Effect of excess ozone on UV-stimulated tritium oxidation

The authors have reported that the oxidation of tritium is considerably accelerated by irradiating a mixture gas of HT(H2)-O2 with UV-photons, and this UV-stimulated HT oxidation is mainly due to the formation of intermediates such as ozone and activated oxygen species. This suggests that the oxidation will be much more enhanced in the presence of excess ozone in the reaction system. To examine this possibility, effects of the excess ozone on the UV-stimulated HT oxidation was experimentally studied on the one hand, and reaction mechanisms were investigated by developing a computer simulation program applicable to the three-component system of HT(H2)-O2-O3. The formation rate of HTO was measured for gas mixtures consisting of O2(75.5 Torr), O3(0.5-2% of O2), H2(0.1-3% of O2) and HT(H2/HT=12000). The experiments showed considerable enhancement of the HTO production rate in the presence of excess ozone by UV-photons from a low pressure mercury lamp(5W). The time course of the reaction was reproduced quite well by computer simulation, indicating that the assumed reaction mechanism is valid. This is also supported by observations that computer simulation reproduced the experimentally observed dependence of ozone decomposition rate on ozone and hydrogen pressures under the UV-irradiation. Those results showed that UV-stimulated HT oxidation was accelerated by about 14000 times in the presence of excess ozone. It strongly suggests that the UV-stimulated oxidation in the presence of excess ozone will be applicable to tritium handling systems as a non-catalytic tritium removal method. (author)