Skip to main content
SpringerLink
Log in

Influence of Proton Transfer on the Formation of Hydrogen-Bonded Complexes of Higher Stoichiometry and on their Dissociation into Free Ions

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

Abstract

Proton transfer in a given H-bond ⊂A—H—B—(H)→⊂A−— H+—B—(H) considerably enhances the strength of the electron donor sites of the first partner and that of proton donor sites possibly present in the second one. This leads to the formation of complexes of higher stoichiometry of the type B— H+—(A−—H—A--H—A--H--)or A−---(H—B+—H----B—H—B—H----) where the self-association bonds are much strengthened. This is due to the high stability of the homoconjugated anions or cations in the corresponding ion pairs. In polar solvents like acetonitrile, the ion pairs may dissociate into free ions. The variety of the entities that can be formed necessitates a diversification of the quantitative concepts connected with the proton transfer process. Besides the average value 〈x1〉 of the fractions of the various complexes in the ionized form, other quantities are defined that can also be used in the case of partial dissociation: (1) the percentage of ionized base molecules and (2) the fraction of donor molecules AH ionized after direct interaction with B. A further characteristic used in this generalized treatment is the average number 〈n〉 of proton donor molecules perturbed by one base molecule. Examples of determinations of these various parameters from calorimetric, infrared, or NMR data from the literature are presented and new quantitative correlations established.

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. P. L. Huyskens and T. Zeegers-Huyskens, J. Chim. Phys., p. 64 (1964).

  2. H. Ratajczak and L. Sobczyk, J. Chem. Phys. 50, 556 (1969).

    Google Scholar 

  3. L. Sobczyk, personal communication, (1998).

  4. J. Jadzyn and J. Malecki, Acta Phys. Pol. A41, 599 (1972).

    Google Scholar 

  5. T. Zeegers-Huyskens and P. Huyskens, in Molecular Interactions, 2, H. R. Orville-Thomas and W. J. Orville-Thomas, eds., (J Wiley, New York, 1980), p. 1.

    Google Scholar 

  6. H. S. Frank and W. Y. Wen, Discussions Faraday Soc. 24, 133 (1957).

    Google Scholar 

  7. V. Gutmann, Struct. Bonding 15, 141 (1973).

    Google Scholar 

  8. F. Kohler and P. Huyskens, Adv. Mol. Relaxation Processes 8, 125 (1976).

    Google Scholar 

  9. H. Kleeberg, in Intermolecular Forces, P. L. Huyskens, W. A. P. Luck, and T. Zeegers-Huyskens, ed., (Springer, Berlin, 1991), p. 251.

