高中化学奥林匹克竞赛辅导讲座：第10讲《氧化还原反应与电化学基础》

NernstpH11Zn(s)+Cu2+(aq)Zn2+(aq)+Cu(s)r)298(0KHm=281.66kJmol11863J.E.DaniellZnSO4DaniellKClUZn(s)Zn2++2eCu2++2eCu(s)Zn(s)+Cu2+(aq)Zn2+(aq)+Cu(s)Zn(s)ZnSO4(1c)CuSO4(2c)Cu(s)PtSn2+(1c),Sn4+('1c)Fe3+(2c),Fe2+('2c)Pt2Fe3+(aq)+Sn2+(aq)Fe2+(aq)+Sn4+(aq)2MFEMFE=)(E)(E10-10MFE0MFE=0)(E0)(E10-225c(Cu2+)=1.0molL1,c(Zn2+)=1.0molL10MFE=1.10V3GibbsGibbsrmG=maxW10-3QmaxW=MFQE=MFzFE10-4FFaradayF=96485Cmol1zrmG=MFzFE10-5r0mG=0MFzFE10-610-5MFEGibbsrmG21()()2H+1.0moll1100kPa2H+(aq)+H2(g)298.15K0)/(2HHE=0Hg2Cl2(s)+2e2Hg(l)+2Cl(aq)0.2415VPtH2(100kPa)H+(1.0moll1)Cu2+(1.0moll1)Cu(s)0MFE=0.340V0MFE=0)(E0)(E=0)/(2CuCuE0)/(2HHE=0)/(2CuCuE0)/(2CuCuE=0.340VM(s)M2+(aq)+zeCu2+(aq)+2eCu(s)0)/(2ZnZnE=0.762V298.15K3NernstNernstaNernstrmG(T)=MFzFE(T)r0mG(T)=0MFzFE(T)rmG(T)=r0mG(T)+RTlnJMFzFE(T)=0MFzFE(T)+RTlnJMFE(T)=0MFE(T)JzFRTln10-7NernstJz0MFE298.15KNernstMFE(298.5K)=0MFE(298.5K)JzVlg0592.010-8298.15KbNernst+zer0mG=0zFErmG=zFE)()(ln0cczFRTEE10-9298.15K)()(lg0592.0)15.298()15.298(0cczVKEKE10-10298.15Kzc()c()Nernstc()c()aAg+/Ag298.15K0)/(AgAgE=0.799VAg+(aq)+eAg(s)Nernst)/(AgAgE=0)/(AgAgE+0.0592lg0)(cAgcNaClAgCl0)(AgClcpK=1.8101000)(0/)(/)(cClcKcAgcAgClspNernst00)(0)/()/(/)(ln0592.0cClcKVEEAgClcpAgAgAgAgc(Cl-)=1.0moll1,00)(0)/()/(/)(ln0592.0cClcKVEEAgClcpAgAgAgAg=0.799V+0.0592ln1.81010=0.222VE(Ag+/Ag)AgCl/Agc(Cl)=1.0molL1AgCl(s)+eAg(s)+Cl(aq))(ln0592.0)/()/(000AgClKVAgAgEAgAgClEsp)/()/(00AgAgEAgAgClE(0spK(0spKbCu2+/Cu298.15KCu2+(aq)+2eCu(s)VE340.00[Cu(NH3)4]2+c(Cu(NH3)24)=c(NH3)=1.0molL102/)(cCuc=])([]/)([/])([24304030243NHCuKcNHccNHCucf=])([12430NHCuKfNernst])([1lg0592.024300)/()/(22NHCuKzVEEfCuCuCuCu=0.340V+121030.21lg20592.0V=0.392V0]/)([243CuNHCuE0.392V)(lg0592.0200)/(0)/(222CuClKVEEfCuCuCuClCu=0.1607V+0.0592Vlg6.91104=0.447V0fK0fK31EE+ze)/(0LiLiELiF2/HF0EF22mrGmrGEMFmrG=MFzFEEMFmrGMFE0mrG0MFE0mrG0MFE=0mrG=0MFE=EEEE()()(E0)()(EEEE1+2=1+20E0MFE0MFE0MFEMFE0.2VMFE0.2V0.2V0MFE0.2VMFE300lnKRTGmr0mrG=0MFzFERTzFEKMF00ln10-11298.15KVzEKMF0592.0lg0010-120MFE=)()(EE0KZn(s)+Cu2+(aq)Zn2+(aq)+Cu(s)298KZn(s)+Cu2+(aq)Zn2+(aq)+Cu(s)0MFE=0)/(0)/(22ZnZnCuCuEE=0.3394V(0.7621V)=1.1015V2128.370592.01015.120592.0lg00VVVzEKMF3701063.1K0K298KAg+(aq)+eAg(s)E0=0.7991V[Ag(NH3)2]+(aq)+eAg(s)+2NH3(aq)E0=0.3719V0)(,23NHAgfKAg+(aq)+2NH3(aq)[Ag(NH3)2]+(aq)K0=0)(,23NHAgfK0MFE=VVVEEAgNHAgAgAg4272.03719.07991.00]/)([0)/(23lgK0=216.70592.04272.010592.00VVVzEMFK0=0)(,23NHAgfK=1.641074VEA/0VEA/02H2O22H2O+O2Hg2++HgHg22Cu+1.229O2H2O2H2O0.69451.7631.229O2HO2OH0.69451.763Cu2+(aq)+eCu+(aq)E0=0.1607VCu+(aq)+eCu