UNIT- IV

FUELS AND COMBUSTION

1. What is proximate analysis? Write its significance.

Proximate analysis of coal

In involves the determination of percentage of

1. Moisture Content
2. Volatile Matter
3. Ash content
4. Fixed Carbon in coal

i) Moisture content
 1 gm of air- dried coal sample in a crucible is heated at 105-110ºc in an electric
hot-air oven for 1 hour and then cooled in a dessicator.
 The loss in weight of sample is found out and the percentage of moisture is
calculated as follows.

loss in weight of the coal

% of moisture in coal = 100
Weight of air-dried coal

ii) Volatile matter:

 Coal sample from process 1 is covered with a lid, and it is heated at 950 ± 20ºC
for 7 minutes in an electric muffle furnace.
 The loss in weight of sample is found out and the percentage of volatile matter is
calculated as follows.

loss in weight of the coal

% of volatile matter in coal = 100
Weight of moisture free coal

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iii) Ash content:
 Now the residue is heated without lid at 700 ± 50 ºC for 30 minutes in a muffle
furnace then cooled and weighed.
 The loss in weight of sample is found out and the percentage of ash content is
calculated as follows.

Weight of ash formed

% of ash in coal = 100
Weight of dried coal

iv) Fixed carbon:

 It is obtained by subtracting the sum total of moisture, volatile and ash
from 100.
% of fixed carbon in coal = 100 - % of (Moisture content+ Volatile matter+ Ash
content)
Significance (Or) Importance of Proximate Analysis
a) Moisture
1. High percentage of moisture reduces the calorific value of coal.
2. It increases the transport cost.
3. More heat is to be supplied to the coal.
b) Volatile matter:
1. Volatile matters also lower the calorific value because it escapes out unburnt.
2. Coal with high percentage of volatile matter will burn with a long flame and high
smoke.
c) Ash content:
1. Ash is a useless component reduces the calorific value.
2. Ash causes obstruction to heat flow
3. Transporting, handling and storage cost increases.
4. It involves additional cost in ash disposal.
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d) Fixed carbon:
1. Fixed carbon determines the quality of coal.
2. High percentage of carbon content greater will be calorific value.

Ultimate analysis and its significance.

In ultimate analysis the percentage of carbon, hydrogen, nitrogen, sulphur and oxygen of
coal is determined.
a. Carbon and Hydrogen:
A small amount of coal sample is burnt completely with O2. The carbon and hydrogen are
converted into CO2 and H2O respectively,
C + O2 C O2
H2 + ½ O2 H2O
CO2 absorbed in KOH and H2O in CaCl2 tubes of known weights respectively.
2KOH + CO2 K2CO3 + H2O
CaCl2 + 7 H2O CaCl2. 7 H2O
Increase in weight of KOH tube and CaCl2 tube determines the % of C and H2 in the coal.
i) % of carbon:
C + O2 CO2
12 16 44 (by molecular weight)
Increase in weight of KOH tube 12
% of carbon taken= × ×100
Weight of coal sample taken 44

ii) % of hydrogen:
H2 + ½ O2 H2O
2 16 18 (by molecular weight)
Increase in weight of CaCl2 tube 2
% of hydrogen = × ×100
Weight of coal sample taken 18

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(b) Nitrogen content:
Coal sample + Con.H2SO4 + K2SO4 (catalyst)
kjeldahl’s flask. Nitrogen Ammonium
sulphate.

2N + 3H2 + H2SO4 (NH4) 2SO4

2NaOH 2 NH3
the liberated ammonia is absorbed in excess known volume of standard N/10 HCl.
NH3 + HCl NH4Cl
Then percentage of nitrogen as,
1.4×Volume of acid consumed×Normality
% of N 2in coal =
weight of coal sample

c) Sulphur
Coal sample (Calorimeter) S SO4. SO4(after extraction) + BaCl2
BaSO4

The BaSO4 precipitate is filtered, dried and weighed.

