Theory of mixed electrolyte solutions and application to a model for aqueous lithium chloride-cesium chloride

Abstract

The general theory of the calculation of the thermodynamic coefficients for electrolyte mixtures from the pair correlation functions for the mixtures is worked out. These correlation functions are computed for several models for aqueous LiCl-CsCl mixtures by means of the hypernetted-chain integral equation, and the theory is applied to them to obtain the free-energy mixing coefficients for these models. Special attention is given to a model having properties close to the experimental ones for this system. The computed results for this model seem to be accurate enough to be useful, judging by three self-consistency tests. The model exhibits three empirically established regularities about as well as experimental systems do. They are Harned's rule, Young's rule that certain mixing coefficients in a common-ion mixture are nearly independent of the common ion, and the rule that the sum of Harned's a coefficients depends linearly on the ionic strength. The model computations also elucidate the role of the mixture limiting law.

The Kirkwood–Buff theory and the effect of cosolvents on biochemical reactions

“…[60][61][62] In the treatment of GuHCl denaturation, one encounters a difficulty in treating dissociative salt solutions via KB theory. 18,19,24,63 We therefore adopt a conventional approximate treatment in which cations and anions are assumed to be indistinguishable. 63 Consequently, ⌬N 23 here refers to the number of total ions and V 3 /2 was used to signify the volume of each ion.…”

“…18,19,24,63 We therefore adopt a conventional approximate treatment in which cations and anions are assumed to be indistinguishable. 63 Consequently, ⌬N 23 here refers to the number of total ions and V 3 /2 was used to signify the volume of each ion. The remaining parameters in Eqs.…”

Recent Applications of Kirkwood–Buff Theory to Biological Systems

“…The application of KB theory to solutions of salts is complicated by correlations between the ions which are a consequence of electroneutrality constraints [72,73]. Hence, one cannot treat salt solutions as ternary systems of solvent, cations, and anions, i.e., one cannot determine derivatives of the chemical potentials with respect to the cation concentration, for example.…”

“…Hence, one cannot treat salt solutions as ternary systems of solvent, cations, and anions, i.e., one cannot determine derivatives of the chemical potentials with respect to the cation concentration, for example. However, one can treat the solution as a binary system of solvent and indistinguishable ions [40,42,67,72]. In this case, the chemical potential and concentration of component 3 are different from that that used experimentally.…”

Local Fluctuations in Solution: Theory and Applications

“…However, the theory lay relatively unused for over 25 years. Presumably, this initial lack of interest was because the theory appeared to be unsuited for the study of salt solutions, 7,8 and/or the theory required radial distribution functions, which are generally unknown, as input data.…”