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。     

高压下二元系超额体积的拟合

利用F函数改进的立方状态方程—FRKS方程,并在二元互作用函数中引入压力项因子,对高压下二元系的超额体积进行拟合。压力项因子的引入,使得该方法能够适用于温度、压力变化的体系。对十个高压下的二元系的拟合结果表明,该方法能给出较好的拟合结果。     

用二元交互作用函数预测高压下多组分体系的气液平衡

用和体系的状态有关且满足不变性条件的二元交互作用函数,结合F函数修改的立方状态--方程FRKS方程,预测高压下多组分体系的气液平衡.选择15个三元体系及其组分二元系来检验方法的可行性,这些体系覆盖了从简单的接近理想溶液行为的体系到高度非理想体系.计算结果表明,该方法不仅能相当精确地关联各种类型二元系的气液平衡,而且能在仅用组分二元系参数的条件下较准确地预测所考察的所有三元体系的气液平衡     

正构烷烃/JP-10二元体系的体积性质

利用Anton PaarDMA55和Ubbelohde黏度管分别测定了正辛烷和正癸烷两种正构烷烃与挂式四氢双环戊二烯{C10H16, exo-tricycle[5.2.1.02.6]decane(JP-10)}组成的二元体系在298.15 K下的密度和黏度, 计算了正构烷烃/JP-10二元体系的超额摩尔体积、组分的表观摩尔体积和偏摩尔体积等体积性质以及组分对超额体积的贡献, 研究结果表明, 烷烃的加入使得二元体系的超额体积均为负值. 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, 熵驱动起主要作用. 从分子间相互作用角度讨论了二元体系体积性质的变化规律.     

超额自由能型汽液相平衡混合规则

较全面地介绍了近几年来发展的各种典型的超额自由能型汽液相平衡混合规则。该类混合规则吸取了状态方程法和活度系数法在相平衡预测方面的优点,并将对于极性体系预测能力非常强的活度系数模型直接应用于状态方程法的相平衡预测中,实现了向高温区的良好外推和对超临界和亚临界组分的连续准确描述。依次发展的HV型、WS型和TC型三个大类的超额自由能型混合规则中,TC型混合规则的预测精确度要略高于HV型、WS型混合规则的预测精确度,而HV型、WS型混合规则的预测精确度大致相当。从发展的角度看,这些超额自由能型混合规则还要接受三元以上体系的汽液相平衡和液液相平衡预测的考验。另外,如何将超额自由能型混合规则扩展到多参数方程来提高相平衡预测精度,也是超额自由能型混合规则的一个值得关注的发展方向。     

正丁醇、乙酸乙酯、正己烷的二元及三元体系的超额焓测量和关联

用等温稀释量热计测定了正己烷+正丁醇、正己烷+乙酸乙酯二元体系在303.15K、308.15K及正丁醇+乙酸乙酯+正己烷三元体系在303.15K的超额焓,用Kretschrner-Wiebe理论组合UNIQUAC方程所得数学模型对二元体系在303.15K的超颠焓进行了关联,并预测了所测三元体系在303.15K的超额焓,预测结果与实验值比较,平均偏差为6％。     

TBP体系活度系数的测定和微扰理论的研究

在前人工作的基础上, 改进了液上空间气相色谱测活度系数的方法, 实验测定了TBP. 稀释剂和水形成的多个二元系、三元系和四元系的活度系数和密度. 选用的稀释剂有n-C_6H_(14)、n-C_7H_(16)、n-C_8H_(18)、C_6H_6、cy-C_6H_(12)、CCl_4和CHCl_3. 在Pierotti理论的基础上, 采用新的硬球作用表达式和径向分布函数, 并计及分子间的排斥能、色散能、取向能和诱导能, 建立了简单的活度系数模型, 并用于TBP和稀释剂体系的计算. 从二元系回归得到的分子参数较好地预测了三元系的活度系数.     

三元——假二元系的过量体积

提出测量三元——假二元系(1-x)[(1-y)A+yC]+z[(1-y)B+yC]的过量热力学函数的方法, 测量了在298.15 K下两种假二元系: A=环己烷, B=苯, C=甲苯, 甲基环己烷的过量体积V~E, 用van der Waals单流体模型对实验结果进行了讨论。     

Flory状态方程理论研究PS/PMMA/SAN相行为

将改进的Flory状态方程理论(EOS)引入含“分子内链段排斥性相互作用”的高分子共混物中,研究含无规共聚物的三元共混体系聚苯乙烯(PS)/聚甲基丙烯酸甲酯(PMMA)/聚苯乙烯-丙烯腈(SAN)无规共聚物的相行为,建立相应的适用于含无规共聚物三元共混体系Spinodal方程.用PS、PMMA、PAN的特征参数及其链段间相互作用参数分别计算相应共聚物的特征参数,由二元相互作用模型计算均聚物-共聚物间的相互作用能参数.在运用EOS理论研究三元均聚物共混体系相行为基础上,进一步预测PS/PMMA/SAN体系的相行为,计算并绘制不同温度下的Spinodal曲线并进行实验验证,理论计算与实验结果吻合.结果表明,EOS理论可以克服经典平均场理论的缺陷,成功描述含分子内排斥作用共混体系相行为与共聚物组成及温度之间的关系.     

