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Rate constants for radical addition to olefins

  • Physical Chemistry
  • Published:
Bulletin of the Academy of Sciences of the USSR, Division of chemical science Aims and scope

Conclusions

  1. 1.

    It has been shown theoretically that the rate constant for a\(\mathop R\limits^ \cdot + {}_ / ^ \setminus C = C\) type reaction is an oscillating function of the heat of reaction. The oscillation frequency is largely determined by the C-C bond vibration frequency. This conclusion has been confirmed by comparison with the results of studies on polymerization reactions. Our results make it possible to use heats of reaction to predict rate constant with considerable accuracy.

  2. 2.

    Alteration of the steric factor increases the reaction rate, the increase being independent of the heat of reaction and the form of the curve showing the logarithm of the rate plotted as a function of the heat of reaction remaining unchanged. The activation energy is a nonlinear function of the heat of reaction.

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Literature cited

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Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 11–16, January, 1977.

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Ponomarev, O.A., Martem'yanova, T.M. & Ivanov, A.I. Rate constants for radical addition to olefins. Russ Chem Bull 26, 4–8 (1977). https://doi.org/10.1007/BF00921480

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  • DOI: https://doi.org/10.1007/BF00921480

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