CHEMICAL KINETICS

& NUCLEAR CHEMISTRY

Rates of chemical reactions; Order of reactions; Rate constant; First order

reactions; Temperature dependence of rate constant (Arrhenius equation).

CONTENTS INTRODUCTION
 Rate of reaction Some chemical reaction occurs within
few micro seconds or milli seconds due
 Elementary reaction to formation of reaction intermediate
 Integrated rate laws (carbocation, carboanion or free radicals).
But some reaction occur in few year or
 Activation energy months because breaking of strong ionic or
metallic bond is a slow process. Under
 Kinetics of some complex first order
reactions chemical kinetics we would study that
reaction which occurs at measurable rate.
 Methods of determining order
In Chemical Kinetics we would be able to
 Nuclear chemistry understand the velocity as well as different
factors which would effect the chemical
 Kinetics of radioactive disintegration
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.

1
 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

x
The quantity is known as average rate, where x is the change in concentration in
t
t time. As we have discussed in chemical equilibrium rate of change of concentration of
reactant decreases as the reaction proceeds. This means that rate of change of concentration
is not constant. If the time interval is quite large then average rate will show large
deviations from the actual rate.

1.2 INSTANTANEOUS RATE

In order to precisely define rate time interval t is made smaller
i.e. instantaneous rate = average rate as t approaches zero.
 [A]  d[A]
=   = dt
t 0  t 

Consider the hypothetical reaction

A  2B 
 3C  D
d[A]
Rate of disappearance of A = 
dt
d[B]
Rate of disappearance of B = 
dt
d[C]
Rate of appearance of C = 
dt
d[D]
Rate of appearance of 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
d[A] 1 d[B]
or  
dt 2 dt
Similarly we can prove that
Chemistry : Chemical Kinetics & Nuclear Chemistry

d[A] 1 d[C]
 
dt 3 dt
d[A] 1 d[B] 1 d[C] d[D]
So, rate of reaction =    
dt 2 dt 3 dt dt
We can also generalize our statement i.e. for a general reaction
m1A  m 2B 
 n1C  n 2D
1 d[A] 1 d[B] 1 d[C] 1 d[D]
Rate of reaction =    
m1 dt m 2 dt n1 dt n 2 dt

Illustration 1 : Dinitrogen pentaoxide decomposes as follows:

1 d [ N 2O5 ]
N 2O5   2 NO2  O2 . If,   K [ N 2O5 ]
2 dt
d [ NO2 ]
 K [ N 2O5 ]
dt
d [O2 ]
 K [ N 2O5 ]
dt
Derive a relation in, K , K '' and K '''
d[N 2O5 ] 1 d[NO2 ] d[O 2 ]
Solution : For the given change    2
dt 2 dt dt
1
On substituting values, K[N 2O5 ]  K[N 2O5 ]  2K[N 2O5 ]
2
or 2K  K  K

EXERCISE 1

1. For the reaction; 4NH3(g) + 5O2(g)  4NO(g) + 6H2O(g), the rate of reaction in terms of
d[NH 3 ]
disappearance of NH3 is  , then write rate expression in terms of O2, NO and
dt
H2O.
2. For the decomposition reaction: N2O4(g)  2NO2(g); the initial pressure of N2O4 falls
from 0.46 atm to 0.28 atm in 30 minute. What is the rate of appearance of NO2?
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

2. ELEMENTARY REACTION
 Chemistry : Chemical Kinetics & Nuclear Chemistry

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.
NO 2(g)  CO(g) 
 NO(g)  CO 2(g) [net chemical equation] …(i)
Suppose this chemical reaction takes place in two steps
NO 2(g)  NO 2(g) 
 NO3(g)  NO(g) [Elementary reaction] …(ii)

NO3(g)  CO(g) 
 NO 2(g)  CO2(g ) [Elementary reaction] …(iii)

Thus net reaction (i) is obtained by the combination of two elementary reaction (ii) and (iii)
and NO3 is a reaction intermediate as it is produced and consumed during the course of
reaction.
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
1 d[A] d[C]
   [A]m [B]n
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]
d[C]
So,  k[A]m [B]n
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.
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
Chemistry : Chemical Kinetics & Nuclear Chemistry

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 it’s 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
d[P] 1 d[Q]
Rate     k[P]m [Q]n
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
dC
 kC n
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.
dC / dt
k
Cn
Units of k: (concentration)1–ntime–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)–1time–1 = l/mol/s
 Chemistry : Chemical Kinetics & Nuclear Chemistry

Illustration 2 :The data given below are for the reaction of NO and Cl2 to form NOCl at 25K
[Cl2] [NO] Initial rate × 103 (mol litre–1sec–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 Cl2 in the reaction?
b) Write the rate expression.
c) Calculate the rate constant
d) Determine the reaction rate when conc. of Cl2 and NO are 0.2 M and 0.4 M
respectively.
Solution : For the reaction; 2NO + Cl2  2NOCl
Rate = k[Cl2]m[NO]n …(1)
Where, m and n are order of reaction w.r.t Cl2 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 Cl2 is 1.

b) Also, rate expression r = k[Cl2]1 [NO2]2

r 1 10 3
c) And rate constant., k   = 8 litre2 mol–2 sec–1
[Cl2 ][NO]2 [0.05]1[0.05]2

d) Further, r = k[Cl2]1 [NO]2 = 8 [0.2]1 [0.4]2

= 0.256 mol litre–1 sec–1
Chemistry : Chemical Kinetics & Nuclear Chemistry

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 + Br2  2NOBr, is supposed to follow the following mechanism,
fast
i) NO + Br2 NOBr2
slow
ii) NOBr2 + NO   2NOBr
Suggest the rate law expression
3. The thermal decomposition of N2O5 occurs in the following steps:
slow
Step I: N2O5   NO2 + NO3
fast
Step II N2O5 + NO3  3NO2 + O2
–––––––––––––––––––––––––––
Overall reaction 2N2O5  4NO2 + O2-
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 [A]0 , which is the concentration at t = 0 and [A]t , the
[A]t t
d[A]
concentration at time t    k  dt
[ A]0
dt 0

