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12mm
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IIT JEE PC-V2_Prelims.indd 1 5/13/2017 11:15:38 AM
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
McGraw Hill Education Offices

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Physical Chemistry for JEE (Main & Advanced) Module-II
Copyright © 2017, McGraw Hill Education (India) Private Limited.
No part of this publication may be reproduced or distributed in any form or by any means, electronic, mechanical, photocopying, recording,
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may be entered, stored and executed in a computer system, but they may not be reproduced for publication.
This edition can be exported from India only by the publishers,

ISBN (13): 978-93-5260-603-0

ISBN (10): 93-5260-603-5
Information contained in this work has been obtained by McGraw Hill Education (India), from sources believed to be reliable. However, neither McGraw Hill
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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 instant 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

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of society from the rudest to the most refined, and in all its grades;
the Doctor used to say they might be called semi-intellectual. The
uses of hunting are obvious wherever there are wild animals which
may be killed for food, or beasts of prey which for our own security it
is expedient to destroy.
Indeed because hunting, hawking and fishing (all which according to

Gwillim and Plato are comprised in the term Venation) tend to the
providing of sustenance for man, Farnesius doth therefore account
them all a species of agriculture. The great heraldic author approves
of this comprehensive classification. But because the more heroic
hunting in which danger is incurred from the strength and ferocity of
the animals pursued, hath a resemblance of military practice, he
delivers his opinion that “this noble kind of venation is privileged from
the title of an Illiberal Art, being a princely and generous exercise;
and those only, who use it for a trade of life, to make sure thereof,
are to be marshalled in the rank of mechanics and illiberal artizans.”
The Doctor admired the refinement of these authors, but he thought
that neither lawful sporting, nor poaching could conveniently be
denominated agricultural pursuits.
He found it not so easy to connect the love of gaming with any

beneficial effect; some kind of mental emotion however, he argued,
was required for rendering life bearable by creatures with whom
sleep is not so compleatly an act of volition, that like dogs they can
lie down and fall asleep when they like. For those persons therefore
who are disposed either by education, capacity, or inclination to
make any worthier exertion of their intellectual faculties, gaming,
though infinitely dangerous as a passion, may be useful as a
pastime. It has indeed a strong tendency to assume a dangerous
type, and to induce as furious an excitement as drunkenness in its
most ferocious form, but among the great card-playing public of all
nations, long experience has produced an effect in mitigating it
analogous to what the practice of inoculation has effected upon the
small-pox. Vaccination would have afforded our philosopher a better
illustration if it had been brought into notice during his life.
Pope has assigned to those women who neither toil or spin, “an old
age of cards,” after “a youth of pleasure.” This perhaps is not now so
generally the course of female life, in a certain class and under
certain circumstances, as it was in his days and in the Doctor's. The
Doctor, certainly was of opinion that if the senescent spinsters and
dowagers within the circle of his little world, had not their cards as
duly as their food, many of them would have taken to something
worse in their stead. They would have sought for the excitement
which they now found at the whist or quadrille table, from the bottle,
or at the Methodist Meeting. In some way or other, spiritual or
spirituous they must have had it;1 and the more scandalous of these
ways was not always that which would occasion the greatest
domestic discomfort, or lead to the most injurious consequences.
Others would have applied to him for relief from maladies which by
whatever names they might be called, were neither more nor less
than the effect of that tædium vitæ which besets those who having
no necessary employment have not devised any for themselves. And
when he regarded the question in this light he almost doubted
whether the invention of cards had not been more beneficial than
injurious to mankind.
1 It happened during one of the lamented Southey's visits here at the Vicarage, West-
Tarring, that a cargo of spirits was run close by. His remark was—“Better spirituous
smuggling than spiritual pride.”
It was not with an unkind or uncharitable feeling, still less with a

contemptuous one that Anne Seward mentioning the death of a lady
“long invalid and far advanced in life,” described her as “a civil social
being, whose care was never to offend; who had the spirit of a
gentlewoman in never doing a mean thing, whose mite was never
withheld from the poor; and whose inferiority of understanding and
knowledge found sanctuary at the card-table, that universal leveller
of intellectual distinctions.” Let not such persons be despised in the
pride of intellect! Let them not be condemned in the pride of self
righteousness!
“Our law,” says the Puritan Matthew Mead, “supposes all to be of
some calling, not only men but women, and the young ladies too;
and therefore it calls them during their virgin state spinsters. But
alas, the viciousness and degeneracy of this age hath forfeited the
title. Many can card, but few can spin; and therefore you may write
them carders, dancers, painters, ranters, spenders, rather than
spinsters. Industry is worn out by pride and delicacy; the comb and
the looking-glass possess the place and the hours of the spindle and
the distaff; and their great business is to curl the locks, instead of
twisting wool and flax. So that both male and females are prepared
for all ill impressions by the mischief of an idle education.”
“There is something strange in it,” says Sterne, “that life should

