CHAPTER 3

COMBUSTION
3.1 Introduction
In this chapter is dealing with the system undergoes the chemical changes
during a process, that is, system that involve chemical reaction known as
combustion.
In practical engines and power plants the source of heat is the chemical
energy of substances called fuels. This energy is released during the
chemical reaction of the fuel with oxygen.
The combustion process takes place in the combustion chamber after
initiation of combustion by an ignition device such as an electric spark. The
most convenient source of oxygen supply is from the atmosphere.
Internal combustion engines are run on liquid fuels which are group as
gasoline (petrol), diesel oil and gaseous fuels. Where as the power plants run
mainly on kerosene and natural gas.
3.2 Basic Chemistry
Atoms the smallest particle that take part in chemical reaction e.g. C, H, O,
S, N etc.
Molecules a combination of atoms that hold together by strong interatomic forces H2, O2, N2 etc.
Relative molecular mass relative masses of the atoms which constitute the
molecule e.g. H2= 2, O2= 32, N2= 32, C= 12, S= 32 etc.

Table 3.1 Chemical compositions of liquid and gases

Compound
Formula
Relative Molecular
Mass
Water/steam
H2O
(2 x 1) + (1 x 16) = 18
Carbon monoxide
CO
(1 x 12) + (1 x 16) = 28
Carbon dioxide
CO2
(1 x 12) + (2 x 16) = 44
Sulphur dioxide
SO2
(1 x 32) + (2 x 16) = 64
Methane
CH4
(1 x 12) + (4 x 1) = 16
Ethane
C2H6
(2 x 12) + (6 x 1) = 30
Propane
C3H8
(3 x 12) + (8 x 1) = 44
n-Butane
C4H10
(4 x 12) + (10 x 1) = 58
Ethylene
C2H4
(2 x 12) + (4 x 1) = 28
Propylene
C3H6
(3 x 12) + (6 x 1) = 42
n-Pentane
C5H12
(5 x 12) + (12 x 1) = 72
Benzene
C6H6
(6 x 12) + (6 x 1) = 78
Toluene
C7H8
(7 x 12) + (8 x 1) = 92
n-Octane
C8H18
(8 x 12) + (18 x 1) =
114
3.3 Fuels
Any materials that can be burned to release thermal energy are called
fuel.
Most familiar fuels are hydrocarbon fuels that consist primarily of
hydrogen and carbon such as coal, gasoline and natural gas.
Coal is a solid fuel contains varying amounts of oxygen, hydrogen,
nitrogen, sulfur, moisture and ash.
Liquid fuels are mixtures of many different hydrocarbons and
obtained from crude oil by distillation. Gasoline is treated as octane,
C8H18 and diesel as dodecane, C12H26. Another common liquid
hydrocarbon is methyl-alcohol (methanol) and used in some gasoline
blends.
Natural gas is produced from gas wells and composed mainly of
methane with small amounts of ethane, propane, hydrogen, helium,
carbon dioxide, nitrogen, hydrogen sulfate and water vapor.
Products of fuel combustion are nitric oxides, carbon monoxide and
hydrocarbons and caused air pollutions to environment.

 Chemical analysis of fuel is called ultimate analysis - analysis by

mass of important elements in the fuel.
For solid fuels such as coal, proximate analysis that gives percentage
of inherent moisture, volatile matter, and combustible solid also can
be used.
3.4 Combustions
A chemical reaction during which a fuel is oxidized and a large
amount of energy is released is called combustion.
The oxidizer most often used in combustion processes is air, for
obvious reasons it is free and readily available. The composition of
dry air can be approximated to 21% of O 2 and 79% of N2 by mole
numbers.
The chemical reaction can be expressed by equation such as:
2H2

O2

2H2O

2 volume H2 + 1 volume O2 2 volumes H2O

analysis)

(based on volume

4kg H2

32kg O2 36kg H2O (based on mass analysis)

1kg H2

8kg O2 9kg H2O

Or

Or
2kmol H2

1kmol O2 2kmol H2O

For the air used in the combustion process;

2 H 2 O2

79
79
N 2 2H 2O
N2
21
21

Since 1kmol of oxygen there are 79/21 kmol of nitrogen.

