Applied Chemistry for ME Stream

Module: 1

Energy; Source, Conversion and Storage

Syllabus
Fuels: Introduction, calorific value, determination of calorific value using bomb
calorimeter, numerical problems on GCV and NCV.
Green fuels: Introduction, power alcohol, synthesis and applications of
biodiesel.
High energy fuels: Production of hydrogen by electrolysis of water and its
advantages.
Energy devices: Introduction, construction, working, and applications of
Photovoltaic cells, Li-ion battery and methanol-oxygen fuel cell.
Self- learning: Plastic recycling to fuels and its monomers or other useful
products.

Course Outcomes
CO1: Identify the terms and processes involved in scientific and engineering
applications
CO2: Explain the phenomena of chemistry to describe the methods of engineering
processes
CO3: Solve for the problems in chemistry that are pertinent in engineering applications
CO4: Apply the basic concepts of chemistry to explain the chemical properties and
processes
CO5: Analyze properties and processes associated with chemical substances in
multidisciplinary situations

Fuels:

Introduction:-

Energy is an important aspect of human activity. Energy is a capacity to

do work. There is various forms of energies like electrical energy, chemical
energy, thermal energy, mechanical energy, etc…..

Fuels are main source of chemical energy. In this chapter we will deals with
chemical energy source.

The chemical energy sources are broadly classified into two types namely.

1. Fuels: - Ex: - Coal, Petroleum, Natural gas, Biomass, Uranium etc….

2. Non-Fuels:- Ex: - Solar, Wind, Tindal, Hydroelectric, etc…..

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Definition of Fuel:-

Fuel is defined as “A naturally occurring (or) an artificially manufactured

combustible carbonaceous material, which serves particularly as a source of
heat and light”.

Definition of a Chemical Fuel:-

“A chemical fuel is a substance, which produce a significant amount of

heat and light energy when burnt in air (or) oxygen”.

Classification of Fuels:-

On the basis of their origin fuels are classified as Primary and Secondary
fuels.

1. Primary Fuels: - Fuels which occur naturally is called Primary fuels.

Ex: - Wood, Coal, Petroleum, Natural gas, etc….

2. Secondary Fuels: - Fuels which are derived from primary Fuels are
called Secondary Fuels.

Ex: - Charcoal, Coke, Petrol, Diesel, etc……

On the basis of Physical state fuels are classified as Solid, Liquid,

Gaseous fuels.

Physical Secondary
Primary Fuel
State Fuel
Solid Wood, Coal Charcoal, Coke
Liquid Petroleum Petrol, Diesel
Gas Natural gas LPG

Calorific Value:-

It is defined as “The total quantity of heat liberated, when a unit mass

(or) unit volume of the fuel is burnt completely in air (or) oxygen”.

Unit of Calorific value:-

For Solids, it is expressed in JKg-1 [joules per Kg]

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For liquids it is expressed in Jm-3 [joules per meter cube].

Grass Calorific Value (or) Higher Calorific value:-

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

QGrass = Sensible heat + Latent heat of condensation of

water.

Net Calorific value (or) Lower calorific value:-

“The amount of heat liberated when a unit mass (or) volume of the fuel
is burnt completely in air (or) oxygen and the products of combustion are
permitted to escape”.

QNET = Q(Grass )-Latent Heat of water vapour Formed

QNET = GCV-[9X mass of H_(2 ) X latent heat of Steam]

QNET = GCV-[0.09X % H_(2 ) X 2454] KJ/Kg

Determination of Calorific value of Solids (or) Liquids using Bomb

Calorimeter:-

Principle:-

A known weight of a liquid (or) solid fuel is completely burnt in excess of

oxygen and the liberated heat is absorbed by a known weight of water &
Calorimeter. Thus the heat liberated by the fuel is equal to heat absorbed by
the water and the calorimeter. By recording the rise in temperature of water
and knowing specific heat of water, calorific value is calculated.

