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Thermodynamics: An Engineering Approach

Seventh Edition in SI Units
Yunus A. Cengel, Michael A. Boles
McGraw-Hill, 2011

Lecture II
CHEMICAL REACTIONS -
COMBUSTION

COMBUSTION
• Combustion or burning is the sequence of exothermic chemical reactions between a fuel
and an oxidant accompanied by the production of heat and conversion of chemical
species.
• The release of heat can result in the production of light in the form of either a glow or a
flame.
• Fuels of interest often include organic compounds (especially hydrocarbons) in the gas,
liquid or solid phase.
• In a complete combustion reaction, a compound reacts with an oxidizing element, such as
oxygen or fluorine, and the products are compounds of each element in the fuel with the
oxidizing element.
1
• For example:
CH4 + 2 O2 → CO2 + 2 H2O + energy
A simple example can be seen in the combustion of hydrogen and oxygen, which is a
commonly used reaction in rocket engines:
2 H2 + O2 → 2 H2O(g) + heat
The result is water vapor.
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COMPLETE VS INCOMPLETE COMBUSTION

• Complete combustion is almost impossible to achieve.
• In reality, as actual combustion reactions come to equilibrium, a wide variety of
major and minor species will be present such as carbon monoxide and pure
carbon (soot or ash).
• Additionally, any combustion in atmospheric air, which is 79% nitrogen on
volume basis, will also create several forms of nitrogen oxides
• A combustion process is incomplete if the combustion products contain any
unburned fuel or components such as C, H2, CO, or OH.
• In incomplete combustion, the reactant burns in oxygen, producing a limited
number of products.

COMPLETE VS INCOMPLETE COMBUSTION CONTD.

• When elements are burned, the products are primarily the most common
oxides.
• When a hydrocarbon burns in oxygen, the reaction will only yield carbon dioxide
and water.
• Carbon will yield carbon dioxide, nitrogen will yield nitrogen dioxide, sulfur will
yield sulfur dioxide, and iron will yield iron(III) oxide.
• Combustion is not necessarily favorable to the maximum degree of oxidation
and it can be temperature-dependent.
2
• For example, sulfur trioxide is not produced quantitatively in combustion of
sulfur. Nitrogen oxides start to form above 1,540 °C and more nitrogen oxides
are produced at higher temperatures.

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COMPLETE VS INCOMPLETE COMBUSTION CONTD.

• Below this temperature, molecular nitrogen (N2) is favored. It is also a function
of oxygen excess.
• In most industrial applications and in fires, air is the source of oxygen (O2). In
air, each mole of oxygen is mixed with approximately 3.76 mole of nitrogen.
• Nitrogen does not take part in combustion, but at high temperatures, some
nitrogen will be converted to NOx, usually between 0.002% and 1%.
• Furthermore, when there is any incomplete combustion, some of carbon is
converted to carbon monoxide
• More complete set of equations for combustion of methane in air is therefore:
CH4 + 2 O2 → CO2 + 2 H2O
2 CH4 + 3 O2 → 2 CO + 4 H2O
N2 + O2 → 2 NO
N2 + 2 O2 → 2 NO2
5

COMPLETE VS INCOMPLETE COMBUSTION CONTD.

Incomplete combustion may be caused by the following:
• Insufficient oxygen: Incomplete combustion will only occur when there is
not enough oxygen to allow the fuel to react completely to produce carbon
dioxide and water.
• It also happens when the combustion is quenched by a heat sink such as a
solid surface or flame trap.
• Insufficient mixing: Incomplete combustion occurs even when more
oxygen is present in the combustion chamber than is needed for complete 3

combustion.
• This may be attributed to insufficient mixing in the combustion chamber
during the limited time that the fuel and the oxygen are in contact.

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COMPLETE VS INCOMPLETE COMBUSTION CONTD.

• Dissociation: Another cause of incomplete combustion is dissociation (the
splitting of a molecule into smaller molecules, atoms, or ions, especially by a
reversible process), which becomes important at high temperatures.
• For most fuels, such as diesel oil, coal or wood, pyrolysis occurs before
combustion.
• In incomplete combustion, products of pyrolysis remain unburnt and
contaminate the smoke with noxious particulate matter and gases.
• Partially oxidized compounds are also a concern; partial oxidation of ethanol
can produce harmful acetaldehyde, and carbon can produce toxic carbon
monoxide

The combustion process is a chemical reaction whereby fuel is oxidized and energy is released.

