DepartmentofChemicalEngineeringandBiotechnology

LinearSweepandCyclicVoltametry:ThePrinciples
Inthissectiontwocloselyrelatedformsofvoltammetryareintroduced
LinearSweepVoltammetry
CyclicVoltammetry
Weshallseehowthesemeasurementscanbeemployedtostudytheelectrontransferkineticsand
transportpropertiesofelectrolysisreactions.

LinearSweepVoltammetry
Inlinearsweepvoltammetry(LSV)afixedpotentialrangeisemployedmuchlikepotentialstep
measurements.HoweverinLSVthevoltageisscannedfromalowerlimittoanupperlimitasshown
below.

Thevoltagescanrate(v)iscalculatedfromtheslopeoftheline.Clearlybychangingthetimetakento
sweeptherangewealterthescanrate.Thecharacteristicsofthelinearsweepvoltammogramrecorded
dependonanumberoffactorsincluding:
Therateoftheelectrontransferreaction(s)
Thechemicalreactivityoftheelectroactivespecies
Thevoltagescanrate
InLSVmeasurementsthecurrentresponseisplottedasafunctionofvoltageratherthantime,unlike
potentialstepmeasurements.ForexampleifwereturntotheFe3+/Fe2+system

thenthefollowingvoltammogramwouldbeseenforasinglevoltagescanusinganelectrolytesolution
containingonlyFe3+resultingfromavoltagesweep

Thescanbeginsfromthelefthandsideofthecurrent/voltageplotwherenocurrentflows.Asthe
voltageissweptfurthertotheright(tomorereductivevalues)acurrentbeginstoflowandeventually
reachesapeakbeforedropping.Torationalisethisbehaviourweneedtoconsidertheinfluenceof
voltageontheequilibriumestablishedattheelectrodesurface.Ifweconsidertheelectrochemical
reductionofFe3+toFe2+,therateofelectrontransferisfastincomparsiontothevoltagesweeprate.
Thereforeattheelectrodesurfaceanequilibrumisestablishedidenticaltothatpredictedby
thermodynamics.YoumayrecallfromequilibriumelectrochemistrythattheNernstequation:

predictstherelationshipbetweenconcentrationandvoltage(potentialdifference),whereEistheapplied
potentialdifferenceandEoisthestandardelectrodepotential.SoasthevoltageissweptfromV1toV2
theequilibriumpositionshiftsfromnoconversionatV1tofullconversionatV2ofthereactantatthe
electrodesurface.Theexactformofthevoltammogramcanberationalisedbyconsideringthevoltage
andmasstransporteffects.AsthevoltageisinitiallysweptfromV1theequilibriumatthesurfacebegins
toalterandthecurrentbeginstoflow:

Thecurrentrisesasthevoltageissweptfurtherfromitsinitialvalueastheequilibriumpositionisshifted
furthertotherighthandside,thusconvertingmorereactant.Thepeakoccurs,sinceatsomepointthe
diffusionlayerhasgrownsufficientlyabovetheelectrodesothatthefluxofreactanttotheelectrodeis
notfastenoughtosatisfythatrequiredbytheNernstequation.Inthissituationthecurentbeginstodrop
justasitdidinthepotentialstepmeasurements.Infactthedropincurrentfollowsthesamebehaviour
asthatpredictedbytheCottrellequation.

Theabovevoltammogramwasrecordedatasinglescanrate.Ifthescanrateisalteredthecurrent
responsealsochanges.Thefigurebelowshowsaseriesoflinearsweepvoltammogramsrecordedat
differentscanratesforanelectrolytesolutioncontainingonlyFe3+

