Phase coexistence in polydisperse charged hard-sphere fluids: mean spherical approximation.

Abstract

Taking advantage of the availability of the analytic solution of the mean spherical approximation for a mixture of charged hard spheres with an arbitrary number of components we show that the polydisperse fluid mixture of charged hard spheres belongs to the class of truncatable free energy models, i.e., to those systems where the thermodynamic properties can be represented by a finite number of (generalized) moments of the distribution function that characterizes the mixture. Thus, the formally infinitely many equations that determine the parameters of the two coexisting phases can be mapped onto a system of coupled nonlinear equations in these moments. We present the formalism and demonstrate the power of this approach for two systems; we calculate the full phase diagram in terms of cloud and shadow curves as well as binodals and discuss the distribution functions of the coexisting daughter phases and their charge distributions.