Chapter 9

Chemical Kinetics

Rate of a reaction
The rate (speed or velocity) of a reaction is the change in
concentration in per unit time.
x
t
or dxdt   xt  tx 
2 1

 2 1 

where x or dx is the concentration change, i.e., (x 2  x1 ) in the

time interval t or dt, i.e., (t  t ) . 2 1

Law of mass action and Rate constant

Law of mass action states that, the rate at which a substance
reacts is directly proportional to its active mass and the rate
at which a reaction takes place is proportional to the product
of the active masses of the reacting substances.
 Rate constant for the reaction, aA  bB  product is
 dx   dx 
Rate     [ A]a [B]b
 dt 
;    k [ A]a [B]b
 dt 

Here, k is rate constant and it is also known as velocity

constant.
If [ A]  [B]  1 mol / litre , then dx
dt
k

1
 Thus, rate constant k is also called specific reaction rate.
 Its value depends on the nature of reactant,
temperature and catalyst. It value is independent of reactants
concentration.
Unit of rate constant   mol
n 1
litre  1
  sec


Here, n is order of reaction.

Some Reactions
S. No. Chemical equation Rate law

 dx 
1. aA  bB  product    k [ A]a [B]b
 dt 

 dx 
2. aA  bB  product    k [ A]2 [B]0
 dt 

 dx 
3. Pt , 
2 H 2 O2   2 H 2 O  O2    k [H 2 O2 ]
 dt 

  dx 
4. CH 3 COOC 2 H 5  H 2 O 
H
    k [CH 3 COOC 2 H 5 ]
 dt 

CH3COOH  C2 H5 OH

2
 
C 12 H 22 O 11  H 2 O   dx 
5. Sucrose
H
   k [C12 H 22 O11 ]
 dt 
C6 H12 O6  C6 H12 O6
Glucose Fructose

 dx 
6. (CH 3 )3 CCl  OH   (CH 3 )3 COH  Cl     k [(CH 3 )3 CCl]
 dt 

  dx 
7. CH 3 Cl  OH  CH 3 OH  Cl     k [CH 3 Cl][OH  ]
 dt 

 dx 
8. 
C6 H 5 N 2 Cl  C6 H5 Cl  N 2    k [C6 H 5 N 2 Cl]
 dt 

 dx 
9. 
CH 3 CHO  CH 4  CO    k [CH 3 CHO ]3 / 2
 dt 

 dx 
10. H 2 O2  2 I   2 H   2 H 2O  I2    k [H 2 O 2 ][ I  ]
 dt 

 dx 
11. 2O3  3O2    k[O3 ] [O 2 ]
 dt 
2

Rate constant and other parameters of different order reactions

Order Rate constant Unit of rate (Half-life period) T50=
constant
0 k0 
x conc. time–1 a
t 2k 0
(mol L–1 s–1)

1 k1 
2 .303  a 
log10   , C  C0 e  k 1 t
time–1 (s–1) 0 .693
t ax  k1

3
 2.303 (a  x1 )
N  N 0 e k 1 t , k1  log10
(t2  t1 ) (a  x 2 )

2 1  1 1 x conc–1 time–1 1
k2      (for the
t  (a  x ) a  ta(a  x) k 2a

case when each reactant has (mol L–1) s–1

equal concentration) L mol–1 s–1
2 . 303  b(a  x ) 
k2  log 10   (for the
t(a  b )  a(b  x ) 
case when both reactants have
different concentration)

3 1  1 1  conc–2 time–1 3
k3    2
2 t  (a  x )2
a  2k 3 a 2
(mol L–1)–2 s–1

L2 mol–2 s–1

n 1  1 1  conc(1–n) time–1 2 n 1  1
kn   n 1
 n 1  ; n  2
(n  1)t  (a  x ) (a)  (n  1)k n (a)n 1
(mol L–1)(1–n) s–1

L(n–1) mol(1–n) s–1

Methods for determination of order of a reaction

Integration method
(i) The value of k is determined and checked for all sets of a, x
and t .
(ii) If the value of k is constant, the used equation gives the
order of reaction.
(iii) If all the reactants are at the same molar concentration,
the kinetic equations are :
4
 k 
2 .303
t
log 10
a
(a  x )
(For first order reactions)
1 1 
k 
1
t  a a  x 
(For second order reactions)
1  1 
k 
1
 
2 t  (a  x ) 2 a 2 
(For third order reactions)

Half-life method: The half-

life may be described as the amount of time it takes for a rea
ctant's concentration to fall to half of its original value.
This method is employed only when the rate law involved only
one concentration term.
t a ; t
1/2
1n
 ka ; log t  log k  (1  n) log a
1/2
1 n
1/ 2

If we plot a graph of log t vs log a, we gets a straight line with 1/ 2

slope (1  n) . We can find the order n by determining the slope.

If half-life at different concentration is given then,

n 1
1 1 (t1 / 2 )1  a 2 
(t1 / 2 )1  ; (t1 / 2 )2  ;  
a1n1 a 2n 1 (t1 / 2 )2  a1 

log10 (t1 / 2 )1  log10 (t1 / 2 )2  (n  1) [log10 a2  log10 a1 ]

log 10 (t1 / 2 )1  log 10 (t1 / 2 )2
n 1
(log 10 a 2  log10 a1 )

This relation can be used to find the ‘n’.

Plots of half-lives Vs concentrations (t1/2  a1–n)

Zero order 1st order 2nd order 3rd order
t1/2 
t1/2 

t1/2 
t1/2 

Conc. Conc. 1/a 1/a2

5
Graphical method:
A graphical method based on the respective rate laws, can
also be used.
(i) If the plot of log( a  x ) Vs t is a straight line, the reaction
follows first order.
(ii) If the plot of (a 1 x ) Vs t is a straight line, the reaction
follows second order.
(iii) If the plot of (a 1x ) Vs 2
t is a straight line, the reaction
follows third order.
(iv) In general, for a reaction of nth order, a graph of 1
(a  x )n 1
Vs
t must be a straight line.

Plots from
Zero order
integrated
1 order 2 order
rate equations
3 order
st nd rd
Conc. [A] 

log. [A] 

t t t t

6
Arrhenius equation
Arrhenius proposed a quantitative relationship between rate
constant and temperature as,
k  Ae  Ea / RT
…..(i)
The equation is called Arrhenius equation.
In which constant A is known as frequency factor. This factor
is related to number of binary molecular collision per second
per litre.
E is the activation energy.
a

T is the absolute temperature and

R is the gas constant
Both A and E are collectively known as Arrhenius a

parameters.
Taking logarithm equation (i) may be written as,
log k  log A 
E
2.303 RT
a
…..(ii)
The value of activation energy (E ) increases, the value of k
a

decreases and therefore, the reaction rate decreases.

log
k2

E a
1 1
   …..(iii)
k1 2 .303 R T T  1 2 

where k and k are rate constant at temperatures

1 2 T1 and T2

respectively (T  T ) . 2 1