1.

Some Fundamental Definitions and Phenomena

Examples of everyday life:

• lighter • candle
• campfire • gas fire

further examples:

• engine • oil-burner
• gas turbine • coal power station

Lots of technical applications are based on combustion processes.

What is combustion?

Simply spoken it is a reaction of fuel with an oxidizer where heat and light is released and which takes
place fast when a certain value of ignition temperature is reached. The final products of an complete
combustion of organic substances are carbon dioxide (CO2) and water (H2O). When using other substances
the corresponding oxides are formed.

Combustion is used to transform energy. Chemical energy is changed into thermal energy (heat), which
then can be changed in mechanical or electrical energy.

chemical
energy

thermal
energy

mechanical electrical
energy energy

advantage of combustion processes: very fast heat release

disadvantages of combustion processes: transformation into heat
formation of pollutants

1
necessary for a combustion:
examples:
fuel coal, hydrogen, natural gas, oil, candle wax, wood, etc.

oxidizer oxygen, air, compounds containing oxygen

Apart from some exceptions most of the fuels are organic compounds which means that they contain
primarily carbon and hydrogen as well as oxygen, nitrogen and other elements in smaller amounts.
Therefore as main products of combustion carbon dioxide and water are produced.

Examples:
Combustion of hydrogen: H2 + 1/2 O2 → H2O
Combustion of carbon: C + O2 → CO2
Combustion of hydrocarbons: CxHy + (x+y/4) O2 → x CO2 + y/2 H2O

Each symbol in such a chemical reaction equation represents 1 mol (6 ·1023 atoms or molecules). Thus, the
first equation means: 1 mol H2 reacts with 1/2 mol O2 to form 1 mol H2O. But by-products appear also, for
example CO (especially in the case of uncomplete combustion) and nitric oxides (NO, NO2)!

Characterization of combustion processes:

1.State of fuel and oxidizer

fuel oxidizer examples

gaseous gaseous gas lighter, gas-fired water heater

liquid gaseous oil-burner, Diesel engine
solid gaseous wood combustion, coal combustion, candle
gaseous liquid rocket engine
liquid liquid rocket engine
solid liquid rocket engine
solid solid rocket engine, firework

Remark: this division only refers to the original state of the fuel. In the case of a candle the wax melts first,
goes through the wick, vaporizes and then finally burns.

2. Way of mixing fuel and oxidizer

premixed combustion:
nonpremixed combustion:
fuel and oxidizer are mixed first and burnt later
example: spark-ignition engine: fuel is mixed with air in the
carburetor and burnt afterwards in the cylinder
fuel and oxidizer are mixed during the combustion process
itself; example: flame of a candle

2
3. Type of fluid flow

laminar
turbulent

Laser light-sheet LIF measurement of a turbulent natural gas-air

premixed jet flame (Dinkelacker et al.)

Variables to characterize a combustion process:

m kg overall mass
mi kg mass of species i in a mixture
wi = mi/m - mass fraction of species i
n mol total mole number
ni mol mole number of species i in a mixture
xi = ni/n - mole fraction of species i in a mixture
Mi kg/mol molar mass of species i (weight of 1 mol)
examples: MC = 12 g/mol, MH = 1 g/mol, MO = 16 g/mol,
MCH4 = 16 g/mol
M = Σ xiMi kg/mol mean molar mass

. 23 -1
NL = Loschmidt-number , Avogadro-constant = 6,023 10 mol = number of particles (atoms, molecules)
in 1 mol

Also used frequently: Mol-%= 100 xi, Mass-% = 100 wi

3
The following relations hold:

M n M x wi w / Mi
wi = S i i = S i i xi = M = S i
Mi
∑ Mj nj ∑ Mj x j ∑ wj / Mj
j =1 j =1 j =1

intensive properties: independent of the size (extent) of a system,

example: temperature, pressure, density etc.
extensive properties: dependent of the size (extent) of a system,
example: mass, number of moles, momentum etc.

density: intensive property, which is defined as the ratio of the corresponding extensive
property and the volume V
3
mass density (density) ρ = m/V unit: kg/m
3
molar density (concentration) c = n/V unit: mol/m

2 5
p Pa pressure 1 Pa = 1 N/m 1 bar = 10 Pa
T K temperature 0° C = 273,15 K
3
V m volume

perfect gas equation of state: pV=nRT good approximation for combustion

processes

R = universal gas constant R = 8,314 J/(mol K)

