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Combustion
Combustion Basics
Any material that can be burned to release thermal
energy is called a fuel.
Most familiar fuels consist primarily of hydrogen and
carbon. They are called hydrocarbon fuels and are
denoted by the general formula CnHm Hydrocarbon fuels
exist in all phases, some examples being coal, gasoline,
and natural gas.
In practical engines and power plants the source of
heat is the chemical energy of substances (fuels). This
energy is released during the chemical reaction of the
fuel with oxygen. Heat is released during the reaction.
Fuel
Fuel
The most important fuel elements are carbon and
hydrogen, and most fuels consists of these and
sometimes a small amount of sulphur.
The fuel may contain some oxygen and a small quantity
of water vapour, nitrogen or ash (incombustibles).
Where fuels contain some oxygen this oxygen is
available for the combustion process, and so the
fuel requires a smaller supply of air.
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Oxygen in Air
For a given amount of fuel there is a definite amount of
Source of Oxygen
The most convenient source of oxygen supply is that of
the atmosphere.
oxygen required for its complete combustion (therefore
Air also contains Nitrogen and traces of other gases.
a definite amount of air).
It is usual in combustion calculations to take air as:
To ensure complete combustion of fuel, it is usual to
supply air in excess of the amount required for
chemically correct combustion.
23.3% O2 and 76.7% N2 by mass;
21% O2 and 79% N2 by volume.
The small traces of other gases in dry air are included in the nitrogen,
which is sometimes called atmospheric nitrogen.
Fuel
Gaseous Fuels (chemically simplest)
Natural gas
Refinery gas
Liquid Fuels (mostly hydrocarbons)
Kerosene
Gasoline, diesel
Alcohol (Ethanol)
Oil
Solid Fuels
Coal (Anthracite, bituminous, subbituminous, lignite)
Wood
C O2 CO2
1
H2 O2 H2 O
2
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C8 H18 A O2 B CO2 D H2 O
C8 H18 A O2 8 CO2 9 H2 O
C8 H18 12.5 O2 8 CO2 9 H2 O
Composition of air:
23.3% O2 and 76.7% N2 by mass;
21% O2 and 79% N2 by volume.
C8 H18 12.5 ( O2 3. 76 N 2 )
8 CO2 9 H2 O 47 N 2
Ultimate Analysis
C8 H18 A O2 B CO2 D H2 O
C8 H18 A O2 8 CO2 9 H2 O
An accurate chemical analysis by mass of
the
important elements in the fuel is called the Ultimate
analysis.
The elements usually included are carbon, hydrogen,
oxygen, nitrogen and sulphur.
C8 H18 12.5 O2 8 CO2 9 H2 O
C8 H18 12.5 ( O2 3. 76 N 2 )
8 CO2 9 H2 O 47 N 2
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Proximate Analysis
Analysis of Liquid Fuels
Proximate analysis gives the percentages of inherent
moisture, volatile matter, and combustible solid called
fixed carbon.
The fixed carbon is found as a remainder by deducting
the other quantities.
Fuel
Analysis by volume of a Typical Natural Gas
Properties of Selected Fuels
CH4
C2H6
C3H8
Other HCs
H2S
Heating Value
(106 J/m3)
(wt%)
Natural gas (No.1)
87.7
5.6
2.4
1.8
2.7
Natural gas (No.2)
88.8
6.4
2.7
2.0
0.0004
86.4
12.7
0.1
(Ultimate analysis)
43.2
41.9
Heating value
(106 J kg-1)
(wt%)
Gasoline (No.2)
(Proximate analysis)
Carbon
Moisture
0.4-0.7
Ash
Heating value
(%)
(%)
(%)
(%)
(106 J kg-1)
Anthracite (PA)
77.1
3.8
5.4
13.7
27.8
Bituminous (PA)
70.0
20.5
3.3
6.2
33.3
Subbituminous (CO) 45.9
30.5
19.6
4.0
23.6
Lignite (ND)
28.2
34.8
6.2
16.8
30.8
Volatile matter
0.1
Data from Flagan and Seinfeld, Fundamentals of Air Pollution Engineering, 1988, Prentice-Hall.
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Combustion Stoichiometry
Stoichiometric air-fuel ratio
Combustion in Oxygen
Cn H m O2 CO2 H 2O
A stoichiometric mixture of air and fuel is one that
contains just sufficient oxygen for the complete
combustion of the fuel.
1.
2.
Can you balance the above equation?
Write the reactions for combustion of methane and
benzene in oxygen, respectively.
