成膜溶剂对聚4-甲基戊烯-1膜形态结构及渗透汽化特性的影响

以聚4－甲基戊烯－1（PMP）为膜材质、分别以环己烷、三氯乙烯以及环己烷／三氯乙烯为溶剂，以浇铸法制备了PMP的均质致密膜。研究了不同溶剂体系的相对溶解能力和挥发速度对PMP膜结晶度和形态结构的影响，并对成膜的渗透汽化特性的影响进行了研究。     

低温氧等离子体改性海藻酸钠膜分离乙醇—水溶液

研究了氧等离子体对海藻酸钠膜的表面改性，并将该膜用于渗透汽化分离乙醇－水溶液。通过红外光谱、表面电阻、接触角等手段测试，表明在海藻酸钠膜表面增加了羟基、羧基及羰基，因而更加亲水。当分别用未处理的原始膜，氧等离子体处理膜处理表面对着原料液，以及处理表面对着减压侧用于渗透汽化法分离乙醇－水混和物时，性能明显不同。其结果是：上表面处理后，渗透通量明显增加，分离系数也较未处理略高；下表面处理后，渗透速度下     

RbCl在H2O-DMF混合溶剂中活度系数的测定

应用Corning-价阳离子选择电极（M~＋－ISE）和Orion氯离子选择电极组成可逆电池，CI~－－ISE|RbCl（m），H2O（1－x），DMF（x）M~ －ISE．测量该电池标准电动势E_m，运用扩展的Debye－Hckel公式，计算RbCl在283．15至318．15K七个温度下由H2O至H2O－DMF混和溶剂的标准迁移自由能ΔG和在不同组成（H2O－DMF）混合溶剂中平均离子活度系数γ±，并对迁移自由能及活度系数随混合溶剂有机物组份的摩尔分数的变化进行了讨论。     

锌基离子液体BMIZn2Cl5的性质研究

合成了对水和空气均稳定的锌基离子液体五氯化二锌-1-甲基-3-丁基咪唑(BMIZn2Cl5). 在313.15～343.15 K温度范围内, 测定了离子液体BMIZn2Cl5的密度和表面张力. 拟合并估算了BMIZn2Cl5的恒压热胀系数和表面熵, 并根据Glasser理论和离子液体的空隙模型, 讨论了BMIZn2Cl5的热力学性质, 估算出其晶格能和标准熵 , 计算了离子液体的恒压热胀系数α, 与实验值基本一致, 说明了空隙模型的合理性. 并利用Kabo和Rebelo的方法估算了锌基离子液体BMIZn2Cl5的正常沸点, 蒸气压, 汽化焓( )等性质参数.     

锌基离子液体BMIZn2Cl5的性质研究

合成了对水和空气均稳定的锌基离子液体五氯化二锌-1-甲基-3-丁基咪唑(BMIZn2Cl5). 在313.15～343.15 K温度范围内, 测定了离子液体BMIZn2Cl5的密度和表面张力. 拟合并估算了BMIZn2Cl5的恒压热胀系数和表面熵, 并根据Glasser理论和离子液体的空隙模型, 讨论了BMIZn2Cl5的热力学性质, 估算出其晶格能和标准熵 , 计算了离子液体的恒压热胀系数α, 与实验值基本一致, 说明了空隙模型的合理性. 并利用Kabo和Rebelo的方法估算了锌基离子液体BMIZn2Cl5的正常沸点, 蒸气压, 汽化焓( )等性质参数.     

非完全汽化法测定棕榈油中微量甲苯、二甲苯

采用正己烷稀释棕榈油样品，在相对较低的汽化温度下直接色谱进样，其中棕榈油不汽化留在汽化室的填充石英棉上，而甲苯和二甲苯汽化后进入毛细管柱进行FID检测，并与顶空气相色谱法进行了比较。该法的精密度比顶空法好，对于测定较高沸点的残留苯系物，检出限也更低。     

DSC法测定氮酮的汽化焓和正常沸点

氮酮 (正十二烷基杂氮庚酮ＡＺＯＮＥ)是促进皮肤对药物吸收的促进剂 ,广泛用于外用药的各种制剂之中[1,2 ] 。它是高沸点化合物 ,其沸点用一般方法很难测定。我们以邻苯二甲酸二丁酯、乙二醇为标准物 ,甘油为对照物 ,用ＤＳＣ(差示扫描量热 )法测定了氮酮的正常沸点和汽化焓 ,为实际生产提供了非常有用的数据。1　实验准确称取邻苯二甲酸二丁酯、乙二醇两种标准物 ,用ＣＤＲ 1差动扫描量热仪 ,自然气氛Ａｌ2 Ｏ3 为参比物 ,升温速率 80° ｍｉｎ ,分别进行ＤＳＣ测定 (标定热值时将样品池密封、标定温度值时样品池要用钢针打一微孔后再压合…     

