电化学原理习题答案

©right&[e-mail]12266KClKClHOHO0.001141.31.010142.31010001000cKKKKcm11λ−−−−×=+=+=+×=×Ω2EVFii=λFEViiλ=10288.0−⋅=+scmVH10050.0−⋅=+scmVK10051.0−⋅=−scmVCl3,62.550121,,,,2−−⋅Ω=−+=eqcmKCloHCloKOHoOHoλλλλ2-14WOccc,cK1.008101.004HH+−===×=2,811c5.510cm1000oHOλκ−−−==×Ω41121,,Cl,tt1,t76.33mol(KCloKCloClcmλλλλλ−−−−+−+−=++=∴==Ω⋅∵121121121,K,Na,Cl73.49mol50.14mol76.31mol(NaClooocmcmcmλλλ++−−−−−−−=Ω⋅=Ω⋅=Ω⋅2121Cl,Na,121Cl,K,mol45.126mol82.142−−−−⋅Ω=+⋅Ω=+−+−+cmcmooooλλλλKClNaCl−Cl,oλ3vscmvscmuvscmuFuaoololoio/1020.5,/1062.7,/1091.7,/24N,24K,24C,C,,−−−×=×=×==++−−λλ5Cu(OH)2==Cu2++2OH-,=y2Cuc+OHc−=2yKS=4y3u=Σui=KH2O+10-3[yλCu2++2yλOH-]oλλy=1.3610-4mol/dm3Ks=4y3=1.00610-11(mol/dm3)36==+=y3AgIO+Ag−3IOAgc+3IOc−=y=ySK2K=iK∑=+yOHK2310−+Agλ+y−3IOλ0λ=+yOHK2310−3AgIOλy=43651074.1104.68101.11030.1−−−×=××−×Lmol/;=ySK2=3.03810−×2)/(Lmol7HAco,λ=HClo,λ+NaAco,λ-NaClo,λ=390.7121−−⋅ΩeqcmHAco,λ=9.02121−−⋅Ωeqcmα0/λλ==0.023==1.69αK_2)1/(Vαα−510−×8IR=iSKSl⋅=Kil,K=1000cλ,IR=1000ilcλ⋅=V79.05.0126101010533≈××××−9log±γ=-0.5115||||+Z−ZI25C°1©right&[e-mail]1±γ=0.9740I=212iizm∑,I=212iicz∑=±m++νm−−νmν12±γ=0.91013±γ=0.64874±γ=0.811410=+Ha±γ+HmpH=-log=-log0.209+Ha4.0×=1.081()+2326623SbOHeSbHO++++()−236HH+6e+:2322323SbOHSbHO++00GEnF∆=−83646F=0.0143V≈E=+0E2.36RTF2232323logHSbOSbHOPaaa==0.0143V0E0602.32.3loglog6SbSbHHRTRTaaFFϕϕϕ+++=+=+2.3logHRTaFϕ+−=∴000.0143SbEEϕϕϕ+−=−===V2(()+22442HOeHO+++)−224HH+4e+:22222HOHO+2220022.3log4HOHOPPRTEEEFa=+=0ϕ+=1.229V0ϕ−=0.000V001.229EVϕϕ+−∴=−=()242SnSne++−+():32222FeeFe++++23422SnFeSnFe2++++++23422022.3log2SnFeSnFeCCRTEEFCC++++=+=0.771-0.15+220.05910.001(0.01)log20.01(0.001)××=0.6505V()(0.1)AgAgme+−+()(1)AgmeAg+++(1)(0.1)AgmAgm++→(1)0(0.1)2.3logAgmAgmaRTEEFa++=+0E1m3AgNO0.4Vγ±=0.1m3AgNO0.72Vγ±=2.310.4log0.0440.10.72RTEVF×∴==×32222|(),()|(),ClHgHgClsKClmClPPt()2222HgClHgCle−−++()222CleCl−++222HgClHgCl2+2©right&[e-mail]3222200002.3log2ClHgHgClPaRTEEEFaϕϕ+−=+==−∵O1.35950.26811.0914(25C)EV∴=−=ECla−Eϕϕ+=−−00Eϕϕ+=−−Cla−ϕ+ϕEϕϕ+=−423,(1)|(1)()HPtHatmHClaAgNOmAg+=()222HHe+−+222()AgeAg+++g2222HAgHA++++Eϕϕϕ+−=−=+02.3log()AgAgAgRTEmFϕγ++±∴=−223|(),()()HgHgClsKClAgNOmAg02.3log()AgAgAgRTEmFϕϕγ++±=+−:23,(1)|(1)Pb()PbHPtHatmHClaNOm+=,22Pb2PbHH++++,220PbPbPb2.3log()2RTEmFϕγ++±∴=−:'232e,(1)|(1)FeCl(),FeCl()FHPtHatmHClamm+=,32+21FeFe2HH++++232302.3log()FeFeFeFeRTEaFϕ++++a∴=−5424(),()ZnZnSOmHgSOsHg22402.3log()2SOZnRTEEaaF−+=−222(),()(),HPbPbClsHClmHPPt-20222.3log()2HHClRTEEaaPF+=+6'2,(1)|(1)(0.1),()HPtHatmHClaKClmAgClsAg+=()AgCleAgCl−