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

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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.


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