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A view of electrolyte solutions

J. C. Rasaiah1

(1) Department of Chemistry, University of Maine, 04473 Orono, Maine

Received: 29 January 1973  

Abstract  The uncertainties in the route to infinite dilution for 2–2 electrolytes are discussed in relation to the practical difficulties of determining the standard emf's of simple reversible cells containing ZnSO4 in H2O and D2O solutions. These difficulties are due to uncertainties in the theory of highly charged ions in aqueous solution. Recent developments in theories of electrolytes, especially those for which numerical results are available, are critically evaluated for their accuracy and adaptability to changes in the solute potential. Simple refinements to the model (i.e., the solute potential) are described, and the changes are interpreted, in terms of the molecular interactions between sets or pairs of ions in the pure solvent. Recent work on the effect of solvent granularity and other molecular properties of the solvent (e.g., dipole moment) on the solute potential is reviewed.

Key Words  Electrolytes - aqueous solutions - heavy water - electromotive force - extrapolation - electrolyte theory - models - thermodynamics - cospheres - solvent granularity

This paper was presented at the symposium, ldquoThe Physical Chemistry of Aqueous Systems,rdquo held at the University of Pittsburgh, Pittsburgh, Pennsylvania, June 12–14, 1972, in honor of the 70th birthday of Professor H. S. Frank.

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  1. Chung, Ting-Horng (2009) The mean activity coefficients of 2:2 electrolyte solutions: An integral equation study of the restricted primitive model. The Journal of Chemical Physics 130(13)
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  2. Patey, G. N. (1975) A Monte Carlo method for obtaining the interionic potential of mean force in ionic solution. The Journal of Chemical Physics 63(6)
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  3. Turq, Pierre (1977) Brownian dynamics: Its application to ionic solutions. The Journal of Chemical Physics 66(7)
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  4. Triolo, R. (1977) Simple electrolytes in the mean spherical approximation. III. A workable model for aqueous solutions. The Journal of Chemical Physics 67(12)
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  5. Stell, G. (1979) Thermodynamics of charged hard spheres. The Journal of Chemical Physics 70(1)
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  6. Friedman, Harold L. (1979) Corresponding states for ionic fluids. The Journal of Chemical Physics 70(1)
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  7. Valleau, John P. (1980) Primitive model electrolytes. II. The symmetrical electrolyte. The Journal of Chemical Physics 72(11)
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  8. Lee, Song Hi (1985) A model for association in electrolytes. Analytic solution of the hypernetted-chain/mean spherical approximation. The Journal of Chemical Physics 83(1)
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  9. Eggebrecht, John (1990) Multipolar electrolyte solution models. I. Computer simulation of the charged and dipolar hard sphere mixture. The Journal of Chemical Physics 93(3)
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  10. Llano-Restrepo, Mario (1994) Monte Carlo simulation of the structural properties of concentrated aqueous alkali halide solutions at 25??C using a simple civilized model. The Journal of Chemical Physics 100(11)
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