二元体系C6H5CH3-DMF在293.15 K时的体积性质

利用Anton Paar DMA4500振动管密度计测量了293.15 K时二元体系甲苯-N,N-二甲基甲酰胺(C6H5CH3-DMF)在C6H5CH3(摩尔分数0~1)中的溶液密度, 利用最小二乘法关联了溶液密度与组成的函数关系, 关联精度为±0.005 kg/m3. 通过密度数据分别计算了二元体系中C6H5CH3和DMF的表观摩尔体积, 并利用非线性最小二乘拟合法, 分别拟合得到了优化的C6H5CH3和DMF的表观摩尔体积和摩尔分数的函数关系, 以及C6H5CH3和DMF的表观摩尔体积和质量分数的函数关系. 通过对函数关系的极限运算得到了C6H5CH3和DMF的极限偏摩尔体积、标准偏摩尔体积和摩尔体积. 还计算了不同组分下体系的超额摩尔体积, 数据可用四参数Redlich-Kister方程关联拟合得到方程系数. 计算关联了C6H5CH3和DMF的超额偏摩尔体积与摩尔分数的关系. 由三参数多项式极限法得到组分的极限超额偏摩尔体积值与Redlich-Kister系数法得到的值在误差范围内一致.     

Calculation of the Density and Activity of Water in ATPS Systems for Separation of Biomolecules

In this study, the perturbed hard sphere chain equation of state is utilized to calculate the activity of water in binary and ternary solutions of polyethylene glycol (PEG), salt and water. The liquid density of the binary and ternary solutions is also predicted. To estimate the water activity in PEG–water binary systems, a linear correlation is obtained for the binary interaction parameter between water and PEG. Then, using this correlation and without introducing any additional binary parameters, the water activities are predicted in ternary solutions of water, salt and PEG with different molecular weights (MW). Our results show that the mean absolute average relative deviation (AARD %) of water activity for binary PEG–water solutions in 298 K is 0.73 %. In addition, the water activity in ternary solutions of water and two PEGs with different MW is predicted within 0.31 % AARD %. Furthermore, the AARD % for prediction of water activities in binary PEG–water solutions over the temperature range 308–338 K is 0.41 %. Also, the water activities of aqueous two-phase systems are predicted with AARD % = 0.64 %. In this regard, no adjustable parameters were correlated between salt and PEG. Finally, liquid densities were predicted in binary solutions of water–PEG and ternary solutions of water–PEG–salt.     

Excess Molar Volumes of (Methyl Ethanoate + 1-Chlorooctane + an n-Alkane) Ternary Mixtures and Their Constituent Binaries at 25°C

Excess molar volumes, at the temperature 25°C and atmospheric pressure over the whole composition range, are reported for the following binary mixtures: methyl ethanoate + (n-octane, n-decane); methyl ethanoate + 1-chlorooctane; 1-chlorooctane + (n-heptane, n-octane, n-nonane, n-decane); and for the ternary mixtures methyl ethanoate + 1-chlorooctane + (n-heptane, n-octane, n-nonane, n-decane). The values of excess molar volumes were calculated from density and composition results. The excess volumes were utilized to test the multiproperty group-contribution model of Nitta et al. using parameter sets available in the literature. Experimental results from ternary mixtures have also been compared to predictions from several empirical and semiempirical models, which utilize, exclusively, results from binary mixtures.     

Thermodynamic behaviour of ethanol+methanol+2-ethoxy-2-methylpropane system. Physical properties and phase equilibria

The densities, refractive indices and speeds of sound of ternary ethanol+methanol+2-ethoxy-2-methylpropane (ETBE) mixtures were determined at 298.15 K and atmospheric pressure, and were used to calculate the corresponding excess molar volumes and the deviations of the molar refractive index and isentropic compressibility from linear dependence on concentration. These excess and deviational quantities were best predicted by the equations of Radojkovic, Kohler and Jacob and Fitzner. Vapour–liquid equilibrium (VLE) data were obtained for the ternary system at 101.32 kPa, shown to pass thermodynamic consistency tests, correlated by means of the equations Wilson, NRTL and UNIQUAC, and compared with the results predicted by the ASOG-KT and original and modified UNIFAC methods and by the equations of Wilson, NRTL and UNIQUAC with interaction parameters obtained from data for the relevant binary systems. The agreement between the experimental data and the latter predictions was as good as was achieved by ASOG-KT and UNIFAC-Dortmund, which were the best of the group contribution methods.     

