135

HETEROGENEOUS
CATALYST & CATALYSIS
Dicky Dermawan
www.dickydermawan.net78.net
dickydermawan@gmail.com

ITK-329 Kinetika & Katalisis
136
Steps in Heterogeneous Catalysis
1. External diffusion of reactant to catalyst
2. Internal diffusion of reactant in catalyst's
macro- and micro pores
3. Adsorption of reactant on catalyst surface
4. Surface Reaction
5. Desorption of products from catalyst surface
6. Internal diffusion of products through micro- and macro pores
7. External diffusion of product away from catalyst
137
3
rd
Step: Adsorption
adalah hubungan antara konsentrasi zat yang teradsorpsi di
permukaan active site dengan tekanan parsial zat itu pada temperatur
tertentu pada saat kesetimbangan terjadi.
Adsorption Isoterm
Langmuirs model for the adsoption of gas on a solid catalyst
138
Adsorption
Molecular Adsorption
CO + S CO.S
CO +
C-O
Dissociative Adsorption
CO + 2S CS + OS
CO +
C O
139
f(T)
k
k
K where
K
C
C P k r C k C P k r
a
a
A
A
AS
v A a s AS a v A a s
= =
(

= =

A
AS
v A S
K
C
C P : thus , 0 r - : m equilibriu At = =
v A A v t AS v t
C P K C C C C C : Balance Site + = + =
Model for Molecular Adsorption
Pt surface
C
H H
C
H H
Pt surface
C
H H
C
H H
C H H
C
H H
CC HH HH
CC
HH HH
v A A AS
C P K C =
A A
t
v
P K 1
C
C
+
=
A A
A t A
AS
P K 1
P C K
C
+

= Langmuirs Adsorption Isoterm
k
a
k
-a
A
(g)
+ S AS
P
A
C
v
C
AS
k
a
k
-a
A
(g)
+ S AS
P
A
C
v
C
AS
140
C
AS
P
A
C
AS
P
A
C
AS
C
AS
P
A
t A
A A
AS
A
C K
P K 1
C
P

+
=
Behavior of Langmuir Adsorption Isoterm
A A
A t A
AS
P K 1
P C K
C
+

=
At low P:
t AS
C C ~
A t A AS
P C K C ~ (1
st

order)
At high P: (0
th
order)
Estimation of the parameters:
A A
A t A
AS
P K 1
P C K
C
+

=
A t A
A A
AS
P C K
P K 1
C
1

+
=
A
t t A AS
A
P
C
1
C K
1
C
P
+

=
P
A
AS
A
C
P
t
C
1
tan = o
P
A
AS
A
C
P
t
C
1
tan = o
141
( )
2 / 1
CO
2 / 1
A
2 / 1
CO t
2 / 1
A
OS
P K 2 1
P C K
C
+

=
|
|
.
|

\
|
=
A
OS CS
2
v CO a A
K
C C
C P k r
A
OS CS
2
v CO A
K
C C
C P 0 r

= =
Pt surface
H H
H H
H
H
H
H
Pt surface
H H
H H
H
H
H
H
Model for Dissociative Adsorption
k
a
k
-a
CO + 2S CS + OS
k
a
k
-a
CO + 2S CS + OS
A
2
OS
2
v CO OS CS
K
C
C P : thus , C C = =
v
2 / 1
CO
2 / 1
A OS
C P K C =
At equilibrium:
Site Balance:
C 2 C C C C C
OS v OS CS v t
+ = + + =
C P K 2 C C
v
2 / 1
CO
2 / 1
A v t
+ =

P K 2 1
C
C
2 / 1
CO
2 / 1
A
t
v
+
=
142
t A
2 / 1
CO A
OS
2 / 1
CO
C K
P K 2 1
C
P

+
=
Estimation of the parameters:
2 / 1
CO A
2 / 1
CO t A
OS
P K 2 1
P C K
C
+

=
2 / 1
CO t A
2 / 1
CO A
OS
P C K
P K 2 1
C
1

+
=
2 / 1
CO
t
t A
OS
2 / 1
CO
P
C
2
C K
1
C
P
+

=
Dissociative Adsorption
P
CO
1/2
AS
2 / 1
CO
C
P
t
C
2
tan = o
P
CO
1/2
AS
2 / 1
CO
C
P
t
C
2
tan = o
Heat of Adsorption
144
Types of Adsorption Isoterm
145
Sample Problem S7-6
The following data were obtained at 70
o
C for the equilibrium
adsorption of n-hexane on silica gel particles.
Consider weather the adsorption is molecular or dissociative and
estimate the corresponding parameters.


