Rate Constants and Products of the OH Reaction with Isoprene-Derived Epoxides

Title:
Rate Constants and Products of the OH Reaction with Isoprene-Derived Epoxides
Authors:
Jacobs, Michael I.; Darer, Adam I.; Elrod, Matthew J.
Abstract:
Recent laboratory and field work has shown that isoprene-derived epoxides (IEPOX) are crucial intermediates that can explain the existence of a variety of compounds found in ambient secondary organic aerosol (SOA). However, IEPOX species are also able to undergo gas phase oxidation, which competes with the aerosol phase processing of IEPOX. In order to better quantify the atmospheric fate of IEPOX, the gas phase OH reaction rate constants and product formation mechanisms have been determined using a flow tube chemical ionization mass spectrometry technique. The new OH rate constants are generally larger than previous estimations and some features of the product mechanism are well predicted by the Master Chemical Mechanism Version 3.2 (MCM v3.2), while other features are at odds with MCM v3.2. Using a previously proposed kinetic model for the quantitative prediction of the atmospheric fate of IEPOX, it is found that gas phase OH reaction is an even more dominant fate for chemical processing of IEPOX than previously suggested. The present results suggest that aerosol phase processing of IEPOX will be competitive with gas phase OH oxidation only under SOA conditions of high liquid water content and low pH.
Citation:
Jacobs, M.I., A.I. Darer, and M.J. Elrod. 2013. “Rate Constants and Products of the OH Reaction with Isoprene-Derived Epoxides.” Environmental Science and Technology 47(22): 12686-12876.
Publisher:
American Chemical Society
DATE ISSUED:
2013
Department:
Chemistry
Type:
Article
PUBLISHED VERSION:
10.1021/es403340g
PERMANENT LINK:
http://hdl.handle.net/11282/332580

Full metadata record

DC FieldValue Language
dc.contributor.authorJacobs, Michael I.en
dc.contributor.authorDarer, Adam I.en
dc.contributor.authorElrod, Matthew J.en
dc.date.accessioned2014-10-09T12:05:18Zen
dc.date.available2014-10-09T12:05:18Zen
dc.date.issued2013en
dc.identifier.citationJacobs, M.I., A.I. Darer, and M.J. Elrod. 2013. “Rate Constants and Products of the OH Reaction with Isoprene-Derived Epoxides.” Environmental Science and Technology 47(22): 12686-12876.en
dc.identifier.issn0013-936Xen
dc.identifier.urihttp://hdl.handle.net/11282/332580en
dc.description.abstractRecent laboratory and field work has shown that isoprene-derived epoxides (IEPOX) are crucial intermediates that can explain the existence of a variety of compounds found in ambient secondary organic aerosol (SOA). However, IEPOX species are also able to undergo gas phase oxidation, which competes with the aerosol phase processing of IEPOX. In order to better quantify the atmospheric fate of IEPOX, the gas phase OH reaction rate constants and product formation mechanisms have been determined using a flow tube chemical ionization mass spectrometry technique. The new OH rate constants are generally larger than previous estimations and some features of the product mechanism are well predicted by the Master Chemical Mechanism Version 3.2 (MCM v3.2), while other features are at odds with MCM v3.2. Using a previously proposed kinetic model for the quantitative prediction of the atmospheric fate of IEPOX, it is found that gas phase OH reaction is an even more dominant fate for chemical processing of IEPOX than previously suggested. The present results suggest that aerosol phase processing of IEPOX will be competitive with gas phase OH oxidation only under SOA conditions of high liquid water content and low pH.en
dc.language.isoen_USen
dc.publisherAmerican Chemical Societyen
dc.identifier.doi10.1021/es403340gen
dc.subject.departmentChemistryen
dc.titleRate Constants and Products of the OH Reaction with Isoprene-Derived Epoxidesen
dc.typeArticleen
dc.identifier.journalEnvironmental Science and Technologyen
dc.subject.keywordSecondary organic aerosolen_US
dc.subject.keywordMass-spectrometryen_US
dc.subject.keywordGas-phaseen_US
dc.subject.keywordHydroxyl radicalsen_US
dc.subject.keywordAmbient aerosolen_US
dc.subject.keywordPhotooxidationen_US
dc.subject.keywordKineticsen_US
dc.subject.keywordOrganosulfatesen_US
dc.subject.keywordEpoxydiolsen_US
dc.subject.keywordTemperatureen_US
dc.identifier.volume47en
dc.identifier.issue22en
dc.identifier.startpage12686en
All Items in The Five Colleges of Ohio Digital Repository are protected by copyright, with all rights reserved, unless otherwise indicated.