华科材料热力学homework #3.doc

Thermodynamics in Materials Science Homework #3 Due Nov. 15, 2004 Chapter 5: Equilibrium in thermodynamic systems State in words and mathematically the set of relationships implied by the statement that a thermodynamic system is isolated from its surroundings during process. 基本特征：1 与外部环境没有物质交换2与外部环境没有能量交换 Δu=0, Δn=0,Δv=0; 就是说这个体系的总内能、总摩尔数、总体积是一个定植。 The development presented in this chapter describes the behavior of an isolated system. Systems of practical interest are rarely isolated from their surroundings in their approach toward equilibrium. How is it them possible to conclude that the results of this development are general, and not limited to an isolated system? 我们假定一个孤立体系来讨论问题，这样可以简化推论过程；同时在一个一般的平衡过程中，体系内部的内能、体积、摩尔数等参量同样是定植，所以结果也是适用的，并不仅仅适用于孤立体系。 Find the extreme values of the function: z = (x - 2)2 + (y – 2)2 + 4. Find the constrained maximum of this function corresponding to the condition x + y = 1. 关于z = (x - 2)2 + (y – 2)2 + 4中(x - 2)2≥0，(y- 2)2≥0 ? z≥4 (当且仅当x=2,y=2时候Zmin=4) 当x + y = 1时候，y=1-x ? z=(x-2)2+(-1-x)2+4 =2x2-2x+9 =2(x-1/2)2+17/2 ? 当x=0.5时y=0.5,Zmin=8.5 The combined statement of the first and second laws for the change in enthalpy of a unary, single-phase system may be written: dH’ = TdS’ + V’dP + ?dn Use this result to write an expression for the change in enthalpy of a two phase (? + ?) system. If the entropy, pressure and total number of moles are constrained to be constant, then the criterion for equilibrium is that the enthalpy is a minimum. Paraphrase the strategy used to deduce the conditions for equilibrium in an isolated system to derive them for a system constrained to constant S’, P, and n. What happens to the condition for mechanical equilibrium? dH’=TdS’+V’dP+μdn dHα=TαdSα+VαdFα+μαdnα dHβ=TβdSβ+VβdPβ+μβdnβ dH = dH + dH 如果P S n 为定值：d S= - d S n + n = n d n= - d n ? dH=(Tα-Tβ)dSα+(μα-μβ)dnα 理想的孤立体系：dU=0 dV=0 dn=0 dW=0 dQ=0 dS= 孤立体系的平衡过程中：T = T , , Chapter 6: Statistical thermodynamics Consider a syst