Partial Pressure of
C
6
H
14
in gas, atm
C
6
H
14
adsorbed, gmol
per gram gel
0.0020 1.05E-04
0.0040 1.60E-04
0.0080 2.72E-04
0.0113 3.46E-04
0.0156 4.30E-04
0.0206 4.73E-04
146
Sample Problem S7-7
The following data were obtained for the equilibrium adsorption
of n-hexane on the same silica gel particles at 110
o
C.
Consider weather the adsorption is molecular or dissociative and
estimate the corresponding parameters.


Partial Pressure of
C
6
H
14
in gas, atm
C
6
H
14
adsorbed, gmol
per gram gel
0.0005 2.60E-05
0.0010 4.50E-05
0.0020 7.80E-05
0.0050 1.70E-04
0.0100 2.70E-04
0.0200 4.00E-04
147
Sample Problem S7-10
148
Sample Problem S7-11
149
Sample Problem
The data below were recorded at constant temperature for the
adsorption of nitrogen on silica gel at -196
o
C. Consider weather
the adsorption is molecular or dissociative and estimate the
corresponding parameters.

Pressure, kPa
Volume of adsorbed per gram
of sample (mL at STP)
0.8 6.1
3.3 12.7
18.7 17.0
30.7 19.7
38.0 21.5
42.7 23.0
57.3 27.7
150
Adsorption Isotherm
Involving More Than One Species
Derive mathematical expression when 2 diatomic gases (say A
2
& B
2
)
simultaneously adsorbed in the same active site at the surface of a
catalyst if:
a. Both A
2
& B
2
molecularly adsorbed, i.e.



b. Both A
2
& B
2
dissociatively adsorbed, i.e.




c. A
2
molecularly adsorbed, B
2
dissociatively adsorbed, i.e.

S B S B
S A S A
2
k
k
2
2
k
k
2
b
b
a
a

BS 2 S 2 B
AS 2 S 2 A
b
b
a
a
k
k
2
k
k
2


+


+

BS 2 S 2 B
S A S A
b
b
a
a
k
k
2
2
k
k
2


+

151
4
th
Step: Surface Reaction
Langmuir Hinshelwood
mechanism for
hydrogenation of ethylene
to ethane
152
1. Langmuir - Hinshelwood: Single Site
Surface Reaction Mechanism
s
s
S
k
k
K

=
|
|
.
|

\
|
=
S
DS CS
BS AS s S
K
C C
C C k r
A
AS BS
B
|
|
.
|

\
|
=
S
BS
AS s S
K
C
C k r
2. Langmuir - Hinshelwood: Dual Site
AS+S S + BS
A B
C
AS + BS CS + DS
A D B C
D
|
|
.
|

\
|

=
S
v BS
v AS s S
K
C C
C C k r
3. Eley Rideal
AS + B CS+ D
A
C
B and D do not adsorbed on catalysts surface active site
|
|
.
|

\
|

=
S
D CS
B AS s S
K
P C
P C k r
153
5
th
Step: Desorption
( )
v C AC CS DC D
C P K C k r =
|
|
.
|

\
|

=
DC
v C
CS DC D
K
C P
C k r
k
d
k
-d
CS C + S
k
d
k
-d
k
d
k
-d
CS C + S
AC
DC
K
1
K =
154
Combining Ideas: Synthesizing Rate Law
Here, we assume that all diffusion processes (1,2,6,7)
are fast, so the overall processes will depend solely
on adsorption, surface reaction, and desorption.
As a base case, consider the decomposition of
cumene to form benzene and propylene:
6 3 6 6
catalyst
2 3 5 6
H C H C ) CH ( CH H C +
Mechanism:
This is a molecular adsorption,
Langmuir-Hinshelwood single site
mechanism
155
Combining Ideas: Synthesizing Rate Law
|
|
.
|

\
|
=
C
CS
v C A A
K
C
C P k r
( )
D
B B v B BS D B
K
1
K P C K C k r = =
|
|
.
|

\
|

=
S
P BS
CS s S
K
P C
C k r
k
A
k
-A
C + S CS
* Molecular adsorption of reactant
* Surface reaction
k
s
k
-s
CS BS + P
* Desorption
k
D
k
-D
BS B + S
Mechanism:
P B C
catalyst
+
C
P B
P
P
P P
K

