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Published November 2, 2023 | Version Published
Journal Article Open

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

Creators

  • 1. ROR icon University of Pennsylvania
  • 2. ROR icon Argonne National Laboratory
  • 3. ROR icon Jet Propulsion Lab
  • 4. ROR icon California Institute of Technology
  • 5. ROR icon Sandia National Laboratories California
  • 6. ROR icon University of California, Davis

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 (kₛᵧₙ = 4.42 × 1011 T^(–7.80)exp(−1401/T) cm³ s⁻¹ and kₐₙₜᵢ = 1.26 × 1011 T^(–7.55)exp(−1397/T) cm³ s⁻¹). 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.

Copyright and License

© 2023 UChicago Argonne, LLC, Operator of Argonne National Laboratory. Published by American Chemical Society.

Acknowledgement

esearch at the University of Pennsylvania was supported by the National Science Foundation under grant CHE-1955068 with partial equipment support from the US Department of Energy–Basic Energy Sciences under grant DE-FG02-87ER13792. This work utilized the Extreme Science and Engineering Discovery Environment (XSEDE), which was supported by the National Science Foundation grant number ACI-1548562 through the allocation TG-CHE190088. C.A.S. acknowledges support from NSF CHE-2102626. Argonne National Laboratory is supported by the USDOE, Office of Science, BES, Division of Chemical Sciences, Geosciences, and Biosciences under Contract No. DE-AC02-06CH11357. Sandia National Laboratories is a multimission laboratory managed and operated by National Technology and Engineering Solutions of Sandia, LLC, a wholly owned subsidiary of Honeywell International, Inc., for the USDOE's National Nuclear Security Administration under contract DE-NA0003525. The operation of the multiplexed photoionization mass spectrometry kinetics experiments and the participation of the Sandia personnel was supported by Chemical Sciences, Geosciences, and Biosciences, Office of Basic Energy Sciences, of the U.S. Department of Energy. This research used resources of the Advanced Light Source, which is a DOE Office of Science User Facility under contract no. DE-AC02-05CH11231. C.R.M. is grateful for support from an A.O. Beckman postdoctoral fellowship. This research was carried out in part by the Jet Propulsion Laboratory, California Institute of Technology, under contract with the National Aeronautics and Space Administration (NASA), supported by the Upper Atmosphere Research and Tropospheric Chemistry program. This paper describes objective technical results and analysis. Any subjective views or opinions that might be expressed in the paper do not necessarily represent the views of the USDOE or the US Government.

Conflict of Interest

The authors declare no competing financial interest.
 

 

Additional Information

Published as part of The Journal of Physical Chemistry virtual special issue "Marsha I. Lester Festschrift".

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Additional details

Identifiers

ISSN
1520-5215
DOI
10.1021/acs.jpca.3c04648

Related works

Is supplemented by
https://pubs.acs.org/doi/suppl/10.1021/acs.jpca.3c04648/suppl_file/jp3c04648_si_001.pdf (URL)

Funding

National Science Foundation
CHE-1955068
United States Department of Energy
DE-FG02-87ER13792
National Science Foundation
ACI-1548562
National Science Foundation
TG-CHE190088
National Science Foundation
CHE-2102626
United States Department of Energy
DE-AC02-06CH11357
United States Department of Energy
DE-NA0003525
United States Department of Energy
DE-AC02-05CH11231
Arnold and Mabel Beckman Foundation
National Aeronautics and Space Administration