UNIT 3: FUELS AND COMBUSTION

Definition: Fuels are the substances containing carbon as a main constituent and other elements or
atoms, which on combustion (reaction with oxygen) produce heat energy that can be utilized economically for
domestic and industrial purposes.
Fuel + Oxygen Combustion products + Heat

Classification of fuel: Fuels are classified on the basis of occurrence and physical state.
(I) On the basis of occurrence:
(i) Natural or Primary: Occurs naturally. E.g. Wood, Dung, Crude oil, Natural gas.
(ii) Derived or Secondary: Derived from natural fuels. E.g. Coke, Charcoal, Petrol, Kerosene, Biogas.

(II) On the basis of physical state:

(i) Solid: E.g. Wood, Dung, Coke, Charcoal.
(ii) Liquid: E.g. Crude oil, Petrol, Kerosene.
(iii) Gaseous: E.g. Natural gas, Biogas.

The classification is conveniently represented as follows (Figure 1),

Figure 1 : Classification of fuels

Characteristics of good fuel: The characteristics of good fuel are listed.

(1) The calorific value should be high since it indicates the amount of heat generated by the combustion
of fuel.
(2) The moisture content should be low as moisture lowers the calorific value.
(3) The ash content should be low as ash being the non-combustible matter lowers the calorific value.

1
 (4) It should have moderate ignition temperature, i.e., the lowest temperature at which fuel starts
burning. If it is too low, then it is dangerous to store and transport fuel safely. If it is too high, then it may
cause difficulty in initial ignition of fuel.
(5) It should have moderate velocity of combustion. If it is too low, then higher temperature cannot be
achieved. If it is too high, then the heat generated may get wasted before utilization.
(6) Its combustion should be easily controllable.
(7) On combustion, it should not produce harmful and pollution creating products.
(8) It should not produce smoke during combustion.
(9) It should be easily available and at affordable cost.
(10) It should be easy to transport and store.
(11) In case of solid fuel, the size of the particles should be uniform.

Calorific value: The calorific value of the fuel is defined as the amount of heat generated when unit
mass of fuel is completely combusted.
The units are,
(i) kilocalorie per kilogram or kcal/kg,
(ii) calorie per gram or cal/g,
(iii) British Thermal Unit per pound or B.Th.U./lb,
(iv) Centigrade heat unit per pound or (C.H.U.).
During the combustion, depending upon whether the combustion product of hydrogen i.e. H2O is
condensed or allowed to escape, calorific value is of two types- Higher or Gross calorific value (HCV or GCV)
and Lower or Net calorific value (LCV or NCV).
Gross calorific value is defined as the amount of heat generated, when a unit mass or volume of the
fuel is completely burnt and the products of the combustion are cooled down to room temperature (18°C).
Net calorific value is defined as the amount of heat generated, when a unit mass or volume of the fuel
is completely burnt and the products of the combustion are allowed to escape.
Comparison of HCV and LCV:
Sr. No. HCV LCV
1. It is defined as the amount of heat It is defined as the amount of heat
generated, when a unit mass or generated, when a unit mass or volume
volume of the fuel is completely burnt of the fuel is completely burnt and the
and the products of the combustion products of the combustion are
are cooled down to room temperature allowed to escape.
(18°C).
2. It is also known as GCV. It is also known as NCV.
3. It is the total energy released when the It is the energy released when the
products are cooled down to the room products are hot.

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 temperature and water has been
condensed out.
4. Byproducts are allowed to condense. Byproducts are allowed to escape.
5. Some of the heat or energy in Heat or energy in byproducts escapes
byproducts can be recovered through the system.
condensation.
6. It has high value compared to LCV. It has low value compared to HCV.

Dulong’s formula: Dulong’s formula is used to calculate Higher or Gross calorific value (HCV or
GCV) and Lower or Net calorific value (LCV or NCV).
Unit: kcal/kg or cal/g

To calculate HCV:
Calorific value of the fuel is the sum of calorific values of each element (heat produced by the
combustion of each element) present in the fuel. When the % composition of elements present in the fuel is
given, Dulong’s formula is as follows:

HCV = 1/100 calorific value of + calorific value of + calorific value of

Carbon Hydrogen available Sulphur
for combustion

∴ HCV = 1/100 [8080 C + 34500 (H – O/8) + 2240 S]

Where C, H, O and S are expressed in percentages.

Element + O2 Combustion product + Heat generated (calories)
C + O2 CO2 + 96960
H2 + ½ O2 H2O + 69000
S + O2 SO2 + 71680
Since 12 g of carbon give 96960 calories of heat, 1 g of carbon would give 96960/12 = 8080 calories
of heat. Similarly, 2 g of hydrogen give 69000 calories of heat, 1 g of hydrogen gives 69000/2 = 34500 calories
of heat. Also, as 32 g of sulphur gives 71680 calories of heat, 1 g of sulphur gives 71680/32 = 2240 calories
of heat.
It should be noted that oxygen present in the fuel is assumed to be present in combined state with
hydrogen as water (i.e., fixed hydrogen). This fixed hydrogen does not contribute to the calorific value of the
fuel. Hence, if oxygen is present in the fuel, the amount of available hydrogen for combustion is given by,
Amount of available hydrogen for combustion = Total hydrogen – Fixed hydrogen
= Total hydrogen – (1/8) mass of oxygen in fuel

∴ Amount of available hydrogen for combustion = H – O/8

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(Since 8 parts of oxygen combine with one part of hydrogen to form water, fixed hydrogen is equivalent to
1/8 mass of oxygen in fuel.)

To calculate LCV:
LCV = HCV – [heat lost due to vaporization of water formed (due to combustion of hydrogen)]

∴ LCV = HCV – (0.09H x Latent heat of steam)

∴ LCV = HCV – (0.09H x 587)

∴ HCV = LCV + (0.09H x 587)

If H = % of hydrogen in fuel, then total mass of H2O from 1 g of fuel = 9H/100 = 0.09H
This can be explained as,
H2 + ½ O2 H2O
2 16 18
(1 8 9)
Thus, 1 part by weight of hydrogen gives 9 parts by weight of water.
Latent heat of vaporization of water at 18°C is 587 kcal/kg or cal/g.
(The latent heat of vaporization is the amount of heat required to convert a unit mass (1 g) of a liquid into its
vapour without a change in temperature.)

