从统计热力学角度理解重要的热力学概念

基于玻尔兹曼统计法,简要总结独立粒子的非定位系统的统计热力学基础,并应用一些实例来分析统计热力学和热力学方法之间的区别和联系,帮助学生从统计热力学角度加深对一些重要的热力学概念(如热容、吉布斯自由能、焓和化学势)的理解,建立微观物理图像,以更好地学习两部分热力学知识,并能够灵活运用于化学问题的求解中。     

国内外典型教材的热力学教学内容及教学思路比较

目前物理化学教学在“量子先行”和“热力学先行”两种策略的选择上依然存在争论,热力学是物理化学的重要组成部分,本文分析和比较了国内外10本典型教材在热力学教学内容安排上的现状,提出了发展方向和建议,希望对物理化学教学和教材建设提供依据。     

从分子图像到热力学框架——物理化学教学的探讨与实践

化学的核心是基于原子分子的图像认识世界、创造物质,化学教育需要培养学生掌握相应的思维方式。在物理化学类课程建设中,浙江大学化学系尝试把宏观化学的基本理论框架,即热力学理论建立在原子分子水平上。具体地是先简述量子化学对单个原子、分子能级结构的处理,然后利用统计热力学的基本原理,从这些量子化的能级导出宏观系统的三个基石性概念(能量、熵、温度)和一条基本定律(熵增加原理),从而建立分子图像的热力学。在教学实践中,强调直接从原子分子层面切入、弱化热机理论、理论与实验结果直接关联。在本文中,我们通过几个教学实例来分享我们的教学经验。     

化学反应的热力学函数计算探究

详细讨论了化学反应过程中4个热力学函数计算公式,包括公式的引出,假设的模型,近似处理办法以及它们之间的关系。这对学好物理化学具有重要作用,对掌握物理化学在实际生产中的应用具有重要的指导意义。     

固液界面纳米气泡的研究进展

根据经典热力学理论,在水中纳米级的气泡难以长期稳定存在.近年来却有大量的实验结果表明固液界面存在纳米气泡,原子力显微镜也直接观察到了纳米气泡.有关纳米气泡的研究具有巨大的理论和实际意义,它对表面科学、流体动力学、生物科学以及一些应用领域都有深远的影响.纳米气泡会引起流体在界面的滑移,减少流动阻力,并与表面粘附、胶体分散、矿石浮选、废渣处理等方面密切相关.目前关于纳米气泡的研究才刚刚开始,对于它的基本物化性质的了解还不多,但其重要性已经引起相关领域的极大关注.本文综述了从提出纳米气泡存在一直到实验证明的过程、纳米气泡的形成机制和形貌、分布特征等基本性质以及纳米气泡的存在对疏水长程作用和流体滑移的影响,并阐述了生物学中一些与纳米气泡存在有关的问题.     

热力学函数关系式教学难点的化解

分4个层次介绍物理化学课程中热力学函数关系式的教学方法,探讨了运用基本公式和偏微商关系进行推导的方法,并举例说明了热力学函数关系式在处理实际问题时的应用。     

用Mathematica作偏摩尔量关系式的证明

简述了溶液热力学中应用的 4维Jacobian的定义及主要运算规则 ,并给出例子说明在MathematicaNotebook界面中应用的方法     

通过物理化学研讨课培养学生的研究能力——以两个连通气泡的变化为例

在物理化学的"界面与胶体化学"部分,表面张力、表面自由能和拉普拉斯公式是非常基础的内容,如何让学生深刻理解、灵活掌握至为重要,也是该章后续学习的关键。本文以分析两个连通气泡的变化为例,结合演示实验,实施研讨式教学,通过多角度(力学、能量等)、多层次(变化的方向、变化的限度)分析,巩固学生对表面张力、表面自由能及拉普拉斯公式的理解,进而与两个连通气球的变化进行类比,分析两个体系的异同点。通过启发引导,培养学生运用知识、分析问题的能力,提高学生综合素质。在物理化学课堂中,以学生为中心实施基于问题的研讨式教学,为相关课程的教学提供了参考。     

用哲学理念来思考物理化学的基本概念和联系

将物理化学中的某些概念和公式的哲学原理提取出来,用哲学理念来思考绝对与相对、广度与强度、真实与近似以及稳态与非稳态之间的关系。     

Determination of the Molecular Area on a Liquid Surface from Thermodynamic Functions: Application to Alkanes

A method is proposed to calculate the molecular area on the surface of a liquid from thermodynamic parameters such as the molar internal energy, the surface free energy, and the surface entropy. When the method is applied to the series of normal alkanes, it allows calculation of the area of the molecules on these liquid surfaces and to deduce the orientation of these molecules. Moreover, the molecular areas of the first terms of the alkane series and of hydrogen are also obtained by extrapolation.     

