Chapter 15

Chemical Reactions

Study Guide in PowerPoint


to accompany


Thermodynamics: An Engineering Approach, 5th edition
by Yunus A. engel and Michael A. Boles



2
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, H
2
.

Examples of hydrocarbon fuels are

CH
4
Methane
C
8
H
18
Octane
Coal Mixture of C, H
2
, S, O
2
, N
2
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.
3
Reactants Products
C O CO
H O H O
+
+
2 2
2 2 2
1
2
For complete or stoichiometric combustion, all carbon is burned to carbon dioxide
(CO
2
) and all hydrogen is converted into water (H
2
O). These two complete
combustion reactions are as follows:
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 H AO B CO D H O
8 18 2 2 2
+ +
Note we often can balance the C and H for complete combustion by inspection.
C H AO CO H O
8 18 2 2 2
8 9 + +
4
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
A
: ( ) ( ) ( )
.
2 8 2 9 1
125
= +
=
C H O CO H O
8 18 2 2 2
125 8 9 + + .
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.

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 H O N
CO H O N
8 18 2 2
2 2 2
12 5 3 76
8 9 47
+ +
+ +
. ( . )
5
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
AF
kmol air
kmol fuel
=
Thus, for the above example, the theoretical air-fuel ratio is
AF
kmol air
kmol fuel
th
=
+
=
12 5 1 376
1
59 5
. ( . )
.
6
On a mass basis, the theoretical air-fuel ratio is
AF
kmol air
kmol fuel
kg air
kmol air
kg fuel
kmol fuel
kg air
kg fuel
th
=
+
=
595
28 97
8 12 18 1
1512
.
.
[ ( ) ( )]
.
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.
Percent theoreticalair =
AF
AF
actual
th
100%
Percentexcessair =
AF AF
AF
actual th
th
100%
7
Show that these results may be expressed in terms of the moles of oxygen only as
Percent theoretical air =
N
N
O
actual
O
th
2
2
100%
Percent excess air =
N N
N
O actual O
th
O
th
2 2
2
100%
Example 15-2

Write the combustion equation for complete combustion of octane with 120 percent
theoretical air (20 percent excess air).
C H O N
CO H O O N
8 18 2 2
2 2 2 2
12 12 5 376
8 9 0 2 12 5 12 47
+ +
+ + +
. ( . ) ( . )
( . )( . ) . ( )
Note that (1)(12.5)O
2
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.
C H O N
CO H O O N
8 18 2 2
2 2 2 2
12 12 5 376
8 9 2 5 12 47
+ +
+ + +
. ( . ) ( . )
. . ( )
8
Second method to balance the equation for excess air (see the explanation of this
technique in the text) is:
C H A O N
CO H O A O A N
O A A
A
th
th th
th th
th
8 18 2 2
2 2 2 2
12 376
8 9 0 2 12 376
12 2 8 2 9 1 0 2 2
12 5
+ +
+ + +
= + +
=
. ( . )
. . ( . )
: . ( ) ( ) ( ) . ( )
.
Incomplete Combustion with Known Percent Theoretical Air

Example 15-3

Consider combustion of C
8
H
18
with 120 % theoretical air where 80 % C in the fuel goes
into CO
2
.
C H O N
CO CO H O X O N
8 18 2 2
2 2 2 2
12 12 5 376
08 0 2 9 12 47
+ +
+ + + +
. ( . ) ( . )
. (8) . (8) . ( )
9
O balance gives
O X
X
: . ( . )( ) . (8)( ) . (8)( ) ( ) ( )
.
12 12 5 2 08 2 0 2 1 9 1 2
33
= + + +
=
Why is X > 2.5?

Then the balanced equation is
C H O N
CO CO H O O N
8 18 2 2
2 2 2 2
12 12 5 376
6 4 16 9 33 12 47
+ +
+ + + +
. ( . ) ( . )
. . . . ( )
Combustion Equation When Product Gas Analysis Is Known

