MODERN THEORY – PRINCIPLES

Electrode Kinetics

Corrosion systems are not at

equilibrium.

When the electrochemical cell is

short-circuited, a vigorous reaction
occurs.
The net oxidation and reduction processes
occur at electrode interfaces, the
potentials of these electrodes will no
longer be at their equilibrium potential.

This deviation from equilibrium potential

is called polarization.

Overvoltage (η) is a measure of

polarization with respect to the
equilibrium potential of an electrode.
Equilibrium conditions dictate that the
rate of oxidation and reduction, r1 and r2
respectively, must be equal.
 Exchange Current Density

 At equilibrium hydrogen electrode there is a finite rate of interchange

between hydrogen molecules and hydrogen ions in solution.

 The exchange current density io is the rate of oxidation and reduction at

an equilibrium electrode expressed in terms of current density.
There is no theoretical way of precisely
determining the exchange current density for
any given system; it must be determined
experimentally.
 POLARIZATION
Electrochemical polarization is divided into two main types :

Activation polarization.

and

Concentration polarization.
ACTIVATION POLARIZATION

It is represented by Tafel equation:

ηa = ± β log (i/io)

Where:
ηa is overvoltage, β is a constant, and i is the
rate of oxidation or reduction in terms of
current density.
At all potentials more noble than the
reversible potential a net oxidation process
occurs.

At all potentials more active or more negative

than the reversible potential a net reduction
occurs.
At the reversible potential, or at
zero overvoltage, there is no net
rate of oxidation or reduction since
both rates are equal at this
intersection point.
 CONCENTRATION
POLARIZATION

At low reduction rates the distribution

of hydrogen ions in the solution
adjacent to the electrode surface is
relatively uniform.
At very high reduction rates the region
adjacent to the electrode surface will
become depleted of hydrogen ions.
If the reduction rate is increased further, a
limiting rate will be reached that determined
by the diffusion rate of hydrogen ions to the
electrode surface.

This limiting rate is the limiting diffusion

current density iL. It represents the
maximum rate of reduction possible for a
given system:
 iL = D n F CB/x

Where:
iL is the limiting diffusion current density,
D is the diffusion coefficient of the reacting ions,
CB is the concentration of the reacting ions in the
bulk solution, and
x is the thickness of the diffusion layer.

Agitation tends to decrease the diffusion layer thickness because of convection

currents and consequently increases the limiting diffusion current density.
Limiting diffusion current density is usually
only significant during reduction processes
and is usually negligible during metal-
dissolution reaction.

Limiting diffusion current density can be

ignored during most metal-dissolution
reactions. The reason for this is, simply, that
there is an almost unlimited supply of metal
atoms for dissolution.
If we consider an electrode in which there is
no activation polarization, then the equation
for concentration polarization is:

ηc = 2.3 (R T/n F) log (1 – i/iL)

As the solution velocity, concentration, or
temperature are increased, limiting diffusion
current increases.
 COMBINED POLARIZATION

Both activation and concentration

polarization usually occur at an electrode.

At low reaction rates, activation polarization

usually controls, whereas at higher reaction
rates concentration polarization becomes
controlling.
 For Anodic dissolution:

ηdiss = ± β log (i/io).

 This equation applies to almost all anodic dissolution reactions except for
metals which demonstrate active-passive behavior.

 For Overall reduction:

ηred = - β log (i/io) + 2.3 (R T/n F) log (1 – i/iL).

 This equation applies to any reduction reaction.

 MIXED-POTENTIAL THEORY
The mixed-potential theory consists of two simple
hypotheses:
1. Any electrochemical reaction can be
divided into two or more partial
oxidation and reduction reactions.

