Phase envelopes for variable width square well chain fluids

Abstract

Discontinuous Molecular Dynamics (DMD) and Thermodynamic Perturbation Theory (TPT) have been used to study square-well (SW) chain molecules with variable well-width SW potentials. Well widths of 1.5, 1.8, and 2.0 are considered for united atom models of ethane, n-hexane, and n-octane. The properties studied are the acentric factor, vapor pressure, and liquid density. DMD of purely repulsive potentials was applied to record the number of interaction sites in different wells, giving estimates of the TPT contributions from the attractive potential. DMD simulations of the complete potential near the coexistence condition were used to refine estimates of the derivative quantities related to the compressibility factor. Evaluations of this approach indicate that it is accurate and efficient at βε>0 and η>0.28. Phase diagrams of pure fluids also indicate quantitative accuracy for DMD/TPT at reduced temperatures less than 0.9. The results show that wider wells improve the representation of thermodynamic properties for longer chains. The well width becomes a function of the molecular weight, however.