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1.
In recent years, great progress has been made in the dissolution of cellulose with ionic liquids (ILs). However, the mechanism of cellulose dissolution, especially the role the IL cation played in the dissolution process, has not been clearly understood. Herein, the mixtures of cellulose with a series of imidazolium‐based chloride ionic liquids and 1‐butyl‐3‐methyl pyridinium chloride ([C4mpy]Cl) were simulated to study the effect that varying the heterocyclic structure and alkyl chain length of the IL cation has on the dissolution of cellulose. It was shown that the dissolution of cellulose in [C4mpy]Cl is better than that in [C4mim]Cl. For imidazolium‐based ILs, the shorter the alkyl chain is, the higher the solubility will be. In addition, an all‐atom force field for 1‐allyl‐3‐methyl imidazolium cation ([Amim]+) was developed, for the first time, to investigate the effect the electron‐withdrawing group within the alkyl chain of the IL cation has on the dissolution of cellulose. It was found that the interaction energy between [Amim]+ and cellulose was greater than that between [C3mim]+ and cellulose, indicating that the presence of electron‐withdrawing group in alkyl chain of the cation enhanced the interaction between the cation and cellulose due to the increase of electronegativity of the cations. These findings are used to assess the cationic effect on the dissolution of cellulose in ILs. They are also expected to be important for rational design of novel ILs for efficient dissolution of cellulose.  相似文献   

2.
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   

3.
Synthesis and Characterization of six novel N,N-dioctylsuccinamate based room temperature ionic liquids (RTILs) bearing imidazolium, pyridinium, ester imidazolium, and quaternary ammonium cations is reported. Extraction of Pb(II) and Co(II) by these RTILs has been investigated. Ionic liquids (ILs) synthesized were [C4mim][N88SA], [C8mim][N88SA], [C4Py][N88SA], [C8Py][N88SA], [α-mim-ester][N88SA] and [N2244][N88SA] termed as L1, L2, L3, L4, L5 and L6 respectively. Liquid-liquid extraction was performed and all the six systems showed excellent extractability results for both Pb(II) and Co(II). During the process of extraction several factors i.e., nature of cation, pH of the aqueous phase, equilibration time, and initial metal ion concentration were investigated. The extraction efficiency of above 98 % for all types of extractants was observed. The nature of cation its concentration, equilibration time, and pH of the aqueous phase significantly influenced the extraction efficiency. Maximum extraction was observed at pH values between 4 and 8 and optimum contact time was observed to be 40–45 min. Increasing the metal ion concentration decreased the extraction efficiency. The extraction efficiency of both metal ions decreased in the order [N88SA][C8mim] (L2) > [α-mim-Ester][N88SA] (L5) > [N88SA][C4mim] (L1). This is evident from the order of extraction behaviour that increasing the bulkiness of cation, results in stronger complexation, hence increasing extraction.  相似文献   

4.
In this work, experimental data of isobaric vapour–liquid equilibria for the ternary system ethanol + water + 1-hexyl-3-methylimidazolium chloride ([C6mim][Cl]) and for the corresponding binary systems containing the ionic liquid (ethanol + [C6mim][Cl], water + [C6mim][Cl]) were carried out at 101.300 kPa. VLE experimental data of binary and ternary systems were correlated using the NRTL equation. In a previous work [N. Calvar, B. González, E. Gómez, A. Domínguez, J. Chem. Eng. Data 51 (2006) 2178–2181], the VLE of the ternary system ethanol + water + [C4mim][Cl] was determined and correlated, so we can study the influence of different ionic liquids in the behaviour of the azeotropic mixture ethanol–water.  相似文献   

