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1.
Electrical conductivities were measured for the pure ionic liquids [C6mim][Br] (1-hexyl-3-methylimidazolium bromide) and [C8mim][Br] (1-octyl-3-methylimidazolium bromide) at 0.1 MPa from 293.15 to 333.15 K. Conductivity measurements were also made for the binary water + [C6mim][Br] and water + [C8mim][Br] systems and their ternary water + [C6mim][Br] + [C8mim][Br] system at 0.1 MPa and 293.15, 298.15, and 303.15 K. The conductivity data of the pure ionic liquids were correlated by the VFT (Vogel-Tamman-Fulcher) equation, and the fitting parameters and mean absolute deviations were determined. New explanations are presented for the molality-dependent behavior of the conductivity of the binary water + [C6mim][Br] and water + [C8mim][Br] systems. The generalized Young’s rule and the semi-ideal solution theory for conductivity were used to predict the conductivities of the ternary water + [C6mim][Br] + [C8mim][Br] system from the conductivities of its corresponding binary water + [C6mim][Br] and water + [C8mim][Br] subsystems. The predictions are in good agreement with the measured values.  相似文献   

2.
The complex formation of anionic copolymer poly(4-styrenesufonic acid-co-maleic acid) sodium salt (PSSA-co-MA) with surfactant tetradecyltrimethylammonium bromide (TTAB) and surface active ionic liquid (SAIL) 1-tetradecyl-3-methylimidazolium bromide ([C14mim][Br]) has been studied in aqueous media by utilizing various techniques such as tensiometry, conductometry and fluorimetry. Conductometric and tensiometric curve of all the investigated systems demonstrate four break points corresponding to four transition states. All the thermodynamic and surface properties of surfactant-polyelectrolyte systems have been determined by conductance and surface tension measurements respectively. The value of cmc decreases with increasing the concentration of polyelectrolyte for studied systems. But it has been observed that, the lowering in cmc values is more in [C14mim][Br]-PSSA-co-MA system than TTAB-PSSA-co-MA system, although the differences in cmc are not much significant. The lowering in cmc of [C14mim][Br]-PSSA-co-MA system shows that ionic attractions between cationic head group [C14mim]+ and anionic parts (SO3? and COOH), are stronger than those in TTA+ and anionic parts (SO3? and COOH). The results indicated that the [C14mim][Br]-PSSA-co-MA complexes are comparatively more surface active than TTAB-PSSA-co-MA complexes. The fluorescence probe behaviour also confirms cmc value and provides aggregation number (Nagg). Finally all the findings of [C14mim][Br] and TTAB have been compared.  相似文献   

3.
Lysozyme crystals in the presence of 1-butyl-3-methylimidazolium tetrafluoroborate ([C4mim]BF4), 1-butyl-3-methylimidazolium chloride ([C4mim]Cl), 1-butyl-3-methylimidazolium bromide([C4mim]Br), and 1,3-dimethylimidazolium iodine([dmim]I) were prepared, and the influence of ionic liquids (ILs) on the structure and activity change of lysozyme was investigated. Fourier transform infrared spectroscopy revealed the major secondary structures of α-helix and β-sheet for lysozyme. It was interesting to note that increases of the band near 2,935 and 1,656 cm?1 from Raman spectroscopy are attributed to the unfolding of lysozyme molecules. A shift in amide III from 1,230 to 1,270 cm?1 in adding [dmim]I occurs, indicating a transformation from β-sheet to random coil. With regard to adding [C4mim]BF4, [C4mim]Cl, and [C4mim]Br, α-helix and β-sheet are the predominant structures for lysozyme. The activity study showed that the ILs used brought a positive effect. Especially, [dmim]I leads to a drastic increase in relative activity, and its value reaches 50 %.  相似文献   

