CATALYSIS

Problems
The following heterogeneous reaction takes place
in which there is an adsorbing gas (inhibitor)
present. The suggested mechanism is:
A (g) + o Ao
Ao + B (g) Co
Co C(g) + o
Derive the Rate laws assuming each of the
following steps as rate limiting. Also sketch the
initial rate in each of the above cases as a
function of total pressure.
1) Adsorption of A 2) Surface reaction
3) Desorption step
2
Case-I: Adsorption is Rate limiting step
) / (
A A V A A A A V A A A
K p k k p k Adsorption of rate Net r u u u u = = =

0 Re = =
C S A B S
k p k action Surface of rate Net u u
0 = =
V C D C D
p k k Desorption of rate Net u u
B S C A B A S C
p K p K / u u u u = =
D V C C
K p / u u =
V
D S B
C
A
K K p
p
u u =
Site balance: u
C
+ u
A
+ u
I
+ u
V
= 1
I I
D
C
D S B
C
V
p K
K
p
K K p
p
+ + +
=
1
1
u
I A V I I
k p k I of Adsorption of rate Net u u

=
V I I I
p K u u =
3
) / (
D S A B v C V A A A
K K K p p p k r u u =
V
e
B C
C A A
K
p p
p k r u )
/
( =
I I
D
C
D S B
C
eq B
C
A A
A
p K
K
p
K K p
p
K p
p
p k
r
+ + +

=
1
) (
Final rate law for Case-1
I I
A A
p K
p k
r
+
=
1
0
Initial rate law for Case-1
4
Initial rate in each of the above cases as a function of
total pressure.
Ke does not include K
I
.
Case-II: Surface reaction is rate limiting step
) / (
S C A B S A
K p k SR of rate Net r u u = =
0 = =
A A v A A
k p k Adsorption of rate Net u u
0 = =
V C D C D
p k k Desorption of rate Net u u
v A A A
p K u u =
D V C C
K p / u u =
Site balance: u
C
+ u
A
+ u
I
+ u
V
= 1
I I
D
C
A A
V
p K
K
p
p K + + +
=
1
1
u
I A V I I
k p k I of Adsorption of rate Net u u

=
V I I I
p K u u =
5
) / (
D S v C v A A B S A
K K p p K p k r u u =
) / (
D S A C A B v A S A
K K K p p p K k r = u
I I
D
C
A A
eq C B A A S
A
p K
K
p
p K
K p p p K k
r
+ + +

=
1
) / (
I I A A
B A A S
p K p K
p p K k
r
+ +
=
1
0
6
Initial rate in each of the above cases as a function of
total pressure.
Case-III: Desorption is rate limiting step
) / (
D v C C D A
K p k Desorption of rate Net r u u = =
0 = =
A A v A A
k p k Adsorption of rate Net u u
0 = =
C S A B S
k p k SR of rate Net u u
v A A A
p K u u =
v A B S A A B S C
p p K K p K u u u = =
Site balance: u
C
+ u
A
+ u
I
+ u
V
= 1
I I B A S A A A
V
p K p p K K p K + + +
=
1
1
u
I A V I I
k p k I of Adsorption of rate Net u u

=
V I I I
p K u u =
7
I I B A S A A A
eq C B A S A D
A
p K p p K K p K
K p p p K K k
r
+ + +

=
1
) / (
) / (
D v C v B A S A D A
K p p p K K k r u u =
) / (
D S A C B A v S A D A
K K K p p p K K k r = u
I I B A S A A A
B A S A D
p K p p K K p K
p p K K k
r
+ + +
=
1
0
8
Initial rate in each of the above cases as a function of
total pressure.
The heterogeneous reaction A
2
2B takes place
according to the following mechanism
A
2
(g) + 2o 2Ao
Ao Bo
Bo B(g) + o
Derive the Rate law assuming surface reaction
step as rate limiting. Also sketch the initial rate
as a function of total pressure.
Check whether you get the overall equilibrium
constant by multiplying the equilibrium constants
of the three steps ??
9
The heterogeneous reaction A + B R + S takes
place according to the following mechanism:
A(g) + o Ao
B(g) + o Bo
Ao + Bo Ro + So
Ro R(g) + o
So S (g) + o
Derive the Rate laws assuming each of the above
steps as rate limiting. What would be the rate
laws in each of the above cases, if an adsorbing
inert is present in the reaction scheme.
10
Catalytic hydrogenation of propylene was studied
and the controlling step was found to be the
surface reaction between adsorbed olefin and
hydrogen which is adsorbed after dissociation.
The product was also found to adsorb on the
catalyst surface. Derive the Rate law.
Problem
The reaction CO
2
+ H
2
CO + H
2
0 was
investigated in the presence of Fe-Cu catalyst.
The controlling step was found to be the surface
reaction between adsorbed CO
2
with a molecule
of hydrogen in gas phase resulting in an adsorbed
CO molecule and H
2
O molecule in the gas phase.
Derive the Rate law.
Problem
11
Problem
Check the validity of the following controlling
steps using the following data on the
hydrogenation of ethylene.
(a) Desorption of product controlling:

(b) Adsorption of H
2
controlling

(c) Surface reaction controlling
4 2
4 2 2
0
H C
H C H
bp a
p p
r
+
=
4 2
2
0
H C
H
bp a
p
r
+
=
3
0
) (
4 2
4 2 2
H C
H C H
bp a
p p
r
+
=
12
Flowrate gmol/s p
H2
(atm) p
C2H4
(atm) r
0
gmol/hr.g
0.000266 0.405 0.595 0.00882
0.000266 0.401 0.599 0.009
0.000362 0.611 0.389 0.01172
0.000698 0.776 0.224 0.01444
0.000564 0.908 0.092 0.01964
0.000766 0.933 0.067 0.02021
0.001062 0.951 0.049 0.02030
0.000360 0.603 0.397 0.01183
13
Problem
A catalytic reaction 2A R is carried out in a
fixed bed reactor and the following data are
obtained.
p
A
(atm) 0.1 0.2 0.4 0.5
-r
A
(gmol/g.hr) 0.139 0.408 0.988 1.893
Show that the data is consistent with the
following rate equation and evaluate the
constants.
2
2
) 1 (
) (
A A
A A
A
p K
p K k
r
+
=
14
Problem
Experimental investigation of a catalytic reaction
reveals the following data:
x
A
0 0.1 0.2 0.3
dx
A
/dW 6.0 6.0 6.0 6.0
The reaction is 2A + B 2R. The feed consists
of A and B in the molar ratio of 3:1 is passed at a
rate of 60 kmol/hr.
Find:
(a) the rate of reaction, when x
A
= 0.2
(b) Weight of catalyst needed for x
A
= 0.35
15
The data below were recorded at constant
temperature for the adsorption of N
2
on silica
gel at -196
0
C. Calculate the surface area of the
catalyst sample using (a) Langmuir Isotherm and
(b) BET isotherm.
p(kpa) 0.8 3.3 18.7 30.7 38.0 42.7 57.3 67.3
V(vol ads/g) 6.1 12.7 17.0 19.7 21.5 23.0 27.7 33.5
Problem
The area covered / molecule of adsorbed N
2
may be taken as 16.2 (A
0)2
.
16
Problem
Oxidation of NO (2NO + O
2
2NO
2
) is
catalyzed by active carbon. The rate equation at
30
0
C and 3 atm is found to be:
2
2
3 2 4
2
10 352 . 1 842 . 4 10 62 . 1 .
NO NO
O NO
NO
p x p x
p p
hr cat g
gmolesNO
r

+ +
=
|
|
.
|

\
|

where p.p are in atm.

It is desired to process 50 tons/day of NO,
using an air-NO mixture containing 1.5 mole%
NO. Find the weight of the catalyst necessary
in a packed bed reactor for obtaining a
conversion of 90%.
17
2A + B 2C
F
A0
= 50 tons/day = 69333 gmol/hr
Composition of the feed:
NO = 1.5% Air: 98.5%
O
2
= 20.685%
N
2
= 77.815%
c
A
= (-0.5)x0.0015
p
A0
= y
A0
x P
T0
= 0.0015x3 atm
) 1 (
) 1 (
0
A A
A
A A
x
x
p p
c +

=
) 1 (
) 5 . 0 79 . 13 (
) 1 (
) / (
0 0
A A
A
A
A A
A B
A B
x
x
p
x
ax b M
p p
c c +

=
+

=
) 1 (
0
A A
A
A C
x
x
p p
c +
=
18
2
0
2 2
0
3
2 3
0
) 1 ( ) 1 ( ) 1 (
) 5 . 0 79 . 13 ( ) 1 (
A A A A A A A A
A A A
A
x x cp x bp x a
x x p
r
c c + + + +

=
}

=
9 . 0
0
0
A
A
A
r
dx
F W
x
A

0.9
1/-r
A

Weight of the catalyst = 135.4 tons
19
Problem
The gas phase reaction CO + 3H
2
CH
4
+ H
2
O
is carried out over a Nickel catalyst.
2
2
4
5 . 1 1
0183 . 0
.
H
CO H
CH
p
p p
hr cat g
gmoles
r
+
=
|
|
.
|

\
|
where p.p are in atm.
It is desired to produce 20 tons/day of CH
4
.
Find the weight of the catalyst necessary in a
packed bed reactor for obtaining a conversion
of 80%. The feed consists of 75% H
2
and 25%
CO at a temperature of 250
0
C and a pressure
of 10 atm.
20
A first order catalytic reaction A B is
carried out in a fixed bed reactor with F
A0
=
12.5 kmol/hr and the following data is obtained.
W (kg) 0.625 1.87 3.125 4.375 6.25 7.5 8.75
x
A
0.058 0.139 0.213 0.288 0.381 0.44 0.493
Calculate the weight of catalyst required for 40%
conversion, if the molar feed rate is increased by 10
times.


***
Problem
21