The sulphur % is calculated as

S + 2O2 SO42- + BaCl2 BaSO4

32 16 233 (by molecular weight)
32 ×Weight of BaSO4 obtained
% of sulphur in coal = 100
233  Weight of coal sample

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d) Ash :
Coal sample is heated without lid at 700 ± 50 ºC for 30 minutes then cooled and
weighed.
Weight of ash formed
% of ash in coal = 100
Weight of dried coal

e) Oxygen: % of oxygen in coal = 100 -% of (C+ H+ N+ S+ ash)

Significance (Or) Importance of Ultimate Analysis

a) Carbon and Hydrogen
 Higher the % of C and H, higher is its calorific value.
 The quality of coal is better
b) Nitrogen
 Nitrogen reduces the calorific value, and its presence is undesirable.
c) Sulphur
 Sulphur increases the calorific value, but produces SO2 and SO3 which are harmful
and corrosive.
d) Oxygen
 Lower the % of oxygen higher is its calorific value.
 On oxygen increase moisture also increases, and the calorific value is reduced

3. How will you manufacture metallurgical coke by Otto- Hofmann

method?
Otto- Hofmann method of coke manufacture:
Metallurgical Coke:
Definition:

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  When bituminous coal is heated strongly in absence of air, the volatile matter
escapes out and the mass become hard, strong, porous and coherent which is
called Metallurgical Coke.
Significance/Advantages:
 Increase the thermal efficiency by the regenerative system of heat economy.
 Recover the valuable by products like tar, ammonia, benzene etc.

Process:
 The oven has number of silica chambers.
 Each silica chamber is about 10 – 12 m long, 3 – 4 m height and 0.4 – 0.45 m wide.
 Each chamber has a door for charging and discharging coal at the top and bottom.
 Coal is introduced into the silica chamber and the chambers are closed.
 The chambers are heated to 12000C by burning preheated air and producer gas
mixture.
 The air and producer gases are preheated by passing through 2& 3 regenerators.
 Hot flue gases produced are passed through 1& 4 regenerators to raise the temp to
10000C.
 1 & 4 regenerators are being heated by hot flue gases. The 2&3 regenerators are
used for heating the incoming air and gas mixture.
 For economical heating, the direction of inlet gases and outlet gases are changed
frequently. This is known as the regenerative system of heat economy.
 Carbonization time is about 12 – 20 hours. Coke yield is 70%.

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Recovery of by-products:
i)Tar : The “Coal gas” is first passed through a tower in which ammonia is sprayed. Tar
is obtained
ii)Ammonia: Water is sprayed in the second tower, Ammonia (NH4OH) is
recovered.
iii)Naphthalene: In the 3rd tower cooled water is sprayed and naphthalene gets
condensed.
iv)Benzene: Petroleum is sprayed on the 4th tower, benzene is recovered.
v) Hydrogen Sulphide: , H2S is recovered by passing the gas through moist Fe2O3 .
Fe2O3 + 3H2S Fe2S3 +3H2O
Advantages of Hoffmann byproduct method:
 Valuable byproducts like Tar, NH3, Benzene etc., are removed
 The carbonization time is less
 Heating is done externally by producer gas.

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4. What is synthetic petrol? How is it manufactured by Bergius process?

Hydrogenation of coal (or) Synthetic Petrol:

Definition:
“The coal is heated with hydrogen to convert into gasoline. The preparation of liquid
fuels from solid coal is called Hydrogenation of coal or synthetic petrol”.

a. BERGIUS PROCESS (DIRECT METHOD)

 Powdered coal is mixed with heavy oil and catalyst (Tin or Ni oleate) and it is
converted into a paste form.
 The paste is pumped to a converter along with H2 gas.
 It is heated to 400 - 450°C under a pressure of 200-250 atm.

 The Polymerization reaction takes place with the help of the catalyst.
 In this process hydrogen combines with coal to form saturated higher
hydrocarbons.
 Saturated higher hydrocarbons undergo further decomposition at high
temperature to yield lower hydrocarbons.
 The mixture is lead into condenser where crude oil is obtained.

