TEMPERATURE COEFFICIENTS OF HALF-WAVE POTENTIALS AND MOLAR TRANSFER PROPERTIES OF NA-BUTANOL( AND TL+ FROM WATER TO ITS MIXTURES WITH T)

Gibbs energies for the transfer of Na+ and Tl+ from water to its mixtu res with t-butanol have been derived from electrochemical measurements employing tile negligible liquid junction potential assumption. Trans fer entropies have been obtained from the temperature coefficients of the half-wave potentials on the basis of the assumption of a negligibl e thermal diffusion potential. Transfer enthalpies have been calculate d from Gibbs energies and entropies of transfer. The Gibbs energies of transfer were found to be monotonic functions of the composition of t he solvent mixtures. Transfer enthalpies and entropies for the Na+ cat ion exhibited both minima and maxima. The changes in the Gibbs energie s of tra ns fer were accounted for as donor-acceptor (coordinative) in teractions. The matrix effects on tile transfer entropies and enthalpi es are discussed on the basis of interactions of the cations with clat hrate-like solvent structures.