顺丁烯二酸酐-癸二酸二丁酯二元体系等温气液平衡

利用改进的沸点仪测定了顺酐-癸二酸二丁酯二元体系在413.15, 433.15和453.15 K下的等温气液平衡数据以及纯癸二酸二丁酯和顺酐的饱和蒸气压数据. 通过与文献值对比, 验证了此方法的可靠性. 同时, 将实验数据回归得到了纯癸二酸二丁酯和顺酐的Antoine常数. 利用NRTL方程进行了气液平衡数据的关联推算, 得到了顺酐-癸二酸二丁酯二元体系的NRTL模型参数. 利用UNIFAC基团贡献法对实验数据进行了预测, 其结果与实验值及运用NRTL方程拟合的结果吻合较好.     

马来酸酐与1，2－环己烷二羧酸二异丁酯的气液平衡

采用小沸点仪测定了马来酸酐和1,2－环己烷二羧酸二异丁酯二元系统在不同配料组成条件下的温度与压力数据，并通过内插法得到不同压力下的温度与配料组成的数据.进一步采用单纯形法优化NRTL方程参数，推算了平衡气液相组成，发现该二元系统具有最高压力恒沸点，且该恒沸点随压力的变化显著.当压力降低至20 kPa时, 由温度随气相组成的变化趋势知该恒沸点将趋于消失.     

乙酸乙酯-水二元物系汽液平衡的研究

本文使用自行设计的带机械搅拌器的平衡釜,在760mmHg压力下,测定了乙酸乙酯-水二元部份互溶物系的汽、液平衡数据.经热力学检验,该数据符合热力学一致性.用NRTL等13个活度系数方程进行热力学关联和计算,获得了满意的结果,尤以McCann方程和NRTL方程拟合的精度最佳.     

双液系气液平衡相图实验的研究

二组分完全互溶的双液系的气液平衡相图实验是物理化学实验的基本内容之一,通常是用沸点仪在常压条件下测定双液系在不同组成时的沸点和气、液两相呈平衡时的组成,从而作出沸点-组成相图。外界压力不同时,同一双液系的相图也不尽相同,所以恒沸点和恒沸混合物组成与外压有关。因此,通常情况下,用标准数据去衡量学生实验所得的恒沸点和恒沸混合物的数据就不够精确。本文是用自制的简易恒压沸点仪,在不同的压力下,对丙酮-氯仿和异丙醇-环己烷体系的恒沸点,恒沸混合物组成进行了研     

部份互溶体系4-甲基-2-戊醇和水的过量焓研究

使用LKB-2107型流动式微量量热计测定了4-甲基-2-戊醇和水这一部份互溶体系在293.15 K、298.15 K和303.15 K的常压过量焓。测量结果用Redlich-Kister方程作了关联。另外,还用该体系富醇区的过量焓数据拟合NRTL模型的参数与温度关系,推算较高温度下该体系的常压汽液平衡(VLE)组成及泡点。推算值与文献值是接近的。实验试剂4-甲基-2-戊醇由粗品经三次蒸馏提纯,沸点为404.95 K,折光率n_D~(20)1.4113,密度d~(20)0.8067 g cm~(-3),与文献值一致。无水乙醇、尿素均为分析纯。液体试剂在使用前均     

含甲基叔丁基醚体系的相平衡测定

测定了在20℃下甲基叔丁基醚-甲醇-水及甲基叔丁基醚-叔丁醇-水两组三元体系的液液平衡数据和在常压下各三元体系中二元配偶物系的汽液平衡数据。并将所测定的两组三元液液平衡数据与二元系数据用NRTL 及UNIQUAC 方程所得的参数推算的结果进行了比较,获得较满意的结果。     

甲醇—乙醇—水—盐体系的等压气液平衡

木文采用CPⅡ型沸点仪测定了在93.33kPa下甲醇-乙醇-水-盐(NaCl,NaBr,Nal,LiCl,CaCl_2)体系的气液平衡数据。实验证明,当三元混合溶剂的相对组成固定时,体系的沸点与加入的盐量呈线性关系,用热力学理论导出了该线性方程,用Gibbs相律探讨了该线性关系的起因。     

多功能汽液平衡测定仪的研究

研制了一种多功能液平衡测定仪－－CS-Ⅱ型VLE测定仪，阐述了该仪器的设计思想，该仪器兼有沸点仪和平衡釜的特点和功能，作为沸点仪，它具有泵结构搅拌器，可适用于拟静态法；作为平衡釜,它具有新型的汽液相取样结构和液相区冷却功能，可适用于安全互溶体系、部分互溶体系和高沸点差体系VLE的测定，本文给出了有关详细的实验考核结果。     

