正丁醇-水-醋酸丁酯三元物系液-液平衡数据的测定、关联和预测

测定了由正丁醇、水和醋酸丁酯形成的三元物系及部分互溶二元物系在20℃、30℃和40℃的LLE(液液平衡)数据,并与文献中已有的正丁醇-水的LLE实测数据核对,说明了测定方法的可靠性.用NRTL和UNIQUAC方程分别进行了三元和二元LLE数据的关联和预测.根据溶液热力学特性对二元LLE模型参数进行了鉴别.在三元LLE数据的关联中,对两种目标函数(摩尔分数和分配系数)进行了比较,并对前一种目标函数中的权重取值问题进行了考察.通过对部分互溶二元物系参数的评选,提高了利用二元参数对三元物系进行预测的准确度.     

Changes in the miscibility of binary and ternary blends having the same chemical components and compositions

The phase behavior of ternary blends of dimethylpolycarbonate (DMPC), tetramethyl polycarbonate (TMPC), styrene-acrylonitrile (SAN) copolymer has been explored. The experimental phase behavior of ternary blends was compared with that of binary blends having the same chemical components and compositions except that the DMPC and TMPC were present in the form of copolycarbonates (DMPC-TMPC). Miscible region of DMPC/TMPC/SAN ternary blends is narrower than that of DMPC-TMPC/SAN binary blends. In addition, phase separation temperature of binary blend was higher than that of corresponding ternary blend. However, the entropic and energetic terms of ternary blends were more favorable for miscibility than those of binary blends. To understand the phase behavior of blends, phase stability conditions of binary and ternary blends were analyzed. Some ternary blends that have negative interaction energy were not miscible because these blends do not satisfy stability conditions. It was revealed that the addition of component, accompanied by the asymmetry in the binary interactions, results in destabilization of blend.     

二甲基硫醚-吡啶-N,N-二甲基乙酰胺体系汽液平衡关联和预测

在101.325 kPa下用沸点仪测定了二甲基硫醚-吡啶、二甲基硫醚-N,N-二甲基乙酰胺、吡啶-N,N-二甲基乙酰胺3个二元体系以及二甲基硫醚-吡啶-N,N-二甲基乙酰胺三元体系不同液相组成时的汽液平衡数据,3个二元体系活度因子分别用Wilson、NRTL、Margules、van Laar和UNIQUAC模型进行关联,用最小二乘法求出了它们的液相活度因子模型参数,用这些模型参数计算它们的汽相组成。根据过量Gibbs自由能函数,采用间接法由Tpx预测了3个二元系的汽相平衡组成。用所得的液相活度因子计算3个二元体系的过量Gibbs自由能。3个二元体系的Wilson、NRTL、Margules、van Laar和UNIQUAC模型参数分别对所测的三元体系数据进行关联,建立该系统汽液平衡的热力学模型并计算平衡时的汽相组成和泡点温度。分别由Herington法和McDermott-Ellis法对3个二元体系和三元体系进行热力学一致性检验,结果表明这些相平衡数据满足热力学一致性。     

Prediction of ternary azeotropes

Interaction constants for binary azeotropic mixtures have been used in conjunction with binary azeotropic information to predict ternary azeotropic compositions and temperature. The method operates within a general classification of liquids based on their hydrogen bonding capabilities, and therefore may be used to predict ternary azeotropic information of a wide variety of mixtures.     

The vapour—liquid equilibria of the binary,ternary and quaternary systems formed by acetone,methanol, propan-2-ol,and water

The vapour-liquid equilibrium data of the binary, ternary and quaternary systems that may be formed by combination of the components acetone, methanol, propan-2-ol and water, have been determined at 760 mmHg by means of an equilibrium still based on the principle of circulation of both phases. The binary data have been correlated by means of the Margules and of the Wilson equation. The data of the ternary and quaternary systems have been predicted by these equations. The results of both equations are discussed and compared.     

DETERMINATION,CORRELATION AND PREDICTION OF LIQUID-LIQUID EQUILIBRIUM DATA OF n-BUTYL ALCOHOL-WATER-BUTYL ACETATE TERNARY SYSTEM

Liquid-liquid equilibrium(LLE)data have been determined for the n-butyl alcohol-water-butyl acetateternary system and the related binary systems at 293.15,303.15 and 313.15 K.The experimentally determinedLLE data for the n-butyl alcohol-water binary system have been found to be in satisfactory agreementwith the available literature data.The correlation and prediction of the LLE data have been done byusing NRTL and UNIQUAC models.The model parameters of binary systems have been identified witha thermodynamic criterion.In the correlation of ternary LLE data,two objective functions(mole fractionand distribution constant)have been used for purpose of comparison.The effect of weighting in the firstobjective function has been examined.In predicting the ternary LLE with different sets of parameter valuesobtained for each of the constitutent binary systems,improved prediction results have been obtained bycomparing the results of different combinations of the sets of parameter values and choosing those givingthe best result.     

