Thermodynamic Aspects of Corrosion

Maria Lekka
Materials science and technology group
Polytechnic Department of Engineering and Architecture
University of Udine
Italy

764977 – mCBEEs - H2020-MSCA-ITN-2017

Chemical reactions obey 2 fundamental laws:
a) The law of mass conservation: matter can be neither created or
destroyed
b) The law of energy conservation: energy can be neither created
or destroyed – it can only be converted from one form to
another

Thermodymanics is the science that studies the interrelationships

between heat, work and the energy content of a system at
equilibrium
• It allows us to determine the spontaneity of a reaction in the
written direction
• Does not provide any information on the rate or pathway of the
reaction (Kinetics)
GIBBS FREE ENERGY
Major goal of chemical thermodynamics is to determine if a
particular reaction or process will occur spontaneously.

A criterion of spontaneity that is based on the state functions of a

system is the Gibbs free energy (G), (for conditions where P and T
are constant)

At constant temperature and pressure,

ΔG = ΔH − TΔS
where all thermodynamic quantities are those of the system

•If ΔG < 0, the reaction occurs spontaneously.

•If ΔG = 0, the system is at equilibrium.
•If ΔG > 0, the reaction goes in the opposite direction
RELATION BETWEEN GIBBS FREE ENERGY AND CELL POTENTIAL

When we have electrochemical reactions, ex. electrochemical cell,

we can express the relation between ΔG and Ecell as:

ΔG= -nFEcell

n: number of moles
F: Faraday constant: the charge of 1 mol of electrons
= 9.64855.104 C/mole

A spontaneous reaction is than characterized by a negative value of

ΔG and a positive value of Ecell
Δ𝐺 𝑜
𝑜
For standard state: ΔG0= -nFE0cell 𝐸𝑐𝑒𝑙𝑙 =−
𝑛𝐹
EMF SERIES – STANDARD HALF-CELL POTENTIALS
𝑜 Δ𝐺 𝑜
𝐸𝑐𝑒𝑙𝑙 =−
𝑛𝐹
• Thermodynamically meaningful
• Gives us information on oxidation
and reduction strength
• Reactants with a potential above
SHE are stronger oxidants than
H+
• Reactants with a potential above
SHE are weaker oxidants than
H+

Standard conditions: 298 K, 1 atm,

activity of ions taking part in the reaction=1
EMF SERIES – STANDARD HALF-CELL POTENTIALS

Calculation of Standard Cell Potentials using

half cell potentials
Zn(s)∣Zn2+(aq, 1 M)∥Cu2+(aq, 1 M)∣Cu(s)

E0Cathode = 0.34 V
E0Anode = -0.76 V

E0Cell = E0Cathode - E0Anode= 1.1 V

EFFECT OF CONCENTRATION ON CELL POTENTIALS – NERNST EQUATION

Electrochemical reaction: aA + bB ⇌ cC + dD
ΔG = Δ𝐺 𝑜 + 𝑅𝑇𝑙𝑛𝑄 Q: reaction quotient – at equilibrium Q=K
𝑜 𝑜 𝑅𝑇
−nF𝐸𝑐𝑒𝑙𝑙 = −𝑛𝐹𝐸𝑐𝑒𝑙𝑙 + 𝑅𝑇𝑙𝑛𝑄 𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑐𝑒𝑙𝑙 − 𝑙𝑛𝑄
𝑛𝐹

𝑐 𝑑
𝑜 𝑅𝑇 𝐶𝐶 ∙ 𝐶𝐷
𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑐𝑒𝑙𝑙 − 2.303 𝑙𝑜𝑔 𝑎 𝑏 Nernst Equation
𝑛𝐹 𝐶𝐴 ∙ 𝐶𝐵

This equation, may be the most important equation of electrochemistry,

allows us
• to calculate potentials under non-standard conditions
• to determine spontaneity of an electrochemical reaction under any
condition as long as the relevant standard electrode potential are
available.
CORROSION REACTIONS
The majority of the corrosion types involves electrochemical reactions
and thus the development on the metals surface of anodic and cathodic
sites
For the occurrence of an electrochemical corrosion reaction
• Minimum two half –cell reactions
• Potential difference between these reactions
• An anode and a cathode (these can be on the same metal)
• Electrolytic conductor
• Electronic conductor
are needed.
When all these requirements are satisfied corrosion takes place
spontaneously
CORROSION REACTIONS
Common Anodic reaction:
M → Mz+ + ze-

Common Cathodic reactions:

Hydrogen evolution reactions
2H+ + 2e- → H2 acid solutions
H2O + e- → 1/2H2 + OH- neutral and alkaline solutions*

Oxygen reduction reactions

O2 + 4H+ + 4e- → 2H2O acid solutions
O2 + 2H2O + 4e- → 4OH- neutral and alkaline solutions*

*In neutral and alkaline solutions the activity of hydrogen ions is too low to take part in the h.e.r.
Thus water molecules act as electron acceptor
THERMODYNAMIC ASPECTS OF CORROSION
• When solution pH increases the nature of corrosion products changes.

