Fuel and Energy Utilization (ECE4433) (WK 5 & 6 - Combustion & Thermochemistry Calculation) PDF

B.
Eng (Hons) Chemical Engineering

Fuel and Energy Utilization
(ECE4433)
Combustion and Thermochemistry

(Week 5 & 6)
PowerPoint Slides
by PS Yap
Chapter Overview
Introduction
A definition of combustion
Combustion modes and flame types
Reactants and products mixtures

Stoichiometry
Absolute (or standardized) enthalpy and

enthalphy of formation
Enthalpy of combustion and heating values
Adiabatic flame temperatures
Last Updated: 22/08/2016 I-Station Solutions Sdn Bhd 2

Learning Objectives
To provide the understanding and knowledge on

combustion, reactants and products mixtures and
adiabatic flame temperatures

Learning Outcomes
Student should be able to understand the combustion,

reactants and products mixtures and adiabatic flame
temperatures

Introduction
A Definition of Combustion
Websters Dictionary provides a useful starting point for
a definition of combustion as rapid oxidation generating
heat; or both light and heat, also slow oxidation
accompanied by relatively little heat and no light. For
our purposes, we will restrict the definition to include only
the rapid oxidation portion, since most practical
combustion devices belong in this realm.
This definition emphasizes the intrinsic importance of
chemical reactions to combustion. It also emphasizes
why combustion is so very important, combustion
transforms energy stored in chemical bonds to heat that
can be utilized in a variety of ways.
Combustion modes and flame type
Combustion can occur in either a flame or nonflame

mode, and flames, in turn, are categorized as being
either premixed flames or nonpremixed (diffusion)
flames. The difference between flame and nonflame
modes of combustion can be illustrated by the processes
occuring in a knocking spark-ignition engine (Fig. 1.6).
In Fig. 1.6a, we see a thin zone of intense chemical
reaction propagating through the unburned fuel-air
mixture. The tin reaction zone is what we commonly
refer to as a flame. Behind the flame are the hot
products of combustion. As the flame moves across the
combustion space, the temperature and pressure rise in
the unburned gas.
Combustion modes and flame type (contd)
Under certain conditions (Fig. 1.6b), rapid oxidation

reactions occur at many locations within the unburned
gas, leading to very rapid combustion throughout the
volume. This essentially volumetric heat release in an
engine is called autoignition, and the very rapid pressure
rise leads to the characteristic sound of engine knock.
Knock is undesirable, and a recent challenge to engine
designers has been how to minimize the occurrence of
knock while operating with lead-free gasolines. In
compression-ignition or diesel engines, however,
autoignition initiates the combustion process by design.

The two classes of flames, premixed and nonpremixed

(or diffusion), are related to the state of mixedness of the
reactants, as suggested by their names. In a premixed
flame, the fuel and the oxidizer are mixed at the
molecular level prior to the occurrence of any significant
chemical reaction. The spark-ignition engine is an
example where premixed flames occur.
Contrarily, in a diffusion flame, the reactants are initially
separated, and reaction occurs only at the interface
between the fuel and oxidizer, where mixing and reaction
both take place. An example of a diffusion flame is a
simple candle. In practical devices, both types of flames
may be present in various degrees.
Diesel-engine combustion is generally considered to

have significant amounts of both premixed and
nonpremixed or diffusion burning. The term diffusion
applies strictly to the molecular diffusion of chemical
species, i.e. fuel molecules diffuse toward the flame from
one direction while oxidizer molecules diffuse toward the
flame from the opposite direction.
In turbulent nonpremixed flames, turbulent convection
mixes the fuel and air together on a macroscopic basis.
Molecular mixing at the small scales, i.e. molecular
diffusion, then completes the mixing process so that
chemical reactions can take place.

