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

Abstract

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 proposedmore » 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.« less

Authors:
 [1];  [2];  [3];  [4];  [1];  [5];  [6];  [3];  [4];  [6];  [3];  [7];  [1]
+ Show Author Affiliations
  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)
Publication Date:
Research Org.:
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE National Nuclear Security Administration (NNSA)
OSTI Identifier:
1262238
Alternate Identifier(s):
OSTI ID: 1249639; OSTI ID: 1379063
Report Number(s):
SAND-2016-6268J
Journal ID: ISSN 0010-2180; PII: S0010218015004459
Grant/Contract Number:  
AC04-94AL85000; DEAC02-05CH11231; AC04-94-AL85000; AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Combustion and Flame
Additional Journal Information:
Journal Volume: 164; Journal Issue: C; Journal ID: ISSN 0010-2180
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; auto-oxidation; chain-branching; highly oxidized multifunctional molecules; peroxides; alternative isomerization; synchrotron VUV photoionization mass spectrometry

Citation Formats

Wang, Zhandong, Zhang, Lidong, Moshammer, Kai, Popolan-Vaida, Denisia M., Shankar, Vijai Shankar Bhavani, Lucassen, Arnas, Hemken, Christian, Taatjes, Craig A., Leone, Stephen R., Kohse-Hoinghaus, Katharina, Hansen, Nils, Dagaut, Philippe, and Sarathy, S. Mani. Additional chain-branching pathways in the low-temperature oxidation of branched alkanes. United States: N. p., 2015. Web. doi:10.1016/j.combustflame.2015.11.035.
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Wang, Zhandong, Zhang, Lidong, Moshammer, Kai, Popolan-Vaida, Denisia M., Shankar, Vijai Shankar Bhavani, Lucassen, Arnas, Hemken, Christian, Taatjes, Craig A., Leone, Stephen R., Kohse-Hoinghaus, Katharina, Hansen, Nils, Dagaut, Philippe, & Sarathy, S. Mani. Additional chain-branching pathways in the low-temperature oxidation of branched alkanes. United States. https://doi.org/10.1016/j.combustflame.2015.11.035
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Wang, Zhandong, Zhang, Lidong, Moshammer, Kai, Popolan-Vaida, Denisia M., Shankar, Vijai Shankar Bhavani, Lucassen, Arnas, Hemken, Christian, Taatjes, Craig A., Leone, Stephen R., Kohse-Hoinghaus, Katharina, Hansen, Nils, Dagaut, Philippe, and Sarathy, S. Mani. Thu . "Additional chain-branching pathways in the low-temperature oxidation of branched alkanes". United States. https://doi.org/10.1016/j.combustflame.2015.11.035. https://www.osti.gov/servlets/purl/1262238.
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@article{osti_1262238,
title = {Additional chain-branching pathways in the low-temperature oxidation of branched alkanes},
author = {Wang, Zhandong and Zhang, Lidong and Moshammer, Kai and Popolan-Vaida, Denisia M. and Shankar, Vijai Shankar Bhavani and Lucassen, Arnas and Hemken, Christian and Taatjes, Craig A. and Leone, Stephen R. and Kohse-Hoinghaus, Katharina and Hansen, Nils and Dagaut, Philippe and Sarathy, S. Mani},
abstractNote = {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.},
doi = {10.1016/j.combustflame.2015.11.035},
journal = {Combustion and Flame},
number = C,
volume = 164,
place = {United States},
year = {2015},
month = {12}
}
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