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

Ranveer Singh
McGraw Hill Education (India) Private Limited

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Physical Chemistry for JEE (Main & Advanced) Module-II
Copyright © 2017, McGraw Hill Education (India) Private Limited.
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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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the regulation of the pendulum is performed by adding to, or
diminishing the mercury, in the part where the tube is widest.”
In addition to the foregoing description of the mechanism of this Time-piece,
obligingly furnished to the Writer of these Memoirs by Mr. Voight, he has been
likewise favoured by Robert Patterson, Esq. director of the mint, with the
following account of the same extremely accurate instrument, which will
greatly assist the reader in understanding the principles on which it is
constructed.
“In the Astronomical Clock made by Dr. Rittenhouse, and now in

the Hall of the Philosophical Society, I do not know,” says Mr.
Patterson, “that there is any thing peculiar, which requires
mentioning, except the pendulum; especially the apparatus for
counteracting the effects of change of temperature.
“For this purpose, there is fastened on the pendulum-rod (which is

of iron or steel) a glass tube of about thirty-six inches long; bent in
the middle into two parallel branches, at the distance of about an
inch from each other; the bend being placed downwards,
immediately above the bob of the pendulum. The tube is open at one
end, and close at the other: the arm which is close at top is filled,
within about two inches of the lower end or bend, with alcohol, and
the rest of the tube, within about one half of an inch of the upper
extremity or open end, with mercury; a few inches of the tube, at this
extremity, being about twice the width of the rest of the tube.
“Now, when the heat of the air encreases, it will expand the
pendulum-rod; and would thus lower the centre of oscillation, and
cause the clock to go slower: but this effect is completely
counteracted, by the expansion of the alcohol chiefly, and of the
mercury in part; which equally raises the centre of oscillation; and
thus preserves an equable motion in all the variable temperatures of
the atmosphere.”
Description of an Hygrometer; first contrived and used by Dr.
Rittenhouse, about the year 1782.[A45]
The essential part of this Hygrometer consists of two very thin

strips of wood, about a foot long and half an inch broad, glued
together, in such a manner that the grain or fibres of the one shall be
at right angles with the other; so that when this compound strip was
placed in erect position, the grain of one of the pieces of wood would
have a vertical, and that of the other an horizontal position. One end
of this simply constructed instrument is to be made fast to a wall, or
plane board, with the edge outward, and the other end is to be at
liberty to move.
Then, as moisture has little or no effect on the length of a piece of

wood, or in the direction of its fibres, but a very sensible one on its
breadth, or transverse direction, especially when thin, it follows, that
on any increase of moisture in the air, this Hygrometer becomes bent
into a curve, convex on the side of the transverse fibres; and vice
versâ. The degrees, from the greatest dryness to the greatest
moisture, are to be marked on a curve drawn on the board or wall,
described by the motion of the free end of the Hygrometer; and an
index, attached to the moving end of it, will point out, on this
graduated arch, the existing state of the atmosphere at the moment,
in relation to its condition of moisture or dryness: The relative degree
of either, on the smallest change from the one to the other, will be
indicated with much precision; and probably, with much more
uniformity and truth, in the results of long-continued observations,
than can be attained to by the use of Hygrometers constructed of
metal, or any other substance than wood.[A46]
Astronomical Observations, made in the years 1776, 1777 and 1778,

at Philadelphia, by the Rev. Dr. W. Smith, and David Rittenhouse,
John Lukens, and Owen Biddle, Esquires: copied from a
manuscript account of those Observations, drawn up by Dr. Smith;
never before published.
ASTRONOMICAL OBSERVATIONS, 1776.

