Formation of Organic Acids and Carbonyl Compounds in n-Butane Oxidation via γ-Ketohydroperoxide Decomposition

Denisia Maria Popolan-Vaida; Arkke J. Eskola; Brandon Rotavera; Jessica F. Lockyear; Zhandong Wang; Mani Sarathy; Rebecca L. Caravan; Judit Zádor; Leonid Sheps; Arnas Lucassen; Kai Moshammer; Philippe Dagaut; David L. Osborn; Nils Hansen; Stephen R. Leone; Craig A. Taatjes

doi:10.1002/ange.202209168

Formation of Organic Acids and Carbonyl Compounds in n-Butane Oxidation via γ-Ketohydroperoxide Decomposition

Denisia Maria Popolan-Vaida, Arkke J. Eskola, Brandon Rotavera, Jessica F. Lockyear, Zhandong Wang, Mani Sarathy, Rebecca L. Caravan, Judit Zádor, Leonid Sheps, Arnas Lucassen, Kai Moshammer, Philippe Dagaut, David L. Osborn, Nils Hansen, Stephen R. Leone, Craig A. Taatjes

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Abstract

A crucial chain-branching step in autoignition is the decomposition of ketohydroperoxides (KHP) to form an oxy radical and OH. Other pathways compete with chain-branching, such as “Korcek” dissociation of γ-KHP to a carbonyl and an acid. Here we characterize the formation of a γ-KHP and its decomposition to formic acid + acetone products from observations of n ‑butane oxidation in two complementary experiments. In jet-stirred reactor measurements, KHP is observed above 590 K. The KHP concentration decreases with increasing temperature, whereas formic acid and acetone products increase. Observation of characteristic isotopologs acetone‑ d 3 and formic acid- d 0 in the oxidation of CH 3 CD 2 CD 2 CH 3 is consistent with a Korcek mechanism. In laser-initiated oxidation experiments of n -butane, formic acid and acetone are produced on the timescale of KHP removal. Modelling the time-resolved production of formic acid provides an estimated upper limit of 2 s ‑1 for the rate coefficient of KHP decomposition to formic acid + acetone.

Original language	English (US)
Journal	Angewandte Chemie
DOIs	https://doi.org/10.1002/ange.202209168 https://doi.org/10.1002/anie.202209168
State	Published - Jul 27 2022

Bibliographical note

KAUST Repository Item: Exported on 2022-09-14
Acknowledgements: This material is based upon work supported by the U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences. The Lawrence Berkeley National Laboratory researchers were supported under contract no. DE-AC02-05CH11231, the gas phase chemical physics program through the Chemical Sciences Division of Lawrence Berkeley National Laboratory.Sandia National Laboratories is a multi-mission laboratory managed and operated by National Technology and Engineering Solutions of Sandia, LLC, a wholly owned subsidiary of Honeywell International, Inc., for the USDOE’s National Nuclear Security Administration under contract DE-NA0003525. This paper describes objective technical results and analysis. Any subjective views or opinions that might be expressed in the paper do not necessarily represent the views of the USDOE or the United States Government. L.S. was supported as part of the Argonne-Sandia Consortium in High-Pressure Combustion Chemistry. The KAUST researchers were supported by competitive research funding from the King Abdullah University of Science and Technology. Argonne National Laboratory is supported by the USDOE, Office of Science, BES, Division of Chemical Sciences, Geosciences, and Biosciences under contract no. DE-AC02-06CH11357.D.M.P.-V. acknowledges financial support provided by the UCF through the Seed Funding Programand the technical support by James Breen, Erik Granlund, and William Thur during the designing and fabrication of the JSR system. P. D. has received funding from the European Research Council under the European Community’s Seventh Framework Programme (FP7/2007-2013)/ERC grant agreement No. 291049-2G-CSafe.

