Kinetics of the Autoreduction of Hexavalent Americium in Aqueous Nitric Acid

Grimes, Travis S.; Horne, Gregory P.; Dares, Christopher J.; Pimblott, Simon M.; Mezyk, Stephen P.; Mincher, Bruce J.

doi:10.1021/acs.inorgchem.7b00990

Kinetics of the Autoreduction of Hexavalent Americium in Aqueous Nitric Acid

Journal Article · Thu Jun 29 00:00:00 EDT 2017 · Inorganic Chemistry

DOI:https://doi.org/10.1021/acs.inorgchem.7b00990· OSTI ID:1471064

^[1]; ^[2]; Dares, Christopher J. ^[3]; Pimblott, Simon M. ^[4]; Mezyk, Stephen P. ^[5]; Mincher, Bruce J. ^[1]

Idaho National Lab. (INL), Idaho Falls, ID (United States)
California State University at Long Beach, Long Beach, CA (United States); Univ. of Notre Dame, Notre Dame, IN (United States)
Florida Intl Univ., Miami, FL (United States)
The Univ. of Manchester, Cumbria (United Kingdom); The Univ. of Manchester, Manchester (United Kingdom)
California State University at Long Beach, Long Beach, CA (United States)

The rate of reduction of hexavalent americium 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 concentration of total americium. This indicates that reduction is due to reaction of hexavalent americium with the radiolysis product 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 range of nitric acid concentrations studied were determined by sensitivity analysis in which mass balance with the known total americium concentration was obtained. The new extinction coefficients and reduction rate constants have been tabulated here. Multi-scale radiation chemical modeling using a reaction set with both known and estimated rate coefficients was employed to achieve excellent agreement with the experimental results, and indicates 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 the highest concentrations of these species occurred at intermediate nitric acid concentrations. In conclusion, this is in agreement with the empirical finding that the highest rate constant for autoreduction occurred at the intermediate acid concentration.

View Accepted Manuscript (DOE)

Research Organization:: Idaho National Laboratory (INL), Idaho Falls, ID (United States)

Sponsoring Organization:: USDOE Office of Nuclear Energy (NE)

Grant/Contract Number:: AC07-05ID14517

OSTI ID:: 1471064

Report Number(s):: INL/JOU--17-41567-Rev000

Journal Information:: Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 14 Vol. 56; ISSN 0020-1669

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (30)

