The solvation potential at the interface between water and methanol + water mixtures

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Abstract

Emf measurements are reported for galvanic cells in which one half-cell contains an aqueous electrolyte solution and the other the same electrolyte in a methanol + water mixture. The electrolytes LiCl, NaCl, KCl, CsCl and HCl have been studied over most of the composition range from pure water to pure methanol in a cell with silversilver chloride electrodes and a newly-designed flowing liquid junction. The new term “solvation potential” is introduced for the component of the liquid junction potential that is due to the ion-coupled transport of solvent molecules through the liquid junction. This component is dependent on the nature of the solvents, the electrolyte concentration and the nature of the ions present, and we have interpreted the data obtained in terms of a new measurable single ionic quantity that we have called the “relative solvation intensity”. The criteria for the prediction of solvation potentials are established and a procedure outlined for obtaining accurate thermodynamic information from cells of the type used in this work.

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