Abstract
The hypernetted-chain integral-equation-approximation method is used to calculate the ion-ion pair correlation functions and the thermodynamic properties of models of the kind previously studied,(1) which are based on an ion-ion pair potential having four terms: the usual Coulomb term, a core repulsion term, a term to represent a well-known dielectric repulsion effect, and a “Gurney” term to represent the effect of the overlap of the structure-modified regions, solvation shells or “cospheres,” when the ions come close together. The coefficientA ij of the last term for each pairi,j of ionic species is the only parameter that is adjusted to fit the solution data. It is determined by fitting excess-free-energy (osmotic-coefficient) data. It is scaled to represent the molar free-energy change of water displaced from the cospheres when they overlap. The corresponding entropy changeS ij and volume changeV ij are determined by fitting, respectively, excessenthalpy and excess-volume data. Problems of finding a uniquely “best” set of parameters are discussed together with many examples of variations of the model, most of which require further investigation. A consistent set of these parameters, which represents much of what is known about the thermodynamic excess functions of these solutions at concentrations up to about 0.5M, is interpreted as far as possible in terms of the data for thermodynamic solvation functions for the same systems.
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References
H. L. Friedman and P. S. Ramanathan,J. Phys. Chem. 74, 3756 (1970).
H. L. Friedman, Computed Thermodynamic Properties and Distribution Functions for Simple Models of Ionic Solutions, inModern Aspects of Electrochemistry, J. O'M. Bockris and B. E. Conway, eds., (Plenum Press, New York, 1971).
P. S. Ramanathan and H. L. Friedman,J. Chem. Phys. 54, 1086 (1971).
J. C. Rasaiah,J. Chem. Phys. 52, 704 (1970).
H. S. Frank and M. W. Evans,J. Chem. Phys. 13, 507 (1945).
S. Lindenbaum and G. E. Boyd,J. Phys. Chem. 68, 911 (1964).
W. Y. Wen, S. Saito, and C. M. Lee,J. Phys. Chem. 70, 1244 (1966); W. Y. Wen and S. Saito,J. Phys. Chem. 68, 2639 (1964).
R. H. Wood and H. L. Anderson,J. Phys. Chem. 71, 1871 (1967); R. H. Wood, H. L. Anderson, J. D. Beck, J. R. France, W. E. deVry, and L. J. Soltzberg,J. Phys. Chem. 71, 2149 (1967).
S. Lindenbaum,J. Phys. Chem. 70, 814 (1966).
W. Y. Wen and K. Nara,J. Phys. Chem. 71, 3907 (1967); W. Y. Wen, K. Nara, and R. H. Wood,J. Phys. Chem. 72, 3048 (1967).
R. L. Kay, C. Zawoyski, and D. F. Evans,J. Phys. Chem. 69, 4208 (1965).
R. W. Gurney,Ionic Processes in Solution (Dover, New York, 1953).
H. S. Frank,Z. Phys. Chem. (Leipzig) 228, 364 (1965).
R. W. Kreis and R. H. Wood,J. Phys. Chem. 75, 2319 (1971).
L. Pauling,The Nature of the Chemical Bond (Cornell University Press, Ithaca, New York, 1960).
J. C. Rasaiah and H. L. Friedman,J. Chem. Phys. 48, 2742 (1968).
C. V. Krishnan and H. L. Friedman, unpublished results.
C. V. Krishnan and H. L. Friedman,J. Phys. Chem. 75, 3598 (1971).
C. V. Krishnan and H. L. Friedman,J. Phys. Chem. 75, 3606, (1971).
C. V. Krishnan and H. L. Friedman,J. Phys. Chem. 74, 2356 (1970).
C. V. Krishnan and H. L. Friedman,J. Phys. Chem. 73, 1572 (1969).
C. V. Krishnan and H. L. Friedman,J. Phys. Chem. 73, 3934 (1969).
D. F. Evans and P. Gardam,J. Phys. Chem. 72, 3281 (1968).
D. F. Evans and P. Gardam,J. Phys. Chem. 73 158 (1969).
R. Lumry and S. Rajendar,Macromol. Rev. 4 (1971).
H. S. Frank,J. Chem. Phys. 13, 478, 493 (1945).
J. E. Leffler and E. Grunwald,Rates and Equilibria of Organic Reactions (John Wiley and Sons, New York, 1963).
C. V. Krishnan and H. L. Friedman,J. Phys. Chem. 75, 388 (1971).
G. A. Jeffrey and R. K. McMullan, inProgr. Inorg. Chem.,8, 43 (1967).
R. K. Mohanty, T. S. Sarma, S. Subramanian, and J. C. Ahluwalia,Trans. Faraday Soc. 67, 305 (1971).
G. R. Haugen and H. L. Friedman,J. Phys. Chem. 67, 1757 (1963).
R. Desantis, A. Smitherman, and H. L. Friedman, Model Calculations for Aqueous Alkaline Earth Halides and Their Mixtures with Alkali Halides, in preparation.
J. C. Ku, Ph.D. Dissertation, University of Pittsburgh, 1971.
W. Kauzmann, Advan. Protein Chem.14, 1 (1959).
R. M. Diamond,J. Phys. Chem. 67, 2513 (1963).
H. S. Frank, private communication.
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This study was aided by a grant from the Office of Saline Water, U.S. Department of Interior.
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Ramanathan, P.S., Krishnan, C.V. & Friedman, H.L. Models having the thermodynamic properties of aqueous solutions of tetraalkylammonium halides. J Solution Chem 1, 237–262 (1972). https://doi.org/10.1007/BF00645104
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DOI: https://doi.org/10.1007/BF00645104