NDLI: Shock wave studies of the pyrolysis of fluorocarbon oxygenates. I. The thermal dissociation of C3F6O and CF3COF

Content Provider	Royal Society of Chemistry (RSC)
Author	Cobos, C. J. Thaler, A. Sölter, L. Hintzer, K. Troe, J. Tellbach, E.
Copyright Year	2017
Abstract	The thermal decomposition of hexafluoropropylene oxide, C3F6O, to perfluoroacetyl fluoride, CF3COF, and CF2 has been studied in shock waves highly diluted in Ar between 630 and 1000 K. The measured rate constant k1 = 1.1 × 1014 exp(−162(±4) kJ mol−1/RT) s−1 agrees well with literature data and modelling results. Using the reaction as a precursor, equimolar mixtures of CF3COF and CF2 were further heated. Combining experimental observations with theoretical modelling (on the CBS-QB3 and G4MP2 ab initio composite levels), CF3COF is shown to dissociate on two channels, either leading to CF2 + COF2 or to CF3 + FCO. By monitoring the CF2 signals, the branching ratio was determined between 1400 and 1900 K. The high pressure rate constants for the two channels were obtained from theoretical modelling as k5,∞(CF3COF → CF2 + COF2) = 7.1 × 1014 exp(−320 kJ mol−1/RT) s−1 and k6,∞(CF3COF → CF3 + FCO) = 3.9 × 1015 exp(−355 kJ mol−1/RT) s−1. The experimental results obtained at [Ar] ≈ 5 × 10−6 mol cm−3 were consistent with modelling results, showing that the reaction is in the falloff range of the unimolecular dissociation. The mechanism of secondary reactions following CF3COF dissociation has been analysed as well.
Starting Page	3151
Ending Page	3158
Page Count	8
File Format	HTM / HTML PDF
ISSN	14639076
Volume Number	19
Issue Number	4
Journal	Physical Chemistry Chemical Physics
DOI	10.1039/c6cp06816b
Language	English
Publisher	Royal Society of Chemistry
Access Restriction	Open
Subject Keyword	Ab initio Fluorine Branching fraction Carbonyl fluoride Hexafluoropropylene oxide Dissociative
Content Type	Text
Resource Type	Article
Subject	Physics and Astronomy Physical and Theoretical Chemistry

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