Dual modulation of the anion-driven thermodynamic properties of aqueous choline halide-based deep eutectic solvents

Prado, Desiree Mae; Prado, Ross Clark; Poling, Kayla; Hood, Phoebe; Samia, Anna Cristina; Burda, Clemens

doi:10.1063/5.0274816

Dual modulation of the anion-driven thermodynamic properties of aqueous choline halide-based deep eutectic solvents

Journal Article · Mon Aug 25 00:00:00 EDT 2025 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/5.0274816· OSTI ID:3026699

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Case Western Reserve Univ., Cleveland, OH (United States)

Deep eutectic solvents (DESs) are considered tunable solvents because their specific properties can be achieved based on the choice of components and their relative concentrations in a mixture. In this article, we investigate the influence of the variation in halide ions (F⁻, Cl⁻, Br⁻, I⁻) of choline salts used on the thermodynamic and physicochemical properties of choline halide-based DESs. Our findings show that the density of choline halide-based DESs decreases nonlinearly with an increasing mole fraction of water, following a trend based on the size of the halides, with choline iodide showing the highest density. Temperature-dependent density data reveal that the thermal expansion coefficient decreases slightly with increasing water content, indicating a more stable volume at a higher mole fraction of water. The excess molar volume (V^E) of the DES mixtures exhibits complex behavior depending on the choline halide used, with both negative and positive V^E values observed across different water mole fractions. These variations are linked to the hydrogen bonding interactions between the DES components and water molecules. In addition, viscosities decrease with increasing water content, suggesting the disruption of hydrogen bonding networks and enhanced mobility of the ions, which contributes to the observed increase in conductivity. The excess molar Gibbs energies, enthalpies, and entropies of activation have also been determined.

View Accepted Manuscript (DOE)

Research Organization:: Case Western Reserve Univ., Cleveland, OH (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0019409

OSTI ID:: 3026699

Journal Information:: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 8 Vol. 163; ISSN 1089-7690; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

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Dual modulation of the anion-driven thermodynamic properties of aqueous choline halide-based deep eutectic solvents

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