化学势在解决相平衡类问题中的应用探究

采用微元法对有关平衡类问题中化学势变化进行了集中分析和讨论,将克劳修斯-克拉贝龙方程、液体的饱和蒸气压与外压的关系式、开尔文公式以及稀溶液的依数性公式等知识点有机的关联起来,显著降低了相关知识内容的学习难度,并对培养学生创新思维起到了有效锻炼和促进作用。     

外压与凝聚态物质饱和蒸气压关系的讨论

应用外压与饱和蒸气压的关系公式,推导了范霍夫公式和开尔文公式。温度一定时,平液面的饱和蒸气压只会大于或等于真空密闭系统中纯物质气液平衡时的饱和蒸气压。毛细管的凹液面还会出现比平液面的饱和蒸气压小的情况。该关系公式称为"凝聚相表面的压力与饱和蒸气压的关系公式"更为合理。     

投影实验之七——溶液的蒸气压下降和沸点升高

在一定温度下,含有不挥发溶质的溶液的蒸气压比纯溶剂的蒸气压低,而这种溶液的沸点则比纯溶剂的沸点高。     

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。     

关于稀溶液依数性讲解中的几个问题讨论

就大一化学中稀溶液依数性讲解中依数性概念、蒸气压下降原因、渗透压定义以及几个图解中存在的问题进行讨论并提出了见解。     

溶液蒸气压下降的微型实验

溶液的蒸气压下降是溶液的重要性质之一,它导致了溶液的沸点升高和凝固点降低,是师专、医药专科、大一基础化学教学的重要内容之一,但未安排这个实验。过去我们在教学中通过课堂演示实验,给学生以感性认识。     

投影实验之十二——“蒸气压下降”实验的改进

拉乌尔定律指出,在一定温度下,溶质为不挥发的物质时,溶液的蒸气压比纯溶剂的蒸气压低。     

柯诺洛夫规则与相图

以柯诺洛夫规则为例,引导学生去探索该规则背后蕴藏的物理图像,即气液相图。从理想溶液和稀溶液气液相图开始,进一步探讨和分析了非理想溶液气液相图中总蒸气压与气液相中A组分物质的量分数之间的定量关系。     

稀溶液中溶剂的化学势及其在依数性上的应用

长期以来,稀溶液中溶剂A的化学势为μA（1）=μ^＊A（1）＋RTlnxA,溶质B的化学势为μB（溶质）=μ^ΞB（溶质）＋RTln（bB／b^Ξ）,两式使用了不同的组成变量：溶剂的摩尔分数xA,溶质的质量摩尔浓度bB。按规定,溶液的组成变量应选用bB,故本文介绍了导出理想稀溶液中μA（1）=μ^＊A（1）-RTMA∑BbB的方法,并从此式出发推导出稀溶液的依数性。     

有关化学热力学的一个问题

《化学通报》编辑部有一个问题百思而不得其解,曾请教过几位教师,并未得出所以然。问题不解决,总是个病,因此去信求教,盼答复。有密闭装置如图,A纯水、B不挥发性非电解质稀水溶液。M将它们隔关。拉乌尔(Raoult)定律指出:纯溶剂的蒸气压大于溶液的蒸气压。因此,A的蒸气压大于B的蒸气压。换言之,系统内的蒸气压必将大于P_B小于P_A。由于大于P_B,蒸气要在B的表面凝结;     

Anomalous Capillary Pressure, Stress, and Stability of Solids-Coated Bubbles

A two-dimensional theoretical model for solids-coated, or "armored," bubbles shows how the armor can support a liquid-vapor interface of reduced or reversed curvature between the particles, giving the bubble zero or even negative capillary pressure. The inward capillary force pulling the particles into the center of the bubble are balanced by large contact forces between the particles in the armor. Thus the bubble is stabilized against dissolution of gas into surrounding liquid, which otherwise would rapidly collapse the bubble. The stresses between particles in such cases are large and could drive sintering of the particles into a rigid framework. Earlier work on solids-coated bubbles assumed that solids can freely enter or leave the bubble surface as the bubble shrinks or expands. In such a case, armored bubbles would not be stable to gas dissolution into surrounding liquid. A new free-energy analysis, however, suggests that a shrunken bubble would not spontaneously expel a solid particle from its armor to relieve stress and allow the bubble to shrink further. Implications and limitations of the theory are discussed. Copyright 1999 Academic Press.     

Pressure effects on the structural,electronic, and optical properties of Sin@SWCNTs

Well‐ordered single, double/four parallel, three/four‐strands helical chains, and five‐strand helical chain with a single atom chain at the center of Si nanowires (NWs) inside single‐walled carbon nanotubes (Si_n@SWCNTs) are obtained by means of molecular dynamics. On the basis of these optimized structures, the structural evolution of Si_n@SWCNTs subjected to axial stress at low temperature is also investigated. Interestingly, the double parallel chains depart at the center and transform into two perpendicular parts, the helical shell transformed into chain, and the strand number of Si NWs increases during the stress load. Through analyzis of pair correlation function (PCF), the density of states (DOS), and the z‐axis polarized absorption spectra of Si_n@SWCNTs, we find that the behavior of Si_n@SWCNTs under stress strongly depends on SWCNTs' symmetry, diameter, as well as the shape of NWs, which provide valuable information for potential application in high pressure cases such as seabed cable. © 2008 Wiley Periodicals, Inc. Int J Quantum Chem, 2009     

Vapor Pressure Determination by Pressure DSC

A new pressure DSC module (Mettler DSC27HP) and its abilities for vapor pressure determination in the range of subambient pressure to 7 MPa are presented. To compare the new to an established method, vapor pressures of caffeine, naphthalene and o-phenacetin have been determined both by pressure DSC and the Knudsen effusion cell method. These results, including the derived heats of evaporation and heats of sublimation, are compared to literature values. This revised version was published online in July 2006 with corrections to the Cover Date.     

