
(nf)2 1 1 2
CaCO3 CaCl2 MgCO3 MgCl2
Back titration if HCl react with NaOH and excess HCl
neutralise by Ca(OH)2 100 111 84 95
weight of 1 equivalent
NaOH + HCl h salt + water 2 2 2 2
(Equivalent of NaOH) = given HCl equivalent – [remaining
It is defined as mass of CaCO3 equivalent to the mass
equivalent of HCl]
of various calcium and magnesium salts present. in 106
HCl + Ca(OH)2 h Product gram of water in dilute solution where the density is
[Remaining equivalent of HCl] = [equivalent of Ca(OH)2] approximately equal to 1 gm/ml.
Solved Examples
1. Balance the following reaction 2. Balance the following reaction

V + H2O h H4V6O17 + H2 NH4OH + Br2 h NH4Br + H2O + N2
0 +1 +5 0 (–3) (0) (–3) (–1) (0)
Sol. V + H 2 O h H 4V6 O17 + H 2 Sol. N H4OH + Br2 NH4Br + H2O + N2
Reduction
Oxidation Reduction
6V h V6 + 30e– [H2 + 2e– h H2]15 Oxidation
Oxidation Reduction
Net reaction:
2N h N2 + 6e– [2e– + Br2 h 2 Br]3
6V + 15 H2 h V6 + 15H2
6V + 15H2O + 2H2O h H2V6O17 + 15H2 Net reaction:
Final reaction: 2N + 3Br2 h N2 + 6Br
6V + 17 H2O h H4V6O17 + 15H2 2NH4OH + 3Br2 + 6NH4OH
h N2 + 6NH4Br + 8H2O

Redox 6.11
Balanced Reaction: Molar mass

6NH4OH + 3Br2 h N2 + 6NH4Br + 8H2O Equivalent wt =
n-factor
3. Find valency factor of H2SO4 in given reaction
n-factor for C12H22O11 = 12|0 – 3| = 36
2NaOH + H2SO4 Æ Na2SO4 + 2H2O
Base Acid 342
E= = 9.5
Sol. Valency factor of base = 1 36
Valency factor of acid = 2 9. What is the equivalent weight of phosphorous in the
Here two molecules of NaOH replaced 2H+ ion from following reaction?
the H2SO4, therefore, per molecule of NaOH replaced
P4 + NaOH h NaH2PO2 + PH3
only one H+ ion of acid so valency factor = 1
Sol. n2 = 4|0 – 1| = 4
4. Find valency factor of H2SO4 in given reaction
NaOH + H2SO4 Æ NaHSO4 + H2O 0 +1 –3
Base acid P4 + NaOH NaH2 PO2 + PH3
Sol. Valence factor of acid = 1
4|0 – 3| = 12 = n1
Here one of molecule of H2SO4 replaced one OH– from
NaOH therefore valency factor for H2SO4 is = 1. P40 + NaOH h NaH 2 PO 2 + PH3
molecular weight of H 2SO 4
E= n1n2
1 nf for disproportion ation nf =
n1 + n2
5. Calculate the normality of a solution containing 15.8 g n1 = 12 (reduction)
of KMnO4 in 50 mL acidic solution. n2 = 4 (oxidation)
W ¥ 1000 12 ¥ 4
Sol. Normality (N) = nf =
E ¥ VmL 12 + 4
where W = 15.8 g, V = 50 mL nf = 3
Molar mass of KMnO 4 Molar mass
E= = 158/5 = 31.6 Equivalent weight =
Valence factor nf
15.8 ¥ 1000 4 ¥ 31 124
So, N = = 10. \ Equivalent weight = = = 41.33
31.6 ¥ 50 3 3
6. Calculate the normality of a solution containing 50 mL 10. What mass of N2H4 can be oxidised to N2 by 24 g of
of 5 M solution K2Cr2O7 in acidic medium.
K2CrO4 which is reduced to Cr(OH) -4 ?
Sol. In acidic medium Cr change its oxidation state +6 to +3
-2 +6 +3 0
\ nf = (6 – 3) ¥ 2 = 6 Sol. N 2 H 4 + K 2 CrO 4 h Cr(OH) 4- + N 2
Normality (N) = Molarity ¥ Valence factor 24gm
= 5 ¥ 6 = 30 N Atomic weight of chromium = 52
7. Find the number of moles of KMnO4 needed to oxidise n-factor of N2H4 = 4 = D O.N of nitrogen in N2H4
one mole Cu2S in acidic medium. n-factor of K2CrO4 = 3 = D O.N of cromium in K2CrO4
The reaction is KMnO4 + Cu2S h Mn2+ + Cu2+ + SO2 Equivalent of N2H4 = Equivalent of K2CrO4
+1 –2 +4
Sol. Valence factor of Cu2S h Cu and S
+2 Ê w ˆ Ê 24 ˆ
ÁË ˜ =Á ˜
32/4 ¯ Ë 194/3 ¯
nf = 2[2 – 1] + 1|–2 –4| = 8
24 ¥ 3 32
+7 +2 w= ¥
Valence factor of KMnO4 h Mn 194 4
18 ¥ 32
nf = 1|7 – 2| = 5 =
194
From law of equivalence w = 2.969 g
Equivalents of Cu2S = Equivalents of KMnO4 11. What will be the moles of permaganate ion that will
Moles of Cu2S ¥ v.f = moles of KMnO4 ¥ Valence factor be needed to react with one mole of Ferrous oxylate in
Moles of Cu2S ¥ 8 = 1 ¥ 5 fi Moles of Cu2S = 5/8 acidic condition?
8. What is the equivalent weight of C12H22O11 in the fol- +7
+2 +3 +4
lowing reaction? Sol. Fe (C2 O 4 ) + MnO 4- h Mn +2 + CO 2 + Fe+3
0
Sol. C12 H 22O11 + 36HNO3 h n-factor of Fe(C2O4) = 1[3 – 2] + 2[4 – 3] = 3
+3 n-factor of MnO -4 = [2 – 7] = 5
6H 2 C2 O 4 + 36NO 2 + 23H 2O

Solving the above three equations we get x, y and M

Equivalent of FeC2O4 = Equivalent of MnO -4
(atomic mass of A)
1¥3 = n¥5
OR
3
n = moles Equivalent of AO + Equivalent of A2O3
5 = Equivalent of K2Cr2O7
12. 2.68 ¥ 10–3 moles of an ion in a solution requires
= Equivalent of AO -4
1.61 ¥ 10–3 moles of permaganate ion for oxidation of
14. To a 25 mL H2O2 solution excess of acidified solution
A+n to AO3- in Acidic medium? What is the value of n?
of potassium iodide was added. The iodine liberate re-
Sol. Here MnO -4 reduced into Mn+2 and A+n oxdise into +5 quire 20 mL of 0.3 N solution Na2S2O3. Calculate vol-
means n < 5 and nf of A+n = (5 – n) ume strength of H2O2 solution?
Oxidise nf = (5 – n) Sol. H2O2 + KI I2 + H 2 O
25 mL excess Na2S2O3 (20 mL, 0.3 N)
+7 +5 +2
+n
A + MnO4– AO–3 + Mn+2 NaI + Na2S4O6
Equivalent of H2O2 = Equivalent of KI reacted
reduce and nf = (7 – 2) = 5 = Equivalent of I2 formed
Equivalence of A+n = Equivalence of MnO -4 = Equivalent of Na2S2O3
(5 – n) ¥ 2.68 ¥ 10–3 = 5 ¥ 1.61 ¥ 10–3 N ¥ 25 = 20 ¥ 0.3
6
5 ¥ 1.61 N= =M ¥2
\ 5–n= 25
2.68
V 3
5 ¥ 1.61 M= =
\ –n = –5 11.2 25
2.68 3
M=
5 ¥ 2.68 - 5 ¥ 1.61 25
n=
2.68 11.2 ¥ 3
V.S. =
5(1.07) 25
n= ª2 V.S. = 1.344
2.68
13. A sample weighing 2.186 g containing a mixture AO 11.2 ¥ N
Since Volume strength = 11.2 ¥ M =
and A2O3 takes .015 moles of potassium dichromate 2
(K2Cr2O7) to oxidise the sample completely to form or Volume strength = 5.6 ¥ N
15. If a 1 L sample of water has 50 mg calcium chloride
AO -4 and Cr+3. If 0.0187 moles of AO -4 is formed, then calculate degree of hardness of this water sample.
what is atomic weight of A? Sol. 111 g CaCl2 equivalent to 100 g CaCO3
+2 +3 +6 +7 +3
100
Sol. AO + A2O3 + K2Cr2O7 AO4– + Cr+3 1 g CaCl2 equivalent to 100 g CaCO3 gram CaCO3
111
Reduction 100
\ 50 mg CaCl2 equivalent to ¥ 50 mg CaCO3
n-factor of K2Cr2O7 = 2|6 – 3| 111
Degree of hardness
=2¥3
=6 100
¥ 50 mg
n-factor of AO [7 – 2 ] = 5 = 111 ¥ 106 PPM
n-factor of A2O3 = 2(7 – 3) = 8 1000 mL = 1000 g
If x mole AO and y mole A2O3 present in mixture. 100 ¥ 50 ¥ 10-3 g
x mole = ¥ 106
111 ¥ 1000 g
+2 +7
100 ¥ 50
AO + K 2Cr2O7 h AO -4 + Cr +3 = = 45 PPM
+3 +7 111
A 2 O3 + K 2Cr2O7 h AO -4 + Cr +3 16. What weight of Na2CO3 of 85% purity would be
y mole required for 45.6 mL of 0.235 N H2SO4 for complete
x ¥ 5 + y ¥ 8 = 0.015 ¥ 6 reaction.
5x + 8y = 0.015 ¥ 6 ...(i) Sol. Milliequivalents of Na2CO3 = Milliequivalents of H2SO4
= 45.6 ¥ 0.235
x[M + 16] + y[2M + 48] = 2.186 ...(ii)
Given x + 2y = 0.0187 ...(iii) WNa 2CO3
\ ¥ 1000 = 45.6 ¥ 0.235
ENa 2CO3

Redox 6.13
WNa 2CO3 x y 40 ¥ 0.1 ¥ 100

fi ¥ 1000 = 45.6 ¥ 0.235 fi ¥ 2 ¥ 1000 + ¥ 2 ¥ 1000 =
106/2 106 138 20
\ WNa 2CO3 = 0.5679 g \ 69x + 53y = 73.14 …(ii)
From Eqs. (i) and (ii), we get
For 85 g of pure Na2CO3, weighed sample = 100 g x = 0.5962 g
\ for 0.5679 g of pure Na2CO3, weighed sample = y = 0.604 g
100 Solutions of Na2CO3 and K2CO3 gives ppt. of BaCO3
¥ 0.5679 = 0.6681 g
85 with BaCl2
17. 20 mL of H2O2 after acidification with dil H2SO4 re- (Milliequivalents of Na2CO3 + Milliequivalents of
N K2CO3) in 20 mL = Milliequivalents of BaCO3
quired 30 mL of KMnO4 for complete oxidation. fi Milliequivalents of HCl for 20 mL mixture = Mil-
12
liequivalents of BaCO3
The strength of H2O2 solution is [Molar mass of H2O2
= 34] fi Milliequivalents of BaCO3 = 40 ¥ 0.1 = 4
1 WBaCO3
Sol. 30 ¥ = 20 ¥ N¢ ¥ 1000 = 40 ¥ 0.1 = 4
12 M BaCO3
30 1 WBaCO3
N¢ = = ¥ 2 ¥ 1000 = 4
12 ¥ 20 8 197
1 \ WBaCO3 = 0.394 g
\ strength = N¢ ¥ equivalent mass = ¥ 17 = 2.12 g/L
8 21. A 20 g sample of only CuS and Cu2S was treated with
18. 3.55 g sample of bleaching powder suspended in H2O 100 mL of 1.25 M K2Cr2O7. The products obtained
was treated with enough acetic acid and KI solution. were Cr3+, Cu2+ and SO2. The excess oxidant was re-
Iodine thus liberated requires 80 mL of 0.2 M hypo for acted with 50 mL of Fe2+ Solution:25 mL of the same
titration. Calculate the % of available chlorine. Fe2+ solution required 0.875 M KMnO4 under acidic
[Available Chlorine = Mass of chlorine liberated/mass condition, the volume of KMnO4 used was 20 mL.
of bleaching powder ¥ 100] Find the % of CuS and Cu2S in the sample.
80 ¥ 0.2 Sol. Equivalents of dichromate initially
Sol. Moles of iodine = Moles of chlorine = ¥ 10–3
= 8 ¥ 10 –3 2 1.25 ¥ 6 ¥ 100
= = 0.75
8 ¥ 71 ¥ 10
–3
1000
so required % = ¥ 100% = 16%
3.55 Equivalents of Fe2+ in 25 mL
19. Calculate the molar ratio in which the following two 0.875 ¥ 5 ¥ 5 ¥ 20
substances would react? = = 0.0875
1000
Ba3(PO4)2 and AlCl3 Equivalents of Fe in 50 mL = 0.0875 ¥ 2 = 0.175
2+
Sol. n-factor of Ba3(PO4)2 = 3 ¥ (+2) = 6 = n1 Equivalents of excess dichromate = 0.175

While n-factor of AlCl3 = 1 ¥ (+3) = 3 = n2 \ equivalents of dichromate consumed by (CuS and
Cu2S)
n1 6 n1 x
= If = = 0.75 – 0.175 = 0.575
n2 3 n2 y If x g is the mass of CuS, the mass of Cu2S is (20 – x) g
y
Molar ratio = (inverse of equivalent ratio) x (20 – x)
x ¥6+ ¥ 8 = 0.475
\ molar ratio in which Ba3(PO4)2 and AlCl3 will react 95.5 159
= 3:6 = 1:2 \ x = 5.74 g
20. 1.20 g sample of Na2CO3 and K2CO3 was dissolved in 5.74
water to form 100 mL of solution. 20 mL of this solu- % CuS = ¥ 100 = 28.7 %
20
tion required 40 mL of 0.1 N HCl for complete neutral- % Cu2S = 71.3%
isation. Calculate the weight of Na2CO3 in the mixture. 22. 2.249 g of a sample of pure BaCO3 and impure CaCO3
If another 20 mL of this solution is treated with excess
containing some CaO was treated with dil. HCl and it
of BaCl2 what will be the weight of the precipitate?
evolved 168 mL of CO2 at N.T.P. From this solution,
Sol. Let weight of Na2CO3 = x g
BaCrO4 was precipitated filtered and washed. The pre-
Weight of K2CO3 = y g
cipitate was dissolved in dil. H2SO4 and diluted to 100
\ x + y = 1.20 g …(i)
For neutralisation reaction of 100 mL mL. 10 mL of this solution when treated with KI solu-
Milliequivalents of Na2CO3 + Milliequivalents of tion liberated iodine which required exactly 20 mL of
K2CO3 = Milliequivalents of HCl 0.05 N Na2S2O3. Calculate the percentage of CaO in
the sample.

Sol. Let weight of BaCO3, CaCO3 and CaO are x, y and z

36.945 ¥ 10 –5
respectively. Volume percent of ozone = ¥ 100
10
\ x + y + z = 2.249
= 3.6945 ¥ 10–3
BaCO3 h BaCrO4 24. Find the volume strength of H2O2 solution prepared by
Redox change Cr6+ + 3e– h Cr3+ mixing of 250 mL of 3N H2O2 & 750 mL of 1 N H2O2
2I– h I2 + 2e– solution:-
Milliequivalents of BaCO3 = Milliequivalents of Ê N V + N 2V2 ˆ 3 ¥ 250 + 750 ¥ 1
Sol. N = Á 1 1 =
BaCrO4 = Milliequivalents of I2 Ë V1 + V2 ˜¯ 1000
x 100 1500
\ ¥ 1000 = 20 ¥ 0.05 ¥ = = 1.5
197/3 10 1000
\ x = 0.657 g ....(1) 1.5 3
Molarity = = 0.75 =
The equivalent weight of BaCrO4 is M/3, therefore for 2 4
BaCO3, it should be M/3 also because mole ratio of 1
fi H 2O2 h H 2O + O2
BaCO3 and BaCrO4 is 1:1. 2
Applying POAC for C atom, in 1L H2O2, 1 Mole H2O2 give O2 = 11.2 L
Moles of C in BaCO3 + Moles of C in CaCO3 = Moles 3
of C in CO2 1L H 2O 2 , 0.75 H 2O 2 h = 11.2 ¥
4
x y 168 h = 8.4 V O 2
\ + =
197 100 22400 fi Volume strength = 8.4 V
fi 200x + 294y = 295.5 ....(2) Alternative volume strength = 5.6 ¥ N = 5.6 ¥ 1.5 = 8.4 V
From Eqs. (1) and (2) 25. Mg can reduce NO3– to NH3 in basic medium.
NO3– + Mg (s) + H2O Æ
y = 0.416 g
Mg (OH)2 (s) + OH– (aq.) + NH3(g)
\ 0.657 + 0.416 + z = 2.249 A 25.0 mL sample of NO3– solution was treated with
z = 1.176 Mg. The NH3 (g) was passed into 100 mL of 0.15 N
1.176 HCl. The excess of HCl required 32.10 mL of 0.10 N
% of CaO = = 52.29% NaOH for neutralisation. What was the molarity of
2.249
NO3– ions in the original sample?
23. For estimating ozone in the air, a certain volume of air Sol. Milliequivalents of NH3 formed
is passed through an alkaline KI solution when O2 is = Milliequivalents of HCl used
evolved and iodide is oxidised to iodine. When such a = 100 ¥ 0.15 – 32.10 ¥ 0.10
solution is acidified, free iodine is evolved which can = 11.79
be titrated with standard Na2S2O3 solution: In an ex- Here, n-factor of NH3 is 1 (acid - base reaction)
periment, 10 L of air at 1 atm and 27°C were passed For redox change,
through an alkaline KI solution, and at the end, the +5 –3
+8e –
iodine was entrapped in a solution which on titration NO3– æææ
Æ NH3 (n-factor = 8)
as above required 1.5 mL of 0.02 N Na2S2O3 solution. \ Milliequivalents of NH3 for n-factor 8 = 8 ¥ 11.79 =
Calculate volume percentage of ozone in the sample. 94.32
Sol. The chemical reaction is H2O + KI + O3 h I2 + O2 +
- miliequivalent 94.32
KOH \ normality of NO3 = = = 3.77
Milliequivalents of iodine = Milliequivalents of KI = V(ml) 25
Milliequivalents of O3 reacted 3.77
Molarity of NO3- = = 0.41725
Milliequivalents of Na2S2O3 = 1.5 ¥ 0.02 = 3 ¥ 10–2 8
26. 30 mL of a solution containing 9.15 g/L of an oxalate
3 ¥ 10 –2
Millimoles of iodine = = 1.5 ¥ 10–2 KxHy (C2O4)z.nH2O are required for titrating 27 mL of
2 0.12 N NaOH and 36 mL of 0.12 N KMnO4 separately.
[ n-factor for iodine = 2] Calculate x, y, z and n. Assume all H atoms (except
Millimoles of ozone = 1.5 ¥ 10–2 = 1.5 ¥ 10–5 moles H2O) are replaceable and x, y, z are in the simple ratio
nRT 1.5 ¥ 10 –5 ¥ 0.0821 ¥ 300 of g atoms.
Volume of ozone = = Sol. Let molecular weight of oxalate salt is M
P 1
(i) n-factor in acid-base reaction = y
= 36.945 ¥ 10–5 L (ii) n-factor in redox titration = 2 ¥ z

Redox 6.15
Sol. Milliequivalents of MnO2 = Milliequivalents of Na2C2O4

( C2O 42- h 2CO2 + 2e)
= 20 ¥ 0.2 ¥ 2 = 8
\ Milliequivalents of acid in 30 mL = Milliequivalents 2-
( C2O 4 Æ 2CO2, n-factor = 2)
of NaOH used
9.15 8
30 ¥ ¥ y = 27 ¥ 0.12 (i) Millimoles of MnO2 = =4
M 4
n-factor = 3
9.15
Also, 30 ¥ ¥ (2z) = 36 ¥ 0.12 (ii)
M MnO–4 + Mn+2
H2O
MnO2 brown (ppt.)
y 27 y 3
From Eqs. (i) and (ii) = fi = (iii)
2 z 36 z 2 n-factor = 2
Also, total cationic charge = total anionic charge
\ x + y = 2z (iv) or 2MnO4– + 3Mn2+ Æ 5MnO2
By Eqs. (iii) and (iv) (Mole ratio is reciprocal of n-factor ratio)
x:y:z::1:3:2
These are in simplest ratio and molecular formula is Millimolesof MnO 4– 2
=
KH3 (C2O4)2.nH2O Millimolesof MnO 2 5
Molecular weight of salt = 39 + 3 + 176 + 18n = 218 + 18n 2
30 ¥ 9.15 ¥ 3 Millimoles MnO 4– = ¥ Millimoles of MnO2
From Eq. (i), M = = 254.16 5
27 ¥ 0.12 2 8
\ 218 + 18n = 254.15 = ¥4=
5 5
\ n=2 2KMnO4 + 5H2O2 + 3H2SO4 Æ
\ Oxalate salt is KH3(C2O4)2.2H2O 2 MnSO4 + K2SO4 + 8H2O + 5O2
27. Hydrogen peroxide solution (20 mL) reacts quantita-
Millimoles of H 2O 2 5
tively with a solution of KMnO4 (20 mL) acidified with =
dilute H2SO4. The same volume of the KMnO4 solution Millimoles of MnO 4– 2
is just decolourised by 10 mL of MnSO4 in neutral me- 5 8
\ millimoles of H2O2 = ¥ = 4
dium simultaneously forming a dark brown precipitate 2 5
of hydrated MnO2. The brown precipitate is dissolved N H2O2 ¥ 20 = 4 ¥ 2 (n-factor for H2O2 = 2)
in 20 mL of 0.2 M sodium oxalate under boiling con-
\ N H2O2 = 0.4
dition in the presence of dilute H2SO4. Write the bal-
anced equations involved in the reactions and calculate Volume strength of H2O2 = 5.6 ¥ N H2O2
the volume strength of H2O2. = 5.6 ¥ 0.4 = 2.24
Exercise
4. 1.60 g of a metal were dissolved in HNO3 to prepare its
LEVEL I nitrate. The nitrate on strong heating gives 2 g oxide.
The equivalent weight of metal is
1. The number of moles of CaCl2 needed to react with (a) 16 (b) 32 (c) 48 (d) 12
excess of AgNO3 to produce 4.31 g of AgCl. 5. How many moles of electron is needed for the reduc-
(a) 0.030 (b) 0.015 (c) 0.045 (d) 0.060 tion of each mole of Cr in the reaction,
2. Calcium carbonate reacts with aqueous HCl to give
CaCl2 and CO2 according to the reaction, CaCO3(s) + CrO5 + H2SO4 h Cr2(SO4)3 + H2O + O2
2HCl(aq) Æ CaCl2(aq) + CO2(g) + H2O(l). (a) 4 (b) 3 (c) 5 (d) 7
The mass of CaCO3 is required to react completely 6. The incorrect order of decreasing oxidation number of
with 25 mL of 0.75 M HCl is S in compounds is
(a) 0.1 g (b) 0.5 g (c) 1.5 g (d) 0.94 g (a) H2S2O7 > Na2S4O6 > Na2S2O3 > S8
3. If ten volumes of dihydrogen gas reacts with five vol-
(b) H2SO5 > H2SO3 > SCl2 > H2S
umes of dioxygen gas, how many volumes of water va-
pour would be (c) SO3 > SO2 > H2S > S8
(a) 10 (b) 20 (c) 48 (d) 12 (d) H2SO4 > SO2 > H2S > H2S2O8

7. Which reaction does not represent autoredox or dispro- 16. Temporary hardness is due to HCO3– of Mg2+ and Ca2+.
portionation: It is removed by addition of CaO.
(a) Cl2 + OH– h Cl– + ClO3– + H2O Ca(HCO3)2 + CaO Æ 2CaCO3 + H2O
(b) 2H2O2 h H2O + O2 Mass of CaO required to precipitate 2 g CaCO3 is
(c) 2Cu+ h Cu+2 + Cu (a) 2.00 (b) 0.56 g (c) 0.28 g (d) 1.12 g
(d) (NH4)2Cr2O7 h N2 + Cr2O3 + 4H2O 17. Bottle (A) contains 320 mL of H2O2 solution and la-
8. Which of the following is a redox reaction? belled with 10 V H2O2 and bottle (B) contains 80 mL
(a) 2CrO 24- + 2H + Æ Cr2O72- + H 2O H2O2 having normality 5 N. Bottle (A) and bottle (B)
(b) CuSO4 + 4NH3 Æ [Cu(NH3)4] SO4 are mixed and solution filled in bottle (C). Select the
(c) Na2S2O3 + I2 Æ Na2S4O6 + NaI correct label for bottle (C) in terms of volume strength
and in terms of g/litre.
(d) Cr2O72- + 2OH - Æ 2CrO 24- + H 2O (a) 13.6 “V” and 41.285 g/L
9. In the reaction (b) 11.2 “V”and 0.68 g/L
xHI + yHNO3 h NO + I2 + H2O (c) 5.6 “V” and 0.68 g/L
(a) x = 3, y = 2 (b) x = 2, y = 3 (d) 5.6 “V” and 41.285 g/L
(c) x = 6, y = 2 (d) x = 6, y = 1 18. 1 mol of iron (Fe) reacts completely with 0.65 mol O2
10. For the redox reaction to give a mixture of only FeO and Fe2O3. Mole ratio of
MnO 4- + C2O 42- + H+ h Mn2+ + CO2 + H2O ferrous oxide to ferric oxide is
(a) 3:2 (b) 4:3
the correct stoichiometric coefficients of MnO 4- , C2O 42-
(c) 20:13 (d) none of these
and H+ are respectively
19. The molar ratio of Fe++ to Fe+++ in a mixture of FeSO4
(a) 2,5,16 (b) 16,5,2 (c) 5,16,2 (d) 2,16,5
and Fe2(SO4)3 having equal number of sulphate ion in
11. Which of the following relations is incorrect?
both ferrous and ferric sulphate is
(a) 3NAl2 (SO4)3 = 0.5 M Al2(SO4)3
(a) 1:2 (b) 3:2
(b) 3M H2SO4 = 6NH2 SO4
(c) 2:3 (d) Cannot be determined
(c) 1 M H3PO4 = 1/3 N H3PO4
20. If a piece of iron gains 10% of its weight due to partial
(d) 1 M Al2 (SO4)3 = 6 N Al2(SO4)3 rusting into Fe2O3. The percentage of total iron that has
12. In the reaction CrO5 + H2SO4 Æ Cr2(SO4)3 + H2O + O2,
rusted is
one mole of CrO5 will liberate how many moles of O2?
(a) 23 (b) 13 (c) 23.3 (d) 25.67
(a) 5/2 (b) 5/4 (c) 9/2 (d) 7/4
21. HNO3 oxidises NH4+ ions to nitrogen and itself gets
13. One gram of Na3AsO4 is boiled with excess of solid
reduced to NO2. The moles of HNO3 required by 1 mol
Kl in presence of strong HCl. The iodine evolved is
of (NH4)2SO4 is
absorbed in Kl solution and titrated against 0.2 N hy-
(a) 4 (b) 5 (c) 6 (d) 2
posolution. Assuming the reaction to be
22. 25 mL of a 0.1 M solution of a stable cation of tran-
AsO34- + 2H + + 2I - h AsO33- + H 2O + I 2 , sition metal Z reacts exactly with 25 mL of 0.04 mL
calculate the volume of thiosulphate hypo consumed. acidified KMnO4 solution. Which of the following is
[Atomic weight of As = 75] most likely to represent the change in oxidation state of
(a) 48.1 mL (b) 38.4 mL Z correctly?
(c) 24.7 mL (d) 30.3 mL (a) Z+ Æ Z2+ (b) Z3+ Æ Z1+
14. 25 mL of 0.50 M H2O2 solution is added to 50 mL of (c) Z Æ Z
3+ 4+
(d) Z2+ Æ Z4+
0.20 M KMnO4 in acid solution. Which of the follow- 23. How many litres of Cl2 at S.T.P. will be liberated by
ing statement is true: oxidation of NaCl with 10 g KMnO4?
(a) 0.010 mole of oxygen is liberated. (a) 3.54 L (b) 7.08 L
(b) 0.005 mole of KMnO4 are left. (c) 1.77 L (d) None of these
(c) 0.030 g atom of oxygen gas is evolved. 24. During the disproportionation of iodine to iodide and
(d) 0.0025 mole H2O2 does not react with KMnO4. iodate ions, the ratio of iodate and iodide ions formed
15. Hydrogen peroxide in aqueous solution decomposes on in alkaline medium is
warming to give oxygen according to the equation (a) 1:5 (b) 5:1 (c) 3:1 (d) 1: 3
2H2O2 (aq) h 2H2O(l) + O2(g) 25. 28 NO3- + 3As2S3 + 4H2O
Under conditions where 1 mole of gas occupies 24 Æ 6 AsO34- + 28NO + 9SO 24- + H+
dm3. 100 cm3 of XM solution of H2O2 produces 3 dm3 What will be the equivalent mass of As2S3 in above
of O2. Thus X is reaction?
(a) 2.5 (b) 1 (c) 0.5 (d) 0.25

Redox 6.17
Molecular weight Molecular weight 34. What volume of 6 M HNO3 is needed to oxidise 8 g of
(a) (b) Fe2+ to Fe3+, HNO3 gets converted to NO?
2 4
(a) 80 mL (b) 7.936 mL
Molecular weight Molecular weight
(c) (d) (c) 32 mL (d) 64 mL
24 28 35. A certain weight of pure CaCO3 is made to react com-
26. When ZnS is boiled with a strong nitric acid, the prod- pletely with 200 mL of an HCl solution to give 224 mL
ucts are zinc nitrate, sulphuric acid and nitrogen diox- of CO2 gas at STP. The normality of the HCl is
ide. What are the changes in the oxidation numbers of (a) 0.05 N (b) 0.1 N (c) 1.0 N (d) 0.2 N
Zn, S and N? 36. Volume V1 mL of 0.1 MK2Cr2O7 is needed for com-
(a) +2, +4, –1 (b) +2, +6, –2 plete oxidation of 0.678 g N2H4 in acidic medium. The
(c) 0, +4, –2 (d) 0, +8, –1 volume of 0.3 M KMnO4 needed for same oxidation in
27. Which of the following solutions will exactly oxidise acidic medium will be
25 mL of an acid solution of 0.1 M Fe (II) oxalate? 2 5
(a) 25 mL of 0.1 M KMnO4 (a) V1 (b) V1 (c) 113 V1 (d) can’t say
5 2
(b) 25 mL of 0.2 M KMnO4 37. If equal volumes of 0.1 M KMnO4 and 0.1 M K2Cr2O7
(c) 25 mL of 0.6 M KMnO4 solutions are allowed to oxidise Fe2+ to Fe3+ in acidic
(d) 15 mL of 0.1 M KMnO4 medium, then Fe2+ oxidised will be
28. 4.9 g of K2Cr2O7 is taken to prepare 0.1 L of the so- (a) more by KMnO4 (b) more by K2Cr2O7
lution. 10 mL of this solution is further taken to oxi- (c) equal in both cases (d) cannot be determined
dise Sn2+ ion into Sn4+ ion. Sn4+ so produced is used in 38. 25.4 g of iodine and 12.2 g of chlorine are made to react
second reaction to prepare Fe3+ ion from ferous ion completely to yield a mixture of ICl and ICl3. Calculate
then the millimoles of Fe3+ ion formed will be (assume the ratio of moles of ICl and ICl3.
all other components are in sufficient amount)? [Molar (a) 1:1 (b) 1:2 (c) 1:3 (d) 2:3
mass of K2Cr2O7 = 294 g] 39. Calculate the weight of iron which will be converted
(a) 5 (b) 20 into its oxide by the action of 18 g of steam on it.
(c) 10 (d) None of these (a) 37.3 g (b) 3.73 g
29. 35 mL sample of hydrogen peroxide gives of 500 mL (c) 56 g (d) 5.6 g
of O2 at 27°C and 1 atm pressure. Volume strength of 40. A 0.1097 g sample of As2O3 required 36.10 mL of
H2O2 sample will be KMnO4 solution for its titration. The molarity of
(a) 10 volume (b) 13 volume KMnO4 solution is
(c) 11 volume (d) 12 volume (a) 0.02 (b) 0.04 (c) 0.0122 (d) 0.3
30. 20 mL of 0.1 M solution of compound Na2CO3. 41. In basic medium, CrO 24- oxidise S2O32- to form SO 24-
NaHCO3.2H2O is titrated against 0.05 M HCl, x mL of and itself changes to Cr(OH) -4 . How many mL of
HCl is used when phenolphthalein is used as an indica- 0.154 M CrO 24- are required to react with 40 mL of
tor and y mL of HCl is used when methyl orange is the
indicator in two separate titrations. Hence (y – x) is 0.246 M S2O32- ?
(a) 40 mL (b) 80 mL (a) 200 mL (b) 156.4 mL
(c) 120 mL (d) None of these (c) 170.4 mL (d) 190.4 mL
31. 0.3 g of an oxalate salt was dissolved in 100 mL solu- 42. 10 mL of 0.4 M Al2(SO4)3 is mixed with 20 mL of 0.6
tion. The solution required 90 mL of N/20 KMnO4 for M BaCl2. Concentration of Al3+ ion in the solution will
complete oxidation. The % of oxalate ion in salt is be
(a) 0.266 M (b) 10.3 M
(a) 33% (b) 66% (c) 70% (d) 40%
(c) 0.1 M (d) 0.25 M
32. A 0.518 g sample of limestone is dissolved in HCl and
43. The weight of sodium bromate required to prepare 55.5
then the calcium is precipitated as CaC2O4. After fil- mL of 0.672 N solution for cell reaction,
tering and washing the precipitate, it requires 40.0 mL
of 0.250 N KMnO4 solution acidified with H2SO4 to BrO3- + 6H+ + 6e– h Br– + 3H2O, is
titrate it. The percentage of CaO in the sample is (a) 1.56 g (b) 0.9386 g (c) 1.23 g (d) 1.32 g
44. NaIO3 reacts with NaHSO3 according to equation
MnO -4 + H+ + C2O 42- h Mn2+ + CO2 + 2H2O
IO3- + 3HSO3- h I - + 3H + + 3SO 24-
(a) 54.0% (b) 27.1% (c) 42% (d) 84%
33. The mass of oxalic acid crystals (H2C2O4. 2H2O) re- The weight of NaHSO3 required to react with 100 mL
quired to prepare 50 mL of a 0.2 N solution is of solution containing 0.68 g of NaIO3 is
(a) 4.5 g (b) 6.3 g (c) 0.63 g (d) 0.45 g (a) 5.2 g (b) 0.2143 g
(c) 2.3 g (d) None of these

45. If 0.5 moles of BaCl2 is mixed with 0.1 moles of 6. 50 mL of 0.1 M solution of a salt reacted with 25 mL
Na3PO4, the maximum amount of Ba3(PO4)2 that can of 0.1 M solution of sodium sulphite. The half-reaction
be formed is for the oxidation of sulphite ion is
(a) 0.7 mol (b) 0.5 mol (c) 0.2 mol (d) 0.05 mol SO32- (aq) + H2O (l) h SO 24- (aq) + 2H+(aq) + 2e–
46. 0.52 g of a dibasic acid required 100 mL of 0.2 N
If the oxidation number of metal in the salt was 3, what
NaOH for complete neutralisation.
would be the new oxidation number of metal?
The equivalent weight of acid is
(a) 0 (b) 1 (c) 2 (d) 4
(a) 26 (b) 52 (c) 104 (d) 156
7. An element A in a compound ABD has oxidation num-
47. 34 g hydrogen peroxide is present in 1120 mL of solu-
tion. This solution is called ber An–. It is oxidised by Cr2O72- in acid medium. In
(a) 10 volume (b) 20 volume the experiment 1.68 ¥ 10–3 moles of K2Cr2O7 were
(c) 30 volume (d) 32 volume used for 3.26 ¥ 10–3 moles of ABD. The new oxidation
48. The number of moles of KMnO4 that will be required number of A after oxidation is
to react with 2 mol of ferrous oxalate is (a) 3 (b) 3 – n (c) n – 3 (d) +n
6 2 4 8. Match List-I (Compounds) with List-II (Oxidation
(a) (b) (c) (d) 1 states of nitrogen) and select answer using the codes
5 5 5
given below the lists:
49. What volume of 0.1 M KMnO4 is needed to oxidise
100 mg of FeC2O4 in acid solution? List-I List-II
(a) 4.1 mL (b) 8.2 mL (c) 10.2 mL (d) 4.6 mL (A) NaN3 1. +5
(B) N2H2 2. +2
(C) NO 3. –1/3
LEVEL II (D) N2O5 4. –1
Code: (A) (B) (C) (D)
1. Chlorine is prepared in the laboratory by treating man- (a) 3 4 2 1
ganese dioxide (MnO2) with aqueous hydrochloric acid (b) 4 3 2 1
according to the reaction (c) 3 4 1 2
4HCl(aq) + MnO2(s) Æ2H2O(l) + MnCl2(aq) + Cl2(g) (d) 4 3 1 2
The grams of HCl react with 5.0 g of manganese diox-
9. 125 mL of 63% (w/v) H2C2O4. 2H2O is made to react
ide will be [Atomic mass of Mn = 55]
with 125 mL of a 40% (w/v) NaOH solution. The re-
(a) 84 g (b) 0.84 g (c) 8.4g (d) 4.2 g
sulting solution is
2. A welding fuel gas contains carbon and hydrogen only.
(a) neutral (b) acidic
Burning a small sample of it in oxygen gives 3.38 g
carbon dioxide, 0.690 g of water and no other products. (c) strongly acidic (d) alkaline
A volume of 10.0 L (measured at STP) of this welding 10. If 10 g of V2O5 is dissolved in acid and is reduced to
gas is found to weigh 11.6 g. The empirical formula, V2+ by zinc metal, how many mole I2 could be reduced
molar mass of the gas and molecular formula will be by the resulting solution if it is further oxidised to VO2+
respectively ions ?
(a) CH2, 30, C2H4 (b) CH, 30, C2H2 [Assume no change in state of Zn2+ ions] (V = 51, O =
(c) CH, 26, C2H2 (d) CH2, 26, C2H4 16, I = 127):
– (a) 0.11 mole of I2 (b) 0.22 mole of I2
3. It takes 0.15 mole of ClO to oxidise 12.6 g of chro-
(c) 0.055 mole of I2 (d) 0.44 mole of I2
mium oxide of a specific formula to Cr2O72- . ClO– be- 11. 0.10 g of a sample containing CuCO3 and some inert
came Cl–. The formula of the oxide is (atomic weight impurity was dissolved in dilute sulphuric acid and vol-
Cr = 52, O = 16) ume made up to 50 mL. This solution was added into
(a) CrO3 (b) CrO2 (c) CrO4 (d) CrO 50 mL of 0.04 M KI solution where copper precipitates
4. 8 g of sulphur is burnt to form SO2 which is oxidised by
as CuI and I– is oxidised into I3- . A 10 mL portion of
Cl2 water. The solution is treated with BaCl2 solution.
this solution is taken for analysis, filtered and made up
The amount of BaSO4, precipitate is
(a) 1 mole (b) 0.5 mole free I3- and then treated with excess of acidic perman-
(c) 0.24 mole (d) 0.25 mole ganate solution. Liberated iodine required 20 mL of
5. 25.0 mL of HCl solution gave, on reaction with excess 2.5 mM sodium thiosulphate solution to reach the end
AgNO3 solution 2.125 g of AgCl. The normality of point. Determine weight percentage of CuCO3 in the
HCl solution is original sample.
(a) 0.25 (b) 0.6 (c) 1.0 (d) 0.75 (a) 7.41 (b) 74.1
(c) 61.75 (d) none of these

Redox 6.19
12. A 150 mL of solution of I2 is divided into two unequal 19. A solution of KMnO4 is reduced to MnO2. The normal-
parts. I part reacts with hyposolution in acidic medium. ity of solution is 1.8. The molariy will be
15 mL of 0.4 M hypo was consumed. II part was added (a) 0.1 M (b) 0.6 M (c) 1.8 M (d) 0.3 M
with 100 mL of 0.3 M NaOH solution. Residual base 20. 40 g Ba(MnO4)2 (molecular weight = 375) sample con-
required 10 mL of 0.3 M H2SO4 solution for complete taining some inert impurities in acidic medium is com-
neutralisation. What was the initial concentration of I2? pletely reacted with 125 mL of “33.6 V” of H2O2. What
(a) 0.08 M (b) 0.1 M is the percentage purity of the sample?
(c) 0.2 M (d) none of these (a) 28.12 % (b) 70.31 %
13. A mixture of H2SO4 and H2C2O4 (oxalic acid) and (c) 85 % (d) None of these
some inert impurity weighing 3.185 g was dissolved
in water and the solution made up to 1 L, 10 mL of this
solution required 3 mL of 0.1 N NaOH for complete LEVEL III
neutralisation. In another experiment 100 mL of the
same solution in hot condition required 4 mL of 0.02M
1. Match the columns.
KMnO4 solution for complete reaction. The weight %
of H2SO4 in the mixture was Column I Column II
(a) 40 (b) 50 (c) 60 (d) 80 (Reaction) (Equivalent
14. 0.80 g of sample of impure potassium dichromate was weight)
dissolved in water and made up to 500 mL solution. 25 (a) NH h NO - (p) M/3
mL of this solution treated with excess of KI in acidic 3 3
medium and I2 liberated required 24 mL of a sodium (b) FeC O h Fe3+ + 2CO 2- (q) M/6
2 4 3
thiosulphate solution. 30 mL of this sodium thiosul-
phate solution required 15 mL of N/20 solution of pure (c) H2SO5 h S8 (r) M/8
potassium dichromate. What was the percentage of (d) KMnO4 h Mn 2+
(s) M/5
K2Cr2O7 in given sample? Reducing
(a) 73.5 % (b) 75.3 % (t)
agent
(c) 36.75 % (d) none of these
15. A 10.0 g samples of a mixture of calcium chloride and 2. Match the column
sodium chloride is treated with Na2CO3 to precipitate Column I Column II
the calcium as calcium carbonate. This CaCO3 is heat- (Acid) (Nature)
ed to convert all the calcium to CaO and the final mass
(a) H3PO4 (p) Monobasic
of CaO is 1.62 g. The % by mass of CaCl2 in the origi-
nal mixture is (b) H3PO3 (q) Pentabasic
(a) 15.2% (b) 32.1% (c) 21.8% (d) 11.7% (c) H3BO3 (r) Tri basic
16. Hydroxyl amine reduces iron (III) according to follow- (d) EDTA (s) Tetra basic
ing equation: (t) Dibasic
NH2OH + Fe2(SO4)3 h
N2(g) + H2O + FeSO4 + H2SO4 3. Match the following
Which statement is correct? Column I Column II
(a) n-factor for Hydroxyl amines is 1.
H + (p) M/2
(b) equivalent weight of Fe2(SO4)3 is M/2. (a) KMnO4 ææÆ Mn+2
(c) 6 meq of Fe2(SO4)3 is contained in 3 millimoles of
ferric sulphate. (b) MgC2O4 h Mg2+ + CO2 (q) M/5
(d) All of these. (c) K2Cr2O7 h Cr+3 (r) M/6
17. Equal volumes of 1 M each of KMnO4 and K2Cr2O7 (d) CrO5 h Cr2O3 (s) M/3
are used to oxidise Sn(II) solution in acidic medium.
(t) Oxidising
The amount of Fe oxidised will be
agent
(a) more with KMnO4
(b) more with K2Cr2O7
Comprehension 1 (Question No. 4 to 7)
(c) equal with both oxidising agents
(d) more with KMnO4 in basic medium Oleum is considered as a solution of SO3 in H2SO4, which is
18. The normality of a mixture obtained by mixing 100 mL obtained by passing SO3 in solution of H2SO4. When 100 g
of 0.2 M H2SO4 with 100 mL of 0.2 M NaOH will be sample of oleum is diluted with desired weight of H2O then
(a) 0.05 N (b) 0.1 N (c) 0.15 N (d) 0.2 N the total mass of H2SO4 obtained after dilution is known as
% labelling in oleum.

For example, a oleum bottle labelled as ‘109% H2SO4’

I2 + Na2S2O3 h I– + S4O6--
means the 109 g total mass of pure H2SO4 will be formed
when 100 g of oleum is diluted by 9 g of H2O which com- If iodine is liberated as a result of chemical reaction involv-
bines with all the free SO3 present in oleum to form H2SO4 as ing oxidation of an idodide ion by a strong oxidising agent
SO3 + H2O h H2SO4 in neutral or acidic medium, the liberated iodine is then ti-
4. What is the % of free SO3 in an oleum that is labelled trated with reducing agent. Iodometry is used to estimate the
as ‘104.5 % H2SO4’? strength of oxidising agent.
(a) 10 (b) 20 For example, the estimation of Cu++ with thiosulphate.
(c) 40 (d) None of these Cu++ + I– h Cu2I2 + I2
5. 9.0 g water is added into oleum sample labelled as
I 2 + S2O3-- h S4O6-- + I -
‘112% H2SO4’ then the amount of free SO3 remaining
in the solution is Starch used as indicator near the end point which form blue
(a) 14.93 L at STP (b) 7.46 L at STP colour complex with I3- . The blue colour disappears when
(c) 3.73 L at STP (d) 11.2 L at STP there is no more of free I2.
6. If excess water is added into a bottle sample labelled as 11. In iodine titration, iodine remains in solution in the
‘112 % H2SO4’ and is reacted with 5.3 g Na2CO3, then form of
find the volume of CO2 evolved at 1 atm pressure and
(a) I3- (b) I2 (c) I3+ (d) I–
300 K temperature after the completion of the reaction.
(a) 2.46 L (b) 24.6 L (c) 1.23 L (d) 12.3 L 12. In the reaction, 2CuSO4 + 4KI Æ Cu2I2 + 2K2SO4 + I2
7. 1 g of oleum sample is diluted with water. The solution the ratio of equivalent weight of CuSO4 to its molecu-
required 54 mL of 0.4 N NaOH for complete neutrali- lar weight is
sation. The % of free SO3 in the sample is (a) 1/8 (b) 1/4 (c) 1/2 (d) 1
(a) 74 (b) 26 13. When 159.50 g of CuSO4 in a solution is reacted with
(c) 20 (d) None of these KI, then the liberated iodine required 100 mL 1 M
Na2S2O3 for complete reaction, then what is the per-
Comprehension 2 (Question No. 8 to 10) centage purity of sample used in making the solution.
The strength of H2O2 is expressed in several ways like molar- (a) 10% (b) 20%
ity, normality, % (w/V), volume strength, etc. The strength of (c) 5% (d) None of these
“10 V” means 1 volume of H2O2 on decomposition gives 10 14. 100 mL of 0.1 N hypo decolourised iodine by the ad-
volumes of oxygen at STP or 1 L of H2O2 gives 10 L of O2 at dition of x g of crystalline blue vitriol to excess of KI.
STP. The decomposition of H2O2 is shown as under. The value of x is
(a) 5 g (b) 2.5 g (c) 10 g (d) 1.25 g
1
H2O2(aq) h H2O(l) + O2(g)
2 Comprehension 4 (Question No. 15 to 18)
H2O2 can acts as oxidising as well as reducing agent. As ox- Iodine titrations: Compounds containing iodine are widely
idising agent H2O2 is converted into H2O and as reducing used in titrations, commonly known as iodine titration. It is
agent H2O2 is converted into O2. In both cases its n-factor of two kinds:
is 2. (i) Iodometric titrations
\ Normality of H2O2 solution = 2 ¥ Molarity of H2O2 solution (ii) Iodimetric titrations
8. What is the molarity of “11.2 V” of H2O2? (i) Iodometric titrations: It is nothing but an indirect method
(a) 1 M (b) 2 M (c) 5.6 M (d) 11.2 M of estimating the iodine. In this type of titration, an oxidising
9. What is the percentage strength (% w/V) of “11.2 V” agent is made to react with excess of KI, in acidic medium or,
H2O2? basic medium in which I– oxidises into I2. Now the liberated
(a) 1.7 (b) 3.4 I2 can be titrated with Na2S2O3 solution.
(c) 34 (d) none of these Oxidising Agent Na S O /H +
10. 20 mL of H2O2 solution is reacted with 80 mL of 0.05 KI ææææææ Æ I2 æææææ2 2 3
Æ I– + Na2S4O6
M KMnO4 in acidic medium then what is the volume Although solid I2 is black and insoluble in water, but it con-
strength of H2O2? verts into soluble I3 ions
(a) 2.8 (b) 5.6 I 2 (s) + I - m I3-
(c) 11.2 (d) none of these Black dark brown
Comprehension 3 (Question No. 11 to 14) Starch is used as indicator near the end point or equivalence
point. Even small amount of I2 molecules, gives blue colour
All such titration which involves the direct titration of iodine with starch. The completion of the reaction can be detected
with a reducing agent are grouped under iodimetry. Iodimetry when blue colour disappears at the end point. In iodimetric
is employed to determine the strength of reducing agent such titration, the strength of reducing agent is determined by re-
as sodium those sulphate: acting it with I2.

