Carbon isotope effects in photodissociation of phosgene. I. Photocatalyzed carbon isotope exchange between phosgene and carbon monoxide

Physics – Chemical Physics

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Kinetic Isotope Effects Including Muonium, Chemical Exchanges

Scientific paper

The exchange reaction 12COCl2+13CO?13COCl2+ 12CO is theoretically expected to have a separation factor of 1.04 at 60°C, and of 1.07 at -35°C. Pure COCl2 and a series of COCl2-CO gaseous mixtures were irradiated either with the 253.7 nm mercury line or the light of a medium pressure mercury lamp (above 200 nm). The 13C distribution in the photostationary state has shown separation factors ranging from 1.092 at 60°C to 1.170 at -35°C for the 253.7 line and from 1.059 at 60°C to 1.067 at 25°C at irradiation with the medium pressure lamp. The increase of the factors above the theoretically predicted values is attributed to differences in the fine structure of 12COCl2 and 13COCl2 predissociation spectra. The possibility of improving the selectivity of the separation process is analyzed.

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