Title: Direct kinetics study of CH₂OO + methyl vinyl ketone and CH₂OO + methacrolein reactions and an upper limit determination for CH₂OO + CO reaction

Abstract

Methyl vinyl ketone (MVK) and methacrolein (MACR) are important intermediate products in atmospheric degradation of volatile organic compounds, especially of isoprene. Here, this work investigates the reactions of the smallest Criegee intermediate, CH₂OO, with its co-products from isoprene ozonolysis, MVK and MACR, using multiplexed photoionization mass spectrometry (MPIMS), with either tunable synchrotron radiation from the Advanced Light Source or Lyman-α (10.2 eV) radiation for photoionization. CH₂OO was produced via pulsed laser photolysis of CH₂I₂ in the presence of excess O₂. Time-resolved measurements of reactant disappearance and of product formation were performed to monitor reaction progress; first order rate coefficients were obtained from exponential fits to the CH₂OO decays. The bimolecular reaction rate coefficients at 300 K and 4 Torr are k(CH₂OO + MVK) = (5.0 ± 0.4) × 10^-13 cm³ s^-1 and k(CH₂OO + MACR) = (4.4 ± 1.0) × 10^-13 cm³ s^-1, where the stated ±2σ uncertainties are statistical uncertainties. Adduct formation is observed for both reactions and is attributed to the formation of a secondary ozonides (1,2,4-trioxolanes), supported by master equation calculations of the kinetics and the agreement between measured and calculated adiabatic ionization energies. Kinetics measurements were also performed for a possible bimolecular CH₂OO + CO reactionmore » and for the reaction of CH₂OO with CF₃CHCH₂ at 300 K and 4 Torr. For CH₂OO + CO, no reaction is observed and an upper limit is determined: k(CH₂OO + CO) < 2 × 10^-16 cm³ s^-1. Lastly, for CH₂OO + CF₃CHCH₂, an upper limit of k(CH₂OO + CF₃CHCH₂) < 2 × 10^-14 cm³ s^-1 is obtained.« less

Authors:

Eskola, Arkke J.  ^[1];

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• Search DOE PAGES for ORCID "0000-0002-2249-2726"

Döntgen, Malte  ^[2];

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• Search DOE PAGES for ORCID "0000-0002-0915-8096"

Rotavera, Brandon  ^[3];

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• Search DOE PAGES for ORCID "0000-0003-0533-7131"

Caravan, Rebecca L.  ^[3];

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• Search DOE PAGES for ORCID "0000-0002-2936-7952"

Welz, Oliver  ^[3];

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• Search DOE PAGES for ORCID "0000-0003-1978-2412"

Savee, John D. ^[3]; Osborn, David L.  ^[3];

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• Search DOE PAGES for ORCID "0000-0003-4304-8218"

Shallcross, Dudley E. ^[4]; Percival, Carl J.  ^[5];

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• Search DOE PAGES for ORCID "0000-0003-2525-160X"

Taatjes, Craig A.  ^[3]

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• Search DOE PAGES for ORCID "0000-0002-9271-0282"

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+ Show Author Affiliations

1. Sandia National Lab. (SNL-CA), Livermore, CA (United States); Univ. of Helsinki (Finland)
2. Univ. of Helsinki (Finland)
3. Sandia National Lab. (SNL-CA), Livermore, CA (United States)
4. The University of Bristol, Cantock's Close (United Kingdom)
5. Univ. of Manchester (United Kingdom)

Publication Date:

Tue Jul 03 00:00:00 EDT 2018

Research Org.:

Sandia National Lab. (SNL-CA), Livermore, CA (United States)

Sponsoring Org.:

USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE National Nuclear Security Administration (NNSA)

OSTI Identifier:

1496987

Alternate Identifier(s):

OSTI ID: 1460007

Report Number(s):

SAND-2019-1626J
Journal ID: ISSN 1463-9076; PPCPFQ; 672573

Grant/Contract Number:  

AC04-94AL85000; AC02-05CH11231; NA0003525

Resource Type:

Accepted Manuscript

Journal Name:

Physical Chemistry Chemical Physics. PCCP

Additional Journal Information:

Journal Volume: 20; Journal Issue: 29; Journal ID: ISSN 1463-9076

Publisher:

Royal Society of Chemistry

Country of Publication:

United States

Language:

English

Subject:

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY