ERT 208/4 REACTION

ENGINEERING:
Catalysis & Catalytic Reaction
Mechanism
Part B: The Rate Limiting
Step…..

By; Mrs Hafiza Binti Shukor

ERT 208/4 REACTION ENGINEERING

SEM 2 (2009/2010)
 Rate Limiting Step??
When heterogeneous reactions are carried out at STEADY
STATE….the rate of each of the 3 reaction step in series
(adsorption, surface reaction & desorption) are equal to one
another.
r '  r
A AD
r r
s D

only ONE particular step in the series is usually found to be

RATE LIMITING @ RATE CONTROLLING
If we could make this particular step GO FASTER, the entire
reaction would proceed at accelerated rate.
It consist of first assuming a sequence of steps in the reaction.
In writing sequence choice, must made some;
a)mechanism (molecular @ atomic)
b)single @ dual sites reaction
ERT 208/4 REACTION ENGINEERING
SEM 2 (2009/2010)
 Rate Limiting Step??.....cont….
ASSUMPTION…..

All the steps are reversible reaction.

Activity of the surface towards adsorption, desorption @

surface reaction is INDEPENDENT of coverage.

The surface is essentially uniform as far as the various steps in

the reaction are concerned.

ERT 208/4 REACTION ENGINEERING

SEM 2 (2009/2010)
Rate Limiting Step??......cont…

EXAMPLE 1: ADSORPTION LIMITED REACTION

Synthesis of Ammonia
3 H  N  2 NH 2 2 3

Over an iron catalyst that proceeds by the following mechanism;

H 2
 2S  2H  S Rapid

N2 S  N2 S
Rate-Limiting
N2 S  S  2N S (adsorption of N2
molecules as an N
N  S  H  S  HN  S  S atom)
NH  S  H  S  H N  S  S 2
Rapid
H 2N S  H S  NH 3
S S
NH 3
S  NH 3
S
ERT 208/4 REACTION ENGINEERING
SEM 2 (2009/2010)
Rate Limiting Step??......cont…

EXAMPLE 2: SURFACE- LIMITED REACTION

Reactions between 2 noxious automobile products, CO
& NO
1
CO  NO  CO
Cu
2
 N 2
2

Over an Copper catalyst that proceeds by the following mechanism;

CO  S  CO  S Rapid
NO  S  NO  S

NO  S  CO  S  CO  N  S  S Rate-Limiting (CO2 & N2

2
are weakly adsorbed)
N S  N S  N2 S
Rapid
N2 S  N S 2

ERT 208/4 REACTION ENGINEERING

SEM 2 (2009/2010)
Rate Limiting Step??......cont…

Synthesizing a Rate Law, Mechanism, and Rate Limiting Step

EXAMPLE 3: DECOMPOSITION OF CUMENE TO FORM
BENZENE & PROPYLENE USING PLATINUM
CATALYZED

C 6 H 5 CH CH 3
2 C 3
H 6
C 3
H 6

C B P
3 STEPS REPRESENT THE MECHANISME FOR CUMENE DECOMPOSITION
C S  B S  P
C
C S  C S P B S  B S P
C B B

catalyst catalyst catalyst catalyst

Adsorption of Surface reaction to form Desorption of
cumene on the adsorbed benzene & benzene from
surface propylene in the gas surface
phase
ERT 208/4 REACTION ENGINEERING
SEM 2 (2009/2010)
Which step is Rate Limiting Step???
Adsorption r  k P C  k C 
AD A C V A C S

C S  C S
k  C C S 
K  r  k  P A
AD A C
CV  

 K 
c
k A
C

Surface Reaction r S  k S C C S  k S P P C B S
C S  B S  P kS  PP C 
K  rS k C  B S

S
k S S  C S 
 K S 

Desorption rD k D
P B S  k D
PB C V

B S  B S K 
1
B
K DB
rD k D
C B S K B
PB C V 

ERT 208/4 REACTION ENGINEERING

SEM 2 (2009/2010)
1) Is the ADSORPTION of cumene is Rate Limiting Step???

C S  C S
The rate of adsorption :

 C C S 
r AD k P CV  
A  C 
 K C 

Assumption For Adsorption Limited Reaction ;

Rate constant for this step (kA) is SMALL with respect to the
specific
rates of other steps (kS and kD).
Ratio rS/kS and rD/kD very SMALL (approximately 0)
Ratio rAD/kA is LARGE
ERT 208/4 REACTION ENGINEERING
SEM 2 (2009/2010)
Is the ADSORPTION of cumene is Rate Limiting Step???..cont..

