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Examples:
Combustion- a chemical reaction during which a fuel is
Gasoline – Octane -C8H18 oxidized and a large quantity of energy is released.
The oxidizer most often used in combustion processes is air.
Diesel Fuel – Dodecane – C12H26 Dry air
Methanol – Methylalcohol – 20.9 % O2
CH3OH 78.1 % N2
0.9 % Argon
Natural Gas- mixture of methane Small amounts of CO2, He, Neon, and H2
and smaller amounts of gases- In the analysis of combustion
sometimes treated as methane – Argon in the air – treated as N2
CH4 gases existing in trace amount are disregarded
Dry air can be approximated as
1 kmol O 2 3.76 kmol N 2 4.76 kmol air 21% O2
79% N2
5
Fuels and Combustion (Cont…)
Note:
Nitrogen Water Vapor (moisture)
At ordinary combustion temperatures,
nitrogen behaves as an inert gas and does not the air that enters a
react with other chemical elements.
But even then the presence of nitrogen greatly
combustion chamber normally
affects the outcome of a combustion process contains some water vapor (or
since nitrogen usually enters a combustion moisture), which also
chamber in large quantities at low deserves consideration.
temperatures and exits at considerably higher
temperatures, absorbing a large proportion of for most combustion
the chemical energy released during processes, the moisture in the
combustion. air can also be treated as an
Throughout this chapter, nitrogen is assumed
inert gas, like nitrogen.
to remain perfectly inert.
6
Fuels and Combustion (Cont…)
8
Example 3.1.
One kmol of octane (C8H18) is burned with air that contains 20 kmol of O 2
, as shown below. Assuming the products contain only CO 2, H2O, O2, and
N2, determine the mole number of each gas in the products and the air-
fuel ratio for this combustion process.
9
Theoretical and Actual Combustion Process
A combustion process is complete if all The minimum amount of air
the carbon in the fuel burns to CO2, all needed for the complete
combustion of a fuel is called the
the hydrogen burns to H2O, and all the stoichiometric or theoretical air.
sulfur (if any) burns to SO2. The theoretical air is also referred
The combustion process is incomplete if to as the chemically correct
the combustion products contain any amount of air, or 100 percent
theoretical air.
unburned fuel or components such as
The ideal combustion process
C,H2,CO, or OH.
during which a fuel is burned
completely with theoretical air is
called the stoichiometric or
theoretical combustion of that
fuel.
10
Theoretical and Actual Combustion Process
(Cont…)
In actual combustion processes, it is common practice to use more air
than the stoichiometric amount :-
to increase the chances of complete combustion or
to control the temperature of the combustion chamber.
The amount of air in excess of the stoichiometric amount is called
excess air.
The amount of excess air is usually expressed in terms of the
stoichiometric air as percent excess air or percent theoretical air.
Amounts of air less than the stoichiometric amount are called
deficiency of air and are often expressed as percent deficiency of air.
11
Example 3.2.1
Calculate the theoretical air-fuel ratio for the combustion of octane, C 8H18.
Example 3.2.2
Methane (CH4) is burned with atmospheric air. The analysis of the products
on a dry basis is as follows: CO2: 10.00 %; O2: 2.37 %; CO: 0.53 %; N2:
87.10 %.
Calculate the air-fuel ratio and the percent theoretical air and determine the
combustion equation.
12
Example 3.2.3
Determine the molal analysis of the products of combustion when octane,
C8H18, burned with 200 % theoretical air, and determine the dew point of
the products if the pressure is 0.1 MPa.
13
Example 3.2.4
Octane (C8H18) is burned with 250 percent theoretical air, which enters the
combustion chamber at 25oC. Assuming complete combustion and a total
pressure of 1 atm, determine,
(a) the air-fuel ratio, and
(b) the dew-point temperature of the products.
