MM435_Corrosion, Degradation and Protection

Fall-2020

By

Ramzan Abdul Karim

GHULAM ISHAQ KHAN INSTITUTE OF ENGINEERING & TECHNOLOGY

FACULTY OF MATERIALS & CHEMICAL ENGINEERING

 Corrosion Kinetics
Upcoming Topics…

➢ Electrical Double Layer

➢ Exchange Current Density

➢ Corrosion Rate Calculations (Faradays Laws of Electrolysis)

➢ Polarization (Evans Diagrams)

➢ Kinetics of Passivity

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 Electrical Double Layer
Distribution of anions and cations at a metal – solution interface (Double Layer):

A compact layer (Helmholtz)

closest to metal surface in which
charge distribution and hence

Metal Surface
potential varies linearly with
distance

A more diffuse inter layer (G. C.

layer) where potential changes
exponentially
Electrolyte Solution

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Electrical Double Layer

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Electrical Double Layer

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Energy-Distance Profile
These are plots of free energy (ΔG) v/s the distance representing the progress of reaction
through the double layer.

➢ The metal atoms are located in energy wells

associated with lattice structure.

➢ A metal atom cannot be detached from

the lattice and pass into the solution until it
crosses an energy barrier, called activation
energy.

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Reversible and Irreversible Processes
Reversible:

where K1 is the constant depending on

temperature, time and activity.

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Reversible and Irreversible Processes
Irreversible:

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Exchange Current Density:
it implies rates of dissolution and deposition reactions are equal when metal
in solution is at equilibrium (Reversible Process)

Exchange current density of Hydrogen (H2) Evolution on various surfaces..??

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Exchange Current Density:
Exchange current density (io) is dependent on:

a) Nature of the redox reaction

b) Electrode composition / surface
c) Concentration ratio of oxidized and reduced species
d) Temperature.

For example,
➢ io for H+ / H2 reaction on platinum
-2
is about 10 A/cm2 and
➢ io for H+ / H2 reaction on mercury
-13 2
is about 10 A/cm ,
➢ This means it is easier to reduce
hydrogen ions from acidic
electrolyte on a platinum
electrode unlike on mercury,
which possesses a high
Hydrogen-overvoltage. MM-435_Corrosion Degradation and Protection 10
 Faraday’s Laws and corrosion rate calculation:
1st Law
The mass of primary products formed at an electrode by electrolysis is directly proportional to the
quantity of electricity passed
I = current in amperes
t = time in seconds
m = mass of the primary product in grams
Z = constant of proportionality (electrochemical equivalent). It is the mass of a substance liberated by 1 ampere-second of a current (1
coulomb).
nd
2 Law
The masses of different primary products formed by equal amounts of electricity are
proportional to the ratio of molar mass to the number of electrons involved with a
particular reaction:

m1, m2 = masses of primary product in grams

M1, M2 = molar masses (g.mol−1)
n1, n2 = number of electrons
Z1, Z2 = electrochemical equivalents.

Combining the first and second laws,

Substituting for Z from 2nd law OR

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Applications of Faraday’s Laws:

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Applications of Faraday’s Laws:

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Applications of Faraday’s Laws:

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 Applications of Faraday’s Laws:
Determination of Penetration depth:

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Applications of Faraday’s Laws:

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Problem
A sample of zinc corrodes uniformly with a current density of 4.2 ×10−6 A/cm2
in an aqueous solution.

(a) What is the corrosion rate of zinc in mdd (mg/dm2/day)?

(b) What is the corrosion rate of zinc in mm/year?
[MZn = 65.38 g/mol, ρ(Zn) = 7.1 g/cm3, F =96 500 C ]

Solution
(a) What is the corrosion
rate of zinc in mdd (mg/dm2/day)?

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 (b) What is the corrosion rate of
zinc in mm/year?

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Applications of Faraday’s Laws:
Current density Penetration rates Mass/Weight loss

Current density

Penetration
rates

Mass/Weight loss

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Applications of Faraday’s Laws:
Corrosion rate determination of an alloy..??

(in mpy)

Composition Atomic Weight Density, ρ

Element
(%) (g/mol) (g/cm2)
Cr 18 52.01 7.10
Ni 10 58.68 8.9
Mo 03 95.95 10.2
Fe 67 55.85 7.86

Mn 02 54.94 7.45

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Kinetics of Corrosion
POLARIZATION

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Polarization:
When electrode reactions take place, the potential will no longer be at equilibrium due to
current flow through an electrochemical cell-causing a change in the electrode reversible
potential. This electrochemical phenomenon is termed as POLARIZATION.
Corroding systems are not in equilibrium → deviation from
thermodynamics.
The Deviation of the potential from its reversible value is
referred to as POLARIZATION.

It is given by:

η = E − Erev
where:
η is the Polarization or deviation of the potential,
E is applied/measured potential and
Erev is the reversible potential.

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 measured

Solution η = E − Erev

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Polarization:
The Deviation of the potential from its reversible value is referred to as POLARIZATION.

Types of Polarization:

Polarization of anode – anodic polarization Types of polarization

Polarization of cathode – cathodic polarization w.r.t type of electrodes

Sub Types:
1. Activation Polarization (Over Potential)
2. Concentration Polarization

Total Polarization:

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Polarization:
Activation Polarization (Over-potential)
Activation polarization is caused by a slow step in the electrode reaction (electrode reaction
requires activation energy in order to reach the final state)
The magnitude of shift of potential in the noble direction is called ‘over potential’ or
‘Activation Polarization’ (ηAct) .
The relationship between activation polarization (over-potential) and the rate of the reaction
(ia and io) is given as:

Tafel relationship.

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Polarization:
Activation Polarization (Over-potential)

Magnitude of io (exchange current density) will indicate as to whether the redox reaction is
reversible or irreversible.

Lower io denotes higher over-potential Irreversibility

Higher io indicates lower over-potential Reversibility

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Polarization:
Concentration Polarization

Polarization resulting from concentration gradients is termed as concentration polarization

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Polarization:
Resistance Polarization

The contribution to polarization due to IR drops is referred to as Resistance polarization

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