Extraction and high performance liquid chromatographic determination of 3-indole butyric acid in pea plants by using imidazolium-based ionic liquids as extractant

In this paper, imidazolium-based ionic liquids [C₄mim][PF₆], [C₆mim][PF₆], [C₈mim][PF₆], [C₆mim][BF₄] and [C₈mim][BF₄] were tested as extracting solvents for removal of 3-indole butyric acid (IBA) from aqueous media with subsequent determination using HPLC. Percent extraction of IBA was strongly affected by pH of aqueous phases and the chemical structures of ionic liquids (ILs). Extraction of IBA was quantitative in the pH values lower than pK_a of IBA. Considering both extraction and stripping efficiencies of IBA, [C₄mim][PF₆] was found to act more efficient than other studied ILs. Capacity of [C₄mim][PF₆] was 17.6 × 10⁻⁴ mmol IBA per 1.0 mL of IL. Ionic strength of aqueous phase and temperature had shown no serious effects on extraction efficiency of IBA. A preconcentration factor of 100 and a relative standard deviation of 1.16% were obtained. It was found that ionic liquid phase was reusable almost five times for extraction/stripping purposes. 3-Indole acetic acid showed interferential effect in the extraction step. In order to assess the applicability of the method, extraction and stripping of IBA from pea plants and some other samples were studied.     

Evaluation and comparison of global scalar properties for the simultaneous interaction of ionic liquids with thiophene and pyridine

Ab initio studies were carried out with mixtures containing ionic liquid with thiophene and pyridine for studying the simultaneous interaction. Global scalar properties such as HOMO/LUMO energies, HOMO–LUMO energy gap, chemical hardness, chemical potential, electronegativity, global hardness, global softness and electrophilicity index were determined for clusters containing ionic liquids with thiophene and pyridine. Ionic liquids containing: 1-butyl-3-methylpyrrolidinium [BUMPYR], 1-benzyl-3-methyimidazolioum [BeMIM] and 1-butyl-3-methylpyridinium [BUMPY] cations combined with inorganic anions containing fluorine ([BF₄] and [PF₆]) were studied in this work. [BeMIM][BF₄] (1-benzyl-3-methyimidazolioum tetrafluoroborate) with a HOMO–LUMO energy gap of 0.1882 Hartrees was found to be the most effective IL. Further a ranking based on all the mentioned scalar parameters also pointed out [BeMIM][BF₄] to be the most desirable IL. The overall ranking after taking into considerations all factors followed: [BeMIM][BF₄] > [BUMPYR][BF₄] > [BUMPY][PF₆] > [BUMPY][BF₄] > [BUMPYR][PF₆]. To validate the findings, infinite dilution activity coefficients were predicted using the quantum chemical based COSMO-RS methodology which gave the same trend as observed using scalar properties.     

Extraction of Metal Ions from Aqueous Solutions Using Imidazolium Based Ionic Liquids

This article represents a step towards how to choose an ionic liquid as the solvent to improve metal ion (Ag⁺ and Pb²⁺) extraction. The liquid-liquid solvent extraction is proposed with the following imidazolium ionic liquids (ILs): 1-ethyl-3-ethylimidazolium, or 1-butyl-3-ethylimidazolium, or 1-hexyl-3-ethylimidazolium bis{(trifluoromethyl)sylfonyl}imide [EEIM][NTf₂], or [BEIM][NTf₂], or [HEIM][NTf₂], or 1-butyl-3-ethylimidazolium hexafluorophosphate [BEIM][PF₆], or 1-hexyl-3-ethylimidazolium hexafluorophosphate [HEIM][PF₆] and the popular 1-butyl-3-methylimidazolium hexafluorophosphate [BMIM][PF₆] for comparison. The effect of anion type (NTf₂⁻ versus PF₆⁻) and the effect of structural components of an ionic liquid including alkyl chain length at the cation and the ethyl substituent instead methyl at the cation, on the extraction and re-extraction processes by using dithizone as a metal chelator, were studied at 296 K. Dithizone was employed to form neutral metal-dithizone complexes with heavy metal ions to extract them from aqueous solution into the ILs. Electronic Supplementary Material  The online version of this article () contains supplementary material, which is available to authorized users. Presented at the 236th ACS National Meeting, August 17–21, Philadelphia, USA.     

