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Isoprene NO_3 Oxidation Products from the RO_2 + HO_2 Pathway

Schwantes, Rebecca H. and Teng, Alexander P. and Nguyen, Tran B. and Coggon, Matthew M. and Crounse, John D. and St. Clair, Jason M. and Zhang, Xuan and Schilling, Katherine A. and Seinfeld, John H. and Wennberg, Paul O. (2015) Isoprene NO_3 Oxidation Products from the RO_2 + HO_2 Pathway. Journal of Physical Chemistry A, 119 (40). pp. 10158-10171. ISSN 1089-5639.

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We describe the products of the reaction of the hydroperoxy radical (HO_2) with the alkylperoxy radical formed following addition of the nitrate radical (NO_3) and O_2 to isoprene. NO_3 adds preferentially to the C_1 position of isoprene (>6 times more favorably than addition to C_4), followed by the addition of O_2 to produce a suite of nitrooxy alkylperoxy radicals (RO_2). At an RO_2 lifetime of ∼30 s, δ-nitrooxy and β-nitrooxy alkylperoxy radicals are present in similar amounts. Gas-phase product yields from the RO_2 + HO_2 pathway are identified as 0.75–0.78 isoprene nitrooxy hydroperoxide (INP), 0.22 methyl vinyl ketone (MVK) + formaldehyde (CH_2O) + hydroxyl radical (OH) + nitrogen dioxide (NO_2), and 0–0.03 methacrolein (MACR) + CH_2O + OH + NO_2. We further examined the photochemistry of INP and identified propanone nitrate (PROPNN) and isoprene nitrooxy hydroxyepoxide (INHE) as the main products. INHE undergoes similar heterogeneous chemistry as isoprene dihydroxy epoxide (IEPOX), likely contributing to atmospheric secondary organic aerosol formation.

Item Type:Article
Related URLs:
URLURL TypeDescription Information
Schwantes, Rebecca H.0000-0002-7095-3718
Teng, Alexander P.0000-0002-6434-0501
Coggon, Matthew M.0000-0002-5763-1925
Crounse, John D.0000-0001-5443-729X
St. Clair, Jason M.0000-0002-9367-5749
Seinfeld, John H.0000-0003-1344-4068
Wennberg, Paul O.0000-0002-6126-3854
Alternate Title:Isoprene NO3 Oxidation Products from the RO2 + HO2 Pathway
Additional Information:© 2015 American Chemical Society. Received: July 2, 2015; Revised: August 27, 2015; Publication Date (Web): September 3, 2015. The authors thank the National Science Foundation (AGS-1240604) and the Electric Power Research Institute for their support of this work. TBN acknowledges support from NSF PRF award AGS-1331360. Development of the GC-ToF-CIMS is supported by an award from the National Science Foundation’s Major Research Instrumentation Program (AGS-1428482). The authors declare no competing financial interest.
Funding AgencyGrant Number
Electric Power Research Institute (EPRI)UNSPECIFIED
Issue or Number:40
Record Number:CaltechAUTHORS:20150928-082640803
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Official Citation:Isoprene NO3 Oxidation Products from the RO2 + HO2 Pathway Rebecca H. Schwantes, Alexander P. Teng, Tran B. Nguyen, Matthew M. Coggon, John D. Crounse, Jason M. St. Clair, Xuan Zhang, Katherine A. Schilling, John H. Seinfeld, and Paul O. Wennberg The Journal of Physical Chemistry A 2015 119 (40), 10158-10171 DOI: 10.1021/acs.jpca.5b06355
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:60558
Deposited By: Tony Diaz
Deposited On:29 Sep 2015 03:35
Last Modified:09 Mar 2020 13:19

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