On Internal Pressure, Its Temperature Dependence, and the Structure of Liquid-Phase Systems

The notions of internal pressure and its temperature coefficient are critically analyzed. The temperature coefficient of internal pressure is correlated with the peculiarities of supramolecular organization of liquid-phase systems. This relationship is characterized.     

聚合物在高压下的结构、形态和性能（下）

聚合物在高压下的结构、形态和性能（下）张雄伟，黄锐（成都科技大学塑料工程系，成都，６１００６５）在上篇中我们介绍了结晶性聚合物在高压下结晶的结构和形态。本篇将介绍聚合物在高压下的结晶动力学和热力学以及聚合物在高压下的退火等方面内容。２高压结晶动力学研...     

Volatilisation,Evaporation and Vapour Pressure Studies Using a Thermobalance

There is considerable interest in performing volatilisation and evaporation measurements by thermogravimetry. A quick and simple method for determining vapour pressure using a conventional thermobalance and standard sample holders has been developed. These yield meaningful thermodynamic parameters such as the enthalpies of sublimation and vaporisation. Under favourable conditions the melting temperature and enthalpy of fusion of such compounds can be obtained. This technique has been used for the study of dyes, UV absorbers and plasticisers. The use of modulated- temperature programs for such work is also described. This revised version was published online in July 2006 with corrections to the Cover Date.     

Pressure and temperature dependence of hydrophobic hydration: volumetric, compressibility, and thermodynamic signatures

The combined effect of pressure and temperature on hydrophobic hydration of a nonpolar methanelike solute is investigated by extensive simulations in the TIP4P model of water. Using test-particle insertion techniques, free energies of hydration under a range of pressures from 1 to 3000 atm are computed at eight temperatures ranging from 278.15 to 368.15 K. Corresponding enthalpy, entropy, and heat capacity accompanying the hydration process are estimated from the temperature dependence of the free energies. Partial molar and excess volumes calculated using pressure derivatives of the simulated free energies are consistent with those determined by direct volume simulations; but direct volume determination offers more reliable estimates for compressibility. At 298.15 K, partial molar and excess isothermal compressibilities of methane are negative at 1 atm. Partial molar and excess adiabatic (isentropic) compressibilities are estimated to be also negative under the same conditions. But partial molar and excess isothermal compressibilities are positive at high pressures, with a crossover from negative to positive compressibility at approximately 100-1000 atm. This trend is consistent with experiments on aliphatic amino acids and pressure-unfolded states of proteins. For the range of pressures simulated, hydration heat capacity exhibits little pressure dependence, also in apparent agreement with experiment. When pressure is raised at constant room temperature, hydration free energy increases while its entropic component remains essentially constant. Thus, the increasing unfavorability of hydration under raised pressure is seen as largely an enthalpic effect. Ramifications of the findings of the authors for biopolymer conformational transitions are discussed.     

Analysis of Hydroxyl,Unsaturated, and Cyclopropane Fatty Acids by High Pressure Liquid Chromatography

Abstract

The investigation describes the HPLC separation of hydroxyl fatty acids as their methoxyphenacyl esters. All separations were performed using two types of reverse phase columns, μ-Bondapak C 18 and Fatty Acid Analysis columns. The solvent system consisted of acetonitrile: water gradient. A simple method for the trifluoroacetylation of the hydroxyl group is described which permits the identification of these specific fatty acids and decreases the lower limit in chain length determination for these fatty acids.

A method for the hydrogenation of unsaturated fatty acid mixtures is described, and the effects of variations in time, temperature, pressure, and the amount of catalyst are examined on the percent hydrogenation of unsaturated to the saturated forms of the fatty acids. Further, the effects of the different variables are related to the percent of hydrogenation of the cyclopropane fatty acids. Evidence is provided on the hydrogenation of the cyclopropane which does not agree with previously described ring opening mechanisms which have been proposed from GLC data which may be due to the difference in temperatures under which the chromatographic processes are carried out. These findings indicated the possibility of isolating an intermediate in the process by HPLC.     

Pressure dependence of the thermal conductivity,thermal diffusivity,and specific heat of some polymers

The pressure dependence of the specific heat of poly(methyl methacrylate), polystyrene, and atactic and isotactic polypropylene was determined from simultaneous measurements of thermal conductivity and diffusivity in a cylindrical geometry at 300°K and in the pressure range 0–37 kbar. The thermal conductivity and the diffusivity both increase strongly with pressure, while the specific heat decreases. The pressure dependencies are most pronounced at low pressures. The results are compared with other experimental results and with theoretical calculations.