COMPUTER-SIMULATION OF VAPOR-LIQUID-EQUILIBRIA OF LINEAR DIPOLAR FLUIDS - DEPARTURES FROM THE PRINCIPLE OF CORRESPONDING STATES

Liquid-vapor equilibrium of linear dipolar fluids has been determined by using the Gibbs ensemble simulation technique. Several elongations and values of the dipole moment were considered. Dipole moment increases the critical temperature and affects slightly the critical density and pressure. Compressibility factor at the critical point decreases as the dipole moment of the molecule increases. Dipole moment provokes deviations from the principle of corresponding states. It is shown that the temperature-density coexistence curve is broadened and that the slope of the vapor pressure curve increases with increasing dipole moment. We propose a new way of reducing the dipole moment so that the increase of the critical temperature becomes almost independent on the molecular elongation. We have also obtained the vapor-liquid equilibrium of models having both a dipole and a quadrupole moment. The obtained data were used to describe the behavior of some relatively complex fluids, namely, 1,1,1-trifluoroethane and 2,2,2-trifluoroethanol. Good agreement for coexistence densities and pressures was obtained. The results presented in this work for linear dipolar fluids along with previous work on linear quadrupolar fluids provide a very comprehensive view of the effect of polar forces on the vapor-liquid equilibrium of linear fluids. © 1995 American Institute of Physics.