The reaction of the cathodic reduction of Dy(III) ions to metal in molten caesium chloride at the temperature range of 963–1063 K on inert molybdenum and active gallium electrodes at inert atmosphere was studied by cyclic, square-wave voltammetry and open-circuit potentiometry. All operations with the experimental cell were carried out in a dry box, excluding the ingress of oxygen and moisture impurities in the reagents used. Cyclic voltammograms of molten CsCl–DyCl3 solutions obtained on a molybdenum inert electrode at different scan rates at 987 K were characterized by the presence of one reduction current peak and one corresponding it oxidation peak. This indicates that the reaction of cathodic reduction of Dy(III) ions to metal proceeds in one stage with the possible participation of three electrons. An asymmetric Gaussian cathode curve with one clearly defined current peak was recorded on a square-wave voltammogram. The number of the exchanged electrons of the electrochemical reaction was calculated from the half-peak width of the cathode curve. It was close to three (n = = 2.89 ± 0.05). So, the mechanism of the cathodic deposition of metallic dysprosium on an inert Mo electrode was established. It was shown that the electrode reaction was proceeded irreversibly, in one stage and was controlled by the charge transfer rate. The diffusion coefficients of complex [DyCl6]3– ions at different temperatures were calculated and the activation energy of the diffusion process was determined. The temperature dependence of the diffusion coefficients of dysprosium(III) ions obeys the Arrhenius law and was described by the equation: logD=−3.15−2010T±0.02. The activation energy of the diffusion process was equal to ‒38.7 kJ/mol. The experimental dependence of the apparent standard potential of Dy(III)/Dy couple vs. the temperature was established. It was described by the linear equation: E_{{{{{\text{Dy}}\left( {{\text{III}}} \right)} \mathord{\left/ {\vphantom {{{\text{Dy}}\left( {{\text{III}}} \right)} {{\text{Dy}}}}} \right. \kern-\delimiterspace} {{\text{Dy}}}}}}^{{\text{*}}} = - \left( {3.921 \pm 0.007} \right) + \left( {6.8 \pm 0.1} \right) \cdot {{10}^{{ - 4}}} \cdot T \pm 0.005\,\,{\text{V}}. The principal thermodynamic characteristics of dysprosium trichloride were calculated. It was established that the reaction of the electrochemical deposition of dysprosium on an active gallium electrode was associated with the process of alloy formation and proceeds with depolarization. The equilibrium potentials of the Dy–Ga alloy were measured and the temperature dependence of the apparent standard potential of the alloy was determined, which was described by the linear equation: E**Dy(Ga)=−(3.069±0.005)+(3.2±0.2)⋅10−4T±0.006V. The scheme of the reaction of the of intermetallic Dy–Ga compounds formation was proposed. The activity coefficients and excess Gibbs partial energy change for the metallic dysprosium in liquid gallium were calculated.
Translated title of the contributionSTUDY OF THE ELECTROCHEMICAL REDUCTION MECHANISM OF DYSPROSIUM(III) IONS ON INERT AND ACTIVE ELECTRODES IN MOLTEN CAESIUM CHLORIDE
Original languageRussian
Pages (from-to)373-383
Number of pages11
JournalРасплавы
Issue number4
DOIs
Publication statusPublished - 2022

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  • 31.00.00 CHEMISTRY

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