Voltammetry

Voltammetry
isacategoryofelectroanalyticalmethods
usedinanalyticalchemistryandvarious
industrialprocesses.
Voltammetrydiffersfromelectrogravimetryand
coulometryintherespectthatwiththelatterpair,
measurearetakentominimizeorcompensateforthe
effectofconcentrationpolarization.

161

ELECTRODES

162

CIRCUIT

163

Voltammetry
History
Thefieldofvoltammetrydeveloped
frompolarography.

Wasdiscoveredbyczechoslovokian
chemistJAROSLAVHEYROVSKYIN
THEEARLY1920S
164

Method
Excitationsignalapplied
Waveresponsebasedonmethod
Linear
Differentialpulse
Squarewave
Cyclic
Developedcurrentrecorded

165

Signals

166

Linearscanvoltammetry
Earlierandsimplestvoltammetric

methods,usuallyinmicroampere
TWOTYPESOFLINEARSCAN
HYDRODYNAMICVOLTAMMETRY
POLOGRAPHY

167

Voltametricinstrument
Asupportingelectrolyte,
inelectrochemistry,accordingtoanIUPAC
definition
Workingelectrode
istheelectrodeinanelectrochemicalsystemon
whichthereactionofinterestisoccurring.
counterelectrode
isanelectrodeusedina
threeelectrodeelectrochemicalcellforvoltammetric
analysis.
168

Electrodes

169

Potentialranges

Numberofusefulelementsfor
electrodes
Pt
Hg
C
Au
Limits
Oxidationofwater
2H2O>4H++O2(g)+4e
Reductionofwater
2H2O+2e>H2+2OH

1610

Overpotential
Overpotentialalwaysreducestheoreticalcell
potentialwhencurrentisflowing
=EcurrentEequilibrium
Overpotentialduetoelectrodepolarization:
concentrationpolarizationmasstransport
limited
adsorption/desorptionpolarizationrateof
surfaceattach/detachment
chargetransferpolarizationrateofredox
reaction
reactionpolarizationrateofredoxreactionof
intermediateinredoxreaction
Overpotentialmeansmustapplygreaterpotential
beforeredoxchemistryoccurs
1611

Voltammograms

Currentagainstappliedvoltage
Increaseincurrentat
potentialatwhichanalyteis
reduced
Reactionrequires
electrons
* suppliedby
potentiostat
Halfwavepotential(E1/2)iscloseto
E0forreductionreaction

Limitingcurrentproportionalto
analyteactivity
1612

Methods
Currentisjustmeasureof
rateatwhichspeciescan
bebroughttoelectrode
surface
Stirred
hydrodynamic
voltammetry
Nernstlayernear
electrode
* Diffusionlayer
* Migration
* convection
1613

Methods

Analyte(A)andproduct(P)
Instirredsolutionconvectiondominates

1614

Methods
Currentisameasureofhowfasttheanalyte
cangotoelectrodesurface

1615

Hydrodynamic
Singlevoltammogramcan
quantitativelyrecordmany
species
Requiressufficient
separationofpotentials
NeedtoremoveO2

1616

HangingHgelectrode
Polarography
Differsfromhydrodynamic
unstirred(diffusion
dominates)
droppingHgelectrode
(DME)isusedas
workingelectrode
currentvariesasdrop
growsthenfallsoff

1617

LinearScan
AdvantagesofDME
cleansurfaceandconstant
mixing
constantcurrentduring
dropgrowth
NoH2formation
DisadvantagesofDME:
Hgeasilyoxidized
cumbersometouse

1618

1619

1620

CyclicVoltammetry
Oxidationandreduction
Variationofrates
Peakpotentials
Anode(bottompeak)
Cathode(toppeak)
Difference0.0592/n
Peakcurrents
Cathode(linetopeak)
Anode(slopetobottom)
Peakcurrentsequal
andoppositesign
Mechanismsandratesof
redox
1621

CVdata

1622

MoltenSaltProcesses
Inorganicphasesolvent
Hightemperatureneededtoformliquidphase
Differentinorganicsaltscanbeusedassolvents
Separationsbasedonprecipitation
Reductiontometalstate
Precipitation
Twotypesofprocessesinnucleartechnology
Fluoridesaltfluid
Chlorideeutectic
Limitedradiationeffects
ReductionbyLi
1623

MoltenSaltReactor
Fluoridesalt
BeF2,7LiF,ThF4,UF4usedasworkingfluid
thoriumblanket
fuel
reactorcoolant
reprocessingsolvent
233PaextractedfromsaltbyliquidBithroughLibased
reduction
Removaloffissionproductsbyhigh7Liconcentration
UremovalbyadditionofHForF2

