Compiled and edited by: Dr Padmalatha Rao Prof & Head: Dept of Chemistry

MODULE II
(Part I)
Corrosion chemistry: Introduction, electrochemical theory of corrosion, types-
differential metal, differential aeration, corrosion control-galvanization, tinning ,
anodization and sacrificial anode method. Corrosion penetration rate (CPR) -
introduction and numerical problem.
CORROSION CHEMISTRY
Corrosion is a natural phenomenon that causes a deterioration of the properties
of the metal due to the destructive action of environment. Corrosion can be defined as
spontaneous destruction or deterioration of a metal or alloys by the surrounding
environment because of chemical or electrochemical reaction. Free metals, as such
possess high energy. Whenever favourable situation arises, they combine with other
elements like oxygen to form compounds and attain the state of minimum energy with
maximum stability. Following figure shows that corrosion can be viewed as the reverse
process of extractive metallurgy.

Some examples for corrosion:

Rusting of iron: 4Fe(s) + 3O2(g) → 2Fe2O3.H2O(s)
Tarnishing of silver: 4Ag(s) +2 H2S(g) + O2(g) → 2Ag2S(s) + 2H2O(l)
Scales on copper: 2Cu(s) + H2O(l) + O2(g) + CO2(g) → [CuCO3 + Cu (OH)2] (s)

TECHNOLOGICAL IMPORTANCE OF CORROSION STUDY

An interdisciplinary area embracing chemistry, material science and mechanics is
involved in the study of corrosion. Some reasons to study corrosion as science and
engineering subjects are:

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Compiled and edited by: Dr Padmalatha Rao Prof & Head: Dept of Chemistry

✓ Human life and safety: Loss of life results when structures collapse due to
combined effects of stress and corrosion. Safety issue can be due to release of
certain toxic product as a result of corrosion, sudden failure of equipment may
cause fire or explosion.
✓ The cost of corrosion: The annual losses due to corrosion are approximately 3-4%
of GDP in many advanced countries and it is even more in developing countries.
✓ Need of conservation of Materials: Damage of metal due to corrosion is observed I
all fields. Thus, corrosion affects the earth’ s material resources.
✓ Academic interest: The study of corrosion is challenging and interesting as
corrosion science is an interdisciplinary area. A blend of chemistry, materials
science and mechanics must be included to understand the various forms of
corrosion

ECONOMIC IMPACT OF CORROSION

✓ Maintenance and operating costs: One fourth of the iron produced is used to replace
bridges, buildings and other structures that have been destroyed by corrosion. The
corrosion causes damage to chemical process plants and other equipment.
✓ Plant shutdowns, loss of production while the plant is inoperable during
repairs/replacement work
✓ Contamination and loss of valuable products- Leaking containers, tanks, pipelines
results in significant losses in product, which have a high cost. Soluble corrosion
products can spoil and contaminate chemical preparations.
✓ Loss of efficiency- the corrosion products decreases the heat transfer rate in heat
exchangers.

CORROSION CLASSIFICATION
Corrosion of metals depends on the environment to which the metals are exposed.
The corrosion of the metals can be classified into two major categories. They are
✓ Dry or chemical corrosion
✓ Wet or electrochemical corrosion
Dry or Chemical Corrosion
This type of corrosion occurs by direct chemical interaction between the
environment and the metals and alloys. Presence of an electrolyte/conducting corrosive

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medium is not at all essential for dry corrosion to occur. Due to the direct interaction
between metal and corrosive environment, it is also known as direct corrosion. Dry
corrosion could be due to oxygen (O2), or by other gases (like SO2, Cl2, H2S and NOx etc.,)
or by liquid metals (Eg: liquid metal mercury dissolving most of the metals forming
amalgams there by corroding them)
Wet or Electrochemical corrosion
For wet corrosion to take place presence of conducting medium is very much
necessary. Wet corrosion occurs due to the formation of separate anodic and catholic
areas. It involves flow of electron between the anodic and cathodic areas through
electronic conductor. This is known as corrosion current. Metal ions formed a t the anode
will combine with anions of electrolyte and forms corrosion product somewhere between
anodic and cathodic areas.
When a metal is in contact with an acid solution or dissimilar metals are dipped
partially in a corrosive environment this type of corrosion can be observed.

