Nature of sulfur centered radicals formed during pulse radiolysis of 2-mercaptopyridine in aqueous solutions

Nature of sulfur centered radicals formed during pulse radiolysis of 2-mercaptopyridine in... Spectral, redox and kinetic properties of the transient species formed by the reaction of 2- mercaptopyridine (2-MPy) with oxidants such as OH, Br¯2 . ; N . 3 and Cl¯2 . radicals and reductants such as e¯aq, H-atoms and (CH3)2 . COH radicals have been studied by pulse radiolysis technique. Reaction of one-electron oxidants with 2-MPy at pH 11.5 led to the formation of 2-pyridyl thiyl radical. The reduction potential for the couple C5H4NS . /C5H4NS¯ was estimated to be 0.84 V vs NHE from the equilibrium studies with I¯2 . /2I¯ couple. At pH 6.8, the reaction of N . 3 radical with 2-MPy gave a cation radical derived from 2-MPy. At pH 6.8 and 11.5, OH radicals react with 2-MPy by addition pathway. Reaction of e¯aq with 2-MPy was found to give a reducing radical capable of transferring electron to methyl viologen. At acidic pH, the reaction of (CH3)2 . COH radicals and H-atoms with 2-MPy gave transient species identical to those produced by the reaction of oxidising radicals, namely, OH radicals, Cl¯2 . and Br¯2 . radicals. http://www.deepdyve.com/assets/images/DeepDyve-Logo-lg.png Research on Chemical Intermediates Springer Journals

Nature of sulfur centered radicals formed during pulse radiolysis of 2-mercaptopyridine in aqueous solutions

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Publisher
Brill Academic Publishers
Copyright
Copyright © 2002 by VSP 2002
Subject
Chemistry; Inorganic Chemistry; Physical Chemistry; Catalysis
ISSN
0922-6168
eISSN
1568-5675
D.O.I.
10.1163/15685670260373362
Publisher site
See Article on Publisher Site

Abstract

Spectral, redox and kinetic properties of the transient species formed by the reaction of 2- mercaptopyridine (2-MPy) with oxidants such as OH, Br¯2 . ; N . 3 and Cl¯2 . radicals and reductants such as e¯aq, H-atoms and (CH3)2 . COH radicals have been studied by pulse radiolysis technique. Reaction of one-electron oxidants with 2-MPy at pH 11.5 led to the formation of 2-pyridyl thiyl radical. The reduction potential for the couple C5H4NS . /C5H4NS¯ was estimated to be 0.84 V vs NHE from the equilibrium studies with I¯2 . /2I¯ couple. At pH 6.8, the reaction of N . 3 radical with 2-MPy gave a cation radical derived from 2-MPy. At pH 6.8 and 11.5, OH radicals react with 2-MPy by addition pathway. Reaction of e¯aq with 2-MPy was found to give a reducing radical capable of transferring electron to methyl viologen. At acidic pH, the reaction of (CH3)2 . COH radicals and H-atoms with 2-MPy gave transient species identical to those produced by the reaction of oxidising radicals, namely, OH radicals, Cl¯2 . and Br¯2 . radicals.

Journal

Research on Chemical IntermediatesSpringer Journals

Published: Oct 13, 2004

References

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