Reactant and product mixtures
Stoichiometry
The stoichiometry quantity of oxidizer is just that amount
needed to completely burn a quantity of fuel. If more
than a stoichiometric quantity of oxidizer is supplied, the
mixture is said to be fuel lean, or just lean, while
supplying less than the stoichiometric oxidizer results in
a fuel-rich, or rich mixture.
The stoichiometric oxidizer (or air) fuel ratio (mass) is
determined by writing simple atom balances, assuming
that the fuel reacts to form an ideal set of products. For a
hydrocarbon fuel given by CxHy, the stoichiometric
relation can be expressed as:

Reactant and product mixtures (contd)
. CxHy +a(O2 + 3.76 N2) => xCO2 + (y/2)H2O + 3.76aN2

where a = x + y/4
For simplicity, we assume throughout this book that the
simplified composition for air is 21 percent and 79
percent N2 (by volume), i.e. that for each mole of O2 in
air, there are 3.76 moles of N2.
The stoichiometric air-fuel ratio can be as:
m 4.76a MWair
( A / F ) stoic = air =
m 1 MW fuel
fuel stoic
Where MWair and Mwfuel are the molecular weights of the
air and fuel, respectively.

Table 2.1 shows stoichiometric air-fuel ratios for

methane and solid carbon. Also shown is the oxygen-
fuel ratio for combustion of H2 in pure O2. For all of these
systems, we see that there is many times more oxidizer
than fuel.

The equivalence ratio, , is commonly used to indicated

quantitatively whether a fuel-oxidizer mixture is rich,
lean, or stoichiometric. The equivalence ratio is defined
as:
( A / F ) stoic ( F / A)
= =
(A/ F) ( F / A) stoic

Reactant and product mixture (contd)
From this definition, we see that for fuel-rich mixtures,

> 1, and for fuel-lean mixtures, < 1. For a
stoichiometric mixture, equals unity. In many
combustion applications, the equivalence ratio is the
single most important factor in determining a systems
performance. Other parameters frequently used to define
stoichiometry are percent stoichiometric air, which
relates to the equivalence ratio as:
100%
% stoichiometric air =

(1 )
% excess air = 100%


Example 2.1
A small, low-emission, stationary gas-turbine engine (see

Fig. 2.4) operates at full load (3950 kW) at an
equivalence ratio of 0.286 with an air flowrate of 15.9
kg/s. The equivalent composition of the fuel (natural gas)
is C1.16H4.32. Determine the fuel mass flowrate and the
operating air-fuel ratio for the engine.
Solution
Given = 0.286, MWair = 28.85, m air =15.9 kg/s,

MWfuel = 1.16(12.01) + 4.32 (1.008) = 18.286
Find: and (A/F)
m fuel

Example 2.1 (contd)
We will proceed by first finding (A/F) and then mfuel.

4.76a MWair
( A / F ) stoic ==
1 MW fuel
Where a = x+y/4 = 1.16 + 4.32/4 = 2.24.

Thus, 4.76a 28.85
( A / F ) stoic == (2.24) = 16.82
1 18.286
( A / F ) stoic 16.82
( A / F ) stoic = = = 58.8
0.286
Since (A/F) is the ratio of the air flowrate to the fuel
flowrate,
m air 15.9
m fuel = = = 0.270 kg / s
( A / F ) 58.8

Example 2.2
A natural gas-fired industrial boiler (refer Fig. 2.5)

operates with an oxygen concentration of 3 mole percent
in the flue gases. Determine the operating air-fuel ratio
and the equivalence ratio. Treat the natural gas as
methane.
Solution:
Given XO2 = 0.03, MWfuel = 16.04, MWair = 28.85
Find (A/F) and
We can use the given O2 mole fraction to find the air-fuel
ratio by writing an overall combustion equation assuming
complete combustion, i.e. no dissociation (all fuel C is
found in CO2 and all fuel H is found in H2O).
Example 2.2 (contd)
CH4 + a(O2+3.76 N2) => CO2 + 2H2O + bO2 + 3.76aN2

Where a and b are related from conservation of O atoms,
2a = 2+ 2 + 2b
or
b = a-2
From the definition of a mole fraction
NO2 b a2
O2 = = =
N mix 1 + 2 + b + 3.76a 1 + 4.76a
Substituting the known value of O2 (=0.03) and then

solving for a yields a2
0.03 =
1 + 4.76a
a = 2.368

Example 2.2 (contd)
The mass air-fuel ratio, in general, is expressed as

N air MWair
(A/ F) = =
N fuel MW fuel
4.76a MWair
(A/ F) =
1 MW fuel
4.76(2.368)(28.85)
(A/ F) = = 20.3
16.04
To find . We need to determine (A/F)stoic. Since a= 2,

hence 4.76(2)(28.85)
( A / F ) stoic = = 17.1
16.04
( A / F ) stoic 17.1
= = = 0.84
(A/ F) 20.3

