On the Hydrolysis of Tetravalent Metal Ions

Abstract

ABSTRACTThe stability constants of the hydroxide complexes of zirconium(IV) and uranium(IV) have been measured at 15, 25 and 35°C [in 1.0 mol dm−3 (Na, H)ClO4] using potentiometry. For zirconium(IV), the results indicate the presence of Zr(OH)3+ and the polymeric species Zr3(OH)48+ and Zr4(OH)88+ whereas the results for uranium(IV) indicate the presence of U(OH)3+ and the polymeric species U4(OH)124+. The hydrolysis of both metal ions was studied at three temperatures allowing the determination of ΔH° and ΔS° of reaction for each species. The results were compared with previous results determined for thorium(IV) under the same experimental conditions to ascertain whether thorium should be used as an analogue for other tetravalent metal ions in safety assessment studies of nuclear repositories.