Me 303 CH12

CHAPTER 12: CHEMICAL REACTIONS (COMBUSTIONS)
Introduction:
In this chapter, the combustion process of hydrocarbon fuels will be considered.
Fuel: Any material which can be burned to release energy is called as fuel. Most familiar fuels are
hydrocarbon fuels (CnHm) such as coal, gasoline, diseloil, fueloil, natural gas, LPG, LNG, etc.
Chemical Reaction: Many thermodynamic problems involve chemical reactions. Among the most
familiar of these is the combustion of hydrocarbon fuels, for this process is utilized in most of power
generating devices. (Combustion=Chemical Reaction)
12.1 Fuels:
Most fuels fall into one of the three categories: 1. COALS (C+O+H+N+S)
2. LIQUID HYDROCARBONS
3. GASEOUS HYDROCARBONS
Coal includes Carbon, Oxygen, Hydrogen, Nitrogen, Sulfur, moisture, and Ash.
Liquid hydrocarbons are mixtures of many different liquid hydrocarbons, but they are chemically
represented with the most dominant component. For example:
Gasoline is treated as Octane (C8H18)
Diesel fuel is treated as Dodecane (C12H26)
Methyl alcohol is treated as Methanol (CH3OH)
Gaseous hydrocarbon (i.e., Natural Gas) is a mixture of methane and smaller amounts of some
other gases. It is sometimes treated as Methane (CH4) for simplicity of analysis.
LPG: Liquified Petrolleum Gas & LNG: Liquified Natural Gas
University of Gaziantep / Mechanical Engineering Department / Prof. Dr. M.Y. GUNDOGDU : ME 303 Thermodynamics II
Fossil Fuels
Remains of vegetations deposit of past
geological ages after subjected to
biochemical reactions, high pressure and
temperature.
Categories:
- Coal
- Liquid hydrocarbon
- Gaseous
hydrocarbon
Hydrocarbon Fuels
One of the most commonly available forms of fuel
is hydrocarbon fuels, which has carbon and
hydrogen as the primary constituents.
The hydrocarbon fuels exits in different phases

such as liquid like gasoline, solid like coal, and
gas like natural gas.
Some of the common hydrocarbon fuels are
gasoline or octane, diesel, methyl alcohol or

methanol, ethyl alcohol or ethanol etc.
Liquid or Gaseous Hydrocarbons

Normally a mixture of many different
hydrocarbons.
- Gasoline consists of 40 different
hydrocarbons
Coal Composition
Coal is mainly composed of
carbon, sulfur, oxygen and
hydrogen with varying
compositions.
Composition changes from

location to location.
Analysis given on a mass

basis, relative moisture
content, volatile matter,
fixed carbon and ash.
Composition of coals from

western USA - % mass
H: 3.5%
C: 48.6%
S: 0.5%
N: 0.7%
O: 12.0%
Ash: 5.8%
Family of Hydrocarbons
Isomers
Two hydrocarbons with the same number of carbon and
hydrogen atoms and different structures.
Family identified by Suffix:
Paraffin Family: - ane ( as propane or Octane)
Olefin Family:
- ylene or -ene (propene and

Octene)
Diolefin Family: - diene (as butadiene)
Napthene Family: Prefix with cyclo (cyclopentane)
Has the same chemical formula as the olefin family, but
has a ring rather than chain structure)
Liquid Hydrocarbons
Most liquid hydrocarbons are derived from

crude oil by distillation or Cracking Processes:
Gasoline, Kerosene, diesel etc.
Each type is characterized by its distillation

curve.
The distillation curve is obtained by slowly

heating the crude so that it vaporizes and
condenses.
The more volatile component is vaporized first.
Gaseous Hydrocarbons
Sources:
1. Natural gas wells
2. Chemical manufacturing processes
Major constituents: Natural gas consists of methane, carbon dioxide,
hydrogen, nitrogen and oxygen with varying composition.
Typical Composition:
Methane: 93.9%
Ethane: 3.6%
Propane: 1.2%
Butanes Plus: 1.3%
Present effort is to produce gaseous fuel or liquid hydrocarbons fuel
from coal, Oil Shales and Tar sands
Usually Hydrocarbons or Hydrogen in Air are used

Other fuels include: CO, NH3, CS2, H2S,
If you use an oxidizer other than air, there is a host of new fuels that can
be used (rocket fuels)
Why hydrocarbons?
Many are liquids - high density, easy to transport
Relatively non-toxic fuel & combustion products
Relatively low explosion hazard
Why Air? (Air = 0.21O2 + 0.79N2)
Its there and FREE! (although much $$ spent to reduce air pollution)
Some Characteristics of Hydrocarbon Families:

FAMILY
STRUCTURE
SATURATION
CnH2n+2
Chain
Yes
Olefin
CnH2n
Chain
No
Diolefin
CnH2n-2
Chain
No
Naphthene
CnH2n
Ring
Yes
Aromatic
Benzene
CnH2n-6
Ring
No
Naphthalene
CnH2n-12
Ring
No
Paraffin(Alkanes)
CFORMULA

