Chapter 2 Adsorption

Adsorption on solid surfaces

Bond Chap 2
1

IR

> 2000 cm-1

1800 2000 cm-1

3 fold
site

4 fold
site

GC Bond

G = H - TS
6

rNi + rH = 0.125 + 0.035

= 0.16 nm

rNi + rNi,vdw + rH + rH,vdw

= 0.125 + 0.08 + 0.035 + 0.08
= 0.32 nm

p
A2

Physically adsorbed molecule

10

11

12

13

Endothermic chemisorption

14

O2Ag

15

Langmuir adsorption isotherm

16

Assumptions of Langmuir adsorption isotherm :

1.

The adsorbed species are held onto definite points of attachment

on the surface.
( This implies that the maximum adsorption possible corresponds
to a monolayer.)
Each site can accommodate only one adsorbed species.

2.

The differential energy of adsorption is independent of surface

coverage.
(This implies that the surface is completely uniform so that there is
the same probability of adsorption on all sites.
A further implication is that adsorbed molecules are localized.)
Attraction or repulsion forces between adjacent adsorbed
molecules are taken to be negligible, so the energy of an adsorbed
species or the probability of adsorption onto an empty site are
independent of whether or not an adjacent site is occupied.
17

Langmuir adsorption isotherm

K1

A
p
pressure

M
n(1-)

K-1

A-M
n

A: the adsorbed molecule -- adsorbate

M: an adsorption site
-- adsorbent

Vacant sites

k: equilibrium constant
b: the adsorption coefficient of A
: fractional surface coverage; = V / Vm
Vm: the monolayer capacity

= X / Xmax; x is the amount adsorbed at a

given pressure and Xm is the maximum amount
that the surface can be taken up

b = 1/p

18

1
2

T3 > T2 > T1

Adsorption is almost always exothermic, b must decrease with increase of temperature.

G Bond
19

20

V/P vs -V

Slop = 1/Vm

1/V vs 1/p

V
=
Vm
Vm: the monolayer capacity
21

22

23

Langmuir
Temkin

Freundlich

24

25

26

Adsorption of hydrogen
on evaporated film

Adsorption of CO

27

Langmuir
microporous
solids

Brunauer,Emmett and Teller (BET)

Brunauer,Emmett and Teller (BET) equation

Po : the saturated pressure of adsorbate at T
Xm ; monolayer capacity

Xm = 1/(I+S)
28

Open-ended
cylindrical pore

Open slit-shaped
capillaries

Open or closed pores

of vaiousradius

29

Hysteresis loop : evaporation of condensed gas in fine pores does not

occur as easily as its condensation; this is because
a molecule evaporating from a highly curved meniscus
has a higher probability of re-condensing than one
evaporating from a plane surface.

Lord Kelvin

30

GC Bond
p25
31

32