Laminar Premixed Flames:

Fuel and oxidizer are premixed before combustion. The flow is laminar.
Examples:

burnt gases conical flame

f
flame front

sinter plate

vu air air
vu

fuel + air fuel

flat flame Bunsen flame

4
A premixed flame is said to be stoichiometric, if fuel (e.g., a hydrocarbon) and oxidizer (e.g., air) consume
each other completely, forming only carbon dioxide (CO2) and water (H2O). If there is an excess of fuel,
the system is called fuel-rich, and if there is an excess of oxygen, it is called fuel-lean. For a combustion
with oxygen the mole fraction of the fuel in a stoichiometric mixture is xfuel,stoich. = 1 / (1+ν). Here ν denotes
the number of O2-molecules in the reaction equation for a complete reaction to CO2 and H2O. If air (xN2
.
= 3,762 xO2) is used as an oxidizer the mole fraction of the fuel is given by: xfuel, stoich. = 1 / (1+4,762 ν).

air equivalence ratio λ = (xair/xfuel)/(xair,stoich./xfuel,stoich.)

fuel equivalence ratio Φ = 1/λ

rich combustion: Φ>1 bzw. λ < 1

stoichiometric combustion: Φ=1 bzw. λ = 1
lean combustion: Φ<1 bzw. λ > 1.

The burning of freely burning premixed laminar flat flame into the unburnt mixture can be characterized
by the laminar burning velocity vL [cm/s], which depends only on the mixture composition, the pressure,
and the initial temperature (details will be shown later).
In the case of a premixed Bunsen flame the flame front can approximately be assumed to be flat (flame
.
thickness << curvature). Then it follows that vL = vu sin φ.

Laminar Nonpremixed Flames (diffusion flames):

Fuel and oxidizer are mixed during the combustion process itself. The flow is laminar.

burnt flame zone (at φ =1) 1)

flame zone gases
porous porous
plate plate
fuel + air

fuel air

burnt fuel air

gases

Nonpremixed flames include more complex chemistry than premixed ones, because the equivalence ratio
covers the whole range 0 < Φ < ∞ (rich combustion occurs on the fuel side, lean combustion on the air side).

Turbulent Premixed Flames:

5
In this case, premixed flame fronts burn and propagate in a turbulent fluid flow. If the turbulence intensity
is not too high, curved and strained laminar premixed flame fronts are formed. The turbulent flame can then
be viewed as an ensemble of many premixed laminar flames (flamelet-concept).

Turbulent Nonpremixed Flames:

In this case, nonpremixed flames burn in a turbulent flow field, and for low turbulence intensities the so-
called flamelet concept can be used again (see part II of the lecture). Because of safety considerations
nonpremixed flames are mostly used in industrial furnaces and burners.

The Bunsen burner as an example for both premixed and nonpremixed flames.

air air

fuel
+
air
fuel

air air

fuel fuel

premixed non-premixed

6
2 Experimental Investigation of Flames

Computer simulations are increasingly part of the discovery and design process. Nevertheless experimen-
tal investigations still remain important to guide them:
improvement of the models
validation of the models
demands
high spatial resolution
high temporal resolution
exact, reproducible results
negligible disturbance of the system

Principle of spectroscopic methods

Molecules can only take certain energy levels (rotation, vibration, electronic state)
Using light the energy level of a molecule can be changed
E=hν h = Planck's constant = 6.63 · 10-34 Js, ν = light frequency
Change of the rotational states: corresponds to the energy of microwaves
Change of the vibrational states: corresponds to the energy of infra-red light
Change of the elecronical states: corresponds to the energy of ultraviolet light

The different energy levels or the differences between them are like a fingerprint of the molecule.

2.1 Density Measurements

Rayleigh-scattering
elastic scattering of light (photons) from particles, which are small compared to the wavelength λ of the
light (d < λ)
Intensity of the scattered light proportional to the concentration.

virtual states

hν L hνS hνL hνS hνL hν S

E4 E4 E4
E3 E3 E3
E2 E2 E2
E1 E1 E1

Stokes- Rayleigh Anti-Stokes-

Raman Raman

Illustration of the basic processes in Rayleigh and Raman spektroscopy, Ei = vibrational levels of the
molecule considered, hνL = energy of the irradiated laser light, hνS = energy of the scattered light (h =
Planck's constant, ν = light frequency)

7
2.2 Concentration Measurements

Probe Sampling:
A suction tube is introduced into the system. The walls of the probe are cooled so that further chemical
reaction of the sample flowing inside the tube is halted (freezing of the reaction). The sample is then
analyzed for its chemical constituents using a wide variety of techniques.
Problem: intrusive.