appear so short in the gross, and yet so long in the detail. Misery
may make it so, you'll say;—but we will exclude it,—and still you'll
find, though we all complain of the shortness of life what numbers
there are who seem quite overstocked with the days and hours of it,
and are constantly sending out into the highways and streets of the
city, to compel guests to come in, and take it off their hands: to do
this with ingenuity and forecast, is not one of the least arts and
business of life itself; and they who cannot succeed in it, carry as
many marks of distress about them, as bankruptcy itself could wear.
Be as careless as we may, we shall not always have the power,—nor
shall we always be in a temper to let the account run thus. When the
blood is cooled, and the spirits which have hurried us on through half
our days before we have numbered one of them, are beginning to
retire;—then wisdom will press a moment to be heard,—afflictions, or
a bed of sickness will find their hours of persuasion:—and should
they fail, there is something yet behind:—old age will overtake us at
the last, and with its trembling hand, hold up the glass to us.”
CHAPTER CXCII.
MORE OF THE DOCTOR'S PHILOSOPHY, WHICH WILL AND WILL NOT BE LIKED
BY THE LADIES, AND SOME OF THE AUTHOR'S WHICH WILL AND WILL NOT BY
THE GENTLEMEN. THE READER IS INTRODUCED TO COUNT CASTIGLIONE,
AND TO SIR JOHN CHEKE.
Ou tend l'auteur à cette heure?

Que fait-il? Revient-il? Va-t-il? Ou s'il demeure?
L'AUTEUR.
Non, je ne reviens pas, car je n'ai pas été;

Je ne vais pas aussi, car je suis arrété;
Et ne demeure point, car, tout de ce pas même
Je pretens m'en aller.
MOLIERE.
The passage with which the preceding Chapter is concluded, is

