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

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Title: Pulse radiolysis studies of the reactions of bromine atoms and dimethyl sulfoxide-bromine atom complexes with alcohols
Authors: Sumiyoshi, Takashi Browse this author →KAKEN DB
Fujiyoshi, Ryoko Browse this author
Katagiri, Miho Browse this author
Sawamura, Sadashi Browse this author
Keywords: Pulse radiolysis
Rate constant
Br
DMSO–Br complex
Alcohol
Issue Date: May-2007
Publisher: Elsevier
Journal Title: Radiation Physics and Chemistry
Volume: 76
Issue: 5
Start Page: 779
End Page: 786
Publisher DOI: 10.1016/j.radphyschem.2006.04.011
Abstract: 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.
Relation: http://www.sciencedirect.com/science/journal/0969806X
Type: article (author version)
URI: http://hdl.handle.net/2115/22085
Appears in Collections:工学院・工学研究院 (Graduate School of Engineering / Faculty of Engineering) > 雑誌発表論文等 (Peer-reviewed Journal Articles, etc)

Submitter: 住吉 孝

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