Abstract
The low-pressure gas-phase thermolysis of several dialkyl peroxides has been investigated in the 250–350°C range. The free radicals were trapped at 77 K and identified by ESR. No primary alkoxyl radicals have been detected. There is evidence for the decomposition of methoxyl and ethoxyl radicals with formation of H and CH 3 radicals, respectively, which readily combine with traces of O 2 to yield HO 2 and CH 3O 2. For higher homologues only RCH 2O 2 radicals have been detected and identified from the hyperfine structure.
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