Equilibrium constants phosphoric acid complexes

Inorganic phosphate ligands are important with respect to the behavior of actinides in the environment and as potential waste forms. There have been a number of experimental studies to determine the equilibrium constants in the actinide-phosphoric acid system, but they have been complicated by the formation of relatively insoluble solid phases and the formation of ternary actinide complexes in solution. 

The application of standard electrode potential data to many systems of interest in analytical chemistry is further complicated by association, dissociation, complex formation, and solvolysis equilibria involving the species that appear in the Nemst equation. These phenomena can be taken into account only if their existence is known and appropriate equilibrium constants are available. More often than not, neither of these requirements is met and significant discrepancies arise as a consequence. For example, the presence of 1 M hydrochloric acid in the iron(Il)/iron(llI) mixture we have just discussed leads to a measured potential of + 0.70 V in 1 M sulfuric acid, a potential of -I- 0.68 V is observed and in 2 M phosphoric acid, the potential is + 0.46 V. In each of these cases, the iron(II)/iron(III) activity ratio is larger because the complexes of iron(III) with chloride, sulfate, and phosphate ions are more stable than those of iron(II) thus, the ratio of the species concentrations, [Fe ]/[Fe ], in the Nemst equation is greater than unity and the measured potential is less than the standard potential. If fomnation constants for these complexes were available, it would be possible to make appropriate corrections. Unfortunately, such data are often not available, or, if they are, they are not very reliable. 

We now consider Fe hydrolysis. The hexaaquaflFerric cation[Fe(H20)e] is more acid than hexaaquaferrous cation [Fe(H20)g]. The equilibrium constant of hydrolysis is approximately one order lower than that in phosphoric acid, whereas the equilibrium constant of the hydrolysis of Fe " is approximately one order higher than that in boric add. During the hydrolysis the following essentially mononuclear complexes are produced [FeOH] ", [Fe(OH)2]" , [Fe(OH)3(aq)]° and [Fe(OH)4]. By other reactions a series of polynuclear complexes is formed, for example, [Fe2(OH)2], [Fe3(OH)4] , [Fe4(OH)g] , etc. (for simplicity, the coordinated water molecules are omitted). First, colloid hydroxo complexes are formed and finally there is a precipitate of hydrated ferric oxide which is in fact a mixture of different polynuclear complexes. The distribution of polynudear complexes depends not only on pH, but also on the initial concentration of iron. In diluted solutions of ferric salts a precipitate of hydrated Fe203 is separated only at a higher pH. The equilibrium between particular polynuclear complexes is established only very slowly. 

Aziz, A., Lyle, S. J., Equilibrium constants for aqneons fluoro complexes of scandium, yttrium, americium(III) and cnrium(III) by extraction into di-2-ethylhexyl phosphoric acid, J. Inorg. Nucl. Chem., 31, (1969), 3471-3480. Cited on page 599. 

---