Dayananda Sagar College of Engineering

DAYANANDA SAGAR COLLEGE OF ENGINEERING

(An autonomous Institute affiliated to VTU, Belagavi)
Accredited by National Assessment and Accreditation Council (NAAC) with “A” Grade,
Shavige Malleshwara Hills, Kumaraswamy Layout, Bengaluru-560078

Department of Chemistry

ME Stream
Applied Chemistry

Module -I
Energy, Source, Conversion and Storage

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Module -I

Energy, Source, Conversion and Storage

Fuels

Introduction

“A chemical fuel is a substance, which on combustion in air or oxygen produces heat energy, which is
used in domestic and industrial purpose conveniently and economically”.

The principal elements present in chemical fuels are carbon and hydrogen, when a chemical fuel
undergoes combustion in air, carbon and hydrogen are converted into CO2 and H2O.

Chemical fuel+ O2 (air) → products (CO2,H2O,etc.,) + heat

(more heat energy content) (Less heat energy content)

The heat content of combustion products is being lower then chemical fuel, hence release heat during
the combustion process.

The primary sources of fuels are coals and petroleum. These are available in earth crust, generally called
fossil fuels.

Classification of fuels

The fossil fuels have been classified according to their

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1.Occurence

1. Natural or Primary fuels

Which are found in nature as such eg. Wood, coal, petroleum, natural gas etc.,
2. Artificial or Secondary fuels
Which are prepared from the primary fuels eg. Charcoal, coke, kerosene, petrol, coal gas,
producer gas. Etc.,

2. The state of aggregation.

a.Primary fuels or natural fuels:

Eg: Solid: wood, peat, lignite, coal.

Liquid: crude oil.
Gas: Natural gas.

b.Artificial or Secondary fuels

Eg: Solid: Coke, charcoal, coal etc.

Liquid: Gasoline, diesel, kerosene, synthetic petrol.
Gases: Producer gas, water gas, coal gas, LPG, Biogas.

Calorific value
The total quantity of heat is liberated, when a unit mass or volume of the fuel is burnt completely in air
or O2.
Units of heat
For solid or liquid

a. Calorie (Cal/g) (C.G.S-system)

b. Kilocalorie (Kcal/Kg) (M.K.S-system)
c. British thermal unit (BTU) (F.P.S-system)
1 BTU=252 cal=0.252 kcal

For gaseous fuel is J/cm3 or KJ/m3

Calorific value has been classified in two ways.

1. Higher (HCV) or Gross Calorific Value (GCV).
2. Lower (LCV) or Net Calorific Value (NCV).

Higher (HCV) or Gross Calorific Value (GCV).

The total amount of heat is produced, when a unit mass or volume of the fuel has been burnt completely
and the products of combustion have been cooled to room temperature.

Lower (LCV) or Net Calorific Value (NCV).

The total amount of heat is produced, when a unit mass or volume of the fuel has been burnt completely
and the products are permitted to escape.
LCV=HCV- Latent heat of water vapour formed.
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= HCV- 0.09H% X Latent heat of steam
= HCV- 0.09H% X 587 X 4.187 KJ/Kg.

Bomb Calorimeter

It is used to find the calorific value of solid and liquid fuels.

Construction
It consists of a strong cylindrical stainless steel bomb in which the combustion of fuel is made
to take place. The bomb has a lid, which can be screwed to the body of bomb so as to make a perfect
gas tight seal. The lid is provided with two stainless steel electrodes and an oxygen inlet valve. One of
the electrodes attached with small ring. In this ring, supported to nickel or stainless steel crucible. The
bomb is placed in a copper calorimeter, which is surrounded by an air-jacket and water-jacket to prevent
heat losses due to radiation. The calorimeter is connected with electrically operated stirrer and
Beckmann’s thermometer, which can read accurately temperature difference upto 1/100 th or 0.010C.

Working
A known mass (about 0.5 to 1.0g) of the given fuel is taken in clean crucible. A fine magnesium
wire touching the fuel sample. The bomb lid is tightly screwed and bomb filled with oxygen to 25 atm
pressure. The bomb is then lowered into copper calorimeter, containing a known mass of water. The
stirrer is worked and initial temperature of the water is noted. The electrodes are then connected to 6-
volt battery and circuit is completed. The sample burns and heat is liberated. Uniform stirring of water
is continued and the maximum temperature attained is recorded.
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Observations
Weight of the fuel = m g
Weight of water in the calorimeter = W1g
Water equivalent of the calorimeter, stirrer, thermometer and bomb =W2g
Initial temperature of water in calorimeter = t10C
Final temperature of water in calorimeter = t20C

Calculations
(i)Determination of higher calorific value (HCV)
Heat gained by water = W1 (t2-t1) S Cal.
Heat gained by calorimeter, stirrer, thermometer and bomb = W2 (t2-t1) S Cal.
(Weight of apparatus X Specific heat)
Total heat gained = W1 (t2-t1) S + W2 (t2-t1) S
= (W1+W2) S (t2-t1) Cal.
Total heat liberated by fuel = m.C
Now, heat liberated by fuel = total heat gained
m.C = (W1+W2) S (t2-t1)

Higher calorific value C =(W1+W2) S (t2-t1) Cal/g.

m
(ii)Determination of lower calorific value (LCV)

LCV=HCV- Latent heat of water vapour formed.

