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−1k(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.