L16 CRE II Heterogeneous Catalysis

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

3
Experimental Methods of Estimating
Pore Volume and Diameter
Two methods are used : one is based on gas
adsorption is suitable for the estimation of pore
sizes in the range 15-200A
0
. (N2
adsorption/desorption method)

Other is based on the volume of mercury which
can be forced under pressure into the pores of a
solid and is suitable in the pore size range 100-10
5

A
0
. (Mercury penetration 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
5
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
=
6
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
7
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 .

8
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
14
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 Plot Method (for microporous materials,)
nm 354 . 0
m
ad
=
n
n
t
n
ad

t
Slope is Proportional to surface
area S
t

18
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
19
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

20
21
Total pore volume and PSD
Hg Intrusion Curves & Pore
Volume Distributions
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
)

Thank You
25