磷酸三丁酯与醇二元混合体系的热力学性质

用量热法测定了298.15 K时, 磷酸三丁酯(TBP)+甲醇/乙醇/正丁醇/正丙醇四个二元混合体系的超额混合焓及293.15 K和303.15 K时部分组成下的超额混合焓, 其值均在−0.3 − 0.3 kJ•mol−1之间, 且基本不受温度的影响. 用无热溶液模型计算了各体系的超额熵、超额Gibbs自由能及各组分的活度系数. 热力学分析表明, TBP+甲醇/乙醇/正丙醇二元体系能较好地符合无热溶液模型, 而TBP+正丁醇体系则不符合无热溶液模型.     

N-甲基哌嗪与乙酸乙酯、乙酸丁酯二元混合体系在298.15～313.15K的体积及黏度性质

测定了N-甲基哌嗪+乙酸乙酯和N-甲基哌嗪+乙酸丁酯2个二元混合体系在298.15,303.15,308.15和313.15 K的密度和黏度数据,并计算了N-甲基哌嗪+酯二元混合体系的超额摩尔体积(VEm)和黏度偏差(Δη),用Redlich-Kister多项式关联了二元体系的超额摩尔体积与组成的关系,用4个半经验公式关联黏度数据并关联了二元体系的黏滞性活化参数.结果表明,N-甲基哌嗪+乙酸乙酯和N-甲基哌嗪+乙酸丁酯二元体系在所测温度范围内的超额摩尔体积为正值,黏度偏差为负值,且二元混合体系在混合过程中焓驱动居于主导地位.     

环己酮-醇二元系统超额焓测定和关联的研究

用MS-80型Calvet微热量计首次测定了环己酮＋乙醇、＋正丙醇、＋正丁醇、＋环戊醇、＋环己醇系统在293.15、298.15、303.15及308.15 K四个温度下的超额焓HE,并拟合为平滑方程,拟合方差很小.环己酮和醇组成的二元混合系统的超额焓在全浓度范围内都为正值,其最大值都处在醇浓度为50％附近.超额焓随着醇分子中含碳原子数的增多而增大；超额焓值受温度的影响很大,且随着温度的升高而增大.     

预测三元系超额焓的一种新方法

提出一种预测三元系超额焓的新方法。该方法利用改进的立方状态方程－－ＦＲＫＳ方程，并以二元互作用参数函数代替单一数值的二地互作用参数，为计算体系提供随状态变化的二元互作用参数数值。对十二个非理想三元系及其组分二元素的计算结果表明，该方法明显提高了二元系超额焓的拟合精度，从而在不引入任何三元参数的条件下较好地改进了三元系超额焓的预测。     

α-蒎烯+对伞花烃和β-蒎烯+对伞花烃二元体系超额焓的测定

采用BT2.15型Calvet微量量热计常压下测定了α-蒎烯+对伞花烃和β-蒎烯+对伞花烃两个二元体系在298.15 K、308.15 K及318.15 K下的超额焓. 实验数据采用Redlich-Kister方程进行关联, 标准偏差较小. 该两个二元体系的超额焓在全浓度范围内均为正值, 其最大值在摩尔分数x1=0.5附近. 温度对超额焓有一定的影响, 超额焓随温度的升高而增大. 相同温度下, α-蒎烯+对伞花烃体系的超额焓比β-蒎烯+对伞花烃体系的大.     

正丁醇/正戊醇+JP-10二元体系的体积性质

在常压下测定了298.15 K时正丁醇/正戊醇+挂式四氢双环戊二烯(C₁₀H₁₆, JP-10)二元体系的黏度和密度. 根据Eyring液体黏性流动理论, 关联了二元体系的黏滞性活化参数, 结果表明, 焓驱动起主要作用. 利用密度数据计算了醇+JP-10二元体系的超额摩尔体积、 超额偏摩尔体积、 表观摩尔体积及偏摩尔体积等体积性质, 结果表明此二元体系的超额摩尔体积为正值.     

等温稀释型量热计的建立和过量焓的测定

本文建立了一套等温稀释型量热计, 该量热计可用于吸热型体系过量焓的测定,量热计灵敏度为2μV.J^-^1, 恒温精度为±8*10^-^3K。经环己烷-苯体系和环己烷-正己烷体系在298.15K时标定, 精确度在15%以内, 测定了缔合体系在乙醇 -苯体系303.15K时溶液的过量焓。     

正烷醇/异丙醇二元体系过量焓的测定

用LKB 2277 Bioactivity Monitor测定了一些正烷醇(甲醇到正己醇)与异丙醇二元体系在298.15K的常压过量焓H^E的数据, 对丙醇/异丙醇, 正丁醇/异丙醇和正戊醇/异丙醇还测定了308.15K和313.15K的常压过量焓数据。同时给出了关联实验结果的多项式方程的各参数。     

