Measurement and modeling of vapor-liquid equilibrium for ternary system water + 2-propanol + 1-butyl-3-methylimidazoliumchloride简

Vapor-liquid equilibrium （VLE） data for water ＋ 2-propanol ＋ 1-butyl-3-methylimidazolium chloride （[bmim]Cl） were measured. Six sets of complete T, x, y data are reported, in which the 2-propanol mole fraction on IL-free basis is fixed separately at 0.1, 0.2, 0.4, 0.6, 0.8, and approximate 0.98, while the IL mass fraction is varied from 0.1 to 0.8, in an interval of 0.1. The non-random-two-liquid （NRTL） and electrolyte non-random-two-liquid （eNRTL） equations are used to correlate the experimental data with satisfactory results. The ternary VLE behavior is also modeled with the parameters obtained by correlating two data sets, in which the mole fraction of 2-propanol on IL-free basis is approximately 0.1 and 0.98. In this way, the six sets of data are reproduced satisfactorily. With the eNRTL model, the root-mean-square deviation for temperature is 0.82 K and that for vapor-phase mole fraction is 0.0078. The influences of IL on activity coefficients and relative volatility of the volatile components are also graphically illustrated.     

Proposal and evaluation of a new norm index-based QSAR model to predict pEC50 and pCC50 activities of HEPT derivatives☆

The search and development of anti-HIV drugs is currently one of the most urgent tasks of pharmacological studies.In this work,a quantitative structure–activity relationship(QSAR) model based on some new norm indexes,was obtained to a series of more than 150 HEPT derivatives(1-[(2-hydroxyethoxy)methyl]-6-(phenylthio)thymine) to find their pEC_(50)(the required effective concentration to achieve 50% protection of MT-4 cells against the cytopathic effect of virus) and pCC_(50)(the required cytotoxic concentration to reduce visibility of 50% mock infected cell) activities.The model efficiencies were then validated using the leave-one-out cross validation(LOO-CV) and yrandomization test.Results indicated that this new model was efficient and could provide satisfactory results for prediction of pEC_(50) and pCC_(50) with the higher R_(train)~2 and the higher R_(test)~2.By using the leverage approach,the applicability domain of this model was further investigated and no response outlier was detected for HEPT derivatives involved in this work.Comparison results with reference methods demonstrated that this new method could result in significant improvements for predicting pEC_(50) and pCC_(50) of anti-HIV HEPT derivatives.Moreover,results shown in this present study suggested that these two absolutely different activities pEC_(50) and pCC_(50) of anti-HIV HEPT derivatives could be predicted well with a totally similar QSAR model,which indicated that this model might have the potential to be further utilized for other biological activities of HEPT derivatives.     

Investigation on characteristics of liquid self-diffusion in slit nanopores using simple quasicrystal model of liquid☆

Dynamical properties of liquid in nano-channels attractmuch interest because of their applications in engineering and biological systems. The transfer behavior of liquid confined within nanopores differs significantly from that in the bulk. Based on the simple quasicrystal model of liquid, analytical expressions of self-diffusion coefficient both in bulk and in slit nanopore are derived from the Stokes–Einstein equation and the modified Eyring's equation for viscosity. The local self-diffusion coefficient in different layers of liquid and the global self-diffusion coefficient in the slit nanopore are deduced fromthese expressions. The influences of confinement by porewalls, pore widths, liquid density, and temperature on the self-diffusion coefficient are investigated. The results indicate that the self-diffusion coefficient in nanopore increaseswith the porewidth and approaches the bulk value as the pore width is sufficiently large. Similar to that in bulk state, the self-diffusion coefficient in nanopore decreases with the increase of density and the decrease of temperature, but these dependences are weaker than that in bulk state and become evenweaker as the porewidth decreases. Thiswork provides a simplemethod to capture the physical behavior and to investigate the dynamic properties of liquid in nanopores.     

Bi-ionic chloride-nitrate equilibrium in a commercial ion-exchange membrane

Chloride-nitrate equilibrium was studied using the Neosepta ACS® anion-exchange membrane. Ion-exchange isotherm and selectivity coefficient were performed on the basis ofthe Donnan equilibrium and Helfferich's equilibrium relationship. Fixed ionic group concentration and water activity coefficients in the membrane were constant for any concentration of the nitrate and chloride ions in the solution. It was shown that the selectivity coefficient is more than unity and that the membrane has a good selectivity for nitrate ions.     

