Catalysis and Catalytic

Reactions
2
Scope:
Catalyst & Catalysis ??
Limited to gas phase reactions
catalyzed by solids
Mechanism & rate laws
Interpretation of data estimation of
rate law parameters
Physical properties of catalysts
estimation
Catalytic reactors
Design of Fixed bed reactor
3
What is a catalyst ??
Alters the rate of reaction
Highly selective
Does it participate in the reaction ??
How does it change the rate ?? Offers an
alternate path with low E.
Does it affect AH
R
, AG
R
, and Eq. constant ??
Does it affect yield & selectivity ??
Does it initiate a reaction ??
4
Every catalytic reaction is a sequence of elementary
steps, in which reactant molecules bind to the catalyst,
where they react, after which the product detaches
from the catalyst, liberating the latter for the next
cycle
5
Potential energy diagram of a heterogeneous catalytic
reaction, with gaseous reactants and products and a solid
catalyst. Note that the uncatalyzed reaction has to
overcome a substantial energy barrier, whereas the
barriers in the catalytic route are much lower.
6
Homogeneous:



Catalytic:




At 600 K the ratio of catalytic to homogeneous rate is
1.44x10
11
Example: Boudart compared the homogeneous versus
catalytic rates of ethylene hydrogenation.
2
43000
exp 10
27
H
p
RT
r
|
.
|

\
|
=
2
13000
exp 10 2
27
H
p
RT
x r
|
.
|

\
|
=
7
What is a catalyst ??
Were in use for making wine, cheese etc.
Small amounts of catalyst
Efficiency depends on activity, properties &
life of the catalyst
Examples:
Ammonia synthesis Promoted iron
SO
2
oxidation Venadium Pentaoxide
Cracking Sylica, alumina
Dehydrogenation Platinum, Molybdenum
8
Classification:
Homogenous catalysis
Heterogeneous catalysis
Catalysts are generally used to:
Speedup reactions
Change the operating temperature level
Influence the product distribution
9
Promoter: is an additive which has no
catalytic properties of its own but
enhances the activity of a catalyst
Promoter results in:
Increase of available surface area
Stabilization against crystal growth
and sintering
Improvement of mechanical
strength
Examples: Alumina, Asbestos
10
Carrier: principally serve as a framework on
which catalyst is deposited - no catalytic
properties of its own
Carrier results in:
Highly porous nature - increase of
available surface area
Improve stability
Improves the heat transfer
characteristics
Examples: Alumina, Asbestos, Carborundum, Iron
oxide, Manganese, Activated carbon, Zinc oxide
11
Accelerator: are substances which can be
added to a reacting system to maintain
the activity of a catalyst by nullifying the
effects of poisons
Poisons: substances which reduce the
activity of a catalyst. They are not
deliberately added but are unavoidably
deposited during the reaction.
Examples: Sulfur, Lead, Metal ions such as Hg,
Pd, Bi, Sn, Cu, Fe etc.
12
Inhibitor: substances added to the catalyst
during its manufacture to reduce its
activity.
Coking/Fouling: deposition of carbonaceous
material on the surface of the catalyst -
Common to reactions involving
hydrocarbons
13
Activity: of a catalyst depends on the
texture and electronic structure. Activity
of a catalyst can be explained by:
Active centers on the surface of the
catalyst
Geometry of surface
Electronic structure
Formation of surface intermediates
Efficiency of a catalyst depends on :
Activity, Selectivity and Life
14
Active site: is a point on the catalyst
surface that can form strong chemical
bonds with an adsorbed atom/molecule.
These sites are unsaturated atoms in the
solid resulting from:
Surface irregularities
Dislocations
Edges of crystals
Cracks along grain boundaries
15
16
Mechanism of Heterogeneous Catalysis:
1. Bulk Diffusion of reacting molecules to the
surface of the catalyst
2. Pore Diffusion of reacting molecules into the
interior pores of the catalyst
3. Adsorption of reactants (chemisorption) on
the surface of the catalyst
4. Reaction on the surface of the catalyst
between adsorbed molecules
5. Desorption of products
6. Pore Diffusion of product molecules to the
surface of the catalyst
7. Bulk Diffusion of product molecules
17
Mechanism of Heterogeneous Catalysis:
18
Mechanism of Heterogeneous Catalysis:
19
20
Pore and film resistances in a catalyst particle
21
Rate-Determining Step (rds)
In a kinetics scheme involving more than one step, it
may be that one change occurs much faster or much
slower than the others (as determined by relative
magnitudes of rate constants).

