Studies on complexation and solvent extraction of lanthanides in the presence of diaza-18-crown-6-di-isopropionic acid.
Stability constants of some lanthanides with K22DAP (diaza-18-crown-6-diisopropionic acid) were determined by potentiometric titration method. The logarithmic values of these constants for La(III), Nd(III), Sm(III), Gd(III), Tb(III), Dy(III), Er(III), and Lu(III) are 11.14, 11.43, 11.78, 11.74, 11.95, 12.09, 11.49, and 10.88, respectively. Solvent extraction studies were carried out on the K22DAP complexes of La(III), Nd(III) and Lu(III) using TTA (thenoyltrifluoroacetone) as an extractant in different diluents. It appears that nitrobenzene, a diluent with high dielectric constant, favors the extraction of the complexes. Extraction rates of the K22DAP complexes of lanthanides were investigated at pH 5.5 and 8.0 with TTA in chloroform. The rates of extraction are found to be dependent upon the nature of the extracted species. Competitive extractions were carried out to see if selective extractions could be achieved.
Metal complex formation with 1,10-diaza-4,7,13,16-tetraoxacyclooctadecane-N,N'-diacetic acid: an approach to potential lanthanide ion selective reagents
The principles of designing lanthanide (Ln) ion selective macrocyclic reagents are discussed. Factors such as the size of the metal ion, the cavity size of the ligand, the stereochemical constraint imposed on the ligand, and the overall coordination number of the multidentate ligand are considered. On the basis of these principles, the macromonocyclic ligand 1,10-diaza-4,7,13,16-tetraoxacyclooctadecane-N,N'-diacetic acid (dacda) has been prepared and characterized. stability constants of dacda complexes of various metal ions are reported. Except for a few metal ions such as copper (II), lead (II), and cadmium (II), dacda shows unique selectivity toward lanthanide ions as a group. Also, for the first time in aqueous solution for a multidentate ligand, the stability constants for Ln-ligand complexes decrease with increasing atomic number for heavy lanthanides and remain roughly unchanged for the lighter lanthanides. These data are discussed, and the structures of the complexes are proposed. 3 figures, 1 table.
Acidic organophosphorus extractants—XVIII: The rate of lanthanide(III) extraction by di(2-ethylhexyl) phosphoric acid from complexing media
Abstract The rate of distribution was studied for the lanthanides(III) from La(III) to Eu(III) and of Y(III) between 0·3 M di(2-ethylhexyl) phosphoric acid + 0·2 M tributyl phosphate in n -dodecane and aqueous solutions of diethylenetriaminepentaacetic and lactic acids at pH 3. Both the forward and back extractions can be described as first order reactions. In extracting trace lanthanide(III) quantities the observed rate constant decreases with increasing atomic number from La to Eu. The effects of the temperature, transfer direction and the concentrations of some components of the system were also studied.