extracted from Sterne's Sermons, one of those discourses in which
he tried the experiment of adapting the style of Tristram Shandy to
the pulpit;—an experiment which proved as unsuccessful as it
deserved to be. Gray however thought these sermons were in the
style which in his opinion was most proper for the pulpit, and that
they showed “a very strong imagination and a sensible head. But
you see him, he adds, often tottering on the verge of laughter, and
ready to throw his perriwig in the face of his audience.”
The extract which has been set before the reader is one of those
passages which bear out Gray's judgement; it is of a good kind, and
in its kind so good, that I would not weaken its effect, by inserting too
near it the following Epigram from an old Magazine, addressed to a
lady passionately fond of cards.
Thou, whom at length incessant gaming dubs,
Thrice honourable title! Queen of Clubs,
Say what vast joys each winning card imparts,
And that, too justly, called the King of Hearts.
Say, when you mourn of cash and jewels spoil'd,
May not the thief be Knave of Diamonds stil'd?
One friend, howe'er, when deep remorse invades,
Awaits thee Lady; 'tis the Ace of Spades!
It has been seen that the Doctor looked upon the love of gaming as
a propensity given us to counteract that indolence which if not thus
amused, would breed for itself both real and imaginary evils. And
dancing he thought was just as useful in counteracting the factitious
inactivity of women in their youth, as cards are for occupying the
vacuity of their minds at a later period. Of the three semi-intellectual
propensities, as he called them which men are born with, those for
hunting and gaming are useful only in proportion, as the earth is
uncultivated, and those by whom it is inhabited. In a well ordered
society there would be no gamblers, and the Nimrods of such a
society, must like the heroes in Tongataboo, be contented with no
higher sport than rat-catching: but dancing will still retain its uses. It
will always be the most graceful exercise for children at an age when
all that they do is graceful; and it will always be that exercise which
can best be regulated for them, without danger of their exerting
themselves too much, or continuing in it too long. And for young
women in a certain rank, or rather region of life,—the temperate
zone of society,—those who are above the necessity of labour, and
below the station in which they have the command of carriages and
horses,—that is for the great majority of the middle class;—it is the
only exercise which can animate them to such animal exertion as
may suffice
“To give the blood its natural spring and play.”1
1 SOUTHEY.
Mr. Coleridge says (in his Table Talk) “that the fondness for dancing
in English women is the reaction of their reserved manners: it is the
only way in which they can throw themselves forth in natural liberty.”
But the women are not more fond of it in this country, than they are
in France and Spain. There can be no healthier pastime for them,
(as certainly there is none so exhilarating, and exercise unless it be
exhilarating is rarely healthful)—provided,—and upon this the Doctor
always insisted,—provided it be neither carried on in hot rooms, nor
prolonged to late hours. They order these things, he used to say,
better in France; they order them better indeed anywhere than in
England, and there was a time when they were ordered better
among ourselves.
“The youth of this city,” says the honest old chronicler and historian
of the metropolis his native place, “used on holidays, after evening
prayers, to exercise their basters and bucklers, at their master's
doors; and the maidens, one of them playing on a timbrel, to dance
for garlands hanged athwart the streets, which open pastimes in my
youth, being now suppressed, worser practises within doors are to
be feared.”
Every one who is conversant with the Middle Ages, and with the
literature of the reigns of Elizabeth, James and Charles I. must have
perceived in how much kindlier relations the different classes of
society existed toward each other in those days than they have since
done. The very word independence had hardly found a place in the
English language, or was known only as denoting a mischievous
heresy. It is indeed, as one of our most thoughtful contemporaries
has well said, an “unscriptural word,”—and “when applied to man, it
directly contradicts the first and supreme laws of our nature; the very
essence of which is universal dependence upon God, and universal
interdependence on one another.”
The Great Rebellion dislocated the relations which had for some
centuries thus happily subsisted; and the money getting system
which has long been the moving principle of British society, has,
aided by other injurious influences, effectually prevented the
recovery which time, and the sense of mutual interest, and mutual
duty, might otherwise have brought about. It was one characteristic
of those old times, which in this respect deserve to be called good,
that the different classes participated in the enjoyments of each
other. There were the religious spectacles, which, instead of being
reformed and rendered eminently useful as they might have been,
were destroyed by the brutal spirit of puritanism. There were the
Church festivals, till that same odious spirit endeavoured to
separate, and has gone far toward separating, all festivity from
religion. There were tournaments and city pageants at which all
ranks were brought together: they are now brought together only
upon the race-course. Christmas Mummers have long ceased to be
heard of. The Morris dancers have all but disappeared even in the
remotest parts of the kingdom. I know not whether a May-pole is now
to be seen. What between manufactures and methodism England is
no longer the merry England which it was once a happiness and an
honour to call our country. Akenside's words “To the Country
Gentlemen of England,” may be well remembered.
And yet full oft your anxious tongues complain

That lawless tumult prompts the rustic throng;
That the rude Village-inmates now disdain
Those homely ties which rul'd their fathers long.
Alas, your fathers did by other arts
Draw those kind ties around their simple hearts.
And led in other paths their ductile will;
By succour, faithful counsel, courteous cheer,
Won them their ancient manners to revere,
To prize their countries peace and heaven's due rites fulfil.
My friend saw enough of this change in its progress to excite in him

many melancholy forebodings in the latter part of his life. He knew
how much local attachment was strengthened by the recollection of
youthful sports and old customs; and he well understood how little
men can be expected to love their country, who have no particular
affection for any part of it. Holidays he knew attached people to the
Church, which enjoined their observance; but he very much doubted
whether Sunday Schools would have the same effect.
In Beaumont and Fletcher's Play of the Prophetess, the countrymen
discourse concerning the abdicated Emperor who has come to
reside among them. One says to the other,
Do you think this great man will continue here?
the answer is
Continue here? what else? he has bought the great farm;

A great man2 with a great inheritance
And all the ground about it, all the woods too
And stock'd it like an Emperor. Now all our sports again
And all our merry gambols, our May Ladies,
Our evening dances on the green, our songs,
Our holiday good cheer; our bagpipes now, boys,
Shall make the wanton lasses skip again,
Our sheep-shearings and all our knacks.
2 Southey has inserted a query here. “Qy Manor or Mansion.” It is usually printed as
in the text.—See Act v. Sc. iii.
It is said however in the Cortegiano, che non saria conveniente che

