Spectroelectrochemistry of EuCl<sub>3</sub> in Four Molten Salt Eutectics; 3 LiCl−NaCl, 3 LiCl−2 KCl, LiCl−RbCl, and 3 LiCl−2 CsCl; at 873 K

Schroll, Cynthia A.; Chatterjee, Sayandev; Levitskaia, Tatiana G.; Heineman, William R.; Bryan, Samuel A.

doi:10.1002/elan.201600048

Cited by 18 publications

(16 citation statements)

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“…The observed trends in diffusion coefficient data are based on the "hopping" mechanism of diffusion through ionic media. This work expands our concerted effort to systematically advance methods for quantitative electrochemical and spectroscopic measurement of lanthanides [29][30][31][32] and actinides within pyroprocessing 29-31 and other nuclear fuel reprocessing flowsheet applications including aqueous separation and detection of lanthanide and transition metal fission products. …”

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confidence: 88%

Electrochemistry of Europium(III) Chloride in 3 LiCl – NaCl, 3 LiCl – 2 KCl, LiCl – RbCl, and 3 LiCl – 2 CsCl Eutectics at Various Temperatures

Schroll

Chatterjee

Levitskaia

et al. 2017

J. Electrochem. Soc.

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Here we report the effect of changing the eutectic melt composition on the electrochemical properties of europium(III) chloride under pyroprocessing conditions. Stoichiometry of electron-transfer, redox potentials and diffusion coefficients were determined using various electrochemical and spectroelectrochemical techniques in four different eutectic mixtures (3 LiCl -NaCl, 3 LiCl -2 KCl, LiCl -RbCl, and 3 LiCl -2 CsCl) while varying the temperature of the melt. It was determined that Eu 3+ undergoes a one electron reduction to Eu 2+ in each melt at all temperatures evaluated. Within each of the melts a positive shift in the redox potential as well as an increase in the diffusion coefficient for Eu 3+ was observed as the temperature increased. Also observed was a positive shift in the redox potential and increase in the diffusion coefficient for Eu 3+ as the weighted average of the cationic radii the melt composition decreased. Pyroprocessing is one of the newest techniques for spent nuclear fuel reprocessing in which the separation is accomplished electrochemically in molten salt media at temperatures of >500• C. 1-3 Some of the advantages of pyroprocessing over the more traditional liquidliquid extraction techniques are that there is no organic solvent that is susceptible to radiolysis, 4,5 lack of pure plutonium product which provides less likelihood for proliferation, 6 generation of the U-Pu alloy product is ready for immediate fabrication into new fuel rods 7 and the ability to do a group separation of all actinides.8 There are also engineering related advantages such as amenability to scaling to the needs of the facility 9 and making the refinement vessel more compact. 10,11The most important information needed to understand pyroprocessing is accurate thermodynamic data for each of the analytes that may be found in used nuclear fuel in each of the possible eutectic melt compositions. We have chosen to investigate europium(III) chloride because it is a non-radioactive analog to the actinides which makes it safer to work with, it has the least negative redox potential of the lanthanides, and it undergoes a change in its absorption spectrum when it is reduced from Eu 3+ to Eu 2+ . 12 Prior research has been performed using europium(III) chloride and evaluating its thermodynamic properties in different melts, such as LiCl, 13 In this work we systematically evaluated the redox potentials and diffusion coefficients for europium(III) chloride using differential pulse voltammetry and cyclic voltammetry in three different eutectic salt compositions over a range of temperatures. The experiments were performed from 673 K to 1173 K in 3 LiCl -NaCl, LiCl -RbCl and 3 LiCl -2 CsCl. This data along with the results from our previous * Electrochemical Society Member.z E-mail: heinemwr@ucmail.uc.edu; sam.bryan@pnl.gov reports (Electrochemistry of Europium in 3 LiCl -2 KCl from 643 to 1123 K 29 and Spectroelectrochemistry of Europium in 3 LiCl -NaCl, 3 LiCl -2 KCl, LiCl -RbCl, and 3 LiCl −2 CsCl at 873 K 30 ) were analyzed ...

