LECTURE NOTES

EME 3125 Combustion System Modeling and Design

MSc Mechanical Engineering

Mechanical Engineering Department JKUAT

2023 Edition

1
Purpose
The aim of this course is to enable the student to understand concepts of combustion modeling
in-order to design and predict performance of combustion devices for particular applications.

Learning Outcome
At the end of this course, the student should be able to;

1. apply thermodynamics concepts in combustion of fuels

2. evaluate and analyze the mechanism of combustion including modeling ame structure

3. model and design efficient and clean combustion devices

Outline
Heats of reaction. Adiabatic flame temperature, and chemical composition of the products of
combustion. Production of pollutants in combustion systems.

Kinetics of reactions. Conservation equations for multi-component reacting flows. Explosions.

Fuel oxidation.

Propagation and structure of laminar premixed flames. Detonations. The role of physical
and chemical processes in combustion. Ignition, flammability, and quenching of combustible
gas mixtures. Laminar and turbulent flames. Flame stabilization.

Combustion of fuel droplets and sprays. Combustion of solid fuels: Chemical and physical
processes in the combustion of wood.

Emissions: Negative effects of combustion products, effect on health, environment. Pollutant

formation, CO, NOx, SOx, Particulate (TPM), Emission quantification.

2
References

1. Colannino J., Modeling of Combustion systems: A practical approach, 1st Ed. 2006,
ISBN-13: 978-0849333651

2. J. Warnatz, U. Maas and R.W. Dibble, Combustion: Physical and chemical fundamen-
tals, modeling, simulation, experiments, pollutant formation, 4th Ed, 2006, ISBN-13:978-
3540259923

3. C.E. Baukal, Industrial Burners Handbook, 1st Ed. CRC Press, 2003, ISBN-13: 978-
0849313868

4. Mahallawy E and Habik S., Fundamentals and Technology of Combustion, 1st Ed. (2002)

5. McAllister S., Chen J. and Carlos F. Fundamentals of Combustion Processes, Springer

Publishers, 2011.

6. Rogers G.F.C. & Mayhew Y.R. (1992) Engineering Thermodynamics, Longman Singapore
Publishers, 4th Ed.

7. Thermodynamics: An Engineering Approach by Yunus Cengel and Michael Boles

3
Tasks

1. Practical 1: Describe the operating principle of a bomb calorimeter. Subsequently use

the bomb calorimeter in the thermodynamics laboratory to determine the higher heating
value of typical fuels diesel, petrol, kerosene.

4
Contents

Outline . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2

1 Combustion Fundamentals 7
1.1 Aims . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
1.1.1 Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
1.2 Basics Concepts of Fuels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
1.2.1 Fuels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
1.2.2 Choice of Fuels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
1.2.3 Related Properties of Fuels . . . . . . . . . . . . . . . . . . . . . . . . . . 11
1.3 Thermodynamic Analysis of Combustion . . . . . . . . . . . . . . . . . . . . . . 12
1.3.1 Mixture Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
1.3.2 Theoretical and Actual Combustion . . . . . . . . . . . . . . . . . . . . . 13
1.3.3 Stoichiometric Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
1.3.4 Quantifying Combustible Mixtures . . . . . . . . . . . . . . . . . . . . . 15
1.4 Exercise . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
1.5 Energy Balance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
1.5.1 Heating value: . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
1.5.2 Estimation of Higher Heating Value . . . . . . . . . . . . . . . . . . . . . 18
1.5.3 Bomb Calorimeter . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
1.5.4 Adiabatic Flame Temperature . . . . . . . . . . . . . . . . . . . . . . . . 19
1.5.5 Iterative enthalpy balance . . . . . . . . . . . . . . . . . . . . . . . . . . 21

5
2 Kinetics of Combustion 24
2.1 Combustion Mechanism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
2.2 Reaction Rate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
2.2.1 Simple Models of Combustion . . . . . . . . . . . . . . . . . . . . . . . . 28
2.2.2 Role of Pressure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
2.2.3 Assumptions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
2.3 Transport Equations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
2.3.1 Review of Heat and Mass Transfer . . . . . . . . . . . . . . . . . . . . . 30
2.3.2 Transport Equations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
2.3.3 Normalized Conservation Equations . . . . . . . . . . . . . . . . . . . . . 34

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Chapter 1

Combustion Fundamentals

1.1 Aims
1. Fuels classifications and properties

2. Thermodynamics of combustion

3. Carry out energy balance on reacting systems

4. Determine the enthalpy of reaction and combustion as well as obtain the heating values
of fuels

5. Obtain the adiabatic flame temperature (highest temperature attained by burning mix-
ture)

Combustion is a chemical reaction in which a fuel is oxidized and a large amount of energy is
released. It involves complex interactions between many disciplines such as; thermodynamics,
chemical kinetics (rates and mechanisms of reactions), fluid mechanics, heat and mass transfer,
turbulence, material structure and behavior. For combustion to occur fuel and an oxidizer
react. Fuel is any material that can be burned to release thermal energy.

1.1.1 Applications

Combustion study is applied in the following areas.

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 1. Power production: Coal and heavy fuel oil combustion in power stations, liquid fuels for
automobiles, aircrafts, ships etc., natural gas for gas turbines, solid and liquid propellants
in rocket motors.

2. Process industry: Production of materials such as steel, glass, ceramics, cement, refined
fuels etc.

3. Fire prevention and fire safety.

4. Household and industrial heating

5. Study of effects on the environment; By products of combustion affects the environment

in the following ways. Combustion lead to formation of pollutants such as NOx, SOx,
CO, soot and lead all of which affects human health. Carbon dioxide a by-product of
combustion is known to be the driving force behind global warming.

