Journal of Solution Chemistry

, Volume 10, Issue 8, pp 533–547 | Cite as

Solvation and hydrophobic hydration of different types of alkylamines inN,N-dimethylformamide and water mixtures

  • Aart C. Rouw
  • Gus Somsen


Enthalpies of solution of twelve amines of different type have been determined at 25°C in mixtures of N,N-dimethylformamide and water over the whole composition range. The enthalpies of transfer from water to the mixtures deviate substantially from a linear dependence on the mole fraction of water. These deviations appear to contain additive contributions of the different alkyl groups. By application of a simple hydration model the enthalpic effect of hydrophobic hydration has been calculated for each amine. For alkylamines this is determined by the number and size of the alkyl groups present in the molecule. The contribution of each alkyl group is the same in primary, secondary and tertiary amines. Results for the different alkyl groups show a close relationship with values for alcohols obtained previously. Differences between alcohols and amines can be attributed to differences in the hydrophobic hydration of the parts of the solute molecules which are adjacent to the polar group. The influence of the polar group does not seem to extend beyond the second carbon atom.

Key Words

Enthalpies of solution enthalpies of transfer alkylamines DMF-water mixtures DMF-NMF mixtures hydrophobic hydration 


Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.


  1. 1.
    W. J. M. Heuvelsland, M. Bloemendal, C. de Visser, and G. Somsen,J. Phys. Chem. 84, 2391 (1980).Google Scholar
  2. 2.
    A. C. Rouw and G. Somsen,J. Chem. Thermodynamics 13, 67 (1981).Google Scholar
  3. 3.
    F. Franks and B. Watson,Trans. Faraday Soc. 65, 2339 (1969).Google Scholar
  4. 4.
    F. M. Jones III and E. M. Arnett,Progr. Phys. Org. Chem. 11, 263 (1974).Google Scholar
  5. 5.
    S. Cabani, G. Conti, and L. Lepori,Trans. Faraday Soc. 67, 1933 (1971).Google Scholar
  6. 6.
    J. Konicek and I. Wadsö,Acta Chem. Scand. 25, 1541 (1971).Google Scholar
  7. 7.
    S. Bergström and G. Olofsson,J. Solution Chem. 4, 535 (1975).Google Scholar
  8. 8.
    S. Bergström and G. Olofsson,J. Solution Chem. 7, 497 (1978).Google Scholar
  9. 9.
    C. V. Krishnan and H. L. Friedman,Solute-Solvent Interactions Vol. 2, J. F. Coetzee and C. D. Ritchie, eds. (M. Dekker, New York, 1976).Google Scholar
  10. 10.
    W. J. M. Heuvelsland, C. de Visser, and G. Somsen,J. Phys. Chem. 82, 29 (1978).Google Scholar
  11. 11.
    I. Wadsö,Sci. Tools 13, 33 (1966).Google Scholar
  12. 12.
    R. R. Dreisbach,Physical Properties of Chemical Compounds Vol. 3, Advances in Chemistry Series No. 29 (Am. Chem. Soc., Washington, 1961).Google Scholar
  13. 13.
    J. C. Verhoef and E. Barendrecht,Anal. Chim. Acta 94, 395 (1977).Google Scholar
  14. 14.
    Z. Pawlak and R. G. Bates,J. Solution Chem. 4, 817 (1975).Google Scholar
  15. 15.
    W. J. M. Heuvelsland, Ph. D. Thesis, Free University, Amsterdam, 1980.Google Scholar
  16. 16.
    C. V. Krishnan and H. L. Friedman,J. Phys. Chem. 75, 3598 (1971).Google Scholar
  17. 17.
    W. J. M. Heuvelsland, C. de Visser, and G. Somsen,J. Chem. Soc. Faraday Trans. I 77, 1191 (1981).Google Scholar
  18. 18.
    W. J. M. Heuvelsland, C. de Visser, G. Somsen, A. LoSurdo, and W. Y. Wen,J. Solution Chem. 8, 21 (1979).Google Scholar
  19. 19.
    A. LoSurdo, W. Y. Wen, C. Jolicoeur, and J. L. Fortier,J. Phys. Chem. 81, 1813 (1977).Google Scholar
  20. 20.
    S. Cabani, G. Conti, A. Martinelli, and E. Matteoli,J. Chem. Soc. Faraday Trans. I 69, 2112 (1973).Google Scholar

Copyright information

© Plenum Publishing Corporation 1981

Authors and Affiliations

  • Aart C. Rouw
    • 1
  • Gus Somsen
    • 1
  1. 1.Department of ChemistryFree UniversityAmsterdamThe Netherlands

Personalised recommendations