∴ Heat absorbed by water (generated as product of combustion from available hydrogen + originally present

from fixed hydrogen) in steam/ vapour formation = (0.09H x 587) kcal/kg or cal/g.

Solved numericals:
Example 1: Calculate the HCV and LCV of a coal sample having the following composition:
C = 85%, H = 5%, O = 4%, S = 4%, N = 1.5% and remaining ash.
Solution:
To calculate HCV,
HCV = 1/100 [8080 C + 34500 (H – O/8) + 2240 S]
= 1/100 [8080 x 85 + 34500 (5 – 4/8) + 2240 x 4]
= 1/100 (686800 + 155250 + 8960)
HCV = 1/100 x 851010

∴ HCV = 8510.10 kcal/kg

To calculate LCV,
LCV = HCV – (9H/100 x 587)
= HCV – (9 x 5/100 x 587)
= 8510.10 – 264.15

∴ LCV = 8245.95 kcal/kg

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Example 2: A sample of coal contains C = 75%, H = 8%, O = 6%, S = 2%, N = 1.8% and remaining ash.
Calculate the HCV and NCV.
Solution:
To calculate HCV,
HCV = 1/100 [8080 C + 34500 (H – O/8) + 2240 S]
= 1/100 [8080 x 75 + 34500 (8 – 6/8) + 2240 x 2]
= 1/100 (606000 + 250125 + 4480)
= 1/100 x 860605

∴ HCV = 8606.05 kcal/kg

To calculate NCV,
NCV = HCV – (9H/100 x 587)
= 8606.05 – (9 x 8/100 x 587)
= 8606.05 – 422.64

∴ NCV = 8183.41 kcal/kg

Example 3: Calculate the GCV and NCV of a hydrocarbon having the following composition:
C = 97%, H = 3%.
Solution:
To calculate GCV,
GCV = 1/100 [8080 C + 34500 (H – O/8) + 2240 S]
= 1/100 [8080 x 97 + 34500 x 3]
= 1/100 (783760 + 103500)
= 1/100 x 887260

∴ GCV = 8872.60 kcal/kg

To calculate NCV,
NCV = HCV – (9H/100 x 587)
= 8872.60 – (9 x 3/100 x 587)
= 8872.60 – 158.49

∴ NCV = 8714.11 kcal/kg

Example 4: Calculate the percentage of hydrogen and HCV of a coal containing C = 78%, S = 5%, O = 7%
and that coal is having LCV of 8449.89 kcal/kg.
Solution:
LCV = HCV – (9H/100 x 587)

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∴ 8449.89 = {1/100 [8080 C + 34500 (H – O/8) + 2240 S]} – (9H/100 x 587)

= {1/100 [8080 x 78 + 34500 (H – 7/8) + 2240 x 5]} – (52.83 H)

= 6302.40 + 345 H – 301.875 + 112 – 52.83 H

∴ 8449.89 = 6112.525 + 292.17 H

∴ 292.17 H = 2337.365

∴H=8

Thus, percentage of hydrogen = 8.00

Using Dulong’s formula,

HCV = 1/100 [8080 C + 34500 (H – O/8) + 2240 S]
= 1/100 [8080 x 78 + 34500 (8 – 7/8) + 2240 x 5]
= 1/100 [630240 + 245812.5 + 11200]
= 1/100 x 887252.5

∴ HCV = 8872.53 kcal/kg

Alternate method:
LCV = HCV – (9H/100 x 587)
8449.89 = HCV – (0.09H x 587)
HCV = 8449.89 + (0.09H x 587)
HCV = (8449.89 + 52.83 H) kcal/kg ……………. (1)
Using Dulong’s formula,
HCV = 1/100 [8080 C + 34500 (H – O/8) + 2240 S]
= 1/100 [8080 x 78 + 34500 (H – 7/8) + 2240 x 5]
= 1/100 (630240 + 34500 H – 30187.5 + 11200)
= 1/100 (611252.5 + 34500 H)

∴ HCV = (6112.525 + 345 H) kcal/kg ……………. (2)

Using (1) and (2),

8449.89 + 52.83 H = 6112.525 + 345 H
345 H – 52.83 H = 8449.89 – 6112.525

∴ 292.17 H = 2337.365

∴ H = 8.00

Thus, percentage of hydrogen = 8.00

Substituting the value of H in (1),
HCV = 8449.89 + 52.83 H
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 = 8449.89 + (52.83 x 8.00)

∴ HCV = 8872.53 kcal/kg

Example 5: Calculate the percentage of hydrogen and HCV of a coal containing C = 85%, S = 1%, O = 2%,
N = 2.5% and remaining ash and that coal is having LCV of 8490.5 kcal/kg.
Solution:
LCV = HCV – (9H/100 x 587)

∴ 8490.5= {1/100 [8080 C + 34500 (H – O/8) + 2240 S]} – (9H/100 x 587)

= {1/100 [8080 x 85 + 34500 (H – 2/8) + 2240 x 1]} – (52.83 H)

= 6868.00 + 345 H – 86.25 + 22.40 – 52.83 H

∴ 8490.5 = 6804.15 + 292.17 H

∴ 292.17 H = 1686.35

∴ H = 5.77

Thus, percentage of hydrogen = 5.77

Using Dulong’s formula,
HCV = 1/100 [8080 C + 34500 (H – O/8) + 2240 S]
= 1/100 [8080 x 85 + 34500 (5.77 – 2/8) + 2240 x 1]
= 1/100 [686800 + 190440 + 2240]
= 1/100 x 879480

∴ HCV = 8794.80 kcal/kg

Analysis of coal: A coal has to be analysed for its quality. The two important analyses to evaluate the
quality of coal are Proximate analysis and Ultimate analysis.
Comparison of Proximate analysis and Ultimate analysis:
Sr. No. Proximate analysis Ultimate analysis
1. Proximate analysis of coal is the Ultimate analysis of coal is the
determination of the presence of determination of the presence of
different compounds and their different chemical elements and their
amounts in coal. amounts in coal.
2. In proximate analysis, composition of In ultimate analysis, composition of
coal according to contents of coal according to contents of carbon,
moisture, volatile matter, ash and hydrogen, nitrogen, sulphur, ash and
fixed carbon is determined. oxygen is determined.
3. The accuracy of proximate analysis is The accuracy of ultimate analysis is
low. high.