Fuels are usually composed of some compound or mixture containing carbon, C, and hydrogen, H2.

Examples of hydrocarbon fuels are: CH4 (Methane), C8H18 (Octane)

4
Coal (Mixture of C, H2, S, O2, N2 and non-combustibles)

Initially, we shall consider only those reactions that go to completion. The components prior to the
reaction are called reactants and the components after the reaction are called products.

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R e a c ta n ts  P r o d u c ts
For complete or stoichiometric combustion, all carbon is burned to carbon dioxide (CO2) and all
hydrogen is converted into water (H2O). These two complete combustion reactions are as follows:
C  O2  C O2
1
H 2  O2  H 2O
2
Example 15-1

A complete combustion of octane in oxygen is represented by the balanced combustion equation. The
balanced combustion equation is obtained by making sure we have the same number of atoms of each
element on both sides of the equation. That is, we make sure the mass is conserved.

C 8 H 18  A O 2  B C O 2  D H 2 O
Note we often can balance the C and H for complete combustion by inspection.
C 8 H 18  A O 2  8 C O 2  9 H 2 O

The amount of oxygen is found from the oxygen balance. It is better to conserve species on a monatomic
basis as shown for the oxygen balance.

O: A ( 2 )  8 ( 2 )  9 (1)
A  1 2 .5

C 8 H 1 8  1 2 .5 O 2  8 C O 2  9 H 2 O
Note: Mole numbers are not conserved, but we have conserved the mass on a total basis as well as a
specie basis. Also, 12.5 kmol of O2 are used to form the CO2 and
H2O. If 15 kmol of O2 were supplied to the process, 2.5 kmol of O2 would be excess oxygen in the
5
products.

The complete combustion process is also called the stoichiometric combustion, and all coefficients are
called the stoichiometric coefficients.

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In most combustion processes, oxygen is supplied in the form of air rather than pure oxygen.

Air is assumed to be 21 percent oxygen and 79 percent nitrogen on a volume basis. For ideal
gas mixtures, percent by volume is equal to percent by moles. Thus, for each mole of oxygen
in air, there exists 79/21 = 3.76 moles of nitrogen. Therefore, complete or theoretical
combustion of octane with air can be written as

C 8 H 18  12 . 5 ( O 2  3 . 76 N 2 ) 
8 CO 2  9 H 2 O  47 N 2

11

Air-Fuel Ratio

Since the total moles of a mixture are equal to the sum of moles of each component, there are 12.5(1 +
3.76) = 59.5 moles of air required for each mole of fuel for the complete combustion process.

Often complete combustion of the fuel will not occur unless there is an excess of air present greater than
just the theoretical air required for complete combustion.

To determine the amount of excess air supplied for a combustion process, let us define the air-fuel ratio
AF as
k m o l a ir
AF 
k m o l fu e l 6

Thus, for the above example, the theoretical air-fuel ratio is

1 2 .5 ( 1  3 .7 6 ) k m o l a ir
A F th   5 9 .5
1 k m o l fu e l

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On a mass basis, the theoretical air-fuel ratio is

k g a ir
2 8 .9 7
k m o l a ir k m o l a ir
A F th  5 9 .5
k m o l fu e l [ 8 ( 1 2 )  1 8 ( 1 ) ] k g fu e l
k m o l fu e l
k g a ir
 1 5 .1 2
k g fu e l

Percent Theoretical and Percent Excess Air

In most cases, more than theoretical air is supplied to ensure complete combustion and to reduce or
eliminate carbon monoxide (CO) from the products of combustion. The amount of excess air is usually
expressed as percent theoretical air and percent excess air.
AF actual
Percent theoretical air  100 %
AF th
AF actual  AF th
Percent excess air  100 %
AF th
13

These results may be expressed in terms of the moles of oxygen only as

N O 2 a c tu a l
P e r c e n t th e o r e tic a l a ir  100%
N O 2 th

N O 2 a c tu a l  N O 2 th
P e r c e n t e x c e s s a ir  100%
N O 2 th
Example 15-2 – Excess Air

