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Combustion

Combustion Basics

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 and are
denoted by the general formula CnHm Hydrocarbon fuels
exist in all phases, some examples being coal, gasoline,
and natural gas.
In practical engines and power plants the source of
heat is the chemical energy of substances (fuels). This
energy is released during the chemical reaction of the
fuel with oxygen. Heat is released during the reaction.

Fuel

Fuel

The most important fuel elements are carbon and

hydrogen, and most fuels consists of these and
sometimes a small amount of sulphur.
The fuel may contain some oxygen and a small quantity
of water vapour, nitrogen or ash (incombustibles).

Where fuels contain some oxygen this oxygen is

available for the combustion process, and so the
fuel requires a smaller supply of air.

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Oxygen in Air
For a given amount of fuel there is a definite amount of

Source of Oxygen
The most convenient source of oxygen supply is that of
the atmosphere.

oxygen required for its complete combustion (therefore

Air also contains Nitrogen and traces of other gases.

a definite amount of air).

It is usual in combustion calculations to take air as:

To ensure complete combustion of fuel, it is usual to
supply air in excess of the amount required for
chemically correct combustion.

23.3% O2 and 76.7% N2 by mass;

21% O2 and 79% N2 by volume.
The small traces of other gases in dry air are included in the nitrogen,
which is sometimes called atmospheric nitrogen.

Fuel

Gaseous Fuels (chemically simplest)

Natural gas
Refinery gas

Liquid Fuels (mostly hydrocarbons)

Kerosene
Gasoline, diesel
Alcohol (Ethanol)
Oil

Solid Fuels
Coal (Anthracite, bituminous, subbituminous, lignite)
Wood

C O2 CO2
1
H2 O2 H2 O
2

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C8 H18 A O2 B CO2 D H2 O

C8 H18 A O2 8 CO2 9 H2 O
C8 H18 12.5 O2 8 CO2 9 H2 O

Composition of air:
23.3% O2 and 76.7% N2 by mass;
21% O2 and 79% N2 by volume.

C8 H18 12.5 ( O2 3. 76 N 2 )
8 CO2 9 H2 O 47 N 2

Ultimate Analysis

C8 H18 A O2 B CO2 D H2 O

C8 H18 A O2 8 CO2 9 H2 O

An accurate chemical analysis by mass of

the

important elements in the fuel is called the Ultimate

analysis.
The elements usually included are carbon, hydrogen,
oxygen, nitrogen and sulphur.

C8 H18 12.5 O2 8 CO2 9 H2 O

C8 H18 12.5 ( O2 3. 76 N 2 )
8 CO2 9 H2 O 47 N 2

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Proximate Analysis

Analysis of Liquid Fuels

Proximate analysis gives the percentages of inherent

moisture, volatile matter, and combustible solid called
fixed carbon.
The fixed carbon is found as a remainder by deducting
the other quantities.

Fuel
Analysis by volume of a Typical Natural Gas

Properties of Selected Fuels

CH4

C2H6

C3H8

Other HCs

H2S

Heating Value
(106 J/m3)

(wt%)

Natural gas (No.1)

87.7

5.6

2.4

1.8

2.7

Natural gas (No.2)

88.8

6.4

2.7

2.0

0.0004

86.4

12.7

0.1

(Ultimate analysis)

43.2
41.9
Heating value
(106 J kg-1)

(wt%)

Gasoline (No.2)
(Proximate analysis)

Carbon

Moisture

0.4-0.7
Ash

Heating value

(%)

(%)

(%)

(%)

(106 J kg-1)

Anthracite (PA)

77.1

3.8

5.4

13.7

27.8

Bituminous (PA)

70.0

20.5

3.3

6.2

33.3

Subbituminous (CO) 45.9

30.5

19.6

4.0

23.6

Lignite (ND)

28.2

34.8

6.2

16.8

30.8

Volatile matter

0.1

Data from Flagan and Seinfeld, Fundamentals of Air Pollution Engineering, 1988, Prentice-Hall.

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Combustion Stoichiometry

Stoichiometric air-fuel ratio

Combustion in Oxygen

Cn H m O2 CO2 H 2O

A stoichiometric mixture of air and fuel is one that

contains just sufficient oxygen for the complete
combustion of the fuel.

1.
2.

Can you balance the above equation?

Write the reactions for combustion of methane and
benzene in oxygen, respectively.