Diolefin -CnH2n-2 Contains one or more C=C bond/Chain
Propane(C3H8)
Butadiene(C4H6)
Napthenes -CnH2n / Rings
H
|
H
|
Olefins- CnH2n, Contains one or more C=C bond/Chain
C=C
H
Ethylene(C2H4)
H
H
H
H
|
C=C-C
H
H
Isomers
H-C-C-H
H
Propene(C3H6)
H
|
Ethane(C2H6)
H H H H
| |
|
|
C=C-C=C
H-C-C-C-H
H
|
Methane(CH4)
H
|
H H
| |
H-C-C-H
H
|
H
|
H
|
H
|
H
|
H
|
H-C-H
H
|
Paraffin (Alkanes) - CnH2n+2
Cyclopropane
(not very stable -lots of
strain in C-C bonds)
Acetylenes - Contains one or more CC bond

H - C C - H Acetylene (very reactive)!

Aromatics - contains one or more six-sided ring structures
H
Benzene
H
H
|
C
C
Hydrogen
H-H
C
H
|
Alcohols - contains one or more -OH groups
Carbon Monoxide C = O
H
Ammonia
H-N
H H
|
|
H - C - C - O H Ethanol
H
|
H
|
H
|
H - C -O H Methanol
More Fuels
H
|
Other Oxygenates
as Fuels or Additives
Ethers ignition improvers for diesels
Dimethylether (DME) proposed as a diesel fuel
(CH3)2O
Methyl tertiary butyl ether (MTBE)
(CH3)3COCH3 Octane improvement in
gasoline engines
Problems: Production of formaldehyde (CH2OH), ground
water, CO reduction, particulate reduction issues
Hydrocarbon
Fuels from
Crude Oil are
Derived from
Distillation
and Cracking
Processes
T
e
m
p
e
r
a
t
u
r
e
C
First
Drop
End
Point
Per Cent Recovered

12.2 The Combustion Process:
Combustion: A chemical reaction during which a fuel is oxidized and a large quantity of energy is
released, is called as COMBUSTION.
The used oxidizer in combustion processes is generally air, since it is free and readily available
in atmosphere. The pure oxygen O2 is also used as an oxidizer in some applications such as
cutting and welding where air can not be used (in space, under water).
1 kmol or volume of Atmospheric Air (actual)
20.9% O2
1 kmol or volume of Atmospheric Air (assumed)
78.1% N2
21% O2
0.9% Argon
79% N2
Small Amounts-CO,CO2, He, H2, H2O
1 kmol air = 0.21 kmol O2 + 0.79 kmol N2

4.76 kmol air = 1 kmol O2 + 3.76 kmol N2
0.79/0.21
During a combustion process; the components which exist before the reaction are called as
REACTANTS and the components which exist after the reaction are called as PRODUCTS.
Reactants
Combustion
Chamber
C O2 CO2
Products
For ex.: 1 kmol of C atom
reacts with 1 kmol of Oxygen
to form 1 kmol of Carbon
dioxide.

However; when a hydrocarbon fuel is burned, both the carbon and the hydrogen are oxidized.
Consider combustion of methane (NG) with pure oxygen as an example;
CH 4 aO2 bCO2 cH 2O a 2, b 1, c 2 from mole balance

CH 4 2O2 CO2 2 H 2O
When the oxygen required for the combustion of methane is supplied from the air, the reaction
can be written as;
CH 4 aO2 a 3.76 N 2 bCO2 cH 2O dN 2 a 2, b 1, c 2, d 7.52 from mole balance
CH 4 2O2 7.52 N 2 CO2 2 H 2O 7.52 N 2
9.52 kmol air

The minimum amount of air that supplies sufficient oxygen for the complete (stoichiometric)
combustion of all the carbon, hydrogen, and any other elements in the fuel that may oxidize, is
called the theoretical air. When complete combustion achieved with theoretical air, the products
contain no free oxygen.
In practice, it is found that complete combustion is not likely to be achieved unless the amount of
air supplied is somewhat greater than the theoretical amount. The amount of air actually supplied is
expressed in terms of percent theoretical air. The complete combustion of methane with 150%
Theoretical combustion with 100%
theoretical air is written as;
CH 4 2O2 7.52 N 2 CO2 2 H 2O 7.52 N 2
theoretical air or with 0% excess air
CH 4 1.5 2O2 7.52 N 2 CO2 2 H 2O O2 11.28 N 2
The combustion with 150%

theoretical air or with 50% excess air

The amount of air actually supplied may also be expressed in terms of percent excess air. The
excess air indicates the amount of air supplied over and above the theoretical air.
When the amount of air is less then the theoretical air required, the combustion is incomplete. If
there is a slight defficiency of air, the usual result is CO in products. If the air is considerably less
than the theoretical air, there may be also unburned hydrocarbons in products.
Even when some excess air is supplied there may also be small amounts of CO present in
products, the exact amount depending on a number of factors including the mixing and the
turbulence during combustion. Thus, the combustion of methane with 110% theoretical air might be
as follows:
CH 4 1.1 2O2 7.52 N 2 0.95CO2 0.05CO 2 H 2O 0.225O2 8.27 N 2
Two important parameters applied to the combustion processes are the air-fuel ratio (AF) and its
reciprocal, the fuel-air ratio (FA). The theoretical air-fuel ratio is the ratio of mass (or moles) of the
theoretical air to the mass (or moles) of fuel.
AFactual
Percent theoretical air
AFmole basis
FAmole basis
moles of air
mass of air
AFmass basis
moles of fuel
mass of fuel
moles of fuel
mass of fuel
FAmass basis
moles of air
mass of air
AFth
N O2 actual
N O2 th
100%
100%
AFactual AFth
100%
AFth
N O actual N O2 th
Percent excess air 2
100%
N O2 th
Percent excess air

