Organophosphorus compounds, such as di(2-ethylhexyl)phosphoric acid (DEHPA), are widely employed for the extracting separation of lanthanoid elements. Although these compounds indicate better selectivity for the mutual separation of lanthanoid elements, multistage extraction processes are required for the precise separation of adjacent elements.Various chromatographic techniques have been developed by employing these compounds as stationary phases. 1-9 Extraction chromatography using support materials loaded with extracting agents as a stationary phase has been widely investigated for the separation of inorganic substances. 1 Organophosphorus extracting reagents, such as DEHPA, 2 tributhylphosphate (TBP), 3 and 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester (EHPA), 4 were applied to extraction chromatography for the separation of lanthanoid elements. Liquid-liquid partition chromatography employing support-free stationary phase, e.g., centrifugal partition chromatography 5,6 and countercurrent chromatography, 7-9 was employed for the mutual separation of lanthanoids with the aid of the DEHPA and EHPA stationary phases.The separation of lanthanoid elements has been achieved by ion-exchange chromatography in the presence of appropriate complexing agents, such as α-hydroxyisobutyric acid in the mobile phase, to enhance the separation selectivity. 10,11 Reversed-phase packed-beds having high performance and high capacity were dynamically modified with alkylsulfonates added to a mobile phase; the stationary phase then acted as a cation exchanger. 12 This "dynamic ion exchanger" gave excellent efficiency and was utilized for lanthanoid separation. 13 In this study, an acidic organophosphorus compound has been applied to reversed-phase high-performance liquid chromatography (RP-HPLC). The reversed-phase stationary phase was dynamically modified with EHPA by flowing the mobile phase of an acetone-water mixture containing the extracting reagent. A preparative modification of the stationary phase is readily available based on the partition of the reagent. This method has greater flexibility for choosing the separation conditions. The chromatographic separation of the trivalent lanthanoid ions was investigated, and the chromatographic retention behavior was compared with liquid-liquid extraction.
Experimental
ApparatusThe HPLC setup consisted of a Model 880-PU pump unit (JASCO Co.), a Rheodyne Model 7125 sample injection valve with a 0.1 cm 3 loop, and an ion chromatographic system (TOSOH Co.) including a Model UV-8010 spectrophotometer, a Model CD-8010 column oven, and a Model CCPM pump unit for a postcolumn reagent solution. A commercial packed column, TSKgel ODS-80TM CTR (TOSOH Co.), was used for the analytical column.
Reagents2-Ethylhexylphosphonic acid 2-ethylhexyl ester (EHPA) was obtained from Daihachi Chemical Ind. Co. Ltd., and purified as described previously.5 Arsenazo III (Dojindo Lab.) was used as a postcolumn reagent for the spectrophotometric detection of lanthanoids. Katahira, Aoba, Japan An acidic...