Write the combustion equation for complete combustion of octane with 120 percent theoretical air (20
percent excess air).
C 8 H 1 8  1.2 ( 1 2 .5 ) ( O 2  3 .7 6 N 2 ) 
7
8 C O 2  9 H 2 O  ( 0 .2 ) ( 1 2 .5 ) O 2  1.2 ( 4 7 ) 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)O2 is found as excess oxygen in the products.
C 8 H 1 8  1. 2 ( 1 2 .5 ) ( O 2  3 .7 6 N 2 ) 
8 C O 2  9 H 2 O  2 .5 O 2  1.2 ( 4 7 ) N 2
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Second method to balance the equation for excess air (see the explanation of this technique in the text) is:

C 8 H 1 8  1.2 A t h ( O 2  3 .7 6 N 2 ) 
8 C O 2  9 H 2 O  0 .2 A t h O 2  1.2 A th ( 3 .7 6 ) N 2

O: 1.2 A th ( 2 )  8 ( 2 )  9 ( 1 )  0 .2 A t h ( 2 )
A th  1 2 .5
NOTE: THIS METHOD WORKS ONLY FOR COMPLETE COMBUSTION!!!

WHEN PERCENT OR EXCESS THEROETICAL AIR IS SUPPLIED TO AN

INCOMPLETE COMBUSTION PROCESS, THE AMOUNT OF SUPPLIED O2 (1.2ATH
IN THIS EXAMPLE) NOT USED FOR FORMING CO2 MUST BE ACCOUNTED FOR
IN THE EXCESS O2 IN THE PODUCTS.

15

Incomplete Combustion with Known Percent Theoretical Air

Example 15-3

Consider combustion of C8H18 with 120 % theoretical air where 80 % C in the fuel goes into CO2.

Theoretical C 8 H 1 8  Ath O 2  8 C O 2  9 H 2 O
Combustion
t h e o r e tic a l O : A th ( 2 )  8 ( 2 )  9 (1)
A t h  1 2 .5
8
The chemical reaction equation for incomplete Combustion with excess theoretical air and X
amount of O2 in products is
C 8 H 1 8  1.2 ( 1 2 .5 ) ( O 2  3 .7 6 N 2 ) 
0 .8 ( 8 ) C O 2  0 .2 ( 8 ) C O  9 H 2 O  X O 2  1.2 ( 4 7 ) N 2

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O balance gives
O: 1.2 ( 1 2 .5 ) ( 2 )  0 .8 ( 8 ) ( 2 )  0 .2 ( 8 ) ( 1 )  9 ( 1 )  X ( 2 )
X  3 .3
Why is X > 2.5, the amount of O2 in the previous complete combustion example?

Then the balanced equation is

C 8 H 1 8  1 .2 ( 1 2 .5 ) ( O 2  3 .7 6 N 2 ) 
6 .4 C O 2  1.6 C O  9 H 2 O  3 . 3 O 2  1.2 ( 4 7 ) N 2

Combustion Equation When Product Gas Analysis Is Known

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.

17

X C 3 H 8  A ( O 2  3 .7 6 N 2 ) 
1 1.5 C O 2  0 .7 C O  2 .7 O 2  B H 2 O  A ( 3 .7 6 ) N 2

The unknown coefficients A, B, and X are found by conservation of mass for each species.
C : X ( 3 )  1 1.5 ( 1 )  0 .7 ( 1 ) X  4 .0 7
H : X (8 )  B ( 2 ) B  1 6 .2 8
O : A ( 2 )  1 1.5 ( 2 )  0 .7 ( 1 )
 2 .7 ( 2 )  B ( 1 ) A  2 2 .6 9
N 2 : A ( 3 .7 6 )  8 5 . 3 1
The balanced equation is
4 .0 7 C 3 H 8  2 2 . 6 9 ( O 2  3 . 7 6 N 2 )  9

1 1.5 C O 2  0 .7 C O  2 .7 O 2  1 6 .2 8 H 2 O  8 5 .3 1 N 2
Second method to find the coefficient A:
Assume the remainder of the 100 kmol of dry product gases is N2.
km ol N 2  1 0 0  ( 1 1.5  0 .7  2 .7 )  8 5 .1
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Then A is
8 5 .1
A   2 2 .6 5 ( fa irly g o o d c h e c k )
3 .7 6

These two methods don’t give the same results for A, but they are close.

