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Mechanical Engineering

Department

Power Plant Engineering


(MEng 5211)

Lecture 3. Fuels and Combustion

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Prepared by: Addisu D. May, 2018
Introduction
 Any matter that is a source of heat is called fuel.
 Fuel releases its energy either through a chemical reaction, such
as during combustion, or via nuclear fission or fusion.
 An important property of a useful fuel is that its energy can be
stored and released only when needed, and that the release is
controlled in such a way that the energy can be harnessed to
produce the desired work.
 Fuels are broadly classified as fossil or organic or chemical fuel,
nuclear fuel, and rocket fuel.
 Fossil fuels are hydrocarbons, primarily coal and petroleum
(liquid petroleum or natural gas), formed from the fossilized
remains of dead plants and animals by exposure to heat and
pressure in the earth’s crust over hundreds of millions of years.
 Fossil fuels generate substantial quantities of heat per unit of
mass or volume by reacting with an oxidant in a combustion
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process.
Introduction
 In most practical applications including combustion in a steam
generator, air is used as the oxidant, although in certain processes
oxygen, oxygen-enriched air and other chemicals are used as the
oxidant.
 Energy generation by a nuclear fuel takes place either by the
process of nuclear fission of heavy fissile elements in a nuclear
reactor resulting in chain reactions or by the process of nuclear
fusion, in which simple atomic nuclei are fused together to form
complex nuclei, as in case of fusion of hydrogen isotopes to form
helium.
 The process of nuclear fusion is also known as a thermonuclear
reaction, which is difficult to control even today. As a result, the
main source of nuclear energy presently available is mainly from
nuclear fission.

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Introduction
 The most common fissile radioactive heavy metals are naturally
occurring isotope of uranium, U235, artificial isotope of uranium,
U233, and artificial element plutonium, P239.
 In a nuclear reactor plutonium, P239, is produced from naturally
occurring isotope of uranium, U238, and U233 is produced from the
naturally occurring element thorium, Th232.
 Nuclear fission of 1 kg of U235 generates about 85*106 MJ of heat,
which is equivalent to the heat generated by combustion of about
5106 kg of coal with a high heating value (HHV) of 17 MJ/kg.
 In nuclear reactions, the product is either isotopes of the reactants
or other nuclei.
 Unlike fossil fuel, rocket fuel does not depend on its surroundings
for the oxidant. The oxidant is carried by the rocket itself. The
propellant is the chemical mixture burned to produce thrust in
rockets and consists of a fuel and an oxidizer.
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Introduction
 The increasing worldwide demand for energy has focused
attention on fuels, their availability and environmental effects.
 The fuels available to utility industry are largely nuclear and
fossil, both essentially nonrenewable. Nuclear fuels originated
with the universe, and it takes nature millions of years to
manufacture fossil fuels.
 Fossil fuels originate from the earth as a result of the slow
decomposition and chemical conversion of organic material. They
come in three basic forms: solid (coal). liquid (oil), and natural
gas.
 Coal represents the largest fossil-fuel energy resource in the
world.
 According to IEA report in 2015, coal is responsible for about 40
percent of electric-power generation in the world. Oil and natural
gas are responsible for another 27 percent. The remaining
5 percentage is mostly due to nuclear and hydraulic generation.
Introduction
 Most widely used fossil fuels for the production of steam in
relation to power are available in all the states of matter.
 Gaseous
✓ natural gas, blast furnace gas, coke-oven gas, refinery gas,
liquefied petroleum gas or (LPG), etc.
 Liquid
✓ high-speed diesel (HSD), light diesel oil (LDO), heavy fuel
oil (HFO), furnace oil (FO), low sulfur heavy stock (LSHS),
naphtha, liquefied natural gas (LNG), etc.
 Solid
✓ bituminous coal, anthracite, lignite, peat, oil shale, biomass,
rice husk, bagasse etc.

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Introduction
 Fossil fuels consist of a large number of complex compounds of
five elements: carbon (C), hydrogen (H), oxygen (O), sulfur (S),
and nitrogen (N). Besides these elements, all fuels contain mineral
matter (A) and moisture (M) to some extent.
 However, there are just three combustible elements of
significance in a fuel, e.g., carbon, hydrogen, and sulfur, of which
carbon is the principal combustible element with a HHV of
32.780 MJ/kg.
 Hydrogen has a very high HHV of 141.953 MJ/kg, but its content
in solid fuel is quite low, about 2 - 4%.
 The HHV of sulfur is only 9.257 MJ/kg, hence as a source of heat
its presence is insignificant, although it is more so since its
presence in coal is small in quantity.
 Major concern regarding sulfur is that it promotes corrosion and
creates atmospheric pollution problems.
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Introduction
 Contrary to solid and liquid fuels, gaseous fuels are mixtures of
combustible and non-combustible gases.
 Natural gas is gaseous fuel occurring in nature and consisting
mostly of organic compounds, normally methane (CH4), ethane
(C2H6), propane (C3H8), and butane (C4H10).
 The calorific value of natural gas varies between 26.1 and 55.9
MJ/m3, the majority averaging 37.3 MJ/m3.
 Natural gas on average contains 80 - 90% methane, 6 - 9% ethane,
and 2 - 5% propane. Noncombustible gases present in minor
quantities in natural gases are nitrogen (0.5 - 2.0%) and carbon
dioxide (0.1 - 1.0%).
 LPG is a material composed predominantly of the following
hydrocarbons or mixtures of them: propane, propylene, n-butane,
isobutene, and butylenes. The mixture is liquefied at room
temperature at very high pressure. An average mixture of LPG is
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Coal
 Fossil solid fuels are available in almost all countries but are distributed
unevenly.
 The majority of countries is not rich in coal production. There are around
70 countries that contain recoverable coal reserves.
 The world currently consumes over 7,700 Mt of coal which is used by a
variety of sectors including power generation, iron and steel production,
cement manufacturing and as a liquid fuel.
 Coal is the major fuel used to generate over 40% of the world’s electricity
demand and provides 30% of global primary energy needs. Coal is also
used in the production of 70% of the world’s steel.
 According to World Energy Council Report in 2016 the largest producer
of coal is the People’s Republic of China (about 3747 million tons of coal
was produced in the year 2015) followed by the United States (813
million tons) , India (677 million tons), Australia (485 million tons),
Indonesia (392 million tons). Russia, South Africa, Germany, Poland, and
Kazakhstan also contribute to global coal production to some extent.
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Coal
 According to geological order of formation, coal may be of the
following types: (1) Peat, (2) Lignite, (3) Subbitumioous, (4)
Bituminous, (5) Subanthracite, and (6) Anthracite, with increasing
percentages of carbon. After anthracite, graphite is formed.
 Anthracite contains more than 86% fixed carbon (in amorphous
form) and less volatile matter. Volatile matter helps in the ignition of
coal. So, it is often difficult to bum anthracite.
 Bituminous coal is the largest group containing 46-86% of fixed
carbon and 20-40% of volatile matter. It can be low-volatile,
medium-volatile and high-volatile. The lower the volatility, the
higher the heating value.
 Lignite is the lowest grade of coal containing moisture as high as
30% and high volatile matter.
 According to ASTM (American Society of Testing and Materials),
peat is not regarded as a rank of coal. Peat contains up to 90%
moisture and is not attractive as a utility fuel.
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Coal Analysis
 There are two methods
➢ ultimate analysis and
➢ proximate analysis.
 The ultimate analysis determines all coal component elements,
solid or gaseous and the proximate analysis determines only
the fixed carbon, volatile matter, moisture and ash percentages.
 The ultimate analysis is determined in a properly equipped
laboratory by a skilled chemist, while proximate analysis can
be determined with a simple apparatus.
 It may be noted that proximate has no connection with the
word “approximate”.