Example 15-4

Propane gas C
3
H
8
is reacted with air such that the dry product gases are 11.5 percent
CO
2
, 2.7 percent O
2
, 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.
10
X C H A O N
CO CO O B H O A N
3 8 2 2
2 2 2 2
376
115 0 7 2 7 376
+ +
+ + + +
( . )
. . . ( . )
The unknown coefficients A, B, and X are found by conservation of mass for each
species.
C X X
H X B B
O A
B A
N A
: ( ) . ( ) . ( ) .
: (8) ( ) .
: ( ) . ( ) . ( )
. ( ) ( ) .
: ( . ) .
3 115 1 0 7 1 4 07
2 16 28
2 115 2 0 7 1
2 7 2 1 22 69
376 8531
2
= + =
= =
= +
+ + =
=
The balanced equation is
4 07 22 69 376
115 0 7 2 7 16 28 8531
3 8 2 2
2 2 2 2
. . ( . )
. . . . .
C H O N
CO CO O H O N
+ +
+ + + +
Second method to find the coefficient A:

Assume the remainder of the 100 kmol of dry product gases is N
2
.
kmol N
2
100 115 07 2 7 851 = + + = ( . . . ) .
11
Then A is
A fairly good check = =
851
376
22 65
.
.
. ( )
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:
C H O N
CO CO O H O N
3 8 2 2
2 2 2 2
557 376
2 83 017 0 66 4 0 20 96
+ +
+ + + +
. ( . )
. . . . .
The actual air-fuel ratio is
AF
kmol air
kg air
kmol air
kmol fuel
kg fuel
kmol fuel
kg air
kg fuel
actual
=
+
+
=
(5. )( . ) .
[ ( ) ( )]
.
57 1 376 28 97
1 3 12 8 1
17 45
12
The theoretical combustion equation is
C H O N
CO H O N
3 8 2 2
2 2 2
5 376
3 4 0 1880
+ +
+ +
( . )
. .
The theoretical air-fuel ratio is
AF
kmol air
kg air
kmol air
kmol fuel
kg fuel
kmol fuel
kg air
kg fuel
th
=
+
+
=
(5)( . ) .
[ ( ) ( )]
.
1 376 2897
1 3 12 8 1
1566
The percent theoretical air is
Percent theoretical air =
= =
AF
AF
actual
th
100%
17 45
1566
100 111%
.
.
13
or
Percent theoretical air =
= =
N
N
O
actual
O
th
2
2
100%
557
5
100 111%
.
The percent excess air is
Percent excess air =

=

=
AF AF
AF
actual th
th
100%
17 45 1566
1566
100 11%
. .
.
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.
14
T T P y P
y
N
N
v
v
e
dp sat v products
water
products
at = =
=

Example 15-5

Determine dew point temperature of the products for Example 15-4.
products
dp sat
4
0.1398
2.83 0.17 0.66 4 20.96
0.1398(100 )
13.98
at13.98kPa
=52.31
v
v v
o
y
P y P kPa
kPa
T T
C
= =
+ + + +
= =
=
=
What would happen if the product gases are cooled to 100
o
C or to 30
o
C?
15
Example 15-6

An unknown hydrocarbon fuel, CXHY is reacted with air such that the dry product
gases are 12.1 percent CO
2
, 3.8 percent O
2
, 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 H A O N
CO CO O B H O D N
X Y
+ +
+ + + +
( . )
. . .
2 2
2 2 2 2
376
121 0 9 38
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 H A O N
CO CO O B H O D N
X Y
+ +
+ + + +
( . )
. . .
2 2
2 2 2 2
376
121 0 9 38
16
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 D
2
100 121 09 38 832 : ( . . . ) . = + + =
O A
D
O A B
B
C X
X
H Y B
Y
2
376
832
376
2213
2 121 2 0 9 1 38 2 1
1154
1 121 1 0 9 1
130
1 2
2308
:
.
.
.
.
: ( ) ( . )( ) ( . )( ) ( . )( ) ( )
.
: ( ) . ( ) ( . )( )
.
: ( ) ( )
.
= = =
= + + +
=
= +
=
=
=
The balanced equation is
C H O N
CO CO O H O N
13 23 08 2 2
2 2 2 2
2213 376
121 0 9 38 1154 832
.
. ( . )
. . . . .
+ +
+ + + +
17
Enthalpy of Formation

When a compound is formed from its elements (e.g., methane, CH
4
, from C and H
2
),
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 H CH + 2
2 4
The conservation of energy for a steady-flow combustion process is
E E
Q H H
Q H H
in out
net
net
=
+ =
=
Reactants Products
Products Reactants
18
Q N h N h
Q h h h
net e e i i
net CH C H
=
= +

