The mechanism for the electrode process that occurs on a molybdenum substrate in LiCl-KCl-PbCl₂ and LiCl-KCl-PbCl₂-PbO melts depending on the concentration of PbO was investigated over the temperature range of 723–823 K using stationary polarization curves and voltammetry techniques. An increase in the concentration of PbO was found to decrease the diffusion-limiting current density for the recovery of lead, which was identified by the appearance of an additional peak in the voltammograms; it can be explained by a decrease in the concentration of Pb²⁺ ions decrease due to the formation of Pb₂O²⁺ complex ions in the electrolyte. The evaluation of the equilibrium constant K_E and the rate constant of the reaction suggests that this reaction is strongly shifted toward the formation of the Pb₂O²⁺ complex ions. A theoretical polarization curve for the diffusion kinetics was calculated.

Thermal analysis was applied to determine liquidus temperatures in the CsCl–PbCl₂–PbO system, with the PbO concentration ranging from 0 to 20 mol%. The temperature dependence of the PbO solubility in the CsCl–PbCl₂ eutectic melt was studied, and the thermodynamic parameters of the PbO dissolution were calculated. The type, morphology, and composition of oxychloride ionic groupings in the melt were determined in situ using Raman spectroscopy.

A new way to reduce the energy consumption during the operation of powerful aluminum reduction cells is suggested via reducing the resistance of the electrolyte, i.e., increasing its electrical conductivity. The electrical conductivity of molten cryolite mixtures NaF-AlF₃-CaF₂-Al₂O₃ with cryolite ratio (CR) of 2.1–3.0 and content of CaF₂ and Al₂O₃, up to 8 wt%, was measured at the temperatures from liquidus to 1300 K. Based on the experimental results, a multifunctional equation for the electrical conductivity of oxide-fluoride cryolite melts was evaluated. The experimental and calculated values of the electrical conductivity agree within 1.5%. The activation energy of the electrical conductivity of the NaF-AlF₃-CaF₂-Al₂O₃ melts was estimated. The activation energy of electrical conductivity for molten NaF-AlF₃ mixtures with CR 3.0 and 2.1, determined by the most mobile cations Na⁺, increased from 15.8 kJ/mol up to 18.5 kJ/mol. It was found that CR had a greater impact on the activation energy than the changes in the Al₂O₃ or CaF₂ concentrations. Based on the ratio of the activation energies of the electrical conductivity and the viscous flow, the correlation between the electrical conductivity and viscosity of molten cryolite mixtures NaF-AlF₃-CaF₂-Al₂O₃ was illustrated.

An anode dissolution of binary metallic lead–bismuth alloys with different concentrations of components has been studied in the KCl–PbCl₂ molten eutectic. The dissolution of lead is found to be a basic process for the alloys of Pb–Bi (59.3–40.7), Pb–Bi (32.5–67.5), Pb–Bi (7.0–93.0) compositions in the whole interval of studied anode current densities. A limiting diffusion current of lead dissolution was observed at 2 A/cm² and 0.1 A/cm² for the alloys of Pb–Bi (5.0–95.0) and Pb–Bi (3.0–97.0) compositions, respectively. The dissolution of bismuth takes place at the anode current densities exceeding the mentioned values. The number of electrons participating in the electrode reactions is detected for each mechanism. Based on the theoretical analysis, the experimental electrolysis of bismuth was performed in the laboratory-scale electrolytic cell with a porous ceramic diaphragm. The final product contained pure bismuth with a lead concentration of 3.5 wt.%.