In the process of combustion of carbon, there are two possibilities will

occur:
(i)

Complete combustion of carbon to carbon dioxide

C O2

79
79
N 2 CO2
N2
21
21

12kg C + 32kg O2 + 105.3kg N2 44kg CO2 + 105.3kg N2

(ii)

Incomplete combustion of carbon

2C O2

79
79
N 2 2CO
N2
21
21

24kg C + 32kg O2 + 105.3kg N2 56kg CO + 105.3kg N2

If a further supply of oxygen available then the combustion can
continue to complete
2CO O2

79
79
N 2 2CO2
N2
21
21

56kg CO + 32kg O2 + 105.3kg N2 88kg CO2 + 105.3kg N2

3.5 Stoichiometric Air-Fuel ratio
Air-fuel ratio (A/F) is defined as the ratio of the mass of air to the mass of
fuel for a combustion process, or
A/ F

mair
m fuel

A stoichiometric mixture of air (theoretical air) and fuel is one that contains
just sufficient oxygen for the complete combustion of fuel. All the carbon in
the fuel burns to CO2, All the hydrogen burns to H2O and all the sulphur (if
any) burns to SO2.
Percentage excess air

actual _ A / F _ ratio stoichiometric _ A / F _ ratio

stoichiometric _ A / F _ ratio

For gaseous fuels the ratios are expressed by volume and for solid and liquid
fuels the ratios are expressed by mass.
Petrol engines have to meet various conditions of load and speed, and
operate over a wide range of mixture strengths:

Mixture _ strength

stoichiometric _ A / F _ ratio
actual _ A / F _ ratio

The working values range between 80% (weak) and 120% (rich).
Example 3.1
One kmol of octane (C8H18) is burned with air that contains 20kmol of
oxygen. Assuming the product contain only CO2, H2O, O2, and N2, determine
the mole number each gas in the products and the air-fuel ratio for this
combustion process
Solution:
Chemical equation for this combustion process;
C 8 H 18 20(O2 3.76 N 2 ) xCO2 yH 2 O zO2 wN 2

Thus, from the equation

C:
H:
O:
N2:

x=8
2y= 18, y= 9
2x + y + z = 40, z= 7.5
w= 75.2

Substituting will give:

C 8 H 18 20(O2 3.76 N 2 ) 8CO2 9 H 2 O 7.5O2 75.2 N 2

A/ F

mair
20 4.76 29

m fuel
8(12) 18(1)

= 24.2kg air/kg fuel

3.6 Exhaust and Flue Gas Analysis

The products of combustion are mainly gaseous
A sample is taken for analysis cooled down to a temperature which
below the saturation of the steam present. The dew point also can be
calculated as the water vapour condensed:
nv , prod

Pv , prod

Pprod

prod

From the dew point temperature, Tdp can be obtained from the
steam table for Pv,prod.
Since the products are gaseous, analysis by volume is usually used
Example 3.2
A sample of dry anthracite has the following composition by mass,
C 90% ; H 3% ; O 2.5% ; N 1% ; S 0.5% ; ash 3%
Calculate:
(i)
the stoichiometric A/F ratio
(ii) the A/F ratio and the dry air and wet analysis of combustion by
mass or by volume, when 20% excess air is supplied
Solution
(i)

Each constituent for complete combustion;

Carbon:
C O2 CO2

12kg C + 32kg O2 44kg CO2

Oxygen required = 0.9 x 32/12 = 2.4kg/kg coal

Carbon dioxide produced = 0.9 x 44/12 = 3.3kg CO2
Hydrogen:
H 2 12 O2 H 2 O

2kg H2 + 16kg O2 18kg H2O

1kg H2 + 8kg O2 9kg H2O

Oxygen required = 0.03 x 8 = 0.24kg/kg coal

Steam produced = 0.03 x 9 = 0.27kg/kg coal
Sulphur:
S O2 SO2

32kg S + 32kg O2 64kg SO2

1kg S + 1kg O2 2kg SO2

Oxygen required = 0.005kg/kg coal

Sulphur dioxide produced = 2 x 0.005 = 0.01kg/kg coal
Constituent
Carbon (C)
Hydrogen (H)
Sulphur (S)
Oxygen (O)
Nitrogen (N)
Ash

