A simple approximation scheme is given for the association constant of a family of models of associating particles introduced and considered by Cummings and Stell, Rasaiah et al., and Stell. The result correctly reduces to the law of mass action at low concentrations. For the ionic‐species version, the theory requires accurate assessment of the cavity function of charged hard spheres, for which we develop a recipe. We show the close similarity (and some differences) between the above models and those considered by Wertheim, through a simple extensions of his models. We also note the equivalence of our approximation and Wertheim’s first‐order thermodynamic perturbation theory.
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G. Stell, SUNY CEAS Report No. 460, March 1985; Invited contribution to the Colston Symposium on Water and Aqueous Solution, University of Bristol, April 1985.
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L. Boltzmann, Lectures on Gas Theory (translated by S. G. Brush, University of California, City, 1964), Part II, Chap. 6.
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This series in powers of η was obtained and analyzed by G. O. Williams (unpublished work, 1985).
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G. Stell and G. O. Williams (to be published). Results presented at 57th Statistical Mechanics Meeting, Rutgers University, May 7, 1987.
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© 1989 American Institute of Physics.
1989
American Institute of Physics
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