Abstract
Ozone formation in the 214-nm photolysis of oxygen at pressures ranging from 380 to 1300 Torr was investigated. The rates of ozone formation increase with the square of oxygen pressure mirroring the pressure dependence of the absorption cross sections of oxygen. This observation demonstrates the importance of the collision-induced changes in oxygen absorbance and points to a need to examine the role of oxygen dimer (O/sub 2/) in reactions initiated by its photodissociation. Because of the high dilution of ozone, its formation was found to be linear with time even though, on the average, its rate of photolysis exceeded the rate of its generation from oxygen. The quantum yield of ozone formation was 1.86 /plus minus/ 0.17 independent of O/sub 2/ pressure. From this result the quantum yield of the primary process O/sub 2/ + hv (214 nm) ..-->.. 2O(/sup 3/P) is estimated as being equal to 0.93 /plus minus/ 0.08 (2sigma). Based on the observed linear buildup of ozone and on model calculations, an upper limit of about 0.03 is estimated for O/sub 3/ photolysis via a channel which leads to O(/sup 3/P) and an excited O/sub 2/ species that can regenerate ozone in its reaction with oxygen.
Published Version
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