Thermodynamics of liquid and fluid mixtures from the kinetic Monte Carlo viewpoint

Abstract

In this study a binary mixture is modelled in a uniform simulation cell at various temperatures using an extended version of the grand canonical kinetic Monte Carlo (GC-kMC) method. The main goal of this study is to consider the thermodynamic properties of binary liquids, gases, and gas–liquid mixtures from a more general point of view than that applied to the particular case of vapour–liquid equilibrium when the pressure and partial chemical potentials in coexisting phases are the same. Particular attention is paid to thermodynamic functions such as chemical potentials, Gibbs free energy and entropy. For the pair potential of unlike molecules a more universal scheme is proposed in comparison with the Lorentz–Berthelot combining rule. The approach is tested on an Ar–Kr mixture in a wide range of temperatures. In all cases, the obtained values of chemical potentials, pressure and internal energy for the entire set of component densities and temperature fully satisfy the Gibbs–Duhem equation with a high degree of accuracy. For the case of vapour–liquid equilibrium, the developed approach made it possible to reproduce the experimental pressure–composition diagrams with the highest accuracy ever achieved in the literature. Despite the fact that the Ar–Kr mixture, according to Raoult's law, is close to an ideal system, it was found that the partial pressures in the liquid phase or in a dense supercritical gas mixture are non-linear functions of the composition, and the partial pressure of the heavier component (Kr) can even be negative.