CHAPTER (2)

Thermodynamics of combustion
2.1 Types of reactions
- In some reactions, the energy that must be absorbed to break the bonds in the reactants is less
than the energy that is released when the new bonds of the products are formed. This means
that in the overall reaction, energy is released as either heat or light. This type of reaction is
called an exothermic reaction.
An exothermic reaction is one that releases energy in the form of heat or light. (Another way of
describing an exothermic reaction is that it is one in which the energy of the products is less
than the energy of the reactants, because energy has been released during the reaction.)

An exothermic reaction is a reaction that results in the system becoming hotter

Heat is given to the surrounding

- In other reactions, the energy that must be absorbed to break the bonds in the reactants is
more than the energy that is released when the new bonds in the products are formed. This
means that in the overall reaction, energy must be absorbed from the surroundings. This type of
reaction is known as an endothermic reaction.
An endothermic reaction is one that absorbs energy in the form of heat or light. (Another way of
describing an endothermic reaction is that it is one in which the energy of the products is
greater than the energy of the reactants, because energy has been absorbed during the
reaction).

An endothermic reaction is a reaction that results in the system becoming colder

Heat is taken in from to the surrounding

Enthalpy (H)(kj /kmol),is the total amount of chemical potential energy in a chemical system.
- The difference in energy (E) between the reactants and the products is known as the heat of
the reaction. It is also sometimes referred to as the enthalpy change of the system (ΔH).
An exothermic reaction ΔH < 0
An endothermic reaction ΔH > 0
The burning of fuel is an example of a combustion reaction; the following equations describe
the combustion of a hydrocarbon:
Fuel + oxygen → heat + water + carbon dioxide
Combustion reactions is an exothermic reactions
Bond energy
The energy which is absorbed when bonds are broken or released when bonds are formed.
Energy change, ΔH =∑ energy absorbed - ∑ energy released
The heat of reaction
The heat of the reaction is represented by the symbol ΔH, where:
ΔH=Eprod − Ereact
In an exothermic reaction
- ΔH is less than zero because the energy of the reactants is greater than the energy of the
products.
- A system releases heat to its surrounding, ΔH is negative
- The reactants have more potential energy than products
- The enthalpy of the products is less than the enthalpy of reactants,(the enthalpy change is
always negative)
- A+B AB + Energy
In an endothermic reaction
- ΔH is greater than zero because the energy of the reactants is less than the energy of the
products.
- A system absorbs heat from its surrounding, ΔH is positive
- The reactants have less potential energy than products
- Energy +A+B AB
Type of reaction Exothermic Endothermic
Energy absorbed or released Released Absorbed
Relative energy of reactants and Energy of reactants greater than Energy of reactants less than
products energy of product energy of product
Sign of ΔH Negative (i.e. <0) Positive (i.e. >0)

The units for ΔH are kJ/mol. In other words, the ΔH value gives the amount of energy that is
absorbed or released per mole of product that is formed. Units can also be written as kJ, which
then gives the total amount of energy that is released or absorbed when the product forms.
2-2 Activation Energy and Activated Complex
For a reaction to happen between two substances, a minimum amount of energy must be
absorbed to break the existing bonds of the reaction. This minimum energy is known as the
activation energy. (The minimum energy which a molecule must possess to be active)
-Activation energy is the minimum amount of energy that is needed to start a chemical reaction.
-Chemical reactions will not take place until the system has some minimum amount of energy
added to it. This energy is called the activation energy.
-When this minimum energy has been absorbed the reactance form a substance known as the
activated complex
-The activated complex (also known as the transition state) represents the structure of the
system as it exists at the peak of the activation energy curve.
-The activated complex is a temporary –high energy –unstable state between reactance and
products
- The activated complex occurs at a maximum potential energy (all kinetic energy is converted
into potential energy stored in chemical bonds needed to hold the complex together
momentarily)
It follows that the overall reaction can be looked upon as taking place by the following two step
process:-
Reactions Activated reactions Products
As shown in Fig.2.1 and Fig.2.2, the energy change for the formation of activated reaction is Ea
(Forward reaction) and Ea (reverse reaction), the enthalpy change of reaction, ΔH is taken to
be negative for an exothermic reaction.
ΔH= Ea (Forward reaction) - Ea (reverse reaction)
ΔH= Ea (reactants) - Ea (products)
The reactants and products contain potential energy, this potential energy is also known as
enthalpy (H)
ΔH= H (products) - H (reactants)
Thus the activation energy of a chemical reaction is the energy of the highest point of the
reaction path over a potential surface connecting reactants and products.
C3H8 + 5O2= 3CO2+8H2O +ΔH (- 2043 kj)
- Exothermic reaction
a) The reactants have more potential energy than products have
b) The extra energy is released to surroundings
c) The enthalpy of the product is less than enthalpy of the reactants
d) The enthalpy change is always negative(ΔH< 0)
- Endothermic reaction
a) The reactants have less potential energy than products have
b) Energy must be input in order to raise the particles up to the higher energy level
c) The enthalpy of the product is greater than enthalpy of the reactants
d) The enthalpy change is always positive(ΔH> 0)
 Fig.2.1 Activation energy diagrams

Fig.2.2 Activation energy diagrams can describe both exothermic and endothermic reactions

Activation energies of the forward reaction can be large, small, or zero (independently, of
course, of the value of ΔH)
Question2.1

Potential energy (kj/mol)

Activated complex
400
B
Products
300
A
C
200

100
Reactants

- The activation energy (Ea) for the reaction is shown by (A)

Ea(forward) =H(Activated complex) – H(reactants)=400-100=300 kj/mol
Ea(reverse) =H(Activated complex) – H(products)=400-300=100 kj/mol
- The enthalpy change for the reaction is shown by (C)
H=H (product) – H (reactants) =300-100=200 kj/mol (endothermic reaction)
Question2.2
Refer to the graph below and then answer the questions that follow:
1. Calculate ΔH.
2. Is the reaction endothermic or exothermic and why?
3. Calculate the activation energy for this reaction.

1- ΔH=energy of products−energy of reactants=10 kJ−45 kJ=−35 kj

2- Since ΔH<0. The reaction is exothermic (We also note that the energy of the reactants is
greater than the energy of the products).
3- activation energy=energy of activated complex−energy of reactants=103−45 kJ=58 kj
.Question 2.3
Refer to the graph below and then answer the questions that follow:

Progress of reaction
a) Does the graph represent endothermic or exothermic reaction?
b) Determine the heat of reaction for this reaction.
c) Determine the activation energy for this reaction.
d) Determine the reverse activation energy for this reaction
Solution 2.3
a. Exothermic
b. ΔH= -20kJ
c. 60kJ
d. 80kJ
.Question 2.4
Carbone monoxide CO (g) reacts with nitrogen dioxide NO2 (g).Carbone dioxide CO2 (g) and
nitrogen monoxide NO (g) are formed. Draw a potential energy diagram to illustrate the
reaction process, indicate on the diagram the activation energy of the forward reaction, Ea,for.
=134kj as well as ΔH=-226 kj.Calculate the activation energy of the reverse reaction,Ea,rev.
Solution 2.4

