Modern Theory of Corrosion –

Principles
By
Dr. Achinta Bera
School of Petroleum Technology
Gandhinagar-382007
 Date: 05 Feb 2021
Principles
Thermodynamic principles

Electrode kinetics principles

A chemical reaction is a reaction in which chemical bodies (neutral

molecules or negatively or positively charged ions) participate
whereas an electrochemical reaction is a reaction in which both
chemical species and free electron charges rake part.

Electrochemical reactions are oxidations if they proceed in the

direction which corresponds to the liberation of negative charge;
they are reductions if they proceed in the direction corresponding
to the absorption of negative charge.

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 Thermodynamics of Corrosion
• Thermodynamics gives the change in energy state, also predicts the
directions of a reaction. 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.

• Thermodynamics cannot predict the rate of reaction.

• Free energy is driving force of a chemical reaction.

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Free Energy Change and Dependency on Path
of Reaction

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 Free Energy
• The free-energy change accompanying an electrochemical reaction
can be calculated by the following equation:
• ΔG = -nFE
Where, n = number of electrons involved in the reaction, F = Faraday
constant, 96500 and E = electromotive force, volts

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 Nernst Equation
• The cell potential can be calculated by Nernst Equation:

• The change in free energy gives an idea of content of energy

displacement. But it does not give the velocity or the rate of
electrochemical reaction. The other limitation equilibrium states,
which are difficult to establish in corrosion reactions. 6
 Applications of Free Energy Calculation
Free energy calculation have been used to determine
Spontaneous direction of a reaction
Estimating the composition of corrosion products
Predicting the environment changes that will reduce the corrosion
rate

• Redox potential or e.m.f. series is a thermodynamic function

• Redox has been utilized to predict the corrosivity of metals in
various environments. For 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 + Oxygen → Corrosion would happen in this case
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Standard Redox Potentials

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Applications of Thermodynamics to Corrosion
• Thermodynamics or, more specifically, half-cell potentials can be
used to state a criteria for corrosion. Corrosion will not occur unless
the spontaneous direction of the reaction indicates metal
oxidation.
• Application of thermodynamics to corrosion can be discussed by
potential-pH diagram called Pourbaix Diagram.

Pourbaix Diagram:-
1. Marcel Pourbaix developed potential-pH diagrams to solve the
thermodynamic state of most metals in dilute aqueous
solutions.
2. These diagrams have curves representing chemical and
electrochemical equilibria between metal and aqueous
environment.
3. These diagrams ultimately show the conditions for immunity,
corrosion or passivation
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 Uses of Pourbaix Diagram
Predicting the spontaneous direction of reactions
Estimating the composition of corrosion products
Predicting environmental changes that will prevent or reduce corrosive
attack

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 Pourbaix Diagram (Contd…)
• 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.
Limitation of Pourbaix Diagram:
These diagrams are purely based on thermodynamics 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 be seriously affect the corrosion rate.
Pourbaix Diagrams deal with pure metals which are not much interest to
the engineers.
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 Electrode Kinetics
• In a short-circuited cell, a vigorous reaction occurs. The zinc
electrode rapidly dissolve in the solution and simultaneously a
rapid evolution of hydrogen is observed at platinum electrode.
Electrons released from the Zn dissolution and consumed in the
hydrogen-reduction reaction

