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Temperature dependence of the yields of methacrolein and methyl vinyl ketone from the OH-initiated oxidation of isoprene under NOx-free conditions
Abstract Yields of methacrolein (MAC) and methyl vinyl ketone (MVK) from the OH-initiated oxidation of isoprene were measured under NOx-free conditions at 303, 323 and 343 K and 1 atm in a quartz reaction chamber coupled to a mass spectrometer. Measured yields of MAC and MVK were approximately 9–11% and 17−22%, respectively at temperatures between 303 and 343 K, in good agreement with previous studies. The measured yields of MAC and MVK, at 303 and 323 K as well as the measured yield of MAC at 343 K were reproduced reasonably well using an explicit model of isoprene oxidation. However, the experimental yields of MVK at 343 K were underestimated by the model, suggesting that a temperature dependent source of MVK was missing. Several recently proposed additions to the isoprene oxidation mechanism, including 1,6- and 1,5-H shift isomerization reactions of isoprene-based hydroxyalkyl peroxy radicals, were tested in order to determine if these mechanisms can explain the observed temperature dependence of the product yields.
Highlights Yields of methacrolein and methyl vinyl ketone from isoprene oxidation were measured. The yield of methacrolein was independent of temperature. The yield of methyl vinyl ketone increased with temperature. Recently proposed additions to the isoprene oxidation mechanism were tested.
Temperature dependence of the yields of methacrolein and methyl vinyl ketone from the OH-initiated oxidation of isoprene under NOx-free conditions
Abstract Yields of methacrolein (MAC) and methyl vinyl ketone (MVK) from the OH-initiated oxidation of isoprene were measured under NOx-free conditions at 303, 323 and 343 K and 1 atm in a quartz reaction chamber coupled to a mass spectrometer. Measured yields of MAC and MVK were approximately 9–11% and 17−22%, respectively at temperatures between 303 and 343 K, in good agreement with previous studies. The measured yields of MAC and MVK, at 303 and 323 K as well as the measured yield of MAC at 343 K were reproduced reasonably well using an explicit model of isoprene oxidation. However, the experimental yields of MVK at 343 K were underestimated by the model, suggesting that a temperature dependent source of MVK was missing. Several recently proposed additions to the isoprene oxidation mechanism, including 1,6- and 1,5-H shift isomerization reactions of isoprene-based hydroxyalkyl peroxy radicals, were tested in order to determine if these mechanisms can explain the observed temperature dependence of the product yields.
Highlights Yields of methacrolein and methyl vinyl ketone from isoprene oxidation were measured. The yield of methacrolein was independent of temperature. The yield of methyl vinyl ketone increased with temperature. Recently proposed additions to the isoprene oxidation mechanism were tested.
Temperature dependence of the yields of methacrolein and methyl vinyl ketone from the OH-initiated oxidation of isoprene under NOx-free conditions
Navarro, Maria A. (author) / Dusanter, Sebastien (author) / Stevens, Philip S. (author)
Atmospheric Environment ; 79 ; 59-66
2013-06-14
8 pages
Article (Journal)
Electronic Resource
English
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