Name:

Branch:

Roll No:

CY1104 – ENGINEERING CHEMISTRY

UNIT – 4 FUELS AND COMBUSTION

LECTURE PLAN

4.1) Introduction – Types of fuel – Comparison

4.2) Proximate and Ultimate analysis of coal

4.3) carbonization –Otto Hoffmann’s method of coke production

4.4) Fractional distillation of petroleum – Cracking

4.5) Synthetic petrol by Bergius process – Fischer Tropsch’s process

4.6) Bio diesel – Power alcohol

4.7) Knocking – octane number –cetane number

4.8) Natural gas - compressed natural gas (CNG) – LPG

4.9) Combustion –– GCV – NCV – Dulong’s formula

4.10) Flue gas analysis – Orsat method

4.11) Ignition Temperature – explosion range

1
 CY8151 – ENGINEERING CHEMISTRY
UNIT – 4 FUELS AND COMBUSTION

4.1-A) INTRODUCTION
Fuel is a carbonaceous material which on burning produces heat energy. The energy produced when
one unit mass of fuel is burnt is known as calorific value.

Requirements of a good fuel

1. It should be cheap and easily available.
2. The storage and transportation of the fuel should be safe and cheap.
3. It should not undergo spontaneous combustion.
4. It should have high calorific value.
5. The combustion should be easily controllable.
6. The combustion products should be non-toxic.
7. It should have low moisture content.

4.1-B) CLASSIFICATION OF FUEL

a) Classification based on occurrence:
1. Primary fuels: It occurs in nature as such. (e.g) Coal, petroleum, natural gas.
2. Secondary fuels: It is derived from primary fuels. (e.g) coke, gasoline, LPG
b) Classification based on the physical state:
1. Solid fuels (e.g) Coal, coke
2. Liquid fuels (e.g) gasoline, diesel
3. Gaseous fuels (e.g) CNG, LPG

2
4.1-C ) COMPARISON OF SOLID, LIQUID AND GASEOUS FUELS
S.No Property Solid fuels Liquid fuels Gaseous fuels
1 Calorific value Due to ash and Higher than Highest value
moisture content, solid fuels. than solid and
calorific value is low. liquid fuels.
2 Combustion Slow Quick Rapid

3 Control of combustion Not easy Easy Easy

4 Air requirement for burning High Low Low

5 Thermal efficiency Least Higher Highest

6 Applicability in IC engine No Yes Yes

7 Production cost Low High High

8 Handling cost More Less Lesser

9 Ignition temperature Highest Moderate Low

10 Pollution Highest Low Lowest

4.2) ANALYSIS OF COAL

When organic vegetation buried under the earth is subjected to high temperature and pressure over a
long period, coal is formed. Based on the carbon content, calorific value and colour, they are
classified as

Wood  peat  Lignite  Bituminous  Anthracite

The process of conversion of wood to Anthracite is known as ‘coalification’. During the process of
coalification, moisture, volatile impurities, H2, O2, S contents are decreasing while carbon, hardness,
calorific values are increasing.

The quality of the coal is determined by a) Proximate analysis b) Ultimate analysis

S.No Proximate analysis Ultimate analysis
1 It determines physical constituents It determines the chemical constituents like carbon,
like moisture, volatile, ash and fixed hydrogen, nitrogen, sulfur and oxygen contents in
carbon contents in coal. coal.
2 It gives approximate composition of It gives the exact composition of the constituents of
the constituents of the coal. coal.

