多元系相界上的活度——一种活度计算的递推公式

据等温等压多相平衡Gibbs能最小原理并应用Lagrange未定乘数法导出多元系组元化学位和平衡成分关系式。由此给出三元系两相共存区边界上由一已知组元活度计算它组元活度的解析递推式。该结果被推广到K元K-1相平衡共存区相界。计算结果与实验值符合得较好。     

由含稳定化合物的二元相图计算化合物的活度

本文提出了一种含稳定化合物相图中化合物的活度计算的新方法,即根据已有的从相图提取活度的公式,结合质量作用定律,由纯组元的活度计算得到化合物的活度.用此方法计算了Al-Ca及In-Sb两个二元系中稳定化合物的活度,计算结果与文献值吻合较好.     

恒压相图中紧邻相区及其边界的关系

本文根据相律导出紧邻相区内不同的相的总数,及其相边界的维数之间的对应关系定理和它在恒压相图中的几条推论。应用这个定理及其推论,可导出相图原理中的边界法则和相区接触法则,亦可说明一、二、三、四元各类相区中紧邻相区及其边界的关系。     

对应关系定理及其推论在温度、压强、组成均可独立变化的多元相图中的应用

本文将文献[3]所导出的对应关系定理应用于温度T、压强P和组成x_i均可独立交化的多元相图,得到适用于这类相图的六条推论,讨论了这类相图中两个紧邻相区中的不同相的总数Φ、紧邻相区的相边界的维数R_1以及两个紧邻相区中共同具有的相的数目△Φ的变化范围和规律。同时又讨论了这类相图中两个紧邻相区的边界的维数R_1~′和Ri、△Φ的关系。根据所有这些规律和关系具体地分析了二元和三元体系的P-T-x相图中紧邻相区及其边界的关系。     

相图中紧邻相区及其边界的对应关系(Ⅱ)

根据相律导出紧邻相区内不同相的总相数Φ及其相边界的维数R₁的对应关系定理和它的六条推论。应用这个定理及其推论,可导出相图原理中的边界法则和相区接触法则,可阐明由简单相图单元构成复杂三元相图所必须遵循的十条经验规则,亦可说明一、二、三、四元相图中紧邻相区及其边界的相互关系,以及其他应用。     

用稳定化合物的熔化自由能从含稀土二元相图提取活度

本文用正规溶液模型，导出了用二元系稳定化合物的熔化自由能提取组元活度的公式，用Ｒｉｃｈａｒｄｓｏｎ假设进行了推广，并预报了Ｆｅ－Ｙ、Ｆｅ－Ｌａ二元系组元的活度。     

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.     

醋酸-水-醋酸乙烯酯三元系气液平衡的研究——Ⅰ.液相完全互溶区

本文报导了醋酸-水、醋酸-醋酸乙烯酯、水-醋酸乙烯酯等三对二元系以及醋酸-水-醋酸乙烯酯三元系在液相完全互溶区的气液平衡实验数据。文中还计算了经校正了醋酸气相缔合后的活度系数,作了热力学一致性校验,并尝试用NRTL式进行关联。当使用三对二元系的NRTL特征参数,对三元系液相完全互溶区的气液平衡进行了预测,与实验结果基本相符。三元系液相部分互溶区的实验数据与热力学关联的结果,将于第Ⅱ报中报导。     

相图中的对应关系定理及其与相律的关系

一、研究紧邻相区及其边界的关系的重要性相图是由若干个相区组成的。以图1的一个二元部分互溶的低共晶相图为例,这个相图由六个相区组成。研究相区组成相图的规律,主要就是要研究:(1)对于给定相区来说,符合什么条件的相区才能与其毗邻?(2) 这些紧邻相区之间的边界的性质如何?这就是说,要研究紧邻相区及其边界的关系。     

相图边界理论与相区接触定律及Gupta方法的比较

综述了恒压相图中与相邻相区及其边界关系有关的经验规则和理论法则, 重点比较了相图的边界理论和相区接触定律, 着重指出相区接触定律的不足, 并显示相图边界理论的确是一个比较基本的相理论. 还比较了Gupta方法和相图边界理论的方法在根据有限的信息构筑多元复杂恒压水平截面图上的优劣.     

