Solvation of small molecules in imidazolium ionic liquids: a simulation study

Hanke, C. G.; Atamas, N. A.; Lynden‐Bell, R. M.

doi:10.1039/b109179b

Cited by 275 publications

(224 citation statements)

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“…[1][2][3] Thus molecular design, synthesis, and characterization of RILs have been the focus of many recent scientific investigations. [4][5][6] However, one of the barriers in the application of RILs is the general lack of physical property data for these compounds toward fundamental understanding of the system.…”

Section: Introductionmentioning

confidence: 99%

Structures of Ionic Liquids with Different Anions Studied by Infrared Vibration Spectroscopy

et al. 2008

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We investigated the structures of ionic liquids (1-butyl-3-methylimidazolium iodide [BMIM][I] and 1-butyl-3-methylimidazolium tetrafluoroborate [BMIM][BF 4 ]) and their aqueous mixtures using attenuated total reflection (ATR) infrared absorption and Raman spectroscopy. The ATR spectrum in the CH x (x ) 1, 2, 3) vibration region from 2800 to 3200 cm [BF 4 ]. These differences are considered to come from the variation in the position of the anion, where I -is expected to be closer to the C(2) hydrogen of the imidazolium cation and interacting more specifically as compared to BF 4 -.

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Section: Introductionmentioning

confidence: 99%

Structures of Ionic Liquids with Different Anions Studied by Infrared Vibration Spectroscopy

et al. 2008

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“…19 Similarly, more recent ATR−Fourier transform infrared (FTIR) and NMR studies involving the interaction of 1-ethyl-3-methylimidazolium tetrafluoroborate ( 4 ] at χ w ≈ 0.3. 30 In addition, large-angle X-ray scattering experiments showed that as the concentration of water increased in [ 29 The same group investigated [C 1 MIM]-[Cl]−water mixtures and observed that at low water concentrations water is either isolated or contained in small water clusters, but at higher concentrations the water molecules form a continuous network. 31 They also found that at higher water concentrations the properties of the IL−water mixture were different from the pure IL.…”

Section: ■ Introductionmentioning

confidence: 99%

Interaction of Water Vapor with the Surfaces of Imidazolium-Based Ionic Liquid Nanoparticles and Thin Films

et al. 2012

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Understanding the interactions of humid air with ionic liquids (ILs) is critical for predicting how their physicochemical properties are affected by water. Using experimental and theoretical techniques, water vapor's interaction with aerosolized nanoparticles and thin films of [C 2 MIM][Cl] and [C 2 MIM][BF 4 ] was studied. Solutions were electrosprayed to produce dry particles. Particles' hygroscopic growth was quantified using tandem nanodifferential mobility analysis as a function of relative humidity (RH). This is the first report of the interaction of water with aerosolized IL nanoparticles. The particles' small size allows true IL−water vapor equilibrium achieved quickly. Growth curves for both ILs show steady water uptake with increasing RH. Water vapor uptake by IL thin films was also examined using ATR-FTIR spectroscopy. . They represent a large class of molecules that have unique and widely tunable physical and chemical properties. 1−3 For example, there is a significant interest in the use of ILs in green chemistry, 2,4,5 due to their negligible vapor pressure at room temperature, 6 and for many other applications including solvents in synthesis and catalysis, 1,6 chemical extraction, 1,2,5 and fuel cells. 7 Physical properties such as conductivity, viscosity, density, and surface tension of ILs are known to depend on the presence of water, both adsorbed and absorbed. 3,8 Water is ubiquitous in the environment, and hygroscopic ILs such as those with imidazolium-based cations can uptake significant amounts of water vapor from ambient air, which alters their physical and chemical properties. 1,3 Thus, quantification of water uptake by hygroscopic ILs and understanding how the presence of water affects the nature of the ion−ion and ion−water interactions are critical for use of ILs in future applications. 8−14 Numerous experimental and theoretical studies have investigated the interaction of imidazolium-based ILs with water. 3,8−35 It is understood that both the cation and the anion have an effect on how ILs interact with water, with the anion having a stronger effect. 3,17,19 Early experimental work by Seddon et al. investigated the miscibility of water with ILs containing 1-nalkyl-3-methylimidazolium ([C n MIM + ], n = number of carbons on the linear alkyl chain) cations and various anions at room temperature. 3 It was determined that, regardless of the alkyl chain length, all halide anions were fully soluble in water and all hexafluorophosphate ([PF 6 − ]) anions were insoluble. 3 However, alkyl chain length did have an effect on water miscibility of [C n MIM + ]-based ILs with tetrafluoroborate ([BF 4 − ]) anions; for chain lengths of n = 2 or 4, the ILs were fully miscible, but for n > 4, the ILs formed biphasic systems. 3 Cammarata et al. performed early attenuated total reflection (ATR) infrared (IR) studies on the molecular states of water

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“…A superior approach to the condensed phase is given by molecular dynamics simulations. Traditional molecular dynamics simulations of ionic liquids employing pair potentials were pioneered by Hanke et al 20,21 and Lynden-Bell. 22 Polarizable force fields have also been tested for molecular dynamics simulations of ionic liquids.…”

Section: Introductionmentioning

confidence: 99%

Cooperativity in ionic liquids

Koßmann

Thar

Kirchner

et al. 2006

The Journal of Chemical Physics

155

173

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Cooperativity in ionic liquids is investigated by means of static quantum chemical calculations. Larger clusters of the dimethylimidazolium cation paired with a chloride anion are calculated within density functional theory combined with gradient corrected functionals. Tests of the monomer unit show that density functional theory performs reasonably well. Linear chain and ring aggregates have been considered and geometries are found to be comparable with liquid phase structures. Cooperative effects occur when the total energy of the oligomer differs from a simple sum of monomer energies. Cooperative effects have been found in the structural motifs examined. A systematic study of linear chains of increasing length ͑up to nine monomer units͒ has shown that cooperativity plays a more important role than expected and is stronger than in water. The Cl¯H distance of the chloride to the most acidic proton increases with an increasing number of monomer units. The average bond distance approaches 218.9 pm asymptotically. The dipole moment grows almost linearly and the dipole moment per monomer unit reaches the asymptotic value of 16.3 D. The charge on the chloride atoms decreases with an increasing chain length. In order to detect local hydrogen bonding in the clusters a new parametrization of the shared-electron number method is introduced. We find decreasing hydrogen bond energies with an increasing cluster size for both the first hydrogen bond to the most acidic proton and the average hydrogen bond.

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Solvation of small molecules in imidazolium ionic liquids: a simulation study

Cited by 275 publications

References 11 publications

Structures of Ionic Liquids with Different Anions Studied by Infrared Vibration Spectroscopy

Structures of Ionic Liquids with Different Anions Studied by Infrared Vibration Spectroscopy

Interaction of Water Vapor with the Surfaces of Imidazolium-Based Ionic Liquid Nanoparticles and Thin Films

Cooperativity in ionic liquids

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