Formation of Organic Acids and Carbonyl Compounds in $\textit{n}$-Butane Oxidation via γ-Ketohydroperoxide Decomposition

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

doi:10.1002/anie.202209168

Title: Formation of Organic Acids and Carbonyl Compounds in $$\textit{n}$$-Butane Oxidation via γ-Ketohydroperoxide Decomposition

Journal Article · Wed Jul 27 00:00:00 EDT 2022 · Angewandte Chemie (International Edition)

DOI:https://doi.org/10.1002/anie.202209168· OSTI ID:1922054

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^[3]; Lockyear, Jessica F. ^[4]; Wang, Zhandong ^[5];

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^[7]; Zádor, Judit ^[8];

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^[10]; Osborn, David L. ^[8];

^[8]; Leone, Stephen R. ^[4];

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Univ. of California, Berkeley, CA (United States); Univ. of Central Florida, Orlando, FL (United States)
Sandia National Lab. (SNL-CA), Livermore, CA (United States); Univ. of Helsinki (Finland)
Sandia National Lab. (SNL-CA), Livermore, CA (United States); Univ. of Georgia, Athens, GA (United States)
Univ. of California, Berkeley, CA (United States)
King Abdullah University of Science and Technology (KAUST), Thuwal (Saudi Arabia); University of Science and Technology of China Hefei (China)
King Abdullah University of Science and Technology (KAUST), Thuwal (Saudi Arabia)
Sandia National Lab. (SNL-CA), Livermore, CA (United States); Argonne National Lab. (ANL), Lemont, IL (United States)
Sandia National Lab. (SNL-CA), Livermore, CA (United States)
Sandia National Lab. (SNL-CA), Livermore, CA (United States); Physikalisch-Technische Bundesanstalt, Braunschweig (Germany)
Centre National de la Recherche Scientifique (CNRS) (France)

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.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: European Research Council (ERC); King Abdullah University of Science and Technology (KAUST); USDOE National Nuclear Security Administration (NNSA); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: AC02-06CH11357; AC02-05CH11231; NA0003525; 291049-2G-CSafe

OSTI ID:: 1922054

Alternate ID(s):: OSTI ID: 1891688

Journal Information:: Angewandte Chemie (International Edition), Vol. 61, Issue 42; ISSN 1433-7851

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

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Title: Formation of Organic Acids and Carbonyl Compounds in $$\textit{n}$$-Butane Oxidation via γ-Ketohydroperoxide Decomposition

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