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UNIT IV
FUELS AND COMBUSTION
Fuels: Introduction: Classification of fuels - Analysis of coal (proximate and ultimate),
Carbonization-Manufacture of metallurgical coke (Otto Hoffmann method). Petroleum and
Diesel: Manufacture of synthetic petrol (Bergius process), Knocking - octane number, diesel oil-
cetane number; Power alcohol and biodiesel-LPG-Water gas
Combustion of fuels: Introduction: Calorific value - higher and lower calorific values,
Theoretical calculation of calorific value; Ignition temperature: spontaneous ignition
temperature, Explosive range; Flue gas analysis - ORSAT Method.
.
FUEL INTRODUCTION
PART - A
1. Write the characteristics of a good fuel (2) [July-2010]

A fuel is a combustible substance, containing carbon as the main constituent, which

on burning gives large amount of heat. During this process of combustion C & H with O
to liberate heat.

C + O2 → CO2 + 94 k cals

H2 + O2 → 2H2O + 68.5 k cals

The primary sources of fuels are coal and petroleum oil.

Characteristic or Requirements of a good fuel

➢ Fuels should be cheap and readily available.

➢ It should be safe and economical for storage and transport
➢ It should have higher calorific value.
➢ It should not undergo spontaneous combustion
➢ It should have moderate ignition temperature.
➢ It should have low moisture content because the moisture content reduces
the calorific value.

CLASSIFICATION OF FUELS

2. How fuel is being classified? Give an example. (2) [Dec-2011]

3. Classify fuels (2) [May-2019]

Chemical Fuels: It is of two types, Primary or Natural Fuel and Secondary or Derived Fuel.

Primary or Natural Fuel: Solid, Liquid & gas. Eg. Wood, peat, petroleum, naturel gas

Secondary or Derived Fuel: Solid, Liquid & gas. Coke, charcoal, Diesel, kerosene, Coal
gas etc.
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Solid fuels – Coal is an important primary solid fuel, that has been formed because of
alteration of vegetable matter under a favourable condition.

COAL AND COKE

4. What is metamorphism of coal? (2) [Dec-2006]

5. How is coal classified? (2) [Jan-2018]

Coalification (or) Metamorphism of coal

The process of conversion of vegetable matter into anthracite is called

coalification or metamorphism of coal.

Coal is classified based on its rank. The rank of coal indicates its degree of
maturity. Various varieties of coal are,

Wood → Peat →Lignite → Bituminous → coal → Anthracite

From wood to anthracite, the following changes will occur,

➢ Decrease in moisture content

➢ Decrease in volatile matter content
➢ Decrease in H, N, S and O content
➢ Increase in carbon content
➢ Increase in calorific value

ANALYSIS OF COAL
6. Distinguish between proximate and ultimate analysis (8) [May-2017]
7. How proximate analysis of coal is carried out? Mention its uses (8)[May-
2019]
8. Explain in detail about Proximate analysis. (8) [Dec-2015]
9. Explain the ultimate analysis of Coal (8) [June-2014, May-2017]
10. Write the Drawback of presence of sulphur in the coal. (2) [May-2015]
11. What is ultimate analysis of coal? Give its significance (16) [Dec-2019]
12. Distinguish between proximate and ultimate analysis (10) [Jan-2019]
13. How is percentages fixed carbon of coal calculated. (2) [Jan-2019]
14. Give a detail procedure of determination of various elements present in
coal (Ultimate analysis) (16) [Dec-2019]

To find the quality of coal the following two types of analysis are carried out,

✓ Proximate Analysis – to analyse the physical constituents

✓ Ultimate Analysis – to analyse the chemical constituents

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Proximate Analysis

Determination of moisture content in coal:

It is the loss in weight of coal caused by heating a weighed quantity of coal sample
for one hour at 105˚C.

% of moisture content = (Loss in weight of coal / Weight of coal taken initially) x 100

Significance of Moisture: High moisture content of the coal is undesirable for the
following reasons:

1) Reduces the calorific value of coal 2) Increases the consumption of coal for
heating purpose. 3) Lengthens the time of heating.

2. Determination of volatile matter in coal: It is the loss in weight of moisture free

powdered coal when heated in a crucible fitted with cover in a muffle furnace at 950˚C
for seven minutes.

% of volatile matter = (Loss in weight of moisture free coal / Weight of coal taken) x 100

Significance of volatile matter:

1. During burning of coal, gases like CO, CO2, CH4, N2, O2, hydrocarbons etc. that
come out are called volatile matter of the coal.

2. It has been found that the coal with higher volatile matter content ignites easily
has lower calorific value burns with long yellow smoky flame will evolve more coal gas
when heated in the absence of air.

3. Determination of ash in coal: It is the weight of residue obtained after burning a

known weight of coal in an open crucible in the presence of air at 750˚C for 30 minutes.

% of ash = (Weight of residue ash formed / Weight of coal taken) x 100

Significance of ash content:

1) Ash in the combination product of mineral matter in the coal. It consists mainly
SiO2, Al2O3 and Fe2O3 with varying amount of other oxides such as Na2O, CaO, MgO etc.

2) Ash containing the oxides of Na, Ca and Mg melt easily.

4. Determination of fixed carbon:

It is determined indirectly by deducting the sum of moisture, volatile matter and

ash percentage from 100.

% of fixed carbon in coal = 100 - % (moisture + volatile matter + ash)

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Significance of Fixed carbon:

It is the pure carbon present in coal. Higher the fixed carbon content of the coal,
higher will be the calorific value of the sample.

ULTIMATE ANALYSIS: Ultimate analysis refers the determination of weight percentage

of carbon, hydrogen, nitrogen, oxygen and sulphur of pure, dry coal. It is useful to the
designing of coal burning equipment and auxiliaries.

a) Determination of carbon and hydrogen in coal: A known amount of coal is burnt

in presence of oxygen thereby converting carbon and hydrogen of coal into-

(i) CO2 (C +O2 CO2) and

(ii) H2O (H2 + ½ O2 H2O) respectively.