• On most of the metals in neutral or near neutral solutions corrosion

products are no more in ionic form - solid reaction (oxides-
hydroxides) products starts to form. This formation and the nature of
the corrosion products can control the corrosion process.

• The stability region of these products and also ionic species

dependent on half-cell potential and pH can be calculated by the help
of thermodynamic principles.

• Potential-pH diagrams are very useful for this purpose, since it is

possible to visualize the stability regions of corrosion products and
their relation with the stability region of water in a glance
POURBAIX DIAGRAMS CONSTRUCTION

• pH is plotted on the x-axis

• Potential is plotted on the y-axis in

Volts relative to the standard
hydrogen electrode SHE. Potential
can be thought as the oxidizing
power of the solution
POURBAIX DIAGRAMS CONSTRUCTION – H2O EQUILIBRIA

2H+ + 2e- ↔ H2
𝑅𝑇 𝑃𝐻2 𝐸𝑜 =0
𝐸𝑟𝑒𝑣 = 𝐸𝑜 − 𝑙𝑛 2 H2O is stable
𝑧𝐹 𝑎𝐻 +
H+ OH-
0.059 𝑃𝐻2 𝑃𝐻2 =1𝑎𝑡𝑚
𝐸𝑟𝑒𝑣 = − 𝑙𝑜𝑔 2
2 𝑎𝐻 +
H2 is stable
0.059 𝑝𝐻=−𝑙𝑜𝑔𝑎𝐻+
𝐸𝑟𝑒𝑣 =2 𝑙𝑜𝑔𝑎𝐻 +
2

𝐸𝑟𝑒𝑣 = −0.059𝑝𝐻
POURBAIX DIAGRAMS CONSTRUCTION – H2O EQUILIBRIA
O2 + 4H+ + 4e- ↔ 2H2O
O2 is stable
2
𝑅𝑇 𝑎𝐻 2𝑂
𝐸𝑜 =1.23𝑉
𝐸𝑟𝑒𝑣 = 𝐸𝑜 − 𝑙𝑛 4
𝑧𝐹 𝑃𝑂2 𝑎𝐻 + H2O is stable

2
0.059 𝑎𝐻 2𝑂
𝑃𝑂2 =1𝑎𝑡𝑚,𝑎𝐻2 𝑂 =1
𝐸𝑟𝑒𝑣 = 1.23 − 𝑙𝑜𝑔 4
4 𝑃𝑂2 𝑎𝐻 +
H2 is stable
0.059 𝑝𝐻=−𝑙𝑜𝑔𝑎𝐻+
𝐸𝑟𝑒𝑣 = 1.23 + 4 𝑙𝑜𝑔𝑎𝐻 +
4

𝐸𝑟𝑒𝑣 = 1.23 − 0.059𝑝𝐻

POURBAIX DIAGRAMS CONSTRUCTION – METAL EQUILIBRIA (ex. Zn)

Zn2+ + 2e- ↔ Zn

𝑅𝑇 𝑎𝑍𝑛 𝐸𝑜 =−0.7628𝑉
𝐸𝑟𝑒𝑣 = 𝐸𝑜 − 𝑙𝑛
𝑧𝐹 𝑎𝑍𝑛2+

0.059 𝑎𝑍𝑛 Zn2+ is stable

𝐸𝑟𝑒𝑣 = −0.7628 − 𝑙𝑜𝑔
2 𝑎𝑍𝑛2+
𝑎𝑍𝑛 =1, 𝑎𝑍𝑛2+ =10−6 ∗ 0.059 Zn is stable
𝐸𝑟𝑒𝑣 = −0.7628 + ∙6
2

𝐸𝑟𝑒𝑣 = −0.9398𝑉

* Arbitrarily set to 10-6M

POURBAIX DIAGRAMS CONSTRUCTION – METAL EQUILIBRIA (ex. Zn)

