Kinetic Study of the Reactions of CF3O2 Radicals with Cl and NO
F Louis, Donald R. Burgess Jr., M Rayez, J P. Sawerysyn
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 (DF/MS). 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} x 10-11 cm 3 molecule-1 s-1 is in very good agreement with all previous values. For the reaction CF3O2 + Cl, we obtain a rate constant 298 K of (4.2 0.8) x 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 ab initio theoretical study was performed to gain insights on the different postulated reaction pathways. There is a significant disagreement between experimental and ab initio 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.
Physical Chemistry Chemical Physics
ab initio, chemical kinetic, environment, HFC's, rate measurement, stratospheric ozone
, Burgess Jr., D.
, Rayez, M.
and Sawerysyn, J.
Kinetic Study of the Reactions of CF<sub>3</sub>O<sub>2</sub> Radicals with Cl and NO, Physical Chemistry Chemical Physics
(Accessed May 29, 2023)