Thermodynamics of the complexing of uranyl ions with 1-phenyl-3-methyl-4-benzoylpyrazolone-5 in aqueous dioxane

The thermodynamics of the complexing between hexavalent U and 1-phenyl-3-methyl-4-benzoylpyrazolone-5 (PMBP) have been studied in 70 vol% aqueous—dioxane medium at 25 and 35±0.1°C following the Bjerrum—Calvin pH titration technique, as applied by Van Uitert and Haas. The ligand is mono-protonic. The refinement of results of formation constants has been accomplished by the method of least squares treatment after an algebraic transformation. The formation of 1:1, 1:2 and 1:3 complexes has been observed, the order of stability being log K₁ > log K₂ > log K₃. The stability invariably increases with an increase in temperature both in aqueous as well as aqueous dioxane media. The changes in ΔG⁰, ΔH⁰ and ΔS⁰ at 25 and 35°C for the overall equilibrium constants have also been evaluated. Uranyl complexes of PMBP are entropy stabilized, the values of enthalpy changes being positive. Other factors which affect chelate stability are briefly discussed.