3
 PROXIMATE ANALYSIS: - By proximate analysis, we can determine
a) Moisture content b) Volatile matter c) Ash content d) Fixed carbon
1 gm of powdered and air dried coal is taken in a crucible; the analysis is done as follows:
Moisture:
About 1 gm of powdered air-dried coal sample is taken in a crucible and is heated at 100 – 105oC in
an electric hot-air oven for 1 hour. The loss in weight of the sample is found out and the % of the
moisture is calculated from the respective formula.
Volatile matter:
After the analysis of moisture content , the crucible with the residual coal sample is covered with a
lid and is heated at 950 ± 20oC for 7 minutes in a muffle furnace. The loss in weight of the sample
is found out and the % of volatile matter is calculated from the respective formula.
Ash content:
After the analysis of volatile matter, the crucible with residual coal sample is heated without lid at
700 ± 50oC for 30 minutes in a muffle furnace. The loss in weight of the sample is found out and
the % of the ash content is calculated from the respective formula.
No Property Temp(oC) Duration Apparatus Formula
1 Moisture 100 - 105 1 hr Hot air oven % = Loss in wt. of coal x 100
Wt. of air dried coal
2 Volatile 950 7 mins Muffle % = Loss in wt. of coal x 100
impurity furnace Wt. of moisture free coal
3 Ash 750 ½ hr Muffle % = Wt of ash formed x 100
furnace Wt. of dried coal
4 Fixed carbon - - - % = 100 – % of ( Moisture +
Volatile impurity + Ash content)
Significance of proximate analysis:
1. Moisture : Moisture should be low. Otherwise it
i) Reduces the calorific value ii) Transportation is difficult iii) Produces smoke
iv) Most of the supplied energy will be wasted for evaporation.
2. Volatile matter: Should be low. Otherwise it
i) Reduces calorific value ii) Produces sooty and smoky flame
iii) Coking is not possible iv) Toxic gases will be evolved.
3. Ash content: Should be low. Otherwise it
i) Reduces calorific value ii) Forms clinkers, disturbing the oxygen supply.
iii) Disposal will cause air and land pollution.
4. Carbon: Should be high, for
i) High calorific value ii) For designing furnace
iii) Classification of coal is based on carbon content.
4
ULTIMATE ANALYSIS:

By this analysis, % of C , H , S , N , Ash and Oxygen in the coal can be determined.

a) Carbon : A known amount ( m gram) of coal sample is burnt in presence of oxygen. The carbon
in the coal reacts with oxygen to form carbon-di-oxide which is absorbed by a KOH tube. Weight
of the KOH tube before and after absorption is noted.

Reactions: C + O2  CO2
CO2 + KOH  K2CO3 + H2O
Calculation: 1) Wt of the sample = m
2) Increase in wt. of KOH tube = x
3) So, wt. of CO2 formed = x
C + O2  CO2
12g 44g
44g of CO2 is having 12g of Carbon

x g of CO2 = 12 X x g of carbon
44
m gram of coal sample contains = 12 X x g of carbon
44
Therefore, % of carbon = 12 X x X 100
44 m
b) Hydrogen : A known amount ( m g) of coal sample is burnt in presence of oxygen. The
Hydrogen in the coal reacts with oxygen to form H2O which is absorbed by a CaCl2 tube. Weight
of the CaCl2 tube before and after absorption is noted.

Reactions: H2 + ½ O2  H2O
7H2O + CaCl2  CaCl2 . 7H2O
Calculation: 1) Wt of the sample = m
2) Increase in wt. of CaCl2 tube = y
3) So, wt. of H2O formed = y
H2 + ½ O2  H2O
2g 18g
18g of H2O is having 2g of Hydrogen

y g of H2O = 2 X y g of Hydrogen
18

m gram of coal sample contains = 2 X y g of hydrogen

18

Therefore, % of Hydrogen = 2 X y X 100

18 m 5
c) Sulphur: m gram of sample is burnt to convert its sulphur to sulphate. Its extract is treated with
BaCl2. The precipitate BaSO4 formed is dried and weighed. (z gram)

S + 2O2  SO42- SO42- + BaCl2  BaSO4↓

32 233
233 g of BaSO4 is having 32g of Sulphur.