1.2 Basics Concepts of Fuels

Fuels generate heat upon reaction with an oxidizer and as such they are therefore an important
element in study of combustion. In practice fuels should be abundant and cheap. For this
reason the most common source are non-renewable fossil fuels. Unfortunately they generate
emissions causing global warming. To overcome this research is underway on utilization of
non-renewable fuels. In the following analysis classification methods are examined.

1.2.1 Fuels

Fuels can be classified in a number of ways. Two common methods of classifications are phase
and source.

Fuel Phase

Based on the phase there exists solid, liquid or gaseous fuels. Solid fuels include biomass
such as wood, lignite, peat and coal. Liquid fuels are derived from crude oil. These include

8
petrol, diesel, kerosene and fuel oils. Gaseous fuels are natural gas, hydrogen and syngas, liquid
petroleum gas etc. Natural gas is gaseous fuels consist methane and small quantities of propane,
ethane, butane and pentane and exist as liquids in compressed form (CNG). Liquid petroleum
fuel (LPG) is a mixture of ethane, propane, butane and pentane obtained from natural gas
processing plants.

Fuel Source

Based on source, two categories of fuels exist.

1. Non-renewable sources: These are exhaustible fuels such as coal, crude, natural gas,
nuclear etc. The world energy demand is increasing due to growth in population as shown
in Figure 1.1. Coupled to this is a rise in carbon emissions. This is due to increased use
of coal in emerging economies. Energy Sources 3

40000
0
~" E 12000
30000 .~
P+
i
~ .,= 11000 / C02 emission "!

[20000 .-
,- o= 4000
] ~ 0
0 I I 1 I i I i ~ 10000
1975 1985 1995 2005 2015
Fig. 1.1 (a): World primary energy supply and CO, emission 1971-2020 [ 1]. Reproduced
by permission of OECD/IEA (International Energy Agency).
Figure 1.1: Energy demand and carbon dioxide emissions
6000

2. Renewable sources: These include solar, wind, biofuels, solid waste, biomass etc. These
9~ 4000 Solid
fuels may provide the long term solution to energy problem. Low energy density (amount
e~
of energy per unit
0
mass) is a challenge associated with solid waste, biomass and biofuels.
= 2 0 0 0is another challenge for solar and wind energy. This is the energy
Low capacity factor
.9 Other renewables
supply within a period of one year.

1975 1985 1995 2005 2015

Fig. 1.1 (b): World primary energy by fuel 1971-2020 [1]. Reproduced by permission of
OECD/IEA (International Energy Agency).

9
Chemical Structure

Organic fuels can be classified based on chemical structure. There are alkanes, alkenes, alkynes
and aromatic compounds. Alkanes may be expressed in a formula as

Cn H2n+2

They include methane (CH4 ), ethane (C2 H6 ), propane (C3 H8 ) and butane (C4 H10 ). The other
names are derived from Greek words based on number of carbon atoms. For example there
is pentane (C5 H12 ), hexane (C6 H14 ), heptane (C7 H16 ), octane (C8 H18 ) etc. Note that as the
number of atoms increase the number of bonds increase in turn increasing the number boiling
point and density of the fuel.
Alkenes and alkynes have a formulae expressed respectively as

Cn H2n and Cn H2n−2

It is possible to derive corresponding alkene or alkyne for each of the alkane. Aromatic com-
pounds are based on benzene and its derivatives.

1.2.2 Choice of Fuels

Air is the main source of oxidation of fuel for combustion to occur. Selection of fuel depends
on the application, local safety and emission regulations. A brief outline of factors influencing
fuel selection is given.

1. Energy density: This is the energy content per volume or mass. For instance liquid
fossil fuels contain 33MJ/L while biofuels such as ethanol have 29MJ/L. Gaseous fuels
have a lower energy density. For example hydrogen has 12 kJ/L. It therefore has to be
compressed (2500 atm) to make its energy density equal to that of other liquid fuels.
For transportation liquid fuels are used. Hydrogen is used as space shuttle fuel. Its
boiling point is -252.76◦ C and this makes storage a challenge due to heat transfer from
surrounding. Storage of liquid hydrogen is an area under research world wide.

10
 2. Safety: Fuels should be safe to handle yet easy to burn. This is affected by the flammabil-
ity, ignition, toxicity etc of fuels. Petrol ignites easily when spilled but is safe in containers.
Ignition and heat release rate are important in fire control.

3. Combustion characteristics: In engine combustion such as petrol engines ignition is an

important factor. This is determined by octane number. For Compression ignition auto
ignition is the corresponding factor and its described by cetane number. For gas turbines
soot point describe ease of formation of soot. The fuel property determining this is the
soot point.

4. Fuel properties: A critical element in fuel properties is the viscosity. This determines
the economy of transportation and combustion. Viscous fuels cannot be transported in
pipelines and have injection problems.

5. Cost: Low cost fuel is selected that is safe and has less emissions. Note that cost element
is the basis behind reliance on fossil fuels which has hindered development of alternative
fuels.

1.2.3 Related Properties of Fuels

1. Flash point: This is the temperature at which the fuel produces sufficient vapor that mix
with oxidizer to burn when a source of ignition is present. For petrol the flash point is
-43◦ C, Kerosene has a flash point of 38◦ C, diesel has a flash point of 51◦ C, biodiesel has
130◦ C, Jet fuel 38◦ C.

2. Pour point: The lowest temperature at which a fluid flows easily. It is temperature that
the fuel still behaves as a fluid.

3. Cloud point: It is temperature at which formation of crystals occur in fuels. It is affected

by use of additives.

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1.3 Thermodynamic Analysis of Combustion
Fundamental equations of thermodynamics are used in combustion analysis. These include the
ideal gas equation of state as well as first and second law of thermodynamics. Note that there
are eight properties encountered in thermodynamics include, temperature, pressure, volume,
internal energy, enthalpy, entropy, helmholtz and gibbs free energy.

