6-7均勻溷合物热力学性质多元系的相平衡.docVIP

绪论 温度与热力学第零定律 热力学建立在四个定律的基础上：热力学第零、第一、第二和第三定律。第一定律说能量是守恒的．第二定律说不是全部的热能可以转化为功。第三定律说我们永远不能达到那个最低的温度． 第零定律说制造温度计是可能的，并给出温度的严格定义。 教材1.4节。 热力学第一定律 热力学第二定律，势函数 纯净流体的热力学性质 纯净物系的相变[20] 相变是物质状态的改变，确切一点说，是同一物质（化学组成不变）的状态突变（不是渐变）。这里强调同一物质，是因为化学反应、核反应也会使物质状态改变，但同时物质本身（分子）也变了，变化之后的物质（分子）不再是以前的物质（分子）；强调是突变，是因为相变之所以叫相变的本质就是物质的某些性质的不连续变化，即突变，比如水变成汽时比容突然变大。 理想气体是“永久气体”。就是说用状态方程PV=nRT描述的气体不会发生相变，不可能凝聚为液体。因为要从气态变到液态，必须靠分子之间的吸引力使它们凝聚起来。而理想气体分子间没有相互作用，因此“聚”不起来。 均匀混合物热力学性质 混合物 Most substances found in nature are mixtures of pure chemical elements or compounds: air, natural gas, seawater (but also tap water), coffee, wine, gasoline, antifreeze, body fluids, etc. The reason for this widespread occurrence is that there is a natural tendency for entropy to increase by the mixing (although energy minimisation might work against, as in liquid vapour equilibrium). Thus, some exergy has to be applied to separate a mixture in its components. The principles of thermodynamics introduced thus far are applicable to systems involving mixtures, but to apply them requires that the properties of mixtures be evaluated. Since an unlimited variety of mixtures can be formed from a given set of pure components by varying the relative amounts present, the properties of mixtures are available in tabular, graphical, or equation forms only in particular cases such as air. Generally, special means are required for determining the properties of mixtures. To describe multicomponent systems, composition must be included in our thermodynamic relations. This leads to the definition and development of several new concepts, including the partial molal property, the chemical potential, and the fugacity. The present discussion is limited to nonreacting mixtures or solutions in a single phase. The effects of chemical reactions and equilibrium between different phases are taken up in the following chapters. Mixture composition To evaluate the properties of a mixture requires knowledge of the composition. The co