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Water Dramatically Accelerates the Decomposition of α-Hydroxyalkyl-Hydroperoxides in Aerosol Particles

Qiu, Junting and Ishizuka, Shinnosuke and Tonokura, Kenichi and Colussi, Agustín J. and Enami, Shinichi (2019) Water Dramatically Accelerates the Decomposition of α-Hydroxyalkyl-Hydroperoxides in Aerosol Particles. Journal of Physical Chemistry Letters, 10 (19). pp. 5748-5755. ISSN 1948-7185.

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α-Hydroxyalkyl-hydroperoxides (α-HHs), from the addition of water to Criegee intermediates in the ozonolysis of olefins, are reactive components of organic aerosols. Assessing the fate of α-HHs in such media requires information on the rates and products of their reactions in aqueous organic matrices. This information, however, is unavailable due to the lack of analytical techniques for the detection and identification of labile α-HHs. Here, we report the mass spectrometric detection (as Cl- adducts) of the α-HH produced in the ozonolysis of a C_(15) diolefin in water (W):acetonitrile (AN) mixtures of variable composition. α-HH decays into a gem-diol + H_2O_2 in τ_(1/e) ~ 52 min in 50% (v:v) water, but persists longer than a day in < 10% water mixtures. The strong non-linear dependence of τ_(1/e) on water content reveals that water content is a major factor controlling the fate of α-HHs in atmospheric particles, and suggests that α-HH decomposes while embedded in W_nAN_m clusters rather than randomly dissolved in molecularly homogeneous W:AN mixtures.

Item Type:Article
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URLURL TypeDescription
Ishizuka, Shinnosuke0000-0002-5915-3576
Tonokura, Kenichi0000-0003-1910-8508
Colussi, Agustín J.0000-0002-3400-4101
Enami, Shinichi0000-0002-2790-7361
Additional Information:© 2019 American Chemical Society. This is an open access article published under an ACS AuthorChoice License, which permits copying and redistribution of the article or any adaptations for non-commercial purposes. Received: July 6, 2019; Accepted: September 9, 2019; Published: September 9, 2019. S. E. is grateful to the JSPS KAKENHI grant number 15H05328 and 19H01154. A.J.C. acknowledges support from the National Science Foundation USA, grant AGS-1744353. Author Contributions: S.E. designed research; J.Q. and S.E. performed experiments; S.E. contributed new reagents/analytic tools. All authors analyzed data and wrote the paper.
Funding AgencyGrant Number
Japan Society for the Promotion of Science (JSPS)15H05328
Japan Society for the Promotion of Science (JSPS)19H01154
Issue or Number:19
Record Number:CaltechAUTHORS:20190909-155045245
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Official Citation:Water Dramatically Accelerates the Decomposition of α-Hydroxyalkyl-Hydroperoxides in Aerosol Particles. Junting Qiu, Shinnosuke Ishizuka, Kenichi Tonokura, Agustín J. Colussi, and Shinichi Enami. The Journal of Physical Chemistry Letters 2019 10 (19), 5748-5755. DOI: 10.1021/acs.jpclett.9b01953
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:98533
Deposited By: George Porter
Deposited On:09 Sep 2019 23:12
Last Modified:09 Mar 2020 13:19

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