In such a case, the overall rate, may be determined
almost entirely by the slowest step, called the rate-
determining step (rds).

The rate of the rds is infinitesimal when compared to
the rates of other steps.

Alternately the rates of other steps are infinite
compared to the rate of rds.
22
Bulk Diffusion:
Diffusion controlled reactions are usually
fast
Design of reactors design of mass
transfer equipment
Increase in mass velocity increases the rate
High L/D ratio reactors (narrow) are
favored
23
Pore Diffusion:
Pore diffusion controlled reactions are few
Design of reactors most complicated
Approaches bulk diffusion if the pore size is
large
Approaches Knudsen diffusion if the pore
size is small.
No effect of temperature or mass velocity
Low L/D ratio reactors (wide) may be used
with consequent reduction in pressure drop
24
25
Chemisorption:
Chemisorption controlled reactions are
usually fast
Rate increases rapidly with increase in temp.
Permits the use of wide reactors
Surface reaction:
70% of the reactions which are not
controlled by diffusion falls under this case
Rate increases rapidly with increase in temp.
Permits the use of wide reactors
26
Desorption:
Desorption of a product could also be rate
controlling in a few cases
Complexities:
Theoretically more than one step can be
rate controlling
Too many possible mechanisms
Experimental data is normally fitted to any
single rate controlling step, which is then
called the most plausible mechanism
27
Item Physical Adsorption Chemisorption
Forces of
attraction
Weak VanderWaals forces Strong valency forces
Specificity Low High
Quantity Large Small
Heat Effects Exothermic, 1-15 kCal/mol Exothermic, 10-100 kCal/mol
Activation
energy
Low High
Effect of Temp. Rapid at low temperatures &
reach equilibrium quickly.
Beyond T
C
of the gas, no ads.
Slow at low temp., Rate increases
with temp.
Effect of
Pressure
Increases with increase in
pressure
Little effect
Surface Whole surface active Fraction of surface only
Layers Multi-layer adsorption Mono-layer adsorption
Physical Adsorption Vs. Chemisorption
28
Chemisorption rates:
Adsorption data is reported in the form of
isotherms
Chemisorption may be considered as a
reaction between a reactant molecule and an
active site resulting in an adsorbed molecule
A + o Ao (or) A + S AS
Turnover Frequency (N): defined as the
number of molecules reacting per active site
per second at the conditions of the
experiment a measure for the activity of
the catalyst
29
Langmuir Isotherm - Assumptions:
Surface is uniformly active
All sites are identical
Amounts of adsorbed molecules will not
interfere with further adsorption
Uniform layer of adsorption
Site balance:
t
v
v
sites total
sites vacant of No
sites vacant of Fraction
o
o
u = = =
.
t
A
A
sites total
sites occupied of No
A by occupied sites of Fraction
o
o
u = = =
.
1 = +
A v
u u
30
Alternately:
number s Avogadro
mass unit sites active of No
sites active of conc Molar C
t
'
/ .
. = =
number s Avogadro
mass unit sites vacant of No
sites vacant of conc Molar C
v
'
/ .
. = =
number s Avogadro
mass unit A by sites of No
A by sites of conc Molar C
AS
'
/ .
. = =
t AS v
C C C = +
Though other isotherms account for non-uniform surfaces, they
have primarily been developed for single adsorbing components.
Thus, the extensions to interactions in multi-component systems is
not yet possible, as with the Langmuir isotherm. Langmuir isotherms
are only used for developing kinetic rate expressions. However, not
all adsorption data can be represented by a Langmuir isotherm.
31
32
Chemisorption rates (molecular adsorption):
A + o Ao
Forward rate = k
1
p
A
u
v
Backward rate = k
2
u
A
At equilibrium: k
1
p
A
u
v
= k
2
u
A

(k
1
/k
2
)p
A
u
v
= u
A

A A
A A
A
p K
p K
+
=
1
u
A A
t A A
AS
p K
C p K
C
+
=
1
1 = +
A v
u u
33
Chemisorption rates (Atomic adsorption):
A
2
+ 2o 2Ao
Forward rate = k
A
p
A
u
v
2

Backward rate = k
-A
u
A
2

At equilibrium: k
A
p
A
u
v
2

= k
-A
u
A
2

(k
A
/k
-A
)p
A
u
v
2

= u
A
2


A A
A A
A
p K
p K
+
=
1
u
t
A A
A A
AS
C
p K
p K
C
+
=
1
What would be u
A
if chemisorption does not
reach equilibrium ??

