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1.
The rheological behavior of unentangled and entangled semidilute solution of anionic polyelectrolyte sodium carboxymethyl cellulose (NaCMC) containing cationic surfactant cetyltrimethylammonium bromide (C16TAB) was investigated. The results reveal that the rheological properties of these semidilute NaCMC solutions depend on the amount of C16TAB added. In the unentangled semidilute NaCMC solution (0.5 g/L), the viscosity decreases with the increase of C16TAB amount in the low surfactant concentration region (below the critical aggregation concentration, CAC). However, in high surfactant concentrations (above CAC), the viscosity decreases sharply with the increase in C16TAB amount. It is found that viscosity change of NaCMC solution could be described using Colby’s model when surfactant concentrations are between CAC and saturated concentration (Cs), suggesting that no inter-polymer interaction exists between C16TAB and NaCMC in the unentangled semidilute solution. However, for the entangled semidilute NaCMC solution (5 g/L), the addition of C16TAB leads to an increase in viscosity. Meanwhile, the solution exhibits an enhanced shear thinning behavior due to adding more C16TAB than 1 mM. The viscosity increase is ascribed to the physical cross linking of surfactant micelles with NaCMC chains. Furthermore, it is suggested that the enhanced shear thinning behavior results from weak interaction between NaCMC chains and C16TAB micelles.  相似文献   

2.
Dynamic rheological behaviors of α-cellulose 1-ethyl-3-methylimidazolium acetate ([Emim]Ac) solutions were investigated in a large range of concentrations (0.1–10 wt %) at 25 °C. On the basis of data from the dynamic viscoelastic test, the exponents of the specific viscosity η sp versus concentration c were determined as 1.0, 2.0 and 4.7 for dilute, semidilute unentangled and entangled regimes respectively, which were in accordance with the scaling prediction for neutral polymer in θ solvent. The intrinsic viscosity [η] of the solution was determined to be 253 mL/g at 25 °C. The linear viscoelastic response of the dilute and semidilute unentangled solutions could be described successfully by the Zimm and Rouse model (ν = 0.5 for θ solution) respectively, suggesting that the motion of cellulose chain in [Emim]Ac changed from Zimm to Rouse model with increasing concentration. At low concentrations, failure of the Cox–Merz rule with steady shear viscosity larger than complex viscosity was observed. While as the concentration increased, the deviation from the Cox–Merz rule disappeared due to the formation of homogeneous entanglement structure in cellulose solution.  相似文献   

3.
《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   

4.
Thermodynamic interaction parameters of water-soluble poly[2-(dimethylamino)ethyl methacrylate] (DMA) and poly[2-(N-morpholino)ethyl methacrylate] (MEMA) homopolymers and their diblock copolymer (DMA–MEMA) were investigated at the temperatures above their glass-transition temperatures (Tg) by inverse gas chromatography (IGC) method. Sorption thermodynamic parameters of some aliphatic, alicyclic and aromatic hydrocarbons, weight fraction activity coefficients, Flory–Huggins interaction parameters, and solubility parameters for hydrocarbons and polymers were calculated. It was observed that sorption thermodynamic parameters on (co)polymers depend on the molecular structures of hydrocarbons. Evaluating both the calculated values of the weight fraction activity coefficients and Flory–Huggins interaction parameters, the solving ability of the hydrocarbons for DMA, MEMA homopolymers, and DMA–MEMA diblock copolymer decreased in the following sequence: Aromatic > alicyclic > aliphatic hydrocarbons.  相似文献   

