Course of Energy Systems

Combustion

Department of Energy

Marco Binotti

Stefano Consonni

Emanuele Martelli

Luca Mastropasqua

Matteo Romano
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Course of Energy Systems – Combustion

Contents

Contents ______________________________________________________________________________ 2

Summary______________________________________________________________________________ 3

1 Generalities _________________________________________________________________________ 4

2 Complete Combustion_________________________________________________________________ 4

2.1 Material balance _____________________________________________________________ 4

2.2 Energy balance ______________________________________________________________ 11

3 Heating Value of a Fuel _______________________________________________________________ 12

4 Adiabatic Flame Temperature __________________________________________________________ 15

Nomenclature _________________________________________________________________________ 16
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Summary

The following document summarises the chief topics related to the thermodynamics of combustion
processes, primarily applied to fossil fuels applications. In particular, subsequently to some general
considerations on the nature of the energy resource, the complete combustion process is explored. The
concepts of global reaction process and elementary chemical reaction steps are compared. Subsequently,
the definitions of oxidant-to-fuel ratio and oxidant excess are introduced with the aid of numerical
examples.

Following a similar approach, mass and energy balances on reactive thermodynamic systems are written, in
order to compute the enthalpy of formation of molecule species. Finally, the definitions and the procedure
for calculating the heating value of a fuel and the adiabatic flame temperature are presented.
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1 Generalities

Combustion process is a redox chemical reaction occurring between a fuel and an oxidant, characterized by
high exothermicity (i.e. release of heat). In the chemical reactions involved in a combustion process, the
reactants (fuel, normally containing carbon and/or hydrogen, and oxidant, normally O2) are transformed
into products converting chemical energy into heat. The thermal energy released by the chemical reaction
is then transferred to the products which consequently increase their temperature. The heat produced in
combustion processes is usually high enough to produce reaction products at sufficiently high temperature
to emit electromagnetic radiation in the visible wavelength range (flame). In addition, the transfer of part
of the heat generated during combustion to the reactants, is usually sufficient to ignite them (i.e. start new
combustion reactions) making the combustion process self-sustaining.

The thermal energy released in the combustion process, which is dependent on the fuel composition (see
Section 3), may be exploited for heating purposes or may be further converted into mechanical energy
through thermodynamic cycles. In this second case, the combustion products may constitute the working
fluid (e.g. in gas turbines, in internal combustion engines) or heat can be exchanged to another fluid
through heat transfer surfaces (e.g. in steam cycles).

Combustion process involves many different and complex phenomena: chemical reactions, fluid-dynamics,
mass transfer, heat transfer via all the possible mechanisms (conduction, convection, radiation), mutually
influencing one each other. From an “energy system” perspective, i.e. assessing combustion processes on a
macro-scale and considering combustors as “black boxes”, detailed assessment of a combustion process is
usually not necessary and just basic concepts are sufficient to solve mass and energy balances with a
proper accuracy. All the complex phenomena listed above have instead to be considered when assessing
for example the presence of hot and cold spots in combustion chambers, that may lead to pollutant
formation or local overheating of the combustor materials.

2 Complete Combustion

2.1 Material balance

In general, the composition of a mixture of different molecules resulting from chemical reactions is
determined by thermodynamics and by kinetics. Thermodynamic properties of substances determine the
chemical equilibrium composition, i.e. the composition of the mixture if it is allowed to react for an infinite
time. Equilibrium composition for a generic reaction 𝑎𝑎𝑎𝑎 + 𝑏𝑏𝑏𝑏 → 𝑐𝑐𝑐𝑐 + 𝑑𝑑𝑑𝑑 is commonly described by the
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chemical equilibrium constant 𝐾𝐾𝑒𝑒𝑒𝑒 (actually not really constant but depending on temperature), relating
the concentrations [_] of the molecules involved in the reaction as follows:

[𝐶𝐶]𝑐𝑐 ∙ [𝐷𝐷]𝑑𝑑
= 𝐾𝐾𝑒𝑒𝑒𝑒
[𝐴𝐴]𝑎𝑎 ∙ [𝐵𝐵]𝑏𝑏

The reaction rate, i.e. the rate of conversion of one of the molecules involved in the reaction, is described
by an equation involving the kinetic constant 𝑘𝑘𝑘𝑘𝑘𝑘𝑘𝑘 (again not rigorously constant, but monotonically
increasing with temperature). The higher the reaction rate, the faster the composition of the products will
approach the equilibrium composition.

Combustion reactions have the following properties: (i) the equilibrium constant is very high, so that at
equilibrium the concentration of reaction products is several order of magnitude higher than the
concentration of the unconverted fuel; (ii) the kinetic constant is very high, so that equilibrium composition
is approached in short times (order of seconds). For these reasons, combustion in industrial processes
normally proceeds close to a complete fuel conversion and can be considered as such in many applications,
when calculating overall mass and energy balances of a combustor.

Combustion of a fuel is normally described by considering the overall reaction, as shown below for the
combustion of methane (CH4):

𝑀𝑀𝑀𝑀
𝐶𝐶𝐻𝐻4 + 2𝑂𝑂2 → 𝐶𝐶𝑂𝑂2 + 2𝐻𝐻2 𝑂𝑂 (𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠) Δℎ𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟 (25°𝐶𝐶) = −800.2
𝑘𝑘𝑘𝑘𝑘𝑘𝑙𝑙𝐶𝐶𝐻𝐻4

where Δℎ𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟 is the heat of reaction (negative in case of exothermic reactions), i.e. the heat released by the
reaction if performed at constant temperature. The global oxidation mechanism simplifies the real
combustion process which is made up of a more complex sequence of many (order of hundreds)
elementary chemical steps. A possible simplified set of elementary reactions may be for example:

𝐶𝐶𝐻𝐻4 + 𝑂𝑂𝑂𝑂 → 𝐶𝐶𝐻𝐻3 + 𝐻𝐻2 𝑂𝑂

𝐶𝐶𝐻𝐻3 + 𝑂𝑂 → 𝐶𝐶𝐻𝐻2 𝑂𝑂 + 𝐻𝐻

𝐶𝐶𝐻𝐻2 𝑂𝑂 + 𝐻𝐻 → 𝐻𝐻𝐻𝐻𝐻𝐻 + 𝐻𝐻2

𝐻𝐻𝐻𝐻𝐻𝐻 + 𝑂𝑂 → 𝐶𝐶𝐶𝐶 + 𝑂𝑂𝑂𝑂

𝐶𝐶𝐶𝐶 + 𝑂𝑂𝑂𝑂 → 𝐶𝐶𝑂𝑂2 + 𝐻𝐻

These chain reactions involve free radical elements (𝑂𝑂, 𝑂𝑂𝑂𝑂, 𝐻𝐻), very unstable and hence reactive species
which foster the proceeding of the single elementary chemical steps. The reason why combustion proceeds
through such a complex path is that it is much faster than the direct single-step oxidation of the overall
reaction. However, the real complex reaction path gives the same products in the same proportions as
described by the overall reaction. Therefore, the overall mass and energy balance of a complete
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combustion process, which only depends on the final reaction products, is independent of the real reaction
path.

The simplest approach to determine the composition of product species in a reactive mixture is that of
complete combustion, which assumes that:

• Carbon atoms 𝐶𝐶 are completely oxidized to 𝐶𝐶𝑂𝑂2 : 𝐶𝐶 + 𝑂𝑂2 → 𝐶𝐶𝑂𝑂2

1 1
• Hydrogen atoms 𝐻𝐻 are completely oxidized to 𝐻𝐻2 𝑂𝑂: 𝐻𝐻 + 𝑂𝑂2 → 𝐻𝐻2 𝑂𝑂
4 2

• Sulphur atoms 𝑆𝑆 are completely oxidized to 𝑆𝑆𝑂𝑂2 : 𝑆𝑆 + 𝑂𝑂2 → 𝑆𝑆𝑂𝑂2

• Nitrogen atoms do not contribute to chemical reactions and remain in the reaction product mixture
as inert gases in their molecular form 𝑁𝑁2
• No other unburnt species or contaminants are considered

The first necessary condition under which the complete combustion may occur is the presence of an
adequate amount of 𝑂𝑂2 .

𝑚𝑚𝑂𝑂2 𝑘𝑘𝑔𝑔𝑂𝑂2
The 𝑂𝑂2 /𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓 mass ratio is defined as: 𝛼𝛼𝑂𝑂2 = 𝑚𝑚 �𝑘𝑘𝑔𝑔 �
𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓 𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓

𝑀𝑀𝑂𝑂2 𝑘𝑘𝑘𝑘𝑘𝑘𝑙𝑙𝑂𝑂2
Similarly, the molar ratio is defined as: 𝛼𝛼�𝑂𝑂2 = 𝑀𝑀 �𝑘𝑘𝑘𝑘𝑘𝑘𝑙𝑙 � and can be derived from the mass ratio
𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓 𝑓𝑓𝑓𝑓𝑓𝑓𝑙𝑙

𝑀𝑀𝑀𝑀𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓 𝑘𝑘𝑘𝑘𝑖𝑖
through 𝛼𝛼�𝑂𝑂2 = 𝛼𝛼𝑂𝑂2 , where 𝑀𝑀𝑀𝑀𝑖𝑖 � � represents the molar mass of chemical specie 𝑖𝑖.
𝑀𝑀𝑀𝑀𝑂𝑂2 𝑘𝑘𝑘𝑘𝑘𝑘𝑙𝑙𝑖𝑖

Similar ratios may be defined for air, since 𝑂𝑂2 is normally supplied through air:

𝑚𝑚𝑎𝑎𝑎𝑎𝑎𝑎 𝑘𝑘𝑔𝑔𝑎𝑎𝑎𝑎𝑎𝑎 𝑀𝑀𝑎𝑎𝑎𝑎𝑎𝑎 𝑘𝑘𝑚𝑚𝑚𝑚𝑚𝑚𝑎𝑎𝑎𝑎𝑎𝑎 𝑀𝑀𝑀𝑀𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓

𝛼𝛼 = � � 𝛼𝛼� = � � = 𝛼𝛼
𝑚𝑚𝑓𝑓𝑢𝑢𝑢𝑢𝑢𝑢 𝑘𝑘𝑔𝑔𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓 𝑀𝑀𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓 𝑘𝑘𝑚𝑚𝑚𝑚𝑚𝑚𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓 𝑀𝑀𝑀𝑀𝑎𝑎𝑎𝑎𝑎𝑎

The minimum amount of oxygen (or air) necessary to completely oxidise the fuel is the stoichiometric one
and the corresponding 𝛼𝛼𝑂𝑂2 (or 𝛼𝛼) is the stoichiometric combustion ratio (𝛼𝛼𝑂𝑂2 or 𝛼𝛼𝑠𝑠𝑠𝑠 ). If an oxidant to fuel
𝑠𝑠𝑠𝑠

ratio lower than the stoichiometric value is adopted, complete combustion is not possible and unburned
species (e.g. C, CO, H2, …) would be present in the reaction products. In this case, the composition of the
products would not be predictable as easily as in the case of complete combustion and should be
calculated through chemical equilibrium and kinetics laws.

In brief, two main conditions are discernible regarding the oxidant to fuel ratio:

• 𝛼𝛼 < 𝛼𝛼𝑠𝑠𝑠𝑠 → fuel-rich mixtures: complete combustion is not possible

• 𝛼𝛼 > 𝛼𝛼𝑠𝑠𝑠𝑠 → fuel-lean mixtures: complete combustion is possible and is usually an excellent
approximation for a real industrial combustion process.
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It is therefore clear the importance of calculating the stoichiometric oxygen to fuel ratio 𝛼𝛼𝑂𝑂2 . This can be
𝑠𝑠𝑠𝑠

made by properly balancing the combustion chemical reaction, according to the assumptions on complete
combustion listed before. For example, for a generic fuel molecule 𝐶𝐶𝑁𝑁𝐶𝐶 𝐻𝐻𝑁𝑁𝐻𝐻 𝑂𝑂𝑁𝑁𝑂𝑂 𝑁𝑁𝑁𝑁𝑁𝑁 𝑆𝑆𝑁𝑁𝑆𝑆 containing 𝑁𝑁𝐼𝐼
atoms of element 𝐼𝐼 and recalling that the number of atoms of each element conserves from reactants to
products (while the number of molecules does not necessarily conserve), the following combustion
reaction can be written:

𝑁𝑁𝐻𝐻 𝑁𝑁𝑁𝑁
𝐶𝐶𝑁𝑁𝐶𝐶 𝐻𝐻𝑁𝑁𝐻𝐻 𝑂𝑂𝑁𝑁𝑂𝑂 𝑁𝑁𝑁𝑁𝑁𝑁 𝑆𝑆𝑁𝑁𝑆𝑆 + 𝑁𝑁𝑂𝑂2 𝑂𝑂2 → 𝑁𝑁𝐶𝐶 𝐶𝐶𝑂𝑂2 + 𝐻𝐻2 𝑂𝑂 + 𝑁𝑁 + 𝑁𝑁2 𝑆𝑆𝑂𝑂2
2 2 2

The stoichiometric number of O2 molecules needed per molecule of fuel can be hence computed as follows,
subtracting to the oxygen needed to completely oxidize C, H and S to CO2, H2O and SO2, the amount of
oxygen carried by the fuel itself:

𝑁𝑁𝐻𝐻 𝑁𝑁𝑂𝑂
𝛼𝛼�𝑂𝑂2 = 𝑁𝑁𝑂𝑂2 = 𝑁𝑁𝐶𝐶 + + 𝑁𝑁𝑆𝑆 −
𝑠𝑠𝑠𝑠 4 2

As an example, consider the stoichiometric combustion of ethanol in 𝑂𝑂2 :

𝐶𝐶2 𝐻𝐻5 (𝑂𝑂𝑂𝑂) + 3𝑂𝑂2 → 2𝐶𝐶𝑂𝑂2 + 3𝐻𝐻2 𝑂𝑂

𝑘𝑘𝑘𝑘
𝑀𝑀𝑀𝑀𝑂𝑂2 = 32
𝑘𝑘𝑘𝑘𝑘𝑘𝑘𝑘
𝑘𝑘𝑘𝑘
𝑀𝑀𝑀𝑀𝐶𝐶2 𝐻𝐻5 (𝑂𝑂𝑂𝑂) = 46
𝑘𝑘𝑘𝑘𝑘𝑘𝑘𝑘

𝑀𝑀𝑂𝑂2 𝑘𝑘𝑘𝑘𝑘𝑘𝑙𝑙𝑂𝑂2 𝑀𝑀𝑀𝑀𝑂𝑂2 𝑘𝑘𝑔𝑔𝑂𝑂2

𝛼𝛼�𝑂𝑂2 = =3 � � 𝛼𝛼𝑂𝑂2 = 𝛼𝛼�𝑂𝑂2 = 2.087 � �
𝑠𝑠𝑠𝑠 𝑀𝑀𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓 𝑘𝑘𝑘𝑘𝑘𝑘𝑙𝑙𝐶𝐶2 𝐻𝐻5(𝑂𝑂𝑂𝑂) 𝑠𝑠𝑠𝑠 𝑠𝑠𝑠𝑠 𝑀𝑀𝑀𝑀𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓 𝑘𝑘𝑔𝑔𝐶𝐶2𝐻𝐻5(𝑂𝑂𝑂𝑂)

As already mentioned, the majority of combustion processes occur using air as oxidant. Thus, let’s consider
the stoichiometric combustion of ethanol in dry air, assuming for simplicity that air is composed only by
79% of N2 and 21% O2 on a molar basis, it is possible to calculate that 79/21=3.76 moles of N2 are brought
in the combustor per mole of O2. hence, the complete combustion global reaction becomes:

𝐶𝐶2 𝐻𝐻5 (𝑂𝑂𝑂𝑂) + 3(𝑂𝑂2 + 3.76𝑁𝑁2 ) → 2𝐶𝐶𝑂𝑂2 + 3𝐻𝐻2 𝑂𝑂 + 11.29 𝑁𝑁2

Or:

3
𝐶𝐶2 𝐻𝐻5 (𝑂𝑂𝑂𝑂) + (0.21 𝑂𝑂2 + 0.79𝑁𝑁2 ) → 2𝐶𝐶𝑂𝑂2 + 3𝐻𝐻2 𝑂𝑂 + 11.29 𝑁𝑁2
0.21

From which the stoichiometric air to fuel ratio can be computed:

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𝑀𝑀𝑎𝑎𝑎𝑎𝑎𝑎 3 𝑘𝑘𝑘𝑘𝑘𝑘𝑙𝑙𝑎𝑎𝑎𝑎𝑎𝑎
𝛼𝛼�𝑠𝑠𝑠𝑠 = = = 14.29 � �
𝑀𝑀𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓 0.21 𝑘𝑘𝑘𝑘𝑘𝑘𝑙𝑙𝐶𝐶2 𝐻𝐻5 (𝑂𝑂𝑂𝑂)

Recalling that the molar mass of a mixture 𝑀𝑀𝑀𝑀𝑚𝑚𝑚𝑚𝑚𝑚 is given by the weighted average of the molar masses of
the mixture components 𝑀𝑀𝑀𝑀𝑖𝑖 , where the weights are the mole fractions 𝑥𝑥𝑖𝑖 , the molar mass of air can be
calculated as follows:

𝑘𝑘𝑘𝑘
𝑀𝑀𝑀𝑀𝑚𝑚𝑚𝑚𝑚𝑚 = ∑𝑥𝑥𝑖𝑖 𝑀𝑀𝑀𝑀𝑖𝑖 ; 𝑀𝑀𝑀𝑀𝑎𝑎𝑎𝑎𝑎𝑎 = 0.21 ∗ 32 + 0.79 ∗ 28 = 28.84 � �
𝑘𝑘𝑘𝑘𝑘𝑘𝑘𝑘

From where:

𝑀𝑀𝑀𝑀𝑎𝑎𝑎𝑎𝑎𝑎 𝑘𝑘𝑔𝑔𝑎𝑎𝑎𝑎𝑎𝑎
𝛼𝛼𝑠𝑠𝑠𝑠 = 𝛼𝛼�𝑠𝑠𝑠𝑠 = 8.96 � �
𝑀𝑀𝑀𝑀𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓 𝑘𝑘𝑔𝑔𝐶𝐶2 𝐻𝐻5 (𝑂𝑂𝑂𝑂)

Since normally oxidant and fuel are not burned in stoichiometric proportions, it is useful to define the fuel
to air equivalence ratio Φ as the ratio between the stoichiometric air amount and the actual air amount in
the combustion process (or, which is the same, the ratio between the stoichiometric air to fuel ratio and
the actual air to fuel ratio):

𝛼𝛼𝑠𝑠𝑠𝑠 𝑘𝑘𝑔𝑔𝑎𝑎𝑎𝑎𝑟𝑟𝑠𝑠𝑠𝑠 𝛼𝛼�𝑠𝑠𝑠𝑠 𝑘𝑘𝑘𝑘𝑘𝑘𝑙𝑙𝑎𝑎𝑎𝑎𝑟𝑟𝑠𝑠𝑠𝑠 Φ < 1 → 𝑙𝑙𝑙𝑙𝑙𝑙𝑙𝑙 𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚

Φ= � �= � �=�
𝛼𝛼 𝑘𝑘𝑔𝑔𝑎𝑎𝑎𝑎𝑎𝑎 𝛼𝛼� 𝑘𝑘𝑘𝑘𝑘𝑘𝑙𝑙𝑎𝑎𝑎𝑎𝑎𝑎 Φ > 1 → 𝑟𝑟𝑟𝑟𝑟𝑟ℎ 𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚

Similarly, the air to fuel equivalence ratio λ can be computed as the reverse of the air to fuel equivalence
ratio Φ

1 λ > 1 → 𝑙𝑙𝑙𝑙𝑙𝑙𝑙𝑙 𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚

λ= =�
Φ λ < 1 → 𝑟𝑟𝑟𝑟𝑟𝑟ℎ 𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚

Another parameter which is usually used to characterise the air/fuel ratio of a combustion process is the
oxidant excess (𝜖𝜖), defined as:

α
ε= −1
αst

From where:

𝛼𝛼 = (1 + 𝜀𝜀)𝛼𝛼𝑠𝑠𝑠𝑠

Note that the same value of the oxidant excess is representative of the mass and molar oxidant to fuel
𝛼𝛼 �
𝛼𝛼
ratio, since = 𝛼𝛼� . Also note that the same value is representative of the combustion in air and in pure
𝛼𝛼𝑠𝑠𝑠𝑠 𝑠𝑠𝑠𝑠
𝛼𝛼 𝛼𝛼𝑎𝑎𝑎𝑎𝑎𝑎 ∙𝑥𝑥𝑂𝑂2 𝛼𝛼𝑂𝑂2
oxygen, since 𝛼𝛼 𝑎𝑎𝑎𝑎𝑎𝑎 = 𝛼𝛼 = 𝛼𝛼
𝑎𝑎𝑎𝑎𝑎𝑎,𝑠𝑠𝑠𝑠 𝑎𝑎𝑎𝑎𝑎𝑎,𝑠𝑠𝑠𝑠 ∙𝑥𝑥𝑂𝑂2 𝑂𝑂2,𝑠𝑠𝑠𝑠
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As an example, the combustion of ethanol with 20% excess air gives the following material balance and air
to fuel ratios:

3
𝐶𝐶2 𝐻𝐻5 (𝑂𝑂𝑂𝑂) + 1.2 (0.21 𝑂𝑂2 + 0.79𝑁𝑁2 ) → 2𝐶𝐶𝑂𝑂2 + 3𝐻𝐻2 𝑂𝑂 + 0.6𝑂𝑂2 + 13.54 𝑁𝑁2
0.21

𝑀𝑀𝑎𝑎𝑎𝑎𝑎𝑎 𝑘𝑘𝑘𝑘𝑘𝑘𝑙𝑙𝑎𝑎𝑎𝑎𝑎𝑎 𝑀𝑀𝑀𝑀𝑎𝑎𝑎𝑎𝑎𝑎 𝑘𝑘𝑔𝑔𝑎𝑎𝑎𝑎𝑎𝑎

𝛼𝛼� = = 17.14 � � 𝛼𝛼 = 𝛼𝛼� ∙ = 10.75 � �
𝑀𝑀𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓 𝑘𝑘𝑘𝑘𝑘𝑘𝑙𝑙𝐶𝐶2 𝐻𝐻5(𝑂𝑂𝑂𝑂) 𝑀𝑀𝑀𝑀𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓 𝑘𝑘𝑔𝑔𝐶𝐶2 𝐻𝐻5(𝑂𝑂𝑂𝑂)

Note that, as previously specified, all the nitrogen involved in the process results in N2 in the products, i.e. it
behaves as an inert in the process. Similarly, the excess oxygen exits as O2 in the products, behaving as an
inert gas as well. In real combustion processes, such N2 and O2 may react and produced molecules as NO,
NO2 and N2O (i.e. NOx). However, a minor portion of the nitrogen and the excess oxygen react to form NOx,
resulting in NOx concentration in the combustion products several order of magnitude lower than the main
products shown in the reaction above. NOx formation is hence insignificant when evaluating mass and
energy balances of a combustion process. In addition, the amount of NOx formed is not easily predictable
with a simple approach as the one here discussed, but needs a detailed assessment of the combustion
process involving reaction kinetics, fluid-dynamic, heat transfer and mass transfer phenomena. For these
reasons, NOx are never included in the combustion products, when the complete combustion calculation
approach is considered.