Redox 6.21
15. When 79.75 g of CuSO4 sample containing inert impu- 20. In the above question number 19, what is the percent-
rity is reacted with KI, the liberated I2 is reacted with age of free SO3 and H2SO4 in the oleum sample respec-
50 mL (1M) Na2S2O3 in basic medium, where it oxi- tively?
dises into SO 4-2 ions, and I2 reduces into I–, then what (a) 60%, 40% (b) 30%, 70%
will be the % purity of CuSO4 in sample? (c) 85%, 15% (d) 40%, 60%
(a) 60% (b) 75% (c) 50% (d) 95% 21. In the above question number 19, what will be the % of
16. When 214 g of KIO3 reacts with excess of KI in pres- combined SO3 in the given oleum sample?
ence of H+, then it produces I2. Now I2 is completely (a) 20% (b) 30% (c) 48.98% (d) 51%
reacted with 1 M Na2S2O3 solution in basic medium, 22. What volume of 1 M NaOH (in mL) will be required to
react completely with H2SO4 and SO3 in 109% labelled
where it converts into SO 4-2 ions. Then what volume
oleum?
of Na2S2O3 is needed to react the end point of the reac- (a) 250 mL (b) 2224 mL
tion? (c) 750 mL (d) 1800 mL
(a) 500 mL (b) 800 mL (c) 1500 mL (d) 750 mL
-2 Multiple Correct Type Questions
17. A solution containing Cu+2 and C2O 4 ions which on
titration with M/10 KMnO4 requires 50 mL. The re- 23. Which of the following samples of reducing agents is/
sulting solution is neutralised with K2CO3, then treated are chemically equivalent to 25 mL of 0.2 N KMnO4 to
with excess of KI. The liberated I2 required 25 mL be reduced to Mn2+ and water?
M/10 Na2S2O3 in acidic solution, then what is the dif- (a) 25 mL of 0.2 M FeSO4 to be oxidised to Fe3+
ference of the number of m mole of Cu+2 and C2O4-2 (b) 50 mL of 0.1 M H3AsO3 to be oxidised to H3AsO4
ions in the solution? (c) 25 mL of 0.1 M H2O2 to be oxidised to O2
(a) 40 (b) 10 (c) 30 (d) 50
(d) 25 mL of 0.1 M SnCl2 to be oxidised to Sn4+
18. When 1.66 g of KI is reacted with excess of KIO3 in
24. For the following balanced redox reaction,
presence of diluted HCl, then I2 is produced. The amount
of KIO3 reacted and the I2 formed are respectively. 2MnO -4 + 4H+ + Br2 m 2Mn+2 + 2BrO3- + 2H2O
(a) 4 ¥ 10–2 mole, 3 ¥ 10–3 mole If the molecular weight of MnO -4 , Br2 be Mx, My re-
(b) 1.5 ¥ 10–2 mole, 5 ¥ 10–3 mole spectively, then
(c) 5 ¥ 10–2 mole, 1.5 ¥ 10–3 mole (a) equivalent weight of MnO -4 is Mx/5
(d) 2 ¥ 10–3 mole, 6 ¥ 10–3 mole (b) equivalent weight of Br2 is My/10
Comprehension 5 (Question No. 19 to 22) (c) the n-factor ratio of Mn+2 to BrO3- is 1:1
(d) None of these
The percentage labelling of oleum is a unique process by
25. When non-stoichiometric compound Fe0.95O is heated
means of which, the percentage composition of H2SO4, SO3
in the presence of oxygen, it converts into Fe2O3, then
(free) and SO3 (combined) is calculated.
which of the following statements are correct?
Oleum is nothing but it is a mixture of H2SO4 and SO3
(a) Equivalent weight of Fe0.95O is M/0.5 where M is
i.e., H2S2O7, which is obtained by passing SO3 in solution
molecular weight of Fe0.95O.
of H2SO4. In order to dissolve free SO3 in oleum, dilution of
(b) The number of moles of Fe+3 and Fe+2 1 moles
oleum is done, in which oleum converts into pure H2SO4. It
Fe0.95O and 0.1 and 0.85 respectively.
is shown by the reaction as given below.
(c) The number of moles of Fe+3 and Fe+2 in 1 mole
H2SO4 + SO3 + H2O h of Fe0.95O are 0.85 and 0.10 respectively
2H2SO4 (pure) or, SO3 + H2O h H2SO4 (pure) (d) The % composition of Fe+2 and Fe+3 in the non
When 100 g sample of oleum is diluted with desired weight stoichiometric compound is 89.47% and 10.53%
of H2O (in g), then the total mass of pure H2SO4 obtained respectively.
after dilution is known as percentage labelling in oleum. 26. When FeS2 is oxidised with sufficient O2, then its
For example, if the oleum sample is labelled as “109% oxidation product is found to be Fe2O3 and SO2, if the
H2SO4” it means that 100 g of oleum on dilution with 9 g of molecular weight of FeS2, Fe2O3 and SO2 are M, M¢
H2O provides 109 g pure H2SO4, in which all free SO3 in 100 and M≤, then which of the following statements are
g of oleum is dissolved. correct?
19. For 109% labelled oleum if the number of moles of (a) Equivalent weight of FeS2 is M/11
H2SO4 and free SO3 be x and y respectively, then what (b) The molar ratio of FeS2 to O2 is 4:11
x+ y (c) The molar ratio of FeS2 to O2 is 11:4
will be the value of ? (d) The molar ratio of Fe2O3 and SO2 is 1:4
x– y
27. 40 g NaOH, 106 g Na2CO3 and 84 g NaHCO3 is dis-
(a) 1 (b) 18 (c) 1/3 (d) 9.9 solved in water and the solution is made 1 L. 20 mL of

this stock solution is titrated with 1N HCl, hence which 33. During the titration of a mixture of NaOH, Na2CO3 and
of the following statements are correct? inert substances against HCl.
(a) The titre reading of HCl will be 40 mL, if phenol- (a) Phenolpthalein is used to detect the end point
phthalein is used indicator from the very begin- when half equivalent of Na2CO3 and full equiva-
ning. lent NaOH is consumed.
(b) The titre reading of HCl will be 60 mL if phenol- (b) Phenolpthalein is used to detect the second end
phthalein is used indicator from the very begin- point.
ning.
(c) Methyl orange is used to detect the final end point.
(c) The titre reading of HCl will be 40 mL if the
(d) Methyl orange is used to detect the first end point.
methyl orange is used indicator after the first end
point. 34. The reaction, 3ClO–(aq) h ClO3- (aq) + 2Cl–(aq) is
(d) The tire reading of HCl will be 80 mL, if methyl an example of
orange is used as indicator from the very begin- (a) Oxidation reaction
ning. (b) Reduction reaction
M (c) Disproportionation reaction
28. 150 mL Ba(MnO4)2 in acidic medium can oxidise (d) Decomposition reaction
10
completely Assertion/Reason
(a) 150 mL 1M Fe+2
(b) 50 mL 1M FeC2O4 (a) Statement 1 is True, Statement 2 is True; Statement 2 is
a correct explanation for Statement 1.
(c) 75 mL 1M C2O 4-2
(b) Statement 1 is True, Statement 2 is True; Statement 2 is
(d) 25 mL 1M K2Cr2O7 solution NOT a correct explanation for Statement 1.
29. Which of the following quantities are dependent on
(c) Statement 1 is True, Statement 2 is False.
temperature?
(d) Statement 1 is False, Statement 2 is True.
(a) Molarity (b) Normality
(c) Molality (d) Mole fraction 35. Statement 1: In the titrations of Na2CO3 with HCl us-
ing methyl orange indicator, the volume required at the
COOH COOK
30 | and | behave as acid are well as reduc- equivalence point is twice that of acid required using
COOH COOH phenolphthalein indicator.
ing agent. Then which of the following are the correct Statement 2: Two moles of HCl are required for com-
COOH COOK
statements regarding | and | ? plete neutralization of one mole of Na2CO3.
COOH COOH 36. Statement 1: The molality of the solution does not
(a) When behaves as reducing agent, then its equiva- change with temperature.
lent weights are equal to half of its molecular Statement 2: The molaltiy is expressed in units of
weight respectively. moles per 1000 gm of solvent.
(b) 1000 mL of 1 N solution of each is neutralised by 37. Statement 1: In the roasting of FeS2, ore is converted
1000 mL 1 N Ca(OH)2. into ferric oxide and SO2 gas. The equivalent mass of
(c) 1000 mL of 1 M solution of each is neutralised by FeS2 is equal to molecular weight /11.
1000 mL of 1 M Ca(OH)2. Statement 2: The n-factor for reducing agent is total
(d) 1000 mL of 1 M solution of each is neutralised by net change in oxidation number per formula unit.
200 mL 2 M of KMnO4 in acidic medium.
38. Statement 1: Molarity and molality of solution change
31. For the reaction,
with temperature
H3PO4 + Ca(OH)2 h CaHPO4 + 2H2O Statement 2: On changing temperature the density of
1 mole 1 mole the solution is changed
then which of the following statements are correct? 39. Statement 1: Atomic weight of P atom in the molecule
(a) The equivalent weight of H3PO4 is 49. 2 yE p
(b) The resulting solution is neutralised by 1 mole of PxOy is where Ep is the equivalent mass of P
KOH atom x
(c) 1 mole of H3PO4 is completely neutralised by 1.5 x
mole of Ca(OH)2 Statement 2: The n factor of P is =
y
(d) None of these 40. Statement 1: 109% H2SO4 represent a way to express
32. 1 mol of H2SO4 will exactly neutralise concentration of industrial H2SO4 because
(a) 2 mol of ammonia (b) 1 mol of Ca(OH)2 Statement 2: It represents that 9 g H2O reacts with 40 g
(c) 0.5 mol of Ba(OH)2 (d) 2 mol of NaOH SO3 to produce 49 g H2SO4 in addition to 100 g H2SO4

Redox 6.23
Integer and Subjective Type Questions 56. 0.5 g of fuming H2SO4 (oleum) is diluted with wa-
ter. The solution requires 26.7 mL of 0.4N NaOH for
41. KMnO4 oxidises Xn+ ion to XO3- , itself changing to complete neutralisation. Find the % of free SO3 in the
Mn2+ in acid medium. 2.68 ¥ 10–3 mole of Xn+ requires sample of oleum.
1.61 ¥ 10–3 mole of MnO -4 . Calculate the atomic mass 57. 1.64 g of mixture of CaCO3 and MgCO3 was dissolved
of X, if the weight of 1 g equivalent of XCln is 56. in 50 mL of 0.8 M HCl. The excess of acid required 16
42. A solution of a 0.4 g sample of H2O2 reacted with 0.632 mL of 0.25 M NaOH for neutralisation. Calculate the
g of KMnO4 in the presence of sulphuric acid. Calcu- percentage of CaCO3 and MgCO3 in the sample.
late the percentage purity of the sample of H2O2. 58. 1.5 g of chalk were treated with 10 mL of 4N – HCl.
43. 5 L of a solution of H2O2 with x N strength is diluted to The chalk was dissolved and the solution made to 100
5.5 L. This 5.5 L H2O2 solution gives 28 L O2 at NTP. mL, 25 mL of this solution required 18.75 mL of 0.2 N
Find the value of x. – NaOH solution for complete neutralisation. Calculate
44. A dilute solution of H2SO4 is made by adding 5 mL the percentage of pure CaCO3 in the sample of chalk?
of 3N H2SO4 to 245 mL of water. Find molarity of the 59. A solution contains Na2CO3 and NaHCO3. 20 mL of
solution ¥ 100. this solution required 4 mL of 1N – HCl for titration
45. V litre volume of 0.40 M H2SO4 is required to produce with Ph indicator. The titration was repeated with the
34.0 g of H2S by the reaction, same volume of the solution but with MeOH. 10.5
8KI + 5H2SO4 Æ 4K2SO4 + 4I2 + H2S + 4H2O? mL of 1 – N HCl was required this time. Calculate the
Find 10 ¥ V. amount of Na2CO3 and NaHCO3.
46. To 50 L of 0.2 N NaOH, 2.5 L of 2N HCl and 15 L of 60. A solution contains a mix of Na2CO3 and NaOH. Us-
0.1 N FeCl3 solutions are added. What weight of Fe2O3 ing Ph as indicator 25 mL of mixture required 19.5 mL
in gram can be obtained from the precipitate? of 0.995 N HCl for the end point. With MeOH, 25 mL
47. Hemoglobin contains 0.25% iron by weight. The mo- of the solution required 25 mL of the same HCl for the
lecular weight of Hemoglobin is 89600. Calculate the end point. Calculate g/L of each substance in the mix-
number of iron atom per molecule of Hemoglobin. ture.
48. Copper froms two oxides. For the same amount of cop- 61. 200 mL of a solution of mixture of NaOH and Na2CO3
per, twice as much oxygen was used to form first oxide was first titrated with Ph and M/10 HCl. 17.5 mL of
than to form second one. If valency of Cu in I oxide is HCl was required for end point. After this MeOH was
2, then find valency of Cu in second oxide? added and 2.5 mL of same HCl was again required for
49. 1.575 g of oxalic acid (COOH)2. xH2O are dissolved next end point. Find out amounts of NaOH and Na2CO3
in water and the volume made upto 250 mL. On in the mix.
titration 16.68 mL of this solution requires 25mL of 62. A solution contains Na2CO3 and NaHCO3. 10 mL of
N/15 NaOH solution for complete neutralisation. Cal- this requires 2 mL of 0.1 M H2SO4 for neutralisation
culate x. using Ph indicator. MeOH is then added when a further
50. A solution containing 4.2 g of KOH and Ca(OH2) is 2.5 mL of 0.2 M H2SO4 was needed. Calculate milli-
neutralised by an acid. It consums 0.1 equivalent of equilivalent strength of Na2CO3 and NaHCO3 in 10 ml.
acid, calculate the percentage composition of KOH. 63. Pottasium acid oxalate K2C2O4.3H2C2O4.4H2O can be
51. 10 g CaCO3 were dissolved in 250 mL of molar HCl oxidised by MnO4 in acid medium. Calculate the vol-
and the solution was boiled. What volume of 2 M KOH ume of 0.1 M KMnO4 reacting in acid solution with 1
in ml would be required to equivalence point after boil- g of the acid oxalate.
ing? Assume no change in volume during boiling. 64. A 1.0 g sample of H2O2 solution containing x% H2O2
52. H3PO4 is a tri basic acid and one of its salt is NaH2PO4. by mass requires x cm3 of a KMnO4 solution for com-
plete oxidation under acidic conditions. Calculate the
What volume of 1 M NaOH solution in ml should be
normality of KMnO4 solution.
added to 12 g of NaH2PO4 to convert it into Na3PO4?
65. Metallic tin in the presence of HCl is oxidised by
53. It required 40.05 mL of 1 M Ce4+ to titrate 20 mL of
K2Cr2O7 to stannic chloride, SnCl4. What volume of
1 M Sn2+ to Sn4+. What is the oxidation state of the
deci-normal dichromate solution would be reduced by
cerium in the product?
1 g of tin.
54. A volume of 12.53 mL of 0.05093 M SeO2 reacted with
66. 5 g sample of brass was dissolved in 1 L dilute H2SO4.
exactly 25.52 mL of 0.1 M CrSO4. In the reaction, Cr2+
20 mL of this solution were mixed with KI, liberating
was oxidised to Cr3+. To what oxidation state was sele-
I2 and Cu+ and the I2 required 20 mL of 0.0327 N hypo
nium converted by the reaction?
solution for complete titration. Calculate the percent-
55. How many mL of 0.1 N HCl are required to react com-
age of Cu in the alloy.
pletely with 1 g mixture of Na2CO3 and NaHCO3 con-
67. 0.84 g iron ore containing x percent of iron was taken
taining equimolar amounts of two?
in a solution containing all the iron in ferrous condi-

tion. The solution required x mL of a dichromatic solu- 80. A 1.0 g sample of Fe2O3 solid of 55.2% purity is dis-
tion for oxidising the iron content to ferric state. Calcu- solved in acid and reduced by heating the solution with
late the strength of dichromatic solution. zinc dust. The resultant solution is cooled and made
68. The neutralisation of a solution of 1.2 g of a substance upto 100.0 mL. An aliquot of 25.0 mL of this solution
containing a mixture of H2C2O4.2H2O, KHC2O4.H2O requires 17.0 mL of 0.0167 M solution of an oxidant
and different impurities of a neutral salt consumed 18.9 for titration. Calculate the number of moles of electrons
mL of 0.5 N NaOH solution. On titration with KMnO4 taken up by the oxidant in the reaction of the above
solution, 0.4 g, of the same substance needed 21.55 mL titration.
of 0.25 N KMnO4. Calculate the % composition of the 81. 1.2475 g of crystalline copper sulphate was dissolved
substance. in water and excess of KI was added. The liberated io-
69. 50 g of a sample of Ca(OH)2 is dissolved in 50 mL dine consumed 50 mL N/10 Na2S2O3 solution to reach
of 0.5 N HCl solution. The excess of HCl was titrated the end point of the titration. Calculate the number of
with 0.3 N – NaOH. The volume of NaOH used was water molecules of hydration in crystalline copper sul-
20cc. Calculate % purity of Ca(OH)2. phate salt.
70. 1 g of impure sodium carbonate is dissolved in water 82. A 1g sample of K2Cr2O7 containing some inert mate-
and the solution is made up to 250 mL. To 50 mL of rial was entirely reduced with concentrated. HCl. The
this made up solution, 50 mL of 0.1 N – HCl is added chlorine liberated was passed through hot solution of
and the mix after shaking well required 10 mL of 0.16 NaOH at 800C, and it completely diproportionates to
N – NaOH solution for complete titration. Calculate the form ClO3- and Cl–. This NaClO3 was isolated and its
% purity of the sample. reduction with KI (aq) liberated iodine, giving Cl–.The
71. What amount of substance containing 60% NaCl, 37% iodine thus liberated required 100 mL of decinormal
KCl should be weighed out for analysis so that after hypo solution for complete titration. What is the per-
the action of 25 mL of 0.1 N AgNO3 solution, excess centage purity of the dichromate sample?
of Ag+ is back titrates with 5 mL of NH4SCN solution. 83. 2.5 g of mixture of crystalline oxalic acid (H2C2O4.
Given that 1 mL of NH4SCN = 1.1. mL of AgNO3. 2H2O) and sodium oxalate (Na2C2O4) was dissolved
72. A bottle labelled with “12 V H2O2” contain 700 mL in 100 mL of water. 50 mL of this solution was titrated
solution. If a student mix 300 mL water in it what is the against N/10 NaOH solution when 119.05 mL of the
g/litre strength volume strength of final solution. base was found necessary to reach the end point with
73. 50 mL of an aqueous solution of H2O2 were treated phenolphthalein as the indicator. 1 g of the mixture
with an excess of KI solution and dilute H2SO4, the was dissolved in water and the solution titrated against
liberated iodine required 20 mL of 0.1 N Na2S2O3 solu- N/10 KMnO4 in the presence of dilute H2SO4. What is
tion for complete interaction. Calculate the concentra- the volume of KMnO4 needed for getting the end point
tion of H2O2 in g/L. with 0.5 g of the mixture?
74. 100 kg hard water contains 5 g MgSO4. Find hardness. 84. 25 mL of a solution containing HCl was treated with
75. 1 L hard water contains 1 mg CaCl2 and 1 mg MgSO4. excess of M/5 KIO3 and KI solution of unknown con-
Find hardness. centration where I2 liberated is titrated against a stan-
76. Calculate the hardness of water sample which contains dard solution of 0.021 M Na2S2O3 solution whose 24
0.001 mol MgSO4 per litre of water. mL were used up. Find the strength of HCl and volume
77. Calculate the amount of lime Ca(OH)2 required to re- of KIO3 solution consumed.
move the hardness in 60 L of pond water containing 85. 0.6213 g of sample contains an unknown amount of
1.62 mg of calcium bicarbonate per 100 mL of water. As2O3. The sample was treated with HCl resulting in-
78. What volume at NTP of gaseous ammonia will be re- formation of AsCl3 (g) which was distilled into a bea-
quired to be passed into 30 cc of N – H2SO4 solution to ker of water. The hydrolysis reaction is as follows:
bring down the acid strength of the latter to 0.2 N. AsCl3 + 2H2O Æ HAsO2 + 3H+ + 3Cl–
79. Calculate the amount (in milligrams) of SeO3-2 in so- The amount of HAsO2 was determined by titration with
lution on the basis of following data 20 mL of M/60 0.04134 M I2, requiring 23.04 mL to reach the equiva-
solution of KBrO3 was added to a definite volume of lence point. The redox products in the titration were
SeO3-2 solution. The bromine evolved was removed H3AsO4 and I–. Find the amount of KMnO4 needed to
by boiling and excess of KBrO3 was back titrated with oxidise As in As2O3 to its maximum possible oxidation
5 mL of M/25 solution of NaAsO2. The reactions are state in acidic medium.
given below. (Atomic mass of K = 39, Br = 80, As = 75, 86. A sample of steel weighing 0.6 g and containing S as an
Na = 23, O = 16, Se = 79) impurity was burnt in a stream of O2, when S was con-
(a) SeO3-2 + BrO3- + H + Æ SeO -4 2 + Br2 + H 2O verted to its oxide SO2.SO2 was then oxidised to SO -- 4
by using H2O2 solution containing 30 mL of 0.04 M
(b) BrO3- + AsO 2- + H 2O Æ Br - + AsO 4-3 + H +

Redox 6.25
NaOH. 22.48 mL of 0.024 M HCl was required to neu- be 123.9 mL. A 1.5 g of the sample requires 150 mL
tralise the base remaining after oxidation. Calculate the of M/10 HCl for complete neutralisation. Calculate the
% of S in the sample> percentage composition of the components of the mix-
87. The mixture of CuS (molar weight = M1) and Cu2S ture.
(molecular weight = M2) oxidised by KMnO4 (mo- 93. 1 L of a mixture of O2 and O3 at STP was allowed to
lecular weight = M3) in acidic medium, the product react with an excess of acidified solution of KI. The
obtained are Cu2+, SO2. Find the equivalent weight of iodine liberated required 40 mL of M/10 sodium thio-
CuS, Cu2S and KMnO4 respectively. sulphate solution for titration. What is the mass per
88. A mixture of two gases, H2S and SO2 is passed through cent of ozone in the mixture? Ultraviolet radiation of
three beakers successively. The first beaker contains wavelength 300 nm can decompose ozone. Assuming
Pb2+ ions, which absorbs S2– forming PbS. The second that one photon can decompose one ozone molecule,
beaker contains 25 mL of 0.0396 N I2 to oxidise SO2 to how many photons would have been required for the
SO 24- . The third contains 10 mL of 0.0345 N thiosul- complete decomposition of ozone in the original mix-
phate solution to retain any I2 carried over from the sec- ture?
ond absorber. A 25 L gas sample was passed through 94. Potassium selenate is isomorphous with potassium sul-
the apparatus followed by an additional amount of N2 phate and contains 45.52% selenium by weight. Cal-
to sweep last traces of SO2 from first and second ab- culate the atomic weight of selenium. Also report the
sorber. The solution from the first absorber was made equivalent weight of potassium selenate.
acidic and treated with 20 mL of 0.0066 M K2Cr2O7 95. Borax in water gives
which converted S2– to SO2. The excess dichromate B4O72- + 7H 2O h 4H3BO3 + 2OH -
was reacted with solid KI and the liberated iodine re-
quired 7.45 mL of 0.0345 N Na2S2O3 solution. The How many gram of borax (Na2B4O7 ◊ 10H2O) are re-
solutions in the second and third absorbers were com- quired to
bined and the resultant iodine was titrated with 2.44 (a) prepare 50 mL of 0.2 M solution?
mL of the same thiosulphate solution. Calculate the (b) neutralise 25 mL of 0.1934 M of HCl and H2SO4
concentrations of SO2 and H2S in mg/L of the sample separately?
89. A 1 g sample containing NaOH as the only basic sub- 96. For estimating ozone in the air, a certain volume of air
stance and some inert impurity was left exposed to at- is passed through an acidified or neutral KI solution
mosphere for a very long time so that part of NaOH when oxygen is evolved and iodide is oxidised to give
got converted into Na2CO3 by absorbing CO2 from at- iodine. When such a solution is acidified, free iodine is
mosphere. The resulting sample was dissolved in water evolved which can be titrated with standard Na2S2O3
and volume made up to 100 mL. A 20 mL portion of solution. In an experiment, 10 L of air at 1 atm and
this solution required 16 mL 0.25 M HCl solution to 27°C were passed through an alkaline KI solution, at
reach the equivalence point when methyl orange was the end, the iodine entrapped in a solution on titration
used as indicator. In a separate analysis, 20 mL por- as above required 1.5 mL of 0.01 N Na2S2O3 solution.
tion of the same solution was taken along with phe- Calculate volume % of O3 in sample.
nolphthalein indicator and mixed with 50 mL of 0.1 M 97. 1.249 g of a sample of pure BaCO3 and impure CaCO3
HCl solution. An additional 9.00 mL 0.1 M Ba(OH)2 containing some CaO was treated with diluted HCl and
solution was required to just restore the pink colour of it evolved 168 mL of CO2 at NTP. From this solution,
solution. Determine mass percentage of NaOH in the BaCrO4 was precipitated, filtered and washed. The
original sample and mass percentage of Na2CO3 in the precipitate was dissolved in dilute sulphuric acid and
sample after exposure to atmosphere. diluted to 100 mL. 10 mL of this solution, when treated
90. Calculate the weight of MnO2 and the volume of HCl with KI solution, liberated iodine which required ex-
of specific gravity 1.2 g mL–1 and 4% nature by weight actly 20 mL of 0.05N Na2S2O3. Calculate the percent-
needed to produce 1.78 L of Cl2 at STP by the reaction. age of CaO in the sample.
91. 3.2 g of pyrolusite was treated with 50 mL of 0.5 M 98. In a quality control analysis for sulphur impurity 5.6
oxalic acid and some sulphuric acid. The oxalic acid g steel sample was burnt in a stream of oxygen and
left undecomposed was raised to 250 mL in a flask. 25 sulphur was converted into SO2 gas. The SO2 was then
mL of this solution when treated with 0.02 M KMnO4 oxidised to sulphate by using H2O2 solution to which
required 32 mL of the solution. Find the % of MnO2 in had been added 30 mL of 0.04M NaOH. The equation
the sample and also the percentage of available oxygen. for reaction is
-
92. A 2.0 g sample of a mixture containing sodium carbon- SO2(g) + H2O2(aq) + 2OH (aq) h SO 4-2(aq) + 2H2O(l)
ate, sodium bicarbonate and sodium sulphate is heated
22.48 mL of 0.024M HCl was required to neutralise the
till the evolution of CO2 ceases. The volume of CO2
at 750 mm Hg pressure and at 298 K is measured to base remaining after oxidation reaction. Calculate % of
sulphur in given sample.

99. A granulated sample of aircraft alloy (Al, Mg, Cu) MnO4– Mn2+
2–
weighing 8.72 g was first treated with alkali and then MnO4
with very dilute HCl, leaving a residue. The residue af- MnO2
ter alkali boiling weighed 2.10 g and the acid insoluble Mn2O3
residue weighed 0.69 g. What is the composition of the
Changes in oxidation number respectively are
alloy?
(a) 1, 3, 4, 5 (b) 5, 4, 3, 2
100. 2.480 g of KClO3 are dissolved in concentrated HCl
(c) 5, 1, 3, 4 (d) 2, 6, 4, 3
and the solution was boiled. Chlorine gas evolved in
8. Oxidation number of Cl in CaOCl2 (bleaching powder
the reaction was then passed through a solution of KI
is ) [AIEEE, 02]
and liberated iodine was titrated with 100 mL of hypo.
(a) Zero, since it contains Cl2
12.3 mL of same hyposolution required 24.6 mL of 0.5
(b) –1, since it contains Cl–
N iodine for complete neutralisation. Calculate % pu-
(c) +1, since it contains ClO–
rity of KClO3 sample.
(d) +1 and –1 since it contains ClO– and Cl–
101. P and Q are two elements which forms P2Q3 and PQ2.
9. Which of the following is a redox? [AIEEE, 02]
If 0.15 mole of P2Q3 weights 15.9 g and 0.15 mole of
(a) 2NaAg(CN)2 + Zn ÆNa2Zn (CN)4 + 2Ag
PQ2 weights 9.3 g, what are atomic weights of P and Q?
(b) BaO2 + H2SO4 Æ BaSO4 + H2O2
(c) N2O5 + H2OÆ 2HNO3
PREVIOUS YEARS’ QUESTIONS (d) AgNO3 + KI Æ AgI + KNO3
OF JEE (MAIN & ADVANCED) 10. In the coordination compound, K4[Ni (CN)6], the oxi-
1. The oxidation number of phosphorus in Ba(H2PO2)2 is dation state of nickel is [AIEEE, 03]
[JEE, 1990] (a) +1 (b) +2 (c) –1 (d) 0
(a) +3 (b) +2 (c) +1 (d) –1 11. Amongst the following, the pair having both the metals
2. The oxidation states of the most electronegative ele- in their highest oxidation state is [JEE, 2004]
ment in the products of the reaction of BaO2 with dilute (a) [Fe(CN)6]3– and [Co(CN)6]3–
H2SO4. [JEE, 1991] (b) [CrO2Cl2] and [MnO4–]
(a) 0 and –1 (b) –1 and –2 (c) TiO3 and MnO2
(c) –2 and 0 (d) –2 and +2
(d) [MnCl4]2– and [NiF6]–2
3. For the redox reaction, [JEE, 1992]
12. The oxidation state of Cr in [Cr(NH3)4Cl2]+ is
MnO 4- + C2O 42- + H+ Æ Mn2+ + CO2 + H2O [AIEEE, 2005]
the correct coefficients of the reactants for the balanced (a) +2 (b) +3 (c) 0 (d) +1
reaction are: 13. The oxidation state of chromium in the final product
MnO -4 C2O 42- H+ formed by the reaction between Kl and acidified potas-
sium dichromate solution is [AIEEE, 05]
(a) 2 5 16
(a) +6 (b) +4 (c) +3 (d) +2
(b) 16 5 2
14. Which of the following chemical reaction depicts the
(c) 5 16 2
oxidising behaviour of H2SO4? [AIEEE, 2006]
(d) 2 16 5
4. How many millilitres of 0.5 M H2SO4 are needed to (a) 2PCl5 + H2SO4 Æ 2POCl3 + 2HCl + SO2Cl2
dissolve 0.5 g of copper II carbonate? [JEE, 1999] (b) 2HI + H2SO4 Æ I2 + SO2 + 2H2
5. Among the following species, in which oxidation state (c) Ca(OH)2 + H2SO4 Æ CaSO4 + 2H2O
of the element is +6? [JEE, 2000] (d) NaCl + H2SO4 Æ NaHSO4 + HCl
- 3-
(a) MnO 4 (b) Cr(CN)6 15. Amount of oxalic acid present in a solution can be de-
termined by its titration with KMnO4 solution in the
(c) NiF62- (d) CrO2Cl2
presence of H2SO4. The titrations gives unsatisfactory
6. How many moles of electron weigh 1 kg: result when carried out in the presence of HCl, because
[JEE, 2002] HCl [AIEEE, 2008]
1 (a) gets oxidised by oxalic acid to chlorine.
(a) 6.023 ¥ 1023 (b) ¥ 1031
9.108 (b) furnishes H+ ions in addition to those from oxalic
6.023 1 acid.
(c) ¥ 1054 (d) ¥ 108 (c) reduces permanganate to Mn2+.
9.108 9.108 ¥ 6.023
(d) oxidises oxalic acid to carbon dioxide and water.
7. MnO -4 is good oxidising agent in different medium 16. Among the following, the number of elements showing
changing to [AIEEE, 2002] only one non-zero oxidation state is O, Cl, F, N, P, Sn,
Tl, Na, Ti. [IIT JEE, 2010]

Redox 6.27
17. The difference in the oxidation numbers of two types of The correct statement(s) in the balanced equation is/are
sulphur atoms in Na2S4O6 is …… [IIT JEE, 2011] (a) Stoichiometric coefficient of HSO -4 is 6
18. Oxidation states of the metal in the minerals haematite (b) Iodide is oxidised
and magnetite, respectively, are [IIT JEE, 2011] (c) Sulphur is reduced
(a) II, III in haematite and III in magnetite (d) H2O is one of the products
(b) II, III in haematite and II in magnetite 21. Match the reactions in Column I with the nature of the
(c) II in haematite and II, III in magnetite reactions/type of the products listed in Column II.
(d) III is haematite and II, III in magnetite
Column I Column II
19. Consider the following reaction:
p. Redox reaction
z a. OQ -2
2 Æ O2 + O2
xMnO 4- + yC2O 24- + zH+ Æ xMn2+ + 2yCO2 + H2O
2 q. One of the prod-
The values of x, y and z in the reaction are, respectively. b. CrO 2- + H + Æ ucts has trigonal
4
planar structure
[JEE Main, 2013]
(a) 5, 2 and 16 (b) 2, 5 and 8 r. Dimetic bridged
(c) 2, 5 and 16 (d) 5, 2 and 8 c. MnOQ Q +
4 + NO 2 + H Æ
tetrahedral metal
20. For the reaction [JEE Advanced, 2014] ion
s. Disproportion-
I– + ClO3- + H2SO4 Æ Cl– + HSO -4 + I2 d. NO3Q + H 2SO 4 + Fe +2 ation
Answer Key
LEVEL I
1. (b) 2. (d) 3. (a) 4. (b) 5. (b) 6. (d) 7. (d) 8. (c) 9. (c) 10. (a)
11. (c) 12. (d) 13. (a) 14. (b) 15. (a) 16. (b) 17. (a) 18. (b) 19. (b) 20. (c)
21. (c) 22. (d) 23. (a) 24. (a) 25. (d) 26. (d) 27. (d) 28. (c) 29. (b) 30. (b)
31. (b) 32. (a) 33. (c) 34. (b) 35. (a) 36. (a) 37. (b) 38. (a) 39. (a) 40. (c)
41. (c) 42. (a) 43. (b) 44. (b) 45. (d) 46. (a) 47. (a) 48. (a) 49. (a)
LEVEL II
1. (c) 2. (c) 3. (b) 4. (d) 5. (b) 6. (c) 7. (b) 8. (a) 9. (a) 10. (a)
11. (b) 12. (b) 13. (a) 14. (a) 15. (b) 16. (d) 17. (b) 18. (b) 19. (b) 20. (b)
LEVEL III
1. (A) Æ r, t; (B) Æ p, t; (C) Æ q; (D) Æ s 2. (A) Æ r; (B) Æ t; (C) Æ p; (D) Æ s

3. (A) Æ q, t; (B) Æ p; (C) Æ r, t; (D) Æ s, t
4. (b) 5. (c) 6. (c) 7. (b) 8. (a) 9. (b) 10. (b) 11. (a) 12. (d) 13. (a)
14. (b) 15. (b) 16. (d) 17. (b) 18. (d) 19. (d) 20. (d) 21. (c) 22. (b) 23. (a, c, d)
24. (a, b, c) 25. (b, d) 26. (a, b, d) 27. (a, c, d) 28. (a, b, c, d) 29. (a, b)
30. (a, b, d) 31. (a, b, c) 32. (a, b, d) 33. (a, c) 34. (a, b, c) 35. (a)
36. (b) 37. (a) 38. (d) 39. (c) 40. (b) 41. (41) 42. (85) 43. (1) 44. (2) 45. (125)
46. (40) 47. (4) 48. (1) 49. (2) 50. (35) 51. (25) 52. (200) 53. (3) 54. (0)
55. 157.89 ml 56. 20.72 % 57. (48.78%, 51.22%) 58. 83.33% 59. 0.424 mg, 0.21 mg
60. 23.2 gm/lit., 22.28 gm/lit. 61. 0.06 gm, 0.0265 gm 62. 0.4 & 0.6 63. 31.5 ml
64. 0.588 N 65. 337.8 ml 66. 41.53% 67. 0.15 N 68. 14.36 % & 81.7%
69. 1.406% 70. 90.1% 71. 0.1281 gm 72. 25.5 gm/L, 8.4 V 73. 0.68gm/L
74. 41.66 ppm 75. 1.734 ppm 76. 100 ppm 77. 0.444 gm 78. (537.6 ml)

79. 84 mg 80. (3) 81. (5) 82. 58.8 % 83. 77.46 mL 84. 0.168N & 0.42 mL 85. 0.06 g
86. 1.76% 87. M1/6, M2/8, M3/5 88. 0.1212 mg/L & 0.7178 mg SO2/L 89. 80% & 36.05 %
90. 241.66 ml 91. (24.44% and 4.5%) 92. 42%, 26.5%, 31.5% 93. 1.2 ¥ 1021
94. 118.2 & 130.1 95. (a) 3.82 g (b) 0.9235 g & 1.847g 96. 1.847 ¥ 10 %
–3
97. 14.09%
98. 0.1875% 99. Al = 75.9%, Mg = 16.2%, Cu = 7.9% 100. 82.32% 101. P = 26, Q = 18
1. (c) 2. (b) 3. (a) 4. 8.097 ml 5. (d) 6. (d) 7. (c) 8. (d) 9. (a)

10. (b) 11. (b) 12. (d) 13. (c) 14. (b) 15. (c) 16. (2) 17 (5) 18. (d) 19. (c)
20. (a), (b), (d) 21. (a) Æ p, s ; (b) Æ r ; (c) Æ p, q ; (d) Æ p
Hints and Solutions

(c) SO3 > SO2 > H2S > S8
LEVEL I Ø Ø Ø Ø
+6 +4 –2 0
1. (b) CaCl2 + 2AgNO3 Æ 2AgCl + Ca(NO3)2 (d) H2SO4 > SO2 > H2S > H2S2O8.
4.31 +6 +4 –2 (6, 6)
n= 7. (d) (NH4)2Cr2O7 h N2 + Cr2O3 + 4H2O
143.5
Decomposition reaction
4.31 1
Moles of CaCl2 = ¥ = 0.015 2.0 0 2.5 -1
143.5 2 8. (c) S2 O5-2 + I 2 h S2 O6-2 + I -
2. (d) CaCO3 + 2HCl Æ CaCl2 + CO2 + H2O
Æ I-
Redn
25 ¥ 0.75 fi Redox reaction Io2 æææ
n= = No.of moles of HCl
S2O3-2 æææ
Æ S2O6-2
Oxd.
1000
25 ¥ 0.75 1 (4, 0) (5, 0, 0, 5)
Moles of CaCO3 required = ¥ 9. (c) xHI + yHNO3 h NO + I2 + H2O
1000 2
25 ¥ 0.75 1 È Æ I 2 + 2e) ¥ 3˘ .....(1)
(2I – ææ
Mass of CaCO3 = ¥ ¥ 100 = 0.9375 g Í ˙
1000 2 Í +5 – +2
˙
3. (a) 2H2 + O2 Æ 2H2O Î(NO3 + 3e ææ Æ N O) ¥ 2 ˚ .....(2)
10 5 Adding (1) and (2)
2 vol. H2 give 2 vol. of H2O vapours
fi 6I– + 2NO3- h 2NO + 3I2
\ 10 vol. H2O vapour will form 10 volume H2O
6HI + 2HNO3 h 2NO + 3I2 + 4H2O
4. (b) Mass of oxide = 2 g
fi x = 6, y = 2
Mass of metal = 1.6 g +7 +3 +4
Mass of oxygen = 0.4 g – –2
10. (a) MnO4 + C2O4 + H+ Mn+2 + 2CO2 + H2O
1.6 ¥ 8 2¥1=2
Equivalent weight of metal = = 32 5
0.4
+6 +3
5. (b) C rO5 Æ C r2 (SO 4 )3 2MnO 4- + 5C2O 4-2 + 16H+ Æ 2Mn+2 + 10CO2 + 8H2O
Number of moles of electron required = 3 Normality
11. (c) Molarity =
6. (d) n factor
O O O O 1 M H3PO4 = 3N H3PO4
(a) O S O S O Na–O S S S S O 12. (d) 2CrO5 + 3H2SO4 h Cr2(SO4)3 + 3H2O + 7/2O2
+6 +6 +5 +5
OH OH O ONa 1 mole CrO5 Liberate h 7/4 mole of O2
H2S2O7 (6, 6) Na2S4O6 (5, 0, 0, 5) +5 +3
–3
O O H 13. (a) AsO4 + 2H+ + 2I– AsO3–3 + H2O + I2
+ – +4 2
(b) NaO S S Na2S2O3 O S O O H
Molar mass Na3AsO4 = 23 ¥ 3 + 75 + 15 ¥ 4
O–Na– O Molar mass = 208
(4, 0) (6)

Redox 6.29
1 Ê 1 ˆ FeO 0.40 4
Equivalent of AsO -4 = =Á ˜ Mole ratio = fi
Ê 208 ˆ Ë 104 ¯ Fe 2O3 0.30 3
ÁË ˜¯ 19. (b) 1 mole of FeSO4 gives 1 mole Fe2+ and 1 mole
2
Equivalent of Na3AsO4 = Equivalent of I2 SO 24- while a mole Fe2(SO4)3 gives 2 a mole Fe2+ and
= Equivalent of Na2S2O3 3 a mole SO 24- .
1
= 0.2 ¥ V according to question.
104
1 [SO -4 - ]FeSO4 = [SO -4 - ]Fe2 (SO4 )3
L = V = 48.1 mL
104 ¥ 0.2 1 ¥ SO -4 - = a ¥ 3 ¥ SO -4 -
14. (b) Milliequivalent of KMnO4 = .2 ¥ 50 ¥ 5 = 50 1
Milliequivalent of H2O2 = 2 ¥ 25 ¥ .5 = 25 a = mole
3
Milliequivalent of KMnO4 remaining = (50 – 25) = 25
2
25 \ number of moles of Fe3+ = 2a = mole
Mole of KMnO4 = ¥ 10–3 = 5 ¥ 10–3 = .005 3
5
Fe 2+ 1 3
100 X Ê 3 ˆ \ = =
15. (a) =Á ˜ ¥2 Fe +3
2/3 2
1000 Ë 24 ¯
Fe : Fe +3 : = 3 : 2
+2
20
X= = 2.5 3
8 20. (c) 2Fe +O2 h Fe2O3
16. (b) Ca(HCO3)2 + CaO h 2CaCO3 + H2O 2
1 mole CaO required for precipitation of 2 mole CaCO3 Initial n excess 0
OR x
n–x
2 ¥ 100 gram CaCO3 obtained by 1 ¥ 56 gram CaO 2
56 Ê xˆ
\ 2 gram CaCO3 obtained by ¥ 2 = 0.56 gram weight (n – x) ¥ 56 + ÁË ˜¯ ¥ 160 = n ¥ 56 ¥ 1.1
200 2
24x = 5.6n
17. (a) (320 mL, 10V H2O2) + (80 mL, 5NH2O2)
Ê xˆ
(A) (B) ÁË ˜¯ = 0.2323
Ê 10 ˆ n
NA = Á
Ë 5.6 ˜¯ % total iron = 23.3%
1
10
¥ 320 + 5 ¥ 80 21. (c) HNO3 + (NH4)2SO4 h N2 + NO2
N AVA + N BVB 5.6
fi NC = =
VA + VB 320 + 80 2¥3=6
571.42 + 400 Milliequivalent of HNO3 = Milliequivalent of NH +4
=
400 Mole ¥ n-factor = Mole ¥ n-factor
= 2.4285 1 ¥ Mole = 1 ¥ 6
N Mole of HNO3 = 6
volume strength = H+
5.6 22. (d) Z+x + KMnO 4 ææÆ Mn 2+ + Z+y
\ volume strength = 5.6 ¥ 2.4285 = 13.6 V Milliequivalent of Z+x = Milliequivalent of KMnO4
volume strength in gram/L = N ¥ 17 25 ¥ 0.1 ¥ (y – x) = 25 ¥ 0.04 ¥ 5
= 2.4285 ¥ 17
= 41.285 gram L–1 0.04 ¥ 5
(y – x) = =2
1 0.1
18. (b) Fe + O2 h FeO Z2+ h Z4+
2
(4 – 2) = 2
1 0.65
|y| > |x| \ Correct Ans. (d)
0 0.15 1
23. (a) Cl– + KMnO4 h Mn2+ + Cl2
1
2FeO + O2 h Fe2O3 Milliequivalent of NaCl = Milliequivalent of KMnO4
2
10 5
1 0.15 Mole ¥ n-factor = ¥
(1 – 0.60) 0.30 158 2
0.4 0.30 10 5
Mole ¥ 1 = ¥
158 2

10 5 29. (b) Volume of O2 at NTP

Volume of Cl2 = ¥ ¥ 22.4 = 3.54 L
158 2 500 ¥ 1 ¥ 273
VO2 =
24. (a) I2 h I + –
IO3- 300
VO2 = 455 mL
I2 Æ 2I– I2 h 2IO3- 35 mL of H2O2 gives 455 mL at N.T.P.
[2e– + I2 Æ 2I–] ¥ 5 I2 + 6H2O h 2IO3- 455
\ 1 mL of H2O2 gives = = 13
35
10e + 5I2 Æ 10I
– –
I2 + 6H2O + 12OH h –
= 13 mL of O2 at NTP
2IO3- + 12H2O + 10e– Hence volume strength of H2O2 = ‘13 V’
\ I2 + 12OH– h 2IO3- + 6H2O + 10e– 30. (b) Half milliequivalent of salt (Na2CO3) in neutralise
using Hph indicator because HPh work in basic me-
\ net reaction
dium.
12OH– + 6I2 h 10I– + 2IO3- + 6H2O 1
milliequivalent of salt = milliequivalent of HCl
IO3- 2 2
Ratio of = = 1: 5
I- 10 1
(20 ¥ 0.1 ¥ 2) = 0.05x (i)
25. (d) Equivalent mass 2
Molecular mass Complete milliequivalent of salt (Na2CO3 ◊ NaHCO3
= ◊ 2H2O) is neutralise using MeOH indicator (Work in
n-factor
acidic medium)
As +2 3 h 2As +5 n-factor 4 Milliequivalent of salt = Meq of HCl
-2 +6 20 ¥ 0.1 ¥ 3 = 0.05y (ii)
S2 h 3S 24 Eq. (ii) – Eq. (i)
Total n-factor = 28 0.05(y – x) = (6 – 2)
Molecular weight 4
Equivalent mass = (y – x) =
28 0.05
+2 –2 +5 +2 +5 +6 +4
26. (d) Zn S + HNO3 h Zn (NO3 ) 2 + H 2SO 4 + NO 2 (y – x) = 80 mL
Change in O.N. of Zn 31. (b) Milliequivalent of KMnO4 = Milliequivalent of C2O 4-2
Zn = 0 1
90 ¥ = 100 ¥ N C O –2 = 100 ¥ 2 ¥ M C O-2
S = 6 – (–2) = 8 20 2 4 2 4
N=5–4=1 9 9
27. (d) Fe(C2O4) + KMnO4 h Fe+3 + CO2 + Mn+2 + H2O mole of oxalate = ¥ 10-3 = ¥ 10-3 mole
2¥2 4
(1 ¥ 1 + 2 ¥ 1) = 3 9
Weight of oxalate = ¥ 88 ¥ 10–3 = 0.198 gram
4
1¥5
0.198
for [a, b, c] % C2O 4-2 = ¥ 100 = 66%
3 ¥ 0.1 ¥ 25 = 5 ¥ M ¥ 25 0.300
0.3 32. (a) Milliequivalent of KMnO4 = Milliequivalent of
M= = 0.06 M
5 C2O 4-2 = Milliequivalent of CaCO3
for [d] 40 ¥ .25 = Milliequivelent of CaO
3 ¥ 0.1 ¥ 25 = 5 ¥ 15 ¥ M 10 ¥ 10-3
\ molarity = 0.1 M = Mole of CaO
2
\ Correct Ans. (d)
28. (c) K2Cr2O7 + Sn2+ h Sn4+ + Cr3+ 5 ¥ 10 –3 ¥ 56 ¥ 100
% CaO =
Sn4+ + Fe2+ h Fe3+ .518
Milliequivalent of Sn4+ = Milliequivalent of K2Cr2O7 CaO = 54%
Milliequivalent of Sn4+ = Milliequivalent of Fe3+ Number of equivalent
33. (c) M =
Milliequivalent of Fe3+ = Milliequivalent of K2Cr2O7 Volume of sol (in L)
4.9 ¥ 6 fi Milliequivalent = 50 ¥ 0.2 = 10
N K 2Cr2O7 = =1
294 ¥ 0.1 10 ¥ 10-3
Millimol ¥ n-factor = NV = nf ¥ MV = 1 ¥ 1 ¥ 10 \ mole = = 5 ¥ 10-3
2
Millimol = 10
Molar mass = 24 + 16 ¥ 4 + 2 + 2 ¥ 18 = 126 gm.