Example 2.2 (contd)
Comment: In the solution, we assumed that the O2 mole

was on a wet basis, i.e. moles of O2 per mole of
moisture-containing flue gases. Frequently, in the
measurement of exhaust species, moisture is removed
to prevent condensation in the analyzers, thus O2 can
also be reported on a dry basis.

enthaply of formation
In dealing with chemically reacting systems, the concept

of absolute enthalpies is extremely valuable.
For any species, we can define an absolute (or
standardized) enthalpy that is the sum of an enthalpy
that takes into account the energy associated with
chemical bonds (or lack thereof), the enthalpy of
formation, hf, and an enthalpy that is associated only
with temperature, the sensible enthalpy change, hs.
Thus, we can write the molar absolute enthalpy for
species i as:

enthalpy of formation
0
h i (T ) = h f ,i (T ref ) + h s ,i (T ref )
0
where h s ,i h i (T ) h f ,i (T ref )
To make practical use of Eq. 2.34, it is necessary to

define a standard reference state. We employ a
standard-state temperature, Tref = 25C (298.15 K), and
standard-state pressure, Pref = P0 = 1 atm (101,325 Pa).
Furthermore, we adopt the convention that enthalpies of
formation are zero for the elements in their naturally
occuring state at the reference state temperature and
pressure. For example, at 25C and 1 atm, oxygen exists
as diatomic molecules.
Example 2.3
A gas stream at 1 atm contains a mixture of CO, CO2,

and N2 in which the CO mole fraction is 0.10 and the
CO2 mole fraction is 0.20. The gas-stream temperature
is 1200 K. Determine the absolute enthalpy of the
mixture on both a mole basis (kJ/kmol) and a mass basis
(kJ/kg). Also, determine the mass fractions of the three
component gases.
Solution
Given: CO = 0.10, T = 1200 K, CO2 = 0.20, P = 1 atm
Find: h mix , h , Y , Y and Y
mix CO CO2 N2

Example 2.3 (contd)
Finding hmix requires the straightforward application of the

ideal-gas mixture law, and to the N2, the knowledge that
i = 1.
Thus, xN2 = 1-xCO2 = 0.70
h mix = xi h i = xCO[h f ,CO + (h(T ) h

0
) ]
f , 298 CO
0
+ xCO2 [h f ,CO 2 + (h(T ) h )
f , 298 CO
2
]+
0
xN 2 [h f , N 2 + (h(T ) h f , 298 N
2
) ]

Example 2.3 (contd)
Substituting values from Appendix A (Table A.1 for CO,

Table A.2 for CO2, and Table A.7 for N2):
h mix = 0.10[110,541 + 28,440]
+ 0.20[393,546 + 44,588]
+ 0.70[0 + 28,118]
h mix = 58,339.1 kJ / kmolmix
To find hmix , we need to det er min e the molecular weight of the mixture
MWmix = i MWi = 0.10(28.01) + 0.20(44.01) + 0.70(28.013)
= 31.212
hmix 58,339.1
hmix = = = 1869.12 kJ / kgmix
MWmix 31.212

Example 2.3 (contd)
Since we have previously found MWmix, calculations on the

individual mass fraction follows simply from their
definitions
28.01
YCO = 0.10 = 0.0897
31.212
44.01
YCO2 = 0.20 = 0.2820
31.212
28.013
YN 2 = 0.70 = 0.6282
31.212
As a check, 0.0897+ 0.2820 + 0.6282 = 1.000

Knowing how to express the enthalpy for mixtures of

reactants and mixtures of products allows us to define
the enthalpy of combustion. Consider the steady-flow
reactor, shown in Fig. 2.7 in which a stoichiometric
mixture of reactants enters and products exits, both at
standard-state conditions (25C, 1 atm).
The combustion process is assumed to be complete, i.e.
all of the fuel carbon is converted to CO2 and all of the
fuel hydrogen is converted to H2O. For the products to
exit at the same temperature as the entering reactants,
heat must be removed from the reactor. The amount of
heat removed can be related to the reactant and product