1.3.1 Mixture Properties

Thermodynamic aspect of combustion involve determination of properties such as internal en-

ergy, enthalpy and specific heats. Combustion gases are mixture of different components,
therefore the analysis utilizes the ideal gas law on each component. The following terms are
encountered in combustion.

1. For a system of K species the mass is given by

K
X
m= mi
i=1

where mi is the mass of each species i

2. Total moles in the system

K
X
N= Ni
i=1
where Ni is the number of moles of species i

3. Mass and mole fractions for ith species are respectively given by
mi Ni
yi = , xi =
m N

4. The sum of mass and mole fractions of all species become

K
X K
X
yi = 1 , xi = 1
i=1 i=1

Note that partial pressure and mole fraction are related in the form
Pi Ni Vi
= = = xi
P N V
where Vi is the partial volume of species i and V is the total volume of the mixture.

12
 5. Knowing the molecular mass of each species Mi , it is possible to determine the average
molecular mass of the mixture in the form
P
m Ni Mi X
M= = i = xi Mi
N N i

6. The properties of the mixture can be found from the mass in a similar manner, that is
P
U mi ui X X X
u= = i = yi ui , h = yi hi , cp = yi cp,i
m m i i i

The properties can also be determined on the basis of moles in the form
P
U mi ûi X X X
û = = i = xi ui , ĥ = xi ĥi , ŝ = xi ŝi
N N i i i

7. Stoichiometric reaction is a unique reaction in which all reactants are consumed.

8. Standard heat of formation is the heat evolved when one mole of substance is formed from
its constituent elements in their respective standard states (298.15K and 1 atmosphere)

9. Adiabatic flame temperature is the temperature of products of a reacting systems taking

place adiabatically and with no work or changes in kinetic or potential energy.

1.3.2 Theoretical and Actual Combustion

Complete combustion occurs when all the fuel is consumed forming carbon dioxide and water.
If C, H2 , CO or OH is present in the products then combustion is incomplete. There are
several causes of incomplete combustion

1. Insufficient oxygen

2. Sufficient oxygen but poor mixing

3. Dissociation of products that occurs at high temperatures

The minimum air needed for complete combustion is called stoichiometric or theoretical air.
The combustion associated with this is stoichiometric combustion. If the quantity of air is less
than the stoichiometric the combustion will be incomplete.

13
1.3.3 Stoichiometric Reactions

A stoichiometric reaction is an ideal combustion process in which the maximum flame temper-
ature is achieved. A typical stoichiometric reaction involving methane with air appears in the
form
79 79
CH4 + a(O2 + N2 ) → bCO2 + cH2 O + d N2 (1.1)
21 21
where air assumed to contain 21% O2 and 79% N2 . The coefficients a, b, c and d are obtained
from mass balance of all elements on both sides of the equation. Upon balancing the following
equation is obtained

79
CH4 + 2(O2 + N2 ) → CO2 + 2H2 O + 7.52N2 (1.2)
21

Note that the mole coefficients are equivalent to volume proportions since the gases are treated
as ideal in which at a fixed temperature and pressure any ideal gas occupy the same volume. The
mass balance is carried out using one mole of fuel. The combustion equation for a hydrocarbon
fuel (Cα Hβ Oγ ) can be expressed in general equation form as

β γ 79 β β γ
Cα Hβ Oγ + (α + − )(O2 + N2 ) → αCO2 + ( )H2 O + (α + − )N2 (1.3)
4 2 21 2 4 2

This formula applies to single component fuels. Suppose the fuel was a mixture of several
components such as 95% methane and 5% hydrogen. There are two approaches to obtaining
balance reaction equations. The first one involves carrying out atomic balance on the equation
below.
79 79
0.95CH4 + 0.05H2 + a(O2 + N2 ) → bCO2 + cH2 O + d N2
21 21
To give

79 79
0.95CH4 + 0.05H2 + 1.925(O2 + N2 ) → 0.95CO2 + 1.95H2 O + 1.925 N2 (1.4)
21 21

The second method involves obtaining balanced stoichiometric reaction equation for each
fuel. Subsequently the equations are multiplied by the mole fractions and added to give equation
1.4.
Exercise: Express stoichiometric reaction equations for combustion of ethane, butane,
hexane and octane in air.

14
1.3.4 Quantifying Combustible Mixtures

1. Air fuel ratio: Actual combustion process contains air quantity that is more than the
stoichiometric amount - fuel lean or a quantity that is less than stoichiometric amount -
fuel rich. Combustion mixtures are quantified based on air fuel ratio (AFR) or fuel air
ratio (FAR - the reciprocal).

mair mf uel
AF R = , F AR =
mf uel mair

For petrol engines the AFR is about 14.7 and in most combustion processes this varies
between 14-20 for complete combustion.

2. Equivalence ratio ϕ involves normalizing the actual air fuel ratio with the stoichiometric
ratio. On this basis reaction between methane and air, Equation 1.2 gives air fuel ratio
as AFR = 17.16

3. Equivalence ratio: The ratio of FAR for actual combustion and that for a stoichiometric
combustion.
(F AR)
ϕ=
(F AR)st
Based on AFR, λ is defined
(AF R) 1
λ= =
(AF R)st ϕ

4. Percent air: Percentage of air exceeding stoichiometric amounts.

   
ma − mas ma
%EA = 100 = 100 −1
mas mas

Given any one of the above terms it is possible to determine the other two as shown in the
Table 1.1 below.

Table 1.1:  
fs f 1−ϕ
f= ϕ
ϕ = fs %EA = 100 ϕ
100.fs 100 1− ff
f= %EA+100
ϕ= %EA+100
%EA = 100 f
s

fs

15
1.4 Exercise
1. Considering a stoichiometric mixture of isooctane and air determine (i) the mole frac-
tion of fuel (ii) the fuel air ratio (iii) the mole fraction of H2 O in the products (iv) the
temperature below which H2 O starts to condense into liquid at 101.3kPa.

