Teknik Pembakaran English Version

SUBJECT :
COMBUSTION ENGINEERING
DEPARTEMEN TEKNIK KIMIA UNIVERSITAS INDONESIA
COMBUSTION
ENGINEERING
Oleh : Dr.Ing Donni Adinata, ST., M. Eng. Sc
SYLLABUS
Introduction
Basics of Combustion
Combustion System
Chemical Kinetics of Combustion

Combustion Chemistry
Laminar Premix Flame
Turbulent Premix Flame
Laminar (Diffusion) Non-Premix Flame
Turbulent Non-Premix Flame
2
REFERENCE
Combustion Fundamental and Application, J. Warnatz,
dkk, 1999
Combustion, I. Glassman, 1996
Simulating Combustion, G.P. Merker, dkk, 2004
Industrial Combustion Pollutants and Control, C.E.
Baukal Jr., 2004
Combustion Physics, C.K. Law, 2006
Combustion Fundamentals and Technology of
Combustion, El-Mahallawi, 2002
Combustion Theory, Williams, 1985
3
SUBJECT :
PENDAHULUAN
INTRODUCTION
Dr. rer. nat. Ir. Yuswan Muharam, M.T.
Oleh : Dr.Ing Donni Adinata, ST., M. Eng. Sc
WHAT IS COMBUSTION?
Main source of driving energy for the technology
community (~85% of world energy consumption
Main source of air pollution;
Utilization
Driving force of aircraft and spacecraft, power plant,
heating, transportation, and material processing
APPLICATION OF COMBUSTION
Gas turbine and jet engines
Rocket thrust
Piston engine
Weapons and explosives
Furnace dan boiler
Synthesis of materials with flame (fullerene, nanomaterial)
Chemical processing (black carbon production)
Material formation
Fire hazards and safety
6
DEFINITION
Technique
Reaction of fuel with oxidant

Exotermic
Self-sustaining,
Through some chemical and physical events
Form water and carbondioxide (the most stable
reaction product)
7
CLASSIFICATION
Conventional Combustion
Oxidation of fuel that is accompanied by flame or
high temperature
Non-conventional Combustion
Oxidation of fuel that is not accompanied by
flame or high temperature
CLASSIFICATION
Subsonic combustion or deflagrasi
Occurs in daily life
Propagation speed of combustion reaction wave is
lower than speed of sound
Supersonic combustion or detonation

Propagation speed of combustion reaction wave is
higher than speed of sound
COMBUSTION PROCESS
Complex interaction of
Physical process
Fluid dynamics
Heat transfer
Mass transfer
Chemical process
thermodynamics
Chemical kinetics
Practical applications involving other disciplines :

aerodynamics, fuel technology, and machine engineering.
10
THERMODYNAMICS
Stoichiometry
Properties of gases and its mixture

Heat of formation
Heat of reaction
Equilibrium
Adiabatic flame temperature
11
TRANSPORT PHENOMENA
Heat Transfer
Conduction
Convection
Radiation
Mass Transfer
Total,
Species
Momentum Transfer
Laminar Flow
Turbulent Flow
Inertia and viscosity effects
Combustion aerodynamics
12
CHEMICAL KINETICS
Application of thermodynamics to the reaction system that produces :
Chemical composition of combustion products
Maximum temperature (adiabatic flame temperature)
However, thermodynamics alone is unable to inform that the system will

reach the equilibrium or not. If the timescale of chemical reactions
involved in combustion process is proportional to the timescale of
physical process (such as diffusion, fluid flow) that occur
simultaneously, then the system may never reach equilibrium.
Therefore, we need rate of chemical reaction in combustion
13
COMPONENTS OF COMBUSTION
Fuel
Fossil-HC based
Natural gas (methane, ethane, and propane)
Petroleum products (gasoline, diesel, jet fuel, oil fuel)
Coal and its products (synthetic gas and liquid)
Oxidant
Oxygen from the air
Hydrogen and oxygen are used to drive rocket and on the fuel
cell
Fuel and oxidant are part of the same molecule

Explosives (such as TNT) and solid propellants
14
HISTORY OF FOSSIL FUEL

Before 1900s: wood,
Early 1900s: coal,

1900s:
Petroleum products (almost all transportation)
Coal (power generation)
End of 1900s : natural gas (heating, cooking, power
generation and transportation)

15
TOTAL PRIMARY ENERGY SUPPLY

IN MTOE
1 Mtoe = 16,3 GJ
Other : geothermal, solar, wind, etc.

Source: International Energy Agency
16
OUTLOOK OF TOTAL PRIMARY

ENERGY SUPPLY IN a MTOE
17
EMISSION
Influencing variable :
Type and composition of fuel,

Ratio of fuel and oxygen,
Design of combustion system,
Operating condition (initial temperature and
pressure),
Additive
18
CLASSIFICATION OF EMISSION
Not a pollutant
CO2 and H2O.
Pollutant :
Unburnt fuel;
Nitrogen oxide(NO, NO2, and N2O, or NOx),
Sulfur oxides (SO2 and SO3, or SOx),
Product of imperfect combustion (PIC),
CO,
Asiri organic compound (VOC), such as ethane, ethylene, propane,
acetylene and solvent, oxygenate (aldehyde, ketone, alcohol, peroxide),
Aromatic,
Polycyclic aromatic carbon (PAH),
Particulate (solid carbon or soot)
Halogenated compound,
Metal
19
20
21
EMISSION
CO2
Source : all combustion ;
Hazard to health
> 5000 ppm > 2 8 hours,
Accelerating the pace
Levels in atmosphere increased from 280 ppm (pre-industrial
times) to > 350 ppm (1990);
Greenhouse gases
Along with other greenhouse gases (exampe : methane),
CO2 absorbs infrared radiation which is emitted by earth,
thus energy in the earth increases and atmospheric
temperature rises.
Become a global issue, after Kyoto Protocol in 1997.
22
World CO2 emissions by fuel source

(in 106 t)
23
World CO2 Emissions by Region

(in 106 t)
24
EMISSION
CO
Source : motor vehicles, industrial processes
Health hazards :
9 ppm (10 mg/m3) > 8 hours,
35 ppm (40 mg/m3) > 1 hour,
Not more than once a year (for both)
Absorbed by the lungs;
Weakening the physical and mental;
Affect embryo development.
25
EMISSION
NOx
Source : motor vehicles; heat and electricity geneartor; nitric
acid; explosives; fertilizer factory.
Hazard to health :
NO2: 0,053 ppm (100 g/m3) > a year;

Reacts with HC and ultraviolet to form oxidant fotochemical
haze,
Respiratory problems and heart disease.
26
EMISSION
SOx
Source : power plant uses thermal from oil and coal containing
sulfur, sulfuric acid plant,
Hazard to health :
SO2:
0,03 ppm (80 g/m3) > a year,
0,14 ppm (365 g/m3) > 24 hours,no more than once a
year,
0,5 ppm (1300 g/m3) > 3 hours.
Causes middle level irritation
Main cause of acid rain.
27
EMISSION
VOC includes ethane, ethylene, acetylene, propane,
butane, pentane, aldehydes, ketones, solvents.

Source : motor vehicles; evaporation of solvent; industrial
processes; disposal of solid waste; burning fuel; oil refineries;
fuel pump station; cleaning clothes; printing; paint.