= HCV- 0.09H% X Latent heat of steam
= HCV- 0.09H% X 587 X 4.187 Cal/g.

PROBLEMS
1. A coal sample with 93% carbon, 5% of Hydrogen and 2% Ash is subjected to combustion in a bomb
calorimeter. Calculate GCV and NCV.
Given that
Mass of the coal sample = 0.95g
Mass of water in copper calorimeter = 2000g.
Water equivalent of calorimeter = 700g.
Rise in temp = 2.8 0C
Latent heat of steam = 2456 KJ/Kg/0C
Specific heat of water = 4.184 KJ/Kg/0C

GCV = (W+w) x S x∆ t
m
= (2000+700) x 10-3 kg x 2.80C x 4.184
0.95 x 10-3 kg

HCV= 33295.83 KJ/kg.

NCV = GCV – 0.09 x %H2 x 587x4.184 J/kg.

= 33295.83 J/kg – 0.09 x 5 x 2456 J/kg.
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LCV= 32190.63 KJ/kg

2.Calculate GCV and NCV of a fuel from the following data. Mass of fuel=0.75g, W=350g. t =3.020C,
Mass of water = 1150g, % H2=2.8.
GCV = (W+w) x ∆t x S
m
= (1150+350) x10-3 x 3.02 x 4.184
0.75 x 10-3
GCV = 25271. 36 KJ/Kg
NCV = GCV –0.09 x H x 587 x 4.184
= 25271.36 – 0.09 x 2.8 x 587 x 4.184
NCV = 24652.44 KJ/Kg
3.Calculate HCV of a coal form the following data. Mass of the coal is 0.6g. Water equivalent and
weight of water in calorimeter is 2200g. Specific value 4.187 Kg/KJ/0C rise in temperature = 6.52 0C.
GCV = (W1+W2) x S x ∆t
m
= (2200) x 10-3 x 4.187 x 6.52
0.6 x 10-3
= 100097.21 KJ/Kg.

GREEN FUELS

Introduction
Green fuel, also known as biofuel, is a type of fuel distilled from plants and animal materials, believed
by some to be more environmentally friendly than the widely-used fossil fuels that power most of the
world.
In creating basic forms of biofuel, crops are broken down into two types: sugar producing and oil
producing.
Sugar and starch producing crops, such as sugar cane or corn, are put through a fermentation process to
create ethanol.
Oil producing plants, like those used in vegetable oils, can be used much like fossil sources of oil; they
create diesel that can be burned by cars or further processed to become biodiesel.

POWER ALCOHOL

Power alcohol is ethyl alcohol blended petrol and can be used as fuel in internal combustion engines.
Power alcohol has petrol and alcohol in the ratio of 4:1.
Awareness of limited availability of the non-renewable fossil fuels gave stimulus to the production of
ethyl alcohol.

Advantages of alcohol blended petrol

1.Alcohol has an octane value of about 90, while petrol has octane value of 60-70. Consequently,
addition of alcohol to petrol increases its octane number.
2. Alcohol blended petrol possesses better anti-knocking properties.
3. Ethanol is obtained from renewable source.
4. Alcohol is capable of absorbing any traces of moisture otherwise enter into the petrol system.

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Disadvantages of alcohol blended petrol
1.The calorific value of alcohol blended petrol is low.
2. Alcohol is easily oxidized to acids hence alcohol may cause corrosion.
3. At low temperature, there is difficulty in starting the engine due to lower vapour pressure of alcohol.

Biodiesel

Biodiesel is an alternative fuel to diesel. It is an ecofriendly fuel obtained from renewable sources like
vegetables oils and animal fats.
Vegetable oils are the triglycerides, which has high viscosity, hence cannot be used as such in diesel
engine.
The triglycerides are need to be converted into biodiesel by transesterification.
The triglycerides are treated with methanol or ethanol in the presence of KOH, forms glycerol and
methyl or ethyl esters of fatty acids (biodiesel).

Production: Bio-diesel is commonly produced by the transesterification of vegetable or animal fat. The
process involves reacting vegetable oils or animal fats catalytically with short chain aliphatic alcohols.