From the material balance of the reaction above, the composition of the resulting combustion gases can be
computed. In particular, the mole fraction 𝑥𝑥𝑖𝑖,𝑃𝑃 of each component 𝑖𝑖 in the product gas can be computed as
follows:

2
⎧𝑥𝑥𝐶𝐶𝑂𝑂2 = = 0.1045
⎪ 2 + 3 + 0.6 + 13.54
⎪ 3
⎪𝑥𝑥𝐻𝐻 𝑂𝑂 = = 0.1567
𝑁𝑁𝑖𝑖,𝑃𝑃 2
2 + 3 + 0.6 + 13.54
𝑥𝑥𝑖𝑖,𝑃𝑃 = =
∑𝑖𝑖 𝑁𝑁𝑖𝑖,𝑃𝑃 ⎨ 𝑥𝑥 = 0.6
𝑂𝑂2 = 0.0313
⎪ 2 + 3 + 0.6 + 13.54
⎪ 13.54
⎪
𝑥𝑥
⎩ 2 2 + 3 + 0.6 + 13.54 = 0.7075
𝑁𝑁 =

The calculation methodology based on the complete combustion approach allows to decouple the
determination of the products composition and the thermal balance of the considered system. In other
words, the material balance can be computed throughout the methodology described (independently of
the energy balance) and the energy balance (e.g. for the computation of the temperature of the
combustion products) can be calculated afterwards as discussed in the following. It should be highlighted
that, for chemical reactions in general, if a chemical equilibrium approach is considered, the mass and
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energy balance decoupling is not possible, due to the dependence of the chemical equilibrium constant on
the temperature of the product mixture.

As a final comment on the completion of a combustion process, in theory the oxidant to fuel ratio can vary
between zero and infinite. However, precise flammability limits exist in a real combustion process,
representing conditions at which combustion is self-sustaining. For a simplified intuitive explanation of the
existence of the flammability limits, consider for example a combustion with a very high air to fuel ratio. In
such a case, the large excess air behaving as inert for combustion reactions, represents a thermal ballast in
the process, so that the temperature of the reaction products (i.e. the adiabatic flame temperature, that
will be presented further on) reduces, so that heat transferred to the reactants is not sufficient to ignite
them. Similarly, for too low air to fuel ratio the heat released by the partial oxidation of the fuel is not
enough to sustain the ignition of the reactants.

Flammability limits depend on the fuel and the oxidant compositions and on the combustion conditions
(reactants temperature and pressure). As an example, in Figure 1 the flammability limits of
methane/nitrogen/oxygen mixtures at ambient temperature and pressure is shown as a shaded area.
Outside these limits, combustion does not occur spontaneously (but may occur in presence of catalysts
favouring combustion at low temperatures).

Stoichiometric line:
O2/CH4 = 2

Air line:
N2/O2=79/21=3.76

Upper flammability limit:

~15% CH4, ~18% O2, ~ 67% N2

Lower flammability limit:

~5% CH4, ~20% O2, ~75% N2

Figure 1 –Flammability limits of methane/nitrogen/oxygen mixtures at ambient temperature and pressure

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2.2 Energy balance

Consider an open and reactive system in steady-state conditions, such as that reported in Figure 2.

𝑊𝑊̇
1 2

𝑀𝑀̇1 ℎ1 𝑀𝑀̇2 ℎ2

𝑄𝑄̇
Figure 2 – Energy balance of open and reactive system in steady-state conditions

Neglecting the kinetic and potential energy contributions, the following equation describes the energy
balance:

𝑀𝑀̇1 ℎ1 = 𝑊𝑊̇ + 𝑄𝑄̇ + 𝑀𝑀̇2 ℎ2

Where ℎ1 and ℎ2 are the enthalpies of the inlet and outlet streams, calculated as weighted average on the
mole fractions 𝑥𝑥𝑖𝑖 of the enthalpies ℎ𝑖𝑖 (in [kJ/kmole]) of the species 𝑖𝑖 forming the mixture 1:

ℎ = � 𝑥𝑥𝑖𝑖 ∙ ℎ𝑖𝑖
𝑖𝑖

The enthalpy of each species can be calculated as:

ℎ𝑖𝑖 = ℎ0,𝑖𝑖 + Δℎ(𝑝𝑝, 𝑇𝑇)0,𝑖𝑖

that for a system at constant pressure (or for an ideal gas with any pressure change) becomes:

𝑇𝑇
ℎ𝑖𝑖 = ℎ0,𝑖𝑖 + � 𝑐𝑐𝑝𝑝,𝑖𝑖 𝑑𝑑𝑑𝑑
𝑇𝑇𝑟𝑟𝑟𝑟𝑟𝑟

where ℎ0,𝑖𝑖 is the enthalpy of formation of the chemical specie 𝑖𝑖. The enthalpy of formation has been
conventionally and arbitrarily set equal to zero for all the pure substances (Csolid, H2, O2, N2, …) in the most
common molecular form (i.e. O2 and not O or O3) at standard conditions (25°C, 1 atm). For molecules
formed by atoms of different species, ℎ0 may be determined from experimental tests, conceptually similar
to that represented in Figure 3 (these values are today available in books and manuals).

1
Alternatively, mass fractions and enthalpy referred to the mass (i.e. in kJ/kg) can be used as well, obtaining the same
result.
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1 𝑚𝑚𝑚𝑚𝑚𝑚/𝑠𝑠 𝐶𝐶 @ 25°𝐶𝐶
1 𝑚𝑚𝑚𝑚𝑚𝑚/𝑠𝑠 𝐶𝐶𝑂𝑂2 @ 25°𝐶𝐶
Adiabatic
combustor
1 𝑚𝑚𝑚𝑚𝑚𝑚/𝑠𝑠 𝑂𝑂2 @ 25°𝐶𝐶

𝑄𝑄̇ = 393.5 𝑘𝑘𝑘𝑘

Figure 3 – Example of system for the determination of ℎ0 for 𝐶𝐶𝑂𝑂2

The system represented in Figure 3 can be calculated by solving the energy conservation equation and the
enthalpy of formation of CO2 can be calculated measuring experimentally the heat released 𝑄𝑄̇ :

