POLYCONDENSED ANIONS OF THE TRANSITION METALS: LIGHT SCATTERING AND ULTRACENTRIFUGATION WITH SCHLIEREN AND INTERFERENCE OPTICS OF ALKALINE NIOBIUM (V) SOLUTIONS

Abstract

Alkaline aqueous niobium(V) solutions prepared by dissolving the salt K14Nb12O37•27H2O were studied by means of light scattering and by equilibrium ultracentrifugation by using both schlieren and interference optics. All three experimental methods indicate that the degree of polymerization of the polycondensed niobate anion is no less than 5 and probably has the value 6. The centrifugation data indicate that only one polycondensed species exists in the solutions. The effective charge of the niobate anion appears to be reduced appreciably by the binding of potassium ions to a value of no greater than −2. The behavior of the solutions is very similar to that observed previously with alkaline tantalum(V) solutions, and it appears very likely that the hexameric anion [HNb6O19]−7 found in niobate crystals also exists in aqueous solutions. The niobate is slightly protonated in comparison to the analogous tantalate. The stability of highly concentrated solutions containing this large polycondensed species is probably the result of the existence of a poly-ion with high symmetry which interacts only weakly with the solvent, water.