1,2-丙二醇水溶液在不同温度下的超额摩尔体积黏度和热容

Experimental densities, viscosities and heat capacities at different temperatures were presented over the entire mole fraction range for the binary mixture of 1,2-propanediol and water. Density values were used in the determination of excess molar volumes, VE. At the same time, the excess viscosity was investigated. The values of VE and E were fitted to the Redlich-Kister equation. Good agreement was observed. The excess volumes are negative over the entire range of composition. They show an U-shaped-concentration dependence and decrease in absolute values with increase of temperature. Values of E are negative over the entire range of the composition, and has a trend very similar to that of VE . The analysis shows that at any temperature the specific heat of mixture is a linear function of the composition as x1 > 20%. All the extended lines intersect at one point. An empirical equation is obtained to calculate the specific heat to mixture at any composition and temperature in the experimental range.     

Density and Excess Molar Volume of Binary Mixtures ofp-Xylene＋Acetic Acid and o-Xylene＋Acetic Acid at Different Temperatures and Pressures

A new apparatus was designed with a thick-walled glass capillary, electric heater tube with red copper and heat preservation. The thick-walled glass capillary was used for its advantages of resistance to acid corrosion and pressure, and ease of observation. The experimental densities over the entire range of mole fraction for the binary mixture of p-xylene＋acetic acid and o-xylene＋acetic acid were measured using the new apparatus at temperatures ranging from 313.15K to 473.15K and pressure ranging from 0.20 to 2,0 MPa. The density values were used in the determination of excess molar volumes, W. The Redlich-Kister equation was used to fit the excess molar volume values, and the coefficients and estimate ot the standard error values were presented. The experimental resuits prove that the density measurement apparatus is successful.     

Isobaric vapor–liquid equilibrium for binary system of aniline+methyl-N-phenyl carbamate

In this study,the quasi-static ebulliometric method was used to measure both of the vapor pressures of methyl N-phenyl carbamate(MPC),and the isobaric vapor–liquid equilibrium(VLE) data of the aniline and MPC binary system.The measured vapor pressure data of MPC,at different temperature ranging from 369.60 to 389.54 K,fitted well with the Antoine equation.The VLE data for the aniline and MPC system at(2.00,4.00,6.00,7.00 and 8.00) k Pa were correlated by both of nonrandom two-liquid(NRTL) and Wilson models.The parameters of the two models were obtained by regressing the experimental data,with the absolute temperature deviations of 0.54 K and 0.53 K,respectively.The relative volatility of the binary system calculated was all far more than 1,which gives the conclusion that the high purity MPC can be separated from aniline and MPC binary system by rectification or distillation technology.     

Excess Molar Volume, Viscosity and Heat Capacity for the Binary Mixture of p-Xylene and Acetic Acid at Different Temperatures

Experimental densities, viscosities and heat capacities at different temperatures were presented over the entire range of mole fraction for the binary mixture of p-xylene and acetic acid. Density values were used in the determination of excess molar volumes, VE. At the same time, the excess viscosity and excess molar heat capacities were calculated. The values of VE, ηE and cpE were fitted to the Redlich-Kister equation. Good agreements were observed. The excess molar volumes are positive with a large maximum value located in the central concentration range. The excess viscosity has an opposite trend to the excess molar volume VE. ηE values are negative over the entire range of the mixture. The cure of dependence of cpE on concentration has a special shape. The molecular interaction between p-xylene and acetic acid is discussed.     

离子液体[C4mim][PF6]与N, N-二甲基甲酰胺二元混合物在298.15 K～318.15 K的密度和粘度

Viscosities and densities for 1-butyl-3-methylimidazolium hexafluorophosphate （[C4mim][PF6]） and N, N-dimethylformamide （DMF） binary mixtures have been measured at the temperature range from 293.15 K to 318.15 K. It is shown that the viscosities and densities decrease monotonously with temperature and the content of DMF. Various correlation methods including Arrhenius-like equation, Sedclon et al.＇s equation, Redlich-Kister equation with four parameters, and other empirical equations were applied to evaluate these experimental data. A model based on an equation of state Ior estimating the viscosity of mixtures containing ionic liquids were proposed by coupling with the excess Gibbs free energy model of viscosity, which can synchronously calculate the viscosity and the molar volume. The results show that the model gives a deviation of 8.29% for the viscosity, and a deviation of 1.05% for the molar volume when only one temperature-independent adjustable parameter is adopted. The correlation accuracy is further improved when two parameters or one temperature-dependent parameter is used.     