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General Medicine

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Popolan-Vaida, D. M., Eskola, A. J., Rotavera, B., Lockyear, J. F., Wang, Z., Sarathy, M., Caravan, R. L., Zádor, J., Sheps, L., Lucassen, A., Moshammer, K., Dagaut, P., Osborn, D. L., Hansen, N., Leone, S. R., & Taatjes, C. A. (2022). Formation of Organic Acids and Carbonyl Compounds in n-Butane Oxidation via γ-Ketohydroperoxide Decomposition. Angewandte Chemie. https://doi.org/10.1002/ange.202209168, https://doi.org/10.1002/anie.202209168

@article{2701d3ab9bee41b08b949883a3137437,

title = "Formation of Organic Acids and Carbonyl Compounds in n-Butane Oxidation via γ-Ketohydroperoxide Decomposition",

abstract = "A crucial chain-branching step in autoignition is the decomposition of ketohydroperoxides (KHP) to form an oxy radical and OH. Other pathways compete with chain-branching, such as “Korcek” dissociation of γ-KHP to a carbonyl and an acid. Here we characterize the formation of a γ-KHP and its decomposition to formic acid + acetone products from observations of n ‑butane oxidation in two complementary experiments. In jet-stirred reactor measurements, KHP is observed above 590 K. The KHP concentration decreases with increasing temperature, whereas formic acid and acetone products increase. Observation of characteristic isotopologs acetone‑ d 3 and formic acid- d 0 in the oxidation of CH 3 CD 2 CD 2 CH 3 is consistent with a Korcek mechanism. In laser-initiated oxidation experiments of n -butane, formic acid and acetone are produced on the timescale of KHP removal. Modelling the time-resolved production of formic acid provides an estimated upper limit of 2 s ‑1 for the rate coefficient of KHP decomposition to formic acid + acetone.",

author = "Popolan-Vaida, {Denisia Maria} and Eskola, {Arkke J.} and Brandon Rotavera and Lockyear, {Jessica F.} and Zhandong Wang and Mani Sarathy and Caravan, {Rebecca L.} and Judit Z{\'a}dor and Leonid Sheps and Arnas Lucassen and Kai Moshammer and Philippe Dagaut and Osborn, {David L.} and Nils Hansen and Leone, {Stephen R.} and Taatjes, {Craig A.}",

note = "KAUST Repository Item: Exported on 2022-09-14 Acknowledgements: This material is based upon work supported by the U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences. The Lawrence Berkeley National Laboratory researchers were supported under contract no. DE-AC02-05CH11231, the gas phase chemical physics program through the Chemical Sciences Division of Lawrence Berkeley National Laboratory.Sandia National Laboratories is a multi-mission laboratory managed and operated by National Technology and Engineering Solutions of Sandia, LLC, a wholly owned subsidiary of Honeywell International, Inc., for the USDOE{\textquoteright}s National Nuclear Security Administration under contract DE-NA0003525. This paper describes objective technical results and analysis. Any subjective views or opinions that might be expressed in the paper do not necessarily represent the views of the USDOE or the United States Government. L.S. was supported as part of the Argonne-Sandia Consortium in High-Pressure Combustion Chemistry. The KAUST researchers were supported by competitive research funding from the King Abdullah University of Science and Technology. Argonne National Laboratory is supported by the USDOE, Office of Science, BES, Division of Chemical Sciences, Geosciences, and Biosciences under contract no. DE-AC02-06CH11357.D.M.P.-V. acknowledges financial support provided by the UCF through the Seed Funding Programand the technical support by James Breen, Erik Granlund, and William Thur during the designing and fabrication of the JSR system. P. D. has received funding from the European Research Council under the European Community{\textquoteright}s Seventh Framework Programme (FP7/2007-2013)/ERC grant agreement No. 291049-2G-CSafe.",

year = "2022",

month = jul,

day = "27",

doi = "10.1002/ange.202209168",

language = "English (US)",

journal = "Angewandte Chemie",

issn = "0044-8249",

publisher = "John Wiley and Sons Ltd",

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Popolan-Vaida, DM, Eskola, AJ, Rotavera, B, Lockyear, JF, Wang, Z, Sarathy, M, Caravan, RL, Zádor, J, Sheps, L, Lucassen, A, Moshammer, K, Dagaut, P, Osborn, DL, Hansen, N, Leone, SR & Taatjes, CA 2022, 'Formation of Organic Acids and Carbonyl Compounds in n-Butane Oxidation via γ-Ketohydroperoxide Decomposition', Angewandte Chemie. https://doi.org/10.1002/ange.202209168, https://doi.org/10.1002/anie.202209168

TY - JOUR

T1 - Formation of Organic Acids and Carbonyl Compounds in n-Butane Oxidation via γ-Ketohydroperoxide Decomposition

AU - Popolan-Vaida, Denisia Maria

AU - Eskola, Arkke J.

AU - Rotavera, Brandon

AU - Lockyear, Jessica F.

