ME 472

(Corrosion Engineering)

Instructor: Dr. Ihsan-Ul-Haq Toor

Office: 63-358/Phone:7493
E-mail: ihsan@kfupm.edu.sa

Reference/Reading: Chapter 5-classnotes

ME472: CORROSION ENGINEERING 1 Dr. Ihsan-ul-Haq Toor

 Objectives;
Kinetics

Equilibrium potential and Faraday’s law

Exchange Current density
Polarization and over voltage (anodic and cathodic polarization)
Polarization diagram
Activation and Concentration Polarization(Butler Volmer Equation)
Mixed potential theory

ME472: CORROSION ENGINEERING 1 Dr. Ihsan-ul-Haq Toor

Faraday’s Law and measurement of mass loss/gain or corrosion current

How much metal is dissolved/reacted or

accumulated can be determined using Faraday’s
law.

 Faraday established a relationship between

current “I” and mass “m” reacted as follows;
m=Iat/ zF
Metal loss

Where;

I= Current involved during a reaction

a= Atomic weight of the material
T= time of reaction
Z= number of equivalents exchanged
F= Faraday’s constant Metal gain

ME472: CORROSION ENGINEERING 1 Dr. Ihsan-ul-Haq Toor

Faraday’s Law and measurement corrosion rate

The rate of metal dissolution or reduction may be expressed as a

current density (A/cm2) according to the Faraday’s law ;
• m=Iat/ zF
• Divide with 1/At on both sides (A=surface area)
m/tA=Iat/ zFAt
r= ia/zF
WHERR
r= mass loss per unit area per unit time

ME472: CORROSION ENGINEERING 1 Dr. Ihsan-ul-Haq Toor

 See handouts for examples of corrosion rate
calculations and
further discussions on penetration rate and
equivalent weight calculation
#CP

ME472: CORROSION ENGINEERING 1 Dr. Ihsan-ul-Haq Toor

Corrosion Kinetics and Application of EC to Corrosion

At Equilibrium Potential

For Cu2+ + 2e  Cu
ECu2+/Cu = EoCu2+/Cu + (RT/zF) ln [Cu2+]
= 0.340 + 0.059/2 ln [Cu2+] at 25 ℃

ME472: CORROSION ENGINEERING 1 Dr. Ihsan-ul-Haq Toor

Exchange current density

M  Mz+ + ze = ia
M
M  Mz+ + ze = ic

Exchange Current Density=

i0= C exp (-ΔG*/RT

See class handouts for equation derivation

ME472: CORROSION ENGINEERING 1 Dr. Ihsan-ul-Haq Toor

Factors affecting exchange current density

• 2H+ + 2e- → H2 (on M)

ME472: CORROSION ENGINEERING 1 Dr. Ihsan-ul-Haq Toor

What is Polarization (anodic and cathodic)

AP

CP

ME472: CORROSION ENGINEERING 1 Dr. Ihsan-ul-Haq Toor

What is Polarization (anodic and cathodic)

ie,a
e-
1) Anodic polarization
ia
M M+z + ze- ………at Eapp > Eeq
ic M+z
ie,a = ia – ic = f(a) M
where Eeq = reversible potential or equil. potential
a = Eapp-Eeq : anodic overpotential or
anodic overvoltage : Eapp > Eeq

ie,c
2) Cathodic polarization e-

ic
M M+z + ze- ............. at Eapp  Eeq
ia

M+z
ie,c = ic –ia = f(c) M
c = Eapp-Eeq cathodic overpotential or
cathodic overvoltage.
: Eapp < Eeq

ME472: CORROSION ENGINEERING 1 Dr. Ihsan-ul-Haq Toor

Relation between current density and overpotental /Tafel equations

ia
ηa  β a log
io
ic
ηc  β c log
io

See class handouts for equations derivation

Fig. Ref: McCafferty’s Book

ME472: CORROSION ENGINEERING 1 Dr. Ihsan-ul-Haq Toor

Corrosion Kinetics and Application of EC to Corrosion

Experimental polarization curve:

how it looks like?

