ENGINEERING CHEMISTRY

MODULE-II
CORROSION AND METAL FINISHING
Definition of corrosion: Corrosion is defined as the destruction of metals or alloys by the
surrounding environment through chemical or electrochemical reactions
Example: When iron is exposed to air in the presence of moisture, hydrated ferric oxide (rust) is
formed. Fe2+ + 2 OH-  Fe(OH)2 
2 Fe(OH)2 + 1/2 O2 + H2O  Fe2O3 .3 H2O (rust)

Chemical /Direct chemical corrosion: corrosion occurs in the absence of moisture or

conducting electrolyte medium, due to the direct chemical reaction between the metal & the
gases present in the corrosion environment is called as direct chemical corrosion or dry
corrosion.
Here direct oxidation (corrosion), of metals and alloys takes place on exposure to O 2 or many
corrosive gases such as halogen,HCl, H2S, SO2, NH3 or anhydrous inorganic liquid.
Two major factors deciding the rate of corrosion are (i) chemical affinity between the metal and
gas And (ii) the nature of the corrosion product formed.

Electrochemical theory of corrosion taking iron as an example: According to

electrochemical theory, when a metal such as iron is exposed to corrosive environment,
following changes occur.
A large number of tiny galvanic cells with anodic and cathodic regions are formed.

O2
Fe2+ OH- H2O
Fe2+ OH-
Cathodic region
Anodic region
Electrons

Iron Metal

R
eactions:
Reaction at anodic region: As mentioned above, oxidation of metal takes place at anode.
e.g. Fe  Fe2+ + 2 e-
Reactions at cathodic region: At cathode, the reaction is either
a) liberation of hydrogen or
b) absorption of oxygen.

a) Liberation of hydrogen ( in the absence of oxygen)

In acidic medium the reaction is
2 H+ + 2 e-  H2 

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In neutral or alkaline medium, the reaction is

2 H2O + 2 e-  2 OH- + H2 

b) Absorption of oxygen ( in the presence of oxygen)

In acidic medium, the reaction is

4 H+ + O2 + 4 e-  2 H2O
In neutral or alkaline medium, the reaction is
2 H2O + O2 + 4 e-  4 OH-
Overall reaction:
Fe2+ + 2 OH-  Fe(OH)2 
2 Fe(OH)2 + 1/2 O2 + H2O  Fe2O3 . 3 H2O (yellow rust)
3 Fe(OH)2 + 1/2 O2  Fe3O4 . 3 H2O (black rust)

Factors affecting the rate of corrosion:

Nature of the metal: Metals with lower electrode potentials are more reactive and are more
susceptible to corrosion. For example, elements such as Mg and Zn, which have low electrode
potentials, are highly susceptible to corrosion. Noble metal such as gold and platinum, which
have higher electrode potentials, are less susceptible to corrosion.

Exceptions: Metals and alloys which show passivity are exceptions for this general trend. Such
metals form a protective coating on the surface which prevents corrosion.
Nature of corrosion product: If the corrosion product is adherent, insoluble, stable, non
volatile 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 non-adherent, soluble, unstable, conducting 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 Cr 2O3 on the surface. But in the case of Zn
and Fe, the corrosion products formed do not have protective value.

Ratio of Anodic and cathodic areas: Smaller the anodic area and larger the cathodic area,
more intense and faster is the corrosion. 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.

Nature of medium-Conductivity: Rate of corrosion increases with increase in conductance of

the medium. As the conductance of the medium increases, ions can move easily through the
medium. This decreases the polarization potential and as a result corrosion increases.
Example: Metal immersed in sea water undergoes fast corrosion than metal in frsh water.

Nature of medium-pH of the medium: In general, lower the p H of corrosion medium, higher is
the corrosion rate. Exception: Metals like Al etc. undergo fast corrosion in media with high p H

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due to the formation of sparingly soluble, conducting and nonporous layer of hydroxides. The P H
of the solutions also decides the type of cathodic reaction, because of the continuous evolution of
H2 gas at the cathode region /cathode.
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 p H 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.

Temperature: Higher the temperature, higher is the rate of corrosion.

