Effects of mercaptans and disulfides on photochemical and high energy radiation induced reactions. Progress report, November 1, 1974--October 31, 1975
A chain reaction may be formulated at alkaline pH in terms of e$sup -$/ sub aq/ acting as a source of $sup -$OH as a reactant and H. regenerating e$sup - $/sub aq/. This may account for radiolytic conversion of CO to formate with high G. $sup 60$Co $gamma$-radiolysis of alkaline aqueous acetonitrile and acetamide gave no evidence of a chain; extensive hydrolysis of methyl acetate is now attributed to non-radiolytic, normal hydrolysis. Aromatic mercaptans are found to retard photoreduction of a benzophenone by aliphatic amines, largely by hydrogen atom-transfer repair reactions. Aliphatic mercaptans accelerate photoreduction, apparently by affecting the reduction to quenching ratio in the intermediate charge-transfer complex. In photoreduction of a benzophenone by 2,3- butylene glycol at pH 3, the glycol is converted, not to 3-hydroxy-2-butanone, but to 2-butanone, and about 4 molecules of this are formed per molecule of ketone reduced. A short chain appears to be established. Mercaptan appears to accelerate the reduction of the ketone and retard the formation of 2-butanone. (auth)
- Research Organization:
- Brandeis Univ., Waltham, Mass. (USA)
- NSA Number:
- NSA-33-019708
- OSTI ID:
- 4096894
- Report Number(s):
- COO--3118-10
- Country of Publication:
- United States
- Language:
- English
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