un gentilhuomo andasse ad honorare con la persona sua una festa
di contado, dove i spettatori, et i compagni fussero gente ignobile.
What follows is curious to the history of manners. Disse allhor' il S.
Gasparo Pallavicino, nel paese nostro di Lombardia non s'hanno
queste rispetti: anzi molti gentil'huomini giovani trovansi, che le feste
ballano tuttol' di nel Sole co i villani, et con esti giocano a lanciar la
barra, lottare, correre et saltare; et io non credo che sia male, perche
ivi non si fa paragone della nobiltà, ma della forza, e destrezza, nelle
quai cose spesso gli huomini di villa non vaglion meno che i nobili; et
par che que quella domestichezza habbia in se una certa liberalità
amabile.—An objection is made to this; Quel ballar nel Sole, rispose
M. Federico, a me non piace per modo alcuno; ne so che guadagno
vi si trovi. Ma chi vuol pur lottar, correr et saltar co i villani, dee (al
parer mio) farlo in modo di provarsi, et (come si suol dir) per
gentilezza, non per contender con loro, et dee l'huomo esser quasi
sicuro di vincere; altramente non vi si metta; perche sta troppo male,
et troppo è brutta cosa, et fuor de la dignità vedere un gentilhuomo
vinto da un villano, et massimamente alla lotta; però credo io che sia
ben astenersi almano in presentia di molti, perche il guadagno nel
vincere è pochissimo, et la perdita nell' esse vinto è grandissima.
That is, in the old version of Master Thomas Hoby; “it were not meet
that a gentleman should be present in person, and a doer in such a
matter in the country, where the lookers-on and the doers were of a
base sort. Then said the Lord Gasper Pallavicino, in our country of
Lombardy these matters are not passed upon; for you shall see
there young gentlemen, upon the holydays, come dance all the day
long in the sun with them of the country, and pass the time with them
in casting the bar, in wrestling, running and leaping. And I believe it
is not ill done; for no comparison is there made of nobleness of birth,
but of force and slight; in which things many times the men of the
country are not a whit inferior to gentlemen: and it seemeth this
familiar conversation containeth in it a certain lovely freeness.” “The
dancing in the sun,” answered Sir Frederick, “can I in no case away
withal; and I cannot see what a man shall gain by it. But whoso will
wrestle, run and leap with men of the country, ought, in my
judgement, to do it after a sort; to prove himself, and (as they are
wont to say) for courtesy, not to try mastery with them. And a man
ought (in a manner) to be assured to get the upper hand, else let him
not meddle withal; for it is too ill a sight, and too foul a matter, and
without estimation, to see a gentleman overcome by a carter, and
especially in wrestling. Therefore I believe it is well done to abstain
from it, at the leastwise in the presence of many; if he be overcome,
his gain is small, and his loss in being overcome very great.”
This translation is remarkable for having a Sonnet, or more correctly

speaking, a quatorzain by Sackville prefixed to it, and at the end of
the volume a letter of Sir John Cheke's to the translator, curious for
its peculiar spelling, and for the opinion expressed in it that our
language ought as much as possible to be kept pure and unmixed.
“I have taken sum pain,” he says, “at your request, cheflie in your
preface; not in the reading of it, for that was pleasaunt unto me,
boath for the roundnes of your saienges and welspeakinges of the
saam, but in changing certein wordes which might verie wel be let
aloan, but that I am verie curious in mi freendes matters, not to
determijn, but to debaat what is best. Whearin I seek not the bestnes
haplie bi truth, but bi mijn own phansie and sheo of goodnes.
“I am of this opinion that our own tung shold be written cleane and
pure, unmixt and unmangeled with borowing of other tunges;
wherein if we take not heed bi tijm, ever borowing and never payeng,
she shall be fain to keep her house as bankrupt. For then doth our
tung naturallie and praiseablie utter her meaning, when she
boroweth no conterfectness of other tunges to attire her self withall,
but useth plainlie her own with such shift as nature, craft, experiens,
and folowing of other excellent doth lead her unto; and if she went at
ani tijm (as being unperfight she must) yet let her borow with suche
bashfulnes, that it mai appear, that if either the mould of our own
tung could serve us to fascion a woord of our own, or if the old
denisoned wordes could content and ease this neede, we wold not
boldly venture of unknoven wordes. This I say, not for reproof of you,
who have scarslie and necessarily used, whear occasion serveth, a
strange word so, as it seemeth to grow out of the matter and not to
be sought for; but for mijn our defens, who might be counted
overstraight a deemer of thinges, if I gave not thys accompt to you,
my freend and wijs, of mi marring this your handiwork.
“But I am called awai. I prai you pardon mi shortnes; the rest of my