2. Determine the mass of air required to burn 55.5 liters of petrol (C8 H18 ).

3. In a model combustion chamber n-heptane is burned under overall lean condition. Mea-
surement of dry exhaust showed mole fractions of CO2 to be 0.084 and O2 to be 0.088.
Determine %EA, ϕ and λ

4. C2 H6 burns completely with air when the air-fuel ratio is 18 on mass basis. Determine the
percent excess or percent deficiency of air as appropriate, the composition of combustion
products and the dew point temperature when combustion products are cooled at 1 atm.

5. One kg of C8 H18 fuel is supplied to an engine with 13 kg of air. Determine the percentage
by volume of CO2 in dry exhaust gas considering exhaust gas to consist of CO2 , CO and
N2 .

6. Assignment: In a boiler coal having 88% C, 3.8% H2 , 2.2% O2 and remaining ash is
burnt in the furnace. It is found that CO2 going with flue gases constitute to be 12% and
temperature of flue gases is 260◦ C. The flue gas sample is analyzed using Orsat apparatus
at room temperature. Determine the percentage of CO2 that would be there for complete
combustion of fuel.

1.5 Energy Balance

When fuel and air undergo combustion heat energy is generated. This energy is then utilized
for various applications.
In this section several terms associated with the resulting heat energy, methods of estimating
the quantity of this energy and maximum temperature that can be attained are presented.

16
1.5.1 Heating value:

This is the amount of heat generated when a substance burns in air at standard conditions
(25◦ C and 1 bar). It is referred as lower heating value (LHV) when water present is in gas
form and higher heating value (HHV) when water is condensed. This because additional heat
(latent heat of vaporization) is extracted. Therefore

mw
LHV = HHV − hf g (1.5)
mf

where mw is mass of water in the products and mf is the mass of fuel, and hf g is 2440kJ/kg.
LHV is also called the heat/enthaply of combustion.
The heating value of a substance is obtained from heat transferred when products are cooled
and water is condensed. It is important to note that the first law of thermodynamics applies
in energy analysis of combustion reactions.

dQ = du + dW = du + P dv (1.6)

Recall also the definition of enthalpy h = u + P v meaning that,

dh = du + vdP + pdv ∴ du = dh − vdP − pdv (1.7)

which also means that energy equation can be written in the form

dQ = dh − vdP (1.8)

For a constant pressure process (constant pressure reactor dP = 0) enthalpy of reactants and
products.
−Qrxn,p = HR − HP (1.9)

Since species forming the reactants are different from products species the Qrxn,p is called the
heat/enthaply of reaction (calculated at constant pressure). It is related to enthalpy of
combustion in the form
Qrxn,p = −QC (1.10)

When a combustion reaction occurs energy is released due to rearrangement of chemical bonds
to form products. This is called heat/enthaply of formation also expressed as ∆h0i . It is the

17
energy needed for formation of products from its constituent elements (at STP). The values of
enthalpy of formation for typical species are available in table form.
The total enthalpy of a reacting system is given by the sum of enthalpy of formation and
the sensible enthalpy (hsi ) in the form

hi = ∆h0i + hsi (1.11)

1.5.2 Estimation of Higher Heating Value

The higher heating value of a fuel can be obtained using a constant pressure reactor vessel. This
is a vessel in which combustion takes place at controlled conditions so that constant pressure
is maintained. Using Equation 1.22 the global equation for the enthalpy of combustion for
reactants and products becomes
X
X
Ni,R ∆h0i,R + hsi,R − Ni,P ∆h0i,P + hsi,P


−Qrxn,p = HR − HP = (1.12)
i i

where Ni is the number of moles of species i. The sensible enthalpies of common reactants and
products are obtained from tables. From Equation 1.12 the term involving heat of formation
can be used to determine the HHV in the form;
X X
−Q0rxn,p = Ni,R ∆h0i,R − Ni,P ∆h0i,P (1.13)
i i

This is due to the fact that at standard conditions the sensible enthalpy terms drop out. When
water in the products is condensed then the HHV is obtained from this value in the form

−Q0rxn,p
HHV = (1.14)
mf

where mf = Nf uel Mf uel

Assignment:
Determination of enthalpy in Equation 1.21 utilizes a constant pressure reactor. Show that the
heating value from a constant volume reactor is in the form

−Q0rxn,p − ( i Ni,P − i Ni,R ) Ru T0

P P
HHV = (1.15)
mf

18
Subsequently show that heating values for a constant pressure reactor and a constant volume
reactor are equal.

X
UR = HR − Ni,R Ru T (1.16)

Ni ∆h0i,R therefore total internal energy of reactants be-

P
Also at standard conditions HR =
come
X X
UR = Ni,R ∆h0i,R − Ni,R Ru T (1.17)

A similar expression can be written for the products so that the final expression becomes

−Qrxn,v = UR − UP (1.18)
X X X X 
0 0
= Ni,R ∆hi,R − Ni,R Ru T0 − Ni,P ∆hi,P − Ni,P Ru T0 (1.19)
X X X X 
= Ni,R ∆h0i,R − Ni,P ∆h0i,P + Ni,P − Ni,R Ru T0 (1.20)

Using Equation 1.21 hhv becomes

−Q0rxn,p − ( Ni,P − Ni,R ) Ru T0

P P
HHV = (1.21)
mf

1.5.3 Bomb Calorimeter

This is a device used for determination of higher heating value experimentally. Shown in Figure
1.2 is a bomb calorimeter consisting of an explosive proof steel container whose volume does
not change during reaction. The vessel is submerged in a liquid and the generated heat is
transferred to the water for measurement.

