THE LINDEMANN-HINSHELWOOD MECHANISM

It is the first successful explanation of unimolecular reactions by

Frederick Lindemann in 1921 and then elaborated by Cyril
Hinshelwood.

A+A

A* + A

(activation)

[ ]

= []2

The excited molecule may undergo:

A* + A

A + A (deactivation of A*)

[ ]

= [ ]

or
A*

(unimolecular decay to product)

[ ]

= [ ]

In order to determine the overall rate law, we apply the steadystate approximation to the net rate formation of A:

=

Solving for [ ]:

[ ] =

[]2
+ []

So the rate of formation of P:

2

= [ ] =

[]2
=

+ []
Case 1: If the rate of deactivation by (A*, A) collision is much
greater than the unimolecular decay, the reaction is first order.
Ka[A*][A]>>Kb[A*] or Ka[A]>>Kb, neglecting Kb since it is small
enough,

= []

(FIRST ORDER)

Case 2: If the concentration (or partial pressure) of A is reduced, the

reaction switches to second order kinetics.
Ka[A*][A]<<Kb[A*] or Ka[A]<<Kb, neglecting Ka[A]

= []2 (SECOND ORDER)

AND SO, if we write the full rate law

[]2
=

+ []
as

= []

[]
+ []

Then the effective rate constant, k, can be arranged to:

1

1
[]

A test of the theory is to plot 1/K against 1/[A] and to expect a

straight line.