Thermochromatographic studies of plutonium oxides

Trace amounts of oxidic plutonium species were studied by thermochromatography in silica glass columns in comparison to oxidic species of Th, Pa, U, Np, and Am. Humid oxygen was used as reactive admixture to the carrier gas helium. The thermochromatographic behavior of plutonium provides evidence for the oxidation of Pu(IV) to Pu(VI) with humid oxygen. The gas chromatographic transport of U, Np, and Pu is governed by the surface reaction MO2(OH)2(g) ↔ MO3(ads) + H2O(g), with M = U, Np, and Pu in the hexavalent state and competitive reactions of the actinide oxides with silica to nonvolatile compounds or solid solutions. There is good agreement with earlier volatility studies and the reported oxidation of PuO2 with water. The oxidation to PuO4 as claimed by Domanov could not be confirmed. (orig.)