Abstract
The apparent enthalpy, free energy and entropy of transfer from aqueous buffer (pH 7) to water-saturated octanol were determined for the aliphatic alcohols methanol to octanol using an isoperibol flow-calorimeter. For the higher homologues, a linear relationship between enthalpy and free energy change is found indicating an enthalpy-entropy compensation effect. The thermodynamics of transfer were rationalized in terms of the thermodynamics of solvation in the separate phases, including water itself as a solute. The role of water as a cosolvent in the octanol phase is discussed.
Similar content being viewed by others
References
W. Riebesehl and E. Tomlinson,J. Phys. Chem. 88, 4770 (1984).
W. Riebesehl, E. Tomlinson, and H. J. M. Grünbauer,J. Phys. Chem. 88, 4775 (1984).
W. Riebesehl, E. Tomlinson, and R. Niemel,J. Solution Chem., in press.
A. E. Beezer, W. H. Hunter, and D. E. Storey,J. Pharm. Pharmacol. 35, 350 (1983).
K. J. Breslauer, L. Witkowski, and K. Bulas,J. Phys. Chem. 82, 675 (1978).
J. F. M. Kinkel, E. Tomlinson, and P. Smit,Int. J. Pharm. 9, 121 (1981).
E. A. Lissi,Acta Sud Amer. Quim.,1 69 (1981).
W. Riebesehl and E. Tomlinson,J. Chem. Soc. Faraday Trans. I 79, 1311 (1983).
K. Shinoda, inPrinciples of Solution and Solubility, (Marcel Dekker, New York, 1966).
A. Leo, C. Hansch and D. Elkins,Chem. Rev. 71, 525 (1971).
D. J. T. Hill and L. R. White,Aust. J. Chem. 27, 1905 (1974).
R. Aveyard and R. Heselden,J. Chem. Soc., Faraday Trans. I 71, 312 (1975).
J. E. Leffler and E. Grunwald, inRates and Equilibria of Organic Reactions, (Wiley, New York, 1963).
R. N. Smith, C. Hansch, and M. M. AmesJ. Pharm. Sci. 64, 599 (1975).
W. J. M. Heuvelsland,Ph. D. Thesis, Free University of Amsterdam, 1980.
C. DeVisser, and G. Somsen,J. Chem. Therm. 4, 313 (1972).
M. Bloemendal and G. Somsen private communication.
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Riebesehl, W., Tomlinson, E. Thermodynamics of non-electrolyte transfer between octanol and water. J Solution Chem 15, 141–150 (1986). https://doi.org/10.1007/BF00646285
Received:
Accepted:
Issue Date:
DOI: https://doi.org/10.1007/BF00646285