Abstract
Pulse radiolysis of (a) aqueous de-aerated solutions of acrylamide, methacrylamide, N-t-butyl acrylamide, acrylic acid and acrylonitrile and (b) styrene and α-methyl styrene in de-aerated cyclohexane, dioxane, tetrahydrofuran and benzene results in intense transient absorption spectra. Those for system (a) are assigned to monomer radical anions, m–1˙, and the products of reaction of a radical with the monomer. Their decay is second order and values of the extinction coefficients and bimolecular rate constants have been determined. Absolute rate constants( M–1 sec–1) were obtained for the reaction of acrylamide with (a) hydrated electrons, (2.1 ± 0.4)× 1010, (b) OH radicals, (2.0 ± 0.5)× 109 and for the reaction of the product of the reaction of the radical and monomer with oxygen and ferricyanide ion, (1.9 ± 0.3 )× 109 and (6.8 ± 0.4)× 106 respectively. For system (b) the absorptions and decay kinetics observed are not completely understood. At least two distinct species are formed, one of which can be ascribed to a radical but neither to a radical anion.
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