CHAPTER THREE

FUEL AND
COMBUSTION
1
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 FUELS AND COMBUSTION
• 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(CnHm ).
• Hydrocarbon fuels exist in all phases
• Examples:-
• Coal------------------ Solid
• Gasoline------------- Liquid
• Natural gas---------- Gas
• The main constituent of coal is carbon and also contains
varying amounts of oxygen, hydrogen, nitrogen, sulfur,
moisture, and ash.
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 Classification of chemical fuels by phase and availability
Naturally available Synthetically produced

Solid Coke
Coal Charcoal
Wood Inorganic Solid Waste
Vegetation
Organic Solid Waste
Liquid
Crude oil Syncrudes
Biological oils Petroleum distillates
Fuel plants Alcohols
Colloidal fuels
Benzene
Gas
Natural gas Natural gas
Marsh Gas Hydrogen
Biogas Methane
Propane
Coal gasification

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 Energetic study of fuels and their use
Electricity net generation
Trillion kilowatthours
13% History 2013 Projections
6
1993 2025 2040

4
31%
27% Natural gas
27%
3
13% 13% 16% Renewables 18%
11%
2
39% 38% Coal 34%
53%
1

Petroleum and other liquids 19% 18%

0 16%
1 1 2 2
Nuclear 2 1% 2 2 1% 2 2 2 2 1%
9 9 0 0 0 0 0 0 0 0 0
9 9 0 0 1 1 2 2 3 3 4
0 5 0 5 0 5 0 5 0 5 0

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 Energetic study of fuels and their use
 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. When more than one type
fuel is simultaneously burned to meet the total heating
requirement, the boiler is said to have a combination firing.

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 Coal
 An encompassing description of coal has been given by van
Krevelen, in which he states: “Coal is a rock, a sediment, a
conglomerate, a biological fossil, a complex colloidal system,
an enigma in solid-state physics and an intriguing object for
chemical and physical analyses.”
 In short, coal is a chemically and physically heterogeneous,
“combustible,” sedimentary rock consisting of both organic and
inorganic material. Organically, coal consists primarily of
carbon, hydrogen, and oxygen, with lesser amounts of sulfur
and nitrogen.
 Inorganically, coal consists of a diverse range of ash-forming
compounds distributed throughout the coal.

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 Coal
 The inorganic constituents can vary in concentration from
several percentage points down to parts per billion of the
coal.
 Coal is the most abundant fossil fuel in the United
States, as well as in the world.
 At the end of 2000, recoverable coal reserves in the
United States, which contains the world’s largest coal
reserves, totaled 274 billion short tons compared to a
total world reserve of 1083 billion short tons .
 On an oil-equivalent basis, there is approximately twice
as much recoverable coal in the world as oil and natural
gas combined.
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 Process of formation of coal

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 Process of formation of coal
PEAT

LIGNITE

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 Process of formation of coal
BITUMINOUS

ANTHRACITE

10
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 Process of formation of coal
• With increase percentage of carbon.
• Decrease volatile matter.
• Decrease moisture content.
• Increasing heating value.

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 Process of formation of coal
• Anthracite:- contains:-
• more than 86% fixed carbon and
• less volatile matter.
• It is difficult to burn anthracite
• Bituminous :- the largest group. Contains:-
• 46-86% of fixed carbon and
• 20-40% of volatile matter.
• The lower volatile, the higher the heating value.
• Lignite:- lowest grade coal. Containing :-
• moisture as high as 30%
• high volatile matter.

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 Process of formation of coal
 According to ASTM ( American Society of
Testing and Materials).
Peat is not regarded as a rank of a coal.
 Peat contains up to 90% moisture and is not
attractive as utility fuel.
 Rank carries the meaning of degree maturation
( carbonization) and is a measure of carbon
content in coal.
 Lignite is considered to be low rank and
anthracite to be high rank.
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 COAL ANALYSIS
 There are two types of coal analysis.
1. Proximate analysis.
2. Ultimate analysis.
PROXIMATE ANALYSIS
 Indicates the behavior of coal when it is heated.
1. When 1 gram sample of coal is subjected to a temperature
of about 1050C for a period of 1 hour, the loss in weight of
the sample gives the moisture content of the coal.
2. When 1 gram sample of coal is placed in covered platinum
crucible and heated to 9500C and maintained at that
temperature for about 7 minute.
 There is a loss in weight due to the eliminating of moisture
and volatile matter.
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 COAL ANALYSIS

3. When 1 gram sample of coal is placed in uncovered

platinum crucible and heated to 7200C until the coal is
completely burned, a constant weight reached, which
indicates that there is only ash remaining in the crucible.
 Complete combustion of coal is determined by repeated
weighing of the sample.
 Percentage by mass
Fixed carbon + volatile matter + moisture + ash =
100
FC = 100-( VM + M + A)

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 COAL ANALYSIS
 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.
 The amount of volatile matter indicates:-
 The coal will burn with a short or long flame.
 It tends to produce smoke.
 The more volatile the coal, the more it will smoke.

