The Rate Limiting Step in A Catalytic

Reaction
Chemical Reaction Engineering (CRE) is the
field that studies the rates and mechanisms of
chemical reactions and the design of the reactors
in which they take place.
 Steps in a Single-Site Catalytic Reactor
 C A S 
Adsorption A S  A S  rA  rAd  k Ad  PACv  
 k A 

 C B S 
Surface Reaction A  S  B  S  rA  rS  k S C A S  
 k C 

Desorption BS  BS  rA  rD  k D C B S  k B PB C B 

Which step is the Rate Limiting Step (RLS)?

2
 The Rate Limiting Step:
Which step has the largest resistance?

Electrical analog to heterogeneous reactions

3
 Collecting and Analyzing Data

Collecting information for catalytic reactor design

4
 Collecting and Analyzing Data

5
 Catalytic Reformers
Normal Pentane Octane Number = 62
Iso-Pentane Octane Number = 95

6
 Catalytic Reformers
0.75 wt% Pt
n-pentane i-pentane
Al2O3

-H2 Al2O3 +H2

n-pentane n-pentene i-pentene i-pentane
Pt Pt

Al2O3
n-pentene i-pentene

N I

7
 Catalytic Reformers
Isomerization of n-pentene (N) to i-pentene (I) over alumina
Al2O3
N I

1. Select a mechanism (Mechanism Single Site)

Adsorption on Surface: N S  N S
Surface Reaction: N S  IS
Desorption: IS  I  S
Treat each reaction step as an elementary reaction when writing rate laws.
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 Catalytic Reformers
2. Assume a rate-limiting step.
Choose the surface reaction first, since more than 75%
of all heterogenous reactions that are not diffusion-
limited are surface-reaction-limited. The rate law for the
surface reaction step is:
N SS  ISS

 C 
 rN   r  rS  k S  C NS 
I
' I S

 KS 

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 Catalytic Reformers
3. Find the expression for the concentrations of
the adsorbed species
CN.S and CI.S. Use the other steps that are not limiting to
solve for CN.S and CI.S. For this reaction:

N S  N S
rAD
From  0: C NS  PN K N C 
kA
IS  I  S
rD PI C 
From  0: C IS   K I PI C 
10
kD KD
 Catalytic Reformers
4. Write a Site Balance.

C t  C   C NS  C IS

5. Derive the rate law. Combine steps 2, 3 and 4 to

arrive at the rate law :
 k 
 k s Ct K N PN  PI K P 
 rN  rS 
1  K N PN  K I PI 
k PN  PI K P 
 rN   rS 
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1  K N PN  K I PI 
Catalytic Conversion of Exhaust Gas

1994 2004 2008

HC 0.41 0.125 0.10
CO 3.4 3.4 3.4
NO 0.4 0.4 0.14

1
CO  NO  CO 2  N 2
2


 Catalytic Conversion of Exhaust Gas

  C 
NO  S NO • S rANO  k NO PNO C V  NO •S  C NO •S  K NO PNO C V
  K NO 

  C 
CO • S CO • S rACO  k CO PCO C V  CO•S  C CO•S  K CO PCO C V
  K CO 

CO • S  NO • S  CO 2  N • S  S rS  k S C CO•S C NO •S 


N •S N •S

N 2 g   2S 
rD  k D C 2N•S  K N 2 PN 2 C 2V  C N•S  C V K N PN 2

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 Catalytic Conversion of Exhaust Gas

rS  k S C NO•SCCO•S 

rS  k SK NOKCO PNOPCO C 2V
C T  C V  C NO•S  CCO•S  C N•S

 C V  C V K NOPNO  C V KCO PCO  C V K N 2 PN 2

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 Catalytic Conversion of Exhaust Gas
Ct
CV 
1  K NO PNO  K CO PCO  K N 2 PN 2
   k  
k S K NO K CO C 2t PNO PCO
  rS 
 rNO
1  K NO PNO  K CO PCO  K N 2 PN 2 
2

kPNO PCO
 
 rNO
1  K NO PNO  K CO PCO  K N 2 PN 2 
2

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 Catalytic Conversion of Exhaust Gas
kPNOPCO
 
rNO
1 K NOPNO  KCOPCO  
2
K N 2 PN 2

Neglect K N 2 PN 2
kPNOPCO
  
rNO 2
1 K NOPNO  KCO PCO 



Catalytic Conversion of Exhaust Gas
kPNOPCO
 
rNO 2
1 K NOPNO  KCO PCO 
Find optimum partial pressure of CO
drNO 
0
dPCO

1 K NOPNO
PCO 
KCO

