A study of samarium ions electroreduction at various electrodes in KCl-NaCl-CsCl melt at T = 823 K

Кушхов, Х. Б.; Vindizheva, M. K.; Karashaeva, R. A.; Tlenkopachev, M. R.

doi:10.1134/s1023193510060145

Cited by 11 publications

(8 citation statements)

References 2 publications

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“…Research has been performed in the past using several different analytes including lanthanides (Eu , Sm ,,) and actinides (U , Pu ,) in different eutectic melts. Most of this research has been limited to specific melt compositions and therefore has not reported the differences in thermodynamic properties that accompany variations in melt compositions.…”

Section: Introductionmentioning

confidence: 99%

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

et al. 2016

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Key electrochemical properties affecting pyroprocessing of nuclear fuel were examined in four eutectic melts using Eu3+/2+ as a representative probe. We report the electrochemical and spectroelectrochemical behavior of EuCl3 in four molten salt eutectics (3 LiCl−NaCl, 3 LiCl−2 KCl, LiCl−RbCl and 3 LiCl−2 CsCl) at 873 K. Cyclic voltammetry was used to determine the reduction potential for Eu3+/2+ and the applied potentials for spectroelectrochemistry. Single step chronoabsorptometry and thin‐layer spectroelectrochemistry were used to obtain the number of electrons transferred, reduction potentials and diffusion coefficients for Eu3+ in each eutectic melt. The reduction potentials determined by thin‐layer spectroelectrochemistry were essentially the same as those obtained using cyclic voltammetry. The diffusion coefficient for Eu3+ was the largest in the 3 LiCl−NaCl melt, showed a negative shift in the 3 LiCl−2 KCl melt, and was the smallest in the LiCl−RbCl and 3 LiCl−2 CsCl eutectic melts. The basic one‐electron reversible electron transfer for Eu3+/2+ was not affected by melt composition.

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Section: Introductionmentioning

confidence: 99%

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

et al. 2016

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Section: Introductionmentioning

confidence: 99%

“…It would also be desirable to develop such a technique into an online monitoring system. The literature on MS online monitoring can be divided into two major groups: spectrophotometric methods − and electrochemical methods. − Spectrophotometric methods suffer from the significant disadvantages of requiring the engineering of sampling access points and being limited to those species containing optically distinct chromophores. Electrochemical methods are suited to redox characterization and do not suffer from these disadvantages, but to date have typically focused on macroelectrode measurements which suffer from low signal-to-noise, a time-dependent signal, iR distortion of the response and sensitivity to convection.…”

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confidence: 99%

Enhanced Electroanalysis in Lithium Potassium Eutectic (LKE) Using Microfabricated Square Microelectrodes

et al. 2014

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Molten salts (MSs) are an attractive medium for chemical and electrochemical processing and as a result there is demand for MS-compatible analysis technologies. However, MSs containing redox species present a challenging environment in which to perform analytical measurements because of their corrosive nature, significant thermal convection and the high temperatures involved. This paper outlines the fabrication and characterization of microfabricated square microelectrodes (MSMs) designed for electrochemical analysis in MS systems. Their design enables precise control over electrode dimension, the minimization of stress because of differential thermal expansion through design for high temperature operation, and the minimization of corrosive attack through effective insulation. The exemplar MS system used for characterization was lithium chloride/potassium chloride eutectic (LKE), which has potential applications in pyrochemical nuclear fuel reprocessing, metal refining, molten salt batteries and electric power cells. The observed responses for a range of redox ions between 400 and 500 °C (673 and 773 K) were quantitative and typical of microelectrodes. MSMs also showed the reduced iR drop, steady-state diffusion-limited response, and reduced sensitivity to convection seen for microelectrodes under ambient conditions and expected for these electrodes in comparison to macroelectrodes. Diffusion coefficients were obtained in close agreement with literature values, more readily and at greater precision and accuracy than both macroelectrode and previous microelectrode measurements. The feasibility of extracting individual physical parameters from mixtures of redox species (as required in reprocessing) and of the prolonged measurement required for online monitoring was also demonstrated. Together, this demonstrates that MSMs provide enhanced electrode devices widely applicable to the characterization of redox species in a range of MS systems.

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“…In order to take full advantage of this technique, fundamental research is needed on lanthanides and actinides in these melts. Some work has been performed in the past to determine redox potentials, electron transfer stoichiometry, and diffusion coefficients of several lanthanides and actinides in different eutectic mixtures such as 3LiCl–2KCl, − NaCl–KCl, − 3LiF–CaF 2 , , and other eutectics. ,− Some groups have also determined thermodynamic properties and separation coefficients of the analytes in solution. ,− Most of the data, however, either is confined to a single temperature or spans a limited temperature range (ca. 100 or 200 K).…”

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Electrochemistry and Spectroelectrochemistry of Europium(III) Chloride in 3LiCl–2KCl from 643 to 1123 K

et al. 2013

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The electrochemical and spectroelectrochemical behavior of europium(III) chloride in a molten salt eutectic, 3LiCl–2KCl, over a temperature range of 643–1123 K using differential pulse voltammetry, cyclic voltammetry, potential step chronoabsorptometry, and thin-layer spectroelectrochemistry is reported. The electrochemical reaction was determined to be the one-electron reduction of Eu3+ to Eu2+ at all temperatures. The redox potential of Eu3+/2+ shifts to more positive potentials, and the diffusion coefficient for Eu3+ increases as temperature increases. The results for the number of electrons transferred, redox potential, and diffusion coefficient are in good agreement between the electrochemical and spectroelectrochemical techniques. This research extends our ability to develop a spectroelectrochemical sensor for lanthanides and actinides into molten salt media.

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A study of samarium ions electroreduction at various electrodes in KCl-NaCl-CsCl melt at T = 823 K

Cited by 11 publications

References 2 publications

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

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

Enhanced Electroanalysis in Lithium Potassium Eutectic (LKE) Using Microfabricated Square Microelectrodes

Electrochemistry and Spectroelectrochemistry of Europium(III) Chloride in 3LiCl–2KCl from 643 to 1123 K

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A study of samarium ions electroreduction at various electrodes in KCl-NaCl-CsCl melt at T = 823 K

Cited by 11 publications

References 2 publications

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

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

Enhanced Electroanalysis in Lithium Potassium Eutectic (LKE) Using Microfabricated Square Microelectrodes

Electrochemistry and Spectroelectrochemistry of Europium(III) Chloride in 3LiCl–2KCl from 643 to 1123 K

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Product

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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

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