The temperature and wavelength dependence of the photo-oxidation of propionaldehyde

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Abstract

Propionaldehyde was photolyzed by flash photolysis in the presence of air or by steady state photolysis in the presence of O2 at 298 or 263 K. For the flash photolysis experiments, the transient absorption of RO2 radicals was monitored and quantum yields were obtained at 293.7, 302.0, 311.7 and 325.0 nm incident radiation. For the steady state photolysis, quantum yields for both CO and C2H6 were monitored at 253.7, 312.8 and 334.1 nm incident radiation. C2H6 was found at 253.7 nm but not at the longer wavelengths. For the steady state photolysis, the difference between the quantum yields for CO and C2H6 corresponds to the quantum yield of C2H5 formation. Good agreement was obtained for the radical yields by both methods. The radical yields decreased with increasing pressure, increasing wavelength or decreasing temperature. At 298 K, the half-quenching pressures were ∞, 7800 Torr, 5100 Torr, about 750 Torr, 308 Torr and 291 Torr at 254 nm, 294 nm, 302 nm, 312 nm, 325 nm and 334 nm respectively. These lead to atmospheric photodissociation coefficients for radical formation at 298 K of 2.4 × 10−5s−1 and 1.6 × 10−5s−1 for solar zenith angles of 30° and 58° respectively.

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