First principles computational studies of spontaneous reduction reaction of Eu(III) in eutectic LiCl-KCl molten salt

Choah Kwon, Seung Hyo Noh, Hoje Chun, Il Soon Hwang, Byungchan Han

Research output: Contribution to journalArticle

2 Citations (Scopus)

Abstract

Using first principles calculations, we study fundamental mechanism of spontaneous reduction reaction of Eu3+ to Eu2+ in eutectic LiCl-KCl molten salt. We decouple the reaction Gibbs free energy into enthalpy and entropy contributions by using rigorous thermodynamic formalism. Key structural features of the solvation shell are characterized by the radial distribution function and the coordination number. Compared with Eu2+, the Eu3+ ion has a more rigid framework of the solvation shells, corroborating its stronger electrostatic interaction with neighboring ligands of Cl ions and a more favorable state on the aspect of enthalpy. Computations on vibrational frequency, however, pose significant contribution of vibrational entropy to the reaction Gibbs free energy for the reduction. Vibration frequency of Eu2+ is smaller than that of Eu3+, driving a more positive change of the entropy in the reduction reaction. Furthermore, an Eu2+ diffuses more quickly than an Eu3+ in the LiCl-KCl molten salt with switching mechanism of ligand Cl ions in the solvation shell. Our results propose that the spontaneity of the reduction reaction is driven by the entropic contribution by overcoming the penalty of the reaction enthalpy.

Original languageEnglish
Pages (from-to)2757-2765
Number of pages9
JournalInternational Journal of Energy Research
Volume42
Issue number8
DOIs
Publication statusPublished - 2018 Jun 25

Fingerprint

Eutectics
Molten materials
Solvation
Salts
Enthalpy
Entropy
Gibbs free energy
Ions
Ligands
Vibrational spectra
Coulomb interactions
Distribution functions
Thermodynamics

All Science Journal Classification (ASJC) codes

  • Renewable Energy, Sustainability and the Environment
  • Nuclear Energy and Engineering
  • Fuel Technology
  • Energy Engineering and Power Technology

Cite this

@article{050a8a497558412585a17fbf98147c22,
title = "First principles computational studies of spontaneous reduction reaction of Eu(III) in eutectic LiCl-KCl molten salt",
abstract = "Using first principles calculations, we study fundamental mechanism of spontaneous reduction reaction of Eu3+ to Eu2+ in eutectic LiCl-KCl molten salt. We decouple the reaction Gibbs free energy into enthalpy and entropy contributions by using rigorous thermodynamic formalism. Key structural features of the solvation shell are characterized by the radial distribution function and the coordination number. Compared with Eu2+, the Eu3+ ion has a more rigid framework of the solvation shells, corroborating its stronger electrostatic interaction with neighboring ligands of Cl− ions and a more favorable state on the aspect of enthalpy. Computations on vibrational frequency, however, pose significant contribution of vibrational entropy to the reaction Gibbs free energy for the reduction. Vibration frequency of Eu2+ is smaller than that of Eu3+, driving a more positive change of the entropy in the reduction reaction. Furthermore, an Eu2+ diffuses more quickly than an Eu3+ in the LiCl-KCl molten salt with switching mechanism of ligand Cl− ions in the solvation shell. Our results propose that the spontaneity of the reduction reaction is driven by the entropic contribution by overcoming the penalty of the reaction enthalpy.",
author = "Choah Kwon and Noh, {Seung Hyo} and Hoje Chun and Hwang, {Il Soon} and Byungchan Han",
year = "2018",
month = "6",
day = "25",
doi = "10.1002/er.4064",
language = "English",
volume = "42",
pages = "2757--2765",
journal = "International Journal of Energy Research",
issn = "0363-907X",
publisher = "John Wiley and Sons Ltd",
number = "8",

}

First principles computational studies of spontaneous reduction reaction of Eu(III) in eutectic LiCl-KCl molten salt. / Kwon, Choah; Noh, Seung Hyo; Chun, Hoje; Hwang, Il Soon; Han, Byungchan.

In: International Journal of Energy Research, Vol. 42, No. 8, 25.06.2018, p. 2757-2765.

Research output: Contribution to journalArticle

TY - JOUR

T1 - First principles computational studies of spontaneous reduction reaction of Eu(III) in eutectic LiCl-KCl molten salt

AU - Kwon, Choah

AU - Noh, Seung Hyo

AU - Chun, Hoje

AU - Hwang, Il Soon

AU - Han, Byungchan

PY - 2018/6/25

Y1 - 2018/6/25

N2 - Using first principles calculations, we study fundamental mechanism of spontaneous reduction reaction of Eu3+ to Eu2+ in eutectic LiCl-KCl molten salt. We decouple the reaction Gibbs free energy into enthalpy and entropy contributions by using rigorous thermodynamic formalism. Key structural features of the solvation shell are characterized by the radial distribution function and the coordination number. Compared with Eu2+, the Eu3+ ion has a more rigid framework of the solvation shells, corroborating its stronger electrostatic interaction with neighboring ligands of Cl− ions and a more favorable state on the aspect of enthalpy. Computations on vibrational frequency, however, pose significant contribution of vibrational entropy to the reaction Gibbs free energy for the reduction. Vibration frequency of Eu2+ is smaller than that of Eu3+, driving a more positive change of the entropy in the reduction reaction. Furthermore, an Eu2+ diffuses more quickly than an Eu3+ in the LiCl-KCl molten salt with switching mechanism of ligand Cl− ions in the solvation shell. Our results propose that the spontaneity of the reduction reaction is driven by the entropic contribution by overcoming the penalty of the reaction enthalpy.

AB - Using first principles calculations, we study fundamental mechanism of spontaneous reduction reaction of Eu3+ to Eu2+ in eutectic LiCl-KCl molten salt. We decouple the reaction Gibbs free energy into enthalpy and entropy contributions by using rigorous thermodynamic formalism. Key structural features of the solvation shell are characterized by the radial distribution function and the coordination number. Compared with Eu2+, the Eu3+ ion has a more rigid framework of the solvation shells, corroborating its stronger electrostatic interaction with neighboring ligands of Cl− ions and a more favorable state on the aspect of enthalpy. Computations on vibrational frequency, however, pose significant contribution of vibrational entropy to the reaction Gibbs free energy for the reduction. Vibration frequency of Eu2+ is smaller than that of Eu3+, driving a more positive change of the entropy in the reduction reaction. Furthermore, an Eu2+ diffuses more quickly than an Eu3+ in the LiCl-KCl molten salt with switching mechanism of ligand Cl− ions in the solvation shell. Our results propose that the spontaneity of the reduction reaction is driven by the entropic contribution by overcoming the penalty of the reaction enthalpy.

UR - http://www.scopus.com/inward/record.url?scp=85044417781&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85044417781&partnerID=8YFLogxK

U2 - 10.1002/er.4064

DO - 10.1002/er.4064

M3 - Article

AN - SCOPUS:85044417781

VL - 42

SP - 2757

EP - 2765

JO - International Journal of Energy Research

JF - International Journal of Energy Research

SN - 0363-907X

IS - 8

ER -