1

Gas Solid Interfaces

Adsorption

) (
adsorbed phase
: adsorbate adsorbent
.
adsorption absorption
:

.



.

:
...
15 C

adsorbent
.


... .
Adsorption of Gases by Solids

C 15

cm3

33

H2

4.7

126

8.0

N2

134

9.3

CO

190

16.2

CH4

304

48

CO2

324

72

HCl

373

99

H2S

Types of
Adsorption

-1

Physical adsorption

.. Van der Waals adsorption

..
.
-2 (Chemical adsorption (Chemisorption
activated

...

3


) (
.
)
40kJmol-1 (


CO H2
kJ mol-1 25
. kJ mol-1 9




.


.


.


.

.
)
(kJ mol-1 80
100 20) ...
(kcal m-1 CO
H2
kJ mol-1 85 kJ 65
-1

. mol

.



.


.

: H2 N2

Ni NH3 O2
.CO CO2

Adsorption Isotherms

4

.
....

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

:

....
-
- .

5
-
- .

:
-1 .
-2 .
P
a+ P

a = K2 / K1

K
K .
P .

a ...
V
P Vm
.
P
P
=
Vm
V

V
Vm

a
Vm

1
Vm

P
V
P

a
Vm

BET

6
The BET Equation for Multimolecular Adsorption

:
site
....

) ( ...

.
.

C 1 P

=
+
V(P P) VmC Vm C P o
o

: V . STP
: P T

.
: V
.
: C :
o

( H ads H liq ) / RT

C = exp

: H Hliq .
Hads> Hliq
II :
Hliq> Hads
III :
ads

C 1

m = CV
m

) (

1
= CV
m

) b (

:
m
1+
b

600

=C

1
m+b

= Vm

7
500
400
( 2

V(cm3
STP

300
P
)V(P P
o

200
100
1.0 0.8 0.6 0.4 0.2
0.0
0.5
)(

0.3 0.2 0.1 0.0

P
Po

0.4
P
Po

)(

)( ) BET(.

77K

) specific surface area
(
Determination of Surface Area

II
B
V
V

:
m

= Vm o . S

S cm

atm 1 273K
23
V S molecules / 10
3

22414 cm = 2.68 x 1019 molecules cm-3 6.02

3

Heat of Adsorption

) ( adsorbed layer

( Solid )

( Gas ) +

)(Heat

200
150

Fe

100

50
0
0

0.2

0.4

0.6

0.8

1.0

Rt