POURBAIX DIAGRAM

Graphical representation of the domains of stability of metal, metal ions, oxides, hydroxide, etc. in aqueous solution.

Potential (E)

H+

OHM MO

M+2 H2O

H+

pH
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Pourbaix Diagram g (cont.) ( )

The Nernst Equation allows us to compute lines on the diagram for equilibrium reactions of interest

Electrochemical reactions of pure charge transfer (horizontal lines since no o H+ o or OH O -d dependence p d - corresponding o po d g to o potentials po a of o equilibria at given concentrations)

Pure acid-base reactions (vertical lines - since no electron transfer and

no dependence on potential - corresponding to equilibrium concentrations of H+ (OH-) for given concentrations of species)

Electrochemical reactions involving charge transfer and H+ (OH-)

(sloping lines).

Pourbaix Diagram (cont.)

(1) Pure Charge Transfer Reaction
Consider Ni2+ + 2e- = Ni So, the Nernst equation becomes, With e0 = -0.25 V, so

e = e0 +

2.303 RT log( Ni 2 + ) 2F

e 0 = 0.25 + 0.03 log( Ni 2 + )

We usually compute for 4 concentrations 100, 10-2, 10-4, 10-6 M

Ni2+

Ni Partial Pourbaix Diagram for Ni2+ + 2e- = Ni

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Pourbaix Diagram (cont.)

(2) Pure AcidAcid - Base Reaction
Consider Ni2+ + 2H2O = Ni(OH)2 + 2H+ There is no charge transfer, so the Pourbaix diagram is a vertical line for a given Ni2+ concentration. We evaluate the equilibrium constant, constant K, K form the standard free energy change for the reaction.

G 0 = RT ln K
or

log( K ) =

G 0
2.303 RT

Pourbaix Diagram (cont.)

( 2 ) Pure AcidAcid - Base Reaction
G0 calculated from the standard free energy of the reactants and products
0 G 0 = pGp + r Gr0

or

log K =

0 0 0 0 GNi 2 + + 2GH O GNi ( OH ) 2G + H 2 2

2.303 RT

G0 values are tabulated tabulated

0 GNi 2+ = 0 GH = 2O 0 GNi( OH)2 = 0 GH = +

and So, at 250C, log K -12

-11,100 cal/mol -56,690 cal/mol -108,300 cal/mol 0 (convention)

Pourbaix Diagram (cont.)

(2) Pure AcidAcid - Base Reaction
For reaction Ni2+ + 2H2O = Ni(OH)2 + 2H+

[ Ni( OH )2 ][ H + ] 2 K= [ Ni 2 + ][ H2O ]
Si Since th the continuous ti phase h H2O and d (solid) ( lid) Ni(OH)2 have h activities ti iti of f 1, 1

[H+ ]2 = 12 log [ Ni 2 + ]
or

log[ H + ] 2 = 12 + log[ Ni 2 + ]

pH = 6 0.5 log[ Ni 2 + ]

Pourbaix Diagram (cont.)

(2) Pure AcidAcid - Base Reaction
Again, we compute for [Ni2+] = 100, 10-2, 10-4 and 10-6 M

Ni

Ni(OH)2

The region to the left of a particular line (i.e., more acid) is the region of stability for Ni2+ So, if we are on the equilibrium line at pH 9 for a Ni2+ concentration of 10-6 M, and we drop the pH to 7 (say), the Ni(OH)2 solid in contact with the solution will dissolve to try and make the concentration to 10-2 M.
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Pourbaix Diagram (cont.)

(3) Reactions Involving Electrons and H +
Consider Ni + H2O = NiO + 2H+ + 2e2.303 RT [ NiO ][ H + ] 2 E=E + log 2F [ Ni ][ H2O ]
0

th N the Nernst t equation: ti

E = E 0 0.059 pH

Calculate E0 So,

E =
0

G 0
nF

0 0 0 GNi GH GNiO 2O

2F

0.11V

E = 0.11-0.059pH

Pourbaix Diagram (cont.)

(3) Reactions Involving Electrons and H +
NOTE We can also depict the Ni H2O reaction as: Ni + 2H2O = Ni(OH)2 + 2H+ + 2eS th So that t
2.303 RT [ Ni( OH )2 ][ H + ] 2 E=E + l log 2F [ Ni ][ H2O ] 2
0

E = E 0 0.059 pH

(as for NiO)

0.11V

With

E =
0

G 0
nF

0 0 0 GNi ( OH )2 GNi 2GH2O

2F

E = 0.11 0.059 pH This is identical with the line for the Ni/NiO equilibrium. i.e., Ni(OH)2 is as likely (thermodynamically) as NiO.

Pourbaix Diagram g (cont.) ( )

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Pourbaix Diagram (cont.)

(4) Stability Lines for Water

In most environments of interest to corrosion, there is not a large concentration of metal ions acting as cathodic reactants. The important cathodic reactions involve water. ( ) 2H+ + 2 (a) 2e- = H2 (b) O2 + 4H+ + 4e- = 2H2O

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Pourbaix Diagram (cont.)

