INVESTIGATION OF THE MECHANISM OF CO-REDUCTION OF THE RARE-EARTH METAL IONS WITH NICKEL IONS IN AN EUTECTIC KCl–NaCl–CsCl MELT

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Abstract

In this work, the electrochemical behavior of dysprosium, neodymium, and lanthanum ions and their co-reduction with nickel ions on tungsten and nickel electrodes in the eutectic melt KCl–NaCl–CsCl at a temperature of 823 K have been studied. It was found that the electroreduction of Ln3+ ions proceed reversibly in one three electron stage up to the polarization rates of 0.2 V/s. At the combined content of lanthanide and nickel ions, the voltampere dependences show the reduction waves of nickel ions at potentials of –0.12… –0.3 V and of lanthanide ions at potentials of –2.13… –2.18 V relative to the chlorosilver reference electrode. Besides these waves on voltammetryograms there are three recovery waves in the region of potentials: –1.68… –1.77 V; –1.95… –2.0 V; –2.13… –2.18 V. The appearance of these waves is connected with the joint electroreduction of lanthanide and nickel ions on the metallic nickel previously separated on the tungsten electrode with a certain depolarization and formation of intermetallic phases of lanthanides and nickel of different composition LnxNiy. The chronopotentiograms of the open circuit revealed plateaus of potential delay corresponding to dissolution of separate phases of intermetallides. Electrolysis in potentiostatic condition at potentials –1.7… –2.1 V and at a certain ratio of concentrations of lanthanide and nickel chlorides the phases of intermetallic compounds LnNi5, Ln2Ni7, Ln2Ni3, LnNi3, LnNi2 were obtained. The synthesized samples of lanthanide and nickel intermetallides were characterized by X-ray phase analysis and scanning electron microscopy. The EMF values for LnxNiy intermetallic compounds in two-phase coexisting states at 823 K have been measured. The relative partial moles of the Gibbs free energy and activity of lanthanide in LnxNiy intermetallic compounds were calculated from the EDS values.

About the authors

Kh. B Kushkhova

Kabardino-Balkarian State University named after H. M. Berbekov

Email: fatya@mail.ru
Nalchik, Russia

A. A Khotov

Kabardino-Balkarian State University named after H. M. Berbekov

Email: fatya@mail.ru
Nalchik, Russia

Zh. Z Aliа

Kabardino-Balkarian State University named after H. M. Berbekov

Email: fatya@mail.ru
Nalchik, Russia

F. A Kishevaa

Kabardino-Balkarian State University named after H. M. Berbekov

Author for correspondence.
Email: fatya@mail.ru
Nalchik, Russia

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