Corrosion and its Control

CY 101 Chemistry

Instructor: Dr. Debayan Sarkar
(Email: sarkard@nitrkl.ac.in, Ph: 7735588382)
(Office: Biomedical 407)






2013
National Institute of Technology,
Rourkela

1
2
Chemistry Deals with compounds :
1. Organic Compounds Simple to Complex.




2. Inorganic Compounds Metals, Alloys.



GOLD
IRON
3
Organo-metallic Compounds :

Carbon- Metal Bond

R----Mg-----X Grignard Reagent
The Key Concepts:
Make a carbon negatively
charged/polarlized so it is
nucleophilic.
Reaction with electrophilic carbons
can make carbon-carbon bonds
This is a Big Deal!
Victor Grignard
Grignard Reagents
Discovered by Victor Grignard
in 1900
Key factors are ethereal solvent
and water-free conditions
Awarded Nobel Prize in 1912
Grignard, Victor , 18711935, French chemist. He shared the 1912 Nobel
Prize in Chemistry for his work in organic synthesis based on his discovery
(1900) of the Grignard Reagent. He taught at the Univ. of Nancy (190919)
and at the Univ. of Lyons (from 1919 until the end of his career).
The First Organometallic Reagents
HYDROGENATION
HETEROGENEOUS CATALYSIS
H H
Alkene Reactions

HETEROGENEOUS CATALYSTS
Do not dissolve in the solvent.
These catalysts are usually powder-
ed metals or metal oxides.
Traditional type
The catalyst is suspended by con-
stantly stirring the solution (this is a
two phase, or heterogenous, system).
Hydrogen is bubbled through the
solution
They adsorb hydrogen on the surface.
H
H
H
H
H
H
H
H
2
Pd, Pt, PtO
2
, Ni
.
.
.
.
.
Hydrogenation of Alkynes
catalyst
catalyst = Pt, Pd, or Ni
+
2 H
2
C C H R H C C R
H
H
H
H
With normal catalysts it is
not possible to stop at the
alkene by the addition of
one mole of H
2
.
Alkenes are more reactive
than the starting alkyne, and
the second addition proceeds
at a faster rate than the first.
Alkynes react twice (two double bonds)
+ H
2
Pd/BaSO
4
quinoline
heat
one
equivalent
C C R R'
C C
H
R
H
R'
stereospecific
Lindlar is a special catalyst that allows
the hydrogenation of an alkyne to stop
after one mole of hydrogen is added.
N
quinoline
syn addition
Most amines, and compounds
containing sulfur, reduce the
activity of catalysts or poison
them.
Lindlar Catalyst
QUINOLINE
QUINOLINE
QUINOLINE
QUINOLINE
POISONING MECHANISM IS UNKNOWN
POISONING MECHANISM IS UNKNOWN
Quinoline binds to sites on the catalyst.
Linear alkynes can appr oach and pick up hydr ogens.
Planar alkenes ar e blocked.
QUINOLINE
QUINOLINE
QUINOLINE
C=C
R R
R R
QUINOLINE
QUINOLINE
R-C C-R
alkyne fits
alkene blocked
A POSSIBLE HYPOTHESIS IS GIVEN HERE
sur face of
Lindlar catalyst
bound quinoline
It is not uncommon that either specific or specially
designed catalysts are used to control the results
in hydrogenation reactions.

For this reason a very large variety of catalysts are
available to the organic chemist.
Pd
Pd on Carbon
Pt
PtO
2
(Adams Catalyst)
Ni (Raney Nickel)
Pd on BaSO
4
with quinoline (Lindlar Catalyst)
Rh
Ru
etc., etc., etc. .
DESIGNER CATALYSTS
Outline
Class 1-3: Introduction to Corrosion,,
Types of Corrosion, and Mechanism of
Corrosion

Class 4: Principle of Corrosion Control
12
What is Corrosion?
Corrodere (Latin) To eat away
Corrosion may be defined as the gradual destruction of metals by the
chemical or electrochemical reaction with the environment. During
corrosion, the metals are converted to their metallic compounds at the
surface.








