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Kinetics and thermodynamics of formation and degradation of α-hydroxyperoxyl radicals
Abstract The enthalpies of formation for fifteen α-hydroxyhydroperoxides and α-hydroxyperoxyl radicals with various structures were calculated. Using the crossing parabolas method, experimental data on the degradation of α-hydroxyperoxyl radicals were analyzed and the kinetic parameters that characterize these reactions were calculated. The activation energies of the degradation rate constants of fifteen α-hydroxyperoxyl radicals were calculated from these parameters. The enthalpies of degradation for six α-hydroxyperoxyl radicals of polyhydric alcohols and the enthalpies of their formation were calculated using the experimental data. The rate constants of the backward reaction, namely, hydroperoxyl radical addition to a number (21) of carbonyl compounds, and the enthalpies and Gibbs energies for H2O2 addition to some aldehydes and ketones to form α-hydroxyhydroperoxides were calculated. The kinetic characteristics of the degradation of α-hydroxyperoxyl radicals are compared to those of other reactions of intramolecular hydrogen-atom transfer in oxygen-centered radicals. An important role of low triplet repulsion in these reactions, which ensures their fast rate, was noted.
Kinetics and thermodynamics of formation and degradation of α-hydroxyperoxyl radicals
Abstract The enthalpies of formation for fifteen α-hydroxyhydroperoxides and α-hydroxyperoxyl radicals with various structures were calculated. Using the crossing parabolas method, experimental data on the degradation of α-hydroxyperoxyl radicals were analyzed and the kinetic parameters that characterize these reactions were calculated. The activation energies of the degradation rate constants of fifteen α-hydroxyperoxyl radicals were calculated from these parameters. The enthalpies of degradation for six α-hydroxyperoxyl radicals of polyhydric alcohols and the enthalpies of their formation were calculated using the experimental data. The rate constants of the backward reaction, namely, hydroperoxyl radical addition to a number (21) of carbonyl compounds, and the enthalpies and Gibbs energies for H2O2 addition to some aldehydes and ketones to form α-hydroxyhydroperoxides were calculated. The kinetic characteristics of the degradation of α-hydroxyperoxyl radicals are compared to those of other reactions of intramolecular hydrogen-atom transfer in oxygen-centered radicals. An important role of low triplet repulsion in these reactions, which ensures their fast rate, was noted.
Kinetics and thermodynamics of formation and degradation of α-hydroxyperoxyl radicals
Denisov, E. T. (author) / Denisova, T. G. (author)
Petroleum Chemistry ; 46 ; 373-383
2006-12-01
11 pages
Article (Journal)
Electronic Resource
English
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