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Photolysis of 1,1,1‐trifluoromethylazomethane as a source of methyl and trifluoromethyl radicals
Author(s) -
Craig N. L.,
Setser D. W.
Publication year - 1974
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.550060407
Subject(s) - chemistry , radical , photodissociation , yield (engineering) , quantum yield , hydrazine (antidepressant) , torr , intramolecular force , photochemistry , trifluoromethyl , medicinal chemistry , organic chemistry , materials science , physics , alkyl , chromatography , quantum mechanics , metallurgy , fluorescence , thermodynamics
The photochemistry of 1,1,1‐trifluoromethylazomethane has been partially characterized. The quantum yield for N 2 formation from photolysis at 366 nm and room temperature was unity at low pressure and decreased to 0.5 at 630 torr. At room temperature the principal products were C 2 H 6 , C 2 F 6 , CH 3 CF 3 (or CH 2 CF 2 + HF at reduced pressures), plus substituted hydrazines, which mainly arise from addition of CF 3 to the parent followed by combination of these radicals with CH 3 or CF 3. These fluorinated methyl hydrazine products detract from the general utility of CF 3 ‐N 2 ‐R compounds as sources for simultaneous study of the chemistry of CF 3 and R radicals. At room temperature the hydrazine products accounted for more than 50% of the total yield; however, these products can be reduced by lowering the temperature and at 195°K their yields are negligible. The quantum yield for intramolecular (direct) formation of CH 3 CF 3 + N 2 was shown to be ≤0.002.