5.
(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   

6.
《Tetrahedron: Asymmetry》2006,17(14):2069-2073
Four commercially available lipases and two native lipases from Aspergillus niger AC-54 and Aspergillus terreus AC-430 were used for the resolution of (RS)-Ibuprofen in systems containing the ionic liquids [BMIM][PF6] and [BMIM][BF4]. The lipases showed higher conversion in a two-phase system using [BMIM][PF6] and isooctane compared to that in pure isooctane. Although the best enzyme was a commercially available lipase from Candida rugosa (E = 8.5), another native lipase, produced in our laboratory, from A. niger gave better enantioselectivity (E = 4.6) than the other lipases tested (E = 1.9–3.3.). After thorough optimization of several reaction conditions (type and ratios of isooctane/ionic liquid, amount of enzyme, and reaction time), the E-value of A. niger lipase (15% w/v) could be duplicated (E = 9.2) in a solvent system composed of [BMIM][PF6] and isooctane (1:1) after 96 h of reaction.  相似文献   

7.
《Chemical physics letters》2006,417(1-3):206-210
Two C–O stretching hot bands, (ν1 + 2ν3)  2ν3 and (2ν1 + ν3)  (ν1 + ν3), of the CCO radical in the ground electronic state were measured. These hot bands are red shifted by approximately 70 cm−1 compared to the C–O stretching fundamental. CCO was produced in a discharge through a flowing mixture of carbon suboxide and helium. The spectra were recorded using a diode laser spectrometer. The band origins were determined to be 1904.32512(62) and 1902.69130(56) cm−1 for (ν1 + 2ν3)  2ν3 and (2ν1 + ν3)  (ν1 + ν3), respectively. The measurements in this band together with previously reported frequencies in the C–C and C–O stretching regions were analysed to determine harmonic frequencies and anharmonicity constants.  相似文献   

8.
Measurements of vapour pressure data were conducted using a quasi-static ebulliometer for systems containing water, methanol, ethanol, and a mixture of {water + ethanol} in the presence of an ionic liquid (IL), namely, 1-methylimidazolium chloride ([MIm]Cl), wherein the IL-content ranged from w2 = (0.10 to 0.50). The vapour pressure data of IL-containing binary systems were correlated by the NRTL model with an overall average absolute relative deviation (AARD) of 0.0103, and the resulting binary parameters were used to predict the vapour pressures of a ternary system {water + ethanol + [MIm]Cl} with an AARD less than 0.0077. Further, the isobaric vapour liquid equilibria (VLE) for the ternary system {water + ethanol + IL} with IL-content of w3 = (0.10, 0.30, and 0.50) for [MIm]Cl and x3 = 0.15 for [MIm]Cl, [C4MIm]Cl, and [C6MIm]Cl were predicted at 101.3 kPa, respectively. It is indicated that [MIm]Cl presents the strongest ability to enhance the relative volatility of ethanol to water in the mixture of {water + ethanol} than that of [C4MIm]Cl and [C6MIm]Cl, which is consistent with the cationic sizes and hence the ionic hydration ability. Therefore, distillation separation of the azeotrope of {water + ethanol} can be sufficiently facilitated by the addition of [MIm]Cl at a specified content.  相似文献   

9.
The reaction of [Cp1IrCl2]2 (Cp* = η5 ? C5Me5) with the tridentate 3-thiapentane-1,5-dithiolate ligand, S(CH2CH2S?)2 (tpdt), led to the formation of [Cp1Ir(η3 ? tpdt)] (1) in 81% isolated yield. Subsequent reactions of 1 with [Cp1IrCl2]2 in 2:1 and 1:1 molar equiv ratios resulted in the formation of [Cp1Ir(μ ? η2:η3 ? tpdt)Cp1IrCl][PF6] (2) and [Cp1Irμ ? η2:η3 ? tpdt)Cp1IrCl][Cp1IrCl3] (3) in 86 and 79% yields, respectively, based on 1, whereas the reactions of 1 with [(COD)IrCl]2 (COD = 1,5-cyclooctadiene) in 2:1 and 1:1 molar equiv ratios resulted in the formation of the homo-bimetallic derivatives Cp1Ir(μ ? η1:η3 ? tpdt)(COD)IrCl (4) (92% yield) and [Cp1Ir(μ ? η2:η3 ? tpdt)(COD)Ir] [(COD)IrCl2] (5) (82% yield). Reactions between 1 and [(COD)RhCl]2, yielded the hetero-bimetallic derivatives Cp1Ir(μ ? η1:η3 ? tpdt)(COD)RhCl (6) and [Cp1Ir(μ ? η2:η3 ? tpdt)(COD)Rh][(COD)RhCl2] (7), in 92 and 93% yields, respectively. The reaction of 1 with methyl iodide gave mono-methylated derivative [Cp1Ir(η3-C4H8S3Me)]I (8) (93% yield). All these compounds have been comprehensively characterized.  相似文献   

