UNIT

THERMODYNAMICS OF COMBUSTION
3
LESSONS COVERED

1.1 Combustion Stoichiometry

1.2 Chemical Energy
1.3 Adiabatic Flame Temperature

DURATION: 21 hours

INTRODUCTION

To achieve efficient combustion several parameters should be considered

such as the amount of air to mix with fuel and the temperature at which the
combustion should occur. With the use of stoichiometry and by balancing the
number of atoms in the formula, the desired amount of fuel and air can be
determined. Those values will be useful in identifying the types of products produced
during combustion as well as the maximum temperature the combustion process can
reach. The heating value of fuel can also be determined and how it is affected by air
and the products of combustion.

OBJECTIVES/COMPETENCIES

At the end of the lesson, the students should be able to:

1. Calculate the stoichiometric amount of air necessary for combustion

2. Identify the type of mixture
3. Identify the effect of phase of water present in the products of combustion to
the heating value of fuel
4. Evaluate the effect of the working temperature to the heating value of fuel
5. Calculate the flame temperature using the constant specific heat method and
the iterative balance method
6. Understand the significance of flame temperature with reactor design

LESSON 3.1: COMBUSTION STOICHIOMETRY

As discussed in Chapter 1, fuel must be oxidized to be able to combust. It is

essential to determine the amount of oxidizer needed to combust a certain
amount of fuel to allow complete combustion. This may be calculated by
establishing the combustion formula.

Combustion Engineering 1
 ( )

m is the number of Carbon atoms in the fuel

n is the number of Hydrogen atoms in the fuel
a is the number of moles of air needed for complete/stoichiometric
combustion
b is the number of mole of Carbon dioxide produced
d is the number of mole of water vapour or moisture produced
e is the number of mole of nitrogen produced

The above equation is the general stoichiometric combustion formula for

hydrocarbon fuel. Oxygen will react with carbon and hydrogen atom to form
carbon dioxide and water, respectively. In the case of nitrogen, it is assumed
that nitrogen is non-reactive and will only be present as nitrogen gas in the
products side. But in the actual combustion process, nitrogen may react with
oxygen to form nitrous oxide, which is a greenhouse gas in certain conditions.
Carbon dioxide, water, and nitrogen are the basic theoretical products of
combustion and collectively known as flue gas.

The left side of the combustion formula is collectively known as the reactants.
is the fuel part and ( ) is air. The oxidizing agent commonly
used for combustion is oxygen, and it is abundant in the surrounding air.

The value of 3.76, which is the number of moles of Nitrogen in air is derived
from knowing that the composition of air by volume is:

Analysis, %
Constituents
By volume By weight

Oxygen (O2) 20.99 23.2

Nitrogen (N2) 78.03
Argon (A) 0.94 76.8
Carbon Dioxide (CO2) 0.03
Other gases 0.01
Total 100 100
Table 3.1 Composition of Atmospheric Air

In general, air is composed of different gases, but it is predominantly oxygen

and nitrogen. By volume, nitrogen is approximated to be 79.01%.

If nitrogen will be expressed per mole of oxygen, we will arrive to the value of

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In performing the combustion formula, the mass and number of atoms are
conserved and not necessarily for moles.

In performing the combustion formula, the following steps are suggested, if

only the mole of fuel is given:

( )

The number of atoms of C

The number of atoms of H2

The number of atoms of O2

The number of atoms for N2

( )

( )

The general stoichiometric combustion formula for one mole of hydrocarbon

fuel is

( )( ) ( ) ( )

For fuel that has carbon, hydrogen and oxygen as the predominant elements
in its composition, like in biomass, the general stoichiometric combustion
formula for one mole is

( )

The number of atoms of C

Combustion Engineering 3
The number of atoms of H2

The number of atoms of O2

The number of atoms for N2

( )

( )

( )( ) ( )

Using the combustion formula above, the theoretical or stoichiometric amount

of air needed to combust one mole of fuel is established. But the amount of air
used in actual combustion is more than the theoretical value to avoid
incomplete combustion. The incomplete combustion will occur even if there is
a theoretical amount of air if there is insufficient mixing in the combustion
chamber during the limited time that the fuel and the oxygen are in contact.

Incomplete combustion will yield unburned fuel or components such as

carbon monoxide (CO), carbon, hydrogen, or free oxygen. To avoid this,
excess air is introduced.

The theoretical combustion formula with excess air for hydrocarbon fuel is:

( )( )( )

( ) ( )( ) ( )( )

The added element in the products of combustion is free oxygen.

