Combustion Science Kap 3 PDF

3 Chemical kinetics of gas-phase reactions
3.1 Basic concepts
Thermodynamics:
Until now we have dealt with
the thermodynamics of Initial Final
matter conversion and state state
energy conversion
There, only the initial state Kinetics:
and the final state (described
as an equilibrium) were of All states
interest in between
Chemical kinetics describe

the temporal behavior of
reactive systems
3.1
IVG, Universität Duisburg-Essen, Combustion Science, Prof. Dr. Christof Schulz
Combustion kinetics
The kinetics of combustion reactions is an important field of the general chemical

kinetics
Since the beginning of combustion science it is known that the chemical reactions
through which the fuels are converted into the combustion products, are particularly
complicated
It is only possible to obtain a detailed understanding of the kinetics of combustion if
the individual molecular reaction paths including the intermediate species and their
reaction coefficients are known
Therefore, we will:
 Develop the terminology of chemical kinetics for homogeneous
gas-phase reactions
 Consider complex gas-phase reactions
 Describe the fundamentals of heterogeneous reactions,
that are relevant to many practical combustion processes
3.2
Reaction rate R
Subject of the kinetics is the temporal evolution of chemical reactions, including all
factors, that have an influence on this evolution
The temporal behavior is expressed by the reaction rate R
The most important factors that influence the reaction rate are:
R  R(p,T,c i )
p : pressure
T : temperatur e
c i : concentrat ion of the reactant i
For the complete description of the chemical evolution of a reaction, the reaction
path (reaction mechanism) must be known
In most cases, this path does not directly lead from the reactants to the products
as described by the overall reaction equation
3.3
Concentration and reaction rate
Example: Reaction A  P
If the concentration of a reaction
product or of a reactant is
measured as a function of time, the RP(t = 0)
slope of such a curve is a measure RP(t )
ci
of the reaction rate
cP
Through a systematic analysis of –RA(t = 0)

cA
the dependences of the reaction
rate, it is sometimes possible to
draw conclusions about the time
reaction mechanism Reaction rates:
Rp  dcP dt  d [P] dt
RA  dc A dt  d [A] dt
3.4
Reaction progress
The reaction progress is measured through the increase of the concentration or

partial pressure of a reaction product or through the decrease of a reactant
In homogeneous systems, the reaction rate usually depends on the concentration
of the reactants. This can happen
 in a simple manner, or
 in a complicated manner
The experimentally-determined dependences often give indications about the way

the reaction works, but they do not always lead to the molecular evolution of a
chemical reaction
3.5
Order of a reaction
Order of a reaction
The observed temporal behavior of a global reaction can be characterized
by the reaction order
The formation rate of a product depends on the concentration of a reactant
to the power of the reaction order:
Reaction
A mechanism P
d [P]
 [A]
dt
 The reaction order  is an experimental value that is not necessarily integer

(integer is: 0, 1, 2, …)
 Not every reaction mechanism can be globally represented by a reaction order

 Non-integer values of  often indicate the presence of a complex reaction
mechanism
3.6
Zeroth-order reaction
Rare. The reaction rate is independent

1.0
of the reactant concentration. This can
occur in catalytic reactions
A→P
0.9
dc A
 k
dt
cA /cA0
Half-life period:
Reduction in cA by 50% 0.8
1 2 : c A  1 2 c A0
1 2  c A0 2k
0.7
t/s
3.7
First-order reaction
Typical in radioactive decay:

Exponential decrease on c
A→P
dc A
 kc A
ln cA /cA0
dt
dc
 cAA  k  dt
ln c A  kt  const
c A  c A0 exp  kt 
Half-life period is independent

on the initial concentration
t/s
1 2 : c A  1 2 c 0
A Determination of the rate constant of a
 1 2  ln 2 k first-order reaction:
The slope of a (ln cA) vs. t diagram yields k
3.8
Second-order reaction
A→P
dc A
 kc A 2
dt
t1/2/s
cA
Half-life period depends on
the initial concentration
1 2 : c A  1 2 c A0 t/s 1/cA0
0
1 2  1 k c A Determination of the rate constant via evaluation
of subsequent half-life periods:
a, b, c, … are half-life periods for different initial
concentrations. If these values are plotted vs. 1/cA
the slope of the resulting straight line equals 1/k
Equivalent:
Determine the slope in a plot (1/cA – 1/cA0) vs. t
3.9
Second-order reaction: Examples
dc A
2A →P  kc A2
dt
dc A
A+B→P  kc AcB
dt
If cB >> cA
dc A
 k c A
A+B→P dt Evaluation by pseudo-first-order approach
3.10
Pseudo first order reaction
A+B+C+…→ P
cB, cC ~ const.
dc A
 kc A
dt
If all reactants but one are available in
ln cA /cA0
excess, the reaction rate depends on the
concentration of this single reactant
This is a well-known method to investigate
the dependence of the over-all rate on the
concentration of the different reactants
The reaction rate can then be obtained like
in a first-order reaction
t/s
3.11
Data evaluation: First or second order?
Analysis of experimental data
First order Second order

lnc A c A0 1 cA
1 c A0
t t
3.12
3.2 Experimental determination of reaction-rate
coefficients
 Slow reactions (1/k ~ minutes): Batch reactor

• Mixing time negligible
• Concentration measurement as a function of time
• Chemical analysis of samples
 Faster reactions (1/k ~ seconds): Flow reactor
• Fast mixing required
• Concentration measurement as a function of location
• Fast sampling and “freezing” of reaction,
optical diagnostics preferred
 Ultrafast reactions (1/k << seconds): Pulsed reaction
• Mixing of reactants not an option
• Sudden “disturbance” of a system:
Start of reaction by photolysis, shock-heating
• Concentration measurement as function of time after the disturbance
• Fast optical diagnostics required
3.13
Detection methods for gas-phase concentrations
 Stable reaction partners

