Thermal decomposition of dialkyl peroxides and heats of formation of the ethoxyl and isopropoxyl radicals

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Abstract
The gas-phase thermal decompositions of diethyl peroxide and di-isopropyl peroxide have been studied in the temperature range 134–185°C using a continuous mass-spectrometric sampling technique. Values of 1016.1±0.7(sec–1) and 37.3±1.2 (kcal mole–1) and 1015.4±0.4(sec–1) and 37.1±0.8 (kcal mole–1) respectively have been obtained for the Arrhenius parameters of the decomposition reactions: C2H5OOC2H5→2C2H5O (CH3)2CHOOCH(CH3)2→2(CH3)2CHO Using these parameters, revised values of –4.4±1.1 and –12.3±2 kcal mole –1 have been derived for the heats of formation of the ethoxyl and of the isopropoxyl radicals. Values of ca. 1012.5 mole–1 cm3 sec–1 have been estimated for the rate of dimerization of ethoxyl and isopropoxyl radicals.