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Chapter Three

Reacting Mixtures and


Combustion
Engineering Thermodynamics II
[MEng 3131 ]
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Content
Chapter 3 Reacting Mixtures and Combustion

• Fuels and Combustion


• Theoretical and Actual Combustion Process
• Experimental Analysis of Products of Combustion (Orsat Analyzer)
• Enthalpy of Formation and Enthalpy of Combustion
• First Law Analysis of Reacting Systems
• Adiabatic Flame Temperature
• Experimental Determination of Heating Values of Fuels (Bomb
Calorimeter)
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Fuels and Combustion

Most liquid hydrocarbon fuels are


 Fuel- any material that can be burned obtained from crude oil by
to release energy. distillation

 Most familiar fuels consist primarily


of hydrogen and carbon. They are
called hydrocarbon fuels - CnHm.
 Liquid hydrocarbon fuels are mixtures
of many different hydrocarbons, they
are usually considered to be a single
hydrocarbon for convenience.
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Fuels can be classified according to whether:
 They occur in nature called primary fuels or are prepared called
secondary fuels;
 They are in Solid, Liquid or gaseous state
Type of fuel: Solid Type of fuel: Liquid
Type of fuel: Gaseous
Natural (primary): Natural (primary):
Natural (primary): Natural
Wood, Peat, Petroleum Gas
Lignite coal
Prepared (Secondary): Prepared (Secondary):
Prepared(Secondary): Petroleum Gas, Producer
Gasoline, Kerosene, Fuel Gas, Coke-oven gas,
Coke, Charcoal, Oil, Alcohol, Benzene, Blast furnace gas,
Briquette Shale Oil Carbureted Gas 4
Fuels and Combustion (Cont…)

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
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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.
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Fuels and Combustion (Cont…)

• Fuel must be brought above its


ignition temperature to start the
combustion. Conservation of Mass Principle
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Fuels and Combustion (Cont…)

 A frequently used quantity in the


analysis of combustion processes
to quantify the amounts of fuel
and air is the air-fuel ratio, AF.
 It is usually expressed on a mass
basis and is defined as the ratio
of the mass of air to the mass of
fuel for a combustion process.
mair
AF 
m fuel

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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.

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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.

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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.

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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.

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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.

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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.

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Experimental Analysis of Products of Combustion (Orsat Analyzer)

 An Orsat analyser is employed in the


experimental analysis of products of
combustion.
 The apparatus , in its simplest form,
consists of
 Measuring tube-the burette surrounded
by a water jacket to maintain constant
temperature,
 Three vessels, A, B, and C containing the
chemicals [absorption ]
 Caustic soda-CO2  Experimental analysis of the dry products of
combustion indicates whether or not a chemical
 Pyrogallic acid – O2
reaction is complete.
 Solution of cuprous chloride - CO  Presence of CO – incomplete combustion
 Presence of O2 – excess air has been supplied 15
Enthalpy of Formation and Enthalpy of Combustion
Reference State and Reference Values
 The values of u, h, and s cannot be measured directly, and they are calculated from measurable
properties using the relations between thermodynamic properties. However, those relations
give the changes in properties, not the values of properties at specified state.
 For water, the state saturated liquid at 0.01oC is taken as the reference state, and the internal
energy and entropy are assigned zero values at that sate.
 For refrigerant 134a, the state saturated

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

chosen has no consequences in the calculations.


