Kinetic information for a given mechanism

Example 1.
Consider an overall reaction A B. It is believed to occur in two steps.
A 
k1
 A*
A* 
k2
B
Determine the kinetic expression for the rate of production of B.

Ans: Pseudo steady state assumption

d  A* 
 k1  A  k1  A*  0
dt
k1
 A*   A
k1

d  B k1
 k2  A*  k2  A  k  A
dt k1
We will get a first order reaction.

Example 2.

Consider an overall reaction 2A  B. It is believed to occur as follows

k1
A k1
A*
A  A* 
k2
B
Determine the kinetic expression for the rate of production of B.

Ans:
d  A* 
 k1  A  k1  A*   k2  A  A*  0
dt
k1  A
 A* 
k1  k2  A

d  B k1  A
2

 k2  A 
*
k2
dt k1  k2  A
Special cases:
d  B
If k-1 << k2[A], then  k2  A*  k1  A
dt

d  B k2 k1
 k2  A*   A
2
If k-1 >> k2[A], then
dt k1

Example 3:
Consider

2 NO   NO 
 k1

k1 2

 NO 2  O2 
k
 2  NO2 
2

Assume that the rate constant values at operating conditions are k2 k1 , k1 and the activation

energy is such that E1   E1  E2  . Determine the rate expression and the effective activation

energy.
Ans:

d  NO 2 
 k1  NO   k1  NO 2   k2  NO 2  O2  0
2

dt

k1  NO 
2
k1
 NO 2   NO (since k2
2
k1 , k1 )
k1  k2 O2  k1

d  NO2  k1k2
 k2  NO 2  O2   NO O2 
2

dt k1
 E1  E2  E1 
k1k2 k10 k20
It appears as a third order reaction. The rate constant can be written as  e RT
k1 k10

Since E1   E1  E2  , the effective activation energy will appear as negative.