Chapter III: Kinetics of Electrochemical Corrosion

III.1. Introduction
The potential of an electrode can be modified by an external action, it is then said that the
the electrode is polarized. This modification leads to a movement of charges: electrons
in the metal, ions in the solution.
Example: Ag Ag+ + é
Electrons pass through the outer conductor in the opposite direction of the current, this
The elimination of electrons is called oxidation.
the Ag ions+ leave the metal network to enter the solution so the metal is
dissolve. Conversely, if the current flows from the solution to the metal, the electrode is called
cathode. The Ag ions+ captures the electrodes arriving via the outer conductor, in direction
inverses the conventional direction of the current and forms a metallic network, we thus have
Electrodeposition this reaction is called reduction.
III.2. Notion and definition
III.2.1. Simple electrodes
When a metal/electrolyte system has a single electrode reaction occurring at the surface, we
qualify this simple electrode system.
Example: Zn immersed in a de-aerated zinc sulfate solution, slightly acidic.
Zn Zn+2+ 2 e-
III.2.2. Resting potential
The resting potential corresponds to the potential that the electrode spontaneously takes in
the absence of an external current. For a simple electrode, the resting potential is equivalent
to reversible potential
E(I = 0)= Erev.
III.2.3. Mixed electrode
Most often, several electrode reactions can occur simultaneously in a
metal-electrolyte system. Such a system is called a 'mixed electrode'
Example:
Metallic zinc immersed in an aerated zinc sulfate solution. Two reactions
partials appear:
Oxidation Zn: Zn Zn+2+ 2 e-
Reducer the O: O2+ 2H+ + 2 e- H2O
Overall reaction: Zn + O2+ 2H+ Zn+2+ H2O
The resting potential of a mixed electrode is called 'corrosion potential'; it is a
kinetic quantity that depends on the parameters that affect the speed of reactions
cathodic and anodic

III.2.4. Polarization
The electrode traversed by an external current is the seat of irreversible phenomena.
The term polarization is used to refer to all of these irreversible phenomena.
The effect of electric current modifies the metal-electrolyte equilibrium potential by a quantity
« » called electrode overvoltage. We can consider three types of polarization.

a. Resistance polarization
It is due to the formation of a film on the surface of the electrode. This film can be solid.
(oxide) or gaseous (hydrogen or oxygen absorbed for example). The film formed on
the electrode introduces an additional resistance to the passage of current and therefore
the intensity of the corrosion current is lower.
b. Concentration polarization
It intervenes when the diffusion rate of an ion towards the cathode limits the speed of
reaction at the electrode. The current intensity approaches a limiting value, very sensitive to
the agitation.
c. Charge transfer polarization (activation)
It corresponds to the variations of free energy of the metal-solution interface, related to the transition.

metal atoms in the state of ions or vice versa. It is the one that is most often involved.
in corrosion phenomena.

III.3. Butler-Volmer equation

Consider the charge transfer polarization at the metal/electrolyte interface, the capture
or the emission of electrons corresponding, for example, to the reaction:
Mnetwork 1 M+n solution + ne−
2

The meaning (1) of the reaction is the emission.

The meaning of the reaction is capture.
Which can be described from the theory of absolute reaction rates. This amounts to
consider that the surface ions must, in order to go into solution, receive, through agitation
thermal, a certain energy to overcome the energy barrier and it is the same
for the reverse process. Because of the existing stable electric field at the metal/interface
electrolyte, the movement of an ion will be facilitated or hindered depending on the direction of the free enthalpy
of activation and which will therefore be decreased or increased by an electrostatic work term.
For every redox couple, the Butler-Volmer equation, for the case where exchanges at the interface
are controlled by the charge transfer step, expresses a relationship between the potential
interfacial and current density, involving the kinetic parameters of both
reverse electrochemical half-reactions, characteristics of the considered redox couple.
For example, if we consider an interfacial electrochemical reaction of the form:
Red Ox + ne-
The "Butler-Volmer" equation that relates the interfacial current delivered by the
Redox couple as a function of electrochemical potential is written as follows:

I = I0[ [(( ‒ ) )/ ]‒ (‒ )/ )]

The equation of "Butler-Volmer" with:

I0: the metal/electrolyte exchange current at equilibrium.
I0=Ia-Ic this quantity characterizes the speed of the transfer of
charges at equilibrium.
By convention(Iais positive andIcis negative.
I: Global current of the reaction,
IaAnodic current of the reaction at the electrode surface,
IcCathodic current of the reaction at the electrode surface,
a: Symmetry factor,
n: number of exchanged electrons,
F: Faraday constant,
: Surge electrode.
We can simplify this equation:
1. For strong positive overvoltages > 0.1 which corresponds to the anodic reaction, we
neglect the term '2' of the equation we will have:
 IaI0[ (( ‒ ) )/ )] (1)

For strong negative surges < -0.1 that correspond to the cathodic reaction, we
neglect the term "1" from the equation we will have:

Ic=- I0[ (‒ )/ )] (2)

III.4. Tafel Coefficients

Equations (1) and (2) can be used in logarithmic form, in this case we will have
Tafel equations can be expressed:

a= (- 0.059/ (1-α) logI0) + (0.059 / (1 - α) log I 3

c= ((- 0.059 /α) logI0) - (0.059/α)log I) (4)

One can introduce the Tafel coefficients:

βa= RT/αnF

βC= RT/ ((1-α) n F)

We therefore find:

I = - I0[ ( / βa) - I0 ( / βc) ]

These relationships are the anodic and cathodic Tafel lines that describe the limits.
anodic and cathodic of the general Butler-Volmer equation.
Note
The Butler-Volmer equation and the Tafel equation (allow for the plotting of Tafel lines.
log(I) = f(E) and deduce the exchange current I0and the potential EeqThe intersection of the lines
anodic and cathodic, extrapolated to the corrosion potential, gives the current density
exchange or the current of corrosion ICorrect(A.cm-2) at equilibrium.

III.5. Polarization curves

During the natural corrosion of a metallic part Ia= |I cIcorr, so every reaction
Electrochemical can be represented by a curve: I= f(E) with Ecorr = Ee+
The rheostat (potentiostat galvanostat) allows for varying the intensity of the current. At the moment
initially, if the circuit is open, the potential of the two electrodes is: EA0for the anode and EK0
for the cathode. If a current with intensity I1circles in the stack, we observe that the potential of
the cathode becomes more negative and takes a value EK1and that of the anode becomes more
positive and takes the value EA1so: EK0EK1presents the cathodic overvoltage c) and EA0-

EA1it is the anode overvoltage a).

By varying the value of the current intensity, one can trace the polarization curves.
cathodic EK= f(I) and anodic polarization EA= f(I). This gives us for a certain
value Ic of intensity, the potential of the anode and the cathode that take the same value
Ec, Icthe maximum intensity is the corrosion intensity of the A-K couple in a medium
given. Ecorris the corrosion potential of the couple (mixed potential) (EVANS diagram)
see figure IV.1

Figure III.1: Polarization curve (AVENS diagram).

Note
To minimize the intensity of the corrosion current, it will be necessary to provide the anodic overvoltage,

cathodic or both surges a value as high as possible. However, if we

wants to make an electrochemical cell that delivers a high current, it will be necessary to avoid the
polarization phenomena by minimizing the overvoltage at the electrodes as much as possible
the help of polarizers MnO2.

III.6. Electrochemical characterization of corrosion

Electrochemical methods are a tool to characterize corrosion phenomena.
They allow for the explanation of processes, to determine the mechanisms involved during the
degradation, to quantify and forecast. They also lead to sometimes choosing more
judiciously the appropriate methods of protection. They can be classified into two
groups. The first includes the so-called stationary techniques that allow access to
potential-time curves, potentiodynamic, cyclic polarization, etc. These techniques
allow to gather information related to the kinetics of the studied system. Nevertheless,
they are subject to limitations, particularly in the case of highly resilient systems or for
the study of reaction mechanisms. Moreover, some of them lead to destruction.
of the sample. To circumvent these limitations, a number of
transient techniques, based on the use of transfer functions and whose
electrochemical impedance spectroscopy (EIS) is part.