z g of BaSO4 = 32 X z g of sulphur
233
m gram of coal sample contains = 32 X z g of sulphur
233
Therefore, % of sulphur = 32 X z X 100
233 m
d) Nitrogen ( Kjeldahl’s method)
m gram of sample is heated with con. H2SO4 and catalyst K2SO4 in a long necked Kjeldahl’s flask.
Ammonium sulphate is formed and a clear solution is obtained.
On adding NaOH, it evolves NH3. NH3 is absorbed by a known volume of (V1) 0.1N HCl. It is
back titrated for unconsumed HCl (V2). So, HCl consumed is (V1 - V2)ml.
2N + 3H2 + H2SO4  (NH4)2SO4 + Clear solution
(NH4)2SO4 + 2NaOH  2NH3 + Na2SO4 + 2H2O
Calculation:
1000ml of 1N HCl ≡ 14g of N2
(V1 - V2)ml of 0.1N HCl ≡ 14 X (V1 - V2) X 0.1
1000 X 1
This is for m gram of sample.
Therefore , N2 % = ≡ 14 X (V1 - V2) X 0.1 X 100
1000 X 1 X m
e) Ash: Similar to proximate analysis
f) Oxygen: O2 % = 100 - % ( C + H + N + S + Ash)
Significance of Ultimate analysis:
1. Carbon: Should be high, for
i) High calorific value ii) Designing furnace and combustion chamber can be done with the
knowledge of carbon content iii) Classification of coal is based on carbon content.
2. Hydrogen: Though Hydrogen % increases the calorific value, its tendency to form moisture
creates problem. So, it should be low.
3. Nitrogen: It is not contributing to calorific value. So, its presence is not preferred.
4.Sulphur: It causes toxic byproducts and sooty, smoky flames like SO2 , SO3. So, it is undesirable.
5. Ash content: Should be low. Otherwise it
i) Reduces calorific value ii) Forms clinkers, disturbing the oxygen supply.
iii) Disposal will cause air and land pollution.
6. Oxygen: Lower the % of oxygen, higher its calorific value. It increases the moisture content. 6
4.3) SECONDARY SOLID FUEL - COKE
On heating the coal strongly in absence of air, it is converted into coke. This process is known as
carbonization. If the coal forms soft coke, it is caking coal. If it forms hard coke, it is coking coal.
Always coking coal is preferred.
Depending upon the temperature, two types of carbonization is possible.
a) Low temperature carbonization –LTC b) High temp. Carbonization - HTC
No. LTC HTC
1 Temp. at 500 – 700oC 900 – 1200oC
2 Yield of coke is 75 – 85% 65 – 75% of coke
3 Soft coke is obtained Hard metallurgical coke is obtained.
4 Strength of coke is low High
5 Used for domestic purpose Used for metallurgy
6 Volatile matter is 5- 15% 1 -3 %
7 Low calorific value High calorific value

Requirement of Metallurgical coke:

1. Purity: Should be high. The impurities like moisture, ash, sulphur, Phosphorous
may contaminate the heating material and reduce the calorific value.
2. Porosity: Should be high for easy oxygen movement.
3. Calorific value: Should be high.
4. Combustibility: Should be high for easy burning.
5. Cost should be low.
6. Strength: Should be high to withstand load.
7. Reactivity: Should be low to avoid any contamination.
OTTO HOFFMANN’S BY-PRODUCT METHOD – COKE MANUFACTURE
Objectives and advantages:
1. By products recovery (Tar, NH3 , Naphthalene, Benzene, H2S)
2. Less time consumption ( 12 -20 Hrs)
3. Increasing thermal efficiency by using the producer gas and flue gas.
Design of chamber and working:
1. It contains a number of silica chambers of Length: Height: Width = 12: 4: 0.4 m.
2. Coal is introduced into the chamber from the top and heated at 1200oC , by burning the preheated
air and producer gas. They are heated by sending them through 2nd and 3rd hot regenerators.
3. During combustion, coal produces flue gas. This hot flue gas is sent through 1st and 4th
regenerators to raise the temperature to 1000oC. 7
 4. For economical heating, the direction of inlet gases and flue gases are changed
frequently. This recycling system is called ‘ heat economical regenerative system’.
5. It takes 12 -20 hours with 70% yield.
6. Once the carbonization is completed, the flue gases are sent to by-product recovery chamber.
No By product Recovered by
1 Tar By spraying Liquid Ammonia to dissolve tar. NH3 is again
recovered by the heating the solution.
2 Ammonia By spraying water. Here ammonia is converted as ammonium
hydroxide.
3 Naphthalene By spraying cold water.
4 Benzene By spraying petroleum
5 Hydrogen sulphide By moist Fe2O3 purifier.
Diagram:

4.4-A) PRIMARY LIQUID FUELS:- PETROLEUM

Petroleum may be of three types:
1. Paraffinic based – straight chain hydrocarbons
2. Naphthenic based – Cyclo paraffins and aromatic
3. Mixed base – both paraffinic and naphthenic
The average composition of crude oil is as follows:
Constituents Percentage (%)
C 80 – 87
H 11 – 15
S 0.1 – 3.5
N+O 0.1 – 0.5
8
Refining of crude oil/ petroleum:
Removal of impurities, water content, sulphur and separating the crude oil into different fractions is
called refining of crude oil. There are three steps.
a) Water removal- Crude oil is fed between two charged electrodes. Here, colloidal water droplets
are combining to form large drops which can be easily removed. This is known as ‘Cottrell’s
process”.
b) Sulphur is removed by adding copper oxide. It is separated as copper sulphide.
c) Fractional distillation: Purified crude oil is heated to 400oC and the vapours are passed at the
bottom of fractionating column. The column has a number of horizontal stainless steel trays. On
passing the vapours through the trays, they get condensed and collected according to their boiling
points. The fractions are :
No Name Boiling point oC C- atoms Uses
1 Gases Below 30 C1 - C4 As LPG
2 Petroleum ether 30-70 C5 - C7 Solvent
3 Petrol 40-120 C5 - C9 Fuel in automobiles
4 Spirit 120-180 C9 - C10 Solvent , Paint industry ,dry cleaning
5 Kerosene 180-250 C10 - C16 Fuel for stoves, jet engines
6 Diesel 250-320 C15 - C18 Diesel engine fuel
7 Heavy oil 320 - 400 C17 - C30 Further cracking
8 Lubricating oil + Above 400 Greater Lubricants, Laying roads.
grease + wax + tar than C30

4.4-B) CRACKING:
Conversion of high boiling point, higher molecular weight hydrocarbons into low boiling point, low
molecular weight hydrocarbons is known as ‘cracking’.
Two types of cracking:
a) Thermal cracking – Cracking is done at higher temperature and pressure without any catalyst.
There are two sub-types of thermal cracking.
a) Liquid phase thermal cracking b) vapour phase thermal cracking 9
b) Catalytic cracking – Cracking is carried out by using catalysts (Eg) Clay, alumina, Aluminium
silicate . There are two sub-types of catalytic cracking.
a) Fixed bed catalytic cracking b) Moving bed catalytic cracking
Advantages of catalytic cracking over thermal cracking:

1. Yield of petrol is higher.

2. Quality is superior.
3. Production cost is less as high temperature and pressure is not required.
4. No external fuel is required for cracking. Heat is obtained from burning the carbon deposited on
the catalyst.
5. Process is easily controllable.
6. Low sulphur content in the product.
7. % of gummy products are low.
4.5-A ) SECONDARY LIQUID FUELS (E.G) SYNTHETIC PETROL- BERGIUS METHOD

Coal contains 4.5% hydrogen whereas 18% for petroleum. So, coal has to be

hydrogenated to form petroleum. This is called ‘ hydrogenation of coal’.

Bergius method (Direct method):

1. Coal powder + catalyst (Tin oleate) + Heavy oil are mixed together to form a paste.

2. Hydrogen gas is pumped to the way of paste to the converter.

3. Converter is heated at 200 -250 atmospheric pressure and 400 – 450oC temp.

4. Here, H2 combined with coal to form saturated hydrocarbons and they undergo decomposition to

lower hydrocarbons. The mixture is led to a condenser where the crude oil is obtained. 10
 5. Crude oil on fractionation yields a) gasoline b) middle oil c) Heavy oil

6. Middle oil is converted to gasoline by further hydrogenation and heavy oil is recycled for paste.

7. The yield is about 60% of the coal used.

FLOWCHART FOR BERGIUS PROCESS

Heavy oil Coal powder Catalyst (Tin oleate)

Paste

Hydrogen

Convertor

450oC / 250 atm

Gases

Condenser

Crude oil

Fractionating column

Heavy oil Middle oil Gasoline

Recycled for paste making Cracked to form gasoline

11
4.5-B ) SYNTHETIC PETROL BY FISCHER TROPSCH’S METHOD (Indirect Method)

1. The coal is converted to coke. Red hot steam at 1200oC is passed over the coke to produce water
gas.
C + H2O ( 1200oC)  CO + H2
Coke steam water gas

2. The water gas is mixed with hydrogen and sent through purifiers. Fe2O3 pack purifier removed
H2S and (Fe2O3 + Na2CO3) pack purifier removes organic sulphur impurities.