Mass Fraction
0.900
0.030
0.005
0.025
0.010
0.030

Oxygen Required
(kg/kg coal)
2.400
0.240
0.005
-0.025
-

Product Mass
(kg/kg coal)
3.30 (CO2)
0.27 (H2O)
0.01 (SO2)
0.01(N2)
-

Total oxygen required per kg of coal = 2.62 kg

Thus, total air required per kg of coal = 2.62/0.233 = 11.245kg
Where air is assumed to contain 23.3% O2 by mass
Stoichiometric air-fuel ratio = 11.245

(ii) For air supply which is 20% in excess,

Actual A/F ratio = 1.2 x 11.245 = 13.494:1
3.7 Practical Analysis of Combustion Product
In combustion process, it is necessary to analyze the product of
combustion for study purposes or improvement on the system
Many of equipment now are available on the market that provides a
quicker, more accurate, and continuous analysis.
(i) Non-dispersive infra-red (NDIR)
The constituent gas is measured by its optical absorption in the infrared spectrum.
(ii) Gas Carbon Dioxide and Oxygen Recorders
A digital instrument that uses to indicate the quality of combustion
process in the boiler
(iii) Gas analyzer
A digital instrument that measures the composition of gas products in
ppm or percentage.
3.8 Dissociation
It is found that during adiabatic combustion the maximum
temperature reached is lower than expected.
For this case, the exothermic combustion process can be reversed if
the temperature is high enough. The reversed process is known as
endothermic.
Example of the combustion process of carbon dioxide and hydrogen
as follows:
2CO O2 2CO2

and

2 H 2 O2 2 H 2 O

To obtain relation for chemical equilibrium in terms of the properties

of the individual components, consider a mixture of four chemical

components A, B, C, and D which exist in equilibrium at a specified

T and P. Now consider a reaction which occurs to an infinitesimal
extent during which differential amounts of reactants A and B are
converted to products C and D a t T remaining constant throughout
the process. Vant Hoff equilibrium box as shown in Figure 3.5 can be
used to study a reversible combustion process:

Figure 3.5
a kmol A + b kmol B c kmol C + d kmol D
The process may proceed equally well in either direction and the
reversal of the process the heat and work transfers would be reversed
in direction
P2
P1

W mRT ln

P2
P1

nT ln

This can be applied to each of the compressors and expanders in the

system
P
P
W A work _ input _ on _ A aT ln A T ln A
P1
P1

 P
P
WB work _ input _ on _ B bT ln B T ln B
P1
P1
P1
PC

WC work _ input _ on _ C cT ln

PC
P1

T ln

P
P
WD work _ input _ on _ D dT ln 1 T ln D
PD
P1

Therefore the net work output of the system

W W A W B WC WD

P
W T ln A
P1

P
ln B
P1

P
ln C
P1

P
ln D
P1

PCc PDd
a b c d
T ln a b ln P1

PA PB

Supposed that in second similar system in the same surroundings the

pressure in the equilibrium box is P' then it will have a net work
output, -W' as

PCc PDd abcd

W T ln a b ln P1
PA PB

Where

P PA PB PC PD

For a combination of two system as shown in Figure 3.6 below:

Figure 3.6
The net work output of the system (-W)-(-W'), thus according to the second
law of thermodynamics, W=W'. Therefore:
PCc PDd ( PC ) c ( PD ) d
K
a b
a
b

P
P
(
P
)
(
P
)
A
B
A B

Where K is the thermal equilibrium or dissociation constant.

