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1.
Vapour pressure osmometery (VPO) measurements at T = 308.15 K for {[C6mim][Cl] + water}, {[C6mim][Cl] + (0.005, 0.0155, and 0.0263) mol · kg−1 PEG2000 + water} and {[C6mim][Cl] + (0.0017, 0.0052, and 0.0088) mol · kg−1 PEG6000 + water} systems and isopiestic measurements at T = 298.15 K for {[C6mim][Cl] + PEG2000 + water} and {[C6mim][Cl] + PEG6000 + water} systems have been carried out. The VPO measurements were carried out at very low concentrations of PEG and from which the values of the water activities, osmotic coefficients, vapour pressure and activity coefficients were obtained. The data obtained from the VPO method show that over the whole concentration range of the ionic liquid (IL), the activity coefficients of [C6mim][Cl] in the presence of PEG2000 are increased. Although, at high IL concentrations, the values of the activity coefficient of [C6mim][Cl] in the presence of PEG6000 are also increased, however for low concentrations of IL the values of the activity coefficient of [C6mim][Cl] in pure water are larger than those in aqueous PEG6000 solutions. For a known IL concentration, the values of water activity coefficient for the binary {[C6mim][Cl] + water} system are larger than those for the ternary {[C6mim][Cl] + PEG + water} systems and decrease by increasing the concentration of PEG or decreasing the molar mass of PEG. The constant water activity lines of the all ternary systems obtained from the isopiestic method show positive deviation from the linear isopiestic relation (Zdanovskii–Stokes–Robinson rule) derived using the semi-ideal hydration model. The results have been interpreted in terms of the solute–water and solute–solute interactions.  相似文献   

2.
(Vapour + liquid) equilibrium data (water activity, vapour pressure, osmotic coefficient, and activity coefficient) of binary aqueous solutions of 1-hexyl-3-methylimidazolium chloride ([C6mim][Cl]), methyl potassium malonate, and ethyl potassium malonate and ternary {[C6mim][Cl] + methyl potassium malonate} and {[C6mim][Cl] + ethyl potassium malonate} aqueous solutions were obtained through the isopiestic method at T = 298.15 K. These results reveal that the ionic liquid behaves as surfactant-like and aggregates in aqueous solutions at molality about 0.4 mol · kg−1. The constant water activity lines of all the ternary systems investigated show small negative deviations from the linear isopiestic relation (Zdanovskii–Stokes–Robinson rule) derived using the semi-ideal hydration model. The density and speed of sound measurements were carried out on solutions of methyl potassium malonate and ethyl potassium malonate in water and of [C6mim][Cl] in aqueous solutions of 0.25 mol · kg−1 methyl potassium malonate and ethyl potassium malonate at T = (288.15 to 308.15) K at atmospheric pressure. From the experimental density and speed of sound data, the values of the apparent molar volume, apparent molar isentropic compressibility and excess molar volume were evaluated and from which the infinite dilution apparent molar volume and infinite dilution apparent molar isentropic compressibility were calculated at each temperature. Although, there are no clear differences between the values of the apparent molar volume of [C6mim][Cl] in pure water and in methyl potassium malonate or ethyl potassium malonate aqueous solutions, however, the results show a positive transfer isentropic compressibility of [C6mim][Cl] from pure water to the methyl potassium malonate or ethyl potassium malonate aqueous solutions. The results have been interpreted in terms of the solute–water and solute–solute interactions.  相似文献   

3.
Heat capacities in a range of temperatures of (5 to 370) K, enthalpies and temperatures of phase transitions for 1-ethyl-3-methylimidazolium bis(triflamide) ([C2mim][NTf2]) and 1-octyl-3-methylimidazolium bis(triflamide) ([C8mim][NTf2]) have been determined by adiabatic calorimetry. [C2mim][NTf2] has been found to form four crystalline phases with different fusion temperatures. Formation of the phases can be controlled by the temperature of annealing during crystallization. [C8mim][NTf2] forms three sequences of crystalline modifications, each including two polymorphs. Based on results of the measurements, thermodynamic functions for the compounds under study have been calculated.A heat-capacity anomaly near T = 230 K reported earlier for [C4mim][NTf2] and [C6mim][NTf2] have been found in some crystalline modifications of both the studied compounds. The position of the anomaly depends on the temperature of annealing of the crystals.  相似文献   