=
156
What if..
Adsorption-controlling
|
|
.
|

\
|
=
C
CS
v C A C
K
C
C P k r
0
K
P C
C k r
S
P BS
CS s S
~
|
|
.
|

\
|

=
k
A
k
-A
C + S CS
Surface reaction will be in equilibrium:
Desorption will be in equilibrium:
P B
S
B
B B
t
v
P P
K
K
P K 1
C
C
+ +
=
S
P BS
CS
K
P C
C

=
v B B BS
C P K C =
( ) 0 P C K C k r
B v B BS D B
~ =
SITE BALANCE:
S
P v B B
v B B v t
CS BS v t
K
P ) C P K (
C P K C C
C C C C

+ + =
+ + =
P B C
catalyst
+
157
What if..
Adsorption-controlling (cont)
Finally, the rate
equation becomes:
P C S
B
K
1
K K
K
=

Consider the overall reaction as

equilibrium process, i.e. C B + P
From thermodynamics:
( )
|
|
|
|
.
|

\
|
=
C
S
P v B B
v C A C
K
K
P C P K
C P k r
P B
S
B
B B
t
v
P P
K
K
P K 1
C
C
+ +
=
S
P BS
CS
K
P C
C

=
v B B BS
C P K C =
|
|
.
|

\
|
=
AC
CS
v C A C
K
C
C P k ' r
|
|
.
|

\
|

+ +
=
B P
C S
B
C
P B
S
B
B B
t
A C
P P
K K
K
P
P P
K
K
P K 1
C
k ' r
P B C
catalyst
+
C S
B
eq , B eq , P
eq , C
K K
K
P P
P

; at equilibrium:
eq , C
eq , P eq , B
P
P
P P
K

=
) K ln( T R G
P
= A
Thus:
B B P B
S
B
P
B P
C 1
C
P K P P
K
K
1
K
P P
P k
' r
+ +
|
|
.
|

\
|

=
t A 1
C k k =
158
What if..
Surface Reaction-controlling
0
K
C
C P k r
C
CS
v C A A
~
|
|
.
|

\
|
=
|
|
.
|

\
|

= =
S
P BS
CS s S C
K
P C
C k r r
Adsorption will be in equilibrium:
Desorption will be in equilibrium:
C C B B
t
v
P K P K 1
C
C
+ +
=
v C C CS
C P K C =
v B B BS
C P K C =
( ) 0 P C K C k r
B v B BS D D
~ =
SITE BALANCE:
v C C v B B v t
CS BS v t
C P K C P K C C
C C C C
+ + =
+ + =
P B C
catalyst
+
k
s
k
-s
CS BS + P
159
What if..
Surface Rxn-controlling (cont)
C C B B
t
v
P K P K 1
C
C
+ +
=
P C S
B
K
1
K K
K
=

|
|
.
|

\
|
= =
S
P BS
CS s S C
K
P C
C k r r
Finally, the rate equation becomes:
P B C
catalyst
+
v B B BS
C P K C =
v C C CS
C P K C =
( )
|
|
.
|

\
|

=
S
P v B B
v C C s C
K
P C P K
C P K k r
|
|
.
|

\
|

+ +
=
P B
S
B
C C
C C B B
t
s C
P P
K
K
P K
P K P K 1
C
k r
|
|
.
|

\
|

+ +

=
P B
C S
B
C
C C B B
t C s
C
P P
K K
K
P
P K P K 1
C K k
r
( )
C C B B
K
P P
C 2
C
P K P K 1
P k
r
P
P B
+ +

=

t C s 2
C K k k =
160
What if..
Desorption-controlling
Derive the rate expression, i.e. r
C

for this case
if desorption of benzene is slow compared to all the
other steps
P B C
catalyst
+
k
A
k
-A
C + S CS
k
s
k
-s
CS BS + P
k
D
k
-D
BS B + S
Mechanism: Adsorption
Surface reaction
Desorption
lambat
cepat
cepat
161
What if..
Desorption-controlling
|
|
.
|

\
|
=
C
CS
v C A A
K
C
C P k r
Adsorption will be in equilibrium:
C C
P
C
C S
t
v
P K
P
P
K K 1
C
C
+ +
=
0
K
P C
C k r
S
P BS
CS s S
~
|
|
.
|

\
|

=
Surface reaction will be in equilibrium:
( )
P
v C C S
P
CS S
BS
P
C P K K
P
C K
C

=

=
v C C CS
C P K C =
( )
B v B BS D D C
P C K C k r ' r = =
SITE BALANCE:
v C C v
P
C
C S v t
CS BS v t
C P K C
P
P
K K C C
C C C C
+ + =
+ + =
P B C
catalyst
+
k
D
k
-D
BS B + S
162
What if..
Desorption-controlling (cont)
Finally, the rate
equation becomes:
P C S
B
K
1
K K
K
=

