多相平衡的杠杆规则

多相平衡的杠杆规则王正烈（天津大学化学系，天津３００Ｏ７２）一、问题的提出杠杆规则在相平衡的计算中很重要，通常所说的杠杆规则，主要用于二组分及三组分系统的两相平衡。二组分系统三相平衡能否应用杠杆规则，一般书上并不提及，有的认为不能应用，但未作说明￣［...     

50℃时P2O5-MgO-NH3-H2O四元体系相平衡研究

本文测定了P2O5-MgO-NH3-H2O四元体系在50℃时的相平衡数据, 绘出了干盐相图。应用Pitzer电解质溶液理论进行了活度系数关联, 计算了所研究体系在50℃的相平衡数据。     

微小液滴化学势及其在界面化学中的应用

推导了微小液滴化学势的关系式及其在界面化学中建立和推导相平衡关系的应用。     

恒压相图的边界理论及其应用

简要阐述了恒压相图的边界理论及其在许多方面的应用。可供与相平衡和相图有关课程的教师和学生参考。     

范特荷夫方程在相平衡中的应用

提出了在把相平衡视为特殊的化学平衡的前提下．利用关于平衡常数的范特荷夫方程可导出相平衡条件下温度、压力及平衡浓度间的关系，与通常的相平衡处理方法相比显得更为简便。     

物理化学课程中相平衡理论的教学策略

针对物理化学相平衡章节体系多变、知识点繁多、相图抽象等问题提出了一套系统的教学策略。首先对相平衡中的基本概念和定律进行论述,并强调重、难点;随后对章节知识点进行总结归纳,通过表格系统罗列相图的体系、相律、应用和术语;最后提出相图解读通行方法,并结合具体例子讲解这些方法、相律以及杠杆规则如何使用。     

基于格子的链状流体分子热力学模型

格子模型是高分子溶液理论最常采用的流体模型,在此基础上建立的分子热力学模型在流体混合物的热力学性质、相平衡行为的计算等方面有广泛的应用．最近,我们对基于格子的混合亥氏函数模型重新进行了审视,采用统计力学理论推导与计算机模拟相结合的现代分子热力学研究方法建立了新的分子热力学模型,可以反映高分子链枝化、配位数、链刚性、共聚物链组成、氢键、压力等的影响,对小分子系统和高分子溶液的热力学性质和相平衡关系的计算不仅与Monte Carlo模拟结果吻合,比现有其他理论预测效果更好,对高分子溶液、离子液体混合物等实际系统的相平衡计算也取得令人满意的结果,显示出模型优越的工程应用价值．本文对上述工作进行了系统总结．     

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。     

多元气-液-固复杂体系相平衡

石油流体中含有气相、液相及可能遇到的固相包括水合物、石蜡和沥青质等,涉及多元气-液-固复杂体系的相平衡问题.为防止这些沉积物堵塞造成安全隐患,需要确定水合物、石蜡、沥青质沉积起始条件以及沉积量.本文针对化学热力学理论在含水合物、石蜡和沥青质的多元-多相平衡研究中的应用进行了综述.水合物相平衡模型较为成熟,主要有两类,其一为基于等温吸附理论的van der Waals-Platteeuw型热力学模型;其二为基于双过程水合物生成机理的Chen-Guo水合物热力学模型.石蜡沉积一般采用活度系数法、状态方程法及多固相模型描述.沥青质絮凝、沉积则可采用溶解度参数模型、状态方程法、胶体模型和标度理论模型进行计算.同时对多元气-液-固复杂体系的相平衡研究发展方向进行了展望.     

含锶卤水体系相平衡和热力学研究进展

相平衡与热力学研究是卤水资源开发利用的理论依据,开展含锶多组分卤水体系相平衡和热力学研究,对于我国含锶卤水资源的开发利用具有重要的意义。从相平衡和热力学研究两方面,归纳总结国内外关于含锶卤水体系的研究现状,并指出了存在的主要问题和发展方向。     

化学平衡制图软件HYDRA/MEDUSA在大学化学教学中的应用

介绍化学平衡制图软件HYDRA/MEDUSA的基本功能与特点。结合大学化学课程在化学平衡教学方面的内容,分别给出了沉淀-溶解平衡、酸碱平衡、配位平衡与氧化还原平衡的应用实例,充分显示了该软件有利于学习大学化学课程中复杂的平衡计算,帮助认识各化学形态之间的化学反应和控制条件,也为涉及到化学平衡体系计算与形态分布的化学研究提供帮助。     

结合PBL的思维导图法在大学化学“四大平衡”教学中的应用

Taking the chemical equilibria including acid-base equilibrium, complexation equilibrium, precipitation equilibrium and redox equilibrium as an example, the application of the mind mapping combined with problem-based learning in university chemistry teaching is introduced.     