1.5.4 Adiabatic Flame Temperature

This is the highest temperature attained during combustion process. It is obtained by appli-
cation of steady flow energy equation to the combustion process. One main assumptions made
is that there is no heat loss from the burning substances (adiabatic process). On this basis the
highest temperature is estimated using constant pressure combustion process in which.

−Qrxn,p = HR − HP = 0 (1.22)

19
 conditions are set for evaluation of heating values. Conservation of energy gives

UP  UR ¼ Q0rxn;v (2.34)

Thermocouple
Stirrer Igniter

Insulated container
filled with water

Reaction chamber
(bomb)

Sample cup

Fig. 2.2 Bomb calorimeter

Figure 1.2: Bomb calorimeter

Meaning that
HP (TP ) = HR (TR ) (1.23)

where
X X
Ni,P ∆h0i,P + hsi,P (TP )


HP (TP ) = Ni,P hi,P =
i i

and a similar expression can be written for reactants. Note that initially the products are not
existent and if they do they are at temperature TR . The enthalpy of reactants is thus higher
than that of the products before combustion. When the combustion begins energy released is
used to heat the mixture until the condition Equation 1.23 is achieved. This condition is shown
in Figure 1.3.
The adiabatic flame temperature TP can be estimated using four methods.

1. Using an average cp value

2. An iterative enthalpy balance

3. Using a simulated flame model

20
 32 2 Thermodynamics of Combustion

HR (T)
HR (TR) = Hp (TP)
HR (TR)
Ο x

Enthalpy Energy
Release
HP(T)

Ο
HP (TR)

Reactant Adiabatic Flame

Temperature Temperature
Temperature, T

Fig. 2.3 Graphical interpretation of adiabatic flame temperature

Figure 1.3: Enthalpy balance for combustion species

is lower than that of the reactant mixture. The energy released from combustion
4. Using the equilibrium state and a computer software (STANJAN, Chemkin and Cantera)
is used to heat up the products such that the condition HP ðTP Þ ¼ HR ðTR Þ is met.
The task is finding the product temperature given the enthalpy of reactants.
The first technique involves use of average values of cp for reactants and products and is least
Three different methods can be used to obtain TP:
accurate. The most accurate method is the flame model as it assumes finite residence time of
1. Using an average cp value,
flames and
2. Annoniterative
equilibrium conditions
enthalpy balance,which is the reality. The final method assumes equilib-
3. Finding
rium (which the equilibrium
is an ideal stateproducing
case) therefore using computer software
very low values (such as Cantera).
of temperature.
The
The four first two produce
techniques methodsnearly
can beequal
performed manually
values of if complete
temperature for leancombustion
combustion.isThey
considered and provide only quick estimates. An equilibrium state solver takes into
howeveraccount
differ after stoichiometric
dissociation combustion
of products at highonwards as shown
temperature, in Figure
making it more1.4.
accurate than
the first two methods.
1.5.5 Method 1: Constant,
Iterative enthalpyaverage cp
balance
From conservation of energy, Hp ðTp Þ ¼ HR ðTR Þ, which can be expressed as
The enthalpy balance equation can be expressed as
X X
Ni;P ½Dh^oi;P þ h^si;P ðTPX
Þ ¼ h^oi;R þ h^si;R ðTR Þ
Ni;R ½DX
iHP (TP ) = HR (TR ) ∴ Ni,Pi hi,P = Ni,R hi,R (1.24)
i i

Rearranging
that further becomesyields
( )
X X X X
Ni;P h^si;P N DPh^oi;P Dh^∆h ^si;R
X X
0 o 0 +h
ðTi,P
PÞ ¼ i,P + hsi,P )  þ ðTR Þ



∆h Ni;P(T = NNi;R
i,R i;R i,R N
si,P (T
i;R h
R ) (1.25)
i i i ii i
X
¼ Q0rxn;p þ Ni;R h^si;R ðTR Þ (2.38)
i

21
 2.4 Adiabatic Flame Temperature 35

2500
Estimate with constant cp

2000
Enthalpy balance

Temperature (K)
1500 Simulated flame

1000 Equilibrium

500

0
0.1 1 10
Equivalence Ratio, φ

Fig. 2.4 Comparison of flame temperatures with different approaches

X Different
Figure 1.4: Xvalues of adiabatic flame temperature
X
HP ðTP Þ ¼ Ni;P h^i;P ¼ Ni;P ½Dh^oi;P þ h^si;P ðTP Þ ¼ HR ðTR Þ ¼ Ni;R h^i;R
i i i
which can be rearranged to become
Next, we rearrange the above equation to find an expression for the sensible
enthalpy of the products
X X as X X
Ni,P hsi,P (TP ) = Ni,R ∆h0i,R − Ni,P ∆h0i,P + Ni,R hsi,P (TR ) (1.26)
X Xi X i X
Ni;P Dh^oi;P þ Ni;P h^si;P ðTP Þ ¼ Ni;R Dh^oi;R þ Ni;R h^si;R ðTR Þ
i i

i i i i
X
which further simplifies to X X X
Ni;P h^si;P ðTP Þ ¼ Ni;R Dh^oi;R  Ni;P Dh^oi;P þ Ni;R h^si;R ðTR Þ (2.45)
i i i i
X X 0
X X
Ni,PÞ ¼
hsi,P 0 P ) = −Qrxn,p
Ni;P h^si;P ðT P Q(Trxn;p þ
+ Þ: Ni,R hsi,P (TR )
Ni;P h^si;R ðTR
(1.27)
i i i i

