Investigation on the electrochemical behavior of neodymium chloride at W, Al and Cd electrodes in molten LiCl-KCl eutectic

Electrochemical behavior of neodymium (III) ion was studied in LiCl-KCl eutectic melt in the temperature range 723-798 K on inert tungsten electrode using various transient electrochemical techniques such as cyclic voltammetry, convolution voltammetry, chronopotentiometry and square wave voltammetry. The reduction of Nd(III) ion to Nd metal on tungsten electrode takes place in two steps- Nd(III)/Nd(II) and Nd(II)/Nd(0). The diffusion coefficient of Nd(III) and Nd (II) ions were determined. Reduction of Nd(III) to Nd(II) showed reversible electrode behavior and that for Nd(II) to Nd metal followed the quasi-reversible behavior. Heterogeneous rate constant for the reduction, Nd(II)/Nd(0) was estimated from the convoluted voltammograms. The apparent standard electrode potentials,ENd(III)/Nd(II)*, ENd(II)/Nd(0)* and ENd(III)/Nd(0)* were estimated from the cyclic voltammograms. The electrode behavior of Nd(III) ion on solid aluminium electrode and liquid cadmium electrode was studied by cyclic voltammetry. Under-potential reduction of Nd(III) ion takes place on Al and Cd cathodes in a single step with three electron transfer. The apparent standard electrode potentials, ENd(III)/Nd(Al)* and ENd(III)/Nd(Cd)* were estimated for different temperatures in the range 698-773 K. The formation of intermetallics, Al11Nd3 and Cd11Nd were studied from open circuit potential measurement on Al and Cd film electrode respectively. The Gibbs energy of formation for these intermetallics was evaluated. The activity of neodymium in Al/Cd, the excess Gibbs energy and the activity coefficient of neodymium in Al/Cd were estimated from the open circuit potential measurement. SEM-EDX analysis and the XRD pattern of the electro-deposit revealed the formation of Al11Nd3 and Cd11Nd on Al and Cd cathodes respectively.