色谱顶空法测活度系数及对三元极性体系液液平衡预测

用气相色谱顶空分析法测定 18组部分互溶三元极性体系在完全互溶区的 3个组分活度系数 ,由此拟合出 U NIQU AC过量自由焓模型参数 ,再用 U NIQUAC方程预测液液平衡。这一方法曾很好地用在水-正烷烃 -醇体系。将此法拓展到含醇、酮、酯 ,醚、卤烷烃和水等多种极性组分的三元体系液液平衡的预测 ,其结果与文献的液液平衡数据比较 ,平均均方根误差 1.4 1% ,表明本法对含极性组分的体系仍然可行     

叔丁醇-水-钾盐体系液液相平衡的研究

将氮化钾或碳酸钾加入到叔丁醇—水体系中时，可产生水富集相和叔丁醉富集相。实验测定了叔丁醇-水—氮化钾、叔丁醇—水—碳酸钾体系在25℃时的液液相平衡数据。结果表明，当水相中氮化钾或碳酸钾浓度较高时产生的叔丁醇富集相中含有可以忽略的盐，水富集相中含有可以忽略的叔丁醇，因此用氮化钾或碳酸钾可以成功地分离叔丁醇-水体系。采用Pitzer方程计算富水相中水的活度，用Wilson、NRTL或UNIQUAC方程计算富有机相中水的活度，将二者结合对液液相平衡数据进行理论计算，计算值与实验值符合较好。     

A crossover‐UNIQUAC model for critical and noncritical LLE calculations

A new model, named the crossover‐UNIQUAC model, has been proposed based on the crossover procedure for predicting constant‐pressure liquid–liquid equilibria (LLE). In this manner, critical fluctuations were incorporated into the classical UNIQUAC equation. Coexistence curves were estimated for systems having a diverse range of asymmetries. These systems included the LLE of five different mixtures, composed of nitrobenzene with one of the members of the alkane homologous family (either pentane, octane, decane, dodecane, or tetradecane), as well as an extra system having a different chemical nature, namely the mixture of n‐perfluorohexane and hexane, to further check the validity of the proposed approach. Using these nonideal mixtures, the validity of the new model was investigated within wide ranges, covering near‐critical to regions falling far away from the critical point. The graphical trends, as well as the quantitative comparison with experimental data indicated the good agreement of the proposed model results with the experimental data. A maximum AARD% value of 3.97% was obtained in calculating molar compositions by the proposed model for such challenging systems covering noncritical, as well as critical regions. In addition, to show the strength of the proposed crossover approach to describe properties other than LLE, molar heat capacities were investigated for the system of nitrobenzene + dodecane. © 2015 American Institute of Chemical Engineers AIChE J, 61: 3094–3103, 2015     

Vapor–liquid equilibria for ethyl acetate + methanol and ethyl acetate + ethanol mixtures: Experimental verification and prediction

This work aims of the determination of a series of vapor–liquid equilibrium (VLE) experimental data at low pressure (70 kPa) for binary mixtures of ethyl acetate with methanol and ethanol. The Fischer's ebulliometer was used for the measurements of VLE data. A complete series of equilibrium data was obtained such as pressure, temperature and compositions of the liquid and vapor phases (PTxy). The two VLE data sets were submitted to a thermodynamic consistence test, where the deviations were evaluated in all variables, using the UNIQUAC activity coefficient equation. The magnitude of the average deviations was within the experimental uncertainty satisfying the Gibbs–Duhen equation. The data sets were also used to test the prediction of the UNIFAC model in its original and modified editions and the results were also within experimental uncertainties. Then a series of binary systems containing alcohols (methanol and ethanol) and esters (methyl and ethyl acetate) were collected from the literature for testing systematically the capability of the UNIFAC contribution method for this type of mixtures.     

Influence of salt concentration on solubility and tie-line data for the system: Formic acid + n-butanol + water

The tie-line and solubility data, i.e. formic acid (FA) + n-butanol + water + NaCl, were resolved at T = 298.15 K and under ambient pressure. The Othmer–Tobias equation was applied in this study. The experimental data were correlated and all linear correlation coefficients were found to be approximately equal to 1. Both the Universal Quasi-chemical Theory (UNIQUAC) and Nonrandom Two Liquid Theory (NRTL) and NRTL models were employed in order to compare the experimental liquid–liquid equilibrium (LLE) and tie-line data. Consequently, the calculated and experimental data proved to be a good fit. Results show that adding salt to the system proved beneficial by increasing the separation of FA from water.     

1-乙氧基-2-丙醇/水/癸烷的液液平衡

引　言石油是目前最重要的能源 ,除了液体石油外 ,油砂和油岩也能作为石油资源 .油岩分散存在于砂岩层中 ,只能通过物理的方法开采 ,乳化是可利用的提取方式之一 .为了了解乳化的原理及其体系的变化动态 ,作者曾经考察了 2 乙氧基乙醇、癸烷和水的液液三相平衡[1] .作为系统研     

Characterization and solubility measurement and prediction of selected arylamines in hexane, methanol and benzene

The solubility of nine arylamine molecules in benzene, methanol and hexane was measured. These molecules were: triphenylamine, N-(4-methyl phenyl) N,N bis phenyl amine, N-(3-methyl phenyl) N,N bis phenyl amine, N,N-bis(4-methyl phenyl) N-phenyl amine, N,N-bis(3-methyl phenyl) N-phenyl amine, tritolylamine (N,N,N-tris-(4-methylphenyl)amine), N,N-bis-(4-methylphenyl)-N-(3-methylphenyl)amine, N,N-bis-(3-methylphenyl)-N-(4-methylphenyl)amine, and N,N,N-tris-(3-methylphenyl)amine. The solubility of these molecules was estimated using ideal solution theory, the Hildebrand equation, and UNIQUAC method. The ideal solution theory and the Hildebrand equation were not able to estimate solubility with high precision. However, UNIQUAC method was able to estimate the solubility with good accuracy. It was found that substitution of methyl group regardless of its number in aryl ring increases the solubility. In addition, meta-substitution always results in higher solubility regardless of the nature of the solvent. Physical properties, as well as electrochemical properties of these materials were also provided. Based on these data, the most promising candidates for device preparation should be: mTTA, TTA, mmmTTA, and mono-TPA. However, the only way to prove the above ranking would be to test the candidates in actual devices, which is outside the scope of this paper.     

含水和界面活性剂2-异丙氧基乙醇的混合物的液液平衡

测定了可用作界面活性剂的2-异丙氧基乙醇、癸烷和水在25℃时的液液相平衡数据,并用热力学模型ExtendedUNIQUAC模型推算了这些实验数据,Extended UNIQUAC模型成功地描述了2-异丙氧基乙醇、癸烷和水的液液三相平衡,准确地推算2-异丙氧基乙醇、癸烷和水混合液的热力学性质,实验结果和计算结果的均方根误差为1.01.