L12 CRE II Heterogeneous

Catalysis
Prof. K.K.Pant
Department of Chemical Engineering
IIT Delhi.
kkpant@chemical.iitd.ac.in
2
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
3
Finding a Mechanism consistent with the experimental data
Deducing Rate law from experimental data (Example 10.2 , 10.3:
Example : Hydrodemethylation of Toluene
4
Use of Multiple regression technique (Rate or CONVERSION Data from
Differential reactor identical to CSTR)

Y = a
0
+ a
1
X
1J
+ a
2
X
2J



A
0
, a
1
are the parameters of the model.

Use regression methods / Polymath, MATLAB,
etc.

k, K
B
, K
T
are the parameters of the equation
Evaluation of Rate law Parameters
Isotherms
Assumptions:
homogeneous surface
(all adsorption sites energetically identical)
monolayer adsorption (so no multilayer adsorption)
no interaction between adsorbed molecules
p K
p K
n n n
m m ad
+
= u =
1
I
n
a
d

p / p
0
Type I Langmuir Adsorption Isotherm
Isotherms
Multilayer adsorption
(starting at B)
Common for pore-free
materials
p / p
n
a
d

0
B
Type II
Type IV
Similar to II at low P
Pore condensation at
high P
n
a
d

p / p
0
B
Isotherms
p K 1
p K
n n n
m m ad
+
= =
I
n

a
d

p / p
0
Type I Langmuir Adsorption Isotherm
8
Assumptions:
homogeneous surface
(all adsorption sites energetically identical)
monolayer adsorption (so no multilayer
adsorption)
no interaction between adsorbed molecules
Isotherms
Multilayer Physical
adsorption (starting at B)
Common for many porous
materials
p / p
n
a
d

0
B
Type II
Type IV
Similar to Type II at low P,
Pore condensation at high
P
n
a
d

p / p
0
B
Isotherms
Type III
Type IV
n
a
d

p / p
0
Strong cohesion force
between adsorbed
molecules, e.g. when water
adsorbs on hydrophobic
activated carbon
n
a
d

p / p
0
Similar to III at low P
Pore condensation at high
P. III and v are rare.
N
2
Physisorption
Adsorption and Desorption Isotherms
Langmuir Adsorption?
strong adsorption
at low P due to
condensation in
micropores
at higher P
saturation due to
finite (micro)pore
volume
Physisorption
Different Adsorbates Used in Physisorption
Studies
Adsorbate Boiling Point (K) A
m
(nm
2
/molecule)
N
2
77.3 0.162
Ar 87.4 0.142
CO
2
194.5 0.17
Kr 120.8 0.152
13
NAME ISOTHERM
EQUATION
APPLICABILITY
Chemisorption
and Physical
adsorption
Henry




Chemisorption
and Physical
adsorption
At low
coverages
Freundlich Chemisorption
and Physical
adsorption
At low
coverages

Langmuir

V bp
==
V 1+bp
n
'
V=k p
( )
1
n
V=kp n > 1
14

Temkin

Chemisorption
Brunauer
Emmett-
Teller(BET)
Multilayer
,physical
adsorption

Polanyi
(c)
physical
adsorption
u
V
= =AlnBp
V
m
( )
p 1 c 1 p
= +
V po - p V c V c po
m m
( )
=RTln po/p
Determination of Surface Area
Physisorb an inert gas such as argon or
nitrogen and determine how many
molecules are needed to form a complete
monolayer
For example, the N
2
molecule occupies
0.162 nm
2
at 77 K, the total surface area
follows directly
Determination of Surface Area
Physisorb an inert gas such as argon or
nitrogen and determine how many
molecules are needed to form a complete
monolayer.

For example, the N
2
molecule occupies
0.162 nm
2
at 77 K, the total surface area
follows directly.

Although this sounds straightforward, in
practice molecules may adsorb beyond the
monolayer to form multilayers.
In addition, the molecules may condense in
small pores. The narrower the pores, the
easier N
2
will condense in them.
This phenomenon of capillary pore
condensation, as described by the Kelvin
equation
Phenomenon can be used to determine the
types of pores and their size distribution
inside a system
N
2
Physisorption
Adsorption and Desorption Isotherms
0
5
10
15
20
25
0 0.2 0.4 0.6 0.8 1
p/p
0
n
a
d

(
m
m
o
l
/
g
)

1
Adsorption
Desorption
Adsorption and Desorption Isotherms
III
n
a
d

p / p
0
VI
n
a
d

p / p
0
V
n
a
d

p / p
0
I
n
a
d

p / p
0
p / p
II
n
a
d

0
B
IV
n
a
d

p / p
0
B
N
2
Physisorption
Pore Size and Shape
Why is it important?
it dictates the diffusion process through the
material.
Why is it important?
directly affect the selectivity of the catalytic
reaction.
Pore Size and Shape
Pore Diameter
micropores (< 2 nm)
mesopores (2 50 nm)
macropores (> 50 nm)

Pore Shape
cylinder
slit
ink-bottle
wedge
v
Pore Size and Shape
Measurement Techniques
1 10 100 1000 10000
Pore diameter (nm)
Micro Meso Macro
2 50
N
2
capillary condensation
Hg porosimetry
Pore volume determination ( Helium -Mercury Method)
The pore volume of the catalyst can be determined by the helium-
Mercury method.
The volume of Mercury and Helium displaced by the catalyst is used
to measured the pore volume of the catalyst.
Since mercury cannot pass through the pores of the catalyst , the
difference in the volume gives the pore volume.
V
mercury
=> extrenal volume of solid, V
He =
pore vol+soild vol.


Pore volume Vg = (V
mercury
V
Helium
)/(Mass of catalyst)
Porosity= e= 1/p - 1/S = p Vg

Pore size distribution
An important property of catalysts is the distribution of pores across the
inner and outer surfaces. The most widely used method for
determining the pore distribution in solids is mercury porosimetry and
BET method.
Mercury Porosimetry:
The pore size distribution is determined by measuring the volume of
mercury that enters the pores under pressure.

is surface tension of Hg = 0.425 N/m
Pressures of 0.1 to 200 MPa allow pore sizes in the range 207500 nm
to be determined.