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CellEMF

CHM1046
GeneralChemistryII
Dr.MichaelBlaber

Electrochemistry
CellEMF
Hereisasummaryofavoltaiccell:

Akeyquestionis:whatcausestheelectronstoflowfromtheanodetothecathode?
Theelectronsflowfromtheanodetothecathodebecauseofadifferenceinthepotentialenergy
oftheelectronsattheanodecomparedtothecathode
Inparticular,thepotentialenergyoftheelectronsishigherattheanodethanatthecathode
Likewatermoleculesinawaterfall,theelectronsmoveinadirectionfromhighpotential
energytolowpotentialenergy(i.e."downhill"inanenergylandscape)

ThepotentialdifferencebetweentwoelectrodesismeasuredinVolts(V)
Onevoltisthepotentialdifference,betweenananodeandacathode,thatwouldberequiredin
ordertoimpart1Jouleofenergytoachargeof1coulomb(note:1coulombisthechargeofa
collectionof6.24x1018electrons)
1V=1J/C(i.e.energyperelectron)
Thepotentialdifferencebetweentwoelectrodesiscalledtheelectromotiveforce,oremf
Theemfofavoltaiccelliscalledthecellpotential,orthecellvoltage
Thecellvoltageofavoltaiccellwillbepositivevalue
Thecellvoltagewilldependuponthespecifichalfreactions,concentrationsofions,andtemperature
Commontabulationsofcellvoltagesareperformedat25Candstandardconditionsof
concentrationsofliquid(i.e.1M)andgascomponents(i.e.1atm)
Understandardconditions,theemfofavoltaiccelliscalledthestandardemforthestandard
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cellpotential(E0cell)
Byconvention,thepotentialassociatewithanelectrodeisthepotentialforreduction
Thestandardcellpotentialisgivenbythestandardreductionpotentialofthecathode,minusthe
standardreductionpotentialoftheanode
E0cell=E0red(cathode)E0red(anode)
IfE0red(cathode)>E0red(anode)thentheelectronflowfromanodetocathodeisspontaneous
StandardReductionPotentials
Thecellpotentialofavoltaiccelldependsuponthetworedoxhalfreactionsthatcomprisethe
functioningcell
Therearemanydifferentcombinationsofredoxhalfreactions.Doweneedtotabulateall
possibleuniquecombinations?
Asyoumighthaveguessed,theanswerisno,wedon't.Inprinciple,wecouldassignaunique
standardpotentialtoeachhalfreactionandbycomparingthesevaluesdeterminethecell
potentialforanycombinationofhalfreactions
Thereisoneproblem,however:wehaveseenthatanisolatedhalfreactiondoesn'tresultinreduction
oroxidationorelectronflow.Therefore,howarewegoingtoassignastandardpotentialtoahalf
reaction?
Wearegoingtouseagenerallyagreeduponreductionreactionasthereferencehalfreaction
againstwhichtocompareandtabulateallpossiblehalfreactions
ThereferencereactionisthereductionofH+ (aq)ionstoproduceH2(g):
2H+ (aq,1M)+2eH2(g,1atm)E0red=0.0V
ThisisaStandardHydrogenElectrode(SHE)

HowdoweusethisSHEtodeterminethestandardreductionpotential,E0red,forsomeredoxhalf
reaction?

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Let'ssayweareinterestedindeterminingthestandardreductionpotentialforZn2+
WewouldsetupavoltaiccellusingaSHEasonehalfcell,andaZincelectrodeastheother
halfcell

Thehalfcellreactionsare:
Zn(s)Zn2+ (aq)+2e(Zincelectrode)
2H+ (aq)+2eH2(g)(SHE)
Theoverallcellreaction:
Zn(s)+2H+ (aq)Zn2+ (aq)+H2(g)
Note:thisisperformedunderStandardConditions,whereconcentrations=1.0M,andp=1
atm
Forthereactionasshown,thezincelectrodeistheanode(oxidation),andtheSHEisthe
cathode(reduction)
Thevoltagefortheoverallcellismeasuredat0.76Volts(i.e.thisisthestandardcell
potential)
Fromthepreviousdefinitionofthestandardcellpotential:
E0cell=E0red(cathode)E0red(anode)
Weknowthevalueforthestandardcellpotential,itis+0.76V.Wealsoknowthevalue
forthereductionpotentialfortheSHE,itis0V.Thus,
0.76V=E0red(cathode)E0red(anode)

