Reaction of methyl radicals with azoethane

Abstract

The methyl radical was generated by the thermal decomposition of di-tert-butyl peroxide in the temperature range 397–444 K. The relative Arrhenius parameters of the H-abstraction and addition reactions ˙CH₃+ C₂H₅NNC₂H₅→ CH₄+ CH₃CHNNC₂H₅(6), ˙CH₃+ C₂H₅NNC₂H₅→ C₂H₅NN(CH₃)C₂H₅(7), log[(k₆/k^1/2₅)/dm^3/2 mol^–1/2 s^–1/2]=(3.1 ± 0.3)–(30.7 ± 2.6) kJ mol^–1/θ, log[(k₇/k^1/2₅)/dm^3/2 mol^–1/2 s^–1/2]=(4.0 ± 0.5)–(40.5 ± 5.1) kJ mol^–1/θ where θ=RT ln 10 and k₅ is the rate constant of the reaction 2 ˙CH₃→ C₂H₆(5) were determined from the rate of accumulation of products in the early stages of the reaction.