Improved Kinetic Model of the Low-Temperature Oxidation of <i>n</i>-Heptane

Pelucchi, Matteo; Bissoli, Mattia; Cavallotti, Carlo; Cuoci, Alberto; Faravelli, Tiziano; Frassoldati, Alessio; Ranzi, E.; Stagni, Alessandro

doi:10.1021/ef501483f

Cited by 105 publications

(108 citation statements)

References 52 publications

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“…All the experimental data presented here are detailed in an SM spreadsheet. The model used for simulations is that newly proposed by the Galway group [9] with formation reactions of diones adapted from [14]. A few changes have been tested in this mechanism and are listed in SM.…”

Section: Experimental and Simulation Resultsmentioning

confidence: 99%

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Measuring hydroperoxide chain-branching agents during n-pentane low-temperature oxidation

Rodriguez

Herbinet

Wang

et al. 2017

Proceedings of the Combustion Institute

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, et al.. Measuring hydroperoxide chain-branching agents during n-pentane low-temperature oxidation. Proceedings of the Combustion Institute, Elsevier, 2017Elsevier, , 36, pp.333 -342. 10.1016Elsevier, /j.proci.2016 AbstractThe reactions of chain-branching agents, such as H2O2 and hydroperoxides, have a decisive role in the occurrence of autoignition. The formation of these agents has been investigated in an atmospheric-pressure jet-stirred reactor during the low-temperature oxidation of n-pentane (initial fuel mole fraction of 0.01, residence time of 2 s) using three different diagnostics: timeof-flight mass spectrometry combined with tunable synchrotron photoionization, time-of-flight mass spectrometry combined with laser photoionization, and cw-cavity ring-down spectroscopy. These three diagnostics enable a combined analysis of H2O2, C1-C2, and C5 alkylhydroperoxides, C3-C5 alkenylhydroperoxides, and C5 alkylhydroperoxides including a carbonyl function (ketohydroperoxides). Results using both types of mass spectrometry are compared for the stoichiometric mixture. Formation data are presented at equivalence ratios from 0.5 to 2 for these peroxides and of two oxygenated products, ketene and pentanediones, which are not usually analyzed during jet-stirred reactor oxidation. The formation of alkenylhydroperoxides during alkane oxidation is followed for the first time. A recently developed model of n-pentane oxidation aids discussion of the kinetics of these products and of proposed pathways for C3-C5 alkenylhydroperoxides and the pentanediones.

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Section: Experimental and Simulation Resultsmentioning

confidence: 99%

“…Figure 4: Temperature evolution of the mole fraction X of hydroperoxides and diones at various equivalence ratios. Experimental (SPI-MS, symbols) and computed (lines with ketohydroperoxide values divided by 125) using model of [9] for hydroperoxides and with changes adapted from [14] for diones.…”

Section: Hydroperoxide and Dione Identification And Quantificationmentioning

confidence: 99%

Measuring hydroperoxide chain-branching agents during n-pentane low-temperature oxidation

Rodriguez

Herbinet

Wang

et al. 2017

Proceedings of the Combustion Institute

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“…The reaction classes investigated were (1) show that, at 650 K, 94% of C 7 carbonyl-hydroperoxides decompose via simple fission of the O-O bond in the hydroperoxyl group. 32 In light of this, we find it adequate to describe the decomposition of C 5 carbonyl-hydroperoxides via unimolecular decomposition alone, given the temperature range of experiments (>640 K) over which the mechanisms have been validated. 19 However, should speciation data become available for the pentane isomers in the low-temperature regime, inclusion of these pathways should not be too strenuous a task.…”

Section: Additional Pathwaysmentioning

confidence: 95%

Revisiting the Kinetics and Thermodynamics of the Low-Temperature Oxidation Pathways of Alkanes: A Case Study of the Three Pentane Isomers

et al. 2015

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This paper describes our developing understanding of low-temperature oxidation kinetics. We have investigated the ignition of the three pentane isomers in a rapid compression machine over a wide range of temperatures and pressures, including conditions of negative temperature coefficient behavior. The pentane isomers are small alkanes, yet have structures that are complex enough to allow for the application of their kinetic and thermochemical rules to larger molecules. Updates to the thermochemistry of the species important in the low-temperature oxidation of hydrocarbons have been made based on a thorough literature review. An evaluation of recent quantum-chemically derived rate coefficients from the literature pertinent to important low-temperature oxidation reaction classes has been performed, and new rate rules are recommended for these classes. Several reaction classes have also been included to determine their importance with regard to simulation results, and we have found that they should be included when developing future chemical kinetic mechanisms. A comparison of the model simulations with pressure-time histories from experiments in a rapid compression machine shows very good agreement for both ignition delay time and pressure rise for both the firstand second-stage ignition events. We show that revisions to both the thermochemistry and the kinetics are required in order to replicate experiments well. A broader validation of the models with ignition delay times from shock tubes and a rapid compression machine is presented in an accompanying paper. The results of this study enhance our understanding of the combustion of straight-and branched-chained alkanes.

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“…To the best of our knowledge, the calculation on the propyl system by Goldsmith is the only reported investigation of OOH + O 2 rates. In other n-heptane mechanisms estimated, identical rate constants for both OOH+O 2 and R+O 2 are used, for example LLNL [17] and POLIMI [52]. The rate rules employed by the current mechanism for these important reactions are expected to be more accurate than previous mechanisms due to their ab-initio origins compared with previously made estimates.…”

Section: Low Temperature Mechanismmentioning

confidence: 99%