Absolute rate constants for reactions of free radicals in the high‐temperature photolysis of formamide vapor. II. Amino radicals

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Abstract
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 NH2 radicals. The decomposition is propagated by the reactions (1) (2) Conditions were chosen so that reaction (1) was rate controlling and NH2 the terminating radical. A flow system was employed with C2F6 as a carrier gas at a pressure of 300 Tort, and the chain reaction was initiated by the photolysis of either formamide or NH3. A value of 4.7(±2.0) × 1010 (M ·sec)−1 was estimated for the termination reaction (3) and a value of 8.4 × 106 (M ·sec)−1 for reaction (1) in the same system, both at 300°C.