Radiolytic reduction of Am (VI) and Am (V) Zaitsev, A. A.; Kosyakov, V. N.; Rykov, A. G. The Soviet Journal of Atomic Energy, Vol. 7, Issue 1 https://doi.org/10.1007/BF01683110	journal	December 1960
The self-reduction of americium(V) and (VI) and the disproportionation of americium(V) in aqueous solution Hall, G. R.; Markin, T. L. Journal of Inorganic and Nuclear Chemistry, Vol. 4, Issue 5-6 https://doi.org/10.1016/0022-1902(57)80011-6	journal	January 1957
New activity coefficients of 0–100 per cent aqueous nitric acid Davis, W.; De Bruin, H. J. Journal of Inorganic and Nuclear Chemistry, Vol. 26, Issue 6 https://doi.org/10.1016/0022-1902(64)80268-2	journal	June 1964
Review of hydrometallurgical recovery of zinc from industrial wastes Jha, M. K.; Kumar, V.; Singh, R. J. Resources, Conservation and Recycling, Vol. 33, Issue 1 https://doi.org/10.1016/S0921-3449(00)00095-1	journal	August 2001
A short history of hydrometallurgy Habashi, Fathi Hydrometallurgy, Vol. 79, Issue 1-2 https://doi.org/10.1016/j.hydromet.2004.01.008	journal	September 2005
Hydrometallurgical recovery of cadmium and nickel from spent Ni–Cd batteries Rudnik, Ewa; Nikiel, Marek Hydrometallurgy, Vol. 89, Issue 1-2 https://doi.org/10.1016/j.hydromet.2007.05.006	journal	September 2007
Hexavalent Actinide Extraction Using N , N -Dialkyl Amides McCann, Kevin; Mincher, Bruce J.; Schmitt, Nicholas C. Industrial & Engineering Chemistry Research, Vol. 56, Issue 22 https://doi.org/10.1021/acs.iecr.7b01181	journal	May 2017
Decay Mechanism of NO ₃ ^• Radical in Highly Concentrated Nitrate and Nitric Acidic Solutions in the Absence and Presence of Hydrazine Garaix, Guillaume; Horne, Gregory P.; Venault, Laurent The Journal of Physical Chemistry B, Vol. 120, Issue 22 https://doi.org/10.1021/acs.jpcb.6b02915	journal	May 2016
Multi-Scale Modeling of the Gamma Radiolysis of Nitrate Solutions Horne, Gregory P.; Donoclift, Thomas A.; Sims, Howard E. The Journal of Physical Chemistry B, Vol. 120, Issue 45 https://doi.org/10.1021/acs.jpcb.6b06862	journal	November 2016
Reevaluation of Neptunium–Nitric Acid Radiation Chemistry by Multiscale Modeling Horne, G. P.; Grimes, T. S.; Mincher, B. J. The Journal of Physical Chemistry B, Vol. 120, Issue 49 https://doi.org/10.1021/acs.jpcb.6b09683	journal	November 2016
Higher Oxidation States of Americium: Preparation, Characterization and Use for Separations Runde, Wolfgang H.; Mincher, Bruce J. Chemical Reviews, Vol. 111, Issue 9 https://doi.org/10.1021/cr100181f	journal	September 2011
Americium and curium Keenan, Thomas K. Journal of Chemical Education, Vol. 36, Issue 1 https://doi.org/10.1021/ed036p27	journal	January 1959
Environmental Speciation of Actinides Maher, Kate; Bargar, John R.; Brown, Gordon E. Inorganic Chemistry, Vol. 52, Issue 7 https://doi.org/10.1021/ic301686d	journal	June 2012
The Kinetics of the Disproportionation of Americium(V) Coleman, James S. Inorganic Chemistry, Vol. 2, Issue 1 https://doi.org/10.1021/ic50005a016	journal	February 1963
Tributylphosphate Extraction Behavior of Bismuthate-Oxidized Americium Mincher, Bruce J.; Martin, Leigh R.; Schmitt, Nicholas C. Inorganic Chemistry, Vol. 47, Issue 15 https://doi.org/10.1021/ic800667h	journal	August 2008
The Pentavalent State of Americium Werner, L. B.; Perlman, I. Journal of the American Chemical Society, Vol. 73, Issue 1 https://doi.org/10.1021/ja01145a540	journal	January 1951
Hexavalent Americium ¹ Asprey, L. B.; Stephanou, S. E.; Penneman, R. A. Journal of the American Chemical Society, Vol. 73, Issue 12 https://doi.org/10.1021/ja01156a065	journal	December 1951
A NEW VALENCE STATE OF AMERICIUM, AM(VI) ¹ Asprey, L. B.; Stephanou, S. E.; Penneman, R. A. Journal of the American Chemical Society, Vol. 72, Issue 3 https://doi.org/10.1021/ja01159a528	journal	March 1950