Sampling in stationary reaction systems, e.g., flames, with a probe system;
concentration measurements by various physical and chemical methods
 Unstable reaction partners, radicals
Can only be detected in the reaction zone itself (in situ):
The composition would be changed immediately during sampling
Investigation of short-lived intermediates

 Spectroscopic detection methods
Optical detection without sampling directly in the reaction zone. Absorption or
emission spectroscopy, laser-induced fluorescence, and light scattering
 Molecular-beam technique
Extraction from the reaction zone with quasi-non-disturbing probe;
concentration detection with mass spectroscopy or other methods
3.14
Principles of the experimental determination of rate
coefficients
The experimental determination of 1. Reactive mixture at rest
rate coefficients requires
concentration measurements of d [AB] d [C] d [A] d [BC]
    k1[A][BC]
as many species as possible dt dt dt dt
These concentrations must be d [AB] dt d [C] dt
k1  or
measured as a function of time or, [A][BC] [A][BC]
in case of stationary flows, as a
function of position in the flow The initial molar concentrations of A and
reactor BC must be known and at least one of
the species concentrations must be
measured as a function of time
Example
2. Stationary flowing reactive mixture
Elementary reaction
d [AB] dx
A  BC 
k1
AB  C  k1[A][BC]
dx dt
u d [AB] dx
k1  u : flow velocity
[A][BC]
3.15
Determination of reaction rates of combustion-relevant

reactions
The difficulties in the diagnostics of combustion reactions arise from:
 Reactions are usually very fast under realistic conditions
 Elementary reactions of interest can be integrated in large reaction schemes
and are hard to isolate
 During many elementary reactions, radicals play an important role. They only
exist in the reaction zone itself and can only be detected through contact-free,
non-intrusive measuring techniques
Rate coefficients can usually not be obtained directly from practical systems. Here,
full reaction schemes (*and transport) are present. Model configurations are:
 Flames*: Especially flat, laminar premixed flames, burning at normal pressure or reduced
pressures. In the case of low pressure flames, the reaction zone is strongly extended
 Flow reactors: Reactions of purposely generated radicals, taking place at pressures
between 1–20 mbar in an inert carrier gas are investigated; T < 1200 K
 Reaction cells: Chemical reactions are started through flashlight or laser photolysis under
almost isothermal conditions; T  300 K
 Shock tubes: Chemical reactions triggered in reactive mixtures through gas dynamic
heating are followed (pulsed chemical reactor). Typical T: 800–10,000 K
3.16
Experimental methods:
Probe techniques versus optical diagnostics
Effects of probes inserted Optical diagnostics:

into the flame:  Non-invasive
 High spatial resolution (< 0.001 mm3)
 High temporal resolution (< 10 ns)
 High spectral resolution (~ MHz)
 Multiplex (multi-species, multi-point)
NO-LIF
thermometry
Flame
photo-
graph
Temp.
250–
Premixed flame 2500 K
Undisturbed pre- disturbed by a
mixed flame thermocouple
3.17
Shock-tube experiment
Fast reactions can be studied in

shock-tube reactors
 Gas mixture is suddenly heated (within
microseconds) to high temperatures by
adiabatic compression of the reactant
gases (behind incident or reflected shock
waves)
 Typical temperatures:
800 K to several thousand Kelvin
 Observation of concentration as a function
of time after arrival of the shock wave by
optical diagnostics
High-pressure shock-wave reactor at IVG, pmax = 500 bar
3.18
Shock wave process
Investigation
Reactive mixture
(metastable at room Test section Driver section
temperature) in the T1 p1 T4 p4
test section Membrane bursts
Pressure
Instantaneous heating T4 p4
T1 p1
of the reactive mixture
Temperature Temperature
via Shock wave

Pressure
a) Incident wave
T4 p4
T1 p1 T2 p2
b) Reflected wave Reflected shock wave

Pressure
Actual temperature T5
determined from p5 T p
2 2 T3 p3
shock wave velocity
3.19
Shock tubes
3.20
Shock tube with absorption measurement
Measurement of the concentrations
of H atoms during the thermal d [H] dt 0
decomposition of CH4
[H]
t
SEV
Reaction mechanism:
Monochromator
CH4  M 
1
CH3  H  M
I0 CH4  H 
2
CH3  H2
Absorption:
I0  I
k1 
d [H] dt 0
A  f ([H])
I0 [CH4 ]0 [M]0
I
 [H]  [H](t)
3.21
Molecular-beam sampling
with mass spectrometry analysis
7
Mean particle diameter dp /nm
H2/O2 =1,0
Low-pressure flame with molecular beam 6 H2/O2 =1,29
system and mass spectrometer H2/O2 =1,8
Sampling of molecules and particles at 5
different positions downstream of the flame 4
2 Conc Sn(CH3)4 = 823 ppm

60 90 120 150 180 210
Pressure to vacuum
control pump Deflection Flow coordinate x /mm
voltage
to
H2/O2/Ar r vacuum
Precursor pump
Molecular
beam Current
30 mbar 10–3 mbar 10–6 mbar
Low-pressure flame Particle mass spectrometer
3.22
3.3 Elementary reactions and reaction mechanisms
Experimental investigations yield:
The reaction between H2 and I2: The reaction between H2 and Br2:
the reaction product is HI the reaction product is HBr
Stoichiometric reaction equation: Stoichiometric reaction equation:
H2 + I2 → 2 HI H2 + Br2 → 2 HBr
Measured reaction rate: Measured reaction rate:
dHI dHBr  k H2  Br  2