Products Reactants
1 1 2
4 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 25
o
C (298 K) and 1 atm (or 0.1 MPa).
Q h
h
net CH
CH
= +
=
1 1 0 2 0
4
4
( ( ) ( ))
h
f
o
h
f
o
This heat transfer is called the enthalpy of formation for methane, . The
superscript (o) implies the 1 atm pressure value and the subscript (f) implies 25oC
data, 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
Q h
kJ
kmol
net f
o
CH
CH
= =
4
4
74 850 ,
19
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.
h
f
o
h
f
o
Substance Formula M kJ/kmol
Air 28.97 0
Oxygen O
2
32 0
Nitrogen N
2
28 0
Carbon dioxide CO
2
44 -393,520
Carbon monoxide CO 28 -110,530
Water (vapor) H
2
O
vap
18 -241,820
Water (liquid) H
2
O
liq
18 -285,830
Methane CH
4
16 -74,850
Acetylene C
2
H
2
26 +226,730
Ethane C
2
H
6
30 -84,680
Propane C
3
H
8
44 -103,850
Butane C
4
H
10
58 -126,150
Octane (vapor) C
8
H
18
114 -208,450
Dodecane C
12
H
26
170 -291,010
20
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 25
o
C (77 F) or 298 K (537 R), 1 atm. The
enthalpy at any other temperature is given as
h h h h
f
o
T
o
= + ( )
Here the term 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
h
o
Based on the classical sign convention, the net heat transfer to the reacting system is
Q H H
N h h h N h h h
net P R
e f
o
T
o
e i f
o
T
o
i
=
= + +

[ ( )] [ ( )]
Products Reactants
In an actual combustion process, is the value of Q
net
positive or negative?
21
Example 15-7

Butane gas C
4
H
10
is burned in theoretical air as shown below. Find the net heat
transfer per kmol of fuel.
Balanced combustion equation:
C H O N
CO H O N
4 10 2 2
2 2 2
65 376
4 5 24 44
+ +
+ +
. ( . )
.
The steady-flow heat transfer is
Q H H
N h h h N h h h
net P R
e f
o
T
o
e i f
o
T
o
i
=
= + +

[ ( )] [ ( )]
Products Reactants
22
Reactants: T
R
= 298 K
h
f
o
h
T
h
o
N h h h
i f
o
T
o
i
[ ( )] + Comp N
i

kmol/kmol
fuel

kJ/kmol

kJ/kmol

kJ/kmol

kJ/kmol fuel
C
4
H
10
1 -126,150 -- -- -126,150
O
2
6.5 0 8,682 8,682 0
N
2
24.44 0 8,669 8,669 0
H N h h h
kJ
kmol C H
R i f
o
T
o
i
= +
=

[ ( )]
,
Reactants
126 150
4 10
Products: T
P
= 1000 K
h
f
o
h
T
h
o
N h h h
e f
o
T
o
e
[ ( )] + Comp N
e

kmol/kmol
fuel

kJ/kmol

kJ/kmol

kJ/kmol

kJ/kmol fuel
CO
2
4 -393,520 42,769 9,364 -1,440,460
H
2
O 5 -241,820 35,882 9,904 -1,079,210
N
2
24.44 0 30,129 8,669 +524,482
23
H N h h h
kJ
kmol C H
P e f
o
T
o
e
= +
=

[ ( )]
, ,
Products
1995188
4 10
Q H H
kJ
kmol C H
net P R
=
= 1869 038
4 10
, ,
Adiabatic Flame Temperature

The temperature the products have when a combustion process takes place
adiabatically is called the adiabatic flame temperature.

Example 15-8

Liquid octane C
8
H
18
(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.
24
The combustion equation is
C H O N
CO O H O N
8 18 2 2
2 2 2 2
4 12 5 376
8 37 5 9 188
+ +
+ + +
( . ) ( . )
.
The steady-flow heat transfer is
Q H H
N h h h N h h h
Adiabatic Combustion
net P R
e f
o
T
o
e i f
o
T
o
i
=
= + +
=

[ ( )] [ ( )]
( )
Products Reactants
0
Thus, H
P
= H
R
for adiabatic combustion. We need to solve this equation for T
P
.
25
Since the temperature of the reactants is 298 K, ( )
i
= 0,
h h
T
o

