Application of Voltammetry to Measurement of Concentrations of Multiple Lanthanide Ions in Molten LiCl-KCl

Rappleye, Devin; Jeong, Seung-Ho; Gonzalez, Mario Alberto; Hansen, Lauryn C.; Simpson, Michael F.

doi:10.7733/jnfcwt.2015.13.s.29

Cited by 5 publications

(10 citation statements)

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“…Speculated causes for the absences of the La oxidation peak have been mentioned previously. 3 However, this anomaly should not affect the electroanalytical results because only the reduction peaks are analyzed.…”

Section: Resultsmentioning

confidence: 99%

“…La 3+ and Gd 3+ reduction commencing at the same potential) and the fitted SD peaks were semi-integrated. 3 Unrealistic fitting was resolved by refitting the SD peaks with the width of the peak on the positive side of the La 3+ reduction peak constrained to avoid excessively broad peaks which is not characteristic of metal electrodeposition. As shown in Figure 9, the La 3+ reduction peak does not extend to the commencement of the Gd 3+ reduction peak as it previously did in Figure 8 of Ref.…”

Section: Resultsmentioning

confidence: 99%

“…However, variations not associated with the concentration of La 3+ and Gd 3+ had a negative impact on the performance of PCR. 3 Possible experimental variations unrelated to concentration of ions are WE surface area and reference potential. Normalizing the CV current by WE surface area is a simple pretreatment can remove most of the error caused by variations in area.…”

Section: Diffusion Coefficients-in Tablementioning

confidence: 99%

“…Electroanalytical work in molten LiCl-KCl eutectic has been limited to single-analyte mixtures with a few exceptions. [1][2][3][4] Single-analyte mixtures do not accurately portray the conditions of a UNF electrorefiner and more importantly do not capture the issues and challenges associated with making quantitative analyses of the measured electrochemical signals in a UNF electrorefiner. When only one analyte is present, key signal features (peaks, plateaus, baselines, etc.)…”

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confidence: 99%

“…A paper previously published by the authors thoroughly covered the qualitative interpretation of electrochemical measurements and presented an initial approach to quantitatively analyze CV measurements in GdCl 3 -LaCl 3 -LiCl-KCl mixtures. 3 In that publication, it was found that the signals from chronopotentiometry (CP) overlapped too significantly to be quantitatively analyzed. CV produced a barely distinguishable pair of reduction peaks.…”

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confidence: 99%

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Electroanalytical Measurements of Binary-Analyte Mixtures in Molten LiCl-KCl Eutectic: Gadolinium(III)- and Lanthanum(III)-Chloride

Rappleye¹,

Jeong²,

Simpson³

2016

J. Electrochem. Soc.

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Electroanalytical measurements, such as cyclic voltammetry and chronopotentiometry, have been applied by other researchers to many eutectic LiCl-KCl mixtures containing a single analyte, typically a rare earth or actinide ion. These measurements have demonstrated the applicability of electroanalytical measurements of concentration in molten LiCl-KCl eutectic, which is prevalently used as an electrolyte in the electrorefining of used nuclear fuel (UNF). However, UNF electrorefiners contain multiple actinide and rare earth ions, necessitating the ability to make electroanalytical measurements in multi-analyte mixtures. The presence of multiple analytes creates interferences and overlapping signals. Chronoamperometry, cyclic voltammetry (CV), chronopotentiometry and open-circuit potential measurements were performed in eutectic LiCl-KCl mixtures containing a range of GdCl3 and LaCl3 concentrations to explore the issues associated with applying electroanalytical techniques in multi-analyte molten salt mixtures and to develop possible solutions. CV was found to be most promising for separating and analyzing each ion's signal. CV measurements were semi-differentiated and correlated to concentration using peak heights and principal component regression (PCR) to determine the concentration from electrochemical signals. The lowest average relative error was obtained using PCR for Gd3+ (6.21%) and using peak height correlations for La3+ (10.4%).

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Diffusion Coefficients-in Tablementioning

confidence: 99%

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confidence: 99%

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confidence: 99%

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