Effect of the range of particle cohesion on the phase behavior and thermodynamic properties of fluids.

Abstract

Molecular simulations are performed for the (m + 1, m) potential to systematically investigate the effect of changing the range of particle cohesion on both vapor-liquid equilibria and thermodynamic properties of fluids. The results are reported for m = 4-11, which represent a progressive narrowing of the potential energy well. The conventional Lennard-Jones potential is used as a reference point for normal fluid behavior. Small values of m result in a broadening of the phase envelope compared with the Lennard-Jones potential, whereas a contraction is observed in other cases. The critical properties are reported, and a relationship between the critical temperature and the Boyle temperature is determined. The low values of the critical compressibility factor when m < 6 reflect the behavior observed for real fluids such as n-alkanes. The results for supercritical thermodynamic properties are much more varied. Properties such as pressure, potential energy, isochoric thermal pressure coefficient, and thermal expansion coefficient vary consistently with m, whereas other properties such as the Joule-Thomson coefficient exhibit much more nuanced behavior. Maximum and minimum values are reported for both the isochoric heat capacity and isothermal compressibility. A minimum in the speed of sound is also observed.