Densities and viscosities for ionic liquids mixtures containing [eOHmim][BF4], [bmim][BF4] and [bpy][BF4]

Densities and viscosities of binary ionic liquids mixtures, 1-(2-hydroxyethyl)-3-methylimidazolium tetrafluoroborate ([eOHmim][BF₄]) + 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF₄]), 1-(2-hydroxyethyl)-3-methylimidazolium tetrafluoroborate ([eOHmim][BF₄]) + N-butylpyridinium tetrafluoroborate ([bpy][BF₄]) and 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF₄]) + N-butylpyridinium tetrafluoroborate ([bpy][BF₄]) were measured over the entire mole fraction from T = (298.15 to 343.15) K. The excess molar volumes were calculated and correlated by Redlich–Kiser polynomial expansions. The viscosities for pure ionic liquids were analyzed by means of the Vogel–Tammann–Fulcher equation and ideal mixing rules were applied for the ILs mixtures.     

Excess molar enthalpies for [Bmmim][BF4] + [Bmim][BF4] or [Emim][BF4] + cyclopentanone or cyclohexanone mixtures

Journal of Thermal Analysis and Calorimetry - In recent years, studies on mixtures consisting of ionic liquids and organic solvents have gained importance for the application of such mixtures for...     

Inhibition ability of ionic liquid [Bmim][NO3], [Bmim][BF4], and [Emim][BF4] on spontaneous coal combustion

Journal of Thermal Analysis and Calorimetry - From TG result, [Bmim][BF4] has the best inhibition ability of spontaneous coal combustion to delay the initial temperature, maximum temperature, and...     

Unstable Supramolecular Structure of [Bmim][BF4] in Aqueous Solution

To unravel the exact composition and structure of aggregates in an aqueous solution of 1-butyl-3-methylimidazolium tetrafluoroborate ([Bmim][BF₄]), we performed static and dynamic light-scattering measurements, as well as transmission electron microscopy (TEM). Results from this work show that the aggregates are vesicles and unstable; herein, we discuss the driving force behind the self-assembly. Apart from the van der Waals forces and repulsive electrostatic interactions between adjacent cation clusters, the hydrogen-bonding forces as well as counterion effects might also contribute to this driving force. The information obtained here is useful for a better understanding of the vital role that aggregation behavior plays in the field of ionic liquid recovery, and its potential use in controlled release, drug delivery, and petroleum recovery.     

Diorganoindium-Kationen. Die Kristallstruktur von [Mes2In][BF4]

Diorganoindium Cations. The Crystal Structure of [Mes₂In][BF₄] (PhCH₃)₂In and Mes₃In react with BF₃ · OEt₂ in a ratio of 3:4 at 80°C in toluene to the corresponding salts [R₂In][BF₄] [R = PhCH₂ ( 1 ), Mes ( 2 )]. The same results could be obtained, when the diorganoindium fluorides (PhCH₂)₂InF and Mes₂InF were treated with BF₃ · OEt₂ at 80°C in toluene. 1 und 2 were characterized by NMR-, IR- und MS-techniques. The arrangement of the ions in 2 could be established by an X-ray structure determination. The cations and anions of 2 are forming infinite chains. The metal centers are coordinated by two BF₄^?-ions, so that every In atom possesses a distorted octahedral coordination sphere.     

[EPy][BF4]和[EPy][PF6]离子对的气相及液相阴阳离子相互作用研究

采用从头算HF/6-31G和密度泛函理论B3LYP/6-31+G(d,p)方法, 对乙基吡啶四氟硼酸盐([EPy][BF4])和乙基吡啶六氟磷酸盐([EPy][PF6])的离子对进行了结构优化和频率分析, 并利用自洽反应场(SCRF)的导体极化连续模型(CPCM)考察了离子对液态下的结构及相互作用, 得到了两种离子对的红外光谱及气相、液相下最稳定结构. 由两种离子对的几何参数可知, 阴阳离子通过氢键相互作用, 两种离子液体的红外光谱特征值与实验值比较吻合. 应用自然键轨道(NBO)理论分析了吡啶阳离子及离子对中的原子电荷分布和电荷转移情况, 结果表明两种离子对中阴阳离子间存在静电相互作用和氢键作用. 通过几何参数、相互作用能及NBO分析研究发现, 液相下由于周围电荷的中和作用, 离子对中阴阳离子的相互作用明显降低.     

