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ChemWiki:TheDynamicChemistryHypertext>AnalyticalChemistry>AnalyticalChemistry2.0>11:ElectrochemicalMethods>11A:Overview
ofElectrochemistry
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.
formsarethepredominatespeciesthereducedformsarethepredominatespeciesintheareasshowninpink.Notethatamorepositivepotential
favorstheoxidizedforms.Atapotentialof+0.500V(greenarrow)Fe3+ reducestoFe2+ ,butSn4+ remainsunchanged.
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.
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.
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.
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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