CHEMISTRY OF FUELS

12/08/21 Dr P B Dwivedi, NMIMS 1

University, Mumbai
• Fuels: substances which undergo combustion in
the presence of air to produce a large amount of
heat that can be used economically for domestic
and industrial purpose.
• This definition does not include nuclear fuel because
it cannot be used easily by a common man.
• The various fuels used economically are wood, coal,
kerosene, petrol, diesel gasoline, coal gas, producer
gas, water gas, natural gas (LPG) etc.

12/08/21 Dr P B Dwivedi, NMIMS 2

University, Mumbai
 Classifications
Fuels can be broadly classified by origin as,
(i)Primary or natural fuels: coal, wood etc
(ii)Secondary or artificial or derived fuels: petrol, diesel
On the basis of physical state, as :
(i) Solid fuels
(ii) Liquid fuels
(iii) Gaseous fuels
12/08/21 Dr P B Dwivedi, NMIMS 3
University, Mumbai
 Basis Origin Physical
State
Source Natural or primary Artificial or
Secondary or
Derived
Wood, peat, lignite, Semi coke, charcoal Solid fuels
coal
Petroleum Petrol, kerosene, Liquid
gas oil, coal tar, fuels
etc.
Producer gas, coke- Gaseous
oven gas, water fuels
gas, blast furnace
gas, compressed
butane gas.
12/08/21 Dr P B Dwivedi, NMIMS 4
University, Mumbai
 Characteristics of Fuels
The physical properties for which fuels are tested and
their ideal requirements are listed below :
(i) Calorific value or specific heat of combustion.
(ii) Ignition temperature
(iii) Flame temperature
(iv) Flash and Fire point.

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University, Mumbai
(v) Aniline point
(vi) Knocking.
(vii) Specific gravity
(viii) Cloud and Pour point
(ix) Viscosity
(x) Coke number.

12/08/21 Dr P B Dwivedi, NMIMS 6

University, Mumbai
The chemical properties include the compositional
analysis of fuel.
For solid and liquids fuels :
(i) Percentage of various elements such as C, H, O,
N, S, etc.
(ii) Percentage of moisture
(iii) Percentage of volatile matter

12/08/21 Dr P B Dwivedi, NMIMS 7

University, Mumbai
For gaseous fuels :
(i) Percentage of combustible gases e.g. – CO, H2,
CH4, C2H4, C2H6, C4H10, H2S etc.
(ii) Percentage of non-combustible gases e.g. N2,
CO2 etc.

12/08/21 Dr P B Dwivedi, NMIMS 8

University, Mumbai
 Calorific Value

• number of units of heat evolved during complete

combustion of unit weight of the fuel.
• A British Thermal Unit: the heat required to raise
the temperature of one pound of water from 60 F to
61 F.
• The Calorie: the heat required to raise the temperature
of one kg of water from 15C to 16C.

12/08/21 Dr P B Dwivedi, NMIMS 9

University, Mumbai
 High and Low Calorific Values

Calorific values are of two types as,

(i)High or Gross Calorific Value (H.C.V. or G.C.V.)
(ii)Low or Net Calorific Value (L.C.V. or N.C.V.)
High calorific value may be defined as, the total
amount of heat produce when one unit of the fuel has
been burnt completely and the combustion products
have been cooled to 16C or 60F.

12/08/21 Dr P B Dwivedi, NMIMS 10

University, Mumbai
• LCV: is the net heat produced when unit mass or
volume of fuel is completely burnt and products are
allowed to escape.
• Net or lower C.V.= Gross C.V. – Latent heat of
water formed
• Or Gross C.V – Mass of hydrogen  9  Latent heat
of steam (587 cal/g)
• (Because 1 part by weight of hydrogen produces 9
parts (1 + 8) by mass of water)

12/08/21 Dr P B Dwivedi, NMIMS 11

University, Mumbai
• The calorific value of fuels (e.g. Coal) is determined
theoretically by Dulong formula, or I.A. Davies
formula.
• Dulong formula can be expressed as,

HCV = 1/100 [8,080 C+ 34,500(H- O/8)+ 2240 S]

Where C = % Carbon, H = % Hydrogen, O = %

Oxygen, S = % Sulphur
12/08/21 Dr P B Dwivedi, NMIMS 12
University, Mumbai
• Oxygen in fuel (coal) is in combined state as
water and hence it does not contribute to
heating value of fuel.
• LCV = [HCV – 0.09 H(%) × 587] cal/g