Zn(OH)2 + 2H+ + 2e- ↔ Zn + 2H2O

2
𝑅𝑇 𝑎𝑍𝑛 𝑎𝐻 2𝑂
𝐸𝑜 =−0.439
𝐸𝑟𝑒𝑣 = 𝐸𝑜 − 𝑙𝑛 2
𝑧𝐹 𝑎𝑍𝑛(𝑂𝐻)2 𝑎𝐻 +

0.059 1
𝐸𝑟𝑒𝑣 = −0.439 − 𝑙𝑜𝑔 2 Zn(OH)2 is stable
2 𝑎𝐻 +

0.059 𝑝𝐻=−𝑙𝑜𝑔𝑎𝐻+ Zn is stable

𝐸𝑟𝑒𝑣 = −0.439 + 2 𝑙𝑜𝑔𝑎𝐻 +
2

𝐸𝑟𝑒𝑣 = −0.439 − 0.059𝑝𝐻

POURBAIX DIAGRAMS CONSTRUCTION – METAL EQUILIBRIA (ex. Zn)
ZnO22- + 4H+ + 2e- ↔ Zn + 2H2O
2
𝑅𝑇 𝑎𝑍𝑛 𝑎𝐻 2𝑂
𝐸𝑜 =−1.215
𝐸𝑟𝑒𝑣 = 𝐸𝑜 − 𝑙𝑛 4
𝑧𝐹 𝑎𝑍𝑛𝑂2− 𝑎𝐻 +
2

𝑎𝑍𝑛𝑂2− =10−6 ZnO22- is stable

0.059 1 2
𝐸𝑟𝑒𝑣 = −1.215 − 𝑙𝑜𝑔 4
2 𝑎𝑍𝑛𝑂2− 𝑎𝐻 +
2

Zn isZnstable
is stable
0.059 0.059
𝐸𝑟𝑒𝑣 = −1.215 + 4 𝑙𝑜𝑔𝑎𝐻 + − 6
2 2
𝑝𝐻=−𝑙𝑜𝑔𝑎𝐻+
𝐸𝑟𝑒𝑣 = −1.392 − 0.118𝑝𝐻
POURBAIX DIAGRAMS CONSTRUCTION – METAL EQUILIBRIA (ex. Zn)
Zn2+ + 2H2O ↔ Zn(OH)2 + 2H+

Zn(OH)2 is stable
Zn2+ is stable
2 2
𝑎𝑧𝑛(𝑂𝐻)2 𝑎𝐻 + 𝑎𝐻 +
𝐾= 2 𝐾=
𝑎𝑍𝑛2+ 𝑎𝐻 2𝑂
𝑎𝑍𝑛2+

𝑙𝑜𝑔𝐾 = 2𝑙𝑜𝑔𝑎𝐻 + − 𝑙𝑜𝑔𝑎𝑍𝑛2+

𝑎𝑍𝑛2+ =10−6 , 𝐾=10−10.6

𝑝𝐻 = 8.3
POURBAIX DIAGRAMS CONSTRUCTION – METAL EQUILIBRIA (ex. Zn)

Zn(OH)2 ↔ ZnO22- + 2H+

Zn(OH)2 is stable

ZnO22- is stable
2
𝑎𝑧𝑛𝑂22− 𝑎𝐻 +
2
𝐾= 𝐾 = 𝑎𝑧𝑛𝑂22− 𝑎𝐻 +
𝑎𝑍𝑛(𝑂𝐻)2

𝑙𝑜𝑔𝐾 = 2𝑙𝑜𝑔𝑎𝐻 + + 𝑙𝑜𝑔𝑎𝑍𝑛𝑂22−

𝑎𝑍𝑛𝑂2− =10−6 , 𝐾=10−29.8

2 𝑝𝐻 = 11.9
POURBAIX DIAGRAMS CONSTRUCTION – Zn

Corrosion is
thermodynamically
impossible
POURBAIX DIAGRAMS CONSTRUCTION – Zn

Corrosion is possible
with the reduction of
H+
POURBAIX DIAGRAMS CONSTRUCTION – Zn

Corrosion is possible
with the reduction of
O2
POURBAIX DIAGRAMS CONSTRUCTION – Zn

Corrosion requires a
strong oxidant
POURBAIX DIAGRAMS CONSTRUCTION – Zn

Corrosion is
thermodynamically
possible, but could
be hindered by the
corrosion products
POURBAIX DIAGRAMS CONSTRUCTION – PRACTICAL RULES

• The horizontal lines represent redox reactions which do not involve H+

or OH-

• The vertical lines represent acid-base equilibria, characterized by a

solubility product

• The sloped lines represent redox reactions which involve metal ions
and water

• The negative slope indicates that the alkaline environment generally

stabilizes the oxidized species
POURBAIX DIAGRAMS – MAIN DOMAINS
Immunity domain: The solid metal form is the
thermodynamically more stable. Corrosion is
thermodynamically impossible

