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IITJEE
CHEMICAL KINETICS &
NUCLEAR CHEMISTRY
C H E MI S T R Y
S T U D Y M A T E R I A L
PHASE  I
NARAYANA INSTITUTE OF CORRESPONDENCE COURSES
F N S H O U S E , 6 3 K A L U S A R A I M A R K E T
S A R V A P R I Y A V I H A R , N E W D E L H I  1 1 0 0 1 6
PH.: (011) 32001131/32/50 FAX : (011) 41828320
Websi t e : w w w . n a r a y a n a i c c . c o m
E mai l : i n f o @ n a r a y a n a i c c . c o m
2004 NARAYANA GROUP
This study material is a part of NARAYANA INSTITUTE OF CORRESPONDENCE COURSES for IITJEE, 200809. This is meant
for the personal use of those students who are enrolled with NARAYANA INSTITUTE OF CORRESPONDENCE COURSES, FNS
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without prior information and written permission of the institute.
PREFACE
Dear Student,
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& Subjective Questions.
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CONT ENT S CONT ENT S CONT ENT S CONT ENT S CONT ENT S
CHEMICAL KINETICS
& NUCLEAR CHEMISTRY
1. Theory
2. Solved Problems
(i) Subjective Type Problems
(ii) Single Choice Problems
(iii) Multiple Choice Problems
(iv) Miscellaneous Problems
Comprehension Type Problems
Matching Type Problems
AssertionReason Type Problems
3. Assignments
(i) Subjective Questions
(ii) Single Choice Questions
(iii) Multiple Choice Questions
(iv) Miscellaneous Questions
Comprehension Type Questions
Matching Type Questions
AssertionReason Type Questions
(v) Problems Asked in IITJEE
4. Answers
C
O
N
T
E
N
T
S
C
O
N
T
E
N
T
S
C
O
N
T
E
N
T
S
C
O
N
T
E
N
T
S
C
O
N
T
E
N
T
S
CHEMICAL KINETICS
& NUCLEAR CHEMISTRY
IITJEE Syllabus
Rates of chemical reactions; Order of reactions; Rate constant; First order
reactions; Temperature dependence of rate constant (Arrhenius equation).
CONTENTS
Rate of reaction
Elementary reaction
Integrated rate laws
Activation energy
Kinetics of some complex first order
reactions
Methods of determining order
Nuclear chemistry
Kinetics of radioactive disintegration
INTRODUCTION
Some chemical reaction occurs within
few micro seconds or milli seconds due
to formation of reaction intermediate
(carbocation, carboanion or free radicals).
But some reaction occur in few year or
months because breaking of strong ionic or
metallic bond is a slow process. Under
chemical kinetics we would study that
reaction which occurs at measurable rate.
In Chemical Kinetics we would be able to
understand the velocity as well as different
factors which would effect the chemical
reaction. Under this we will be studying
the mechanism of the reaction. Here
mechanism of reaction means how
reactants are converted into product or in
how many intermediate steps reactant is
converted into product. And which
intermediate step is rate determining step.
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Chemistry : Chemical Kinetics & Nuclear Chemistry
1. RATE OF REACTION
Rate of a reaction is defined as the increase in molar concentration of a product per unit
time or decrease in molar concentration of a reactant per unit time. Molar concentration is
normally measured in moles per litre, the rate of a reaction is specified in mole per litre per
time.
1.1 AVERAGE RATE
The quantity
x
t
(
(
=
d[A]
dt
Consider the hypothetical reaction
A 2B 3C D + +
Rate of disappearance of A =
d[A]
dt
Rate of disappearance of B =
d[B]
dt
Rate of appearance of C =
d[C]
dt
+
Rate of appearance of D =
d[D]
dt
+
But from the stoichiometry it is apparent that when one mole of A is reacted, two moles of
B are also consumed.
i.e. rate of disappearance of B = 2 rate of disappearance of A
d[B] d[A]
2
dt dt
=
or
d[A] 1 d[B]
dt 2 dt
=
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Similarly we can prove that
d[A] 1 d[C]
dt 3 dt
+ =
So, rate of reaction =
d[A] 1 d[B] 1 d[C] d[D]
dt 2 dt 3 dt dt
= = =
We can also generalize our statement i.e. for a general reaction
m A
1 2 1 2
m B n C n D + +
Rate of reaction =
1 2 1 2
1 d[A] 1 d[B] 1 d[C] 1 d[D]
m dt m dt n dt n dt
= = + = +
Illustration 1 : Dinitrogen pentaoxide decomposes as follows:
2 5 2 2
1
2
2
N O NO O + . If,
2 5
2 5
[ ]
[ ]
d N O
K N O
dt
=
2
2 5
[ ]
[ ]
O
K N O
dt
=
d N
2
2 5
[ ]
[ ] K N O
dt
=
d O
Derive a relation in, , '' ''' K K and K
Solution : For the given change
2 5 2 2
d[N O ] 1 d[NO ] d[O ]
2
dt 2 dt dt
= + = +
On substituting values,
2 5 2 5 2 5
1
[N O ] K [N O ] 2K [N O ]
2
= = K
or 2K K K = =
EXERCISE 1
1. For the reaction; 4NH
3(g)
+ 5O
2(g)
4NO
(g)
+ 6H
2
O
(g)
, the rate of reaction in terms of
disappearance of NH
3
is
3
d[NH ]
,
dt
then write rate expression in terms of O
2
, NO and
H
2
O.
2. For the decomposition reaction: N
2
O
4(g)
2NO
2(g)
; the initial pressure of N
2
O
4
falls
from 0.46 atm to 0.28 atm in 30 minute. What is the rate of appearance of NO
2
?
3. A chemical reaction 2A 4B + C; in gaseous phase shows an increase in concentration
of B by 5 10
3
M in 10 second. Calculate:
a) rate of appearance of B,
b) rate of the reaction,
c) rate of disappearance of A
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2. ELEMENTARY REACTION
An elementary reaction is a single molecular event, such as collision of molecules resulting
in a reaction. The set of elementary reactions whose overall effect is given by the net
chemical equation is called reaction mechanism.
Let us consider an example for the reaction of nitrogen dioxide with carbon monoxide.
(i)
2(g) (g) (g) 2(g)
NO CO NO CO [net chemical equation] + +
Suppose this chemical reaction takes place in two steps
(ii)
2(g) 2(g) 3(g) (g)
NO NO NO NO [Elementary reaction] + +
(iii)
3(g) (g) 2(g) 2(g)
NO CO NO CO [Elementary reaction] + +
Thus net reaction (i) is obtained by the combination of two elementary reaction (ii) and (iii)
and is a reaction intermediate as it is produced and consumed during the course of
reaction.
3
NO
2.1 MOLECULARITY
It is defined as the number of molecules taking part on the reactant side of an elementary
reaction. A unimolecular reaction is an elementary reaction involves one reactant molecule,
a bimolecular reaction is an elementary reaction that involves two reactant molecules.
2.2 DIFFERENTIAL RATE LAW
It is a relationship that relates the variation of rate of reaction with the concentration of
reactants.
Consider the reaction
2A 3B C + + D
as we have seen
m n
1 d[A] d[C]
[A] [B]
2 dt dt
=
[law of mass action states that rate of reaction is directly proportional to the product of the
active masses of reactants raised to some powers]
So,
m n
d[C]
k[A] [B]
dt
=
k is known as velocity constant or rate constant or specific reaction rate. m is known as
order with respect to A, n is known as order with respect to B. Sum m + n is known as
overall order of the reaction.
2.3 ORDER OF REACTION
It is defined as the sum of exponents or powers which are raised to concentration terms in
the rate law expression of a reaction.
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Difference between order and Molecularity : Molecularity of a reaction can be used to
describe only an elementary process and molecularity can be predicted just be viewing the
elementary reaction. Whereas order of a reaction refers to the overall reaction and can be
determined experimentally, however for elementary process the order and molecularity
are same. Molecularity has got no meaning for an overall reaction and order cannot be
predicted from a balanced chemical equation.
Note : If a reaction can be written as a combination of several elementary reaction then its the
slowest step that governs the rate of reaction i.e. the slowest step is the rate determining step.
Differential Rate Law :
Consider reaction
P 2Q + R
The differential rate law is written as
m n
d[P] 1 d[Q]
Rate k[P] [Q]
dt 2 dt
= = =
Value of m and n can be determined by performing the reaction in laboratory i.e. order
w.r.t P is m and order w.r.t. Q is n and overall order will be m + n.
4.4 UNITS OF k
In general rate law for a nth order reaction can be written as
n
dC
kC
dt
=
Where k is rate constant, k is characteristic of a reaction at a given temperature. It changes
only when temperature changes and n is the order of reaction.
n
dC/ dt
k
C
=
Units of k: (concentration)
1n
time
1
For a zero order reaction (n = 0)
Units of k = mol/L/s
For a first order reaction (n = 1)
Units of k = time
1
For a second order reaction (n = 2)
Units of k = (mol/l)
1
time
1
= l/mol/s
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Illustration 2 :The data given below are for the reaction of NO and Cl
2
to form NOCl at 25K
[Cl
2
] [NO] Initial rate 10
3
(mol litre
1
sec
1
)
0.05 0.05 1
0.15 0.05 3
0.05 0.15 9
a) What is the order with respect to NO and Cl
2
in the reaction?
b) Write the rate expression.
c) Calculate the rate constant
d) Determine the reaction rate when conc. of Cl
2
and NO are 0.2 M and 0.4 M
respectively.
Solution : For the reaction; 2NO + Cl
2
2NOCl
Rate = k[Cl
2
]
m
[NO]
n
(1)
Where, m and n are order of reaction w.r.t Cl
2
and NO, respectively.
From the given data:
1 10
3
= k[0.05]
m
[0.05]
n
(2)
3 10
3
= k [0.15]
m
[0.05]
n
(3)
9 10
3
= k[0.05]
m
[0.15]
n
(4)
By equations (2) and (3),
m = 1
By equations (2) and (4)
n = 1
a) order with respect to NO is 2 and w.r.t. to Cl
2
is 1.
b) Also, rate expression r = k[Cl
2
]
1
[NO
2
]
2
c) And rate constant.,
3
2 1
2
r 1 10
k
[Cl ][NO] [0.05] [0.05]
= =
2
= 8 litre
2
mol
2
sec
1
d) Further, r = k[Cl
2
]
1
[NO]
2
= 8 [0.2]
1
[0.4]
2
= 0.256 mol litre
1
sec
1
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EXERCISE 2 :
