Chapter 3

Principles of corrosion
 Metals occur in nature in the form of their compounds (ores).
Metal
∴Metals are less stable than
E
their compounds.

Ore
(Cpd)
 Corrosion
 Corrosion may be defined as destruction of a
material due to the contact with its surrounding
environment.

 Types of Corrosion
1. Direct or Chemical Corrosion (Dry Corrosion).

2. Indirect or Electrochemical Corrosion (Wet Corrosion).

 CLASSIFICATION OF CORROSION

Chemical corrosion (dry corrosion) Electrochemical corrosion (wet corrosion)

It is a direct chemical reaction It is an electrochemical reaction between
occurs between metal or alloy metals and the environment.
surface and environment Takes place at the anodes of the micro
Takes place by direct combination of electrochemical corrosion cells formed on the
metal and its environment . There is metal surface
no transport of electric charge.
ex: A C A C C A
•Dissolution of metals in contact with A
C A A
non-conducting organic media. C C
•Destruction of metals attacked at high A A
temperatures by aggressive gases. A C C A C A

The five essential components of the

corrosion cell are:
1- Anodic zones (A)
2-Cathodic zones (C)
3-electrical contact between them
4-an (ionically) conducting solution
5- cathodic reactant
Requirements for Electrochemical
Corrosion:

Electronic Path

ANODE CATHODE

Ionic – Current Path Cathodic

Where
Reaction
Corrosion
Occurs!!!!
 Oxidation Reduction

 LOSS of electrons (Zn  Zn2+ + 2e) • GAIN of electrons (Cu2+ + 2e  Cu)

 Removal of H or gain of O • Removal of O or gain of H
 Take place at anode (dissolution) • Take place at cathode (deposition)
 Oxidation Reaction  Anodic • Reduction Reaction  Cathodic Reaction
Reaction • Reduced species carried a more
 Oxidized metal carry a more negative charge (less positive).
positive charge (less negative) • For strong acidic medium (pH<4)
 Metal  Positive Ion + Electron(s) 2H + + 2e-  H2
 M  M n+ + ne- (n=1,2,3,…) • For neutral or basic medium (pH= 4-10)
 Na  Na + + e- & Fe  Fe 2+ + 2e- • 1/2 O2 + H2O + 2e-  2OH-
&2014Al- II Al 3+ + 3e- 9
 The corrosion cell reactions
 The anodic reaction is:
M → M+z + ze
 The most common cathodic reactions are:
(I) O2 + 4H+ + 4e-  2H2O eo = 1.23 V O2 rich acidic media
OR
(II) O2 + 2H2O + 4e-  4OH- eo = 0.401 V O2 rich non acidic media
OR
(III) 2H+ + 2e-  H2 eo = 0.0 V O2 poor acidic media
OR
(IV) 2H2O + 2e-  H2 + 2OH- eo = -0.828 V O2 poor non acidic media
pH-scale
It’s a scale to determine the acidity or alkalinity
strength.

0 4 4 7 7 10 10 14

Strong acid Weak acid Weak base Strong base

Sulfuric acid Acetic acid Ammonia Sodium hydroxide

Hydrochloric acid Oxalic acid Potassium hydroxide
Phosphoric acid Citric acid
Electrochemical Cells

Galvanic Electrolytic
(Voltaic) Cell Cell
using electricity to force a
generating electricity by chemical reaction to occur
using a spontaneous (one that is non-spontaneous,
chemical reaction (one DG = + ve).
with DG = - ve) The two electrodes are
connected with an external
source of potential..
Electrochemical cells

Galvanic cell
Chemical Electrical
Electrolytic cell
Energy Energy

Galvanic corrosion cell

concentration corrosion cell
Corrosion cell

Electrolytic corrosion cell

Galvanic cell
I- Galvanic
(Voltaic) Cell
Observe the
electrodes
to see what Salt bridge –
is occurring. KCl in agar
Provides conduction
between half-cells

Zn Cu

1.0 M ZnSO4 1.0 M CuSO4

What about half-cell What about the sign
reactions? of the electrodes?

Why? - +
anode half-cell cathode half-cell
Zn  Zn+2 + 2e- Cu+2 + 2e-  Cu

Zn Cu
electrode What plates out
corrodes happened or
or Zn at each Cu deposits
dissolves electrode? on
electrode
1.0 M ZnSO4 1.0 M CuSO4
II-Electrolytic - + power
Cell battery
source
e-
e-

conductive
medium

(-) (+)
vessel inert
electrodes
Sign or polarity of electrodes
 Ex: Molten NaCl Electrolysis
At the microscopic level
- +
battery
e-

NaCl (l)

cations anions
migrate Na+ migrate
toward Cl- Na+ toward
(-) (+)
e-
electrode (-) Cl- (+) electrode

cathode Cl- Na+ anode

Na+ + e-  Na 2Cl-  Cl2 + 2e-

 Remember
The corrosion cell reactions
 The anodic reaction is:
M → M+z + ze
 The most common cathodic reactions are:
(I) O2 + 4H+ + 4e-  2H2O eo = 1.23 V O2 rich acidic media
OR
(II) O2 + 2H2O + 4e-  4OH- eo = 0.401 V O2 rich non acidic media
OR
(III) 2H+ + 2e-  H2 eo = 0.0 V O2 poor acidic media
OR
(IV) 2H2O + 2e-  H2 + 2OH- eo = -0.828 V O2 poor non acidic media
 The Electrochemical Series

