Thermodynamics in

Corrosion Engineering

Utility of Thermodynamics in Electrochemistry

Thermodynamic considerations allow the

determination of whether a reaction can
occur spontaneously
If metal dissolution is unfavorable
thermodynamically in a given set of
circumstances the job of the corrosion
engineer is done

Example: Copper in pure deoxygenated water

Objectives

To relate your thermodynamic knowledge

with the thermodynamics of corrosion-related
electrochemistry
To describe the need for and characteristics
of reference electrodes
To describe the origin, use, and limitations of
electrochemical phase diagrams (such as
Pourbaix diagram)

Free Energy: Driving Force of a Chemical Reaction

Spontaneous

Spontaneous

Relation of G and emf

G EnF

G is in Joules
E is emf in volts
n is the number of electrons
involved in the reaction
F is the Faraday (96500
C/equivalent)

The larger the value of E for any cell more is the

tendency for the overall cell reaction to proceed
Ecell = Ecathode - Eanode

The Nernst Equation

General Reaction for a Galvanic Cell

lL mM qQ rR
Nernst Equation:
q

RT aQ .aR ...
EE
ln l m
nF aL .aM ...
0

Half Cell Potential

When a metal M is immersed in an aqueous

electrolyte, it acquires a certain potential. If
the activity of the metal ions M++ in the
aqueous environment is unity, then the
acquired potential is known as standard
potential 0
Potential of each electrode can be calculated
using Nernst equation

Example: Zinc Electrode

2

Zn 2e Zn
RT
Zn
0
Zn Zn
ln 2
2 F Zn

Hydrogen Electrode

It is assumed arbitrarily
that the standard
potential for the
following reaction is
equal to zero at all
temperatures

So

Standard Hydrogen Electrode (SHE)

The potential of the electrode equals zero if the

hydrogen ion activity and the pressure of hydrogen
gas in atmospheres are both unity. This is the
standard hydrogen potential
The half - cell potential for any electrode is equal to
the emf of a cell with the standard hydrogen
electrode as the other electrode.
The half - cell potential for any electrode expressed
on this basis is said to be on the normal hydrogen
scale or on the standard hydrogen scale ,
sometimes expressed as H or ( S.H.E. )

Convention of Signs and Calculation of EMF

Zn2 2e Zn

Zn - 2e Zn

0 0.763 V
0.763 V
0

It was agreed at the 1953 meeting of the

International Union of Pure and Applied Chemistry
that the reduction potential for any half - cell
electrode reaction would be called the potential

Pt; H2,

+
H ,

2+
Zn ;

Zn Cell

Ecell = Ecathode Eanode= ??

Reference Half Cells

It is not always convenient to have a

hydrogen electrode in the laboratory
Other reference half-cells (reference
electrodes) have been introduced.

Calomel reference electrode

Ag-AgCl half cell
The Saturated Copper-Copper Sulfate half cell

Calomel Reference Electrode

Ag-AgCl Reference Electrode

Cu-CuSO4 Half Cell

Number Line for Potential Conversion Among

Different Reference Electrode Scales

Oxygen Electrode

Oxygen Electrode and Differential Aeration Cell

Consider two O2 electrodes:

one in contact with O2 at 1 atm

other in contact with O2 at 0.2 atm

Oxygen Electrode and Differential Aeration Cell

The reaction is not thermodynamically possible as

written
Thus, the electrode 1 is cathode electrode 2 the
anode.
In a differential aeration cell, the electrode in lower
O2 pressure acts as the anode and the one in higher
O2 pressure acts as the cathode

EMF Series

All metals have been arranged in a series according

to their standard potential (0) values.
The more positive value corresponds to noble
metals and the more negative value corresponds to
more reactive metals (when arranged according to
reduction potential)
Of the EMF series if two metals make up a cell,
the more active metal acts as the anode and the
more noble metal of the two will act as cathode

EMF Series

Problems with EMF Series

In real situation, the activities of the metal ions in equilibrium with

the respective metals usually do not equal unity

The position of a metal in the EMF series with respect to another

metal may change because of complex formation as is the case
with tin (Sn) and steel (Fe)

Alloys are not included in the EMF series

In oxidizing environment, some metals undergo passivation and

are known as active-passive metals. Transition metals usually
show passive behaviour in aerated aqueous environment. This
dual position of some metals is not reflected in the EMF series.

Galvanic Series

Galvanic series is an arrangement of both

metals and alloys according to their actual
measured potentials in a particular
environment. There would be one Galvanic
series for each environment

Metals and alloys showing active-passive

behaviour are listed in both active and
passive states.

Galvanic Series in Seawater

Pourbaix Diagram

Marcel Pourbaix developed potential-pH diagrams to

show the thermodynamic state of most metals in
dilute aqueous solutions
With pH as abscissa and potential as ordinate,
these diagrams have curves representing chemical
and electrochemical equilibria between metal and
aqueous environment
These diagrams ultimately show the conditions for
immunity, corrosion or passivation.

Simplified Pourbaix Diagram for Iron

Pourbaix Diagram for Iron

Pourbaix Diagram for Iron at 25C

Benefits of Pourbaix Diagram

Pourbaix diagrams offer a large volume of thermodynamic

information in a very efficient and compact format.
The information in the diagrams can be beneficially used to
control corrosion of pure metals in the aqueous environment
By altering the pH and potential to the regions of immunity and
passivation, corrosion can be controlled. For example, on
increasing the pH of environment in moving to slightly alkaline
regions, the corrosion of iron can be controlled
Changing the potential of iron to more negative values eliminate
corrosion, this technique is called cathodic protection.
Raising the potentials to more positive values reduces the
corrosion by formation of stable films of oxides on the surface of
transition metals

Limitations of Pourbaix Diagrams

These diagrams are purely based on

thermodynamic data and do not provide any
information on the reaction rates

Consideration is given only to equilibrium conditions

in specified environment and factors, such as
temperature and velocity are not considered which
may seriously affect the corrosion rate

Pourbaix diagrams deal with pure metals which are

not of much interest to the engineers