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 The crude oil is then fractionated to yield,
(i) Gasoline (ii) Middle oil (iii) Heavy oil
(ii) The middle oil is again hydrogenated to yield more gasoline.
(iii) The heavy oil is recycled with coal dust.
The yield of gasoline is about 60%.

5. Explain the following i) Knocking ii)Octane number iii) Cetane

number iv) Leaded petrol
i)Knocking
i) Definition:
 Knocking is a kind of explosion due to rapid pressure rise in an IC engine.
 It is expressed by Octane Number
ii)Causes of Knocking in S.I Engine (Spark Ignition or petrol engine).
 In petrol engine the ratio of gasoline+ air mixture is 1:17.
 It is ignited by electric spark and continues smooth combustion.
 But in some cases the rate of combustion will not be uniform due to unwanted
chemical constituents of gasoline.
 The gasoline+ air mixture ignited spontaneously produce an explosive sound known
as Knocking.
iii)Chemical structure of Knocking:
The knocking tendency decreases in the following oreder,
Straight Chain paraffins > Branched Chain paraffins > Cycloparaffins > Olefins
>aromatics.
iv)Anti knocking agents:
 Substances that reduces knocking property of the fuel are called anti-knocking
agents.
Ex: TEL, Aromatic phosphates
v)Improvements of antiknock characteristics (Octane Number)
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 The octane number of fuel can be improved by
i) Blending petrol of high octane number with petrol of low octane number.
ii) The addition of anti-knock agents like Tetra-Ethyl Lead.
iii) Now a day’s aromatic phosphate are used.

Octane number (OR) Octane Rating:

 It is used to express knocking characteristics of petrol.
 It is defined as ‘the percentage of iso-octane present in a mixture of iso-
octane and n-heptane’.
 Iso-octane has best antiknocking property

Leaded petrol( Antiknocking agent)

Definition:
 The petrol containing Tetra Ethyl Lead (TEL)(C2H5)4 Pb is called leaded petrol.
 It improves anti-knocking property of gasoline.
Mechanism:
 Knocking follows free radical mechanism, leading to a chain growth which results
in an explosion.
 Knowing will be stopped if the chain is terminated before growth.
 TEL decomposes to form ethyl free radicals which combines with growing chain
and stops the chain growth.
Disadvantages of Using TEL:
 TEL converts into metallic lead and lead oxide in petrol.

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  The lead is harmful to sparkplug and engine.
 To avoid this ethylene bromide is added which gives lead bromide during ignition.
Pb + CH2 Br PbBr2 + CH2=CH2.
 Even lead bromide creates pollution.
 So, nowadays Aromatic phosphates are added instead of TEL.

Diesel Oil:
Definition:
 It is a fraction obtained between 250- 3200 C during fractional distillation of
petroleum. It is a mixture of C15H32 to C18H38 hydrocarbons.
 The calorific value is about 11000 kcal/ Kg.
Causes of knocking in I.C Engine (Diesel Engine):
 In a diesel engine first air is alone compressed and this increases the temperature of
the cylinder to about 5000 C.
 Then oil is sprayed over heated air.
 This increases temperature and pressure.
 The expanding gas push the piston and power stroke begins.
 The combustion of a fuel in a diesel engine is not instantaneous and the time
between the injection of the fuel and its ignition is called Ignition Lag or Ignition
Delay.
 This delay leads to knocking in diesel engine.

Cetane number of diesel oil:

Definition:
 The cetane number is defined as ‘the percentage of hexa decane(cetane) present in
a mixture of hexa decane and α-methyl naphthalene”
.