saienges should be but praise and exhortacion in this your doinges,
which at moar leisor I shold do better.
From my house in Wood street

the 16 of July 1557.
Yours assured
JOAN CHEEK.”
Sir John Cheke died about two months after the date of this letter:
and Hoby's translation was not published till 1561, because “there
were certain places in it, which of late years being misliked of some
that had the perusing of it, the Author thought it much better to keep
it in darkness a while, then to put it in light, imperfect, and in
piecemeal, to serve the time.” The book itself had been put in the list
of prohibited works, and it was not till 1576 that the Conte Camillo
Castiglione, the author's son, obtained permission to amend the
obnoxious passages and publish an expurgated edition.
It would have vexed Sir John if he had seen with how little care the
printer, and his loving friend Master Hoby observed his system of
orthography, in this letter. For he never used the final e unless when
it is sounded, which he denoted then by doubling it; he rejected the
y, wrote u when it was long, with a long stroke over it, doubled the
other vowels when they were long, and threw out all letters that were
not pronounced. No better system of the kind has been proposed,
and many worse. Little good would have been done by its adoption,
and much evil, if the translators of the Bible had been required to
proceed upon his principle of using no words but such as were true
English of Saxon original. His dislike of the translation for corrupting
as he thought the language into vocables of foreign growth, made
him begin to translate the New Testament in his own way. The
Manuscript in his own hand, as far as it had proceeded, is still
preserved at Bene't College,3 and it shows that he found it
impracticable to observe his own rule. But though as a precisian he
would have cramped and impoverished the language, he has been
praised for introducing a short and expressive style, avoiding long
and intricate periods, and for bringing “fair and graceful writing into
vogue;” he wrote an excellent hand himself, and it is said that all the
best scholars in those times followed his example, “so that fair
writing and good learning seemed to commence together.”
3 This has been since printed with a good Glossary by the Rev. James Goodwin,
Fellow and Tutor of Corpus Christi Coll. Cambridge, and is very curious. All that
remains is the Gospel according to St. Matthew. As an instance of Cheke's
Englishisms I may refer to the rendering of προσήλυτον in c. xxiij. v. 15, by freschman.
Some little of the MS. is lost.—See Preface, p. 10.
O Soul of Sir John Cheke, thou wouldst have led me out of my way,
if that had been possible,—if my ubiety did not so nearly resemble
ubiquity, that in Anywhereness and Everywhereness I know where I
am, and can never be lost till I get out of Whereness itself into
Nowhere.
CHAPTER CXCIII.
MASTER THOMAS MACE, AND THE TWO HISTORIANS OF HIS SCIENCE, SIR
JOHN HAWKINS AND DR. BURNEY. SOME ACCOUNT OF THE OLD LUTANIST
AND OF HIS “MUSIC'S MONUMENT.”
This Man of Music hath more in his head

Than mere crotchets.
SIR W. DAVENANT.
Thou wast informed, gentle Reader, in the third Volume and at the
two hundred and sixth page of this much-hereafter-to-be-esteemed
Opus, that a Tattle de Moy was a new-fashioned thing in the Year of
our Lord 1676. This was on the authority of the good old Lutanist,
whom, I then told you, I took leave of but for a while, bethinking me
of Pope's well known lines,
But all our praises why should Lords engross?

Rise, honest Muse! and sing the MAN OF ROSS.
And now gentle reader, seeing that whether with a consciousness of

second sight or not, Master Mace, praiseworthy as the Man of Ross,
has so clearly typified my Preludes and Voluntaries, my grave
Pavines and graver Galliards, my Corantoes and Serabands, my
Chichonas, and above all my Tattle-de-Moys, am I not bound in
gratitude to revive the memory of Master Mace; or rather to extend it
and make him more fully and more generally known than he has
been made by the two historians of his science Sir John Hawkins
and Dr. Burney. It is to the honour of both these eminent men, who
have rendered such good services to that science, and to the
literature of their country, that they should have relished the
peculiarities of this simple-hearted old lutanist. But it might have
been expected from both; for Dr. Burney was as simple-hearted
himself, and as earnestly devoted to the art: and Sir John who
delighted in Ignoramus and in Izaak Walton, could not fail to have a
liking for Thomas Mace.
“Under whom he was educated,” says Sir John, “or by what means
he became possessed of so much skill in the science of music, as to
be able to furnish out matter for a folio volume, he has no where
informed us; nevertheless his book contains so many particulars
respecting himself, and so many traits of an original and singular
character, that a very good judgement may be formed both of his
temper and ability. With regard to the first, he appears to have been
an enthusiastic lover of his art; of a very devout and serious turn of
mind; and cheerful and good humoured under the infirmities of age,
and the pressure of misfortunes. As to the latter his knowledge of
music seems to have been confined to the practice of his own
instrument; and so much of the principles of the science as enabled
him to compose for it; but for his style in writing he certainly never
had his fellow.”
This is not strictly just as relating either to his proficiency in music, or

