Lecture 14 Thursday 2/21/08

Pseudo Steady State Hypothesis

(PSSH)

Net Rate of Reaction of Active Intermediates is Zero
Hall of Fame Reaction: 2NO +O
2
2NO
2


An active intermediate is a molecule that is in a highly energetic and reactive
state It is short lived as it disappears virtually as fast as it is formed. That is,
the net rate of reaction of an active intermediate, A*, is zero.



The assumption that the net rate of reaction is zero is called the Pseudo
Steady State Hypothesis (PSSH)

r
A*
= r
iA

=0

Example

The rate law for the reaction



is found from experiment to be





How did this rate law come about? Suggest a mechanism consistent with the
rate law.

AB+C

r
A
=
kC
A
2
1+ ' k C
A
For reactions with active intermediates, the reaction coordinated discussed in
Chapter 3 now has trough in it and the active intermediate, A*, sits in this
trough
Solution

(1)



(2)



(3)


A+A
k
1
A*+A

A*+A
k
2
A+A

A*
k
3
B+C

r
2A*
= k
2
C
A*
C
A

r
3A*
= k
3
C
A*

r
1A*
= k
1
C
A
2
Rates
Laws

Reaction (1) (1)

Reaction (2) (2)

Reaction (3) (3)

Relative Rates

(4)

r
1A*
= k
1
C
A
2

r
2A*
= k
2
C
A
C
A*

r
3A*
= k
3
C
A*

r
1A
= r
1A*
, r
3B
= r
3A*
Net Rates: Rate of Formation of Product

(4)

(5)

(6)

Solving for

(7)

r
B
= r
3B
= r
3A*
= k
3
C
A*

r
A*
= r
1A*

=r
1A*
+r
2A*
=r
3A*

= k
1
C
A
2
k
2
C
A
C
A*
k
3
C
A*
= 0

C
A*
=
k
1
C
A
2
k
3
+ k
2
C
A

C
A*
Substituting for in Equation (4) the rate of formation of B is

(8)

Relative rates overall





(9)

C
A*

r
B
=
k
1
k
3
C
A
2
k
3
+ k
2
C
A

AB+C

r
A
1
=
r
B
1

r
A
= r
B
=
k
1
k
3
C
A
2
k
3
+k
2
C
A
For high concentrations of A, we can neglect with regard to , i.e.,


and the rate law becomes

(10)

Apparent first order.



k
3

k
2
C
A

k
2
C
A
>> k
3

r
A
=
k
1
k
3
k
2
C
A
= kC
A
For low concentrations of A, we can neglect with regard to , i.e.,


and the rate law becomes

(11)

Apparent second order

Dividing by and letting and we have the rate law we
were asked to derive


(12)

k
3
>> k
2
C
A

r
A
=
k
3
k
1
k
3
C
A
2
= 2k
1
C
A
2

r
A
=
kC
A
2
1+ ' k C
A

k
3

' k =
k
2
k
3

k = k
1

Active Intermediates
A B + C
Propose a mechanism



Treat each step as elementary



But C*
A
cannot be measured since it is so small



The rate law found experimentally matches this proposed reaction mechanism
A
A
A
C k
kC
r
` 1
2
+
=
C B A
A A A A
A A A
k
k
k
+
+ +
+
3
2
1
* ) 3 (
* ) 2 (
* ) 1 (
*
3
*
3 * 3
*
3 A
*
2 * 2
2
1 * 1

C
B : Product
A B A A A
A B A A
A A
C k r r C k r
C k r C k r
C k r
= = =
= =
=
B+C
A+A
A*
A
A
A
A
A
A
A
A
A
A
A A A A A
A A A A A A A A
C k
kC
C k k
C k
C k k
C k k
r
C k k
C k
C
C k C C k C k r PSSH
C k C C k C k r r r r
` 1 1

0 , 0 set
2
3 2
2
1
2 3
2
1 3
2 3
2
1
*
*
3
*
2
2
1 *
*
3
*
2
2
1 * 3 * 2 * 1 *
+
=
+
=
+
=
+
=
= =
= + + =
What about
A
A
A A A
C k
kC
r kC r
` 1

+
= =
C B A
I A I A
I A I A
k
k
k
+
+ +
+ +
3
2
1
* ) 3 (
* ) 2 (
* ) 1 (
C B A
A A A A
I A I A
I A I A
k
k
k
k
+
+ +
+ +
+ +
4
3
2
1
) 4 (
* ) 3 (
* ) 2 (
* ) 1 (
2NO + O
2
2NO
2





Product NO
2

NO
NO NO
k
NO NO
k
O NO
NO
k
C C k r NO NO N
C k r O NO N
C C k r NO O N
*
3
*
2
3
*
3
*
2
2
2
*
3
1
3
3
2
*
3
2
2
2
*
3
1
1
*
3 2
2 O ) 3 (
O ) 2 (
O ) 1 (
= +
= +
= +
2 2
2
2
2
*
3
*
3
*
3
2
*
3
*
3
3 2
2
2
3 1
3 2
3 2
2
3 1
3 2
1
3 2 1
3 3
2
C high at very except k 2
0
2 2
O NO NO
NO
O NO
NO
NO
O NO
NO
NO
NO NO
O NO
NO
NO
NO
NO NO
C C
k
k k
r
k
C k k
C C k k
r
C k k
C C k
C
C C k C k C C k r
C C k r r
~
>>
+
=
+
=
= =
= =