The molecular properties governing solubilities of organic nonelectrolytes in water

Abstract

Among the important problems in solutions chemistry, hitherto unresolved, is that of identifying and evaluating the solute and solvent molecular properties governing solubilities of organic non-electrolytes in water. There are few subjects having such widespread ramifications. The treatment of solubility phenomena in terms of molecular properties of both solutes and solvents is made particularly explicit in the approach in which the endoergic formation of a solvent cavity suitable for the solute molecule is opposed, on insertion of the solute, by exoergic terms involving solute–solvent intermolecular interactions. Recently¹, we used this approach, together with our intermolecular-force parameterizations, called solvatochromic parameters^2,3, to correlate and predict octanol/water partition coefficients for non-hydrogen-bond donor aliphatic solutes. We now report linear solvation energy relationships which, we believe, represent a resolution of the problem for non-hydrogen bonding, hydrogen-bond acceptor and weak hydrogen-bond donor liquid aliphatic solutes.