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 Proximate analysis: It involves the determination of % moisture, % volatile matter, % ash and %
fixed carbon.

(1) % Moisture determination: A known weight of powdered and air dried coal sample (m) is taken
in a previously weighed crucible. The crucible is then kept in an electric oven at 105-110°C for 1 hour. After
1 hour, the crucible is taken out and cooled in a desiccator. The crucible is reweighed till constant weight is
obtained. The weight of coal sample is calculated (m1). Weight of moisture in the coal sample can be
calculated as loss in weight of coal due to moisture (m – m1).
Weight of moisture
% Moisture = _____________________ x 100
Weight of coal (air dried)
m – m1
% Moisture = ________ x 100
m
Significance: Moisture lowers the calorific value of coal since considerable amount of heat is required
to drive off the moisture during combustion of fuel. Also, moisture increases the weight of the coal and hence
the transportation cost rises. Hence, a good coal should contain less amount of moisture.

(2) % Volatile matter determination: It can be carried out by starting with either moisture free coal
or air dried coal.
(i) Starting with moisture free coal: The moisture free coal (m1) in a crucible is kept at 925 ± 25°C for 7
minutes in a muffle furnace with vented lid. After 7 minutes, the crucible is taken out and cooled in a
desiccator. The crucible is reweighed again till constant weight is obtained. The weight of coal sample is
calculated (m2). Weight of volatile matter in the coal sample can be calculated as loss in weight of coal due
to volatile matter (m1 – m2).
Weight of volatile matter
% Volatile matter = _____________________ x 100
Weight of coal (air dried)
m1 – m2
% Volatile matter = __________ x 100
m

(ii) Starting with air dried coal: A known weight of powdered and air dried coal sample (m) is taken in a
previously weighed crucible. The crucible is then kept at 925 ± 25°C for 7 minutes in a muffle furnace with
vented lid. After 7 minutes, the crucible is taken out and cooled in a desiccator. The crucible is reweighed
again till constant weight is obtained. The weight of coal sample is calculated (m3). Weight of volatile matter
in the coal sample can be calculated as loss in weight of coal due to volatile matter (m – m3). Weight of
volatile matter and moisture can be calculated as loss in weight of coal due to moisture and volatile matter.
Weight of volatile matter and moisture
% Volatile matter = ________________________________ x 100 – % Moisture
Weight of coal (air dried)
8
 m – m3
% Volatile matter = ________ x 100 – % Moisture
m
Significance: Volatile matter is the material that escapes unburnt during combustion of fuel. Thus,
volatile matter lowers the calorific value of fuel. Fuel with high volatile matter burns with a long flame giving
high smoke. Therefore, furnace providing larger combustion space is required in such cases. Hence, a good
coal should contain less amount of volatile matter.
On the other hand, in coal gas manufacture and carbonization plants where main aim is the by-product
recovery, fuel with high volatile content is desirable.

(3) % Ash (non-combustible matter) determination: A known weight of coal sample is taken in a
previously weighed crucible. The crucible is then kept at 750 ± 50°C for half an hour in a muffle furnace
without lid. After half an hour, the crucible is taken out and cooled in a desiccator. The crucible is reweighed
again till constant weight is obtained. Weight of residue remained is calculated.
Weight of residue
% Ash = _____________________ x 100
Weight of coal (air dried)

Significance: Since ash is the non-combustible matter present in the fuel, it lowers the calorific value
of coal. Hence, a good coal should possess low ash content.

(4) % Fixed carbon determination: It is the combustible matter in the sample calculated by
subtracting the moisture, volatile matter and ash from the sample.
% Fixed carbon = 100 – (% Moisture + % Volatile matter + % Ash)
Significance: During combustion, fixed carbon present in the fuel burns in the solid state. Thus, it
increases the calorific value of coal. Hence, a good coal should possess high fixed carbon percent. The
information regarding percentage of fixed carbon is useful for designing the furnace and firebox.

Numericals:
Example 1: 3.5 g of air dried coal sample was kept in an electric oven for 1 hour at 110°C. The weight reduced
to 3.325 g. Further it was kept in a muffle furnace in a crucible with vented lid at 950 ± 25°C for exactly 7

minutes. The weight of coal reduced to 3.02 g. It was then burnt in a furnace at 750°C for half an hour. The
residue weighed 0.40 g. Report the proximate analysis results.
Solution:
(i) To find % Moisture,
Weight of coal (air dried) = 3.5 g
Weight of coal after losing moisture = 3.325 g
Weight of moisture = 3.5 – 3.325 = 0.175 g

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 Weight of moisture
% Moisture = _____________________ x 100
Weight of coal (air dried)
0.175
= ______ x 100
3.5

∴ % Moisture = 5.00

(ii) To find % Volatile matter,

Weight of coal after losing volatile matter = 3.02 g
Weight of volatile matter = 3.325 – 3.02 = 0.305 g
Weight of volatile matter
% Volatile matter = _____________________ x 100
Weight of coal (air dried)
0.305
= ______ x 100
3.5

∴ % Volatile matter = 8.71

(iii) To find % Ash,

Weight of residue after burning = 0.4 g
Weight of residue
% Ash = _____________________ x 100
Weight of coal (air dried)
0.4
= _____ x 100
3.5

∴ % Ash = 11.43

(iv) To find % Fixed carbon,

% Fixed carbon = 100 – (% Moisture + % Volatile matter + % Ash)
= 100 – (5.00 + 8.71 + 11.43)

∴ % Fixed carbon = 74.86

The proximate analysis results are,

(i) % Moisture = 5.0
(ii) % Volatile matter = 8.71
(iii) % Ash = 11.43
(iv) % Fixed carbon = 74.86