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:
Reactants Products
C O2 CO2
1
H2 O2 H2 O
2
Example 1: Write the theoretical combustion equation of octane with pure oxygen.
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.
C8 H18 A O2 B CO2 D H2 O
Note we often can balance the C and H for complete combustion by inspection.
C8 H18 A O2 8 CO2 9 H2 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 12.5
C8 H18 12.5 O2 8 CO2 9 H2 O
Note: Mole numbers are not conserved, but we have conserved the mass on a total basis as well
as a specie basis. The complete combustion process is also called the stoichiometric combustion,
and all coefficients are called the stoichiometric coefficients.

Example 2: Calculate the theoretical air-fuel ratio for the combustion of octane.
C8 H18 A O2 3.76 N 2 BCO2 CH 2O DN 2

Where : B 8, C 9, A 12.5, D 47
C8 H18 12.5 O2 3.76 N 2 8CO2 9 H 2O 47 N 2
There are 12.5(1 + 3.76) = 59.5 kmoles of air required for each kmole 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. Thus,
the theoretical air-fuel ratio is;
AFth molebasis 12.51 3.76 59.5 kmoleair
1
kmolefuel
12.51 3.76 28.97
kgair
AFth massbasis
15.0
1
114 .2
kgfuel
M air
AFth massbasis AFth molebasis
M fuel
1kmoleair 0.21O2 0.79 N 2

M air 0.21 32 0.79 28
1kmoleC8 H18
M fuel 8 12 18 1

Example 3: Write the combustion equation for complete combustion of octane with 120 percent
theoretical air (20 percent excess air).
C8 H18 1.212.5 O2 3.76 N 2 8CO2 9 H 2O (0.2)(12.5)O2 1.2(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)O2 is found as excess oxygen in the products.
C8 H18 1.212.5 O2 3.76 N 2 8CO2 9 H 2O 2.5O2 56.4 N 2
Example 4: Determine the molal analysis of the products of combustion when octane is burned with
200% theoretical air and determine the dew point of the products if the pressure is 0.1 MPa.
C8 H18 212.5 O2 3.76 N 2 8CO2 9 H 2O (1)(12.5)O2 2(47) N 2

C8 H18 212.5 O2 3.76 N 2 8CO2 9 H 2O 12.5O2 94 N 2
Total kmol es of prod ucts 8 9 12.5 94 123.5 kmoles

Molal analysis of products;
NH O
PH O
0
.
0729
Pv 0.0729 100kPa 7.29kPa

8
N
P
mix
mix
CO2
100 6.47%
123.5
Tdp Tg @ P 39.7 0C
9
H 2O
100 7.29%
123.5
***The condensed liquid water from the combustion products may be
12.5
quite corrosive due to contained dissolved gases. For this reason, the
O2
100 10.12%
123.5
temperature of products are often kept above the dew point until
94
exhausted to atmosphere for preventing liquid water in the products.
N2
100 76.12%
123.5
2

Otto Cycle: Ideal Spark Ignition Engine
L
P4,Teg=T4
Combustion products
(Exhaust gas)
Q hAT h DL Texhaustgas T1
where,
T4 Teg ( x) Tdp Tdp Tg @ P
H 2O
P1,Teg>Tdp
Convective cooling
T1(atmospheric temp.)
& PH 2O
N H 2O
P1
N

Example 5: The producer gas from bituminous coal with volumetric analysis,
CH 4 3%
H 2 14%
N 2 50.9%
O2 0.6%
CO 27%
CO2 4.5%
is burned with 20% excess air. Calculate the air-fuel ratio on a volumetric basis and on a mass basis.
SOLN: To calculate the theoretical air requirement, let us write the theoretical combustion equations
for the combustible components present in 1 kmol of fuel gas.
0.03CH 4 0.06O2 0.03CO2 0.06 H 2O

0.14 H 2 0.07O2 0.14 H 2O
0.27CO 0.135O2 0.27CO2
kmol oxygen
required
kmol fuel
kmol oxygen
0.006
present i n fuel gas
kmol fuel
kmol oxygen
0.259
should come from air
kmol fuel
0.265
Therefore, the complete combustion equation for 1kmol of fuel gas is;
0.03CH 4 0.14 H 2 0.27CO 0.006O2 0.509 N 2 0.045CO2 0.259 O2 3.76 N 2 0.345CO2 0.2 H 2O 1.482 N 2
1 kmol Fuel gas
1.233 kmol air

supplied
Products

0.03CH 4 0.14 H 2 0.27CO 0.006O2 0.509 N 2 0.045CO2 0.259 O2 3.76 N 2 0.345CO2 0.2 H 2O 1.482 N 2
0.03CH 4 0.14 H 2 0.27CO 0.006O2 0.509 N 2 0.045CO2 1.2 0.259 O2 3.76 N 2 0.345CO2 0.2 H 2O 0.052O2 1.169 N 2
AFth molebasis 0.259(1 3.76) 1.233 kmolair

