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The kinetics and mechanism of reactions of aliphatic stable nitroxyl radicals with alkyl and peroxide radicals during styrene oxidation

Abstract

A kinetic study (EPR, microvolumometry), quantum-chemical analysis (DFT B3LYP/6-31G*), and kinetic simulation of the antioxidant activity of aliphatic stable nitroxyl radicals during styrene oxidation was performed. The key reactions constituting the detailed mechanism of the process were analyzed. It was shown that the inhibiting action of nitroxyl radicals was caused by their reaction not only with alkyl radicals but also with substrate peroxy radicals, which resulted in the regeneration of nitroxyl radicals in chain-termination steps.

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Correspondence to E. M. Pliss.

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Original Russian Text © E.M. Pliss, I.V. Tikhonov, A.I. Rusakov, 2012, published in Khimicheskaya Fizika, 2012, Vol. 31, No. 5, pp. 41–49.

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Pliss, E.M., Tikhonov, I.V. & Rusakov, A.I. The kinetics and mechanism of reactions of aliphatic stable nitroxyl radicals with alkyl and peroxide radicals during styrene oxidation. Russ. J. Phys. Chem. B 6, 376–383 (2012). https://doi.org/10.1134/S1990793112020108

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Keywords

  • styrene
  • stable nitroxyl radicals
  • inhibited oxidation
  • multiple chain termination