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Title: Additional chain-branching pathways in the low-temperature oxidation of branched alkanes

Journal Article · · Combustion and Flame
 [1];  [2];  [3];  [4];  [1];  [5];  [6];  [3];  [4];  [6];  [3];  [7];  [1]
  1. King Abdullah Univ. of Science and Technology, Thuwal (Saudi Arabia)
  2. Univ. of Science and Technology of China, Anhui (People's Republic of China)
  3. Sandia National Lab. (SNL-CA), Livermore, CA (United States)
  4. Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  5. Physikalisch-Technische Bundesanstalt, Braunschweig (Germany)
  6. Bielefeld Univ., Bielefeld (Germany)
  7. CNRS, INSIS, Orleans Cedex (France)
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Chain-branching reactions represent a general motif in chemistry, encountered in atmospheric chemistry, combustion, polymerization, and photochemistry; the nature and amount of radicals generated by chain-branching are decisive for the reaction progress, its energy signature, and the time towards its completion. In this study, experimental evidence for two new types of chain-branching reactions is presented, based upon detection of highly oxidized multifunctional molecules (HOM) formed during the gas-phase low-temperature oxidation of a branched alkane under conditions relevant to combustion. The oxidation of 2,5-dimethylhexane (DMH) in a jet-stirred reactor (JSR) was studied using synchrotron vacuum ultra-violet photoionization molecular beam mass spectrometry (SVUV-PI-MBMS). Specifically, species with four and five oxygen atoms were probed, having molecular formulas of C 8 H 14 O 4 (e.g., diketo-hydroperoxide/keto-hydroperoxy cyclic ether) and C 8 H 16 O 5 (e.g., keto-dihydroperoxide/dihydroperoxy cyclic ether), respectively. The formation of C 8 H 16 O 5 species involves alternative isomerization of OOQOOH radicals via intramolecular H-atom migration, followed by third O 2 addition, intramolecular isomerization, and OH release; C 8 H 14 O 4 species are proposed to result from subsequent reactions of C 8 H 16 O 5 species. The mechanistic pathways involving these species are related to those proposed as a source of low-volatility highly oxygenated species in Earth's troposphere. At the higher temperatures relevant to auto-ignition, they can result in a net increase of hydroxyl radical production, so these are additional radical chain-branching pathways for ignition. The results presented herein extend the conceptual basis of reaction mechanisms used to predict the reaction behavior of ignition, and have implications on atmospheric gas-phase chemistry and the oxidative stability of organic substances.

Research Organization:
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE National Nuclear Security Administration (NNSA)
Grant/Contract Number:
AC04-94AL85000; DEAC02-05CH11231; AC04-94-AL85000; AC02-05CH11231
OSTI ID:
1262238
Alternate ID(s):
OSTI ID: 1249639; OSTI ID: 1379063
Report Number(s):
SAND-2016-6268J; PII: S0010218015004459
Journal Information:
Combustion and Flame, Vol. 164, Issue C; ISSN 0010-2180
Publisher:
ElsevierCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 89 works
Citation information provided by
Web of Science

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The fate of the tert-butyl radical in low-temperature autoignition reactions journal May 2017
Mechanisms and kinetics of the low-temperature oxidation of 2-methylfuran: insight from DFT calculations and kinetic simulations journal January 2020

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
auto-oxidation
chain-branching
highly oxidized multifunctional molecules
peroxides
alternative isomerization
synchrotron VUV photoionization mass spectrometry