In physical adsorption, the individuality of the adsorbate and the adsorbent are preserved. In chemisorption, there is a transfer or sharing of electron, or breakage of the adsorbate into atoms or radicals which are bound separately.
Physical adsorption from a gas occurs when the inter-molecular attractive forces between molecules of the solid adsorbent and the gas are greater than those between molecules of the gas itself. In effect, the resulting adsorption is like condensation, which is exothermic and thus is accompanied by the release of heat.
Physical adsorption occurs quickly and may be mono-molecular (unimolecular) layer or monolayer, or 2, 3 or more layers thick (multi-molecular). As physical adsorption takes place, it begins as a monolayer. It can then become multi-layer, and then, if the pores are close to the size of the molecules, more adsorption occurs until the pores are filled with adsorbate. Accordingly, the maximum capacity of a porous adsorbent can be more related to the pore volume than to the surface area.
In contrast, chemisorption involves the formation of chemical bonds between the adsorbate and adsorbent is a monolayer, often with a release of heat much larger than the heat of condensation. Chemisorption from a gas generally takes place only at temperatures greater than 200 oC, and may be slow and irreversible. Most commercial adsorbents rely on physical adsorption; while catalysis relies on chemisorption.