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Adsorption Isotherms

Adsorption is generally described through isotherms. Isotherms represent equilibrium nature of


adsorption. In simpler words, amount of solute adsorbed on per unit amount of adsorbent and also
the solute concentration in the solution at equilibrium. Various Isotherm models are Langmuir,
Freundlich, BET, Dubinin and Radushkevich, Temkin and Genralized Isotherm. We are going to focus
on Langmuir and Freundlich only.

Langmuir Isotherm : In 1916, Irving Langmuir developed a model Isotherm for adsorption which is
based on four assumptions.

1. The surface of adsorbent is uniform; all the adsorption sites are equivalent.
2. Adsorbed molecules donot interact
3. All adsorption occurs through the same mechanism
4. Adsorption takes place only on the free surface of the adsorbent; monolayer adsorption

These conditions are very difficult to meet all the times. The mechanism of adsorption may differ
form first molecule to last one adsorbed and monolayer adsorption happens in rare cases. This
problems are eliminated in BET Isotherm.

The linear form of Langmuir Isotherm is given as:


1 1 1 1
= +( )∗
𝑞𝑒 𝐶𝑚 𝐾𝐿 𝐶𝑚 𝐶𝑒
where,
𝐶𝑒 = concentration of solute in the solution at equilibrium
𝑞𝑒 =adsorption capacity at equilibrium
𝐶𝑚 = adsorption capacity when monolayer is complete
𝐾𝐿 = related to affinity of binding curves

Separation factor (𝑅𝐿 ), a dimensionless quantity determines the feasibility and favourability of
adsorption process for Langmuir isotherm model. It is given as:
1
𝑅𝐿 =
𝐾𝐿 𝐶𝑜
where,
𝐶𝑜 = intial concentration of solution

𝑅𝐿 >1, then adsorption is unfavourable


𝑅𝐿 =1, adsorption is linear and 𝑅𝐿 <1, adsorption process is highly favourable
𝑅𝐿 =0, adsorption process is irreversible

Freundlich Isotherm: This model is used to describe heterogeneous adsorption system. Freundlich
gave an empirical equation which is represented as:
𝑥
= 𝐾𝐹 𝐶𝑒 1⁄𝑛
𝑚
The linear form of the above empirical equation is given as:
𝑥 1
log ( ) = log(𝐾𝐹 ) + log(𝐶𝑒 )
𝑚 𝑛
where,
x=amount of dye adsorbed
m=weight of adsorbent used
𝐾𝐹 =adsorption capacity
1
=heterogeneity factor and n>1 shows favourable adsorption
𝑛