1
kmolfuel
AF20%excessair molebasis 1.2 AFth molebasis 1.2 1.233 1.48 kmolair
kmolfuel
AF20%excessair massbasis AF20%excessair molebasis
M air
28.97
kgair
1.48
1.73
M fuel
24.74
kgfuel
Example 6: Consider combustion of C8H18 with 120 % theoretical air where 80 % C in the fuel goes
into CO2.
C H 12
. (12.5) (O 3.76 N )
8
18
0.8(8) CO2 0.2(8) CO 9 H2 O X O2 12

. (47) 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

Example 7: Propane gas C3H8 is reacted with air such that the dry product gases are 11.5% CO2,
2.7% O2, and 0.7% 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?
SOLN: 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 )
115
. CO2 0.7 CO 2.7 O2 B H2 O A(3.76) N 2
C: X (3) 115
. (1) 0.7(1)
H: X (8) B (2)
O: A(2) 115
. (2) 0.7(1)
2.7(2) B (1)
N 2 : A(3.76) 85.31
X 4.07
B 16.28
A 22.69
The balanced equation is

Second method to find the coefficient A:
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
Assume the remainder of the 100 kmol of dry product gases is N2.
kmol N 100 (115

. 0.7 2.7) 851
.
Then A is
2
851
.
A
22.65 ( fairly good check )
3.76
These two methods dont 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
Actual
by 4.07:
Theoretical
C3 H8 557
. (O2 3.76 N 2 )
C3 H8 5 (O2 3.76 N 2 )
2.83 CO2 017
. CO 0.66 O2 4.0 H2 O 20.96 N 2
3 CO2 4.0 H2 O 18.80 N 2
kg air
kmol air
AFth
kg fuel
1kmol fuel[ 3(12) 8(1)]
kmol fuel
kg air
kmol air
kg fuel
1kmol fuel[3(12) 8(1)]
kmol fuel
kg air
17.45
kg fuel
(5)(1 3.76) kmol air 28.97
(5.57)(1 3.76) kmol air 28.97
AFactual
AFactual
100%
AFth
17.45
100 111%
15.66
AFactual AFth
100%
AFth
17.45 15.66
100 11%
15.66
Percent excess air
15.66
OR
kg air
kg fuel
N O2 actual
N O2 th
100%
557
.
100 111%
5
4
0.1398
2.83 0.17 0.66 4 20.96
Pv yv Pproducts 0.1398(100 kPa )
yv
13.98 kPa
Tdp Tsat at13.98 kPa
=52.31o C

Example 8: Methane is burned with atmospheric air. The analysis of the products on a dry basis is as
follows;
CO2 10.0%
O2 2.37%
CO 0.53%
N 2 87.1%
In a dry basis analysis, H2O in products is not listed (measured)
Calculate the air-fuel ratio and the percent theoretical air, and determine the combustion equation.
SOLN: 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.
aCH 4 b O2 3.76 N 2 10CO2 0.53CO 2.37O2 cH 2O 87.1N 2
N : 3.76b 87.1 b 23.16

C : a 10 0.53 10.53
H : 4a 2c c 2a 21.06
O : 2 x 23.16 20 0.53 2 x 2.37 21.06(OKEY )
10.53CH 4 23.16 O2 3.76 N 2 10CO2 0.53CO 2.37O2 21.06 H 2O 87.1N 2
CH 4 2.2 O2 3.76 N 2 0.95CO2 0.05CO 0.225O2 2 H 2O 8.27 N 2 Actual

CH 4 2 O2 3.76 N 2 CO2 2 H 2O 7.52 N 2 Theoretical
2.2(4.76)
kmolair
2(4.76)
kmolair
10.47
AFth
9.52
1
kmolfuel
1
kmolfuel
AFact
10.47
Percenttheoreticalai r
100
100 110 %
AFth
9.52
AFact

Example 9: An unknown hydrocarbon fuel, CXHY is reacted with air such that the dry product gases
are 12.1% CO2, 3.8% O2, and 0.9% CO by volume. What is the average makeup of the fuel?
SOLN: 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
C X HY A (O2 3.76 N 2 )
unknown fuel.
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.
D
83.2
22.13
3.76 3.76
O: A( 2) (12.1)(2) ( 0.9)(1) ( 38
. )(2) B (1)
B 1154
.
O2 : A
N 2 : D 100 (12.1 0.9 38

. ) 83.2
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 )

12.1 CO2 0.9 CO 38
. O2 1154
. H2 O 83.2 N 2

12.3 Enthalpy of Formation:
Up to now, we considered substances with a fixed chemical composition and therefore we can
used the thermodynamic tables for the evaluation of their enthalpy values. However, if we consider
chemical reactions, the chemical compositions of reactants change through the reaction.
So that, we must choose a reference state for this purpose. Universally accepted the reference
state is 250C(2980K) and 0.1 MPa(1 atm). At reference state, the enthalpy of all the elements is
accepted as zero.
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 followings.
Carbondioxide
CO2
O2
Exothermic reaction
Exothermic reaction
Qnet=-393522 kJ
Qnet=-74850 kJ
C O2 CO2
Qcv H P H R
Qcv H P H R
Qcv ne he ni hi
Qcv ne he ni hi
P
Qcv nCO hCO nC hC nO hO

