Kinetics and mechanisms of the reactions of OH with some oxygenated compounds of importance in tropospheric chemistry

The kinetics of the reactions have been studied in a discharge flow system under pseudo-first-order conditions. The OH concentration was monitored by laser induced fluorescence and helium was used as the carrier gas. Values of k1 = (8.1 ± 1.7) × 10−13, k2 = (1.31 ± 0.26) × 10−11, k3 = (2.6 ± 0.5) × 10−11, and k4 = (2.5 ± 0.4) × 10−11 cm3 molecule−1 s−1, at 298 K and 1 torr total pressure, were obtained. To validate the newly constructed system the rate constant for the reaction was determined in a similar manner. The value of k5 = (6.7 ± 0.9) × 10−12 cm3 molecule−1 s−1 at 298 K and 1 torr total pressure is in very good agreement with other literature values. The mechanisms for the atmospheric degradation of these compounds have been constructed to allow their incorporation in a photochemical trajectory computer model, to assess their impact on photochemical ozone creation in the troposphere. © 1994 John Wiley & Sons, Inc.