Fluid multiphase equilibria and critical phenomena in binary and ternary mixtures of carbon dioxide, certain n-alkanols and tetradecane

Experimental results of fluid multiphase equilibria occurring in ternary mixtures of near-critical carbon dioxide, certain n-alkanols and tetradecane are presented. The following n-alkanols were used in this investigation: decanol, octanol, heptanol, hexanol and pentanol. In the ternary systems with decanol, octanol or heptanol a closed loop liquid-vapor two-phase region in the three-phase surface liquid-liquid-vapor was found. As far as the ternary system with decanol is concerned, this phenomenon is in agreement with an earlier and unexpected finding of Patton et al. (1993). In addition, it was also found in this study that the phase diagrams of the ternary mixtures with hexanol or pentanol as the n-alkanol show further complications.     

Liquid-liquid equilibrium of aqueous two-phase systems composed of poly(ethylene oxide) 1500 and different electrolytes ((NH4)2SO4, ZnSO4 and K2HPO4): Experimental and correlation

Phase diagrams of aqueous two-phase systems composed of PEO1500 + salt (di-potassium phosphate + potassium hydroxide or ammonium sulfate or zinc sulfate) + water were determined at (283.15, 298.15, and 313.15) K. All systems produce a large two-phase region; however the influence of temperature on the binodal position seems to be very small. By analyzing the effects of ammonium sulfate or zinc sulfate, it was observed that zinc was more effective in promoting phase separation than ammonium. The consistency of the tie-line data was ascertained by applying the Othmer-Tobias correlation. In this paper, aqueous two-phase systems data for nine ternary systems are correlated by using the NRTL model and UNIFAC for the activity coefficient. The results are very satisfactory, with root mean square deviations between experimental and calculated compositions as low as 0.99 and 1.21%, respectively. However the NRTL model better represents the systems in study, when compared with UNIFAC.     

Orientation of tie-lines in the phase diagram of DOPC/DPPC/cholesterol model biomembranes

We report the direction of tie-lines of coexisting phases in a ternary diagram of DOPC/DPPC/cholesterol lipid bilayers, which has been a system of interest in the discussion of biological rafts. For coexisting Ld and Lo phases, we find that the orientation angle α of the tie-lines increases as the cholesterol concentration increases and it also increases as temperature increases from T = 15 °C to T = 30 °C. Results at lower cholesterol concentrations support the existence of a different two-phase coexistence region of Ld and So phases and the existence of a three-phase region separating the two two-phase regions. Our method uses the X-ray lamellar D-spacings observed in oriented bilayers as a function of varying hydration. Although this method does not obtain the ends of the tie-lines, it gives precise values (±1°) of their angles α in the ternary phase diagram.     

Thermodynamic characterization of ternary compounds. II. The case of extensive defect association

The thermodynamic characterization of an isolated ternary compound having a fixed cationic content is extended to include the effects of association of multiply charged point defects. BaTiO₃ containing a stoichiometric excess of TiO₂ is again used as a specific example. Defect association can remove the commonality of defect types originating from different sources, e.g., from nonideal cation ratios and from changes in nonmetal activity. As a result, the strong dependence of cation activities on the nonmetal activity can be greatly reduced in certain cases, and the possibility that changes in nonmetal activity will drive the compound into a two-phase region may be decreased accordingly.     

盐对正负离子表面活性剂双水相性质的影响

主要研究了盐对SDS/CTAB/H₂O混合系统双水相相行为的影响, 并对双水相上相的液晶性质进行了初步的探索. 结果表明: 盐能促使阴离子双水相区和阳离子双水相区分别向SDS和CTAB方向移动, 并使双水相区加宽. 反离子扩散双电层中盐的离子半径越大, 其对ATPS区的位置及相区宽度的影响程度越大. 盐的浓度达到一定值时, 它对双水相的影响可以达到饱和状态. ATPS_a区的饱和盐浓度值大于ATPS_c区的饱和盐浓度值. 异号盐离子对反离子层的限制作用与其离子半径有关.     

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.     