2
Qcv H P 1xhCO h fo
2
C 2 H2 CH4
CO 2
Enthalpy of
formation
Qcv nCH hCH nC hC n H hH

4
o
393522kJ / kmol Qcv H P 1xhCH h f
4
CH 4
Enthalpy of
formation
74850kJ / kmol

h fo
The enthalpy of formation

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
Air
h fo
kJ/kmol
28.97
Table A.13 (van Wylen)

Table A.26 (engel)
Oxygen
O2
32
Nitrogen
N2
28
Then, enthalpy at any other temperature;
Carbon dioxide
CO2
44
-393,520
hT , P h fo hT , P
Carbon monoxide
CO
28
-110,530
Water (vapor)
H2Ovap
18
-241,820
hT , P h fo hTo h fo
Water (liquid)
H2Oliq
18
-285,830
Methane
CH4
16
-74,850
Acetylene
C 2H 2
26
+226,730
Ethane
C 2H 6
30
-84,680
Propane
C 3H 8
44
-103,850
Butane
C4H10
58
-126,150
Octane (vapor)
C8H18
114
-208,450
Dodecane
C H
170
-291,010
Table A.11 (van Wylen)

Tables A.(18-25) (engel)
If tables are not available, the enthalpy
difference due to the temperature difference
can be calculated from
12 26
University of Gaziantep / Mechanical
Engineering Department / Prof. Dr. M.Y. GUNDOGDU : ME 303 Thermodynamics II
Table A.13SI
Enthalpy of Formation
Van Wylen
Table A.11SI
(Van Wylen)

12.4 First Law Analysis of Reacting Systems:
Consider SSSF Combustion Process in a CV
Q cv H R Wcv H P
Q cv W cv H P H R
Q cv W cv ne he ni hi
P
KE= PE=0
For reactions at refrence state(25C, 0.1MPa)
Q cv W cv ne h fo h e ni h fo h
P
For reactions at any other temperature
Consider Combustion Process in a Closed Chamber
Q UR W UP
KE= PE=0
Q W UP UR
Molal internal energies are not tabulated in text books tables
Q W ne ue ni ui
P
Q W n h
Q W ne h fo R T
P
P
o
f
ni h fo R T
R
h R T
For reactions at refrence state(25C, 0.1MPa)
ni h fo h R T
R
For reactions at any other temperature

Example 10: Butane gas C4H10 is burned in theoretical air as shown below. Find the net heat
transfer per kmol of fuel. SOLN:
Balanced combustion equation:
C4 H10 6.5 (O2 3.76 N 2 )
4 CO2 5 H2 O 24.44 N 2
Qnet H P H R
N [h
e
o
f
(hT h o )]e
Products
Reactants: TR = 298 K
h fo
Comp
Ni
kJ/kmol
kmol/k
mol fuel
N [h
i
o
f
(hT h o )]i
Reactants
Products: TP = 1000 K
hT
kJ/kmol
kJ/km
ol
N i [h (hT h )]i
o
f
kJ/kmol fuel
Com
p
Ne
kmol/kmo
l fuel
h fo
kJ/kmol
hT
ho
kJ/kmol
kJ/km
ol
N e [h fo (hT h o )]e
kJ/kmol fuel
C4H10
-126,150
--
--
-126,150
CO2
-393,520
42,769
9,364
-1,440,460
O2
6.5
8,682
8,682
H2O
-241,820
35,882
9,904
-1,079,210
N2
24.44
8,669
8,669
N2
24.44
30,129
8,669
+524,482
HR
N [h
i
o
f
HP
(hT h o )]i
Reactants
126,150
N [h
e
o
f
(hT h o )]e
Products
kJ
kmol C4 H10
Qnet H P H R
1,869,038
1,995,188
kJ
kmol C4 H10
kJ
kmol C4 H10

Example 11: Consider the following reaction, which occurs in a SSSF process.
CH 4 2O2 CO2 2 H 2O l
The reactants and products are each at a total pressure of 0.1 MPa and 25oC. Determine the heat
transfer per kmole of fuel entering the combustion chamber.
SOLN:
Qcv ne he ni hi
Qcv nCO h fo
2
CO 2
o
f H O
2
where;1
h
h
h
nH
o
f CH
4
74850kJ / kmol
o
f CO
2
393520kJ / kmol
o
f H O (l )
2
n h
CH 4
o
f CH
4
0, element@RS
nO h fo
O2
From Table A.26

