ME4227

Internal Combustion Engines

Part II
Lecture 1: Fundamental of combustion theory

Zhang Huangwei, Dept. Mechanical Engineering

(huangwei.zhang@nus.edu.sg)

No dissemination without permission 1

 Syllabus
o There are six lectures in total for the 2nd part of this module:
– Lecture 1: Fundamental of combustion theory
– Lecture 2: Fuel and flows in internal combustion engines
– Lecture 3: Combustion in spark-ignition engines
– Lecture 4: Combustion in compression-ignition engines
– Lecture 5: Pollutant formation and control
– Lecture 6: Wrap-up and revision of Part 2

o Target student: undergraduate students

o Prerequisite module: Other modules related to fluid mechanics,
thermodynamics and heat transfer

o Lecturer: Zhang Huangwei, Email: huangwei.zhang@nus.edu.sg,

Office: EA-05-22, Tel.: 6516 2557 2
CA

❑ Example Paper 1: 4 Questions (Choose to 3 of 4)

❑ Example Paper 2: 4 Questions (Choose to 3 of 4)

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Overall objective
Aims:
❑ To introduce some fundamental physical aspects of combustion
❑ To describe the characteristics of traditional and alternative fuels for IC
engines
❑ To introduce the flame dynamics, performance and pollutant control from
IC engines
Objectives:
On completion, you are supposed to have:
❑ good understanding of basic concepts to analyse IC combustion problems
❑ ability to undertake engineering calculations for IC combustion problems
❑ good foundation for pursuing further research on combustion and IC
engines
❑ A detailed knowledge of a particularly chosen aspect of engines and fuel
combustion in engineering

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 Reference textbooks

Internal Combustion Engine Principles of Combustion

Fundamentals K. K. Kuo
Combustion Physics An Introduction to
J H Heywood Penn State University
C. K. Law Combustion
MIT Introduction to internal Princeton University S R Turn
Combustion Engines Penn State University
Richard Stone
University of Oxford
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Lecture 1: Outline

• Basic concepts of combustion

• Law of mass action and Arrhenius law
• Classification of combustion phenomena
• Significant flame or combustion parameters

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What is combustion?

o Chemically reacting flows with highly exothermic, temperature-

sensitive reactions

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Combustion around us
Transportation
Energy
Fire

Defence

Life

Pollution

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Combustion as a science
o Combustion is a multi-disciplinary science (NOT a brand new subject)

Fluid Chemical
mechanics kinetics

Thermo- Transport
dynamics Phenomenon

o Combustion is as a multi-scale science

• Flow / turbulent mixing

• Inter- or intra-molecular interactions
• Nanoparticle formation
• ……
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Stoichiometry
o Stoichiometrically balanced reaction for methane/oxygen reaction:

The ratio of the mass of fuel

to the mass of oxidizer

Equivalence ratio

The ratio of the mass of fuel to the

mass of oxidizer under
<1: fuel-lean mixture stoichiometric condition

𝜙 = =1: stoichiometric mixture

<1: fuel-rich mixture

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Stoichiometry

For a hydrocarbon fuel given by CxHy, the stoichiometric relation can be

written as:

[example] A small, low emission engines operates at a full load at an

equivalence ratio of 0.286 with an air flowrate of 15.9 kg/s. The
equivalence composition of the fuel is C1.16H4.32. Determine the fuel mass
flow rate and the operating air-fuel ratio for the engine.

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Multiple reactions
H2-CO reaction system
Generalized multiple reactions:

o Forward and backward reactions

o What is K & N?
o Stoichiometric coefficients?

Many reactions! Many species!

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Element conservation
o Element conservation requires that atoms are neither destroyed or
generated in chemical reactions.

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Energy conservation
o For a generalized chemical reaction,

o The heat of reaction can be calculated from:

Stoichiometric coefficients Heat of formation

If the heat of formation of the products is less than that of the reactants, then 𝑞ത𝑝 𝑇 𝑜 < 0.
The reaction is exothermic (combustion releases heat into the system).
Otherwise, 𝑞ത𝑝 𝑇 𝑜 > 0. The reaction is endothermic (energy is taken from the system to
sustain the reaction). 14
Absolute enthalpy &
formation enthalpy
• Absolute enthalpy is the sum of an enthalpy that takes into account
the energy associate with chemical bonds, the formation enthalpy,
and an enthalpy associated only with the temperature, the sensible
enthalpy change:

• Selection of standard reference state pressure and temperature

• Formation enthalpies are zero for the elements in their naturally
occurring state at the reference state temperature and pressure 15
Formation enthalpy
o For a given substance, ℎത 𝑖𝑜 is positive if heat is absorbed by the
system and negative if heat is release.