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6. What are LPG & CNG? Discuss advantages of LPG over gaseous fuel
and CNG over LPG
1. Compressed Natural Gas (CNG):
Definition:
 When Natural gas is compressed at 3,000 or 3600 psi it is called Compressed
Natural Gas.
 When Natural gas is compressed at 20-150 psi it is called Compressed Natural Gas.
Constituents:
The main Constituent is methane
Constituents Percentage
1. Methane 88.5
2. Ethane 5.5
3. Propane 3.7
4. Butane 1.8
5. Pentane 0.5

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*Properties: 1. Cheap, Clean and environmental friendly fuel.
2. Vehicle pollution is less by CNG
3. Less expensive than petrol and diesel.
4. Ignition temperature is about 5500 C
5. Requires more air for ignition.
*Uses: As a Fuel in automobiles.
Advantages of CNG over LPG:
1. It produces less pollutant than LPG.
2. It is cheaper and cleaner than LPG
3. Does not evolve Sulphur and Nitrogen gas.
4. It mixes with air very easily.
5. Noise level is much less than diesel.
6. Octane rating is high and hence efficiency is more.
2. Liquified Petroleum Gas (LPG)
 LPG is obtained during Fractional distillation of Crude oil.
 It consists of propane and butane.
 It can be readily liqiufied under pressure.
Composition:
Main Composition is

Constituents Percentage
n- Butane 38.5%,
Iso-Butane 37%
Propane 24.5%

Calorific value : 25,000 Kcal/ m3

*Properties: 1.Cheap, Clean and environmental friendly fuel.

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*Uses: 1. As a Fuel in domestic and in industries. 2. It is also used as motor fuel.
Advantages:
1. It burns cleanly without any residue.
2. Calorific value is 7 times higher than coal gas and 3 times than natural
gas.
3. High thermal efficiency.
4. Less health hazard even incase of leakage.
5. Easy to manipulate
6. Need little care for maintanence
7. It is free from CO.
Disadvantage:
1. Leakage cannot be easily detected due to faint odour.
2. Octane value is low.
3. Handling must be under high pressure.

7. Write a note on power alcohol and biodiesel.

POWER ALCOHOL:
Definition:
 When ethyl alcohol is blended with petrol at a concentration of 5-10% it is
called Power alcohol.
 In other words absolute alcohol (100% ethyl alcohol) is also called power alcohol.
 When ethyl alcohol is blended with diesel it is called Ediesel.

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Manufacture:
There are two steps
Step I: Manufacture of ethyl alcohol:
 Fermentation of molasses (the residue after the crystallization of sugar) generates
alcohol. It yields about 20% alcohol.
C6H1206 YEAST 2C2H5OH + 2CO2
Glucose Ethyl alcohol
 The concentration can be further increased to 97.6% by fractional distillation.
 Above 97.6% it forms constant boiling mixture with water.
Step II: Conversion of ethyl alcohol into power alcohol:
For the use of IC engines 100% alcohol is prepared by removing water from
alcohol. It is done by
 Passing benzene over alcohol will leave absolute alcohol.
 Alcohol is distilled in the presence of dehydrating agents which holds the water.
Properties:
 Lower calorific values (7000 kcal/ Kg)
 High octane number.
 Good anti-knocking properties.
 10% more power than gasoline.
Uses: Very good fuel for motor.
Advantages:
 Cheaper than petrol.
 It absorbs moisture.
 Burns completely without any residues.

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Disadvantages:
 Calorific value is lower than petrol.
 Output power is less.
 It will lead to starting trouble due to high surface tension.
 It may lead to corrosion due to the formation of acetic acid.

Bio Diesel
 Vegetable oil comprises of 90-95% of triglycerides with small amount of
diglycerides, free fatty acids, phospholipids, etc.
 Triglycerides are ester of long chain fatty acids like stearic acid, palmitic acid.
 Viscosity and molecular weight of vegetable oil is three times higher than that of
diesel fuel.
Problems in using vegetable oils directly:
 High viscosity and low atomization leads to incomplete combustion.
 Oxidation and thermal polymerisation leads to deposit formation.
 High viscosity lead to misfire and ignition delay.
 Vegetable oil requires modification for diesel engine design.
Manufacture: Trans-esterification (OR) alcoholysis:
 Biodiesel is manufactured by the process known as Trans-esterification (OR)
alcoholysis.
 Alcoholysis is nothing but displacement of alcohol from an ester by another
alcohol.
 Vegetable oil (sunflower oil, palm oil etc) is treated with excess of methanol in
the presence of catalyst give mono ethyl ester of long chain fatty acids and
glycerine.
 Biodiesel is defined as mono- alkyl esters of long chain fatty acids derived from
vegetable oils.
 It is a pure fuel before blending with diesel fuel.

