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Corrosion-2

The document discusses factors affecting the rate of corrosion, including the nature of metals and the corroding environment, highlighting aspects such as galvanic series, over voltage, and impurities. It also outlines methods for controlling corrosion, such as cathodic protection, proper design, and the use of inhibitors. The document provides detailed explanations of various corrosion control techniques and their applications.
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0% found this document useful (0 votes)
18 views13 pages

Corrosion-2

The document discusses factors affecting the rate of corrosion, including the nature of metals and the corroding environment, highlighting aspects such as galvanic series, over voltage, and impurities. It also outlines methods for controlling corrosion, such as cathodic protection, proper design, and the use of inhibitors. The document provides detailed explanations of various corrosion control techniques and their applications.
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd
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Welcome to CY1161: Engineering Chemistry

Date: 19-02-2025

Dr. G. Rajeshkhanna
Assistant Professor
Department of Chemistry
[email protected]
Factors affecting rate of corrosion:
i) Nature of metals
ii) Nature of the corroding environment.

Nature of metals:
1) Position in galvanic series:-The metal higher in series is more
active and suffers corrosion. The rate and extent of corrosion is directly
proportional to electrode potential difference between them.
2) Over voltage: - when a metal, which occupies a high position in
galvanic series (say Zinc), is placed in H2SO4, it undergoes corrosion
forming a film and hydrogen gas.

The initial rate of reaction is quite slow, because of high over voltage
(0.73 V) of the zinc metal, which reduces the effective electrode
potential to a small value. However, if few drops of copper sulphate
(CuSO4) are added, the corrosion rate of zinc is accelerated, because
some copper gets deposited on the zinc metal forming minute
cathodes.
Hence rate of corrosion of Zn in presence of cu becomes more.
Thus metals for which over voltages are more get corrode
slowly, where as those which have lower over voltages, the rate
of corrosion is high.

Ex: corrosion of Zn rod dipped in H2SO4 is very slow. When


small amount of CuSO4 solution is added to H2SO4 , Cu gets
deposited on the Zn rod and acts as cathode and the rate of
corrosion of Zn increases.
3) Purity of metal: - Impurity of a metal generally causes heterogeneity
and form minute electrochemical cells and the anodic part gets corroded. For
eg: Zn metal containing impurity such as Pb ( or) Fe undergoes corrosion .
The rate and extent of corrosion increases with extent of impurities.

4) Nature of the surface film: - when metals are exposed to atmosphere,


practically all metals get covered with a thin surface film of metal oxide. The
ratio of the volume of metal oxide to the metal is known as specific volume
ratio. Greater the specific volume ratio, lesser is the oxidation corrosion rate.
For eg: the specific volume ratio of Ni, Cr, W are 1.6, 2.0 and 3.6 respectively.
Consequently the rate of oxidation corrosion is least for (w) tungsten.

5) Nature of the corrosion product:-


a) Solubility of corrosion products : If the corrosion product is soluble
in the corroding medium, then corrosion proceeds at a faster rate otherwise if
it is insoluble, corrosion will be suppressed e.g: PbSO4 formation in case of Pb
in H2SO4.
b)Volatility of corrosion products : - If the corrosion product is volatile ,
it evaporates as soon as it is formed, there by leaving the underlying metal
surface exposed for further attack.
This causes rapid and continuous corrosion.
For eg: Mo forms MoO3 volatile oxide.
Nature of the corroding environment:-
i) Temperature: With increase of temperature, the corrosion
rate also increases because the reaction as well as diffusion
rate of ions in the corrosion medium increases.

ii) Humidity: The higher the humidity of the atmosphere the


greater is rate and extent of corrosion because the moisture acts
as medium for O2 in air and behaves as an electrolyte.

