Combustion and Emissions – ME 537

Chapter 2
Favre- andChemical
Reynolds-Averaged
Kinetics Velocity
Measurements: Interpreting
and LDA and
PIV in Combustion
The Chemistry of Combustion

Dr M. Mustafa Kamal
Assistant Professor
 Objectives
• Introduce chemical kinetics concept

• Simple model for fuel consumption rate

• Use NO formation as an example
• Qualitative description for hydrocarbon combustion

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 Chemical Kinetics

Motion or Velocity, rate or rate

Kinetics
movement of change

• Chemical kinetics, a specialized field of physical chemistry, deals with the study of the
elementary reaction and their rates.
o Detailed chemical pathways leading from reactants to products, and to measure or
calculate their associated rates.
o Construct computer models that simulate reacting systems.

• In many combustion processes, chemical reaction rates control the rate of combustion, and, in
essentially all combustion process, chemical rates determine pollutant formation and
destruction.

• Ignition and flame extinction are intimately related to chemical processes.

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 Chemical kinetics
Global and Elementary Reactions – l
How do we go from reactants to products?
• Chemical reactions involves re-distribution of how atoms are bonded together in the
molecule.

• Chemical reactions occur as a result of “effective” molecular collision between two species.

• Chemical bonds must be broken during the impact (i.e. molecules must have sufficient K.E.)
and other bonds must be formed.

• Consider the chemical equation for the oxidation of methane:

𝐶𝐻4 + 2𝑂2 ⟶ 𝐶𝑂2 + 2𝐻2 𝑂 (Global Rxn.)
o However this equation does not represent the chemical kinetics of methane oxidation.
o Collisionally and energetically a three body collision of one molecule of 𝐶𝐻4 and two of
𝑂2 to yield 𝐶𝑂2 and 𝐻2 𝑂 is most improbable.

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Chemical kinetics
Global and Elementary Reactions – ll
The overall combustion process follows hundreds or thousands of elementary reactions and
many species and radicals appear.
Radicals or free radicals are
𝐶𝐻4 + 2𝑂2 𝐶𝑂2 + 2𝐻2 𝑂 (Global Rxn.) highly reactive intermediates
(unstable molecules or atoms)
like 𝑂, 𝐻, 𝑂𝐻, or 𝐶𝐻3

The series of elementary reactions

that describes the overall process is
called a reaction mechanism or
detailed chemical mechanism

The concept of global reaction helps us visualize the overall process and
stoichiometry. But it is only when we identify the elementary reactions
that we can talk in detail about what really happens inside the flame.

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Chemical kinetics
Reaction mechanism or detailed chemical mechanism – l
The mechanism of a chemical reaction is the sequence of actual events that take place as
reactants are converted into products.
• Each of these events constitutes an elementary step (reaction) that can be represented as
o a coming-together of discrete particles ("collision") or
o as the breaking-up of a molecule ("dissociation") into simpler units.
• The molecular entity that emerges from each step may be a final product of the reaction, or it
might be an intermediate. Intermediate: A species that is created in one elementary
step and destroyed in a subsequent step, and therefore
does not appear in the net reaction equation.

Example: Decomposition of 𝑁𝑂2 : 𝟐 𝑵𝑶𝟐 𝒈 ⟶ 𝟐 𝑵𝑶 𝒈 + 𝑶𝟐 (𝒈)

The mechanism of this reaction involve the following two elementary steps: Reaction mechanisms
may involve only a few
1) 2 𝑁𝑂2 ⟶ 𝑁𝑂3 + 𝑁𝑂 steps (i.e., elementary
2) 𝑁𝑂3 ⟶ 𝑁𝑂 + 𝑂2 reactions) or as many
Note that the intermediate species 𝑁𝑂3 has only a transient existence and as several hundred.
does not appear in the net equation.