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Advantage:
 It is biodegradable.
 It can be prepared from renewable resources.
 Pollution less fuel.
 It can be produced from various types of vegetable oils.
 Best engine performance.
Disadvantages:
 Biodiesel gels in cold weather.
 Bio- materials are hygroscopic.
 It decreases the horse power of engine.
 It evolves 10% above NOx than petroleum.

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Gross calorific value (GCV) or High Calorific Value (HCV)
The gross calorific value is defined as“the total amount of heat evolved, when a
unit mass of the fuel is completely burnt and the products of combustion is cooled to
room temperature C”.
Gross calorific value calculated by Dulong’s formula
1   %O  
 8080  %C  34500  % H    2240  % S  kcal / kg p
100   8  

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

The net calorific value of fuel is defined as “the net amount of heat evolved, when
a unit mass of the fuel is completely burnt and the products of combustion are allowed
to escape”
NCV = GCV – Latent heat of condensation of water vapour
= GCV – Mass of hydrogen x 9 x Latent heat of condensation of water
= HCV - 9/100 H x 587 kcal/kg

8. With a neat diagram explain the analysis of Flue gas by ORSAT

apparatus and mention the precautions to be followed.
Flue gas analysis by using Orsat’s apparatus :
 It is the mixture of CO2, O2, CO, etc coming out from the combustion chamber is
called flue gases.
 The analysis gives an idea about the complete or incomplete combustion process.
Description of ORSAT apparatus:
 It is carried out by using Orsat’s apparatus.
 It consists of a horizontal tube.
 At one end, U – tube containing fused CaCl2 is connected through 3 – way stop
cock.
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  The other end is connected with burette.
 The burette is surrounded by a water-jacket and connected to a water reservoir by
rubber tube.
 The horizontal tube is connected with three absorption bulbs

I – bulb: It contains ‘potassium hydroxide’ solution, and it absorbs only CO2.

II – bulb: It contains ‘alkaline pyrogallol’ solution, and it absorbs CO2 andO2.
III – bulb: It contains ‘ammoniacal cuprous chloride’ solution, and it absorbs CO2, O2
and CO
Working:
 The 3 –way stop –cock is opened and the burette is filled with water.
 Now the flue gas is sucked into the burette for a volume of 100 cc.
 Then the 3-way stop cock is closed.

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i)Absorption of CO2
 The absorption bulb-I (KOH) is opened, the flue gas enters where CO2 is absorbed
by KOH.
 This process is repeated for complete absorption of CO2.
 The decrease in volume level indicates the volume of CO2 in the flue gas.

ii) Absorption of O2
 Stop-cock of bulb- I is closed and stop- cock of absorption bulb-II (‘alkaline
pyrogallol’) is opened, the flue gas enters where O2 is absorbed.
 The decrease in volume level indicates the volume of O 2.

iii) Absorption of CO:

 Stop-cock of bulb- II is closed and stop- cock of absorption bulb-III (‘ammoniacal
cuprous chloride’) is opened, the flue gas enters where CO is absorbed.
 The decrease in volume level indicates the volume of CO.
 The remaining gas in the burette after the absorption of CO2, O2 & CO is taken as
nitrogen.
Significance:
 This process gives an idea about complete or incomplete combustion process.
 If the flue gas consists of CO it indicates incomplete combustion process.
 If the flue gas consists of O2 it indicates complete combustion process.

Precautions:
 The reagents in the bulbs 1,2,3 should be brought to etched mark level one by one
by raising and lowering the reservoir bottle.
 CO2, O2 and CO are absorbed in that order only.
 As the CO content is very small it must be measured carefully.
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