React with Nox and ultraviolet to form photochemical oxidants.
Acute exposure causes irritation of the eyes, nose and throat;
chronic exposure causes cancer.
28
EMISSION
29
CONVENSIONAL
COMBUSTION CONTROL
Design of reactor or combustor that has resistant to high
temperatures generated
For example :
o Combustion engine cylinder of gasoline-fueled vehicles,
o Alloy tube which has resistant in high temperature on energy
generating system such as gas turbine and furnace.
Design of combustion process

o Operating condition,
o Fuel composition,
o Ratio of fuel and air
30
NON-CONVENSIONAL
COMBUSTION CONTROL
T is lower than flame temperature
For example :
H2-air fuel cell at 80 C, while the hydrogen-air flame
at 2000 C.
Catalytic combustor operates at 800oC and fuel is
processed at wide temperature range.
31
SUBJECT :
COMBUSTION
FUNDAMENTALS
Oleh : Dr.-Ing Donni Adinata, ST., M. Eng. Sc
32
INTRODUCTION
Three fundamental components :
Fuel + Oxidizer + Diluents Combustion Products
33
FUEL
Gaseous Fuels
Liquid Fuels
Solid Fuels
34
GASEOUS FUELS
Predominant fuel source in most of application.
Contain multiple components such as methane, hydrogen,

propane, nitrogen and carbon dioxide.
Sometimes referred to as refinery fuel gases.
The easiest to control because no vaporization is required.
Simpler to control to minimize pollution emissions because
they are more easily staged.
35
GASEOUS
FUELS
36
LIQUID FUELS
Used in some limited applications.
Waste liquid fuels are used in incineration processes.
Challenges of using oils
o Vaporizing the liquid into small enough droplets to burn completely.
Improper atomization produces high unburned hydrocarbon
emissions and reduces fuel efficiency
Steam and compressed air are commonly used to atomize liquid
fuels
The atomization requirements often reduce the options for
modifying the burner design to reduce pollutant emissions.
o Containing impurities like nitrogen and sulfur
In the case of fuel-bound nitrogen, so-called fuel NOx emissions
increase
In the case of sulfur, all of the sulfur in a liquid fuel converts to
SOx emissions
37
Liquid fuels
38
LIQUID FUELS
39
LIQUID FUELS
The advantages of liquid fuel
o The flames much more luminous

Caused by the high solid carbon content which produces
infrared radiation when heated.
Enhance the radiation heat transfer from the flame to the
material being processed.
Indirectly reduce pollution emissions because the higher heat
transfer can improve the thermal efficiency which means that
less fuel needs to be burned.
40
SOLID FUELS
Not commonly used in most industrial combustion
applications.
The most common solid fuels
o Coal in power generation
o Coke in some primary metals production processes.
o Sludge (pseudosolid fuel) in incinerators.
Contain
o Impurities such as nitrogen and sulfur
o Hazardous chemicals
41
OXIDIZER
Air (oxidant) air/fuel combustion
79% nitrogen diluent

21% oxygen oxidizer
Oxygen-enhanced combustion (OEC)
Air blended with pure O2
High purity O2 oxy/fuel combustion
42
AIR/FUEL BURNER
43
AIR ENRICHED WITH O2 BURNER
44
O2 LANCING BURNER
45
OXY/FUEL
46
AIR-OXY/FUEL
47
INTERNAL COMBUSTION ENGINE

The combustion of fuel and an oxidizer
(typically air) occurs in a confined space called
a combustion chamber.
This exothermic reaction creates gases at high

temperature and pressure, which are permitted
to expand.
Useful work is performed by the expanding hot
gases acting directly to cause movement of
solid parts of the engine, by acting on pistons,
rotors, or even by pressing on and moving the
entire engine itself.
48
INTERNAL COMBUSTION ENGINE
49
DILUENT
To reduce and moderate the flame temperatures that reduce NOx
emissions.
To change the heat-transfer distribution from the flame. The flame
can be stretched to make the flame radiation more uniform by
dilution.
To increase the convection heat transfer in the furnace (by adding
to the flame).
Example:
o Products of combustion that are recycled back toward or into the burner.
o Water, steam, and gases like nitrogen or carbon dioxide.

50
RECIRCULATION
Furnace gas recirculation (FuGR)
The combustion products are drawn back into the

flame inside the furnace.
Flue gas recirculation (FlGR)
The combustion products are drawn back into the
flame outside the furnace.
51
RECIRCULATION
For improved thermal efficiency
Enhanced convective heat transfer inside the combustor due to
the improved fluid flow and the increased residence time of the
hot gases in the combustor.
Reduced NOx emissions.

Reduces the peak flame temperatures in the combustion zone
that are the primary source of thermal NOx emissions
52
SUBJECT :
COMBUSTION CONTROL
53
COMBUSTION CONTROL
Performance parameters of the combustion process:
- Energy;
- Flame temperature;
- Pollutants;
- Otoignisi;
- Flame propagation speed;
Control parameters in combustion process:

Reactor design (the engine) that resists with high temperatures,
- Cylinder design of gasoline engine and diesel.
- Alloy tube power systems (gas turbine and furnace).
Design of the combustion process

- Operating conditions, fuel composition, the ratio of fuel and air.
54
COMBUSTION CONTROL
Necessary to control the combustion
o Chemistry of combustion
- Chemical reaction;
- Chemical kinetics;
- Thermodynamics.
o Fluid dynamics
- Mass balance,
- Energy balance,
- Motion equations,
- Transport parameters (diffusion, turbulence, dispersion),
- Material properties (viscosity, density, thermal conductivity, heat
capacity).
55
FLAME TYPE
Premix Flame
o Laminar
o Turbulen
Non- Premix Flame (Diffusion)
o Laminar
o Turbulent
Parsial Premix Flame
o Laminar
o Turbulent
56
LAMINAR (TURBULENT)
PREMIX FLAME
Fuel (gas) and oxidizer are mixed homogeneously
before burning
Laminar flow (turbulent)
Premix turbulent flame:
o Combustion in gasoline engines
o Combustion in gas turbines
57
COMBUSTION IN GASOLINE ENGINE
58
LAMINAR (TURBULENT)
PREMIX LAMINAR
Stoichiometry:
o Premix flame is called stoichiometric if the reactant

mixture containing oxidizer in the appropriate
quantities to react with the fuel (burned) is perfect.
o If the fuel is in excess: fuel rich system.
o If the oxygen is in excess fuel poor system
o Standard air composition:
59
LAMINAR (TURBULENT)
PREMIX LAMINAR
Stoichiometry:
o (A / F) Stoic
Mass ratio of air-fuel
(air mass) / (fuel mass)
o (A / F) Stoic = [5 (32 +3.762 * 28)] / (44) = 15.6

o = equivalence ratio of fuel
(A / F) Stoic / (A / F) actual
60
LAMINAR (TURBULENT)
PREMIX LAMINAR
stoichiometry:
o = 1: combustion stiochiometry
o <1: thin mixture , lean combustion
o > 1: rich mixture , rich combustion
o The European and the Japanese Convention use air
equivalence ratio,
=1/
61
LAMINAR (TURBULENT)
NON-PREMIX LAMINAR
Fuel (gas) and oxidizer are mixed during the combustion
process
Examples of laminar non-premix flame:
- Wax flame
Examples of turbulent non premix flame:
- Hydrogen rocket engine
- diesel engines
62
LAMINAR (TURBULENT)
NON-PREMIX LAMINAR
Wax Flame
63
EXAMPLE OF COMBUSTION SYSTEM
64
SUBJECT :
COMBUSTION
STOICHIOMETRY
65
COMBUSTION STOICHIOMETRY
.
To calculate how much air is used to oxidize the fuel
.
. completely into CO2, H2O, N2 and SO2.
. Complete combustion of CH4 in the air:
.
66
Volume ratio of the stoichiometric air-methane, AFRv,:
Mass ratio of the stoichiometric air-methane, AFRm,:
67
NON-STOICHIMETRY MIXTURE
Poor fuel mixture:
- Lack of fuel than the stoichiometric ratio;

- Combustion may be perfect;
- Excess oxygen in the product.
Rich fuel mixture:

- Excess fuel than the stoichiometric ratio;
- Combustion may not be complete;
- Intermediate in the product.