The influence of raw materials composition on the properties of fired clay products

One factor controlling formation of ceramic structures is the initial mineralogical composition which has a great influence on processing and fabrication stages and the properties of the product. This paper investigates the relationship between the mineral content of raw compositions and the product properties after thermal treatment. Optimum compositions have been established for binary and ternary systems of kaolinite, hydromica, montmorillonite and also their genetic varieties. The trends have been used to develop new ceramic compositions with improved properties.     

Phase Equilibria in the System La2O3—Iron Oxide in Air

Phase equilibria data are presented for compositions in the system La₂O₃-iron oxide in air. Liquidus and solidus curves were obtained by the quenching method in the iron-rich portion of the system. The remainder of the diagram was determined using a strip-furnace technique. Two compounds have been found, the ortho-rhombic perovskite LaFeO₃ and a compound with the magnetoplumbite structure corresponding to a composition LaFe₁₂O₁₉. LaFeO₃ was determined to melt congruently at about 1890°C. whereas LaFe₁₂O₁₉ has both a stability minimum and maximum at 1380° and 1421°C., respectively. The iron-rich portion of the system is essentially ternary whereas the remainder can be considered to be a simple binary. Liquid compositions have been determined and are plotted in terms of the ternary system La₂O₃-Fe₂O₃-FeO.     

三元水盐体系冰点和共晶点的测定、相图表达及计算

针对Na⁺//Cl^-,NO₃^--H₂O、Na⁺//Cl^-,SO₄^2--H₂O和Na⁺,K⁺//Cl^--H₂O 3个三元水盐体系,测定了不同组成时溶液的冰点、共晶点以及降温过程的析盐规律,绘制出三元体系温度-组成立体相图。结果表明：三元体系的冰点、共晶点、相关系与组成可用三棱柱表达,3个三元水盐体系在共晶点温度下均无复盐存在,各含有1个两盐与冰的共晶点,3条单盐与冰或盐盐的共晶线,1个冰和两个单盐结晶区;用三元体系温度-组成立体相图能更直观地表达三元水盐体系的结晶区、冰点、共晶点和溶液组成的关系,可以判断溶液降温过程中的盐或冰的析出类型、温度;同时建立了冰点经验公式,应用经验公式和过量吉布斯自由能模型预测三元体系的冰点和共晶点,计算值和实验值吻合良好。     

The phase behavior of ternary blends containing polycarbonate,phenoxy, and polycaprolactone

Ternary blends comprising bisphenol-A polycarbonate (PC), the polyhydroxyether of bisphenol-A (Phenoxy), and poly(ε-caprolactone) (PCL) were found to be generally miscible at PCL levels greater than 60% by weight and to show multiple amorphous phases at lower PCL levels. The melting point depression of PCL in the miscible region of the ternary and in the miscible binary blends with PC and Phenoxy was examined to obtain the enthalpic interaction parameters, B_ij, for each of the three binary interactions. The parameters associated with the miscible binary blends were negative, as expected, and indicated that PCL interacts more exothermically with Phenoxy than with PC. The parameter associated with Phenoxy/PC interaction was strongly positive as expected from the complete immiscibility shown by these materials. The interaction parameters were used to calculate the locus of compositions for which the heat of mixing is zero. The locus was found to agree well with the observed boundary between miscible and multiphase behavior in the ternary. This suggests that the phase behavior of ternary blends is largely determined by the same enthalpic considerations known to govern the phase behavior of binary blends.     

A local composition model for multicomponent liquid mixture thermal conductivities

A local composition model for multicomponent, liquid mixture thermal conductivity has been developed and tested. Only binary equilibrium thermodynamic information is used in the model to obtain local compositions. No mixture thermal conductivity data are required and no adjustable parameters are used. Predictions based on this model agreed, within experimental uncertainty, with the experimental results for eighteen different binary mixtures at 1 atm and various temperatures. An average absolute percent deviation from experiment of 1.0% was obtained over the entire composition range for the eighteen systems. The maximum deviation at any of the tested compositions was 3.5%. Thermal conductivities for ternary systems have also been computed.     

A direct method for calculating ternary vapor compositions from total-pressure measurements

Ternary vapor compositions have been successfully calculated from total-pressure measurements for four systems by means of a modified direct method, which involves the previously proposed concept of hypothetical binary mixtures, and permits the numerical integration using a simple P-x relationship. The results of the systems tested further indicate that the ternary y values predicted from only binary P-x data are not significantly different from the y values obtained when binary together with ternary P-x values were used in the calculation, provided that the initial fit of binary P-x data is successful.     

Low-temperature anti-icing reagents in aqueous salt systems containing acetates and formiates

Ice-melting polytherms in binary and ternary aqueous salt systems containing metal and ammonium acetates and formiates were studied in the temperature range of 0 to ?70°C. A number of salt mixtures that form low-temperature eutectics with ice were revealed to be promising as a basis for the development of anti-icing reagents. The properties of these salt mixtures, such as ice-melting ability, the character of their action on cement concrete, and corrosion activity with respect to metals and alloys, were estimated. An efficient corrosion inhibitor was selected.     

