title: Redox reactions of Pu(IV) and Pu(III) in the presence of acetohydroxamic acid in HNO(3) solutions.
abstract: The reduction of Pu(IV) in the presence of acetohydroxamic acid (HAHA) was monitored by vis-NIR spectroscopy. All experiments were performed under low HAHA/Pu(IV) ratios, where only the Pu(IV)-monoacetohydroxamate complex and Pu uncomplexed with HAHA were present in relevant concentrations. Time dependent concentrations of all absorbing species were resolved using molar extinction coefficients for Pu(IV), Pu(III), and the Pu(AHA)(3+) complex by deconvolution of spectra. From fitting of the experimental data by rate equations integrated by a numeric method three reactions were proposed to describe a mechanism responsible for the reduction and oxidation of plutonium in the presence of HAHA and HNO(3). Decomposition of Pu(AHA)(3+) follows a second order reaction mechanism with respect to its own concentration and leads to the formation of Pu(III). At low HAHA concentrations, a two-electron reduction of uncomplexed Pu(IV) with HAHA also occurs. Formed Pu(III) is unstable and slowly reoxidizes back to Pu(IV), which, at the point when all HAHA is decomposed, can be catalyzed by the presence of nitrous acid.
authors.affiliation: Radiation Center, Oregon State University, Corvallis, Oregon 97331, USA.
authors.forename: Peter
authors.initials: P
authors.lastname: Tkac
authors.forename: Martin
authors.initials: M
authors.lastname: Precek
authors.forename: Alena
authors.initials: A
authors.lastname: Paulenova
mesh_terms: D006877:Hydroxamic Acids / Q000737:chemistry*; D017942:Nitric Acid / Q000737:chemistry*; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D010084:Oxidation-Reduction; D011005:Plutonium / Q000737:chemistry*; D012996:Solutions; D013997:Time Factors
chemical_list: D006877:Hydroxamic Acids; D009942:Organometallic Compounds; D012996:Solutions; D017942:Nitric Acid; C006358:acetohydroxamic acid; D011005:Plutonium