1. The reaction; 2A + B + C D + 2E; is found to be I order in A II order in B and zero
order in C.
a) Write the rate expression
b) What is the effect on rate on increasing the conc. of A, B and C two times.
2. The reaction; 2NO + Br
2
2NOBr, is supposed to follow the following mechanism,
i) NO + Br
2
NOBr
fast
2
ii) NOBr
2
+ NO 2NOBr
slow
2
+ NO
3
Step II N
2
O
5
+ NO
3
3NO
fast
2
+ O
2
Overall reaction 2N
2
O
5
4NO
2
+ O
2
Suggest the rate expression
3. INTEGRATED RATE LAWS
The differential rate laws show how the rates of reaction depend on the concentrations of
reactants. It is also useful to known how the concentration is depend on time, this
information can be obtained from the differential rate law by integration.
3.1 FIRST ORDER REACTION
A reaction is said to be first order if its rate is determined by the change of one
concentration term only.
Consider a first order reaction
A Products
The differential rate law equation will be
d[A]
k[A]
dt
=
Integrating both sides taking limits [ , which is the concentration at t = 0 and [A , the
concentration at time t
0
A]
t
]
t
0
[A]
[A]
d[A]
dt
=
t
0
k dt
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0
t
[A]
ln kt
[A]
= or
0
t
[A] 2.303
k log
t [A
=
]
A Products
t = 0 a
t = t a x
2.303 a
k log
t a
=
x
3.2 CHARACTERISTICS OF A FIRST ORDER REACTION
A first order reaction must follow above form of rate law for all time instants. This means
if we are given value of a i.e. initial concentration and values of x at different time instants
i.e. a x is known to us. If values of K are calculated for different time instants by using
above expression, if the reaction is following a first order kinetics then all values of K will
approximately be equal to each other.
3.3 HALF LIFE PERIOD
It is defined as the time in which half of the reactants are reacted for a first order reaction.
2.303 a
k log
t a
=
x
at
1/ 2
a
t t ; x =
2
=
1/ 2
2.303 a
k log
t a
=
/ 2
1/ 2
0.6932
t
k
=
In fact we can define any life suppose we want to define 7/8 life.
2.303 a
k log
t a
=
x
at
718
7a
t t ; x=
8
=
at
718
2.303 a
k log
7a
t
a
8
=
718
2.303 2.303
t log8 3
k k
= = log 2
7/ 8 1/ 2
t 3 t =
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Important thing is that in a first order reaction time required for the completion of a definite
fraction is independent of initial concentration of reactants.
3.4 HALF LIFE FOR NTH ORDER REACTION
Let A products is following nth order kinetics.
i.e.
n
A]
k[A] , it can be shown that
dt
=
d[
n 1
1/ 2 n 1
0
2 1
t
k(n 1)a
1/ 2 n 1
0
1
i.e.t (n 2)
a
Expression for first order reaction is
2.303 a
k log
t a
=
x
or
2.303 a
t log
K a
=
x
=
2.303
[loga log(a x)]
k
2.303 2.303
t loga log(a x)
k k
=
Comparing this equation with Y = mx + C
So a plot of t vs log (a x) will be straight line with a intercept of
2.303
loga
k
and a slope
of
2.303
k
2.303
loga
K
2.303
slope
K
=
log(a x)
t
i
m
e
3.5 EXAMPLES OF FIRST ORDER REACTION
3.5.1 Decomposition of H
2
O
2
2 2 2 2
2H O 2H O O +
2 2 2
H O H O O [slow i.e. rate determining step] +
[fast]
2
O O O +
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So
1
2 2
Rate [H O ]
or
2 2
R k[H O = ]
2
x
Order = 1
Kinetics of this reaction can be studied by withdrawing a definite volume of reaction
mixture after regular interval of time and titrating it against KM solution in presence of
dil.
4
nO
2 4
H SO
4 2 4 2 4 4 2
2KMnO 3H SO K SO 2MnSO 3H O 5O + + + +
5
2 2 2 2
[H O O H O O ] + +
4 2 4 2 2 2 4 4 2
2KMnO 3H SO 5H O K SO 2MnSO 8H O 5O + + + + +
Since H
2
O
2
is undergoing self decomposition so quantity of H
2
O
2
present in a definite
volume will also go on decreasing, KMnO
4
is reacting with H
2
O
2
so titre value i.e. volume
of KMnO
4
used will also go on decreasing.
Let and be the volumes of KM used at zero time and after t time respectively.
0
V
t
V
4
nO
then [a = initial conc. of ]
0
V a
2 2
H O
[a x = conc. of after t time]
t
V a
2 2
H O
0
t
V a
V a
=
x
0
t
V 2.303
og
t V
= k l
Illustration 3 :From the following data show that the decomposition of hydrogen peroxide in
aqueous solution is a first  order reaction. What is the value of the rate
constant ?
Time in minutes 0 10 20 30 40
VolumeV/(ml) 25.0 20.0 15.7 12.5 9.6
where V is the number of ml of potassium permanganate required to decompose a
definite volume of hydrogen peroxide solution.
Solution : The equation for a first order reaction is
1
2.303 a
k log
t a
=
x
The volume of KMnO
4
used, evidently corresponds to the undecomposed
hydrogen peroxide.
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Hence the volume of KMnO
4
used, at zero time corresponds to the initial
concentration a and the volume used after time t, corresponds to (a  x) at that
time. Inserting these values in the above equation, we get
when t = 10 min. k
1
=
2.303
10
log
25
20.0
= 0.022287 min
1
= 0.000314 s
1
when t = 20 min. k
1
=
1 1
2 .303 25
log 0.023230 min 0.0003871 s
10 15.7
= =
when t = 30 min. k
1
=
1 1
2.303 25
log 0.02369 min 0.0003948 s
30 12.5
= =
when t = 40 min. k
1
=
1 1
2.303 25
log 0.023897 min 0.0003983 s
40 9.6
= =
The constancy of k, shows that the decomposition of H
2
O
2
in aqueous solution is a
first order reaction.
The average value of the rate constant is 0.0003879 s
1
.
3.5.2 Decomposition of NH
4
NO
2
in aqueous solution
4 2 2 2
NH NO N 2H O +
1
4 2
Rate [NH NO ]
4 2
Rate K[NH NO ] =
order = 1
Kinetics of this reaction may be studied by collecting the nitrogen evolved and measuring
its volume after regular intervals of time
Let and be the volumes of liberated after t time and at the end of reaction.
t
V V
2
N
4 2 2 2
NH NO N 2H O +
Initial conc. a 0
Conc. after t time a x x
Conc. at t = 0 a
t
V x
V
a
x or
t
V V a
t
V a
V V a x
=
t
V 2.303
k log
t V
=
V
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Note: t = indicates that sufficient time is provided to the reaction i.e., the reaction has
practically gone to completion.
Illustration 4 : From the following data for the decomposition of diazobenzene chloride, show
that the reaction is of first order:
Time (min) 20 50 70
Volume of N
2
(mL) 10 25 33 162
Solution : C
6
H
5
N
2
Cl C
6
H
5
Cl + N
2
initial concentration a
Concentration of after time t (a x) x
At time, i.e., when the reaction is complete, the whole of C
6
H
5
N
2
Cl converts
into N
2
. Hence volume of N
2
at time corresponds to the initial concentration a
while volumes of N
2
at different time intervals correspond to x as shown above.
For t = 20 min,
1
1
2.303 162
k log 0.0032min
20 162 10
= =
For t = 50 min,
1
1
2.303 162
k log 0.0033min
50 162 25
= =
For t = 70 min,
1
1
2.303 162
k log 0.0032min
70 162 33
= =
The constant of k
1
shows that the decomposition of C
6
H
5
N
2
Cl; is a first order
reaction.
3.5.3 Conversion of NChloroacetinalide into pchloro acetanialide
N
Cl
CH
3
O
rearrangement
isomerism
N
H
CH
3
O
Cl
NchloroNphenylacetamide
N(4chlorophenyl)acetamide
1
Rate [Nchloroacetinalide]
order = 1
Kinetics of this reaction may be studied by withdrawing a definite volume of the reaction
mixture after regular intervals of time, adding excess of KI and titrating the liberated
against standard sodium thiosulphate solution.
2
I
Nchloroacetinalide reacts with KI and liberates but pchloroacetinalide does not.
2
I
I
2 2 2 3 2 4 6
2Na S O Na S O 2NaI + +
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Nchloroacetinalide P chloroacetinalide
t = 0 a 0
t = t a x x
Let and be the volumes of sodium thiosulphate used at t = 0 and t = t respectively,
then
0
V
t
V
0
V a
t
V a x
0
t
V a
V a x
=
0
t
V 2.303
k log
t V
=
Illustration 5 : Acetochloracetanilide (Nchloroacetanilide) is converted into p
chloroacetanilide, it is followed by the addition of KI which acts only on the
former compound. The progress of reactionis studied by titrating the iodine
liberated with standard hypo solution and the following results are obtained.
Time (hour) 0 1 2 6
ml of hypo solution 45 32 22.5 5.7
Show that the reaction is unimolecualr. Calculate the velocity constant of the
reaction and also determine the fraction of Nchloroacetanilide which has
reacted in three hours.
Solution : The velocity constant of the first order reaction is given by
2.303 a
k log
t a
=
x
Here the initial concentration a corresponds to the volume of hypo used against
liberated iodine at time 0, a = 45, (a x) corresponds to the volume of hypo used
for titrations at different intervals of time, i.e. when t = 1 hour, (a x) = 32, and so
on.
Substituting the values in the above equation,
(i) When t = 1 hour, (a x) = 32
2.303 45
log 0.3411
1 32
= = k
(ii) When t = 2 hours, (a x) = 22.5
2.303 45
log 0.3468
t 22.5
= = k
(iii) When t = 6 hours, (a x) = 5.7
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2.303 45
k log 0.3443
6 5.7
= =
Since the value of K in all the three cases is nearly same, the reaction must be
unimolecular.
Calculation of fraction that has reacted in 3 hours
Let the amount reacted in 3 hours = x moles
Given a = 45, t = 3 hours, (a x) = 45 x
Substituting these values in the reaction
2.303 a
log
t a
=
k
x
2.303 45
300 log
t (45
=
0.
x)
45 x = 16.03
x = 28.97
Hence fraction of Nchloroacetanilide reacted in 3 hours =
28.97
0.643
45
=
3.6 PSEUDO FIRST ORDER REACTION
If molecularity of a reaction is 2 but order is 1 then the reaction is known as pseudo first
order reaction or pseudo unimolecular reaction.
Hydrolysis of tertiary butyl bromide :
3 3 3 3
(CH ) CBr OH (CH ) OH Br
+ +
This reaction takes place in two steps.
i)
slow
C H
3
CH
3
CH
3
Br C H
3
CH
3
CH
3