Solubility of H2S in ionic liquids [hmim][PF6], [hmim][BF4], and [hmim][Tf2N]

The solubility of hydrogen sulphide in three ionic liquids, viz. 1-hexyl-3-methylilmidazolium hexafluorophosphate ([hmim][PF₆]), 1-hexyl-3-methylimidazolium tetrafluoroborate ([hmim][BF₄]), and 1-hexyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([hmim][Tf₂N]), at temperatures ranging from 303.15 K to 343.15 K and pressures up to 1.1 MPa were determined. The solubility values were correlated using the Krichevsky–Kasarnovsky equation and Henry’s constants were obtained at different temperatures. Partial molar thermodynamic functions of solvation such as standard Gibbs free energy, enthalpy, and entropy were calculated from the solubility results. Comparison of the values obtained show that the solubility of H₂S in these three ionic liquids was in the sequence: [hmim][BF₄] > [hmim][PF₆] ≈ [hmim][Tf₂N].     

Ionic Association of the Ionic Liquids [C4mim][BF4], [C4mim][PF6], and [Cnmim]Br in Molecular Solvents

Considering the ionic nature of ionic liquids (ILs), ionic association is expected to be essential in solutions of ILs and to have an important influence on their applications. Although numerous studies have been reported for the ionic association behavior of ILs in solution, quantitative results are quite scarce. Herein, the conductivities of the ILs [C_nmim]Br (n=4, 6, 8, 10, 12), [C₄mim][BF₄], and [C₄mim][PF₆] in various molecular solvents (water, methanol, 1‐propanol, 1‐pentanol, acetonitrile, and acetone) are determined at 298.15 K as a function of IL concentration. The conductance data are analyzed by the Lee–Wheaton conductivity equation in terms of the ionic association constant (K_A) and the limiting molar conductance (Λ_m⁰). Combined with the values for the Br^? anion reported in the literature, the limiting molar conductivities and the transference numbers of the cations and [BF₄]^? and [PF₆]^? anions are calculated in the molecular solvents. It is shown that the alkyl chain length of the cations and type of anion affect the ionic association constants and limiting molar conductivities of the ILs. For a given anion (Br^?), the Λ_m⁰ values decrease with increasing alkyl chain length of the cations in all the molecular solvents, whereas the K_A values of the ILs decrease in organic solvents but increase in water as the alkyl chain length of the cations increases. For the [C₄mim]⁺ cation, the limiting molar conductivities of the ILs decrease in the order Br^?>[BF₄]^?>[PF₆]^?, and their ionic association constants follow the order [BF₄]^?>[PF₆]^?>Br^? in water, acetone, and acetonitrile. Furthermore, and similar to the classical electrolytes, a linear relationship is observed between ln K_A of the ILs and the reciprocal of the dielectric constants of the molecular solvents. The ILs are solvated to a different extent by the molecular solvents, and ionic association is affected significantly by ionic solvation. This information is expected to be useful for the modulation of the IL conductance by the alkyl chain length of the cations, type of anion, and physical properties of the molecular solvents.     