10.
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   

11.
Densities (ρ) and viscosities (η) of aqueous 1-methylpiperazine (1-MPZ) solutions are reported at T = (298.15 to 343.15) K. Refractive indices (nD) are reported at T = (293.15 to 333.15) K, and surface tensions (γ) are reported at T = (298.15 to 333.15) K. Derived excess properties, except excess viscosities (Δη), are found to be negative over the entire composition range. The addition of 1-MPZ reduces drastically the surface tension of water. The temperature dependence of surface tensions is explained in terms of surface entropy (SS) and enthalpy (HS). The measured and derived properties are used to probe the microscopic liquid structure of the bulk and surface of the aqueous amine solutions.  相似文献   

12.
This paper reports a new solvent, room-temperature ionic liquid (RTIL), for the preparation of dodecanethiol self-assembled monolayers (C12SH-SAMs) on polycrystalline gold. The quality of C12SH-SAMs was characterized by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). From CV experiments, we find that the differential capacitance Cd values of the C12SH-SAM prepared in RTIL, 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM]PF6) containing 10 μL neat C12SH for 24 h (C12SH-SAMs[BMIM]PF6,10 μL,24 h) are independent of the scan rate, the effective thickness deff value and the average cant angle φ value of this monolayer are 18 ± 1 Å and 27 ± 4°, respectively. The difference value of the current density at −0.2 and 0.5 V (Δip) is only 0.73 ± 0.18 μA cm−2. EIS experiments show that the phase angle value at 1 Hz Φ1 Hz, the charge transfer resistance Rct value and surface coverage θ value of this C12SH-SAM are 88.2 ± 0.7°, 3.44 ± 1.91  cm2 and 99.998 ± 0.001%, respectively. These results indicate that high-quality C12SH-SAMs can be formed in [BMIM]PF6. In addition, the rate of formations of high-quality C12SH-SAMs in RTIL can be substantially improved by ultrasound.  相似文献   

13.
Two new blue light-emitting polymers, poly{[2,5-bis(4-phenylene)-1,3,4-oxadiazole]-[9,9-dihexylfluorene-2,7-diyl]-[N-(4-(9H-carbazol-9-yl)phenyl)-N,N-bis(p-phenylene)aniline]} (POFPA) and poly{[2,5-bis(4-phenylene)-1,3,4-oxadiazole]-[9,9-dihexylfluorene-2,7-diyl]-[4-(3,6-(di-9H-carbazol-9-yl)-9H-carbazol-9-yl)-N,N-bis(p-phenylene)-aniline]} (POFCPA), were synthesized by Suzuki coupling reactions. By GPC analysis against a linear polystyrene standard POFPA and POFCPA were found to have Mn of 1.68 × 104 and 3.70 × 103, respectively. In contrast to POFPA, the main absorption peak of POFCPA in dilute toluene solution was blue-shifted by Δλ = 26 nm owing to its backbone of relatively shorter π-conjugation length and more carbazole units in side chain. The absolute fluorescence quantum yield (Φf) of POFCPA in dilute toluene solution was determined as 73%, much higher than that of POFPA (Φf  58.9%) measured under the same conditions. An electroluminescence device based on POFCPA displays a stable blue emission having color coordinates of (0.15, 0.20), a maximum brightness of 4762 cd/m2, and a maximum current efficiency of 1.79 cd/A. By using this polymer as the host material doped with 1 wt.% 4,4′-bis[2-(4-(N,N-diphenylamino)phenyl)vinyl]biphenyl, the achieved highest brightness, maximum current efficiency and maximum power efficiency are 13,613 cd/m2, 3.38 cd/A, and1.84 lm/W, respectively.  相似文献   