The products of combustion CO2 and H2O are passing over weighed tubes of
anhydrous CaCl2 and KOH which absorb H2O and CO2 respectively. The increase in the
weight of CaCl2 tube represents the weight of water formed while the increase in the
weight of KOH tube represents the weight of CO2 formed. The percentage of carbon and
hydrogen in coal can be calculated in the following way-

The weight of coal sample taken =mg

The increase in the weight of KOH tube = X g The

increase in the weight of CaCl2 tube = Y g

Consider the following reaction

C (12) + O2 CO2 (44)

44 g of CO2 contains 12 g of carbon

44 g of CO2 contains = 𝑋 𝑥 12/44 g of carbon.

m g of coal contains = 𝑋 𝑥12 /44 g carbon

100 gms of coal contains = 12𝑥𝑋 𝑋100/𝑚

44

𝐼𝑛𝑐𝑟𝑒𝑎𝑠𝑒𝑑 𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝐾𝑂𝐻 𝑡𝑢𝑏 12

% of carbon in coal = 𝑋100
𝑊𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑐𝑜𝑎𝑙 𝑠𝑎𝑚𝑝𝑙𝑒 𝑡𝑎𝑘𝑒𝑛 44

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(b)Determination of hydrogen:

Consider the following reaction.

H2 (2) + ½ O2 H2O(18)

18 g of water contains 2 g of hydrogen.

Y g of water contains = 2𝑥𝑦 g of hydrogen

18

m g of coal contains = 2𝑥𝑦 𝑔 𝑜𝑓 ℎ𝑦𝑑𝑟𝑜𝑔𝑒𝑛

18

100
100 g of coal contains = 2𝑥𝑦 𝑥 g of hydrogen
18 𝑚

𝐼𝑛𝑐𝑟𝑒𝑎𝑠𝑒𝑑 𝑖𝑛 𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝐶𝑎𝐶𝑙2 𝑡𝑢𝑏𝑒 2

% of hydrogen in coal = 𝑥 𝑥 100

𝑊𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑐𝑜𝑎𝑙 𝑠𝑎𝑚𝑝𝑙𝑒 𝑡𝑎𝑘𝑒𝑛 18

(b) Determination of nitrogen: This is done by Kjeldahl’s method. A known amount of

powdered coal is heated with concentrated sulphuric acid in the presence of K 2SO4 and
CuSO4 in a long necked Kjeldhal’s flask. This converts nitrogen of coal to ammonium
sulphate. When the clear solution is obtained (ie., the whole of nitrogen is converted into
ammonium sulphate), it is heated with 50 % NaOH solution and the following reaction
occurs.

(NH4)2SO4 + 2 NaOH Na2SO4 + 2 NH3 + H2O

The ammonia thus formed is distilled over and is absorbed in a known quantity of
standard 0.1 N H2SO4 solution. The volume of unused 0.1 N H2SO4 is then determined by
titrating against standard NaOH solution. Thus, the amount of acid neutralized by
liberated ammonia from coal is determined using the formula.

The weight of coal sample taken = m g

Initial volume of N/10 HCl = V1 mL

Volume of unused N/10 HCl = V2 mL

Therefore, acid neutralized by ammonia = (V1-V2) mL

As we know that,

1000 mL of 1 N HCl = 1 mole of HCl = 1 mole of NH3

14 g of N2 = 17g of NH3
𝑁
14 𝑥 (𝑉1−𝑉2)
(V1-V2) mL of N/10 HCl = 10 g of nitrogen
1000 𝑥1
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𝑁
14 𝑥 (𝑉1−𝑉2)
m g of coal sample contains = 10 g of nitrogen
1000 𝑥1
𝑁
14 𝑥 (𝑉1−𝑉2)
100 g of coal sample contains = 10 𝑥 100 g of nitrogen
1000 𝑥1 𝑚

14 𝑥 𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑎𝑐𝑖𝑑 𝑐𝑜𝑛𝑠𝑢𝑚𝑒𝑑 𝑥 𝑛𝑜𝑟𝑚𝑎𝑙𝑖𝑡𝑦

% of Nitrogen in coal = 𝑥 100
1000 𝑥 𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑐𝑜𝑎𝑙 𝑠𝑎𝑚𝑝𝑙𝑒 𝑡𝑎𝑘𝑒𝑛

1.4 𝑥 𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑎𝑐𝑖𝑑 𝑐𝑜𝑛𝑠𝑢𝑚𝑒𝑑 𝑥 𝑛𝑜𝑟𝑚𝑎𝑙𝑖𝑡𝑦

Or % of nitrogen in coal =
𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑐𝑜𝑎𝑙 𝑠𝑎𝑚𝑝𝑙𝑒 𝑡𝑎𝑘𝑒𝑛

(c) Determination of sulphur in coal: A known amount of coal is burnt completely in

Bomb calorimeter in presence of oxygen. Ash thus obtained contains sulphur of coal as
sulphate which is extracted with dil. HCl. The acid extract is then treated with BaCl 2
solution to precipitate sulphate as BaSO4.The precipitate is filtered, washed, dried and
weighed. From the weight of BaSO4, the percentage of sulphur in coal is calculated in the
following way.

The weight of coal sample taken = m g

The weight of BaSO4 precipitate = X g

Consider the following equations

S (32) + 2O2 SO42-

BaCl2 BaSO4 ↓ (233)

233 g of BaSO4 contains 32 g of sulphur.

x g of BaSO4 contains = 32 𝑥 𝑋 g of sulphur

233

m g of coal sample contains = 32 𝑥 𝑋 g of sulphur

233

100
100 g of coal sample contains = 32 𝑥 𝑋 𝑥 g of sulphur
233 𝑚

% of S in coal = 32 𝑥 𝑋
𝑥 100
233 𝑥 𝑚

32 𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝐵𝑎𝑆𝑂4 𝑜𝑏𝑡𝑎𝑖𝑛𝑒𝑑 233 𝑥 𝑥 10

% of S in coal =
𝑊𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑐𝑜𝑎𝑙 𝑠𝑎𝑚𝑝𝑙𝑒 𝑡𝑎𝑘𝑒𝑛

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Ash content

Determination of ash content is carried out as in proximate analysis

Oxygen content

The % of oxygen is = 100 - % of (C +H+N+S+ash)

Significance of Ultimate analysisC and H contents

✓ Higher the % of C better is the quality of the fuel and it has higher calorific value.
✓ It is used to classify the coal

Nitrogen contents

✓ Nitrogen does not have calorific value and its presence is highly undesirable to
coal.
✓ A good quality of coal must have less nitrogen content.

