.

Thermochemistry of Fuel

CH. 3

1
Fuels:
Fuel is any material when burnt will produce heat energy.
Various fuels commonly used are as follows:
1. Solid Fuels:
Coal is the most important solid fuel; there are other types of
solid fuels, such as: nuclear fuels, solid wastes (wood, sugar-
cane). Coal is divided into groups according to their chemical
and physical properties.
2. Liquid Fuels:
Liquid fuels are widely used for I.C.E. Practically all liquid
fuels have two basic combustible elements; carbon and
hydrogen, present separately or in a combination called
hydrocarbons, there are principal commercial types of liquid
fuels:
2
Petroleum and its Derivatives
They are easy to handle, store, and burn and have nearly
constant heating values. They are usually a mixture of
hydrocarbons that may be represented by the molecular
formula of the form , where m is a function of n that depends
upon the family of the hydrocarbon.
Combustion of Fuels:
Combustion of fuel is accomplished by mixing fuel with air at
elevated temperature: Fuel + Air Products of Combustion +
Heat. The oxygen contained in the air unites chemically with
carbon, hydrogen and other elements in fuel to produce heat.
The amount of heat liberated during the combustion process
depends on the amount of oxidation of the constituent of fuel
and the nature of fuel. In order that the combustion of fuel
may3 take place with high efficiency:
following conditions must be fulfilled:
1. The amount of air supplied should be sufficient.
2. The air and fuel should be thoroughly mixed.
3. The temperature of the reactants should be high enough to
ignite the mixture.
4. Sufficient time should be available to burn fuel completely
Combustion Chemistry: 1. Chemical Equation:
The chemical equation shows how the atoms of the reactants
are arranged to form products. Before the chemical equation
can be written it is necessary to know the number of atoms of
elements in the molecules of the reactants and products.
During combustion process the atoms are rearranged to form
new molecules, and the total number of atoms of each element
is unchanged. A chemical equation expresses the principle of
the 4conservation of mass in terms of the conservation of atoms
i- Combustion of Carbon
C+
1 kmol C + 1 kmol→ 1 kmol
12 kg C + 32 kg4 kg
If any of the reactants or products is in solid or liquid phase,
the volume occupied by them can be neglected. It follows that:
0 vol. C + 1vol 1vol.
If insufficient oxygen is present for all carbon to burn to
carbon dioxide, some will burn to carbon monoxide, then:
C + 1/2CO
ii- Combustion of Hydrogen
+ 1/2 1 kmol + 1/2 kmol 1 kmol
2kg + 32*1/2 kg 18kg
1 vol. + 1/2 vol. vol.(vapour)
5
In most engineering combustion systems the necessary oxygen
is obtained by mixing the fuel with air (except rockets) and it
is necessary to use accurate and consistent analysis of air by
mass and by volume. It is usual in combustion calculations to
take air as 23.3%, 76.7% by mass, and 21% , 79%by volume.
The small traces of other gases in dry air are included in the
nitrogen, which is sometimes called "atmospheric nitrogen".
The moisture or humidity in atmospheric air varies over wide
limits, depending on meteorological conditions. Its presence in
most cases simply implies an additional amount of inert
material. The molar mass of AIR can be taken as 32 kg/kmol,
and that ofas 28kg/kmoland air 29 kg/kmol. Since oxygen is
accompanied by nitrogen when air is supplied for combustion,
then this nitrogen should be included in the combustion
equation, it will appear on both sides of the equation.
6
With one mole of there are 79/21=3.762moles of N2,

A frequently used quantity in the analysis of combustion

process is the air-fuel ratio A/F. it is defined as the ratio of the
mass of air to the mass of fuel for a combustion process.

7
The mass m of a substance is related to the number of moles n
through the relation: m = nM, where M is the molar mass.
The reciprocal of A/F ratio is called the fuel-air ratio. The
minimum amount of air needed for the complete combustion
of a fuel is called the stoichiometric or theoretical air. In
actual combustion processes, it is common practice to use
more air than the stoichiometric amount. The amount of extra
air than the stoichiometric is called (excess air). Amount of
air less than stoichiometric amount is called (deficiency of
air). Equivalence ratio is the ratio of the actual fuel- air ratio
to the stoichiometric fuel-air ratio. Sometimes this ratio is
given in term of A/F ratio and called mixture strength.