( 4 ) Stability Lines for Water
The Nernst equation gives Line (a) on Pourbaix diagram For line (b) similarly.. With

eH + / H = 0.059 pH
2

eO2 = e

0 O2

pO2 [ H + ] 4 0.059 + log [ H 2O ] 2 2

[H2O] = 1 pO = 1atm
2

0 eO = 1.23V 2

(for diagram)

Therefore, line (b) is:

eO2 = 1.23 0.059 pH

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Pourbaix Diagram (cont.)

(4) Stability Lines for Water

O2 + 4H+ + 4e- = 2H2O

2H+ + 2e- = H2

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Pourbaix Diagram (cont.)

(4) Stability Lines for Water 2H+ + 2e- H2 2H2O + 2e- H2 + 2OHhydrogen evolution in acids hydrogen evolution in neutral/bases

(th above (the b t two reactions ti are equivalent i l t reactions) ti )

O2 + 2H2O + 4e- 4OHO2 + 4H+ + 4e- 2H2O

oxygen reduction in neutral/bases oxygen reduction in acids

(the above two reactions are equivalent reactions)

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Pourbaix Diagram g (cont.) ( )

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Pourbaix Diagram g for Zinc

for 2.0 2 0Equilibrium Zn(OH)2 + 2OH- ZnO22- + 2H2O 1.6 1.2 0.8 Potential 0.4 0.0
Zn(OH)2 stable

Equilibrium for Zn2+ + 2OH- Zn(OH)2

E ilib i Equilibrium f for solid Zn2+ stable - stable in Zn(OH) + 2eEquilibrium for Zn + 2OH 2 2+ + 2e-0.4 Zn Zn in solution solution Equilibrium q for -0.8 0.8 Zn + 4OH- ZnO22- + 2H2O + 2e-1.2 Zn metal stable -1.6 0 7 14 pH
16

ZnO22-

Pourbaix Diagram g for Zinc

For indicating corrosion trends, we can use simplified versions

2.0 1.6 12 1.2 0.8 Potenti ial 0.4 0.0 -0.4 -0.8 -1.2 -1.6 16 0

Corrosion possible with oxygen reduction Corrosion is possible, but Corrosion likely to be stifled by solid possible ibl with ih corrosion product hydrogen evolution Zn(OH)2 Corrosion
2ZnO Corrosion requires strong 2 Corrosion is solid Zn2+ stable oxidising agent stable in thermodynamically impossible in solution solution

stable

Immunity Zn metal stable 7 14

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Pas ssivity

Co orrosion

Pourbaix Diagram g for Gold

20 2.0 1.6 1.2 0.8 Potential 0.4 0.0 -0.4 -0.8 0.8 -1.2 -1.6 0 7 14
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Passivity C

Gold metal stable Immunity

Gold cant corrode with oxygen reduction or hydrogen evolution

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Use of Pourbaix Diagram g (Cu) ( )

Corrosion requires strong oxidizing agent

Corrosion possible with O2 reduction

Corrosion is possible but likely to be stifled by solid corrosion product Corrosion is thermodynamically impossible

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Pourbaix Diagram g for Ti (I) ()

Ti is thermodynamically reactive, but is nevertheless very corrosion resistant because of a highly resistant passive film that is stable at all ll pHs H i in oxidizing idi i potentials. t ti l

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Use of Pourbaix Diagram g

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Validity y of Pourbaix Diagram g - Example p

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Validity y of Pourbaix Diagram g - Example p

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Use of Pourbaix Diagram

(Hot(Hot - dipped AlAl - Zn coated steel)
Widely used for fences and roofs after painting painting. Act as a sacrificial anode Expected service life: 20 to 30 yrs. In some locations, although the metalized coatings were still present, the underlying steel had corroded at defects.

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Use of Pourbaix Diagram

(Hot(Hot - dipped AlAl - Zn coated steel)

To function as a sacrificial anode, anode Al & Zn must remain active/unfilmed state.

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Use of Pourbaix Diagram

(Hot(Hot - dipped AlAl - Zn coated steel)

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Pourbaix Diagram g for Tertiary y Systems y

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Limitations of Pourbaix Diagrams g

Tell us what can happen, not necessarily what will happen. No information on rate of reaction Can only C l be b plotted l d for f pure metals l and d simple i l solutions, l i not for f alloys.

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References

M. Pourbaix, Lectures on Electrochemical Corrosion, Plenum Press, New York, 1973. M. Pourbaix, Atlas of Electrochemical Equilibria in Aqueous Solutions, NACE International, Houston, TX.

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Homework Problems
1) Using the Pourbaix diagram for nickel, Fig. 2.11 (d), give the anodic and cathodic reactions that occur on Ni in water for the following conditions, assuming activity of 10-6 for all soluble species:
a) ) b) c) ) d) Deaerated p pH 2 Deaerated pH 10 Aerated pH 2 Aerated p pH 10

2) Problems #9 of Chapter 2 in textbook.

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