General kinetics of the radical isomerization of 3,3,3-trichloro-2-bromopropene
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The general kinetics of the radical isomerization of 3,3,3-trichloro-2-bromopropene was studied in the interval 293–323°K. In the case of irradiation of 3,3,3-trichloro-2-bromopropene with the complete spectrum of a PRK-4 lamp, the reaction is second order with respect to the starting material, and the summary rate constants satisfy the equation k=79 exp(−9500/RT). In the case of irradiation of the starting material with UV light with wavelength <300μ, the order is first.
The quantum yield, calculated using the liquid phase actinometer K3Fe(C2O4)3, is ∼103, which indicates a radical chain character of the reaction.
The mechanisms of initiation and termination of the kinetic chain were studied, and a scheme of the reaction was proposed on the basis of this.
KeywordsLiquid Phase Quantum Yield Radical Chain Complete Spectrum Kinetic Chain
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