Br +
ii)
fast
C H
3
CH
3
CH
3
OH C H
3
CH
3
CH
3

OH +
Since slowest step is rate determining step.
1 0
3 3
Rate [(CH ) CBr] [OH ]
=
3 3
K[(CH ) CBr]
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Order = 1
So the reaction is pseudo unimolecular
3.6.1 Hydrolysis of Ester catalysed by an acid
H
3 2 5 2 3 6 5
CH COOC H H O CH COOH C H OH
+
+ +
3 2 5 2
Rate [CH COOC H ][H O]
Since water is in large excess so its concentration almost remains constant
1
3 2
Rate [CH COOC H ]
5
5
t
a
x
3 2
Rate k[CH COOC H ] =
order = 1
Molecularity = 2
So the reaction is pseudo unimolecualr reaction. Kinetics of this reaction can be studied by
withdrawing a definite volume of reaction mixture after regular intervals of time and
titrating against NaOH solution. This reaction mixture is chilled during titration by adding
ice cold water. Chilling checks hydrolysis of ester during titration. Chilling also checks
reaction of ester with NaOH (second order and biomolecular).
Let and V
0
V , V
be the volumes of NaOH used at 0 time, t time and at the end of
reaction respectively. The volume of NaOH used at 0 time ( ) corresponds to the
concentration of catalyst and volume of NaOH used after t time (V corresponds to the
concentration of catalyst and acetic acid formed.
0
V
t
)
H
3 2 5 2 3 2 5
CH COOC H H O CH COOH C H OH
+
+ +
t = 0 a 0
t = t a x x
t = 0 a
V
t 0 3
V x [x conc. of CH COOH formed after t time] =
V V
0
(V
0 t 0
V ) (V V ) a x
t
V V a
0
t
V V a
V V a x
=
0
t
V V 2.303
og
t V
k l
V
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Illustration 6 :5 ml of ethylacetate was added to a flask containing 100 ml of 0.1 N HCl placed
in a thermostat maintained at 30C. 5 ml of the reaction mixture was withdrawn
at different intervals of time and after chilling, titrated against a standard alkali.
The following data were obtained :
Time (minutes) 0 75 119 183
ml of alkali used 9.62 12.10 13.10 14.75 21.05
Show that hydrolysis of ethyl acetate is a first order reaction.
Solution : The hydrolysis of ethy acetate will be a first order reaction if the above data
confirm to the equation.
0
1
t
2.303 V V
k log
t V
=
V
Where V
0
, V
t
and V
 V
0
= 21.05  9.62 = 11.43
Time V
 V
t
0
1
t
303
g
t V V
2. V V
lo k
=
75 min 21.05  12.10 = 8.95
1
2.303 11.43
log 0.003259 min
75 8.95
=
119 min 21.05  13.10 = 7.95
1
2.303 11.43
log 0.003264 min
119 7.95
=
83 min 21.05  14.75 = 6.30
1
2.303 11.43
log 0.003254 min
183 6.30
=
A constant value of k shows that hydrolysis of ethyl acetate is a first order reaction
3.6.2 Inversion of Cane Sugar
H
12 22 11 2 6 12 6 6 12 6
Cane sugar glu cose fructose
C H O H O C H O C H O
+
+ +
12 22 11 2
Rate [C O O ][H O]
Since water is solvent its concentration is constant.
So Rate = K[
12 22 11
C H O ]
Molecularity = 2
Order = 1
So the reaction is pseudo unimolecular
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If some inert liquid is used as solvent then concentration of water can be changed and rate
changes on changing the concentration of water. The reaction then becomes second order.
Rate of this reaction is also proportional to the concentration of catalyst H
+
. But
concentration of catalyst remains constant during the reaction. If we change concentration
of water as well as that of H
+
then reaction becomes 3
rd
order.
12 22 11 2
Rate [C H O ][H O][H ]
+
Cane sugar
Glucose
Fructose
dextro rotatory
dextro rotatory
Laevo rotatory
Prism
Kinetics of this reaction can be studied by taking cane sugar solution in a polarimeter and
measuring the angles of rotation after regular intervals of time.
Let and be the angles of rotation at 0 time, after t time and at the end of reaction.
0
r , r
t
r
t
r
0
r
90 90
180
0
So, (i)
0 t
r r x
(ii)
0
r r a
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0 0 t
(r r ) (r r ) a x
or r r
t
a x
0
t
r r a
r r a x
=
0
t
r r 2.303
k log
t r
=
r
Illustration 7 :The optical rotations of sucrose in 0.5 N HCl at 35C at various time intervals
are given below. Show that the reaction is of first order :
Time (minutes) 0 10 20 30 40
Rotation (degree) +32.4 +28.8 +25.5 +22.4 +19.6 11.1
Solution : The inversion of sucrose will be first order reaction if the above data confirm to
the equation , k
t
r r
r r
t
1
0
2 303
=
.
log
Where r
0
, r
t
and r
k
10 min +28.8 39.9
2.303 43.5
log
10 39.9
= 0.008625 min
1
20 min +25.5 36.6
2.
= 0.008625 min
303 43.5
log
20 36.6
1
0 min +22.4 33.5
2.
= 0.008694 min
303 43.5
log
30 33.5
1
40 min +19.6 30.7
2.
= 0.008717 min
303 43.5
log
40 30.7
1
The constancy of k
1
indicates that the inversion of sucrose is a first  order reaction.
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EXERCISE 3 :
1. From the data obtained for decomposition of H
2
O
2
, show that decomposition of a first
order reaction.
Time in minutes 0 10 20 30 40
Volume of KMnO
4
(ml) 25.0 20.0 15.7 1.5 9.6
2. From the following data for the decomposition of ammonium nitrite in aqueous solution,
show that the reaction is a first order.
Time in minutes 10 15 20 15
Volume of N
2
(ml) 6.25 9.00 11.4 13.65 35.05
3. A certain volume of ethyl acetate was added to a flask containing HCl (as catalyst)./ 5 m l
of reaction mixture was withdrawn at different intervals of time and titrated against a
standard alkali. The following data were obtained
Time in minutes 0 75 119 183
Volume of NaOH(ml) 9.62 12.1 13.1 12.75 21.05
Show that hydrolysis of ester is a first order reaction.
4. ACTIVATION ENERGY (E)
For a chemical reaction to take place reactant molecules must make collisions among
themselves. Actually a fraction of collisions are responsible for the formation of products
i.e. not all collisions are effective enough to give products. The collisions which converts
the reactants into products are known as effective collisions. Effective collisions between
the molecules which have energies equal to or above a certain minimum value. This
minimum value of energy which must be possessed by the molecules in order to make
effective collision is called threshold energy. Now most of the times, the reactants do not
possess threshold energy. So in order to make effective collisions an additional energy is
needed. This additional energy which is absorbed by the molecules so that they achieve
threshold energy is called as activation energy.
b
E a
E
P
o
t
e
n
t
i
a
l
e
n
e
r
g
y
Reaction coordinate
Reactants
Products
Threshold energy
H
b
E
a
E
Reaction coordinate
Reactants
Products
H
Products
Threshold energy
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= activation energy of forward reaction
a
E
= activation energy of backward reaction
b
E
= Heat of reaction H
b
b
=
a
H E E =
a b
H E E
Since Since E E
a
E E >
a b
<
So, > i.e. reaction is endothermic So, i.e. reaction is exothermic H 0 H 0 <
4.1 FACTORS INFLUENCING THE RATE OF A REACTION
(i) Concentration of the reactants: More the concentration of the reactants more will be
the rate.
(ii) Temperature: The rate of a reaction increases with an increase in temperature.
(iii) Nature of reactants: Physical and chemical state of the reactants also affects the rate
of reaction.
(iv) Effect of Catalyst: A reaction proceeds much faster in the presence of a catalyst.
(v) Effect of radiations: Photochemical reactions are faster than thermal ones because in
the former all the energy of photons is completely used in exciting molecules. While in
latter the energy is distributed into various forms like translational, rotational and
vibrational
4.2 EFFECT OF TEMPERATURE ON REACTION RATE
The increase of temperature generally increases rate and therefore rate constant of a
reaction.
Temperature coefficient =
T 10
T
k
+
k
= rate constant tC
T
k
= rate constant at T + 10C
T 10
k
+
Normally T and T+ 10 are taken as 25C and 35C.
The value of temperature coefficient at room temperature lies between 2 and 3.
Temperature coefficient is only an approximate method of indicating influence of
temperature on reaction rate. The exact variation of rate constant with temperature is
given by Arrhenius equation.
2
d nk E
dT RT
=
(i)
E Energy of activation
T Temperature is Kelvin scale
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R Gas constant
2
E
d nk dT.
RT
=
{E is supposed to be constant]
E 1
nk C
R T
 
= +

\ .
or
E
nk C
RT
= +
nK
E
slope
R
=
1/ T
(iv)
on comparing this equation with Y = mx + C
4.3 ANOTHER FORM OF ARRHENIUS EQUATION
E/ RT
k Ae
=
A frequency factor
E/ RT
e
=
or
2 2
1 1
k T E
log
k 2.303R TT
=
1
2
T
Illustration 8: The activation energy of a noncatalysed reaction at 37C is 200 kcal/ mol and
the activation energy of the same reaction when catalysed decreased to only 6.0
kcal/mol. Calculate the ratio of rate constants of the two reactions.
Solution : We know that:
a
E / RT
k Ae
=
Let k = rate constant for noncatalysed reaction and k
c
rate constant for catalysed
reaction. E
a
be the activation energy of noncatalysed reaction and E
ac
be the
energy of activation of catalysed reaction.
1.
a
E / RT
k Ae
=
2.
a
E / RT
c
k Ae
=
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ac a
1
(E E )
RT
c
k
e
k
=
ac c
c
k 1
log (E E )
k 2.303RT
=
3 3
c
k 1
log (6 10 200 10 )
k 2.303 2 310
=
c
k
log 9.8
k
=
10 9 c
c
k k
1.56 10 or 6.3 10
k k
= =
Illustration 9 : A first order reaction A B requires activation energy of 70 kJ/mol. When
20% solution of A was kept at 25C for 20 minutes, 25% decomposition too
place. What will be the percent decomposition in the same time in a 30%
solution maintained at 40C? Assume that the activation energy remains
constant in this range of temperature.
Solution : Note: it does not matter whether you take 20%, 3%, 40% or 70% of A.
At 25C, 20% of A decomposes 25%
0
t
C
kt 2.303log
C
=
100
k(40) 2.303log
75
=
1
k(at 25C) = 0.0143min
40 2 1
25 1 2
k Ea T
log
k 2.303R TT
 
=

\ .
T
3
40
k 70 10 40 2
log
0.0143 2.303 8.31 298 313
 
=

\ .
5
1
k (at 40C)=0.055min
Now calculate the % decomposition at 40C using first order kinetics
0
t
C
kt 2.303log
C
=
100
0.055 40 2.303log
100 x
=
= decomposition of A at 40C. x 67.1 67.1%
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4.4 ACTIVATION ENERGY AND TEMPERATURE DEPENDENCY
The temperature dependency of reactions is determined by activation energy and
temperature level given below is a graph showing the temperature dependency of the
reaction rate.
Following conclusions are drawn from this graph.
(i) From Arrhenius law a plot of
1
k vs
T
ln gives a straight line, with large slope for large
E and small slope for small E.
(ii) Reactions with high activation energy are far more temperature sensitive then reactions
with low activation energy.
nK
T 1000 =
5
10
20
100
1000 K 463 K
High E
Low E
E
slope
R
=
for doubling rate
T 87 =
for doubling rate
1/ T
50
200
2000 K 376 K
iii) A given reaction is much more temperature sensitive at low temperatures then at high
temperatures.
EXERCISE 4 :
1. (i) Which reaction will have the greater temperature dependence for the rate constant,
one with small value of E
a
or one with large value of E
a
(ii) For a reaction, rate constant is given as lnK(min
1
) = 31.33
11067
. Evaluate, K,E
T
and A for the chemical reaction at 25C.
2. For a particular first order reaction at 27C, the concentration of reactant is reduced to one
half of its initial value after 5000s. At 37C, the concentration is halved after 1000s.
Calculate (a) the rate constant of the reaction at 27C, (b) the time required for the
concentration to be reduced to one quarter of its value at 37C, (c) the activation energy
of the reaction.
3. The Arrhenius equations for the rate constant of decomposition of methyl nitrite and ethyl
nitrate are
1 1
1 13 1 14
1 2
152300Jmol 157700Jmol
k (s ) 10 exp and k (s ) 10 exp
RT RT
   
= =
 
\ . \ .
respectively. Find the temperature at which the rate constants are equal.
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4.5 EFFECT OF CATALYST ON RATE OF REACTION
A catalyst is a substance that takes part in a reaction. It increases the rate of reaction by
providing a new pathway.
Now let us consider a reaction i.e. hydrolysis of an ester catalysed by an acid.
H
2
Ester + H O acid alcohol
+
+
The rate of the reaction is given as
Rate k[ester][H
+
= ]
Since concentration of H in the beginning and
at the end is same so.
+
Rate k [Ester] =
where k k[H ]
+
=
k is known as pseudo or effective rate constant
P
o
t
e
n
t
i
a
l
e
n
e
r
g
y
b
E
a
E
Reaction coordinate
Reactants
H
Products
Alternative path
provided by the
catalyst.
Now according to the definition of the catalyst are substances which increases the rate of
reaction by their presence but their presence is not required for the reaction to occur. Now
according to this definition, absence of should not let the reaction to happen, therefore
the rate of reaction in the absence of should be,
H
+
H
+
Rate K[ester] =
If [ M then rate of reaction would becomes less than the rate which we had in its
absence. In order to avoid above controversies, we are required to go through the
functioning of catalyst.
H ] 1
+
<
There are two types of catalyst.
a) Reactant catalyst b) Nonreactant catalyst.
Former increases the rate of reaction by existing in the rate law. Therefore, in the absence
of reactant catalyst the reaction rate will be zero i.e. no reaction will take place.
The nonreacting catalyst on the other hand do not exist in the rate expression. Changing
the concentration of nonreacting catalyst has no effect on the rate. These catalyst increase
the rate of reaction by either decreasing activation energy or by increasing Arrhneius
constant.
5. KINETICS OF SOME COMPLEX FIRST ORDER REACTIONS
5.1 PARALLEL REACTIONS
First order parallel chain reaction: If A decomposes into B and C parallely following two
paths with first order rate constants k
1
and k
2
respectively, then it is known as first order
parallel chain reaction. Let the overall rate constant of A is k
0
by which decay into B and C.
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1
k
A
B
C 2
k
 
