GalvanicCells

Redox reactionsinvolvethetransferofelectronsfromonereactantto another.Anelectriccurrentisaflowofelectronsinacircuit. Thesetwoconceptsformthebasisofelectrochemistry,whichisthe studyoftheprocessesinvolvedinconvertingchemicalenergyto electricalenergy,andinconvertingelectricalenergytochemical l l d l l h l energy. F FromREDOX,weknowthatazincstripreactswithasolution REDOX k th t i ti t ith l ti containingcopper(II)ions,formingzincionsandmetalliccopper.The reactionisspontaneous.Itreleasesenergyintheformofheat,i.e.it reaction is spontaneous. It releases energy in the form of heat, i.e. it isexothermic: Zn(s)+Cu2+(aq)Zn2+(aq)+Cu(s) Thereactionoccursonthesurfaceofthezincstrip,whereelectrons p, aretransferredfromzincatomstocopper(II)ionswhentheseatoms andionsareindirectcontact.Acommontechnologicalinvention, calledagalvaniccell,usesredox reactions,suchastheonedescribed above,toreleaseenergyintheformofelectricity.

TheGalvanicCell The Galvanic Cell

A l i Agalvaniccell,alsocalledavoltaiccell,isa ll l ll d lt i ll i devicethatconvertschemicalenergytoelectrical energy. energy Thekeytothisinventionistopreventthe reactantsinaredox reactionfromcominginto reactants in a redox reaction from coming into directcontactwitheachother.Instead,electrons flowfromonereactanttotheotherthroughan externalcircuit,whichisacircuitoutsidethe reactionvessel. Thisflowofelectronsthroughtheexternalcircuit h fl f l h h h l isanelectriccurrent.

Example:TheDaniell Cell
Onehalfofthecellconsistsofapieceofzincplacedinazinc sulfate solution The other half of the cell consists of a piece of solution.Theotherhalfofthecellconsistsofapieceof copperplacedinacopper(II)sulfate solution. Aporousbarrier,sometimescalledasemipermeablemembrane, separatesthesetwohalfcells.Itstopsthecopper(II)ionsfrom h h lf ll I h (II) i f comingintodirectcontactwiththezincelectrode. In a Daniell cell, the pieces of metallic zinc and copper act as InaDaniell cell,thepiecesofmetalliczincandcopperactas electricalconductors.Theconductorsthatcarryelectronsintoand outofacellarenamedelectrodes. Th i Thezincsulfate andcopper(II)sulfate actaselectrolytes. lf t d (II) lf t t l t l t Electrolytesaresubstancesthatconductelectricitywhendissolved inwater. *NOTE Thefactthatasolutionofanelectrolyteconductselectricitydoes notmeanthatfreeelectronstravelthroughthesolution.An not mean that free electrons travel through the solution An electrolytesolutionconductselectricitybecauseof ion movements,andthelossandgainofelectronsattheelectrodes.

 Theredox reactiontakesplaceinagalvaniccellwhenanexternal circuit,suchasametalwire,connectstheelectrodes.The , , oxidationhalfreactionoccursinonehalfcell,andthereduction halfreactionoccursintheotherhalfcell.FortheDaniell cell: Oxidation(lossofelectrons):Zn(s)Zn (aq)+2e Oxidation (loss of electrons): Zn(s) Zn2+(aq) + 2e Reduction(gainofelectrons):Cu2+(aq)+2eCu(s) The electrode at which oxidation occurs is named the anode. In Theelectrodeatwhichoxidationoccursisnamedtheanode.In thisexample,zincatomsundergooxidationatthezincelectrode. Thus,thezincelectrodeistheanodeoftheDaniell cell. Th l t d t hi h d ti Theelectrodeatwhichreductionoccursisnamedthecathode. i d th th d Here,copper(II)ionsundergoreductionatthecopperelectrode. Thus,thecopperelectrodeisthecathodeoftheDaniell cell. Freeelectronscannottravelthroughthesolution.Instead,the externalcircuitconductselectronsfromtheanodetothecathode ofagalvaniccell. of a galvanic cell
Hello, I am a RED CAT (REDUCTION at th t the CATHODE)

 Attheanodeofagalvaniccell,electronsarereleased g , byoxidation.Forexample,atthezincanodeofthe Daniell cell, zinc atoms release electrons to become cell,zincatomsreleaseelectronstobecome positivezincions.Thus,theanodeofagalvaniccellis negativelycharged.Relativetotheanode,thecathode negatively charged Relative to the anode the cathode ofagalvaniccellispositivelycharged.Ingalvaniccells, electronsflowthroughtheexternalcircuitfromthe electrons flow through the external circuit from the negativeelectrodetothepositiveelectrode.