Example 2: An air dried coal sample weighing 3.2 g was taken for volatile matter determination. After heating
the coal sample for 1 hour at 950 ± 25°C, the sample weighed 2.82 g. If it contains 5.7% moisture, find out
the %volatile matter in it.
Solution:
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Weight of coal (air dried) = 3.2 g
Weight of coal after losing volatile matter and moisture = 2.82 g
% Moisture = 5.7
Weight of volatile matter and moisture = 3.2 – 2.82 = 0.38 g
Weight of volatile matter and moisture
% Volatile matter = ________________________________ x 100 – %Moisture
Weight of coal (air dried)
0.38
= _______ x 100 – 5.7
3.2

∴ % Volatile matter = 6.18

Alternate method,
Weight of coal after losing moisture = m1
Weight of moisture
% Moisture = _____________________ x 100
Weight of coal (air dried)

Weight of coal (air dried) – m1

% Moisture = ____________________________ x 100
Weight of coal (air dried)
Since moisture is expressed in percentage,
5.7 3.2 – m1
_____ = _________
100 3.2

∴ m1 = 3.018 g

∴ Weight of moisture = 3.2 – 3.018 = 0.182 g

Weight of volatile matter and moisture = 3.2 – 2.82 = 0.38 g

Weight of volatile matter = Weight of volatile matter and moisture – Weight of moisture

∴ Weight of volatile matter = 0.38 – 0.182 = 0.198 g

Weight of volatile matter

% Volatile matter = _____________________ x 100
Weight of coal (air dried)
0.198
= ______ x 100
3.2

∴ % Volatile matter = 6.18

Example 3: 3.0 g of air dried coal sample was taken in a silica crucible. After heating it in an electric oven at
105-110°C for 1 hour, the residue weighed 2.80 g. This residue was heated in a silica crucible covered with
vented lid at a temperature 950 ± 20°C for exactly 7 minutes. After cooling, the weight of residue was found

11
to be 2.15 g. The residue was then ignited at 750°C to a constant weight of 0.352 g. Calculate the percentage
of fixed carbon in a coal sample.
Solution:
(i) To find % Moisture,
Weight of coal (air dried) = 3.0 g
Weight of coal after losing moisture = 2.80 g
Weight of moisture = 3.0 – 2.8 = 0.2 g
Weight of moisture
% Moisture = _____________________ x 100
Weight of coal (air dried)
0.2
= _____ x 100
3.0

∴ % Moisture = 6.67

(ii) To find % Volatile matter,

Weight of coal after losing volatile matter = 2.15 g
Weight of volatile matter = 2.8 – 2.15 = 0.65 g
Weight of volatile matter
% Volatile matter = _____________________ X 100
Weight of coal (air dried)
0.65
= ______ X 100
3.0

∴ % Volatile matter = 21.67

(iii) To find % Ash,

Weight of residue after ignition = 0.352 g
Weight of residue
% Ash = _____________________ x 100
Weight of coal (air dried)
0.352
= ______ x 100
3.0

∴ % Ash = 11.73

(iv) To find % Fixed carbon,

% Fixed carbon = 100 – (% Moisture + % Volatile matter + % Ash)
= 100 – (6.67 + 21.67 + 11.73)

∴ % Fixed carbon = 59.93

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 Ultimate analysis: It involves the determination of % carbon, % hydrogen, % nitrogen, % sulphur, %
ash and % oxygen.
(1) Determination of % Carbon and % Hydrogen by combustion method: A known weight of
coal sample is burnt in presence of oxygen in a combustion tube (Figure 2). Carbon and hydrogen from coal
are converted to CO2 and H2O respectively and are allowed to pass through previously weighed KOH tube/
bulb and CaCl2 tube respectively. The increase in weight of KOH tube/ bulb and CaCl2 tube is calculated
which is used to determine % carbon and % hydrogen in the coal sample.

Figure 2 : Combustion method

12 100
% C = Increase in weight of KOH bulb x ____ x _________________________
44 Weight of coal sample taken

2 100
% H = Increase in weight of CaCl2 tube x ____ x _________________________
18 Weight of coal sample taken

Significance: More the amount of carbon and hydrogen, more is the calorific value of coal. Hence, a
good coal should have higher amount of carbon and hydrogen. Hydrogen is generally associated with volatile
matter, thus influencing the use of coal.

(2) Determination of % Nitrogen by Kjeldhal’s method: A known weight of coal sample is heated
with H2SO4 and K2SO4 in a Kjeldahl’s flask (Figure 3). Nitrogen from coal is converted to NH4SO4 salt. The
contents are made alkaline where NH4SO4 is converted to NH3 and passed through a known volume of
standard acid. Initially, the same volume of acid is titrated against a standard base (Blank titration reading).The
unreacted acid left over after the neutralisation with ammonia is titrated against the same standard base (Back
titration reading). The acid consumed for neutralising the ammonia is equivalent to the Blank minus Back
titration readings.

13
 Figure 3 : Kjehldal’s method

Volume of acid consumed in neutralizing NH3 x Normality of acid x 1.4

% N = ___________________________________________________________
Weight of coal taken

Volume of acid consumed in neutralizing NH3 = Blank titration reading – Back titration reading
Significance: Nitrogen does not contribute to the calorific value. Hence, its presence in the coal is
undesirable.

(3) Determination of % Sulphur by BaSO4 method: A known weight of coal sample is used to
determine the calorific value in Bomb calorimeter experiment. The washings obtained in the experiment
contain S in the form of sulphate. The washings are treated with BaCl2 where sulphate is converted to BaSO4
precipitate. From the weight of BaSO4 precipitate, % sulphur is determined.
32 100
% S = Weight of BaSO4 obtained x ____ x__________________________
233 Weight of coal sample taken
Significance: Even though sulphur contributes to the calorific value of coal, oxides of sulphur are
corrosive in nature, mainly in presence of moisture. Moreover, they lead to atmospheric pollution.

(4) Determination of % Ash: As determined in proximate analysis.

Significance: Same as discussed in proximate analysis.
(5) Determination of % Oxygen: It is determined by subtracting percentages of carbon, hydrogen,
nitrogen, sulphur and ash from 100.
% Oxygen = 100 – (% Carbon + % Hydrogen + % Nitrogen + % Sulphur + % Ash)
Significance: Oxygen is present in the coal in the form of moisture. Thus, it decreases the calorific
value of coal. Hence, a good coal should have low moisture content.