Electrochemical theory of corrosion:

According to electrochemical theory of corrosion, when a metal is exposed to
corrosive environment, the process of corrosion sets in by the formation of number of
anodic and the cathodic areas on the metal surface (micro galvanic cell). The potential
difference in between anodic and cathodic areas is the driving force for electrons to flow
from the anodic area to the cathodic areas. Corrosion always occurs at the anodic area
of the metal due to oxidation process and thus electrons are liberated.
Electrochemical theory of corrosion can be schematically represented as follows:

Four conditions are necessary for electrochemical corrosion to occur. These are

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Compiled and edited by: Dr Padmalatha Rao Prof & Head: Dept of Chemistry

An anodic reaction (oxidation)

A cathodic reaction (reduction)
A metallic path of contact between anodic and cathodic sites (electronic conductor)
An electrolytic path of ions from corrosive medium towards cathodic areas.

Reactions which are taking place during electrochemical corrosion are summarised
below:
Anodic reaction:
M → Mn+ + n𝑒 −
Zn → Zn2+ + 2𝑒 −
Cathodic reactions:
The electrons set free at the anodic area flow through the metallic conductor and are
consumed at the cathodic area. Depending upon the nature of corrosive medium different
cathodic reactions are possible in the absence and in presence of oxygen. They are:
(i) Hydrogen reduction in acid medium in absence of oxygen
2H+ (aq) + 2e− → H2
(ii) Hydrogen reduction in acidic medium in presence of oxygen
4H+ + O2 + 4e- → 2H2O
(iii) Reduction of water in absence of oxygen
2H2O + 2e− → H2 (g) + 2OH− (aq)
(iv) Reduction of water in presence of oxygen
O2 (aq) + 2H2O + 4e− → 4OH−(aq)
Hydrogen reduction and oxygen reduction are the most common cathode reaction,
since any aqueous solution in contact with air contains dissolved oxygen.
From, electrochemical theory, it is clear that no corrosion take place at the
cathodic area, since cathodic reaction does not involve metal dissolution. Corrosion and
hence metal dissolution take place only at anodic area. Cathodic area stimulates corrosion
of the anodic part by utilizing the electrons produced at anodic area.

Mechanism of rusting:
Rusting is the name more commonly referred for the corrosion of iron. When iron
is exposed to atmosphere, in the presence of moisture, it undergoes corrosion. Depending

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upon the concentration of oxygen present in the environment different types of corrosion
products are produced. Following figure illustrates the mechanism of rusting:

Reactions :
At anodic sites: Fe → Fe 2+ + 2e−
Electrons liberated at the anode migrate to the cathode causing corrosion current. The
Fe2+ ions formed at the anode combine with OH- liberated at the cathode to form the
corrosion product (ferrous hydroxide) somewhere between the anode and cathode, after
diffusing towards each other through the conducting me
At cathodic sites: O2 (g) + 2H2O (l) + 4e− → 4OH−(aq)
Overall reaction: 2Fe + O2 (g) +2H2O (l) → 2Fe2+ (aq)+ 4OH−(aq) → 2Fe (OH)2
In presence of enough oxygen, ferrous hydroxide reacts with moisture and oxygen to give
yellow rust.
4 Fe (OH)2 + 2 H2O + O2 → 2 [ Fe2O3. 3H2O] (Yellow rust)
If the supply of oxygen is limited, the corrosion product is black rust - anhydrous
magnetite.
6 Fe (OH)2 + O2 → 2 [ Fe3O4. 3H2O] (Black Rust)
Rust is a brittle substance that easily flakes off the surface to expose more iron atoms and
the process starts over again. It is too porous to shield the underlying metal from further
oxidation.
Differences between dry corrosion and wet corrosion
Dry Corrosion Wet Corrosion
Involves direct attack of Occurs due to existence of separate
atmospheric gases like anodic and cathodic areas between
O2, SO2 and liquid metal

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which current flows through the

medium

No need of aqueous Needs an aqueous conducting

corrosive electrolyte corrosive electrolyte
Types include oxidation Types include galvanic, pitting, stress
corrosion, liquid metal and inter- granular
corrosion and corrosion
by gases
Less prevailing More common

CORROSION TYPES:
1. Galvanic corrosion / Differential metal corrosion
This form of corrosion occurs when two dissimilar metals are in physical contact in
an aqueous electrolyte. Metal with lower standard reduction potential has tendency to
undergo oxidation. Hence it undergoes corrosion. Metal with higher standard reduction
potential will acts as cathode and remains un-attacked. Driving force for galvanic
corrosion is potential difference between two metals.

When zinc is made to be in contact with copper, zinc acts as anode and undergoes
corrosion because of lower standard reduction potential ( - 0.76V) and copper remains
unaffected since its SRP is high ( + 0.34V)
Anodic reaction : Zn → Zn2+ + 2e− ( corrosion )
Cathodic reaction depends upon the nature of corrosive environment:
2H+ (aq) + 2e− → H2 ( Hydrogen evolution)
O2 (g) + 2H2O (l) + 4e− → 4OH−(aq) ( oxygen absorption)

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Compiled and edited by: Dr Padmalatha Rao Prof & Head: Dept of Chemistry

Some examples of galvanic corrosion are given below:

• Copper piping connected to steel tanks.
• Zinc coated screws in a sheet of copper
• Steel propeller shaft in bronze bearing
Galvanic corrosion also occurs in the atmosphere. The severity depends largely on the
type and the amount of the moisture present. Corrosion is greater in the seashore than in
a dry rural atmosphere. Condensate near a sea shore contains salt and therefore is more
conductive (and corrosive) and a better electrolyte than condensate in an inland location.
Accelerated corrosion due to galvanic effects is usually greatest near the junction with
attack decreasing with increasing distance from that point. In the galvanic couple like
Zn/Fe, Fe/Sn, Fe/Cu, Zn/Sn, Zn/Cu; the first metal is anodic with respect to the second
metal and hence undergoes corrosion. It is to be noted that nuts, bolts, and hinges are
made up of one single metal or alloy in order to prevent the galvanic corrosion.

2.Differential aeration corrosion

Differential aeration corrosion, which is also known as concentration cell
corrosion happens when a metal is exposed to different concentrations of air or oxygen.
The part of the metal exposed to less oxygen acts as anode and part of the metal exposed
to more oxygen acts as cathode.
Eg: A plate of pure zinc which is partially immersed in an aerated solution of sodium
chloride.

Anodic reaction at lower immersed portion of metal : Zn → Zn2+ + 2e

Cathodic reaction near the water surface : ½ O2 + H2O + 2e − → 2OH-

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Water line corrosion and pitting corrosion are best examples for differential aeration
corrosion
Water line corrosion:
Waterline corrosion is common in water lifting pipes under water. When a storage
tank is used to collect water upto certain level, just below the water line concentration of
oxygen is less. Above the water line metal is exposed to large excess of oxygen/air. Just
below the water line material will become anode and corrosion products will be
deposited. Ocean going ships also suffer from this type of corrosion. Ships sunk under
water for several years do not undergo corrosion, as they are exposed to equal
concentrations of oxygen.

Pitting Corrosion
Pitting corrosion is a localized attack that results in extreme cases holes in the
metal. Surface appears rough as pits are sometimes isolated or close together. Generally
a pit may be described as a cavity or hole with the surface diameter about the same length
as or less than the depth. Pitting is localized and intense form of corrosion and failure
often occurs with extreme suddenness without prior indication.
The important reasons for the pitting corrosion include surface roughness or non-
uniform finish, scratches or cut edges, local straining of metal due to non- uniform stress
and Deposition of extraneous matter such as sand, scale, water drop and dust .
Whenever dust particles are deposited, owing to the different amount of oxygen
in contact, with metal, the small part beneath the impurity becomes the anodic areas and
the surrounding large parts become the cathodic areas. Intense corrosion starts just
underneath the impurity. It is shown schematically in the following figure :

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Other examples for pitting corrosion include: peeling of tin coat on iron

CORROSION CONTROL TECHNIQUES:

Different techniques are being adopted to control corrosion. The technique
adopted to control/minimise corrosion largely depends upon the nature of corrosion. For
example: differential metal corrosion can be prevented by selecting materials having very
less potential difference or by placing a thin layer of an insulator between two metals of
different electrode potential. At the same time differential aeration corrosion can be
prevented by metallic coating etc
Application of protective coating is one of the important methods of corrosion
control. The protective coating prevents the metallic corrosion by forming a barrier film
on the surface of the metal. Deposition of a protective metal over the surface of the base
metal is known as metallic coating. There are two types of metal coating. They are anodic
coating and cathodic coating
In anodic metal coating coated metal is more active than the base metal. Hence
coated metal will corrode when exposed to corrosive environment and protects the base
metal from undergoing corrosion. Best example is galvanisation. Galvanisation is coating
of iron with a layer of zinc. Cathodic metal coating is coating the base metal with more
noble metal. Coated metals are less reactive than the base metal and are less susceptible
for corrosion. Eg: Tinning, where iron is coated with noble metal tin

Galvanisation:
Giving a Zn metal coating on iron / mild steel is known as galvanization. When the
coating covers the entire surface of the substrate metal, the coating isolates it from the
environment and protects it against corrosion. When the coating breaks or cracks zinc
act as anode and the substrate iron and mild steel acts as cathode. Thus, zinc becomes

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Compiled and edited by: Dr Padmalatha Rao Prof & Head: Dept of Chemistry

sacrificial anode and provides protection to iron and mild steel sheets, pipes, wires are
usually galvanized. Galvanisation is done by hot dipping process as discussed below:

Pretreatment: The metal surface is cleaned to remove organic matter like grease/oil by
washing with organic solvents. The rust and other deposits are removed by washing
with dilute sulfuric acid and the surface is finally washed with water and air dried.
Process: Galvanization is done by hot dipping processes. Melting point of Zn is 419 oC. Zn
is melted and kept at 425-430 oC. Ammonium chloride flux is spread over it to prevent its
oxidation by air. Iron and mild steel objects are degreased, pickled and cleaned. They are
then dipped in molten Zn bath. Pair of hot rollers wipes out excess of zinc coating to
produce a thin uniform coating on the objects which are then cooled. It is shown
schematically in above figure. Galvanized sheets cannot be used to prepare tins or cans
for storing food materials, because zinc salts are toxic.
Applications: Used in the manufacture of fencing wire, roofing sheets, buckets, bolts,
nuts, nails and screws
Main advantage of galvanisation is that, base metal will never undergo corrosion
even if the coating is ruptured. However galvanised articles should not be used for
preparing and preserving food stuffs since zinc dissolves in dilute acids present in food
stuffs producing toxic zinc compounds

Tinning:
Steel sheet is washed with organic solvents to remove grease/oil deposits. It is
then treated with dilute sulfuric acid to remove rust deposits and finally washed with
water and air dried.
Process: Tinning is done by hot dipping. Melting point of Sn is 232 oC. Cleaned sheet is
passed through molten ZnCl2 and NH4Cl flux to help molten tin to adhere on the metal
surface. It is the dipped into molten tin maintained at 250 ℃. Finally passed through
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series of rollers immersed in palm oil. The rollers wipe out excess tin and oil prevents
oxidation of tin
Metal coated with tin are mainly used for storing food stuffs such as jam , food
items, milk products etc., However, tin coating provides complete protection against
corrosion only if it covers the steel surface completely. If small crack is formed in the
coating the galvanic cell formed with exposed steel/iron as anode and tin coating as
cathode. An intense localised corrosion occurs at the exposed iron surface because of
large cathodic area (tin) and small anodic area.
Differences between galvanisation and tinning:

Galvanization
A process of coating Zn over
iron/steel to prevent it from
rusting (anode metal coating)
Hot rollers used to wipe excess coat
are not immersed in oil
Galvanized containers cannot be
used to store acidic foodstuffs
because zinc reacts with food acids
forming highly toxic zinc
compounds.
Zinc protects the underlying iron
by sacrificial action
Tinning
A process of coating Sn over
iron
to prevent it from corrosion
(cathode metal coating)
Hot rollers are immersed in
Palm oil
Tin coated containers can
be used to store foodstuffs
because tin is nontoxic and
does not react to cause any
food poisoning
Tin protects the base metal
iron due to its noble nature.