The negative and positive signs indicate that the formation reactions
of CO and HI are exothermic and endothermic, respectively.

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Enthalpy of combustion

• Knowing how to express the enthalpy for mixtures of reactants and

mixtures of products allows us to define the enthalpy of reaction
when dealing specifically with combustion reactions, the enthalpy of
combustion.

The amount of heat removed can be

related to the reactant and product
absolute enthalpies by:

Steady flow
reactor Enthalpy of combustion
(Enthalpy of reaction)

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Heat of combustion

• Heat of combustion is numerically equal to the enthalpy of reaction

(or enthalpy of combustion), but with opposite sign:
∆ℎ𝑐 = −∆ℎ𝑅

• Higher heating value (HHV) is the heat of combustion calculated

assuming that all of the water in the products has condensed to liquid.
This scenarios liberate most amount of energy.
• Lower heating value (LHV) corresponds to the case where none of the
water is assumed to condense.

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HHV and LHV (from handbook)

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Adiabatic flame temperature

• We can define two adiabatic flame temperatures from: (1) constant-

pressure combustion and (2) for constant-volume combustion.
• If a fuel-air mixture burns adiabatically at constant pressure, the
absolute enthalpy of the reactants at the initial state equals the
absolute enthalpy of the products at the final state:

𝑇𝑎𝑑 : adiabatic flame temperature

[Example] Estimate the constant-pressure adiabatic flame temperature for the
combustion of a stoichiometric methane-air mixture. The pressure is 1atm and the
initial reactant temperature is 298 K.
Assume: (1) complete reaction (the product species is N2, O2 and N2);
(2) The product mixture enthalpy is estimated using constant specific heats
evaluated at 1200 K (≈0.5(Ti+Tad), where Tad is assumed to be 2100 K) 20
Adiabatic flame temperature
• If a given uniform mixture with an initial temperature and
composition is made to approach chemical equilibrium through an
adiabatic, isobaric process at pressure 𝑝, then the final temperature
is the adiabatic flame temperature, 𝑇𝑎𝑑 .
• Different fuels and conditions (such as equivalence ratio) would lead
to different adiabatic flame temperatures.

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Adiabatic flame temperature

• Fuel equivalence ratio has the strongest effects on adiabatic flame

temperature.
• The parameter that has the next strongest influence on Tad is the C/H
ratio of the fuel molecule, with Tad increasing with increasing C/H
ratio.

1. species with large C/H ratios often contain more double

and triple C-C bonds, which can hold more potential
energy than the single bond.
2. Enthalpy of combustion:
3. the oxidation of one mole of ethylene requires a smaller
amount of oxygen (3 versus 3.5 moles), and hence there
is less nitrogen in the combustion product that needs to
be heated up.
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The law of mass action
For a single, forward chemical reaction:

reactant product
The change rate in the molar concentration 𝑐𝑖 of species 𝑖 reads:

𝜔
ෝ𝑖 is related to of species j (another species different from species 𝑖)
through:

𝜔 is the reaction rate of the foregoing forward reaction.

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The law of mass action

The phenomenological law of mass action states that 𝜔 is

proportional to the product of the concentrations of the reactants

Specific reaction rate Product of the molar

constant concentration

For elementary reaction H + HO2 → OH + OH

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Reversible reactions
o For a backward chemical reaction:

The net reaction rate in the presence of forward and backward

reactions

An equilibrium constant 𝐾𝑐 can be defined as:

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The Arrhenius Law

• The specific reaction rate constant gives the functional dependence

of the reaction rate on temperature.
• For an elementary reaction, the Arrhenius Law states that

𝐸𝑎 : activation energy, unit of cal/mole or joule/mole.

• If 𝐸𝑎 is a constant with respect to temperature, one can integrate

the foregoing equations and has:

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The Arrhenius Law
Gas constant

Frequency factor Activation energy

or preexponential factor

• If A is a function of temperature, then the specific reaction rate

constant can be written as

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The Arrhenius Law
• The kinetic parameters are usually determined by the numerical
fitting of the experimental data.
• Specific temperature range should be given for the kinetic
parameters.
• The Arrhenius law is for individual elementary reactions.
• For one-step global reaction or multi-step semiglobal reaction
scheme, the description of the chemical kinetics expression is more
complicated.