The loss of materials due to corrosion has become a great problem. The
most common example for corrosion is the rusting of iron when it is
exposed to atmospheric conditions. The rusting is due to the formation
of hydrated ferric oxide on the surface. Another example is the
formation of green film of basic copper carbonate on the surface of Cu,
when exposed to moist air containing CO
2
.
13
14
4
Corrosion: Metallurgy in Reverse
2
2
Fontana, M.G., Corrosion Engineering. 3rd ed. 1986, New York: McGraw-Hill.
15
3
E
n
v
i
r
o
n
m
e
n
t
s

i
n

C
o
r
r
o
s
i
o
n
1
1
Sheir, L.L., R.A. Jarman, and G.T. Burstein, eds. Corrosion. 3rd ed. Vol. 1. 2000, Butterworth-Heinemann: Oxford.
Environments
in corrosion
Corrosion case studies
16
1988
19-year old Boeing 737 operated by Aloha Airlines lost a major
portion of the upper fuselage in full flight at 24000 ft
6
Aloha Incident
Bhopal Gas Leak
17
In the early morning of December 3, 1984, water
inadvertently entered the methylisocyanate storage
tank, where >40 metric tons of methylisocyanate were
being stored. The addition of water to the tank caused
a runaway chemical reaction, resulting in a rapid rise in
pressure and temperature. The heat generated by the
reaction, the presence of higher than normal
concentrations of chloroform, and the presence of
an iron catalyst, produced by the corrosion of
the stainless steel tank wall, resulted in a reaction
of such momentum that gases formed could not be
contained by safety systems.
Losses due to Corrosion
18
12
Losses due to Corrosion
4
4
Uhlig, H.H. and R.W. Revie, Corrosion and Corrosion Control. 3rd ed. 1985, New York: John Wiley & Sons.
Loss of metal by corrosion is a waste not only of the metal, but
also of the energy, the water, and the human effort that was used
to produce and fabricate the metal structures in the first place.
In addition, rebuilding corroded equipment requires further
investment of all these resources metal, energy, water, and
human.
19
Direct losses include the costs of replacing corroded structures
and machinery or their components, such as condenser tubes,
mufflers, pipelines, and metal roofing, including necessary labor.
Other examples are (a) repainting structures where prevention of
rusting is the prime objective and (b) the capital costs plus
maintenance of cathodic protection systems for underground
pipelines.


Direct losses include the extra cost of using corrosion - resistant
metals and alloys instead of carbon steel where the latter has
adequate mechanical properties but not sufficient corrosion
resistance; there are also the costs of galvanizing or nickel plating
of steel, of adding corrosion inhibitors to water, and of
dehumidifying storage rooms for metal equipment.

Indirect losses are more difficult to assess.
Losses due to Corrosion
Why study Corrosion?
20
1. Materials are Precious resources
2. Engineering design is incomplete without knowledge
of corrosion
3. Applying knowledge of corrosion protection can
minimize disasters
4. Corrosion- may contaminate stored food, dairy
products , etc
5. Corrosion products cause pollution
6. Artificial implants for the human body ?
21
Books to be followed :

1. Chemistry for Engineers Abhijit Mallick


2. Corrosion Engineering Mars G. Fonatana
Types of Corrosion
22
1. Direct Chemical Corrosion or Dry Corrosion
This type of corrosion occurs mainly through the direct chemical
action of atmospheric gases such as O
2
, halogens, H
2
S, CO
2
, SO
2
, N
2
,
H
2
or liquid metals on metal surface in the absence of moisture.

2. Electrochemical Corrosion or Wet Corrosion
This type of corrosion occurs when :
a. A metal is in contact with a conducting liquid
b.Two dissimilar metals or alloys are immersed partially in a
conducting solution.

This corrosion is due to the existence of separate anodic and
cathodic areas between which current flows through the conducting
solution.

Direct Chemical Corrosion or Dry
Corrosion

23
and other gases
Direct Chemical Corrosion or Dry Corrosion
Type 1: Oxidation corrosion
24
It is brought about by the direct action of O
2
present in the
atmosphere on metals at low or medium temperature in the
absence of moisture to form metallic oxides. Alkali and alkaline
earth metals are rapidly oxidised even at low temperature. At
high temperature almost all metals except (Ag, Au, Pt, Pd) are
attacked.
25
Direct Chemical Corrosion or Dry Corrosion
Type 1: Oxidation corrosion
26
OXIDATION CORROSION :

1. Stable Oxide - The oxide appears as tightly adhering film to protect the
underneath metal. Oxides are formed according to the following reactions :

Al + O
2
= Al
2
O
3

Both Alumina and copper oxide act as protective coating.