AU - Wang, Zhandong

AU - Sarathy, Mani

AU - Caravan, Rebecca L.

AU - Zádor, Judit

AU - Sheps, Leonid

AU - Lucassen, Arnas

AU - Moshammer, Kai

AU - Dagaut, Philippe

AU - Osborn, David L.

AU - Hansen, Nils

AU - Leone, Stephen R.

AU - Taatjes, Craig A.

N1 - KAUST Repository Item: Exported on 2022-09-14 Acknowledgements: This material is based upon work supported by the U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences. The Lawrence Berkeley National Laboratory researchers were supported under contract no. DE-AC02-05CH11231, the gas phase chemical physics program through the Chemical Sciences Division of Lawrence Berkeley National Laboratory.Sandia National Laboratories is a multi-mission laboratory managed and operated by National Technology and Engineering Solutions of Sandia, LLC, a wholly owned subsidiary of Honeywell International, Inc., for the USDOE’s National Nuclear Security Administration under contract DE-NA0003525. This paper describes objective technical results and analysis. Any subjective views or opinions that might be expressed in the paper do not necessarily represent the views of the USDOE or the United States Government. L.S. was supported as part of the Argonne-Sandia Consortium in High-Pressure Combustion Chemistry. The KAUST researchers were supported by competitive research funding from the King Abdullah University of Science and Technology. Argonne National Laboratory is supported by the USDOE, Office of Science, BES, Division of Chemical Sciences, Geosciences, and Biosciences under contract no. DE-AC02-06CH11357.D.M.P.-V. acknowledges financial support provided by the UCF through the Seed Funding Programand the technical support by James Breen, Erik Granlund, and William Thur during the designing and fabrication of the JSR system. P. D. has received funding from the European Research Council under the European Community’s Seventh Framework Programme (FP7/2007-2013)/ERC grant agreement No. 291049-2G-CSafe.

PY - 2022/7/27

Y1 - 2022/7/27

N2 - A crucial chain-branching step in autoignition is the decomposition of ketohydroperoxides (KHP) to form an oxy radical and OH. Other pathways compete with chain-branching, such as “Korcek” dissociation of γ-KHP to a carbonyl and an acid. Here we characterize the formation of a γ-KHP and its decomposition to formic acid + acetone products from observations of n ‑butane oxidation in two complementary experiments. In jet-stirred reactor measurements, KHP is observed above 590 K. The KHP concentration decreases with increasing temperature, whereas formic acid and acetone products increase. Observation of characteristic isotopologs acetone‑ d 3 and formic acid- d 0 in the oxidation of CH 3 CD 2 CD 2 CH 3 is consistent with a Korcek mechanism. In laser-initiated oxidation experiments of n -butane, formic acid and acetone are produced on the timescale of KHP removal. Modelling the time-resolved production of formic acid provides an estimated upper limit of 2 s ‑1 for the rate coefficient of KHP decomposition to formic acid + acetone.

AB - A crucial chain-branching step in autoignition is the decomposition of ketohydroperoxides (KHP) to form an oxy radical and OH. Other pathways compete with chain-branching, such as “Korcek” dissociation of γ-KHP to a carbonyl and an acid. Here we characterize the formation of a γ-KHP and its decomposition to formic acid + acetone products from observations of n ‑butane oxidation in two complementary experiments. In jet-stirred reactor measurements, KHP is observed above 590 K. The KHP concentration decreases with increasing temperature, whereas formic acid and acetone products increase. Observation of characteristic isotopologs acetone‑ d 3 and formic acid- d 0 in the oxidation of CH 3 CD 2 CD 2 CH 3 is consistent with a Korcek mechanism. In laser-initiated oxidation experiments of n -butane, formic acid and acetone are produced on the timescale of KHP removal. Modelling the time-resolved production of formic acid provides an estimated upper limit of 2 s ‑1 for the rate coefficient of KHP decomposition to formic acid + acetone.

UR - http://hdl.handle.net/10754/679920

UR - https://onlinelibrary.wiley.com/doi/10.1002/ange.202209168

U2 - 10.1002/ange.202209168

DO - 10.1002/ange.202209168

M3 - Article

C2 - 35895936

SN - 0044-8249

JO - Angewandte Chemie

JF - Angewandte Chemie

ER -

Formation of Organic Acids and Carbonyl Compounds in n-Butane Oxidation via γ-Ketohydroperoxide Decomposition

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