Redox 6.31
fi Mass of H2C2O4.2H2O 42. (a) Al2(SO4)3 + BaCl2 h BaSO4 Ø + AlCl3

= 126 ¥ 5 ¥ 10–3 = 0.63 gm Initial 10 ¥ 0.4 ¥ 6 20 ¥ 0.6 ¥ 2 0 0
34. (b) Milliequivalent of HNO3 = Milli- n-factor = 3 24 24
equivalent of Fe2+ Finally 0 0 24 24
+5 2+
8 (NO3 NO) 24
or 6¥3¥V= [Al3+] = = 0.266 M
56 30 ¥ 3
V = 7.936 ¥ 10–3 L = 7.936 ml 43. (b) Milliequivalent of NaBrO3 = 55.5 ¥ 0.672 = 37.296
35. (a) CaCO3 + HCl Æ CaCl2 + H2O + CO2 (224 mL) Let weight of NaBrO3 = W
224 W
CO2 mole = = 10–2 \ ¥ 6 ¥ 1000 = 37.296
22400 M NaBrO3
10 –2 1 W
HCl (M) = HCl (N) = = = 0.05 \ ¥ 6 ¥ 1000 = 37.296
200 ¥ 10 –3
20 151
36. (a) KMnO4 (n factor in acidic medium) = 5 \ W = 0.9386 gram
K2Cr2O7 (n factor in acidic medium) = 6 44. (b) Milliequivalent of NaHSO3 = Milliequivalent of
6 ¥ 0.1 ¥ V1 = 5 ¥ 0.3 ¥ V2 NaIO3 = N ¥ V =
0.68
¥ 6 ¥ 1000
6 198
V1 = V2 WNaHSO3 0.68
15 \ ¥ 2 ¥ 1000 = ¥ 6 ¥ 100
M NaHSO3 198
2
V2 = V1
5 0.68 ¥ 6 ¥ 100 ¥ 104
WNaHSO3 = = 0.2143
37. (b) K2Cr2O7 have greater n factor as compared to 198 ¥ 1000
KMnO4 so same volume of K2Cr2O7 will oxidise more
45. (d) Let us first solve this problem by writing the com-
amount of Fe+2.
plete balanced reaction.
38. (a)
I2 + 2Cl2 Æ ICl + ICl3 3BaCl2 + 2Na3PO4 h Ba3(PO4)2 Ø + 6NaCl
254 g 142 g 1 : 1 3
We can see that the moles of BaCl2 used are times
25.4 g 14.2 g 0.1 : 0.1 2
but Cl2 given is only 12.2 g (less than normal ratio the moles of Na3PO4. Therefore, to react with 0.1 mol
hence limiting reagent) of Na3PO4, the moles of BaCl2 required would be 0.1
14.2 g Cl2 produces Æ 0.1 moles of each 3
¥ = 0.15. Since BaCl2 is 0.5 mol, we can conclude
0.1 2
12.2 g Æ = ¥ 12.2 = 0.086 mole of each that Na3PO4 is the limiting reagent. Therefore, moles of
14.2
hence molar ratio remain equal (1:1) Ba3(PO4)2 formed is
39. (a) 2Fe + 3H2O Æ Fe2O3 + 3H2 1
54 g H2O(g) convert 112 g Fe to its oxide 0.1 ¥ = 0.05 mol
2
112 46. (a) Milliequivalent of Acid = Milliequivalent of NaOH
\ 18 gram H2O(g) convert ¥ 18 = 37.3 g
54 0.52
n-factor = 5 ¥ 1000 = 100 ¥ 0.2
E
40. (c) As2O3 + MnO4– 3–
2AsO4 + Mn2+ \ E = 26
n-factor = 4 34
47. (a) Weight of H2O2 in 1 mL = g
Let, molarity of KMnO4 solution be M 1120
\ Equivalent of As2O3 = Equivalent of KMnO4 solution 1
H2O2 Æ H2O + O2
2
0.1097 36.10 ¥ M ¥ 5
¥4= 34 g of H2O2 gives 11200 mL of O2 at STP
198 1000
34 11200 34
198 \ g of H 2O 2 ∫ ¥
(Equivalent weight As2O3 = ) 1120 34 1120
4
Molarity = 0.0122 M = 10 mL of O2 at STP.
41. (c) Milliequivalent of S2O32- = Milliequivalent of CrO 24- 48. (a) Mn7+ + 5e– Æ Mn2+] ¥ 3
Fe2+ Æ Fe3+ + e–
40 ¥ 0.246 ¥ 8 = V ¥ 0.154 ¥ 3
\ V = 170.4 mL C2O 42- Æ 2CO2 + 2e–

3 moles of KMnO4 = 5 moles of FeC2O4 2.517 25

6 or = ¥N
\ 2 mol of ferrous oxalate ∫ mole of KMnO4 170 1000
5 Hence N = 0.6
49. (a) Milliequivalent of KMnO4 = Milliequivalent of FeC2O4 6. (c) Number of equivalent = Mole ¥ n-factor
n-factor = 2 SO3-2 + H2O h SO 4-2 + 2H+ + 2e– (1)
MnO4– + FeC2O4 + H+ Mn2+ + Fe3+ + 2CO2 + H2O n-factor for reaction is 2
n-factor = 5 fi 50 ¥ .1 ¥ n = 25 ¥ .1 ¥ 2
n-factor = 1 2.5 ¥ 2
n=
5
n=1
LEVEL II fi Final oxidation state will be (3 – 1) = 2
7. (b) Milliequivalent of K2Cr2O7 = Milliequivalent of ABD
1. (c) 4HCl + MnO2 Æ MnCl2 + Cl2 + 2H2O n-factor of K2Cr2O7 in acidic medium = 6.
5 6 ¥ 1.68 ¥ 10–3 = x ¥ 3.26 ¥ 10–3
n= x=3
87
5 fi New oxidation state of A–n will be = –n + 3
Moles of HCl reacted = ¥4 8. (a) NaN3 h N3- h N h –1/3
87
5 N2H2 h N h –1
Mass of HCl = ¥ 4 ¥ 36.5 = 8.4 gram
87 NO h N h +2 fi 5(A)
2. (c) \ 10 L volume at STP = 11.6 g N2O5 h N h +5
11.6 ¥ 22.4 9. (a) 63% (w/v) H2C2O4.2H2O
\ 22.4 L volume = fi 100 mL contains = 63 g
10
M.W = 26 63
EF = CH, MF = C2H2 125 mL h = ¥ 125 g
100
3. (b) ClO– + Cr2OX Æ Cl– + Cr2O72- 63 ¥ 125 Ê 5 ˆ
Mole of H2C2O4 = =Á ˜
2(6 – x) 126 ¥ 100 Ë 8 ¯
Number of equivalent of ClO– = Number of equivalent 40 x
of Cr2OX for NaOH =
100 125
12.6 125 ¥ 40 Ê 5 ˆ
0.15 ¥ 2 = ¥ 2(6 – x) Mole of NaOH = =Á ˜
(104 + 16 x) 100 ¥ 40 Ë 4 ¯
or 31.2 + 4.8x = 151.2 – 25.2x
H2C2O4 + 2NaOH h Na2C2O4 + 2H2O
x=4
Hence formula = Cr2O4 or CrO2 2 ¥ mole of Acid = Mole of NaOH for neutralisation
4. (d) S + O2 Æ SO2 = 5/4
8 Ê 5ˆ
Moles of SO2 produced from 8 g of sulphur = = 0.25 and will have Á ˜ mole of NaOH
32 Ë 4¯
2-
SO2 + Cl2 water Æ SO 4 + 2Cl– \ Solution is neutral
10 10 10
Moles of SO 24- produced = Moles of SO2 = 0.25 10. (a) Mole of V2O5 = = =
51 ¥ 2 + 5 ¥ 16 102 + 80 182
Now SO 24- + BaCl2 Æ BaSO4 + 2Cl– =.055
Moles of BaSO4 produced = moles of SO 24- = 0.25 Mole of V+2 = .055 ¥ 2
= .1098 mole 0.11
5. (b) AgNO3 + HCl Æ AgCl + H+ + NO3- +4
170 g 143.5 g V +2 h V O +2 + 2e
143.5 g AgCl is produced by 170 gm of AgNO3 I 2 + 2e h 2I –
170 ¥ 2.125
\ 2.125 g AgCl is produced by fi Mole of I2 = Mole of V+2 = 0.11 mole
= 2.517 of AgNO 143.5
3 11. (b) Milliequivalent of I2 = Milliequivalent of Hypo
Now for the reaction equivalent of AgNO3 = equivalent solution
of HCl
= 20 ¥ 2.5 ¥ 10–3

Redox 6.33
Milliequivelent of 10 ml I– = Milliequivelent of I2 = 20 milliequivelent of Na2S2O3 h milliequivelent

¥ 2.5 ¥ 10–3 = 0.05 of K2Cr2O7
Milliequivelent of 100 mL I– = 0.5 1 1
Milliequivelent of CuCO3 = 0.5 30 ¥ N = 15 ¥ N=
20 40
w milliequivelent of I2 = milliequivelent of Hypo
¥ 1000 = 0.5 w = 0.06175
123.5 milliequivelent of I2 = milliequivelent of KI
0.06175 milliequivelent of KI = milliequivelent of K2Cr2O7
% purity = ¥ 100 = 61.75%
0.1 1
24 ¥ = milliequivelent of 25 mL K2Cr2O7
12. (b) I2 + Na2S2O3 Æ I– + S4O62- 40 24 500
let x mL of I2 react with Hypo milliequivelent of 500 mL K2Cr2O7 = ¥
40 25
milliequivelent of I2 = milliequivelent of Hypo w¥6
xN = 15 ¥ 0.4 xN = 6 (i) ¥ 1000 = 12 w = 0.588
294
milliequivelent of H2SO4 used by base = 10 ¥ 0.3 ¥ 2 = 6
0.588
milliequivelent of NaOH used by I2 = (30 – 6) % purity = ¥ 100 = 73.5%
0.8
(150 – x) N = 24 (ii)
15. (b) Let the mass of CaCl2 in sample = x g
Equation (ii) divided by (i)
CaCl2 + Na2CO3 Æ CaCO3 + 2NaCl
150 – x 111 g 100 g
= 4 fi 5x = 150
x \ 111 g CaCl2 produces Æ 100 g CaCO3
x = 30 mL 30 N = 6 100 x
1 x g CaCl2 produces g CaCO3
N= N = M ¥ n-factor 111
5 D
1 CaCO3 ææ Æ CaO + CO2
=M¥2 100 g 56 g
5
1 \ 100 g CaCO3 produces Æ 56 g CaO
M= = 0.1 Ê 100 x ˆ 56 100
10 ÁË ˜ CaCO3 produces Æ ¥ g CaO =
13. (a) Let a g H2SO4 and (3.185 – a) g H2C2O4 111 ¯ 100 111
milliequivelent of 10 mL mixture = 0.3 56 x
g CaO
milliequivelent of 1000 mL mixture = 0.3 ¥ 1000 = 30 111
milliequivelent of H2SO4 + milliequivelent of H2C2O4 since mass of CaO finally produced = 1.62 g = 56x/111
= 30 x = 3.21 g
a (3.185 – a ) 3.21
¥ 1000 + ¥ 1000 = 30 (i) % of CaO in sample = ¥ 100 = 32.1%
49 45 10
–1 0
In another example 16. (d) 2 N H 2OH Æ N 2
milliequivelent of 100 mL mixture = milliequivelent of n-factor = 1
KMnO4 = 4 ¥ 0.02 ¥ 5 +3 +2
milliequivelent of 100 mL mixture = 0.4 F e 2 (SO 4 )3 Æ 2 F eSO 4
milliequivelent of 1000 mL mixture = 4 n-factor =2
milliequivelent of H2C2O4 = 4 Molar mass
Equivalent weight =
3.185 – a 2
¥ 1000 = 4 (ii) 17. (b) In acidic medium
45
MnO -4 h Mn+2 nf = 5
a
\ ¥ 1000 = 30 - 4 = 26
49 Cr2O72- h 2Cr+3 nf = 6
26 ¥ 49 Hence the amount of Fe(II) oxidised is more with
a= = 1.274
1000 Cr2O72-
1.274 18. (b) Milliequivelent of H2SO4 = 100 ¥ 0.2 ¥ 2 = 4
% of H 2SO 4 = ¥ 100 = 40%
3.184 Milliequivelent of NaOH = 100 ¥ 0.2 ¥ 1 = 20
14. (a) K2Cr2O7 + KI h I2 + Cr3+ milliequivelent of H2SO4 remains un neutralised = 20
Number of g equivalent of H2SO4 = N ¥ V
I2 + Na2S2O3 h I2 + S4O62-
Na2S2O3 + K2Cr2O7 h 200 200
=N¥ , N = 0.1
100 1000,

N aVa - N bVb 9 1
or N mix = = moles of SO3 combined with water = = mole
Va + Vb 18 2
7+ 4+ 2 1 1
19. (b) K Mn O 4 h Mn O 2 \ moles of free SO3 remains = – = mole
3 2 6
n=3 1
Normality 1.8 \ volume of free SO3 at STP = ¥ 22.4 = 3.73L
Molarity = = = 0.6 6
n-factor 3 6. (c) Na2CO3 + H2SO4 h Na2SO4 + H2O + CO2
20. (b) milliequivalent of Ba(MnO4)2 = milliequivelent of Moles of CO2 formed = moles of Na2CO3 reacted =
Ê 33.6 ˆ 5.3
H2O2 Á\ M = fi 3˜ nf of Ba(MnO4)2 = 10 = 0.05
Ë 11.2 ¯ 106
w 3 ¥ 125 ¥ 2 Volume of CO2 formed at 1 atm pressure and 300 K =
¥ 10 ¥ 1000 =
375 1000 0.05 ¥ 24.63 = 1.23 L
w = 28.125 7. (b) Equivalent of H2SO4 + Equivalent of SO3 = Equiv-
w 28.125 alent of NaOH
% purity = ¥ 100 = ¥ 100 = 70.31
40 40 x (1 – x) ¥ 2
¥2+ = 54 ¥ 0.4 ¥ 10–3
98 80
LEVEL III 1 – 0.74
% of free SO3 = ¥ 100 = 26%
1
1. (a - r,t), (b - p,t), (c - q), (d - s) Comprehension 2
–3 +5
N H3 h N O3- n-factor = 8, 8. (a) 1 L of H2O2(aq.) provide 11.2 L of O2 at STP
Equivalent weight = Mw/8
11.2
+2 +3 +3 +4 Moles of O2 = = 0.5
F e C 2 O4 h F e +++
+2 C O3–– n-factor = 3, 22.4
Equivalent weight = Mw/3 nH2O2 required 0.5 ¥ 2
+6 0
H 2 S O5 h S8 n-factor = 6, nH2O2
M H 2O 2 = =1M
Equivalent weight = Mw/6 Vsolution
+2 9. (b) Strength in percentage mean how many g H2O2
KMnO 4 h M n n-factor = 5, present per 100 mL
Equivalent weight = Mw/5 M fi 1 and molecular weight of H2O2 = 34
2. (a - r), (b - t), (c - p), (d - s) \ 34 gram H2O2 present per litre of solution or 3.4
H3PO4 is tribasic acid (n = 3); H3PO3 is dibasic acid gram H2O2 present per 100 mL of solution.
(n = 2); H3BO3 is monobasic acid (n = 1) and EDTA is 10. (b) Milliequivalent of H2O2 = Milliequivalent of KMnO4
tetrabasic acid (n = 4) 20 ¥ N = 0.05 ¥ 5 ¥ 80 fi N = 1
3. (a – q,t), (b – p), (c – r,t), (d – s,t) Volume strength of H 2O 2
+7 +2
N=
5.6
K M nO 4 h M n +2 (n-factor = 5)
fi Volume strength of H2O2 = 5.6
+3 +4
Mg C 2 O 4 h Mg +2 + 2 C O 2 (n-factor = 2) Comprehension 3
+6 +3 11. (a) In aqueous solution iodine exist in polyiodide ion
K 2 Cr 2 O7 h 2 C r +3 (n-factor = 6)
(I3- )
+6 +3
Cr O5 h Cr 2 O3 (n-factor = 3) +2 +1
12. (d) 2 C uSO 4 h C u 2 I 2 , n-factor = 1
Comprehension 1 13. (a) Equivalent of CuSO4 = Equivalent of I2 = Equiva-
4. (b) H2O + SO3 h H2SO4; lent of hypo
18 g water combines with 80 g SO3 Weight
\ 4.5 g of H2O combines with 20 g of SO3 ¥ 1000 = 100 ×1×1
Equivalent weight CuSO 4
\ 100 g of oleum contains 20 g of SO3 or 20% free SO3
5. (c) Initial moles of free SO3 present in oleum 100
Weight of CuSO4 = ¥ 159.5 = 15.95 gm
12 2 1000
= = moles \ % purity = 10%
18 3

Redox 6.35
14. (b) Equivalent of Hypo = Equivalent of CuSO4.5H2O 21. (c) 98 g H2SO4 contains 80 g SO3
x \ 60 g H2SO4 contains = 48.98 g
100 ¥ 0.1 = ¥ 1000, x = 2.5 gm % of combined SO3 in oleum = 48.98%
249.5
22. (b) Use, Milliequivalent of NaOH = Milliequivalent of
Comprehension 4
SO3 + Milliequivalent of H2SO4
15. (b) Milliequivalent of CuSO4 reacted = Milliequivalent 23. (a, c, d) Milliequivelent of KMnO4 = 25 ¥ .2 = 5
of Na2S2O3 reacted (nf = 8) = 50 ¥ 1 ¥ 8 = 400 25 ¥ .2
+2 +6 (a) Milliequivelent of FeSO4 = =5
S2O3–2 h SO–2
4
1
(c) Milliequivelent of H2O2 = 25 ¥ .1 ¥ 2 = 2.5 ¥ 2 = 5
nf = 2(6 – 2) = 8 (d) Milliequivelent of SnCl2 = 25 ¥ .1 ¥ 2 = 5
24. (a, b, c)
Weight 400 Weight
= = nf = 2[5 – 0] = 10
Equivalent weight 1000 149.5
59.8 +7 0 +2 +5 –
\ Weight = 59.8 g; % purity ¥ 100 = 75% 2 M nO–4 + 4H+ + Br2 Æ 2M+2
n + 2 BrO3 + 2H2O
79.75
16. (d) 214 g KIO3 = 1 mole of KIO3 (nf = 5) nf = 1 ¥ [7 – 2] = 5
= 3 mole of I2 (in the balanced chemical reaction) = 6
Equivalent of I2 (n f = 2) = 6000 Milliequivelent of I2 n-factor for MnO -4 = 5
Let the volume of Na2S2O3 = x mL, then Equivalent weight = Mx/5
(x ¥ 1) ¥ 8 = 6000 x = 750 mL n-factor for Br2 = 10
17. (b) 5KI + KIO3 + 6HCl h 3I2 + 6KCl + 3H2O Equivalent weight = My/10
+2 +7
1
m mole of KMnO4 used = 50 ¥ =5 Ratio of n-factor M n +2 Æ M nO 4– , n f = 5
10
Milliequivalent of KMnO4 used (nf = 5) = 25 Milli- +5 0
2 B rO3- Æ Br2 = n f = 5 \ ratio 1:1
equivalent of C2O 4-2
25. (b, d) Fe0.95O + O2 Æ Fe2O3
-2 25
m mole of C2O 4 (nf = 2) = = 12.5 Let x is the fraction of Fe+3 in the compound then Fe+2
2 = (0.95 – x)
Milliequivalent of Na2S2O3 = 2.5 = Milliequivalent of x ¥ 3 + (0.95 – x) ¥ 2 – 2 = 0 x = 0.1
Cu+2 (n = 1) Milliequivalent of Cu+2 (n = 1) = 2.5
0.85
Difference in number of m moles of Cu+2 and C2O 4-2 = % of Fe+2 = ¥ 100 = 89.47%
0.95
12.5 – 2.5 = 10
18. (d) 5KI + KIO3 + 6HCl h 3I2 + KCl + 3H2O 11
26. (a, b, d) 2FeS2 + O 2 Æ Fe 2O3 + 4SO 2
2
1.66
= 10 –2 mole KI n-factor = 11
166 Equivalent weight = M/11
1 27. (a, c, d) NaOH and NaHCO3 in solution react together
Moles of KIO3 reacted = ¥ 10–2 = 2 ¥ 10–3
5 NaOH + NaHCO3 Æ Na2CO3 + H2O
Moles of I2 formed = 3 ¥ 2 ¥ 10–3 = 6 ¥ 10–3 40 g 84 g
Comprehension 5 40 84
= 1 mol = 1 mol
9 40 84
19. (d) 109% labelled oleum will contain mole SO3 After reaction solution will have two moles of Na2CO3
= 40 g free SO3, & 60 g H2SO4 18
in 1 L
40 g (free) SO3 = mole SO3 (free) = y = 0.5 For phenolphthalein Milliequivalent of Na2CO3 = Mil-
60 g (H2SO4) = 0.6122 mole H2SO4 = x liequivalent of HCl
x + y 1.1122 20 ¥ 2 ¥ 1 = V ¥ 1 fi V = 40 mL
fi = = 9.9
x – y 0.1122 For methyl orange after first end point
20. (d) In 100 g oleum sample Milliequivalent of NaHCO3 = Milliequivalent of
Weight of SO3 = 40 g Na2CO3 = Milliequivalent of HCl
Weight of H2SO4 = 60 g 2 ¥ 20 ¥ 1 = 1 ¥ V fi V = 40 mL
% of SO3 = 40% and For methyl orange if used from very begining
% of H2SO4 = 60% Milliequivalent Na2CO3 + Milliequivalent of NaHCO3
= Milliequivalent of HCl

2 ¥ Milliequivalent of Na2CO3 = Milliequivalent of HCl NaOH + HCl h NaCl + H2O (Full equivalent of
2 ¥ 20 ¥ 2 = 1 ¥ V fi V = 80 mL NaOH)
+7 +2 Na2CO3 + HCl h NaHCO3 + NaCl (1/2 equivalent
28. (a, b, c, d) Ba(M nO 4 ) 2 Æ 2 M n ++ of Na2CO3)
n-factor = 10 methyl orange is used to detect final end point. Where
Milliequivelent of Ba(MnO4) in 150 mL rest of 1/2 equivalent of Na2CO3 will be neutralised.
NaHCO3 + HCl h NaCl + H2CO3 h (H2O + CO2)
1
fi 150 ¥ 10 ¥ = 150 Milliequivelent +1 +5 –1
10 34. (a, b, c) 3C lO – Æ C lO3– + 2 C l –
Milliequivelent of 1 M Fe+2 Æ Fe+3 = 150 ¥ 1 = 150
+2 +3 +4 It is a disproportionation reaction, which incluces both
Milliequivelent of 50 mL 1 M FeC2 O 4 Æ Fe +3 + 2CO 2 oxidation and reduction of same element.
= 50 ¥ 3 = 150 Milliequivelent
+3 +4 Assertion/Reason
Milliequivelent of 75 mL 1 M C2 O 4–– Æ 2 CO 2
35. (a) Na2CO3 + HCl h NaHCO3 + NaCl
= 75 ¥ 2 = 150 Milliequivelent
NaHCO3 + HCl h NaCl + H2O + CO2
Milliequivelent of 25 mL 1 M Cr2O7-- Æ 2Cr+3
= 75 ¥ 2 = 150 Milliequivelent From the above reactions it is clear that two moles
29. (a, b) molarity and normality involves the use of of HCl are required for complete neutralisation of
volume of solution and we know V μ T Na2CO3. The titre value with methyl orange correspond
COOH COOK to complete neutralisation of Na2CO3 and with phenol-
30. (a, b, d) For | and | phthalein correspond to half neutralisation of Na2CO3.
COOH COOH 36. (b) Molality does not depend upon volume thus it does
When behave as reducing agent not depend upon temperature.
(COOH)2 2CO2 n-factor = 2, eq wt. = M/2 2+ 1– 3+ 4+
O
COOK 37. (a) FeS2 ææÆ
2
Fe 2 O3 + SO 2
| h 2CO2 n-factor = 2, eq wt. = M/2 38. (d) Density change means (m = d ¥ V) mass of solu-
COOH
for neutralization Milliequivelent of one reactant = tion per unit volume changed hence mass of solute per
Milliequivelent of other reactant can be neutralised unit volume changed and therefore molarity will be
1000 ¥ 2 = 1000 ¥ 2 changed but molality independent of temperature.
31. (a, b, c) H3PO4 + Ca(OH)2 h CaHPO4 + 2H2O 2y
39. (c) n factor of P will be and atomic mass = Equiva-
n-factor for H3PO4 = 2 (since 2H+ ions are replaced) x
M 98 lent mass of P ¥ n-factor of
Equivalent weight = = = 49 2y
2 2 P = Ep ¥
resulting solution of CaHPO4 have only are replacable x
H+ 40. (b) Industiral H2SO4 is Oleum (H2S2O7) in which con-
so nf = 1 centration is represented by this method.
hence number of equivalent = 1 for 1 mole so can be 9 g water is added
neutralised by 1 mole of KOH SO3 + H2O Æ H2SO4
equivalent of CaHPO4 = equivalent of KOH 0.5 mL 0.5 mL
For complete neutralisation - Number of equivalent of SO3 also present as 0.5 mol or 40 g
H3PO4 -
41. KMnO4 + X+n h XO3 + Mn+2
= Number of equivalent of Ca(OH)2
= 1 ¥ 3 = 1.5 ¥ 2 can be neutralised. 1.61 ¥ 10–3 2.63 ¥ 10–3
32. (a, b, d) number. of equivalent of H2SO4 = moles ¥ n Equivalent of KMnO4 = Equivalent of X+n
factor = 1 ¥ 2 = 2 1.61 ¥ 10–3 ¥ 5 = 2.63 ¥ 10–3 ¥ (5 – n)
Number of equivalent of Ca(OH)2 = 1 ¥ 2 = 2 (neutralised) M
n=2 fi 56 = M = 41
Number of equivalent of NaOH = 2 ¥ 1 = 2 (neutralised) 2
Number of equivalent of NH3 = 2 ¥ 1 = 2 (neutralised) 42. Milliequivalent of H2O2 = Milliequivalent of KMnO4
H2SO4 + Ca(OH)2 = CaSO4 + 2H2O weight x 0.632
2NaOH + H2SO4 h Na2SO4 + 2H2O = =
Equivalent weight 34/2 158/5
2NH3 + H2SO4 h (NH 4 ) 2 SO 4 \ x = 0.34
33. (a, c) In presence of phenolphthalein to detect first end x
point. \ % Purity = ¥ 100 = 85%
0.4

Redox 6.37
43. Normality of 5.5 L H2O2 49. Milliequivalent of oxalic acid in 16.68 mL = Milli-
4 28 1 1
= = ¥ equivalent of NaOH = 25 ¥
5.6 5.6 5.5L 15
\ Milliequivalent of oxalic acid in 250 mL
28 1
Now, 5 ¥ x = 5.5 ¥ ¥ \ x =1 1 250 w
5.6 5.5 = 25 ¥ ¥ = ¥ 1000
15 16.68 Equivalent
Ê 5 ¥ 3ˆ 0.06
44. N = ÁË ˜ = 0.06 M = = 0.03 n-factor = 2
250 ¯ 2 \ 24.98 =
1.575
¥ 1000
45. 1 mole of H2S ∫ 5 moles of H2SO4 (90 + 18 x)/2
34 g of H2S ∫ 5 moles of H2SO4 \ xª2
0.40 ¥ VH2SO4 = 5 50. n1 ¥ 56 + n2 ¥ 74 = 4.2 (1)
n1 ¥ 1 + n2 ¥ 2 = 0.1 (2)
5
\ VH2SO4 = = 12.5 L n1 ¥ 56
0.40 % of KOH = ¥ 100 = 35%
4.2
46. Equivalent of NaOH = 50 ¥ 0.2 = 10
Ca(OH)2 = 65%
Equivalent of HCl = 2.5 ¥ 2 = 5 51. CaCO3 + 2HCl h CaCl2 + CO2 + H2O
Equivalent of NaOH left after reaction with HCl 0.1 mole 0.25
= 10 – 5 = 5 – 0.05
D
FeCl3 + NaOH Æ Fe (OH)3 Ø ææ Æ Fe2O3 HCl + KOH h KCl + H2O
FeCl3 reacts with NaOH to give Fe(OH)3 which on ig- 0.05 2¥V
nition gives Fe2O3 .05
V= L = 25 mL
\ Equivalent of NaOH used for FeCl3 = Equivalent 2
of Fe(OH)3 52. 2NaOH + NaH2PO4 h Na3PO4 + 2H2O
= Equivalent of Fe2O3 = 15 ¥ 0.1 = 1.5 12
\ Equivalent of NaOH left finally = 5 – 1.5 = 3.5 1¥V = 0.1 Mole
120
WFe2O3 V ¥ 1 = 0.1 ¥ 2
¥ 6 = 1.5 (n-factor for Fe2O3 = 6)
M Fe2O3 V = 0.2 L = 200 mL
53. Ce+4 + Sn+2 h Sn+4 + Cen
1.5 ¥ 160 40.05 + 20 mL
WFe2O3 = = 40 g
6 1M 1M
47. 100 g Haemoglobin has = 0.25 g Fe Milliequivalent of Ce+4 = Milliequivalent Sn+2
0.25 ¥ 86600 40.05 ¥ 1 ¥ (4 – n) = 20 ¥ 1 ¥ 2
\ 86600 g Haemoglobin has = g 20 ¥ 2
100 (4 – n) = 1
= 224 g Fe 40.05
n=3
i.e., 1 mole or NA molecules of Haemoglobin has =
+4
224
g atom Fe = 4 g atom Fe 54. SeO 2 + CrSO4 h Cr+3 + Sen
56 Milliequivalent of SeO2 = Milliequivalent of CrSO4
\ 1 molecule of Haemoglobin has 4 atom of Fe. 12.53 ¥ 0.05093 ¥ (4 – n) = 25.52 ¥ .1 ¥ 1
48. Let valencies of Cu in two oxides be x and y, then I 4–n 4fin=0
oxide is Cu2Ox; II oxide is Cu2Oy 55. n ¥ 106 + n ¥ 84 = 1 (1)
In I oxide: Equivalent of Cu = equivalent of oxygen n ¥ 2 + n ¥ 1 = 0.1 ¥ V ¥ 1000 (2)
w a V = 157.89 mL
= (1)
A /x 8 56. Equivalent of H2SO4 = Equivalent of NaOH
where w, x, A and a are weight of Cu, atomic weight of n ¥ 2 = 0.0267 ¥ 0.4
Cu, valency of Cu and weight of oxygen. n = [0.0267 ¥ 0.2] mole of H2SO4 total.
w a [n ¥ 98 – 0.5] = mass of H2O added
In II oxide: = (2) mole of H2O = mole of SO3
A /y 2 ¥ 8
( Oxygen used half of I) % of SO3 = 20.72%
By Eqs. (1) and (2) 57. CaCO3 + 2HCl h CaCl2 + H2O + CO2
x mole 2x
x 2
= 2/y = 2/1 fi y = 1 MgCO3 + 2HCl h MgCl2 + H2O + CO2
y 1 y mole 2y
the valancy of Cu second oxide is 1

(50 ¥ 0.8 - 16 ¥ 0.25) 64. H2O2 + KMnO4 h Mn+2 + O2

2x + 2y = fi x + y = 0.018 (1)
1000 1 ¥ x /100
¥ 1000 = x ¥ N
x ¥ 100 + y ¥ 84 =1.64 (2) (34/2)
x ¥ 100
% CaCO3 = ¥ 100 = 48.78% N=
20
= 0.5882
1.64 34
% MgCO3 = 51.22% 65. Sn + K2Cr2O7 h SnCl4 + Cr+3
58. Milliequivalent of CaCO3 = Milliequivalent of HCl – 1 0.1 N V ml
Milliequivalent of NaOH
Ê 1 ˆ
ÁË ˜ ¥ 1000 = 0.1 ¥ V fi V = 337.8 mL
w
¥ 1000 = 10 ¥ 4 -
100
¥ 18.75 ¥ 0.2 = 25 118.7/4 ¯
(100/2) 25 1000
66. Milliequivalent of Cu = [20 ¥ 0.0327] = 32.7
w = 1.25 g 20
w
Ê 1.25 ˆ ¥ 1000 = 32.7 fi w = 2.07645 g
% CaCO3 = Á ¥ 100 = 83.33%
Ë 1.5 ˜¯ (63.5/1)
59. Na2CO3 + NaHCO3 2.07645
% Cu = ¥ 100 = 41.53%
x y milli mole 5
x=4¥1 (1) 67. Milliequivalent of Fe = Milliequivalent of K2Cr2O7
2x + 4 = 10.5 ¥ 1 0.84 ¥ x /100
y = 2.5, x = 4 ¥ 1000 = x ¥ N
56
Na2CO3 = 4 ¥ 106 mg = 0.424 mg N = 0.15
NaHCO3 = 0.21 gm 68. H2C2O4 ◊ 2H2O ◊ KHC2O4 ◊ H2O + NaOH Æ product
60. Na2CO3 NaOH x mole y mole 18.9 ml, 0.5 N
x y m mole
H2C2O4 ◊ 2H2O KHC2O4 ◊ H2O + KMnO4 Æ Mn+2 + CO2
x + y = 19.5 ¥ 0.995 = 19.4025 (1)
2x + y = 25 ¥ 0.995 = 24.875 (2) x y
mol mol 21.55 mL, 0.25 N
x = 5.4775 m mole in 25 ml 4 4
5.4725 ¥ 106 18.9 ¥ 0.5
Na2CO3 = = 23.2 g/L x¥2+y¥1= (1)
25 1000
NaOH = 22.28 g/L Ê x yˆ
61. NaOH + Na2CO3 ÁË + ˜¯ ¥ 2 ¥ 1000 = 21.55 ¥ 0.25 (2)
4 4
x y m mole
% H2C2O4 ◊ 2H2O = 14.36%
1
x+y= ¥ 17.5 = 1.75 (1) % KH2C2O4 ◊ H2O = 81.7%
10 69. Milliequivalent of Ca(OH)2 = Milliequivalent of HCl –
1 Milliequivalent of NaOH
y= ¥ 2.5 = 0.25 (2)
10 Ê w ˆ
x = 1.5, y = 0.25 m mole ÁË ˜ ¥ 1000 = (50 ¥ 0.5 – 0.3 ¥ 20)
74/2 ¯
1.5 ¥ 40 w = 0.703
NaOH = g = 0.06 g
1000 0.703
% Ca(OH)2 = ¥ 100 = 1.406%
0.25 ¥ 106 50
Na2CO3 = = 0.0265 g
1000 70. Milliequivalent of Na2CO3 = Milliequivalent of HCl –
62. Na2CO3 NaHCO3 Milliequivalent of NaOH
x y Milliequivalent w
x = 2 ¥ 0.2 = 0.4 …(1) ¥ 1000 = 50 ¥ 0.1 – 10 ¥ 0.16
106/2
y + x = 2.5 ¥ 0.4 = 1 …(2)
y = 0.6 x = 0.4 w
% purity = ¥ 100 = 90.1%
+3 +3 +4 1
63. K 2 C2 O 4 ◊ 3H 2 C2 O 4 ◊ 4H 2O + MnO 4- Æ Mn +2 + CO 2 71. x g substance
V ml. 0.1M 0.6 x g NaCl, 0.37 x g KCl
È 1 ˘ Ê 0.6 x 0.37 x ˆ
¥ 8 ¥ 1000 = V ¥ 0.1 ¥ 5 ÁË + ˜ ¥ 1000 = 25 ¥ 0.1 – 5.5 ¥ 0.1
ÎÍ 508 ˚˙ 58.5 74.5 ¯
fi V = 31.68 mL x = 0.1281 g

Redox 6.39
72. 12 = 5.6 ¥ N fi N = 2.1428.57

m moles of ClO3- = 2
700 ¥ 2.1428 = 1000 ¥ N
N1 = 1.5 = M1 ¥ 2 6H2O + 6Cl2 h 10Cl– + 2ClO3- + 12H+
M1 = 0.75 fi g/L = 0.75 ¥ 34 = 25.5 gram/L 2 m moles so moles of Cl2 = 6 m moles
Volume strength of final solution = 5.6 ¥ 1.5 6e– + 14H+ + Cr2O7-2 h 2Cr+3 + 7H2O
= 8.4 volume
73. 50 ¥ N = 20 ¥ 0.1 (2Cl– h Cl2 + 2e–) 3
N = 0.04 = M ¥ 2 14H+ + Cr2O7-2 + 6Cl– h 3Cl2 + 2Cr+3 + 7H2O
M = 0.02 fi g/L = 0.02 ¥ 34 = 0.68 gram/L 6m moles
5 106 \ m moles of Cr2O7-2 = 2 m moles
74. ¥ 100 ¥ = 41.66 ppm
120 100 ¥ 103 Weight of Cr2O7-2 = 2 ¥ 10–3 ¥ 294 = 0.588 g
Ê 1 1 ˆ (Cr2O7-2 ) % purity = 58.8%
˜ ¥ 10 ¥ 100
–3
ÁË +
111 120 ¯ 83. Let H2C2O4 . 2H2O Æ x g in 100 mL
75. ¥ 106 = 1.734 ppm
1000 On reaction with NaOH with phenolphthalein
0.001 ¥ 100 x¥2
76. ¥ 106 = 100 ppm g equivalent of acid in 50 mL =
1000 2 ¥ 126
77. 100 mL h 1.62 mg Ca(HCO3)2 1
g equivalent of NaOH = ¥ 0.11905
1.62 10
60 ¥ 103 mL h ¥ 60 ¥ 103 = 972 mg
100 x¥2 0.11905
Ca(OH)2 + Ca(HCO3)2 h 2CaCO3 + 2H2O so = fi x = 1.5 g
2 ¥ 126 10
w È 0.972 ˘ so mass of Na2C2O4 = 2.5 – 1.5 = 1 g
74 ÍÎ 162 ˙˚
Now, in 0.5 g of same mixture
Ê 0.972 ˆ H2C2O4 ◊ 2H2O h 0.3 g
w = ÁË ˜ ¥ 74 = 0.444 g
162 ¯ Na2C2O4 h 0.2 g
78. H2SO4 + 2NH3 h (NH4)2SO4 0.3 ¥ 2
g equivalent of H2C2O4 ◊2H2O =
(30 – 25) Milliequivalent 25 Milliequivalent 126
(30 ¥ 0.2) Milliequivalent 0.2 ¥ 2
g equivalent of Na2C2O4 =
VNH3 = 25 ¥ 10–3 ¥ 22400 = 537.6 mL 134
79. Milliequivalent of SeO3-2 = Milliequivalent of BrO3- g equivalent of KMnO4 =
V
¥ 10–3
used 10
w È 1 1 ˘ 0.3 ¥ 2 0.2 ¥ 2 V ¥ 10 –3
¥ 2 ¥ 1000 = Í20 ¥ ¥5–5¥ ¥ 2˙ so + =
M Î 60 25 ˚ 126 134 10
w = 0.084 g = 84 mg \ V = 77.46 mL
1 ¥ 0.552 100 84. First HCl will react with KIO3 to from I2 and Cl2 then
80. ¥ 1000 = ¥ 17 ¥ 0.0167 ¥ n
160 25 this Cl2 produced will again react with KI to form I2.
\ n=3 Let initially x moles of KIO3 were mixed with y moles
81. Milliequivalent of Hypo = 5 = Milliequivalent of I2 of HCl then
Moles of I2 = 2.5 m moles 2IO3- + 10Cl– h I2 + 5Cl2
2CuSO4 + 4KI h Cu2I2 + 2K2SO4 + I2 x y
From reaction moles of CuSO4 = 2.5 ¥ 2 = 5 m moles y y
Mw of hydrated CuSO4 = 159.5 + 18x –
Cl2 + 2KI h I2 + 2KCl 10 2
1.2475 y
so = 5 ¥ 10–3 x = 5. excess 0 0
159.5 + 18x 2
1 y
82. Milliequivalent of Hypo = 100 ¥ = 10 = Milli- – – y
10 2
equivalent of I2 y y 3y
Total moles of I2 formed = + =
Milliequivalent of ClO3- = 10 10 2 5
3 y 0.021 ¥ 24 ¥ 10 –3
nf of ClO3- = 5 so = fi y = 0.00042 mole
5 2

0.00042 y
so concentration of HCl = = 0.0168 M for SO2 ¥2
0.025 = 0.0168 N 64
2y
0.00042 = (25 ¥ 0.0396 – 12.44 ¥ 0.0345) ¥ 10–3
Moles of KIO3 consumed = 64
5
2y
0.00042 ¥ 5 = 0.56082 ¥ 10–3
Volume of KIO3 consumed = = 0.00042 L 64
5 = 0.42 mL y = 17.94624 g
85. As2O3 + 6HCl h 2AsCl3 + 3H2O Concentration of H2S
AsCl3 + 2H2O h HAsO2 + 3H+ + 3Cl– 3.031525
Gram equivalent of I2 = Gram equivalent of HAsO2 = = ¥ 10–3 = 0.1212 mg/L
25
Gram equivalent of AsCl3 = Gram equivalent of As2O3 Concentration of SO2
Gram equivalent of As2O3 = 2 ¥ 0.04134 ¥ 23.04 ¥ 10–3
17.94624
= 0.9524 ¥ 10–3 ¥ 2 = = 0.7178 mg SO2/L
Gram equivalent of KMnO4 = 0.9524 ¥ 10–3 ¥ 2 25
Let amount of KMnO4 used = w g then 89. In presence of methyl orange, the whole NaOH and
Na2CO3 are neutralised
w¥5
= 0.9524 ¥ 10–3 ¥ 2 fi milliequivalent of HCl = 16 ¥ 0.25 = 4 = milli-
158.5 equivalent of (NaOH + Na2CO3) = milliequivalent of
w = 0.06 g NaOH original
86. 4OH– + 2H2O + SO2 h SO 24- + 4H2O + 2e– fi Total milliequivalent of NaOH in original 1.0 g
4OH– + SO2 h SO 24- + 2H2O + 2e– (1) sample = 4 ¥
100
= 20
2H2O + H2O2 + 2e– h 2H2O + 2OH– 20 20 ¥ 40 ¥ 100
fi mass % of NaOH (original) = = 80
H2O2 + 2e– h 2OH– (2) 1000
Eq. (1) + (2) Now, let us assume that in 20 mL, x m mol of NaOH
2OH– + H2O2 + SO2 h SO 24- + 2H2O (3) has got converted to Na2CO3
fi In 20 mL, m mol of NaOH = 4 – x
NaOH + HCl h NaCl + H2O
x
Milliequivalent m mol of Na2CO3 =
30 ¥ 0.04 0.024 ¥ 22.48 – – 2
1.2 0.53952 In second titration, HCl used in titration of NaOH +
0.66048 ¥ 10–3 0 Na2CO3 = 50 ¥ 0.1 – 9 ¥ 0.2 = 3.2
From Eq. (3) fi Up to phenolphthalein end point, m mol of HCl
1 x x
required = 4 – x + =4– = 3.2
\ moles of SO2 = 0.33024 ¥ 10–3 = nNaOH ¥ 2 2
2 fi x = 1.6
weight of sulphur = 0.33024 ¥ 10–3 ¥ 32
x 5x
= 10.5676 × 10–3 fi Total Na2CO3 formed = ¥5= =4
2 2
10.5676 ¥ 10-3 m mol of NaOH left unreacted = 20 – 4 ¥ 2 = 12
% of S in sample = ¥ 100 =1.76%
0.6 fi weight of 1.0 g of exposed sample
87. CuS + Cu2S + KMnO4 h Mn+2 + Cu+2 + SO2 8 ¥ 40 8 ¥ 40
6 8 5 = 1- + = 1.176 g
1000 1000
Equivalent weight of CuS = M1/6
fi weight % of Na2CO3 in exposed sample
Equivalent weight of Cu2S = M2/8
Equivalent weight of KMnO4 = M3/5 4 ¥ 106
= ¥ 100 = 36.05%
88. H2S + SO2 1000 ¥ 1.176
x y 90. MnO2 + 4 HCl h MnCl2 + 2H2O + Cl2
S–2 h SO 24- (n -factor = 6) 1.78
Number of moles of Cl2 = = 0.07946
x 22.4
for H2S ¥ 6= 0.534975 ¥ 10–3 = (20 ¥ 0.0066 ¥ 6 – Number of moles of MnO2 = 0.07946
34
\ mass of MnO2 = 0.0794 ¥ 87 = 6.913 g
7.45 ¥ 0.0345) ¥ 10–3
\ number of moles of HCl = 4 ¥ 0.07946 = 0.3178
x = 3.031525 ¥ 10–3
Mass of HCl = 0.3178 ¥ 36.5. Let the volume of HCl =
SO2 h SO 24- (n-factor = 2) V mL

Redox 6.41
4 0.4725
\ V ¥ 1.2 ¥ = ¥ 0.3178 ¥ 36.5 = 241.66 mL Percentage of Na2SO4 = ¥ 100 = 31.5%
100 1.5
91. Redox changes are 1
93. Total moles of the mixture =
C2O 42- h 2CO2 (n-factor = 2) 22.4
= 0.0446 = 4.46 ¥ 10–2
MnO -4 h Mn2+ (n-factor = 5) 40 1
MnO2 h Mn2+ (n-factor = 2) Equivalents of Na2S2O3 solution = ¥ = 4 ¥ 10–3
1000 10
Milliequivalent of MnO2 = Milliequivalent of oxalic Equivalents of I2 = 4 ¥ 10–3
acid taken – Milliequivalent of oxalic acid left Equivalents of KI = 4 ¥ 10–3
250 Equivalents of O3 = 4 ¥ 10–3
= 50 ¥ 0.5 ¥ 2 – 32 ¥ 0.02 ¥ 5 ¥ (in 250 mL) = 18
25 when O3 reacts with KI it converts to O2 and O–2
WMnO2 the ‘n’ factor for O3 in this reaction is 2
¥ 2 ¥ 1000 = 18
Molar mass 4 ¥ 10-3
Moles of O3 = = 2 ¥ 10–3
WMnO2 2
fi ¥ 2 ¥ 1000 = 18,
87 Moles of O2 = 4.46 ¥ 10–2 – 2 ¥ 10–3 = 4.26 ¥ 10–2
\ WMnO2 = 0.7821 g Mass percent of ozone in the mixture =
2 ¥ 10-3 ¥ 48
0.7821 ¥ 100 = 6.57%
\ % of MnO2 = ¥ 100 = 24.44 % 2 ¥ 10 ¥ 48 + 4.26 ¥ 10-2 ¥ 32
-3
3.2
Milliequivalent of MnO2 = Milliequivalent of O2 Number of O3 molecules = 2 ¥ 10–3 ¥ 6.023 ¥ 1023 =
WO2 1.2 ¥ 1021
¥ 4 ¥ 1000 = 18, \ WO2 = 0.144 g Number of photons required = 1.2 ¥ 1021
32 94. Potassium selenate is isomorphous to K2SO4 and thus
0.144 its molecular formula is K2SeO4.
% of available O2 = ¥ 100 = 4.5%
3.2 Now molecular weight of K2SeO4 = (39 ¥ 2 + a + 4 ¥ 16)
92. Out of Na2CO3, NaHCO3 and Na2SO4 only NaHCO3 de- = (142 + a)
composes on heating to give CO2 gas, according to the where a is atomic weight of Se
equation 2NaHCO3 h Na2CO3 + CO2 + H2O moles (142 + a)g K2SeO4 has Se = a gram
PV 750 ¥ 123.9 a ¥ 100
of CO2 = = = 5 ¥ 10 –3 \ 100 g K2SeO4 has Se =
RT 760 ¥ 1000 ¥ 0.082 ¥ 298 142 + a
\ % of Se = 45.52
\ moles of NaHCO3 = 2 ¥ 5 ¥ 10–3 = 0.01 \ = 45.52
150 ¥ (1/10) \ a = 118.2
Equivalents of HCl used = = 1.5 ¥ 10–2 Also equivalent of K2SeO4
1000
Equivalents of NaHCO3 in 1.5 g = 0.01 ¥
1.5 Molecular weight 2 ¥ 39 + 118.2 + 64
= = = 130.1
2 2 2
= 7.5 ¥ 10 –3
Ê Normality ˆ
\ equivalents of Na2CO3 = 1.5 ¥ 10–2 – 7.5 ¥ 10–3 95. Á Molarity = –˜
= 7.5 ¥ 10–3 Ë Number of replaceable OH ¯
7.5 ¥ 10-3 N=M¥2
Moles of Na2CO3 =
2 Thus Milliequivalent of borax in solution = 50 ¥ 0.2 ¥
(when Na2CO3 reacts with HCl it gives NaCl, CO2 and 2 = 20
H2O. No atom undergoes change in oxidation state. \ w
\ ¥ 1000 = 20
‘n’ factor of Na2CO3 = 2) m /2
= 3.75 ¥ 10–3 w
Mass of NaHCO3 in 1.5 g = 7.5 ¥ 10–3 ¥ 84 = 0.63 g \ ¥ 1000 = 20/w = 3.82 g
382/2
Mass of Na2CO3 in 1.5 g = 3.75 ¥ 10–3 ¥ 106 = 0.3975 g
For neutralisation of HCl
\ mass of Na2SO4 = 1.5 – 0.63 – 0.3975 = 0.4725 g
Milliequivalent of HCl = Milliequivalent of borax
0.63
Percentage of NaHCO3 = ¥ 100 = 42% w
1.5 25 ¥ 0.1934 = ¥ 1000
382/2
0.3975
Percentage of Na2CO3 = ¥ 100 = 26.5% \ Weight of borax = 0.9235 g
1.5

