Azide mechanisms for the production of NCl metastables

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Abstract
The production of both the b1Σ+ and a1Δ states of NCl has been observed from the reaction of HN3 with flowing streams of Cl and F atoms. The results suggest that a two‐step reaction sequence is responsible for the production of excited NCl, as follows: equation image The rate contant (all products) for the first step is k(F + HN3) > 1 × 10−11 cm3/molecule sec. Comparison of this value to results obtained in a previous study of the F + HN3 system yields a value k(F + N3) = 2 × 10−12 cm3/molecule sec. The rate constant for the reaction of chlorine atoms with HN3 was determined to be k(Cl + HN3) 1 × 10−12 cm3/molecule sec. The difference between the Cl + HN3 and F + HN3 rates is interpreted in terms of an addition–elimination mechanism.