The chlorination of plutonium dioxide

We investigated the conversion of PuO/sub 2/ to PuCl/sub 3/ with a number of chlorinating agents, sources of PuO/sub 2/, and reaction conditions, including temperature. We examined Cl/sub 2/, HCl, CCl/sub 4/, Cl/sub 2/-CCl/sub 4/, and HCl-CCl/sub 4/ as potential chlorinating agents. Our study showed tyhat Cl/sub 2/-CCl/sub 4) was the superior chlorinating agent. Using this agent, low-fired PuO/sub 2/--formed by calcining plutonium (III) oxalate at temperatures below 500/degree/C--is more reactive toward chlorination than high-fired PuO/sub 2/, which is formed by calcining plutonium (III) oxalate at 850/degree/C. Both the low- and high-fired PuO/sub 2/ feed materials are more reactive than when PuO/sub 2/ is produced by burning plutonium metal at 400--500/degree/C (foundry oxide). The conversion efficiency of PuO/sub 2/ to PuCl/sub 3/ is relatively constant over a batch-size range of 10--300 g. 21 refs., 10 figs., 2 tabs.