Having Equation
With 1.27 the guess
an initial flameoftemperature is estimated
flame temperature, iteratively
Tp1, one evaluates by
Hp(Tp1 ) from tables
such as those in Appendix 3. If Hp(Tp1) < HR(TR), we guess a higher flame temper-
1. Assuming p2. Onetemperature
an Tinitial
ature, repeats this process until the Ttwo
of products f 1 closest temperatures are found
such that Hp(Tf1) < HR(TR) < Hp(Tf2). The product temperature can be estimated by
linear interpolation. This method, although more accurate, still assumes complete
2. If HP (Tfcombustion
1 ) < HR (T ) amajor
toRthe higher flame temperature is guessed Tf 2 .
products.
Method 3: Equilibrium State (Free software: Cantera; Commercial software:
3. The process is repeated until two closest temperatures are found such that HP (Tf 1 ) <
Chemkin)
< HP (Tf 2 ) of products at high temperature (T > 1,500 K at ambient pressure) can
5
HR (TR ) Dissociation
take a significant portion of energy from combustion and hence the product

4. The final temperature is found by linear interpolation

5
Dissociation is the separation of larger molecules into smaller molecules. For example,
2H2O ↔2H2 + O2.
Assignment

1. Calculate the heat transferred when 0.2kg of ethane in Example 1 is burnt at constant
pressure in a cylinder containing 4 kg of dry air. Assume that the temperatures of
reactants and products are 40◦ C and 540◦ C respectively.

22
2. A space shuttle burns liquid hydrogen and oxygen in the main engine. To estimate the
maximum flame temperature, consider combustion of 1 mol of gaseous hydrogen with 0.5
mol of gaseous O2 at 101.3 kPa. Determine the adiabatic flame temperatures.

23
Chapter 2

Kinetics of Combustion

In the previous chapter thermodynamics of combustion was examined that dealt with steady
state analysis of combustion process. In practical situation combustion is an unsteady/transient
phenomena. The chemical kinetics deals with this transient reaction process. It is therefore
necessary to consider the chemical kinetics which involves analysis of mechanism of combustion
and rates of reactions.
Combustion reaction generates a large amount of energy. This energy raises the temperature
of reactants increasing the rate of reaction. This knowledge give insight to designers so as to
develop systems that ensure sufficient time for combustion reaction. This knowledge is also
useful in control of emissions from combustion reactions.
In this chapter the kinetics of combustion (mechanism and rate of reaction) shall be ex-
amined. This will then be followed by analysis of conservation equations that include mass,
momentum and energy equations. All these assist in modeling of combustion process.

2.1 Combustion Mechanism

It has been established that combustion reaction may be represented in form of a balanced
chemical equation. For example a reaction involving hydrogen and oxygen produces water in
the form
1
H2 + O2 → H2 O (2.1)
2

24
This is an overall representation. However at the molecular level combustion proceeds via a
series of elementary reactions. The study of these elementary reactions is called mechanism of
combustion reaction and this is demonstrated by further analysis of the reaction.
Table 2.1 shows the species and semiglobal reactions possible different fuels. For a hydrocar-

Table 2.1: Reactions and Species

Fuel Species Reactions
H2 9 21
CH4 53 400
i − C8 H18 857 3606

bon fuel the species and reactions increase based on the structure of the molecules. Modeling
of such system of reactions demands computational resources.
There a four steps in formation of semiglobal equations. These include chain initiation, chain
branching, chain termination/ recombination as well as chain propagating. In the following
analysis these stages are examined for combustion of hydrogen.

1. Chain Initiation: This involves reactions for breaking of bonds structure to form unstable
compounds called radicals. In hydrogen burning H and O radicals are formed.

H2 + M → H + H + M , O2 + M → O + O + M

Note that M must have sufficient energy to break the bonds within the reactants.

2. Chain Branching: This involves formation of OH radicals through a rapid process due to
collisions within the mixture.
H + O2 → OH + O (2.2)

O + H2 → H + OH (2.3)

In these reactions the one radical generated at each of the initiation stage is consumed
to generate two more radicals. This is a rapid process that causes the explosive nature
of combustion reactions. It is characterized by rapid formation of large number radicals

25
 due to corresponding growth in collisions. This radical formation rate and collisions are
related in the form
R = 2N (2.4)

where N is the number of collisions. Thus radicals multiplication occur instantly (order
of 109 per second at standard conditions).

3. Chain Terminating or Recombination: This is level where radicals react among themselves
forming stable species. enough third bodies are present. Typical reactions are depicted
in the form.
H + O2 + M → H2 O + M (2.5)

O + H + M → OH + M (2.6)

H + OH + M → H2 O + M (2.7)

This step causes a rapid decrease in number of radicals

4. Chain propagating step: In these steps radicals are present on reactants and products
side. conserved as follows.
H2 + OH → H2 O + H (2.8)

It is noted that 1 mole of OH radical produces 1 mole of H radical. At this stage a lot
of water is produced in a hydrogen combustion. This is the step accounts for the largest
amount of end products noticed in a combustion reaction.

In the next section the rate at which these reactions occur is examined.

2.2 Reaction Rate

In this section the reaction rates during combustion process are analyzed. The rate of reaction
refers to rate at which moles of a typical species are consumed or produced. A typical elementary
reaction can be represented by the following form.

aA + bB → cC + dD (2.9)

26
where a, b, c and d are stoichiometric proportions. These proportions are numerically 1 or 2.
The reaction rate involving A and B is based on the law of mass action which states that the
reaction rate is proportional to the concentration of reactants. This can be expressed in the
form
q̇ = k[A]a [B]b (2.10)

where the constant of proportion k is called Arrhenius rate constant given by

 
Ea
k = A0 exp − (2.11)
Ru T

and [A] and [B] refers to concentration of the reactants.