Solubility of CO2 in 1-(2-hydroxyethyl)-3-methylimidazolium ionic liquids with different anions

The solubility of carbon dioxide in a series of 1-(2-hydroxyethyl)-3-methylimidazolium ([hemim]⁺) based ionic liquids (ILs) with different anions, viz. hexafluorophosphate ([PF₆]^?), trifluoromethanesulfonate ([OTf]^?), and bis-(trifluoromethyl)sulfonylimide ([Tf₂N]^?) at temperatures ranging from 303.15 K to 353.15 K and pressures up to 1.3 MPa were determined. The solubility data were correlated using the Krichevsky–Kasarnovsky equation and Henry’s law constants were obtained at different temperatures. Using the solubility data, the partial molar thermodynamic functions of solution such as Gibbs free energy, enthalpy, and entropy were calculated. Comparison showed that the solubility of CO₂ in the ILs studied follows the same behaviour as the corresponding conventional 1-ethyl-3-methylimidazolium ([emim]⁺) based ILs with the same anions, i.e. [hemim][NTf₂] > [hemim][OTf] > [hemim][PF₆] > [hemim][BF₄].     

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.     

Organic reactions in ionic liquids: Ionic liquid‐promoted efficient synthesis of N‐alkyl and N‐arylphthalimides

Phthalic anhydride reacts rapidly with Aromatic and aliphatic amines in ionic liquid [Bmim][PF₆] or [Bmim][BF₄] at 130 °C to give N‐aryl and N‐alkylphthalimides in excellent yields.     

The physicochemical properties of some imidazolium-based ionic liquids and their binary mixtures

The density, viscosity and conductivity of ionic liquids (ILs), 1-octyl-3-methylimidazolium tetrafluoroborate ([omim][BF4]), 1-octyl-3-methylimidazolium chloride ([omim][Cl]), 1-hexyl-3-methylimidazolium tetrafluoroborate ([hmim] BF4]), 1-hexyl- 3-methylimidazolium chloride ([hmim][Cl]), 1-hexyl-3-methylimidazolium hexafluorophosphate ([hmim][PF6]), and the [omim][BF4] + [omim][Cl], [hmim][BF4] + [hmim][Cl], and [hmim][PF6] + [hmim][Cl] binary mixtures were studied at dif- ferent temperatures. It was demonstrated that the densities of both the neat ILs and their mixtures varied linearly with temper- ature. The density sensitivity of a binary mixture is between those of the two components. The excess molar volumes (VE) of [hmim][BF4] + [hmim][Cl] and [hmim][PF6] + [hmim][Cl] mixtures are positive in the whole composition range. For [omim][BF4] + [omim][Cl], the VE is also positive in the [omim][Cl]-rich region, but is negative in the [omim][BF4]-rich re- gion. The viscosity or conductivity of a mixture is in the intermediate of those of the two neat ILs. For all the neat ILs and the binary mixtures studied, the order of conductivity is opposite to that of the viscosity. The Vogel-Tammann-Fulcher (VTF) equations can be used to fit the viscosity and conductivity of all the neat ILs and the binary mixtures. The neat ILs and their mixtures obey the Fractional Walden Rule very well, and the values of the Walden slopes are all smaller than unit, indicating obvious ion associations in the neat ILs and the binary mixtures.     

Palladium‐Catalyzed Enyne Cyclization of 2′‐Alkenyl 2‐Alkynoates in Imidazolium‐Type Ionic Liquids

The use of [bmim][BF₄], [bmim][PF₆], and [bmim][Cl] ILs as the solvents in Pd(II)‐catalyzed enyne cyclization of 2′‐alkenyl 2‐alkynoates in the presence of cupric chloride has been investigated. The Z/E stereoselectivity of the reaction could range from 90:10 to 4:96 by tuning the amount of LiCl in ILs. After the separation of the product, the IL–catalyst mixture could be recovered by treatment with hydrochloric acid and recycled several times without an obvious loss of catalytic activity.     