Sulphur content

✓ The presence of S is increasing the calorific value even though its presence is
undesirable to coal due to the formation of SO2 and SO3 which are harmful and
corrosion effects on equipment.
✓ It affects the property of metal so for the preparation of metallurgical coke it is not
suitable.

Oxygen content

✓ Lower the % of oxygen higher is its calorific value.

✓ As the oxygen content increases its moisture holding capacity increases and the
calorific value of the fuel is reduced.

CARBONISATION

15. How is coke superior than coal? (2) [May-2011]

16. What is the difference between caking coal and coking coals (2) [Dec-2012]
17. Describe the Otto-Hoffman process for the manufacture of metallurgical
coke. (8) [Jun-2009, Dec-2009, Dec-2014, May-2015, Dec-2015, June-2016]
18. Why coke is used in metallurgical process than coal (2) [Dec-2007,Dec-
2009]
19. Describe the synthesis of metallurgical coke by otto- hoffmans by product
oven method and explain how various by products recovered? (16) [Dec-
2019]

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When coal is heated strongly in absence of air, it is converted into lustrous, dense,
porous, and coherent mass know as coke. This process of converting coal into coke is
known as carbonisation.

Caking coal and Coking coals

When coal is heated strongly, the mass becomes soft plastic and fuses to give a
coherent mass. These are called Caking coals. But if the mass so produced is hard, porous
and strong then the coals are called Coking coals. It is used for manufacturing the
metallurgical coke.

Types of Carbonisation

Based on the temperature, used for carbonisation, carbonisation is classified into

two types.

✓ Low Temperature Carbonisation (LTC) (500 – 700 oC)

✓ High Temperature Carbonisation (HTC) (900 – 1300oC)

MANUFACRURE OF METALLURGICAL COKE (OTTO-HOFMANN PROCESS)

When bituminous coal (coal containing about 90 % carbon) is heated strongly in

absence of air, the volatile matter escapes out and a while, lustrous, dense, strong, porous
and coherent mass is left which is called metallurgical coke.

Characteristics of metallurgical coke: The most important industrial fuel is the

metallurgical coke. This is used in the metallurgical industry, especially in the blast
furnace. A good metallurgical coke must have following requirements:

Purity: Low moisture and ash content are desirable in metallurgical coke. It must contain
minimum % of phosphorous and sulphur.

Porosity: High porosity is desirable in furnace coke to obtain high rate of combustion.

Strength: The coke should be hard and strong to withstand pressure of ore, flux etc. in
the furnace.

Size: Metallurgical coke must be uniform and medium size.

Calorific value: This should be high.

Combustibility: It should burn easily.

Reactivity: It refers to its ability to react with O2, CO2, steam and air. The metallurgical
coke must have low reactivity.

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Cost: It must be cheap and readily available.

In order to 1. increase the thermal efficiency of the carbonization process and

2. recover valuable by-products like coal gas, ammonia, benzol oil, tar etc. Otto
Hoffmann developed a modern by-product coke oven. The oven consists of a number of
silica chambers, each about 10-12 m long, 3-4 mtall and 0.4-0.45 m wide. Each chamber is
provided with a charging hole at the top, it alsoprovided with a gas off valve and iron door
at each end for discharging coke.

Coal is introduced in to the silica chamber and the chambers are closed. The chambers are
heated to 12000C by burning the preheated air and the producer gas mixture in the interspaces
between the chambers.

The air and gas are prepared by sending them through 2nd and 3rd hot
regenerators. Hot flue gases produce during carbonization are allowed to pass through
1st and 4th regenerators until the temperature has been raised to 10000C. While 1st and
4th regenerators are heated by hot flue gases, the 2nd and 3rd regenerators are used for
heating the incoming air and gas.

For economical heating, the direction of inlet gases and flue gases are changed
frequently. The above system of recycling the flue gases to produce heat energy is known
as the regenerative system of heat economy. When the process is complete, the coke is
removed and quenched with water. Time taken for complete carbonization is about 12-
20 hours. The yield of coke is about 70%. The valuable by products like coal gas, tar,
ammonia, H2S and benzol, etc. can be removed from flue gas.

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Recovery of by-products: The gas coming out of the retort is known as coke oven gas.
This consist of tar, ammonia, moisture, aromatic hydrocarbons (naphthalene, benzene),
H2S etc. It can be used as a fuel after removing coal tar and ammonia.

i) Tar: The coke oven gas is first passed through a tower in which liquid ammonia
is sprayed. Tar and dust get collected in a tank below, which is heated by a steam coil to
recover back the ammonia sprayed.

ii) Ammonia: The coke oven gas is passed through another tower in which water
is sprayed. Gaseous ammonia goes into solution as NH4OH.
iii) Naphthalene: After recovering ammonia, the remaining gases are led through
another tower where water is sprayed at low temperature when naphthalene gets
condensed.
iv)Benzene: The resultant gas from the previous step is sprayed with petroleum
whereby benzene and its homologues can be recovered.

iv) H2S: The gases are then passed through a purifier, packed with moist
Fe2O3. Hydrogen sulphide is retained here.

Fe2O3 + 3 H2S Fe2S3 + 3 H2O

When all the Fe2O3 is converted into Fe2S3, the purifier on exposure to the
atmosphere, regenerates Fe2O3 in the following manner.

Fe2S3 + 4 O2 2 FeO + 3 SO2

4 FeO + O2 2 Fe2O3

Advantages:
• Valuable by products are obtained like ammonia, benzene, naphthalene etc.
• It combust with very short period.
• It gives 70 % yield.

