EFFECTS OF MERCAPTANS AND DISULFIDES ON FREE RADICAL, LIGHT AND HIGH ENERGY RADIATION INDUCED REACTIONS. Progress Report for Period November 1, 1960-November 1, 1961
The photochemical conversion of benzophenone in 2propanol to benzopinacol and acetone is retarded and inbibited by certain mercaptans and disulfides present in low concentration. The retarded reactions start at time zero and proceed at constant rate with zero order kinetics. Inhibition does not lead to consumption of the inhibitor, initially present mercaptan or disulfide being converted to an equilibrium mixture of the two. An inhibited reaction carried out in (+) 2-octanol leads to racemization; irradiation of (+) 2-octanol with benzophenone or disulfide separately does not lead to racemization. Inhibition results from repeated reaction of the sulfur compounds in their two valence states with the normal free radical intermediates, the sulfur compounds being converted to their alternate, still reactive, valence states, the radicals being converted to the starting materials. The Co/sup 60/ gamma -ray induced conversion of benzophenone to benzopinacol in 2propanol is also inhibited by mercaptans and disulfides, presumably for a similar mechanism. (auth)
- Research Organization:
- Brandeis Univ., Waltham, Mass.
- NSA Number:
- NSA-16-005370
- OSTI ID:
- 4805550
- Report Number(s):
- TID-14441
- Country of Publication:
- United States
- Language:
- English
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