Abstract
This paper describes a new model to calculate the mean activity coefficients of dissociated electrolytes in concentrated solutions. It is based on three assumptions: (i) a quasi-lattice arrangements of ions in solution; (ii) a contribution from ion-water interactions to the mean activity coefficients; (iii) a concentration dependence of the dielectric constant. The mean activity coefficients of thirteen strong electrolytes from moderately dilute solutions to saturated solutions are found to correlate well by this model. For dilute solutions, a limiting equation in which only ion-specific parameters are required is proposed. It is suggested that specific ionwater interactions might be the major source of the nonideality of strong electrolyte solutions at high concentrations.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
H. S. Harned and B. B. Owen,The Physical Chemistry of Electrolyte Solution, 3rd edn., (Reinhold, New York, 1943).
K. S. Pitzer,J. Phys. Chem. 77, 268 (1973).
K. S. Pitzer and J. J. Kim,J. Am. Chem. Soc. 96, 5701 (1974).
K. S. Pitzer,Activity Coefficients in Electrolyte Solution, R. M. Pytkowicz, ed., (CRC Press, Boca Raton, 1979).
J. L. Cruz and H. Renon,AJChE J. 24, 817 (1978).
C. C. Chen, H. I. Britt, J. F. Boston and L. B. Evans,AIChEJ. 28, 588 (1982).
Y. D. Liu, A. H. Harvey and J. M. Prausnitz,Chem. Eng. Comm. 77, 43 (1989).
Y. Liu, M. Wimby and U. Gren,Comput. Chem. Eng. 13, 405 (1989).
B. Sander, A. Fredenslund, P. Rasmussen,Chem. Eng. Sci. 41, 1171 (1986).
J. C. Justice,J. Solution Chem. 20, 1017 (1991).
J. L. Martin, J. L. Gomez-Estevez and M. J. Canales,J. Solution Chem. 16, 87 (1987).
L. Rosta, Ph. D. Dissertation, Forida State University, (1987).
H. H. Haung,J. Solution Chem. 18, 1069 (1989).
H. Ohtaki and N. Fukushima,J. Solution Chem. 21, 23 (1992).
J. E. Enderby, S. Cummings, G. J. Herdman, G. W. Neilson, P. S. Salmon and N. Skipper,J. Phys. Chem. 91, 5851 (1987).
B. Jayaram, D. L. Beveridge,J. Phys. Chem. 95, 2506 (1991).
K. Heinzinger, I. Okada, Y. Kitusno, H. G. Lee, H. Ohtaki,Ions and Molecules in Solution, (Elsevier, Amsterdam, 1986).
G. Seeley and T. Keyes,J. Chem. Phys. 91, 5581 (1989);
G. Seeley, T. Keyes, and B. Madan,J. Phys. Chem.,96, 4074 (1992).
M. Bucher and T. L. Porter,J. Phys. Chem. 90, 3406 (1986).
S. Ehrenson,J. Phys. Chem. 91, 1868 (1987).
B. Jayaram, R. Fine, K. Sharp, and B. Honing,J. Phys. Chem. 93, 4320 (1989).
A. A. Rashin and B. Honing,J. Phys. Chem. 89, 5588 (1985).
J. J. Aqvist,J. Phys. Chem.,94, 8021 (1990).
J. B. Hasted, D. M. Ritson, and C. H. Coolie,J. Chem. Phys.,16, 1 (1948).
R. A. Robinson and R. H. Stokes,Electrolyte Solutions, 2nd ed., (Butterworths, London, 1970).
N. A. Lange,Handbook of Chemistry, Handbook Publishers, Sandusky, Ohio (1977).
E. Hückel,Phys. Zeits. 26, 93 (1925).
R. D. Shannon,Acta Cryst. A32, 751 (1976).
M. M. Lobo and J. L. Quarresma,Electrolyte Solutions: Literature Data on Thermodynamic and Transport Properties, (University of Coimbra), Portugal, 1981).
R. Pottel,Water, a Comprehensive Treatise, F. Franks, ed., (Plenum Press, New York, 1973).
F. Franks,Water, A Comprehensive Treatise, (Plenum Press, New York, 1973).
Y. Marcus,Ion Solvation, (Wiley, New York, 1985)
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Chen, JF., Choppin, G.R. Activity coefficients of single electrolytes in concentrated solutions derived from a quasi-lattice model. J Solution Chem 24, 465–484 (1995). https://doi.org/10.1007/BF01004478
Received:
Revised:
Issue Date:
DOI: https://doi.org/10.1007/BF01004478