Formation, thermal decomposition and atmospheric implications of the CF2(OH)CF2OONO2 and CF3CF2OONO2 peroxynitrates. A theoretical study

• Autores: Badenes, Maria Paula
• Año de publicación: 2017
• Idioma: inglés
• Tipo de recurso: artículo
• Materia: Peroxynitrates; Cf2(Oh)Cf2oono2; Cf3cf2oono2; Quantum-Chemical Calculations
• Institución: Consejo Nacional de Investigaciones Científicas y Técnicas

A SACM/CT study of the CF2(OH)CF2OO + NO2 → CF2(OH)CF2OONO2 and CF3CF2OO + NO2 → CF3CF2OONO2 recombination reactions and their reverse unimolecular decomposition process was performed. The electronic energy along the reaction pathways was calculated at the G4(MP2) level. High-pressure rate coefficients of 1.53 × 10−12 (T/300)0.37 cm3 molecule−1 s−1 and 1.79 × 1016 (T/300)0.40 exp(−24.4 kcal mol−1/RT) s−1 were derived at 200–300 K for the direct and backward reactions of CF2(OH)CF2OONO2, while for CF3CF2OONO2, the expressions 1.01 × 10−12 (T/300)0.39 cm3 molecule−1 s−1 and 1.05 × 1016 (T/300)0.44 exp(−23.0 kcal mol−1/RT) s−1 were obtained. A decomposition lifetime profile was derived for CF2(OH)CF2OONO2, indicating that it could act as transport and reservoir of CF2(OH)CF2OO and NO2 in the stratosphere.
Fil: Badenes, Maria Paula. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina