Abstract
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.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
W. J. M. Heuvelsland, M. Bloemendal, C. de Visser, and G. Somsen,J. Phys. Chem. 84, 2391 (1980).
A. C. Rouw and G. Somsen,J. Chem. Thermodynamics 13, 67 (1981).
F. Franks and B. Watson,Trans. Faraday Soc. 65, 2339 (1969).
F. M. Jones III and E. M. Arnett,Progr. Phys. Org. Chem. 11, 263 (1974).
S. Cabani, G. Conti, and L. Lepori,Trans. Faraday Soc. 67, 1933 (1971).
J. Konicek and I. Wadsö,Acta Chem. Scand. 25, 1541 (1971).
S. Bergström and G. Olofsson,J. Solution Chem. 4, 535 (1975).
S. Bergström and G. Olofsson,J. Solution Chem. 7, 497 (1978).
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).
W. J. M. Heuvelsland, C. de Visser, and G. Somsen,J. Phys. Chem. 82, 29 (1978).
I. Wadsö,Sci. Tools 13, 33 (1966).
R. R. Dreisbach,Physical Properties of Chemical Compounds Vol. 3, Advances in Chemistry Series No. 29 (Am. Chem. Soc., Washington, 1961).
J. C. Verhoef and E. Barendrecht,Anal. Chim. Acta 94, 395 (1977).
Z. Pawlak and R. G. Bates,J. Solution Chem. 4, 817 (1975).
W. J. M. Heuvelsland, Ph. D. Thesis, Free University, Amsterdam, 1980.
C. V. Krishnan and H. L. Friedman,J. Phys. Chem. 75, 3598 (1971).
W. J. M. Heuvelsland, C. de Visser, and G. Somsen,J. Chem. Soc. Faraday Trans. I 77, 1191 (1981).
W. J. M. Heuvelsland, C. de Visser, G. Somsen, A. LoSurdo, and W. Y. Wen,J. Solution Chem. 8, 21 (1979).
A. LoSurdo, W. Y. Wen, C. Jolicoeur, and J. L. Fortier,J. Phys. Chem. 81, 1813 (1977).
S. Cabani, G. Conti, A. Martinelli, and E. Matteoli,J. Chem. Soc. Faraday Trans. I 69, 2112 (1973).
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Rouw, A.C., Somsen, G. Solvation and hydrophobic hydration of different types of alkylamines inN,N-dimethylformamide and water mixtures. J Solution Chem 10, 533–547 (1981). https://doi.org/10.1007/BF00646934
Received:
Revised:
Issue Date:
DOI: https://doi.org/10.1007/BF00646934