H N h
kJ
kmol C H
R i f
o
i
=
= + +
=

Reactants
1 249 950 4 12 5 0 4 12 5 376 0
249 950
4 10
( , ) ( . )( ) ( . )( . )( )
,
Since the products are at the adiabatic flame temperature, T
P
> 298 K
2
2
2
2
2 2
2 2
Products
, ,
, ,
4 10
[ ( )]
8( 393, 520 9364)
9( 241, 820 9904)
37.5(0 8682)
188(0 8669)
( 7, 443, 845 8 9
37.5 188 )
P
P
P
P
P
P P
P P
o o
P e f T e
T CO
T H O
T O
T N
T CO T H O
T O T N
H N h h h
h
h
h
h
h h
kJ
h h
kmol C H
= +
= +
+ +
+ +
+ +
= + +
+ +

26
Thus, setting H
P
= H
R
yields
N h h h h h
e T e
oducts
T CO T H O T O T N
P P P P P
,
Pr
, , , ,
.
, ,

= + + +
=
8 9 375 188
7 193895
2 2 2 2
To estimate T
P
, assume all products behave like N
2
and estimate the adiabatic flame
temperature from the nitrogen data, Table A-18.
2425 7 193895
29 6655
985
2
2
2
. , ,
, .
,
,
h
h
kJ
kmol N
T K
T N
T N
p
P
P
=
=
~
Because CO
2
and H
2
O are triatomic gases and have specific heats greater than
diatomic gases, the actual temperature will be somewhat less than 985 K. Try T
P
=
960 K and 970K.
h
K 960
h
K 970
N h
e T e
P
,
Produts

N
e

CO
2
8 40,607 41,145
H
2
O 9 34,274 34,653
O
2
37.5 29,991 30,345
N
2
188 28,826 29,151
7,177,572 7,259,362
27
Interpolation gives: T
P
= 962 K.
Example 15-9

Liquid octane C
8
H
18
(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?
Let A be the excess air; then combustion equation is
C H A O N
CO A O H O A N
8 18 2 2
2 2 2 2
1 12 5 376
8 12 5 9 1 12 5 376
+ + +
+ + + +
( )( . ) ( . )
. ( )( . )( . )
28
The steady-flow heat transfer is
Q H H
N h h h N h h h
Adiabatic combustion
net P R
e f
o
T
o
e i f
o
T
o
i
=
= + +
=

[ ( )] [ ( )]
( )
Products Reactants
0
Here, since the temperatures are known, the values of 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.
h
T
P
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 C
3
H
8
when the fuel enters the steady-flow reaction chamber at 298 K
and the air enters at 400 K.

The combustion equation is
C H A O N
CO A O H O A N
3 8 2 2
2 2 2 2
1 376
3 5 4 1 376
+ + +
+ + + +
( )(5) ( . )
( )(5)( . )
29
where A is the value of excess air in decimal form.

The steady-flow heat transfer is
Q H H
N h h h N h h h
Adiabatic combustion
net P R
e f
o
T
o
e i f
o
T
o
i
=
= + +
=

[ ( )] [ ( )]
( )
Products Reactants
0
Percent Excess
Air
Adiabatic Flame
Temp. K
0 2459.3
20 2191.9
50 1902.5
100 1587.1
217 1200
30
Enthalpy of Reaction and Enthalpy of Combustion

When the products and reactants are at the same temperature, the enthalpy of
reaction h
R
, 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 h
C
. The enthalpy of combustion can be calculated at any
value of the temperature, but it is usually determined at 25
o
C or 298 K.
h H H when T T C K
N h N h
C P R P R
o
e f
o
e
i f
o
i
= = = =
=

25 298
Products 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 h
C
=
The lower heating value, LHV, is the heating value when water appears as a gas in
the products.
LHV h h with H O in products
C C gas
= =
2
31
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 h h with H O in products
C C liquid
= =
2
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 25
o
C. 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 h
H O fgH O
= +
2 2
32
Example 15-11

The enthalpy of combustion of gaseous octane C
8
H
18
at 25
o
C with liquid water in the
products is -5,500,842 kJ/kmol. Find the lower heating value of liquid octane.
8 18 8 18 2 2
2
8 18 8 18 2
8 18
5, 500,842 9 (44, 010)
5,104, 752
gas gas
C H C H H O fg H O
LHV HHV N h
kJ kmol H O kJ
kmol C H kmol C H kmol H O
kJ
kmol C H
=
=
=
8 18 8 18 8 18
8 18
8 18
(5,104752 41, 382)
5, 063, 370
liq gas
C H C H fgC H
liq
LHV LHV h
kJ
kmol C H
kJ
kmol C H
=
=
=
Can you explain why LHV
liq
< LHV
gas
?
33
Closed System Analysis

