Thermal cracking of JP-10: Kinetics and product distribution

Rao, P. Nageswara; Kunzru, Deepak

doi:10.1016/j.jaap.2005.10.003

Cited by 91 publications

(24 citation statements)

References 5 publications

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“…Previously, the CHO-2008 parameter set has been applied to study the initiation mechanism and kinetic parameters of large hydrocarbons. For JP-10, which is a single-component jet fuel, initiation mechanisms and Arrhenius parameters were obtained by Chenoweth et al, which were in good agreement with experimental results. Since the development of a new ReaxFF C/H/O description also focuses on reproducing the success stories of the CHO-2008 description, JP-10 pyrolysis would be an obvious test case to consider.…”

Section: Resultssupporting

confidence: 66%

Extension of the ReaxFF Combustion Force Field toward Syngas Combustion and Initial Oxidation Kinetics

2017

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A detailed insight of key reactive events related to oxidation and pyrolysis of hydrocarbon fuels further enhances our understanding of combustion chemistry. Though comprehensive kinetic models are available for smaller hydrocarbons (typically C or lower), developing and validating reaction mechanisms for larger hydrocarbons is a daunting task, due to the complexity of their reaction networks. The ReaxFF method provides an attractive computational method to obtain reaction kinetics for complex fuel and fuel mixtures, providing an accuracy approaching ab-initio-based methods but with a significantly lower computational expense. The development of the first ReaxFF combustion force field by Chenoweth et al. (CHO-2008 parameter set) in 2008 has opened new avenues for researchers to investigate combustion chemistry from the atomistic level. In this article, we seek to address two issues with the CHO-2008 ReaxFF description. While the CHO-2008 description has achieved significant popularity for studying large hydrocarbon combustion, it fails to accurately describe the chemistry of small hydrocarbon oxidation, especially conversion of CO from CO, which is highly relevant to syngas combustion. Additionally, the CHO-2008 description was obtained faster than expected H abstraction by O from hydrocarbons, thus underestimating the oxidation initiation temperature. In this study, we seek to systemically improve the CHO-2008 description and validate it for these cases. Additionally, our aim was to retain the accuracy of the 2008 description for larger hydrocarbons and provide similar quality results. Thus, we expanded the ReaxFF CHO-2008 DFT-based training set by including reactions and transition state structures relevant to the syngas and oxidation initiation pathways and retrained the parameters. To validate the quality of our force field, we performed high-temperature NVT-MD simulations to study oxidation and pyrolysis of four different hydrocarbon fuels, namely, syngas, methane, JP-10, and n-butylbenzene. Results obtained from syngas and methane oxidation simulation indicated that our redeveloped parameters (named as the CHO-2016 parameter set) has significantly improved the C chemistry predicted by ReaxFF and has solved the low-temperature oxidation initiation problem. Moreover, Arrhenius parameters of JP-10 decomposition and initiation mechanism pathways of n-butylbenzene pyrolysis obtained using the CHO-2016 parameter set are also in good agreement with both experimental and CHO-2008 simulation results. This demonstrated the transferability of the CHO-2016 description for a wide range of hydrocarbon chemistry.

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Section: Resultssupporting

confidence: 66%

Extension of the ReaxFF Combustion Force Field toward Syngas Combustion and Initial Oxidation Kinetics

2017

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“…More recently, CPD has been identified as a major product during the pyrolysis of the jet fuel JP-10 with branching fractions greater than 15% reported over the 1300–1600 K temperature range . These product fractions are in good agreement with prior experimental studies conducted over a wide range of temperatures and pressures, suggesting CPD as a major product. ,− Vandewiele et al examined the secondary reaction products of JP-10 pyrolysis and found that CPD was the central first ring involved in the formation of PAHs such as naphthalene and indene. Theoretical models also suggest that the addition of the cyclopentadienyl radical to the neutral CPD molecule provides additional routes to naphthalene and indene .…”

Section: Introductionsupporting

confidence: 53%

Kinetic Investigations of the CH (X²Π) Radical Reaction with Cyclopentadiene

et al. 2019

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The reaction of the ground state methylidyne radical (CH (X 2 Π)) with cyclopentadiene (C 5 H 6 ) is studied in a quasi-static reaction cell at pressures ranging from 2.7 to 9.7 Torr and temperatures ranging from 298 to 450 K. The CH radical is generated in the reaction cell by pulsed-laser photolysis (PLP) of gaseous bromoform at 266 nm, and its concentration monitored using laser-induced fluorescence (LIF) with an excitation wavelength of 430.8 nm. The reaction rate coefficient is measured to be 2.70(±1.34) × 10 −10 cm 3 molecule −1 s −1 at room temperature and 5.3 Torr and found to be independent of pressure or temperature over the studied experimental ranges. DFT and CBS-QB3 methods are used to calculate the reaction potential energy surface (PES) and to provide insight into the entrance channel of the reaction. The combination of the experimentally determined rate constants and computed PES supports a fast, barrierless entrance channel that is characteristic of CH radical reactions and could potentially lead to the formation of benzene isomers.