his style as an author. Mace says of himself, “having said so much
concerning the lute, as also taken so much pains in laying open all
the hidden secrets thereof, it may be thought I am so great a lover of
it, that I make light esteem of any other instrument besides; which
truly I do not; but love the viol in a very high degree; yea close unto
the lute; and have done much more, and made very many more
good and able proficients upon it, than ever I have done upon the
lute. And this I shall presume to say, that if I excel in either, it is most
certainly upon the viol. And as to other instruments, I can as truly
say, I value every one that is in use, according to its due place; as
knowing and often saying, that all God's creatures are good; and all
ingenuities done by man, are signs, tokens, and testimonies of the
wisdom of God bestowed upon man.”
So also though it is true that Thomas Mace stands distinguished

among the writers on Music, yet it could be easy to find many fellows
for him as far as regards peculiarity of style. A humourist who should
collect odd books might form as numerous a library, as the man of
fastidious taste who should confine his collection to such works only
as in their respective languages were esteemed classical. “The
singularity of his style,” says Sir John, “remarkable for a profusion of
epithets and words of his own invention, and tautology without end,
is apt to disgust such as attend less to the matter than manner of his
book; but in others it has a different effect; as it exhibits, without the
least reserve all the particulars of the author's character, which was
not less amiable than singular.”—“The vein of humour that runs
through it presents a lively portraiture of a good-natured, gossipping
old man, virtuous and kind-hearted.”—The anxious “precision with
which he constantly delivers himself, is not more remarkable than his
eager desire to communicate to others all the knowledge he was
possessed of, even to the most hidden secrets.”—“The book
breathes throughout a spirit of devotion; and, agreeable to his
sentiments of music is a kind of proof that his temper was improved
by the exercise of his profession.”—There is no pursuit by which, if it
be harmless in itself, a man may not be improved in his moral as well
as in his intellectual nature, provided it be followed for its own sake:
but most assuredly there is none however intrinsically good, or
beneficial to mankind, from which he can desire any moral
improvement, if his motive be either worldly ambition, or the love of
gain.—Ἀδύνατον ἐκ φαύλης ἀφορμῆς ἐπὶ τὸ τέλος ἐυδραμεῖν.1
1 IAMBLICHUS.
To give an account of “Music's Monument,” which Dr. Burney calls a
matchless book, not to be forgotten among the curiosities of the
seventeenth century! will be to give the character of Thomas Mace
himself, for no author ever more compleatly embodied his own spirit
in his writings.
It is introduced with an Epistle Dedicatory, which by an easy

misrepresentation has been made to appear profane.
To Thee, One-Only-Oneness, I direct

My weak desires and works.
Thou only art The Able True Protector;
Oh be my shield, defender and director,
Then sure we shall be safe.
Thou know'st, O Searcher of all hearts how I,
With right, downright, sincere sincerity,
Have longed long to do some little good,
(According to the best I understood)
With thy rich talent, though by me made poor,
For which I grieve, and will do so no more,
By thy good Grace assisting, which I do
Most humbly beg for. Oh, adjoin it to
My longing ardent soul; and have respect
To this my weak endeavour, and accept,
In thy great mercy, both of it and me,
Even as we dedicate ourselves to Thee.
An Epistle, in verse, follows “to all Divine Readers, especially those

of the Dissenting Ministry, or Clergy, who want not only skill, but
good will to this most excelling part of divine service, viz. singing of
psalms, hymns and spiritual songs, to the praise of the Almighty, in
the public Assemblies of his Saints: and yet more particularly, to all
great and high Persons, Supervisors, Masters, or Governors of the
Church, (if any such there should be) wanting skill, or good will
thereunto.”
He says to those “high men of honour,” that