The Heats of Formation of AmO ₂ ⁺ (aq) and AmO ₂ ⁺⁺ (aq) in 1 M HClO ₄ ¹ Gunn, S. R.; Cunningham, B. B. Journal of the American Chemical Society, Vol. 79, Issue 7 https://doi.org/10.1021/ja01564a011	journal	April 1957
Effects of Track Structure on the Ion Radiolysis of the Fricke Dosimeter Pimblott, Simon M.; LaVerne, Jay A. The Journal of Physical Chemistry A, Vol. 106, Issue 41 https://doi.org/10.1021/jp020830u	journal	October 2002
Experimental Coordination Environment of Uranyl(VI) in Aqueous Solution Neuefeind, J.; Soderholm, L.; Skanthakumar, S. The Journal of Physical Chemistry A, Vol. 108, Issue 14 https://doi.org/10.1021/jp037997n	journal	April 2004
Electronic Structure and Bonding in Actinyl Ions and their Analogs Denning, Robert G. The Journal of Physical Chemistry A, Vol. 111, Issue 20 https://doi.org/10.1021/jp071061n	journal	May 2007
Monte Carlo Simulation of Range and Energy Deposition by Electrons in Gaseous and Liquid Water Pimblott, Simon M.; LaVerne, Jay A.; Mozumder, Asokendu The Journal of Physical Chemistry, Vol. 100, Issue 20 https://doi.org/10.1021/jp9536559	journal	January 1996
γ-Radiolysis study of concentrated nitric acid solutions Jiang, Pei-Yun; Nagaishi, Ryuji; Yotsuyanagi, Tadasu J. Chem. Soc., Faraday Trans., Vol. 90, Issue 1 https://doi.org/10.1039/FT9949000093	journal	January 1994
Stochastic models of multi-species kinetics in radiation-induced spurs Clifford, Peter; Green, Nicholas J. B.; Oldfield, Mark J. Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, Vol. 82, Issue 9 https://doi.org/10.1039/f19868202673	journal	January 1986
The separation and purification of americium-241 and the absorption spectra of tervalent and quinquevalent americium solutions Hall, G. R.; Herniman, P. D. Journal of the Chemical Society (Resumed) https://doi.org/10.1039/jr9540002214	journal	January 1954
Diamylamylphosphonate Solvent Extraction of Am(VI) from Nuclear Fuel Raffinate Simulant Solution Mincher, Bruce J.; Martin, Leigh R.; Schmitt, Nicholas C. Solvent Extraction and Ion Exchange, Vol. 30, Issue 5 https://doi.org/10.1080/07366299.2012.671108	journal	August 2012
Electrochemical oxidation of 243Am(III) in nitric acid by a terpyridyl-derivatized electrode Dares, C. J.; Lapides, A. M.; Mincher, B. J. Science, Vol. 350, Issue 6261 https://doi.org/10.1126/science.aac9217	journal	November 2015
Americium(III) oxidation by copper(III) periodate in nitric acid solution as compared with the action of Bi(V) compounds of sodium, lithium, and potassium Sinkov, Sergey I.; Lumetta, Gregg J. Radiochimica Acta, Vol. 103, Issue 8 https://doi.org/10.1515/ract-2014-2315	journal	January 2015
The redox chemistry of neptunium in γ -irradiated aqueous nitric acid Mincher, Bruce J.; Precek, Martin; Mezyk, Stephen P. Radiochimica Acta, Vol. 101, Issue 4 https://doi.org/10.1524/ract.2013.2013	journal	April 2013

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Neptunium( iv )-hydroxamate complexes: their speciation, and kinetics and mechanism of hydrolysis Edwards, S.; Andrieux, F.; Boxall, C. Dalton Transactions, Vol. 48, Issue 2 https://doi.org/10.1039/c8dt02194e	journal	January 2019
Electrochemical oxidation of trivalent americium using a dipyrazinylpyridine modified ITO electrode Lopez, Michael J.; Sheridan, Matthew V.; McLachlan, Jeffrey R. Chemical Communications, Vol. 55, Issue 28 https://doi.org/10.1039/c9cc00837c	journal	January 2019
Relationship Between Structure and Coordination Strength of N and N,O -Hybrid Donor Ligands with Trivalent Lanthanides Nakase, Masahiko; Kobayashi, Tohru; Shiwaku, Hideaki Solvent Extraction and Ion Exchange, Vol. 36, Issue 7 https://doi.org/10.1080/07366299.2018.1532137	journal	November 2018

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