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 ULTIMATE ANALYSIS
 The ultimate analysis gives the chemical elements that
comprise the coal substance, together with ash and
moisture.
 The coal substance consists of organic compounds of
carbon, hydrogen and oxygen derived from the original
vegetable matter.
 The analysis shows the following components on mass
basis:-

C + H + O + N + S + M + A= 100%

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 COAL PROPERTIES
 There are certain properties of coal which are important in
power plant application.
1. Sulphur content:-
 sulphur content in a coal is combustible and generates
some energy by its oxidation to SO2.
 SO2 ( sulphurdioxide) is a major source of atmospheric
pollution.
 The operating cost of SO2 removal equipment need to be
considered while selecting a coal with a high sulphur.

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2. Heating value ( calorific value)
The heat transferred when the products of complete combustion of a
sample of fuel are cooled to the initial temperature of air and fuel.
 It is normally determined in a standard test in a bomb
calorimeter,
 where a coal sample of known mass is burnt with pure
oxygen supply completely in a stainless steel bomb or
vessel surrounded by a known mass of water and the rise
in water temperature is noted.
 Two different heating values are cited for fuel.
1. Higher heating value (HHV)
2. Lower heating value (LHV)

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 Bomb calorimeter

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 2. Heating value ( calorific value)
 Higher heating value:- assumes that the water vapor in the
products condenses and thus includes the latent heat of
vaporization of the water vapor formed by combustion.
 Lower heating value:-assumes that the water vapor formed by
combustion leaves the vapor it self.
LHV= HHV – mWhfg
 If the ultimate analysis is known, the HHV of anthracite and
bituminous coals can be determined approximately by using
Dulong and Petit formulas as
HHV = 33.83C + 114.45( H-O/8) + 9.38S in MJ/Kg
 The latent heat of vaporization hfg at the partial pressure of
water vapor in the combustion products as 2.395MJ/Kg.
 The lower heating value of coal is given by
LHV = HHV- 2.395 mw
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 ASH SOFTENING TEMPERATURE
 The ash softening temperature is the temperature at which
the ash softens and becomes plastic.
 This is some times below the melting point of the ash.
 The design of the steam generator greatly depends on the
ash softening temperature of the coal.
 If the furnace temperature is higher than the ash softening
temperature all the ash will melt and would come out of the
furnace bottom continuously as molten slag.
 For a furnace that would discharge ash in the form of solid,
a high ash softening temperature would be required.

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 Combustion
Definition
 A chemical reaction during which a fuel is oxidized and a
large quantity of energy is released is called combustion.
 The oxidizer most often used in combustion processes is air,
for obvious reasons—it is
Free
Readily available.
 Pure oxygen O2 is used as an oxidizer only in some
specialized applications, such as cutting and welding, where
air cannot be used.

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 Combustion
 On a mole (volume) basis dry air is composed of:-
 20.9 percent oxygen,
 78.1 percent nitrogen,
 1 percent argon, and small amounts of carbon dioxide, helium,
neon, and hydrogen.
 dry air can be approximated as 21 percent oxygen and 79 percent
nitrogen by mole numbers.

 During combustion, nitrogen behaves as an inert gas and does not react
with other elements.
 The presence of nitrogen greatly affects the outcome of a combustion
process.
 Nitrogen usually enters a combustion chamber in large quantities at low
temperatures and exits at considerably higher temperatures. Absorbing a
large proportion of the chemical energy released during combustion.
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 Combustion
 Nitrogen is assumed to remain perfectly inert.
 At very high temperatures, such as those encountered in
internal combustion engines, a small fraction of
nitrogen reacts with oxygen, forming hazardous gases
such as nitric oxide.
 Air that enters a combustion chamber normally contains
some water vapor (or moisture), which also deserves
consideration.
 For most combustion processes, the moisture in the air
and the H2O that forms during combustion can also be
treated as an inert gas, like nitrogen.

