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Electrochemical and thermodynamic properties of Pu(III) ions at the Mo electrode in LiCl–KCl eutectics

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Abstract

To enhance the extraction of remaining fissile nuclides from spent nuclear fuel through pyrochemical reprocessing, the operational lifetime of such fuels can be extended, ultimately leading to increased cost efficiency and a reduction in the amount of radioactively contaminated waste generated by fast-neutron reactors. Understanding the electrochemical behavior of fissile nuclides in LiCl–KCl is pivotal to the success of molten salt electrorefining pyrochemical reprocessing. In this pursuit, a comprehensive study of Pu(III) salt was conducted to comprehend its electrochemical characteristics within molten chloride salt mixtures. To achieve this, PuCl3 was meticulously prepared by reacting PuO2 with HCl in a LiCl–KCl mixture. Subsequently, we investigated the reduction mechanism, the diffusion coefficient of Pu(III) (DPu(III)), and the apparent standard reduction potential of Pu(III)/Pu(0) (E0*Pu(III)/Pu(0)) in situ, using a Mo working cathode. Our findings revealed that Pu(III) undergoes a single-step reduction to Pu(0), involving the exchange of three electrons. Furthermore, the rate of diffusion governs the reduction of Pu(III) at the Mo cathode. The relationship between the diffusion coefficient and temperature was described by lnD = − 5.51 to 4244.2/T, with an activation energy of 35.28 kJ/mol. Additionally, we examined the temperature-dependent variations of E0*Pu(III)/Pu(0) and the Gibbs free energy of formation for PuCl3 (ΔGPuCl3). These dependencies were found to be E0*Pu(III)/Pu(0) = − 3.194 + 6.4 × 10−4 T and ΔGPuCl3 = − 924.5 + 0.185 T, respectively.

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Acknowledgements

We gratefully acknowledge the financial support provided by the National Natural Science Foundation of China (Grant No. U2167223).

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Authors and Affiliations

  1. Department of Radiochemistry, China Institute of Atomic Energy, Beijing, 102413, China

    Rushan Lin, Zhaokai Meng, Hui Chen, Peng Song, Yanhong Jia, Hui He & Guoan Ye

  2. State Key Laboratory of Nuclear Resources and Environment, East China University of Technology, Nanchang, 330013, Jiangxi, China

    Youqun Wang & Yunhai Liu

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  1. Rushan Lin
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Contributions

RL: Methodology, writing—original draft. ZM: Investigation, writing—original draft. YW: Data analysis. HC: Investigation. PS: Investigation. YJ: Data analysis YL: Writing—editing and review, supervision, resources. HH: Resources, methodology, writing − editing and review, supervision. GY: Conceptualization, writing—editing and review, supervision.

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Correspondence to Rushan Lin or Guoan Ye.

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Lin, R., Meng, Z., Wang, Y. et al. Electrochemical and thermodynamic properties of Pu(III) ions at the Mo electrode in LiCl–KCl eutectics. J Radioanal Nucl Chem 333, 23–30 (2024). https://doi.org/10.1007/s10967-023-09237-0

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