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.
Increase in temperature increases the ionic conductivity of the corrosive medium. This also
contributes to the increase in corrosion rate.
Types of corrosion:
1. Differential metal /Galvanic corrosion:

Zn metal Fe metal Fe metal Cu metal

Anode Cathode Anode Cathode

This type of corrosion occurs when two dissimilar metals are in contact with each other and are
exposed to a corrosive environment. The two metals differ in their electrode potentials. The
metal with lower electrode potential acts as anode and the other metal with higher electrode
potential acts as cathode.
The anodic metal undergoes oxidation and gets corroded. A reduction reaction occurs at the
cathodic metal. The cathodic metal does not undergo corrosion.
The reactions may be represented as follows:
At anode: M  Mn+ + n e-
At cathode: 2 H2O + O2 + 4 e-  4 OH-
Higher the potential difference between the anodic and cathodic metals, higher is the rate of
corrosion. Also on the ratio of anodic area to cathodic area, environmental factors, tendency of
metal to exhibit passivity.
Example: When iron is in contact with zinc, iron acts as cathode and zinc acts as anode because
zinc has lower electrode 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 electrode
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

2 Differential aeration corrosion:

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This type of corrosion occurs when two different parts of the same metal are exposed to different
oxygen concentrations. (e.g. An iron rod partially dipped in water.) 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.
The reactions may be represented as follows:
At anode: M  Mn+ + n e- (Oxidation of M)
At cathode: 2 H2O + O2 + 4 e  4 OH-
-
(Reduction of O2
Other examples:
Iron

More O2,
(Cathode)

Less O2,
(Anode)
Water

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.

3. Pitting corrosion: This is an example of differential aeration corrossionWhen a small

dust particle gets deposited on a steel surface, the region below the dust particle is exposed to
less oxygen compared to the remaining part. As a result, the region below the dust particle

acts as anode undergoes corrosion and forms a pit. The remaining region of the metal acts as
cathode and is unaffected.
The reactions may be represented as follows:

At anode: M  Mn+ + n e-
At cathode: 2 H2O + O2 + 4 e-  4 OH-
Formation of a small anodic area and a large cathodic area results in intense corrosion below the
dust particle.

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4. Water line corrosion: This is an example of differential aeration corrosion.

More oxygen,
((Cathode) Rust

Less
Oxygen Water
(Anode)

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 dissolved 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.
The reactions may be represented as follows:
At anode: M  Mn+ + n e- (Oxidation of metal, M)
At cathode: 2 H2O + O2 + 4 e  4 OH-
-
(Reduction of oxygen)
Other example: Ships which remain partially immersed in sea water for a long time undergo
water line corrosion.

Corrosion control
1. Inorganic coatings
Anodizing (Anodizing of aluminum): When aluminum metal is made anodic in an electrolytic
bath with sulphuric acid or chromic acid as the electrolyte, a thin layer of aluminium oxide
(Al2O3) is formed on the surface. This process is called anodizing of aluminium or anodic
oxidation of aluminum.
Process: The article is subjected to decreasing and polishing and then made as anode. Chromic
acid electrolyte is maintained at about 35 0C and suitable voltage is maintained to get desired
thickness of the oxide film. After anodizing it is subjected to sealing which involves heating with
boiling water or steam. When anodized aluminium is exposed to a corrosive environment, the
Al2O3 layer on the surface acts as a protective coating. Hence corrosion is prevented.

Dc Power
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Other metals such as Mg, Ti etc. can also be anodized.

(Note: 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.)
Applications: Metals such as Al, Mg, Ti etc. are anodized to control corrosion.
METAL COATINGS
Metal coating definition: Metallic coatings are applied on a metal in order to protect metal from
corrosion.
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.
Process: 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.
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.
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.) And because of the formation of small cathodic area
and larger anodic area corrosion process will not be there.
(Note: Galvanized articles are not used for preparing and storing food because zinc dissolves in
dilute acids producing toxic zinc compounds)

3. Cathodic protection:-
(a) Cathodic protection:-sacrificial anode method:

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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, by connecting
auxiliary anode which is more active metal such as Al, Mg, or Zn.

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 buried pipe lines.
Mg blocks are connected to buried oil storage tank.

(b) Cathodic protection:- 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.

Battery

Metal to be protected inert anode

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.

METAL FINISHING
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Definition of metal finishing:

Metal finishing is the process of deposition of a layer of one metal on the surface of substrate
(metal, plastic etc) or the process of conversion of a surface layer of atoms on a metal into an
oxide film. (Note: Metal finishing is the process of surface modification of a metal)
Electroplating and electroless plating are two important techniques of metal finishing.
Technological importance of metal finishing: Metal finishing is carried out to obtain
technologically important surface properties. These properties are:
1. A decorative appearance.
2. An improved corrosion resistance.
3. An improved heat resistance.
4. An improved surface hardness.
(an improved resistance to wear and tear, an improved resistance to abrasion.)
5. An improved solderability.
6. Good thermal conductivity.
7. Good electrical conductivity.
8. Good thermal reflectivity.
9. Good optical reflectivity.
Electroplating:
Definition: Electroplating is the process of electrolytic deposition of a metal on the surface of
another metal/substrate; the substrate may be another metal, a polymer, a ceramic or a
composite.
Electroplating of chromium: (Decorative Cr and Hard Cr)
There are two types of chromium coating.
Decorative Cr plating: Thin deposit of 0.25 to 0.75 µM applied over Cu-Ni or Ni under coat to
give pleasing look & non tarnishing nature to the plated article &

Hard Cr plating: Industrial of engg Cr, directly on to the substrate thickness 2.5 to 300 µM.
The surface of the object is cleaned thoroughly. Organic substances are removed by solvent
cleaning and alkali cleaning. Inorganic substances are removed by mechanical cleaning and
pickling. Finally, the surface is washed with deionized water. Then, chromium plating is done
under the following conditions.

