TEMPERATURE COEFFICIENTS OF ELECTRODE-POTENTIALS AND GIBBS ENERGIES, ENTROPIES AND ENTHALPIES OF TRANSFER OF AG-DIMETHYLTHIOFORMAMIDE AND WITH WATER(, NA+ AND TL+ FROM N,N)

Gibbs energies of transfer for Ag+, Na+ and Tl+ from N,N-dimethylforma mide (DMF) into its mixtures with N,N-dimethylthioformamide (DMTF) and with water were derived from electrochemical measurements on the basi s of the bis(biphenyl)chromium assumption. Transfer entropies were obt ained from the temperature coefficients of the half-wave potentials or electrode potentials employing the assumption of a negligible thermal -diffusion potential. Gibbs energies and entropies of transfer were us ed to calculate transfer enthalpies. The Gibbs energies of Ag+, Na+ an d Tl+ into these two solvent mixtures are interpreted on the basis of hard and soft solvent donor properties. The entropies were influenced by the structure of the solvents. The transfer enthalpies were affecte d by both the solvent donor properties and the solvent structure.