Assignment 1 Key learning objectives

Anke Fan 45205824

1. Use of E-log(i) diagrams to explain the kinetics of corrosion

When a corrosion take place in the surface of metal, it involves both cathodic and anodic
process with different equilibrium potentials. When it comes to kinetics of corrosion,
we must introduce current density i (current density i = current/surface area) as well as
the corrosion rate to determine the main chrematistics of the whole corrosion process
on the purpose of slowing down the corrosion rate in practical metal protection.

In real electronic process, cathodic and anodic process won’t work in the condition of
the equilibrium potentials and exchange current density. The actual potential will
deviation from equilibrium potential, which is the polarization. The overpotential value
𝜂 = 𝐸 − 𝐸0 . uulter-Volumer is introduced to find out the relationship between the
overpotential and real current density i.

The E-log i diagram also called Evans diagram is plotted through simplifying the
𝑖
uutler-Volmer Equation to Tafel equation (𝜂 = 𝛽𝑎(𝑐) log 𝑖 ) and then expressing the
0

relationship in the form of y=mx+b ( 𝐸 = 𝐸0 + 𝛽𝑎 (𝑐) (log 𝑖 − log 𝑖0 ) ). The Evans

diagram shows how potential changes with the current density of each process (anodic
and cathodic) varies, hence identifying corrosion working conditions.

Figure 1 Evans diagram

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Through a zinc corrosion in an oxygen-free acid. We know that two processes take place:

𝑍𝑛 → 𝑍𝑛2+ + 2𝑒 −

2𝐻 + + 2𝑒 − → 𝐻2

When two half-cell reactions occur simultaneously on a metal surface, both of them
will change the potential to the corrosion potential. We can see from the diagram that
each electrode has 2 corresponding slopes which is oxidation (upward) reaction and
reduction (downward) reaction.

When we extend hydrogen cathode line and the zinc anode line, the corrosion potential
Ecorr & corrosion current density icorr will be known at the crossing point. At the
corrosion potential all the rates (current densities) are equal: icathode = ianode = icorr.

Some other information we can obtain from the diagram:

1. Each side reaction starts from the standard potential and then polarizes to the new
potential Ecorr
2. Each reaction accelerates the other reaction. The exchange current density of H+, it
goes all the way to icorr. It’s the same with zinc, exchange current density shifts to
the right side which is new value icorr

Figure 2 Evans diagram of Zinc in acid

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The experimental polarization curve is based on mixed potential theory and Evans
diagram. From the diagram, we can obtain the data of Ecorr as well as icorr. uy using icorr,
we can calculate the corrosion rate CR (CR=iEw/FD).

Figure 3 Example of experimental polarization curve

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2. The construction and usefulness of the E-pH diagram for Fe
According to the Nernst equation, we can get the relationship between the potential and
the concentration of the H+. Through a typical reaction as shown below, we can obtain
the expression of potential E by connecting it with the pH value.

uy identifying the reactions take place under different conditions, we can plot the
relevant curve in the E-pH diagram which is also known as the Pourbaix diagram. This
diagram reflects the relationship between the equilibrium potential of the electrode
system and the pH value of the dielectric system as well as reveals the intendency of
the occurrence of corrosion under different pH values and potentials. The Pourbaix
diagram for iron is shown below:

Figure 4 Pourbaix diagram for iron at 25℃

Line a and line b are the equilibrium potential versus pH of hydrogen electrode and
oxygen electrode respectively. The diagram shows different products of Fe-H2O system

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under different pH values and potentials at 25℃: Fe(s), Fe2+, Fe3+, Fe (OH)3, Fe (OH)2,

HFeO2-

The horizontal lines which are below -0.4V are the conversing reaction of Fe2+ to Fe
under different concentration of Fe2+ ion (100,10-2,10-4,10-6mol/L). This reaction is
merely relevant with potential instead of pH value of solution.