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“…The single-component hydrocarbon fuel Jet Propellant-10 (JP-10) is used in detonation engines, missiles, and supersonic combustion ramjets, where a fuel is required to have high thermal stability, high-energy density, and low freezing point. Because of its broad applications, the principal constituent of JP-10, tricyclo[5.2.1.0 , ]decane ( exo -tetrahydrodicyclopentadiene; exo -TCD; C 10 H 16 ; Figure ), has attracted significant attention of researchers, and numerous experimental, theoretical, and modeling studies of its pyrolysis and combustion have been reported in the literature. − A detailed overview on the JP-10 studies was provided in our recent publication, and here we only briefly reiterate its key points.…”

Section: Introductionmentioning

confidence: 99%

A Theoretical Study of Pyrolysis of exo-Tetrahydrodicyclopentadiene and Its Primary and Secondary Unimolecular Decomposition Products

2018

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Theoretical calculations of the rate constants and product branching ratios in the pyrolysis of exo-tetrahydrodicyclopentadiene (JP-10) and its initial decomposition products at combustion-relevant pressures and temperatures were performed and compared to the experimental results from the recently reported molecular beam photoionization mass spectrometry study of the pyrolysis of JP-10 ( Zhao et al. Phys. Chem. Chem. Phys. 2017 , 19 , 15780 - 15807 ). The results allow us to quantitatively assess the decomposition mechanisms of JP-10 by a direct comparison with the nascent product distribution-including radicals and thermally labile closed-shell species-detected in the short-residence-time molecular beam photoionization mass spectrometry experiment. In accord with the experimental data, the major products predicted by the theoretical modeling include methyl radical (CH), acetylene (CH), vinyl radical (CH), ethyl radical (CH), ethylene (CH), allyl radical (CH), 1,3-butadiene (CH), cyclopentadienyl radical (CH), cyclopentadiene (CH), cyclopentenyl radical (CH), cyclopentene (CH), fulvene (CH), benzene (CH), toluene (CH), and 5-methylene-1,3-cyclohexadiene (CH). We found that ethylene, allyl radical, cyclopentadiene, and cyclopentenyl radical are significant products at all combustion-relevant conditions, whereas the relative yields of the other products depend on temperature. The most significant temperature trends predicted are increasing yields of the C2 and C4 species and decreasing yields of the C1, C6, and C7 groups with increasing temperature. The calculated pressure effect on the rate constant for the decomposition of JP-10 via initial C-H bond cleavages becomes significant at temperatures above 1500 K. The initially produced radicals will react away to form closed-shell molecules, such as ethylene, propene, cyclopentadiene, cyclopentene, fulvene, and benzene, which were observed as the predominant fragments in the long-residence-time experiment. The calculated rate constants and product branching ratios should prove useful to improve the existing kinetic models for the JP-10 pyrolysis.

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Thermal cracking of JP-10: Kinetics and product distribution

Cited by 91 publications

References 5 publications

Extension of the ReaxFF Combustion Force Field toward Syngas Combustion and Initial Oxidation Kinetics

Extension of the ReaxFF Combustion Force Field toward Syngas Combustion and Initial Oxidation Kinetics

Kinetic Investigations of the CH (X²Π) Radical Reaction with Cyclopentadiene

A Theoretical Study of Pyrolysis of exo-Tetrahydrodicyclopentadiene and Its Primary and Secondary Unimolecular Decomposition Products

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Thermal cracking of JP-10: Kinetics and product distribution

Cited by 91 publications

References 5 publications

Extension of the ReaxFF Combustion Force Field toward Syngas Combustion and Initial Oxidation Kinetics

Extension of the ReaxFF Combustion Force Field toward Syngas Combustion and Initial Oxidation Kinetics

Kinetic Investigations of the CH (X2Π) Radical Reaction with Cyclopentadiene

A Theoretical Study of Pyrolysis of exo-Tetrahydrodicyclopentadiene and Its Primary and Secondary Unimolecular Decomposition Products

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Kinetic Investigations of the CH (X²Π) Radical Reaction with Cyclopentadiene