Eachhalfcellcontainsasolutionofaneutralcompound.InaDaniell cell,these solutionsareaqueouszincsulfate andaqueouscopper(II)sulfate.Howcanthese solutions are aqueous zinc sulfate and aqueous copper(II) sulfate How can these electrolytesolutionsremainneutralwhenelectronsareleavingtheanodeofone halfcellandarrivingatthecathodeoftheotherhalfcell? Tomaintainelectricalneutralityineachhalf cell,someionsmigratethroughthe To maintain electrical neutrality in each halfcell, some ions migrate through the porousbarrier.Negativeions(anions)migratetowardtheanode,andpositiveions (cations)migratetowardthecathode.

Theseparatorbetweenthehalfcellsdoesnotneedtobeaporousbarrier.An Th t b t th h lf ll d t dt b b i A alternativedevice,calledasaltbridge,containsanelectrolytesolutionthatdoes notinterfereinthereaction.Theopenendsofthesaltbridgearepluggedwitha porousmaterial,suchasglasswool,tostoptheelectrolytefromleakingout porous material, such as glass wool, to stop the electrolyte from leaking out quickly.Theplugsallowionmigrationtomaintainelectricalneutrality.

SupposethesaltbridgeofaDaniell cellcontainsammoniumchloridesolution, Suppose the salt bridge of a Daniell cell contains ammonium chloride solution NH4Cl(aq).AspositiveZnionsareproducedattheanode,negativeCl ionsmigrate fromthesaltbridgeintothehalfcellthatcontainstheanode.AspositiveCu(II) ionsareremovedfromsolutionatthecathode,positiveammoniumionsmigrate i df l ti t th th d iti i i i t fromthesaltbridgeintothehalfcellthatcontainsthecathode.Otherelectrolytes, suchassodiumsulfate orpotassiumnitrate,couldbechosenforthesaltbridge. Neitheroftheseelectrolytesinterferesinthecellreaction. Silvernitratewouldbeapoorchoiceforthesaltbridge,however.Positivesilver ionswouldmigrateintothehalfcellthatcontainsthecathode.Zincdisplacesboth g p copperandsilverfromsolution,sobothcopper(II)ionsandsilverionswouldbe reducedatthecathode.Thecopperproducedwouldbecontaminatedwithsilver.

GalvanicCellNotation Aconvenientshorthandmethodexistsforrepresenting A convenient shorthand method exists for representing galvaniccells.TheshorthandrepresentationofaDaniell cellis asfollows: Zn|Zn2+||Cu2+|Cu Thephasesorstatesmaybeincluded. Zn(s)|Zn2+(aq)||Cu2+(aq)|Cu(s) Z ( )| Z 2 ( )|| C 2 ( ) | C ( ) Inadiagram,theanodemayappearontheleftoronthe right. right Intheshorthandrepresentation,however,theanodeis y f g alwaysshownontheleftandthecathodeontheright. Eachsingleverticalline,|,representsaphaseboundary betweentheelectrodeandthesolutioninahalfcell.For example,thefirstsingleverticallineshowsthatthesolidzinc l th fi t i l ti l li h th t th lid i andaqueouszincionsareindifferentphasesorstates.The , ||, p p doubleverticalline,||,representstheporousbarrierorsalt bridgebetweenthehalfcells.Spectatorionsareusually omitted.

InertElectrodes
ThezincanodeandcoppercathodeofaDaniell cellareboth h h f ll ll b h metals,andcanactaselectricalconductors.However,some redox reactions involve substances that cannot act as reactionsinvolvesubstancesthatcannotactas electrodes,suchasgasesordissolvedelectrolytes.Galvanic cellsthatinvolvesuchredox reactionsuseinertelectrodes. Aninertelectrodeisanelectrodemadefromamaterialthat p isneitherareactantnoraproductofthecellreaction.The figureshowsacellthatcontainsoneinertelectrode.The chemicalequation,netionicequation,andhalfreactionsfor thiscellaregivenbelow: hi ll i b l Chemicalequation:Pb(s)+2FeCl3(aq)2FeCl2(aq)+ PbCl2(aq) PbCl2( ) Netionicequation:Pb(s)+2Fe3+(aq)2Fe2+(aq)+Pb2+(aq) Oxidationhalfreaction:Pb(s)Pb2+(aq)+2e h lf b( ) b ( ) Reductionhalfreaction:Fe3+(aq)+eFe2+(aq)

 The reduction half reaction does not include a solid conductor of electrons Thereductionhalfreactiondoesnotincludeasolidconductorofelectrons, soaninertplatinumelectrodeisusedinthishalfcell.Theplatinum electrodeischemicallyunchanged,soitdoesnotappearinthechemical equationorhalf reactions.However,itisincludedintheshorthand equation or halfreactions However it is included in the shorthand representationofthecell. Pb |Pb2+||Fe3+,Fe2+|Pt A comma separates the form las Fe3+ and Fe2+ for the ions in ol ed in the AcommaseparatestheformulasFe3+andFe2+fortheionsinvolvedinthe reductionhalfreaction.Theformulasarenotseparatedbyaverticalline, becausethereisnophaseboundarybetweentheseions.TheFe3+and Fe2+ionsexistinthesameaqueoussolution. Fe2+ ions exist in the same aqueous solution

Homework

Homework