PETROLEUM AND DIESEL

20. What is Cottrell’s process in crude oil refining (2) [Jul-2009]

21. Why should leaded petrol not to be used? (2) [Apr-2001]
22. Explain the petroleum refinery process in detail with neat sketches. What
are the properties and applications of various fractions (8) [June-2013]
23. Give the classification of petroleum. (2) (Dec-2019)

Petroleum is coming under a liquid fuel. It exits in dark brown or black coloured
oil found deep in the earth. Crude oil contains a mixture of paraffinic and olefinic
hydrocarbons with a minimum quantity of N, O and S.

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PETROLEUM PROCESSING AND FRACTIONS: Petroleum or crude oil is a dark greenish-

brown, viscous oil found deep in earth crust. It is composed mainly of various
hydrocarbons (like straight-chain paraffins, cycloparaffins or naphthalene, olefins and
aromatics), together with small amounts of organic compounds containing oxygen,
nitrogen and sulphur.

Mining of petroleum: It is done by drilling holes in the earth’s crust and sinking pipes
up to the oil-bearing porous rocks.

Refining of crude oil: The process of removing impurities and separating the crude oil
into various fractions having different boiling points is called refining of petroleum,

Step 1: Separation of water (Cottrell’s process): The crude oil from the oil well is an
extremely stable emulsion of oil and salt water. The process of freeing oil from water
consists in allowing the crude to flow between two highly charged electrodes. The colloidal
water-droplets coalesce to form large drops, which separate out from the oil.

Step 2: Removal of harmful sulphur compounds: This involves in treating oil with
copper oxide. A reaction occurs with sulphur compounds, which results in the formation
of copper sulphide (a solid), which is then removed by filtration.

Step 3: Fractional distillation: The crude oil is then heated to about 400OC in an
iron retort whereby all volatile constituents, except the residue (asphalt or coke) are
evaporated. The hot vapours are then passed up a fractionating column, which is a tall
cylindrical tower containing several horizontal stainless-steel trays at short distances.
Each tray is provided with small chimney, covered with a loose cap. As the vapours go up,
they become gradually cooler and fractional condensation takes place at different heights
of column. Higher boiling fraction condenses first, while the lower boilingfractions turn-
by-turn.

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Approximate
Approximate number of
Fraction boiling point carbon Important uses
S.No. range atoms per
molecule
1. Natural gas <20oC C1-C4 Cooking gas (LPG)
Petrochemical
2. Naphtha 70oC C5-C9
products
C5-C12
3. Gasoline 120oC Used in IC engine
(mostly C6-C8)
Fuel for jet aircraft,
Kerosene
4. 170oC C10-C15 kerosene lamp and
(paraffin)
kerosene stove
Diesel engines,
5. Diesel oil 270oC C15-C25 buses, lorries and
trains
Lubricants
(including Lubricant in
6. petroleum jelly, 340-500oC C20-C50 engines; waxes and
grease and polishes.
paraffin wax)
Fuels for ships,
7. Fuel oil 600oC C20-C70 factories and
centralized heating
Residue -
Used for surfacing
Bitumen (tar);
8. >500oC >C70 roads and roofing;
asphalt and
Used as fuel
coke

Various fractions, composition and their uses

MANUFACTURE OF SYNTHETIC PETROL (BERGIUS PROCESS)

24. How is synthetic petrol manufacture by Bergius Process? (8) (10) (8) (8)
[Dec-2005, Dec 2006, Jun-2014, Jan-2022]

In countries like Germany and South Africa which do not have extensive
petroleum deposits, motor fuels are derived from non-petroleum sources. Petroleum can
be produced from coal by the following method.

BERGIUS PROCESS: (HYDROGENATION OF COAL): This method was first proposed by

Bergius in Germany. It consists of converting low grade coals such as bituminous coal into
liquid and gaseous fuels by hydrogenating them in presence of iron oxide as catalyst.
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The raw materials used in the process are coal dust, heavy oil and nickel oleate or
tin oleate. A coal paste is prepared by mixing coal dust with heavy oil and catalyst. It is
then pumped into the converter where the paste is heated to 450˚C under 200-250
atmosphere in pressure of hydrogen. The reaction products mainly contain mixture of
petroleum hydrocarbons

Since the reaction is exothermic, the vapours leaving the converters are condensed in the
condenser to give synthetic petroleum or crude oil. The oil is then fractionally distilled
to give (i) petrol (ii) middle oil (iii) heavy oil.

Middle oil is again hydrogenated in presence of solid catalyst to produce more

amount of petroleum. Heavy oil is used for making paste with fresh coal dust which is
required for this process.

Bergius process
KNOCKING

25. What is meant by cetane number (2) [Jun -2010, May-2011, Jan-2022]
26. Describe the process of knocking (2) [Jan-2019]
27. How will you improve the anti-knocking characteristics of diesel (2) [Dec-
2006]
28. Explain octane & cetane number and how it can be improved? (8) [May-
2019]

Knocking is a kind of explosion due to rapid pressure rise occurring in an IC engine.

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In an internal combustion engine, a mixture of gasoline (petroleum) vapour and

air is used as a fuel. After the initiation of the combustion reaction by spark in the cylinder,
the flame should spread rapidly and smoothly through the gaseous mixture; thereby the
expanding gas drives the piston down the cylinder. The ratio of the gaseousvolume in the
cylinder at the end of the suction stroke to the volume at the end of compression stroke
of the piston is known as the compression ratio. The efficiency of an internal combustion
engine increases with the compression ratio.

However, successful high compression ratio is dependent on the nature of the

constituents present in the gasoline used. In certain circumstances, due to the presence
of some constituents in the gasoline used, the rate of oxidation becomes so great that the
last portion of the fuel air mixture gets ignited instantaneously producing an explosive
violence known as knocking. The knocking results in loss of efficiency since this
ultimately decreases the compression ratio.

Chemical structure of knocking: The knocking tendency of fuel hydrocarbon mainly

depends on the chemical structures. The knocking tendency decreases in the following
order.

