ChemInform Abstract Two series of experiments are conducted. In the first one, only peroxyls are generated from tert. butyl hyponitrite according to (tBu-O-N)2 → tBu-O.; tBu-O. + (R1-CH2-R2/O2 or R1R2CH-OOH) → R1R2CH-O. 2. In the second one, both alkoxyls 1R2CH-O. and peroxyls R1R2CH-O. 2 are generated from the respective hyponitrite (R1R2CH-O-N)2. The decay of pairs of both the alkoxyl and peroxyl radicals then leads to excited ketones (acetophenone, cyclohexanone, 1-tetralone studied) which are trapped with a uorescent derivative of anthracene. By this procedure the ratios of excited ketones that arise from the self-reactions of peroxyls (2 R1R2CH-O. 2 → (R1-CO-R2)* + R1-CHOH-R2 + O2; less efficient) and alkoxyls (2 R1R2CH-O. → (R1-CO-R2)* + R1-CHOH-R2; more efficient) are measured.
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