2.3 Reaction Rate

The basic theories of reaction kinetics are based on the assumption that molecular collisions
are in one way or another responsible for the occurrence of the reaction.
Arrhenius suggested an experimental formulation of the effect of temperature on the reaction
rates in the following equation:-
K=A.e –Ea / RuT
K=the reaction rate constant at some temperature, T
Ea = the activation energy (joules per mole)
Ru= the universal gas constant =8.314 J/ mol .k.
T = the absolute temperature (ok)
A = the frequency factor

The effect of a change of temperature (Using the Arrhenius equation)

You can use the Arrhenius equation to show the effect of a change of temperature on the rate
constant - and therefore on the rate of the reaction. If the rate constant doubles, for example, so
also will the rate of the reaction. Look back at the rate equation, what happens if you increase
the temperature by 10°C from, say, 20°C to 30°C (293 K to 303 K)?
The frequency factor, A, in the equation is approximately constant for such a small temperature
change. We need to look at how e- E/ RuT changes - the fraction of molecules with energies equal
to or in excess of the activation energy.
ln( K1/K2)= (Ea /Ru )[ (1/T2 ) – (1/T1)]
Let's assume activation energy of 50 kJ /mol. In the equation, we have to write that as 50000 J
/mol. The value of the gas constant, R, is 8.314 J/ mol. K .
At 20°C (293 K) the value of the fraction is:
e - E/ RuT =e – 50000/ (8.314x293) = 1.21x10-9
By raising the temperature just a little bit (to 303 K), this increases:
e - E/ RuT = e – 50000/ (8.314x303) = 2.38x10-9
You can see that the fraction of the molecules able to react has almost doubled by increasing
the temperature by 10°C. That causes the rate of reaction to almost double.
ln(K)=-(E/Ru.T)+constant =-(1/T)(E/Ru)+constant
ln(K) versus (1/T) should give a straight line with a slope of –E/Ru

ln(K) Slope = -E/Ru

α
1/T
Effect of temperature on reaction rate

Question 2.5
Consider an elementary reversible reaction; the forward rate constant is measured to be 2.0
L/mol.s at 45oC and 4.3 L/mol.s at 75oC,the reaction is exothermic by 40 kj/mol.detrmine :-
a) The activation energy of forward reaction
b) The reverse rate constant at 75oC
Solution 2.5
K2/K1= (4.3/2) =e^ [Ea / R (1/T1-1/T2)] = e^ [(Ea / 0.008314) (1/318 – 1/348]
2.15 = e^ 0.0326Ea
The activation energy of forward reaction, Ea=23.48 kj/mol.
Activation energy = the activation energy of forward reaction + (ΔH) = 63.48 kj/mol.
Factors that affect reaction rate
1. Particle size
A smaller particle size results in more surface area exposed. Therefore more particles react
and the process speeds up (ex: wood shavings burn better than logs)
2. Temperature
A higher temperature gives more particles the amount of kinetic energy to react. Thus a faster
reaction (ex. all reactions increase in speed when the temperature is increased)
3. Presence of a catalyst
A catalyst speeds up reactions by lowering the activation energy (ex: the presence of salt speeds
up the corrosion of iron magnesium alloys)
4. Concentration
If there is a higher concentration of reactants, there are more collisions happening. therefore,
the speed of reaction increases as more particles are reacting (ex. concentrated hydrochloric
acid reacts much faster with zinc than dilute hydrochloric acid will)
5. Pressure (only affects gasses)
Higher pressure will "push" the gasses closer together, which will force the gas particles to
collide more often, resulting in a faster reaction rate (ex. hydrogen and nitrogen react much
faster when pressure is increased)
2.4 Minimum Ignition Energy and Ignition Temperature
Minimum ignition energy (MIE) is the minimum amount of energy required to ignite a
combustible vapor, gas ,combustion is initiated by ignition, the purpose of which is to raise the
system represented by the mixture, to a level at which the combustion reaction becomes self-
propagating. The ignition process is considered to be chain reaction, or thermal explosion.
Reaction velocity will be proportional to concentration of fuel, Cf and of oxygen Co and also
exponentially proportional to temperature to temperature as :-
Vreact = k.Cf .Co .e -E/RT

Where;-
E=the activation energy
R= absolute gas constant
T=absolute temperature
K= reaction velocity constant
Ignition temperature can be considered as the minimum temperature below which reaction
cannot occure.Depending on external conditions, development of enough heat to compensate
for heat dissipated will permit such temperature to be reached. Ignition energy is required at
the flammable limits, of an air –gas mixture is greater than the stoichiometric mixture by an
amount which can be 20 to 50 times.similary, an increase in proportion of inert gas increases
the minimum ignition energy.
The ignition temperature is the minimum temperature at which the substance ignites, without
the presence of an external spark or flame. The concept of ignition temperature postulates a
minimum temperature below which ignition cannot occur. Depending on external conditions,
development of enough heat to compensate for beat dissipated will permit such a temperature to
be reached.
The amount of energy required to initiate the combustion reaction can be measured and is
expressed as the minimum ignition energy. For natural gas the value is 0.30 MJ and applies to
an air-to-gas ratio of 1.5:1 or approximately 17% excess air. The minimum ignition energy
values are usually given as the energy required to ignite the most reactive mixture of fuel and
air. A flammable mixture that is close to either the upper or lower limits may require a higher
amount of energy than the minimum ignition energy to ignite. The minimum ignition energy
(MIE) is a function of the gas concentration of the mixture. Figure 2.3 shows the minimum
ignition energies for different hydrocarbon fuels as U-shaped functions of the gas
concentration. The minimum ignition energy, MIE, is defined as the minimum value of the U-
shaped function. It should be noticed that the fuel-air equivalence ratioΦ at which the MIE
occurs increases with increasing carbon number, exhibited a steady shift toward fuel rich
conditions. Due to the higher diffusivities, MIE of molecules lighter than air (for example like
hydrogen and methane) occurs in lean mixture, i.e. when the fuel equivalence ratio,
Φ < 1. Figure 2.3 shows MIE value of methane is slightly higher than those of the higher
alkanes. The amount of energy required increases for other ratios as shown in Figure 2.3 and
approaches infinity at the limits of flammability. Minimum ignition energy is also related to the
laminar burning velocity:

Qmin = Cp (a/Δ) 3(Tf -To)

