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Extracted Water Induces Concentration Fluctuations in Model Ternary Liquid-Liquid Extraction System
Brittany L Bonnett1, Pubudu N Wimalasiri1, Dina Sheyfer2
1Chemical Sciences and Engineering Division, Argonne National Laboratory, Lemont, Illinois 60439, United States.
The Journal of Physical Chemistry. B
|July 30, 2025
Summary
Water extraction enhances organic phase aggregation in liquid-liquid extraction by increasing spinodal temperature. This impacts metal ion separation by promoting concentration fluctuations and structure formation.
Area of Science:
- Chemical Engineering
- Materials Science
Background:
- Organic phase aggregation and phase splitting are crucial in metal ion liquid-liquid extraction.
- Previous work linked structure in binary mixtures to concentration fluctuations and third-phase formation.
- Understanding how aqueous components influence these fluctuations in complex systems is key.
Purpose of the Study:
- Investigate organic phase structural changes upon water contact in a ternary system.
- Determine the effect of extracted water on concentration fluctuations and phase behavior.
- Elucidate the mechanism of solute-induced aggregation in liquid-liquid extraction.
Main Methods:
- Small-angle X-ray scattering (SAXS) for structural analysis.
- Molecular dynamics (MD) simulations for molecular-level insights.
- Temperature variation studies to determine critical exponents.
Main Results:
- Critical exponents were consistent with mean-field theory.
- Increased water content linearly correlated with increased spinodal temperature.
- Different linear alkane diluents showed similar relationships between water concentration and spinodal temperature.
Conclusions:
- Water extraction enhances organic phase concentration fluctuations by forming polar extractant-water complexes.
- This increases the spinodal temperature, effectively reducing the distance to phase instability.
- The findings explain solute-induced aggregation and may apply to complex systems with high acid/metal loading.
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