12/08/21 Dr P B Dwivedi, NMIMS 13

University, Mumbai
Sr. Property Solid Fuels Liquid Fuels Gaseous Fuels
No.
1. Calorific value Low Higher Highest

2. Specific gravity Highest Medium Lowest

3. Ignition point High Low Lowest

4. Efficiency Poor Good Best

5. Air required for Large and excess Less excess of air Slight excess of air
combustion of air

6. Use in I.C. engine Cannot be used Already in use Can be used

7. Mode of supply Cannot be piped Can be piped Can be piped

8. Space for storage Large 50% less than solid Very high space
fuel

9. Relative cost Cheaper Costly More costly than

other two

10. Care in storage and Less care required Care is necessary Great care required
transport

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University, Mumbai
 Classification of Coal

Sr Types Moisture C H O Ash Calorific Uses

No of Coal of Air % % % % Value
Dried At (kcal/kg)
40C
1. Peat 25 57 6 35 2 5400 Power generation and
domestic purpose.
2. Lignite 20 67 5 20 8 6500 Manufacture of
producer gas, thermal
power plants.
3. Bitumi 4 83 5 15 7 8000 For metallurgical
nous coke, coal gas, boiler,
domestic purpose
4. Anthra 2 92 3 2 3 8600 Boilers, metallurgical
cite fuel, domestic

12/08/21 Dr P B Dwivedi, NMIMS 15

University, Mumbai
 Analysis of Coal

The proximate analysis is easy and quicker and it gives a fair

idea of the quality of coal.

The ultimate analysis is essential for calculating heat

balances in any process for which coal is employed as a fuel.
12/08/21 Dr P B Dwivedi, NMIMS 16
University, Mumbai
 Moisture
• It is determined by heating about one gm. of finely
powdered coal at 105C to 110C for an hour in
electric oven. The loss in weight is reported as due to
moisture.
• % Moisture = [loss in wt of sample × 100]/wt of coal
taken

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University, Mumbai
 Ash

• A known weight of sample is taken in a crucible and

the coal is burnt completely at 700C – 750C in
muffle furnace until a constant weight is obtained.
The residue left in the crucible is ash content in coal
which is calculated as
• % of Ash = [wt of residue left in crucible 100]/ wt
of coal taken

12/08/21 Dr P B Dwivedi, NMIMS 18

University, Mumbai
 Volatile matter

• For determining volatile matter content, a known

weight of dried sample is taken in a crucible with
properly fitting lid. It is then heated at 950C  20C
for exactly seven minutes in previously heated muffle
furnace. The loss in weight is due to volatile matter
which is calculated as
• Volatile matter = [loss in wt at 9500C × 100]/wt of
coal sample
12/08/21 Dr P B Dwivedi, NMIMS 19
University, Mumbai
iv) Fixed carbon :
% of Fixed carbon = 100 – (% of moisture + % of ash +
% of volatile matter)
• In any good sample of coal, the percentages of
moisture, ash, volatile matter should be as low as
possible and thus the percentage of fixed carbon
should be as high as possible.

12/08/21 Dr P B Dwivedi, NMIMS 20

University, Mumbai
 Determination of C & H
• Accurately weighed coal sample is burnt in a current
of oxygen in a combustion apparatus, which is heated
to about 350C.
• Carbon and hydrogen of coal are converted into
carbon-dioxide and water vapour. The gaseous
products of combustion are absorbed in anhydrous
CaCl2 and KOH tubes of known weights.
• After complete absorption of H2O and CO2, the
tubes are again weighted.
12/08/21 Dr P B Dwivedi, NMIMS 21
University, Mumbai
 C + O2  CO2
12 parts  44 parts
2H2 + O2  2H2O
4 parts  36 parts
• % of Carbon = [increase in wt of KOH tube × 12 ×
100]/wt of coal taken × 44
• % of Hydrogen =[increase in wt of CaCl2 tube × 4
100]/wt of coal taken × 36

12/08/21 Dr P B Dwivedi, NMIMS 22

University, Mumbai
 Nitrogen
Nitrogen is calculated by Kjehldals Method.
% N = [vol of acid consumed in neutralizing NH3 × N × 1.4]/wt
of coal taken
% Sulphur: [wt of BaSO4 obtained × 32× 100]/wt of coal taken ×
233
(v) Oxygen:
The oxygen is determined indirectly by calculation as
% of Oxygen = 100 – (% of C + % of H + % of N + % of S + %
of Ash)