2. Unstable Oxide Metal oxides formed on the metal surface decompose back
To the metals and oxygen. Silver ( Ag), Gold ( Au) and Platinum ( Pt) oxides are
Highly unstable and hence they do not undergo oxidation corrosion. Thus silver,
Gold and Platinum are highly stable and not susceptible to oxidation corrosion.

3. Volatile Oxide : MoO
3

4. Porous oxide : If the specific volume of oxide, formed on the surface is less
than that of metal, the oxide film, thus produced on the metal surface
becomes porous, allowing continuous aeration through pores and thereby,
helps continue the corrosion till all the metal has been exhausted.

Volume of the metal oxide
Specific volume of the pore = -----------------------------------------
Volume of metal

27
28
Direct Chemical Corrosion or Dry Corrosion
Type 1: Oxidation corrosion
29
Direct Chemical Corrosion or Dry Corrosion
Type 2: Corrosion by other gases
30
If the film formed is
protective or non-porous
(AgCl film, resulting from the
attack of Cl
2
on Ag)
If the film formed is
non-protective or porous
(dry Cl
2
gas on Sn forming
volatile SnCl
4
)
The intensity or extent
of attack decreases
The intensity or extent
of attack increases
Direct Chemical Corrosion or Dry Corrosion
Type 2: Corrosion by other gases
31
Direct Chemical Corrosion or Dry Corrosion
Type 3: Liquid Metal Corrosion
It is due to the action of liquid metal at high
temperature on solid metal or alloy.

This type of corrosion is found in nuclear power plants.

Corrosion takes place either due to the dissolution of
solid metal by the liquid metal or due to the
penetration of liquid metal in to the solid metal.

For e.g. Sodium metal leads to corrosion of cadmium
in nuclear reactor
32
Wagners Theory of Oxidation of Metals :

According to this theory corrosion may occur by any of the following processes.

(i) Metal ions may migrate outwards,

(ii) Oxide ions may migrate inwards.


(iii) Molecular oxygen may penetrate to the metal/ oxide interface,

(iv) Both the Processes (i) and (ii) occur simultaneously.
33
MECHANISM OF GROWTH OF OXIDE FILMS



(a) P-TYPE OXIDES: oxides deficient in metals.
e.g., NiO, Cu
2
O etc

(b) n- TYPE OXIDES : Oxides with excess of ions.
e.g., ZnO, CdO etc.

In n-type ZnO crystals, Zn
2+
ions , generated at the interface, move
towards the bulk and occupy interstitial voids to neutralise these excess
cations electrons will flow inwards. So, chemical formula of zinc oxide
should be Zn
x
O ,where, x>1.

Metal oxides , formed on the metal surface , are usually non-stoichometric
and hence posses either deficient or excess of cations.
Tese are called semi-conducting oxides.

O
2-
+ - + - + - + - + - + - + - + - + - + -
+ - + - + - + - + - + - + - + - + - + -
+ - + - + - + - + - + - + - + - + - + -
+ - + - + - + - + - + - + - + - + - + -
+ - + - + - + - + - + - + - + - + - + -



34


Zn
2+


Zn
2+



Zn
2+


Zn
2+

Fig.12.1(b) Mechanism of growth of n-type oxide film.
Electrons are
moving from
the surface
to the bulk of
the crystal to
neutralise
excess Zn
2+


n-type (ZnO)
At the interface
: O
2
+ 2e O
2-


Zn Zn
2+
+ 2e

35
Growth of oxide film usually follows any
one of the following laws:

(i) Parabolic law:
(dx/dt) (1/x), on integration, we get X
2
=2kt+C
where, x=thickness of oxide layer and C is constant
Co, Fe, Cr, Ni, Cu and alkaline earth metals follow this law.


(ii) Linear law:
(dx/dt)=k (constant), on integration, we get x=kt+C,
here a protective layer of a definite thickness layer is formed,
as thickness increased oxide film breaks. Alkali metals follow
this law.


36
37
According to electrochemical theory, corrosion of metals
occurs due to the following changes, when they are exposed to
the environment.

