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Oxidation of alcohols involving two types of peroxyl radicals
Abstract Liquid-phase oxidation of alcohols (R1R2CHOH) occurs as a chain reaction involving two peroxyl radicals, namely, R1R2C(OH)O 2 · and HO 2 · . Using the model of crossing parabolas, the activation energy and the rate constant were calculated for the reactions of α-hydroperoxyl radicals with four alcohols. A kinetic analysis of this reaction as a two-center chain process in which two peroxyl radicals that differ in reactivity (R1R2C(OH)O 2 · and HO 2 · ) participate in chain propagation was performed. The relative amounts of the peroxyl radicals and their contribution to chain propagation under different oxidation conditions (temperature, alcohol concentration) were calculated for the oxidation of four alcohols: ethanol, 2-propanol, cyclohexanol, and α-phenylethanol. A change in the ratio between radicals due to the accumulation of a carbonyl compound and the fast addition of hydroperoxyl radicals to the carbonyl group during alcohol oxidation was considered and its effect on the chain propagation step in the oxidation reaction was discussed.
Oxidation of alcohols involving two types of peroxyl radicals
Abstract Liquid-phase oxidation of alcohols (R1R2CHOH) occurs as a chain reaction involving two peroxyl radicals, namely, R1R2C(OH)O 2 · and HO 2 · . Using the model of crossing parabolas, the activation energy and the rate constant were calculated for the reactions of α-hydroperoxyl radicals with four alcohols. A kinetic analysis of this reaction as a two-center chain process in which two peroxyl radicals that differ in reactivity (R1R2C(OH)O 2 · and HO 2 · ) participate in chain propagation was performed. The relative amounts of the peroxyl radicals and their contribution to chain propagation under different oxidation conditions (temperature, alcohol concentration) were calculated for the oxidation of four alcohols: ethanol, 2-propanol, cyclohexanol, and α-phenylethanol. A change in the ratio between radicals due to the accumulation of a carbonyl compound and the fast addition of hydroperoxyl radicals to the carbonyl group during alcohol oxidation was considered and its effect on the chain propagation step in the oxidation reaction was discussed.
Oxidation of alcohols involving two types of peroxyl radicals
Denisov, E. T. (author) / Denisova, T. G. (author)
Petroleum Chemistry ; 46 ; 305-313
2006-10-01
9 pages
Article (Journal)
Electronic Resource
English
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