核壳型聚丙烯酸丁酯/聚(苯乙烯-甲丙烯酸甲酯)乳胶粒子形态设计及模拟

在简化及限制的实验条件下，提出了一套界面张力的简化推算方法，通过计算证实了采用该简化算法所得界面张力可较为准确地预测丙苯体系复合乳胶粒子的热力学平衡形态．并且根据性能要求，通过界面自由能变化最小的热力学判据对核壳型聚丙烯酸丁酯／ 聚（ 苯乙烯 甲基丙烯酸甲酯） 复合乳胶粒子进行形态设计，采用种子半连续乳液聚合法制备复合乳胶，利用电镜对设计粒子的最终核壳形态进行了证实．     

PU/PSt型复合乳液粒子热力学平衡形态预测

以水性聚氨酯分散液为种子采用无皂乳液聚合新技术合成出了具有核壳结构的聚氨酯 聚苯乙烯(PU PSt)型复合聚合物乳液 .采用界面张力简化计算方法 ,通过界面自由能变化最小的热力学判据对合成的复合乳液粒子的热力学平衡形态进行了预测 .并利用透射电子显微镜和接触角法测定的膜的表面极性对其进行了证实 .结果表明 ,界面自由能变化的最小判据可以推广到PU PSt体系 ,文中给出的界面张力的简化计算方法是可行的 .     

聚氨酯/聚丙烯酸酯复合乳液粒子热力学平衡形态预测

以水性聚氨酯分散液为种子采用无皂乳液聚合新技术合成出了具有核壳结构的聚氨酯/聚丙烯酸酯（PU/PA）复合聚合物乳液。采用界面张力简化计算方法计算了聚合物与聚合物之间以及聚合物和水之间的界面张力,通过界面自由能变化最小的热力学判据对合成的复合乳液粒子的热力学平衡形态进行了预测。并利用透射电子显微镜观察和用接触角法测定的膜的表面极性对其进行了证实。结果表明：界面自由能变化的最小判据可以推广到PU/PA 体系,本文给出的界面张力的简化计算方法是可行的。     

非平衡热力学在界面传递过程中的应用

21世纪以来，随着各学科之间的交叉渗透，化学工程的研究对象越来越复杂，界面传递对多相化工过程的影响越来越显示出它的重要性，传统的传递模型已经很难对界面复杂动态的传递行为进行定量描述．本文应用线性非平衡态热力学理论，对传统物质传递模型进行描述，分析界面传递过程速率，强化的三个因素：界面传质系数K、传递截面积A、界面化学位梯度△u．以含钾化合物作为模型体系，基于非平衡热力学原理建立了描述和预测固一液界面处介质传递速率的模型，并建立了描述其溶解速率的通用模型和测定钾离子动力学数据的实验方法，通过分析探讨了多相过程速率强化的途径．     

纳米材料热力学的研究现状及展望

本文分别从纳米材料的热容、晶格参数、结合能、内聚能、界面能、界面应力、热稳定性、熔点、熔解焓、熔解熵、相图及纳米材料参与反应时反应体系的化学平衡、吸附能等方面对纳米材料热力学的研究进展进行了阐述,并对纳米材料热力学的研究和应用前景进行了展望。     

物理化学中的热力学方法、拓展及应用

主要依托物理化学中的热力学基本原理,浅议热力学方法、简介化工热力学方法和工程热力学方法及应用等。热力学方法主要有循环法、特性函数法、变量变换法、标准状态法、平衡法及极值法、微元法等,并归纳了各种方法的特点、作用及意义。对于学生学习物理化学中的热力学,具有一定的指导意义,拓展了热力学的基本知识。     

氨基酸在固/液界面的吸附作用

本文介绍了氨基酸在固/液界面吸附等温线的特点,氨基酸液相吸附热力学和活性炭、硅胶、二氧化钛、氧化铝、蒙脱土等自水中吸附氨基酸的机制。     

超分子体系的物理化学研究进展

本文介绍了超分子化学领域的研究进展, 评述了其中与物理化学有关的研究成果, 并从化学热力学、电化学、化学动力学、胶体与界面化学等几个主要方面加以讨论, 描述了超分子物理化学的基本框架。     

有机/无机纳米复合粒子平衡型态的热力学计算

有机/无机纳米复合粒子是一种应用广泛的复合材料, 采用细乳液聚合方法是制备此类复合粒子的有效途径, 其中分裂/融合过程是一种新型的制备工艺. 纳米复合粒子的型态控制是一个非常重要的方面, 从热力学角度出发, 把界面Gibbs自由能最低这一基本热力学原理应用于计算细乳液聚合、采用新型分裂/融合工艺制备的有机/无机纳米复合粒子平衡型态, 并推导了核壳型、半球型、夹心型和分离型复合粒子平衡型态的热力学方程. 通过比较特定制备条件下不同形态复合粒子的界面Gibbs自由能, 可以预测最稳定的有机/无机纳米复合粒子平衡型态.     

