Thermodynamic Properties of Dilute Solutions of Lead(II) Oxide in an Equimolar Mixture of KCl–PbCl<sub>2</sub>

Pershin, P. S.; Batukhtin, V.P.; Шуров, Н. И.; Архипов, П. А.; Zaikov, Yu. P.

doi:10.1021/je300649f

Cited by 9 publications

(9 citation statements)

References 10 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The literature on this field is extremely limited. Several works describe the corrosion behavior of ceramic materials based on the yttria stabilized zirconia electrolyte [36][37][38][39][40][41], but the corrosion instability of ZrO 2 -based ceramic electrolytes in Li + -containing melts was found. Therefore, the search for the new materials with complex properties such as high oxygen-ion conductivity and corrosion resistance in halide melts is extremely important.…”

Section: Introductionmentioning

confidence: 99%

The Gd2−xMgxZr2O7−x/2 Solid Solution: Ionic Conductivity and Chemical Stability in the Melt of LiCl-Li2O

et al. 2022

View full text Add to dashboard Cite

Materials with pyrochlore structure A2B2O7 have attracted considerable attention owing to their various applications as catalysts, sensors, electrolytes, electrodes, and magnets due to the unique crystal structure and thermal stability. At the same time, the possibility of using such materials for electrochemical applications in salt melts has not been studied. This paper presents the new results of obtaining high-density Mg2+-doped ceramics based on Gd2Zr2O7 with pyrochlore structure and comprehensive investigation of the electrical properties and chemical stability in a lithium chloride melt with additives of various concentrations of lithium oxide, performed for the first time. The solid solution of Gd2−xMgxZr2O7−x/2 (0 ≤ x ≤ 0.10) with the pyrochlore structure was obtained by mechanically milling stoichiometric mixtures of the corresponding oxides, followed by annealing at 1500 °C. The lattice parameter changed non-linearly as a result of different mechanisms of Mg2+ incorporation into the Gd2Zr2O7 structure. At low dopant concentrations (x ≤ 0.03) some interstitial positions can be substituted by Mg2+, with further increasing Mg2+-content, the decrease in the lattice parameter occurred due to the substitution of host-ion sites with smaller dopant-ion. High-density ceramics 99% was prepared at T = 1500 °C. According to the results of the measurements of electrical conductivity as a function of oxygen partial pressure, all investigated samples were characterized by the dominant ionic type of conductivity over a wide range of pO2 (1 × 10–18 ≤ pO2 ≤ 0.21 atm) and T < 800 °C. The sample with the composition of x = 0.03 had the highest oxygen-ion conductivity (10−3 S·cm−1 at 600 °C). The investigation of chemical stability of ceramics in the melt of LiCl with 2.5 mas.% Li2O showed that the sample did not react with the melt during the exposed time of one week at the temperature of 650 °C. This result makes it possible to use these materials as oxygen activity sensors in halide melts.

show abstract

Section: Introductionmentioning

confidence: 99%

The Gd2−xMgxZr2O7−x/2 Solid Solution: Ionic Conductivity and Chemical Stability in the Melt of LiCl-Li2O

et al. 2022

View full text Add to dashboard Cite

show abstract

“…Raman spectroscopy data illustrates the presence of coordination polyhedrons of the Pb n Cl 3n n− type, where n ≤ 4 in the molten potassium and lead chlorides with PbCl 2 concentration ≤50 mol %. 19 Based on the data on the thermodynamics of lead oxide dissolution in chloride melts 37 the equilibrium between the complexes in the KCl−PbCl 2 melt may be described by the following equation…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…Raman spectroscopy data illustrates the presence of coordination polyhedrons of the Pb n Cl 3 n n – type, where n ≤ 4 in the molten potassium and lead chlorides with PbCl 2 concentration ≤50 mol % . Based on the data on the thermodynamics of lead oxide dissolution in chloride melts the equilibrium between the complexes in the KCl–PbCl 2 melt may be described by the following equation Therefore, lead oxide dissolution in the chloride melt may proceed according to the following mechanism The addition of the double charged oxygen anion into the melt in the form of lead oxide makes the melt structure more complex because of the formation of oxygen bridges between the melt polyhedrons, in which one of the chloride anions is substituted by the O 2– anion. In addition, the molar volume of the melt increases.…”

Section: Resultsmentioning

confidence: 99%

Interaction between PbO and the KCl–PbCl₂–PbO System for Lead Electrochemical Refining

2020

View full text Add to dashboard Cite

A KCl–PbCl2 (50.0–50.0 mol %) molten system was used as an electrolyte for secondary lead refining. As a result, pure lead and an anode product containing 52.81 mol % Sb, 33.66 mol % Bi, 7.54 mol % Pb, 3.74 mol % Ag, and 2.24 mol % As were obtained. Long-term electrochemical refining was found to be possible in the KCl–PbCl2 electrolyte. Thermal analysis was applied to determine liquidus temperatures of the KCl–PbCl2 (50.0–50.0 mol %) mixture with the PbO concentration ranging from 0 to 20 mol %. The temperature dependence of the PbO solubility in the KCl–PbCl2 (50.0–50.0 mol %) melt was studied, and the thermodynamic parameters of the PbO solubility were calculated. Electrical conductivities and densities of oxy-chloride melts were measured.

