Surface structures of equimolar mixtures of imidazolium-based ionic liquids using high-resolution Rutherford backscattering spectroscopy

Surface structures of equimolar mixtures of imidazolium-based ionic liquids (ILs) having a common cation (1-butyl-3-methylimidazolium ([C₄MIM]) or 1-hexyl-3-methylimidazolium ([C₆MIM])) and different anions (bis(trifluoromethanesulfonyl)imide ([TFSI]), hexafluorophosphate ([PF₆]) or chlorine) are studied using high-resolution Rutherford backscattering spectroscopy (HRBS). Both cations and anions have the same preferential orientations at the surface as in the pure ILs. In the mixture, the larger anion is located shallower than the smaller anion. The [TFSI] anion is slightly enriched at the surface relative to [PF₆] with coverage of ~ 60% for the equimolar mixtures of [C₄₍₆₎MIM] [TFSI] and [C₄₍₆₎MIM] [PF₆]. No surface segregation is observed for [C₆MIM] [TFSI]_0.5[Cl]_0.5 and [C₆MIM] [PF₆]_0.5[Cl]_0.5. These results are different from the recent TOF-SIMS measurement where very strong surface segregation of [TFSI] was concluded for the mixture of [C₄MIM] [TFSI] and [C₄MIM] [PF₆].     

Electronic structures of imidazolium-based ionic liquids

Electronic structures of ionic liquids formed by 1-buthyl-3-alkylimidazolium ion [C_nmim]⁺ (n = 4 and 8) with various inorganic and organic anions have been investigated by ultraviolet photoemission, X-ray photoemission, inverse photoemission and soft X-ray emission spectroscopies (SXES). The comparison of the calculated density of states with the observed spectra revealed that the molecular orbital energies of these ionic liquids are significantly affected by the electrostatic Madelung potential among the ions. The SXES results clearly show that the both highest occupied and lowest unoccupied states of [C₄mim]⁺PF₆⁻ are derived from the cation as a result of strong Madelung potential. On the other hand, the SXES results show the valence electronic structures of ionic liquids with larger anion molecules, [C_nmim]⁺Tf₂N⁻ and [C_nmim]⁺OTf⁻ are contributed from the both cation and anion.     

Aggregates in mixtures of ionic liquids

Surfactant-like ionic liquids (C₁₆MIMCl, C₁₆MIMBF₄) aggregate in mixtures with another ionic liquid (EAN). Critical aggregate concentrations and estimations of object sizes are given and compared to aqueous systems and other relevant literature data. The investigated mixtures are stable up to more than 200 °C and can probably be used to extend the limited temperature range of water-based colloids.     

Solvophobic solvation and interaction of small apolar particles in imidazolium-based ionic liquids

We report results of molecular dynamics simulations characterizing the solvation and interaction of small apolar particles such as methane and xenon in imidazolium-based ionic liquids (ILs). The simulations are able to reproduce semiquantitatively the anomalous temperature dependence of the solubility of apolar particles in the infinite dilution regime. We observe that the "solvophobic solvation" of small apolar particles in ILs is governed by compensating entropic and enthalpic contributions, very much like the hydrophobic hydration of small apolar particles in liquid water. In addition, our simulations clearly indicate that the solvent mediated interaction of apolar particles dissolved in ILs is similarly driven by compensating enthalpic and entropic contributions, making the "solvophobic interaction" thermodynamically analogous to the hydrophobic interaction.     

A perturbed hard-sphere equation of state extended to imidazolium-based ionic liquids

A perturbed hard-sphere equation of state (EOS) has been previously employed to predict pressure–volume–temperature properties of some ionic liquids (ILs) with phosphonium-, pyridinium-, and pyrrolidinium cations. In this work, we have extended the considered EOS to another class of ILs in compressed states. This class consists of 14 imidazolium-based ILs. The predicted densities were compared with those obtained from the experiment, over a broad pressure range from 0.1 to 200 MPa. From 1,122 data points examined for the aforementioned ILs, the total average absolute deviation was found to be 1.05%.     

振动颗粒混合物中的三明治式分离

在竖直振动两种颗粒的混合物的实验中，观察到了一种新的分离现象——“三明治”式分离，即大而重的颗粒被夹在两层小的轻颗粒之间.这不同于“巴西果”效应导致的大而重的颗粒在上的两层有序结构.实验表明当振动加速度大于某个临界值时这种三层有序将取代两层结构，而且是稳定的.实验中观察到导致“三明治”式分离的两种不同的分离过程.对这两种过程的物理机理及其与振动加速度、振动频率及颗粒尺寸等因素的关系做了研究，并给出了相图. 关键词： 颗粒物质 振动 有序结构 三明治式分离 巴西果效应     

Structure and diffusion in mixtures of ionic liquids

The properties of ionic mixtures of LiBr-KBr are investigated on the basis of molecular dynamics calculations, using the Tosi-Fumi pair-potentials. The determination of the excess internal energy of mixing indicates the predominant negative contribution of the coulomb energy. The position of the first peak of the anion-cation radial distribution function depends strongly on the size of the ions and its height is much influenced by the strength of the coulomb forces. It is shown that the equivalent coordination numbers vary from about 4 for the Li-Br pair to 6 for the K-Br pair. These numbers do not change very much when the composition is varied.