The rate of adsorption :  C C S  ….(1)

r AD k P CV  
A  C 
 K C 
r: C '  r AD  r S  r D ….(2)
For steady state operation
 PP C  ….(3)
The surface reaction rate expressionr is : k S C  B S

S  C S 
 K S 
For adsorption limited reaction, kS is large…..so, we set
rS ;
 0 ….(4)
kS
So, rS  PP C 
  C C S
 B S
0

kS  K S 
PP C We evaluate CB.S to express
C C S  B S
….(5)
K S
CC.S in term of partial
pressure
ERT 208/4 REACTION ENGINEERING
SEM 2 (2009/2010)
Is the ADSORPTION of cumene is Rate Limiting Step???..cont..

The desorption rate expression is r:D  k D C B S  K B P B C V  ….(6)

For adsorption limited reaction, kD is large…..so, we set

rD ;
 0 ….(7)
rD kD
So,  C B S
K B
PB C V   0
kD
C B S
K B
PB C V ….(8)

Combine (5) and (8),

K B PB PP C V ….(9)
C C S 
K S

ERT 208/4 REACTION ENGINEERING

SEM 2 (2009/2010)
Is the ADSORPTION of cumene is Rate Limiting Step???..cont..

We know that ,,

 C C S 
r AD k P CV  
A  C 
 K C 
Put (9) in above equation;

 K B PB C V PP 
r AD k P CV   This terms is simply the overall
A  C  partial pressure equilibrium
 K SK C  constant for this reaction.
C  B P
 K B PB PP 
r AD k CV P  
A  C 
 K SK C  Where…
 PB PP  
K SK
….(11)
 P  
C
r AD k CV ….(10) K P
A C
K
 K P  B

ERT 208/4 REACTION ENGINEERING

SEM 2 (2009/2010)
Is the ADSORPTION of cumene is Rate Limiting Step???..cont..

To eliminate Cv, we use SITE BALANCE,

Total sites ,Ct Cv + CC.S. + CB.S ….(12)
=
Vacan Occupied Site
t Site (cumene &
Put (8) and (9) in (12)…….. benzene adsorb
K B PB C V PP on the surface)
Ct C  V
K B
PB C V
K S

Solving for Cv,

K B PB PP
Ct C V
1  K B
PB 
K S
Ct
So… C V  ….(13)
K B P B PP
1 K B
PB
K S
ERT 208/4 REACTION ENGINEERING
SEM 2 (2009/2010)
Is the ADSORPTION of cumene is Rate Limiting Step???..cont..
Now, we put (13) in (10)……..

 PB PP 
r AD k A
CV  P 
C

 K P 
 
 
r AD k  Ct  P  PB PP 

A
 K B PB PP  C

 
K
1  K B
PB P

 K S 
So…
k A C t ( PC P PP / K P )
r ' r  S
….(14)
1  K B PB PP / K K
c AD

S B
PB

ERT 208/4 REACTION ENGINEERING

SEM 2 (2009/2010)
Is the ADSORPTION of cumene is Rate Limiting Step???..cont..
Now, we wish to sketch a plot of the initial rate as a function of
partial pressure of cumene,Pco
Initially, no product are present, so…P p  P B  0

So…the initial rate,

k A C t ( PC P PP / K P )
r ' r  S

1  K B PB PP / K K
c AD

S B
PB

r CO
'  k A C t PCO  kP CO

If the cumene initial rate, r CO '

decomposition is
ADSORPTION LIMITED,
then the initial rate will be
linear with the initial
partial pressure of initial partial pressure of cumene,Pco
cumene ERT 208/4 REACTION ENGINEERING
SEM 2 (2009/2010)
2) Is the SURFACE REACTION of cumene is Rate Limiting
Step???
C S  B S  P

The rate of SURFACE REACTION :

 PP C 
rS k C  B S
 ….(1)
S  C S 
 K S 

Since we cannot readily measure the conc of the adsorbed species, we must utilize the
adsorption & desorption step to eliminate CC.S and CB.S from this equation.

Assumption For SURFACE REACTION Limited Reaction ;

Rate constant for kA is LARGE (rAD)
Rate constant for kD is LARGE (rD)
Rate constant for kS is SMALL (rAD)
Ratio rAD/kA and rD/kD very SMALL (approximately 0)
Ratio rS/kS is LARGE ERT 208/4 REACTION ENGINEERING
SEM 2 (2009/2010)
Is the SURFACE REACTION of cumene is Rate Limiting
Step???..cont..
 C   ….(2)
The adsorption rate expression isr :  k  P C   C S

  AD A C V

 K  C

For adsorption limited reaction, kA is large…..so,;

r AD
0 ….(3)
So, kA

r AD C C .S
P C
CV 
kA K C

C C .S
0 P C
CV 
K C

C C .S K C
PC C V ….(4)

ERT 208/4 REACTION ENGINEERING

SEM 2 (2009/2010)
Is the SURFACE REACTION of cumene is Rate Limiting
Step???..cont..