The percent excess of air is calculated by

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 ( )

A frequently used quantity in the analysis of the combustion process is the air-
fuel ratio. It is 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.

It may be expressed as A/Ftheoretical if the mass of air used is the stoichiometric

value and A/Factual if the mass of air used is the actual air, with excess air.

Now for the mass of air, there are two ways to calculate it.

( ) ( ( ))

The above equation used the theoretical composition of air

Others calculate the mass of air using the molecular weight of air.

The approximate molecular weight of air is 29 kg/kmol, accounting for the

mass of the other gases.

An alternate approach is to determine the amount of fuel needed for a given

amount of air. The quantity being used is the fuel-air ratio.

A measure of how much fuel is actually supplied is called the equivalence

ratio, Φ

When Φ < 1, the mixture is lean, there is excess air

Φ = 1, the mixture is stoichiometric,
Φ > 1, the mixture is rich, there is deficiency of air

An alternative to the normalized quantity of fuel in the mixture, λ (lambda) is

used.

When < 1, the mixture is rich, there is deficiency of air

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 = 1, the mixture is stoichiometric,
> 1, the mixture is lean, there is excess air

The combustion formula is also useful in establishing the dew point

temperature of the products of combustion. Dew point temperature refers to
the temperature at which the moisture in the products of combustion will start
to condense. This value is the saturation temperature corresponding to the
partial pressure of the water vapor. Knowing this value is an important
parameter in the design of combustion chambers because the vapor in the
products of combustion contains corrosive elements that when it liquefies,
could severely damage the piping as well as the chamber itself.

The vapor pressure is obtained, by knowing the working pressure of the

chamber and multiplying it with the mole fraction of water vapor. This is in line
with Dalton’s law of partial pressure, where the total pressure exerted by the
mixture is equal to the sum of the individual pressure of the gas.

Using the steam table, the saturation pressure can be obtained by using the
calculated partial pressure of vapour as reference.

Example 3.1

Determine the mass of air, using the molecular weight of air necessary to burn one
kilogram of methane.

Solution:

( )

The number of carbon in the reactant side is 1, so to solve for b

The number of hydrogen atoms in the reactant side is 4;

The number of oxygen atoms in the reactant side is 2a;

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 ( )

Then the number of nitrogen atoms in the reactant side is 7.52a;

( )

( )

The complete combustion of methane will be:

( )

To check if the combustion formula is correct, the mass of reactants should be equal
to the mass of the products.

( ( )) [ ( )]

( ) ( )

The combustion formula is balance. Now for the mass of air necessary to burn 1 kg
of methane

1 kmol of CH4 will react with 2(4.76) = 9.52 kmol air

On the mass basis,

( )

It reacts with

( )

For every kilogram of methane, it needs 17.255 kg of air to burn completely.

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Example 3.2

One kmol of octane (C8H18) is burned with air, determine the mole number of each
gas in the products and the air – fuel ratio for the stoichiometric combustion process.

Solution:

( )

The number of atoms of C

The number of atoms of H2

The number of atoms for O2

( )

The number of atoms for N2

( )

( )

( )

To check if the combustion formula is correct,

( ) ( )

( ) ( )

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 ( )

( )

( )

For the air – fuel ratio

Mass of air using the components

Mass of air using the molecular weight of air

( ) ( )

There is a little difference with the value for the mass of air and both are acceptable
values, but for the rest of our discussion, we will be using the A/F ratio formula of

Activity
Using the data from example 3.1, perform the gravimetric and
volumetric analysis on the products of combustion.

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Example 3.3

If octane is burned with 20 kmol of O2, what is the fuel – air ratio and the mole
number of each gas in the stoichiometric combustion process.

Solution:

( )

The number of atoms of N2

( )

The number of atoms of O2

( ) ( )

The number of atoms for C

( )

The number of atoms for H2

( )

Substitute (2) and (3) to (1)

( )

Then

The combustion formula is

( )

To check if the combustion formula is correct,

* ( ) ( )+

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 ( ) ( )

( )

( )

( )

Example 3.4

Consider the stoichiometric combustion of dry pines at 1 atm pressure. Assume that
the ultimate analysis of pine is 51% C, 7% H, 42% O, <0.1% N and <0.1% S. Find
the air – fuel ratio and the mass of the composition of products of combustion.