The ionic dynamics is analysed through the brownian-like formalism which gives a useful connection between the structure and the particle motion. Two mechanisms are involved in the diffusion process: an oscillation of the particle in the force field of the neighbouring particles and a collective mode of motion which has a longer relaxation time. The strong anion-cation correlation, which mainly affects the smallest cation, dominates when the charge ordering (quasi-lattice structure) vanishes.     

Correlation of volumetric properties of binary mixtures of some ionic liquids with alcohols using equation of state

In our previous paper, we extended the Tao and Mason equation of state (TM EOS) to pure ionic liquids. Here we apply TM EOS based on statistical?Cmechanical perturbation theory to binary mixtures of ionic liquids. Three temperature-dependent quantities are needed to use the equation of state: the second virial coefficient, B ₂, effective van der Waals co-volume, b, and a scaling factor, ??. The second virial coefficients are calculated from a correlation that uses the normal boiling temperature and normal boiling density. ?? and b can also be calculated from the second virial coefficient by scaling. In this procedure, the number of input parameters, for calculation of B ₂, ??, and b reduced from 5 (i.e., critical temperature, critical pressure, acetric factor, Boyle temperature T _B, and the Boyle volume ?? _B) to 2 (i.e., T _bp and ?? _bp). At close inspection of the deviations given in this work, the TM EOS predicts the densities with a mean AAD of 1.69%. The density of selected system obtained from the TM EOS has been compared with those calculated from perturbed-hard-sphere equation of state. Our results are in favor of the preference of the TM EOS over another equation of state. The overall average absolute deviation for 428 data points that calculated by perturbed-hard-sphere equation of state is 2.60%.     

垂直振动作用下二元混合颗粒分层的动态循环反转

在对垂直振动下的铜颗粒和氧化铝颗粒混合物的研究中,除了观测到巴西果分层和混合分层外,还发现了一种新的随时间周期变化的分离形态. 此分离形态可随着时间的演化,在巴西果、反巴西果和三明治这几种分层构型之间进行动态的循环反转. 给出了这种反转态出现的相区,并且观测了其动态转变的规律. 根据碰撞、磨擦及空气的耗散作用所产生的耗散结构对循环反转态的出现给出了定性的解释,并通过实验证实这种分层构型与空气的存在有密切的关系. 关键词： 颗粒物质 巴西果效应 相分离     

Phase separation of highly dissymmetric binary ionic mixtures

We study the phase separation of binary ionic mixtures involving two species of classical point ions in a rigid uniform neutralizing background of degenerate electrons. The thermodynamic properties of the ionic fluid are calculated on the basis of the HNC integral equation for the three partial pair distribution functions. We develop a systematic technique which allows the properties of mixtures of arbitrary composition to be expressed in terms of infinitely dilute solutions. Phase diagrams and critical parameters are determined for 12 different binary systems involving ionic charge ratios between 2 and 8. The dependence of the critical temperature on the ionic charges, on the pressure and an ionic quantum corrections is examined in detail.     

振动颗粒混合物中的周期性分聚现象与能量耗散

在垂直振动的激励下, 铜和玻璃珠组成的二元颗粒混合样品存在依次出现分界清晰的三明治, 巴西果, 反巴西果三种分聚结构的周期循环变化现象, 其中出现三明治结构的时段最长(大于90%). 循环周期随振动台频率的增加而增大, 随加速度的增加而减小. 对三种分聚结构的样品能量耗散功率的测量显示, 在相同的振动条件下反巴西果结构的能耗功率最大, 巴西果结构的最小. 利用Hong的凝聚和渗透两机理相互竞争的观点, 并结合能耗功率的测量结果, 可定性解释这个周期性分聚现象.     

Surface segregation in binary alloys: A semiempirical approach

The preferential segregation concentration of one component in a binary alloy can be estimated, as a function of depth from the surface, from relative X-ray photoemission signal intensities. The details of this semiempirical calculation are outlined. In addition, common approximations applied to these calculations as well as typical experimental errors are analyzed to assess the effects upon the resulting calculated segregation profiles. The semiempirical analysis has been applied to previously published data for Cu₁₇N₈₃ and Fe₇₂Cr₂₈ binary alloys.     

