Linear solvation energy relationships. Part 9. - Correlations of gas/liquid partition coefficients with the solvatochromic parameters, π*, α and β

Mortimer J. Kamlet, Robert W. Taft, Peter W. Carr, Michael H. Abraham

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Abstract

When referenced to an alkane solute of similar molecular volume, i.e. log (Ksolute/Kalkane), gas/liquid partition coefficients for nitromethane, methylethylketone, dioxan, toluene and ethanol solutes are well correlated by the solvatochromic parameters, π*, δ, α and β. For nitromethane and dioxan solutes the partition coefficients depend only on the dipolarity/polarizability parameters (π*, δ). For methylethylketone, there is also a measurable dependence on hydrogen-bond donor acidity (α) of protic solvents. For ethanol in aliphatic non-hydrogen-bond donor solvents the dominant effects are solvent dipolarity/polarizability and solvent hydrogen-bond acceptor basicity (β). For toluene solute there appears to be a negative or desolvation effect in protic solvents which is attributed to a 'hydroxyphobic effect' of weakly basic solutes in alcohol solvents.

Original languageEnglish (US)
Pages (from-to)1689-1704
Number of pages16
JournalJournal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases
Volume78
Issue number6
DOIs
StatePublished - 1982

Bibliographical note

Funding Information:
It is more fruitful to use solute characteristics such as the output a, b and s values in eqn (2) and (3) that refer to the (monomeric) solute at infinite dilution. The work by R. W.T. was supported in part by a grant from the Public Health Service. The work by M.J.K. was done under Naval Surface Weapons Center Independent Research Task IR-201. Part 8.-R. W. Taft and M. J. Kamlet, Org. Magn. Reson., 1980, 14, 485. M. J. Kamlet, J. L. M. Abboud and R. W. Taft, Prog. Phys. Org. Chem., 1981, 13, 485. M. J. Kamlet, J. L. M. Abboud and R. W. Taft, J. Am. Chem. SOC., 1977,99, 6027. M. J. Kamlet, T. N. Hall, J. Boykin and R. W. Taft, J. Org. Chem., 1979, 44, 2599. J. L. M. Abboud, M. J. Kamlet and R. W. Taft, J. Am. Chem. SOC., 1977,99, 8327. J. L. M. Abboud and R. W. Taft, J. Phys. Chem., 1979, 83, 412. H. Block and S. Walker, Chem. Phys. Lett., 1973, 19, 363. 0. Kolling, Trans. Kansas Acad. Sci., 1981, 84, 32. V. Bekarek, CON. Czech. Chem. Commun., 1980, 45, 2063. lo V. Bekarek, J. Phys. Chem., 1981, 85, 722. l 1 (a) R. W. Taft and M. J. Kamlet, J. Chem. SOC., Perkin Trans. 2, 1979, 1723; (b) M. J. Kamlet and R. W. Taft, J. Chem. SOC., Perkin Trans. 2,1979,349; ( c ) R. W. Taft and M. J. Kamlet, J. Am. Chem. Soc., 1976, 98, 2886. l 2 R. W. Taft et al., paper on a scale in preparation. l3 M. J. Kamlet and R. W. Taft, J. Am. Chem. SOC., 1976, 98, 377. l4 M. J. Kamlet, J. L. M. Abboud, M. E. Jones and R. W. Taft, J. Chem. SOC., Perkin Trans. 2, 1979, l 5 M. J. Kamlet, A. Solomonovici and R. W. Taft, J. Am. Chem. SOC., 1979, 101, 3734. l6 C. Reichardt, Solvent Effects in Organic Chemistry (Verlag Chemie, Weinheim, 1979). l7 R. W. Taft, J. L. M. Abboud and M. J. Kamlet, J. Am. Chem. SOC., 1981, 103, 1080. l9 M. J. Kamlet, C. Dickinson and R. W. Taft, J. Chem. SOC., Perkin Trans. 2, 1981, 353. 2o P. W. Carr, J. Chromatogr., 1980, 194, 105. 21 L. Rohrschneider, Anal. Chem., 1973, 45, 1241. 22 L. R. Snyder, J. Chromatogr. Sci., 1978, 16, 223. t Unfortunately, complications caused by this effect have led us to revise published a values more 342. M. J. Kamlet, C. Dickinson and R. W. Taft, Chem. Phys. Lett., 1981, 77, 69. frequently than we would care to admit.1704 LINEAR SOLVATION ENERGY RELATIONSHIPS 23 J. H. Hildebrand and R. L. Scott, The Solubility of Nonelectrolytes (Dover Publications, New York, 3rd edn, 1964); J. H. Hildebrand and R. L. Scott, Regular Solutions (Prentice Hall, Englewood Cliffs, N.J., 1962). 24 M. H. Abraham, A. Nasezadeh, J. J. Moura Ramos and J. Reisse, J. Chem. SOC., Perkin Trans. 2, 1980, 854. 25 M. H. Abraham and G. F. Johnson, J. Chem. SOC. A, 1971, 1610. 26 M. H. Abraham, J. Am. Chem. SOC., 1979, 101, 5477. 27 S. Ehrenson, J. Org. Chem., 1979, 44, 1793. 28 J. Shorter, Correlation Analysis in Organic Chemistry (Clarendon Press, Oxford, 1973). 29 C. Duboc, Spectrochim. Acta, Part A, 1974, 30, 431, 440. 30 M. H. Abraham, J. Am. Chem. SOC., 1980, 102, 5910. 31 P. L. Huyskens, J. Am. Chem. SOC., 1977, 99, 2579. (PAPER O / 1858)

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