1) A large number of minute galvanic cells are formed which
acts as anodic and cathodic areas.
2) At anode the metal undergoes oxidation and electrons are
liberated which migrates towards cathodic region
3) Oxygen of the atmosphere undergoes reduction at cathodic
area in the presence of moisture forming hydroxyl ions at the
cathode
Electrochemical Corrosion or Wet Corrosion
38
Electrochemical corrosion:

When corrosion occurs through the formation of galvanic cells , the
phenomenon is called electrochemical corrosion.
To complete the cell circuit flow of ions and electrolyte medium in
needed.
The galvanic cell has two electrodes, cathode and anode. Corrosion
occur at anode and reduction occur at cathode
The mechanism of reduction process:
In absence of oxygen reduction process:
39
Explain the electrochemical theory of
corrosion?
40
The cell e.m.f is given by : E= E
c
E
a

Where, E
c
and E
a
are the oxidation potentials of cathode and anode
respectively. The free energy change is given by :

G = -nFE----------------------(1)

Where, n is number of electrons ,F =faradays constant=96,500 C/mole,
E is the cell e.m.f , and G is the free energy change.

Again we know that, G=G
0
+ RT ln K
a
--------------- - (2)

Where, K
a
is the equilibrium constant for the

following reaction:
aA + bB lC + mD, where, A & B are the reactants and C & D are the
products.

K
a
= a
C
l
. a
D
m
/a
A
a
.a
B
b
G
0
= (lG
C
0
+ mG
D
0
) (aG
A
0
+ bG
B
0
) = -nFE
0
--------------- (3)

Combining equation (1), (2) and (3) , we get,
E=E
0
(RT/n F) ln K
a


41
DIFFERENCE BETWEEN CHEMICAL AND ELECTROCHEMICAL CORROSION
chemical corrosion

Electrochemical corrosion

1.It occurs in dry condition

1. It occurs in wet condition


2.Corrosion occurs through
chemical reaction with
environment


2. Corrosion occurs through the
formation of various galvanic cells


3.It is slow and uniform process


3. It is a fast and non-uniform
process

4.It occurs in both on
homogeneous and heterogeneous
surfaces


4.It occurs only on heterogeneous
surfaces

42
43
Rusting of iron:
The chemical reactions responsible for rusting of iron are given below:
Anodic reaction: 2Fe 2Fe
2+
+ 4e
Cathodic reaction: O
2
+ 2H
2
O + 4e 4OH
-

_________________________________________
2Fe + 2H
2
O 2Fe
2+
+ 4OH
-

2Fe
2+
+ 2H
2
O + O
2
2Fe(OH)
2

Fe(OH)
2
gets oxidised to Fe(OH)
3
, which exist as

Fe
2
O
3
.xH
2
O. Usually the
value of x is 3. Thus, the chemical formula of rust is Fe
2
O
3
.3H
2
O.

2Fe(OH)
2
+ 2H
2
O + O
2
Fe
2
O
3
.3H
2
O
The Figure 12.3 illustrates the formation of rust.


Corrosion product
Profusely aerated
(cathode)
Pit(less aerated)
anode
Profusely aerated
(cathode)
Fig : Schematic representation of formation of rust
Types of Electrochemical Corrosion
45
1. Galvanic corrosion or Bimetallic corrosion

When two dissimilar metals or alloys are electrically connected and
exposed to an electrolyte, the metal higher in electrochemical
series under goes corrosion. Thus when Zn and Cu are connected, Zn
being higher in the series act as anode and undergoes corrosion and
Cu which is lower in the series act as cathode and gets protected.
Ex: Steel pipe connected to
copper plumbing and
Lead antimony solder
around copper wire.

46
47
What is Galvanic series?
48
The arrangement of elements in the order of their standard
reduction potential is referred to as emf or electrochemical
series. Such a arrangement of few elements given in the table.
49
1) A negative value indicates oxidation tendency and a positive
value indicates reduction tendency with respect to hydrogen.

2) The metal with lower electrode potential are more reactive
and as the electrode potential increases, the reactivity
decreases and metals with higher electrode potentials are more
noble.

3) Metals with lower electrode potentials have the tendency to
replace metals with higher electrode potential from their
solutions for example, Zn displaces Cu, Cu displaces Ag.

4) Metals with negative electrode potentials can liberate
hydrogen from acidic solutions.

