Thermodynamic properties of Ba-Pb alloys determined by EMF measurements using binary CaF2-BaF2 electrolyte

Jarrod Gesualdi, Thomas P. Nigl, Timothy Lichtenstein, Nathan D. Smith, Hojong Kim

Research output: Contribution to journalArticle

Abstract

The thermodynamic properties of Ba-Pb alloys (activities, phase transitions, and partial molar quantities of Gibbs energy, entropy and enthalpy) were determined based on electromotive force (emf) measurements for thirteen mole fractions (xBa = 0.05–0.76) from 700–1060 K using an electrochemical cell: Ba(s) | CaF2-BaF2 | Ba(in Pb). The activity of Ba in liquid Pb was found to be as low as 2.0 × 10–10 at xBa = 0.05 and 973 K, reflecting a large excess partial molar Gibbs energy of –156 kJ mol–1 due to strong chemical interactions between Ba and Pb. Emf measurements were most reliable in the presence of a liquid phase, but were less reliable for high-melting compositions due to the formation of metastable phases during thermal cycling, confirmed by thermal and structural analyses using differential scanning calorimetry and X-ray diffraction. The experimentally-determined activity values of Ba-Pb alloys provide a new, reliable data set for further refinement in the assessment of thermodynamic properties for the Ba-Pb system.

Original languageEnglish (US)
Pages (from-to)D268-D275
JournalJournal of the Electrochemical Society
Volume166
Issue number8
DOIs
StatePublished - Jan 1 2019

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Electrolytes
Thermodynamic properties
Gibbs free energy
Electric potential
Electromotive force
Metastable phases
Electrochemical cells
Force measurement
Liquids
Thermal cycling
Differential scanning calorimetry
Enthalpy
Melting
Entropy
Phase transitions
X ray diffraction
Chemical analysis
Hot Temperature

All Science Journal Classification (ASJC) codes

  • Electronic, Optical and Magnetic Materials
  • Renewable Energy, Sustainability and the Environment
  • Surfaces, Coatings and Films
  • Electrochemistry
  • Materials Chemistry

Cite this

Gesualdi, Jarrod ; Nigl, Thomas P. ; Lichtenstein, Timothy ; Smith, Nathan D. ; Kim, Hojong. / Thermodynamic properties of Ba-Pb alloys determined by EMF measurements using binary CaF2-BaF2 electrolyte. In: Journal of the Electrochemical Society. 2019 ; Vol. 166, No. 8. pp. D268-D275.
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Thermodynamic properties of Ba-Pb alloys determined by EMF measurements using binary CaF2-BaF2 electrolyte. / Gesualdi, Jarrod; Nigl, Thomas P.; Lichtenstein, Timothy; Smith, Nathan D.; Kim, Hojong.

In: Journal of the Electrochemical Society, Vol. 166, No. 8, 01.01.2019, p. D268-D275.

Research output: Contribution to journalArticle

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