Catalysis – continue

(Adsorption resistance
controlling)
For the catalytic reaction A+BC

We will have four main intermediate steps; adsorption of A and B by the surface of the catalyst, surface reaction of both adsorbed A and B, and desorption of
the produced C from the surface of the catalyst.
This class we will consider the adsorption of A is the controlling step:

Adsorption (controlling)
  𝐴+ 𝑋 ↔ 𝐴 ∗ 𝑋
 𝐵 + 𝑋↔ 𝐵∗𝑋
Surface Reaction   𝐴 ∗ 𝑋+ 𝐵 ∗ 𝑋 ↔ 𝐶 ∗ 𝑋 + 𝑋

Desorption 𝐶 ∗ 𝑋 ↔𝐶 + 𝑋
 
The rate of reaction for controlling step (Adsorption of A) is
  𝐶 𝐴∗ 𝑋
−𝑟 𝐴𝑑𝑠 . 𝐴 =𝑘 𝐴𝑓
( 𝐶𝐴 𝐶𝑣 −
𝐾𝐴 )
But the surface concentration for B and C were developed previously as

𝐶
  𝐵∗𝑋= 𝐾𝐵 𝐶𝐵 𝐶𝑣
𝐶
  𝐶 ∗ 𝑋 =𝐾 𝐶 𝐶 𝐶 𝐶 𝑣

But from the surface reaction step we have:

𝐶𝐶 ∗ 𝑋 𝐶 𝑣
 𝐾 =
𝑆
=
 
𝐶 𝐴∗ 𝑋 𝐶𝐵∗ 𝑋
 The site balance is

𝐶
  =𝐶
𝑇 𝐴 ∗ 𝑋 +𝐶 𝐵 ∗ 𝑋 +𝐶 𝐶 ∗ 𝑋 +¿ 𝐶 𝑣 ¿

 𝐾 𝐶 𝐶𝐶 𝐶 𝑣
or 𝐶𝑇 = + 𝐾 𝐵 𝐶 𝐵 𝐶 𝑣 + 𝐾 𝐶 𝐶 𝐶 𝐶 𝑣 +¿ 𝐶 𝑣 ¿
𝐾 𝑆 𝐾𝐵 𝐶𝐵

𝐶 𝑇 =𝐶 𝑣 ¿
 

 
=

  = =
   =   =

  =

  =
or
 Catalysis – continue
(Desorption resistance
controlling)
Adsorption
  𝐴+ 𝑋 ↔ 𝐴 ∗ 𝑋
 𝐵 + 𝑋↔ 𝐵∗𝑋
Surface Reaction   𝐴 ∗ 𝑋+ 𝐵 ∗ 𝑋 ↔ 𝐶 ∗ 𝑋 + 𝑋

Desorption (controlling)  
𝐶 ∗ 𝑋 ↔𝐶 + 𝑋
The rate of reaction for controlling step (Desorption of C) is
  𝐶𝐶 𝐶 𝑣
−𝑟 𝐷𝑒𝑠 .𝐶 =𝑘 𝑐𝑓 ( 𝐶𝐶∗𝑋 −
𝐾𝐶 )
But the surface concentration for A and B were developed previously as

𝐶
  𝐵∗ 𝑋= 𝐾𝐵 𝐶 𝐵 𝐶𝑣
𝐶  𝐴 ∗ 𝑋 =𝐾 𝐴 𝐶 𝐴 𝐶 𝑣
And the surface equilibrium reaction

 𝐾 = 𝐶𝐶 ∗ 𝑋 𝐶 𝑣  
𝑆 Re-arrange to get
𝐶 𝐴∗𝑋 𝐶𝐵∗𝑋

𝐶
  𝐵∗𝑋= 𝐾𝐵 𝐶𝐵 𝐶𝑣
 
𝐶  𝐴 ∗ 𝑋 =𝐾 𝐴 𝐶 𝐴 𝐶 𝑣

or 𝐶  𝐶 ∗ 𝑋 =𝐾 𝑆 𝐾 𝐴 𝐾 𝐵 𝐶 𝐴 𝐶 𝐵 𝐶 𝑣
  𝐶𝐶 𝐶 𝑣
(
−𝑟 𝐷𝑒𝑠 .𝐶 =𝑘 𝑐𝑓 𝐾 𝑆 𝐾 𝐴 𝐾 𝐵 𝐶 𝐴 𝐶 𝐵 𝐶 𝑣 −
𝐾𝐶 )
  𝐶𝐶
(
−𝑟 𝐷𝑒𝑠 .𝐶 =𝑘 𝑐𝑓 𝐶 𝑣 𝐾 𝑆 𝐾 𝐴 𝐾 𝐵 𝐶 𝐴 𝐶 𝐵 −
𝐾𝐶 )
 The site balance is
𝐶  𝐶 ∗ 𝑋 =𝐾 𝑆 𝐾 𝐴 𝐾 𝐵 𝐶 𝐴 𝐶 𝐵 𝐶 𝑣
𝐶
  =𝐶
𝑇 𝐴 ∗ 𝑋 +𝐶 𝐵 ∗ 𝑋 +𝐶 𝐶 ∗ 𝑋 +¿ 𝐶 𝑣 ¿

or
𝐶
  = 𝐾 𝐶 𝐶 +𝐾 𝐶 𝐶 +𝐾 𝐾 𝐾 𝐶 𝐶 𝐶 +¿ 𝐶 ¿
𝑇 𝐴 𝐴 𝑣 𝐵 𝐵 𝑣 𝑆 𝐴 𝐵 𝐴 𝐵 𝑣 𝑣

𝐶
  =𝐶 ( 𝐾 𝐶 + 𝐾 𝐶 + 𝐾 𝐾 𝐾 𝐶 𝐶 +1 )
𝑇 𝑣 𝐴 𝐴 𝐵 𝐵 𝑆 𝐴 𝐵 𝐴 𝐵

 
=
Substitute the vacant site in the rate equation

  𝐶𝐶
−𝑟 𝐷𝑒𝑠 .𝐶 =𝑘 𝑐𝑓 𝐶 𝑣 ( 𝐾 𝑆 𝐾 𝐴 𝐾 𝐵 𝐶 𝐴 𝐶𝐵 −
𝐾𝐶 )
  𝐶𝑇
−𝑟 𝐷𝑒𝑠 . 𝐶 =𝑘 𝑐𝑓 ¿ ¿

  𝐶𝐶

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

 • If the denominator in the rate expression is raised to a power of 2 and contains the
expressions , then the controlling step is surface reaction of type I

• If the denominator contains only then the controlling step is surface reaction of type II
where B is reacted in gas phase with adsorbed A

• If the denominator contains a fraction of concentration of a species with respect to other

species such as , then adsorption of the remaining species is controlling, here the
remaining species is A

• If the denominator contains multiplication of concentration of more than one species such
as , then a desorption step of the remaining species is controlling. Here the desorption
step of the missing species C is the controlling.