3. Then, the pure gas is subjected to 5 – 25 atm and 200-300oC in a converter.

4. A catalytic bed of Cobalt + Thoria + Magnesia + Kieselguhr earth of 100 : 5: 8: 200) parts
ratio is used in the converter.

5. In converter, a mixture of saturated and un saturated hydrocarbons are produced.

nCO + 2n H2  CnH2n + n H2O ( Unsaturated hydrocarbons)

nCO + (2n+1) H2  CnH2n+2 + nH2O ( Saturated hydrocarbons)

6. The gas is condensed to crude oil . It is cracked to obtain more gasoline.

12
4.6-A) BIODIESEL
Biodiesel is defined as the alkyl esters of long chain fatty acids. It is derived from vegetable fats
and oils. The biodiesels are named so as they are derived from vegetable source.
The vegetable oil cannot be used directly as a fuel because:
a) As the viscosity of vegetable oils are high, the combustion may not be complete.
b) On oxidation, they cause unwanted deposit formation.
c) Their high viscosity causes ignition delay.
d) It needs modification of conventional diesel engine design.
These problems are overcome by reducing the viscosity of the vegetable oils by trans-esterification
or alcoholysis.
Alcoholysis is the displacement of alcohol from an ester by another alcohol.
Manufacture of biodiesel
Biodiesel is produced from oils and fats by trans-esterification. It is a reaction of one mole of fats
and oils with three moles of alcohol to form esters and glycerol.
This trans-esterification can be catalysed by bases (NaOH, KOH) or acids (H2SO4) or by enzymes
(lipase) but the base catalysts are the most efficient.
The methyl-esters of fatty acids thus formed are known as biodiesel. Biodiesel can be blended with
petroleum diesel.
For production of biodiesel, methanol is favored due to its fast reactivity.

Advantages of biodiesel
1. Biodiesel is biodegradable
2. It is prepared from renewable sources
3. The gaseous pollutants are less when compared to conventional fuel
4. Less smoke emission
5. High flash point (148oC) compared to petrol (52oC)
6. High cetane number
7. It operates in compression ignition engine with no need of engine modification. 13
4.6-B) POWER ALCOHOL

Absolute alcohol (100% alcohol) is known as power alcohol. They are used in internal combustion

(IC) engine. When 90% gasoline is added with 10% ethanol, it is known as gasohol.

Manufacture of power alcohol

Step 1: Manufacture of ethyl alcohol

The residue left after crystallization of sugar is known as molasses. The fermentation of molasses

with yeast generates 20% alcohol. The molasses contains 50 – 60% sucrose. At 30oC and pH of 4 –

5 the enzyme invertase converts the sucrose into glucose and fructose. They are further converted

into ethanol by the enzyme zymase within the time period of 36 – 38 hours.

Invertase Zymase
C12H22O11 + H2O C6H12O6 + C6H12O6 4C2H5OH + 4CO2
Sucrose Glucose Fructose Ethanol

The fractional distillation of alcohol yields rectified spirit of 97.6%. The concentration of alcohol

cannot be increased by distillation above 97.6%.

Step 2: Conversion of ethyl alcohol into power alcohol

The absolute alcohol (power alcohol (or) 100% alcohol) is prepared by removing last traces of

water from rectified spirit. It is done by two methods.

a) Distillation with benzene

b) Distillation with a dehydrating agent

Advantages
1. High octane number

2. Good anti-knocking property

3. High compression ration

4. Less starting trouble

5. It generates 10x more power than the gasoline of same quantity

Disadvantages
1. Low calorific value

2. It is oxidized to organic acids which causes corrosion. 14

4.7-A) KNOCKING AND ITS MECHANISM:
1. The noisy explosion due to sudden rise in pressure inside the engines is known as knocking. It is
common in petrol and diesel engine.
2. In petrol engine, petrol and air are sent simultaneously in 1:17 ratio. Using a spark plug, a spark
is introduced to burn the fuel mixture. It vapourises and increases the pressure. This causes
pushing down of piston in cylinder. But, if the petrol contains impurities, they will vaporize earlier
and cause ‘premature combustion’. So, suddenly it creates a rapid pressure rise. So, the piston is
pushed down suddenly to cause noisy explosion. This is called the ‘knocking’ process.
3. Knocking in petrol engine is referred by ‘ octane number’.
4. Octane number is defined as the percentage of iso-octane present in a mixture of iso-octane and
n-heptane.
CH3 - (CH2)5 – CH3
n-heptane (octane number=0)

