Electrode Reaction of Cerium into Liquid Bismuth in the Eutectic LiCl-KCl

Electrochemical behaviour of terbium in the eutectic LiCl-KCl in Cd liquid electrodes.- Evaluation of the thermochemical properties of the TbCdx intermetallic compounds

“…The regression analysis of the data and its residual analysis indicate a positive correlation of the values, and that this correlation is compatible with a linear model, indicating a mass transport controlled by diffusion both in the salt and the metallic phase. (ii) The ratio of the anodic and cathodic peaks currents, Ip a /Ip c , remained close to unity, thereby according to the theory of cyclic voltammetry [13] the diffusion coefficients D Tb(III) in LiCl-KCl and D Tb into the liquid metal are expected to be of the same order, as it has been shown before for other lanthanides [9,[14][15][16], and actinides [6,17,20] in liquid metals. (iii) After correction of the ohmic drop, and despite the difficulty of measuring the cathodic peak potential, Ep c , it has been observed that both Ep c and Ep a , do not change with increasing sweep rate for values lower than 0.050 V s À1 , whereas for higher sweep rates a slightly shift towards more cathodic and anodic values respectively is detectable, indicating that the electrochemical system is close to the reversibility but not fully reversible.…”

“…As it has been reported previously [9,15], the mol fraction of Tb in the liquid metal, X TbinCd , needed in equation (7), can be calculated by means of Equation (10):…”

“…Taken into account, as it is shown by equation (8) [9,14,15], that the half-wave potential of the cyclic voltammograms becomes the equilibrium potential adopted by the liquid metal electrode, E eq TbinCd , if the concentrations of Tb(III) in the melt LiCl-KCl and Tb (0) in the Cd phase, expressed in mol cm À3 , are equal.…”

“…In order to compare the experimental results with the predictions of the theory, it is mandatory to maintain the concentration of the deposited metal in the Cd interphase below its solubility in the liquid metal [9,[13][14][15][16][17][18]. If the amount of Tb exceeds its solubility, the electrode loses its homogeneity, and separate solid phases (i.e.…”

“…Cyclic voltammetry using liquid metals as working electrodes, has been proposed as an alternative approach for the acquisition of basic data on electrolytic alloy formation, in the same way that polarography has been used in aqueous solution [9,[13][14][15][16][17]. In order to compare the experimental results with the predictions of the theory, it is mandatory to maintain the concentration of the deposited metal in the Cd interphase below its solubility in the liquid metal [9,[13][14][15][16][17][18].…”