UV absorption cross sections between 230 and 350 nm and pressure dependence of the photolysis quantum yield at 308 nm of CF3CH2CHO

Ultraviolet (UV) absorption cross sections of CF3CH2CHO were determined between 230 and 350 nm by gas-phase UV spectroscopy. The forbidden n -> pi* transition was characterized as a function of temperature (269-323 K). In addition, the photochemical degradation of CF3CH2CHO was investigated at 308 nm. The possible photolysis channels are: CF3CH2 + HCO (R1a), CF3CH3 + CO (R1b), and CF3CH2CO + H (R1c). Photolysis quantum yields of CF3CH2CHO at 308 nm, Phi(lambda=308nm), were measured as a function of pressure (25-760 Torr of synthetic air). The pressure dependence of Phi(lambda=308nm) can be expressed as the following Stern-Volmer equation: 1/Phi(lambda=308nm) = (4.65 +/- 0.56) + (1.51 +/- 0.04) x 10(-18) [M] ([M] in molecule cm(-3)). Using the absorption cross sections and the photolysis quantum yields reported here, the photolysis rate coefficient of this fluorinated aldehyde throughout the troposphere was estimated. This calculation shows that tropospheric photolysis of CF3CH2CHO is competitive with the removal initiated by OH radicals at low altitudes, but it can be the major degradation route at higher altitudes. Photodegradation products (CO, HC(O)OH, CF3CHO, CF3CH2OH, and F2CO) were identified and also quantified by Fourier transform infrared spectroscopy. CF3CH2C(O) OH was identified as an end-product as a result of the chemistry involving CF3CH2CO radicals formed in the OH + CF3CH2CHO reaction. In the presence of an OH-scavenger (cyclohexane), CF3CH2C(O) OH was not detected, indicating that channel (R1c) is negligible. Based on a proposed mechanism, our results provide strong evidences of the significant participation of the radical-forming channel (R1a).