ISSN:
1573-9171
Keywords:
hydrocarbon oxidation
;
peroxyl radicals
;
chemiluminescence
;
electronic excitation
Source:
Springer Online Journal Archives 1860-2000
Topics:
Chemistry and Pharmacology
Notes:
Abstract The absolute yields (ϕ*) of excitation of the triplet benzophenone, a product of disproportionation of peroxyls in the chemiluminescent oxidation reaction of diphenylmethane, were measured. The ϕ* value is independent of the temperature and viscosity of the medium, but decreases with increase in its polarity: it is 0.003 in CCl4 and 0.0015 in MeCN. Semiempirical MNDO calculations of the structure of intermediates and the energy profile of their decomposition were carried out. A conclusion was made that the excitation of the3nπ* state of the ketone occurs during the decomposition of the intermediate tetroxide Ph2CHOOOOCHPh2 after the transition state, but before isolation of the Ph2COOO biradical, which thereafter decomposes to benzophenone and O2.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1007/BF01435378
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