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Coal Analysis: Proximate Analysis
Measurement of Moisture
 When 1 g sample of coal is subjected to a temperature of about
105oC for a period of 1 hour, the loss in weight of the sample
gives the moisture content of the coal.

Significance of Moisture:
 High moisture content of the coal is undesirable for the following
reasons:
1) Reduces the calorific value of coal
2) Increases the consumption of coal for heating purpose.
3) Lengthens the time of heating.

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Coal Analysis: Proximate Analysis
Measurement of Volatile Matter
 When 1 g sample of coal is placed in a covered platinum crucible and
heated to 950 oC and maintained at that temperature for about 7 min,
there is a loss in weight due to the elimination of moisture and volatile
matter. The latter may now be determined since moisture has been
calculated from the previous test.

Significance of volatile matter:


 During burning of coal, gases like CO, CO2, CH4, N2, O2,
hydrocarbons etc. that come out are called volatile matter of the coal.
 It has been found that the coal with higher volatile matter content
ignites easily has lower calorific value burns with long yellow smoky
flame will evolve more coal gas when heated in the absence of air.

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Coal Analysis: Proximate Analysis
Measurement ash in coal
 By subjecting 1 g sample of coal in an uncovered crucible to a
temperature of about 720 oC until the coal is completely burned,
a constant weight is reached, which indicates that there is only
ash remaining in the crucible. Complete combustion of coal is
determined by repeated weighing of the sample.

 High ash content in coal is undesirable because it


i. increases transporting, handling and storage costs
ii. is harder and stronger
iii. has lower calorific value

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Coal Analysis: Proximate Analysis
Measurement of fixed carbon
 Fixed carbon is the difference between 100% (original sample) and
the sum of the percentages of moisture, ash and volatile matter.
However, this difference does not represent all the carbon that was in
the coal. Some of the carbon may have been in the form of
hydrocarbons which may have been distilled off while determining
the volatile matter. It is also possible that some of this fixed carbon
may include Sulphur, nitrogen and oxygen.
% of fixed carbon in coal =
100 - % (moisture + volatile matter + ash)
 Fixed carbon is the pure carbon present in coal. Higher the fixed
carbon content of the coal, higher will be the calorific value of the
sample.
 So, the proximate analysis of coal gives
FC + VM + M+ A = 100% by mass
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Coal Analysis

Ultimate Analysis
 The ultimate analysis indicates the various elemental chemical
constituents such as Carbon, Hydrogen, Oxygen, Nitrogen,
Sulphur of pure dry coal. This analysis gives the elementary,
ultimate constituents of coal.
 It is useful in determining the quantity of air required for
combustion and the volume and composition of the combustion
gases.
 This analysis is essential for calculating heat balances in any
process for which coal is employed as a fuel.
 It is useful to the designing of coal burning equipment and
auxiliaries. This information is required for the calculation of
flame temperature and the flue duct design etc.

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Coal Analysis: Ultimate Analysis
a) Determination of carbon and hydrogen in coal:
 A known amount of coal is burnt in presence of oxygen thereby
converting carbon and hydrogen of coal into-
(i) CO2 (C + O2 → CO2) and (ii) H2O (H2 + ½ O2 → H2O)
respectively.
The products of combustion CO2 and H2O are passing over
weighed tubes of anhydrous CaCl2 and KOH which absorb H2O
and CO2 respectively.
 The increase in the weight of CaCl2 tube represents the weight of
water formed while the increase in the weight of KOH tube
represents the weight of CO2 formed.
 The percentage of carbon and hydrogen in coal can be calculated in
the following way-

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Coal Analysis: Ultimate Analysis

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Coal Analysis: Ultimate Analysis
(b) Determination of hydrogen:

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Coal Analysis: Ultimate Analysis
(c) Determination of nitrogen:
This is done by Kjeldhal’s method.
 A known amount of powdered coal is heated with concentrated
sulphuric acid in the presence of potassium sulfate (K2SO4) and
copper sulfate (CuSO4) in a long necked Kjeldhal’s flask.
 This converts nitrogen of coal to ammonium sulphate. When the
clear solution is obtained (i.e., the whole of nitrogen is converted
into ammonium sulphate), it is heated with 50 % sodium
hydroxide (NaOH) solution and the following reaction occurs:

 The ammonia thus formed is distilled over and is absorbed in a


known quantity of standard 0.1 N H2SO4 solution. The volume of
unused 0.1 N H2SO4 is then determined by titrating against
standard NaOH solution. Thus, the amount of acid neutralized by
20 liberated ammonia from coal is determined using the formula.
Coal Analysis: Ultimate Analysis

(d) Determination of sulphur in coal:


 A known amount of coal is burnt completely in Bomb calorimeter
in presence of oxygen. Ash thus obtained contains sulphur of coal
as sulphate which is extracted with dil. HCl.
 The acid extract is then treated with BaCl2 solution to precipitate
sulphate as BaSO4. The precipitate is filtered, washed, dried and
weighed. From the weight of BaSO4, the percentage of sulphur in
coal is calculated in the following way.

