Solvation of molecular cosolvents and inorganic salts in ionic liquids: A review of molecular dynamics simulations

We present a derivation of generalized Poisson-Boltzmann equations starting from classical theories of binary fluid mixtures, employing an approach based on the Legendre transform as recently applied to the case of local descriptions of the fluid free energy. Under specific symmetry assumptions, and in the linearized regime, the Poisson-Boltzmann equation reduces to a phenomenological equation introduced by (Bazant et al., 2011), whereby the structuring near the surface is determined by bulk coefficients.

show abstract

“…This phenomenon has been observed in numerous experiments and simulations, see e.g. [3][4][5][6][7]; for a review, see [8].…”

Section: Introductionmentioning

confidence: 59%

Structural interactions in ionic liquids linked to higher-order Poisson-Boltzmann equations

2017

View full text Add to dashboard Cite

show abstract

“…A successful route towards gaining a deeper understanding is through the study of ILs with different compositions. A lot of effort has been made to study cation behavior, whereas recent studies of anion effects also reveal distinct solvation properties . In brief, some results indicated that apolar solutes such as benzene are better dissolved in ILs that have larger anions such as bis(trifluoromethanesulfonyl)imide (TFSI) or smaller cation/anion size ratios .…”

Section: Introductionmentioning

confidence: 99%

Properties of Apolar Solutes in Alkyl Imidazolium‐Based Ionic Liquids: The Importance of Local Interactions

et al. 2015

View full text Add to dashboard Cite

The solvation and the dynamic properties of apolar model solutes in alkyl imidazolium-based ionic liquids (IL) are studied by using all-atom molecular dynamics simulations. In regards to specific IL effects, we focused on the often used 1-ethyl-3-methyl imidazolium cation in combination with the anions tetrafluoroborate, acetate, and bis(trifluoromethanesulfonyl)imide. Our findings reveal that the size of the anion crucially influences the accumulation behavior of the cations, which results in modified IL solvation properties. Deviations between the different alkyl imidazolium-based IL combinations can be also observed with regard to the results for the radial distribution functions, the number of surrounding molecules, and the molecular orientation. The analysis of the van Hove function further shows pronounced differences in the dynamic behavior of the solutes. The simulations verify that the solute mobilities are mainly influenced by the composition of the local solvent shell and the properties of the underlying Lennard-Jones interactions. Additional simulations with regard to modified short-range dispersion energies for alkyl imidazolium-based ILs validate our conclusions.

show abstract

“…7A, which were very much in line with a previously reported finding that the size of water cluster is strongly dependent on the hydrophobicity of the caion. 32,64 This finding has been illustrated by the above mentioned W-W RDFs. Fig.…”

Section: Statistical Analysis Of Water Aggregationmentioning

confidence: 55%

“…Lastly, relatively heavy clustering of water for both homogeneous and hydrophobic phases is observed, as shown by the heights of the first peaks of the W-W RDFs, which is in agreement with previously reported results. 32 …”

Section: Rdfmentioning

confidence: 99%

Dynamic phase change and local structures in IL-containing mixtures: classical MD simulations and experiments

Wang

Liu

et al. 2017

Phys. Chem. Chem. Phys.

View full text Add to dashboard Cite

The dynamic phase change between a homogeneous mixture and a liquid-liquid biphase and separation of phases are explored in three-component mixtures composed of 1-butyl-3-methylimidazolium hexafluorophosphate ([Bmim][PF]), 1-butyl-3-methylimidazolium tetrafluoroborate ([Bmim][BF]), and water through a classical simulation method and experiment. Different experimental and theoretical tools, including density measurement, dynamic light scattering study, radial distribution, mean square displacement, an interstice model, and statistical function, are used to describe the structural modifications of the ions as a function of solution concentration. An analysis of the relation between the phase and the state of the component ions indicates that the phase separation pattern is governed by the hydrophilicity/hydrophobicity of anions. We proposed the existence of a critical point, that is, 1 : 3 : 8 for [Bmim][PF]/[Bmim][BF]/HO (mole fraction). Before this critical point, obvious phase separation was seen in the mixtures. The separation phase became homogeneous with the addition of [Bmim][BF] after this critical point. However, this homogeneous mixed solution was phase separated again upon the addition of [Bmim][PF] or water. The existing nanostructures were present in the [Bmim][PF]/[Bmim][BF]/HO mixtures, and their size abruptly decreased close to the critical point. We provided evidence of the formation of double salt ionic liquids of [Bmim][PF][BF]·2HO and discussed the interactions involved in these systems by examining their physicochemical properties. The ionic phase response of such three-component mixtures could be useful in various applications, especially in the dynamic control of extraction/separation processing.

show abstract

Solvation of molecular cosolvents and inorganic salts in ionic liquids: A review of molecular dynamics simulations

Cited by 79 publications

References 95 publications

Structural interactions in ionic liquids linked to higher-order Poisson-Boltzmann equations

Structural interactions in ionic liquids linked to higher-order Poisson-Boltzmann equations

Properties of Apolar Solutes in Alkyl Imidazolium‐Based Ionic Liquids: The Importance of Local Interactions

Dynamic phase change and local structures in IL-containing mixtures: classical MD simulations and experiments

Contact Info

Product

Resources

About