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 Combustion Fundamentals

Fire Triangle and Tetrahedron

• Three basic factors
required for
combustion:
– Fuel
– Oxygen
– Heat
• Chemical chain
reactions keep the fire
burning.

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 Combustion Fundamentals
 At very high temperatures, however, some water vapor
dissociates into H2 and O2 as well as into H, O, and OH.
 When the combustion gases are cooled below the dew-point
temperature of the water vapor, some moisture condenses.
 It is important to be able to predict the dew-point
temperature since the water droplets often combine with
the sulfur dioxide that may be present in the combustion
gases, forming sulfuric acid, which is highly corrosive.

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 Combustion Fundamentals
 During a combustion process, the components that exist
before the reaction are called reactants and the components
that exist after the reaction are called products.

 Consider, for example, the combustion of 1 kmol of carbon

with 1 kmol of pure oxygen, forming carbon dioxide,

 If carbon is burned with air instead of pure oxygen, both

sides of the combustion equation will include N2.
 The N2 will appear both as a reactant and as a product.

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 Combustion Fundamentals
 We should also mention that bringing a fuel into
intimate contact with oxygen is not sufficient to start a
combustion process. (Thank goodness it is not.
Otherwise, the whole world would be on fire now.)
1. The fuel must be brought above its ignition temperature
to start the combustion.
 The minimum ignition temperatures of various
substances in atmospheric air are :-
 260°C for gasoline.
 400°C for carbon.
 580°C for hydrogen.
 610°C for carbon monoxide.
 630°C for methane.
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 Combustion Fundamentals
2. The proportions of the fuel and air must be in
the proper range for combustion to begin.
Example, natural gas does not burn in air in
concentrations less than 5 percent or greater than
about 15 percent.

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 Combustion Fundamentals

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 Combustion Fundamentals
 Chemical equations are balanced on the basis of the
conservation of mass principle (or the mass balance).
 The total mass of each element is conserved during a
chemical reaction.

 The total number of atoms of each element is conserved

during a chemical reaction .
 The total number of atoms is equal to the total mass of the
element divided by its atomic mass.
 The total number of moles is not conserved during a
chemical reaction.

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 Combustion Fundamentals
 A frequently used quantity in the analysis of combustion processes to quantify
the amounts of fuel and air is the air–fuel ratio.
 It is usually expressed on a mass basis and is defined as the ratio of the mass
of air to the mass of fuel for a combustion process.

ge n
o xy 2kg hydrogen
k g
16 16kg oxygen

2kg
hydrogen
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THEORETICAL AND ACTUAL COMBUSTION PROCESSES
 A combustion process is complete if all the carbon in the
fuel burns to CO2, all the hydrogen burns to H2O, and all the
sulfur (if any) burns to SO2.

 All the combustible components of a fuel are burned to

completion during a complete combustion process.
 The combustion process is incomplete if the combustion
products contain any unburned fuel or components such as
C, H2, CO, or OH.
 Insufficient oxygen is an obvious reason for incomplete
combustion, but it is not the only one.

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 THEORETICAL AND ACTUAL COMBUSTION PROCESSES
 Incomplete combustion occurs even when more oxygen is present in
the combustion chamber than is needed for complete combustion.
 This may be attributed to insufficient mixing in the combustion
chamber during the limited time that the fuel and oxygen are in
contact.
 Oxygen has a much greater tendency to combine with hydrogen than
it does with carbon.
 The hydrogen in the fuel normally burns to completion, forming
H2O, even when there is less oxygen than needed for complete
combustion.
 Some of the carbon, however, ends up as CO or just as plain C
particles (soot) in the products.
 The minimum amount of air needed for the complete
combustion of a fuel is called the stoichiometric or theoretical air.

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 THEORETICAL AND ACTUAL COMBUSTION PROCESSES

 When a fuel is completely burned with theoretical air, no

uncombined oxygen is present in the product gases.
 The theoretical air is also referred to as the chemically
correct amount of air, or 100 percent theoretical air.
 A combustion process with less than the theoretical air is
bound to be incomplete.
 The ideal combustion process during which a fuel is burned
completely with theoretical air is called the stoichiometric or
theoretical combustion of that fuel

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 THEORETICAL AND ACTUAL COMBUSTION PROCESSES

 For example, the theoretical combustion of methane is

 Notice that the products of the theoretical combustion

contain no unburned methane and no C, H 2, CO, OH, or free
O2.
 In actual combustion processes, it is common practice to use
more air than the Stoichiometric amount to :-
 Increase the chances of complete combustion
 Control the temperature of the combustion chamber.