5.
The solubilities of 1alkyl‐3‐methylimidazolium chloride, [Cnmim][Cl], where n=4, 8, 10, and 12, in 1octanol and water have been measured by a dynamic method in the temperature range from 270 to 370 K. The solubility data was used to calculate the 1octanol/water partition coefficients as a function of temperature and alkyl substituent. The melting point, enthalpies of fusion, and enthalpies of solid–solid phase transitions were determined by differential scanning calorimetry, DSC. The solubility of [Cnmim][Cl], where n=10 or 12 in 1octanol is comparable and higher than that of [C4mim][Cl] in 1octanol. Liquid 1n‐octyl‐3‐methylimidazolium chloride, [C8mim][Cl], is not miscible with 1octanol and water, consequently, the liquid–liquid equilibrium, LLE was measured in this system. The differences between the solubilities in water for n=4 and 12 are shown only in α1 and γ1 solid crystalline phases. Additionally, the immiscibility region was observed for the higher concentration of [C10mim][Cl] in water. The intermolecular solute–solvent interaction of 1butyl‐3‐methylimidazolium chloride with water is higher than for other 1alkyl‐3‐methylimidazolium chlorides. The data was correlated by means of the UNIQUAC ASM and two modified NRTL equations utilizing parameters derived from the solid–liquid equilibrium, SLE. The root‐mean‐square deviations of the solubility temperatures for all calculated data are from 1.8 to 7 K and depend on the particular equation used. In the calculations, the existence of two solid–solid first‐order phase transitions in [C12mim][Cl] has also been taken into consideration. Experimental partition coefficients (log P) are negative at three temperatures; this is evidence for the possible use of these ionic liquids as green solvents.  相似文献   

6.
The solubility of CO2 in imidazolium ionic liquids (ILs), 1-butyl-3-methyl imidazolium tetrafluoroborate ([bmim][BF4]), 1-hexyl-3-methyl imidazolium tetrafluoroborate ([hmim][BF4]) and 1-octyl-3-methyl imidazolium tetrtafluoroborate ([omim][BF4]) was determined at 305-25 K and pressures from 1 to 9 MPa. The influence of chain length of alkyl substituents on the imidazolium cation on the solubility of CO2 was investigated. The differences in solubility with chain length are in the sequence [omim][BF4] > [hmim][BF4] > [bmim][BF4]. The solubility data were correlated by the extended Henry's law, and enthalpy, Gibbs free energy and entropy changes were obtained.  相似文献   

7.
The effect of different anions within the ionic liquid in the characteristics of solid polymer electrolytes (SPEs) based on P(VDF‐TrFE) has been investigated. 1‐ethyl‐3‐methylimidazolium acetate, [C2mim][OAc], 1‐ethyl‐3‐methylimidazolium triflate, [C2mim][(CF3SO3)], 1‐ethyl‐3‐methylimidazolium lactate, [C2mim][Lactate], 1‐ethyl‐3‐methylimidazolium thiocyanate, [C2mim][SNC] and 1‐ethyl‐3‐methylimidazolium hydrogen sulfate [C2mim][HSO4] have been used in SPE prepared by solvent casting. The polymer phase, thermal and electrochemical properties of the SPE have been determined. The thermal and electrical properties of the SPEs strongly depend on the selected IL, as determined by their different interactions with the polymer matrix. The room temperature ionic conductivity increases in the following way for the different anions: [SNC]>[CF3SO3)]>[HSO4]>[Lactate]>[OAc], which is mainly dependent on the viscosity of the ionic liquid.  相似文献   

8.
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 [Cnmim]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 (KA) and the limiting molar conductance (Λm0). 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 Λm0 values decrease with increasing alkyl chain length of the cations in all the molecular solvents, whereas the KA 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 KA 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.  相似文献   

9.
At present, there is a considerable amount of work devoted to the study of the thermophysical properties of pure ionic liquids, which contrasts with the few data available for their mixtures. One of the most appealing characteristics of ionic liquids is the capability of subtly changing the chemical structure of the cation and anion in order to design appropriate solvents for specific applications. Mixtures of ionic liquids increase enormously this specificity, due to the unlimited combinations that arise from mixing two or more ionic liquids. In this context, the study of the thermophysical properties of these mixtures is revealed as a fundamental task. In this work the viscosities of the ionic liquid binary mixtures with a common ion ([C6mim] + [C2mim])[BF4], ([C6mim] + [C4mim])[BF4], [C4mim]([BF4] + [MeSO4]) and [C4mim]([PF6] + [BF4]) were determined within the temperature range (298.15–308.15) K. The temperature dependence of the viscosity for pure liquids is analyzed by means of the Vogel-Tammann-Fulcher equation and several mixing rules are applied for the mixtures.  相似文献   

10.
Density, speed of sound and refractive index of the imidazolium-based ionic liquids (ILs), 1-methyl-3-octylimidazolium chloride [C8mim][Cl], 1-butyl-3-methylimidazolium methyl sulfate [C4mim][C1OSO3], and 1-butyl-3-methylimidazolium octyl sulfate [C4mim][C8OSO3], have been measured in the temperature range from 283.15 to 343.15 K. Experimental density and speed of sound have been used to calculate the internal pressure p i of the ILs. The p i values were found to be higher than those of water and molecular organic liquids, but lower than those of classical molten salts. We also calculated molar refraction R M from the measured refractive index n D in the temperature range from 288.15 to 343.15 K. Refractive indices of ILs were also higher than those of normal organic liquids, but comparable to long-chain hydrocarbon organic solvents. The structure-property correlation of the ILs has been discussed and the results have been compared to our earlier studies (Kumar in J. Solution Chem. 37:203–214, 2008).  相似文献   

