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Like dissolves like: A first-principles theory for predicting liquid miscibility and mixture dielectric constant

Zhuang, Bilin and Ramanauskaite, Gabriele and Koa, Zhao Yuan and Wang, Zhen-Gang (2021) Like dissolves like: A first-principles theory for predicting liquid miscibility and mixture dielectric constant. Science Advances, 7 (7). Art. No. eabe7275. ISSN 2375-2548. PMCID PMC7880597.

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Liquid mixtures are ubiquitous. Miscibility and dielectric constant are fundamental properties that govern the applications of liquid mixtures. However, despite their importance, miscibility is usually predicted qualitatively based on the vaguely defined polarity of the liquids, and the dielectric constant of the mixture is modeled by introducing mixing rules. Here, we develop a first-principles theory for polar liquid mixtures using a statistical field approach, without resorting to mixing rules. With this theory, we obtain simple expressions for the mixture’s dielectric constant and free energy of mixing. The dielectric constant predicted by this theory agrees well with measured data for simple binary mixtures. On the basis of the derived free energy of mixing, we can construct a miscibility map in the parameter space of the dielectric constant and molar volume for each liquid. The predicted miscibility shows remarkable agreement with known data, thus providing a quantitative basis for the empirical “like-dissolves-like” rule.

Item Type:Article
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URLURL TypeDescription Materials CentralArticle
Zhuang, Bilin0000-0003-2934-4264
Wang, Zhen-Gang0000-0002-3361-6114
Additional Information:© 2021 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works. Distributed under a Creative Commons Attribution License 4.0 (CC BY). Submitted 11 September 2020; Accepted 24 December 2020; Published 12 February 2021. We thank D. Tirrell, I. Nakamura, R. Wang, K. Shen, P. Zhang, N. Alsaifi, and J. Jiang for helpful discussions throughout this work. We also thank the anonymous reviewers whose comments have helped to improve this work. Funding: This work was supported by the Yale-NUS College Start-Up Grant and the Yale-NUS College Summer Research Programme. Acknowledgement is also made to the donors of the American Chemical Society Petroleum Research Fund (53404-ND5) for partial support of this research. Author contributions: B.Z. and Z.-G.W. conceived the research. B.Z. formulated the theory. B.Z., G.R., and Z.Y.K. performed the numerical calculations and analyzed the data. B.Z. and Z.-G.W. wrote the manuscript. Competing interests: The authors declare that they have no competing interests. Data and materials availability: All data needed to evaluate the conclusions in the paper are present in the paper and/or the Supplementary Materials. Additional data related to this paper may be requested from the authors.
Funding AgencyGrant Number
American Chemical Society Petroleum Research Fund53404-ND5
Issue or Number:7
PubMed Central ID:PMC7880597
Record Number:CaltechAUTHORS:20210216-121335555
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Official Citation:B. Zhuang, G. Ramanauskaite, Z. Y. Koa, Z.-G. Wang, Like dissolves like: A firstprinciples theory for predicting liquid miscibility and mixture dielectric constant. Sci. Adv. 7, eabe7275 (2021).
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:108065
Deposited By: Tony Diaz
Deposited On:16 Feb 2021 21:44
Last Modified:24 Feb 2021 19:44

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