Atomic resonance fluorescence for rate constants of rapid bimolecular reactions. Part 5—Hydrogen atom reactions; H + NO2and H + O3

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Abstract
Direct determinations of the rate constants k1 and k2(cm3 molecule–1 s–1) are reported, for the reactions of H 2S atoms with NO2 and O3, using atomic resonance fluorescence in a discharge–flow system to detect hydrogen atoms. Measurements of k1 for reaction (1) at four temperatures from 298 to 653 K were made: H + NO2[graphic omitted] NO + OH; (1) the following overall Arrhenius expression was obtained: log10k1=(–9.319 ± 0.084)–(174 ± 31)/T(2σ). Measurements of k2 for reaction (2) were made at three temperatures between 298 and 638 K: H + O3[graphic omitted] O2+ OH.(2) These results gave the expression: log10k2=(–10.005 ± 0.102)–(224 ± 26)/T(2σ).