Group contributions to the thermodynamic properties of non-ionic organic solutes in dilute aqueous solution

The thermodynamic properties ΔGho,ΔHho, and ΔCp,hoassociated with the transfer of non-ionic organic compounds from gas to dilute aqueous solution and the limiting partial molar properties Cpo,2 and V22 of these compounds in water are described through a simple scheme of group contributions. A distinction is made between groups made only of carbon and hydrogen, and functional groups i.e. groups containing at least one atom different from carbon and hydrogen. Each group is assigned a contribution, for each property, through a least squares procedure which utilizes only molecules containing at most one functional group. Finally, for compounds containing more than one functional group, correction parameters are evaluated as the differences between the experimental values and those calculated by means of the group contributions. The different behavior of hydrophilic compared with hydrophobic groups is discussed for the various properties. A rationale for the correction parameters, i.e. for the effects of the interactions among hydrophilic groups on the thermodynamic properties, is attempted.

[1]  A. Leo,et al.  Dependence of hydrophobicity of apolar molecules on their molecular volume. , 1976, Journal of medicinal chemistry.

[2]  A. Bondi,et al.  Physical properties of molecular crystals liquids, and glasses , 1968 .

[3]  W. Kauzmann.  Some factors in the interpretation of protein denaturation. , 1959, Advances in protein chemistry.

[4]  D. R. Stull,et al.  The chemical thermodynamics of organic compounds , 1969 .

[5]  H. Høiland,et al.  Partial Molal Volumes and Additivity of Group Partial Molal Volumes of Alcohols in Aqueous Solution at 25 and 35 degrees C. , 1976 .

[6]  Alarich Weiss,et al.  Arnold Bondi: Physical Properties of Molecular Crystals, Liquids, and Glasses. John Wiley and Sons, New York, London, Sydney 1968. 502 Seiten. Preis: 175 s. , 1968, Berichte der Bunsengesellschaft für physikalische Chemie.

[7]  J. Guthrie.  Additivity schemes permitting the estimation of partial molar heat capacities of organic compounds in aqueous solution , 1977 .

[8]  R. Reid,et al.  The Properties of Gases and Liquids , 1977 .

[9]  C. Jolicoeur,et al.  Thermodynamic properties of aqueous organic solutes in relation to their structure. Part III. Apparent molal volumes and heat capacities of low molecular weight alcohols and polyols at 25 °C , 1976 .

[10]  E. Matteoli,et al.  Heat capacities of hydration of saturated uncharged organic compounds at 25° C , 1978 .

[11]  F. Shahidi,et al.  Partial molar volumes of organic compounds in water. VI. α,ω-diaminoalkane hydrochlorides , 1978 .

[12]  J. T. Edward,et al.  Relation between van der Waals and Partial Molal Volumes of Organic Molecules in Water , 1975 .

[13]  S. Gill,et al.  An equation of state describing hydrophobic interactions. , 1976, Proceedings of the National Academy of Sciences of the United States of America.

[14]  Charles Tanford,et al.  The Hydrophobic Effect: formation of micelles and biological membranes''John Wiley & Sons , 1991 .

[15]  Henry S. Frank,et al.  Free Volume and Entropy in Condensed Systems III. Entropy in Binary Liquid Mixtures; Partial Molal Entropy in Dilute Solutions; Structure and Thermodynamics in Aqueous Electrolytes , 1945 .

[16]  I. Wadsö,et al.  Additivity relations for the heat capacities of non-electrolytes in aqueous solution☆ , 1976 .

[17]  S. Arakawa,et al.  Contribution of hydrogen bonds to the partial molar volumes of nonionic solutes in water , 1975 .

[18]  P. Gianni,et al.  Thermodynamic functions of hydration of saturated uncharged organic compounds. Free energies, enthalpies and entropies at 25°C , 1979 .

[19]  J. Hine,et al.  Structural effects on rates and equilibriums. XIX. Intrinsic hydrophilic character of organic compounds. Correlations in terms of structural contributions , 1975 .

[20]  R. Pierotti,et al.  Aqueous Solutions of Nonpolar Gases1 , 1965 .

[21]  F. Hirata,et al.  Molar Volume of Ions , 1973 .

[22]  H. Høiland.  Volumes of ionization of dicarboxylic acids in aqueous solution from density measurements at 25°C , 1975 .

[23]  A. Bondi.  van der Waals Volumes and Radii , 1964 .