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Types of Adsorption

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Subject > Chemistry > Chemistry IV > Surface Chemistry > Types of Adsorption
Depending on the nature of attractive forces existing between the adsorbate and adsorbent,
adsorption can be classified as:

i) Physical adsorption

ii) Chemical adsorption

i) Physical adsorption (Physisorption)

In physical adsorption, the forces of attraction between the molecules of the adsorbate and the adsorbent
are of the weak van der Waals' type. Since the forces of attraction are weak, the process of physisorption
can be easily reversed by heating or decreasing the pressure of the adsorbate (as in the case of gases).

ii) Chemical adsorption (Chemisorption)

In chemisorption, the forces of attraction between the adsorbate and the adsorbent are very strong; the
molecules of adsorbate form chemical bonds with the molecules of the adsorbent present in the surface.

Adsorption is generally accompanied by release of energy, that is, most adsorption processes are
exothermic in nature. Adsorption is a spontaneous process; therefore its free energy change is negative
(DG<0). However, the entropy change associated with adsorption is generally negative because the
adsorbate molecules lose their translation freedom when they get attached to the surface of the adsorbent.
Therefore, in order for DG to be negative, the enthalpy change (DH) must be sufficiently negative, such that,
(DG=DH-TDS)<0. This explanation accounts for exothermic adsorption processes. In cases, where
endothermic adsorption occurs as in the case of hydrogen adsorption on glass, the entropy change DS is
sufficiently positive such that DG remains negative. Enthalpy of adsorption, which is the enthalpy change for
the adsorption of one mole of an adsorbate on an adsorbent surface, is usually in the range of 20 kJ/mole to
40kJ/mole while for chemisorption, the values are an order of magnitude high, that is, 200 kJ/mole to 400
kJ/mole.
The differences between physisorption and chemisorption are summarized in the below table.

Comparison between Physisorption and Chemisorption

Physisorption Chemisorption

Forces of attraction are vander Waals’ forces Forces of attraction are chemical bond forces

High enthapy of adsorption (200 - 400

Low enthalpy of adsorption (20 - 40 k.J/mole)
k.J/mole)

This process is observed under conditions of low

This process takes place at high temperatures
temperature

It is not specific It is highly specific

Multi-molecular layers may be formed Generally, monomolecular layer is formed

This process is reversible This process is irreversible

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