Russian Chemical Bulletin

, Volume 44, Issue 12, pp 2282–2286 | Cite as

Negative activation energies and compensation effects for the reactions of diarylaminyl radicals with phenols

  • V. T. Varlamov
  • N. N. Denisov
  • V. A. Nadtochenko
Physical Chemistry


The temperature dependence of the rate constants of the reaction of 4,4′-disubstituted diphenylaminyl radicals (ArAr′N) with phenols has been studied by a laser pulse photolysis technique. The linear relationships between activation energiesE1 (negative in the majority of cases) and logarithms of pre-exponential factors logA1 have been established. These results coincide with the two-parametric correlations of logk1 with σ+ constants of substituents in phenol and aminyl radicals under isothermal conditions. The reaction rate constants decrease considerably when toluene is used instead ofn-decane.

Key words

aminyl radicals phenols negative temperature coefficient isoparametric correlations 


Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.


  1. 1.
    V. T. Varlamov, N. N. Denisov, V. A. Nadtochenko, E. P. Marchenko, I. V. Petrov, and L. G. Plekhanova,Kinet. Katal., 1994,35, 838 [Kinet. Catal., 1994,35 (Engl. Transl.)].Google Scholar
  2. 2.
    V. T. Varlamov, N. N. Denisov, V. A. Nadtochenko, and E. P. Marchenko,Kinet. Katal., 1994,35, 833 [Kinet. Catal., 1994,35 (Engl. Transl.)].Google Scholar
  3. 3.
    I. A. Leenson and G. B. Sergeev,Usp. Khim., 1984,53, 721 [Russ. Chem. Rev., 1984,53 (Engl. Transl.)].Google Scholar
  4. 4.
    D. F. Bowman, T. Gillan, and K. U. Ingold,J. Am. Chem. Soc., 1971,93, 6555.Google Scholar
  5. 5.
    K. Adamic, D. F. Bowman, T. Gillan, and K. U. Ingold,J. Am. Chem. Soc., 1971,93, 902.Google Scholar
  6. 6.
    L. M. Hadel, V. M. Maloney, M. S. Platz, W. G. McGimpsey, and J. C. Scaiano,J. Phys. Chem., 1986,90, 2488.Google Scholar
  7. 7.
    I. V. Khudyakov, P. P. Levin, and V. A. Kuz'min,Usp. Khim., 1980,49, 1990 [Russ. Chem. Rev., 1980,49 (Engl. Transl.)].Google Scholar
  8. 8.
    P. P. Levin and V. A. Kuz'min,Usp. Khim., 1987,56, 527 [Russ. Chem. Rev., 1987,56 (Engl. Transl.)].Google Scholar
  9. 9.
    R.-R. Lii, R. A. Gorse, Jr., M. C. Sauer, Jr., and S. Gordon,J. Phys. Chem., 1979,83, 1803.Google Scholar
  10. 10.
    W. Hack, O. Horie, and H. G. Wagner,J. Phys. Chem., 1982,86, 765.Google Scholar
  11. 11.
    G. B. Sergeev, V. A. Batyuk, and T. N. Boronina,Kinet. Katal., 1983,24, 283 [Kinet. Catal., 1983,24 (Engl. Transl.)].Google Scholar
  12. 12.
    V. I. Sklyarenko, A. S. Tatikolov, V. A. Kuz'min, and M. A. Al'perovich,Izv. Akad. Nauk SSSR, Ser. Khim., 1989, 1745 [Bull. Acad. Sci. USSR, Div. Chem. Sci., 1989,38, 1597 (Engl. Transl.)].Google Scholar
  13. 13.
    P. K. Das, M. V. Encinas, S. Steenken, and J. C. Scaiano,J. Am. Chem. Soc., 1981,103, 4162.Google Scholar
  14. 14.
    V. A. Nadtochenko and I. V. Rubtsov,Zh. Fiz. Khim., 1991,65, 1057 [Russ. J. Phys. Chem., 1991,65 (Engl. Transl.)].Google Scholar
  15. 15.
    V. T. Varlamov,Kinet. Katal, 1992,33, 27 [Kinet. Catal., 1992.33 (Engl. Transl.)].Google Scholar
  16. 16.
    A. J. Gordon and R. A. Ford,The Chemist's Companion, Wiley-Interscience Publ., New York-London-Sydney-Toronto, 1972.Google Scholar
  17. 17.
    J. S. Hogg, D. H. Lohman, and K. E. Russell,Can. J. Chem., 1961,39, 1588.Google Scholar
  18. 18.
    J. C. McGowan, T. Powell, and R. Raw,J. Chem. Soc., 1959, 3103.Google Scholar
  19. 19.
    A. J. Elliot, K. L. Egan, and J. K. S. Wan,J. Chem. Soc., Faraday Trans., 1, 1978, 2111.Google Scholar
  20. 20.
    L. R. Mahoney and M. A. DaRooge,J. Am. Chem. Soc., 1975,97, 4722.Google Scholar
  21. 21.
    L. R. Mahoney and M. A. DaRooge,J. Am. Chem. Soc., 1972,94, 7002.Google Scholar
  22. 22.
    O. A. Raevsky, V. Yu. Grigor'ev, D. B. Kireev, and N. S. Zefirov,Quant. Struct.-Act. Relat., 1992,11, 49.Google Scholar
  23. 23.
    S. Singh, K. R. Bhaskar, and C. N. R. Rao,Can. J. Chem., 1966,44, 2657.Google Scholar
  24. 24.
    A. S. N. Murthy and A. R. Redda,J. Chem. Soc., Faraday Trans. 1, 1982, 1867.Google Scholar

Copyright information

© Plenum Publishing Corporation 1996

Authors and Affiliations

  • V. T. Varlamov
    • 1
  • N. N. Denisov
    • 1
  • V. A. Nadtochenko
    • 1
  1. 1.Institute of Chemical Physics in ChernogolovkaRussian Academy of SciencesChernogolovka, Moscow RegionRussian Federation

Personalised recommendations