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

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.

doi:10.1021/acs.jpca.3c04648

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

Journal Article · Mon Oct 23 00:00:00 EDT 2023 · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory

DOI:https://doi.org/10.1021/acs.jpca.3c04648· OSTI ID:2311366

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Univ. of Pennsylvania, Philadelphia, PA (United States)
Argonne National Laboratory (ANL), Argonne, IL (United States)
California Institute of Technology (CalTech), Pasadena, CA (United States). Jet Propulsion Lab. (JPL)
Sandia National Lab. (SNL-CA), Livermore, CA (United States)
Sandia National Lab. (SNL-CA), Livermore, CA (United States). Combustion Research Facility
Sandia National Lab. (SNL-CA), Livermore, CA (United States). Combustion Research Facility; Univ. of California, Davis, CA (United States)

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 (k_syn = 4.42 × 10¹¹ T^–7.80exp(-1401/T) cm³ s^–1 and k_anti = 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.

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Research Organization:: 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 Organization:: 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)

Grant/Contract Number:: NA0003525; FG02-87ER13792; AC02-06CH11357; AC02-05CH11231; CHE-1955068; ACI-1548562; CHE-2102626

OSTI ID:: 2311366

Report Number(s):: SAND-2023-13335J

Journal Information:: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Vol. 127, Issue 43; ISSN 1089-5639

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Chemical calculations
Energy
Kinetics
Molecular structure
Photoionization

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

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