(engel)
285830kJ / kmol
Qcv 1x 393520 2 285830 1x 74850 2 0

Qcv 890330kJ
Example 12: A small gas turbine uses C8H18(l) for fuel and 400% theoretical air. The air and fuel
enter at 25oC and the products of combustion leave at 900 K. The output of the engine and the fuel
consumption are measured and it is found that the specific fuel consumption is 0.25 kg/s of fuel per
megawatt output. Determine the heat transfer from the engine per kmol of fuel. Assume complete
combustion.
SOLN: The theoretical combustion equation is; C8 H18 (l ) 12.5 O2 3.76 N 2 8CO2 9 H 2O 47 N 2
The actual combustion equation is; C8 H18 (l ) 4 x12.5 O2 3.76 N 2 8CO2 9 H 2O 37.5O2 188 N 2
Qcv ni h fo h i Wcv ne h fo h e
R
where;
0, element 0, RS
0, RS
ni h fo h i 1x h fo h C H
Reactants, 298 K (RS)
R
P
P
o
f
o
f
o
f
18
(l )
50 x h fo h
o
f
CO 2
Table A.20
0, RS
0, element
H 2O
Table A.23
O2
188 x h fo h
0, element
o
f
N2
O2
Table A.19
CO 2
Table A.26

249950kJ / kmolfuel
n h h 8 x h h 9 x h h 37.5 x h h 188 x h h
n h h 8 x 393520 28041 9 x 241820 21924 37.5 x 0 19246 188 x 0 18221
8
Products, 900 K
h fo
C 8 H 18 (l )
0, element
o
f
H 2O
N2
Table A.18
O2
2923832 1979064 721725 3425548 755623kJ / kmolfuel
Qcv Wcv ne h fo h e ni h fo h i
P
kJ
s x114 .23 kg 755623 249950 48753kJ / kmolfuel

kg
kmolfuel
0.25
Qcv
1000
N2

Example 13: A mixture of 1 kmol C8H18 gas and 200 percent excess air at 25oC, 1 atm, is burned
completely in a closed system (a bomb) and is cooled to 1200 K. Find the heat transfer from the
system and the system final pressure.SOLN:
Apply the first law closed system:
Assume that the reactants and products are ideal gases; then
PV NRu T
The balanced combustion equation for 200 percent excess (300 percent theoretical) air is
C8 H18 (3)(12.5) (O2 3.76 N 2 )

8 CO2 25 O2 9 H2 O 141 N 2

Qnet 8( 393,520 53,848 9364 8.314(1200)) CO2
9( 241,820 44,380 9904 8.314(1200)) H2 O
25(0 38,447 8682 8.314(1200)) O2
141(0 36,777 8669 8.314(1200)) N 2
1( 208,450 h298 K h o 8.314(298)) C8 H18
37.5(0 8682 8682 8.314(298)) O2
141(0 8669 8669 8.314(298)) N 2
112
. 106
but V2 = V1.
kJ
kmol C8 H18
To find the final pressure, we assume that

the reactants and the products are ideal-gas
mixtures.
1 1
1 u 1
PV N R T
PV
2 2 N 2 Ru T2
where state 1 is the state of the mixture of
the reactants before the combustion process
and state 2 is the state of the mixture of the
products after the combustion process takes
place. Note that the total moles of reactants
are not equal to the total moles of products.
PV
N 2 Ru T2
2 2
PV
N1 Ru T1
1 1

12.5 Adiabatic Flame Temperature:
The temperature of the products when a combustion process takes place adiabatically and no work
or changes in KE and PE, is called the adiabatic flame temperature. This is the maximum
temperature that can be achieved for the given reactants because any heat transfer from the
reacting substances and any incomplete combustion would tend to lower the temperature of the
products.
Consider SSSF Adiabatic Combustion Process in a CV
Qcv H R Wcv H P W=Q=KE= PE=0

HR HP
ni h fo h i ne h fo h
R
Consider Adiabatic Combustion Process in a Closed Chamber
W=Q=KE= PE=0
Q UR W UP
U R U P
ni h fo R T i ne h fo R T e
R
ni h fo h R T i ne h fo h R T e
R
Example 14: Liquid octane C8H18(liq) is burned with 400 percent theoretical air in a SSSF process.
Find the adiabatic flame temperature when the reactants enter at 298 K, 0.1 MPa, and the products
leave at 0.1MPa.
C8 H18 4(12.5) ( O2 3.76 N 2 )
8 CO2 37.5 O2 9 H2 O 188 N 2

Qnet H P H R
N [h
e
Products
o
f
( hT h o )]e
N [h
i
o
f
( hT h o )]i
Reactants
0 ( Adiabatic Combustion)

Thus, HP = HR for adiabatic combustion. We need to solve this equation for TP.
Since the temperature of the reactants is 298 K, (
HR
o
N
h
i fi
hT h o )i = 0,
C8 H18 4(12.5) ( O2 3.76 N 2 )

8 CO2 37.5 O2 9 H2 O 188 N 2
Reactants
1( 249,950) 4(12.5)(0) 4(12.5)(3.76)(0)

kJ
249,950
kmol C4 H10
Since the products are at the adiabatic flame temperature, TP > 298 K
HP
Products
N e [h fo (hTP h o )]e
8(393,520 hTP 9364)CO2

9(241,820 hTP 9904) H 2O
37.5(0 hTP 8682)O2
188(0 hTP 8669) N 2
(7, 443,845 8hTP , CO2 9hTP , H 2O
37.5hTP , O2 188hTP , N2 )
kJ
kmol C4 H10

Thus, setting HP = HR yields
N h
Pr oducts
e TP , e
8hTP , CO2 9hTP , H2 O 37.5hTP , O2 188hTP , N 2

7,193,895
To estimate TP, assume all products behave like N2 and estimate the adiabatic flame
temperature from the nitrogen data, Table A-18.
242.5hTP , N 2 7,193,895
hTP , N 2 29,6655
.
kJ
kmol 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
40,607
41,145
H2O
34,274
34,653
O2
37.5
29,991
30,345
N2
188
28,826
29,151
7,177,572
7,259,362
N h
Produts
e TP , e
Interpolation gives: TP = 962 K.