34
Effect of increasing temperature

V
o
l
u
m
e

o
f

g
a
s


a
d
s
o
r
b
e
d

How to check for Molecular Adsorption /
Atomic adsorption ??

35
Langmuir adsorption isotherm for associative adsorption
for three values of the equilibrium constant, K
A A
A A
A
p K
p K
+
=
1
u
36
Surface Reaction: reaction between the adsorbed
molecules on the surface of the catalyst may
proceed in a number of ways:

Single site mechanism: Ao Ro

Dual site mechanism: Ao + o Ro + o


Ao + Bo Ro + So
Ao + Bo Ro + o
Langmuir-Hinshelwood kinetics

37
Ao + B(g) Ro

Ao Ro + S(g)


Ao + B(g) Ro + S(g)
Ao + Bo Ro + o + S(g)
Eley Riedel Mechanism

38
Surface reaction rates:
(1) Ao Ro
Forward rate = k
S
u
A
Backward rate = k
-S
u
R
At equilibrium: k
S
u
A
= k
-S
u
R

A R S
K u u / =
(2) Ao + o Ro + So
V A S R S
K u u u u / =
(3) Ao + Bo Ro + So
B A S R S
K u u u u / =
B A S R S
p p K u u / =
(4) Ao + B(g) Ro + S(g)
(5) Ao Ro + S(g)
A S R S
p K u u / =
39
Desorption rates:
Ro R + o
(Desorption of R is the Reversal of adsorption of R)
Forward rate = k
D
u
R
Backward rate = k
-D
p
R
u
V
At equilibrium: k
D
u
R
= k
-D
p
R
u
V

V R R D V R R
p K K p u u u = = /
40
Synthesizing a rate law Algorithm
(Langmuir-Hinshelwood Approah)

1. Assume a sequence of steps
2. Write rate laws for each step assuming all
steps to be reversible
3. Assume a rate limiting step
4. Equate the rate of rds to the overall rate
5. The rates of other steps are equated to zero
(equilibrium)
6. Using the rates of other steps eliminate all
coverage dependent terms
7. If the derived rate law does not agree with
expt., goto (3)

41
Approach is similar to non-elementary reactions
In the case of non-elementary reactions there
is only one rate law for a given mechanism
But in the case of solid catalyzed gas phase
reactions, there could be many (equal to the
number of steps) rate laws for a given
mechanism
In a given mechanism, even after assuming each
of the steps as rds, and none of them satisfy
the experimental data, start with a new
mechanism and repeat

42
Example: C
6
H
5
CH(CH
3
)
2
C
6
H
6
+ C
3
H
6
Cumene Benzene + Propylene
Suggested Mechanism:
C + o Co (Adsorption of cumene)
Co Bo + P(g) (Surface reaction)
Bo B + o (Desorption of Benzene)
Rate laws for each of the steps:
C A V C A
k p k Adsorption of rate Net u u

=
P B S C S
p k k reaction Surface of rate Net u u

=
V B D B D
p k k Desorption of rate Net u u

=
43
Case-I: Adsorption is Rate limiting step
C A V C A C
k p k Adsorption of rate Net r u u

= =
) / (
A C V C A C
K p k r u u =
0 Re = =
P B S C S
p k k action Surface of rate Net u u
0 = =
V B D B D
p k k Desorption of rate Net u u
S P B C
K p / u u =
D V B B
K p / u u =
V
D S
B P
C
K K
p p
u u =
Site balance: u
C
+ u
B
+ u
V
= 1
D
B
D S
B P
V
K
p
K K
p p
+ +
=
1
1
u
44
) / (
A C V C A C
K p k r u u =
) ( ) (
eq
B P
C V A V
D S A
B P
V C A C
K
p p
p k
K K K
p p
p k r = = u u u
D
B
D S
B P
eq
B P
C A
C
K
p
K K
p p
K
p p
p k
r
+ +

