Molecular dynamics simulation study on the mass transfer across vapor-liquid interfaces in azeotropic mixtures

Mass transfer through fluid interfaces is an important phenomenon in industrial applications as well as in naturally occurring processes. In this work, we investigate the mass transfer across vapor-liquid interfaces in binary mixtures using molecular dynamics simulations. We investigate the influence of interfacial properties on mass transfer by studying three binary azeotropic mixtures known to have different interfacial behaviors. Emphasis is placed on the effect of the intermolecular interactions by choosing mixtures with the same pure components but different cross-interactions such that different azeotropic behaviors are obtained. The molar flux is created by utilizing a non-stationary molecular dynamics simulation approach, where particles of one component are inserted into the vapor phase over a short period of time before the system's response to this insertion is monitored. From a direct comparison of the density profiles and the flux profiles in close proximity to the interface, we analyze the particles' tendency to accumulate in the interfacial region throughout the different stages of the simulation. We find that for mixtures with strong attractive cross-interactions, the inserted particles are efficiently transported into the liquid phase. For systems with weak attractive cross-interactions, the inserted particles show a tendency to accumulate in the interfacial region, and the flux through the system is lower. The results from this work indicate that the accumulation of particles at the interface can act as a hindrance to mass transfer, which has practical relevance in technical processes.