Where Qmin = minimum ignition energy

Cp= specific heat of mixture
a=thermal diffusivity of mixture = k / (ρ.Cp)
k= conductivity of air- gas mixture
ρ= mixture density
Δ= laminar burning velocity of mixture
Tf = flame temperature
To = initial air-gas mixture temperature
The minimum amount of energy supplied that is needed for combustion is the minimum ignition
energy. Every different fuel – air mixture will have different minimum ignition energies.
Factors that affect the minimum ignition energy are:
a) The temperature
b) The total energy supplied
c) The rate at which energy is supplied, or time period over which it is delivered
d) The area over which energy is delivered
The minimum ignition energies at stoichiometric conditions for propane and butane are 0.30
MJ and 0.38 MJ respectively, compared with 0.34 MJ for natural gas. Where heat is used to
initiate combustion the minimum ignition temperature is appropriate, which for natural gas is
approximately 650oC.
Figure 2.3: Minimum capacitive ignition energies of various gaseous alkanes/air mixtures as a
function of the volumetric ratio of fuel and air
2.5 Flammability limits
The minimum concentration of a particular combustible gas or vapour necessary to support its
combustion in air is defined as the Lower Explosive Limit (LEL) for that gas. Below this level,
the mixture is too “lean” to burn. The maximum concentration of a gas or vapour that will burn
in air is defined as the Upper Explosive Limit (UEL). Above this level, the mixture is too “rich”
to burn. The range between the LEL and UEL is known as the flammable range for that gas or
vapor. The upper (rich) and lower (lean) flammability limits define the range of concentrations
of a gas or vapour in air that can be ignited and sustain combustion. Any composition outside
of these limits cannot be ignited. The lower flammability limit decreases slightly as pressure is
increased. However, the upper flammability limit can increase substantially as pressure
increases.
The graph below, Fig.2.4 shows the effect of pressure on the flammability range of methane in
air. While these trends are consistent for all hydrocarbons, each fuel has a different
flammability range.
Other factors that widen the flammability range include:
1. Increased temperatures
2. Increased energy of the ignition source
3. If pure oxygen, instead of air, mixes with a hydrocarbon
4. Moisture and other contaminants will also affect the flammability range.
Lower Flammable Limit (LFL) Upper Flammable Limit (UFL)
% by volume of air % by volume of air

Gasoline (100 octane) 1.4% 7.6%

Methane 5.0% 15.0%

Propane 2.1% 9.5%
Diesel fuel 0.6 7.5%

2.6 Enthalpy of formation

In combustion processes, reactants are consumed to form products and energy is released. This
energy comes from a rearrangement of chemical bonds in the reactants to form the products.
The standard enthalpy of formation, Δ h̅of , quantifies the chemical bond energy of a chemical
species at standard conditions. The enthalpy of formation of a substance is the energy needed
for the formation of that substance from its constituent elements at STP conditions (25oC and 1
atm).
The standard enthalpy of formation is defined as the change in enthalpy when one mole of a
substance in the standard state (1 atm of pressure and 298.15 K) is formed from its pure
elements under the same conditions.
It becomes necessary to have a common reference state for all substances. The chosen
reference state is 25°C and 1 atm, which is known as the standard reference state. Property
values at the standard reference state are indicated by a superscript (°) (such as h° and u°).
Elements in their most stable forms, such as C (graphite), H2, O2, and N2, have enthalpies of
formation of zero
We can use the existing tables by subtracting the property values at the standard reference state
from the values at the specified state. The ideal-gas enthalpy of N2 at 500 K relative to the
standard reference state, for example, is ̅h500 K -̅h° = 14581 - 8669 = 5912 kJ/kmol.
The (molar) enthalpy of formation is the heat released (Δ̅hf <0) or absorbed (Δ̅hf >0 ) in a
chemical reaction at constant pressure when simple substances combine into a more complex
substance. At standard conditions of pressure and temperature (1 atm and 298 K), it is denoted
Δ̅hof . For elements in their standard states, Δ̅hof =0. For gases, the standard state is the atom or
molecule existing at standard state conditions.
The standard enthalpy of formation is a measure of the energy released or consumed when one
mole of a substance is created under standard conditions from its pure elements. The symbol of
the standard enthalpy change of formation is Δ̅hof.
Δ = change in enthalpy
The superscript ( ̅ ) implies the molar enthalpy (kj/mol).
o = it's a standard enthalpy change (298°K and 1 atm).
f = indicates that the substance is formed from its elements
The equation for the standard enthalpy change of formation is equal to the sum of the standard
enthalpies of formation of the products minus the sum of the standard enthalpies of formation of
the reactants.
Δ̅hof =̅hT -̅ho =sensible enthalpy relative to the standard reference state ( the difference between
the sensible enthalpy at the specified state and the sensible enthalpy at the standard reference
state of 25°C and 1 atm)
The enthalpy at any other temperature is given as
̅ =h
h ̅ of + (̅hT -̅ho)
Here the term ̅h is the enthalpy of any component at 298 K. The enthalpies at the temperatures
o

T and 298 K can be found from tables. If tables are not available, the enthalpy difference due to
the temperature difference can be calculated from
(̅hT -̅ho) = C̅p (T-298)
Enthalpy of the stable elements (such as O2, N2, H2, and C) at the standard reference state is
assigned a value zero [The enthalpy of the elements or their stable compounds is defined to be
ZERO at 25oC (298 K) and 1 atm (or 0.1 MPa)].
Example 2.6
Determine the enthalpy of combustion of liquid octane (C8H18) at 25°C and 1 atm, using
enthalpy-of-formation data from Table. Assume the water in the products is in the liquid form.
Solution 2.6
The stoichiometric equation for this reaction is
C8H18(ℓ) + ath (O2 + 3.76N2 ) 8CO2 + 9H2O(ℓ)+3.76athN2
N2 and O2 are stable elements, and thus their enthalpy of formation is zero.
The enthalpy of formation at 25°C and 1 atm

̅hof (kJ/kmol)
CO2 -393,520
H2O -285,830
C8H18(ℓ) -249,950
The enthalpy of combustion of C8H18
̅hc = Hprod - Hreact
̅hc =∑ ( nh̅of )p - ∑( n. ̅hof )R
= (nh̅°f )CO2 + (nh̅°f )H2O -(nh̅°f )C8H18
= (8 kmol) (-393,520) + (9 kmol) (-285,830) – (1kmol) (-249,950)
= -5,471,000 kJ/kmol C8H18 = - 47,891 kJ/kg C8H18

2.7 First Law analysis for steady- state reaction system

When the changes in kinetic and potential energies are negligible, the steady-flow energy
balance relation can be expressed:-
Rate of net energy transfer in by heat, work and mass = Rate of net energy transfer out by heat,
work and mass.
The steady-state combustion process will transfer heat and may be product work.an energy
balance would be:-
Q+HR = W+HP
HR=the total enthalpy of all the reactions
Hp= the total enthalpy of all the products
Q=the heat transfer required to carry-out the reaction
Q +∑ (ni.h̅i)r =W +∑( nj.h̅j)p
Q +∑ nr [h̅of +h̅T -̅ho] r =W+∑ np [h̅of +h̅T -̅ho ]p

Where np and nr represent the molal flow rates of the product (p) and the reactant(r),
respectively. Based on the classical sign convention, the net heat transfer to the reacting system
is
Qnet = HP - HR
In combustion analysis, it is more convenient to work with quantities expressed per mole of fuel.
Such a relation is obtained by dividing each term of the equation above by the molal flow rate
of the fuel, yielding

Qnet =Q-W=∑ Np [̅hof + ̅hT -h̅o] p - ∑ Nr [h̅of + h̅T -̅ho ] r

Where Nr and Np represent the number of moles of the reactant(r) and the product (p),
respectively, per mole of fuel.

