M.

Hamid Mahboob Roll No: 138 Pharm-d(1 st

Prof.)

Adsorption Isotherm
It is the graph between the amounts of adsorbate (x) adsorbed on the surface of
adsorbent (m) and pressure at constant temperature.
Basic Adsorption Isotherm
 In adsorption, adsorbate gets adsorbed on adsorbent.

According to Le-Chatelier principle or "The Equilibrium Law”;

➢It describes what happens to a system when something momentarily takes it away
from equilibrium.
At a high pressure a stage is reached when all the sites are occupied and further increase
in pressure does not cause any difference in adsorption process. At high pressure,
adsorption is independent of pressure.

1) FREUNDLICH ADSORPTION ISOTHERM:

In 1909, Freunlich gave an empirical expression representing the isothermal variations.
Adsorption of a quantity of gas absorbed by unit mass of solid adsorbent with pressure.

Freundlich Equation:

This equation is known as Freundlich, Adsorption Isotherm or Freundlich Adsorption

equation or simply Freundlich
Isotherm.
Where; X is mass of gas adsorbed on mass
m is mass of adsorbent at pressure
P,K and n are constants
Freundlich isotherm correctly established the relationship of adsorption with pressure at
lower values; it failed to predict the value of adsoption at higher pressure.

At low pressure graph is nearly straight line.

2- Langmuir Isotherm:

In 1916 Langmuir proposed another Adsorption Isotherm known as Langmuir

Adsorption isotherm.
• This isotherm was based on dynamic equilibrium exists between adsorbed gaseous
molecules and the free gaseous molecules.

Where A (g) is unabsorbed gaseous molecule, B(s) is unoccupied metal surface and AB is
Adsorbed gaseous molecule.
Monolayer is formed
Adsorption at fixed active sites
Rate of adsorption was related to unoccupied sites
Rate of desorption was related to occupied sites
Where ;
•θ the number of sites of the surface which are occupied with gaseous
molecule,
•P represents pressure and
•K is the equilibrium constant for distribution of adsorbate between the surface and the
gas phase .
The basic limitation of Langmuir adsorption equation is that it is valid at low pressure
only.
•At lower pressure, KP is so small, that factor (1+KP) in denominator can almost be
ignored.
So Langmuir equation reduces to:
θ=KP
• at high pressure KP is so large, that factor (1+KP) in denominator is nearly equal to KP.
• So Langmuir equation reduced to

3) BET ADSORPTION ISOTHERM:

BET Theory put forward by Brunauer, Emmett and Teller
multilayer formation is the true picture of physical Adsorption.
BET theory linked to type II isotherms
BET equation is given as
p/Y(p0-p) = 1/ Ymb + (b-1)/Ymb (p/p0)
•p is pressure of adsorbate molecules
•Y is mass of vapours adsorbed per gram of adsorbent
•p0 is the saturation vapours pressure
•Ym is mass of vapours adsorbed per gram of adsorbent when monolayer is complete
•b is the constant that is proportional to difference
between the heat of adsorption (first layer) and the latent heat of condensation
(successive layers)
For simple monolayer BET equation reduces to Langmuir equation.
BET (multilayers) equation is given as:
p/Y(p0-p) = 1/ Ymb + (b-1)/Ymb (p/p0)
Langmuir (monolayer) equation is given as:
p/Y = 1/ Ymb + p/Ym

Types of Adsorption Isotherm

There are FIVE types of isotherm:

Type I, Type II, Type III, Type IV ,Type V

Isotherm Type of Nature of adsorbent Graph

adsorption
Type-| Langmuir type Is found for porous
material with small
pores e.g. Adsorption
of Nitrogen (N2) or
Hydrogen (H) on
charcoal

Type-|| Sigmoid type e.g. Nitrogen (N2

(g) adsorption on silica
gel

Type-||| Hyperbolic type Bromine (Br2) at 790C

on silica gel or Iodine (I2)
at 790C
on silica gel.

Type-|V Sharp approach adsorption of

to the line p° Benzene on Iron Oxide
(Fe2O3) at
500C and adsorption of
Benzene
on silica gel at 500C

Type-V Elongated type e.g. adsorption of

krypton on carbon black
at 90K