无机化学(周祖新)习题解答第五章

-512As2O3KO2NH4+Cr2O72-Na2S2O3Na2O2CrO5Na2PtCl6N2H2Na2S52As2O3+3KO2+1NH4+-3Cr2O72-+3Na2S2O3+2Na2O2-1CrO5+10Na2PtCl6+4N2H2-1Na2S5-2/53342FeCl3+CuFeCl2+CuCl2Cu+CuCl2+4HCl2H2[CuCl3]Cu2O+H2SO4Cu+CuSO4+H2O4FeCl3FeCl2CuCuCl2CuCl22H2[CuCl3]Cu2H2[CuCl3]Cu2OCuCu2OCuSO45--2FeCl2+3Br22FeBr3+4Cl-Fe2++NO3-+4H+Fe3++NO+2H2O5(1)(2)6FeCl2+3Br22FeBr3+4FeCl33Fe2++NO3-+4H+3Fe3++NO+2H2O6EE655(()66AgCl/AgHg2Cl2/Hg(H2H+,O2OH-,Cl2Cl-)(Fe3+Fe2+Sn4+Sn2+)7788K2Cr2O7K2Cr2O7H+S2-S2-HNO3CuSS2-HgSHgSKOSPS2-HNO3HgSS2-991010H+(1.000mol?L-1100kPaH+[Hg2Cl2(s)+2e-2Hg(l)+2Cl-(aq)]Cl-Cl-111112EE12EEEE(0.2V)EE(0.2V)EEE13()ZnZnSO4(1mol?L-1)CuSO4(1mol?L-1)Cu()ZnSO4CuSO4CuSO4H2S10min?1310min?Cu2+Zn2+65.38:63.5514141515EE16161717181919O2CO220CuSO4FeFe2+Fe3+FeCl3FeCl220EO(Fe2+/Fe)=-0.44VEO(Fe3+/Fe2+)=0.771VEO(Cu2+/Cu)=0.340VEO(Fe2+/Fe)EO(Cu2+/Cu)EO(Fe3+/Fe2+)FeFe2+Fe3+21211-MnO4-+Cl-Mn2++Cl2Mn2++NaBiO3MnO4-+Bi3+Cr3++PbO2Cr2O72-+Pb2+C3H8O+MnO4-C3H6O2+Mn2+HClO3+P4Cl-+H3PO4I-+H2O22+H2OMnO4-+H2O2Mn2++O2+H2OCu2S+HNO3Cu(NO3)2+S+NO+H2O1MnO4-+8H++5e-Mn2++4H2O22Cl-2e-Cl252MnO4-+10Cl-+16H+==2Mn2++5Cl2+8H2OMn2++4H2O5e-MnO4-+8H+2NaBiO3+6H++2e-Bi3++3H2O52Mn2++5NaBiO3+14H+==2MnO4-+5Bi3++7H2O2Cr3++7H2O6e-Cr2O72-+14H+1PbO2+4H++2e-Pb2++2H2O32Cr3++2PbO2+H2O===2Cr2O72-+2Pb2++2H+MnO4-+8H++5e-Mn2++4H2O4C3H8O4e-+2H2OC3H6O2+6H+54MnO4-+5C3H8O+2H+===4Mn2++5C3H8O+6H2OHClO3+5H++6e-Cl-+3H2O10P4+16H2O20e-4H3PO4+20H+310HClO3+3P4+18H2O===10Cl-+12H3PO4+10H+H2O2+2H++2e-2H2O12I-2e-21H2O2+2H++2I-===2H2O+I2MnO4-+8H++5e-Mn2++4H2O2H2O22e-O2+2H+52MnO4-+5H2O2+6H+===2Mn2++5O2+8H2OHNO3+3H++3e-NO+2H2O4Cu2S4e-2Cu2++S34HNO3+12H++3Cu2S===4NO+6Cu2++3S+8H2O16HNO3+3Cu2S===4NO+6Cu(NO3)2+3S+8H2O2CrO42-+HSnO2-CrO2-+HSnO3-