Defence University

College of Engineering
Department of Chemical Engineering
Specialization: Electrochemical Engineering

Advances in Corrosion Engineering(CE-7341)

Chapter 3. Corrosion Thermodynamics

Instructor: Wondalem Misganaw(PhD., M.Tech, B.Tech)

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 Introduction
 Corrosion studies can be carried-out by two methods
1. Thermodynamics
2. By electrode Kinetics
 Thermodynamics give the change in energy state , also predicts the
directions of a reactions.
 For spontaneous reactions , the systems must decrease their Free-
energy and move to a lower energy state, e.g. Corrosion is a
spontaneous reaction.
 For non-spontaneous reactions energy must be added to the system
in order to facilitate the reaction .
Fe → Fe2O3 spontaneous ( - ∆G )
Fe ← Fe2O3 Non-spontaneous ( + ∆G )
 By thermodynamic rate of reaction can not be predicted.
2 Free Energy: Driving Force of a Chemical Reaction
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Examples

Mg+H2O(l) +½O(g)→Mg(OH)2 (s) …… ∆Go = - 596,600 J Spontaneous

Cu+H2O(l) +½O(g)→Cu(OH)2 (s) …… ∆Go = - 119,700 J Spontaneous
Au+3/2H2O(l)+3/4O(g)→Au(OH)3 (s) …… ∆Go = + 65,700 J Non-Spontaneous

Spontaneous
direction

Fig.(1) mechanical analogy of free Fig.(2) Effect of reaction path on reaction rate.
energy change.
 Corrosion Thermodynamics
 Corrosion is thermodynamically driven to lower the overall
energy of the system
 Involves electron/charge transfer
 Controls the spontaneous direction for corrosion
 Thermodynamics provides an understanding of the energy
changes involved in corrosion
 Thermodynamics show how conditions may be adjusted to
prevent corrosion, i.e., ΔG>0
 Thermodynamics can indicate corrosion is possible, i.e., ΔG<0,
but thermodynamics cannot predict the rate.
 At equilibrium condition, ΔG = 0
 Change in E or the electron activity or availability at a metal
surface has a profound effect on corrosion rate

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Corrosion Thermodynamics

1 – Spontaneous direction of a reaction .

2 – Estimating the composition of corrosion products.
3 – Predicting the environment changes that will reduce the
corrosion rate.
2 & 3 could be explained by the potential vs. pH diagram of
a metal ( also called pourbaix diagrams ) . e.g. iron in water .
 Corrosion Thermodynamics
Redox potential or e.m.f. series is a thermodynamic function – redox
has been utilized to predict the corrosivity of metals in various
environments. e.g. metals (-ve) to hydrogen electrode would corrodes
in acids but metals (+ve) to hydrogen electrode would not corrode in
the absence of oxygen.
( -ve ) such as ( Fe or Zn ) + Acid → Corrosion
( +ve ) such as ( Cu or Ag ) + Acid → no corrosion
( Cu or Ag ) + Acid + O2 → Corrosion would happen in this case .
Cu + H2SO4 → No corrosion ( Cu/Cu+2 more + than H2/ H+ )
Cu + H2SO4 + O2 → 2CuSO4 + 2H2O ( O2/ H2O more + than Cu/Cu+2 )

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 Cell potentials
The cell potential, E, is a measure of how well a cell reaction can
push and pull electrons through a circuit
The electrical energy generated by the spontaneous reaction is
proportional to the cell potential.
For the example, the reactions occuring are:
Cathode: Cu2+(aq) + 2e-  Cu(s)
Anode: Zn(s)  Zn2+(aq) + 2e-
The shorthand notation for this cell is:

Zn(s) | Zn2+(aq) || Cu2+(aq) | Cu(s)

The standard cell potential (the cell potential measured when all the
species are in their standard states) is given by:

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E°cell = E°cathode + E°anode
 Examples
Example 1 : A galvanic cell consist of ( Zn ) electrode in( ZnSO4 ) solution with ( 1
mole ) concentration . The other is of ( Ni ) electrode in ( NiSO4 ) solution with ( 1
mole ) concentration . The two electrodes are separated with porous partition to
prevent mixing of the two solutions . The two electrodes are contacted with
conductive wire . Find.

a ) On which electrode the

oxidation reaction will be .
b ) Which electrode will be the Zn electrode Ni electrode

anode .
c ) Which electrode will
corroded . NiSO4
d ) what is the EMF for this
galvanic cell , circuit close.

