Fuels

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 SYLLABUS

 Definition, classification, characteristics of a good fuel.

 Calorific value- Definition, Units, Gross or Higher calorific value & Net or lower calorific value.
 Dulong’s formula & numerical for calculations of Gross and Net calorific values.
 Analysis of coal- Proximate and Ultimate Analysis (theory and numericals).
 Combustion- Calculations for requirement of only oxygen and air (by weight and by volume only) for
given fuels.
 Power alcohol.
 Green fuel : Biodiesel (Synthesis and advantages)

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 INTRODUCTION

A fuel is a combustible substance containing carbon as the main constituent which on proper burning gives a
large amount of heat that can be used economically.

For example: wood, coal, kerosene, petrol, diesel and water gas.

Combustion reaction of a fuel can be represented as follows:

 CnH2n+2 + O2 → CO2(g) + H2O (g) + heat

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 Classification of fuel
Fuel

Primary Secondary
or or
natural fuel Artificial fuel

Solid Liquid Gaseous Solid Liquid Gas

(wood, (petroleum)(Natural (Charcoal) (petrol) (coal
coal) gas) gas)

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 Calorific value

• Calorific value of a fuel is the total quantity of heat liberated when one unit of fuel is burnt
completely.

• Gross or Higher calorific value (G.C.V or H.C.V): It is the total quantity of heat liberated
when one unit of fuel is burnt completely and products of combustion has been cooled to room
temperature(15oC)

• Net or Lower calorific value (N.C.V or L.C.V) ): It is the total quantity of heat liberated
when one unit of fuel is burnt completely and products of combustion has been permitted to
escape.
L.C.V= H.C.V – Latent heat of water vapour formed
= =[H.C.V-0.09H x 587]kcal/kg
(Latent heat of steam= 587 cal/gm)

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 Units of Calorific value

Units of Solid fuel Liquid fuel Gaseous

calorific value fuel
CGS method cal/g cal/g cal/cm3
MKS method Kcal/Kg Kcal/Kg Kcal/m3

FPS method B.Th.U/Ib B.Th.U/Ib BTU/ft3

SI method Joule/Kg Joule/Kg Joule/m3

1 Kcal/kg= 1.8 B.Th.U/Ib

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1 Kcal/m 3 = 0.1077 B.Th.U/ft3
 Characteristic of good fuel

A good fuel should have

• high calorific value
• moderate ignition temperature
• low moisture content
• low non combustible matter content
• low cost and easy availability
• easy to transport and storage cost should be low
• products of combustion should not be harmful.
• burn in air without much smoke
• combustion should be easily controllable.
•Should no undergo spontaneous combustion
•Should burn in air with efficiency,without much smoke.
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 Theoretical calculation of calorific value using
Dulongs formula

H.C.V= 1/100[8080C + 34500(H-O/8)+ 2240 S] kcal/kg

Where,

C= % of carbon in the fuel

H= % of hydrogen in the fuel
O= % of oxygen in the fuel
S= % of sulphur in the fuel
And
Calorific value of carbon= 8080 kcal/kg
Calorific value of hydrogen= 34500 kcal/kg
Calorific value of sulphur= 2240 kcal/kg

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Theoretical calculation of calorific value using Dulongs
formula

L.C.V= H.C.V – Latent heat of water vapour formed

=[H.C.V-9H x 587/100]kcal/kg
=[H.C.V-0.09H x 587]kcal/kg
*N and Ash are non combustible matter , don’t consider for calculations.

*This is based on the fact that 1 part of H by mass gives 9 parts of H2O and latent heat of
steam is 587 Kcal/Kg.