This year exhibiting little else but scenes of confusion and distress
amidst the calamities of an unhappy war, scarce any attention was
paid, by the members of the American Philosophical Society, to
astronomical or any other literary subjects. It was agreed, however,
by Mr. Rittenhouse, Mr. Lukens and myself, to look out whether
Mercury would touch the Sun’s disc the 2d of November this year; as
a very small difference of latitude from what the Tables give, would
have carried the planet clear of the Sun: but, from our observation of
the transit of this planet, in 1769, we had reason to expect it would
pass further on the Sun, than Halley’s Catalogue gives it.
The following were the observations made, viz.
Nov. 2d, 1776. I got ready the two f. reflector with the largest
object-glass, and shortest eye-tube, magnifying about 95 times.
At 4h per clock—No appearance of the planet on the Sun, and did

not expect it until about half an hour past 4; but as Mr. Lukens and
Mr. Rittenhouse had not yet come to me in the college, I sent to
hasten them.
At 4h 5′ per clock—took my eye from the tube to adjust it, and fix
the smoked glass, to give clearer vision, the atmosphere being hazy.
Having fixed the smoked glass in the proper place, so as to prevent
its sliding or falling with its own weight, and before I had applied my
eye to the telescope again, Mr. Rittenhouse came in; and I desired
him to see if the focus and dark glass were all suitable to his eye, as
they were to mine. I had been about 4′ employed in this adjustment.
At 4h 9′, Mr. Rittenhouse having put his eye to the tube,

immediately called out, that he saw the planet on the Sun.
h
At 4 10′ per clock, we judged ☿ had entered one-third of his
diameter on the Sun.
At 4h 17′, we clearly noted the internal contact of the limbs.

At 4h 45′, we judged the least distance of the nearest limbs to be
rather more than one diameter of ☿; or that the distance of the limbs
was 10″. We-did not apply the micrometer to make any measures; as
we presumed that we could judge the distance as accurately by the
eye, as it could be measured; on account of the haziness of the
atmosphere and the small altitude of the Sun. We kept viewing the
planet till sun-set, the distance of the limbs continuing so nearly the
same, that we could scarce perceive any diminution thereof; though
we were sure also, that it did increase above 10″.[A47]
The following were the Observations made for ascertaining the

Going of the Clock, by William Smith.
Equal Altitudes.
dh ′ ″ h ′ \″
Nov. 39 14 9 2 37 12 ☉ on Merid. per clock h ′ ″
15 44 2 35 35 or mean noon 11 55 40
Equat. Correspond. Alt. + 14.4
Correct Noon per Clock 11 55
54.4
49 32 48 20 56 Mean Noon, or ☉ on 11 56 53
34 33 19 13 Merid. per. Clock
36 14 17 31 Equat. of equal + 13.8
37 20 16 23 Altitudes
14 39
40 54 2 12 53 Correct Noon per Clock 11 57 6.8
78 51 9 9 29 Mean 12 0 19
Noon
52 37 80 per Equat Eq. Alt. + 12
Clock
54 1 3 6 37 12 0 19
Cor. 12 0 31
Noon
per Clock
Per Meridian Mark.
d h ′ ″
8 ☉ West Limb on Merid. 12 0 36
East Limb on do. 12 2 52
—-——
Centre 12 1 44
Correct Noon per Clock.
Applied to Going of Clock.

Nov. 3d, at Noon ′ ″
Clock slower than ☉ 4 5.6 Daily gaining of the Clock over
☉ faster than mean time 16 11 mean or equal time.
Clock faster than m. time 12 5.4
4th,
Clock slower than ☉ 2 53.2 ′ ″
☉ faster than mean time 16 9 From 3d to 4th 1 10.4
Clock faster than m. time 13 15.8
7th,
Clock faster than ☉ 0 31
From 4th mean to
☉ faster than mean time 16 00 7 that a mean 1 5.1
Clock faster than m. time 16 31 per day
8th,
Clock faster than ☉ 1 44
☉ faster than mean time 15 56 From 7th to 8th 1 9
Clock faster than m. time 17 40
Thus the Clock gains at a
mean, per day, 1′ 8″.
Whence, Nov. 2d, at noon, the Clock was 10′ 57″ faster than mean
time, gaining 68″ per day; and 4h 17′ gains 12″, wherefore at the
internal contact, the Clock was 11′ 9″ faster than mean time.
Whence the contact was at 4h 5′ 51″ mean time; or 4h 21′ 2″

apparent time.
Eclipse of the Sun, January 9th, 1777.
The Gregorian Reflector, with the magnifying power of 95, was

made use of for this Observation; which, as well as the Observation
of the Transit of Mercury, was made in the College-Library, to which
the Telescope belongs.
While Mr. Rittenhouse was endeavouring to adjust the two-f.