=
1
) (
Final rate law for Case-1
Case-II: Surface reaction is rate limiting step
C A V C A
k p k Adsorption of rate Net u u

=
P B S C S
p k k reaction Surface of rate Net u u

=
V B D B D
p k k Desorption of rate Net u u

=
45
V C A C C A V C A
p K k p k Adsorption of rate Net u u u u = = =

0
P B S C S C
p k k reaction Surface of rate Net r u u

= =
D V B B V B D B D
K p p k k Desorption of rate Net / 0 u u u u = = =

) / (
S P B C S C
K p k r u u =
Site balance: u
C
+ u
B
+ u
V
= 1
D
B
C A
V
K
p
p K + +
=
1
1
u
) / ( ) / (
S D A P B C V A S S D V P B V C A S C
K K K p p p K k K K p p p K k r = = u u u
D
B
C A
eq
B P
C A S
C
K
p
p K
K
p p
p K k
r
+ +

=
1
) (
Final rate law for Case-2
46
Case-III: Desorption is rate limiting step
P C S B P B S C S
p K p k k reaction Surface of rate Net / 0 u u u u = = =

) / (
D V B B D V B D B D C
K p k p k k Desorption of rate Net r u u u u = = =

V C A C C A V C A
p K k p k Adsorption of rate Net u u u u = = =

0
Site balance: u
C
+ u
B
+ u
V
= 1
P C S A C A
V
p p K K p K / 1
1
+ +
= u
P V C A S B
p p K K / u u =
) / / (
D V B P V C A S D C
K p p p K K k r u u =
) / / (
D S A B P C V A S D C
K K K p p p K K k r = u
C S A C P A P
eq
B P
C S A D
P C S A C A
eq
B
P C S A D
C
p K K p p K p
K
p p
p K K k
p p K K p K
K
p
p p K K k
r
+ +

=
+ +

=
) (
/ 1
) / (
47
D
B
D S
B P
eq
B P
C A
C
K
p
K K
p p
K
p p
p k
r
+ +

=
1
) (
D
B
C A
eq
B P
C A S
C
K
p
p K
K
p p
p K k
r
+ +

=
1
) (
C S A C P A P
eq
B P
C S A D
C
p K K p p K p
K
p p
p K K k
r
+ +

=
) (
Case-1
Case-2
Case-3
) (
) (
term Adsorption
Force Driving term Kinetic
Rate =
What would be
the effect of
an inert ??
48
Effect of increasing reactant concentration:
Increasing the reactant concentration increases
both the driving force and adsorption inhibition
terms.
C
A
rate

Volcano shape results from a competition between kinetic
driving force and adsorption inhibition terms.

49
Term Case-1 Case-2 Case-3
Kinetic
k
A
k
S
K
A
k
D
K
A
K
S
Driving
Force

Adsorption
eq
B P
C
K
p p
p
eq
B P
C
K
p p
p
eq
B P
C
K
p p
p
D
B
D S
B P
K
p
K K
p p
+ + 1
D
B
C A
K
p
p K + + 1
C S A C P A P
p K K p p K p + +
50
V C A
p K u
V C A
p K u
V
D S
B P
K K
p p
u
P V C A S
p p K K / u
D V B
K p / u
D V B
K p / u
Coverage Case-1 Case-2 Case-3
u
C

u
B

51
52
53
54
For a given mechanism, the driving force is
unique, irrespective of RDS
The product of equilibrium constant of all steps
in the mechanism yield the overall eq. constant
In the kinetic term, the rate constant of RDS
will appear
If adsorption of A is not RDS, then K
A
p
A
will
appear in the adsorption term
If desorption of B is not rate limiting, then
p
B
/K
D
will appear in the adsorption term
If SR is RDS, then the adsorption term will be
raised to the power equal to the number of
sites involved in the SR step.