丙烯腈、己二腈和丙腈与水的二元体系液-液相平衡数据的测定和关联(英文)

采用平衡法测定了丙烯腈+水、己二腈+水、丙腈+水三个二元体系在不同温度(303.15、313.15、323.15、333.15K)下的液-液相平衡数据;并采用NRTL(α=0.2,α=0.3)模型和UNIQUAC模型对液-液平衡数据进行了关联.结果显示,NRTL和UNIQUAC模型对三个二元体系在不同温度下的互溶度关联的目标函数值均小于1×10-17,实验值与计算值吻合较好,绝对偏差小于0.009,关联精度较高.该研究结果可为丙烯腈、丙腈和水三元平衡溶解度数据的模拟和预测提供可靠的基础数据,并对电解二聚法生产己二腈中电解液的分离提纯工艺具有一定的指导意义.     

用FRKS状态方程预测三元系超额体积

利用改进的立方状态方程－ＦＲＫＳ方程，并以二元互作用函数代替单一数值的二元互作用参数关联二元系的超额体积，得到二元参数，在不引入任何三元参数的情况下，直接用组分二元系作用函数的引入预测三元系的超额体积，对十二个三元系及其组分二元系的计算结果表明，二元互作用函数的引入明显提高了二元超额体积的拟合精度，从而使状态方程法能精确地预测三元系的超额体积。     

Excess molar volume measurements of ternary mixtures [2-propanol+ethyl acetate+n-hexane] and their binary constituents at 298.15, 308.15 and 313.15 K

The excess molar volume of the ternary mixture [2-propanol?+?ethyl acetate?+?n-hexane], and its binary constituents; [2-propanol?+?ethyl acetate], [2-propanol?+?n-hexane] and [ethyl acetate?+?n-hexane] were evaluated by the mixtures density measurements over the whole concentration range at three temperatures 298.15, 308.15 and 313.15?K. The excess molar volumes data were fitted to the Redlich–Kister (RK) type equation and the parameters of this equation have been calculated and presented for the studied mixtures.     

Densities and Viscosities of the Ternary Mixture (Benzene + 1-Propanol + Ethyl Acetate) at 298.15 K

Abstract

Densities and viscosities of the ternary mixture (benzene + 1-propanol + ethyl acetate) and the corresponding binary mixtures (benzene + 1-propanol, benzene + ethyl acetate and 1-propanol + ethyl acetate) have been measured at the temperature 298.15 K. From these measurements excess volumes, V^E , excess viscosities, η^E, and excess Gibbs energies of activation for viscous flow, G*^E , have been determined. The equation of Redlich-Kister has been used for fitting the excess properties of binary mixtures. The excess properties of the ternary system were fitted to Cibulka's equation.     

Analog calorimetry and UNIQUAC group contributions approaches to the miscibility of pvc with eva copolymers

The miscibility of blends of poly(vinyl-chloride) (PVC) with poly(ethylene-co-vinyl acetate) (EVA) was investigated through analog calorimetry and a group contribution procedure based on the UNIQUAC model. The group contribution parameters quantifying the pair interactions between the structural features of the above polymers were calculated from experimental excess enthalpies of a series of binary mixtures of chlorocompounds, esters and hydrocarbons. Enthalpy data were also collected for the ternary mixtures (2-chloropropane+ethyl acetate+n-heptane) and (2-chlorobutane + methyl acetate+n-heptane), chosen as possible models for the studied macromolecular mixtures. The miscibility window of the PVC-EVA blends is fairly predicted by the group contribution method. It is also acceptably predicted by the enthalpic behaviour of the first ternary set, but only when the latter is calculated with binary data. A slightly narrower miscibility range is predicted by the binary interaction model. The results of these procedures are compared and the higher reliability of the group contribution procedure is emphasized in terms of its capability to reproduce the exact structure of the macromolecules and the non-univocal choice of the model molecules involved in the analog calorimetry approach. This revised version was published online in July 2006 with corrections to the Cover Date.     

Excess Enthalpies of Ethyl tert-Butylether + 2,2,4-Trimethylpentane + Decane or Dodecane at 25°C

Measurements of excess molar enthalpies at 25°C in a flow microcalorimeter, are reported for the two ternary mixtures ethyl tert-butylether + 2,2,4-trimethylpentane + n-decane and ethyl tert-butylether + 2,2,4-trimethylpentane + n-dodecane. Smooth representations of the results are described and used to construct constant-enthalpy contours on Roozeboom diagrams. It is shown that useful estimates of the ternary enthalpies can be obtained from the Liebermann–Fried model using only the physical properties of the components and their binary mixtures.     

