无机及分析化学第六章课后习题答案(高等教育出版社,第二版)69167.pptVIP

6-20 Hg2Cl2(s)+ 2e = 2Hg（1）＋2Cl－(aq） E ?(Hg2Cl2 /Hg) ＝ 0.28V Hg22+ + 2e = 2Hg（1） E ?(Hg2Cl2 /Hg) ＝ 0.80V 将上述两极反应组成原电池 (－)Pt|Hg（1)| Hg2Cl2(s)|Cl－ ‖Hg22+ |Hg（1) |Pt(＋) 电池反应 Hg22+ + 2Cl－ = Hg2Cl2(s) E? ＝ 0.80 - 0.28 = 0.52V 反应平衡常数 lgK? = 2 ×0.52 /0.0592 = 17.56 K? = 1017.56 K?SP (Hg2Cl2) = 1/ K? ＝1/1017.56 =2.8 ×10-18 * (－)Pt∣Fe 2+（C1）,Fe 3+(C2)‖MnO4-(C3),Mn2+(C4)∣Pt (＋) E? ＝ 1.51V-0.771V=0.739V 3) E＝ ?(+)－?(-)＝ ?(+)?＋ - ?(-)? =1.51V+0.0592/5 lg108 –0.771V =0.83V 6-10, E＝ E(+)－E(-)＝1.51V [E(Ag+/Ag)?+0.0592V lg(Ag+)]-E(Zn2+/Zn)?+ 0.0592V lg(Zn2+)] =1.51V 由于C(Ag+)=0.10 mol/L 所以 C(Zn2+)=0.57 mol/L 6-11 查表， E(Sn2+/Sn)?=-0.136V, E(Pb2+/Pb)?=-0.126V 因为， E? ＝ E(+)? －E(-)? 0.22V=-0.136V- E(-)? E(-)? = E(PbSO4/Pb)? =-0.356V= E(PbSO4/Pb)= E(Pb2+/Pb)?+ 0.0592/2 lgC(Pb2+) = -0.126V + 0.0592/2 lgK?SP (PbSO4)/C(SO42-) lgK?SP (PbSO4)= - 7.77 K?SP (PbSO4)=1.7 ×10-8 6-12 反应式： Pb + Cu 2+ = Pb 2+ + Cu 正极 : E( Cu2+/Cu) = E(Cu2+/Cu)? + = 0.337V + 0.0592/2 lg0.5 = 0.33 V 负极: E(Pb2+/Pb) = E(Pb2+/Pb)? + =-0.126V + 0.0591/2 lg0.1 = -0.16 E = E(Cu2+/Cu) - E(Pb2+/Pb) = 0.33-(-0.16)= 0.49V lgK? = nE?/0.0592 = 2 ×[0.337-(-0.126)]/0.0592 = 15.64 K? =4.4 ×1015 2) 反应式： 2H+ + Sn = Sn 2+ + H2 正极 : E( H+ /H2) = E(H+/H2)? + = 0.0000V 负极: E( Sn2+ /Sn) = E(Sn2+/Sn)? + =-0.136V + 0.0591/2 lg0.05 = -0.17 E = E(+) - E(-) = 0.0000 -(-0.17)= 0.17V lgK? = nE?/0.0592 = 2 ×[0.0000-(-0.136)]/0.0592 = 4.59 K? =3.9 ×104 4) 反应式：2H++H2= 2H++H2 正极 : E( H+/H2) = E(H+/H2)? + = 0.0000V 负极: E(H+/H2) = E(H+/H2)? + = 0.0000 + 0.0591/2 (lg0.012/1) = -0.12V E = E(+) - E(-) = 0.0000 -(-0.12)= 0.12V lgK? = nE?/0.0592 =[2 ×0.0000]/0.0592 = 0