Theory-based constraints on variations of infinite dilution partial molar volumes of aqueous solutes at various temperatures and water densities

Known theoretical relations provide constraints on variations of the partial molar volume of an infinitely diluted solute at: (1) low solvent densities (as follows from the truncated virial EoS), (2) at the critical point of the solvent (as follows from the near-critical theory of dilute mixtures); and (3) at conditions where repulsive interactions dominate, i.e. at ρc1>1.5ρc1>1.5 close to and above the Boyle temperature of a solvent, and ρc1>3ρc1>3 close to the melting temperature of a solvent (as follows from the theory of mixtures of hard spheres). These constraints are discussed for the case of aqueous solutions at various temperatures and water densities. The constraints provide rigorous checks of the quality of models proposed to correlate or predict V2∞ values, and, if applied properly, can significantly improve the reliability of predictions of both V2∞ and the fugacity coefficients ϕ2∞.