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Chemical kinetics
Reaction mechanism or detailed chemical mechanism – ll
Example: Detailed chemical mechanism involves 100s of elementary reaction, 10s of species.
Even for a simplest hydrocarbon, 𝐶𝐻4

Ref: Combust. Flame, 160, p.56-75, 2013, Nikolaou, Chen, Swaminathan 7

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 Chemical kinetics
Law of Mass Action
This concept relates how quickly the reaction proceeds as a function of how much reactant is available. It is
valid only for elementary reactions. Consider a generic elementary reaction:
𝑎, 𝑏 → stoich. coefficients
𝑎1 𝑅1 + 𝑎2 𝑅2 + 𝑎3 𝑅3 + ⋯ + 𝑎𝑀 𝑀 𝑏1 𝑃1 + 𝑏2 𝑃2 + 𝑏3 𝑃3 + ⋯ + 𝑏𝑀 𝑀 ∵
𝑅, 𝑃 → reactants, products
The rates of reactants consumption and products formation are given by:
𝑑 𝑅1 𝑑 𝑅2 𝑑 𝑅3 𝑑 𝑃1 𝑑 𝑃2 𝑑 𝑃3
= −𝑎1 𝜔 , = −𝑎2 𝜔 , = −𝑎3 𝜔 , … . = 𝑏1 𝜔 , = 𝑏2 𝜔 , = 𝑏3 𝜔 , … .
𝑑𝑡 𝑑𝑡 𝑑𝑡 𝑑𝑡 𝑑𝑡 𝑑𝑡
𝑑𝑀 If 𝑏𝑀 = 𝑎𝑀 , the 𝑀 is called the third body: it may not be altered, but its presence is crucial for the
= 𝑏𝑀 𝜔 − 𝑎𝑀 𝜔 reaction, as it provides energy to, or takes energy away from, the collision between reactants.
𝑑𝑡
𝑎1 𝑎2 𝑎3 𝑘 → reaction rate constant
with 𝜔 being the reaction rate: 𝜔 = 𝑘 𝑅1 𝑅2 𝑅3 …. ∵
𝑅1 → concentration kmolΤm3 of 𝑅1
The above equation is the Law of Mass Action and states that “the chemical reaction rate is proportional to
the reactants concentrations, raised to their respective stoichiometric coefficients”.
NOTE: The amount of products does not affect 𝜔. The 𝑘 is
not a function of the reactants concentration and it is
specific to the elementary reaction.
The greater the concentrations of the reactants, then the
greater will be the number of collisions and hence the
rate of interaction between them.
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 Chemical kinetics
Rate Law
𝑎1 𝑅1 + 𝑎2 𝑅2 + 𝑎3 𝑅3 + ⋯ + 𝑎𝑀 𝑀
𝑎, 𝑏 → stoich. coefficients
𝑏1 𝑃1 + 𝑏2 𝑃2 + 𝑏3 𝑃3 + ⋯ + 𝑏𝑀 𝑀 ∵
𝑅, 𝑃 → reactants, products

Experimentally, it has been found out that the reaction rate, 𝜔 may not necessarily depend on the
stoichiometric coefficients but only on some partial amount of the total concentration of reactants,
say 𝑛 and 𝑚. i.e.,

𝜔 = 𝑘 𝑅1 𝑛 𝑅2 𝑚…. where 𝑛 and 𝑚 may or may not be equal to 𝑎1 and 𝑎2 .

• Thus, Rate Law is the expression which expresses the 𝜔 in terms of the molar concentration of the
reactants, with each term raised to a power which may or may not be equal to the stoichiometric
coefficient of the reactant in the balanced chemical equation.

• Unlike the Law of Mass Action, the Rate Law cannot be determined by just looking at the given
chemical equation but, instead, can be determined only experimentally.

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 Chemical kinetics
Rate Law vs Law of Mass Action
𝑛
Rate Law: Rate of reaction ∝ Reactants concentration

𝑎
Law of Mass Action: Rate of reaction ∝ Reactants concentration

• 𝑛 represents the effective collision, whereas 𝑎 represents the total collisions.

• Effective collisions is the number of collisions that actually convert reactants to products.

• The total collision is more than the effective collision.; and we know that all the collisions are
not effective for the reaction.

• The sum of effective collision represents the order of reaction (Explained later!)

• Order of a chemical reaction can not be determined from the Law of Mass Action.

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