Influences of propylene/propyne addition on toluene pyrolysis in a single-pulse shock tube

Sun, Wenyu; Hamadi, Alaa; Abid, Souhir; Chaumeix, Nabiha; Comandini, Andrea

doi:10.1016/j.combustflame.2021.111799

Cited by 13 publications

(16 citation statements)

References 47 publications

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“…In Fig. 5a-c, the dashed lines represent simulations obtained with the ICARE chemical kinetic mechanism 35 for PAH for- mation and growth. This mechanism was previously validated against species profiles vs. temperature conditions from single-pulse shock tube experiments for pyrolysis of many single fuels at a nominal pressure of 20 bar.…”

Section: Resultsmentioning

confidence: 99%

“…temperature conditions from single-pulse shock tube experiments for pyrolysis of many single fuels at a nominal pressure of 20 bar. Some of the datasets used to develop the model were toluene 34,35 (100–200 ppm, T 5 1050–1700 K), and ethylbenzene 36 (100 ppm, T 5 950–1700 K) and their mixtures with small aliphatics (including reactions toluene + C 2 H x 37 and toluene + C 3 H x 35 at similar conditions). The simulations were performed with ANSYS CHEMKIN-Pro 2021 software using the batch reactor model with variable pressure.…”

Section: Resultsmentioning

confidence: 99%

“…In Fig. 5a–c , the dashed lines represent simulations obtained with the ICARE chemical kinetic mechanism 35 for PAH formation and growth. This mechanism was previously validated against species profiles vs .…”

Section: Resultsmentioning

confidence: 99%

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External standard calibration method for high-repetition-rate shock tube kinetic studies with synchrotron-based time-of-flight mass spectrometry

Cano Ardila,

Nagaraju,

Tranter

et al. 2024

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

See 1 more Smart Citation

External standard calibration method for high-repetition-rate shock tube kinetic studies with synchrotron-based time-of-flight mass spectrometry

Cano Ardila,

Nagaraju,

Tranter

et al. 2024

Analyst

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“…• + C 3 H 3 • → C 10 H 8 /1-methylene-1H-indene was highlighted among the main pathways responsible for naphthalene formation. 50 Instead, Figure 9d shows that in the updated model, naphthalene is mostly produced from C 9 H 6 CH 3 -1, C 9 H 7 CH 2 (i18), and 1-methylene-1H-indene isomers, which largely derive from methyl recombination with indenyl. Finally, it is noted that reactions on the C 7 H 5…”

Section: Fulvenallenyl Plus Methylacetylene the Pattern Of The C 7 Hmentioning

confidence: 95%

Fulvenallenyl Radical (C₇H₅^·)-Mediated Gas-Phase Synthesis of Bicyclic Aromatic C₁₀H₈ Isomers: Can Fulvenallenyl Efficiently React with Closed-Shell Hydrocarbons?

Mebel,

Li,

Pratali Maffei

et al. 2024

J. Phys. Chem. A

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To understand the reactivity of resonantly stabilized radicals, often found in relevant concentrations in gaseous environments, it is important to determine their main reaction pathways. Here, it is investigated whether the fulvenallenyl radical (C 7 H 5• ) reacts preferentially with closed-shell molecules or radicals. Electronic structure calculations on the C 10 H 9 potential energy surface accessed by the reactions of C 7 H 5• with methylacetylene (CH 3 CCH) and allene (H 2 CCCH 2 ) were combined with RRKM-ME calculations of temperature-and pressure-dependent rate constants using the automated EStokTP software suite and kinetic modeling to assess the reactivity of C 7 H 5 • with closed-shell unsaturated hydrocarbons. Experimentally, the reactions were attempted in a chemical microreactor heated to 998 ± 10 K by preparing fulvenallenyl radicals via pyrolysis of trichloromethylbenzene (C 7 H 5 Cl 3 ) and seeding the radicals in methylacetylene or allene carrier gas, with product identification by means of photoionization mass spectrometry. The measured photoionization efficiency curve of m/z = 128 was assigned to a linear combination of the reference curves of two C 10 H 8 isomers, azulene (minor) and naphthalene (major), presumably resulting from the C 7 H 5• plus C 3 H 4 reactions. However, the calculations demonstrated that these reactions are too slow, and kinetic modeling of processes in the reactor allowed us to conclude that the observation of naphthalene and azulene is due to the C 7 H 5• plus C 3 H 3 • reaction, where propargyl is produced by direct hydrogen atom abstraction by chlorine (Cl) atoms from allene or methylacetylene and Cl stem from the pyrolysis of C 7 H 5 Cl 3 . Modeling results under the copyrolysis conditions of toluene and methylacetylene in high-temperature shock tube experiments confirmed the prevalence of the fulvenallenyl reaction with propargyl over its reactions with C 3 H 4 even when the concentrations of allene and methylacetylene largely exceed that of propargyl. Overall, the reactions of fulvenallenyl with both allene and methylacetylene were found to be noncompetitive in the formation of naphthalene and azulene thus attesting the inefficiency of the fulvenallenyl radical reactions with the prototype closed-shell hydrocarbon species. In the meantime, the new reaction pathways revealed, including Hassisted isomerizations between C 10 H 8 isomers and decomposition reactions of various C 10 H 9 isomers, emerge as relevant and are recommended for inclusion in combustion kinetic models for naphthalene formation.

