03/03/2015

ElectromotiveForce(EMF)

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ElectromotiveForce(EMF)
Skillstodevelop
Explainelectromotiveforce.
Constructthereferencehydrogenelectrodeandexplainwhyitisareference.
Distinguishreductionpotentialsfromoxidationpotentials.
Calculatethestandardpotentialfromthereductionpotentials.

ElectromotiveForce(EMF)
Theelectromotiveforce(EMF)isthemaximumpotentialdifferencebetweentwoelectrodesofa
galvanicorvoltaiccell.Thisquantityisrelatedtothetendencyforanelement,acompoundoranion
toacquire(i.e.gain)orrelease(loss)electrons.Forexample,themaximumpotentialbetweenZnand
Cuofawellknowncell
Zn(s)|Zn2+ (1M)||Cu2+ (1M)|Cu(s)
hasbeenmeasuredtobe1.100V.A
concentrationof1Minanidealsolutionis
definedasthestandardcondition,and
1.100Visthusthestandard
electromotiveforce,Eo,orstandardcell
potentialfortheZnCugalvaniccell.
Thestandardcellpotential,Eo,ofthea
galvaniccellcanbeevaluatedfromthe
standardreductionpotentialsofthetwo
halfcellsEo.Thereductionpotentialsare
measuredagainstthestandardhydrogen
electrode(SHE):
Pt(s)|H2(g,1.0atm)|H+ (1.0M).
Itsreductionpotentialoroxidationpotentialisdefinedto
beexactlyzero.
Thereductionpotentialsofallotherhalfcellsmeasuredin
voltsagainsttheSHEarethedifferenceinelectricalpotential
energypercoulombofcharge.
NotethattheunitforenergyJ=Coulombvolt,andtheGibbs
freeenergyGistheproductofchargeqandpotential
differenceE:
GinJ=qEinCV
forelectricenergycalculations.

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ElectromotiveForce(EMF)

EvaluatingStandardCellPotentialEofGalvanicCells
Agalvaniccellconsistsoftwohalfcells.Theconventioninwritingsuchacellistoputthe
(reduction)cathodeontherighthandside,andthe(oxidation)anodeonthelefthandside.For
example,thecell
Pt|H2|H+ ||Zn2+ |Zn
consistsoftheoxidationandreductionreactions:
H2=2e+2H+ ....anode(oxidation)reaction
Zn2+ +2e=Zn....cathode(reduction)reaction
IftheconcentrationsofH+ andZn2+ ionsare1.0MandthepressureofH2is1.0atm,thevoltage
differencebetweenthetwoelectrodeswouldbe0.763V(theZnelectrodebeingthenegative
electrode).TheconditionsspecifiedabovearecalledthestandardconditionsandtheEMFso
obtainedisthestandardreductionpotential.
Notethattheabovecellisinreverseordercomparedtothatgiveninmanytextbooks,butthis
arrangementgivesthestandardreductionpotentialsdirectly,becausetheZnhalfcellisareduction
halfcell.Thenegativevoltageindicatesthatthereversechemicalreactionisspontaneous.This
correspondstothefactthatZnmetalreactswithanacidtoproduceH2gas.
Asanotherexample,thecell
Pt|H2|H+ ||Cu+ |Cu
consistsofanoxidationandareductionreaction:
H22e+2H+ ....anodereaction
Cu2+ +2eCu....cathodereaction
andthestandardcellpotentialis0.337V.Thepositivepotentialindicatesaspontaneousreaction,
Cu2+ +H2Cu+2H+
butthepotentialissosmallthatthereactionistooslowtobeobserved.

Example1
Whatisthepotentialforthecell
Zn|Zn2+(1.0M)||Cu2+(1.0M)|Cu
Solution
Fromatableofstandardreductionpotentialswehavethefollowingvalues
Cu2+ +2eCu...E=0.337(1)
ZnZn2+ +2e...E*=0.763(2)
Add(1)and(2)toyield
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ElectromotiveForce(EMF)

Zn+Cu2+ Zn2+ +Cu...E=E+E*=1.100V

NotethatE*istheoxidationstandardpotential,andEisthereductionstandardpotential,E*=
E.ThestandardcellpotentialisrepresentedbydE.
Discussion
Thepositivepotentialconfirmsyourobservationthatzincmetalreactswithcupricionsin
solutiontoproducecoppermetal.

Example2
Whatisthepotentialforthecell
Ag|Ag+(1.0M)||Li+(1.0M)|Li
Solution
Fromthetableofstandardreductionpotentials,youfind
Li+ +eLi...E=3.045,(3)
Ag=Ag+ +e...E*0.799,(4)
Accordingtotheconventionofthecell,thereductionreactionisontheright.Thecellonyour
lefthandsideisanoxidationprocess.Thus,youadd(4)and(3)toobtain
Li+ +AgAg+ +Li...dE=3.844V
Discussion
Thenegativepotentialindicatesthatthereversereactionshouldbespontaneous.
Somecalculatorsusealithiumbattery.TheatomicweightofLiis6.94,muchlighterthanZn
(65.4).

Summary
Theelectromotiveforce(EMF)isthemaximumpotentialdifferencebetweentwoelectrodes
ofagalvanicorvoltaiccell.
ThestandardreductionpotentialofMn+ ,1M/Mcoupleisthestandardcellpotentialofthe
galvaniccell:
Pt|H2,1atm|H+ ,1M||Mn+ ,1M|M
ThestandardeoxidationpotentialofM|Mn+ ,1Mcoupleisthestandardcellpotentialofthe
galvaniccell:
M|Mn+ ,1M||H+ ,1M|H2,1atm|Pt
Ifthecellpotentialisnegative,thereactionisreversed.Inthiscase,theelectrodeofthe
galvaniccellshouldbewritteninareversedorder.

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ElectromotiveForce(EMF)

ConfidenceBuildingQuestions
Inwhichcelldoesreductiontakesplace?Therighthandcellorthelefthandcellinthe
notation
|left|left+||right+|right|?
Answer...Right
Consider...
Oxidationtakesplaceinthelefthandcell.
ReductiontakesplaceintheRighthandcellorcathode.
Reductionpotentialsofhalfcellsaremeasuredagainstwhat?
A. ThezinchalfcellZn|Zn2+1M.
B. ThehydrogenhalfcellPt|H2|H+1M.
C. ThehydrogenhalfcellH+1M|H2|Pt.
D. ThecopperhalfcellCu2+1M|Cu.
E. ThehydrogenhalfcellPt|H2|H+107M.
Answer...B.
Consider...
Pt|H2|H+ 1M||right+ |right
givesthereductionpotential.
Isthepotentialforthebattery
Pt|H2|H+||Cl2|Cl|Pt
positiveornegative?
Answer...Positive
Consider...
Cl2+2e2Cl...E=1.36
H22H+ +2e...E=0.00

Cl2+H22HCl...E=1.36V
Thereactionisspontaneous.
cchieh@uwaterloo.ca

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