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Single-Ion Contributions to Activity Coefficient Derivatives, Second Moment Coefficients, and the Liquid Junction Potential
Authors:Fernando O Raineri  Harold L Friedman  George Stell
Institution:(1) Department of Chemistry, State University of New York at Stony Brook, Stony Brook, New York, 11794–3400
Abstract:We discuss several interrelated single-ion thermodynamic properties required to calculate the liquid junction potential PSgr between two solutions of the same binary electrolyte. According to a previously reported molecular theory of nonuniform electrolyte solutions in nonequilibrium, PSgr is determined by the transport numbers of the ions, and by the second moment coefficients H agr (2) of the charge densities around the ions. The latter may be viewed as the single-ion contributors to the second moment condition of Stillinger and Lovett. For a solution of a single binary electrolyte, we relate the H agr (2) (R) to the derivatives of the single-ion activity coefficients gammaagr with respect to the ionic strength. In the light of these results, we examine, in some detail, the role played by the specific short-range interionic interactions in determining PSgr. We investigate this matter by means of integral equation calculations for realistic models of LiCl and NaCl aqueous solutions in the 0–1 mol-dm–3 range. In addition to the hypernetted-chain (HNC) relation, we perform calculations under a new integral equation closure that is a hybrid between the HNC and Percus–Yevick closures. Like the HNC approximation, the new closure satisfies the Stillinger and Lovett condition. However, for the models considered in this study, the two closures predict different dependence of the H agr (2) and of PSgr on the specific part of the interionic interactions.
Keywords:Liquid junction potential  single-ion properties  second moment coefficients  generalized ionic compressibilities  specific interactions  hypernetted-chain  Percus–  Yevick  concentration dependence
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