14
 Formulae derivation:
 Determination of % Carbon and % Hydrogen by combustion method.

12 g Carbon on combustion gives 44 g CO2 (C + O2 CO2)

2 g Hydrogen on combustion gives 18 g H2O (H2 + ½ O2 H2O)

CO2 is absorbed by KOH and H2O is absorbed by CaCl2 to increase the respective weights.
12 100
% C = Increase in weight of KOH bulb x ____ x _________________________
44 Weight of coal sample taken

2 100
% H = Increase in weight of CaCl2 tube x ____ x _________________________
18 Weight of coal sample taken

Increase in weight of KOH bulb = Weight of CO2 formed

Increase in weight of CaCl2 tube = Weight of H2O formed

 Determination of % Nitrogen by Kjeldhal’s Method

The nitrogen present in the coal is first converted to NH3 (ammonia) and passed through a known
volume of standard acid (x N). Initially, the same volume of acid is titrated against a standard base (Blank
titration reading). The unreacted acid left over after the neutralisation with ammonia is titrated against the
same standard base (Back titration reading). The acid consumed for neutralising the ammonia is equivalent to
the Blank minus Back titration readings.

∴ Volume of acid consumed in neutralizing NH3 = (Blank – Back) mL

1000 ml of 1 N acid ≡ 14 g of Nitrogen

(Blank – Back) x x N x 14
∴ (Blank – Back) ml of x N acid ≡ ______________________ g of Nitrogen
1000

Since the NH3 is formed from Nitrogen in the coal,

(Blank – Back) x x N x 14
If ‘w’ g of coal contains _____________________ g of Nitrogen
1000
100 g of coal contains,

(Blank – Back) x x N x 14 100

______________________ x _____ g of Nitrogen
1000 w

15
 Volume of acid consumed in neutralizing NH3 x x N x 14 100
∴ % N = _________________________________________________ x ____
1000 w
Volume of acid consumed in neutralizing NH3 x x N x 1.4
∴ % N = _______________________________________________
Weight of coal taken

 Determination of % Sulphur by BaSO4 method

The sulphur from coal is reacted with BaCl2 and corresponding BaSO4 is precipitated.
Sulphur from Coal (S) ≡ BaSO4
32 g ≡ 233 g
32 100
∴ % S = Weight of BaSO4 obtained x ____ x __________________________
233 Weight of coal sample taken

 Determination of % Ash (non-combustible matter) - Same as done in Proximate Analysis

 % O = 100 – (% C + % H + % N + % S + % Ash)

Numericals:
Example 1: 3.2 g of coal sample was taken for carbon and hydrogen determination by combustion method.
The increase in weight of tube containing anhydrous CaCl2 was 2.7 g and increase in weight of bulb containing
KOH solution was 5.48 g. Calculate percentage of carbon and hydrogen in the coal sample. If the coal sample
contains only C, H and O, calculate percentage of oxygen.
Solution:
Weight of coal sample taken = 3.2 g
Increase in weight of CaCl2 tube = 2.7 g
Increase in weight of KOH bulb = 5.48 g
(i) To find percentage of Carbon,
12 100
% C = Increase in weight of KOH bulb x ____ x _________________________
44 Weight of coal sample taken
12 100
= 5.48 x ____ x ____
44 3.2

∴ % C = 46.70

(ii) To find percentage of Hydrogen,

2 100
% H = Increase in weight of CaCl2 tube x ____ x _________________________
18 Weight of coal sample taken

16
 2 100
= 2.7 x ____ x ____
18 3.2

∴ % H = 9.38

(iii) To find percentage of Oxygen,

% O = 100 – (% C + % H + % N + % S + % Ash)
= 100 – (46.70 + 9.38 + 0 + 0 + 0)

∴ % O = 43.92

Example 2: 4.0 g of coal was heated in Kjeldhal’s flask and ammonia evolved was absorbed in 45 mL of
0.5 N H2SO4. After absorption, the excess acid required 20.5 mL of 0.5 N KOH for neutralization. 3.5 g of
coal in quantitative analysis gave 0.55 g BaSO4. Calculate % N and % S.
Solution:
(i) To calculate percentage of Nitrogen,
Weight of coal = 4.0 g
Blank reading = 45 mL
Normality of H2SO4 = 0.5 N
Back reading = 20.5 mL
Normality of KOH = 0.5 N
Volume of acid consumed in neutralizing NH3 x Normality of acid x 1.4
% N = ____________________________________________________________
Weight of coal taken
(Blank – Back) x Normality of acid x 1.4
% N = ___________________________________
Weight of coal taken

(45 – 20.5) x 0.5 x 1.4

= ____________________
4

∴ % N = 4.29

(ii) To calculate percentage of Sulphur,

Weight of coal = 3.5 g
Weight of BaSO4 obtained = 0.55 g
32 100
% S = Weight of BaSO4 obtained x ____ x __________________________
233 Weight of coal sample taken
32 100
= 0.55 x ____ x ____
233 3.5

∴ % S = 2.16

17
Example 3: 2.66 g of a coal sample was heated in Kjehldahl’s flask and ammonia gas evolved was absorbed
in 70 mL of 0.1 N H2SO4. After absorption the excess (residual) acid required 30 mL of 0.2 N NaOH for
neutralization. 1.62 g of the coal sample in an analysis gave 0.151 g BaSO4. Calculate the % N and % S in the
coal sample.
Solution:
(i) To calculate percentage of Nitrogen,
Weight of coal = 2.66 g
Blank reading = 70 mL
Normality of H2SO4 = 0.1 N
Back reading = 30 mL
Normality of NaOH = 0.2 N
Since strengths of H2SO4 and NaOH are different, back titration reading has to be converted in terms of
normality of H2SO4.
N1V1 = N2V2
(H2SO4) (NaOH)
0.1 x V1 = 0.2 x 30

∴ V1 = 60 mL

∴ In terms of normality of H2SO4, back titration reading = 60 mL

Volume of acid consumed in neutralizing NH3 x Normality of acid x 1.4

% N = ____________________________________________________________
Weight of coal taken
(Blank – Back) x Normality of acid x 1.4
% N = ___________________________________
Weight of coal taken
(70 – 60) x 0.1 x 1.4
= __________________
2.66