Applications of biodiesel
Improved energy balance and security
Reduced emission and improved air quality
Optimized engine operation
Greater environmental safety

High energy fuels

Zip fuel, also known as high energy fuel (HEF), is any member of a family of jet fuels containing
additives in the form of hydro-boron compounds, or boranes. Zip fuels offer higher energy density than
conventional fuels, helping extend the range of jet aircraft.

A number of aircraft were designed to make use of zip, including the XB-70 Valkyrie, XF-108 Rapier,
as well as the BOMARC, and even the nuclear-powered aircraft program. The Navy considered
converting all of their jet engines to Zip and began studies of converting their aircraft carriers to safely
store it.

Types of hydrogen fuel

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Grey hydrogen
Grey hydrogen is hydrogen produced using fossil fuels such as natural gas or coal. Grey hydrogen
accounts for roughly 95% of the hydrogen produced in the world today. The two main production
methods are steam methane reforming and coal gasification. Both of these processes release carbon
dioxide (CO2). If the carbon dioxide is released into the atmosphere, then the hydrogen produced is
referred to as grey hydrogen. Grey hydrogen is not considered a low-carbon fuel.
Blue hydrogen
Blue hydrogen is similar to grey hydrogen, except that most of the CO2 emissions are sequestered
(stored in the ground) using carbon capture and storage (CCS). Capturing and storing the carbon dioxide
instead of releasing it into the atmosphere allows blue hydrogen to be a low-carbon fuel. The two main
production methods are steam methane reforming and coal gasification, both with carbon capture and
storage. Blue hydrogen is a cleaner alternative to grey hydrogen, but is expensive since carbon capture
technology is used.
Green hydrogen
Green hydrogen is hydrogen produced using electricity from clean energy sources. Green hydrogen is
considered low or zero-emission hydrogen because it uses energy sources such as wind and solar which
don’t release greenhouse gases when generating electricity. Green hydrogen is made when water (H2O)
is split into hydrogen (H2) and oxygen (O2). Water splitting is also known as electrolysis, and requires
an energy input. The method of supplying electricity to split water is an expensive process, but much
more environmentally-friendly compared to the production of grey hydrogen.

Grey, blue and green are most common colours, black, brown, red, pink, yellow, turquoise and white
exist as colours for molecular hydrogen.

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Hydrogen as Fuel
Hydrogen fuel is a zero carbon fuel burned with oxygen; provided it is created in a zero carbon way. It can
be used in fuel cells or internal combustion engines.
Regarding hydrogen vehicles, hydrogen has begun to be used in commercial fuel cell vehicles, such as
passenger cars, and has been used in fuel cell buses for many years. It is also used as a fuel
for spacecraft propulsion.
In the early 2020s, most hydrogen is produced by steam methane reforming of fossil gas. Only a small
quantity is made by alternative routes such as biomass gasification or electrolysis of water or solar
thermochemistry.
1. ELECTROLYTIC PROCESSES
Electrolysis of water is the process of using electricity to decompose water into oxygen and hydrogen gas
by a process called electrolysis. Hydrogen gas released in this way can be used as hydrogen fuel.

2 H2O(l) → 2 H2(g) + O2(g)

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Advantage
1. Renewable and Readily Available
2. Hydrogen fuel cells do not produce any CO2 emissions
3. The refuelling process for hydrogen fuel cells is easy and takes about three minutes
4. the energy density of hydrogen fuel cells is very high
Disadvantage:
1. It is expensive
2. Highly Flammable
3. Storage and transportation of hydrogen is more complex
4. This hydrogen production process is costly and emits carbon dioxide

Energy Conversion Devices.

Energy conversion is the transformation of one form of energy into another form. More specifically, the
term energy conversion refers to the process through which energy is changed into forms that are useful
to humans.
For hundreds of years, humans have used an array of devices and systems for this purpose. A familiar
example is the early windmill, which transformed the kinetic (moving) energy of wind into mechanical
energy to pump water or grind grain. A modern and more complex extension of this is the wind turbine,
which is part of a system that converts wind energy into mechanical or electrical energy through a series
of intermediate steps.

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SOLAR ENERGY
Photovoltaic cells or Solar cells are the semiconductor devices which converts sunlight into direct
current electricity on illumination The radiations reaching earth from the sun and converting them in to
different useful forms of energy is called solar energy.
The utilization of solar energy is of two types – Direct solar power and indirect solar power.