 
1
t
d B
k A
dt
+ = (i)
 
 
2
t
d C
k A
dt
+ = (ii)
 
 
0
t
d A
k A
dt
= (iii)
      d A d B d C
dt dt dt
= + + (iv)
Putting equations (i), (ii) and (iii) in equation (iv), we get
k A      
0 1 2
t t
k A k A = +
t
2
or,
0 1
k k k = +
From equation (i) and (ii), we get
 
 
1
t
d B
k A
dt
=
or, (v)      
1
t
B d B k A = =
t
dt
t
dt Similarly,   (vi)    
2
t
C d C k A = =
Divide equation (v) by equation (vi), we find
 
 
t 2
1
t
B
k
C k
= (at any time t) (vii)
       
0 t t
A A B C = + +
t
t
or (viii)        
0 t t
A A B C = +
( )
 
 
0
1 2
t
A
k k t 2.303log
A
+ =
If k
1
and k
2
, t and [A]
0
is known, then [A]
t
can be calculated then by solving equations
(vii) and (viii), the concentration of B and C at any time i.e., [B]
t
and [C]
t
can be calculated.
(b) Half lives of A in different path of parallel chain reaction.
for parallel chain reaction
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1
k
A
B
C 2
k
k
0
= k
1
+ k
2
or k
0
> k
1
and k
0
> k
2
Let the rate of formation of B is x% rate of decomposition of A.
    d B d A
x%
dt dt
+ =
k
1
[A]
t
= x % k
0
[A]
t
or, k
1
= x% k
0
( ) ( )
1/ 2 1/ 2
1 overall
n 2 x n 2
t 100 t
=
l l
or, ( )
( )
1/ 2
overall
1/ 2
1
100 t
t
x
=
where (t
1/2
)
1
is the half life of A, while it is converting into B and (t
1/2
)
overall
is the half life
of A.
Similarly, halflife of A, i.e. (t
1/2
)
2
while it is converting into C will be
( )
( )
( )
1/ 2
overall
1/ 2
2
100 t
t
100 x
(c) For the first order parallel chain reaction
1
k
A
2
k
mB
nC
 
 
t 1
2
t
B
mk
C mk
=
and k
overall
= k
1
+ k
2
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5.2 CONSECUTIVE OR SEQUENTIAL REACTIONS
Consider the following consecutive reaction
1 2
K K
A B C
B will exist in the sequential reaction provided that the rate of formation of B must be
higher than is rates of decay; which is governed by its rate constant of formation and
deformation. The stage of the reaction where the rate of formation of B is equal to its rate
of decay is known as steady state.
Now from the sequential reaction, it is very clear that
 
   
k, t
1
t t
d A
k A A A e
dt
= =
0
(i)
 
   
1 2
t t
d B
k A k B
dt
+ =
or
 
     
1
k t
1 1
t t 0
d B
k B k A k A e
dt
+ = = (ii)
Solving first degree differential equation (ii) with integrating factor , then we get
concentration of B at any time t.
2
k t
e
 
 
1 2
1 k t k t 0
t
2 1
k A
B e
k k
(
=
e
(b) Time at which concentration of B is maximum
2
2 1 1
1 k
t n
k k k
=
l
(c) Maximum concentration of B
   
x
2
max 0
1
k
B A
k
 
=

\ .
where
2
1 2
k
x
k k
=
(d) Time at which
  d B
dt
is maximum
2
1 2
2 k
t l
k k k
=
1
n
(e) At steady state,
k
1
[A]
t
= k
2
[B]
t
(f) If k
1
< < k
2
, then sequential reaction converts into
1
k
A C
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1
t
d A
k A
dt
=
Illustration 10 :
227
Ac has a halflife of 22.0 years with respect to radioactive decay. The decay
follows two parallel, paths, one leading to
222
Th and the other to
223
Fr. The
percentage yields of these two daughter nuclides are 2.0 and 98.0 respectively.
What are the decay constants () for each of the separate paths?
Solution : The rate constant of the decay is
k =
1
2
693 0.693
t 2
=
0.
2
If k
1
and k
2
are the rate constants of the reactions leading to
222
Th and Fr
223
,
respectively we have
k
1
+ k
2
=
0.693
22
;
1
2
k 2
k 9
=
8
On solving for k
1
and k
2
, we get
k
2
= 0.03087 y
1
k
1
= 0.00063 y
1
EXERCISE 5 :
1. An organic compound A decomposes following two parallel first order mechanisms.
5 1 1
1
2
k 1
and k 1.3 10 s
k 9
= =
A
B
C
Calculate the concentration ratio of C to A, if an experiment is allowed to start with only
A for one hour.
2. For a consecutive first order reaction A B the values of K
1 2
K K
C,
1
and K
2
are
45 sec
1
and 15 sec
1
respectively. If the reaction is carried out with pure A at a
concentration of 1.0 mol dm
3
,
a) How much time till be required for the concentration of B to reach a minimum.
b) What will be the maximum concentration of B.
c) What will be the composition of the reacting system after a time interval of 10
minute.
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5.3 REACTIONS INVOLVING OPPOSING OR REVERSIBLE REACTIONS
Such reactions results in equilibrium. In other words the reactant changes to product and
vice versa.
Say we have an opposing reaction in which both forward and backward reactions are first
order, viz.,
(k
1
and k
2
are rate constant of forward and backward reaction)
Say initial conc. of A and B are a and b mol L
1
respectively.
If after time t, x moles/L of A change into B, then conc. of A and B will be (a x) and
(b + x) respectively.
The net rate of the reaction would be given as :
Rate = k
1
(a x) k
2
(b + x) (i) [ both processes occur simultaneously]
When equilibrium is reached, the net rate is zero
Thus, k
1
(a x
e
) = k
2
(b + x
e
) (e = equilibrium)
Hence, (b + x
e
)
2
1
k
k
= (a x
e
) or b =
2
1
k
k
(a x
e
) x
e
Substituting value of b in eqn. (i)
Rate of reaction,
(
+ x x ) x a (
k
k
k ) x a ( k
dt
e e
2
1
2 1
=
dx
on solving, we get
Rate = (k
1
+ k
2
) (x
e
x)
After rearranging and integrating the equation, we get an equation similar to first order
reaction as shown below.
or
or
dt ) k k (
x x
dx
2 1
e
+ =
0
x t
1 2
x 0
e
dx
(k k )dt
x x
= +
log t ) k k (
x x
x x
2 1
e
0 e
+ =
A B
k
1
k
2
Or
x x
x x
log
t
1
) k k (
e
0 e
2 1
= +
The equation is similar to first order reaction except that the measured rate constant is now
the sum of the forward and the reverse rate constants.
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5.4 PRESSURE CHANGE METHOD
This method is used for gaseous reactions.
As reaction proceeds there is change in pressure.
For a reaction, A
(g)
B
(g)
+ C
(g)
Initial pressure at t = 0 P
0
0 0
Pressure at time (t) (P
0
x) x x
(Here x is no. of moles of A which change to produce)
Thus, total pressure (P
t
) at time (t) = P
0
x + x + x
or P
t
= P
0
+ x, x = P
t
P
0
a x = P
0
(P
t
P
0
) = 2P
0
P
t
Thus,
0
0 t
P 2.303
k log
t (2P
=
P )
6. METHODS OF DETERMINING ORDER
(i) Integration Method : In this method, the data is substituted into integrated rate
equations for different order reactions. The equation which gives a constant value of K
decides the order of reaction. Suppose we have to check whether a reaction is
following first order kinetics or not then we will calculate values of K by using
expression.
0
t
1 [A]
K ln
t [A]
= . If for different values of t and [ K comes constant then order of
reaction will be 1 other wise we will switchover to higher order expressions.
t
A] ,
Integrated Expressions for various reactions
Zero order
0
x
t
= k
First order
1
2.303 a
og
t (a
k l
x)
Second order
2
1 x
k
t a(a x)
=
`
)
Third order
3 2 2
1 x(2a x)
k
t a (a x )
=
`
)
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(ii) Graphical Method: In this method the data are plotted according to different
integrated rate equations so as to yield a straight line suppose log (ax) vs t is a straight
line then order of reaction will be 1.
(a x)
Zero order
t
log(a x)
First order
t
Second order
t
1
(a x)
Third order
t
2
1
(a x)
(iii) Half life Method: As we have seen for nth order reaction
1/ 2 n 1
1
t
a
Let
2
t be the half life at initial concentration a and be the half life at intial
concentration
1/
1 1
1/ 2
2
t
2
a .
Then
1/ 2
1 n 1
1
1
t
a
1/ 2
2 n 1
2
1
t
a
1/ 2
1/ 2
n 1
1
2
2 1
t
a
t a
 
