The rate constants for the reaction of the hydroxyl radical with methyl, n ‐propyl, and n ‐butyl nitrites

The kinetics of the reaction of OH radicals with methyl, n ‐propyl, and n ‐butyl nitrite\documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm OH + RONO} \to {\rm products} $$\end{document}have been studied in a discharge flow system under pseudo first‐order conditions. The OH radicals were generated by the reaction of H atoms with NO 2 and the concentration of OH; monitored by resonance fluorescence, was followed as a function of time in an excess of each nitrite. Values of k (CH 3 ONO) = (0.6 ± 0.09) × 10 9 dm 3 mol −1 s −1 k ( n – C 3 H 7 ONO) = (1.39 ± 0.20) × 10 9 dm 3 mol −1 s −1 , and k ( n – C 4 H 9 ONO) = (2.89 ± 0.43) × 10 9 dm 3 mol −1 s −1 at 295 K were obtained. These results agree with previous relative rate measurements from this laboratory but the value for k (CH 3 ONO) is a factor of 7 greater than the value obtained by relative rate measurements elsewhere using a different OH source.