Construction and working of photovoltaic cells

The Solar cells or Photovoltaic cells are made out of semiconductors which have the capacity to absorb
light. When n-type and p-type semiconductor are bought together a semiconductor diode is formed. The
semiconductor diode separates and collects the carriers and conducts the generated electrical current
preferentially in a specific direction.
A typical silicon photovoltaic cell is composed of a thin wafer consisting of an ultra-thin layer of
phosphorus doped. (n-type) silicon on top of boron doped (p-type) silicon. Hence a p-n junction is
formed. A metallic grid forms one of the electrical current contacts of the diode and allows light to fall
on the semiconductor between the grid lines. An antireflective layer between the grid lines increases the
amount of light transmitted to the semiconductor. The cell’s other electrical contacts are formed by a
metallic layer on the back of the solar cell. When light radiation falls on the p-n junction diode, electron
– hole pairs are generated by the absorption of the radiation. The electrons are drifted to and collected
at the n-type end and the holes are drifted to ptype end. When these two ends are electrically connected
through a conductor, there is a flow of current between the two ends through the external circuit. Thus
photoelectric current is produced.

Applications of PV cell

 Telecommunication repeater stations

 Water pumps
 Navigational aids
 Laptop computers
 Cottages and remote residences
 Parks in remote regions
 Supplying occasional power
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Battery
A Battery is a combination of two or more galvanic cells arranged in series or parallel. Which converts
chemical energy into electrical energy through redox reactions.
Li-ion Battery
Li-ion battery has more advantages than traditional rechargeable battery:
i) High voltage: Lithium batteries have voltages up to about 4 V, depending on the cathode material, ii)
highly stable iii) wide operating temperature (ie. from -40oC to +70oC) iv) Flat discharge
Characteristics v) High specific energy and energy density:

It consists of a lithiated carbon (anode) and lithiated metal oxide (cathode), electrolyte LiPF6 is dissolved
in dimethyl carbonate and ethylene carbonate and separator polyolefine/polypropylene is used to
separate electrode materials.

Construction
Anode (-ve electrode): Lithiated carbon
Cathode (+ve electrode): Lithiated metal oxide LiMO2(M=Co, Mn, Ni)
Electrolyte: LiPF6 in dimethyl carbonate and ethylene carbonate.
Separator: polyolefine/polypropylene.

Working
Reactions
At anode: During discharge of battery, Li atoms present in graphite layer are oxidized, liberating
electrons and lithium ions. Electrons flow through external circuit to cathode and lithium ions flow
through electrolyte towards cathode. At cathode, lithium ions are reduced to lithium atoms and are
inserted into layered structure of metal oxide.

At cathode: During the charging of battery, lithium atoms in metal layered structure are oxidized,
liberating electrons and lithium ions. Electrons flow through external circuit to anode and lithium ions
flow through electrolyte towards anode. At anode lithium ions are reduced to lithium atoms and inserted
into layered structure of graphite.

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Applications
It is used in cell phones, laptops, automobiles, defense and aerospace applications.

Fuel cells

Fuel cell is device in which chemical energy of a conventional fuel is directly converted into electrical
energy.

Distinguish between battery and fuel cell

S. Battery Fuel Cell

No
1 Electrodes are not embedded Electrodes are not embedded with catalyst
with catalyst
2 Active materials are Active materials are not incorporated with
incorporated with electrodes electrodes
3 Create pollution in the Pollution free
atmosphere
4 Recharging of the cell is Recharging is not required
required
5 It is not expensive It is expensive

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Methanol-oxygen fuel cell

Direct Methanol Fuel Cell (DMFC) Direct Methanol Fuel Cell (DMFC) is a fuel cell that runs
directly on methanol (or various liquid fuels) without having to first convert those fuels into hydrogen
gas. It consists of two electrodes separated by a proton exchange membrane (PEM) and connected via
an external circuit that allows the conversion of free energy from the chemical reaction of methanol with
air or oxygen to be directly converted into electrical energy.

The direct methanol fuel cell is a proton exchange membrane (PEM) fuel cell that is fed with an
aqueous solution of methanol.

The two catalytic electrodes where the methanol oxidation (anode) and the oxygen reduction
(cathode) are separated by a membrane which conducts protons from anode to cathode, while other
compounds diffusion is blocked. The combination of electrodes and membranes is called membrane
electrode assembly (MEA). MEA was prepared with Pt/Ru black at anode and Pt black cathode on either
side of a Nafion membrane. Each electrode is made of a gas diffusion layer and a catalytic layer (Figure).

Membrane Nafion was created by addition of sulfonic acid groups into the bulk polymer matrix
of Teflon. These sites have strong ionic properties and act as proton exchange sites.

Aqueous methanol is fed at the anode side. It diffuses through the diffusion layer to the catalytic
layer where it is electrochemically oxidized into mainly carbon dioxide, protons and electrons.
Protons formed during this reaction diffuse through the Nafion membrane to the cathode
catalytic layer. They participate in oxygen reduction to form water at cathode side. Oxygen may be pure
but can also come from air. Electrons are collected by graphite bipolar plates which are the two poles of
the cell. The structure of the cell is described in Figure.