4.
A protocol for Pd-catalyzed stereoselective co-polymerization of propene and carbon monoxide using chiral ligands, such as (2S,3S)-DIOP and (R)-P-Phos in [C4mim][PF6]/[C6mim][PF6] as an ionic liquid medium was developed. With (2S,3S)-DIOP as chiral ligand and [C4mim][PF6] as medium, the Pd-catalyzed co-polymerization of propene and CO gave almost completely regioregular polyketones, and the product polymer showed moderate stereoregularity (61% of ℓ-diads). The highest molar optical rotation = +15.9 and polydispersity = 1.2 were attained when (R)-P-Phos was used as the ligand and [C6mim]PF6 as the solvent. The co-polymer exhibited regioregularity of H–H/H–T/T–T (%) = 17:66:17.  相似文献   

5.
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   

6.
The solubilities of ionic liquids in the ternary systems (ionic liquid + H2O + inorganic salt) were reported at 298.15 K and atmospheric pressure. The examined ionic liquids are [C4mim][PF6] (1-n-butyl-3-methylimidazolium hexafluorophosphate), [C8mim][PF6] (1-n-octyl-3-methylimidazolium hexafluorophosphate), and [C8mim][BF4] (1-n-octyl-3-methylimidazolium tetrafluoroborate). The examined inorganic salts are the chloride-based salts (sodium chloride, lithium chloride, potassium chloride, and magnesium chloride) and the sodium-based salts (sodium thiocyanate, sodium nitrate, sodium trifluoroacetate, sodium bromide, sodium iodide, sodium perchlorate, sodium acetate, sodium hydroxide, sodium dihydrogen phosphate, sodium phosphate, sodium tetrafluoroborate, sodium sulfate, and sodium carbonate). The effects of the cations and the anions of the ionic liquids and of the inorganic salts on the solubility of the ionic liquids in the ternary solutions were systematically compared and discussed.  相似文献   

7.
The alkyl chain length of 1-alkyl-3-methylimidazolium bromide ([Rmim][Br], R = propyl (C3), hexyl (C6), heptyl (C7), and octyl (C8)) was varied to prepare a series of room-temperature ionic liquids (RTILs), and experimental measurements of density and speed of sound at different temperatures ranging from (288.15 to 308.15) K for their aqueous and methanolic solutions in the dilute concentration region (0.01 to 0.30) mol · kg?1 were taken. The values of the compressibilities, expansivity and apparent molar properties for [Cnmim][Br] in aqueous and methanolic solutions were determined at the investigated temperatures. The obtained apparent molar volumes and apparent molar isentropic compressibilities were fitted to the Redlich–Mayer and the Pitzer’s equations from which the corresponding infinite dilution molar properties were obtained. The values of the infinite dilution molar properties were used to obtain some information about solute–solvent and solute–solute interactions. The thermodynamic properties of investigated ionic liquids in aqueous solutions have been compared with those in methanolic solutions. Also, the comparison between thermodynamic properties of investigated solutions and those of electrolyte solutions, polymer solutions, cationic surfactant solutions and tetraalkylammonium salt solutions have been made.  相似文献   

8.
Partition coefficients for a series of dinitrophenylated (DNP) amino acids in biphasic systems composed of hydrophobic ionic liquids and water were experimentally determined. The ionic liquids used were three 1-alkyl-3-methylimidazolium tetrafluoroborates, [Cnmim][BF4], with alkyl chain substituents hexyl, octyl, and decyl. The liquid–liquid phase diagram for the system ([C10mim][BF4] + water) was experimentally determined. DNP amino acids distribute preferentially to the IL-rich phase and ([C10mim][BF4] + water) was found to be the system with the lowest partition coefficients for the solutes studied. The experimental partition coefficients decrease as the size of the alkyl side chain in the ionic liquids increases. The free energy of transfer of a methylene group between phases was calculated through the partition coefficients, which provides a measure of the relative hydrophobicity of the equilibrium phases. It was found that the system ([C10mim][BF4] + water) presents a lower free energy (and thus a lower relative hydrophobicity) than the system ([C8mim][BF4] + water). In order to better understand this result, the micellar behavior of the three ionic liquids was studied. Electrical conductivities of several aqueous solutions of the ionic liquids were measured to determine the critical micelle concentration (CMC) and the degree of micelle ionization, α, of the three ionic liquids. From these two properties it was possible to obtain the free energy of micellization, ΔGmic, for the ionic liquids.  相似文献   

