KYAMBOGO UNIVERSITY

FACULTY OF SCIENCE
PHYSICAL CHEMISTRY
GROUP WORK
TOPIC: APPLICATIONS OF ELECTROCHEMISTRY
AND CHEMISTRY OF CORROSION.

Applications of electrochemistry

Electrochemistry is present in a wide range of application in our daily life

1.Making of electrical batteries: The principles of cells are used to make electrical
batteries. Batteries are made of electrochemical devices such as one or more
galvanic cells or fuel cells. Batteries are used in torches, electrical appliances such
as cellphones.
2.Electroplating: This is the process of coating an electrically conductive object
with a thin layer of metal using an electrical current. Reasons for electroplating:
1. Corrosion protection
2. Abrasion and wear resistance
3. Production of jewelry
3.Applied in the process of electro synthesis for in chloroalkali industry: This
attributes to production of chlorine and sodium hydroxide through the electrolysis
of the raw material brine. Brine is a saturated aqueous solution of sodium chloride.
4.Extraction of metals from ores such as aluminum: Aluminum can be extracted
from bauxite through electrolysis.

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5.Purification of metals: The raw material/ metal can be dissolved in the anode of
the cell and redeposited at the cathode.
6.Useful in analysis techniques: The instrumental measurement of ph. is based on
the measure of the electrode potential in a galvanic cell where one of the electrodes
is sensitive to ph. Other applications include determination of solubility constants,
feasibility of reaction and titrations.
7.Study of corrosion processes: Corrosion is due to dissolution of a metal due to
the undesired formation of local galvanic cell on the surface of the metal. The
purpose of the electrochemistry in this field is to understand the mechanisms of
corrosion and to devise methods to avoid it.
8.Other applications include; treatment of residual water, elimination of organic
material by electro-oxidation, recovery of heavy metals by electrodeposition,
electrocoagulation, electro dialysis, and also the use of microbial electrodes to
obtain energy from the degradation of waste waters.

Corrosion
This is a spontaneous redox reaction in which a metal is attacked by some
compound or substance in its environment and it is converted to an unwanted
compound. It stands material or metal detoriation or surface damage in an
aggressive environment. The corroded metal/material transfers electrons to the
environment and undergoes a valence change from zero to a positive value z. the
environment may be a liquid, gas or hybrid soil- liquid. These environments are
called electrolytes since they have their own conductivity for electron transfer.
The corrosion process is chemical in nature and requires at least two reactions that
must occur in corrosive environment. These are classified as anodic and Cathodic,
where there is oxidation at the anodic and reduction at the Cathodic.

Common examples of corrosion

a) Rusting of steel and cast iron in water and humid air.
b) Corrosion of copper, aluminum and cast iron in automotive cooling systems.

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 c) Corrosion of iron- base, copper-base, nickel- base alloys in the chemical
process industry.
d) Corrosion of turbine blades in gas turbines by hot combustion gases.
e) Corrosion of automotive exhaust systems by direct reaction of the metal
with high temperature gases.

Rusting as a corrosion process

The formation of rust on the surface of iron occurs through the following
steps.

(i) At the anodic region. Iron in contact with water forms anode and gets
oxidized to Fe2+ in the absence of or in the presence of limited oxygen.
Anodic region: Fe(s) →Fe2+ (aq) + 2e–
The released electrons move to another portion of the iron sheet. This
portion of the iron sheet serves as cathode.

(ii)At the Cathodic region. At this Cathodic portion of the surface,

oxygen in the presence of H+ ions (produced due to the ionization of
water molecules) get reduced to form H2O.

Cathodic region:

O2(g) + 4H+(aq) + 4e– →2H2O(l)

The overall reaction of the local cell is the sum of the Cathodic and
anodic reactions.