Reactions
Anode reaction -: CH3OH + H2O→ CO2 + 6H+ + 6e- E0 =0.02V
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Cathode reaction -: 3/2O2 + 6H+ + 6e- → 3H2O E0 =1.23V
______________________________________________________________________
Overall reaction -: CH3OH + 3/2O2 → CO2 + 3H2O E0 =1.21V

At anode, the methanol is oxidized into carbon dioxide and six protons (as hydronium ions) plus six
electrons. The six protons formed react at the cathode with oxygen to form water. The overall reaction
looks like a combustion reaction and is thus sometimes referred to as cold combustion. Actually the cell
is a mean to control this reaction and use it to produce current directly. The standard cell voltage for a
DMFC at 25ºC is 1.21V. However, this potential is never obtained in reality. The open circuit potential
is usually about 0.6 to 0.8V.

Applications

1. Using a liquid fuel for power.

2. The cells find application in military and large-scale power production.
3. A simpler system design, with the potential for low-volume, lightweight packaging.
4. Eliminating the requirement for fuel reforming and/or onboard hydrogen storage.
5. Classification as a zero-emission power system.

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DAYANANDA SAGAR COLLEGE OF ENGINEERING

(An autonomous Institute affiliated to VTU, Belagavi)
Accredited by National Assessment and Accreditation Council (NAAC) with “A” Grade,
Shavige Malleshwara Hills, Kumaraswamy Layout, Bengaluru-560078

Department of Chemistry

ME Stream
Applied Chemistry

Module-2
Corrosion Science and Engineering

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Module-2
Corrosion Science and Engineering
Corrosion:

The destruction/deterioration of metals/alloys by the surrounding environment through

chemical/electrochemical changes. It is known as corrosion.

• The process of corrosion is transformation of pure metal into its undesired metallic compounds.

• Corrosion can be a fast/slow process depending upon the nature metal and the environment where
metal undergo corrosion.

Examples

1. Rusting of iron-Reddish brown color-Fe2O3.3H2O

2. Green color scale on copper –CuCO3+Cu(OH)2

Types of corrosion

1. Dry or direct chemical corrosion

Corrosion is due to direct chemical reaction between metal and gases such as HCl, H2S, SO2, Cl2,
F2, NH3 etc. present in environment in the absence of moisture or conducting medium.

2. Wet or electrochemical theory of corrosion

Metal undergo corrosion in the presence of moisture or conducting medium.

Electrochemical Theory of Corrosion

Metal undergo corrosion in the presence of moisture/conducting medium. It is known as wet/electrochemical

corrosion.

Electrochemical chemical theory- “corrosion of metals takes place due to formation of anodic and cathodic
regions on the same metal surface/when two different metals are in contact with each other in the presence of
conducting medium”.

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Anodic region-Oxidation

Cathodic region- Reduction

Corrosion current-flow of electron from anode to cathode

Corrosion product deposit between anode and cathode

Corrosion reactions
a) Anodic reaction- At the anodic area, oxidation take place, resulting in the corrosion of iron

1. Anode - M → Mn+ + ne-

Example -Fe → Fe2+ +2e-

2. At cathode- It’s depends on corrosion environment

Types of cathodic reactions

a. Liberation of hydrogen

(i) In Acidic medium- 2H+ +2e- → H2

(ii) In neutral/alkaline medium- 2H2O +2e-→ 2OH- + H2

b. Absorption of oxygen

(i) In Acidic medium- 2H+ + ½ O2 +2e- → H2O

(ii)In neutral/alkaline medium - H2O + ½ O2 +2e- →2OH-

RUST FORMATION

(i) In the presence of excess oxygen

Fe2+ + 2OH- → Fe(OH)2

2Fe(OH)2 + 1/2O2 + H2O →Fe2O3.3H2O (Reddish brown)

(ii) In the presence of limited oxygen

3Fe(OH)2 + 1/2O2 →Fe3O4.3H2O (Black colour)

TYPES OF CORROSION

1. Differential metal /Galvanic Corrosion

When two different metals are in contact with each other and exposed to atmosphere. The metal
which is a lower reduction potential gets corroded and the metal has a higher reduction potential is
unaffected. This is known as differential metal /galvanic Corrosion.
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Examples

a. Zn and Cu; EoZn= -0.76 V and EoCu= 0.34V

b. Zn and Ag; EoZn= -0.76 V and EoAg= 0.80V

c. Fe and Cu; EoFe= -0.44 V and EoCu= 0.34V

i. Steel screws in brass

ii. Steel pipe connected to copper plumbing

H2O + ½ O2 +2e- →2OH-

Fe → Fe2+ +2e-

2. Differential aeration Corrosion

When a metal is exposed to different oxygen concentration. The part of the metal exposed to
higher oxygen concentration acts as cathode and the part of the metal exposed to lower oxygen
concentration acts as an anode. Consequently, the poor oxygenated region undergoes corrosion.

