Thermodynamics of

Corrosion
POURBAIX DIAGRAM
Introduction
In an aqueous solution,
◦ Dissolution of metal and stability of products depend on
◦ nature of metal,
◦ oxidizing power of solution, and
◦ pH of solution

Stability of different metals is estimated by using potential-

pH diagrams
◦ Suggested by Marcel Pourbaix
Pourbaix Diagram
Diagram constructed from calculations based on Nernst equation and solubility
(activity) data for various metal compounds
Predicts reaction products of metal that exist at equilibrium at a given electrode
potential and pH
Show values of pH and potential conditions at which metal reacts to form
complex anions or oxides or where metal is immune to corrosion

Illustrates the thermodynamic state of a metal

Purpose of Pourbaix Diagrams

Predict spontaneous direction of reactions

Determine the potential/pH regions in which the metal is stable
and where corrosion is thermodynamically impossible
Estimate the nature and composition of corrosion products
Evaluate equilibrium conditions of metal/electrolyte interface
 Limitations of Pourbaix Diagram

Cannot be used to predict the rates of reactions

Evaluate only conditions for formation of barrier films on the metals
Cannot estimate their effectiveness in protecting in different
environments

All metals have a limiting critical value of their activities (about a concentration of <10-6 g of ions per liter)
Regions of
electrochemical stability
of water
Used to predict the properties of a
metal in aqueous solutions when the
metal’s potential is known at given pH
Line “b” electrode constructed using
reversible potential for hydrogen evolution
reaction in an acidic solution

Line “a” corresponds to region where

oxygen is formed

Area between a and b = water is stable

For corrosion to occur

Cathodic reaction (consumes electron)

must take place

To balance the anodic reaction (produces

electrons) of metal dissolving

In pure water, there are 2 possible

reactions

𝑂2 + 4𝐻+ + 4𝑒 − → 2𝐻2 𝑂

2𝐻+ + 2𝑒 − → 𝐻2
Above the line- OXIDIZED species
are stable
Below the line- REDUCED species are
stable (if there is a suitable anode
available)
In general, any metal “M” reacts anodically
in the presence of water through the
following general reactions
Oxidation of metal to aqueous cations

𝑀 → 𝑀+ + 𝑛𝑒 −
Oxidation of metal to oxide or hydroxide

𝑀 + 𝑛𝐻2 𝑂 → 𝑀(𝑂𝐻)𝑛 +𝑛𝐻 + + 𝑛𝑒 −

Oxidation of metal to aqueous anions

𝑀 + 𝑛𝐻2 𝑂 → 𝑀𝑂𝑛𝑛− + 2𝑛𝐻 +

Construction of the Pourbaix Diagram
1. Determine Species
2. Identify the Couples [# of couples = (n-1)!]
3. Balance the chemical reactions
◦ Reduction
◦ Non-electrochemical
4. Write complete Nernst Equation
5. Plot lines and determine Stability Regions
Example 1: Construction of the Al
Pourbaix Diagram
Step 1: Four species were considered (Al, Al3+, Al2O3 and AlO2-)
Species ΔG (J/mol)
Al 0
Al3+ -485344
Al2O3 -1582275
AlO2- -830900
H2O -237141
H+ 0
 Electrochemical Couple

Al Al3+
Al Al2O3
Step 2: 6 couples were
identified (4-1)! = 6 Al AlO2-
Al3+ Al2O3
Al3+ AlO2-
Al2O3 AlO2-
Step 3: Balanced Chemical Reactions

Electrochemical Couple Chemical Reaction ΔG (J/mol)

Al Al3+ Al3+ + 3e- ↔ Al 485344

Al Al2O3 Al2O3 + 6 H+ + 6e- ↔ 2Al + 3 H2O 870852

Al AlO2- AlO2- + 4 H+ + 3 e- ↔ Al + 2 H2O 356618

Al3+ Al2O3 Al2O3 + 6H+ ↔ 2Al3+ + 3H2O -99836

Al3+ AlO2- AlO2- + 4H+ ↔ Al3+ + 2 H2O -128726

Al2O3 AlO2- 2 AlO2- + 2H+ ↔ Al2O3 + H2O -157616

Step 4: Nernst Equation
The standard reduction potential for the electrochemical reactions were
obtained by:
∆𝑮
𝑬° = −
𝒏𝑭
For systems with e- transfer, the Nernst equation can be used since you
can express K as a function of pH
. 𝟎𝟓𝟗𝟐
𝑬 = 𝑬° − 𝒍𝒐𝒈𝑲
𝒏
𝒑𝑯 = −𝐥𝐨𝐠[𝑯+ ]
Step 4: Nernst Equation

