Probing the thermal decomposition of plutonium (III) oxalate with IR and Raman spectroscopy, X-ray diffraction, and electron microscopy

The thermal decomposition of Pu(III) oxalate was analyzed by Raman microspectroscopy, infrared spectroscopy, scanning electron microscopy, and powder X-ray diffraction. These data show that crystalline Pu2(C2O4)3 & BULL;9H2O progressively loses water and oxalate ligands as it is heated, which leads to a decrease in long-range lattice ordering, though minimal changes are observed in gross crystalline morphology. The onset of PuO2 formation was observed between 200 - 250 celcius. Thermal decomposition of oxalate ligands leads to the formation of CO2 and plutonium oxalate-carbonate moieties, which had not been observed in previously published thermogravimetric measurements of Pu(III) oxalate. Formation of plutonium oxalate-carbonate moieties is believed to be associated with a change in the plutonium oxidation state from 3+ to 4+, which occurs prior to PuO2 formation. The data provided herein demonstrate the rich spectroscopic nature of a rather underexplored, and technologically relevant, plutonium system. Ideally these results will further future investigations into the Pu(III) oxalate system both experimentally and computationally.

Automated summary

The thermal decomposition of Pu(III) oxalate was analyzed using various spectroscopic and microscopic techniques. It was found that as the oxalate is heated, water and oxalate ligands are progressively lost from the crystalline structure of Pu2(C2O4)3 & BULL;9H2O, leading to a decrease in lattice ordering. The formation of PuO2 and plutonium oxalate-carbonate moieties were also observed, which provide valuable insights into the plutonium system.