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CorrosionElectrochemistry1

MicheleCurioni
LectureOverview
UnderstandanduseFaradayslaw
Chargemassrelationship
Currentandmassloss
Currentandcorrosiondepth
NernstEquation
Equilibriumpotentialsandactivity
Pourbaix Diagrams
FeandZndiagrams
UseofPourbaix Diagrams
LimitationsofPourbaix Diagrams
MetalOxidation

2e Cu0 Cu2+

2e Cu0 Cu2+

2e Cu0 Cu2+

2e Cu0 Cu2+

MetallicCopper Electrolyte
UnderstandanduseFaradayslaw
AnodicReaction

Cu0 Cu2++2e

2e Cu0 Cu2+

2e Cu2+ NetCharge=0 NetCharge=0


Cu0

2e Cu0 Cu2+

2e Cu0 Cu2+

MetallicCopper Electrolyte
UnderstandanduseFaradayslaw
ChargeNeutrality
ChargeneutralitymustbemaintainedinALL phases(metalandsolution)atALL times

Coppermetalcannotbecame
negativelycharged.
2e Cu0 Cu2+
Electrolytecannotbecome
positivelycharged.
2e Cu0 Cu2+

2e Cu0 Cu2+

Cu0 Cu2+
Howcharge
2e
neutralityis
maintained?

MetallicCopper Electrolyte
UnderstandanduseFaradayslaw
CathodicReaction

+
EXTERNALCIRCUIT

2e Cu0 Cu2+ Cu2+ Cu0 2e

2e Cu0 Cu2+ Cu2+ Cu0 2e

2e Cu0 Cu2+ Cu2+ Cu0 2e

2e Cu0 Cu2+ Cu2+ Cu0 2e

MetallicCopper Electrolyte MetallicElectrode


UnderstandanduseFaradayslaw
CathodicReactionI

8e 8e 8e

WORKMUSTBE
PROVIDEDBY
THEEXTERNAL
2e Cu0 Cu2+ Cu2+ Cu0 2e CIRCUITFORTHIS
REACTIONTO
2e Cu0 Cu2+ Cu2+ Cu0 2e PROCEEDAT
FINITESPEED!
2e Cu0 Cu2+ Cu2+ Cu0 2e

2e Cu0 Cu2+ Cu2+ Cu0 2e

MetallicCopper Electrolyte MetallicElectrode


UnderstandanduseFaradayslaw
CathodicReactionII

8e 8e 8e

Inprincipleit
couldhappened
O2(g) withoutexternal
2e Cu0 Cu2+ 4OH 4e workatsomepH
(04)
2e Cu0 Cu2+ 2H2O(l) (butthereis
smalldriving
2e Cu0 Cu2+ force)
O2(g)
2e Cu0 Cu2+ 4OH 4e

2H2O(l)

MetallicCopper Electrolyte MetallicElectrode


UnderstandanduseFaradayslaw
CathodicReactionIII

+ 8e 8e 8e

WORKMUSTBE
PROVIDEDBY
H2(g) THEEXTERNAL
2e Cu0 Cu2+ 2OH 2e CIRCUITFORTHIS
REACTION!
2e Cu0 Cu2+ 2H2O(l)
NOT
2e Cu0 Cu2+ SPONTANEOUS!
H2(g)
2e Cu0 Cu2+ 2e
2OH

2H2O(l)

MetallicCopper Electrolyte MetallicElectrode


UnderstandanduseFaradayslaw
Corrosion

2e Cu0 Cu2+
2e Cu0 Cu2+

O2(g)
4e 4OH

2H2O(l)
Currentandreactions
AnodicReaction CathodicReaction
4Al 4Al3++ 12e 3O2(g)+ 6H2O(l) + 12e 12OH

Movewithinthemetal
Electriccurrent

Movewithintheelectrolyte

Directrelationshipbetweenthecurrentflowingintothemetaland
theamountofmetaloxidized
CathodicReactionExample
Mostusualcathodicreactionsare
Oxygenreduction
Hydrogenevolution
Metal(re)deposition

Writecompleteandbalancedcellreaction(anodic+cathodic)for
Aluminium
(hint: AlinsolutionbecomesAl3+,anduseOxygenreduction)
Solution
AnodicReaction

Al Al3+ + 3e 1AlinbothsidesCharge=0inbothsides

CathodicReaction
4Oxygeninbothsides,4Hydrogenin
O2(g) + 2H2O(l) + 4e 4OH
bothsides,Charge=4inbothsides

CellReaction NotBalanced

Al + O2(g) + H2O(l) Al3+ + OH

CellReaction Balanced 4Alinbothsides

4Al + 3O2(g)+ 6H2O(l) 4Al3+ + 12OH 12Oinbothsides


12Hinbothsides
Charge=0inbothsides
Canwemeasurechargeflow?
Current Electriccurrentisaflowofelectricchargethroughamedium.