The thermochemistry of solvation of imidazolium-based ionic liquids in benzene

ABSTRACT

The present work is devoted to the thermochemical study of solvation of ionic liquids (IL) in benzene. The solution enthalpies of 1-ethyl-3-methylimidazolium tricyanomethanide [EMIM][C(CN)₃], 1-butyl-3-methylimidazolium tetrafluoroborate [BMIM][BF₄], 1-hexyl-3-methylimidazolium hexafluorophosphate [HMIM][PF₆], 1-octyl-3-methylimidazolium tetrafluoroborate [OMIM][BF₄], 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide [EMIM][NTf₂], 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide [BMIM][NTf₂] and 1-butyl-3-methylimidazolium trifluoromethanesulfonate [BMIM][TfO] in benzene were measured. The solvation enthalpies of imidazolium-based IL were calculated. Molar refractions of imidazolium-based IL form literature data on density and refractive indexes of IL were also calculated. The linear correlation between solvation enthalpy and molar refraction of IL was observed. This correlation can be used to calculate the vaporization enthalpy of imidazolium-based IL from solution calorimetry data.     

Effects of temperature and anion species on CO2 permeability and CO2/N2 separation coefficient through ionic liquid membranes

The permeability of carbon dioxide (CO₂) through imidazolium-based ionic liquid membranes was measured by a sweep gas method. Six species of ionic liquids were studied in this work as follows: [emim][BF₄], [bmim][BF₄], [bmim][PF₆], [bmim][Tf₂N], [bmim][OTf], and [bmim][dca]. The ionic liquids were supported with a polyvinylidene fluoride porous membrane. The measurements were performed at T = (303.15 to 343.15) K. The partial pressure difference between feed and permeate sides was 0.121 MPa. The permeability of the CO₂ increases with temperature for the all ionic liquid species. Base on solution diffusion theory, it can be explained that the diffusion coefficient of CO₂ in an ionic liquid affects the temperature dependence more strongly than the solubility coefficient. The greatest permeability was obtained with the [bmim][Tf₂N] membrane. The membrane of [bmim][PF₆] presents the lowest permeability.The separation coefficient between CO₂ and N₂ through the ionic liquid membranes was also investigated at the volume fraction of CO₂ at feed side 0.10. The separation coefficient decreases with the increase of temperature for the all ionic liquid species. The membrane of [emim][BF₄] and [bmim][BF₄] gives the highest separation coefficient at constant temperature. The lowest separation coefficient was obtained from [bmim][Tf₂N] membrane which presents the highest permeability of CO₂.     

Solubility of selected dibasic carboxylic acids in water,in ionic liquid of [Bmim][BF4], and in aqueous [Bmim][BF4] solutions

The solubilities of three dibasic carboxylic acids (adipic acid, glutaric acid, and succinic acid) in water, in the ionic liquid of 1-butyl-3-methyl-imidazolim tetrafluoroborate ([Bmim][BF₄]), and in the aqueous [Bmim][BF₄] solutions have been measured by a solid-disapperance method. The binodal curve of water + [Bmim][BF₄] was also determined experimentally from solid–liquid–liquid coexistence temperature up to near the upper critical solution temperature. Experimental results showed that each acid-containing binary behaved as a simple eutectic system. The solid–liquid equilibrium (SLE) data were correlated with the NRTL model for each binary system. The NRTL model with these determined binary parameters predicted the solid-disappearance temperatures of the aqueous ternary mixtures containing [Bmim][BF₄] and the dibasic acids to within an average absolute deviation of 2.0%.     

