Corrosion Science: Department of Chemistry, RVCE

Department of chemistry, RVCE
CORROSION SCIENCE
Corrosion is a universal phenomenon associated with certain metals and alloys. A

phenomenon that occurs in various environments like air, water, soil etc. Every country spends
almost 3.5% of its GDP in combating this problem. Corrosion costs manifest in the form of
premature deterioration or failure necessitating replacement, maintenance and repairs. As
majority of the commercially available metals are susceptible for corrosion, an understanding of
the mechanism of corrosion and techniques available for its prevention would be of great
importance to an engineer
Definition:
It is defined as the destruction or deterioration and consequent loss of metal / alloy due to
chemical or electrochemical attack on its surface by the environment.
OR
It is a process where a metal or alloy is transformed from its metallic state to the
undesired combined state due to interaction with the environment through chemical or
electrochemical attack.
Example: When iron is exposed to air in the presence of moisture, hydrated ferric oxide (rust) is
formed.
Fe2+ + 2OH- Fe(OH)2
2Fe(OH)2 + 11/2 O2 + H2O Fe2O3.3H2O rust(brown

colour)
Other Examples:
1. Rusting of iron-a reddish brown scale formation on iron and steel objects. It is due to
formation of hydrated ferric oxide.
2. Green scales formed on copper vessel. It is due to formation of basic carbonate

(CuCO3+Cu(OH)2).
The term corrosion generally applies to the degradation of metals and alloys.
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Reason behind corrosion

Metals are thermodynamically unstable. Naturally, metals are present in the form of
metallic compounds (oxidized form) in their ores. During extraction, lot of energy is put into
reduce metal ions to metal atoms. Hence, metals are always at higher energy state and are
thermodynamically unstable. So metals are tried to come back to its original state
(Thermodynamically stable) by undergoing oxidation. Undergoing oxidation is nothing but
corrosion
Classification of corrosion
(a) Dry corrosion (b) Wet corrosion
Dry Corrosion
Dry corrosion occurs when oxygen in the air reacts with metal or alloy in the absence of
water or any liquid medium.
This type of corrosion occurs mainly by the direct chemical action of the environment
i.e., by the direct attack of atmospheric gases such as O2, halogens, H2S, SO2, N2, mineral acids
etc. on the metal surface with which they are in contact.
There are 3 main types of chemical corrosion.
1) Corrosion by oxygen (or) oxidation corrosion.
2) Corrosion by other gases like SO2, CO2, H2S and F2 etc.
3) Liquid metal corrosion.
Oxidation corrosion:
It is brought about by direct action of oxygen at low (or) high temperatures, usually in the
absence of moisture. At high temperatures all metals are attacked by oxygen and are oxidized –
except noble metals like Ag, Au, Pt. However alkali metals – Li, Na, K, Rb etc. and alkaline
earth metals – Be, Ca, Sr etc. are attacked very rapidly and get oxidized readily.
Corrosion by other gases:
This type of corrosion may occur when the gasses like SO2, CO2, Cl2, H2S, etc attacks on
the metal surface. The extent of corrosion mainly depends on the chemical affinity between the
metal and the gas involved. The degree of attack depends on the nature of the layer formed.
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i) For e.g. when Ag metal is attacked by Cl2 gas, they form AgCl layer, which is
protective. Hence further corrosion of Ag by Cl2 will be stopped. ii) When Sn is attacked by dry
Cl2 gas, it forms SnCl4 which evaporates immediately thus leaving the fresh metal for further
attack.
Liquid metal corrosion:

It is due to chemical action of flowing liquid metal at high temperatures on solid metal or
alloy. Such corrosion occurs in nuclear power devices.
The corrosion reaction involves either dissolution of a solid metal by molten metal (or)
internal penetration of the molten metal into the solid metal. Both these types of corrosion cause
weakening of the solid metal. For eg in nuclear reactors liquid sodium corrodes Cd rods.
Wet Corrosion (Atmospheric corrosion)
It is common type of corrosion of metal in an aqueous/ humid corrosion environment. It
occurs when a liquid is present in environment. This usually involves aqueous solutions or
electrolytes and accounts for the greatest amount of corrosion.
Ex: corrosion of steel in presence of moisture
Difference between Dry Corrosion and Wet Corrosion
Sl No Dry corrosion Wet corrosion

1 It occurs in dry condition. It occurs in wet condition.
2 If the corrosion takes place due to direct If the corrosion takes place due to
chemical attack (in the absence of electrochemical attack in presence of
moisture), corrosion is known as dry moisture or a conducting medium
corrosion. ,corrosion is known as wet corrosion
3 Corrosion is uniform. Corrosion is not uniform.
4 Corrosion products accumulate at the Corrosion take place at anode but products
place where corrosion occurs. accumulate near the cathode.
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Electrochemical theory of corrosion
According to electrochemical theory, when a metal such as iron is exposed to corrosive

environment, following changes occur.
(a) Formation of anodic and cathodic areas
These anodes and cathodes are formed due to the heterogeneities at the interfaces of the metal
and environment. The heterogeneities on a metal surface could develop due to several factors
like,
(i) if a metal surface exposed to different concentrations of oxygen, the more aerated/oxygenated
area acts as cathode and less oxygen/aerated area acts as anode.
(ii) When two different metals are in contact and exposed to corrosive environment, one acts as
cathode while other acts anode.
(iii) If metal surface subjected to stress (area under stress acts as anode).
(b) Presence of an electrolyte solution or conducting solution in contact with these areas resulting
tiny electrochemical cells.
When there is a chance for formation of such tiny electrochemical cells, chemical
reactions starts leading to corrosion.
The metal acts as electronic conductor and the solution (or water) on it completes the circuit by
conducting ions (electrolytic conductor).
At anode
Oxidation of metal takes place at the anodic region.
Ex: Fe  Fe2+ + 2 e-
The liberated electrons travel through the metal from the anodic region to cathodic region.
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At cathode
In this area, the reaction takes place either by, a) liberation of hydrogen or b) absorption of
oxygen.
 Reduction of O2 or H+ takes place at the cathodic region as per the reaction shown in the
table below.
 The metal is unaffected at the cathodic region.
Fe2+ and OH- ions travel through the aqueous medium and form corrosion product.
Fe2+ + 2OH- Fe(OH)2
Primary corrosion product (unstable)

The above corrosion product may undergo further oxidation to form rust.
2Fe(OH)2 + 11/2 O2 + H2O Fe2O3.3H2O
Summary of the above reactions is as fallows
At Anode Fe Fe2+ + 2e-
At cathode In absence of oxygen In presence of oxygen

In acidic
2H+ + 2e- H2
medium 4 H+ + O2 + 4 e- → 2OH- + H2↑
In neutral 2H2O + 2e- 2OH- + H2
or alkaline 2H2O + O2 + 4 e- → 4 OH-
medium
Final reactions
Fe2+ + 2OH- Fe(OH)2
Primary corrosion product (unstable)

2Fe(OH)2 + 11/2 O2 + H2O Fe2O3.3H2O
Hydrated ferric oxide
Final corrosion product (stable)
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Types of corrosion
1. Differential metal corrosion/Galvanic Corrosion

This type of corrosion occurs when, two dissimilar metals are in contact and jointly exposed
to corrosive environment.
During galvanic corrosion the metal having lower SRP (Standard reduction potential) value
becomes anode and corrodes. The metal with higher SRP value acts as cathode undergoes
reduction. The potential difference between the two metals is driving force for corrosion. The
greater the electrode potential difference, the higher is the corrosion rate. Thus anodic area
always undergoes corrosion and cathodic area remains unaffected.
The reactions may be represented as follows:
Cell reactions:
At anode : M Mn+ + ne- (Oxidation of metal M)

At cathode : O2 + 2H2O + 4e- 4OH- (Reduction of oxygen)
Higher the potential difference between the anodic and cathodic metals, higher is the rate of
corrosion.
Example: When iron is in contact with zinc, iron acts as cathode and zinc acts as anode because
zinc has lower reduction potential compared to iron. Therefore zinc undergoes corrosion. On
the other hand, when iron is in contact with tin, iron acts as anode because iron has lower
reducton potential compared to tin. Hence iron undergoes corrosion.
Other examples:
1. Steel screws in copper sheet.
2. Steel screws with copper washer.
3. Bolt and nut made of different metals.
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Preventive Measures
(i) Selecting materials having very less potential difference.
(ii) Providing insulating material between the two metals.
Galvanic Series
The galvanic series is used to provide sufficient information in predicting the corrosion
behavior of metals and alloys in different environmental conditions. Oxidation potential
measurements of various metals and alloys have been made using the standard calomel electrode
as the reference electrode and immersing the metals and alloys in sea water. These are arranged
in decreasing order of activity and this series is known as the galvanic series. The galvanic series
gives more practical information on the relative corrosion tendencies of the metals and alloys.
Characteristics of galvanic series:
1. Galvanic series was prepared by studying the corrosion of metals and alloys in a given
environmental condition like sea water.
2. The position of a metal, when present in the form of an alloy is different from that of pure
metal.
3. This series comprises of metals and alloys.
4. Since alloys are included in this series, so their corrosion can be studied from this series.
5. It predicts the relative corrosion tendencies.
The differences between Galvanic series and Electrochemical series are as follows:
Sl Electrochemical Series Galvanic Series
No
1 This series was developed by studying This series is developed by studying
corrosion of metals and alloys in their salt corrosion of metals and alloys in
solution of 1M concentration without any oxide unpolluted sea water without their oxide
film on them. film.
3 There is no information regarding position of The corrosion of alloys are also studied
alloys in this series.
4 The position of the metal is permanently fixed. The position of metal when present in
form of alloy is different from that of
pure metal.
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5 This series predicts the relative displacement This series predicts the relative
tendencies. corrosion tendencies.
6 This series comprises of metals and non-metals. This series comprise of metals and
alloys.
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2. Differential aeration corrosion:

This type of corrosion occurs when two different parts of the same metal are exposed to
different oxygen concentrations.
The part of the metal which is exposed to less oxygen concentration acts as anode. The part
which is exposed to more oxygen concentration acts as cathode. The anodic region undergoes
corrosion and the cathodic region is unaffected.

Cell reactions:
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Other examples:
1. Part of the nail inside the wall undergoes corrosion.
2. When a dirt particle sits on a metal bar, the part under the dirt undergoes corrosion.
3. Partially filled iron tank undergoes corrosion inside water.
Wire fence
Cases of differential aeration corrosion.
(A) Pitting corrosion: This is a case of differential aeration corrosion.
This type of corrosion is initiated by the deposition of matter such as sand, dust, water drop, etc.
The metal below the deposit is exposed to lower oxygen concentration, acts as anode and
undergoes corrosion. The metal surrounding the deposit acts as cathode since it is exposed to
higher concentration of oxygen. Because of the small anode and large cathode,
intense/accelerated corrosion occurs just below the deposit. Since large cathodic area puts up
high demand for electrons that have to be generated by small anodic area. So metal gets oxidized
rapidly.
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Cell reactions:

(B) Waterline corrosion:

This is another case of differential aeration corrosion.
More oxygen,
(Cathode) Rust
Less Oxygen
(Anode) Water
When a steel tank is partially filled with water for a long time, the inner portion of the tank
below the water line is exposed only to dissolve oxygen, where as, the portion above the water
line is exposed to more oxygen. Thus the portion below the water line acts as anode and
undergoes corrosion. The upper portion acts as cathode and is unaffected.
A distinct brown line is formed just below the water line due to the deposition of rust.
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Cell reactions:

Other example: Ships which remain partially immersed in sea water for a long time undergo
water line corrosion.
4. Stress corrosion:
Stress corrosion occurs when stressed region of metals are exposed to corrosive environments.
The stressed region acts as anode and undergoes corrosion. The unstressed region acts as
cathode and is unaffected.
Stress corrosion is highly specific in nature. For corrosion to occur, the presence of both stress
and a specific corrosive environment are necessary. For example, stressed regions of mild steel
undergo stress corrosion in the presence of NaOH solution.
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Caustic embrittlement
Caustic embrittlement in boilers is an example of stress corrosion. Here alkaline (NaOH) water
enters the hairline cracks on the boiler wall (mild steel). The water evaporates off leaving behind
a concentrated solution of NaOH in the crack. When the concentration of NaOH increases to
10%, an electrochemical cell is set up with the stressed region acting as anode. The iron
surrounded by dilute NaOH acts as cathode. The anodic region undergoes corrosion leading to
crack propagation which may result in boiler failure.
Boiler
Anode
Cathode
Soft water =
Very dilute NaOH
Ex: The water of the steam boiler is softened by the addition of small amounts of Na2CO3, which
makes water alkaline due to the action of Na2CO3 at high pressure
Na2CO3 + 4H2O 2NaOH + CO2
NaOH remains in the cracks and Carbon dioxide escapes. A concentration cell of the type shown
below is formed.
Iron (in the crack)/ Concentrated NaOH // Dilute NaOH / Iron (stressed part)
The NaOH formed flows into hairline cracks through capillary action. When the concentrations
of caustic soda reached a sufficient level (10%), it reacts with iron and forms Na2FeO2 (sodium
ferrate) which decomposes to give Fe3O4 and NaOH.
2NaOH + Fe Na2FeO2 + H2
3 Na2FeO2 + 4H2O Fe3O4 + H2 + 6NaOH
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NaOH thus formed, further reacts with iron to cause stress corrosion cracking.
How to prevent caustic embrittlement?
It can be prevented by the addition of compounds such as sodium sulphate, tannin, lignin,
phosphates, etc, which block the cracks or crevices thereby preventing the entry of alkali.
Factors affecting the rate of corrosion
1. Nature of the metal:
It is the main factor which determines the rate of corrosion. When two dissimilar metals in
contact and exposed to atmosphere are with each other, there results in galvanic corrosion. The
tendency of the metal to undergo corrosion is dependent on the nature of the metal. Higher the
difference in electrode potentials, faster is the rate of corrosion.
For example, elements such as Mg and Zn, which have low electrode potentials, are highly
susceptible to corrosion. Whereas noble metal such as gold and platinum, which have higher
electrode potentials, are less susceptible to corrosion.
Potential difference between anodic and cathodic regions: Larger the potential difference
between the anodic and cathodic regions, higher is the rate of corrosion. For example, the
potential difference between iron and copper is 0.78 V, and between iron and tin is 0.3 V.
Therefore, corrosion is faster when iron is in contact with copper.
The use of dissimilar metals should be avoided wherever possible. Otherwise, the anodic metal
gets corroded.
Exceptions: Metals and alloys which show passivity are exceptions for this general trend. Such
metals (Al, Cr etc.,) form a protective coating on the surface which prevents corrosion.
Additional Information:
Eg. Iron corrodes faster when in contact with copper but not in contact with tin or zinc.
The potential difference between iron and copper is more (Eo Fe++Fe = -0.44 V; Eo Cu++Cu = 0.34 V
and potential difference is 0.78 V) than that between iron and tin (Eo Fe++Fe = -0.44 V; Eo Sn++Sn = -0.1 4
V and potential difference is 0.3 V). Hence, iron corrodes faster when in contact with copper than in
contact with tin.
Therefore, the use of different metals in contact with each other should be avoided to prevent the
14 and washer should be made of the same metal or
formation of galvanic corrosion. Bolt & nut or screw
alloy.
2. Nature of corrosion product: The nature of the corrosion product largely decides the rate of
further corrosion. The corrosion formed on the surface of the metal may or may not act as a
protective film.
If the corrosion product is insoluble, stable and non-porous, then it acts as a protective film
which prevents further corrosion. The film acts as a barrier between the fresh metal surface and
the corrosive environment. On the other hand, if the corrosion product is soluble, unstable and
porous, then the corrosion process continues even after the formation of corrosion product.
Example: Aluminium, titanium and chromium form a protective film of metal oxide on the
surface. Stainless steel forms a protective film of Cr2O3 on the surface. But in the case of Zn
and Fe, the corrosion products formed do not have protective value.
It is also observed that the passivation is related with the specific volume (volume per unit
weight) of the corrosion product.
Volume of the Metal oxide

Specific volume ratio =
Volume of the metal
When specific volume of the metal oxide is more than that of metal (specific volume ration
greater than 1), it covers the metal surface well, forming a nonporous layer.
Ex: W, Cr, Ni etc
In case of metal like Mg, Na, Ca, Na, Fe, etc specific volume ratio is less than, the oxide layer is
porous and hence non-protective hence corrosion occurs.
Pilling –Bedworth rule: The oxide layer acts as a protective or non-porous barrier, 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 layer is less than the volume of the metal, the oxide
layer is porous and hence non-protective. Because it cannot prevent the access of oxygen to the
fresh metal surface below. If the specific volume ration is small, then rate of corrosion is large.
For example, alkali and alkaline earth metals like Li, Na, K, Mg forms oxides of volume less
than volume of metals.
These layers are porous and non-protective. Hence these metals undergo corrosion more rapidly.
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On the other hand metals like Aluminum forms oxide whose volume is greater than the volume
of the metal. Therefore Al forms a tightly adhering non-porous protective layer.
3. Relative Areas of Anode and Cathode (Area effect)
The rate of corrosion is greatly influenced by the relative sizes of anodic and cathodic
areas. If a metal has small anodic area and large cathodic area, then the corrosion is more. At
anode, oxidation takes place and electrons are liberated. At the cathode, these electrons are
consumed. As anodic area is smaller and cathode region is large all the electrons liberated at the
anode are rapidly consumed at the cathode region.
For example, a broken coating of tin on iron surface results in intense corrosion at the broken
region. Iron is anodic to tin. Exposed region of iron acts as anode with small area. Tin acts as
cathode which has large area.
4. Polarization:
Polarization is defined as a process where there is a variation of electrode potential due to

formation of product around the electrode or due to variation in electrolyte concentration around
the electrode.
Anodic polarization occurs due to the accumulation of metal ions in the vicinity of anodic region.
This retards the formation of new metal ions by oxidation. Thus the corrosion process is
retarded.
Anodic and cathodic polarizations: The polarization at anode and cathode decreases the rate of
Corrosion generally.
Cathodic polarization occurs due to the accumulation of hydroxyl ions in the vicinity of cathodic
region. This accumulation retards the movement of cathodic reactant (oxygen) towards the
cathodic surface. Hence, the rate of cathodic reaction decreases. A retarded cathodic reaction
results in retardation of anodic reaction also. Thus the corrosion process is slowed down.
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5. pH of the medium: In general, lower the pH of corrosion medium, higher is the corrosion
rate.
This is due to the following reasons
(i) H+ ions help for cathodic reaction facilitating anodic oxidation of the metal
2H+ + 2 e- →H2↑
(ii) The corrosion product which is usually an oxide dissolves in acidic medium exposing
fresh metal surface for corrosion.
Iron does not undergo corrosion at pH greater than 10. This is due to the formation of protective
coating of hydrous oxides of iron. Between pH 10 and 3, the presence of oxygen is essential for
corrosion. If the pH is less than 3, corrosion occurs even in the absence of oxygen.
Exception: Metals like Al, Zn etc. undergo fast corrosion in media with high pH
7. Temperature:
In general, the rate of a chemical reaction increases with increase in temperature.

Corrosion is one such chemical reaction. Therefore, the rate of corrosion increases as the
temperature increases.
This is due to
(i) Increase in conductance of the medium-ions migrates fast at higher temperature.

(ii) Decrease in the polarization effects at the anodic and cathodic sites.
(iii) Increase in solubility of the corrosion product in the medium.
(iv) Breakdown in the protective film that might exist on the surface.
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Corrosion control
(I) Protective coating, (II) Cathodic protection and (III) Corrosion Inhibitors
I. Protective coating
In order to protect metals from corrosion, it is necessary to cover the surface by means of
protective coatings. These coatings act as a physical barrier between the coated metal surface and
the environment. They afford decorative appeal and impart special properties like hardness,
oxidation resistance and thermal insulation.
Protective coatings can be broadly classified into
(a) Metallic coating (b) Inorganic coating (c) organic coating
_____________________________________________________________________________
Galvanizing: Galvanizing is the process of coating a metal surface such as iron with zinc metal.
Galvanizing of iron is an example of anodic metal coating on the surface of a cathodic metal.
Galvanization is carried out by hot dipping method. It involves the following steps.
1. The metal surface is washed with organic solvents to remove organic matter on the surface.
2. Rust is removed by washing with dilute sulphuric acid(Pickling)
3. Finally, the article is washed with water and air-dried.
4. The article is then dipped in a bath of molten zinc. (Molten zinc is covered with a flux of
ammonium chloride to prevent the oxidation of molten zinc.)
5. The excess zinc on the surface is removed by passing through a pair of hot rollers.
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Application: Galvanization of iron is carried out to produce roofing sheets, fencing wire,
buckets, bolts, nuts, pipes etc.
(Note: Even if the Zn coating falls off at some places, the base metal (Fe) does not get corroded
at those places. This is because the base metal acts as cathode. In corrosion process, the
cathodic metal always remains unaffected.)
Note: Galvanized articles are not used for preparing and storing food because zinc dissolves in
dilute acids producing toxic zinc compounds.
Tinning: Tinning is the process of coating the surface of a base metal (such as iron) with tin.
Tinning of iron metal is an example of cathodic metal coating on an anodic base metal.
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Tinning of iron is carried out by hot dipping method. It involves the following steps.
1. The metal surface is washed with organic solvents to remove organic matter on the surface.
2. Rust is removed by washing with dilute sulphuric acid.
3. Finally, the article is washed with water and air-dried.
4. It is then passed through molten zinc chloride flux. The flux helps the molten tin to adhere
strongly on the surface.
5. It is then dipped in a bath of molten tin.
6. The excess tin on the surface is removed by passing through a series of rollers immersed in
palm oil. The oil prevents the oxidation of tin coating.
Applications: Tin-coated steel is used for manufacturing containers.
Q: Galvanized articles are preferred over tinned articles. Why?

Ans: Galvanizing is preferred to tinning because tin is cathodic to iron, where as zinc is anodic
to iron. So, if the protective layer of the tin coating has any cracks, iron will corrode. If the
protective layer of zinc coating has any cracks, iron being cathodic does not get corroded. The
corrosion products fill up the cracks, thus preventing corrosion.
Additional information: In tin-coated iron, if a small crack is formed in the tin coating, an
intense and accelerated corrosion of iron occurs at the exposed region because of the formation
of a small anodic area (iron) and large cathodic area (tin).
Note: Copper utensils are coated with tin to prevent contamination of food with poisonous
copper salts.)
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Differences between Galvanizing and Tinning.
Sl Galvanizing Tinning
No
1 A process of covering iron with a thin coat of A process of covering iron with a thin coat
'Zinc' to prevent it from rusting of 'tin' to prevent it from corrosion.
2 Zinc protects the iron sacrificially.(Zinc Tin protects the base metal without
undergo undergo any corrosion (non sacrificially)
corrosion)
3 Zinc continuously protects the base metal A break in coating causes rapid
even if broken at some places. corrosion of base metal
4 Galvanized containers cannot be used for Tin is non-toxic in nature of any

strong acidic food stuffs as Zinc becomes medium
toxic in acidic medium.
1. Anodizing (Anodizing of aluminum):
It is a method of developing an oxide layer on the surface by induced oxidation, in an

oxidizing environment, making the object anode and passing the current.
Process: Aluminum article is first subjected to cleaning prior to anodizing. The pre-treatment
includes degreasing followed by electro polishing. Aluminum is connected to the positive
terminal (made as an anode) and steel or copper is made a cathode. The electrolyte consists of 5-
10 % chromic acid. The temperature of the bath is maintained at 40oC. The voltage is
programmed to increase from 0 to 50 V (optimum 40 V).
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The electrode reactions occurring during anodizing process are:
At anode: 2 Al + 3 H2O  Al2O3 + 6 H+ + 6e-
At cathode: 6 H+ + 6 e-  3H2↑
Over all reaction: 2 Al + 3H2O  Al2O3 + 3 H2↑
On anodizing, Al2O3 is formed on the surface as a porous layer. The layer may be made compact
by sealing, which involves heating with boiling water or steam. During sealing, Al 2O3 is
converted into Al2O3.H2O which occupies higher volume. Therefore, the pores are sealed.
Note: Other metals such as Mg, Ti etc. can also be anodized.

Applications: Metals such as Al, Mg, Ti etc. are anodized to control corrosion.
Electrodes:
Anode: Cleaned Aluminum article, cathode: Lead/copper/steel
Bath conditions:
Electrolyte: 5-10 % chromic acid/ Oxalic acid, Temperature of the bath: 40 °C, voltage-40 V.
2. Phosphating: Converting the surface metal atoms into their phosphates by chemical or
electrochemical reactions is called phosphating.
A modern Phosphating bath contains three essential components.
(a) Free phosphoric acid (b) a primary metal phosphate and (c) an accelerator
Bath conditions: (i) pH range 1.8-3.2 (ii) Temperature of the bath is maintained at 35o C.
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The majorities of metal phosphates is insoluble in water but are soluble in mineral acids. This
constitutes the basis for a phosphate coating reaction. Accelerators are used to speed up the
reaction (coating rate) and reduce the crystal size. The commonly used accelerators include
nitrites, nitrates, chlorates and peroxides. At the present time, nitrite accelerators are the most
widely used.
The Phosphating involves the following steps

(i) The dissolution of the metal ie., by undergoing oxidation.
(ii) Metal ions combine with phosphate ions to form metal phosphate
(iii) Deposition of an insoluble phosphate layer.
3Fe + 2 H3PO4 → Fe3(PO4)2 + 3 H2↑

Applications: Phosphate coating is given as an under layer before painting the car bodies,
refrigerators and washing machines.
Organic coating (Coating with paints and enamels): Metal corrosion may be controlled by the
application of an organic coating of paint on the surface. The organic coating acts as a barrier
between the metal surface and the corrosive environment.
A primer coat such as phosphate coating is generally applied as an undercoat before painting.
Organic coatings are applied by different methods such as brushing, spraying, roller coating etc.
Paints, varnish, lacquers and enamels are the main organic coatings.
Paints
Paint is a viscous suspension of finely divided solid pigment in a fluid medium which on drying
yields an impermeable film having considerable hiding power.
When paint is applied to a metal surface, the thinner evaporates, while the drying oil slowly
oxidizes forming a dry pigmented film.
Requirements of a good paint:

A good paint should essentially have the following:
1. A good paint should form a good impervious and uniform film on the metal surface.
2. It should have a high hiding (covering) power.
3. The film should not crack on drying
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4. A good paint should adhere well to the surface.

5. It should spread on the metal surface easily.
6. It should give a glossy film
7. It should be corrosion resistant.
8. A good paint should give a stable and decent color on the metal surface.
Constituents of paint and their functions:
The important constituents of paint are as follows:
(1) Pigments (2) Vehicle or drying oils or medium (3) Thinners (4) Driers (5) Fillers or extenders
(6) Plasticizers (7) Anti-skinning agents.
(1) Pigments:
It is a solid substance which imparts color to the paint. It is an essential constituent of paint.
Its functions are to
i) Give opacity (cloudiness) and color to the film
ii) Provide strength to the paint.
iii) Provide an aesthetical appeal
iv) Give protection to the paint film by reflecting UV light.
v) Increase weather resistance of the film
vi)Provide resistance to paint film against abrasion.
The most commonly used pigments in paints and the compounds required as as follows:
White pigments - White lead, ZnO, BaSO4, TiO2, ZrO2
Blue pigments - Prussian blue, ultramarine blue
Black pigments - Graphite, carbon black, lamp black
Red pigments - Red lead, Fe3O4, carmine
Green pigments - Chromium oxide, chrome green
Brown pigments - Burnt umber, ochre
Yellow pigments - Chrome yellow, lead chromate
(2) Vehicle or drying oils or medium: The liquid portion of the paint in which the pigment is
dispersed is called a medium or vehicle. This is the film forming constituent of the paint.
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Vehicles are high molecular weight fatty acids present in animal and vegetable oils, Ex., Linseed
oil, dehydrated castor oil, soyabean oil and fish oil.
Functions:
i) To hold the pigment on the metal surface
ii) To form the protective film by evaporation or by other means.
iii) To impart water repellency, durability and toughness to the film
iv)To improve the adhesion of the film
(3) Thinners: Thinners are added to paints to reduce the consistency or viscosity of the paints
so that they can be easily applied to the metal surface.
Thinners are volatile in nature and evaporate easily after application of the paint, e.g. turpentine
andpetroleum spirit
Functions:
i) To reduce the viscosity of the paint
ii) To dissolve vehicle and the additives in the vehicle
iii) To suspend the pigments
iv) To increase the penetration power of the vehicle
v) To increase the elasticity of the paint film
vi)To help the drying of the paint film.
(4) Driers: Driers are used to accelerate or catalyze the drying of the oil film by oxidation,
polymerization and condensation, e.g. naphthenates, borates and tungstates of lead, cobalt and
manganese.
(5) Fillers or extenders: Fillers are used to reduce the cost and increase the durability of the
paint,
Ex: Talc, china clay, calcium sulphate and calcium carbonate.
(6) Plasticizers: Plasticizers are chemicals added to paints to give elasticity to the film and to
prevent cracking of the film, Ex., Triphenyl phosphate and tricresyl phosphate.
25
(7) Anti-skinning agents: They are chemicals added to the paint to prevent skinning of the paint,
Ex: Polyhydroxy phenols.
Varnish
Varnish is a homogenous colloidal dispersion of natural or synthetic resin in oil or thinner or
both. It is used as a protective and decorative coating to surfaces. It provides a hard, transparent,
glossy, lustrous and durable film to the coated surface.
Difference between paint and Varnish
Sl Paint Varnish
No
1 It has a pigment There is no pigment
2 It can be applied to both metal and It can be applied only wooden articles
wooden articles
3 It is opaque It is transparent
Enamels: These are pigment varnishes. On drying, they yield a thick, coherent, lustrous glossy
coat on the surface of the material. The properties of enamels depend upon the resin, drying oil
and thinner used. The enamel can dry in air by the process of oxidation and polymerization or at
high temperature in the absence of oxygen.
Main components: (i) Vehicle (ii) Driers (iii) Thinners
Lacquer:
It is a colloidal dispersion of cellulose derivatives, resins and plasticizers in solvents and
diluents.
Lacquers dry by the evaporation of the solvent and diluents.
II. Cathodic protection:-
The reduction or prevention of corrosion by making metallic structure as cathode in the

electrolytic cell is called cathodic protection. Since there will not be any anodic area on the
26
metal, corrosion does not occur. There are two methods of applying cathodic protection to
metallic structures.
a) Sacrificial anodic protection (galvanic protection) b) Impressed current cathodic protection
a) Sacrificial anode method
Electrical conductor
Steel pipe Cathode
Mg Block
(Anode)
In cathodic protection, the metal to be protected is completely converted into a cathode. Since
cathodes do not undergo corrosion, the metal is protected against corrosion.
In sacrificial anode method, the metal to be protected is electrically connected to a more active
metal. For example, when steel is to be protected, it may be connected to a block of Mg or Zn.
In such a situation, steel acts as cathode and is unaffected. Mg and Zn act as anode and undergo
sacrificial corrosion. When the sacrificial anode gets exhausted, it is replaced with new ones.
Other examples: Mg bars are fixed to the sides of ships to act as sacrificial anode.
Mg blocks are connected to burried pipe lines.
Advantages:
1. Low installation and operating cost.
2. Capacity to protect complex structures.
3. Applied to wide range of severe corrodents.
Limitations:
1. High starting current is required.
27
2. Uncoated parts cannot be protected.
3. Limited driving potential, hence, not applicable for large objects.
a) Impressed current method (impressed voltage method)
In cathodic protection, the metal to be protected is completely converted into a cathode. Since
cathodes do not undergo corrosion, the metal is protected against corrosion.
In impressed current method, the metal to be protected is connected to the negative terminal of
an external d.c. power supply. The positive terminal is connected to an inert electrode such as
graphite. Under these conditions, the metal acts as cathode and hence does not undergo
corrosion. The inert electrode acts as anode; but it does not undergo corrosion because it is inert.
Battery
Protected metal
Inert anode
Impressed current method
III. Corrosion inhibitors:

Corrosion inhibitors are chemical substances which are added in small quantities to the corrosive
environment to decrease the rate of corrosion. Inhibitors slow down the anodic reaction or the
cathodic reaction generally by forming a protective film on the anodic region or the cathodic
region.
There are two types of corrosion inhibiters namely anodic corrosion inhibiters and cathodic
corrosion inhibitors.
28
Anodic corrosion inhibitors: Compounds such as chromates, molybdates and tungstates are
used as anodic corrosion inhibitors. They react with the surface atoms at the anodic region and
form a protective film of oxide or metallate. This protective film acts as a barrier between the
metal surface and the corrosive environment.
Na3PO4→ 3 Na+ + PO4-3
Fe → Fe +2 + 2 e-
Fe +2 + PO4-3→ Fe3 (PO4 )2↓
Anodic corrosion inhibitors must be added in sufficient quantities. If insufficient quantity is

added, then a part of the anodic region is covered with the protective film leaving the remaining
anodic region exposed to the environment. Formation of small anodic area results in intense
corrosion.
Cathodic corrosion inhibitors:
The cathodic reaction may be (i) liberation of hydrogen or (ii) absorption of oxygen.
(i) When the cathodic reaction is liberation of hydrogen, the cathodic reaction can be
retarded (a) by forming an adsorbed layer on the cathode surface or (b) by increasing the
hydrogen over voltage.
(a) When compounds such as amines, urea and thiourea are added to the corrosion medium,
they are adsorbed on the cathodic region forming a protective film. The protective film prevents
the migration of H+ ions on to the cathodic surface.
29
Protective film of
absorbed molecular
Cathodic Region
H+ ion can not reach the
Cathodic surface
(b) When oxides of arsenic and antimony are added to the corrosive medium, they form a
metallic film on the cathode surface. Since the hydrogen over voltage on these metals is high,
hydrogen liberation is retarded.
(ii) When the cathodic reaction is absorption of oxygen, salts such as ZnSO4, MgSO4 etc. are
added to the corrosive medium. The cations of these salts (Zn2+, Mg2+) react with the hydroxyl
ions formed at the cathode, depositing insoluble hydroxides (Zn(OH)2, Mg(OH)2) on the cathode
surface. The hydroxide film acts as a protective film. It prevents the migration of oxygen to the
cathode surface.
Thus, a retarded cathodic reaction retards the anodic reaction also. Hence, corrosion is
controlled.
Protective film of
Mg (OH)2 or Zn(OH)2
Cathodic Region
O2 cannot reach the
Cathodic surface
30
31

Corrosion Science: Department of Chemistry, RVCE

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Corrosion Science: Department of Chemistry, RVCE

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Department of chemistry, RVCE

Corrosion is a universal phenomenon associated with certain metals and alloys. A

Fe2+ + 2OH- Fe(OH)2

2Fe(OH)2 + 11/2 O2 + H2O Fe2O3.3H2O rust(brown

2. Green scales formed on copper vessel. It is due to formation of basic carbonate

Reason behind corrosion

Liquid metal corrosion:

Ex: corrosion of steel in presence of moisture

Difference between Dry Corrosion and Wet Corrosion

Sl No Dry corrosion Wet corrosion

3 Corrosion is uniform. Corrosion is not uniform.

Electrochemical theory of corrosion

According to electrochemical theory, when a metal such as iron is exposed to corrosive

(a) Formation of anodic and cathodic areas

Fe2+ + 2OH- Fe(OH)2

Primary corrosion product (unstable)

At cathode In absence of oxygen In presence of oxygen

Fe2+ + 2OH- Fe(OH)2

Primary corrosion product (unstable)

1. Differential metal corrosion/Galvanic Corrosion

At anode : M Mn+ + ne- (Oxidation of metal M)

2. Differential aeration corrosion:

The reactions may be represented as follows:

The reactions may be represented as follows:

At anode : M Mn+ + ne- (Oxidation of metal M)

(B) Waterline corrosion:

The reactions may be represented as follows:

At anode : M Mn+ + ne- (Oxidation of metal M)

Very dilute NaOH

Na2CO3 + 4H2O 2NaOH + CO2

3 Na2FeO2 + 4H2O Fe3O4 + H2 + 6NaOH

Factors affecting the rate of corrosion

1. Nature of the metal:

Volume of the Metal oxide

3. Relative Areas of Anode and Cathode (Area effect)

Polarization is defined as a process where there is a variation of electrode potential due to

This is due to the following reasons

In general, the rate of a chemical reaction increases with increase in temperature.

(i) Increase in conductance of the medium-ions migrates fast at higher temperature.

Protective coatings can be broadly classified into

(a) Metallic coating (b) Inorganic coating (c) organic coating

Q: Galvanized articles are preferred over tinned articles. Why?

Differences between Galvanizing and Tinning.

4 Galvanized containers cannot be used for Tin is non-toxic in nature of any

1. Anodizing (Anodizing of aluminum):

It is a method of developing an oxide layer on the surface by induced oxidation, in an

The electrode reactions occurring during anodizing process are:

At anode: 2 Al + 3 H2O  Al2O3 + 6 H+ + 6e-

Over all reaction: 2 Al + 3H2O  Al2O3 + 3 H2↑

Note: Other metals such as Mg, Ti etc. can also be anodized.

A modern Phosphating bath contains three essential components.

The Phosphating involves the following steps

3Fe + 2 H3PO4 → Fe3(PO4)2 + 3 H2↑

Requirements of a good paint:

4. A good paint should adhere well to the surface.

Difference between paint and Varnish

II. Cathodic protection:-

The reduction or prevention of corrosion by making metallic structure as cathode in the

a) Sacrificial anodic protection (galvanic protection) b) Impressed current cathodic protection

a) Sacrificial anode method

Steel pipe Cathode

1. Low installation and operating cost.

2. Capacity to protect complex structures.