Dimerization of hard sphere fluid in inert solvent

Abstract

Statistical-thermodynamic analysis of the dimerization equilibrium within a hard sphere model in the presence of an inert solvent was carried out. Calculation of the dimerization equilibrium at constant temperature and pressure requires the solution of two equations: the mass action law (MAL) and the equation of state (EOS). Both positive and negative deviations from ideality in a dimerizing hard sphere system with an inert solvent can be simply described by using the minimum number of parameters that characterize the ratio of the components' sizes in the mixture. The enthalpy of mixing varies from the pure endothermic to that of alternating with the exothermic effect at moderate and high concentrations, which are dependent on the ratio of the dimerizing species and the solvent hard-sphere diameters.