一氧化碳在苯酚+乙醇中的溶解度测量和关联

The solubility of carbon monoxide in phenol＋ethanol mixed solvents at elevated pressures is reported in this article. The experimental results revealed the influence of pressure on the solubility of CO in phenol＋ethanol mixtures. These mixtures are a poorer solvent for carbon monoxide. The solubility of CO is a linear function of pressure, and the extended Henry＇s constants were presented at different concentrations of phenol. The cubic Soave-Redlich-Kwong equation of state was used to correlate the experimental gas liquid equilibrium data and to predict the solubility of CO. At the same time, the binary interaction parameters, kO, for CO-phenol, CO-ethanol and phenol-ethanol systems were estimated by fitting experimental GLE data at 303.15 K and at 2.0-9.0 MPa. Hence, a model was suggested for the solubility of CO in phenol＋ethanol mixed solvents. The agreement between experimental and calculated solubilities with the proposed model was rather satisfactory.     

二元混合物环丁酚和对二甲苯、乙苯在温度范围为303.15—353.15K下的密度、黏度及其相关性质

Densities and viscosities of the binary systems of sulfolane ＋ ethylbenzene, sulfolane ＋ p-xylene have been experimentally determined in temperature interval 303.15—353.15 K and at atmospheric pressure for the whole composition range. The excess molar volumes and viscosity deviations were computed. The computed quantities have been fitted to Redlich-Kister equation. Excess molar volumes and viscosity deviation show a systematic change with increasing temperature. Two mixtures exhibit negative excess volumes with a minimum which occurs approximately at χ = 0.5. The effect of the size, shape and interaction of components on excess molar volumes and viscosity deviations is discussed.     

不同温度压力下纯水、醋酸+水、对二甲苯+醋酸+水黏度测定(英文)

The viscosities of pure water, the acetic acid + water binary system, and the p-xylene + acetic acid + water ternary system at different concentrations were determined with a rolling-ball viscometer at temperatures from 313.15 to 473.15 K and pressures from 0.10 to 3.20 MPa. The viscosity data were fitted by a correlation equation for the estimation of the mixture viscosities. The average absolute deviations (AAD) of the correlation for binary and ternary systems are 2.48% and 1.77%, respectively.     

288.15K-308.15K(Poloxamerl88+乙醇/丙酮+水)三元体系的密度和黏度

The densities and viscosities of ternary systems(Poloxamer 188+ethanol/acetone+water)were meas- ured at 288.15,293.15,298.15,303.15,308.15 K and atmospheric pressure for different mass fractions of Poloxamer 188(0 to 0.02)in aqueous solution and different solvent volume fractions of ethanol/acetone(0 to 0.3)in Poloxamer 188 aqueous solution.The densities were measured by a pycnometer,while the viscosities were measured using two Ubbelohde capillary viscometers.The correlations of density and viscosity of these ternary systems are obtained by fitting the experimental data at different temperatures,mass fractions and volume fractions.     

Molecular dynamics simulation for the binary mixtures of high pressure carbon dioxide and ionic liquids简

Molecular dynamics simulation with an all-atom force field has been carded out on the two binary sys- tems of [bmim][PF6]-CO2 and [bmim][NO3]-CO2 to study the transport properties, volume expansion and micro- structures. It was found that addition of CO2 in the liquid phase can greatly decrease the viscosity of ionic liquids （ILs） and increase their diffusion coefficient obviously. Furthermore, the volume expansion of ionic liquids was found to increase with the increase of the mole fraction of CO2 in the liquid phase but less than 35% for the two simulated systems, which had a significant difference with CO2 expanded organic solvents. The main reason was that there were some void spaces inter and intra the molecules of ionic liquids. Finally, site to site radial distribution functions and corresponding number integrals were investigated and it was found that the change of microstructures of ILs bv addition CO2 had a great influence on the orooerties of ILs.     

