The complexation between uranium() and acetate in 1.05 mol kg Ϫ1 NaClO 4 was studied at variable temperatures (25, 35, 45, 55 and 70 ЊC). The formation constants of three successive complexes, UO 2 (OOCCH 3 ) ϩ , UO 2 (OOCCH 3 ) 2 and UO 2 (OOCCH 3 ) 3 Ϫ , and the molar enthalpies of complexation were determined by potentiometry and calorimetry. Extended X-ray Absorption Fine Structure Spectroscopy (EXAFS) provided structural information to identify the coordination modes of the acetate in the complexes in solution, which helped to interpret the trends in the enthalpy and entropy of the complexation. The effect of temperature on the stability of the complexes is discussed in terms of the electrostatic model.

The hydrolysis of uranium(VI) in tetraethylammonium perchlorate (0.10 mol dm(-3) at 25 degrees C) was studied at variable temperatures (10-85 degrees C). The hydrolysis constants (*beta(n,m)) and enthalpy of hydrolysis (Delta H(n,m)) for the reaction mUO(2)(2+) + nH(2)O = (UO(2))(m)(OH)(n)((2m-n))+) + nH(+) were determined by titration potentiometry and calorimetry. The hydrolysis constants, *beta(1,1), *beta(2,2), and *beta(5,3), increased by 2-5 orders of magnitude as the temperature was increased from 10 to 85 degrees C. The enthalpies of hydrolysis, Delta H(2,2) and Delta H(5,3), also varied: Delta H(2,2) became more endothermic while Delta H(5,3) became less endothermic as the temperature was increased. The heat capacities of hydrolysis, Delta C(p(2,2)) and Delta C(p(5,3)), were calculated to be (152 +/- 43) J K(-1) mol(-1) and -(229 +/- 34) J K(-1) mol(-1), respectively. UV/Vis absorption spectra supported the trend that hydrolysis of U(VI) was enhanced at elevated temperatures. Time-resolved laser-induced fluorescence spectroscopy provided additional information on the hydrolyzed species at different temperatures. Approximation approaches to predict the effect of temperature were tested with the data from this study.

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