ME472: CORROSION ENGINEERING 1 Dr. Ihsan-ul-Haq Toor

Plotting overpotential Vs log i-Polarization Diagram

ME472: CORROSION ENGINEERING 1 Dr. Ihsan-ul-Haq Toor

 Both AP & CP are affected by:

1: Activation Polarization/ charge transfer polarization

2: Concentration Polarization

ME472: CORROSION ENGINEERING 1 Dr. Ihsan-ul-Haq Toor

Effect of Activation and Concentration on Cathodic Polarization

Fig. Ref: McCafferty’s Book

ME472: CORROSION ENGINEERING 1 Dr. Ihsan-ul-Haq Toor

Effect of Activation and Concentration on Anodic Polarization

Fig. Ref: McCafferty’s Book

ME472: CORROSION ENGINEERING 1 Dr. Ihsan-ul-Haq Toor

 Two Types of polarization (1:Activation polarization)

For charge transfer reaction in metal/solution interface:

M(in lattice)  Mz+ (hydrated in sol.) + ze-

Actually,. M, lattice
 M,lattice Mz+,sol
M, adsorbed M,ad

Mz+, sol

ME472: CORROSION ENGINEERING 1 Dr. Ihsan-ul-Haq Toor

 1:Activation polarization

Activation polarization is due to retarding factors that are an inherent part of the
kinetics of all electrochemical reactions.
“when some step in the half cell reaction controls the rate of charge (electron)
flow, reaction is said to be under activation or charge transfer control and
activation polarization results”

EXAMPLE
• 2H+ + 2e- → H2 (on M)

• H+ + e- → Hads

• Hads + Hads →H2

Sufficient H2 molecules combine together to nucleate a hydrogen

bubble on the surface

ME472: CORROSION ENGINEERING 1 Dr. Ihsan-ul-Haq Toor

 Two Types of polarization (1:Activation polarization)

Volmer Butler Equation

ME472: CORROSION ENGINEERING 1 Dr. Ihsan-ul-Haq Toor

 Two Types of polarization (1:Activation polarization)
Example of activation polarization of hydrogen reaction

At equilibrium;
E =0, i =1mA
0

If anodic Tafel
constant is 0.1V/ If current is allowed to
decade, what will flow, over potential can
be anodic over- be calculated by:
potential?
= 0.1 * log 10/1

ᵦa and ᵦc are usually taken as 0.03~.15V/decade

ME472: CORROSION ENGINEERING 1 Dr. Ihsan-ul-Haq Toor

 2: Concentration polarization

• One of the assumptions in the derivation of the Volmer- Butler eq. is

the uniformity of concentration near the electrode.

• This assumption fails at high current densities because migration of

ions towards the electrode from the bulk is slow and may become
rate determining.

• A larger overpotential is then needed to produce a given current

because the supply of reducible or oxidizable species has been
depleted.

• This effect is called conc. polarization.

•

ME472: CORROSION ENGINEERING 1 Dr. Ihsan-ul-Haq Toor

 2: Concentration polarization

A frequent case of concentration polarization

occurs when the cathodic processes depend
on the reduction of dissolved O2 since it is
usually in ppm concentrations

O2 conc. as a function of distance from the

electrode surface
O2+2H2O+ 4e-----4OH-

 The conc. Near the electrode surface

depends on diffusion process of ions

ME472: CORROSION ENGINEERING 1 Dr. Ihsan-ul-Haq Toor

 2: Concentration polarization

For well-mixed solutions, the conc. Is constant in the bulk or convective regi
on (C = CO or CB)

There is also a region where the concentration drops, falling to zero at the electrode
surface (CS).

The Nernst diffusion layer associated with this drop has a specific thickn
ess (d ) that depends upon the nature of the solution into which it extends.

For stirred aqueous solutions the thickness of the diffusion layer varies betwee
n 0.01 and 0.001 mm.

c = RT/zF ln (1 - i/iL) = 0.059/z log (1 - i/iL) at 298 K.

See class handouts for equations derivation

ME472: CORROSION ENGINEERING 1 Dr. Ihsan-ul-Haq Toor

 Concentration polarization (Limiting current density)
iL is increased by

• higher solution concentration, CB;

• higher temperature which increases diffusivity, D;
• higher solution agitation, which decreases .
Concentration polarization only becomes important when the current density approaches iL

Fig. Ref: DA Jones Book

ME472: CORROSION ENGINEERING 1 Dr. Ihsan-ul-Haq Toor