𝐹𝑒 2+ + 2𝑒 − → 𝐹𝑒

The vertical lines above 0.8V reveal the reaction below:

𝐹𝑒 3+ + 3𝐻2 𝑂 → 𝐹𝑒(𝑂𝐻)3 + 3𝐻 +

These reactions under different concentration Fe3+ are only connected with the pH of
solution instead of potential. Another reaction between pH=6~10, E=-0.6~0V shows
the conversion between Fe2+ and Fe (OH)2:

𝐹𝑒 2+ + 2𝐻2 𝑂 → 𝐹𝑒(𝑂𝐻)2 + 2𝐻 +

The slopping lines are reactions with both acid-base and redox (both pH and potential
related). These reactions reveal the conversion of two products which locates above and
below the slopping lines:

𝐹𝑒(𝑂𝐻)3 + 3𝐻 + + 𝑒 − → 𝐹𝑒 2+ + 3𝐻2 𝑂

𝐹𝑒(𝑂𝐻)3 + 𝐻 + + 𝑒 − → 𝐹𝑒(𝑂𝐻)2 + 𝐻2 𝑂

𝐹𝑒(𝑂𝐻)2 + 2𝐻 + + 2𝑒 − → 𝐹𝑒 + 2𝐻2 𝑂

𝐻𝐹𝑒𝑂2 − + 3𝐻 + + 2𝑒 − → 𝐹𝑒 + 2𝐻2 𝑂

𝐹𝑒(𝑂𝐻)3 + 𝐻 + + 2𝑒 − → 𝐻𝐹𝑒𝑂2 − + 𝐻2 𝑂

Through plotting curves on the E-pH diagram by combining reactions as well as the
Nernst equations. We can see several areas divided by different lines and curves which
is shown in figure 5.
The area on the left side in the diagram where Fe2+ and Fe3+ exist are corrosion area
which is above -0.6V and pH<9.5. In practical use, we must avoid the corrosion taking

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place in this area. On the right side of the diagram, we can see the production of Fe
(OH)3 and Fe (OH)2, which means the passivation takes place on the metal surface. And
the passivation film could protect the iron metal from corrosion. We could also notice
that when the negative potential is added under -0.5V, it’s hard for iron metal to corrode.
The iron metal will be in a stable state. At very alkaline conditions, complex HFeO2-
ions occur. As a result, the common use of this diagram is the advice for the protection
in practical use:
1) Iron can be protected by cathodic protection criterion through changing the
potential till its potential is below the oxidation potential of the metal. A common
practice is connecting a more active metal such as Mg or Zn to the iron or steel
object.
2) Anodic passivation protection criterion is keeping the iron metal under relative
alkaline and high positive potential to ensure the formation of passivation film.
3) Limitation of Pourbaix diagram still exists. Corrosion rate, effect of other ions,
poverty of passivation film and temperature should be further studied before
practical metal protection.
4)

Figure 5 Different zones of Pourbaix diagram for iron

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Reference:
uranko N. Popov, 2015. Chapter 2 - Thermodynamics in the Electrochemical Reactions
of Corrosion. In Corrosion Engineering. Elsevier u.V, pp. 29–92.

Iron E-pH (Pourbaix) Diagram, Module Four of CCE 281 Corrosion: Impact, Principles,
and Practical Solutions 2020, corrosion doctors, viewed on 14th April 2021,
<https://www.corrosion-doctors.org/Corrosion-Thermodynamics/Potential-pH
diagram-iron.htm>

Jeffrey D. Venezuela 2021, Week 4 Kinetics of Corrosion (Part II): Polarization and
Mixed Potential Theory, PowerPoint slides, University of Queensland, urisbane.

Pedeferri, Pietro, 2018. Evans Diagrams. In Corrosion Science and Engineering.

Engineering Materials. Cham: Springer International Publishing, pp. 103–118.

Pourbaix Diagrams, The LibreTexts libraries 2020, viewed 14th April 2021, the
Department of Education Open Textbook Pilot Project,
<https://chem.libretexts.org/uookshelves/Inorganic_Chemistry/uook%3A_Introducti
on_to_Inorganic_Chemistry/04%3A_Redox_Stability_and_Redox_Reactions/4.06%3
A_Pourbaix_Diagrams>

Rahim.rahman 2017, Corrosion: Evans Diagram, Steemit, viewed on 14th April 2021,
< https://steemit.com/corrosion/@rahim.rahman/corrosion-evans-diagram>

Ruth Knibbe 2021, Week 3 Thermodynamics of Corrosion, PowerPoint slides,

University of Queensland, urisbane.

Verink, E. D, 2011. Simplified Procedure for Constructing Pourbaix Diagrams. In

Uhlig's Corrosion Handbook. Hoboken, NJ, USA: John Wiley & Sons, Inc, pp. 93–101.