𝑀𝑀̇𝐶𝐶 ℎ𝐶𝐶 + 𝑀𝑀̇𝑂𝑂2 ℎ𝑂𝑂2 = 𝑀𝑀̇𝐶𝐶𝑂𝑂2 ℎ𝐶𝐶𝑂𝑂2 + 𝑄𝑄̇

25°𝐶𝐶 25°𝐶𝐶 25°𝐶𝐶

0𝐶𝐶 + �
1 ∙ �ℎ� 𝑐𝑐𝑝𝑝 𝑑𝑑𝑑𝑑� + 1 ∙ �ℎ�
0𝑂𝑂2 + � 𝑐𝑐𝑝𝑝 𝑑𝑑𝑑𝑑� = 1 ∙ �ℎ0𝐶𝐶𝑂𝑂 + � 𝑐𝑐𝑝𝑝 𝑑𝑑𝑑𝑑� + 𝑄𝑄̇
𝐶𝐶 𝑂𝑂2 2 𝐶𝐶𝑂𝑂2
25°𝐶𝐶 25°𝐶𝐶 25°𝐶𝐶
=0 =0

𝑄𝑄̇ 393.5 𝑘𝑘𝑘𝑘 𝑘𝑘𝑘𝑘

ℎ0𝐶𝐶𝑂𝑂 = − = = −393.5
2 𝑀𝑀̇𝐶𝐶𝑂𝑂2 1 𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝐶𝐶𝐶𝐶2 ⁄𝑠𝑠 𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝐶𝐶𝐶𝐶2

3 Heating Value of a Fuel

The heating value 𝐻𝐻𝐻𝐻 of a fuel is the thermal energy released by the combustion of a mass or mole unit of a
fuel with O2, considering reactants and final products at standard conditions (25°C, 1 atm).

𝑀𝑀̇𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓 @ 25°𝐶𝐶
𝑀𝑀̇𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝 @ 25°𝐶𝐶
Adiabatic
combustor
𝑀𝑀̇𝑂𝑂2 @ 25°𝐶𝐶

𝑄𝑄̇

Figure 4 – Example of system for the determination of the heating value of a fuel

By solving the energy balance equation, considering again that at standard conditions ℎ = ℎ0 :

𝑀𝑀̇𝑜𝑜𝑜𝑜𝑜𝑜 ℎ0,𝑜𝑜𝑜𝑜𝑜𝑜 + 𝑀𝑀̇𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓 ℎ0,𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓 = 𝑄𝑄̇ + 𝑀𝑀̇𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝 ℎ0,𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝

𝑘𝑘𝑘𝑘 𝑄𝑄̇ 𝑀𝑀̇𝑜𝑜𝑜𝑜𝑜𝑜 ℎ0,𝑜𝑜𝑜𝑜𝑜𝑜 + 𝑀𝑀̇𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓 ℎ0,𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓 − 𝑀𝑀̇𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝 ℎ0,𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝

𝐻𝐻𝐻𝐻 � �= =
𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓 𝑀𝑀̇𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓 𝑀𝑀̇𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓
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The same balance can be written on a mass basis resulting in the same type of calculation. It is always
possible to convert the heating value from mole to mass basis, through the molar mass of the fuel:

𝑀𝑀𝑀𝑀
𝑀𝑀𝑀𝑀 𝐻𝐻𝐻𝐻 � �
𝑘𝑘𝑘𝑘𝑘𝑘𝑘𝑘𝑘𝑘𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓
𝐻𝐻𝐻𝐻 � �= �
𝑘𝑘𝑘𝑘𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓 𝑘𝑘𝑘𝑘
𝑀𝑀𝑀𝑀
𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓 �𝑘𝑘𝑘𝑘𝑘𝑘𝑘𝑘𝑘𝑘�

Note that the presence of any inert specie (e.g. excess oxygen, nitrogen in air) in the combustion process
would not modify the final result. Their enthalpy flow in the reactants and in the products (left and right
hand side of the previous energy balance equation) would be the same and could be simplified. Therefore,
the heating value of the fuel is an intrinsic property of the fuel and does not depend on how the
combustion process is performed.

The amount of thermal energy generated in the reaction process is dependent upon the phase of the
products. While it is straightforward to consider the reaction products in the gaseous phase for most the
molecules normally considered, this is not for water. In particular, when cooling real combustion products
that contain water to 25°C, part of the water will condense to liquid phase and part will remain in the gas
phase. The condensation of the steam generated in the reaction determines a rise in the released thermal
energy. Being the amount of condensed water strictly dependent on other contingent factors (i.e. pressure,
oxidant composition, oxidant excess), which are independent of the properties of the inlet fuel, the heating
value is usually calculated following two conventions representing the two extreme conditions:

• Lower Heating Value (LHV): assuming that the steam generated in the combustion process remains
totally in vapour phase
• Higher Heating Value (HHV): assuming that the steam generated in the combustion process is
totally condensed to liquid phase

Example of calculation of LHV and HHV of 𝑪𝑪𝑯𝑯𝟒𝟒 (molar-based calculation):

Considering the system represented in Figure 4 with water in the products at vapour phase, the following
relations hold (where enthalpies of formation are taken from databases):

𝐶𝐶𝐻𝐻4 + 2𝑂𝑂2 → 𝐶𝐶𝑂𝑂2 + 2𝐻𝐻2 𝑂𝑂

- Reactants:
𝑘𝑘𝑘𝑘
o CH4: 1 𝑘𝑘𝑘𝑘𝑘𝑘𝑘𝑘𝐶𝐶𝐻𝐻4 , ℎ0,𝐶𝐶𝐶𝐶4 = −74.87 ;
𝑘𝑘𝑘𝑘𝑘𝑘𝑘𝑘

o O2: 2 𝑘𝑘𝑚𝑚𝑚𝑚𝑚𝑚𝑂𝑂2 , ℎ0,𝑂𝑂2 = 0

- Products:
𝑘𝑘𝑘𝑘
o CO2: 1 𝑘𝑘𝑚𝑚𝑚𝑚𝑚𝑚𝐶𝐶𝑂𝑂2 , ℎ0𝐶𝐶𝑂𝑂2 = −393.52 ;
𝑘𝑘𝑘𝑘𝑘𝑘𝑘𝑘
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𝑘𝑘𝑘𝑘
o H2O: 2 𝑘𝑘𝑘𝑘𝑘𝑘𝑘𝑘𝐻𝐻2 𝑂𝑂 , ℎ0,𝐻𝐻2 𝑂𝑂,𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠 = −241.83
𝑘𝑘𝑘𝑘𝑘𝑘𝑘𝑘

From where:

2 ∗ 0 + 1 ∗ (−74.87) − �1 ∗ (−393.52) + 2 ∗ (−241.83)� 𝑘𝑘𝑘𝑘

𝐿𝐿𝐿𝐿𝐿𝐿𝐶𝐶𝐶𝐶4 = = 802.31
1 𝑘𝑘𝑘𝑘𝑘𝑘𝑘𝑘𝐶𝐶𝐶𝐶4

It is possible to calculate the HHV of methane using the enthalpy of formation of liquid water instead of
that of steam. Note that the difference between the steam and liquid water enthalpy of formation is the
heat of phase change, so that:

𝑘𝑘𝑘𝑘 𝑘𝑘𝑘𝑘 𝑘𝑘𝑘𝑘

ℎ0,𝐻𝐻2 𝑂𝑂 𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠 − ℎ0,𝐻𝐻2 𝑂𝑂 𝑙𝑙𝑙𝑙𝑙𝑙 = Δℎ𝑒𝑒𝑒𝑒 (25°𝐶𝐶) = 2442 = 44.0 → ℎ0,𝐻𝐻2 𝑂𝑂 𝑙𝑙𝑙𝑙𝑙𝑙 = −285.8
𝑘𝑘𝑘𝑘 𝑘𝑘𝑘𝑘𝑘𝑘𝑘𝑘𝑘𝑘 𝑘𝑘𝑘𝑘𝑘𝑘𝑘𝑘𝑘𝑘

Therefore:

2 ∗ 0 + 1 ∗ (−74.87) − �1 ∗ (−393.52) + 2 ∗ (−285.8)� 𝑘𝑘𝑘𝑘

𝐻𝐻𝐻𝐻𝐻𝐻𝐶𝐶𝐶𝐶4 = = 89.25
1 𝑘𝑘𝑘𝑘𝑘𝑘𝑘𝑘𝐶𝐶𝐶𝐶4

Example of calculation of LHV and HHV of 𝑪𝑪𝑯𝑯𝟒𝟒 (mass-based calculation):

With the same procedure shown before, material flows and enthalpies need to be converted to mass basis.

- Reactants:
𝑘𝑘𝑘𝑘 𝑘𝑘𝑘𝑘
o CH4: 𝑀𝑀𝑀𝑀𝐶𝐶𝐶𝐶4 = 16 → 16 𝑘𝑘𝑘𝑘𝐶𝐶𝐻𝐻4 , ℎ0,𝐶𝐶𝐶𝐶4 = −4667 ;
𝑘𝑘𝑘𝑘𝑘𝑘𝑘𝑘𝑘𝑘 𝑘𝑘𝑘𝑘
𝑘𝑘𝑘𝑘
o O2: 𝑀𝑀𝑀𝑀𝑂𝑂2 = 32 → 64 𝑘𝑘𝑔𝑔𝑂𝑂2 , ℎ0,𝑂𝑂2 = 0
𝑘𝑘𝑘𝑘𝑘𝑘𝑘𝑘𝑘𝑘

- Products:
𝑘𝑘𝑘𝑘 𝑘𝑘𝑘𝑘
o CO2: 𝑀𝑀𝑀𝑀𝐶𝐶𝐶𝐶2 = 44 → 44 𝑘𝑘𝑘𝑘𝐶𝐶𝑂𝑂2 , ℎ0𝐶𝐶𝑂𝑂2 = −8942 ;
𝑘𝑘𝑘𝑘𝑘𝑘𝑘𝑘𝑘𝑘 𝑘𝑘𝑘𝑘
𝑘𝑘𝑘𝑘 𝑘𝑘𝑘𝑘
o H2O: 𝑀𝑀𝑀𝑀𝐻𝐻2𝑂𝑂 = 18 → 36 𝑘𝑘𝑘𝑘𝑘𝑘𝑘𝑘𝐻𝐻2 𝑂𝑂 , ℎ0,𝐻𝐻2 𝑂𝑂,𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠 = −13423
𝑘𝑘𝑘𝑘𝑘𝑘𝑘𝑘𝑘𝑘 𝑘𝑘𝑘𝑘

From where:

64 ∗ 0 + 16 ∗ (−4667) − �44 ∗ (−8942) + 36 ∗ (−13423)� 𝑘𝑘𝑘𝑘

𝐿𝐿𝐿𝐿𝐿𝐿𝐶𝐶𝐶𝐶4 = = 50125
16 𝑘𝑘𝑘𝑘𝐶𝐶𝐶𝐶4
𝑘𝑘𝑘𝑘
Considering that ℎ0,𝐻𝐻2 𝑂𝑂,𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠 = −15865 , the higher heating value can also be calculated:
𝑘𝑘𝑘𝑘

64 ∗ 0 + 16 ∗ (−4667) − �44 ∗ (−8942) + 36 ∗ (−15865)� 𝑘𝑘𝑘𝑘

𝐻𝐻𝐻𝐻𝐻𝐻𝐶𝐶𝐶𝐶4 = = 55620
16 𝑘𝑘𝑘𝑘𝐶𝐶𝐶𝐶4

Note that the general energy balance equation of a system including fuel combustion can be written
making explicit the heating value of the fuel, leaving only the physical enthalpy terms:
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Course of Energy Systems – Combustion

𝑚𝑚̇𝑜𝑜𝑜𝑜𝑜𝑜 ℎ𝑜𝑜𝑜𝑜𝑜𝑜 + 𝑚𝑚̇𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓 (ℎ𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓 + 𝐿𝐿𝐿𝐿𝐿𝐿) = 𝑊𝑊̇ + 𝑄𝑄̇ + 𝑚𝑚̇𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝 ℎ𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝

𝑇𝑇
ℎ=� 𝑐𝑐𝑝𝑝 𝑑𝑑𝑑𝑑
25°𝐶𝐶

This notation is particularly useful when enthalpy of formation of the fuel is not available as in the case of
solid fuels, which are constituted by complex not easily identifiable molecules. In such cases, the heating
value is directly provided.

4 Adiabatic Flame Temperature

The adiabatic flame temperature is the temperature that the products of combustion reach if there is no
heat exchange between the system and the surrounding environment.

