參考物理化學(xué)-chapter

Chapter BasicconceptsofTherearetwopathwayforsomeForexample：Zn＋Cu2+→Ina Ina2e-SaltWElectrochemicalchemicalprimarycell(Galvanic[ɡ?l?v?n?k]cell)electricchemicalelectrolyticasciencethatstudiestherelationshipbetweenelectricandchemicalphenomenaandtheconversiondisciplinesbetweenelectricandchemicalenergygalvanicchemical electricElectrolyticGalvanicelectrolyticanode：['?n?ud(陽(yáng)極),cathode['k?θ?ud(陰極)positiveelectrode(正極)negativeelectrode(負(fù)極正極(positiveelectrode)——電勢(shì)高的電極負(fù)極(negativeelectrode)——電勢(shì)低的電極(anode)——發(fā)生氧化作用的電極陽(yáng)陽(yáng)陰原電-+電解+-TheActivityofElectrolyticSolution(p231)Non-electrolyteThesoluteisnotpresentasElectrolyteThesoluteisionizedandtheionsgenerallyinteractstronglywitheachFor

Mz

zNumbersofionsinthezChargesofionsinthechemicalzBa(NO3

Ba22NO

2:13434

2NaSO

1:244

Ba2SO

2:2Foridealsolutionordiluterealsolutionsofnon-electrolytes (T)RTmBBBmFornonidealsolutionofnon-BB(T)RTlnBB,maB,mB,mmForelectrolyticsolutionsuchasdiluteHClsolution:HClHCl(aHCl) (aH) aamamHH(T)RTlnHH(T)RTlnH H()RT(HH)()RT(HH)aala Forθ

aRTln

a aaBecausesolutiononlycontainingsingleiondoesnotexist,theactivityofindividualionisunmeasurable.aMeanactivity:a

(av v

)1/

vv

vMeanactivity

v 1/))Mean

(mvmv

)1/aam mavavBav( mm)vExample:m

(mvmv

)1/0.005molkg-1K2SO4,=pleasecalculate111)3a0.00794Meanactivity1921,Ionic2I2

mz2

iZ:Chargesofionsinthechemical例分別計(jì)算m=0.500mol·kg-1的KNO3、K2SO4K4Fe(CN)6溶液的離子強(qiáng)度

I1mz解：KNO3K++

BI1[0.512

0.5(1)2]molkg1

0.5molkg1K 2K+SO2 I1[(20.5)12

0.5(2)2]molkg1

1.5molkg1K 4K+ I1[(40.5)12

0.5(4)2]molkg1

5molkg1II12m2 B1(m2 z2z -z)1[0.01120.00122(0.0120.001)122選擇某電解質(zhì)溶液的濃度m0.05molkg1，離子強(qiáng)度I=0.15molkg1，該電解質(zhì)是 A. B.C. D.答案TheDebye-HückellimitinglawwhenI<0.01m(P233-234)lnlnAZZ ln1.172ZZ ln1.172ZZ Ilg

ZZ25℃時(shí)，用極限公式計(jì)算強(qiáng)電解質(zhì)AB、AB2、AB3在 I2

1(0.0001m m

0.000112)

0.0001lglgAzz I0.50911 0.00010.00500.988

IlglgAzz I0.50912 0.00030.0176

1(0.00012m m

0.000212)

0.0003 0.960

0.9177.3ReversibleCellandReversibleElectrodeThedefinitionofReversibleconversionofchemicalenergytoelectricenergyinathermodynamicreversibleMeaningofthermodynamicReversibleReversibleI（Daniel）電池(銅-鋅電VA-+VA-+A

Zn：ZnZn2+2eCu(+)：Cu2++2e→CuZn+Cu2+→Zn2++ZnZn2+2eZnCu(-)Cu→Cu2++2eZn2++Cu→Zn+

充電時(shí)

Cu2+(s)

放電反應(yīng)

陰極Zn2Zn22eCu(s)Cu2充電反應(yīng)