    Google Scholar 

  10. H. Kleeberg, D. Klein, and W. A. P. Luck, J. Phys. Chem 91, 3200 (1987).

    Google Scholar 

  11. L. Ojamäc and K. Hermansson, J. Phys. Chem. 98, 4271 (1994).

    Google Scholar 

  12. A. Karpfen, J. Phys. Chem. 100, 13474 (1996).

    Google Scholar 

  13. A. Karpfen, in Molecular Interactions, S. Scheiner, ed., (J Wiley, New York, 1997), p. 263.

    Google Scholar 

  14. P. L. Huyskens, J. Amer. Chem. Soc. 99, 2578 (1977).

    Google Scholar 

  15. D. Reyntjens-Van Damme, and T. Zeegers-Huyskens, Bull. Soc. Chim. Belg. 88, 1003 (1979).

    Google Scholar 

  16. J. P. Muller, G. Vercruysse, and T. Zeegers-Huyskens, J. Chim. Phys. 69, 1439 (1972).

    Google Scholar 

  17. D. Clotman, D. Van Lerberghe, and T. Zeegers-Huyskens, Spectrochim. Acta A26, 1621 (1970).

    Google Scholar 

  18. R. M. Fuoss and F. Accascina, Electrolyte Conductance [Wiley (Interscience), New York, 1959].

    Google Scholar 

  19. I. M. Kolthoff and M. K. Chantooni, J. Phys. Chem. 66, 1675 (1962).

    Google Scholar 

  20. I. M. Kolthoff and M. Chantooni, J. Amer. Chem. Soc. 87, 4428 (1965).

    Google Scholar 

  21. I. M. Kolthoff and M. Chantooni, J. Amer. Chem. Soc. 93, 7025 (1971).

    Google Scholar 

  22. J. F. Coetzee, Prog. Phys. Org. Chem., p. 45 (1967).

  23. J. F. Coetzee and G. P. Cunningham, J. Amer. Chem. Soc. 87, 258O (1965).

    Google Scholar 

  24. J. F. Coetzee and G. R. Padmanabhan, J. Phys. Chem. 69, 3193 (1965).

    Google Scholar 

  25. M. C. Haulait and P. Huyskens, J. Solution Chem. 4, 853 (1975).

    Google Scholar 

  26. M. C. Haulait and P. Huyskens, J. Phys. Chem. 79, 1812 (1975).

    Google Scholar 

  27. D. Neerinck, A. Van Audenhaege, L. Lamberts, and P. Huyskens, Nature 218, 461 (1968).

    Google Scholar 

  28. P. Ballinger and F. A. Long, J. Amer. Chem. Soc. 82, 795 (1960).

    Google Scholar 

  29. H. C. Ho, W. F. O'Hara, T. Hu, and L. G. Hepler, J. Amer. Chem. Soc. 86, 1003 (1964).

    Google Scholar 

  30. T. L. Brown, J. Phys. Chem. 61, 820 (1957).

    Google Scholar 

  31. A. I. Biggs and R. A. Robinson, J. Chem. Soc., p. 388 (1961).

  32. D. H. McDaniel and H. C. Brown, J. Amer. Chem. Soc. 77, 3756 (1955).

    Google Scholar 

  33. F. Fiefer and P. Rumpf, C. R. Acad. Sci. 238, 360, 700 (1954).

    Google Scholar 

  34. L. K. Creamer, A. Fisher, B. R. Mann, J. Packer, R. B. Richards, and J. Vaugham, J. Org. Chem. 26, 3148 (1961).

    Google Scholar 

  35. R. A. Robinson, J. Res. Natl. Bur. Std. A68, 159 (1964).

    Google Scholar 

  36. M. M. Fickling, A. Fisher, B. R. Mann, J. Packer, and J. Vaughan, J. Amer. Chem. Soc. 81, 4226 (1959).

    Google Scholar 

  37. E. A. Braude and F. C. Nachod, Determination of Organic Structure by Physical Methods, (Academic Press, New York, 1955).