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 THEORETICAL AND ACTUAL COMBUSTION PROCESSES

 The amount of air in excess of the stoichiometric amount is

called excess air.
 The amount of excess air is usually expressed in terms of the
stoichiometric air as percent excess air or percent
theoretical air.
For example, 50 percent excess air is equivalent to 150 percent
theoretical air, and 200 percent excess air is equivalent to
300 percent theoretical air.
 The stoichiometric air can be expressed as 0 percent excess
air or 100 percent theoretical air.

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 THEORETICAL AND ACTUAL COMBUSTION PROCESSES

 Amounts of air less than the stoichiometric amount are

called deficiency of air and are often expressed as percent
deficiency of air.
For example, 90 percent theoretical air is equivalent to 10
percent deficiency of air.
 The amount of air used in combustion processes is also
expressed in terms of the equivalence ratio.
 which is the ratio of the actual fuel–air ratio to the
stoichiometric fuel–air ratio.

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 Combustion Stoichiometry

• Thus for every mole of fuel burned, 4.76( n + m/4) mol of air
are required and 4. 76( n + m/4) + m/4 mol of combustion
products are generated.
• The molar fuel/air ratio for stoichiometric combustion is 1/[4.
76( n + m/4)].
• Gas compositions are generally reported in terms of mole
fractions since the mole fraction does not vary with temperature
or pressure as does the concentration (moles/ unit volume).
• The product mole fractions for complete combustion of this
hydrocarbon fuel are

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 Combustion Stoichiometry

• The large quantity of nitrogen diluent substantially reduces the

mole fractions of the combustion products from the values they
would have in its absence.
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 Exercises

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 Example
Elemental analysis of food waste

FW Elemental Composition %
C 45.405

H 7.655

O 42.915

N 3.945

S 0.4
The biochemical reaction equation used for this analysis is taken from Wu et al [15], and is reproduced in equation

CnHaObNcSd + c1H2O = c2CO2 + c3CH4 + c4NH3 + c5H2S

C: n = c2 + c3
H: a + 2c1 = 4c3 + 3c4 + 2c5
O: b + c1 = 2c2
N: c = c4
S: d = c5
Where,
c1 = n – a/4 – b/2 + (3/4)*c + d/2
c2 = n/2 – a/8 + b/4 + (3/8)*c + d/4

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 Example
c3 = n/2 + a/8 - b/4 - (3/8)*c - d/4
c4 = c
c5 = d

Balance of biochemical reaction

MOLAR RATIOS AND COEFFICIENT CALCULATIONS

  Left Right
C N n/2 + n/2 = n
H a + 2*[ n – a/4 – b/2 + (3/4)*c + d/2] 4[n/2 + a/8 - b/4 - (3/8)*c - d/4] + 3c + 2d
= 2n + a/2 - b + (3/2)*c + d = 2n + a/2 -b + (3/2)*c + d
O b + [n – a/4 – b/2 + (3/4)*c + d/2] 2*[ n/2 – a/8 + b/4 + (3/8)*c + d/4]
= n –a/4 + b/2 + (3/4)*c + d/2 = n –a/4 + b/2 + (3/4)*c + d/2
N C C
S D D

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 Combustion Stoichiometry

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 Complete combustion ...
Initial state Final state

Combustion
Fuel + Air
products

Total completion of the combustion process

requires ...
Complete combustion …
1. sufficiently of oxygen (>stoichiometric)
(total reactions)
2. high temperature (> 850 C)
C + O2  CO2 + energy
3. long residence time (some sec.)
H2 + 1/2 O2  H2O + energy
4. good turbulence (mixing fuel-air)
S + O2  SO2 + energy
 COMBUSTION
Dominating gases for thermal processing of wood
with varying air supply at 800 °C

H2 (g)
Stoichiometric
combustion
CO (g)
Pyrolysis

Gasification Combustion

CO2 (g)

H2O (g)
CH4 (g) O2 (g)

