J.

Rusling

Spring,2014

Yourname____________________________________________________
CHEM5336ELECTROANALYTICALCHEMISTRY
Exam1,6March2014
(openbook&notes,nocomputers,iPADsorcellphones,thereare7pagesand6
questions)
1.20pts.Apotential(E)stepfrom0to0.7VvsSCEatastationary,planarHgfilm
electrodein0.1MNaNO3solution(pointofzerocharge{PZC}oftheelectrode
is0.3V)withoutanyelectroactivespeciespresentinthesolutionleadstoa
decayingcurrent(I)vs.time(t)response:
(a)(7pts)Whateventsoccurattheelectrodesolutioninterfacethatarethecausesof
thecurrentflowanddecay;
(b)(7pts)WriteanexpressionthatdescribestheIvstresponse,anddefineall
parameters.
(c)(6pts)Explainhowthedataobtainabovecouldbeusedtoobtainuseful
informationaboutthetimeconstantoftheelectrochemicalcell.
(a) chargingoftheelectrodedoublelayer(dl),theelectrodesurfacebecomes
negativeandwillattractNa+intothedoublelayer
(b)

Idl = (E /Rs )exp{t /Cd Rs}

Idlisthechargingcurrent,Eisthepotentialstep,Cdisdifferentialcapacitance,
andRsisthecell/solutionresistance

(c) Fitcurrentvs.ttogetunknownparametersRsandRsCd,thelatteristhetime
constant.Alternativeislinearizeto

ln Idl = ln(E /Rs ) t /Cd Rs

plotlnIdlvs.ttogetstraightlinewhereslopeis1/RsCd,

2.20pts.TheAg/AgCl(saturatedKCl)referenceelectrodehalfcellisusefulin
manyelectrochemicalexperiments,anditcanbesimplymadeinthelab.
(a)ExplainhowyoucouldmakeaAg/AgClhalfcellinthelaboratorythatcouldbe
usedasareferenceelectrodeforvoltammetry.Includealabeleddrawing.
(b)ShowhowtheNernstequationcanbeusedtoprovethatthepotentialofthis
referencehalfcellelectrodewillbeconstantatconstantTwhencontactingan
electrolytesolution.
(a) Ag/AgClwireinatubefilledwithSaturatedKClwithasaltbridgecontact
(ceramic,gel,etc)atthebottom

(b)AgCl+e=Ag+Cl
E = E 0 (RT / nF)ln{[Ag][Cl]/[AgCl]}
theconcentrationtermsareactivities,sothattheactivityofthesolidsisdefinedas
one.Then
E = E 0 (RT / nF)ln{[Cl]}
andthehalfcellpotentialdependsonlyon[Cl]

3. 20 pts The Butler-Volmer equation below is the classic kinetic relationship

between Faradaic current (I) in an electrochemical cell and the applied potential (E)
for the electrochemical electron-transfer reaction with O dissolved in solution:
kf
O + neR
kb

Inet = nFAksho {Co (0,t)exp((E E o ')F /RT) Cr (0,t)exp((1 )(E E o ')F /RT)}

a. (8 pts) Define all terms in the Butler-Volmer equation, and indicate if they are
constants. If they are not constants briefly mention how they can be measured in an
o
electrochemical experiment. How is k sh
related to kf and kb?
n = no. of electrons in reaction
F = Faradays constant, A = electrode area
ksho =standardheterogenousrateconstantdeterminedfromshapeofRDVcurves;

orTafelplots
C(0,t) terms are concentrations of O or R at the electrode surface cannot be
electrochemically determined, but can be calculated from theory, can be measured
spectroscopically
electrochemical transfer coefficient, estimated from shape of steady state
voltammetry, or TAfel plots
E = electrode potential (applied)
Eo = formal potential; R = gas constant; T = absolute temp.
Blue terms are constant
b. (6 pts) What is the working definition of the parameter kosh (often called ko) and
what does is mean in terms of reversibility in most steady state voltammetry
experiments when kosh>1 cm/s and when kosh<10-5 cm/s.
rate constant at the Eo for the reaction

