Thermodynamic properties of La–Ga–Al and U–Ga–Al alloys and the separation factor of U/La couple in the molten salt–liquid metal system

Новоселова, А. В.; Smolenski, Valeri; Volkovich, Vladimir A.; Ivanov, Alexander B.; Осипенко, А. Г.; Griffiths, Trevor R.

doi:10.1016/j.jnucmat.2015.08.010

Cited by 33 publications

(13 citation statements)

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“…Understanding the properties of lanthanides in chloride melts is highly desirable for a variety of cases including fission products and the recovery of rare earth metals by molten salt electrolysis. − In addition, LaCl 3 has long been studied as a structural analogue to UCl 3 ,, and more experimental data exists for LaCl 3 than UCl 3 , partly due to its lower cost and ease of handling. Mixtures of LaCl 3 in alkali halides also serve as excellent surrogate systems for understanding UCl 3 fuel salt mixtures for molten salt nuclear reactors (MSRs). , Iwadate published an extensive review on the structure of molten salts and thoroughly discussed the state of the art at the time on MCl 3 -containing salts.…”

Section: Introductionmentioning

confidence: 99%

Complete Description of the LaCl₃–NaCl Melt Structure and the Concept of a Spacer Salt That Causes Structural Heterogeneity

et al. 2022

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Lanthanides are important fission products in molten salt reactors, and understanding their structure and that of their mixtures is relevant to many scientific and technological problems including the recovery and separation of rare earth elements using molten salt electrolysis. The literature on molten salts and specifically on LaCl 3 and LaCl 3 −NaCl mixtures is often fragmented, with different experiments and simulations coinciding in their explanation for certain structural results but contradicting or questioning for others. Given the very practical importance that actinide and lanthanide salts have for energy applications, it is imperative to arrive at a clear unified picture of their local and intermediate-range structure in the neat molten state and when mixed with other salts. This article aims to unequivocally answer a set of specific questions: is it correct to think of long-lived octahedral coordination structures for La 3+ ? What is the nature as a function of temperature of networks and intermediate-range order particularly upon dilution of the trivalent ion salt? Is the so-called scattering first sharp diffraction peak (FSDP) for neat LaCl 3 truly indicative of intermediate-range order? If so, why is there a new lower-q peak when mixed with NaCl? Are X-ray scattering and Raman spectroscopy results fully consistent and easily described by simulation results? We will show that answers to these questions require that we abandon the idea of a most prominent coordination state for M 3+ ions and instead think of multiple competing coordination states in exchange due to significant thermal energy in the molten state.

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Section: Introductionmentioning

confidence: 99%

Complete Description of the LaCl₃–NaCl Melt Structure and the Concept of a Spacer Salt That Causes Structural Heterogeneity

et al. 2022

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“…6 On the other hand, group IIIA elements such as aluminum (Al) and gallium (Ga), basically have prominent potentials to be an ideal media in the selective An recovery and separation from the Ln elements, by electrolytic and chemical extraction processes. [7][8][9][10][11][12] Typically, liquid gallium (Ga) can promote the separation factor with several orders of magnitude higher than that achieved with any other low-melting metals (Zn, Sn, Pb, Bi, In, Cd, Tl).…”

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confidence: 99%

Evaluation of the Electroextractions of Ce and Nd from LiCl-KCl Molten Salt Using Liquid Ga Electrode

Liu

Chai

et al. 2017

J. Electrochem. Soc.

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The aim of this work is to explore the electroextractions and related thermodynamic properties of Ln (Ce and Nd) as actinide surrogates on the liquid Ga media, aiming at further Ln/An separation. The activities, activity coefficients and solubilities of Ce and Nd in the liquid Ga media were determined by open circuit potential at the temperature range from 698 to 798 K. The electroextractions of Ce and Nd and their corresponding current efficiencies on a static liquid Ga electrode were investigated by gavanostatic electrolysis. The electrochemical behaviors of Ce and Nd on a liquid Ga electrode in LiCl-KCl eutectic were explored by the cyclic voltammetry. It was found that both of the reductions of Ce(III) and Nd(III) on a liquid gallium electrode start at about −1.1 V at 773 K and are a one-step process with three electrons transferred. Semi-differential method was applied so as to more accurately determine the apparent standard potential of Nd(III)/Nd(II) which actually hadn't been well clarified in literatures. Open circuit potential technique was also utilized to determine the apparent standard potentials of Ce(III)/Ce and Nd(III)/Nd redox couples and to evaluate the thermodynamic properties of Ce and Nd in the liquid Ga media. Galvanostatic electrolyses on the static liquid Ga electrode were conducted to extract the Ln elements with or without the formation of intermetallic compounds at 723 or 773 K. The current efficiencies for the electroextraction of Ce and Nd were calculated to be about 90%. X-ray diffraction (XRD) characterizations identified the formation of intermetallic compounds CeGa6 and NdGa6 after the electrolysis. The Gibbs free energies for the formation of LnGa6 were also calculated.