For neutralisation of H2SO4 Now 64 g SO2 required = 32g S

Milliequivalent of borax = Milliequivalent of H2SO4 32 ¥ 0.021
0.021g SO2 required = = 0.0105 g
w 64
¥ 1000 = 25 ¥ 0.1934 ¥ 2
382/2 0.0105
\ Weight of borax = 1.847 g % of S = ¥ 100 = 0.1875%
5.6
96. The reactions are
H2O + 2KI + O3 h 2KOH + I2 + O2 99. Let Al, Mg and Cu be a, b and c g respectively.
2Al + 2NaOH h 2NaAlO2 + 3H2
Also 2e– + I2 h 2I–
Mg + 2HCl h MgCl2 + H2
And 2S22+ h S4+5/2 + 2e–
Cu + HCl h No reaction
\ Milliequivalent of I2 = Milliequivalent of
i.e., only Al reacts with NaOH and then only Mg reacts
Na2S2O3 = 1.5 ¥ 0.01 = 1.5 ¥ 10–2
or mM of I2 = 7.5 ¥ 10–3 with HCl
mM of O3 = mM of I2 = 7.5 ¥ 10–3 \ a + b + c = 8.72
(Mole ratio of O3 : I2 :: 1 : 1) b + c = 2.10 (Residue left after alkali treatment)
c = 0.69 (Residue left after acid treatment)
nRT 7.5 ¥ 10 –6 ¥ 0.0821 ¥ 300 \ b = 6.62g
PO3 = =
V 10 6.62
-7
= 184.725 ¥ 10 atm \ % of Al = ¥ 100 = 75.9
8.72
\ Volume % of O3 = 184.725 ¥ 10–7 ¥ 100 1.41
= 1.847 ¥ 10–3% % of Mg = ¥ 100 = 16.2
8.72
168
97. nCaCO3 + nBaCO3 = = 7.5 ¥ 10-3 (1) 0.69
22400 % of Cu = ¥ 100 = 7.9
8.72
2BaCO3 h 2BaCrO4 h BaCr2O7 h I2 + Na2S2O3
Equivalent of Na2S2O3 = Equivalent of I2 = Equivalent 100. 2KClO3 + 12HCl h 2KCl + 6H2O + 6Cl2
of BaCr2O7 Cl2 + 2KI h 2KCl + I2
20 ¥ 10-3 ¥ 0.05 ¥ 100 [ NHypo12.3 = 24.6 ¥ 0.5; \ NHypo = 1]

= = 1 ¥ 10–2
10 Also Milliequivalent of Cl2 = Milliequivalent of Hypo
1 = 100 ¥ 1
Moles of BaCr2O7 = ¥ 10–2 2 ¥ mM of Cl2 2 ¥ 50 50
2 Also mM of KClO3 = = =
2 6 6 3
Moles of BaCrO4 = (1 ¥ 10–2)
6 w 50
Also ¥ 1000 =
1 122.5 3
Moles of BaCO3 = ¥ 10–2 = 3.33 ¥ 10–3 (2)
3 È Weight ¥ 1000 ˘
Weight of BaCO3 = 0.650 g Ímilli-mole (mM) = Molecular weight ˙
From Eqs. (1) and (2), we get Î ˚
= 4.17 ¥ 10–3 2.042
Weight of CaCO3 = 100 ¥ 4.17 ¥ 10–3 = 0.417 g % of KClO3 = ¥ 100 = 82.32%
2.48
Weight of CaO = 1.249 – 0.656 – 0.417 = 0.176
101. Let atomic weight of P and Q are a and b respectively
0.176
% of CaO = ¥ 100 = 14.09% Molecular weight of P2Q3 = 2a + 3b and Molecular
1.249 weight of PQ2 = a + 2b
98. Milliequivalent of alkali added = 30 ¥ 0.04 = 1.2 Now given that 0.15 mole of P2Q3 weigh 15.9 g
Milliequivalent of alkali left = 22.48 ¥ 0.024 = 0.54
Milliequivalent of alkali for SO2 and H2O2 = 1.2 – 0.54 15.9 Ê Weight ˆ
(2a + 3b) = ÁË = mole˜
= 0.66 0.15 Molecular weight ¯
0.66 ¥ 40
Weight of alkali used = = 0.0264 9.3
1000 Similarly, (a + 2b) =
0.15
80g NaOH reacts with 64g SO2 Solving these two equations
64 ¥ 0.0264 b = 18, a = 26 \ P = 26 and Q = 18
0.0264 g NaOH reacts = = 0.021g SO2
80

Redox 6.43
7. (c)
PREVIOUS YEARS’ QUESTIONS (i) 7–2=5
OF JEE (MAIN & ADVANCED) (ii) 7–6=1
1. (c) 2 + 2(2 + x – 4) = 0 [ Ba(H2PO2) is neutral mol- (iii) 7–4=3
ecule] or 2x – 2 = 0 fi x = +1 (iv) 7–3=4
2. (b) O Cl+1
(i) Write balance chemical equation for given 8. (d) Ca
Cl–1
change.
9. (a) In this oxidation number of N is changing
BaO2 + H2SO4 Æ BaSO4 + H2O2
10. (b) +4 + x – 6 = 0 fi x = 2
(ii) Identify most electronegative element in the reac-
11. TIPS/Formulae:
tion and has the oxidation states of –1 (in H2O2)
The highest O.S. of an element is equal to the number
and –2(in BaSO4). In H2O2, peroxide ion is present.
of its valence electrons
3. (a) Balanced the reaction by ion electron method
(a) [Fe(CN)6]3–, O.N. of Fe = +3
Oxidation reaction: [ C2O 4-2 Æ 2CO2 + 2e] ¥ 5
[Co(CN)6]3–, O.N. Of Co = +3
Reduction reaction:
(b) CrO2Cl2, O.N. of Cr = +6,
MnO -4 + 8H+ + 5e– Æ Mn2+ + 4H2O] ¥ 2
(Highest O.S. of Cr)
Net reaction:
[MnO4]– O.N. of Mn = +7,
2MnO 4- + 16H + + 5C2O 42- Æ
(Highest O.S. of Mn)
2Mn2+ + 10CO2 + 8H2O
(c) TiO3, O.N. of Ti = +6,
4. Use molarity equation to find volume of H2SO4 solu-
MnO2 O.N. of Mn = +4
tions.
(d) [MnCl4]–2, O.N of Mn = +2
CuCO3 + H 2SO 4 h CuSO4 + H2O + CO2≠
63.5 +12 + 48.98 98g [NiF6]–2 O.N of Ni = +4
=123.5g
12. (d) x + 4(0) – 2 = +1
\ For 123.5 g of Cu(II) carbonate 98 g of H2SO4 x=3
are required. For 0.5 g of Cu(II) carbonate weight of 13. (c) Final product will be Cr2O3 in this oxidation state of
98 ¥ 0.5 Cr is +3
H2SO4 required = g = 0.39676 g H2SO4
123.5 14. (b) 2e + S6+ Æ S4+
Weight of required H2SO4 = 0.39676 g 2I– Æ I2 + 2e
0.39676 1000 15. (c) HCl being stronger reducing agent reduces Mn O -4
M= ¥
98 V(ml) to Mn2+ and result of the titration becomes unsatisfac-
0.39676 ¥ 1000 tory.
\ V= mL = 8.097 mL 16. (2) Na, F show only one non-zero oxidation state.
90 ¥ 0.5
Na = +1
5. (d) Oxidation state of Mn in MnO -4 = +7 F = –1
Oxidation state of Cr in Cr(CN)36- = +3 O O
2– +5 0 0 +5
Oxidation state of Ni in NiF62-
= +4 17. (5) S4O6 : O S S S S O
Oxidation state of Cr in CrO2Cl2 = +6 O O
6. (d) So difference in oxidation numbers of two types of S =
(i) Mass of one electron = 9.108 ¥ 10–31 (5 – 0) = 5.
(ii) 1 mole of electron = 6.023 ¥ 1023 electrons \ 18. (d) Haematite:Fe2O3 fi Oxidation state of Fe = III
weight of 1 mole of electron Magnetite: Fe3O4 ∫ FeO.Fe2O3
= Mass of one electron ¥ Avogadro number Oxidation state of Fe = II, III
= 9.108 ¥ 10–31 ¥ 6.023 ¥ 1023 kg 19. (c) The half-equations of the reaction are
\ Number of moles of electrons in 1 kg
Mn O -4 Æ Mn2+
1
= -31
9.108 ¥ 10 ¥ 6.023 ¥ 1023 C2 O 42- Æ CO2
1 The balanced half-equations are
= ¥ 108
9.108 ¥ 6.023 Mn O -4 + 8H– + 5e– Æ Mn2+ + 4H2O

(b) Æ r
C2 O 24- Æ 2CO2 + 2e–
+6 +6
On equating number of electrons, we get 2Cr O 24- + H + Æ Cr2 O72- + H 2O
2Mn O -4 + 16H + 10e– Æ 2Mn2+ + 8H2O (no change in +6 oxidation state of Cr)
Structure is
5C2 O 24- Æ 10CO2 + 10e–
O O O
On adding both the equations, we get Cr Cr
2Mn O -4 + 5C2 O 24- + 16H– Æ O OO O
16 It is a dimeric bridged tetrahedral metal ion
2Mn2+ + 2 ¥ 5CO2 + H2O
2 (c) Æ p, q
\ x, y and z are 2, 5 and 16 are respectively.
[5e– + Mn OQ
4 Æ Mn ]
2+
(Reduction)
20. (a, b, d)
[NOQ
2 Æ NO3Q -
+e ] (Oxidation)
ClO3- + 6e– + 6H+ Æ Cl– + 3H2O
O
ClO3- + 6I– + 6H+ Æ 3I2 + Cl– + 3H2O
Structure of NO3Q : O N O
ClO3- + 6I– + 6H2SO4 Æ 3I2 + Cl– + 3H2O + 6HSO4–
2
21. (a) Æ p, s; (b) Æ r; (c) Æ p, q; (d) Æ p [sp hybridisation and hence trigonal planar in shape]
(a) Æ p, s (d) Æ p
Fe2+ Æ Fe3+ + e– (Oxidation)
Reduction
3e– + NO3Q Æ NO (Reduction)
– 2–
O2 O2 + O2
–1 0 –1
2
Oxidation

Thermo-
dynamics and
Chapter
7
Thermo-
chemistry
Key Concepts
A large portion of thermodynamics deals with flow of energy Surroundings ____________________________
and its impact on the properties of the substance. Everything except system is known as surrounding.
Thermodynamic laws are applicable on macro scopic lev- Surrounding is very large but only that part of surround-
els. ing is significant in which appreciable change is taking place.
Few terms used in thermodynamics Any change taking place in surrounding is very small
1 compared to the change in the system.
PV = mn Vrms 2
System + Surrounding = Universe
3
Sum of microscopic properties give macroscopic proper-
ties. Boundary _______________________________
System: That region in space which is studied for thermo- The interface at which mass and energy are/may be ex-
dynamics aspect is known as system. changed between system and surrounding.
System may be very small, or as large as earth. Boundary may be real or imaginary, rigid or non-rigid.
System is further classified as * Properties of the system: Property defines the state of any
1. Open system system.
2. Closed system * Extensive Properties: Those properties of the system
3. Isolated system which depend upon the amount of the substance are known
Mass Energy Example as extensive properties.
Exchange Exchange Extensive properties are additive in nature.
Open Possible Possible Hot cup of coffee For example, mass, length, area, volume, heat capacity (ms)
Closed Not possible Possible Hot cup of coffee E or U (internal Energy), H(Enthalpy), S(Entropy),
covered with lid. G(Gibbs free entropy)
Isolated Not possible Not possible Hot cup of coffee * Intensive Properties
covered isolately. Those properties of the system which is independent of the
Laws of thermodynamics are not applicable on open sys- amount and depend on the nature are known as intensive
tem because mass is changing. properties.
Earth is treated as an isolated system for small thermody- For example, pressure, temperature, boiling point, melting
namic changes. point, surface tension, vapour pressure, refractive index,
Universe is treated as an isolated system and laws applica- m m m
, , = density
ble on isolated system will be applicable on universe as well. L A V

Ratio of extensive property is intensive properties TKE = Translational Kinetic Energy

ms RKE = Rotational Kinetic Energy
= heat capacity per mole
n VKE = Vibrational Kinetic Energy
= molar heat capacity
= (intensive properties) Process: Change in state is known as process:
1. Isobaric process
Standard emf of the cell (E°) is intensive property.
P = constant
Fe h Fe+2 +2e E° = +0.44 V DH = x dp = 0
2Fe h 2Fe+2 + 4e– E° = +0.44 V DH = 2x P
* State and Path function
State functions are those functions which do not depend upon A B
the process and depend only on the state. D C
For example, E(U), H, G, A, S, P, V, T
Path Function
V
Those properties of the system which depend on the state as
well as on the process by which the state has been achieved, V P
are called path function. D
For example, w, q B
A B
Ú SF = 0 C
* Characteristic of state function A D C
1. P T T
A
P1 2. Isochoric process
II III
I V = constant
P2 B dV = 0
\ work = 0
P V
V A B
A D
DSF is same for all path (A Æ B)
(DPAÆB)I = (DPAÆB)II = (PAÆB)III
= P2 – P1 B C
WI < WII < WIII
2. Ú SF = 0, Ú path function π 0 V T
wπ0 P
qπ0
P
A
A B D
C
C T
V 3. Isothermal process
T = constant
Internal Energy (U) and total energy of the system at dT = 0
constant volume (E) dE = 0 fi (If phase change is not taking place)
E = KE + PE + U P
P
KE = due to motion
PE = External electric or magnetic field
U = (TKE + RKE + VKE + …)
In thermodynamics, usually system is at rest KE = 0 and T2
external electric or magnetic field not applied T1
\ PE = 0 and \ E = U V T

Thermo- dynamics and Thermo- chemistry 7.3
V * Characteristics of Reversible Process

1. Reversible process is a slow process.
2. It takes infinite time for the completion.
3. Reversible process is imaginary process because mass-
less and frictionless piston do not exist.
4. When reversible process A h B is changed into B
h A, it traces its original path.
T 5. Work done in reversible process is maximum.
4. Adiabatic process 6. Each state between A to B, system is in equilibrium
P
for adiabatic process; with the surrounding.
A
dq = 0 Irreversible Process: Those processes in which driving
i.e., no heat will enter into force is much greater than opposing force.
the system or leave the sys- Isothermal DF = F or OF = dF
tem. Adiabatic
B
Cyclic Process
P
If any system undergoes different V A
processes and finally comes to its 5 atm
initial state, then such processes are called cyclic process. 1 atm 1 atm B
P P 5 atm
Isobaric Ideal Gas 5 atm
A B V1 V2 V
Isochoric A B
Isothermal C Characteristics of Irreversible Process
* Irreversible processes are fast process.
V V * Between A and B, system will not be at equilibrium.
* All naturally occurring processes are irreversible pro-
DP = DV = DT = DE = DH = DS = 0 cess.
wπ0 * It takes place in finite time.
qπ0 * Work done in irreversible process is less as compared
to reversible process.
Reversible and Irreversible Process * Exact path of irreversible process can be obtained only
Reversible: Those processes in which driving force is by experiments.
infinitesimally greater than opposing force, such processes * A to B and B to A do not follow same path.
are called reversible process.
Reasons for Irreversibility
DF = F + dF and OF = F Most important reason are:
fi Friction
fi May be temperature gradient
Sand fi Any reversible process A h B and B h A has effect
Massless &
on the surrounding.
Ideal Gas 5 atm Frictionless piston
5
HEAT AND WORK

If sand is removed slowly, state A comes to state B.
* Heat and Work: Energy transfer or energy exchanged
P
A by system and surrounding by virtue of temperature
5
difference only is known
Diathermic wall
Reversible process as heat, rest all form of
energy transfer is re-
System
3 B ferred as work.
T1
* Work is a high quality
energy while heat is a E
fi
V1 V2 V low quality energy.

Heat transfer

w = 4.18 J 1 Cal = heat Q. Whenever heat is added to the system, its temperature will
rise. fi false statement.
Convert into Engine 2 J = work H2O(l) h H2O(g) [in phase change
1 calorie
100°C 100°C [temperature constant]
2.18 J (heat loss) Relation between total energy of
Both heat and work are path function and are not the the system at constant volume (E) and Gas
property of the system. total energy of the system at constant
pressure (H) enthalpy:
P T
Reversible Reversible H = E + PV (1)
1 1
H = f(P, V, T, n)
2 2 E = f(P, V, T, n)
DH = DE + D(PV) (2)
V S = DE + (P2V2 – P1V1)
Work Heat
If pressure is constant.
Both work and heat are boundary phenomena and work
transfer or heat transfer takes place at the interface of DH = DE + PDV (3)
system and surrounding. = DE + P(V2 – V1)
Sign Convection: For any ideal gas undergoing through certain process at
Work constant pressure P, we can say that
Heat
nRT
V=
If work done on the system P
q(–) Gas
then, W(+ve) nR
DV = ◊ DT
P
System Compression DH = DE + nRDT (4)
q(+) For chemical reaction:
Work done by on the system
Heat absorbed Gas then, W(–ve)
by the system a A(g) Æ b B(g)
then, (q +ve)
Expansion
Thermodynamic Equilibrium H = E + PV
Any isolated process is said to be thermodynamic equilib- DH = DE + D(PV)
rium when no changes occur in its macroscopic properties
If P is constant
spontaneously.
All isolated system tends towards thermodynamic equi- DH = DE + PDV
librium. DH = DE + PDV = DE + (P2V2 – P1V1)
For existence of thermodynamic equilibrium, following Assuming gas to be ideal
three equilibrium must be held:
nRT
fi Thermal Equilibrium: When system and surrounding V=
are at same temperature. P
fi Mechanical Equilibrium: No net force should exist on If T and P are constant then,
the system. RT
DV = Dn
Material Equilibrium P
DH = DE + RTDn
Physical Equilibrium: Chemical Equilibrium
Phase Change Dn = Dng = Sn(gas) Product – Sn(gas) Reactant
N2 + 3H2 2NH3
H2O(s) H2O(l) at 1 atm and 0°C fi DH = DE + DngRT
At standard state Pressure = 1 bar (1 atm = 1.01 bar) If Dng > 0 fi DH > DE
DH = DH° ; 1 atm
If Dng = 0 fi DH = DE
DG = DG° Temprature : 25°C (298 K)
or Dng < 0 fi DH < DE
E = E°
else specified
Concentration: 1 Mole L–1

Homogenous and Heterogeneous System Prove CP – CV = R (For 1 mole ideal gas)

For one mole gas (PV = RT)
Homogenous Heterogeneous H = E + RT
1. Only one Phase present. 1. More than one phase. Ê ∂H ˆ Ê ∂E ˆ
e.g., Pure solid e.g., Solid + Solid \ ÁË ˜¯ = ÁË ˜¯ + R
∂T P ∂T V
Pure liquid H2O(l) + Oil(l)
Gas (X) + Gas (Y) H2O(l) + H2O(g) at equilib- CP = CV + R
H2O(l) + NaCl(s) = Solution rium CP – CV = R
H2O(l) + NH3(g) = Solution H2O(S) + H2O(l) at equilib-
2. In homogenous system rium
composition is same RELATION BETWEEN CHANGE
throughout. IN ENTHALPY AND CP FOR
ANY PROCESS
H = f(P, T, V, n)
HEAT CAPACITY (HC)
H = f(P, T) in closed system for any process.
Ê ∂H ˆ Ê ∂H ˆ
q = msDt (In Physics) \ dH = Á ◊ ∂T + Á ◊ dP
Ë ∂T ˜¯ P Ë ∂P ˜¯ T
(1)
q = mcDt (In Chemistry)
dH = change in enthalpy due to change in temperature and
q dq
H.C = mc = or change in pressure.
Dt dT
Ê ∂H ˆ
Cal J ÁË ˜ ◊ ∂T = change in enthalpy due to change in tempera-
Unit : , ∂T ¯ P
∞C ∞C
ture only.
Heat capacity is a extensive property of the system.
For Ideal gas,
Ê ∂H ˆ
SPECIFIC HEAT ÁË ˜ =0
∂P ¯ T
For Real gas
q = msDt
Ê ∂H ˆ
q Ê Cal ˆ ÁË ˜ π0
C=S= (intensive property) ∂P ¯ T
mDt ÁË gm – °C ˜¯ For Solids and Liquids
For solids and liquids, specific heat depends upon nature dp 0
of the substance. Under above set of condition; Eq. (1) may be written as
For gases, C depends upon nature as well as the process.
Ê ∂H ˆ
dH = Á ◊ dT
At constant volume (CV) At constant Pressure (CP) Ë ∂T ˜¯ P
dE = dq + w
gas x
1 gm gas 1 atm dE = dq – PdV
1 gm
25°C 25°C dq = dE + PdV
qp V(l) dqp = dH (2)
qv
{H = E + PV \ dH = dE + PdV}
Purpose: (Dt = +1°C) (Dt = +1°C) At constant pressure
Work = 0 \ Work done by the system DH = DU + V(P2 – P1)
q Ê Cal ˆ dH Ê ∂H ˆ
q CP = =Á ˜
CV = mDt ÁË gm – r ˜¯ dT Ë ∂T ¯ P
mDt
dq p Ê ∂H ˆ
fi =Á
_______________________ dT Ë ∂T ˜¯ P
Molar Specific Heat are of two types:
CP = Molar specific heat at constant pressure = CV ¥ Molar Ê ∂H ˆ
fi CP = Á
Mass Ë ∂T ˜¯ P
CV = Molar specific heat at constant pressure = CP ¥ Molar
Mass
fi Ú ∂H = Ú C P ∂T (3)

Case 1: ÚdU = Ú(a + bT + cT2)∂T

Where CP is temperature independent 1 mole
T2 b c
DH = CP Ú dT DU = a (T2 - T1 ) + (T22 - T12 ) + (T23 - T13 ) (5)
T1
2 3
= CP(T2 – T1) (For one mole)
For ‘n’ moles KIRCHOFF’S EQUATION (For
DH = nCPDT (4) Chemical Equation)
Case 2: Reaction N2 + 3H2 Æ 2NH3
CP is temperature dependent.
7 7
CP = a + bT + cT2 CP R R 4R
2 2
T2
Ú dH = ÚT 1
(a + bT + cT 2 )dT DrCP = S(vPCP)Product – S(vRCP)Reactant
b c È 7 7 ˘
DH = a (T2 - T1 ) + (T22 - T12 ) + (T23 - T13 ) (5) = [2 ¥ 4R] – Í1 ¥ R + 3 ¥ R ˙
2 3 Î 2 2 ˚
Internal energy and specific heat at constant volume = 8R – 14R fi –6R
U = f(P, T, V, n) Gas. CP CV
U = f(T, V)- in closed system for any process Mono atomic, He, Ne 5/2R 3/2R
Ê ∂U ˆ Ê ∂U ˆ Diatomic H2, O2 7/2R 5/2R
dU = Á ◊ dT + Á ◊ dV
Ë ∂T ˜¯ V Ë ∂V ˜¯ T
(1)
Polyatomic Linear (CO2) 9/2R 7/2R
For ideal gas Polyatomic Non-linear NH3 4R 3R
Ê ∂U ˆ D r H o = S (v p DH of ) Products - S (vR DH of )Reactants
ÁË ˜ ◊ dV = 0 [isochoric condition dV = 0]
dV ¯ T
For real gas, Ê KJ ˆ
DHf : Heat of formation in Á
Ê ∂U ˆ Ë mole ˜¯
ÁË ˜ π 0; dH = CPdT : Process
dV ¯ T
For solid/liquid, d DrH = DrCP.dT : For chemical reaction
T2 T2
dV 0
Under these set of condition Ú d DrH = Ú Dr CP ◊ dT
T1 T1
Ê ∂U ˆ ÏdU = dq + W ¸
dU = Á ◊ dT Ì ˝ Since W = PdV = 0
T2
Ë ∂T ˜¯ V Ó\ dU = dqV ˛ [ DH T2 - DH T2 ] = Ú Dr CP ◊ dT
T1
dqV Ê ∂U ˆ
=Á ˜ Case 1: If CP is independent of temperature
dT Ë ∂T ¯ V
DH T2 - DH T1 = DrCP (T2 - T1 )
Ê ∂U ˆ
CV = Á
Ë ∂T ˜¯ V
dT DH T2 - DH T1
= DrCP
T2 - T1
Ú ∂U = Ú CV ∂T (3)
Similarly,
Case 1: If CV is temperature independent DE2 - DE1
= DrCV
T2 T2 - T1
DU = CV Ú dT Case 2: If CP and CV are temperature dependent
T1
AhB+C
fi DU = CV(T2 – T1) (for 1 mole)
(CP)A = a + bT
For ‘n’ moles
(CP)B = a¢ + b¢T
DU = n ¥ CV(T2 – T1) (4)
(CP)C = a≤ + b≤T
Case 2: If CV is temperature dependent
DrCP = (a¢ + a≤ – a) + (b¢ + b≤ – b)T
CV = a + bT + cT2
= Da + DbT

T2 T2 DE = q + w
Ú d DrH = Ú DCP ◊ dT q=0
T1 T1
DH = DE + nRDT
T2
DH T2 - DH T1 = Ú (Da + DbT ) ◊ dT =0
T1 3. Irreversible isothermal expansion of ideal gas.
Db 2 P
= Da (T2 - T1 ) + (T2 - T12 ) A (1l, 10 atm)
2 10
Zeroth law of thermodynamics: A B Reversible Expansion

If A and B is in thermal equilibrium q
q q q q 1 B (1 atm, 10l)
and A and C are in thermal equilib- E
Irreversible Expansion
rium then, B and C must be in ther-
C
mal equilibrium. D DV C V
|Wrev.exp.| > |Wirr.exp.|
Calculation of Work in Different Process _____
fi Area ABCDA > Area BCDEB
1. Reversible isothermal expansion of ideal gas.
4. Irreversible isothermal expansion of ideal gas in two stages.
P
A |Wrev., exp.| > |Wirr.2stage, exp.| > |Wirr.one stage, exp.|
P1
5. Irreversible isothermal compression of ideal gas
P A E
10
P2 B Irreversible compression
B
V1 V2 V
dW = –Pext. ◊ dV D DV C V
dW = –Pgas ◊ dV |Wrev.comp.iso.| < |Wirr.comp.iso.|
W = Ú dW = - Ú PdV fi Area ABCDA > Area AECDA
V2 6. Irreversible isothermal two-stage compression of ideal gas.
1
= - nRT Ú dV
V P
V1
= - nRT [ln V ]V2

V A
10
1
V2 1 6
W = - nRT ln Pμ B
V1 V
P1
W = - nRT ln
P2
2. Isothermal reversible compression of ideal gas. DV V
P |Wrev.comp.iso.| < |Wirr.twostage| < |Wirr.onestage|

A
P1 7. Work done in entire irreversible cycle.
P
A IIC (IIC) Irreversible isothermal
P2 B compression
(IIE) Irreversible isothermal
W Expansion
IIE
V1 V2 V
V
|Wrev.iso.exp.| = |Wrev.iso.comp.|
|WAB| π |WBA|
(-) (+)
WAB + WBA = 0 (For entire reversible cycle) WAB + WBA π 0

Applying first law of thermodynamic for cycle A Æ B, B Æ A here |WBA| > |WAB| means work done on the system greater
than work done by the system. \ network +ve.

8. Work done during chemical equation taking place in closed Calculation of work done
rigid vessel. nRT1
W = –Pext. DV V1 = (6)
W = 0 because dv = 0 P1
9. Work done in chemical reaction occurring at constant nRT2
pressure ‘P’ and constant temprature ‘T’. = –Pext.(V2 – V1) V2 =
P2
nRT Dng RT Prove TVg – 1 = constant for reversible adiabatic process.
A(g) h B(g) + C(g) V= ; \ DV =
P P dq = 0 or q = 0
ÚdW = –Pext.ÚdV dU = dq + dw
W = –Pext. (V2 – V1) nRT
nCvdT = - dV
= –Pext.DV V
Dng ◊ RT dT
=-
R dV
= -P ◊ T Cv V
P
T2 dT dV
W = –Dng ¥ RT V2
ÚT1 T = ÚV1 - (g - 1) V
Adiabatic Process
T V
dq = 0 (1) ln 2 = - (g - 1) ln 2
T1 V1
dE = dq + dw g -1
T2 Ê V1 ˆ
dE = dw (2) =
T1 ÁË V2 ˜¯
For ideal gas
dE = nCVdT OR
g–1
dW = –Pext dV Pext = External Pressure TV = Constant.
g
T2 V2 \ PV = Constant
Ú nCvdT = - Pext Ú dV \ P1–gTg = Constant
T1 V1
Assuming CV temperature independent Work done in irreversible adiabatic expansion
nCV(T2 – T1) = Pext(V2 – V1) (3) nCv Ú dT = - Pext Ú dV
P2V2 È nRT2 nRT1 ˘
= T2 (4) nCv[T2 - T1 ] = - Pext Í -
nR
Î P2 P1 ˙˚
Putting values of Eq. (4) into Eq. (3)
PextV1 + nCV T1 Compression of isothermal expansion (reversible) and adia-
V2 = (5) batic expansion (reversible) of ideal gas.
PC
Pext. + 2 V Case 1: When final volume is same.
R
In reversible process Pexternal = Pgas P
dW = –Pext. dV = –Pgas ◊ dV A
Rev. Iso. Expansion
and dE = nCVdT = –PdV = dw Piso. B
W = nCV(T2 – T1) Pad. C
C P – CV = R
CP R V
fi -1=
CV CV Case 2: When final pressure is same.
R
fi g -1=
CV A
Rev. Iso. Expansion
R
fi CV =
g -1 Pf
adi
nR(T2 - T1 ) P2V2 - P2V1 C B

W= =
g -1 g -1
Vadi. VISO

Comparison of work done in reversible isothermal compres- Calculation of molar specific heat for any polytopic
sion of ideal gas and reversible adiabatic compression of process. (Cm)
ideal gas. According to first law of thermodynamics,
Case 1: When final volume is same. dE = dq + dw
fi n.CV ◊ dT = nCmdT – PdV
Patm fi n.CmdT = n.CV.dT + PdV
Piso B
ad. |Wad.| > |Wiso.| P dV P nR
Cm = CV + ◊ fi CV + ◊
n dT n P (1 - x)
Iso. thermo A
R
Cm = CV +
Vf
(1 - x)
R R
Case 2: When final pressure is same. Cm = +
g -1 1- x
B C Work done in polytropic process:

P For any ideal gas undergoing through reversible polytropic
process.
PV x = K = PV
1 1 = P2V2
x x
A
dw = –Pext.dV
fi dw = –Pgas ◊ dV (for reversible process)
V
Viso Vad. V2
Slope of reversible P fi W = Ú dw = - Ú KV - x ◊ dV
adiabatic process: V1
PVg = constant -K
= [V - x +1 ]VV12
PV = nRT g
(- x + 1)
NH3 1.33 K
dP P = [V21- x - V11- x ]
= -g H2 1.40
( x - 1)
dv V He 1.67
|slope| μ |g| 1
V W= [ P2V2 - PV
1 1]
Polytrophic process ( x - 1)
PVx = constant (x π g)
Ideal gas reversible polytrophic process, Limitations of first law of thermodynamics:
1. First law of thermodynamics does not tell us about the
PV = nRT
direction of flow of energy.
fi K.V–x ◊ V = nRT 2. According to first law of thermodynamics, PMM-2 is
fi KV–x+1 = nRT possible which is not possible.
3. First law doesnot tells about feasibility, i.e., where the
P x=0 process will be spontaneous or non-spontaneous.
4. First law does not tells about extent of reaction.
x=1
x=2
x=3
ENTROPY(S)
x=
Entropy is a measure of randomness or disorder of molecules.
V Higher the disorder, higher will be entropy. It is extensive
dV property.
fi K (- x + 1) ◊ V - x ◊ = nR
dT È J ˘
Unit Æ Í
dV n.R.V x Î K - mole ˙˚
= Entropy is a state function.
dT K (1 - x)
Measurement of entropy measurement of entropy is dif-
dV nR ficult. However, change in entropy can be measured.
fi =
dT P(1 - x)

Order of Entropy: T1 then h1 ˘

Crystalline Solid < Amorphous Solid < Liquid < Gas
T2 Æ 0 K then h Æ 1˙˚
* If which is not possible
Entropy is proportional to complexcity of molecule.
(i) NO2 < N2O4 Carnot’s Cycle
(ii) Hg < MeOH < EtOH Carnot’s cycle consist of following four reversible steps:
(iii) H < H2 (a) Reversible isothermal expansion of ideal gas at T = T1.
(iv) H2O + NaCl > H2O (b) Reversible adiabatic expansion of ideal gas.
Entropy is also proportional to molecular weight.
(c) Reversible isothermal compression of ideal gas at T = T2.
O2 > N2 (d) Reversible adiabatic compression of ideal gas.
Entropy change is always positive in the following process:
fi Expansion of ideal gas. P
fi Following phase transformation. 1 P1V1
q1
2 P2V2
Solid Æ Liquid ˘ T1
Liquid Æ Gas ˙˙ DS > 0
P4V4 4
Solid Æ Gas ˙˚ T2
q2 3P3V3
fi Dissolution of solute in solvent.
fi In a chemical reaction where Dng > 0, V
in such case DS > 0. Process 1-2
PCl5(g) h PCl3(g) + Cl2(g)
DE1 = 0 = q1 + w1
D
CaCO3(s) ææ
Æ CaO(s) + CO2(g) fi q1 = –w1
If ng = 0DS 0
V2
2HI h H2 + I2 q1 = + nRT1 ln (1)
V1
Spontaneous and non-spontaneous process Process 2-3
Those process in which DSuniverse ≥ 0, are known as spontane- q=0
ous process and DS universe < 0 are known as non-spontane- DE2 = w2
ous process.
w2 = nCV(T2 – T1)
DS = 0 reversible
Process 3-4
DS > 0 irreversible DE3 = 0
Carnot’s Heat Engine fi q2 = –w3
Reservoier or V4
Sources T1 fi nRT2 ln (2)
V3
q1 Process 4-1
q=0
H.E. W
fi DE4 = w4
q2 fi w4 = nCV(T1 – T2)
sin K T2 For entire cycle
(T2 < T1)
DET = 0
First Law DET = (q1 + q2) + (w1 + w2 + w3 + w4)
q1 = w + q2
Process 2-3
w q1 + (- q2 )
h= = T1 ¥ V2g -1 = T2 ¥ V3g -1 (3)
q1 q1
Process 4-1
q2 T
=1- =1- 2 T2 ¥ V4g -1 = T1 ¥ V1g -1 (4)
q1 T1
Equation (3)/(4)
* T2 is always less than T1. Hence, efficiency of heat en-
gine is always less than 1. V2 V3
= (5)
V1 V4

Putting Eq. (5) in Eq. (2) DE = q + w

V (for T constant) DE = 0
q2 = –nRT2 ln 2 (6)
V1 q = –w
Efficiency of Carnot Cycle: Since w1 π w2 π w3
q +q \ q1 π q2 π q3
h= 1 2
q1
Calculation of entropy for different cases:
Putting values of q1 and q2 from Eqs. (1) and (6),
A. General heating or cooling
V2 V
nRT1 ln - nRT2 ln 2 dq
h=
V1 V1 dS =
V T
nRT1 ln 2 nCdT
V1 dS =
T
T1 - T2
h= T2 CdT
T1 fi Ú dS = n ÚT1 T
Claussius Inequality: If C is temperature Independent
Êq +q ˆ T
hrev. = Á 1 2 ˜ = 1 - 2 DS = nCP ln
T2
at constant pressure
Ë q1 ¯ T1 T1
q2rev. T2
fi 1+ =1- T2
q1rev. T1 DS = nCV ln at constant volume
T1
(q1 ) rev. (q2 ) rev.
fi + =0 If C is temperature dependent
T1 T2
C = a + bT + cT 2
q
fi S rev. = 0 T2 Ê a + bT + cT ˆ
2
T = nÚ Á ˜¯ dT
T1 Ë T
qrev.
fi Ú T =0 È T c ˘
qrev. DS = n Ía ln 2 + b(T2 - T1 ) + (T22 - T12 ) ˙
is a state function and is named change in entropy. Î T1 2 ˚
T
qrev. B. Entropy change during phase change:
Ú T
=0 A(s) + heat(x) m A(l); DH = +x
If Cycle is irreversible then, DH fusion
DSfusion =
hirr. < hrev. T
Ê q1 + q2 ˆ T2 A(l) + heat (y) m A(g); DHvap = +y
fi ÁË q ˜¯ < 1 - T
1 irr. 1 y = DHvapourisation at T = Boiling point TB
(q1 )irr. (q2 )irr. DH vaporisation
fi + <0 DS vaporisation =
T1 T2 TB
q DSvaporisation > DSfusion > 0
S irr. < 0
T Entropy change during allotropic transition
qirr.
does not specify any state. nP4 4 Pn
T white phosphorus Red phosphorus
Change in Entropy from A to B (isothermal condition) DH trans.
DS trans. =
IRev. Ttrans.
IIIrr. Isothermal (T)
A B C. Entropy change during chemical reaction:
aA + bB h cC
IIIIrr. (DS)f = Svp(Sf)P – SvR(Sf)R
q q q q
DS = SB – SA = DSI = DSII = DSIII = rev. = 1 π 2irr. π 3irr. = [c.(Sf)C] – [a.(Sf)A + b.(Sf)B]
T T T T

DrCP = SvP(CP)P – SvR ◊ (CP)R (ii) If CV is temperature dependent and is given by

c(CP)C – [a(CP)A + b(CP)B] CV = a + bT + cT2
T2 nCV V2 nR
nC Ú dS = ÚT ◊ dT + Ú ◊ dV
Ú dS = Ú T dT T
1 V1 V
T2 (a + bT + cT 2 ) V2 1
= nÚ ◊ dT + nR Ú ◊ dV
fi for chemical reaction T1 T2 V1 V
D r C. È T Ê T ˆ˘
Ú d (D r S ) = Ú
T
dT = n Ía ln 2 + b(T2 - T2 ) + C (T22 - T12 ) + nR Á ln 2 ˜ ˙
ÍÎ T1 Ë T1 ¯ ˙˚
fi at constant pressure
Second law of thermodynamics:
T2 T2
D r CP 1. PMM-2 is not possible.
Ú d (D r S ) = Ú T
◊ dT 2. Heat cannot be completely converted in to work.
T1 T1
3. Entropy of the universe always increases during irre-
(i) If DrCP is temperature independent: versible spontaneous process
4. Efficiency of engine can not be equal to 1.
T2
( D r S )T2 - ( D r S )T1 = D r CP ln Third law of thermodynamics:
T1
According to third law of thermodynamics, entropy of per-
If CV is temperature independent: fect crystalline solid is 0 at 0K.
T2 H – Cl at 0K NO/CO at 0K
( D r ) ST2 - ( D r ) ST1 = DrCv ln
T1
H Cl H Cl CO CO CO
(ii) DrCP is temperature dependent: OC OC OC
Cl H Cl H
If DrCP = a + bT + cT2 CO CO CO
H Cl H Cl OC OC OC
T2 (a + bT + cT 2 )
( D r ) ST2 - ( Dr ) ST1 = Ú ◊ dT SHCL (0K) π 0 SCO (0K) = 0
T1 T
T c Size of H, Cl is not Size of C, O is comparable
= a ln 2 + b(T2 - T1 ) + [T22 - T12 ] comparable
T1 2
However, there are substances in which even at 0K there
D. Entropy change involving ideal gas: will be some disorder and hence there will be some residual
First law entropy even at 0K.
dU = dq + dw Measurement of entropy
fi nCVdT = TdS – PdV A( s ) ææ
I
Æ A( s ) ææ
Æ A(l ) ææÆ
II III
fi TdS = nCVdT + PdV at 0 K assuming at Tm at Tm

perfect crystalline
T2 dT V2 nR ˘ nRT
fi Ú dS = ÚT1 nCV T + ÚV1 V dV ˙˚ P=
V
IV
A(l ) ææÆ A( g ) ææ
Æ A( g )
V
at TB at TB at TK
(i) If CV of ideal gas is temperature independent
T V DS = DSI + DSII + DSIII + DSIV + DSV
DS = nCV ln 2 + nR ln 2
T1 V1 assuming molar entropy of A gas at TK to be ST.
PV PV Tm CPm ( S ) DH fussion
We know 1 1
= 2 2 ST - 0 = Ú dT + +
T1 T2 0 T Tm
P1 T2 V2 TB C P ◊ m (l ) dT DH vap. T CP , m ( g )
\ ◊ =
P2 T1 V1 ÚTm T
+
TB
+Ú
TB T
dT
T2 È P T ˘
So DS = nCV ln + nR Íln 1 + ln 2 ˙
T1 Î P2 T1 ˚ GIBB’S ENERGY (G)
T P
= (nCV + nR) ln 2 + nR ln 1 DSuniverse = DSsystem + DSsurrounding
T1 P2
T2 P DH surrunding
DS = nCP ln + nR ln 1 DSuniverse = DSsystem +
T1 P2 T

DH system For chemical reaction

DSuniverse = DSsystem – aR h bP
T
fi –TDSuniverse = DHsystem – TDSsystem P2
DHSystem = –DHsurrounding
Ú d (DrG) = ÚP 1
( DrV ) ◊ dP
fi DG = DH – TDS (at constant T and P) DrGP2 - DrGP1 = DrV ◊ ( P2 - P1 )

For feasible/spontaneous Non-spontaneous For ideal gas:
1. DSuniverse > 0 1. DSuniverse < 0 nRT P2
2. DG < 0 2. DG > 0 Ú dG = ÚP P
dP
1
In reversible reaction at equilibrium P
1. DSuniverse = 0 DG = nRT ln 2
P1
2. DG = 0
Now, DG = DH – TDS at constant pressure
dG = –SdT
No. DH DS T DG Example
Ê ∂G ˆ
1. (–) (+) high – ÁË ˜ = -S
7 ∂T ¯ P
2. (–) (+) low – C2H5OH(l) + 2 O2(g) Æ
aR h bP
2CO2(g) + 3H2(g) + heat
T2 T2
3. (+) (–) high + 2CO2 + 3H2O Æ C2H5OH + = Ú d ( DrG ) = - DrS Ú dT
T1 T1
4. (+) (–) low + 7
O DrGT2 - DrGT1 = – DrS [T2 - T1 ]
2 2
5. (–) (–) high + CaO(s) + CO2(g) Æ
6. (–) (–) low – CaCO3(s) + heat Standard Gibb’s Energy of Formation: ( DG of )
7. (+) (+) high – When 1 mole of any compound is formed from its most sta-
ble constituents. Then, change in Gibb’s energy under stan-
8. (+) (+) low + D
CaCO3(s) + heat ææ
Æ dard condition is said as DG of
CaO(s) + CO2(g)
For element and molecules in their most stable form, DG of
Since G = H – TS assumed to be 0.
\ DG = DH – TDS here (s) = solid, (l) = liquid, (g) gas
= –nFE C(graphite)
= DG° + RT ln Q Q = Reaction Quotient S(rhombic)
H2(g) Na(s)
= –Wuseful = (maximum available non PV work)
fi for all DG f = 0
o
O2(g) Ca(s)
DG° = DH° – TDS° ˘ Fe(s) Fe(s)
= –nFE° ˙ fi At Standard Condition F2(g) Hg(l)
˙
= –RT ln Keq ˙˚ Cl2(g)
We know G = H – TS Br2(l)
I2(s)
fi DG = dH – d(TS)
= dE + d(PV) – d(TS) Gas
DHvap
= dq + dw + d(PV) – d(TS) S DS =
TB
= TdS – PdV + PdV + VdP – TdS – SdT
Entropy
Liquid T CP
DS = Ú TB dT
= VdP – SdT M T
DHf
dG = VdP – SdT DSs–l =
T
at constant temperature Solid
dG = VdP
Tm TB Temperature
Ê ∂G ˆ
ÁË ˜ =V and DSS–l < DSl-g
∂P ¯ T

Entropy change of ideal gas in following expansion process:
Process DSsystem DSsurrounding DST

(1) Reversible isothermal V2 qrev.
DS = nR ln = –DSsystem 0
V1 T
(2) Irreversible isothermal free expansion V2

DS = nR ln 0 >0
DE ∞ = q + w ∞ V1
(3) Irreversible intermediate isothermal Expansion -q

(+ve) DS = >0
DE ∞ = q + w T
(4) Reversible adiabatic Expansion V2 T
DE = q ∞ + wrev DS = nR ln + nCV ln 2 = 0
V1 T1 0 >0
(+ve) (–ve)
(5) Irreversible adiabatic free expansion V2
DE = q ° + w ° DS = nR ln (+ve) 0 >0
V1
(6) Irreversible adiabatic intermediate Expansion V2 T
DS = nR ln + nCV ln 2 + ve
DE = q ∞ + wirr. V1 T1 0 >0
(+ve)
Endothermic Reaction:
THERMOCHEMISTRY
Thermochemistry is that part of thermodynamics which deals PE

DH
with heat exchanged between system and surrounding during
any chemical reaction or phase change.
Exothermic and endothermic reaction: Reaction coordinate
R h P + q (heat) q(heat) + R h P
q + HR = HP
Potential energy
fi DH = HP – HR
Thershold = +q
PE energy
DH Eaf = Eab + DH
HR Examples:
HP
(a) Decomposition reaction
Reaction coordinate (b) Elimination reaction
HR = Enthalpy of reactant, Hp = Enthalpy of Product DH or DE for the reaction

Enthalpy change of the reaction at constant pressure is
First law HR = HP + q known as DH.
DH = HP – HR Enthalpy change of the reaction at constant volume is
known as DE.
= –q
DH and DE depends on following factors:
Eaf = Eab + DH (including sign) 1. Reaction condition, i.e., whether pressure is constant or
DH in magnitude is always less than Eab. volume is constant.
Examples of exothermic reaction: DH = DE + DngRT
(a) Combustion reaction If Dng > 0 fi DH > DE
(b) Addition reaction Dng = 0 fi DH = DE
(c) Acid-base neutraliation Dng < 0 DH < DE
In Bomb calorimeter: V-constant

