Kinetics of the Autoreduction of Hexavalent Americium in Aqueous Nitric Acid
Abstract
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 intermediatemore »
- Authors:
-
[1];
[2];
- 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)
- Publication Date:
- Research Org.:
- Idaho National Lab. (INL), Idaho Falls, ID (United States)
- Sponsoring Org.:
- USDOE Office of Nuclear Energy (NE)
- OSTI Identifier:
- 1471064
- Report Number(s):
- INL/JOU-17-41567-Rev000
Journal ID: ISSN 0020-1669
- Grant/Contract Number:
- AC07-05ID14517
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Inorganic Chemistry
- Additional Journal Information:
- Journal Volume: 56; Journal Issue: 14; Journal ID: ISSN 0020-1669
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS; Americium Reduction; Reduction Kinetics; Hexavalent Americium Reduction
Citation Formats
Grimes, Travis S., Horne, Gregory P., Dares, Christopher J., Pimblott, Simon M., Mezyk, Stephen P., and Mincher, Bruce J. Kinetics of the Autoreduction of Hexavalent Americium in Aqueous Nitric Acid. United States: N. p., 2017.
Web. doi:10.1021/acs.inorgchem.7b00990.
Grimes, Travis S., Horne, Gregory P., Dares, Christopher J., Pimblott, Simon M., Mezyk, Stephen P., & Mincher, Bruce J. Kinetics of the Autoreduction of Hexavalent Americium in Aqueous Nitric Acid. United States. https://doi.org/10.1021/acs.inorgchem.7b00990
Grimes, Travis S., Horne, Gregory P., Dares, Christopher J., Pimblott, Simon M., Mezyk, Stephen P., and Mincher, Bruce J. Thu .
"Kinetics of the Autoreduction of Hexavalent Americium in Aqueous Nitric Acid". United States. https://doi.org/10.1021/acs.inorgchem.7b00990. https://www.osti.gov/servlets/purl/1471064.
@article{osti_1471064,
title = {Kinetics of the Autoreduction of Hexavalent Americium in Aqueous Nitric Acid},
author = {Grimes, Travis S. and Horne, Gregory P. and Dares, Christopher J. and Pimblott, Simon M. and Mezyk, Stephen P. and Mincher, Bruce J.},
abstractNote = {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.},
doi = {10.1021/acs.inorgchem.7b00990},
journal = {Inorganic Chemistry},
number = 14,
volume = 56,
place = {United States},
year = {Thu Jun 29 00:00:00 EDT 2017},
month = {Thu Jun 29 00:00:00 EDT 2017}
}
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Works referenced in this record:
Review of hydrometallurgical recovery of zinc from industrial wastes
journal, August 2001
- Jha, M. K.; Kumar, V.; Singh, R. J.
- Resources, Conservation and Recycling, Vol. 33, Issue 1
A short history of hydrometallurgy
journal, September 2005
- Habashi, Fathi
- Hydrometallurgy, Vol. 79, Issue 1-2
Hydrometallurgical recovery of cadmium and nickel from spent Ni–Cd batteries
journal, September 2007
- Rudnik, Ewa; Nikiel, Marek
- Hydrometallurgy, Vol. 89, Issue 1-2
Experimental Coordination Environment of Uranyl(VI) in Aqueous Solution
journal, April 2004
- Neuefeind, J.; Soderholm, L.; Skanthakumar, S.
- The Journal of Physical Chemistry A, Vol. 108, Issue 14
Electronic Structure and Bonding in Actinyl Ions and their Analogs
journal, May 2007
- Denning, Robert G.
- The Journal of Physical Chemistry A, Vol. 111, Issue 20
Environmental Speciation of Actinides
journal, June 2012
- Maher, Kate; Bargar, John R.; Brown, Gordon E.
- Inorganic Chemistry, Vol. 52, Issue 7
Tributylphosphate Extraction Behavior of Bismuthate-Oxidized Americium
journal, August 2008
- Mincher, Bruce J.; Martin, Leigh R.; Schmitt, Nicholas C.
- Inorganic Chemistry, Vol. 47, Issue 15
Diamylamylphosphonate Solvent Extraction of Am(VI) from Nuclear Fuel Raffinate Simulant Solution
journal, August 2012
- Mincher, Bruce J.; Martin, Leigh R.; Schmitt, Nicholas C.
- Solvent Extraction and Ion Exchange, Vol. 30, Issue 5
Hexavalent Actinide Extraction Using N , N -Dialkyl Amides
journal, May 2017
- McCann, Kevin; Mincher, Bruce J.; Schmitt, Nicholas C.
- Industrial & Engineering Chemistry Research, Vol. 56, Issue 22
A NEW VALENCE STATE OF AMERICIUM, AM(VI) 1
journal, March 1950
- Asprey, L. B.; Stephanou, S. E.; Penneman, R. A.
- Journal of the American Chemical Society, Vol. 72, Issue 3
Hexavalent Americium 1
journal, December 1951
- Asprey, L. B.; Stephanou, S. E.; Penneman, R. A.
- Journal of the American Chemical Society, Vol. 73, Issue 12
The Pentavalent State of Americium
journal, January 1951
- Werner, L. B.; Perlman, I.
