Electrochemical measurement of high concentrations of UCl3 and GdCl3 in molten LiCl-KCl eutectic

• Published in: Electrochimica acta Vol. 290; no. C; pp. 429 - 439
• Main Authors: Zhang, Chao, Wallace, Jaron, Simpson, Michael F.
• Format: Journal Article
• Language: English
• Published: United Kingdom Elsevier Ltd 10-11-2018; Elsevier
• Subjects: Chronoamperometry; Cyclic voltammetry; Molten salt; Normal pulse voltammetry; Pyroprocessing; Cyclic voltammetry; Normal pulse voltammetry; Chronoamperometry; Pyroprocessing; Molten salt
• ISSN: 0013-4686; 1873-3859
• DOI: 10.1016/j.electacta.2018.08.087

Electrochemical methods have been developed to measure metal ion concentrations in spent nuclear fuel electrorefiner by correlating concentration with current response. Analytes UCl3 and GdCl3 were studied in LiCl-KCl eutectic solvent at 773 K. A mixture matrix, which consisted of varying concentrations of UCl3 and GdCl3 from 1 to 10 wt% and from 1 to 3 wt%, respectively, was tested. Optimized normal pulse voltammetry (NPV) measurements were made on this mixture matrix and used for the concentration correlations. The accuracy of the prediction was improved by including solution resistance compensation and minimizing the working electrode surface area. The presence of GdCl3 showed no effect on the U3+ NPV reduction current, but high U concentrations affected the Gd3+ NPV reduction current. This is speculated to be due to increased migrational current in the molten salt mixture. The average relative measurement errors obtained were 1.6% and 2.7% for UCl3 and GdCl3 respectively.