GIBBS ENERGIES, ENTROPIES AND ENTHALPIES OF TRANSFER FOR DIVALENT-CATIONS TO SEVERAL SOLVENTS

Citation
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
ISSN journal
09565000
Volume
91
Issue
21
Year of publication
1995
Pages
3843 - 3850
Database
ISI
SICI code
0956-5000(1995)91:21<3843:GEEAEO>2.0.ZU;2-Q
Abstract
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.