Optimization of ion-pairing HPLC method for mutual separation of rare earth elements: unveiling the “diad-effect” appraisal utilizing periodic variations in their properties

Abstract

A new ion-pairing HPLC method has been developed for the analytical separation of rare earth elements (REEs), utilizing the unique “diad-effect” of the lanthanides. A chemometric approach was used to optimize the separation process, examining the impact of mobile phase pH and ion-pairing reagent concentration on resolution and elution time. A triple gradient elution program was proposed, involving changes in the pH of the mobile phase from 3.5 to 4.5, the ion-pairing reagent concentration from 25 mM to 0.05 M, and the mobile phase complexing additive (hydroxyisobutyric acid) concentration from 0.05 M to 0.5 M. With the proposed method, all REEs, including pairs that are typically difficult to separate (Pr–Nd, Eu–Gd, and Dy–Y), were effectively separated in less than eight minutes. The method validation conducted following ICH guidelines showed accurate results, with an accuracy of 99–108% across a concentration range of 50–150% of the target concentration for REEs. It also exhibited good linearity (0.9998–0.9992) across a concentration range of 5–15 µg/mL for REEs and a detection limit of 0.27–0.98 µg/mL for the various species. The proposed HPLC method proved reliable and successfully separated a commercial sample of yttrium-group oxides.