Zn(s)Zn(s)充

E

為不可逆電放Zn(s)放充充

H2H2可逆電池的書(shū)寫(xiě)方式可逆電池的書(shū)寫(xiě)方式原電池的書(shū)寫(xiě)方式負(fù)極（陽(yáng)極，氧化反應(yīng)，失去電子）在左邊正極（陰極，還原反應(yīng)，得到電子）在右邊相界面用“|”表示，“||”表示鹽橋Zn(s)┃Zn(s)┃H2SO4(a)A-+Pt(s)|H2(

)|HCl(a)|AgCl(s)|Ag(s)|AgCl(s)|HCl(a1)||AgNO3(a2)|Kindsofreversiblethefirst-classmetalelectrodegaselectrodemetal–metalionConsistingofametalplateimmersedinasolutioncontainingthecorrespondingmetalions.ionCu(s)Cu2+:Cu2++2e–CuZn2++2e–+xHgZn(Hg)xAg(s)Ag(CN)2–:Ag(CN)2–+e–Ag+2Gaselectrode:H2H+solutionPtplatehydrogenhydrogenPt(s)Pt(s)H2(p)OH-2H++2e-2H2O+2e-oxygenelectrode

oxygenelectrodeO2+4H++4e-2

O2+2H2O+4e-Thesecond-classmetal–insolublesalt-anionconsistingofametalplatecoatedwithinsolublesaltcontainingthemetal,andimmersedinasolutioncontainingtheanionsofthesalt.ElectrodeAgCl(s)AgCl(s)+ Ag(s)+Cl-Hg(l)Hg2Cl2(s)Cl-Hg2Cl2(s)+2e-2Hg(l)+2Cl-Pb(s)PbSO4(s)SO42-PbSO4(s)+2e-Pb(s)+SO42-metal–insolublemetaloxide/H+,OH-Ag—Ag2OBasicsolution：OH-|Ag2O(s)|Electrodereaction：Ag2O+H2O+2e→2Ag+Acidicsolution：H+|Ag2O(s)|Electrodereaction：Ag2O+2H++2e→2Ag+Sb|Sb2O3H+┃Sb2O3(s)|Sb2O3+6H++6e2Sb+OH-┃Sb2O3(s)|Sb2O3+3H2O+6e2Sb+6 Thethird-classelectrode:oxidation-reductionimmersionofaninertmetalcollector(usuallyPt)inasolutionwhichcontainstwoionsofthesameelementormoleculesindifferentstatesofoxidation.Pt(s)Sn4+,SnSn4+(c1)+ Pt(s)Fe(CN)3-(c),Fe(CN)4- Fe(CN)63-(c1)+e-Fe(CN)64-DesignofthereversibleWritethetwohalf-Determineelectrodes(andWritecellMakeoxidation-reductionZn+CuSO4=ZnSO4+CuZn–2e-=Zn2+;Cu2++2e-=CuAnode:ZnZn2+; Cathode:CuCu2+;electrolyte:ZnSO4;CuSO4;saltbridgeZn(s)ZnSO4(a1)CuSO4(a2)Pb(s)+HgO(s)→Hg(l)+(－):Pb(s)+2OH－(a)→PbO(s)+H2O+2e HgO(s)+H2O+2e→Hg(l)+Pb(s)|PbO(s)|OH－(a)|HgO(s)|PbO2(s)+Pb(s)+4H+(m)+2SO42- (－):Pb(s)+SO2-(m)→PbSO(s)+ PbO2(s)+SO2-(m)+4H+(m)+2e→PbSO(s)+ Pb(s)|PbSO4(s)|H2SO4(m)|PbSO4(s)|nonoxidation-reduction(1)H2O=H++H2O+1/2H2(p)→H++OH-+1/2H2–e-=H+;H2O+e=1/2H2+Anode:Pt(s)H2(p)H+;Cathode:Pt(s)H2(p)OH-;electrolyte:H+,OH-;saltbridgePt(s)H2(p)H+(a1)||OH-(a2)H2(p) AgCl(s)+I-→AgI(s)+AgCl(s)+I-+Ag(s)→AgI(s)+Cl-+∴Ag|AgI|I-||Cl-|AgClNernstequationandstandardelectromotiveforceofTheconversionofchemicalenergyintoelectricalAtconstantAtconstantTand

