Skip to main content
SpringerLink
Log in

The behavior of ion pairs in high frequency electric fields exemplified by acetonitrile solutions of Bu4NBr

  • Published:
Journal of Solution Chemistry Aims and scope Submit manuscript

Abstract

Permittivity data from 0.9 to 40 GHz for acetonitrile and 0.05 to 1.4 molar acetonitrile solutions of Bu4NBr at 25°C are used to exemplify the behavior of ion pairs in high frequency electric fields. Measurements were excuted by the method of travelling waves with equipment known to produce data of high precision. Data analysis of the acetonitrile spectrum shows a single relaxation process at relaxation time of 3.5 ps for the solvent reorientation; the spectra of the salt solutions reveal two relaxation processes with relaxation times increasing from 3.5 to 6.8 ps for the solvent and decreasing from 120 to 70 ps for the ion pair [Bu4NBr]o at increasing salt concentration. The association constant of Bu4NBr in acetonitrile determined by permittivity measurements agrees well with that from conductance measurements. The concentration-dependence of the ion-pair relaxation times reveals the rate constants of ion-pair formation and decomposition.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. C. J. F. Böttcher and P. Bordewijk,Theory of Electric Polarization, Vol. II, (Elsevier, Amsterdam, 1978).

    Google Scholar 

  2. J. Barthel, H. J. Gores, G. Schmeer, and R. Wachter, “Non-Aqueous Solutions in Chemistry and Modern Technology”, F. Boschke ed.,Topics in Current Chemistry 111, (Springer, Heidelberg, 1983) p. 33.

    Google Scholar 

  3. J. Barthel and H.-J. Wittmann, unpublished results

  4. J. Barthel,Ionen in Nichtwäßrigen Lösungen (Dietrich Steinkopff Verlag, Darmstadt, 1976).

    Google Scholar 

  5. R. Pottel and O. Lossen,Ber. Bunsenges. Phys. Chem. 71, 135–146 (1967).

    Google Scholar 

  6. H. Behret, F. Schmithals, and J. Barthel,Z. Phys. Chem. 96, 73 (1975).

    Google Scholar 

  7. J. Barthel, J. Krüger, and E. Schollmeyer,Z. Phys. Chem. 104, 59 (1977).

    Google Scholar 

  8. J. Barthel and F. Feuerlein,J. Solution Chem. 13, 393 (1984).

    Google Scholar 

  9. P. Winsor and R. H. Cole,J. Phys. Chem. 86, 2486 (1982).

    Google Scholar 

  10. J. Barthel, R. Buchner and H. J. Wittmann,Z. Phys. Chem. NF 139, 23 (1984).

    Google Scholar 

  11. U. Kaatze,Z. Phys. Chem. NF 135, 51 (1983).

    Google Scholar 

  12. R. Pottel,Ber. Bunsenges. Phys. Chem. 69, 363 (1965).

    Google Scholar 

  13. U. Kaatze, V. Lönnecke and R. Pottel,J. Phys. Chem. 91, 2206 (1987).

    Google Scholar 

  14. M. Delsignore, H. E. Maaser and S. Petrucci,J. Phys. Chem. 88, 2405 (1984).

    Google Scholar 

  15. M. Delsignore, H. Farber, and S. Petrucci,J. Phys. Chem. 89, 4968 (1985).

    Google Scholar 

  16. H. Cachet, M. Fekir, and J.-C. Lestrade,Can. J. Chem. 59, 1051 (1981).

    Google Scholar 

  17. H. Farber, D. E. Irish, and S. Petrucci,J. Phys. Chem. 87, 3515 (1983).

    Google Scholar 

  18. H. E. Maaser, M. Delsignore, M. Newstein, and S. Petrucci,J. Phys. Chem. 88, 5100 (1984).

    Google Scholar 

  19. H. Farber and S. Petrucci,J. Phys. Chem. 85, 2987 (1981).

    Google Scholar 

  20. H. Delsignore, H. Farber and S. Petrucci,J. Phys. Chem. 90, 66 (1986).

    Google Scholar 

  21. J. Barthel and R. Buchner,Pure Appl. Chem. 58, 1077 (1986).

    Google Scholar 

  22. T. J. Buchanan,Proc. Inst. Elec. Eng. Part III 99, 61 (1952).

    Google Scholar 

  23. J. Barthel,Pure Appl. Chem. 51, 2093 (1979).

    Google Scholar 

  24. J. Barthel, R. Buchner and H. Steger,Wiss. Z. Tech. Hochsch. Chem. Leuna-Merseburg 31, 409 (1989).

    Google Scholar 

  25. J. Barthel, R. Wachter und H. J. Gores, inModern Aspects of Electrochemistry, Vol. 13, B. E. Conway and J. O'M. Bockris, eds., (Plenum, New York, 1979) Chap. 1.

