A possible role of triplet-state species as chain-initiators in high-temperature oxidations of aromatic hydrocarbons

Photooxidation of benzene at 254 nm has been studied in 10-KAr matrices. Both CO and CO 2, which are believed to be secondary photodissociation products of initial peroxy-adducts or their dialdehyde isomers from the reaction of the triplet benzene with O 2, were found to be the major observable oxid...

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Bibliographic Details
Published in:Combustion and flame 1981-01, Vol.42, p.139-146
Main Authors: Lin, M.C., Tevault, D.E.
Format: Article
Language:English
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Summary:Photooxidation of benzene at 254 nm has been studied in 10-KAr matrices. Both CO and CO 2, which are believed to be secondary photodissociation products of initial peroxy-adducts or their dialdehyde isomers from the reaction of the triplet benzene with O 2, were found to be the major observable oxidation products by IR analysis. Formation of these products has been studied as a function of photolysis time and of O 2 concentration. On the basis of this result and estimates of transition state calculations, it can be concluded that at 2500K, the C 6H 6(T 1) + O 2 reaction is at least as important as the hydrogen abstraction reaction, C 6H 6 + O 2 å C 6H 5 + HO 2, for chain-initiation. The T 1-state reaction is expected to be more important as its energy decreases for the larger members of the homologous series.
ISSN:0010-2180
1556-2921
DOI:10.1016/0010-2180(81)90152-8