Construction:-

 The Bomb calorimeter consists of a stainless steel vessel with an airtight

lid. This vessel is called Bomb.
 The bomb has an inlet valve for providing oxygen atmosphere inside the
bomb and an electrical ignition coil for starting of combustion of fuel.
 The bomb is placed in a insulated copper calorimeter.
 The calorimeter has a mechanical stirrer for dissipation of heat and a
thermometer for reading the temperature.
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Working:-

 A known weight of the fuel in the form of pellet is taken in a crucible and
placed inside the bomb. The lid is close tightly.
 The Bomb is kept inside a copper calorimeter containing a known weight
of water. Initial temperature [t1] of water is noted after stirring.
 Oxygen is pumped into the bomb through oxygen valve.
 The fuel is ignited using electric current and liberating heat is absorbed
by water and calorimeter.
 The maximum temperature [t2] attained by water is noted.

Observation and calculation:- Oxygen

Mass of fuel = m Kg.

Initial temperature of water = t°1C.
B
Maximum temperature of water = t°2C.
Stirrer
Rise in temperature of water = [t10-t20] C = Δ t°C.
Mass of water in the calorimeter = W1 Kg.
Water equivalent of calorimeter = W2 Kg.
Wires for ignition
Specific heat of water = S JKg-1C-1. Thermometer

Lid

Sample

Heat released by the fuel = Heat absorbed by water and Apparatus.

mQGrass = (W 1 +W 2 ¿ X S X ∆ t

( W 1+W 2 ) XS X ∆ t
QGrass= KJ / Kg.
m

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Green Fuels: -

Power Alcohol: -

When Ethyl Alcohol is used as an additive to motor fuels to act as a fuel

for internal combustion engines, it is called power Alcohol.

The addition of alcohol to petrol increases the octane number and

alcohol blended petrol posses better antiknock properties. Blends containing
up to 25% alcohol with petrol are used.

The important raw materials for production of power alcohol are

saccharine material [such as molasses, sugar beets, sugar cane etc...], starchy
materials [such as starch, potatoes, cereal grains etc…], and cellulose material
and hydrocarbon gases.

Production of Ethyl alcohol from Molasses:-

Molasses is a dark coloured viscous fluid left after the crystallization of

cane sugar from cane juice. It contains 50-55% of total sugar out of which 30-
35% is cane sugar. [sucrose].

Molasses is diluted with water to bring down the concentration of sugar

to 10-12%, PH is kept acidic to favors the function of enzymes by adding
sulphuric acid and allow for fermentation for about 48-60 hours.

C 12 H 22 O11 C 6 H 12 O6+ C6 H 12 o 6
Glucose Fructose
C 6 H 12 O6 2 C2 H 5 OH +2 C O2
Glucose Ethyl alcohol

It is distilled to get ethyl alcohol which is mixed with water. Repeated

distillation and condensation can raise the alcohol content to 97.6% [Absolute
alcohol].

Advantages:-
 Power output is high.
 Addition of alcohol reduces the emission of CO and volatile organic
compounds.

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 Ethanol is obtained from agricultural product.

 Ethanol is biodegradable.
 Ethanol contains higher percentage of oxygen than MTBE and hence
brings about complete & effective combustion of petrol. Therefore power
alcohol has better Antiknocking characteristics than unleaded petrol.
 Lubrication in case of power alcohol and pure petrol are same, hence
required for complete combustion is less.

Disadvantages:-

 The calorific value of alcohol is low hence alcohol blended petrol has low
calorific value.
 Alcohol is easily oxidized to acids and it is able to cause corrosion.
 Air entering the cylinder needs to be regulated as less air is required for
combustion.
 Alcohol absorbs moisture and as a result separation of alcohol and petrol
layers takes place especially at low temperature. To avoid this, blended
agent like benzene (or) toluene is used.

Biodiesel:-

Biodiesel is a source of energy obtained from renewable sources of plant

origin.

