Thermodynamic descriptors of sensible heat driven liquid-liquid phase separation

Sanadhya, Sidharth; Tucker, Zachary D.; Gulotty, Eva M.; Boggess, William G.; Ashfeld, Brandon L.; Moghaddam, Saeed

doi:10.1016/j.molliq.2022.119440

Cited by 7 publications

(4 citation statements)

References 28 publications

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“…The presented results indicate that above the LCST, DME molecules migrate extensively from the concentrated lower phase to the dilute upper phase with increasing temperature, resulting in an increase in the upper phase volume. Our findings echo previous studies about liquid–liquid miscibility gaps. ,− Different systems, such as protein solutions − and ionic liquids − have been investigated, and some of them have shown similar closed-loop behavior. ,, Yet, liquid–liquid phase separations in electrolyte solutions are considered unique, − constituting a subject of interest and an important topic for in-depth thermodynamic research.…”

Section: Discussionsupporting

confidence: 87%

“…38,44−48 Different systems, such as protein solutions 49−52 and ionic liquids 53−55 have been investigated, and some of them have shown similar closed-loop behavior. 39,56,57 Yet, liquid−liquid phase separations in electrolyte solutions are considered unique, 58−60 constituting a subject of interest and an important topic for in-depth thermodynamic research.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

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Understanding the Unique Thermodynamic Behavior of MgTFSI₂/DME Solutions. Part 1: Phase Diagram, Partial Volumes, and Densities

Holin,

Gofer,

Major

et al. 2023

J. Phys. Chem. C

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A unique thermodynamic behavior was observed for solutions of magnesium bis(trifluoromethanesulfonyl) imide in 1,2-dimethoxyethane (DME), highly promising solutions for rechargeable Mg batteries: between 287 and 373 K, the solution exists as two immiscible phases, each with a different salt concentration, volume, and density. These characteristics depend strongly on temperature. To study this dependence, a phase diagram was constructed. In addition, partial phase volumes and densities were measured as a function of temperature. We observed that the temperature–molar fraction phase diagram exhibits closed-loop behavior, which is circumscribed by 287 and 373 K, with 333 K as an inversion locus. Below 287 K, the solution exists as a single homogeneous phase. At 287 K and above, the solution separates into two immiscible phases: a concentrated and dense lower phase and a dilute upper phase. As the temperature increases to 333 K, the lower phase becomes more concentrated and denser, and its partial volume decreases. The reverse trends are observed for the upper phase. From 333 K and above, the trends reverse: the upper phase becomes more concentrated but its partial volume continues to grow at the expense of the lower phase, while the lower phase concentration decreases. At 373 K, the two phases merge into a single homogeneous phase.

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Section: Discussionsupporting

confidence: 87%

Section: ■ Experimental Sectionmentioning

confidence: 99%

Understanding the Unique Thermodynamic Behavior of MgTFSI₂/DME Solutions. Part 1: Phase Diagram, Partial Volumes, and Densities

Holin,

Gofer,

Major

et al. 2023

J. Phys. Chem. C

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“…Thus, higher temperatures are used to increase the solubility of reactants in ILs before a slow cooling process promotes crystallization. Furthermore, many ILs are now commercially available, and the vast range of cation–anion combinations allows for the design of task-specific ILs in order to identify those critical structure–function relationships between actinyl crystal growth and IL structure. ,, …”

Section: Introductionmentioning

confidence: 99%

“…Furthermore, many ILs are now commercially available, and the vast range of cation−anion combinations allows for the design of task-specific ILs in order to identify those critical structure−function relationships between actinyl crystal growth and IL structure. 11,13,14 Due to their ready availability, the ILs used to synthesize uranyl compounds are largely imidazolium based. Earlier studies have produced monomeric and dimeric structures built from uranyl ions, 15−21 chains and sheets, 19−29 isolated clusters, 20,30,31 and a few metal−organic frameworks.…”

Section: ■ Introductionmentioning

confidence: 99%

Utilizing Ionic Liquids as Bifunctional Reagents for the Ionothermal Synthesis of Uranyl Compounds

Felton,

Kohlgruber,

Tucker

et al. 2023

Crystal Growth & Design

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The extraction of actinides, specifically uranyl and other actinyl ions, from fission products is a critical aspect of spent nuclear fuel reprocessing. In this study, ionothermal syntheses were conducted to control the formation of uranyl (UO2)2+ salt complexes generated by exposure to a selection of ionic liquids (ILs). The high-thermal stability and ligation potential of ILs were exploited in a multifaceted approach toward uranyl salt complexation by enabling ligation of the IL anionic component while simultaneously providing polar reaction media to promote speciation. Furthermore, an evaluation of uranyl complex templating by the IL cation revealed that small, heterocyclic cationic molecules resulted in more densely packed anionic clusters. The uranium source was also varied to determine the oxidizing effect of nitrate on the ILs and the propensity for nitrate and acetate byproduct formation. Uranyl triflate was found to be the optimal uranium source for the production of pure uranyl complexes. The degree to which nitrate oxidizes the ILs was investigated to determine what oxidation products form and subsequently coordinate to the uranyl ion. Finally, it was shown that a uranyl succinate framework can be synthesized in high yield from an IL that contains succinate as the anion.

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Scaled water sigma potential as a descriptor of LCST and UCST behavior in aqueous ionic liquid solutions

Sanadhya,

Durling,

Ashfeld

et al. 2024

Journal of Ionic Liquids

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Thermodynamic descriptors of sensible heat driven liquid-liquid phase separation

Cited by 7 publications

References 28 publications

Understanding the Unique Thermodynamic Behavior of MgTFSI₂/DME Solutions. Part 1: Phase Diagram, Partial Volumes, and Densities

Understanding the Unique Thermodynamic Behavior of MgTFSI₂/DME Solutions. Part 1: Phase Diagram, Partial Volumes, and Densities

Utilizing Ionic Liquids as Bifunctional Reagents for the Ionothermal Synthesis of Uranyl Compounds

Scaled water sigma potential as a descriptor of LCST and UCST behavior in aqueous ionic liquid solutions

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Thermodynamic descriptors of sensible heat driven liquid-liquid phase separation

Cited by 7 publications

References 28 publications

Understanding the Unique Thermodynamic Behavior of MgTFSI2/DME Solutions. Part 1: Phase Diagram, Partial Volumes, and Densities

Understanding the Unique Thermodynamic Behavior of MgTFSI2/DME Solutions. Part 1: Phase Diagram, Partial Volumes, and Densities

Utilizing Ionic Liquids as Bifunctional Reagents for the Ionothermal Synthesis of Uranyl Compounds

Scaled water sigma potential as a descriptor of LCST and UCST behavior in aqueous ionic liquid solutions

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Product

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Understanding the Unique Thermodynamic Behavior of MgTFSI₂/DME Solutions. Part 1: Phase Diagram, Partial Volumes, and Densities

Understanding the Unique Thermodynamic Behavior of MgTFSI₂/DME Solutions. Part 1: Phase Diagram, Partial Volumes, and Densities