2. Temperature: 1
DH T2 - DH T1 C(graphite) + 2H2(g) + O2(g) h CH3OH(l)
= DrCP 2
T2 - T1 7C(graphite) + 3H2(g) + O2(g) h C6H5COOH(s)
DE2 - DE1 3 1
= DrCV 2C(graphite) + H2(g) + N2(g) h CH3 – CN(g)
T2 - T1 2 2
fi if T2 > T1 1 1
N 2 (g) + 2H 2 (g) + Cl2 (g) h NH 4Cl(s)
If DrCP > 0 DH2 > DH1 2 2
DrCP = 0 DH2 = DH1
DrCP < 0 DH2 < DH1 H2(g) + S(rhombic) + 2O2(g) h H2SO4(l)
3. Pressure: 1 1
DH, DE depends on pressure: H 2 (g) + Cl2 (g) h HCl(g)
2 2
4. Different allotropic forms: 3
C(graphite) + O2(g) h CO2(g) + 393.5 kJ/mole H 2 (g) + P(white) + 2O 2 (g) h H3PO 4 (l)
2
C(diamond) + O2(g) h CO2(g) + 395.4 kJ/mole
5. Different isomeric form:
Application of DH f
o
C4H8 + 6O2 h 4CO2 + 4H2O + x kJ/mole
Cis-2-butene 1. Calculation of standard enthalpy of the reaction:
C4H8 + 6O2(g) h 4CO2 + 4H2O + y kJ/mole D r H ∞ = Sn p ( DH fo ) p - Sn R ( DH fo ) R n = No of moles
trans-2-butene x>y
6. Phase: 2. Calculation of relative stability of isomers and allo-
tropes:
1
H 2 (g) + O 2 (g) h H 2 O(g) + x 1
2 Stability μ (including sign)
1 DH fo
H 2 (g) + O 2 (g) h H 2 O(l) + y x < y
2 If DH fo for A 10 J and for A¢ (12 J) then A is more
Standard Conditions: stable
Pressure = 1 bar Explosive compound should have high +ve value of
Temperature = Specified (298 K) DH fo
activity = 1
Standard enthalpy change of combustion:
for dilute solution
When 1 mole compound is completely combusted in the
|activity| = |concentration| in Molarity |M|
presence of sufficient oxygen then, enthalpy of the reaction
7. Solvent:
Na+(g) + Cl–(g) h NaCl(s) DH1 under standard conditions is known as DH combustion
o
Na+(aq) + Cl–(aq) h NaCl(s) DH2 DH combustion

o
is always negative or else reaction is not con-
Na+(alc) + Cl–(alc) h NaCl(s) DH3 sidered to be combustion reaction.
DH1 π DH2 π DH3
Èheat + F2 + 1/2O 2 h OF2 ˘
Standard enthalpy of formation DH f :
o
Íheat + N + O h 2NO ˙ not a combustion reaction
When 1 mole compound is formed from its most stable con- Î 2 2 ˚
stituents then, enthalpy change of reaction is termed as DH f .
o Reason: BDE of N ∫ N More than 900 kJ/mole
For elements and molecules listed below DH f is taken
o 1
C + O 2 h CO(g) + heat (parital combustion)
as 0. 2
C(graphite), H2(g) N2(g) S(rhombic) P (White) Normal combustion products of element:
DH fo may be +ve or –ve. CHSPNOLiCa h CO2(g) N2(g)
H2O(l) Li2O(s)
Write down thermochemical equation for the formation SO2(g) CaO(s)
following compounds: P4O10(s)
CO2(g), H2O(l), C2H2(g), CH3OH(l), C6H5COOH(s), CH3– Q. Write down thermo-chemical equation for the combus-
CN(g), NH4Cl(s), H2SO4(l), HCl(g), H3PO4(l) tion of following compounds:
C(graphite) + O2(g) h CO2(g) C(graphite), C(diamond), H2(graphite), S(rhombic),
P(white),
1
H 2 (g) + O 2 (g) h H 2O(l) CH4(g), C2H4(g), C2H2(g), CH3OH(l), C6H5COOH(s)
2 CH3 – CN(g), PH3(g)
2C(graphite) + H2(g) h C2H2(g) C(graphite) + O2 h CO2(g)

C(diamond) + O2 h CO2(g) HOC order x > y > z

Since stability order trans-2 butene > Cis-2 butene > 1-bu-
1
H 2 (g) + O 2 h H 2O(g) tene
2
In comparing stability of different members of
S(rhombic) + O2 h SO2(g)
homologous series.
5 1
P(white) + O 2 h P4 O10 (s) Cyclo alkane Æ CnH2n
4 4
CH4(g) + 2O2 h CO2(g) + 2H2O(l) + O2 h 3CO2 + 3H2O + x kJ/mole
C2H4(g) + 3O2 h 2CO2(g) + 2H2O(l)
+ O2 h 4CO2 + 4H2O + y kJ/mole
5
C2 H 2 (g) + O 2 h 2CO 2 (g) + H 2 O(l)
2 + O2 h 5CO2 + 5H2O + z kJ/mole
3
CH3OH(l) + O 2 h CO 2 (g) + 2H 2 O(l)
2 + O2 h 6CO2 + 6H2O + w kJ/mole
15
C6 H5 COOH(s) + O 2 h 7CO 2 (g) + 3H 2 O(l)
2 HOC = x < y < z < w
11 3 1 Since, HOC μ No of Carbon or Molar mass
CH3 - CN(g) + O 2 h 2CO 2 (g) + H 2 O + N 2 1
4 2 (l) 2 (g) \ | DH comb.
o
| per CH 2 μ
Stability
1 3
PH3 (g) + 2O 2 h P4 O10 (s) + H 2 O(l) x y z w
4 2 > > >
3 4 5 6
Application of DH combutation
o
Since stability of cycloalkane
fi In calculation of = D r H o = DH reaction
o
< < < >

DrH ∞ = Sn R ( DH comb
o
) R - Sn p ( DH comb.
o
)p
for reaction CH4(g) + SO2(g) h CO2 + H2O + S In estimating calorific value of any fuel.
Since DH° combution for SO2, CO2, H2O = 0 |DH comb.
o
|
C.V. = KJ/g
GMM
DrH° = (DHComb.)CH4 – (DHcomb.)S
CH4 + 2O2 h CO2 + 2H2O + 800 kJ/mole
fi C3H8 + H2 h C2H6 + CH4 DrH° = –55.7 kJ 800
= 50 KJ/g
fi - 55.7 = [(1 ¥ DH comb.
o
C3H8 ) + (1 ¥ DH comb.
o
H 2 )] 16
- [(1 ¥ DH comb. (C2 H 6 ) + 1 ¥ DH comb. CH 4 )]
o o 1
H 2 + O 2 h H 2O + 300 KJ/mole
300
= 150 KJ/g
In estimation of stability of allotropes 2 2
C(diamond) If calorific value ≠ fuel more efficient.
P.E.
1.9 KJ/mole
more stable DH BDE
o
(Bond dissociation energy)
C(graphite) When 1 mole bonds are broken from gaseous reactants to
gaseous products then, enthalpy change of reaction under
standard conditions is known as DH BDE
o
.
It is always positive.
395.4 395.5 KJ/mole CO2 (i) H2(g) Æ 2H(g) DH o = DH BDE
o
1 (ii) Cl2(g) Æ 2Cl(g)

\ | DH comb.
o
|μ
Stability (iii) O2(g) Æ 2O(g)
\ graphite more stable. (iv) CH4(g) Æ CH3(g) + H(g) DH1
In comparing stability of different isomers CH3(g) Æ CH2(g) + H(g) DH2
C4H8 + O2(g) h 4CO2(g) + 4H2O(l) + Heat of combution CH2(g) Æ CH(g) + H(g) DH3
CH(g) Æ C (g) + H(g) DH4
C4H8 + O2(g) Æ 4CO2(g) + 4H2O(l) + Heat of combution
CH4(g) Æ C(g) + 4H(g) DH
4CO2(g) + 4H2O + x kJ/mole DH = DH1 + DH2 + DH3 + DH4
H H DH
4CO2(g) + 4H2O + y kJ/mole DH B.D.E. of C - H in CH 4 =
4
H 4CO2(g) + 4H2O + z kJ/mole
H Br2(l) Æ 2Br DH o π DH BDE
o

Application of B.E. data DH transition. (+ve or –ve)

fi In comparing stability of bonds: 1 mole C(graphite) h 1 mole C(diamond) DH = DH transi-
1. C – C > Si – Si > Ge – Ge > Sn – Sn > Pb – Pb tion.
2. P–P>N–N DH neutralisation
3. Cl – Cl > Br – Br > F – F > I – I When 1 g of equivalent of strong acid reacts with 1 g equiv-
4. S–S>O–O alent of strong base, energy is always released and enthal-
fi In calculating DH for the reaction: py change for the reaction is always same and is equal to
DHneutralisation
DH = S(B.D.E.)R – S(B.D.E.)P
Strong Acid (SA) and Strong Base (SB) taken
It is applicable for only gaseous reactants and gaseous prod-
ucts. \ dissociation energy of acid and base = 0
If reactants and products are not in gaseous state (any one) HA (SA) + BOH (SB)
then, calculate DH for reaction by the following method: 1 gm – eq. 1 gm – eq.
DH = Eabsorbed – Ereleased Ø gives Ø gives
Q. Calculate DH for following reaction: H+ + OH– h H2O + 57.3 kJ/mole
H2(g) + Cl2(g) h 2HCl(g) B.D.E. = kJ/mol. 1 g – eq. 1 g – eq. (13.7 KCal/mole)
EH–H = x, ECl–Cl = y, EH–Cl = z nf = 1 nf = 1
DH = (x + y) – 2z
1 g – mole (H+) 1 g-mole (OH–) = 1 Mole H2O
Q. Calculate DH for the following reaction:
H2(l) + Cl2(s) Æ 2HCl(l) DHneut. = –57.3 kJ/mole.
B.DE = kJ/mol Case of weak acid and weak base
EH–H = x, ECl–Cl = y, EH–Cl = z, ( DH vap ) H2 = m , Weak acid and weak base do not dissociate completely into
( DH sub )Cl2 = p , (DHvap)HCl = n respective ions and some amount of heat is consumed in dis-
sociation of weak acid and weak base. Hence,
Sol. H2(l) + Cl2(s) Æ 2HCl(l) |DHneut.| < 57.3 kJ/mole
≠m + x ≠p + y Ø2n + 2z HA + BOH
DH = (m + x + p + y) – 2(n + z)
WA WB
DHatomisation 1 g eq. 1 g-eq.
When 1 mole gaseous atoms are formed from any substance + Ø x kJ + Ø y kJ
then, DHreaction is known as DHatomisation. H+ + OH– h H2O + 57.3 kJ/mole
It is always +ve.
1 g-eq. 1 g-eq.
C(dia) Æ C(g) ¸ nf = 1 nf = 1
C(gr) Æ C(g) Ô 1 g-mole 1 g-mole
Ô
1 Ô DHneut. = –[57.3 – (x + y)]kJ/mole
H 2 (g) Æ H(g) ˝ DH ∞ = DH atom
o
2 Ô Case of HF(WA)
1 Ô Although, HF is a weak acid still its
Br2 (l) Æ Br(g) Ô
2 ˛ |DHneut.| > 57.3 kJ/mole with strong base.
HF + NaOH
Enthaphly of phase change: (WA) (SB)
DHsublimation 1 g eq. 1 g eq.
A(s) + heat Æ A(g) DH = DHSub always +ve + Øx Ø
1 mole A at temperature T (< Tm) F–(g) + H+ OH– + Na+
DH fusion
F(–) (aq.) + H.E.
A(s) + heat Æ A(l) DH = DHfusion always +ve H2O + 57.3
1 mole A at Tm charge
Since hydration μ
DH vaporisation size
A(l) + heat Æ A(g) DH = DHvap. always +ve F– size very small \ |HE| > |X|
1 mole A at Temperature Boiling Point DHneut. = –[57.3 + H.E. – x]
DHsub. = DHfusion + DHvap. H.E> > x
If \ DrCp Æ 0 DH T2 = DH T1 and Hydration energy (HE) for other acid negligible due to
bigger size of anion.

(i) DHhydration for ions

When one mole of gaseous ion is treated with excess
RESONANCE ENERGY (RE) water, the energy is always released and enthalpy change is
known as DHhyd. always –Ve.
P.E. A+n(g) + aq. Æ A+n(aq.) DH = DHhyd of A+n(–ve)
B–m(g) + aq. Æ B–n(aq.) DH = DH hydration of B–m(–ve)
Dewar structure
charge
|DH hyd.| μ
size
Kekule structure
(ii) DHhydration for molecules
R.E.
Resonance hybrid When 1 mole of anhydrous-solid or partially hydrated
solid is further hydrated, enthalpy change for the process is
known as DHhyd. (may be +ve or –ve)
Resonance energy is defined as difference in energy between aq.
most stable R.S. (hypothetical) and actual resonance hybrid. CuSO4 (anhydrous solid) ææÆ CuSO4 ◊ 2H2O
Resonance energy is always negative. (1 mole)
aq.
R.E. = ( DH fo ) th ( DH fo )actual CuSO4 ◊ H2O(s) ææÆ CuSO4 ◊ 5H2O(s)
(1 mole)
= ( DH co ) th ( DH oc )actual
DH solution
All theortical calculations are done with respect to most When 1 mole of solute is dissolved in large excess of sol-
stable R.S, (Resonating structure) while actual experimental vent (more than 200 moles) the enthalpy change is known as
data are related with actual R.H. (Resonance hybrid) DHsolution.
If R.H. appears on the reactant side then, resonance energy Solvent
is absorbed otherwise it is released. 1 mole A (soluteof solid/liquid/gas) ææææ
large
Æ A(solution)
From the following observation calculate the R.E. of ben- (excess)
zene. DH = DHsolution
IF + 3H2 + y KJ/mole At C Æ 0 M or infinite dilution.
there is no solute-solute interaction.
+ H2 + x KJ/mole solvent A(solution)
DHIES A(solute) 1 mole ææææææÆ
specified Amount. C1M
P.E. |DH|
y – 3x = R.E. (I) (II) (III)
3x
y DHIES
x
ant. y solvent
R.E. of benzene = y – 3x DH dilution

Lattice Dissociation Enthalpy: Amount of energy required + solvent
A(solution - 1) ææææææ
(given amount)
Æ A(solution - 2)
to break 1 mole ionic crystal into constituent gaseous ion. C1M C2 M
Always positive
NaCl(s) Æ Na+(g) + Cl–(g) DH = DHL.D.E. (C1 > C2) DH diln of AC1 Æ C2
(1 mole) DHI.E.
+3
Al2 (SO 4 )3 (s) Æ 2Al (g) + 3SO --
4 (g) [A(g) + I.E.1 Æ A+(g) + e–] at 0 K
(1 mole) DH = DH L.D.E.of Al2 (SO4 )3 DHIE is at temp ‘T’ K
charge DH I.E. - I.E. 5
DH L.D.E. μ = ( DrCp ) = R
size T -0 2
DHhydration are of two types For monoatomic gaseous atom

DHIE = I.E. + 5/2RT fi DHI.E. = I.E.

5 Hess’s law _______________________________

because I.E. >> RT According to Hess’s, whether any chemical reaction occurs
2
DHE.A. in one step or more than one step, DH is same.
DH1
[A(g) + e– Æ A–(g) + E.A. (energy released)] A B
DH E.A. - E.A. DH3 DH4
= ( DrCp)
T -0
C D
5 DH3
DH E.A. = E.A. - RT | DH EA| | EA |
Ø 2 DH1 = DH2 + DH3 + DH4
(with sign)
In other words, we can treat that thermochemical equation as
algebraic equation.
Solved Examples
1. Any real gas is subjected to change in its state from 10 1.26

atm, 5l to 3 atm, 2l. DU = 20 l – atm. Calculate DH for enthalpy change for 1 mole fi
fi 2.52 ¥ 102 kJ 5 ¥ 10 –3
the process.
Sol. DH = DU + (P2V2 – P1V1) 4. One mole of ideal gas is allowed to expand reversibly
= 20 + (6 – 50) and adiabatically from a temperature of 27°C. If the
= –24l atm work done by the gas in the process is 3 kJ, the final
2. 0.5 A current from a 20 V supply is passed for 203 sec. temperature will be equal to (CV = 20 J/K mol)
through a water sample. 0.9 g water vapourises at 1 (a) 100 K (b) 450 K (c) 150K (d) 400 K
atm at its boiling point. Calculate DE and DH for the Sol. (c) for adiobatic process DU = W because q = 0
vapourisation of 1 mole water. fi 3000 = CV(T2 – T1)
Sol. H2O(l) h H2O(g) 3000
0.9 g T 2 – T1 =
20
T2 = T1 + 150 = 450 K
atm 5. Five moles of an ideal gas at 300 K, expanded isother-
mally from an initial pressure of 4 atm to a final pres-
373 K sure of 1 atm against a constant external pressure of 1
atm. Calculate q, w, DU and DH. Calculate the corre-
sponding value of all if the above process is carried out
0.5 A reversibly.
È nRT nRT ˘
203 sec Sol. Wirr = - Pext [V2 - V1 ] = -1 Í -
20 V
Î P2 P1 ˙˚
W = q ¥ V = Charge ¥ Voltage
= i ¥ t ¥ V = 0.5 ¥ 203 ¥ 20 J È1 1˘ È P˘
= - nRT Í - ˙ = - nRT Í1 - 2 ˙
= 2030 J = 2.03 kJ Î P2 P1 ˚ Î P1 ˚
For one mole or 18 g water heat supplied = DH Ê 1ˆ
= - 5 ¥ 8.314 ¥ 300 Á1 – ˜
2.03 Ë 4¯
DH = ¥ 18 = 40.6 KJ/mole
0.9 Wirr = –9.353 kJ
3. 50.0 mL of 0.10 M HCl is mixed with 50.0 mL of 0.10 ÊV ˆ
M NaOH. The solution temperature rises by 3.0°C. Wrev = –2.303 nRT 1og Á 2 ˜
Ë V1 ¯
Calculate the enthalpy of neutralization per mol of
HCl. Wrev = –2.303 ¥ 5 ¥ 8.314 ¥ 300 log 4
(a) –2.5 ¥ 102 kJ (b) –1.3 ¥ 102 kJ Wrev = –17.29 kJ
(c) –8.4 ¥ 101 kJ (d) –6.3 ¥ 101 kJ and Dq = DE – W
Sol. HCl + NaOH h NaCl + H2O at DT Æ 0 DE Æ 0 DH Æ 0
for water C = 4.2 J/gram Wrev = –q = 17.29 kJ
enthalpy change = mCdT = 100 ¥ 4.2 ¥ 3 = 1.26 kJ 6. 1 mole of CO2 gas at 300 K is expanded under revers-
enthalpy change for 5 millimole = 1.26 kJ ible adiabatic condition such that its volume becomes
27 times.

(a) What is final temperature? 5R(T2 – 350) = (750R – 2RT2)

(b) What is work done? 5T2 – 1750 = 1400 – 2T2
Given g = 1.33 and CV = 25.08 J mol–1 K–1 for 7T2 = 3150 \ T2 = 450 K
CO2. W = 2 ¥ CV(450 – 350)
Sol. n1 = 1 5
T1 = 300 V2 = 27 V1 T1V1g–1 = T2V2g–1 = 2 ¥ R ¥ (100) = 500 R
2
g –1 1 9. The standard enthalpy of formation of water liquid is
Ê T1 ˆ Ê V2 ˆ Ê 1 ˆ3
ÁË T ˜¯ = ÁË V ˜¯ T2 = 300 Á ˜ –285.76 kJ at 298 K. Calculate the value at 373K. The
2 1 Ë 27 ¯ molar heat capacities at constant pressure (CP) in the
T2 = 100 K given temperature range of H2(g), O2(g) and H2O(l) are
Adiabatic condition q = 0 fi DE = W = nCV(T2 – T1) respectively 38.83, 29.16 and 75.312 JK–1 mol–1.
W = 1 ¥ 25 ¥ –200 W = –5.000 kJ/mole 1
Sol. H2(g) + O2(g) h H2O(l)
7. A sample of a fluorocarbon was allowed to expand re- 2
versibly and adiabatically to twice its volume. In the DH T2 - DH T1
expansion, the temperature dropped from 298.15 to Use kirchoff equation = DrCP
T2 - T1
248.44 K. Assume the gas behaves perfectly. Estimate
1
the value of CV. D r CP = CPH2O(l) - CPH 2 (g) - CPO2 (g)
Sol. Process reversibly adiabatic 2
\ TV g = constant 1
= 75.312 – 38.83 – ¥ 29.16
T1 = 298.15 K V2 = 2V1 2
D C = 21.90 kJ
r p
T2 = 248.44 K
10. Methane (Considered to be an ideal gas) initially at
T1V1g–1 = T2V2g–1 25°C and 1 bar pressure is heated at constant pressure
g –1 until the volume has doubled. The variation of the mo-
Ê T1 ˆ Ê V2 ˆ Ê 298.15 ˆ g –1
ÁË T ˜¯ = ÁË V ˜¯ ÁË ˜ =2 lar heat capacity with absolute temperature is given by:
248.44 ¯
2 1 CP = 22.34 + 48.1 ¥ 10–3 T. where CP is in JK–1 mol–1.
1.2 = 2g–1 log 1.2 = log 2 ◊ (g–1) Calculate molar (a) DH (b) DU.
log 1.2 Sol. CP = 22.34 + 48.1 ¥ 10–3 T JK–1 mol–1
g–1= g – 1 = 0.263
log 2 n =1 T2
P V – PV nR(T2 – T1 )
DH = Ú nCpdT = Ú (22.34 + 48.1 ¥ 10–3T)
W = nCV(T2 – T1) = 2 2 1 1 = T1
g –1 (g – 1)
48.1 ¥ 10 –3 ¥ 298 ¥ 3
Ê R ˆ DH = 22.34 ¥ 298 + ¥ 298
CV = Á 2
Ë g – 1˜¯ DH = 13.064 kJ/mole
W = –P(V2 – V1) = –nR(T2 – T1)
8.314
CV = CV = 31.61 W = –2477 J = –2.477 kJ
0.263 DE = 13.064 – 2.477
8. Two moles of an ideal gas ÊÁ CV = Rˆ˜ was compressed DE = 10.587 kJ
5
Ë 2 ¯ 11. One mole of NaCl(s) on melting absorbed 30.5 kJ of
adiabatically against constant pressure of 2 atm which heat and its entropy increased by 28.8 JK–1. What is the
was initially at 350 K and 1 atm pressure. The work melting point of sodium chloride?
involve in the process is equal to? Sol. DSf = 28.8 J/K DHf = 30.5 kJ
(a) 250 R (b) 300 R (c) 400 R (d) 500 R DH f
Sol. (d) in irreversible process if final pressure not given DS f =
Tmp
means Pext = Pfinal = P2
Irreverssible adiabatic process 30.5 ¥ 103
\ Tmp = = 1059 K
Ê nRT2 nRT1 ˆ 28.8
W = - Pext Á – P2 = Pext = 2 atm
Ë P2 P1 ˜¯ 12. Find Wa, Wb and Wc and total work from given graph
P1 = 1 atm T1 = 300 K P
a
È 2( R) ◊ T2 2 R(350) ˘ 1
W = –(2 atm) Í –
Î 2 atm 1 atm ˙˚ P(atm) b
c
5 0.5
and W = 2CV(T2 – 350) = 2 ¥ R (T2 – 350)
2
Liter
20 40 V

Sol.
10000T2 - (T2 ) 2 = 10000T2 - 360 ¥ 104
P
Wa = –1 ¥ 20 = –PDV (isobaric) T2 = 1897.36 K + (T2 ) 2 = + 360 ¥ 104
a
1
P(atm) b Wb = 0 14. A Carnot cycle is plotted on the following T-S curve.
c
0.5 WC = –nRT ln V2/V1 T
= –2.303 ¥ 20 ¥ log 20/40 1000 K
1 2
isoentropic DS = 0
Liter
20 40 V
200 K 3
PV = nRT 4
PV .5 ¥ 40
nT = = 400 500
R R S Entropy J/K
0.5 ¥ 40 20
\ WC = - 2.303R ¥ log Calculate the following:
R 40 1. Heat absorbed from the source.
= +13.86 l-atm 2. Heat released to the sink
DE = DH = DS = DG = 0 for entire cycle 3. Work done in one cycle
fi DE = q + w 4. Efficiency of the cycle
q = –w = WT 5. How many cycles per second will be required to
R = 8.314 J/mol – K perform in order to illuminate 104 bulbs of 40 W
= 2 cal/mol – K each.
l - atm q
= 0.082 Sol. 1. DS = rev
mol - K T
q1 = DS ¥ T1 = 100 ¥ 1000 = 105 J
101.3
fi 1l – atm = 101.3 J = Cal 2. q2 = DS ¥ T2 = –100 ¥ 200 = –0.2 ¥ 105 J
4.18
3. W = –0.8 ¥ 105 J fi q1 = q2 + W
WT = Wa + Wb + Wc (l – atm)
W 0.8 ¥ 105
–20 + 13.86 = –6.14l – atm 4. h = = ¥ 100 = 80%
13. From given figure, if hA = hB find T2 q1 105
10000 K 5. Energy required per second = 40 ¥ 104 J/sec
q1 = (P ¥ t) ¥ No of bulb
w1 fi 4 ¥ 104 = x ¥ 0.8 ¥ 105
A
fi x = 5 cycle sec–1
T2 15. The entropy change when two moles of ideal monoat-
omic gas is heated from 200°C to 300°C reversibly and
B w2
isochorically?
3 Ê 300 ˆ 5 Ê 573 ˆ
R ln Á
Ë 273 ˜¯
360 K (a) R ln Á ˜ (b)
2 Ë 200 ¯ 2
Sol. If 10000 K
q1 Ê 573 ˆ 3 Ê 573 ˆ
(c) 3R ln Á
Ë 473 ˜¯
R ln Á
Ë 473 ˜¯
T2
(d)
A w1 hA = 1 – 2
10000
ÊT ˆ
T2 Sol. (c) DS = nCV ln Á 2 ˜ for isochoric change.
Ë T1 ¯
360
B w2 hB = 1 – Ê 3 ˆ Ê 573 ˆ
T2 DS = 2 ¥ Á R˜ ln Á
Ë 2 ¯ Ë 473 ˜¯
360 K
Ê 573 ˆ
If hA = hB DS = 3R Á
Ë 473 ˜¯
T2 can be calculated as
16. When two equal sized pieces of the same metal at dif-
T2 360
1- =1- ferent temperatures Th (hot piece) and Tc (cold piece)
10000 T2 are brought into thermal contact and isolated from its
10000 - T2 T2 - 360 surrounding. The total change in entropy of system is
=
10000 T2 given by? [Cv (J/K) = heat capacity of metal]

Tc + Th T2 18. What is the free energy change (DG) when 1.0 mole
(a) Cv ln (b) Cv ln of water at 100°C and 1 atm pressure is converted into
2Tc T1
steam at 100°C and 1 atm pressure?
(Tc + Th ) 2 (T + T ) 2 (a) 80 cal (b) 540 cal (c) 620 cal (d) zero
(c) Cv ln (d) Cv ln c h
2Th ◊ Tc 4Th ◊ Tc Sol. (d) H2O(l) h H2O(g)
Sol. (d) The net heat absorbed by hot and cold body is equal 373 K 373 K
to zero. 1 atm 1 atm
qh + qc = 0 DH vap
DS =
Let CV is the total heat capacity of hot and cold body. T
CV(Tf – TC) + CV(Tf – Th) = 0 DG = DHf – DHi = 0
= CVTf – CVTC + CVTf – CVTh 19. If PH3(g) h P(g) + 3H(g) DH = 954 kJ
= 2CVTf = CV[Th + TC] P2H4(g) h 2P(g) + 4H(g) DH = 1485 kJ
find P-P bond energy
Th + TC
fi Tf = 954
2 Sol. EP–H = = 318 KJ
Entropy change 3
DSTotal = DShot body + DScold body because in PH3(g) 3P-H bond present
EP–P + 4 ¥ 318 = 1485 = EP–P + 4EP–H
Ê Tf ˆ
DShot body = CV ◊ ln Á ˜ EP–P = 1485 – 1272
Ë Th ¯ = 213 kJ
Ê Tf ˆ 20. Compute DrG for the reaction
DScold body = CV ◊ ln Á ˜ H2O (l, 1 atm, 323 K) Æ H2O (g, 1 atm, 323 K)
Ë TC ¯ Given that DvapH at 373 K = 40.639 kJ mol–1, CP(H2O,
Ê Tf Tf ˆ l) = 75.312 J K–1 mol–1,
DSTotal = CV Á ln + ln ˜ CP(H2O, g) = 33.305 J K–1 mol–1.
Ë Th TC¯
Sol. DrCp = 33.305 – 75.312 = – 42.007 J/K mole
Ê T f2 ˆ DH 40639
= CV Á ln ˜ DrS323 = = = 108.95 J/K mole
Ë Th ◊ TC ¯ T 323
È (T + TC ) 2 ˘ D r C p dT
DSTotal = CV ln Í f d(DrS) =
˙ T
ÍÎ 4Th ◊ TC ˙˚ T
DrS373 – DrS323 = DrCp ln 2
OR T1
DSTotal = DSI + DSII Ê 373 ˆ
DrS373 = 108.95 – Á – 42.007 ln ˜
Th + TC h C T +T Ë 323 ¯
1 1
= CV Ú 2dT + CV Ú 2 dT = 115 J/K mole
Th T TC T
d(DrH) = DrCpdT
È Th + TC Th + TC ˘
DrH373 – DrH323 = –42.007 (50)
Í ˙
= CV Íln 2 + ln 2 ˙ DrH373 = 42739.35 J/mole
Î Th T C ˚
DrG323 = 42739.35 – 323 (115)
È ÊT + T ˆ2 ˘ = 5594.35 J = 5.59 kJ/mole
Í Á h C˜ ˙
Ë 2 ¯ ˙
= CV Íln
21. Enthalpy of neutralisation of HCl by NaOH is –57.32
ÍÎ Th ¥ TC ˚˙ kJ mol–1 and by NH4OH is –51.34 kJ mol–1. Calculate
the enthalpy of dissociation of NH4OH.
17. For the reaction at 300 K
Sol. See DHneutralization case of weak acid and weak base.
A(g) + B(g) h C(g)
DHneut = –[57.34 – (x + y)] È x = 0 for strong acid ˘
DE = –3.0 kcal; DS = –10.0 cal/K value of DG is?
–51.32 = –57.34 + y Í y = 0 for strong base ˙
(a) –600 cal (b) –6600 cal
y = 5.98 kJ mol–1 Î ˚
(c) –6000 cal (d) None
OR
Sol. (a) DH = DE + DngRT
H+(aq) + NH4OH(aq) Æ NH4+(aq) + H2O(l)
= –3000 + [1 – 2] ¥ 2 ¥ 300
DrH = –51.34 kJ mol–1
= –3600 cal
we may consider neutralisation in two steps:
DG = DH – TDS = –3600 – 300 ¥ (–10)
(i) ionisation
= –600 cal
NH4OH(aq) Æ NH4+(aq) + OH–(aq) DrH1?

(ii) neutralisation C=O 728.02 kJ mol–1

H+ (aq) + OH–(aq) Æ H2O(l)
C–O 351.46 kJ mol–1
DrH2 = –57.32 kJ mol–1
Thus, DrH = DrH1 + DrH2 O–H 462.75 kJ mol–1
Therefore, Enthalpy of atomisation
DrH1 = DrH – DrH2
= –51.34 + 57.32 = 5.98 kJ/mol–1 C 718.39 kJ atom–1
22. Calculate DrH° for the reaction H 217.94 kJ atom–1
Ag+(aq) + Cl–(aq) = AgCl (s) at 25°C. O 247.52 kJ atom–1
Given:
The observed DfH° for acetic acid is –438.15 kJ mol–1.
DfH° (Ag+, aq) = 105.58 kJ mol–1,
Compute the resonance energy of acetic acid.
DfH° (Cl–, aq) = –167.16 kJ mol–1 and
Sol. The desired reaction for the formation of CH3COOH is
DfH° (AgCl, s) = –127.07 kJ mol–1
2C(s) + 2H2(g) + O2(g) Æ CH3COOH(l)
Sol. For the reaction
DrHº = –3 ¥ 413.38 – 1 ¥ 347.69 – 728.02 – 351.46 –
Ag+(aq) + Cl–(aq) Æ AgCl(s)
462.75 + 2 ¥ 718.39 + 4 ¥ 217.94 + 2 ¥ 247.52
we have,
= –326.48 kJ mol–1
DrH° = DfH° (AgCl, s)– DfH° (Ag+, aq)
Resonance energy = DH°observed – DH°theoretical
–DfH° (Cl–, aq) = –438.15 + 326.48
= [–127.07 – 105.58 – (–167.16)] = –111.67 kJ mol–1
= –65.49 kJ mol–1 25. A gas mixture 3.67 L in volume contain C2H4 and CH4
23. The enthalpy of formation of ethane, ethylene and ben- is proportion of 2: 1 by moles and is at 25°C and 1 atm.
zene from the gaseous atoms are –2839.2, –2275.2 and If the DHC (C2H4) and DHC (CH4) are –1400 and –900
–5536 kJ mol–1 respectively. Calculate the resonance kJ/mol find heat evolved on burning this mixture:
energy of benzene, compared with Kekule structure. (a) 20.91 kJ (b) 50.88 kJ
The bond enthalpy of C – H bond is given as equal to (c) 185 kJ (d) 160 kJ
410.87 kJ mol–1. PV
Sol. Bond enthalpy of C – C bond Sol. (c) nC2H4 =
RT
= Enthalpy required to break C2H6 into gaseous
2 1
atoms –6 ¥ bond enthalpy of C – H bond VC2H4 = ¥ 3.67 VCH4 = ¥ 3.67
= 2839.2 kJ mol–1 – 6 ¥ 410.87 kJ mol–1 3 3
= 373.98 kJ mol–1 1 ¥ 2 ¥ 3.67 3.67
nC2H4 = nCH4 =
Bond enthalpy of C = C bond = Enthalpy requried to 0.082 ¥ 3 ¥ 298 3 ¥ 0.082 ¥ 298
break C2H4 into gaseous atoms –4 ¥ bond enthalpy of 2 ¥ 3.67
C – H bond Heat evolved = ¥ (1400)
3 ¥ 0.082 ¥ 298
= 2275.2 kJ mol–1 – 4 ¥ 410.87 kJ mol–1
= 631.72 kJ mol–1 3.67
Heat evolved = ¥ 900
For the formation of benzene having Kekule structure, 3 ¥ 0.082 ¥ 298
we have to form 3 C – C bonds, 3 C = C bonds and 6 Total heat evolved from mixture = 140 + 45 = 185 kJ
C – H bonds for which enthalpy released is 26. The bond dissociation energy of gaseous H2, Cl2 and
[3(–373.98) + 3(–631.72) + 6(–410.87)] HCl are 104, 58 and 103 kcal mol–1 respectively. The
= –5482.32 kJ mol–1 enthalpy of formation for HCl gas will be
But the given value of DfH is (a) –44.0 kcal (b) –22.0 kcal
DfH (actual) = –5536 kJ mol–1 (c) 22.0 kcal (d) 44.0 kcal
Hence resonance energy compared to Kekule structure 1 1
Sol. (b) H 2 + Cl2 h HCl
= DfH (actual) – DfH (Kekule structure) 2 2
= (–5536 + 5482.32) (DHf)HCl = 52 + 29 – 103 = –22 kcal
= –53.68 kJ mol–1 27. Determine DHo of the following reaction using the list-
24. Using bond enthalpy data given below, estimate en- ed heats of formation:
thalpy of formation of acetic acid. 4HNO3(l) + P4O10(s) Æ 2N2O5(s) + 4HPO3(s)
Bond Bond enthalpies DHof HNO3(l) = –174.1 kJ/mole
C–H 413.38 kJ mol–1 DHof N2O5(s) = –43.1 kJ/mole
C–C 347.69 kJ mol–1 DHof P4O10(s) = –2984.0 kJ/mole
DHof HPO3(s) = –948.5 kJ/mole

(a) –176.3 (b) –199.8 29. For which of the following change DH π DE?
(c) +276.2 (d) –242.4 (a) H2(g) + I2(g) h 2HI(g)
Sol. (b) DrH = [2( DH f ) N2O5 + 4( DH f ) HPO3 – 4( DH f ) HNO3 (b) HCI(aq) + NaOH(aq) h NaCl(aq) + H2O(l)
(c) C(s) + O2(g) h CO2(g)
– ( DH f ) P4O10 ]
(d) N2(g) + 3H2(g) h 2NH3(g)
DHr = [2(–43.1) + 4(–948.5) – 4(–174.1) – (–2984.0)] Sol. (d) Since, DH = DE + DngRT
= –199.8 For Dng = 0, DH = DE
28. Use the given bond enthalpy data to estimate the DHo Dng π 0, DH π DE
(kJ) for the following reaction: 30. 4 grams of sodium hydroxide pellets were dissolved in
(C – H = 414 kJ, H – Cl = 431 kJ, Cl – Cl = 243 kJ, 100 cm3 of water. The temperature before adding the
C – Cl = 331 kJ). sodium hydroxide pellets was 25°C, and after adding
CH4(g) + 4Cl2(g) Æ CCl4(g) + 4HCl(g) the pellets it was 35°C. Calculate the enthalpy change
(a) 620 (b) 330 (c) 420 (d) 105 in kJ/mole of the reaction (Specific heat capacity of
water = 4.2 J/K/g)
Sol. (c) D r H o = S(BDE)R – S(BDE)P
(a) 42 kJ/mole (b) 4.2 kJ/mole
D r H o = [4DH (c) 4200 kJ/mole (d) none
C-H + 4DHCl-Cl – 4DHC-Cl – 4DHH-Cl]
Sol. (a) Heat evolve = mCVDT = 100 ¥ 4.2 ¥ 10 = 4.2 kJ
= [4 ¥ 414 + 4 ¥ 243 – 4 ¥ 331 – 4 ¥ 43] for 0.1 mole the enthalpy change = 4.2 kJ
D r H o = – 420 kJ for 1 mole the enthalpy change = 42 kJ
Exercise
6. For a monatomic gas, the value of the ratio of Cp.m and
LEVEL I Cv.m is
5 7 9 9
1. What is the change in internal energy DU, for a sys- (a) (b) (c) (d)
tem that does 70 J of work as it absorbs 45 J of heat? 3 5 7 11
(a) 115 J (b) 25 J (c) –25 J (d) –115 J 7. Two moles of an ideal monoatomic gas are allowed to
2. If the internal energy of an ideal gas decreases by the expand adiabatically and reversibly from 300 K and
same amount as the work done by the system, the pro- 200 K. The work done in the system is (Cv = 12.5 J/K/
cess is mol)
(a) cyclic (b) isothermal (a) –12.5 kJ (b) –2.5 kJ
(c) adiabatic (d) isolated (c) –6.25 kJ (d) 500 kJ
3. When 1 mol gas is heated at constant volume, tempera- 8. The difference between heats of reaction at constatnt
ture is raised from 298 to 308 K. Heat supplied to the pressure and constant volume for the reaction 2C6H6(l)
gas is 500 J. Then which of the following statements is + 15O2 (g) Æ 12CO2(g) + 6H2O(l) at 25° in kJ mol–1 is:
correct? (a) –7.43 (b) +3.72 (c) –3.72 (d) +7.43
(a) q = W = 500 J, DU = 0 9. A block of ice at –10°C is slowly heated and converted
(b) q = DU = 500 J, W = 0 into steam at 100°C. Which of the following curves
(c) q = W = 500 J, DU = 0 represents the phenomenon qualitatively?
(d) DU = 0, q = W = –500 J, Y Y
4. Internal energy does not include R T P
(a) vibrational energy (a) (b) Q R
T P T
(b) rotational energy Q
(c) nuclear energy X X
O Heat supplied O Heat supplied
(d) energy arising by gravitational pull Y Y
5. Which one of the following quantity is dependent on R Q S
path? (c) (d) R
P
(a) molar internal energy T Q T P
(b) volume X X
O Heat supplied O Heat supplied
(c) w
(d) q + w 10. If water vapour is assumed to be a perfect gas, molar
enthalpy change for vapourisation of 1 mol of water at

1 bar and 100°C is 41kJ mol–1. Calculate the internal (a) DU = 0, DH = 0

energy change, when 1 mol of water is vapourised at 1 (b) DU = +202.6 J, DH = +202.6 J
bar pressure and 100°C. (c) DU = –202.6 J, DH = –202.6 J
(a) 37.904 kJ mol–1 (b) 41.00 kJ mol–1 (d) DU = 0, DH = +202.6 J
–1
(c) 44.00 kJ mol (d) 39.67 kJ mol–1 21. 1 mole of an ideal gas at 25°C is subjected to expand
11. The reaction of Cyanamide, NH2CN(s), with dioxygen reversibly and adiabatically to ten times of its initial
was carried out in a bomb calorimeter, and DU was volume. Calculate the change in entropy during expan-
found to be –742.7 kJ mol–1 at 298 K. Calculate the sion (in J K–1 mol–1).
enthalpy change for the reaction at 298 K. (a) 19.15 (b) –19.15 (c) 4.7 (d) Zero
3 22. What is the heat of formation of CS2, if heat of combus-
NH 2CN(s) + O 2 (g) h N 2 (g) + CO 2 (g) + H 2O(l) tion of C, S and CS2 are “x, y and z” kJ mol–1?
2
(a) 2y – x + z (b) x – 2y + z
(a) –702.5 (b) –741.5 (c) 523 (d) –523
12. Calculate the number of kJ of heat necessary to raise (c) x + 2y – z (d) x + y + z
the temperature of 60.0 g of aluminum from 35°C to N
23. The amount of heat released when 100 mL of H 2SO 4
55°C. Molar heat capacity of Al is 24 J mol–1 K–1. N 10
(a) 0.09 kJ (b) 2.71 kJ is mixed with 150 mL of NaOH solution is
10
(c) 1.09 kJ (d) –2.07 kJ
(a) 5.73 kJ (b) 57.3 kJ (c) 57.3 J (d) 573 J
13. Which of the following has maximum internal energy
24. A sample of oxygen gas expands its volume from 3 L to
at 298 K?
(a) Helium gas (b) Oxygen gas 5 litre against a constant pressure of 3 atm. If the work
(c) Ozone gas (d) Equal done during expansion be used to heat 10 mole of water
14. 0.410 mol of a monoatomic gas fills a 1dm3 container initially present at 290 K, its final temperature will be
to a pressure of 1.013 MPa. It is expanded reversibly (a) 296.0 K (b) 290.8 K
and adiabatically until a pressure of 0.1013 MPa is (c) 298.0 K (d) 285 K
reached. Which is correct? 25. Using the following information calculate the heat of
(a) T2 = 421.28 K (b) W = –923.7 J formation of NaOH in kJ mol–1.
(c) T2 = 280 K (d) W = –12 J 2 Na(s) + 2 H2O(l) Æ 2 NaOH(s) + H2(g)
15. Enthalpy of combustion of carbon to CO2 is –393.5 kJ DHo = – 281.9 kJ
mol–1. Calculate the heat released upon formation of DHof H2O(l) = –285.8 kJ/mole
35.2 g of CO2 from carbon and dioxygen gas. (a) – 141.6 (b) – 712.6
(a) –397kJ (b) –315 kJ (c) – 426.8 (d) – 650.4
(c) +207 kJ (d) –105 kJ 26. A monoatomic gas X and a diatomic gas Y, both initial-
16. Given: N2(g) + 3H2(g) Æ 2NH3(g); DrH° = –92.4 kJ ly at the same temperature and pressure are compresed
mol–1 adiabatically from a volume V to V/2, which gas will
What is the standard enthalpy of formation of NH3 gas? be at higher temperature?
(a) –11.7 (b) –46.2 (c) 32.5 (d) –52.3 (a) X (b) Y
17. The equilibrium constant for a reaction is 10. What will (c) Both are same (d) Cannot say
be the value of DG°? 27. Heat of neutralisation of oxalic acid is –53.35 kJ mol–1
(R = 8.314 JK–1 mol–1, T = 300 K) using NaOH. Hence DH of H 2C2O 4 m C2O 42– + 2H +
(a) –1.24 kJ/mol (b) –5.744 kJ/mol
(a) 5.88 kJ (b) –5.88 kJ
(c) +1.27 kJ/mol (d) –1.27 kJ /mol
(c) –13.7 kcal (d) 7.9 kJ
18. DHvap for water is 40.73 kJ mol–1 and DSvap is 109 JK–1
28. The standard heat of formation values of SF6(g), S(g)
mol–1. The temperature at which water is in equilibrium
and F(g) are –1100, 275 and 80 kJ mol–1: respectively.
with water vapours is
Then the average S — F bond energy in SF6 is
(a) 100.67°C (b) 260.87 K
(a) 52.5 kJ mol–1 (b) 320 kJ mol–1
(c) 128.69 K (d) 460 K –1
(c) 309 kJ mol (d) 280 kJ mol–1
19. Molar heat capacity of water in equilibrium with ice at
29. One mole of an ideal diatomic gas (CV = 5 cal) was
constant pressure is
transformed from initial 25°C and 1 L to the state when
(a) Zero (b) Infinity
temperature is 100°C and volume 10 L. The entropy
(c) 40.45 kJ K–1 mol–1 (d) 75.48 kJ K–1 mol–1
change of the process can be expressed as (R = 2 calo-
20. A vessel contains 100 L of a liquid x. Heat is supplied
ries/mol/K):
to the liquid in such a fashion that, Heat given = change
in enthalpy. The volume of the liquid increases by 2 L. 298 373
(a) 3 ln + 2 ln 10 (b) 5 ln + 2 ln 10
If the external pressure is one atm, and 202.6 J of heat 373 298
were supplied then, [U Æ total internal energy] 1 atm 373 373 1
L = 101.3 J (c) 7 ln + 2 ln (d) 5 ln + 2 ln
298 298 10