68
Equivalence ratio, :
< 1 poor fuel;

> 1 rich fuel.
69
Air-fuel relative ratio, 1 /:
AFRactual/AFRstoichiometry;
Also called an equivalence ratio of oxidizing agent
Percent theoretical air, 100 / ;
Percent excess air, EA:
70
a, a1, a2 . = coefficient;
= equivalence ratio;
Other species can be added on the right side;
71
If = 1, so complete reaction
become :
72
If <1 and the complete reaction, a2 = a4 = 0;
from the atom balance sheet of C, H, and O :

a1=x, a3=y/2, and a5=a(1-)/.
(1-)/ is called "excess air".
73
If > 1, the composition of the final product should be
calculated using the equilibrium (there is CO and H2 , so

the amount of unknown variables is more than
equations).
74
EXAMPLE
Hydrocarbon fuels the composition are 84.1% mass C
and 15.9% mass of H has a molecular weight of 114.15.

Calculate the moles amount of air required for
stoichiometric combustion moles amount of product
produced per mole of fuel. Calculate AFR stoichiometric!
75
ANSWER
Assume fuel composition is CaHb.
Molecular Weight = 114.15 = 12.011a + 1.008b

Gravimetric analysis:
a = 8 ; b = 18
fuel is octane
76
ANSWER
77
ANSWER
Stoichiometric Combustion
1 mol of fuel 59,66 mol air
64,16 mol product.
AFRstoichiometric = 59,66
78
SUBJECT :
FIRST LAW OF
THERMODYNAMICS
79
ENERGY BALANCE AND ENTHALPY
80

Constant Volume, TR = TP = T
becomes
Heat reaction at constant volume

in T (per mol)
81

Constant Pressure, TR = TP = T
becomes
Heat reaction at constant

pressure at T (per mole)
82
Relation of (H)P,T and (U)V,T :

83

Combustion product is H2O in vapor and liquid phase
84

Fuel in gas and liquid phase
85
ENTHALPY OF FORMATION
Formation enthalpy of a compound:
o The increase of enthalpy is associated with formation reaction of
one mole compound from its elements, where each elements is at its
standard thermodynamic state at a certain temperature.
Default state:
o At 1 atm pressure and certain temperature.
Datum state:
o All other thermodynamic state were referred to this state;
o Usually at 298.15 K (25oC) and 1 atm;
o Enthalpy of the elements in its reference state at datum temperature
is zero ;
o Element reference state is a stable standard state :
Oxygen at 298.15 K, the reference state is gaseous O2.
86
ENTHALPY OF FORMATION
Enthalpy of products at the standard state is relative to
the datum enthalpy:
Enthalpy of reactants at the standard state is relative to

the datum enthalphy:
The increase of enthalpy:
87
EXAMPLE
Calculate the enthalpy of products and reactants and the
increase of energy in the stoichiometric mixture reaction

of methane and oxygen at 298.15 K!
88
ANSWER
89
STANDARD ENTHALPY
Standard
Enthalpy
Sensibel
Enthalpy
Temperature function of enthalpy :
Consists of two sets of coefficients (NASA program):

1. 300 K 1000 K
2. 1000 K 5000 K
90
STANDARD ENTHALPY
91
HEAT VALUE
If the fuel composition is not known, the enthalpy of the
reactants can not be calculated from its enthalpy of
formation;
Heat value of fuel:
a. Reaction heat at constant pressure (volume) at standard
temperature (usually 25 C) for complete combustion of fuel;

b. Measured in the calorimeter;
c. J / kg or J / kmol of fuel.
92
HEAT VALUE
High heating value (gross heating value):
o All H2O condensed into a liquid phase;
Low heating value (net heating value)

o All H2O is in the vapor phase.
93
ADIABATIC COMBUSTION
Adiabatic combustion in constant volume :
The data of internal energy or enthalpy is given relative

to its value at the reference temperature T0, U(T) - U(T0)
94
Adiabatic combustion in constant pressure :
95
Adiabatic flame temperature

96
SUBJECT :
CHEMICAL KINETICS
97
CHEMICAL REACTION
The different species molecules collide, producing one or more
new molecules;
Atoms of reactant molecules are distributed back to the new
molecules;
Reactant molecules must have enough kinetic energy to break
chemical bonds during the collision and new bonds are formed;
Energy content of the collision products differs from the energy
content of molecules that collide Basis of release or absorption
of heat in chemical reactions.
98
GLOBAL REACTION (OVERALL)

Combustion of 1 mole of CH4 and 2 moles of O2 to produce 1 mole
of CO2 and 2 moles of H2O (complete reaction).
Number of reactant molecules which collide to produce products are
not the same as indicated by the global reaction.
The molecules that collide may not
have enough kinetic energy to reach so many replication
of the bonds required by the global equation.
99
ELEMENTARY REACTION
Reactions that occur at the molecular level which
are described in accordance with the equation

of chemical reaction.
shows that 2 moles of H2 react with 1 mole of O2 to

produce 1 mole of H2O NOT TRUE!
100
ELEMENTARY REACTION
Reality: a sequential process that
involves several intermediate species:
First reaction termination of the H-H and O-O bonds, the

formation of two O-H bonds and an atomic H.
101
ELEMENTARY REACTION
Radicals or free radicals or reactive species : reactive
molecules or atoms that have unpaired electrons.

Complete description for burning process of H2 with O2
more than 20 elementary reactions.
102
CHAIN REACTION
Combustion of hydrocarbons
Tens to hundreds of species and radicals;
Hundreds to thousands of elementary reactions that arrange the
overall reaction reaction mechanism or detail chemical
mechanisms;
The process of producing products, initiate other similar processes
automatic continuity.
103
CHAIN REACTION
2.50: chain initiation (reactive intermediate is formed through the
action of heat or something like O2 molecules).

2:51: chain branching (making more radical).
2:52: chain propagation ( change of radical identity, but the amount
are still same).

2:53: chain termination (radicals is consumed and the chain ends).
104
TYPE OF ELEMENTARY REACTION

Based on the number of reactant molecules :
o Elementary reactions
overall order (a1 + a2 + a3 + ...),

a1 is order of the reactants R1 ,etc.
o Overall order is called molecularity.
105
TYPE OF ELEMENTARY REACTION

Based on its molecularity:
- unimolecular reaction
- bimolecular reaction
- trimolecular reaction
106
REACTION RATE COEFFICIENT

DEPENDENCE ON TEMPERATURE
Arrhenius law:
o A = pre-exponential factor;
o Ea = activation energy;
o exp(- Ea/RT): the proportion of collisions that occur
between molecules that have kinetic energy greater
than Ea.
107
REACTION RATE COEFFICIENT

DEPENDENCE ON TEMPERATURE
Binary reactions:
o Arrhenius behavior in the middle temperature range;
o Dependence of the rate coefficient on temperature is in
the exponent.
Low activation energy reaction with a wide temperature

range:
o Behavior of "non-Arrhenius" modified Arrhenius
108
REACTION RATE
COEFFICIENT DEPENDENCE ON PRESSURE
Decomposition reaction (unimolecular)
AB+C
and recombination (bimolecular)
A+BC+D
o Rate depends on the pressure;
o The reaction is not elementary (consisting of a number
of reactions);
o Lindemann Model: study on the rate coefficient dependence on
pressure
109
REACTION RATE
Unimolecular decomposition :
o Need energy to break its bonds;
o Energy is transferred to the molecule through collisions with
molecules M (to stimulate the molecule vibrations);
o Excited molecule decomposes into a product, or is deactivated
through the second collision, depending on the strength of stimulation.
110
REACTION RATE
reaction rate
d A *
ka A M k a A * M ku A *
dt
111
REACTION RATE
d A *
ka A M k a A * M ku A *
dt
Assumption: the concentration of A * in is quasi-steady
state
112
REACTION RATE
Extreme condition
o P <<<
[M] <<<
Second order
Border stage : the activation

o P >>>
[M] >>>
First order
Border stage: the decomposition of A *.

