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Issue 9, 1989
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Preferential solvation of ions in mixed solvents. Part 4.—Comparison of the Kirkwood–Buff and quasi-lattice quasi-chemical approaches

Abstract

The relation of the Kirkwood–Buff integrals Gij=∫04πr2[gij(r)–1]dr where i is an ion solute and j one of two solvents in their mixture, to measurable quantitites is examined in the light of recent work of Ben-Naim and Newman. The derived local excess of one of the solvents δxij is compared with the same quantity calculated for the author's quasi-lattice quasi-chemical mode. The results for three aqueous solvent mixtures, involving a protic solvent (methanol), a strong donor aprotic solvent (dimethyl sulphoxide) and a weak donor aprotic solvent (acetonitrile) and several ions are compared and discussed. It is concluded that the need for the derivative of the standard Gibbs free energy of transfer of the ion with respect to the solvent composition limits the reliability of the Kirkwood–Buff approach.

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Article type: Paper
DOI: 10.1039/F19898503019
Citation: J. Chem. Soc., Faraday Trans. 1, 1989,85, 3019-3032
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    Preferential solvation of ions in mixed solvents. Part 4.—Comparison of the Kirkwood–Buff and quasi-lattice quasi-chemical approaches

    Y. Marcus, J. Chem. Soc., Faraday Trans. 1, 1989, 85, 3019
    DOI: 10.1039/F19898503019

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