L15 CRE II Heterogeneous Catalysis

Prof. K.K.Pant
Department of Chemical Engineering
IIT Delhi.
kkpant@chemical.iitd.ac.in
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


3
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

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
A
(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, S= 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
11
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.
12
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
13
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

14
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)
15
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