Langmuir’s adsorption isotherm

According to Langmuir the phenomenon of adsorption can be explained theoretically on

the basis of the following assumptions:
 Valencies at the surface of adsorbent atoms are not fully satisfied and, therefore, they
can share electrons with atoms present in the adsorbate to form bonds resembling a
covalent linkage.
 If this bond is weak, a physical adsorption takes place. On the other hand, if bond is
stronger, chemisorption occurs.
 The residual valency force on the surface of adsorbent is effective only up to a small
distance (about 2 x 10-8 cm) and hence, the adsorbed gas layer is only one molecule
thick.
 (iii) The phenomenon of adsorption consists of two opposing processes, namely,
condensation of the molecules of the adsorbate on the surface of the adsorbent and
evaporation of the adsorbed molecules from the surface of the adsorbent.
 As the surface becomes progressively covered, the rate of condensation gradually
decreases; while the rate of evaporation of the condensed molecules gradually
increases.
 Ultimately a dynamic equilibrium is set up, when the rate of condensation becomes
equal to the rate of evaporation.
Consider a surface on which the molecules of a gas are condensing and evaporating. Let
 = fraction of the total surface covered at a particular instant, then (l - ) = fraction of the
surface still bare

Adsorbed
Fraction
molecules
adsorbed evaporate Gas molecules
to be adsorbed Fraction bare

 1– 

Figure 6: Gas molecules condensing and evaporating on surface

Where K1 is the specific condensation rate constant and P is the pressure of the gas

Rate of evaporation r2  K 2 . … (ii)

At equilibrium: r1  r2 or

K1 (1   ) P  K 2 . or
 K1
P
K1 P K2 aP
   …. (iii)
K 2  K1 P K 1  aP
1 1 P
K2

where a = K1/K2.

But, the quantity of gas adsorbed per unit mass of the adsorbent, w is proportional to
the surface covered, i.e.,

w  K. … (iv)

From (iii) and (iv), we get:

KaP bP
w  (b  Ka) ... (v)
1  aP 1  aP

This equation is called Langmuir's adsorption equation. The above equation may be re-
P 1 a
written as   P … (vi)
w b b

Thus, if we plot P/w against P, we should get a straight line. This equation has found
valid in all cases (see Fig. 7).

Case I: At very low pressures, aP becomes negligible in comparison with 1, hence; equation (v)
reduces to: W = bP ... (vii)

amount of adsorption per unit weight of adsorbent at a given temperature is directly

proportional to the pressure of the gas at low pressures. (see Fig 7)


 a

 b

P/w 

Slope = tan = a/b

1/b

P
 Figure 7: Plot of P/w Vs P at very low pressure

Case II: At high pressures, aP is very high as compared with 1 and, therefore, (v) takes the form

bP b
w   constant … (viii)
aP a

i.e., at high pressures, the extent of adsorption at a given temperature is independent of

pressure of the gas, because the surface becomes completely covered.

Applications of adsorption on pollution abatement

1. In gas masks where activated charcoal adsorbs poisonous gases.

2. Refining of petroleum and decolouring cane juice.
3. Creating vacuum by adsorbing gases on activated charcoal.
4. The adsorbents used in air pollution control include activated carbon, carbon molecular
sieves, polymers, silica alumina, and zeolites. Activated carbon is the most widely used
adsorbent. It can adsorb a broad range of pollutants with varying dimensions by its
broad pore distribution of micro- and mesopores.
5. Adsorption on activated carbon is capable of a deep elimination of minor amounts of
almost all low to medium volatile pollutants from a gas stream.
6. Impregnated carbons: Impregnated carbons are developed for pollutants that are
difficult to control with standard activated carbons. Such adsorbents retain specific
contaminants long enough for their conversion by the chemical impregnating agent,
forming a stable compound within the carbon. They are used in a wide range of air, gas
and water purification and industrial process applications.
7. Zeolites, also called molecular sieves, are crystalline silicates.
8. Silicagel is used for sorption of polar compounds, organic vapors, removal of easy
condensing vapours and gases.
9. Activated alumina is used as an adsorbent are for removal of oxygenates and
mercaptans from hydrocarbon feed streams, fluoride ions from water, etc.
10. Removal of colouring matter from solution: (i) Animal charcoal removes colours of
solutions by adsorbing coloured impurities. (ii) Animal charcoal is used as decolouriser in
the manufacture of cane sugar.

Impregnating agent wt. % Quantity Application

Sulfuric acid 2 – 25 Gas purification from ammonia, amine,
mercury
Potassium carbonate 10 – 20 Gas purification from acid gases: HCl,
HF, SO2, NO2
Manganese IV oxide no data Gas purification from aldehyde
Triethylene diamine 2–5 Gas protection from radioactive methyl
iodide
Zinc oxide 10 In gas masks against hydrogen cyanide
Chromium – copper – 10 – 20 Military and civil protection: phosgene,
silver salts chlorine, arsine, sarin and other nerve
gases
Silver 0.1 – 3 Domestic drinking water filters