Table A8
Saturated ice-vapor
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Reacting Mixtures
 When chemical reaction occurs, reactants disappear and products are formed, so
differences can not be calculated for all substances involved.
 An enthalpy datum for the study of reacting systems can be established by
assigning arbitrarily a value of zero to the enthalpy of the stable elements at a
state called the standard reference state and defined by T ref=298.15K(25 0C) and
Pref=1 atm.
 Using the datum introduced above, enthalpy values can be assigned to
compounds for use in the studyh fof reacting systems.
 The enthalpy of formation ( ) is the energy released or absorbed when the
compound is formed from its elements, the compound and elements all being at
Tref and Pref.
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3.4. Enthalpy of Formation and Enthalpy of Combustion
• Assuming that the atoms of each reactant
 We ignored chemical energy up to now. remains intact (no nuclear reactions) and
Only focused on sensible and latent disregarding any changes in kinetic and
energies. potential energies,
 During a chemical reaction, some • the energy change of a system during a
chemical bonds that bind the atoms into chemical reaction will be due to a change
molecules are broken, and new ones are in state and a change in chemical
formed. composition. That is,
 The chemical energy associated with Esys  Estate  Echem
these bonds, in general, is different for the • In thermodynamics we are concerned with the
reactants and the products. changes in the energy of a system during a
 A process that involves chemical reactions process, and not the energy values at the
particular states.
will involve changes in chemical energies,
• We can choose any state as the reference state
which must be accounted for in an energy
and assign a value of zero to the internal energy
balance.
or enthalpy of a substance at that state.
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Enthalpy of Formation (Cont…)
• It is necessary to have a common • When analyzing reacting systems, we
reference state for all must use property values relative to the
standard reference state.
substances.
• However, it is not necessary to prepare a
• The chosen reference state is new set of property tables for this
250C (770F) and 1 atm, which is purpose.
known as the standard reference • We can use the existing tables by
sate. subtracting the property values at the
standard reference state from the values
• Property values at the standard at the specified state.
reference sate are indicated by a • The ideal-gas enthalpy of N2 at 500K
superscript “0” (such as h0 and relative to the standard reference state,
u0) for example, is

  h 500 K  h  14,581  8669  5912kJ / kmol.
Enthalpy  h  (h  h ) (kJ/kmol)
f 19
Enthalpy of Formation
 The enthalpy of formation of the elements found naturally as diatomic
elements, such as nitrogen, oxygen, and hydrogen, is defined to be
zero. Substance Formula M o
hf kJ/kmol

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

Acetylene C2H2 26 +226,730


Ethane C2H6 30 -84,680
Propane C3H8 44 -103,850
Butane C4H10 58 -126,150
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Octane (vapor) C8H18 114 -208,450
Dodecane C12H26 170 -291,010
 Enthalpy change will be different for different
reactions, and it would be very desirable to hC  H prod  H react
have a property to represent the changes in
chemical energy during a reaction.
 This property is the enthalpy of reaction, hR,
 A more practical approach would be
which is defined as the difference between the to have a more fundamental
enthalpy of the products at a specified state property to represent the chemical
and the enthalpy of the reactants at the same energy of an element or a compound
state for a complete reaction. at some reference state.
 For combustion processes, the enthalpy of  This property is the enthalpy of
reaction is usually referred to as the enthalpy formation, hf, which can be viewed
of combustion, hc, which represents the as the enthalpy of a substance at a
amount of heat released during a steady-flow specified state due to its chemical
combustion process when 1 kmol (or 1 kg) of composition.
fuel is burned completely at a specified
temperature and pressure 21
Enthalpy of Formation (Cont…)

 To establish a starting point, we assign


the enthalpy of formation of all stable
elements (such as O2,N2,H2, and C) a
value of zero at the standard reference
state of 250C and 1 atm.


h  0 for all stable elements.
f

(This is no different from assigning the internal energy


of saturaded liquid water a value of zero at 0 C.)
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Enthalpy of Formation (Cont…)
 Heating value
 the amount of heat released
when a fuel is burned • Higher Heating Value (HHV)-
completely in a steady-flow
process and the products are when the H2O in the products
returned to the state of the is in the liquid form
reactants. • Lower Heating Value (LHV)-
 equals to the absolute value of when the H2O in the products
the enthalpy of combustion of
is in the vapor form
the fuel

Heating value  hC HHV  LHV  ( N h fg ) H 2O (kJ/kg fuel)


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First Law Analysis of Reacting Systems
The energy balance(or 1st Law) relations developed earlier are applicable to both reacting and
non-reacting systems.
However, chemically reacting systems involve changes in their chemical energy, and thus it is
more convenient to rewrite the energy balance relations so that the changes in chemical
energies are explicitly expressed.
Steady-Flow Systems
 
Enthalpy  h  (h  h ) (kJ/kmol)
f

The term in the parentheses represents the sensible enthalpy


relative to the standard reference state.
Which is the difference b/n h(the sensible enthalpy at the
specified state) and ho(the sensible enthalpy at the standard
reference state to 25 oC and 1 atm).
This definition enable us to use enthalpy values from tables
regardless of the reference state used in their construction. 24
3.5. First Law Analysis of Reacting Systems
 
Neglecting changes in Kinetic and potential energies , E in  E out ,
for a chemically reacting steady  flow system :
     
Q in  W in   n r (h  h  h ) r  Q out  W out   n p (h  h  h ) p
   
f f
                        
Rate of net energy tranfer in Rate of net energy tranfer out
by heat, work, and mass by heat, work, and mass
 
where n p and n r represent the molal flow rates of the product p and
the reacant r , respectively.

