EPR and UV/VIS spectroscopic investigations of VO2+ complexes and compounds formed in alkali pyrosulfates

The catalytically important molten salt-gas system M2S2O7-M2SO4-V2O5/SO2(g) (M = Na. K, Rb, Cs) has been investigated by X- and Q-band EPR spectroscopy. In order to obtain information about the V(IV) complex formation in the melts, samples rather dilute in V2O5 were quenched from the molten state at 450-460degreesC to 0degreesC. EPR spectra of the quenched samples were recorded on samples with alkali to vanadium (M/V) ratios 40, 80 and 160. The spectra show that two V(IV) complexes dominate in the melt regardless of the type of alkali metal ion. In systems with low activity of sulfate a paramagnetic V(IV) complex with g(parallel to) = 1.915, g(perpendicular to) = 1,978 and line widths 5-15 Gauss is observed. In systems saturated with M2SO4 the obtained EPR spectra show a paramagnetic complex with the g-tensors g(parallel to) = 1.930, g(perpendicular to) = 1.980 and line widths 20-60 Gauss. These results fit very well with the assumption that the species VO(SO4)(2)(2-) and SO42- are in equilibrium with VO(SO4)(3)(4-). It has also been shown for the system M2S2O7-M2SO4(sat)-V2O5/SO42-(g) that the line widths in the system increase with higher cation radius, and depend linearly on the volume fraction of the sample occupied by the cation. This indicates that spin-spin relaxation effects are the major contribution to line broadening. Combining information from UV/VIS and EPR spectra shows that the VO2+ unit in the molten salt solvent exhibits electronic properties close to aqueous solutions of V(IV).