Solution:

From the given data, the predominant element on the fuel is carbon, hydrogen and
oxygen, and all are presented by its weight percentage. For the combustion formula,
the value should by presented by its volume

Assuming 100 kg of dry pine is used

n (kmol)
Constituent mass (kg) MW (kg/kmol) =m/MW

Carbon 51 12 4.25

Hydrogen 7 2 3.5

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 Oxygen 42 32 1.3125

Total 100

For one mole of fuel, the combustion formula is

( )

Using the established relation of a, b, d and e with respect to m, n and p

( )

The combustion formula is

( )

For the air – fuel ratio

( )
( ) ( )

For the mass of the products of composition

( )

( )

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 ( )

Products of % weight = ( )
Mass (kg)
Combustion
CO2 187 27.14
H2O 31.5 4.57
N2 470.47 68.29
Total 688.97 100

Example 3.5

Ethane (C2H6) is burned with 20% excess air. Provide the gravimetric and volumetric
analysis for the dry flue gas of the combustion with excess air, and the type of
mixture.

Solution:

For theoretical combustion:

( )

( )

( )

( )
( )

For actual combustion

( )( ) ( )

Using the value established from the theoretical combustion,

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 ( )( ) ( ) ( )
( )

( )

( )( )
( )

For the normalized air – fuel ratio

The mixture is a lean type since the normalized value is greater than 1.

For the gravimetric and volumetric analysis of dry flue gas

Constituent n (kmol) yi =100xni/nTotal

CO2 2 10.82
H2O - -
N2 15.792 85.40
O2 0.7 3.78
Total 18.492 100

Constituent MW m (kg) = xi
(kg/kmol) nMW =100(mi/mTotal)
CO2 44 88 15.93
H2O - - -
N2 28 442.176 80.02
O2 32 22.4 4.05
Total 552.576 100

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Example 3.6

A certain natural gas has the following volumetric analysis: 72% CH 4, 9% H2, 14%
N2, 2% O2, and 3% CO2. This gas is burned with the stoichiometric amount of air
determine the dew point temperature of the products for the total pressure of 1 atm.

Solution:

The fuel component is a mixture of different gases and when oxidized will yield CO 2,
H2O and N2 in the products since combustion is supposed to be stoichiometric.

Assuming 100 kmol of fuel

( )

Determine the coefficients

( ) ( )

( ) ( )

( ) ( ) ( )

( ) ( )

( ) ( )( )

( )

To determine the partial pressure of water vapour in the products

( )

Combustion Engineering 15
 ( )

Then

The working temperature of the combustion chamber should not be lower than this
value to avoid condensation of the water vapour.

Example 3.7

Octane (C8H18) is burned with dry air. The volumetric analysis of the products on a
dry basis is: CO2 = 10.02%, O2 = 5.62%, CO = 0.88%, N2 = 83.48%.
Determine the air – fuel ratio and the percentage of the excess air used. Determine
the amount of water vapour that condenses as the products are cooled to 250C at
100 kPa.

Solution:

Assuming 100 kmol of dry products

( )

Although the given products of combustion do not contain the data for the amount of
water, water is a basic component of the flue gas.

Balance the number of atoms to find the value of x, a and b.

Balance the carbon atoms

Balance the hydrogen atoms

( )

Balance the nitrogen atoms

( ) ( )

Just to check for the value of a, balance the oxygen atoms

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 ( ) ( )

( ) ( )

Although the value obtained using nitrogen and oxygen atoms differ by only 0.01, to
verify the number, mass balance should be performed.

( )

For one kmole of fuel, the combustion formula will be:

( )

For the air – fuel ratio

( )
( )

For the amount of condensed water vapour, let us first establish the dew point
temperature in which the water vapour will start to condense

( )

Then

The working temperature is 250C and it is lower than the calculated dew point
temperature, thus some of the water vapor has condensed. At 25 0C, the vapor
pressure is 3.169 kPa. The water vapor is less at this point and the total moles of the
products of combustion will also be less.

( )

Combustion Engineering 17
 ( )

( )

The majority of the water vapour, 73.31% of it will condense.

Activity
Using the data from example 3.7, solve for the percentage of excess
air.

REFERENCES

Cengel, Y., & Boles, M. (2002). Thermodynamics An Engineering Approach, Fourth

Edition. New York: McGraw-Hill .
McAllister, S., Chen, J., & Fernandez - Pello, A. (2011). Fundamentals of
Combustion Processes. New York: Springer.
Ragland, K., & Bryden, K. (2011). Combustion Engineering, Second Edition. New
York: CRC Press.

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