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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

Abstract

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 

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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

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