2.8 Enthalpy and Internal energy of combustion

1-Enthalpy of combustion
Δ̅hoc =∑(nj.h̅oj)p-∑(ni.h̅oi)r
2-Internal energy of combustion
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 )= Uprod - Ureact kJ/kmol fuel
Where Uprod represents the internal energy of the products and Ureact represents the internal
energy of the reactants.
ΔU=Up-UR= (H-PV)p – (H-PV)r
H-PV = N(̅h°f + ̅hT – h̅°) – PV
= N(h̅°f + h̅T – h̅° – Pv̅ )
Q-W= ΔU =∑ Np [ h̅of + ̅hT - h̅o - Pv̅ ] p - ∑ Nr [h̅of + h̅T -̅ho - Pv̅ ] r
ΔU = ΔH - R̅T (∑Np - ∑Nr )
The Pv̅ terms are negligible for solids and liquids, and can be replaced by RuT for gases that
behave as an ideal gas. Also, if desired, the terms. h̅T - Pv̅ can be replaced by u̅.
2.9 Heating value of the fuel
Heating value is the positive number equal to the magnitude of the enthalpy of combustion or
heat of reaction at constant pressure or at constant volume at standard reference state
Heating value of the fuel is defined as the amount of heat released when a fuel is burned
completely in a steady-flow process and the products are returned to the state of the reactants.
-Heating values of a fuel (units of kJ/kg or MJ/kg) are traditionally used to quantify the
maximum amount of heat that can be generated by combustion with air at standard conditions
(STP) (25oC and 101.3 kPa).
- The amount of heat release from combustion of the fuel will depend on the phase of water in
the products. If water is in the gas phase in the products, the value of total heat release is
denoted as the lower heating value (LHV). When the water vapor is condensed to liquid,
additional energy (equal to the latent heat of vaporization) can be extracted and the total
energy release is called the higher heating value (HHV).
-The value of the LHV can be calculated from the HHV by subtracting the amount of energy
released during the phase change of water from vapor to liquid as:-
LHV =HHV- (NH2O,P MH2O hfg )/Nfuel.Mfuel
NH2O,P = the number of moles of water in the products.
Latent heat for water at STP is hfg = 2.44 MJ/kg = 43.92 MJ/kmol.
- In combustion literature, the LHV is normally called the enthalpy or heat of combustion (QC)
and is a positive quantity.
In other words, the heating value of a fuel is equal to the absolute value of the enthalpy of
combustion of the fuel. That is,
Heating value = absolute (hc )
QHVp = - ΔH│p=c ,T ; QHVv= - ΔU│v=c , T
The heating value depends on the phase of the H2O in the products. The heating value is called
the higher heating value (HHV) when the H2O in the products is in the liquid form, and it is
called the lower heating value (LHV) when the H2O in the products is in the vapor form
The two heating values are related by
- At constant pressure
QHHV │p=c = QLHV│p=c + (m.h̅fg)H2O kJ/kg fuel

- At constant volume
QHHV │v=c = QLHV│v=c + (m.u̅fg)H2O kJ/kg fuel
ΔH=ΔU+Δn.R̅T
QHHV │p=c = QHHV │v=c + Δn.R̅T
Δn=∑np-∑nR
Where m is the mass of H2O in the products per unit mass of fuel and h̅fg is the enthalpy of
vaporization of water at the specified temperature. Higher and lower heating values of common
fuels are given in table.
The heating value or enthalpy of combustion of a fuel can be determined from knowledge of the
enthalpy of formation for the compounds involved.
Determination of HHV for Combustion Processes at Constant Pressure
A control volume analysis at constant pressure with no work exchanged can be used to
theoretically determine the heating values of a particular fuel. Suppose reactants with 1 kmol of
fuel enter the inlet of a control volume at standard conditions and products leave at the exit. A
maximum amount of heat is extracted when the products are cooled to the inlet temperature and
the water is condensed. Conservation of energy for a constant pressure reactor, with HP and HR
denoting the respective total enthalpies of products and reactants, gives:-
- Qout,p =HR - Hp
The negative value of -Qout,p indicates heat transfer out of the system to the surroundings. It
follows from above that the heating value of the fuel is the difference in the enthalpies of the
reactants and the products. However, in combustion systems, the evaluation of the enthalpies is
not straightforward because the species entering the system are different than those coming out
due to chemical reactions. Qout,p is often referred to as the enthalpy of reaction or heat of
reaction, with the subscript p indicating that the value was calculated at constant pressure. The
enthalpy of reaction is related to the enthalpy of combustion by Qout,p = -Qc .
- Qout,p =∑ nr [h̅of +h̅T -̅ho] r - ∑ np [h̅of +h̅T -̅ho ] p
When the products are cooled to the same conditions as the reactants, the amount of heat
transfer from the constant-pressure reactor to the surroundings is defined as the heating value.
At STP the sensible enthalpy terms drop out for both reactants and products and the heat
release is
- Qoout,p =∑ nr [h̅of ]r - ∑ np [h̅of ] p

Assuming that water in the products is liquid, HHV is determined:

HHV = - Qoout,p /NfuelMfuel
Determination of HHV for Combustion Processes at a Constant-Volume Reactor
A constant-volume reactor is more convenient than the constant-pressure reactor to
experimentally determine the HHV of a particular fuel. For a closed system, conservation of
energy yields
- Qout;v = UR - Up
The internal energy will be evaluated by using its relation to enthalpy. Note that relation h
=u+pv is mass based and the corresponding molar base relation is h̅ =u̅+ R̅uT. At STP, the
total internal energy of the reactants, UR, inside the closed system is
UR = HR -PV=∑ nr [h̅of ] r -∑ nr R̅u To [To=25oC]
Up = Hp -PV=∑ np [h̅of ] p -∑ np R̅u To
- Qout;v =∑ nr [h̅of ]r - ∑ np [h̅of ] p +[∑ np -∑ nr ]R̅uTo
Therefore, HHV for combustion processes is calculated as
HHV= {- Qout;v - [ ∑ np -∑ nr ]R̅uTo}/ NfuelMfuel
-The composition of gaseous fuel is common expressed in molar volume fraction of the chemical
compounds found in it
-The heating value of gaseous fuel is expressed in units of energy per unit volume (kj/lit or
kj/m3)
-The heating value (kj /m3)ψ(ρgases) which ψ(Pabs and 1/Tabs) , but heating value ( kj/kg )is
independent of Pgas and Tgas
-The heating value for Combustion Processes from a Constant-Volume Reactor,HVv of the
mixture of fuel gas =∑HVi
- If HVv at Pr ,Tr is known then:-( HVVv )P,T =( HVVv )Pr,Tr (P/Pr )(Tr /T)
- HVVv at some temperature and pressure can be converted into a gravimetric heating value
,HVVm by multiplying the volumetric value by the specific volume ,v of the gas at the same
pressure and temperature. HVVm = HVVv * v
v=V/m =RT/P = (Ru/M) (T/P)
Ru=the universal gas constant =8.314kj/kmol.k
-The specific gravity (SG) of gaseous fuel is expressed as the density or specific weight of the
fuel at 15.56oC and 1atm to that of air at 15.56oC and 1atm.
(SG)fuel= ρ(fuel )at 15.56oC and 1atm / ρ(air )at 15.56oC and 1atm.
- If the fuel is considered as ideal gas
- The molar density, ̅ρ= P/RuT kmol/m3
- The specific gravity,SG=(M/R̅)(P/T)gas /(M/R̅)(P/T)air =Mgas /Mair
The above equation shows the gaseous fuel having a specific gravity of less than 1.0 is lighter
than air where a fuel having SG >1.0 is heavier than air .This can be an important factor is gas
leakage and safety requirements for storing handling gaseous fuel.
Example 2.7
Calculate the higher heating value, in kj/m3 and kj/kg, at 10oC and 3 atm for a gas mixture with
the following composition: 94.3% CH4, 4.2% C2H6 and 1.5% CO2