P B C
catalyst
+
( )
B v B BS D C
P C K C k ' r =
v C C CS
C P K C =
v
P
C
C S BS
C
P
P
K K C =
C C
P
C
C S
t
v
P K
P
P
K K 1
C
C
+ +
=
( )
B v B BS D C
P C K C k ' r =
|
|
.
|

\
|
=
B v B v
P
C
C S D C
P C K C
P
P
K K k ' r
|
|
.
|

\
|

+ +
=
B B
P
C
C S
C C
P
C
C S
t
D C
P K
P
P
K K
P K
P
P
K K 1
C
k ' r
|
|
.
|

\
|

+ +

=
B
C S
B
P
C
C C
P
C
C S
t C S
D C
P
K K
K
P
P
P K
P
P
K K 1
C K K
k ' r
|
|
.
|

\
|

+ +

=
P B
C S
B
C
P C C C C S P
t C S
D C
P P
K K
K
P
P P K P K K P
C K K
k ' r
( )
P C C C C S P
K
P P
C 3
C
P P K P K K P
P k
' r
P
P B
+ +

=

t C S D 3
C K K k k =
163
Summary for
k
A
k
-A
C + S CS
k
s
k
-s
CS BS + P
k
D
k
-D
BS B + S
P B C
catalyst
+
( )
B B P B
K
K
K
P P
C 1
C
P K P P 1
P k
' r
S
B
P
B P
+ +

=

( )
C C B B
K
P P
C 2
C
P K P K 1
P k
' r
P
P B
+ +

=

Mechanism:
( )
P C C C C S P
K
P P
C 3
C
P P K P K K P
P k
' r
P
P B
+ +

=

Adsorption
Surface reaction
Desorption
If adsorption is rate-limiting:
If surface reaction is rate-limiting:
If desorption is rate-limiting:
t A 1
C k k =
t C S D 3
C K K k k =
t C s 2
C K k k =
eq , C
eq , P eq , B
P
P
P P
K

=
B
C S
P
K
K K
K

=
) K ln( T R G
P
= A
Actually, which one is
the rate-limiting step?
term) adsorption (
term) force driving ( term) kinetic (
rate

=
164
The Use of Initial-Rate Method
P B C
catalyst
+
( )
B B P B
K
K
K
P P
C 1
C
P K P P 1
P k
' r
S
B
P
B P
+ +

=

( )
C C B B
K
P P
C 2
C
P K P K 1
P k
' r
P
P B
+ +

=

( )
P C C C C S P
K
P P
C 3
C
P P K P K K P
P k
' r
P
P B
+ +

=

If adsorption is rate-limiting:
If surface reaction is rate-limiting:
If desorption is rate-limiting:
Carried out experiments using pure C at various P
C,0
Thus.Initially P
B
= P
P
= 0
Read the rate of reaction at t = 0, i.e. r
C,0

( )
0 , C 1 0 , C
P k ' r =
( )
0 , C C
0 , C 2
0 , C
P K 1
P k
' r
+

=
( )
' k
P K K
P k
' r
3
C C S
C 3
C
=


=
-r
C

P
C,0
-r
C

P
C,0
' r
C

0 , C
P
' r
C

0 , C
P
-r
C,0

P
C,0
-r
C,0

P
C,0
165
The Use of Initial-Rate Method
P B C
catalyst
+
( )
C C B B
K
P P
C 2
C
P K P K 1
P k
' r
P
P B
+ +

=

Thus..


Experiment shows surface reaction is rate-limiting:
( )
0 , C C
0 , C 2
0 , C
P K 1
P k
' r
+

=
Experimental data:
166
Dual Site Mechanism
This is a molecular adsorption,Langmuir-Hinshelwood dual site mechanism
k
A
k
-A
C + S CS
k
s
k
-s
CS + S BS + PS
Mechanism:
Adsorption
Surface reaction
Desorption
k
D1
k
-D1
BS B + S
k
D2
k
-D2
PS P + S
If Surface Reaction is controlling:
( )
( )
2
P P C C B B
K
P P
C 2
C
P K P K P K 1
P k
' r
P
P B
+ + +

=

What if (a) adsorption (b) desorption is the rate-limiting step?
167
Dissociative Adsorption &
Dual Site Mechanism
P B C
catalyst
+
( )
( )
2
P P C C B B
K
P P
C 2
C
P K P K P K 1
P ' k
' r
P
P B
+ + +