The chain terminating steps have low activation energy as they involve three molecules.
The terms A0 and Ea are determined by carrying out experiments and determining reaction
rate and temperature so as to plot ln k against 1/T . Note that the logarithmic function makes
the equation become  
Ea
ln k = ln A0 + − (2.12)
Ru T
The activation temperature (Ta ) is the gradient while the collision frequency is the Y intercept.
The rate of reaction can therefore be obtained from Equation 2.10. For example species A is
consumed at a rate given by
d[A]
= −aq̇ = ṙA (2.13)
dt
Typical relationships for some methane semi-global reactions are shown in in Figure 2.1. For a
reversible reaction involving dissociation of species Equation 2.9 becomes

aA + bB ⇌ cC + dD (2.14)

So that the net rate of reaction can be expressed for both as the difference between forward
and backward rates in the form

q̇ = kx [A]a [B]b − ky [C]c [D]d (2.15)

At equilibrium both rates are the same thus

a+b−c−d
[C]c [D]d

kx Ru T
Kc = = = Kp (T ) (2.16)
ky [A]a [B]b 101.3

27
 Distance From Injection (cm)
1 cm ≅ 0.71 m sec

Fig. 3.2 Experimental measurements of the reaction rate of methane/air (Reprinted with permis-
sion from Dryer and Glassman [2])

35
H+HO2=2OH
30
CH2O+H=HCO+H2
25

OH+H2=H2O+H
20
log(k)
CH4+H=CH3+H2
15

10
H+O2=OH+O
5

0
0 0.5 1 1.5 2 2.5 3 3.5
1000/T

Fig. 3.3 Rate constant k ¼ k(T) for reactions in main pathway of methane-air combustion
(Appendix 4 Figure
Table B)2.1: Propagating reactions for methane combustion

where 3.2.2 Equilibrium Constants

agA0 + bgB0 − cgC0 − dgD
0
 
Kp (T ) = exp
Ru T
The above procedure can be generalized to reversible reactions
g is the gibbs free energy obtained from gi = hi − T si obtained from tables.
aA þ bB $ cC þ dD
Assignment: Prove the above expression (3.12)

2.2.1 Simple Models of Combustion

Combustion involves a large number of semi global reactions and species as earlier seen. These
reactions grow exponentially with increasing carbon molecules in the fuel. Modeling such
systems require large CFD resources to track each step. It is possible to study these reactions
using simplified models using the following procedure.
One method of simplification is to consider global one step reaction. In this the reaction
rate is obtained from Equation 2.10 for the fuel and oxidant in the form.
 
Ea
ṙ = A0 exp − [F uel]a [O2 ]b (2.17)
Ru T

The constants A0 , Ea , and the exponents a and b have been obtained experimentally and are
available in tables (to be supplied) for different fuels. Note that a and b are not stoichiometric

28
coefficients of the global reaction equation. The units of concentrations of reactants are typically
mol/cm3 thus q̇ is in mol/cm3 − s . Rate of reaction is dependent on temperature and also on
equivalence ratio (temperature depends on equivalence ratio).
Example: Consider combustion of stoichiometric methane-air at a constant temperature
of 1,800 K and 101.3 kPa. Using a one-step reaction formulation for the rate constant, estimate
the amount of time required to completely consume the fuel.

2.2.2 Role of Pressure

The progress of the reaction depends on the pressure. This can be realized by expressing
the concentration terms in the rate expression in terms of pressure. This is facilitated by the
equation of state.

2.2.3 Assumptions

Several assumptions are made when estimating the rate and mechanism of combustion. These
include

1. Partial equilibrium: Combustion process is a non equilibrium process. This causes difficul-
ties in measuring radical concentrations at high temperatures. By assuming equilibrium
for some reactions it is possible to obtain the reaction rate of certain radicals. Typical
reactions in a hydrogen combustion that are assumed to be at equilibrium are

H + O2 ⇌ OH + O( R1)

O + H2 ⇌ OH + H( R2)

H2 + OH ⇌ H2 O + H( R3)

Typical concentration of the radicals can be estimated at equilibrium. For example

q
[OH] = Kc,1 Kc,2 [O2 ][H2 ]

2. Quasi-steady state: The combustion reaction occurs is an unsteady process. It involves

formation of intermediate species that are consumed at a much faster rate. For simplicity

29
 these rates are assumed to be equal. For example formation of carbon species can be
estimated as
d[C]
= ωp − ωc ≈ 0 ∴ ωp = ωc
dt
where ωp and ωc are the net production and consumption rates.

Assignment: Show that the rate of consumption of species is proportional to pressure.

Example: The formation of nitric oxide occurs through Zeldovich Mechanism. Assuming
N atoms in a quasi-steady state derive an expression for N in terms of other species
Tutorial:

1. The O atom is an important species involved in the formation of thermal NO (Zeldovich

Mechanism N 2 + O → N O + N ). Estimate the mole fraction of radical O in air when it
is heated to 2,000 K.

2. In a gas turbine burner, engineers estimate the flame temperature to be 2,200 K and wish
to reduce the nitric oxide (NO) formation rate. As NO formation is very sensitive to
temperature, one solution is to inject a small amount of water into the combustor so that
the flame temperature is reduced. The NO production rate is modeled by the following
rate equation

2.3 Transport Equations

The conservation equations obtained from fluid and heat transfer are used in describing trans-
port of species participating in combustion process. These equations have extra terms that
account for combustion reactions and they are considered in this section. To understand how
the extra terms fit in the already known transport equations a review of mass and heat concepts
are examined first.

2.3.1 Review of Heat and Mass Transfer

Recall that heat transfer can occur through three modes. These are conduction, convection and
radiation. Mass transfer occurs due to convection and diffusion. These concepts are reviewed

30
in the following analysis.

1. The rate at which is conduction is governed by the fourier law given by

dT
q̇cond = −Ak (2.18)
dx
where A, k, T and x are the cross-sectional are, conductivity, temperature and thickness
respectively. Note that this conduction occurs due to collisions that occur at molecular
level.