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 Numerical problems based on calorific value

Problem 1: In a sample of coal containing carbon 85%, hydrogen 8%, sulphur 1%, nitrogen 2%
and ash 4%. Calculate the gross calorific value (G.C.V) and net calorific value (N.C.V).
(Latent heat of steam=587 cal/gm)

Solution:
H.C.V= 1/100 [8080C + 34500(H-O/8)+ 2240 S] kcal/kg
=1/100[8080*85+34500(8-0/8)+2240*1]
=1/100[686,800+276,000+2240] =9650.4 kcal/kg
L.C.V= H.C.V – Latent heat of water vapour formed
=[H.C.V-9H x 587/100]kcal/kg
=9650.4-0.09*8*587=9227.76 kcal/kg

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Problem 2: Calculate the gross calorific value (G.C.V) and net calorific value
(N.C.V) of a sample of fuel containing carbon 80%, hydrogen 7%, oxygen
3%,sulphur 3.5%, nitrogen 2.1% and ash 4.4%.
(Latent heat of steam = 587 cal/g)

Ans:[GCV=8828.025 kcal/kg ; NCV=8458.21 kcal/kg ]

Problem 3: In a sample of coal containing carbon 75%, hydrogen 5.2%, oxygen

12.1%, nitrogen 3.2% and remaining ash. Calculate the gross calorific value
(G.C.V) or Higher calorific value (H.C.V) using Dulong’s formula.

Ans:[GCV=7332.19 kcal/kg ; NCV=7057.41 kcal/kg ]

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 Criteria for selecting a Fuel

• Calorific value should be high

• Moisture content should be low

• Ash content should be low

• Sulphur and phosphorus contents of coal should be low

• Size of coal should be uniform

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Combustion Numericals:Theoretical Calculation of Minimum Air
required for Combustion

1)Combustion reactions:
Combustion of Carbon: C(S) + O2 (g) → CO2 (g)(by weight)
12 32 44
Combustion of Hydrogen: 2H2 (g) + O2 (g) → 2H2O (g) (by weight)
2*2=4 32 2*18=36
Combustion of Sulphur: S (s) + O2 (g) → SO2(g) (by weight)
32 32 64

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2)Theoretical amount of oxygen required for the complete combustion of 1kg of
solid or liquid fuel.
Theoretical minimum O2 = [32/12xC+8xH-O+S] kg
Where C,H,O and S represents the masses of carbon, hydrogen, sulphur and oxygen respectively per kg of
fuel.

3)Air contains 21% of oxygen by volume and 23% by weight.

The amount of air required theoretically for combustion of 1 kg of the fuel is,
Air (theoretical) = 100/23 [32/12xC+8xH-O+S] kg
4)22.4 L(or 22400 mL) of any gas at STP(i.e.0OC and 760 mm pressure) has a mass equal to
its 1 mole. (44 is the molecular weight of CO2 )
Thus,22.4 L of CO2 at STP will have a mass of 44g.
5)Molecular mass of air is taken as 28.94 gmol-1.
6)Minimum oxygen required
=Theoretical oxygen required - O2 present in fuel.
7)The mass of any gas can be converted to its volume at certain temperature and
pressure by using the gas equation: PV=nRT
Where P=Pressure of gas in atmosphere ;V =Volume of gas in liters ; n= No. of mole of the gas
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Volume of Air Required for Complete Combustion of Gaseous
Combustible Matters

 Combustion reactions:
 i)H2 (g) + 1/2O2 (g) → H2O (g)
1 vol. 0.5vol.
1 volume of H (g) requires 0.5 vol. of oxygen
 ii) CH4 + 2 O2 → CO2 + 2 H2O
1 vol 2 vol
1 volume of CH4 requires 2.0 volume of oxygen
 iii) CO(g) + ½ O2 CO2
1 vol 0.5 vol
1 volume of CO requires 0.5volume of oxygen
iv)C2H4(g) + 3O2 → 2CO2 + 2H2O
1 vol 3 vol
1 volume of C2H4 (g) requires 3.0 vol. of oxygen 06-12-2024 15
 Example 1:A sample of coal was found to contain : C=80% ; H=5%; O=1%;N=2%;
remaining being ash. Calculate the amount of minimum air required for complete
combustion by 1 kg of coal sample. Also calculate volume of air.
 Solution:1 kg of coal contains : C=0.80 kg, H=0.05kg O=.01 kg and N=0.20 kg
 Combustion reactions:
C(S) + O2 (g) → CO2 (g)(by weight)
12 32 44
2H2 (g) + O2 (g) → 2H2O (g) (by weight)
2x2=4 32 2x18=36
Weight of oxygen required=[32/12xC+8xH-O+S] kg
=[32/12x0.80+8x0.05-0.01)] kg
=2.536kg
Weight of air required=100/23x2.536
=11.026kg
Volume of air required for combustion=11.026x22.4/28.94
=8.543 m3