Overall cell reaction: 2Fe(s) + O2(g) + 4H+(aq) →2Fe2+(aq) + 2H2O(l)

Fe2+ ions move through the water on the surface of the iron sheet.
Presence of electrolytes (e.g., sodium chloride, SO2, CO2 etc.) in water
helps in carrying more current through the local cell on the surface of
iron. The increased flow of current enhances the rate of corrosion. The
Fe2+ ions are further oxidized by atmospheric oxygen to Fe3+, and form

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hydrated iron(III) oxide, expressed as Fe2O3.xH2O. The hydrated ferric
oxide is called rust.

4Fe2+ (aq) + O2(g) + 4H2O(l) → 2Fe2O3(s) + 8H+

Fe2O3(s) + xH2O (l) → Fe2O3.xH2O rust

H+ ions produced in the above reaction help further in the rusting of

iron. Impurities present in iron also enhance rusting by setting a number
of localized cells. Pure iron does not rust.

Types of corrosion
1. General attack corrosion:
This is also known as uniform attack corrosion, general attack corrosion is the
most common type of corrosion and is caused by a chemical or electrochemical
reaction that results in the deterioration of the entire exposed surface of the metal.
General attack corrosion accounts for the greatest amount of metal destruction by
corrosion but it is considered as a safe form of corrosion due to the fact that it is
predictable, manageable and often preventable.
2. Localized corrosion:
Unlike general attack corrosion, localized corrosion specifically targets one area of
the metal structure. Localized corrosion is classified as one of the three types;
Pitting: Pitting results when a small hole or cavity forms in the metal, usually as a
result of de-passivation of a small area. This area becomes anodic, while part of the
remaining metal becomes Cathodic, producing a localized galvanic reaction. The
deterioration of this small area penetrates the metal and can lead to failure. This
form of corrosion is often difficult to detect.
Crevice corrosion: similar to pitting, crevice corrosion occurs at specific location.
This type of corrosion is often associated with a stagnant microenvironment like

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those under gaskets, washers and clamps. Acidic conditions or depletion of oxygen
in a crevice can lead to crevice corrosion.
Filiform corrosion: Occurs under painted or plated surfaces when water bleaches
the coating. Filiform corrosion begins at small defects in the coating and spreads to
cause structural weakness.
3. Galvanic corrosion:
Galvanic corrosion or dissimilar metal corrosion occurs when two different metals
are located together in a corrosive electrolyte. A galvanic couple forms between
the two metals where one metal becomes the anode and the other cathode. The
anode or sacrificial metal corrodes and deteriorates faster than it would alone while
the cathode deteriorates more slowly than it would otherwise.
Conditions for galvanic corrosion
 Electrochemically dissimilar metals must be present
 The metals must be in electrical contact.
 The metals must be exposed to an electrolyte

4. Environmental cracking/ corrosion:

Environmental cracking is a corrosion process that can result from a combination
of environmental conditions affecting the metal. Chemical, temperature and stress
related conditions can result in the following types of environmental corrosion
a. Stress corrosion cracking(SCC)
b. Corrosion fatigue
c. Hydrogen- induced cracking
d. Liquid metal embrittlement

5. Flow- assisted corrosion(FAC)

Flow- assisted corrosion or flow accelerated corrosion, results when a protective
layer of oxide on a metal surface is dissolved or removed by wind or water,
exposing the underlying metal to further corrode and deteriorate.
6. Intergranular corrosion
Intergranular corrosion is a chemical or electrochemical attack on the grain
boundaries of a metal. This often occurs due to impurities in the metal, which tend

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to be present in higher contents near grain boundaries. These boundaries can be
more vulnerable to corrosion than the bulk of the metal.

7. De-Alloying:
De-alloying, or selective leaching, is the selective corrosion of a specific element
in an alloy. The most common type of de-alloying is de-zincification of
unstabilized brass. The result of corrosion in such cases is a deteriorated and
porous copper.

8. Fretting corrosion:
Fretting corrosion occurs as a result of repeated wearing, weight and/or vibration
on an uneven, rough surface. Corrosion, resulting in pits and grooves, occurs on
the surface. Fretting corrosion is often found in rotation and impact machinery,
bolted assemblies and bearings, as well as to surfaces exposed to vibration during
transportation.