乙醇-水体系的气-液平衡

对非理想溶液平衡蒸气组成进行计算,有助于联系和检验实验数据。散见在各种文献上的这种计算方法很多,繁简和精确程度也不一。本文介绍的一种方法其特点为道理浅显,计算也不繁杂,在一次计算中可以同时解出具有某一组成的溶液沸点及其平衡蒸气组成。作者使用这种方法对乙醇-水体系的气-液平衡进行了计算,与实验数据对比,得到的结果一般是满意的。     

水-环己酮-甲基异丁基酮液液相平衡数据的测定与关联

为了给以甲基异丁基酮为溶剂含环己酮废水萃取过程的设计和流程模拟计算提供数据支撑,本文测定了常压下,水+环己酮+甲基异丁基酮（MIBK）三元体系在303.15、313.15及323.15 K的液液相平衡数据。据相平衡数据计算了分配系数和分离因子,所有的分离因子均远大于1,表明MIBK从水中萃取环己酮是可行的;Hand方程和Bachman方程的相关系数在0.99以上,表明实验数据具有较好的一致可靠性。同时,采用NRTL和UNIQUAC活度状态方程对实验数据进行了关联,回归得到了该三元物系的二元交互参数,结果表明两种模型均能很好关联实验数据,实验值和模拟值的相对均方根差（RMSD）低于0.5%。     

Isobaric (vapor + liquid) equilibria of the binary system maleic anhydride and diethyl phthalate at p = (2.67, 5.33, and 8.00) kPa

Saturated vapor pressures of pure diethyl phthalate were measured with the ebulliometer. And isobaric (vapor + liquid) equilibrium data for the binary system (maleic anhydride + diethyl phthalate) at p = (2.67, 5.33, and 8.00) kPa were determined using the ebulliometric method. The parameters of the NRTL model for the binary system were obtained by calculating equilibrium compositions of the liquid and vapor phase with the experimental equilibrium temperatures, pressures and feed compositions. Moreover, (vapor + liquid) equilibrium data for the binary system were predicted by use of the UNIFAC model. Predicted results were compared with those from the ebulliometric method, and showed good agreement.     

Isobaric vapor–liquid equilibria of the binary system maleic anhydride and di-isobutyl hexahydrophthalate at 2.67, 5.33 and 8.00 kPa

Isobaric vapor–liquid equilibrium (VLE) data for the binary system maleic anhydride (MAN) + di-isobutyl hexahydrophthalate (DIBE) at 2.67, 5.33 and 8.00 kPa were measured with a modified ebulliometer. Also, saturated vapor pressures of pure DIBE were measured and Antoine constants were obtained. These data were used to calculate equilibrium vapor and liquid compositions for this binary system using the NRTL model. Prediction of the VLE was done with the universal quasi-chemical functional-group activity coefficients (UNIFAC) model. The predicted results generally agree with those from experiment.     

Isobaric vapor–liquid equilibrium for methyltrichlorosilane–dimethyldichlorosilane–benzene system

Isobaric vapor–liquid equilibrium (VLE) for the system methyltrichlorosilane–dimethyldichlorosilane–benzene and that of the three binary systems were measured with a new pump-ebulliometer at the pressure of 101.325 kPa. These binary compositions of the equilibrium vapor were calculated according to the Q function of molar excess Gibbs energy by the indirect method and the resulted VLE data agreed well with the thermodynamic consistency. Moreover, the experimental data were correlated with the Wilson, NRTL, Margules and van Laar equations by means of the least-squares fit, the acquired optimal interaction parameters were fitted to experimental vapor–liquid equilibrium data for binary systems. The binary parameters of Wilson equation were also used to calculate the bubble point temperature and the vapor phase composition for the ternary mixtures without any additional adjustment. The predicted vapor–liquid equilibrium for the ternary system accorded well with the experimental results. The separation factor of methyltrichlorosilane against dimethyldichlorosilane in benzene was also reported. The VLE of binary and multilateral systems provided essential theory for the production of the halogenated silane.     

Combined chemical and phase equilibrium for the hydration of ethylene to ethanol calculated by means of the Peng-Robinson-Stryjek-Vera equation of state and the Wong-Sandler mixing rules

Due to the economics of the ethylene market and the subsidized production of fermentation-based ethanol in some countries, use of the ethylene hydration process to make ethanol has been steadily declining. The economics of this process might improve by combining the reaction and separation in a reactive distillation column, whose conceptual design requires a study of the combined chemical and phase equilibrium (CPE) of the reacting system. In this work, the Peng-Robinson-Stryjek-Vera equation of state was combined with the UNIQUAC activity coefficient model through the Wong-Sandler (WS) mixing rules in order to correlate the available experimental data for the vapor-liquid equilibria (VLE) of the ethylene-water, ethylene-ethanol, and ethanol-water binary systems at 200 °C. The interaction energies of the UNIQUAC model and the binary interaction coefficient of the WS mixing rules were used as the fitting parameters. From the optimum values of these parameters, both the VLE and the combined CPE of the ethylene-water-ethanol ternary system were predicted at 200 °C and various pressures. At this temperature, the catalytic activity of a H-pentasil zeolite has already been reported to exhibit a maximum for ethylene hydration, and also the experimentally measured two-phase region of the ternary system is sufficiently wide. By means of the reactive flash method, the chemical equilibrium compositions of the liquid and vapor phases were determined for several pressures, and the equilibrium conversion and the vapor fraction were calculated as functions of the ethylene to water feed mole ratio. It turns out that the vapor-liquid mixed-phase hydration of ethylene achieves equilibrium conversions much higher than those computed for a vapor-phase reaction that would hypothetically occur at the same conditions of pressure and feed mole ratio. It was found that the reactive phase diagram of the ternary system exhibits a critical point at 200 °C and 155 atm.     