Phase separation in strongly coupled binary ionic mixtures at zero temperature

The ground-state energy of strongly coupled binary ionic mixtures is evaluated by solving the hypernetted-chain (HNC) equations for the pair distribution functions. The point ions are immersed in a rigid and uniform neutralizing background of relativistic electrons. We have calculated the equation of state and the pair structure of these binary fluids for three concentrations and over a rather extensive range of densities. The miscibility essentially depends on the statistics of the species and on the coupling. We show that the phase separation is very sensitive to the choice of the wave function used to describe the mixture.     

Surface tension of the restrictive primitive model for ionic liquids

Hybrid molecular dynamics and Monte Carlo simulations are performed to study the liquid-vapor interface of the restricted primitive model (RPM) of ionic fluids. We report for the first time simulation results of the surface tension associated to this interface. The RPM accurately predicts experimental surface tensions of ionic salts and good agreement with theoretical predictions that include the idea of ion association is found. The simulation results indicate that the structure of an ionic liquid-vapor interface is rather rough. This is reflected in the interfacial thickness, larger than that observed in simple fluids and water.     

Surface and bulk interchange energy in binary mixtures of chain molecules

The interchange (interaction) parameter, controlling the phase behaviour of a binary mixture, is determined for the bulk and the surface of binary mixtures of different types of chain molecules, using surface tensiometry and a mean-field theory. For all mixtures and concentrations studied an identical behaviour is observed at the surface, depending only on the square of the reduced chain length mismatch , where and are the difference in and average of the number of carbons of the two components.Received: 21 December 2003, Published online: 25 March 2004PACS: 61.30.Hn Surface phenomena: alignment, anchoring, anchoring transitions, surface-induced layering, surface-induced ordering, wetting, prewetting transitions, and wetting transitions - 68.35.Md Surface thermodynamics, surface energies - 68.03.Cd Surface tension and related phenomena     

Structure,thermodynamic and transport properties of imidazolium-based bis(trifluoromethylsulfonyl)imide ionic liquids from molecular dynamics simulations

Molecular dynamics (MD) simulations have been performed in order to investigate the properties of [C _n mim⁺][Tf₂N^?] (n?=?4,?8,?12) ionic liquids (ILs) in a wide temperature range (298.15?498.15?K) and at atmospheric pressure (1 bar). A previously developed methodology for the calculation of the charge distribution that incorporates ab initio quantum mechanical calculations based on density functional theory (DFT) was used to calculate the partial charges for the classical molecular simulations. The wide range of time scales that characterize the segmental dynamics of these ILs, especially at low temperatures, required very long MD simulations, on the order of several tens of nanoseconds, to calculate the thermodynamic (density, thermal expansion, isothermal compressibility), structural (radial distribution functions between the centers of mass of ions and between individual sites, radial-angular distribution functions) and dynamic (relaxation times of the reorientation of the bonds and the torsion angles, self-diffusion coefficients, shear viscosity) properties. The influence of the temperature and the cation's alkyl chain length on the above-mentioned properties was thoroughly investigated. The calculated thermodynamic (primary and derivative) and structural properties are in good agreement with the experimental data, while the extremely sluggish dynamics of the ILs under study renders the calculation of their transport properties a very complicated and challenging task, especially at low temperatures.     

Thermophysical properties of ionic liquids and their mixtures from a new equation of state

In our previous work, a perturbed hard-trimer-sphere equation of state (PHTS EOS) was developed for modeling the phase equilibria of pure ionic liquids (ILs) (M.M. Alavianmehr et al., Ionics 22 (2016) 2447–2459). In this work, we have successfully extended the model to the mixtures of IL + IL and IL + solvent. Two temperature-dependent parameters appearing in the EOS are correlated with two microscopic scaling constants σ, the effective hard-sphere diameter, and ε, the non-bonded interaction energy. The overall average absolute deviation (AAD) of the estimated densities from the literature data using the proposed model with and without non-additivity parameter (λ _ij) was found to be 0.44 and 0.79%, respectively. A modified Enskog equation and rough hard-sphere (RHS) theory are combined with our proposed equation of state to calculate the viscosity coefficient of ionic liquids and their mixtures. Finally, from the results obtained, a linear relation between logarithm of surface tension and viscosity property of ionic liquid was developed.     

Activity coefficient models to describe isothermal vapor-liquid equilibrium of binary systems containing ionic liquids

Isothermal vapor-liquid equilibrium data of binary mixtures containing ionic liquids are correlated using three activity coefficient models: UNIQUAC, Wilson, and NRTL. Twenty binary systems taken from the literature were selected for this study. A genetic algorithm is used to determine the interaction parameters for the three models. The results given by the three models have been compared with experimental data, and show that the UNIQUAC model is the best method to correlate and predict the vapor-liquid equilibrium of this type of systems.