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Coal Analysis: Ultimate Analysis

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Coal Analysis: Ultimate Analysis
e) Determination of oxygen in coal:
 It is calculated indirectly in the following way-
% of oxygen in coal = 100 - % (C + H + N + S + ash)
Significance:
 The less the oxygen content, the better is the coal. As the
oxygen content increases,
 its moisture holding capacity also increases.

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Coal Analysis
Table : Proximate and ultimate analysis of some U.S. coals

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HEATING VALUE
 The heating value, J/kg of fuel, is the heat transferred when the
products of complete combustion of a sample of coal or other
fuel are cooled to the initial temperature of air and fuel.
 It is determined in a standard test in a bomb calorimeter.
 There are two determinations:
 The higher heating value (HHV) or gross calorific value
(GCV), assumes that the water vapor in the products
condenses and thus includes the latent heat of vaporization
of the water vapor in the products;
 When the latent heat of vaporization of water vapor
contained in the combustion products is subtracted from the
HHV we get the lower heating value (LHV) or net calorific
value (NCV) of fuel.
 Therefore,
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HEATING VALUE
LHV = HHV − 𝑚𝑤 ℎ𝑓𝑔
where mw is the mass of water vapour formed given by
𝑚𝑤 = 𝑀 + 9𝐻 + 𝛾𝐴 𝑤𝐴
 where M and H are the mass fractions of moisture and hydrogen
in the coal, 𝛾𝐴 is the specific humidity of atmospheric air and 𝑤𝐴
is the actual amount of air supplied per kg of coal.\
 If the ultimate analysis is known, the HHV of anthracite and
bituminous coals can be determined approximately by using
Dulong and Petit formula as given below:
O
HHV = 33.83 C + 144.45 H − + 9.38 S, in MJ/kg
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 where C, H, 0 and S are mass fractions of carbon, hydrogen,
oxygen and sulphur in coal.

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HEATING VALUE
 Assuming the latent heat of vaporization hfg at the partial pressure
of water vapour in the combustion products as 2.395 MJ/kg, the
lower heating value of coal is given by
LHV = HHV − 2.395 𝑚𝑤 in MJ/kg
 For lower-rank fuels the Dulong and Petit formula usually
underestimates the HHV.

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COMBUSTION REACTIONS
 Combustion is the high temperature oxidation of the combustible
elements of a fuel with heat release.
 In combustion reactions, rapid oxidation of combustible elements
of the fuel results in energy release as combustion products are
formed.
 The three major combustible chemical elements in most common
fuels are carbon, hydrogen, and sulfur. Sulfur is usually a
relatively unimportant contributor to the energy released, but it
can be a significant cause of pollution and corrosion problems.
 Combustion is complete when all the carbon present in the fuel is
burned to carbon dioxide, all the hydrogen is burned to water, all
the sulfur is burned to sulfur dioxide, and all other combustible
elements are fully oxidized. When these conditions are not
fulfilled, combustion is incomplete.

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COMBUSTION REACTIONS
 The combustible elements in coal and fuel oil are carbon, hydrogen and
sulphur. The basic chemical equations for co1nplete combustion are
C + O2 → CO2
2H2 + O2 →2H2O
S + O2 → SO2
 When insufficient oxygen is present, the carbon will be burned incompletely
with the formation of carbon monoxide.
2C + O2 → 2CO
 When dealing with chemical reactions, it is necessary to remember that mass
is conserved, so the mass of the products equals the mass of the reactants.
 The total mass of each chemical element must be the same on both sides of
the equation, even though the elements exist in different chemical
compounds in the reactants and products.
 However, the number of moles of products may differ from the number of
moles of reactants. for example. . . consider the complete combustion of
hydrogen with oxygen
1
29 1H2 O
+ 2 2
→ 1H2 O
COMBUSTION REACTIONS
 In this case, the reactants are hydrogen and oxygen. Hydrogen is
the fuel and oxygen is the oxidizer. Water is the only product of the
reaction.
 The numerical coefficients in the equation, which precede the
chemical symbols to give equal amounts of each chemical element
on both sides of the equation, are called stoichiometric
coefficients. In words,
1
1 kmol H2 + kmol O2 → 1 kmol H2 O
2
 Note that the total numbers of moles on the left and right sides of
are not equal. However, because mass is conserved, the total mass
of reactants must equal the total mass of products.
 Since 1 kmol of H2 equals 2 kg, 1 kmol of O2 equals 16 kg, and 1/2
kmol of H2O equals 18 kg, the above equation can be interpreted
as stating
30 2 kg H2 + 16 kg O2 → 18 kg H2 O
COMBUSTION REACTIONS
 ln order to bum a fuel completely, four basic conditions must be
fulfilled:
1. Supply enough air for complete combustion of fuel.
2. Secure enough turbulence for thorough mixing of fuel and air.
3. Maintain a furnace temperature high enough to ignite the
incoming fuel air mixture.
4. Provide a furnace volume large enough to allow time for
combustion to be completed.
 Apart from adequate air supply, the three T's, viz., time,
temperature and turbulence have to be kept in mind while
designing a furnace.
 Since the complete mixing of the fuel and air is virtually
impossible, excess air must be supplied to ensure complete
combustion. The greater is the rate of mixing or turbulence, the
lower would be the excess air required.
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FUELS
 A fuel is simply a combustible substance.
In this chapter emphasis is on hydrocarbon
fuels, which contain hydrogen and carbon.
Sulfur and other chemical substances also
may be present.
 Hydrocarbon fuels are denoted by the
general formula CnHm.
 Hydrocarbon fuels exist in all phases, some
examples being coal, gasoline, and natural
gas
 Liquid hydrocarbon fuels are commonly
derived from crude oil through distillation
and cracking processes. Examples are
gasoline, diesel fuel, kerosene, and other
types of fuel oils.

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FUELS
 Most liquid fuels are mixtures of hydrocarbons for which
compositions are usually given in terms of mass fractions. For
simplicity in combustion calculations, gasoline is often modeled as
octane, C8H18, and diesel fuel as dodecane, C12H26.
 Gaseous hydrocarbon fuels are obtained from natural gas wells or
are produced in certain chemical processes. Natural gas normally
consists of several different hydrocarbons, with the major
constituent being methane, CH4. The compositions of gaseous fuels
are usually given in terms of mole fractions.
 The main constituent of coal is carbon. Coal also contains varying
amounts of oxygen, hydrogen, nitrogen, sulfur, moisture, and ash.
It is difficult to give an exact mass analysis for coal since its
composition varies considerably from one geographical area to the
next and even within the same geographical location.

