Shock tube/laser absorption studies of the decomposition of methyl formate

Ren, Wei; Lam, King-Yiu; Pyun, Sung Hyun; Farooq, Aamir; Davidson, David F.; Hanson, Ronald K.

doi:10.1016/j.proci.2012.05.071

Cited by 30 publications

(29 citation statements)

References 25 publications

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“…In Table 3, the Arrhenius parameters calculated from the reaction rate constants are listed at different temperatures. In general, there is good agreement with the values obtained previously 8,43 (Figure 10 and Figures S16–S20 in ESI) but with deviation at low temperatures. Below 1500 K, the partition functions differ by many orders of magnitude making the rate constants very sensitive to the vibrational frequencies from the electronic structure calculations.…”

Section: Resultssupporting

confidence: 89%

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Probing the pyrolysis of methyl formate in the dilute gas phase by synchrotron radiation and theory

et al. 2022

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The thermal dissociation of the atmospheric constituent methyl formate was probed by coupling pyrolysis with imaging photoelectron photoion coincidence spectroscopy (iPEPICO) using synchrotron VUV radiation at the Swiss Light Source (SLS). iPEPICO allows threshold photoelectron spectra to be obtained for pyrolysis products, distinguishing isomers and separating ionic and neutral dissociation pathways. In this work, the pyrolysis products of dilute methyl formate, CH 3 OC(O)H, were elucidated to be CH 3 OH + CO, 2 CH 2 O and CH 4 + CO 2 as in part distinct from the dissociation of the radical cation (CH 3 OH +• + CO and CH 2 OH + + HCO). Density functional theory, CCSD(T), and CBS-QB3 calculations were used to describe the experimentally observed reaction mechanisms, and the thermal decomposition kinetics and the competition between the reaction channels are addressed in a statistical model. One result of the theoretical model is that CH 2 O formation was predicted to come directly from methyl formate at temperatures below 1200 K, while above 1800 K, it is formed primarily from the thermal decomposition of methanol.

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Section: Resultssupporting

confidence: 89%

Section: Kinetic Analysissupporting

confidence: 89%

Probing the pyrolysis of methyl formate in the dilute gas phase by synchrotron radiation and theory

et al. 2022

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“…In the studies [16,17] the MF decomposition to CH 3 OH + CO was identified as most favored, related to the calculated reaction barriers. Later, Ren et al [18,19] measured species time histories of MF pyrolysis in the shock tube opening the opportunity to derive experimental reaction rate constants for this decomposition channel. Their results agree to the estimated rate constant provided by Dooley et al [9].…”

Section: Dmementioning

confidence: 99%

Experimental and theoretical investigations of methyl formate oxidation including hot β-scission

Minwegen

Döntgen

Hemken

et al. 2019

Proceedings of the Combustion Institute

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“…Possible unimolecular pericyclic reactions were considered by analogy with that of methyl formate, whose decomposition has been thoroughly investigated in the literature. − Methyl formate has indeed a structure close to that of diphosgene, with H atoms replacing Cl atoms. Three reactions can occur: Both theoretical calculations , and experiments in a shock tube found that reaction yielding methanol and CO was, by far, the major products channel.…”

Section: Chemical Kinetic Model Developmentmentioning

confidence: 99%

“…Three reactions can occur: Both theoretical calculations , and experiments in a shock tube found that reaction yielding methanol and CO was, by far, the major products channel. From theoretical rate constants, calculated at the high-pressure limit by Metcalfe et al, the branching ratios at 1300 K are 99.6%, 0.3%, and 0.1% for reactions , , and , respectively, whereas measurements in shock tube between 1202 and 1607 K under 1.3–1.7 atm led to branching ratios of 91.5%, 3.2%, and 5.3% at 1300 K, respectively. Similar reaction routes were investigated in the case of diphosgene.…”

Section: Chemical Kinetic Model Developmentmentioning

confidence: 99%

Thermal Decomposition of Phosgene and Diphosgene

Lizardo-Huerta

Sirjean

Verdier³

et al. 2017

J. Phys. Chem. A

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Phosgene (COCl) is a toxic compound used or formed in a wide range of applications. The understanding of its thermal decomposition for destruction processes or in the event of accidental fire of stored reserves is a major safety issue. In this study, a detailed chemical kinetic model for the thermal decomposition and combustion of phosgene and diphosgene 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 from the literature. It is predicted that the degradation of diphosgene is mainly ruled by a pericyclic reaction producing two molecules of phosgene and, to a lesser extent, by a roaming radical reaction yielding CO and CCl. Phosgene is much more stable than diphosgene under high-temperature conditions, and its decomposition starts at higher temperatures. Decomposition products are CO and Cl. An equimolar mixture of the latter molecules can be considered as a surrogate of phosgene from the kinetic point of view, but the important endothermic effect of the decomposition reaction can lead to different behaviors, for instance, in the case of autoignition under high pressure and high temperature.

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Shock tube/laser absorption studies of the decomposition of methyl formate

Cited by 30 publications

References 25 publications

Probing the pyrolysis of methyl formate in the dilute gas phase by synchrotron radiation and theory

Probing the pyrolysis of methyl formate in the dilute gas phase by synchrotron radiation and theory

Experimental and theoretical investigations of methyl formate oxidation including hot β-scission

Thermal Decomposition of Phosgene and Diphosgene

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