nor|ve|：theabsolutevalueofthestoichiometricnumbertheelectronintheelectrochemicalE：electromotiveF:Faradayconstant①①H2(p)+Cl2(p)→2H+(a+)+2Cl-(a-②1/2H2(p)+1/2Cl2( )→H+(a+)+Cl-(a-rGm

rGm

E1ForageneralelectrochemicalcC+dD=gG+KKa agahacadCDRTlnGagahacad

rGmrGm

EE

aln a

acad NernstGnFERTlnKrmE

RTlnK

Foranyreactionthatcanbedesignedtotakeplaceinaelectrochemicalcell,itsequilibriumconstantcanbemeasuredelectrochemically例

E

aln a acad試計(jì)算25°C時(shí)，下面電池的電動(dòng) H2

kg-

EQ

g±解：電池反應(yīng)為21H Ag+HCl(m=0.1molkg-1)22E=E0

0.05916

a(Ag)a(Hl){p(H2)

1/

EE

aln a acad

p(H)=p0=100 =av=

m±

=(mv+

)1/

2 2E=

{0.05916

TheCalculationofOtherThermodynamicPropertiesofCell-rGm=withrespecttotemperature,werGm)EPSnFTPQQTSnFTETrmrmT nFEnFTETrmnFE ETTPBymeasuringEand(E/T),thermo- tiesofthecellreactioncanbedetermined.BecauseEand(E/T)pcanbeeasilymeasuredwithhighaccuracy,historically,thethermodynamicdatausuallymeasuredusingelectrochemicalotherthanthermal

rGm=-nF

SSnFETPrmnF ETT PEQQRnFTETPQRQRTSnFT(E)(2PHnFEnFT(E)(3TP討論熱效應(yīng)：QP= 比較（2）,（3）QRH呢？QP= 注意：（4）式適用范圍無(wú)非體積功：Wnonpv對(duì)于可逆電池反應(yīng)：Wnonpv0，所以不能用H表示電池反應(yīng)的熱效應(yīng)（盡管電池反PTHPTHnFEnFT(E)(3PTTSnFT(E)(2)Q無(wú)論通過(guò)電池反應(yīng)或熱化學(xué)反應(yīng)，兩者的始、終態(tài)相同，所以其H相同，但熱效應(yīng)不同。若電池反應(yīng)自發(fā)，E0，QR（電）QP（熱）即電池反應(yīng)與熱反應(yīng)相比，更易從環(huán)境吸熱（或更少向環(huán)境放熱）其差額即為電（nFE）125℃時(shí)，電池：Cd｜CdCl222H2O(飽和溶液)｜AgCl｜Ag的＝0.67533V，求該溫度下反應(yīng)的ΔrGm、ΔrSm和ΔrHm及Qr。已知

左極氧化：Cd21HOCl(a) HO 右極還原

2AgCl2e2Ag2Cl 電池反應(yīng)：Cd21HO2AgCl HO nΔrGm=-＝-296485Cmol-1＝-130.32kJmol- 296485Cmol1-6.510-4VK-1-125.4JK-1mol-

296485Cmol1 MF [298.15K6.510-4VK-1167.7kJmol-Qr=TrSm=298.15K(-125.4JK-1mol–1)=-37.39kJmol-進(jìn)行，則Qr=-37.39kJmol-1Qp與Qr之差為電W'r=-167.7kJmol-1-(-37.38kJmol-1)=-130.32kJmol-若E若T