1624

Pyroprocesses

Electrorefining
Reductionofmetalionstometallicstate
Differencesinfreeenergybetweenmetalionsandsalt
Avoidsproblemsassociatedwithaqueouschemistry
Hydrolysisandchemicalinstability
Thermodynamicdataathandoreasytoobtain
Sequentialoxidation/reduction
Cationstransportedthroughsaltanddepositedoncathode
Depositionofionsdependsuponredoxpotential

1625

ElectrochemicalSeparations
Selectionofredoxpotentialallowsseparations
Canusevarietyofelectrodesforseparation
DevelopedforIFRandproposedforATW
DissolutionoffuelanddepositionofUonto
cathode
Hightemperature,thermodynamicdominate
CsandSrremaininsalt,separatedlater

1626

Electrorefining
Electrorefining

1627

Reductionofoxidefuel
Input
445kgoxide(fromstep1)
135kgCa
1870kgCaCl2
Output
398kgheavymetal(tostep3)
Tostep8
2kgCs,Sr,Ba
189kgCaO
1870kgCaCl2
1kgXe,Krtooffgas

Step2

Metal

OperatingConditions
T=1125K,8hours
4100kg/1PWRassembly1628

UraniumSeparation

Step3
Input
398kgheavymetal(fromstep2)
385kgU,20kgU3+(enriched,6%)
3.98kgTRU,3.98kgRE
188kgNaClKCl
Output
392kgUoncathode
Tostep4(anode)
15gTRU,14gRE,2.8kgU,5kgNobleMetal
MoltenSalttostep5
10kgU,3.9kgTRU,
3.9kgRE,188kgNaClKCl

Anode

OperatingConditions
1629
T=1000K,I=500A,265hours
4100kg/1PWRassembly

PolishingReducesTRUDischarge

Step4
InputfromAnode#3
5kgNobleMetal,2.8kgU,15gTRU,14gRE,1.1
kgU3+,18.8kgNaClKCl
Output
Anode
5kgNobleMetal,0.15gU,0.045gTRU,0.129gRE
Cathode
1.5gNobleMetal,2.9kgU
MoltenSalt(to#3)
28gNobleMetal,1kgU,15gTRU,14gRE,18.8
kgNaClKCl

Metal
Anode

OperatingConditions
1630
T=1000K,I=500A,2hours
1PWRassembly

ElectrowinningProvideFeedforFuel
Step5

Inputfrommoltensaltfrom#3
10kgU,4kgTRU,4kgRE,4.3kgNaas
alloy,188kgNaClKCl
Output
Cathode
Uextraction9.2kg
U/TRU/REextraction,1kgU,4kgTRU,0.5
kgRE
MoltenSalt(to#7)
3.5kgRE,192kgNaClKCl

Metal

OperatingConditions
1631
T=1000K,I=500A,3.7hoursforU/TRU/RE,6.2hoursforU
1PWRassembly

ReductionofRareEarths
Input
MoltenSaltfrom#5
3.4kgRE
1.7kgNaasalloy
188kgNaClKCl
Output
MoltenSalt(tostep3)
189kgNaClKCl
MetalPhase
3.4kgRE

Step7

Metal

OperatingConditions
T=1000K,8hours
1632

RecycleSalt:ReductionofOxide

Step8
Input
Chlorination
189kgCaO,1870kgCaCl2,239kgCl2
Electrowinning
2244kgCaCl2
Output
Chlorination
2244kgCaCl2,54kgO2
Electrowinning(to#2)
1870kgCaCl2,135kg
Ca,(239kgCl2)

OperatingConditions
1633
T=1000K,I=2250A,80hours

U,TRU,andFissionProductSeparation

Step10
Input
45kgfromStep9(includesZr)
Includes9.5kgTRU,0.5kgRE
Output
Anode
33kgNM,2kgU
MoltenSalt(to#11)
SmallamountsofU,TRU,RE
Cathode(to#12)
MostTRU,RE

Anode

TRU

OperatingConditions
1634
T=1000K,I=500A,6.7hours

ElectrowinningTRUforSaltRecycle

Step11
Inputfrommoltensaltfrom#10
1.7kgU,7.4kgTRU,0.5kgRE,2.8kg
Naasalloy,188kgNaClKCl
Output
Cathode(to#12)
U/TRU/REextraction,1.7kgU,7.4kg
TRU,0.1kgRE
MoltenSalt(to#13)
0.4kgRE,191kgNaClKCl

Metal

OperatingConditions
T=1000K,I=500A,6.1hoursforU/TRU/RE
Saltfrom10electrorefiningsystems

1635

ReductiontoRemoveRareEarths
Step13

Input
0.4kgRE(from#11),188kg
NaClKCl,0.2kgNaasalloy
Output
MoltenSalt
188kgNaClKCl
MetalPhase
0.4kgRE

Metal

OperatingConditions
T=1000K,8hours
1636