Intermolecular interactions and solvation effects of dimethylsulfoxide on type III deep eutectic solvents

Shah, Dhawal; Mansurov, Ulan; Mjalli, Farouq S.

doi:10.1039/c9cp02368b

Cited by 33 publications

(26 citation statements)

References 34 publications

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“…A detailed comparison of density data for neat reline available in the literature can be found elsewhere. 20 Figure 1b compares the ρ(x 1 ) data obtained in this study at 298.15 K with those of Shah et al 17 As noted above, we investigated only a limited number of samples at this temperature (Table S1 of the Supporting Information) due to the tendency of some of the prepared mixtures to precipitate. According to Figure 1b, the present ρ(x 1 ) data are generally somewhat larger than those of ref 17, but they follow the same trend.…”

Section: ■ Results and Discussionmentioning

confidence: 54%

Variation of Density, Viscosity, and Electrical Conductivity of the Deep Eutectic Solvent Reline, Composed of Choline Chloride and Urea at a Molar Ratio of 1:2, Mixed with Dimethylsulfoxide as a Cosolvent

Agieienko

Buchner

2020

J. Chem. Eng. Data

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We investigated the variation of density (ρ), dynamic viscosity (η), and electrical conductivity (κ) of mixtures of the deep eutectic solvent (DES) reline, composed of choline chloride and urea at a molar ratio of 1:2, with dimethylsulfoxide (DMSO) covering the entire miscibility range. Data for these properties were obtained as a function of temperature in the range 308.15 K ≤ T ≤ 363.15 K for ρ and η, whereas κ was recorded between 308.15 and 338.15 K. While ρ depended linearly on T, η and κ were best fitted by the empirical Vogel−Tammann−Fulcher (VFT) equation. The ρ(x 1 ) and η(x 1 ) datawith x 1 as the DES mole fractionwere used for calculating excess molar volumes (V E ) and excess logarithmic viscosities (ln η E ) of the studied system. With respect to volumetric properties, reline/DMSO mixtures deviate largely from ideality, possessing negative V E values over the entire range of T and x 1 . The temperature dependence of V E suggests that nonspecific interactions (packing effects) are mainly responsible for the system contraction. However, specific interactions (including H-bonding) cannot be excluded as ln η E values are positive and exhibit a temperature dependence characteristic for systems with strong interspecies interactions. Similar to conventional electrolytes and to mixtures of ionic liquids with a molecular solvent, κ as a function of x 1 shows a maximum at x 1 ≈ 0.25, indicating a concentration at which rising viscosity and the formation of ion pairs and larger aggregates compensate the conductivity rise caused by increasing charge carrier density. Changes in the VFT parameters point at a transition from electrolyte solution-like behavior to molten salt-like behavior at x 1 ≈ 0.6.

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Section: ■ Results and Discussionmentioning

confidence: 54%

Variation of Density, Viscosity, and Electrical Conductivity of the Deep Eutectic Solvent Reline, Composed of Choline Chloride and Urea at a Molar Ratio of 1:2, Mixed with Dimethylsulfoxide as a Cosolvent

Agieienko

Buchner

2020

J. Chem. Eng. Data

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“…Similarly, mixtures of [Ch] + [Cl] − , urea and DMSO have been studied by Shah et al . with MD simulations [40] . It was found that the number of H‐bonds between urea and DMSO became significant at DMSO fractions higher than 70 %.…”

Section: Introductionmentioning

confidence: 98%

Solvation and Ion‐Pairing Effects of Choline Acetate Electrolyte in Protic and Aprotic Solvents Studied by NMR Titrations