This is classified into two types

a. Water line corrosion

It is the differential aeration corrosion observed in iron or steel partially in contact with water. Usually observed
in water storage tanks, ship water lifting pipes etc. The portion under water will be exposed to less concentration
of oxygen and will act as the anode and undergo corrosion while the portion above water act as cathode and
will remain unaffected. The extend of corrosion will be maximum just below the waterline and hence is called
waterline corrosion. For example, in water storage tank the metal tank part inside water level exposed only to
dissolved oxygen get corroded(anode) while the part above water line is exposed to higher oxygen
concentration is protected(cathode).

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Reactions

At anode - Fe → Fe2+ + 2 e-

At cathode - H2O + ½ O2 +2e- →2OH-

b. Pitting corrosion

It occurs when small particles of dust, water drop on metal surface or breakdown of protective film. A typical
pitting corrosion is illustrated as shown in figure. The metal portion covered by dust act as anode due to less
oxygenated and undergoes corrosion beneath the dust forming a pit. The metal part free from dust exposed to
higher oxygen concentration become cathode and protected from corrosion. The corrosion rate is higher in this
case due to small anode area and large cathode area. All the electrons liberated at anode (pit) are absorbed by
large cathode area for reduction reaction.

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Stress Corrosion

During the manufacture of metallic equipments, metals undergo different processes such as bending,
pressing, rolling, quenching, and annealing etc., which causes stress on certain areas of the metal. The
areas under stress act as anode, whereas other areas act as cathode.

The stressed part of the metal acquires higher energy as compared to the unstressed part and becomes
chemically active towards the corrosive environment and get corroded.

Caustic embrittlement

Caustic embrittlement is a form of stress corrosion that taking place in the high pressure boilers. Caustic
embrittlement occurs at stressed parts of the boiler such as cracks, rivets, bends and joints. Boiler walls
certain parts under stress by the action of caustic soda.

The high pressure boilers, excess Na2CO3 is added to remove hardness of water, hydrolysis of
Na2CO3 to give NaOH and CO2 makes water alkaline.

Na2CO3 + H2O → 2NaOH + CO2

When this dilute alkaline water flows into the cracks in boiler walls, water gets evaporated and leaving
behind NaOH in the cracks.

On the basis of electrochemical theory, the corrosion cell can be represented as follows,

Fe under stress (anode)/Conc. NaOH/Dil.NaOH/ Fe stress free (Cathode)

The iron in contact with concentrated alkali being under stress, becomes anode, while stress free iron
surrounded by dilute alkali becomes cathode. Corrosion takes place at the stressed region, results in
boiler failure of explosion.
Caustic embrittlement can be prevented by the addition of compounds such as sodium sulphate,
tannin, lignin, phosphate tec., which blocks the cracks or crevices.

Metal Coatings

The coating metal deposited on base metal is known as metal coating. Metal coatings are done by hot dipping,
electroplating, electroless plating, thermal spraying etc.

The metal coating is classified into two types 1. Anodic coatings 2. Cthodic coatings.

Anodic coatings.

Base metal coated with anodic and active metals, which are anodic to base metal. For example, iron is coated
with active metals like Mg, Zn, Al etc.

Galvanization is an example for anodic coating. It is extensively used to protect iron and steel materials.
It is done by hot dipping.

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The following steps are involved in the galvanization process

1) The iron sheet is washed with solvent to remove grease & oily materials(degreasing).

2) The iron sheet is washed with dil.H2SO4 to remove oxide film (descaling) and rinsed with distilled
water.

3) The sheet is then treated with a mixture of aqueous solution of zinc chloride and ammonium chloride
& dried.

4) The dried sheet is dipped in molten zinc at 430 – 450 0C

5) Excess Zn is removed by rolling, wiping etc.

Surface conversion coatings

Conversion coatings refer to the coatings produced by a chemical or electrochemical treatment of the
metallic surface using coating solutions. During the conversion process, part of the metal surface is
converted into a protective surface layer.

Examples of conversion coatings include chromate conversion coating (CCC), phosphate conversion
coating (PCC), and black oxide coating.

Anodized coating of Aluminium.

Anodized coating is generally produced on non-ferrous metals like Al, Zn, Mg made as anode,
Pb is generally used as cathode in an electrolyte by passing direct current. The most commonly used
electrolytes are H2CrO4, H2SO4, H3PO4, (COOH)2, H3BO3 or their mixtures.

The anodic metal oxide is porous and provides good adherence for paints and dyes.

