Progress in Understanding Low‐Temperature Organic Compound Oxidation Using a Jet‐Stirred Reactor

Herbinet, Olivier; Battin‐Leclerc, Frédérique

doi:10.1002/kin.20871

Cited by 87 publications

(81 citation statements)

References 102 publications

(258 reference statements)

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“…The classical low-temperature auto-oxidation reaction scheme presented in Scheme 1 has been confirmed via gas-phase measurements of the key intermediates such as hydroperoxyalkyl radicals [30], alkylhydroperoxides [31,32], large alkenes [32][33][34][35], cyclic ethers [31,34,36,37], and keto-hydroperoxides [33,35,[38][39][40][41][42]. Experiments on liquid-phase auto-oxidation by Korcek and coworkers [43][44][45][46] identified the presence of monohydroperoxides, dihydroperoxides, and keto-hydroperoxides, while recent computational studies [47,48] have shown that subsequent decomposition pathways of keto-hydroperoxides to acids are favorable.…”

Section: Introductionmentioning

confidence: 73%

“…The experiments were performed at Terminal 3 of the Chemical Dynamics Beamline of the Advanced Light Source at the Lawrence Berkeley National Laboratory, USA. The SVUV-PI-MBMS enables detection of reactive oxidation intermediates, e.g., peroxides [31,42,51]. The stoichiometric DMH (1%)/O 2 /Ar mixtures were investigated under quasi-atmospheric pressures and residence times of 0.933 bar and 2 s, respectively.…”

Section: Experimental and Theoretical Methodsmentioning

confidence: 99%

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

Wang

Zhang

Moshammer

et al. 2016

Combustion and Flame

100

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a b s t r a c tChain-branching reactions represent a general motif in chemistry, encountered in atmospheric chemistry, combustion, polymerization, and photochemistry; the nature and amount of radicals generated by chainbranching 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 ultraviolet 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/ketohydroperoxy 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.

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Section: Introductionmentioning

confidence: 73%

Section: Experimental and Theoretical Methodsmentioning

confidence: 99%

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

Wang

Zhang

Moshammer

et al. 2016

Combustion and Flame

100

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“…A heated isothermal jet-stirred reactor, already used in many organic compounds oxidation studies [16], has been connected to the three following analytical devices:…”

Section: Experimental Setup and Proceduresmentioning

confidence: 99%

Revisiting 1-hexene low-temperature oxidation

Meng

Rodriguez

Herbinet

et al. 2017

Combustion and Flame

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The low-temperature oxidation of 1-hexene has been studied in a jet-stirred reactor for temperatures from 500 to 1100 K, at atmospheric pressure, for equivalence ratios from 0.5 to 2 with a high dilution in helium. Product formation has been investigated using gas chromatography, as well as laser-singlephoton-ionization time-of-flight mass spectrometry and cw-cavity-ring down spectroscopy. These two last techniques have allowed the quantification of ketene, C1-C3 alkylhydroperoxides, hexenyl hydroperoxides, C6 unsaturated ketohydroperoxides, and hydrogen peroxide.Starting from a previous model generated automatically, a new model has been developed for 1-hexene oxidation by updating some determinant reaction kinetics based on newly published theoretical calculations. This new model allows a good prediction of most of the newly obtained experimental results, as well as satisfactory simulation of literature data obtained for the high-temperature oxidation in a high-pressure jet-stirred reactor, in a rapid compression machine, and in two shock tubes.

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“…Stirring is achieved by four turbulent jets from nozzles connected to an injection cross located at the center of the sphere. This ensures homogeneity in concentration inside the reactor and makes this type of reactor well adapted for a wide-range of gas-phase kinetic studies 45 with a limited effect of possible wall reactions 46 . To ensure thermal homogeneity inside the vessel, the reactor is preceded by an annular preheating zone in which the temperature of the gases is progressively increased up to the reactor temperature.…”

Section: Experiments: Jet-stirred Reactormentioning

confidence: 99%

Experimental and Kinetic Modeling Study of 2-Methyl-2-Butene: Allylic Hydrocarbon Kinetics

et al. 2015

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Two experimental studies have been carried out on the oxidation of 2-methyl-2-butene, one measuring ignition delay times behind reflected shock waves in a stainless steel shock tube, and the other measuring fuel, intermediate, and product species mole fractions in a jet-stirred reactor (JSR) . The shock tube ignition experiments were carried out at three different pressures, approximately 1.7 atm, 11.2 atm, and 31 atm, and at each pressure, fuel-lean =0.5), stoichiometric (=1.0), and fuel-rich (=2.0) mixtures were examined, with each fuel/oxygen mixture diluted in 99% Ar, for initial post-shock temperatures between 1330 and 1730K. The JSR experiments were performed at nearly-atmospheric pressure (800 Torr), with stoichiometric fuel/oxygen mixtures with 0.01 mole fraction of 2M2B fuel, a residence time in the reactor of 1.5s, and mole fractions of 36 different chemical species were measured over a temperature range from 600 to 1150K. These JSR experiments represent the first such studies reporting detailed 2 species measurements for an unsaturated, branched hydrocarbon fuel larger than iso-butene. A detailed chemical kinetic reaction mechanism was developed to study the important reaction pathways in these experiments, with particular attention on the role played by allylic C-H bonds and allylic pentenyl radicals. The results show that, at high temperatures, this olefinic fuel reacts rapidly, similar to related alkane fuels, but the pronounced thermal stability of the allylic pentenyl species inhibits low temperature reactivity, so 2M2B does not produce "cool flames" or negative temperature coefficient behavior. The connections between olefin hydrocarbon fuels, resulting allylic fuel radicals, the resulting lack of low temperature reactivity, and the gasoline engine concept of Octane Sensitivity are discussed.

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Progress in Understanding Low‐Temperature Organic Compound Oxidation Using a Jet‐Stirred Reactor

Cited by 87 publications

References 102 publications

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

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

Revisiting 1-hexene low-temperature oxidation

Experimental and Kinetic Modeling Study of 2-Methyl-2-Butene: Allylic Hydrocarbon Kinetics

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