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ReferenceelectrodeWikipedia,thefreeencyclopedia

Referenceelectrode
FromWikipedia,thefreeencyclopedia

Areferenceelectrodeisanelectrodewhichhasastableandwellknownelectrodepotential.Thehigh
stabilityoftheelectrodepotentialisusuallyreachedbyemployingaredoxsystemwithconstant(buffered
orsaturated)concentrationsofeachparticipantsoftheredoxreaction.[1]
Therearemanywaysreferenceelectrodesareused.Thesimplestiswhenthereferenceelectrodeisusedas
ahalfcelltobuildanelectrochemicalcell.Thisallowsthepotentialoftheotherhalfcelltobedetermined.
Anaccurateandpracticalmethodtomeasureanelectrode'spotentialinisolation(absoluteelectrode
potential)hasyettobedeveloped.

Contents
1Aqueousreferenceelectrodes
2Nonaqueousreferenceelectrodes
3Pseudoreferenceelectrodes
4Seealso
5Furtherreading
6References
7Externallinks

Aqueousreferenceelectrodes
Commonreferenceelectrodesandpotentialwithrespecttothestandardhydrogenelectrode:
Standardhydrogenelectrode(SHE)(E=0.000V)activityofH+=1
Normalhydrogenelectrode(NHE)(E0.000V)concentrationH+=1
Reversiblehydrogenelectrode(RHE)(E=0.000V0.0591*pH)
Saturatedcalomelelectrode(SCE)(E=+0.241Vsaturated)
Coppercopper(II)sulfateelectrode(CSE)(E=+0.314V)
Silverchlorideelectrode(E=+0.197Vsaturated)
pHelectrode(incaseofpHbufferedsolutions,seebuffersolution)
Palladiumhydrogenelectrode
Dynamichydrogenelectrode(DHE)
Mercurymercuroussulfateelectrode(E=+0.64Vinsat'dK2SO4,E=+0.68Vin0.5MH2SO4)
(MSE)
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StandardHydrogen
Electrode

CuCu(II)reference
electrode

AgAgClreference
electrode

Nonaqueousreferenceelectrodes
Whileitisconvenienttocomparebetweensolventstoqualitativelycomparesystemsitisnotquantitatively
meaningful.MuchaspKaarerelatedbetweensolvents,butnotthesame,soisthecasewithE.Whilethe
SHEmightseemtobeareasonablereferencefornonaqueousworkasitturnsouttheplatinumisrapidly
poisonedbymanysolventsincludingacetonitrilecausinguncontrolleddriftsinpotential.BoththeSCEand
saturatedAg/AgClareaqueouselectrodesbasedaroundsaturatedaqueoussolution.Whileforshortperiods
itmaybepossibletousesuchaqueouselectrodesasreferenceswithnonaqueoussolutionsthelongterm
resultsarenottrustworthy.Usingaqueouselectrodesintroducesundefined,variable,andunmeasurable
junctionpotentialstothecellintheformofaliquidliquidjunctionaswellasdifferentioniccomposition
betweenthereferencecompartmentandtherestofthecell.[2]Thebestargumentagainstusingaqueous
referenceelectrodeswithnonaqueoussystems,asmentionedearlier,isthatpotentialsmeasuredindifferent
solventsarenotdirectlycomparable.[3]
ThepotentialfortheFc0/+coupleissensitivetosolvent.[4]
Fc0/+couple,NBu4PF6at298K
solvent
MeCN

E
0.40

CH2Cl2 0.46
THF

0.56

DMF

0.45

acetone 0.48
AQuasiReferenceElectrode(QRE)avoidstheissuesmentionedabove.AQREwithferroceneorsimilar
internalstandard(cobaltocene)referencedbacktoferroceneisidealfornonaqueouswork.Sincetheearly
1960sferrocenehasbeengainingacceptanceasthestandardreferencefornonaqueousworkforanumber
ofreasons,andin1984,IUPACrecommendedferrocene(II/III)asastandardredoxcouple.[5]The
preparationoftheQREelectrodeissimple,allowingforafreshreferencetobepreparedwitheachsetof
experiments.SinceQREsaremadefresh,thereisalsonoconcernwithimproperstorageormaintenanceof
theelectrode.QREsarealsomoreaffordablethanotherreferenceelectrodes.
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Tomakeaquasireferenceelectrode(QRE):
1. InsertapieceofsilverwireintoconcentratedHClthenallowthewiretodryonalintfreecleaning
cloth.ThisformsaninsolublelayerofAgClonthesurfaceoftheelectrodeandgivesyouan
Ag/AgClwire.RepeatdippingeveryfewmonthsoriftheQREstartstodrift.
2. ObtainaVycorglassfrit(4mmdiameter)andglasstubingofsimilardiameter.AttachVycorglass
frittotheglasstubingwithheatshrinkTeflontubing.
3. RinsethenfillthecleanglasstubewithsupportingelectrolytesolutionandinsertAg/AgClwire.
4. Theferrocene(II/III)coupleshouldliearound400mVversusthisAg/AgClQREinanacetonitrile
solution.Thispotentialwillvaryingupto200mVwiththespecificundefinedconditions.Thus
addinganinternalstandardsuchasferroceneatsomepointduringtheexperimentisalways
necessary.