The desorption rate expression is r:D  k D C B S  K B P B C V  ….(5)

For SURFACE REACTION limited reaction, kD is large…..so, we set ;

rD
 0 ….(6)
kD
rD
So,  C B S
K B
PB C V   0
kD
C B S
K B
P B C V ….(7)

ERT 208/4 REACTION ENGINEERING

SEM 2 (2009/2010)
Is the SURFACE REACTION of cumene is Rate Limiting
Step???..cont..

Now, put (4) and (7) in (1)….

 PP C 
rS k C  B S

S  C S 
 K S 
 PP K B PB C V 
rS k K PC C V  
S  C 
 K S 
 PP K B PB 
rS k CV K PC  
S  C 
 K S 
We know that,,
 PP PB 
rS k K CCV  P   ….(8) K SK
S C
C
K ….(9)
 K P  K B
P

ERT 208/4 REACTION ENGINEERING

SEM 2 (2009/2010)
Is the SURFACE REACTION of cumene is Rate Limiting
Step???..cont..

Site Balance….

Ct  C C
V B S
C C S ….(10)

Ct C K V P
PB C V K C
PC C V
Ct C V
(1  K B P B K C
PC )
Ct ….(11)
CV 
1  K B PB K C
PC

ERT 208/4 REACTION ENGINEERING

SEM 2 (2009/2010)
Is the SURFACE REACTION of cumene is Rate Limiting
Step???..cont..

Put (11) in (8)….

 Ct  PP PB 
rS k K   P  
S C 1  K K  C

 B
PB C
PC  K P 

k S K C C t ( PC P P /K )
r'  r  P B P

1 K P K P
c S

B B C C

ERT 208/4 REACTION ENGINEERING

SEM 2 (2009/2010)
Is the SURFACE REACTION of cumene is Rate Limiting
Step???..cont..
Now, we wish to sketch a plot of the initial rate as a function of
partial pressure of cumene,Pco
Initially, no product are present, so…P p  P B  0

So…the initial rate, k S K C C t ( PC P K /K )

r'  r  P B P

1 K P K
c S

B B C
PC

k S K C C t PCO
r'  r 
1  K C PCO
c CO

kP CO
where,
r'  r 
c CO
1  K C PCO k k S
K CCt

ERT 208/4 REACTION ENGINEERING

SEM 2 (2009/2010)
Is the SURFACE REACTION of cumene is Rate Limiting
Step???..cont..
At low partial pressure of K C PCO  1
cumene,
kP CO
We observed that the initial rate  r ' c  r CO 
will increase linearly with the 1  K C PCO
initial pressure of cumene. r CO '  kP CO

At high partial pressure of cumene,K C PCO  1

kP CO
r'  r 
We observed that the initial rate c CO
1  K C PCO
will independent with the initial
pressure of cumene. kP CO k
r'  r
c CO
 
K C PCO K C

ERT 208/4 REACTION ENGINEERING

SEM 2 (2009/2010)
Is the SURFACE REACTION of cumene is Rate Limiting
Step???..cont..

Figure show that the initial rate of reaction as a function of initial

partial pressure of cumene for the case of surface reaction
controlling..
initial rate,  r CO '

initial partial pressure of cumene,Pco

ERT 208/4 REACTION ENGINEERING

SEM 2 (2009/2010)
3) Is the DESORPTIONof cumene is Rate Limiting Step???
B S  B S
The rate of DESORPTION:

rD k D
C B S K B
PB C V  ….(1)

Assumption For DESORPTION Limited Reaction ;

Rate constant for kA is LARGE (rAD)
Rate constant for kS is LARGE (rS)
Rate constant for kD is SMALL (rD)
Ratio rAD/kA and rS/kS very SMALL (approximately 0)
Ratio rD/kD is LARGE

ERT 208/4 REACTION ENGINEERING

SEM 2 (2009/2010)
Is the DESORPTIONof cumene is Rate Limiting Step???..
cont..

 C C S  ….(2)
The adsorption rate expression isr AD:  k A P CV  
 C 
 K C 
For adsorption limited reaction, kA is large…..so,;
r AD
0 ….(3)
So, kA

r AD C C .S
P C
CV 
kA K C

C C .S
0 P C
CV 
K C

C C .S K C
PC C V ….(4)

ERT 208/4 REACTION ENGINEERING

SEM 2 (2009/2010)
Is the DESORPTION of cumene is Rate Limiting Step???..
cont..

