CHAPTER

3
Reacting Mixtures
and
Combustion
1
 Contents

Fuels and Combustion

Theoretical and Actual Combustion Process
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)
2
 3.1. Fuels and Combustion

 Fuel- any material that can be Most liquid hydrocarbon fuels are
obtained from crude oil by
burned 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.

3
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 Natural Natural (primary):

(primary): (primary): Natural Gas
Wood, Peat, Petroleum
Lignite coal Prepared
Prepared (Secondary):
Prepared (Secondary): Petroleum Gas,
(Secondary): Gasoline, Kerosene, Producer Gas, Coke-
Coke, Charcoal, Fuel Oil, Alcohol, oven gas, Blast
Briquette Benzene, Shale Oil furnace gas,
Carbureted Gas 4
 3.1. Fuels and Combustion (Cont…)

Examples:  Combustion- a chemical reaction during which a

 Gasoline – Octane -C8H18 fuel is oxidized and a large quantity of energy is
released.
 Diesel Fuel – Dodecane –  The oxidizer most often used in combustion
C12H26 processes is air.
 Dry air
 Methanol – Methylalcohol
 20.9 % O2
– CH3OH
 78.1 % N2
 Natural Gas- mixture of  0.9 % Argon
methane and smaller  Small amounts of CO2, He, Neon, and H2
amounts of gases-  In the analysis of combustion
sometimes treated as  Argon in the air – treated as N2
methane – CH4  gases existing in trace amount are disregarded
 Dry air can be approximated as
 21% O2

1 kmol O 2  3.76 kmol N 2  4.76 kmol air  79% N2

5
 3.1. Fuels and Combustion (Cont…)

Note: Water Vapor (moisture)

Nitrogen
 At ordinary combustion temperatures, the air that enters a
nitrogen behaves as an inert gas and does combustion chamber normally
not react with other chemical elements. contains some water vapor (or
But even then the presence of nitrogen moisture), which also
greatly affects the outcome of a deserves consideration.
combustion process since nitrogen usually for most combustion
enters a combustion chamber in large processes, the moisture in the
quantities at low temperatures and exits at air can also be treated as an
considerably higher temperatures, inert gas, like nitrogen.
absorbing a large proportion of the
chemical energy released during
combustion.
Throughout this chapter, nitrogen is
assumed to remain perfectly inert.
6
 3.1. Fuels and Combustion (Cont…)

• Fuel must be brought above its

ignition temperature to start the
combustion.
Conservation of Mass Principle
7
 3.1. 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

8
 3.2. Theoretical and Actual Combustion Process
 A combustion process is complete  The minimum amount of air
if all the carbon in the fuel burns needed for the complete
to CO2, all the hydrogen burns to combustion of a fuel is called the
H2O, and all the sulfur (if any) stoichiometric or theoretical air.
burns to SO2.  The theoretical air is also referred
 The combustion process is to as the chemically correct
incomplete if the combustion amount of air, or 100 percent
products contain any unburned theoretical air.
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.

9
 3.2. 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.

10
3.4. Enthalpy of Formation and Enthalpy of Combustion

11
 Thermodynamics Tables
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 0.01 oC 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
Table A7
liquid at -40oC is taken as the reference state,
6

and the enthalpy and entropy are assigned

A ed r )
b le eat po
h a
T a er r v
up (o
Saturated liquid- S ter

zero values at that state. vapor region

Table A4 T entry
w
a

Table A5 P entry

 In thermodynamics we are concerned with the

changes in properties, and the reference Table A8
Saturated ice-vapor

chosen has no consequences in the calculations.

12
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 Tref=298.15K(25 0C) and Pref=1 atm.
 Using the datum introduced above, enthalpy values can be
assigned to compounds for use in the study of reacting systems.
 The enthalpy of formation ( h ) is the energy released or absorbed

f

when the compound is formed from its elements, the compound

and elements all being at Tref and Pref.

13
 3.4. Enthalpy of Formation and Enthalpy of Combustion
•Assuming that the atoms of each
 We ignored chemical energy up to reactant remains intact (no nuclear
now. Only focused on sensible and reactions) and disregarding any
latent energies. changes in kinetic and potential
 During a chemical reaction, some energies,
chemical bonds that bind the atoms •the energy change of a system during a
into molecules are broken, and new chemical reaction will be due to a
ones are formed. change in state and a change in
 The chemical energy associated with chemical composition. That is,
these bonds, in general, is different Esys  Estate  Ech em
for the reactants and the products.
 A process that involves chemical •In thermodynamics we are concerned with the
reactions will involve changes in changes in the energy of a system during a
process, and not the energy values at the
chemical energies, which must be particular states.
accounted for in an energy balance. •We can choose any state as the reference state
and assign a value of zero to the internal
energy or enthalpy of a substance at that state.

