Engineering Chemistry Unit -4 Part-II

Unit -4
[Fuels: Fuels and Combustion: Definition, Classification, Characteristics of a good fuel, Calorific Values,
Gross & Net calorific value, Determination of calorific value by Bomb Calorimeter, Theoretical calculation of
calorific value by Dulong’s method, Ranking of Coal, Analysis of coal by Proximate and Ultimate analysis
method, Numerical problems, Chemistry of Biogas production from organic waste materials and their
environmental impact on society.]

Fuel Analysis [Part II ]

Fuel is a combustible substance which during combustion gives large amount of heat that can be used
economically for domestic and industrial purpose.
For e.g. Coke, charcoal, petroleum, diesel, kerosene oil etc.
Classification of Fuels:
These can be classified on the basis of their (i) Occurrence and (ii) Physical state
(i) On the basis of occurrence they are of two types:
a) Primary Fuels: Fuels which occur in nature as such are called primary fuels or natural fuels. For e.g.,
wood, peat, coal, petroleum, and natural gas.
b) Secondary Fuels: The fuels which are derived from the primary fuels by further chemical processing are
called secondary fuels or artificial fuels. For e.g., coke, charcoal, kerosene, coal gas, producer gas etc.
(ii) On the basis of physical state they are classified as:
a) Solid Fuels: For e.g., Wood, coke, charcoal etc.
b) Liquid Fuels: For e.g. Crude oil, petrol, diesel etc.
c) Gaseous Fuels: For e.g., Natural gas, LPG, coal gas, biogas, CNG etc.

Characteristics of a Good Fuel:

(i) High Calorific value
(ii) Ignition Temperature: A good fuel should have moderate ignition temperature.
(iii) Moisture content: Should be low.
(iv) Ash content: Should be low.
(v) Rate of combustion: It should be moderate.
(vi) Cheap and readily available.
(vii) Free from objectionable substances: Like smoke, H2S, CO, SO2 etc.
(viii) Low storage cost and conveniently transportable.

Calorific Value
• It is defined as the total quantity of heat liberated when a unit mass of a fuel is burnt completely.
• A good fuel should have high calorific value i.e. it should produce large amount of heat on burning.
• The quantity of heat can be measured in the following units:

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(i) Calorie 1 calorie = 4.187 Joules

(ii) Kilo Calorie 1 k cal = 1000 cal

a) Higher or Gross Calorific Value (HCV or GCV) :-

It is total quantity of heat generated when a unit quantity of fuel is completely burnt in
excess supply of oxygen and the products of combustion are cooled down at room
temperature.
b) Lower or Net Calorific Value (LCV or NCV) :-
It is total quantity of heat generated when a unit quantity of fuel is completely burnt in excess supply of
oxygen and the products of combustion are allowed to escape.
NCV = GCV - 0.09H x 587 cal/g

NCV = HCV - Latent heat of water vapors formed during burning

Latent heat of steam is 587 cal/g.

H2 + ½ O2 H2 O
2gm 18 gm

2 gm hydrogen gives 18 gm water on combustion.

Therefore, 1 gm hydrogen gives 9 gm water on combustion.
Since 1 part by mass of hydrogen gives 9 parts by mass of water.

NCV= GCV - weight of hydrogen x 9 x Latent heat of water vapors

Let H is the percentage of hydrogen in the fuel.

Amount of water produced by burning unit mass of fuel=9H/100 g

Latent heat of steam=587cal/g

Q. Explain when will the value od GCV=NCV?
NCV = GCV - 9H/100 x 587 Ans. If the % of hydrogen is zero.
%H = 0
= GCV - 0.09H x 587 cal/g NCV = GCV - 0.09H x 587 cal/g
NCV = GCV

Determination of the Calorific value

It is used to determine the solid and non-volatile liquid fuel.
Principle:
▪ A known amount of the fuel is burnt in excess of oxygen
▪ Heat liberated is transferred to a known amount of water.
▪ The calorific value of the fuel is then determined by applying the principle of calorimetery i.e.
Heat gained = Heat lost
Construction of Bomb Calorimeter:

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▪ It consists of a strong cylindrical stainless steel bomb in which combustion of the fuel takes place.
▪ The bomb has a lid which is screwed to the body of the bomb to make a perfect gas tight seal.
▪ The lid has two stainless steel electrodes and an oxygen inlet valve (See Figure).
▪ The bomb is placed in a copper calorimeter surrounded by air and water jacket (which prevents heat loss
due to radiation).
▪ An electrically operated stirrer and Beckmann’s thermometer (which measures bath of a degree) is
placed in the water jacket to maintain uniform distribution of heat and measure the increase in
temperature respectively.

