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Fuels and Combustion

Introduction
• A chemical fuel is defined as a combustible substance
containing carbon as the main constituent, which on
complete combustion gives large amount of heat that can
be used economically for domestic and industrial
purposes.

Different Energy Sources


• Non-renewable Fossil Fuels
• Renewable Sources such as solar energy, wind energy,
biofuels etc.
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Characteristics of a good fuel


 High Calorific value
 Moderate ignition temperature
 Low moisture content
 Low ash content
 Moderate velocity of combustion
 Less hazardous combustion products
 Low cost
 Easy Storage
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Classification of fuels
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Calorific value
• To grade a fuel and assess its quality, it is important to find the
calorific value of the fuel.

• Calorific value of a fuel is "the total quantity of heat liberated,


when a unit mass (or volume) of the fuel is burnt completely."

Units
(1) CGS: Calorie/g
(2) SI unit: Joule/g
(3) British Thermal unit/pound (B.T.U./lb)
1 Calorie = 4.187 J
1 B.T.U. = 252 cal = 0.252 kcal 1 kcal = 3.968 B.T.U.
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Gross Calorific Value & Net Calorific Value


 Gross Calorific Value (GCV)
GCV of a fuel can be defined as the total amount of heat obtained on
complete combustion of unit mass of a solid or liquid fuel or unit volume
of a gaseous fuel (STP) and on cooling the products of combustion to
15°C. The gross calorific value is also called as higher calorific value.

 Net Calorific Value (NCV)


NCV is defined as the amount of heat obtained practically on complete
combustion of unit mass of solid or liquid fuel or unit volume of a gaseous
fuel at STP and the products of combustion are allowed to escape with
some heat. NCV is also called as lower calorific value.
NCV = GCV- [mass of steam x specific latent heat of condensation of
water]
.
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• General Principle of Calorimetry

• Methods of determination of calorific value

• Bomb calorimeter
• Principle
• Construction
• Working
• Formula
• Corrections
• Numericals
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Calorimetry
• General Principle
The basic principle of calorimetry is the Law of Conservation of Energy
A calorimeter is an instrument used in calorimetry for measuring the
amount of heat released or absorbed in chemical or physical reactions. It
can determine heat content, latent heat, specific heat, and other thermal
properties of substances.

• Depending on the state of the fuel, there are two methods of determination
of CV
• Bomb Calorimeter (Solid/Non-volatile liquid fuels)
• Boy’s Calorimeter (Volatile liquid/ Gaseous fuels)
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Bomb Calorimeter
• Principle of Bomb Calorimeter
A known weight of solid / non-volatile liquid fuel is burnt in
the presence of excess oxygen in the closed pot, and the
products of combustion are cooled, to get GCV of the fuel.

https://www.youtube.com/watch?v=nJ
OH29SGcCk
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Diagram of Bomb Calorimeter


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Calculations

Mass of fuel = x g
Mass of water in calorimeter = W g
Water equivalent of calorimeter set = w g
Gross Calorific value of fuel = L cal/g
Rise in temperature of water = (t2 – t1) oC

Heat liberated by burning fuel = Heat absorbed by water and calorimeter


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Corrections

(i) Fuse wire correction (f) The heat liberated includes the heat given out
by ignition of the fuse wire used.
(ii) Acid correction (a)
S + O2 → SO2
2SO2 + O2 + 2H2O → 2H2SO4 ∆H = -6.03 x 105 J
4N + 2H2O + 5O2 → 4HNO3 ∆H = - 2.39 x 105 J

(iii) Cooling correction (tc)


Corrected formula for GCV
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Numericals

1) The coal containing 5% hydrogen (dry / moisture free basis) and 10%
moisture has gross calorific value of 33.5 MJ/kg. Calculate Net Calorific
Value of Coal. Latent heat of water vapour is 2.45 MJ/kg.

2) 0.72 g of a fuel containing 80% Carbon, when burnt in a bomb


calorimeter, increased the temperature of water from 27.3°C to 29.1°C. If
the calorimeter contains 250 g of water and its water equivalent is 150 g,
calculate GCV of the fuel.
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3) The temperature of 950.0 g of water increased from 25.5 0C to 28.5 0C.


On burning, 0.75 g of solid fuel in a Bomb calorimeter. Water equivalent
of copper calorimeter and latent heat of steam are 400 g and 587 cal/g
respectively. If the fuel contains 0.65% of hydrogen, calculate net
calorific value.