界面现象与材料的生物相容性

用界面化学基本理论阐明生物体与高分子材料接触时的界面现象，并研究界面热力学参数与材料生物相容性之间的内在联系及规律性，这是研制生物相容性，特别是血液相容性生物医用高分子材料的重要依据。本文就此领域的基本理论，主要方法有研究进展作了综合性介绍和述评。     

关于弯曲界面气液两相相平衡化学势相等热力学判据的讨论

Thermodynamic criterion of equal chemical potential for phase equilibrium between gas and liquid in curved interface has been introduced in many textbooks and papers. In this paper, the process of the derivation of the criterion is proved to be wrong with analysis. In order to solve the problem, a proof procedure for the thermodynamic criterion of equal chemical potential is provided based on the definition of chemical potential. At the same time, a new thermodynamic criterion of two-phase equilibrium in curved interface is established using Gibbs interface thermodynamics and a new method for derivation of Kelvin equation is put forward based on the thermodynamic criterion of two-phase equilibrium. The new criterion which is derived directly from the second law of thermodynamics has a specific thermodynamic significance and clear physical model.     

Thermodynamics of nanoadsorption from solution: Theoretical and experimental research

In this study, the effect of nanoparticle size on adsorption thermodynamics was investigated. The results of theoretical and experimental studies show that particle size significantly affects the equilibrium constant and thermodynamic properties of nanoadsorption. Relationships between the equilibrium constant, thermodynamic properties and particle size were derived using the thermodynamic theory of nanoadsorption. The equilibrium constant and thermodynamic properties were obtained by investigating the adsorption of Cu²⁺ onto different sizes of nano-ZnO and the adsorption of Ag⁺ onto different sizes of nano-TiO₂. Good agreement was achieved between results obtained by experiments and predicted by theoretical analyses. The equilibrium constant and the molar Gibbs free energy of nanoadsorption were found to increase with smaller nanoparticle size. However, the effects of particle size on the molar enthalpy and the molar entropy are uncertain. In addition, the molar Gibbs free energy, the molar enthalpy, the molar entropy and the logarithm of the equilibrium constant are linearly related to the reciprocal of the diameter of the nanoparticle. The thermodynamic properties revealed in this study may provide important guidelines for research and application in the field of nanoadsorption.     

Thermodynamics of the solution equilibria of 3-hydroxypyridine and pyridoxine in water-dioxane mixtures

The thermodynamics of tautomeric and microscopic ionization equilibrium constants of 3-hydroxypyridine and pyridoxine have been determined in waterdioxane mixtures (0–70% weight fraction in dioxane) ranging from 10°C to 50°C. Generally, for both types of processes, the entropic contributions to the Gibbs energy predominate and this tendency increase concomitantly with the dioxane content in the media. The thermodynamic parameters are consistent with the corresponding values obtained from macroscopic ionization processes. An equation for the equilibrium constant K as a function of temperature and a solvent characteristic parameter is proposed to predict the K values throughout the whole range of the temperature and solvent compositions studied.     

关于等温循环方法推导开尔文公式的讨论

等温循环方法是物理化学教材中推导开尔文公式的一个经典方法。本文从热力学基本原理出发,明确指出其中小液滴可逆相变为气体的吉布斯自由能变化值应由吉布斯自由能判据求解,并对温度恒定、两相压强分别恒定时的判据进行了重新推导。同时,本文还提出了一种对推导开尔文公式的等温循环法的新理解方式,该方式在建立的"箱管模型"辅助下,意义明确,便于理解,更适宜教学使用。     

Ag3PO4溶解热力学函数的晶面效应与温度效应

在室温下制备了立方体{100}、 四面体{111}、 菱形十二面体{110}和块体Ag₃PO₄微晶, 并进行了表征. 测定了其在不同温度下水溶液中的电导率, 结合强电解质溶液和溶解热力学理论, 得到了Ag₃PO₄微晶的溶解热力学函数. 以具有不同晶面的Ag₃PO₄微晶为模型, 研究了纳米材料溶解热力学函数的晶面效应和温度效应. 结果表明, 具有{110}晶面的菱形十二面体Ag₃PO₄的标准摩尔溶解吉布斯自由能()、 标准摩尔溶解焓()和标准摩尔溶解熵()最大, 具有{100}晶面的立方体Ag₃PO₄次之, 具有{111}晶面的四面体Ag₃PO₄最小; 溶解平衡常数(K_{\mathrm{SP}})和随着温度的升高而增大.     

