Multiscale Modeling of Plutonium Radiation Chemistry in Nitric Acid Solutions. 1. Cobalt-60 Gamma Irradiation of Pu(IV)

Kynman, Amy Elizabet; Grimes, Travis S.; Conrad, Jacy Kathleen; Pimblott, Simon M.; Horne, Gregory Peter

doi:10.1021/acs.inorgchem.4c00138

Title: Multiscale Modeling of Plutonium Radiation Chemistry in Nitric Acid Solutions. 1. Cobalt-60 Gamma Irradiation of Pu(IV)

Journal Article · 23 April 2024 · Inorganic Chemistry

DOI: https://doi.org/10.1021/acs.inorgchem.4c00138 · OSTI ID:2345708

^[1];

^[1]

Idaho National Laboratory (INL), Idaho Falls, ID (United States). Center for Radiation Chemistry Research

We report careful manipulation of the plutonium oxidation states is essential in the study and utilization of its rich redox chemistry. To achieve this level of control, a comprehensive mechanistic understanding of radiation-induced plutonium redox chemistry is critical due to the unavoidable exposure of plutonium to ionizing radiation fields, both inherent and from in-process applications. To this end, we have developed an experimentally evaluated multiscale computer model for the prediction of gamma radiation-induced Pu(IV) redox chemistry in concentrated nitric acid solutions (1.0, 3.0, and 6.0 M). Under these acidic, aqueous solution conditions, cobalt-60 gamma irradiation afforded marginal net conversion of Pu(IV) to Pu(VI), the extent of which was dependent on the concentration of HNO₃ and absorbed gamma dose. Multiscale calculations, which are in excellent agreement with experimental data, indicate that this observation is due to a combination of inherent plutonium disproportionation reactions and several radiation-induced processes, including redox cycling between Pu(IV) and Pu(III), as achieved by the reduction of Pu(IV) by nitrous acid and hydrogen peroxide, the oxidation of Pu(III) by nitrate and hydroxyl radicals, and the sequential oxidation of Pu(IV) to Pu(V) and Pu(VI) by the remaining available yield of nitrate radicals.

View Accepted Manuscript (DOE)

Cite

Export

Save

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:: 2345708

Report Number(s):: INL/JOU24-76152-Revision-0

Journal Information:: Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 18 Vol. 63; ISSN 0020-1669

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (40)