Working -
▪ The small amount of substance under investigation is taken in a crucible.
▪ The vessel is filled with excess of oxygen at a pressure of 20 to 25 atmospheres and then sealed.
▪ This apparatus is dipped in an insulated water bath which is provided with a mechanical stirrer and a
thermometer.
▪ Make electrical connections from battery to electrodes.
▪ The initial temperature is noted and the final temperature is recorded from the thermometer in the water
bath.
▪ Then the quantity of heat produced by burning a fuel is calculated.

Calculations:
Let weight of the fuel sample taken = x g
Weight of water in the calorimeter = W g
Water equivalent of the Calorimeter, stirrer, bomb, thermometer = w g
[Note: = mass x specific heat of apparatus]
w =m x S
Initial temperature of water = t1oC
Final temperature of water = t2oC

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Higher or gross calorific value = C cal/g or G.C.V

Heat gained by water = W . Δt Note: Heat absorbed= w x Δt x Specific heat

= W . (t2-t1) cal Specific heat of water = 1 cal/g0C
Heat gained by Calorimeter = w . (t2-t1) cal
Heat gained by water and calorimeter = (W+w) (t2-t1) cal
Heat liberated by the fuel = x . C cal
Heat liberated by the fuel = Heat gained by water and
calorimeter
x C = (W + w) (t2-t1) cal

HCV or C = (W + w) ( t2- t1) cal/g

x
LCV = HCV – 0.09 H x 587 Cal/g or Kcal/Kg
Corrections: For getting accurate results the following corrections are also incorporated:

Where,
tc = Cooling Correction
CA = Acid Correction
CT = Cotton thread Correction
CF = Fuse wire Correction

Corrections: For getting accurate results the following corrections are also incorporated:

(a) Fuse wire correction: As Mg fuse wire is used for ignition, the heat generated by burning of Mg fuse
wire is also included in gross calorific value. Hence this amount of heat has to be subtracted from the
total value.

(b) Cotton thread correction: Cotton thread correction is made by the weight of dry cotton thread used
for firing which is added into acid and fuse wire correction.

(c) Acid correction: During combustion, sulphur and nitrogen present in the fuel are oxidized to their
corresponding acids under high pressure and temperature.

S + O2 SO2

2SO2 + O2 + 2H2O 2H2SO4

2N2 + 5O2 + 2H2O 4HNO3

The corrections must be made for the heat liberated in the bomb by the formation of H2SO4 and HNO3.

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(d) Cooling correction: As the temperature rises above the room temperature, the loss of heat does
occur due to radiation during cooling down of water in calorimeter. If the time taken for the water in the
calorimeter to cool down from the maximum temperature attained to the room temperature is x minutes
and the rate of cooling is dt/min, then the cooling correction = x  dt. This should be added to the
observed rise in temperature.

Dulong’s method
It is used for calculating the calorific value of the solid and liquid fuel .
Dulong’s Formula: If C, H, O and S are the percentage of carbon, hydrogen, oxygen and sulphur in a fuel then
the higher calorific value is given by:
𝟏
HCV = [8080 %C + 34500 (%H – %O/8) + 2240 %S] Kcal/Kg or cal/g
𝟏𝟎𝟎
% of Oxygen = 100 - % of [C + H + N + S + Ash]

Q. Describe how the calorific value of coal or liquid fuel is determined by Bomb Calorimeter. The
following data is obtained in a Bomb Calorimeter experiment :
Weight of crucible = 3.649 gm
Weight of crucible + fuel = 4.678 gm
Water equivalent of calorimeter = 570 gm
Water taken in the calorimeter = 2200 gm
Observed rise the temperature = 2.3 °C
Cooling correction = 0.047°C
Acid correction = 62.6 calories
Fuse wire correction = 3.8 calories
Cotton thread correction = 1.6 calories
Calculate the gross calorific value of the fuel sample. If the fuel contains 6.5% H, determine the net
calorific value.
Ans.