Liquid structures of 1-butyl-3-methylimidazolium tetrafluoroborate and carbon dioxide mixtures by X-ray diffraction measurements

X-ray diffraction measurements for the ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate, [BMIM][BF₄], mixed with CO₂ were carried out at high pressures using our developed polymer cell. The intermolecular distribution functions obtained for [BMIM][BF₄]–CO₂ mixtures showed that CO₂ molecules are preferentially solvated to the [BF₄]⁻ anion. The similar preferential solvation was previously observed in analogous 1-btuyl-3-methylimidazolium hexafluorophosphate, [BMIM][PF₆], with a different anion, which is in harmony with the present results in [BMIM][BF₄]–CO₂.     

Isobaric vapor–liquid equilibria for ethanol–water system containing different ionic liquids at atmospheric pressure

Isobaric vapor–liquid equilibrium (VLE) data for ethanol–water systems containing ionic liquids (ILs) 1-methyl-3-methylimidazolium dimethylphosphate ([MMIM][DMP]), 1-ethyl-3-methylimidazolium diethylphosphate ([EMIM][DEP]), 1-butyl-3-methylimidazolium bromide ([BMIM][Br]), 1-butyl-3-methylimidazolium chloride ([BMIM][Cl]) and 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM][PF₆]) at atmospheric pressure (101.32 kPa) were measured with a circulation still. The results showed that the VLE of ethanol–water systems in the presence of different ILs was obviously different from that of the IL-free system. All ILs studied showed a salting-out effect, which gave rise to a change of the relative volatility of ethanol, and even to an elimination of the azeotropic point. It was found that the salting-out effect followed the order of [BMIM][Cl] > [BMIM][Br] > [BMIM][PF₆] and [MMIM][DMP] > [EMIM][DEP], which was ascribed to the preferential solvation ability of the ions resulting from the dissociation of the IL.     

Measurement and Correlation of the Ionic Conductivity of Ionic Liauid-Molecular Solvent Solutions

The ionic conductivity of the solutions formed from 1-n-butyl-3-methylimidazolium tetrafluoroborate （[Bmim][BF4]） or 1-n-butyl-3-methylimidazolium hexafluorophosphate （[Bmim][PF6]） and different molecular solvents （MSs） were measured at 298.15 K. The molar conductivity of the ionic liquids （ILs） increased dramatically with increasing concentration of the MSs. It was found that the molar conductivity of the IL in the solutions studied in this work could be well correlated by the molar conductivity of the neat ILs and the dielectric constant and molar volume of the MSs.     

Experimental methodology for precise determination of density of RTILs as a function of temperature and pressure using vibrating tube densimeters

A specific calibration procedure that allows the accurate determination of densities of room temperature ionic liquids, RTILs, as a function of temperature and pressure using vibrating tube densimeters is presented. This methodology overcomes the problems of common calibration methods when they are used to determine the densities of high density and high viscosity fluids such as RTILs. The methodology is applied for the precise density determination of RTILs 1-ethyl-3-methylimidazolium tetrafluoroborate [Emim][BF₄], 1-butyl-3-methylimidazolium tetrafluoroborate [Bmim][BF₄], 1-hexyl-3-methylimidazolium tetrafluoroborate [Hmim][BF₄], and 1-octyl-3-methylimidazolium tetrafluoroborate [Omim][BF₄] in the temperature and pressure intervals (283.15 to 323.15) K and (0.1 to 60) MPa, respectively. The viscosities of these substances, needed for the estimation of the viscosity-induced errors, were estimated at the same conditions from the experimental measurements in the intervals (283.15 to 323.15) K and (0.1 to 14) MPa and from a specific extrapolation procedure. The uncertainty in the density measurements was estimated in ±0.30 kg · m^?3 which is an excellent value in the working intervals. The results of these RTILs have demonstrated that viscosity-induced errors are relevant and they must be taken into account for a precise density determination. Finally, an alternative tool for a simpler application of this procedure is presented.     

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].     