4) A sample of coal containing 5% H when allowed to undergo combustion


in Bomb Calorimeter, the following data were
obtained
weight of coal burnt = 0.95 g
weight of water taken = 700 g
water equivalent of bomb calorimeter = 2000 g
rise in temperature = 2.48 °C
cooling correction = 0.02 °C
fuse wire correction = 10 cal
acid correction = 60 cal
Calculate Gross and Net Calorific Value of Coal.
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COAL

https://www.youtube.com/watch?v=nIYz4Ck3w-k
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Analysis of Coal

Proximate analysis Ultimate analysis


1. Moisture 1. Hydrogen
2. Volatile Matter 2. Nitrogen
3. Ash
3. Sulphur
4. % Fixed carbon
4. Oxygen
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 Volatile Matter (V.M.) %

 Ash %

Fixed carbon %
Fixed carbon % = 100 – (% Moisture + % V. M. + % ash)
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Significance of proximate analysis


• Mositure: Lower moisture content implies that the quality
of coal is good

• Volatile matter: Lower VM better is the quality of coal

• Ash: Low ash content implies good quality coal

• Carbon: Higher the carbon content better the quality of


coal.
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Numericals
• 1)1.508 g of coal sample was heated at 110 oC for 1h. On cooling the
weight of the sample was found as 1.478 g. Strong heating of the
sample at 950 oC for 7 min. carried out in a closed crucible. The sample
on cooling weighed 1.058g. Calculate % moisture and % volatile
matter present in the sample.

• 2) 1.2 g of coal sample heated at 105-110 oC for 1 h, after heating the


sample weighed 1.16 g. This remaining sample of coal ignited at
constant weight of 0.09 g. In another experiment, 1.2 g of sample was
heated in a crucible at 950 oC for 7 min. After cooling the residue
weighed 0.8 g. Calculate % of fixed carbon
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Ultimate Analysis

1) Estimation of Carbon and hydrogen

2) Estimation of nitrogen

3) Estimation of Sulphur

Numericals
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Ultimate Analysis of Coal


The analysis of coal in which percentages of C, H, N, S and O
elements are found out, is known as ultimate analysis.

Estimation of Carbon and Hydrogen


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Estimation of Sulphur

Estimation of Nitrogen
.
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Numericals
• 1) 0.25 g of a coal sample on burning in a combustion chamber in the
current of pure oxygen was found to increase weight of U-tube with
anhydrous CaCl2 by 0.075 g and of KOH U-tube by 0.52gm. Find C
and H percentages in coal.

• 2) Find the % of C and H in coal sample from the following data- 0.20
g of coal on burning in a combustion tube in presence of pure oxygen
was found to increase in the weight of CaCl2 tube by 0.08 g and KOH
tube by 0.12 g.
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Liquid Fuels -Petroleum

Petroleum is a naturally occurring substance consisting of organic


compounds in the form of gas, liquid, or semisolid. Organic
compounds are carbon molecules that are bound to hydrogen (e.g.,
hydrocarbons) and to a lesser extent sulphur, oxygen, or nitrogen.
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Classification of petroleum
• There are three types
1) Paraffinic base type: Saturated hydrocarbons from CH4 to
C35H72

2) Asphaltic base type: Cycloparaffins with little amount of


paraffins and aromatic hydrocarbons

3) Mixed base type: Both paraffinic and asphaltic hydrocarbons


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Refining of Petroleum
• The refining of petroleum consists of

• (i) Removal of water

• (ii) Removal of sulphur

• (iii) Fractional Distillation

• https://www.youtube.com/watch?v=J2-tDV8KYEA&t=30s
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Fractional Distillation of Petroleum


Principle of Fractional Distillation
Separation of a liquid mixture into fractions differing in boiling point (and hence
chemical composition) by means of distillation, typically using a fractionating
column.

Portion of fractionating tower

Fractionating tower
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Various fractions of crude oil


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Octane Number of Petrol


• Knocking of Petrol engine: The intense vibrations, strong rattling metal noises
produced in petrol engine due to pre-ignition of petrol, is called knocking.

• Octane Number
• Definition: Octane number of a petrol sample is defined as the % of iso-octane
• in the mixture of iso-octane and n-heptane, which has similar knocking to the
petrol sample.
• Aromatics > Cycloalkanes > alkenes > Br. alkane > n-alkane

https://www.youtube.com/watch?v=uWx1cXR
7x_M
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Anti-knocking Agents
• Tetraethyl lead Pb(C2H5)4 0.5ml/litre
• Branched chain alkane of higher molecular weight
• Benzene, toluene, xylene
• Methyl t-butyl ether (MTBE) or ethyl t-butyl ether.
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Cetane Number of Diesel


• Knocking of Diesel engine: The intense vibrations, strong rattling metal
noises produced in diesel engine due to time lag or delay in ignition of
diesel, is called knocking.
• Cetane number
• Definition: Cetane number of a diesel is defined as the % of n-hexadecane in
the mixture of n-hexadecane and 2-methyl naphthalene which has same ignition
character like the ignition character of the diesel under test
• 2-Methyl napthalene n-Hexadecane / Cetane
• Cetane no. 0 Cetane no. 100

• CH3-(CH2)14-CH3
• Relative order of cetane no. values
• n-alkanes > cycloalkanes > alkenes > branched alkanes > aromatics
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How to increase cetane number

 Alkyl nitrates (principally 2-ethylhexyl nitrate) and di-tert-


butyl peroxide are used as additives to raise the cetane number.

