Studies on the extraction and separation of lanthanide ions with a synergistic extraction system combined with 1,4,10,13-tetrathia-7,16-diazacyclooctadecane and lauric acid

Abstract

1,4,10,13-Tetrathia-7,16-diazacyclooctadecane (ATCO) and its binary extraction system containing lauric acid were studied extensively as extractants of lanthanide (M 3+=La 3+, Ce 3+, Pr 3+, Nd 3+, Sm 3+, Eu 3+ and Gd 3+) in 1,2-dichloroethane solution. The percentage extraction of Ce 3+ and Eu 3+ by ATCO were only measured to be less than 5% during a pH range 5.5–7.0 in NCS −, ClO 4 − and PF 6 − mediums respectively, which indicates that ATCO alone has very low extractability to lanthanide, due to the bad fit of metal ions in its cavity. However, when lauric acid was added to the ATCO organic phase, because of forming rare earth adduct, the percentage extraction for lanthanide until Gd 3+ was enhanced in the binary system in comparison with that did not adopt the lauric acid within the pH range 6–7. The extraction species and extraction equilibrium constants log K ex were found to be CeLA 3⋅3HA, −8.5, EuLA 3⋅HA, −6.7, and GdLA 2NO 3⋅2HA, −1.8, respectively. The separation factor between Eu 3+ and Ce 3+ was found to be 2.5, however, poor selectivity for lanthanide was observed. From Gd 3+ to Er 3+ and Lu 3+, the synergistic effect of the binary extraction system decreases with increasing atomic number. For gadolinium, the synergistic effect becomes much weaker than that of Ce 3+ and Eu 3+, no synergistic effect existed for erbium and lutetium. Thermodynamic data for synergistic solvent extraction are also reported in this paper. The order of organic phase stability constants of the extraction species is Sm (5.8)>Pr (5.7)>Eu (5.6)>Ce (5.3)>La (5.2)>Gd (2.8).