1
 k H2  I2  
dt dt 1  HBr  m Br2 
In this case, the reaction equation does

In this case, the reaction equation is
obviously not describe the actual reaction
equal to the elementary reaction
progress!
equation
3.23
Reaction mechanism
The previous example (3.23) showed that the kinetic progress of a reaction does
not necessarily follow the scheme described by the global reaction equation
H2  Br2  2 HBr Global reaction equation
The detailed kinetics in case of the HBr-formation is known:

Br2 → 2Br● Species like Br• and H• are called
Br● + H2 → HBr + H● “radicals“. They are intermediates
H● + Br2 → HBr + Br● with broken chemical bonds. Their
H● + HBr → H2 + Br● unpaired electron makes them very
Br● + HBr → Br2 + H● reactive
Br● + Br● → Br2 Reverse reactions that appear in theis
mechanism lead to a formation of an equilibrium
H● + Br● + M → HBr + M
The reaction product HBr is formed according to the reaction mechanism,
which consists of individual elementary reactions
Intermediates like H and Br atoms (radicals!) play a crucial role
3.24
Results of the analysis of the HBr formation
 The kinetics of the HBr formation from H2 and Br2 follows

a sequence of elementary reactions
 The combination of all elementary reactions is called
the reaction scheme or reaction mechanism
 Atoms (radicals) like H• and Br• are, as intermediates, important elements
of the reaction mechanism. They are crucial but need to be present in
small concentrations only. The are called reaction carriers
 The initial reaction, here Br2 → 2 Br•, is a requirement for the
start of the reaction. It creates the first radicals
 The reaction is a so called chain reaction
 In propagation reactions radicals appear as both reactants and products
 Radicals can disappear in a termination reaction. This happens for example
if radicals hit the reactor wall or recombine to form stable molecules again
3.25
Elementary reactions
Only few global reactions proceed in one

step. In general the reaction progress takes
place through a sequence of elementary
reactions
Examples:
An elementary reaction is the smallest
elementary reaction step within a reaction Br  H2  HBr  H
mechanism
According to a molecular dynamics view, an

elementary reaction occurs through
 Collisions between molecules or atoms, or OH  H2  H2O  H
 Through the spontaneous decomposition
of an activated species
3.26
Molecularity
The molecularity of a Bimolecular reactions:

chemical reaction gives the
Collision of two molecules
number of elementary
reaction partners that form CO  O 2
an activated complex, which CO  O2  (CO  O2 )#
CO2  O
then decomposes into the Activated
reaction products complex
The activated complex is a

Classes of reactions:
pseudo-molecule or an atom
configuration, which exists CO  O2  CO 2  O  Exchange
for a short time during the OH  H2  H2 O  H  reaction
collisional interaction of, e.g.,
two molecules or atoms
O2  M  O *2  M  Activation and
 disactivation
A*  M  A  M  reaction
3.27
Uni- and trimolecular reactions

Unimolecular (mono-molecular) Trimolecular reactions:
reactions: Reactive three-body collisions:
Spontaneous decay of a molecule,
particle or activated complex CO  O  M  (CO  O  M)#
(one reactant)
 CO2  M
A  B  C H  H  M  H2  M
C2H6  CH3  CH3
Ra  He  Rn Trimolecular reactions are generally
exothermal reactions
Examples:
The third collision partner M removes
 Initiation of combustion reactions part of the reaction enthalpy from the
 Radioactive decay of radium into reacting particles (heat sink)
helium and radon Three-body collisions become more
likely at elevated pressures
Elementary reactions with a higher molecularity than 3 can be neglected
3.28
3.4 Reaction rate, change of molar concentrations
The reaction progress of an elementary reaction can be described through the

increase of the mole numbers of the reaction products per unit of time or by the
temporal decrease of the reactants
The change in concentrations due to an elementary reaction j can be described by
the reaction progress variable j:
1 V Definition of the reaction progress variable (cf. chapter 2)

d j  dni  dci
ij ij
Example: A  B 
j
 2C  D
dj dn dn 1 dnC dnD
 A  B  
dt dt dt 2 dt dt
The changes in the mole numbers nA, nB, nC, and nD of the species that take part
in the reaction j are not independent from each other. They depend on the
reaction progress variable together with the stoichiometric coefficients ij
3.29
Rate of change of concentrations
The reaction rate Rj of an elementary reaction j is defined as the temporal variation

of the reaction progress variable j per unit volume:
1 d j 1 dc i 1 V c i  ni V
Rj  or: R j  with: d j  dni  dc i
V dt  ij dt  ij  ij c i : molar concentration
Through a transformation of the above equation, one obtains the change in

concentration ci of species i as a function of the reaction rate Rj.
If ci is changed by several elementary reactions j (within a reaction mechanism)
it follows:
dc i
  ij R j The value dci / dt is the rate of change of concentration ci
dt j
   ij " ij 'R j
In case species i appears both as product (with ij”) and dc i
reactant (with ij’) in the equation the equation changes to: dt j
3.30
Example: Reaction rate / rate of change of concentrations
Reaction mechanism for the CO oxidation Rate of change of molar concentrations after
in the presence of traces of H2O including the reaction rates
CO  O2 
1
CO2  O j=1 dc CO
 k1cCOcO2  k 3cCOcOH  k 5cCOcOc M
O  H2O 
2
OH  OH j=2 dt
dc O2
CO  OH 
3
CO2  H j=3  k1cCOcO2  k 4cHcO2
dt
H  O2  OH
4
 O j=4 dc CO2
 k1cCOcO2  k 3cCOcOH  k 5cCOcOcM
CO  O  M  CO2  M
5
j=5 dt
dc OH
Reaction rates  2k 2cOcH2O  k 3cCOcOH  k 4cHcO2
dt
R1  k1cCOcO2 R4  k 4cHcO2 dcH
 k 3cCOcOH  k 4cHcO2
R2  k 2cOcH2O R5  k 5cCOcOcM dt
dc O
R3  k 3cCOcOH  k1cCOcO2  k 2cOcH2O  k 4cHcO2  k 5cCOcOcM
dt
Rate of change of molar concentrations dcH2O
 k 2 c O c H2 O
dc CO dc O2 dt
 R1  R3  R5  R1  R4
dt dt
System of ordinary, nonlinear differential
dc CO2 dc OH
 R1  R3  R5  2R2  R3  R4 ... equations for the molar concentrations
dt dt
3.31
3.5 Dependences of the reaction rate Rj
The reaction rate Rj of an elementary reaction is a function of temperature,

pressure, and of the concentrations of the participating species
R j  R j T,p,c i   R j T,c i 
This dependence can be written in form of a product:

R j T,c j   k j T  Fj c j  k j T  : Rate coefficient
For elementary reactions, the function Fj (depending on the molecularity of the

reaction) can be written as a product, the order of the reaction equals the sum of the
stoichiometric coefficients:
Fj c i    c i  ij
R j T,c i   k j T   c i  ij mol cm–3 s–1

The reaction rate Rj describes the molecular collision process and is proportional to
the number of successful (i.e., reactive) collisions between molecules
3.32
Temperature dependence of the reaction-rate coefficient
For many reactions, the temperature dependence of the reaction rate coefficients
kj(T) is very strong. At room temperature an increase of temperature by 10 K is
often sufficient to double the reaction rate!
In 1889 Arrhenius empirically found a principle representation of the reaction rate
coefficient, that is still valid today and named after him:
k (T )  k0 exp   Ea RmT  k0: Frequency factor

Ea: Activation energy
 The Arrhenius law is universally valid for elementary reactions

 The frequency factor k0 and the activation energy Ea can be weak functions of
temperature, which is often neglected
 Rate coefficients of elementary reactions must be determined experimentally.
They are evaluated in so-called Arrhenius diagrams:
In these ln(k) over 1/T diagrams, a linear dependence is often found.
The slope then depends on the activation energy Ea
3.33
Examples of Arrhenius diagrams
Arrhenius diagram:
Plot of ln k vs. 1/T
 The slope gives –Ea/R
 The offset at 1/T = 0 gives k0
Example: CH3CHO decomposition
In tables you often find the activation

energy represented as
 Energy (Ea in kJ/mol) or as
 Temperature (Ea/R in K)
1000 700
T/K
3.34
Examples of Arrhenius diagrams
Elementary reaction H + O2 → OH + O Thermal decomposition of CH4

Results obtained by different authors CH4  M 
1
CH3  H  M
CH4  H 
2
CH3  H2
2500 2000 1800 1600 K 2300 2000 1800 K
1010
Rate coefficient / cm3mol–1s–1

Rate coefficient / cm3mol–1s–1
1013
8 k1 = 4.7×1017exp(–46900 K/T)cm3mol–1s–1
6 109
5
4
3 108
107
1012
106
0.4 0.5 0.6 0.45 0.50 0.55
1000 K / T 1000 K / T
3.35
Example for temperature-independent reactions:

Fast bimolecular exchange reactions
There are many very fast bimolecular exchange reactions, for which the rate
coefficients are practically independent of temperature: No activation energy must
be overcome and every single collision is reactive
NO  N 
1
N2  O, k1  2.4  1013 cm3mol 1s 1
CN  O 2 
2
NCO  O, k 2  4.9  1012 cm3mol 1s 1
CN  O 
3
CO  N, k 3  1.8  1013 cm3mol 1s 1
Rate coefficients for many elementary reactions can be found in:

„Evaluated Kinetic Data for High Temperature Reactions“
Baulch, Drysdale, Horne, Lloyd, Vol. 1 – 3, Butterworth, London
3.36
Gas-kinetic interpretation of the T-dependence of Rj
Comparison of the temperature dependence of the reaction rate according to
Arrhenius and according to collision frequency based on the kinetic theory of gases:
Reaction rate according to Arrhenius A  BC  j

 AB  C
(bimolecular reaction): R j  k j c A cBC
R j  c A cBC k0 exp   Ea RmT 
If each gas kinetic collision would lead to a chemical conversion, the reaction rate Rj
would be equal to the gas-dynamic collision rate Z
Collision rate according to gas kinetics: N : Avogadro number A
: Mean collision cross-section

 2,2  Mi : Molar mass of species i
Z  c A cBC NA   v A, BC 
2
 2,2 
 : Correction factor for
Lennard-Jones potential
8 RmT M A MBC
v A, BC  : Mean relative velocity  A, BC  : Reduced mass of the A / BC system
 A, BC M A  MBC
 Rj and Z show a fundamentally different temperature dependence
3.37
Modified collision model
Not every collision of reactive species (A-B-C)#

Energy
leads to chemical conversion!

Obviously, not all the atoms and Ea Activation
molecules are “ready” for a reaction energy
A + BC
The “readiness” to react depends in the E1
energy content of the collision complex AB + C
E2
Only collisions are successful (i.e.

reactive) where the collision complex Reaction coordinate
has sufficient energy to overcome the
activation barrier Ea (i.e., the energy
required to form the activated complex) The reaction must overcome an
“energy barrier”, the so-called
activation energy Ea
3.38
Activation energy
E1 : Average energy of the species A and BC before the collision

E 2 : Average energy of species AB and C after reaction
Though E2  E1 (overall exothermal reaction) not every molecular collision
leads to a successful reaction, because the activation energy as an “energy
barrier” must be overcome
 The activation energy of a chemical reaction is an explanation for the
macroscopically-observed inhibition of chemical reactions (cf. inhibited
equilibrium)
 Only “particularly strong” collisions of reaction partners that lead to a collision
complex with an energy Ea above the average energy E1 can overcome the
energy barrier and lead to chemical conversion
 The theoretical maximum value for Ea is the sum of all bond energies
 Ea is often significantly smaller than this theoretical maximum due to the
simultaneous formation of new bonds
Which fraction of the molecules has enough energy to overcome the barrier?
3.39
Maxwell velocity distribution