Volumetric Properties for Binary and Ternary Mixtures Containing Benzyl Alcohol,Ethyl Butyrate and Diethyl Malonate at <Emphasis Type="Italic">T</Emphasis> = (293.15–313.15) K and <Emphasis Type="Italic">p</Emphasis> = 0.087 MPa

The densities of binary and ternary mixtures of benzyl alcohol + ethyl butyrate and/or diethyl malonate were measured at T = (293.15–313.15) K and p = 0.087 MPa. From these data, the excess molar volumes, partial molar volumes, excess partial molar volumes, partial molar volumes at infinite dilution, thermal expansion coefficients and their excess values were calculated. The Redlich–Kister equations were fitted to the excess molar volumes data. The results show that the excess molar volumes for all considered binary and ternary systems are negative and decrease with increasing temperature. The same behavior was observed for the excess thermal expansion coefficients. Data for excess volumes in ternary system were fitted with the Nagata–Tamura and Cibulka models for which the Cibulka equation showed better fitting. The intermolecular interactions between molecules in these mixtures are discussed and explained based on these experimental data.     

Excess molar volumes ofn-alkanes-thiophene mixtures at 25°C

The excess molar volumes of binary mixtures of n-hexane, n-octane, n-decane, n-dodecane, and n-hexadecane with thiophene have been measured at 25°C over the whole mole fraction range. All the experimental values, except those for n-hexane-thiophene in the thiophene rich region, are positive. The Flory theory was used to determine the influence of molecular contact sites on the excess volumes. A new calculation procedure has been suggested by introducing a new parameter S. This method greatly improved the theoretical results.     

Volumetric and acoustic properties of the ternary system (1-butanol+1,4-dioxane+cyclohexane)

Densities and speeds of sound for the ternary system 1-butanol+1,4-dioxane+cyclohexane have been measured at the temperatures of 298.15 and 313.15 K. Excess molar volumes and excess isentropic compressibilities have been calculated from experimental data and fitted by the Redlich-Kister equation for ternary mixtures. The ERAS model has been used to calculate excess molar volumes of the ternary mixture from parameters obtained from the constituent binary mixtures.     

Excess molar volumes of N,N-dimethylformamide + 2-pentanone + alkan-1-ols mixed solvent systems at 303.15 K

Accurate excess molar volumes (V^E), at ambient pressure and 303.15 K, have been determined in the ternary liquid mixtures of N,N-dimethylformamide (DMF) + 2-pentanone (PE) + 1-alkan-1-ols (C₃-C₆) and in the binary mixtures of PE + alkan-1-ols (C₃-C₆) as a function of composition. The alkanols include 1-propanol, 1-butanol, 1-pentanol and 1-hexanol. The intermolecular interactions and structural effects were analyzed on the basis of the measured and derived properties. Excess molar volumes increase in magnitude with increase in chain length of alcohol. Valuable information on the behavior and governing factors of the liquid structure of the strongly associated solvents studied were inferred from the parameters deduced. The V^E results were correlated and fitted by the Redlich-Kister equation for binary mixtures and by the Cibulka equation for ternary mixtures, as a function of mole fraction. Several predictive empirical relations were applied to predict the excess volumes of ternary mixtures from the binary mixing data. An analysis of the data indicates a good agreement between experimental results and predicted values in all ternary systems. A discussion is presented and deviations are interpreted in terms of size, shape, the position of ketone group, the chain length of alkanol and hydrogen bond effects in the liquid mixtures studied to explain chemical and thermophysical behavior.     

Thermodynamic properties of the mixture benzene+cyclohexane+2-methyl-2-butanol at the temperature 298.15 K: excess molar volumes prediction by application of cubic equations of state

Excess molar volumes, changes of refractive indices, and changes of isentropic compressibilities of the ternary mixture benzene (1)+cyclohexane (2)+2-methyl-2-butanol (3), and the corresponding binary mixtures benzene (1)+2-methyl-2-butanol (3), and cyclohexane (2)+2-methyl-2-butanol (3) have been evaluated from density, refractive index, and speed of sound measurements at 298.15 K, and atmosphere. These derived properties of binary, and ternary mixtures were fitted to Redlich–Kister, and Nagata equations, respectively, the correlation parameters being gathered. In spite of the high non-ideality observed, the excess molar volumes were satisfactorily predicted by means of cubic equations of state with simple mixing rules.