HCV = (2200 +570) (2.3 +0.047) – (62.6 + 3.8 +1.6)

(4.687-3.649)
= 6251.88 cal/gm
Since the fuel contains 6.5% hydrogen,
LCV=HCV - 0.09H x 587 cal/g
=66251.88 - 0.09 x 6.5 x 587 cal/g
= 5908 cal/g

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Q. The following data were obtained in a bomb calorimeter experiment:

Weight of coal burnt = 0.994 gm
Weight of water in calorimeter = 2592 gm
Weight of bomb , calorimeter etc = 3940 gm
Rise in temp.=2.732 oC
mean specific heat of the apparatus = 0.098 cal/ gm oC .
Find the gross calorific value of the fuel.
Ans.

Q. The analysis of coal gave following results:

C = 70%, O = 20%, H = 8% S = 1%, N = 0.5%, ash = 0. 5%.Calculate GCV and NCV of coal.

Ans. GCV = 1/100 [8080% C + 34500 (%H – %O/8) + 2240 %S] Kcal/Kg or cal/g
GCV =1/100[8080 x 70 + 34500 (8 – 20/8) + 2240 x 1 ] Kcal/Kg or cal/g
= 7575.9 Kcal/Kg or cal/g
NCV = GCV – 0.09 H x 587 Cal/g or Kcal/Kg
= 7575.9 – 0.09 x 8 x 587
= 7153.26 Kcal/Kg or cal/g

Q. A coal has the following composition by weight:

C = 92%, O = 2.0%, S = 0.5%, N = 0.5%, ash = 1. 5%. Net calorific value of the coal was found to
be 9,430 Kcal/Kg . Calculate the percentage of hydrogen and higher calorific value of coal.

Ans. GCV = 1/100 [8080% C + 34500 (%H – %O/8) + 2240 %S] Kcal/Kg
GCV =1/100[8080 x 92 + 34500 (%H – 2/8) + 2240 x 0.5 ]
GCV = 7433.60 +345%H -86.25 +11.2
GCV = 7358.55 + 345%H…………………(i)
NCV = GCV – 0.09 %H x 587 Kcal/Kg
9430 = GCV – 0.09%H X 587
GCV= 9430 +52.83%H………………………(ii)
From (i) and (ii)

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7358.55 +345%H = 9430 +52.83%H

292.17%H = 2071.45
%H = 2071.45 / 292.17
= 7.08
Therefore , GCV= 9430 +52.83%H
=9430 +52.83 x7.08
= 9804.6 Kcal/Kg

Q. Calculate the GCV and NCV of coal having the following compositions: Carbon = 85%, Hydrogen =
8%, Sulphur = 1%, Nitrogen = 2% and Ash = 4%, oxygen= 0% The latent heat of combustion of steam
= 587 cal/g.

Ans. We know,
HCV = 1/100[8080 C + 34500 (H – O/8) + 2240 S] Kcal/Kg or cal/g
HCV = 1/100[8080 x 85 + 34500 (8 – 0/8) + 2240 x 1] cal/g
= 1/100 [6,86,800+2,76,000+2,240] cal/g
= 9,650.4 cal/g
LCV = HCV – 0.09 H x 587
LCV = 9,650.4 – 0.09 x 8 x 587 cal/g
= 9,650.4 – 422.64 cal/g
LCV = 9227.76 cal/g

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Coal Analysis

Coal is regarded as a fossil fuel produced from the vegetable debris (cellulosic matter) under conditions of
high temperature and pressure over millions of years. It is mainly composed of C,H, N, O and non-
combustible inorganic matter. Pressure and heat compact the material into a solid and this process known as
coalification.

Coal is analyzed in two ways:

A) Proximate analysis:
1.Determination of Moisture Content
2. Determination of volatile matter
3.Determination of Ash content
4. Determination of Fixed Carbon

B) Ultimate analysis
1. Determination of Carbon and Hydrogen
2. Determination of Nitrogen
3. Determination of Sulphur
4. Determination of Ash
5. Determination of Oxygen

Proximate Analysis: It is the simplest type of analysis of coal which includes the determination of
moisture, ash, volatile matter and fixed carbon in coal.

1. Determination of Moisture Content: Air dried moisture is determined by heating a known amount of coal
to 105-110 oC in an electric hot air oven for about one hour. After one hour, it is taken out from the oven and
cooled in a desiccators and weighed.
Loss in weight
Percentage of moisture = x 100
weight of coal sample

Significance: Excees of moisture is undesirable in coal. It reduces the calorific value of the coal. It also increases
transportation cost and some amount of heat is wasted for its evaporation from coal during combustion.