Raman-Spectroscopy:
Absorption of a laser photon, virtual state with a short half-life of ca. 10 femtoseconds, emission of
Rayleigh, Stokes- (or anti-Stokes-) Raman-scattering light
simultaneous measurement of different species is possible
two-dimensional measurements (e.g., in turbulent flames) are possible but difficult
disadvantage: Raman effect is very weak, only species with concentrations above 1% can be routinely
studied

CARS Spectroscopy (coherent anti-Stokes Raman spectroscopy):

Advantage: three laser beams (two pump beams and one Stokes beam) have to coincide; special
geometrical configurations therefore allow high spatial resolution.

Laser Induced Fluorescence (LIF):

Excitation of electronic states in a molecule or atom
Large difference in energy between ground state and excited states, energetic light (UV-light, ultraviolet
light) has to be used
The excited states return to states with lower energy, accompanied by a radiation of light (fluorescence)
different vibrational levels can be reached

E 4*
E 3* real states
E 2*
E 1*

hνL hνLIF

E4
E3
E2
E1

Illustration of the basic processes in laser induced fluorescence. Ei* = vibrational levels of the electronically
excited molecules, Ei = vibrational levels in the electronic ground state, νL = laser frequency, νLIF =
fluorescence light frequencies
advantage: high sensitivity disadvantage of LIF: difficult to quantify
particularly interesting: simultanious two-dimensional measurements with laser light sheets.

8
Two-dimensional laser light sheet measurements (OH-LIF) in an Otto test-engineat lower (left hand side) and
higher (right hand side) turbulence; the higher turbulence case is leading to distinct flame quenching which is
responsible for unburnt hydrocarbon emission (Becker et al. 1991)

2.3 Temperature Measurements

Thermocouples: pairs of junctions between different metals

Induced voltage is approximately proportional to the temperature difference between the two junctions
(thermoelekctric effect)
Depending on the temperature range different metal combinations are used (for instance, platinum/
platinum-rhodium or tungsten/tungsten-molybdenium).
Disadvantage: intrusive method (catalytic reactions at surface, conductive heat losses via wires, disturbance
of the flow field), radiative heat losses.

Na-Line-Reversal-Method: Here sodium-containing compounds are added to the reactants. Sodium

atoms can absorb or (at elevated temperatures) radiate yellow light. The yellow Na-emission of added Na
in comparison with a black body disappears if the Na-atoms have exactly the same temperature as the black
body. If the temperature is higher, more light is emitted than absorbed; if the temperature is lower, more
light is absorbed than emitted.

CARS Spectroscopy: Besides species concentrations, temperatures can be measured by CARS

spectroscopy. For this high resolution spectra are compared with simulated spectra which can be derived
theoretically from molecular properties of the species under consideration.
advantages: high spatial (about 1 mm3) and temporal (about 10 ns) resolution,
disadvantages: high costs and complicated evaluation of the data

Laser-Induced Fluorescence: The selective excitation of different energy levels in molecules (e. g., in
OH-radicals) can be used to determine the population distribution of the energy levels. Assuming a
Boltzmann distribution, temperatures can be determined.

9
2.4 Pressure Measurements

conventional manometers or electrical capacity manometers

piezoelectric pressure transducer

2.5 Velocity Measurements

Anemometry (Velocimetry)

hot-wire-anemometer:
An electrical heated platinum wire is suspended normal to the flow. The heat transfer from
the wire is related to the approeach velocity.
disadvantages: Disturbance of the flow field, catalytic surface

particle tracking method

Particles with a size in the order of 1μm are added to the flow. The traces of the particles are
determined by taking pictures with sufficient long times of exposure. In this way velocities
and even velocity fields can be measured.
disadvantages: Added particles disturbe the flow field, particles have to follow the flow field

PIV (particle image velocimetry):

A thin planar sheet of light from a pulsed laser illuminates particles. Due to the multiple
pulses of laser light, the particle images are dots displaced in space, and the displacement can
be related to the velocity.
Disadvantages: Added particles disturbe the flow field, particles have to follow the flow field

Laser-Doppler-Anemometry LDA (Laser-Doppler-Velocimetry LDV)

Particles are added to the flow. As with all particle scattering of light, conservation of
momentum leads to a Doppler-Effekt (slight shift of frequency of the scattered light)
disadvantages: Added particles disturbe the flow field, particles have to follow the flow field

2.6 Measurement of Particle Sizes

In multi-phase combustion systems (spray-combustion, coal combustion etc.) not only velocity, temperature,
and concentrations, but also the size and the distribution of fuel particles (coal particles, droplets) are
desired.

