Department of Mechanical Engineering

Chittagong University of Engineering and Technology

Metal
∆G~ (Energy Barrier)

 
∆𝐺
Free Energy, G

Ore
Corrosion
Products

Reaction Coordinate

MSc/PhD Course # ME 6351 Corrosion Kinetics Page # 1

 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

Figure 1: Energy profile for Ore, Metals and compounds [4]

 
The size of the free energy of activation (G~) which determines the rate of corrosion ()
= KCorr [Reactants] , where KCorr = A exp (-∆G~/RT) or

MSc/PhD Course # ME 6351 Corrosion Kinetics Page # 2

 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

 
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..
 
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) , the current is positive and copper dissolves
b) , the current is negative and copper deposited

MSc/PhD Course # ME 6351 Corrosion Kinetics Page # 3

 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

 
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.
 
Polarisation or Overpotential or Over voltage: The potential difference between measured
potential to the expected potential from Nernst equation during ineqilibrium condition is called
polarization. Or, The difference between the free corrosion potential with the electrode
potential when a metal is not in equilibrium with a solution of its ions. Or, The difference
between the resultant potential (E) and each individual reaction equilibrium potential (Eeq) is
called polarization and is quantified in terms of overpotential (η ) described

The polarization is said to be anodic when the anodic processes on the electrode are
accelerated by moving the potential in the positive (noble) direction or cathodic when the
cathodic processes are accelerated by moving the potential in the negative (active) direction.
There are three distinct types of polarization and these are additive. [4,5,10]

MSc/PhD Course # ME 6351 Corrosion Kinetics Page # 4

 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

 
Polarisation of Single electrodes
Activation or charge transfer polarization: If the taking up or giving off electrons are the rate determining
step, it is called activation Polarisation. Activation polarization is caused by a slow electrode reaction. The
reaction at the electrode requires an activation energy in order to proceed.
The rates of all chemical reaction obey the well-known Arrhenius equation

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

where i= reaction is the anodic or cathodic current, = 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)

MSc/PhD Course # ME 6351 Corrosion Kinetics Page # 5

 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

 
When reaction is cathodic, that is, negative, the second term in the Butler-Volmer equation becomes negligible
and the cathodic current density () can be expressed by a simpler equation where
Similarly, when 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
where
Written in the forms - and are known as Tafel equations and & are Tafel constants for anodic and cathodic
reactions respectively
 
In equilibrium, = 0
At large polarization,

MSc/PhD Course # ME 6351 Corrosion Kinetics Page # 6

 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

0.20 V

0.10 V

Polarisation (V)

0.00 V

io

- 0.10 V

- 0.20 V
-4 -3 -2 -1
10 10 10 10 1
2
Current Density A/ m

Figure: Theoretical Tafel Plot [4]

𝑖  𝑚𝑒𝑎𝑠=𝑖 𝑎 −𝑖 𝑐 =0.1− .001=0.099 𝐴 𝑚− 2

MSc/PhD Course # ME 6351 Corrosion Kinetics Page # 7

 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

-
0.20 V

z+

0.10 V

Polarosation (V) ECorr

0.00 V

io
- 0.10 V

- 0.20 V
-4 -3 -2 -1
10 10 10 10 1
2
Current Density (A/m )

Figure: An idealized practical Tafel plot [4]

MSc/PhD Course # ME 6351 Corrosion Kinetics Page # 8

 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

  𝑖

  𝑖𝑐

  𝑖𝑎

MSc/PhD Course # ME 6351 Corrosion Kinetics Page # 9

 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

Concentration polarization: The polarization component caused by concentration changes in the

environment adjacent to the surface as illustrated in figure. When a chemical species
participating in a corrosion process is in short supply, the mass transport of that species to the
corroding surface can become rate controlling. A frequent case of concentration polarization
occurs when the cathodic processes depend on the reduction of dissolved oxygen since it is
usually in low concentration, that is, in parts per million (ppm)

Figure: Concentration changes in the vicinity of an electrode causing a concentration polarization effect.

MSc/PhD Course # ME 6351 Corrosion Kinetics Page # 10

 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

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.

Figure: The processes occurring at an electrochemical interface [5]

MSc/PhD Course # ME 6351 Corrosion Kinetics Page # 11

 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

 
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

where JO is the flux of species O (mol s−1 cm−2), DO is the diffusion coefficient of species O (cm2 s−1)
= The concentration gradient of species O across the inter-face between the metallic surface and the bulk environ-ment (mol

cm−3), The Nernst diffusion layer or diffuse layer (cm)

MSc/PhD Course # ME 6351 Corrosion Kinetics Page # 12

 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

c Co C

Electrodes
b

 Distance from electrode

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.

MSc/PhD Course # ME 6351 Corrosion Kinetics Page # 13

 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

 
Polarisation resistance: 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

 
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.
 

MSc/PhD Course # ME 6351 Corrosion Kinetics Page # 14

 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

Evans Diagram or Mixed potential theory:

According to the mixed-potential theory underlying these diagrams, any electrochemical reaction can be
algebraically divided into separate oxidation and reduction reactions with no net accumulation of electrical
charge. Under these circumstances the net measurable current is zero and the corroding metal is charge
neutral, that is, all electrons produced by the corrosion of a metal have to be consumed by one or more cathodic
processes. In order to model a corrosion situation with mixed potential diagrams, one must first gather the
information concerning the
(1) Activation overpotential for each corrosion process involved and
(2) Any additional information for processes that could be affected by concentration overpotential.

Potential (V) SHE

0.00

E corr
(M)
-
e
z+ +Z
M

M
o
E (M)

lg io(H2) lg io(M) lg icorr(M)

lg (Current Density)

MSc/PhD Course # ME 6351 Corrosion Kinetics Page # 15

 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

E corr

Potential (V) c
lg io

ECorr (Cell)

- lg iL
e
2+ +2
Zn

Zn lg(icell)
a
E corr

lg io

lg (Current Density)

MSc/PhD Course # ME 6351 Corrosion Kinetics Page # 16

 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

Potential (V) 0.0

-0.1

-0.2
-

2e
-0.3 2+
+
Fe E corr(Couple)
-0.4 Fe

-0.5
-

2e
2+
+
-0.6
Zn

- 0.7
Zn

-0.8
-11 -10 -9 -8 -7 -6 -5 -4 -3 -2 -1
10 10 10 10 10 10 10 10 10 10 10
Current Density

MSc/PhD Course # ME 6351 Corrosion Kinetics Page # 17

 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

MSc/PhD Course # ME 6351 Corrosion Kinetics Page # 18

 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

MSc/PhD Course # ME 6351 Corrosion Kinetics Page # 19

 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

MSc/PhD Course # ME 6351 Corrosion Kinetics Page # 20

 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

MSc/PhD Course # ME 6351 Corrosion Kinetics Page # 21

 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

MSc/PhD Course # ME 6351 Corrosion Kinetics Page # 22