What is Galvanic series?
Pitting Corrosion
50
Pitting corrosion is a localized accelerated attack resulting in
the formation of pin holes, pits and cavities on the metal
surface. It is due to the breakdown or cracking of the
protective film on the metal at specified points. This gives rise
to the formation of small anodic and large cathodic areas. Once
a small pit is formed the rate of corrosion will be increased.
Presence of external impurities like sand, dust, water drops
etc on the surface of the metal can also be a cause for this
type of corrosion. In this case, the small part below the
impurity acts as the anodic area while the rest of the metal
acts as the cathode area. Due to corrosion a small pit is
formed at the anodic area which grows gradually.
51
Concentration Cell Corrosion
52
This type of corrosion is due to electrochemical
attack on the metal surface exposed to an
electrolyte of varying concentrations. Metal in
contact with lower concentration will act as anode
and undergoes corrosion. It is observed in chemical
plants and storage tanks and also in marine
structures like ships. Differential aeration corrosion
is the most important.
Differential aeration Corrosion
53
This type of corrosion occurs when one part of the metal is
exposed to a different air concentration from the other part.
This causes a difference in potential between differently
aerated areas. It is found that less oxygenated part acts as
anode and more oxygenated part acts as cathode.

Corrosion of metals partially immersed in a solution is due to
differential aeration corrosion. Consider a Mg rod partially
immersed in NaCl solution. The areas of Mg rod above and just
below the water line are more oxygenated and will act as
cathode. The remaining part of the rod which is well under the
solution is less oxygenated and act as anode and undergone
corrosion.
At anode
Water Line Corrosion
54
It is another type of differential aeration corrosion. Corrosion in
storage tanks, H
2
O tanks, marine structures etc is called water
line corrosion. When water is stored in an iron tank, it is found
that maximum corrosion occurs along a line just below the water
level. The area above the H
2
O line is highly oxygenated and acts
as cathode while the area just below the H
2
O line is less
oxygenated and acts as anode and undergoes corrosion.
Factors Affecting Corrosion
55
The rate and extent of corrosion depends mainly upon
two factors

1. Nature of the metal or metallic conditions

2. Nature of the environment
Nature of the metal or metallic conditions
56
a. Position in Galvanic Series
Metal higher in the galvanic series are more likely to undergo
corrosion.

b. Relative anodic and cathodic areas
Corrosion is more rapid if the anodic area is small because there
is more demand for electrons by the larger cathodic area.

c. Purity of the metal
Impurities in a metal form minute electrochemical cells and the
anodic part gets corroded.
57
Nature of the metal or metallic conditions
d. Physical state of metal
The rate of corrosion is influenced by the physical state of the
metal such as size, orientation of crystals, stress etc. The
smaller the size of metal greater will be the corrosion and the
stressed port of the metal also undergo more corrosion.

e. Nature of corrosion product
Metals like Fe, Mg etc form a non protective porous oxide film
which causes maximum corrosion while metals like Al, Cr, Ni etc
forms protective oxides .

f. Solubility of corrosion product
In electrochemical corrosion, if the corrosion product is soluble
in the medium, then the corrosion proceeds at a faster rate.

g. Volatility of corrosion product
If the corrosion product is volatile rapid and continuous corrosion
occurs.
Nature of Environment
58
a. Temperature
Rise of temperature increases the rate of corrosion.

b. Humidity
Humidity air is directly related to the rate of corrosion. In
humid condition atmospheric gases easily form electrochemical
cell by which corrosion occurs to a great extent.

c. Effect of pH
Generally acidic media is pH<7 is more corrosive than alkaline
and neutral media.

d. Formation of O
2
concentration cell
If there is a difference in O
2
conc
n
around the metal, then the
less oxygenated metal part becomes anode and the more
oxygenated part becomes cathode and an O
2
concentration cell
is set up resulting corrosion.
59
Nature of Environment
e. Nature of ions
Presence of anions like silicate ions in the medium leads to the
formation of insoluble reaction products which inhibit further
corrosion. On the other hand Cl- ions and NH
4
+
ions etc destroy
the protective surface film thereby exposing fresh metal surface
for corrosion. Rapid corrosion of Al in sea water is an example.

f. Presence of suspended particulars or compounds
Particulars like NaCl, (NH
4
)
2
SO
4
etc along with moisture act as
powerful electrolyte and promote corrosion.

