AbstractThe literature results for the pyrolysis of bis trifluoromethyl peroxide are reexamined and compared with those for dimethyl peroxide. The thermochemistry yields the result that the π‐bond energy in carbonyl fluoride is 96 ± 10 kcal/mol compared to 74 kcal/mol for that in formaldehyde. Thermodynamic additivity contributions are derived for the C(F)3(O) and O(C)(F) groups. Some conclusions are drawn in relation to the oxidation of halogeno methyl radicals and the chemistry of the atm