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

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

Journal Article · Wed Apr 24 00:00:00 EDT 2024 · Inorganic Chemistry

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

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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)

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

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Related Subjects

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

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

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