Example:
Al2O3 + 6 H+ + 6e- ↔ 2Al + 3 H2O
𝐽
870852
𝐸° = − 𝑚𝑜𝑙 = −1.5040𝑉
𝐶
6 96500
𝑚𝑜𝑙
.0592 1
𝐸 = 𝐸° − log + 6
6 𝐻
.0592 1
𝐸 = 𝐸° − log + 6
6 𝐻
𝐸 = −1.5040𝑉 − 0.0592𝑝𝐻
Step 4: Nernst Equation
For couples with no electron transfer, the pH can be determined by
∆𝑮 = −𝟐. 𝟑𝟎𝟑𝑹𝑻𝒍𝒐𝒈𝑲

Example:
Al2O3 + 6H+ ↔ 2Al3+ + 3H2O
𝐴𝑙 3+ 2
∆𝐺 = −2.303𝑅𝑇𝑙𝑜𝑔
𝐻+ 6
∆𝐺 = −2.303𝑅𝑇(2𝑙𝑜𝑔 𝐴𝑙 3+ − 6 log 𝐻+ )
∆𝐺
− 2.303𝑅𝑇 − 2log[𝐴𝑙 3+ ]
𝑝𝐻 =
6
Step 5: Plot the
Lines and
Determine
Stability Regions
Step 5: Plot the
Lines and
Determine
Stability Regions
Example 2: Construction of Fe Pourbaix
Diagram
Given species: Fe3+, Fe3O4, Fe2O3

Species ∆𝑮°𝟐𝟗𝟖
kcal/mol
Fe3+ -2.52
Fe2O3 -177.1
Fe3O4 -242.4
H2O -56.59
Notes:
1. Diagrams are drawn for equilibrium situations
2. Most diagrams consider pure metals in solutions
3. Metal in region of passivity may be protective or not.
4. pH used on diagrams is the pH of the solution in contact
with the metal, not the bulk solution.
5. Pourbaix diagrams can shift based on the ion
concentrations used in construction.
Applications of Pourbaix Diagram to
Corrosion
1. The resistance of metals to uniform corrosion in
aqueous solutions.
2. The basis for establishing which metals can be expected
to have passivity ober a wide range of conditions of pH
and potential
3. Evaluation of the possible use of oxidizing inhibitors.
Corrosion
metal is degraded by the
environment
Passivation
Loss of chemical reactivity of
metals (might be due to
formation of a passivation
layer)
Immunity
Metal is not degraded by the
environment
Passivation
Phenomenon observed during corrosion of certain
metals/arroys
Involves the loss of chemical reactivity under certain
conditions.
Production of thin passivation layer that acts as barrier for
the reaction of the metal with the environment
Iron has 9 reduction and
oxidation reactions over a pH
range of 0-14

This diagram is plotted at

25C

Fe|Fe2+
Fe| Fe(OH)2
Fe| HFeO2-
Fe| Fe(OH)2
Fe(OH)2|HFeO2-
Fe2+| Fe(OH)3
Fe3+| Fe(OH)3
HFeO2-| Fe(OH)3
Fe(OH)2|Fe(OH)3
 At pH=7, Fe will corrode

To protect Fe:
• Apply negative potential
(cathodic protection)
• Increase pH (passivation)
• Apply positive potential
(anodic protection)
• Apply coating/oxidizing
inhibitor.
Activity
Construct the Pourbaix diagram for Zn metal. Show which areas are the
corrosion, passivity and immunity regions.

Given:
Species: Zn, ZnO, ZnO22-, Zn2+
[Zn2+]= 10-6 M; [ZnO22-]= 10-6 M
Standard E :
◦ Zn|Zn2+ = -0.762 V
◦ Zn|ZnO = -0.439 V