Zinc continues to protect iron by Tin protects the iron till the
sacrificial action in the event of coating is perfect and any
puncture/break in coating break causes rapid
corrosion of iron

Sacrificial anode method

In sacrificial anode method, more reactive metal is kept in contact with the metal
structure to be protected. The reactive metal becomes anodic part and the structure
becomes cathodic part of the corrosion cell. The anode is sacrificed to protect the
structure. Hence this method is called sacrificial anode method.

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Mg is generally used as sacrificial anode for protecting iron article. Mg is more reactive
metal than iron and hence it is usually used as anode. It becomes anodic part when in
contact with iron. Following reaction take place when Mg is made to couple with Iron.
At Anode: 2Mg(s) → 2Mg2+ (aq) + 4e−
At Cathode: O2 (g) + 2H2O (l) + 4e− → 4OH−(aq)
Net reaction: 2Mg (s) + O2 (g) + 2H2O (l) → 2Mg(OH)2
Advantages: No external power supply is necessary.
Can be used in remote and difficult to reach areas.
Low installation and maintenance cost.
Replacement is much cheaper than replacing the tank/oil pipeline

Corrosion control by anodization:

Anodization is an example for inorganic chemical conversion coating. In this
surface of metal is converted into a compound by chemical or electrochemical reactions.
The resultant product forms a barrier between the metal and corrosive environment.
These chemical conversion coatings are integral part of metal itself. Eg: Al, Zn, Mg etc.,
Anodization of aluminum :

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Anode: aluminum
Cathode: Steel/copper/lead
Electrolytic bath: chromic acid/sulfuric acid/phosphoric acid
Temperature: 35 ℃
Current density: 10-20 mA/cm2
Thickness of oxide layer formed: 2-8 𝜇m
Anodization carried out by using phosphoric acid bath tends to be porous and provides
good adherence for paints and dyes.
Anodised articles are used as in soap boxes, tiffin carriers and window frames etc.,

Corrosion penetration rate: (CPR)

Rate at which material losses its weight as a consequence of corrosion is known
as corrosion rate. Corrosion rate is a measure of corrosion resistance. Corrosion rates
can be expressed in a variety of ways. They are % weight loss, mg /cm2/day, g/inch2/hr
etc, However, these do not express corrosion resistance in terms of penetration.
From an engineering view point, the rate of penetration, or thinning of a structural
piece is a useful tool to predict the life of a given component. The expression mils per
year (mpy) is the most desirable way of expressing corrosion rate. It can also be
expressed by milli mils per year (mmpy) (1mil = 0.001inch)
𝐾𝑥𝑊
In general corrosion penetration rate (CPR) =
𝐷 𝑥𝐴 𝑥 𝑇

Parameters Significance CPR ( in mpy) CPR ( in mmpy)

( Units to be taken) ( Units to be taken)
K Constant 534 87.6
W Weight loss mg mg
D Density g/cm 3 g/cm3
A Area inch2 cm2
T Time duration Hours hours
1inch = 6.4516cm
2 2

1 year = 1x365 x24 = 8760hr

1kg = 106 mg
Numerical Problems:
1. A 5.5 kg of iron metal piece of density 8.1g/cm3 with area 10.0 inch2 was
submerged in sea water for 10.5 years. Weight of the remaining metal was found
to be 2.4 kg. Calculate CPR in mpy and mmpy

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𝐾𝑥𝑊
CPR =
𝐷 𝑥𝐴 𝑥 𝑇
534 𝑥 3.1𝑥106
= = 222.19 mpy
8.1 𝑥10 𝑥 10.5 𝑥365𝑥24
87.6 𝑥 3.1𝑥106
= = 5.64 mmpy
8.1 𝑥10𝑥 6.4516 𝑥 10.5 𝑥365𝑥24
Numerical problem for practice:
1. Corrosion penetration rate of square iron metal weighing 5.5 kg was reported to be
222.19mpy and 5.65 mmpy. It was submerged in sea water for 16.2 years. At the end of this
time period, metal weighed 1.9 kg . What was area of the metal? Express your answer in cm2
and inch2 [Given density = 8.1g/cm3]
2. 7.8 kg of iron piece of density 8.1g/cm3 with area 12.5 inch2 was submerged in sea
water for 13.5 years. Weight of the remaining metal was found to be 4.8 kg. Calculate
CPR in mpy and mmpy

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