Adsorption at liquid interfaces: The generalized Frumkin isotherm and interfacial structure

The thermodynamics of adsorption of amphiphilic surface-active compounds at the interface between two immiscible liquids is considered. At the interface, these molecules are supposed to replace a few of the adsorbed molecules of both solvents. Classical isotherms of adsorption (Frumkin, Frumkin-Damaskin, Langmuir, Henry) were based on the model of non-penetrable interface, where an adsorbate can substitute only molecules of one solvent. At the interface between two immiscible electrolytes, nonpolar oil/water interfaces, and liquid membranes amphiphilic molecules can substitute molecules of both solvent and classic isotherms cannot be used. The generalization of Frumkin isotherm for permeable and non-permeable interfaces, known as the Markin-Volkov isotherm, gives the possibility to analyze adsorption in a general case. The adsorption isotherms of pentafluorobenzoic acid at the octane/water interface at different pHs were measured by the drop-weight method. The thermodynamic parameters of pentafluorobenzoic acid (PFBA) adsorption at octane/water interface were determined. From the measurements of PFBA adsorption, the structure of the octane/water interface was determined. Substitution of one adsorbed octane molecule requires approximately three adsorbed PFBA molecules. This result shows that the orientation of solvent molecules at the interface is different from the bulk. Adsorbed octane molecules have a lateral orientation with respect to the interface. Gibbs free energy of adsorption equilibrium and thermodynamic parameters of PFBA adsorption show that the adsorption of PFBA at the octane/water interface is accompanied by a reduction in the attraction between adsorbed PFBA molecules as the pH decreases to the acidic region. Published in Russian in Elektrokhimiya, 2006, Vol. 42, No. 10, pp. 1194–1200. The text was submitted by the authors in English.     

不同粒度八面体纳米钼酸镉的表面热力学性质

室温条件下,采用反相微乳液法制备了一系列不同粒度的八面体纳米CdMoO4,并对其组成、结构及形貌进行了表征.基于纳米CdMoO4与块体CdMoO4热力学性质的本质差异,结合化学热力学基本理论与热动力学原理,导出了获取纳米CdMoO4表面热力学性质的关系式;在此基础上,利用原位微量热技术成功获得了所制备的不同粒度八面体纳米CdMoO4的表面热力学函数,如比表面Gibbs自由能、比表面焓和比表面熵.本文为获取纳米材料表面热力学函数提供了一种有效而普适的新方法.     

Ag3PO4微晶表面热力学函数的温度及形貌效应

在室温下采用离子交换法制备了四足状、 立方体状和十二面体状Ag₃PO₄微晶及Ag₃PO₄块体, 并进行了表征. 以Ag₃PO₄微/纳米和块体材料热力学性质的区别为基础, 结合化学热力学理论和热动力学基本原理, 导出摩尔表面热力学关系式. 在此基础上, 采用原位微量热技术获取Ag₃PO₄的化学反应动力学信息和表面热力学函数, 讨论了形貌和温度对表面热力学性质变化的影响. 结果表明, 四足状Ag₃PO₄的摩尔表面焓(\begin{array}{c}{H}_m^s\end{array})、 摩尔表面Gibbs自由能(\begin{array}{c}{G}_m^s\end{array})和摩尔表面熵(\begin{array}{c}{S}_m^s\end{array})最大, 立方体状次之, 十二面体状最小; \begin{array}{c}{H}_m^s\end{array}和\begin{array}{c}{S}_m^s\end{array}随温度的升高而增大, \begin{array}{c}{G}_m^s\end{array}则随温度的升高而减小.     

Small Systems and Limitations on the Use of Chemical Thermodynamics

Limitations on using chemical thermodynamics to describe small systems are formulated. These limitations follow from statistical mechanics for equilibrium and nonequilibrium processes and reflect (1) differences between characteristic relaxation times in momentum, energy, and mass transfer in different aggregate states of investigated systems; (2) achievements of statistical mechanics that allow us to determine criteria for the size of smallest region in which thermodynamics can be applied and the scale of the emergence of a new phase, along with criteria for the conditions of violating a local equilibrium. Based on this analysis, the main thermodynamic results are clarified: the phase rule for distorted interfaces, the sense and area of applicability of Gibbs’s concept of passive forces, and the artificiality of Kelvin’s equation as a result of limitations on the thermodynamic approach to considering small bodies. The wrongness of introducing molecular parameters into thermodynamic derivations, and the activity coefficient for an activated complex into the expression for a reaction rate constant, is demonstrated.     

在非平衡态热力学的基础上探索建立催化理的新途径

平衡态热力学一直被认作多相催化理论的基石之一。但是,它并不能概括工作中的催化剂的状态和行为,这主要是这里还发生一些非平衡过程。催化体系常常处于非平衡状态之下,而非平衡态条件下体系状态和行为,同时取决于体系的动力学和热力学。联系动力学和热力学最一般的关系式并非原来的De Donder不等式：Ar≥0,而是新的De Donde方程ln r^-/r^-=A/RT。同时发生的总反应之间的热力学耦合对总反应的作用只是形式上的,远不及催化反应链中各基元步骤之间在动力学上的耦合那么重要。通过在动力学方程中引入反应亲和力（热力学位）得到的动力学-热力学结合近似分析,可以用来分析非平衡态的催化反应和催化剂状态。非平衡态热力学在建立多相催化理论中,较之原来的平衡态热力学将能提供更能采纳的和更有意义的物理化学背景。