Chiral recognition of the Schiff bases by NMR spectroscopy in the presence of a chiral dirhodium complex. Deuterium isotope effect on 13C chemical shift of the optically active Schiff bases and their dirhodium adducts

The dirhodium method has been successfully applied in chiral recognition of the optically active Schiff bases, derivatives of ortho-hydroxyaldehydes existing in the NH-form. or at tautomeric equilibrium. The position of the equilibrium of Schiff bases as well as their adducts has been established on the basis of measurements of deuterium isotope effects on 13C chemical shifts. The presence of the proton transfer equilibrium or NH-tautomer has promoted the adduct formation. At the equilibrium state, formation of the adducts has shifted the proton transfer equilibrium towards the NH-form. The binding site was the oxygen atom of the proton donor group.     

土壤和水体中铝的化学平衡

详细综述了土壤环境中铝的形态及三大化学平衡：沉淀溶解平衡、水解平衡、络合平衡。     

信号流图在氧化还原反应平衡系统建模与计算中的应用

利用信号流图集成了化学平衡基本物理量之间的关系,为获取化学平衡计算公式提供便利.举例说明了氧化还原反应平衡系统信号流图模型的建模和利用信号流图模型求解平衡浓度的过程.     

支化高分子溶胶-凝胶相变的热力学

以典型的Aa-Bb型缩聚反应为例, 应用统计力学和热力学的基本原理对反应体系的一些平衡特征进行研究. 基于从两种不同角度所构造的正则配分函数, 导出反应体系的平衡自由能以及质量作用定律的解析形式, 同时指出获得数量分布函数的新方法, 并通过计算反应体系的等温压缩系数从而得到反应体系的凝胶化条件. 进一步利用数量分布函数的不变性, 给出临界点后溶胶相和凝胶相的平衡自由能, 探讨了溶胶-凝胶相变的相关问题.     

Effects of nonequilibrium on velocity and plate height in reactive capillary electrophoresis

Models for velocity and plate height for reactive CE are developed under the formalism of generalized nonequilibrium theory, as described by Giddings. The resultant equations are consistent with chromatographic theory and validated with an independent stochastic simulation. Moreover, unlike prior methods for CE, this model allows calculation of thermodynamic equilibrium constants and kinetic rate constants from a single, undistorted peak. The theoretical development shows that velocity is directly dependent on the equilibrium constant and is independent of the rate constant. On the other hand, plate height varies little with equilibrium constant and is inversely proportional to rate constant. The ability to evaluate equilibrium constants from velocity and rate constants from plate height is most greatly influenced by electric field strength and mobility difference. The accuracy in calculated equilibrium constants is limited by mobility difference; however, the accuracy in rate constants is limited by plate height and equilibrium constant.     

Pseudopartial wetting and precursor film growth in immiscible metal systems

We explore the equilibrium wetting behavior and precursor film growth in pure and alloy metallic systems. The systems exhibit equilibrium "pseudopartial" wetting, that is, a thin film in equilibrium with a nonzero contact angle in both liquid and solid states. The film spreading kinetics clearly indicates a diffusive transport mechanism. The alloying has only a small impact on the equilibrium wetting properties but strongly affects the transport during the growth of the precursor film.     

Reaction and phase equilibria of esterification of isoamyl alcohol and acetic acid at 760 mm Hg

The thermodynamic behavior of esterification reaction equilibrium and vapor–liquid equilibrium (VLE) of acetic acid and isoamyl alcohol mixture and its products, isoamyl acetate and water were investigated in this study. The experiments of chemical and phase equilibria were conducted in an Othmer type equilibrium cell. Since this esterification reaction proceeds very slowly, thus, a commercial Y type zeolite, NaY catalyst, was added to accelerate reaction rate such that the reaction equilibrium will be reached sooner and before phase equilibrium is considered. Using experimental data and phase and reaction equilibrium equations, the reaction equilibrium constants were calculated at different temperatures. The experimental results showed that the reaction equilibrium constant was very slightly dependent on temperature. The experimental data were then correlated by the Wilson, NRTL, and UNIQUAC models with the consideration of association effect of acetic acid in vapor phase. The concept of transformation composition by Barbosa and Doherty [D. Barbosa, M.F. Doherty, 1987, Proc. R. Soc. London Ser. A 413, 443–459.] was applied to construct three-dimensional figures showing experimental data and the calculated composition surfaces. It is observed from figures that the reactive azeotropy described by Barbosa and Doherty does not exist for this quaternary mixture. This study provides the required thermodynamic information for the development and design of this esterification process.