Direct kinetic measurements and theoretical predictions of an isoprene-derived Criegee intermediate
Abstract
Isoprene has the highest emission into Earth’s atmosphere of any nonmethane hydrocarbon. Atmospheric processing of alkenes, including isoprene, via ozonolysis leads to the formation of zwitterionic reactive intermediates, known as Criegee intermediates (CIs). Direct studies have revealed that reactions involving simple CIs can significantly impact the tropospheric oxidizing capacity, enhance particulate formation, and degrade local air quality. Methyl vinyl ketone oxide (MVK-oxide) is a four-carbon, asymmetric, resonance-stabilized CI, produced with 21 to 23% yield from isoprene ozonolysis, yet its reactivity has not been directly studied. We present direct kinetic measurements of MVK-oxide reactions with key atmospheric species using absorption spectroscopy. Direct UV-Vis absorption spectra from two independent flow cell experiments overlap with the molecular beam UV-Vis-depletion spectra reported recently [M. F. Vansco, B. Marchetti, M. I. Lester, J. Chem. Phys. 149, 44309 (2018)] but suggest different conformer distributions under jet-cooled and thermal conditions. Comparison of the experimental lifetime herein with theory indicates only the syn-conformers are observed; anti-conformers are calculated to be removed much more rapidly via unimolecular decay. We observe experimentally and predict theoretically fast reaction of syn-MVK-oxide with SO2 and formic acid, similar to smaller alkyl-substituted CIs, and by contrast, slow removal in the presence of water. Wemore »
- Authors:
- Publication Date:
- Research Org.:
- Univ. of Pennsylvania, Philadelphia, PA (United States); Argonne National Laboratory (ANL), Argonne, IL (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division; USDOE National Nuclear Security Administration (NNSA); National Science Foundation (NSF); Academia Sinica and Ministry of Science and Technology
- OSTI Identifier:
- 1615850
- Alternate Identifier(s):
- OSTI ID: 1632275; OSTI ID: 1633328; OSTI ID: 1782234
- Grant/Contract Number:
- FG02-87ER13792; NA0003525; AC02-06CH11357; AC02-05CH11231
- Resource Type:
- Published Article
- Journal Name:
- Proceedings of the National Academy of Sciences of the United States of America
- Additional Journal Information:
- Journal Name: Proceedings of the National Academy of Sciences of the United States of America Journal Volume: 117 Journal Issue: 18; Journal ID: ISSN 0027-8424
- Publisher:
- National Academy of Sciences
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 09 BIOMASS FUELS; Criegee intermediates; ab initio calculations; atmospheric chemistry; chemical kinetics; Computational kinetics; Unimolecular decay; Spectroscopy; Global chemical modelling
Citation Formats
Caravan, Rebecca L., Vansco, Michael F., Au, Kendrew, Khan, M. Anwar H., Li, Yu-Lin, Winiberg, Frank A. F., Zuraski, Kristen, Lin, Yen-Hsiu, Chao, Wen, Trongsiriwat, Nisalak, Walsh, Patrick J., Osborn, David L., Percival, Carl J., Lin, Jim Jr-Min, Shallcross, Dudley E., Sheps, Leonid, Klippenstein, Stephen J., Taatjes, Craig A., and Lester, Marsha I. Direct kinetic measurements and theoretical predictions of an isoprene-derived Criegee intermediate. United States: N. p., 2020.
Web. doi:10.1073/pnas.1916711117.
Caravan, Rebecca L., Vansco, Michael F., Au, Kendrew, Khan, M. Anwar H., Li, Yu-Lin, Winiberg, Frank A. F., Zuraski, Kristen, Lin, Yen-Hsiu, Chao, Wen, Trongsiriwat, Nisalak, Walsh, Patrick J., Osborn, David L., Percival, Carl J., Lin, Jim Jr-Min, Shallcross, Dudley E., Sheps, Leonid, Klippenstein, Stephen J., Taatjes, Craig A., & Lester, Marsha I. Direct kinetic measurements and theoretical predictions of an isoprene-derived Criegee intermediate. United States. https://doi.org/10.1073/pnas.1916711117
Caravan, Rebecca L., Vansco, Michael F., Au, Kendrew, Khan, M. Anwar H., Li, Yu-Lin, Winiberg, Frank A. F., Zuraski, Kristen, Lin, Yen-Hsiu, Chao, Wen, Trongsiriwat, Nisalak, Walsh, Patrick J., Osborn, David L., Percival, Carl J., Lin, Jim Jr-Min, Shallcross, Dudley E., Sheps, Leonid, Klippenstein, Stephen J., Taatjes, Craig A., and Lester, Marsha I. Wed .
"Direct kinetic measurements and theoretical predictions of an isoprene-derived Criegee intermediate". United States. https://doi.org/10.1073/pnas.1916711117.
@article{osti_1615850,
title = {Direct kinetic measurements and theoretical predictions of an isoprene-derived Criegee intermediate},
author = {Caravan, Rebecca L. and Vansco, Michael F. and Au, Kendrew and Khan, M. Anwar H. and Li, Yu-Lin and Winiberg, Frank A. F. and Zuraski, Kristen and Lin, Yen-Hsiu and Chao, Wen and Trongsiriwat, Nisalak and Walsh, Patrick J. and Osborn, David L. and Percival, Carl J. and Lin, Jim Jr-Min and Shallcross, Dudley E. and Sheps, Leonid and Klippenstein, Stephen J. and Taatjes, Craig A. and Lester, Marsha I.},
abstractNote = {Isoprene has the highest emission into Earth’s atmosphere of any nonmethane hydrocarbon. Atmospheric processing of alkenes, including isoprene, via ozonolysis leads to the formation of zwitterionic reactive intermediates, known as Criegee intermediates (CIs). Direct studies have revealed that reactions involving simple CIs can significantly impact the tropospheric oxidizing capacity, enhance particulate formation, and degrade local air quality. Methyl vinyl ketone oxide (MVK-oxide) is a four-carbon, asymmetric, resonance-stabilized CI, produced with 21 to 23% yield from isoprene ozonolysis, yet its reactivity has not been directly studied. We present direct kinetic measurements of MVK-oxide reactions with key atmospheric species using absorption spectroscopy. Direct UV-Vis absorption spectra from two independent flow cell experiments overlap with the molecular beam UV-Vis-depletion spectra reported recently [M. F. Vansco, B. Marchetti, M. I. Lester, J. Chem. Phys. 149, 44309 (2018)] but suggest different conformer distributions under jet-cooled and thermal conditions. Comparison of the experimental lifetime herein with theory indicates only the syn-conformers are observed; anti-conformers are calculated to be removed much more rapidly via unimolecular decay. We observe experimentally and predict theoretically fast reaction of syn-MVK-oxide with SO2 and formic acid, similar to smaller alkyl-substituted CIs, and by contrast, slow removal in the presence of water. We determine products through complementary multiplexed photoionization mass spectrometry, observing SO3 and identifying organic hydroperoxide formation from reaction with SO2 and formic acid, respectively. The tropospheric implications of these reactions are evaluated using a global chemistry and transport model.},
doi = {10.1073/pnas.1916711117},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
number = 18,
volume = 117,
place = {United States},
year = {Wed Apr 22 00:00:00 EDT 2020},
month = {Wed Apr 22 00:00:00 EDT 2020}
}
https://doi.org/10.1073/pnas.1916711117
Web of Science
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