11Cd121HOAgCl1CdCl1HOA22222222At298K,Ag(s)-AgCl(s)KCl(m)Hg2Cl2(s)-Hg(l),E=0.0455V,(E/T)P3.3810-4VK-1.WritethecellandcalculaterGm,rSm,rHm,andAg(s)+?Hg2Cl2(s)AgCl(s)+rGm=-nFE=-196500=-4.391kJmol-rSm=nF=1965003.3810-4VK-=32.62Jmol-1K-rHm=nF[T(E/T)P=196500[2983.3810-4=5.329kJmol-Q=TrSm=nFT=9.720kJmol-例 已知電Zn(s)|Zn2+(a1=1)||Cu2+(a2=在298.15KE=1.103V,313.15KE=1.096Vn=2298.15KΔrGm、ΔrHmΔrSmK?QR解:ΔrGm－nEF=－212.9kJmol-(E/T)P=(ΔE/ΔT)P== VK-ΔrSm=nF(E/T)P=2×96500×(－4.7×10－4)=－90.7JK-1mol-1ΔrHm=－nEF+nFT=－212.9+(－90.7)×298.15×10-=－212.9－27.0=－239.9kJmol- 因?yàn)樵撾姵胤磻?yīng)為Zn(s)+Cu2+(a2=1)→Zn2+(a1=1)+參與反應(yīng)的物質(zhì)皆處于各自的標(biāo)準(zhǔn)狀態(tài)EE?,所以，298.15K時(shí)lnln nEF21.1038.314 =TheThermodynamic forAqueousions(P240)ErGm,rSm,rHm,and m, m, tiesforaqueous112H(p)212Cl(p)HCl2112H( )122Cl( ) (aq)Cl(aq)2HH[H(aq)]H[ClrmfmfmThecustomaryconventionistotakethestandardfreeenergyofformationofH+(aq)atanytemperaturestobezero(p240).GG[H(aq)]fmH[H(aq)]fmS[H(aq)]mHH[H(aq)]H[Clrmfmfm167kJmolH[Cl(aq)]167kJmolfmTableStandardfreeenergiesofformationofaqueousionsat298.3K /kJmol-m /kJmol-m--------At298(Pt)H2(p?)KOH(aq)HgO(s)-E?=0.926V,productofwaterKw=10-GivenG?ofHgO(s)is–58.5kJmol- calculate

?ofOH- H2(p?)+HgO(s)=Hg(l)+G?=-296500 =-178.82kJmol-1=G?(HO(l))- H2O=H++G?=G?(H+)+G?(OH-)-G?(H fGm(OH-)=-157.3kJmol-MechanismofProductionofelectromotiveforcesAA-+Theelectromotiveforcesincludethreepotentialsdifferenceofinterface Liquid-liquidinterfaceliquidjunctionpotentialdifference,diffusionpotentialdifference（液接電位、擴(kuò)散電Liquid-metal：electrodepotentialDiffusiondoubleThepotentialsforthemetal:MThepotentialsfortheLiquid:1,Equlibriumstate:Liquid-metalelectrodepotentialdifferenceε=│M－1│金屬表面帶正電還是帶負(fù)電，與金屬的晶格能和水化能的相對(duì)大小有關(guān)：水化能大于晶格能，金屬表面帶負(fù)電。如：ZnGd、Mg、Fe等水化能小于晶格能，金屬表面帶正電。如：CuAu、Pt等Liquid-liquidinterface：liquidjunctionpotentialdifference,diffusionpotentialWhentwoelectrolyteswithdifferentcompositioncontact,apotentialdifferencewillestablishacrosstheboundarybetweenthetwosolutions.InducedbydifferenceofionicdiffuseForexampleUH+UCl，Q左 Q右，to difference，E()，E()canreduceUH+andincreaseUCltill

=

，diffusionequilibrium，

Hjunctionpotentialdifference,diffusionpotentialdifferenceHThecharacteristicofliquidjunctionpotentialdifference：Thediffusionofionsresultsisirreversible,whichdestroysthereversibilityofthecell.Becausethevalueofliquidpotentialdifferenceisdifficulttodetermine，wewilltrytodecreaseoreliminateit. junctionpotentialdifference：SinglesolutionThesaltbridgeisoftenusedtoconnectthetwoelectrodecompartmentstoreducethejunctionTheroleofsaltsaltbridge——Dissolve3gofagar-agarin20-30mlhotKClsaturated-solutionand ytransferittoUtubethenallowitstandforseveralmin.thefactortoformsaltbridge：(1)t+≈t-(2)highconcentration；(3)doesnotwitheitherthereasontodecreaseoreliminateSalt

∴El,1＋j2≤2j

j(j1=-jThesaltbridgeintroducestwoliquidjunctionswhoseemfsareoftenopposedtooneanother,andthenetjunctionpotentialisverysmall.TheofElectrodePotentialZn(s)|ZnSO4(aq)CuSO4(aq)| E=ε++ε－+ε+=Cu－εj