Solution 2.7
From table:-
At 25oC and 1 atm
HHVm,for CH4 = 55530 kj/kg
HHVm,for C2H6 = 51900 kj/kg
HHVm,for CO2 = 0 kj/kg
Mmix =0.943(16) +0.042(30) +0.015(44) = 17 kg/kmol
HHVm,for mixture= 0.943(55530)(16/17)+0.042(51900)(30/17)+0.015(0) = 53131 kj/kg
v =RT/P= (Ru/M)(T/P)=(8.314/17)(298/101.3)= 1.439 m3/kg
HHVv,for mixture= HHVm,for mixture/v=53131/1.439 =36922 kj/m3
At 10oC and 3 atm
HHVv ,for mixture=36922 (P/Pr)(Tr /T)= 36922 (3/1)(298/283)= 116637 kj/m3
v =RT/P= (Ru/M)(T/P)=(8.314/17)(283/3x101.3)= 0.4554 m3/kg
HHVm,for mixture=116637x0.4554 =53116 kj/kg

Example 2.8
If the enthalpy of evaporation of propane is 370 kj/kg, calculate the enthalpy of combustion of
propane at 25oC on both kmol and kg basis under the following conditions:-
1) Liquid propane with (H2O)L
2) Liquid propane with (H2O)g
3) Gaseous propane with(H2O)L
4) Gaseous propane with(H2O)g
Solution 2.8
C3H8+5O2 →3CO2+4H2O
h̅of (C3H8)g= -103900 kj / kmol
h̅of (C3H8)L= -103900 - 44(370)= - 120180 kj / kmol
1) Liquid propane with (H2O)L
HP- HR =3(-393522) +4(-285830) +120180= - 2203706 kj/kmol
= -2203706/44= - 50084 kj/kg
So the higher heating value (QHHV) for liquid propane = 50084kj/kg
2) Liquid propane with (H2O)g
HP- HR =3(-393522) +4(-241826) +120180= - 2203706 kj/kmol
= - 2027690 /44 = - 46084 kj/kg
So the lower heating value (QLHV) for liquid propane = 46084 kj/kg
3) Gaseous propane with (H2O)L
HP- HR =3(-393522) +4(-285830) +103900 = -2219986 kj/kmol
= -2219986/44 =50386 kj/kg
So the higher heating value (QHHV) for Gaseous propane =50386 kj/kg
4) Gaseous propane with (H2O)g
HP- HR =3(-393522) +4(-241826) +103900 = -2043970 kj/kmol
=-2043970/44= - 46454 kj/kg
So the lower heating value (QLHV) for Gaseous propane =46454 kj/kg

Wobbe Number or Wobbe index

Wobbe Number The ultimate objective is to obtain a fixed thermal output rate when fuels are
changed. The Wobbe Index is used to compare the combustion energy output of different
composition fuel gases Wobbe number provides a relation between the volume-based heating
value and the density of fuel, and is a measure of the interchangeability of gaseous fuels.
Similar Wobbe number assures similar thermal output rate. The volume flow rate of a gas
through an orifice is given,
Q̇= V x A
Q̇ = A√2𝛥𝑃/𝜌) = A (2Pg /ρ) 1/2
Where Pg= the gage pressure drop across the orifice
ρ = the gas density
A= the cross-sectional area.
The thermal output rate =Ḣ= Q̇ (HHV') = A (HHV') (2Pg/ρa) 1/2(ρa /ρ) 1/2
HHV` = the higher heating value per unit volume
ρa = the air density.
H = A (2Pg /ρa ) 1/2. Wo
Wo =Wobbe number = HHV'/ (ρ/ρa )1/2 kJ/m3
Where the term ρ/ρa called the specific gravity (Sg) of the gas. If the gas line pressure is
constant (typically 15 cm of water for residential burners), the heat throughput Ḣ is also the
same for identical values of Wo when the gaseous fuel is changed. The lower the value of Wo,
the lower is the heat release rate. If the Wobbe number changes, then the burner velocity must
be altered (and the burner dimensions must sometimes be changed) to obtain a fixed value of
the heat release, which may he consequences for flame stability. Not that similar Wo does not
imply similar volume flow rates; thus, if HHV is higher, the volume flow rate through same
burner will be lower for fixed Wo.
When the combustion characteristics of gaseous are matched with a particular gas burner, the
fuel engine interface requirement cannot be based on selecting fuels having an equal heating
value or specific gravity alone. In fact, in order to pass a constant energy rates through a given
burner orifice, gaseous fuels with equal operating gas Wobbe number, Wo ,where;-
Wobbe number, Wo =HHV for gaseous fuel / √𝑆𝐺
Example 2.9
Natural gas (NG) with is 37925 kJ/m3 higher heating value and a specific gravity of 0.592 is to
be replaced with a propane—air (P-A) mixture (HHV = 96755 kJ/m3 and specific gravity =
1.552).
(a) What is the volume fraction x of propane for identical thermal output and upstream
pressure?
(b) What will be the ratio of volume flow rate (V̇) of the replacement gas (P-A) to that of the
original gas (NG)?
Solution 2.9
For similar Wo
HHV'PA / (ρPA/ρa) 1/2 = HHV'NG / (ρNG/ρa) 1/2
ρPA =x.ρP +(1-x)ρa
ρPA/ρa= x.(ρP / ρa )+(1-x)
HHV'PA=x. HHV'P + (1-x) HHV’A, then HHV’PA = x. HHV'P
x. HHV'P / [x. (ρP / ρa) + (1-x)] 1/2= HHV'NG / (ρNG/ρA) 1/2
96755x / [1.552x+ (1-x)] 1/2 =37925/0.5921/2=49290.7
x /[1.552x + (1-x)] 1/2=0.5094
x2 =0.26[0.552x+ 1],then x = 0.586
ρPA =0.586(1.552)+0.414=1.323
V̇PA /V̇NG = (ρNG / ρPA) 1/2= (0.592/1.323)1/2 =0.669
Hence, the propane—air (P-A) volume flow rate through the line is only 66.9% of natural gas
flow for same heat throughput rate and the same upstream pressure

