Identification and time evolution of thionyl chloride (SOCl2) radiolysis products

Conrad, Jacy K.; Woods, Michael E.; Horne, Gregory P.

doi:10.1515/ract-2024-0288

Identification and time evolution of thionyl chloride (SOCl₂) radiolysis products

Journal Article · Fri Jun 21 00:00:00 EDT 2024 · Radiochimica Acta

DOI:https://doi.org/10.1515/ract-2024-0288· OSTI ID:2396678

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Idaho National Laboratory (INL), Idaho Falls, ID (United States)

In this study, innovative solutions are needed to reduce the amount of high-level waste generated by used nuclear fuel recycling strategies to support the widespread adoption of sustainable nuclear fission energy technologies. To this end, a new sulfur chloride-based process has been developed to recycle zirconium alloy-based materials, which make up a significant fraction of high-level radioactive waste. To support the continued development of this process, we present new data on the potential reaction pathways over time of the products arising from the gamma and electron beam radiolysis of neat thionyl chloride (SOCl₂). Interrogation of the gamma irradiated liquid by Raman spectroscopy provided more conclusive identification of the SOCl₂ degradation products, specifically sulfur dichloride (SCl₂), molecular chlorine (Cl₂), sulfur dioxide (SO₂), and sulfuryl chloride (SO₂Cl₂). In comparison, the high dose rate (~10⁷ Gy s^-1) electron beam irradiations formed significantly more degradation products. For both cobalt-60 gamma and electron beam irradiations, the observed degradation products were found to evolve as a function of time post-irradiation via the same reaction pathways, with indication of a solvent regeneration mechanism. These findings are fortuitous for process development, as such a mechanism would be beneficial for process longevity and cost effectiveness.

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:: 2396678

Report Number(s):: INL/JOU--24-76150-Rev001

Journal Information:: Radiochimica Acta, Journal Name: Radiochimica Acta Journal Issue: 11 Vol. 112; ISSN 0033-8230

Publisher:: de GruyterCopyright Statement

Country of Publication:: United States

Language:: English

References (14)

Sulfur Compounds Weil, Edward D.; Sandler, Stanley R. Kirk‐Othmer Encyclopedia of Chemical Technology https://doi.org/10.1002/0471238961.1921120623050912.a01	reference-book	December 2000
Zirconium Alloys for LWR Fuel Cladding and Core Internals Yagnik, Suresh; Garde, Anand Structural Alloys for Nuclear Energy Applications, p. 247-291 https://doi.org/10.1016/B978-0-12-397046-6.00007-1	book	August 2019
Process Metallurgy—An Argosy Through Time Seetharaman, Seshadri Treatise on Process Metallurgy, p. 3-13 https://doi.org/10.1016/B978-0-323-85935-6.00031-3	book	February 2024
A novel protocol to recycle zirconium from zirconium alloy cladding from used nuclear fuel rods Vestal, Breanna K.; Travis, Jordan; Albert, Austin Journal of Nuclear Materials, Vol. 578 https://doi.org/10.1016/j.jnucmat.2023.154339	journal	May 2023
Process Development Studies for Zirconium Recovery/Recycle from used Nuclear Fuel Cladding Collins, E. D.; DelCul, G. D.; Spencer, B. B. Procedia Chemistry, Vol. 7 https://doi.org/10.1016/j.proche.2012.10.013	journal	January 2012
Radiolytic evaluation of select sulfur chlorides (S2Cl2 and SOCl2) for advanced low temperature chlorination of zirconium-based used nuclear fuel cladding Conrad, Jacy K.; Woods, Michael E.; Horne, Gregory P. Radiation Physics and Chemistry, Vol. 206 https://doi.org/10.1016/j.radphyschem.2022.110732	journal	May 2023
Corrigendum to “Radiolytic evaluation of select sulfur chlorides (S2Cl2 and SOCl2) for advanced low temperature chlorination of zirconium-based used nuclear fuel cladding” [Radiat. Phys. Chem. 206 110732] Conrad, Jacy K.; Woods, Michael E.; Horne, Gregory P. Radiation Physics and Chemistry, Vol. 220 https://doi.org/10.1016/j.radphyschem.2024.111628	journal	July 2024
Spectroscopic and kinetic studies of the SO radical and the photolysis of thionyl chloride Donovan, R. J.; Husain, D.; Jackson, P. T. Transactions of the Faraday Society, Vol. 65 https://doi.org/10.1039/tf9696502930	journal	January 1969
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
Medicine in the United States Wainerdi, H. R. BMJ, Vol. 2, Issue 4523 https://doi.org/10.1136/bmj.2.4523.431-a	journal	September 1947
The Vibrational Spectra of Sulphuryl and Thionyl Halides Gillespie, R. J.; Robinson, E. A. Canadian Journal of Chemistry, Vol. 39, Issue 11 https://doi.org/10.1139/v61-289	journal	November 1961
RAMAN SPECTRUM OF CRYSTALLINE AND LIQUID SO₂ Anderson, A.; Savoie, R. Canadian Journal of Chemistry, Vol. 43, Issue 8 https://doi.org/10.1139/v65-307	journal	August 1965
Low Temperature Raman Spectra of Dichlorosulfane (SCl₂), Tetrachlorosulfurane (SCl₄), Dichlorodisulfane (S₂Cl₂) and Dichlorodiselane (Se₂Cl₂) Steudel, Ralf; Jensen, Detlef; Plinke, Bettina Zeitschrift für Naturforschung B, Vol. 42, Issue 2 https://doi.org/10.1515/znb-1987-0208	journal	February 1987
Advanced Low-Temperature Chlorination of Zirconium Bruffey, Stephanie; Hunt, Rodney; Vestal, Breanna Oak Ridge National Laboratory (ORNL) https://doi.org/10.2172/1841491	report	August 2021

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38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
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degradation products
radiation chemistry

Identification and time evolution of thionyl chloride (SOCl2) radiolysis products

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References (14)

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Identification and time evolution of thionyl chloride (SOCl₂) radiolysis products