Pseudoreferenceelectrodes
Apseudoreferenceelectrodeisatermthatisnotwelldefinedandbordersonhavingmultiplemeanings
sincepseudoandquasiareoftenusedinterchangeably.Theyareaclassofelectrodesnamedpseudo
referenceelectrodesbecausetheydonotmaintainaconstantpotentialbutvarypredictablywithconditions.
Iftheconditionsareknown,thepotentialcanbecalculatedandtheelectrodecanbeusedasareference.
Mostelectrodesworkoveralimitedrangeofconditions,suchaspHortemperature,outsideofthisrange
theelectrodesbehaviorbecomesunpredictable.Theadvantageofapseudoreferenceelectrodeisthatthe
resultingvariationisfactoredintothesystemallowingresearcherstoaccuratelystudysystemsoverawide
rangeofconditions.
Yttriastabilizedzirconia(YSZ)membraneelectrodesweredevelopedwithavarietyofredoxcouples,e.g.,
Ni/NiO.TheirpotentialdependsonpH.WhenthepHvalueisknown,theseelectrodescanbeemployedas
areferencewithnotableapplicationsatelevatedtemperatures.[6]

Seealso
Cyclicvoltammetry
Workingelectrode
Auxiliaryelectrode
Tableofstandardelectrodepotentials

Furtherreading
Ives,DavidJ.G.GeorgeJ.Janz(1961).ReferenceElectrodes,TheoryandPractice(1sted.).
AcademicPress.
Zanello,P.(20031001).InorganicElectrochemistry:Theory,Practice,andApplication(1ed.).
RoyalSocietyofChemistry.ISBN0854046615.
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Bard,AllenJ.LarryR.Faulkner(20001218).ElectrochemicalMethods:Fundamentalsand
Applications(2ed.).Wiley.ISBN0471043729.

References
1. ^Bard,AllenJ.Faulkner,LarryR.(20001218).ElectrochemicalMethods:FundamentalsandApplications(2
ed.).Wiley.ISBN0471043729.
2. ^Pavlishchuk,VitalyV.AnthonyW.Addison(January2000)."Conversionconstantsforredoxpotentials
measuredversusdifferentreferenceelectrodesinacetonitrilesolutionsat25C"
(http://www.sciencedirect.com/science?_ob=ArticleURL&_udi=B6TG53YDGGKF
J&_user=10&_rdoc=1&_fmt=&_orig=search&_sort=d&view=c&_acct=C000050221&_version=1&_urlVersion=
0&_userid=10&md5=949c49796859c129c5fdfdfa8dc96704).InorganicaChimicaActa298(1):97102.
doi:10.1016/S00201693(99)004077(https://dx.doi.org/10.1016%2FS00201693%2899%29004077).Retrieved
20090417.
3. ^Geiger,WilliamE.(20071101)."OrganometallicElectrochemistry:Origins,Development,andFuture".
Organometallics26(24):57385765.doi:10.1021/om700558k(https://dx.doi.org/10.1021%2Fom700558k).
4. ^Connelly,N.G.,Geiger,W.E.,"ChemicalRedoxAgentsforOrganometallicChemistry",Chem.Rev.1996,
96,877.
5. ^Gritzner,G.J.Kuta(1984)."Recommendationsonreportingelectrodepotentialsinnonaqueoussolvents"
(http://iupac.org/publications/pac/56/4/0461/).PureAppl.Chem.56(4):461466.doi:10.1351/pac198456040461
(https://dx.doi.org/10.1351%2Fpac198456040461).Retrieved20090417.
6. ^R.W.Bosch,D.Feron,andJ.P.Celis,"ElectrochemistryinLightWaterReactors",CRCPress,2007.

Externallinks
carbongraphenenanofiberjunctionreferenceelectrode
(http://pubs.acs.org/doi/abs/10.1021/ac201072u)
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