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ChemWiki:TheDynamicChemistryHypertext>AnalyticalChemistry>AnalyticalChemistry2.0>11:ElectrochemicalMethods>11A:Overview
ofElectrochemistry

11A: Overview of Electrochemistry

Thefocusofthischapterisonanalyticaltechniquesthatuseameasurementofpotential,charge,orcurrenttodetermineananalytesconcentrationor
tocharacterizeananalyteschemicalreactivity.Collectivelywecallthisareaofanalyticalchemistryelectrochemistrybecauseitsoriginatedfrom
thestudyofthemovementofelectronsinanoxidationreductionreaction.
Despitethedifferenceininstrumentation,allelectrochemicaltechniquesshareseveralcommonfeatures.Beforeweconsiderindividualexamplesin
greater detail, lets take a moment to consider some of these similarities. As you work through the chapter, this overview will help you focus on
similaritiesbetweendifferentelectrochemicalmethodsofanalysis.Youwillfinditeasiertounderstandanewanalyticalmethodwhenyoucanseeits
relationshiptoothersimilarmethods.

11A.1 Five Important Concepts

Tounderstandelectrochemistryweneedtoappreciatefiveimportantandinterrelatedconcepts:
1. theelectrodespotentialdeterminestheanalytesformattheelectrodessurface
2. theconcentrationofanalyteattheelectrodessurfacemaynotbethesameasitsconcentrationinbulksolution
3. inadditiontoanoxidationreductionreaction,theanalytemayparticipateinotherreactions
4. currentisameasureoftherateoftheanalytesoxidationorreductionand
5. wecannotsimultaneouslycontrolcurrentandpotential.

The Electrodes Potential Determines the Analytes Form

InChapter6weintroducedtheladderdiagramasatoolforpredictinghowachangeinsolutionconditionsaffectsthepositionofanequilibrium
reaction.Foranoxidationreductionreaction,thepotentialdeterminesthereactionsposition.Figure11.1,forexample,showsaladderdiagramfor
theFe3+ /Fe2+ andtheSn4+ /Sn2+ equilibria.IfweplaceanelectrodeinasolutionofFe3+ andSn4+ andadjustitspotentialto+0.500V,Fe3+ reduces
toFe2+ ,butSn4+ remainsunchanged.
You may wish to review the earlier treatment of oxidationreduction reactions in Section 6D.4 and the development of ladder diagrams for
oxidationreductionreactionsinSection6F.3.

Figure11.1RedoxladderdiagramforFe3+ /Fe2+andforSn4+ /Sn2+ redoxcouples.Theareasinblueshowthepotentialrangewheretheoxidized

formsarethepredominatespeciesthereducedformsarethepredominatespeciesintheareasshowninpink.Notethatamorepositivepotential
favorstheoxidizedforms.Atapotentialof+0.500V(greenarrow)Fe3+ reducestoFe2+ ,butSn4+ remainsunchanged.

Interfacial Concentrations May Not Equal Bulk Concentrations

InChapter6weintroducedtheNernstequation,whichprovidesamathematicalrelationshipbetweentheelectrodespotentialandtheconcentrations
ofananalytesoxidizedandreducedformsinsolution.Forexample,theNernstequationforFe3+ andFe2+ is
E=Eo(RT/nF)log([Fe2+ ]/[Fe3+ ])=Eo(0.05916/1)log([Fe2+ ]/
[Fe3+ ]

11.1

whereEistheelectrodespotentialandEoisthestandardstatereductionpotentialforthereactionFe3+Fe2+ +e .Becauseitisthepotentialof
the electrode that determines the analytes form at the electrodes surface, the concentration terms in equation 11.1 are those at the electrode's
surface,nottheconcentrationsinbulksolution.
Thisdistinctionbetweensurfaceconcentrationsandbulkconcentrationsisimportant.SupposeweplaceanelectrodeinasolutionofFe3+ andfixits
potential at 1.00 V. From the ladder diagram in Figure 11.1, we know that Fe3+ is stable at this potential and, as shown in Figure 11.2a, the
concentration of Fe3+ remains the same at all distances from the electrodes surface. If we change the electrodes potential to +0.500 V, the
concentrationofFe3+ attheelectrodessurfacedecreasestoapproximatelyzero.AsshowninFigure11.2b,theconcentrationofFe3+ increasesaswe
move away from the electrodes surface until it equals the concentration of Fe3+ in bulk solution. The resulting concentration gradient causes
additionalFe3+fromthebulksolutiontodiffusetotheelectrodessurface.
WecallthesolutioncontainingthisconcentrationgradientinFe3+ thediffusionlayer.WewillhavemoretosayaboutthisinSection11D.2.

Figure11.2ConcentrationofFe3+ asafunctionofdistancefromtheelectrodessurfaceat(a)E=+1.00Vand(b)E=+0.500V.Theelectrodeis
showningrayandthesolutioninblue.