Measurement of vapor-liquid equilibrium in systems with components of very different volatility by the total pressure static method

To make feasible the experimental study of vapor-liquid equilibrium (VLE) in the systems mentioned in the title, a static apparatus for accurate measurement of total vapor pressures of solutions was constructed. Mixtures of known composition are prepared synthetically in a thermostated equilibrium cell by weight from pure degassed components and the total pressure is measured by a quartz Bourdon gage. A procedure was developed for degassing pure liquids to a degree corresponding to the high precision of pressure determination required. The static assembly was tested by comparing obtained isothermal vapor pressures and calculated excess Gibbs free energies with literature data for the benzene - cyclohexane system at 14 and 20°C, respectively. Additional experimental vapor-pressure data are presented for pure cyclohexane, benzene, and N-methylpyrrolidone (abbreviated throughout this paper as NMP) at 6–24°C and for the binary systems of benzene-cyclohexane at 8°C and cyclohexane - NMP and benzene - NMP at 8, 14, and 20°C over the entire composition range. The binary data were reduced by a modified Barker's method to evaluate excess Gibbs free energies and vapor phase compositions.     

Thermodynamic properties of new heat pump working pairs: 1,3-Dimethylimidazolium dimethylphosphate and water,ethanol and methanol

Ionic liquid 1,3-dimethylimidazolium dimethylphosphate ([MMIM][DMP]) + water/ethanol/methanol mixtures exhibit properties which render them suitable as candidates for working pairs in industrial applications of absorption heat pumps or chillers. In this paper, the thermodynamic properties including vapor pressure, density, viscosity, heat capacity as well as excess enthalpy of these binary systems were measured at various temperatures with different ionic liquid concentrations. The thermodynamic properties were correlated by different equations, respectively. The correlated values were significantly consistent with the experimental ones. In conclusion, the vapor–liquid equilibrium (VLE) data indicated that the vapor pressures of the three solvents in [MMIM][DMP] displayed a considerable negative deviation from Raoult's law, and the excess enthalpies of the three binary systems are negative. These characteristics are necessary and important for an absorption working pair.     

苯—正庚烷—乙醇三元体系加压汽液平衡的研究

用双循环武加压汽液平衡装置测定了苯-正庚烷-乙醇三元体系在101.3、302.5、506.8、709.3、810.6 kPa下的汽液平衡数据。根据有关二元体系在对应压力下的汽液平衡数据所求得的能量配偶参数,对该体系的汽液平衡进行了预测,计算值与实验值符合良好。     

Multiphase equilibria for binary and ternary mixtures containing propionic acid,n-butanol,butyl propionate,and water

Isothermal vapor–liquid equilibrium (VLE) data were measured for propionic acid + butyl propionate at 373.15 and 393.15 K, and isothermal vapor–liquid–liquid equilibrium (VLLE) data were also measured for n-butanol + water, butyl propionate + water, and water + n-butanol + butyl propionate at temperatures ranging from 323.15 to 393.15 K. No azeotrope was found in propionic acid + butyl propionate. The mutual solubility data of the binary aqueous systems were correlated well with the NRTL model accompanying with temperature-dependent parameters. Improvement on the calculation of saturated vapor compositions has been made by using two-term virial equation with one adjustable binary interaction parameter to represent the non-ideality of the vapor phase. The model parameters determined from the binary VLLE data of n-butanol + water and butyl propionate + water and the binary VLE data of n-butanol + butyl propionate are capable of predicting satisfactorily the VLLE properties for the ternary system of water + n-butanol + butyl propionate.     

从过量体积推算液相活度系数与汽液平衡数据

本文运用统计热力学导出了一个直接由过量体积数据推算液相活度系数的新模型--EVLAC模型,本模型主要从“双液胞腔”与“局部组成”等概念出发,通过配分函数导出y-x表达式和V^E-x表达式,仅需要一个温度下的V^E-x数据即可推算出不同温度下盼恒温y-x,数据和不同压力下的恒压y-x数据,在不需要增加多元可调参数的情况下,可推广应用至多元体系。