CaltechAUTHORS
  A Caltech Library Service

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

Li, Minglun and Zhuang, Bilin and Lu, Yuyuan and An, Lijia and Wang, Zhen-Gang (2021) Salt-Induced Liquid–Liquid Phase Separation: Combined Experimental and Theoretical Investigation of Water–Acetonitrile–Salt Mixtures. Journal of the American Chemical Society, 143 (2). pp. 773-784. ISSN 0002-7863. https://resolver.caltech.edu/CaltechAUTHORS:20210114-164619058

[img] PDF (Experimental methods, thermodynamics of the water–acetonitrile–salt system) - Supplemental Material
See Usage Policy.

1044Kb

Use this Persistent URL to link to this item: https://resolver.caltech.edu/CaltechAUTHORS:20210114-164619058

Abstract

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.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1021/jacs.0c09420DOIArticle
ORCID:
AuthorORCID
Li, Minglun0000-0002-1286-6915
Zhuang, Bilin0000-0003-2934-4264
Lu, Yuyuan0000-0002-4073-678X
Wang, Zhen-Gang0000-0002-3361-6114
Additional Information:© 2021 American Chemical Society. Received 1 September 2020. Published online 8 January 2021. Y.L. and L.A. acknowledge the National Natural Science Foundation of China (Grant Nos. 21790340 and 21674113) and the Programs of Chinese Academy of Sciences (Grant No. QYZDY-SSW-SLH027) for financial support. Y.L. also acknowledges the Key Science and Technology Project of Jilin Province (Grant No. 20200504001YY) for financial support. We thank Dr. Pengfei Zhang (Donghua University) for helpful discussions, and we thank the anonymous reviewers whose comments have helped improve the presentation of our work. Author Contributions. M.L. and B.Z. contributed equally to this work. The authors declare no competing financial interest.
Funders:
Funding AgencyGrant Number
National Natural Science Foundation of China21790340
National Natural Science Foundation of China21674113
Chinese Academy of SciencesQYZDY-SSW-SLH027
Key Science and Technology Project of Jilin Province20200504001YY
Subject Keywords:Salts, Free energy, Ions, Mixtures, Hydration
Issue or Number:2
Record Number:CaltechAUTHORS:20210114-164619058
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20210114-164619058
Official Citation:Salt-Induced Liquid–Liquid Phase Separation: Combined Experimental and Theoretical Investigation of Water–Acetonitrile–Salt Mixtures. Minglun Li, Bilin Zhuang, Yuyuan Lu, Lijia An, and Zhen-Gang Wang. Journal of the American Chemical Society 2021 143 (2), 773-784; DOI: 10.1021/jacs.0c09420
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:107494
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:15 Jan 2021 15:26
Last Modified:26 Jan 2021 17:45

Repository Staff Only: item control page