Oxygen Coefficient of Uranium Oxides and Current Efficiency as Influenced by Electrolysis Parameters and Composition of Molten Salt Electrolytes in the Na2WO4-Na2W2O7-UO2WO4 System

The oxygen coefficient of uranium oxides, their structure, and current efficiency were studied as influenced by the electrolyte composition, deposition potential, and temperature of electrolysis. On passing from Na₂WO₄-UO₂WO₄ binary system to lower-melting ternary systems the dependences of the oxygen coefficient in the cathodic product on the electrolyte composition and electrolysis parameters remain essentially similar. Significant deviation of the experimental current efficiency with respect to uranium oxides from the theoretical value suggests significant chemical interaction between the cathodic product and electrolyte. The corrosion rate increases and the current efficiency decreases with increasing temperature and concentration of W₂O₇ ^2- ions. The structure of the resulting cathodic deposits is predominantly determined by their specific electrical conductivity, which is a function of the chemical composition of the electrolyte. The dendrite structure is typical for higher oxides.     

Sequential recovery of uranium oxides by electrolysis of M2WO4-M2W2O7-UO2WO4 melts (M = Li, Na, K, Cs)

The effect of the electrolyte composition and solvent salt cation on the oxygen coefficient of the cathode product (O/U atomic ratio) and on the main characteristics of potentiostatic electrolytic deposition of UO₂ (cathode current efficiency, current density, product deposition rate) in sequential recovery of uranium oxides from electrolytes of the system M₂WO₄-M₂W₂O₇-UO₂WO₄ (M = Li, Na, K, Cs) in air was examined. The dependence of the oxygen coefficient of the cathode product on the electrolyte composition and solvent salt cation does not differ essentially from that observed previously in short experiments with low melt depletion of U. The current efficiency, initial current density, and product deposition rate decrease with the electrolyte depletion of U. The results obtained are satisfactorily accounted for in terms of the model of ionic composition of uranyl-containing oxide salt electrolytes, based on the concept of complexation and stepwise solvolysis of uranyl ions, taking into account formation of lower valence forms of U due to chemical corrosion of the cathode product.     

Influence of the electrolysis conditions and composition of electrolytes in the M2WO4-M2W2O7-UO2WO4 system (M = Li, Na, K, Cs) on the oxygen coefficient of uranium oxide

The oxygen coefficient (O/U atomic ratio) of the cathodic product prepared by potentiostatic electrolysis of tungstate melts was studied in relation to the electrolyte composition, deposition potential, temperature of electrolysis, and cation of the solvent salt. With increasing temperature, the oxygen coefficient of the cathodic product increases. With shifting the deposition potential toward more negative potentials, with increasing concentration of W₂O ₇ ^2? anions, and with decreasing concentration of UO₂WO₄ in the tungstate electrolytes, uranium oxides with smaller oxygen coefficients are formed. The oxygen coefficient decreases with increasing radius of the salt cation, other conditions being equal. The abnormal behavior of melts based on Li₂WO₄ is probably due to lower activity of O^2? anions capable to form strong Li₃O⁺ complexes with lithium cations in the melt. The experimental results can be accounted for using the model of the ionic composition of uranyl-containing tungstate melts based on the concepts of complexation and stepwise solvolysis of uranyl ions.