g. Conductance of the corroding medium
In the case of underground and submerged structures, the
conductance of the medium influences the rate of corrosion.
Conductance of dry sandy soil is lower than that of clayey and
mineralized soil. Hence the corrosion rate of metallic structures in
lower in dry sandy soil than in clayey and mineralized soil.
60
17
Distribution of disciplines in which active
corrosion engineers have graduated
Distribution of disciplines in which
active corrosion engineers have graduated
61
18
So .. What would be expected from You (a
Corrosion Engineer)?
Ensuring maximum life of new equipment
Preservation of existing equipment
Protecting or improving the quality of a product in order to
maintain or improve a competitive position.
Avoiding costly interruptions of production.
Reducing or eliminating losses of valuable products by spillage
or leaks.
Refitting of equipment withdrawn from service because of
corrosion.
Reducing hazards to life and property that might be associated
with corrosion:
Explosions of pressure vessels or piping systems
release of poisonous or explosive gases or vapors
are a few examples.
So ..What would be expected from a
corrosion engineer?
62
The important methods used to control corrosion are,

1. Design and selection of the materials.

2. Protective coatings.
a) Organic coatings paints and enamels.
b) Inorganic coatings
i) Metal coatings anodic and cathodic
ii) Surface conversion coatings anodizing, phosphating.

3) Corrosion inhibitors.

4) Cathodic protection.

5) Anodic protection.
Corrosion Control or Protection from
Corrosion
Corrosion Control or Protection from
Corrosion
63
Cathodic Protection

In this method, the corroding metal is forced to behave like a
cathode. There are two types of cathodic protection.


a. Sacrificial Anodic protection on Galvanic protection
In this method, the metallic structure which is to be protected
from corrosion is connected to a more anodic metal by a wire so
that the entire corrosion is concentrated on this more active
metal. The more active metal loses electrons and get corroded
and this metal is called sacrificial anode. Metals commonly
employed as sacrificial anode are Mg, Zn, Al and their alloys.
Sacrificial Anodic protection on Galvanic
protection
64
Applications
Important applications of sacrificial anodic method include
protection of buried pipe lines, underground cables, marine
structures etc.
Impressed Current Cathodic Protection
65
In this method, an impressed current is applied in the opposite
direction to nullify corrosion current so as to convert the
corroding metal from anode to cathode. Impressed current can
be derived from a direct current source like battery. An inert
or insoluble electrode like graphite or silica act as anode to
complete the circuit. The surroundings of anode should be
filled with salts and carbon to increased the conductivity.

Applications
This type of cathodic protection
has been applied to water coolers,
water tanks, buried oil and
water pipes, transmission towers
etc.

Inorganic Coatings
66
i) Metal coatings anodic and Cathodic
ii) Surface conversion coatings anodizing, phosphating.

i) Metal coatings
Deposition of protective metal over the surface of base
metal(metal to be procted from corrosion) is known as metallic
coatings. It is divided into Anodic and Cathodic metal coatings.

a) Anodic metal coatings:
Anodic metal coatings involve coating the base metal with more
active metals, which are anodic to the base metal.
Example: Galvanization

b) Cathodic coatings: Cathodic coatings involve coating a base metal
with more noble metals, which are cathodic to the base metal.
Metals such as Copper, Nickel, and Tin Silver etc are coated on
Iron. One of the disadvantage of Cathodic coatings is if coating
ruptures it leads more corrosion because of small anodic area and
large cathodic area. Example: Tinning
Surface Conversion Coatings
67
Surface conversion coatings are chemical conversion coatings. The
surface layer of the base metal is converted into a compound by
chemical or electrochemical reactions, which prevents the base
metal form corrosion. The coating can be done by chemical dip,
spray or by electrolytic method. The coating helps in the increased
electrical insulation, enhanced adherence for paints and prevention
of corrosion.

Example: Anodizing , Phosphating
Explain the Process of Galvanization
68
It is a process of coating the base metal surface with Zinc, tin,
lead, or aluminium metal. Example: coating Zinc on Iron by hot
dipping Method. It involves the following steps.

The Iron metal surface is washed with organic solvents to
remove oil, grease etc content on the metal surface.

Then the metal is passed through dilute sulphuric acid to remove
rust and other depositions. Finally the metal is washed with water
and dried.

The metal is then dipped in molten Zinc and passed through
Ammonium chloride and Zinc chloride flux to prevent oxidation of
Zinc. The excess Zinc is removed by passing through the rollers or
by wiping.

