Electrochemistry of lanthanides in molten chloroaluminates: Part I. The electrochemical behaviour of Eu(III), Yb(III) and Sm(III)

The electrochemical behaviour of Eu(III), Yb(III,II) and Sm(III,II) has been investigated in NaCl-AlCl₃ mixtures, in a temperature range between 150 and 250°C. Principal investigation methods are cyclic voltammetry, pulse polarography and chronoamperometry. The three tervalent lanthanides can be reduced reversibly and solutions of divalent oxidation states are stable. E_1/2 potentials measured with respect to an Al electrode in a saturated melt are located respectively at 2.295 V (Eu), 1.630 V (Yb) and 1.080 V (Sm). In acidic chloroaluminates, the three investigated lanthanides are more oxidizing than in other more complexing solvents. If the acidity of the melt is decreased, precipitation of the trichloride (or the dichloride) occurs and the solubility product of the different species is directly related to the cationic size.