Amine basicity: measurements of ion pair stability in ionic liquid media

The stability constants relevant to the formation of amine/p-nitrophenol ion pairs have been determined in [bmim][BF₄] solution, in the presence of butylamine, piperidine, and triethylamine, by using spectrophotometric measurements. In order to evaluate how the ion pair stability is affected by ionic liquid structure, piperidine has been chosen as model amine for studies in [bmim][PF₆], [bmim][NTf₂], [bm₂im][NTf₂] and in several [bmim][BF₄]/1,4-dioxane binary mixtures. Data obtained in ionic liquid solutions have been compared with those previously reported in conventional organic solvents.     

Synthesis of crosslinked PEG/IL blend membrane via one-pot thiol–ene/epoxy chemistry

Poly(ethylene glycol) (PEG)-based membranes have obtained considerable attentions for CO₂ separation for their promising CO₂ separation performance and excellent thermal/chemical resistance. In this work, a one-pot thiol–ene/epoxy reaction was used to prepare crosslinked PEG-based and PEG/ionic liquids (ILs) blend membranes. Four ILs of the same cation [Bmim]⁺ with different anions ([BF₄]⁻, [PF₆]⁻, [NTf₂]⁻, and [TCM]⁻) were chosen as the additives. The chemical structure, thermal properties, hydrophilicity, and permeation performance of the resultant membranes were investigated to study the ILs' effects. An increment in CO₂ permeability (~34%) was obtained by optimizing monomer ratios and thus crosslinking network structures. Adding ILs into optimized PEG matrix shows distinct influences in CO₂ separation performance depending on the anions' types, due to the different CO₂ affinities and compatibilities with PEG matrix. Among these ILs, [Bmim][NTf₂] was found the most effective in enhancing CO₂ transport by simultaneously increasing the solubility and diffusivity of CO₂. © 2020 The Authors. Journal of Polymer Science published by Wiley Periodicals LLC. J. Polym. Sci. 2020 , 58, 2575-2585     

离子液体型表面活性剂研究

以1-甲基咪唑为原料, 制备了6个常规离子液体: 1-正丁基-3-甲基咪唑四氟硼酸盐及六氟磷酸盐(简称[bmim][BF₄]及[bmim][PF₆])、1-正己基-3-甲基咪唑四氟硼酸盐及六氟磷酸盐(简称[hmim][BF₄]及[hmim][PF₆])、1-正十六烷基-3-甲基咪唑四氟硼酸盐及六氟磷酸盐(简称[C₁₆mim][BF₄]及[C₁₆mim][PF₆])和4个功能化离子液体: 1-(2-羟乙基)-3-甲基咪唑四氟硼酸盐及六氟磷酸盐(简称[2-hemim][BF₄]及[2-hemim][PF₆])、1-乙氧羰基甲基-3-甲基咪唑四氟硼酸盐及六氟磷酸盐(简称[eocmmim][BF₄]及[eocmmim][PF₆]). 研究了这两类离子液体的一些物理性能, 旨在挖掘离子液体在香料香精化妆品工业中的应用价值. 分别检测了它们与一般溶剂的互溶性, 并测定了它们的表面张力和发泡性能, 实验结果表明, 仅[C₁₆mim][BF₄]和[C₁₆mim][PF₆]具有发泡性能, 发泡力分别为68和120 mm.     

Experiments and model for the surface tension of (MDEA + [Bmim][BF4]) and (MDEA + [Bmim][Br]) aqueous solutions

The surface tension (γ) of 1-butyl-3-methylimidazolium tetrafluoroborate ([Bmim][BF₄]), 1-butyl-3-methylimidazolium bromide ([Bmim][Br]), (N-methyldiethanolamine(MDEA) + [Bmim][BF₄]) and (MDEA + [Bmim][Br]) aqueous solutions were measured by using the BZY-1 surface tension meter. The temperature ranged from (293.2 to 323.2) K. The mass fraction of MDEA ranged from 0.35 to 0.45. A thermodynamic equation was proposed to model the surface tension of (MDEA + ionic liquids) (ILS) aqueous solutions and the calculated results agreed well with the experiments. The effects of temperature, mass fractions of MDEA and ILS on the surface tension were demonstrated on the basis of experiments and calculations.