(contd)
absolute enthalpies by applying the steady-flow form of the

first law:
qcv = ho hi = hprod hreac
The definition of the enthalpy of reaction, or the enthalpy of
combustion, hR (per mass of mixture), is
hR = qcv = hprod - hreac
Or, in terms of extensive properties
HR = Hprod- Hreac
The enthalpy of combustion can be illustrated graphically,
as shown in Fig. 2.8. Consistent with the heat transfer
being negative, the absolute enthalpy of the products lies

(contd)
below that of the reactants. For example, at 25C and 1

atm, the reactants enthalpy of a stoichiometric mixture of
CH4 and air, where 1 kmol of fuel reacts is -74.831 kJ. At
the same conditions (25C, 1 atm),the combustion
products have an absolute enthalpy of -877,236 kJ.
Thus,
HR = -877,236-(-74,831) = -802,405 kJ.
This value can be adjusted to a per-mass-of-fuel basis:
hR(kJ/kgfuel) = HR/MWfuel
hR(kJ/kgfuel) = (-802,405/16.043) = -50,016.

Enthalpy of combustion and heating value
(contd)

(contd)
This value can, in turn, be converted to a per-unit-mass-of-

mixture basis:
kJ kJ m fuel
hR = hR
kg m
kg mix fuel mix
m fuel m fuel 1
= =
mmix mair + m fuel ( A / F ) +1
From Table 2.1, we see that the stoichiometric air-fuel ratio

for CH4 is 17.11, thus
kJ 50,016
hR = 2761.8
kg
mix 17. 11 + 1
Note that the value of the enthalpy of combustion depends

on the temperature chosen for its evaluation since the

(contd)
Enthalpies of both the reactants and products vary with

temperature, i.e. the distance between Hprod and Hreac
lines in Fig. 2.8 is not constant.
The heat of combustion, hc (known also as the heating
value), is numerically equal to the enthalpy of reaction,
but with opposite sign. The upper or high heating value,
HHV, is the heat of combustion calculated assuming that
all of the water in the products has condensed to liquid.
This scenario liberates the most amount of energy,
hence the designation upper. The lower heating value,
LHV, corresponds to the case where none of the water is
assumed to condense. For CH4, the upper heating value

(contd)
is approximately 11 percent larger than the lower.

Standard-state heating values for a variety of
hydrocarbon fuels are given in Appendix B.

Example 2.4
A. Determine the upper and lower heating values at 298 K

of gaseous n-decane, C10H22, per kilomole of fuel and
per kilogram of fuel. The molecular weight of n-decane
is 142.284.
B. If the enthalpy of vaporization of n-decane is 359
kJ/kgfuel at 298 K, what are the upper and lower
heating values of liquid n-decane?
Solution
A. For 1 mole of C10H22, the combustion equation can be
written as
C10H22 (g) + 15.5 (O2+3.76N2) => 10CO2 + 11H2O (l or g)
+15.5(3.76)N2
Example 2.4 (contd)
For either the upper or lower heating value,

Hc = -HR = Hreac-Hprod
Where the numerical value of Hprod depends on whether
the H2O in the products is liquid (determining higher
heating value) or gaseous (determining lower heating
value). The sensible enthalpies for all species involved
are zero since we desire Hc at the reference state
(298K). Furthermore, the enthalpies of formation of the
O2 and N2 are also zero at 298K. Recognizing that
H =N h reac H = N h
i i prod i i
reac prod
0 0 0
H c , H 2O (l ) = HHV = (1)h f ,C10 H 22 [10h f ,CO2 + 11h f , H 2O ( l ) ]

Example 2.4 (contd)
Table A.6 (Appendix A) gives the enthalpy of formation

for gaseous water and the enthalpy of vaporization. With
these values, we can calculate the enthalpy of formation
for the liquid water.
h f , H 2O (l ) = h f , H 2O ( g ) h fg = 241,847 44,010 = 285,857kJ / kmol
Using this value, together with enthalpies of formation
given in Appendices A and B, we obtain the higher
heating value
kJ kJ kJ
H c , H 2O ( l ) = (1) 249,659 10 393,546 + 11 285,857
kmol kmol kmol
= 6,830,096kJ
H c 6,830,096 kJ
hc = = = 6,830,096 kJ / kmol C10 H 22
N C10 H 22 1 kmol