4.
Experimental measurements of density at different temperatures ranging from 293.15 to 313.15 K, the speed of sound and osmotic coefficients at 298.15 K for aqueous solution of 1-ethyl-3-methylimidazolium bromide ([Emim][Br]), and osmotic coefficients at 298.15 K for aqueous solutions of 1-butyl-3-methylimidazolium chloride ([Bmim][Cl]) in the dilute concentration region are taken. The data are used to obtain compressibilities, expansivity, apparent and limiting molar properties, internal pressure, activity, and activity coefficients for [Emim][Br] in aqueous solutions. Experimental activity coefficient data are compared with that obtained from Debye-Hückel and Pitzer models. The activity data are further used to obtain the hydration number and the osmotic second virial coefficients of ionic liquids. Partial molar entropies of [Bmim][Cl] are also obtained using the free-energy and enthalpy data. The distance of the closest approach of ions is estimated using the activity data for ILs in aqueous solutions and is compared with that of X-ray data analysis in the solid phase. The measured data show that the concentration dependence for aqueous solutions of [Emim][Br] can be accounted for in terms of the hydrophobic hydration of ions and that this IL exhibits Coulombic interactions as well as hydrophobic hydration for both the cations and anions. The small hydration numbers for the studied ILs indicate that the low charge density of cations and their hydrophobic nature is responsible for the formation of the water-structure-enforced ion pairs.  相似文献   

5.
《Fluid Phase Equilibria》2006,242(2):147-153
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.  相似文献   

6.
Density, sound velocity and conductivity measurements are carried out on 1-heptyl-3-methylimidazolium bromide ([C7mim][Br]) in pure water and in aqueous solutions of sodium di-hydrogen citrate, di-sodium hydrogen citrate and tri-sodium citrate over a range of temperatures at atmospheric pressure. The experimental density and sound velocity data are used to calculate the apparent molar volume and isentropic compressibility as a function of temperature and concentration. The effects of temperature and charge on the anion of sodium citrate salts on the apparent molar volume and isentropic compressibility of [C7mim][Br] are studied. It was found that both of the apparent molar volume and isentropic compressibility of [C7mim][Br] in aqueous sodium citrate solutions are larger than those in pure water and increase by increasing temperature. The effects of temperature and charge on the anion of sodium citrate salts on the conductivity behavior of the investigated IL solutions are also studied.  相似文献   

7.
The modulation of aggregation behaviour of ionic liquids (ILs) in aqueous media is one of the important research topics. In the present work, aggregation behaviour of 1-dodecyl-3-methylimidazolium bromide ([C12mim]Br) modulated by beta-cyclodextrin (β-CD) has been investigated by using conductivity, volume, fluorescence, dynamic light scattering and transmission electron microscopy techniques. The results suggested that the addition of β-CD significantly affects the aggregation of [C12mim]Br in aqueous solutions. For example, the apparent critical micelle concentration increases with the increase of β-CD concentration; the average micellar size reduced with the increasing concentration of β-CD, and the process for micelle formation of [C12mim]Br in aqueous β-CD solution is driven by entropy at lower temperature, while driven by enthalpy at higher temperature. It is expected that findings in this study would shed light on the potential applications of IL in supramolecular chemistry.  相似文献   

8.
The effect of imidazolium-based ionic liquids, ([C12mim][Cl] and [C8mim][Cl]), on the acid-base equilibria of two sulfonated indicators has been studied. The presence of ILs leads to decreased pK a values because of the stronger electrostatic interaction of cationic ILs with the basic forms of the indicators with more negative charge. The longer alkyl side chain of [C12mim][Cl] compared to [C8mim][Cl] results in stronger hydrophobic interaction of this IL with the basic forms of the dyes leading to a more effective decrease in the pK a values. Also, the transition points and transition intervals of the acid-base titration curves of the indicators were affected by the presence of ILs. It was found that the IL interaction with acid-base indicators also results in sharpening the acid-base titration curves of the indicators. From these observations, it is concluded that the presence of ILs can tune the pK a values of indicators. All the experiments were performed spectrophotometrically and the results were obtained using curve fitting methods.  相似文献   