(Or)

Biodiesel is a mixture of monoalkyl esters of long chain fatty acids.

Biodiesel is synthesized by Transesterification process with methyl

alcohol using NaOH as a catalyst.

Transesterification is alcoholysis of the triglyceride oil in the presence of

a base, resulting mixture of monoalkyl esters of fatty acids is referred to as
biodiesel.

Where R1, R2, R3 are the long chain fatty acids in the oil.
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Advantages:-

 It is biodegradable and renewable.

 It is cheaper than diesel.
 It has higher cetane number compared to diesel.
 Use of biodiesel reduces greenhouse gases.
 Burns more efficiently than petroleum diesel.
 Biodiesel has higher lubricity hence it can reduce engine wear and hence
prolong engine life.

Disadvantages:-

 Calorific value of biodiesel is less compared to pure diesel.

 Purely obtained from plant origin & hence modification is required.

High Energy Fuels:-

Green fuels are liquid or gaseous fuels produced with electricity from
renewables.
Ex: - Synthetic Natural Gas (SNG), Hydropower, Solar Power, Wind Power,
Biomass etc.,

Green Hydrogen: -

It is hydrogen produced by splitting water by electrolysis.

Production of Hydrogen by Electrolysis of Water: -

It is a process of splitting of water into a hydrogen and oxygen using

electricity.

Process:-

 It consists two pair of platinum electrodes with water and H 2SO4 electrolyte.
 At the anode, water is oxidized to oxygen gas and hydrogen ions.
 At the cathode, hydrogen ions are reduced to hydrogen.

Anode Cathode

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Properties of Hydrogen pertaining to fuel:-

 Hydrogen can be produced from renewable resources.

 Hydrogen burns with a pale-blue.
 Hydrogen is highly flammable.
 It has a high energy.
 It combines with oxygen, gives water.

Advantages of Hydrogen as fuel: -

 Hydrogen is an ideal, highly efficient, renewable, clean and sustainable

energy source.
 It is abundant from various sustainable sources (biomass or water)
 Energy content of hydrogen is 122 kJ/Kg, which is 2.75 times greater than
hydrocarbon fuels like petrol and diesel.
 The combustion product is water, which is not a pollutant.
 It can be used as a fuel in fuel cell for production of electric current.
 It can be used as chemical fuel and burnt directly to produce heat energy.
 It has high storage capability, thus considered as an ideal alternative
source of energy for fossil fuels.

Energy devices

Solar Energy:

Introduction:

Solar energy is one of the solutions for sustainable energy conversion

processes. Solar radiation coming from sun is highly useful in photosynthesis
and is the major energy source for ecosystem. Solar energy is non-depleting,
non-polluting and available freely & can be utilized for various applications.

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 Applied Chemistry for ME Stream

Radiations from the sun constitute solar energy.

It is a clean and renewable source of energy available in abundance.

Photovoltaic Cells:-

Photovoltaic cells are semiconductor device which convert solar energy

into electrical energy.

Photovoltaic cells can generate electricity as long as Sun light is available.

Construction and working of Photovoltaic cells:-

Photovoltaic cell is composed of a thin mater consisting of an ultra thin

layer of phosphorous doped [n-type] silicon on the top of boron doped [p-type]
silicon. Hence P-n junction is formed b/w the two.

 A metallic grid forms one of the electrical contacts of the diode and allows
light to fall on the semiconductor b/w grid lines.
 An antirefractive layer b/w the grid lines increase the amount of light
transmitted to the semiconductor.
 The cells other electrical contact is formed by a metallic layer on the back of
the solar cell.
Sunligh
t Antireflective
layer
Metal grid
N-type
layer
h+ P- Type
layer
e
-

e-
Metallic
layer

Working:-

 When light radiation falls on the P-n junction diode, electrons-hole pairs are
generated by the absorption of the radiation.
 The electrons are drifted and collected at n-type end and the holes are
drifted and collected at the P-type end.
 When these two ends are electrically connected through a conductor, there
is a flow of current b/w the two ends through the external circuit. Thus
Photoelectric current is produced and available for use.