Per mole of fuel


     
 Q out  Wout   N p (h  h  h ) p   N r (h  h  h ) r
   
Q in  W in f f
                         
Rate of net energy transfer in Rate of net energy transfer out
by heat, work, and mass by heat, work, and mass

Where Nr and Np represent the number of moles of the reactant r and the product p
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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  W  H prod - H reacat (kJ/kmol fuel)



If the enthalpy of combustion forh c a particular reaction is available, the steady-
flow energy equation per mole of fuel can be expressed as

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.

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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

It expresses that the heat output during a combustion process is


simply the difference between the energy of the reactants entering
and the energy of the products leaving the combustion chamber.
Closed Systems
The general closed-system energy balance relation Ein  Eout  Esystem
can be expressed for a stationary chemically reacting closed
system as:

(Qin  Qout )  (Win  Wout )  U prod  U react (kJ/kmol 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
   

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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

 Balanced combustion equation:

C4 H10  6.5 (O2  3.76 N 2 )  29

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.

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Example 3.4.2.
Consider the following reaction, which occurs in a steady-state, steady-flow process.

CH 4  2O2  CO2  2 H 2O(l )


The reactants and products are each at a total pressure of 0.1 MPa and 25 oC. Determine
the heat transfer per kilo mole of fuel entering the combustion chamber.

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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.
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Adiabatic Flame Temperature (Cont…)

For a typical steady-flow combustion process

Qout   N p ( h fo  h  h o ) p   N r ( h fo  h  h o ) r

For a typical closed combustion process

Qout   N r ( h  h  h  RuT ) r   N p ( h  h  h  RuT ) p


o
f
o o
f
o

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.

For a typical steady-flow combustion process

 p f
N ( h o
 h (T *
)  h o
) p   r f
N ( h o
 h  h o
)r

For a typical closed combustion process

 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*

T* is obtained by assuming a value to satisfy the energy balance by


trial and error. Note that the specific heat is not a constant, and
thus a table of values would be needed.

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

 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, T P 298 K,

40
Adiabatic Flame Temperature
HP   e f TP )]e
N [h o

Products
 ( h  h o

 8( 393,520  hTP  9364) CO2


 9( 241,820  hTP  9904) H2 O
 37.5(0  hTP  8682) O2
 188(0  hTP  8669) N 2

H P  ( 7,443,845  8hTP , CO2  9hTP , H2 O


kJ
 37.5hTP , O2  188hTP , N 2 )
kmol C4 H10
41
Adiabatic Flame Temperature
 Thus, setting HP = HR yields
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.

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

 Interpolation gives: TP = 962 K

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

Find: the adiabatic temperature for


(a) complete combustion with 100% theoretical air,
(b) complete combustion with 400% theoretical air,
(c) incomplete combustion (with CO) with 90% theoretical air
44
Example 1 (continued)
(a) The combustion equation
C8H18(l)+12.5(O2+3.76N2-> 8CO2+9H2O+47N2
Energy balance for steady-flow system

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

200% Excess Air


T1 = 25oC
Qnet
P1 = 1 Atm Rigid
52
T2 = 1200 K Container
The Enthalpy of Reaction and Enthalpy of Combustion
Closed System Analysis:

 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

Qnet  8( 393,520  53,848  9,364  8.314(1200)) CO2


 9( 241,820  44,380  9,904  8.314(1200)) H2 O
 25(0  38,447  8,682  8.314(1200)) O2
 141(0  36,777  8,669  8.314(1200)) N 2
 1( 208,450  h298 K  h o  8.314(1200)) C8 H18
 25(0  8,682  8,682  8.314(1200)) O2
 141(0  8,669  8,669  8.314(1200)) N 2
kJ
 112
.  106
kmol C8 H18 54

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