Evidence of different stoichiometries for the limiting carbonate complexes of lanthanides(3)

Two stoichiometries have been proposed by different laboratories to interpret measurements on the limiting carbonate complexes of An3+ and Ln3+ cations. The study of the solubility of double carbonates (AlkLn(CO3)2,xH2O) in concentrated carbonate solutions at room temperature and high ionic strengths has shown that on the one hand the lightest lanthanides (La and Nd) form Ln(CO3)45- whereas the heaviest (Eu and Dy) form Ln(CO3)33- in the studied chemical conditions, and on the other hand, that the kinetics of precipitation of double carbonates depends on the alkali metal and the lanthanide ions. The existence of two stoichiometries for the limiting carbonate complexes was confirmed by capillary electrophoresis hyphenated to an inductively coupled plasma mass spectrometer (CE-ICP-MS), used to extend the study to the whole series of lanthanides (except Ce, Pm and Yb). Two behaviours have been put forward comparing the electrophoretic mobilities: La to Tb form Ln(CO3)45- while Dy to Lu form Ln(CO3)33-. Measurements by time resolved laser fluorescence spectroscopy (TRLFS) on Eu(III) indicate small variations of the geometry of Eu(CO3)33- complex, specially with Cs+. Although analogies are currently used among the 4f-block trivalent elements, different aqueous speciations are evidenced in concentrated carbonate solutions across the lanthanide series. (author)