Effects of Electrolytes on Thermodynamics and Structure of Oligo(ethylene oxide)/Salt Solutions and Liquid–Liquid Equilibria of a Squalane/Tetraethylene Glycol Dimethyl Ether BlendClick to copy article linkArticle link copied!
- Zhengyuan ShenZhengyuan ShenDepartment of Chemical Engineering and Material Science, University of Minnesota, 421 Washington Avenue SE, Minneapolis, Minnesota 55455-0132, United StatesDepartment of Chemistry, University of Minnesota, 207 Pleasant Street SE, Minneapolis, Minnesota 55455-0431, United StatesChemical Theory Center, University of Minnesota, 207 Pleasant Street SE, Minneapolis, Minnesota 55455-0431, United StatesMore by Zhengyuan Shen
- Qile P. ChenQile P. ChenDepartment of Chemical Engineering and Material Science, University of Minnesota, 421 Washington Avenue SE, Minneapolis, Minnesota 55455-0132, United StatesDepartment of Chemistry, University of Minnesota, 207 Pleasant Street SE, Minneapolis, Minnesota 55455-0431, United StatesChemical Theory Center, University of Minnesota, 207 Pleasant Street SE, Minneapolis, Minnesota 55455-0431, United StatesMore by Qile P. Chen
- Shuyi XieShuyi XieDepartment of Chemistry, University of Minnesota, 207 Pleasant Street SE, Minneapolis, Minnesota 55455-0431, United StatesMore by Shuyi Xie
- Timothy P. Lodge*Timothy P. Lodge*Email: [email protected]Department of Chemical Engineering and Material Science, University of Minnesota, 421 Washington Avenue SE, Minneapolis, Minnesota 55455-0132, United StatesDepartment of Chemistry, University of Minnesota, 207 Pleasant Street SE, Minneapolis, Minnesota 55455-0431, United StatesMore by Timothy P. Lodge
- J. Ilja Siepmann*J. Ilja Siepmann*Email: [email protected]Department of Chemical Engineering and Material Science, University of Minnesota, 421 Washington Avenue SE, Minneapolis, Minnesota 55455-0132, United StatesDepartment of Chemistry, University of Minnesota, 207 Pleasant Street SE, Minneapolis, Minnesota 55455-0431, United StatesChemical Theory Center, University of Minnesota, 207 Pleasant Street SE, Minneapolis, Minnesota 55455-0431, United StatesMore by J. Ilja Siepmann
Abstract
Gibbs ensemble Monte Carlo simulations for salt-doped oligo(ethylene oxide) (OEO, Mw = 90–266 g/mol) solutions show that the presence of ions leads to significant increases in the cohesive energy density (ΠCED) and the enthalpy of vaporization for OEO chains but that compensation by entropic contributions leads to only small changes in the Gibbs free energy of transfer and vapor pressure. At the same relative ion concentration (r) and temperature, the ΠCED values of the salt-doped systems order as LiClO4 > LiF > CsClO4 ≈ CsF. Structural analysis indicates significant ion clustering in addition to coordination of cations by OEO chains. After accounting for ion clustering via the van’t Hoff factor, the solvent vapor pressures are well described by Raoult’s law. Experiments and simulations for a squalane/tetraethylene glycol dimethyl ether blend (xW,OEO = 0.65) show that the addition of LiClO4 does not significantly alter the miscibility gap below 0.95 TCP,free, the critical temperature of the salt-free blend. However, the coexistence curve for the LiClO4-doped system does not close with the usual power-law scaling at T > 0.95 TCP,free as transfer of OEO chains to the squalane-rich phase leads to an increase in r in the OEO-rich phase, which, in turn, makes it a less hospitable environment for squalane.
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This article is cited by 2 publications.
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, 6639-6648. https://doi.org/10.1021/acs.macromol.1c00995
- Evgenii O. Fetisov, Marcel D. Baer, J. Ilja Siepmann, Gregory K. Schenter, Shawn M. Kathmann, Christopher J. Mundy. The Statistical Mechanics of Solution-Phase Nucleation: CaCO$$_3$$ Revisited. 2021, 101-122. https://doi.org/10.1007/978-981-33-6639-8_5
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