8
9
The composition of a hydrocarbon fuel are carbon and
hydrogen, n and m can be determined for 1 kg of fuel as
follows:

Exhaust and Flue Gas Analysis:

The products of combustion are mainly gaseous. When a
sample is taken for analysis it is usually cooled down to a
temperature which is below the saturation temperature of the
steam present. The steam content is therefore not included in
the analysis, which is then quoted as the analysis of dry
products. Since the products are gaseous, it is usual to quote
the analysis by volume. An analysis which includes the steam
in 10the exhaust is called a wet analysis.
Example (3 – 1):
Find the stoichiometric A/F ratio for the combustion of ethyl-
alcohol (OH) in a petrol engine. Calculate the A/F ratios for
0.9&1.2 equivalence ratios(ϕ). Determine the wet and dry
analyses by volume of the exhaust gas for each equivalence
ratio.

Mass of air required for complete burning of one mole of fuel

is: 11
12
For ϕ = 0.9; air supplied is 1/0.9 = 1.11 times as much air
supplied for complete combustion, then: combustion equation
becomes:

i.e. The total number of moles of products = 2+3+0.33+12.54

=17.87. Hence wet analysis is:
Total dry moles = 2+0.33+12.54=14.87
Hence wet analysis is:

13
 This means that 1/1.2 = 0.834of the stoichiometric air is
supplied. The combustion cannot be complete & is usual to
assume that all the hydrogen is burned to O, since atoms
have a greater affinity for oxygen than C atoms. The carbon
in the fuel will burn to CO and C:
OH+0.834(3+3x3.762)aC+bCO+3O +0.834 × 3 × 3.762
C balance: 2 = a + b
O balance: 1+2 × 0.834 × 3=2a+b+3
Subtracting the equations gives: a=1.004
and then: b =2 – 1.004 =0.996

14
i.e. The products are:1.004 moles C+ 0.996 moles CO+3 moles + 9.41
molesThe total moles of products = 1.004+0.996 +3+9.41 =14.41
Hence wet analysis is:

The total dry moles = 1.004+0.996+9.41=11.41

Hence dry analysis is:

15
16
17
18
Dew Point Temperature
The dew point temperature for the product gases is
the temperature at which the water in the product
gases would begin to condense when the products
are cooled at constant pressure. The dew point
temperature is equal to the saturation temperature of
the water at its partial pressure in the products.
19
Example:An unknown hydrocarbon fuel, CXHY is reacted with air
such that the dry product gases are 12.1 percent CO2, 3.8 percent O2,
and 0.9 percent CO by volume. What is the average makeup of the
fuel?
We assume 100 kmol (do you have to always assume 100 kmol?) of
dry product gases; then the percent by volume can be interpreted to be
mole numbers. We do not know how much air was supplied or water
formed to get the 100 kmol of dry product gases, but we assume 1
kmol of unknown fuel.
C X HY  A (O2  3.76 N 2 ) 
12.1 CO2  0.9 CO  38
. O2  B H2 O  D N 2
The five unknown coefficients A, B, D, X, and Y are found by
conservation of mass for each species, C, H, O, and N plus one other
equation. Here we use the subtraction method for the nitrogen to
generate the fifth independent equation for the unknowns.
C X HY  A (O2  3.76 N 2 ) 
20
12.1 CO2  0.9 CO  38
. O2  B H2 O  D N 2
The unknown coefficients A, B, D, X, and Y are found by conservation of
mass for each species. Here we assume the remainder of the dry product
gases is nitrogen.
N 2 : D  100  (12.1  0.9  38
. )  83.2
D 83.2
O2 : A    22.13
3.76 3.76
O: A( 2)  (12.1)(2)  (0.9)(1)  ( 38. )(2)  B (1)
B  1154
.
C: 1( X )  12.1(1)  (0.9)(1)
X  13.0
H: 1(Y )  B ( 2)
Y  23.08
The balanced equation is
C13 H23.08  22.13 (O2  3.76 N 2 ) 
21
12.1 CO2  0.9 CO  38
. O2  1154
. H2 O  83.2 N 2
Octane Number:
The property that describes how well petrol will or will not
self-ignite is called the octane number of petrol or just octane.
The higher the octane number of petrol, the less likely it will
self-ignite. Engines with low compression ratios can use petrol
with lower octane numbers, but high-compression engines
must use high-octane petrol to avoid self-ignition and knock.
Common octane numbers (anti-knock index) for petrol used in
cars range from 87 to 95, with higher values available for
special high-performance and racing engines. A 93- octane
petrol is more knock resistant than an 89-octane petrol.
Reciprocating SI aircraft engines usually use low-lead fuels
with octane numbers in the 85 to 100 range.