14
Experimental Analysis of Products of Combustion (Orsat Analyzer)
Compresse Liquid
liquid at -40oC is taken as the reference state,
Table A7
and the enthalpy and entropy are assigned
6
A d )
e ate por
zero values at that state. l
b e a
Ta erh r v
p (o
Su ter
In thermodynamics we are concerned with the Saturated liquid-
vapor region w
a
Table A4 T entry
changes in properties, and the reference Table A5 P entry
Air 29 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
h 0 for all stable elements.
f
Where Nr and Np represent the number of moles of the reactant r and the product p
25
3.5. First Law Analysis of Reacting Systems (Cont…)
Q W N p (h h h ) p N r (h h h ) r
f f
Q h c N p (h h ) p N r (h h ) r
The energy balance relations above are sometimes written without the
work term since most steady-flow combustion processes do not involve
any work interactions.
26
A combustion chamber normally involves heat output but no heat input.
Then the energy balance for a typical steady-flow combustion process
becomes
Qout N r (h f h h ) r N p (h f h h ) p
Energy in by mass Energy out by mass
per mole of fuel per mole of fuel
To avoid using another property-the internal energy of formation u f we
utilize the definition of enthalpy
(u h Pv or u f u u h h h Pv)
f
Q W N p (h f h h Pv) p N r (h f h h Pv) r
28
Enthalpy of Formation
Example:
Butane gas C4H10 is burned in theoretical air as shown below. Find the net heat transfer per
kmol of fuel.
Fuel CO2
Reaction Chamber
C4H10 H2O
Theoretical N2
Air
Products
Reactants TP ,PP
TR ,PR Qnet
4 CO2 5 H2 O 24.44 N 2
Enthalpy of Formation
The steady-flow heat transfer is
Qnet H P H R
N [h
Products
e f
o
(hT h o )]e N [h
Reactants
i f
o
(hT h o )]i
Reactants: TR = 298 K
Comp Ni h fo hT ho N i [h fo (hT h o )]
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
HR N [h
Reactants
i f
o
(hT h o )]i
30
kJ
126,150
kmol C4 H10
Enthalpy of Formation
Products: TP = 1000 K
Ne o
Comp kmol/kmol fuel h f
o
hT h N e [h fo (hT h o )]
kJ/kmol kJ/kmol kJ/kmol kJ/kmol fuel
CO2 4 -393,520 42,769 9,364 -1,440,460
H 2O 5 -241,820 35,882 9,904 -1,079,210
N2 24.44 0 30,129 8,669 +524,482
HP e f T )]e
N [h o
Products
( h h o
kJ
1,995,188
kmol C4 H10
Qnet H P H R
kJ 31
1,869,038
kmol C4 H10
Example 3.4.1
Acetylene gas (C2H2) is burned completely with 20 percent excess
air during a steady-flow combustion process. The fuel and the air
enter the combustion chamber at 25 0C, and the products leave at
1500 K. Determine,
(a) the air-fuel ratio, and
(b) the heat transfer for this process.
32
Example 3.4.2.
Consider the following reaction, which occurs in a steady-state, steady-flow process.
33
Adiabatic Flame Temperature
When W=0 and changes in kinetic In the limiting case of no heat loss to
or potential energies, the surroundings (Q=0), the
the chemical energy released temperature of the products will
during a combustion process either reach a maximum, which is called
is:- the adiabatic flame or adiabatic
lost as heat to the surroundings combustion temperature of the
or reaction.
used internally to raise the
temperature of the combustion
products.
The smaller the heat loss, the
larger the temperature rise.
34
Adiabatic Flame Temperature (Cont…)
Qout N p ( h fo h h o ) p N r ( h fo h h o ) r
35
Adiabatic flame temperature
Assume:
(a)Heat transfer from the system is zero, i.e., adiabatic combustion.
Thus:
(a) All the heat of reaction, HRP, goes into the products.
(b) The temperature in this case is called the adiabatic flame temperature.
p f
N ( h o
h (T *
) h o
) p r f
N ( h o
h h o
)r
r f
N ( h o
h h o
Ru T ) r p f
N ( h o
h (T *
) h o
Ru T *
)p
T* - adiabatic flame temperature36
Adiabatic Flame Temperature
• Not unique
• Depends on the:-
state of the reactants,
degree of completion of the reaction (products),
amount of air used.
• The actual maximum temperature encountered in a combustion chamber is
lower than the theoretical adiabatic flame temperature, due to:-
incomplete combustion (bad mixing),
heat loss,
dissociation of products.
