Molecular models for 267 binary mixtures validated by vapor–liquid equilibria: A systematic approach

Abstract

By assessing a large number of binary systems, it is shown that molecular modeling is a reliable and robust route to vapor–liquid equilibria (VLE) of mixtures. A set of simple molecular models for 78 pure substances from prior work is taken to systematically describe all 267 binary mixtures of these components for which relevant experimental VLE data is available. The mixture models are based on the modified Lorentz–Berthelot combining rule. Per binary system, one state independent binary interaction parameter in the energy term is adjusted to a single experimental vapor pressure. The unlike energy parameter is altered usually by less than 5% from the Berthelot rule. The mixture models are validated regarding the vapor pressure at other state points and also regarding the dew point composition, which is a fully predictive property in this work. In almost all cases, the molecular models give excellent predictions of the mixture properties.