Uses: Galvanisation is used for roofing sheets, buckets, bolts,
nuts, nails, pipes etc.
69
Explain the Process of Tinning
Tinning is a process of coating the base metal with Tin (Sn). It is
carried out by hot dipping method as fallows.

The base metal surface is washed with organic solvents to
remove oil, grease etc content on the metal surface.

Then the metal is passed through dilute sulphuric acid to remove
rust and other depositions. Finally the metal is washed with water
and dried.

The metal is passed through Ammonium chloride and Zinc
chloride flux and then dipped in molten Tin. Finally it is dipped in
palm oil to prevent oxidation of Tin. The excess Tin is removed by
passing through the rollers or by wiping.

Tinning is widely used for coating steel, Cu and brass sheets which
are used for making containers for storing food studs, oils,
kerosene & packing food materials. Tinned Cu sheets are used for
making cooking utensils & refrigeration equipments.
Electroplating or Electrodeposition
70
It is probably the most important and most frequently applied
industrial method of producing metallic coatings. Electroplating
is carried out by a process called electrolysis. Thus in this
process, the coating metal is deposited on the base metal by
passing direct current through an electrolyte containing the
soluble salt of the coating metal. The base metal to be
electroplated is made the cathode of the electrolytic cell
whereas the anode is either made of the coating metal itself or
an inert material of good electrical conductivity like graphic.
Objectives:
1. To increase the resistance to corrosion.
2. To increase resistance to chemical attack.
3. To increase physical appearance and hardness.
4. To improve the surface properties.
5. To increase the decorative and commercial values of the
metal.
71
For electroplating of Ni, NiSO
4
and NiCl
2
are used as the electrolyte.
For electroplating of Cr, chromic acid is used as the electrolyte. For
Au plating, AuCl
3
solution is taken as the electrolyte. For Cu plating
CuSO
4
solution is used as the electrolyte. In silver plating, AgNO
3

solution is used as the electrolyte.
Use of Corrosion Inhibitors
72
Chemicals which are added in small quantities to the corroding
medium in order to reduce the corrosion rate are called corrosion
inhibitors. They reduce corrosion by forming a protective film
either at the cathode or anode. Thus there are two types of
corrosion inhibitors anodic inhibitors and cathodic inhibitors.


Anodic inhibitors

Chromates (CrO
4
) phosphate (PO
4
), and Tungstates (WO
4
)
transition metals are used as anodic inhibitors. They react with
the newly produced metal ions at the anode forming a protective
film or barrier there by preventing further corrosion.
73
Cathodic Inhibitors

These are the substance, which slow down the cathodic reaction.
The cathodic reactions involve liberation of hydrogen in acidic
solution or OH-ions in alkaline and neutral medium. The cathodic
organic inhibitors include amines, thiourea, sulphoxides etc. The
two types of cathodic inhibition reactions are liberation of
hydrogen, absorption of oxygen and formation of hydroxyl ions.

i) Inhibition of Oxygen absorption and Hydroxyl ions

ii) Inhibition of Hydrogen liberation

Use of Corrosion Inhibitors
Cathodic Inhibitors
74
i) Inhibition of oxygen absorption and hydroxyl ions

H
2
O + O
2
+ 2 e
-
2 OH
-


The formation of OH
-
ions can be prevented either by removing O
2

from the medium or by decreasing the diffusion of O
2
in to the
cathode. O
2
is removed either by adding reducing agents like Na
2

SO
3
, N
2
H
4
etc or by mechanical dearation.

O
2
+ NH
2
NH
2
N
2
+ 2H
2
O
2 Na
2
SO
3
+ O
2
2Na
2
SO
4

Salts of Zn, Mg or Ni are added to the corroding medium to reduce
the diffusion of O
2
towards cathode. These salts react with OH
-

ions at the cathode forming insoluble hydroxides which are
adsorbed at the cathode.
75
Cathodic Inhibitors
ii) Inhibition of Hydrogen Liberation

2H
+
+ 2 e
-
H
2
(g)

Evolution of H
2
can be prevented by slowing down the diffusion
of H
+
ions to the cathode or by increasing H
2
over voltage.
Diffusion of H
+
ions can be prevented by adding organic inhibitors
such as amines, urea, thiourea etc. These are adsorbed at the
surface as a film. Arsenic oxide or antimony oxide is added to
increase the H
2
over voltage. These oxides form adherent film of
metallic arsenic or antimony at the cathodic areas.