“Also some C (s)” Air

 COMBUSTION
• Almost 90 % of primary energy generated in the world is obtained
through combustion processes.
• Oxidation reactions involving fuels are usually strongly exothermic.
• In industrial processes the most common oxidizer is ambient being free
and easy to get. Ambient air composition (By Volume) :
• 78 % N2
• 21 % O2
• 1 % Ar
• XN2 = Moles of N2/Moles of Air =78/100= 0.78
• XO2 = Moles of O2/Moles of Air = 21/100= 0.21
• XAr = Moles of Ar/Moles of Air = 1/100= 0.01
• This is what is defined as dry air and is almost constant everywhere in the
world. However, in general, actual air condition is :
• Actual Air = Dry Air + Humidity (Moisture)
• Air = O2 + 3.76 N2
 COMBUSTION
• So if we need precisely evaluate performances of a
plant we need to know humidity composition.
• In general, in chemical reaction, mass is conserved but
not molecules.
• However, in general, we even not interested in what
happens to molecules unless we don’t need every detail
descriptions of the combustion chemical reaction.
• Fuel Mixture : Biomass is basically made up of
C,H,O,N,S
• At high temperature these 5 atoms forms gaseous
compounds (Volatile reaction)
• But fuel is more complicated that this.
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 COMBUSTION

Mixture of C,H,O,N,S : Volatile Fraction

Fuel
Moisture (H2O) liquid phase

Ashes : Very complex mixture of compounds ,

they are almost chemically inert and so they don’t
Participate in the processes.
 COMBUSTION
• Note : Even if they don't participate in the combustion process , but we need to
consider them in writing mass and energy balance.
• Almost the same holds for water vapor.
• Ash contents usually one of the indicators of the quality of the fuel.
• If the fuel contains large amount of ash, the design of the combustor will be
complicated and the cost of combustor increases.
• In general ashes:
•
yash = kg of ash/kg of fuel;
0 for gaseous fuel

0-0.1 % for liquid fuels

Fuel
5-30 % for coal

10- 20 % for Biomass

Solid Fuels
15- 30 for municipal solid waste
 COMBUSTION
Moisture content
ywater = kg of water/kg of fuel;

0 for gaseous fuel

0 for liquid fuels

5-15 % for coal

Fuel
15- 30 % for Biomass Solid Fuels

20- 35 % for municipal solid waste

 Exercise and Solution

• A coal from Utah which has an ultimate analysis (by mass)

as 61.40 % C, 5.79 % H2, 25.31 % O2, 1.09 % N2 ,1.41 % S
and 5 % ash (non combustibles) is burned with 25 % excess
air in an industrial boiler. Assuming complete combustion
and the pressure in the boiler smokestack is 1 atm.
Calculate the minimum temperature of the combustion
products before liquid water begins to form in the
smokestack.

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 Exercise and Solution
• Coal whose mass percentages are specified is burned with 25 % excess air.
The dew-point temperature of the products is to be determined.

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 Exercise and Solution

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 Exercise

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 Exercise

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 Exercise

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 Note
 Predicting the composition of the products is relatively easy
when the combustion process is assumed to be complete and
the exact amounts of the fuel and air used are known.
 All one needs to do in this case is simply apply the mass
balance without needing to take any measurements.
 Things are not so simple, however, when one is dealing with
actual combustion processes.
 Actual combustion processes are hardly ever complete, even in
the presence of excess air.
 It is impossible to predict the composition of the products on
the basis of the mass balance alone.

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 Note
 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.
 Sample of the combustion gases is collected and cooled to room temperature
and pressure, at which point its volume is measured.
 The sample is then brought into contact with a chemical that absorbs the CO2.
 The remaining gases are returned to the room temperature and pressure, and
the new volume they occupy is measured.
 The ratio of the reduction in volume to the original volume is the volume
fraction of the CO2, which is equivalent to the mole fraction if ideal-gas
behavior is assumed.
 The volume fractions of the other gases are determined by repeating this
procedure.
 In Orsat analysis the gas sample is collected over water and is maintained
saturated at all times.
 The vapor pressure of water remains constant during the entire test.
60
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 Note
 For this reason the presence of water vapor in the test
chamber is ignored and data are reported on a Dry Basis.
 The amount of H2O formed during combustion is easily
determined by balancing the combustion equation.

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 COMBUSTION
 The balanced combustion equation is obtained
by making sure we have the same number of
atoms of each element on both sides of the
equation.
 That is we make sure the mass is conserved.

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 COMBUSTION
 Mole numbers are not conserved but we have conserved the
mass on a total basis as well as a specie basis.
 The complete combustion process is also called the
Stoichiometric combustion, and all coefficients are called
the Stoichiometric coefficients.
 In most combustion processes oxygen is supplied in the
form of air rather than pure oxygen.
 Air is assumed to be 21% oxygen and 79% nitrogen on a
volume basis.
 For ideal gas mixtures, percent by volume is equal to percent
by moles.

