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<p><span lang="EN-US">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</span><span lang="EN-US">-</span><span lang="EN-US">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.</span></p>