Kinetics and Thermodynamics of Atmospherically Relevant Aqueous Phase Reactions of α-Pinene Oxide

Title:
Kinetics and Thermodynamics of Atmospherically Relevant Aqueous Phase Reactions of α-Pinene Oxide
Authors:
Bleier, Dylan B.; Elrod, Matthew J.
Abstract:
Recent work has demonstrated that isoprene-derived epoxide intermediates are responsible for a wide variety of chemical species found in ambient secondary organic aerosol (SOA). Since the second most abundant biogenic hydrocarbon, α-pinene, is also known to form an epoxide intermediate, nuclear magnetic resonance techniques were used to study products, kinetics, and equilibria of the aqueous phase reactions of that epoxide, α-pinene oxide. The present results indicate that α-pinene oxide will react very quickly with aqueous atmospheric particles, even under low acidity conditions. Depending on the acid concentration of the aqueous solutions, a number of new products are observed from the reaction of α-pinene oxide, some of which are expected to partition back to the gas phase. In contrast to some previous results, no long-lived organosulfate or organonitrate species are observed, and no species which retain the α-pinene bicyclic carbon backbone are observed. Rather, the overall product distribution can be explained by various rearrangements of the initial carbocation intermediate formed in the ring opening of α-pinene oxide, all of which can be rationalized by the thermodynamically driven relief of the bicyclic ring strain in the α-pinene carbon backbone.
Citation:
Bleier, D.B. and M.J. Elrod. 2013. “Kinetics and Thermodynamics of Atmospherically Relevant Aqueous Phase Reactions of α-Pinene Oxide.” Journal of Physical Chemistry 117(20): 4223-4232.
Publisher:
American Chemical Society
DATE ISSUED:
2013
Department:
Chemistry
Type:
Article
PUBLISHED VERSION:
10.1021/jp402093x
PERMANENT LINK:
http://hdl.handle.net/11282/332501

Full metadata record

DC FieldValue Language
dc.contributor.authorBleier, Dylan B.en
dc.contributor.authorElrod, Matthew J.en
dc.date.accessioned2014-10-09T12:04:22Zen
dc.date.available2014-10-09T12:04:22Zen
dc.date.issued2013en
dc.identifier.citationBleier, D.B. and M.J. Elrod. 2013. “Kinetics and Thermodynamics of Atmospherically Relevant Aqueous Phase Reactions of α-Pinene Oxide.” Journal of Physical Chemistry 117(20): 4223-4232.en
dc.identifier.issn1089-5639en
dc.identifier.urihttp://hdl.handle.net/11282/332501en
dc.description.abstractRecent work has demonstrated that isoprene-derived epoxide intermediates are responsible for a wide variety of chemical species found in ambient secondary organic aerosol (SOA). Since the second most abundant biogenic hydrocarbon, α-pinene, is also known to form an epoxide intermediate, nuclear magnetic resonance techniques were used to study products, kinetics, and equilibria of the aqueous phase reactions of that epoxide, α-pinene oxide. The present results indicate that α-pinene oxide will react very quickly with aqueous atmospheric particles, even under low acidity conditions. Depending on the acid concentration of the aqueous solutions, a number of new products are observed from the reaction of α-pinene oxide, some of which are expected to partition back to the gas phase. In contrast to some previous results, no long-lived organosulfate or organonitrate species are observed, and no species which retain the α-pinene bicyclic carbon backbone are observed. Rather, the overall product distribution can be explained by various rearrangements of the initial carbocation intermediate formed in the ring opening of α-pinene oxide, all of which can be rationalized by the thermodynamically driven relief of the bicyclic ring strain in the α-pinene carbon backbone.en
dc.language.isoen_USen
dc.publisherAmerican Chemical Societyen
dc.identifier.doi10.1021/jp402093xen
dc.subject.departmentChemistryen
dc.titleKinetics and Thermodynamics of Atmospherically Relevant Aqueous Phase Reactions of α-Pinene Oxideen
dc.typeArticleen
dc.identifier.journalThe Journal of Physical Chemistryen
dc.subject.keywordSecondary organic aerosolen_US
dc.subject.keywordIsopreneen_US
dc.subject.keywordEpoxidesen_US
dc.subject.keywordPhotooxidationen_US
dc.subject.keywordHydrolysisen_US
dc.subject.keywordOrganosulfatesen_US
dc.subject.keywordIsomerizationen_US
dc.identifier.volume117en
dc.identifier.issue20en
dc.identifier.startpage4223en
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