113
REACTION RATE
At P <<<, k tends toward k so that k is

almost independent of P.
At >>> P, k ~
linear dependence.
114
REACTION MECHANISM
Reactants which are consumed and produced arises
from the sum of the contribution of each elementary

reaction.
Example:
The rate of CH3 formation and CH4 consumption
115
REACTION MECHANISM
Mechanism consists of R elementary reactions from
S species,
where r = 1, 2, ..., R,
= stoichiometric coefficients of reactants and products.
Formation rate of species i:
where i = 1, 2, ..., S.
116
ANALYSIS OF REACTION MECHANISM

Detailed reaction mechanism of hydrocarbon combustion
consists of hundreds of elementary reaction. However,
some of them are not important so it can be eliminated.
Analytical methods are needed to eliminate unimportant
reactions, among them:
Sensitivity analysis: identifying the rate limiting reaction steps.
Reaction flow analysis: identifying the characteristics of the
reaction pathway.
Information obtained from these two methods can

be used to dispose unimportant reactions to make
mechanism becomes simple or reduced.
117
SENSITIVITY ANALYSIS
Rate law of a reaction mechanism consisting of R
reaction among S species can be written as a system
of first-order differential equations,
t: independent variable, ci: the dependent variable, kr : the

system parameters.
Solution of ordinary differential equations system

depends on initial conditions and system parameters.
118
SENSITIVITY ANALYSIS
On a number of elementary reactions, changes of kr almost
have no effect on system output

- The reaction is eliminated;
- kr does not need to be accurate.
On a number of other elementary reactions, changes in kr is
very influential on the system output
- kr needs to be accurate;
- Rate limiting or determining stage.
Dependence of ci solution on kr is called sensitivity.
119
ANALYSIS OF REACTION FLOW

Reaction flow analysis calculate the contribution
percentage of each reaction to the establishment or use

of chemical species.
120
SUBJECT :
FLAME TEMPERATURE
121
ADIABATIC FLAME TEMPERATURE
Two-stage analysis,
a. First: the reaction at 298.15 K: heat is released; amount
of heat is calculated based on the amount of fuel and the heat
of combustion;
b. Second: the heat resulted form first stage is used to raise the
temperature of the product from 298.15 K to the final
temperature.
122
ADIABATIC FLAME TEMPERATURE

From the amount of enthalpy , we calculate the temperature in which the
rise of total enthalpy is equal to the heat released by combustion. We can
obtain the final product temperature (calculate Tf in such a way so that
the First Law of Thermodynamics are fulfilled:
ni hi Tin ni hi T f
i 1
reak i 1
prod
Tf is reduced if :
o There is heat loss from the system,
o Tin is less than 298.15 K,

o Phase change, for example some of the heat used for evaporation
123
EXAMPLE
Calculate the adiabatic flame temperature at constant
pressure
for
propane
which
is
burned
with air in composition of 21% O2 and 79% N2 (by

volume)
at
=1. Assume complete combustion
occurs, Pin = Pf = 1 atm and Tin = 60 F.
124
DATA
125
ANSWER
On the stoichiometric and complete combustion conditions:
For propane:
C3H8 + 5(O2 + (0,79/0,21)N2) 3CO2 + 4H2O + (5*0,79/0,21)N2
Composition of air : O2 = 21% volume ; N2 = 79% volume

Initial temperature = 60 F = 520 R
Initial pressure = 1 atm;
R = 0.7302 3/lbmol/R
126
ANSWER
Assume initial volume of the mixture = 1 ft3
Mole of mixture (propane, oxygen and nitrogen) in the vessel

n = (PV) / (RT)
n = (1 atm)(1 ft3) / (0.7302 atm.ft3/lbmol/R
(520 R)
n = 0.00263 lbmol.
Stoichiometric fuel = (1/5) x volume of O2
= (1/5) x 21 = 4.2
127
ANSWER
For gas, volume fraction = mole fraction, then
o Mole fraction of propane = (4.2) / (4.2 +21 +79) = 0.04031
o Mole fraction of oxygen = (21) / (4.2 +21 +79) = 0.20154
o Mole fraction of nitrogen (79) / (4.2 +21 +79) = 0.75816
reactant
o nC3H8 = (0,04031)(0,00263) = 0,00011 lbmol
mC3H8 = (0,00011 lbmol)(44 lb/lbmol) = 0,00484 lb
o nO2 = (0,20154)(0,00263) = 0,00053 lbmol
o nN2 = (0,75816)(0,00263) = 0,00199 lbmol
128
ANSWER
Product
o nCO2 = (3)(0,00011) = 0,00033 lbmol

mCO2 = (0,00033 lbmol) (44 lb/lbmol) = 0,01452 lb
o nH2O = (8)(0,00011)/2 = 0,00044 lbmol
mH2O = (0,00044 lbmol)(18 lb/lbmol) = 0,00792 lb
o nN2 = 0,00199 lbmol
mN2 = (0,00199 lbmol)(28 lb/lbmol) = 0,05572 lb

129
ANSWER
Solved to obtain T;
T = 3556 R = 3096 F = 1702 oC
130
EXAMPLE
If propane is replaced by methane with the same number
of moles (0.00011 lb mol) and burned with air

stoichiometrically, how much is the adiabatic flame
temperature?
131
ANSWER
CH4 + 2(O2 + (0,79/0,21)N2) CO2 + 2H2O + (2*0,79/0,21)N2
Reactant
o CH4 = 0,00011 lbmol = 0,00176 lb
o O2 = 2(0,00011) = 0,00022 lbmol
o N2 = (0,75816)(0,00263) = 0,00083 lbmol
Product
o CO2 = (1)(0,00011) = 0,00011 lbmol = 0,00484 lb
o H2O = (4)(0,00011)/2 = 0,00022 lbmol = 0,00396 lb

o N2 = 0,00083 lbmol = 0,02324 lb
132
ANSWER
Solved to obtain T
T = 3584 R = 3124 F = 1717 C
What if the mole number of fuel is different?
133
HOMEWORK
What is the adiabatic flame temperature of
an ethylene (ethene, C2H4)-air mixture that contains exactly and twice as much
oxygen as is necessary (K-1)
a n-heptane-air mixture that contains exactly and twice as much oxygen as is
necessary (K-2)
a isooctane-air mixture that contains exactly and twice as much oxygen as is
necessary (K-3)
a n-octane-air mixture that contains exactly and twice as much oxygen as is
necessary (K-4)
to burn the fuel completely to CO2 and H2O? Initial mixture temperature
is 298 K and combustion takes place at constant pressure of 1 atm.
Assume complete combustion and no dissociation
134
HEAT OF NON-ADIABATIC
COMBUSTION
135
EXERCISE
Calculate the amount of heat released by combustion
of 0.00484 lb propane with a stoichiometric air at 60 F

and constant pressure of 1 atm, and if the temperature of
exit flue gas is 1400F!
136
Enthalpy curve of water, CO, CO2 and SO2 at T > 60 F

