Determination of kinetic properties of Sm(III)/Sm(II) reaction in LiCl–KCl molten salt using cyclic voltammetry and electrochemical impedance spectroscopy

Yoon, Dalsung; Pormatikul, Jinnapat; Shaltry, Michael; Phongikaroon, Supathorn; Allahar, Kerry

doi:10.1007/s10967-019-06796-z

Title: Determination of kinetic properties of Sm(III)/Sm(II) reaction in LiCl–KCl molten salt using cyclic voltammetry and electrochemical impedance spectroscopy

Abstract

Electrochemical and kinetic properties of samarium (Sm) in LiCl-KCl eutectic salt were explored at various concentrations and temperatures. Cyclic voltammetry (CV) were performed to determine diffusion coefficient and the rate constant (k0). In addition, electrochemical impedance spectroscopy (EIS) was conducted for additional understandings on the kinetic behaviors of Sm(III)/Sm(II) couple. The values of the diffusion coefficients were in the range of 3.54 × 10^-6 to 9.58 × 10^-5 cm² s^-1 and the values of k⁰ were estimated to be in the range of 0.63 × 10^-2 to 1.11 × 10^-2 cm s^-1. The values of i₀ for Sm(III)/Sm(II) were computed by obtaining the charge transfer resistance from the curve fitting analysis, ranging from 1.04 ×10^-3 to 2.97×10^-3 A cm^-2.

Authors:

^[1]; Pormatikul, Jinnapat ^[2]; Shaltry, Michael ^[3]; Phongikaroon, Supathorn ^[2]; Allahar, Kerry ^[4]

Virginia Commonwealth Univ., Richmond, VA (United States); Korea Atomic Energy Research Inst., Daejeon (South Korea)
Virginia Commonwealth Univ., Richmond, VA (United States)
Idaho National Lab. (INL), Idaho Falls, ID (United States)
Boise State Univ., ID (United States)

Publication Date:: 2019-09-26

Research Org.:: Idaho National Lab. (INL), Idaho Falls, ID (United States)

Sponsoring Org.:: USDOE

OSTI Identifier:: 1575283

Report Number(s):: INL/JOU-17-41558-Rev000
Journal ID: ISSN 0236-5731; TRN: US2001340

Grant/Contract Number:: AC07-05ID14517

Resource Type:: Accepted Manuscript

Journal Name:: Journal of Radioanalytical and Nuclear Chemistry

Additional Journal Information:: Journal Volume: 322; Journal Issue: 2; Journal ID: ISSN 0236-5731

Publisher:: Springer

Country of Publication:: United States

Language:: English

Subject:: 11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS; samarium, exchange current density, molten salt, impedance spectroscopy

Citation Formats


                    Yoon, Dalsung, Pormatikul, Jinnapat, Shaltry, Michael, Phongikaroon, Supathorn, and Allahar, Kerry. Determination of kinetic properties of Sm(III)/Sm(II) reaction in LiCl–KCl molten salt using cyclic voltammetry and electrochemical impedance spectroscopy.  United States: N. p., 2019. 
Web.  doi:10.1007/s10967-019-06796-z.

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                    Yoon, Dalsung, Pormatikul, Jinnapat, Shaltry, Michael, Phongikaroon, Supathorn, & Allahar, Kerry. Determination of kinetic properties of Sm(III)/Sm(II) reaction in LiCl–KCl molten salt using cyclic voltammetry and electrochemical impedance spectroscopy.  United States.  https://doi.org/10.1007/s10967-019-06796-z

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                    Yoon, Dalsung, Pormatikul, Jinnapat, Shaltry, Michael, Phongikaroon, Supathorn, and Allahar, Kerry. Thu .  
"Determination of kinetic properties of Sm(III)/Sm(II) reaction in LiCl–KCl molten salt using cyclic voltammetry and electrochemical impedance spectroscopy".  United States.  https://doi.org/10.1007/s10967-019-06796-z.  https://www.osti.gov/servlets/purl/1575283.

