Ionic properties in acetonitrile + water mixtures and dimethylformamide + water mixtures

Emf measurements at 298 K are reported for Wagner-type galvanic cells with flowing liquid junctions in which one half-cell contains an aqueous electrolyte solution and the other contains the same electrolyte in either acetonitrile (AN) + water mixtures or dimethylformamide (DMF) + water mixtures of...

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Bibliographic Details
Published in:Journal of electroanalytical chemistry (Lausanne, Switzerland) Switzerland), 1994-07, Vol.372 (1), p.75-84
Main Authors: Gregory, Raymond E., McTigue, Peter T., Perera, Jilska M.
Format: Article
Language:English
Subjects:
Chemistry
Exact sciences and technology
General and physical chemistry
Solutions
Solvation. Solvent properties
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Summary:Emf measurements at 298 K are reported for Wagner-type galvanic cells with flowing liquid junctions in which one half-cell contains an aqueous electrolyte solution and the other contains the same electrolyte in either acetonitrile (AN) + water mixtures or dimethylformamide (DMF) + water mixtures of varying composition. The electrolytes LiCl, NaCl and KCl have been studied in the AN + water system using Ag/AgCl electrodes, while LiCl, NaCl, KCl and NaBr have been studied in the DMF + water system using flowing amalgam electrodes in each half-cell. The data have been combined with standard Gibbs energies of transfer data from the literature and conductance data, much of it reported here for the first time, to obtain solvation potentials for the cells. Transport numbers for these electrolytes are also reported. The results show that DMF displaces water in the cation solvation sheath as the organic content of the mixed solvent increases, whilst AN shows a similar but less marked effect.
ISSN:1572-6657
1873-2569
DOI:10.1016/0022-0728(93)03280-3