14.
Quaternary (liquid + liquid) equilibrium (LLE) data of the aqueous two-phase poly (ethylene glycol), poly (N,N-dimethylacrylamide-t-butylacrylamide) with abbreviation name poly (DMAM–TBAM) as a hydrophobic association water-soluble copolymer and KH2PO4 has been determined experimentally at T = 338.15 K. Furthermore, the generalized Flory–Huggins theory with two electrostatic terms (the Debye–Hückel and Pitzer–Debye–Hückel) was used for correlation of the phase behavior of the quaternary system and the interaction parameters between all species were calculated.It was found that addition of poly (DMAM–TBAM) copolymer as well as changing the temperature can shift the binodal curves of aqueous two-phase systems containing polyethylene glycol (PEG) and salt. Also, the phase behavior of the DMAM–TBAM copolymer with some salts containing sodium chloride, ammonium hydrogen phosphate, potassium hydrogen phosphate, and sodium carbonate were studied experimentally at T = 338.15 K and the effect of the salt type on the their binodal curves was determined.  相似文献   

15.
Density, speed of sound and viscosity measurements of binary aqueous solutions of tri-potassium citrate were performed from dilute up to near saturated concentration range at T = (293.15, 298.15, 303.15, 308.15, and 313.15) K. Volumetric and transport properties of ternary aqueous solutions of (tri-potassium citrate + KCl) have also been measured within the molality range of KCl (0.05, 0.15, 0.25, 0.35, 0.45, and 0.55) at different temperatures. Apparent molar volume and apparent molar isentropic compressibility have been calculated from the density and speed of sound for binary and ternary aqueous solutions of tri-potassium citrate. Apparent molar volume and apparent molar isentropic compressibility of ternary aqueous solutions of (tri-potassium citrate + KCl) have been correlated with the Redlich–Mayer equation. Viscosity values of ternary aqueous solutions of (tri-potassium citrate + KCl) have been fitted with the Jones–Dole equation. The results obtained have been interpreted in elucidating the effect of tri-potassium citrate on the interaction of KCl–H2O. Density and viscosity values of ternary aqueous solutions of (tri-potassium citrate + KCl) have been predicted successfully using the methods proposed by Laliberte (2007), Laliberte and Cooper (2004) [9], [10] and Zafarani-Moattar and Majdan-Cegincara (2009) [11].  相似文献   

16.
The kinematic viscosity ν for (ethane-1,2-diol  +  1,2-dimethoxyethane  +  water) was measured at 14 different ternary compositions covering the whole miscibility field, and at 19 temperatures in the range 263.15 ⩽T /  K 353.15. The experimental values were fitted using empirical equations of the type ν = ν (T) and ν = ν (xi), respectively, in order to provide reliable models to account for the behaviour of the system. The excess kinematic viscosity νEhas been determined and interpreted in terms of the type and nature of the interactions among the components of the mixture. Using the experimental ν data, the thermodynamic properties ( ΔG * , ΔH * ,ΔS *  ) of the viscous flow have been obtained from the Eyring’s approach and standard thermodynamic equations. Furthermore, excess mixing functions, such asΔG * E , have been determined, and found to evidence the existence of quite strong specific interactions among the components, probably due to the formation of hydrogen bonds and dipolar networks. However, all the calculated excess mixing properties suggest the absence of stable three-component adducts.  相似文献   

