Phase Equilibria of Quadrupolar Fluids by Simulation in the Gibbs Ensemble

Abstract

Vapour-liquid phase diagrams for pure fluids and mixtures of molecules with Lennard-Jones plus quadrupole-quadrupole interaction potentials were determined by Monte Carlo simulation in the Gibbs ensemble [I]. This is the first reported application of the method to molecular fluids. We have demonstrated that the Gibbs method works reliably for strongly interacting molecular fluids at liquid densities. Pure fluid calculations were performed for reduced quadrupole strengths, Q* = Q/(epsilon sigma(5))(1/2) equal to I and root 2, typical of molecules like C2H2 and C2H4. It was found that the critical temperature of the quadrupolar fluid increased rapidly with increasing quadrupolar strength, in good agreement with previous computer simulation and theoretical results. A single mixture with components characterized by identical Lennard-Jones parameters and Q(1)* = +1, Q(2)* = -1 was studied at three temperatures. A negative azeotrope was observed at the lowest temperature studied, as seen experimentally in the CO2/C2H2 mixture. The perturbation theory calculations are in good agreement with the simulation results for all properties except coexisting liquid densities. The results illustrate some of the strengths and limitations of perturbation theories based on the Pade approximant for the free energy of polar fluids.