9.
The interfacial behavior of β-casein and BSA solutions have been investigated in the presence of imidazolium-based ionic liquid surfactant ([C14mim]Br) at the decane/water interface with the oscillating the drop and interfacial tension relaxation measurements. Both the electrostatic and the hydrophobic interaction between protein and [C14mim]Br played crucial roles as [C14mim]Br concentration increases. Furthermore, it was found that the dilational rheology parameters provided information of the adsorbed layers structure, and the dynamics properties of the adsorbed layers depend on the bulk [C14mim]Br concentration. Moreover, with the concentration of [C14mim]Br increasing, β-casein in the interfacial layer was subject to conformational changes where it gave space to [C14mim]Br molecules in the form of co-adsorb; for BSA/[C14mim]Br solutions, the globule protein BSA deformed and then co-adsorb with [C14mim]Br molecules at the decane/water interface. These results will contribute to elucidation of the influence of the surfactant on the different structure proteins and the wide applications of protein/surfactant systems in practice.  相似文献   

10.
A calorimetric study of dissolution of the ionic liquids (ILs) 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide ([C2mim][NTf2]), 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide ([C6mim][NTf2]), and 1-hexyl-3-methylimidazolium tris(trifluoromethylsulfonyl)methide ([C6mim][CTf3]) into chloroform (CHCl3) is presented with particular focus on [C2mim][NTf2]. The interpretation of the calorimetric data for [C2mim][NTf2] was aided by additional NMR self-diffusion measurements and viscosity measurements that through the Stokes–Einstein equation provided information about the average size of the species present. It is evident that the main equilibrium species are ion pairs and aggregates. An estimate for the enthalpy contribution from aggregate formation for [C2mim][NTf2] was found to be ?2.09 kJ per mol of added IL at 288.2 K and slightly decreasing in magnitude to ?1.11 kJ·mol?1 at 318.2 K. While all three ILs release heat upon dissolution into CHCl3, different temperature trends are observed demonstrating the fine balance of competing contributions from breaking IL interactions, cavity formation for the solutes to reside in, and the establishment of new solute–solvent interactions.  相似文献   

11.
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.  相似文献   

12.
The aim of this work is to obtain further evidence about the salting-out effect produced by the addition of tri-sodium citrate to aqueous solutions of water miscible ionic liquid 1-butyl-3-methylimidazolium bromide ([C4mim][Br]) by evaluating the effect of tri-sodium citrate on the thermodynamic properties of aqueous solutions of this ionic liquid. Experimental measurements of density and sound velocity at different temperatures ranging from (288.15 to 308.15) K, the refractive index at 308.15 K and the liquid–liquid phase diagram at different temperatures ranging from (288.15 to 338.15) K for aqueous solutions containing 1-butyl-3-methylimidazolium bromide ([C4mim][Br]) and tri-sodium citrate (Na3Cit) are taken. The apparent molar volume of transfer of [C4mim][Br] from water to aqueous solutions of Na3Cit have positive values and it increases by increasing salt molality. Although at high IL molality, the apparent molar isentropic compressibility shows similar behaviour with that of the apparent molar volume. However at low concentrations of IL, the apparent molar isentropic compressibility of transfer of [C4mim][Br] from water to aqueous solutions of Na3Cit have negative values. The effects of temperature and the addition of Na3Cit and [C4mim][Br] on the liquid–liquid phase diagram of the investigated system have been studied. It was found that an increase in temperature caused the expansion of the one-phase region. The presence of Na3Cit triggers a salting-out effect, leading to significant upward shifts of the liquid–liquid de-mixing temperatures of the system. The effect of temperature on the phase-forming ability in the system investigated has been studied based on a salting-out coefficient obtained from fitting the binodal values to a Setschenow-type equation for each temperature. Based on cloud point values, the energetics of the clouding process have been estimated and it was found that both of entropy and enthalpy are the driving forces for biphasic formation.  相似文献   

13.
The influence of two salts as additives namely sodium chloride and sodium sulphate and a nonelectrolyte, 2-butoxyethanol on surface chemical and aggregation characteristics of ionic liquids (IL) of 1-octyl-3-methylimidazolium chloride, [C8mim][Cl], 1-octyl-3-methylimidazolium bromide, [C8mim][Br], and 1-octyl-3-methylimidazolium iodide, [C8mim][I] in aqueous media were monitored through surface tension and small angle neutron scattering measurements. The addition of salts drastically decreased the critical aggregation concentration (CAC) and increased the area per adsorbed IL molecule. The co-ions of salts modify the surface of IL molecules and aggregates through various interactions such as charge neutralization, specific interactions and dehydration The results obtained by analyzing the SANS curves in the whole Q range showed that the oblate ellipsoidal shape of the aggregates of ionic liquids is un-altered upon the addition of additives. However the additives facilitate the growth of the aggregates in to microstructures with cubic packing at high salt concentrations.  相似文献   