reflector belonging to the Library of the city of Philadelphia, made by
Short, and which had been borrowed on this occasion, I observed
with the greatest certainty the first contact of ☾’s limb with the ☉,
which was shining very bright, and the telescope in the best order,
viz. at 8h 57′ 27″ per clock.
The same was visible, in about 3″ more, to Mr. Lukens, with the
equal altitude instrument, magnifying about 25 times.
Mr. Rittenhouse had not got the other reflector ready to observe
the beginning of the eclipse: but the end was observed by both of us
to the same instant, viz. at 11h 48′ 50″ per clock.
The clock, at noon, was 23″ slower than mean time, whence
Beginning of the Eclipse 8h 49′ 55″

Apparent time.
End of the same 11 41 15
N.B. The clock stopped once during the Observation, owing, it was
supposed, to the cold weather; but was oiled a little, and set a going
again by a stop-watch that beats seconds, and which was set with
the clock at the beginning of the eclipse: so that she lost no time.
She was examined at noon, and found as above by the meridian
mark. But this mark itself, having been lately shaken with the stormy
weather, is to be re-examined, and also equal altitudes taken the
following days.
The annexed micrometer measures were taken for determining

the quantity of the eclipse, chiefly by Mr. Rittenhouse. More would
have been taken, but the Sun was hid under clouds for about an
hour after the middle of the eclipse, and broke out again a little
before the end.
Micrometer Measures.
h ′ ″ inches. tenths. 500ths.
9 15 0 2 2 6
distances of the cusps.
31 0 3 1 ½
10 17 5 1 1 14 enlightened parts
22 0 1 1 23 remaining.
11 37 0 1 7 6
38 46 1 5 21 distances of the cusps.
42 26 1 2 18
Continuation of the Observations for adjusting the Clock.

Jan. 11th. W. limb on Merid. [A48]
☉’s
E. limb on do.
Centre on do.
Whence clock faster than mean time 0 1′ 46″ per merid. mark.
Equal Altitudes.
h ′ ″
20th. 9 37 20 59 49
39 1 58 6 Mean noon per clock 12 18 34
40 41 2 56 26
21st. W. limb on Merid. 12 20 3
E. limb on do. 22 22
Centre on do. 12 21 12.5
Eq. Alt.
22d. 9 14 10 3 31 10 Mean noon per clock 12 23 50
Eclipse of the Sun, June 24, 1778: Observed by D. Rittenhouse,

John Lukens, Owen Biddle, and William Smith, at the College of
Philadelphia.
The morning being very cloudy, the beginning of the eclipse was
not seen.
At 10h 7′ 40″ per clock, the following micrometer-measure of the

enlightened parts was taken, while the Sun appeared for a few
minutes between clouds, viz. 1in. 9-10ths. 13-500ths. = 16′ 23″.
11h 6′ 57″ per clock end of eclipse distinctly seen, the Sun having
shone clearly for several minutes, the clouds now wholly dispersing,
and the remainder of the day continuing clear.
Observations upon the Clock.

h ′ ″
27th. ☉ on meridian per clock 11 54 50
☉’s app. time of passing meridian 12 2 33.5
Clock slow of app. time 0 7 43.5
July 2d. ☉ on meridian per clock 11 54 50.5

☉’s app. time of passing meridian 12 3 33
Clock slow of app. time 0 8 42.5
A versification of “The Zephyrs”—from Gesner’s Idyls;—a fragment:

copied from a loose scrap of paper, containing, in the hand-writing
of the late Dr. Rittenhouse, all but the three last verses; which have
been now added, by a lady.
First Zephyr.
Why, amidst these blooming roses,

