Abstract
In this paper we present a generalization of the van der Waals equation of state for mixtures based on a new concept of calculating the accessible volume of the molecules. The conventional approach for calculating the accessible volume is based on hard-spheres models. With such models it is impossible to incorporate directly the influence of binary interactions which affect the volume occupied by the molecules. On the basis of the original ideas of van der Waals we introduce the concept of apparent size as probed by a particular molecule, in order to approximate the excluded volume for mixtures. With this new concept it is possible to describe the influence of binary interactions on the accessible volume directly.
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