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Journal of Solution Chemistry

, Volume 8, Issue 1, pp 53–82 | Cite as

Electrolytic conductance for Gurney-Friedman models

  • Werner Ebeling
  • Rainer Feistel
  • Rainer Sändig
Article

Abstract

Starting from hierarchy of diffusion equations for the distribution functions in coordinate space, the general theory of conductance is developed and applied to Gurney-Friedman models for ion-ion interactions. The interaction potentials used consist of a hard core with Pauling radii and a Gurney cosphere with a steplike interaction law converging to the Coulomb law outside the Gurney sphere. For the simplest case of step potentials explicit formulas for the conductivity are given. For higher concentrations an integral equation corresponding to the mean-spherical approximation in equilibrium is proposed. The theory is compared with experimental data for 17 alkali halide electrolytes by fitting the Gurney parameters. It is shown that the variant of the theory which includes the feedback of the relaxation and electrophoretic forces describes also the data for associating 2-2 electrolytes.

Key words

Conductance Debye-Hückel approximations mean spherical approximations Gurney-Fiedman models alkali halides ionic association 

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References

  1. 1.
    H. L. Friedman and W. T. Dale, Electrolyte Solutions at Equilibrium, inTheoretical Chemistry, Vol. 5, B. J. Berne, ed. (Plenum Press, New York, 1977); H. L. Friedman, C. V. Krishnan, and L. P. Hwang, Solute-Solute Interactions, inStructure of Water and Aqueous Solutions (Verlag Chemie, Marburg, 1974).Google Scholar
  2. 2.
    H. C. Anderson and D. Chandler,J. Chem. Phys. 57, 1918 (1972); J. S. Høye and G. Stell,J. Chem. Phys. 67, 524 (1977).Google Scholar
  3. 3.
    E. Waisman and J. L. Lebowitz,J. Chem. Phys. 52, 4307 (1970);56, 3086 (1972);56, 3093 (1972).Google Scholar
  4. 4.
    L. Blum,Mol. Phys. 30, 1529 (1975); L. Blum and J. S. Høye,J. Phys. Chem. 81, 1311 (1977); R. Triolo, J. R. Grigera, and L. Blum,J. Phys. Chem. 80, 1858 (1976).Google Scholar
  5. 5.
    J. C. Rasaiah and H. L. Friedman,J. Phys. Chem. 72, 3352 (1968);J. Chem. Phys. 48, 2742 (1968); J. C. Rasaiah,J. Chem. Phys. 52, 704 (1970).Google Scholar
  6. 6.
    P. S. Ramanathan and H. L. Friedman,J. Chem. Phys. 54, 1086 (1971); H. L. Friedman, A. Smitherman, and R. DeSantis,J. Solution Chem. 2, 59 (1973).Google Scholar
  7. 7.
    D. Kremp, H. Ulbricht, and G. Kelbg,Z. Phys. Chem. (Leipzig) 240, 65, 80 (1969);Google Scholar
  8. 7a.
    D. Kremp,Ann. Phys. (Leipzig) 18, 237, 246 (1966).Google Scholar
  9. 8.
    M. C. Justice and J. C. Justice, Colloques Internationaux du C.N.R.S., No. 246,L'Eau et les Systemes Biologiques, Paris (1975), p. 243.Google Scholar
  10. 9.
    J. C. Justice and M. C. Justice,Faraday Discuss. Chem. Soc., No. 64 (1977).Google Scholar
  11. 10.
    J. C. Justice and W. Ebeling, J. Solution Chem., to be published.Google Scholar
  12. 11.
    W. Ebeling and R. Feistel,Chem. Phys. Lett. 36, 404 (1975); W. Ebeling, R. Feistel, and D. Geisler,Z. Phys. Chem. (Leipzig) 257, 337 (1976).Google Scholar
  13. 12.
    R. Sändig, R. Feistel, H. Ulbricht, C. Baudisch, and H. Künstner,Wiss. Z. Univ. Rostock 26, 635 (1977); W. Ebeling, D. Geisler, W. D. Kraeft, and R. Sändig,Wiss. Z. Univ. Rostock 23, 903 (1974).Google Scholar
  14. 13.