Ni2+
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 Solution :
The half cells reactions are :

(a)Oxidation reaction will take place on Zn electrode .Because the

potential deference in Zn half cell more negative (- 0.763 V)
compare with (-0.250 V) for Ni half Cell .
(b) From previous answer, Zn electrode is the anode , because the
oxidation reaction take place on anode electrode.
(c) In galvanic cell , the anode electrode is the corroded electrode , for
that Zn electrode will corroded.
(d) Cell potential is the sum of the two half cells potential.

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 The result of the Cell reaction . Ni potential changed with respect to standard
potential cell .This is due to its potential in the EMF series . Also if we
connect Pt electrode with Cu electrode we get :
Pt+2+2e Pt Eo=+1.200V
Cu+2+2e Cu Eo=+0.337V
By subtraction the lower potential from the higher we get
Pt+2+2e Pt Eo=+1.200V
Cu Cu+2+2e Eo=-0.337V
Eo= +0.863V

If the galvanic Cell contain two electrodes , One of them with ( - ve ) potential
and the other with ( + ve ), such as Zinc with Copper .
Zn+2+2e Zn Eo=-0.763V
Cu+2+2e Cu Eo=+0.337V
In this case ,if we subtract Cu potential from Zn potential the result is :
Cu+2+2e Cu Eo=+0.337V
Zn Zn+2+2e Eo=+0.763V
Eocell=+1.10V

We change reduction sign to get the cell potential difference .

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Cell potential and Free energy
 The cell in open circuit generates an electromotive force (emf) or
potential or voltage. This is the potential to perform work
 Energy is charge moving under applied voltage

1J  1C  1V G   nFE
Standard conditions (1 M, 1 atm, 25°C)

G   nFE
where ΔG° is the change in Gibbs Free Energy( J)
n is the number of moles of electrons
F is the Faraday (96500 C/equivalent)
E°cell is the standard cell potential (V)
 Have relationship between Gibbs Free Energy and
Equilibrium constant:
ΔG° = - RT lnK
ΔG for a reaction depends on the concentration by:
ΔG = ΔG° + RT ln Q where Q is the reaction quotient = [product]
[reactant]

But ΔG = -n F Ecell and ΔG° = - n F E°cell

-nFEcell = -nFE°cell + RT ln Q

Ecell = E°cell – RT ln Q (Nernst Equation)

nF

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 The electromotive force series
 When a metal is immersed in an electrolyte, a dynamic
equilibrium is established across the interface with a potential
difference between the metal and electrolyte.
 If a metal is immersed in a solution of its own ions , such as
Zn in ZnSO4 solution ,or copper in CuSO4 the potential
obtained is called the reversible potential ( Erev ) .
 If the metals are in their standard stats , such that activities of
the metallic ions are equal to unity or gases are at 1 bar
pressure , the potentials obtained are called' Standard
Electrode Potentials '.
 A standard potential refers to the potential of pure metal
measured with reference to a hydrogen reference electrode (
H2 / H+ ) which is arbitrarily defined as Zero .It is not possible
to establish a reversible potential for alloys containing two or
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more reactive components.
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The electromotive force series

 The Electromotive Series or emf series is an orderly arrangement
of the standard Electrode Potentials of all metals.
 The electrical potential difference between an electrode and a
reference electrode.
 We cannot measure the absolute potential of an electrode;
therefore, the electrode potential must always be referred to an
"arbitrary zero point", defined by the potential of the reference
electrode.
 Consequently, it is very important always to note the type of
reference electrode used in the measurement of the electrode
potential. Not to be confused with electrochemical potential.
 The Electro Motive Series ( EMF )

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 The Standard EMF Series

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 Limitations of the EMF Series
 Only pure metal are listed in emf series, because it is not possible to

establish a reversible potential for alloys containing two or more

reactive components. But in most engineering applications the
galvanic couple usually has one or more alloys.

 The emf series takes no account of the effect of surface films which

may form on metals under a variety of conditions.

 The emf series takes no account of the effect of pH .

 Effect of temperature has not been considered in the emf series .

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 Galvanic series of metals and alloys
 In actual corrosion problems, galvanic coupling between metals in

equilibrium with their ions rarely occurs.