Potential after coupling -0.66 V

Short-circuited cell containing zinc and hydrogen electrodes 12

 Overvoltage
• The Figure shows the overall
reaction of Zn dissolution and
hydrogen evolution. The
potentials of these electrodes
will no longer be at their
equilibrium potential. This
deviation from equilibrium
potential is called Polarization
(the displacement of electrode
potential resulting from a net
current). It is measured in
terms of overvoltage (η). The
overvoltage is stated in terms
Schematic of Zn corroding
of volts to equilibrium
potential (zero reference).
 The excess potential required for the discharge of an ion at an electrode over and
above the equilibrium potential of the electrode
 Voltage in excess of the normal operating voltage of a device or circuit
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 Exchange Current Density
• If the electrode potential vs.
reaction rate is plotted, it is
possible to establish a point
corresponding to the platinum-
hydrogen electrode. This point
represents the particular exchange
reaction rate of electrode
expressed in terms of moles
reacting per square centimeter per
second, no net reaction.
• Oxidation rate = reduction rate =
exchange reaction rate
• Exchange reaction rate can be
expressed in terms of current
density, and current density can be
directly derived from Faraday’s
law. Hydrogen-hydrogen ion exchange
on platinum
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Some Values of Exchange Current Densities

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 Date: 08Feb 2021

Exchange Current Density and Polarization

• Exchange current density depends on:-
1. Redox potential of a metal
2. Composition of electrode
3. Temperature of the system
4. The ratio of oxidized and reduced species

Polarization means the reduction in corrosion rate either by slowing down

the anodic or cathodic reaction. It is two types.
1. Activation Polarization
2. Concentration Polarization

 Activation polarization refers to the condition wherein the reaction rate is

controlled by the one step in the series that occurs at the slowest rate. The
term “activation” is applied to this type of polarization because an
activation energy barrier is associated with this slowest, rate-determining
step.
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Rate Determining Step of Hydrogen Production
• Activation polarization refers to an
electrochemical process that is
controlled by the reaction sequence
at the metal-electrolyte interface.
• S-1: the species must first be
adsorbed to the surface before the
reaction
• S-2: electron transfer must occur
resulting in a reduction of the
species
• S-3: two H atoms then combine to
form hydrogen gas
• S-4: the produced hydrogen gas is
released as bubble of hydrogen
The speed of reduction of hydrogen
ions will be controlled by the
Representation of possible steps in slowest of these steps.
hydrogen reduction. The rate of which is
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controlled by activation polarization.
 Activation Polarization
• For activation polarization, the relationship between overvoltage and
current density is
β = 2.3RT/αnF
• This equation is called Tafel Equation, where, β is a constant (Tafel
constant) and i is the rate of oxidation or reduction in terms of current
density. The parameter, i0, is termed as exchange current density. i0 is the
exchange current density.
• Equilibrium for some particular half-cell reaction is really a dynamic state
on the atomic level. That is, oxidation and reduction processes are
occurring, but both at the same rate, so that there is no net reaction. For
example, for the standard hydrogen cell reduction of hydrogen ions in
solution will take place at the surface of the platinum electrode according
to: 2H+ + 2e → H2
• With a corresponding rate r(red) similarly, hydrogen gas in the solution
will experience oxidation as H2 → 2H+ + 2e

• At rate r (oxd) equilibrium exists when r (red) = r (oxd) 18

Activation Polarization of Hydrogen Electrode

Standard hydrogen reference

half-cell 19
 Faraday’s Law

Where,
• W = corrosion rate in weight gain or loss (g)
• i = exchange current density (A/cm2)
• t = exposure time (sec)
• M = atomic weight of the metal (g/mol)
• n = no. of electrons transferred
• F = Faraday’s constant (96500 coulombs)
• I = current (A)
• A = Corroded surface area (cm2) 20
 Polarization Electrode (Reversible)
• Polarization at a reversible electrode is mainly due to the disturbance caused
in the equilibrium reaction taking place at that electrode. This is observed
when the electric current flows through the electrode. Such a phenomenon is
called electrolytic polarization and the electrode is said to be polarized.

Polarization electrode for zinc

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 Concentration Polarization
• Concentration polarization exists when the reaction rate is limited by
diffusion in the solution.