Straight chain paraffins (n-paraffins) > branched chain paraffins (iso paraffins) >
olefins > cycloparaffins (naphthalene) > aromatics.

Thus, olefins of the same carbon chain length possess better antiknock properties
than the corresponding paraffins and so on.

OCTANE NUMBER:

Octane number is introduced to express the knocking characteristic of petrol. It

has been found that n-heptane knocks very badly and hence, its anti – knock value has
been given zero. On the other hand, iso – octane gives very little knocking and so its anti
–knock value has been given 100.

Thus, Octane number is defined as the percentage of iso-octane present in a

mixture of iso octane and n-heptane. Thus, if a sample of petrol gives as much of knocking
as a mixture of 75 parts of iso-octane and 25 parts of n-heptane, then its octane number
is taken as 75. The octane ratings of some common hydrocarbons are given in the table.

CH3 – CH2 – CH2 - CH2 – CH2 - CH2 – CH3

Isooctane (octane number = 100) n- heptane (Octane number = 0)

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Fuels with octane rating greater than 100 are quite common nowadays and they
are rated by comparison with a blend of iso-octane with tetra ethyl lead (TEL) which
greatly diminishes the knocking tendency of any hydrocarbon with which it is mixed. The
value of octane number in such cases is determined by extrapolation.

Leaded Petrol

The anti-knocking properties of gasoline can be improved by the addition of

suitable additives. Tetra Ethyl Lead (TEL) is an important additive which is added to the
petrol. The petrol containing TEL is called Leaded Petrol.

Mechanism of Knocking

TEL lessens the propensity of hydrocarbon to knock. A chain grows as a result of

knocking, which uses a free radical process to cause an explosion. Knocking will stop if
the chains are broken before they expand. The chain growth is terminated as a result of
TEL's thermal breakdown into ethyl free radicals, which mix with the knocking process's
increasing free radicals.

Disadvantages of Using TEL

The TEL is transformed into lead oxide and metallic lead when the leaded gasoline
is utilised as a fuel. This lead builds up on the cylinder walls and spark plug, which is bad
for the longevity of the engine. To prevent this, TEL is combined with a little amount of
ethylene dibromide. Ethylene dibromide, which is released with exhaust gases, combines
with lead and lead oxide to produce volatile lead bromide.

DIESEL OIL

It is a fraction obtained between 250 – 320OC during fractional distillation of

petroleum. It is a mixture of C15H32 to C18H38 hydrocarbons. Its calorific value is about
11000 kcal/kg.

Causes of knocking in CI engine

In a diesel engine, only the air is compressed initially. The cylinder's temperature
rises to around 500oC as a result of this compression. The hot air is then sprayed with the
oils. Pressure and temperature are both further increased as a result. As the gases expand,
they push the piston, starting the power stroke. The interval between the injection of a
fuel and its ignition is known as ignition lag or ignition delay, and it occurs in a diesel
engine where fuel combustion is not instantaneous. This delay results from the time
15
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needed for oil droplets to vaporise and for the vapour to reach its ignition temperature.
Long ignition delays cause more vapour to build up in the cylinder, which explodes during
ignition. The cause of diesel knock is this. Diesel knock won't happen if there is a short
ignition lag.

CETANE NUMBER: In a diesel engine, the fuel is exploded not by a spark but by the
application of heat and pressure. Diesel engine fuels consist of longer chain hydrocarbons
than internal combustion engine fuels. In other words, hydrocarbon molecules in a diesel
fuel should be as far as possible the straight chain ones, with a minimum admixture of
aromatics and side chain hydrocarbon molecules. The suitability of a diesel fuel is
determined by its cetane value which is the percentage of hexadecane in a mixture of
hexadecane and 2-methyl naphthalene, which has the same ignition characteristics
as the diesel fuel in question.

The cetane number of a diesel fuel can be raised by the addition of small quantity
of certain pre-ignition dopes like ethyl nitrite, isoamyl nitrite, acetone peroxide. The
cetane number is decreased in the following order:

Straight chain paraffins > Cycloparaffins > Olefins > branched paraffins >
Aromatics.

S.No. Petrol Diesel

This is the low boiling fraction
1.
ofpetroleum.
It is the fuel for spark
2.
ignition Engines
Knocking is the result of
3.
premature Ignition
Knocking is measured in
4.
terms of octane rating.
Adding of TEL improves the
5.
anti-knock property.
6. Thermal efficiency is low
7. Consumption is more
Contains C10 to C16 hydrocarbons and
constitutes the high boiling fraction of
petroleum.
It is the fuel for compression
ignition engines
Knocking occurs due to delay in the
ignition.
Knocking is measured in terms of
cetane rating.
Doping with isoamyl nitrate improves
anti- knocking
High thermal efficiency
Consumption is less

16
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POWER ALCOHOL

29. What is power alcohol? Mention the advantages. (2) [Jun-2014]

When ethyl alcohol is blended with petrol at concentration of 5-10%. It is called

power alcohol .in other words absolute alcohol (100% ethyl alcohol) is also called power
alcohol. Ethyl alcohol is used in an internal combustion (IC) engine. The addition of ethyl
alcohol to petrol increases its octane number. When ethyl alcohol is blended with diesel
it is called E- diesel.
Manufacture of power alcohol involves in the following 2 steps,

Step 1:
Manufacture of ethyl alcohol

Ethyl alcohol can be synthesized by fermentation of carbohydrates (sugar

materials). Fermentation of molecules which is the residue left after the crystallization of
sugar, with yeast generates alcohol. This fermentation yields only about 20 % alcohol.
C6H12O6 Yeast 2C5H5OH+2CO2
Concentration of alcohol can be increased up to 97.6% by fractional distillation
yields rectified spirit. The concentration of alcohol cannot be increased by distillation
above 97.6 %. Because it forms a constant boiling mixture with water. The constant boiling
point has a lower boiling point than alcohol.
Step 2:

Conversion of ethyl alcohol into power alcohol.

✓ But for IC engine, 100% alcohol (absolute alcohol) is prepared by removing last trace
of water from rectified spirit. It can be done by the following two methods.
✓ alcohol containing trace of water, is distilled with benzene. When benzene passes over
with a portion of alcohol and water, it leaves behind absolute (power)alcohol.