[A]0 2.303 [A]0

ln  kt or k  log
[A]t t [A]t
 Chemistry : Chemical Kinetics & Nuclear Chemistry

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
a
at t  t 1/ 2 ; x =
2
2.303 a
k log
t1/ 2 a/2
0.6932
t1/ 2 
k
In fact we can define any life suppose we want to define 7/8 life.
2.303 a
k log
t ax
7a
at t  t 718 ; x=
8
2.303 a
at k log
t 718 7a
a
8
2.303 2.303
t 718  log 8   3log 2
k k
t 7 / 8  3  t1/ 2
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

Chemistry : Chemical Kinetics & Nuclear Chemistry

Let A  products is following nth order kinetics.

d[A]
i.e.  k[A]n , it can be shown that
dt
2 n 1  1
t1/ 2 
k(n  1)a 0n 1
1
i.e.t1/ 2  (n  2)
a 0n1
Expression for first order reaction is
2.303 a
k log
t ax
2.303 a 2.303
or t log = [log a  log(a  x)]
K ax k
2.303 2.303
t log a  log(a  x)
k k
Comparing this equation with Y = mx + C
2.303
So a plot of t vs log (a – x) will be straight line with a intercept of log a and a slope
k
2.303
of 
k

2.303
slope  
2.303 K
time

log a
K

log(a  x)

3.5 EXAMPLES OF FIRST ORDER REACTION

3.5.1 Decomposition of H2O2

2H 2O 2 
 2H 2O  O 2

H 2O 2 
 H 2O  O [slow i.e. rate determining step]

 O2 [fast]
O  O 

So Rate  [H 2O 2 ]1
or R  k[H 2O 2 ]
Order = 1
 Chemistry : Chemical Kinetics & Nuclear Chemistry

Kinetics of this reaction can be studied by withdrawing a definite volume of reaction

mixture after regular interval of time and titrating it against KMnO 4 solution in presence of
dil. H 2SO 4

2KMnO 4  3H 2SO 4 
 K 2SO 4  2MnSO 4  3H 2O  5O

 H 2O  O 2 ] × 5
[H 2O 2  O 
––––––––––––––––––––––––––––––––––––––––––––––––
2KMnO 4  3H 2SO 4  5H 2O 2 
 K 2SO 4  2MnSO 4  8H 2O  5O 2
Since H2O2 is undergoing self decomposition so quantity of H2O2 present in a definite
volume will also go on decreasing, KMnO4 is reacting with H2O2 so titre value i.e. volume
of KMnO4 used will also go on decreasing.
Let V0 and Vt be the volumes of KMnO 4 used at zero time and after t time respectively.
then V0  a [a = initial conc. of H 2O2 ]
Vt  a  x [a –x = conc. of H 2O2 after t time]
V0 a

Vt a  x
2.303 V
k log 0
t Vt
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
2.303 a
k1  log
t a-x
The volume of KMnO4 used, evidently corresponds to the undecomposed
hydrogen peroxide.
Hence the volume of KMnO4 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
2.303 25
when t = 10 min. k1 = log = 0.022287 min-1 = 0.000314 s-1
10 20.0
2 .303 25
when t = 20 min. k1 = log  0.023230 min -1  0.0003871 s -1
10 15.7
Chemistry : Chemical Kinetics & Nuclear Chemistry

2.303 25
when t = 30 min. k1 = log  0.02369 min -1  0.0003948 s -1
30 12.5
2.303 25
when t = 40 min. k1 = log  0.023897 min -1  0.0003983 s -1
40 9.6
The constancy of k, shows that the decomposition of H2O2 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 NH4NO2 in aqueous solution

NH 4 NO 2 
 N 2  2H 2O
Rate  [NH 4 NO 2 ]1
Rate  K[NH 4 NO 2 ]
order = 1
Kinetics of this reaction may be studied by collecting the nitrogen evolved and measuring
its volume after regular intervals of time
Let Vt and V be the volumes of N 2 liberated after t time and at the end of reaction.
NH 4 NO 2 
 N 2  2H 2O
Initial conc. a 0
Conc. after t time a–x x
Conc. at t =  0 a
Vt  x
V  a
or V  Vt  a  x
V a

V  Vt a  x
2.303 V
k log
t V  Vt

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 N2 (mL) 10 25 33 162
Solution : C6H5N2Cl  C6H5Cl + N2
 Chemistry : Chemical Kinetics & Nuclear Chemistry

initial concentration a
Concentration of after time t (a – x) x
At  time, i.e., when the reaction is complete, the whole of C6H5N2Cl converts
into N2. Hence volume of N2 at  time corresponds to the initial concentration ‘a’
while volumes of N2 at different time intervals correspond to x as shown above.
2.303 162
For t = 20 min, k1  log  0.0032 min 1
20 162  10
2.303 162
For t = 50 min, k1  log  0.0033min 1
50 162  25
2.303 162
For t = 70 min, k1  log  0.0032min 1
70 162  33
The constant of k1 shows that the decomposition of C6H5N2Cl; is a first order
reaction.

3.5.3 Conversion of N-Chloroacetinalide into p-chloro acetanialide

O O
Cl H
N CH3 N CH3

rearrangement

isomerism


N-chloro-N-phenylacetamide
Cl
N-(4-chlorophenyl)acetamide

Rate  [N-chloroacetinalide]1
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
I2 against standard sodium thiosulphate solution.
N-chloroacetinalide reacts with KI and liberates I 2 but p-chloroacetinalide does not.
I 2  2Na 2S2O 3 
 Na 2S4O 6  2NaI
N-chloroacetinalide 
 P  chloroacetinalide
t=0 a 0
t=t a–x x
Let V0 and Vt be the volumes of sodium thiosulphate used at t = 0 and t = t respectively,
then
V0  a
Vt  a  x
Chemistry : Chemical Kinetics & Nuclear Chemistry

V0 a

Vt a  x
2.303 V
k log 0
t Vt
Illustration 5 : Acetochloracetanilide (N-chloroacetanilide) 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 N-chloroacetanilide 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
k log  0.3411
1 32
(ii) When t = 2 hours, (a – x) = 22.5
2.303 45
k log  0.3468
t 22.5
(iii) When t = 6 hours, (a – x) = 5.7
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
 Chemistry : Chemical Kinetics & Nuclear Chemistry

2.303 a
k log
t ax
2.303 45
0.300  log
t (45  x)
45 – x = 16.03
 x = 28.97
28.97
Hence fraction of N-chloroacetanilide reacted in 3 hours =  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 :
(CH 3 )3 CBr  OH  
(CH 3 )3 OH  Br 
This reaction takes place in two steps.

i) CH3 CH3
slow
H3C Br 
 H3C  Br -
CH3 CH3

ii) CH3 CH3

fast
H3C  OH-  H3C OH
CH3 CH3

Since slowest step is rate determining step.