H2O2+CrO22-CrO42-CuS+CN-Cu(CN)43-+S2-+NCO-CN-+O2CO32-+NH3Al+NO2-Al(OH)4-+NH3S2O32-+Cl2SO42-+Cl-+H2O2CrO42-+2H2O+3e-CrO22-+4OH-2HSnO2-+2OH-2e-HSnO3-+H2O32CrO42-+3HSnO2-+H2O===2CrO22-+3HSnO3-+2OH-H2O2+2e-2OH-3CrO2-+4OH-3e-CrO42-+2H2O23H2O2+2CrO2-+2OH-===2CrO2-+4H2OCuS+4CN-+e-Cu(CN)43-+S2-2CN-+2OH-2e-NCO-+H2O12CuS+9CN-+2OH-===2Cu(CN)43-+2S2-+NCO-+H2OO2+4H2O+4e-8OH-1CN-+3OH-2e-CO32-+NH322CN-+O2+4H2O===2CO32-+2NH3+2OH-NO2-+5H2O+6e-NH3+7OH-1Al+4OH-3e-Al(OH)4-2NO2-+5H2O+2Al+OH-===NH3+2Al(OH)4-Cl2+2e-2Cl-4S2O32-+10OH-8e-2SO42-+5H2O14Cl2+S2O32-+10OH-===8Cl-+2SO42-+5H2O3KMnO4K2Cr2O7FeCl3H2O2I2Cl2SnCl4PbO2NaBiO33EO(F2/F-)EO(H2O2/H2O)EO(MnO4-/Mn2+)EO(PbO2/Pb2+)EO(Cr2O72-/Cr3+)EO(Cl2/Cl-)EO(Br2/Br-)EO(Fe3+/Fe2+)EO(I2/I-)F2H2O2MnO4-PbO2Cr2O72-Cl2Br2Fe3+I2HFH2OMn2+Pb2+Cr3+Cl-Br-Fe2+I-4SnCl2KIH2H2O2FeCl2ZnAlNa2SMnCl24EO(Mg2+/Mg)EO(Al3+/Al)EO(Zn2+/Zn)EO(H2/H+)EO(S/H2S)EO(Sn4+/Sn2+)EO(I2/I-)EO(Fe3+/Fe2+)MgAlZnH2H2SSnCl2KIFeCl2Mg2+Al3+Zn2+H+SSn4+I2Fe3+52Ag++FeFe2++2Ag2Ag+2HIAgI(s)+H2(g)Cl2(g)+2I-2(s)+2Cl-MnO4-+5Fe2++8H+Mn2++5Fe3++4H2O5()FeFe2+(c1)Ag+(c2)Ag()Ag++e-AgFe2e-Fe2+()AgAgII-(c1)+(c2)H2(Pt)()2H++2e-2Ag+I-e-AgI()(Pt)I2I-(c1)Cl-(c2)Cl2(Pt)()Cl2+2e-2Cl-2I-2e-I2()(Pt)Fe2+(c1)Fe3+(c2)MnO4-(c3)Mn2+(c4)H+(c5)(Pt)()MnO4-+8H++5e-Mn2++4H2OFe2+e-Fe3+6ECd+Zn2+Cd2++Zn6Mn2++5Cr2O72-+11H2O6MnO4-+10Cr3++22H+K2S2O8+2KCl2K2SO4+Cl26EO(Zn2+/Zn)=0.76VEO(Cd2+/Cd)=0.403VEO(MnO4-/Mn2+)=1.51VEO(Cr2O72-/Cr3+)=1.36VEO(S2O82-/SO42-)=1.96VEO(Cl2/Cl-)=1.3583V7ZnZn2+(0.01mol?L-1)Fe2+(0.001mol?L-1)FePtFe2+(0.01mol?L-1),Fe3+(0.001mol?L-1)Cl-(2.0mol?L-1)Cl2(pO)PtAgAg+(0.01mol?L-1)Ag+(0.1mol?L-1)Ag7E=E(Fe2+/Fe)E(Zn2+/Zn)=EO(Fe2+/Fe)+0.0592/2lgc(Fe2+)[EO(Zn2+/Zn)+0.0592/2lgc(Zn2+)]=0.447+0.