2.10 Adiabatic Flame Temperature (Adiabatic combustion process)

The temperature of the products in an adiabatic combustion of fuel without applying any shaft
work is defined as the “Adiabatic Flame Temperature”. In combustion process the heat
produced during the exothermic chemical reaction is released to their product and the
temperature of the products is raised. There is no possibility for dissipation of the heat to the
surrounding and the process will be adiabatic as there is no heat loss to the surrounding. As a
result, the temperature of the products suddenly increases and it produces a flame. This will
heat up the product gases in flame region and the temperature rise will be maximum. This
highest temperature is known as the adiabatic flame temperature. The temperature rise depends
on the amount of excess air used or the air-fuel ratio. The flame temperature has the highest
value for using pure oxygen gas and it decreases by using air. So, the exact stoichiometric air is
to be supplied for better result. With too large amount of excess air the flame temperature will
be reduced. When the heat loses to the environment or diluted by the inert gases and there is an
incomplete combustion. So, the temperature of the products will be less. The flame temperature
is determined from the energy balance of the reaction at equilibrium. There are two type of
adiabatic flame temperature: constant pressure adiabatic flame temperature and constant
volume adiabatic flame temperature.
Adiabatic Flame Temperature is defined as the flame temperature achieved with the assumption
of No work and No change in kinetic or potential energies (Qc.v =Wc.v =0) that can be achieved
for the given reactants, because any heat transfer from the reacting substance and any
incomplete combustion would tend to lower the temperature of the products.
The energy liberated on combustion is transferred from reactor in two ways:
1- Energy accompanying the exiting combustion products at temperature(Tp)
2- Heat transferred to the surrounding:Qc.v ,in adiabatic combustion,heat transferred to the
surrounding,Qc.v=0,then all is taken out by the exiting combustion products at
temperature(Tp)
The temperature (Tp) corresponding to the exiting combustion products is called adiabatic
flame temperature or adiabatic combustion process temperature. In other words, if Hp=HR,then
the temperature of products is called the adiabatic flame temperature, which is the maximum
temperature achieved for the given reactants.
- Adiabatic constant volume ,Up-UR=0
- Adiabatic constant pressure ,Hp-HR=0
A graphic below explain of how the adiabatic flame temperature is determined. At the initial
reactant temperature, the enthalpy of the product mixture is lower than that of the reactant
mixture. The energy released from combustion is used to heat up the products such that the
condition HP(TP)= HR(TR) is met.
∑ Np [̅hof + ̅hT -h̅o ] p =∑ NR [̅hof + h̅T -h̅o] R

For a given reaction, the adiabatic flame temperature is computed by trial and error. The
energy of reactants,HR being known , a suitable temperature is chosen for the products so that
 the energy of the products at that temperature becomes equal the energy of reactants.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. The maximum temperature in a
combustion chamber can be controlled by adjusting the amount of excess air, which serves as
a coolant.
Note that the adiabatic flame temperature of a fuel is not unique. Its value depends on
(1) The state of the reactants.
(2) The degree of completion of the reaction.
(3) The amount of air used.
For a specified fuel at a specified state burned with air at a specified state, the adiabatic
flame temperature attains its maximum value when complete combustion occurs with the
theoretical amount of air.
2.11 Combustion efficiency
Theoretical complete combustion is obtained by stoichiometric amount of air and products of
combustion (POC) should not contain CO. But in actual combustion of any fuel does not occur
with just stoichiometric amount of air, excess air is required. Excess air depends on type of fuel.
Normally solid fuels require more excess air than liquid and gaseous fuels. Mixing of fuel and
air is important, simply because one mole of oxygen is accompanied by 3.76 moles of N2.In an
air, the probability of finding nitrogen in neighborhood of carbon is more than oxygen .Thus
mixing determines combustion efficiency, i.e. the ability of a device (used for mixing of fuel and
air) to convert potential energy of fuel into thermal energy. Inefficiency in combustion is due to
poor mixing which may lead to formation of CO. Poor combustion efficiency leads to wastage
of fuel and environmental pollution. So excess air has to be used to increase combustion
efficiency. Increase in excess air decreases CO in products of combustion but at the same time
increases amount of products due to increase in nitrogen and oxygen. Fig.2.5. illustrates the
relationship between excess O2, CO and heat losses.
-Increase in excess air increases percent O2 in POC and CO decreases by using slight amount
of excess air. Beyond around 1 to 2% O2, CO in POC disappears completely .But increase in
excess air increases O2 in POC. Heat losses decreases with excess air and become minimal at
around 1% O2 which is due to decrease in CO. Beyond around 1% O2 heat losses increases due
to increasing nitrogen and oxygen in POC.
 Loss due to heat in stack
Loss due to un-burnt fuel

Fig.2.5. the relationship between excess O2, CO and heat losses.

- Nitrogen reduces combustion efficiency :-
1. Absorbing heat from combustion of fuel and diluting the flue gases (reduces heat
available)
2. Increases the volume of combustion by-products, which then have to travel through
heat exchanger and up the stack faster to allow the introduction of additional fuel
air mixture.
3. Nitrogen can combine with oxygen (at high flame temperature)to produce oxides of
nitrogen NOx which are toxic pollutants
- Under certain conditions .Carbone may also combine with oxygen to form Carbon
Monoxide, which results in the release of a smaller quantity of heat.
- Natural gas contains more hydrogen and less Carbone per kg than fuel oils and such
produces more water vapour.Consequently, more heat will be carried away by exhaust
while firing natural gas.
- A very specific amount of O2 is needed for perfect combustion and some additional
(excess) air is required for ensuring complete combustion. However, too much excess air
will result in heat and efficiency losses.
Control of air and analysis of flue gas
Chemical analysis of flue gas is an objective method that helps in achieving finer air control.
By measuring carbon dioxide, CO2 or oxygen, O2 in the flue gases by Orsat apparatus or
portable fyrite, the excess air level as well as stack losses can be estimated with the graph as
shown in Fig.2.6 and Fig.2.7.The excess air to be supplied depends on the type of fuel and the
firing system. For optimum combustion of fuel oil, the CO2 or O2 in flue gases should be
maintained at 14-15% in case of CO2 and 2-3%in case of O2.
 Fig.2.6. Relation between CO2 and excess air for fuel oil

Fig.2.7. Relation between residual oxygen and excess air

During the combustion process, a fraction of fuel’s chemical energy is not fully released inside
the engine. The engine can be considered as open system.
HR (Ta)- Hp (Ta) =net chemical energy released during combustion
=∑ NR [̅hof + h̅T -h̅o] R - ∑ Np [̅hof + ̅hT -h̅o ] p

𝐹𝑟𝑎𝑐𝑡𝑖𝑜𝑛 𝑜𝑓 𝑡ℎ𝑒 𝑓𝑢𝑒𝑙 𝑒𝑛𝑒𝑟𝑔𝑦 𝑟𝑒𝑙𝑒𝑎𝑠𝑒𝑑

Combustion efficiency,ηc =
𝑎𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑓𝑢𝑒𝑙 𝑒𝑛𝑒𝑟𝑔𝑦 𝑠𝑢𝑝𝑝𝑙𝑖𝑒𝑑

