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Effect of solute structure on the nature of .OH radical reaction with organic sulfur compounds: A pulse radiolysis study

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The nature of .OH radical reaction with organic sulfides is observed to depend strongly on the nature of the functional group, chain length between sulfur and the functional group and pH of the solution. The sulfur-centered dimer radical cations are observed in the neutral solutions of dialkyl sulfides whereas high acid concentration is required to generate the dimer radical cations of 2,2′-thiodiethanoic acid. The concentration of acid required to form the sulfur-centered dimer radical cations depends on the electron-withdrawing power of the functional group. The presence of the aryl group changes the site of attack of .OH radical from sulfur to the benzene ring, and benzene-centered monomer radical cations are observed.

Affiliations: 1: Radiation Chemistry and Chemical Dynamics Division, Bhabha Atomic Research Centre, Trombay, Mumbai 400 085, India


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