Calculation of immersion enthalpy data from adsorption isotherms

The thermodynamic equations for the calculation of binary and ternary immersion data in excess formalism are presented. Immersion enthalpies and entropies of the n-hexane/n-octane, n-octane/n-tetradecane and n-hexane/n-tetradecane binary mixtures as well as the n-hexane/n-octane/n-tetradecane ternary mixture on activated carbon are calculated from the temperature dependence of adsorption isotherms. In order to evaluate the quality of the calculations, the calculated immersion enthalpies of the binary mixtures on activated carbon are compared with those that were measured calorimetrically. It is shown that phenomenological thermodynamics can be used successfully to predict calorimetric data on the basis of adsorption excess isotherms.     

Isothermal vapor–liquid equilibria and excess molar volumes for the ternary mixtures containing 2-methyl pyrazine

Isothermal vapor–liquid equilibrium (VLE) data at 353.15 K and excess molar volumes (V^E) at 298.15 K are reported for the binary systems of ethyl acetate (EA)+cyclohexane and EA+n-hexane and also for the ternary systems of EA+cyclohexane+2-methyl pyrazine (2MP) and EA+n-hexane+2MP. The experimental binary VLE data were correlated with common g^E model equations. The correlated Wilson parameters of the constituent binary systems were used to calculate the phase behavior of the ternary mixtures. The calculated ternary VLE data using Wilson parameters were compared with experimental ternary data. The experimental excess molar volumes were correlated with the Redlich–Kister equation for the binary mixtures, and Cibulka’s equation for the ternary mixtures.     

Temperature Dependence of Excess Molar Volumes of Ethanol + Water + Ethyl Acetate

In order to design and optimize equipment needed for production of distilled alcoholic beverages, an adequate knowledge of their physical properties and phase equilibria is necessary. The key thermodynamic information needed is for those chemicals that are the main components in terms of nonideal behavior. In this paper we present the temperature dependence of the excess molar volumes of the ternary system ethanol + water + ethyl acetate in the range 288.15–323.15 K at atmospheric pressure, due to the importance of ethyl acetate among the flavor compounds contained in this type of beverage. The observed excess molar volumes are usually negative over the whole homogeneous composition range, but take on positive values as the binary ethanol + ethyl acetate system is approached and the liquid phase separation region is observed. Because the current process designs are strongly computer oriented, the accuracy of theoretical model predictions was examined. The experimental data were used to test the capability of the Soave–Redlich–Kwong (SRK) equation of state to predict the ternary mixture behavior from binary mixture interaction parameters, which were obtained from previously published data. Derived properties, such as partial the excess molar volumes, excess isobaric expansibility, and the pressure derivative of excess molar enthalpy at constant temperature were calculated, due to their importance in the study of specific molecular interactions.     

Excess enthalpies of the ternary mixtures: tetrahydrofuran + (diisopropyl ether or 2-methyltetrahydrofuran) + n-heptane at 298.15 K

Excess molar enthalpies, measured at 298.15 K in a flow microcalorimeter, are reported for the ternary mixtures (tetrahydrofuran + diisopropyl ether + n-heptane) and (tetrahydrofuran + 2-methyltetrahydrofuran + n-heptane). Smooth representations of the results are described and used to construct constant excess molar enthalpy contours on Roozeboom diagrams. The latter are compared with diagrams obtained when the model of Liebermann and Fried is used to estimate the excess enthalpies of the ternary mixtures from the physical properties of the components and their binary mixtures.     

Association model of fluids. Simultaneous representation of excess Gibbs energies and excess enthalpies for liquid mixtures with alkanols

The binary excess Gibbs energies and excess enthalpies of liquid mixtures of alkanols and hydrocarbons, acetone, methyl acetate, acetonitrile, organic acid, etc., are simultaneously correlated with a new association model whose equilibrium constants are defined in terms of the modified segment fractions of chemical species. The model predicts ternary vapor-liquid, liquid-liquid equilibria and excess molar enthalpies of those mixtures well using only binary parameters.     

Thermodynamics of the ternary mixture propan-1-ol + tetrahydrofuran + n-heptane at 298.15 K. Experimental results and ERAS model calculations of G, H and V

Excess molar enthalpies H^E and excess molar volumes V^E have been measured at 298.15 K and 0.1 MPa for the ternary mixture tetrahydrofuran (THF) + propan-1-ol (PrOH) + n-heptane including the three binary mixtures using flow calorimetry and a vibrating tube densitometer, respectively.

Molar excess Gibbs energies G^E have been measured at 298.15 K using a static VLE apparatus equipped with a chromatographic sampling technique for the vapor phase as well as for the liquid phase. Experimental results have been compared with predictions of the ERAS model.