Tracking Molecular Transport Across Oil/Aqueous Interfaces: Insight into “Antagonistic” Binding in Solvent Extraction

Premadasa, Uvinduni I.; Bocharova, Vera; Lin, Lu; Genix, Anne-Caroline; Heller, William T.; Sacci, Robert L.; Ma, Ying-Zhong; Thiele, Nikki A.; Doughty, Benjamin L.

doi:10.1021/acs.jpcb.3c00386

Tracking Molecular Transport Across Oil/Aqueous Interfaces: Insight into “Antagonistic” Binding in Solvent Extraction

Journal Article · Mon May 22 00:00:00 EDT 2023 · Journal of Physical Chemistry. B

DOI:https://doi.org/10.1021/acs.jpcb.3c00386· OSTI ID:1976036

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Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division
Centre National de la Recherche Scientifique (CNRS), Montpellier (France)
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Neutron Scattering Division

Liquid/liquid (L/L) interfaces play a key, yet poorly understood, role in a range of complex chemical phenomena where time-evolving interfacial structures and transient supramolecular assemblies act as gatekeepers to function. Here, for this study, we employ surface-specific vibrational sum frequency generation combined with neutron and X-ray scattering methods to track the transport of dioctyl phosphoric acid (DOP) and di-(2-ethylhexyl) phosphoric acid (DEHPA) ligands used in solvent extraction at buried oil/aqueous interfaces away from equilibrium. Our results show evidence for a dynamic interfacial restructuring at low ligand concentrations in contrast to expectation. These time-varying interfaces arise from the transport of sparingly soluble interfacial ligands into the neighboring aqueous phase. These results support a proposed “antagonistic” role of ligand complexation in the aqueous phase that could serve as a holdback mechanism in kinetic liquid extractions. These findings provide new insights into interfacially controlled chemical transport at L/L interfaces and how these interfaces vary chemically, structurally, and temporally in a concentration-dependent manner and present potential avenues to design selective kinetic separations.

View Accepted Manuscript (DOE)

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Laboratory Directed Research and Development (LDRD) Program; USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1976036

Journal Information:: Journal of Physical Chemistry. B, Journal Name: Journal of Physical Chemistry. B Journal Issue: 21 Vol. 127; ISSN 1520-6106

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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nonlinear optics

Tracking Molecular Transport Across Oil/Aqueous Interfaces: Insight into “Antagonistic” Binding in Solvent Extraction

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