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FORMATION OF BETA-HYDROXYCARBONYLS FROM THE OH RADICAL-INITIATED REACTIONS OF SELECTED ALKENES (R825252)
Citation:
Aschmann, S. M., J. Arey, AND R. Atkinson. FORMATION OF BETA-HYDROXYCARBONYLS FROM THE OH RADICAL-INITIATED REACTIONS OF SELECTED ALKENES (R825252). ENVIRONMENTAL SCIENCE & TECHNOLOGY. American Chemical Society, Washington, DC, 34:1702-1706, (2000).
Description:
-Hydroxycarbonyls can be formed from the gas-phase
reactions of alkenes with the OH radical, both in the presence
and in the absence of NO. To date, because of analytical
difficulties, few data have been reported for the formation
of this class of compound from the reactions of the OH
radical with alkenes. We have determined that -hydroxyketones can be readily analyzed by gas chromatography,
and in this work we have shown that in 1 atm of air the-hydroxyalkoxy radicals formed in the reactions of the
OH radical with trans-2-butene, trans-3-hexene, 1-butene,
and 
-pinene in the presence of NO primarily decompose
rather than react with O2. Rate constant ratios kd/kO2 (or
lower limits thereof), where kd and kO2 are respectively
the rate constants for the decomposition and the reaction
with O2 of the intermediate -hydroxyalkoxy radicals,
have been obtained for the reactions of the CH3CH(
)CH(OH)CH3, CH3CH2CH()CH2OH, and CH3CH2CH()CH(OH)CH2CH3 radicals at 296 ± 2 K and atmospheric pressure.
Using the O3 reactions with the alkenes to generate OH
radicals, the reactions of the OH radical with trans-2-butene,
trans-3-hexene, and -pinene in the absence of NO lead
to the formation of the expected -hydroxycarbonyls and (at
least for trans-2-butene) the ,-diol.