Abstract
The criterion of ideal behavior of a mixture of a few molecules within a separate zeolite cavity is formulated on the basis of the statistical thermodynamics. The criterion determines the dependence of the Helmholtz free energy, internal energy, and entropy of a molecular aggregate on the ratio of the number of molecules of components 1 and 2. The similarity between this criterion and the criterion of ideal behavior for bulk solutions is shown. Expressions of excess thermodynamic functions of the molecular mixture in a cavity are obtained. The negative magnitude of these excess functions is proposed to be due to rearrangement of molecules under influence of energetic heterogeneity. The calculation procedure of the excess functions has been demonstrated for the system CO2-C2 H6-zeolite NaX, the information of both isotherms and isosteric adsorption heats being used simultaneously. The approach offered allows the state of adsorbed mixture in a separate cavity to be analyzed from pure-component and multicomponent experimental data.
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