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 COMBUSTION
 Complete combustion of the fuel will not occur unless there is an
excess of air present greater than just the theoretical air required for
complete combustion.
  To determine the amount of excess air supplied for a combustion
process, let us define the air-fuel ratio, AF as

 the theoretical air fuel ratio

 Mole basis

 Mass Basis

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 COMBUSTION
Percent Theoretical and Percent Excess Air
 In most cases more than theoretical air is
supplied to insure complete combustion and to
reduce or eliminate carbon monoxide (CO) from
the products of combustion.
 The amount of excess air is usually expressed as
percent theoretical air and percent excess air.

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 COMBUSTION
 Write the combustion equation of octane with 120% theoretical
air (20% excess air).

 Note that (1)(12.5)O2 is required for complete combustion to

produce 8 kmol of carbon dioxide and 9 kmol of water.
 therefore, (0.2)(12.5)O2 is found as excess oxygen in the
products.
 Second method to balance the equation for excess air:-

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 COMBUSTION

Incomplete Combustion With Known % Theoretical Air

 Consider combustion of C8H18 with 120 % Theoretical air where
80 % C in the fuel goes into CO2 :-

 Why is X>2.5?
  Then the balanced equation is

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 COMBUSTION
Combustion Equation When Product Gas Analysis Is
Known
Example
 Propane gas C3H8 is reacted with air such that the
dry product gases are 11.5% CO2, 2.7% O2, and
0.7% CO by volume.
What percent theoretical air was supplied?
What is the dew point temperature of the products if the
product pressure is 100 kPa?

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 COMBUSTION
 The unknown coefficients A, B, and X are found by conservation
of mass for each species.

 The balanced equation is

Second method to find A:

 Assume the remainder of the 100 kmol of dry product gases is N2.

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 COMBUSTION
 Generally we should write the combustion equation per kmol of fuel.
 To write the combustion equation per unit kmol
of fuel divide by 4.07:

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 COMBUSTION
 The actual air-fuel ratio is

 The theoretical combustion equation is

 The theoretical air-fuel ratio is

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 COMBUSTION
 The percent theoretical air is

 The percent excess air is

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 COMBUSTION
DEW POINT TEMPERATURE:
 The dew point temperature for the product gases
is the temperature at which the water in the
product gases would begin to condense when the
products are cooled at constant pressure.
 The dew point temperature is equal to the
saturation temperature of the water at its partial
pressure in the products.

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 COMBUSTION
Dew Point Temperature:

 What would happen if the product gases are cooled to 1000C or to

300C?

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 COMBUSTION
Dew Point Temperature:
Example
  An unknown hydrocarbon fuel, CXHY is reacted
with air such that the dry product gases are
12.1% CO2, 3.8% O2, and 0.9% CO by volume.
What is the average make-up of the fuel?

  We assume 100 kmol (Do you have to always

assume 100 kmol?) of dry product gases; then
the percent by volume can interpreted to be mole
numbers.
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 COMBUSTION
 We do not know how much air was supplied or
water formed to get the 100 kmol of dry product
gases. But, we assume 1 kmol of unknown fuel.

 The 5 unknown coefficients A, B, D, X, and Y

are found by conservation of mass for each
species, C, H, O, and N plus one other equation.
 Here we use the subtraction method for the
nitrogen to generate the fifth independent
equation for the unknowns.
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 COMBUSTION
 The unknown coefficients A, B, and X are found
by conservation of mass for each species.

 The balanced equation is

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 Exercises

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 COMBUSTION
Enthalpy of Formation
 When a compound is formed from its elements
( e.g. Methane, CH4, from C and H2), heat
transfer occurs.
When heat is given off, the reaction is called exothermic.
When heat is required, the reaction is called endothermic.
Methane
C Reaction CH4

2H2
Chamber

Reactants Products
Qnet TP =298K
TR = 298 K
PP = 1 Atm
PR = 1 Atm

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 COMBUSTION
Enthalpy of Formation

 The conservation of energy for a steady-flow

combustion process is

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 COMBUSTION
Enthalpy of Formation
 We need to establish a common reference state
for the enthalpies of reacting components.
 The enthalpy of the elements or their stable
compounds is defined to be zero at 250C (298 K)
and 1 atm (or 0.1 MPa).

 This heat transfer is called the enthalpy of formation for

methane
 The superscript (o) implies the 1 atm pressure
value and the subscript (f) implies 25oC data.
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 COMBUSTION
Enthalpy of Formation
 During the formation of methane from the
elements at 298 K, 0.1 MPa, heat is given off (an
exothermic reaction) such that

 The enthalpy of formation, , is tabulated for

typical compounds.
 The enthalpy of formation of the elements in
their stable form is taken as zero.

