Topography of phase diagrams in binary fluid mixtures: A mean-field lattice density functional study

Abstract

We employ mean-field lattice density functional theory to calculate complete phase diagrams of binary fluid mixtures composed of molecules of equal size. We consider asymmetric binary mixtures in which the attraction strength between like molecules of either species differs as well as the attractivity between a pair of unlike molecules. Focusing on the topology of phase diagrams in the space spanned by the thermodynamic fields temperature , (mean) chemical potential , and incremental chemical potential (, are chemical potentials of pure mixture components A and B, respectively), we present an argument which precludes the existence of tricritical points (TCPs) in binary mixtures in general. This is a consequence of a purely geometrical argument based upon an analysis of the number of ways in which coexistence surfaces can be joined in the (Euclidian) space of , , and . However, we show that by the same token, TCPs may exist in cases where the mixture possesses some special symmetry. These latter results are in qualitative agreement with earlier works where, however, only special cuts through the complete phase diagrams were considered so that the important relation between existence of TCPs and symmetry properties of the mixture cannot be fully appreciated.