Addition of hydroperoxyl radicals to double bonds

Combustion and oxidation reactions produce oxygen atoms and hydroxyl and hydroperoxyl radicals as oxidizing agents. The first two have already been discussed. The hydroperoxyl radical, which was noted as an annoying interference in the attempts to determine the kinetics of hydroxyl radical chemistry, has been studied in far less detail, and the kinetics determined are not considered to be very accurate. What little experimental evidence that has accumulated is recorded in Table 42. The third entry in the table is an estimated collection of parameters derived to be consistent with those for related reactions, and probably these are much closer to the true values than are the experimental ones. 

The problem in this system is that there are oxygen atoms, as well as the HO2 radicals present in the mixtures used, and the former react with the organic substrates perhaps one hundred times faster than the latter. In 

Avramenko et al. [152a] produced HO2 radicals by the addition of hydrogen atoms to O2 

HO2 + CH2-CH2 CH2CH2OOH CH2CH2OOH CH20HCH20-CH20H-CH20- - CHjOH + CHjO CH2OH + 02 CH2O + HO2  

In a reaction system as complex as this, the estimated kinetic parameters of the initial interaction of the HO2 with ethylene, determined from the rate of formation of formaldehyde, is bound to be the subject of considerable uncertainty  

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