Thermodynamics of the salting effect; free energies, enthalpies, entropies, heat capacities, and volumes of the ternary systems electrolyte–alcohol–water at 25 °C

Abstract

The thermodynamic pair interaction parameters of the ternary systems electrolyte (alkali halides and tetraalkylammonium bromides)–nonelectrolyte (n-alcohols and tert-butylalcohol)–water were measured at 25 °C through enthalpies of solution, of mixing and of dilution, densities and heat capacities per unit volume. Some freezing point and electromotive force data were also combined with previously published data to obtain free energies. From these pair parameters the complete thermodynamics of the salting in and salting out of alcohols can be derived and were used to test various theoretical approaches. Most results are consistent with the cosphere overlap structural model, and the various trends can also be correlated through the scaled-particle theory.