30. Calculate the total entropy change for the transition at 41. Calculate the standard enthalpy of formation of
368 K of 1 mol of sulphur from the monoclinic to the CH3OH(l) from the following data:
rhombic solid state, is DH = –401.7 J mol–1 for the tran- 3
sition. Assume the surrounding to be an ice-water both CH3OH(l) + O2(g) Æ CO2(g) + 2H2O(l);
2
at 0°C. DrHo = –726 kJ mol–1 (1)
(a) –1.09 JK–1 (b) 1.47 JK–1
–1 C(graphite) + O2(g) Æ CO2(g); DH f = –393 kJ mol–1
o
(c) 0.38 JK (d) None of these
(2)
31. The maximum efficiency of a heat engine operating be- 1
H2(g) + O2(g) Æ H2O(l); DH fo = –286 kJ mol–1 (3)
tween 100°C and 25°C is 2
(a) 20% (b) 22.2% (c) 25% (d) None (a) –239 kJ mol–1 (b) –127 kJ mol–1
32. A heat engine operating between 227°C and 27°C ab- (c) +57 kJ mol –1
(d) –55 kJ mol–1
sorbs 2 kcal of heat from the 227°C reservoir reversibly 42. For the reaction,
per cycle. The amount of work done in one cycle is? 2A(g) + B(g) Æ 2D(g)
(a) 0.4 kcal (b) 0.8 kcal (c) 4 kcal (d) 8 kcal
33. At a particular temperature DU° = –10.5 kJ and DS° = –44.1 JK–1
H+(aq) + OH–(aq) h H2O(l); DH = –57.1 kJ. The ap- Calculate DG° for the reaction at 300 K.
proximate heat evolved when 400 mL of 0.2 M H2SO4 (a) 0.164 kJ (b) 0.236 kJ
is mixed with 600 mL of 0.1 M KOH solution will be (c) 0.017 kJ (d) 0.0019 kJ
(a) 3.426 kJ (b) 13.7 kJ 43. Calculate DrGo for conversion of oxygen to ozone,
(c) 5.2 kJ (d) 55 kJ 3/2O2(g) m O3(g) at 298 K. If KP for this conversion
34. When a monoatomic gas undergoes an adiabatic pro- is 2.47 ¥ 10–29.
cess, its temperature and volume are related by the (a) 152 kJ mol–1 (b) 163 kJ mol–1
–1
equation TVn = constant, the value of n will be (c) 121 kJ mol (d) 174 kJ mol–1
(a) 1.33 (b) 0.33 (c) 2.33 (d) 1 44. For the gas - phase decomposition,
35. Molar heat capacity of water at constant pressure P is D
PCl5(g) PCl3(g) + Cl2(g):
75 J K–1. When 1 kJ of heat is supplied to 100 g of wa- (a) DH < 0, DS < 0 (b) DH > 0, DS > 0
ter which is free to expand, the increasing temperature (c) DH > 0, DS < 0 (d) DH < 0, DS > 0
of water is 45. A reaction has DH = –33 kJ and DS = –58 J/K. This
(a) 1.2 K (b) 2.4 K (c) 4.4 K (d) 6.6 K reaction would be
36. The D r H o for CO2(g) + H2(g) Æ CO(g) + H2O(g) is (a) spontaneous at all temperature
DHf CO2(g) = –393.5 kJ mol–1 (b) non-spontaneous at all temperature
DHf CO(g) = –110.5 kJ mol–1 (c) spontaneous above a certain temperature only
(d) spontaneous below a certain temperature only
DHf H2O(g) = –241.8 kJ mol–1 46. Calculate the work obtained in 1000 cycles of a revers-
(a) +524.1 kJ mol–1 (b) +41.2 kJ mol–1 ible engine operating between 1000 K and 300 K if heat
–1
(c) –262.5 kJ mol (d) –41.2 kJ mol–1 absorbed at the higher temperature is 2.1 kJ cycle–1. If
37. One mole of ice is converted into water at 273 K. The this engine operates in the reverse direction, how much
entropies of H2O(s) and H2O(l) are 38.20 and 60.01 J of work is needed to transfer 2.1 kJ of heat from the
mol–1 K–1 respectively. The enthalpy change for the sink (300 K)?
conversion is (a) 1.470 kJ (b) 4.9 kJ
(a) 59.54 J mol–1 (b) 5954 J mol–1 (c) 10.8 kJ (d) 62 kJ
–1
(c) 594.5 J mol (d) 320.6 J mol–1 47. For the given heat of reaction,
38. An ideal gas expands in volume from 10–3 m3 to 10–2 (i) C(s) + O2(g) h CO2(g) + 97 kcal
m3 at 300 K against a constant pressure of 105 N m–2. (ii) CO2(g) + C(s) h 2CO(g) – 39 kcal
The work done is The heat of combustion of CO(g) is
(a) 900 kJ (b) –900 kJ (c) 270 kJ (d) –900 J (a) 68 kcal (b) – 68 kcal
39. For a reversible process at T = 300 K, the volume of 2 (c) + 48 kcal (d) –48 kcal
moles of ideal gas is increased from 1 L to 10 L, the DH 48. The heat of combustion of sucrose, (C12H22O11(s)) at
for isothermal change is constant volume is –1348.9 kcal mol–1 at 25°C, then
(a) 11.47 J (b) 4.98 kJ (c) 0 (d) 11.47 kJ the heat of reaction at constant pressure, when steam is
40. Enthalpies of formation of CO(g), CO2(g), N2O(g) and produced, is
N2O4(g) are –110, – 393, 81 and 9.7 kJ mol–1 respec- (a) –1348.9 kcal (b) +1342.344 kcal
tively. Find the value of DrH for the reaction: (c) +1250 kcal (d) –1250 kcal
N2O4(g) + 3CO(g) h N2O(g) + 3CO2(g) 49. For the given reaction
(a) –778 kJ (b) –573 kJ (c) –105 kJ (d) +877 kJ H2(g) + F2(g) h 2HF(g) DH° = –124 kcal

H2(g) h 2H(g) DH° = 104 kcal they are neutralised by a common base. The acidic
F2(g) h 2F(g) DH° = 37.8 kcal character obeys which of the following order?
(a) A > B > C > D (b) A > D > C > B
then the value of DH° for
(c) D > C > B > A (d) D > B > C > A
H(g) + F(g) h HF(g) is
59. In C2H4 energy of formation of (C + C) and (C – C) are
(a) 142 kcal (b) –132.9 kcal
–145 kJ/mol and –80 kJ/mol respectively. What is the
(c) 132 kcal (d) 134 kcal
enthalpy change when ethylene polymerises to form
50. At constant temperature and pressure which one of the
polythene?
following statements is correct for the reaction?
(a) +650 kJ/mol (b) +65 kJ/mol
CO(g) + 1/2O2(g) h CO2(g) (c) –650 kJ/mol (d) –65 kJ/mol
(a) DH = DE 60. For the reaction shown, which is closest to the value of
(b) DH < DE DH?
(c) DH > DE 2Cr+3(aq) + 3Ni(s) Æ 2Cr(s) + 3Ni+2(aq)
(d) DH is independent physical state of reactant +3 +2
51. The heats of combustion of yellow phosphorus and red DH 0f of Cr(aq) and Ni (aq) are -143 and - 54 kJ/mol
phosphorous are –9.19 kJ an –8.78 kJ respectively, then
(a) 124 kJ (b) 89 kJ
heat of transition of yellow phosphorous to red phos-
(c) –89 kJ (d) –124 kJ
phorous is
61. If bond enthalipies of N ∫ N, H–H and N–H are x, y
(a) –17.97 kJ (b) +0.41 kJ and z kJ/mol respectively. Then enthalpy of formation
(c) +17.97 kJ (d) –0.41 kJ of NH3 is
52. For the reaction,
x 3y
C7H8(l) + 9O2(g) Æ 7CO2(g) + 4H2O(l), the calculated (a) x + 3y – 6z (b) + - 3z
heat of reaction is 232 kJ/mol and observed heat of re- 2 2
x 3y
action is 50.4 kJ/mol, then the resonance energy is (c) 3 z - - (d) 6z – x2 – 3y
2 2
(a) –182.2 kJ/mol (b) +182.2 kJ/mol
(c) 172 kJ/mol (d) –172 kJ/mol 62. When a certain amount of ethylene was burnt 6226 kJ
53. The heat of transition for CDiamond Æ CAmorphus from the heat was evolved. If heat of combustion of ethylene is
following is 1411 kJ, the volume of air (at NTP) that entered in the
reaction is
CDiamond + O2(g) h CO2(g) DH = –94.3 kcal
(a) 296.5 litre (b) 1482.5 litre
CAmorphus + O2(g) h CO2(g) DH = –97.6 kcal (c) 6226 ¥ 22.4 L (d) 22.4 L
(a) 3.3 kJ/mol (b) 3.3 kcal/mol 63. If, H2(g) + Cl2(g) Æ 2HCl; DHo = –44 kcal
(c) –3.3 kJ/mol (d) –3.3 kcal/mol 2Na(s) + 2HCl(g) Æ 2NaCl(s) + H2(g);
54. The heat of neutralisation of HCl by NaOH is –55.9 DH = –152 kcal
kJmol–1. If the heat of neutralisation of HCN by NaOH then, DH for 2Na + Cl2 h 2NaCl is
is –12.1 kJ/mol, the energy of dissociation of HCN is (a) 108 kcal (b) –196 kcal
(a) –43.8 kJ (b) 43.8 kJ (c) –98 kcal (d) 54 kcal
(c) 68 kJ (d) –68 kJ 64. Use the given standard enthalpies of formation to de-
55. Heat of neutralisation of a strong acid by a strong base termine the heat of reaction of the following reaction:
is equal to DH of TiCl4(g) + 2H2O(g) Æ TiO2(g) + 4HCl(g)
(a) H+ + OH– Æ H2O
(b) H2O + H+ Æ H3O+ DHofTiCl4(g) = –763.2 kJ/mole
(c) 2H2O + O2 = 2H2O DHof TiO2(g) = –944.7 kJ/mole
(d) CH3COOH + NaOH = CH3COONa + H2O
DHof H2O(g) = –241.8 kJ/mole
56. For which change DH π DE?
(a) Sucrose + H2O(l) m glucose + fructose DHof HCl(g) = –92.3 kJ/mole
(b) HCl(aq) + NaOH(aq) Æ NaCl(aq) + H2O (a) –278.1 (b) +369.2 (c) +67.1 (d) –67.1
(c) C(s) + O2(g) Æ CO2(g) 65. The heats of formation of CO2(g) and H2O(l) are –394
(d) 2SO2(g) + O2(g) m 2SO3(g) kJ/mole and –285.8 kJ/mole respectively. Using the
57. The amount of heat evolved when one mole of H2SO4 data for the following combustion reaction, calculate
reacts with two mole of NaOH is the heat of formation of C3H8(g).
(a) 13.7 kcal (b) Less than 13.7 kcal C3H8(g) + 5O2(g) Æ 3CO2(g) + 4H2O(l)
(c) More than 13.7 kcal (d) Cannot say DHo = –2221.6 kJ
58. The heats of neutralisation of four acids A, B, C, D are
(a) 212.2 (b) –143.3 (c) 185.4 (d) –103.6
–13.7, –9.4, –11.2 and –12.4 kcal respectively when

66. The heats of formation of CO2(g) and H2O(l) are –394 6. One mole of an ideal monoatomic gas at temperature T
kJ/mole and –285.8 kJ/mole respectively. Using the and volume 1 L expands to 2 L against a constant ex-
data for the following combustion reaction, calculate ternal pressure of one atm under adiabatic conditions,
the heat of formation of C2H2(g) in kJ mol–1. then final temperature of gas will be
2 C2H2(g) + 5 O2(g) Æ 4 CO2(g) + 2 H2O(l) 2 2
(a) T + (b) T –
3 ¥ 0.0821 3 ¥ 0.0821
DHo = –2601 kJ
(a) – 238.6 (b) 253.2 (c) 238.7 (d) 226.7 T T
(c) 5/3 -1 (d) 5/3 +1
2 2
7. The P–T graph as given below was observed for a pro-
LEVEL II cess of an ideal gas, which of the following statement
is true?
1. Given that Y
2H2(g) + O2(g) h 2H2O(g), DH = –115.4 kcal, the P
bond energy of H - H and O = O bond respectively is A B
104 kcal and 119 kcal, then the O – H bond energy in
water vapour is T
X
(a) 110.6 kcal/mol (b) – 110.6 kcal (a) w = +ve, DH = +ve (b) w = –ve, DH = –ve
(c) 105 kcal/mol (d) – 105 kcal (c) w = –ve, DH = +ve (d) w = +ve, DH = –ve
2. The piece of zinc at a temperature of 20.0°C weighing 8. How much energy must be supplied to change 36 g of
65.38 g is dropped into 180 g of boiling water (T = ice at 0°C to water at room temperature 25°C. Data
100°C). The specific heat of zinc is 0.400 J g–1 °C –1
for water, H2O DH fusion
o
= 6.01 kJ mol–1Cp.liquid = 4.18
and that of water is 4.20 J g–1 °C–1. What is the final –1 –1
J.K g
common temperature reached by both the zinc and wa-
(a) 12 kJ (b) 15.78 kJ (c) 19 kJ (d) 16 kJ
ter?
9. One mole of an ideal monoatomic gas expands isother-
(a) 97.3°C (b) 33.4°C
mally against constant external pressure of 1 atm from
(c) 80.1°C (d) 60.0°C
initial volume of 1L to a state where its final pressure
3. How much heat, in joules, must be added to 0.250 mol
becomes equal to external pressure. If initial tempera-
of Ar(g) to raise its temperature from 20°C to 36.0°C at
ture of gas is 300 K then total entropy change of system
constant pressure?
in the above process is
(a) 50.0 (b) 83.2 (c) 187 (d) 200
(R = 0.082 L atm mol–1 K–1 = 8.3 mol–1 K–1)
4. In thermodynamics, a process is called reversible
(a) 0 (b) Rln(24.6)
when
(c) Rln (2490) (d) Rln(24.6)
(a) surroundings and system change into each other.
10. The enthalpy change for a given reaction at 298 K is –x
(b) there is no boundary between system and sur-
J mol–1 (x being positive). If the reaction occurs spon-
roundings.
taneously at 298 K, the entropy change at that tempera-
(c) the surrounding are always in equilibrium with
ture
the system.
x
(d) the system changes into the surroundings sponta- (a) can be negative but numerically larger than .
neously. 298
5. One mole of an ideal monoatomic gas is caused to go (b) can be negative but numerically smaller than
through the cycle as shown in figure. Then the change x
.
in the internal energy in expanding the gas from a to c 298
along the path abc is (c) cannot be negative.
(d) cannot be positive.
2P0 c 11. If DG = –177 K cal for reaction (1)
3
2Fe(s) + O2 (g) h Fe2O3(s)
Pressure
2
T0 and DG = –19 K cal for reaction (2)
P0 b
a 4Fe2O3(s) + Fe(s) h 3Fe3O4(s)
What is the Gibbs free energy of formation of Fe3O4?
V0 4V0
Volume k cal k cal
(a) + 229.6 (b) –242.3
mol mol
(a) 3P0V0 (b) 6RT0
(c) 4.5RT0 (d) 10.5RT0 k cal k cal
(c) –727 (d) –229.6
mol mol

12. Given the following data: 17. For which of the following reactions. DS will the maxi-
Substance DH°f (kJ/mol) S° (J/mol K) mum?
FeO (s) –266.3 57.49 (a) N2(g) + 3H2(g) m 2NH3(g)
C(Graphite) 0 5.74 (b) CaCO3(s) m CaO(s) + CO2(g)
Fe(s) 0 27.28 (c) N2(g) + O2(g) m 2NO(g)
CO(g) –110.5 197.6 (d) 2HI(g) m H2(g) + I2(s)
Determine at what temperature the following reaction 18. What can be concluded about the values of DH and DS
is spontaneous? from this graph?
FeO(s) + C(graphite) h Fe(s) + CO(g)
(a) 298 K
(b) 668 K +100
DG kJ mol–1
(c) 966 K +50
(d) DG° is positive, hence the reaction will never be 0
spontaneous –50
13. Out of boiling point (I), entropy (II), pH (III) and e.m.f. –100
of a cell (IV) Intensive properties are:
100 200 300 400 500
(a) I, II (b) I, II, III Temperature, K
(c) I, III, IV (d) all of these
14. q, w, DE and DH for the following process ABCD for a (a) DH > 0, DS > 0 (b) DH > 0, DS < 0
monoatomic gas are: (c) DH < 0, DS > 0 (d) DH < 0, DS < 0
19. What amount of heat energy (kJ) is released in the
P A B combustion of 12.0 g of C3H4?
P0
(Atomic weights: C = 12.01, H = 1.008, O = 16.00).
Isothermal C3H4(g) + 4O2(g) Æ 3CO2(g) + 2H2O(l)
DH° = –1939.1 kJ
C
D (a) 725 (b) 504 (c) 783 (d) 581
20. The standard enthalpy of formation of propene, C3H6,
V0 2V0 4V0
V is +20.6 kJ/mole. Calculate the heat of combustion of
C3H6. The heats of formation of CO2(g) and H2O(l) are
(a) w = –2P0V0 ln 2, q = 2P0V0 ln 2, DE = 0, DH = 0
–394 kJ/mole and –285.8 kJ/mole respectively.
(b) w = –2P0V0 ln 2, q = 2P0V0 ln 2, DE = 0, DH =
(a) 1721.2 (b) –1939.1 (c) 2060.0 (d) 2221.6
2P0V0 ln 2
21. The fat, glyceryl trioleate, is metabolised via the fol-
(c) w = –P0V0 (1+ln2), q = P0V0 (1 + ln 2), DE = 0,
lowing reaction. Given the enthalpies of formation, cal-
DH = 0
culate the energy (kJ) liberated when 1.00 g of this fat
(d) w = –P0V0 ln 2, q = P0V0 ln 2, DE = 0, DH = 0
reacts.
15. One mole of a real gas is subjected to heating at con-
(Atomic weights: C = 12.01, H = 1.008, O = 16.00).
stant volume from (P1, V1, T1) state to (P2, V1, T2)
state. Then it is subjected to irreversible adiabatic com- C57H104O6(s) + 80O2(g) Æ 57CO2(g) + 52H2O(l)
pression against constant external pressure P3 atm till DHo C57H107O6 = –70870 kJ/mole
system reaches final state (P3, V2, T3). If the constant DHo H2O(l) = –285.8 kJ/mole
volume molar heat capacity of real gas is Cv, find out
DHo CO2(g) = –393.5 kJ/mole
correct expression for DH from state 1 to state 3.
(a) Cv(T3 – T1) + (P3V1 – P1V1) (a) 40.4 (b) 33.57 (c) 37.98 (d) 42.6
(b) Cv(T2 – T1) + (P3V2 – P1V1) 22. Using the enthalpies of formation, calculate the energy
(c) Cv(T2 – T1) + (P3V1 – P1V1) (kJ) released when 3.00 g of NH3(g) reacts according
(d) Cp(T2 – T1) + (P3V1 – P1V1) to the following equation:
16. A system is changed from an initial state to a final state (Atomic weights: B = 10.81, O = 16.00, H = 1.008).
by a manner such that DH = q. If the same change from 4 NH3(g) + 5 O2(g) Æ 4 NO(g) + 6 H2O(g)
the initial state to the final state were made by a differ- DH° NH3(g) = –46.1 kJ/mole
ent path, which of the following statements are correct?
DH° NO(g) = +90.2 kJ/mole
(a) DH remain the same.
(b) DH will depend upon the type of path. DH° H2O(g) = –241.8 kJ/mole
(c) Heat exchanged q will be same if the path is iso- (a) 34.3 (b) 30.8 (c) 39.9 (d) 42.6
baric. 23. A sheet of 15.0 g of gold at 25.0°C is placed on a 30.0 g
(d) Heat exchanged q will be different if the path is sheet of copper at 45.0°C. What is the final temperature
not isobaric. of the two metals assuming that no heat is lost to the

surroundings. The specific heats of gold and copper are if the molar ratio of C2H4 to CH3CHO is 8: 1 in a set of
0.129 J/g°C and 0.385 J/g°C respectively. product gases, then the energy involved in the decom-
(a) 42.1 (b) 40.1 (c) 41.1 (d) 43.4 position of 1 mole of ethanol is
24. Calculate the heat of combustion (kJ) of propane, C3H8 (a) 65.98 kJ (b) 48.137 kJ
using the listed standard enthapy of reaction data: (c) 48.46 kJ (d) 57.22 kJ
C3H8(g) + 5O2(g) Æ 3CO2(g) + 4H2O(g) 30. Reactions involving gold have been of particular inter-
3C(s) + 4H2(g) Æ C3H8(g) DHo/kJ = –103.8 est to a chemist. Consider the following reactions:
C(s) + O2(g) Æ CO2(g) DHo/kJ = –393.5 Au(OH)3 + 4HCl h HAuCl4 + 3H2O,
DH = –28 kcal
H2(g) + 1/2O2(g) Æ H2O(g) DHo/kJ = –241.8
Au(OH)3 + 4HBr h HAuBr4 + 3H2O,
(a) –2043.9 (b) –1532.9 DH = –36.8 kcal
(c) –1021.9 (d) –739.1
In an experiment there was an absorption of 0.44 kcal
25. Calculate the value of DHo/kJ for the following reac-
tion using the listed thermochemical equations: when one mole of HAuBr4 was mixed with 4 moles
of HCl. What is the percentage conversion of HAuBr4
2C(s) + H2(g) Æ C2H2(g)
into HAuCl4?
2C2H2(g) + 5O2(g) Æ 4CO2(g) + 2H2O(l) (a) 0.5 % (b) 0.6 %
DHo/kJ = –2600 kJ (c) 5 % (d) 50%
C(s) + O2(g) Æ CO2(g) DHo/kJ = –390 kJ
2H2(g) + O2(g) Æ 2H2O(l) DHo/kJ = –572 kJ LEVEL III
(a) +184 (b) +214 (c) +202 (d) +234
26. Use the given standard enthalpies of formation to de- 1. Match the following:
termine the heat of reaction of the following reaction:
C2H5OH(l) + 3O2(g) Æ 2CO2(g) + 3H2O(g) Column I Column II
DH fo C2 H5OH(l) = - 277.7 kJ/mole (A) H2O (l, 1 atm, 263 K) Æ (P) DrG > 0
H2O (S, 1 atm, 263 K)
DH fo CO 2 (g) = - 393.5 kJ/mole (B) H2O (l , 1 atm, 363 K) Æ (Q) DrS > 0
DH fo H 2O(g) = - 241.8 kJ/mole H2O (g, 1 atm, 363 K)
(a) –1456.3 (b) –1234.7 (C) H2O (l, 1 atm, 373 K) Æ (R) DrH < 0
(c) –1034.0 (d) –1119.4 H2O (g, 1 atm, 373 K)
27. Calculate DH°/kJ for the following reaction using the (D) H2O (S, 1 atm, 373 K) (S) DrE > 0
listed standard enthapy of reaction data: Æ H2O (l, 1 atm, 373 K)
2N2(g) + 5O2(g) Æ 2N2O5(s) 2. Match the following:
N2(g) + 3O2(g) + H2(g) Æ 2HNO3(aq)
DHo/kJ = –414.0 Column I Column II
N2O5(s) + H2O(l) Æ 2HNO3(aq) (A) Endothermic 1
DHo/kJ = –86.0 reactions (P) H2(g) + O2(g) Æ H2O(l)
2
2H2(g) + O2(g) Æ 2H2O(l)
DHo/kJ = –571.6 (B) Exothermic (Q) NH3(g) Æ N(g) + 3H(g)
reaction
(a) –84.4 (b) –243.6 (c) –71.2 (d) –121.8
28. Determine DHo/kJ for the following reaction using the (C) |DH| = |DE| (R) CH4(g) + 2O2(g) Æ CO2(g) +
listed enthalpies of reaction: 2H2O(l)
4CO(g) + 8H2(g) Æ 3CH4(g) + CO2(g) + 2H2O(l) 1 1
(D) |DH| π |DE| (S) H2(g) + Cl2(g) Æ HCl (g)
C(graphite) + 1/2O2(g) Æ CO(g) DHo/kJ = –110.5 kJ 2 2
CO(g) + 1/2O2(g) Æ CO2(g) DHo/kJ = –282.9 kJ
3. Match the following:
H2(g) + 1/2O2(g) Æ H2O(l) DHo/kJ = –285.8 kJ
Column I Column II
C(graphite) + 2H2(g) Æ CH4(g) DHo/kJ = –74.8 kJ
(a) –622.4 (b) –686.2 (c) –747.5 (d) –653.5 (A) B (P) Temperature is
29. Ethanol undergoes decomposition to form two sets of increasing
products? P
1 A
C2H4(g) + H2O(g) DH° = 45.54 kJ
C2H5OH(g)
2 CH CHO(g) + H (g) DH° = 68.91 kJ
3 2
V

(B) (Q) Isotherm NH3 is equal to one-third of the energy of dissociation of NH3
because there are three N-H bonds and those of C—H bond
in CH4 is equal to one-fourth of the energy of dissociation of
P A B CH4. Heat of a reaction = Bond energy of reactants - Bond
energy of products.
6. The enthalpy changes for the reaction
T H2O(g) h H(g) + OH(g) and
OH(g) h O(g) + H(g) are 501.87 kJ mol–1
(C) A (R) Isochoric
and 423.38 kJ mol–1. The bond enthalpy of O–H bond is
(a) –462.625 kJ mol–1 (b) 462.625 kJ mol–1
P (c) –713.54 kJ mol–1 (d) 713.54 kJ mol–1
B 7. In which of the following , the bond enthalpy and bond
dissociation enthalpy are identical?
T (a) H– H bond enthalpy in H2 (g)
(b) O–H bond ehthalpy in H2O (g)
(D) B (S) Pressure is in-
(c) C– H bond enthalpy in CH4(g)
creasing
(d) N– H bond enthalpy in NH3 (g)
8. Find the bond enthalpy of S–S bond from the following
P A data:
C2H5 – S–C2H5 (g) DH fo = –147.23 kJ mol–1
T C2H5 – S–S–C2H5 (g) DH fo = –201.92 kJ mol–1
S (g) DH f = 222.80 kJ mol–1
o
4. Match the following:
(a) –277.49 kJ mol–1 (b) 277.49 kJ mol–1
Column I Column II
(c) –349.15 kJ mol–1 (d) 349.15 kJ mol–1
1 (P) Standard
CO(g) + O2(g) Æ CO2(g) enthalpy of Comprehension 2 (Questions 9 to 11)
(A) 2
formation Two vessels A and B are connected via a stopcock. The vessel
of CO2 A is filled with a gas at a certain pressure and the vessel B is
C(graphite) + O2(g) Æ CO2(g) (Q) Enthalpy completely evacuated. The entire assembly is immersed in a
(B)
of reaction large vat of water and is allowed to come to thermal equilib-
(R) Enthalpy rium with the water. The stopcock is opened and the gas is al-
1
H2(g) + O2(g) Æ H2O(l) of combus- lowed to expand till both the vessels are uniformly occupied.
(C) 2 After sometime when the vessel has again come to thermal
tion of CO
(g) equilibrium, temperature of the water is recorded. The result
shows that the temperature of water after the experiment is
2H2(g) + O2(g) Æ 2H2O(g) (S) Standard
the same as that before.
enthalpy of
(D) 9. For the expansion referred to above, which of the fol-
formation
lowing is true?
of H2O(l)
(a) du = 0 (b) du >0 (c) du < 0 (d) dq > 0
5. Match the following: 10. Taking ‘u’ as a function of T and V, under the given
conditions of the experiment. Choose the correct state-
Column I Column II ment.
A. Isothermal process P. q = DU (a) The change in energy of a gas with change of vol-
B. Adiabatic process Q. w = –P×DV ume at constant temperature is a positive quantity.
(b) The energy of the gas is a function of temperature
C. Isobaric process R. w = DU
only.
D. Isochoric process S. w = –n RT ln V2/V1) (c) The change in energy of a gas with change of vol-
ume at constant temperature is a negative quantity.
Comprehension 1 (Questions 6 to 8) (d) The result is applicable to both ideal and real gases.
The bond dissociation energy of a diatomic molecule is also 11. The expansion that occurred is
called bond energy. However, the bond dissociation energy (a) isothermal reversible expansion
depends upon the nature of bond and also the molecule in (c) isothermal irreversible expansion
which the bond is present .The bond energy of N—H bond in (c) adiabatic reversible expansion
(d) isothermal free expansion

Comprehension 3(Questions 12 to 16) CF4 –679.6

Standard Gibb’s energy of reaction (DrG°) at a certain tem- CCl4 –106.6
perature can be computed as DrG° = DrH° – T. DrS° and the 17. The enthalpy change for reaction (i).
change in the value of DrH° and DrS° for a reaction with tem- (a) 100.23 kJ/mol (b) 127.5 kJ/mol
perature can be computed as follows: (c) –127.5 kJ/mol (d) –100.23 kJ/mol
18. (i) Use the expressions
D r H To2 – D r H To1 = D r C op (T2 – T1 ) CX4(g) h C(s) + 2X2(g) DH= –DHf
ÊT ˆ C(s) h C(g) ; DH=718 kJ/mol and
D r STo2 – D r STo1 = D r C op ln Á 2 ˜ 2X2(g) h 4X(g) ; DH = 2D(X – X)
Ë T1 ¯
where X = F,Cl, to the enthalpy change for the two pro-
DrG° = DrH° – T ◊ DrS° and by DrG° = –RT ln Keq. cesses
Consider the following reaction: CX4(g) h C(g) + 4X(g)
CO(g) + 2H2(g) m CH3OH(g) What is the average C–X bond energies for the species
Given: CX4(g) (where X = F, Cl).
DfH° (CH3OH, g) = –201 kJ/mol ; (a) 329.5 kJ/mol, 426.75 kJ/mol
DfH° (CO, g) = – 114 kJ/mol (b) 426.75 kJ/mol, 329.5 kJ/mol
S°(CH3OH, g) = 240 J/K–mol ; S°(H2, g) = 29 JK–1 mol–1 (c) –329.5 kJ/mol, –426.75 kJ/mol
S°(CO, g) = 198 J/mol–K ; C op , m (H2) = 28.8 J/mol–K (d) –426.75 kJ/mol, –329.5 kJ/mol
19. Given that the C–H bond energy is 416.1 kJ/mol, the
C op , m (CO) = 29.4 J/mol–K ; C op , m (CH3OH) = 44 J/mol–K order of relative chemical reactivities of C–H, C–F, and
C–Cl bonds.
Ê 320 ˆ (a) C – H > C – Cl > C – F
and ln Á
Ë 300 ˜¯
= 0.06, all data at 300 K
(b) C – F > C – Cl > C – H
12. DrS° at 300 K for the reaction is (c) C – Cl > C – H > C – F
(a) 152.6 J/K–mol (b) 181.6 J/K–mol (d) C – Cl > C – F > C – H
(c) –16 J/K–mol (d) none of these Multiple Correct Type Questions
13. DrH° at 300 K for the reaction is
(a) –87 kJ/mol (b) 87 kJ/mol 20. A 0.138 g sample of solid magnesium (molar mass =
24.30 g mol–1) is burned in a constant volume bomb
(c) –315 kJ/mol (d) –288 kJ/mol
calorimeter that has a heat capacity of 1.77 kJ/°C.
14. DrS° at 320 K is
The calorimeter contains 300 mL of water (density 1g
(a) 155.18 J/mol–K (b) 150.02 J/mol–K
mL–1) and its temperature is raised by 1.126°C . Which
(c) 172 J/mol–K (d) none of these
of the following is/are correct?
15. DrH° at 320 K is
(a) qcombustion = –3.405 kJ
(a) –288.86 kJ/mol (b) –289.1 kJ/mol (b) DU = –599.5 kJ/mol
(c) –87.86 kJ/mol (d) none of these (c) DH = –602.08 kJ/mol
16. DrG° at 320 K is (d) DH = –300 kJ/mol
(a) –48295.2 kJ/mol (b) –240.85 kJ/mol 21. By how much does the entropy of 3 mol of an ideal gas
(c) 240.85 kJ/mol (d) –83.56 kJ/mol change in going from a pressure of 2 bar to a pressure
Comprehension 4(Questions 17 to 20) of 1 bar, without any change in temperature. If the sur-
roundings too are at 1 bar pressure and 300 K, and the
The industrial preparation of a polymer, PTFE, is based on expansion is against the constant external pressure of
the synthesis of the monomer CF2 = CF2, which is produced the surroundings.
according to reaction (i) below. (a) q = (12.47 JK–1)T (b) DSsurr = –12.47 JK–1
2CHClF2(g) h CF2= CF2(g) + 2HCl (i) (c) DSTotal = +ve (d) DSTotal = –ve
The monomer CF2= CF2 is also obtained by reaction (ii) be- 22. For which of the following processes, total entropy of
low: universe increases?
2CHF3(g) h CF2= CF2(g) + 2HF(g) ; DH = 198.1kJ/mol (a) Melting one mole of ice to water at 0°C.
(b) Freezing one mole of water to ice at 0°C.
(ii)
(c) Freezing one mole of water to ice at – 10°C.
Consider the information below to answer the questions: (d) Melting one mole of ice at 10°C into water.
Compound DHf MoleculeX–X D(X–X) 23. One mole of helium is mixed with 2 mol of neon, both
HCl(g) –92.3 F–F 154.7 at the same temperature and pressure. Calculate DS for
CHClF2(g) –485.2 Cl–Cl 246.7 this process if the total volume remains constant.
(a) DSHe = 9.136 JK–1 (b) DSNe = 5.743 JK–1
CF2 = CF2(g) –658.3
(c) DSmix = 15.879 JK–1 (d) DSHe = 2.6 JK–1

24. 20 g of N2 at 300 K is compressed reversibly and adia- 36. The heat of combustion of glycogen is about 480
batically from 20 dm3 to 10 dm3 . Which of the follow- kJ/mol of carbon. Assume that average heat loss by an
ing is/are correct? adult male is 150 watt. If we were to assume that all
(a) T2 = 396 K (b) DU = 1424.69 J the heat comes from oxidation of glycogen, how many
(c) DH = 1994.56 J (d) T2 = 200 K units of glycogen (1mole carbon per unit) must be oxi-
dised per day to provide for this heat loss?
Integer and Subjective Type Questions
37. Calculate DH fo for chloride ion from the following
25. The enthalpy change involved in the oxidation of glu- data:
cose is –2880 kJ mol–1. Twenty five percent of this 1 1
energy is available for muscular work. If 100 kJ of H 2 (g) + Cl2 ( g ) h HCl(g); DH fo = - 92.4 kJ
2 2
muscular work is needed to walk 1 km, what is the + -
maximum distance in km that a person will be able to HCl(g) + nH 2O h H (aq) + Cl(aq) ; DH o = - 74.8 kJ
walk after eating 125 g of glucose? +
DH fo H (Aq) = 0.0 kJ
26. Calculate the enthalpy change in kcal when infinite-
ly dilute solutions of CaCl2 and Na2CO3 are mixed. 38. A constant pressure calorimeter consists of an insulated
DH fo for Ca2+(aq.), CO32- and CaCO3(s) are –129.80, beaker of mass 92 g made up of glass with heat capac-
–161.65 and –288.45 kcal mol–1 respectively. ity 0.75 J/K/g. The beaker contains 100 mL of 1 M HCl
27. An intimate mixture of ferric oxide and aluminium is of 22.6°C to which 100 mL 1M NaOH at 23.4°C is
used as solid fuel in rockets. Calculate the fuel value added. The final temperature after the reaction is com-
in kcal per cm3 of the mixture. Heats of formation and plete is 29.3°C. What is DH in kJ/mole for this neutrali-
densities are as follows: sation reaction? Assume that the heat capacities of all
H f (Al2O3 ) = –399 kcal mol–1; solutions are equal to that of same volumes of water.
39. The standard enthalpy of combustion at 25°C of hydro-
H f (Fe2O3 ) = –195.92 kcal mol–1 gen, cyclohexene (C6H10) and cyclohexane (C6H12) are
Density of F2O3 = 5.2 g/cm3; Density of Al = 2.7 g/cm3. –241, – 3800 and – 3920 kJ/mole respectively. Calcu-
28. Calculate the entropy change for the following revers- late the heat of hydrogenation of cyclohexene.
ible process at 13°C. 40. Calculate enthalpy change of the following reaction:
a – Tin m b – Tin (DHtrans = 2288 J mol–1) H2C = CH2(g) + H2(g) h H3C – CH3(g)
1 mol at 1 atm 1 mol at 1 atm The bond energy of C – H, C – C, C = C, H – H are 414,
29. Heat of neutralisation between HCl and NaOH is –13.7 347, 615 and 435 kJ/ mol respectively.
k. cal. If heat of neutralisation between CH3 COOH 41. For the reaction, N2(g) + 3H2(g) h (2NH3(g);
and NaOH is –11.7 k. cal. Calculate heat of ionisation DH = –95.4 kJ and DS = –198.3 J/K. Calculate the max-
of CH3COOH in kcal. imum temperature at which the reaction will proceed in
30. A gas occupies 2 L at STP. It is provided 58.63 J heat forward direction.
so that its volume becomes 2.5 L at 1 atm. Calculate 42. Assume that for a domestic hot water supply 150 kg
change in its internal energy in Joule. of water per day must be heated from 10°C to 65°C
31. A sample of ideal gas (g = 1.4) is heated at constant
and gaseous fuel propane C3H8 is used for this purpose.
pressure. If an amount of 85 J of heat is supplied to gas,
What moles and volume of propane ( in litre at STP )
find DU in Joule.
would have to be used for heating domestic water. DH
32. Calculate the free energy change in kJ when 1 mole of
for combustion of propane is –2050 kJ/ mol and spe-
NaCl is dissolved in water at 298 K. Given,
(a) Lattice energy of NaCl = 778 kJ mol–1 cific heat of water is 4.184 ¥ 10–3 kJ/g.
(b) Hydration energy of NaCl = –775 kJ/mol–1 43. A gas expands from 3 dm3 to 5 dm3 against a constant
(c) Entropy change at 300 K = 40 J mol–1 pressure of 3 atm. The work done during expansion is
33. Calculate the maximum work done in kJ expanding 16 used to heat 10 mole of water of temperature 290 K.
g of oxygen at 300 K and occupying a volume of 5dm3 Calculate (DT ¥ 10) of water. Specific heat of water =
isothermally until the volume becomes 25dm3 . 4.184 J/ g/K.
34. What is the entropy change for the conversion of 1 g 44. Diborane is a potential rocket fuel which undergoes
of ice to water at 167 K and one atmospheric pressure? combustion according to the reaction,
[DHfusion = 6.025 kJ mol–1]. B2H6(g) + 3O2(g) h B2O3(s) + 3H2O(g)
35. At 300 K, the standard enthalpies of formation of From the following data, calculate the enthalpy change
C6H5COOH(s), CO2(g) and H2O(l) are –408, –393 and for the combustion of diborane:
–286 kJ/ mol respectively. Calculate the heat of com- Ê 3ˆ
bustion of benzoic acid at (i) 2B(s) + ÁË ˜¯ O2(g) h B2O3(s); DH = –1273
2
(i) constant pressure (ii) constant volume kJ/mol

Ê 1ˆ 54. Find the work done when one mole of the gas is ex-
(ii) H2(g) + ÁË ˜¯ O2(g) h H2O(l); DH = –286 kJ/ panded reversibly and isothermally from 5 atm to 1 atm
2
mol at 25°C?
(iii) H2O(l) h H2O(g); DH = 44 kJ/ 55. Oxygen is heated from 300 K to 600 K at a constant
mol pressure of 1 bar. What is the increases in molar en-
(iv) 2B(s) + 3H2(g) h B2H6(g) ; DH = 36 kJ/mol tropy? The molar heat capacity in JK–1 mol–1 for the O2
45. By using the following data draw an appropriate ener- is.
gy cycle & calculate the enthalpy change of hydration CP = 25.5 + 13.6 ¥ 10–3 T – 42.5 ¥ 10–7 T2
of (i) the chloride ion ; (ii) the iodide ion.
56. Calculate the free energy change at 298 K for the reac-
Comment on the difference in their values.
tion:
* enthalpy change of solution of NaCl(s) = – 2 kJ/mol.
Br2(l) + Cl2(g) h 2BrCl(g). For the reaction DH° =
* enthalpy change of solution of NaI(s) = + 2 kJ/mol.
29.3 kJ and the entropies of Br2(l), Cl2(g) and BrCl(g)
* enthalpy change of hydration of Na+ (g)
= –390 kJ/mol. at the 298 K are 152.3, 223.0, 239.7 J mol–1 K–1 respec-
* lattice energy of NaCl = – 772 kJ/mol. tively.
* lattice energy of NaI = – 699 kJ/mol. 57. Using the date given below, establish that the vaporisa-
46. The gas is cooled and loses 65 J of heat. The gas con- tion of CCl4(l) at 298K to produce CCl4(g) at 1 atm
tracts as it cools and work done on the system equal to pressure occur spontaneously or not.
20 J which is exchanged with the surroundings. Find Given: CCl4 (l, 1 atm) h CCl4 (g, 1 atm) ;
the value of DE? DS° = 94.98 JK–1 mol–1
47. The enthalpy of combustion of glucose is –2808 kJ DH°f (CCl4, g) = –106.7 kJ mol–1 and DH°f(CCl4, l) =
mol–1 at 25°C. How many grams of glucose do you –139.3 kJ mol–1
need to consume [Assume weight = 62.5 kg]. 58. The increase in entropy of 1 kg of ice at 200 K which is
(a) To climb a flight of stairs rising through 3 m. heated to 400 K (super heated steam) at constant atmo-
(b) To climb a mountain of altitude 3000 m? spheric pressure, will be what?
Assume that 25% of enthalpy can be converted to use- Given that Cp (ice) = 2.09 ¥ 103 J/kg degree ; Cp(water)
ful work. = 4.18 ¥ 103 J/kg degree
48. What is DE when 2.0 mole of liquid water vaporises at Cp(steam) = 2.09 ¥ 103 J/kg degree ; Lf (C, 273 K) =
100°C? The heat of vaporisation, of water at 100°C is 3.34 ¥ 105 J/kg ;
40.66 kJ mol–1. Lv (water, 273 K) = 22.6 ¥ 105 J/kg
49. If 1.0 kcal of heat is added to 1.2 L of O2 in a cylinder 59. Calculate workdone in adiabatic compression of one
of constant pressure of 1 atm, the volume increases to mole of an ideal gas (monoatomic) from an initial pres-
1.5 L. Calculate DE and DH of the process. sure of 1 atm to final pressure of 2 atm. Initial tempera-
50. When the following reaction was carried out in a bomb ture = 300 K.
calorimeter, DE is found to be –742.7 kJ/mol of NH2CN (a) If process is carried out reversibly.
(s) at 298 K. (b) If process is carried out irreversible against 2 atm
3 external pressure.
NH2CN(s) + O2(g) h N2(g) + CO2(g) + H2O(l) (c) The final volume reached by gas in two cases.
2
Calculate DH298 for the reaction. 60. 20.0 dm3 of an ideal gas (diatomic Cv,m = 5 R/2) at 673
51. When 1 mole of ice melt at 0°C and at constant pres- K and 0.7 MPa expands until pressure of the gas is 0.2
sure of 1 atm. 1440 calories of heat are absorbed by MPa. Calculate q, w, DU and DH for the process if the
the system. The molar volumes of ice and water are expansion is
0.0196 L and 0.0180 L respectively. Calculate DE for (i) isothermal and reversible.
the reaction. (ii) adiabatic and reversible.
52. Water expands when it freezes. Determine amount of (iii) isothermal and adiabatic.
work in joules, done when a system consisting of 1.0 L (iv) against 0.2 MPa and adiabatic.
of liquid water freezes under a constant pressure of 1.0 (v) against 0.2 MPa and isothermal.
atm and forms 1.1 L of ice. 61. One mole of an ideal gas is expanded isothermally at
53. One mole of solid Zn is placed in excess of dilute 298 K until its volume is tripled. Find the values of
H2SO4 at 27°C in a cylinder fitted with a piston. Find DStotal under the following conditions:
the value of DE, q and w for the process if the area of (i) Expansion is carried out reversibly.
piston is 500 cm2 and it moves out by 50 cm against a (ii) Expansion is carried out irreversibly where 836.6
pressure of 1 atm during the reaction. The heat given to J of heat is less absorbed than in (i)
surrounding is 36.5 kJ. (iii) Expansion is free.
Zn(s) + 2H+(aq) m Zn2+(aq) + H2(g)

62. 10 g of neon initially at a pressure of 506.625 kPa and PCl5(g) m PCl3(g) + Cl2(g)
temperature of 473 K expand adiabatically to a pres- Also, calculate the standard entropy change if
sure of 202.65 kPa. Calculate entropy change of the DHº = 28.40 kJ mol–1.
system and total entropy change for the following ways 74. One mole of a perfect monoatomic gas is put through a
of carrying out this expansion: cycle consisting of the following three reversible steps:
(i) Expansion is carried out reversibly. T2
T1
(ii) Expansion occurs against a constant external (20, 1) (20, 10)
pressure of 202.65 kPa. A B
(iii) Expansion is free expansion.
63. Pressure over 1000 mL of a liquid is gradually increas- P
es from 1 bar to 1001 bar under adiabatic conditions.
C
If the final volume of the liquid is 990 mL, calculate T1 (2, 10)
DU and DH of the process, assuming linear variation of
V
volume with pressure. (Use 1 L-atm = 100 J)
64. One mole of ideal monoatomic gas was taken through (CA) Isothermal compression from 2 atm and 10 L to
reversible isochoric heating from 100 K to 1000 K. 20 atm and 1 L.
Calculate DSsystem, DSsurr, and DStotal (AB) Isobaric expansion to return the gas to the origi-
(i) when the process is carried out reversibly. nal volume of 10 L with T going from T1 to T2.
(ii) when the process is carried out irreversibly (one (BC) Cooling at constant volume to bring the gas to the
step). original pressure and temperature.
65. Fixed amount of an ideal gas contained in a sealed rigid The steps are shown schematically in the figure shown.
vessel (V = 24.6 L) at 1.0 bar is heated reversibly from (a) Calculate T1 and T2.
27°C to 127°C. Determine change in Gibb’s energy (in (b) Calculate DE, q and w in calories, for the cycle.
Joule) if entropy of gas S = 10 + 10–2 T (J/K). 75. A monoatomic ideal gas of two moles is taken through
66. A 32 g sample of CH4 gas initially at 101.325 kPa and a cyclic process starting from A as shown in figure. The
300 K is heated to 550 K. CP,m/JK–1 mol–1 = 12.552 V V
+ 8.368 ¥ 10–2 T/K. Assuming CH4 behaves ideally, volume ratios are B = 2 and D = 4. If the tempera-
VA VA
compute w, q, DU and DH for (a) an isobaric reversible ture TA at A is 27ºC, calculate
process and (b) an isochoric reversible process.
V
67. At 298 K, DH combustion
o
(sucrose) = – 5737 kJ/mol and
D C
VD
DGcombustion
o
(sucrose) = –6333 kJ/mol. Estimate addi-
tional non-PV work that is obtained by raising temper- VB
ature to 310 K. Assume DrCP = 0 for this temperature B
VA
change. A
68. During 200J work done on the system, 140 J of heat is O T
TA TB
given out. Calculate the change in internal energy.
69. A gas absorbs 200 J of heat and expands against the (a) the temperature of the gas at point B.
external pressure of 1.5 atm from a volume of 0.5 L. (b) Total Heat absorbed or released by the gas in cy-
Calculate the change in internal energy. clic process.
70. Two litre of N2 at 0oC and 5 atm pressure are expanded (c) the total work done by the gas during complete
isothermally against a constant external pressure of 1 cycle.
atm until the pressure of gas reaches 1 atm. Assuming 76. Calculate the work done when 50 g of iron reacts with
gas to be ideal, calculate work of expansion. hydrochloric acid in
71. The enthalpy of vaporisation of liquid diethyl ether – (i) a closed vessel of fixed volume.
(C2H5)2O, is 26.0 kJ mol–1 at its boiling point (35.0ºC). (ii) an open beaker at 25°C.
Calculate DS for conversion of: (a) liquid to vapour, 77. The internal energy change in the conversion of 1.0
and (b) vapour to liquid at 35ºC. mole of the calcite form of CaCO3 to the aragonite
72. Calculate the free energy change when 1 mole of NaCl form is +0.21 kJ. Calculate the enthalpy change when
is dissolved in water at 25ºC. Lattice energy of NaCl the pressure is 1.0 bar; given that the densities of the
= 777.8 kJ mol–1 ; DS for dissolution = 0.043 kJ mol–1 solids are 2.71 g cm–3 and 2.93 g cm–3 respectively.
and hydration energy of NaCl = –774.1 kJ mol–1. 1
78. For a reaction M2O(s) Æ 2M(s) + O2(g); DH = 30 kJ
73. The equilibrium constant for the reaction given below 2
is 2.0 × 10–7 at 300 K. Calculate the standard free en- mol–1 and DS = 0.07 kJ K–1 mol–1 at 1 atm. Calculate up
ergy change for the reaction; to which temperature, the reaction would not be spon-
taneous.