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FUELS
 For combustion calculations, the composition of coal is usually
expressed as an ultimate analysis.
 The ultimate analysis gives the composition on a mass basis in terms
of the relative amounts of chemical elements (carbon, sulfur,
hydrogen, nitrogen, oxygen) and ash.
 Most liquid hydrocarbon fuels are a mixture of numerous
hydrocarbons and are obtained from crude oil by distillation.
 The most volatile hydrocarbons vaporize first, forming what we
know as gasoline. The less volatile fuels obtained during distillation
are kerosene, diesel fuel, and fuel oil.
 The composition of a particular fuel depends on the source of the
crude oil as well as on the refinery.

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FUELS
 Although liquid hydrocarbon fuels are mixtures of many different
hydrocarbons, they are usually considered to be a single
hydrocarbon for convenience.
 For example, gasoline is treated as octane, C8H18, and the diesel
fuel as dodecane, C12H26. Another common liquid hydrocarbon
fuel is methyl alcohol, CH3OH, which is also called methanol and
is used in some gasoline blends. The gaseous hydrocarbon fuel
natural gas, which is a mixture of methane and smaller amounts of
other gases, is often treated as methane, CH4, for simplicity.
 Natural gas is produced from gas wells or oil wells rich in natural
gas. It is composed mainly of methane, but it also contains small
amounts of ethane, propane, hydrogen, helium, carbon dioxide,
nitrogen, hydrogen sulfate, and water vapor.

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COMBUSTION AIR
 Oxygen is required in every combustion reaction. Pure oxygen is
used only in special applications such as cutting and welding.
 In most combustion applications, air provides the needed oxygen.
 On a mole or a volume basis, dry air is composed of 20.9 percent
oxygen, 78.1 percent nitrogen, 0.9 percent argon, and small amounts
of carbon dioxide, helium, neon, and hydrogen.
 In the analysis of combustion processes, the argon in the air is
treated as nitrogen, and the gases that exist in trace amounts are
disregarded.
 Then dry air can be approximated as 21 percent oxygen and 79
percent nitrogen by mole numbers. Therefore, each mole of oxygen
entering a combustion chamber is accompanied by 0.79/0.21 = 3.76
mol of nitrogen.

1 kmol O2 + 3.76 kmol N2 = 4.76 kmol air


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COMBUSTION AIR
 For the combustion calculations, air is considered to be 21%
oxygen and 79% nitrogen on a molar basis. With this idealization
the molar ratio of the nitrogen to the oxygen is 0.79/0.21 = 3.76.
When air supplies the oxygen in a combustion reaction, therefore,
every mole of oxygen is accompanied by 3.76 moles of nitrogen.
 We also assume that the nitrogen present in the combustion air does
not undergo chemical reaction. That is, nitrogen is regarded as inert.
 The nitrogen in the products is at the same temperature as the other
products, however, so the nitrogen undergoes a change of state if
the products are at a temperature other than the air temperature
before combustion.
 At very high temperatures, such as those encountered in internal
combustion engines, nitrogen can form compounds such as nitric
oxide and nitrogen dioxide. Even trace amounts of oxides of
nitrogen appearing in the exhaust of internal combustion engines
37 can be a source of air pollution.
AIR–FUEL RATIO
 Two parameters that are frequently used to quantify the amounts of fuel
and air in a particular combustion process are the air–fuel ratio and its
reciprocal, the fuel–air ratio.
 The air–fuel ratio is simply the ratio of the amount of air in a reaction to
the amount of fuel. The ratio can be written on a molar basis (moles of
air divided by moles of fuel) or on a mass basis (mass of air divided by
mass of fuel). Conversion between these values is accomplished using
the molecular weights of the air, Mair, and fuel, Mfuel,

 where 𝐴𝐹 is the air–fuel ratio on a molar basis and AF is the ratio on a


mass basis. For the combustion calculations the molecular weight of air
is taken as 28.97.
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THEORETICAL AIR
 The minimum amount of air that supplies sufficient oxygen for the
complete combustion of all the carbon, hydrogen, and sulfur present
in the fuel is called the theoretical (stoichiometric) amount of air.
 For complete combustion with the theoretical amount of air, the
products would consist of carbon dioxide, water, sulfur dioxide, the
nitrogen accompanying the oxygen in the air, and any nitrogen
contained in the fuel. No free oxygen would appear in the products.
 for example.. . let us determine the theoretical amount of air for the
complete combustion of methane. For this reaction, the products
contain only carbon dioxide, water, and nitrogen. The reaction is

 where a, b, c, and d represent the numbers of moles of oxygen,


carbon dioxide, water, and nitrogen. In the reaction equation above
3.76 moles of nitrogen are considered to accompany each mole of
oxygen.
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THEORETICAL AIR
 Applying the conservation of mass principle to the carbon, hydrogen,
oxygen, and nitrogen, respectively, results in four equations among the
four unknowns

 Solving these equations, the balanced chemical equation is

 The coefficient 2 before the term (O2 + 3.76N2) is the number of moles
of oxygen in the combustion air, per mole of fuel, and not the amount
of air. The amount of combustion air is 2 moles of oxygen plus 2 x 3.76
moles of nitrogen, giving a total of 9.52 moles of air per mole of fuel.
 Thus, for the reaction given, the air–fuel ratio on a molar basis is 9.52.

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THEORETICAL AIR
 The air–fuel ratio on a mass basis can be calculated as

 Normally the amount of air supplied is either greater or less than the
theoretical amount.
 The amount of air actually supplied is commonly expressed in terms of
the percent of theoretical air. For example, 150% of theoretical air
means that the air actually supplied is 1.5 times the theoretical amount
of air.
 The amount of air supplied can be expressed alternatively as a percent
excess or a percent deficiency of air. Thus, 150% of theoretical air is
equivalent to 50% excess air, and 80% of theoretical air is the same as
a 20% deficiency of air.