二氧化硫和二氧化碳在离子液体支撑液膜中的渗透率和选择性

Permeabilities and selectivities of gases such as carbon dioxide (CO2), sulfur dioxide (SO2), nitrogen (N2) and methane (CH4) in six imidazolium-based ionic liquids ([emim][BF4], [bmim][BF4], [bmim][PF6], [hmim][BF4], [bmim][Tf2N] and [emim][CF3SO3]) supported on polyethersulfone microfiltration membranes are investigated in a single gas feed system using nitrogen as the environment and reference component at temperature from 25 to 45ºC and pressure of N2 from 100 to 400 kPa. It is found that SO2 has the highest permeability in the tested supported ionic liquid membranes, being an order of magnitude higher than that of CO2, and about 2 to 3 orders of magnitude larger than those of N2 and CH4. The observed selectivity of SO2 over the two ordinary gas components is also striking. It is shown experimentally that the dissolution and transport of gas components in the supported ionic liq-uid membranes, as well as the nature of ionic liquids play important roles in the gas permeation. A nonlinear in-crease of permeation rate with temperature and operation pressure is also observed for all sample gases. By considering the factors that influence the permeabilities and selectivities of CO2 and SO2, it is expected to develop an optimal supported ionic liquid membrane technology for the isolation of acidic gases in the near future.     

Progress in the Study on the Phase Equilibria of the CO2·H2O and CO2-HeO-NaCI Systems

To study the feasibility of CO2 geological sequestration,it is needed to understand the complicated mul- tiple-phase equilibrium and the densities of aqueous solution with CO2 and multi-ions under wide geological condi- tions（273.15—473.15K,0—60MPa）,which are also essential for designing separation equipments in chemical or oil-related industries.For this purpose,studies on the relevant phase equilibria and densities are reviewed and analyzed and the method to improve or modify the existing model is suggested in order to obtain more reliable predictions in a wide temperature and pressure range.Besides,three different models（the electrolyte non random two-liquid（ELECNRTL）,the electrolyte NRTL combining with Helgeson model（ENRTL-HG）,Pitzer activity coefficient model combining with Helgeson model（PITZ-HG））are used to calculate the vapor-liquid phase equilib- rium of CO2-H2O and CO2-H2O-NaCl systems.For CO2-H2O system,the calculation results agree with the experimental data very well at low and medium pressure（0—20MPa）,but there are great discrepancies above 20MPa.For the water content at 473.15K,the calculated results agree with the experimental data quite well.For the CO2-H2O-NaCl system,the PITZ-HG model show better results than ELECNRTL and ENRTL-HG models at the NaCl concentration of 0.52mol·L ^-1 .Bur for the NaCl concentration of 3.997mol·L ^-1 ,using the ELECNRTL and ENRTL-HG models gives better results than using the PITZ-HG model.It is shown that available experimental data and the thermodynamic calculations can satisfy the needs of the calculation of the sequestration capacity in the temperature and pressure range for disposal of CO2 in deep saline aquifers.More experimental data and more accurate thermodynamic calculations are needed in high temperature and pressure ranges（above 398.15K and 31.5MPa）.     

对二甲苯和醋酸二元液体混合物在不同温度下的超额摩尔体积、粘度和热容

Experimental densities, viscosities and heat capacities at different temperatures were presented over the entire range of mole fraction for the binary mixture of p-xylene and acetic acid. Density values were used in the determination of excess molar volumes, VE. At the same time, the excess viscosity and excess molar heat capacities were calculated. The values of V^E, η^E and cE/p were fitted to the Redlich-Kister equation. Good agreements were observed. The excess molar volumes are positive with a large maximum value located in the central concentrationrange. The excess viscosity has an opposite trend to the excess molar volume V^E. η^E values are negative over the entire range of the mixture. The cure of dependence of c E/p on concentration has a special shape. The molecularinteraction between v-xvlene and acetic acid is discussed.     