The Life of a Surface Bubble

Surface bubbles are present in many industrial processes and in nature, as well as in carbonated beverages. They have motivated many theoretical, numerical and experimental works. This paper presents the current knowledge on the physics of surface bubbles lifetime and shows the diversity of mechanisms at play that depend on the properties of the bath, the interfaces and the ambient air. In particular, we explore the role of drainage and evaporation on film thinning. We highlight the existence of two different scenarios depending on whether the cap film ruptures at large or small thickness compared to the thickness at which van der Waals interaction come in to play.     

Thermodynamic Properties of Liquid Na-TI

Abstract

New measurements of the free energy and entropy of mixing and association thermodynamic properties of liquid Na-TI alloys at three temlperatures are reported. A thermodynamic model is developed and fitted to these with success but the failure of the model to fit the properties of Na-Ga is reported. The problems involved in fitting thermodynamic models are discussed.     

Thermodynamic Properties of Liquid n-Pentadecane

Abstract

This paper reports experimental results concerning the isobaric heat capacity C_p of Liquid n-pentadecane as a function of pressure (up to 100 MPa) and temperature (313.15 to 373.15 K). The measurements were performed with a modified C80 SETARAM calorimeter based on the Calvet principle. These calorimetric data, combined with density data, were used to evaluate derived thermophysical properties such as the isochoric heat capacity C_v , the isentropic compressibility k_s and the speed of sound u in the same ranges of pressure and temperature. The pressure-temperature behaviour of these properties was then discussed as a model for simple organic liquids.     

室温离子液体BMIGaCl4热力学性质研究

An ionic liquid （IL） BMIGaCh was prepared by directly mixing GaCl3 and 1-methyl-3-butylimidazolium chloride with molar ratio of 1/1 under argon atmosphere. The densities and surface tensions of this pure ionic liquid were determined in the temperature range of 268.15 to （338.15±0.1） K. A new theoretical model of ionic liquids, an interstice model, was applied to calculate the thermal expansion coefficient of IL BMIGaCh, a, and the magnitude order of its value calculated by the theory was the same as experimental one. Both Raman scattering and ab initio calculations indicate that GaCl4^- is the only species containing Ga in the ionic liquid BMIGaCl4.     

Thermodynamic Properties of Liquid Alkali Metals

Abstract

Modified form of the pressure equation appropriate to liquid alkali metals is applied to the calculations of the thermal pressure coefficient and the thermal expansion coefficient. Comparison is made with the hard sphere reference system to understand the role of softness in the pair potential on the thermodynamic properties of alkali metals.     

Thermodynamic Properties of Multicomponent Liquid Mixtures

Considering a ternary liquid mixture to be made up of three binary mixtures, by means of cell model using Sutherland type potential function for pair interaction between molecules, a statistical theory for binary liquid mixtures has been extended for ternary systems. In the light of above extension, excess volume ( V E ), excess energy ( E E ) and excess entropy ( TS E ) have been computed for three binary (benzene + cyclohexane, benzene + chlorobenzene and cyclohexane + chlorobenzene) and the resultant ternary system (benzene + cyclohexane + chlorobenzene) at 298.15 K. All the above mentioned excess properties have been computed from the data of ultrasonic velocity and density only.     

Surface Tension of a Liquid under the Conditions of a Fast Surface Renewal during Evaporation

A new capillary method of measuring surface tension under the conditions of a fast surface renewal due to evaporation is considered. At the highest rates reached for n-pentane and water evaporation (0.6 and 0.14 kg m^–2 s^–1, respectively), the deviations of from its equilibrium values may be explained by a change in the meniscus shape under the conditions of intense heat exchange.     

Thermodynamic Properties of Liquid Alloys of the System Iron-Nickel-Cobalt

The integral molar excess Gibbs energy and the enthalpy of mixing of liquid alloys of the ternary system iron-nickel-cobalt at 1600°C were calculated by various methods from data on the boundary binary systems. The data for the boundary binary systems are analyzed in detail.     

Thermodynamic Properties of Liquid Alloys of the System Nickel-Copper-Cobalt

The integral thermodynamic characteristics and copper activity in liquid alloys of the system nickel-copper-cobalt at 1600°C were calculated by various methods from data on boundary binary systems.__________Translated from Zhurnal Prikladnoi Khimii, Vol. 78, No. 1, 2005, pp. 59–65.Original Russian Text Copyright © 2005 by Morachevskii, Tsymbulov, Kolosova, Tsemekhman.