• For hydrogen reduction, the above schematic representation of the H+

distribution in the vicinity of the cathode for (a) low reduction/reaction
rates and/or high concentrations, and (b) high reduction/reaction rates
and/or low concentration wherein a depletion zone is formed that gives22
rise to concentration polarization
 Concentration Polarization (Contd…)
• In concentration polarization, limiting diffusion current density (iL) can be
calculated. It represents the maximum rate of reduction possible for a
given system. The equation is given as follows:

Where,
• iL = limiting diffusion current density ; F = Faraday’s constant
• D = diffusion coefficient of the reacting ions
• n = number of electrons involved
• CB = concentration of the reacting ions in the bulk solution
• X = thickness of the diffusion layer
The diffusion-layer thickness is influenced by the shape of the particular
electrode, the geometry of the system, and by agitation. If we consider no
activation polarization, then the equation for concentration polarization is
as follows:
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 Concentration Polarization
• For reduction reactions, schematic plots of overvoltage vs.
logarithm of current density for concentration polarization

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 Effect of Velocity, Temperature and
Concentration
• The below Figure illustrate the effects of changing limiting diffusion
current on the shape of the polarization curve encountered during
concentration polarization. As the solution velocity, concentration, or
temperature are increased, limiting diffusion current increases since all of
these factors exert an influence as indicated in the equation.

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 Combined Polarization
• Both activation and concentration polarization usually occur at an
electrode. Al low reaction rates, activation polarization usually controls
while at higher reaction rates concentration polarization becomes
controlling. The total polarization of an electrode is the sum of the
contributions of activation polarization and concentration polarization.
• Corrosion rates from polarization data

• Equation for the kinetic of anodic dissolution is given by:

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Activation and Concentration Polarization

For reduction reactions, schematic plots of overvoltage vs. logarithm of

current density for combined activation-concentration polarization
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 Mixed-Potential Theory
The mixed-potential theory consists of two simple hypothesis:
1. Ant electrochemical reaction can be divided into two or more
partial oxidation and reduction reactions.
2. There can be no net accumulation of electrical charge during an
electrochemical reaction

• The first hypothesis is quite obvious, and it can be experimentally

demonstrated that electrochemical reactions are composed of two
or more partial oxidation or reduction reactions.

• The second hypothesis is merely a restatement of law of

conservation of charge. That is, a metal immersed in an electrolyte
cannot spontaneously accumulate electric charge.

• During the corrosion of an electrically isolated metal sample, the

total rate of oxidation must equal the total rate of reduction.
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 Mixed Electrodes/Evans Diagram for Zinc
• A mixed electrode is an electrode or metal sample that is in contact with two
or more oxidation-reduction systems.

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Evans Diagram for Iron

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Evans Diagram for a Metal “M” in Acidic Solution
with Ferric Salt

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 Passivity
• Passivity refers to a corrosion preventative mechanism whereby an
oxidation layer forms a continuous film on a metal's surface that
prevents further corrosion. Passivity is the loss of electrochemical
reactivity, thereby decreasing the corrosion rate of the metal under
particular environmental conditions.
• Fe, Ni, Cr, Ti, Al and their alloys can undergo passivation in certain
conditions.

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Anodic Dissolution Behavior of an Active-Passive
Metal

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Effect of Temperature and Acid Concentration on Anodic
Dissolution Behavior of an Active-Passive Metal

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Behavior of an Active-Passive Metal Under Corrosion
Conditions

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 Transpassivation
• If a metal is immersed in an acid solution and oxidizing power of this
solution is increased, the corrosion rate of metals continuously
increases.
• A slight increase in the solution's oxidizing power causes a
corresponding rapid increase in the corrosion rate. But, as more
oxidizing agent is added, the corrosion rate shows a sudden decrease,
due to the formation of a highly protective but very thin film on the
metal surface, making it noble. The film is non-porous, insoluble and
self-healing in nature. This corresponds to the beginning of the passive
region.
• At very high concentrations of oxidizers, or in the presence of very
powerful oxidizers, the corrosion rate again increases with increased
oxidizing power. This region is known as the transpassive region, where
the thin film will dissolve and the corrosion rate increases again.
• Metals showing passivity exhibit outstanding corrosion resistance in
oxidizing environments. Some of the metals showing passivity include
titanium, aluminum and chromium.

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