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L14 CRE II Heterogeneous Catalysis

Prof. K.K.Pant
Department of Chemical Engineering
IIT Delhi.
kkpant@chemical.iitd.ac.in
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
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.
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
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 + pore ,
V
He =
volume occupied by the solid material.

density of soild (
s
)
Pore volume Vg = (V
mercury
V
Helium
)/(Mass of catalyst, m)
Porosity= = mv
g
/ (m vg+ 1/
S
)= ( 1/p - 1/
s)
= p Vg = void volume/total
volume
p (density of porous particle) = mass of pellet /volume of mercury displaced by
sample


Mercury Porosimetry
Pore Size Distribution r (nm)= 6300/p(atm abs.)
or r (A
0
) = 8.75X 10
5
/ P (psia)




Hg does not wet surfaces; pressure is needed to force intrusion
From a force balance:
(d in nm, p in bar)
Convenient method for determining pore volume versus pore
size
p
d
14860
p
=
Pressure force. (p() r = -surface tension force, (2 r)
12
Dynamic method for estimating Surface Area (N2 adsorbed, He does
not adsorbed)
13
14
The assumptions of BET isotherm are:

Gas adsorbs on a flat, uniform surface of the solid with a uniform heat of
adsorption due to vander Waals forces between the gas and the solid.

There is no lateral interaction between the adsorbed molecules.

After the surface has become partially covered by adsorbed gas molecules,
additional gas can adsorb either on the remaining free surface or on top of the
already adsorbed layer.

The adsorption of the second and subsequent layers occurs with a heat of
adsorption equal to the heat of liquefaction of the gas

0
,
1
, ...,
n
= Surface area covered (/cm2) by 0, 1, ..., n layers of adsorbed molecules
At Equilibrium 0, 1, 2 must remain constant =>
Rate of Evaporation from First Layer = Rate of Condensation onto Bare Surface
k-11 = k1 P 0
&
Rate of Condensation on the Bare Surface +Rate of Evaporation from the second layer
=
Rate of Condensation on the 1st Layer + Rate of Evaporation from the first Layer =>
k
1
P
0
+ k
-2

2
= k
2
P
1
+ k
-1

1

BET Isotherm
Modification of Langmuir isotherm
Both monolayer and multilayer adsorption
Layers of adsorbed molecules divided in:
First layer with heat of adsorption AH
ad,1
Second and subsequent layers with H
ad,2
= AH
cond
BET isotherm:
BET equation does not fit entire adsorption isotherm
different mechanisms play a role at low and at high p
( )
0
m m
0
ad
1 1
p
p
C n
C
C n p p n
p

+ =

|
.
|

\
|
A A
=
RT
H H
C
cond ad
exp
divide the surface into areas that are uncovered
(fraction
0
), covered by a single monolayer (
1
), two
monolayers (
2
), or by i layers (
i
).

To derive the BET isotherm the surface is divided into regions covered
by i adsorbate layers; each region is characterized by a fractional
coverage
i
.
Suppose there are N
0
sites on the surface, then the
number of atoms adsorbed is N
a


N
a
= N
0
i
i
(1)


i=0


Where we have the usual sum rule
i
=1

i=0
If we now assume that this surface at temperature T
is in equilibrium with a gas then the adsorption rate
equals the desorption rate
Since the atoms/molecules are physisorbed in a
weak adsorption potential
reality model
u
5
u
4
u
3
u
2
u
1
u
0
( ) ... 3 2 1
2 1 0 m ad
+ u + u + u = = u

n n
i
1 - n n 1 - n
1
0
n n 1 - n
1
0 1 0
1
0
1 1
1
0
0
u = u = u u = u
u = u = u u = u

p K p
k
k
k p k
p K p
k
k
k p k
d
a n
d
n
a
d
a
d a
1
st
layer
n
th
layer
For every layer
Langmuir model
Assume
RT
H
RT
H
RT
H
K K K
K K
cond n
ads
e e
e
0 , n 0 , n n
0 , 1 1
A

~ =
=
( )
|
|
.
|

\
|
+
|
|
.
|

\
|

=
0
0
0
m
ad
1 1 1
p
p
C
p
p
p
p
C
n
n
RT
H H
C
cond ads
e
A A
=
with
BET Isotherm
BET Isotherm
At equilibrium we have Ist Layer K-11 = k1 P 0

II layer, k
1
P
0
+ k
-2

2
= k
2
P
1
+ k
-1

1
==>

k
-2

2
= k
2
P
1





In general k
-i

i
= k
i
P
i-1

i
/
i-1
= ki/k-i P


Where F is the incoming flux per site F = P/[N
o
(2mk
B
T)], and E
i
d
is the desorption
energy from layer i.
Note that, due to the change in substrate from the first to the second layer, there
may be a difference between E
1
d
and E
2
d
.
However, for i = 1 and higher we consider desorption essentially as sublimation
from a multilayer of gas, and hence E
2
d
= E
i>2
d
and k
1
k
2
= k
3
= ... = k

.