Mie-Scattering:
Scattering of light by particles, which are larger than the wavelength of the light
Probe Sampling

10
3 Conservation Equations for Laminar Flat Flames

3.1 Physical and Chemical Processes in Flames

How does a combustion work?

fuel + oxidizer → products and heat

reaction must be initiated,e.g., by an ignition

raection must propagate on it's own

Example: premixed combustion (typical temperatures of the burnt gas > 2000 K)

m / mges T

products propagated
flame front

oxidator
heat conduction

fuel
heat release due to
intemediates chemical reaction

x
unburnt reaction burnt gases
mixture zone

Molecular Transport (diffusion, heat conduction, friction)

Example: stationary system, no chemical reaction

∂Y ∂2Y
= D
∂t ∂z 2

Y: considered variable, e.g.., temperature T, concentration c, . . .

D: proportionality factor, e.g. heat conductivity, diffusion coefficient, . . .
t:time
z: spatial coordinate

1 ⎛ z2 ⎞
special solution for Gaussian-distribution: Y ( z,t ) = Y 0 ⋅ ⋅ exp ⎜ − ⎟
4πDt ⎝ 4 Dt ⎠

11
 w

w i0
D=1 t=0

t = 1/16

t = 1/4

0 z
-1 0 1

typical diffusion process

Convection

Example: no chemical reaction, no molecular transport

∂Y ∂Y
= −v (Y = wi , T )
∂t ∂z
Convection with a velocity v. Analytic solution:

Y(z,t) = Y(z-vt,0) .

t=0

t=2

t=1

Convective process, profile moves by a distance v·t, shape doesn't change

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Example 3: stationary system without molecular transport (A = B = 0)

∂wi
∂t
(
= Ω i wi , w2 ,K, wns , T , p )
Ωi = chemical rate of production of species i
wi = mass fraction, p = pressure, T = temperature

In flames all these processes occure in a coupled way!

3.2 Assumptions and general form of the conservation equations

The conservation equations for a laminar flat flame shall be derived in the following (chapter 1).
Assumptions:
• The perfect gas law can be used.
• External forces are negligible (e. g., gravitation).
• The system is continuous (the mean free path of the molecules is small compared to the flame
thickness).
• The pressure is constant (spatial pressure fluctuations are weak).
• The kinetic energy of the gas flow is negligible.
• The reciprocal thermal diffusion effect (Dufour-Effekt) can be neglected.
• Heat fluxes caused by radiation (e.g., of glowing soot particles) is negligible.
• The system is in local thermal equilibrium.
• The flame is stationary, i.e., there are no temporal changes.

Abgas J

z
z
Flammenfront

Sinterbrenner

dz
Frischgas Fläche F

For any conserved variable E (z = spatial coordinate, t = time) in a one-dimensional system we have the
general relation
∂W ∂J
+ = Q holds.
∂t ∂z
W = density of the conserved variable = E/volume
J = flux density of the conserved variable = E/(surface · time)
Q = source of the conserved variable = E/(volume · time)

13
3.3 Conservation of the Overall Mass m

W = ρ = density (total mass density)

J = ρv = mass flux
Q = 0
Here v denotes the velocity of the center of mass, also called flow velocity of the mixture. Insertion leads
to the continuity equation:

∂ρ ∂ ( ρv)
+ = 0
∂t ∂z

3.4 Conservation of the Masses mi of Species i

Wi = ρi = mi/V = wi ρ = partial density of species i

Ji = ρi vi = wi ρ vi = = mass flux of species i
Q = Mi (∂ci/∂t)chem = ri = chemical rate of production of species i