14
 3.4. Enthalpy of Formation (Cont…)
• It is necessary to have a • When analyzing reacting systems, we
common reference state for all must use property values relative to
substances. the standard reference state.
• The chosen reference state is • However, it is not necessary to
prepare a new set of property tables
250C (770F) and 1 atm, which is
for this purpose.
known as the standard
• We can use the existing tables by
reference sate.
subtracting the property values at the
• Property values at the standard reference state from the
standard reference sate are values at the specified state.
indicated by a superscript “0” • The ideal-gas enthalpy of N2 at 500K
(such as h0 and u0) relative to the standard reference
state, for example, is

15
 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
16
Octane (vapor) C8H18 114 -208,450
Dodecane C12H26 170 -291,010
 Enthalpy change will be different for  For combustion processes, the enthalpy
different reactions, and it would be of reaction is usually referred to as the
very desirable to have a property to enthalpy of combustion, hc, which
represent the changes in chemical represents the amount of heat released
energy during a reaction. during a steady-flow combustion process
when 1 kmol (or 1 kg) of fuel is burned
 This property is the enthalpy of
completely at a specified temperature
reaction, hR, which is defined as the and pressure
difference between the enthalpy of
the products at a specified state
and the enthalpy of the reactants
at the same state for a complete  A more practical approach would be
reaction.
to have a more fundamental
property to represent the chemical
energy of an element or a
compound at some reference state.
 This property is the enthalpy of
formation, hf, which can be viewed
as the enthalpy of a substance at a
specified state due to its chemical
composition. 17
 3.4. 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.

18
 3.4. Enthalpy of Formation (Cont…)
 Heating value • Higher Heating Value (HHV)-
when the H2O in the products is
 the amount of heat
in the liquid form
released when a fuel is
• Lower Heating Value (LHV)-
burned completely in a
when the H2O in the products is
steady-flow process and
in the vapor form
the products are returned
to the state of the
reactants.
 equals to the absolute
value of the enthalpy of
combustion of the fuel

19
 3.5. 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 h0(the sensible enthalpy at the
standard reference state to 25 0C and 1 atm).
This definition enable us to use enthalpy values from
tables regardless of the reference state used in their
construction.

20
 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 , respective ly.

Per mole of fuel

         
Q in  W in  Q out  Wout   N p ( h  h  h ) p   N r (h  h  h ) r
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
21
 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 forhacparticular 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.

22
A combustion chamber normally involves heat output but no heat input.
Then the energy balance for a typical steady-flow combustion process
becomes

Qo u t   N r (h f  h  h ) r   N p (h f  h  h ) p
   

               
En erg yin b y mass En ergyo u t by mass
p er mo le of fu el p er mole o f fu el

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.

23
 Closed Systems
The general closed-system energy balance relation Ein  Eout can
Ebe
system
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
   

24
 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
  N2
Theoretical
Air
Products
Reactants TP ,PP
TR ,PR Qnet

 Balanced combustion equation:

C4 H10  6.5 (O2  3.76 N 2 )  25

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
26
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
H2 O 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 27
 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.

28
 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 0C. Determine the heat transfer per kilo mole of fuel entering
the combustion chamber.

29
 Quiz 1
One kmol of a liquid octane (C8H18) is burned with air
that contains 20 kmol of O2, as shown in Fig. Assuming
the products contain only CO2, H2O, O2, and N2,
determine the mole number of each gas in the
products and the air–fuel ratio for this combustion
process. Also, determine the net heat released during
the combustion when the air enter at 370C and fuel at
250C, the product at 1300K

30
 PROBLEM 2
Ethane (C2H6) is burned with 20 percent excess
air during a combustion process, as shown
below. Assuming complete combustion and a
total pressure of 100 kPa,
a) determine the air–fuel ratio
b) the dew point temperature of the products

31
 PROBLEM 3
Octane (C8H18) is burned with dry air. The volumetric
analysis of the products on a dry basis is
• CO2: 10.02 percent
• O2: 5.62 percent
• CO: 0.88 percent
• N2: 83.48 percent
Determine (a) the air–fuel ratio, (b) the percentage of
theoretical air and excess air used,

32
 3.6. Adiabatic Flame Temperature
 When W=0 and changes in kinetic or  In the limiting case of no heat loss to
potential energies, the surroundings (Q=0), the
 the chemical energy released during temperature of the products will
a combustion process either is:- reach a maximum, which is called
 lost as heat to the surroundings the adiabatic flame or adiabatic
or combustion temperature of the
reaction.
 used internally to raise the
temperature of the combustion
products.
 The smaller the heat loss, the larger
the temperature rise.

33
 3.6. 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 fo  h  h o  RuT ) r   N p ( h fo  h  h o  RuT ) p

34
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.

35
 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 temperature

36
 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 o
 ( h  h o
 i f T )]i
N [h o
 ( h  h o
39
Products Reactants

 0 ( Adiabatic Combustion)
 Adiabatic Flame Temperature
 Thus, HP = HR for adiabatic combustion. We need to solve this equation
for TP.
o
h 
  Since the reactants are at 298 K, ( T ) = 0, h
i

HR  Nh
Reactants
i
o
f i

 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,

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 , H2O  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 o
h fo 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)) H2O
 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 54
.  106
 112
kmol C8 H18