Pulse radiolysis studies of the reactions of bromine atoms and dimethyl sulfoxide-bromine atom complexes with alcohols

Sumiyoshi, Takashi, Fujiyoshi, Ryoko, Katagiri, Miho, Sawamura, Sadashi

doi:10.1016/j.radphyschem.2006.04.011

Dimethylsulfoxide (DMSO)–Br complexes were generated by pulse radiolysis of DMSO/bromomethane mixtures and the formation mechanism and spectral characteristics of the formed complexes were investigated in detail. The rate constant for the reaction of bromine atoms with DMSO and the extinction coefficient of the complex were obtained to be 4.6×109 M−1 s−1 and 6300 M−1 cm−1 at the absorption maximum of 430 nm. Rate constants for the reaction of bromine atoms with a series of alcohols were determined in CBrCl3 solutions applying a competitive kinetic method using the DMSO–Br complex as the reference system. The obtained rate constants were 108 M−1 s−1, one or two orders larger than those reported for highly polar solvents. Rate constants of DMSO–Br complexes with alcohols were determined to be 107 M−1 s−1. A comparison of the reactivities of Br atoms and DMSO–Br complexes with those of chlorine atoms and chlorine atom complexes which are ascribed to hydrogen abstracting reactants strongly indicates that hydrogen abstraction from alcohols is not the rate determining step in the case of Br atoms and DMSO–Br complexes.

Pulse radiolysis studies of the reactions of bromine atoms and dimethyl sulfoxide-bromine atom complexes with alcohols

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Pulse radiolysis studies of the reactions of bromine atoms and dimethyl sulfoxide-bromine atom complexes with alcohols

この論文をさがす

説明

収録刊行物

キーワード

詳細情報 詳細情報について

書き出し

問題の指摘

詳細情報詳細情報について