137
JAWAB
Enthalpy curve of hydrogen, air and oxygen at T> 60 F

138
JAWAB
Enthalpy curve of carbon dioxide

139
JAWAB
Enthalpy curve of nitrogen

140
Enthalpy curve of water

141
PRESSURE CONVERSION
142
ANSWER
Mass
mH2O =
mCO2 =
mN2 =
mC3H8 =
At 1400 F
hH2O =
hCO2 =
hN2 =
Q=
143
Heat generated from the

combustion of refinery gas in
T0 = 60 F and the exit temperature
Tf exit.
144
EFFICIENCY OF COMBUSTION
Energy fuel which is

supplied to the control volume
145
CHEMICAL EQUILIBRIUM
Reactant: vi (-); product: vi (+)
Second Law of Thermodynamic

The equilibrium constant at constant pressure
p0 = standard pressure (usually 1 atm)

146
Effect of temperature on the equilibrium:
SUBSTITUTION
G 0
H 0

T2
T p
d ln K p H 0
ln K p

dT
RT 2
T p
H 0
d ln K p
dT
2
RT
147
- Kirchhoff equation
- In a specific scale
d h 0 c p dT
- Substitution of the specific heat:
- The result:
d h0 a1 a2T a3T 2 a4T 3 a5T 4 RdT

148
o Integration
a
a
a
a
h0 h00 a1T 2 T 2 3 T 3 4 T 4 5 T 5 R
2
3
4
5
o Substitution of the specific enthalpy

0 a T a2 T 2 a3 T 3 a4 T 4 a5 T 5 R
h
0
1
h0
2
3
4
5
dT
d ln K p
dT
2
2
RT
RT
o integration
h00
a
a
a
a
ln Kp
a1 ln T 2 T 3 T 2 4 T 3 5 T 4 C
RT
2
6
12
20
149
Effect of pressure on the equilibrium:
= 0: Changes of pressure do not affect the composition;

> 0: mole fraction of dissociation products decreases with increase of
pressure;
<0: mole fraction of reactant decreases with increase of pressure;
150
The equilibrium constant Kc
Relation of Kc and Kp relations (p0 = 1 atm)
151
HOMEWORK
Develop a general equation for Kp as a function of
temperature and calculate Kp at temperature of 1000

C for following water-gas reaction :
152
SUBJECT :
SIMPLE
THERMOCHEMICAL MODEL
153
SIMPLE THERMOCHEMICAL MODEL

Known : mixture of fuel and air at P and T.
Assumptions:
o Combustion chemistry:
Fuel + v Air Product,
o Total Stoichiometric:
1 Kmol fuel requires v kmol of air;
1 kg fuel needs S kg of air;
S = v MWair/MWfuel.
154

Global kinetics:
o yfu = mass fraction of fuel;

o yox = mass fraction of oxygen.
155

Fuel mass balance:
Energy balance:
Equations of motion:
156

These three equations are solved using the boundary
conditions;
Result :
o Concentration profile (conversion) of fuel;
o Oxygen concentration profile (with a stoichiometric relationship);
o Transient temperature profile along the combustion chamber;
o Flame propagation velocity profile;
157
COMPLETE THERMOCHEMICAL MODEL

Using reaction mechanism;
The rate of formation reaction / consumption of all species;
Mass balance of all species (hundreds of species, hundreds of
equations);
Energy balance (an equation);
Motion equations (one equation);
Hundreds of differential equations with boundary conditions solved

using the program
o Homrea
o Chemkin
o Mixfla
158

RESULT
o Concentration profile (conversion) of fuel;
o Concentration profile of O2, CO2, CO, H2O, H2, formaldehyde,
acetaldehyde, propionaldehida, methane, ethane, butane,
propane, ethylene, acetylene, butene, methanol, ethanol,

propanol, ketones, etc.
o Delay time of ignition;
o Flame propagation velocity profile.
159

Setting the operating conditions (P and T), equivalence
ratio and fuel composition:

o Minimize pollutants,
o Set the flame temperature;
o Set the speed of flame propagation;

o Know the delay time of ignition.
160
SUBJECT :
FLAME
161
FLAME
Reaction zone that moves relative to the gas that
sustains it.
Rapid exothermic reaction
Accompanied with light emission
162
FLAME
Premixed flame :
o Reactants are mixed before approaching zone of flame.
o Mixture of initial fuel and oxidant is between particular
composition limit (flammability limit)
Diffusion flame :
o Mixing fuel and oxidant, and combustion occurs in inter-phase
163
FLAME
premixed
diffusion
164
PREMIXED FLAME
Has adiabatic flame temperature and flame rate (flat
front flame rate that is normal to the flame surface and

relative to non-burning reactants)
Occurs if the initial mixture is between the particular
composititon limit (flammability limit).
165
FLAMMABILITY LIMIT
Lower flammability limit (lean limit) :
o Flash point is reached when the fuel gas in small amounts are
added little by little into the air ;
Upper flammability limit (rich limit) :
o Point that is reached if fuel is added again when the mixture is
no longer cause flame.
Flammablility range becomes wider if :
o Temperature of mixture increases
o Mixture pressure increases above atmospheric pressure

The broadening occurs at the upper limit.
166
167
FLAMMABILITY LIMIT
Safety :
o Flammable gas storage area should be ventilated;

o Note the specific gravity of gas; lighter gas is
concentrated in the ceiling, heavy gas at the base;
o Ventilation (natural or mechanical) must be able to

limit the concentration of flammable gas up to 25%
LFL.
168
FLAME TEMPERATURE
Temperature of flue gas leaving the reaction zone, Tf;
Premixed flame :
o Mixture composition is easily known ;
o Mixture enters the flame with a fixed temperature and pressure;
o Flame temperature is easily calculated from the thermodynamic
properties of mixtures;
Diffusion flame :
o Composition of the mixture is difficult to be known so it is difficult to
calculate the flame temperature;
o Because the flame is produced at stoichiometric interphase, the
maximum flame temperature is high (near the adiabatic flame
temperature)
169
FLAME TEMPERATURE
Flame temperature of fuel/ air ~ 2000 K. Near the fllamability limit,
lower temperature 1400-1500 K.
Flame temperature of stable gas phase (homogeneous) combustion
: > 1400oC (between 1500 and 1900oC); This high temperature
heats fuel and air which comes in conduction, convection or
radiaton.
Maximum temperature of premixed flame can be controlled through
the air dilution.
The maximum temperature of difussion flame is higher (~2000oC for
natural gas and ~2200oC for diesel) because of the stoichiometry on

the flame front. As a result, diffusion flame is more stable.
170
HIGH FLAME TEMPERATURE

Advantages :
o Better process
o Stable flame
o High efficiency of energy conversion
Disadvantages :
o At high temperature, nitrogen molecule in the air reacts with oxygen to
form Nox; the higher temperature, the reaction becomes faster.
o At high temperature, production of soot increases
o The maximum flame temperature in combustion system should be
limited
171
EQUILIBRIUM NO
CONCENTRATION
172
FLAME
Laminar premixed flame of methane:

Little of fuel-rich ( = 1, left), fuel-rich and sooting ( > 1,middle), and
diffusion flame (right).
Flame luminosity increases with raising of equivalence

ration because the production of soot increases.
173
FLAME
Picture shows the probe of sampling withdrawal from the flame.

Measurement of samples :
o Provide information of chemical flame;
o Understand the chemical and mechanism of combustion
Flame contains hundreds of intermediate substances.