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 Example 2:A coal sample has the following composition: C = 85%, H = 10%, S =
5. Calculate the minimum quantity of oxygen and air by weight and volume
required for the complete combustion of 2 kg of fuel.

 Solution:1 kg of coal contains : C=0.85 kg, H=0.10kg and S=0.05 kg

Combustion reactions: C(S) + O2 (g) → CO2 (g)(by weight)
12 32 44
2H2 (g) + O2 (g) → 2H2O (g) (by weight)
2x2=4 32 2x18=36
Weight of oxygen required=[32/12xC+8xH-O+S] kg
=[32/12x0.85+8x0.10+0.05)] kg
=3.12kg and For 2 Kg of Fuel=2x3.12=6.24kg
Weight of air required =100/23x6.24
= 27.10kg
Volume of air required =27.10x22.4/28.94
 =20.97m3
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 Example 3:A fuel sample has the following composition: H2 = 50%, C2H2 =
20%, CO = 8%, CO2 = 1% and rest is nitrogen. Calculate the volume of
oxygen and air required for complete combustion of 2 m3 of fuel. Also
calculate weight of air required for combustion.
 Solution:1m3 of gaseous fuel contains: H2 = 0.50m3, C2H2 = 0.20m3, CO =
0.08m3, CO2 = 0.01m3 and N remaining

 Combustion reactions:
 i)H2 (g) + 1/2O2 (g) → H2O (g)
0.50 x 0.5 =0.25
 ii) C2H2 + 2.5 O2 → 2CO2 + 2H2O
0.20 x 2.5 =0.50
 iii) CO(g) + ½ O2 → CO2
0.08 x 0.5=0.04
iv) CO2 and N2 are noncombustible.

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 Volume of oxygen required for combustion of 2m3 of fuel
=2[0.25+0.50+0.04]
=1.58m3

 Volume of air required for combustion of 2m3 of fuel

=100/21[1.58]
= 7.52m3

weight of air required for combustion of 2m3 of fuel

=7.52x28.94/22.4
=9.71 Kg

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 For practice:
 Example 4:A fuel sample has the following composition: H2 = 50%, CH4 = 30%,
C2H4 = 3%, C2H6 = 5%, CO = 7%, water vapour = 3% and rest is nitrogen.
Calculate the volume and weight of air required for complete combustion of
2 m3 of fuel.
 [Given: Mol. Wt. of air=28.94 kg]
 Ans: For 2 Kg of sample,
 Volume of air required= 2x5.48 m3 =10.96
 Weight of air required=2x7.08kg=14.16

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Need for analysis:
 The composition of coal varies widely according to source and age.
The purposes for coal analysis are:

 i)to fix the price of coal

 ii)to assess the quality of coal

 iii)to calculate theoretical calorific value

 iv)to design the furnace box for burning of coal

 v)to classify the coal for different purposes

 vi)to calculate oxygen and air requirement for complete combustion

of coal.

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Proximate Analysis:
Constituents of coal Temperature & Time Significance of determination
of determination

1 Moisture 100-110 oC, 1hour (oven) i)Reduces calorific value

ii)Increases transportation cost

2 Volatile matter 900-950 oC,7 minutes (muffle i)Lowers calorific value

furnace)
ii)affect furnace design

3 Ash 700-750oC (until constant weight) i) Reduces calorific value

ii)creates disposal problem

4 Fixed carbon 100- (Moisture+ Volatile matter i)higher % of carbon, greater is the C.V.
+Ash)
ii)Helps in designing furnace and shape of the
fire box

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Numericals : Proximate analysis

 Example [1] A sample of coal was analyzed as follows: Exactly 2.500 g was weighed
into a silica crucible. After heating for 1 hour at 110oC,the residue weighed 2.415g.The
crucible next was covered with a vented lid and strongly heated for exactly seven minutes
at 950 ± 20ºC.The residue weighted 1.528g.The crucible was then heated without lid, until
constant constant weight was obtained. The last residue found to 0.245g.Calculate percent
result of above analysis.

