物理化学（Ⅰ）.6.ppt

* 物理化学(Ⅰ) PHYSICAL CHEMISTRY （6） P4.3 A block of copper of mass 2.00kg(Cp,s=0.385 J K g-1) and temperature 0 oC is introduced into an insulated container in which there is 1.00 mol H2O(g) at 100 oC and 1 atm. (a) Assuming all of the steam is condensed to water, what will be the final temperature of the system, the heat transferred from water to copper, and the entropy change of the water copper and the total system? (b) In fact , some water vapour is present at equilibrium. From the vapour pressure of water at the temperature calculated in (a), and assuming that the heat capacities of both gaseous and liquid water are constant and given by their values at that temperature, obtain an improved value of final temperature, the heat transferred and the various entropies. Cu(s) 2.00g 273K + H2O(g) 1mol 373K, 1atm 2.00g Cu(s) 1mol H2O(l) T, 1atm ΔH = 0 1mol H2O(l) 373K, 1 atm ΔH = -ΔvapHm(H2O)+Cp,m(H2O,l) (T-373K)+ mCp,s(Cu)(T-273K) = 0 T = 330 K ΔS = -ΔvapHm/373K + Cp,m(H2O,l)×ln(330K/373K)+ + mCp,s(Cu)×ln(330K/273K) = 27.9 J K-1 Cu 2.00 kg 273K + H2O(g) 1mol 373K, 1atm Cu 2.00g H2O (g) x mol H2O (l) 1-x mol T , p ΔU= 0 Cu ( 273K) Cu ( T) x H2O (g, 373K, 1atm) x H2O(g, T , p) (1-x) H2O(g, 373K,1 atm) (1-x) H2O (l , 373K,1atm) (1-x) H2O (l , T, p) ΔU = m CV,s(Cu)(T-273K) + 0.806×[ΔglUm + CV,m(H2O,l) ×(T-373K)] +0.194×CV,m(H2O,g)×(T-373K) = 0 T = 317 K P = p*(H2O,330K)=17.4 kPa x = 0.194 mol Δ S = m Cp,s×ln(T/273K) + 0.806×[(- ΔvapHm/373K) + Cv,m(H2O,l)×ln(T/373K)] + 0.194×[Rln(101.325kPa/p) + Cp,m(H2O,g)×ln(T/373K)] = 19.2 J K-1 热力学第一、二定律复习 一、内容小结： 1. 基本概念：热力学平衡状态、状态函数、 2 . 封闭系统热力学第一、二定律：形式、条件 4. 理想气体各种简单物理变化过程热力学量的 计算 5. 化学反应ΔH 、ΔU、 ΔS 、ΔA、 ΔG的 计算---途径法的应用 6. 封闭系统热力学基本关系式： 形式、条件、应用。 3. Q, W, U, H, S