✓ Finally absolute alcohol is mixed with petrol at concentration of 5-10% to get power
alcohol.
Properties

✓ Power alcohol has a lower calorific value (7000K.Cal/Kg)

✓ It has high octane number (90)
✓ Its anti-knocking properties are good.
✓ It generates 10% more power than the gasoline of same quality.
✓ Its compression ratio is also high.
17
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Uses:
It is used as a very good fuel in motors.

Advantages and disadvantages of power alcohol

Advantages

✓ It is cheaper than petrol

✓ If any moisture is present, power alcohol absorbs it.
✓ As ethyl alcohol contains oxygen atoms complete combustion occurs, so emission
of CO2,hydrocarbon particulates are reduced.
Disadvantages
✓ As the calorific value of power alcohol (7000 Cal/gm) is lower than petrol (11,500
Cal/gm), specially designed engine is required.
✓ Output power is reduced up to 35%
✓ Due to its high surface tension, atomization of power alcohol is difficult, so it
causes starting trouble.
✓ It may undergo oxidation to give acetic acid, which corrodes engine part.

BIO-DIESEL

Vegetable oils comprise of 90-95% triglycerides with small amount of diglycerides,

free fatty acids, phospholipids, etc. triglycerides are esters of long chain fatty acids, like
stearic acids and palmitic acids. The viscosity of vegetable oils is higher and their
molecular weight are in the range of 600 to 900 which are about 3 times higher than those
of the diesel fuels.

Problems in using Vegetable oils directly

✓ As the viscosity of vegetable oils are high, atomization is very poor and hence
inefficient mixing of oil with air leads to incomplete combustion.
✓ Oxidation and thermal polymerization of vegetable oil cause deposit formation.
✓ Their high viscosity causes misfire and ignition delay.
✓ Their high volatility and consequent high flash point leads to more deposit
formation.
✓ The use of vegetable oils as direct fuel requires modification of the conventional
diesel engine design

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Manufacture : Trans-esterification or alcoholysis

The above problems are overcome by reducing the viscosity of the vegetable oils
by the processknown as trans-etherification or alcoholysis. Alcoholysis is nothing but
displacement of alcohol from an ester by anther alcohol.
It involves treatment of vegetable oil (sunflower oil, palm oil, soybean oil mustard
oil, etc) with excess of methanol in presence of catalyst to give mono ethyl ester of long
chain fatty acid and glycerin. It is allowed to stand for some time and glycerin is separated.

Methyl ester of fatty acid thus formed are called Bio-Diesel is defined as mono-alkyl
ester of long chain fatty acid derived from vegetable oils or fats. It is a pure fuel before
blending with conventional diesel fuel. Bio-diesel can be blended with petroleum diesel.
Advantages

✓ Bio-diesel is biodegradable.
✓ It is from renewable resources.
✓ The gaseous pollutant is lesser as compared to the vegetable oils.
✓ Bio-diesel can be produced from different types of vegetable oils.
✓ Best engine performance and less smoke emission are achieved.
Disadvantages
✓ Bio-diesel gels in cold weather.
✓ As Bio-diesel are hygroscopic, Bio-Diesel can absorb water from atmosphere.
✓ Bio-diesel decreases the horsepower of the engine.
✓ Bio-diesel degrades and soften the rubber and plastics that are used in some old
cars.
✓ Bio-diesel has about 10% higher nitrogen-oxide (NOx) emission than
conventional petroleum.

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Liquified Petroleum Gas (LPG)

LPG is also known as bottled gas or refinery gas.
Production
It is obtained as a by product during the cracking of heavy oils or from natural gas. It is
dehydrated, desulfurized and trace amount of odorous organic sulphides(mercaptans) are
added to give warning of gas leak. It is supplied under pressure in steel or iron containers.
Its calorific value is 28000 k.cal/m3.
The main constituents of LPG are

No Constituents Percentage
1 n-butane 30-35
2 Isobutane 30-35
3 Butylene 15-20
4 Propane 20-25
5 Propylene & rest
ethane

Uses
1. It is used as domestic and industrial fuel.
2. It is also used as motor fuel.
Advantages of LPG over other gaseous fuels:
1. It burns cleanly without leaving any residue.
2. It has higher calorific value than coal gas & natural gas.
3. It has high thermal efficiency.
4. It needs little care for maintenance.
5. It is free from CO & so less hazardous

WATER GAS

It is a mixture of combustible gases, CO(41%) and H2 (51%) with small

amount of noncombustible gases, CO2(4%) and N2(4%). Its calorific value is
about 2800.
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Manufacture
 The water gas producer consists of a tall steel vessel, lined inside with
refractory bricks. It is provided with cup and cone feeder at the top and a
side opening for water gas exit. At the bottom it is provided with two inlet
pipes for passing air and steam

 When steam and little air is passed alternatively over a red hot coke
maintained at about 900 - l000°C in a reactor, water gas is produced.

Manufacture of water gas

Water gas outlet

Steam supply Air supply

Refractory brick lining Ash outlet

The reactions of water gas production involves the following two steps.
Step 1
In the first step, steam is passed through the red hot coke, where CO &
H2 gases are produced. The reaction is endothermic. Hence, the
temperature of the coke bed falls.
C + H2O CO + H2 endothermic – 29 k cal
Step 2
In the second step, in order to raise the temperature of the coke bed to
1000 C , the steam supply is temporarily cut off and air is blown in. The
reaction is exothermic.
C +O2 CO2 exothermic H + 95 k cal
2C + O2 2CO exothermic H + 59 k cal
Thus the steam – run and air blow are repeated alternatively to
maintain proper temperature.