Nobel Prize for Chemistry in 1903

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Activation energy

• The sensitivity of a chemical reaction to temperature variation

depends critically on the activation energy, which represents the
minimum energy the colliding molecules must possess for the
reaction to be possible.
• To further demonstrate the importance of the concept of large
activation energy reactions, consider the first-order reaction of a
homogeneous mixture whose reaction rate is

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Classification of combustion phenomena
Premixed versus non-premixed combustion
• At the global level, a combustion system frequently consists of two
reactants: a fuel and an oxidizer. These two reactants must be brought
together and mixed at the molecular level before reaction can take place.
• In a premixed system, the reactants are already well mixed before
reaction is initiated.
• In a nonpremixed system the reactants are initially separated and are
brought together, through the molecular process of diffusion and the bulk
convective motion, to a common region where mixing and subsequently
reaction take place.
• What is the role of diffusion
(thermal and species) in premixed
and nonpremixed combustion?

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Premixed versus non-premixed combustion

Premixed flame front Nonpremixed flame front

Reactant A

Products Reactant A Reactant B

Reactant B

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Laminar versus Turbulent combustion
• A flame can also be featured by the nature of the flow, whether it is
laminar or turbulent.
• In a turbulent flame, fluctuations of velocity, temperature and species
concentration considerably fluctuate.
• The existence of turbulence generally promotes the reactant mixing
process.
• Turbulent combustion is
ubiquitous in real-world
applications

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Subsonic versus supersonic combustion

• Another way to characterize combustion according to the nature of

the flow is the flow velocity, whether it is subsonic or supersonic.

• In a subsonic flow, the molecular collision processes of diffusion are

predominant while reactions also have more time to complete.

• In supersonic combustion the high flow velocity usually renders

convective transport to dominate diffusive transport. Reactions also
have less time to proceed.

Subsonic Supersonic

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Homogeneous vs heterogeneous
combustion
• A combustion phenomenon is called homogeneous if both reactants
initially exist in the same fluid phase, either gas or liquid.
• If the two reactants initially exist in different phases, whether gas–liquid,
liquid–solid, or solid–gas, then the combustion is heterogeneous.

Gaseous flame (gaseous fuels) Spray flame (liquid fuels)

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Candle flame

zero g normal g

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 Various propulsion systems with
fuel combustion

Internal combustion engine Gas turbine engine

(airplane and power plant)
Rocket engine

Detonation engine
(higher efficiency)
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 Flame ignition
No chemical reactions
Flame front radius

Success
Ignition Chemical reactions initiated
Ignition failure

time
Flame kernel

Spontaneous Forced Other

ignition ignition approaches

Proper conditions Spark ignition

Laser ignition
Chemical ignition
……
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 Spontaneous ignition
• Spontaneous ignition vs. autoignition
• Proper conditions are required to achieve spontaneous ignition
• Spontaneous ignition is composed of two-stages, which correspond to
two ignition delays: chemical time and thermal time.
• In generally, chemical time is much longer than the thermal time.
• The first stage: build to the degenerate branching step or the critical
concentration of radical
• The second stage: associated with the steady reaction step; the reaction
system reaches the thermal explosion condition

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Ignition delay time

H2-O2-Ar mixture n-Heptane-air mixture

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 Forced ignition

• There are many approaches to force ignition of a reactive mixture, but

the most commonly studied concepts are those associated with
various processes that take place in the spark ignition, automotive
engine.
• The spark is the first and most common form of forced ignition. In the
automotive cylinder it initiates a flame that travels across the cylinder.
The spark is fired before the piston reaches top dead centre and, as
the flame travels, the combustible mixture ahead of this flame is being
compressed.
• Forced ignition can also be brought about by pilot flames or by flowing
hot gases, which act as a jet into the cold mixture to be ignited.

time 40
Minimum ignition energy

• Minimum ignition energy (MIE) has been introduced as a test method

for evaluating the ignitability of various fuel–air mixtures or any
system that has exoergic characteristics.
Minimum ignition energy

Fraction of stoichiometric percentage of combustible in air

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 Laminar flame speed

• Laminar flame speed is an intrinsic characteristic of premixed

combustible mixtures that plays a key role in understanding a mixture’s
reactivity, diffusivity, and exothermicity.

CH4-air mixture H2-air mixture

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Laminar flame speed
• Flame speed increases rapidly when the temperature of the fresh gas
increases but decrease when pressure increases.

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Summary

• Basic concepts of combustion

• Law of mass action and Arrhenius law
• Classification of combustion phenomena
• Significant flame or combustion parameters

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Extended reading
• Chapter 1/2 in An introduction to Combustion: Concepts and
Applications

An Introduction to
Combustion
S R Turn
Penn State University

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