𝑀𝑀̇𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓 𝑘𝑘𝑘𝑘𝑘𝑘𝑘𝑘 @ 𝑇𝑇𝑓𝑓

𝑀𝑀̇𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝 𝑘𝑘𝑘𝑘𝑘𝑘𝑘𝑘 @ 𝑇𝑇𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓
Adiabatic
reactor
𝑀𝑀̇𝑜𝑜𝑜𝑜𝑜𝑜 𝑘𝑘𝑘𝑘𝑘𝑘𝑘𝑘 @ 𝑇𝑇𝑜𝑜𝑜𝑜𝑜𝑜
Figure 5 – System for the calculation of the adiabatic flame temperature

Performing the energy balance on the adiabatic reactor, the following equation can be written:

𝑚𝑚̇𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓 ℎ𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓 + 𝑚𝑚̇𝑜𝑜𝑜𝑜𝑜𝑜 ℎ𝑜𝑜𝑜𝑜𝑜𝑜 = 𝑚𝑚̇𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝 ℎ𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝

Considering again for simplicity and isobaric process:

𝑇𝑇𝑓𝑓 𝑇𝑇𝑜𝑜𝑜𝑜𝑜𝑜
𝑚𝑚̇𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓 �ℎ0𝑓𝑓 + � 𝑐𝑐𝑝𝑝 𝑑𝑑𝑑𝑑� + 𝑚𝑚̇𝑜𝑜𝑜𝑜𝑜𝑜 �ℎ
𝑓𝑓 �� �+�
0𝑜𝑜𝑜𝑜𝑜𝑜 𝑐𝑐𝑝𝑝
𝑜𝑜𝑜𝑜𝑜𝑜
𝑑𝑑𝑑𝑑�
𝑇𝑇𝑟𝑟𝑟𝑟𝑟𝑟 =25°𝐶𝐶 𝑇𝑇𝑟𝑟𝑟𝑟𝑟𝑟 =25°𝐶𝐶
=0

𝑇𝑇𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓
= 𝑚𝑚̇𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝 �ℎ0𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝 + � 𝑐𝑐𝑝𝑝 𝑑𝑑𝑑𝑑�
𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝
𝑇𝑇𝑟𝑟𝑟𝑟𝑟𝑟 =25°𝐶𝐶

𝑇𝑇𝑓𝑓 𝑇𝑇𝑜𝑜𝑜𝑜𝑜𝑜 𝑇𝑇𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓

𝐿𝐿𝐿𝐿𝐿𝐿 + � 𝑐𝑐𝑝𝑝 𝑓𝑓 𝑑𝑑𝑑𝑑 + 𝛼𝛼 ∙ � 𝑐𝑐𝑝𝑝 𝑑𝑑𝑑𝑑 = (1 + 𝛼𝛼) ∙ � 𝑐𝑐𝑝𝑝 𝑑𝑑𝑑𝑑
𝑜𝑜𝑜𝑜𝑜𝑜 𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝
𝑇𝑇𝑟𝑟𝑟𝑟𝑟𝑟 =25°𝐶𝐶 𝑇𝑇𝑟𝑟𝑟𝑟𝑟𝑟 =25°𝐶𝐶 𝑇𝑇𝑟𝑟𝑟𝑟𝑟𝑟 =25°𝐶𝐶

From where the adiabatic flame temperature 𝑇𝑇𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓 can be obtained, being the only unknown variable.
Depending on the functional form of the specific heat of the products 𝑐𝑐𝑝𝑝 , the calculation of 𝑇𝑇𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓 may
𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝

be either explicit or implicit, requiring numerical computational procedures.

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It is important to note that, differently from the heating value, the adiabatic flame temperature is not only
a property of the fuel but also of the combustion process. Oxidant excess and composition and oxidant and
fuel temperatures all influence the adiabatic flame temperature. In general, the higher the temperature of
the reactants and the lower the oxidant excess, the higher the adiabatic flame temperature.

Nomenclature

𝑚𝑚̇ [𝑘𝑘𝑘𝑘 𝑠𝑠 −1 ] Mass flow rate

ℎ [𝐽𝐽 𝑘𝑘𝑔𝑔−1 ] or [𝐽𝐽 𝑘𝑘𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚 −1 ] Enthalpy
ℎ0 [𝐽𝐽 𝑘𝑘𝑔𝑔−1 ] or [𝐽𝐽 𝑘𝑘𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚 −1 ] Enthalpy of formation
𝑐𝑐𝑝𝑝 [𝐽𝐽 𝑘𝑘𝑔𝑔−1 𝐾𝐾 −1 ] Mass specific heating value
𝑇𝑇 [𝐾𝐾] Temperature
𝑀𝑀̇ [𝑘𝑘𝑘𝑘𝑘𝑘𝑘𝑘 𝑠𝑠−1 ] Molar flow rate
𝐿𝐿𝐿𝐿𝐿𝐿 [𝑘𝑘𝑘𝑘 𝑘𝑘𝑔𝑔−1 ] Lower Heating Value
𝐻𝐻𝐻𝐻𝐻𝐻 [𝑘𝑘𝑘𝑘 𝑘𝑘𝑔𝑔−1 ] Higher Heating Value
𝑊𝑊̇ [𝑊𝑊] Mechanical work rate exchanged by the system with the environment
𝑄𝑄̇ [𝑊𝑊] Thermal power exchanged by the system with the environment
𝑥𝑥 [−] Molar fraction
−1
𝛼𝛼 [𝑘𝑘𝑔𝑔𝑜𝑜𝑜𝑜𝑜𝑜 𝑘𝑘𝑔𝑔𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓 ] Mass based oxidant-to-fuel ratio
−1
𝛼𝛼� [𝑘𝑘𝑚𝑚𝑚𝑚𝑚𝑚𝑜𝑜𝑜𝑜𝑜𝑜 𝑘𝑘𝑚𝑚𝑚𝑚𝑚𝑚𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓 ] Molar based oxidant-to-fuel ratio
−1
𝑀𝑀𝑀𝑀 [𝑘𝑘𝑘𝑘 𝑘𝑘𝑘𝑘𝑘𝑘𝑙𝑙 ] Molecular mass
Φ [−] Mass based equivalence ratio
𝜖𝜖 [−] Oxidant excess