Corrosion domain: Ions are thermodynamically

more stable and the corrosion products are
soluble in water

Passivation domain:
The solid stable form is an oxide, hydroxide,
an hydride or a salt which tends to cover the metal isolating it from the
environment. The corrosion or passivity depends on the nature of the solid
product, the adhesion to the substrate and the kinetics of the reaction.
The oxide could form a continuous, porous free, adherent to the metal substrate
film which prevents the further corrosion (passivity)
The oxide could be porous, and prevent only partially the contact between the
electrolyte and the substrate (corrosion).
Passivation does not necessarily imply the absence of corrosion
THERMODYNAMIC NOBILITY AND PRACTICAL NOBILITY
Thermodynamic nobility
• A metal is thermodynamically noble or non-noble according as its immunity
domain shows or does not show a section in common with the
thermodynamic stability domain of water (area between lines a and b)
• The nobility of a metal is greater, the largest the surface common both to its
immunity domain and the stability domain of water
Practical nobility
Not considering the kinetics factors and assuming that the passivating films are
perfectly protective we consider a metal more noble:
• The greater the surface common both to the total of the immunity and
passivation domains and the stability domain of water
• In the case of metals where these surfaces are perceptibly identical, it is
accepted that the “practical nobility” is greater the more the immunity and
passivation domains extended below and above the stability domain or water
and the more these domains overlap the section of the diagrams which
corresponds to pH values between 4 and 11 (most frequently met in practice)
THERMODYNAMIC NOBILITY AND
PRACTICAL NOBILITY
POURBAIX DIAGRAMS – LIMITATIONS

• Equilibrium is assumed
• The diagrams are derived for specific temperature and pressure
conditions and species concentrations
• Most diagrams consider pure metals and pure water. Additional
computations are needed if other species are involved
• In the areas where Pourbaix diagrams show oxides to be
thermodynamically stable, these oxides are not necessarily of a
protective (passivating) nature
• No information about kinetics is given
POURBAIX DIAGRAMS – USES
• Corrosion prediction and corrosion protection
• Electrodeposition
• Geosciences
POURBAIX DIAGRAMS – EXAMPLES

1.Fe2++2e−→Fe(s)
2.Fe3++e−→Fe2+
3.2Fe3++3H2O→Fe2O3(s)+6H+
4.2Fe2++3H2O→Fe2O3(s)+6H++2e−
5.2Fe3O4(s)+H2O→3Fe2O3(s)+2H++2e−
POURBAIX DIAGRAMS – EXAMPLES
POURBAIX DIAGRAMS – EXAMPLES
POURBAIX DIAGRAMS – EXAMPLES
POURBAIX DIAGRAMS – ROLE OF CONCENTRATION ON STABILITY AREA
POURBAIX DIAGRAMS – ROLE OF CONCENTRATION ON STABILITY AREA
POURBAIX DIAGRAMS – ROLE OF TEMPRATURE

The construction of Pourbaix diagrams at elevated temperatures is

similar to this at 25°C, except it is necessary to add a temperature
correction for the free energy change of each reaction. The
temperature affects:

• The electrode potential E of the electrochemical reactions

through the relationship ΔG=-nFE, in which the free energy
change ΔG is a function of temperature
• The Nernst equation, through the factor 2.303RT/F
• The equilibrium constant K in acid-base reactions through the
relationship ΔG=-RTlnK, changing both ΔG and of course T
POURBAIX DIAGRAMS – ROLE OF TEMPERATURE