    W. Ebeling, R. Feistel, G. Kelbg, and R. Sändig,J. Non-Equilib. Thermodyn. 3, 11 (1978).Google Scholar
  15. 14.
    H. L. Friedman,Physica 30, 537 (1964);J. Chem. Phys. 42, 450 (1965).Google Scholar
  16. 15.
    H. Falkenhagen and W. Ebeling,Phys. Lett. 15, 131 (1965); W. Ebeling,Ann. Phys. (Leipzig) 16, 147 (1965); C. I. Ivanov and W. Ebeling,Acta Phys. Pol. A52, 329 (1977); H. Falkenhagen, W. Ebeling, and H. G. Hertz,Theorie der Elektrolyte (S. Hirzel Verlag, Leipzig, 1971); H. Falkenhagen, W. Ebeling, and W. D. Kraeft, in:Ionic Interactions, Vol. 1, S. Petrucci, ed. (Academic Press, New York, 1971), Chapter 2.Google Scholar
  17. 16.
    H. Yamakawa:J. Chem. Phys. 53, 436 (1970); B. U. Felderhof,Physica 89A, 373 (1977).Google Scholar
  18. 17.
    W. Olivares and D. A. McQuarrie,J. Chem. Phys. 65, 3604 (1976).Google Scholar
  19. 18.
    D. N. Card and J. P. Valleau,J. Chem. Phys. 52, 6232 (1970); B. P. Chassovskikh and P. N. Vorontsov-Velyaminov,Teplofiz. Temp. 14, 379 (1976).Google Scholar
  20. 19.
    E. Bich, W. Ebeling, and H. Krienke,Z. Phys. Chem. (Leipzig) 257, 549 (1976).Google Scholar
  21. 20.
    H. Wiechert, H. Krienke, R. Feistel, and W. Ebeling,Z. Phys. Chem. (Leipzig) in press.Google Scholar
  22. 21.
    J. C. Justice,J. Solution Chem., in press.Google Scholar
  23. 22.
    R. Sändig, Doctoral Thesis, W. Pieck University, Rostock (1973).Google Scholar
  24. 23.
    R. Feistel, Doctoral Thesis, W. Pieck University, Rostock (1976); R. Feistel,Z. Phys. Chem. (Leipzig) 259, 369 (1978).Google Scholar
  25. 24.
    R. M. Fuoss and F. Accascina,Electrolytic Conductance (Interscience Publishers, New York, 1959); R. M. Fuoss,Proc. Nat. Acad. Sci. U.S.A. 71, 4491 (1974); R. M. Fuoss, L. Onsager, and J. F. Skinner,J. Phys. Chem. 69, 2581 (1965); P. C. Carman,J. Phys. Chem. 74, 1653 (1970); J. Barthel, J. C. Justice, and R. Wachter,Z. Phys. Chem. 84, 100 (1973); E. Renard and J. C. Justice,J. Solution Chem. 3, 633 (1974); M. S. Chen and L. Onsager,J. Phys. Chem. 81, 2017 (1977); M. S. Chen,J. Phys. Chem. 81, 2022 (1977); J. Quint and A. Viallard,J. Solution Chem. 7, 137 (1978);7, 525 (1978);7, 533 (1978).Google Scholar
  26. 25.
    R. L. Kay,J. Am. Chem. Soc. 82, 2099 (1960); R. L. Kay, inElectrolytes, B. Pesce, ed. (Pergamon Press, New York, 1962).Google Scholar
  27. 26.
    R. Sändig, R. Feistel, J. Einfeldt, and A. Grosch, submitted toZ. Phys. Chemie (Leipzig).Google Scholar
  28. 27.
    J. Einfeldt, R. Feistel, A. Grosch, and R. Sändig,Wiss. Z. Univ. Rostock 24, 681 (1975); R. Sändig, Manuskript SPUR 122 (1978), Sektion Physik der Wilhelm-Pieck-Universität, Rostock.Google Scholar
  29. 28.
    A. D. Pethybridge and D. J. Spiers,J. Chem. Soc. Faraday Trans. l 73, 768 (1977).Google Scholar
  30. 29.
    W. D. Kraeft and W. Ebeling,Z. Phys. Chem. (Leipzig) 240, 141 (1969); W. D. Kraeft and R. Sändig,J. Chim. Phys. 67, 1265 (1970).Google Scholar
  31. 30.
    W. D. Kraeft and R. Sändig,Z. Phys. Chem. (Leipzig) 247, 343 (1971); R. Sändig and W. D. Kraeft,Electrokhimiya 8, 152 (1972).Google Scholar
  32. 31.
    R. Sändig and R. Feistel,J. Solution Chem., to appear.Google Scholar

Copyright information

© Plenum Publishing Corporation 1979

Authors and Affiliations

  • Werner Ebeling
    • 1
  • Rainer Feistel
    • 1
  • Rainer Sändig
    • 1
  1. 1.Sektion Physik der Wilhelm-Pieck-Universität RostockRostockDDR

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