Molecular velocity distribution (Maxwell dnv  f (v )dv
distribution) for gases in equilibrium
One-dimensional: Symmetrical Gaussian dnv: Number of molecules with velocity v in the
interval dv
velocity distribution (average velocity v x  0 )
v: Molecular velocity
f(v): Velocity distribution function
Three-dimensional: 4 v 2n  mv 2 
f (v )  exp  
Grey value (2 kT / m )3 / 2  2kT 
indicates the
probability of m: Molecular mass
different velocities k: Boltzmann constant
n: Particle per volume
T1 T: Temperature
Volume
4v2dv f(v)

T2 > T1  f (v )dv  n
0
Integration of three-dimensional velocities over
the volume element 4v2/dv yields the Maxwell
distribution
v
3.40
Average velocities
 Average velocity 8kT
(expected value from Boltzmann v 
m
distribution, center of the distribution)
 Most probable velocity 2kT

vw 
(maximum of Boltzmann distribution) m
 Average squared velocity 3kT

(from average energy) v2 
m
 Typical values at room temperature H2 : v  1750 m s
N2 : v  500 m s
CO2 : v  330 m s
 Reminder: For relative velocities of M A MB

collisions between A and B: Replace the  AB 
M A  MB
mass m by the reduced mass µ
3.41
Energy distribution function

m 2
Instead of the distribution function dn  f (v )dv E v
2
f(v) for the molecular velocities, a dE  mv dv
distribution function f(E) for the dn  f (E )dE
kinetic energy of the molecules
2n 4E  E 
can be introduced f (E )  exp  
kT kT  kT 
For the calculation of collision f (E ) : Energy distribution function
energies the relative velocity of
the collision partners is required For reactive collisions the available relative
energy of the colliders is determining
Only the part of molecules with
E > Ea are ready for reaction E: Relative energy of the
colliding species
f(E)
Fraction of collider pairs
with sufficient energy to
overcome Ea
Em Ea E
3.42
Number of reactive collisions
Only molecular collisions with a relative energy E > Ea can lead to chemical
reactions. The total collision number Z given earlier (see 3.37) can be obtained
by integrating the full molecular velocity distribution function:

1
Z     2
dv
0
2
The number of reactive collisions ZR with relative energies E > Ea is smaller
than the total collision number Z and follows after integration with the activation
energy as lower limit 
ZR     dE
2
Ea
 E   E 
In this case the result is: ZR  Z  a  1 exp   a 
 RmT   RmT 
 The expression can be directly compared to the macroscopic reaction rate Rj
 It shows the typical T-dependence of a rate coefficient according to Arrhenius
3.43
3.6 Complex gas-phase reactions

3.6.1 Reverse reactions
Chemical reactions do not result in a total

conversion of reactants to products
They proceed only until an equilibrium is reached A  B 
k1
C  D
k1
This observation can be easily explained by A  B 
 C  D
k 1
assuming not only a forward but also a
reverse reaction
In the first case, the formation of C and D only
stops, if one of the reactants is used up
(complete chemical reaction)
In the second case, the backward reaction
becomes more and more important with
increasing concentrations of C and D
dc C dcD
The reverse reaction is then in competition   R1  R1
dt dt
with the forward reaction and prevents
 k1c A cB  k 1cCcD
complete conversion of the reactants
3.44
Kinetic interpretation of the chemical equilibrium
In case of equilibrium, the net temporal changes of all concentrations become zero,
i.e., the rates of the forward and backward reaction must be equal
dc i
0
dt
R1  R1
k1c A cB  k 1cCcD
c C cD k Compare to thermodynamic interpretation
 1  KC
c A cB k 1 of equilibrium (chapter 2)!
We recognize: The chemical equilibrium is a dynamic equilibrium
The ratio of the rate coefficients of the forward and backward reaction is equal
to the equilibrium constant Kc
The chemical reactions do not stop once the equilibrium is reached – but forward
and backward reactions are then balanced, i.e. have identical rates
3.45
Generalization: Chemical reactions with reverse reaction
k
 j

The expression of the reaction rate Rj  ij Ai 

  A ij i
is based on a single rate coefficient k j
only i
 ij
 The reverse reaction is considered kj  p 
 K c , j  K p, j  0 
through the equilibrium constant k j  RmT 
Kc,j of reaction j
 The rate coefficient k–j of the
reverse reaction can be Kp = exp(–RG/RT)
determined from kj and the
thermodynamic determination i
of the equilibrium constant  ij

kj  p 
 exp  G RT   0 
k j  RmT 
3.46
The path towards equilibrium
The reaction rate Rj of a reaction A P

with reverse reactions is:
1
R j  k j  ci  k  j  ci
 ij  ij
Concentration / [A]0
[P]
 c 
ij
1
R j  k j  ci
ij
1 
i

c
ij 0.5
 Kc , j i  [A]
At start of reaction =1
In equilibrium =0
0 1 2 3 4 5
Time / 1/2
The reaction rate approaches

R = 0 before the reactants are
In the chosen representation, all
completely used up
stoichiometric coefficients are positive
3.47
3.6.2 Subsequent reactions:

Quasi-steady-state approximation
For simple chain reactions without

branching it is often possible to determine A BP
the reaction rate by assuming the
d [B]
concentration of a reaction intermediate 0 [B]  const.
(i.e., radical) to be in ‘steady state’ dt
The assumption of a quasi-steady state means:
 Constant radical concentration during [A]