(2)
To proceed, sample of unknown area is mounted in a
small volume and cooled to low temperature (75 K if we
use N
2
)
The equilibrium pressure (P
0
) for N
2
at 75 K is 750 mbar
The amount of gas adsorbed is then measured as a
function of the pressure, and can conveniently be
expressed in terms of the amount of gas adsorbed in
one monolayer.
0 0
) 1 ( 1
) ( p cv
p c
c v p p v
p
m m

+ =

Plotting P/[V
a
(P
0
P)] versus P/P
0
yields a straight line
with slope S = (c 1)/ c V
0
, crossing the y-axis at I= 1/ c
V
0,


The volume adsorbed in the first monolayer is found as
V
0
= 1/(S + I)


The volume V
0
can be converted into the number of
molecules adsorbed by N
0
= PV
0
/RT and if we know
how big an area each molecule occupies (A
0
) then the
total area, A= N
0
A
0
, can be found
Physisorption
Surface area measurement
S = n
m
A
m
N
monolayer
capacity (mol/g)
specific surface area
(m
2
/g)
area occupied by one
molecule (m
2
/molecule)
Avogadros number
(molecules/mol)
BET model: S
BET
t model: S
t
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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.
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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
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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

26
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)
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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
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 Nitrogen
adsorption/desorption method.

N
2
Physisorption versus Hg
Porosimetry
Hg cannot penetrate small (micro)pores, N
2

can
Uncertainty of contact angle and surface
tension values
Cracking or deforming of samples
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Mercury Porosimetry
Pressure force. (p() r = -surface tension force, (2 r)
Surface tension (Hg)= 450-475 dyne/cm
Pore Size Distribution r (nm)= 6300/p( atm abs.)
or r (A
0
) = 8.75X 10
5
/ P (psia)










Hg does not wet surfaces; pressure is needed to force intrusion
From a force balance:
(d in nm, p in bar)
Convenient method for determining pore volume versus pore
size
p
d
14860
p
=
31
Mercury Porosimetry:
The pore size distribution is determined by
measuring the volume of mercury that
enters the pores under pressure.


Pressures of 0.1 to 200 MPa allow pore
sizes in the range 207500 nm to be
determined.
u 2cos
p=
r
p
32
Gas Adsorption Method:
The gas adsorption method of
estimating pore volume and diameter is
based upon the fact that gas condenses
to liquid in narrow pores at pressure
less than the saturated vapour pressure
of the adsorbate .

33
P 2Vcos
ln( ) = -
P rRT
0
By relating the relative pressure and the pore
radius the pore size distribution of the catalyst
is determined for pore size below 20nm.
The vapor pressure decreases as the capillary size
decreases as the capillary size decreases, such
condensation will occur in smaller pore. At saturation all
pores will get filled with adsorbed nitrogen.
If pressure is reduced by small increment , small amount of
nitrogen will evaporate from the meniscus of largest pore. (in
which V.P of nitrogen is greater than chosen pressure.
N2 Desorption Method (Kelvin equation) :
The BET method can be used to determine the pore size distribution of
porous materials with diameters less than 200, except that high relative
pressures are used for condensing N
2
in the catalyst pores. Capillary
condensation occurs in the pores in accordance with the Kelvin
equation:( variation of V.P WITH CURVATURE effect)


P= V.P of liquid over a curved surface, P
0
= V.P of liquid over a plane
surface, = surface tension of liquid adsorbate ( 8.85 dyne/cm for
nitrogen), V = molar volume of liquid adsorbate (35 cm
3
/mol for N
2
)
By relating the relative pressure and the pore radius the pore size
distribution of the catalyst is determined for pore size below 20nm.
0
2 cos
ln( )
P V
P rRT
o u
=
Pore Size Distribution
Kelvin Equation
Cylindrical pore
Ink-bottle pore
Pore with shape of interstice
between close-packed particles
Adsorbed layer
t
d
p
d
m

r (pore radius) =
t + 2o VCos u /(RT (ln p/p0))
Kelvin Equation
t-Method
BET
only valid in small pressure interval
interpretation not very easy
thickness (t) of adsorbed layer can be calculated
plot of t versus p for non-porous materials is the same (has been
checked experimentally)
t-plot helps in interpretation
0.354 nm
0
2 cos
ln( )
P V
P rRT
o u
=
Kelvin Equation
Pore filling Model
Cylindrical Pore Channel
Pore Size Distribution
Kelvin Equation
39
Total pore volume and PSD
o
k
Po 2 V
In =
P r RT
o
k
2 V
r = +r
P
Po
RTln
P
| |
|
|
\ .
1
3
5
t =4.3
Po
ln
P
Adsorbed layer thickness
= 8.85 dyne/cm, nitrogen , V=35 cm
3
/mol, t (A
0
)= 9.52 (log p
0
/p)
-1/3

r
p
-t (A
0)
= 9.52 (log p
0
/p)
-1
Kelvin Equation
Pore Size Distribution
-alumina

0.0
0.1
0.2
0.3
0.4
0.5
1 10 100 1000
d
p
(nm)
d
V
/
d
d

(
m
l
/
g
/
n
m
)
r = t + 2oVCos u /(RT (ln p/p0))
N
2
Adsorption Isotherms & Pore Volume Distributions
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



wide-pore silica -alumina
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
0.00
0.02
0.04
0.06
0.08
0.10
1 10 100 1000
d
pore
(nm)
d
V
/
d
d

(
m
l
/
g
/
n
m
)

0.0
0.1
0.2
0.3
0.4
0.5
1 10 100 1000
d
pore
(nm)
d
V
/
d
d

(
m
l
/
g
/
n
m
)

N
2
Adsorption Isotherms & Pore Volume Distributions
Pore Size Distribution
t-Method
nm 354 . 0
m
ad
=
n
n
t
n
ad

t
Proportional to S
t

43
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
44
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
V
STP
p
Nitrogen

Linear region
Mono Layer ads

0.00
0.02
0.04
0.06
0.08
0.10
1 10 100 1000
d
pore
(nm)
d
V
/
d
d

(
m
l
/
g
/
n
m
)

Hg Intrusion Curves & Pore
Volume Distributions
Hg Intrusion Curves & Pore
Volume Distributions
Thank You
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