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@article{osti_1575283,

  title        = {Determination of kinetic properties of Sm(III)/Sm(II) reaction in LiCl–KCl molten salt using cyclic voltammetry and electrochemical impedance spectroscopy},

  author       = {Yoon, Dalsung and Pormatikul, Jinnapat and Shaltry, Michael and Phongikaroon, Supathorn and Allahar, Kerry},

  abstractNote = {Electrochemical and kinetic properties of samarium (Sm) in LiCl-KCl eutectic salt were explored at various concentrations and temperatures. Cyclic voltammetry (CV) were performed to determine diffusion coefficient and the rate constant (k0). In addition, electrochemical impedance spectroscopy (EIS) was conducted for additional understandings on the kinetic behaviors of Sm(III)/Sm(II) couple. The values of the diffusion coefficients were in the range of 3.54 × 10-6 to 9.58 × 10-5 cm2 s-1 and the values of k0 were estimated to be in the range of 0.63 × 10-2 to 1.11 × 10-2 cm s-1. The values of i0 for Sm(III)/Sm(II) were computed by obtaining the charge transfer resistance from the curve fitting analysis, ranging from 1.04 ×10-3 to 2.97×10-3 A cm-2.},

  doi          = {10.1007/s10967-019-06796-z},

  journal      = {Journal of Radioanalytical and Nuclear Chemistry},

  number       = 2,

  volume       = 322,

  place        = {United States},

  year         = {2019},

  month        = {9}

}

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Works referenced in this record:

Chemical basis for pyrochemical reprocessing of nuclear fuel
journal, January 1991

Ackerman, John P.
Industrial & Engineering Chemistry Research, Vol. 30, Issue 1
DOI: 10.1021/ie00049a022

Anodic dissolution of U, Zr and U–Zr alloy and convolution voltammetry of Zr4+|Zr2+ couple in molten LiCl–KCl eutectic
journal, October 2011

Ghosh, Suddhasattwa; Vandarkuzhali, S.; Gogoi, Nibedita
Electrochimica Acta, Vol. 56, Issue 24
DOI: 10.1016/j.electacta.2011.06.027

Determining the Exchange Current Density and Tafel Constant for Uranium in LiCl/KCl Eutectic
journal, October 2014

Rose, M. A.; Williamson, M. A.; Willit, J.
ECS Electrochemistry Letters, Vol. 4, Issue 1
DOI: 10.1149/2.0101501eel

Electron-transfer kinetics from cyclic voltammetry. Quantitative description of electrochemical reversibility
journal, June 1981

Klingler, R. J.; Kochi, J. K.
The Journal of Physical Chemistry, Vol. 85, Issue 12
DOI: 10.1021/j150612a028

Electrochemical impedance spectroscopy study of indium couples in LiCl-KCl eutectic at 450 °C
journal, June 1996

Mohamedi, M.; Bouteillon, J.; Poignet, J. C.
Electrochimica Acta, Vol. 41, Issue 9
DOI: 10.1016/0013-4686(95)00401-7

Limitations in the analysis of ac impedance data with poorly separated faradaic and diffusional processes
journal, February 1991

VanderNoot, T. J.
Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 300, Issue 1-2
DOI: 10.1016/0022-0728(91)85395-6

An electrochemical study of samarium ions in the molten eutectic LiCl+KCl
journal, October 2004

Cordoba, G.; Caravaca, C.
Journal of Electroanalytical Chemistry, Vol. 572, Issue 1
DOI: 10.1016/j.jelechem.2004.05.029

Electrochemical Formation of Divalent Samarium Cation and Its Characteristics in LiCl–KCl Melt
journal, June 2018

Bae, Sang-Eun; Jung, Tae Sub; Cho, Young-Hwan
Inorganic Chemistry, Vol. 57, Issue 14
DOI: 10.1021/acs.inorgchem.8b00909

Electrochemical Properties and Analyses of CeCl ₃ in LiCl-KCl Eutectic Salt
journal, January 2015

Yoon, D.; Phongikaroon, S.
Journal of The Electrochemical Society, Vol. 162, Issue 10
DOI: 10.1149/2.0401510jes

Evaluation of the Electrochemical Behavior of CeCl3 in Molten LiCl-KCl Eutectic Utilizing Metallic Ce as an Anode
journal, January 2011

Marsden, K. C.; Pesic, B.
Journal of The Electrochemical Society, Vol. 158, Issue 6
DOI: 10.1149/1.3575637

Electrochemical Impedance Spectroscopy and its Applications
book, January 2002

Lasia, Andrzej; Conway, B. E.; Bockris, J. O'M.
Modern Aspects of Electrochemistry, p. 143-248
DOI: 10.1007/0-306-46916-2_2

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Title: Determination of kinetic properties of Sm(III)/Sm(II) reaction in LiCl–KCl molten salt using cyclic voltammetry and electrochemical impedance spectroscopy

Abstract

Citation Formats

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Electrochemical impedance spectroscopy study of indium couples in LiCl-KCl eutectic at 450 °C journal, June 1996

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An electrochemical study of samarium ions in the molten eutectic LiCl+KCl journal, October 2004

Electrochemical Formation of Divalent Samarium Cation and Its Characteristics in LiCl–KCl Melt journal, June 2018

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