 Solution:
 Mass of moisture in coal sample=2.500-2.415=0.085g
 Mass of volatile matter=2.415-1.528=0.887g
 Mass of ash=0.245g
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Percent of moisture =Loss in weight/weight of coalx100
=0.085x100/2.500
=3.40%
Percent of volatile matter = Loss in weight/weight of coalx100
=0.887x100/2.500
=35.48%

Percent of ash = weight of residue/weight of coal x100

=0.245x100/2.500
=9.80%
Percent of fixed carbon=100-%(Moisture+ Volatile matter+Ash)
=100-(3.40+35.48+9.80)
=51.32% 06-12-2024 25
 Example [2] 3.5 gm of air dried coal sample was taken in a silica crucible, after heating
it in an electric oven at 105-110ºC for 1 hour, the residue was weighed 2.92 gm. The
residue was heated in a silica crucible covered with vented lid at a temperature 950 ±
20ºC for exactly 7 minutes. After cooling, the weight of residue was found to be 2.70
gm. The residue was then ignited at 750ºC to a constant weight of 0.10 gm. Report the
proximate analysis results.

Solution:
 Mass of moisture in coal sample=3.5-2.92=0.58g
 Mass of volatile matter=2.92-2.70=0.22g
 Mass of ash=0.10g

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Cont.

Percent of moisture =Loss in weight/weight of coalx100

=0.58x100/3.5
=16.57%
Percent of volatile matter = Loss in weight/weight of coalx100
=0.22x100/3.5
=6.28%

Percent of ash = weight of residue/weight of coal x100

=0.10x100/3.5
=2.85%
Percent of fixed carbon=100-%(Moisture+ Volatile matter+Ash)
=100-(16.57+6.28+2.85)
=74.30%
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Significance of proximate analysis:
 Moisture: During burning of coal it evaporates. It takes some of the heat in the form of
latent heat of evaporation. Thus lowers the calorific value of coal. It reduces the efficiency
of fuel. More ever its presence increases transportation cost and causes difficulty in
handling.

 ii)Volatile matter: A high volatile matter means that high portion of fuel will distil over as
gas or large portion of which remain unburnt hence higher volatile matter is undesirable. A
high volatile matter containing coal burns with long smoky flame and has low calorific value.
So lesser the volatile matter, better is the quality of coal. Volatile matter affects the furnace
volume and arrangement of heating space.

 iii)Ash: ash consists of SiO2, Al2O3, Fe2O3 and small quantities of MgO and Cao. It is
useless, non-combustible matter and it reduces the calorific value of coal. It causes
hindrance to the flow of air and heat. It increases transporting, handling, and storage costs.
It involves additional cost in ash disposal. This signifies that lesser the ash content in a fuel,
better is its quality.

 iv)Fixed carbon: Higher the percentage of fixed carbon, higher is its calorific value and
better its quality. The knowledge of fixed carbon helps in designing the furnace and shape
of the fire box.

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Ultimate analysis (Elemental analysis):

 Coal is composed primarily of carbon along with variable quantities of

other elements chiefly hydrogen, oxygen, sulphur and nitrogen.
 Ultimate analysis is also known as elemental analysis, It is the method
to determine hydrogen, oxygen, sulphur and nitrogen content present
in solid fuel.
 It is useful in classification of coal and in combustion calculations as it
basically determines the percentage of constituents.
 Ultimate analysis is useful in calculating heat balance for the
equipment in which fuel is used.