174
CONCENTRATION PROFILE OF
LAMINER PREMIXED FLAME
Concentration profile of species in the fuel rich methane
flame (premixed flame) along the flame or on the surface

of the burner.
175
CONCENTRATION PROFILE OF SPECIES THROUGH

FRONT OF LAMINER DIFFUSION FLAME
Ethylene from left diffuses oxygen from right and
completed in the flame zone when the peak temperature
(1600oC) is reached.
176
BEHAVIOUR OF PREMIXED FLAME

AND DIFFUSION FLAME
Intermediate behavior in diffusion flame and premixed
flame is same.
Contact pattern of fuel and oxidant in diffusion flame
and premixed flame is very different.
Reaction mechanism premix flame and diffusion flame
is same.
177
SUBJECT :
IGNITION PROCESS
178
IGNITION PROCESS
Rapid reaction between fuel-oxygen
Type :
o Otoignition (in diesel engine);
Thermal Ignition
Chain Ignition
o Ignition of induction (in gasoline engine)
179
OTOIGNITION-CHAIN IGNITION
Vacum empty vessel (T0 and P0);

Entering reactant directly reach P and T0;
Evolution of temperature (figure b);
After a period of time (ignition delay time), the temperature rise drastically, fuel is
burnt, then temperature drops again because of heat loss through the walls;
It is called otoignition or spontaneous ignition (chain).
180
Influenced by chain branching process ;
RH + O2 R* + HO2 (initiation stage, slow)

RH + HO2 R* + H2O2 (propagation)
H2O2 OH + OH (chain branching)
RH + OH R* + H2O (propagation, fast)
181
During the ignition delay period, the population of radical
pool increases exponentially. However, the amount of

consumed fuel and realesed heat is too small to be
detected.
Chain branching reaction occurs during the induction

time, while the temperature remains constant.
Finally, the radical pool becomes large enough to
consume most of the fuel, and ignition occurs fast

182
DEFINITION OF
IGNITION DELAY TIME
Fuel consumption;
Formation of CO;
Formation of OH;
The increase of pressure at constant volume;
The increase of temperature in adiabatic vessel.
183
OTOIGNITION-THERMAL IGNITION
Occurs at high temperature (or
high pressure);
There is enough energy to
initiate the mixture ;
log T
R1C CR2 R1C*+ *CR2

(initiation);
Waktu
Temperature directly increases.
184
IGNITION OF INDUCTION
Caused by sources of ignition (electric leap, matches,
etc.);
Sources of ignition heats the local volume of mixture so it
has otoignition (thermal or chain);
Flame spreads and heats other mixture volume;
Combustion occurs in self-sustained.
185
OTOIGNITION OF METHANE
Green : lean; Red: stoichiometric; Blue : rich

186
OTOIGNITION OF N-PENTANE
187
OTOIGNITION OF N-HEPTANE
188
OTOIGNITION OF
SOME N-PARAFIN
189
ROLE OF OTOIGNITION
Safety aspects: otoignition occurs when a flammable substance (coal, oil)
are stored.
Controlling phenomena in diesel engines: the fuel is injected into the air
with high pressure and temperature; combustion starts spontaneously
after ignition delay time.
Controlling phenomena in gasoline engine: when the flame propagates
along the cylinder, or when the compression, the increased
pressure will heat the unburned mixture so it can ignite spontaneously (it is
called as knock).
Other applications of combustion (example : gas turbines): fuel
and air are mixed before reaching the combustion chamber so it is
dangerous if otoignition occurs; structural damage occurs.
Because of its role, the otoignition time of a mixture needs to be calculated.
o It requires chemical description, initial temperature and pressure and
other parameters of flow, such as heat loss.
190
OTOIGNITION WITHOUT HEAT LOSS

When a mixture is stagnantly homogeneous, adiabatic, constant
volume, there is no convection and diffusion; energy equation
become:
The last equation describes the evolution of temperature versus

time.
191
SENSITIVITY OF IGNITION DELAY TIME
Initial temperature (T at t = 0)
Pressure (density)
Concentration of fuel and oxygen.
192
IGNITION LIMIT
Limit of temperature-pressure that separates the fast
reaction region and slow reaction region for certain ratio

of fuel-oxygen,
It is applied for certain equivalent ratio.
193
IGNITION LIMIT OF H2-O2
At a certain P and T, mixture of H2-O2 in the vessel will burst spontaneously after
ignition delay time.
If the pressure is lowered to P1 (P1 <P), the reaction occurs slowly,
no spontaneous explosion;
If the pressure is increased to P2, (P2> P), reaction occurs slowly, no

spontaneous explosion;
This phenomenon is illustrated in the diagram of pT explosion.
194

T = 800 K, p <5 mbar not
ignite
Reactive radicals, which are
p/bar
eksplosi
formed in the gas

phase diffuses into the
Reaksi lambat
wall to join back into a stable

species.
At low P, the rate of diffusion is
eksplosi
faster than the rate of radical

production in the gas
Reaksi lambat
T/K
phase so that the ignition does

not occur.
800 K
195

If at T = 800 K, the pressure is
raised above the first ignition limit,
p/bar
eksplosi
the rate of radical diffusion to the

wall is reduced to less than the
Reaksi lambat
rate of radical production
spontaneous ignition occurs.

The first explosion limit depends
on the surface of the vessel in
eksplosi
Reaksi lambat
which reaction of chain

termination occurs.
T/K
800 K
196

If at T = 800 K, the pressure is
increased to 100 mbar, the second
explosion limit occurs because
of competition between branching a
nd chain termination reactions in the
gas phase.
p/bar
eksplosi
Reaksi lambat
At pressures below 100 mbar, the

chain branching reaction
H + O2 OH + O
OH and O react rapidly with the

fuel that produces H then reacts
according to the above reaction
produces more radical. Radicals
increases with an exponential rate
(the base of the explosion).
eksplosi
Reaksi lambat
T/K
800 K
197

The second explosion limit occurs
because the chain branching reaction
competes with trimolecular reaction.
p/bar
eksplosi
H + O2 + M HO2 + M
produces HO2 radical that has
moderate reactivity (chain
termination).
The increase of trimolecular reaction
rate with pressure is faster than
bimolecular reaction. At a certain
pressure range, the rate of timolecular
reaction is larger than its competitors
bimolecular reaction rate (slow
reaction).
Reaksi lambat
eksplosi
Reaksi lambat
T/K
800 K
198

At higher pressures, there was third
explosion limit (thermal explosion li
p/bar
eksplosi
mit) that occurs because of

competition between the heat
Reaksi lambat
generated by chemical reaction and
heat loss to the vessel wall.

If the pressure is increased further
then the heat production per
eksplosi
Reaksi lambat
increased volume so explosion

occurs at high pressure.
T/K
800 K
199
IGNITION LIMIT OF HYDROCARBONS

It is unlike the third explosion limit;
Because of the additional chemical

processes (such as the formation
of peroxides);
o Ignition occurs after the pulse
emission of short light
(multistage ignition)
o Combustion occurs at low
temperatures (cool flame).
200
IGNITION LIMIT OF HYDROCARBONS

Inhibitors of ignition in the area of cold flame (eg. CH4/O2)
o CH3 + O2 CH3O2
o CH3O2 + CH4 CH3OOH + CH3
o CH3OOH CH3O + OH
(a)
(b)
(c)
The reactions above form mechanism of chain branching

that causes ignition.
Rising of temperature could shift the equilibrium of
reaction (a). At higher temperatures CH3O2 is
decomposed; chain branching step (c) is no longer fed by
the reaction of (a).
It is called failure of chain when T rises or negative
temperature coefficient (NTC).
201
IGNITION LIMIT OF HYDROCARBON

12
Propana
10
Etana
Metana
Pressure
Tekanan
(atm)
6
4
0
200
300
400
500
600
700
800
Temperatur (C)
202
H2 COMBUSTION CHEMISTRY
203
SENSITIVITY ANALYSIS OF H2
COMBUSTION
204
OH CONCENTRATION PROGRESS
205
IGNITION DELAY TIME H2
206
FLAME VELOCITIES OF H2
207
PROFILE OF
H2,O2,AND H2O
208
COMBUSTION CHEMISTRY OF CH4
Combustion chemistry of CH4 is very complex.