Uses.
1. It is used for the production of H2 and in the synthesis of ammonia.
2. It is also used as a source of and illuminating gas and fuel gas
[Type here]

COMBUSTION OF FUELS

30. What is meant by calorific value of a fuel? (2) [Jul-2010, Jun-2016]

31. What is calorie? (2) [Jan-2018]
32. Name the important units of Calorific values (2) [Jan-2018]
33. What is calorific value? What are its types? Explain. (2) [May-2019]
34. Define calorific value of a fuel. (2) [Jan-2019]

A fuel burns in the presence of oxygen during the quick exothermic oxidation
process known as combustion, which produces heat and light as it does so.

The goal of combustion is to extract the most heat possible from a

combustible material in the shortest period. Most combustion materials are carbon and
hydrogen enriched. They go through thermal decomposition during combustion to
produce simpler compounds, which are then oxidised to CO2, H2O, etc.

C + O2 → CO2: Exothermic

H2 + ½ O2 → H2O: Exothermic

From the above reaction large amount of heat is liberated.

CALORIFIC VALUE

Calorific value is defined as the total amount of heat liberated, when a unit mass
of fuel is burnt completely.

Units of calorific values

The amount of heat can be measured in the following units,

1. Calorie
2. Kilocalorie
3. British thermal Unit (B.T.U)
4. Centigrade Heat Unit (C.H.U)

Calorie :

Calorie is defined as the amount of heat required to raise the temperature of 1

gram of water through 1oC.
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HIGHER AND LOWER CALORIFIC VALUE

35. Define GCG and NCV of a Fuel. (2) [Dec-2005, Jun-2006]

Higher or Gross Calorific Value (GCV)

It is defined as the total amount of heat produced, when a unit quantity of the fuel
is completely burnt, and the products of combustion are cooled to room temperature.

Burning a fuel containing hydrogen produces steam, which is made of the hydrogen.
Steam condenses into water when the combustion products are cooled to room
temperature, which releases latent heat. The latent heat of steam condensation is thus
added to the total calorific value.

Lower or Net Calorific Value (NCV)

It is defined as the net heat produced, when a unit quantity of the fuel is completely
burnt and the products of combustion are allowed to escape.

NCV = GCV – Latent heat of condensation of water vapour produced

= GCV – Mass of H X 9 X Latent heat of condensation of water vapour

1 part by weight of H2 produces 9 parts by weight of H2O as follows. The latent heat of
steam is 587 cal/gm.

H2 + O2 → H2O

2 gms 16gms 18 gms

1 8 9

Thus , NCV = GCV – 9/100 H x 587

= GCV – 0.09H X 587

THEORETICAL CALCULATION OF CALORIFIC VALUES

Dulong’s formula
Dulong’s formula for the theoretical calculation of calorific value is,
GCV or HCV
1
= [8080 𝐶 + 34500 (𝐻 − 𝑂) + 2240 𝑆] 𝑘 𝑐𝑎𝑙/𝑘𝑔
100 8
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Where, C, H, O and S represent the Percentage of the corresponding elements in the fuel.

It is based on the assumption that the caloric values of C, H and S are found to be
8080, 34500 and 2240 kcal, when 1 kg of the fuel is burnt completely. However, all the
oxygen in the fuel is assumed to be present in combination with hydrogen in the ratio H:O
𝑂
as 1:8 by weight. So the surplus hydrogen available for combustion is 𝐻 −
8

9
NCV or LCV = [𝐻𝐶𝑉 − 𝐻 𝑋 587] kcal/kg
100

PROBLEMS BASED ON CALORIFIC VALUE

Calculate the gross and net calorific values of coal having the following
compositions, carbon = 85%, hydrogen = 8%, sulphur = 1%, nitrogen = 2% and ash
= 4%, latent heat of steam = 587 cal/gm. (8) [Jan-2022]

Given, C, H, S,N, ash and Latent heat

Asked = GCV and NCV

GCV = 1
[8080 𝐶 + 34500 (𝐻 − 𝑂) + 2240 𝑆] 𝑘 𝑐𝑎𝑙/𝑘𝑔
100 8

1 0
=
100
[8080 𝑥 85 + 34500 (8 − 8) + 2240 𝑥 1] 𝑘 𝑐𝑎𝑙/𝑘𝑔

1
= [6,86,800 + 2,76,000 + 2240]𝑘 𝑐𝑎𝑙/𝑘𝑔
100

1
= [9,65,040]𝑘 𝑐𝑎𝑙/𝑘𝑔
100

= 9650.4 kcal/kg
9
NCV = [𝐺𝐶𝑉 − 100 𝑋 8 𝑋 587] kcal/kg

9
= [9650.4 − 𝑋8 𝑋 587] kcal/kg
100

= [9650.4 − 422.64] kcal/kg

= 9227.76 kcal/kg

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Calculate the gross and net calorific values of a coal sample having the following
composition C= 90%, H = 7%, S= 3.5%, O = 3%, N = 2.8 % and ash = 4.7%.

Given = C,H,N,S,O and ash %

Asked = GCV and NCV

GCV = 1
[8080 𝐶 + 34500 (𝐻 − 𝑂) + 2240 𝑆] 𝑘 𝑐𝑎𝑙/𝑘𝑔
100 8

1 3
=

100
[8080 𝑥 90 + 34500 (7 − 8) + 2240 𝑥 3.5] 𝑘 𝑐𝑎𝑙/𝑘𝑔

1
= [7,27,200 + 34500 (7 − 0.375) + 2240 𝑥 3.5]𝑘 𝑐𝑎𝑙/𝑘𝑔
100

= [7272 + 2285.6 + 78.4] 𝑐𝑎𝑙/𝑘𝑔

= [9636] 𝑐𝑎𝑙/𝑘𝑔
9
NCV = [𝐺𝐶𝑉 − 100 𝑋 𝐻 𝑋 587] kcal/kg

9
=[9636 − 𝑋 7 𝑋 587] kcal/kg
100

= 9636 − 369.8] kcal/kg

= 9266.2 kcal/kg

IGNITION TEMPERATURE

36. What is ignition Temperature (2) [Jun-2014]

37. Define ignition temperature (2) [May-2019]
38. Define spontaneous ignition temperature (2) [Dec-2014]

The lowest temperature to which the fuel must be heated, so that its starts burning
smoothly. Coal ignites at a temperature of roughly 300oC. The ignition temperature for
liquid fuels is known as the flash point, and it is between 200 and 450oC. The ignition
temperature for gaseous fuels is around 800oC. Spontaneous Ignition Temperature (SIT)
It is defined as the minimum temperature at which the fuel catches fire (ignites)
spontaneously without external heating.