Example 2.4 (contd)
kJ
h c 6,830,096 kmol
hc = = = 48,003kJ / kgC10 H 22
MWC10 H 22 142.284 kg
kmol
hc = 44,601 kJ / kg C10 H 22
B. For C10H22, in liquid state

0
H reac = (1)(h f ,C10 H 22 ( g ) h fg )
hc (liquid fuel ) = hc ( gaseous fuel ) h fg
Thus
hc (higher ) = 48,003 359 = 47,644 kJ / kg C10 H 22
hc (lower ) = 44,601 359 = 44,242 kJ / kg C10 H 22

Adiabatic flame temperatures
We define two adiabatic flame temperatures: one for

constant-pressure combustion and one for constant-
volume. If a fuel-air mixture burns adiabatically at
constant pressure, the absolute enthalpy of the reactants
at the initial state (say, T = 298 K, P = 1 atm) equals the
absolute enthalpy of the products at the final state
(T=Tad, P = 1atm), results in
Hreac(Ti, P) = Hprod(Tad, P)
or, equivalently, on a per-mass-of mixture basis,
hreac(Ti,P) = hprod(Tad, P)

Adiabatic flame temperatures (contd)
This first-law statement, Eqn. 2.40, defines, what is

called the constant-pressure adiabatic flame
temperature. This definition is illustrated graphically in
Fig. 2.10. Conceptually, the adiabatic flame temperature
is simple, however, evaluating this quantity requires
knowledge of this composition of the combustion
products.
At typical flame temperatures, the products dissociate
and the combustion products. At typical flame
temperatures, the products dissociate and the mixture
comprises many species. As shown in Table 2.1 and
Table B.1 in Appendix B, flame temperatures are
typically several thousand kelvins. Calculating the
complex composition
Adiabatic flame temperatures (contd)
By invoking chemical equilibrium is the subject of the

next section. The following example illustrates the
fundamental concept of constant-pressure adiabatic
flame temperatures, while making crude assumptions
regarding the product mixture composition and
evaluation of the product mixture enthalpy.

Example 2.5
Estimate the constant-pressure adiabatic flame

temperature for the combustion of a stoichiometric CH4-
air mixture. The pressure is 1 atm and the initial reactant
temperature is 298 K.
Use the following assumptions:
1. Complete combustion (no dissociation), i.e. the
product mixture consists of only CO2, H2O, and N2.
2. The product mixture enthalpy is estimated using
constant specific heats evaluated at 1200 K (~ 0.5(Ti
+Tad), where Tad is guessed to be about 2100 K.

Example 2.5 (contd)
Solution
Mixture composition:
CH4 +2(O2+3.76N2) => 1CO2 + 2H2O + 7.52N2
NCO2 = 1, NH2O = 2, NN2 = 7.52
Properties (Appendices A and B)
Species Enthalpy of Specific Heat
Formation @298K @1200 K
h f , i (kJ/kmol) c p ,i (kJ/kmolK)
CH4 -74,831 -
CO2 -393,546 56.21
H2O -241,845 43.87
N2 0 33.71
O2 0 -
Example 2.5 (contd)
First law (Eq. 2.40):

H reac = N i h i = H prod = N h i i
reac prod
H react = (1)(74,831) + 2(0) + 7.52(0) = 74,831) + 2(0) + 7.52(0)

= 74.831kJ
H prod = N i [h f ,i + c p (Tad 298)]
= (1)[393,546 + 56.21(Tad 298)] + (2)[241,845 + 43.87(Tad 298]] + (7.52)[0 + 33.71(T ad 298)]
Equating H react to H prod and solving for Tad yields
Tad = 2318K

Example 2.6
Estimate the constant-volume adiabatic flame

temperature for a stoichiometric CH4-air mixture using
the same assumptions as in Example 2.5. Initial
conditions are Ti = 298 K, P = 1 atm (= 101,325 Pa).
Solution
The same composition and properties used in Example
2.5 apply here. We note, however, that the cp,i values
should be evaluated at a temperature somewhat greater
than 1200 K, since the constant-volume Tad will be
higher than the constant-pressure Tad. Nonetheless, we
will use the same values as before.