Remarks:
55
Exercise: Al
2
O
3

N-pentane I-Pentane
Suggested Mechanism:
N + o No
No + o Io + o
Io I + o
Rate laws for each of the steps:
N A V N A
k p k Adsorption of rate Net u u

=
v I S v N S
k k reaction Surface of rate Net u u u u

=
V I D I D
p k k Desorption of rate Net u u

=
56
Case-I: Adsorption is Rate limiting step
N A V N A N
k p k Adsorption of rate Net r u u

= =
) / (
A N V N A N
K p k r u u =
0 Re = =
v I S v N S
k k action Surface of rate Net u u u u
0 = =
V I D I D
p k k Desorption of rate Net u u
S I N
K / u u =
D V I I
K p / u u =
V
D S
I
N
K K
p
u u =
Site balance: u
C
+ u
B
+ u
V
= 1
D
I
D S
I
V
K
p
K K
p
+ +
=
1
1
u
57
) / (
A N V N A N
K p k r u u =
) ( ) (
eq
I
N V A V
D S A
I
V N A N
K
p
p k
K K K
p
p k r = = u u u
D
I
D S
I
Eq I N A
N
K
p
K K
p
K p p k
r
+ +

=
1
) / (
Rate law for Case-1
Case-II: Surface reaction is rate limiting step
N A V N A
k p k Adsorption of rate Net u u

=
v I S v N S
k k reaction Surface of rate Net u u u u

=
V I D I D
p k k Desorption of rate Net u u

=
58
V N A N N A V N A
p K k p k Adsorption of rate Net u u u u = = =

0
v I S v N S N
k k reaction Surface of rate Net r u u u u

= =
D V I I V I D I D
K p p k k Desorption of rate Net / 0 u u u u = = =

) / (
S I N v S N
K k r u u u =
Site balance: u
C
+ u
B
+ u
V
= 1
D I N A
V
K p p K / 1
1
+ +
= u
) / ( ) / (
2
S D A I N v A S S D V I V N A V S N
K K K p p K k K K p p K k r = = u u u u
2
) / 1 (
) / (
D I N A
Eq I N A S
N
K p p K
K p p K k
r
+ +

=
Rate law for Case-2
59
Case-III: Desorption is rate limiting step
N S I v I S v N S
K k k reaction Surface of rate Net u u u u u u = = =

0
) / (
D V I I D V I D I D N
K p k p k k Desorption of rate Net r u u u u = = =

V N A N N A V N A
p K k p k Adsorption of rate Net u u u u = = =

0
Site balance: u
C
+ u
B
+ u
V
= 1
N S A N A
V
p K K p K + +
=
1
1
u
V N A S I
p K K u u =
) / (
D V I V N A S D N
K p p K K k r u u =
) / (
D S A I N V A S D N
K K K p p K K k r = u
N S A N A
Eq I N S A D
N
p K K p K
K p p K K k
r
+ +

=
1
) / (
Rate law for Case-3
60
How to verify which one is rate limiting step ??
For this initial rate data is normally used
D
B
C A
eq
B P
C A S
C
K
p
p K
K
p p
p K k
r
+ +

=
1
) (
C
C
C A
C A S
bp
ap
p K
p K k
r
+
=
+
=
1 1
0
In the absence of any products initially, the
rate law simplifies to:
61
Case-1
Case-2
N S A N A
eq
I
N S A D
N
p K K p K
K
p
p K K k
r
+ +

=
1
) (
2
) / 1 (
) (
D I N A
eq
I
N A S
N
K p p K
K
p
p K k
r
+ +

=
D
I
D S
I
eq
I
N A
N
K
p
K K
p
K
p
p k
r
+ +

=
1
) (
N A
p k r =
0
2
0
) 1 (
N A
N A S
p K
p K k
r
+
=
Case-3
N S A N A
N S A D
p K K p K
p K K k
r
+ +
=
1
0
62
Simplified rate laws:
Over limited pressure range, the Langmuir
isotherm u = Kp/(1+Kp) can be replaced by an
approximation u = kp
n
In such cases the rate law assumes the form:
r = k p
A
m
p
B
n
p
C
o
Such rate laws may be reasonably accurate
Example: CO + Cl
2
COCl
2
(Over charcoal)
2
) 1 (
2 2 2 2
2 2
2
COCl COCl Cl Cl
Cl CO Cl CO
COCl
p K p K
p p K kK
r
+ +
=
L-H approach
2 / 1
2 2
Cl CO COCl
p kp r =
Simplified equation
63
How to verify whether the rate law confirms
to experimental data or not ??
D
B
C A
eq
B P
C A S
C
K
p
p K
K
p p
p K k
r
+ +