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THEORETICAL AIR
 for example.. . consider the complete combustion of methane with
150% theoretical air (50% excess air). The balanced chemical
reaction equation is

 In this equation, the amount of air per mole of fuel is 1.5 times the
theoretical amount determined previously. Accordingly, the air–fuel
ratio is 1.5 times higher.
 Since complete combustion is assumed, the products contain only
carbon dioxide, water, nitrogen, and oxygen. The excess air supplied
appears in the products as uncombined oxygen and a greater amount of
nitrogen than the equation based on the theoretical amount of air.
 The equivalence ratio is the ratio of the actual fuel–air ratio to the
fuel–air ratio for complete combustion with the theoretical amount
of air. The reactants are said to form a lean mixture when the
equivalence ratio is less than unity. When the ratio is greater than
unity, the reactants are said to form a rich mixture.
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E X A M P L E 1. Determining the Air–Fuel Ratio
 Determine the air–fuel ratio on both a molar and mass basis for the
complete combustion of octane, C8H18, with (a) the theoretical
amount of air, (b) 150% theoretical air (50% excess air).
Analysis:
 (a) For complete combustion of C8H18 with the theoretical amount of
air, the products contain carbon dioxide, water, and nitrogen only.
That is

 Applying the conservation of mass principle to the carbon, hydrogen,


oxygen, and nitrogen, respectively, gives

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E X A M P L E 1. Determining the Air–Fuel Ratio

 Solving these equations, a = 12.5, b = 8, c = 9, d = 47. The


balanced chemical equation is

 The air–fuel ratio on a molar basis is

 The air–fuel ratio expressed on a mass basis is

 For 150% theoretical air, the chemical equation for complete


combustion takes the form
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E X A M P L E 1. Determining the Air–Fuel Ratio
 Applying conservation of mass

 Solving this set of equations, b = 8, c = 9, d = 70.5, e = 6.25, giving a


balanced chemical equation

 The air–fuel ratio on a molar basis is

 On a mass basis, the air–fuel ratio is 22.6 kg (air) / kg (fuel), as can be


verified.
 Note: When complete combustion occurs with excess air, oxygen appears
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in the products, in addition to carbon dioxide, water, and nitrogen.
Example 2
 A certain coal has the following analysis on a mass basis: 82
percent C, 5 percent H2O, 2 percent H2, 1 percent O2, and 10
percent ash. The coal is burned with 50 percent excess air.
Determine the air–fuel ratio.
 Analysis: The composition of the coal is given on a mass basis,
but we need to know the composition on a mole basis to balance
the combustion equation.
 Considering 1 kg of coal, the numbers of mole of the each
component are determined to be

46
Example 2

47
Dew Point Temperature
 The saturation temperature at the partial pressure of water vapour is
called the dew point temperature (d.p.t.).
 The partial pressure of water vapour in the mixture of gases
constituting the flue gas is given by
𝑃𝐻2 𝑂 = 𝑥𝐻2 𝑂 𝑃
 where P is the total pressure of the exhaust gas mixture and is 𝑥𝐻2 𝑂 is
the mole fraction of water vapour in the exhaust gas mixture
𝑛𝐻2 𝑂
𝑥𝐻2 𝑂 =
𝑛𝑡𝑜𝑡𝑎𝑙
 The flue gases arc cooled in heat exchangers like economizer and air
preheater so as to minimize the exhaust losses through chimney. These
gases, however, should never be cooled below the dew point
temperature. If cooled below the d.p.t., the water vapour condenses
into liquid droplets which react with S02 or S03 to form acid. This acid
corrodes the metal surfaces of the ducts through which the flue gas
48 flows
Example 3
 Ethane (C2H6) is burned with 20 percent excess air during a
combustion process, as shown in Fig. below. Assuming complete
combustion and a total pressure of 100 kPa, determine (a) the air–
fuel ratio and (b) the dew-point temperature of the products

 Solution The fuel is burned completely with excess air. The AF


and the dew point of the products are to be determined.
 Assumptions 1 Combustion is complete. 2 Combustion gases are
ideal gases.
 Analysis The combustion products contain CO2, H2O, N2, and
some excess O2 only. Then the combustion equation can be
49 written as
Example 3

 where ath is the stoichiometric coefficient for air. We have


automatically accounted for the 20 percent excess air by using
the factor 1.2ath instead of ath for air.
 The stoichiometric amount of oxygen (athO2) is used to oxidize
the fuel, and the remaining excess amount (0.2athO2) appears in
the products as unused oxygen. Notice that the coefficient of N2
is the same on both sides of the equation, and that we wrote the
C and H balances directly since they are so obvious.
 The coefficient ath is determined from the O2 balance to be

50
Example 3
 (a) The air–fuel ratio is determined by taking the ratio of the mass
of the air to the mass of the fuel,

 That is, 19.3 kg of air is supplied for each kilogram of fuel during
this combustion process.
 (b) The dew-point temperature of the products is the temperature at
which the water vapor in the products starts to condense as the
products are cooled at constant pressure.
 The dew-point temperature of a gas–vapor mixture is the saturation
temperature of the water vapor corresponding to its partial pressure.
Therefore, we need to determine the partial pressure of the water
vapor Pv in the products first. Assuming ideal-gas behavior for the
51
combustion gases, we have
Example 3

52
EXAMPLE 4. Combustion of a Gaseous Fuel with Moist Air
 A certain natural gas has the following volumetric analysis: 72
percent CH4, 9 percent H2, 14 percent N2, 2 percent O2, and 3
percent CO2. This gas is now burned with the stoichiometric
amount of air that enters the combustion chamber at 20°C, 1
atm, and 80 percent relative humidity. Assuming complete
combustion and a total pressure of 1 atm, determine the dew-
point temperature of the products.

53
EXAMPLE 4. Combustion of a Gaseous Fuel with Moist Air
 Assumptions 1 The fuel is burned completely and thus all the carbon in
the fuel burns to CO2 and all the hydrogen to H2O. 2 The fuel is burned
with the stoichiometric amount of air and thus there is no free O2 in the
product gases. 3 Combustion gases are ideal gases.
 Properties The saturation pressure of water at 20oC is 2.3392 kPa
 Analysis We note that the moisture in the air does not react with
anything; it simply shows up as additional H2O in the products.
Therefore, for simplicity, we balance the combustion equation by using
dry air and then add the moisture later to both sides of the equation.