14.
咪唑基离子液体的物理化学性质估算及预测(英文)   总被引:1,自引:0,他引:1  
根据经验和半经验方程及空隙模型理论,可以估算及预测离子液体在298.15K的物理化学性质.本文讨论了离子液体的分子体积,密度,标准熵,晶格能,表面张力,等张比容,摩尔蒸发焓,空隙体积,空隙率和热膨胀系数.通过实验测得的三种离子液体1-乙基-3-甲基咪唑硫酸乙酯([C2mim][EtSO4)]),1-丁基-3-甲基咪唑硫酸辛酯([C4mim][OcSO4])和1-乙基-3-甲基咪唑双三氟甲磺酰亚胺盐([C2mim][NTf2])的密度和表面张力估算了它们的其它物理化学性质.由这三种离子液体的分子体积及等张比容预测了同系列中其它离子液体[Cnmim][EtSO4],[Cnmim][OcSO4]和[Cnmim][NTf2](n=1-6)的分子体积及等张比容,由此计算出它们的密度及表面张力.进而预测了它们的物理化学性质.将预测的离子液体[C4mim][NTf2]和[C2mim][OcSO4]的密度值与文献报导的实验值进行比较,其偏差在实验误差范围内.最后,将由Kabo经验方程计算的七个离子液体[C2mim][EtSO4]、[C4mim][OcSO4]、[C2mim][NTf2]、[C4mim][NTf2]、丁基三甲基铵双三氟甲磺酰亚胺盐([N4111][NTf2])、甲基三辛基铵双三氟甲磺酰亚胺盐([N8881][NTf2])和1-辛基-3-甲基吡啶四氟硼酸盐([m3opy][BF4])的摩尔蒸发焓与由Verevkin简单规则预测的摩尔蒸发焓进行比较,发现两者符合很好.因此,在缺乏密度和表面张力实验数据的情况下,可以用Verevkin简单规则来预测离子液体的摩尔蒸发焓.  相似文献   

15.
Compared to the general ionic liquids (ILs), a significant deviation of the binary mixtures of 1-decyl-3-methylimidazolium tri(hexafluoroacetylaceto)-copper(II) ([C10mim][Cu(hfacac)3]) with methanol was found, indicating the way methanol interacts with ILs might be governed by the special structure of the chelating anion. IR results showed that the (C2-H) of 1-decyl-3-methylimidazolium hexafluoroacetylacetonate ([C10mim][hfacac]) blue-shifted more significantly than that of [C10mim][Cu(hfacac)3], meanwhile the (C=O) red-shifted in [C10mim][Cu(hfacac)3], which is contrast with that in [C10mim][hfacac]. Two-dimensional correlation analysis of the FTIR spectra indicated that the chelating cavity has little effect on the sequence of the ILs sites that interact with methanol. Combined with small angle X-ray scattering (SAXS) results, the picture of mixing processes in these two systems were proposed. Methanol interacts directly with the anion followed by the cation in [C10mim][hfacac], while methanol preferentially enters the chelating cavity and enhances the packing effect in the [C10mim][Cu(hfacac)3] system.  相似文献   

16.
离子液体型表面活性剂研究   总被引:2,自引:0,他引:2  
易封萍  李积宗  陈斌 《化学学报》2008,66(2):239-244
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.  相似文献   

