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Corrosion

Pourbaix diagrams graphically represent the thermodynamic equilibrium states of a metal-electrolyte system by plotting electrode potential vs. pH. They define different corrosion and passivation zones based on the predominant metal species. Horizontal and vertical lines indicate pH-independent and pH-dependent reactions, while diagonal lines represent pH-dependent redox reactions. Pourbaix diagrams allow determining the corrosion behavior and equilibrium state of a metal under various water solution conditions.

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Shubham Baxla (CSEAIML23310662409:30)
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19 views26 pages

Corrosion

Pourbaix diagrams graphically represent the thermodynamic equilibrium states of a metal-electrolyte system by plotting electrode potential vs. pH. They define different corrosion and passivation zones based on the predominant metal species. Horizontal and vertical lines indicate pH-independent and pH-dependent reactions, while diagonal lines represent pH-dependent redox reactions. Pourbaix diagrams allow determining the corrosion behavior and equilibrium state of a metal under various water solution conditions.

Uploaded by

Shubham Baxla (CSEAIML23310662409:30)
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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POURBAIX DIAGRAM

Pourbaix diagram is used to determine the


corrosion behavior of a metal in water
solutions

It is a graphical presentation of the


thermodynamic equilibrium states of a metal-
electrolyte system. Pourbaix diagrams are plotted
b/w Electrode potential of the metal vs. pH of
the electrolyte.
Oxidizing conditions are
described by the top part of
the diagram (high positive
electrode potential).
Reducing conditions are
described by the bottom part
of the diagram (high negative
electrode potential).
Acidic solutions are presented
in the left side of the diagram
(PH lower than 6).
Alkaline solutions are
presented in the right side of
the diagram (PH higher than 6).
The lines of the diagrams dividing different zones of the
equilibrium states are calculated by the Nernst equation:
E = E0 - (0.059/n)*lnCion
Where:
E0 - Standard electrode potential, V;
n - number of electrons transferred;
Cion - molar activity (concentration) of ions.

Pourbaix diagrams allow to determine the corrosion


behavior of a metal in water solutions i.e. the direction of
electro-chemical processes and the equilibrium state of the
metal at a certain electrode potential in a water solution at
a certain value of pH.
The diagram defines the following zones of the equilibrium states:

below the line a-b-j: Solid


iron (immunity zone). The
electrochemical reactions
in this zone proceed in the
direction of reduction of
ions. No corrosion occurs
in this zone.
a-b-n-c-d-e: Aqueous
solution of ion Fe2+
(corrosion zone). Metallic
iron oxidizes in this zone.
e-d-f-g-k: Aqueous solution
of ion Fe3+ (corrosion zone).
Metallic iron oxidizes
(corrodes) in this zone.
The diagram defines the following zones of the equilibrium states:

h-f-g-m: Aqueous solution


of ion FeO42- (corrosion
zone).
c-d-f-h-i: Solid ferrous oxide
Fe2O3 (passivation zone).
Iron oxidizes in this zone
however the resulted oxide
film depresses the oxidation
process causing passivation
(corrosion protection of the
metal due to formation of a
film of a solid product of
the oxidation reaction).
The diagram defines the following zones of the equilibrium states:

n-c-i-p: Solid oxide


Fe3O4 (Fe2O3*FeO)
(passivation zone).
The oxide film causes
passivation.
b-n-p-j: Solid
hydroxide (II) Fe(OH)2
/ FeO*nH2O / green
rust (passivation
zone).
Horizontal lines of the Poubaix diagrams correspond to
the redox reactions, which are independent of pH.
Vertical lines of the Poubaix diagrams correspond to the
non-redox reactions (electrons are not involved), which
are dependent on pH.
Diagonal lines of the Poubaix diagrams correspond to
the redox reactions, which are dependent on pH.
Some of the reactions and the corresponding lines of the Fe-H2O
Pourbaix diagram

a-b: Fe(s) = Fe2+(aq) + 2e- Redox reaction independent of pH. The


equilibrium occurs at the electrode potential value -0.44V, which
is equal to the standard electrode potential of iron .

e-d: Fe2+(aq) = Fe3+(aq) + e- Redox reaction independent of pH.


d-f: 2Fe3+(aq) + 3O2- = Fe2O3(s) Non-redox reaction dependent on
pH.
b-n: Fe2+(aq) + 2OH-(aq) = Fe(OH)2(s) Non-redox reaction
dependent on pH.
c-d: 2Fe2+(aq) + 3H2O = Fe2O3(s) + 6H+(aq) +2e- Redox reaction
dependent on pH.
b-j: Fe(s) + 2OH-(aq) = Fe(OH)2(s) + 2e- Redox reaction dependent
on pH.
Limitations of Pourbaix diagrams:
 The diagrams provide no information about the kinetic
parameters of the corrosion reactions.
 The diagrams consider pure metals and aqueous
solutions at standard conditions (temperature 298K,
pressure 1 bar, ion concentration 10-6M).
Thermodynamic conditions of corrosion for alloys and
for non-standard conditions differ from those described
by Pourbaix diagrams.
 The diagram do not take into account non-ideal
behavior of aqueous solutions.
 Some thermodynamic data used for building diagrams
are not precise enough.

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