2. Determination of volatile matter: It is determined by heating a known weight of moisture free coal sample
in a covered platinum crucible at 950 ± 20oC for 7 minutes in a muffle furnace.
loss of weight due to volatile matter
Percentage of volatile matter = x 100
Initial Weight of coal sample

Significance: A high percent of volatile matter reduces the calorific value of fuel. Such coal burns with low
flame and high smoke.

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3. Determination of Ash content: Ash content is determined by heating the residue left after the removal of
volatile matter at 700  50oC for ½ an hour without covering
Weight of the ash
Percentage of ash = Initial Weight of the coal× 100

Significance: The high percentage of ash is undesirable. It reduces the calorific value of coal. The ash may
restrict the lower the rate of combustion.

4. Determination of Fixed Carbon:. The percentage of fixed carbon is determined by:

Percentage of fixed carbon = 100 - [% of moisture + volatile matter + ash content]

Significance: Higher the percentage of fixed carbon, greater its calorific value and hence better is the quality of
coal.

Q. A sample of coal was analyzed as follows: Exactly 2.00g was weighed into silica crucible. After heating
for one hour at 110 oC, the residual weighed 1.975g.The crucible next was covered with a vented lid and
strongly heated for exactly seven minutes at 950 oC. The residual weighed 1.328 g . The crucible was then
heated without the cover ,until a constant weight was obtained. The last residue was found to weight
0.205g.Calculate the percentage results of the above analysis.

Ans.

Ultimate analysis: Ultimate analysis includes the exact estimation of carbon, hydrogen,
sulphur, nitrogen and oxygen in the fuel.

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1. Determination of Carbon and Hydrogen:

• A known amount of coal is burnt in dry oxygen.

• C and H are converted into CO2 and H2O respectively.
• The products of combustion are passed over weighed tubes of anhydrous CaCl 2 and KOH.
• The increase in the weight of CaCl2 tube represents the weight of water formed.
• The increase in the weight of KOH tube represents the weight of CO2 formed.

Increase in wt.of KOH tube x 12

% of Carbon = x 100
Wt.of Coal sample x 44

Increase in wt. of CaCl2 x 2

% of Hydrogen = x 100
Wt.of Coal sample x 18

Significance: High percentage of carbon and hydrogen increase the calorific value of coal.

2. Determination of Nitrogen:

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• Nitrogen present in coal sample can be estimated by Kjeldahl’s method.

• 1 g coal sample is heated with conc. H2SO4 & K2SO4 (catalyst) in Kjeldahl’s flask.
• Nitrogen in the compound converted into ammonium sulphate.
• The ammonium sulphate is heated with excess NaOH and liberate ammonia .
• The liberated NH3 is absorbed in standard solution of H2SO4.
• The unused acid is then determined by back titration with standard NaOH.

•
NaOH (excess)
N2 + H2SO4 (NH4)2SO4 Na2SO4 + NH3 + H2O
2NH3 + H2SO4 (NH4)2SO4

1.4 x Normality x Volume of acid used

% of Nitrogen =
Wt.of Coal sample

Significance: Nitrogen is an inert and non-combustible material. It has no calorific value. Its presence is
undesirable.

Q. A 3.25 g of coal sample was Kjeldahlized and NH3 gas thus evolved was absorbed in 45 mL of 0.1 N
H2SO4. After absorption, the excess acid required 11.5 mL of 0.1 N NaOH for exact neutralization.
Determine the % of N in the sample of coal.

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3. Determination of Sulphur:
• A known weight of coal sample is burnt completely in Bomb Calorimeter in a current of oxygen where
sulphur converts to sulphates.
• The percentage of sulphur is then determined by the washings of bomb calorimeter.
• The washings are treated with BaCl2 solution which makes BaSO4 precipitate.
• It is now filtered washed and heated to constant weight.

Wt.of BaSO4 x 32
% of Sulphur = x 100
Wt.of Coal Sample x 233

Significance: Sulphur has its calorific value and hence, it contributes to the calorific value of the fuel. However,
the combustion products of sulphur i.e. SO2 and SO3 etc. cause air pollution and corrosion of equipment.

