When the forces of attraction existing between adsorbate particles and adsorbent almost of the same strength as chemical bonds, the adsorption is called chemical adsorption. This type of adsorption is also known as chemisorptions. Since forces of attraction existing between adsorbent and adsorbate are relatively strong, therefore, this type of adsorption cannot be easily reversed.
Characteristics of chemisorptions
Some important characteristics of chemisorptions are as follows:
(i) High specificity: chemisorptions is highly specific in nature. It occurs only if there is a possibility of bond formation between adsorbent and adsorbate molecules. For example O2 is adsorbed on metals by virtue of oxide formation and H2 is absorbed by transition metals due to hydride formation.
(ii) Irreversibility: as chemisorptions involve the compound formation between adsorbent and adsorbate, it is generally irreversible.
(iii) Enthalpy of adsorption: attractive forces between adsorbent and adsorbate molecules are strong chemical bonds and therefore, molar heat of adsorption is high and is of the order of 200-400 kJ mol-1.
(iv) High activation energy: although chemisorptions is exothermic, yet the process is slow at low temperature. It is because of high activation energy required for chemical process to occur. Like most of the chemical changes the extent of chemisorption increases initially with rise in temperature. High pressure is also supporting for chemisorption.
(v) Surface area: like physisorption, chemisorption also increases with increase in surface area of adsorbent.
(vi) State of adsorbate: since chemical reaction takes place in this type of adsorption, therefore, the molecular state of adsorbate molecules may be altered. For example, oxygen exists as O2, but on the surface where it is chemisorbed, it may exist as O2-, O22-, O-, O, O3-, etc.
(vii) Activation energy: chemical adsorption involves a chemical reaction between adsorbent and adsorbate; therefore, it requires high activation energy.
The adsorption of N2 on iron under two different conditions provides distinction between physisorption and chemisorption. At 83 K nitrogen gas undergoes physical adsorption on iron surface. N2 molecules are amount of N2 adsorbed decreases with further rise in temperature. At room temperature there is almost again shows adsorption as N atoms on the iron surface. This mode of adsorption is chemical adsorption as atoms form chemical bonds with iron atoms.