The oxidation of some transition-metal cyanide compounds by hydroxyl radical in aqueous media has been investigated by pulse radiolysis. For compounds of the type, M(CN)64-where M is Fe, Ru, and Os, and for Mo(CN)s4-, the mechanism of their reaction with hydroxyl radical involves single electron transfer with the formationofthe intensely colored metalcomplexes of the same stoichiometry as the startingmaterials. The u.v.-visible absorption spectra for these products for the iron, ruthenium, and osmium systems are reported along with the associated second order rate constants for their formation. The reaction of Mo(CN)s4-with hydroxyl radical has been studied by a competition technique using sodium bicarbonate. The values of the second order rate constants are near those expected of diffusion-controlled reactions and they range between cn. 5 x lo9 to I x 101° M-I s-l. Can.

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