Rate  [(CH 3 ) 3 CBr]1[OH  ]0
= K[(CH3 )3 CBr]
Molecularity = 2
Order = 1
So the reaction is pseudo unimolecular

3.6.1 Hydrolysis of Ester catalysed by an acid


H
CH3COOC 2H 5  H 2O   CH 3COOH  C6H 5OH

Rate  [CH 3COOC 2H 5 ][H 2O]

Since water is in large excess so its concentration almost remains constant
Rate  [CH 3COOC 2H 5 ]1
Chemistry : Chemical Kinetics & Nuclear Chemistry

Rate  k[CH 3COOC2 H 5 ]

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 V0 , Vt and 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 ( V0 ) corresponds to the
concentration of catalyst and volume of NaOH used after t time (Vt ) corresponds to the
concentration of catalyst and acetic acid formed.

H
CH3COOC 2H 5  H 2O   CH 3COOH  C 2H 5OH
t=0 a 0
t=t a–x x
t= 0 a

Vt  V0  x [x  conc. of CH 3COOH formed after t time]

V  V0  a
(V  V0 )  (Vt  V0 )  a  x
V  Vt  a  x
V  V0 a

V  Vt a  x
2.303 V  V0
k log 
t V  Vt

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 30°C. 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.
 Chemistry : Chemical Kinetics & Nuclear Chemistry

2.303 V  V0
k1  log 
t V  Vt
Where V0, Vt and V represent the volumes of alkali used at the commencement
of the reaction, after time t and at the end of the reaction respectively, Hence
V - V0 = 21.05 - 9.62 = 11.43
2.303 V  V0
Time V - Vt log   k1
t V  Vt
2.303 11.43
75 min 21.05 - 12.10 = 8.95 log  0.003259 min -1
75 8.95
2.303 11.43
119 min 21.05 - 13.10 = 7.95 log  0.003264 min -1
119 7.95
2.303 11.43
83 min 21.05 - 14.75 = 6.30 log  0.003254 min -1
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
C12H 22O11  H 2O   C6H12O6  C6H12O6
Cane sugar glu cose fructose

Rate  [C12O 22O11 ][H 2O]

Since water is solvent its concentration is constant.
So Rate = K[C12H 22O11 ]
Molecularity = 2
Order = 1
So the reaction is pseudo unimolecular
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 3rd order.
Rate  [C12H 22O11 ][H 2O][H  ]

But under ordinary conditions H 2O and H  are constant so,

Rate  [C12 H 22O11 ]

The initial solution of cane sugar is destrorotatory but the product mixture is laevorotatory.
Since the reaction involves inversion in the sign of rotation, ths is known as inversion of
cane sugar.
Chemistry : Chemical Kinetics & Nuclear Chemistry


H
C12H 22O11  H 2O   C 6H12O6  C6 H12O6
Dextrorotatory Dextrorotatory Laevorotatory

Specific rotation +52.5° 92

 
laevorotatory

Fructose

Laevo rotatory

Glucose

Prism dextro rotatory

Cane sugar

dextro rotatory

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 r0 , rt and r be the angles of rotation at 0 time, after t time and at the end of reaction.
0°
r rt

r0

-90° 90°

180°

So, r0  rt  x …(i)
r0  r  a …(ii)
(r0  r )  (r0  rt )  a  x
or rt  r  a  x
r0  r a

rt  r a  x
2.303 r r
k log 0 
t rt  r
Illustration 7 :The optical rotations of sucrose in 0.5 N HCl at 35°C 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
 Chemistry : Chemical Kinetics & Nuclear Chemistry

Solution : The inversion of sucrose will be first order reaction if the above data confirm to
2.303 r r
the equation , k 1  log 0 
t rt  r
Where r0, rt and r represent optical rotations at the commencement of the reaction
after time t and at the completion of the reaction respectively
n the case a0 = r0 - r = +32.4 - (-11.1) = +43.5

The value of k at different times is calculated as follows :

Time rt rt - r k

2.303 43.5
10 min +28.8 39.9 log = 0.008625 min-1
10 39.9

2.303 43.5
20 min +25.5 36.6 log = 0.008625 min-1
20 36.6

2.303 43.5
0 min +22.4 33.5 log = 0.008694 min-1
30 33.5

2.303 43.5
40 min +19.6 30.7 log = 0.008717 min-1
40 30.7
The constancy of k1 indicates that the inversion of sucrose is a first - order reaction.

EXERCISE 3 :
1. From the data obtained for decomposition of H2O2, show that decomposition of a first
order reaction.