0592/2lg0.001(0.7618+0.0592/2lg0.01)=0.2852VZn+Fe2+Fe+Zn2+E=E(Cl2/Cl-)E(Fe3+/Fe2+)=EO(Cl2/Cl-)+0.0592/2lg[p(Cl2)/pO]/c2(Cl-)[EO(Fe3+/Fe2+)+0.0592lgc(Fe3+)/c(Fe2+)]=1.35830.0592lg2.0(0.771+0.0592lg0.001/0.01)=0.629VCl2+2Fe2+2Cl-+2Fe3+E=E1(Ag+/Ag)E2(Ag+/Ag)=EO(Ag+/Ag)+0.0592lgc1(Ag+)[EOAg+/Ag)+0.0592lgc2(Ag+)]=0.0592lgc1(Ag+)/c2(Ag+)=0.0592lg0.1/0.01=0.0592VAg+Ag+(0.1mol?L-1)Ag+Ag+(0.01mol?L-1)80.01mol?L-1FeSO40.1mol?L-1MnSO40.02V8E=E(Fe2+/Fe)E(Mn2+/Mn)=EO(Fe2+/Fe)+0.0592/2lgc(Fe2+)[EO(Mn2+/Mn)+0.0592/2lgc(Mn2+)]=0.447+0.0592/2lg0.01(1.185+0.0592/2lg0.1)=0.6788VlgKO===24.9324KO=8.5610240.02VMnSO4x0.0592/2lg0.1/(0.1/x)=0.02x=2.1779CuS0.1mol?L-1Cu2+H2S0.670VECu2+/Cu=0.337VEZn2+/Zn=-0.763VH2SKa1=1.310-7Ka2=7.110-15CuS9E=E(Cu2+/Cu)EO(Zn2+/Zn)=EO(Cu2+/Cu)+0.0592/2lgc(Cu2+)EO(Zn2+/Zn)lgc(Cu2+)=[EEO(Zn2+/Zn)EO(Cu2+/Cu)]2/0.059=(0.6700.76180.3419)2/0.0592=14.6520c(Cu2+)=2.2310-15mol?L-1Cu2++H2S==CuS(s)+2H+c(H+)=20.1=0.2mol?L-1c(S2-)===2.3410-21mol?L-1KOSP(CuS)=c(Cu2+)c(S2-)=2.2310-152.3410-21=5.2210-3610EO(Cu2+/Cu=0.337VECu2+/Cu+=0.153VKspCuCl=1.210-6Cu2++Cu+2Cl-=2CuClK10Cu2++Cl-+e-2CuCl(s)EO(Cu2+/CuCl)=EO(Cu2+/Cu+)+0.0592lgc(Cu2+)/c(Cu+)=EO(Cu2+/Cu+)+0.0592lgc(Cu2+)/[KOSP(CuCl)/c(Cl-)]=EO(Cu2+/Cu+)0.0592lgKOSP(CuCl)=0.1530.0592lg1.210-6=0.5035VCu+2Cl-e-2CuCl(s)EO(CuCl/Cu)=EO(Cu+/Cu)+0.0592lgc(Cu+)=EO(Cu+/Cu)+0.0592lg[KOSP(CuCl)/c(Cl-)]EO(Cu+/Cu)=2EO(Cu2+/Cu)EO(Cu2+/Cu+)=20.3370.153=0.521VEO(CuCl/Cu)=0.521+0.0592lg1.210-6=0.1705VEO(Cu2+/CuCl)EO(CuCl/Cu)lgKO===5.625KO=4.2210511EO(Tl3+/T1+)=1.25VEO(Tl3+/T1)=0.72Va-TlT1+Tl3+Tl+b-TlT1+Tl3+Tl+Pt+c-TlT13+Tl3+Tl+Pt+rGmO11EO(Tl+/T1)=3EO(Tl3+/T1)2EO(Tl3+/T1+)=30.7221.25=0.34VaTl3++2Tl==3Tl+EO=EO(Tl3+/T1)EO(Tl+/T1)