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 1000 ml of 1N ammonia solution=14 gms of N
 (Blank-back) ml 1N ammonia solution= (Blank-back)x Normalityx14 gms of N
1000
W gms of coal contains (Blank-back)x Normalityx14 gms of N
1000
Therefore,100 gms of coal contains=(Blank-back)xNx14 x100
1000 W

 % N =(Blank-back)xNx1.4
1000

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06-12-2024 35
Determination of Ash
 Ash is determined as in proximate analysis.
 A known weight of dried sample is taken in a open silica crucible and heated
to open air at 700-750oC in a muffle furnace until a constant weight is
obtained. The weight of residue is reported as ash.
 Percent of ash = weight of residue/weight of coal x100

Determination of Oxygen:
% of Oxygen =100-%(C+H+N+S+Ash)

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Significance of Ultimate analysis:

 By knowing the percentage of the constituent elements in a sample of coal,

their effects on the quality of coal can be determined.

 Carbon: Grater the percentage of carbon, better is the coal in calorific value
and quality. The quantity of carbon is necessary for designing furnace and fire
box.

 Hydrogen: is mostly associated with moisture and volatile matter hence it

reduces the calorific value of fuel. Smaller the H % better is the coal quality.

 Nitrogen: has no calorific value, hence its presence in coal is undesirable. It is

non-combustible and non-supporter of combustion.

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 Sulphur: Sulphur in coal is of special interest because of potential air pollution
problems. Although sulphur increases the heating value of coal, on
combustion produces SO2 and SO3 gases. These gases have harmful effects of
corroding equipment and also causing atmospheric pollution. Presence of
sulphur is highly undesirable in coal to be used for making coke for iron
industry.

 Oxygen: Oxygen content is inversely related to carbon content. The oxygen

present in the fuel lowers its calorific value by 1.7%.As the percentage of
oxygen in the coal increases the capacity of the coal to hold moisture also
increases. Also coking power decreases. This results in lowering of calorific
value. Hence oxygen is undesirable in coal.

 Thus a good quality of coal should have higher percentage of carbon and
lower percentage of nitrogen, sulphur, oxygen and hydrogen.

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06-12-2024 39
Numericals : Ultimate analysis

 1.5 gm of coal sample was burnt in a combustion apparatus and products of

combustion were collected in previously weighed KOH bulb and CaCl2 tube. The
increase in weights of KOH bulb and CaCl2 tube were found to be 3.922 and 1.25gm
respectively. Calculate percentage carbon and hydrogen in the sample.
 ANS:C=71.31% , H=9.26%

 1.2 gm coal was heated in Kjeldahl’s flask and ammonia gas evolved was absorbed in
45 ml of N/5 H2SO4. The excess acid required 35 ml of N/5 KOH for neutralization. 1.1
gm of the same coal sample in a Bomb-calorimeter experiment gave 0.32 gm BaSO4.
Calculate percentage of N and S in the coal sample.
 ANS:N=2.33%. S=3.99%

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 2.8 g coal was heated in Kjeldahl’s flask and ammonia gas evolved was
absorbed in 40 mL of 0.5 N H2SO4. After absorption, the excess acid required
19 mL of 0.5 N NaOH for neutralization. The same sample of coal weighing 1.3
g in a Bomb-calorimeter experiment gave 0.42 g BaSO4. Calculate percentage
of N and S in the coal sample.
 ANS:5.25% S=4.44%

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Liquid fuels:

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Power alcohol:
 When ethyl alcohol is used as fuel for internal combustion engine, it is called
as ‘power alcohol’. Ethyl alcohol is used as a additive to motor fuel. Blends
with 25% of alcohol with petrol is used.

Advantages of alcohol blended petrol:

i)Addition of alcohol to petrol increases its octane number
ii)posses better antiknock properties
Iii)Alcohol is capable of absorbing any traces of moisture present in petrol.
iv)Alcohol petrol blends have lesser starting difficulties.
Dis-advantages of alcohol blended petrol:
i)Alcohol lowers the calorific value of petrol.(petrol cv=11,250kcal/kg, alcohol=7,500 kcal/kg)
ii)Specific arrangement for combustion is required.
iii)Alcohol is easily oxidised to acids. Hence may cause corrosion.