5. The knocking property is based on chemical structure.

Straight chain alkane > Branched alkanes > Cyclic alkanes > alkene> aromatics
6. Reduction of knocking:
a) By adding anti-knocking agents (eg)Tetra Ethyl Lead (TEL),aromatic phosphates
b) By blending low octane numbered fuel with high octane numbered fuel.
c) By proper cracking
7. Mechanism of anti-knocking :
a) In petrol knocking, free radical mechanism is taking place. The straight chains present in the
petrol are forming free radicals in propagation step. If we terminate the free radical mechanism,
then the knocking will be prevented.
b) As an anti-knocking agent , TEL (C2H5)4Pb is added to petrol.
c) TEL forms ethyl radicals (C2H5.) and combine with long chain radicals and terminate the
reaction.
d) But the lead and lead oxide with be deposited over the spark plug. To avoid this deposition,
ethylene bromide is added. It forms lead bromide which causes severe air pollution.
Pb + CH2Br – CH2Br  PbBr2↑ + C2H4

So, instead of using TEL, we are using aromatic phosphates. 15

4.7-B) KNOCKING IN DIESEL ENGINE:

1. Diesel oil is a fraction obtained between 250 – 320o C during fractional distillation of petroleum.

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

2. In diesel (Compression) engine, the diesel and air are not sent at the same time.

3. The compressed air is sent first. The compression raises the temperature around 500oC. Now, the

diesel oil is sprayed. This further increases the temperature and pressure. The expanding gases push

the piston and power stroke begins.

4. The time difference between the diesel injection and its ignition is known as ‘ignition lag’.

5. If diesel contains any impurity, the ignition will be delayed. This delayed ignition lag increases

the accumulation of vapour, hence increases the pressure rapidly and knocking occurs.

6. Knocking of diesel engine is referred by ‘ cetane number’.

7. Cetane number is defined as ‘ the % of cetane present in a mixture of cetane and α – methyl

naphthalene.

