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Absolute rate constants for reactions of free radicals in the high‐temperature photolysis of formamide vapor. II. Amino radicals
Author(s) -
Back R. A.,
Yokota T.
Publication year - 1973
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.550050612
Subject(s) - chemistry , radical , formamide , photodissociation , reaction rate constant , decomposition , photochemistry , chain reaction , kinetics , organic chemistry , physics , quantum mechanics
The rotating‐sector method has been applied to the photoinitiated radical‐chain decomposition of formamide at 300°C to measure the rate constant for the bimolecular disappearance of NH 2 radicals. The decomposition is propagated by the reactions (1)\documentclass{article}\pagestyle{empty}\begin{document}$$ NH_2 + NH_2 CHO \to NH_3 + NH_2 CO $$\end{document}(2)\documentclass{article}\pagestyle{empty}\begin{document}$$ NH_2 CHO \to N_2 + CO $$\end{document}Conditions were chosen so that reaction (1) was rate controlling and NH 2 the terminating radical. A flow system was employed with C 2 F 6 as a carrier gas at a pressure of 300 Tort, and the chain reaction was initiated by the photolysis of either formamide or NH 3 . A value of 4.7(±2.0) × 10 10 (M ·sec) −1 was estimated for the termination reaction (3)\documentclass{article}\pagestyle{empty}\begin{document}$$ 2NH_2 \to N_2 H_4 $$\end{document}and a value of 8.4 × 10 6 (M ·sec) −1 for reaction (1) in the same system, both at 300°C.