2. Convection of heat is facilitated by movement of fluid causing conduction and advection

(bulk fluid motion). This may be described by Newton law of cooling across a thermal
boundary layer in the form
q̇convec = Ah(Th − Tc ) (2.19)

where h is the heat transfer coefficient. This term has different representation based on
the geometry and the flow conditions. For convection and free convection the expressions
are respectively
k k
h = C Rea P rb , h = C Gra P rb (2.20)
L L
where L, Re and Pr are characteristic lengths, Renolds number and Prandtl number
respectively. C, a and b are empirical constants. Gr is the Grashoff number that is a ratio
of buoyancy to viscous force.

3. Radiation is heat transfer due to electromagnetic waves. No medium is required between

two temperature regions at different temperatures. The equation governing such transfer
is
q̇rad = F12 Aεσs (Th4 − Tc4 ) (2.21)

where ε is the emissivity and σs Stefan-Boltzmann constant and F12 is the geometric
factor.

4. Mass transport is governed by advection (bulk fluid motion) and diffusion. These two
modes can be represented by the mass flux and diffusion terms respectively in the form

ṁi = ρi u (2.22)

31
 where ρi is the density of the typical species. If the overall density of the mixture is known
then ρi = ρyi . Diffusion on the other hand is represented by Fick’s law of difusion
∂yi
ṁi = ρDi (2.23)
∂x
Diffusion can be visualized as starting from the interface between fuel and oxidizer.This
involves movement of species particles from regions of high to low concentrations as shown
4 Review of Transport Equations and Properties
in Figure 2.2. Recall that from section 2.2 that the rate of consumption or generation is

iffusion
move
ation
entration
fraction
as
High concentration Low concentration

Figure 2.2: Diffusion of fuel and oxidizer

1.0 t=1000 s
t=200 s
know and can0.8
be expressed as t=100 s
Mole Fraction

t=10 s
ṁi = ri Mi t=1 s (2.24)
0.6
where r and Mi are the rates and molecular mass of the species respectively.
0.4
2.3.2 Transport Equations
0.2
The equations of conservation of mass, momentum and heat apply for the whole mixture and
0
these are reviewed in this section. Note besides the overall equations of the mixture further
equations exist for the-20 -10A one dimension case is considered.
various species.
0 10 20
Distance (cm)
Continuity Equation

The overall mass of the mixture is conserved through the continuity equation given by
species, i, can be created or destroyed∂m
by chemical
∂m reactions at a
+ =0 (2.25)
∂t ∂x

m_ 000 ^i Mi
i;gen ¼ r
32 (4.10)
 79
Each of the active species is created or destroyed and thus the conservation equation must
reflect this. A one dimensional control volume may be considered as shown in Figure 2.3.

dx

mi,gen
mi¢¢,x mi¢¢,x+ dx

CV

Figure 2.3: One dimensional control volume

Note that the mass of each species can be solved for the control volume in the form.

combustion creates and ∂ ṁ destroys individual

∂t
i
= ṁ − ṁ + ṁ
i,x dx
i,x+dx i,gen (2.26)

of balance laws,
where mass prediction
inflow is given of combustion
by the sum of the convective and diffusion terms in the form

o track each chemical species. ṁ = ρuy + ρDi,x

For
∂y
∂x
gaseous
i i
i
(2.27)

ation equation
and can be derived on the basis
∂ ṁ
nd generation due to chemical∂x reactions.ṁ = ṁ +
i,x+dx dx i,x
i,x
(2.28)

The final mass conservation for a typical species can be expressed in the form.
with a differential width dx and unity area
∂ ẏi ∂ ẏi ∂ 2 ẏi
ρ + ρu = ρDi 2 + ṙi Mi (2.29)
∂t ∂x ∂x

area is V ¼ dx1 ¼ dx. Conservation

Note that the terms on the right hand side are not present in cold flow case
with unity
33
Momentum Conservation

The conservation of momentum for one dimensional case have been derived previously (Fluids
mechanics and CFD course).

∂ρu ∂ρu ∂P ∂ 2u
+u =− +µ 2 +X (2.30)
∂t ∂x ∂x ∂x

where u and X are flow velocity and body force respectively.

Energy Conservation

Combustion process involves energy generation. In modeling combustion conservation of energy

is critical. In this section a one dimension conservation equation for the combustion process is
derived.
Terms encountered in the overview section are used in derivation of energy equation. These
include the conduction term Equation 2.18 (based on fourier law), advection (energy convection)
term based on Equation 2.19, radiation based on Equation 2.21 and internal energy generation
based on q̇ = ṙf uel Qc V .
Exercise: Show that the energy carried by mass diffusion of species is zero that is
n
X
ρvi yi hi = 0
i

Assignment: Show that the one dimensional energy equation for a combustion process is
given by
∂T ∂T ∂ 2T A
ρcp + ρcp u = k 2 − εσs (Th4 − Tc4 ) + ṙQc (2.31)
∂t ∂x ∂x V
A
where Qc is the heat of combustion and V
is the area to volume ratio of soot particles that
radiate heat.

2.3.3 Normalized Conservation Equations

Conservation equations are normalized based on values at the boundary. When such values
are not available other terms called characteristic terms are defined. By this method non
dimensional terms result and are substituted in the conservation equations.

34
 The characteristic quantities are defined as follows

t x T u P
t̄ = , x̄ = , T̄ = , ū = , P̄ = (2.32)
tc lc Tc uc Pc

Substitution of these terms in the conservation equations brings about other non dimensional
group of terms such as the

ρuc Ic u2c
1. In the momentum equation the Reynolds number Re = µ
and Froude number F r = gIc

Ic uc α
2. In the continuity and energy equation the Peclet number P e = α
, Lewis number Le = D
flow time Ic /uc
and Damkohler Da = chemistry time
= ρyc /ṙi
Mi

35