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 COMBUSTION
Enthalpy of Formation
 The enthalpy of formation of the elements found
naturally as diatomic elements, such as nitrogen,
oxygen, and hydrogen, is defined to be zero.
Substance Formula M
kJ/kmol
Air 29 0
Oxygen O2 32 0
Nitrogen N2 28 0
Carbon Dioxide CO2 44 -393,520
Carbon CO 28 -110,530
Monoxide
Water (vapor) H2Ovap 18 -241,820
Water (liquid) H2Oliq 18 -285,830
Methane CH4 16 -74,850
Acetylene C2H2 26 +226,730
Ethane C2H6 30 -84,680
Propane C3H8 44 -103,850
Butane C4H10 58 -126,150
Octane (vapor) C8H18 114 -208,450
Dodecane C12H26 170 -291,010
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 COMBUSTION
ENTHALPY OF FORMATION
 The enthalpies are calculated relative to a common
base or reference called the enthalpy of
formation.
 The enthalpy of formation is the heat transfer
required to form the compound from its elements at
250C (77 F) or 298 K (537 R), 1 atm.
 The enthalpy at any other temperature is given as

 Here the term is the enthalpy of any component

at 298 K.
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 COMBUSTION
Enthalpy of Formation
 If tables are not available, the enthalpy
difference due to the temperature difference can
be calculated from:

 When the reactants and products are at

temperatures other than 298 K, the enthalpy is
given by
  The heat transfer is

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 COMBUSTION
Enthalpy of Formation
Example:
 Butane gas C4H10 is burned in theoretical air as
shown below. Find the net heat transfer per kmol
of fuel. Fuel Reaction Chamber
CO 2
C4H10 H2O
  N2
Theoretical
Air
Products
Reactants TP ,PP
TR ,PR Qnet

 Balanced combustion equation:

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 COMBUSTION
Enthalpy of Formation
 The steady-flow heat transfer is

 Reactants: TR = 298 K
Comp Ni
kmol/kmol kJ/kmol kJ/kmol kJ/kmol kJ/kmol fuel
fuel
C4H10 1 -126,150 - - -126,150
O2 6.5 0 8,682 8,682 0
N2 24.44 0 8,669 8,669 0

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 COMBUSTION
Enthalpy of Formation
 Assume products: TP = 1000 K
Ne
Comp kmol/kmol fuel
kJ/kmol kJ/kmol kJ/kmol kJ/kmol fuel
CO2 4 -393,520 42,769 9,364 -1,440,460
H2 O 5 -241,820 35,882 9,904 -1,079,210
N2 24.44 0 30,129 8,669 +524,482

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 COMBUSTION
Adiabatic Flame Temperature
 The temperature the products have when a
combustion process takes place adiabatically is
called the adiabatic flame temperature.
Example:
 Liquid octane, C8H18(liq) is burned with 400%
theoretical air. Find the adiabatic flame
temperature when the reactants enter at 298 K,
0.1 MPa and the products leave at 0.1MPa.

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 Adiabatic Flame temperature

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 COMBUSTION
Adiabatic Flame Temperature
 The combustion equation is
CO2
Fuel Combustion
C8H18 Chamber O2
400% H2O
TheoAir
N2
Reactants Products
Qnet = 0
TR = 298 K TP = ?
PR = 0.1 MPa PP = 0.1MPa

 The steady-flow heat transfer is

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 COMBUSTION
Adiabatic Flame Temperature
 Thus, HP = HR for adiabatic combustion. We
need to solve this equation for TP.
  Since the reactants are at 298 K, ( )i = 0,

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 COMBUSTION
Adiabatic Flame Temperature

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 COMBUSTION
Adiabatic Flame Temperature
 Thus, setting HP = HR yields

 To estimate TP, assume all products behave like N2 and

estimate the adiabatic flame temperature from the
nitrogen data.