2. There can be no net accumulation of

electric charge during an electrochemical
reaction (the law of conservation of
charge).
This means that the total rate of oxidation
must equal the total rate of reduction.
MIXED ELECTRODE

 A mixed electrode is an electrode or

metal sample that is in contact with
two or more oxidation-reduction
systems.
Examples:

1. Attack on zinc by hydrochloric

acid (air-free HCl)

If a piece of zinc is inserted in HCl

containing some zinc ions, the electrode
cannot remain at either of these two
reversible potentials but must lie at some
other potential where the total rate of
oxidation equals the total rate of reduction
(Ecorr).
Only at this point (Ecorr) is charge
conservation maintained.

The current density corresponding to this

point is usually called corrosion current
density, icorr, since it represents the rate of
zinc dissolution.

Here, icorr also corresponds to the rate at

which hydrogen gas is evolved.
2. Corrosion behavior of iron in dilute
hydrochloric acid solution.

 The steady state of this particular system

occurs at the intersection between the
polarization curves for iron dissolution
and hydrogen evolution.
Although the free energy for the dissolution
of iron is lower than that of zinc (the cell
potential for iron and hydrogen electrode
under standard conditions is (- 0.44) volt as
contrasted to (- 0.76) volt for zinc), the
corrosion rate of iron is greater than that of
pure zinc when exposed to identical
concentrations of hydrochloric acid.
This is due to the very low exchange current
density for hydrogen-evolution reaction on
zinc surfaces.

 Thus, although the free-energy change for

the corrosion of zinc is negative and greater
than that for iron, the corrosion rate of zinc
is less than that of iron.
This illustrates the error that may be
introduced by assuming that free-energy
change and corrosion rate are proportional.
3. A frequent impurity in commercial HCl is
ferric ion, present as FeCl3;

The point at which the total rate of oxidation

equals the total rate of reduction (at steady
state) is the mixed or corrosion potential of
this system.
A horizontal line is drawn in Ecorr since the
metal is equipotential.

The rate of metal dissolution or the

corrosion current is given by icorr.
The rate of ferric-ion reduction is equal
to i (Fe3+ → Fe2+).

The rate of hydrogen evolution is given

by i (H+ → H2).
 In the absence of oxidizers, the corrosion rate of metal M is given by the
intersection of the hydrogen-reduction and metal dissolution polarization
curves.
The addition of an oxidizer, such as ferric
ions, shifts the corrosion potential to Ecorr
and consequently increases corrosion rate
from i’corr to icorr and decreases hydrogen
evolution from i’corr to i (H+ → H2).
In oxidizer-free acids icorr = rate of H2
evolution.
4. Corrosion of metal M under reduction-
diffusion control

A corrosion of a metal M in a weak acid

solution where the reduction process is
under diffusion control.

In this example, the metal M follows the

typical anodic dissolution reaction under
activation control.
Initially, the reduction rate of hydrogen ions
under activation control; at higher reduction
currents it is controlled by concentration
polarization.

The corrosion rate of this system is equal to

icorr or iL and, as before, is determined by the
intersection between the total reduction rate
and total oxidation rate.
 PASSIVITY
It is defined as a loss of chemical reactivity
under certain environment conditions.
 If a small piece of iron or steel is immersed
in nitric acid of approximately 70%
concentration at room temperature, no
reaction is observed.

If water is now added, diluting the nitric

acid approximately 1 to 1, no change occurs.
If the iron is scratched with a glass rod or if
the beaker is shaken violently so that the
sample strikes the sides, a violent reaction
occurs. The iron rapidly goes into solution,
and large volumes of nitrogen oxide gases
are released.

A similar effect occurs if the iron is directly

introduced into diluted nitric acid.
Iron, chromium, nickel, titanium and alloys
containing major amounts of these elements
demonstrate active-passive transitions.

The behavior of the active-passive metal

initially demonstrates behavior similar to
non-passivating metals (follows Tafel
behavior). This is the active region.
At more noble potentials, dissolution rate
decreases to a very small value and remains
essentially independent of potential over a
considerable potential region. This is termed
the passive region.
Finally, at very noble potentials,
dissolution rate again increases with
increasing potential in the transpassive
region.
The transpassive region where dissolution
rate again increases with increasing potential
is apparently due to the destruction of the
passive film at very positive potentials.