Example 15: 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?
C8 H18 (1 A)(12.5) (O2 3.76 N 2 )

8 CO2 12.5 A O2 9 H2 O (1 A)(12.5)(3.76) N 2
The steady-flow heat transfer is
Qnet H P H R
N [h
e
o
f
(hT h o )]e
Products
N [h
i
o
f
(hT h o )]i
Reactants
0 ( Adiabatic combustion)
Here, since the temperatures are known, the values of hTP 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.
A3
Thus, 300 percent excess, or 400 percent theoretical, air is supplied.

Example 16: 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.
C3 H8 (1 A)(5) (O2 3.76 N 2 )

3 CO2 5 A O2 4 H2 O (1 A)(5)(3.76) N 2
The combustion equation is
where A is the value of excess air in decimal form.

The steady-flow heat transfer is
Qnet H P H R
o
o
N
[
h
(
h
h
e f T )]e
Products
o
o
N
[
h
(
h
h
i f T )]i
Reactants
0 ( Adiabatic combustion)
Percent Excess
Air
Adiabatic Flame Temp.

K
2459.3
20
2191.9
50
1902.5
100
1587.1
217
1200

12.5 Enthalpy and Internal Energy of Reaction or 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 25 oC
See Table A.27, tabulated values for fuels
or 298 K.
Similarly, internal energy of combustion is defined as;
hC H P H R when TP TR 25o C 298 K
o
N
h
e fe
Products
o
N
h
i fi
uC u RP U p U R whenTP TR 298 K
uC N e h fo R T e N i h fo R T
Reactants
Heating Value
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.
HV hC
The lower heating value, LHV, is the heating value when water appears as a gas in the products.
LHV hC hC with H2 Ogas in products
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.
HHV hC hC with H2 Oliquid in products

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 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 H2 O h fg H2 O
Example 17: 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.
LHVC8 H18 gas HHVC8 H18 gas N H2O h fg H 2O
LHVC8 H18 liq LHVC8 H18 gas h fg C8 H18
5,500,842
kJ
kmol H 2O
kJ
9
(44,010)
kmol C8 H18 kmol C8 H18
kmol H 2O
(5,104752 41, 382)
5,104,752
kJ
kmol C8 H18
5, 063, 370
kJ
kmol C8 H18
kJ
kmol C8 H18 liq
Can you explain why LHVliq< LHVgas?


12.6 Second Law Analysis of Reacting Systems:
Second law for the open system
The entropy balance relations developed
in Chapter 7 are equally applicable to both
reacting
and
nonreacting
systems
provided that the entropies of individual
constituents are evaluated properly using
a common basis.
Taking the positive direction of heat
transfer to be to the system, the entropy
balance relation can be expressed for a
steady-flow combustion chamber as
Qk
SReact S Prod S gen SCV
( kJ / k )
For an adiabatic, steady-flow process, the entropy balance relation reduces to
S gen , adiabatic SProd SReact 0
The third law of thermodynamics states that the entropy of a pure crystalline substance at absolute
zero temperature is zero. The third law provides a common base for the entropy of all substances,
and the entropy values relative to this base are called the absolute entropy.
The ideal-gas tables list the absolute entropy values over a wide range of temperatures but at a
fixed pressure of Po = 1 atm. Absolute entropy values at other pressures P for any temperature T
are determined from
P
o
s (T , P ) s (T , Po ) Ru ln
Po
[ kJ / ( kmol K )]

For component i of an ideal-gas mixture, the absolute entropy can be written as
si ( T , Pi ) sio (T , Po ) Ru ln
yi Pm
Po
[ kJ / ( kmol K )]
where Pi is the partial pressure, yi is the mole fraction of the component, and Pm is the total
pressure of the mixture in atmospheres.
Example 18: A mixture of ethane gas C2H6 and oxygen enters a combustion chamber at 1 atm,
25oC. The products leave at 1 atm, 900 K. Assuming complete combustion, does the process
violate the second law?
The balanced combustion equation is
C2 H6 35
. O2 2 CO2 3 H2 O
The mole fractions for the reactants and the products are
1
1
1 3.5 4.5
35
.
3.5
1 3.5 4.5
2
2
23 5
3
3
23 5
yC2 H6
yO2
yCO2
y H2 O

Now calculate the individual component entropies.
For the reactant gases:
S React
N s
i i
Reactants
1(242.0) 3.5(207.1)
966.9
kJ
kmolC2 H6 K
For the product gases:
S Prod
N s
e e
Products
2(2712
. ) 3(232.6)
1240.2
kJ
kmolC2 H6 K