+++∴02.3logClRTaFϕϕ−++=−0ϕ+=0.2224V0.79Vγ±=0.22240.0591log(0.790.1)0.2876EVϕ+∴==−×=7'2.312.31loglogaClClRTRTEFaFa−−=−'2.3logClClaRTFa−−==0.01m=0.1ma'a0.10.780.078,()Claaa′−±±′′=×==0.010.9040.00904,()Claaa−±±′′′′′′=×==2.32log(bRTEtaaF+±′′′=)±2.30.078(21)log()(20.3891)0.0591log0.01230.00904baRTEEtaaVFϕ+±±′′′∴−==−=×−×=−0.0591,0.046abEVEV==0.01baEEVϕ=−=−822,(1)|(1)|(),PtHatmHIaIsPt=©right&[e-mail]4+−+222()222HHe()IeI−++I222HIH+0202.3log()2HIRTEEaEF=−=030.53460.1310(3525)0.5333EV−=−××−=0,E∵∴00ln2965000.5333102.9GnFERTKkJ∆=−=−=−××=−0lnRTEKnF=2965000.5333ln40.198.314298K××==×172.8610K=×E00151.52GGk′∆=∆=−J85.3510KK′==×+−+2222HgCleHgCl9:()222HHe,()−++++,222222HHgClHgClH−+++022.3log()22HClRTEEaaF+−=−,0.790.1Cla−=×02.32.3loglogHClRTRTaEEaFF+−−=−+lolog6.9Ha+−≈glog14HOHaa+−+=7.18107.9410OHa−−−==×:00.0591logClaϕϕ−++=−0.0591log0.0591HapHϕ+−==−Eϕϕ+−=−6.90.0591EpHϕ+−∴==7.183107.9410()OHamoldm−−−==×102222HgHge++22242HgSOHgSO+−+4242422HgSOHgSOe−++222202.3log2HgHgHgRTaFϕϕ++=+222402.32.3loglog22HgHgSORTRTKsaFFϕ+−=+−2224440,2.3log2HgHgSOSOSORTaFϕϕ−−=−222442007,2.30.0591log0.7986log(6.510)0.63822HgHgSOSOHgHgRTKsVFϕϕ−+−∴=+=+×=()AgClAgCle−−++()2212HgCleHgCl−+++2212AgHgClAgClHg++1965000.04554.391GnFEkJm∆=−=−××=−ol343911965002980.338105.329PEHGnFTkJmolT−∂⎛⎞∆=∆+=−+××××=⎜⎟∂⎝⎠31965002980.3381032.617PESnFTJmolKT−∂⎛⎞∆==××××=⎜⎟∂⎝⎠i12()22ZnZn+−+e()22CueCu+++22ZnCuCuZn++++©right&[e-mail]51.1031.1012965001.101296500293189.8298293PEQpHnFEnFTkJmolT∂−⎛⎞=∆=−+=−××+×××=−⎜⎟∂−⎝⎠1.1031.10129650077.2298293PESnFTJmolKT∂−⎛⎞∆==××=⎜⎟∂−⎝⎠ilnGnFERTK∆=−=−∵221ZnCuaa++==0021.101,log37.262.32.30.00581nFEEEKRTRT×∴====377.9510K=×22GGGFFCu22CueCu+++010.337Vϕ=eCu++020.520Vϕ=000000312123ϕϕϕ∆=∆−∆=−+=−00031220.33720.5200.154Vϕϕϕ∵∴=−=×−=00330.1549650014861GFJmϕ∆=−=−×=−ol0lnRTKnFϕ=132KKK=0002331212ln(lnln)()RTRTRTFFKKKFFFRTRTϕϕϕ==−=−544+−+22442OHeHO++++()001220.1Vϕϕ−=()()224HHe22222HOHOg+1KKp=∵22222lnln44HOHOpRTRTEKFFp=−p()222228122247602.312.30.05910.0591logloglog(9.710)log1.226444411HOHOpRTRTEVFKpFpp−−−∴=−=×−=×22.30.0591loglog(0.020.544)0.0622HHRTaVFϕ+==×=−()2220222.30.0591(loglog)1.229log(0.020.544)log247601.1622OOHOHRTapFϕϕ+⎡⎤=+−=+×−=⎣⎦V()221.160.061.22OHEVϕϕ∴=−=−−=2Zn+2Cu+H+22202.30.0591log0.763log(0.010.39)0.8322ZnZnZnRTaVFϕϕ+++=+=−+×=−22202.30.0591log0.337log(0.010.41)0.2722CuCuCuRTaVFϕϕ+++=+=+×=2.3log0.0591(5)0.30HHRTaVFϕ++==×−=−Cu2HZn©right&[e-mail]0i→220.05910.83log2CuCuaϕ++∴−=+22log(0.830.337)39.490.0591Cua+=−−=−2403.2410Cua+−=×240403.24107.9100.41CuaCγ+−−±×==