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 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 NO₂ 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(CH₃ONO) = (0.6 ± 0.09) × 10⁹ dm³ mol^?1 s^?1 k(n – C₃H₇ONO) = (1.39 ± 0.20) × 10⁹ dm³ mol^?1 s^?1, and k(n – C₄H₉ONO) = (2.89 ± 0.43) × 10⁹ dm³ 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 (CH₃ONO) is a factor of 7 greater than the value obtained by relative rate measurements elsewhere using a different OH source.