Journal of Solution Chemistry

, Volume 17, Issue 3, pp 245–265 | Cite as

Excess enthalpies of solution of some primary and secondary alcohols in sodium dodecylsulfate micellar solutions

  • R. De Lisi
  • S. Milioto


The exces enthalpies of solution of some primary and secondary alcohols in aqueous sodium dodecylsulfate micellar solutions were measured and the results were explained by considering the distribution of alcohols between aqueous and micellar phases. The distribution constant and the enthalpy of transfer (and the standard free energy and entropy of transfer) were obtained. The thermodynamic parameters for the transfer of secondary alcohols from the aqueous to the sodium dodecylsulfate (NaDS) micellar phase differ slightly from those of the corresponding primary alcohols. For both series of alcohols the additivity rule holds for free energies of transfer whereas enthalpies and entropies display convex curves. The present data are compared to those for the transfer of the same solutes from the aqueous to the dodecyldimethylamine oxide (DDAO) and dodecyltrimethylammonium bromide (DTAB) micellar phases. The role of the hydrophilic interactions between the OH group and the micelles' head groups is formulated. The thermodynamics of the branched methyl group were determined. Furthermore, the thermodynamics of solvation of primary alcohols in water, in NaDS micelles, and in octane have been calculated using reference states based on the assumption that the empty space around alcohols in the initial and final states is the same. It is shown that the solvation of alcohols in NaDS micellar phase is enthalpy driven and that the thermodynamic properties of solvation vs. the length of the alcohol tail is the same for water and NaDS micelles whereas it is different for octane. A possible explanation for this difference is that the alkyl chain of alcohols folds in octane.

Key words

methanol ethanol propanol butanol pentanol hexanol heptanol 2-propanol 2-butanol 2-pentanol 2-hexanol 2-heptanol sodium dodecylsulfate enthalpies of solution mixed micelles thermodynamics of transfer of alcohols from water to micelles 


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  1. 1.
    R. De Lisi, C. Genova, and V. Turco Liveri,J. Colloid Interface Sci. 95, 428 (1983).Google Scholar
  2. 2.
    R. De Lisi, C. Genova, R. Testa, and V. Turco Liveri,J. Solution Chem. 13, 121 (1984).Google Scholar
  3. 3.
    R. De Lisi, V. Turco Liveri, M. Castagnolo, M. and A. Inglese,J. Solution Chem. 15, 23 (1986).Google Scholar
  4. 4.
    R. De Lisi, A. Lizzio, S. Milioto, and V. Turco Liveri,J. Solution Chem. 15, 23, (1986).Google Scholar
  5. 5.
    R. De Lisi, S. Milioto, and V. Turco Liveri,J. Colloid Interface Sci. 117, 64 (1987).Google Scholar
  6. 6.
    R. De Lisi, S. Milioto, M. Castagnolo, and A. Inglese,J. Solution Chem. 16, 373 (1987).Google Scholar
  7. 7.
    S. Milioto and R. De Lisi,J. Colloid Interface Sci. (in press).Google Scholar
  8. 8.
    R. De Lisi and S. Milioto,J. Solution Chem. 16, 767 (1987).Google Scholar
  9. 9.
    S. Milioto, D. Romancino, and R. De Lisi,J. Solution Chem. In press.Google Scholar
  10. 10.
    E. E. Tucker and S. D. Christian,Faraday Symp. Chem. Soc. 17, 11 (1982).Google Scholar
  11. 11.
    C. Treiner,J. Colloid Interface Sci. 90, 444 (1982).Google Scholar
  12. 12.
    A. H. Roux, D. Hétu, G. Perron, and J. E. Desnoyers,J. Solution Chem. 13, 1 (1984).Google Scholar
  13. 13.
    R. De Lisi and V. Turco Liveri,Gazzetta Chim. Ital. 113, 371 (1983).Google Scholar
  14. 14.
    F. Yamashita, G. Perron, J. E. Desnoyers, and J. C. T. Kwak,A.C.S. Symposium Ser. No. 311, 79 (1986).Google Scholar
  15. 15.
    G. Roux-Desgranges, A. H. Roux, J. P. Grolier, and A. Viallard,J. Solution Chem. 11, 357 (1982).Google Scholar
  16. 16.
    A. Rohde and E. Sackmann,Ber. Bunseges. Phys. Chem. 82, 978 (1978).Google Scholar
  17. 17.
    R. Bury and C. Treiner,J. Colloid Interface Sci. 103, 1 (1985).Google Scholar
  18. 18.
    R. Aveyard and A. S. C. Lawrence,Trans. Faraday Soc. 60, 2265 (1964).Google Scholar
  19. 19.
    D. Hallen, S. O. Nilsson, W. Rothschild, and I. Wadsö,J. Chem. Thermodyn. 18, 429 (1986).Google Scholar
  20. 21.
    R. Zana, S. Yiv, C. Strazielle, and P. Lianos,J. Colloid Interface Sci. 80, 208 (1981).Google Scholar
  21. 21.
    W. McMillan and J. Mayer,J. Phys. Chem. 13, 176 (1945).Google Scholar
  22. 22.
    P. Mukerjee, K. J. Mysels, and P. Kapauan,J. Phys. Chem. 71, 4166 (1967).Google Scholar
  23. 23.
    E. D. Goddard and G. C. Benson,Can. J. Chem. 35, 986 (1957).Google Scholar
  24. 24.
    E. M. Woolley and T. E. BurchfieldJ. Phys. Chem. 88, 2155 (1984).Google Scholar
  25. 25.
    M. Manabe, K. Shirahama, and M. Koda,Bull. Chem. Soc. Jpn 49, 2904 (1976).Google Scholar
  26. 26.
    K. Hayase and S. Hayano,Bull. Chem. Soc. Jpn. 50, 83 (1977).Google Scholar
  27. 27.
    P. Stilbs,J. Colloid Interface Sci. 87, 385 (1982).Google Scholar
  28. 28.
    C. Treiner, A. K. Chattopadhyay, and R. Bury,J. Colloid Interface Sci. 104, 569 (1985).Google Scholar
  29. 29.
    P. Lianos and R. Zana,J. Colloid Interface Sci. 84, 100 (1981).Google Scholar
  30. 30.
    K. W. Herrmann,J. Phys. Chem. 66, 295 (1962).Google Scholar
  31. 31.
    N. A. Mazer, G. B. Benedek, and N. C. Carey,J. Phys. Chem. 80, 1075 (1976).Google Scholar
  32. 32.
    D. F. Evans and P. J. Wightman,J. Colloid Interface Sci. 86, 515 (1982).Google Scholar
  33. 33.
    J. E. Desnoyers, M. Billon, S. Léger, G. Perron, and J.-P. Morel,J. Solution Chem. 5, 681 (1976).Google Scholar
  34. 34.
    J. A. V. Butler, C. N. Ramchandani, and D. W. Thomson,J. Chem. Soc. 280 (1935).Google Scholar
  35. (35a.)
    M. Goffredi and V. Turco Liveri,J. J. Solution Chem. 10, 693 (1981);Google Scholar
  36. (35b.)
    R. De Lisi and V. Turco Liveri, unpublished data for methanol.Google Scholar

Copyright information

© Plenum Publishing Corporation 1988

Authors and Affiliations

  • R. De Lisi
    • 1
  • S. Milioto
    • 1
  1. 1.Istituto di Chimica FisicaUniversitè di PalermoPalermoItaly

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