17.
The oily sludge would cause environment pollution, and would cause the heavy oil waste. Therefore, it was vital for us to find novel methods to obtain heavy oil from the oily sludges. In this study, the [C12mim][PF6] and [C12mim][Br] ionic liquids(ILs) were used to enhance the oil recovery. The toluene could obtain the highest oil recovery, and both the two ILs could increase the oil recovery. Toluene could obtain the highest oil recovery (89.4 wt%), and n-octane could obtain the lowest oil recovery (76.8 wt%). [C12mim] [PF6] could efficiently increase the heavy oil recovery to 91.2 wt%(by toluene). The [C12mim][Br] could increase the heavy oil recovery further. Both the [C12mim] [PF6] and the [C12mim][Br] ionic liquids could increase the heavy ois C/H ratio, decrease heavy oil viscosity and increase the sands hydrophilicity. The [C12mim][Br] ionic liquids showed better effect. In addition, the ionic liquids could increase the solvents recovery, and the ionic liquids recovery were high. Therefore, the ionic liquids enhanced oil recovery could be recycled to ten times. The two ionic liquids could effectively decrease the heavy oil interaction force, and when the ionic liquids increased to 200 ppm, the force remained stable. In the end, the ionic liquids enhancing solvent extraction mechanism was put forward.  相似文献   

18.
The activity and stability of laccase and their kinetic mechanisms in water soluble ionic liquids (ILs): 1-butyl-3-methyl imidazolium chloride [C4mim][Cl], 1-octyl-3-methyl imidazolium chloride [C8mim][Cl], and 1-decyl-3-methyl imidazolium chloride [C10mim][Cl] were investigated. The results show that an IL concentration up to 10% is satisfactory for initial laccase activity at pH 9.0. The laccase stability was well maintained in [C4mim][Cl] IL when compared to the control. The inactivation of laccase increases with the length of the alkyl chain in the IL: [C10mim][Cl] > [C8mim][Cl] > [C4mim][Cl]. The kinetic studies in the presence of ABTS as substrate allowed calculating the Michaelis–Menten parameters. Among the ILs, [C4mim][Cl] was the suitable choice attending to laccase activity and stability. Alkyl chains in the ions of ILs have a deactivating effect on laccase, which increases strongly with the length of the alkyl chain.  相似文献   

19.
Densities and viscosities were measured for pure ionic liquid [C6mim][Br] (1-hexyl-3-methylimidazolium bromide) and the binary system (water + [C6mim][Br]) at 0.1 MPa and in the (293.15 to 333.15) K range. The excess molar volume and viscosity deviation were calculated and correlated by Redlich–Kister polynomial expansions. The fitting parameters and the standard deviations were determined.  相似文献   

20.
Several imidazolium-based ionic liquids (ILs) with varying cation alkyl chain length (C4–C10) and anion type (tetrafluoroborate ([BF4]), hexafluorophosphate ([PF6]) and bis(trifluoromethylsulfonyl)imide ([Tf2N])) were used as reaction media in the microwave polymerization of methacrylate-based stationary phases. Scanning electron micrographs and backpressures of poly(butyl methacrylate-ethylene dimethacrylate) (poly(BMA-EDMA)) monoliths synthesized in the presence of these ionic liquids demonstrated that porosity and permeability decreased when cation alkyl chain length and anion hydrophobicity were increased. Performance of these monoliths was assessed for their ability to separate parabens by capillary electrochromatography (CEC). Intra-batch precision (n = 3 columns) for retention time and peak area ranged was 0.80–1.13% and 3.71–4.58%, respectively. In addition, a good repeatability of RSDRetention time = <0.30% and ∼1.0%, RSDPeak area = <1.30% and <4.3%, and RSDEfficiency = <0.6% and <11.5% for intra-day and inter-day, respectively exemplify monolith performance reliability for poly(BMA-EDMA) fabricated using 1-hexyl-3-methylimidazolium tetrafluoroborate ([C6mim][BF4]) porogen. This monolith was also tested for its potential in nanoLC to separate protein digests in gradient mode. ILs as porogens also fabricated different alkyl methacrylate (AMA) (C4–C18) monoliths. Furthermore, employing binary IL porogen mixture such as 1-butyl-3-methylimidazolium tetrafluoroborate ([C4mim][BF4]) and 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([C4mim][Tf2N]) successfully decreased the denseness of the monolith, than when using [C4mim][Tf2N] IL alone, enabling a chromatographic run to be performed with 1:1 ratio produced baseline separation for the analytes. The combination of ILs and microwave irradiation made polymer synthesis very fast (∼10 min), entirely green (organic solvent-free) and energy saving process.  相似文献   

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