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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
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Signals
166
Linearscanvoltammetry
Earlierandsimplestvoltammetric
methods,usuallyinmicroampere
TWOTYPESOFLINEARSCAN
HYDRODYNAMICVOLTAMMETRY
POLOGRAPHY
167
Voltametricinstrument
Asupportingelectrolyte,
inelectrochemistry,accordingtoanIUPAC
definition
Workingelectrode
istheelectrodeinanelectrochemicalsystemon
whichthereactionofinterestisoccurring.
counterelectrode
isanelectrodeusedina
threeelectrodeelectrochemicalcellforvoltammetric
analysis.
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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
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CyclicVoltammetry
Oxidationandreduction
Variationofrates
Peakpotentials
Anode(bottompeak)
Cathode(toppeak)
Difference0.0592/n
Peakcurrents
Cathode(linetopeak)
Anode(slopetobottom)
Peakcurrentsequal
andoppositesign
Mechanismsandratesof
redox
1621
CVdata
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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
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Electrorefining
Electrorefining
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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
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