KINETICS AND MECHANISMS OF THE REACTIONS OF OH WITH SOME OXYGENATED COMPOUNDS OF IMPORTANCE IN TROPOSPHERIC CHEMISTRY

The kinetics of the reactions (1) OH + (CH3)(3)COH --> products (2) OH + (CH3)(2)CHCH2CH2OH --> products [GRAPHICS] 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 k(1) = (8.1 +/- 1.7) x 10(-13), k(2) = (1.31 +/- 0.26) x 10(-11), k(3) = (2.6 +/- 0.5) X 10(-11), and k(4) = (2.5 +/- 0.4) x 10(-11) cm(3) molecule(-l) s(-l), at 298 K and 1 torr total pressure, were obtained. To validate the newly constructed system the rate constant for the reaction (5) OH + cyclo-C6H12 --> products was determined in a similar manner. The value of k(5) = (6.7 +/- 0.9) X 10(-12) cm(3) molecule(-l) s(-l) 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. (C) 1994 John Wiley and Sons, Inc.