Revised Pourbaix diagrams for the vanadium – water system

  • Igor Povar Joint Institute for Nuclear Research, Joliot-Curie Str., 6, 141980, Dubna, Russia; Institute of Chemistry of the Academy of Sciences of Moldova, 3 Academiei str., MD 2028, Chisinau, Republic of Moldova.
  • Oxana Spinu Institute of Chemistry of the Academy of Sciences of Moldova, 3 Academiei str., MD 2028, Chisinau
  • Inga Zinicovscaia Joint Institute for Nuclear Research, Joliot-Curie Str., 6, 141980, Dubna, Russia; Institute of Chemistry of the Academy of Sciences of Moldova, 3 Academiei str., MD 2028, Chisinau, Republic of Moldova and Horia Hulubei National Institute for R&D in Physics and Nuclear Engineering, 30 Reactorului Str. MG-6, Bucharest - Magurele, Romania.
  • Boris Pintilie Institute of Chemistry of the Academy of Sciences of Moldova, 3 Academiei str., MD 2028, Chisinau
  • Stefano Ubaldini Institute of Environmental Geology and Geoengineering of the Italian National Research Council, Rome
Keywords: Potential-pH diagrams, thermodynamic analysis, thermodynamic stability, vanadium species

Abstract

The forms of occurrence of vanadium metal are determined by the major chemical reactions in the aquatic environment such as hydrolysis, oxidation, reduction, and precipitation. Depending on pH, potential and total concentration of inorganic ions and organic ligands, vanadium compounds may undergo various transformations to produce a whole range of chemical forms in aqueous systems. In this paper, a novel approach has been applied for calculating potential-pH (Pourbaix) diagrams, based on the developed thermodynamic analysis of chemical equilibria in the V–H2O system. On the basis of currently revised thermodynamic data for V(III), V(IV) and V(V) hydrolysis and original thermodynamic and graphical approach used, the repartition of their soluble and insoluble chemical species has been investigated. By means of ΔG–pH diagrams, the areas of thermodynamic stability of V(IV) and V(V) hydroxides have been established for a number of analytical concentrations of vanadium in heterogeneous mixtures. The obtained results, based on the thermodynamic analysis and graphic design of calculated data, are in good agreement with available experimental data.

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Published
28-02-2019
Section
Electrochemical Science