25°C 200°C

H. E. Townsend, Jr., Corros. Sci., 10, 343 (1970)

POURBAIX DIAGRAMS – ROLE OF TEMPERATURE

J. B. Lee, Corrosion, 37, 467 (1981)

POURBAIX DIAGRAMS – ROLE OF TEMPERATURE

J. B. Lee, Corrosion, 37, 467 (1981)

POURBAIX DIAGRAMS – ROLE OF OTHER SPECIES
POURBAIX DIAGRAMS – ROLE OF OTHER SPECIES
[Fe 2+2+
[Fe ]=10 -6M
]=10 -6M

[CO32-]=1M
T=25°C
T=25°C
[Fe2+]=10-6M
[CO32-]=0.1M
T=25°C
POURBAIX DIAGRAMS – ROLE OF OTHER SPECIES

M. H. Froning, M. E. Shanley, E.D. Verink, Corrosion Science, 1976, 16, 371-377

POURBAIX DIAGRAMS – ROLE OF OTHER SPECIES
[Cu2+]=10-6M
T=25°C

[Cu2+]=10-6M
[Cl-]=0.1M
T=25°C

[Cu2+]=10-6M
[Cl-]=1M
T=25°C
POURBAIX DIAGRAMS – ROLE OF OTHER SPECIES

Pb in H2O Pb in H2O with CO2

POURBAIX DIAGRAMS – ROLE OF OTHER SPECIES
[Ag+]=10-6M
T=25°C

[Ag+]=10-6M
[S2-]=1M
T=25°C
POURBAIX DIAGRAMS – USES
• Corrosion prediction and corrosion protection
1. The resistance of metals to uniform corrosion in aqueous solutions.

2. The basis for establishing which metals can be expected to have

passivity over a wide range of conditions of pH and potential.

3. Evaluation of the possible use of oxidizing inhibitors.

4. Identification of the set of internal conditions within a localized

corrosion cell
POURBAIX DIAGRAMS – USES
• Corrosion prediction and corrosion protection
POURBAIX DIAGRAMS – USES
• Electrodeposition
1. Define the cathodic and anodic processes in a range of pH

2. Find the appropriate complexes for the deposition of alloys

POURBAIX DIAGRAMS – USES
• Electrodeposition of Ni from simple salts
Cathodic reactions
At pH ~ 4.5 and EH ~ -0.4V we can
have the reduction of Ni++, H+ and O2
but the required overpotentials for O2
and H+ are considerable higher than
those of Ni2+. Good efficiency
At pH ~ 2 and EH ~ -0.4V the amount
of reduced H+ is much higher. Lower
efficiency and evolution of H2
At pH ~ 6 and EH ~ -0.3V there is no H2
evolution but Ni(OH)2 can be formed
and codeposited in the Ni deposit
POURBAIX DIAGRAMS – USES
• Electrodeposition of Ni from simple salts
Anodic reactions (soluble anode)
At pH above 6 the anode passivates

At pH ~ 4.5 there is the dissolution of

the anode to Ni++. Also in this case
there could be passivation of the
anode as the required overpotentials
and current densities are quite high.
Addition of Cl- in the baths or S in the
anodes
POURBAIX DIAGRAMS – USES
• Electrodeposition of metals using complex salts

Mardsen J., House, I., The Chemistry of Extraction Gold, SME Pub, 2nd edn, 1974
H.H. Huang, The Eh-pH Diagram and Its Advances, Metals 2016, 6, 23; doi:10.3390/met6010023
POURBAIX DIAGRAMS – USES
• Electrodeposition of alloys
POURBAIX DIAGRAMS – USES
• Electrodeposition of alloys
POURBAIX DIAGRAMS – QUESTIONS
Suppose that an acid flux is inadvertently left on the surface of a silver contact
and that in the presence of a thin film of condensed moisture, the acid residue
has a pH of 5.0. Under what range of electrode potentials could the corrosion of
silver occur in the thin-film electrolyte?
POURBAIX DIAGRAMS – QUESTIONS
Palladium is a noble metal. However, the Pourbaix diagram for palladium
contains a region where palladium is subject to corrosion. Can palladium
corrode by the following reaction:
Pd(s) + 2H+(aq) −→ Pd2+(aq) + H2(g)
POURBAIX DIAGRAMS – QUESTIONS
If iron is immersed in a solution of pH 3.0, what electrode potential must be
maintained to prevent the evolution of hydrogen gas?
POURBAIX DIAGRAMS – QUESTIONS
Will copper corrode in pure O2-free water at pH 4?
POURBAIX DIAGRAMS

• The Pourbaix diagrams express what is energetically possible or

energetically impossible

• They do not necessarily show what actually occurs (numerous

electrochemical reactions are irreversible)

• Experimental kinetic studies are required

• Pourbaix diagrams can serve as a guide in carrying out the

experimental studies and in the interpretation of the results
USEFULL FREE-SOFTWARES

Hydra – Medusa
https://sites.google.com/site/chemdiagr/

Phreeplot
http://www.phreeplot.org/
FOR MORE DETAILED READING…

M. Pourbaix, “Atlas of Electrochemical Equilibria in Aqueous

Solutions”, National Association of Corrosion
Engineers, Houston, TX (1974).

E. McCafferty, Introduction to Corrosion Science, ISBN 978-1-

4419-0454-6, Springer New York Dordrecht Heidelberg
London