TOWARDS A MOLECULAR THEORY FOR THE VAN DER WAALS–MAXWELL DESCRIPTION OF FLUID PHASE TRANSITIONS

We briefly review developments of theories for phase transitions of molecular fluids and mixtures, from semi-phenomenological approaches providing equations of state with adjustable parameters to first-principles microscopic methods qualitatively correct for a variety of molecular models with realistic interaction potentials. We further present the generalization of the van der Waals–Maxwell description of fluid phase diagrams to account for chemical specificities of polar molecular fluids, such as hydrogen bonding. Our theory uses the reference interaction site model (RISM) integral equation approach complemented with the new closure we have proposed (KH approximation), successful over a wide range of density from gas to liquid. The RISM/KH theory is applied to the known three-site models of water, methanol, and hydrogen fluoride. It qualitatively reproduces their vapor-liquid phase diagrams and the structure in the gas as well as liquid phases, including hydrogen bonding. Furthermore, phase transitions of water and methanol sorbed in nanoporous carbon aerogel are described by means of the replica generalization of the RISM approach we have developed. The changes as compared to the bulk fluids are in agreement with simulations and experiment. The RISM/KH theory is promising for description of phase transitions in various associating fluids, in particular, electrolyte as well as non-electrolyte solutions and ionic liquids.