Molecules of fuel, before produce CO2 and H2O, undergo
Molekul bahan bakar, sebelum menghasilkan CO2 dan H2O,
undergo a complex series of reaction steps that makes a lot of
intermediate.
209

The reaction series of CO2 formation :
Oxidation of CO
o The last series in the combustion of CH4 and other hydrocarbons.
o Occurs through reaction with OH,
Radical of OH (and H, O)
o Free radicals are important in the process of burning flame,
o In the same time, it forms the radical pool in the flame through the chain
branching reactions.
210

Chain branching reaction:
o Basis of H2 combustion,
o Important submechanism in combustion of all hydrocarbon fuels.
Destruction of the fuel and the formation and destruction of all

intermediate occurs through free radical reactions.
211

Important reactions in the flame:
o Radicals reaction is caused by radical concentration at high flame
front.
o HC fuel is attacked by active radicals of H,O, and OH.
o Alkyl radicals decompose into smaller alkyl radical and the alkene.
o Smallest alkyl radical (CH3 and C2H5) is thermally decomposed
relatively slow and compete with the recombination reaction and the
oxidation reaction with O or O2 (the rate controlling step in the flame
of alkanes and alkenes).
212

Methane in the flame is attacked by the radicals of
H, OH, and O,
213

CH3 radicals have to undergo dehydrogenated
recombination to form various species of C2 which have

high enough concentration in the fuel-rich flame.
214

Vinyl radical in the fuel-lean mixture is oxidized become
CO and CO2,
215

In the fuel-rich mixture, growth of molecule become
aliphatic, aromatic, and polyaromatic C3-C6 occurs.
216

The reaction of benzene and naphthalene (C10H8) produces
greater polyaromatic hydrocarbons(PAH).

Subsequent growth of hydrocarbon byproducts forms species
with very low vapor pressure. This species condense and
undergo dehydrogenation to form a heterogeneous core

(liquid) for the formation of soot.
Soot is an important
characteristic of the fuel-rich flame.
217
SCHEME OF SOOT
FORMATION THROUGH
PAH
218
FLOW REACTION
ANALYSIS OF CH4-AIR
STOICHIOMETRY
219
SENSITIVITY ANALYSIS OF CH4-AIR

STOICHIOMETRICALLY
220
IGNITION DELAY TIME OF CH4-O2
Green
lean, Red:
stoichiometric;
rich
Hijau:: lean;
merah:
stoikiometri;Blue
biru:: rich
221
FLAME VELOCITIES OF CH4
222
DEPENDENCE OF FLAME VELOCITY

ON MIXTURE COMPOSITION
223
DEPENDENCE OF FLAME VELOCITY

ON PRESSURE AND TEMPERATURE
224
CHEMICAL OF FLAME
ON LONG HYDROCARBON
Chemical combustion of long hydrocarbon (propane, butane,
gasoline) involves reactions that have been discussed before.

First, fuel decomposes into reactive intermediates and lowmolecular-mass fragments such as methane and ethylene. This
decomposition products determine the chemical flame and emission
from tools for combustion of long hydrocarbon fuel.
Chemical aspects of combustion is very helpful in developing
a detailed kinetic mechanisms for combustion of all kinds
hydrocarbon fuels.
225
CHEMICAL OF FLAME
ON LONG HYDROCARBON
Although the detailed mechanism of chemical kinetic for the
long hydrocarbon consists of several hundreds species which
are involved in thousands of elementary chemical reactions,
but the types of its reactions are limited.
Based on these observations, we can formulate all reactions
that occur in combustion and oxidation of long hydrocarbons
together with its rate coefficient by using simple rules.
Each rule describes a specific type of reaction.
226
CHEMICAL OF FLAME
ON LONG HYDROCARBON
Types of reactions:
o Decomposition of hydrocarbons;
o Abstraction of H atom by active radicals;
o Radical break in the position,
o Abstraction of internal H atom (isomerization),

o Addition of radical to the O2 molecule,
o Termination of O-O bond;
o Addition of radicals to the double bond.
227
CHEMICAL OF FLAME
ON LONG HYDROCARBON
Rate coefficient (C> 4) depends on:
o Radically legible abstraction of H atom from alkanes,

alkenes, aldehydes, ketones or cyclicether;
o Type of abstracted H atom (primary, secondary,
tertiary);
o Amount of equivalent H atoms ;
o Size of the intermediate ring structure (5, 6, 7 or 8
members).
228
CHEMICAL OF FLAME ON LONG

HYDROCARBON
229
CHEMICAL OF FLAME
ON LONG HYDROCARBON
Reaction group :
o Reaction at high temperature;

o Reactions at low temperatures;
230
REACTION AT HIGH TEMPERATURE

Molecular decomposition of alkanes
o C-H> C-C,
o Relative strength of CH and CC: primary> secondary>
tertiary.
231

Abstraction of H atom from alkanes :
o The rate coefficient depends on the

legible abstraction radical,
type of abstracted H atom,
amount of equivalent H atoms.
o Tertiary C-H < seondary C-H <primary C-H;
o Abstraction of H atom from fuel through the attack of oxygen molecules
which act as initiation reaction. At low temperature, the reaction is rather
slow because of high activation energy (> 167 kJ / mol). However, the
reaction is still running as the R radical starts the chain.
232

Decomposition of alkyl radical
o Termination of bond at position to the radical site.
o It is important only at high temperature (T > 900 K) due to high

activation energy.
o At low temperature, the important reaction is the addition of alkyl
radical to oxygen molecule (zero activation energy).
233

Isomerization of alkyl radical
o Alkyl radical transfers H atom from one position to radical

position to generate new radical location.
o Coefficient of rate depends on :

Energy barrier of chain strain, which is described in amount
of atoms in chain structure at transition state (including H),
Type of abstracted H atom,

Amount of equivalent H atom.
234

Oxidation of alkyl radical to form alkene
o Irreversible reaction,
o Energy barrier is not large,
o It forms alkene conjugate.

o Rate coefficient depends on
Type of abstracted H atom;

235

Decomposition of alkene
o Occurs through various path of reaction;

o The most important is reaction that forms allyl radical
(low activation energy ~ 290 kJ/mole),
236

Abstraction of allyl H atom
vinyl
allyl
alkenyl
237

Abstraction of allyl H atom
o It forms resonance-stabilized radicals which further break

in a position to produce, for example, 1-3-butadiene.
o Rate coefficient depends on :

Type of allyl H atom;
238

Abstraction of vinyl H atom
o Two types of vinyl H :
Secondary
Tertiary
o The Reaction is more difficult than allyl H atom.

o Rate coefficient depends on :
Type of vinyl H atom
239

Abstraction of alkenyl H atom
o It has role in the reaction of
long chain alkene that produce

products which is observed in
experiments such as dialkene
(eg. C5H8)
o Rate coefficient :
It is same as abstraction of H atom from alkane;
It depends on type of H atom;

It depends on amount of equivalent H atom.
240

Addition of H to the double bond
o Very exothermic;
o Inverse of alkyl radical decomposition at position.
241

Addition of CH3 to the double bond
o Inverse of alkyl radicals decomposition at position.
242

Addition of O to the double bond
o It forms ketyl radical dan short alkyl radical.
243

Addition of OH to the double bond
o It forms aldehyde or ketone.
244

Addition of HO2 to the double bond
o It forms hydroperoxy alkyl radical, ROOH, which then

decomposes to form cyclic ether, aldehyde or ketone.
245

Reaction of retroena
o Reaction of 1,5 hydrogen shift which is followed by

dissociation;
o It forms two short chain alkene.
o For example, reaction of 1-heptane produces 1-
butene and propene.
246

