Abstract
A modified Wilson model is tested for its ability to correlate and predict distribution coefficients in two representative systems: 1-butanol-water and cyclohexanewater. The model is fitted to ternary equilibrium data for various solutes in these systems using a procedure involving minimization of the least-squares distance between calculated and experimental logarithmic distribution ratios. In addition, benzene-water, hexane-water, and cyclohexane-water distribution coefficients for infinitely diluted liquid solutes are predicted using only binary system information. All computations involve using both van der Waals and molar volumes as structural parameters to account for the geometry of the molecules studied. Satisfactory representations of experimental distribution ratios and fairly accurate distribution coefficients at infinite dilution are obtained for both systems. However, in a number of cyclohexane-water systems, miscibilities of constituent binary mixtures are poorly predicted from ternary system information when van der Waals volumes are used. Replacement of van der Waals volumes by molar volumes has little influence on the fit, but significant improvement is observed for the prediction of both binary miscibility properties and for distribution coefficients at infinite dilution in all the solvent-water systems considered.
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References
H. J. M. Grünbauer, T. Bultsma, and R. F. Rekker,Eur. J. Med. Chem. 17, 411 (1982).
H. J. M. Grünbauer and E. Tomlinson,Int. J. Pharm. 21, 61 (1984).
T. Tsuboka and T. Katayama,J. Chem. Eng. Japan 8, 181 (1975).
D. S. Abrams and J. M. Prausnitz,Am. Inst. Chem. Eng. Journal 21, 116 (1975).
S. Srebrenik and S. Cohen,J. Phys. Chem. 80, 996 (1976).
I. Kojima and S. S. Davis,Int. J. Pharm. 20, 247 (1984).
A. Bondi,J. Phys. Chem. 68, 441 (1964).
S. Terasawa, H. Itsuki, and S. Arakawa,J. Phys. Chem. 79, 2345 (1975).
J. T. Edward and P. G. Farrell,Can. J. Chem. 53, 2965 (1975).
F. Shahidi,J. Solution Chem. 12, 295 (1983).
J. M. Sørensen, T. Magnussen, P. Rasmussen, and A. Fredenslund,Fluid Phase Equilibria 3, 47 (1979).
R. F. Rekker,The Hydrophobic Fragmental Constant, (Elsevier, Amsterdam, 1977) and unpublished compilation of fragmental values in alkane-water systems.
J. A. Riddick and W. B. Bunger, ‘Organic Solvents’ inTechniques of Chemistry, Vol. 2, (Wiley Interscience, New York, 1970).
D. M. Marquardt,J. Soc. Ind. Appl. Math. 11, 431 (1963).
C. Hansch and A. Leo,Substituent Constants for Correlation Analysis in Chemistry and Biology, (Wiley, New York, 1979) and Supplements of the Pomona College Medicinal Chemistry Project Data File.
J. M. Sørensen and W. Arlt,Liquid-Liquid Equilibrium Data Collection, (Chemistry Data Series, DECHEMA, Frankfurt/Main, 1980), Vol. 5.
H. Hoiland and E. Vikingstad,Acta. Chem. Scand. A30, 182 (1976).
J. H. Vera, S. G. Sayegh, and G. A. Ratclif,Fluid Phase Equilibria 1, 113 (1977).
T. Magnussen, J. M. Sørensen, P. Rasmussen, and A. Fredenslund,Fluid Phase Equilibria 4, 151 (1980).
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Presentation to First International Symposium on Solubility Phenomena, University of Western Ontario, London, Ontario, August 21–23, 1984.
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Grünbauer, H.J.M., Tomlinson, E. Correlation and prediction of liquid-liquid distribution coefficients in aqueous systems using a modified Wilson model. J Solution Chem 14, 499–512 (1985). https://doi.org/10.1007/BF00646981
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DOI: https://doi.org/10.1007/BF00646981