The Analyte May Participate in Other Reactions

Figure11.2showshowtheelectrodespotentialaffectstheconcentrationofFe3+ ,andhowtheconcentrationofFe3+ variesasafunctionofdistance
from the electrodes surface. The reduction of Fe3+ to Fe2+ , which is governed by equation 11.1, may not be the only reaction affecting the
concentrationofFe3+ inbulksolutionorattheelectrodessurface.TheadsorptionofFe3+ attheelectrodessurfaceortheformationofametal
ligandcomplexinbulksolution,suchasFe(OH)2+ ,alsoaffectstheconcentrationofFe3+ .

Current is a Measure of Rate

ThereductionofFe3+ toFe2+ consumesanelectron,whichisdrawnfromtheelectrode.Theoxidationofanotherspecies,perhapsthesolvent,ata
second electrode serves as the source of this electron. The flow of electrons between the electrodes provides a measurable current. Because the
reductionofFe3+ toFe2+ consumesoneelectron,theflowofelectronsbetweentheelectrodesinotherwords,thecurrentisameasureoftherate
of the reduction reaction. One important consequence of this observation is that the current is zero when the reaction Fe3+ Fe2+ + e is at
equilibrium.
Therateofthereaction
Fe3+ Fe2+ e
isthechangeintheconcentrationofFe3+ asafunctionoftime.

We Cannot Simultaneously Control Both Current and Potential

IfasolutionofFe3+ andFe2+ isatequilibrium,thecurrentiszeroandthepotentialisgivenbyequation11.1.Ifwechangethepotentialawayfrom
its equilibrium position, current flows as the system moves toward its new equilibrium position. Although the initial current is quite large, it

decreases over time reaching zero when the reaction reaches equilibrium. The current, therefore, changes in response to the applied potential.
Alternatively,wecanpassafixedcurrentthroughtheelectrochemicalcell,forcingthereductionofFe3+ toFe2+ .BecausetheconcentrationsofFe3+
andFe2+ areconstantlychanging,thepotential,asgivenbyequation11.1,alsochangesovertime.Inshort,ifwechoosetocontrolthepotential,then
wemustaccepttheresultingcurrent,andwemustaccepttheresultingpotentialifwechoosetocontrolthecurrent.

11A.2 Controlling and Measuring Current and Potential

Electrochemicalmeasurementsaremadeinanelectrochemicalcellconsistingoftwoormoreelectrodesandtheelectroniccircuitryforcontrolling
andmeasuringthecurrentandthepotential.Inthissectionweintroducethebasiccomponentsofelectrochemicalinstrumentation.
The simplest electrochemical cell uses two electrodes. The potential of one electrode is sensitive to the analytes concentration, and is called the
working electrode or the indicator electrode. The second electrode, which we call the counter electrode, completes the electrical circuit and
providesareferencepotentialagainstwhichwemeasuretheworkingelectrodespotential.Ideallythecounterelectrodespotentialremainsconstant
sothatwecanassigntotheworkingelectrodeanychangeintheoverallcellpotential.Ifthecounterelectrodespotentialisnotconstant,wereplace
itwithtwoelectrodes:areferenceelectrodewhosepotentialremainsconstantandanauxiliaryelectrodethatcompletestheelectricalcircuit.
Because we cannot simultaneously control the current and the potential, there are only three basic experimental designs: (1) we can measure the
potential when the current is zero, (2) we can measure the potential while controlling the current, and (3) we can measure the current while
controllingthepotential.EachoftheseexperimentaldesignsreliesonOhmslaw,whichstatesthatacurrent,i,passingthroughanelectricalcircuit
ofresistance,R,generatesapotential,E.
E=iR
Eachoftheseexperimentaldesignsusesadifferenttypeofinstrument.Tohelpusunderstandhowwecancontrolandmeasurecurrentandpotential,
we will describe these instruments as if the analyst is operating them manually. To do so the analyst observes a change in the current or the
potentialandmanuallyadjuststheinstrumentssettingstomaintainthedesiredexperimentalconditions.Itisimportanttounderstandthatmodern
electrochemicalinstrumentsprovideanautomated,electronicmeansforcontrollingandmeasuringcurrentandpotential,andthattheydosobyusing
verydifferentelectroniccircuitry.
Forfurtherinformationaboutelectrochemicalinstrumentation,seethischaptersadditionalresources.

Potentiometers
To measure the potential of an electrochemical cell under a condition of zero current we use a potentiometer. Figure 11.3 shows a schematic
diagram for a manual potentiometer, consisting of a power supply, an electrochemical cell with a working electrode and a counter electrode, an
ammeterformeasuringthecurrentpassingthroughtheelectrochemicalcell,anadjustable,slidewireresistor,andatapkeyforclosingthecircuit
throughtheelectrochemicalcell.UsingOhmslaw,thecurrentintheupperhalfofthecircuitis
iup=EPS/Rab
whereEPSisthepowersupplyspotential,andRabistheresistancebetweenpointsaandboftheslidewireresistor.Inasimilarmanner,thecurrent
inthelowerhalfofthecircuitis
ilow=Ecell/Rcb
whereEcellisthepotentialdifferencebetweentheworkingelectrodeandthecounterelectrode,andRcbistheresistancebetweenthepointscandb
oftheslidewireresistor.Wheniup=ilow=0,nocurrentflowsthroughtheammeterandthepotentialoftheelectrochemicalcellis

