Vapor-Liquid Interfaces: Molecular Simulation, Density Gradient Theory, and Experiments

Properties of vapor-liquid interfaces play an important role in many processes, but corresponding data is scarce, especially for mixtures. Therefore, two independent routes were employed in the present work to study them: molecular dynamics (MD) simulations using classical force fields as well as density gradient theory (DGT) in combination with theoretically-based equations of state (EOS). The investigated interfacial properties include: interfacial tension, adsorption, and the enrichment of components, which quantifies the interesting effect that in many systems the density of certain components in the interfacial region is much higher than in either of the bulk phases. As systematic investigations of the enrichment were lacking, it was comprehensively studied here by considering a large number of Lennard-Jones (LJ) mixtures with different phase behavior; also the dependence of the enrichment on temperature and concentration was elucidated and a conformal solution theory for describing the interfacial properties of LJ mixtures was developed. Furthermore, general relations of interfacial properties and the phase behavior were revealed and the relation between the enrichment and the wetting behavior of fluid interfaces was elucidated. All studies were carried out by both MD and DGT, which were found to agree well in most cases. The results were extended to real mixtures, which were studied not only by simulations but also in laboratory experiments. In connection with these investigations, three literature reviews were prepared which cover: a) simulation data on thermophysical properties of the LJ fluid; b) the performance of different EOS of the LJ fluid on that simulation data; c) data on the enrichment at vapor-liquid interfaces. Electronic databases were established for a) - c). Based on c), a short-cut method for the prediction of the enrichment from readily available vapor-liquid equilibrium data was developed. Last not least, an MD method for studying the influence of mass transfer on interfacial properties was developed and applied to investigate the influence of the enrichment on the mass transfer