Horvath Kawazoe method to determine the pore size

distribution in micropore region

Based on average potential energy in a slit shape pore to obtain pore size distribution from
the information of isotherm data
Obtain a relation between a gas phase pressure and potential energy.

The micropore size distribution can be determined by employing the Horvath and Kawazoe
(HK) method. The method is based on the relationship between slit-shaped micropores and
the adsorption energies. The average potential energy for a slit-shaped pore can be obtained
from the experimental isotherm data (Webb and Orr, 1997; Everett and Powl, 1976).

Although Horvath-Kawazoe (HK) method is mainly for slit-shaped pores, it can be used to
other pore shapes with slight modifications to the model (Horvath and Kawazoe 1983).
Integration of the resulting adsorption potential gives the following equation:


(2.9)



Where;
U
0
= adsorbate-adsorbent energy
U
a
= dsorbate-adsorbate interaction energy











L is varied in order to obtain the corresponding values of P/P
o
. By assuming this relationship, an integral PSD
can be obtained from the adsorption capacity at each relative filling pressure, P/P
o
.





a o
o
U U
P
P
RT + = ln
( ) ( ) ( )
(
(

|
|
.
|

\
|
+
|
|
.
|

\
|

|
|
.
|

\
|

|
|
.
|

\
|

+
=
9
10
3
4
9
10
3
4
4
) 2 / ( ) 2 / ( ) 2 / ( 1 ( 9 ) 2 / ( 1 ( 3
ln
d d d d d L
A N V N
N
P
P
RT
B B A A
AV
o
o o o o
o
(

=

05014 . 0
) 32 . 0 (
10 7087 . 2
) 32 . 0 (
10 895 . 1
) 64 . 0 (
38 . 62
ln
9
7
3
3
L
x
L
x
L P
P
o

differentiation, the integral PSD gives rise to PSD. For nitrogen adsorption, the value of
N
A
is 3.845 10
15
molec.cm
-2
. The value of N
B
can be calculated from the liquid N
2
density
as 6.7 10
14
molec.cm
-2
. The value of is 0.275 nm. With the necessary physical data for
N
2
adsorption on carbon adsorbents, equation (2.11) can be transformed into the
following expression;









Where;
L is the distance between nuclei of two layers (pore width).

The HK model has been proven to be valid for the pores with a size less than 1.34 nm
(Horvath and Kawazoe, 1983).