Abstract
Adsorption on a nonporous, nonswelling adsorbent and adsorption in micropores represent two limiting cases of physical adsorption which are clearly distinguishable thermodynamically. In the first case, the chemical potential of the adsorbent is independent of the amount of the adsorbed substance; in the second case, it varies with it. The works of Brunauer, which made a whole epoch in the theory of adsorption, belong to the first type of adsorption phenomena; adsorption in micropores, however, is beyond the framework of his investigations. It should be treated in terms of volume filling, and not of layer-by-layer coverage of the surface. In computational methods of the theory in hand, a substantial role is played by the concept of the temperature invariance of free energy of adsorption as a function of the degree of filling. An analysis of this concept is given and the limits of its applicability are assessed. Exact and approximate expressions for the calculation of the basic thermodynamic functions in adsorption in micropores have been obtained. A generalized thermal equation of adsorption, i.e., ψ( θ, p, T) = 0, applicable to the quantitative description of adsorption of molecules sharply differing in electronic structure on microporous adsorbents widely different in nature (active carbons, zeolites, etc.) is considered.
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