et al. 2021

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Choline-based electrolytes have been proposed as environmentally friendly and low-cost alternatives for secondary zinc air batteries. Choline acetate [Ch] + [OAc] À in protic (D 2 O) and aprotic (DMSO-d 6 ) solvents has been studied by means of concentration-dependent 1 H NMR, viscosity, and density measurements. The viscosities have been calculated on the basis of the Jones-Dole equation and showed that the dominant contribution originates from short-range ion-solvent interactions. Site-specific association affinities were assigned from NMR chemical shift titrations. In DMSO-d 6 , the hydroxyl group of choline was found to have the smallest dissociation constant followed by the methyl group of acetate. The corresponding Gibbs energies at low concentration were found to be in agreement with a solvent-separated ion pair (2SIP) configuration, whereas at concentrations above 300 mM, a solventshared ion pair (SIP) configuration was assigned. For [Ch] + [OAc] À in D 2 O, association effects were found to be weaker, attributed to the high dielectric constant of the solvent. On time scales on the order of 100 ms, NMR linewidth perturbations indicated a change in the local rotational dynamics of the ions, attributed to short-range cation-solvent interactions and not to solvent viscosity. At 184 mM, �40 % of the cations in DMSO-d 6 and �10 % in D 2 O were found to exhibit short-range interactions, as indicated by the linewidth perturbations. It was found that at about 300 mM, the ions in DMSO-d 6 exhibit a transition from free to collective translational dynamics on time scales on the order of 400 ms. In DMSO-d 6 , both ions were found to be almost equally solvated, whereas in D 2 O solvation of acetate was stronger, as indicated by the obtained effective hydrodynamic radii. For [Ch] + [OAc] À in DMSO-d 6 , the results suggest a solvent-shared ion association with weak H-bonding interactions for concentrations between 0.3-1 M. Overall, the extent of ion association in solvents such as DMSO is not expected to significantly limit charge transport and hinder the performance of choline-based electrolytes.[a] E.

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“…Fuelled by searching for environmentally friendly solvents for sustainable chemical processes, deep eutectic solvents (DESs) have emerged as green designer solvents with a wide range of applications. − A typical DES consists of an HB acceptor (HBA) and an HB donor (HBD), mixed in the eutectic molar ratio. ,− DES nanostructures, stabilized by intercomponent HB interactions, can be further tuned by the addition of cosolvents capable of disrupting the native HB networks. − As water can act as both HBA and HBD, these neoteric solvents are highly water-miscible and hygroscopic. , Recent reports demonstrate that water addition in the eutectic mixtures influences the DES nanostructures and consequently impacts their physicochemical properties . Trends in these properties suggest an upper limit of DES hydration, above which DES behaves like an aqueous solution. − …”

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confidence: 99%

Transition of a Deep Eutectic Solution to Aqueous Solution: A Dynamical Perspective of the Dissolved Solute

Sakpal

Deshmukh

Chatterjee

et al. 2021

J. Phys. Chem. Lett.

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Disruption of the deep eutectic solvent (DES) nanostructure around the dissolved solute upon addition of water is investigated by polarization-selective two-dimensional infrared spectroscopy and molecular dynamics simulations. The heterogeneous DES nanostructure around the solute is partially retained up to 41 wt % of added water, although water molecules are gradually incorporated in the solute’s solvation shell even at lower hydration levels. Beyond 41 wt %, the solute is observed to be preferentially solvated by water. This composition denotes the upper hydration limit of the deep eutectic solvent above which the solute senses an aqueous solvation environment. Interestingly, our results indicate that the transition from a deep eutectic solvation environment to an aqueous one around the dissolved solute can happen at a hydration level lower than that reported for the “water in DES” to “DES in water” transition.

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Intermolecular interactions and solvation effects of dimethylsulfoxide on type III deep eutectic solvents

Abstract: Intermolecular interactions within the mixtures of DMSO and reline, a typical type III Deep Eutectic Solvent (DES), composed of urea and choline chloride, is examined along with the mixtures' physical properties.

Cited by 33 publications

References 34 publications

Variation of Density, Viscosity, and Electrical Conductivity of the Deep Eutectic Solvent Reline, Composed of Choline Chloride and Urea at a Molar Ratio of 1:2, Mixed with Dimethylsulfoxide as a Cosolvent

Variation of Density, Viscosity, and Electrical Conductivity of the Deep Eutectic Solvent Reline, Composed of Choline Chloride and Urea at a Molar Ratio of 1:2, Mixed with Dimethylsulfoxide as a Cosolvent

Solvation and Ion‐Pairing Effects of Choline Acetate Electrolyte in Protic and Aprotic Solvents Studied by NMR Titrations

Transition of a Deep Eutectic Solution to Aqueous Solution: A Dynamical Perspective of the Dissolved Solute

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