Idly fluttering, dost thou stay?
Come with me to yonder valley,
There we’ll spend the cheerful day.
There, in purest crystal fountain,
Sportive, bathe the am’rous maids;
Where tall willows, on the margin,
Form the closest deepest shades.
Second Zephyr.
No, with thee I will not wander;

To the vale alone repair:
Fan the nymphs you so admire;
A sweeter task employs my care.
Here, in the bosom of these roses,
I cool my wings in pearly dew,
As I lightly skim them over,
Gath’ring all their fragrance too.
First Zephyr.
Your wings in dew of roses steep’d

With all their grateful fragrance stor’d;—
Can you find employment sweeter,
Than yonder cheerful nymphs afford?
Second Zephyr.
Yes, in this path, along the mount,

Each rosy morn a maid appears,
To yon lonely cot advancing,
A basket on her arm she bears.
Two tender infants, and their mother,
Are by her constant bounty fed:
A helpless widow, there residing,
From her receives her daily bread.
See! where she comes,—of all the graces,
The youngest and the fairest too;
Her cheeks, with sweetest blushes glowing,
Are moist’ned with the morning dew.
I haste, with fragrant airs, so cooling,
To fan her tender glowing cheek,—
And kiss the pearly drops, while falling
From her blue eyes, so chaste and meek.[A49]
First Zephyr.
Yes! much more pleasing is your task;

I would imbrue my wings in dew,
And bear the fragrance of these flow’rs,
Melinda to refresh, like you.
But see! she breaks through yonder grove,
Refulgent as a summer’s morn;
Her step is grace—her lip of rose
The smiles of modest worth adorn.
Like you, transported, let me fan her;
Like you, admire the bounteous maid:
For, sure, a fairer face I never
Spread forth my cooling wings to aid.
Diploma.
Praeses et Professores Collegii, seu Universitatis, Gulielmi et

Mariæ, omnibus at quos præsentes literæ pervenerint, Salutem.—
Cum eum in finem gradus academici majoribus nostris prudenter
instituti fuerint, ut viri optimé meriti, seu in gremio nostræ matris
educati, seu aliundi bonarum artium disciplinis eruditi, istis insignibus
a literatorum vulgo secernerentur; sciatis, quod nos, ea sola quæ
possumus viâ, gradu Artium Magistri libenter studioséque concesso,
testamur quanti facimus Davidem Rittenhouse Philosophorum
Principem, qui ingenio nativo Machinam celeberrimam, motus et
phænomena cœlestium manifestius exhibentem, commentus est:—
Idcirco, in solenni convocatione, tricessimo die decembris, Anno
Domini millesimo septingentesimo octogesimo quarto, habito,
conspirantibus omnium suffragiis, eundem virum egregium, Davidem
Rittenhouse, Artium Magistrum creavimus et constituimus.—In
cujus rei testimonium, sigillum Universitatis, quo in hac parte utimur,
præsentibus apponi fecimus. Datum in domo nostræ convocationis,
anno domini, die et mense, prædictis.
J. Madison, Præses, et prof. Ma. and Nat. Phil. G. Wythe, Leg. et

Polit. Prof. Robertus Andrews, Math. Prof. Carolus Bellini,
Neot. Ling. Prof.
Diploma.
Præses et Curatores Collegii Neo-Cæsariensis, omnibus has

Literas lecturis, plurimam Satutem.
Quandoquidem æquum sit et ratione prorsus, consentaneum, ut ii

qui labore et studio bonas didicerunt artes præmia suis meritis digna
referant ut et ipsis benè sit, et aliorum provoceter industria.
Quando etiam huc potissimum spectant amplissima illa jura nostro

