Criticality and phase behavior in the restricted-primitive model electrolyte: Description of ion association

Abstract

Ion association is incorporated into the restricted-primitive model electrolyte to account for the strong attraction between unlike ions. Two methods are investigated within the McMillan–Mayer framework: first is the binding mean-spherical approximation (BIMSA) based on the Wertheim Ornstein–Zernike integral equation formalism; and the second is the combination of the BIMSA with a simple interpolation scheme based on the Wertheim thermodynamic perturbation theory. The latter gives a better description. Four different association constants are used to calculate the degree of dissociation, the critical point, and the vapor–liquid coexistence curve. An increase in the association constant leads to a lower critical temperature and a higher critical density, and better agreement with computer simulations. When unlike ions are fully paired, corresponding to a charged hard dumbbell system, we obtain the best agreement with the most recent computer simulations of the RPM electrolyte.