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Galvaniccell
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Agalvaniccell,orvoltaiccell,namedafter
LuigiGalvani,orAlessandroVoltarespectively,
isanelectrochemicalcellthatderiveselectrical
energyfromspontaneousredoxreactionstaking
placewithinthecell.Itgenerallyconsistsoftwo
differentmetalsconnectedbyasaltbridge,or
individualhalfcellsseparatedbyaporous
membrane.

Voltawastheinventorofthevoltaicpile,the
firstelectricalbattery.Incommonusage,the
word"battery"hascometoincludeasingle
galvaniccell,butabatteryproperlyconsistsof
multiplecells.[1]

Contents
1 History
2 Description
3 Cellvoltage
4 Galvaniccorrosion
5 Celltypes
6 Seealso
7 References
8 Externallinks

History
In1780,LuigiGalvanidiscoveredthatwhentwodifferentmetals(e.g.,copperandzinc)areconnectedandthen
bothtouchedatthesametimetotwodifferentpartsofanerveofafrogleg,thenthelegcontracts.[2]Hecalledthis
"animalelectricity".Thevoltaicpile,inventedbyAlessandroVoltainthe1800s,consistsofapileofcellssimilar
tothegalvaniccell.However,VoltabuiltitentirelyoutofnonbiologicalmaterialinordertochallengeGalvani's
(andthelaterexperimenterLeopoldoNobili)animalelectricitytheoryinfavourofhisownmetalmetalcontact
electricitytheory.[3]CarloMatteucciinhisturnconstructedabatteryentirelyoutofbiologicalmaterialinanswer
toVolta.[4]ThesediscoveriespavedthewayforelectricalbatteriesVolta'scellwasnamedanIEEEMilestonein
1999.[5]

ItwassuggestedbyWilhelmKnigin1940thattheobjectknownastheBaghdadbatterymightrepresentgalvanic
celltechnologyfromancientParthia.Replicasfilledwithcitricacidorgrapejuicehavebeenshowntoproducea
voltage.However,itisfarfromcertainthatthiswasitspurposeotherscholarshavepointedoutthatitisvery
similartovesselsknowntohavebeenusedforstoringparchmentscrolls.[6]

Description
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Initssimplestform,ahalfcellconsistsofasolidmetal
(calledanelectrode)thatissubmergedinasolution
thesolutioncontainscationsoftheelectrodemetaland
anionstobalancethechargeofthecations.Inessence,
ahalfcellcontainsametalintwooxidationstates
insideanisolatedhalfcell,thereisanoxidation
reduction(redox)reactionthatisinchemical
equilibrium,aconditionwrittensymbolicallyas
follows(here,"M"representsametalcation,anatom
thathasachargeimbalanceduetothelossof"n"
electrons):

Mn+(oxidizedspecies)+neM(reduced
species)

Agalvaniccellconsistsoftwohalfcells,suchthatthe
electrodeofonehalfcelliscomposedofmetalA,and
theelectrodeoftheotherhalfcelliscomposedof
metalBtheredoxreactionsforthetwoseparatehalf
SchematicofZnCugalvaniccell
cellsarethus:

An++neA
Bm++meB

Ingeneral,then,thesetwometalscanreactwitheachother:

mA+nBm+nB+mAn+

Inotherwords,themetalatomsofonehalfcellareabletoinducereductionofthemetalcationsoftheotherhalf
cellconverselystated,themetalcationsofonehalfcellareabletooxidizethemetalatomsoftheotherhalfcell.
WhenmetalBhasagreaterelectronegativitythanmetalA,thenmetalBtendstostealelectronsfrommetalA(that
is,metalBtendstooxidizemetalA),thusfavoringonedirectionofthereaction:

mA+nBm+ nB+mAn+

Thisreactionbetweenthemetalscanbecontrolledinawaythatallowsfordoingusefulwork:

Theelectrodesareconnectedwithametalwireinordertoconducttheelectronsthatparticipateinthe
reaction.

Inonehalfcell,dissolvedmetalBcationscombinewiththefreeelectronsthatareavailableattheinterface
betweenthesolutionandthemetalBelectrodethesecationsaretherebyneutralized,causingthemto
precipitatefromsolutionasdepositsonthemetalBelectrode,aprocessknownasplating.
ThisreductionreactioncausesthefreeelectronsthroughoutthemetalBelectrode,thewire,andthemetalA
electrodetobepulledintothemetalBelectrode.Consequently,electronsarewrestledawayfromsomeof
theatomsofthemetalAelectrode,asthoughthemetalBcationswerereactingdirectlywiththemthose
metalAatomsbecomecationsthatdissolveintothesurroundingsolution.
Asthisreactioncontinues,thehalfcellwiththemetalAelectrodedevelopsapositivelychargedsolution
(becausethemetalAcationsdissolveintoit),whiletheotherhalfcelldevelopsanegativelycharged
solution(becausethemetalBcationsprecipitateoutofit,leavingbehindtheanions)unabated,this
imbalanceinchargewouldstopthereaction.