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
Kinetics of the Autoreduction of Hexavalent Americium in Aqueous Nitric Acid Grimes, Travis S.; Horne, Gregory P.; Dares, Christopher J. Inorganic Chemistry, Vol. 56, Issue 14 https://doi.org/10.1021/acs.inorgchem.7b00990	journal	June 2017
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
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
Plutonium(III) oxidation under α-irradiation in nitric acid solutions Andreychuk, N. N.; Frolov, A. A.; Rotmanov, K. V. Journal of Radioanalytical and Nuclear Chemistry Articles, Vol. 143, Issue 2 https://doi.org/10.1007/bf02039611	journal	December 1990
Kinetics and Mechanisms for the Oxidation of Trivalent Plutonium by Nitrous Acid ¹ Dukes, E. K. Journal of the American Chemical Society, Vol. 82, Issue 1 https://doi.org/10.1021/ja01486a003	journal	January 1960
The study of reactivity of actinide ions towards hydrated electrons and hydrogen atoms in acid aqueous solutions by a pulse radiolysis method Gogolev, A. V.; Shilov, V. P.; Fedoseev, A. M. International Journal of Radiation Applications and Instrumentation. Part C. Radiation Physics and Chemistry, Vol. 37, Issue 3 https://doi.org/10.1016/1359-0197(91)90031-V	journal	January 1991
Radiation chemistry of actinides Vladimirova, M. V. Journal of Radioanalytical and Nuclear Chemistry Articles, Vol. 143, Issue 2 https://doi.org/10.1007/BF02039613	journal	December 1990
Molecular Hydrogen Yields from the α-Self-Radiolysis of Nitric Acid Solutions Containing Plutonium or Americium Gregson, Colin R.; Horne, Gregory P.; Orr, Robin M. The Journal of Physical Chemistry B, Vol. 122, Issue 9 https://doi.org/10.1021/acs.jpcb.7b12267	journal	February 2018
The Chemistry of the Actinide and Transactinide Elements Morss, Lester R.; Edelstein, Norman M.; Fuger, Jean https://doi.org/10.1007/1-4020-3598-5	book	January 2006
The Oxidation of Fe ⁺⁺ to Fe ⁺⁺⁺ by the Irradiation with X‐Rays of Solutions of Ferrous Sulfate in Sulfuric Acid Fricke, Hugo; Hart, Edwin J. The Journal of Chemical Physics, Vol. 3, Issue 1 https://doi.org/10.1063/1.1749558	journal	January 1935
Recent achievements of actinide radiation chemistry Vladimirova, M. V. Journal of Alloys and Compounds, Vol. 271-273 https://doi.org/10.1016/S0925-8388(98)00195-9	journal	June 1998
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
Inhibition of Radiolytic Molecular Hydrogen Formation by Quenching of Excited State Water Horne, Gregory P.; Pimblott, Simon M.; LaVerne, Jay A. The Journal of Physical Chemistry B, Vol. 121, Issue 21 https://doi.org/10.1021/acs.jpcb.7b02775	journal	May 2017
Optimization and plutonium equilibrium Silver, G. L. https://doi.org/10.2172/7248905	report	October 1976
Plutonium and Americium Alpha Radiolysis of Nitric Acid Solutions Horne, Gregory P.; Gregson, Colin R.; Sims, Howard E. The Journal of Physical Chemistry B, Vol. 121, Issue 4 https://doi.org/10.1021/acs.jpcb.6b12061	journal	January 2017
Radiolyticaily Generated Hydrogen and Oxygen from Plutonium Nitrate Solutions Kuno, Yusuke; Hina, Tetsuro; Masui, Jinichi Journal of Nuclear Science and Technology, Vol. 30, Issue 9 https://doi.org/10.1080/18811248.1993.9734566	journal	September 1993
Radiation-energy partition among mixture components: Current ideas on an old question Swallow, A. John; Inokuti, Mitio International Journal of Radiation Applications and Instrumentation. Part C. Radiation Physics and Chemistry, Vol. 32, Issue 2 https://doi.org/10.1016/1359-0197(88)90182-8	journal	January 1988
Formation and decay of peroxynitrous acid: a pulse radiolysis study Loegager, T.; Sehested, K. The Journal of Physical Chemistry, Vol. 97, Issue 25 https://doi.org/10.1021/j100127a016	journal	June 1993
Gamma Radiation‐Induced Degradation of Acetohydroxamic Acid (AHA) in Aqueous Nitrate and Nitric Acid Solutions Evaluated by Multiscale Modelling Conrad, Jacy K.; Mezyk, Stephen P.; Isherwood, Liam H. ChemPhysChem, Vol. 24, Issue 5 https://doi.org/10.1002/cphc.202200749	journal	December 2022
On the Oxidation of Plutonium (III) by Hydrogen Peroxide–Probable Formation of an Unstable Plutonium (III) Peroxy Complex Mazumdar, A. S. Ghosh; Vaidyanathan, S. ract, Vol. 19, Issue 4 https://doi.org/10.1524/ract.1973.19.4.165	journal	April 1973
Radiolytically generated gases in plutonium-nitric acid solutions Kazanjian, A. R.; Horrell, D. R. Radiation Effects, Vol. 13, Issue 3-4 https://doi.org/10.1080/00337577208231191	journal	April 1972
