ADAMA SCIENCE AND TECHNOLOGY

UNIVERSITY

SCHOOL OF MECHANICAL, CHEMICAL & MATERIALS ENGINEERING

THERMAL ENGINEERING PROGRAM
Combustion (ThE 6206)
Kinetics of Combustion

Welcome to our presentation

 Introduction
 Fuel is a material that carries energy in chemical form.
 When the fuel is reacted (e.g. through combustion), most of the energy is released as heat
 The energy is released via chemical reactions. Each fuel undergoes different reactions,
with different rates.
 The r/ship between thermodynamics and kinetics
 Thermodynamics –does a reaction takes place???
 Kinetics-how fast does a reaction proceed???

 The rate of reaction can be: instantly , evolving at a sizeable pace , at a negligible rate .
 Law of Mass Action
The law of mass action states that the combining power of two reactants A and B depends
up on their nature as well as their active concentration.
Also this law suggests that, the ratio of the reactant concentration and the product
concentration is constant at a state of chemical equilibrium.
 …. cont
Consider the following simple reversible reaction where A & B are the reactants whereas
C & D are the products
A  B    C  D

This relation can be equated as follows

Kc 
 C   D
 A  B 
The law of mass action dictates that the equilibrium constant, at a given constant
temperature, is equal to the product of the concentration of products raised to the
respective stoichiometric coefficients divided by the product of the reactant
concentrations, each raised to the corresponding stoichiometric coefficient.
 ……cont
For a balanced reaction of the type,

aA  bB    cC  dD
For the forward reaction, this is given by

 C   D
c d

KC 
 A  B 
a b

The equilibrium constant for the reverse reaction is

 A  B 
a b

K 'c  1/ K c 
 C   D
c d
 Reaction Rates

 Not all chemical reaction proceed at equal speed. For example

Rippening of fruits-takes few days

 weathering of stone-it takes more than decade

 Breakdown of plastic in the environment-it takes more than hundred years. However

Combustion of gasoline or the explosion of gun powder occurs in a few second.

Reaction rate:- is the speed at which a chemical reaction takes place,

 ….. cont
Reaction rates are usually expressed as the concentration of reactant consumed or the
concentration of product formed per unit time.
 For a simple reaction,

 The rate of reaction is expressed in terms of a reactant concentration as

A 
B

 In terms of product concentration, the rate of reaction is given by

  A  A f   A i
r 
t t

  B  B f   B i
r 
t t
 Simple and complex reactions

simple reaction complex reactions.

 takes place in a single step  Occurs in multi (or) many steps.

 Overall order values are small. order  Overall order values are large and greater
values lie between 0,1,2 and 3. than 3.0.

 No side reactions  Many side reactions are present

 Products are formed directly from the  In some complex reactions products are not
reactants formed in steps directly involving the
reactants
 Reaction order and Molecularity

Reaction order
 A reaction has an individual order “with respect to” or “in” each reactant. For the simple
reaction A → products:
 If the rate doubles when [A] doubles, the rate depends on [A]1 and the reaction is first
order with respect to A.
 If the rate quadruples when [A] doubles, the rate depends on [A]2and the reaction is second
order with respect to [A].
 If the rate does not change when [A] doubles, the rate does not depend on [A], and the
reaction is zero order with respect to A.
 Determining Reaction Orders

For the general reaction A + 2B → C + D, the rate law will have the form

Rate = k[A]m[B]n. To determine the values of m and n, we run a series of experiments in which one reactant
concentration changes while the other is kept constant, and we measure the effect on the initial rate in each case.

Molecularity

The molecularity of a reaction is the number of molecules in an elementary reaction step at the microscopic
(molecular) level

 Unimolecular: one molecule in the elementary step,

 Bimolecular: two molecules in the elementary step, and

Termolecular: three molecules in the elementary step.

(It is uncommon to see ter molecular processes…statistically improbable for an effective collision to occur.)

There are only three possible cases for the molecularity (one example for each case):
Con…….
monomolecular (= unimolecular) reactions:
CH3NC → CH3CN (2.19)
bimolecular reactions:
O+H2 → OH + H (2.20)
termolecular reactions:
H+O2+M → HO2+M (2.21)
Note: Events where more than three species come together in the right configuration and react
are extremely unlikely and do not play a role.
 Arrhenius Law
Arrhenius discovered that most reaction-rate data obeyed an equation based on three
factors:!
(1) The number of collisions per unit time!
(2) The fraction of collisions that occur with the correct orientation!
(3) The fraction of the colliding molecules that have energy greater than or equal to Ea!
 Activation Energy
Arrhenius: Molecules must possess a minimum amount of energy to react. Why?
(1) In order to form products, bonds must be broken in the reactants.
(2) Bond breakage requires energy.
(3) Molecules moving too slowly, with too little kinetic energy, don’t react when they collide.
 The Activation energy, Ea, is the minimum energy required to initiate a chemical reaction
 Ea is specific to a particular reaction
. Determining the Activation Energy
One can determine the activation energy of a reaction by measuring the rate constant at two
temperatures:
Writing the Arrhenius equation for each temperature:
Con……..