If the ignition temperature of the fuel is low, it can catch fire very quickly. On the

23
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other hand, if the ignition temperature is high, it is difficult to ignite the fuel. If the heal
evolved in a system is unable to escape, temperature of the system goes on increasing and
when SIT is reached, the system burns on its own.

EXPLOSIVE RANGE OR LIMITS OF INFLAMMABILITY

39. Define Explosive range of a fuel (2) [Jun-2014]

All gaseous fuels have two limits called upper limit and lower limit. These limits
represent percentage by volume of fuel present in fuel-air mixture.

1. Lower limits represent the smallest proportion of combustible gas.

2. Upper limit represents the largest proportion of combustible gas.

The range covered by these limits is termed as explosive range of the fuels. For
continuous burning the amount of fuel present in the fuel-air mixture should not go below
the lower limit or above the upper limit.

Example,

Petrol has an explosive range of 2-4.5. This indicates that the mixture will burn upon
ignition when the concentration of gasoline vapour in the gasoline-air mixture is between
2 and 4.5 by volume. The mixture won't ignite if the amount of gasoline vapour in it is less
than 2% (lower limits) or more than 4.5% (higher limits) by volume. The table lists some
of the inflammability limits.

Lower limit of Upper limit of

Gas
inflammability inflammability

Hydrogen 4 74

Acetylene 3 80

Natural gas 5 14

As a result, explosive range or explosive limit refers to the

composition of a gas-air mixture beyond which the mixture will not ignite and will instead
continue to burn.

24
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FLUE GAS ANALYSIS – ORSAT’S APPARATUS

40. How is the flue gas analysis carried out? Explain with neat diagram. Mention
the significance of such analysis (8) [Jul, May, Dec-2009, Dec-2012,]
41. Explain the flue gas analysis by orsat method with a suitable diagram (10)
[May-2017]
42. Explain the functioning of orsat apparatus (8) [Jan-2019]
43. With a neat diagram of Orsat apparatus, explain flue gas analysis (16) [Jan-
2018]
44. How is analysis of flue gas is done? Explain with neat diagram (8) [May-
2019]

The mixture of gases like CO2, O2, CO etc. coming out from the combustion chamber
is called flue gas.

Importance of Flue Gas Analysis:

(i) The analysis gives the idea of whether a combustion process is complete or
not.

(ii) The C and H present in a fuel undergo combustion forming CO2 and H2O
respectively. Any N present is not at all involved in the combustion. ie., the
products of combustion are CO2, H2O and N2.

(iii) If analysis of a flue gas indicates the presence of CO; it is suggestive of

incomplete combustion. (Wastage of heat is inferred)

(iv) If there is considerable amount of oxygen, it shows that there is excess supply
of O2 although combustion would have been complete.

Analysis: The flue gas analysis is carried out by using Orsat’s apparatus. The
analysis of flue gas generally deals with the determination of CO2, O2 and CO by absorbing
them in the respective solution of KOH, alkaline pyrogallol and ammonium cuprous
chloride.

Description of Orsat’s apparatus:

Orsat’s apparatus consists of a horizontal tube having 3-way stopcock at one end
and a water jacketed measuring burette at the other end. The horizontal tube is connected
to three different absorption bulbs for the absorption of CO2, O2 and CO respectively. The
lower end of the burette is connected to the levelling bottle by means of rubber tube.

The level of water in the levelling bottle (water reservoir) can be raised or lowered
by raising or lowering the water reservoir. By changing the level of water, the flue gas can
be moved into various parts of the apparatus during analysis.

25
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It is essential to follow the order of absorbing the gases- CO2 first; O2 second and
CO last. This is because the absorbent used for O2 (ie., alkaline pyrogallol) can also absorb
some amount of CO2 and the percentage of CO2 left would be less.

Bulb Reagent Function

I KOH Absorbs only CO2
II Alkaline pyrogallol Absorbs CO2 and O2
Ammoniacal cuprous chloride
III Absorbs CO2, O2 and CO
solution
Absorption of CO2

Flue gas is passed into the bulb I via its stopcock by raising the water reservoir.
CO2 present in the flue gas is absorbed by KOH. The gas is sent again and again to bulb I.
The decrease in the volume of the flue gas in the burette indicates the volume of CO 2 in
100 cc of the flue gas.

Absorption of O2

Stop-cock of bulb I is closed and stop cock of bulb -II is opened. The gas is again
sent into the absorption bulb -II, where O2 present in the flue gas is absorbed by alkaline
pyrogallol. The decrease in volume of the flue gas in the burette indicates the volume of
O2.

Absorption of CO

Now stop-cock of bulb II is closed and bulb III is opened. The remaining gas is sent
into the absorption bulb-III, where CO present in the flue gas is absorbed by ammoniacal
cuprous chloride. The decrease in volume of flue gas in the burette indicates the volume
of CO. The remaining gas in the burette after absorption of CO2, O2 and CO is taken as
nitrogen.
Significance or uses of flue gas analysis,

1. Flue gas analysis gives an idea about the complete or incomplete combustion process
2. If the flue gases contain considerable amount of CO, It indicates that incomplete
combustion is occurring and it also indicates that the short supply of air.
3. If the flue gases contain considerable amount of O2, it indicates that complete
combustion is occurring and also it indicates that the excess of O2 is supplied.

Precautions

1. Care must be taken in such a way that, the reagents in the absorption bulb 1,2 and
3 should be brought to the etched marked level one by one by raising and lowering
the reservoir bottle.

26
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2. All the air from the reservoir bottle is expelled to atmosphere by lifting thereservoir bottle.
3. It is essential that CO2, O2 and CO are absorbed in that order only
4. As the CO content in flue gas is very small, it should be measure quite carefully.

27
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