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Atmospheric Fate of Methacrolein. 1. Peroxy Radical Isomerization Following Addition of OH and O_2

Crounse, John D. and Knap, Hasse C. and Ørnsø, Kristian B. and Jørgensen, Solvejg and Paulot, Fabien and Kjaergaard, Henrik G. and Wennberg, Paul O. (2012) Atmospheric Fate of Methacrolein. 1. Peroxy Radical Isomerization Following Addition of OH and O_2. Journal of Physical Chemistry A, 116 (24). pp. 5756-5762. ISSN 1089-5639. doi:10.1021/jp211560u.

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Peroxy radicals formed by addition of OH and O_2 to the olefinic carbon atoms in methacrolein react with NO to form methacrolein hydroxy nitrate and hydroxyacetone. We observe that the ratio of these two compounds, however, unexpectedly decreases as the lifetime of the peroxy radical increases. We propose that this results from an isomerization involving the 1,4-H-shift of the aldehydic hydrogen atom to the peroxy group. The inferred rate (0.5 ± 0.3 s^(–1) at T = 296 K) is consistent with estimates obtained from the potential energy surface determined by high level quantum calculations. The product, a hydroxy hydroperoxy carbonyl radical, decomposes rapidly, producing hydroxyacetone and re-forming OH. Simulations using a global chemical transport model suggest that most of the methacrolein hydroxy peroxy radicals formed in the atmosphere undergo isomerization and decomposition.

Item Type:Article
Related URLs:
URLURL TypeDescription
Crounse, John D.0000-0001-5443-729X
Paulot, Fabien0000-0001-7534-4922
Kjaergaard, Henrik G.0000-0002-7275-8297
Wennberg, Paul O.0000-0002-6126-3854
Additional Information:© 2012 American Chemical Society. Received: December 1, 2011; Revised: March 12, 2012; Published: March 27, 2012. We thank N. C. Eddingsaas for the design and construction of the chamber used in this work, M. R. Beaver for assistance with experiments, J. M. St. Clair for instrumental assistance, and K. M. Spencer for providing CIMS calibrations of glycolaldehyde and hydroxyacetone. We thank J. Peeters for helpful initial discussions regarding the feasibility of the 1,4-H-shift of MACR-1-OH-2-OO. We thank NASA (NNX08AD29G) and NSF (ATM-0934408), the Danish Council for Independent Research - Natural Sciences, and the Danish Center for Scientific Computing (DCSC) for funding. F.P. acknowledges support from NASA earth and space science fellowship.
Funding AgencyGrant Number
Danish Council for Independent Research Natural SciencesUNSPECIFIED
Danish Center for Scientific Computing (DCSC)UNSPECIFIED
NASA Earth and Space Science FellowshipUNSPECIFIED
Issue or Number:24
Record Number:CaltechAUTHORS:20120713-101645825
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Official Citation:Atmospheric Fate of Methacrolein. 1. Peroxy Radical Isomerization Following Addition of OH and O2 John D. Crounse, Hasse C. Knap, Kristian B. Ørnsø, Solvejg Jørgensen, Fabien Paulot, Henrik G. Kjaergaard, and Paul O. Wennberg The Journal of Physical Chemistry A 2012 116 (24), 5756-5762
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:32419
Deposited By: Jason Perez
Deposited On:13 Jul 2012 18:01
Last Modified:09 Nov 2021 21:27

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