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“…Smolenski et al. systematically studied the thermodynamical properties of lanthanides and actinides on liquid metal electrode in LiCl‐KCl system . Moreover, our team also reported the formation of Al−Sm, Al‐Pr and Zn‐Pr relevant research in this field.…”

Section: Introductionmentioning

confidence: 64%

Electrochemical Synthesis and Thermodynamic Properties of Pr‐Ni Intermetallic Compounds in a LiCl‐KCl‐NiCl₂‐PrCl₃ Melt

et al. 2019

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In this report, the electrochemical behaviors of Pr(III) and Ni(II) ions on a W electrode were investigated in LiCl-KCl eutectic by cyclic voltammetry (CV), square wave voltammetry (SWV), chronopotentiometry (CP) and open-circuit chronopotentiometry (OCP) techniques. From the results of electrochemical methods, different signals corresponding to seven kinds of intermetallic compounds in the phase diagram of PrÀ Ni were observed. The thermodynamic properties of intermetallic compounds in the temperature range of 823-923 K were investigated by open-circuit chronopotentiometry. With the eval-uated apparent standard potentials of PrÀ Ni intermetallic compounds, the Gibbs energies, enthalpies and entropies of formation were also calculated. The co-reduction products by galvanostatic and potentiostatic electrolysis were characterized based on X-ray diffraction (XRD) and scanning electron microscopy (SEM) coupled with energy dispersive X-ray spectroscopy (EDS). The shape of the alloy obviously changes from granular to bulk, and the alloy phase changes from Pr-rich to Ni-rich. The co-reduction products of PrNi 5 , PrNi 2 and PrNi were identified.

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Thermodynamic properties of La–Ga–Al and U–Ga–Al alloys and the separation factor of U/La couple in the molten salt–liquid metal system

Cited by 33 publications

References 33 publications

Complete Description of the LaCl₃–NaCl Melt Structure and the Concept of a Spacer Salt That Causes Structural Heterogeneity

Complete Description of the LaCl₃–NaCl Melt Structure and the Concept of a Spacer Salt That Causes Structural Heterogeneity

Evaluation of the Electroextractions of Ce and Nd from LiCl-KCl Molten Salt Using Liquid Ga Electrode

Electrochemical Synthesis and Thermodynamic Properties of Pr‐Ni Intermetallic Compounds in a LiCl‐KCl‐NiCl₂‐PrCl₃ Melt

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Thermodynamic properties of La–Ga–Al and U–Ga–Al alloys and the separation factor of U/La couple in the molten salt–liquid metal system

Cited by 33 publications

References 33 publications

Complete Description of the LaCl3–NaCl Melt Structure and the Concept of a Spacer Salt That Causes Structural Heterogeneity

Complete Description of the LaCl3–NaCl Melt Structure and the Concept of a Spacer Salt That Causes Structural Heterogeneity

Evaluation of the Electroextractions of Ce and Nd from LiCl-KCl Molten Salt Using Liquid Ga Electrode

Electrochemical Synthesis and Thermodynamic Properties of Pr‐Ni Intermetallic Compounds in a LiCl‐KCl‐NiCl2‐PrCl3 Melt

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Complete Description of the LaCl₃–NaCl Melt Structure and the Concept of a Spacer Salt That Causes Structural Heterogeneity

Complete Description of the LaCl₃–NaCl Melt Structure and the Concept of a Spacer Salt That Causes Structural Heterogeneity

Electrochemical Synthesis and Thermodynamic Properties of Pr‐Ni Intermetallic Compounds in a LiCl‐KCl‐NiCl₂‐PrCl₃ Melt