Reduction of ytterbium(III) species in alkali chloride based melts

Tropin, O. A.; Volkovich, Vladimir A.

doi:10.1063/1.5002942

Cited by 5 publications

(10 citation statements)

References 14 publications

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“…2a). 25 The excitation spectrum of the melt shows a notable peak at 270 nm and shoulder peaks between 300-375 nm (Fig. 2b).…”

Section: Resultsmentioning

confidence: 95%

“…In NaCl-KCl-CsCl, the diffusion coefficient of Sm(II) is also slightly larger than Eu(II), and in both LiCl-KCl and 1-butyl-3-methylimidazolium chloride ionic liquid the diffusion coefficient of Sm(III) is also larger than that of Eu(III). 25,39,40 The obvious difference is the reaction of the Eu metal with the AlCl 3 -NaCl melts and the redox potential of Eu(II)/Eu(III). There is also a potential difference between Eu and Sm in organic solvents: 41 (1) The dissolution of europium metal in AlCl 3 -NaCl melts produces Eu(II) and Aluminum.…”

Section: Resultsmentioning

confidence: 99%

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Electrochemical and Spectroscopic Properties of Europium in AlCl₃-NaCl Melts

Chen

Zhong

et al. 2023

J. Electrochem. Soc.

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The physicochemical properties of Eu cations in AlCl3-NaCl melt have been studied for the purpose of spent nuclear fuel recycling via electrochemical and spectroscopic methods. Eu metal dissolves in the AlCl3-NaCl melt to generate divalent europium and Al metal while releasing chlorine gas. The effect of Lewis acidity of melt on the electrochemical behaviors of Eu(II) has been studied. In Lewis base melt of AlCl3-NaCl, Eu3+, and AlCl4- can be co-reduced at the potential between Al deposition and Eu(II) oxidation. With the enhanced Lewis acidity of the molten salt, Eu(II) diffusion becomes more facile. The in-situ absorption spectra of Eu(II) in AlCl3-NaCl melt reveal that the complexation ligand of Eu(II) changes with the melt Lewis acidity, thereby affecting the electrochemical behaviors of Eu(II) species. In addition, the redox potential of the Eu(II)/Eu(III) conversion reaction is more positive than that of Sm(II)/Sm(III).

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“…2a). 25 The excitation spectrum of the melt shows a notable peak at 270 nm and shoulder peaks between 300-375 nm (Fig. 2b).…”

Section: Resultsmentioning

confidence: 95%

Section: Resultsmentioning

confidence: 99%

Electrochemical and Spectroscopic Properties of Europium in AlCl₃-NaCl Melts

Chen

Zhong

et al. 2023

J. Electrochem. Soc.

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“…There is also a wide intermediate absorption band from 400 to 600 nm. Bae and Volkovich once measured the absorption spectra of Sm(II) in LiCl‐KCl melt at 723 K and 823 K, [9a,14] in which strong absorption peaks appeared from 300 to 600 nm. In general, the absorption spectra of Sm in molten AlCl 3 ‐NaCl measured in this work show typical characteristic of 4f 6 →4f 5 5d transition of Sm(II) and no transition signal related to Sm(III) is found (Figure S3), excluding the presence of Sm(III) in this molten salt system.…”

Section: Resultsmentioning

confidence: 99%

Electrochemical Behaviour and Chemical Species of Sm(II) in AlCl₃‐NaCl with Different Lewis Acidity

Chen

Zhong

Zhang

et al. 2022

Chemistry A European J

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AlCl 3 -NaCl was utilized as an electrolyte in this work due to its low melting point and Lewis acidity, in which samarium exists in two oxidation states, Sm(III) and Sm(II), resulting in unique electrochemical behaviours. Sm metal dissolves in AlCl 3 -NaCl melt to form SmCl 2 , which is verified by electrochemical and spectroscopic techniques. As the Lewis acidity of the melt increases, the diffusion coefficient of Sm(II) gradually increases, and the activation energy of diffusion decreases. Moreover, an additional co-reduction peak of Sm 3 + and AlCl 4À is observed to be more positive than that of Al(0)/Al(III) in Lewis basic melt, which may be tightly correlated with the variation of Sm(II) coordination in AlCl 3 -NaCl melt and ligand variation from Cl À to AlCl 4 À and Al 2 Cl 7 À as the Lewis acidity of the AlCl 3 -NaCl melt increases, according to the in situ electronic absorption spectra of Sm in this melt.

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“…Electrochemical behavior of ytterbium cations in the LiCl-KCl melt was investigated by electrochemical and UV-VIS absorption spectroscopy methods by Bae et al (30). High temperature electronic absorption spectroscopy and electrochemical methods at 823-1123 K were applied to study Yb(III) in an equimolar NaCl-KCl mixture and in eutectic mixture of NaCl-KCl-CsCl (31). A spectroelectrochemical study of Yb(II) in the same melts has been done by Volkovich et al (32).…”

Section: Introductionmentioning

confidence: 99%

Kinetic and Thermodynamic Properties of Ytterbium Chloride and Fluoride Complexes in Chloride Melts

Kuznetsov¹,

Stulov²,

Gaune‐Escard³

2022

ECS Trans.

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The electrochemical behavior of ytterbium in NaCl-KCl, KCl and CsCl melts was studied in the temperature range 973-1173 K by different electrochemical methods. The diffusion coefficients (D) of Yb(III) and Yb(II) were determined by linear sweep voltammetry, chronopotentiometry and chronoamperometry methods. The standard rate constants of charge transfer (k s) for the Yb(III)/Yb(II) redox couple were calculated on the basis of cyclic voltammetry data using Nicholson’s equation. The formal redox potentials E* Yb(III)/Yb(II) were obtained in alkali chlorides melts from the cyclic voltammetry data. The influence of fluoride ions on the standard rate constants in the NaCl-KCl melt was investigated.

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Reduction of ytterbium(III) species in alkali chloride based melts

Cited by 5 publications

References 14 publications

Electrochemical and Spectroscopic Properties of Europium in AlCl₃-NaCl Melts

Electrochemical and Spectroscopic Properties of Europium in AlCl₃-NaCl Melts

Electrochemical Behaviour and Chemical Species of Sm(II) in AlCl₃‐NaCl with Different Lewis Acidity

Kinetic and Thermodynamic Properties of Ytterbium Chloride and Fluoride Complexes in Chloride Melts

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Reduction of ytterbium(III) species in alkali chloride based melts

Cited by 5 publications

References 14 publications

Electrochemical and Spectroscopic Properties of Europium in AlCl3-NaCl Melts

Electrochemical and Spectroscopic Properties of Europium in AlCl3-NaCl Melts

Electrochemical Behaviour and Chemical Species of Sm(II) in AlCl3‐NaCl with Different Lewis Acidity

Kinetic and Thermodynamic Properties of Ytterbium Chloride and Fluoride Complexes in Chloride Melts

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Electrochemical and Spectroscopic Properties of Europium in AlCl₃-NaCl Melts

Electrochemical and Spectroscopic Properties of Europium in AlCl₃-NaCl Melts

Electrochemical Behaviour and Chemical Species of Sm(II) in AlCl₃‐NaCl with Different Lewis Acidity