Context (archaeology)

Salt water

Catalysis

Separation (statistics)

Phase (matter)

Salt (chemistry)

Liquid liquid

Engineering

Chemical physics

Biology

Geotechnical engineering

Chromatography

Computer science

Ternary operation

Paleontology

Thermodynamics

Physics

Extraction (chemistry)

Organic chemistry

Salting out

Liquid–liquid extraction

Liquid water

Aqueous solution

Phase diagram

Chemistry

Programming language

Ionic liquid

Acetonitrile

Machine learning

Liquid phase

Journal of the American Chemical Society

Salt-induced liquid–liquid phase separation in liquid mixtures is a common phenomenon in nature and in various applications, such as in separation and extraction of chemicals. Here, we present results of a systematic investigation of the phase behaviors in water–acetonitrile–salt mixtures using a combination of experiment and theory. We obtain complete ternary phase diagrams for nine representative salts in water–acetonitrile mixtures by cloud point and component analysis. We construct a thermodynamic free energy model by accounting for the nonideal mixing of the liquids, ion hydration, electrostatic interactions, and Born energy. Our theory yields phase diagrams in good agreement with the experimental data. By comparing the contributions due to the electrostatic interaction, Born energy, and hydration, we find that hydration is the main driving force for the liquid–liquid separation and is a major contributor to the specific ion effects. Our theory highlights the important role of entropy in the hydration driving force. We discuss the implications of our findings in the context of salting-out assisted liquid–liquid extraction and make suggestions for selecting salt ions to optimize the separation performance.

Salt-Induced Liquid–Liquid Phase Separation: Combined Experimental and Theoretical Investigation of Water–Acetonitrile–Salt Mixtures