Abstract

Experimental determination, theoretical modeling, and molecular simulation have been combined to describe the bulk phase equilibria (i.e., pressure, liquid, and vapor saturated mass densities) and interfacial properties (i.e., interfacial concentration, adsorption, and interfacial tension) for methane + n-decane, n-dodecane, n-tetradecane and n-hexadecane binary mixtures at 344.15 K and in a pressure range between 0.1 and 30 MPa. Experimental determinations are carried out using a combined apparatus that includes a high-pressure vibrating tube densimeter and a high-pressure pendant drop tensiometer. The theoretical approach is based on the van der Waals gradient theory coupled to the Statistical Associating Fluid Theory of Variable Range employing a Mie potential (SAFT-VR-Mie) equation of state, where the fluids are described as Coarse Grained (CG) atoms. Molecular dynamics simulation for the same systems based on the CG Mie potential are reported. The three approaches are able to indepen independently predict phase equilibrium and interfacial properties, showing a very good agreement amongst themselves. For the systems and conditions studied here, the vapor mass density increases; the liquid mass density and interfacial tensions decrease as the pressure increases, and with a fixed temperature and pressure, the liquid mass density and interfacial tensions increase as the n-alkane molecular chain length increases. It is observed that methane is adsorbed along the interfacial region, whereas the n-alkanes (n-decane, ndodecane, n-tetradecane, n-hexadecane) do not exhibit surface activity. The relative Gibbs adsorption of methane increases significantly with pressure until it reaches a maximum denoting the adsorption saturation limit. It is also observed that the adsorption of methane only slightly increases with the chain length of the n-alkane. (C) 2021 Elsevier B.V. All rights reserved.