=

If Surface Reaction is controlling:
k
A
k
-A
C + 2 S CS + CS
k
s
k
-s
CS +CS BS + PS
Mechanism: Adsorption
Surface reaction
Desorption
k
D1
k
-D1
BS B + S
k
D2
k
-D2
PS P + S
What if (a) adsorption (b) desorption is the rate-limiting step?
168
P10-3
A
169
Consider:
Influence of Adsorbed Inert
|
|
.
|

\
|
=
I
IS
v I I I
K
C
C P k r
Adsorbed inert will use some of the vacant site which should be used to
adsorbed the reactants, thus reducing the available site for the reaction.
This will retard the rate of overall reaction.
P B C
catalyst
+
k
A
k
-A
C + S CS
k
s
k
-s
CS BS + P
k
D
k
-D
BS B + S
Mechanism: Adsorption
Surface reaction
Desorption
k
I
k
-I
I+S IS
k
I
k
-I
k
I
k
-I
I+S IS
Adsorbed inert
|
|
.
|

\
|
=
C
CS
v C A A
K
C
C P k r
( )
B v B BS D B
P C K C k r =
|
|
.
|

\
|
=
S
P BS
CS s S
K
P C
C k r
Use Langmuir Hinshelwood approach to verify the abovementioned
conclusion if the reaction is:
a. Adsorption limiting
b. Desorption limiting
c. Surface reaction limiting

170
Effect of Adsorbed Inert:
If Adsorption-controlling
|
|
.
|

\
|
=
C
CS
v C A C
K
C
C P k r
0
K
P C
C k r
S
P BS
CS s S
~
|
|
.
|

\
|

=
k
A
k
-A
C + S CS
Surface reaction will be in equilibrium:
Desorption will be in equilibrium:
I I P B
S
B
B B
t
v
P K P P
K
K
P K 1
C
C
+ + +
=
S
P BS
CS
K
P C
C

=
v B B BS
C P K C = ( ) 0 P C K C k r
B v B BS D B
~ =
SITE BALANCE:
v I I
S
P v B B
v B B v t
IS CS BS v t
C P K
K
P ) C P K (
C P K C C
C C C C C
+

+ + =
+ + + =
P B C
catalyst
+
Inert will be in equilibrium:
0
K
C
C P k r
I
IS
v I I I
~
|
|
.
|

\
|
=
v I I IS
C P K C =
171
Effect of Adsorbed Inert
If Adsorption-controlling (cont)
Finally, the rate
equation becomes:
( )
|
|
|
|
.
|

\
|

=
C
S
P v B B
v C A C
K
K
P C P K
C P k ' r
|
|
.
|

\
|

+ + +
=
B P
C S
B
C
I I P B
S
B
B B
t
A C
P P
K K
K
P
P K P P
K
K
P K 1
C
k ' r
I I B B P B
S
B
P
B P
C 1
C
P K P K P P
K
K
1
K
P P
P k
' r
+ + +
|
|
.
|

\
|

=
S
P BS
CS
K
P C
C

=
v B B BS
C P K C =
|
|
.
|

\
|
=
AC
CS
v C A C
K
C
C P k ' r
P B C
catalyst
+
eq , C
eq , P eq , B
P
P
P P
K

=
) K ln( T R G
P
= A
v I I IS
C P K C =
I I P B
S
B
B B
t
v
P K P P
K
K
P K 1
C
C
+ + +
=
t A 1
C k k =
172
Summary
for the Effect of
Adsorbed Inert
P B C
catalyst
+
( )
B B P B
K
K
K
P P
C 1
C
P K P P 1
P k
' r
S
B
P
B P
+ +

=

( )
C C B B
K
P P
C 2
C
P K P K 1
P k
' r
P
P B
+ +

=

( )
P C C C C S P
K
P P
C 3
C
P P K P K K P
P k
' r
P
P B
+ +

=

k
A
k
-A
C + S CS
k
s
k
-s
CS BS + P
k
D
k
-D
BS B + S
Mechanism:
Adsorption
Surface reaction
Desorption
If adsorption is rate-limiting:
If surface reaction is rate-limiting:
If desorption is rate-limiting:
k
I
k
-I
I+S IS
k
I
k
-I
k
I
k
-I
I+S IS
Adsorbed inert
( )
I I B B P B
K
K
K
P P
C 1
C
P K P K P P 1
P k
' r
S
B
P
B P
+ + +

=

( )
I I C C B B
K
P P
C 2
C
P K P K P K 1
P k
' r
P
P B
+ + +

=

( )
P I I P C C C C S P
K
P P
C 3
C
P P K P P K P K K P
P k
' r
P
P B
+ + +

=

173
Reversible vs Irreversible Surface
Reactions
Compare the rate equations for hypothetical Langmuir Hinshelwood single-
site mechanism cases when surface reactions are rate-controlling.

