Reaction of Dihydroxymethyl Radical with Molecular Oxygen in Aqueous Solution

Dihydroxymethyl radical (1) was found to react with oxygen diffusion controlled (k = 4.5 x 109 M _ 1 s 1 ) . The final products of the reaction are formic acid and 1/2 hydrogen peroxide. The precursor of H2O2 was shown to be O2' which is formed with G(02" -) = 6.3 (a value which includes the 02"~ formed by H atoms and oxygen (G(H) = 0.55)). If it is assumed that dihydroxymethylperoxyl radicals are formed as intermediates the rate constant of 0 2 ' ~ formation must be > 10 6s 1 . A bimolecular reaction of two dihydroxymethylperoxyl radicals forming tetroxides does not occur at the dose rates used. The rate constants for the establishment of the equilibrium