Journal of Solution Chemistry

, Volume 37, Issue 4, pp 451–457 | Cite as

Solvent Effects on the Enthalpy and Entropy of Activation for the Hydrolysis of β-Lactones

  • José A. Manso
  • M. Teresa Pérez-Prior
  • María del Pilar García-Santos
  • Emilio Calle
  • Julio Casado


The hydrolysis of β-propiolactone and β-butyrolactone in binary water + dioxane mixtures was investigated by kinetic studies. The following conclusions were reached: First, β-propiolactone is more reactive than β-butyrolactone across the range of water + dioxane compositions. This observation was rationalized in terms of the electric charge flow caused by the β-butyrolactone’s methyl substituent. Second, hydrolysis of these lactones is essentially enthalpy controlled. Third, an increase in the dioxane percentage, which relaxes the intermolecular hydrogen bonds in the ordered structure of water, reduces the enthalpy of activation ΔH # and simultaneously increases the entropy of activation ΔS #(absolute value) for solvent compositions up to 60% dioxane. Fourth, plotting ΔH #S # against the solvent composition yields an N-shaped curve. This results is a consequence of the quadratic and cubic terms appearing in the expressions of ΔH # and ΔS # as functions of the solvent media composition. Fifth, an ABC classification was set up to characterize the behavior of ΔH #S # for the solvolysis of these lactones.


Lactones Mixed solvents Hydrolysis 


Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.


  1. 1.
    García-Santos, M.P., Calle, E., Casado, J.: Amino acid nitrosation products as alkylating agents. J. Am. Chem. Soc. 123, 7506–7510 (2001) CrossRefGoogle Scholar
  2. 2.
    García-Santos, M.P., González-Mancebo, S., Hernández-Benito, J., Calle, E., Casado, J.: Reactivity of amino acids in nitrosation reactions and its relation to the alkylating potential of their products. J. Am. Chem. Soc. 124, 2177–2182 (2002) CrossRefGoogle Scholar
  3. 3.
    García-Santos, M.P., Calle, E., Casado, J.: A method for the kinetic study of amino acid nitrosation reactions. Polyhedron 22, 1059–1066 (2003) CrossRefGoogle Scholar
  4. 4.
    Lawley, P.D.: Carcinogenesis by alkylating agents. In: Searle, C.E. (ed.) Chemical Carcinogens, Chap. 7, 2nd edn. ACS Monograph, vol. 182. American Chemical Society, Washington (1984) Google Scholar
  5. 5.
    Pérez-Prior, M.T., Manso, J.A., García-Santos, M.P., Calle, E., Casado, J.: Reactivity of lactones and GHB formation. J. Org. Chem. 70, 420–426 (2005) CrossRefGoogle Scholar
  6. 6.
    Manso, J.A., Pérez-Prior, M.T., García-Santos, M.P., Calle, E., Casado, J.: A kinetic approach to the alkylating potential of carcinogenic lactones. Chem. Res. Toxicol. 18, 1161–1166 (2005) CrossRefGoogle Scholar
  7. 7.
    CRC Handbook of Chemistry and Physics, 85th edn. CRC Press, Boca Raton (2004–2005) Google Scholar
  8. 8.
    Van Duuren, B.L.: Carcinogenic epoxides, lactones, and halo-ethers and their mode of action. Ann. N.Y. Acad. Sci. 163, 633–651 (1969) CrossRefGoogle Scholar
  9. 9.
    Tommila, E.: The influence of the solvent on reaction velocity XII. The solvolysis of alkyl benzenesulphonates in acetone-water and dioxane-water mixtures. Acta Chem. Scand. 9, 975–988 (1951) Google Scholar
  10. 10.
    Leffler, E., Grunwald, E.: Rates and Equilibria of Organic Reactions as Treated by Statistical, Thermodynamic, and Extrathermodynamic Methods. Dover, New York (1963), pp. 397–402 Google Scholar
  11. 11.
    Winstein, S., Fainberg, A.H.: Correlation of solvolysis rates. IV. Solvent effects on enthalpy and entropy of activation for solvolysis of t-butyl chloride. J. Am. Chem. Soc. 79, 5937–5950 (1957) CrossRefGoogle Scholar
  12. 12.
    Tommila, E., Jutila, J.: Hydrolysis and alcoholysis of sulphonic esters. Acta Chem. Scand. 6, 844–853 (1952) CrossRefGoogle Scholar
  13. 13.
    Tommila, E., Merikallio, E.: Effect of the solvent on reaction velocity. (VI) Hydrolysis of alkyl esters of benzenesulfonic acid in dioxane-water mixtures. Suom. Kemistil. 26B, 79–80 (1953) Google Scholar
  14. 14.
    Tommila, E., Tiilikainen, M., Voipio, A.: Effect of the solvent on reaction velocity. (X) Solvolysis of alkyl halides in acetone-water mixtures. Ann. Acad. Sci. Fenn. 65, 1–26 (1955) Google Scholar

Copyright information

© Springer Science+Business Media, LLC 2008

Authors and Affiliations

  • José A. Manso
    • 1
  • M. Teresa Pérez-Prior
    • 1
  • María del Pilar García-Santos
    • 1
  • Emilio Calle
    • 1
  • Julio Casado
    • 1
  1. 1.Departamento de Química FísicaUniversidad de SalamancaSalamancaSpain

Personalised recommendations