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General kinetics of the radical isomerization of 3,3,3-trichloro-2-bromopropene

Conclusions

  1. 1.

    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.

  2. 2.

    The quantum yield, calculated using the liquid phase actinometer K3Fe(C2O4)3, is ∼103, which indicates a radical chain character of the reaction.

  3. 3.

    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.

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Literature cited

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    A. N. Nesmeyanov, R. Kh. Freidlina, and V. N. Kost, Dokl. Akad. Nauk SSSR,113, 828 (1957).

  2. 2.

    A. N. Nesmeyanov, R. Kh. Freidlina, and V. N. Kost, Izv. Akad. Nauk SSSR, Ser. Khim., 1199 (1958).

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    M. Ya. Khorlina and V. N. Kost, Dokl. Akad. Nauk SSSR,137, 1133 (1961).

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    R. Kh. Freidlina, V. N. Kost, T. T. Vasil'eva, and A. N. Nesmeyanov, ibid.,137, 1385 (1961).

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    R. G. Gasanov, T. T. Vasil'eva, and R. Kh. Freidlina, ibid.,193, 1058 (1970).

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    R. G. Gasanov and R. Kh. Freidlina, Izv. Akad. Nauk SSSR, Ser. Khim., 559 (1972).

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    J. Calvert and J. Pitts, Photochemistry [Russian translation], Mir (1968), pp. 625, 635.

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    S. Benson, Fundamentals of Chemical Kinetics [Russian translation], Mir (1964).

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    F. W. R. Steacie, Atomic and Free Radical Reactions, New York (1954).

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Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2458–2462, November, 1972.

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Gasanov, R.G., Vasil'eva, T.T. & Freidlina, R.K. General kinetics of the radical isomerization of 3,3,3-trichloro-2-bromopropene. Russ Chem Bull 21, 2392–2395 (1972). https://doi.org/10.1007/BF00850077

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Keywords

  • Liquid Phase
  • Quantum Yield
  • Radical Chain
  • Complete Spectrum
  • Kinetic Chain