Enthalpies of Solution of Organic Compounds inWater/Octan-1-ol Mixtures. A Rationale Based ona Model of Structural Organization of the SolventMedium

Limiting enthalpies of solution _solnH°(oct/w) of several monofunctionalcompounds (tetrahydropyran, diethylamine, pyrrolidine, piperidine,1-methylpiperidine) in water–octan-1-ol mixtures with water content ranging from zero tosaturation have been determined at 25°C. The observed phenomenology hasbeen interpreted by supposing that the solvent medium undergoes a microphasetransition at water mole fraction of about 0.08. In the water-poor region theexperimental behavior is consistent with the presence of water molecules inprevailingly monodispersed form, while in the water-rich region the formationof organized pseudomicellar water aggregates is suggested. Two different simplemodels have also been proposed to describe quantitatively the observed trendsof _solnH°(oct/w) vs. mole fraction of water.Deceased while this research was in progress. The coauthors wish to dedicate this work to his memory