Abstract
In order to clarify some aspects of the hydrophobic interactions, the enthalpies of dilution of monoethylurea, 1,3-dimethylurea, and 1,3-diethylurea have been determined calorimetrically at 25°C. The calorimetric data, expressed in terms of excess enthalpy, permit the evaluation of the pair and triplet interaction coefficients. The analyses of these and of the analogous coefficientsg xx andg xxx, derived from osmotic data, indicate a driving force favorable to the interactions among the hydrated solute molecules. Nevertheless, the positive values of theh xx andh xxx coefficients seem to suggest that the source of the effect is a rearrangement of the water molecules rather than a direct association of the solute molecules. There are evidences of a strict correlation between the enthalpic and the entropic effects.
Similar content being viewed by others
References
P. H. von Hippel and K. Y. Wong,J. Biol. Chem. 240, 3909 (1965).
J. Konicek and I. Wadsö,Acta Chem. Scand. 25, 1541 (1971).
J. S. Rowlinson,Liquids and Liquid Mixtures, 1st and 2nd edns. (Butterworths, London, 1959; 1969).
A. Johansson and P. A. Kollman,J. Am. Chem. Soc. 94, 6196 (1972).
W. Kauzmann,Adv. Protein Chem. 14, 1 (1959).
J. J. Kozak, W. S. Knight, and W. Kauzmann,J. Chem. Phys. 48, 675 (1968).
W. G. McMillan, Jr., and J. E. Mayer,J. Chem. Phys. 13, 276 (1945).
H. L. Friedman and C. V. Krishnan,J. Solution Chem. 2, 119 (1973).
F. Franks, M. Pedley, and D. S. Reid,J. Chem. Soc. Faraday Trans. 1 72, 359 (1976).
R. B. Cassel and R. H. Wood,J. Phys. Chem. 78, 2465 (1974).
T. H. Lilley and R. P. Scott,J. Chem. Soc. Faraday Trans. 1 72, 184 (1976).
J. E. Desnoyers, G. Perron, L. Avédikian, and J. P. Morel,J. Solution Chem. 5, 631 (1976).
J. J. Savage and R. H. Wood,J. Solution Chem. 5, 733 (1976).
J. A. Gordon and W. P. Jencks,Biochemistry 2, 47 (1963).
C. Tanford,Adv. Protein Chem. 23, 122 (1968).
J. R. Warren and J. A. Gordon,J. Biol. Chem. 245, 4097 (1970).
T. T. Herskovits, H. Jaillet, and B. Gadegbeku,J. Biol. Chem. 245, 4544 (1970).
T. T. Herskovits, H. Jaillett, and A. T. De Sena,J. Biol. Chem. 245, 6511 (1970).
G. Barone, C. Galbiati, E. Rizzo, and V. Volpe,Proceedings of the First European Biophysics Congress, Vol. 1 (Verlag der Wiener Medezinischen Akademie, Vienna, 1971), p. 49.
D. Eagland, inWater—A Comprehensive Treatise, Vol. 4, Chap. V. F. Franks, ed. (Plenum Press, New York, 1975).
M. F. Emerson and A. Holtzer,J. Phys. Chem. 71, 3320 (1967).
D. R. Robinson and W. P. Jencks,J. Am. Chem. Soc. 87, 2462 (1965).
V. Crescenzi, F. Quadrifoglio, and A. Cesàro,Int. J. Protein Res. 3, 49 (1971).
M. Roseman and W. P. Jencks,J. Am. Chem. Soc. 97, 631 (1975).
P. R. Philip, G. Perron, and J. E. Desnoyers,Can. J. Chem. 52, 1709 (1974).
G. Barone, E. Rizzo, and V. Vitagliano,J. Phys. Chem. 74, 2230 (1970).
G. Barone, G. Castronuovo, C. Della Volpe, and V. Elia,J. Solution Chem. 6, 117 (1977).
G. Barone, E. Rizzo and V. Volpe,J. Chem. Eng. Data 21, 59 (1976).
P. Monk and I. Wadsö,Acta Chem. Scand. 22, 1842 (1968).
P. Monk and I. Wadsö,Acta Chem. Scand. 23, 29 (1969).
J. M. Sturtevant, inTechniques of Chemistry, Vol. I, Part V, A. Weissberger and B. W. Rossiter, eds. (Wiley-Interscience, New York, 1971), pp. 402 and 403.
I. M. Klotz and R. K. Rosenberg, inChemical Thermodynamic (Benjamin, Menlo Park California, 1964).
J. L. Fortier, P. A. Leduc, P. Picker, and J. E. Desnoyers,J. Solution Chem. 2, 467 (1973).
H. L. Friedman,J. Solution Chem. 1, 387 (1972).
G. C. Kresheck,J. Phys. Chem. 73, 2441 (1969).
F. T. Gucker and H. B. Pickard,J. Am. Chem. Soc. 62, 1464 (1940).
E. P. Egan and B. B. Luff.J. Chem. Eng. Data 11, 192 (1966).
S. J. Gill and E. L. Farquhar,J. Am. Chem. Soc. 90, 3039 (1968).
D. Hamilton and R. H. Stokes,J. Solution Chem 1, 223 (1972).
G. Barone, G. Castronuovo, V. Elia, and A. Menna, submitted toJ. Solution Chem.
H. L. Friedman,Ionic Solution Theory (Interscience, New York, 1962).
H. L. Friedman,J. Phys. Chem. 32, 1351 (1960).
F. Franks and D. S. Reid, inWater—A Comprehensive Treatise, Vol. 3, F. Franks, ed. (Plenum Press, New York, 1973), Chap. V.
F. Franks, inWater—A Comprehensive Treatise, Vol. 4, F. Franks, ed. (Plenum Press, New York, 1975), Chap. I.
J. A. V. Butler,Trans. Faraday Soc. 33, 235 (1937).
D. D. Eley,Trans. Faraday Soc. 35, 1281 (1939).
H. S. Frank and M. W. Evans,J. Chem. Phys. 13, 507 (1945).
F. Franks and D. J. G. Ives,Q. Rev. (London) 20, 1 (1966).
E. R. Nightingale, Jr., inChemical Physics of Ionic Solutions, B. E. Conway and R. G. Barradas, eds. (Wiley, New York, 1966), p. 87.
G. Nemethy and H. A. Scheraga,J. Chem. Phys. 36, 3382, 3401, (1962).
C. Tanford,The Hydrophobic Effect (Wiley-Interscience, New York, 1973).
A. Ben-Naim,An Introduction to a Molecular Theory of Water and Aqueous Solutions (Plenum Press, New York, 1974).
R. Lumry and S. Rajander, inEnthalpy-Entropy Compensation Phenomena in Water Solutions and Small Molecules, M. Goodman, ed. (Interscience, New York, 1970).
Author information
Authors and Affiliations
Additional information
To whom correspondence should be addressed.
Rights and permissions
About this article
Cite this article
Barone, G., Castronuovo, G., Crescenzi, V. et al. The hydrophobic effect in aqueous solutions of nonelectrolytes. I. Self-interactions of alkylureas. J Solution Chem 7, 179–192 (1978). https://doi.org/10.1007/BF00650525
Received:
Revised:
Issue Date:
DOI: https://doi.org/10.1007/BF00650525