Kinetics studies of the OH-initiated oxidation of 2-butyne, propyne, and acetylene were conducted at 100 Torr and 298 K using turbulent flow chemical ionization mass spectrometry. The major oxidation products were identified, and with the aid of supporting electronic structure thermodynamics calculations, a general OH-initiated oxidation mechanism for the alkynes is proposed. The major product branching ratio and the product-forming rate constants for the 2-butyne-OH adduct + O(2) reaction were experimentally determined as well. The atmospheric implications of the chemical oxidation mechanism and kinetics results are discussed.

A direct kinetics study of the product-forming channels of the reaction of isoprenederived hydroxyalkylperoxy radicals with NO has been performed at 100 Torr pressure and 298 K using the turbulent flow technique with high-pressure chemical ionization mass spectrometry for the detection of reactants and products. For comparative purposes, a similar study was also performed for the reaction of 1-and 2-butene-derived hydroxyalkylperoxy radicals with NO. The measured hydroxyalkylnitrate product channel branching ratios were determined to be 0.061, 0.068, and 0.070 for the 1-butene, 2-butene, and isoprene systems, respectively. The results are compared to previous measurements of the hydroxyalkylnitrate-branching ratios for these systems, and the atmospheric significance of the results is discussed.

The overall rate constants of the NO reaction with chloroalkylperoxy radicals derived from the Cl-initiated oxidation of several atmospherically abundant alkenes-ethene, propene, 1-butene, 2-butene, 2-methylpropene, 1,3-butadiene, and isoprene (2-methyl-1,3-butadiene)-were determined for the first time via the turbulent flow technique and pseudo-first-order kinetics conditions with high-pressure chemical ionization mass spectrometry for the direct detection of chloroalkylperoxy radical reactants. The individual 100 Torr, 298 K rate constants for each monoalkene system were found to be identical within the 95% confidence interval associated with each separate measurement, whereas the corresponding rate constants for 1,3-butadiene and isoprene were both approximately 20% higher than the monoalkene mean value. Our previous study of the reaction of hydroxylalkylperoxy radicals (derived from the OH-initiated oxidation of alkenes) with NO yielded identical rate constants for all of the alkenes under study, with a rate constant value within the statistical uncertainty of the value determined here for the NO reaction of chloroalkylperoxy radicals derived from monoalkenes. Thus, the reaction of NO with chloroalkylperoxy radicals derived from dialkenes is found to be significantly faster than the NO reaction with either chloroalkylperoxy radicals derived from monoalkenes or hydroxyalkylperoxy radicals derived from either mono- or dialkenes.

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