Electronic absorption spectra of niobium species in halide melts

Abstract

The results of spectroscopic studies of Nb anodic dissolution, dissolution of NbCl5 and reaction of various niobium oxides with HCl in different chloride melts at 450-750°C are presented. Nb(III) species, NbCl6 3-, is the major product of niobium anodic dissolution at current densities up to 40 mA/cm2. Addition of NbCl5 to alkali chloride melts predominantly leads to the formation of Nb(V) species, NbCl6 -. Upon increasing Nb(V) concentration NbCl6 - tend to decompose to Nb(IV) and Cl2. Reaction of NbO and NbO 2 with HCl proceeds via an intermediate oxygen-containing Nb(IV) complexes. Oxygen-free Nb(IV) ions, NbCl6 2-, were obtained by exchange reactions between metallic niobium and melts containing Bi(III), Ag(I) or Ni(II) chloro-ions. Electroreduction of Nb(III) on a tungsten working electrode below -1.45 V vs. Cl2/Cl-led to the formation of metallic niobium, no evidence of intermediate reduction products was obtained. Copyright © 2012 by The Electrochemical Society.