    Google Scholar 

  26. J. E. O'Donnel, J. T. Ayres and C. K. Mann,Anal. Chem. 37, 1161 (1965).

    Google Scholar 

  27. J. Barthel and H. Utz, unpubished data

  28. T. T. Bopp,J. Chem. Phys. 47, 3621 (1967).

    Google Scholar 

  29. K. E. Arnold and J. Yarwood,Mol. Phys. 48, 451 (1983).

    Google Scholar 

  30. S. H. Glarum,J. Chem. Phys. 33, 1371 (1960).

    Google Scholar 

  31. S. H. Glarum,J. Chem. Phys. 33, 639 (1960).

    Google Scholar 

  32. E. S. Rittner,J. Chem. Phys. 19, 1030 (1951).

    Google Scholar 

  33. W. R. Gilkerson and J. L. Steward,J. Phys. Chem. 65, 1465 (1961).

    Google Scholar 

  34. D. Menard and M. Chabanel,J. Phys. Chem. 79, 1081 (1975).

    Google Scholar 

  35. E. A. S. Cavell, P. C. Knight and M. A. Sheikh,J. Chem. Soc. Faraday Trans. 67, 2225 (1971).

    Google Scholar 

  36. T. G. Scholte,Physica 15, 437 (1949).

    Google Scholar 

  37. C. Treiner and R. Fuoss,Z. Phys. Chem. Leibzig 228, 343 (1965).

    Google Scholar 

  38. G. A. Forcier and J. W. Olver,Electrochim. Acta 14, 135 (1969).

    Google Scholar 

  39. A. C. Harkness and H. M. Daggett,Can. J. Chem. 43, 1215 (1965).

    Google Scholar 

  40. D. F. Evans, C. Zawoyski and R. L. Kay,J. Phys. Chem. 69, 3878 (1965).

    Google Scholar 

  41. C. G. Seefried, Thesis, Yale (1969).

  42. G. Kabisch,Ber. Bunsenges. Phys. Chem. 80, 602 (1976).

    Google Scholar 

  43. G. Kabisch,Schwingungsspektroskopische und Kernresonanzuntersuchungen an Tetraalkylammoniumsalzlösungen (Akademie-Verlag, Berlin, 1979).

    Google Scholar 

  44. J. E. Anderson,J. Chem. Phys. 51, 3578 (1969).

    Google Scholar 

  45. J. E. Anderson,Ber. Bunsenges. Phys. Chem. 75, 294 (1971).

    Google Scholar 

  46. H. Strehlow and W. Knoche,Fundamentals of Chemical Relaxations (Verlag Chemie, Weinheim, 1977).

    Google Scholar 

  47. J.-C. Lestrade, J.-P. Badiali and H. Cachet inDielectric and Related Molecular Processes, Vol. II, (The Chemical Society, London, 1975).

    Google Scholar 

  48. J. Barthel, R. Buchner, B. Gill, K. Bachhuber, and M. Kleebauer,Chem. Phys. Lett. in preparation.

  49. F. Accascina, S. Petrucci and R. M. Fuoss,J. Am. Chem. Soc. 81, 1301 (1959).

    Google Scholar 

  50. J. B. Hubbard and L. Onsager,J. Chem. Phys. 67, 4850 (1977).

    Google Scholar 

  51. J. B. Hubbard,J. Chem. Phys. 68, 1649 (1978).

    Google Scholar 

  52. J. B. Hubbard, P. Colonomos, and P. J. Wolynes,J. Chem. Phys. 71, 2652 (1979).

    Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Institut für Physikalische und Theoretische Chemie, Universität Regensburg, D-8400, Regensburg, Federal Republic of Germany

    J. Barthel & M. Kleebauer

Authors
  1. J. Barthel
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. M. Kleebauer
    View author publications

    You can also search for this author in PubMed Google Scholar

Rights and permissions

Reprints and permissions

About this article

Cite this article

Barthel, J., Kleebauer, M. The behavior of ion pairs in high frequency electric fields exemplified by acetonitrile solutions of Bu4NBr. J Solution Chem 20, 977–993 (1991). https://doi.org/10.1007/BF00663997

Download citation

  • Received:

  • Issue Date:

  • DOI: https://doi.org/10.1007/BF00663997

Key words

Search

Navigation