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Effect of nonideality of solution on the diffuse layer properties near the point of zero charge in a nonsymmetrical electrolyteстатья
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Дата последнего поиска статьи во внешних источниках: 18 июля 2013 г.
- Авторы: Grafov B.M., Damaskin B.B.
- Журнал: Russian Journal of Electrochemistry
- Том: 34
- Номер: 11
- Год издания: 1998
- Издательство: Maik Nauka/Interperiodica Publishing
- Местоположение издательства: Russian Federation
- Первая страница: 1143
- Последняя страница: 1148
- Аннотация: The diffuse layer equations are analyzed near the point of zero charge in a nonsymmetrical electrolyte at any concentration dependence of the ionic activity coefficients. The standard equality of two thermodynamic expressions for the Esin-Markov coefficients is shown to turn into an identity only if the equality (∂μ+/∂n-)n = (∂μ-/∂n+)n- is fulfilled. Here, μ+ and μ- are chemical potentials of cations and anions, while n+ and n- denote the ratios of concentrations of cations and anions to the solvent concentration. Our conclusion is that, in the first order by the electrode charge, the differential of the Gibbs thermodynamic potential within the diffuse layer may be written in a form that formally corresponds to neutral, rather than charged, species. In the point of zero charge, an expression is found for the diffuse layer capacitance that represents a generalization of the Gouy-Chapman theory for the case of an actual nonsymmetrical electrolyte. Comparing with the experimental data on the differential capacitance of the mercury electrode in sodium and lanthanum sulfate solutions shows that the deviation of the measured capacitance from that calculated with the Gouy-Chapman theory is caused largely by a strong dependence of the ionic activity coefficient on the oppositely charged ion’s concentration. Partial derivatives of the ionic activity coefficients with respect to the concentration of the oppositely charged ion are found with an experiment. © 1998 MAHK Hayka/Interperiodica Publishing.
- Добавил в систему: Дамаскин Борис Борисович