G. Gritzner et F. Horzenberger, GIBBS ENERGIES, ENTROPIES AND ENTHALPIES OF TRANSFER FOR DIVALENT-CATIONS TO SEVERAL SOLVENTS, Journal of the Chemical Society. Faraday transactions, 91(21), 1995, pp. 3843-3850
Citations number
31
Categorie Soggetti
Chemistry Physical","Physics, Atomic, Molecular & Chemical
Gibbs energies of transfer for the divalent cations Cu2+, Zn2+, Cd2+,
Ba2+ and Pb-2+ from the reference solvent N,N-dimethylformamide have b
een derived from reversible polarographic half-wave potentials via the
bis(biphenyl)chromium assumption. Entropies of transfer were calculat
ed from temperature coefficients of the half-wave potentials employing
the assumption of a negligible thermal diffusion potential. Enthalpie
s of transfer were calculated from the equation Delta(t)H degrees = De
lta(t)G degrees + T Delta(t)S degrees. Thermodynamic transfer properti
es for Cu2+, Zn2+ Cd2+, Ba2+ and Pb2+ for up to 23 solvents were obtai
ned. The Gibbs energies of transfer and the enthalpies of transfer ref
lected the principle of hard and soft acids and bases; the entropies o
f transfer of the divalent cations depended linearly on each other for
all solvents. The solvent effects on the transfer properties are acco
unted for as first-sphere interactions between the cations and the sol
vent molecules and by interactions of these entities with the surround
ing solvent matrices.