Variations of activity coefficients in concentrated electrolyte solutions at constant lonic strength |
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Authors: | F. W. J. Huijgen C. L. de Ligny A. G. Remijnse N. J. Ruitenbeek |
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Affiliation: | (1) Laboratory for Analytical Chemistry, University of Utrecht, Utrecht, The Netherlands |
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Abstract: | Measurements of different types on various (trace) electrolytes in HClO4–Na(Li)ClO4 solutions at several (constant) values of the ionic strength have been used to determine the variation of their activity coefficients with changing amount of perchloric acid in the solution. These variations (with respect to the hydrogen ion) differ considerably among different cations and anions. The results for the alkali metal ions and the anions are interpreted in the light of the recent work of Pitzer on short-range ionic interactions. The results for the cations with outerd-electrons and the alkaline earth metal ions are interpreted in terms of ion-solvent interactions. It is concluded that the use of HClO4–NaClO4 solutions of high ionic strength (rather than the use of HClO4–LiClO4 solutions) is advisable in studies where the variation in activity coefficients must be accounted for. Finally, it is shown that the usual interpretation of the influence of the salt medium in studies of complex equilibria and reaction kinetics is sometimes questionable. |
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Keywords: | Activity coefficients mixtures of electrolytes electrolytes ionic strength Harned's rule medium effects |
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