- Journal of the American Chemical Society, Vol. 73, Issue 1
The Heats of Formation of AmO 2 + (aq) and AmO 2 ++ (aq) in 1 M HClO 4 1
journal, April 1957
- Gunn, S. R.; Cunningham, B. B.
- Journal of the American Chemical Society, Vol. 79, Issue 7
The Kinetics of the Disproportionation of Americium(V)
journal, February 1963
- Coleman, James S.
- Inorganic Chemistry, Vol. 2, Issue 1
The separation and purification of americium-241 and the absorption spectra of tervalent and quinquevalent americium solutions
journal, January 1954
- Hall, G. R.; Herniman, P. D.
- Journal of the Chemical Society (Resumed)
The self-reduction of americium(V) and (VI) and the disproportionation of americium(V) in aqueous solution
journal, January 1957
- Hall, G. R.; Markin, T. L.
- Journal of Inorganic and Nuclear Chemistry, Vol. 4, Issue 5-6
Americium and curium
journal, January 1959
- Keenan, Thomas K.
- Journal of Chemical Education, Vol. 36, Issue 1
The redox chemistry of neptunium in γ -irradiated aqueous nitric acid
journal, April 2013
- Mincher, Bruce J.; Precek, Martin; Mezyk, Stephen P.
- Radiochimica Acta, Vol. 101, Issue 4
Reevaluation of Neptunium–Nitric Acid Radiation Chemistry by Multiscale Modeling
journal, November 2016
- Horne, G. P.; Grimes, T. S.; Mincher, B. J.
- The Journal of Physical Chemistry B, Vol. 120, Issue 49
Monte Carlo Simulation of Range and Energy Deposition by Electrons in Gaseous and Liquid Water
journal, January 1996
- Pimblott, Simon M.; LaVerne, Jay A.; Mozumder, Asokendu
- The Journal of Physical Chemistry, Vol. 100, Issue 20
Effects of Track Structure on the Ion Radiolysis of the Fricke Dosimeter
journal, October 2002
- Pimblott, Simon M.; LaVerne, Jay A.
- The Journal of Physical Chemistry A, Vol. 106, Issue 41
Stochastic models of multi-species kinetics in radiation-induced spurs
journal, January 1986
- 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
Multi-Scale Modeling of the Gamma Radiolysis of Nitrate Solutions
journal, November 2016
- Horne, Gregory P.; Donoclift, Thomas A.; Sims, Howard E.
- The Journal of Physical Chemistry B, Vol. 120, Issue 45
Decay Mechanism of NO 3 • Radical in Highly Concentrated Nitrate and Nitric Acidic Solutions in the Absence and Presence of Hydrazine
journal, May 2016
- Garaix, Guillaume; Horne, Gregory P.; Venault, Laurent
- The Journal of Physical Chemistry B, Vol. 120, Issue 22
Higher Oxidation States of Americium: Preparation, Characterization and Use for Separations
journal, September 2011
- Runde, Wolfgang H.; Mincher, Bruce J.
- Chemical Reviews, Vol. 111, Issue 9
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
journal, January 2015
- Sinkov, Sergey I.; Lumetta, Gregg J.
- Radiochimica Acta, Vol. 103, Issue 8
Radiolytic reduction of Am (VI) and Am (V)
journal, December 1960
- Zaitsev, A. A.; Kosyakov, V. N.; Rykov, A. G.
- The Soviet Journal of Atomic Energy, Vol. 7, Issue 1
Electrochemical oxidation of 243Am(III) in nitric acid by a terpyridyl-derivatized electrode
journal, November 2015
- Dares, C. J.; Lapides, A. M.; Mincher, B. J.
- Science, Vol. 350, Issue 6261
New activity coefficients of 0–100 per cent aqueous nitric acid
journal, June 1964
- Davis, W.; De Bruin, H. J.
- Journal of Inorganic and Nuclear Chemistry, Vol. 26, Issue 6
γ-Radiolysis study of concentrated nitric acid solutions
journal, January 1994
- Jiang, Pei-Yun; Nagaishi, Ryuji; Yotsuyanagi, Tadasu
- J. Chem. Soc., Faraday Trans., Vol. 90, Issue 1
Works referencing / citing this record:
Relationship Between Structure and Coordination Strength of N and N,O -Hybrid Donor Ligands with Trivalent Lanthanides
journal, November 2018
- Nakase, Masahiko; Kobayashi, Tohru; Shiwaku, Hideaki
- Solvent Extraction and Ion Exchange, Vol. 36, Issue 7
Neptunium( iv )-hydroxamate complexes: their speciation, and kinetics and mechanism of hydrolysis
journal, January 2019
- Edwards, S.; Andrieux, F.; Boxall, C.
- Dalton Transactions, Vol. 48, Issue 2
Electrochemical oxidation of trivalent americium using a dipyrazinylpyridine modified ITO electrode
journal, January 2019
- Lopez, Michael J.; Sheridan, Matthew V.; McLachlan, Jeffrey R.
- Chemical Communications, Vol. 55, Issue 28