Formation of Organic Acids and Carbonyl Compounds in n ‐Butane Oxidation via γ‐Ketohydroperoxide Decomposition
- Department of Chemistry and Physics University of California, Berkeley Berkeley CA 94720 USA, Department of Chemistry University of Central Florida Orlando FL 32816 USA
- Combustion Research Facility Sandia National Laboratories Livermore CA 94551 USA, Department of Chemistry University of Helsinki 00014 Helsinki Finland
- Combustion Research Facility Sandia National Laboratories Livermore CA 94551 USA, Department of Chemistry and College of Engineering University of Georgia Athens GA 30602 USA
- Department of Chemistry and Physics University of California, Berkeley Berkeley CA 94720 USA
- King Abdullah University of Science and Technology (KAUST) Clean Combustion Research Center (CCRC) Thuwal 23955-6900 Saudi Arabia, National Synchrotron Radiation Laboratory University of Science and Technology of China Hefei Anhui 230029 P. R. China
- King Abdullah University of Science and Technology (KAUST) Clean Combustion Research Center (CCRC) Thuwal 23955-6900 Saudi Arabia
- Combustion Research Facility Sandia National Laboratories Livermore CA 94551 USA, Chemical Sciences and Engineering Division Argonne National Laboratory Lemont IL 60439 USA
- Combustion Research Facility Sandia National Laboratories Livermore CA 94551 USA
- Combustion Research Facility Sandia National Laboratories Livermore CA 94551 USA, Physikalisch-Technische Bundesanstalt 38116 Braunschweig Germany
- Centre National de la Recherche Scientifique (CNRS) INSIS ICARE 45071 Orléans Cedex 2 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.
- Sponsoring Organization:
- USDOE
- OSTI ID:
- 1891654
- Journal Information:
- Angewandte Chemie, Journal Name: Angewandte Chemie Vol. 134 Journal Issue: 42; ISSN 0044-8249
- Publisher:
- Wiley Blackwell (John Wiley & Sons)Copyright Statement
- Country of Publication:
- Germany
- Language:
- English
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