…….
 Chain Reactions
In most instances, two reacting molecules do not react directly,
rather one molecule dissociates first to form radicals.
Radicals are produced by dissociation of a reactant in the
initiation process.
Con…

  In the following, we illustrate some of the features of chain reactions by exploring a
hypothetical chain mechanism,
+ →2AB
 + → A + A + (Chain initiation)
+ M → B + B + M (Chain initiation)
B+ → AB + A (Chain carrying/ propagating)
A+ → AB + B (Chain carrying/propagating)
A+B+M → AB + M (Chain terminating)
 Con…

  Elementary reaction can be classified as

Chain initiating
Chain branching
Chain carrying
Chain terminating
Chain propagating
 Chain initiating

+MA+A+M
Con…

  Chain-propagating/Carrying
A + AB + B
B + AB + A
Chain terminating
A+B+M AB + M
Chain branching
 Steady-State Approximation(SSA)
 In many chemical systems of interest to combustion, highly reactive intermediate species, e.g., radicals or
carriers are formed.
 Analyses of such systems can sometimes be simplified by applying the so-called steady-state
approximation to these reactive intermediates or radicals.
 Thus on the basis of SSA, we can write the rate law for the thermal decomposition of acetaldehyde as
follows:
CH3CHO (g) → CH4 (g) + CO (g) d[CH4]/dt = k[CH3CHO] 3/2
• The mechanism for this reaction known as Rice-Herzfeld mechanism is as follows:
 ……..continued
 The rate equation can be derived on the basis of steady-state approximation. The rate of change
of intermediates may be set equal to zero.
 The Partial Equilibrium Assumption(PEA)

Most combustion systems entail oxidation mechanisms with numerous individual

reaction steps. Under certain circumstances a group of reactions will proceed rapidly
and reach a quasi-equilibrium state. Concurrently, one or more reactions may
proceed slowly.
If the rate or rate constant of this slow reaction is to be determined and if the reaction
contains a species difficult to measure, it is possible through a partial equilibrium
assumption to express the unknown concentrations in terms of other measurable
quantities.
Partial equilibrium assumption says that the slower reaction in the mechanism is the
rate determining reaction
 ……..continued
Example: determining the rate of formation of CO2 using PEA
A specific example can illustrate the use of the partial equilibrium assumption. Consider, for instance, a
complex reacting hydrocarbon in an oxidizing medium. By the measurement of the CO and CO2
concentrations, one wants to obtain an estimate of the rate constant of the CO 2 reaction.
A slow reaction

Reactions rapidly reaching equilibrium:

 Chain-Branching Reactions: Explosions
 Compounds, which are highly stable at normal temperatures, usually emulate the noble gases (helium,
argon, etc.) in the configuration of their electrons. That is, these highly inert gases have outer electron shells
empirically filled by 2 and 8 electrons in the case of He and Ne, respectively.
 An example is a hydrogen molecule, H2 which looks like He in the sense that each hydrogen atom shares its
electron with the other atom so that there are two electrons in the configuration. Similarly, a water
molecule, H2O, looks like Ne where there are total of 8 electrons being shared, 6 from the outer shell in
oxygen and 2 from each of the hydrogen atoms.
 ……..continued
 Radicals

 In chain branching reactions there is a net production of radicals. Chain branching reactions lead to rapid
production of radicals, which causes the overall reaction to proceed extremely fast an explosively.
 The reaction comes to completion through chain termination reactions, where the radicals recombine to form
final products.
 Radicals usually have positive heats of formation, which means that energy is required for their formation from
the standard state elements. They soak up collision energy in their formation and wish to give up this energy in
attacking other species in the path toward reaction completion.
 ……..continued
 Radicals are extremely important in the kinetic schemes relevant to atmospheric pollution. Examples of
reactions producing nitric oxide (NO) as a harmful air pollutant, which is called the thermal mechanism of
NO for formation, are

 Some chemical reactions develop in time smoothly while others ‘‘explosively’’ and are usually accompanied
by some unexpected phenomena such as a flash, acoustic effects, etc. The important features of explosions
are that the rate of the reaction varies extremely rapidly with temperature. Thus, for example, at room
temperature and atmospheric pressure hydrogen and oxygen hardly react over a period of many years.
 However, if the pressure or temperature are raised sufficiently high, or being kept at temperature just slightly
higher 450 C and the pressure in the vessel at a few torr, a violent exothermic reaction will be initiated with
the product, water being formed. Such a fast, exothermic reaction is called an explosion.
 ……..continued
Unlike an ordinary reaction, an explosive reaction is characterized by the
existence of a temperature at which the reaction rate changes very rapidly,
almost discontinuously.
This temperature is called the ignition (or self-ignition) temperature. An
equally rapid change in the reaction rate can be obtained by changing the
pressure at a given temperature.
In observing an explosive reaction, the first impression is that for
temperatures and pressures below critical nothing is happening in the
mixture, but when the critical parameters are reached everything reacts all at
once. This is the reason for calling the reaction explosive.
 Explosion
 An explosion is a rapid expansion in volume associated with an extremely
vigorous outward release of energy

Explosio
n

Thermal Chain
 Flammability and explosion limits
 FL vs EL
 LFL &UFL

Gas LFL UFL Gas LFL UFL

Acetone 2.6 13 Heptane 1.1 6.7

Ammonia 15 28 Hexane 1.2 7.4

Benzene 1.3 7.9 Hydrogen 4 75

CO 12.5 74 Methane 5 15

Dibornate 0.8 88 Propane 2.1 9.5

Hydrogen-oxygen reaction: Explosion limits
 CO oxidation reaction: Explosion limits

 
Hydrocarbons oxidation reaction: Explosion limits
 Certain experimental combustion characteristics

Hydrocarbons exhibit induction intervals

Their rate of reaction is inhibited strongly by adding surface
They form aldehyde groups
They exhibit cool flames
They exhibit negative temperature coefficients
They exhibit two-stage ignition
 y o u
h a n k
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