SURFACE CHEMISTRY

Absorption Adsorption

1. movement of a material Movement of a material from

from one phase to one phase to another only
another distributing on the surface
throughout surface

2. bulk phenomenon Surface phenomenon

3. slow process Fast

4. requires porous structure Depends on the surface area

5. attainment of equilibrium Equilibrium is attained easily

takes some time

Dr. E. Laxminarayana
Chemisorption
involves the formation of chemical bonds between adsorbed
molecule and solid surface, and often the breaking of preexisti
ng bonds in the adsorbed molecule. In some cases the chemiso
rption step requires an activation energy.

physisorption
involves forces similar to the van der Waals forces that lead
to condensation of vapors to liquid.

Dr. E. Laxminarayana
Comparison between physical and chemical adsorption
S.No Property Physical adsorption Chemical Adsorption
1 Nature of The forces operating The forces operating are
forces are weak vanderwaal’s similar to those of
2 Extent of forces. chemical bond.
adsorption Weak adsorption Strong adsorption
3 Rate of It is quick process It is slow process
adsorption
4 Reversibility It is reversible It is irreversible
5 Nature of Multilayers are formed Unimolecular layer is
molecular formed
layer
6 Heat of It is 20 to 40 kJ/mol. It is in the range of 80-240
adsorption Low kJ/mol.
7 Activation High
energy Non specific
8 Specificity Specific

Dr. E. Laxminarayana
 isotherm

Adsorption increases with

increase of pressure under
low pressure. While at high
pressure, adsorption attains
maximum value.

adsorption isotherm:
an expression that gives the fraction  of a surface that is
covered by adsorbed molecules in equilibrium at constant
temperature as a function of pressure or concentration.
Dr. E. Laxminarayana
Langmuir adsorption isotherm
The basic assumptions
1. If the bond between adsorbate and adsorbent is weak, a physos
orption takes place, on the ether hand if bond is stronger chemi
sorption occurs.
2. The residual valency force is effective only one molecule thick.
3. It consists two opposing forces, namely condensation and evap
oration (desorption).
4. When adsorption starts condensation is highest, while desorptio
n is smallest.

Dr. E. Laxminarayana
 As the surface becomes covered, the rate of condensation decreases,
while the evaporation increases. Ultimately a dynamic equilibrium is set
up.
Let  is fraction the total surface covered, then (1-) is fraction of surface
still bare

Rate condensation r1 rads  k1 (1   ) P

Rate evaporation r2 rdes  k 2

At Equilibrium r1 = r2
k1 P aP
 
k 2  k1 P 1  aP

k1 a (adsorption coefficient) :
a
k 2 the kinetic equilibrium constant
of the adsorption and desorption
Dr. E. Laxminarayana
BET adsorption isotherm
In 1938, Brunauer-Emmett-Teller drived.

Basic assumptions
1) uniform surface;
2) multilayer adsorption;
3) the heat of the layer other than the first layer is the conde
nsation heat;
4) desorption only occur at the layer exposed to the gas

Dr. E. Laxminarayana
For the isotherms the multi layer adsorption is responsible for a
condensation of large amount of adsorbate. Then the derivation is more
complicated than Langmuir but going in similar lines we obtain:

P 1 c 1 P
 
( P0  P)V Vm c Vm c P 0

Where P and P0 equilibrium pressure and saturation pressures of

adsorbate at adsorption temparature.
V is adsorbed gas quantity in volume units
Vm is the monolayer adsorbed gas quantity
Dr. E. Laxminarayana
 Surface area

c 1
P
( P0  P )V Vm c

1 Where
Vm c N- Avogadro no
S- Adsorption cross section
P Vm- Molar volume of adsorbent gas
P0 V- volume of monolayer adsorption
BET Plot

Dr. E. Laxminarayana
Adsorption indicators:

Indicators like eosin used in precipitation titration such as KBr versus

AgNO3
KBr + AgNO3AgBr + KBr
AgBr precipitate formed at the end point of the reaction preferentially
adsorb eosin, producing a brick red color change.
 For softening of hardwater by zoelite resin.
 As surface active agents like wetting agents, emulsifiers, soaps and
detergents.
Eg:- generally oil drops or dirts remain isolated as drops.In presence of
good wetting agents, the drops spread into a thin film and become
surface active(for adsorption)
 In the manufacture of sulphuric acid, finely divided platinum is used

Dr. E. Laxminarayana