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Quasi-thermodynamics of Viscous Flow of Electrolyte Solutions in Aqueous, Non-aqueous and Mixed Aqueous Solvents

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Abstract

Viscosity B-coefficients for cesium chloride and lithium sulfate in methanol + water mixtures at 25 and 35 °C are reported. A general treatment of the quasi-thermodynamics of viscous flow of electrolyte solutions is described. ΔG Θ3 (1→1′), the contribution made to the Gibbs energy of activation of the solution by the influence of the solute on the solvent, is a function of solute–solvent interactions only; but, ΔH Θ3 (1→1′) and ΔS Θ3 (1→1′) also reflect the solvent–solvent interactions. In aqueous solution all alkali-metal ions except Li+ are sterically unsaturated, having solvent co-ordination numbers n<n max , the maximum allowed sterically. Such complexes exchange molecules with the solvent more readily than saturated ones and have energy–reaction co-ordinate diagrams in forms that explain the negative B or ΔG Θ3 (1→1′) values found in aqueous solution. Saturated complexes are the norm in non-aqueous solvents, and the ΔG Θ3 (1→1′) values are determined mainly by the secondary solvation. Behavior in mixed solvents reflects the transition from aqueous to non-aqueous behavior across the range of solvent composition.

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  1. David Feakins

    Present address: , 350 Bristol Road, Birmingham, B5 7SN, UK

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  1. School of Chemistry and Chemical Biology, University College Dublin, Belfield, Dublin, 4, Ireland

    David Feakins, Fiona M. Bates & W. Earle Waghorne

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  1. David Feakins
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Correspondence to David Feakins.

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Feakins, D., Bates, F.M. & Waghorne, W.E. Quasi-thermodynamics of Viscous Flow of Electrolyte Solutions in Aqueous, Non-aqueous and Mixed Aqueous Solvents. J Solution Chem 37, 727–747 (2008). https://doi.org/10.1007/s10953-008-9271-5

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