物理化学第三章练习题.pptVIP

00-8-15 1 5 7 9 10 ′ 12 ′ 13 16 ′ 17 ′ 19 22 ′ 24 ′ 24 ′ 24 30 ′ 32 ′ 27 ′ 33 44  49 28 ① nRT=PV P2= ② △H= △H1+ △H2=0.1×25.104+0= 2.5104KJ ③ W=0 Q= △U= △H - △(PV)≈ △H –P2V2 = (2.5104+25.662×10×10-3)KJ=2.2538KJ 101.325kPa 0.1mol 液 35.51℃ 101.325KPa 0.1mol 气 35.51℃ P2 不可逆 相变 0.1mol 气 35.51℃ 101.325KPa ① ② 已知298.15K时液态水的标准摩尔生成吉布斯函数 ?fG?m (H2O,l)=－237.129 kJ?mol－1 . 298.15K时水的饱和蒸气压为3.1663kPa . 求298.15K时水蒸汽的标准摩尔生成吉布斯函数m . H2O (l) 100kPa ?fG?m ′ H2O (l) 3.1663kPa ?G1 H2O (g) 3.1663kPa ?G2 ?G3 (1/2)O2(g) 100kPa H2O (g) 100kPa H2(g) 100kPa ?fG?m 恒温298.15K下 ?fG?m ′ =－237.129 kJ?mol－1 ?G 2 = 0 ?fG?m = ?G1+ ?G2 + ?G3 + ?fG?m ′ = －228.57 kJ?mol－1 H2(g) + (1/2)O2(g) ? H2O(g) ?fG?m (H2O,g) = ?fG?m (H2O,l) +?G ?G1 H2O (l) 100kPa H2O (l) 3.1663kPa H2O (g) 3.1663kPa ?G2 ?G3 H2O (g) 100kPa ?G 34 假设终态N2分压 =(120 – 101.325)kPa=18.675kPa H2O (l) 101.325kPa H2O (g) 72kPa H2O (g) 101.325kPa ② ① W= - P △V = -RT△n = -8.314×373.15×3 = -9.308kJ △U = Q +W = 112.696kJ N2 120kPa N2 48kPa 3 △A = △U - T△S = 112.696 -373.15×350.72×10-3=-18.176kJ △G = △H - T△S= 122.004 -373.15×350.72×10-3=-8.868kJ dA = -SdT - PdV nH2O (g) P2 =101.325kPa t,, V1≠V n H2O (g) V=100dm3 P1=120kPa t=100 ℃ n1H2O (g) n2H2O (l) P2=101.325kPa V , t ② ① 不可逆 相变 35 n=P1V/RT=3.868mol n1=P2V/RT=3.266mol n1= 0.602mol ①理想气体恒温可逆变化 △H1＝0 △S1＝nRlnP1/P2=5.44J.K-1 ②可逆相变过程 △H2＝－n △VapH＝-24.479 kJ △S2= △H2 /T=-65.601J.K-1 △H= △H1 + △H2= -24. 479 kJ △S= △S1 + △S2= -60. 161J. K-1 W=0 Q= △U= △H- △(PV)= △H -V△P=-22.449kJ △G = △H- T△S=-2.030kJ 或 △G= △G1 + △G2= △G1＝ nRTlnP1/P2 =-2.030kJ △A = △U- T△S=-0.162kJ 错误：Q=Q1+Q2 △S= Q/T=△U/T 36 100℃ H2O(g) 101.325 kPa 100℃ H2O(l) 101.325 kPa 120℃ H2O(l) 101.325 kPa 120℃ H2O(g) 101.325 kPa 不可逆相变 (2) 可逆相变 (1) (3) dG = -SdT + VdP △G = △H - T△S = -119.77kJ * 若某可逆热机分别从(a)600K, (b)1000K的高温热源吸热, 向300K的冷却水放热, 问每吸100kJ热各能作多少功? Q2 W可 Q1 热源T1 热源T2 可 (a) T1 = 600K, T2 =