Collegio publico Diplomate collata. Quumque clarissimus vir David
Rittenhouse sit non tantum Moribus inculpatus et Ingenio insignis,
sed et sibi tantam in Artibus liberalibus cognitionem Industria
laudabili acquisivit, ut summos Honores Academicos probe
mereatur.
Idcirco notum sit omnibus, quod nos, Senatus-consulto Academico

nec non Facultatis Artium decreto, supradictum Davidem
Rittenhouse Titulo Graduque Doctoris in Legibus adornandum,
et dehinc pro Adepto et Doctore habendum volumus; cujus, hæc
Membrana, Sigillo nostri Collegii rata et Chirographis nostris munita,
Testimonio sit.
Datum Aulæ Nassovicæ, Pridie Calendas Octobris Anno
MDCCLXXXIX.
Joannes Witherspoon, Præses. Joannes Rodgers, Joannes

Bayard, Joannes Woodhull, Guls. Paterson, Isaacus Snowden,
Jacobus Boyd, Joannes Beatty, Guliel. M. Tennent, Andreas Hunter,
Curatores.
An English Obituary Notice of Dr. Rittenhouse: Extracted from the

European Magazine, for July, 1796.
In the sixty-fourth year of his age, died David Rittenhouse, The

American Philosopher. His history is curious, from the admiration in
which his character was held.
Rittenhouse was a native of America; and, in the early part of his

life, he mingled the pursuits of science with the active employments
of a farmer and watch-maker.[A50] In 1769, he was invited by the
American Philosophical Society to join a number of gentlemen who
were then occupied in making some astronomical observations,
when he particularly distinguished himself by the accuracy of his
calculations and the comprehension of his mind. He afterwards
constructed an observatory,[A51] which he superintended in person,
and which was the source of many important discoveries, as well as
greatly tending to the diffusion of knowledge in the western world.
During the American war, he was an active assertor of the cause of
independence. Since the establishment of the peace, he
successively filled the offices of Treasurer of the State of
Pennsylvania and Director of the National Mint; in both of which
capacities, he was alike distinguished for strength of judgment and
integrity of heart. He succeeded the illustrious Franklin in the office
of President of the Philosophical Society; a situation which the bent
of his mind and the course of his studies had rendered him eminently
qualified to fill: and towards the close of his days, he retired from
public life to the enjoyment of domestic happiness; when he formed
a circle of private friends, who will continue to admire his Virtues as a
Man, while the world will applaud his Talents as a Philosopher.
Letter from the Rev. Mr. Cathcart, to the Writer of these Memoirs.
York, 13th. Nov, 1812.
Dear Sir,
The following is a statement of the conversation which took place

between Drs. Sproat and Rittenhouse, mentioned by me to Bishop
White.
At a time when Dr. Rittenhouse was confined by sickness to his

room, or perhaps to his bed,[A52] he sent for the Rev. Dr. Sproat to
visit him. The Doctor was somewhat surprised, on receiving the
message: but as he had made it an uniform rule to visit all who sent
for him, he expressed his surprise at being sent for; observing, that
he could offer no comfort or consolation to any person, who was not
a Believer in the Christian Religion. On hearing this declaration, Dr.
Rittenhouse immediately asked, if Dr. Sproat considered him among
the number of such? To which the Doctor answered; that the world
had generally classed him with them. Dr. Rittenhouse on hearing
this, with great mildness and a smile on his countenance, replied,
that the opinion of the world was sometimes wrong; and, as it
respected himself, he could with truth declare, that ever since he had
examined Christianity and thought upon the subject, he was a firm
believer in it; and, that he expected salvation only in the way and
manner, as proposed in the Gospel.
The above is the substance of what Dr. Sproat mentioned to

myself; and I might add, that when the good old man told it, his eyes
overflowed with tears of joy. It gives me pleasure to be able to
furnish you with this satisfactory proof of Dr. Rittenhouse’s faith; and
which I once introduced into a sermon preached in the city, as justice
due to the character of the deceased, and who had been
triumphantly claimed by the Infidels. I am happy to find that you are
engaged in the laudable business of writing the Life of that worthy
Man. Yours, respectfully,
Robert Cathcart.
William Barton, Esquire.
Character of Dr. Rittenhouse:
Communicated to the Author of the Memoirs of his Life, in a letter

