RESUMO
The carbonate complexation of curium(III) in aqueous solutions with high ionic strength was investigated below solubility limits in the 10-70 degrees C temperature range using time-resolved laser-induced fluorescence spectroscopy (TRLFS). The equilibrium constant, K(3), for the Cm(CO(3))(2-) + CO(3)(2-) right harpoon over left harpoon Cm(CO(3))(3)(3-) reaction was determined (log K(3) = 2.01 +/- 0.05 at 25 degrees C, I = 3 M (NaClO(4))) and compared to scattered previously published values. The log K(3) value for Cm(III) was found to increase linearly with 1/T, reflecting a negligible temperature influence on the corresponding molar enthalpy change, Delta(r)H(3) = 12.2 +/- 4.4 kJ mol(-1), and molar entropy change, Delta(r)S(3) = 79 +/- 16 J mol(-1) K(-1). These values were extrapolated to I = 0 with the SIT formula (Delta(r)H(3) degrees = 9.4 +/- 4.8 kJ mol(-1), Delta(r)S(3) degrees = 48 +/- 23 J mol(-1) K(-1), log K(3) degrees = 0.88 +/- 0.05 at 25 degrees C). Virtually the same values were obtained from the solubility data for the analogous Am(III) complexes, which were reinterpreted considering the transformation of the solubility-controlling solid. The reaction studied was found to be driven by the entropy. This was interpreted as a result of hydration changes. As expected, excess energy changes of the reaction showed that the ionic strength had a greater influence on Delta(r)S(3) than it did on Delta(r)H(3).