show abstract

“…12 These systems were found to have a negative deviation from Raul's law. Such behavior was explained by the formation of complex compounds, particularly Pb 2 OCl 2 .…”

Section: Discussionmentioning

confidence: 99%

The Electrodeposition of Lead in LiCl-KCl-PbCl₂and LiCl-KCl-PbCl₂-PbO Melts

Pershin

Khalimullina

Архипов

et al. 2014

J. Electrochem. Soc.

View full text Add to dashboard Cite

The mechanism for the electrode process that occurs on a molybdenum substrate in LiCl-KCl-PbCl 2 and LiCl-KCl-PbCl 2 -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 Pb 2+ ions decrease due to the formation of Pb 2 O 2+ 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 Pb 2 O 2+ complex ions. A theoretical polarization curve for the diffusion kinetics was calculated.Investigating the kinetics of electrode processes allows one to determine the kinetic parameters of reactions, to calculate the activation energies of these reactions and to establish the limiting stages of electrode processes. 1 Additionally, data related to the mechanism of the electrode processes is valuable for developing the scientific basis for electrochemical technologies that meet the current ecological and energy saving requirements.In the literature, considerable attention is focused on the electrorecovery of lead from molten salts. The authors 2,3 reported that the electro recovery of Pb 2+ ions from a LiCl-KCl melt is a diffusioncontrolled, single-stage reaction.Haaberg et al. 4 investigated the lead electrodeposition process in LiCl-KCl melts and in pure PbCl 2 and determined that the migration of Pb 2+ ions controls the rate of the cathode process in the pure PbCl 2 melt at temperatures from 823 to 858 K. A diffusion regime of the process was observed in the LiCl-KCl melt; the diffusion coefficient for the Pb 2+ ions was equal to 2 · 10 −5 sm 2 /s. The cathode behavior of lead ions on a molybdenum substrate in LiCl-KCl-PbCl 2 and LiCl-KCl-PbCl 2 -MgCl 2 melts was studied using voltammetry and chronopotentiometry techniques in later works. 5 The extraction of lithium from the initially deposited lead was found to result in the formation of a Li-Pb alloy in LiCl-KCl-PbCl 2 and LiPb-Mg melts with the addition of MgCl 2 . The diffusion coefficient of Pb 2+ ions was determined using various techniques, and its value was found to be 2.26 · 10 −5 sm 2 /s. In a number of studies, there are considerable differences regarding the mechanism of the cathode process. Therefore, Strenberg et al. 6 established a two-stage mechanism for the recovery of Pb 2+ ions through the stage of the formation of monovalent Pb + ions.These works were primarily performed during the second half of the XX th century and were related to dilute solutions of lead in alkali metal chlorides, free of oxide ions. There is no information available regarding the mechanisms of electrode processes in oxide-chloride melts. The structures and compositions of ...

show abstract

Thermodynamic Properties of Dilute Solutions of Lead(II) Oxide in an Equimolar Mixture of KCl–PbCl₂

Cited by 9 publications

References 10 publications

The Gd2−xMgxZr2O7−x/2 Solid Solution: Ionic Conductivity and Chemical Stability in the Melt of LiCl-Li2O

The Gd2−xMgxZr2O7−x/2 Solid Solution: Ionic Conductivity and Chemical Stability in the Melt of LiCl-Li2O

Interaction between PbO and the KCl–PbCl₂–PbO System for Lead Electrochemical Refining

The Electrodeposition of Lead in LiCl-KCl-PbCl₂and LiCl-KCl-PbCl₂-PbO Melts

Contact Info

Product

Resources

About

Thermodynamic Properties of Dilute Solutions of Lead(II) Oxide in an Equimolar Mixture of KCl–PbCl2

Cited by 9 publications

References 10 publications

The Gd2−xMgxZr2O7−x/2 Solid Solution: Ionic Conductivity and Chemical Stability in the Melt of LiCl-Li2O

The Gd2−xMgxZr2O7−x/2 Solid Solution: Ionic Conductivity and Chemical Stability in the Melt of LiCl-Li2O

Interaction between PbO and the KCl–PbCl2–PbO System for Lead Electrochemical Refining

The Electrodeposition of Lead in LiCl-KCl-PbCl2and LiCl-KCl-PbCl2-PbO Melts

Contact Info

Product

Resources

About

Thermodynamic Properties of Dilute Solutions of Lead(II) Oxide in an Equimolar Mixture of KCl–PbCl₂

Interaction between PbO and the KCl–PbCl₂–PbO System for Lead Electrochemical Refining

The Electrodeposition of Lead in LiCl-KCl-PbCl₂and LiCl-KCl-PbCl₂-PbO Melts