Structure of Equations for Multicomponent Mixtures in Heterogeneous Systems According to Size Fluctuations and the Intermolecular Degrees of Freedom of Components

Abstract

An approach to calculating the effects of density fluctuations is generalized with allowance for the movement of molecules in small condensed multicomponent heterogeneous systems (e.g., droplets, microcrystals, and adsorption on microcrystal faces). The collective character of statistical sums of vibrational, rotational, and translational motions of separate molecules in dense phases is expressed in dependences of these statistical sums on the local configurations of neighboring molecules. Using the quasi-chemical approximation with allowance for interparticle interactions reflecting the effects of direct short-range correlations, a relationship is derived between the statistical sum of a system consisting of a multicomponent mixture of molecules and the statistical sums of individual components. A structure is formulated for isotherm equations associating the density of mixture components and their chemical potentials in a thermostat, and for pair distribution functions.