Q. A 0.1 g of coal sample was used in a bomb calorimeter for the determination of calorific The ash
formed in the bomb calorimeter was extracted with acid and the acid extract was heated with barium
chloride solution and a precipitate of barium sulphate was obtained. value. The precipitate was filtered,
dried and weighed. The weight of precipitate was found to be 0.01 g. Calculate the % of S in the coal
sample.

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4. Determination of Ash: Ash content is determined by heating the coal after the
removal of volatile matter at 700  50oC for ½ an hour without covering
Weight of the residue left
Percentage of ash = × 100
Weight of the coal

5. Determination of Oxygen:

% of Oxygen = 100 - % of [C + H + N + S + Ash]

Significance: A good quality of coal should contain low percentage of oxygen as it lower the calorific value of
coal.

COMBUSTION

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Important points for Air quantity calculation:

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Q. Calculate the weight and volume of air required for the combustion of 500gm of carbon.

Ans.

Q. The percentage composition of coal sample is C = 85%, O = 6%, N = 4%, S = 2%, H= 5% and
moisture = 3%. Calculate the minimum amount of air and volume of air needed in combustion of 1 kg
of coal.

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Q. A gas has the following composition by volume: H2 = 22% ; CH4 = 4%, ;CO = 20 %;CO2 = 6 %
;O2=3% and N2 = 45 %. If 25 % excess air is used, find the weight of air actually supplied per m 3 of this
gas.

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Q.A sample of coal was found to have the following % composition: C=75% ; H= 5.2% ; O=12.1%;N=
3.2% and ash = 4.5%.
(i) Calculate the minimum air required for complete combustion of 1 kg of coal.
(ii) Also calculate the higher calorific value and lower calorific value of coal sample.
Ans.

Q. Calculate the minimum weight and volume of air required for complete combustion of 2.5 Kg of fuel
containing C = 90%, H = 3.5%, O = 3%, S =0.5%, H 2O =1%, N =0.5% and Ash = 1.5%

Ans. Weight of air required = 28.86 Kg

Volume of air required (L)= 22.125 L

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Biogas

• Methane, carbon dioxide, and hydrogen sulfide are the main gases that makeup biogas.
• Bio gas is produced by the degradation of biological matter by the bacterial action of the anaerobic
bacteria in the absence of free oxygen.
• It is a renewable source of energy.
• It can also be produced from the sewage waste and other organic wastes.

Composition of biogas: The average composition of biogas is:

(i) CH4 = 50 – 60% (a combustible gas)

(ii) CO2 = 30-40 % (a non-combustible gas)
(iii) H2 = 5-10 % (a combustible gas)
(iv) N2 = 2-6 %(a non-combustible gas)
(v) H2S = traces (a combustible gas)
Out of these the constituent methane (an extremely good fuel) makes biogas an excellent fuel.

Construction and working :

• A biogas plant consists of an underground tank called digester, which is made of bricks and has a
dome-shaped roof.
• The dome acts as a gas-holder.
• There is a gas outlet at the top of the dome having a valve.
• There is a sloping inlet chamber connected to a mixing tank and a rectangular outlet chamber
connected to the overflow tank.
• Cow dung and water are mixed in equal proportions in the mixing tank to prepare the slurry.
• This slurry is fed into the digester tank through the inlet chamber to fill the tank up to the cylindrical
level.
• Then, the cow-dung undergoes anaerobic degradation with the evolution of biogas which collects in
the dome.
• The pressure of biogas on the slurry forces the spent slurry to go into the overflow tank through outlet
chamber, from where it is removed.

Steps involved in obtaining biogas:

1. Hydrolysis- Enzymes convert large organic molecules into simpler units.
2. Fermentation- Organic materials are broken down by bacteria in anaerobic conditions.
3. Methane formation- Production of methane gas.
4. Spent slurry- Residue left after the formation of biogas.

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Schematic diagram of a Floating dome biogas plant

Uses of bio gas:

(i) Used as a fuel to run engine.
(ii) Used for lighting and power purposes.
(iii) Used for production for cooking and thermal applications
Advantage:
i. Biogas is a safe, cheap, renewable source of energy.
ii. It is eco-friendly and does not cause any pollution.
iii. Large amount of heat is generated as compared to direct burning of cattle dung.
iv. The residue left after the production of biogas can be used as manure.
v. No harmful CO product.
Limitations:
Biogas should be used within 10 meters of the biogas plant.

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