Electrochemical Behavior of Niobium and Titanium Complexes in Chloride-Fluoride Melts with Addition of Alkaline Earth Metal Cations

Abstract

The standard rate constants of charge transfer (k s) for the Nb(V)/Nb(IV) redox couple in the NaCl-KCl(equimol.)-NaF(10 wt%)-K2NbF7 melt with addition of alkaline Earth metal cations (Mg2+, Ca2+, Sr2+, Ba2+) were determined. It was found that addition of alkaline Earth metal cations resulted in increasing of k s to the certain ratio of Me2+/Nb(V) for the all alkaline Earth metal cations due to substitution of Na+ and K+ cations by Me2+ in the second coordination sphere of niobium complexes that leads to decreasing of niobium fluoride complexes stability. Further addition brought to some decrease of the standard rate constants because the viscosity of melts increasing, which brings to decrease of the diffusion coefficients. The standard rate constants increase with increasing of the ionic potential and reach maximum values for the complexes with outer-sphere magnesium cations. Comparative analysis of the electrochemical behavior of Nb(V)/Nb(IV) and Ti(IV/Ti(III)) redox couples in the NaCl-KCl(equimol.)-NaF(10 wt%) melt without and with addition of alkaline Earth metal cations has been done. It was determined that mechanism of electron transfer from the cathode to niobium and titanium complexes in melts containing alkaline Earth metal cations is the same and has a bridge nature.