The efficient separation of platinum group metals using centrifugal partition chromatography.
Committee ChairFreiser, Henry
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PublisherThe University of Arizona.
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AbstractCentrifugal Partition Chromatography (CPC) is a multistage liquid-liquid countercurrent distribution technique which utilizes rotating teflon cartridges to hold a liquid phase stationary while the other liquid phase is pumped at a constant flow rate. It has been demonstrated to be a valuable technique for the base line separations of families of metal ions such as the platinum group metals (PGM)--Pt, Pd, Rh and Ir. The separations of these metals as their anionic chloro complexes were achieved using the heptane-water phase pair with a stable and relatively inexpensive extractant trioctylphosphine oxide (TOPO) functioning as a ligand in its neutral form and as a cation in its protonated form. A striking feature of the chromatograms of the complexes and ion pairs were their much poorer efficiencies compared to the efficiency of an organic analyte like 3-picoline under identical distribution rations. The inefficiencies of the PGM separations were also a function of the concentrations of the aqueous and organic phase components. These inefficiencies could be attributed to slow kinetics of the back extraction of the complexes and ion pairs and could be used to derive the mechanisms of these slow chemical kinetic steps. A correlation was established for the Pd(II) system between the CPC inefficiencies and the half lives of the slow reactions measured independently by stopped flow in micelles. This correlation was utilized to derive the rate constants for the back extraction of the TOPO complexes and ion pairs of Pt and Ir. The mechanisms of the extraction reactions were derived using the principle of microscopic reversibility based on the mechanisms of the back extraction reactions. This was then used to obtain estimates for the rate constants for the extraction reactions as well. The PGM were thus separated and their equilibrium and kinetics (extraction and back extraction) completely characterized using CPC. This is a significant development with CPC because such complete equilibrium and kinetic characterizations are hard to achieve with conventional liquid chromatographic techniques.