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Thermodynamics of Electrolytes. 13. Ionic Strength Dependence of Higher-Order Terms; Equations for CaCl2 and MgCl2

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Abstract

While the original ion-interaction (Pitzer) equations of 1973 were adequate for many electrolytes to the limit of solubility, additional terms are needed for some systems of large solubility. A simple pattern of ionic-strength dependence is proposed for third, fourth, and higher virial coefficients. It is found to be very effective in representing the complex behavior of CaCl2(aq) as well as that of MgCl2(aq) at 25°C. Equations without ion association are presented for each system that are valid for the full range to 11.0 and 5.9 mol-kg−1, respectively, as well as simpler equations for limited molality ranges.

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REFERENCES

  1. K. S. Pitzer, J. Phys. Chem. 77, 268 (1973).

    Google Scholar 

  2. K. S. Pitzer and G. Mayorga, J. Phys. Chem. 77, 2300 (1973).

    Google Scholar 

  3. H. L. Friedman, Ionic Solution Theory, Chap. 3 (Wiley-Interscience, New York, 1962).

    Google Scholar 

  4. K. S. Pitzer and J. J. Kim, J. Am. Chem. Soc. 96, 5701 (1974).

    Google Scholar 

  5. K. S. Pitzer, in Activity Coefficients in Electrolyte Solutions, 2nd edn., Chap. 3, K. S. Pitzer, ed. (CRC Press, Boca Raton, FL, 1991).

    Google Scholar 

  6. C. E. Harvie and J. H. Weare, Geochim. Cosmochim. Acta 44, 981 (1980).

    Google Scholar 

  7. V. K. Filippov and V. I. Nokhrin, Russ. J. Inorg. Chem. 30, 282, 289 (1985).

    Google Scholar 

  8. V. K. Filippov, N. A. Charykov, and V. Rumyantsev, Dokl. Akad. Nauk, SSSR, Fiz. Khim. 296, 665 (1987) (Engl. Transl. p. 936).

    Google Scholar 

  9. R. G. Anstiss and K. S. Pitzer, J. Solution Chem. 20, 849 (1991).

    Google Scholar 

  10. J. A. Rard and S. L. Clegg, J. Chem. Eng. Data 42, 819 (1997).

    Google Scholar 

  11. J. Ananthaswamy and G. Atkinson, J. Chem. Eng. Data 30, 120 (1985).

    Google Scholar 

  12. D. G. Archer, J. Phys. Chem. Ref. Data 20, 509 (1991).

    Google Scholar 

  13. D. G. Archer, J. Phys. Chem. Ref. Data 21, 793 (1992).

    Google Scholar 

  14. S. L. Clegg, J. A. Rard, and K. S. Pitzer, J. Chem. Soc. Faraday Trans. 90, 1875 (1994).

    Google Scholar 

  15. R. C. Phutela and K. S. Pitzer, J. Solution Chem. 12, 201 (1983).

    Google Scholar 

  16. N. A. Hewish, G. W. Neilson, and J. E. Enderby, Nature 297, 138 (1982).

    Google Scholar 

  17. J. A. Rard, A. Habenschuss, and F. H. Spedding, J. Chem. Eng. Data 22, 180 (1977).

    Google Scholar 

  18. R. A. Robinson and R. H. Stokes, Electrolyte Solutions, 2nd edn. revised, (Butterworths, London, 1965).

    Google Scholar 

  19. D. G. Archer and P. Wang, J. Phys. Chem. Ref. Data 19, 371 (1990).

    Google Scholar 

  20. R. N. Goldberg and R. L. Nuttall, J. Phys. Chem. Ref. Data 7, 263 (1978).

    Google Scholar 

  21. J. A. Rard and D. G. Miller, J. Chem. Eng. Data 26, 33, 38 (1981).

    Google Scholar 

  22. R. H. Stokes, Trans. Faraday Soc. 41, 642 (1945).

    Google Scholar 

  23. R. A. Robinson and R. H. Stokes, Trans. Faraday Soc. 36, 733 (1940).

    Google Scholar 

  24. R. A. Robinson and V. E. Bower, J. Res. Natl. Bur. Stand. U.S. A70, 305 (1966).

    Google Scholar 

  25. R. F. Platford, J. Phys. Chem. 72, 4053 (1968).

    Google Scholar 

  26. Y. C. Wu, R. M. Rush, and G. Scatchard, J. Phys. Chem. 72, 4048 (1968); 73, 2047 (1969).

    Google Scholar 

  27. Yu. G. Frolov, V. P. Nikolaev, M. Kh. Karapet'yants, and K. K. Vlasenko, Russ. J. Phys. Chem. 45, 1054 (1971).

    Google Scholar 

  28. J. Padova and D. Saad, J. Solution Chem. 6, 57 (1977).

    Google Scholar 

  29. D. Saad, J. Padova, and Y. Marcus, J. Solution Chem. 4, 983 (1975).

    Google Scholar 

  30. F. Kuschel and J. Seidel, J. Chem. Eng. Data 30, 440 (1985).

    Google Scholar 

  31. H. F. Gibbard, Jr., and A. F. Gossmann, J. Solution Chem. 3, 385 (1974).

    Google Scholar 

  32. H. S. Harned, in The Structure of Electrolytic Solutions, Chap. 10, W. J. Hamer, ed., (Wiley, New York, 1959).

    Google Scholar 

  33. K. S. Pitzer and G. Mayorga, J. Solution Chem. 3, 539 (1974).

    Google Scholar 

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Pitzer, K.S., Wang, P., Rard, J.A. et al. Thermodynamics of Electrolytes. 13. Ionic Strength Dependence of Higher-Order Terms; Equations for CaCl2 and MgCl2 . Journal of Solution Chemistry 28, 265–282 (1999). https://doi.org/10.1023/A:1022695525943

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  • DOI: https://doi.org/10.1023/A:1022695525943

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