Skip to main content
SpringerLink
Log in

Ester decomposition as a two-center synchronous reaction

  • Published:
Kinetics and Catalysis Aims and scope Submit manuscript

Abstract

Experimental data on the molecular decomposition of esters with various structures into an olefin and the corresponding acid in the gas phase are analyzed in terms of the intersecting parabolas method. Enthalpies and kinetic parameters characterizing this decomposition have been calculated for 33 reactions. Ester decomposition is a concerted two-center reaction characterized by a very high classical potential barrier of thermoneutral reaction (148–206 kJ/mol). The totality of reactions examined is divided into eight classes. Activation energies and rate constants have been calculated for 38 reactions using the kinetic parameters obtained. The activation energies and rate constants of the reverse bimolecular reaction of acid addition to olefins have been calculated by the intersecting parabolas method. Factors in the activation energy of ester decomposition and formation reactions are discussed.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. Semenov, N.N., Izbrannye trudy (Selected Works), vol. 3: O nekotorykh problemakh khimicheskoi kinetiki i reaktsionnoi sposobnosti (Some Problems of Chemical Kinetics and Reactivity), Moscow: Nauka, 2004.

    Google Scholar 

  2. Decomposition and Isomerisation of Organic Compounds, Comprehensive Chemical Kinetics, vol. 5, Amsterdam: Elsevier, 1972, p. 443.

  3. Pokidova, T.S. and Denisov, E.T., Neftekhimiya, 2006, vol. 46, no. 2, p. 100 [Pet. Chem. (Engl. Transl.), vol. 46, no. 2, p. 84].

    CAS  Google Scholar 

  4. Pokidova, T.S. and Denisov, E.T., Khim. Fiz., 2006, vol. 25, no. 6, p. 33.

    CAS  Google Scholar 

  5. Pokidova, T.S., Denisov, E.T., and Shestakov, A.F., Neftekhimiya, 2009, vol. 49, no. 5, p. 363 [Pet. Chem. (Engl. Transl.), vol. 49, no. 5, p. 343].

    CAS  Google Scholar 

  6. Pokidova, T.S. and Denisov, E.T., Butlerov Commun., 2008, vol. 14, no. 4, p. 29.

    Google Scholar 

  7. Denisov, E.T., Denisova, T.G., and Pokidova, T.S., Handbook of Free Radical Initiators, Hoboken, N.J.: Wiley, 2003.

    Book  Google Scholar 

  8. Denisov, E.T., Usp. Khim., 1997, vol. 66, no. 10, p. 953 [Russ. Chem. Rev. (Engl. Transl.), vol. 66, no. 10, p. 859].

    CAS  Google Scholar 

  9. Denisov, E.T., in General Aspects of the Chemistry of Radicals, Alfassi, Z.B., Ed., Chichester: Wiley, 1999.

    Google Scholar 

  10. Pokidova, T.S. and Denisov, E.T., Kinet. Katal., 2001, vol. 42, no. 6, p. 805 [Kinet. Catal. (Engl. Transl.), vol. 42, no. 6, p. 729].