ε-=l－2l1=lE=ε++E=Cu－Zn=+－ E=+ Whenemfofacellwasmeasured,we,infact,measurethepotentialdifferencebetweenthetwoelectrodes. electrodes,i.e.,electromotiveofthecellE=+canbe

Electrodepotentialitselfisofgreattheoreticalandpracticalimportance.ThepotentialofindividualelectrodecanbeonlyobtainedbysettinganarbitraryNormalorStandardHydrogenElectrodeIn1953,InternationalUnionofPureandAppliedChemistry(IUPAC)definednormalhydrogenelectrodeasthereferenceformeasurementofelectrodePt(s)PPH2PmHHHH+/H2=0.000000

StandardelectrodeThepotentialofotherelectrodecanbeobtainedbycombinationofNHEandanyotherunknownelectrodeintoanelectrochemicalcellwithNHEservingasnegativeelectrodeandtheunknownelectrodeaspositiveelectrode（-）NHEunknownelectrodeThesignandthevalueoftheemfofthiscellisthusthesignandvalueofthepotentialoftheunknownelectrodeSHECu2+E=theelectrodepotentialoftheCuCu2+(a=0.1)electrodeisthusCu2+/Cu=PP,H(P)|Ht2H1)||Zn2E=- Zn

的意義>0：表明在上述電池中，電極x實(shí)際發(fā)生越正，表明還原反應(yīng)的<0：表明在上述電池中，電極x實(shí)際發(fā)越負(fù)，表明氧化反因此：↑，說(shuō)明電極上的還原反應(yīng)越容易易的標(biāo)志，故亦稱作還原電極電勢(shì)) writteninthereductionform. + (reduction)(standard)electrodeNernstequationforSHECu2+(a=0.1)CuCellrecation:H2(po)+Cu2+(a)=2H+(a=1)+EEEaHaaH2a2Cu2/H/Cu2/H/2RTlnCu2/Cu2/RTlnaRTlnRTlnForgeneralelectrodereaction:cC+dD+ne-=gG+hH

lni Nernstequationforelectrodereactionorhalf-cellreactionReferenceProblemswithNHE(primaryTheplatinizedplatinumelectrodeiseasilypoisonedbytheadsorptionofimpuritiesfromthesolutionandthegas.Theadsorptionoftheimpuritieshinderstheestablishmentoftheequilibriumatthesurfaceandtheelectrodenolongerbehavesreversibly.Anelaboratepurificationtrainisrequiredtopurifythehydrogenbeforeitispassedthroughthecell,whiakestheuseofthehydrogenelectrodecumbersome.Amoretrivialannoyanceisthatchangesinbarometricpressureorinthedepthofimmersionoftheelectrodeinthesolutionproduceasmallvariationinthepotentialoftheelectrode.Someelectrodeswithstablepotentialusuallyusedasthesecondarystandard,namedasreferenceelectrode.Thereferenceelectrodeusedmainlybasedonthemercury-mercuroussalectrodesbecauseoftheirgoodreproducibilityandeaseofconstructionandmaintenanceCalomel_Cl-┃Hg2Cl2(s)—Hg(l)Hg2Cl2+2e2Hg+2Cl-_(Hg2Cl2)

(Hg2Cl2)

RTF

a(ClCl/Hg2Cl2,0.1.otherreference4Themercury-mercuroussulfateelectrode:Hg(l)Hg2SO4(s)SO2-(m)4?＝+0.640Themercury-mercuricoxideelectrode:?＝+0.098TheSilver-silverChloride?＝0.197ThekindsofThekindsofChemicalConcentrationChemical