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confidence: 88%

Electrochemistry of Europium(III) Chloride in 3 LiCl – NaCl, 3 LiCl – 2 KCl, LiCl – RbCl, and 3 LiCl – 2 CsCl Eutectics at Various Temperatures

Schroll

Chatterjee

Levitskaia

et al. 2017

J. Electrochem. Soc.

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“…1 Many spectroscopic techniques have been paired successfully with electrochemistry, including infrared, 2 Raman, 3,4 electron paramagnetic resonance, 5 nuclear magnetic resonance, 6 UV−vis absorption, 7−9 and fluorescence, 7,8,10−12 in aqueous as well as molten-salt media. 13,14 Also, a number of sensing platforms combine multiple spectroscopic techniques with electrochemistry to detect a single species. 15 Spectroelectrochemistry in an optically transparent thin-layer electrode (OTTLE) cell has the advantages of fast and complete electrolysis coupled with optical monitoring.…”

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confidence: 99%

Optically Transparent Thin-Film Electrode Chip for Spectroelectrochemical Sensing

et al. 2017

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A novel microfabricated optically transparent thin-film electrode chip for fluorescence and absorption spectroelectrochemistry has been developed. The working electrode was composed of indium tin oxide (ITO); the quasi-reference and auxiliary electrodes were composed of platinum. The stability of the platinum quasi-reference electrode was improved by coating it with a planar, solid state Ag/AgCl layer. The Ag/AgCl reference was characterized with scanning electron microscopy and energy-dispersive X-ray spectroscopy. Cyclic voltammetry measurements showed that the electrode chip was comparable to a standard electrochemical cell. Randles-Sevcik analysis of 10 mM K[Fe(CN)] in 0.1 M KCl using the electrode chip gave a diffusion coefficient of 1.59 × 10 cm/s, in comparison to the value of 2.38 × 10 cm/s using a standard electrochemical cell. By using the electrode chip in an optically transparent thin-layer electrode (OTTLE), the absorption based spectroelectrochemical modulation of [Fe(CN)] was demonstrated, as well as the fluorescence based modulation of [Ru(bpy)]. For the fluorescence spectroelectrochemical determination of [Ru(bpy)], a detection limit of 36 nM was observed.

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“…Combining spectroscopy with electrochemistry in spectroelectrochemistry is particularly valuable for the interrogation and control of conditions present in the salt. Spectroelectrochemistry has been used in molten salt systems for both its ability to determine speciation and for controlling the oxidation states of specific species within these systems (Nagai et al, 2005;Polovov et al, 2007;Volkovich et al, 2007;Polovov et al, 2008;Abramov et al, 2010;Nagai et al, 2011;Park et al, 2011;Nagai et al, 2013;Schroll et al, 2016). Corrosion products such as Cr, Fe, Ni, Mo, Ti, and Mn have been studied using spectroelectrochemical methods (Volkovich et al, 2007;Abramov et al, 2010).…”

Section: Online Monitoring Of Systems That Contribute To Off-gas Loadingmentioning

confidence: 99%

Molten Salt Reactor Engineering Study for Off-Gas Management

McFarlane

Riley

Holcomb

et al. 2020

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Spectroelectrochemistry of EuCl₃ in Four Molten Salt Eutectics; 3 LiCl−NaCl, 3 LiCl−2 KCl, LiCl−RbCl, and 3 LiCl−2 CsCl; at 873 K

Cited by 18 publications

References 54 publications

Electrochemistry of Europium(III) Chloride in 3 LiCl – NaCl, 3 LiCl – 2 KCl, LiCl – RbCl, and 3 LiCl – 2 CsCl Eutectics at Various Temperatures

Electrochemistry of Europium(III) Chloride in 3 LiCl – NaCl, 3 LiCl – 2 KCl, LiCl – RbCl, and 3 LiCl – 2 CsCl Eutectics at Various Temperatures

Optically Transparent Thin-Film Electrode Chip for Spectroelectrochemical Sensing

Molten Salt Reactor Engineering Study for Off-Gas Management

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Spectroelectrochemistry of EuCl3 in Four Molten Salt Eutectics; 3 LiCl−NaCl, 3 LiCl−2 KCl, LiCl−RbCl, and 3 LiCl−2 CsCl; at 873 K

Cited by 18 publications

References 54 publications

Electrochemistry of Europium(III) Chloride in 3 LiCl – NaCl, 3 LiCl – 2 KCl, LiCl – RbCl, and 3 LiCl – 2 CsCl Eutectics at Various Temperatures

Electrochemistry of Europium(III) Chloride in 3 LiCl – NaCl, 3 LiCl – 2 KCl, LiCl – RbCl, and 3 LiCl – 2 CsCl Eutectics at Various Temperatures

Optically Transparent Thin-Film Electrode Chip for Spectroelectrochemical Sensing

Molten Salt Reactor Engineering Study for Off-Gas Management

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Product

Resources

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Spectroelectrochemistry of EuCl₃ in Four Molten Salt Eutectics; 3 LiCl−NaCl, 3 LiCl−2 KCl, LiCl−RbCl, and 3 LiCl−2 CsCl; at 873 K