Case A: Irreversible Reaction Case B: Reversible Reaction
Mechanism:
Surface reaction
k
A
k
-A
A + S AS
k
s
k
-s
AS BS
k
D
k
-D
BS B + S
Adsorption
Desorption
Surface reaction
k
A
k
-A
A + S AS
k
s
k
-s
AS BS
k
D
k
-D
BS B + S
Adsorption
Desorption
k
A
k
-A
A + S AS
k
A
k
-A
k
A
k
-A
A + S AS
k
s
k
-s
AS BS
k
s
k
-s
k
s
k
-s
AS BS
k
D
k
-D
BS B + S
k
D
k
-D
k
D
k
-D
BS B + S
Adsorption
Desorption
( )
B B A A
K
P
A t A s
S A
P K P K 1
P C K k
r ' r
P
B
+ +

= =
( )
B B A A
A t A s
S A
P K P K 1
P C K k
r ' r
+ +

= =
Mechanism:
Surface reaction
k
A
k
-A
A + S AS
k
s
AS BS
k
D
k
-D
BS B + S
Adsorption
Desorption
Surface reaction
k
A
k
-A
A + S AS
k
A
k
-A
k
A
k
-A
A + S AS
k
s
AS BS
k
D
k
-D
BS B + S
k
D
k
-D
k
D
k
-D
BS B + S
Adsorption
Desorption
Using the usual Hougen - Watson technique, it can be found that:
B A
catalyst
B A
catalyst

174
Langmuir Hinshelwood Single Site & Dual Site
Mechanism
Consider hypothetical case when irreversible surface reactions are rate-
controlling:
Langmuir - Hinshelwood: Dual Site
Mechanism:
Surface reaction
k
A
k
-A
A + S AS
k
s
AS +S S + BS
k
D
k
-D
BS B + S
Adsorption
Desorption
Surface reaction
k
A
k
-A
A + S AS
k
A
k
-A
k
A
k
-A
A + S AS
k
s
AS +S S + BS
k
D
k
-D
BS B + S
k
D
k
-D
k
D
k
-D
BS B + S
Adsorption
Desorption
Langmuir - Hinshelwood: Single Site
Mechanism:
Surface reaction
k
A
k
-A
A + S AS
k
s
AS BS
k
D
k
-D
BS B + S
Adsorption
Desorption
Surface reaction
k
A
k
-A
A + S AS
k
A
k
-A
k
A
k
-A
A + S AS
k
s
AS BS
k
D
k
-D
BS B + S
k
D
k
-D
k
D
k
-D
BS B + S
Adsorption
Desorption
Using the usual Hougen - Watson technique, it can be found that:
( )
B B A A
A t A s
S A
P K P K 1
P C K k
r ' r
+ +

= =
( )
( )
2
B B A A
A t A s
S A
P K P K 1
P C K k
r ' r
+ +

= =
B A
catalyst

B A
catalyst

What if (a) adsorption (b) desorption is the rate-limiting step?
175
Langmuir - Hinshelwood and Eley-Rideal
Mechanism
Consider hypothetical case when irreversible surface reactions are rate-
controlling:
Eley Rideal: Langmuir - Hinshelwood:
Using the usual Hougen - Watson technique, it can be found that:
( )
B B A A
D A t A s
S A
P K P K 1
P P C K k
r ' r
+ +

= =
( )
( )
2
D D B B A A
d A t A s
S A
P K P K P K 1
P P C K k
r ' r
+ + +

= =
Mechanism:
k
A
k
-A
A + S AS
k
s
AS + D
(g)
BS
k
D
k
-D
BS B + S
Adsorption
Surface reaction
Desorption
k
A
k
-A
A + S AS
k
A
k
-A
k
A
k
-A
A + S AS
k
s
k
s
AS + D
(g)
BS
k
D
k
-D
BS B + S
k
D
k
-D
k
D
k
-D
BS B + S
Adsorption
Surface reaction
Desorption
B D A
catalyst
+
B D A
catalyst
+
What if (a) adsorption (b) desorption is the rate-limiting step?
Mechanism:
k
A1
k
-A1
A + S AS
k
s
AS+DS BS + S
k
D
k
-D
BS B + S
Adsorption
Surface reaction
Desorption
k
A2
k
-A2
D + S DS
k
A1
k
-A1
A + S AS
k
A1
k
-A1
k
A1
k
-A1
A + S AS
k
s
AS+DS BS + S
k
s
AS+DS BS + S
k
D
k
-D
BS B + S
k
D
k
-D
k
D
k
-D
BS B + S
Adsorption
Surface reaction
Desorption
k
A2
k
-A2
k
A2
k
-A2
D + S DS
176
Behavior of Single Site, Dual Site, and Eley-
Rideal Mechanism (cont)
( )
B B A A
A t A s
S A
P K P K 1
P C K k
r ' r
+ +