17.
Water activity measurements by the isopiestic method have been carried out on the aqueous ternary system of {l-serine + 1-(2-carboxyethyl)-3-methylimidazolium chloride[HOOCEMIM][Cl]} ionic liquid and the aqueous binary system of IL at T = 298.15 K and atmospheric pressure. The data obtained were used to calculate the vapor pressure and osmotic coefficient of solution as a function of concentration. The experimental results for the activity of water were accurately correlated with segment-based local composition models of modified NRTL and UNIQUAC. The fitting quality of the above models has been favorably compared with the NRTL and Wilson models. From these data, the corresponding activity coefficients have been calculated. For the same system, the solubility of the l-serine at various [HOOCEMIM][Cl] ionic liquid concentrations was measured at T = 298.15 K using the gravimetric method. A chemical model was employed to describe the dissociation equilibria of all amino acid species with hydrogen ions in water. Moreover, for l-serine, the chemical model indicated that the formation of cations is insignificant in the [HOOCEMIM][Cl] solution. Also the above local composition models were used to predict the solubility of l-serine in aqueous IL solutions. To provide information regarding (solute + solute) interactions, transfer Gibbs free energies (ΔGtr) of amino acid from water to aqueous IL solutions have been determined.  相似文献   

18.
Twenty-three different Rh complexes of the (NHC)RhCl(cod) and (NHC)RhCl(CO)2 type were synthesized from [RhCl(cod)]2. The electron donating nature of the NHC ligands was changed in a systematic manner. The redox potentials of the various (NHC)RhCl(cod) and the ν(CO) of the various (NHC)RhCl(CO)2 were determined. A correlation of the Rh redox potentials and the Rh ν(CO), respectively, with the related data from analogous (NHC)IrCl(cod) and (NHC)IrCl(CO)2 complexes established two linear relationships. The linear regression (R2 = 0.993) of the Rh and the Ir redox potentials results in an equation for the redox potential transformation: E1/2(Ir) = 1.016 · E1/2(Rh) ? 0.076 V. The linear regression (R2 = 0.97) of the Rh and Ir νav(CO) results in an equation for the νav(CO) transformation: νav(CO)Ir = 0.8695 · νav(CO)Rh + 250.7 cm?1. In this manner the Rh and the Ir-scale for the determination of the electron donating properties of NHC ligands are unified.  相似文献   

19.
(Liquid + liquid) equilibrium (LLE) data of quaternary aqueous system containing polyoxyethylene (20) cetyl ether (with abbreviation name Brij 58, non-ionic surfactant), diammonium hydrogen phosphate, and poly ethylene glycol (PEG) with three molar masses {MW = (1000, 6000, and 35,000) g · mol?1} have been determined experimentally at T = 313.15 K.Furthermore, the Flory–Huggins theory with two electrostatic terms (Debye–Hückel and Pitzer–Debye–Hückel equations) have been used to calculate the phase behavior of the quaternary systems and (surfactant + polymer) interaction parameter as well as interaction parameters between other species. Temperature dependency of the parameters of the Flory–Huggins theory has been obtained.Also an effort have been done to show that addition of PEG as well as increasing the temperature can shift the binodal curves of the ternary aqueous system containing surfactant and salt to lower mole fraction of salt. Also the effect of polymer molar mass on the binodal diagram displacement has been discussed.  相似文献   

20.
In the present study, influence of the alkyl group and temperature on the interactions between the carboxylic acid and ionic liquid (IL) mixtures were discussed in term of density and sound velocity measurements. The IL used in this study was 1-butyl-3-methylimidazolium thiocyanate ([BMIM]+[SCN]). The density (ρ), and sound velocity (u), of the IL, acetic acid, propionic acid, and their corresponding binary systems {[BMIM]+[SCN] (x1) + acetic or propionic acid (x2)} have been measured at T = (293.15, 298.15, 303.15, 308.15 and 313.15) K and at p = 0.1 MPa. The excess molar volumes, VmE, isentropic compressibility, κs, and deviation in isentropic compressibility, Δκs, were calculated using experimental density and sound velocity data, respectively. The Redlich–Kister polynomial equation was used to fit the excess/deviation properties. These results are useful for describing the intermolecular interactions that exist between the IL and carboxylic acid mixtures.  相似文献   

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