Here vi = v + Vi denotes the mass velocity, Vi the velocity relative to the center of mass, Mi the molar mass
and(∂ci/∂t)chem the molar chemical rate of production of species i. Insertion leads to:
∂wi ∂wi ∂ji
ρ + ρv + = ri
∂t ∂z ∂z

ji denotes the diffusion flux density of species i (in the center of mass system) ji = ρwiVi = ρiVi.
∂wi
ji ≈ − Di , M ρ Di,M = diffusion coefficient for species i into the mixture
∂z

3.5 Conservation of the Specific Enthalpy h of the Mixture

W = Σρjhj = Σwjρhj,
J = Σρjvjhj + jq = Σρwjvjhj + jq
Q = 0

Here hj denotes the specific enthalpy of species j and jq a heat flux, which corresponds to the diffusion flux
ji introduced above and is caused by transport of energy due to temperature gradients. Insertion yields:

∂h j ∂h j ∂h j ∂jq
ρv ∑ w j + ρ ∑ wj + ∑ h j rj + ∑ j j + = 0
j ∂z j ∂t j j ∂z ∂z

∂T
jq = −λ λ = heat conductivity
∂z

14
3.6 The Complete Description of a Laminar Flat Flame Front

For a complete description of laminar flat flame fronts, the temperature T, the pressure p, the velocity v
and the partial densities ρi (i = 1,...,S for S species) or the overall density ρ and the S-1 linearly independent
mass fractions w1,...,wS-1 (wS = 1 - w1- ... - wS-1) have to be known as functions of the spatial coordinate z.

pressure p:
The pressure is assumed to be constant and equal to the surrounding pressure.

density ρ:
The density can be calculatedfrom temperature, pressure and composition using the perfect gas law.

velocity v:
The velocity is obtained from the continuity equation. Because the flame is assumed to be stationary
it results ρv = const.. Using the given mass flux (ρv)u of the unburnt gases, v can be calculated at each
point in the flame.

mass fractions wi (i = 1 , ... , S-1):

Inserting the diffusional mass flux ji into the species conservation equation leads approximately to:

∂wi ∂ ⎛ ∂w ⎞ ∂wi
ρ = ⎜ Di, M ρ i ⎟ − ρv + ri
∂t ∂z ⎝ ∂z ⎠ ∂z

temperature T:
Inserting the heat flux jq and using cp,j dT = dhj ; cp = Σwjcpj (specific heat capacity of the mixture at
constant pressure) yields

∂T ∂ ⎛ ∂T ⎞ ∂T
ρc p = ⎜λ ⎟ − ( ρvc p + ∑ j j c p, j ) − ∑ h j rj
∂t ∂z ⎝ ∂z ⎠ j ∂z j

Now all the equations required to solve the problem are given.

3.7 Numerical Solution of the Conservation Equations, Examples

General form of the conservation equations:

∂Y ∂ 2Y ∂Y
= A + B + C
∂t ∂z 2 ∂z

In general this partial differential equation system cannot be solved analytically. Therefore, a numerical
solution is necessary.

15
Discretization:

The solution of the equation system is performed for distinct (discrete) points spatial points
Derivatives → difference quotients finite differences
also a discretization in time necessary

Initial values and boundary conditions have to be specified.

Example: Fourier's equation for heat conduction

2 2
The problem ∂T/∂t = λ∂ T/∂z is an initial value problem with respect to time t: The initial value of the
temperature profile T = T(z) must be specified at t = t0, in order to begin the numerical solution.
Furthermore, the problem is a boundary value problem with respect to variable z: for all times t the
boundary values TA = T(zA) and TE = T(zE) must be specified.

The differential equation describes the time behaviour of the temperature profile T = T(z). For sufficientlylarge
t a "stationary" (i.e. time-independent) solution is obtained: The profile no longer changes with time t (For
the Fourier equation a linear profile is obtained, since the temporal change, and thus the curvature of the
temperature, have to vanish.).
In a similar way, the numerical simulation of a laminar flat flame demands one initial value for each of
the spatial locations (one integration constant for the first derivative in time) and two boundary conditions
(two integration constants for the second derivatives in space) for all times.

reactants
T, w reactants T T, w
T

products products

intermediates
intermediates

z z

structure of laminar flat flames

16
Profiles of temperature and mole fractions of stable species in a flat acetylene-oxygen-flame at p = 100
mbar; different hydrocarbons lead to corresponding results; the concentration profiles are measuredwith
a mass spectrometer, the temperature is determined using the Na-Line-Reversal-Method.

17