Ecell=(Rcb/Rab)EPS

11.2

TodetermineEcell we momentarily press the tap key and observe the current at the ammeter. If the current is not zero, we adjust the slide wire
resistorandremeasurethecurrent,continuingthisprocessuntilthecurrentiszero.Whenthecurrentiszero,weuseequation11.2tocalculateEcell.
Usingthetapkeytomomentarilyclosethecircuitcontainingtheelectrochemicalcell,minimizesthecurrentpassingthroughthecellandlimitsthe
changeinthecompositionoftheelectrochemicalcell.Forexample,passingacurrentof109Athroughtheelectrochemicalcellfor1schangesthe
concentrationsofspeciesinthecellbyapproximately1014moles.Modernpotentiometersuseoperationalamplifierstocreateahighimpedance
voltmetercapableofmeasuringthepotentialwhiledrawingacurrentoflessthan109A.

Figure11.3Schematicdiagramofamanualpotentiometer:CisthecounterelectrodeWistheworkingelectrodeSWisaslidewireresistorTisa
tapkeyandiisanammeterformeasuringcurrent.

Galvanostats
Agalvanostat allows us to control the current flowing through an electrochemical cell. A schematic diagram of a constantcurrent galvanostat is
showninFigure11.4.Thecurrentflowingfromthepowersupplythroughtheworkingelectrodeis
i=EPS/(R+Rcell)
whereEPSisthepotentialofthepowersupply,Ristheresistanceoftheresistor,andRcellistheresistanceoftheelectrochemicalcell.IfR>>Rcell,
thenthecurrentbetweentheauxiliaryandworkingelectrodesis
i=EPS/Rconstant
Tomonitorthepotentialoftheworkingelectrode,whichchangesasthecompositionoftheelectrochemicalcellchanges,wecanincludeanoptional
referenceelectrodeandahighimpedancepotentiometer.

Figure11.4Schematicdiagramofagalvanostat:AistheauxiliaryelectrodeWistheworkingelectrodeRisanoptionalreferenceelectrode,Eisa
highimpedancepotentiometer,andiisanammeter.Theworkingelectrodeandtheoptionalreferenceelectrodeareconnectedtoaground.

Potentiostats
Apotentiostatallowsustocontrolthepotentialoftheworkingelectrode.Figure11.5showsaschematicdiagramforamanualpotentiostat.The
potentialoftheworkingelectrodeismeasuredrelativetoaconstantpotentialreferenceelectrodethatisconnectedtotheworkingelectrodethrougha
highimpedance potentiometer. To set the working electrodes potential we adjust the slide wire resistor, which is connected to the auxiliary
electrode. If the working electrodes potential begins to drift, we can adjust the slide wire resistor to return the potential to its initial value. The

current flowing between the auxiliary electrode and the working electrode is measured with an ammeter. Modern potentiostats include waveform
generatorsthatallowustoapplyatimedependentpotentialprofile,suchasaseriesofpotentialpulses,totheworkingelectrode.

Figure11.5Schematicdiagramforamanualpotentiostat:WistheworkingelectrodeAistheauxiliaryelectrodeRisthereferenceelectrodeSW
isaslidewireresistor,Eisahighimpendancepotentiometerandiisanammeter.

11A.3 Interfacial Electrochemical Techniques

Becausethischapterfocusesoninterfacialelectrochemicaltechniques,letsclassifythemintoseveralcategories.Figure11.6providesoneversionof
a family tree highlighting the experimental conditions, the analytical signal, and the corresponding electrochemical techniques. Among the
experimentalconditionsunderourcontrolarethepotentialorthecurrent,andwhetherwestirtheanalytessolution.
At the first level, we divide interfacial electrochemical techniques into static techniques and dynamic techniques. In a static technique we do not
allow current to pass through the analytes solution. Potentiometry, in which we measure the potential of an electrochemical cell under static
conditions,isoneofthemostimportantquantitativeelectrochemicalmethods,andisdiscussedindetailinsection11B.
Dynamic techniques, in which we allow current to flow through the analytes solution, comprise the largest group of interfacial electrochemical
techniques.Coulometry,inwhichwemeasurecurrentasafunctionoftime,iscoveredinSection11C.Amperometryandvoltammetry,inwhichwe
measurecurrentasafunctionofafixedorvariablepotential,isthesubjectofSection11D.

Figure11.6Familytreehighlightinganumberofinterfacialelectrochemicaltechniques.Thespecifictechniquesareshowninred,theexperimental
conditionsareshowninblue,andtheanalyticalsignalsareshowningreen.

The material in this sectionparticularly the five important conceptsdraws upon a vision for understanding electrochemistry outlined by Larry
FaulknerinthearticleUnderstandingElectrochemistry:SomeDistinctiveConcepts,J.Chem.Educ.1983,60,262264.Seealso,Kissinger,P.T.
Bott,A.W.ElectrochemistryfortheNonElectrochemist,CurrentSeparations,2002,20:2,5153.
11BPotentiometricMethods

Contributors
DavidHarvey(DePauwUniversity)
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