∴ % N = 0.53

(ii) To calculate percentage of Sulphur,

Weight of coal = 1.62 g
Weight of BaSO4 obtained = 0.151 g
32 100
% S = Weight of BaSO4 obtained x ____ x __________________________
233 Weight of coal sample taken
32 100
= 0.151 x ____ x ____
233 1.62

∴ % S = 1.28

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Example 4: 2.0 g of coal sample was analysed for nitrogen content by Kjeldahl’s method. After absorbing
excess acid in 0.4 N alkali, the volume of acid consumed by ammonia was found to be 10 mL with 0.4 N acid.
Calculate % N in the coal sample.
Solution:
To calculate percentage of Nitrogen,
Weight of coal = 2.0 g
Normality of acid = 0.4 N
Normality of KOH = 0.4 N
Volume of acid consumed in neutralizing NH3 = 10 mL
Volume of acid consumed in neutralizing NH3 x Normality of acid x 1.4
% N = ____________________________________________________________
Weight of coal taken
10 x 0.4 x 1.4
= _____________
2.0

∴ % N = 2.8

Combustion:
Weight based combustion numericals:
In general, if a fuel consists of Carbon, Hydrogen, Oxygen, Nitrogen and Sulphur, then the combustion
equations of these elements can be given as follows:
C + O2 CO2
12 32 44

H2 + ½ O2 H2O
2 16 18

S + O2 SO2
32 32 64
If oxygen is already present in the fuel, then it will be deducted from the total quantity of oxygen required for
combustion.

The minimum quantity of oxygen required for the complete combustion of fuel will be,
= (32/12 C + 16/2 H + 32/32 S – O) kg
= (32/12 C + 8 H + S – O) kg
Where C, H, O and S are expressed per kg

19
 Assuming air contains 23% oxygen by weight, the minimum quantity of air required for complete
combustion = 100/23 x (32/12 C + 16/2 H + 32/32 S – O) kg
= 100/23 x (32/12 C + 8 H + S – O) kg
As air is a mixture of gases, average molecular weight of air is 28.94 g

∴ 28.94 g air occupies 22.4 L at STP

Or
28.94 kg air at STP occupies 22.4 m3 volume
(1 m3 = 1000 L and 1 kg = 1000 g)

Numericals:
Example 1: A coal sample has the following composition by weight.
C = 82%, H = 7%, N = 3.5%, S = 1%, O = 2% and remaining ash.
Calculate the minimum quantity of air required for the complete combustion of 7 kg of this fuel. Express the
air requirement in terms of volume.
Solution:
Coal composition Per kg
C = 82% 0.82
H = 7% 0.07
N = 3.5% 0.035
S = 1% 0.01
O = 2% 0.02
Ash = 4.5% 0.045

Combustion equations are as follows:

C + O2 CO2
H2 + ½ O2 H2O
S + O2 SO2
The minimum quantity of oxygen required per kg of coal
= 32/12 C + 8 H + S – O
= (32/12 x 0.82) + (8 x 0.07) + 0.01 – 0.02
= 2.19 + 0.56 + 0.01 – 0.02
= 2.74 kg
For 1 kg of coal, oxygen required = 2.74 kg

∴ For 7 kg of coal, oxygen required = 2.74 x 7 = 19.18 kg

Assuming air to be a mixture of 77% nitrogen and 23% oxygen by weight, the minimum quantity of
air required for 7 kg coal = 19.18 x 100/23 = 83.39 kg

20
 To calculate volume of air required,
28.94 kg air at STP occupies 22.4 m3
83.39 kg air at STP occupies 64.55 m3
Volume of air required for 7 kg fuel = 64.55 m3

Example 2: Calculate the weight of air needed for complete combustion of 0.3 kg (300 g) of coal containing:
C = 74%, H = 12%, N = 5%, O = 7% and remaining ash. Express the air requirement in terms of volume.
Solution:
Coal composition Per kg
C = 74% 0.74
H = 12% 0.12
N = 5% 0.05
O = 7% 0.07
Ash = 2% 0.02

Combustion equations are as follows:

C + O2 CO2
H2 + ½ O2 H2O
S + O2 SO2
The minimum quantity of oxygen required per kg of coal
= 32/12 C + 8 H + S – O
= (32/12 x 0.74) + (8 x 0.12) – 0.07
= 1.97 + 0.96 – 0.07
= 2.86 kg
For 1 kg of coal, oxygen required = 2.86 kg
For 0.3 kg (300 g) of coal, oxygen required = 2.86 x 0.3 = 0.858 kg (858 g)
Assuming air to be a mixture of 77% nitrogen and 23% oxygen by weight, the minimum quantity of
air required for 0.3 kg coal = 0.858 x 100/23 = 3.730 kg
To calculate volume of air required,
28.94 kg air at STP occupies 22.4 m3
3.730 kg air at STP occupies 2.887 m3
Volume of air required for 0.3 kg fuel = 2.887 m3

Example 3: A coal sample has the following composition by weight.

C = 76%, H = 8%, N = 1.5%, S = 3%, O = 8% and remaining ash.
Calculate the minimum quantity of air required for the complete combustion of 5 kg of this fuel. Express the
air requirement in terms of volume.
Solution:
21
 Coal composition Per kg
C = 76% 0.76
H = 8% 0.08
N = 1.5% 0.015
S = 3% 0.03
O = 8% 0.08
Ash = 3.5% 0.035

Combustion equations are as follows:

C + O2 CO2
H2 + ½ O2 H2O
S + O2 SO2
The minimum quantity of oxygen required per kg of coal
= 32/12 C + 8 H + S – O
= (32/12 x 0.76) + (8 x 0.08) + 0.03 – 0.08
= 2.03 + 0.64 + 0.03 – 0.08
= 2.62 kg
For 1 kg of coal, oxygen required = 2.62 kg

∴ For 5 kg of coal, oxygen required = 2.62 x 5 = 13.1 kg

Assuming air to be a mixture of 77% nitrogen and 23% oxygen by weight, the minimum quantity of
air required for 5 kg coal = 13.1 x 100/23 = 56.96 kg
To calculate volume of air required,
28.94 kg air at STP occupies 22.4 m3
56.96 kg air at STP occupies 44.09 m3
Volume of air required for 5 kg fuel = 44.09 m3