Time in minutes 0 10 20 30 40
Volume of KMnO4 (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 N2(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
Chemistry : Chemical Kinetics & Nuclear Chemistry

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.
Threshold energy
Ea Eb Ea
Potential energy

Eb
Products Products
H Reactants
H
Products
Reactants
Threshold energy

Reaction co-ordinate Reaction co-ordinate

E a = activation energy of forward reaction

E b = activation energy of backward reaction

H = Heat of reaction
H  E a  E b H  E a  E b
Since Ea  E b Since Ea  Eb
So, H  0 i.e. reaction is endothermic So, H  0 i.e. reaction is exothermic

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.
 Chemistry : Chemical Kinetics & Nuclear Chemistry

(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.
k
Temperature coefficient = T 10
kT
k T = rate constant t°C
k T 10 = rate constant at T + 10°C
Normally T and T+ 10 are taken as 25°C and 35°C.
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.
dnk E
 …(i)
dT RT 2
E  Energy of activation
T  Temperature is Kelvin scale
R  Gas constant
E
 dnk   RT 2
dT. {E is supposed to be constant] nK
E
slope  
E 1 R
nk     C
R T
1/ T
E
or nk   C …(iv)
RT
on comparing this equation with Y = mx + C

4.3 ANOTHER FORM OF ARRHENIUS EQUATION

k  Ae E / RT
A  frequency factor
e  E / RT  fraction of molecules which have energy equal to or greater than activation
energy.
Chemistry : Chemical Kinetics & Nuclear Chemistry

Let k1 is rate constant at temperature T1 and k 2 is rate constant at temperature T2 .

E
nk1   C
RT1
E
nk 2   C
RT2
E1 1
nk 2  nk1 
  
R  T1 T2 
k E T T
n 2   2 1
k1 R T1T2
k2 E T T
or log   2 1
k1 2.303R T1T2
Illustration 8: The activation energy of a non-catalysed reaction at 37°C 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: k  Ae Ea / RT
Let k = rate constant for non-catalysed reaction and kc rate constant for catalysed
reaction. Ea be the activation energy of non-catalysed reaction and Eac be the
energy of activation of catalysed reaction.
1. k  Ae Ea / RT
2. k c  Ae Ea / RT
1
k (E ac  Ea )
  e RT
kc
k 1
 log  (E ac  E c )
k c 2.303RT
k 1
 log  (6 103  200 103 )
k c 2.303  2  310
k
 log  9.8
kc
k kc
  1.56  1010 or  6.3 109
kc k
Illustration 9 : A first order reaction A  B requires activation energy of 70 kJ/mol. When
20% solution of A was kept at 25°C for 20 minutes, 25% decomposition too
place. What will be the percent decomposition in the same time in a 30%
solution maintained at 40°C? 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.
 Chemistry : Chemical Kinetics & Nuclear Chemistry

At 25°C, 20% of A decomposes 25%

C0
 kt  2.303log
Ct
100
 k(40)  2.303log
75
 k(at 25°C) = 0.0143min -1

k 40 Ea  T2  T1 
log   
k 25 2.303R  T1T2 

k 40 70 103  40  25 
log   
0.0143 2.303  8.31  298  313 
 k (at 40°C)=0.055min -1
Now calculate the % decomposition at 40°C using first order kinetics
C0
kt  2.303log
Ct
100
 0.055  40  2.303log
100  x
 x  67.1  67.1% decomposition of A at 40°C.

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.
1
(i) From Arrhenius law a plot of ln k vs gives a straight line, with large slope for large
T
E and small slope for small E.
(ii) Reactions with high activation energy are far more temperature sensitive then reactions
with low activation energy.
Chemistry : Chemical Kinetics & Nuclear Chemistry

High E
200
Low E
100

50
E
nK slope  
20 R

10
T  1000 T  87
5 for doubling rate for doubling rate

2000K 1000K 463K 376K

1/ T

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 Ea or one with large value of Ea
11067
(ii) For a reaction, rate constant is given as lnK(min–1) = 31.33 – . Evaluate, K,E
T
and A for the chemical reaction at 25°C.
2. For a particular first order reaction at 27°C, the concentration of reactant is reduced to one
half of its initial value after 5000s. At 37°C, the concentration is halved after 1000s.
Calculate (a) the rate constant of the reaction at 27°C, (b) the time required for the
concentration to be reduced to one quarter of its value at 37°C, (c) the activation energy
of the reaction.
3. The Arrhenius equations for the rate constant of decomposition of methyl nitrite and ethyl
nitrate are
 152300Jmol 1   157700Jmol1 
k1 (s 1 )  1013 exp   and k 2 (s 1
)  1014
exp  
 RT   RT 
respectively. Find the temperature at which the rate constants are equal.

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
Ester + H 2O   acid  alcohol
The rate of the reaction is given as
Rate  k[ester][H  ]
 Chemistry : Chemical Kinetics & Nuclear Chemistry

Since concentration of H  in the beginning and Alternative path

provided by the
at the end is same so. Ea catalyst.

Potential energy
Rate  k[Ester] Eb
Reactants
H
where k  k[H  ]
Products

k  is known as pseudo or effective rate constant

Reaction co-ordinate

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 H  should not let the reaction to happen, therefore
the rate of reaction in the absence of H  should be, Rate  K[ester]
If [H  ]  1 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.
There are two types of catalyst.
a) Reactant catalyst b) Non-reactant 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 non-reacting catalyst on the other hand do not exist in the rate expression. Changing
the concentration of non-reacting 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 k1 and k2 respectively, then it is known as first order
parallel chain reaction. Let the overall rate constant of A is k0 by which decay into B and C.
k1 B

k2 C

d  B
   k1  A t …(i)
dt
d  C
   k 2  A t …(ii)
dt
d A
   k 0  A t …(iii)
dt
Chemistry : Chemical Kinetics & Nuclear Chemistry

d A d B d C

    …(iv)
dt dt dt
Putting equations (i), (ii) and (iii) in equation (iv), we get
k 0  A t  k1  A t  k 2  A t

or, k 0  k1  k 2

From equation (i) and (ii), we get

d  B
 k1  A t
dt
or,  Bt   d  B  k1   A t dt …(v)

Similarly, C t   d  C   k 2   A t dt …(vi)

Divide equation (v) by equation (vi), we find

 Bt k2
 (at any time t) …(vii)
 Ct k1

  A 0   A t   Bt   Ct
or  A 0   A t   Bt  Ct (viii)

 A 0
  k1  k 2  t  2.303log
 A t
If k1 and k2 , 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
k1 B

k2 C

k0 = k1 + k2
or k0 > k1 and k0 > k2
Let the rate of formation of B is x% rate of decomposition of A.
d  B d  A
   x%  
dt dt
 k1 [A]t = x % × k0 [A]t
or, k1 = x% × k0
 Chemistry : Chemical Kinetics & Nuclear Chemistry

ln2 x ln2
  
 t1/ 2 1 100  t1 / 2 overall
100   t1/ 2 overall
or,  t1 / 2 1 
x
where (t1/2)1 is the half life of A, while it is converting into B and (t1/2)overall is the half life
of A.

