CHEMISTRY OF FUELS
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.
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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
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Basis
Origin
Source Natural or
primary
Artificial
Secondary
Derived
Physical
State
or
or
Wood, peat, lignite, Semi coke, charcoal Solid fuels
coal
Crude oil,
Vegetable oils
Petrol,
kerosene,
gas oil, coal tar,
alcohol
Liquid
fuels
Natural gas
Producer gas, cokeoven gas, water
gas, blast furnace
gas, compressed
butane gas, LPG
Gaseous
fuels
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.
- efficiency of fuel: how much heat it produces
(ii)
Ignition temperature
(iii)
Flame temperature
(iv)
Flash and Fire point.
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(v)
Aniline point
(vi)
Knocking.
(vii) Specific gravity
(viii) Cloud and Pour point
(ix)
Viscosity
(x)
Coke number.
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
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.
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 gm of water by 1C (15C to 16C) at standard
atmospheric pressure.
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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 produced when one unit of the fuel
has been burnt completely and the combustion
products have been cooled to 16C or 60F.
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LCV: is the net heat produced when unit mass or
volume of fuel is completely burnt and products are
allowed to escape.
Net or Low C.V.= Gross C.V. loss due to water
formed
Or Gross C.V Mass of hydrogen 9 Latent heat
of steam (587 cal/g) (1 gram of water at 100 C changes to 1 gram
of steam at 100 C by absorbing 540 calories)
(Because 1 part by weight of hydrogen produces 9
parts (1 + 8) by mass of water)
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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] cal/g
Where C = % Carbon, H = % Hydrogen, O = %
Oxygen, S = % Sulphur
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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
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Bomb Calorimeter
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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 by fuel = heat absorbed by water, apparatus
so, xL = (W+w)(t2-t1)
L = (W+w)(t2-t1)/x cal/g or kcal/kg
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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
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Sr.
No.
Property
Solid Fuels
Liquid Fuels
Gaseous Fuels
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
combustion
Large and excess Less excess of air
of air
Slight excess 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
other two
10.
Care in storage and
transport
Less care required
Care is necessary
Great care required
than
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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 :
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C + O2 CO2
2H2 + O2 2H2O
OR H2 + (O) H2O
S + O2 SO2
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
i)
ii)
iii)
iv)
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Hint to Solve Problems on Calculation of Quantity of Air
Required for Combustion of Fuel :
1. First write the appropriate chemical reaction with oxygen and find their relation between the
element or compound on weight or volume basis.
C
+
O2
CO2
(12 gm) +
(32 gm)
(44gm)
1
1
1
e.g
by weight
by volume
2H2 +
O2
by weight
(4 gm) +
by volume
2
S
by weight
by volume
+
O2
(32 gm) +
1
2H2O
(32 gm)
(36gm)
1
2
SO2
(32 gm)
(64gm)
1
1
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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 28.94g
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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
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Weight of
elements per kg.
of coal
Weight of O2 required
for complete combustion
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 kg
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Weight of oxygen for required for 5 kg. of coal
= 3.01 5
= 15.05 kg.
Volume of oxygen = 22.4/ 32 x 15050g = 10535 litres = 10.53m 3
Weight of Air required for 5 kg. of coal
=
100/23 15050g = 65.43 kg.
Volume of Air required for 5 kg. of coal
= 100/21 x 10535 = 50166 litres or 50.166 m 3of air
or
Volume of air= 22.4/ 28.94 x 65430g = 50643 litres or 50.643 m 3air
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Classification of Coal
Sr Types
No of Coal
Moisture
of Air
Dried At
40C
C
%
H
%
O
%
Ash
%
Calorific
Value
(kcal/kg)
Uses
1.
Peat
25
57
35
5400
Power generation and
domestic purpose.
2.
Lignite
20
67
20
6500
Manufacture
of
producer gas, thermal
power plants.
3.
Bitumi
nous
83
15
8000
For
metallurgical
coke, coal gas, boiler,
domestic purpose
4.
Anthra
cite
92
8600
Boilers, metallurgical
fuel, domestic
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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.
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Moisture
It is determined by heating about one gm. of finely
powdered coal at 105C to 110C 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
Decreases calorific value of coal
Takes away heat in the form of latent heat
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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 950C 20C 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
Decreases calorific value
Forms smoke and pollutes air
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Ash (non combustible matter)
A known weight of sample is taken in a crucible and the
coal is burnt completely at 700C 750C 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
Reduces calorific value as it is non burning part
Ash disposal is a problem
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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.
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Determination of C & H
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Accurately weighed coal sample is burnt in a current
of oxygen in a combustion apparatus, which is heated
to about 350C.
Carbon and hydrogen of coal are converted into water
vapour and carbon-dioxide. The products of
combustion are absorbed in anhydrous CaCl2 and
KOH tubes respectively of known weights.
After complete absorption of H2O and CO2, the tubes
are again weighted.
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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
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Determination of Nitrogen
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Procedure
The method consists of heating a substance with sulphuric acid, which
decomposes the organic substance by oxidation to liberate the reduced
nitrogen as ammonium sulphate. In this step potassium sulphate is added to
increase the boiling point of the medium (from 337 C to 373 C) . Chemical
decomposition of the sample is complete when the initially very dark-coloured
medium has become clear and colourless.
The solution is then distilled with a small quantity of sodium hydroxide, which
converts the ammonium salt to ammonia. The amount of ammonia present,
and thus the amount of nitrogen present in the sample, is determined by back
titration. The end of the condenser is dipped into a solution of boric acid. The
ammonia reacts with the acid and the remainder of the acid is then titrated with
a sodium carbonate solution by way of a methyl orange pH indicator.
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Degradation:
Sample + H2SO4 (NH4)2SO4(aq) + CO2(g) + SO2(g) + H2O(g)
Liberation of ammonia:
(NH4)2SO4(aq) + 2NaOH Na2SO4(aq) + 2H2O(l) + 2NH3(g)
Capture of ammonia:
B(OH)3 + H2O + NH3 NH4+ + B(OH)4
Back-titration:
B(OH)3 + H2O + Na2CO3 NaHCO3(aq) + NaB(OH)4(aq) + CO2(g) + H2O
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Determination of Nitrogen
Nitrogen is calculated by Kjehldals Method.
The nitrogen is converted to NH3 and passed through a known volume
of standard acid. On neutralization, the excess acid is back titrated
with a base.
1000 ml of x N acid
14 gm of Nitrogen
% N = volume of acid consumed in neutralizing NH3 N x 14 x 100
wt of coal taken x 1000
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Determination of Sulphur
% Sulphur: [wt of BaSO4 obtained 32 100]/wt
of coal taken 233
Determination of Oxygen:
The oxygen is determined indirectly by calculation
as
% of Oxygen = 100 (% of C + % of H + % of N +
% of S + % of Ash)
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Importance of Ultimate analysis:
Carbon: Greater the % carbon, better is the quality and calorific value of
coal
Hydrogen: most of hydrogen is in form of moisture and volatile matter.
Only a small % is combustible, hence it decreases C.V. Smaller the H%
better is quality of coal
Nitrogen: does not burn, hence it has no C.V. Negligible N% is good coal
Sulphur: it increases C.V, but causes Sox pollution. Hence lower S% is
better
Oxygen: most of oxygen is in form of moisture, hence it decreases C.V.
Smaller the H% better is quality of coal
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