Combustion efficiency,ηc = [ HR(Ta) - Hp(Ta)]/ ṁf QHHV

 Sheet (2-A)
1- What is enthalpy of combustion? How does it differ from the enthalpy of reaction?
2- What is enthalpy of formation? How does it differ from the enthalpy of combustion?
3- What are the higher and the lower heating values of a fuel? How do they differ? How is
the heating value of a fuel related to the enthalpy of combustion of that fuel?
4- When are the enthalpy of formation and the enthalpy of combustion identical?
5- Does the enthalpy of formation of a substance change with temperature?
6- The h̅of of N2 is listed as zero. Does this mean that N2 contains no chemical energy at the
standard reference state?
7- Which contains more chemical energy, 1 kmol of H2 or 1 kmol of H2O?
8- Derive an energy balance relation for a reacting closed system undergoing a quasi-
equilibrium constant pressure expansion or compression process.
9- Consider a complete combustion process during which both the reactants and the
products are maintained at the same state. Combustion is achieved with (a) 100 percent
theoretical air, (b) 200 percent theoretical air, and (c) the chemically correct amount of
pure oxygen. For which case will the amount of heat transfer be the highest? Explain.
10- -Consider a complete combustion process during which the reactants enter the
combustion chamber at 20°C and the products leave at 700°C. Combustion is achieved
with (a) 100 percent theoretical air, (b) 200 percent theoretical air, and (c) the
chemically correct amount of pure oxygen. For which case will the amount of heat
transfer be the lowest? Explain.

Sheet (2-B)
a) - CHOOSE THE CORRECT ANSWER:-
1 - Gross & net calorific value is the same for
a) If its hydrogen compound content is zero.
b) Under no circumstances.
c) If its ash content is zero.
d) If its carbon content is very low.
2 - Combustion reaction of fuels is a/an ---------- reaction.
a) Endothermic
b) Exothermic
c) None of these
3 - Higher efficiency in the combustion of solid fuel can not be achieved by
a) Keeping the flue gas exhaust temperature very high.
b) Proper fuel preparation.
c) Adopting efficient-fuel firing technique & equipment.
d) Supplying correct quantity of combustion air.
4 - Stack heat losses can be minimised by
a) Controlling the excess air.
b) Oxygen enrichment of combustion air.
c) Using low C.V. fuels.
d) Maintaining proper draft in the furnace.
5 - The internal energy of the combustion products is compared to that of reactants.
a) Same
b) Less
 c) More or less; (depends on the state of fuel.)
d) More
6 - Presence of in a dry gaseous fuel does not contribute to its calorific value.
a) Carbon
b) Hydrogen
c) Oxygen
d) sulphur
7- High excess air in combustion of fuels results in
a) Increased fuel consumption
b) Smoky flame
c) Incomplete combustion
d) None of these
8- If the specific heat of gaseous products of combustion of a fuel is high, the adiabatic flame
temperature will be
a) high
b) very high, if the fuel is of low calorific value
c) low
d) none of these
9- The maximum adiabatic flame temperature is attained, when the fuel is burnt with
a) Less than theoretically required amount of air.
b) Theoretically required amount of air.
c) Theoretically required amount of oxygen.
d) More than theoretically required amount of air.
10- Higher fuel combustion efficiency can not be achieved by
a) Adopting proper fuel firing technique & fuel preparation.
b) Reducing sulphur content in the fuel.
c) Preheating of fuel gases & combustion air.
d) Supplying correct amount of combustion air.
11- If the specific heat of gaseous products of combustion of a fuel is high, the adiabatic flame
temperature will be
a) low
b) high
c) very high if fuel is of low calorific value
d) none of these
12- Use of excess of combustion air in the combustion of fuels results in
a) heat losses
b) long flame
c) condensation of water vapor from the flue gas
d) none of these
13- Which of the following constituents of fuel does not contribute to its calorific value on
combustion?
a) hydrogen
b) sulfur
c) carbon
d) none of these
14- High sulfur content in a fuel
a) increases the dew point of the flue gases
b) decreases the dew point of the flue gases
c) reduces combustion efficiency by limiting the permissible temperature reduction of the
flue gases
d) both (a) and (c)
15- Chemical kinetics can predict the
a) rate of reaction
b) feasibility of reaction
c) both (a) and (b)
d) none of these
16- Velocity of a chemical reaction
a) decreases with increase in temperature
b) increases with increase of pressure of reactant for all reactions
c) decreases with increase of reactant concentration
d) none of these
17- A fuel containing carbon and carbon monoxide (but containing the hydrogen or its
compounds) is burnt in pure oxygen at constant pressure. Its gross calorific value as compared
to the net calorific value will be
a. more
b. less
c. same
d. data insufficient; can't be predicted
18- Which of the following statement is wrong? In an exothermic reaction
a) The reactants have more potential energy than products have
b) The extra energy is released to surroundings
c) The enthalpy of the product is less than enthalpy of the reactants
d) The enthalpy change is always positive
19- Which of the following statement is wrong? The activated complex
a) Known as the transition state
b) Represents the structure of the system as it exists at the peak of the activation
energy curve.
c) is a temporary –high energy –unstable state between reactance and products
d) occurs at a minimum potential energy
20- The energy of activation of a chemical reaction
a) is same as heat of reaction at constant pressure
b) Is the minimum energy which the molecules must have before the reaction can take
place
c) varies as fifth power of the temperature
d) Both (b) and (c)
 b)- COMPLETE THE FOLLOWING
1-An exothermic reaction is that it is one in which the energy of the products is ---------- the
energy of the reactants
a) More than
b) Less than
c) Equal to
2- Excess air can be derived by measuring percentage of ____________ in exit flue gas
a) CO
b) NO2
c) CO2
d) CH4
3- With increase in excess air for combustion which of the following will result in flue gas
a) % Oxygen decreases
b) % CO2 decreases
c) % Oxygen and CO2 decreases
d) % Oxygen and CO2 increases
4-An exothermic reaction is a reaction that results in the system becoming --------------
a) Hotter
b) Colder
c) None of the above
5- An endothermic reaction is that it is one in which the energy of the products is ---------- the
energy of the reactants
a) More than
b) Less than
c) Equal to
6- An endothermic reaction is a reaction that results in the system becoming ---------
a) Hotter
b) Colder
c) None of the above
7- Combustion reactions is an ------- reactions
a) Exothermic
b) Endothermic
c) None of the above
8- Chemical reactions will not take place until the system has some minimum amount of energy
added to it. This energy is called --------- energy.
a) The kinetic
b) The internal
c) The activation
9- The activated complex is a temporary -----------state between reactance and products
a) high energy –unstable
b) low energy –stable
c) high energy –stable
10- Arrhenius equation shows the variation of -------------with temperature
a) Reaction rate
b) Rate constant
c) Energy of activation
d) Frequency factor