from Andrew Ellicott, Esq.
Lancaster, December 30th, 1812.
Dear Sir,
I felt no small degree of pleasure and satisfaction, on

understanding that you are about publishing Memoirs of the Life of
Dr. Rittenhouse; knowing, from your connexion, and intimacy with
him for many years, you have it in your power to delineate, and
transmit his true character and a knowledge of his rare virtues to
posterity, with as much, if not more accuracy than any other person.
As I also have had the pleasure and advantage of Dr. Rittenhouse’s
acquaintance and friendship, I request you to accept of the following
short sketch of his character, as a small testimony of my esteem for
him when living, and of my veneration for his memory, now he is no
more. I am, dear Sir, your sincere friend,
Andrew Ellicott.
William Barton, Esq.
I became acquainted with the late Dr. Rittenhouse, in the sixteenth

year of my age, being first introduced to him, after he removed to the
city of Philadelphia, by the late Joseph Galloway, Esq. and my
Father; both of whom were sincerely attached to him, not only on
account of his scientific talents and acquirements, but for his public
and private virtues. From that period, to the end of his life, we
enjoyed an uninterrupted friendship.
In my scientific pursuits, I was frequently aided by him; particularly,

in that part which relates to Astronomy, with which he was better
acquainted, both in theory and practice, than any other person in this
country; and when he ceased to calculate the Almanacks for the
middle states, at his request I continued them several years.
In the years 1784 and 1785, Dr. Rittenhouse and myself were
engaged in determining the boundaries between this commonwealth
and the state of Virginia; and in the year 1786, in determining the
boundary between this commonwealth and the state of New-York. In
those arduous employments, I had many opportunities of witnessing
his address in overcoming the numerous difficulties we necessarily
had to encounter, in the then wilderness, in which our operations
were performed.
As a gentleman of general science, Dr. Rittenhouse would have

held a respectable rank in any country; but as a Mechanist and
Astronomer, he has had but few equals. It has been frequently
asked,—why he has not left more evidences of his talents, for the
use of posterity? In answer to this question, it is to be observed, that
almost from his childhood, he had a complaint in his breast; which
increased so much with his age, that for the last fifteen years of his
life,—and in which he had the most leisure for composition,—it was
painful for him to support the position a person must occupy, when
writing. This circumstance I have frequently heard him lament, in a
feeling manner; as it prevented him from answering letters with
promptitude, and writing to his friends as often as he wished.
Though Dr. Rittenhouse had not the advantage of a liberal

education, he wrote not only correctly but with ease: he made
himself master of the German language, to which he was partial: and
of the French, so far as to read the scientific works in that tongue,
with facility.
As an Husband, and a Father, he might be taken as an example
and a pattern, in the most virtuous community that ever existed. He
was a good Citizen,—and warm and sincere in his friendships; and
though reserved in large mixed companies, he was cheerful and
communicative, when in a small circle of his friends. His mind
appeared formed for contemplation, and therefore not calculated for
the noisy and busy scenes of this world: from this placid turn of mind,
he had a singular antipathy to all mobs and riots; and I recollect to
have heard him speak of the riots of the Paxton-boys, (as they were
called,) with greater acrimony than on any other occasion,—more
than twenty years after they happened. Being a philanthropist by
nature, he wished the happiness and welfare of the whole human
race; and viewed slavery, in all its forms, with feelings of horrour:
from this attachment to the happiness, the rights, and the liberty of
his fellow-creatures, he was led to take an active and useful part in
favour of our revolution, which separated the colonies (now the
United States,) from the mother-country.
His contemplative mind naturally carried him to piety; but his

liberality was so great, that he did not appear to give a very decided
preference to any one of the sects into which Christianity is divided:
he practised the morality of a sincere Christian, without troubling
himself about the dogmas of the different churches.
His manners were plain and unassuming, though not without a

sufficient share of dignity; and, from a consciousness of his own
talents, he did not envy those of others.
It has too frequently happened, for the honour of science and

