Catalysis

The General procedure for

determination reaction
mechanism
This lecture is related to determination the rate limiting step in catalysis if it is adsorption, surface reaction or

desorption step. This can be done by measuring the initial rate of reaction as a function of concentration (or

pressure) graphically.

To do that, let us assume the following as reaction rate controlling steps and see what is the
response of varying the concertation (or pressure) on the rate of reaction.

1. Case 1. Surface reaction controlling

  𝐶𝐶
𝐶𝐴 𝐶𝐵−
𝐾 𝑒𝑞
− 𝑟 𝑠𝑢𝑟𝑓𝑎𝑐𝑒 =𝑘 𝑓 2
( 1+ 𝐾 𝐴 𝐶 𝐴 + 𝐾 𝐵 𝐶 𝐵 + 𝐾 𝐶 𝐶𝐶 )
  Assume initially there is no concertation of C, i.e

  Assume initially the concentration of A is equal to that of B, i.e

 
  Po   Po

  𝐶𝐶
𝐶𝐴 𝐶𝐵−
𝐾 𝑒𝑞
Substitute in the reaction − 𝑟 𝑠𝑢𝑟𝑓𝑎𝑐𝑒 =𝑘 𝑓 2
( 1+ 𝐾 𝐴 𝐶 𝐴 + 𝐾 𝐵 𝐶 𝐵 + 𝐾 𝐶 𝐶𝐶 )
rate expression, to obtain
an expression as a function 𝑃0 𝑃0
of pressure
 
− 𝑟 𝑠𝑢𝑟𝑓𝑎𝑐𝑒 = 𝐾 1
( )( )
2 2
−0
2
𝑃 𝑃
( 1+ 𝐾 (𝐴
2 )
+ 𝐾 ( 2 )+ 0)
0
𝐵
0
 2
  𝑃0 𝑃0 𝑃0

− 𝑟 𝑠𝑢𝑟𝑓𝑎𝑐𝑒 = 𝐾 1
( )( )2 2
−0
=𝐾
( ) 2
=
𝐾 𝑃 2
2
𝑜
2 1 2 2
𝑃 𝑃 𝑃 ( 1+ 𝐾 𝑃 )
(1+ 𝐾 ( 2 )+ 𝐾 ( 2 )+ 0) (1+( 𝐾 + 𝐾 ) ( 2 ))
𝐴
0
𝐵
0
𝐴 𝐵
0 3 0

 
• At low pressure, Po the denominator in the
expression above becomes 1>
  𝐾 3 𝑃0 and
can be neglected when comparing to 1.
2
−𝑟
  𝑠𝑢𝑟𝑓𝑎𝑐𝑒 = 𝐾 2 𝑃𝑜

 
• At high pressure, Po the denominator in the
expression above becomes 1<  𝐾 3 𝑃0 and

the number 1 can be neglected when

comparing to .

=  constant
 2. Case 2. Surface reaction controlling where B in gas phase

  𝐶𝐶
𝐶 𝐴 𝐶𝐵 −
𝐾 𝑒𝑞
− 𝑟 𝑠𝑢𝑟𝑓𝑎𝑐𝑒 =𝑘 𝑆𝑓 𝐾 𝐴 𝐶 𝑇
( 1+ 𝐾 𝐴 𝐶 𝐴 + 𝐾 𝐶 𝐶 𝐶 )

  Again, assume initially there is no concertation of C, i.e and

  =

   
• At low pressure, Po the denominator in the • At high pressure, Po the denominator in the
expression above becomes 1>
  𝐾 3 𝑃0 and expression above becomes 1<  𝐾 3 𝑃0 and

can be neglected when comparing to 1. the number 1 can be neglected when

−𝑟 2
  0 = 𝐾 2 𝑃𝑜 comparing to .

 − 𝑟 0 = 𝐾 4 𝑃 0
When plotting the initial rate of reaction with initial pressure we get the shape
 3. Case 3. Adsorption controlling

  =

  Assume initially there is no concertation of C, i.e and

  =

   
• At low pressure, Po the denominator in the • At high pressure, Po the denominator in the
expression above becomes 1>
  𝐾 2 𝑃0 and expression above becomes 1<  𝐾 2 𝑃0 and

can be neglected when comparing to 1. the number 1 can be neglected when

−𝑟
  0 =𝑘 1 𝑃0 comparing to .

 − 𝑟 0 =𝑐 𝑜𝑛𝑠𝑡𝑎𝑛𝑡
When plotting the initial rate of reaction with initial pressure we get the shape
 4. Case 4. Desorption controlling

  𝐶𝐶

− 𝑟 𝐷𝑒𝑠 . 𝐶 =𝑘 𝑐𝑓 𝐶 𝑇
( 𝐾𝑆𝐾 𝐴 𝐾 𝐵 𝐶𝐴 𝐶𝐵−
𝐾𝐶 )
¿¿

  Assume initially there is no concertation of C, i.e and

  𝑃0 𝑃0

−𝑟 𝐷𝑒𝑠 .𝐶 =𝑘 𝑐𝑓 𝐶 𝑇
( 𝐾𝑆𝐾 𝐴 𝐾𝐵
2 2
−0 )
¿¿

  𝐾 1 𝑃2𝑜
−𝑟 𝑜 = 2
( 1+ 𝐾 2 𝑃 0 + 𝐾 3 𝑃 𝑜)
   𝐾 1 𝑃2𝑜
− 𝑟𝑜 =
( 1+ 𝐾 2 𝑃 0 + 𝐾 3 𝑃2𝑜 )

 
• At low pressure, Po the denominator in the expression above becomes

2
 − 𝑟 0 = 𝐾 1 𝑃 𝑜

 
• At intermediate pressure, Po the denominator in the expression above becomes

=
 
   𝐾 1 𝑃2𝑜
− 𝑟𝑜 =
( 1+ 𝐾 2 𝑃 0 + 𝐾 3 𝑃2𝑜 )

• At high pressure, Po the denominator in the

expression above becomes

 1+ 𝐾 2
2 𝑃 0 < 𝐾 3 𝑃 𝑜

and the rate becomes constant.

 − 𝑟 0 =𝑐 𝑜𝑛𝑠𝑡𝑎𝑛𝑡