INIFTA   05425
INSTITUTO DE INVESTIGACIONES FISICO-QUIMICAS TEORICAS Y APLICADAS
Unidad Ejecutora - UE
artículos
Título:
Shock wave and modeling study of the thermal decomposition reactions of Pentafluoroethane and 2-H Heptafluoropropane
Autor/es:
C. J. COBOS; L. SOLTER; E. TELLBACH.; J. TROE
Revista:
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
Editorial:
ROYAL SOC CHEMISTRY
Referencias:
Lugar: CAMBRIDGE; Año: 2014 vol. 16 p. 9797 - 9807
ISSN:
1463-9076
Resumen:
The thermal decompositions of CF3CF2H and CF3CFHCF3 have been studied in shock waves by monitoring the appearance of CF2 radicals. Temperatures in the range 1400 ? 2000 K and Ar bath gas concentrations in the range (2-10) x 10-5 mol cm-3 were employed. It is shown that the decompositions are initiated by C-C bond fission and not by HF elimination. Differing conclusions about the primary decomposition products from experiments at very low pressures are attributed to unimolecular falloff effects. By increasing the initial reactant concentrations in Ar from 60 to 1000 ppm, a retardation of CF2 formation is observed while the final CF2 yields remain close to two CF2 per C2F5H or three CF2 per C3F7H. This is explained by a series of secondary bimolecular reactions which lead to comparably stable transient species like CF3H releasing CF2 at a slower rate. Quantum-chemical calculations and kinetic modeling help to identify the reaction pathways and provide estimates of rate constants for a series of primary and secondary reactions of the decomposition mechanisms.