III.6.1. Stationary techniques

Measurement of open circuit potential (OCP)
This technique allows for tracking the evolution of the working electrode potential in a circuit.
open. The measurement of this electrochemical magnitude provides indications about the
corrosion behavior in a known solution. In practice, the curves of
Potential as a function of time can present different aspects. (See TP brochure)
the potentiodynamic polarization curves
To plot these curves, we vary the potential applied to the metal to be studied using a
potentiostat and for each voltage value, we record the intensity of the current flowing
between the two electrodes and we record the variation of the potential taken by the metal.
Figure III.2: Logarithmic polarization curves indicating the domains and the lines of
Anodic and cathodic table.

The corrosion rate measurement by extrapolating Tafel lines is used to determine the
corrosion current Icorrthen, by Faraday's law, to calculate the corrosion rate of
the electrode in the corrosive solution. For a system involving only one reaction
anodic and cathodic
The corrosion rate Vcorris generally expressed in units of length (μm, mm, etc.)
per unit of time (s, min, year, etc.).

icorr: current density (A.cm)-2)

t: time in seconds corresponding to a year,
M: molar mass (g.mol-1),
the valence
F: Faraday constant (C.mol-1),
d: density (g.cm-3).
Polarization resistance
This method has the advantage of involving the polarization curve in the vicinity.
the corrosion potential of the working electrode, in this region where this curve is linear.
The measurement of corrosion rate by extrapolating Tafel lines requires certain
conditions and its use therefore poses certain difficulties, such as: uniform corrosion
of metal, corrosion products in ionic form, negligible ohmic effects. So the
The polarization resistance technique helps avoid these difficulties. The slope ΔE/ΔI of the
The linear portion of the polarization curve can be determined experimentally. The more the
The value of ΔE/ΔI is high and the corrosion current intensity is lower.

Figure III.3: Measurement of resistance Rp

III.6.2. The transitional techniques

Use of electrochemical impedance measurements
It is a new technical study of the electrochemical corrosion process based on the
electrode impedance measurement. This method involves measuring the electrode's response
in the face of a low amplitude sinusoidal modulation of the potential E as a function of the
frequency f:
ΔE= ΔE sinωt
Here, ΔE denotes the amplitude of the disturbance and ω = 2πf the angular frequency. An excitation signal.

of low amplitude (~10 mV) allows to remain in a pseudo-linear domain. The

The sinusoidal perturbation of the potential induces a sinusoidal current ΔI, superimposed on the current.
stationary, and phase-shifted by an angle ϕ with respect to the potential.

ΔI = ΔI sin(ωt − ϕ)

The impedance Z(ω)The system is the ratio between the imposed sinusoidal voltage and the
resultant current. It can be defined by a complex number:

Z= ΔE/ΔI
Z(ω) can thus be represented in the complex plane by its real part and its part
imaginary in a so-called Nyquist diagram, or by its modulus Z and its phase as a function of
the frequency in so-called Bode diagrams.
A metal-solution interface can be represented by an equivalent electrical circuit known as
Randles circuit. In this circuitecorresponds to the resistance of the electrolyte between the
two measuring electrodes, Cdcrepresents the capacity of the double layer and the process
faradic described by a pure charge transfer resistance Rtc.

Figure III.4: Equivalent electrical circuits of the Randles interface electrode/solution with
Faradaic reaction without diffusion control (a) and its representation in the complex plane
of Nyquist(b).

The reaction mechanism corresponding to Randles' model does not take into account either the

mass transport, nor adsorption phenomena. A more realistic equivalent circuit is

So considered. It always includes the ohmic resistance Re and the capacity of the double.
layer Cdc, on the other hand, the transfer resistance Rtcis replaced by the faradic impedance
ZF composed of one or more circuit elements, in series or in parallel according to the
reactive mechanism. When transport phenomena occur, one or more
The elements of this circuit will be a Warburg diffusion impedance (Z)W).