The strength and corrosion resistance of the anodized film can be increased by sealing, which
involves heating in boiling water or steam or metal salt solutions. The treatment changes porous alumina
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at the surface of coating into its monohydrate (Al 2O3.H2O), which occupies more volume, thereby the
pores are sealed.

Anodized aluminium can be produced in a number of coloured finishes.

1. An organic dye is adsorbed on the freshly anodized surface and it is then sealed.
2. A metal Ni, Co, Sn is deposited into the porous, resulting electro colouring process.

Electrolytic cell for anodizing aluminium.

The electrode reactions occurring during anodising process are:

At anode: 2Al + 3H2O → Al2O3 + 6 H+ + 6e-
At cathode: 6H+ + 6e- → 3H2
Over all reaction: 2Al + 3H2O → Al2O3 + 3H2

Cathodic Protection

Corrosion of metal can be prevented by removing anodic area and converting entire metal surface
into cathodic area. This process is known as cathodic protection.

There are two types of cathodic protections namely,

1) Impressed voltage method
2) Sacrificial anode method

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Sacrificial anode method
In this the metal structure to be protected is connected to a more anodic metal like Mg, Zn and
Al which acts as anodic. In practice active metal Mg or Zn is connected to metal structure to be protected.
The more active metal Mg or Zn becomes anodic and corrodes but the metal structure becomes cathodic
is protected. Since the anode metal sacrifices to protect the metal structure the method is known as
Sacrificial anode method.
Examples:
1. Mg block connected to ships floating on water surface.
2. Mg block connected to underground buried pipe line/oil storage tank.

Corrosion testing by weight loss method

Corrosion rate is determined by weight loss method. in this the metal or alloy is subjected to cleaning
process. The cleaned coupon is weighted, placed into corrosive environment and removed after a
reasonable time interval. The coupon is then cleaned to remove corrosion product on that and reweighed.

Weight loss determination has a number of attractive features.

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1. Simple- No sophisticated instrumentation is required.
2. Direct- A direct measured is obtained.
3. Versatile- It is applicable to all corrosive environments.

Corrosion penetration rate (CPR)

Corrosion penetration rate (CPR) = kW/ ρAt

k = constant
W = metal lost
ρ = density of metal
A= area exposed for corrosion
t = duration of corrosion
Corrosion rate can also be calculated by the amount of metal undergoing corrosion in time, is given by
m = iM/ nFt
M = atomic weight of metal
I = current
n = number of electrons
F = faraday constant
t = time

Problems:
1) An iron metal lost 2.4 х10 -3 g of weight when it is immersed in deaerated acidic solution for 2
hrs. Calculate the corrosion penetration rate (CPR) for the exposed area of 4 cm2. Given k =534
and the density of metal = 5.37 g cm-3. Express the CPR in terms of meter per second.
Solution: CPR = kW
ρAt
Given k = 534, W = 2.4 х 10 -3 g, A = 4 cm2, ρ= 5.37 g cm-3
CPR = 2.4 х10 -3 g х 534
5.37 g cm-3 х 2 hrs х 4 cm2
CPR = 0.0298 cm / hrs
CPR in terms of meter per second is
CPR = 0.0298 х 10 -2 m
60 х 60 second
CPR = 8.27 х 10 -8 meter/ second

2) An iron metal lost 3.3 x 10-3 g of weight when it is immersed in deaerated acidic solution
for 3 hours. Calculate the corrosion penetration rate for the exposed area of 5 cm2. Given, K=
534 and the density of metal = 5.37 g/cm3.

Solution:
CPR = kW
ρAt
Given k = 534, W = 3.3 х 10-3 g, A = 5 cm2, ρ= 5.37 g cm-3

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CPR = 3.3 х10 -3 g х 534
5.37 g cm-3 х 3 hrs х 5 cm2
CPR = 0.0218 cm / hrs

3) If the corrosion current in an iron specimen immersed in a deaerated acidic solution is

4.21 х10 -1 Am-2, calculate the corrosion rate of iron in milligrams per square decimetre perday
(mg dm-2d-1). Given atomic weight of iron =55.8 gmol-1 faraday=96490 cmol-1, t=1 second,
density of iron=7.87gcm-3.
Solution:
i) Amount of iron m, undergoing corrosion in time ‘t’ is given by
i=4.21 х10 –1, n = 2, F = 96490 cmol-1,
ii) t= 1 sec, M= 55.8 g
m=iM
nFt
m = 4.21 х10 –1 Am-2 х 55.8 gmol-1
2 х 96490 cmol-1

m = 4.21 х10 –1 Am-2 х 55.8 х10 3 mgmol-1 (since C=AS)

2 х 96490cmol-1
m = 0.122 mg m-2 S-1

1m= 10 dm
iii) To calculate m in mg dm -3
1d = 24 х 60 х 60 S
m = 0.122mg = (24x 3600)S
m2 S 1 1S = d
m = 0.122mg 24 x 3600
(10 dm)2 х d
(24 х 3600)
m = 0.122mg х 24 х 3600 = 105.408 mg dm-2d-1
100 dm2 . d

Metal Finishing

Metal finishing is a process of coating metal on metal, metal on an alloy or metal on a polymer or
forming oxide film to modify surface properties. Major techniques used are electroplating and
electroless plating.

