The products of radiolysis of penicillamine in 1 M HCIO4 are reported and their yields discussed. The reactions of • and -CH2OH are qualitatively similar to those observed for cysteine and produce primarily RS• radicals. However, the secondary reactions of RS• radicals give rise to a substantially higher yield of trisulfide (RSSSR) than is observed with cysteine. This appears to be due to the presence of weaker C-S bonds in the tertiary C-SH compound and to the fact that this bond can be broken as a result of interactions between RS• and RSH, possibly via the formation of a RSS(H)R intermediate. The magnitude of the rate constant ratio fe3(fc4 + ke)-1 at 1 ± 1 °C is 0.54 ± 0.10. At 23 6C it was found to be 0.50 ± 0.10 in good agreement with an earlier value of O.44.11
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