kosh>1 cm/s reversible reaction

kosh<10-5 cm/s, irreversible reaction
c. (6 pts) Draw the shape of the predicted Butler-Volmer current Inet from a value of E
= Eo (0 V) to about -2.0 V. What are the limitations of this prediction for describing
an experiment like steady state voltammetry? How does the predicted Inet compare
with experimental steady state I vs. E observations

exponential increase in I vs E, does not happen experimentally, SSV gives a limiting

current

4.20pts.Masstransportandelectrodekinetics.Observetheshapesofthe
followinglinearsweepvoltammogramsdoneinstirredandquietsolutions,
respectively.Assumethatelectrontransferoccursatamoderaterate.

steadystatevoltammetry(stirring)scaninquietsolution
A.(10Pts)First,describethefundamentalreasonwhythecurrentinstirred
solutionreachesaconstantlimitingcurrent,andwhyinthequietsolutionapeak
isfound.
Stirredcurrentbecomeslimitedbyconvectionwhichprovidesaconstant
supplyofreactanttothesolution
Quietsolutioncurrentislimitedbydiffusionwhichcreatesaregionof
depletedreactantneartheelectrodethatdecreasesinreactantconcentrationwith
time,decayfollowstheCottrelleqn.
B.(10pts)Nowidentifyseparatemajorfactorsthatinfluencethe(a)rising
portionsofbothcurves,and(b)limitingcurrentontheleft,and(c)thecurrent
decaybeyondthepeakontheright.
Risingportionsofthecurvearecontrolledbythermodynamics(Nernsteq)orby
electrodekinetics,dependingontherateofelectrontransfer

5.20pts.Masstransport:AnEstepexperimentfromE1toE2involvingasimple,
fast,reversibleO+e=Relectrontransferundergoingsemiinfinitelineardiffusion
attheworkingelectrodeforE2<<Eoindone.Initially,thereareonlyOandinert
electrolyteinsolution.Thecurrenttimecurveforthisexpressioncanbeobtainedby
solvingFickssecondLaw.
UseofLaplacetransformstosolvethisequationgavethefollowingexpressionfor
thedistancedependentconcentrationinLaplacespace
C(x,s) =

wherethex=distancefromtheelectrode,
A(s)isanconstantofintegration,sistheLaplaceparameter,Disdiffusion
coefficient,andtheC*isbulkconcentration.SinceE2<<EoassoonastheEstepis
applied,theconcentrationofOattheelectrodegoestozero.Thisdefinesaboundary
conditiononC(x,t)thatcanbeusedtofindA(s).UsethisapproachtofindA(s),
then
usetheFicksfirstlawexpressionrelatingfluxtocurrent
J o (o,t ) =

C*
+ A' (s)exp[(s / D)1/ 2 x]
s

dC
(o,t )
I
= D

nFA
dx x=0

todevelopanequationthatdescribestheIvs.tresponseinthischronoamperometric
experiment.Showandexplaineachstepinyourderivation.(Laplacetransformsare
onp.771ofBardandFaulkner)

6.Shortanswerquestions,1pointeach,nopartcredit
(a)Whyarethreeelectrodepotentiostatsusedinelectroanalyticalexperiments?
TocompensateforIR(ohmic)drop

(b)WhatisthekeyexperimentalfeaturethatmadetheinventionofDCpolarography
byJ.Heyrovskyhighlysignificantforitstime.
Droppingmercuryelectrodeproducedacleanelectrodesurfaceallowingquantitative
measurements

(c)WhatdoRudyMarcus(Marcustheory)andJ.Heyrovskyhaveincommon?
WonNobelPrize

(d)WhatismainprocessthatprovidesFaradaiccurrentinanelectrochemicalcell?
Electrontransfer

(e)InMarcustheory,theelectrontransferrateconstantdependsonthestandardfree
energyandwhatotherenergeticparameter?
Reorganizationenergy