离子液体[BMIM][DBP]+水+甲醇/乙醇三元工质溶液蒸汽压的测量和预测(英文)

The ionic liquid, 1-butyl-3-methylimidazolium dibutylphosphate ([BMIM][DBP]) was prepared and the vapor pressures of three set of binary solutions H2O(1)/CH3OH(1)/C2H5OH(1) + [BMIM][DBP](2) were measured at different temperature and in the ILs mole fraction range from 0.1 to 0.6 with a static equilibrium apparatus. The measured vapor pressures were correlated with Non-Random Two Liquid (NRTL) activity coefficient model and the average relative deviations (ARD) between experimental and correlated vapor pressures for these binary solutions were 3.19%, 2.42% and 2.95%, respectively. Then, the vapor pressures of two set of ternary solutions H2O(1) + CH3OH(2)/C2H5OH(2) + [BMIM][DBP](3) were measured with an inclined boiling apparatus and further predicted with NRTL activity coefficient model based on the binary interaction parameters coming from fitting the vapor pressures of the binary solutions. The results indicated that the ternary solutions containing [BMIM][DBP] were shown a strong negative deviation from Raoult’s Law when the mole fraction of [BMIM][DBP] was larger than 0.2, which meant that ternary solutions could absorb the refrigerant vapors at the same or below solution temperature. Meanwhile, the average relative deviations between experimental and predicted vapor pressures for ternary solutions were 2.92% and 3.06%, respectively. Consequently, the NRTL active coefficient model used for non-electrolyte solutions was still valid for predicting vapor-liquid equilibrium of binary or ternary solutions containing ILs.     

Conductivities of AlCl3/Ionic Liquid Systems and Their Application in Electrodeposition of Aluminium

Solubilities and conductivities of anhydrous AlCl3 in six kinds of ionic liquids (ILs) were measured. Among the six kinds of ILs [bmim]Cl, [bmim]Br, [bmim]BF4, [bmim]PF6, [emim][EtSO4] and [bmim][HSO4], anhydrous AlCl3 could be dissolved in the first five kinds but was hardly dissolved in [bmim][HSO4]. The results showed that the nominal solubilities of AlCl3 in ILs increased in the order of [bmim][HSO4] < [bmim]PF6 < [emim][EtSO4] < [bmim]BF4 < [bmim]Cl < [bmim]Br. Conductivities of the AlCl3/ILs systems depended apparently on the nominal molar ratio of AlCl3 to ILs. The conductivities of AlCl3/[bmim]Cl, AlCl3/[bmim]Br and AlCl3/[bmim]PF6 systems had a similar tendency as a function of the nominal molar ratio, that is, as the molar ratio was increased, conductivities increased first and then decreased, with the maximum conductivity obtained at approximately 0.9:1, 1.0:1 and 0.5:1, respectively. Conductivities of the AlCl3/[bmim]BF4 exhibited a dentate change and decreased with the molar ratio of AlCl3 to [bmim]BF4 increasing in general. With the increasing of the anhydrous AlCl3 amount in [emim][EtSO4], conductivity of AlCl3/[emim][EtSO4] monotonically decreased. AlCl3/[bmim]Cl system was chosen as the electrolyte for the electrodeposition of Al. Preliminary experimental results showed that dense, adherent and homogeneous Al coatings could be electrodeposited on stainless steel by means of constant potential technique and the surface coverage was quite satisfactory.     

Determination of Vapor Pressures for Binary and Ternary Mixtures Containing Ionic Liquid 1-propyl-3-methylimidazolium Bromide

Vapor pressure values of binary systems water + ethanol, water + ionic liquid 1-propyl-3-methylimidazolium bromide ([PMIM][Br]), ethanol + [PMIM][Br] and ternary system water + ethanol + [PMIM][Br] at different temperatures were measured by using a modified boiling point method in various concentrations of (16.66%, 33.7%), (17.4%, 33.9%) and (16.5%, 32%) mass percent of ionic liquid, respectively. The experimental vapor pressures of solvent were well correlated by the Antoine-type equation, and the overall average absolute deviation (AAD) was found to be 0.39%. The experimental results for mixtures containing ionic liquid indicate that the vapor pressure of the solvents can be decreased noticeably to different extent due to the affinity difference between ionic liquid and solvent, which is similar to the salt effect of common inorganic salts. As a result, ionic liquid may find industrial applications in extractive distillations for the system with a low separation factor or even for an azeotropic mixture.     