    Article  Google Scholar 

  11. Aleksandrov, I.V., Teor. Eksp. Khim., 1976, vol. 12, p. 299.

    CAS  Google Scholar 

  12. NIST Standard Reference Database 19A: Positive Ion Energetics, Version 2.02, Gaithersburg, Md.,1994.

  13. Domalski, E.S., J. Phys. Chem. Ref. Data, 1993, vol. 2, p. 805.

    Article  Google Scholar 

  14. Blades, A.T., Can. J. Chem., 1954, vol. 32, p. 366.

    Article  CAS  Google Scholar 

  15. Gill, M.T. and Taylor, R., J. Chem. Soc., Perkin Trans. 2, 1990, p. 1715.

  16. Louw, R., Tinkelenberg, A., and Wernet, E.S.E., Rec. Trav. Chim. Pays-Bas, 1983, vol. 102, p. 519.

    CAS  Google Scholar 

  17. De Burgh, Norfolk S. and Taylor, R., J. Chem. Soc., Perkin Trans. 2, 1976, p. 280.

  18. Scheer, J.C., Kooyman, E.C., and Sixma, F.L.J., Rec. Trav. Chim. Pays-Bas, 1963, vol. 82, p. 1123.

    CAS  Google Scholar 

  19. Tinkelenberg, A., Kooyman, E.C., and Louw, R., Rec. Trav. Chim. Pays-Bas, 1972, vol. 91, p. 3.

    CAS  Google Scholar 

  20. Taylor, R., J. Chem. Soc., Perkin Trans. 2, 1979, p. 1730.

  21. Chuchani, G., Martin, I., and Avila, I., Int. J. Chem. Kinet., 1979, vol. 11, p. 561.

    Article  CAS  Google Scholar 

  22. Taylor, R., Smith, G.G., and Wetzel, W.H., J. Am. Chem. Soc., 1962, vol. 84, p. 4817.

    Article  CAS  Google Scholar 

  23. Barnard, J.A., Cocks, A.T., and Parrott, T.K., J. Chem. Soc., Faraday Trans. 1, 1976, vol. 72, p. 1456.

    Article  CAS  Google Scholar 

  24. Kairaitis, D.A. and Stimson, V.R., Aust. J. Chem., 1968, vol. 21, p. 1349.

    CAS  Google Scholar 

  25. Taylor, R., J. Chem. Soc., Perkin Trans. 2, 1975, p. 1025.

  26. Chuchani, G., Martin, I., Hernadez, J.A., Rotinov, A., and Flaile, G., J. Phys. Chem., 1980, vol. 84, p. 944.

    Article  CAS  Google Scholar 

  27. Taylor, R., J. Chem. Soc., Perkin Trans. 2, 1978, p. 1255.

  28. Kraus, M., Vavruska, N., and Bazant, V., Collect. Czech. Chem. Commun., 1957, vol. 22, p. 484.

    CAS  Google Scholar 

  29. Warrick, E. and Fugassi, P., J. Phys. Chem., 1948, vol. 52, p. 357.

    Article  Google Scholar 

  30. Smith, G.G., Bagley, F.D., and Taylor, R., J. Am. Chem. Soc., 1961, vol. 83, p. 3647.

    Article  CAS  Google Scholar 

  31. Chuchani, G., Martin, I., Yepez, M., and Diaz, M., React. Kinet. Catal. Lett., 1977, vol. 6, p. 449.

    Article  CAS  Google Scholar 

  32. Rudi, C.E., Fugassi, Jr., and Fugassi, P., J. Phys. Chem., 1948, vol. 52, p. 357.

    Article  Google Scholar 

  33. Emovan, E.U. and Maccoll, A., J. Chem. Soc., 1962, p. 335.

  34. Gordon, E., Price, S.G.W., and Trotman-Dickenson, A.F., J. Chem. Soc., 1957, p. 2813.

  35. Cordova, C.M., Martin, I., and Chuchani, G., React. Kinet. Catal. Lett., 1984, vol. 24, p. 243.

    Article  Google Scholar 

  36. Al-Avadi, N.A., El-Dusougui, O.M.E., and Mathew, T., Int. J. Chem. Kinet., 1997, vol. 29, p. 289.

    Article  Google Scholar 

  37. Al-Avadi, N.A., Al-Bashir, R.F., and El-Dusougu, O.M.E., Tetrahedron, 1996, vol. 46, p. 2119.

    Google Scholar 

  38. Denisov, E.T., Kinetika gomogennykh khimicheskikh reaktsii (Kinetics of Homogeneous Chemical Reactions), Moscow: Vysshaya Shkola, 1988, p. 72.

    Google Scholar 

  39. Pokidova, T.S., Denisov, E.T., and Shestakov, A.F., Kinet. Katal., 2009, vol. 50, no. 5, p. 674 [Kinet. Catal. (Engl. Transl.), vol. 50, no. 5, p. 647].

    Google Scholar 

  40. Pokidova, T.S., Denisov, E.T., and Shestakov, A.F., Neftekhimiya, 2008, vol. 48, no. 3, p. 175 [Pet. Chem. (Engl. Transl.), vol. 48, no. 3, p. 174].

    Google Scholar 

  41. Drozdova, T.I., Denisov, E.T., Shestakov, A.F., and Emel’yanova, N.S., Kinet. Katal., 2006, vol. 47, no. 1, p. 111 [Kinet. Catal. (Engl. Transl.), vol. 47, no. 1, p. 106].

    Article  CAS  Google Scholar 

  42. Denisov, E.T., Kinet. Katal., 2008, vol. 49, no. 3, p. 333 [Kinet. Catal. (Engl. Transl.), vol. 49, no. 3, p. 313].

    Google Scholar 

  43. Denisov, E.T. and Denisova, T.G., Usp. Khim., 2004, vol. 73, no. 11, p. 1181 [Russ. Chem. Rev. (Engl. Transl.), vol. 73, no. 11, p. 1091].

    Google Scholar 

  44. Denisov, E.T. and Tumanov, V.E., Usp. Khim., 2005, vol. 74, no. 9, p. 905 [Russ. Chem. Rev. (Engl. Transl.), vol. 74, no. 9, p. 825].

    Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Institute of Problems of Chemical Physics, Russian Academy of Sciences, Chernogolovka, Moscow oblast, 142432, Russia

    T. S. Pokidova & E. T. Denisov

Authors
  1. T. S. Pokidova
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. E. T. Denisov
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to E. T. Denisov.

Additional information

Original Russian Text © T.S. Pokidova, E.T. Denisov, 2009, published in Kinetika i Kataliz, 2009, Vol. 50, No. 5, pp. 663–673.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Pokidova, T.S., Denisov, E.T. Ester decomposition as a two-center synchronous reaction. Kinet Catal 50, 636–646 (2009). https://doi.org/10.1134/S0023158409050048

Download citation

  • Received:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1134/S0023158409050048

Keywords

Search

Navigation