J.

Rusling

Spring,2012

Yourname____________________________________________________
CHEM5336ELECTROANALYTICALCHEMISTRY
Exam1,6March2014
(openbook&notes,nocomputersorcellphones,thereare7pagesand6
questions)
1.20pts.Apotential(E)stepfrom0to0.5VvsSCEatastationaryHgdrop
electrodein0.1MNaNO3solution(pointofzerocharge{PZC}oftheelectrode
is0.3V)withoutanyelectroactivespeciespresentinthesolutionleadstoa
decayingcurrent(I)vs.time(t)response:
(a)(7pts)Whateventsoccurattheelectrodesolutionthatarethecausesofthe
currentflowanddecay;
(b)(7pts)WriteanexpressionthatdescribestheIvstresponse,defineall
parameters.
(c)(6pts)Explainhowthedataobtainabovecouldbeusedtoobtainuseful
informationaboutthetimeconstantoftheelectrochemicalcell.

2.20pts.TheAg/AgCl(3MKCl)referenceelectrodecellisusefulinmany
electrochemicalexperiments.
(a)DrawandclearlylabelaconfigurationofanAg/AgClhalfcellrefernceelectrode
(b)ShowhowtheNernstequationcanbeusedtoprovethatthepotentialofthis
referencehalfcellelectrodewillbeconstantatconstanttemperature

3. 20 pts Butler-Volmer equation 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
a. Write the Butler-volmer equation for I vs. E curves and define all terms in the
equation
b. 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.
c. What are the limitation of the Butler Volmer equation in anaysis of real
electrochemical experiments.

4.20pts.Reversibilityofanelectrodereactionisafundamentalconceptin
electroanalyticalchemistry.For
kf
O+ne
R
kb
(a)(7pt)Explainbrieflywhatreversibilitymeans.Thenwriteanequation(and
defineallvariables)thatdescribestheIvsEbehaviorofthereversiblereaction
aboveforanysteadystatevoltammetrymethod.
(b)(6pts)Describehowtousesteadystatevoltammetryandaccompanyingdata
analysistodistinguishbetweenareversibleandirreversibleelectrochemicalreaction.
(c)(7pt)forthereversiblereaction;
O+xH++e
R
Describesteadystatevoltammetryexperimentsandanalysisoftheresultingdatathat
willprovidethenumber(x)ofprotonsinvolvedinthereaction.

5.20pts.Masstransport:Thegraphbelowrepresentsaconcentrationprofile(Cbis
bulkconcentration;isNernstDiffusionlayerthickness;xisdistancefromthe
electrode).ForaEstepexperimentfromE1toE2involvingasimple,fast,reversible
O+e=RelectrontransferattheworkingelectrodeforE2<<<Eostartingwithonly
Oandinertelectrolyteinsolution,startwiththeequationrelatingfluxJotocurrent
J o (o,t ) =

dC
(o,t )
I
= D

nFA
dx x=0

toshowhowanequationthatdescribestheIvstresponseinthisamperometric
experimentcanbeobtained.Explaineachstep.

6.Shortanswerquestions,1pointeach,nopartcredit
(a)WhatisFaradayslaw

(b)WhatelectrochemicaltechniquewasinventedbyJ.Heyrovskyin1922.

(c)WhatdoRudyMarcusandJ.Heyrovskyhaveincommon?

(d)WhatismainioniccontributiontononFaradaic(charging)current?

(e)ThecommonassumptionofkinetictransitionstatetheoryandMarcustheoryis
thattherateconstantdependsonwhatenergeticparameter?