Experimental Confirmation of the Low‐Temperature Oxidation Scheme of Alkanes

Battin‐Leclerc, Frédérique; Herbinet, Olivier; Glaude, Pierre‐Alexandre; Fournet, René; Zhou, Zhongyue; Deng, Linhua; Guo, Huijun; Xie, Ming; Qi, Fei

doi:10.1002/anie.200906850

Cited by 180 publications

(189 citation statements)

References 24 publications

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“…Dagaut et al also verified that the macro-mixing was good and that the temperature of the gas phase was homogeneous using a thermocouple [43]. Since then this reactor has often been used for numerous gas phase kinetic studies of hydrocarbons and oxygenated compounds oxidation [16,[44][45][46].…”

Section: Experimental Methodsmentioning

confidence: 95%

Experimental and modeling investigation of the low-temperature oxidation of n-heptane

Herbinet

Husson

Serinyel

et al. 2012

Combustion and Flame

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The low-temperature oxidation of n-heptane, one of the reference species for the octane rating of gasoline, was investigated using a jet-stirred reactor and two methods of analysis: gas chromatography and synchrotron vacuum ultra-violet photo-ionization mass spectrometry (SVUV-PIMS) with direct sampling through a molecular jet. The second method allowed the identification of products, such as molecules with hydroperoxy functions, which are not stable enough to be detected using gas chromatography. Mole fractions of the reactants and reaction products were measured as a function of temperature (500-1100K), at a residence time of 2s, at a pressure of 800 torr (1.06 bar) and at stoichiometric conditions. The fuel was diluted in an inert gas (fuel inlet mole fraction of 0.005). Attention was paid to the formation of reaction products involved in the low temperature oxidation of n-heptane, such as olefins, cyclic ethers, aldehydes, ketones, species with two carbonyl groups (diones) and ketohydroperoxides. Diones and ketohydroperoxides are important intermediates in the low temperature oxidation of n-alkanes but their formation have rarely been reported. Significant amounts of organic acids (acetic and propanoic acids) were also observed at low temperature. The comparison of experimental data and profiles computed using an automatically generated detailed kinetic model is overall satisfactory. A route for the formation of acetic and propanoic acids was proposed. Quantum calculations were performed to refine the consumption routes of ketohydroperoxides towards diones.

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Section: Experimental Methodsmentioning

confidence: 95%

Experimental and modeling investigation of the low-temperature oxidation of n-heptane

Herbinet

Husson

Serinyel

et al. 2012

Combustion and Flame

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169

240

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“…In alkane fuels, the rate of the isomerization depends on the number of C atoms in this transition state ring, and on the energy of the C-H bond that is broken by the internal abstraction by the RO 2 . Different transition state rings have different contributions to ignition rates, because each ring size makes a different contribution to the overall rate of chain branching and chain propagation [68][69][70][71][72]. Transition state rings with 5 atoms, which abstract the H atom adjacent to the C-O-O• which is abstracting the H atom, lead almost entirely to chain propagation, producing mainly an olefin species and HO 2 radicals, and 6-membered transition state rings lead to products that decompose rapidly into one OH radical and two relatively stable intermediate species.…”

Section: Homogeneous Autoignition Of Biodiesel Fuelsmentioning

confidence: 99%

Detailed chemical kinetic reaction mechanisms for soy and rapeseed biodiesel fuels

Westbrook

Naik²,

Herbinet³

et al. 2011

Combustion and Flame

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A detailed chemical kinetic reaction mechanism is developed for the five major components of soy biodiesel and rapeseed biodiesel fuels. These components, methyl stearate, methyl oleate, methyl linoleate, methyl linolenate, and methyl palmitate, are large methyl ester molecules, some with carbon-carbon double bonds, and kinetic mechanisms for them as a family of fuels have not previously been available. Of particular importance in these mechanisms are models for alkylperoxy radical isomerization reactions in which a C=C double bond is embedded in the transition state ring. The resulting kinetic model is validated through comparisons between predicted results and a relatively small experimental literature. The model is also used in simulations of biodiesel oxidation in jet-stirred reactor and intermediate shock tube ignition and oxidation conditions to demonstrate the capabilities and limitations of these mechanisms.Differences in combustion properties between the two biodiesel fuels, derived from soy and rapeseed oils, are traced to the differences in the relative amounts of the same five methyl ester components. † Lawrence

