Thermochemical investigations of associated solutions: calculation of solute--solvent equilibrium constants from solubility measurements.
A simple solution model that has lead to successful predictive equations for the partial molar excess properties of a solute in simple binary solvent mixtures containing only nonspecific interactions is extended to include association between the solute and one of the solvent components. An expression is derived and tested for its ability to describe anthracene solubilities in binary solvent mixtures containing benzene. The best description of the experimental solubilities requires the formation of a 1:1 anthracene-benzene complex, with a molarity-based equilibrium constant of KcAC approximately equal to 0.107 M-1. In comparison, a stoichiometric complexation model which attributes all solubility enhancement to the formation of anthracene-benzene complexes requires a somewhat larger equilibrium constant (KcAC approximately equal to 0.228 M-1) to describe the solubility behavior of anthracene in the benzene-n-heptane system. The results of these calculations illustrate that the determination of solute-solvent equilibrium constants from solubility data depends on the theoretical model used and the manner in which nonspecific interactions are incorporated into the model.
D055598:Chemical Phenomena; D002627:Chemistry, Physical; D008956:Models, Chemical; D012995:Solubility; D012996:Solutions; D012997:Solvents; D013816:Thermodynamics
D012996:Solutions; D012997:Solvents