? Electronflowiseasiertomeasurethanionicflowaswecanuse
aresistorandapplyOhmslaw
Resistance=R

OhmsLaw
Anions()
V=RI
Current=I
Cations (+)
I=V/R
Cathode Anode Voltage=V
(measured)
ChargeandCurrent
1Coulomb(C)=6.241x1018 electrons
1Ampere(A)=1Coulomb/Second
1molis6.022x1023 units(ofanything)

Thechargeofonemolofelectronsis
6.022 10 23 C Faradays
0.96485 10 96485
5

6.241 10 18
mol Constant

FaradaysConstantisneededwhen
convertingcurrent/chargeinmass
Summary
Weknowhowmany(molof)electronsweneedtooxidize
each(moleof)metalatom
Weknowthatweneedanexternalcircuittohaveacell
reaction
Wecanmeasurethecurrentandchargepassingthroughthe
externalcircuit
Weknowhowmuchchargethereisinamolofelectrons

Wecanworkouttherelationshipbetween
thecurrentwemeasureandthemetalwe
oxidize
FaradaysLawI

ChargePassed(C) C
= = molesofoxidizedmetal(mol)
ValenceNumber FaradaysConstant(C/mol) n F

ChargePassed= Current(A)xtime(s)

Mass(g)= Molarmass(g/mol)xnumberofmol

ChargePassed(C)xMolarmass(g/mol) CM
= = massofoxidizedmetal(g)
ValenceNumber FaradaysConstant(C/mol) n F
FaradaysLawII
ChargePassed(C)xMolarmass(g/mol) CM
= = massofoxidizedmetal(g)
ValenceNumber FaradaysConstant(C/mol) n F

Mass(g)
Volume(cm3)= =densityg/cm3
Density
(g/cm3)
CM
= VolumeofOxidizedMaterial
nF

C=current(A)xtime(s)=Ixt

ItM
= VolumeofOxidizedMaterial
nF
FaradaysLawIII

ItM
= VolumeofOxidizedMaterial
nF

Volumeofoxidizedmaterial=Electrodearea(cm2)xThickness(cm)=Axh

ItM
= Thickness
n F A
FaradaysLawappliedtocorrosion
Ifonemetalelectrodeinagivenenvironmentonlysupportan
anodicreaction,anditiscoupledtoanotherelectrodebyan
externalcircuit(whichmightormightnotprovideworktothe
cell),then

ItM Note:ifI(t)isnotconstantyouneedto
Oxidizedmaterialattimet= calculatetheintegralofI(t)dt between
n F A 0andttogetthecharge

IM
Corrosionrate=
n F A
NernstEquation
ElectrochemicalPotential

???? Howmuchworkcanweproducefromthissystem?

Cu Zn
Zn2+ +2 e Zn
Cu2+ +2 e Cu

Cu2+ Zn2+

Seeexamplecell
HydrogenReferenceElectrode
Standardconditions

Concentration1moldm3butinfinitedilution
behavior
Temperature298.15K(25C)
Pressure1Bar

Whydoweneedstandardconditions?
StandardCellPotential/Hydrogen
electrode
GibbsFreeEnergy
Gibbsfreeenergyaccountsforthenon
mechanicalworkthatcanbedonebyasystem

G H TS
Foranelectrochemicalcell(standardconditions)

G 0 RT ln K eqst
Where Reduced
species
[ products ] INSTANDARD
K st
eq CONDITIONS
[reagents] Oxidizedspecies
EquilibriumConstants
Keq canbecalculatedfromconcentrations
Reducedspecies

Oxidizedspecies Reducedspecies Oxidizedspecies


NernstEquationI
Gibbsfreeenergyaccountsforthenon
mechanicalworkthatcanbedonebyasystem
G 0 RT ln K eqst
Inan electrochemicalcell,thisisalso
equivalenttotheelectricalwork

G 0 welectrical (Q)(V ) ( I )(t )(V )


NernstEquationII
G 0 welectrical (Q)(V ) ( I )(t )(V )

Foronemol

G (n)( F )( E )
0 0
cell

So
RT ln K (n)( F )( E )
st
eq
0
cell

G 0
G 0
NernstEquationIII
STANDARDCONDITIONS

RT ln K st
0

eq
E cell
nF

NONSTANDARDCONDITIONS

1 2
[a p1a p 2 ...]
G RT ln K
0 st
eq RT ln 1 1
[a r1a r1...]
NernstEquation Thebasisof
Pourbaix diagrams

Oxidizedspecies Reducedspecies

0.059 [C 1 p1C 2 p 2 ...]