The reaction of the precursor of the hydrated electron with electron scavengers Jonah, Charles D.; Miller, John R.; Matheson, Max S. The Journal of Physical Chemistry, Vol. 81, Issue 17 https://doi.org/10.1021/j100532a003	journal	August 1977
Equilibrium constant of the reaction ·OH + HNO₃ ⇆ H₂O + NO₃. in aqueous solution Poskrebyshev, G. A.; Neta, P.; Huie, R. E. Journal of Geophysical Research: Atmospheres, Vol. 106, Issue D5 https://doi.org/10.1029/2000JD900702	journal	March 2001
Radiolytic degradation of formic acid and formate in aqueous solution: modeling the final stages of organic mineralization under advanced oxidation process conditions Horne, Gregory P.; Zalupski, Peter R.; Daubaras, Dayna L. Water Research, Vol. 186 https://doi.org/10.1016/j.watres.2020.116314	journal	November 2020
Plutonium(IV) peroxide formation in nitric medium and kinetics Pu(VI) reduction by hydrogen peroxide Maillard, C.; Adnet, J. -M. Radiochimica Acta, Vol. 89, Issue 8 https://doi.org/10.1524/ract.2001.89.8.485	journal	January 2001
Influence of plutonium oxidation state on the formation of molecular hydrogen, nitrous acid and nitrous oxide from alpha radiolysis of nitric acid solution Perrin, Brandon; Venault, Laurent; Broussard, Emilie Radiochimica Acta, Vol. 110, Issue 5 https://doi.org/10.1515/ract-2021-1136	journal	April 2022
Alpha radiolysis of nitric acid aqueous solution irradiated by 238Pu source Liu, Zhe; Fang, Zhong; Wang, Liang Nuclear Science and Techniques, Vol. 28, Issue 4 https://doi.org/10.1007/s41365-017-0200-4	journal	March 2017
Recovery and Purification of Plutonium by Anion Exchange Ryan, J. L.; Wheelwright, E. J. Industrial & Engineering Chemistry, Vol. 51, Issue 1 https://doi.org/10.1021/ie50589a038	journal	January 1959
Redox chemistry of plutonium and plutonium surrogates in vitrified nuclear wastes Darab, John G.; Li, Hong; Bucher, Jerome J. Journal of the American Ceramic Society, Vol. 105, Issue 11 https://doi.org/10.1111/jace.18632	journal	July 2022
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
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
Multiscale modelling of the radical-induced chemistry of acetohydroxamic acid in aqueous solution Conrad, Jacy K.; Pilgrim, Corey D.; Pimblott, Simon M. RSC Advances, Vol. 12, Issue 46 https://doi.org/10.1039/D2RA03392E	journal	January 2022
Critical Review of rate constants for reactions of hydrated electrons, hydrogen atoms and hydroxyl radicals (⋅OH/⋅O ⁻ in Aqueous Solution Buxton, George V.; Greenstock, Clive L.; Helman, W. Phillips Journal of Physical and Chemical Reference Data, Vol. 17, Issue 2 https://doi.org/10.1063/1.555805	journal	April 1988
Effect of Ionizing Radiation on the Redox Chemistry of Penta- and Hexavalent Americium Horne, Gregory P.; Grimes, Travis S.; Bauer, William F. Inorganic Chemistry, Vol. 58, Issue 13 https://doi.org/10.1021/acs.inorgchem.9b00854	journal	June 2019
Radiation chemical effects on radiochemistry: A review of examples important to nuclear power Mincher, Bruce J.; Mezyk, Stephen P. Radiochimica Acta, Vol. 97, Issue 9 https://doi.org/10.1524/ract.2009.1646	journal	January 2009
Radiation chemistry of aqueous solutions of actinides Pikaev, Alexei K.; Shilov, Vladimir P.; Gogolev, Andrei V. Russian Chemical Reviews, Vol. 66, Issue 9 https://doi.org/10.1070/RC1997v066n09ABEH000284	journal	September 1997
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
Picosecond pulse radiolysis. V. Yield of electrons in irradiated aqueous solution with high concentrations of scavenger Wolff, R. K.; Aldrich, J. E.; Penner, T. L. The Journal of Physical Chemistry, Vol. 79, Issue 3 https://doi.org/10.1021/j100570a005	journal	January 1975

Similar Records

Predicting Radiation-Induced Plutonium Redox Chemistry using Multi-scale Modeling Methods

Conference · 2024 · OSTI ID:2468787

Kynman, Amy Elizabeth; Holmbeck, Gregory Peter

Re-evaluation of the Gamma Radiolysis Radiation Chemistry of Neptunium

Journal Article · 2016 · Transactions of the American Nuclear Society · OSTI ID:22991841

Horne, G. P.; Mezyk, S. P.

Purification Techniques for Actinide Radiolysis Studies

Conference · 2024 · OSTI ID:2472996

Kynman, Amy Elizabeth; Grimes, Travis S; Holmbeck, Gregory Peter

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
plutonium
multi-scale modeling
cobalt-60 gamma irradiation
nitric acid

Title: Multiscale Modeling of Plutonium Radiation Chemistry in Nitric Acid Solutions. 1. Cobalt-60 Gamma Irradiation of Pu(IV)

Citation Formats

References (40)

Similar Records

Related Subjects