79. Predict whether the entropy change of the system in 88. Calculate the heat of formation of benzene from the
each of the following process is positive or negative. following data, assuming no resonance. Bond energies:
(a) CaCO3(s) Æ CaO(s) + CO2(g) C–C = 83 kcal, C=C = 140 kcal, C–H = 99 kcal
(b) N2(g) + 3H2(g) Æ 2NH3(g) Heat of atomisation of C = 170.9 kcal
(c) N2(g) + O2(g) Æ 2NO(g) Heat of atomisation of H = 52.1 kcal
(d) HCl(g) + NH3(g) Æ NH4Cl(s) 89. At 25º C, 1 mole MgSO4 was dissolved in water. The
(e) 2SO2(g) + O2(g) Æ 2SO3(g) heat evolved was found to be 91.211 kJ. One mole of
(f) Cooling of N2(g) from 20°C to –50°C MgSO4. 7H2O on dissolution gives a solution of the
80. Calculate the boiling point of bromine from the follow- same composition accompained by an absorption of
ing data: 13.807 kJ. Find the enthalpy of hydration, i.e., DH for
DHº and DSº values of Br2(l) Æ Br2(g) are 30.91 kJ/ the reaciton,
mole and 93.2 J/mol. K respectively. Assume that DH MgSO4(s) + 7H2O(l) Æ MgSO4 . 7H2O(s)
and DS do not vary with temperature. Given that
81. The efficiency of the Carnot engine is 1/6. On decreas- (i) MgSO4 (s) + aq Æ MgSO4 (aq) DrH1 = –91.211
ing the temperature of the sink by 65K, the efficiency kJ mol–1
increases to 1/3. Find the temperature of the source and (ii) MgSO4 . 7H2O (s) + aq Æ MgSO4 (aq) DrH2 =
the sink. +13.807 kJ mol–1
82. (a) One mole of an ideal gas expands isothermally 90. The specific heats of iodine vapour and solid are 0.031
and reversible at 25ºC from a volume of 10 L to a and 0.055 cal/g respectively. If heats of sublimation of
volume of 20 L. iodine is 24 cal/g at 200°C, what is its value at 250ºC?
(i) What is the change in entropy of the gas? 91. When 2 moles of C2H6 are completely burnt 3120 kJ of
(ii) How much work is done by the gas? heat is liberated. Calculate the heat of formation, DH fo
(iii) What is q(surroundings)?
for C2H6. Give DH fo for CO2(g) and H2O(l) are –395
(iv) What is the change in the entropy of the sur- and –286 kJ respectively.
roundings? 92. The heat of solution of anhydrous CuSO4 is –15.9 kcal
(v) What is the change in the entropy of the sys- and that of CuSO4.5H2O is 2.8 kcal. Calculate the heat
tem plus the surroundings? of hydration of CuSO4.
(b) Also answer the questions (i) to (v) if the ex- 93. A swimmer breaths 20 times in one minute when swim-
pansion of the gas occurs irreversibly by simply ming and inhale 200 mL of air in one breath. Inhalded
opening a stopcock and allowing the gas to rush air contain 20% O2 by volume and exhaled air contain
into an evacuated bulb of 10-L volume. 10% O2 by volume. If all oxygen are consumed in com-
83. The molar heat of formation of NH 4 NO3(s) is
bustion of glucose in the body and 25% of energy ob-
–367.54 kJ and those of N2O(g), H2O(l) are 81.46 tained from combustion is available for muscular work.
and –285.8 kJ respectively at 25°C and 1 atmo- Determine the maximum distance this swimmer can
sphere pressure. Calculate DH and DE of the reaction
swim in one hour if 100 kJ energy is required for 1.0 km
NH 4 NO3(s) h N 2O(g) + 2H 2O(l) swimming. Standard molar enthalpy of combustion of
84. Given the following standard molar enthalpies: DHfoof glucose is –2880 kJ/mol and body temperature is 37°C.
CH3CN (g) = 88 kJ/mol, DH fo of C2H6 = – 84 kJ/mol, 94. If the enthalpy of formation of HCl (g) and Cl– (aq) are
DH Sublimation
o
of C(gr) = 717 kJ/mol, bond dissociation –92.3 kJ/mole and –167.44 kJ/mol, find the enthalpy of
energy of N2 (g) and H2 (g) are 946 and 436 kJ/mole solution of hydrogen chloride gas.
respectively, B.E. (C—H) = 410 kJ/mol. Determine 95. When 1.0 g of fructose C6H12O6(s) is burned in oxygen
C—C and C∫N bond energies. in a bomb calorimeter, the temperature of the calorim-
85. The heats of combustion of C2 H 4(g) , C2 H 6(g) and eter water increases by 1.56°C. If the heat capacity of
H 2(g) are –1409.5, –1558.3 and –285.6 kJ respectively. the calorimeter and its contents is 10.0 kJ/°C. Calculate
the enthalpy of combustion of fructose at 298 K.
Calculate heat of hydrogenation of ethylene.
96. Consider the following thermodynamic data:
86. DH for combustion of ethane and ethyne are –341.1
and –310.0 kcal respectively. Which is the better gas Enthalpy of formation of CaC2 (s) = – 60 kJ/mol;
welder and why? Enthalpy of sublimation of Ca (s) = 179 kJ/mol;
87. The heat of formation of methane is –17.9 kcal. If the Enthalpy of sublimation of C (s) = 718 kJ/mol;
heats of atomisation of carbon and hydrogen are 170.9 First ionization energy of Ca (g) = 590 kJ/mol;
and 52.1 kcal per mole, calculate the C–H bond energy Second ionization energy of Ca (g) = 1143 kJ/mol;
in methane.

Bond energy of C2 (g) = 614 kJ/mol; 104. Using the data (all values are in kJ/mol at 25°C) given
First electron affinity of C2 (g) = –315 kJ/mol; below :
Second electron affinity of C2 (g) = +410 kJ/mol; (i) Enthalpy of polymerization of ethylene = – 72.
Draw a clear Born-Haber cycle and determine lattice (ii) Enthalpy of formation of benzene (l) = 49
energy of CaC2 (s). (iii) Enthalpy of vaporization of benzene (l) = 30
97. The enthalpy change for the following process at 25°C (iv) Resonance energy of benzene (l) = – 152
and under constant pressure at 1 atm are as follows: (v) Heat of formation of gaseous atoms from the ele-
CH4(g) h C(g) + 4H(g) DrH = 396 kcal/mole ments in their standard states H = 218, C = 715.
C2H6(g) h 2C(g) + 6H(g) DrH = 676 kcal/mole Average bond energy of C—H = 415. Calculate
Calculate C–C bond energy in C2H6 and heat of forma- the B.E. of C—C and C= C.
tion of C2H6(g)
Given: Dsub C(s) = 171.8 kcal/mole
B.E. (H–H) = 104.1 kcal/mole PREVIOUS YEARS’ QUESTIONS
98. Cesium chloride is formed according to the following OF JEE (MAIN AND ADVANCED)
equation:
Cs(s) + 0.5Cl2(g) h CsCl(s). 1. The reversible expan-
sion ob an ideal gas (p1, V1, T1)
The enthalpy of sublimation of Cs, enthalpy of disso-
ciation of chlorine, ionisation energy of Cs and electron under adiabatic and Isothermal
affinity of chlorine are 81.2, 243.0, 375.7 and –348.3 kJ isothermal conditions P (p2, V2, T2)
mol–1. The energy change involved in the formation of is shown in the figure. Adiabatic (p3, V3, T3)
CsCl is –388.6 kJ mol–1. Calculate the lattice energy of Which of the following
statement(s) is (are) cor- V
CsCl.
99. The enthalpy of formation of ethane, ethylene and ben- rect? [2012]
zene from the gaseous atom are –2839.2, –2275.2 and (a) T1 = T2
–5506 kJ mol–1 respectively. Calculate the resonance (b) T3 > T1
energy of benzene. The bond enthalpy ofC–H bond is (c) Wisothermal > Wadiabatic
given as equal to +410.87 kJ/mol. (d) DUisothermal > DUadiabatic
100. Determine resonance energy of benzene [C6H6 (l)] 2. For an ideal gas, consider
from the following information : only P-V work in going
DH fo of C6H6 (l) = + 49 kJ ; from initial state X to the X Y
p(atmosphere)
final state Z. The final state
DH fo of C2H2(g) =+75 kJ DH°v of C6H6 (l) = + 45 kJ Z can be reached by either
B.E.C ∫ C (930 kJ/mol) ; C = C (615 kJ/mol) ; of the two paths shown in Z
C — C (348 kJ/mol) the figure. [2012]
101. A bomb containing 5.4g of Al and 15.97g of Fe2O3 is [Take DS as change in en-
placed in an ice calorimeter containing initially 8 kg of tropy and W as work done] V(litre)
ice and 8 kg of water. The reaction 2Al(s) + Fe2O3(s) Which of the following
Æ Al2O3(s) + 2Fe(s) is set off by remote control and it choice(s) is (are) correct?
is then observed that the calorimeter contains 7.746 kg (a) DSX Æ Z = DSX Æ Y + DSY Æ Z
of ice and 8.254 kg of water. Find the DH for the above (b) WX Æ Z = WX Æ Y + WY Æ Z
reaction. (c) WX Æ Z Æ Z = WX Æ Y
DHfusion (ice) = 1.436 kcal/mole (d) DSX Æ Y Æ Z = DSX Æ Y
102. The heat of combustion of formaldehyde(g) is 3. Using the data provided, calculate the multiple bond
–134 kcal mole–1 and the heat of combustion of energy (kJ mol–1) of a C ∫ C bond in C2H2. That energy
paraformaldehyde(s) is –122 kcal per (1/n) (CH2O)n. is (take the bond energy of a C – H bond as 350 kJ
Calculate the heat of polymerisation of formaldehyde mol–1) [2012]
to paraformaldehyde. 2C(s) + H2(g) h C2H2(g); DH = 225 kJ mol–1
103. For the reaction cis-2-butene Æ trans-2-butene and 2C(s) h 2C(g); DH = 1410 kJ mol–1
cis-2-butene Æ 1-butene, DH = – 950 and + 1771 cal/ H2(g) h 2H(g); DH = 330 kJ mol–1
mol respectively. The heat of combustion of 1-butene (a) 1165 (b) 837 (c) 865 (d) 815
is –649.8 kcal/mol. Determine the heat of combustion (Passage From Q. No. 4 to Q. No. 5)
of trans-2-butene. Also calculate the bond energy of
C=C bond in trans-2-butene. Given B.E of C = O = A fixed mass m of a gas is subjected to transformation of
196, O—H = 110, O = O = 118, C—C = 80 and C—H states from K to L to M to N and back to K as shown in the
= 98 kcal/mol respectively. DHv(H2O) = 11 kcal/mol. figure. [2013 Adv.]

K L rimeter, is 1364.47 kJ mol–1 at 25°C. Assuming ideality

the enthalpy of combustion, DCH, for the reaction will
Pressure be (R = 8.314 J K–1 mol–1)
(a) –13.66 kJ mol–1 (b) –1361.95 kJ mol–1
–1
(c) –1460.50 kJ mol (d) –1350.50 kJ mol–1
N M
10. An ideal gas in thermally insulated vessel at internal
Volume
pressure = p1, volume = V1 and absolute temperature =
4. The pair of isochoric processes among the transforma- T1 expands irreversibly against zero external pressure,
tion of states is as shown in the diagram.
(a) K to L and L to M (b) L to M and N to K The final internal pressure, volume and absolute tem-
(c) L to M and M to N (d) M to N and N to K perature of the gas are p2, V2 and T2, respectively. For
5. The succeeding operations that enable this transforma- this expansion [2014 Adv.]
tion of states are pext = 0
(a) heating, cooling, heating, cooling pext = 0 Irreversible
(b) cooling, heating, cooling, heating
(c) heating, cooling, cooling, heating p1, V1, T1 p2, V2, T2
(d) cooling, heating, heating, cooling
6. Benzene and naphthalene form an ideal solution at room Thermal insulation
temperature. For this process, the true statement(s)
is(are) [2013 Adv.] (a) q = 0 (b) T2 = T1
(a) DG is positive (b) DSsystem is positive (c) p2V2 = p1V1
g
(d) p2V2 = p1V1
g
(c) DSsurrounding = 0 (d) DH = 0
7. A piston filled with 0.04 mole of an ideal gas expands 11. For the process, H2O(l) h H2O(g) [2014 Adv.]
reversibly from 50.0 mL to 375 mL at a constant tem- at T = 100°C and 1 atmosphere pressure, the correct
perature of 37.0°C. As it does so, it absorbs 208 J of choice is
heat. The values of q and W for the process will be (a) DSsystem > 0 and DSsurrounding > 0
[2013 Main] (b) DSsystem > 0 and DSsurrounding < 0
(R = 8.314 J/mol K, ln 7.5 = 2.01) (c) DSsystem < 0 and DSsurrounding > 0
(a) q = +208 J, W = –208 J (d) DSsystem < 0 and DSsurrounding < 0
(b) q = –208 J, W = –208 J 12. The following reaction is performed at 298K.
(c) q = –208 J, W = +208 J [2015 Main]
(d) q = +208 J, W = +208 J 2NO(g) + O2(g) 2NO2(g)
8. The standard enthalpies of formation of CO2(g), H2O(l) The standard free energy of formation of NO(g) is 86.6
and glucose(s) at 25°C are –400 kJ/mol, –300 kJ/mol kJ/mol at 298 K. What is the standard free energy of
and –1300 kJ/mol, respectively. The standard enthalpy formation of NO2(g) at 298 K? KP = 1.6 ¥ 1012
of combustion per gram of glucose at 25°C is (a) R(298) In (1.6 ¥ 1012) – 86600
[2013 Adv.] (b) 86600 + R(298) ln (1.6 ¥ 1012)
(a) +2900 kJ (b) –2900 kJ ln (1.6 ¥ 1012 )
(c) –16.11 kJ (d) +16.11 kJ (c) 86600 –
R(298)
9. For the complete combustion of ethanol, [2014 Main]
C2H5OH(l) + 3O2(g) h 2CO2(g) + 3H2O(l), the (d) 0.5[2 ¥ 86600 – R(298) ln (1.6 ¥ 1012)]
amount of heat produced as measured in bomb calo-
Answer Key
LEVEL I
1. (c) 2. (c) 3. (b) 4. (d) 5. (c) 6. (a) 7. (b) 8. (a) 9. (a) 10. (a)
11. (b) 12. (c) 13. (c) 14. (b) 15. (b) 16. (b) 17. (b) 18. (a) 19. (b) 20. (d)
21. (d) 22. (c) 23. (d) 24. (b) 25. (c) 26. (a) 27. (d) 28. (c) 29. (b) 30. (c)
31. (a) 32. (b) 33. (a) 34. (b) 35. (b) 36. (b) 37. (b) 38. (d) 39. (c) 40. (a)
41. (a) 42. (b) 43. (b) 44. (b) 45. (d) 46. (a) 47. (b) 48. (a) 49. (b) 50. (b)

51. (d) 52. (a) 53. (b) 54. (b) 55. (a) 56. (d) 57. (c) 58. (b) 59. (b) 60. (a)
61. (b) 62. (b) 63. (b) 64. (d) 65. (d) 66. (d)
LEVEL II
1. (a) 2. (a) 3. (b) 4. (c) 5. (d) 6. (b) 7. (c) 8. (b) 9. (b) 10. (b)
11. (b) 12. (c) 13. (c) 14. (a) 15. (c) 16. (a) 17. (b) 18. (a) 19. (d) 20. (c)
21. (c) 22. (c) 23. (a) 24. (a) 25. (d) 26. (b) 27. (a) 18. (c) 29. (b) 30. (c)
LEVEL III
1. (A) Æ R; (B) Æ P, Q, S; (C) Æ Q, S; (D) Æ Q, S 2. [(A) Æ Q; (B) Æ P, R, S; (C) Æ S; (D) Æ P, Q, R]

3. [(A) Æ P, S; (B) Æ P; (C) Æ Q; (D) Æ P, R, S] 4. [(A) Æ R, Q; (B) Æ P, Q; (C) Æ S, Q; (D) Æ Q]
5. [(A) Æ S; (B) Æ R; (C) Æ Q; (D) Æ P]
6. (b) 7. (a) 8. (b) 9. (a) 10. (a) 11. (d) 12. (c) 13. (a) 14. (d) 15. (c)
16. (d) 17. (b) 18. (b) 19. (c) 20. (a, b, c) 21. (a, b, c) 22. (c, d) 23. (a, b, c)
24. (a, b, c) 25. (5) 26. (3) 27. (4) 28. (8) 29. (2) 30. (8) 31. (55) 32. (–9) 33. (–2)
34. (2) 35. (i) –3201 kJ, (ii) –3199.75 kJ 36. (27) 37. (–167.2 kJ) 38. (–57) 39. (–121) 40. (–125)
41. (481) 42. (377) 43. (8) 44. (–2035 kJ) 45. (–384 KJ, –307 KJ) 46. (–45 J)
47. (0.4807 g), (0.4807 kg) 48. (75.118 kJ) 49. (0.993 kcal) 50. (–741.46 KJ)
51. (1440.03877 Cal) 52. (10.13 J) 53. (–36.5 KJ, –2.5 KJ, –39.03 KJ) 54. (–3.988 kJ)
55. (20.618 kJ) 56. (–1721.8 J) 57. (Non spontenous) 58. (9383.4 J/°C)
59. (a) 1195.37 J, (b) 1496.52 J, (c) 16.25 L and 17.24 L 60. See solution 61. (i) 0, (ii) 2.807 J/K, (iii) 2.807 J/K
62. (i) 0,0 (ii) 0.957 J/K, 0.957 J/K (iii) 3.81 J/K, 3.81 J/K 63. (DU = 501 J & DH = 99.5 kJ)
Ê 3 3 ˆ Ê3 3 3 ˆ
64. (i) Á 0, – R ln 10, - R ln 10˜ (ii) Á R ln 10, – R (0.9), R (1.402)˜ 65. (– 530 J)
Ë 2 2 ¯ Ë 2 2 2 ¯
66. (a) (W = –4.15 kJ, q = DH = 24.04 kJ, DU = 19.9 kJ) (b) (W = 0, q = DU = 19.9 kJ, DH = 24.04 kJ)
67. (24 kJ/mole) 68. (+60 J) 69. (+124.025 J) 70. (–810.4 joule)
71. (a) (+84.41 JK–1 mol–1) (b) (–84.41 JK–1 mol–1) 72. (–9.114 kJ mol–1) 73. (–33.6 JK–1)
74. (a) (243.6 K, 2436 K (b) (DE = 0; q = 3262.88 cal; w = –3262.88 cal)
75. (a) (600 K); (b) (–1200 cal); (c) (1200 cal) 76. (–2212.22 J) 77. (209.72 J)
78. (T < 428.57 K) 79. ((a) positive (b) negative (c) impossible to predict (d) negative (e) negative (f) negative
80. (331.6 K) 81. (390 K, 325 K)
82. (a) (i) 5.76 J/K (ii) –1718 J (iii) 1718 J (iv) –5.76 J/K (v) 0 (b) (i) 5.76 J/K (ii) 0 (iii) 0 (iv) 0 (v) –5.76 J/K
83. (–122.6 kJ, –125.077 kJ) 84. (366 KJ, 877 KJ) 85. (136.8 KJ) 86. (C2H2)
87. (+99.3 kcal/mole) 88. (75.0 kcal) 89. (–105.018 kJ mol–1) 90. (22.8 cal/g)
91. (–88 kJ/mol) 92. (–18.7 kcal) 93. (1.132 km) 94. (–75.14 kJ/mol) 95. (–2808 kJ)
96. (– 2889 kJ/mole) 97. (84 kcal) 98. (– 618.6 kJ mol–1) 99. (–23.68 kJ/mol) 100. (–32)
101. (–202.6 kcal) 102. (12 Kcal) 103. (–604079 cal mol–1, 192.91 kcal mol–1)
104. (343.66 kJ, 615.33 kJ)
1. (a, c, d) 2. (a, c) 3. (d) 4. (b) 5. (c) 6. (b, c, d) 7. (a) 8. (c) 9. (a) 10. (a, b, c)
11. (b) 12. (d)

Hints and Solutions

11. (b) DH = DU + DngRT
LEVEL I Ê 3ˆ
DH = –742.7 kJ mol–1 + ÁË 2 - ˜¯ ¥ 8.3 ¥ 10–3 ¥ 298
2
1. (c) DU = q + w = –741.5 kJ mol–1
heat absorb (q) = 45 J 12. (c) Atomic weight of Al = 27
since w = –70 joule The heat capacity required to raise the temperature of
Work done by the system. 27g Al through 1 K is 24 Joules
DU = q + w = 45 – 70 = –25 J 60 ¥ 24 ¥ 20 ¥ 10-3
2. (c) Decrease in internal energy = –DU for 60 g Al = KJ = 1.066 kJ
27
Work done by the system = –w
13. (c) At constant T, the molecule with maximum atoms
–DU = –w fi DU = w fi q = 0
have greatest internal energy.
The process is adiabatic.
3. (b) At constant volume DV = 0 14. (b) PV = nRT
\ W = –Pext DV = 0 1.013 ¥ 106 ¥ 1 = 0.4 ¥ 8.314 ¥ T1
\ DU = q first law T1 = 304.6 K
4. (d) The energy due to external field is not included in g -1
T2 Ê V1 ˆ
internal energy like gravitational field, earth’s magnet- =
ic field, etc. T1 ÁË V2 ˜¯
5. (c) Heat and work are path dependent, or indefinite T2 = 121.28 K
quantity. nR
6. (a) For monoatomic ideal gas total degree of freedom = 3 w= (T2 - T1 )
g -1
Three translational mode of motion
w = - 923.7 J
1 3
CV = 3 ¥ R = R 15. (b) Heat of combustion is defined as heat evolved when
2 2
5 one mole of compound is completly oxidised in exces
CP = CV + R = R of air (or oxygen)
2
CP 5 35.2 ¥ - 393.5
and g = = = - 314.8 kJ
CV 3 44
16. (b) Enthalpy of formation of a compound is defined as
7. (b) Work done in adiabatic process
heat evolved or absorbed in formation of one mole of
DU = W = nCVDT
compound starting from its elemental level
W = (2)(12.5)(200 – 300)
17. (b) DG° = –2.303 RT log Keq
8. (a) Heat of reaction at constant pressure = DH
Heat of reaction at constant volume = DE = –2.303 ¥ 8.314 ¥ 10–3 ¥ 300 ¥ log 10
DH = DE + DngRT DH vapourisation
Dng = –3 18. (a) DS vapourisation =
Tb
DH – DE = (–3RT)
= –3 ¥ 8.314 ¥ 298 ¥ 10–3 = –7.431 40.73 ¥ 103
\ Tb =
9. (a) Fusion and vaporisation are example of isothermal 109
processes 19. (b) When ice m liquid: the process is reversible fu-
sion. The fusion is isothermal process.
dq dq
100°C R T C =
T Vaporisation dT 0
0
fusion 20. (d) DU = q + w
Q P = constant since DH = qp
–10
Heat
X 202.6 = DU + 1 atm (2 L)
T f < Tb PQ – Tf RT – Tb fi DU = 202.6 – 2(L atm) (101.325 J/L atm)
10. (a) DH = DE + DngRT DU = 0
q
41 kJ mol–1 = DE + (1) ¥ 8.3 ¥ 10–3 ¥ 373 21. (d) For reversible adiabatic process DS = rev
qrev = 0 fi DSsystem = 0 T
DE = 37.904 kJ mol–1

22. (c) C + 2S h CS2 DrH = ? H+ + OH– h H2O; DH = –57.3 kJ (ii)

DrH = (DHcombution)R – (DHcombution)P Subtracting Eq. (ii) from Eq. (i), we get
DrH = (x + 2y) – (z) 1 1
H 2C2O 4 h C2O 42– + H + ; DH = +3.95
OR 2 2
C + 2S Æ CS2 ± ‘a’ kJ a=? \ H 2C2O 4 ææ
Æ C2O 42– + 2H + ; DH = +7.90
C + O2 Æ CO2 + x kJ (1) 28. (c) S(s) + 3F2 SF6 DHf = –1100 KJ mol–1
S + O2 Æ SO2 + y kJ (2) (g) (g)
CS2 + 3O2 Æ CO2 + 2SO2 + z kJ (3) +275 +6 ¥ 130

Equation 2 multiplying with 2, we get SF6 + 1100
S 6F
2S + 2O2 Æ 2SO2 + 2y kJ (4) (g) (g)
6 ¥ [ES–F]
1 + 4 – 3 we get C + 2S Æ CS2 + x + 2y – z
23. (d) The heat of neutralisation is defined as heat evolved
only when 1 g equivalent of acid is completely neu- Since reactants are not in gaseous state
tralised by 1 g equivalent of base in dilute solution \ DH = Eabsorbed – Ereleased
Number of gram equivalent of H2SO4 –1100 = [275 + 6 ¥ 80] – [6 ¥ ES – F]
Bond energy of S – F = 309 kJ mol–1
1
= 100 ¥ = 10 meq T2 ÊV ˆ
10 29. (b) DS = nCV ln + nR ln Á 2 ˜
Number of gram equivalent of NaOH T1 Ë V1 ¯
1 Ê 10 ˆ
= 150 ¥ = 15 meq DS = 5 ln
373
+ R ln Á ˜
10 298 Ë 1¯
10
¥ 57.3 = 0.573 kJ DH transition
1000 30. (c) Using DStransition =
H2SO4 + 2NaOH Æ Na2SO4 + 2H2O Ttransition
5 mm 15 mm — — –DH trans
0 5 mm 5m 10 mm DSsurr =
T
24. (b) Work done in expansion
= P ¥ DV – 401.7
DStrans =
We have 1 L atm = 101.3 J 368
Work done = 6 ¥ 101.3 J = 607.8 J + 401.7
DSsurr = , temperature of ice bath = 273 K
Let DT be the change in temperature of water 273
Therefore, PDV = m ¥ C ¥ DT
– 401.7 401.7
607.8 = 180 ¥ 4.18 ¥ DT DStotal = +
368 273
DT = 0.81 K
Tf = T1 + DT = 290.8 K T1 – T2
31. (a) h =
25. (c) DrH = [SVP(DHf)P + SVR(DHf)P] T1
DrH = [2(DHf)NaOH – 2(DHf)H2O] 373 – 298 Ê 75 ˆ
h= =Á
– 281.9
= ( DH f ) NaOH + 285.8 373 Ë 373 ˜¯
2
75
( DH f ) NaOH = - 426.75 kJ mol-1 h ¥ 100 = ¥ 100
373
T1 – T2
26. (a) T1V1g –1 = T2V2g –1 32. (b) h =
T1
g –1
T2 Ê V1 ˆ
\ = = 2g –1 500 – 300 2
T1 ÁË V2 ˜¯ h= =
500 5
Since g is more for the gas X, the temperature will also W
be more for it. h= fi W = (h) (qsource)
qsource
27. (d) By the definition of heat of neutralisation, we have
1 1 Ê 2ˆ
H2C2O4 + NaOH h Na2C2O4 + H2O; = Á ˜ (2 kcal) = 0.8 kcal
2 2 Ë 5¯
DH = 53.35 kJ
33. (a) Number of equivalent of H2SO4 taken
1 1 2-
or H C O + OH– h C2O 4 + H2O; 0.2 ¥ 2 ¥ 400
2 2 2 4 2 = = 0.16
1000
DH = –53.5 kJ (i)

Number of equivalent of KOH added ÈT - T ˘

600 ¥ 0.1 46. (a) w = q ¥ Í 1 2 ˙
= = 0.06 Î T1 ˚
1000
Ê 700 ˆ
Number of equivalents of acid and bases which neu- = 2.1 ¥ Á = 1.47 kJ
tralised each other = 0.06 Ë 1000 ˜¯
\ Heat evolved = 0.06 ¥ 57.1 kJ = 3.426 kJ 47. (b) C + O 2 Æ CO 2 + 97 Kcal …(i)
34. (b) For adiabatic process; TVg–1 = Constant (S) (g) (g)
4 CO 2 + C Æ 2CO - 39 Kcal …(ii)

For monoatomic gas, g = = 1.33; n = 1.33 – 1 = 0.33 (g) (g)
3
35. (b) q = nCPDT 1
To find CO + O 2 Æ CO 2 + ?
100 2
1000 = ¥ 75 ¥ DT
18 Subtracting eq. (ii) from (i)
DT = 2.4 K - CO 2 + O 2 Æ CO 2 - 2CO + 97 + 39
36. (b) DrH = SvP(DHf)P – SvR(DHf)R
2CO + O 2 Æ 2CO 2 + 136 Kcal
= [(–110.5) + (–241.8)] – [–393.5] KJ mol–1
1
= 41.2 KJ mol–1 \ CO + O 2 Æ CO 2 + 68 Kcal
OR 2
(i) C(s) + O2(g) h CO2(g) ; 48. (a) The combustion equation of sucrose is
DHf = –393.5 kJ mol–1 C12H22O11(s) + 12O2(g) Æ 12CO2(g) + 11H2O(g)
1 Here,
(ii) C(s) + O2(g) h CO(g) ; Dng = sum of gaseous product moles – sum of gaseous
2
DHf = –110.5 kJ mol–1 reactant moles
1 Dng = 12 + 11 – 12
(iii) H2(g) + O2(g) h H2O(g) ; As we know,
2
DHf = –241.8 kJ mol–1 DH = DE + DngRT, where DH = heat of reaction at con-
For getting CO2(g) + H2(g) h CO(g) + H2O(g), stant pressure
add (ii) and (iii) and subtract (i). DE = heat of reaction at constant volume
Thus –110.5 – 241.8 + 393.5 = 393.5 – 352.3 = 41.2 Here, DE = –1348.9 kcal
37. (b) DG = DH – TDS. R = 2.0 cal, T = 25 + 273 = 298 K
At equilibrium ; DG = 0, so DH = TDS \ DH = (–1348.9 ¥ 1000) + 11 ¥ 2 ¥ 298
= 273 ¥ (60.01 – 38.20) = 5954 J/mol) = –1348900 + 6556 = –1342344 cal
38. (d) Work done by a gas = –Pext ¥ DV = –1342.344 kcal
49. (b) Now for the reaction,
= –105(10–2 – 10–3)
H2(g) + F2(g) h 2HF(g);
= –105(0.009) = –900 J
DH° = –124 kcal
39. (c) For isothermal process DU = DH = 0
\ DH° = SB.DE. (ractants) – SB.DE. of (products)
40. (a) Use DrH = SvP(DHf)P – SvR(DHf)R
or –124 = DHH–H + DHF–F – 2DHH–F
1 = 104 + 37.8 – 2DHH–F
41. (a) Cgraphite + 2H2 + O2 Æ CH3OH DH = x
2 \ 2 DH H-F = 104 + 37.8 + 124
o
x = (2) + 2 ¥ (3) – (1) = 265.8 kcal
= –239 KJ mol–1 265.8
42. (b) DH = DU + DngRT Bond energy of H – F = = 132.9 kcal
2
DG0 = DH0 – TDS0 \ DH° for the given reaction = –132.9 kcal
43. (b) DG0 = –2.303 RT log Kp 50. (b) As we know, DH = DE + DngRT
= –2.303 ¥ 8.314 ¥ 298 ¥ log 2.47 ¥ 10–29 For the reaction,
= 163.228 kJ/mole CO(g) + 1/2O2(g) h CO2(g)
44. (b) For dissociation reactions Dng = 1 – (1 + 1/2) = –1/2
DH > 0 and Dng > 0 fi DrS > 0 \ DH = DE – 1/2RT
45. (d) DG = DH – TDS \ DH < DE
DG = –33000 – [T(–58)] 51. (d)
DG = –33000 + 58T (i) P4 (yellow) + 5O2(g) h P4O10 + 9.19 kJ (1)
at T = 568.96 K DG = 0 (ii) P4 (red) + 5O2(g) h P4O10 + 8.78 kJ (2)
spontaneous below 568.96 K temperature. P4 (yellow) Æ P4 (red) + 0.41 kJ
so, heat of transition of yellow to red phosphorous is
–0.41 kJ

52. (a) As we know that, resonance energy = DH° (ob- 63. (b) By adding (i) and (ii),
served) – DH° (calculated) 2Na + Cl2 h 2NaCl; DH = –196 kcal
= (50.4 – 232.6) kJ/mol = –182.2 kJ mol–1
53. (b) Given 64. (d) D r H = [( DH f )TiO2 + 4( DH f ) HCl - ( DH f )TiCl4
CD + O2(g) h CO2(g) DH = –94.3 kcal (1) - 2( DH f ) H2O ]
CA + O2(g) h CO2(g) DH = –97.6 kcal (2) DrH = –944.7 – (4 ¥ 92.3) + 763.2 + (2 ¥ 241.8)
Subtracting Eq. (2) from Eq. (1):
DrH = –67.1 kJ/mole
CDiamond h CAmorphous DH = 3.3 kcal
54. (b) DHN = –[55.9 – (x + y)] 65. (d) D r H = [ Sn P ( DH f ) P - Sn R ( DH f ) R ]
–12.1 = –[55.9 – (x + y)] D r H = [3( DH f )CO2 + 4( DH f ) H2O - ( DH f )C3H8 ]
–12.1 = –55.9 + x Since y = 0
x = 55.9 – 12.9 –2221.6 = 3 ¥ (–394) – 4(285.8) – (DHf)C3H8
x = +43.8 kJ (DHf)C3H8 = – 103.6 kJ/mole
55. (a) Since heat of neutralisation of strong acid and 66. (d) D r H = [ Sn P ( DH f ) P - Sn R ( DH f ) R ]
strong base is equal to the formation of one mole of
water, i.e., NaOH + HCl Æ NaCl + H2O + Q D r H = [4( DH f )CO2 + 2( DH f ) H2O - 2( DH f )C2 H 2 ]
where Q = heat of neutralisation –2601 = – 4(394) – 2(285.8) – 2(DHf) C2H2
fi Na+ + OH– + H+ + Cl– Æ Na+ + Cl– H2O + Q 2(DHf)C2H2 = 226.7
OR H+ + OH– Æ H2O + Q
56. (d) DH = DE + DngRT
LEVEL II
57. (c) H2SO4 + 2NaOH Æ Na2SO4 + 2H2O;
DH = 2 ¥ (–13.7) = –27.4 kcal
1. (a) We know that the heat of reaction
58. (b) Lower the heat of neutralisation, more is the dis-
DH = SB.DE. (reactant) – SB.DE. (product)
sociation energy and weaker is the acid
For the reaction,
\ Correct order of Acidic strength A > D > C > B
2H – H(g) + O = O(g) h 2[H – O – H](g)
59. (b) One double bond break and one single bond formed DH = –115.4 kcal, B.E. of H – H = 105 kcal; B.E.
per molecule of C2H4 in polymerisation of O = O = 119 kcal
n C = C Æ (—C—C—)n Since one H2O molecule contains two O – H bonds
DH = S(B.D.E)Reactants – S(B.D.E)Products – 115.4 = (2 ¥ 104) + 119 – 4 (O – H) bond energy
= +145 – (+80) = 65 kJ/mol \ 4 ¥ (O – H) bond energy = (2 ¥ 104) + 119 + 115.4
Note: C – H bonds are common in both reactants and (2 ¥ 104) + 119 + 115.4
i.e., O – H bond energy = =
products. 4
110.6 kcal mol–1
60. (a) DH = 3 ¥ (–54) – 2(–143) = –162 + 286
2. (a) mZn ◊ SZn ◊ (Tf – Ti) + mH2O ◊ SH2O ◊ (Tf – Ti) = 0
= 124 kJ
(65.38) (0.4) (Tf – 20°) + 180 gm (4.20) ¥ (Tf – 100°) = 0
61. (b) N ∫ N + 3H – H 2 H–N–H
fi [(65.38)(0.4) + 180(4.20)] ¥ Tf
= (65.38)(0.4)(20) + (180)(4.20)(100)
H
+x +3y È (65.38)(0.4)(20) + (180)(4.20)(100) ˘
Tf = Í ˙ = 97.3°C
Î (65.38)(0.4) + (180)(4.20) ˚
–6z 3
\ for the formation of 2 mole NH3 DH 3. (b) Ar = monoatomic ideal gas CV = R
= Eabsorbed – Ereleased 2
At constant pressure q = DH = nCPDT
= x + 3y – 6z
5
x 3 = 0.25 ¥ ¥ 8.314 ¥ 16 = 83.2
\ for 1 mole DH = + y - 3 z 2
2 2 4. (c) Reversible process-involve infinitesimally small
OR driving force. Hence system and surrounding remains
DH = S(B.D.E)Reactants – S(B.D.E)Products in equilibrium.
62. (b) C2H4 + 3O2 h 2CO2 + 2H2O PV
5. (d) Temperature at ‘a’ = T0 =
6226 ¥ 3 ¥ 22.4 R
Thus, VO2 used = = 296.5 litre P0V0
1411 at (a) T0 = (i)
R
20
= ¥ volume of air (2 P0 )(4V0 )
100 at (C) TC = = 8T0
\ Volume of air = 1482.5 L R

3
DU = nCV (Tf – Ti) = R(8T0 – T0) DSsyst >
2
21RT0 Hence DSsyst can be negative but numerically
DU = = 10.5 RT0
2 smaller than .
6. (b) The case of irreversible adiabatic process.
11. (b) Formation of Fe3O4
Wirr = –Pext(V2 – V1)
3Fe(s) + 2O2(g) h Fe3O4(s) ; DG =?
fi nCV (T2 – T1) = – P(V2 – V1) n = 1
3
CV = R T1 = T
2
Pext = 1 atm
–1(V2 – V1 ) (1 atm)(2L – 1L)
T2 = +T =T - 12. (c) T =
1 CV 3
( R) DH° = –110 – (–266.3)
2
2( L atm) DS° = 197.6 + 27.28 – 5.74 – 57.49
T2 = T - Above this temperature, the process becomes sponta-
3 ¥ 0.0821( L atm k –1mole –1 )
neous.
7. (c) VB > VA and TB > TA
DH = nCP(TB – TA) > 0 13. (c) Intensive property =
w = –Pext (VB – VA) < 0 pH μ concentration = mole/volume
8. (b) H2O(s) ææÆ
q1
H2O(l) ææÆ H2O(l)
q2 though pH is a dimensionless number and intensive
property
0°C 0°C 25°C
Ê 36
q1 = DHfusion(kJ/mole) ¥ Á mole˜ˆ EMF = = Intensive property
Ë 18 ¯
q1 = 6.01 ¥ 2 = 12.02 kJ Boiling point (Tb) = temperature = intensive property
q2 = mCDT = (36 g)(4.18 J/K g)25 Entropy (s) = = extensive property
È (36)(25)(4.18) ˘
qNET = q1 + q2 = Í12.02 + ˙˚ kJ
Î 1000
14. (a) Temperature at A(TA) =
= 12.02 + 3.76 = 15.78
RT
9. (b) Initial pressure P =
V
P = 300 R = (300 ¥ 0.0821) atm
final pressure = 1 atm
final volume; PfVf = PiVi
PV Ê (300) R ˆ
fi Vf = i i
=Á
Ë 1 ˜¯
= 24.6 L
Pf
V2
DS = nRT ln for isothermal
V1 Since BC curve isothermal
Ê 24.6 ˆ
DS = R ln Á \
Ë 1 ˜¯
10. (b) For spontaneous reactions DStotal > 0
DStotal = DSsystem + DSsurr
Ê DH Surr ˆ now
DStotal = DSsystem + Á
Ë T ˜¯ TD – TA
\ DU = DH = 0
= DSsystem +
DStotal > 0 fi DSsys + >0

3C + 3H2 h C3H6 DH = 20.6 kJ/mole

C + O2 h CO2 DH = –394 kJ/mole
H2 + O2 h H2O DH = –285.8 kJ/mole
15. (c) = [3 ¥ (–394) – 3(285.8) – 20.6]

= –2060 kJ/mole
21. (c)
DHC = [52(–285.8) + 57(–393.5) – (– 70870)]
= –14861.6 – 22429.5 + 70870 = 33578.9
energy liberated for 1 g fat
DHT = DH1 + DH2
DH1 = DU1 + (P2V1 – P1V1) = = 37.98 kJ/mole
DH1 = CV(T2 – T1) + (P2V1 – P1V1)
22. (c)
DH2 = DU2 + (P3V2 – P2V1)
DrH = [4(90.2) + 6(–241.8) + 4(46.1)]
In adiabatic process DU = W = –Pext (Vf – Vi)
= 360.8 – 1450.8 + 184.4 = –905.6
\ DU2 = –P3[V2 – V1]
DH2 = –P3 (V2 – V1) + (P3V2 – P2V1) heat released for 3 g = ¥ 3 = 39.9
DH2 = P3V1 – P2V1
23. (a) Heat lost by copper = heat gain by gold
DHT = CV(T2 – T1) + (P2V1 – P1V1) + P3V1 – P2V1
30 ¥ 0.385(318 – T) = 15 ¥ 0.129 (T – 298)
DHT = CV(T2 – T1) + P3V1 – P1V1 Final temperature T = 315.1 K
16. (a) DH = qp T = 42.1°C
since H is state function DH will remain same from 24. (a) Applying Hess’s law.
both path-isobaric and non-isobaric. 25. (d) 2 C2H2(g) + 5 O2(g) Æ 4 CO2(g) + 2 H2O(l) (i)
DHo/kJ = –2600 kJ
C(s) + O2(g) Æ CO2(g) DHo/kJ = –390 kJ (ii)
2 H2(g) + O2(g) Æ 2 H2O(l) DHo/kJ = –572 kJ (iii)
DrH for 2C(s) + H2(g) Æ C2H2(g) can be calculated by
But q = qp only when path was isobaric.

DH = qp only for isobaric path.
17. (b) Greater the Dng greater the value of DS.
18. (a) DG = DH – TDS DrH = – (–1300) + 2(–390) + ¥ (–572)
y = C + mX DrH = 234
fi DH = C
m = –DS 26. (b)
from intercept C > 0 fi DH > 0 DrH=
m < 0 fi –DS < 0
fi DS > 0 DrH = [2(–393.5) + 3(–241.8) – (–277.7)]
DrH = –1234.7 kJ/mole
19. (d) Heat evolve = ¥ 12 = 581.73
27. (a) N2(g) + 3 O2(g) + H2(g) Æ 2 HNO3(aq) (i)
20. (c) C3H6 + O2 h 3CO2 + 3H2O DH /kJ = –414.0
o
N2O5(s) + H2O(l) Æ 2 HNO3(aq) (ii)

here
DHo/kJ = –86.0
2 H2(g) + O2(g) Æ 2 H2O(l) (iii)
DHo/kJ = –571.6
DrH for 2N2(g) + 5O2(g) Æ 2N2O5 (s) can be calculated
by 2 ¥ (i) – 2 ¥ (ii) – (iii)
OR DrH = [2(–414) + 2(86) + 571.6]
DrH = –84.4 kJ
C3H6 + O2 h 3CO2 + 3H2O

Comprehension 2 (Question 9 to 11)

28. (c)
DHr = [3(110.5) – 28.9 + 2(–285.8) + 3(–74.8)] 9. (a) The gas exapands against a zero opposing pressure.
= –747.5 Since dw = –Pext. ¥ V, it is obvious that the work in-
29. (b) C2H5OH h C2H4 + H2O ... (i) DH = 45.54 volved in the expansion in zero.
8a 8a du = dq + dw
Hence du = dq
C2H5OH h CH3CHO + H2 ...(ii) DH = 68.91
Since there is no change in temperature dq = 0
a a Hence du = 0
8a + a = 1 10. (a) u = f(T, V)
a=
Energy involved in (i) reaction = 45.54 ¥

Since dT = 0; du = 0
Energy involved in (ii) reaction = 68.91 ¥
Total involved in (i) + (ii) are fi 48.137 kJ

Since dV π 0, follows that
30. (c) HAuBr4 + 4HCl h HAuCl4 + 4HBr DH = 8.8
% conversion = ¥ 100 = 5%
Since it is a free expansion, it is applicable to only ideal
LEVEL III gases.
11. (d) If the external pressure is only infinitesimally
1. (A) Æ R; (B) Æ P, Q, S; (C) Æ Q,S; (D) Æ Q, S smaller than the pressure of the gas, the expansion is
2. [A Æ Q, (B) Æ P, R, S, (C) Æ S , (D) Æ P, Q, R] said to take place reversibly. If, however, the external
3. [(A) Æ P, S, (B) Æ P, (C) Æ Q, (D) Æ P, R, S] pressure is much smaller than the gas pressure, the ex-
4. [(A) Æ R, Q; (B) Æ P, Q; (C) Æ S, Q; (D) Æ Q] pansion occurs irreversibly. If the external pressure is
5. [A Æ S; (B) Æ R; (C) Æ Q; D Æ P] zero, the expansion is known as free expansion.
Comprehension 1 (Question 6 to 8) Comprehension 3 (Question 12 to 16)
6. (b) The enthalpy of dissociation of the O–H bond de- 12. (c) DrS° = S°(CH3OH, g)
pends on the molecular species from which H-atom is – [S°(CO, g) + 2 ¥ S°(H2, g)]
being separated. = 240 – 198 – 29 ¥ 2 = – 16 J/K–mole
H2O(g) h H(g) + OH (g); DH0 = 501.87 kJ mol–1 13. (a) DrH° = DHf°(CH3OH, g) – DHf°(CO, g)
However to break O–H bond in hydroxyl a different = – 201 – (114) = –87 kJ/mol
quantity of heat (423.38 kJ mol–1) is
14. (d)
B.E. (O – H) =
= 462.625 kJ mol–1 = 44 – (29.4 + 2 ¥ 28.8) = – 43 J/K-mol

7. (a) In case of diatomic gaseous molecules, bond enthal-
py and bond dissociation enthalpy are identical because
each refers to the reaction = – 13.42 J/K-mol
H2(g) Æ 2H(g); BE (H – H) = 433.93 kJ mol–1
8. (b) C2H2S – SC2H Æ C2H5 – S – C2H5 + S DH 15. (c)
S – S bond enthalpy = DH – (–87) = –43(320 – 300)
= –87.86 kJ/mol
16. (d)
= – 87860 – 320 (–13.42) = 83565.6
DGo = 83.565 kJ/mol

Comprehension 4 (Question 17 to 20) Since DT = 0, therefore DE = 0 and according to the

first law of thermodynamics. DE = q + W
17.
\
DrH =
= [–658.3 + 2(–92.3) – 2(–485.2)]
= 127.5 kJ/mole
18. Add Eq. (i), (ii) and (iii)
CX4(g) h C(g) + 4X Substituting the values, we get
DH = –DHf + 718 + 2D(X – X)
If X = F, then
DH = +679.6 + 718 + 2 ¥ 154.7
DH = 1707
Average bond energy of C – F bond =

= 426.75 kJ/mole
If X = Cl, then DStotal = DSsys + DSsurr
DH = 106.6 + 718 + 2(246.7) = 1318 = (17.29 – 12.47) JK–1, which is positive.
Average bond energy of C – Cl bond = 329.5 kJ Since DSTotal is positive, the processes is irreversible.
19. (c) C – Cl bond energy = 329.5 22. (c, d) Melting of H2O(s) at 0°C and 1 atm is a revers-
C – H bond energy = 416.1 ible process fi DSTotal = 0
C – F bond energy = 426.75 Vaporisation of H2O(l) at 373 K is a reversible process
Order of reactivity C – Cl > C – H > C – F DSTotal = 0
20. (a, b, c) We have Below 0°C [H2O(s) h H2O(l)] is non spontaneous
qwater = mwater ¥ Swater ¥ DT not feasible.
= {(300 mL) (1g mL–1)} (4.184 J g–10 C–1) H2O(l) h H2O(s) (freezing) is feasible below 0°C
(1.126°C) H2O(s) h H2O(l) not feasible below 0°C and fea-
= 1413 J = 1.413 kJ sible above 0°C fi DG = negative for melting process
qbomb = (mbomb ¥ Sbomb) DT = (heat capacity)bomb ¥ DT fi DSTotal increases
= SbombDT 23. (a, b, c) Both the gases before mixing are at the same
= (1.77 kJ° C–1) (1.126°C) temperature and pressure. Since the amount of neon is
= 1.992 kJ twice as that of helium, it is obvious that
\ Total heat released in combution of 0.138 gram VNe = 2VHe
Mg at constant volume Now the volume of the gas after mixing will be
= –(qwater + qbomb) Vtotal = VHe + VNe = VHe + 2VHe = 3VHe
= –(1.413 + 1.992) kJ = –3.405 kJ Each of the two gases will suffer entropy change due to
\ Heat released in the combustion of 1 mole or 24.30 the volume change. Thus,
Mg at constant volume.
For the reaction,

2Mg(s) + O2(g) Æ 2MgO(s) Dng = –1
DH = DE + (Dng) RT
= –599.60 + (–1)(8.314 ¥ 10–3 ¥ 298 K)
= (–599.60 – 2.48) kJ mol–1 = –602.08 mol–1 Thus
21. (a, b, c) Entropy change of the gas at constant tempera- DSmix = DSHe + DSNe = 9.136 + 6.743 = 15.879 JK–1
ture. 24. (a, b, c) Amount of
T1 = 300 K; V1 = 20 dm3; V2 = 10 dm3
For an adiabatic reversible process
g -1
R / CV ,m R / CV ,m T2 Ê V1 ˆ
T2V2 = T1V1 =
T1 ÁË V2 ˜¯
Entropy change of the surroundings.

