High-temperature chemistry of HCl and Cl2

Pelucchi, Matteo; Frassoldati, Alessio; Faravelli, Tiziano; Ruščić, Branko; Glarborg, Peter

doi:10.1016/j.combustflame.2015.04.002

Cited by 48 publications

(38 citation statements)

References 130 publications

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“…Recently, a new mechanism for HCl combustion has been proposed by Pelucchi et al 29 A mechanism specific to chloropicrin has been developed in this work, in which were included unimolecular initiations, chlorine-atom abstractions, decomposition of the radicals formed, chlorine-nitrogen coupling reactions, as well as some oxidation reactions not included in kinetic models of chlorinated and nitrogenous species. The thermochemical properties were taken from the literature in the case of light species involved in the nitrogen and chlorine sub-mechanisms [27][28][29] , and theoretically calculated for chloropicrin and related products. Main species theoretically studied are presented in Table 1.…”

Section: Methodsmentioning

confidence: 99%

Combustion and Pyrolysis Kinetics of Chloropicrin

Lizardo-Huerta

Sirjean

Verdier³

et al. 2018

J. Phys. Chem. A

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Chloropicrin (CClNO) is widely used in agriculture as a pesticide, weed-killer, fungicide or nematicide. It has also been used as a chemical agent during World War I. The precise understanding of its combustion chemistry for destruction processes or in the event of accidental fire of stored reserves is a major safety issue. A detailed chemical kinetic model for the combustion and pyrolysis of chloropicrin is proposed for the first time. A large number of thermo-kinetic parameters were calculated using quantum chemistry and reaction rate theory. The model was validated against experimental pyrolysis data available in the literature. It was shown that the degradation of chloropicrin is ruled by the breaking of the C-N bond followed by the oxidation of the trichloromethyl radical by NO through the formation of the adduct CClONO, which can decompose to NO, chlorine atom, and phosgene. Phosgene is much more stable than chloropicrin and its decomposition starts at much higher temperatures. Combustion and pyrolysis simulations were also compared and demonstrated that the addition of oxygen has very little effect on the reactivity or product distribution due to the absence of hydrogen atoms in chloropicrin.

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Section: Methodsmentioning

confidence: 99%

Combustion and Pyrolysis Kinetics of Chloropicrin

Lizardo-Huerta

Sirjean

Verdier³

et al. 2018

J. Phys. Chem. A

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“…The thermodynamic data of all the species of the mechanism can be found in the "thermo" .txt file (Supplementary Material). The thermodynamic data of the species involved in the reactions of Table 1 were taken from the database of Burcat [25] taken from the literature [18] determined by ab initio calculations, or calculated by the Thergas software [26] based on group additivity method (the reader can refer to the file for the origin of the thermodynamic properties).…”

Section:  Reactions Of Isomerization Between Ch2ococh2cl and Ch3ococmentioning

confidence: 99%

First Study of the Pyrolysis of a Halogenated Ester: Methyl Chloroacetate

Vin

Battin‐Leclerc

Herbinet

2019

Ind. Eng. Chem. Res.

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The pyrolysis of a halogenated ester, methyl chloroacetate (MC), under dilute atmosphere and quasiatmospheric pressure was studied at temperatures from 473 to 1048 K using an alumina tubular reactor. MC was chosen as a surrogate to model the thermal decomposition of ethyl bromoacetate, a chemical warfare agent. A maximum MC conversion of 99.8% was observed at a residence time of 2 s, a temperature of 1048 K, and an inlet mole fraction of 0.01. The following products were quantified: CO, CO2, HCl, methane, ethylene, ethane, propene, chloromethane, dichloromethane, vinyl chloride, chloroethane, and dichloroethane. For the first time, a detailed kinetic model of MC pyrolysis was developed and gave a good prediction of the global reactivity and the formation of most of the major products. Flow rate and sensitivity analyses were made to highlight the different pathways of decomposition during the MC pyrolysis. In a first attempt to extrapolate the results obtained with methyl chloroacetate to ethyl bromoacetate, simulations were run with a modified version of the model developed in this study taking into account the differences in bond dissociation energies induced by the change of the chlorine atom by a bromine one. Supplementary MaterialKinetic mechanism used in this work given under CHEMKIN format.Thermodynamic data of all species of the mechanism.Scheme of the experimental setup used for running pyrolysis experiments, measured temperature profile in the TR in absence of reaction, and the carbon, oxygen, and chlorine balances, SCF energy, zero-point corrected electronic energy, frequencies and geometry of molecules, radicals and transition states, calculated at the CBS-QB3 level of theory, comparison of the kinetic parameters of reaction R30 in Table 1 with literature data, experimental mole fractions of species in a tabular form.

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“…The chemical kinetic model consists of oxidation mechanisms for methane and methyl chloride. The methane mechanism was adopted from the recent work by Hashemi et al 45 The methyl chloride scheme was based on the HCl/Cl 2 subset from Pelucchi et al, 46 extended in the present work with reactions describing conversion of simple chlorinated hydrocarbons.…”

Section: Chemical Kinetic Modelmentioning

confidence: 99%

Ab initio calculations and kinetic modeling of thermal conversion of methyl chloride: implications for gasification of biomass

Singla

Rasmussen

Hashemi

et al. 2018

Phys. Chem. Chem. Phys.

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Limitations in current hot gas cleaning methods for chlorine species from biomass gasification may be a challenge for end use such as gas turbines, engines, and fuel cells, all requiring very low levels of chlorine. During devolatilization of biomass, chlorine is released partly as methyl chloride. In the present work, the thermal conversion of CH3Cl under gasification conditions was investigated. A detailed chemical kinetic model for pyrolysis and oxidation of methyl chloride was developed and validated against selected experimental data from the literature. Key reactions of CH2Cl with O2 and C2H4 for which data are scarce were studied by ab initio methods. The model was used to analyze the fate of methyl chloride in gasification processes. The results indicate that CH3Cl emissions will be negligible for most gasification technologies, but could be a concern for fluidized bed gasifiers, in particular in low-temperature gasification. The present work illustrates how ab initio theory and chemical kinetic modeling can help to resolve emission issues for thermal processes in industrial scale.

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High-temperature chemistry of HCl and Cl2

Cited by 48 publications

References 130 publications

Combustion and Pyrolysis Kinetics of Chloropicrin

Combustion and Pyrolysis Kinetics of Chloropicrin

First Study of the Pyrolysis of a Halogenated Ester: Methyl Chloroacetate

Ab initio calculations and kinetic modeling of thermal conversion of methyl chloride: implications for gasification of biomass

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