=

\ .
So by knowing half life at two different initial concentrations, order of reaction can be
calculated.
Initial Rate Method
In this method concentration of one of the reactants is varied by a known factor and its
effect on the initial rate of the reaction is studied for example if the rate doubles on
doubling the concentration of a reactant then order with respect to that reactant will be
1. If rate becomes four times on doubling the concentration then order with respect to
that reactant will be two. This way by changing the concentration of all the reactants
one by one and keeping the concentrations of rest all reactants constant we can find
order with respect to each of reacting species.
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7. NUCLEAR CHEMISTRY
7.1 INTRODUCTION
In chemical reactions, atoms of the reactants combine by a rearrangement of extra nuclear
electrons but nuclei of the atoms remains unchanged. In a nuclear reaction on the other
hand, it is the nucleus of the atom which is involved.
7.2 RADIOACTIVITY
This can be defined as the spontaneous emission of certain kinds of radiations by some
elements and the elements emitting such radiation are called radioactive elements.
Radiation emitted by radioactive substances are of three types :
Sl.
No.
particles particles rays.
1. 2 units +ve charge & 4
units mass.
Unit ve charge with no
mass
Electromagnetic waves
of short wavelength.
2.
Represented as
2
or
4
He
He
++
Represented as
o
1
e Represented as
0
0
dt
N.
N number of atoms of radioactive isotope.
Time
N
o
.
o
f
a
t
o
m
s
o
f
A
Time
R
a
t
e
o
f
d
e
c
a
y
o
f
A
dN
N
dt
or
dN
dt
= N (i)
is known as decay constant or disintegration constant.
If dt = 1 second.
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Then
dN
N
=
Decay constant ( ) : Thus decay constant ( ) is equal to the fraction of radioactive
isotope disintegrating per second.
From equation (i)
dN
d
N
=
t
log N t C = +
where C is integration constant
when t = 0; N = No. (initial number of atoms)
log N = C
0
So log N = t log
0
N
0
N
t log
N
=
0
N 1
ln
t N
=
0
N 2.303
log
t N
=
All radioactive decay follows first order kinetics.
8.1 ACTIVITY AND UNITS OF ACTIVITY
The unit of radioactivity is measured as the rate at which it changes into daughter nucleus.
It has been derived on the scale of disintegration of radium. Let us consider 1 g of Ra (at.
Wt. 223 and years).
1/ 2
t 1600 =
Rate of decay (activity ) No. of atoms in 1 g Ra. =
23
10
.6932 1 6.023 10
3.7 10 dps
1600 365 24 60 60 223
=
=
= Becque rrel
10
3.7 10
1 curie = 3. dps = Becquerrel
10
7 10
10
3.7 10
1 Rutherford = 10 dps.
6
Initial activity Initial amount
Activity after `t time amount left undisintegrated after t time.
2.303 initial activity
log
t activity after t time
=
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as we have seen
0
ln N t ln N =
0
N
ln t
N
=
t
0
N
e
N
=
or
t
N No e
=
Half life period (t : It is the time after which activity of a radioactive isotope reduces
to half of its initial value.
1/ 2
)
When
1/ 2 0/ 2
t t , N N = =
0
N 2.303
log
t N
=
0
1/ 2
0/ 2
N 2.303
t log
N
=
1/ 2
0.6932
t =
Unit of
1
time =
Specific activity : This is defined as activity per unit mass of the sample.
Average life (K) : The reciprocal of decay constant is defined as average life of radioactive
isotope.
Average life
1
=
1/ 2
t 1
K
0.6932
= =
1/ 2
K 1.44 t =
8.2 RADIOACTIVE EQUILIBRIUM
238 234 234 234
92 90 91 92
U Th Pa U
Suppose a radioactive isotope. A is producing another radioactive substance B, which in
turn is producing C.
A B C
1
Rate of decay of A is no. of atoms of A].
1
N [ N
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Rate of decay of A = is decay constant of A]
1 1 1
N [
2
Rate of decay of B is no. of atoms of B]
2
N [N
= is decay constant of B]
2 2 2
N [
at radio active equilibrium
Rate of formation of B = Rate of decay of B
But rate of formation of B = Rate of decay of A
So at equilibrium
=
1 1 2 2
N N
1 2
2 1
N 0.6932/ T
N 0.6932/ T
= =
1
2
1 2
2 1
N T
N T
= =
1
2
but
1
K
=
so
1 2 2
2 1 1
K N
K N T
= = =
1
2
T
1
H
1
8.3 CARBON DATING
14 1 14 1
7 0 6
atomspheric cos mic
nitrogen rays
N n C + +
14
6
C is radiocarbon ( emitter)
14 14 0
6 7
C N +
Carbon dating is based upon the fact that radio carbon 14 is produced in the atmosphere
by the action of cosmic rays C is a emitter with a half life of 5730 years. Its rate of
formation has been constant so the atmosphere has an equilibrium concentration of C
corresponding to nearly 16 disintegration per minute per gram of carbon. All living plants
and animals contains this equilibrium concentration but when a plant or animal dies no
further exchange between it and environment takes place and C content start decreasing
as a result of radio active decay. After 5730 years there will remain only 8 disintegration
per minute per gram of carbon. By measuring the activity of a fresh piece and the old piece,
the age of old piece may be determined.
14
14
14
0
N 2.303
log
t N
=
0
N 2.303
log
t N
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2.303 Initial activity
log
t activity after t time
=
14 12
14 12
C / C in fresh sample 2.303
log
t C / C in old sample
=
8.4 MINERAL DATING (GEOCHRONOLOGY).
Determination of age of rocks, earth etc. is known as mineral dating
0
N 2.303
log
t N
=
2.303 P D
log
t P
+
=
P = no. of atoms of parent element
D = no. of atoms of daughter element.
Illustration 13 :Radioactive decay is a first order process. Radioactive carbon wood sample
decays with a half life of 5770 years. What is the rate constant in (years)
1
for
the decay? What fraction would remain after 11540 years?
Solution :
5770
693 . 0
T
693 . 0
K
2 / 1
= =
= 1.201 10
4
year
1
t
0
N
N
log
t
303 . 2
K =
1.201 10
4
t
0
N
N
log
11540
303 . 2
=
4.002 =
t
0
N
N
0
t
N
N
(Remaining fraction) =
002 . 4
1
EXERCISE 6 :
1. The bones of a prehistoric bison were found to have a
14
C activity of 2.80 dis/min. g
carbon. Approximately how long ago did the animal live? (t
1/2
= 5730 years)
14
C activity
of fresh sample = 15.3 dis/min/gC.
2. Potassium contains 9.310 atom %
39
K, having mas 38.9637 u; 0.0118 atom %
40
K, which
has mass of 40.0 u and is radioactive with t
1/2
= 1.3 10
9
y and 6.88 atom %
41
K having a
mass of 40.96184u. Calculate the specific activity of naturally occurring potassium.
3. A mixture of
239
Pu and
240
Pu has a specific activity of 6 10
9
dis/s/g, The half lives of the
isotopes are 2.44 10
4
y and 6.08 10
3
y specific activity of naturally occurring
potassium.
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SECTION I
SUBJECTIVE TYPE PROBLEMS
Problem 1: The half life of a chemical reaction at a particular concentration is 100 min. When
the concentration of the reactant is doubled, the half life becomes 50 min, then what is
the order of the reaction ?
Solution :
n 1
1/ 2 1 2
1/ 2 2 1
(t ) a
(t ) a
,
n 1
100 2
50 1
_
,
2 = 2
(n1)
= n 1
n = 2
Problem 2: An optically active drug has one chiral center and only dextrorotatory isomer is
effective. Moreover it becomes ineffective when its optical activity reduces to 60% of
the original in the equilibrium mixture at 27C and at one 127C, its optical activity
reduces upto 80%. Then find out H of the reaction assuming that the specific rotation
of the isomers remains constant during this temperature range. [log 3 =.477]
Solution : Let the dextrorotatory isomer A and laevoratatory is B
0
= initial observed rotation
t
= observed rotation at time t
A !!"
#!!
B
t = 0
0
0
0
From question,
0
= 100,
t
= 60
60 = 100 2
= 20 =
0
= 100 20
At 27C,r
K
eq.
= K
1
=
[B] 20 1
[A] 80 4
Similarly, at 127C.
K
eq.
= K
2
=
[B] 10 1
[A] 90 9
since
2.30 log =
1/ 4 H 1 1
1/ 9 R 300 400
1
1
]
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2.303 log
9 H 100
4 R 300 400
1
]
2.303 [log 9 log 4] =
H 1
R 1200
p = 3q
Again, p + q = 36
4q = 36
q = 9
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p = 27
Now k
1
40 = 2.303 log
a
a 27
2
1.2 10 40 a
log
2.303 a 27
0.208 =
a
log
a 27
a
a 27
= 1.6
a = 72
Now, for 60 seconds, let the amount of X converted into Z is p and the amount of Y
converted into Z is q.
2
1.2 10 60 72
log
2.303 72 p'
0.313 =
72
log
72 p
2.050 =
72
72 p
p = 36.88
q = 12.29
mole percentage of Z is = p + q = 49.17%
Problem 4: What is the amount of activation energy in kilo joules at 298 K for 10
3
% molecule to
cross over the energy barrier? Given that, ln10
5
=11.515.
Solution : Fraction of molecules crossing over the energy barrier = a
E / RT
e
=
a
3
E / RT
10
e
100
10
5
= a
E / RT
e
11.515 =
a
E
RT
E
a
= 11.515 8.314 298 Joule
= 28.53 KJ
Problem 5 : The reaction given below, involving the gases is observed to be first order with rate
constant 7.48 10
3
sec
1
.Calculate the time required for the total pressure in a
system containing A at an initial pressure of 0.1 atm to rise to 0.145 atm and also find
the total pressure after 100 sec.
2A(g) 4B(g) + C(g)
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Solution : 2A(g) 4B(g) + C(g)
P
o
0 0
P
o
P 2P P/2
P
total
=P
o
P + 2P + P/2 = P
o
+
3P'
2
P =
2
3
(0.145 0.1) =0.03 atm
k =
o
o
P 2.303
log
t P P'
t =
3
2.303 0.1
log
0.07 7.48 10
_
,
t = 47.7 sec
Also, k =
o
2.303 0.1
log
t P P'
_
,
7.48 10
3
=
2.303 0.1
log
100 0.1 P'
_
,
0.1 P = 0.047
P = 0.053
P
total
= 0.1 +
3
2
(0.053) 0.180 atm.
Problem 6 : For the reaction :
C
2
H
5
I +OH
C
2
H
5
OH +I
the rate constant was found to have a value of 5.03 10
2
mol
1
dm
3
s
1
at 289 K and
6.71 mol
1
dm
3
s
1
at 333 K. What is the rate constant at 305 K.
Solution : k
1
= 5.03 10
2
mol
1
dm
3
s
1
at T
1
= 289 K
k
2
= 6.71 mol
1
dm
3
s
1
at T
2
= 333 K
log
2
6.71
5.03 10
_
,
=
a
E 333 289
2.303 8.314 333 289
_
,
On solving we get, E
a
= 88.914 kJ