用气相色谱、气相色谱－质谱对萘普生重要中间体6－甲氧基－2－乙酰萘合成反应的研究

 在优良抗风湿药物萘普生的重要中间体６－甲氧基－２－乙酰素的合成中存在溶剂硝基苯的毒性及所带来的污染。而改用二氯乙烷作溶剂，只加少量硝基苯即可。为配合合成工艺的优化，用气相色谱（ＧＣ）、气相色谱－质谱（ＧＣ／ＭＳ）对反应产物、副产物及多个杂质进行了定性分析研究，并在５％ＯＶ－１０１ＣｈｒｏｍｏｓｏｒｂＷＡＷＤＭＣＳ柱上完成了产物的内标定量分析。从而减少了副反应和高沸点杂质的生成，最终生产出了９５％以上含量的６－甲氧基－２－乙酰萘产品，收率达到６０％。     

用气相色谱、气相色谱－质谱对萘普生重要中间体6－甲氧基－2－乙酰萘合成反应的研究

在优良抗风湿药物萘普生的重要中间体６－甲氧基－２－乙酰素的合成中存在溶剂硝基苯的毒性及所带来的污染。而改用二氯乙烷作溶剂，只加少量硝基苯即可。为配合合成工艺的优化，用气相色谱（ＧＣ）、气相色谱－质谱（ＧＣ／ＭＳ）对反应产物、副产物及多个杂质进行了定性分析研究，并在５％ＯＶ－１０１ＣｈｒｏｍｏｓｏｒｂＷＡＷＤＭＣＳ柱上完成了产物的内标定量分析。从而减少了副反应和高沸点杂质的生成，最终生产出了９５％以上含量的６－甲氧基－２－乙酰萘产品，收率达到６０％。     

等价无穷小与合比定律在物理化学教学中的应用

利用等价无穷小的理论结合物理化学中环境熵变、理想稀溶液溶剂化学势和高聚物的相关概念分析了环境熵变、理想稀溶液溶剂化学势的计算公式和"黏度法测定高聚物相对分子质量"实验中的关键理论推导。利用合比定律与物理化学的杠杆规则、离子迁移数等知识点推导出杠杆定律和离子迁移数的相关公式。使抽象的、不易掌握的物理化学知识具体化,便于学生理解、掌握和运用。     

Computer-aided product design of alternative solvents based on phase equilibrium synergism in mixtures

A systematic methodology is proposed to find binary azeotropic mixtures as new alternative solvents for the extraction process of volatile aroma molecules widely used in perfume and cosmetic industries. We investigated the use of the reverse engineering approach with computer-aided product design (CAPD) instead of the traditional “trial and error” approach. First, the design problem is defined from the real functionalities of the classical solvents. The latter are translated into physicochemical properties and the corresponding boundary values for each property are defined. The reverse engineering method coupled with CAPD consists in using optimization techniques for building molecular structures that match as best as possible the complete set of target physicochemical properties, thus defining for each candidate a performance index. Property values are evaluated by using group contribution methods for each molecular structure generated by a CAPD tool or by using database values. Acknowledging the contradictory relationship between two selected physicochemical properties, that is, low boiling temperature and high flash point, which is rarely found in pure components, binary azeotropic mixtures were studied to enhance the global performance of solvent candidates. Dimethyl carbonate used as a solvent for the extraction of aroma molecules from plants exhibits between the boiling temperature and the flash point. It was selected as the key component for designing binary azeotropic mixtures. The global performance of the binary azeotropic mixtures was verified by means of calculations of the vapor–liquid and liquid–liquid equilibrium using modified universal functional activity coefficient (UNIFAC) method as a thermodynamic method.     

Application of the wilson-equation to azeotropic mixtures

Stephan, K. and Wagner, W., 1985. Application of the Wilson-equation to azeotropic mixtures. Fluid Phase Equilibria, 19: 201-219. The Wilson model is appropriate to describe low pressure phase equilibria. For binary mixtures only two parameters are needed. A diagram was developed, based on the Wilson model, allowing us to distinguish azeotropic from nonazeotropic binary systems. To apply this diagram the Wilson constants, and in addition the vapour pressure or boiling temperature and the molar entropy of vaporization of the pure componentes must be known. A few examples for the application of the method are discussed.     

Determination of the boiling point distribution of sulfur compounds in light cycle oil using GC with a flame photometric detector and pyrolyzer

A method has been developed to determine the boiling point distribution of sulfur compounds in light cycle oils (LCO'S). The method chosen for this analysis was GC with a flame photometric detector (FPD) and pyrolyzer. Tests were carried out to evaluate the recovery efficiency, repeatability, and accuracy of the method. Repeatabilities within 2% were obtained. The recovery of benzothiophenes and dibenzothiophenes was close to 100%; this was important because these are the major sulfur components in LCO's. No hydrocarbon or solvent interferences were observed with the use of the pyrolyzer, even for a 95% solvent level. Comparison with results from other techniques showed that the method accurately determined the levels of sulfur compounds in the LCO boiling point range.     