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Manufacture of Alcohol:

 In India, alcohol is manufactured from molasses.

Invertage

 C12H22O11 + H2O C6H12O6 + C6H12O6

(surose) (in yeast) (Glucose) (Fructose)

C6H12O6 2 C2H5OH + 2CO2(g)

(in yeast)

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Flow chart of production of alcohol:

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 The molasses(contains about 50-60% sucrose +glucose and fructose) are diluted with water to
bring its sugar concentration to 10-12%.
 Then ,some nutrients like(ammonium sulphate and ammonium phosphate) and some
sulphuric acid are added to bring its pH value between 4 and 5.
 Then proper quantity of yeast(an enzyme mixture)is added and temperature is
maintained between 30oC.
 The invertase (of the yeast) converts sucrose into glucose and fructose , and
 The zymase (of the yeast) converts glucose and fructose into ethyl alcohol and
carbon di oxide, the latter produces a lot of froth during this so called
fermentation process.
 The total time required for the completion of fermentation is about 36-48
hours.
 The fermented liquid contains about 18-20% of alcohol.
 After fractional distillation, the fraction rectified spirit which contains 90-95%
of alcohol.

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Biodisel:
 Biodiesel is a cleaner burning renewable alternative to diesel fuel
that is made from biological sources; namely vegetable oil or
animal fats (triglycerides).
 It is mixable with diesel, stable in mixture, and can be burned in
an unmodified diesel engine at any concentration.
 Biodiesel is made through a transesterification reaction.
Transesterification is the chemical process through which one
ester (a chemical having the general structure R’COOR’’) is
changed into another.

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Trans-estrification reaction:

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Synthesis of Bio-diesel:

 This involves vegetable or animal fats and oils being reacted with
short-chain alcohols (typically methanol or ethanol).
 The alcohols used should be of low molecular weight. Ethanol is the
most used because of its low cost, however, greater conversions into
biodiesel can be reached using methanol. (catalyst-sodium)
 Although the transesterification reaction can be catalyzed by either
acids or bases, the base-catalyzed reaction is more common. This
path has lower reaction times and catalyst cost than those acid
catalysis.
 However, alkaline catalysis has the disadvantage of high sensitivity to
both water and free fatty acids present in the oils.

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Flow chart of Bio-diesel synthesis:

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Advantages of the Use of Biodiesel:

 Some of the advantages of using biodiesel as a replacement for diesel fuel are
Renewable fuel, obtained from vegetable oils or animal fats.
 Low toxicity, in comparison with diesel fuel.
 Bio-degradable
 Lower emissions of contaminants: carbon monoxide, particulate matter,
polycyclic aromatic hydrocarbons, aldehydes.
 Lower health risk, due to reduced emissions of carcinogenic substances.
 No sulphur dioxide (SO2) emissions.
 Higher flash point (100oC minimum).
 Its cetane number is 46-52.
 Recycled oil, fat soyabean seeds can be used

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Disadvantages of the Use of Biodiesel:
 Slightly higher fuel consumption due to the lower calorific value of biodiesel.
 Slightly higher nitrous oxide (NOx) emissions than diesel fuel.
 Higher freezing point than diesel fuel. This may be inconvenient in cold
climates.
 It is less stable than diesel fuel, and therefore long-term storage (more than
six months) of biodiesel is not recommended.
 May degrade plastic and natural rubber gaskets and hoses when used in pure
form, in which case replacement with Teflon components is recommended.
 Costly
 Calorific value of bio-diesel fuel=8000-10000 Kcal/Kg &diesel
fuel=11840Kcal/Kg

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Text books &Reference books

Text books:
1. Engineering Chemistry - Jain & Jain (DhanpatRai)
2. Engineering Chemistry – Dara &Dara (S Chand)

Reference Books:
1. Engineering Chemistry - Wiley India (ISBN – 9788126519880)
2. A Textbook of Engineering Chemistry – Shashi Chawla (DhanpatRai)
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