(s)E0=0.5180V2Cu+(aq)Cu2+(aq)+Cu(s)0MFE=VVVEECuCuCuCu3573.01607.05180.00]/[0)/(20MFE0Cu+0E0E0/CBE0/BAEBB0E0EBACB0mrG0E0)(xmrG=0)1(mrG+0)2(mrG+0)3(mrG0xxFEz=011FEz022FEz033FEzxxzEzEzEzE0330220110A+z1eB0)1(mrG=011FEzB+z2eC0)2(mrG=022FEz+)C+z3eD0)3(mrG=033FEzABCD01Ez1z202E03Ez30xEzxABC0E0E0E321zzzzx11MnO2NH4ClZnCl2NH4ClZn2e=Zn2+Zn+2MnO2+2NH4=2MnO(OH)+2NH3+Zn2+MnO2NH4H2NH4MnO2H2MnO(OH)MnO2ZnMnO2HgOKOHZnHgOKOHZn(s)+2OHZn(s)+H2O+2eHgO(s)+H2O+2eHg(1)+2OHZn(s)+HgO(s)ZnO(s)+Hg(1)1.35VZnAg2O1.5V3.2V22NH4+2e=2NH3+H2+H2+2MnO2=2MnO(OH)4PbO230%H2SO41.2kgL1PbO2Pb2+PbPb2+Pb2+SO24Pb(s)+SO24PbSO4+2ePbO2(s)+4H++SO24+2ePbSO4(s)+2H2OH2SO41molPb2molH2SO42molH2O1.05kgL1PbSO4(s)+2H2OPbO2(s)+4H++SO24+2ePbSO4(s)+2ePb+SO243H2(g)+1/2O2(g)=H2O(1)1molH2237kJ237kJ40%=95kJ200kJ75%KOHH2O2KOH1/2O2(g)+H2O+2e=2OHH2(g)+2OH=2H2O+2eH2(g)+1/2O2(g)=H2O21Ni+Cl2=Ni2++2Cl0/0/0)(0)(022NiNiCLCLEEEEE=1.360.25=1.61VCl2+2e=2ClNi2e=Ni2+Ni2++2Cl=Ni+Cl21.60VNi2++2e=Ni219341mol96500C1mol1mol/g/CNa++eNa2396500Mg2++2eMg24.3296500Al3++3eAl27.039650096500Cmol1=/100%114HCl+MnO2MnCl2+Cl2+2H2O216HCl+2KMnO4=2KCl+2MnCl2+5Cl2+8H2O34HCl+O22Cl2+2H2OKMnO4MnO2O22NaCl2Cu2+ISO2H+Fe3+123Fe3+Cu2+H+NaICl2SO22Fe3++Fe=3Fe2+Fe3+Cu2++Fe=Cu+Fe2+Cu2+2H++Zn=H2+Zn2+H+4Na+O2==2Na2ONa2I+Br2=I2+2BrICl2+H22HClCl2Cl2+H2O=HCl+HClOCl2SO2+2H2S=3S+2H2OSO22SO2+O22SO3SO2CuCl2===450o======3MnO4+C3H7OHMn2++C2H5COOH1MnO4Mn2+C3H7OHC2H5COOH2H+H2OMnO4+8H++5e=Mn2++4H2OC3H7OH+H2O=C2H5COOH+4H++4e34+54MnO4+5C3H7OH+12H+=5C2H5COOH+4Mn2++11H2O44289KFe3+Fe2+NaOHFe(OH)3Fe(OH)2c(OH)=1.0molL1E(Fe3+/Fe2+)Fe3+(aq)+eFe2+(aq)Fe3+Fe2+NaOHFe3+(aq)+3OH(aq)Fe(OH)3(s)30030)(,01]/)(][/)([113cOHccFecKKOHFespFe2+(aq)+2OH(aq)Fe(OH)2(s)20020)(,02]/)(][/)([112cOHccFecKKOHFespc(OH)=1.0molL10)(,00)(,0333]/)([)(OHFespOHFespKcOHcKcFec0)(,00)(,0222]/)([)(OHFespOHFespKcOHcKcFec)/(23FeFeE=0)/(23FeFeE0302/)(/)(lg0592.0cFeccFeczV=0)/(23FeFeE0)(,0)(,32lg0592.0OHFespOHFespKKzV=0.769V3917108.21086.4lg10592.0V=0.55Vc()c()(0spK(0spK51MnO2(s)+4HCl(aq)MnCl2(aq)+Cl2(g)+2H2O(l)252MnO2(s)HClCl2(g)?1MnO2(s)+4H+(aq)+2eMn2+(aq)+2H2O(l)E0=1.2293VCl2(g)+2e2Cl(aq)E0=1.360V0MFE=0)/(22MnMnOE0)/(2ClClE=1.2293V1.360V=0.131V02Cl2(g)HCl12molL1Nernstc(Mn2+)=1.0molL1p(Cl2)=100kPaHClc(H+)=12molL1c(Cl)=12molL1)/(22MnMnOE=0)/(22MnMnOE4002]/)([/)(lg20592.0cHccMncV=1.2293V4121lg20592.0V=1.36V)/(2ClClE=0)/(2ClClE0220/)(]/)([lg20592.0pClpcClcV=1.360V0.0592Vlg12=1.30V0MFE=0)/(22MnMnOE0)/(2ClClE=1.36V1.30V=0.06V0MnO2HClCl2Cl26298KCl2(g)+2Br(aq)=Br2(l)+2Cl(aq)21Cl2(g)+Br(aq)=21Br2(l)+Cl(aq)01K02Kz1=2z2=10)/(2ClClE0)/(2BrBrE0MFECl2(g)+2