Similarly, half–life of A, i.e. (t1/2)2 while it is converting into C will be

100   t1/ 2 overall

 t1 / 2  2 
100  x 
(c) For the first order parallel chain reaction

k1 mB

k2 nC

 B t mk1

 C t mk 2

and koverall = k1 + k2
Chemistry : Chemical Kinetics & Nuclear Chemistry

5.2 CONSECUTIVE OR SEQUENTIAL REACTIONS

Consider the following consecutive reaction
K1 K2
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
d A
  k1  A t   A t  A 0e  k,t …(i)
dt
d  B
  k1  A t  k 2  Bt
dt
d  B
or  k  Bt  k1  A t  k1  A 0 e k1t …(ii)
dt
Solving first degree differential equation (ii) with integrating factor e k 2 t , then we get
concentration of B at any time t.
k1  A 0
 Bt   e  k1t  e k 2 t 
k 2  k1  

(b) Time at which concentration of B is maximum

1 k
t ln 2
k 2  k1 k1

(c) Maximum concentration of B

x
k  k2
 Bmax   A 0  2  where x 
 k1  k1  k 2

d B
(d) Time at which is maximum
dt
2 k
t ln 2
k1  k 2 k1

(e) At steady state,

k1 [A]t = k2 [B]t
(f) If k1 < < k2, then sequential reaction converts into
k
A 
1
C
d A
   k1  A t
dt
 Chemistry : Chemical Kinetics & Nuclear Chemistry

Illustration 10 : 227Ac has a half-life of 22.0 years with respect to radioactive decay. The decay
follows two parallel, paths, one leading to 222Th and the other to 223Fr. 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
0.693 0.693
k= 
t 12 22
222
If k1 and k2 are the rate constants of the reactions leading to Th and Fr223,
respectively we have
0.693
k1 + k2 = ;
22
k1 2

k 2 98
On solving for k1 and k2, we get
k2 = 0.03087 y1
k1 = 0.00063 y1

EXERCISE 5 :
1. An organic compound A decomposes following two parallel first order mechanisms.
B
k1 1
A  and k1  1.3  105 s1
k2 9
C
Calculate the concentration ratio of C to A, if an experiment is allowed to start with only
A for one hour.
K1 K2
2. For a consecutive first order reaction A   B   C, the values of K1 and K2 are
–1 –1
45 sec and 15 sec 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.
Chemistry : Chemical Kinetics & Nuclear Chemistry

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.,
(k1 and k2 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 = k1 (a – x) – k2 (b + x) … (i) [  both processes occur simultaneously]
When equilibrium is reached, the net rate is zero
Thus, k1 (a – xe) = k2 (b + xe) (e = equilibrium)
k1 k1
Hence, (b + xe)  (a – xe) or b= (a – xe) –xe
k2 k2
Substituting value of b in eqn. (i)
dx k 
Rate of reaction,  k 1 (a  x )  k 2  1 (a  x e )  x e  x 
dt k2 
on solving, we get
Rate = (k1 + k2) (xe – x)
After rearranging and integrating the equation, we get an equation similar to first order
reaction as shown below.
dx k
or  ( k 1  k 2 )dt A k1 B
xe  x 2

x dx t
   (k1  k 2 )dt
x0 xe  x 0

xe  x0
log  (k 1  k 2 ) t
or xe  x

1 x  x0
Or (k 1  k 2 )  log e
t xe  x

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.
 Chemistry : Chemical Kinetics & Nuclear Chemistry

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 P0 0 0
Pressure at time (t) (P0 – x) x x
(Here x is no. of moles of A which change to produce)
Thus, total pressure (Pt) at time (t) = P0 – x + x + x
or Pt = P0 + x, x = Pt – P0
a – x = P0 – (Pt – P0) = 2P0 – Pt
2.303 P0
Thus, k log
t (2P0  Pt )

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.

1 [A]0
K  ln . If for different values of t and [A]t , K comes constant then order of
t [A]t
reaction will be 1 other wise we will switchover to higher order expressions.
Integrated Expressions for various reactions
x
Zero order k0 
t
2.303 a
First order k1 log
t (a  x)

1 x 
Second order k2   
t  a(a  x) 

1  x(2a  x) 
Third order k3   2 
t  a (a  x 2 ) 
Chemistry : Chemical Kinetics & Nuclear Chemistry

(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 (a–x) vs t is a straight
line then order of reaction will be 1.

Zero order First order 1

(a  x) log(a  x)
(a  x) Second order

t t t

1
(a  x)2 Third order

(iii) Half life Method: As we have seen for nth order reaction

1
t1/ 2 
a n1

Let t11/ 2 be the half life at initial concentration a1 and t 21/ 2 be the half life at intial
concentration a 2 .

1
Then t11/ 2 
a1n 1

1
t 21/ 2 
a n21
n 1
t11/ 2 a 
 2 
t 21/ 2  a1 

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.
 Chemistry : Chemical Kinetics & Nuclear Chemistry

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.  -particles -particles  -rays.