22
Cetane Number
In a compression ignition engine, self-ignition of the
air-fuel mixture is a necessity. The correct fuel must
be chosen which will self-ignite at the precise proper
time in the engine cycle. It is therefore necessary to
have knowledge and control of the ignition delay time
of the fuel. The property that quantifies this is called
the cetane number. The larger the cetane number, the
shorter is the ID and the quicker the fuel will self-
ignite in the combustion chamber environment. A low
cetane number means the fuel will have a long ID.
Normal cetane number range is about 40 to 60.
23
 One kmol of octane (C8H18) is burned with air that
contains 20 kmol of O2, as shown in Fig. Assuming
the products contain only CO2, H2O, O2, and N2,
determine the mole number of each gas in the products
and the air–fuel ratio for this combustion process.

24
 For air

25
Example
Write the combustion equation for complete
combustion of octane with 120 percent theoretical air
(20 percent excess air).
C8 H18  12
. (12.5) (O2  3.76 N 2 ) 
8 CO2  9 H2 O  (0.2)(12.5) O2  12
. (47) N 2
Note that (1)(12.5)O2 is required for complete
combustion to produce 8 kmol of carbon dioxide
and 9 kmol of water; therefore, (0.2)(12.5)O 2 is
found as excess oxygen in the products.
C8 H18  12
. (12.5) (O2  3.76 N 2 ) 
8 CO2  9 H2 O  2.5 O2  12
. ( 47) N 2
26
Example 15-6
An unknown hydrocarbon fuel, is reacted with air such that the dry
product gases are 12.1 percent CO2, 3.8 percent O2, and 0.9 percent
CO by volume. What is the average makeup of the fuel?
We assume 100 kmol (do you have to always assume 100 kmol?) of
dry product gases; then the percent by volume can be interpreted to be
mole numbers. We do not know how much air was supplied or water
formed to get the 100 kmol of dry product gases, but we assume 1
kmol of unknown fuel.
C X HY  A (O2  3.76 N 2 ) 
12.1 CO2  0.9 CO  38
. O2  B H2 O  D N 2
The five unknown coefficients A, B, D, X, and Y are found by
conservation of mass for each species, C, H, O, and N plus one other
equation. Here we use the subtraction method for the nitrogen to
generate the fifth independent equation for the unknowns.
C X HY  A (O2  3.76 N 2 ) 
27 12.1 CO2  0.9 CO  38. O2  B H2 O  D N 2
O balance gives
O: 12
. (12.5)(2)  0.8(8)(2)  0.2(8)(1)  9(1)  X (2)
X  3.3

Then the balanced equation is

C8 H18  12
. (12.5) (O2  3.76 N 2 ) 
6.4 CO2  16
. CO  9 H2 O  3.3 O2  12
. (47) N 2

Combustion Equation When Product Gas Analysis

Is Known
28
Example 15-4
Propane gas C3H8 is reacted with air such that the dry
product gases are 11.5 percent CO2, 2.7 percent O2,
and 0.7 percent CO by volume. What percent
theoretical air was supplied? What is the dew point
temperature of the products if the product pressure is
100 kPa?
We assume 100 kmol of dry product gases; then the
percent by volume can be interpreted to be mole
numbers. But we do not know how much fuel and air
were supplied or water formed to get the 100 kmol of
dry product gases.
X C3 H8  A (O2  3.76 N 2 ) 
29 115
. CO2  0.7 CO  2.7 O2  B H2 O  A( 3.76) N 2
The unknown coefficients A, B, and X are found by conservation of mass
.for each species C: X (3)  115 . (1)  0.7(1) X  4.07
H: X (8)  B (2) B  16.28
O: A(2)  115. (2)  0.7(1)
 2.7(2)  B (1) A  22.69
N 2 : A(3.76)  85.31
The balanced equation is
4.07 C3 H8  22.69 (O2  3.76 N 2 ) 
115. CO2  0.7 CO  2.7 O2  16.28 H2 O  85.31 N 2