Molecular interpretation of Trouton’s and Hildebrand’s rules for the entropy of vaporization of a liquid

The entropy of vaporization at a liquid’s boiling point is well approximated by Trouton’s rule and even more accurately by Hildebrand’s rule. A cell method is used here to calculate the entropy of vaporization for a range of liquids by subtracting the entropy of the gas from that of the liquid. The liquid’s entropy is calculated from the force magnitudes measured in a molecular dynamics simulation based on the harmonic approximation. The change in rotational entropy is not accounted for except in the case of liquid water. The predicted entropies of vaporization agree well with experiment and Trouton’s and Hildebrand’s rules for most liquids and for water except other liquids with hydrogen bonds. This supports the idea that molecular rotation is close to ideal at a liquid’s boiling point if hydrogen bonds are absent; if they are present, then the rotational entropy gain must be included. The method provides a molecular interpretation of those rules by providing an equation in terms of a molecule’s free volume in a liquid which depends on the force magnitudes. Free volumes at each liquid’s boiling point are calculated to be ～1 Å³ for liquids lacking hydrogen bonds, lower at ～0.3 Å³ for those with hydrogen bonds, and they decrease weakly with increasing molecular size.     

The gelation rule of the polyol acetal derivatives in binary solvent mixtures

The tendency of a gelator to gel in mixed solvents is strongly correlated with its gelation behaviors in the corresponding single solvents.     

芴和芴酮最低共熔点的测定

采用X-4数字显示显微熔点测定仪测定了不同组成的芴与芴酮混合物试样的熔点,用最小二乘法近似处理组成与熔点数据,得到芴和芴酮的最低共熔点为57.4°C,其摩尔分数为芴39%和芴酮61%。该测定芴与芴酮最低共熔点的简单方法,可用于本科生的基础化学实验教学。     

Synthesis of indium nanoparticles: digestive ripening under mild conditions

Here we report the synthesis of monodispersed indium nanoparticles by evaporation/condensation of indium shot using the solvated metal atom dispersion (SMAD) technique, followed by digestive ripening in low boiling point (BP 38 °C) methylene chloride and in a high boiling point (BP 110 °C) toluene solvent. The as-prepared SMAD indium nanoparticles are polydispersed with particle size ranging from 25 to 50 nm, but upon digestive ripening (heating of colloidal material at the boiling point of solvent in presence of excess surface active ligands) in methylene chloride, a remarkable reduction of particle size was achieved. In higher boiling solvent (toluene), where the indium nanoparticles at reflux temperature are probably melted, it does not allow the best result, and less monodispersity is achieved. We employed different surface active ligands (amine, phosphine, and mixed ligands) to passivate these indium nanoparticles. The temporal evolution of the surface plasmon of indium nanoparticles was monitored by in situ UV-vis spectroscopy, and particles were characterized by transmission electron microscopy (TEM) and X-ray diffraction (XRD). The merits of this synthesis procedure are the use of bulk indium as starting material, tuning the particle size in low boiling point solvent, particle size adjustment with the choice of ligand, and a possible scale up.     

PVT properties of di-(2-ethyl hexyl) phosphoric acid

Di-(2-ethyl hexyl) phosphoric acid (hereafter referred as D2EHPA) is an important solvent for solvent extraction industry. It is also used in nuclear solvent extraction as a solvent for TALSPEAK and REVERSED TALSPEAK processes for actinide (III)–lanthanide (III) separation. Its PVT properties are not available in literature. In this work, group-contribution approach was used to predict its PVT properties as well as selected physical properties like normal boiling point.     

The Solution Precursor Plasma Spray Coatings: Influence of Solvent Type

The influence of solvent type on splat formation and coating microstructure using the Solution Precursor Plasma Spray process was studied. Droplet with a high surface tension and high boiling point solvent experiences incomplete solvent evaporation process in the plasma jet leading to a porous coating. Droplet created from a low surface tension and low boiling point solvent undergoes rapid solvent evaporation, solute precipitation, pyrolysis, melting process in the plasma jet and forms splat upon impacting on the substrate; the build-up of splats results in a dense coating.     

The coalescence of polystyrene in correlated binary solvents

The solution behavior of solvophobic polymers is crucial to the development of polymer coatings and polymeric drug delivery vehicles. In this article, the role of dipolar interactions is investigated in the solvophobic coalescence of polystyrene in binary correlated polar solvent mixtures. A simple model for coalescence thermodynamics is derived from correlations between thermally rotating dipole moments in the solvent. The stabilizing correlations lost to the solvent due to a solute's presence give rise to a driving force for the coalescence of solutes. This stabilization is offset by the entropy of mixing that favors the dispersion of solutes. Predictions are compared to the measured point of coalescence of polystyrene in acetone when different alcohols are titrated. The model is shown to capture this point of coalescence and conformation for a variety of systems. Our results suggest the significant property determining the solubility of nonpolar polymers in a polar liquid is a free energy resulting from attractive dispersion interactions between thermally rotating solvent dipole moments. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 948–955