Answer
m
m
C n H m n O2 nCO2 H 2O
4
2
CH 4 2O 2 CO 2 2 H 2O
C6 H 6 7.5O2 6CO2 3H 2O
Combustion Stoichiometry
Combustion in Air (O2 = 21%, N2 = 79%)
Air-Fuel Ratio
Air-Fuel (AF) ratio
AF = m Air / m Fuel
Cn H m (O2 3.78N 2 ) CO2 H 2O N 2
Where:
1.
2.
Can you balance the above equation?
Write the reactions for combustion of methane and benzene
in air, respectively.
Answer
m
m
m
C n H m n (O 2 3.78N 2 ) nCO2 H 2O 3.78 n N 2
4
2
4
CH 4 2(O 2 3.78 N 2 ) CO 2 2 H 2O 7.56 N 2
m air = mass of air in the feed mixture
m fuel = mass of fuel in the feed mixture
Fuel-Air ratio: FA = m Fuel /m Air = 1/AF
Air-Fuel molar ratio
AFmole = nAir / nFuel
Where:
nair = moles of air in the feed mixture
nfuel = moles of fuel in the feed mixture
C6 H 6 7.5(O2 3.78 N 2 ) 6CO2 3H 2O 28.35N 2
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Air-Fuel Ratio
Rich mixture
- more fuel than necessary
(AF) mixture < (AF)stoich
Weak mixture
- more air than necessary
(AF) mixture > (AF)stoich
Percentage Excess Air
actual A/F ratio - stoichiome tric A/F ratio
stoichiome tric A/F ratio
A-
Air
F-
Fuel
Most combustion systems operate under lean conditions.
Why is this advantageous?
Consider the combustion of methanol in an engine. If the Air-Fuel
ratio of the actual mixture is 20, is the engine operating under rich
or lean conditions?
Mixture Strength
Stoichiome tric A/F ratio
Mixture Strength
Actual A/F ratio
Exhaust and Flue Gas Analysis
The products of combustion are mainly gaseous and
include vapour.
For analysis, the samples are usually cooled to a
temperature below saturation temperature of the
steam.
When steam is NOT included, the analysis is said to
be dry.
An analysis that includes the steam (from the
exhaust) is called a wet analysis.
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Example 7.1 from Eastop & McConkey
One kmol of octane (C8H18) is burned with air that contains
A sample of dry anthracite has the following composition
by mass:
20 kmol of O2. Assuming the products contain only CO2,
C 90%; H 3%; O 2.5%; N 1%; S 0.5%; ash 3%.
H2O, O2, and N2, determine the mole number of each gas in
the products and the airfuel ratio for this combustion
process.
Calculate:
(i) the stoichimetric A/F ratio;
(ii)the actual A/F ratio and the dry and wet analysis of the
products of combustion by mass and by volume, when
20% excess air is supplied.
(i)
(ii)
11.245
13.494 / 1
Problem 1
Problem 2
A sample of bituminous coal gave the following ultimate
analysis by mass:
Calculate the stoichiometric A/F ratio for benzene
(C6H6), and wet and dry analysis of the combustion
C 81.9%; H 4.9%; O 6%; N 2.3%; ash 4.9%.
products.
Calculate:
(i) the stoichimetric A/F ratio;
(ii) the analysis by volume of the wet and dry products of
combustion when 25% excess air is supplied.
(i)
(ii)
10.8/1
CO2 14.14%; H2O 5.07%; O2 4.08%; N2 76.71%; CO2
14.89%; O2 4.30 %; N2 80.81%
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Problem 2
Example 7.3 & 7.4 from Eastop & McConkey
Calculate the stoichiometric A/F ratio for benzene
Ethyl alcohol is burned in a petrol engine. Calculate:
(C6H6), and wet and dry analysis of the combustion
(i) The stoichiometric A/F ratio;
products.
(ii) The A/F ratio and the wet and dry analyses by volume of
the exhaust gas for a mixture strength of 90%;
13.2/1; [wet:]CO2 16.13%; H2O 8.06%; N2 75.81%;
[dry:] CO2 17.54%; N2 82.46%
(iii) The A/F ratio and the wet and dry analyses by volume of
the exhaust gas for a mixture strength of 120%.
Example 7.3 & 7.4 from Eastop & McConkey
Example 7.3 & 7.4 from Eastop & McConkey
Ethyl alcohol is burned in a petrol engine. Calculate:
For the stoichiometric mixture (just calculated), calculate:
(i) The stoichiometric A/F ratio;
(i) the volume of the mixture per kilogram of fuel at a
(ii) The A/F ratio and the wet and dry analyses by volume of
the exhaust gas for a mixture strength of 90%;
(iii) The A/F ratio and the wet and dry analyses by volume of
the exhaust gas for a mixture strength of 120%.
