The electrophoretic mobilities (mu ep,Ln) of twelve lanthanides (not Ce, Pr and Yb) were measured by CE-ICP-MS in 0.15 and 0.5 mol L(-1) Alk2 CO3 aqueous solutions for Alk+ = Li+, Na+, K+ and Cs+. In 0.5 mol L(-1) solutions, two different mu ep,Ln values were found for the light (La to Nd) and the heavy (Dy to Tm) lanthanides, which suggests two different stoichiometries for the carbonate limiting complexes. These results are consistent with a solubility study that attests the Ln(CO3)3(3-) and Ln(CO3)4(5-) stoichiometries for the heavy (small) and the light (big) lanthanides, respectively. The Alk+ counterions influence the mu ep,Ln Alk2 CO3 values, but not the overall shape of the mu ep,Ln Alk2 CO3 plots as a function of the lanthanide atomic numbers: the counterions do not modify the stoichiometries of the inner sphere complexes. The influence of the Alk+ counterions decreases in the Li+ > Na+ >> K+ > Cs+ series. The K3,Ln stepwise formation constants of the Ln(CO3)3(3-) complexes slightly increase with the atomic numbers of the lanthanides while K4,Ln, the stepwise formation constants of Ln(CO3)4(5-) complexes, slightly decrease from La to Tb, and is no longer measurable for heavier lanthanides.
Ca(2+) complexation by both sulfate and selenate ligands was studied by CE. The species were observed to give a unique retention peak as a result of a fast equilibrium between the free ions and the complexes. The change in the corresponding retention time was interpreted with respect to the equilibrium constant of the complexation reaction. The results confirmed the formation of CaSO(4)(aq) and CaSeO(4)(aq) under our experimental conditions. The formation data were derived from the series of measurements carried out at about 15, 25, 35, 45 and 55 degrees C in 0.1 mol/L NaNO(3) ionic strength solutions, and in 0.5 and 1.0 mol/L NaNO(3) ionic strength solutions at 25 degrees C. Using a constant enthalpy of reaction enabled to fit all the experimental data in a 0.1 mol/L medium, leading to the thermodynamic parameters: Delta(r)G(0.1M)(25 degrees C)=-(7.59+/-0.23) kJ/mol, Delta(r)H(0.1 M)=5.57+/-0.80 kJ/mol, and Delta(r)S(0.1 M)(25 degrees C)=44.0+/-3.0 J mol(-1) K(-1) for CaSO(4)(aq) and Delta(r)G(0.1 M)(25 degrees C)=-(6.66+/-0.23) kJ/mol, Delta(r)H(0.1 M)=6.45+/-0.73 kJ/mol, and Delta(r)S(0.1 M)(25 degrees C)=44.0+/-3.0 J mol(-1) K(-1) for CaSeO(4)(aq). Both formation reactions were found to be endothermic and entropy driven. CaSO(4)(aq) appears to be more stable than CaSeO(4)(aq) by 0.93 kJ/mol under these experimental conditions, which correlates with the difference of acidity of the anions as expected for interactions between hard acids and hard bases according to the hard and soft acids and bases theory. The effect of the ionic medium on the formation constants was successfully treated using the Specific ion Interaction Theory, leading to significantly different binary coefficients epsilon(NA+,SO(2-)(4)) = -(0.15 +/- 0.06) mol/kg-1 and epsilon(NA+,SO(2-)(4)) = -(0.26 +/- 0.10) mol/kg-1.
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