title: Mechanism of photo-oxidation of heptafluorobutyric anhydride in the presence of NO2. Synthesis and characterization of heptafluoropropyl peroxynitrate, CF3CF2CF2OONO2.
abstract: The photolysis of heptafluorobutyric anhydride at 254 nm in the presence of NO(2) and O(2) has been studied. It leads to the formation of CF(3)CF(2)CF(2)OONO(2), CF(3)CF(2)OONO(2), and CF(2)O as the only fluorine-containing carbonaceous products. The formation of the new heptafluoropropyl peroxynitrate (HFPN, CF(3)CF(2)CF(2)OONO(2)), as one of the main products, is a consequence of the formation of CF(3)CF(2)CF(2)OO(•) radicals followed by the reaction with NO(2). To characterize HFPN, the UV absorption cross sections and their temperature dependence between 245 and 300 K have been measured over the wavelength range 200-300 nm as well as the infrared absorption cross sections. Kinetic parameters for its thermal decomposition are also presented in the temperature range between 281 and 300 K. The Rice-Ramsperger-Kassel-Marcus calculation reveals that the rate coefficient for the thermal decomposition at 285 K is almost independent of total pressure. The mechanism for the decomposition of CF(3)CF(2)CF(2)OONO(2) in the presence of NO was adjusted by a kinetic model, which enabled the calculation of important rate coefficients.
authors.affiliation: Instituto de Investigaciones en Físico Química de Córdoba (INFIQC) CONICET-UNC, Departamento de Físico Química, Facultad de Ciencias Químicas, Universidad Nacional de Córdoba, Ciudad Universitaria, X5000HUA Córdoba, Argentina.
authors.forename: Adriana G
authors.initials: AG
authors.lastname: Bossolasco
authors.forename: Fabio E
authors.initials: FE
authors.lastname: Malanca
authors.forename: Maxi A
authors.initials: MA
authors.lastname: Burgos Paci
authors.forename: Gustavo A
authors.initials: GA
authors.lastname: Argüello
mesh_terms: D005466:Fluorocarbons / Q000737:chemistry*; D009585:Nitrogen Dioxide / Q000737:chemistry*; D010084:Oxidation-Reduction; D010545:Peroxides / Q000737:chemistry*; D055668:Photochemical Processes; D011789:Quantum Theory; D013696:Temperature
chemical_list: D005466:Fluorocarbons; D010545:Peroxides; C007924:heptafluorobutyric anhydride; D009585:Nitrogen Dioxide