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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:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [3]; ORCiD logo [3];  [3]; ORCiD logo [3];  [4]; ORCiD logo [5]; ORCiD logo [3]
  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:
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 (Print)
Additional Journal Information:
Journal Name: Physical Chemistry Chemical Physics. PCCP (Print); 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

Citation Formats

Eskola, Arkke J., Döntgen, Malte, Rotavera, Brandon, Caravan, Rebecca L., Welz, Oliver, Savee, John D., Osborn, David L., Shallcross, Dudley E., Percival, Carl J., and Taatjes, Craig A. Direct kinetics study of CH2OO + methyl vinyl ketone and CH2OO + methacrolein reactions and an upper limit determination for CH2OO + CO reaction. United States: N. p., 2018. Web. doi:10.1039/C8CP03606C.
Eskola, Arkke J., Döntgen, Malte, Rotavera, Brandon, Caravan, Rebecca L., Welz, Oliver, Savee, John D., Osborn, David L., Shallcross, Dudley E., Percival, Carl J., & Taatjes, Craig A. Direct kinetics study of CH2OO + methyl vinyl ketone and CH2OO + methacrolein reactions and an upper limit determination for CH2OO + CO reaction. United States. doi:https://doi.org/10.1039/C8CP03606C
Eskola, Arkke J., Döntgen, Malte, Rotavera, Brandon, Caravan, Rebecca L., Welz, Oliver, Savee, John D., Osborn, David L., Shallcross, Dudley E., Percival, Carl J., and Taatjes, Craig A. Tue . "Direct kinetics study of CH2OO + methyl vinyl ketone and CH2OO + methacrolein reactions and an upper limit determination for CH2OO + CO reaction". United States. doi:https://doi.org/10.1039/C8CP03606C. https://www.osti.gov/servlets/purl/1496987.
@article{osti_1496987,
title = {Direct kinetics study of CH2OO + methyl vinyl ketone and CH2OO + methacrolein reactions and an upper limit determination for CH2OO + CO reaction},
author = {Eskola, Arkke J. and Döntgen, Malte and Rotavera, Brandon and Caravan, Rebecca L. and Welz, Oliver and Savee, John D. and Osborn, David L. and Shallcross, Dudley E. and Percival, Carl J. and Taatjes, Craig A.},
abstractNote = {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 reaction 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.},
doi = {10.1039/C8CP03606C},
journal = {Physical Chemistry Chemical Physics. PCCP (Print)},
number = 29,
volume = 20,
place = {United States},
year = {2018},
month = {7}
}

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    Works referencing / citing this record:

    Theoretical investigation on the reaction mechanism and kinetics of a Criegee intermediate with ethylene and acetylene
    journal, January 2019

    • Sun, Cuihong; Xu, Baoen; Lv, Liqiang
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