Chromium plating Decorative chromium Hard chromium

Anode Insoluble anodes like Pb-Sn or Insoluble anodes like Pb-Sn or
Pb-Sb coated with PbO2 Pb-Sb coated with PbO2
Cathode Object to be plated Object to be plated
Bath composition 100:1 chromic acid and H2SO4 100:1 chromic acid and H2SO4
Current Density 145-430 A/ft2 290-580 A/ft2
Temperature 45-60 oC 45-60 oC
Current Efficiency 10-15 % 17–21 %
Application Provides durable and good Extensively used in industrial and
finish on automobiles, surgical engineering applications.
instruments.

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Anodic reaction Liberation of oxygen:

Cathodic reaction

In chromic acid, chromium is present in 6+ oxidation state. It is first reduced to 3+ state by a

complex anodic reaction in the presence of sulphate ions. The Cr 3+ then gets reduced to Cr on
the substrate surface. For a good deposit, the Cr 3+ concentration must be low. The PbO 2 oxidizes
a part of Cr3+ to Cr6+, thus reducing the concentration of Cr3+.
In chromium plating we do not use chromium metal as anode due to the following reasons.
1. If chromium dissolves at anode, there will be a high concentration of Cr 3+ in solution. In
such cases, a black deposit is obtained.
2. In acidic solutions, chromium may undergo passivation.

ELECTROLESS PLATING
Definition of electroless plating: Electroless plating is a method of depositing a metal over a
substrate by controlled chemical reduction of metal ions by a suitable reducing agent without
using electrical energy.
Principal components/Composition of an electroless plating bath: An electroless plating bath
contains the following components:
1. A source of electro active metal in the form of a soluble salt. e.g. NiCl2, CuSO4
2. Reducing agent to reduce metal ions into metal atoms. e.g. Sodium hypophosphite,
formaldehyde.
3. Complexing agents to form complex compounds with metal ions.
4. Exaltant (accelerator) to increase the rate of plating. 5. Stabilizer to give more stability to
solution. 6. Addition agents such as brighteners. 7. Buffer to control pH.
Electroless plating of Copper
Before electroless plating, the surface is cleaned thoroughly. Insulators such as plastics and
printed circuit boards are activated by dipping first in stannous chloride (SnCl 2) and then in
palladium chloride (PdCl2). Then, the electroless plating is done under the following conditions:

Plating/Coating solution CuSO4 solution (30g/ dm3)

Reducing agent: Formaldehyde 37% solution 170 mL/dm3
Buffer: NaOH (15g/L) + Rochelle salt (14g/L)
Complexing agent & exaltant EDTA (17 g/L)
PH 11
Temperature 25oc
Anode reaction 2HCHO + 4OH- 2HCOO- +2H2O + H2 +2e-
Cathode reaction Cu2+ + 2e- Cu
Overall reaction Cu2+ + 2HCHO + 4OH- Cu +2HCOO- +2H2O + H2

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Formaldehyde and copper sulphate are added to the plating bath periodically.

Applications: 1. Used for metalizing printed circuit boards.

2. Used to produce through-hole connections.-PCBs

Application-Through-hole connection is PCB’s:

For PCB’s with double sided circuits, through-hole connection is required. The through-hole
connection is made by electroless plating technique

To start with, the two sides of a plastic board is electroplated with copper. Selected areas are
protected and the remaining areas are etched away. Thus two circuits are produced on two sides.
The connection between two sides is made by drilling hole followed by plating through-holes by
electroless plating.

Differences between electroplating and electroless plating:

Property Electroplating Electroless plating
1. Driving force Power supply Autocatalytic redox reaction

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2. Anode reaction Reducing agent  Oxidized product

+ n e-
3. Cathode reaction
[Link] of anode reaction Separate anode Article to be plated

[Link] of cathode Article to be plated Article to be plated ( with a catalytic

reaction surface)
6. Anode reactant M or H2O Reducing agent
7. Nature of deposit Pure metal or definite alloy Usually metal contaminated with
reducing agent-derived species.

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