= =
( )
( )
2
B B A A
A t A s
S A
P K P K 1
P C K k
r ' r
+ +

= =
2
2
3
2
2
1
wire Pt
3
H N NH +
2
) 111 ( Rh
2
2
1
CO O CO +
177
Integration
e tan pen i e tan pen n
3 2
O Al , Pt wt 75 , 0

( )
( )

P 08 , 1 P 39 , 1 1
P 954 , 0 P 10 14 , 2
' r
2
I N
I N
4
N
+ +

=

I N
catalyst

How long would it takes to achieve 30% conversion in a batch reaction
starting with pure N at PN0 = 10 atm?

What if we start with PN0 = 10 atm & PH0 = 1 atm.
H = n-hexane, considered as inert, KH= 1.4
Atm/detik
178
Deduction of Reaction Mechanism
from Rate Equation
( )
( )
2
E D B
2 / 1
A
D A
3
A
P 36 , 5 P 21 , 7 P 76 , 2 P 49 , 0 1
P P 10 087 , 2
' r
+ + + +

=

term) adsorption (
term) force driving ( term) kinetic (
rate

=
C B D A
catalyst
+ +
From driving force term:
- Irreversible reaction
From adsorption term:
- A, B, D, & E adsorbed in catalyst surface
-A dissociatively adsorbed
-B, D, & E molecularly adsorbed
-E: adsorbed inert
-C do not adsorbed/weakly adsorbed soon after formed
-Dual site mechanism
-Surface reaction control

179
Sample Problem for
Deduction of Reaction Mechanism from
Rate Equation
( )
min cat kg
toluene gmol

P 038 , 1 P 39 , 1 1
P P 10 7 , 8
' r
T B
H T
4
T
+ +

=

4 6 6
catalyst
2 3 5 6
CH H C H CH H C + +
From driving force term:
- Irreversible reaction
From adsorption term:
- B & T adsorbed in catalyst surface, both molecularly
- M & H do not OR weakly adsorbed
- Single site mechanism
- Surface reaction control

M B H T
catalyst
+ +
k
A
k
-A
T + S TS fast
k
s
TS + H BS + M slow
k
D
k
-D
BS B + S fast
Mechanism: Adsorption
Surface reaction
Desorption
Hidrodealkylation of toluene:
180
Sample Problem for
Deduction of Reaction Mechanism from
Rate Equation
( )
( )
min cat kg
toluene gmol

P 038 , 1 P 39 , 1 1
P P 10 7 , 8
' r
2
T B
H T
4
T

+ +

=

4 6 6
catalyst
2 3 5 6
CH H C H CH H C + +
From driving force term: - Irreversible reaction
From adsorption term: - B & T adsorbed in catalyst surface, both molecularly
- M & H do not OR weakly adsorbed
- Dual site mechanism
- Surface reaction control

M B H T
catalyst
+ +
k
A
k
-A
T + S TS fast
k
s
TS + S BS + MS slow
k
D
k
-D
BS B + S fast
Mechanism: Adsorption
Surface reaction
Desorption
Hidrodealkylation of toluene:
What if:
k
D
k
-D
MS M + S fast
181
Sample Problem for
Deduction of Reaction Mechanism from
Rate Equation
( )
( )

P 08 , 1 P 39 , 1 1
P 954 , 0 P 10 14 , 2
' r
2
I N
I N
4
N
+ +

=

e tan pen i e tan pen n
3 2
O Al , Pt wt 75 , 0

From driving force term:
- Reversible reaction with K
P
= 1/0.954
From adsorption term:
- N & I adsorbed in catalyst surface, both molecularly
- Dual site mechanism
- Surface reaction control

I N
catalyst

k
A
k
-A
N + S NS fast
k
s
NS + S S + IS slow
k
D
k
-D
IS I + S fast
Mechanism: Adsorption
Surface reaction
Desorption
Isomerization of pentane:
182
Sample Problem for
Deduction of Reaction Mechanism from
Rate Equation
( )
( )