54
EXAMPLE 4. Combustion of a Gaseous Fuel with Moist Air

55
EXAMPLE 4. Combustion of a Gaseous Fuel with Moist Air

56
EXAMPLE 4. Combustion of a Gaseous Fuel with Moist Air

57
DETERMINING PRODUCTS OF COMBUSTION
 Combustion is the result of a series of very complicated and rapid
chemical reactions, and the products formed depend on many factors.
 When fuel is burned in the cylinder of an internal combustion engine,
the products of the reaction vary with the temperature and pressure in
the cylinder.
 In combustion equipment of all kinds, the degree of mixing of the fuel
and air is a controlling factor in the reactions that occur once the fuel
and air mixture is ignited.
 Although the amount of air supplied in an actual combustion process
may exceed the theoretical amount, it is not uncommon for some
carbon monoxide and unburned oxygen to appear in the products. This
can be due to incomplete mixing, insufficient time for complete
combustion, and other factors.
 When the amount of air supplied is less than the theoretical amount of
air, the products may include both CO2 and CO, and there also may be
58
unburned fuel in the products.
DETERMINING PRODUCTS OF COMBUSTION
 The products of combustion of an actual combustion process and
their relative amounts can be determined only by measurement.
 Among several devices for measuring the composition of products
of combustion are the Orsat analyzer, gas chromatograph, infrared
analyzer, and flame ionization detector. Data from these devices
can be used to determine the mole fractions of the gaseous products
of combustion.
 The analyses from these devices are often reported on a “dry” basis.
In a dry product analysis, the mole fractions are given for all
gaseous products except the water vapor.
 If the gaseous products of combustion are cooled at constant
mixture pressure, the dew point temperature is reached when water
vapor begins to condense. Since water deposited on duct work,
mufflers, and other metal parts can cause corrosion, knowledge of
the dew point temperature is important
59
Example 5
 A natural gas has the following molar analysis:
CH4, 80.62%; C2H6, 5.41%; C3H8, 1.87%; C4H10, 1.60%; N2, 10.50%.
The gas is burned with dry air, giving products having a molar
analysis on a dry basis:
CO2, 7.8%; CO, 0.2%; O2, 7%; N2, 85%.
(a) Determine the air–fuel ratio on a molar basis.
(b) Assuming ideal gas behavior for the fuel mixture, determine the
amount of products in kmol that would be formed from 100 m3 of
fuel mixture at 300 K and 1 bar.
(c) Determine the percent of theoretical air.

60
Example 5
Analysis:
 (a) The solution can be conducted on the basis of an assumed amount
of fuel mixture or on the basis of an assumed amount of dry products.
Let us illustrate the first procedure, basing the solution on 1 kmol of
fuel mixture. The chemical equation then takes the form

 The products consist of b kmol of dry products and c kmol of water


vapor, each per kmol of fuel mixture.
 Applying conservation of mass to carbon

Solving gives b = 12.931.


 Conservation of mass for hydrogen results in

61 which gives c = 1.93.


Example 5

 The unknown coefficient a can be found from either an oxygen


balance or a nitrogen balance. Applying conservation of mass to
oxygen

giving a = 2.892.
 The balanced chemical equation is then

 The air–fuel ratio on a molar basis is

62
Example 5
 (b) By inspection of the chemical reaction equation, the total amount
of products is b + c = 12.931 + 1.93 = 14.861 kmol of products per
kmol of fuel. The amount of fuel in kmol, nF, present in 100 m3 of fuel
mixture at 300 K and 1 bar can be determined from the ideal gas
equation of state as

 Accordingly, the amount of product mixture that would be formed


from 100 m3 of fuel mixture is (14.861)(4.01) = 59.59 kmol of product
gas
 (c) The balanced chemical equation for the complete combustion of
the fuel mixture with the theoretical amount of air is

63
Example 5
 The theoretical air–fuel ratio on a molar basis is

 The percent theoretical air is then

64
Example 6
 Octane (C8H18) is burned with dry air. The volumetric analysis of
the products on a dry basis is

 Determine (a) the air–fuel ratio, (b) the percentage of theoretical


air used, and (c) the amount of H2O that condenses as the products
are cooled to 25°C at 100 kPa.
 Solution Combustion products whose composition is given are
cooled to 25°C. The AF, the percent theoretical air used, and the
fraction of water vapor that condenses are to be determined.
 Assumptions Combustion gases are ideal gases.
 Properties The saturation pressure of water at 25°C is 3.1698 kPa

65
Example 6
 Analysis: Note that we know the relative composition of the
products, but we do not know how much fuel or air is used during the
combustion process. However, they can be determined from mass
balances. The H2O in the combustion gases will start condensing when
the temperature drops to the dewpoint temperature.
 For ideal gases, the volume fractions are equivalent to the mole
fractions. Considering 100 kmol of dry products for convenience, the
combustion equation can be written as

66
Example 6
 The O2 balance is not necessary, but it can be used to check the
values obtained from the other mass balances, as we did previously.
Substituting, we get

67
Example 6

68
Example 6

69
Enthalpy of Combustion and Enthalpy of Formation
 Enthalpy of combustion hC, which represents the amount of heat
released during a steady-flow combustion process when 1 kmol (or 1
kg) of fuel is burned completely at a specified temperature and
pressure . It is expressed as

 The enthalpy of combustion of a particular fuel is different at


different temperatures and pressures.
 Since there are so many different fuels and fuel mixtures it is not
practical to list hC values for all possible cases. Besides, the enthalpy
of combustion is not of much use when the combustion is
incomplete.
 Therefore a more practical approach would be to have a more
fundamental property to represent the chemical energy of an element
or a compound at some reference state. This property is the
enthalpy of formation ℎത𝑓 , which can be viewed as the enthalpy of a
70
substance at a specified state due to its chemical composition.
Enthalpy of Combustion and Enthalpy of Formation
 The enthalpy of formation of all stable
elements (such as O2, N2, H2, and C) is
taken as zero at the standard reference
state of 25°C and 1 atm. That is, ℎത𝑓 = 0
for all stable elements.
 Consider the formation of CO2 (a
compound) from its elements C and O2 at
25°C and 1 atm during a steady-flow
Fig. The enthalpy of formation of a
process. The enthalpy change during this
compound represents the amount of
process is -393,520 kJ/kmol. However,
energy absorbed or released as the
Hreact = 0 since both reactants are component is formed from its stable
elements at the standard reference state, elements during a steady-flow
and the products consist of 1 kmol of process at a specified state.
CO2 at the same state. Therefore, the
enthalpy of formation of CO2 at the
standard reference state is - 393,520
kJ/kmol. That is,
71
Enthalpy of Combustion and Enthalpy of Formation
 The negative sign is due to the fact that the enthalpy of 1 kmol of CO2
at 25°C and 1 atm is 393,520 kJ less than the enthalpy of 1 kmol of C
and 1 kmol of O2 at the same state. In other words, 393,520 kJ of
chemical energy is released (leaving the system as heat) when C and
O2 combine to form 1 kmol of CO2.
 Therefore, a negative enthalpy of formation for a compound indicates
that heat is released during the formation of that compound from its
stable elements. A positive value indicates heat is absorbed.
 Another term commonly used in conjunction with the combustion of
fuels is the heating value of the fuel, which is defined as 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. In
other words, the heating value of a fuel is equal to the absolute value
of the enthalpy of combustion of the fuel. That is,