The rate constsnt at 305 K may be determined from the relation:
log
a 2
1 1 2
E k 1 1
k 2.303R T T
_
,
log
2
2
k 88914 1 1
2.303 8.314 298 305 5.03 10
_ _
, ,
On solving we get, k
2
= 0.35 mol
1
dm
3
s
1
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Problem 7 : The decomposition of Cl
2
O
7
at 400 K in the gas phase to Cl
2
and O
2
is of I order. After
55 sec at 400 K, the pressure of Cl
2
O
7
falls from 0.062 to 0.044 atm. Calculate :
(a) The rate constant.
(b) Pressure of Cl
2
O
7
after 100 sec.
Solution : Cl
2
O
7
Cl
2
+
7
2 2
O
Mole at t = 0 a 0 0
Mole at t = 55 sec. (a x) x 7x/2
(a) Since Pressure of Cl
2
O
7
is given and therefore,
a 0.062
(a x) 0.044
$
K =
10
2.303 0.062
log
t 0.044
K = 6.23 10
3
sec
1
.
(b) Let at t = 100 sec, (a x) P
6.23 10
3
=
10
2.303 0.062
log
100 P
P = 0.033 atm.
Problem 8: A radioactive element A says to B I am half of what you were when you are one
fourth of what I was. Moreover I was 1.414 time than what you were. I f the half life
of A is 8 days, what is the half life of B?
Solution : Let the initial number of nuclide of X be x
0
Let the initial number of nuclide of Y be y
0
Let the number of nuclide of X after time t be x
t
Let the number of nuclide of Y after time t be y
t
x
t
= y
0
; y
t
= x
0
x
0
= 1.414 y
0
Now, x
t
=
1
t
0
e
x = y
0
(1)
y
t
= y
0
2
t
e
= x
0
.(2)
Dividing equation. (1) by (2)
( )
2 1
t
0 0
0 0
2y e
y
x
x
( )
2 1
2
t
0
2
0
2 e
y
x
Since x
0
=
2
y
0
2 2
0 0
2y x
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2 =
( )
2 1
t
2e
( )
2 1
t
e
= 1
Since t is not zero, hence
2
=
1
. Therefore the half life of the other radioactive element is
also 8 days.
Problem 9 : On analysis a sample of Uranium was found to contain 0.277 g of
82
Pb
206
and 1.667 g
of
92
U
238
. The half life period of
92
U
238
is 4.51 10
9
years. I f all the lead were assumed
to have come from decay of
92
U
238
, what is the age of the earth?
Solution :
92
U
238
= 1.667 g =
1.667
238
mole
82
Pb
206
= 0.227g =
0.227
206
mole
$ All the lead have come from decay of U.
Moles of Pb formed =
0.277
206
moles of U decayed =
0.277
206
Total moles of Uranium =
1.667
238
+
0.277
206
, ie N
0
Also N for U
238
=
1.667
238
$ for U
238
t =
0
N 2.803
log
k N
=
9
2.303 4.51 10
0.693
log
1.667 0.277
238 206
1.667
238
+
t = 1.143 10
9
yrs .
Problem 10 : An optically active compound A is hydrolysed by dilute acid to give
two optically compounds B and C according to the following chemical equation,
A +H
2
O 2B +C. The angle of rotation after 40 minutes was observed to be
26 and that after completion of reaction was 10 at 27C. Find the half  time of the
reaction assuming it to follow pseudo first order kinetics. The observed rotation per
mole of A,B and C are 60, 50 and 80. A plot of logarithm of rate constant of the
above reaction vs T
1
give straight line with intercept equal 15.046 on log K axis.
Calculate at what temperature half  time of the reaction will be 31.1 min.
Solution : A + H
2
O 2B + C
a excess 0 0
(ax) const. x 2x
0 const. 2a a
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After completion of reaction 50 29 + (80) a = 10, a = 0.5
After 40 minute. 60(ax) + 50 2x 80 x = 26
x = 0.1
K =
2.303 a 2.303 0.5 2.303
log log
t (a x) 40 0.5 0.1 40
log 5/4
K = 5.57 10
3
min
1
t
1/2
=
0.693
K
=
0.693
0.00557
= 124.4 min
From Arrhenius equation, K = Ae
Ea/RT
LogK =
Ea
2.303RT
1
300
+ 15.046
E
a
= 99.37 kJ /mol
In order that t
1/2
of reaction may decrease from 124.4 min, rate constant will have to
increase 4 time.
Log (4 5.57 10
3
) =
99370
2.303 8.314
1
T
+ 15.046
1.652 15.046 =
99370
2.303 8.314
1
T
T = 310.80 K
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SECTION II
SINGLE CHOICE PROBLEMS
Problem 1: The progress of the reaction A
!!"
#!!
nB with time is presented in the figure, the value of n
is
(a) 2 (b) 3
(c) 4 (d) 5
1 3 5 7
0.3
C
o
n
.
o
l
/
l
i
t
r
e
Time/hour
A
B
0.6
Solution : A !!"
#!!
nB
t = 0 0.06 0 (initial conc. in mol L
1
)
At equi. 0.6 x nx (conc. at equilibrium)
From the graph
0.6 x = 0.3
Also from the graph
nx = 0.6
n = 2
(a)
Problem 2 : For the elementary reaction, 2NO + H
2
N
2
O + H
2
O; the half life time is 19.2 sec at
820C when partial pressure of NO and H
2
are 600 mm of Hg and 10 mm of Hg respectively.
The value of half time at the same temperature when partial pressure of NO and H
2
are
600 mm of Hg and 20 mm of Hg respectively would be
(a) 19.2 sec (b) 10 sec
(c) 830 sec (d) 415 sec
Solution : According to Ostwald isolation method of order determination, the concentration terms of
reactants present in excess remain virtually unchanged and thus can be merged with the
rate constant. In this case, the rate of the reaction depends only on the concentration o f that
reactant which is not present in excess. The reaction is known to be pseudo first order.
The partial pressure of NO is very large in comparison to that of hydrogen. Thus, we may
consider the rate of reaction to be independent of P
NO
and hence reaction will follow the
rate law.
2
2
(N O)
2
H NO
dp
k P ; where k k(P )
dt
= Pseudo first order reaction rate constant.
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Halflife time of first order reaction is independent of initial concentration. Hence the required
halflife time will be 19.2 sec.
(a)
Problem 3 : Two reactions one of first order and other of second order have same values of rate constants
(k
1
= k
2
) when concentration are expressed in mole dm
3
. If the concentrations are expressed
in mole ml
1
the relation between their rate constants k
1
and k
2
will be
(a) k
1
= k
2
(b) k
2
10
3
= k
2
(c) k
2
10
3
= k
1
(d) k
1
= 10k
2
Solution : Since
1 n
k [a]
1
k 1
So k is constant and independent of unit of a, Therefore k
1
= k
1
For second order reaction
2
1
k
a
2
3 3 1
1 1
k
a mole dm a 10 mole ml
1 2
1
k
a mole ml
3
2 2 1
k k 10 k
(c)
Problem 4 : For the first order reaction 3A B
concentration varies with time as shown
in the adjacent graph. The halflife of the
reaction would be
(a) 2 minutes
(b) 4 minutes
Conc.
(In M)
Time (in minutes)
2 4 6 8
A
B
(c) 8 minutes
(d) 16 minutes
Solution : From graph it follows that at time 4 minute from the start of the reaction
[A] = [B]
3A B
t = 0 a
t = 4 min a x x/3
x 3a
a x x
3 4
3a a
a x a
4 4
i.e., in 4 minutes concentration of A has reduced to 25% of the initial value therefore,
t
3/4
= 4 min. As t
3/4
= 2t
1/2
for a first order reaction, so halflife of this reaction = 2 min
(a)
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Problem 5 : The inversion of cane sugar proceeds with halflife of 500 minute at pH 5 for any
concentration of sugar. However if pH = 6, the halflife changes to 50 minute. The rate law
expression for the sugar inversion can be written as
(a) r = K[sugar]
2
[H]
6
(b) r = K[sugar]
1
[H]
0
(c) r = K[sugar]
0
[H
+
]
6
(d) r = K[sugar]
0
[H
+
]
1
Solution : Since t
1/2
does not depends upon the sugar concentration means it is first order respect to
sugar concentration. t
1/2
[sugar]
1
.
t
1/2
a
n1
= k
( )
( )
1 n
1/ 2
1 1
1 n
1/ 2 2
2
t
[H ]
t [H ]
+
+
1 n
5
6
500 10
50 10
,
10 = (10)
1n
Hence n = 0
(b)
Problem 6 : Two substances A and B are present such that [A
0
] = 4[B
0
] and halflife of A is 5 minute
and that of B is 15 minute. If they start decaying at the same time following first order
kinetics how much time later will the concentration of both of them would be same.
(a) 15 minute (b) 10 minute
(c) 5 minute (d) 12 minute
Solution : Amount of A left in n
1
haves =
1
n
0
1
[A ]
2
_
,
Amount of B left n
2
halves =
2
n
0
1
[B ]
2
_
,
At the end, according to the question
1 2
0
0
n n
[B ] [A ]
2 2
[ ]
1 2
0 0
n n
4 1
, [A ] 4[B ]
2 2
1
1 2
2
n
n n 2
1 2
n
2
4 2 (2) n n 2
2
2 1
n (n 2) (1)
Also
1 1/ 2(A)
t n t
2 1/ 2(B)
t n t
(Let concentration both become equal after time t)
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1 1/ 2(A)
1 1
2 1/ 2(B) 2 2
n t
n 5 n
1 1 3
n t n 15 n
(2)
For equation (1) and (2)
n
1
= 3, n
2
= 1
t = 3 5 = 15 minute
(a)
Problem 7 : The reaction A(g) + 2B(g) C(g) + D(g) is an elementary process. In an experiment, the
initial partial pressure of A and B are P
A
= 0.60 and P
B
= 0.80 atm. When P
C
= 0.2 atm the
rate of reaction relative to the initial rate is
(a) 1/48 (b) 1/24
(c) 9/16 (d) 1/6
Solution :
1
R K[A][B]
2
K[0.6][0.80]
After reaction
A + 2B
C + D
0.6 0.2 0.8 0.4 0.2 0.2
0.4 0.4 0.2 0.2
2
2
2
1
R K(0.4)(0.4) 1
R 6 (0.6)(0.8)
(d)
Problem 8 : A first order reaction : A Products and a second order reaction :
2R Products both have half  time of 20 minutes when they are carried out taking 4
mole L
1
of their respective reactants. Number of mole per litre of A and R remaining
unreacted after 60 minutes from the short of the reaction, respectively will be.
(a) 1 and 0.5 (b) 0.5 and negligible
(c) 0.5 and 1 (d) 1 and 0.25
Solution : In the case of first order reaction t
1/2
will remain constant independent of initial concentration
so.
4 mole L
1
20 min
2 mole L
1
20 min
1 mole L
1
20 min
0.5 moile L
1
.
That is, after 60 minutes 0.5 mole L
1
of A will be left unreacted.
In the case of second order reaction t
1/2
is inversely proportional to initial concentration of
reactant i.e., t
1/2
will go on doubling as concentration of reactant will go on getting half.
That is, t
1/2
a will be constant, so.
4 mole L
1
20 min
2 mole L
1
40 min
1 mole L
1
.
That is, after 60 minutes, the concentration of R remaining unreacted will be 1 mole L
1
.
Note that t
1/2
a = 20 4 = 40 2 = 80 mole L
1
min, a constant.
(b)
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Problem 9 : The thermal decomposition of acetaldehyde : CH
3
CHO CH
4
+ CO, has rate constant
of 1.8 10
3
mole
1/2
L
1/2
min
1
at a given temperature. How would
3
d[CH CHOO]

