Charge Transfer Kinetics of the Ti(IV)/Ti(III) Redox Couple in the Cesium Chloride-Cesium Fluoride Melt with Addition of Alkaline Earth Metal Cations

Abstract

The electrochemical behavior of the Ti(IV)/Ti(III) redox couple in the CsCl-CsF(10 wt%)-K2TiF6 melt was studied by cyclic voltammetry. The diffusion coefficients of the Ti(IV) complexes were calculated using the Randles-Sevcik equation. The standard rate constants of charge transfer for the Ti(IV)/Ti(III) redox couple in the CsCl-CsF(10 wt%)-K2TiF6 melt without and with additions of alkaline Earth metal cations (Mg2+, Ca2+, Sr2+, Ba2+) were determined. It was found that the rate constants of charge transfer increase with increasing ionic potential of the addition, reaching a maximum value for complexes with outer-sphere cations of magnesium, and this dependence is rectilinear. The activation energies of the charge transfer process in melts with additions of alkaline Earth metal cations were calculated and these values are significantly lower than the activation energy of the initial system CsCl-CsF(10 wt%)-K2TiF6. The kinetic parameters of the Ti(IV)/Ti(III) redox couple in chloride-fluoride melts with different second coordination sphere composition of the complexes were compared.