Applied Chemistry

Unit-3

CORROSION AND ITS CONTROL

Department of Applied Chemistry

Bhilai Institute of Technology, Durg (C.G.)
B.Tech. First / Second Semester, BIT Durg, Applied Chemistry; Unit-3
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 SYLLABUS
UNIT – III: Corrosion CO3
Types of corrosion, Dry corrosion: Oxidation corrosion & its mechanism, Nature of oxide
film, Wet corrosion- Electrochemical theory of corrosion, Galvanic corrosion, Concentration
cell corrosion , Differential aeration corrosion: Pitting, Water line & stress corrosion, factors
affecting corrosion, Galvanic Series ,Protection against corrosion: Modifying the
environment, Use of Inhibitors, Proper design & material selection, Cathodic Protection:
Sacrificial anode method, Impressed current Cathodic protection, Anodic & cathodic
coating. [8Hrs]

Course Outcome:
CO3: Apply the concept of corrosion to increase the life of materials of operating units.

UNIT-3
CORROSION AND ITS CONTROL
Introduction: Most metals (with the exception of noble metals such as Au, Pt, etc.) exist in
nature in combined forms as their oxides, carbonates, hydroxy carbonates, sulphides,
chlorides and silicates. These are reduced to their metallic states from their ores, during their
extraction processes. During extraction of metals, a considerable amount of energy is
required. Consequently, isolated pure metals can be regarded in excited state (a higher energy
state) than their corresponding ores, and they have a natural tendency to revert back to
combined state (or lower energy state). Hence, when metals are put into use, in various
forms, they are exposed to environment (such as dry gases, moisture, liquids, etc), the
exposed metal surfaces begin to decay (i.e., conversion into more stable metal compounds)
more or less rapidly, when they come in contact with gaseous and / or liquid environment (or
surroundings). In other words, destruction or deterioration of the metal starts at the surface.
This type of metallic destruction may be due to direct chemical attack (by the environment)
or electrochemical attack (i.e., similar to reaction in a Daniel cell).

Any process of deterioration (or destruction) and consequent loss of a solid metallic material,
through an unwanted (or unintentional) chemical or electrochemical attack by its
environment, starting at its surface, is called corrosion. Thus, corrosion is a process “reverse
of extraction of metals”.

The most familiar example of corrosion is rusting of iron, when exposed to the atmospheric
conditions. During this, a layer of reddish scale and powder of oxide (Fe3O4) is formed, and
the iron becomes weak. Another common example is formation of green film of basic
carbonate [CuCO3 + Cu(OH)2] on the surface of copper, when exposed to moist-air
containing carbon dioxide.

Dry or Chemical Corrosion: This type of corrosion occurs mainly through the direct
chemical action of environment / atmospheric gases such as oxygen, halogen, hydrogen

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sulphide, sulphur dioxide, nitrogen or anhydrous inorganic liquid with metal surfaces in
immediate proximity. There are three main types of chemical corrosion:

1. Oxidation corrosion is brought about by the direct action of oxygen at low or high
temperatures on metals, usually, in the absence of moisture. At ordinary temperatures, metals,
in general, are very slightly attacked. However, alkali metals (Li, Na, K, Rb, etc.) and
alkaline-earths (Be, Ca, Sr, etc.) are even rapidly oxidised at low temperatures. At high
temperatures, almost all metals (except Ag, Au, and Pt) are oxidised.

The reactions in the oxidation corrosion are:

 2Mn   2ne
2M  (Loss of electrons)
Metal ions

n
O2  2ne 
 n O2  (Gain of electrons)
2 Oxideions

n
or 2M n   n O2 
2M  O 2 
2 Meal ions Oxideions
 
Metal oxide

Mechanism: Oxidation occurs first at the surface of the metal and the resulting metal oxide
scale forms a barrier that tends to restrict further oxidation. For oxidation to continue either
the metal must diffuse outwards through the scale to the surface or the oxygen must diffuse
inwards through the scale to the underlying metal. Both transfers occur (see Fig. 1), but the
outward diffusion of metal is, generally, much more rapid than the inward diffusion of
oxygen, since the metal ion is appreciably smaller than the oxygen ion and consequently, of
much higher mobility.

Nature of the oxide formed plays an important part in oxidation corrosion process.

Metal + Oxygen 
 Metal oxide (corrosion product)

When oxidation starts, a thin layer of oxide is formed on the metal surface and the nature of
this film decides the further action. If the film is:

(i) Stable: A stable layer is fine-grained in structure and can get adhered tightly to the parent
metal surface. Hence, such a layer can be of impervious nature (i.e., which cuts-off
penetration of attacking oxygen to the underlying metal). Such a film behaves as protective
coating in nature, thereby shielding the metal surface. The oxide films on Al Sn, Pb, Cu, Pt,
etc., are stable, tightly-adhering and impervious in nature. Consequently, further oxidation
corrosion is prevented.

(ii) Unstable, i.e., the oxide layer formed, decomposes back into the metal and oxygen.

Metal oxide = Metal + Oxygen

Consequently, oxidation corrosion is not possible in such a case. Thus, Ag, Au, and Pt do not
undergo oxidation corrosion.

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(iii) Volatile, i.e., the oxide layer volatilizes as soon as it is formed, thereby leaving the
underlying metal surface exposed for further attack. This causes rapid and continuous
corrosion, leading to excessive corrosion, e.g., molybdenum oxide (MoO3) is volatile.

(iv) Porous, i.e., having pores or cracks. In such a case, the atmospheric oxygen have access
to the underlying surface of metal, through the pores or cracks of the layer, thereby the
corrosion continues unobstructed, till the entire metal is completely converted into its oxide.

Pilling-Bedworth rule: According to it “an oxide is protective or non-porous, if the volume

of the oxide is at-least as great as the volume of the metal from which it is formed”. On the
other hand, “if the volume of the oxide is less than the volume of metal, the oxide layer is
porous (or non-continuous) and hence, non-protective, because it cannot prevent the access of
oxygen to the fresh metal surface below.” Thus, alkali and alkaline-earth metals (like Li, K,
Na, Mg) form oxides of volume less than the volume of metals. Consequently, the oxide layer
faces stress and strains, thereby developing cracks and pores in its structure. Porous oxide
scale permits free access of oxygen to the underlying metal surface (through cracks and
pores) for fresh action and thus, corrosion continues non-stop.

Wet or Electrochemical Corrosion: This type of corrosion occurs: (i) where a conducting
liquid is in contact with metal or (ii) when two dissimilar metals or alloys are either immersed
or dipped partially in a solution. This corrosion occurs, due to the existence of separate
‘anodic’ and ‘cathodic’ areas / parts, between which current flows through the conducting
solution. At anodic area, oxidation reaction (i.e., liberation of free electrons) takes place, so
anodic metal is destroyed by either dissolving or assuming combined state (such as oxide,
etc.) Hence, corrosion always occurs at anodic areas.

At anode:

 M H  n e 
M  (Oxidation)
(Metal) ( Metal ion)

M H 
 Dissolves in solution
( Metal ion)


 Forms compound such as oxide.

On the other hand, at cathodic areas, reduction reaction (i.e., gain of electrons) takes place.
Usually, cathode reactions do not affect the cathode, since most metals cannot be further
reduced. So at cathodic part, dissolved constituents in the conducting medium accept the
electrons to form some ions (like OH , O2 ). The metallic ions (al anodic part) and non-
metallic ions (formed at cathodic part) diffuse towards each other through conducting
medium and form a corrosion product somewhere between anode and cathode. The electrons
set free at the anode flow through the metal and are finally consumed in the cathodic reaction.
Thus, we may sum up that electrochemical corrosion involves: (i) the formation of anodic
and cathodic areas or parts in contact with each other, (ii) presence of a conducting medium,
(iii) corrosion of anodic areas only, and (iv) formation of corrosion product somewhere
between anodic and cathodic areas.

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Mechanism of Wet or Electrochemical Corrosion: Electrochemical corrosion involves
flow of electron-current between the anodic and cathodic areas. The anodic reaction (i.e., at
anodic area) involves in dissolution of metal as corresponding metallic ions with the
liberation of free electrons.

At anodic area:  M H  n e
M (Oxidation)

On the other hand, the cathodic reaction consumes electrons with either by: (a) evolution of
hydrogen or (b) absorption of oxygen, depending on the nature of the corrosive environment.

(a) Evolution of hydrogen-type corrosion occurs, usually, in acidic environments.

Considering metal like Fe, the anodic reaction is dissolution of iron as ferrous ions with the
liberation of electrons.

 Fe2  2e
Fe  (Oxidation)

These electrons flow through the metal, from anode to cathode, where H+ ions (of acidic
solution) are eliminated as hydrogen gas.

2H   2e 
 H 2  (Reduction)

The overall reaction is: Fe  2H  

 Fe2  H 2 

Mechanism of wet corrosion by hydrogen evolution

Thus, this type of corrosion causes “displacement of hydrogen ions from the acidic solution
by metal ions.” Consequently, all metals above hydrogen in the electrochemical series have a
tendency to get dissolved in acidic solution with simultaneous evolution of hydrogen.

Note: It may be pointed here that in hydrogen evolution-type of corrosion, the anodes are,
usually very large areas; whereas the cathodes are small areas.

(b) Absorption of oxygen: Rusting of iron in neutral aqueous solution of electrolytes (like
NaCl solution) in the presence of atmospheric oxygen is a common example of this type of
corrosion. The surface of iron is, usually, coated with at thin film of iron oxide. However, if
this iron oxide film develops some cracks, anodic areas are created on the surface; while the
well-metal parts act as cathodes.
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 Mechanism of wet corrosion by oxygen absorption

It follows that the anodic areas are small surface parts; while nearly the rest of the surface of
the metal forms large cathodes.

At the anodic areas of the metal (iron) dissolves as ferrous ions with liberation of electrons.

 Fe2  2e
Fe  (Oxidation)

The liberated electrons flows from anodic to cathodic areas, through iron metal, where
electrons are intercepted by the dissolved oxygen as:

1
O 2  H 2O  2e  
 2OH (Reduction)
2

The Fe2+ ions (at anode) and OH ions (at cathode) diffuse and when they meet, ferrous
hydroxide is precipitated.

Fe2  2OH 
 Fe(OH)2 

(i) If enough oxygen is present, ferrous hydroxide is easily oxidised to ferric hydroxide.

4Fe(OH)2  O2  2H 2O 
 4Fe(OH)3

This product, called yellow rust, actually corresponds to Fe2O3 .H 2O.

Galvanic (or Bimetallic) Corrosion: When two dissimilar metals (e.g., zinc and copper) are
electrically connected and exposed to an electrolyte, the metal higher in electrochemical
series undergoes corrosion. This type of corrosion is called “galvanic corrosion”. In the above
example, zinc (higher in electrochemical series) forms the anode and is attacked and gets
dissolved; whereas copper (lower in electrochemical series or more noble) acts as cathode.

Mechanism: In acidic solution, the corrosion occurs by the hydrogen evolution process;
while in neutral or slightly alkaline solution, oxygen absorption occurs. The electron-current
flows from the anodic metal, zinc, to the cathodic metal, copper.

 Zn2  2e
Zn  (Oxidation)

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Thus, it is evident that the corrosion occurs at the anodic metal; while the cathodic part is
protected from the attack.

Concentration Cell Corrosion: This type of corrosion is due to electrochemical attack on

the metal surface, exposed to an electrolyte of varying concentrations or of varying aeration.
This may be the result of local difference in metal-ion concentrations, caused by local
temperature differences or inadequate agitation or slow diffusion of metal-ions, produced by
corrosion.

Differential aeration corrosion (the most common type of concentration cell corrosion) occurs
when one part of metal is exposed to a different air concentration from the other part. This
causes a difference in potential between differently aerated areas. It has been found
experimentally that “poor-oxygenated parts are anodic”. Consequently, a differential aeration
of metal causes a flow of current, called the differential current.

Differential aeration accounts for the corrosion of metals, partially immersed in a solution,
just below the waterline. Thus, if a metal (say Zn) is partially immersed in a dilute solution of
a neutral salt (say NaCl) and the solution is not agitated properly, then, the parts above and
closely adjacent to the waterline are more strongly aerated (because of the easy access of
oxygen) and hence, become cathodic. On the other hand, parts immersed to greater depth
(which have less access of oxygen) show a smaller oxygen concentration and thus, become
anodic. So, a difference of potential is created, which causes a flow of current between the
two differentially-aerated areas of the same metal. Zinc will dissolve at the anodic areas, and
oxygen will take up electrons at the cathodic areas to form hydroxyl ions.

 Zn2   2e
Zn  (Oxidation)

1
O2  H 2O  2e 
 2OH (Reduction)
2

The circuit is completed by migration of ions, through the electrolyte, and flow of electrons,
through the metal, from anode to cathode.

Pitting Corrosion: Pitting corrosion is a localized accelerated attack, resulting in the

formation of cavities around which the metal is relatively unattached. Thus, pitting corrosion
results in the formation of pinholes, pits and cavities in the metal. Pitting is, usually, the result
of the breakdown or cracking of the protective film on a metal at specific points. This gives
rise to the formation of small anodic and large cathodic areas.

In the correct environment, this produces corrosion current. Breakdown of the protective film
may be caused by: (i) surface roughness or non-uniform finish, (ii) scratches or cut edges,
(iii) local straining of metal, due to non-uniform stresses, (iv) alternating stresses, (v) sliding
under load, (vi) pingement attack (caused by the turbulent flow of a solution over a metal
surface), and (vii) chemical attack.

Waterline Corrosion: When water is stored in a steel tank, it is generally found that the
maximum amount of corrosion takes place along a line just beneath the level of the water
meniscus. The area above the waterline (highly-oxygenated) acts as the cathodic and is
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completely unaffected by corrosion. However, if the water is relatively free from acidity,
little corrosion takes place.

The problem of waterline corrosion is also that concerns marine engineers. In the case of
ships, this kind of corrosion is often accelerated by marine plants attaching themselves to the
sides of ships. The use of special antifouling paints restricts this to some extent.

Stress Corrosion: Stress corrosion (or stress cracking) “is the combined effect of static
tensile stresses and the corrosive environment on a metal.” It is characterized by a highly
localized attack occurring, when overall corrosion is negligible. For stress corrosion to occur:
(i) presence of tensile stress, and (ii) a specific corrosive environment are necessary. The
corrosive agents are highly specific and selective such are: (a) caustic alkalis and strong
nitrate solution for mild steel; (b) traces of ammonia for brass; (c) acid chloride solution for
stainless steel.

This type of corrosion is seen in fabricated articles of certain alloys (like high-zinc brasses
and nickel brasses) due to the presence of stresses caused by heavy working like rolling,
drawing or insufficient annealing. However, pure metals are relatively immune to stress
corrosion.

Stress corrosion involves in a localized electrochemical corrosion, occurring along narrow

paths, forming anodic areas with respect to the more cathodic areas at the metal surface.
Presence of stress produces strains, which, result in localized zones of higher electrode
potential. These become so chemically-active that they are attacked, even by a mild corrosive
environment, resulting in the formation of a crack, which grows and propagates in a plant
(perpendicular to the operating tensile stress), until failure occurs or it may stop, after
progressing a finite distance.

Some typical examples of stress corrosion are given below:

Season cracking

Caustic embrittlement

It is a very dangerous form of stress corrosion, occurring in mild steel exposed to alkaline
solutions at high temperatures and stresses. The failure is often associated with steam-boilers
and heat-transfer equipments in which water of high alkalinity attacks the mild steel plates,
particularly at the crevices near rivets. Boiler-water, usually, contains a certain proportion of
sodium carbonate, added for water softening purposes. In high-pressure boilers, this breaks
up to give sodium hydroxide and carbon dioxide, and makes boiler-water alkaline.

Na 2CO3  H2O 
 2NaOH  CO2 

This very dilute alkaline boiler-water (in boiler) flows into the minute hair-cracks and
crevices (by capillary action), where water evaporates and the caustic soda concentration
builds up. This concentrated alkali dissolves iron as sodium fermate (hypoferrite) in crevices,
cracks, where the metal is stressed and the concentration of alkali is much higher than that in

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the body of the liquid. The sodium ferroate (Na2FeO2) decomposes, a short distance away
from its point of formation, according to either of the following reactions:

3Na 2FeO2  4H2O 

 6NaOH  Fe3O4  H2

or 6Na 2FeO2  6H2O  O2 

12NaOH  2Fe2O4

Sodium hydroxide is regenerated and magnetite (Fc3O4) is precipitated, thereby enhancing

further dissolution of iron.

Caustic embrittlement can be explained by considering the following electrochemical cell:

+
Iron | Concentrated NaOH | Dilute NaOH | Iron–

The iron surrounded by the dilute NaOH (main body) is the cathodic side; while the iron in
contact with rather concentrated caustic soda (e.g., crevices, hair-cracks, rivets) is the anodic
portion, undergoing corrosion and is thus dissolved.

Galvanic Series: In the electrochemical series (reduction electrode potential arranged down
in an increasing order), a metal high in the series is more anodic and undergoes corrosion
faster than the metal below it. For example, Li corrodes faster than Mg; Zn corrodes faster
than Fe; Fe corrodes faster than Sn; Cu corrodes faster than Ag and so on. However, some
exceptions to this generalization are known. For example, Ti (above Ag in the
electrochemical series) is less reactive than Ag. In Zn-Al couple, Zn (below Al in the
electrochemical series) is corroded; while Al acts cathodic and is protected. These
observations, exactly opposite to that predicted by the emf series, are due to the fact that
metals like Ti and Al develop, strongly adhering oxide layers on their surfaces, thereby
making their effective electrode potential more positive (or less negative).

From the above, it is clear that electrochemical series does not account for the corrosion of all
metals and alloys. Consequently, a more practical series, called galvanic series (see Table 1)
have been prepared by studying the corrosion of metals and alloys in a given environment
like sea-water. Thus, galvanic series give real and useful information for studying the
corrosion of metals and alloys.

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 Table 1: Galvanic series

Factors Influencing Corrosion: The rate and extent of corrosion, depends on the following
factors:

1. Nature of the metal: (i) Position in galvanic series: When two metals or alloys are in
electrical contact, in presence of an electrolyte, the more active metal (or higher up in the
series) suffers corrosion. The rate and severity of corrosion, depends upon the difference in
their positions, and greater is the difference, the faster is the corrosion of the anodic metal /
alloy.

(ii) Relative areas of the anodic and cathodic parts: When two dissimilar metals or alloys
are in contact, the corrosion of the anodic part is directly proportional to the ratio of areas of
the cathodic part and the anodic part.

Corrosion is more rapid and severe, and highly localized, if the anodic area is small (e.g., a
small steel pipe fitted in a large copper tank), because the current density at a smaller anodic
area is much greater, and the demand for electrons (by the large cathodic areas) can be met by
smaller anodic areas only by undergoing “corrosion more briskly”.

(iii) Purity of metal: Impurities in a metal, generally, cause “heterogeneity”, and form
minute / tiny electrochemical cells (at the exposed parts), and the anodic parts get corroded.
For example, zinc metal containing impurity (such as Pb or Fe) undergoes corrosion of zinc,
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due to the formation of local electrochemical cells. The rate and extent of corrosion increases
with the increasing exposure and extent of the impurities. Consequently, corrosion resistance
of a metal may be improved by increasing its purity.

(iv) Physical state of metal: The rate of corrosion is influenced by physical state of the metal
(such as grain size, orientation of crystals, stress, etc.). The smaller the grain-size of the metal
or alloy, the greater will be its solubility and hence, greater will be its corrosion. Moreover,
areas under stress, even in a pure metal, tend to be anodic and corrosion takes place at these
areas.

(v) Nature of surface film: In aerated atmosphere, practically all metals get covered with a
thin surface film (thickness = a few Angstroms) of Metal oxide. The ratio of the volumes of
the metal oxide to the metal, is known as a “specific volume ratio.” Greater the specific
volume ratio, lesser is the oxidation corrosion rate. The specific volume ratios of Ni, Cr, and
W are 1.6, 2.0 and 3.6 respectively. Consequently, the rate of oxidation of tungsten is least,
even at elevated temperatures.

(vi) Passive character of metal: Metal like Tl, Al, Cr, Mg, Ni, and Co are passive and they
exhibit much higher corrosion-resistance than expected from their positions in galvanic
series, due to the formation of highly protective, but very thin film (of oxide) on the metal or
alloy surface. Moreover, the film is of such a “self-healing” nature, if broken, repairs itself on
re-exposure to oxidizing conditions. Thus, corrosion-resistance of stainless steel is due to
passivating character of chromium present in it.

(vii) Solubility of corrosion products: In electrochemical corrosion, if the corrosion product

is soluble in the corroding medium, then corrosion proceeds at a faster rate. On the contrary,
if the corrosion product is insoluble in the medium or it interacts with the medium to form
another insoluble product (e.g., PbSO4 formation in case of Pb in H2SO4 medium), then the
corrosion product functions as physical barrier, thereby suppressing further corrosion.

(viii) Volatility of corrosion products: If the corrosion product is volatile, it volatilizes as

soon as it is formed, thereby leaving the underlying metal surface exposed for further attack.
This causes rapid and continuous corrosion, leading to excessive corrosion. For example,
molybdenum oxide (MoO3), the oxidation corrosion product of molybdenum, is volatile.

2. Nature of the corroding environment:

(i) Temperature: With increase of temperature of environment, the reaction as well as

diffusion rate increase, thereby corrosion rate is generally enhanced.

(ii) Humidity of air is the deciding factor in atmospheric corrosion. “Critical humidity” is
defined as the relative humidity above which the atmospheric corrosion rate of metal
increases sharply.

(iii) Presence of impurities in atmosphere: Atmosphere, in the vicinity of industrial areas,

contains corrosive gases like CO2, H2S, SO2, and fumes of HCl, H2SO4, etc. In presence of
these gases, the acidity of the liquid, adjacent to the metal surfaces, increases and its electrical

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conductivity also increases. This consequently, results in an increase of corrosion current
flowing in the local electrochemical cells on the exposed metal surfaces.

(iv) Presence of suspended particles in atmosphere: In case of atmospheric corrosion: (a)

if the suspended particles are chemically active in nature [like NaC1, (NH4)2SO4], they
absorb moisture and act as strong electrolytes, thereby causing enhanced corrosion; (b) if the
suspended particles are chemically inactive in nature (e.g., charcoal), they absorb both
sulphur gases, and moisture and slowly enhance corrosion rate.

(v) Influence of pH: Generally, acidic media (i.e., pH < 7) are more corrosive than alkaline
and neutral media. However, amphoteric metals (like Al, Zd, Pb, etc.) dissolve in alkaline
solutions as complex ions. The corrosion rate of iron in oxygen-free water is slow, until the
pH is below 5. The corresponding corrosion rate in presence of oxygen is much higher.

Corrosion Control (Protection against Corrosion): Some of the corrosion control methods
are described as follows:

1. Proper designing: The design of the material should be such that “corrosion, even if it
occurs, is uniform and does not result in intense and localized corrosion”. Important design
principles are:

(i) Avoid the contact of dissimilar metals in the presence of a corroding solution: If this
principle is not followed, then corrosion is localized on the more active metal (in the
immediate vicinity of contact); while the less active metal remains protected.

(ii) When two dissimilar metals are to be in contact, the anodic material should have as large
area as possible; whereas the cathodic metal should have as much smaller area as possible.

(iii) If two dissimilar metals in contact have to be used, they should be as close as possible to
each other in the electrochemical series.

(iv) Whenever the direct joining of dissimilar metals, is unavoidable, an insulating fitting
may be applied in-between them to avoid direct metal-metal electrical contact.

(v) The anodic metal should not be painted or coated.

2. Using pure metal: Impurities in a metal cause heterogeneity, which decreases corrossion-
resistance of the metal. Thus, the corrosion-resistance of a given metal may be improved by
increasing its purity.

3. Using metal alloys: Noble, but precious metals such as platinum and gold are corrosion-
resistant. Corrosion-resistance of most metals is best increased by alloying them with suitable
elements, but for maximum corrosion-resistance, alloy should be completely homogeneous.

4. Cathodic protection: The principle involved in this method is to force the metal to be
protected to behave like a cathode, thereby corrosion does not occur. There are two types of
cathodic protections:

(i) Sacrificial anodic protection method: In this protection method, the metallic structure
(to be protected) is connected by a wire to a more anodic metal, so that all the corrosion is
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concentrated at this more active metal. The more active metal itself gets corroded slowly;
while the parent structure (cathodic) is protected. The more active metal so-employed is
called “sacrificial anode”, The corroded sacrificial anode block is replaced by a fresh one,
when consumed completely, Metals commonly employed as sacrificial anodes are
magnesium, zinc, aluminium and their alloys. Important applications of sacrificial anodic
method include protection of buried pipelines, underground cables; marine structures, ship-
hulls, water-tanks, piers, etc. (see Fig, 2).

In cathodic protection, an anode of a more strongly reducing metal is

sacrificed to maintain the integrity of the protected object (e.g., a pipeline, bridge,
ship shull or boat).

(ii) Impressed current cathodic protection: In this method, an impressed current is applied
in opposite direction to nullify the corrosion current, and convert the corroding metal from
anode to cathode. Usually, the impressed current is derived from a direct current source (like
battery or rectifier on a.c. line) with an insoluble anode (like graphite, high silica iron, scrap
iron, stainless steel or platinum). Usually, a sufficient d.c. current is applied to an insoluble
anode, buried in the soil (or immersed in the corroding medium), and connected to the
metallic structure to be protected. The anode is, usually, in a backfill (composed of coke
breeze or gypsum) so as to increase the electrical contact with the surrounding soil. This type
of cathodic protection has been applied to open water-box coolers, water-tanks, buried oil or
water pipes, condensers, transmission line towers, marine piers, laid-up ships, etc. This kind
of protection technique is, particularly, useful for large structures for long-term operations.

5. Modifying the environment: The corrosive nature of the environment can be reduced
either: (i) by the removal of harmful constituents, or (ii) by the addition of specific
substances, which neutralize the effect of corrosive constituents of the environment.

(a) Deaeration: In oxygen concentration type of corrosion, exclusion of oxygen from

aqueous environment reduces metal corrosion. Expulsion of dissolved oxygen is done by
adjustment of temperature, together with “mechanical agitation”. The method also reduces
the CO2 - content of water, thereby decreasing the corrosion rate of steel pipelines carrying
steam condensates from boilers.

(b) Deactivation involves the addition of chemicals, capable of combining rapidly with the
oxygen in aqueous solution. For example, sodium sulphite (Na2SO3).

2Na 2SO 3  O2 
 2Na 2SO 4

Hydrazine hydrate ( NH2 .NH2 .H 2O) is advantageous over the sodium sulphite, because the
reaction products are N2 (g) and water.
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 N 2 H 4  O2 
 N 2  2H 2O

(c) Dehumidification reduces the moisture content of air to such an extent that the amount of
water condensed on metal is too small to cause corrosion. Alunnina or silica gels, which
adsorb moisture preferentially on their surfaces, are used only in closed areas like air-
conditioning shop.

(d) Alkaline neutralization is prevention of corrosion by neutralizing the acidic character of

corrosive environment (due to the presence of H2S, HO, CO2, SO2, etc.). Such alkaline
neutralizers (like NH3, NaOH, lime, naphthenic soaps, etc.) are, generally, injected either in
vapour or liquid form to the corroding system or to its parts. This method has been widely
used in controlling the corrosion of refinery equipments.

6. Use of inhibitors: A corrosion inhibitor is “a substance which when added in small

quantities to the aqueous corrosive environment effectively decreases the corrosion of a
metal”. Inhibitors are:

(i) Anodic inhibitors (such as chromates, phosphates, tungstates or other ions of transition
elements with a high oxygen content) are those that stifle the corrosion reaction, occurring at
the anode, by forming a sparingly soluble compound with a newly produced metal ion. They
are adsorbed on the metal surface, forming a protective film or barrier, thereby reducing the
corrosion rate. Although this type of control is effective, yet it may be dangerous, since sever
local attack can occur, if certain areas are left unprotected by depletion of the inhibitor.

(ii) Cathodic inhibitors like amines, mercaptans, hetrocyclic nitrogen compounds,

substituted ureas and thioureas, heavy metal soaps.

7. Application of protective coatings: Protecting the surface of an object by the application

of coating is probably the oldest of the common procedures for corrosion prevention. A
coated-surface isolates the underlying metal from the corroding environment. The only
limitations of this method is the service behaviour of the protective coatings: (i) The coating
applied must be chemically inert to the environment under particular conditions of
temperature and pressure. (ii) Moreover, coatings must prevent the penetration of the
environment to the material, which they protect.

(i) Anodic coatings are produced from coating-metals, which are “anodic” to the base metal
(i.e., which is to be protected). For example, coating of Zn, Al and Cd on steel are anodic,
because their electrode potentials are lower than that of the base metal, iron. If any pores,
breaks or discontinuities occur in such an anodic coating, a galvanic cell is formed between
the coating-metal and the exposed part of base metal, e.g., in case of galvanised steel, zinc,
the coating-metal (being anodic) is

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14
 Functioning of anodic coating. In galvanized steel, Zn serves an anode;
while iron of steel serves as the cathode. Therefore, the iron is protected,
even if it is exposed, when a part of the zinc coating is scrapped off.

attacked; leaving the underlying cathodic metal (iron) unattacked. Galvanic cell is formed
between Zn and the exposed iron. Zinc (being anodic to iron) dissolves anodically; whereas
the iron (being cathodic) is protected. Thus, no attack on the iron occurs, until practically all
the zinc has first corroded in the vicinity of the exposed iron spot. So, zinc coating protect
iron ‘sacrificially’.

(ii) Cathodic coatings are obtained by coating a more noble metal (i.e., having higher
electrode potential) than the base metal. They protect the base metal, because they have
higher corrosion-resistance than the base metal. Cathodic coating provides effective
protection to the base metal only when they are completely continuous and free from pores,
breaks or discontinuities.

If such coatings are punctured, much more corrosion damages can be done to the base metal
than to metal without it. For example, a tin-coating on a sheet of iron provides protection only
as long as the surface of the metal is completely covered, since tin is lower than iron in
electromotive series. However, if the surface coating is punctured, the tin becomes the
cathode; while the exposed iron (which is above tin in the electromotive series) acts as anode.
A galvanic cell is set up and an intense localized attack at the small exposed part occurs,
resulting in severe pitting and perforation of the base metal, iron. Such combination of a
small anode and large cathode area is always very dangerous.

B.Tech. First / Second Semester, BIT Durg, Applied Chemistry; Unit-3

15
 Tin-plated steel. The tin protects the iron, when the coating is continuous.
When the coating is broken, the iron of the steel becomes the anode
and is subjected to accelerated local corrosion.

Methods of application of metal coatings:

Hot dipping is used for producing a coating of low-melting metal such as Zn (m.p. = 419oC),
Sn (m.p. = 232oC), Pb, Al, etc., on iron, steel and copper, which have relatively higher
melting points.

(a) Galvanizing is the process of coating iron or steel sheets with a thin coat of zinc to
prevent them from rusting.
(b) Tinning is coating tin over the iron or steel articles.

(iii) Metal cladding is the process by which a dense, homogeneous layer of coating metal is
bonded firmly and permanently to the base metal on one or both sides.

Text Book:

1. A Text book of Engineering, Chemistry, P. C. Jain and Monika Jain, 16 th Edition 2013,
Dhanpat Rai Publishing Company (P) LTD, New
2. Engineering Chemistry O. G. Palanna, 1st Edition 2011, Mc Graw Hill, Education (India),
Private Limited, Chennai.
3. A Text book of Engineering, Chemistry S. S. Dara, 1st Edition 2010, S. Chand & Company
Ltd., New Delhi

♦♦♦

Questions:

1. Explain the electrochemical theory of wet corrosion, giving its mechanism.

2. What is the chemical formula of rust?
3. Discuss the various (any three) factors affecting rate of corrosion.
4. Explain the mechanism of following types of corrosion:
(i) Water-line corrosion
(ii) Pitting corrosion
(iii) Stress corrosion
(iv) Differential aeration corrosion
5. Define corrosion.
6. Explain Dry corrosion.
7. Iron corrodes faster than aluminium, even though iron is placed below aluminium in
the electrical series. Why?

♦♦♦

B.Tech. First / Second Semester, BIT Durg, Applied Chemistry; Unit-3

16
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