title: Reaction of plutonium dioxide with water: formation and properties of PuO(2+x)
abstract: Results show that PuO(2+x), a high-composition (x </= 0.27) phase containing Pu(VI), is the stable binary oxide in air. This nonstoichiometric oxide forms by reaction of dioxide with water and by water-catalyzed reaction of dioxide with oxygen. The PuO(2) + H(2)O reaction rate is 0.27 nanomoles per meter squared per hour at 25 degrees C; the activation energy at 25 degrees to 350 degrees C is 39 kilojoules per mole. Slow kinetics and a low lattice parameter-composition dependence for fluorite-related PuO(2+x) are consistent with a failure to observe the phase in earlier studies. Perplexing aspects of plutonium oxide chemistry can now be explained.
authors.affiliation: 11003 Willow Bend Drive, Waco, TX 76712, USA. Los Alamos National Laboratory, Los Alamos, NM 87545, USA.
authors.initials: JM
authors.lastname: Haschke
authors.initials: TH
authors.lastname: Allen
authors.initials: LA
authors.lastname: Morales