Advantages:-

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 They are Environmental friendly.

 They need no recharging.
 They do not corrode.
 They operate at low temperature.
 No emission, no combustion.
 High public acceptance and excellent record.
 Low operating cost.
 No moving parts and so no wear and tear.

Disadvantages:-

 High installation cost.

 Energy can be produced only during the day time.
 Poor reliability of auxiliary elements including storage.
 Sun light is a diffuse, ie, it is relatively low density energy.

Batteries : -

A device enables the energy liberated in a chemical reaction to be

converted directly into electricity.

Ex: - Lead-Acid battery, Nickel-Cadmium battery, Li-ion battery, etc….

Basic components of a Battery:-

A battery is made up of anode and cathode which are surrounded by

their electrolytes. The anode and cathode are separated by separator. The
outer surface of the battery is covered by plastic layer and in modern batteries
the ventilator are also provided to escape the accumulated gases during the
process.

A battery consists of four major components.

Ventilator

Cathode
Anode

Electrolyte

Separator

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1. Anode: - In a battery anode is a negative e -de. It releases electrons into

the external circuit by undergoing oxidation reaction. In rechargeable
battery it acts as positive terminal (cathode) during charging. It gives the
electrons to the external circuit.
M(S) Mn+(aq) + ne-

Zinc, Lithium, Nickel, Cadmium, and Lead are extensively used as

anodes and of these Lithium tops, the list because it readily
gives off electrons. (Reduction potential is highest. (-3.05V)).

2. Cathode: - In a battery cathode is a positive e -de. It accepts the

electrons from the external circuit. There by reduction of the active
species occurs. In rechargeable battery it acts as negative terminal
(anode) during charging.
Mn+(aq) + ne- M(S)
Graphite rod, Zinc, Lead, Nickel and Cadmium are used as
cathodes. Sometimes both anode and cathode are made up of same
material like lead as in the case of lead-acid battery.
3. Electrolyte: - It provides the medium for transfer of ions inside the cell
b/w the anode and cathode. A solution of an acid, alkali (or) salt
having high ionic conductivity is commonly used as an electrolyte.
4. Separator: - It is used to separate anode and cathode compartments in
a battery to prevent internal short circuiting. The main function of the
separator is to transport ions from anode to cathode and vice versa. It is
highly resistance towards electrolyte.
Ex: - Cellulose, vinyl polymer, polyolifine membranes etc….
In addition cathode & anode current collector, terminals, seal and
container make a battery complete.

Classification of Batteries:-

Batteries are classified as, 1. Primary Batteries (Non-rechargeable

Batteries)
2. Secondary Batteries (Rechargeable
Batteries)
3. Reserve Batteries.
1. Primary Battery: -

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The batteries which produce electrical energy at the expense of free

energy of active materials and produce energy only as long as active
materials are present.
(OR)
The battery which cannot be recharged and discarded when the
battery has delivered all its electrical energy is called as a primary battery.
Ex: - Zn-Mno2 battery, Li-Mno2 battery, etc…..
In these batteries, the reaction is spontaneous but irreversible. These
batteries have a higher capacity and initial voltage than rechargeable
batteries.
2. Secondary Battery: -
The batteries which produce electrical energy at the expense of free
energy of active materials. These active materials are capable of restoring at
respective electrodes on recharge and prepare for discharge once again. These
are rechargeable batteries and can be used again and again.
(OR)
A battery which after discharge, can be charged again by passing the
electric current through it in the opposite direction to that of the discharge is
known as secondary battery.
Ex: - Lead-Acid battery, Nickel-Cadmium battery, etc…..
In these batteries the reaction is reversible.
3. Reserve Battery: -
These are batteries which may be stored in inactive state and are made
activated just before they are needed. The activation involving by adding
electrolyte because one component of the electrolyte is isolated and stored
separately when the battery is required.
Ex: - Mg-H2O activated battery, Zn-Ag2O battery, Li-V2O5 battery etc…….

