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Issue 18, 2018
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Thermal decomposition of FC(O)OCH3 and FC(O)OCH2CH3

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Abstract

The thermal decomposition of methyl and ethyl formates has been extensively studied due to their importance in the oxidation of several fuels, pesticidal properties and their presence in interstellar space. We hitherto present the study of the thermal decomposition of methyl and ethyl fluoroformates, which could help in the elucidation of the reaction mechanisms. The reaction mechanisms were studied using FTIR spectroscopy in the temperature range of 453–733 K in the presence of different pressures of N2 as bath gas. For FC(O)OCH3 two different channels were observed; the unimolecular decomposition which is favored at higher temperatures and has a rate constant kFC(O)OCH3 = (5.3 ± 0.5) × 1015 exp[−(246 ± 10 kJ mol−1/RT)] (in units of s−1) and a bimolecular channel with a rate constant kFC(O)OCH3 = (1.6 ± 0.5) × 1011 exp[−(148 ± 10 kJ mol−1/RT)] (in units of s−1 (mol L)−1). However for ethyl formate, only direct elimination of CO2, HF and ethylene operates. The rate constants of the homogeneous first-order process fit the Arrhenius equation kFC(O)OCH2CH3 = (2.06 ± 0.09) × 1013 exp[−(169 ± 6 kJ mol−1/RT)] (in units of s−1). The difference between the mechanisms of the two fluoroformates relies on the stabilization of a six-centered transition state that only exists for ethyl formate. First principles calculations for the different channels were carried out to understand the dynamics of the decomposition.

Graphical abstract: Thermal decomposition of FC(O)OCH3 and FC(O)OCH2CH3

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Publication details

The article was received on 27 Dec 2017, accepted on 28 Mar 2018 and first published on 29 Mar 2018


Article type: Paper
DOI: 10.1039/C7CP08656C
Citation: Phys. Chem. Chem. Phys., 2018,20, 12817-12826
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    Thermal decomposition of FC(O)OCH3 and FC(O)OCH2CH3

    M. Berasategui, G. A. Argüello and M. A. Burgos Paci, Phys. Chem. Chem. Phys., 2018, 20, 12817
    DOI: 10.1039/C7CP08656C

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