Eachcurvehasthesameformbutitisapparentthatthetotalcurrentincreaseswithincreasingscan
rate.Thisagaincanberationalisedbyconsideringthesizeofthediffusionlayerandthetimetakento
recordthescan.Clearlythelinearsweepvoltammogramwilltakelongertorecordasthescanrateis
decreased.Thereforethesizeofthediffusionlayerabovetheelectrodesurfacewillbedifferent
dependinguponthevoltagescanrateused.Inaslowvoltagescanthediffusionlayerwillgrowmuch
furtherfromtheelectrodeincomparisontoafastscan.Consequentlythefluxtotheelectrodesurfaceis
considerablysmalleratslowscanratesthanitisatfasterrates.Asthecurrentisproportionaltotheflux
towardstheelectrodethemagnitudeofthecurrentwillbeloweratslowscanratesandhigherathigh
rates.ThishighlightsanimportantpointwhenexaminingLSV(andcyclicvoltammograms),although
thereisnotimeaxisonthegraphthevoltagescanrate(andthereforethetimetakentorecordthe
voltammogram)dostronglyeffectthebehaviourseen.Afinalpointtonotefromthefigureistheposition
ofthecurrentmaximum,itisclearthatthepeakoccursatthesamevoltageandthisisacharacteristicof
electrodereactionswhichhaverapidelectrontransferkinetics.Theserapidprocessesareoftenreferred
toasreversibleelectrontransferreactions.
Thisleavesthequestionastowhatwouldhappeniftheelectrontransferprocesseswere'slow'(relative
tothevoltagescanrate).Forthesecasesthereactionsarereferredtoasquasireversibleorirreversible
electrontransferreactions.Thefigurebelowshowsaseriesofvoltammogramsrecordedatasingle
voltagesweepratefordifferentvaluesofthereductionrateconstant(kred)

Inthissituationthevoltageappliedwillnotresultinthegenerationoftheconcentrationsattheelectrode
surfacepredictedbytheNernstequation.Thishappensbecausethekineticsofthereactionare'slow'
andthustheequilibriaarenotestablishedrapidly(incomparisontothevoltagescanrate).Inthis
situationtheoverallformofthevoltammogramrecordedissimilartothatabove,butunlikethereversible
reactionnowthepositionofthecurrentmaximumshiftsdependinguponthereductionrateconstant
(andalsothevoltagescanrate).Thisoccursbecausethecurrenttakesmoretimetorespondtothethe
appliedvoltagethanthereversiblecase.

CyclicVoltammetry
Cyclicvoltammetry(CV)isverysimilartoLSV.Inthiscasethevoltageissweptbetweentwovalues
(seebelow)atafixedrate,howevernowwhenthevoltagereachesV2thescanisreversedandthe
voltageissweptbacktoV1

Atypicalcyclicvoltammogramrecordedforareversiblesingleelectrodetransferreactionisshownin
below.Againthesolutioncontainsonlyasingleelectrochemicalreactant

TheforwardsweepproducesanidenticalrepsonsetothatseenfortheLSVexperiment.Whenthescan
isreversedwesimplymovebackthroughtheequilibriumpositionsgraduallyconvertingelectrolysis
product(Fe2+backtoreactant(Fe3+).Thecurrentflowisnowfromthesolutionspeciesbacktothe

electrodeandsooccursintheoppositesensetotheforwardseepbutotherwisethebehaviourcanbe
explainedinanidenticalmanner.ForareversibleelectrochemicalreactiontheCVrecordedhascertain
welldefinedcharacteristics.
I)Thevoltageseparationbetweenthecurrentpeaksis

II)Thepositionsofpeakvoltagedonotalterasafunctionofvoltagescanrate

III)Theratioofthepeakcurrentsisequaltoone

IV)Thepeakcurrentsareproportionaltothesquarerootofthescanrate

AswithLSVtheinfluenceofscanrateisexplainedforareversibleelectrontransferreactionintermsof
thediffusionlayerthickness.
TheCVforcaseswheretheelectrontransferisnotreversibleshowconsiderablydifferentbehaviour
fromtheirreversiblecounterparts.Thefigurebelowshowsthevoltammogramforaquasireversible
reactionfordifferentvaluesofthereductionandoxidationrateconstants.

Thefirstcurveshowsthecasewhereboththeoxidationandreductionrateconstantsarestillfast,
however,astherateconstantsareloweredthecurvesshifttomorereductivepotentials.Againthismay
berationalisedintermsoftheequilibriumatthesurfaceisnolongerestablishingsorapidly.Inthese
casesthepeakseparationisnolongerfixedbutvariesasafunctionofthescanrate.Similarlythepeak
currentnolongervariesasafunctionofthesquarerootofthescanrate.
Byanalysingthevariationofpeakpositionasafunctionofscanrateitispossibletogainanestimatefor
theelectrontransferrateconstants.