Example 15-12

A mixture of 1 kmol C
8
H
18
gas and 200 percent excess air at 25
o
C, 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.
Apply the first law closed system:
34
Assume that the reactants and products are ideal gases; then
PV NR T
u
=
The balanced combustion equation for 200 percent excess (300 percent theoretical)
air is
C H O N
CO O H O N
8 18 2 2
2 2 2 2
3 12 5 376
8 25 9 141
+ +
+ + +
( )( . ) ( . )
35
Q
h h
kJ
kmol C H
net CO
H O
O
N
K
o
C H
O
N
= +
+ +
+ +
+ +
+
+
+
=
8 393 520 53 848 9364 8 314 1200
9 241820 44 380 9904 8 314 1200
25 0 38 447 8682 8 314 1200
141 0 36 777 8669 8 314 1200
1 208 450 8 314 298
37 5 0 8682 8682 8 314 298
141 0 8669 8669 8 314 298
112 10
2
2
2
2
8 18
2
2
298
6
8 18
( , , . ( ))
( , , . ( ))
( , . ( ))
( , . ( ))
( , . ( ))
. ( . ( ))
( . ( ))
.
To find the final pressure, we assume that the reactants and the products are ideal-
gas mixtures.
PV N R T
PV N R T
u
u
1 1 1 1
2 2 2 2
=
=
36
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
PV
N R T
N R T
u
u
2 2
1 1
2 2
1 1
=
but V
2
= V
1
.
37
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
Q
T
S S S S kJ k
k
k
gen CV
+ + >
React Prod
A ( / )
38
For an adiabatic, steady-flow process, the entropy balance relation reduces to
S S S
gen adiabatic ,
= >
Prod React
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 P
o
= 1 atm. Absolute entropy values at other
pressures P for any temperature T are determined from
s T P s T P R
P
P
kJ kmol K
o
o u
o
( , ) ( , ) ln [ / ( )] =
For component i of an ideal-gas mixture, the absolute entropy can be written as
s T P s T P R
y P
P
kJ kmol K
i i i
o
o u
i m
o
( , ) ( , ) ln [ / ( )] =
where P
i
is the partial pressure, y
i
is the mole fraction of the component, and P
m
is
the total pressure of the mixture in atmospheres.
39
Example 15-13

A mixture of ethane gas C
2
H
6
and oxygen enters a combustion chamber at 1 atm,
25
o
C. The products leave at 1 atm, 900 K. Assuming complete combustion, does the
process violate the second law?
The balanced combustion equation is
C H O CO H O
2 6 2 2 2
35 2 3 + + .
40
The mole fractions for the reactants and the products are
y
y
y
y
C H
O
CO
H O
2 6
2
2
2
1
1 35
1
4 5
35
1 35
35
4 5
2
2 3
2
5
3
2 3
3
5
=
+
=
=
+
=
=
+
=
=
+
=
. .
.
.
.
.
Now calculate the individual component entropies.

For the reactant gases:
41
S N s
kJ
kmol K
i i
C H
React
Reactants
=
= +
=

1 242 0 35 2071
9669
2 6
( . ) . ( . )
.
42
For the product gases:
43
S N s
kJ
kmol K
e e
C H
Prod
Products
=
= +
=

2 2712 3 232 6
12402
2 6
( . ) ( . )
.
The entropy change for the combustion process is
S S
kJ
kmol K
kJ
kmol K
C H
C H
Prod React
=

( . . )
.
1240 2 966 9
2733
2 6
2 6
Now to find the entropy change due to heat transfer with the surroundings. The
steady-flow conservation of energy for the control volume is
Q H H
N h h h N h h h
net sys P R
e f
o
T
o
e i f
o
T
o
i
=
= + +

[ ( )] [ ( )]
Products Reactants
44
Q
h h
kJ
kmol C H
net sys CO
H O
K
o
C H
O
= +
+ +
+
+
=
2 393 520 37 405 9364
3 241820 31828 9904
1 214 820
35 0 8682 8682
1306 10
2
2
2 6
2
298
6
2 6
( , , )
( , , )
( , )
. ( )
.
Q
T
Q
T
kJ
kmol C H
K
kJ
kmol C H K
k
k
net sys
o

=
=

+
=

1306 10
25 273
4 383
6
2 6
2 6
.
( )
,
45
The entropy generated by this combustion process is
Since S
gen
, or AS
net
, is 0, the second law is not violated.