For eg: atmospheric corrosion of iron is slow in dry air


compound to moist air. Iron combines with O2 and water to
form ferrous hydroxide which combines with atmospheric CO2
to form ferrous bicarbonate.
2Fe + O2 + 2H2O –-------> 2Fe(OH)2
Fe(OH)2 + CO2 –------>Fe(HCO3)2
iii) Effect of pH: - Generally acidic media are more corrosive
than alkaline and neutral media. Hence metals may be
virtually classified according to pH range in which they will be
affected (or) resistant.
However atmospheric metals like Al, Pb etc. are corroded in
alkaline medium and
the corrosion rate of iron in O2 free water is slow, Zn is rapidly
corroded in weakly acidic solutions.

iv) Presence of impurities in atmosphere


v) Presence of suspended particles in atmosphere
vi) Nature of ions present
vii) Conductunce of corroding medium
viii) Formation of oxygen concentration cell
ix) Flow velocity of process steam
x) Plarization of electrodes
How can we control corrosion?
Protection against Corrosion (Corrosion Control)
The various methods by which corrosion can be controlled and
prevented are as follows

1. Cathodic protection or electrochemical protection

2. Protection by proper designing

3. Use of inhibitors

2. Material selection

3. Modifying the environment

4. Modification of properties of the metal

7. Use of protective coating.


How can we control corrosion?

CORROSION CONTROL
1) Cathodic protection : The principle involved in this method
is to force the metal to be protected to behave like a cathode
thereby corrosion doesn’t occur. There are two types of cathodic
protection.
i) Sacrificial anodic protection method: - In this method
the metallic structure to be protected is connected by a wire to a
more anodic metal, so that all the corrosion is concentrated at
this more active metal implies the more active metal itself gets
corroded slowly. While the parent structure which is cathodic is
protected. The more active metal so employed is called
“sacrificial anodic” whenever the sacrificial anode is consumed
completely. It is replaced by a fresh one. Metal commonly
employed as sacrificial anodes are Mg, Zn, Al and their alloys.
Sacrificial anodes are used for the protection of buried pipe
lines underground cables, marine structures, ship hulls, water
tanks etc.
(ii) Impressed current–cathodic protection: - In this method an
impressed current is applied in opposite direction to nullify the
corrosion current and current the corroding metal from anode to
cathode. Usually the impressed current is derived from a direct current
source (like battery or rectifier on ac line) with an insoluble anode, like
graphite, high silica iron, scrap iron, stainless steel or platinum. Usually
a sufficient d.c is applied to an insoluble anode, buried in the soil ( or
immersed in the corroding medium) and connected to the metallic
structure to be protected.

The anode is buried is a backfill such as coke breeze or gypsum to


increase the electrical contact between itself and the surrounding soil.
Applications:- This type of protections is used in buried
structures such as tanks and pipelines, transmission line towers,
marine piers, laid up ships etc.,

Advantages: - They can be automatically controlled which


reduce maintenance and operational costs.
Protection by proper designing
Corrosion can be prevented by using proper design.
Important design principles are as follows
(i) Avoid direct contact of two dissimilar metals in a corroding medium. If it
cannot be avoided then use an insulating fitting between them to avoid direct
metal–metal electrical contact.
For example, metal washers should be covered with plastic washers to avoid
direct contact between the two metals.

(ii) When two dissimilar metals in direct contact are to be used then
• They should be as close as possible in the galvanic series.
• The anodic material should have a large area and the area of cathodic material
should be as small as possible.
• The screws, bolts, nuts and welds should be of less reactive metals so that
they can act as cathode with small area.
For example, copper rivets are used to fasten steel sheets and not vice versa
because copper is nobler than steel and hence acts as a cathode. Owing to the
small area of the cathode, the cathodic reaction is limited and corrosion of
anodic steel proceeds slowly.
(iii) Joints should be welded with same metal/alloy (Fig.). Riveting or bolting
with other metal results in crevice corrosion.
Use of Inhibitors

A substance that when added to the corrosive medium effectively


decreases the corrosion of the metal is known as a corrosion inhibitor.
Inhibitors are of two types

(i) Anodic inhibitors They get adsorbed on the anodic surface forming a
passive film on it (example chromates, phosphates, tungstates, etc.), thereby
decreasing the corrosion rate.

(ii) Cathodic inhibitors They slow down the reactions taking place at the
cathode (i.e. , H2 evolution in acidic medium).
For example, organic inhibitors like amines, mercaptans, substituted ureas and
thioureas, heavy metal soaps, etc, decrease the H2 evolution process by
decreasing the diffusion of H+ ions considerably.

Inhibitors like Mg, Zn or Ni salts react with the hydroxyl ions at the cathode
forming corresponding hydroxides that deposit at the cathode and decrease
the O2 absorption process.

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