A standard thermodynamics equilibrium constant, K , is defined in
dimensionless form by referring each partial pressure to a pressure of 1bar,
P
K ln C
P

PD

P

ln

PA

P

ln

PB

P

ln

Or in general
Pi

ln K ln
i

where

i= stoichiometric coefficient

These expressions can be applied in the combustion process such as

CO 12 O2 CO2

With molar proportions for CO, O2, and CO2 of 1, 0.5, and 1. Thus,

P ( P ) 2
CO2

ln K ln

PCO ( PO2 ) 2

For the combustion of hydrogen,

H 2 12 O2 H 2 O

With molar proportions 1, 0.5, and 1. Thus,

P ( P ) 2
H 2O

PH 2 ( PO2 ) 2

In the combustion of hydrocarbon fuels both of the above reactions may

occur simultaneously and another equilibrium constant can be defined by
dividing

P (P ) 2
H 2O

P (P ) 2
CO2

1
2

PH 2 ( PO2 )

by

1
2

PCO ( PO2 )

Thus,
PH 2O ( PCO )

PH 2 ( PCO2 )

The value of K can be used to determine the reaction temperature from the
table.
Example 3.3
A combustible mixture of carbon monoxide and air which is 10% rich is
compressed to a pressure of 8.28bar and a temperature of 282C. The
mixture is ignited and combustion occurs adiabatically at constant volume.
When the maximum temperature is attained analysis shows 0.228kmol of

CO present for 1kmol of CO supplied. Show that the maximum temperature

reached is 2695C.
Solution:
CO 12 O2 (3.76 12 N 2 ) 2CO2 (3.76 12 N 2 )
CO 0.5O2 1.88 N 2 CO2 1.88 N 2

Actual A/F ratio = stoichiometric A/F ratio x 100/110

= stoichiometric A/F ratio/1.1
Thus, the actual reactants are
CO (0.5O2 1.88 N 2 ) / 1.1

With dissociation there will be some break up of CO 2 giving CO and O2,

thus
CO (0.5O2 1.88 N 2 ) / 1.1 aCO2 bCO cO2 (1.88 / 1.1) N 2

The question states that b= 0.228, therefore

CO 0.455O2 1.709 N 2 aCO2 0.288CO cO2 1.709 N 2

Carbon : 1 = a + 0.228 ,
a= 0.772
Oxygen: 1 + (2 x 0.455) = 2a + 0.228 +2c , c= 0.069
For the reaction

CO 12 O2 CO2

P (P ) 2
CO2

PCO ( PO2 ) 2

And
Therefore

PCO2

a
P2 ,
n2

PCO

b
P2 ,
n2

PO2

c
P2
n2

a n2 P
b cP2

(1)

Where P2= total pressure at the required temperature

n2 = total amount of substance of products
n2= a + b + c + 1.709 = 0.772 + 0.228 + 0.069 + 1.709 = 2.778kmol
At ignition
P1= 8.28bar

and

P1V n1T1

and

T2= 273 + 282 = 555K

P2V n 2 T2

and

V= constant

Therefore
P2 P1

n 2T2
n1T1

Where n1 = 1 + 0.455 + 1.709 = 3.164 and T 2 = 273 + 2695 = 2968K

(assuming)
P2 P1

n 2T2
2.778( 2968)
8.28
38.88bar
n1T1
3.164(555)

Substitute in (1),
K

a
b

n2 P
0.772
2.788 1

3.446
cP2
0.228 0.069 38.88

Therefore, ln K 1.237 , P2= 38.88bar and from the table, the reaction
temperature is 2968K where the assumption made is correct.
3.9 Enthalpy of Formation and Enthalpy of Reaction
The molecules of a system possess various forms of energy, such as sensible
energy, latent energy, chemical energy and nuclear energy.

Process which involves chemical reactions will involve changes in chemical

energy and must be considered in energy balance. In absence of nuclear
reactions, kinetic and potential energy changes, the energy balance is
Esys Estate Echem

The common practice to choose a reference state is at 25C and 1atm. This is
known as the standard reference state, and the properties at this state are
denoted by a superscript o.
3.9.1 Enthalpy of Reaction hR
For combustion processes, the hR is usually referred to as the enthalpy of
combustion h hc, which represents the amount of heat released during a
steady-flow combustion process when 1kg (or 1 kmol) of fuel is burnt
completely at a specified temperature and pressure. It is expressed as
hc h p hr

Where hp is the enthalpy of the products and hr is the enthalpy of reactants.