离子液体[Bmim][BF_4]中卟啉的三线态动力学

室温离子液体由于其几乎不挥发、稳定性突出、良好的电化学性能以及结构与性能的可设计性等优点,在诸多领域得到了深入的研究和广泛的应用。与传统的普通溶剂不同,离子液体的本质特点之一是其内部的微观结构具有微不均匀性。本文通过对四苯基卟啉(TPP)分子在离子液体[Bmim][BF_4]中的三线态动力学研究,发现在激光作用下,TPP的三线态寿命由2.95μs显著增加到184μs。进一步分析表明,这一现象很可能是由于离子液体的微结构在激光诱导下发生变化,被激光场或者离子诱导极化的氧气分子在离子液体微不均匀性环境中发生重新分布而引起的。     

Ionic Liquid [bmim][BF4] as a Green Medium for Passerini Reaction

The Passerini reaction, a three-component condensation reaction of carboxylic acid, aldehyde and isocyanide constructing an α-acyloxycarboxamide in a single step, was first discovered by Passerini about 80 years ago1. Since then, this reaction has been w…     

离子液体四氟硼酸-1-戊基-3-甲基咪唑的物理化学性质的估算

根据标准加入法原理配制一系列含有已知微量水的离子液体四氟硼酸-1-戊基-3-甲基咪唑([C5mim][BF4])样品,在278.15～338.15 K温度范围内,样品的密度与其含水量呈很好线性关系. 利用外推方法确定了含水量为零时[C5mim][BF4]的密度ρ,得到了密度随温度变化的经验方程:ln ρ=0.120 11-5.79×10-4(T-298.15)和离子液体的热膨胀系数α=5.79×10-4K-1. 根据Glasser理论估算了[C5mim][BF4]的标准熵、表面能和晶格能,晶格能较小使离子液体在室温下能以液态形式存在. 利用空隙模型计算得到了[C5mim][BF4] 热膨胀系数α(计算),与实验测定值在数量级上一致,说明空隙模型有一定的合理性.     

Synthesis and Characterization of Na5[VO4][O] and Na4[VO4][OH]

Na₅[VO₄][O] and Na₄[VO₄][OH] were obtained from reactions of V₂O₅ with Na₂O and additional NaOH in the latter case, respectively, at 600‐700 °C in sealed Ag containers under Ar atmosphere. The crystal structures have been determined from X‐ray single crystal data. The structures contain isolated [VO₄]^3? complexes and non‐coordinating oxide and hydroxide anions, respectively. Raman and infrared data is compared for both compounds and hydrogen bonding is discussed for Na₄[VO₄][OH].     

The Physical Properties of Aqueous Solutions of the Ionic Liquid [BMIM][BF4]

We report here the systematic study of the effect of concentration on the physical properties of aqueous solutions of the room-temperature ionic liquid [BMIM][BF₄]. The measurements of density, ρ, refractive index △n, viscosity η, specific conductivity κ and surface tension, γ, were made over the whole concentration range. The equivalent conductance Λ _m was calculated. The observed linear variations of density and refractive index with the molar concentration are established as those of an ideal solution. The surface tension varied most rapidly in the dilute region whereas the viscosity changed much more rapidly in the concentrated region. Two regions with different composition dependences were found after the analyses of the relationship between the conductivity and the concentration of [BMIM][BF₄]. A proposed model for a structural change in the mixtures was described. The physical origin of the observed concentration dependence of these properties is discussed. The physical properties of the solutions vary with changes of association between anions and cations and the interaction between [BMIM][BF₄] and water.     

Synthesis and Crystal Structures of [TeI3][GaI4] and [TeI3][InI4]

The compounds [TeI₃][MI₄] (M = Ga, In) were obtained as air sensitive black crystals by the reactions of Te, I₂ and Ga or In in vacuum sealed ampoules. The gallium compound crystallizes in the structural type of [SCl₃][AlCl₄]: monoclinic system, space group Pc (No. 7), a = 7.211(11), b = 7.2340(9), c = 15.67(2) Å and β = 102.51(6)°. The indium derivative crystallizes in the orthorhombic space group Pna2₁ (No. 33), a = 14.752(2), b = 7.1915(6) and c = 23.391(5) Å, with two crystallographically independent formula units per asymmetric unit. The structures consist of tetrahedral GaI₄^– or InI₄^– and trigonal pyramidal TeI₃⁺ units. Additionally, in both structures the tellurium atoms establish three weak interactions with iodine atoms of the MI₄^– units to form a distorted octahedral Te_{3 + 3} coordination sphere.