Example is the thing;
There's but one way, which is yourselves to sing.
This sure will do it; for when the vulgar see
Such worthy presidents their leaders be,
Who exercise therein and lead the van,
They will be brought to't, do they what they can.
But otherwise for want of such example,
Tis meanly valued, and on it they trample;
And by that great defect, so long unsought,
Our best Church Music's well-nigh brought to nought.
Besides,
No robes adorn high persons like to it;
No ornaments for pure Divines more fit.
That Counsel given by the Apostle Paul

Does certainly extend to Christians all.
Colossians the third, the sixteenth verse;
(Turn to the place:) that text will thus rehearse,
Let the word of Christ dwell in you plenteously,
(What follows? Music in its excellency.)
Admonishing yourselves, in sweet accord,
In singing psalms with grace unto the Lord,
Sed sine arte, that cannot be done,
Et sine arte, better let alone.
Having thus “fronted this Book with the divine part, and preached his
little short sermon” upon the last of St. Paul, he says that his first and
chief design in writing this book was only to discover the occult
mysteries of the noble lute, and to shew the great worthiness of that
too much neglected and abused instrument, and his good will to all
the true lovers of it, in making it plain and easy, giving the true
reasons why it has been formerly a very hard instrument to play well
upon, and also why now it is become so easy and familiarly
pleasant. “And I believe,” says he, “that whosoever will but trouble
himself to read those reasons,—and join his own reason, with the
reasonableness of those reasons, will not be able to find the least
reason to contradict those reasons.”
He professed that by his directions “any person, young or old, should
be able to perform so much and so well upon it, in so much or so
little time, towards a full and satisfactory delight and pleasure, (yea, if
it were but only to play common toys, jigs or tunes,) as upon any
instrument whatever; yet with this most notable and admirable
exception, (for the respectable commendation of the lute,) that they
may, besides such ordinary and common contentments, study and
practice it all the days of their lives, and yet find new improvements,
yea doubtless if they should live unto the age of Methusalem, ten
times over; for there is no limitation to its vast bounds and bravery.” It
appears that the merit of this book in this respect is not overstated,
one of his sons attained to great proficiency on this instrument by
studying the book without any assistance from his father; and Sir
John Hawkins affirms on his own knowledge that Mr. John Immyns,
lutanist to the Chapel Royal, has the like experience of it. “This
person who had practised on sundry instruments for many years,
and was able to sing his part at sight, at the age of forty took to the
lute, and by the help of Mace's book alone, became enabled to play
thorough base, and also easy lessons on it; and by practice had
rendered the tablature as familiar to him, as the notes of the scale.”
The notation called the tablature is minutely explained in the work. It