SinglesolutioncellsDoublesolutioncellsSinglesolutioncellsDoublesolutioncellsChemicalcellwithsinglePt,H2(P)HCl(m)AgCl+AgPt,H2(P)HCl(m)AgCl+AgForageneralelectrochemicalH2(P)+2AgCl(s)2HCl(m)+2Ag單液化學(xué)電池EΘ≠電池凈反應(yīng)為化學(xué)反E與溶液活度有關(guān)，有一種電解質(zhì)溶液ChemicalcellwithdoubleZnZnCl2(m1)HCl(m2)H2(P),ZnZnCl2(m1)HCl(m2)H2(P),ForageneralelectrochemicalZn(s)+2H+(m2)Zn2+(m1)+H2雙液化學(xué)電池EΘ≠電池凈反應(yīng)為化學(xué)反E與溶液活度有關(guān)，有兩種電解質(zhì)溶液Concentrationcellwithsingle電池總反應(yīng)僅為物質(zhì)從高濃狀態(tài)低濃狀11）K(Hg)(a1)KCl(m)K(Hg)反應(yīng)式）Ka1eK+）K+(m)+eK電池總反應(yīng)Ka1)KK(a1)KEE

RTlna2 a1RTlna2 a1

RTln aPt,Cl2(P1)HCl(m)Cl2(P2),）2Cl(m)2eCl2+）Cl2(P2)+2e2Cl總反應(yīng) Cl2(P2)Cl2Cl2(P2)Cl2EE

RTlnP1 RTln P

RTlnP2 P1單液濃差電池EΘ=ConcentrationcellwithdoubleAgAgNO3(m1)AgNO3(m2)電池反應(yīng)：）AgeAg++）Ag+(m2)+eAg+(m2)Ag+Ag+(m2)Ag+E

RT

m1

RT

m2 m2

m1電池反應(yīng)Cl(m1ClE

RT

m2

RT

m1 m1 m2Ag|AgNOAg|AgNO3(a1)||AgNO3(a2)(-)Ag→Ag+(a1)+(+)Ag+(a2)+e→ Ag+(a2)→Ag+ E

ln (-)Ag+Cl－(a1)→AgCl(s)+ (+)AgCl(s)+e→Ag+ Cl(a)Cl(a E

ln 雙液濃差電池特EΘ=E僅與溶液活度有關(guān)，有兩種電解質(zhì)溶液Applicationofelectrodepotentialand1.DirectionofrGm

nFE

nF

左

例：試判斷下述反應(yīng)標(biāo)態(tài)下向哪方進(jìn)行？并求離子為標(biāo)態(tài)時(shí)反應(yīng)轉(zhuǎn)向

aAg

設(shè)計(jì)成電池

Pt|Fe2,

|查表

(Ag

/

/Fe2)

正向自(Ag

/Ag

0.05916lg

0.771aAg

0.339例題 用電動(dòng)勢(shì)E的數(shù)值判斷在298.15KFe2I2還原為Fe2+(a=1)+?I2(s)→Fe3+(a=1)+I－(a=I2,I=0.5355V，F(xiàn)e3解:把反應(yīng)設(shè)計(jì)為電池Pt|Fe2+,Fe3+||I－|I2(s),離子的活度均等于1EI2,II2,IFe3=0.5355－0.771=－0.235VΔrGm=－nEF=－1×(－0.235)×9648522.674kJmol-1,ΔrGm0,反應(yīng)非自發(fā)Fe2I2還原為I－Fe3I－I2Advanceofreaction(equilibriumconstants)GθRTlnKθ KθKθexpθ 計(jì)算298.15K時(shí)AgBr的活度積Ksp

Ag,解:這實(shí)際上是計(jì)算AgBr(s)溶解平衡的平衡常數(shù)K? Ag++把反應(yīng)設(shè)計(jì)成電池Ag(s)|Ag+(a1)||Br－(a2)|AgBr(s)+負(fù)極 Ag(s)→Ag+(a1)+ AgBr(s)+e→Ag(s)+電池反應(yīng):AgBr(s)Ag+(a1)+EEAgBr,Ag,lnlnKln0.7278964858.314E?0表明該反應(yīng)非自對(duì)計(jì)算Ksp無(wú)影響例寫(xiě)出下列電池電動(dòng)勢(shì)的 方程，并計(jì)298.15K時(shí) Pt|H2(g,100kPa)|H+||OH|H2(g,100kPa)|Pt1H(g,100kPa)-e?H+ H2O+e?OH+2H2