a) The activation energy for the forward reaction is equal to --------

b) The activation energy for the reverse reaction is equal to --------
c) The enthalpy change for the reaction equal to --------
d) The reaction type is -----------------
 Sheet (2-C)
1- Methane (CH4) is burned completely with the stoichiometric amount of air during a steady-
flow combustion process. If both the reactants and the products are maintained at 25°C and 1
atm and the water in the products exists in the liquid form, determine the heat transfer from
the combustion chamber during this process. What would your answer be if combustion were
achieved with 100 percent excess air?
----------------------------------------------------------------------------------------------------------
2- Hydrogen (H2) is burned completely with the stoichiometric amount of air during a steady-
flow combustion process. If both the reactants and the products are maintained at 25°C and 1
atm and the water in the products exists in the liquid form, determine the heat transfer from
the combustion chamber during this process. What would your answer be if combustion were
achieved with 50 percent excess air?
-------------------------------------------------------------------------------------------------------
3- Liquid propane (C3H8) enters a combustion chamber at 25°C at a rate of 1.2 kg/min where it
is mixed and burned with 150 percent excess air that enters the combustion chamber at 12°C. If
the combustion is complete and the exit temperature of the combustion gases is 1200 K,
determine
(a) The mass flow rate of air
(b) The rate of heat transfer from the combustion chamber.
------------------------------------------------------------------------------------------------------------
4- Acetylene gas (C2H2) is burned completely with 20 percent excess air during a steady-flow
combustion process. The fuel and air enter the combustion chamber at 25°C, and the products
leave at 1500 K. Determine
(a) The air–fuel ratio
(b)The heat transfer for this process.
-----------------------------------------------------------------------------------------------------------
5- Benzene gas (C6H6) at 25°C is burned during a steady-flow combustion process with 95
percent theoretical air that enters the combustion chamber at 25°C. All the hydrogen in the fuel
burns to H2O, but part of the carbon burns to CO. If the products leave at 1000 K, determine
(a) The mole fraction of the CO in the products
(b) The heat transfer from the combustion chamber during this process.
------------------------------------------------------------------------------------------------------------
6- Diesel fuel (C12H26) at 25°C is burned in a steady flow combustion chamber with 20 percent
excess air that also enters at 25°C. The products leave the combustion chamber at 500 K.
Assuming combustion is complete; determine the required mass flow rate of the diesel fuel to
supply heat at a rate of 2000 kJ/s.
-------------------------------------------------------------------------------------------------------------------
7- Octane gas (C8H18) at 25°C is burned steadily with 30 percent excess air at 25°C, 1 atm, and
60 percent relative humidity. Assuming combustion is complete and the products leave the
combustion chamber at 600 K, determine the heat transfer for this process per unit mass of
octane.
---------------------------------------------------------------------------------------------------------
8- Ethane gas (C2H6) at 25°C is burned in a steady-flow combustion chamber at a rate of 5 kg/h
with the stoichiometric amount of air, which is preheated to 500 K before entering the
combustion chamber. An analysis of the combustion gases reveals that all the hydrogen in the
fuel burns to H2O but only 95 percent of the carbon burns to CO2, the remaining 5 percent
forming CO. If the products leave the combustion chamber at 800 K, determine the rate of heat
transfer from the combustion chamber.
------------------------------------------------------------------------------------------------------------
9 - A constant-volume tank contains a mixture of 120 g of methane (CH4) gas and 600 g of O2 at
25°C and 200 kPa. The contents of the tank are now ignited, and the methane gas burns
completely. If the final temperature is 1200 K, determine
(a) The final pressure in the tank
(b) The heat transfer during this process.
------------------------------------------------------------------------------------------------------------
10- A closed combustion chamber is designed so that it maintains a constant pressure of 300
kPa during a combustion process. The combustion chamber has an initial volume of 0.5 m3 and
contains a stoichiometric mixture of octane (C8H18) gas and air at 25°C. The mixture is now
ignited, and the product gases are observed to be at 1000 K at the end of the combustion
process. Assuming complete combustion, and treating both the reactants and the products as
ideal gases, determines the heat transfer from the combustion chamber during this process.
-----------------------------------------------------------------------------------------------------------
11- Liquid ethyl alcohol (C2H5OH(ℓ)) at 25°C is burned in a steady-flow combustion chamber
with 40 percent excess air that also enters at 25°C. The products leave the combustion chamber
at 600 K. Assuming combustion is complete; determine the required volume flow rate of the
liquid ethyl alcohol, to supply heat at a rate of 2000 kj/s. At 25°C the density of liquid ethyl
alcohol is 790 kg/m3, the specific heat at a constant pressure is 114.08 kJ/ kmol.K, and the
enthalpy of vaporization is 42,340 kJ/kmol.
------------------------------------------------------------------------------------------------------------
12- A rigid vessel initially contains 2 kmol of carbon and 2 kmol of oxygen at 25°C, 200 kPa.
Combustion occurs, and the resulting products consist of 1 kmol of carbon dioxide, 1 kmol of
carbon monoxide, and excess oxygen at a temperature of 1000 K. Determine the final pressure
in the vessel and the heat transfer from the vessel during the process.
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13- The combustion of heptane C7H16 takes place in a steady flow burner where fuel and air
are added as gases at Po, To. The mixture has 125% theoretical air and the products are going
through a heat exchanger where they are cooled to 600 K.Find the heat transfer from the heat
exchanger per kmol of heptane burned.
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14- In a new high-efficiency furnace, natural gas, assumed to be 90% methane and 10% ethane
(by volume) and 110% theoretical air each enter at 25°C, 100 kPa, and the products (assumed
to be 100% gaseous) exit the furnace at 40°C, 100 kPa. What is the heat transfer for this
process?
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15- Pentene, C5H10 is burned with pure oxygen in a steady flow process. The products at one
point are brought to 700 K and used in a heat exchanger, where they are cooled to 25°C. Find
the specific heat transfer in the heat exchanger.
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16- Gaseous propane mixes with air, both supplied at 500 K, 0.1 MPa. The mixture goes into a
combustion chamber and products of combustion exit at 1300 K, 0.1 MPa. The products
analyzed on a dry basis are 11.42% CO2, 0.79% CO, 2.68% O2, and 85.11% N2 on a volume
basis. Find the equivalence ratio and the heat transfer per kmol of fuel.
17- Liquid pentane is burned with dry air and the products are measured on a dry basis as:
10.1% CO2, 0.2% CO, 5.9% O2 remainder N2. Find the enthalpy of formation for the fuel and
the actual equivalence ratio.
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18- The fuel gas has a composition of 50% methane, 45% carbon dioxide, and 5% hydrogen on
a volumetric basis. Determine the lower heating value of this fuel gas mixture per unit volume.
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19- A burner receives a mixture of two fuels with mass fraction 40% n-butane and 60%
methanol, both vapor. The fuel is burned with stoichiometric air. Find the product composition
and the lower heating value of this fuel mixture (kJ/kg fuel mix).
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20- Blast furnace gas in a steel mill is available at 250°C to be burned for the generation of
steam. The composition of this gas is, on a volumetric basis,
Component CH4 H2 CO CO2 N2 H2O
Percent by volume 0.1 2.4 23.3 14.4 56.4 3.4
3
Find the lower heating value (kJ/m ) of this gas at 250°C and ambient pressure.
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21- In an engine a mixture of liquid octane and ethanol, mole ratio 9:1, and stoichiometric air
are taken in at To, Po. In the engine the enthalpy of combustion is used so that 30% goes out as
work, 30% goes out as heat loss and the rest goes out the exhaust. Find the work and heat
transfer per kilogram of fuel mixture and also the exhaust temperature.