Infrared and Raman Spectroscopic Investigations of the Nb(V) Fluoro and Oxofluoro Complexes in the LiF−NaF−KF Eutectic Melt with Development of a Diamond IR Cell

A vacuum-tight cell for infrared spectroscopic investigations of extremely corrosive melts, e.g., molten fluorides, has been constructed and tested up to 750 °C. The cell has a gold-lined sample chamber and a diamond window transparent for the infrared light. It can be furnished with a gold piston that enables the recording of short-path-length FTIR spectra of liquid samples. Solutions of Nb(V) in LiF−NaF−KF eutectic (FLINAK) with and without oxide additions have been investigated by FTIR and Raman spectroscopy. The presence of NbF7 2-, NbOF5 2-, and NbO2F4 3- complexes was established in the molten state at 600 °C. After solidification NbF7 2- was still the only Nb(V) all-fluoro complex present. Three oxofluoro complexes, NbOF6 3-, NbOF5 2-, and NbO2F4 3-, have been identified in the solid state. Typical frequency regions for the different complexes are established. Finally, it was shown that K2NbF7 can be used as an indicator to determine the oxide content of the sample melts.