=
1
) (
A S
D
B
C A
C
eq
B P
C
K k
K
p
p K
r
K
p p
p
+ +
=

1
B C
C
eq
B P
C
cp bp a
r
K
p p
p
+ + =

Use regression
How to decide whether the fit is reasonable ??
If the fit is reasonable, evaluate the
constants
64
Design of Fixed Bed Reactor:
65
66
Design Equation
General Mass Balance Equation:

Rate of input = rate of output + accumulation
+ rate of disappearance
F
A
= F
A
+ dF
A
+ 0 + (-r
A
) dW
- dF
A
= (-r
A
) dW

F
A0
dx
A
= (-r
A
) dW
dW
A A
r dW dF = /
67
}
=
A
x
A A A
r dx F W
0
0
/ /
General design equation for a FBR:
dt
dN
W Weight unit time unit
d disappeare A of Moles
r
A
A
1
) )( (

= =
Definition of rate of reaction:
When the rate is expressed in terms of catalyst weight,
mass transfer effects between the catalyst and the bulk
fluid & also within the catalyst are ignored. Such mass
transfer aspects could be important in some cases.
68
Fixed Bed Reactor Integral form
}
=
A
x
A A A
r dx F W
0
0
/ /
1 /-r
A
x
A

W / F
A0
69
Fixed Bed Reactor differential form
A A
r dW dF = /
F
A
W
-r
A x
A
W/F
A0

-r
A
A A A
r dW dx F = /
0
70
How to find the rate data ??
How can we calculate the weight of the
catalyst needed for obtaining the given
conversion ??
D
B
A A
eq
B C
A A S
A
K
p
p K
K
p p
p K k
r
+ +

=
1
) (
}
=
A
x
A A A
r dx F W
0
0
/ /
Express the partial pressures in terms of x
A

A A
A
A
A
x
x
p
p
c +

=
1
1
0 A A
A R
A
R
x
x a r M
p
p
c +
+
=
1
) / (
0
) (
A A
x f r =
Use numerical / graphical integration
71
Physical properties of catalysts:
Bulk density
Surface area
Pore volume
Pore size distribution
For Silica-Alumina catalyst:
Surface area = 200 500 m
2
/gm
Pore volume = 0.2 0.7 ml/gm
72
Measurement of Surface area:
Measuring the surface area active for
chemisorption is difficult because of:
highly selective nature
fraction of surface
physical adsorption + chemisorption
presence of promoter, carrier etc.
Universally surface area of a catalyst is
measured using physical adsorption
principles. It is approximated that the more
the area the more would be the activity of
the catalyst.
73
Experiment:
The amount of N
2
adsorbed at equilibrium at the
normal boiling point temp (-195.8
0
C) is measured
over a wide range of N
2
partial pressures below
1 atm.
Identify the amount required to cover the
entire surface by a mono-layer
V
STP
p
Nitrogen

Linear region
Mono Layer ads

p/p
0
< 0.1 Mono layer
0.1 < p/p
0
< 0.4 Multi layer
0.4 < p/p
0
< 1.0 Capillary condensation
74
m m m N
N
N
v
p
Kv v
p
v
v
Kp
Kp
+ = =
+
=
1
1
2
2
2
u
1. Langmuir Isotherm:
p/v

p
Slope = 1/v
m

75
0 0
) 1 ( 1
) ( p cv
p c
c v p p v
p
m m

+ =

2. BET Isotherm:
p/[v(p
0
-p)]

p/p
0

Slope = (c-1)/cv
m

P
0
= vapor pressure / Satn pressure
1/cv
m

v
m
= 1/(slope + Intercept)
76
Convert v
m
to no. of molecules
o = area covered by one molecule
o
|
.
|

\
|
=
22400
0
N v
S
m
3 / 2
0
09 . 1
|
|
.
|

\
|
=

o
N
M
For Nitrogen:
= 0.808 g/cc at -195.8
0
C
o = 16.2x10
-16
cm
2
= 16.2 (A
0
)
2

m
v S
4
10 35 . 4 =
v
m
is in CC at STP
Specific Surface area = S/W cm
2
/gm
77
ANY CLARIFICATIONS ?
Colton, Charles Caleb
Examinations are formidable, even to the best prepared, for the
greatest fool may ask more than the wisest man can answer.