has not the least relation to the musical character; the six strings of
the lute are represented by as many lines, “and the several frets or
stops by the letters a, b, c, d, e, f, g, h, y (a preference to i as being
more conspicuous) k; the letter a ever signifying the open string in all
positions.” Many persons have been good performers on the lute,
and at the same time totally ignorant of the notes of the Gamut. His
printer, he said, “had outdone all music work in this kind ever before
printed in this nation; and was indeed the only fit person to do the
like, he only having those new materials, the like to which was never
had made before in England.” They might have been more distinct,
and more consistent;—five being common English characters, the c
more resembling the third letter in the Greek alphabet than any thing
else, the b reversed serving for g, and the d in like manner for e.
The characters for the time of notes he compares to money, as
supposing that most people would be ready enough to count them
the better for that. Considering therefore the semi-breve as a groat,
the minim becomes two pence, the crotchet a penny, the quaver a
half-penny, and the semi-quaver a farthing. Trouble not yourself for
the demi-quaver, he says, till you have a quick hand, it being half a
semi-quaver.
But besides these, there are marks in his notation for the fifteen
graces which may be used upon the lute, though few or none used
them all. They are the Shake, the Beat, the Back-fall, the Half-fall,
the Whole-fall, the Elevation, the Single Relish, the Double Relish,
the Slur, the Slide, the Spinger, the Sting, the Tutt, the Pause and
the Soft and Loud Play, “which is as great and good a grace as any
other whatever.”
“Some,” says Master Mace, “there are, and many I have met with,
who have such a natural agility in their nerves, and aptitude to that
performance, that before they could do any thing else to purpose,
they would make a shake rarely well. And some again can scarcely
ever gain a good shake, by reason of the unaptness of their nerves
to that action, but yet otherwise come to play very well. I, for my own
part, have had occasion to break both my arms; by reason of which,
I cannot make the nerve-shake well, nor strong; yet by a certain
motion of my arm, I have gained such a contentive shake, that
sometimes my scholars will ask me, how they shall do to get the
like? I have then no better answer for them, than to tell them, they
must first break their arm, as I have done; and so possibly after that,
by practice, they may get my manner of Shake.”
Rules are given for all these graces, but observe he says “that
whatever your grace be, you must in your farewell express the true
note perfectly, or else your pretended grace, will prove a disgrace.”
“The Spinger is a grace very neat and curious, for some sort of
notes, and is done thus: After you have hit your note, you must just
as you intend to part with it, dab one of your rest fingers lightly upon
the same string, a fret or two frets below, (according to the air,) as if
you did intend to stop the string, in that place, yet so gently, that you
do not cause the string to sound, in that stop, so dab'd; but only so
that it may suddenly take away that sound which you last struck, yet
give some small tincture of a new note, but not distinctly to be heard
as a note; which grace, if well done and properly is very taking and
pleasant.”
The Sting is “another very neat and pretty grace,” it makes the sound
seem to swell with pretty unexpected humour, and gives much
contentment upon cases.
The Tut is easily done, and always with the right hand. “When you
would perform this grace, it is but to strike your letter which you
intend shall be so graced, with one of your fingers, and immediately
clap on your next striking finger upon the string which you struck; in
which doing, you suddenly take away the sound of the letter; and if
you do it clearly, it will seem to speak the word, Tut, so plainly, as if it
were a living creature, speakable!”
While however the pupil was intent upon exhibiting these graces, the
zealous master exhorted him not to be unmindful of his own, but to
regard his postures, for a good posture is comely, creditable and
praiseworthy, and moreover advantageous as to good performance.
“Set yourself down against a table, in as becoming a posture, as you
would choose to do for your best reputation. Sit upright and straight;
then take up your lute, and lay the body of it in your lap across. Let
the lower part of it lie upon your right thigh, the head erected against
your left shoulder and ear; lay your left hand down upon the table,
and your right arm over the lute, so that you may set your little finger
down upon the belly of the lute, just under the bridge, against the
treble, or second string: and then keep your lute stiff, and strongly
set with its lower edge against the table-edge; and so, leaning your
breast something hard against its ribs, cause it to stand steady and
strong, so that a bystander cannot easily draw it from your breast,
table, and arm. This is the most becoming, steady and beneficial
posture.”
“Your left hand thus upon the table, your lute firmly fixed, yourself
and it in your true postures,—bring up your left hand from the table,
bended, just like the balance of a hook, all excepting your thumb,
which must stand straight and span'd out; your fingers also, all
divided out from the other in an equal and handsome order; and in
this posture, place your thumb under the neck of the lute, a little
above the fret, just in the midst of the breadth of the neck; all your
four-fingers in this posture, being held close over the strings on the
other side, so that each finger may be in a readiness to stop down
upon any fret. And now in this lively and exact posture, I would have
your posture drawn, which is the most becoming posture I can direct
unto for a lutanist.”
“Know that an old lute is better than a new one.” Old instruments
indeed, are found by experience to be far the best, the reasons for
which Master Mace could no further dive into than to say, he
apprehended, “that by extreme age, the wood and those other
adjuncts, glue, parchment, paper, linings of cloth, (as some used) but
above all the varnish, are by time very much dried, limped, made
gentle, rarified, or to say better, even airified; so that that stiffness,
stubbornness, or clunguiness which is natural to such bodies, are so
debilitated and made pliable, that the pores of the wood, have a
more free liberty to move, stir or secretly vibrate; by which means the
air (which is the life of all things both animate and inanimate) has a
more free and easy recourse to pass and repass, &c. Whether I
have hit upon the right cause, I know not, but sure I am that age
adds goodness to instruments.”
The Venice lutes were commonly good; and the most esteemed
maker was Laux Malles, whose name was always written in text
letters. Mace had seen two of his lutes, “pitiful, old, battered, cracked
things;” yet for one of these, which Mr. Gootiere, the famous lutanist
in his time showed him, the King paid an hundred pounds. The other
belonged to Mr. Edward Jones, one of Gootiere's scholars; and he
relates this “true story” of it; that a merchant bargained with the
owner to take it with him in his travels, on trial; if he liked it, he was
on his return to give an hundred pounds for it; otherwise he was to

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