    Google Scholar 

  38. A. Fisher, G. J. Leary, R. D. Topsom, and J. Vaughan, J. Chem. Soc., p. 686 (1967).

  39. J. Juilliard, Bull. Soc. Chim. Fr., p. 1727 (1966).

  40. J. M. Birchall and R. N. Haszeldine, J. Chem. Soc., p. 3653 (1959).

  41. V. E. Bower and R. A. Robinson, J. Phys. Chem. 64, 1078 (1960).

    Google Scholar 

  42. R. A. Robinsons, M. M. Davis, M. Paabo, and V. E. Bower, J. Res. Natl. Bur. Std. 64, 347 (1960).

    Google Scholar 

  43. R. G. Bates and G. Schwarzenbach, Helv. Chim. Acta 37, 1069 (1954).

    Google Scholar 

  44. G. Kortüm and Z. Wilski, Z. Phys. Chem. 2, 256 (1966).

    Google Scholar 

  45. J. W. Smith, J. Chim. Phys. 61, 125 (1964).

    Google Scholar 

  46. L. Lamberts and P. Huyskens, conference proceeding (1969).

  47. A. Van Audenhaege, Ph.D. Thesis, Leuven, 1970.

  48. P. Huyskens, Ind. Chim. Belg. 37, 15–24 (1972).

    Google Scholar 

  49. T. Zeegers, Ph.D. Thesis, Leuven, 1969.

  50. Z. Pawelka and T. Zeegers-Huyskens, Bull. Soc. Chim. Belg. 106, 481 (1997).

    Google Scholar 

  51. M. Ilczyszin and H. Ratajzak, J. Mole. Liquids 67, 126 (1995).

    Google Scholar 

  52. R. W. Alder, P. S. Bowman, W. R. S. Steele, and D. R. Winterman, Chem. Commun., p. 723 (1968).

  53. H. Einspahr, J. B. Robert, R. E. Narsh, and J. D. Roberts, Acta Crystallogr. B29, 1611 (1973).

    Google Scholar 

  54. B. Brzezinski, T. Glowiak, E. Grech, Z. Malarski, and L. Sobczyk, Croat. Chem. Acta 65, 191 (1992).

    Google Scholar 

  55. M. Szafran and S. Dega-Szafran, J. Mol. Struct. 99, 189 (1983).

    Google Scholar 

  56. D. Pyzalska, R. Pyzalski, and T. Borowiak, J. Crystall. Spectrosc. Res. 13, 211 (1983).

    Google Scholar 

  57. E. Grech, Z. Malarski, and L. Sobczyk, J. Mol. Struct. 129, 35–43 (1985).

    Google Scholar 

  58. E. Grech, I. Stefaniak, I. Ando, M. Yoshimiza, G. A. Webb, and L. Sobczyk, Bull. Soc. Chim. Jpn. 63, 2716 (1990).

    Google Scholar 

  59. T. Glowiak, Z. Malarski, and E. Grech, J. Mol. Struct. 270, 441 (1992).

    Google Scholar 

  60. M. Eckert and G. Zundel, J. Phys. Chem. 92, 7016 (1988).

    Google Scholar 

  61. F. Bohlmann, Chem. Ber. 91, 2157 (1958).

    Google Scholar 

  62. K. Platteborze and T. Zeegers-Huyskens, Bull. Polish Acad. Sci. Chem. 42, 377 (1994).

    Google Scholar 

  63. P. Huyskens, K. Platteborze, and T. Zeegers-Huyskens, J. Mol. Struct., Ratajczak Issue 436–437, 91 (1997).

    Google Scholar 

  64. B. Brzezinski, E. Grech, Z. Malarski, and L. Sobczyk, J. Chem. Soc. Perkins Trans. 2 2, 1267 (1991).

    Google Scholar 

  65. B. Brzezinski, E. Grech, Z. Malarski, and L. Sobczyk, J. Chem. Soc. Faraday Trans. 86, 1777 (1990).

    Google Scholar 

  66. B. Brzezinski and G. Zundel, J. Mol. Struct. 368, 195 (1996).

    Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Department of Chemistry, University of Leuven, Celestijnenlaan 200F, B-3001, Heverlee, Belgium

    Pierre L. Huyskens & Thérèse Zeegers-Huyskens

  2. Faculty of Chemistry, University of Wroclaw., 14 F Joliot-Curie street, Pl 50-383, Wroclaw, Poland

    Zbigniev Pawelka

Authors
  1. Pierre L. Huyskens
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Thérèse Zeegers-Huyskens
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Zbigniev Pawelka
    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

Huyskens, P.L., Zeegers-Huyskens, T. & Pawelka, Z. Influence of Proton Transfer on the Formation of Hydrogen-Bonded Complexes of Higher Stoichiometry and on their Dissociation into Free Ions. Journal of Solution Chemistry 28, 915–932 (1999). https://doi.org/10.1023/A:1021788332418

Download citation

  • Issue Date:

  • DOI: https://doi.org/10.1023/A:1021788332418

Search

Navigation