二甲基硫醚-二硫化碳-甲醇体系等压汽液平衡

用泵式沸点仪测定了100 kPa下二甲基硫醚-二硫化碳、二甲基硫醚-甲醇2个二元系以及二甲基硫醚-二硫化碳-甲醇三元系在不同液相组成时的汽液平衡数据,用Wilson、NRTL、Margules和van Laar模型分别对2个二元系活度系数进行关联,用最小二乘法求出其液相活度系数模型参数,用这些模型参数来计算其汽相组成y,根据过量Gibbs自由能函数Q(GE/RT),采用间接法由Tpx推算了2个二元系的汽相平衡组成。用所得的液相活度系数计算2个二元系的过量吉布斯自由能函数GE/RT,并由2个二元系与三元系回归出二硫化碳-甲醇二元系的NRTL模型参数。用3个二元系NRTL模型参数对所测的三元系数据进行关联,建立三元系汽液平衡的热力学模型并计算平衡时的汽相组成y和泡点温度。分别由Herington法和McDermott-Ellis法对2个二元系和三元系进行热力学一致性检验,结果表明这些相平衡数据满足热力学一致性。     

The physicochemical properties of the mixed solvent of 2-piperidineethanol,sulfolane and water

The physicochemical properties of the mixed solvent of 2-piper-idineethanol (2-PE), sulfolane (TMS) and water were determined over a wide range of temperatures and compositions. The density, the viscosity and the dissociation constant, as well as the solubility of N₂O in this mixed solvent were correlated as a function of temperature and composition over the entire experimental range. The models are useful not only for the ternary solvent system, but also for the binary solvent systems, such as 2-PE+H₂O and TMS+H₂O. From the regression, it has been found that the interaction of aqueous 2-PE solution and aqueous TMS solution is negligible.     

Free volume as an internal material parameter to probe interfaces in ternary polymer blends: A positron lifetime study

A new method to characterize individual interfaces in ternary polymer blends from experimentally measured fractional free volume from Positron Annihilation Lifetime Spectroscopy (PALS) has been developed. By this, we derive the composition dependent miscibility level in ternary polymer blends. This method has its genesis in KRZ (Kirkwood–Risemann–Zimm) theory which introduces hydrodynamic interaction parameter as a measure of excess friction generated at the interface between dissimilar polymer chains resulting in energy dissipation. The method successfully applied for binary blends has been theoretically modified to suit ternary blends in the present work. The efficacy of this method has been tested for two ternary blends namely polycaprolactone/poly(styrene‐co‐acrylonitrile)/poly(vinyl chloride) (PCL/SAN/PVC) and polycaprolactone/poly(vinyl chloride)/poly(vinyl acetate) (PCL/PVC/PVAc) in different compositions. We obtained a maximum effective hydrodynamic interaction (α_eff) of ?12.60 at composition 80/10/10 of PCL/PVC/PVAc while PCL/SAN/PVC showed ?1.60 at 68/16/16 composition. These results suggest that these compositions produce high miscibility level as compared to other compositions. DSC measurements have also been used to supplement positron results. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3335–3344, 2013     

Calculation of ternary equilibrium vapor compositions from total vapor pressure-liquid composition data

A simple and direct method for evaluating ternary vapor-liquid equilibrium compositions from measurements of the total vapor pressure exerted by the liquid phase along lines of constant liquid mole fraction ratio is presented. Application has been successfully made to the ternary system nitrogen-argon-oxygen at 180°r. The proposed method modifies that for binary systems and can be conveniently applied to ternary systems at low to medium pressures.     

乙醚-甲醇-正丁醇多元系汽液平衡的热力学性质

用新型泵式沸点仪测定了在101.325 kPa下乙醚-甲醇、乙醚-正丁醇、甲醇-正丁醇3个二元系以及乙醚-甲醇-正丁醇三元系在不同液相组成时的沸点,并用间接法Tpx推算了3个二元系的汽相平衡组成y.3个二元体系活度系数分别用Wilson模型、NRTL模型、Margules模型和van Laar模型进行关联,用最小二乘法...     

EXCESS ENTHALPIES FOR TERNARY MIXTURES PHENOL-3-METH YLPHENOL-1 -HEX ANOL, 3-METHYLPHENOL-l-HEXANOL- CYCLOHEXANOL AND THEIR CONSTITUENT BINARIES AT 318.15 K

Excess enthalpies H^E for two ternary systems, phenol-3-methylphenol-l-hexanol and 3-methylphenol-l-hexanol-cyclohexanol and four constituent binaries have been measured with Calvet-type micro-calorimeter at 318.15 K. The UNIFAC group contribution method and a version, the UNIFAC(3Q), as well as the Redlich-Kister equation have been applied in predicting ternary excess enthalpies. Based on the binary H^E data, new interaction parameters have been determined.     

甲醇-甲基丙烯酸甲酯-水三元系汽液平衡和液液汽平衡的研究(Ⅱ)三元系部分

本工作测定了25、35、45、55和60℃时甲醇-甲基丙烯酸甲酯-水三元系互溶区蒸汽压以及部分互溶区的液液平衡和蒸汽压数据.用各对二元系修正的UNIQUAC模型参数推算得到的三元系相平衡数据与实验值符合良好,表明这些模型参数可作为对该三元系进行由低压至常压的相平衡计算基础数据.