Issue 22, 1999

Kinetic study of the reactions of CF3O2 radicals with Cl and NO

Abstract

Kinetic studies of the reactions CF3O2+Cl and CF3O2+NO were performed at room temperature in the gas phase using the discharge flow mass spectrometric technique (DFMS). The reactions were investigated under pseudo-first-order conditions with Cl or NO in large excess with respect to the CF3O2 radicals. The rate constant for the reaction CF3O2+NO was measured at 298 K and the value of (1.6±0.3)×10-11 cm3 molecule-1 s-1 is in very good agreement with all previous values. For the reaction CF3O2+Cl, we obtain a rate constant at 298 K of (4.2±0.8)×10-11 cm3 molecule-1 s-1 in excellent agreement with the only published value. Product analysis shows that this reaction occurs via the major reaction pathway CF3O2+Cl→CF3O+ClO at room temperature. In addition, an abinitio theoretical study was performed to gain insights on the different postulated reaction pathways. There is a significant disagreement between experimental and abinitio values recommended for the formation enthalpies of CF2O, CF3O and related molecules produced in this system. Consequently, we provide self-consistent values of enthalpies based on isodesmic reactions for the CF3O2+Cl reaction system using the G2, G2(MP2) and CBS-Q methods. These values are also compared with BAC-MP4 heats of formation calculated in this work.

Supplementary files

Article information

Article type
Paper

Phys. Chem. Chem. Phys., 1999,1, 5087-5096

Kinetic study of the reactions of CF3O2 radicals with Cl and NO

F. Louis, D. R. Burgess, D. R. B. Jr., M. R. J. S., M. Rayez and J. Sawerysyn, Phys. Chem. Chem. Phys., 1999, 1, 5087 DOI: 10.1039/A905933D

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