9. High-Temperature Corrosion:
Fuels used in gas turbines, diesel engines and other machinery, which contain
vanadium or sulfates can, during combustion, form compounds with a low melting
point. These compounds are very corrosive towards metal alloys normally resistant
to high temperatures and corrosion, including stainless steel. High temperature
corrosion can also be caused by high temperature oxidization, suffixation and
carbonization.

Prevention of corrosion
Corrosion prevention can take a number of forms depending on the circumstances
of the metal being corroded. Corrosion prevention techniques can be generally
classified into 6 groups:

 Environmental Modifications
 Metal Selection and Surface Conditions
 Cathodic Protection
 Corrosion Inhibitors
 Coating
 plating

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Environmental Modification:
Corrosion is caused through chemical interactions between metal and gases in the
surrounding environment. By removing the metal from, or changing, the type of
environment, metal deterioration can be immediately reduced. This may be as
simple as limiting contact with rain or seawater by storing metal materials indoors,
or could be in the form of direct manipulation of the environmental affecting the
metal.
for example, feed water for water boilers can be treated with softeners or other
chemical media to adjust the hardness, alkalinity or oxygen content in order to
reduce corrosion on the interior of the unit.

Metal Selection and Surface Conditions:

No metal is immune to corrosion in all environments, but through monitoring and
understanding the environmental conditions that are the cause of corrosion,
changes to the type of metal being used can also lead to significant reductions in
corrosion. Proper monitoring and the elimination of unnecessarily vulnerable
surface conditions, along with taking steps to ensure that systems are designed to
avoid reactive metal combinations and that corrosive agents are not used in the
cleaning or maintenance of metal parts are all also part of effective corrosion
reduction program.

Cathodic Protection:
Galvanic corrosion occurs when two different metals are situated together in a
corrosive electrolyte. Cathodic protection works by converting unwanted anodic
(active) sites on a metal's surface to Cathodic (passive) sites through the
application of an opposing current. This opposing current supplies free electrons
and forces local anodes to be polarized to the potential of the local cathodes.
Cathodic protection can take two forms.
The first is the introduction of galvanic anodes. This method, known as a sacrificial
system, uses metal anodes, introduced to the electrolytic environment, to sacrifice
themselves (corrode) in order to protect the cathode. Here metallic ions move from
the anode to the cathode, which leads the anode to corrode more quickly than it
otherwise would. As a result, the anode must regularly be replaced.
A second method of Cathodic protection is referred to as impressed current
protection. This method, which is often used to protect buried pipelines and ship
hulls, requires an alternative source of direct electrical current to be supplied to the
electrolyte

Corrosion Inhibitors:

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Corrosion inhibitors are chemicals that react with the metal's surface or the
environmental gases causing corrosion, thereby, interrupting the chemical reaction
that causes corrosion. Inhibitors can work by adsorbing themselves on the metal's
surface and forming a protective film. These chemicals can be applied as a solution
or as a protective coating via dispersion techniques.

Coatings:
Paints and other organic coatings are used to protect metals from the degradative
effect of environmental gases.

Plating:
Metallic coatings, or plating, can be applied to inhibit corrosion as well as provide
aesthetic, decorative finishes.

There are four common types of metallic coatings:

Electroplating: A thin layer of metal - often nickel, tin or chromium - is deposited

on the substrate metal (generally steel) in an electrolytic bath. The electrolyte
usually consists of a water solution containing salts of the metal to be deposited.
Mechanical plating: Metal powder can be cold welded to a substrate metal by
tumbling the part, along with the powder and glass beads, in a treated aqueous
solution. Mechanical plating is often used to apply zinc or cadmium to small metal
parts
Electroless: A coating metal, such as cobalt or nickel, is deposited on the substrate
metal using a chemical reaction in this non-electric plating method.
Hot dipping: When immersed in a molten bath of the protective, coating metal a
thin layer adheres to the substrate metal.

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