Abstract
The stoichiometry of the polyanions formed by the action of nitric acid on sodium tungstate (< 0.01M) has been studied by means of electrometric techniques involving pH-potentiometric and conductometric titrations. The well defined inflections and breaks in the titration curves provide evidence for the existence of the polyanions, para-W12O41(10-) and meta-W12O39(6-) corresponding to the ratio of H+:WO4(2-) as 7:6 and 9:6 in the pH ranges 5.7-6.0 and 3.6-4.1, respectively. The interaction of lanthanum nitrate with sodium tungstate solutions, at specific pH levels 8.0, 5.9 and 4.0 was also studied by pH and conductometric titrations, in aqueous and alcoholic media, with each of the reagents alternatively used as titrant. The electrometric experiments provide definite evidence of the formation of normal-La2O3.3WO3, para-5La2O3.36WO3 and meta-La2O3.12WO3 tungstates in the vicinity of pH 6.3, 5.0 and 4.2, respectively. Analytical investigations on the precipitates formed confirm the results of the electrometric study.
Highlights
In aqueous solutions molybdates, tungstates, vanadates, and to smaller extent, niobates, tantalates, and chromates, undergo complex hydrolysis-polymerization reactions upon acidification
There is no doubt that the formation of isopolytungstates on acidification of the solutions of normal tungstate, WO42, is the most complex and the least understood system [2]
A series of pH and conductometric titrations was performed by direct and reverse methods, i.e. when lanthanum nitrate solution from the microburette was added to sodium tungstate solution and vice versa (Table 2). 25.00 mL of ethanolic solution (20%) was taken in the cell, which was thermostated at 25.0±0.1oC
Summary
Tungstates, vanadates, and to smaller extent, niobates, tantalates, and chromates, undergo complex hydrolysis-polymerization reactions upon acidification. A series of pH and conductometric titrations was performed by direct and reverse methods, i.e. when lanthanum nitrate solution from the microburette was added to sodium tungstate solution and vice versa (Table 2).
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