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Rapid Aqueous-Phase Hydrolysis of Ester Hydroperoxides Arising from Criegee Intermediates and Organic Acids

Zhao, Ran and Kenseth, Christopher M. and Huang, Yuanlong and Dalleska, Nathan F. and Kuang, Xiaobi M. and Chen, Jierou and Paulson, Suzanne E. and Seinfeld, John H. (2018) Rapid Aqueous-Phase Hydrolysis of Ester Hydroperoxides Arising from Criegee Intermediates and Organic Acids. Journal of Physical Chemistry A, 122 (23). pp. 5190-5201. ISSN 1089-5639. http://resolver.caltech.edu/CaltechAUTHORS:20180521-153616529

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Abstract

Stabilized Criegee intermediates react with organic acids in the gas phase and at the air–water interface to form a class of ester hydroperoxides, α-acyloxyalkyl hydroperoxides (αAAHPs). A number of recent studies have proposed the importance of αAAHPs to the formation and growth of secondary organic aerosol (SOA). The chemistry of αAAHPs has not been investigated due to a lack of commercially available chemical standards. In this work, the behavior of αAAHPs in condensed phases is investigated for the first time. Experiments were performed with two synthesized αAAHP species. αAAHPs decomposed rapidly in the aqueous phase, with the rate highly dependent on the solvent, temperature, solution pH, and other compounds present in the solution. The measured 1st-order decomposition rate coefficient varied between 10^(–3) and 10^(–5) s^(–1) under the conditions examined in this work. Elucidation of the reaction mechanism is complicated by byproducts arising from the synthetic procedure, but observations are consistent with a base-catalyzed hydrolysis of αAAHPs. The rapid hydrolysis of αAAHPs observed in this work implies their short lifetimes in ambient cloud and fog waters. Decomposition of αAAHPs likely gives rise to smaller peroxides, such as H_2O_2. The loss of αAAHPs is also relevant to filter extraction, which is commonly practiced in laboratory experiments, potentially explaining contradictory results reported in the existing literature regarding the importance of αAAHPs in SOA.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1021/acs.jpca.8b02195DOIArticle
ORCID:
AuthorORCID
Zhao, Ran0000-0002-1096-7632
Kenseth, Christopher M.0000-0003-3188-2336
Dalleska, Nathan F.0000-0002-2059-1587
Paulson, Suzanne E.0000-0003-0855-7615
Seinfeld, John H.0000-0003-1344-4068
Additional Information:© 2018 American Chemical Society. Received: March 5, 2018; Revised: May 16, 2018; Published: May 21, 2018. The authors thank Dwight and Christine Landis for their generous contributions and Prof. Paul Wennberg for helpful discussions. LC-ESI-MS and TOC analyses were performed in the Caltech Environmental Analysis Center (EAC). This work was supported by National Science Foundation Grants AGS-1523500 and CHE-1508526. R.Z. also acknowledges support from the Natural Science and Engineering Research Council of Canada Postdoctoral Fellowship (NSERC-PDF). The authors declare no competing financial interest.
Funders:
Funding AgencyGrant Number
NSFAGS-1523500
NSFCHE-1508526
Natural Science and Engineering Research Council of Canada (NSERC) UNSPECIFIED
Record Number:CaltechAUTHORS:20180521-153616529
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20180521-153616529
Official Citation:Rapid Aqueous-Phase Hydrolysis of Ester Hydroperoxides Arising from Criegee Intermediates and Organic Acids. Ran Zhao, Christopher M. Kenseth, Yuanlong Huang, Nathan F. Dalleska, Xiaobi M. Kuang, Jierou Chen, Suzanne E. Paulson, and John H. Seinfeld. The Journal of Physical Chemistry A 2018 122 (23), 5190-5201 DOI: 10.1021/acs.jpca.8b02195
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:86526
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:21 May 2018 22:49
Last Modified:05 Jul 2018 17:15

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