37
Determining T*
38
Adiabatic Flame Temperature
The combustion equation is
CO2
Fuel Combustion
C8H18 Chamber O2
400% H2O
TheoAir
N2
Reactants Products
Qnet = 0
TR = 298 K TP = ?
PR = 0.1 MPa PP = 0.1MPa
C8 H18 4(12.5) (O2 3.76 N 2 )
8 CO2 37.5 O2 9 H2 O 188 N 2
The steady-flow heat transfer is
Qnet H P H R
e f T )]e
N [h
Products
o
( h h o
i f T )]i
N [h o
Reactants
( h h o
39
0 ( Adiabatic Combustion)
Adiabatic Flame Temperature
Thus, HP = HR for adiabatic combustion. We need to solve this equation for TP.
Since the reactants are at 298 K, ( hT h o )
i = 0,
HR i fi
N h o
Reactants
40
Adiabatic Flame Temperature
HP e f TP )]e
N [h o
Products
( h h o
To estimate TP, assume all products behave like N2 and estimate the
adiabatic flame temperature from the nitrogen data.
242.5hTP , N 2 7,193,895
kJ
hTP , N 2 29,6655
.
kmol N 2
Tp 985 K
42
Adiabatic Flame Temperature
Because of the tri-atomic CO2 and H2O, the actual temperature will be somewhat less than
985 K. Try 960 K and 970K.
Ne
h960 K h970 K
CO2 8 40,607 41,145
H2O 9 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
43
Example 1 – adiabatic flame T
C8H18(l)
25 ° C, 1 atm CO2
Combustion Tp
H2O
chamber 1 atm N2
Air O2
25 °C, 1 atm
N p ( h h (T ) h ) p N r ( h h h ) r
o
f
* o o
f
o
45
Example 1 (continued)
Substance
h fo o
h298 K hT *
C8H18(l) -249,950 h -
O2 0 8682 -
N2 0 8669 ?
CO2 -393,520 9364 ?
H2O(g) -241,820 9904 ?
46
Example 1 (continued)
(8kmol CO2)[(-393520+hCO2,T*-9364)kJ/kmolCO2]
+(9kmol H2O)[(-241,820+hH2O,T*-9904)kJ/kmol H2O]
+(47kmol N2)[(0+hN2,T*-8669)kJ/kmol N2]
= (1kmol C8H18)[-249950kJ/kmol C8H18]
which yields
8hCO2,T*+9hH2O,T*+47hN2,T*=5646081kJ
Assume the value of T* until
Left=right=5646081kJ
T*=2394.5 K
47
Example 1 (continued)
(b) The combustion equation
C8H18(l)+50(O2+3.76N2->8CO2+9H2O+37.5O2+188N2
Repeat the procedure in (a)
T*=962 K
48
Example 1 (continued)
(c) The combustion equation
C8H18(l)+11.25(O2+3.76N2->5.5CO2+2.5CO+9H2O+42.3N2
Repeat the procedure in (a)
T*=2236 K
49
Notice that
• the adiabatic flame temperature decreases as a
result of incomplete combustion or using excess
air.,
• the maximum adiabatic flame temperature is
achieved when complete combustion occurs with
the theoretical amount of air .
50
Remark!
In combustion chambers, the highest
temperature to which a material can be
exposed is limited by metallurgical
considerations.
Therefore, the adiabatic flame temperature
is an important consideration in the design
of combustion chambers, gas turbines, and
nozzles.
The maximum temperatures that occur in
these devices are considerably lower than
the adiabatic flame temperature; however,
since the combustion is usually
incomplete, some heat loss takes place,
and some combustion gases dissociate at
high temperatures.
51
The Enthalpy of Reaction and Enthalpy of
Combustion
Closed System Analysis:
Example:
A mixture of 1 kmol C8H18 gas and 200% excess air at 250C, 1 atm is
burned completely in a closed system (a bomb) and is cooled to 1200
K. Find the:-
Heat transfer from the system
System final pressure.
Wnet
1 kmol C8H18 gas
Assume that the reactants and products are ideal gases, then
53
The Enthalpy of Reaction and Enthalpy of Combustion
The balanced combustion equation for 200% excess (300% theoretical) air