Isomerization of alkenyl radical
o It produces resonance-stabilized radicals.

o The fastest isomerization : involving transition state
which contains five or six atoms.
o At 1100 K, isomerization of alkenyl radical produces
allyl radical 5-10 times faster than termination of .
247

Decomposition of ally radical
o Bond termination at position from radical position;

o It produces dialkene (eg 1,3-butadiene and 1,3pentadiene).
248

Decomposition of vinyl radical
o Bond termination at position from radical position to

produce dialkene;
o It produces alkyne
249

Decomposition of alkenyl radical
o This is an important reaction if isomerization of alkenyl

radical may not occur because the alkenes is too short.
o It occurs through the termination of that produces :
Dialkene and alkyl radical;
Alkene and short alkenyl radical.
250
REACTION AT
HIGH TEMPERATURE
251
REACTION AT LOW TEMPERATURE

Addition of alkyl on O2
o At T <, reacton of alkyl termination at position and
isomerization is slow because Ea (113-167 kJ/mole).
o Most important alkyl reaction at T< is the addition of alkyl on O2.
Exothermic, reversible and Ea <<< .

If T , reaction to the left; RO2 looses and its concentration
is very low.
252

Isomerization of alkylperoxy
o Through the transfer of H (1,4-, 1,5-,1,6- dan 1,7-)
o Coefficient of reaction rate depends on

Energy barrier of chain strain (5-, 6-, 7- and 8- members)
Type of abstracted H (primary, secondary, tertiary),
Amount of equivalent H.
253

Abstraction of H from alkane by alkylperoxy
o Coefficient of reaction rate depends on :

Type of abstracted H,
Amount of equivalent H.
254

Reaction of alkylperoxy with HO2
Reaction of alkylperoxy with H2O2
255

Termination of O-O hydroperoxide bond
Decomposition of alkoxy
256

Addition of alkyl hydroperoxy on O2
Decomposition of alkyl hydroperoxy
257

Termination of O-O pada alkyl hydroperoxy
Oxidation of alkyl hydroperoxy
258

Formation of cyclic ether from alkyl hidroperoxide
o Consists of :
Termination of O-O,
Formation of cyclic ether.
o Ea depends on the size of the cyclic ring.

o Cyclic ether : oksirana, oksetana, tetrahidrofurana,
tetrahidropirana.
259

Isomerization of alkyl peroxide hidroperoxide.
260

Termination of O-O at alkyl dihidroperoxide
Decomposition of ketohydroperoxide
261

Decomposition of O=RO
Abstraction of H from cyclic ether
262

Abstraction of H from aldehyde or ketone
Decomposition of Ketyl
263
264
185 species,
1186 elementary reactions
N-PENTANE
265
486 species,
2008 elementary reactions.
N-HEPTANE
266
486 species,
N-HEPTANE
267
486 species,
N-HEPTANE
268
486 species,
N-HEPTANE
269
486 species,
N-HEPTANE
270
N-HEPTANE
486 species,
271
N-HEPTANE
486 species,
272
N-HEPTANE
486 species,
273
N-HEPTANE
486 species,
274
ISO-OCTANE
950 species,
275
ISO-OCTANE
950 species,
276
ISO-OCTANE
950 species,
277
ISO-OCTANE
950 species,
278
ISO-OCTANE
950 species,
279
ISO-OCTANE
950 species,
280
ISO-OCTANE
950 species,
281
1253 species,
N-DECANE
282
1253 species,
N-DECANE
283
1253 species,
N-DECANE
284
1253 species,
N-DECANE
285
1253 species,
N-DECANE
286
1253 species,
N-DECANE
287
1253 species,
N-DECANE
288
SENSITIVITY
ANALYSIS
N-heptane
289
SENSITIVITY
ANALYSIS
N-heptane
290
SENSITIVITY
ANALYSIS
N-heptane
291
SENSITIVITY
ANALYSIS
N-heptane
292
SENSITIVITY
ANALYSIS
N-heptane
293
N-PARAFIN
294
PATHWAYS OF CO REACTION
295
296
297
PATHWAYS OF CO2 REACTION
298
299

At 1250 K
300
PATHWAYS OF CH2O REACTION
301
PATHWAYS OF CH2O REACTION
302
NITROGEN FORMATION
In the flame, nitrogen and oxygen molecules interact each
other according to the mechanism of Zeldovich or thermal
NO,
The second reaction will be important if it is above 1500oC.

Diffusion flame is very vulnerable to produce high
concentration of NO at high flame temperature.
303
NITROGEN FORMATION
Formation of NO also occurs through the mechanism of NO,
and from source of nitrogen in the fuel.
In the mechanism of NO, radical reaction of CH with N2

produces NO.
304
NITROGEN FORMATION
Mechanism of this reacton also plays a role in the

process of thermal deNOx to remove NO from
combustion products using NH3.
305

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SUBJECT :

DEPARTEMEN TEKNIK KIMIA UNIVERSITAS INDONESIA

Chemical Kinetics of Combustion

DEPARTEMEN TEKNIK KIMIA UNIVERSITAS INDONESIA

Oleh : Dr.Ing Donni Adinata, ST., M. Eng. Sc

Reaction of fuel with oxidant

Supersonic combustion or detonation

Practical applications involving other disciplines :

Properties of gases and its mixture

However, thermodynamics alone is unable to inform that the system will

Therefore, we need rate of chemical reaction in combustion

Fuel and oxidant are part of the same molecule

HISTORY OF FOSSIL FUEL

Early 1900s: coal,

generation and transportation)

TOTAL PRIMARY ENERGY SUPPLY

Other : geothermal, solar, wind, etc.

OUTLOOK OF TOTAL PRIMARY

Type and composition of fuel,

World CO2 emissions by fuel source

World CO2 Emissions by Region

NO2: 0,053 ppm (100 g/m3) > a year;

butane, pentane, aldehydes, ketones, solvents.

fuel pump station; cleaning clothes; printing; paint.

chronic exposure causes cancer.

generating system such as gas turbine and furnace.

Design of combustion process

Fuel + Oxidizer + Diluents Combustion Products

Contain multiple components such as methane, hydrogen,

they are more easily staged.

o The flames much more luminous

79% nitrogen diluent

AIR ENRICHED WITH O2 BURNER

INTERNAL COMBUSTION ENGINE

This exothermic reaction creates gases at high

INTERNAL COMBUSTION ENGINE

o Water, steam, and gases like nitrogen or carbon dioxide.

The combustion products are drawn back into the

Reduced NOx emissions.

Control parameters in combustion process:

Design of the combustion process

COMBUSTION IN GASOLINE ENGINE

o Premix flame is called stoichiometric if the reactant

o Standard air composition:

o (A / F) Stoic = [5 (32 +3.762 * 28)] / (44) = 15.6

EXAMPLE OF COMBUSTION SYSTEM

Mass ratio of the stoichiometric air-methane, AFRm,:

- Lack of fuel than the stoichiometric ratio;

Rich fuel mixture:

- Intermediate in the product.

< 1 poor fuel;

from the atom balance sheet of C, H, and O :

calculated using the equilibrium (there is CO and H2 , so

and 15.9% mass of H has a molecular weight of 114.15.

Molecular Weight = 114.15 = 12.011a + 1.008b

ENERGY BALANCE AND ENTHALPY

ENERGY BALANCE AND ENTHALPY

Heat reaction at constant volume

ENERGY BALANCE AND ENTHALPY

Heat reaction at constant

ENERGY BALANCE AND ENTHALPY

Relation of (H)P,T and (U)V,T :

ENERGY BALANCE AND ENTHALPY

ENERGY BALANCE AND ENTHALPY