Abstract
A novel method is described for determining the kinetic isotope effect on the reaction in which a free radical abstracts a hydrogen atom from a H-donor such as a thiol, RSH. The radical is generated by gamma irradiation of an appropriate precursor, and the isotope effect is obtained by comparing the results of two experiments: in the first, the radical is allowed to react with tritiated RSH; in the second, the radical reacts with tritium-labeled RSD. The validity of this system was tested by generating the cyclohexyl radical in two different ways: radiolysis of cyclohexane and decomposition of the perester ${\rm C}_{6}{\rm H}_{5}-{\rm CO}_{2}-{\rm OC}_{4}{\rm H}_{9}-t$ . The $k_{{\rm H}}/k_{{\rm D}}$ ratios from these independent methods are in excellent agreement. The utility of the method was demonstrated by radiolyzing the ethyl ester of N,N-dimethylglycine. The isotope effect for abstraction of a hydrogen from thiols by the $({\rm CH}_{3})_{2}{\rm N}-...
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