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Title: Formation of Organic Acids and Carbonyl Compounds in n ‐Butane Oxidation via γ‐Ketohydroperoxide Decomposition

Journal Article · · Angewandte Chemie
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3];  [4];  [5]; ORCiD logo [6]; ORCiD logo [7];  [8]; ORCiD logo [8]; ORCiD logo [9]; ORCiD logo [9]; ORCiD logo [10];  [8]; ORCiD logo [8];  [4]; ORCiD logo [8]
  1. Department of Chemistry and Physics University of California, Berkeley Berkeley CA 94720 USA, Department of Chemistry University of Central Florida Orlando FL 32816 USA
  2. Combustion Research Facility Sandia National Laboratories Livermore CA 94551 USA, Department of Chemistry University of Helsinki 00014 Helsinki Finland
  3. Combustion Research Facility Sandia National Laboratories Livermore CA 94551 USA, Department of Chemistry and College of Engineering University of Georgia Athens GA 30602 USA
  4. Department of Chemistry and Physics University of California, Berkeley Berkeley CA 94720 USA
  5. 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
  6. King Abdullah University of Science and Technology (KAUST) Clean Combustion Research Center (CCRC) Thuwal 23955-6900 Saudi Arabia
  7. Combustion Research Facility Sandia National Laboratories Livermore CA 94551 USA, Chemical Sciences and Engineering Division Argonne National Laboratory Lemont IL 60439 USA
  8. Combustion Research Facility Sandia National Laboratories Livermore CA 94551 USA
  9. Combustion Research Facility Sandia National Laboratories Livermore CA 94551 USA, Physikalisch-Technische Bundesanstalt 38116 Braunschweig Germany
  10. 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

References (38)

Determination of organic acids (C1-C10) in the atmosphere, motor exhausts, and engine oils journal November 1985
Experimental Confirmation of the Low-Temperature Oxidation Scheme of Alkanes journal April 2010
Isomeric hexyl-ketohydroperoxides formed by reactions of hexoxy and hexylperoxy radicals in oxygen journal January 2003
The multiplexed chemical kinetic photoionization mass spectrometer: A new approach to isomer-resolved chemical kinetics journal October 2008
New Pathways for Formation of Acids and Carbonyl Products in Low-Temperature Oxidation: The Korcek Decomposition of γ-Ketohydroperoxides journal July 2013
Synchrotron Photoionization Mass Spectrometry Measurements of Product Formation in Low-Temperature n -Butane Oxidation: Toward a Fundamental Understanding of Autoignition Chemistry and n -C 4 H 9 + O 2 / s -C 4 H 9 + O 2 Reactions journal November 2013
Advances and challenges in laminar flame experiments and implications for combustion chemistry journal August 2014
Probing the low-temperature chain-branching mechanism of n -butane autoignition chemistry via time-resolved measurements of ketohydroperoxide formation in photolytically initiated n- C 4 H 10 oxidation journal January 2015
Exploring hydroperoxides in combustion: History, recent advances and perspectives journal July 2019
Emission of specific pollutants from a compression ignition engine. Influence of fuel hydrotreatment and fuel/air equivalence ratio journal January 2001
Quantitative Detection of Products and Radical Intermediates in Low-Temperature Oxidation of Cyclopentane journal May 2021
An experimental and chemical kinetic modeling study of 1,3-butadiene combustion: Ignition delay time and laminar flame speed measurements journal November 2018
Detection and Identification of the Keto-Hydroperoxide (HOOCH 2 OCHO) and Other Intermediates during Low-Temperature Oxidation of Dimethyl Ether journal February 2015
New reaction classes in the kinetic modeling of low temperature oxidation of n-alkanes journal May 2015
Recent contributions of flame-sampling molecular-beam mass spectrometry to a fundamental understanding of combustion chemistry journal April 2009
A jet-stirred reactor for kinetic studies of homogeneous gas-phase reactions at pressures up to ten atmospheres (≈1 MPa) journal March 1986
Research needs for future internal combustion engines journal November 2008
Products from the Oxidation of Linear Isomers of Hexene journal January 2014
Fuel chemistry and cetane effects on diesel homogeneous charge compression ignition performance, combustion, and emissions journal February 2007
Influence of the Ether Functional Group on Ketohydroperoxide Formation in Cyclic Hydrocarbons: Tetrahydropyran and Cyclohexane journal March 2019
C 1 −C 5 Organic Acid Emissions from an SI Engine:  Influence of Fuel and Air/Fuel Equivalence Ratio journal July 2001
Near-threshold absolute photoionization cross-sections of some reaction intermediates in combustion journal February 2008
Liquid-phase autoxidation of organic compounds at elevated temperatures. 2. Kinetics and mechanisms of the formation of cleavage products in n-hexadecane autoxidation journal April 1981
An experimental and modelling study of n-pentane oxidation in two jet-stirred reactors: The importance of pressure-dependent kinetics and new reaction pathways journal January 2017
Kinetics of elementary reactions in low-temperature autoignition chemistry journal August 2011
Improved Kinetic Model of the Low-Temperature Oxidation of n -Heptane journal October 2014
Initiation in hydrocarbon autoxidation at elevated temperatures journal October 1990
Hydroperoxides with zero, one, two or more carbonyl groups formed during the oxidation of n-dodecane journal July 2001
Effect of non-thermal product energy distributions on ketohydroperoxide decomposition kinetics journal January 2015
Pressure-Dependent Competition among Reaction Pathways from First- and Second-O 2 Additions in the Low-Temperature Oxidation of Tetrahydrofuran journal August 2016
Liquid-phase autoxidation of organic compounds at elevated temperatures. 1. The stirred flow reactor technique and analysis of primary products from n-hexadecane autoxidation at 120-180.degree.C journal December 1979
Experimental Confirmation of the Low-Temperature Oxidation Scheme of Alkanes journal April 2010
Identification of the hydroperoxide formed by isomerization reactions during the oxidation of n-heptane in a reactor and CFR engine journal June 1991
Detailed product analysis during the low temperature oxidation of n-butane journal January 2011
Performance of the vacuum ultraviolet high-resolution and high-flux beamline for chemical dynamics studies at the Advanced Light Source journal May 1997
Kinetics and mechanism of the autoxidation of pentaerythrityl tetraheptanoate at 180-220°C: AUTOXIDATION OF PETH journal September 1980
Photoionization cross sections for reaction intermediates in hydrocarbon combustion journal December 2005
Chemical dynamics, molecular energetics, and kinetics at the synchrotron journal January 2010

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