H2O

H+E0=

0{H

H2

j0

H22E02

RTlnK 2j0{H2

H2(g)}=

0

H2

RTlnK j0wj0w

10-2\j0{H2

H2

RTlnK =0.05916

-今欲求AgCl的活度積，則應(yīng)設(shè)計(jì)的（）Ag(s)｜AgCl(s)｜HCl(aq)Pt｜Cl2(P)｜HCl(aq)Ag(s)｜AgCl(s)｜HCl(aq)答案DeterminationofmeanionactivitycoefficientsForexample，298K，pθ，±forHCl(m)2Pt|H(p2

1H(p

H22() AgCl(s)eAg(s)221H(p)

Ag(s)Cl+HEE(Cl(Cl|AgCl,Ag)RTln2mFmE和E,可求出Determinationof1909,Sorensendefined:pH=-logModernHpHlogaH

isnotaoperationalHydrogen (Pt)H2(p?)HEEH/HRTlgHSCEpH

[ESCE

0.05916例已知已知25℃時(shí)，下列電池的電動(dòng)勢(shì)E=0.6095V，試計(jì)待測(cè)溶液的pHPt

待測(cè)

oldm-

Cl2(s)解j

0.333VpH=E-E甘=0.6095-GlassMembraneglassthemembranepotentialcanbedevelopedbyexchangeofionsbetweenglassmembraneandthesolution.Ag(s)AgCl(s)Cl-glassGlassAg(s)+AgCl(s)|HCl(m=2.303RTF2.303RTFH

lnaToforma Ag+AgClHCl(0.1m)玻璃膜pH(x)E=SCE=SCE

2.303RTFpH

SCE

Intheequation,GE?isaconstant,whichisrelatedtothepropertyandusedtimeofglasselectrode.ThedifferentglasselectrodecangetdifferentvalueofGE?.Forcertainglasselectrode,thevalueofwillchangeastimeThepHmeter,asitisoftencalled,iscalibratedbymeansofbutterofknownpHbeforeitisusedtomeasurethepHofanunknownsolutionabutterofknownpHpH

pH

pH(pH(x)pH(s)填空若原電Ag(s|AgCl(s)|HCl(a|Cl2(g,p|Pt(s)的電池1 Cl 2Ag(s)+Cl2g)

則 解答個(gè)值，即1=2；2。所以△rG(1)=-FE，△rG(2)=-2△rG(1)=填空已知下列兩電池的標(biāo)準(zhǔn)電動(dòng)勢(shì)分別 EΘ和E 2PtH(g,pΘ)H+{a(H+)=1}Fe3+{a(Fe3+)=1},Fe2+{a(Fe+)=1} 22PtH(g,pΘ)H+{a(H+)=1}Fe3+{a(Fe3+)=1} 22PtH(g,pΘ)H+{a(H+)=1}Fe2+{a(Fe2+)=1} 2與3上述原電池（3）的標(biāo)準(zhǔn)電動(dòng)勢(shì)E與3EΘ和EΘ的關(guān)系式為 解答以E1ΘE2Θ和E3Θ分別為對(duì)應(yīng)電池的正極Fe3+e

(1)

m(1)=

FEQFe33eFe22e

(2) (3)

m(2)= m(3)=

3FEQ2FEQ(2)- D

m(2)-

GQmr-2FEQ(3)=mr

(2)- 1EQ Inthecell

Cu2(aq)thereductionhalfreaction

Cu(s)

Cu2

Cu2(aq)

Cu(s)2Ag(s)

2Ag(aq)2e2Ag(s)Answer:Freeenergychange(ΔG)isrelatedtothee.m.f.ofacell(E)asG(a)G

(d

GnFEEnFGGGAnswer:The

lbelongstothelgasinertmetal 齊）metal-metalinsolubleAnswer:Theentropychange(ΔS)foracellreactionisgivenbynF(EnF[E

nF(E

RTnF

Answer:AhalfcellreactionisoneoccursatonegoesonlyhalfwaytoinvolvesahalfmoleoftheconcentrationofthesolutionalwaysAnswer:TocalculatethesolubilityproductofAgI,thecellwasconstructedA

Ag,I

Ag(s)AIfEoisthestandardelectrodepotential,thenKspisgivenas

nFE0loglog

RTlnKKspKsplnKspE0

E0 ln

nF[(