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“…6,11−13 Specifically for DME, the low-temperature oxidation (400−700 K) of dimethyl ether was studied in a jetstirred reactor using molecular-beam mass spectrometry (MBMS), and the detection and identification of the ketohydroperoxide hydroperoxymethyl formate (HPMF, HOO-CH 2 OCHO) were reported in a recent study that included the present authors. 6 However, the described detection and identification of elusive intermediates 6,11 can only provide initial guidance for testing the predictive capabilities of chemically detailed mechanisms for low-temperature combustion and for understanding the underlying chemistry. It was mentioned above that more powerful validation targets become available to test the accuracies of the model predictions if reliable quantitative information about these elusive intermediates can be extracted from the experimental data.…”

Section: Introductionmentioning

confidence: 99%

Quantification of the Keto-Hydroperoxide (HOOCH₂OCHO) and Other Elusive Intermediates during Low-Temperature Oxidation of Dimethyl Ether

et al. 2016

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This work provides new temperature-dependent mole fractions of elusive intermediates relevant to the lowtemperature oxidation of dimethyl ether (DME). It extends the previous study of Moshammer et al. [J. Phys. Chem. A 2015, 119, 7361−7374] in which a combination of a jet-stirred reactor and molecular beam mass spectrometry with singlephoton ionization via tunable synchrotron-generated vacuumultraviolet radiation was used to identify (but not quantify) several highly oxygenated species. Here, temperature-dependent concentration profiles of 17 components were determined in the range of 450−1000 K and compared to up-to-date kinetic modeling results. Special emphasis is paid toward the validation and application of a theoretical method for predicting photoionization cross sections that are hard to obtain experimentally but essential to turn mass spectral data into mole fraction profiles. The presented approach enabled the quantification of the hydroperoxymethyl formate (HOOCH 2 OCH 2 O), which is a key intermediate in the low-temperature oxidation of DME. The quantification of this ketohydroperoxide together with the temperature-dependent concentration profiles of other intermediates including H 2 O 2 , HCOOH, CH 3 OCHO, and CH 3 OOH reveals new opportunities for the development of a next-generation DME combustion chemistry mechanism.

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Experimental Confirmation of the Low‐Temperature Oxidation Scheme of Alkanes

Cited by 180 publications

References 24 publications

Experimental and modeling investigation of the low-temperature oxidation of n-heptane

Experimental and modeling investigation of the low-temperature oxidation of n-heptane

Detailed chemical kinetic reaction mechanisms for soy and rapeseed biodiesel fuels

Quantification of the Keto-Hydroperoxide (HOOCH₂OCHO) and Other Elusive Intermediates during Low-Temperature Oxidation of Dimethyl Ether

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Experimental Confirmation of the Low‐Temperature Oxidation Scheme of Alkanes

Cited by 180 publications

References 24 publications

Experimental and modeling investigation of the low-temperature oxidation of n-heptane

Experimental and modeling investigation of the low-temperature oxidation of n-heptane

Detailed chemical kinetic reaction mechanisms for soy and rapeseed biodiesel fuels

Quantification of the Keto-Hydroperoxide (HOOCH2OCHO) and Other Elusive Intermediates during Low-Temperature Oxidation of Dimethyl Ether

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Quantification of the Keto-Hydroperoxide (HOOCH₂OCHO) and Other Elusive Intermediates during Low-Temperature Oxidation of Dimethyl Ether