应用于离子液体体系汽液平衡测定的液相配制、气相分析方法

面向离子液体应用于萃取精馏,讨论了离子液体体系汽液平衡测定的液相配制、气相分析方法,提出了改进的气相回流器和沸腾器结构。基本思路来源于韩世钧先生研究团队发展的汽液平衡测定的拟静态法和置换法,以及能够主动提供气化中心的沸腾器结构。提出了液相组成计算方法和误差估计,适用于含多个挥发性组分和多个非挥发性组分体系的任意组分。上述方法能够实测获得挥发性组分的活度系数,并避免较为繁琐的含离子液体液相的分析。通过连续配制测定,能够获得活度系数随组成的变化规律,并应用于萃取精馏溶剂性能的评价及筛选。     

水盐体系汽液平衡的热力学模型研究

水盐体系的相平衡性质是化工单元操作的基础,在化学化工、海洋、地质等领域有着重要的研究价值。国内外许多学者对水盐体系汽液平衡进行了实验和理论的研究,构筑了各具特色的经验和半经验的模型。针对水盐体系,在NRTL理论的基础上,基于水化作用和混合盐假设建立了能够预测混合体系汽液平衡的活度系数扩展模型。通过对21组二元水盐体系和14组混合体系的关联计算,验证了该模型的可行性;同时,该模型可以采用二元体系参数直接预测计算混合水盐体系汽液平衡。     

Generalized LIQUAC model for the single‐ and mixed‐solvent strong electrolyte systems

A generalized strong electrolyte LIQUAC model is presented to describe the vapor–liquid equilibria, osmotic coefficients, mean ion activity coefficients, and solid–liquid equilibria for the single‐ and mixed‐solvent electrolyte systems over the entire concentration range from infinite dilution to saturated solutions. An appropriate reference state for the ions was first applied to test the capability of the model in simultaneously describing the mean ion activity coefficients and the solubility of a salt in a binary solvent mixture. The influence of salt on the vapor–liquid equilibrium behavior is predicted with the new correlated parameters. The generalized activity coefficient formulations are presented through the investigation of thermodynamic properties and phase phenomena in the single‐ and mixed‐solvent electrolyte systems. This work is a continuous study for the LIQUAC activity coefficient model. A reliable representation of the single‐ and mixed‐solvent salt solutions is obtained. © 2010 American Institute of Chemical Engineers AIChE J, 2011     

基于MPHC活度系数模型关联烃－水体系液－液平衡

基于普遍化范德华配分函数理论，应用由局部组成概念导出的方阱流体配位数模型导出了链状分子混合物的配位数模型，并由此建立了一个新的活度系数模型；将其应用于高度非理想体系汽－液平衡活度系数的关联，结果与Ｗｉｌｓｏｎ方程相当，但方程参数随温度变化较小；其于Ｎｅｗｔｏｎ－Ｒａｐｈｓｏｎ－Ｇａｕｓｓ液－液平衡算法，应用新模型对烃－水体系的液－液平衡进行了关联计算，结果优于ＮＲＴＬ方程     

基于MPHC活度系数模型关联烃－水体系液－液平衡

基于普遍化范德华配分函数理论，应用由局部组成概念导出的方阱流体配位数模型导出了链状分子混合物的配位数模型，并由此建立了一个新的活度系数模型；将其应用于高度非理想体系汽－液平衡活度系数的关联，结果与Ｗｉｌｓｏｎ方程相当，但方程参数随温度变化较小；其于Ｎｅｗｔｏｎ－Ｒａｐｈｓｏｎ－Ｇａｕｓｓ液－液平衡算法，应用新模型对烃－水体系的液－液平衡进行了关联计算，结果优于ＮＲＴＬ方程     

流体汽液相平衡混合规则研究进展

混合工质汽液相平衡学术内涵丰富且应用广泛，而混合规则是决定混合物性描述准确与否的关键因素。综述了具有代表性的混合规则，包括原始的二次型、非二次型、密度型、状态方程-超额自由能型等混合规则，评价了其在流体汽液相平衡的描述能力，辅以数学推导介绍了其发展的动机及存在的优劣，以期对将来混合规则发展提供思路。     

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     

基于COSMO-SAC模型的离子液体萃取剂的选择

COSMO-SAC模型是计算无限稀释活度因子的一种有效方法,只需知道分子结构,即可进行有机物或离子液体的无限稀释活度因子计算。COSMO-SAC模型中最耗时的计算步骤是产生σ-图谱(σ-profile)的量子化学计算。利用Materials Studio软件中的DMol3模块,建立了包含32种离子液体阴离子和191种离子液体阳离子的σ-图谱数据库。利用σ-图谱数据库和COSMO-SAC模型,针对离子液体液液萃取过程,提出了离子液体萃取剂的计算机辅助分子设计方法。以乙醇-乙酸乙酯体系为研究对象,选择了适宜的离子液体萃取剂,采用乙醇-乙酸乙酯-离子液体三元体系的液液平衡文献数据进行了验证。     

乙苯或二甲苯和异丙醇二元体系等压汽液相平衡

用经E llis汽液平衡釜验证的自制汽液平衡釜测定了异丙醇+乙苯及异丙醇+邻二甲苯、间二甲苯、对二甲苯4个二元液系在压力为99.80 kPa时的等压汽液平衡数据,并进行了热力学一致性检验。用UNIQUAC模型处理了实验数据,得出了二元体系的混合自由能。这不仅为二元液系混合体系充实了实验数据,还为二元液系的热力学研究丰富了理论依据。