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 COMBUSTION
Adiabatic Flame Temperature
 Because of the tri-atomic CO2 and H2O, the
actual temperature will be somewhat less than
985 K. Try 960 K and 970K.
Ne

CO2 8 40,607 41,145

H2O 9 34,274 34,653
O2 37.5 29,991 30,345
N2 188 28,826 29,151
7,177,572 7,259,362

 Interpolation gives: TP = 962 K

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 COMBUSTION
Adiabatic Flame Temperature
Example
  Liquid octane, C8H18(liq) is burned with excess air. The
adiabatic flame temperature is 960 K when the reactants
enter at 298 K, 0.1 MPa and the products leave at
0.1MPa. What percent excess air is supplied?
CO2
Fuel Combustion O2
C8H18(liq) Chamber
H2O
Excess
Air N2

Reactants Products

TR = 298 K Qnet = 0 TP = 960 K

PR = 0.1 MPa PP = 0.1MPa

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 COMBUSTION
Adiabatic Flame Temperature
  Let A be the excess air; then combustion equation is:-

 The steady-flow heat transfer is

 Here, since the temperatures are known, the are

known.
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 COMBUSTION
Adiabatic Flame Temperature
 The product gas mole numbers are unknown but are
functions of the amount of excess air, A. The energy
balance can be solved for A.

 Thus 300% excess, or 400% theoretical, air is supplied.

Example
 Tabulate the adiabatic flame temperature as a function of
excess air for the complete combustion of C3H8 when
the fuel enters the reaction chamber at 298 K and the air
enters at 400 K.

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 COMBUSTION
  The combustion equation is:

 Where A is the value of excess air in decimal form.

 The steady-flow heat transfer is

% Excess Air Adiabatic Flame Temp. K

0 2459.3
20 2191.9
50 1902.5
100 1587.1

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 COMBUSTION
 The Enthalpy of Reaction and Enthalpy of
Combustion
 When the products and reactants are at the same
temperature, the enthalpy of reaction hR, is the
difference in their enthalpies.
 When the combustion is assumed to be complete with
theoretical air supplied the enthalpy of reaction is called
the enthalpy of combustion, hC.
 The enthalpy of combustion can be calculated any value
of the temperature but it is usually determined at 250C or
298 K.

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 COMBUSTION
 The Enthalpy of Reaction and Enthalpy of
Combustion
Heating Value
 The heating value, HV, of a fuel is the absolute value of
the enthalpy of combustion or just the negative of the
enthalpy of combustion.
 The lower heating value, LHV, is the heating value
when water appears as a gas in the products.

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 COMBUSTION
 The Enthalpy of Reaction and Enthalpy of
Combustion
Heating Value
 The lower heating value is often used as the amount of
energy per kmol of fuel supplied to the gas turbine
engine.
 The higher heating value, HHV, is the heating value
when water appears as a liquid in the products.

 The higher heating value is often used as the amount of

energy per kmol of fuel supplied to the steam power
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 COMBUSTION
 The Enthalpy of Reaction and Enthalpy of
Combustion
Heating Value
 The higher and lower heat values are related by the
amount of water formed during the combustion process
and the enthalpy of vaporization of water at the
temperature.

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 COMBUSTION
 The Enthalpy of Reaction and Enthalpy of
Combustion
Heating Value
Example
 The enthalpy of combustion of gaseous C8H18 at 250C
with liquid water in the products is -5,512,200 kJ/kmol.
Find the lower heating value of liquid octane.

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 COMBUSTION
 The Enthalpy of Reaction and Enthalpy of
Combustion
Closed System Analysis:
Example:
 A mixture of 1 kmol C8H18 gas and 200% excess
air at 250C, 1 atm is burned completely in a
closed system (a bomb) and is cooled to 1200 K.
Find the
Heat transfer from the systemW net

1 kmol C H8 18 gas
System final pressure.
200% Excess Air
T1 = 25oC
Qnet
P1 = 1 Atm Rigid
T2 = 1200 K Container 114
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 COMBUSTION
 The Enthalpy of Reaction and Enthalpy of
Combustion
Closed System Analysis:

 Assume that the reactants and products are ideal gases,

then

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 COMBUSTION
 The Enthalpy of Reaction and Enthalpy of
Combustion
 The balanced combustion equation for 200% excess
(300% theoretical) air

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 Pollutant formation - Greenhouse gas emission
 Fossil fuels are mainly carbon based.
 The combustion of fossil fuel results in formation of Carbon Dioxide (CO2)
 After combustion of the fuels, the CO2 is usually released into the
atmosphere
 This gas absorbs the infrared part of radiation from the earth and
reradiates it back to the earth, creating the effect of a greenhouse.
 Due to green house effect of carbon dioxide, the average global temperature of
earth is increasing.
 The increased temperature of the earth due to greenhouse gas effect will
results in erratic weather pattern, floods, droughts, submerging of low-lying
areas due to melting of ice at poles,etc.

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