How iodide anions inhibit the phase-transfer catalyzed reactions of carbanions

The inhibitory effect of iodide anions on the phase-transfer catalyzed reactions of carbanions generated in liquid-liquid two-phase systems by aqueous NaOH is due to preferential location of these anions in the interfacial region of the two-phase system—organic phase/concd aqueous NaOH. In such situation, the basic activity of NaOH in this region is decreased and the equilibrium of deprotonation of the carbanion precursors is disfavoured.     

Surfactant-free oil/water and bicontinuous microemulsion composed of benzene, ethanol and water

<正>Generally,a microemulsion consists of oil,water,surfactant and sometimes cosurfactant.Herein,we report a novel suffactant-free microemulsion(denoted as SFME) composed of benzene,water and ethanol without the amphiphilic molecular structure of traditional surfactant.The phase behavior of the ternary system was investigated,finding that there were a single-phase region and a two-phase region in ternary phase diagram.The electrical conductivity measurement was employed to investigate the microregion of the single-phase region,and a bicontinuous microregion and a benzene-in-water(O/W) microemulsion microregion were identified,which was confirmed by freeze-fracture transmission electron microscopy(FF-TEM) observations.The sizes of the microemulsion droplets are in the range of 20-50 nm.     

X-ray kinematography of phase transformations of three-component lipid mixtures: a time-resolved synchrotron X-ray scattering study using the pressure-jump relaxation technique

By using the pressure-jump relaxation technique in combination with time-resolved synchrotron small-angle X-ray diffraction (TRSAXS), the kinetics of lipid phase transformations of ternary lipid mixtures serving as model systems of heterogeneous raftlike membranes were investigated. To this end, we first established the temperature-pressure phase diagram of a model lipid raft mixture, 1,2-dioleoyl- sn-glycero-3-phosphatidylcholine (DOPC)/1,2-dipalmitoyl- sn-glycero-3-phosphatidylcholine (DPPC)/cholesterol (1:2:1), using Fourier transform infrared spectroscopy and SAXS, covering the pressure range from 1 bar to 10 kbar at temperatures in the range from 7 to 80 degrees C. We then studied the kinetics of interlamellar phase transitions of the ternary lipid system involving transitions from the fluidlike (liquid-disordered, l d) phase to the liquid-ordered (l o)/liquid-disordered (l d) two-phase coexistence region as well as between the two- and three-phase coexistence regions of the system, where also solid-ordered phases (s o) are involved. The phase transition from the all-fluid l d phase to the l o+l d two-phase coexistence region turns out to be rather rapid. Phases appear or disappear within the 25 ms time resolution of the technique, followed by a slow lattice relaxation process, which, depending on the pressure-jump amplitude, takes several seconds. Contrary to many one-component phospholipid phase transitions, the kinetics of the l d <--> l o+l d transition follows a similar time scale and mechanism for the pressurization and depressurization direction. A similar behavior is observed for the phase transition kinetics of the s o+l o+l d <--> l o+l d transformation and even for the s o+l o+l d <--> l d transformation, jumping across the l o+l d two-phase region. All transitions are fully reversible, and no intermediate states are populated. As indicated by the complex relaxation profiles observed, the overall rates observed seem to reflect the effect of coupling of various dynamical processes through the transformation, involving fast conformational changes in the sub-millisecond time regime and slow relaxation of the lattices growing, probably being largely controlled by the transport and redistribution of water into and in the new phases of the multilamellar vesicle assemblies.     

PVC–rubber blends. VI. The structure

The dependence of the dynamic shear modulus of blends of polyvinyl chloride and rubber on the temperature and concentration of the rubber was investigated. For a calculation of a theoretical value of the modulus a formula recently derived by Uemura and Takayanagi was adopted. This formula is based on the assumption of a two-phase system, in which one phase is a continual matrix and the other is discrete spherical particles, and of perfect adhesion between the phases. Most of the theories that clarify the part played by rubber in rubber-modified vitreous materials are based on these assumptions. In most cases we have found a good conformity between the theoretical and experimental values of the modulus. In a certain system with an outstanding impact strength, however, a severe discrepancy has been found. This implies that the present structural explanation of the high impact strengths of two-phase systems is not quite generally applicable.