9.
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   

10.
A new amino acid ionic liquid (AAIL) [C3mim][Val] (1-propyl-3-methylimidazolium valine) was prepared by the neutralization method. Using the solution-reaction isoperibol calorimeter, molar solution enthalpies of the ionic liquid [C3mim][Val] with known amounts of water and with different concentrations in molality were measured at T = 298.15 K. In terms of standard addition method (SAM) and Archer’s method, the standard molar enthalpy of solution for [C3mim][Val] without water, ΔsHm = (−55.7 ± 0.4) kJ · mol−1, was obtained. The hydration enthalpy of the cation [C3mim]+, ΔH+ ([C3mim]+) = −226 kJ · mol−1, was estimated in terms of Glasser’s theory. Using the RD496-III heat conduction microcalorimeter, the molar enthalpies of dilution, ΔDHm(mi  mf), of aqueous [C3mim][Val] with various values of molality were measured. The values of ΔDHm(mi  mf) were fitted to Pitzer’s ion-interaction model and the values of apparent relative molar enthalpy, φL, calculated using Pitzer’s ion-interaction model.  相似文献   

11.
Partitioning in aqueous biphasic systems (ABS) is widely recognized today as a rapid, gentle, and highly efficient technique for the separation of soluble as well as particulate biomaterials. This technique has gained increasing attention as the separation method of choice in biotechnology. In recent years, a new approach has been proposed based on the use of ionic liquids (ILs) as adjuvants for the separation and purification of bio-molecules using polymer-based ABS. In this regard, the influence of IL 1-butyl-3-methylimidazolium bromide ([C4mim]Br) on the phase behavior and extraction capability of {PEG 600 + tri-potassium citrate (K3C6H5O7)} ABS for l-tyrosine (Tyr) is investigated here. For this purpose, phase diagrams and the liquid–liquid equilibrium (LLE) data for the {PEG 600 + K3C6H5O7} ABS with the addition of small quantities of IL were determined at T = 298.15 K. It was found that, for the studied polymer-based ABS, the addition of 5 wt% of [C4mim]Br to ABS caused the expansion of two-phase area in the salt-rich region; while, for the PEG-rich region no change was observed. The partition coefficients of l-tyrosine (KTyr) within the studied system were determined at T = 298.15 K. The results obtained indicate that the addition of small quantities of [C4mim]Br to the {PEG 600 + K3C6H5O7} ABS could enhance the extraction efficiency for l-tyrosine. In addition, the experimental data are correlated using the NRTL model. The comparisons between the correlation and the experimental data reveal a good agreement.  相似文献   

12.
13.
In the catalytic hydrogenation of benzene to cyclohexane, the separation of unreacted benzene from the product stream is inevitable and essential for an economically viable process. In order to evaluate the separation efficiency of ionic liquids (ILs) as a solvent in this extraction processes, the ternary (liquid + liquid) equilibrium of 1-alkyl-3-methylimidazolium hexafluorophosphate, [Cnmim][PF6] (n = 4, 5, 6), with benzene and cyclohexane was studied at T = 298.15 K and atmospheric pressure. The reliability of the experimentally determined tie-line data was confirmed by applying the Othmer–Tobias equation. The solute distribution coefficient and solvent selectivity for the systems studied were calculated and compared with literature data for other ILs and sulfolane. It turns out that the benzene distribution coefficient increases and solvent selectivity decreases as the length of the cation alkyl chain grows, and the ionic liquids [Cnmim][PF6] proved to be promising solvents for benzene–cyclohexane extractive separation. Finally, an NRTL model was applied to correlate and fit the experimental LLE data for the ternary systems studied.  相似文献   

