Photochemical precipitation of thorium and cerium and their separation from other ions in aqueous solution

Thorium was precipitated from homogeneous solution by exposing solutions of thorium and periodate in dilute perchloric acid to 253.7 nm radiation from a low-pressure mercury lamp. Periodate is reduced photochemically to iodate which causes the formation of a dense precipitate of the basic iodate of thorium(IV). The precipitate was redissolved, the iodate reduced, the thorium precipitated first as the hydroxide, then as the oxalate and ignited to the dioxide for weighing. Thorium(IV) solutions containing 8-200 mg of ThO(2) gave quantitative results with a standard deviation (s) of 0.2 mg. Separations from 25 mg each of iron, calcium, magnesium, 50 mg of yttrium and up to 500 mg of uranium(VI) were quantitative (s = 0.25 mg). Separations from rare earths, except cerium, were accomplished by using hexamethylenetetramine rather than ammonia for the precipitation of the hydroxide. Cerium(III) was similarly precipitated and converted into CeO(2) for weighing. Quantitative results were obtained for 13-150 mg of CeO(2) with a standard deviation of 0.2 mg. Separations from 200 mg of uranium were quantitative. Other rare earths and yttrium interfered seriously. The precipitates of the basic cerium(IV) and thorium iodates obtained are more compact than those obtained by direct precipitation and can be handled easily. Attempts to duplicate Suzuki's method for separating cerium from neodymium and yttrium were not successful.