It is evident that, hc is a usefull property for analyzing the combustion
processes. However, it is impractical to list the value of hc for all possible
fuel and fuel mixture. Therefore, a more practical approach would be to have
a fundamental property that would represent the chemical energy of an
element or compound at some reference state. The enthalpy of formation hf
is such a fundamental property which is the enthalpy of substance at a
specified state owing to its chemical composition.
All stable elements, such as O2, N2 , H2, and C have a zero value as their
enthalpy of formation at the standard reference state (25C and 1 atm). That
o
is, h f 0 for all stable elements.
Let us consider,
C O2 CO2

If the reaction is carried out at the standard reference state, the heat
transferred from the system is given by,

o
q ho hpo hro hCO
hCo hOo 2
2

o
o
o
Since hC hO 0 , therefore q hCO 393,520kJ
2

The negative sign indicates that heat is released during the formation of the
compound from its stable elements.
Heating value or Calorific value- defined as the amount of energy
released when a fuel is burnt completely in a steady flow process and the
products are returned to the state of reactants. The heating value (HV) of a
fuel is equal to the absolute value of the enthalpy of combustion of the fuel,
HV hc

The HV depends on the phase of the H2O in the products. It is called the
higher heating value, HHV when the H2O is the liquid form but it is called
the lower heating value, LHV when the H2O in the vapor form. Thus, these
two values are related by
HHV LHV ( nh fg ) H 2 O

Where n is the no. of moles of H2O in the vapor form and hfg is the enthalpy
of vaporization of water at the specified temperature.
3.9.2 For open systems
When the kinetic and potential energies are negligible, the energy equation
can be expressed as
Q W H p Hr

Where

H p n p h of h h o

and

H r nr h of h h o

Therefore,
Q W n p h of h h o p nr h of h h o r

Or in terms of enthalpy of combustion

rewritten as

Q W hco n p h h o

nr h h o

hCo ,

energy equation above can be

Example 3.4
Determine the enthalpy of combustion of gaseous propane (C3H8) at 25C
and 1 atm. Assume that water in the product is in liquid form.
Solution:
The stoichiometric equation for this reaction;
C3 H 8 a (O2 3.76 N 2 ) 3CO2 4 H 2O 3.76aN 2

Thus,

hc h p hr

or

n h

hc n p h of

(nh of )CO2 (nh of ) H 2 O (nh of )C3 H 8

o
f r

Using the enthalpy table, we get

hc 3( 393,520) 4( 285,830) 1( 103,850) 2,220,030kJ / kmol

3.9.3 For closed systems

For a chemically reacting closed system, the conservation of energy relation
can be expressed as
Q W U p Ur

By definition,
u h P

Or

u of u u o hof h h o P

Thus,

Q W n p h of h h o P

n h
p

o
f

h h o P

For solids and liquids, the P terms are negligible and for gases which
behave as an ideal gas the P terms can be replaced by RT.
Example 3.5
Methane gas is burnt with the stoichiometric amount of oxygen gas. The
water is the product in the gas phase. Determine the heat released or
observed if the reaction occurs at 25C and 1 atm.
Solution:
The combustion equation is
CH 4 2O2 CO2 2 H 2O

The heat transfer is a steady flow combustion and W= 0. Thus,

Q n p h of h h o

n h
r

o
f

h ho

Q n p h of p nr h of r 1(393,520) 2( 241,820) 1(74,850) 2(0)

Or

= -802,310 kJ/kmol CH4

3.10 Adiabatic Flame Temperature
The chemical energy loss to surrounding or is used internally to raise the
temperature of the combustion products for the absence of kinetic and
potential energies. Since no heat loss case, Q=0 the temperature of products
will reach a maximum which is called the adiabatic flame temperature of the
reaction.
For steady flow combustion process, the adiabatic flame temperature is
determined from (Q=0 and W=0):

n h
p

o
f

h ho

nr h of h h o

For the case of no excess air, the adiabatic flame temperature is called the
theoretical adiabatic flame temperature for the fuel. It is the highest
temperature that can be achieved from the fuel used in the combustion.
3.11 Power Plant Thermal Efficiency
The overall thermal efficiency o is defined as
o

work _ output
fuel _ energy _ sup plied

The fuel energy supplied can be considered either Qgr,P or Qnet,P.