72
Enthalpy of Combustion and Enthalpy of Formation
 The heating value depends on the phase of
the H2O in the products.
 The heating value is called the higher
heating value (HHV) when the H2O in the
products is in the liquid form, and it is
called the lower heating value (LHV)
when the H2O in the products is in the
vapor form. The two heating values are
related by

 where m is the mass of H2O in the


products per unit mass of fuel and hfg is the
enthalpy of vaporization of water at the
specified temperature.
 The heating value or enthalpy of
combustion of a fuel can be determined
from a knowledge of the enthalpy of
73 formation for the compounds involved.
Example 7: Evaluation of the Enthalpy of Combustion
 Determine the enthalpy of combustion of liquid octane
(C8H18) at 25°C and 1 atm, using enthalpy-of-formation data
from Enthalpy of formation Table. Assume the water in the
products is in the liquid form.
 Properties The enthalpy of formation at 25°C and 1 atm is -
393,520 kJ/kmol for CO2, -285,830 kJ/kmol for H2O(l), and -
249,950 kJ/kmol for C8H18 (l)
 Analysis The stoichiometric equation for combustion of C8H18
is

 Both the reactants and the products are at the standard


reference state of 25°C and 1 atm. Also, N2 and O2 are stable
elements, and thus their enthalpy of formation is zero. Then
the enthalpy of combustion of C8H18 becomes
74
Example 7: Evaluation of the Enthalpy of Combustion

 Since the water in the products is assumed to be in the liquid phase,


this hC value corresponds to the HHV of liquid C8H18.
 It can be shown that the result for gaseous octane is -5,512,200
kJ/kmol or -48,255 kJ/kg.
 For fuels that exhibit considerable variations in composition depending
on the source, such as coal, natural gas, and fuel oil, it is more practical
to determine their enthalpy of combustion experimentally by burning
them directly in a bomb calorimeter at constant volume or in a steady-
75
flow device.
FIRST-LAW ANALYSIS OF REACTING SYSTEMS
Steady-Flow Systems
 The specific enthalpy of a compound at a state other than the
standard state is found by adding the specific enthalpy change ∆ℎത
between the standard state and the state of interest to the enthalpy
of formation

 That is, the enthalpy of a compound is composed of associated


with the formation of the compound from its elements, and ∆ℎത
associated with a change of state at constant composition.
 An arbitrary choice of datum can be used to determine ∆ℎ ത since it
is a difference at constant composition. Accordingly, ∆ℎത can be
evaluated from tabular sources such as the steam tables, the ideal
gas tables when appropriate, and so on.

76
FIRST-LAW ANALYSIS OF REACTING SYSTEMS
 When the changes in kinetic and potential energies are negligible,
the steady-flow energy balance relation 𝐸ሶ 𝑖𝑛 = 𝐸ሶ 𝑜𝑢𝑡 can be
expressed for a chemically reacting steady-flow system more
explicitly as

 In combustion analysis, it is more convenient to work with


quantities expressed per mole of fuel.

77
FIRST-LAW ANALYSIS OF REACTING SYSTEMS
 where Nr and Np represent the number of moles of the reactant r
and the product p, respectively, per mole of fuel. Note that Nr = 1
for the fuel, and the other Nr and Np values can be picked directly
from the balanced combustion equation.
 Taking heat transfer to the system and work done by the system to
be positive quantities, the energy balance relation just discussed can
be expressed more compactly as

78
FIRST-LAW ANALYSIS OF REACTING SYSTEMS
 A combustion chamber normally involves heat output but no heat
input. Then the energy balance for a typical steady-flow combustion
process becomes

79
EXAMPLE 8. First-Law Analysis of Steady-Flow Combustion
 Liquid propane (C3H8) enters a combustion chamber at 25°C at a
rate of 0.05 kg/min where it is mixed and burned with 50 percent
excess air that enters the combustion chamber at 7°C, as shown in
the Fig. An analysis of the combustion gases reveals that all the
hydrogen in the fuel burns to H2O but only 90 percent of the carbon
burns to CO2, with the remaining 10 percent forming CO. If the exit
temperature of the combustion gases is 1500 K, determine (a) the
mass flow rate of air and (b) the rate of heat transfer from the
combustion chamber.

80
EXAMPLE 8. First-Law Analysis of Steady-Flow Combustion
Analysis
 We note that all the hydrogen in the fuel burns to H2O but 10
percent of the carbon burns incompletely and forms CO. Also, the
fuel is burned with excess air and thus there is some free O2 in the
product gases.
 The theoretical amount of air is determined from the stoichiometric
reaction to be

81
EXAMPLE 8. First-Law Analysis of Steady-Flow Combustion

82
EXAMPLE 8. First-Law Analysis of Steady-Flow Combustion

83
EXAMPLE 8. First-Law Analysis of Steady-Flow Combustion

84
ADIABATIC FLAME TEMPERATURE
 In the absence of any work interactions and any changes in kinetic
or potential energies, the chemical energy released during a
combustion process either is lost as heat to the surroundings or is
used internally to raise the temperature of the combustion products.
The smaller the heat loss, the larger the temperature rise.
 In the limiting case of no heat loss to the surroundings (Q = 0), the
temperature of the products reaches a maximum, which is called
the adiabatic flame or adiabatic combustion temperature of the
reaction
Fig. The temperature of a
combustion chamber becomes
maximum when combustion is
complete and no heat is lost to the
surroundings (Q = 0).