Determination and Correlation of Solubilities of Four Novel Benzothiazolium Ionic Liquids with PF6^- in Six Alcohols

Four novel benzothiazolium ionic liquids with 6PF- （[C1Bth][PF6], [C4Bth][PF6], [C5Bth][PF6] and [C6Bth][PF6]） were synthesized, and the rang of their melting points were determined between 358.35 K-424.05 K. The relationship of their melting points and the length of the straight alkyl chain on cation reflected‘S’ type ten-dency. Then, the solubilities of the four ionic liquids in six lower alcohols （methanol, ethanol, 1-propanol, 2-propanol, 1-butanol and 2-methyl-1-propanol） were measured in the temperature rang of 253.15-383.15 K at at-mospheric pressure with static analytical method, respectively. It was found that [C6Bth][PF6] in all investigated ionic liquids had the largest solubility in six alcohols and the solubility of [C4Bth][PF6] in methanol was very sensi-tive for temperature in 313.15-333.15 K, which was so-called “temperature-sensitivity”. This feature is of great significance to their application of catalyzing reaction or extraction process, and makes the recovery and reuse of ionic liquids （ILs） become easier. Moreover, the experimental solubility data were correlated with the modified Apelblat equation andλh equation, respectively. It was found that the result of correlation using two divided tem-perature ranges was better than that of using the whole temperature range.     

Sorption and Diffusion Behavior of Carbon Dioxide into Poly（l-lactic acid） Films at Elevated Pressures

Equilibrium sorption amount, desorption diffusion coefficients and sorption diffusion coefficients of CO2 in poly（l-lactic acid） （PLLA） films at elevated pressures were determined by the gravimetric method, in which the Fick＇s diffusion model was applied to analyze both the desorption and sorption processes. The equilibrium sorption amount of CO2 in PLLA increased with lowering temperature and elevating pressure at the temperature range from 40 to 60 ℃ and pressure from 10^4 to 2x10^4 kPa. Desorption diffusion coefficients were greatly influenced by the equilibrium sorption amount, and they were in the same order of magnitude as the sorption diffusion coefficients. The scan electron microscope （SEM） photos demonstrated that there was no foaming phenomenon of the PLLA film during desorption and sorption processes. The XRD spectra implied that the crystalline degree of PLLA film decreased after CO2 processing. It was concluded that PLLA polymer could be well swollen and plasticized by supercritical CO2.     

利用石英晶体微量天平测定紫杉醇在二氧化碳中的溶解度

A quartz crystal microbalance (QCM) is used to determine the phase equilibrium of paclitaxel-carbon dioxide system in the pressure range of 0-11 MPa and at temperatures of 35 °C,40 °C and 45 °C.The experimental results indicated that gaseous CO2 could be absorbed poorly into paclitaxel.The swelling of paclitaxel film in CO2 was observed before paclitaxel dissolved into supercritical carbon dioxide (ScCO2) with the increase of pressure.It was found that ScCO2 was not a good solvent for paclitaxel.The mole fraction of paclitaxel in ScCO2 was in the range of (4.5×10-9)-(7.8×10-9) under all our experimental conditions.Therefore,a much higher pressure than the CO2 supercritical point and/or a cosolvent must be used in any processes wherever paclitaxel dissolution in ScCO2 is required.     

苯乙烯/二氧化碳/聚苯乙烯三元混合物的相平衡预测

A lattice fluid model,Sanchez-Lacombe equation,is used to predict the phase behavior for a styrene/CO2/polystyrene ternary system.The binary parameters involved in the equation were optimized using experimental data.Phase diagrams and the distribution coefficients of styrene between polymer phase and fluid phase are obtained over a wide rang of pressure,temperature and composition.The analysis of ternary phase diagrams indicates that this system at relatively high pressure or low temperature may display two-phase equilibrium,and at low pressures or high temperatures three-phase equilibrium may appear.The distribution coefficients of styrene between the fluid phase and the polymer phase increase asymptotically to unity when the concentration of styrene increases.The results provide thermodynamic knowledge for further exploitation of supercritical carbon dioxide assisted devolatilization and impregnation.