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:

C 3 H 8  5 .5 7 ( O 2  3 .7 6 N 2 ) 
2 .8 3 C O 2  0 .1 7 C O  0 .6 6 O 2  4 .0 H 2 O  2 0 .9 6 N 2
The actual air-fuel ratio is
k g a ir
( 5.5 7 )( 1  3 .7 6 ) k m o l a ir 2 8 .9 7
k m o l a ir
A Fa ctu a l 
k g fu e l
1 k m o l fu e l [ 3 ( 1 2 )  8 ( 1 ) ]
k m o l fu e l
k g a ir
 1 7 .4 5
k g fu e l 19

The theoretical combustion equation is

C 3 H 8  5 ( O 2  3 .7 6 N 2 ) 
3 C O 2  4 .0 H 2 O  1 8 .8 0 N 2
The theoretical air-fuel ratio is
k g a ir
(5 )( 1  3 .7 6 ) k m o l a ir 2 8 . 9 7
k m o l a ir
A F th 
k g fu e l
1 k m o l fu e l [ 3 ( 1 2 )  8 ( 1 ) ]
k m o l fu e l
k g a ir
 1 5 .6 6
k g fu e l
The percent theoretical air is
10
A F a c tu a l
P e r c e n t th e o r e tic a l a ir  100%
A F th
1 7 .4 5
 100  111%
1 5 .6 6

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or
N O 2 a c tu a l
P e r c e n t th e o r e tic a l a ir  100%
N O 2 th

5 .5 7
 100  111%
5
The percent excess air is
A F a c tu a l  A F th
P e r c e n t e x c e s s a ir  100%
A F th
1 7 .4 5  1 5 .6 6
 100  11%
1 5 .6 6
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.

21

T d p  T s a t a t Pv  y v Pp ro d u c ts
N w a te r
yv 
 N
p ro d u c ts
e

Example 15-5

Determine dew point temperature of the products for Example 15-4.

4
yv   0 .1 3 9 8
2 .8 3  0 .1 7  0 .6 6  4  2 0 .9 6
Pv  y v Pp r o d u c ts  0 .1 3 9 8 (1 0 0 k P a )
11
 1 3 .9 8 k P a
Tdp  T s a t a t 1 3 .9 8 k P a
= 5 2 .3 1 o C
What would happen if the product gases are cooled to 100oC or to 30oC?

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Example 15-6

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 H Y  A ( O 2  3 .7 6 N 2 ) 
1 2 .1 C O 2  0 . 9 C O  3 .8 O 2  B H 2 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 H Y  A ( O 2  3 .7 6 N 2 ) 
1 2 .1 C O 2  0 .9 C O  3 .8 O 2  B H 2 O  D N 2

23

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  1 0 0  ( 1 2 .1  0 .9  3 .8 )  8 3 .2
D 8 3 .2
O2: A 
N2   2 2 .1 3
3 .7 6 3 .7 6
O : A ( 2 )  ( 1 2 .1 ) ( 2 )  ( 0 .9 ) ( 1 )  ( 3 .8 ) ( 2 )  B ( 1 )
B  1 1.5 4
C : 1 ( X )  1 2 .1 ( 1 )  ( 0 .9 ) ( 1 )
X  1 3 .0
H : 1( Y )  B ( 2 )
12
Y  2 3 .0 8
The balanced equation is
C 1 3 H 2 3 . 0 8  2 2 .1 3 ( O 2  3 .7 6 N 2 ) 
1 2 .1 C O 2  0 .9 C O  3 .8 O 2  1 1.5 4 H 2 O  8 3 .2 N 2

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ENTHALPY OF FORMATION
When a compound is formed from its elements (e.g., methane, CH4, from C and H2), heat transfer occurs.
When heat is given off, the reaction is called exothermic. When heat is required, the reaction is called
endothermic. Consider the following.