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Thesolutionsareconnectedbyasaltbridgeoraporousplateinordertoconducttheions(boththemetalA
cationsfromonesolution,andtheanionsfromtheothersolution),whichbalancesthechargesofthe
solutionsandtherebyallowsthereactionbetweenmetalAandmetalBtocontinuewithoutopposition.

Bydefinition:

Theanodeistheelectrodewhereoxidation(lossofelectrons)takesplaceinagalvaniccell,itisthe
negativeelectrode,aswhenoxidationoccurs,electronsareleftbehindontheelectrode.[7]Theseelectrons
thenmigratetothecathode(positiveelectrode).However,inelectrolysis,anelectriccurrentstimulates
electronflowintheoppositedirection.Thus,theanodeispositive,andthestatementanodeattractsanionsis
true(negativelychargedionsflowtotheanode,whileelectronsareexpelledthroughthewire).ThemetalA
electrodeistheanode.
Thecathodeistheelectrodewherereduction(gainofelectrons)takesplaceinagalvaniccell,itisthe
positiveelectrode,aslessoxidationoccurs,fewerionsgointosolution,andlesselectronsareleftonthe
electrode.[7]Instead,thereisagreatertendencyforaqueousionstobereducedbytheincomingelectrons
fromtheanode.However,inelectrolysis,thecathodeisthenegativeterminal,andattractingpositiveions
fromthesolution.Inthissituation,thestatementthecathodeattractscationsistrue(positivelycharged,
oxidizedmetalionsflowtowardcathodeaselectronstravelthroughthewire).ThemetalBelectrodeisthe
cathode.

CopperreadilyoxidizeszincfortheDaniellcelldepictedinthefigure,theanodeiszincandthecathodeiscopper,
andtheanionsinthesolutionsaresulfatesoftherespectivemetals.Whenanelectricallyconductingdevice
connectstheelectrodes,theelectrochemicalreactionis:
2+ 2+
Zn+Cu Zn +Cu

Thezincelectrodeisdissolvedandcopperisdepositedonthecopperelectrode.

Galvaniccellsaretypicallyusedasasourceofelectricalpower.Bytheirnature,theyproducedirectcurrent.The
Westoncellhasananodecomposedofcadmiummercuryamalgam,andacathodecomposedofpuremercury.The
electrolyteisa(saturated)solutionofcadmiumsulfate.Thedepolarizerisapasteofmercuroussulfate.Whenthe
electrolytesolutionissaturated,thevoltageofthecellisveryreproduciblehence,in1911,itwasadoptedasan
internationalstandardforvoltage.

Abatteryisasetofgalvaniccellsthatareconnectedtogethertoformasinglesourceofvoltage.Forinstance,a
typical12Vleadacidbatteryhassixgalvaniccellsconnectedininserieswiththeanodescomposedofleadand
cathodescomposedofleaddioxide.Largebatteryrooms,forinstanceinatelephoneexchangeprovidingcentral
officepowertouser'stelephones,mayhavecellsconnectedinbothseriesandparallel.

Cellvoltage
Thestandardelectricalpotentialofacellcanbedeterminedbytheuseofastandardpotentialtableforthetwohalf
cellsinvolved.Thefirststepistoidentifythetwometalsreactinginthecell.Thenonelooksupthestandard
electrodepotential,E0,involts,foreachofthetwohalfreactions.Thestandardpotentialforthecellisequaltothe
morepositiveE0valueminusthemorenegativeE0value.

Forexample,inthefigureabovethesolutionsareCuSO4andZnSO4.Eachsolutionhasacorrespondingmetal
stripinit,andasaltbridgeorporousdiskconnectingthetwosolutionsandallowingSO42ionstoflowfreely
betweenthecopperandzincsolutions.Inordertocalculatethestandardpotentialonelooksupcopperandzinc's
halfreactionsandfinds:

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Cu2++2e Cu:E0=+0.34V

Zn2++2e Zn:E0=0.76V

Thustheoverallreactionis:

Cu2++ZnCu+Zn2+

Thestandardpotentialforthereactionisthen+0.34V(0.76V)=1.10V.Thepolarityofthecellisdetermined
asfollows.Zincmetalismorestronglyreducingthancoppermetalequivalently,thestandard(reduction)potential
forzincismorenegativethanthatofcopper.Thus,zincmetalwillloseelectronstocopperionsanddevelopa
positiveelectricalcharge.Theequilibriumconstant,K,forthecellisgivenby

whereFistheFaradayconstant,RisthegasconstantandTisthetemperatureinkelvins.FortheDaniellcellKis
approximatelyequalto1.51037.Thus,atequilibrium,afewelectronsaretransferred,enoughtocausethe
electrodestobecharged.[8]

ActualhalfcellpotentialsmustbecalculatedbyusingtheNernstequationasthesolutesareunlikelytobeintheir
standardstates,

whereQisthereactionquotient.Thissimplifiesto

where{Mn+}istheactivityofthemetalioninsolution.Themetalelectrodeisinitsstandardstatesobydefinition
hasunitactivity.Inpracticeconcentrationisusedinplaceofactivity.Thepotentialofthewholecellisobtainedby
combiningthepotentialsforthetwohalfcells,soitdependsontheconcentrationsofbothdissolvedmetalions.