Answer
m
m

C n H m n O2 nCO2 H 2O
4
2

CH 4 2O 2 CO 2 2 H 2O
C6 H 6 7.5O2 6CO2 3H 2O

Combustion Stoichiometry
Combustion in Air (O2 = 21%, N2 = 79%)

Air-Fuel Ratio
Air-Fuel (AF) ratio
AF = m Air / m Fuel

Cn H m (O2 3.78N 2 ) CO2 H 2O N 2

Where:
1.
2.

Can you balance the above equation?

Write the reactions for combustion of methane and benzene
in air, respectively.

Answer
m
m
m

C n H m n (O 2 3.78N 2 ) nCO2 H 2O 3.78 n N 2

4
2
4

CH 4 2(O 2 3.78 N 2 ) CO 2 2 H 2O 7.56 N 2

m air = mass of air in the feed mixture

m fuel = mass of fuel in the feed mixture

Fuel-Air ratio: FA = m Fuel /m Air = 1/AF

Air-Fuel molar ratio

AFmole = nAir / nFuel
Where:

nair = moles of air in the feed mixture

nfuel = moles of fuel in the feed mixture

C6 H 6 7.5(O2 3.78 N 2 ) 6CO2 3H 2O 28.35N 2

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Air-Fuel Ratio
Rich mixture
- more fuel than necessary
(AF) mixture < (AF)stoich
Weak mixture
- more air than necessary
(AF) mixture > (AF)stoich

Percentage Excess Air

actual A/F ratio - stoichiome tric A/F ratio

stoichiome tric A/F ratio
A-

Air

F-

Fuel

Most combustion systems operate under lean conditions.

Why is this advantageous?
Consider the combustion of methanol in an engine. If the Air-Fuel
ratio of the actual mixture is 20, is the engine operating under rich
or lean conditions?

Mixture Strength

Stoichiome tric A/F ratio

Mixture Strength
Actual A/F ratio

Exhaust and Flue Gas Analysis

The products of combustion are mainly gaseous and
include vapour.
For analysis, the samples are usually cooled to a
temperature below saturation temperature of the
steam.
When steam is NOT included, the analysis is said to
be dry.
An analysis that includes the steam (from the
exhaust) is called a wet analysis.

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Example 7.1 from Eastop & McConkey

One kmol of octane (C8H18) is burned with air that contains

A sample of dry anthracite has the following composition

by mass:

20 kmol of O2. Assuming the products contain only CO2,

C 90%; H 3%; O 2.5%; N 1%; S 0.5%; ash 3%.

H2O, O2, and N2, determine the mole number of each gas in
the products and the airfuel ratio for this combustion
process.

Calculate:
(i) the stoichimetric A/F ratio;
(ii)the actual A/F ratio and the dry and wet analysis of the
products of combustion by mass and by volume, when
20% excess air is supplied.
(i)
(ii)

11.245
13.494 / 1

Problem 1

Problem 2

A sample of bituminous coal gave the following ultimate

analysis by mass:

Calculate the stoichiometric A/F ratio for benzene

(C6H6), and wet and dry analysis of the combustion

C 81.9%; H 4.9%; O 6%; N 2.3%; ash 4.9%.

products.

Calculate:
(i) the stoichimetric A/F ratio;
(ii) the analysis by volume of the wet and dry products of
combustion when 25% excess air is supplied.
(i)
(ii)

10.8/1
CO2 14.14%; H2O 5.07%; O2 4.08%; N2 76.71%; CO2
14.89%; O2 4.30 %; N2 80.81%

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Problem 2

Example 7.3 & 7.4 from Eastop & McConkey

Calculate the stoichiometric A/F ratio for benzene

Ethyl alcohol is burned in a petrol engine. Calculate:

(C6H6), and wet and dry analysis of the combustion

(i) The stoichiometric A/F ratio;

products.

(ii) The A/F ratio and the wet and dry analyses by volume of
the exhaust gas for a mixture strength of 90%;

13.2/1; [wet:]CO2 16.13%; H2O 8.06%; N2 75.81%;

[dry:] CO2 17.54%; N2 82.46%

(iii) The A/F ratio and the wet and dry analyses by volume of
the exhaust gas for a mixture strength of 120%.

Example 7.3 & 7.4 from Eastop & McConkey

Example 7.3 & 7.4 from Eastop & McConkey

Ethyl alcohol is burned in a petrol engine. Calculate:

For the stoichiometric mixture (just calculated), calculate:

(i) The stoichiometric A/F ratio;

(i) the volume of the mixture per kilogram of fuel at a

(ii) The A/F ratio and the wet and dry analyses by volume of
the exhaust gas for a mixture strength of 90%;
(iii) The A/F ratio and the wet and dry analyses by volume of
the exhaust gas for a mixture strength of 120%.

