Kinetics of the Autoreduction of Hexavalent Americium in Aqueous Nitric Acid

• Published in: Inorganic chemistry Vol. 56; no. 14; pp. 8295 - 8301
• Main Authors: Grimes, Travis S, Horne, Gregory P, Dares, Christopher J, Pimblott, Simon M, Mezyk, Stephen P, Mincher, Bruce J
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 17.07.2017; American Chemical Society (ACS)
• Subjects: Americium Reduction; Hexavalent Americium Reduction; NUCLEAR FUEL CYCLE AND FUEL MATERIALS; Reduction Kinetics
• ISSN: 0020-1669; 1520-510X
• DOI: 10.1021/acs.inorgchem.7b00990

The rate of reduction of hexavalent 243Am due to self-radiolysis was measured across a range of total americium and nitric acid concentrations. These so-called autoreduction rates exhibited zero-order kinetics with respect to the concentration of hexavalent americium, and pseudo-first-order kinetics with respect to the total concentration of americium. However, the rate constants did vary with nitric acid concentration, resulting in values of 0.0048 ± 0.0003, 0.0075 ± 0.0005, and 0.0054 ± 0.0003 h–1 for 1.0, 3.0, and 6.5 M HNO3, respectively. This indicates that reduction is due to reaction of hexavalent americium with the radiolysis products of total americium decay. The concentration changes of Am­(III), Am­(V), and Am­(VI) were determined by UV–vis spectroscopy. The Am­(III) molar extinction coefficients are known; however, the unknown values for the Am­(V) and Am­(VI) absorbances across the studied range of nitric acid concentrations were determined by sensitivity analysis in which a mass balance with the known total americium concentration was obtained. The new extinction coefficients and reduction rate constants have been tabulated here. Multiscale radiation chemical modeling using a reaction set with both known and optimized rate coefficients was employed to achieve excellent agreement with the experimental results, and indicates that radiolytically produced nitrous acid from nitric acid radiolysis and hydrogen peroxide from water radiolysis are the important reducing agents. Since these species also react with each other, modeling indicated that the highest concentrations of these species available for Am­(VI) reduction occurred at 3.0 M HNO3. This is in agreement with the empirical finding that the highest rate constant for autoreduction occurred at the intermediate acid concentration.