 Antioxidant to improve oxidation resistance during storage.

 Lubricity additives for lubrication of fuel injection system.


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Combustion
• Combustion is a high-temperature exothermic redox chemical
reaction between a fuel (the reductant) and an oxidant, usually
atmospheric oxygen.
• Substances always combine in definite proportions. These proportions are
determined by their molecular masses.
• C + O2 → CO2 (12:32:44)
• 22.4 L of any gas at 0°C and 760mm Hg pressure (STP) has a mass equal
to its 1 mol.
• Air contain 21% of oxygen by volume and 23% of oxygen by mass.
• 28.94 g/mol is taken as molar mass of air.
• O2 required for combustion = theoretical O2 required - O2 present in the
fuel.

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• For solid or Liquid fuels:


• Where C, H, S and O are amounts of elements in Kg.

• Air quantity =

For Gaseous fuels
O2 volume required = volume gas component in m3 x
volume of O2per volume of gas.
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Numericals
• 1) A petrol sample contains 14% H and 86% carbon. Calculate the
quantity of air required for complete combustion of 1 kg petrol.

• 2) Volumetric analysis of producer gas is, H2 = 20 % CO = 22 % N2 =


50 %, CH4 = 2 % and CO2 = 6 %. Find volume of air required for
complete combustion of 1 m3 of the gas.

• 3) A gas has following composition by volume, H2 = 20 %, CH4 = 6%,


CO = 18%, O2 = 5%, N2 = 43 %. If 25 % excess air is used. Find
volume of air actually supplied per m3 of the gas.
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• 4) A gas has following composition by volume: H2 = 20 %; CH4 = 6% ,


CO = 22%, CO2 = 44%
O2= 4% N2 = 4%. Calculate the volume of air required for complete
combustion of 1 m3 of the fuel.

5) A sample of coal requires 20% excess air for complete combustion.
Calculate weight of air for 250 g of the coal, if its composition is C =
81%, H = 4%, N = 1.5%, S = 1.2%, O = 3%, ash = 9.35.

• 6) A gas used in internal combustion engine contains, H2 = 45 %, CO =


15%, CH4 =35%, N2= 5 % Find the minimum quantity (volume) of air
required per 1 m3 of the gas for complete combustion.
Photovoltaic cell
Definition of fuel cell
Fuel cells are electrochemical cells consisting of two
electrodes and an electrolyte which convert the chemical
energy of chemical reaction between fuel and oxidant
directly into electrical energy.
Ordinary combustion process of fuel is
Fuel + Oxygen Combustion products +heat
The process of fuel cell is
Fuel + Oxygen Oxidation products + electricity
Why fuel cells are more efficient?

The conventional process in heat engines to


produce electrical energy is
Chemical energy Heat Mechanical energy
Electrical energy

The process in fuel cell is


Chemical energy Electrical energy
The efficiency of energy conversion in fuel cell approaches 70%.
It is only 15-20% in gasoline powered engines and 30 – 35% in
diesel engines
Typical fuel cell
Fuel cell consist of electrodes, electrolyte and catalyst to facilitate the
electrochemical redox reaction
The basic arrangement of the fuel cell can be represented as
Fuel | Electrode | Electrolyte | Electrode | Oxidant
Fuel cell system
• The fuel (directH2 or reformed H2)undergoes
oxidation at anode and releases electrons.
• These electrons flow through the external circuit to
H2 – O2 fuel cell
the cathode.
• At cathode, oxidant (O2 from air)gets reduced.
• The electrons produce electricity while passing
through the external circuit. Electricity is generated
continuously as long as fuel and the oxidant are
continuously and separately supplied to the
electrodes of the cell from reservoirs outside the
electrochemical cell
• The cell reaction is as follows
At anode : 2 H2 4 H+ + 4 e-
At cathode: O2 + 4 H+ + 4 e- 2 H2O
Net reaction: 2 H 2 + O2 2 H2O
• Large number of these cells are stacked together in
series to make a battery called as fuel cell battery or
fuel battery
Applications of fuel cells
• The first commercial use of fuel cell was in NASA space
program to generate power for satellites and space capsules

• Fuels are used for primary and backup power for


commercial, industrial and residential buildings in remote
and inaccessible area

• They are used to power fuel cell vehicles including


automobiles, aeroplanes,boats and submarines
Advantages & Limitations of fuel cell
Advantages Limitations
• High efficiency energy • High initial cost
conversions • Life times of the cells are not
• Low noise pollution accurately known
• Saves fossil fuels for its efficient • Large weight and volume of
use
gas fuel storage system
• Fuels are less polluting
• High cost of pure hydrogen
• H2 – O2 fuel cell produce drinking
water of potable quality • Hydrogen can be stored in
• Design is modular therefore the lesser volume by
parts are exchangeable liquefaction but liquefaction
• Low maintenance cost itself require 30% of the
• The heat is cogenerated hence stored energy
increase efficiency of high • Lack of infrastructure for
temperature systems distributing hydrogen
Thank you

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