98 Theories of reaction rates

Arrhenius equation and collision theory

The Arrhenius equation is

k2  A exp   Ea / RT  ... (8)
and according to the collision theory, the rate constant is given by
1/ 2
2  8kT 
k2  pN A AB   exp   E0 / RT  ... (9)
 µ 
Equation (9) may be written as
k2  K T exp   E0 / RT  ... (10)
where K represent a term which is independent of temperature and is given by
1/2
 8k 
2
K  pN A  AB  ... (11)
µ
The relation between the activation energy Ea (appeared in equation (8)) and the minimum energy E0 (appeared
in equation (10) may be obtained through the derivation of the expression d n  k / k 0  / dT . Equation (8)
gives
E0
n  k 2 / k 0   n  A / k 0  
RT
d n  k 2 / k 0  Ea
i.e.  ... (12)
dT RT 2
And equation (10) gives
1 E
n  k 2 / k 0   n  K / K 0   n  T / K   0 ... (13)
2 RT
d n  k 2 / k 0  1 E
i.e.   02 ... (14)
dT 2T RT
Equation (12) with (14), we have
Ea 1 E
2
  02
RT 2T RT
RT
Or, Ea 
2
 E0
www.careerendeavour.com ... (15)
Thus, the activation energy Ea shows temperature dependence. Since E0 is usually much larger than RT/2,
the difference between the Arrhenius activation energy Ea and the minimum energy E0 of the simple kinetic
theory is not sufficient.
Substitution of equation (15) and (10), we get
k2  K T exp   Ea  RT / 2  / RT 

Or, k2  K T e1/ 2 exp   Ea /RT 

Comparing the above relation with the Arrhenius equation, we have
A  K T e1/ 2
1/ 2
2  8k 
i.e. A  pN A AB   T e1/ 2 ... (16)
µ
Z AB 1/2
Or, A  pN A e ... (17)
N A* N B*
Theories of reaction rates 99
Problem: In collision theory of bimolecular gaseous reactions, the Collision frequency does not depend on
(a) Pressure of the system (b) Number of molecles of each gas
(c) Temperature of the system (d) Reduced mass of the system
Soln. Correct option is (a)

Lindemann theory of unimolecular reaction

Postulates:
1. The reactive molecules aquire activation energy for making collision with another.
2. The activation molecule does not decompose immediately
3. The activated molecule may disappear by either of the following two processes
(a) decomposition (b) deactivation
4. The process of deactivation by colliding with less energetic molecule will be favoured at high pressure and
the process of decomposition will be favoured at low pressure.
Step-1 : Activation process
k1
A  A   A*  A
Step-2 : Deactivation process (at high pressure)
A*  A k2
 A A
Step-3 : Deactivation process (at low pressure)
k3
A*   product
From step-1 and step-2

k1
A  A   *
A A  fast 
k 2

k3
A*   product  slow 
Therefore, the rate of reaction,
r  k3  A*  ... (1)
d
Apply SSA,  A*   0
dt  
2 *
k1  A  k2  A*   A  k3  A  0
www.careerendeavour.com
2
k1  A   A*   k 2  A  k3 
2
* k1  A
 A  
k3  k2  A
From (1),
2
k1k3  A
r
k3  k2  A

The above equation is known as rate law expression.

Since,   A  PA 
k1k3 PA2
r ... (2)
k3  k2 PA