8. The cetane number decreases as

Straight chain alkane > Cyclo alkane > Alkene > Branched alkane > Aromatics
9. To increase the cetane number, we can add additives called ‘dopes’.
(eg) Iso amyl nitrate , ethyl nitrate
DIFFERENCES BETWEEN PETROL (GASOLINE) AND DIESEL
S.No Petrol Diesel
1 Fuel for SI engines Fuel for CI engine
2 Low boiling fraction High boiling fraction
3 Liberates more pollutants Less pollutants
4 Knocking is due to premature Knocking is due to delayed ignition lag.
ignition.
5 Knocking is referred by octane By cetane number
number.
6 Knocking is prevented by anti- Knocking is prevented by dopes ( Iso
knocking agents (eg) TEL amyl nitrate)
16
4.8) GASEOUS FUELS:
1. NATURAL GAS:
Natural gas is always found above the oil in the oil wells. It is also called Marsh gas. It consists of
methane and other saturated hydrocarbons.
Composition :
Constituents %
Methane 88.5
Ethane 5.5
Propane 4
Butane 1.5
Pentane 0.5
Calorific value 12,000 – 14,000 kcal/m3
If natural gas contains lower hydrocarbon like methane and ethane, it is called as lean or dry gas.
If it contains higher hydrocarbons like propane and butane also, it is called as rich or wet gas.
Uses:
1. It is used as a domestic and industrial fuel.
2. It is used as a raw material for the production of carbon black and hydrogen.
3. It is used for electricity generation in fuel cells.
2. CNG - COMPRESSED NATURAL GAS
When Natural gas is compressed it forms CNG. It is stored in a tank at 3500 psi (Pounds per square
inch). It can be liquefied as LNG (Liquefied Natural gas) at around 20 – 150 psi.
Composition :
Constituents %
Methane 88.5
Ethane 5.5
Propane 4
Butane 1.5
Pentane 0.5
Calorific value 12,000 – 14,000 kcal/m3
Properties and Advantages:
1. CNG is the cheapest, cleanest and least eco-friendly alternative fuel.
2. It is cheaper than petrol and diesel.
3. CNG has more thermal efficiency because of high octane rating.
4. It emits lesser pollutants like carbon monoxide and hydrocarbon than petrol.
Pollutant Petrol vehicle CNG vehicle
CO ( g / km) 0.92 0.05
Hydrocarbons (g / km) 0.36 0.24
5. It is used to run automobiles also.
6. Noise level is much less than diesel. 17
3. LPG – LIQUEFIED PETROLEUM GAS
Fractional distillation of petroleum results in various product. One such product is LPG. It is easily
liquefied under pressure and stored, transported in cylinders.
Composition:
n-Butane 38.5%
Iso butane 37%
Propane 24.5%
Calorific Vale 25000 kcal/m3
Advantages of LPG over other fuels:
1. LPG produces no smoke, no ash.
2. LPG has high calorific value. Its calorific value is 7 times higher than coal gas and 3 times higher
than natural gas.
3. It is easy to store and transport LPG.
4. The combustion of LPG can be easily controlled.
5. LPG is used in domestic applications, industries and automobiles.
6. It is free from CO. So, it is less hazardous.
Disadvantages:
1. LPG is almost odorless. So, leakage detection is difficult. To avoid this, thio-alcohols must be
added to it.
2. It has low octane value.
3. High pressure is maintained during handling and filling of LPG.
4. It is suitable only for the engines working under high compression ratio.
4.9) COMBUSTION – GCV & NCV
Combustion is an exothermic, rapid , oxidation process during which the fuel is burnt completely to
produce heat energy. The amount of heat produced when one unit mass of fuel is burnt completely
is known as calorific value.
The units of calorific value are Calorie , British Thermal Unit, Centigrade Heat unit
Calorie: Amount of heat required to increase the temperature of 1g of water through 1oC.
Types of Calorific Value:
a) Gross calorific value : The amount of heat liberated when one unit mass of fuel is burnt
completely and the combustion products are cooled to room temperature. It is otherwise known as
Higher calorific value (GCV / HCV)
b) Net Calorific value: The amount of heat liberated when one unit mass of fuel is burnt
completely and the combustion products are allowed to escape. It is otherwise known as Lower
calorific value (NCV / LCV). 18
DULONG’S FORMULA:
GCV = 1 { 8080C + 34500 [H – O ] + 2240 S } Kcal / Kg
100 8

NCV = GCV - ( 0.09H x 587 ) Kcal / Kg

Problem:
1. Calculate the gross and net calorific values of a coal sample having the following
composition. C = 80%, H = 7%, O = 3%, S = 3.5%, N = 2.5% and ash = 4.4%.
Formula for GCV:

GCV = 1 { 8080C + 34500 [H – O ] + 2240 S } Kcal / Kg

100 8

GCV = 1 { 8080 (80) + 34500 [7 – 3 ] + 2240 (3.5) } Kcal / Kg

100 8

GCV = 8828.0 Kcal / Kg.

Formula for NCV:
NCV = GCV - ( 0.09H x 587 ) Kcal / Kg
NCV = (8828) - ( 0.09[7] x 587 ) Kcal / Kg
NCV = 8458.2 Kcal / Kg.

2. Calculate the gross and net calorific values of a coal sample having the following
composition. C = 85%, H = 8%, S = 1%, N = 2% and ash = 4%.
Formula for GCV:
GCV = 1 { 8080C + 34500 [H – O ] + 2240 S } Kcal / Kg
100 8

GCV = 1 { 8080 (85) + 34500 [8 – 0 ] + 2240 (1) } Kcal / Kg

100 8

GCV = 9650.4 Kcal / Kg.

Formula for NCV:
NCV = GCV - ( 0.09H x 587 ) Kcal / Kg
NCV = (9650.4) - ( 0.09[8] x 587 ) Kcal / Kg
NCV = 9227.8 Kcal / Kg.
19
4.10) FLUE GAS ANALYSIS – ORSAT METHOD:

1. The mixture of gases coming from the combustion chamber is called flue gas. It may contain

gases like CO2 , O2 , CO.