14.
In the present work, (liquid + liquid) equilibrium data have been determined experimentally for aqueous two-phase systems formed by the imidazolium ionic liquids of [Cnmim][CH3COO] (n = 4, 6, 8) and inorganic salts of K3PO4, K2HPO4, and K2CO3 at T = 298.15 K. Combined with available data in the literature, the effect of alkyl chain length of cations, type of anions of the ionic liquids, and nature of the inorganic salts were examined on the binodal curves of the systems. Then the binodal curves were fitted to a four-parameter empirical equation, and the tie-lines were described by the Othmer–Tobias and Bancroft equations. In addition, the extraction capacity of the {[Cnmim][CH3COO] (n = 4, 6, 8) + K3PO4} aqueous two-phase systems was evaluated through their application to the extraction of l-tryptophan. The high extraction efficiency suggests that these aqueous two-phase systems are feasible to be used in the extraction and separation process.  相似文献   

15.
In this work the (solid + liquid) equilibria (SLE) of the solution of sustainable solvents with five high-value compounds, thymol, ferulic acid, vanillic acid, caffeic acid and caffeine, was investigated. The sustainable solvents studied were liquid poly(ethylene glycol) of average molecular mass 200 and 400 – (PEG200 and PEG400), respectively as well as imidazolium ionic liquids with bistriflamide and triflate anions ([C4mim][NTf2] and [C4mim][OTf]). The obtained SLE data were correlated using the semi-empirical equation proposed by Grant. The activity coefficients of the studied solutes were calculated. Based on these correlations and calculations as well as on the thermo-physical properties of the pure constituents, the SLE behavior of the studied solutions was analyzed and discussed.  相似文献   

16.
New experimental results are presented for the solubility of carbon dioxide, hydrogen sulfide in the ionic liquid 1-octyl-3-methylimidazolium hexafluorophosphate ([C8mim][PF6]) at temperatures range from (303.15 to 353.15) K and pressures up to about 2 MPa. The solubility of the mixture of CO2/H2S in [C8mim][PF6] under various feed compositions were also measured at temperatures of (303.15, 323.15 and 343.15) K and the pressure up to 1 MPa. The solubility of carbon dioxide and hydrogen sulfide increased with increasing pressure and decreased with increasing temperature and the solubility of H2S is about three times that of CO2 in the particular ionic liquid studied. The measured data were correlated using extended Henry’s law included Pitzer’s virial expansion for the excess Gibbs energy, and the generic Redlich–Kwong cubic equation of state proposed for gas/ionic liquid systems. The correlations from the two models show quite good consistency with the experimental data for CO2/IL and H2S/IL binary mixtures within experimental uncertainties. For CO2/H2S/IL ternary mixtures, the RK model shows better correlation with the experimental values. We also studied the effect of cation alkyl chain length on the CO2 and H2S solubility by comparison of the experimental data of this study with those of previous reports. As the cation alkyl chain length became longer, the solubility of CO2 and H2S increased in the ionic liquid. Additionally, the influence of the anion on the solubility is studied by comparing the solubility of CO2 and H2S in [C8mim][PF6] with those in [C8mim][Tf2N]. As a result, CO2 and H2S have higher solubility in the IL with [Tf2N] as the anion.  相似文献   

17.
In this work, solubility, volumetric and viscosity behavior were studied for the systems containing the environmentally acceptable compounds: liquid poly(ethylene glycol) (PEG200) and three ionic liquids: 1-butyl-3-methylimidazolium dicyanamide ([C4mim][dca]), trihexyltetradecyl phosphonium dicyanamide ([P6,6,6,14][dca]) and 1-hexyl-3-methylimidazolium bis{(trifluoromethyl)sulfonyl}amide ([C6mim][NTf2]). The studies were performed in a temperature range (288.15 to 328.15) K and at a pressure of 0.1 MPa. For the only system that evidenced limited miscibility, namely (PEG200 + [P6,6,6,14][dca]), the temperature-composition phase diagram at 0.1 MPa was determined, mapping the existing one- and two-phase regions. In the homogeneous region of this diagram, densities and viscosities were measured and the excess molar volumes, as well as deviations in viscosity were calculated. For the other two systems, as they are always homogeneous in the temperature ranges of the present work, these measurements and calculations were performed in the full range of compositions. The molecular interactions in the studied systems were scrutinized using the obtained excess molar volumes, deviations of viscosity, as well as Kamlet–Taft parameters of PEG200 and the ionic liquids. In addition, the excess molar Gibbs free energies of activation of viscous flow and the related enthalpies and entropies were calculated and introduced to take into consideration the differences in size of the molecules.  相似文献   

