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Pulse Radiolysis Study of Cf3CCl2 and Cf3CCl2O2 Radicals in the Gas Phase At 295 K

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The ultraviolet absorption spectra and self reaction kinetics of CF3CCl2 and CF3CCl2O2 radicals have been studied in the gas phase at 295K. Absorption cross sections were quantified over the wavelength range 220-300 nm. Measured cross sections near the absorption maxima were σCF3CCl2(230 nm) = (9.70 ± 1.47) x 10-18 and σCF3CCl2O2(250 nm) = (1.70 ± 0.26) x 10-18 cm2 molecule-1. Errors are statistical (2σ) together with our estimate of potential systematic errors. Rate constants for the self reaction of CF3CCl2 and CF3CCl2O2 radicals were measured to be k6 = (2.46 ± 0.43) x 10-12 and k7obs = (3.33 ± 0.53) × 10-12 cm3 molecule-1 s-1, respectively. Results are discussed with respect to the existing database concerning halogenated peroxy radicals.

Affiliations: 1: Ford Research Laboratory, SRL-E3083, Ford Motor Company, Dearborn, Michigan 48121-2053, U.S.A; 2: Section for Chemical Reactivity, Environmental Science and Technology Department, Risø National Laboratory, DK-4000 Roskilde, Denmark


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