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Title: Hydroxyacetone production from C 3 Criegee intermediates

Hydroxyacetone (CH 3C(O)CH 2OH) is observed as a stable end product from reactions of the (CH 3) 2COO Criegee intermediate, acetone oxide, in a flow tube coupled with multiplexed photoionization mass spectrometer detection. In the experiment, the isomers at m/z = 74 are distinguished by their different photoionization spectra and reaction times. Hydroxyacetone is observed as a persistent signal at longer reaction times at a higher photoionization threshold of ca. 9.7 eV than Criegee intermediate and definitively identified by comparison with the known photoionization spectrum. Complementary electronic structure calculations reveal multiple possible reaction pathways for hydroxyacetone formation, including unimolecular isomerization via hydrogen atom transfer and –OH group migration as well as self-reaction of Criegee intermediates. Varying the concentration of Criegee intermediates suggests contributions from both unimolecular and self-reaction pathways to hydroxyacetone. As a result, the hydroxyacetone end product can provide an effective, stable marker for the production of transient Criegee intermediates in future studies of alkene ozonolysis.
Authors:
 [1] ;  [2] ;  [1] ;  [3] ;  [1] ;  [1] ;  [4] ; ORCiD logo [2]
  1. Sandia National Lab. (SNL-CA), Livermore, CA (United States)
  2. Univ. of Pennsylvania, Philadelphia, PA (United States)
  3. Univ. of Nebraska, Lincoln, NE (United States)
  4. Univ. of Kansas, Lawrence, KS (United States)
Publication Date:
Report Number(s):
SAND-2017-0649J
Journal ID: ISSN 1089-5639; 650605
Grant/Contract Number:
AC04-94AL85000
Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
Additional Journal Information:
Journal Volume: 121; Journal Issue: 1; Journal ID: ISSN 1089-5639
Publisher:
American Chemical Society
Research Org:
Sandia National Lab. (SNL-CA), Livermore, CA (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1340694

Taatjes, Craig A., Liu, Fang, Rotavera, Brandon, Kumar, Manoj, Caravan, Rebecca, Osborn, David L., Thompson, Ward H., and Lester, Marsha I.. Hydroxyacetone production from C3 Criegee intermediates. United States: N. p., Web. doi:10.1021/acs.jpca.6b07712.
Taatjes, Craig A., Liu, Fang, Rotavera, Brandon, Kumar, Manoj, Caravan, Rebecca, Osborn, David L., Thompson, Ward H., & Lester, Marsha I.. Hydroxyacetone production from C3 Criegee intermediates. United States. doi:10.1021/acs.jpca.6b07712.
Taatjes, Craig A., Liu, Fang, Rotavera, Brandon, Kumar, Manoj, Caravan, Rebecca, Osborn, David L., Thompson, Ward H., and Lester, Marsha I.. 2016. "Hydroxyacetone production from C3 Criegee intermediates". United States. doi:10.1021/acs.jpca.6b07712. https://www.osti.gov/servlets/purl/1340694.
@article{osti_1340694,
title = {Hydroxyacetone production from C3 Criegee intermediates},
author = {Taatjes, Craig A. and Liu, Fang and Rotavera, Brandon and Kumar, Manoj and Caravan, Rebecca and Osborn, David L. and Thompson, Ward H. and Lester, Marsha I.},
abstractNote = {Hydroxyacetone (CH3C(O)CH2OH) is observed as a stable end product from reactions of the (CH3)2COO Criegee intermediate, acetone oxide, in a flow tube coupled with multiplexed photoionization mass spectrometer detection. In the experiment, the isomers at m/z = 74 are distinguished by their different photoionization spectra and reaction times. Hydroxyacetone is observed as a persistent signal at longer reaction times at a higher photoionization threshold of ca. 9.7 eV than Criegee intermediate and definitively identified by comparison with the known photoionization spectrum. Complementary electronic structure calculations reveal multiple possible reaction pathways for hydroxyacetone formation, including unimolecular isomerization via hydrogen atom transfer and –OH group migration as well as self-reaction of Criegee intermediates. Varying the concentration of Criegee intermediates suggests contributions from both unimolecular and self-reaction pathways to hydroxyacetone. As a result, the hydroxyacetone end product can provide an effective, stable marker for the production of transient Criegee intermediates in future studies of alkene ozonolysis.},
doi = {10.1021/acs.jpca.6b07712},
journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
number = 1,
volume = 121,
place = {United States},
year = {2016},
month = {12}
}