Molecular Dynamics Simulations of Vapor-Liquid Interface Properties of n-Heptane/Nitrogen at Subcritical and Transcritical Conditions.

Vapor-liquid interfacial properties of n-heptane/nitrogen at various temperatures and pressures in the ranges of 270-648 K and 10-60 bar were investigated using molecular dynamics (MD) simulations. Additionally, density gradient theory (DGT) was used to predict the binary system interface for qualitative comparison purposes. Results show that surface tension decreases with the increases in both temperature and pressure, but the rate of decrease against the latter is smaller. The interface thickness, which is of the order of several nanometers, was also shown to have a much stronger dependence on temperature and almost invariant with respect to pressure. MD also reveals the phenomenon of nitrogen enrichment in the outer interfacial region at low subcritical temperatures. A sensitivity analysis of influence parameters on DGT results revealed that surface tension values are a stronger function of n-heptane influence parameter and almost invariant with respect to nitrogen influence parameter. The velocity distribution function (VDF) shows that the molecules in and away from the interface follow the Maxwellian distribution of kinetic theory at subcritical conditions. The VDF of the velocity component normal to the interface of the evaporated n-heptane molecules adjacent to the interface exhibits a deviation from the Maxwellian distribution. The VDF of all three components of velocity of n-heptane molecules at supercritical conditions exhibits a departure from the Maxwellian distribution as well.