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Chemical Reactions
Study Guide in PowerPoint
to accompany
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
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.
2
Reactants Products
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 CO2
1
H2 O2 H2 O
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.
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 3. 76 N 2 )
8 CO2 9 H2 O 47 N 2
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
kmol air
AF
kmol fuel
Thus, for the above example, the theoretical air-fuel ratio is
AFth
12.5(1 3.76)
kmol air
59.5
1
kmol fuel
kg air
kmol air
kmol air
AFth 59.5
kmol fuel [8(12) 18(1)] kg fuel
kmol fuel
28.97
1512
.
kg air
kg fuel
AFactual
100%
AFth
AFactual AFth
100%
AFth
6
Show that these results may be expressed in terms of the moles of oxygen only as
N O2 actual
N O2 th
100%
N O2 actual N O2 th
N O2 th
100%
Example 15-2
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)O2 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
Second method to balance the equation for excess air (see the explanation of this
technique in the text) is:
C8 H18 12
. Ath (O2 3.76 N 2 )
8 CO2 9 H2 O 0.2 Ath O2 12
. Ath (3.76) N 2
O:
12
. Ath (2) 8(2) 9(1) 0.2 Ath (2)
Ath 12.5
C8 H18 12
. (12.5) (O2 3.76 N 2 )
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
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
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 )
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)
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
10
Then A is
A
851
.
22.65
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 by 4.07:
C3 H8 557
. (O2 3.76 N 2 )
2.83 CO2 017
. CO 0.66 O2 4.0 H2 O 20.96 N 2
The actual air-fuel ratio is
kg air
kmol air
kg fuel
1kmol fuel[3(12) 8(1)]
kmol fuel
kg air
17.45
kg fuel
11
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
kmol air
AFth
kg fuel
1kmol fuel[3(12) 8(1)]
kmol fuel
(5)(1 3.76) kmol air 28.97
kg air
15.66
kg fuel
The percent theoretical air is
AFactual
100%
AFth
17.45
100 111%
15.66
12
or
N O2 actual
N O2 th
100%
557
.
100 111%
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.
13
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?
14
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 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 )
12.1 CO2 0.9 CO 38
. O2 B H2 O D N 2
15
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
C: 1( X ) 12.1(1) (0.9)(1)
X 13.0
H: 1(Y ) B (2)
Y 23.08
16
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.
C 2 H2 CH4
The conservation of energy for a steady-flow combustion process is
Ein Eout
Qnet HReactants HProducts
Qnet HProducts HReactants
17
Qnet
N h
e e
Products
Nh
i i
Reactants
During the formation of methane from the elements at 298 K, 0.1 MPa, heat is given
off (an exothermic reaction) such that
Qnet h fo CH 74,850
4
kJ
kmolCH4
18
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
28.9
7
Oxygen
O2
32
Nitrogen
N2
28
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
19
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 (hT h o )
o
Here the term h 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
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
20
Example 15-7
Butane gas C4H10 is burned in theoretical air as shown below. Find the net heat
transfer per kmol of fuel.
N [h
e
Products
o
f
(hT h o )]e
N [h
i
o
f
(hT h o )]i
Reactants
21
Reactants: TR = 298 K
kJ/kmol
N i [h fo (hT h o )]i
kJ/kmol fuel
--
--
-126,150
8,682
8,682
8,669
8,669
h fo
Comp
Ni
kmol/kmol
fuel
C4H10
-126,150
O2
6.5
N2
24.44
kJ/kmol
HR
hT
kJ/kmol
N [h
i
o
f
ho
(hT h o )]i
Reactants
126,150
Products: TP = 1000 K
Comp
h fo
Ne
kmol/kmol
fuel
kJ/kmol
kJ
kmol C4 H10
hT
kJ/kmol
N e [h fo (hT h o )]e
kJ/kmol
kJ/kmol fuel
ho
CO2
-393,520
42,769
9,364
-1,440,460
H2O
-241,820
35,882
9,904
-1,079,210
N2
24.44
30,129
8,669
+524,482
22
HP
N [h
e
o
f
(hT h o )]e
Products
1,995,188
kJ
kmol C4 H10
Qnet H P H R
1,869,038
kJ
kmol C4 H10
23
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.
24
Nh
HR
Reactants
hT h o )i = 0,
o
f i
kJ
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
kJ
kmol C4 H10
25
N h
Pr oducts
e TP , e
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
26
27
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 hT are known. The product
P
gas mole numbers are unknown but are functions of the amount of excess air, A. The
energy balance can be solved for A.
A3
N [h
e
o
f
(hT h o )]e
Products
N [h
i
o
f
(hT h o )]i
Reactants
0 ( Adiabatic combustion)
Percent Excess
Air
2459.3
20
2191.9
50
1902.5
100
1587.1
217
1200
29
o
N
h
e fe
Products
o
N
h
i fi
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.
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 LHV N H2 O h fg H2 O
31
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.
kJ
kmol H 2O
kJ
9
(44, 010)
kmol C8 H18
kmol C8 H18
kmol H 2O
5,104, 752
kJ
kmol C8 H18
kJ
kmol C8 H18
kJ
5, 063,370
kmol C8 H18 liq
Can you explain why LHVliq< LHVgas?
32
33
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
34
kJ
kmol C8 H18
To find the final pressure, we assume that the reactants and the products are idealgas mixtures.
PV
1 1 N 1 Ru T1
PV
2 2 N 2 Ru T2
35
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
but V2 = V1.
36
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
T SReact SProd S gen SCV
k
( kJ / k )
37
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
s (T , P ) s o (T , Po ) Ru ln
P
Po
[ kJ / ( kmol K )]
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.
38
Example 15-13
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?
39
The mole fractions for the reactants and the products are
1
1
yC2 H6
1 35
.
4.5
35
.
35
.
yO2
1 35
.
4.5
2
2
yCO2
23 5
3
3
y H2 O
23 5
Now calculate the individual component entropies.
For the reactant gases:
40
S React
N s
i i
Reactants
1(242.0) 35
. (207.1)
kJ
966.9
kmolC2 H6 K
41
42
S Prod
N s
e e
Products
2(2712
. ) 3(232.6)
kJ
1240.2
kmolC2 H6 K
The entropy change for the combustion process is
kJ
kmolC2 H6 K
kJ
273.3
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
N [h
e
Products
o
f
(hT h o )]e
N [h
i
o
f
(hT h o )]i
Reactants
43
kJ
kmol C2 H6
Qk Qnet sys
T T
k
o
kJ
kmol C2 H6
(25 273) K
kJ
4,383
kmol C2 H6 K
1306
.
106
44
45