11.
Song and Mason equation of state (EOS) with a simple modification has been extended to modelling PVT properties of ionic liquids (ILs). The considered ILs are [C1mim][MeSO4], [C1mim][CH3OC2H5SO4], [C1mim][(CH3)2PO4], [C2mim][MeSO4], [C2mim][BF4], [C2mim][SCN], [C2eim][NTf2], [C4mim][C(CN)3], [C4mim][CF3SO3], [C4mim][SCN], [C5mim][NTf2], [C8mim][NTf2], [(C6H13)3P(C14H29)][Cl], [(C6H13)3P(C14H29)][NTf2], [(C6H13)3P(C14H29)][Ac], [C3mpyr][NTf2], [C4mpyr][NTf2] and [Py][C2H5OC2H4SO4]. Three temperature-dependent parameters in the proposed EOS have been scaled as functions of reduced temperature with the use of the law of corresponding states. It is shown that the knowledge of just critical temperature and critical density is sufficient to predict the PVT properties of these ILs. The overall average absolute deviation of calculated densities from literature values for 1347 data points of 18 ILs was found to be 0.58%. The predicted density of ILs from proposed EOS has been compared with those obtained by other literature work. Moreover, we indicate that the Zeno line regularity can well be predicted by proposed model for ILs.  相似文献   

12.
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   

13.
Pretreatment of lignocellulosic biomass with ionic liquids (ILs) has been extensively studied, being regarded as one of the most promising methods for obtaining fermentable sugars. In this research, it was investigated the production of ethanol from sugars released from sugarcane bagasse pretreated with the ionic liquids [C4mim][OAc] and [C2mim][OAc], hydrolysed with Penicillium echinulatum enzymes and using Saccharomyces cerevisiae and Schizosaccharomyces pombe. Yields of about 43 and 56% of ethanol were observed for S. cerevisiae and biomass pretreated with [C2mim][OAc] and [C4mim][OAc], respectively. S. pombe yielded 52 and 78% ethanol for [C2mim][OAc] and [C4mim][OAc], respectively. These results indicate that S. pombe showed best performance for alcoholic fermentation from sugars released from pretreated biomass by ILs.  相似文献   

14.
Micellization behavior of the twin-tailed surfactants can be modulated by the addition of various modifiers. Ionic liquids (ILs) are one of them and are documented here. The beauty of these environmentally benign neoteric molecules lies in their structural versatility. Here, we have investigated the effect of three ILs: 1-butyl-3-methylimidazolium bromide ([C4mim][Br]), 1-hexyl-3-methylimidazolium bromide ([C6mim][Br]), and 1-octyl-3-methylimidazolium bromide ([C8mim][Br]) on the aggregation and surface adsorption behavior of cationic gemini surfactant, bis(hexadecyldimethyl ammonium)propane dibromide (16-3-16) through experimentally measured electrical conductivities, surface tensions, and by spectral methods (UV-vis absorbance and fluorescence measurements). The main focus of the study is to observe the effect of added ILs on the critical micelle concentration (cmc), various surface parameters, aggregation number, and size of the aggregates of gemini surfactant. The results show that the more hydrophobic ILs, that is, [C6mim][Br] and [C8mim][Br] behave as electrolyte at lower concentration and cosurfactant at higher concentration, whereas moderately hydrophobic IL [C4mim][Br] acts as an electrolyte at all concentration ranges studied. The modulating effects of ILs were also compared with conventional electrolyte (NaBr) at similar conditions.  相似文献   

15.
Solubilities of ammonia in basic imidazolium ionic liquids   总被引:1,自引:0,他引:1  
Solubilities of ammonia in four conventional imidazolium ionic liquids: [Cnmim][BF4] (n = 2, 4, 6, 8) have been measured. Isothermally fixed temperatures are 293.15, 303.15, 313.15, 323.15 and 333.15 K; the pressure is from 0 to 1.0 MPa. High solubilities of ammonia are found, and it is also found that the solubilities of ammonia increase when the length of cations’ alkyl increases (the ILs have the same anion), that is: [C8mim]+ > [C6mim]+ > [C4mim]+ > [C2mim]+. The solubility data have been correlated by the Krichevisky–Kasarnovsky equation, and then Henry's constants and partial molar volumes of NH3 at infinite dilution are obtained. The thermodynamic properties such as solution enthalpy (ΔsolH), solution Gibbs free energy (ΔsolG), solution entropy (ΔsolS), and solution heat capacity (ΔsolCp) of these systems are obtained.  相似文献   

