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MSC/PHD Course # Me 6351: Corrosion Kinetics
MSC/PHD Course # Me 6351: Corrosion Kinetics
Metal
∆G~ (Energy Barrier)
∆𝐺
Free Energy, G
Ore
Corrosion
Products
Reaction Coordinate
The size of the free energy of activation (G~) which determines the rate of corrosion (𝜗)
~
𝝑 = KCorr × [Reactants] , where KCorr = A exp (-∆G~/RT) or 𝑘 = 𝐴𝑒
Exchange current: Exchange current is the current in equilibrium when the anodic current
density is equal to cathodic current density that is no current flows in the circuit but current
flowing in equal and opposite direction which cannot be measured. 𝑖 = 𝑖 = − 𝑖 .
The copper electrode reaction is shown is shown below where Ia and Ic are the anodic current
and cathodic current respectively. The anodic current is counted positive and cathodic current
is counted negative.
Ic
Cu2+ + 2e- Cu
Ia
I. In equilibrium, the forward and reverse reactions are equal and opposite, so no current flows.
Mathematically, Ia + Ic = 0
II. If there is no equilibrium a net current I flows to or from the electrode, I = Ia + Ic.
Two cases that can arise as the external current represents a net chemical reaction.
a) 𝐼 > 𝐼 , the current is positive and copper dissolves
b) 𝐼 < 𝐼 , the current is negative and copper deposited
Single electrode: An electrode at which only one reaction occurs is called single electrode.
Poly electrode: Electrodes where two or more reactions occur simultaneously are called
polyelectrode.
When charged species take part in the reaction, the energy barrier is influenced by electric field.
When there is no equilibrium, the net current is given by Butler-Volmer relationship
𝑖= 𝑖 exp − exp
where i= reaction is the anodic or cathodic current, 𝛼 = the charge transfer barrier (symmetry coefficient)
for the anodic or cathodic reaction, usually close to 0.5, n = The number of participating electrons, R =
The gas constant, that is, 8.314 J mol−1 K−1, T is absolute temperature (K) and F is 96,485 C/(mol of
electrons)
When 𝜂,reaction is cathodic, that is, negative, the second term in the Butler-Volmer equation becomes
negligible and the cathodic current density ( 𝑖 ) can be expressed by a simpler equation 𝑖 =
Similarly, when 𝜂 reaction is anodic, that is, positive, the first term in Butler-Volmer equation becomes
negligible and the anodic current density (ia) can be expressed by the equation
Written in the forms - 𝜂 = 𝛽 𝑙𝑛𝑖 − 𝛽 ln 𝑖 and 𝜂 = 𝛽 𝑙𝑛𝑖 − 𝛽 ln 𝑖 are known as Tafel equations and
𝛽 &𝛽 are Tafel constants for anodic and cathodic reactions respectively
In equilibrium, 𝑖 = 𝑖 + 𝑖 = 0
At large polarization, 𝜂 > 0.1 𝑉
Figure: Concentration changes in the vicinity of an electrode causing a concentration polarization effect.
Mass transport to a surface is governed by three forces - diffusion, migration, and convection. In
the absence of an electrical field the migration term is negligible since it only affects charged
ionic species while the convection force disappears in stagnant conditions.
For purely diffusion controlled process - mass transport, the flux of a species O to a surface from the bulk is
described with Fick’s first law
𝛿𝐶
𝐽 = −𝐷
𝛿𝑥
where JO is the flux of species O (mol s−1 cm−2), DO is the diffusion coefficient of species O (cm2 s−1)
𝛿𝐶 = The concentration gradient of species O across the inter-face between the metallic surface and the bulk environ-ment
(mol cm−3), 𝛿𝑥 = The Nernst diffusion layer or diffuse layer (cm)
Electrodes
Figure: Nernst diffusion layer for a limiting current situation [5, 10]
Figure illustrates the concentration-distance profile at the electrode surface approximated by a simple
gradient. In this diagram the metallic surface is positioned at the ordinate axis while the x-axis
expresses the distance away from the electrode and the y-axis the concentration of the chemical species
being reacted. For well-mixed solutions, the concentration is constant in the bulk or convective region.
Polarisation resistance(𝑅 ): The Ohmic overpotential appears as the simple product of a resistance and a
current between the anodic and cathodic sites of a corrosion process When the separation of the anodic and
cathodic sites are important factor in the corrosion progress, for example, galvanic corrosion, or even an integral
part of a particular protection scheme, for example, anodic and cathodic protection. For small polarization, a
simplified equation
𝜂 𝑛𝐹 𝑖𝑅𝑇 𝑅𝑇
𝑖 = 𝑖 ~ 𝜂= ~ 𝑅 =
𝑅𝑇 𝑖 𝑛𝐹 𝑖 𝑛𝐹
For many corrosion situations these sites are adjacent to each other and the ohmic drop is negligible, particularly
so when the environment itself is a good electrolytic conductor, that
is, seawater.
c
a
e -
2
+
2+
Fe
Fe
e -
2
+
2+
Zn
Zn