(i) 8.957/1; (ii) 9.952/1, [dry:]13.45% of CO2, 84.31% of N2;

temperature of 650C and a pressure of 1.013 bar;

(ii) The volume of the products of combustion per kilogram
of fuel after cooling to a temperature of 1200C at a
pressure of 1 bar.

(i) 9.219 m3 (ii) 9.219 m3

(iii) 7.47/1, [dry:] 8.77% of CO2, 82.46% of N2.

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Problem 3

Problem 4

In the actual combustion of benzene (C6H6) in an

The analysis of a supply gas is as follows: H2 49.4%;

engine the A/F ratio was 12/1. Calculate the wet and

CO 18%; CH4 20%; C4H8 2%; O2 0.4%; N2 6.2%; CO2 4%.

dry analysis of the combustion products.

Calculate:
(i) The stoichiometric A/F ratio;
(ii) the wet and dry analysis of the products of

CO2 13.38%; CO 3.94%; H2O 8.66%; N2 74.03%

combustion if the actual mixture is 20% weak

(i) 4.062 (by volume)

(ii) wet: CO2 9.0%, H2 O 17.5%, O2 3.08%, N2 70.4%

Problem 5

Problem 6

Propal alcohol (C3H7OH) is burned with 50 percent

A fuel mixture of 20 percent by mass methane (CH4)

excess air. Write the balanced reaction equation for

and 80 percent by mass ethanol (C2H6O), is burned

complete combustion and determine the air-to-fuel

completely with theoretical air. If the total flow rate of

ratio.

the fuel is 31 kg/s, determine the required flow rate of

air.
15.5 kg air/kg fuel
330 kg/s

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Problem 6

Problem 7

A certain natural gas has the following volumetric

Methane (CH4) is burned with dry air. The volumetric

analysis: 65 percent CH4, 8 percent H2, 18 percent N2,

analysis of the products on a dry basis is 5.20 percent

3 percent O2, and 6 percent CO2. This gas is now

CO2, 0.33 percent CO, 11.24 percent O2, and 83.23

burned completely with the stoichiometric amount of

percent N2.

dry air. What is the airfuel ratio for this combustion

Determine (a) the airfuel ratio and (b) the percentage

process?

of theoretical air used.

9.42 kg air/kg fuel

(a) 34.5 kg air/kg fuel, (b) 200 percent

Theoretical And Actual Combustion Processes

Complete combustion: If all the carbon in the fuel burns to
CO2, all the hydrogen burns to H2O, and all the sulfur (if any)
The combustion reaction is a particular kind of
reaction

in

which

products

are

formed

burns to SO2.

from

reactants with the release or absorption of energy as

heat is transferred to or from the surroundings.

A combustion process is complete if all the combustible components

of the fuel are burned to completion.

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Theoretical And Actual Combustion Processes

THEORETICAL AND ACTUAL

COMBUSTION PROCESSES
Reasons for incomplete combustion:

Incomplete combustion: If the combustion products contain

1. Insufficient oxygen;

any unburned fuel or components such as C, H2, CO, or OH.

2. insufficient mixing in the combustion chamber during the

limited time that the fuel and the oxygen are in contact, and

Reasons for incomplete combustion: 1 Insufficient oxygen,

3. dissociation (at high temperatures).

2 insufficient mixing in the combustion chamber during the

Oxygen has a much greater tendency to combine with

limited time that the fuel and the oxygen are in contact, and 3

hydrogen than it does with carbon. Therefore, the hydrogen in

dissociation (at high temperatures).

the fuel normally burns to completion, forming H2O.

Some of the carbon, however, ends up as CO or just as plain
C particles (soot) in the products.
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Stoichiometric or theoretical air: The minimum amount of air

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Excess air: The amount of air in excess of the stoichiometric

needed for the complete combustion of a fuel. Also referred to

amount. Usually expressed in terms of the stoichiometric air as

as the chemically correct amount of air, or 100% theoretical air.

percent excess air or percent theoretical air.

Stoichiometric or theoretical combustion: The ideal

50% excess air = 150% theoretical air

combustion process during which a fuel is burned completely

200% excess air = 300% theoretical air.

with theoretical air.

90% theoretical air = 10% deficiency of air

The complete combustion process with no free oxygen in

the products is called theoretical combustion.

