[理学]研究生课程-第三章-溶液热力学基础.ppt

Chapter 3  Basic on Solution Thermodynamics §3-1 Characteristics of Partial Molar Property §3-2 Basic Thermodynamic Equation §3-3 Fugacity and Its Calculation §3-4 Activity and its Calculation §3-5 state of equation §3-6 calulation of fugacity for pure gas and the mixture §3-7 calulation of fugacity for pure liquid and the solid §3-8 calulation of fugacity for the liquid mixture 一、 Definition of Partial molar property The equation defines the partial molar property of species I in solutin, where the generic symbol may stand for the partial molar internal energy , the partial molar enthalpy , the partial molar entropy , the partial molar Gibbs energy ,etc. 二、Physical interpretation It is a response function(响应函数）, representing the change of total property due to addition at constant T and p of a differential amount of species i to a finite amount of solution. Note: Partial Molar Property is an intensive property and It is function of T , p and composition. 三、 Characteristics of Partial Molar Property summability relation 集合性 tangent Intercept 截距性 Example3-1 The need arises in a laboratory for 2000 cm3 of an antifreeze solution consisting of 30-mol-%methanol in water. What volume of pure methanol and pure water at 25 ℃ must be mixed to form the 2000 cm3 of antifreeze, also at 25 ℃? Partial molar volume for methanol and water in a 30-mol-% methanol solution and their pure-species molar volumes ,both at 25℃ ,are: 25℃, pure methanol(1) V1=40.727 cm3?mol-1 pure water(2) V2 =18.068 cm3?mol -1 Value of for the binary solution methanol(1)-water(2) at 25 ℃ are plotted in figure as function of x1. The is a requirement of Gibbs-Duhem equation , where here becomes: Division of this equation by dx1 and rearrangement gives: This result shows that the s