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“…Understanding the mechanism of molecular growth chemistry in combustion of hydrocarbons is fundamental to the kinetic modeling of the formation of polycyclic aromatic hydrocarbons and particulate matters. Reaction pathways for the molecular growth of hydrocarbons are highly complicated, and various mechanisms have been suggested to contribute to the formation and growth of aromatic rings. − One of the important classes of reactions for the ring formation and growth involves recombination between resonance-stabilized radicals. ,,− In addition to the well-studied first-ring formation from the recombination of the propargyl radicals, ,, several reaction mechanisms involving the resonance-stabilized radicals have been proposed for the formation of polycyclic compounds. ,,,− …”

Section: Introductionmentioning

confidence: 99%

Ring Growth Mechanism in the Reaction between Fulvenallenyl and Cyclopentadienyl Radicals

Matsugi,

Suzuki

2024

J. Phys. Chem. A

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Recombination between resonance-stabilized hydrocarbon radicals is an important class of reactions that contribute to molecular growth chemistry in combustion. In the present study, the ring growth mechanism in the reaction between fulvenallenyl (C 7 H 5 ) and cyclopentadienyl (C 5 H 5 ) radicals is investigated computationally. The reaction pathways are explored by quantum chemical calculations, and the phenomenological and steady-state rate constants are determined by solving the multiplewell master equations. The primary reaction routes following the recombination between the two radicals are found to be as follows: formation of the adducts, isomerization by hydrogen shift reactions, cyclization to form tricyclic compounds, and their isomerization and dissociation reactions, leading to the formation of acenaphthylene. The overall process can be approximately represented as C 7 H 5 + C 5 H 5 → acenaphthylene + 2H with the bimolecular rate constant of about 4 × 10 −12 cm 3 molecule −1 s −1 . A reaction mechanism consisting of 20 reactions, including the formation, isomerization, and dissociation processes of major intermediate species, is proposed for use in kinetic modeling.

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Influences of propylene/propyne addition on toluene pyrolysis in a single-pulse shock tube

Cited by 13 publications

References 47 publications

External standard calibration method for high-repetition-rate shock tube kinetic studies with synchrotron-based time-of-flight mass spectrometry

External standard calibration method for high-repetition-rate shock tube kinetic studies with synchrotron-based time-of-flight mass spectrometry

Fulvenallenyl Radical (C₇H₅^·)-Mediated Gas-Phase Synthesis of Bicyclic Aromatic C₁₀H₈ Isomers: Can Fulvenallenyl Efficiently React with Closed-Shell Hydrocarbons?

Ring Growth Mechanism in the Reaction between Fulvenallenyl and Cyclopentadienyl Radicals

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Influences of propylene/propyne addition on toluene pyrolysis in a single-pulse shock tube

Cited by 13 publications

References 47 publications

External standard calibration method for high-repetition-rate shock tube kinetic studies with synchrotron-based time-of-flight mass spectrometry

External standard calibration method for high-repetition-rate shock tube kinetic studies with synchrotron-based time-of-flight mass spectrometry

Fulvenallenyl Radical (C7H5·)-Mediated Gas-Phase Synthesis of Bicyclic Aromatic C10H8 Isomers: Can Fulvenallenyl Efficiently React with Closed-Shell Hydrocarbons?

Ring Growth Mechanism in the Reaction between Fulvenallenyl and Cyclopentadienyl Radicals

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Product

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Fulvenallenyl Radical (C₇H₅^·)-Mediated Gas-Phase Synthesis of Bicyclic Aromatic C₁₀H₈ Isomers: Can Fulvenallenyl Efficiently React with Closed-Shell Hydrocarbons?