16.
Absalan G  Akhond M  Sheikhian L 《Talanta》2008,77(1):407-411
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 pKa 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.  相似文献   

17.
1-烷基-3-甲基咪唑双三氟甲基磺酰胺型离子液体(Cnmim][NTf2])被认为是最有希望用于核燃料循环中的分离试剂之一, 虽然其化学结构在辐照过程中变化不大, 但在受到γ辐照后会发生明显的变色, 因此有必要研究该类离子液体的变色原因. 本文以60Co为辐照源, 系统研究了辐照后不同C(1)-烷基链长和咪唑环上C(2)位上的H被甲基取代后离子液体的紫外-可见(UV-Vis)吸收光谱行为, 并结合辐照后离子液体荧光光谱和质谱的变化, 分析了导致该类离子液体辐照后颜色加深的原因. 结果表明, 随着咪唑环上C(1)―烷基链长度和剂量增大, 离子液体颜色加深; 而C(2)位上的H被甲基取代后颜色明显变浅. 辐照后咪唑型离子液体的变色主要来自于辐照后产生的烷基侧链含双键的咪唑阳离子, 咪唑阳离子二聚体和含氟咪唑化合物. 此外, γ辐照引起咪唑阳离子易发生π-π堆积, 而聚集态含量增加也会引起颜色加深.  相似文献   

18.
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   

19.
Many applications of ionic liquids (ILs) are closely related with their microstructure in mixtures. For example, morphology and pore size of the MCM-41 prepared in aqueous ILs are greatly dependent on the aggregation behavior of the ILs in water. Therefore, the study on the microstructure of ILs in aqueous solutions is of great importance. In this work, 1H NMR, dynamic light scattering and attenuated total reflection infrared spectroscopy have been used to investigate the temperature effect on the structures of aqueous 1-butyl-3-methylimidazolium tetrafluoroborate ([C4mim][BF4]) solutions. It was shown that the size of the IL aggregates becomes larger with decreasing temperature. When the system temperature is below the upper critical solution temperature (UCST) of the binary mixture at about 4 °C, the aggregate size of the IL is larger than 1000 nm. Additionally, the two-dimensional IR results reveal that at low IL concentrations, H2O can interact with [BF4] prior to the CH groups of the imidazolium ring, whereas cation and anion of the IL tend to form aggregate at high IL concentrations. With the decrease of temperature, the interactions between cation and anion of the IL become stronger, but those between the IL and water become weaker, thereby resulting in the growth of the aggregate of cation with anion of the IL. This result may give a reasonable explanation for the origin of the UCST behavior of aqueous [C4mim][BF4] solution.  相似文献   

20.
Cao Q  Quan L  He C  Li N  Li K  Liu F 《Talanta》2008,77(1):160-165
Enzyme activity and partition behavior in aqueous biphasic systems (ABSs) consisting of ionic liquid (IL) and salt (IL-ABSs) were investigated to increase our understanding of IL-ABSs and shed light on their application potential as enzyme extraction system. With horseradish peroxidase (HRP) as the model enzyme, several effects of alkylimidazolium chloride-K2HPO4 ABSs on activity and partition behavior of enzyme were studied including alkyl chain length of ILs and concentrations of each component. High lyotropic ILs (1-butyl-3-methylimidazolium and 1-ethyl-3-methylimidazolium chloride) and adequate water content (>40%) were both essential for the activity maintenance of HRP in IL-ABS. 1-Butyl-3-methylimidazolium chloride ([C4mim]Cl) was found to be an appropriate IL for phase forming and HRP activity retaining. After optimization of phase condition, about 80% HRP amount was distributed in the IL-rich upper phase, and greater than 90% enzyme activity was obtained. Moreover, compared with the commonly used polymer-based ABSs, this [C4mim]Cl-ABS has a much lower viscosity, which is very beneficial to the experimental operation. Therefore, the tested IL-ABS could be considered as a potential enzyme extraction system.  相似文献   

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