Origins of Clustering of Metalate-Extractant Complexes in Liquid-Liquid Extraction.

Effective and energy-efficient separation of precious and rare metals is very important for a variety of advanced technologies. Liquid-liquid extraction (LLE) is a relatively less energy intensive separation technique, widely used in separation of lanthanides, actinides, and platinum group metals (PGMs). In LLE, the distribution of an ion between an aqueous phase and an organic phase is determined by enthalpic (coordination interactions) and entropic (fluid reorganization) contributions. The molecular scale details of these contributions are not well understood. Preferential extraction of an ion from the aqueous phase is usually correlated with the resulting fluid organization in the organic phase, as the longer-range organization increases with metal loading. However, it is difficult to determine the extent to which organic phase fluid organization causes, or is caused by, metal loading. In this study, we demonstrate that two systems with the same metal loading may impart very different organic phase organizations and investigate the underlying molecular scale mechanism. Small-angle X-ray scattering shows that the structure of a quaternary ammonium extractant solution in toluene is affected differently by the extraction of two metalates (octahedral PtCl62- and square-planar PdCl42-), although both are completely transferred into the organic phase. The aggregates formed by the metalate-extractant complexes (approximated as reverse micelles) exhibit a more long-range order (clustering) with PtCl62- compared to that with PdCl42-. Vibrational sum frequency generation spectroscopy and complementary atomistic molecular dynamics simulations on model Langmuir monolayers indicate that the two metalates affect the interfacial hydration structures differently. Furthermore, the interfacial hydration is correlated with water extraction into the organic phase. These results support a strong relationship between the organic phase organizational structure and the different local hydration present within the aggregates of metalate-extractant complexes, which is independent of metalate concentration.