Ic = critical anodic current density for

passivity, and Epp = primary passive
potential.
Effect of increasing temperature and acid
concentration on behavior of an active-passive
metal.
Both temperature and hydrogen-ion
concentration tend to increase the critical
anodic current density and usually have
relatively little effect on the primary passive
potential and passive dissolution rate.

A similar effect is noticed upon increasing

chloride additions in the case of stainless
steels and other ferrous-base alloys.
A single reduction process such as hydrogen
evolution with three different possible
exchange current densities.
Case 1: Titanium in dilute, air-free sulfuric
or hydrochloric acid.

Under these conditions, titanium corrodes

rapidly and cannot passivate.
Case 2: Chromium in air-free sulfuric
acid and iron in dilute nitric acid.
Case 3: Stainless steels and titanium in acid
solution containing oxidizers such as ferric
salts or dissolved oxygen and also iron in
concentrated nitric acid.
Spontaneous passivation only occurs if
the cathodic reduction process clears the
tip of the nose of the anodic dissolution
curve.
MODERN THEORY–APPLICATIONS
What effect will increasing temperature have
on the life of equipment?

Will increasing velocity cause an increase or

decrease in corrosion rate?

If dissimilar metals are used, will this affect

corrosion rate?
 Effect of Oxidizers :

Generally:

When an oxidizing agent is added to a

corroding system containing a non-passivating
metal, corrosion rate is increased.
A typical active-passive metal M
immersed in an electrolyte containing a
redox agent such as ferric, cupric, or
chromate ions.
Addition: A, B, C, D, G, H, I, J
Reduction: J, I, H, G, F, E, B, A
An oxidizer concentration of 4 is
required to produce passivity,
whereas a concentration of oxidizer
as low as 2 can maintain passivity.
Iron in concentrated HNO3 = point H(5);

If diluted to 2-4, then scratching is

dangerous.
 Effect of Velocity

A metal M immersed in a corrosive system in

which the reduction process is under diffusion
control.
As velocity is increased to 4+, the reduction
reaction becomes activated control.

As a consequence, the corrosion rate

becomes independent of velocity at very high
velocity.
The effect of velocity on an active-
passive metal is illustrated below:
Galvanic Coupling
Since hydrogen-hydrogen ion exchange
current density is very high on platinum and
very low on zinc, the total rate of hydrogen
evolution is effectively equal to that on the
platinum surface.
The increase in corrosion rate of zinc
observed when this metal is coupled to
platinum is the result of the higher exchange
current density for hydrogen evolution on
platinum surface and not due to the noble
reversible potential of platinum-platinum-ion
electrode.
 AREA EFFECT

Increasing the area of an electrode increases

its exchange current.

If relative area of the anode in a galvanic

couple is increased, its overall corrosion rate
is reduced.
Unusual behavior
This unusual behavior only occurs if the
passive region of the metal begins at a
potential more active than the reversible
potential of the redox system.

Only two metals, titanium and chromium, if

coupled with platinum produce spontaneous
passivation in the absence of oxygen or
oxidizers.
 Alloy Evaluation
Oxygen is the most common oxidizer. It is
slightly soluble in water and aqueous
solutions, therefore, its reduction is usually
under diffusion control.

In air-saturated non-agitated solutions, the

limiting diffusion current density for oxygen
reduction is approximately 100 μA/cm2
If an active-passive metal is exposed to an
aerated corrosive medium, it spontaneously
passivates if its critical anodic current density
is equal to or less than approximately 100
μA/cm2.

Thus, if the anodic dissolution behavior of a

metal or alloy is known, it is possible to
predict whether or not it will passivate in an
aerated solution.
Addition of Cr & Ni to iron increase the
ease of passivation.
The addition of small amounts of 2% Mo to
austenitic stainless steels produces a further
decrease in Ic, and passivated in not
completely air-saturated solutions.