Keywords
Bismuth Chloride, Molten Salt, Diffusivity, Standard Potential, Cyclic Voltammetry, Chronopotentiometry, Liquid Metal, Electrorefining, Pyroprocessing
Abstract
Bismuth has been investigated as a potential liquid electrode for molten salt electrorefining, but the electrochemical behavior of Bi3+/Bi redox couple has received scant attention in eutectic LiCl-KCl melts and no studies were found in the ternary LiCl-KCl-CaCl2 melts. LiCl-KCl-CaCl2 melts offer some advantages over eutectic LiCl-KCl, such as a lower melting point. Cyclic voltammetry, square wave voltammetry, chronoamperometry, chronopotentiometry and open-circuit chronopotentiometry were used to measure electrochemical parameters, such as diffusivity and standard apparent potential of bismuth electrodeposition, in LiCl-KCl and LiCl-KCl-CaCl2 eutectics. The mean diffusivity values of 6.71 x 10-6 cm2 s-1 and 8.93 x 10-6 cm2 s-1 were recommended for BiCl3 in the LiCl-KCl and LiCl-KCl-CaCl2 eutectics, respectively. Although the diffusivity values differed slightly between eutectics, they had too significant of error (± ~30%) to conclusively establish any effect from the presence of CaCl2. The standard apparent potentials of 0.1166 V vs. Ag/AgCl (4.75 mol%) and 0.1187 V vs. Ag/AgCl (4.75 mol%) in the molten LiCl-KCl and LiCl-KCl-CaCl2 eutectics, respectively, at 680 ± 2.1 K were less uncertain (± ~0.5%). These values provide estimates for key properties of the Bi3+/Bi redox couple and their associated errors. Challenges were also identified, most notably the ICP-MS analysis of BiCl3 content, which limited the accuracy of the results. Some improvements were made to the accuracy of the results by utilizing a more thorough drying procedure for CaCl2.
Original Publication Citation
Chipman, G., Johnson, B., Vann, C., Whitesides, L., & Rappleye, D. (2024). Experimental determination of the electrochemical properties of bismuth chloride in eutectic LiCl–KCl and LiCl–KCl–CaCl2 molten salts. Journal of Radioanalytical and Nuclear Chemistry. https://doi.org/10.1007/s10967-024-09354-4
BYU ScholarsArchive Citation
Chipman, Greg; Johnson, Bryant; Vann, Cameron; Whitesides, Lance; and Rappleye, Devin, "Experimental Determination of the Electrochemical Properties of Bismuth Chloride in Eutectic LiCl-KCl and LiCl-KCl-CaCl2 Molten Salts" (2024). Faculty Publications. 7540.
https://scholarsarchive.byu.edu/facpub/7540
Document Type
Peer-Reviewed Article
Publication Date
2024-02-07
Publisher
Springer Nature
Language
English
College
Ira A. Fulton College of Engineering
Department
Chemical Engineering
Copyright Status
© 2023 CC-BY-NC-ND license. https://creativecommons.org/licenses/by-nc-nd/4.0/ This version of the article has been accepted for publication, after peer review and is subject to Springer Nature’s AM terms of use, but is not the Version of Record and does not reflect post-acceptance improvements, or any corrections. The Version of Record is available online at: Chipman, G., Johnson, B., Vann, C., Whitesides, L., & Rappleye, D. (2024). Experimental determination of the electrochemical properties of bismuth chloride in eutectic LiCl–KCl and LiCl–KCl–CaCl2 molten salts. Journal of Radioanalytical and Nuclear Chemistry. https://doi.org/10.1007/s10967-024-09354-4
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