Example 4: Calculate the minimum quantity of air and the volume of air required for complete combustion of
6 kg fuel containing the following composition.
C = 92%, H = 8%.
Solution:
Coal composition Per kg
C = 92% 0.92
H = 8% 0.08

Combustion equations are as follows:

C + O2 CO2
H2 + ½ O2 H2O
22
S + O2 SO2
The minimum quantity of oxygen required per kg of coal
= 32/12 C + 8 H + S – O
= (32/12 x 0.92) + (8 x 0.08)
= 2.45 + 0.64
= 3.09 kg
For 1 kg of coal, oxygen required = 3.09 kg

∴ For 6 kg of coal, oxygen required = 3.09 x 6 = 18.54 kg

Assuming air to be a mixture of 77% nitrogen and 23% oxygen by weight, the minimum quantity of
air required for 6 kg coal = 18.54 x 100/23 = 80.61 kg
To calculate volume of air required,
28.94 kg air at STP occupies 22.4 m3
80.61 kg air at STP occupies 62.39 m3
Volume of air required for 6 kg fuel = 62.39 m3

Volume based combustion numericals:

Here, the composition of air is considered to be 21% oxygen and 79% nitrogen.
For any hydrocarbon, to balance the combustion reaction, the following formula is useful-
CxHy + (x + y/4)O2 xCO2 + y/2H2O

Numericals:
Example 1: A sample of gaseous fuel has the following composition:
H2 = 32%, CO2 = 15%, C2H4 = 4%, N2 = 49%
Calculate the volume of air required for the complete combustion of 2 m3 of this fuel.
Solution:
Combustion equations are as follows:
H2 + ½ O2 H2O
C2H4 + 3O2 2CO2 + 2H2O

Composition Volume in 1 m3 of fuel Volume of O2 required (m3)

H2 = 32% 0.32 0.32 x 0.5 = 0.16
CO2 = 15% 0.15 -
C2H4 = 4% 0.04 0.04 x 3 = 0.12
N2 = 49% 0.49 -
Total O2 required = 0.28 m3
Volume of O2 required for complete combustion = Total O2 required – O2 present in the fuel
= 0.28 m3

23
For 1 m3 of fuel, volume of O2 required = 0.28 m3
For 2 m3 of fuel, volume of O2 required = 2 x 0.28 m3 = 0.56 m3
Assuming air to be a mixture of 79% nitrogen and 21% oxygen by volume, volume of air required for
2 m3 fuel = 0.56 x 100/21 = 2.67 m3

Example 2: A fuel has the following composition by volume:

CH4 = 44%, C2H2 = 24% rest is ash.
Calculate the volume and the weight of air required for the complete combustion of 4 m3 of this fuel.
Solution:
Combustion equations are as follows:
CH4 + 2O2 CO2 + 2H2O
C2H2 + 2.5O2 2CO2 + H2O

Composition Volume in 1 m3 of fuel Volume of O2 required (m3)

CH4 = 44% 0.44 0.44 x 2 = 0.88
C2H2 = 24% 0.24 0.24 x 2.5 = 0.6
Ash = 32% 0.32 -
Total O2 required = 1.48 m3
Volume of O2 required for complete combustion = Total O2 required – O2 present in the fuel
= 1.48 m3
For 1 m3 of fuel, volume of O2 required = 1.48 m3
For 4 m3 of fuel, volume of O2 required = 4 x 1.48 m3 = 5.92 m3
Assuming air to be a mixture of 79% nitrogen and 21% oxygen by volume, volume of air required for
4 m3 fuel = 5.92 x 100/21 = 28.19 m3
To calculate weight of air required,
22.4 m3 air at STP weighs 28.94 kg
28.19 m3 air at STP weighs 36.42 kg
The weight of air required for the complete combustion = 36.42 kg

Example 3: A fuel has the following composition by volume:

H2 = 18%, CH4 = 40%, C2H6 = 10%, C4H8 = 2%, CO = 6%, CO2 = 7%, O2 = 1% and rest is nitrogen.
Calculate (i) the volume of oxygen and air required for the complete combustion of 10 m3 of this fuel; (ii) the
weight of air required for the complete combustion of 10 m3 of this fuel.
Solution:
Combustion equations are as follows:
H2 + ½ O2 H2O
CH4 + 2O2 CO2 + 2H2O

24
C2H6 + 3.5O2 2CO2 + 3H2O
C4H8 + 6O2 4CO2 + 4H2O
CO + ½ O2 CO2
Composition Volume in 1 m3 of fuel Volume of O2 required (m3)
H2 = 18% 0.18 0.18 x 0.5 = 0.09
CH4 = 40% 0.40 0.40 x 2 = 0.80
C2H6 = 10% 0.10 0.10 x 3.5 = 0.35
C4H8 = 2% 0.02 0.02 x 6 = 0.12
CO = 6% 0.06 0.06 x 0.5 = 0.03
CO2 = 7% 0.07 -
O2 = 1% 0.01 -
N2 = 16% 0.16 -
Total O2 required = 1.39 m3
Volume of O2 required for complete combustion = Total O2 required – O2 present in the fuel
= 1.39 – 0.01
= 1.38 m3
For 1 m3 of fuel, volume of O2 required = 1.38 m3

∴ For 10 m3 of fuel, volume of O2 required = 1.38 x 10 = 13.8 m3

Assuming air to be a mixture of 79% nitrogen and 21% oxygen by volume, volume of air required
for 10 m3 fuel = 13.8 x 100/21 = 65.71 m3
To calculate weight of air required,
22.4 m3 air at STP weighs 28.94 kg
65.71 m3 air at STP weighs 84.90 kg
The weight of air required for the complete combustion = 84.90 kg

Example 4: A gas has the following compounds by volume:

H2 = 22%, C3H6 = 14%, CO = 23%, O2 = 7%, CO2 = 17%, N2 = 17%.
Calculate the volume of air for complete combustion of 8 m3 of fuel.
Solution:
Combustion equations are as follows:
H2 + ½ O2 H2O
C3H6 + 4.5O2 3CO2 + 3H2O
CO + ½ O2 CO2
Composition Volume in 1 m3 of fuel Volume of O2 required (m3)
H2 = 22% 0.22 0.22 x 0.5 = 0.11
C3H6 = 14% 0.14 0.14 x 4.5 = 0.63

25
 CO = 23% 0.23 0.23 x 0.5 = 0.115
O2 = 7% 0.07 -
CO2 = 17% 0.17 -
N2 = 17% 0.17 -
Total O2 required = 0.855 m3
Volume of O2 required for complete combustion = Total O2 required – O2 present in the fuel
= 0.855 – 0.07
= 0.785 m3
For 1 m3 of fuel, volume of O2 required = 0.785 m3

∴ For 8 m3 of fuel, volume of O2 required = 0.785 x 8 = 6.28 m3

Assuming air to be a mixture of 79% nitrogen and 21% oxygen by volume, volume of air required
for 8 m3 fuel = 6.28 x 100/21 = 29.90 m3

Power alcohol: Ethyl alcohol is used as an additive to motor fuels. When it is blended with petrol at
concentrations of 5-10%, it is called power alcohol. The addition of ethyl alcohol to petrol increases its octane
number.
Manufacture of Ethyl alcohol: Ethyl alcohol is manufactured by the fermentation process.
Fermentation is the slow decomposition of complex organic compounds into simpler compounds by the action
of enzymes. Ethyl alcohol is manufactured by the fermentation of cheap sugar materials such as molasses and
starchy materials using enzymes. Enzymes such as invertase, zymase are produced by microorganisms like
yeast.
(1) Using molasses as raw material: Molasses is dark brown coloured mother liquor left after the
crystallization of cane sugar from concentrated sugarcane juice. It contains nearly 50% fermentable sugar.
The diluted solutions of molasses containing 8-10% sugar is taken in a big deep stainless steel tanks
and a small quantity of ammonium sulphate, ammonium phosphate and other nutrients are added. The pH is
maintained at 5 by adding a small quantity of sulphuric acid. Yeast is now added and the mixture is allowed
to stand for 2-3 days, the temperature being maintained at 25°-30°C. The fermentation sets in and the enzymes
invertase and zymase present in yeast decompose the sugar into ethyl alcohol with the evolution of CO2.
invertase
C12H22O11 + H2O C6H12O6 + C6H12O6
Sucrose Glucose Fructose
zymase
C6H12O6 2C2H5OH + 2CO2
Glucose Ethyl alcohol

(2) Using starchy material as raw material: When starchy materials such as potatoes, barley, maize or
cellulose derivatives are used, they are first hydrolysed and then fermented by enzymes.

26
 Advantages: The advantages of power alcohol are as follows:
(1) Ethyl alcohol is a good antiknocking agent. The octane value of petrol is 65 while that of power
alcohol is 90.
(2) The moisture content present is absorbed by alcohol.
(3) Ethyl alcohol contains oxygen atoms, which help for complete combustion of power alcohol
thereby reducing the emissions of pollutants such as CO.
(4) Power alcohol is cheaper than petrol.
(5) Alcohol petrol blends have lesser starting difficulties.

Disadvantages: The disadvantages of power alcohol are as follows:

(1) The calorific value of ethyl alcohol is 7000 cal/g, while that of petrol is 11500 cal/g. Thus, ethyl
alcohol has much lower calorific value than that of petrol. (This problem could be overcome by using a
specially designed engine with higher compression ratio.)
(2) Compared to petrol, the output of the power generated using power alcohol is reduced up to 35%.
(3) Ethyl alcohol has high surface tension and its atomization is difficult, especially at lower
temperature, thereby causing starting problem.
(4) It may undergo oxidation to form acetic acid, which corrodes engine parts.
(5) As it contains oxygen atom, the amount of air required for complete combustion is less. Therefore,
the carburetor and engine need to be modified.

Green fuel: Green fuel, also known as biofuel, a carbon-neutral or carbon-free alternative to fossil
fuels that is produced from renewable sources.
It is believed by some to be more environmentally friendly than the widely-used fossil fuels that power
most of the world. One of the green fuels is the biodiesel.

Biodiesel: Biodiesel is an alternative fuel similar to conventional or ‘fossil’ diesel. It is alkyl (methyl,
ethyl or propyl) ester of long chain free fatty acids. Biodiesel can be produced from straight vegetable oil,
animal oil/fats, tallow and waste cooking oil (triglyceride) using alcohol and base as a catalyst by the chemical
process called transesterification, as given below (Figure 4). Transesterification is a process of converting one
ester to the other ester. An oil is glycerol esters of three fatty acids which is converted to alkyl esters. In the
process of transesterification, glycerine (glycerol) is obtained as a byproduct.
Biodiesel has many environmentally beneficial properties. The main benefit of biodiesel is that it is
‘carbon neutral’. This means that the fuel produces no net output of carbon in the form of carbon dioxide
(CO2), hence it is green fuel.

27
 Figure 4 : Synthesis of Biodiesel

Process for the synthesis of biodiesel: The process involves treating the oil with excess of alcohol
generally methanol (CH3OH), in presence of base as a catalyst such as sodium hydroxide (NaOH), sodium
methoxide (CH3ONa). The mixture is heated when monomethyl esters of long chain free fatty acids (biodiesel)
and glycerine are obtained. The mixture is allowed to settle down at the bottom of the tank through gravity
separation method. Glycerine is then drawn off from the bottom of the vessel. The excess methanol is removed
by distillation.

Advantages: The advantages of biodiesel are as follows:

(1) Biodiesel is produced from animal and vegetable fat i.e. Renewable Resources. It can be
produced on demand and it also causes less pollution than petroleum diesel.
(2) Biodiesel can be used in existing diesel engines with little or no modifications at all and can
replace fossil fuels to become the most preferred primary transport energy source.
(3) Using biodiesel instead of petroleum diesel can reduce greenhouse gases up to 78%.
(4) Since the source of biodiesel is renewable raw materials availability, production and distribution
can be done locally.
(5) Biodiesel is biodegradable and non-toxic in nature.

28