2H2O + 2e-  H2 + 2OH- -0.828

Au3+ + 3e- ⇋ Au E0 = 1.420 V
Strong tendency to occur as a reduction
(i.e. as written Au3+ + 3e-  Au)

Na+ + e- ⇋ Na E0 = -2.71 V
Strong tendency to occur as an oxidation
(i.e. Na  Na+ + e-)
O2 + 4H+ + 4e- ⇋ 2H2O eo = 1.23 V O2 rich acidic media

Cu+ + 1e ⇋ Cu eo = 0.52V
O2 + 2H2O + 4e- ⇋ 4OH- eo = 0.401 V O2 rich non acidic media
2X Cu2+ + 2e ⇋ Cu eo = 0.34V

2H+ + 2e- ⇋ H2 eo = 0.0 V O2 poor acidic media

Fe3+ + 3e ⇋ Fe eo = -0.04V
Fe2+ + 2e ⇋ Fe eo = -0.44V
2H2O + 2e- ⇋ H2 + 2OH- eo = -0.828 V O2 poor non acidic media
O2 + 2H 2Cu2H
4H+2O+ +2Cu  2Cu
2 O 2+ 2Cu
+ + 2+ - in O rich non-acidic
4OH 2 acidic media
media
Polarization
the shift of the electrode potential
from its equilibrium value
The rate of electrochemical reaction is limited by
various physical and chemical factors.

The electrochemical reaction is retarded by

several physical and chemical factors.

Polarization is inversely proportional to the

corrosion rate.
 Steps of electrochemical reaction:
1. Ion transfer from the bulk of solution to the surface through the
diffusion layer (mass transfer step)
2. Chemical reaction between ions and electrons. (Oxidation or reduction)
(charge transfer step)
3. Material transfer from the surface of metal to the bulk of solution through
the diffusion layer. (mass transfer step).
Example: Reduction of hydrogen:
2H+ + 2e-  H2(g)

H H+

Metal (1) mass transfer step

H (2) Charge (electron) transfer step
Chemical reaction

(3) mass transfer step

-the first and third steps are mass transfer steps.

-the second step is chemical reaction step.
Polarization can be conveniently
divided into two types:
Concentration polarization
Refers to electrochemical reaction that’s controlled by the mass transfer (diffusion)
step in the electrolyte.
Condition: the mass transfer step is slower than the chemical reaction.
Occurs in diluted solutions

Activation polarization
Refers to electrochemical reaction that’s controlled by the chemical reaction
sequence at the metal surface.
Condition: the chemical reaction is slower than the mass transfer.
Occurs in concentrated solutions
Examples:
Corrosion rate in concentrated electrolyte is chemical reaction controlled. (Act. Pol.) slow step 2
Corrosion rate in diluted electrolyte is diffusion controlled. (Conc. Pol.) slow step 1 or 3

Corrosion rate  polarization  25

 Passivity Environment Iron Aluminum

Some metals and alloys under particular Air Non passive passive
environmental condition loss their Nitric acid passive Non passive
chemical reactivity and become passive. (HNO3)

Passivity may be defined as the formation of a thin protective film (1-10 nm

thickness) on a metal surface due to its reaction with the surrounding
environment under oxidizing conditions. (Passive film is protective only if: (1)
adherent (2) non-porous, dense and compact)., e.g., the formation of oxide
layers of Al2O3, TiO2, Cr2O3. this is why Cr is added to Fe to prepare stainless
steel

Passivity depends mainly on:

• The nature of the metal or alloy.
• Type of the environment (composition,
temp., humidity, …. ).

Potentiodynamic polarization Passivity curve

 Potentiodynamic
polarization

Active behaviour
Fe/HCl Active/passive metals

Current density
Current density

Zn/NaOH
The magnitude of the anodic
current is a measure of the rate
of the anodic reaction
Passive region

Anodic Potential Anodic Potential

Epass ipass

ipass is a measure of the rate of dissolution

through the passive layer
Current density

High ipass means poorly protective

Potentiostatpassive
Passive behaviour layer Anode
Al/H2SO4 Small ipass value
(oxidation)
reflects good metal
protection by the passive layer
Passive region

Anodic Potential
ipass
Current density

Passive region

Anodic Potential Active region: in this region, a slight

Epass
increase in the potential or oxidizing
power of the solution causes rapid
increase in the corrosion rate.

Passive region: by increasing the oxidizing power

the corrosion rate show sudden decrease and
further increase in the oxidizing power produce no
change( rate is constant).

 Trans passive region: at very high values of oxidizing power, the corrosion rate or the
rate of another oxidation process again increases as oxidizing power increase.
Corrosive environment
Air, water, soil, gases, and acids may acts as corrosive
environment.
Types of corrosive environment:
 Air:
 Moist and humid air is more corrosive than dry air.
 Hot air is more corrosive than cold air.
 Polluted air is more corrosive than fresh air.
 Water:
 Hot water is more corrosive than cold water.
 Salty water is more corrosive than fresh water.
 Polluted water is more corrosive than pure water.

 Gases:

Acidic gases (SOx, NOx, and H2S.) are more corrosive than Basic
gases (NH3).
 Soil:
Presence of water, salts, gases, stray current, pollutants, affects the
corrosion rate greatly.
 Acid Mineral Organic Fatty
 Acids:
Strength Very strong Weak Very weak
Acids are very corrosive
Examples H2SO4, Acetic and Animals
environment. HNO3, Formic acid and plant
H3PO4, oils
HCl……

 Bases:
Strong bases (sodium hydroxide, potassium hydroxide) are more
corrosive than weak bases (ammonia solution).