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Deficiency of air: Amounts of air less than the stoichiometric

Predicting the composition of the

products is relatively easy when
the combustion process is
assumed to be complete.

amount. Often expressed as percent deficiency of air.

With actual combustion

processes, it is impossible to
predict the composition of the
products on the basis of the
mass balance alone.

Equivalence ratio: The ratio of the actual fuelair ratio to the

stoichiometric fuelair ratio.

Then the only alternative we

have is 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.

Determining the mole fraction of the

CO2 in combustion gases by using
the Orsat gas analyzer.

The results are reported on a

dry basis.
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ENTHALPY OF FORMATION AND

ENTHALPY OF COMBUSTION
Disregarding any changes in kinetic and potential energies, the energy change
of a system during a chemical reaction is due to a change in state and a change
in chemical composition:

46

ENTHALPY OF FORMATION h f
The standard enthalpy of formation of a compound is the
change of enthalpy that accompanies the formation of 1
mole of a substance in its standard state from its
constituent elements in their standard states.
(The most stable form of the element at 1 bar of pressure
and the specified temperature, usually 298.15 K or 25
degrees Celsius).

The microscopic form of energy of a

substance consists of sensible, latent,
chemical, and nuclear energies.

When the existing chemical bonds

are destroyed and new ones are
formed during a combustion process,
usually a large amount of sensible
energy is absorbed or released.
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ENTHALPY OF FORMATION h f

ENTHALPY OF FORMATION h f

The standard enthalpy change of formation is measured in

The standard enthalpy change of formation is used in

units of energy per amount of substance. Most are defined

thermodynamics to find the standard enthalpy change of

in kilojoules per mole, or kJ mol1.

reaction.

All elements in their standard states (oxygen gas, solid

This is done by subtracting the sum of the standard

carbon in the form of graphite, etc.) have a standard

enthalpies of formation of the reactants from the sum of

enthalpy of formation of zero, as there is no change

the standard enthalpies of formation of the products, as

involved in their formation.

shown in the equation below.

To establish a starting point, we assign the enthalpy of formation of all

stable elements (such as O2, N2, H2, and C) a value of zero at the
standard reference state of 25C and 1 atm.

The molar enthalpy of reaction may be calculated using:

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Heating value: The amount of heat

released when a fuel is burned
completely in a steady-flow process
and the products are returned to the
state of the reactants. The heating
value of a fuel is equal to the
absolute value of the enthalpy of
combustion of the fuel.

The enthalpy of formation hf : The amount of energy

absorbed or released as the component is formed from its
stable elements during a steady-flow process at a specified
state.

Higher heating value (HHV): When

the H2O in the products is in the
liquid form.
Lower heating value (LHV): When
the H2O in the products is in the
vapor form.
The higher heating value of a fuel is equal to the sum of the lower heating
value of the fuel and the latent heat of vaporization of the H2O in the products.
For the fuels with variable
composition (i.e., coal, natural gas,
fuel oil), the heating value may be
determined by burning them
directly in a bomb calorimeter.

53

Problem 5

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Problem 5

Calculate the molar enthalpy of reaction at 250C of

ethyl alcohol, C2H5OH.

The

enthalpy of combustion of propane gas, C3H8, at

250C

with the H2O in the products in the liquid phase is

-50 360 kJ/kg. Calculate the enthalpy of combustion

-1 231 428 kJ/kmol

with the H2O in the vapour per unit mass of fuel and
per unit amount of substance of fuel.
-46 364 kJ/kg; -2 040 030 kJ/kmol

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Partial Combustion

BOMB CALORIMETER
A calorimeter is a device used for calorimetry, the science of
measuring the heat of chemical reactions or physical changes as
well as heat capacity.

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Specific heat is the amount of heat per unit mass required to

raise the
temperature by one Kelvin:
Substance
Aluminum

c in cal/gm K

0.9

0.215

Bismuth

0.123

0.0294

Copper

0.386

0.0923

Brass

Q = heat added (energy)

c = specific heat
m = mass
T = change in temperature

c in J/gm K

Please attempt problems 7.1 to 7.12

0.38

0.092

Gold

0.126

0.0301

Lead

0.128

0.0305

Silver

0.233

0.0558

Tungsten

0.134

0.0321

Zinc

0.387

0.0925

0.14

0.033

2.4

0.58

Mercury
Alcohol(ethyl)
Water

4.186

Ice (-10 C)

2.05

0.49

Granite

0.79

0.19

Glass

0.84

0.2

Acknowledgement:
Prepared by: Ying Li

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