No.
1. 2 units +ve charge & 4 Unit –ve charge with no Electromagnetic waves
units mass. mass of short wavelength.
2. Represented as 2 He4 or Represented as –1 eo Represented as 0  0
He 
3. They have high ionizing Ionizing power is less than Ionizing power is very
power that of  particle less
4. These have low Penetrating power is 100 Penetrating power is 100
penetrating power times that of  particle times that of  particle.
5. Velocity is of the order of Velocity is of the order of Velocity is same as that
2  109 cm/s 2.8  1010 cm/s of velocity of light
( 3 1010 m/s).
6. When an  -particle is When a  particle is There is no change in
emitted atomic number emitted, atomic number atomic number or atomic
decreases by 2 units and increases by one unit and mass.
atomic mass decreases by atomic mass remains
4 units unchanged

7.3 STABILITY OF NUCLEI

At some point, you may have wondered, ‘‘If positive charges repel one another, how is it
possible for protons to be packed so closely in the nuclei of atoms ?’’ The answer is that
there are attractive nuclear forces that are much stronger than electrostatic forces. The
strengths of these forces are closely related to the numbers of protons and neutrons in a
nucleus. We begin with some observations about the naturally occurring stable nuclides.
(i) About 160 stable nuclides have an even number of protons and an even number of
neutrons, for example, 126 C
Chemistry : Chemical Kinetics & Nuclear Chemistry

(ii) About 50 stable nuclides have an even number of protons and an odd number of
neutrons, for example, 25
12 Mg .

(iii) About 50 stable unclides have an odd number of protons and an even number of
neutrons, for example, 199 F .

(iv) Only 4 stable nuclides have an odd number of protons and an odd number of neutrons.
They are 12 H, 63 Li, 105 B, and 147 N .
One theoretical approach to nuclear stability is the nuclear shell theory. In simplest terms,
this theory proposes that the protons and the neutrons each exist in shells within the
nucleus. This is much like the existence of electrons in shells outside the nucleus. The
similarity extends to the special stability associated with the closing of shells, similar to
what is seen with the noble gases in electrons configuration. In the nuclear shell theory, a
special stability is associated with nuclei that have any of the following numbers as
numbers of protons or neutrons.
2, 8, 20, 28, 50, 82, 126
These numbers are called magic numbers because scientists recognized their significance
in relation to nuclear stability before they had developed a theory to explain them.
One observation consistent with these magic numbers is the fact that alpha particles are
very stable; they have 2 protons and 2 neutrons and are ‘‘doubly magic.’’ Another
observation is that tin (Z = 50) has ten naturally occurring stable nuclides, more than any
other element. The magic number of protons (50) seems to allow for a greater variation in
the number of neutrons in the tin nucleus than in others. Also, the uranium-238 radioactive
decay series terminates in the nuclide 206 207
82 Pb ; the uranium-235 series, in 82 Pb ; and the
208
thorium-232 series, in 82 Pb . All these terminating includes have the magic number 82 in
208
lead (Z = 82); 82 Pb is doubly magic, with 82 protons and 126 neutrons.
A crucial factor in the stability of a nucleus is the ratio of the neutron number (N) to the
proton number (Z). Some nuclides of the lightest elements have an N/Z ratio of 1, and as a
group these nuclides have an average ratio slightly greater than 1. Examples of nuclides in
this group are 42 He, 16 27 39 40
8 O, 13 Al, 19 K, and 20 Ca . Nuclides with Z > 20 require a large number

of neutrons than protons to moderate the effect of increasing proton repulsions. For
example, the N/Z ratio in 56 133 209
26 Fe is 30/26 = 1.15; in 55 Cs it is 78/55 = 1.42, and in 83 Bi ,

126/83 = 1.52. For nuclides with Z > 83, the protons repulsions are too large to be
overcome by proton-neutron interactions, and the nuclides are all radioactive.
The general pattern for nuclear stability in terms of neutron and proton numbers is shown
in figure, a graph of neutron number (N) versus proton number (Z). All of the naturally
occurring stable nuclides are indicated by dots within the belt labeled the belt of stability.
However, other nuclides in this belt that are not shown are radioactive. Also all nuclides
falling outside the belt are radioactive, and their mode of decay is one that brings the
nuclides formed in the decay process into the belt. Nuclides above the belt decay by beta
emission, and those below the belt by positron emission and electron capture. Many of the
nuclides in the upper right corner decay by alpha emission. If the numbers 114 and 184 are
 Chemistry : Chemical Kinetics & Nuclear Chemistry

also magic numbers, as some scientists think they are, there might be a small island of
stability centered on the nuclide with Z = 114 and N = 184. This nuclide may someday be
synthesized, and there have even been unsuccessful attempts to find element 114 in natural
sources.

118 234
Illustration 11 :Which of the following would you expect to be radioactive, 50 Sn, 91 Pa, 54
25 Mn,
74
30 Zn ?
118
Solution : 50 Sn : This nuclide has 50 protons and (118 – 50) = 68 neutrons. This is an even-
even combination, the most common for stable nuclides. Also, the neutron :
proton ratio of 68:50 lies within the belt of stability so 118
50 Sn is non-radioactive.

234
91 Pa : Atomic number 91 exceeds the limit for the naturally occurring stable
234
nuclides (Z > 83). 91 Pa is radioactive.
54
Mn : This nuclide has 25 protons and (54 – 25) = 29 neutrons. This is an odd-
25
odd combination found only in four stable nuclides of low atomic numbers. We
should expect that it is radioactive.
74
30 Zn : This nuclide has 30 protons and (74 – 30) = 44 neutrons. So Z = 30, the
74
upper limit of the belt of stability is at about N = 40. The nuclide 30 Zn lies above
the belt and is radioactive.

7.4 MODE OF DECAY

Chemistry : Chemical Kinetics & Nuclear Chemistry

Alpha-particle emission : An alpha (a ) particle has the same composition as a helium

nucleus : two protons and two neutrons. Thus an a particle has a mass of 4 u and a charge
of 2+. Because they carry a positive charge, a particles are deflected in electric and
magnetic fields. The penetrating power of alpha particles through matter is low; the
particles can generally be stopped by a sheet of paper. The symbol for an alpha particles is
4
2 He . We can represent a -particle emission with a nuclear equation, as in the radioactive

decay of uranium-238.
Sum of mass numbers : 238 234 + 4 = 238
238 234 4
92 U ¾¾
® 90Th + He 2