The reaction equation is

C  2H2  CH4
The conservation of energy for a steady-flow combustion process is
E in  E o u t
Q n e t  H R e a c ta n ts  H P r o d u c ts

Q n e t  H P r o d u c ts  H R e a c ta n ts 25

Q net   N e he 
P ro d u c t s
 N i hi
R e a c ta n ts

Q n et  1h C H 4  (1h C  2 h H 2 )
A common reference state for the enthalpies of all reacting components is established as
The enthalpy of the elements or their stable compounds is defined to be ZERO at 25oC
(298 K) and 1 atm (or 0.1 MPa).
Q n e t  1h C H 4  (1( 0 )  2 ( 0 ) )
 hCH 4
This heat transfer is called the enthalpy of formation for methane, h fo. The superscript (o) 13
implies the 1 atm pressure value and the subscript (f) implies 25°C data, h fo is given in Table A-26.

During the formation of methane from the elements at 298 K, 0.1 MPa, heat is given off (an
exothermic reaction) such that
kJ
Q n e t  h fo C H   7 4 ,8 5 0
4 k m o lC H 4
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The enthalpy of formation h fo is tabulated for typical compounds. The enthalpy of formation of the
elements in their stable form is taken as zero. The enthalpy of formation of the elements found naturally
as diatomic elements, such as nitrogen, oxygen, and hydrogen, is defined to be zero. The enthalpies of
formation for several combustion components are given in the following table.
Substance Formula M h fo kJ/kmol
Air 28.97 0

Oxygen O2 32 0
Nitrogen N2 28 0
Carbon dioxide CO2 44 -393,520
Carbon monoxide CO 28 -110,530
Water (vapor) H2Ovap 18 -241,820
Water (liquid) H2Oliq 18 -285,830
Methane CH4 16 -74,850
Acetylene C2H2 26 +226,730
Ethane C2H6 30 -84,680
Propane C3H8 44 -103,850
Butane C4H10 58 -126,150
Octane (vapor) C8H18 114 -208,450
Dodecane C12H26 170 -291,010 27

The enthalpies are calculated relative to a common base or reference called the enthalpy of formation.
The enthalpy of formation is the heat transfer required to form the compound from its elements at
25oC (77 F) or 298 K (537 R), 1 atm. The enthalpy at any other temperature is given as
h  h fo  ( h T  h o )
Here the term h o is the enthalpy of any component at 298 K. The enthalpies at the temperatures T and
298 K can be found in Tables A-18 through A-25. If tables are not available, the enthalpy difference
due to the temperature difference can be calculated from

Based on the classical sign convention, the net heat transfer to the reacting system is
Q net  H P  H R 14

  N e [ h fo  ( h T  h o ) ] e 
P ro d u c ts
 N i [ h fo  ( h T  h o ) ] i
R e a c ta n ts

In an actual combustion process, is the value of Qnet positive or negative?

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Example 15-7

Butane gas C4H10 is burned in theoretical air as shown below. Find the net heat transfer per kmol of
fuel.

Balanced combustion equation:

C 4 H 1 0  6 .5 ( O 2  3 .7 6 N 2 ) 
4 C O 2  5 H 2 O  2 4 .4 4 N 2
The steady-flow heat transfer is
Q net  H P  H R
  N e [ h fo  ( h T  h o ) ] e 
P ro d u c ts
 N i [ h fo  ( h T  h o ) ] i
R e a c ta n ts

29

Reactants: TR = 298 K
Comp Ni h fo hT h o
N i [ h fo  ( h T  h o )] i
kmol/kmol fuel kJ/kmol kJ/kmol kJ/kmol kJ/kmol fuel

C4H10 1 -126,150 -- -- -126,150

O2 6.5 0 8,682 8,682 0
N2 24.44 0 8,669 8,669 0

H R   N i [ h fo  ( h T  h o ) ] i
R e a c ta n t s

kJ
  1 2 6 ,1 5 0
Products: TP = 1000 K k m o l C 4 H 10

Comp Ne h fo hT h o
N e [ h fo  ( h T  h o )] e
15
kmol/kmol fuel kJ/kmol kJ/kmol kJ/kmol kJ/kmol fuel

CO2 4 -393,520 42,769 9,364 -1,440,460

H2O 5 -241,820 35,882 9,904 -1,079,210
N2 24.44 0 30,129 8,669 +524,482

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H P   N e [ h fo  ( h T  h o ) ] e
P r o d u c ts
Q net  H P  H R

kJ kJ
  1 ,8 6 9 , 0 3 8
  1 , 9 9 5 ,1 8 8 k m o l C 4 H 10
k m o l C 4 H 10

Adiabatic Flame Temperature

The temperature of the products of combustion

when the process takes place adiabatically is
called the adiabatic flame temperature.