The SURFACE REACTION rate expression is :

 PP C 
rS k C  B S
 ….(5)
S  C S 
 K S 
For DESORPTION limited reaction, kS is large…..so, we set ;
rS
 0 ….(6)
kS

rS  PP C 
So,   C C S
 B S
0

K S  K S 

K S C C S ….(7)
C B S

PP

ERT 208/4 REACTION ENGINEERING

SEM 2 (2009/2010)
Is the DESORPTION of cumene is Rate Limiting Step???..
cont..

Now, put (4) and (7) in (1)….

rD k D
C B S K B
PB C V 

K C C S 
rD k D
 S
K B
PB C V 
 PP 
K K C Pc C V  We know that,,
rD k D
 S
K B
PB C V 
 PP  K SK Gas phase
C
K equilibrium
P 
P
PB K
rD k D
K SK C
  c
C V ….(8)
B
constant
P P
K P 

ERT 208/4 REACTION ENGINEERING

SEM 2 (2009/2010)
Is the DESORPTION of cumene is Rate Limiting Step???..
cont..

Site Balance….

Ct  C C
V B S
C C S ….(9)

K S C C S
Ct C KV c
Pc C V 
PP
K S K C PC
Ct C V
(1  K C PC  )
PP
Ct
CV  ….(10)
K S K C PC
1  K C PC 
PP

ERT 208/4 REACTION ENGINEERING

SEM 2 (2009/2010)
Is the DESORPTION of cumene is Rate Limiting Step???..
cont..

Put (10) in (8)….

 
 
P PB  Ct 
rD k KCK   C

D S
 K C K S PC 
P P
K P  1  K C
PC  
 PP 
P PB  K C K S PC
rD k D
C tK C K S
  C
 / 1  K C
PC 
P P
K P  PP

 PB PP 
kDC tK C K  P 
S C

r ' r   K P  ….(11)
K P K
C D
PP C
PC P C
K S PC

ERT 208/4 REACTION ENGINEERING

SEM 2 (2009/2010)
Is the DESORPTION of cumene is Rate Limiting Step???..
cont..

To determine the dependence of the initial rate on partial

pressure of cumene, we again set:
Initially, no product are present, so…P p  P B  0

 PB PP 
So…the initial rate, kDC tK C K  P 
S C

r '  rD   K P 
K P K
CO
PP C
PC P C
K S PC

initial rate,
r '
r CO
'  rD k D
Ct
CO

Initial rate independent of

the initial partial pressure of
cumene

initial partial pressure of cumene,Pco ERT 208/4 REACTION ENGINEERING

SEM 2 (2009/2010)
SUMMARY OF THE CUMENE DECOMPOSITION…

The experimental observation of –rco as a function of Pco are

shown in figure..from that, we clearly can see that either
adsorption nor desorption is RATE
C H LIMITING…
CH CH   C H  C H
initial rate,  r CO '
6 5 3 2 3 6 3 6

C B P

initial partial pressure of cumene,Pco

The rate law derived by assuming that SURFACE REACTION is
RATE LIMITING agrees with experimental data.
Eley-Rideal
Mechanism-reaction
k S K C C t ( PC P K /K )
r'  r  P B P between adsorbed
1 K P K molecule & a
c S
PC
P B C molecule in the gas
phase.
ERT 208/4 REACTION ENGINEERING
SEM 2 (2009/2010)
ALGORITHM FOR DETERMINING REACTION
MECHANISM & RATE LIMITING STEP…
1) Select a mechanism for adsorption, surface reaction &
desorption (treat each reaction step as an elementary
reaction when writing rate law)
2) Assume a rate limiting step. Choose the SURFACE REACTION
first since >than 75% of all heterogeneous reactions that are
not diffusion limited are surface reaction limited.
3) Write down the rate law for surface reaction step
4) Solve concentration of adsorbed species using other step
that are not limiting reaction. (expression for adsorption &
desorption rate law)
5) Assume, ratio rAD/kA and rD/kD very SMALL (approximately 0)
6) Write a site balance
7) Derive the rate law by combining step (2,3,4,5,6)
8) Compare with data experiment- if they agree, its mean you
have found the correct mechanism & rate limiting step. If not,
assume a different rate limiting step ENGINEERING
ERT 208/4 REACTION and different
SEM 2 (2009/2010)
mechanism.
End of Part B

ERT 208/4 REACTION ENGINEERING

SEM 2 (2009/2010)