Journal
KINETICS AND CATALYSIS
Volume 47, Issue 5, Pages 662-671Publisher
PLEIADES PUBLISHING INC
DOI: 10.1134/S0023158406050028
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The enthalpies of the addition of 11 alkyl radicals to ortho- and para-benzoquinones and substituted para-benzoquinones and the enthalpies of formation of various alkoxyphenoxyl radicals have been calculated. Experimental data for the addition of alkyl radicals to quinones are analyzed in terms of the intersection of two parabolic potential curves, and parameters characterizing this class of reactions are calculated. The classical potential barrier of the thermally neutral reaction of alkyl radical addition to benzoquinone is E-e,E- 0 = 82.1 kJ/mol. This class of reactions is compared to other classes of free-radical addition reactions. The interaction between the electrons of the reaction center and the pi electrons of the aromatic ring is a significant factor in the activation energy. Activation energies, rate constants, and the geometric parameters of the transition state have been calculated for 40 reactions of alkyl radical addition to quinones. Strong polar interaction has been revealed in the addition of polar macroradicals to quinones, and its contribution to the activation energy has been estimated. Kinetic parameters, activation energies, and rate constants have been calculated for the reverse reactions of alkoxyphenoxyl radical decomposition to quinone and alkyl. The competition between chain termination and propagation reactions in alkoxyphenol-inhibited hydrocarbon oxidation is discussed.
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