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Technological Importance of Metal Finishing

 To increase the corrosion resistance

 To increase thermal resistance
 To increase the durability of the metal
 To impart hardness
 To provide electrical and thermal conducting surface
 Manufacturing electrical and electronic components such as PCB, capacitors etc.
 Decorative purpose

ELECTROPLATING

Coating a layer of metal over the surface of another metal, alloy or any other conducting material
by applying an electric current is called as electroplating.

Electroplating is carried out in a device called an electrolytic cell.

In electroplating practice, the current is usually introduced from an external source and the anode
is the positive electrode and cathode is a negative electrode. The cathode is the electrode where
the electrochemical reduction reaction occurs. The anode is that where the
electrochemical oxidation reaction occurs. The electroplating process uses an anode and a
cathode. In electroplating, the metal dissolved from the anode can be plated onto the
cathode. The anode is provided with direct current, oxidizing and dissolving its metal atoms in
the electrolyte solution. At the cathode, the dissolved metal ions are decreased and the metal is
placed on the product.

Electrolytic cell

At cathode: The metal ions are reduced to metal atoms and get deposited over it.
Mn+(aq) + ne- → M(s)

At anode: oxidation of metal atoms to metal ions.

M(s) → Mn+(aq) + ne-

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Electroplating of chromium (hard and decorative)

Chrome plating is to provide corrosion resistance, decorative finishing, and hardness of a surface.

Parameter Decorative Cr coating Hard Cr coating

Bath solution Chromic acid(250g), Chromic acid(250g),

Sulfuric acid (25 g) Sulfuric acid (25 g)

Anode Insoluble anodes like Pb- Insoluble anodes like Pb-

Sb/Pb-Sn alloy coated with Sb/Pb-Sn alloy coated with
PbO2. PbO2.
Cathode Object to be plated Object to be plated
Current Density 100-200mA/Cm2 250-500mA/Cm2

(mA cm-2)
Temperature 45-60 degree Celsius 45-60 degree Celsius

Current Efficiency (%) 10-12 % 15-21 %

Applications Corrosion resistance, Corrosion resistance,

decorative finishing and decorative finishing and
hardness to surface. hardness to surface.

During Chromium plating, chromium rod is not used as anode because

1. chromium rod get passivated in acidic medium (i.e. Anode efficiency is five time more than cathode
efficiency)

2. it can cause the increasing in concentration of Cr3+ ions leading to burnt deposit.

Chromium is generally porous in nature. As increase the thickness of chromium plating cracks develop
on coating. However, Cr coating is always done on thin layer of copper and zinc undercoats.

Electroless plating

This is a method of depositing a metal or alloy over an article (metallic or nonmetallic) by the
reduction of metal ions using suitable reducing agents, without using electrical energy. The surface to
be platted should be catalytically active.

The process con be represented as:

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Metal ion + Reducing agent → Metal atom + oxidized product

• Involves the oxidation of a soluble reducing agent which supports the cathodic deposition of
metal on a catalytic surface
• This process uses only one electrode and no external source of electric current.
• The solution needs to contain a reducing agent so that the reaction can proceed.

ELECTROLESS PLATING OF NICKEL

1. Pretreatment- Degreasing followed by descaling

2. Activation

i. Al, Fe, Cu and Brass-they can be plated without activation.

ii. Stainless steel- it is activated by dipping a hot 1:1 H2SO4.
iii. Mg Alloys- making thin layer of Cu and Zn.
iv. Insulators- like plastics, ceramics etc are activated by dipping a solution containing SnCl2 and
HCl followed by PdCl2 solution.

SnCl2 + HCl → SnCl4 + Pd

Electroless nickel plating

Electroless plating of nickel offers excellent corrosion resistance to common corrodents such as
salt water, carbon dioxide, oxygen and hydrogen sulphide.

Coating solution: NiCl2 solution

Reducing agent: Sodium hypophosphite
Buffer solution: Sodium acetate
Complexing agent and exhaltant: Sodium succinate
Optimum pH: 4.5
Optimum Temperature: 93 0C

Cathodic: Ni2+ + 2e- → Ni

Anodic: H2PO2- + H2O → H2PO3- + 2H+ + 2e-

hypophosphite ion orthophosphite ion

Overall: Ni2+ + H2PO2- + H2O → H2PO3- + 2H+ + Ni

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