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<p>Thermo-electromotive force (thermo-EMF) of Pd–Ag, Rh-Ag, Pt–Ag and Ag-C couples was measured in temperature range 45.5—715.2 ºC at the cold end temperature of 25 ºC. A cold-end temperature of 25&#xa0;°C proved to be the most convenient and stable in the following electrochemical experiments. All measurements were carried out by Autolab PGSTAT 302N potentiostat/galvanostat with using the chronopotentiometry method. Thermo-EMF values of Pd–Ag, Rh-Ag, Pt–Ag and Ag-C couples have the same sign. It leads to additive effect for these values for platinoid – C couple and enlarged shift to negative side value of electrode potentials up to 20&#xa0;mV in electrochemical experiments. These data were used for correction of thermodynamic data on noble metal chloride formation in low-temperature LiCl–KCl-CsCl melt. When thermo-EMF is taken into account, formal electrode potentials have a shift of values up to 10 mV. Recalculation of ∆<i>G*,</i> ∆<i>H</i>*, ∆<i>S</i>* also demonstrates the shift of its values up to 2&#xa0;kJ·mol<sup>−1</sup>, 3&#xa0;kJ·mol<sup>−1</sup> and 7&#xa0;J·mol<sup>−1</sup>·K<sup>−1</sup>, correspondingly. These are important changes for building the mathematical model of platinoid separation process in low-temperature LiCl–KCl-CsCl melt at working temperature of 450 ºC.</p>

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Study of the effect of the Pd-Ag, Rh-Ag, Pt-Ag, Ag-C thermo-electromotive force on the measured values of the electrode potential

  • 期刊论文

  • 发表日期：

    2025年10月6日

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  • Anastasia Osipenko,
  • Alexander Osipenko

摘要

Thermo-electromotive force (thermo-EMF) of Pd–Ag, Rh-Ag, Pt–Ag and Ag-C couples was measured in temperature range 45.5—715.2 ºC at the cold end temperature of 25 ºC. A cold-end temperature of 25 °C proved to be the most convenient and stable in the following electrochemical experiments. All measurements were carried out by Autolab PGSTAT 302N potentiostat/galvanostat with using the chronopotentiometry method. Thermo-EMF values of Pd–Ag, Rh-Ag, Pt–Ag and Ag-C couples have the same sign. It leads to additive effect for these values for platinoid – C couple and enlarged shift to negative side value of electrode potentials up to 20 mV in electrochemical experiments. These data were used for correction of thermodynamic data on noble metal chloride formation in low-temperature LiCl–KCl-CsCl melt. When thermo-EMF is taken into account, formal electrode potentials have a shift of values up to 10 mV. Recalculation of ∆G*, ∆H*, ∆S* also demonstrates the shift of its values up to 2 kJ·mol−1, 3 kJ·mol−1 and 7 J·mol−1·K−1, correspondingly. These are important changes for building the mathematical model of platinoid separation process in low-temperature LiCl–KCl-CsCl melt at working temperature of 450 ºC.