Thus, 0.5 ¥ 1.987 ¥ 4.184

R / CV ,m 3 ˆ 2/5
=- = - 50.63 J
ÊV ˆ Ê 20 dm 0.0821
T2 = T1 Á 1 ˜ = (300 K) Á ˜
Ë V2 ¯ Ë 10 dm3 ¯ Since, Work is carried out at constant P and thus irre-
versible process.
= (300 K)(1.32) = 396 K
From first law of thermodynamics
Hence, DE = q + w
5 = 58.63 – 50.63
DE = W = nCV DT = 0.714 ¥ ¥ 8.314 ¥ 96 =8J
2
= 1424.69 J 5 7
31. Gas is diatomic as g = 1.4, thus, CV = R and C p = R
7 2 2
DH = nCP DT = 0.714 ¥ ¥ 8.314 ¥ 96 and DH = 85 J at constant pressure
2 DH = nCPDT
= 1994.56 J
85 85 ¥ 2 30
25. (5) Energy available for muscular work \ DT = = =
nC p n ¥ 7 ¥ R nR
2880 ¥ 25
= = 720 kJ/mol. 30
100 Now, W = –nRDT = –nR ¥ = –30 J
\ energy available for muscular work for 125 nR
125 1 DH = DE + nRDT
grams glucose = 720 ¥ ¥ = 5 km 85 = DE + 30
180 100
DE = 55 J
26. (3) On mixing CaCl2 (aq.) and Na2CO3
32. DHdissolution = DH(ionization) + DH(hydration)
CaCl2 + Na2CO3 h CaCO3 + 2NaCl
= 778 – 775 = 3 kJ mol–1 = 3000 J mol–1
Solutions are very dilute and thus, 100% dissociation
DSdissolution = 40 J mol–1
occurs.
DG(dissolution) = DH – TDS fi 3000 – 300 ¥ 40 = –9000 J;
Ca2+ (aq.) + 2Cl– (aq.) + 2Na+ (aq.) + CO32- (aq.) h DG = –9 kJ
CaCO3 + 2Na+ (aq.) + 2Cl– (aq.) 33. Reversible work is maximum work.
or Ca2+ (aq.) + CO32- (aq.) h CaCO3(s) ÊV ˆ
\ w = –2.303nRT log Á 2 ˜
Ë V1 ¯
D r H = [ Sn P ( DH fo ) P ] - [ Sn R ( DH of ) R ] 16 25
= –2.303 ¥ ¥ 8.314 ¥ 300 log
= DH foCaCO3 - [ DH foca 2+ + DH foCO2- ] 32 5
3 = –2.01 ¥ 103 J = –2 kJ
DrH of a compound 34. DHfusion = 6.025 ¥ 1000 J mol–1
= DrH = –288.45 – (–129.80 – 161.65) = 3 k cal 6025 -1
27. (4) The required equation is = Jg = 334.72 J g–1
18
2Al + Fe2O3 h Al2O3 + 2Fe, DH = ?
DH fusion 334.72
DH = DH f (products) - DH f (reactants) DSfusion = = = 2 JK -1g -
Tf 167 K
= [ DH f (Al2O3 ) + 2 DH f (Fe) ]
35. (i) –3201 kJ, (ii) –3199.75 kJ
- [2 DH f (Al) + DH f (Fe2O3 ) ] Given,
7C(s) + 3H2(g) + O2(g) h C6H5COOH(s);
= (–399 + 2 ¥ 0) – [2 ¥ 0 + (–195.92)]
DH0 = –408 kJ (i)
= –399 + 195.92 = –203.8
C(s) + O2(g) h CO2(g) DH0 = –393 kJ (ii)
At. mass of aluminum = 27, Mol. mass of Fe2O3 = 160
1
160 2 ¥ 27 H2(g) + O2(g) h H2O(l) DH0 = –286 kJ (iii)
\ Volume = + = 50.77 cm3 2
5.2 2.7
15
- 203.08 C6H5COOH(s) + O2(g) h 7CO2(g) + 3H2O(l);
\ Fuel value per cm3 = = 4 kcal DH = ? 2 (iv)
50.77
By (ii) ¥ 7 + (iii) ¥ 3 – (i)
DH trans 2288
28. (8) DS trans = = = 8 JK -1mol-1 15
T 286 C6H5COOH(s) + O2(g) h 7CO2(g) + 3H2O(l)
2
29. (2) Q = 13.7 – 11.7 = 2
30. (8) Work done = –Pext ¥ dV = –1 ¥ (2.5 – 2.0) DHo = [–393 ¥ 7 – 286 ¥ 3 + 408]
= –0.5 L – atm \ DHo = –3201 kJ

Also DH = DE + DngRT
- 95.4 ¥ 10+3
\ = 3201 = DE + (–0.5) ¥ 8.314 ¥ 10–3 ¥ 300 > T or 481.0 > T
\ DE = –3201 + 1.2471 = –3199.75 kJ -198.3
36. Total energy required in the day Thus, if temperature of system is lesser than 481 K,
150 ¥ 24 ¥ 60 ¥ 60 the reaction would be spontaneous. At 481 K, the reac-
= kJ (1 W = J/ sec) tion will be in equilibrium. An increase in temperature
1000
= 12960 kJ above 481 K will develop non-spontaneity for the reac-
12960 tion.
Units of glycogen required = = 27 42. Heat taken up by water = mCDT
476
= 150 ¥ 1000 ¥ 4.184 ¥ 10–3 ¥ 55 = 34518 kJ
1 +
37. Given, H 2 (g) + aq. h H (aq) + e; DHo = 0 (i) 2050 kJ heat is provided by 1 mole C3H8
2 \ 34518 kJ heat is provided by = 34518/2050
1 1 = 16.83 mole of C3H8
H 2 (g) + Cl2 (g) h HCl(g); DHo = –92.4 kJ
2 2 (ii) Volume of C3H8 at NTP = 16.83 ¥ 22.4 L
+ - = 3.77 ¥ 102 L
HCl(g) + nH2O(l) h H (aq) + Cl(aq) ; DH0 = –74.8 kJ
43. Work is done aganist constant P \ irreversible
(iii)
DV = 5 – 3 = 2dm3 = 2 L; P = 3 atm.
Add Eqs. (ii) and (iii)
\ W = –Pext ◊ DV = –3 ¥ 2 litre atm = –6 ¥ 101.3
1 1 + - = –607.8 kJ
H 2 (g) + Cl2 (g) + nH 2O h H (aq) + Cl(aq) ;
2 2 Now this work is used up in heating water
DH0 = –167.2 kJ (iv) \ W = n ¥ C ¥ DT
Subtract Eq. (i) from (iv) = (10 ¥ 18) ¥ 4.184 ¥ DT = 607.8
\ DT = 0.80
1
\ Cl2 (g) + aq. + e - h Cl(aq)
-
; DH = –167.2 kJ \ DT ¥ 10 = 8
2 44. The concerned chemical reaction is
-
Heat of formation for Cl(aq) = –167.2 kJ B2H6(g) + 3O2(g) h B2O3(s) + 3H2O(g), DH = ?
38. Initial average temperature of the acid and base = The enthalpy change can be calculated in the following
22.6 + 23.4 way:
= 23.0°C [Since mass same]
2 Here D r H = ( DH C ) B2H6
Rise in temperature = (29.3 – 23.0) = 6.3°C
D r H = Sn P ( DH fo ) P - Sn R ( DH fo ) R
Total heat produced = (92 ¥ 0.75 + 200 ¥ 4.184) =
(905.8) ¥ 6.3 = 5706.54 J D r H = [ DH B2O3 (S) + 3DH H2O(g) ] - DH B2H6 (S)
5706.54
Enthalpy of neutralisation = - ¥ 1000 ¥ 1 ( DH fo of O 2 = 0)
100
= – 57065.4 J = – 57 kJ DH H2O(g) can be obtained by adding DH H O and
2 (I)
39. + H2 Dr H = ? DH H2O(g)
See heat of combution i.e., – 286 + 44 = –242 kJ mol–1

DH = [–1273 + 3 (–242)] – 36 kJ mol–1
D r H = [ SvR ( DH combution ) R - SvP ( DH combution ) P ] = –1273 – 726 – 36
= (- 241) + (- 3800) - (- 3920) = –2035 kJ mol–1
= -121 kJ/mole 45. Given:
+ -
40. DHreaction = Bond energy data for the formation of bond NaCl(s) + aq h Na (aq) + Cl(aq) DH = –2 kJ/mole
+ -
+ Bond energy data for the dissociation of bond Na (g) + Cl(g) h NaCl(s) DH = –772 kJ/moles
= –[1(C – C) + 6(C – H)]
+ - + -
+ [1(C = C) + 4(C – H) + 1(H – H)] so Na (g) + Cl(g) + aq. h Na (g) + Cl(aq.) DH = –774
= –347 – 2 ¥ 414 + 615 + 435 + +
= – 125 kJ and Na (g) + aq. h Na (aq.) DH = –390
–
Enthalpy change for the reaction = –125 kJ So enthalpy of hydration of Cl = –384
41. DG = DH – TDS Similarly, enthalpy of hydration of I– = –307
For a reaction to be spontaneous, DG = –ve 46. q = –65 J, w = 20 J
DH DE = q + w
DH – TDS = –ve or DH > TDS or > T or
DS = –65 + 20 = –45 J

47. (a) DHglucose = –2808 kJ mol = 2.303 ¥ 25.5 log 2 + 13.6 ¥ 10–3 ¥ 300 – 42.5 ¥
Energy need to climb 3 m = Mgh = 62.5 ¥ 10 ¥ 3 (6002 – 3002 )
Dq = 1875 Joule 10–7
2
Now useful energy from 1 mole of glucose
DS = 20.618 kJ
25 56. Br2(l) + Cl2(g) h 2BrCl(g), DH° = 29.3 kJ
= 2808 ¥ = 702 kJ
100 DSBr2(l) = 152.3
fi Number of mole of glucose required DSCl2(g) = 223.0
1875 DSBrCl(g) = 239.7 J mol–1 K–1
=
702 ¥ 103 DrS = 2 ¥ 239.7 – 223 – 152.3 = 104.1
= 2.67 ¥ 10–3 mole DrG = DH – TDrS
Grams of glucose = 180 ¥ 2.67 ¥ 10–3 = 0.4807 g = 29300 – 298 ¥ 104.1 = –1721.8 J
(b) Energy need to climb 3000 m = 0.4807 ¥ 3000/3 57. CCl4(l) h CCl4(g)
= 0.4807 kg P = 1 atm
48. DH = DE + DngRT T = 298 K DS = 94.98 JK–1
40.66 ¥ 2 = DE + 2 ¥ 8.314 ¥ 373 D r H = Sn P ( DH fo ) P - Sn R ( DH fo ) R
fi DE = (81.32 – 6.202) kJ = (–106.7 + 139.3) kJ
DE = 75.118 kJ = 32.6 kJ/mol
49. DH = 1 kcal DrG = DrH – TDS
DH = DE + PDV DrG = 32.6 ¥ 103 – 298 ¥ 94.98
1 ¥ 103 ¥ 4.18 = DE + 1.013 ¥ 105 ¥ 3 ¥ 10–3 DrG = 4.296 kJ/mol
Ê 4149.70 ˆ positive hence non spontaneous
DE = (4180 – 30.39) Joule = Á
Ë 4.18 ˜¯
cal
58. Since entropy and latent heat given in per kg, so mass
DE = 0.993 kcal
taken in kg.
3
50. NH4CN(s) + O2(g) h N2(g) + CO2(g) + H2O(l) Step 1
2 Ice (200 K) h Ice (273 K)
1 8.314 ¥ 298
DH298 = DE + DngRT = –742.7 + ¥ T 273
2 1000 DS1 = m Cp ln 2 = 1 ¥ 2.09 ¥ 103 ln
DH298 = –741.46 kJ T1 200
51. DH =1440 cal DS1 = 650.312 J/°C
DH = DE + P(V2 – V1) Step 2
101.3 Ice (273 K) m Water (273 K)
= DE + 1[0.018 - 0.0196] ¥
4.18 DH f 3.34 ¥ 105
DS2 = = = 1223.44 J/°C
0.0016 ¥ 101.3 273 273
1440 = DE - Cal Step 3
4.18 Water (273 K) h Water (373 K)
DE = 1440 + 0.03877 373
= 1440.03877 Cal DS3 =1 ¥ 4.18 ¥ 103 ln = 1304.6 J/°C
273
52. W = –Pext[V2 – V1] = – [1.10 ¥ 1.0] ¥ 101.3 J Step 4
= 10.13 J Water (373 K) m Steam (373 K)
53. Zn(s) + 2H+(aq) m Zn2+(aq) + H2(g)
DH v 22.6 ¥ 105
q = DH = –36.5 kJ DS4 = = = 6058.98 J/°C
È 500 ¥ 50 ˘ 373 373
W = –Pext(V2 – V1) = – 1 ¥ Í ¥ 101.3 J Step-5
Î 1000 ˙˚ Steam (373 K) h Steam (400 K)
W = –2.53 kJ
\ DE = q + W fi –36.5 – 2.53 = –39.03 kJ 400
DS5 = 1 ¥ 2.09 ¥ 103 ln = 146.06 J/°C
ÊPˆ 373
54. W = – 2.303 nRT log Á 1 ˜ DST = 9383.4 J/°C
Ë P2 ¯
5
Ê 5ˆ 59. g = , P = 1 atm, T1 = 300 K, P2 = 2 atm
= –2.303 ¥ 1 ¥ 8.314 ¥ 298 log Á ˜ 3 1
Ë 1¯
W = –3.988 kJ (a) PVg = constant
nC p dT P1 – g Tg = constant
55. DS =
T TP(1 – g)/g = constant
T1P1(1 – g)/g = T2P2(1 – g)/g
Ê 25.5 ˆ
=1¥ ÚÁ + 13.6 ¥ 10-3 - 42.5 ¥ 10-7 T ˜ dT
Ë T ¯ Ê 1ˆ
–2/5
T2 = 300 ÁË ˜¯ = 395.85
2

3 V2
w = DU = n CvdT = 1 ¥ ¥ 8.314 ¥ 95.85 DSsys.= nR ln = 1 ¥ 8.314 ln 3 = 9.134 J/K
w = 1195.37 J 2 V1
nRT2 For reversible process
V2 = = 16.25 L DST = 0
P2
DSsurr.= – DSsys.= – 9.134 J/K
(b) DU = w
(ii) DSsys.= 9.134 J/K
1 ¥ 1.5 ¥ 8.314 (T2 – 300) = –Pext[V2 – V1]
– qirrev. È q – 836.6 ˘
Ê RT RT ˆ DSsurr.= = - Í rev. ˙˚
= – 2 ¥ 101.3 Á 2 – 1 ˜ T Î 298
Ë P2 P1 ¯
= – DSsys. + 2.807
Ê T ˆ DST = DSsys. + (–DSsys. + 2.807) = 2.807 J/K
(T2 – 300) = 1.333 Á 300 – 2 ˜
Ë 2¯ (iii) For free expansion system does not absorb any
heat so q = 0
nRT2
T2 = 420 K and V2 = = 17.24 L DSsys. = 0
P2 DST = DSsys. = 2.807 J/K
w = DU = 1.5 ¥ 8.314 (420 – 300) 62. (i) DSsys. = 0, DSsurr. = 0, DST = 0
w = 1496.52 J (ii) DE = w = n Cv (T2 – T1) = – Pext[V2 – V1]
60. V1 = 20 L, g = 7/5, T1 = 673 K, 0.5 ¥ 1.5 ¥ 8.314 (T2 – 473)
P2 = 0.2 MPa = 2 atm, P1 = 0.7 MPa = 7 atm Ê T2 473 ˆ
ÁË – ˜
PV = –101.3 ¥ 2 ¥ 0.5 ¥ 0.0821 2 5 ¯
n= 1 1
= 2.5
RT1 Ê T2 ˆ
ÁË – 94.6˜¯
(i) DU = DH = 0 T2 – 473 = – 1.333 2
P 7 T2 = 359.49 K
q = –w = nRT ln 1 = 2.5 ¥ 8.314 ¥ 673 ln
P2 2 È T P˘
DSsys. = n ÍC p ln 2 + R ln 1 ˙
q = 17.52 kJw = –17.52 kJ Î T1 P2˚
(ii) P1V1g = P2V2g
È 359.49 5˘
7(20)g = 2(V2)g fi V2 = (3.5)5/7 = 48.92 L = 0.5 Í2.5 ¥ 8.314 ln + 8.314 ln ˙
Î 473 2˚
P2V2
T2 = = 470.46 K DSsys. = 0.957 J/K
nR since no heat is transferred q = 0
q = 0, w = DU = nCV[T2 – T1] DSsurr. = 0
= 2.5 ¥ 2.5 ¥ 8.314(470.46 – 673) = –10.524 kJ DST = DSsys. = 0.957 J/K
w = DU = – 10.524 kJ (iii) In free expansion q = w = DU = 0
DH = 2.5 ¥ 3.5 ¥ 8.314 (470.46 – 673)= – 14.73 kJ T is constant.
(iii) q = w = DU = DH = 0 P 5
(iv) q = 0, DU = w = nCV[T2 – T1] = –Pext[V2 – V1] DSsys. = nR ln 1 = 0.5 ¥ 8.314 ¥ ln = 3.81 JK
P2 2
2.5 ¥ 2.5 ¥ 8.314 (T2 – 673)
ÊT Tˆ DSsurr. = 0
= – 101.3 ¥ 2 ¥ 2.5 ¥ 0.0821 ÁË 2 – 1 ˜¯ DST = DSsys = 3.81 J/K
2 7
63. P1 = 1 atm, V1 = 1 L
ÊT ˆ P2 = 1001 atm, V2 = 0.99L Let P = a + bV
T2 – 673 = – 0.79 Á 2 – 96.142˜
Ë 2 ¯ On finding a = 100001, b = –105 so
T2 = 536.91 K
P = (100001 – 105V)
w = DU = 2.5 ¥ 2.5 ¥ 8.314 (–136) = – 7.1 kJ V2
DH = 2.5 ¥ 3.5 ¥ 8.314 (–136) = – 9.9 kJ w = – Ú PdV = Ú (100001 – 105 V) dV
V1
(v) DU = DH = 0
nRT 2.5 ¥ 0.821 ¥ 673 105 2
V2 = = w = – 100001 (V2 – V1) + (V2 – V12 )
= 69 L 2
P2 2
w = –Pext[V2 – V1] = –2 ¥ 49 = –98.13 L-atm 105
w = – 100001 (–0.01) + (–0.0199)
w = –98.13 ¥ 101.3 = –9940.9 J = 5.01 L-atm 2
w = – 9.94 kJ q = –w = 9.94 kJ w = 501 J DU = w = 501 J
61. (i) The entropy change of the system DSsys. will be DH = DU + (P2V2 – P1V1)
same in all the three process as it is state function. = 501 + (1001 ¥ 0.99 – 1 ¥ 1) ¥ 100 = 99500 J
DH = 99.5 kJ

T2 3 1000 3 67. At 298 K,

64. (i) DSsys.= n Cv ln = 1 ¥ R ln = R ln 10 DG° = – 6333 kJ/mole
T1 2 100 2
DH° = – 5737 kJ/mole
DST = 0 (Reversible process) and DG° = DH° – TDS°
3 so DS° = 2 kJ/mole
DSsurr.= –DSsys.= - R ln 10
2 At 310 K
3 DG = – 5737 – 2 ¥ 310 = –6357 kJ/mole
(ii) DSsys.= R ln 10 Additional non-PV work = |DG – DG°| = 24 kJ/mole
2
68. w = 200 J; q = –140 J;
w=0 DV = 0 for isochoric
q = DE + (–w); where –w is work done by the system
3
q = –DE = - R (900) = –nCVDT DE = q + w
2 DE = –140 + 200 = +60 J
q –3R (900)
DSsurr.= – =
3
= - R (0.9) 69. w = –PextDV = –1.5 ¥ (1.0 – 0.5) = –0.75 L atm
T 2 ¥ 1000 2 = –0.75 ¥ 101.3 J = –75.975 J
3 3 3 1 L atm = 101.3 J
DST = R ln 10 – R (0.9) = R (1.402) Now, DE = 200 – 75.975 = +124.025 J
2 2 2
70. Since the external pressure is greatly different from the
65. We know
pressure of N2 and thus, process is irreversible.
G = H – TS = U + PV – TS
w = –Pext (V2 – V1)
dG = dU + PdV + VdP – TdS – SdT w = –1 ¥ (V2 – V1)
w = 0, dV = 0, dV = dq = T dS so Given, V1 = 2 L V2 =? T = 273 K
dG = TdS + VdP – TdS – SdT P1 = 5 atm P2 = 1 atm
dG = VdP – SdT fi DG = VDP –ÚSdT \ P1V1 = P2V2 for isothermal
VdP = V (P2 – P1) 2¥5
\ V2 = = 10 L
P2 P1 P 1 4 1
= fi 2 = fi P2 = \ w = –1 ¥ (10 – 2) = –8 litre atm = 8 ¥ 101.3 J
T2 T1 400 300 3
= –810.4 J
VdP = 24.6 (4/3 – 1) = 8.2 L-atm = 820 J DH vap. 26 ¥ 103
T2 71. (a) DSvap. = = = +84.41 JK–1 mol–1
ÚSdT = ÚT
1
(10 + 0.01T ) dT T 308
= 10(T2 – T1) + 0.005(T22 – T12) DH cond. 26 ¥ 103
(b) DScond. = =– = –84.41 JK–1 mol–1
SdT = 10(100) + 0.005 (4002 – 3002) = 1350 T 308
DG = 820 – 1350 = – 530 J ( Hcond = –26 kJ)
66. (a) n = 2 72. DHdissolution = Lattice energy + Hydration energy
2 ¥ 0.0821 ¥ 300 = 777.8 – 774.1 = 3.7 kJ mol–1
V1 = = 49.26 L Now DG = DH – TDS
1
V1 V2 49.26 V2 = 3.7 – 298 ¥ 0.043 = 3.7 – 12.814
= fi = fi V2 = 90.31 L DG = –9.114 kJ mol–1
T1 T2 300 550
73. DG° = –2.303 RT log Keq
(i) w = – PDV = 1(90.31 – 49.26) = – 41.05 L-atm DG° = –2.303 ¥ 8.314 ¥ 300 log [2.0 ¥ 10–7]
w = – 41.05 ¥ 101.3 = – 4158.36 J = –4.15 kJ = +38479.8 J mol–1 = +38.48 kJ mol–1
q = DH = ÚnCpdT Also, DG° = DH° – TDS°
È 8.368 ¥ 10 –3 2 ˘ DH o – DG o 28.40 – 38.48
= 2 Í12.552(T2 – T1 ) + (T2 – T12 ) ˙ \ DS o = =
Î 2 ˚ T 300
È 8.368 ¥ 10 –2 ˘ = –0.0336 kJ = –33.6 JK–1
q = DH = 2 Í12.552(250) + (212500)˙
Î 2 ˚ 74. We know,
Path CA – Isothermal compression
q = DH = 24.04 kJ
Path AB – Isobaric expansion
Cv = Cp – R = 4.238 + 8.368 ¥ 10–2 T
Path BC – Isochoric change
DU = ÚnCvdT = 19.9 kJ
Let Vi and Vf are initial volume and final volume at re-
(b) w = 0
spective points,
Since, DV = 0 for isochoric
For temperature T1 (For C): PV = nRT1
q = DU = 19.9 kJ
2 ¥ 10 = 1 ¥ 0.0821 ¥ T1
DH = ÚnCpdT = 24.04 kJ
\ T1 = 243.60 K

PV PV 5
For temperature T2 (For C and B): 1 1
= 2 2 For (i) qA Æ B = +n ¥ CP ¥ DT = +2 ¥ ¥ R ¥ 300 =
T1 T2 2
2 ¥ 10 20 ¥ 10 +1500 ¥ 2 = +3000 cal(R = 2 cal)
= (ii) qBÆC = DE – w (DE = 0)
T1 T2
V
T2 \ qBÆC = DE – w = + ÚPdV = +nRT ln D
\ = 10 VB
T1 4
= +2 ¥ 2 ¥ 600 ln = +1.663 + 103 cal
\ T2 = 243.60 ¥ 10 = 2436.0 K 2 3
(iii) qCÆD = n ¥ Cv ¥ DT = 2 ¥ ¥ 2 ¥ – 300 =
V 2
Path CA: w = +2.303 nRT1 log i –1800 cal
Vf VA 1
10 (iv) qDÆA = +nRTA ln = +2 ¥ 2 ¥ 300 ln =
= 2.303 ¥ 1 ¥ 2 ¥ 243.6 log VD 4
1
= +1122.02 cal –2 ¥ 2 ¥ 300 ¥ 1.386 = –1.663 ¥ 10 cal 3
DE = 0 for isothermal compression; Also q = w \ Q = qAÆB + qBÆC + qCÆD + qDÆA =

Path AB: w = –P(Vf – Vi) 3000 + 1663 – 1800 – 1663 = 1200 cal
= –20 ¥ (10 – 1) = –180 litre atm (c) Since the process ABCDA is a cyclic process
–180 ¥ 2 \ DE = 0 or Q = DE – Q = –w
= = – 4384.9 cal or Q = –1200 cal
0.0821
i.e., work done on the system = 1200 cal
Path BC: w = –P (Vf – Vi) = 0 ( Vf – Vi = 0)
76. We know,
since volume is constant for monoatomic gas heat
(i) Vessel is of fixed volume, hence DV = 0.
change at constant volume = qv = DE.
No work is done, w = –PextDV = 0
Thus for path BC qv = Cv ¥ n ¥ DT = DE
(ii) The H2 gas formed drives back the atmosphere
3 hence.
\ qv = R ¥ 1 ¥ (2436 – 243.6)
2 w = –Pext ◊ DV = –DngRT
3 where n is the number of mole of H2 gas obtained
qv = ¥ 2 ¥ 1 ¥ 2192.4 = 6577.2 cal from n mole of Fe(s).
2
Since process involves cooling Fe(s) + 2HCl(aq) Æ FeCl2(aq.) + H2(g)
\ qv = DE = –6577.2 cal 1 mole 1 mole
Also in path AB, the intenal energy in state A and state 50
\ n= = 0.8929 mole
C is same. Thus during path AB, an increase in inter- 56
nal energy equivalent of change in internal energy dur- \ w = –0.8929 ¥ 8.314 ¥ 298 = –2212.22 J
ing path BC should take place. Thus DE for path AB = The reaction mixture in the given system does
+6577.2 cal 2.212 kJ of work driving back to atmosphere.
Now q for path AB = DE – wAB = 6577.2 + 4384.9 = 77. DH = DE + PDV
10962.1 cal Given, DE = +0.21 kJ mol–1 = 0.21 ¥ 103 J mol–1
Cycle: DE = 0 ; q = –w = – [wPathCA + wPathAB + wPathBC] P = 1.0 ¥ 105 Pa
= – [+1122.02 + –4384.9 + 0] DV = V(aragonite) – V(Calcite)
\ q = –w = +3262.88 cal Ê 100 100 ˆ
75. For the given cyclic process, = ÁË – ˜ cm3 mol–1 of CaCO3
2.93 2.71¯
VB V = –2.77 cm3 = –2.77 ¥ 10–6 m3
= 2, D = 4, TA = 300 K
VA VA \ DH = 0.21 ¥ 103 – 1 ¥ 105 ¥ 2.77 ¥ 10–6
(a) For isobaric process AB = 209.72 J = 0.20972 kJ mol–1
VA VB 78. Given, for the change, DH = 30 ¥ 103 J mol–1, DS = 70
= JK–1 mol–1
TA TB
For a non-spontaneous reaction
VB DG = +ve
\ TB = TA ¥ = 300 ¥ 2 = 600 K Since DG = DH – TDS
VA
(b) The following process are there in complete cycle \ DH – TDS should be positive
(i) A Æ B Isobaric expansion or DH > TDS
(ii) B Æ C Isothermal expansion DH 30 ¥ 103
(iii) C Æ D Isochoric compression or T< fiT < fi T < 428.57 K
DS 70
(iv) D Æ A Isothermal compression

79. Gaseous substances generally possess more entropy 1718

than solids. So whenever the products contain more (iv) DSsurr = = –5.76 J/K.
298
moles of a gas than the reactants, the entropy change is
probably positive. And hence, DS is As entropy of the system increases by 5.76
(a) positive J, the entropy of the surroundinig decreases
(b) negative by 5.76 J, since the process is carried out re-
(c) small, the sign of DS is impossible to predict versible.
Dng = 0 (v) DSsys + DSsurr = 0 ... for reversible process.
(d) negative (b) (i) DS = 5.76 J/K, which is the same as above
(e) negative because S is a state function.
(f) negative (ii) w = 0. ( pext = 0)
[Note: For a given substance at a given temperature, (iii) No heat is exchanged with the surroundings.
Sgas > Sliquid > Ssolid] (iv) DSsurr = 0
80. Consider the process: Br2(l) Æ Br2(g) (v) The entropy of the system plus surroundings
The b.p. of a liquid is the temperature at which the liq- increases by 5.76 J/K, as we expect entropy
uid and the pure gas coexist at equilibrium at 1 atm. to increases in an irreversible process.
\ DG = 0 83. We have to find DH for
As it is given that DH and DS do not change with tem- NH 4 NO3(s) h N 2O(g) + 2H 2O(l) ; DH = ?
perature
DH = DH° = 30.91 kJ D r H = Sn P ( DH fo ) P - Sn R [ DH fo ]R
DS = DS° = 93.2 J/K = 0.0932 kJ/K = DH of N 2O + 2 DH f H 2O – DH of
o
NH 4 NO3
We have, DG = DH – TDS = 0 at equilibrium
DH 30.91 Given, DH N O = +81.46 kJ, DH H2O = –285.8 kJ,
\ T= = 331.6 K
2
=
DS 0.0932 DH NH4 NO3 = –367.54 kJ
This is the temperature at which the system is in equi- \ DHreaction = +81.46 + 2(–285.8) – (–367.54)
librium, that is, the BP of bromine. DH = –122.6 kJ
81. We have, Further DH = DE + DngRT
T1 – T2 (Dng = 1 – 0 = 1, R = 8.314 J and T = 298 K)
h= , where T1 and T2 are the temperatures of
T1 \ –122.6 ¥ 103 = DE + 1 ¥ 8.314 ¥ 298
sink and source respectively. \ DE = –125077 joule
= –125.077 kJ
T1 – T2 1 84. Given,
\ h= = ...(i)
T1 6 3 1
Now the temperature of the sink is reduced by 65 K. 2C(s) + H2(g) + N2(g) h CH3CN(g)
2 2
\ temperature of the sink = (T2 – 65) DH = 88 (i)
T1 – (T2 – 65) 1 2C(s) +3H2(g) h C2H6(g) DH = –84 (ii)
\ h= = ...(ii) C(s) h C(g) DH = 717
T1 3
N2(g) h 2N(g) DH = 946
On solving Eqs. (i) and (ii), we get, H2(g) h 2H(g) DH = 436
T1 = 325 K BC–H = 410
T2 = 390 K from equation (i)
V (2 ¥ 717 + 1.5 ¥ 436 + 0.5 ¥ 946) – (3 ¥ 410 +
82. (a) (i) DS = 2.303nR log 2 BC–C +BC∫N) = 88
V1
20 BC–C + BC∫N = 1243 (iii)
= 2.303 ¥ 1 ¥ 8.314 ¥ log = 5.76 J/K. from equation (ii)
10
V2 (2 ¥ 717 + 3 ¥ 436) – (BC–C + 6 ¥ 410) = –84
(ii) wrev = 2.303 nRT log BC–C = 366 kJ/mole from equation (iii)
V1
20 BC ∫ N = 877 kJ/mole
= –2.303 ¥ 1 ¥ 8.314 ¥ 298 ¥ log 85. C2H4 + H2 h C2H6
= –1718 J. 10
here DrH = DHhydrogenation
(iii) For isothermal process, DE = 0 and heat is
absorbed by the gas, \ D r H = [ DH combustion
o
]R - [ DH combution
o
]P
qrev = DE – W = 0 – (–1718) = 1718 J = [(–1409) + (–285.6)] - [-1558.3]
\ qsurr = 1718 J. ( process is reversible)
= –136.8 kJ

OR
We have to find C
C C
C2 H 4(g) + H 2(g) h C2 H 6(g) ; DH = ? DH = ?
C C
C
Given, C2 H 4(g) + 3O 2(g) h 3CO 2(g) + 2H 2O(g) ;
DH = –1409.5 kJ (1) For reactants:

Heat of atomisation of 6 moles of C = 6 ¥ 170.9 kcal
7
C2 H 6 + O 2(g) h 2CO 2(g) + 3H 2O(g) ; Heat of atomisation of 6 moles of H = 6 ¥ 52.1 kcal
2 For products:
DH = –1558.3 kJ ...(2) Heat of formation of 6 moles of C – H bonds = –6 ¥ 99
Heat of formation of 3 moles of C – C bonds = –3 ¥ 83
1 Heat of formation of 3 moles of C = C bonds = –3 ¥ 140
H 2 + O 2(g) h H 2O(g) ; DH = –285.6 kJ ...(3)
2 On adding, we get heat of formation of C6H6, i.e.,
Adding Eqs. (1) and (3) DH = 6 ¥ 170.9 + 6 ¥ 52.1 – 6 ¥ 99 – 3 ¥ 83 – 3 ¥ 140
= 75.0 kcal.
7 89. MgSO4 ◊ 7H2O (s) + aq Æ MgSO4 (aq) D rH 2
C2 H 4(g) + O 2(g) + H 2(g) h 2CO 2(g) + 3H 2O(g) ;
2 = +13.807 kJ mol–1 ...(ii)
DH = –1695.1 kJ ...(4) Equation (i) can be written as follows:
Subtracting Eq. (2) from (4) MgSO4(s) + 7H2O(l) + aq Æ MgSO4(aq)
7 DrH = –91.211 kJ mol–1 ...(iii)
C2 H 6(g) + O 2(g) h 2CO 2(g) + 3H 2O(g) Equation (iii) – (ii) will give
2
MgSO4(s) + 7H2O(l) Æ MgSO4 ◊ 7H2O(s)
DH = –1558.3 kJ ...(5)
– – – – + DrH = –91.211 – 13.807 = –105.018 kJ mol–1.
C2 H 4(g) + H 2(g) ææ
Æ C2 H 6(g) ; 90. Given, I 2(s) h I 2(v) ; DH = 24 cal/g at 200°C
DH = –136.8 kJ DrCP = CP of product – CP of reatant

\ heat of hydrogenation of C2H4 = 136.8 kJ = 0.031 – 0.055
86. A better gas welder is one which posses high calorific = –0.024 cal/g
value, i.e., heat produced by 1 g of fuel. Now DH T2 - DH T1 = DrCP (T2 – T1)
DHcombustion for C2H6 = –341.1 kcal DH T2 – 24 = –0.024 ¥ (523 – 473)
– 341.1 \ DH T2 = 24 – 1.2 = 22.8 cal/g.
\ calorific value = kcal/g = –11.37 kcal/g
30
DHcombustion for C2H2 = –310.0 kcal 91. C2H6 + O2 h 2 CO2 + 3 H2O 2 mol
for 1 mole DH = – 1560 kJ
–310.0
\ calorific value = kcal/g = –11.92 kcal/g D r H = Sn P ( DH fo ) P - Sn R [ DH fo ]R
26
\ C2H2 is a better gas welder. –1560 = 2 (–395) + 3(286) – ( DH f )C2H6
o
87. Given that

DH°f = –790 – 858 + 1560 = – 88 kJ/mol
C(s) + 2H2(g) Æ CH4(g); DH = –17.9 kcal
DH
Energy change in reactants: 92. CuSO4 + 5H2O CuSO4 ◊ 5H2O
Heat of atomisation of 1 mole of C = 170.9 kcal
–15.9 kcal +2.8
Heat of atomisation of 4 moles of H = 4 ¥ 52.1 kcal
Energy change in product: CuSO4(aq.)
Heat of formation of 4 moles of C–H bonds = 4 ¥ x Applying Hess’s law DH + 2.8 = –15.9
kcal. DH = –15.9 – 2.8 DH = –18.7 kcal
(where x is the energy of formation of C–H bonds in 93. O2 consumed by body in 1 hr.
kcal/mole). = 20 ¥ 60 ¥ 200 (0.2 – 0.1) = 24000 mL. at 37°C
Since the algebraic sum of all the heat changes is equal So, volume at 273 K can be calculated by
to the heat of formation of the above given equation, V 24000
we have =
273 310
170.9 + 4 ¥ 52.1 + 4x = –17.9; x = –99.3 kcal
Thus the bond energy = +99.3 kcal/mole. V = 21135.48 mL = 0.9435 mole O2
88. We have to calculate DH for the reaction C6H12O6 + 6O2 h 6CO2 + 6H2O
6C(s) + 3H2(g) Æ C6H6(g) DH = –2880 kJ/mol

0.9435 100. Given,

moles of glucose h 6C(s) + 3H2(g) h C6H6(l) DH = 49
6
2880 ¥ 0.9435 C6H6(l) h C6H6(g) DH = 45
Heat released = = 452.9 kJ so 6C(s) + 3H2(g) h C6H6(g) DH = 94 (i)
6
Heat used for muscular work = 452.9 ¥ 0.25 = 113.22 kJ 2C(s) + H2(g) h C2H2(g) DH = 75 (ii)
so distance = 1.132 km (i) – 3 ¥ (ii)
1 H + 1 Cl –92.3 HCl(g) 3C2H2(g) h C6H6(g) = –131
94. 2 2 2 2
–167.44 3[BC∫C + 2BC–H] – [3BC–C + 3BC=C + 6BC–H – R.E.] = –131
x
H+ (aq.) Cl– (aq.) 3[BC ∫ C – BC – C– BC = C] + RE = –131
–92.30 + x = –167.44 R.E. = –131 + 99 = –32
x = –75.14 kJ/mol 101. 2Al(s) + Fe2O3(s) h Al2O3(s) + 2Fe(s)
95. C6H12O6(s) + 6O2(g) h 6CO2(g) + 6H2O(l) 0.2 mole 0.1 mole — —
1.0 g — — 0.1 0.2
DE = mCDT Since, 0.254 kg ice melted
DE = –10 kJ ¥ 1.56 = 15.6 kJ – 254 ¥ 1.436
\ DH = = 20.26 kcal
Since Dng = 0 \ DH = DE 18
for 1 mole = 15.6 ¥ 180 = –2808 kJ Heat liberated for 0.1 mole = 20.26 kcal
96. Ca(s)hCa(g) h Ca+1(g) h Ca+2(g) Æ CaC2(s) Heat liberated for 1 mole = –202.6 kcal
- -2
2C(s) h 2C(g) h C2(g) h C2(g) h C2(g) DH
102. CH2 O (CH2O)
–60 = [179 + 590 + 1143 + 718 ¥ 2 –134
–122
– 614 – 315 + 410 + L.E.]
L.E. = –2889 kJ/mole nCO2 + nH2O
–676 Applying Hess law
97. 2C(g) + 6H(g) C2H6(g)
DH – 122 = – 134 DH = 12 Kcal
2 ¥ 171.8 3(104.1) 103.
2C(s) + 3H2(g) DHt
DrH= –676 + 343.6 + 312.3 = –676 + 655.9 = 20.1
Potential energy
1-butene
4 (C – H) = 396 (C–C) + 6(99) = 676 1771
C – H = 99 K (C–C) = 676 –594 = 84 Cis-butene 649800
950
Cs(s) + 1 Cl2(g)
–388.6 trans-butene
CsCl(s)
98. 2 Heat of combution
1 (243) 4CO2 + 4H2O of trans-butene
81.2
2
Reaction coordinate
Cs(g) Cl
x = LE \ Heat of combution of trans-2 butene
375.7 –348.3 = –649800 + 1771 + 950
= –604079
Cs (g) Cl (g)
CH3 H
81.2 + 375.7 + 121.5 – 348.3 + x = –388.5 C C + 6O2 4CO2 + 4H2O
578.4 – 348.3 + 388.5 = –x
H CH3
–x = 966.9 – 348.3
x = –618.6 kJ mol–1 DHC = DrH = S(BDE)R – S(BDE)P = –603.079
– 2839.2
99. 2C(g) + 6H(g) ææææ Æ C2H6 = [2 BC – C + BC = C + 8 ¥ BC – H] + 6 ¥ BO = O
– 2275.2 – 8 ¥ BC = O – 8 ¥ BO – H = –603.079
2C(g) + 4H(g) ææææ
Æ C2H4 BC = C = 192.921 kcal/mole
– 5506
6C(g) + 6H(g) æææÆ C6H6 OR
(C – C) + 6(C – H) = –2839.2 fi C – C = 373.98 Given
(C = C) + 4(C – H) = –2275.2 fi C = C = 637.72 CH3 CH3
CH3 HC CH
–6(410.87) + 3(373.98) + 3(631.72) + R.E. = –5506 HC CH CH3
–5482.3 + RE = 0.5506 cal k cal
DH1 = –950 = –0.95 (i)
R.E. = –23.68 kJ/mol mole mole

CH3 CH3 ÆCH2 = CH – CH2 – CH3 (d) DU = nCvDT

HC CH
In isothermal process, DU = 0 as DT = 0
cal k cal In adiabatic process, DU = nCv(T3 – T1) < 0 as T3
DH2 = +1771 = 1.771 (ii)
mole mole < T1.
CH2 = CH – CH2 – CH3 + 6O2 h 4CO2 + 4H2O fi DUisothermal > DUadiabatic
k cal Note: Here only magnitudes of work is being
DH3 = –649.8 (iii) considered otherwise both works have negative
mole
(ii) + (iii) – (i) sign.
CH3 2. (a, c)
HC CH + 6O2 Æ 4CO2 + 4H2O(l) (a) Entropy is state function, change in entropy in a
CH3 cyclic process is zero.
DH = –647.079 (iv) Therefore, DSX Æ Y + DSY Æ Z + DSZ Æ Y = 0
H2O(l) h H2O(g) fi –DSZ Æ X = DSX Æ Y + DSY Æ Z
k cal = DSX Æ Z
DH4 = 11 (v) Work is a path function.
mole
(iv) + 4 ¥ (v) Therefore, WX Æ Y Æ Z = WX Æ Y. Also, work is the area
+6CO2 Æ 4CO2 + 4H2O(g) under the curve on p-V diagram.
DH = –603.079 X Y X Y
[2 BC – C + BC = C + 8 BC – H] WX Æ Y
= WX Æ Y Æ Z
+ 6BO = O–8 BC = O–8BO – H = –603.079 P Z P WX Æ Y Z
= [2 BC – C + BC = C + 8 ¥ BC – H] + 6 ¥ BO = O
– 8 × BC = O – 8 ¥ BO – H = –603.079
BC = C = 192.921 kcal/mole V V
104. Given,
n(CH2=CH2) Æ (–CH2–CH2–)n DH = – 72 As shown above WX Æ Y + WY Æ Z = WX Æ Y = WXÆYÆZ
i.e., BC = C – 2 BC – C = – 72 (i) but not equal to WX Æ Z.
6C(s) + 3H2(g) h C6H6(l) DH = 49 (ii) 3. (d) 2C(s) + H2 H —C∫C—H
C6H6(l) h C6H6(g) DH = 30 (g)
2 ¥ (–350) + EC∫C
R.E. of C6H6 = –152 +1 ¥ 1410 +330
1 absorbed energy released energy
H2 h H DH = 218
2 DrH = Eabs – Erel
C(s) h C(g) DH = 715 255 = [1 ¥ 1410 + 330] – [2 ¥ 350 + EC ∫ C]
BC–H = 415 for equation (ii)
\ EC ∫ C = 815 KJ/mole
(6 ¥ 715 + 6 ¥ 218) – (3BC–C + 3BC=C + 6 ¥ 415 – RE)
OR
= 49
For calculation of C ∫ C bond energy, we must first
BC–C + BC=C = 959 (iii)
from equation (i) and (iii) calculate dissociation energy of C2H2 as
BC–C = 343.66 BC = C = 615.33 C2H2(g) h 2C(g) + 2H(g) (i)
Using the given bond energies and enthalpies:
C2H2(g) h 2C(g) + 2H(g); DH = –225 kJ (ii)
PREVIOUS YEARS’ QUESTIONS 2C(s) h 2C(g); DH = 1410 kJ (iii)
OF JEE (MAIN AND ADVANCED) H2(g) h 2H(g) DH = 330 kJ (iv)
1. (a, c, d) adding Eqs. (ii), (iii) and (iv) gives Eq. (i).
(a) Since, change of state (p1, V1, T1) to (p2, V2, T2) is fi C2H2(g) h 2C(g) + 2H(g); DH = 1515 kJ
isothermal therefore, T1 = T2. fi 1515 kJ = 2 ¥ (C – H) BE + (C∫C)BE
(b) Since, change of state (p1, V1, T1) to (p3, V3, T3) is = 2 ¥ 350 + (C ∫ C)BE
an adiabatic expansion it brings about cooling of fi (C ∫ C)BE = 1515 – 700 = 815 kJ/mol
gas, therefore, T3 < T1.
(c) Work done is the area under the curve of p-V dia- (Passage from Q.No. 4 to Q. No. 6)
gram. As obvious from the given diagram, magni- 4. (b) L Æ M At constant V – isochoric.
tude of area under the isothermal curve is greater NÆK
than the same under adiabatic curve, hence Wiso- 1
5. (c) By Boyle’s law at constant temperature P μ
thermal > Wadiabatic
V

By Charle’s law at constant pressure, V μ T = –1364.47 – 2.4776 = –1366.9476 kJ/mol

Process taking place at or = –1366.95 kJ/mol
Constant temperature – isothermal 10. (a, b, c) Hint: This problem includes concept of iso-
Constant pressure – isobaric thermal adiabatic irreversible expansion.
Constant volume – isochoric Process is adiabatic because of the use of thermal inso-
Constant heat – adiabatic lution therefore, q = 0
pext = 0
K Æ L At constant P, V μ T \ heating
w = pext ◊ DV = 0 ¥ DV = 0
L Æ M At constant V, P μ T \ cooling Internal energy can be written as
M Æ N At constant p, V μ T \ cooling DE = q + W = 0
N Æ K At constant V, P μ T \ heating Because, DE = nCVDT
6. (b, c, d) DE = 0
Mixing of solute and solvent is spontaneous process for \ DT = 0
ideal solution. \ T1 = T2
DHmix = 0, DVmix = 0 and DGmix < 0 So, in isothermal condition PV = constant whereas PV g
DGmix = DHmix – TDSmix = 0 – TDSmix = constant for adiabatic only
11. (b) At 100°C and 1 atmosphere pressure,
DGmix < 0 and DSmix > 0 \ DSsurrounding = 0
7. (a) The process is isothermal expansion, hence H2O(l) m H2O(g) is at equilibrium.
q = –W At equilibrium, DStotal = 0 = (for reversible process)
DE = 0 and DSsystem + DSsurrounding = 0
V As we know during conversion of liquid to gas entropy
W = –2.303 nRT log 2 of system increases, in a similar manner entropy of sur-
V1
335 rounding decreases.
= –2.303 ¥ 0.04 ¥ 8.314 ¥ 310 ¥ log
50 \ DSsystem > 0 and DSsurrounding < 0
= –208 J
q = +208 J, W = –208 J 12. (d) For the given reaction,
( Work done by the system) 2NO(g) + O2(g) m 2NO2(g)
8. (c) C6H12O6 + 6O2 Æ 6CO2 + 6H2O D rH = ? Given, DGfo (NO) = 86.6 kJ / mol
D r H = DH C = Sn P ( DH fo ) P - Sn R ( DH fo ) R DGfo (NO 2 ) = ?
= [(6 ¥ (- 400) + 6 ¥ (- 300) - (1 ¥ -1300)]
K p = 1.6 ¥ 1012
= - 2400 - 1800 + 1300
Now, we have,
= - 2900 KJ per mole
- 2900 DGfo = 2 DGfo(NO2 ) - [2 DGfo (NO) + DGfo(O2 ) ]
= KJ/gram = -16.11 KJ/gram
180 = - RT ln K p = 2 DGfo(NO2 ) - [2 ¥ 86,600 + 0]
9. (a) C2H5OH(l) + 3O2(g) h 2CO2(g) + 3H2O(l)
1
DE = –1364.47 kJ/mol DGfo(NO2 ) = [2 ¥ 86600 - R ¥ 298 ln (1.6 ¥ 1012 )]
DH = DE + DngRT 2
Dng = –1 DGfo(NO2 ) = 0.5[2 ¥ 86,600 - R ¥ (298) ln (1.6 ¥ 1012 )]
Ê -1 ¥ 8.314 ¥ 298 ˆ
DH = ÁË -1364.7 + ˜¯ KJ
1000

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Physical Chemistry for JEE (Main & Advanced) Module-II

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IIT JEE PC-V2_Prelims.indd 5 5/13/2017 11:15:41 AM

● Level-II contains slightly difficult questions suitable for JEE Advanced.

comprehension, match the column and single digit integer).

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4. Solid State 4.1–4.31

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Thermodynamics deals with the feasibility of the reaction but

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DC È[ R]t2 - [ R]t1 ˘ [ P]t2 - [ P]t1 At T Æ ; maximum rate

t1 Time C (6) Surface area

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2. In the formation of sulphur trioxide by contact process, k1

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