PVT behaviour of fluids with potential models optimised for phase equilibria

Abstract

NPT and NVT Monte Carlo simulations are applied to models for methane and water to predict the PVT behaviour of these fluids over a wide range of temperatures and pressures. The potential models examined in this paper have previously been presented in the literature with their specific parameters optimised to fit phase coexistence data. The exponential-6 potential for methane gives generally good prediction of PVT behaviour over the full range of temperature and pressures studied with the only significant deviation from experimental data seen at high temperatures and pressures. The NSPCE water model shows very poor prediction of PVT behaviour, particularly at dense conditions. To improve this, the charge separation in the NSPCE model is varied with density. Improvements for vapour and liquid phase PVT predictions are achieved with this variation. No improvement was found in the prediction of the oxygen–oxygen radial distribution by varying charge separation under dense phase conditions.