(i) 8.957/1; (ii) 9.952/1, [dry:]13.45% of CO2, 84.31% of N2;
temperature of 650C and a pressure of 1.013 bar;
(ii) The volume of the products of combustion per kilogram
of fuel after cooling to a temperature of 1200C at a
pressure of 1 bar.
(i) 9.219 m3 (ii) 9.219 m3
(iii) 7.47/1, [dry:] 8.77% of CO2, 82.46% of N2.
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Problem 3
Problem 4
In the actual combustion of benzene (C6H6) in an
The analysis of a supply gas is as follows: H2 49.4%;
engine the A/F ratio was 12/1. Calculate the wet and
CO 18%; CH4 20%; C4H8 2%; O2 0.4%; N2 6.2%; CO2 4%.
dry analysis of the combustion products.
Calculate:
(i) The stoichiometric A/F ratio;
(ii) the wet and dry analysis of the products of
CO2 13.38%; CO 3.94%; H2O 8.66%; N2 74.03%
combustion if the actual mixture is 20% weak
(i) 4.062 (by volume)
(ii) wet: CO2 9.0%, H2 O 17.5%, O2 3.08%, N2 70.4%
Problem 5
Problem 6
Propal alcohol (C3H7OH) is burned with 50 percent
A fuel mixture of 20 percent by mass methane (CH4)
excess air. Write the balanced reaction equation for
and 80 percent by mass ethanol (C2H6O), is burned
complete combustion and determine the air-to-fuel
completely with theoretical air. If the total flow rate of
ratio.
the fuel is 31 kg/s, determine the required flow rate of
air.
15.5 kg air/kg fuel
330 kg/s
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Problem 6
Problem 7
A certain natural gas has the following volumetric
Methane (CH4) is burned with dry air. The volumetric
analysis: 65 percent CH4, 8 percent H2, 18 percent N2,
analysis of the products on a dry basis is 5.20 percent
3 percent O2, and 6 percent CO2. This gas is now
CO2, 0.33 percent CO, 11.24 percent O2, and 83.23
burned completely with the stoichiometric amount of
percent N2.
dry air. What is the airfuel ratio for this combustion
Determine (a) the airfuel ratio and (b) the percentage
process?
of theoretical air used.
9.42 kg air/kg fuel
(a) 34.5 kg air/kg fuel, (b) 200 percent
Theoretical And Actual Combustion Processes
Complete combustion: If all the carbon in the fuel burns to
CO2, all the hydrogen burns to H2O, and all the sulfur (if any)
The combustion reaction is a particular kind of
reaction
in
which
products
are
formed
burns to SO2.
from
reactants with the release or absorption of energy as
heat is transferred to or from the surroundings.
A combustion process is complete if all the combustible components
of the fuel are burned to completion.
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Theoretical And Actual Combustion Processes
THEORETICAL AND ACTUAL
COMBUSTION PROCESSES
Reasons for incomplete combustion:
Incomplete combustion: If the combustion products contain
1. Insufficient oxygen;
any unburned fuel or components such as C, H2, CO, or OH.
2. insufficient mixing in the combustion chamber during the
limited time that the fuel and the oxygen are in contact, and
Reasons for incomplete combustion: 1 Insufficient oxygen,
3. dissociation (at high temperatures).
2 insufficient mixing in the combustion chamber during the
Oxygen has a much greater tendency to combine with
limited time that the fuel and the oxygen are in contact, and 3
hydrogen than it does with carbon. Therefore, the hydrogen in
dissociation (at high temperatures).
the fuel normally burns to completion, forming H2O.
Some of the carbon, however, ends up as CO or just as plain
C particles (soot) in the products.
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Stoichiometric or theoretical air: The minimum amount of air
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Excess air: The amount of air in excess of the stoichiometric
needed for the complete combustion of a fuel. Also referred to
amount. Usually expressed in terms of the stoichiometric air as
as the chemically correct amount of air, or 100% theoretical air.
percent excess air or percent theoretical air.
Stoichiometric or theoretical combustion: The ideal
50% excess air = 150% theoretical air
combustion process during which a fuel is burned completely
200% excess air = 300% theoretical air.
with theoretical air.
90% theoretical air = 10% deficiency of air
The complete combustion process with no free oxygen in
the products is called theoretical combustion.