Shown here is the view of the riser tubes during

the combustion process inside a steam power
plant boiler.
Photo courtesy of Progress Energy Carolinas,
Inc.

31

Example 15-8

Liquid octane C8H18(liq) is burned with 400 percent theoretical air. Find the adiabatic flame temperature
when the reactants enter at 298 K, 0.1 MPa, and the products leave at 0.1MPa.

16

The combustion equation is

C 8 H 1 8  4 ( 1 2 .5 ) ( O 2  3 .7 6 N 2 ) 
8 C O 2  3 7 .5 O 2  9 H 2 O  1 8 8 N 2
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The steady-flow heat transfer is

Q net  H P  HR
  N e [ h fo  ( h T  h o )] e 
P ro d u c ts
 N i [ h fo  ( h T  h o ) ] i
R e a c ta n ts

 0 ( A d ia b a tic C o m b u s tio n )

Thus, HP = HR for adiabatic combustion. We need to solve this equation for TP.

Since the temperature of the reactants is 298 K, ( h T  h )oi = 0,

H R   N i h fo i
R e a c ta n ts

 1 (  2 4 9 , 9 5 0 )  4 ( 1 2 .5 ) ( 0 )  4 ( 1 2 .5 ) ( 3 .7 6 ) ( 0 )
kJ
  2 4 9 ,9 5 0
k m o l C 4 H 10
33

Since the products are at the adiabatic flame temperature, TP > 298 K
H P  
P r o d u c ts
N e [ h fo  ( h T P  h o ) ] e

 8 (  3 9 3 , 5 2 0  hT P  9 3 6 4 ) C O 2
 9 (  2 4 1, 8 2 0  h T P  9 9 0 4 ) H 2 O
 3 7 .5 ( 0  h T P  8 6 8 2 ) O 2
 1 8 8 ( 0  hT P  8 6 6 9 ) N 2
 (  7 , 4 4 3 , 8 4 5  8 hT P , C O 2  9 hTP , H 2 O
17
kJ
 3 7 .5 h T P , O 2  1 8 8 h T P , N 2 )
k m o l C 4 H 10
Thus, setting HP = HR yields

 N e h T P , e  8 h T P , C O 2  9 h T P , H 2 O  3 7 .5 h T P , O 2  1 8 8 h T P , N 2
P r o d u c ts

 7 ,1 9 3 ,8 9 5 34
 1 /2 0 /2 0 2 4

To estimate TP, assume all products behave like N2 and estimate the adiabatic flame
temperature from the nitrogen data, Table A-18.
2 4 2 .5 h T P , N 2  7 ,1 9 3 ,8 9 5
kJ
h T P , N 2  2 9 , 6 6 5 .5
km ol N 2

Tp  985 K
Because CO2 and H2O are triatomic gases and have specific heats greater than diatomic gases, the
actual temperature will be somewhat less than 985 K. Try TP = 960 K and 970K.
Ne h960 K h970 K

CO2 8 40,607 41,145

H2O 9 34,274 34,653
Interpolation gives: TP = 962 K. O2 37.5 29,991 30,345
N2 188 28,826 29,151
7,177,572 7,259,362
 N e hTP ,e
P r o d u ts
35

Example 15-9

Liquid octane C8H18(liq) is burned with excess air. The adiabatic flame temperature is 960 K when the
reactants enter at 298 K, 0.1 MPa, and the products leave at 0.1MPa. What percent excess air is supplied?