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0.76V=0E0red(anode)
E0red(anode)=0.76V
Inotherwords,inreferencetotheSHE,thestandardreductionpotentialforthezincelectrodeis
determinedtobe0.76V.
Thismayseemalittlestrangebecausethecellreads+0.76Vandyetthedeterminedreduction
potentialforthezincelectrodeis0.76V.
Thekeyhereisthattheoriginaldefinitionofthestandardcellpotentialissetupsuchthateach
cellisreferencedasareductionreaction.
Inotherwordswhatwehaveactuallydeterminedisthehalfcellpotential(inreferencetothe
SHE)forthereductionofzinc:
Zn2+ (aq)+2eZn(s)E0red=0.76V
Wheneverweassignapotentialtoahalfreactionusingtheequationforthestandardcellpotential,it
isalwaysdoneinreferencetoareductionreaction
Thus,inreferencetotheSHE,theoxidationofZn(s)isassociatedwithahalfcellpotentialof
+0.76V(thisisthespontaneousdirectionforthereactionthereductionofZn2+ andthe
oxidationofH2(g)isnotspontaneous)
Thestandardcellpotential(Voltage)describesthepotentialperunitchargethatthereactionproduces
Thisvalueofthepotentialperunitcharge(i.e.electron)isaconstantthatisapropertyofthe
twohalfreactionsthatarereactinginthecell.Itisindependentofthestoichiometryoramount
ofthereactantsinthecell
Somestandardreductionpotentialsat25C:

StandardPotential,
(E0red)inVolts

ReductionHalfReaction

0.80

Ag+ (aq)+eAg(s)

0.34

Cu2+ (aq)+2eCu(s)

2H+ (aq)+2eH2(g)

0.76

Zn2+ (aq)+2eZn(s)

3.05

Li+ (aq)+eLi(s)

ThemorepositivethevalueofE0redthegreaterthedrivingforceforreduction
InreferencetoH+ /H2(g),Ag+ willpreferentiallybereducedtoAg(s)andH2(g)willbe
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oxidizedtoH+(aq).InreferencetoH+ /H2(g),Zn(s)willpreferentiallybeoxidizedandH+will
bereducedtoH2(g).
Thecathodeistheelectrodewherereductionoccurs,therefore,inorderforacelltooperate
spontaneously,thehalfreactionatthecathodemusthaveamorepositivevalueofE0redthan
thehalfreactionattheanode
Thegreaterdrivingforceforreductionatthecathodecanforcethereactionattheanode
tooperate"inreverse"i.e.toundergotheoxidationreaction
Thedifferencebetweenthestandardreductionpotentialsofthetworeactions,E0red
(cathode)E0red(anode),istheexcesspotentialthatcanbeusedtodriveelectrons
throughthecell,E0cell

Asilverlithiumbatteryisavoltaiccellwithasilvercathodeandalithiumanode.Whatisthevoltage
ofthisvoltaiccell?
E0cell=E0red(cathode)E0red(anode)
E0cell=0.8V(3.05V)=3.85Volts
WhatwillhappenifascienceprojectonbatteriessuggeststhatacathodebemadeoutofZincandthe
anodeofCopper?
E0cell=E0red(cathode)E0red(anode)
E0cell=0.76V(0.34V)=1.10Volts
Thebatterywillrun"backwards".Inotherwords,thegreaterreductionpotentialofCopperwill
actuallydriveoxidationoftheZinc.Ifavoltmeterisconnectedtothecellwiththeassumptionthat
theZincisthecathode,thenthevoltagewillreadnegative1.10volts
OxidizingandReducingAgents
Intheabovediscussionofreductionpotentialsandtheirrelationshiptooneanotherinhalfreactions,
wecanpredictwhichdirectioncurrentwillflowinavoltaiccell.Inotherwords,wecanpredictwhich
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reactantwillbeoxidizedandwhichwillbereduced
Thesameinformationcanbeusedforredoxreactionswherethecompoundsareindirect
contact,andnotseparatedintohalfcells.
Forexample,fromtheexampleabove,wewouldpredictthatsilverionwilloxidizelithium
metalasaspontaneousredoxreaction.Alternatively,wewouldpredictthatthereductionof
lithiumionbysilvermetalisnotaspontaneousreaction(andwouldrequiretheinputofenergy
todrive)
ThemorepositivetheE0redvalueofahalfreaction,thegreaterthetendencyofthecompoundtobe
reducedandthereforetooxidizeanothercompound(i.e.thegreaterthetendencytoactasan
oxidizingagent)
Substancesthatarestrongoxidizingagentsaresubsequentlyweakreducingagents.Likewise,
substancesthatarestrongreducingagentsareweakoxidizingagents.
2000Dr.MichaelBlaber

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