Criticality and phase behavior in the restricted-primitive model electrolyte: Effect of ionic association

Ion association is incorporated into the restricted-primitive model (RPM) 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 (SIS) 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 (CHDB) system, we obtain the best agreement with the most recent computer simulations of the RPM electrolyte