Ecell Ecell
0
log 1 1
n [C r1C r1...]
Example2
1reactant(halfcell)
Cupotentialat0.1MCuSO4 and0.5MCuSO4
2reactants(fullcell)
CellpotentialofCuZncellata)0.1MCuSO4 and
0.5MZnSO4
Pourbaix Diagrams
Pourbaix Diagrams

Pourbaix Diagramslinkpotential, pHandspeciesin


solutionorontheelectrodesurface

NernstequationprovidesatoolfordrawingPourbaix
Diagrams
Pourbaix Diagramsrelatetothethermodynamicsof
corrosion.Theywilltellifcorrosionispossibleornot
foragivensetofpHorelectrodepotential
Veryimportantinpredictingpossiblecorrosion
issues
Example
GeneralrulesforPourbaix diagrams
Ifequilibriuminvolvesonlymetalandmetalions,itwillbe
affectedonlybypotential.Thisgenerateshorizontallineson
Pourbaix diagrams.
Example:AlAl3+ +3e
Ifequilibriumdoesnotinvolveoxidationorreductionof
species,itwillgenerateaverticallineonPourbaix diagrams
Example:Al2O3.H2O+2H+ 2Al(OH)2+
Ifequilibriuminvolvesoxidationofmetal,buttheresulting
ionscontainshydrogenorhydroxideions,itwillgeneratea
diagonallineinthepourbaix diagrams
Example:Al+2H2OAlO2 +4H++3e
Pourbaix diagrams
ChangesinpHonlyaffectreactionsthathave
hydrogenorhydroxideionsinthereactantor
products.
Zn Zn2+ +2e

0.059 [ Zn]
ER E
0
R
n
log

Zn 2
0.059 [1]
ER E 0
R log NOpHeffectonpotential
n [Const ]
Pourbaix diagrams
ChangesinpHonlyaffectreactionsthathave
oxygenorhydrogenionsinthereactantor
products.
Zn(OH)2 +2e Zn+2OH

2
0 . 059 [ Zn ][OH ]
ER ER
0
log pHaffectspotential!!
2 [ Zn (OH ) 2 ]
The Pourbaix (E-pH) Diagram

2.0
1.6
O2 is stable
1.2
0.8
Potential

0.4 H2O is stable


0.0
-0.4
-0.8
-1.2 H2 is stable
-1.6
0 7 14
pH
Pourbaix Diagram for Zinc

2.0
1.6
1.2
0.8 Zn(OH)2
Potential

0.4 stable
ZnO22-
0.0 Zn2+ stable
solid
stable in
-0.4 solution
in solution
-0.8
-1.2
Zn metal stable
-1.6
0 7 14
pH
Pourbaix Diagram for Zinc

2.0
1.6
1.2

Corrosion
Passivity
0.8 Zn(OH)2
Potential

0.4 Corrosion stable


ZnO22-
0.0 Zn2+ stable
solid
stable in
-0.4 solution
in solution
-0.8
-1.2 Immunity
Zn metal stable
-1.6
0 7 14
pH
Pourbaix Diagram for Gold

2.0
1.6 C Passivity
1.2 C
0.8
Potential

0.4
Gold Gold
metalcant corrode
stable
0.0 with oxygen reduction
Immunity
-0.4 or hydrogen evolution
-0.8
-1.2
-1.6
0 7 14
pH
Pourbaix diagram for Copper

2.0

CuO22- stable in soln.


1.6
Cu oxides
1.2
stable
0.8 Cu2+ stable
Potential

0.4 in solution
0.0
-0.4
-0.8 Cu metal stable
-1.2
-1.6
0 7 14
pH
Pourbaix Diagram for Iron

2.0
1.6
1.2
Fe3+
0.8
Potential

0.4 Fe oxides
0.0 stable
-0.4 Fe2+ stable
-0.8
-1.2 Fe metal stable
-1.6
0 7 14
Pourbaix diagram for Aluminium

1.2
0.8
0.4
0.0
Potential

-0.4
-0.8 Al3+
Al2O3
-1.2 AlO2-
-1.6
-2.0 Al
-2.4
0 7 14
pH
Zinc in Acid
Zn Zn2+ + 2e-

Zn
Oxidation current > Reduction current

2H+ + 2e- H2 HCl

Reduction current > Oxidation current