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Title: Bimolecular Reaction of Methyl-Ethyl-Substituted Criegee Intermediate with SO2

Abstract

Methyl-ethyl-substituted Criegee intermediate (MECI) is a four-carbon carbonyl oxide that is formed in the ozonolysis of some asymmetric alkenes. MECI is structurally similar to the isoprene-derived methyl vinyl ketone oxide (MVK-oxide) but lacks resonance stabilization, making it a promising candidate to help us unravel the effects of size, structure, and resonance stabilization that influence the reactivity of atmospherically important, highly functionalized Criegee intermediates. We present experimental and theoretical results from the first bimolecular study of MECI in its reaction with SO2, a reaction that shows significant sensitivity to the Criegee intermediate structure. Using multiplexed photoionization mass spectrometry, we obtain a rate coefficient of (1.3 ± 0.3) × 10–10 cm3 s–1 (95% confidence limits, 298 K, 10 Torr) and demonstrate the formation of SO3 under our experimental conditions. Through high-level theory, we explore the effect of Criegee intermediate structure on the minimum energy pathways for their reactions with SO2 and obtain modified Arrhenius fits to our predictions for the reaction of both syn and anti conformers of MECI with SO2 (ksyn = 4.42 × 1011 T–7.80exp(-1401/T) cm3 s–1 and kanti = 1.26 × 1011 T–7.55exp(-1397/T) cm3 s–1). In conclusion, our experimental and theoretical rate coefficients (which are in reasonable agreement atmore » 298 K) show that the reaction of MECI with SO2 is significantly faster than MVK-oxide + SO2, demonstrating the substantial effect of resonance stabilization on Criegee intermediate reactivity.« less

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [1];  [3];  [4];  [5]; ORCiD logo [5]; ORCiD logo [6]; ORCiD logo [3]; ORCiD logo [3]; ORCiD logo [5]; ORCiD logo [2]; ORCiD logo [1]; ORCiD logo [2]
+ Show Author Affiliations
  1. Univ. of Pennsylvania, Philadelphia, PA (United States)
  2. Argonne National Laboratory (ANL), Argonne, IL (United States)
  3. California Institute of Technology (CalTech), Pasadena, CA (United States). Jet Propulsion Lab. (JPL)
  4. Sandia National Lab. (SNL-CA), Livermore, CA (United States)
  5. Sandia National Lab. (SNL-CA), Livermore, CA (United States). Combustion Research Facility
  6. Sandia National Lab. (SNL-CA), Livermore, CA (United States). Combustion Research Facility; Univ. of California, Davis, CA (United States)
Publication Date:
Research Org.:
Sandia National Lab. (SNL-CA), Livermore, CA (United States); Argonne National Laboratory (ANL), Argonne, IL (United States); California Institute of Technology (CalTech), Pasadena, CA (United States). Jet Propulsion Lab. (JPL)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); National Science Foundation (NSF); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS); National Aeronautics and Space Administration (NASA)
OSTI Identifier:
2311366
Report Number(s):
SAND-2023-13335J
Journal ID: ISSN 1089-5639
Grant/Contract Number:  
NA0003525; FG02-87ER13792; AC02-06CH11357; AC02-05CH11231; CHE-1955068; ACI-1548562; CHE-2102626
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
Additional Journal Information:
Journal Volume: 127; Journal Issue: 43; Journal ID: ISSN 1089-5639
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Chemical calculations; Energy; Kinetics; Molecular structure; Photoionization

Citation Formats

Zou, Meijun, Liu, Tianlin, Vansco, Michael F., Sojdak, Christopher A., Markus, Charles R., Almeida, Raybel, Au, Kendrew, Sheps, Leonid, Osborn, David Lewis, Winiberg, Frank F., Percival, Carl J., Taatjes, Craig A., Klippenstein, Stephen J., Lester, Marsha I., and Caravan, Rebecca L. Bimolecular Reaction of Methyl-Ethyl-Substituted Criegee Intermediate with SO2. United States: N. p., 2023. Web. doi:10.1021/acs.jpca.3c04648.
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Zou, Meijun, Liu, Tianlin, Vansco, Michael F., Sojdak, Christopher A., Markus, Charles R., Almeida, Raybel, Au, Kendrew, Sheps, Leonid, Osborn, David Lewis, Winiberg, Frank F., Percival, Carl J., Taatjes, Craig A., Klippenstein, Stephen J., Lester, Marsha I., & Caravan, Rebecca L. Bimolecular Reaction of Methyl-Ethyl-Substituted Criegee Intermediate with SO2. United States. https://doi.org/10.1021/acs.jpca.3c04648
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Zou, Meijun, Liu, Tianlin, Vansco, Michael F., Sojdak, Christopher A., Markus, Charles R., Almeida, Raybel, Au, Kendrew, Sheps, Leonid, Osborn, David Lewis, Winiberg, Frank F., Percival, Carl J., Taatjes, Craig A., Klippenstein, Stephen J., Lester, Marsha I., and Caravan, Rebecca L. Mon . "Bimolecular Reaction of Methyl-Ethyl-Substituted Criegee Intermediate with SO2". United States. https://doi.org/10.1021/acs.jpca.3c04648.
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@article{osti_2311366,
title = {Bimolecular Reaction of Methyl-Ethyl-Substituted Criegee Intermediate with SO2},
author = {Zou, Meijun and Liu, Tianlin and Vansco, Michael F. and Sojdak, Christopher A. and Markus, Charles R. and Almeida, Raybel and Au, Kendrew and Sheps, Leonid and Osborn, David Lewis and Winiberg, Frank F. and Percival, Carl J. and Taatjes, Craig A. and Klippenstein, Stephen J. and Lester, Marsha I. and Caravan, Rebecca L.},
abstractNote = {Methyl-ethyl-substituted Criegee intermediate (MECI) is a four-carbon carbonyl oxide that is formed in the ozonolysis of some asymmetric alkenes. MECI is structurally similar to the isoprene-derived methyl vinyl ketone oxide (MVK-oxide) but lacks resonance stabilization, making it a promising candidate to help us unravel the effects of size, structure, and resonance stabilization that influence the reactivity of atmospherically important, highly functionalized Criegee intermediates. We present experimental and theoretical results from the first bimolecular study of MECI in its reaction with SO2, a reaction that shows significant sensitivity to the Criegee intermediate structure. Using multiplexed photoionization mass spectrometry, we obtain a rate coefficient of (1.3 ± 0.3) × 10–10 cm3 s–1 (95% confidence limits, 298 K, 10 Torr) and demonstrate the formation of SO3 under our experimental conditions. Through high-level theory, we explore the effect of Criegee intermediate structure on the minimum energy pathways for their reactions with SO2 and obtain modified Arrhenius fits to our predictions for the reaction of both syn and anti conformers of MECI with SO2 (ksyn = 4.42 × 1011 T–7.80exp(-1401/T) cm3 s–1 and kanti = 1.26 × 1011 T–7.55exp(-1397/T) cm3 s–1). In conclusion, our experimental and theoretical rate coefficients (which are in reasonable agreement at 298 K) show that the reaction of MECI with SO2 is significantly faster than MVK-oxide + SO2, demonstrating the substantial effect of resonance stabilization on Criegee intermediate reactivity.},
doi = {10.1021/acs.jpca.3c04648},
journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
number = 43,
volume = 127,
place = {United States},
year = {Mon Oct 23 00:00:00 EDT 2023},
month = {Mon Oct 23 00:00:00 EDT 2023}
}
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