Abstract
The transient species produced in the reactions of solvated electrons and ..cap alpha..-hydroxyalkyl radicals with 4-nitroazobenzene have been studied by spectrophotometric pulse radiolysis in 2-propanol and methanol. Solvated electrons were found to react with rate constants of 1.6 x 10/sup 10/ and 2.3 x 10/sup 10/ M/sup -1/ s/sup -1/ in 2-propanol and methanol, respectively, giving the anion as primary product. The same species is produced by electron transfer from both alcohol radicals, with rate constants ca. 10/sup 9/ M/sup -1/ s/sup -1/ for (CH/sub 3/)/sub 2/COH and ca. 6 x 10/sup 7/ M/sup -1/ s/sup -1/ for CH/sub 2/OH. Protonation of the anion is observed in the microsecond time scale, leading to the hydrazyl radical. pK values for the protolytic dissociation of this species are evaluated to be 14.8 and 12.3 in 2-propanol and methanol, respectively. Association of the hydrazyl with the starting compound is observed in 2-propanol. Complete reduction of the azo bond occurs by very efficient second-order disproportionation of hydrazyl and/or dimer radicals. 18 references, 7 figures.
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