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Voltammetric investigation of the kinetics of alkali metal cation reduction in N,N-dimethylformamide

Diggle, J.W., Parker, A.J. and Owensby, D.A. (1975) Voltammetric investigation of the kinetics of alkali metal cation reduction in N,N-dimethylformamide. Australian Journal of Chemistry, 28 (2). pp. 237-241.

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The standard electron-transfer heterogeneous rate constant of lithium, potassium, sodium and caesium amalgams in N,N-dimethylformamide was ascertained employing cyclic voltammetry in an effort to relate the presence of a non-equilibrium electrode reaction at the dropping lithium amalgam electrode to the variation of the lithium amalgam electrode potential with amalgam electrode con- figuration, i.e. whether streaming, dropping or stationary. Such variations are not observed at other alkali metal amalgam electrodes. In the dipolar aprotic solvents the standard electron-transfer heterogeneous rate constant for the Li(Hg) electrode increases as the solvating power for Li+ decreases, i.e. dimethyl sulphoxide < di- methylformamide < propylene carbonate. Water is a much stronger solvator of Li+ than is propylene carbonate, but the electron transfer is faster in water than in propylene carbonate; the important role of entropic contributions in ion solvation is discussed as an explanation.

Item Type: Journal Article
Murdoch Affiliation(s): School of Mathematical and Physical Sciences
Publisher: Commonwealth Scientific and Industrial Research Organization Publishing
Copyright: © 1975 CSIRO
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