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Experimental Evidence of Dioxole Unimolecular Decay Pathway for Isoprene-Derived Criegee Intermediates

Journal Article · · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
 [1];  [2];  [3];  [3];  [4];  [5];  [5];  [6];  [3];  [7];  [7];  [4];  [5]
  1. Univ. of Pennsylvania, Philadelphia, PA (United States); University of Pennsylvania
  2. California Institute of Technology (CalTech), Pasadena, CA (United States). Jet Propulsion Lab. (JPL); Sandia National Lab. (SNL-CA), Livermore, CA (United States); Argonne National Lab. (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. Univ. of Pennsylvania, Philadelphia, PA (United States)
  6. Sandia National Lab. (SNL-CA), Livermore, CA (United States
  7. Bristol Univ. (United Kingdom)
+ Show Author Affiliations

Ozonolysis of isoprene, one of the most abundant volatile organic compounds emitted into the Earth’s atmosphere, generates two four-carbon unsaturated Criegee intermediates, methyl vinyl ketone oxide (MVK-oxide) and methacrolein oxide (MACR-oxide). The extended conjugation between the vinyl substituent and carbonyl oxide groups of these Criegee intermediates facilitates rapid electrocyclic ring closures that form 5-membered cyclic peroxides, known as dioxoles. This research discusses the first experimental evidence of this novel decay pathway, which is predicted to be the dominant atmospheric sink for specific conformational forms of MVK-oxide (anti) and MACR-oxide (syn) with the vinyl substituent adjacent to the terminal O atom. The resulting dioxoles are predicted to undergo rapid unimolecular decay to oxygenated hydrocarbon radical products, including acetyl, vinoxy, formyl, and 2-methyl-vinoxy radicals. In the presence of O2, these radicals rapidly react to form peroxy radicals (ROO), which quickly decay via carbon-centered radical intermediates (QOOH) to stable carbonyl products that are identified in this work. The carbonyl products are detected under thermal conditions (298 K, 10 torr He) using multiplexed photoionization mass spectrometry (MPIMS). The main products (and associated relative abundances) originating from unimolecular decay of anti-MVK-oxide and subsequent reaction with O2 are formaldehyde (88 ± 5%), ketene (9 ± 1%) and glyoxal (3 ± 1%). Those identified from the unimolecular decay of syn-MACR-oxide and subsequent reaction of O2 are acetaldehyde (37 ± 7%), vinyl alcohol (9 ± 1%), methylketene (2 ± 1%), and acrolein (52 ± 5%). In addition to the stable carbonyl products, the secondary peroxy chemistry also generates OH or HO2 radical co-products.

Research Organization:
Univ. of Pennsylvania, Philadelphia, PA (United States); Argonne National Laboratory (ANL), Argonne, IL (United States); Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division; USDOE National Nuclear Security Administration (NNSA); National Aeronautics and Space Administration (NASA); National Science Foundation (NSF)
Grant/Contract Number:
FG02-87ER13792; NA0003525; AC02-06CH11357; AC02-05CH11231; AC04-94AL85000
OSTI ID:
1633329
Alternate ID(s):
OSTI ID: 1644072
OSTI ID: 1660372
OSTI ID: 1782236
Journal Information:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Journal Name: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory Journal Issue: 18 Vol. 124; ISSN 1089-5639
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

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Cited By (1)

Functionalized Hydroperoxide Formation from the Reaction of Methacrolein-Oxide, an Isoprene-Derived Criegee Intermediate, with Formic Acid: Experiment and Theory journal May 2021

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