Reactions of nitrosodimethylaniline with free radicals

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Abstract
The changes in absorption spectra of aqueous Ar-, N2O- or O2-saturated, solutions of p-nitro-sodimethylaniline(P) subjected to γ-rays under steady-state conditions or to 2.9 MeV electron pulses, and the effects on these of various OH radical scavengers S, (and some e– aq scavengers) have been measured. The optical density of the solutions at 440 nm, where P absorbs strongly, initially diminishes rapidly due to reactions of P with e– aq(k= 3.4 × 1010 M–1 sec–1), confirmed by measurement of the effect of P on G(2) for γ-radiolysis, and OH(k= 1.8 ×1010 M–1 sec–1), and then undergoes partial or complete, rapid or slow, recovery, dependent on the nature of both S and the dissolved gas. Rate constants of reactions of P with the oxidized form of S have been measured. O– 2 does not react with P but the complexities of the secondary reactions prevent the calculation of reliable values of k for OH + S from the effect of S on G(–P) for steady-state conditions. However, the effect of S on the maximum O.D. change at 440 nm following pulse radiolysis of O2-saturated solutions can be used to obtain trustworthy values of k(OH + S) in specified cases.

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