Sum of atomic numbers : 92 90 + 2 = 92

When a nucleus emits an alpha particles, its atomic number decreases by 2 and its mass
number decreases by 4. The new nuclide is that of a different element than the decaying
nuclide.
Beta-particles emission : Beta (β - ) particles are electrons. Like all electrons, they have
very little mass and carry a charge of 1–. Beta particles are deflected in electric and
magnetic fields, but in the opposite direction from alpha particles. Beta particles are more
penetrating than a particles. They can pass through aluminum foil 2 to 3 mm thick. The
symbol for a beta particle is - 01 e .
Although an atomic nucleus contains the protons and neutrons that make up an alpha
particle, a nucleus does not contain electrons. Instead, a neutron in converted to a proton
and an electron, represented in the following nuclear equation.
1
0 ® 11p + - 01e
n ¾¾
Because the atomic number represents the positive charge on a particle, the neutron has an
atomic number of 0 (no charge). The electron has the equivalent of an atomic number of –
1; it carries the same charge as a proton, but negative in sign. An example of a radioactive
decay that produces beta particles is shown below :
Sum of mass numbers : 234 234 + 0 = 234
234 234 0
90 Th ¾¾
® 91Pa + -1e
Sum of atomic numbers : 90 91 + - 1 = 90
When a nucleus emits a beta particle, its atomic number increases by 1 and its mass
number is unchanged. The new nuclide is that of a different element than the decaying
nuclide.
Gama-ray emission : Gamma (γ) rays are a highly penetrating form of electromagnetic
radiation. They consist of photons, and thus they are not particles of matter. They are
emitted by energetic nuclei as a means of reaching a lower energy state. In a nuclear
equation for gama-ray emission, we represent the energetic nucleus by affixing the symbol
m to its mass number. For example, in the radioactive decay of uranium-238 by alpha-
particle emission, 23% of the thorium-230 nuclei formed are in an excited state : 230m
90 Th .

These nuclei then emit energy as gamma rays.

 Chemistry : Chemical Kinetics & Nuclear Chemistry

Sum of mass numbers : 230 230 + 0 = 230

234m 230
90 Th ¾¾
® 90Th + g
Sum of atomic numbers : 90 90 + 0 = 90
When a nucleus emits a gamma ray, both its atomic number and mass number remain
constant. The new and old nuclide are of the same element. As we would expect for a form
of electromagnetic radiation, gamma rays are unaffected by electric and magnetic fields.
Positron emission : Positrons are particles having the same mass as electrons but carrying
a charge of 1+. They are sometimes called positive electrons and referred to as b +
particles. Their penetrating power through matter is very limited because when a positron
comes into contact with an electron, the two particles annihilate each other and are
converted to two gamma rays. Positrons are formed in the nucleus through the conversion
of a proton to a neutron and a positron.
1
1 ® 10 n + 10e
p ¾¾
Positrons are most commonly emitted in the radioactive decay of certain nuclides of the
lighter elements. The radioactive decay of alumium-26 is 82% by positron emission.
Sum of mass numbers : 26 26 + 0 = 26
26 26 0
13Al ¾¾
® 12Mg + e
1

Sum of atomic numbers : 13 12 + 1 = 13

When a decaying nucleus emits a positron, its atomic number decreases by 1 and its mass
number is unchanged. The new nuclide is that of a different element from the decaying
nuclide.
Electron capture : Electron capture (EC) is a process in which the nucleus absorbs an
electron from an inner electronic shell, usually the first or second. An X ray is released
when an electron from a higher quantum level drops to fill the level vacated by the
captured electron. Once inside the nucleus, the captured electron. Once inside the nucleus,
the captured electron combines with a proton to form a neutron.
0
-1 e + 11P ¾ ¾
® 10 n
Nuclear equations for electron capture usually show the captured electrons as a reactant.
Iodine-125, used in medicine to diagnose pancreatic function and intestinal fat absorption,
decays by electron capture.
Sum of mass numbers : 125 0 125
125 0 125
53I + e
-1 ¾¾
® 52 Te
Sum of atomic numbers : 53 -1 52
The result of electron capture is the same as positron emission. The atomic number of the
nucleus decreases by 1, and the mass number is unchanged. The new nuclide is that of a
different element than the decaying nuclide.
Chemistry : Chemical Kinetics & Nuclear Chemistry

84
Illustration 12 :What kind of radioactive decay would you expect the nuclide 40 Zr to undergo ?
Solution : When we check the belt of stability at Z = 40, we see that a nuclide with N = 44
lies below the belt. This confirms that the nuclide is radioactive. We would expect
a decay that moves the neutron:proton ratio closer to the belt. This means
converting a proton to a neutron. The atomic number goes down by one, and the
mass number remains the same. These changes are achieved either by positron
emission or electron capture.
84 84
Positron emission : 40 Zr ¾ ¾
® 39 Y + 10e
84
Electron capture : 40 Zr + - 01e ¾ ¾
® 84
39 Y
84
Notice that in each case, the neutron:proton ration increases from 44/40 in 40 Zr to
84
45/39 in Y .39

7.5 NUCLEAR FISSION

Splitting of a nucleus into lighter nucleus is known as nuclear fission. U 235 isotope is
unstable and when it is hited by slow moving neutrons, it splits into a number of fragments,
each of which has mass smaller that that of Uranium with the evolution of large amount of
energy. This process is called nuclear fission.

56 Ba140 36 Kr 93  30 n1
144
92 U 235  0 n1 54 Xe 38 Sr 90  20 n1
55 Cs144 37 Rb 90  20 n1
It has been observed that during nuclear fission, the sum of the masses of the products
formed is slightly less than the masses of target species and bombarding neutrons. This loss
is known as mass defect. This loss in mass is converted to energy. Loss in lamu produces
931.48 Mev energy.

