Artículo
Thermal decomposition of FC(O)OCH3 and FC(O)OCH2CH3
Fecha de publicación:
02/2018
Editorial:
Royal Society of Chemistry
Revista:
Physical Chemistry Chemical Physics
ISSN:
1463-9076
e-ISSN:
1463-9084
Idioma:
Inglés
Tipo de recurso:
Artículo publicado
Clasificación temática:
Resumen
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.
Palabras clave:
Atomospheric chemistry
,
Termal decomposition
,
Fluorine
Archivos asociados
Licencia
Identificadores
Colecciones
Articulos(INFIQC)
Articulos de INST.DE INVESTIGACIONES EN FISICO- QUIMICA DE CORDOBA
Articulos de INST.DE INVESTIGACIONES EN FISICO- QUIMICA DE CORDOBA
Citación
Berasategui, Matias; Argüello, Gustavo Alejandro; Burgos Paci, Maximiliano Alberto; Thermal decomposition of FC(O)OCH3 and FC(O)OCH2CH3; Royal Society of Chemistry; Physical Chemistry Chemical Physics; 20; 18; 2-2018; 12817-12826
Compartir
Altmétricas