:Second method to find the coefficient A

.Assume the remainder of the 100 kmol of dry product gases is N2

30
kmol N 2  100  (115
.  0.7  2.7)  851
.
Then A is 851.
A  22.65 ( fairly good check )
3.76
These two methods don’t give the same results for A, but they
are close.
What would be the units on the coefficients in the balanced
combustion equation?
Later in the chapter we will determine the energy released by
the combustion process in the form of heat transfer to the
surroundings. To simplify this calculation it is generally better
to write the combustion equation per kmol of fuel. To write the
combustion equation per unit kmol of fuel, divide by 4.07:

C3 H8  557
. (O2  3.76 N 2 ) 
31
2.83 CO2  017
. CO  0.66 O2  4.0 H2 O  20.96 N 2
 The actual air-fuel ratio is
kg air
(5.57)(1  3.76) kmol air 28.97
kmol air
AFactual 
kg fuel
1kmol fuel[3(12)  8(1)]
kmol fuel
kg air
 17.45
kg fuel

32
The theoretical combustion equation is
C3 H8  5 (O2  3.76 N 2 ) 
3 CO2  4.0 H2 O  18.80 N 2
The theoretical air-fuel ratio is
kg air
(5)(1  3.76) kmol air 28.97
kmol air
AFth 
kg fuel
1kmol fuel[3(12)  8(1)]
kmol fuel
kg air
 15.66
kg fuel
The percent theoretical air is
AFactual
Percent theoretical air  100%
AFth
17.45
 100  111%
33
15.66
 or N O2 actual
Percent theoretical air  100%
N O2 th
557
.
 100  111%
The percent excess air is 5
AFactual  AFth
Percent excess air  100%
AFth
17.45  15.66
 100  11%
15.66
Dew Point Temperature
The dew point temperature for the product gases is the
temperature at which the water in the product gases would
begin to condense when the products are cooled at constant
pressure. The dew point temperature is equal to the saturation
temperature of the water at its partial pressure in the products.
34
 Tdp  Tsat at Pv  yv Pproducts
O2  376
. N2 ) 
N water
017
. CO  0.66 O2  4.0 H2 O  20.96 N 2 yv 
 Ne
products

Example 15-5: Determine dew point temperature of the

.products for Example 15-4 4
yv   0.1398
2.83  0.17  0.66  4  20.96
Pv  yv Pproducts  0.1398(100 kPa )
 13.98 kPa
Tdp  Tsat at13.98 kPa
=52.31oC
What would happen if the product gases are cooled to 100oC or
?to 30oC
35
Example 1:
A gas consists of 70% propane (C3H8) and 30% butane
(C4H10) by volume. Find:
(a)The stoichiometric air-to-fuel ratio and
(b) The percentage excess air present if a dry
analysis of the combustion products shows 9% CO2
(assume complete combustion).
Solution:
The combustion reactions for propane and butane are:
C3 H 8  5 O2  18.8 N 2  3 CO2  4 H 2O  18.8 N 2

C4 H10  6.5 O2  24.5 N 2  4 CO2  5 H 2O  24.5 N 2

36
• (a)Stoichiometric Air Requirement
On the basis of 1 volume of the fuel gas, the
propane content requires
0.7 × (5 + 18.8) = 16.7 vols air
and the butane requires
0.3 × (6.5 + 24.5) = 6.3 vols air
Hence the stoichiometric air-to-fuel ratio is 23:1.

37
(b) Excess Air
The combustion products (dry) will contain
(0.7 × 3) + (0.3 × 4) = 3.3 vols CO2
(0.7 × 18.8) + (0.3 × 24.5) = 20.5 vols N 2
plus υ volumes excess air, giving a total volume of
products of (23.8 + υ ).
Given that the measured CO2 in the products is 9%,
we can write: 9 3.3

100 (23.8   )
hence υ = 12.87 vols
The stoichiometric air requirement is 23 vols so the
12.87
percentage excess air is:  100%  55.9%
23 38