dt
will
change if concentration of acetaldehyde is doubled keeping the temperature constant?
(a) will increase by 2.828 times (b) will increase by 11.313 times
(c) will not change (d) will increase by 4 times
Solution : Unit of the rate constant mole
1/2
L
1/2
.min
1/2
suggests that the reaction obeys kinetics of 1.5
order.
Rate = k [CH
3
CHO]
3/2
or k =
1 1
3/ 2 1 3/ 2
3
Rate moleL min
[CH CHO] (mole L )
= Mole
1/2
, L
1/2
.min
1
So, by doubling the concentration of acetaldehyde the rate will increase 2
1.5
i.e., 2.828
times.
(a)
Problem 10 : The reaction ; 2O
3
3O
2
, is assigned the following mechanism.
I. O
3
O
2
+ O
II. O
3
+ O 2O
2
(slow)
The rate law of if the reaction will, therefore be
(a) r [O
3
]
2
[O
2
] (b) r [O
3
]
2
[O
2
]
1
(c) r [O
3
] (d) r [O
3
] [O
2
]
2
Solution : Step II, being r.d.s.
Rate of overall reaction = rate of Step II = K
II
[O
3
][O]
Putting the value of [O] from the equilibrium of Step I,
Rate =
2
II C 3
2
K K [O ]
[O ]
(b)
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SECTION III
MULTIPLE CHOICE PROBLEMS
Problem 1: Arrhenius equation may be represented as
(a)
A Ea
ln
k RT
(b)
d lnk Ea
dt RT
(c)
Ea
logA logk
2.303RT
+
(d)
Ea k
log
RT A
_
,
Solution : (a, c)
(a) is correct as explained below :
k = Ae
Ea/RT
Ea / RT
k
e
A
k Ea A Ea
ln ln
A RT k RT
(b) is not correct
d d d Ea
(ln A) (ln k)
dT dt dt RT
_
,
2
d Ea
(ln k)
dT RT
[ln A does not change with T]
2
d Ea
(ln k)
dT RT
(c) is correct. k = Ae
Ea/RT
ln k = ln A Ea/RT ln A = ln k + Ea/RT
Ea
logA logk
2.303RT
+
Hence (d) is not correct it follows from explanation of (a), (b) and (c).
Problem 2 : A positive catalyst
(a) increase the average kinetic energy of the reacting molecules
(b) decreases the activation energy
(c) alters the reaction mechanism
(d) increases collision frequency
Solution : (b, c)
(b) is correct because the catalyst lowers down the activation energy by altering the
mechanism.
(c) is correct because it provides alternative shortcut path or mechanism of the reaction.
(a) is not correct because K.E. T.
(d) is wrong because collision frequency is increased by temperature and pressure.
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Problem 3: For first order reaction
(a) the degree of dissociation is equal to (1 e
kt
)
(b) a plot of reciprocal of conc. of reactant vs time gives a straight line
(c) t
75%
= 3t
1/2
(d) The preexponential factor in Arrhenius equation has the dimension of time T
1
.
Solution : (a, d)
(a) is correct
kt
kt 0 0 0
0 0
[A ] [A] [A ] [A ]e
1 e
[A ] [A ]
(d) is correct, k = Ae
Ea/RT
Units of preexponential factor A = units of k = mol L
1
s
1
Dimension of time in A is T
1
, i.e., s
1
.
(b) is not correct because log (conc.) vs time is straight line.
(c) is not correct because t
75%
= 2t
1./2
Problem 4 : For the reaction
H
2
(g) + Br
2
(g) 2HBr (g)
Which of the following statements are wrong
(a) order is 2, molecularity is 2 (b) order is 3/2, molecularity is 2
(c) order is 1, molecularity is 2 (d) order is 2, molecularity is 1
Solution : (a, c, d)
(a) is correct because it is a wrong statement as order cannot be determined theoretically.
(c) is correct because it is a wrong statement as order is 1.5 and not 1.
(d) is correct becasue it is a wrong statement as mostly order is not greater than molecularity.
(b) is not correct as it is a correct statement because experimentally, order of this reaction is
found to be 3/2 and it involves two molecules. molecularity is 2.
Problem 5 : Which of the following statements are correct.
(a) A plot of log k
p
vs 1/T is linear
(b) A plot of log A vs time is linear for 1st order reaction
(c) A plot of log P vs 1/T is linear at constant volume
(d) A plot of P vs 1/V is linear at constant temperature
Solution : (a, b, d)
(a) is correct because
Ea
lnk ln A
RT
(b) is correct because
0
[A ] 2.303
k log
t [A]
at constant temperature.
(c) is not correct because
P T
.
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Problem 6 : Which of the following is a first order reaction
(a) decomposition of NH
4
NO
2
to N
2
and H
2
O
(b) catalytic decomposition of ammonia
(c) decomposition of H
2
O
2
in aqueous solution
(d) all of these
Solution : (a, c)
(a) is correct as it is observed that the rate of reaction is directly proportional to the
concentration of NH
4
NO
2
(The amount of NH
4
NO
2
reacted is known by measuring the
volume of N
2
formed).
(c) is correct as it is observed that the rate of reaction is directly proportional to the
concentration of NO
2
.
(b) is a 2nd order reaction. It follows that (d) cannot be correct.
Problem 7 : Which of the following will emit positron
(a)
13
7
N (b)
30
15
P
(c)
3
1
H (d)
14
6
C
Solution : (a, b)
(a) is correct
13 13 0
7 6 1
n
1 N C e
p
+
< + $
(positron)
(b) is correct
n
1
p
$
but still it is radioactive isotope or phosphorus and emits positron so as
to increase n/p ratio.
30 30 0
15 14 1
P Si e
+
+
While (c) and (d) are incorrect.
Problem 8 : Which of the following statements is/are correct?
(a) Nuclear fusion involves chain reaction
(b) Nuclear fusion forms products which are radioactive
(c) Nuclear fusion takes place at high temperature (10
6
K)
(d) Nuclear fusion produces more energy than nuclear fission.
Solution : (b, c, d)
(b) is correct because nuclear fission forms the product which are radioactive.
(c) is correct because high temperature of the order of 10
6
K is required so as to overcome
repulsion between the nuclei to be fused together.
(d) is correct because in fusion reaction energy released is more than fission reaction e.g.,
sun is source of energy due to fusion reaction between isotopes of hydrogen.
(a) is not correct because nuclear fusion does not involve chain reaction.
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Problem 9 : If n/p is less than 1, the nucleide can
(a) emit positron (b) Kcapture
(c) emit particle (d) emit particle
Solution : (a, b)
(a) is correct because n/p increases during positron emission because proton gets converted
into neutron.
(b) kcapture means capture of electrons which will convert proton into neutron increasing
n/p ratio.
1 0 0
1 1 1
p e n
+
(c) particle emission leads to decrease in n/p ratio.
(d) particle emission leads to increase in n/p ratio but n/p should not be less than 1 in parent
nucleides.
e.g.,
238 234 4 238 234
92 90 2 92 90
n n
U Th He; for Uis1.58; for Th is1.60.
p p
+
Problem 10 : Which of the following are used for measuring radioactivity?
(a) Gieger Muller counter (b) Wilson cloud chamber
(c) Scintillation counter (d) none of these
Solution : (a, b, c)
Geiger Muller Counter, Wilson Cloud Chamber, Scintillation counter are used for measuing
radioactivity (a), (b), (c) are correct.
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MISCELLANEOUS PROBLEMS
SECTION IV
COMPREHENSION TYPE PROBLEMS
Write up I
Nucleus is considered to resemble a liquid drop in which nucleons are present having very rich
density i.e. 130 trillion tonnes m
3
which is about trillion times the density of water. It has high
surface tension of about 1.24 10
18
times, the surface tension of water. The high surface tension
keeps the nucleons together against the force of repulsion.
Problem 1 : The nuclear volume is
(a) directly proportional to mass number (b) inversely proportional to mass number
(c) inversely proportional to atomic number (d) independent of mass number
Solution : Ans. (a)
The nuclear volume =
3
4
r
3
1/ 3
r [A] , V A
1/3
where A is mass number.
Problem 2 : The radius of nucleus of
12
C is equal to
(a) 3.5 10
15
m (b) 4 10
15
m
(c) 5 10
15
m (d) 6.0 10
15
m
Solution : Ans. (a)
r = 1.4 10
15
(12)
1/3
= 1.4 10
15
2.3 = 3.2 10
15
m
Problem 3 : Radius of nucleus is directly proportional to
(a) [A]
2
(b) [A]
1/3
(c) [A]
3
(d) [A]
Solution : Ans. (b)
r [A]
1/3
where A is mass number
Writeup I I
For a particular first order reaction at 27C, the concentration of reactant is reduced to one half of
its initial value after 5000s. At 37C, the concentration is halved after 1000s.
Problem 4 : The constant of the reaction at 27C is :
(a) 1.386 10
4
s
1
(b) 6.93 10
4
s
1
(c) 11.231 10
4
s
1
(d) 9.232 10
4
s
1
Solution : Ans. (a)
(T
50
)
300 K
= 5000s
k
1
(3000 k) =
50 300 k
0.693 0.693
(T ) 5000
= 1.386 10
4
s
1
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Problem 5 : What is the time required for the concentration to be reduced to one quarter of its value at
37C?
(a) 1000 s (b) 500 s
(c) 2000 s (d) 1500 s
Solution : Ans. (c)
(T
50
)
310 k
= 1000 s
k
2
(310 k) =
4 1
0.693
6.93 10 s
1000
T
75
= 2 T
50
for first order reaction, (when concentration is reduced to one quarter i.e.. 75%
reaction)
Hence, T
75
(310 k) = 2000 s
Problem 6 : The activation energy of the reaction is :
(a) 124.46 kJ/mol (b) 650 kJ/mol
(c) 229.12 kJ/mol (d) 693.15 kJ/mol
Solution : Ans. (a)
1 2 2
a 10
2 1 1
2.303 RTT k
E log
T T k
= 124.46 kJ/mol
MATCHING TYPE PROBLEM
7. Column (I ) Column (I I )
(a)
9 4 12 1
4 2 6 0
Be He C n + + (p) Hydrogen bomb
(b)
24 4 27 1
12 2 14 0
He n Mg Si + + (q) Radiolysis in Redox systems
(c)
2 3 4 1
1 1 2 0
n D T He 17.6 MeV + + + (r) Artificial transmutation
(d)
NaCl
3 2 3
BrO 3I Br I IO
+ + + (s) Induced radioactivity
Sol. (a) (r), This reaction is the transmutation of
9
4
Be to
12
6
C by using
4
2
He as projectile.
(b) (r), (s); This reaction is an artificial transmutation leading to the formation of unstable nuclei
27
14
Si which gives stable
27
13
Al
27 27 0
14 13 1
Si Al e
+
+
(c) (p) ; This is the reaction taking place in a hydrogen bomb.
(d) (q); This is radiolysis where a substance is exposed to high energy radiation such as gamma
rays. It involves two stages
Primary stage :
High energy
Radiation
A A e
+
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Secondary stage : A
+
+ e
A
or M + e
A
+
+ M
+ M
Here NaCl is the one which induces this reaction which is redox reaction.
ASSERTIONREASON TYPE PROBLEMS
The question given below consist of an ASSERTI ON and the REASON. Use the following key for the
appropriate answers
(a) If both Assertion and Reason are correct and Reason is the correct explanation for Assertion
(b) If both Assertion and Reason are correct and Reason is not the correct explanation for
Assertion
(c) If Assertion is correct but Reason is not correct.
(d) If Assertion is incorrect but Reason is correct.
8. Assertion : Photochemical reactions are zero order reactions.
Reason : Photochemical reactions involve free radicals and they are very fast reactions.
Solution : Photochemical reactions are extremely fast, therefore, lead to completion. Their rate is not
affected by concentration of reactant.
Ans. (a)
9. Assertion : 2FeCl
3
+ SnCl
2
2FeCl
2
+ SnCl
4
is a 3rd order reaction.
Reason : The rate constant for third order reaction has unit L
2
mol
2
s
1
.
Solution : rate = k [FeCl
3
]
2
[SnCl
2
]
1
rate = k[A]
3
mol L
1
s
1
= k [mol L
1
]
3
k = L
2
mol
2
s
1
Ans. (b)
10.Assertion : particles are emitted by nucleus
Reason : In nucleus,
1 1 0
0 1 1
n p e
+
Solution : A is correct, R is correct and R is correct explanation of A
Ans. (a)
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ASSIGNMENTS
SECTION I
SUBJECTIVE QUESTIONS
LEVEL  I
1. The isomerism of cyclopropane to propene is of first order with k = 8.25 10
4
s
1
at 500C. If
cyclopropane is enclosed in a heated tube at 500C. What will be the minimum time needed to yield at
least 10% propene in resultant gas sample.
2. For a reaction, A B + C, it was found that the end of 10 minutes from the start the total optical
rotation of the system ws 50 and when the reaction is complete, it was 100. Assuming that only B
and C are optically active and dextro rotatory. What would be the rate constant of this first order
reaction.
3. At a given instant thee are 25% undecayed radioactive nuclei in a sample. After 10 seconds the
number of undecayed nuclei reduces to 12.5%. What is the time in which the number of undecayed
nuclei will further reduce to 6.25% of the reduced number.
4. Naturally occurring potassium consist of 0.01% K
40
, which has a half life of 1.28 10
9
yr. What would
be the activity of 1.0 g sample of KCl.
5. A catalyst lowers the activation energy of a reaction from 20 kJ mole
1
to 10 kJ mole
1
. What is the
temperature at which the uncatalysed reaction will have the same rate as that of the catalysed at 27C.
