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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- 1.A. N. Nesmeyanov, R. Kh. Freidlina, and V. N. Kost, Dokl. Akad. Nauk SSSR,113, 828 (1957).Google Scholar
- 2.A. N. Nesmeyanov, R. Kh. Freidlina, and V. N. Kost, Izv. Akad. Nauk SSSR, Ser. Khim., 1199 (1958).Google Scholar
- 3.M. Ya. Khorlina and V. N. Kost, Dokl. Akad. Nauk SSSR,137, 1133 (1961).Google Scholar
- 4.R. Kh. Freidlina, V. N. Kost, T. T. Vasil'eva, and A. N. Nesmeyanov, ibid.,137, 1385 (1961).Google Scholar
- 5.R. Kh. Freidlina, R. G. Gasanov, T. T. Vasil'eva, and V. A. Petukhov, ibid.,189, 350 (1969).Google Scholar
- 6.R. G. Gasanov, T. T. Vasil'eva, and R. Kh. Freidlina, ibid.,193, 1058 (1970).Google Scholar
- 7.R. G. Gasanov and R. Kh. Freidlina, Izv. Akad. Nauk SSSR, Ser. Khim., 559 (1972).Google Scholar
- 8.J. Calvert and J. Pitts, Photochemistry [Russian translation], Mir (1968), pp. 625, 635.Google Scholar
- 9.S. Benson, Fundamentals of Chemical Kinetics [Russian translation], Mir (1964).Google Scholar
- 10.F. W. R. Steacie, Atomic and Free Radical Reactions, New York (1954).Google Scholar