A possible role of triplet-state species as chain-initiators in high-temperature oxidations of aromatic hydrocarbons
✍ Scribed by M.C. Lin; D.E. Tevault
- Publisher
- Elsevier Science
- Year
- 1981
- Tongue
- English
- Weight
- 463 KB
- Volume
- 42
- Category
- Article
- ISSN
- 0010-2180
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✦ Synopsis
Photooxidation of benzene at 254 nm has been studied in 10-K Ar matrices. Both CO and CO 2, which are believed to be secondary photodissociation products of initial pemxy-adducts or their dialdehyde isomers from the reaction of the triplet benzene with 02, 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 02 concentration. On the basis of this result and estimates of transition state calculations, it can be concluded that at 2500K, the C6H6(TI) + 0 2 reaction is at least as important as the hydrogen abstraction reaction, C6H 6 + 02 ~ C6H 5 + HO2, for chain-initiation. The Trstate reaction is expected to be more important as its energy decreases for the larger members of the homologous series. O2(IAg), the value is expected to be much higher. This reaction, too, deserves a careful study at high temperatures.