12/08/21 Dr P B Dwivedi, NMIMS 23

University, Mumbai
 Bomb Calorimeter

12/08/21 Dr P B Dwivedi, NMIMS 24

University, Mumbai
• Let x = mass in g of fuel taken in crucible
• W = mass of water in calorimeter
• w = water equivalent in g of calorimeter, stirrer, thermometer,
bomb etc.
• t1 & t2 are initial & final temperatures of water in calorimeter
• L = higher calorific value of fuel in cal/g
• Then heat liberated by buring of fuel = xL
• Heat absorbed by water & apparatus = (W+w)(t2-t1)
• But heat liberated = heat absorbed
• so, xL = (W+w)(t2-t1)
• L = (W+w)(t2-t1)/x cal/g or kcal/kg

12/08/21 Dr P B Dwivedi, NMIMS 25

University, Mumbai
• If H = % of hydrogen in fuel
• 9H/100 g = mass of water from 1 g of fuel= 0.09H g
• So heat taken by water in forming steam = 0.09 H ×
587 cal
• LCV = HCV - 0.09 H × 587 cal/g
• By considering fuse wire correction, acid correction
& cooling corection
• L = [{(W+w)(t2-t1+ cooling correction)}- {acid +fuse
correction}]/x cal/g or kcal/kg

12/08/21 Dr P B Dwivedi, NMIMS 26

University, Mumbai
 Combustion
• Combustion is a process in which oxygen from the
air reacts with the elements or compounds to give
heat.
• As the elements or compounds combine in indefinite
proportions with oxygen, we need to calculate what is
minimum oxygen or air required for the complete
combustion of compounds. The commonly involved
combustion reactions are :
12/08/21 Dr P B Dwivedi, NMIMS 27
University, Mumbai
i) C + O2  CO2
ii) 2H2 + O2  2H2O OR H2 + (O)  H2O
iii) S + O2  SO2
iv) 2CO + O2  2CO2 OR CO + (O) 
CO2
v) CH4 + 2O2  CO2 + 2H2O
vi) 2C2H6 + 7O2  4CO2 + 6H2O
vii) C2H4 +3O2­ 2CO2 + 2H2O
viii) 2C2H2 + 5O2  4CO2 + 2H2O

12/08/21 Dr P B Dwivedi, NMIMS 28

University, Mumbai
 Hint to Solve Problems on Calculation of Quantity of Air
Required for Combustion of Fuel :

• First write the appropriate chemical reaction with

oxygen and find their relation between the element or
compound on weight or volume basis.
e.g C + O2  CO2
(12 gm) + (32 gm)
2H2 + O2  2H2O
(4 gm) + (32 gm)
S + O2  SO2
(32 gm) + (32 gm)
12/08/21 Dr P B Dwivedi, NMIMS 29
University, Mumbai
2) Calculate the oxygen required on the basis of unit quantity of
fuel.
3) Calculate the total oxygen required for the combustion and
subtract the oxygen which is present in the fuel.
4) The oxygen calculated should be converted into air by
knowing that air contains 23 parts by weight of oxygen OR 21
parts by volume of oxygen.
5) The average molecular weight of air is 28.94 gm.

12/08/21 Dr P B Dwivedi, NMIMS 30

University, Mumbai
Calculate the weight and volume of air required
for complete combustion of 5 kg. coal with
following compositions, C = 85%; H = 10%;
O = 5%
Soln. :
Combustion reactions :
C + O2  CO2
12 + 32  44
H2 + O2  H2O
2 + 16  18
12/08/21 Dr P B Dwivedi, NMIMS 31
University, Mumbai
 Weight of Weight of O2 required
elements per kg. for complete combustion
of coal in kg.
C = 0.85 0.85 32/12 = 2.26 kg.
H = 0.1 0.1  8 = 0.8 kg.
O = 0.05 –
Total oxygen = 3.06 kg.

Weight of oxygen required

= Weight of oxygen needed – weight of oxygen present
= 3.06 – 0.05 = 3.01
12/08/21 Dr P B Dwivedi, NMIMS 32
University, Mumbai
 Air required for complete combustion
= 3.01  100/23
= 13.08 kg. per 1 kg. coal.
 Air required for 5 kg. of coal
= 13.08  5 = 65.40 kg.
Volume of Air
 28.94 kg. of air = 22,400 ml volume at NTP
65.4 kg. of air =22400× 65.4/ 28.94
=50815.8 ml. Air
=50.8158 litres of air

12/08/21 Dr P B Dwivedi, NMIMS 33

University, Mumbai