6. For the first order reaction A
(g)
2B
(g)
+ C
(g)
, the initial pressure is P
A
= 90 mm Hg, the pressure after
10 minutes is found to be 180 mm Hg. What is the rate constant of the reaction ?
7. The activity of a radioactive sample reduced from 20 Ci to 1.25 Ci in 2000 years. What are the half 
life of the sample and its decay constant.
8. In the sequential chain reaction
1 2
k k
A B C at the steady state, the half life of B is 30 seconds,
then what will be the half life of A? Given that at any time, the number of atoms of A is twice the
number of atoms of B.
9. What is the percentage fraction of the molecule crossing over the energy barrier at 27C. Given that
Ea(b) = 80 cal, H = 20 cal and antilog (0.072) = 1.181.
10. At 278C the half life period for the first order thermal decomposition of ethylene oxide is 363 min and
the energy of activation of the reaction in 52,00 cal/mole. From these data estimate the time required
for ethylene oxide to be 75% decomposed at 450C.
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LEVEL  II
1. For the following reaction, the rate law has been determined to be
rate = k[A][B]
2
with k = 2 10
6
mol
2
L
2
sec
1
2A + B + C A
2
B + C
For this reaction the initial conc of the various species.
[A] = 0.1 mol L
1
; [B] = 0.2 mol L
1
; [C] = 0.8 mol L
1
. Determine the rate after 0.04 mol L
1
of A has
reacted.
2. For the reaction process A + B products, the rate is first order w.r.t A and second order w.r.t
B. If 1 mol each of A and B were introduced into a 1 L vessel, and the initial rate were 1 10
2
(mol/
L)sec
1
. Calculate the rate when half the reactants have been turned into products.
3. 10g atoms of an active radioisotope are disintegrating in a sealed container. In one hour helium gas
collected at STP is 11.2 litre. Calculate the halflife of the radioisotope.
4. The gas phase decomposition of dimethyl ether follows firstorder kinetics.
3 3(g) 4(g) 2(g) (g)
CH OCH CH H CO + +
The reaction is carried out at constant volume in a container at 500C and has a halflife of 14.5
minutes. Initially only dimethyl ether is present at a pressure of 0.40 atmosphere. What is the total
pressure of the system after 12 minutes? Assume ideal gas behaviour.
5. In the Arrhneius equation for a certain reaction, the value of A and E
a
(activation energy) are 4 10
13
s
1
and 98.6 kJ mol
1
, respectively. If the reaction is of first order, at what temperature will its halflife
period be ten minutes?
6. The reaction 2NO
(g)
+ 2H
2
N
2(g)
+ 2H
2
O
(g)
has been studied at 904C
Sl. No. Initial Concentration Rate of appearance of N
2
(mol litre
1
sec
1
NO H
2
1. 0.42M 0.122M 0.136
2. 0.21M 0.122M 0.0339
3. 0.21M 0.244M 0.0678
4. 0.105M 0.488M 0.0339
Determine the reaction order
7. The decomposition of N
2
O
5
according to the equation 2N
2
O
2(g)
+ O
2(g)
is a first order reaction. After 30
min from start of decomposition in a closed vessel the total pressure developed is found to be 284.5 mm
Hg. On complete decomposition, the total pressure is 584.5 mm Hg. Calculate the rate constant of the
reaction.
8. A certain physiologically important first order reaction has an activation energy equal to 45.0 kJ/mol at
normal body temperature (37C). Without a catalyst, the rate constant for the reaction is 5.0 10
4
s
1
. To be effective in the human body, where the reaction is catalysed by an enzyme, the rate constant
must be at least 2.0 10
2
s
1
. If the activation energy is the only factor affected by the presence of the
enzyme, by how much must the enzyme lower the activation energy of the reaction to achieve the
desired rate?
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9. The halflife period for the reaction,
2 5 2 2
1
N O 2NO O
2
+
is 2.4 hours at 30C. What time would
be required to reduce 5 10
10
molecules of N
2
O
5
to 10
8
molecules?
10. For a certain reaction, it takes 5 minutes for the initial concentration of 0.5 mole/L to become 0.25
mole/L and another 5 minutes to become 0.125 mole/L.What is the order and specific rate constant of
the reaction?
LEVEL  III
1. Two I order reactions having same reactant concentration proceed at 25C at the same rate. The
temperature coefficient of the rate of the first reaction is 2 and that of second reaction is 3. Find the
also of the rates of these reactions at 75C.
2. In a certain reaction B
m+
is getting converted to B
(n+4)+
in solution. The rate constant of this reaction is
measured by titrating a volume of the solution with a reducing agent which reacts only with B
n+
and
B
(n+4)+
. In this process, it converts B
n+
to B
(n2)+
and B
(n+4)+
to B
(n1)+
. At t = 0, the volume of reagent
consumed is 25 mL and at t = 10 min, the volume used is 32 mL. Calculate the rate constant of the
conversion of B
n+
to B
(n+4)+
assuming it to be a first order reaction.
3. For the reaction
2NO + H
2
N
2
O + H
2
O
the value of
dp
dt
=
(c)
0 t
C C
k ln
2t
=
(d)
0
t
C
k
C
=
3. The rate expression for the reaction A
(g)
+ B
(g)
C
(g)
is rate =
2 1/ 2
A B
kC C . What changes in the initial
concentrations of A and B will cause the rate of reaction to increase by a factor of eight?
(a) C
A
2; C
B
2 (b) C
A
2; C
B
+ 4
(c) C
A
1; C
B
4 (d) C
A
4; C
B
1
4. In an exothermic reaction X Y, the activation energy is 100kJ mol
1
of X. The enthalpy of the
reaction is 140 kJ mol
1
. The activation energy of the reverse reaction Y X is
(a) 40 kJ mol
1
(b) 340 kJ mol
1
(c) 240 kJ mol
1
(d) 100 kJ mol
1
5. The rate constant, the activation energy and the preexponential factor of a chemical reaction at 25C
are 8.0 10
4
s
1
, 112 kJ mol
1
and 4 10
15
s
1
respectively. The value of the rate constant as T
is
(a) 8 10
16
s
1
(b) 4 10
4
s
1
(c) 4 10
15
s
1
(d) 112 10
12
s
1
6. Two first order reactions have halflives in the ratio 3:2. Calculate the ratio of time intervals t
1
: t
2
; t
1
is
the time period for 25% completion of the first reaction and t
2
for 75% completion of the second
reaction.
(a) 0.311:1 (b) 0.420:1
(c) 0.273:1 (d) 0.119:1
7. Which of the following rate law has an overall order of 0.5 for the reactions involving substances x,y,z?
(a) Rate = k(Cx) (Cy) (Cz) (b) Rate = k (Cx)
0.5
(Cy)
0.5
(Cz)
0.5
(c) Rate = k(Cx)
1.5
(Cy)
1
(Cz)
0
(d) Rate =
( )( )
( )
o
2
R Cx Cz
Cy
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8. The reaction A(g) + 2B(g) C(g) + D(g) is an elementary process. In an experiment, the initial
partial pressure of A & B are P
A
= 0.60 and P
B
= 0.80 atm. When P
C
= 0.2 atm the rate of reaction
relative to the initial rate is
(a) 1/48 (b) 1/24
(c) 9/16 (d) 1/6
9. For a second order reaction of the type rate = k [A]
2
, the plot of [A]
t
versus t is linear with a
(a) positive slope and zero intercept
(b) positive slope and non zero intercept
(c) negative slope and zero intercept
(d) negative slope and non zero intercept
10. If concentration are measured in mole/lit and time in minutes, the unit for the rate constant of a 3
rd
order reaction are
(a) mol lit
1
min
1
(b) lit
2
mol
2
min
1
(c) lit.mol
1
min
1
(d) min
1
11. Radioactivity is affected by
(a) Temperature (b) Pressure
(c) State of chemical combination (d) None
12. No. of particles emitted during the change
b d
a c
X Y is
(a)
a d
4
(b)
a d
c b
2
+ +
(c)
b d
c a
2
+
(d)
a d
c b
2
+
13. For two atoms
1
1
A
Z
X and
2
2
A
Z
X where
1 2
Z Z and
1 2
A A , A
1
2Z
1
= A
2
2Z
2
, the species
would be called
(a) Isotonic (b) Isodiaphers
(c) Isoters (d) none
14. Which statement is true about N/P ratio
(a) It increases by emission (b) It increases by emission
(c) It increases by emission (d) None of these
15. How many and particles should be eliminated so that an isodipher is formed
(a) n , n (b) n , (n + 1)
(c) n (d) n
16.
235 1 236 1 11
92 0 92 0
U n U Pr oducts x n 3.2 10 J
(c)
1
2 1
2
a x 2.302
t t log
k a x
)
(a) unit of
is time
1
(b) value of
(d) 2 10
4
9. (A) follows first order reaction. (A) product
Concentration of A, changes from 0.1 M to 0.025 M in 40 minutes. Find the rate of reaction of A when
concentration of A is 0.01 M: (2004)
(a) 3.47 10
4
M min
1
(b) 3.47 10
5
M min
1
(c) 1.73 10
4
M min
1
(d) 1.73 10
5
M min
1
10. Which of the following statement for order of reaction is not correct? (2005)
(a) Order can be determined experimentally
(b) Order of reaction is equal to sum of the power of concentration terms in differential rate law
(c) It is not affected with stoichiometric coefficient of the reactants
(d) Order can not be fractional
B. More than one options are correct (Objective Question)
1. The nuclear reactions accompanied with emission of neutron (s) are (1988)
(a)
17 4 30
13 2 15
Al He P + (b)
12 1 14
6 1 7
C H N +
(c)
30 30 0
15 14 1
P Si e + (d)
241 4 244 0
96 2 97 1
Am He Bk e + +
2. Decrease in atomic number is observed during : (1988)
(a) alpha emission (b) beta emission
(c) positron emission (d) electron capture
SUBJECTIVE
1. The time required for 10% completion of a first order reaction at 298 K is equal to that required for
its 25% completion at 308 K. If the preexponential factor for the reaction is
9 1
3.56 10 s , calculate
its rate constant at 318 K and also the energy of activation.
[IIT 1997]
2. The rate constant of a reaction is
7 1
1.5 10 sec
at 50C and
7 1
4.5 10 sec
at 100C. Evaluate the
Arrhenius parameters A and
a
E . [IIT 1998]
3. A first order reaction A B requires activation energy of 70 kJ
1
mol
. When a 20% solution of
A was kept at 25C for 20 minute, 25% decomposition took place. What will be the per cent decomposition
in the same time in a 30% solution maintained at 40C ? Assume that activiation energy remains
constant in this range of temperature. [IIT 1993]
4. A 1
st
order reaction is 50% complete in 30 minute at 27C and in 10 minute at 47C. Calculate the :
(a) Rate constant for reaction at 27C and 47C
(b) Energy of activation for the reaction.
(c) Energy of activation for the reverse reaction if heat of reaction is 50 kJ
1
mol
. [IIT 1988]
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5. At 380C, the half life period for the first order decomposition of
2 2
H O is 360 min. The energy of
activation of the reaction is 200 kJ
1
mol
. Calculate the time required for 75% decomposition at
450C. [IIT 1995]
6. A hydrogenation reaction is carried out at 500 K. If the same reaction is carried out in presence of a
catalyst at the same rate, the temperature required is 400 K. Calculate the activation energy of the
reaction if the catalyst lowers the activation energy barrier by 20 kJ
1
mol
. [IIT 2000]
7. The rate constant for the first order decomposition of a certain reaction is given by the equation,
4
1
1.25 10
ln K(sec ) 14.34
T
=
Calculate :
(a) The energy of activation
(b) The rate constant at 500 K.
(c) At what temperature will its half life period be256 minute? [IIT 1997]
8. Two reactions (I) A
Products (II) B
=
10. P
t
= 268.11 mm Hg, t
7/8
= 43.76 min
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SECTION  II
(Single Choice Questions)
1. (d) 2. (b)
3. (b) 4. (c)
5. (c) 6. (a)
7. (c) 8. (d)
9. (b) 10. (b)
11. (d) 12. (c)
13. (b) 14. (b)
15. (c) 16. (c)
17. (c) 18. (b)
19. (b) 20. (d)
SECTION  III
(Multiple Choice Questions)
1. (a, b, c, d) 2. (a, b, c, d)
3. (a, b, c, d) 4. (a, c)
5. (a, b, c) 6. (a, b)
7. (a, b) 8. (a, b, c)
9. (a, c) 10. (a, b, c, d)
SECTION  IV
(Comprehension Type Questions)
1. (a) 2. (c)
3. (d) 4. (a)
5. (b) 6. (a)
(Multiple Matching Type Questions)
7. (a) (q) (b) (r)
(c) (s) (d) (p)
8. (a) (r, s) (b) (s)
(c) (p, q) (d) (q)
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(Assertion Reason Type Questions)
9. (a) 10. (c)
11. (b) 12. (c)
13. (b) 14. (a)
15. (a)
SECTION  V
(Problems asked in IITJEE)
A. Only one option is correct (Objective Questions)
1. (c) 2. (d)
3. (a) 4. (d)
5. (d) 6. (d)
7. (a) 8. (c)
9. (a) 10. (d)
B. More than one option are correct (Objective Questions)
1. (a, d) 2. (a, c, d)
SUBJECTIVE
1. K
318
= 9.22 10
4
sec
1
Ea = 18.3 kcal mol
1
2. Ea = 2.2 10
4
J mol
1
A = 5.42 10
10
3. 67.21%
4. (a) K
1
at 27C = 2.31 10
2
min
1
K
2
at 47C = 6.93 10
2
min
1
(b) Ea = 43.85 kJ mol
1
(c) 93.85 kJ mol
1
5. 20.39 min 6. 100 kJ mol
1
7. 24.83 k cal mol
1
, 2.35 10
5
sec
1
; T = 513 K
8. 0.0327 min
1
9. (i) 2 and 1
(ii) 2.66 10
8
litre
2
mol
2
sec
1
(iii) 55.33 kJ
(iv) 1.140 10
18
10. 311.35 K