SURFACE CHEMISTRY

Adsorption
Sorption: movement of a material from one phase to another.
only on the surface: adsorption

distributing throughout: absorption

Adsorbate: the material being adsorbed. Adsorbent: the material doing the adsorbing.

gas

Adsorbed molecules

solid
Adsorption of gas molecules

Absorption

Adsorption

1.

movement of a material from one phase to another distributing throughout surface

bulk phenomenon

Movement of a material from one phase to another only on the surface

Surface phenomenon

2.

3. 4. 5.

slow process requires porous structure attainment of equilibrium takes some time

Fast Depends on the surface area Equilibrium is attained easily

Chemisorption

involves the formation of chemical bonds between adsorbed molecule and solid surface, and often the breaking of preexisting bonds in the adsorbed molecule. In some cases the chemisorption step requires an activation energy.

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

Comparison between physical and chemical adsorption

S.No Property 1 Nature of forces 2 Extent of adsorption 3 Rate of adsorption 4 Reversibility 5 Nature of molecular layer 6 Heat of adsorption 7 Activation energy 8 Specificity Physical adsorption The forces operating are weak vanderwaals forces. Weak adsorption It is quick process
It is reversible Multilayers are formed

Chemical Adsorption The forces operating are similar to those of chemical bond. Strong adsorption It is slow process
It is irreversible Unimolecular layer is formed It is in the range of 80240 kJ/mol. High

It is 20 to 40 kJ/mol. Low

Non specific

Specific

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.

Langmuir adsorption isotherm The basic assumptions

1. If the bond between adsorbate and adsorbent is weak, a physosorption takes place, on the ether hand if bond is stronger chemisorption occurs.
Irving Langmuir

2. The residual valency force is effective only one molecule thick. 3. It consists two opposing forces, namely condensation and evaporation (desorption). 4. When adsorption starts condensation is highest, while desorption is smallest.

1932 Noble Prize

for his discoveries and investigations in surface chemistry.

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

(1-) Rate condensation r1

rads k1 (1 ) P

Rate evaporation r2
At Equilibrium r1 = r2

rdes k2

k1P aP k2 k1P 1 aP

k1 a the kinetic equilibrium constant of the adsorption k 2 and desorption

a (adsorption coefficient) :

Quantity of the gas adsorbed

kaP bP w k 1 aP 1 aP

at low pressure, aP << 1,

w bP

at high pressure, aP >> 1, w

1
bP 1 aP

p 1 ap w b b y c mx

p w

a b

bP

1 b

BET adsorption isotherm

In 1938, Brunauer-Emmett-Teller derived. Basic assumptions
1) uniform surface; 2) multilayer adsorption;

3) the heat of the layer other than the first layer is the condensation heat; 4) desorption only occur at the layer exposed to the gas

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 0 ( P0 P)V Vm c Vm c P
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

Surface area
P ( P0 P)V

c 1 Vm c

1 Vm c
P P0
BET Plot

Where
N- Avogadro no

S- Adsorption cross section

Vm- Molar volume of adsorbent gas V- volume of monolayer adsorption

a-Mol. Wt of adsorbed gas