Articles written in Journal of Chemical Sciences

    • Pulse radiolysis of some aromatic sulphoxides in aqueous solutions

      K Kishore G R Dey P N Moorthy

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      Reactions ofeaq and H-atoms with aromatic sulphoxides such as dibenzyl, diphenyl and di-4-chlorophenyl sulphoxides have been studied at various pH values and the spectral and kinetic properties of the transients determined.eaq addition to dibenzyl sulphoxide was found to lead to the scission of the C−S bond giving benzyl radicals, but such bond breakage was not observed in other cases.

    • Effect of phenyl moiety on the formation of radicals and radical cations of thioamides in n-butyl chloride: a pulse radiolysis study

      G R DEY

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      The formation of radical cations and radicals of thioamides (R)(NH2)CS, where R represents CH3 in thioacetamide (TA) and C6H5 in thiobenzamide (TBA) in n-butyl chloride has been studied using pulse radiolysis technique. The radical cations of TA and TBA are observed in n-butyl chloride, and on their subsequentdeprotonation, respective radicals are generated. In this study on thioamide solutions in n-butyl chloride, the transient species formed at 1.2 μs after the electron pulse exhibiting absorption maxima in 400 nm region are attributed to their radical cations. In the presence of 0.1 M ethanol (C2H5OH), a radical cation scavenger, the absorbance values at corresponding peaks are reduced substantially, revealing the formation of their respective radical cations. Moreover, at a later time, the generation of radical species takes place through deprotonation of radical cations and also through direct reactions during electron pulse irradiation. The mechanisms for the formation of radical cations and radicals of these two thioamides under pulse radiolysis have been revisited inbutyl chloride medium wherein the charge transfer reactions are more prominent. Results of quantum chemical calculation support the mechanistic explanation and provide information on the reactivity of parent molecules, and the charge distribution on radical cations and radicals species of thioamides.

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