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Deficiency of air: Amounts of air less than the stoichiometric
Predicting the composition of the
products is relatively easy when
the combustion process is
assumed to be complete.
amount. Often expressed as percent deficiency of air.
With actual combustion
processes, it is impossible to
predict the composition of the
products on the basis of the
mass balance alone.
Equivalence ratio: The ratio of the actual fuelair ratio to the
stoichiometric fuelair ratio.
Then the only alternative we
have is to measure the amount
of each component in the
products directly.
A commonly used device to
analyze the composition of
combustion gases is the Orsat
gas analyzer.
Determining the mole fraction of the
CO2 in combustion gases by using
the Orsat gas analyzer.
The results are reported on a
dry basis.
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ENTHALPY OF FORMATION AND
ENTHALPY OF COMBUSTION
Disregarding any changes in kinetic and potential energies, the energy change
of a system during a chemical reaction is due to a change in state and a change
in chemical composition:
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ENTHALPY OF FORMATION h f
The standard enthalpy of formation of a compound is the
change of enthalpy that accompanies the formation of 1
mole of a substance in its standard state from its
constituent elements in their standard states.
(The most stable form of the element at 1 bar of pressure
and the specified temperature, usually 298.15 K or 25
degrees Celsius).
The microscopic form of energy of a
substance consists of sensible, latent,
chemical, and nuclear energies.
When the existing chemical bonds
are destroyed and new ones are
formed during a combustion process,
usually a large amount of sensible
energy is absorbed or released.
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ENTHALPY OF FORMATION h f
ENTHALPY OF FORMATION h f
The standard enthalpy change of formation is measured in
The standard enthalpy change of formation is used in
units of energy per amount of substance. Most are defined
thermodynamics to find the standard enthalpy change of
in kilojoules per mole, or kJ mol1.
reaction.
All elements in their standard states (oxygen gas, solid
This is done by subtracting the sum of the standard
carbon in the form of graphite, etc.) have a standard
enthalpies of formation of the reactants from the sum of
enthalpy of formation of zero, as there is no change
the standard enthalpies of formation of the products, as
involved in their formation.
shown in the equation below.
To establish a starting point, we assign the enthalpy of formation of all
stable elements (such as O2, N2, H2, and C) a value of zero at the
standard reference state of 25C and 1 atm.
The molar enthalpy of reaction may be calculated using:
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Heating value: The amount of heat
released when a fuel is burned
completely in a steady-flow process
and the products are returned to the
state of the reactants. The heating
value of a fuel is equal to the
absolute value of the enthalpy of
combustion of the fuel.
The enthalpy of formation hf : The amount of energy
absorbed or released as the component is formed from its
stable elements during a steady-flow process at a specified
state.
Higher heating value (HHV): When
the H2O in the products is in the
liquid form.
Lower heating value (LHV): When
the H2O in the products is in the
vapor form.
The higher heating value of a fuel is equal to the sum of the lower heating
value of the fuel and the latent heat of vaporization of the H2O in the products.
For the fuels with variable
composition (i.e., coal, natural gas,
fuel oil), the heating value may be
determined by burning them
directly in a bomb calorimeter.
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Problem 5
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Problem 5
Calculate the molar enthalpy of reaction at 250C of
ethyl alcohol, C2H5OH.
The
enthalpy of combustion of propane gas, C3H8, at
250C
with the H2O in the products in the liquid phase is
-50 360 kJ/kg. Calculate the enthalpy of combustion
-1 231 428 kJ/kmol
with the H2O in the vapour per unit mass of fuel and
per unit amount of substance of fuel.
-46 364 kJ/kg; -2 040 030 kJ/kmol
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Partial Combustion
BOMB CALORIMETER
A calorimeter is a device used for calorimetry, the science of
measuring the heat of chemical reactions or physical changes as
well as heat capacity.
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Specific heat is the amount of heat per unit mass required to
raise the
temperature by one Kelvin:
Substance
Aluminum
c in cal/gm K
0.9
0.215
Bismuth
0.123
0.0294
Copper
0.386
0.0923
Brass
Q = heat added (energy)
c = specific heat
m = mass
T = change in temperature
c in J/gm K
Please attempt problems 7.1 to 7.12
0.38
0.092
Gold
0.126
0.0301
Lead
0.128
0.0305
Silver
0.233
0.0558
Tungsten
0.134
0.0321
Zinc
0.387
0.0925
0.14
0.033
2.4
0.58
Mercury
Alcohol(ethyl)
Water
4.186
Ice (-10 C)
2.05
0.49
Granite
0.79
0.19
Glass
0.84
0.2
Acknowledgement:
Prepared by: Ying Li
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