Li – ion Battery:-

The batteries in which lithium ions are used instead of lithium metal and
movement of lithium ion through electrolyte takes place from one electrode to
another electrode, such batteries ae called Lithium – ion batteries.

Ex: Li – Polymer Battery, Li Cobalt oxide Battery, etc,

Construction and working of LiCoO2 Battery:-

Construction:-
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Anode: Lithium Carbon Material (LixC6)

Cathode: Lithiated Cobalt Oxide (Li1-xCoO2)

Electrolyte: Lithium Salts Dissolved in Organic Solvents.

Separator: Polyethylene or Polypropylene

−¿¿
e ⇅ ⇅e−¿¿

Li+
Cathode
(Li1-
xCoO2)

Anod
e
(LixC6
Separato
Li – Salts in
r
Working: - org. Solvents
(Electrolyte)

Applications:-
 Mobile devices
 Radio controlled aircraft
 Electric vehicles, Digital Camera
 Fertilizer and Fish feeding devices
 Blood pressure devices, Blood sugar indicators, Insulin pump etc.,

Fuel Cells:

Introduction: -

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Fuel cells are the galvanic cells which converts chemical energy of fuels into
electrical energy by the combustion of fuels.
(OR)
Fuel cells are the galvanic cells which converts chemical energy of the
fuels into electrical energy through catalyzed redox reactions with elimination
of minimum harmful byproducts.
A fuel cell has two electrodes with catalysts and electrolyte. In this
device fuel and oxidizing agents are continuously and separately supplied to
the respective electrodes at which they undergo redox reaction to produce
electrical energy.
Fuel cells produce electrical energy as long as fuels are supplied at
respective electrodes.
It is represented by

Fuel Electrode Electrolyte Electrode Oxidant

At Anode, fuel undergo oxidation Fuel Oxidation product + ne -

At Cathode, Oxidant gets reduced Oxidant + ne - Reduction
product

Limitations of Fuel cells:-

 Fuel cells produce energy only as long as fuels and oxidants are supplied.
 Electrodes are very costly.
 Power output is moderate.
 Fuels in the form of gases and oxygen need to be stored in tanks under high
pressure.
 Reactions are constantly supplied and the products are constantly removed
from the cell.

Advantages of the Fuel cells:-

 They operate very silently.
 Their power efficiency is high.
 The cells have high energy density.
 They are ecofriendly.
 Space required for fuel cell is less.
 Produce harmless biproducts.
 Produces direct current for a long time.

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 Applied Chemistry for ME Stream

Methanol – oxygen Fuel Cell:-

Methanol is preferred as a fuel in fuel cells because of the following
reasons.
 It has low carbon content.
 It possesses a readily oxidizable alcoholic group.
 It has high solubility in aqueous electrolytes.
Construction:-
 It consists of anodic and cathodic compartments and both the
compartments contain platinum electrodes.
 Methanol containing H2SO4 is passed through anodic
compartments.
 Oxygen is passed through cathodic compartments.
 Electrolyte consists of sulphuric acid [3.7M]
 A membrane is provided which prevents the diffusion of methanol
into the cathode.
CO2

CH3OH O2

Cathode
Anode
Membrane

H2SO4 (electrolyte)

Excess Oxygen
and water
CO2

Working: - At anode, CH3OH undergoes oxidation to CO2 liberates electrons,

the liberated electrons taken by oxygen gets reduced into water with liberation
of energy at cathode..

Reactions:-
At Anode: - CH3OH + H2O CO2 +6H+ + 6e-
3
At Cathode: - O2 + 6H+ + 6e- 3H2O
2
3
Net reaction: - CH3OH + O2 CO2 + 2H2O
2

The cell potential is 1.21V at 25°C.

Uses: -
It is used in Military applications.
USED as electric power source in space vehicles.

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Used in large scale power production.

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