18
Let A be the excess air; then combustion equation is
C 8 H 1 8  ( 1  A ) ( 1 2 .5 ) ( O 2  3 . 7 6 N 2 ) 
8 C O 2  1 2 .5 A O 2  9 H 2 O  ( 1  A ) ( 1 2 .5 ) ( 3 .7 6 ) N 2

36
 1 /2 0 /2 0 2 4

The steady-flow heat transfer is

Q net  H P  HR
  N e [ h fo  ( h T  h o ) ] e 
P ro d u c ts
 N i [ h fo  ( h T  h o ) ] i
R e a c ta n ts

 0 ( A d ia b a tic c o m b u s tio n )

Here, since the temperatures are known, the values of h T P are known. The product gas mole numbers
are unknown but are functions of the amount of excess air, A. The energy balance can be solved for A.
A  3
Thus, 300 percent excess, or 400 percent theoretical, air is supplied.
Example 15-10

Tabulate the adiabatic flame temperature as a function of excess air for the complete combustion of C3H8
when the fuel enters the steady-flow reaction chamber at 298 K and the air enters at 400 K.

The combustion equation is

C 3 H 8  ( 1  A ) ( 5 ) ( O 2  3 .7 6 N 2 ) 
3 C O 2  5 A O 2  4 H 2 O  ( 1  A ) ( 5 ) ( 3 .7 6 ) N 2
37

where A is the value of excess air in decimal form.

The steady-flow heat transfer is

Q n et  H P  HR
  N e [ h fo  ( h T  h o ) ] e   N i [ h fo  ( h T  h o ) ] i
P r o d u c ts R e a c ta n ts

 0 ( A d ia b a tic c o m b u s tio n )
Percent Excess Air Adiabatic Flame Temp. K

0 2459.3
19
20 2191.9

50 1902.5

100 1587.1

217 1200

38
 1 /2 0 /2 0 2 4

Enthalpy of Reaction and Enthalpy of Combustion

When the products and reactants are at the same temperature, the enthalpy of reaction hR, is the
difference in their enthalpies. When the combustion is assumed to be complete with theoretical air
supplied the enthalpy of reaction is called the enthalpy of combustion hC. The enthalpy of combustion
can be calculated at any value of the temperature, but it is usually determined at 25oC or 298 K.
hC  H P  H R w h e n TP  TR  2 5 o C  2 9 8 K
  N e h fo e   N i h fo i
Heating Value P ro d u c t s R e a c ta n t s

The heating value, HV, of a fuel is the absolute value of the enthalpy of combustion or just the negative
of the enthalpy of combustion.
H V  hC
The lower heating value, LHV, is the heating value when water appears as a gas in the products.

L H V  h C   h C w ith H 2 O g a s in p r o d u c ts
39

The lower heating value is often used as the amount of energy per kmol of fuel supplied to the gas turbine
engine.

The higher heating value, HHV, is the heating value when water appears as a liquid in the products.

H H V  h C   h C w ith H 2 O liq u id in p r o d u c ts

The higher heating value is often used as the amount of energy per kmol of fuel supplied to the steam
power cycle.

See Table A-27 for the heating values of fuels at 25oC. Note that the heating values are listed with units
of kJ/kg of fuel. We multiply the listed heating value by the molar mass of the fuel to determine the 20
heating value in units of kJ/kmol of fuel.

The higher and lower heating values are related by the amount of water formed during the combustion
process and the enthalpy of vaporization of water at the temperature.
HHV  LHV  N H 2O h fg H 2 O
40
 1 /2 0 /2 0 2 4

Example 15-11

The enthalpy of combustion of gaseous octane C8H18 at 25oC with liquid water in the products is -
5,500,842 kJ/kmol. Find the lower heating value of liquid octane.
L H V C 8 H 18 gas  H H V C 8 H 18 gas
 N H 2O h fg H 2 O
kJ km o l H 2O kJ
 5, 5 00, 8 42 9 (44, 010)
k m o l C 8 H 18 k m o l C 8 H 18 km o l H 2O
kJ
 5,1 0 4 , 7 5 2
k m o l C 8 H 18
L H V C 8 H 1 8 li q  L H V C 8 H 1 8 g a s  h fg C 8 H 1 8
kJ
 ( 5 , 1 0 4 7 5 2  4 1, 3 8 2 )
k m o l C 8 H 18
kJ
 5, 0 6 3, 3 7 0
k m o l C 8 H 1 8 l iq
Can you explain why LHVliq< LHVgas?

41

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