Hydration counteracts the separation of lanthanides by solvent extraction

The extraction of lanthanides from aqueous nitrate solutions by quaternary ammonium nitrate ionic liquids (e.g., [A336][NO(3)]) shows a negative sequence (i.e., light lanthanides are more efficiently extracted than heavy lanthanides), which conflicts with the lanthanide contraction. In this study, we explored the origin of the negative sequence by investigating the extraction of lanthanides from ethylammonium nitrate by [A336][NO(3)]. The extraction shows a positive sequence, which is converted to a negative sequence with the addition of water. The transformation from positive to negative sequences reveals that the negative sequence is caused by the hydration of lanthanide ions: hydration of lanthanide ions counteracts the extraction. Therefore, the use of solvents that have weak solvation with lanthanide ions might enhance the separation of the elements by solvent extraction.