Example 2.6 (contd)
H reac H prod R u ( N reacTinit N prod Tad ) = 0

or
N h N h R (N
reac
i i
prod
i i u T
reac init N prod Tad )
H react = (1)(74,831) + 2(0) + 7.52(0) = 74,831kJ

H prod = (1)[393,546 + 56.21(T ad 298)] + (2)[241,845 + 43.87(Tad 298)] + (7.52)(0 + 33.71(Tad 298)]
= 877,236 + 397.5(Tad 298)kJ
Ru ( N reacTinit N prod Tad = 8.314(10.52)(298 Tad )
where N reac = N prod = 10.52kmol
=> Tad = 2889 K

References
1. Turns, S.R. (2012). An introduction to combustion-

concepts and applications. 3rd Edition, McGraw-Hill.

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B.

Eng (Hons) Chemical Engineering

Combustion and Thermochemistry

Combustion modes and flame types

Reactants and products mixtures

Absolute (or standardized) enthalpy and

Adiabatic flame temperatures

Last Updated: 22/08/2016 I-Station Solutions Sdn Bhd 2

To provide the understanding and knowledge on

Last Updated: 22/08/2016 I-Station Solutions Sdn Bhd 3

Student should be able to understand the combustion,

Last Updated: 22/08/2016 I-Station Solutions Sdn Bhd 4

Combustion can occur in either a flame or nonflame

Under certain conditions (Fig. 1.6b), rapid oxidation

Last Updated: 8/22/2016 I-Station Solutions Sdn Bhd 7

The two classes of flames, premixed and nonpremixed

Diesel-engine combustion is generally considered to

Last Updated: 8/22/2016 I-Station Solutions Sdn Bhd 10

Last Updated: 8/22/2016 I-Station Solutions Sdn Bhd 11

. CxHy +a(O2 + 3.76 N2) => xCO2 + (y/2)H2O + 3.76aN2

Last Updated: 8/22/2016 I-Station Solutions Sdn Bhd 12

Table 2.1 shows stoichiometric air-fuel ratios for

Last Updated: 8/22/2016 I-Station Solutions Sdn Bhd 13

The equivalence ratio, , is commonly used to indicated

Last Updated: 8/22/2016 I-Station Solutions Sdn Bhd 14

From this definition, we see that for fuel-rich mixtures,

Last Updated: 8/22/2016 I-Station Solutions Sdn Bhd 15

A small, low-emission, stationary gas-turbine engine (see

Given = 0.286, MWair = 28.85, m air =15.9 kg/s,

Last Updated: 8/22/2016 I-Station Solutions Sdn Bhd 16

We will proceed by first finding (A/F) and then mfuel.

Where a = x+y/4 = 1.16 + 4.32/4 = 2.24.

Last Updated: 8/22/2016 I-Station Solutions Sdn Bhd 17

A natural gas-fired industrial boiler (refer Fig. 2.5)

CH4 + a(O2+3.76 N2) => CO2 + 2H2O + bO2 + 3.76aN2

Substituting the known value of O2 (=0.03) and then

Last Updated: 8/22/2016 I-Station Solutions Sdn Bhd 19

The mass air-fuel ratio, in general, is expressed as

To find . We need to determine (A/F)stoic. Since a= 2,

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Comment: In the solution, we assumed that the O2 mole

Last Updated: 8/22/2016 I-Station Solutions Sdn Bhd 21

In dealing with chemically reacting systems, the concept

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To make practical use of Eq. 2.34, it is necessary to

A gas stream at 1 atm contains a mixture of CO, CO2,

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Finding hmix requires the straightforward application of the

h mix = xi h i = xCO[h f ,CO + (h(T ) h

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Substituting values from Appendix A (Table A.1 for CO,

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Since we have previously found MWmix, calculations on the

As a check, 0.0897+ 0.2820 + 0.6282 = 1.000

Last Updated: 8/22/2016 I-Station Solutions Sdn Bhd 27

Knowing how to express the enthalpy for mixtures of

Last Updated: 8/22/2016 I-Station Solutions Sdn Bhd 28

absolute enthalpies by applying the steady-flow form of the

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below that of the reactants. For example, at 25C and 1

Last Updated: 8/22/2016 I-Station Solutions Sdn Bhd 30

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This value can, in turn, be converted to a per-unit-mass-of-