The entropy change for the combustion process is
S Prod S React (1240.2 966.9)

273.3
kJ
kmolC2 H6 K
kJ
kmolC2 H6 K
Now to find the entropy change due to heat transfer with the surroundings. The steady-flow
conservation of energy for the control volume is
Qnet sys H P H R
Qk Qnet sys
To
kJ
kmol C2 H6
(25 273) K
kJ
4,383
kmol C2 H6 K
N [h
e
o
f
(hT h o )]e
Products
1306
.
106
N [h
i
o
f
(hT h o )]i
Reactants
Qnet sys 2( 393,520 37,405 9364) CO2

3( 241,820 31,828 9904) H2 O
1( 214,820 h298 K h o ) C2 H6
The entropy generated by this combustion process is
3.5(0 8682 8682) O2

1306
.
106
kJ
kmol C2 H6
Since Sgen, or Snet , is 0, the second law is not violated.


Me 303 CH12

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CHAPTER 12: CHEMICAL REACTIONS (COMBUSTIONS)

The hydrocarbon fuels exits in different phases

Some of the common hydrocarbon fuels are

gasoline or octane, diesel, methyl alcohol or

Liquid or Gaseous Hydrocarbons

Composition changes from

Analysis given on a mass

Composition of coals from

- ylene or -ene (propene and

Most liquid hydrocarbons are derived from

Each type is characterized by its distillation

The distillation curve is obtained by slowly

The more volatile component is vaporized first.

CHAPTER 12: CHEMICAL REACTIONS (COMBUSTIONS)

Usually Hydrocarbons or Hydrogen in Air are used

Some Characteristics of Hydrocarbon Families:

CHAPTER 12: CHEMICAL REACTIONS (COMBUSTIONS)

Olefins- CnH2n, Contains one or more C=C bond/Chain

Paraffin (Alkanes) - CnH2n+2

Acetylenes - Contains one or more CC bond

CHAPTER 12: CHEMICAL REACTIONS (COMBUSTIONS)

Alcohols - contains one or more -OH groups

CHAPTER 12: CHEMICAL REACTIONS (COMBUSTIONS)

CHAPTER 12: CHEMICAL REACTIONS (COMBUSTIONS)

Per Cent Recovered

CHAPTER 12: CHEMICAL REACTIONS (COMBUSTIONS)

1 kmol or volume of Atmospheric Air (assumed)

Small Amounts-CO,CO2, He, H2, H2O

1 kmol air = 0.21 kmol O2 + 0.79 kmol N2

CHAPTER 12: CHEMICAL REACTIONS (COMBUSTIONS)

CH 4 aO2 bCO2 cH 2O a 2, b 1, c 2 from mole balance

CH 4 aO2 a 3.76 N 2 bCO2 cH 2O dN 2 a 2, b 1, c 2, d 7.52 from mole balance

CH 4 2O2 7.52 N 2 CO2 2 H 2O 7.52 N 2

9.52 kmol air

CH 4 2O2 7.52 N 2 CO2 2 H 2O 7.52 N 2

theoretical air or with 0% excess air

CH 4 1.5 2O2 7.52 N 2 CO2 2 H 2O O2 11.28 N 2

The combustion with 150%

CHAPTER 12: CHEMICAL REACTIONS (COMBUSTIONS)

CH 4 1.1 2O2 7.52 N 2 0.95CO2 0.05CO 2 H 2O 0.225O2 8.27 N 2

Percent theoretical air

Percent excess air

CHAPTER 12: CHEMICAL REACTIONS (COMBUSTIONS)

C8 H18 12.5 O2 8 CO2 9 H2 O

CHAPTER 12: CHEMICAL REACTIONS (COMBUSTIONS)

C8 H18 A O2 3.76 N 2 BCO2 CH 2O DN 2

AFth molebasis 12.51 3.76 59.5 kmoleair

1kmoleair 0.21O2 0.79 N 2

CHAPTER 12: CHEMICAL REACTIONS (COMBUSTIONS)

C8 H18 1.212.5 O2 3.76 N 2 8CO2 9 H 2O (0.2)(12.5)O2 1.2(47) N 2

C8 H18 1.212.5 O2 3.76 N 2 8CO2 9 H 2O 2.5O2 56.4 N 2

C8 H18 212.5 O2 3.76 N 2 8CO2 9 H 2O (1)(12.5)O2 2(47) N 2

Total kmol es of prod ucts 8 9 12.5 94 123.5 kmoles

Pv 0.0729 100kPa 7.29kPa

CHAPTER 12: CHEMICAL REACTIONS (COMBUSTIONS)

CHAPTER 12: CHEMICAL REACTIONS (COMBUSTIONS)

0.03CH 4 0.06O2 0.03CO2 0.06 H 2O

1 kmol Fuel gas

1.233 kmol air

CHAPTER 12: CHEMICAL REACTIONS (COMBUSTIONS)

AFth molebasis 0.259(1 3.76) 1.233 kmolair

AF20%excessair molebasis 1.2 AFth molebasis 1.2 1.233 1.48 kmolair

AF20%excessair massbasis AF20%excessair molebasis