1

Gas Solid Interfaces

Adsorption

)
(
adsorbed phase : adsorbate
adsorbent

.
adsorption
: absorption


.



.

Adsorption of

Gases by Solids

:
...
15
C

adsorbent
.


...
.
o

15

cm3

33

H2

4.7

126

8.0

N2

134

9.3

CO

Types of

190

16.2

CH4

Adsorption

-1

304

48

CO2

324

72

HCl

Physical

adsorption

H2S

99
373
.. adsorption
Van der Waals

..
.
-2
activated


...
)Chemical adsorption (Chemisorption

)
.
(
.
)
)
(kJ mol-1 80
40kJmol-1

(
100 20) ...

(kcal m-1

CO H2
CO H2
85

kJ mol-1 . kJ mol-1 65
kJ mol-1 25 kJ mol-1 9

.











.
.





.

.




.
.

: H2 N2
.
Ni NH3
O2

4
.CO CO
2

Adsorption Isotherms

5

.
....

II

I
Vm

Vads

Vads
P

III

P P

IV

Vads

Vads

P P

VI

Vads

Vads

P P
O

The Langmuir Adsorption Isotherm Equation

:

....
-

6
- .
-
- .

:
-1 .
-2
.
P

= aP

a = K2 / K1

K
K .
P .

a
...
V
P Vm
.
a
P
P
+
=V
V
V
m

V
Vm

=
P
V

1
Vm

7
P
a
Vm

BET

The BET Equation for Multimolecular Adsorption

:
site

....

) ( ...

.
C 1 P

o .
Vm C P

1
Vm C

= ) P

P
o

V(P

: V . STP
: P
T

.
: V
.
: C :
o

H ads H liq / RT

exp

=C

: H
.
II :
III :
ads

Hliq

Hads> Hliq
Hliq> Hads

8
C 1
CVm

=m

) (

1
CVm

= b

) (

:
1+

m
b

=C

1
mb

= Vm

600
500
( 2

3
400
V(cm3
STP

300
P
)V(P P
o

200
100
0.2
0.3

1
0.6 0.4
0.5 0.4
)(

0.8

0.1 0.0

1.0
0.0

P
Po

0.2
)(

P
Po

) 77K(
) BET(.

specific surface area
) (
Determination of Surface Area

II B


V
m

9
V


:
m

= Vm o . S

S cm

atm 1
273K
23
V S molecules / 22414 10
3

cm3 = 2.68 x 1019 molecules cm-3 6.02

o

Heat of Adsorption

) ( adsorbed layer

) ( Solid

( Gas ) +
) (Heat

200
150

Fe

100

Rt

50
0

0
0.2

0.4

0.6

0.8

1.0