For example, in a plant the boiler efficiency B is obtained by the following
equation:

Heat _ transfer ed _ to _ fluid

B
Qgr,P _ or _ Qnet,P
3.12 Practical Determination of Calorific Values
Calorific value is used to measure the total energy available in the fuels.
Since, the types of fuel are can be in the forms of solid, liquid and gases.
Thus, the instruments used to determine the calorific value also depend on
the type of fuel. For solid and liquid fuels are usually tested in a bomb
calorimeter and for gaseous fuels in a Boys calorimeter as described briefly
bellows:
(i)
Solid and Liquid Fuels
In a bomb calorimeter combustion occurs at constant volume and is a
non-flow process.
The bomb is a small stainless steel vessel in which a small mass of the
fuel is held in a crucible (see Figure 3.12) as a pellet.

Figure 3.12 Bomb Calorimeter

The pellet is estimated such that the temperature rise to be measured does
not exceed 2-3K. The pellet is ignited by fusing a piece of platinum or
nichrome wire which in contact with it.
The crucible carrying the pellet is located in the bomb, a small quantity
of distilled water is put into the bomb to absorb the vapors formed by
combustion and to ensure that the water vapors produced is condensed,
and the top bomb is screwed down.
After fifth minute the charge is fired and temperature readings are taken
every 10 seconds during this period. When the temperature readings start
to fall, the frequency of readings is taking every minute.

The water equivalent of the calorimeter is determined by burning a fuel

of known calorific value in the bomb. The calculation for the test is then
as follows:
Mass of fuel calorific value = (mass of water + water equivalent of
bomb) corrected temperature rise specific heat capacity of water
From this equation the calorific value of fuel can be obtained.
(ii) Gaseous Fuels
In a Boys calorimeter the gas is burnt continuously under steady flow
conditions and the gas is metered and passed at constant pressure into the
calorimeter, where it is burned in an ample supply of air (see Figure
3.13).

Figure 3.13 Boys Calorimeter

Products of combustion are cooled as nearly as possible to the initial
temperature of the reactants by a continuously circulation supply of
cooling water.

The temperature rise of the circulating water is measured, and the

condensate from the products of combustion is collected. The water flow
rate is measured and condensate is weighed. Thus, calorific value of fuel
can be obtained by
(Volume of fuel at 1.013bar and 15C) calorific value = (mass of water
circulated) specific heat capacity of water (temperature rise of water)
3.13 Air and Fuel-Vapor Mixtures
The mixture supplied to an engine fitted with a carburetor is one air and fuel
vapor, and the quality of the mixture is controlled by the carburetor.
If the mixture is saturated with fuel vapor then the relative proportion of fuel
to air can be determined from the knowledge of the temperature-pressure
relationship for the saturated fuel.
Example 3.6:
For a stoichiometric mixture of ethyl alcohol of 0.022kmol/kg and air
substance of 0.309kmol/kg, calculate the temperature above which there will
be no liquid fuel in the mixture. The pressure of the mixture is 101.3kPa.
Solutions:
nC2 H 6O 0.022kmol / kg and n Air 0.309kmol / kg
nTotal nC2 H 6O n Air 0.331kmol / kg

nC2 H 6O
PC2 H 6O
nTotal

Pmixture 0.022kmol / kg

From the table of C2H6O:

T (oC)

10

20

30

40

50

60

P (kPa)

1.62

3.14

5.28

Thus,
6.7 5.84
10 21.85C
10.49 5.84

T 20

10.49

18.00

26.60

46.90