P k P k 1
P P k
" r
3
H 3 GeCl 2
H GeCl 1
Dep
2 2
2 2
+ +

=
(g) ) s ( ) g ( 2 ) g ( 2
HCl 2 Ge H GeCl + +
From driving force term:
- Irreversible
From adsorption term:
- GeCl
2
& H
2
adsorbed, Ge &HCl do not adsorbed
- GeCl
2
adsorbed molecularly H
2
adsorbed dissociatively
- Triple site mechanism
- Surface reaction control

Chemical Vapor Deposition:
k
A
k
-A
GeCl
2
+ S GeCl
2
.
S fast
k
s
GeCl
2
.S + 2 HS Ge + 2 HCl + 3 S slow
none
Mechanism: Adsorption
Surface reaction
Desorption
k
A
k
-A
H
2
+ 2 S 2 H
.
S fast
183
Sample Problem for
Deduction of Reaction Mechanism from
Rate Equation
184
Sample Problem for
Deduction of Reaction Mechanism from
Rate Equation
185
P10-7B
Sample Problem for
Deduction of Reaction Mechanism from Rate Equation
186
P10-11B
Deduction of Reaction Mechanism from Rate Equation
187
Bentuk Persamaan
Mekanisme
PercoBaan
Data Kinetik
Regresi Estimasi Parameter
Metode Least Square
V

2
c
Penyederhanaan
Interpretation of Kinetic Data
188

P
1
0
-
5
B


I
n
t
e
r
p
r
e
t
a
t
i
o
n

o
f

K
i
n
e
t
i
c

D
a
t
a

189

P
1
0
-
5
B


I
n
t
e
r
p
r
e
t
a
t
i
o
n

o
f

K
i
n
e
t
i
c

D
a
t
a

190
P10-8B
Interpretation of Rate Data
191
P10-9C
Interpretation of Rate Data
192
P
1
0
-
1
0
B

I
n
t
e
r
p
r
e
t
a
t
i
o
n

o
f

R
a
t
e

D
a
t
a

193
INTERPRETASI DATA KINETIK
OH
+ H
2
O
A B + C
Rx 10
5
P
A
P
B
P
C
3.3 1 1 1
1.05 5 1 1
0.565 10 1 1
1.826 2 5 1
1.49 2 10 1
1.36 3 0 5
1.08 3 0 10
0.862 1 10 10
0 0 5 8
1.37 3 3 3
194
Catalyst Deactivation



Types of Decay

1.) Sintering
2.) Coking
3.) Poisoning
4.) Slow Decay Temperature-Time Trajectories
5.) Moderate Decay Moving Bed
6.) Rapid Decay STTR
baru masih katalisnya saat laju
t berumur katalis saat laju
a
t
=
195
Catalyst Deactivation
Separable Kinetics:
Decay reaction order n (empirical):
n
d
a k
dt
da
=
n = 0 (linear) : Conversion of p-hidrogen on tungsten
poisoned with oxygen

n = 1 (exponential) : & ethylene hydrogenation on Cu
poisoned with CO
& paraffin dehydrogenation on Cr
.
Al
2
O
3
& cracking of gas oil
& vinyl chloride monomer formation

n = 2 (hyperbolic) : % vinyl chloride monomer formation
% cyclohexane deydrogenation on Pt/Al
2
O
3
% isobutylene hydrogenation on Ni
|
.
|

\
|
=
RT
E
exp A k
d
d d Decay constant usually follow Arrhenius form:
196
Integration of Decay Reaction Order n
t k 1
1
a
t k 1
a
1
t k 1 .
a
1
dt k
a
da
d
d
d
d
2

} }
+
=
+ =
=
=
t k
e a
D
d
t
1
d
a
1
t k
1
a
ln
dt . k
a
da

=
} }
=
|
.
|

\
|
=
1
st
order decay:
2nd order decay:
197
1
st
order decay:
Investigating Rate of Decay
t, hour 0 1 2
X,% 3 2.3 2.0
a
3
/
3
2.3
/
3
2.0
/
3
-ln a

t

Set Intersept = 0
2
nd
order decay:
Set Intersept = 1
t

a
1
1
t k
e a
D

=
t k 1
1
a
d
+
=
198
Example P
10-25C


T,hari 0 20 40 60 10 120
X,% 1 0.7 0.56 0.45 0.38 0.29
a
T = 500
o
C

T = 550
o
C
T,hari 0 5 10 15 20 30 40
X,% 2 1,2 0,89 0,69 0,57 0,42 0,33
a