Products of the quenching of NO A 2R+ (v = 0) by N2O and CO2

MAXI A. BURGOS PACI; GOWRIE SARAH; JULIAN FEW; GUS HANCOCK

PHYSICAL CHEMISTRY CHEMICAL PHYSICS

ROYAL SOC CHEMISTRY

Lugar: Cambridge; Año: 2013 vol. 15 p. 2554 - 2564

1463-9076

 The photolysis of heptafluorobutyric anhydrideat 254 nm in the presence of NO2 and O2 has been studied. Itleads to the formation of CF3CF2CF2OONO2, CF3CF2OONO2,and CF2O as the only fluorine-containing carbonaceous prod-ucts. The formation of the new heptafluoropropyl peroxynitrate(HFPN, CF3CF2CF2OONO2), as one of the main products, isa consequence of the formation of CF3CF2CF2OO? radicalsfollowed by the reaction with NO2. To characterize HFPN, theUV absorption cross sections and their temperature dependencebetween 245 and 300 K have been measured over thewavelength range 200−300 nm as well as the infrared absorption cross sections. Kinetic parameters for its thermal decompositionare also presented in the temperature range between 281 and 300 K. The Rice−Ramsperger−Kassel−Marcus calculation reveals thatthe rate coefficient for the thermal decomposition at 285 K is almost independent of total pressure. The mechanism for thedecomposition of CF3CF2CF2OONO2 in the presence of NO was adjusted by a kinetic model, which enabled the calculation ofimportant rate coefficients.