85
ADIABATIC FLAME TEMPERATURE
 The adiabatic flame temperature of a steady-flow combustion
process is determined by setting Q = 0 and W = 0. It yields

 Once the reactants and their states are specified, the enthalpy of
the reactants Hreact can be easily determined. The calculation of the
enthalpy of the products Hprod is not so straightforward, however,
because the temperature of the products is not known prior to the
calculations.
 Therefore, the determination of the adiabatic flame temperature
requires the use of an iterative technique unless equations for the
sensible enthalpy changes of the combustion products are
available.
86
ADIABATIC FLAME TEMPERATURE
 A temperature is assumed for the product gases, and the Hprod is
determined for this temperature. If it is not equal to Hreact, calculations
are repeated with another temperature. The adiabatic flame temperature
is then determined from these two results by interpolation.
 When the oxidant is air, the product gases mostly consist of N2, and a
good first guess for the adiabatic flame temperature is obtained by
treating the entire product gases as N2.
 In combustion chambers, the highest temperature to which a material
can be exposed is limited by metallurgical considerations. Therefore, the
adiabatic flame temperature is an important consideration in the design
of combustion chambers, gas turbines, and nozzles.
 The maximum temperatures that occur in these devices are considerably
lower than the adiabatic flame temperature, however, since the
combustion is usually incomplete, some heat loss takes place, and some
combustion gases dissociate at high temperatures
 The maximum temperature in a combustion chamber can be controlled
87 by adjusting the amount of excess air, which serves as a coolant.
Example 9. Adiabatic Flame Temperature in Steady
Combustion
 Liquid octane (C8H18) enters the combustion chamber of a gas
turbine steadily at 1 atm and 25°C, and it is burned with air
that enters the combustion chamber at the same state, as
shown in Fig. below. Determine the adiabatic flame
temperature for (a) complete combustion with 100 percent
theoretical air, (b) complete combustion with 400 percent
theoretical air, and (c) incomplete combustion (some CO in
the products) with 90 percent theoretical air.

88
Example 9. Adiabatic Flame Temperature in Steady
Combustion

89
Example 9. Adiabatic Flame Temperature in Steady
Combustion

 It appears that we have one equation with three unknowns. Actually


we have only one unknown—the temperature of the products Tprod
since h = h(T ) for ideal gases. Therefore, we have to use an
equation solver programs or a trial-and-error approach to determine
the temperature of the products
90
Example 9. Adiabatic Flame Temperature in Steady Combustion
 A first guess is obtained by dividing the right-hand side of the
equation by the total number of moles, which yields 5,646,081/(8 + 9
+ 47) = 88,220 kJ/kmol. This enthalpy value corresponds to about
2650 K for N2, 2100 K for H2O, and 1800 K for CO2.
 Noting that the majority of the moles are N2, we see that Tprod should
be close to 2650 K, but somewhat under it. Therefore, a good first
guess is 2400 K. At this temperature,

 This value is higher than 5,646,081 kJ. Therefore, the actual


temperature is slightly under 2400 K. Next we choose 2350 K. It
yields

 which is lower than 5,646,081 kJ. Therefore, the actual temperature


of the products is between 2350 and 2400 K. By interpolation, it is
91 found to be Tprod = 2395 K.
Example 9. Adiabatic Flame Temperature in Steady
Combustion

92
Exercises
1. Propylene (C3H6) is burned with 50 percent excess air during a
combustion process. Assuming complete combustion and a
total pressure of 105 kPa, determine (a) the air–fuel ratio and
(b) the temperature at which the water vapor in the products
will start condensing.
2. One kilogram of butane (C4H10) is burned with 25 kg of air
that is at 30°C and 90 kPa. Assuming that the combustion is
complete and the pressure of the products is 90 kPa, determine
(a) the percentage of theoretical air used and (b) the dew-point
temperature of the products.
3. A certain natural gas has the following volumetric analysis: 65
percent CH4, 8 percent H2, 18 percent N2, 3 percent O2, and 6
percent CO2. This gas is now burned completely with the
stoichiometric amount of dry air. What is the air–fuel ratio for
93 this combustion process?
Exercises
4. A certain coal has the following analysis on a mass basis: 82
percent C, 5 percent H2O, 2 percent H2, 1 percent O2, and 10
percent ash. The coal is burned with 50 percent excess air.
Determine the air–fuel ratio.
5. Methane (CH4) is burned with dry air. The volumetric analysis
of the products on a dry basis is 5.20 percent CO2, 0.33 percent
CO, 11.24 percent O2, and 83.23 percent N2. Determine (a) the
air–fuel ratio and (b) the percentage of theoretical air used.
6. Liquid propane (C3H8) enters a combustion chamber at 25°C at
a rate of 1.2 kg/min where it is mixed and burned with 150
percent excess air that enters the combustion chamber at 12°C.
If the combustion is complete and the exit temperature of the
combustion gases is 1200 K, determine (a) the mass flow rate
of air and (b) the rate of heat transfer from the combustion
94 chamber.
Exercises
7. Ethane gas (C2H6) at 25°C is burned in a steady-flow
combustion chamber at a rate of 5 kg/h with the stoichiometric
amount of air, which is preheated to 500 K before entering the
combustion chamber. An analysis of the combustion gases
reveals that all the hydrogen in the fuel burns to H2O but only
95 percent of the carbon burns to CO2, the remaining 5 percent
forming CO. If the products leave the combustion chamber at
800 K, determine the rate of heat transfer from the combustion
chamber.
8. Diesel fuel (C12H26) at 25°C is burned in a steady flow
combustion chamber with 20 percent excess air that also enters
at 25°C. The products leave the combustion chamber at 500 K.
Assuming combustion is complete, determine the required
mass flow rate of the diesel fuel to supply heat at a rate of
95
2000 kJ/s.
Exercises
9. Acetylene gas (C2H2) at 25°C is burned during a steady-flow
combustion process with 30 percent excess air at 27°C. It is
observed that 75,000 kJ of heat is being lost from the
combustion chamber to the surroundings per kmol of
acetylene. Assuming combustion is complete, determine the
exit temperature of the product gases.
10. Hydrogen (H2) at 7°C is burned with 20 percent excess air that
is also at 7°C during an adiabatic steady-flow combustion
process. Assuming complete combustion, determine the exit
temperature of the product gases.

96
End of Lecture 3

Next Lecture
Lecture 4: Steam Generators (Boilers)

97

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