literature, that men of great and commanding talents, have been
obstinately dogmatical, and impatient of contradiction;—of those
blemishes, Dr. Rittenhouse had not the least tincture.
To conclude,—if Dr. Rittenhouse was not the greatest man, of the

age, his character has fewer blemishes in it; and, if his talents were
not of that kind which are usually considered the most brilliant, they
were—like those of Washington—of the most solid and useful
order.
Some particulars concerning the Residence, the Tomb, &c. of
Copernicus: communicated to the late Dr. Rittenhouse, Pres. A. P.
S. by the Earl of Buchan.
“In the year 1777,” says his Lordship, “my learned friend John
Bernouilli, of Berlin, on one of his tours having happened to meet
with the Bishop of Warmia,[A53] in the Abbey of Oliva, near Dantzic,
was informed by that prelate, that he had the pleasure to discover, in
the Cathedral of Frauenburg, the Tomb of Copernicus, so long
fruitlessly sought for.
“In the year 1778, Mr. Bernouilli having occasion to pass through
Frauenburg, on his road to St. Petersburg, did not fail to visit the
Cathedral, and explore the Monument of Copernicus. Acquainted
with no one in the place, he was yet lucky enough to meet with a
Canon, in the street, whose countenance invited him to accost him
on this subject, and who proved very attentive to his researches. He
informed him, that as for the Ashes of Copernicus, they were
mingled in the charnel-house with the bones of the fraternity of the
Canons; but that, for the Tombstone of the Philosopher, it was no
more than a tablet of marble, simple, as the mode was of his days,
and had no other inscription than these words—Nic. Copernicus,
Thor:—-That this tablet had remained hidden for some time, in
rubbish; and when recovered, was placed in the chapter-house, till a
more suitable place should be destined for it. Mr. Bernouilli
expresses his regret to me, that he had not urged the Canon to
indulge him with a sight of this Stone; and to look for a further
inscription, to support the assertion of Gassendi, who mentions
(page 325), That the Bishop Martin Cromer, an eminent Polish
historian, caused a mural marble monument to be inscribed and
erected to the memory of Copernicus, with the following inscription:
D. O. M.
R. D. NICOLAO COPERNICO,
Torunensi, Artium et
Medicinæ Doctori,
Canonico Warmiensi,
Præsenti Astrologo, et
Ejus Disciplinæ
Instauratori;
Martinus Cromerus,
Episcopus Warmiensis,
Honoris, et ad Posteritatem
Memoriæ, Causâ, posuit;
M. D. L. X. X. X. I.
“Gassendi adds, that this Monument was not erected until thirty-six
years after the death of Copernicus, which does not agree with this
date of 1581.
“The good Canon informed Bernouilli, that he was lodged in the

apartment of Copernicus, of which he was very proud; and invited
the Prussian Philosopher to visit him in that place, which he
accordingly did; and was shewn by the Canon another place, above
the Dormitories, which had been used by Copernicus as his study
and observatory, in which the Canon had a portrait of that eminent
man, concerning the original of which he would not say. This little
Observatory had an extensive view; but when Copernicus had
occasion for one more extensive, he was wont to observe on the
gallery of the steeple, which communicates with this place.
“Charmed with these classic footsteps, Bernouilli forgot to look at

the Monument on the chapter-house, above mentioned. In a
repository adjoining to the Cathedral, the Canon shewed Bernouilli
the remains of a hydraulic machine said to have been invented and
used by Copernicus. The construction seemed interesting, but in
great disrepair; and Bernouilli had not leisure to examine it
particularly. The use of the machine was to force and convey water
into the most elevated apartments of the house of the Canons, who
are now under the necessity of having it fetched from a distance,
from the lower Town.”
“I remember to have seen (says Bernouilli), in some old German

Journal, that the Library of the ancient town of Konigsberg contained
some books, chiefly mathematical, which were part of the Library of
Copernicus; and also his Portrait, which had been purchased at
Thorn, where the remains of his family still possessed the house in
which he was born, as late as the year 1720. In P. Freher’s Theatrum
Virorum eruditorum, there is a Chronostick on the year of
Copernicus’s death, 1543. p. 1447.
eX hoC eXCessIt trIstI CopernICVs eVo,

