ABSTRACT
The present paper is dedicated to the quantitative determination of oxygen-containing impurities in the LiF-NaF-KF eutectic using electrochemical (cyclic and square-wave voltammetry) and reduction melting methods. The LiF-NaF-KF melt was analyzed before and after purifying electrolysis. The amount of oxygen-containing impurities removed from the salt during purification was determined. It was found that after electrolysis, the concentration of oxygen-containing impurities decreased by 7 times. The results obtained via electrochemical techniques and reduction melting were well-correlated, which made it possible to evaluate the quality of the LiF-NaF-KF F melt. To verify the analysis conditions, mechanical mixtures of LiF-NaF-KF containing Li2O were analyzed using the reduction melting method. The oxygen concentration in the mixtures varied from 0.672 to 2.554 wt. %. Based on the analysis results, the dependence approximated by the straight line was obtained. These data may be used to draw calibration curves and to further develop the procedure of oxygen analysis of fluoride melts.
ABSTRACT
The electrochemical behavior of rhenium ions in the molten KF-KBF4-B2O3 salt was systematically studied, and pure metallic rhenium was obtained at the cathode. The processes of rhenium ions reduction and diffusion in molten KF-KBF4-B2O3 were determined using cyclic voltammetry, stationary galvanostatic and polarization curves analyses. The values of diffusion coefficients were 3.15 × 10-5 cm2/s and 4.61 × 10-5 cm2/s for R1 and R2, respectively. Rhenium electrodeposition was carried out at a constant potential. The process of rhenium cathode reduction in KF-KBF4-B2O3 at 773 K was found to be a one-step reaction Re(VII) â Re, and rhenium electrodeposition presumably occurred from two types of complex rhenium ions (KReO4 and K3ReO5). Both processes are quasi-reversible and controlled by diffusion. The obtained cathode deposit was analyzed by SEM, EDX, ICP-OES and XRD methods. The obtained deposit had a thread structure and rhenium was the main component.