18.
Two novel ionic liquids based on serine [Cnmim][Ser] (n = 3, 4) were prepared by the neutralization method and their structures were confirmed by 1H NMR spectroscopy and differential scanning calorimetry (DSC). The density, surface tension, and refractive index of the two ILs were measured from T = (298.15 to 338.15) K. Since these ILs [Cnmim][Ser] (n = 3, 4) could form strong hydrogen bonds with water, small amount of water in the ILs is difficult to removed by common methods. In order to eliminate the effect of trace of water, the standard addition method (SAM) was applied to these measurements. On the basis of the experimental data, the speed of sound (μ), thermal expansion coefficient (α), molecular volume (Vm), standard entropy (S0298), entropy of surface (Sa), energy of surface (Ea), parachor (P), molar polarization (Rm), and polarization coefficient (αp) were calculated, and the relationship between each of these properties of [Cnmim][Ser] (n = 3, 4) and temperatures was discussed. According to the additivity, the average value of anionic parachor, P(ave), was 180.81 for [Ser]. At the same time, the surface tension of these serine ionic liquids could be estimated from their parachor and refractive index. The estimated values of the surface tension and the corresponding experimental data were almost identical.  相似文献   

19.
(Liquid + liquid) equilibrium for the {1-ethyl-3-methylimidazolium tetrafluoroborate ([C2mim]BF4)/1-propyl-3-methylimidazolium tetrafluoroborate ([C3mim]BF4) + organic salt + H2O} aqueous two-phase systems (ATPSs) have been experimentally ascertained at T = 298.15 K. Three empirical equations were used to correlate the binodal data. On the basis of the empirical equation of the binodal curve with the highest accuracy and lever rule, the (liquid + liquid) equilibrium data were calculated by MATLAB. The reliability of the tie line compositions was proved by the empirical correlation equations given by the Othmer–Tobias and Bancroft equations. The effective excluded volume (EEV) values obtained from the binodal model for these systems were determined. The EEV and the binodal curves plotted in molality both indicate that the salting-out abilities of the four salts follow the order: Na3C6H5O7 > (NH4)3C6H5O7 > Na2C4H4O4  Na2C4H4O6, while the phase-separation abilities of the investigated ILs are in the order of [C3mim]BF4 > [C2mim]BF4. In the systems investigated, the effect of salts on the phase-forming capability was also evaluated in the shape of the salting-out coefficient obtained from fitting the tie-line data to a Setschenow-type equation. The phase-forming ability increases with the increase of salting-out coefficient.  相似文献   

20.
Surface and bulk properties of 1-hexyl-3-methylimidazolium chloride [C6mim][Cl] as an ionic liquid (IL) have been investigated by surface tension and electrical conductivity techniques at various temperatures. Results reveal that the ionic liquid behaves as surfactant-like and aggregates in aqueous solution. Critical aggregation concentration (cac) values obtained by conductivity and surface tension measurements are in good agreement with values found in the literature. A series of important and useful adsorption parameters including cac, surface excess concentration (Γ), and minimum surface area per molecule (Amin) at the air + water interface were estimated from surface tension in the presence and absence of different electrolytes. Obtained data show that the surface tension as well as the cac of [C6mim][Cl] is reduced by electrolytes. Also, values of surface excess concentration (Γ) show that the IL ions in the presence of electrolyte have much larger affinity to adsorption at the surface and this affinity increased in aqueous electrolyte solution in the order of I? > Br? > Cl? for counter ion of salts that was explained in terms of a larger repulsion of chloride anions from interface to the bromide and iodide anion as well as difference in their excess polarizability.  相似文献   

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