普通化学-第四章习题解答.docVIP

电化学与金属腐蚀-----习题解答 4-2. 选择题: (1)b; (2) b; (3) b; (4) a,b 4-4. 答 正极: Fe2+ (aq) + 2e ＝ Fe (s) 负极: Zn (s) - 2e ＝ Zn2+ (aq); 正极: Fe3+ (aq) + e ＝ Fe2+ (aq) 负极: 2I- (aq) - 2e ＝ I2 (s);. 正极: Sn4+ (aq) + e ＝ Sn2+ (aq) 负极: Ni (s) - 2e ＝ Ni2+ (aq); 正极: MnO4- (aq) + 8H + 5e ＝ Mn2+ (aq) + 4H2O 负极: Fe2+ (aq) - e ＝ Fe3+ (aq); 4-7. 解 (1) (-) Sn ( Sn2+ (aq, 0.0100 mol·dm-3) || Pb2+ (aq, 1.00 mol·dm-3) ( Pb (+) E = (?Pb2+/Pb - (?Sn2+/Sn + (RT/nF)ln(CPb2+/C?)/(CSn2+/C?) = (-0.126 – (-0.138)) + (0.0592/2)log(1/0.0100) = 0.0712 V 正极: Pb2+ (aq) + 2e ＝ Pb (s) 负极: Sn (s) - 2e ＝ Sn2+ (aq); 总反应式: Pb2+ (aq) + Sn (s) ＝ Pb (s) + Sn2+ (aq) (2) (-) Pb ( Pb2+ (aq, 1.00 mol·dm-3) || Sn2+ (aq, 0.0100 mol·dm-3) ( Sn (+) E = (? Sn2+/Sn - (? Pb2+/Pb + (RT/nF)ln(CSn2+/C?)/ (CPb2+/C?) = (-0.138 – (-0.126)) + (0.0592/2)log(1/0.100) = 0.018 V 正极: Sn (s)+ 2e ＝ Sn2+ (aq) 负极: Pb2+ (aq) - 2e ＝ Pb (s); 总反应式: Pb (s) + Sn2+ (aq) ＝ Pb2+ (aq) + Sn (s) 4-9. 解 2Fe3+ (aq) + 2I- (aq) ＝ 2Fe2+ (aq) + I2 (s) E? = (? Fe3+/ Fe2+ - (? I2/ I_ = 0.775 – 0.535 = 0.236 (2) (-) Pt ( I2 (s) ( I- (aq, 1 mol·dm-3) || Fe3+ (aq, 1 mol·dm-3), Fe2+ (aq, 1 mol·dm-3) ( Pt (+) ΔG? = - nFE? = -2×96485×0.236 / 1000 (KJ) = -45.5 KJ (4) E = E? + (RT)/nF ln(CFe3+/C?)(CI-/C?)/ (CFe2+/C?) = 0.0236 + (0.0592/2)log (10-2)2/(10)2 = 0.0584 V 4-10 解 已知: 2MnO4-(aq) + 16H+(aq) + 10Cl-(aq) ===== 2Mn2+(aq) + 5Cl2(g) + 8H2O(l) 正极为: MnO4-(aq) + 8H+(aq) + 5e- ===== Mn2+(aq) + 4H2O 负极为 2Cl-(aq) ==== Cl2(g) + 2e pH = 5.0 时: ( MnO4-/Mn2+ = (? MnO4-/Mn2+ + (RT/nF)ln[(C MnO4-/C?) (CH+/C?)8]/ (Mn2+/C?) = 1.033 V (Cl2/Cl- = (?Cl2/Cl- = 1.358 V E = ( MnO4-/Mn2+ - (Cl2/Cl- 0 因此这个反应正向不能进行或逆向自发进行 4-11. 解 2H+ (aq) + Ni (s) ===== H2 (g) + Ni2+(aq) 根据题意: E = (? H+/H2 - (?Ni2+/Ni + (RT/nF)ln(CH+/C?)2/ [(CNi2+/C?) (PH2/P?)] = 0.315 V 0 - (?Ni2+/Ni + (0.0592/2)log1/[0.01×1] = 0.315 V (?Ni2+/Ni = -0.256 V 4-14. 解 (1) Cr2O72- (aq) + 14H+ (aq) + 6Br- (aq) ==== 2Cr3+ (aq) + 3Br2 (l) + 7H2O(l) Cr2O72- + 14H+ (aq) + 6e ====== 2Cr