Rate constants for radical addition to olefins

  • O. A. Ponomarev
  • T. M. Martem'yanova
  • A. I. Ivanov
Physical Chemistry


  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.



Polymerization Activation Energy Oscillation Frequency Nonlinear Function Vibration Frequency 
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Copyright information

© Plenum Publishing CorporationPlenum Publishing Corporation 1977

Authors and Affiliations

  • O. A. Ponomarev
    • 1
  • T. M. Martem'yanova
    • 1
  • A. I. Ivanov
    • 1
  1. 1.Institute of ChemistryBashkir Branch of the Academy of Sciences of the USSRUfa

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