Electrochemical studies on the redox mechanism of uranium chloride in molten LiCl–KCl eutectic

Reddy, B. Prabhakara; Vandarkuzhali, S. Anbu Anjugam; Subramanian, T.; Venkatesh, P.

doi:10.1016/j.electacta.2004.02.002

Cited by 145 publications

(63 citation statements)

References 13 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The cyclic voltammogram displayed in Figure 4 was recorded after the glass coating had been in contact with the molten salt for more than 13 h and is characteristic of CV measurements made with the GSWE. Its features are consistent with CVs reported in the literature [4,9,13,[21][22][23][24][25] which were measured without a glass coating. These previous studies have identified the prominent pair of peaks at approximately 0 V in Figure 4 as the reduction of U 3+ and oxidation of U metal.…”

Section: Electrochemical Behavior Of Uclsupporting

confidence: 91%

“…In Figure 8, the U 3+ reduction peaks recorded in CV at each concentration are plotted from 50 to 200 mV s -1 which has been identified in the literature to be the limit of electrochemical reversibility for U 3+ reduction [22][23][24][25]. When an electrodeposition reaction is reversible, the Berzins-Delahay reaction is applicable to CV reduction peak [27]: (1) where is the number of electrons transferred, is Faraday's constant, is the universal gas constant, is temperature, is the diffusion coefficient, is the scan rate and is concentration.…”

Section: Cyclic Voltammetrymentioning

confidence: 98%

“…It has been speculated that these peak are either the adsorption of uranium ions or the formation of a metal monolayer [21,22].…”

Section: Electrochemical Behavior Of Uclmentioning

confidence: 99%

See 2 more Smart Citations

Investigation of the effects of uranium(III)-chloride concentration on voltammetry in molten LiCl-KCl eutectic with a glass sealed tungsten electrode

Rappleye

Teaford

Simpson

2016

Electrochimica Acta

View full text Add to dashboard Cite

One of the major sources of error for electroanalytical measurements in high-temperature molten salts is from the measurement of the working electrode (WE) area. A glass sealed working electrode (GSWE) was developed in order to set the exposed area of tungsten and reduce the error associated with WE area. The insulating property of the glass while in contact with molten salt was verified by observing the independence of electrochemical signals with adjustments in the WE position. The integrity of the glass coating was also confirmed by observing the stability of electrochemical signals (±1.9%) over several hours. Cyclic voltammetry (CV) and normal pulse voltammetry (NPV) were applied at 10 different concentrations of UCl 3. Above 0.17 mol dm-3 UCl 3 , the electrochemical signals from CV and NPV deviate significantly from linearity with concentration, but in opposite directions. A shift from reversible to quasi-reversible behavior and migration are theorized to cause the non-linearity for CV and NPV, respectively. A model is proposed to account for migration in NPV resulting in a significant error reduction in the electrochemical concentration measurement.

show abstract

Section: Electrochemical Behavior Of Uclsupporting

confidence: 91%

Section: Cyclic Voltammetrymentioning

confidence: 98%

See 1 more Smart Citation

Investigation of the effects of uranium(III)-chloride concentration on voltammetry in molten LiCl-KCl eutectic with a glass sealed tungsten electrode

Rappleye

Teaford

Simpson

2016

Electrochimica Acta

View full text Add to dashboard Cite

show abstract

“…This pair of peaks was located between the U 3+ /U 0 reduction peak and the U 3+ /U 4+ oxidation peak and has been attributed to adsorption/desorption [10,16]. Most of these studies have found the reduction of U 3+ to U 0 metal to be reversible up to 200 mV/s at 773 K, except for one [14] which reported it as irreversible due to decreasing peak potentials with increasing scan rate.…”

Section: Introductionmentioning

confidence: 99%

“…Several studies have been performed on uranium in LiCl-KCl eutectic [9][10][11][12][13][14][15]. They have found that uranium has two stable valence states, +3 and +4, within the potential window of LiCl-KCl eutectic.…”

Section: Introductionmentioning

confidence: 99%

Electroanalytical measurements of binary-analyte mixtures in molten LiCl-KCl eutectic: Uranium(III)- and Magnesium(II)-Chloride

Rappleye

Newton

Zhang

et al. 2017

Journal of Nuclear Materials

View full text Add to dashboard Cite

The electrochemical behavior of MgCl 2 in molten LiCl-KCl eutectic was investigated to evaluate its suitability as a surrogate for PuCl 3 in studies related to the eletrorefining of used nuclear fuel. The reduction of Mg 2+ was found to be electrochemically reversible up to 300 mV s-1 at 773 K. The diffusion coefficient for Mg 2+ was calculated to be 1.74 and 2.17 × 10-5 cm 2 s-1 with and without U 3+ present, respectively, at 773 K using cyclic voltammetry (CV). Upon comparison to literature data, the diffusion coefficient of Mg 2+ differs by only 8.8% (with U 3+ present) from that of Pu 3+ and the difference in peak potentials was only 79 mV. Binary-analyte mixtures of UCl 3 and MgCl 2 in eutectic LiCl-KCl were further investigated using CV, normal pulse voltammetry (NPV), chronoamperometry (CA) and open-circuit potential (OCP) measurements for the purpose of comparing each technique's accuracy in measuring U 3+ and Mg 2+ concentrations. Of all the techniques tested, NPV resulted in the lowest error which was, on average, 11.4% and 9.81% for U 3+ and Mg 2+ , respectively.

show abstract

The Actinides

Stoll¹

2006

Encyclopedia of Electrochemistry

View full text Add to dashboard Cite

The sections in this article are Introduction Actinium Aqueous Solutions Electrodeposition Thorium Aqueous Solutions Nonaqueous Solutions Molten‐salt Solutions Electrodeposition Organometallic and Coordination Compounds Protactinium Aqueous Solutions Electrodeposition Nonaqueous Solutions Uranium Aqueous Solutions Electrodeposition Molten‐salt Solutions Nonaqueous Solutions Neptunium Aqueous Solutions Electrodeposition Nonaqueous Solutions Molten‐salt Solutions Plutonium Aqueous Solutions Electrodeposition Molten‐salt Solutions Americium Aqueous Solutions Molten‐salt Solutions Nonaqueous Solutions Electrodeposition Curium Electrodeposition Berkelium Californium Einsteinium Fermium Mendelevium Nobelium

show abstract

Electrochemical studies on the redox mechanism of uranium chloride in molten LiCl–KCl eutectic

Cited by 145 publications

References 13 publications

Investigation of the effects of uranium(III)-chloride concentration on voltammetry in molten LiCl-KCl eutectic with a glass sealed tungsten electrode

Investigation of the effects of uranium(III)-chloride concentration on voltammetry in molten LiCl-KCl eutectic with a glass sealed tungsten electrode

Electroanalytical measurements of binary-analyte mixtures in molten LiCl-KCl eutectic: Uranium(III)- and Magnesium(II)-Chloride

The Actinides

Contact Info

Product

Resources

About