7.6 NUCLEAR FUSION

What would you thing of constructing one giant nuclear reactor out in space that would
transmit abundant energy to Earth almost forever ? Well, that’s exactly what we earthlings
have in our sun, 92 million miles away. The sun is powered by the fusion of atomic nuclei,
and its fuel supply–mostly 11 H —will last for billions of years.
On Earth, scientists have unleashed the extraordinary energy of uncontrolled fusion
reactions in hydrogen bombs. In a hydrogen bomb, nuclear fusion is initiated by the fission
reaction in a fission (atomic) bomb. However, such a totally uncontrolled fusion reaction
cannot be used for practical purposes. Control of fusion reactions as energy sources is
probably still decades away.
Scientists face a daunting challenge in developing a fusion energy source. The most
promising nuclear reaction is the deuterium-tritium reaction.
2
1 H  13H 
 24 He  10 n
 Chemistry : Chemical Kinetics & Nuclear Chemistry

Before they will fuse, however, the nuclei of deuterium and tritium must be forced
extremely close together. And because the positively charged nuclei repel one another so
strongly, close approach requires that the nuclei have enormously high thermal energies. At
the required temperature, gases are completely ionized into a mixture of atomic nuclei and
electrons known as plasma. A temperature of over 40,000,000 K is necessary to initiate
self-sustaining fusion–a nuclear reaction that releases more energy than it takes to get it
started. Another requirement is that the plasma be confined at an enormously high density
long enough for the fusion to plasma be confined at an enormously high density long
enough for the fusion to occur. Moreover, this confinement must be done without the
plasma contacting the walls of the reactor, where it would immediately lose heat and thus
its capability to fuse. One method is to confine the plasma in a magnetic field.

8. KINETICS OF RADIOACTIVE DISINTEGRATION

Rate of decay of disintegration : Rate of disintegration of radioactive isotope is
proportional to it’s number of atoms.
Rate of decay  N
dN
–  N.
dt
N 
 number of atoms of radioactive isotope.
Rate of decay of A
No. of atoms of A

Time Time

dN
– N
dt
dN
or –  N … (i)
dt
 is known as decay constant or disintegration constant.
If dt = 1 second.
dN
Then – 
N
Decay constant (  ) : Thus decay constant (  ) is equal to the fraction of radioactive
isotope disintegrating per second.
From equation (i)
dN
–   dt
N 
– log N  t  C
where C is integration constant
Chemistry : Chemical Kinetics & Nuclear Chemistry

when t = 0; N = No. (initial number of atoms)

–log N 0 = C
So –log N =  t – log N0
N0
t  log
N
1 N
  ln 0
t N
2.303 N
 log 0
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 t1/ 2  1600 years).
Rate of decay (activity )    No. of atoms in 1 g Ra.
.6932 1 6.023 10 23
  3.7  1010 dps
1600  365  24  60  60 223
 3.7 1010 Becque rrel
1 curie = 3.7 1010 dps = 3.7  1010 Becquerrel
1 Rutherford = 106 dps.
Initial activity  Initial amount
Activity after `t’ time  amount left undisintegrated after t time.
2.303 initial activity
 log
t activity after t time
as we have seen
– ln N  t – ln N 0
N
ln  – t
N0
N
 e – t
N0

or N  No e – t
Half life period (t1/ 2 ) : It is the time after which activity of a radioactive isotope reduces
to half of it’s initial value.
 Chemistry : Chemical Kinetics & Nuclear Chemistry

When t  t1/ 2 , N  N 0/ 2
2.303 N
 log 0
t N
2.303 N
t1/ 2  log 0
 N 0/ 2
0.6932
t1/ 2 

Unit of   time –1
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.
1
Average life 

1 t
K  1/ 2
 0.6932
K  1.44 t1/ 2

8.2 RADIOACTIVE EQUILIBRIUM

– – –
92 U 238   90 Th 234   91Pa 234   92 U 234
Suppose a radioactive isotope. A is producing another radioactive substance B, which in
turn is producing C.
A 
 B 
C
Rate of decay of A  N1 [ N1 is no. of atoms of A].
Rate of decay of A = 1N1 [ 1 is decay constant of A]

Rate of decay of B  N 2 [N 2 is no. of atoms of B]

  2 N 2 [ 2 is decay constant of B]
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
1N1   2 N 2
1 N 2 0.6932 / T1
 
 2 N1 0.6932 / T2
Chemistry : Chemical Kinetics & Nuclear Chemistry

1 N 2 T1
 
 2 N1 T2
1
but 
K
1 K 2 N T
so   2  1
 2 K1 N1 T2

8.3 CARBON DATING

14
7 N  0 n1 
 6C14  1H1
atomspheric cos mic
nitrogen rays

6 C14 is radiocarbon (  -emitter)

6 C14 
 7 N14  –1 0
Carbon dating is based upon the fact that radio carbon –14 is produced in the atmosphere
by the action of cosmic rays C14 is a  emitter with a half life of 5730 years. It’s rate of
formation has been constant so the atmosphere has an equilibrium concentration of C14
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 C14 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.
2.303 N
 log 0
t N
2.303 N 0
 log
t N
2.303 Initial activity
 log
t activity after t time
2.303 C / C in fresh sample
 log 14 12
t C14 / C12 in old sample

8.4 MINERAL DATING (GEOCHRONOLOGY).

Determination of age of rocks, earth etc. is known as mineral dating
2.303 N
 log 0
t N
2.303 PD
 log
t P
P = no. of atoms of parent element
D = no. of atoms of daughter element.
 Chemistry : Chemical Kinetics & Nuclear Chemistry

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?
0.693 0.693
Solution : K 
T1/ 2 5770
= 1.201  10–4 year–1
2.303 N
K log 0
t Nt
2.303 N
1.201  10–4  log 0
11540 Nt
N0
4.002 =
Nt
Nt 1
 (Remaining fraction) =
N0 4.002

EXERCISE 6 :
1. The bones of a prehistoric bison were found to have a 14C activity of 2.80 dis/min. g
carbon. Approximately how long ago did the animal live? (t1/2 = 5730 years) 14C activity
of fresh sample = 15.3 dis/min/gC.
2. Potassium contains 9.310 atom % 39K, having mas 38.9637 u; 0.0118 atom % 40K, which
has mass of 40.0 u and is radioactive with t1/2 = 1.3 × 109 y and 6.88 atom % 41K having a
mass of 40.96184u. Calculate the specific activity of naturally occurring potassium.
3. A mixture of 239Pu and 240Pu has a specific activity of 6 × 109 dis/s/g, The half lives of the
isotopes are 2.44 × 104y and 6.08 × 103y specific activity of naturally occurring
potassium.