2. Significance and principle of flue gas analysis:

The analysis of the flue gas gives idea about the nature of combustion.

a) If it contains considerable amount of CO2 , the combustion process is quite okay. No need of

alterations in the combustion setup.

b) If it contains considerable amount of O2, it shows the complete combustion is taking place and

no need of extra oxygen supply. It is the time to cut the air supply.

c) If it contains considerable amount of CO, it shows the incomplete combustion and need of

oxygen supply.

3. Construction of ORSAT apparatus:

a) Orsat apparatus contains a horizontal tube(with a 3way stop cock) which is

connected to a U-tube at one end and graduated burette at another end. The burette is connected

with a water reservoir . By adjusting the height of the reservoir, we can adjust the water level in the

burette. The burette is covered with a water jacket to maintain the temperature of gases constant.

b) In between the u-tube & burette, 3 bulbs (with stopper) are connected.

Bulb Chemicals present To absorb

Bulb – 1 KOH CO2

Bulb – 2 Alkaline pyrogallol O2 and CO2

Bulb – 3 Ammoniacal Cuprous chloride CO, O2 and CO2

U tube Anhydrous CaCl2 Moisture

4. Working of Orsat apparatus:

Step -1: The burette is filled with water to expel the gases to the atmosphere. Then flue gas is sent

through U-tube. The volume of the flue gas is adjusted to 100cc by adjusting the reservoir. The

3 way stop cock is closed.

20
Step – 2: By opening the stopper in bulb-1 and sending the gases, the bulb-1 absorbs CO2. The

process is repeated several times to ascertain the complete absorption of CO2. The decrease in the

burette reading indicates the amount of CO2. Stopper cock 1 is closed.

Step – 3: By opening the stopper in bulb-2 and sending the gases, the bulb-2 absorbs O2. The

process is repeated several times to ascertain the complete absorption of O2. The decrease in the

burette reading indicates the amount of O2. Stopper cock 2 is closed.

Step – 4: By opening the stopper in bulb-3 and sending the gases, the bulb-3 absorbs CO. The

process is repeated several times to ascertain the complete absorption of CO. The decrease in the

burette reading indicates the amount of CO.

The remaining gas is taken as Nitrogen.

5. Precautions:

a) The order of analysis i.e CO2, O2 , CO should not be changed.

b) CO is in very small quantity. So, its estimation needs special care.

c) Before the analysis, all the air from the burette must be thoroughly expelled.

6. Diagram:

21
4.11-A) IGNITION TEMPERATURE
The lowest temperature to which the fuel must be heated for its smooth burning is known as
ignition temperature. In case of liquid fuels, ignition temperature is known as flash point.
Examples
S.No Type of fuel Ignition temperature (oC)
1 Solid coal 300
2 Liquid fuels 200 – 450
3 Gaseous fuels 800
The minimum temperature at which the fuel catches fire spontaneously without any external
heating is known as Spontaneous Ignition Temperature (SIT).
Pulvarised coal, oil rags, cotton wastes get oxidized slowly. If the heat evolved is unable to escape,
the temperature in the system goes on increasing and when SIT is reached, the system catches fire
on its own.
Significance of SIT:
A low SIT value indicates the ready ignition of the fuel and also means a fire hazard.

4.11-B)EXPLOSIVE RANGE (LIMITS OF INFLAMMABILITY)

For a fuel to burn, it should be mixed with air in proper ratio.
The fuel should be present in the fuel – air mixture in a particular range.
The gaseous fuels have two extreme limits in the mixture – a) Upper limit b) Lower limit
The range covered by these two extreme (Upper and lower) limits are known as explosive range or
limits of inflammability.
Significance:
For continuous burning, the amount of fuel present in fuel – air mixture should not go below the
lower limit or above the upper limit.
For example, the explosive range of petrol is 2 – 4.5. This means, when the concentration of petrol
vapour in petro-air mixture is between 2 – 4.5 by volume, the mixture will burn on ignition. When
it is below 2% or above 4.5% by volume, the burning will not be proper.
Example:
S.No Fuel Explosive range %
1 Hydrogen 4 – 75
2 Carbon monoxide 13 – 74
3 Acetylene 3 – 80
4 Natural gas 5 – 14
22