Rate coefficients for the reaction of chlorine atoms with Fs(O<SUB>2</SUB>)O and Fs(O<SUB>2</SUB>)OCl at 298 k
The kinetics of the recombination reaction Cl + FS(O2)O → FS(O2)OCl (1) has been studied by using an ArF excimer laser flash photolysis technique over the 25-950 mbar total pressure range of the bath gases He, N2 and CF4 at 298 K. The reaction was found to be essentially in the second-order regime....
Guardado en:
| Autores principales: | , , , |
|---|---|
| Formato: | Articulo |
| Lenguaje: | Inglés |
| Publicado: |
2005
|
| Materias: | |
| Acceso en línea: | http://sedici.unlp.edu.ar/handle/10915/175803 |
| Aporte de: |
| Sumario: | The kinetics of the recombination reaction Cl + FS(O2)O → FS(O2)OCl (1) has been studied by using an ArF excimer laser flash photolysis technique over the 25-950 mbar total pressure range of the bath gases He, N2 and CF4 at 298 K. The reaction was found to be essentially in the second-order regime. The derived limiting high-pressure rate coefficient is k1,∞=(1.3±0.3)x10-10 cm3 molecule-1 s-1. For the reaction Cl + FS(O2)OCl → FS(O2)O + Cl2 (2) a rate coefficient of k2 = (2.1±0.9)x10-11 cm3 molecule-1 s-1 was measured. The ratio between both rate coefficients of 0.16 agrees very well with data determined by Vasini and Schumacher. Quantum chemical calculations carried out at the G3MP2//B3LYP/6- 311+G(3df) level of theory allow to determine an standard heat of formation of -136.5 kcal mol-1 for FS(O2)OCl. Rate coefficient calculations in the framework of the phase space theory, performed on a G3MP2B3 electronic potential, indicate that central forces mainly dominate the present recombination reaction. |
|---|