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Kinetics and Products of the Acid-Catalyzed Ring-Opening of Atmospherically Relevant Butyl Epoxy Alcohols

Eddingsaas, Nathan C. and VanderVelde, David G. and Wennberg, Paul O. (2010) Kinetics and Products of the Acid-Catalyzed Ring-Opening of Atmospherically Relevant Butyl Epoxy Alcohols. Journal of Physical Chemistry A, 114 (31). pp. 8106-8113. ISSN 1089-5639. http://resolver.caltech.edu/CaltechAUTHORS:20100823-101349556

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Abstract

Epoxydiols are produced in the gas phase from the photo-oxidation of isoprene in the absence of significant mixing ratios of nitrogen oxides (NO_x). The reactive uptake of these compounds onto acidic aerosols has been shown to produce secondary organic aerosol (SOA). To better characterize the fate of isoprene epoxydiols in the aerosol phase, the kinetics and products of the acid-catalyzed ring-opening reactions of four hydroxy-substituted epoxides were studied by nuclear magnetic resonance (NMR) techniques. Polyols and sulfate esters are observed from the ring-opening of the epoxides in solutions of H_2SO_4/Na_2SO_4. Likewise, polyols and nitrate esters are produced in solutions of HNO_3/NaNO_3. In sulfuric acid, the rate of acid-catalyzed ring-opening is dependent on hydronium ion activity, sulfate ion, and bisulfate. The rates are much slower than the nonhydroxylated equivalent epoxides; however, the hydroxyl groups make them much more water-soluble. A model was constructed with the major channels for epoxydiol loss (i.e., aerosol-phase ring-opening, gas-phase oxidation, and deposition). In the atmosphere, SOA formation from epoxydiols will depend on a number of variables (e.g., pH and aerosol water content) with the yield of ring-opening products varying from less than 1% to greater than 50%.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/jp103907c DOIArticle
http://pubs.acs.org/doi/full/10.1021/jp103907cPublisherArticle
ORCID:
AuthorORCID
Eddingsaas, Nathan C.0000-0003-1539-5415
Wennberg, Paul O.0000-0002-6126-3854
Additional Information:© 2010 American Chemical Society. Received: April 29, 2010; Revised Manuscript Received: June 22, 2010. Publication Date (Web): July 21, 2010. N. C. E. was supported by the Camille and Henry Dreyfus Postdoctoral Program in Environmental Chemistry. We also thank ManNin Chan, Fabien Paulot, Havala Pye, and Jason Surratt for helpful discussions.
Funders:
Funding AgencyGrant Number
Camille and Henry Dreyfus FoundationUNSPECIFIED
Record Number:CaltechAUTHORS:20100823-101349556
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20100823-101349556
Official Citation:Kinetics and Products of the Acid-Catalyzed Ring-Opening of Atmospherically Relevant Butyl Epoxy Alcohols Nathan C. Eddingsaas, David G. VanderVelde, Paul O. Wennberg The Journal of Physical Chemistry A 2010 114 (31), 8106-8113
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:19586
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:23 Aug 2010 20:38
Last Modified:06 Apr 2017 23:44

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