Concentration
[P]
the main part of the reaction
 Time-dependent concentration of all
other species’ concentrations [B]
These assumptions do not hold at the start

and the termination of a reaction
t
3.48
Quasi steady states: Analytical solution
1
k1 k2 [P]
A B P
0.5
Rate laws:
[A]
d [A]
 k1[ A ] [B]
dt
d [B] 0 1 2 3 4 5
 k1[ A ]  k 2 [B]
dt Time / 1/2
d [P] Analytical solutions:
 k 2 [B]
dt [A]  [A]0 exp( k1t )
Initial conditions:  k1 
[B]  [A]0  exp( k2t )  exp( k1t ) 
[ A ]( t 0 )  [ A ]0  k1  k2 
[B]( t 0 )  0  k1 k2 
[P]  [A]0  1  exp( k2t )  exp( k1t ) 
[P]( t 0 )  0  k1  k2 k1  k2 
3.49
Quasi steady states: Simplified solution
Steady state assumption: 1

[P]
d [A]
  k 1[ A ]
dt
d [B] 0.5
 k1[ A ]  k 2 [B]  0
dt [A]
d [P]
 k 2 [B] [B]
dt
0 1 2 3 4 5
[ A ]  [ A ]0 exp( k1t ) Time / 1/2
[B]  k1 k 2 [ A ]  k1 k 2 [ A ]0 exp( k1t )
d [P]
 k1[ A ]0 exp( k1t )
dt
[P]  [ A ]0 1  exp( k1t )
3.50
Subsequent reactions with equilibria:
Pressure dependence according to Lindemann (1922)
Rate coefficients of dissociation reactions are pressure dependent. A monomolecular decay
is only possible if the molecule has sufficient energy for example from collisions with other
molecules M. Activated molecules A* can be deactivated by further collisions
ka
A + M → A* + M (Activation)
k –a
A* + M → A + M (Deactivation)
ku
A* → P (unimolecular reaction)
d [P] d [A*] k [A][M]
 ku [A*]  k a [A][M]  k  a [A*][M]  ku [A*] = 0 [A*]  a
dt dt k  a [M]  ku
The assumption of quasi-stationary [A*] leads to two limiting cases:
Low-pressure limit: [M] (i.e., p) is low, resulting in a reaction of second order. The activation of
A is slow and rate determining  The reaction rate is pressure dependent
[ A* ]  k a k u [ A][M] d [P]
 k a [ A][M]
dt
High-pressure limit: [M] (i.e., p) is high, resulting in a first-order reaction. The decay of A* is
rate determining  The reaction rate is pressure independent
d [P] kuk a
[A*]  k a k  a [A]  [A]  k  [A]
dt ka
3.51
Pressure dependence of reaction rate coefficients
 The rate coefficient k of the reaction d[P]/dt = k [A] depends on pressure. In the
high-pressure limit it becomes pressure independent (k∞), at low pressure it is
k’[M] and thus pressure dependent
 The pressure-dependent plot is called fall-off curve
Example:
k/k Fall-off curves for monomolecular decay C2H6 → CH3 + CH3

300 K
0,5 520 K 873 K 1350 K
0,2 1700 K
2000 K
0,1
0,05 The individual k curves are

normalized to the high-pressure
maximum k∞. The absolute k values
-1 0 1 2 3 4 5 increase with temperature
log (p/mbar)
3.52
3.6.3 Chain reactions: General scheme
Pyrolysis and oxidation reactions of fuels do not proceed in a single-step.

They consist of a sequence of radical reactions
Radical-chain reaction: A sequence of elementary reactions, in which radicals play
a mayor role. The reaction products of one elementary reaction are needed for the
subsequent reactions
Example: Hydrogen combustion (simplified)

Start: H2 + O2  2 OH• Formation of radicals
Propagation: OH• + H2  H2O + H• Conservation of radicals
Branching: H• + O2  OH• + O• Increase in radical

concentration
O• + H2  OH• + H•
Termination: 2 H• + M  H2 + M
Depletion of radicals
H• + O2 + M  HO2• + M (HO2 is still a radical, but a quite inactive one, cf. 3.67)
3.53
Chain reactions in combustion science

Chain reactions consist of two types of mechanisms that differ in the
behavior of the radicals:
Chain reactions without chain branching:

The concentration of radicals remains limited
Example: Pyrolysis reactions
Chain reactions with chain branching:

The number of radicals can increase very fast (exponentially)
Example: Combustion reactions, explosions
Characteristic for combustion reactions is the self-acceleration of the reaction

After ignition, the reaction rates increase exponentially
 The reaction maintains itself
3.54
3.7 Pyrolysis reactions
Pyrolysis:
Thermal decomposition of larger molecules (e.g. hydrocarbons) to smaller products.
Reactions proceed without oxygen or with oxygen deficiency at high temperatures.
Pyrolysis reactions play an important role during the oxidation of fuels
Example: Pyrolysis of ethane C2H6 ↔ H2, C2H4, CH4

At temperatures above e.g. 550°C the products H2, C2H4, and CH4 were found
Pyrolysis reactions proceed according to simple laws. In the past, they have been
erroneously described as elementary reactions
Today they have been recognized as chain reactions
Experimentally observed reaction law: dC2H4  dt  C2H6 

This first order does not indicate that the reaction is an elementary reaction!
3.55
Pyrolysis of C2H6
During the decomposition of C2H6 the radicals H and CH3 were detected as
intermediates. This proved that the decay proceeds as a chain reaction
Meanwhile the following chain mechanism has been accepted:
R1 C2H6 
1
CH3  CH3
R2 CH3  C2H6 
2
CH4  C2H5
R3 C2H5 
3
C2H4  H
R4 H  C2H6 
4
C2H5  H2
R5 H  C2H5 
5
C2H6 (preferred in the presence of a collision partner M)
The elementary reactions can be grouped into different types:

R1 Initiation reaction start the total mechanism
R2, R3, R4 Chain propagation reactions do not change the over-all radical
concentration
R2 Conversion reaction: CH3 is converted to C2H5
R5 Chain termination: Radicals are converted back to stable species.
A collision partner M is usually required to “cool” the product
3.56
Reaction mechanism C2H6 pyrolysis
Reaction rates Rate of change of the molar

concentrations
R1  k1[C2H6 ] d [CH3 ]
For radicals:
 2R1  R2
R2  k 2 [CH3 ][C2H6 ] dt
R3  k 3 [C2H5 ] d [H ]
 R3  R4  R5
 dt
R4  k 4 [H ][C 2H6 ]
d [C2H5 ]
 
R5  k 5 [H ][C 2H5 ]  R2  R3  R4  R5
dt
d [C2H4 ]
For product:  R3
dt
The resulting equations form a system of coupled non-linear differential
equations. It can only be solved numerically
 Reaction mechanisms – like that of ethane pyrolysis – can be found as a
result of experiments
3.57
Simplified description of pyrolysis

with steady-state assumption
Mechanism: See last section After some transformations, combining all three
Experimentally-observed reaction law: algebraic equations and solving for [C2H5]:
d C2H4   12

 C2H6   k1  k1  k1k 4  
2
dt

[C2H ]  
5 ss      [C2H6 ]
 2k 3  2k 3  k 3 k 5  
 
With the steady-state assumption for the 12
kk  k1
radical concentrations and the reaction   1 4  [C 2H6 ] w ith  1
scheme of the C2H6 pyrolysis reaction  k3k5  2k 3
(shown above) it follows: According to the differential equations shown
above, d[C2H4]/dt can be directly calculated
d [CH3 ] using the steady-state concentration of [C2H5]ss:
0  2k 1[C2H6 ] k 2[CH3 ][C2H6 ]
dt
d [H ] d [C2H4 ]
0  k 3[C2H5 ] k 4[H ][C2H6 ]   R3  k 3[C2H5 ] k 3[C2H5 ]ss
dt dt
1/ 2
k 3[H ][C2H5 ] d [C2H4 ] k k k 
  1 3 4  [C2H6 ]
d [C2H5 ] dt  k5 
0  k 2[CH3 ][C2H6 ]  
dt  [C2H6 ]
ss: steady state
3.58
3.8 Explosions, chain branching
In the chain reactions discussed so far, the formation and consumption of radicals
was balanced. Therefore, the radical concentrations stayed at low, limited values
In contrast, mechanisms of the oxidation of fuels include chain-branching reactions
that strongly increase the radical concentration
Example: Chain-branching reactions in the H2/O2 system:
H  O 2  OH  O
O  H2  OH  H
A single radical (H or O) initiates the formation of two radicals (OH and O) and
(OH and H), respectively
The increasing number of radicals accelerates the reaction (avalanche effect)
3.59
Theory of chain explosion

Process with a “fast” release of thermal energy: The temporal behavior of systems is
an important indicator (this is not a complete reaction equation, A, P, R represent classes of species not
individual species!)
A  R 
k
 P  β R
A: Reactant concentration
d [A]
  k0 [R ] P: Product concentration
dt R: Radical concentration
d [R ]  describes the relative increase in radical concentration
 k0 β  1 [R ]
dt Description of d[A]/dt as pseudo-first order reaction (see 3.11)
Example:
Linear system d [R  ]
 0 [A]0 = 1019 molecules/cm³
behavior  = 1 dt
[R]0 = 1 molecules/cm³
(Quasi stationary) k0 = 108 collisions/s
Simplification: Every
 Reaction time > 1011 s collision is successful
“Explosive” system d [R ] Initial conditions as above,

 k 0 [R ]
behavior:  = 2 dt =2
[R  ]  expkt   Reaction time approx. 10–6 s
3.60
Conditions for an explosion
Because of chain-branching reactions, the total number of radicals can increase

strongly, i.e., explosively. There is no steady-state condition for the radicals in
systems with chain branching. The reactions get faster and faster  Explosion
Formal representation of a reaction mechanism with chain branching:
(these are not complete reaction
A 
k1
 R  A Chain initiation equations, A, P, R represent classes
R  A 
k2
 R  A Chain branching of species not individual species!)
R  A 
k3
 P Product formation A: Reactants and intermediates
P: Stable product
R 
k4
A Chain termination, gas R : Radical
> 1
R  
k5
 A Chain termination, wall
 Describes the relative increase
in radical concentration
Condition for an explosion:

The formation rate of the reaction products becomes very large
and increases “beyond all limits”
3.61
Explosion limits
Formation rate of the reaction products and of the radicals R according to the
formal chain branching mechanism:
d [P]
 k3 [R ][A]
dt
If [R] increases strongly the product
d [R ] formation rate d[P]/dt increases
 k1[A]  k 2 (  1)[R ][A]  k3 [R ][A]
dt accordingly
 k 4 [R ]  k5 [R ]  Explosion
d [R ]
0
dt
If the expression in the
 k1[A]
[R ]  denominator vanishes, the
k3 [A]  k 4  k5  k 2 (  1)[A] reaction rate becomes infinite
d [P] k3k1[A]2 and the requirement for an
 explosion is fulfilled
dt k3 [A]  k 4  k5  k 2 (  1)[A]
3.62
Explosion limits
From the condition “denominator = zero”, a limiting value crit for chain branching
can be determined for chain explosions:
For  > crit the system is explosive

k [A]  k 4  k5
crit  1 3 for  < crit the reaction product is formed in a
k 2 [A] slow reaction
 k  k  k5 In gas phase reactions: [A] ~ p
crit   1  3   4
 k 2  k 2 [A]
The reaction coefficients are T-dependent
This results in pressure- and temperature-dependent explosion limits

for a fuel/oxidizer mixture
The existence of explosion limits is typical for chain-branching reactions
 Chain branching must compensate radical losses due to gas-phase and
wall-induced termination reactions
3.63
Explosion limits for H2/O2 mixtures
Experimental determination Example

of explosion limits: At T = 750 K and p = 1 bar, an
The mixture is filled into a glass vessel extremely slow reaction takes
inside an oven at controlled temperature place inside the system
An explosion occurs after
 isothermal compression to 10 bar
or
 pressure reduction to 10–2 bar!
Results are presented in the