Thevalueof2.303R/Fis0.19845103V/K,soat25C(298.15K)thehalfcellpotentialwillchangeby
iftheconcentrationofametalionisincreasedordecreasedbyafactorof10.

Thesecalculationsarebasedontheassumptionthatallchemicalreactionsareinequilibrium.Whenacurrent
flowsinthecircuit,equilibriumconditionsarenotachievedandthecellpotentialwillusuallybereducedby
variousmechanisms,suchasthedevelopmentofoverpotentials.[9]Also,sincechemicalreactionsoccurwhenthe
cellisproducingpower,theelectrolyteconcentrationschangeandthecellvoltageisreduced.Aconsequenceof
thetemperaturedependencyofstandardpotentialsisthatthevoltageproducedbyagalvaniccellisalso
temperaturedependent.

Galvaniccorrosion

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Galvaniccorrosionisaprocessthatdegradesmetalselectrochemically.Thiscorrosionoccurswhentwodissimilar
metalsarelocatedincontactwitheachotherinthepresenceofanelectrolyte,suchassaltwater,forminga
galvaniccell.Acellcanalsobeformedifthesamemetalisexposedtotwodifferentconcentrationsofelectrolyte.
Theresultingelectrochemicalpotentialthendevelopsanelectriccurrentthatelectrolyticallydissolvestheless
noblematerial.

Celltypes
Concentrationcell
Electrolyticcell
Electrochemicalcell
Lemonbattery
Thermogalvaniccell

Seealso
Bioelectrochemicalreactor Electrohydrogenesis
Biologicalcellvoltage Electrosynthesis
Bionanogenerator Enzymaticbiofuelcell
Cellnotation Galvanicseries
Desulfation Isotopeelectrochemistry
Electrochemicalengineering Sacrificialanode
Electrodepotential
Electrohydrogenesis
References
1."battery"(def.4b)(http://www.merriamwebster.com/dictionary/battery),MerriamWebsterOnlineDictionary(2008).
Retrieved6August2008.
2.Keithley,JosephF(1999).DaniellCell.JohnWileyandSons.pp.4951.ISBN0780311930.
3.Kipnis,Nahum(2003)"Changingatheory:thecaseofVolta'scontactelectricity"(http://ppp.unipv.it/Collana/Pages/Libri/
Saggi/Nuova%20Voltiana5_PDF/p__143162.pdf),NuovaVoltiana,Vol.5.UniversitdeglistudidiPavia,2003ISBN
8820332736.pp.144146
4.Clarke,EdwinJacyna,L.S.(1992)NineteenthCenturyOriginsofNeuroscientificConcepts(https://books.google.com/b
ooks?id=38SjkpJlPcC&pg=PA198),UniversityofCaliforniaPress.ISBN0520078799.p.199
5."Milestones:Volta'sElectricalBatteryInvention,1799".IEEEGlobalHistoryNetwork.IEEE.Retrieved26July2011.
6.Haughton,Brian(2007)HiddenHistory:LostCivilizations,SecretKnowledge,andAncientMysteries.CareerPress.
ISBN1564148971.pp.129132
7."Anintroductiontoredoxequilibria".Chemguide.Retrieved20July2014.
8.Atkins,PdePaula(2006).PhysicalChemistry.J.(8th.ed.).OxfordUniversityPress.ISBN9780198700722.
Chapter7,sectionson"Equilibriumelectrochemistry"
9.Atkins,PdePaula(2006).PhysicalChemistry.J.(8th.ed.).OxfordUniversityPress.ISBN9780198700722.
Section25.12"WorkingGalvaniccells"

Externallinks
Howtobuildagalvaniccellbattery(http://www.miniscience.com/link/Airbattery.htm)from
MiniScience.com
GalvanicCell(http://www.mhhe.com/physsci/chemistry/essentialchemistry/flash/galvan5.swf),ananimation
InteractiveanimationofGalvanicCell(http://www.chem.iastate.edu/group/Greenbowe/sections/projectfolde
r/flashfiles/electroChem/voltaicCell20.html).ChemicalEducationResearchGroup,IowaStateUniversity.

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Categories: Galvaniccells Corrosion

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