Shock Wave Study of the Thermal Dissociations of C3F6 and c-C3F6. II. Dissociation of Hexafluorocyclopropane and Dimerization of CF2

C. J. COBOS; L. SOELTER; E. TELLBACH; J. TROE

JOURNAL OF PHYSICAL CHEMISTRY A

AMER CHEMICAL SOC

Lugar: Washington; Año: 2014 vol. 118 p. 4873 - 4879

1089-5639

The thermal dissociation of c-C3F6 has been studied in shock waves over the range 620 ?1030 K monitoring the UV absorption of CF2. The reaction was studied close to its high pressure limit, but some high temperature falloff was accounted for. Quantum-chemical and kinetic modeling rationalize the experimental data. The reaction is suggested to involve the 1,3 biradical CF2CF2CF2 intermediate. CF2 formed by the dissociation of c-C3F6 dimerizes to C2F4. The measured rate of this reaction is also found to correspond to the falloff range. Rate constants for 2 CF2  = C2F4 as a function of temperature and bath gas concentration [Ar] are given and shown to be consistent with literature values for the high pressure rate constants from experiments at lower temperatures and dissociation rate constants obtained in the falloff range at higher temperatures. The onset of falloff at intermediate temperatures is analyzed.3F6 has been studied in shock waves over the range 620 ?1030 K monitoring the UV absorption of CF2. The reaction was studied close to its high pressure limit, but some high temperature falloff was accounted for. Quantum-chemical and kinetic modeling rationalize the experimental data. The reaction is suggested to involve the 1,3 biradical CF2CF2CF2 intermediate. CF2 formed by the dissociation of c-C3F6 dimerizes to C2F4. The measured rate of this reaction is also found to correspond to the falloff range. Rate constants for 2 CF2  = C2F4 as a function of temperature and bath gas concentration [Ar] are given and shown to be consistent with literature values for the high pressure rate constants from experiments at lower temperatures and dissociation rate constants obtained in the falloff range at higher temperatures. The onset of falloff at intermediate temperatures is analyzed.