 In general, the positions of metals and alloys in the galvanic series

agree closely with their constituent elements in the emf series .

 To overcome some of limitations of the emf series the so-called

galvanic series can be used.

 This series is an arrangement of metals and alloys in accordance with

their actual measured potentials in a given environment.

 The galvanic series of metals in contact with sea water is given.

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Applications of Galvanic Series
1. Metals and alloys at the top of the series , i. e., at the noble end
are corroded least , while metals and alloys at the bottom , i.e.,
at the active end are corroded to the maximum extent.

2. The further apart metal and alloys are in the series, the greater is
the potential generated. Therefore, metals and alloys which are
further apart in the series should not be connected together.

3. When metals and alloys within the same group are coupled
together there is little danger of corrosion.
 Limitations of Galvanic Series
1. In case of EMF series only one series exists but there can
be several galvanic series because of differing tendencies of
various environments to form surface films.
2. Galvanic Series like EMF series cannot be used to predict
the effect of a change in solution pH on corrosion tendency
 To overcome some of limitations of the emf and galvanic
series a system of showing the effect of both potential and
pH has been evolved by Pourbaix in the form of Potential/pH
diagrams.
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 Pourbaix diagram
 Pourbaix diagram (Electrode potential / PH diagram) is a
graphical presentation of the thermodynamic equilibrium states
of a metal-electrolyte system.
 Pourbaix diagrams are plotted in the axes Electrode potential of
the metal vs. PH of the electrolyte.
 Pourbaix diagram maps out possible stable (equilibrium) phases
of an aqueous electrochemical system.
 Predominant ion boundaries are represented by lines. As such a
Pourbaix diagram can be read much like a standard phase
diagram with a different set of axes.
 Similarly to phase diagrams, they do not allow for reaction
rate or kinetic effects.
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.
 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.
 Oxidizing conditions are described by the top part of the
diagram (high positive electrode potential) and Reducing
conditions are described by the bottom part of the diagram
(high negative electrode potential).

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 Pourbaix diagram
 Acidic solutions are presented in the left side of the diagram (pH
lower than 6) and Alkaline solutions are presented in the right side
of the diagram (pH higher than 6).
 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.
 Normally the Poubaix diagrams are built for the water solutions
with the concentrations of metal ions 10-6M and at the temperature
298K (77ºF/25ºC).
 These diagrams ultimately show the conditions for immunity,
corrosion or passivation

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 Pourbaix Diagram for Iron

Corrosion
Passivation

Corrosion
Immunity

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 Pourbaix Diagram for Fe-H2O at 25 °C

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 Pourbaix Diagram Domains
 Diagrams have three domains:
1. Immunity – region of
thermodynamic stability of the
pure metal. Corrosion is
thermodynamically
impossible.
2. Corrosion - region of
thermodynamic stability of the
metal ion and dissolution will Passivation
occur. As iron is transformed
to soluble species, it is
expected that iron would
corrode.
3. Passivity - region of
Immunity Corrosion
thermodynamic stability of the
metal oxide. Corrosion is
mitigated by the formation of a
31 “passive” protective oxide.
 Benefits of Pourbaix Diagram
 According to E/pH diagram, following methods can be used to reduce
corrosion
1. Pourbaix diagrams offer a large volume of thermodynamic
information in a very efficient and compact format.
2. The information in the diagrams can be beneficially used to control
corrosion of pure metals in the aqueous environment
3. 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, so that a passive film is formed and the corrosion of iron
can be controlled.
4. Changing the potential of iron
 By lowering the electrode potential down into the region of
immunity, e.g., by cathodic protection.
 By raising the electrode potential up into region of passivity ,e .g
., by anodic protection.
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 Limitations of Pourbaix Diagrams
1. These diagrams are purely based on thermodynamic data and do
not information about the kinetic parameters of the corrosion reactions
(reaction rates).
2. Consideration is given only to equilibrium conditions in specified
environment and factors, such as room temperature. Other factors such
as change in temperature and velocity are not considered which may
seriously affect the corrosion rate
3. The effect of impurities in solution is difficult to consider.
4. 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.
5. The diagram do not take into account non-ideal behavior of aqueous
solutions.
6. Pourbaix diagrams deal with pure metals which are not of much interest
to the engineers (The effect of alloy element has not been considered)
7. Some thermodynamic data used for building diagrams are not precise
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enough.
End of Chapter 3

Thank You