Effect of solute structure on the nature of center dot OH radical reactionwith organic sulfur compounds: A pulse radiolysis study

The nature of (OH)-O-. radical reaction with organic sulfides is observed t o depend strongly on the nature of the functional group, chain length betwe en sulfur and the functional group and pH of the solution. The sulfur-cente red 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 re quired to form the sulfur-centered dimer radical cations depends on the ele ctron-withdrawing power of the functional group. The presence of the aryl g roup changes the site of attack of (OH)-O-. radical from sulfur to the benz ene ring, and benzene-centered monomer radical cations are observed.