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Tracking Molecular Transport Across Oil/Aqueous Interfaces: Insight into "Antagonistic" Binding in Solvent
Uvinduni I Premadasa1, Vera Bocharova1, Lu Lin1
1Chemical Sciences Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, United States.
The Journal of Physical Chemistry. B
|May 22, 2023
Summary
Dynamic restructuring at liquid/liquid interfaces was observed, driven by ligand transport into the aqueous phase. This finding offers new insights into controlling kinetic separations in solvent extraction.
Area of Science:
- Physical Chemistry
- Chemical Engineering
- Materials Science
Background:
- Liquid/liquid (L/L) interfaces are crucial in chemical phenomena, but their structure and dynamics are poorly understood.
- Time-evolving interfacial structures and transient assemblies control function in complex chemical systems.
Purpose of the Study:
- To investigate the transport of specific ligands (dioctyl phosphoric acid and di-(2-ethylhexyl) phosphoric acid) at buried oil/aqueous interfaces.
- To understand dynamic interfacial restructuring and its impact on chemical transport away from equilibrium.
Main Methods:
- Surface-specific vibrational sum frequency generation spectroscopy.
- Neutron and X-ray scattering techniques.
- Analysis of ligand transport at oil/aqueous interfaces under non-equilibrium conditions.
Main Results:
- Observed dynamic interfacial restructuring at low ligand concentrations, contrary to expectations.
- Identified ligand transport into the aqueous phase as the cause of time-varying interfaces.
- Provided evidence for an "antagonistic" role of aqueous phase ligand complexation.
Conclusions:
- Interfacial structure at L/L interfaces is chemically, structurally, and temporally variable in a concentration-dependent manner.
- Aqueous phase complexation can act as a holdback mechanism in kinetic liquid extractions.
- Findings offer new avenues for designing selective kinetic separations.
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