IngenIo astronVM et CognItIone potens.
“In the above mentioned book, p. 1442, there is a neat little Print of
Copernicus. In Hartknoch’s Alter und newes Preusen, here is a print
of Copernicus, from a picture on wood which hangs in what they call
his Cenotaph, at Thorn; and which represents him kneeling, in his
canonicals, before a Crucifix;—and below this portrait are these
sapphic verses:
Non parem Pauli gratiam requiro,

Veniam Petri neque posco; sed quam
In Crucis ligno dederas sationi,
Sedulus oro.
(a little lower)
Nicolao Copernico, Thoruniensi, absolutæ subtilitatis

mathematico, ne tanti viri apud exteros celeb. in sua patria periret
memoria, hoc monumentum positum.
Mort. Varmiæ, in suo Canonicatu, Anno 1543—

die 4 + ætatis LXXIII.
(lastly, lowest.)
Nicolaus Copernicus, Thoruniensis, Mathematicus celeberrimus.
“This Monument of Copernicus was erected by Melchior
Pyrnesius, M. D., who died in 1589.
“On the same altar-piece, or picture, is represented the portrait of

John D’Albert, with the following inscription.
Illustris Princeps Dn. Joh. Albertus, Polo. Rex, apoplexiâ hic

Thoru. mortuus, Anno 1501, die 17 Maii, ætat. 41; cujus viscera hic
sepulta, Corpore Craco translato; Reg. Ann. VIII.
“Upon the whole,” concludes Lord Buchan, “it appears the likeness
I send, of Copernicus, is most to be depended on; and, as such, I
flatter myself it will be an Heir-loom to infant America! Concerning
Napier, it is needless for me to enlarge; the learned Dr. Minto having
enabled me to do justice to his memory.”
Although the following particulars respecting Dr. Rittenhouse were

not communicated by the writer, Professor Barton, until it was too
late to give them a place in the body of the work, the Author
nevertheless is glad to have an opportunity of presenting to the
public, even at the close of his book, the interesting circumstances
this communication contains.
As Optics were one of his favourite studies, so he at one time

contemplated a course of public, and I think popular, lectures on this
beautiful and important branch of physics. On this subject he
mentioned to me his intention in the winter of 1785-1786. The
enthusiasm, indeed, with which he developed his design, and I may
add the warmth of zeal with which his manner at the time inspired
me, I can never forget. And, indeed, I cannot but regret, that our
excellent friend never made his appearance in publick, as a
LECTURER. As such, he would, unquestionably, have greatly
advanced the love and the knowledge of natural philosophy in the
United-States. He may, perhaps, have wanted some of the

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Chemistry Module II Physical Chemistry

II for IIT JEE main and advanced

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McGraw Hill Education (India) Private Limited

McGraw Hill Education Ofﬁces

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Published by McGraw Hill Education (India) Private Limited

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

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This edition can be exported from India only by the publishers,

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

Cover Designer: Creative Designer

visit us at: www.mheducation.co.in

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

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

comprehension, match the column and single digit integer).

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4. Solid State 4.1–4.31

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Thermodynamics deals with the feasibility of the reaction but

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Conc. Rate Rate

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

t1 Time C (6) Surface area

700∞C Rate Constant (K)/Velocity constant/Specific reaction

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Catalyst increases rate constant ‘k’. Molecularity

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Zero order reaction K [ A]

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Time Time 0.693 ln 2 1

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

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Kbxe = Kfa – Kfxe Activation energy (Ea)

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For example manufacture of NH3 by Haber’s process:

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

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1. At 10°C for any reaction rate constant = K, what will be

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

= 9.9 ¥ 1010 sec. If k1 : k2 = 1 : 9 and k1 = 1.3 ¥ 10–5 s–1

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14. The reaction k1 k

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

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

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