H2, O2 explosion diagram
1 bar
3.64
Explosion limits of stoichiometric H2/O2 mixtures
. 10
For T > 850 K:

Explosion at all pressures
1
Slow reaction
Pressure / bar
At 675 K < T < 850 K:
Explosion or slow reaction, 10–1
depending on pressure
Explosion
10–2
For T < 675 K:
Slow reaction at all pressures
10–3
. Temperature / K
3.65
Qualitative cross-section through the explosion diagram of

a stoichiometric H2/O2 mixture
d H 2 O 
dt T = 750 K
Pressure dependence
of the rate of formation
2nd Explosion limit
3rd Explosion limit

1st Explosion limit
of the reaction product

H2O at T = 750 K (in the
“intermediate”
temperature range)
At the explosion limits and

in the explosion regions,
high formation rates of
H2O are reached. Chain Stationary Thermal
Of course, in reality no explosion reaction explosion
“unlimited” values are
achieved
log p
3.66
Explanation for the explosion limits
Lower (first) explosion limit: Because of low pressure and long mean free paths, the
chain termination reactions at the wall are stronger than the radical production
Important are: H 
Deactivation at the wall
OH  
Second explosion limit: Balance of radical production and destruction in the gas
phase, the latter e.g., through:
H  O 2  M  HO2  M
HO2  wall
The radical HO2 is relatively inactive, can diffuse to the walls, and be deactivated
Between the first and second explosion limit:  Chain explosion
Third explosion limit: Heat release is faster than heat conduction
Increasing temperature accelerates the reaction  Thermal explosion
Increasing temperature enables
 HO2  H2  H2O 2  H
HO2 to undergo further chain-
branching reactions H2O 2  M  OH  OH  M
 Rapidly increase in radical concentration
3.67
Theory of thermal explosions

In this case the self acceleration of chemical reactions is described through the
release of chemical bond energy and the associated temperature rise. The latter
results in an additional acceleration of the reaction rate
(Thermal explosions are often also called heat explosions)
Model by Semenov: Heat source (reaction):
Single-step reaction: F → P  J m3s 1 
q   R h R
 E 
with R  F k0 exp  a 
 RT 
Rh : Specific reaction enthalpy
R: Reaction rate (here: first order)
F : Fuel density (assumed constant)
k0 : Frequency factor
Heat loss (heat conduction through wall):

q    A V T  T0  J m 3 1
s 
: Heat transfer coefficient
T: Gas temperature (assumed homogeneous)
T0: Wall temperature
3.68
Conditions for thermal explosions
Temperature effect through comparison of heat fluxes
dT 1  1  R  E  
  q  q      hm F k0 exp  a    A T  TW  
dt  cV  cV   RT  
q   q    0 : Stationary reaction

The heat released by the chemical reaction is removed from the system
 Constant temperature
 Constant reaction rate
q   q    0 : Explosion
The released heat remains in the system
 Increasing temperature
 Increasing reaction rate: Self-acceleration!
3.69
q 
instable T03 q  for different
The following facts are obvious: q  stationary c T02
q  point wall temperatures
T01
stable
 There is an exponential stationary
T01  T02  T03
temperature dependence point
b
of q  according to the
Arrhenius law for R a
 There is a linear
dependence of q  on T T
q   q 
according to the law of
heat exchange
T01
Explosion
T02
T03
T
3.70
The following cases are possible:
T0 = T01: Relatively high wall temperature, no interception

between q  and q  . q   q   is always positive,
 Explosion!
T0 = T03: Two interceptions between q  and q  . For the
initial condition T = T0 a stationary gas
temperature Ta is reached. The same is reached
for T0 < Tc. Only for T0 > Tc the reaction is
self-accelerating
T0 = T02: Limiting case with T = Tb . The initial temperature
equals the auto-ignition temperature. This is the
limiting temperature for a self accelerating reaction
3.71
Theory by Frank-Kamenetskii
Semenov theory
 Uses simplification of spatially-invariant temperature distribution
Frank-Kamenetskii theory is more general:

 Includes temperature inhomogeneities
 The gas temperature at the wall equals the wall temperature
 Assumption: Single-step reaction without change in fuel concentration
 Description depends on the geometry of the system (for one-dimensional
geometries it must be distinguished between infinite gap, infinite cylinder and
sphere)
3.72
Temporal behavior of explosions
Thermal explosion Chain explosion

log T log T
ind
t t
During the induction time ind in chain explosions: Important radical chain reactions
are in progress (initiation, chain branching) that do not significantly increase the
temperature
Inhibition of explosions: Through the addition of water vapor or other inert gases, the
explosion limits can be shifted
3.73
3.9 Ignition delay
The behavior found in larger

hydrocarbons causes a delayed
ignition that is characterized by
Pressure / bar
an induction period with

subsequent fast reactions
Explosion Within the induction period:
Occurrence of so-called cool
flames where the fuel is partially
Methane oxidized while only minor energy
release is observed
Ethane
Here, a decrease in reaction rates
Steady reaction Propane
can be observed despite of
increasing temperatures
Cool Temperature / °C
flame
3.74
Ignition delay: Hydrocarbons
Ignition delay times are strongly temperature-dependent because of the

temperature-dependence of the underlying chemical reactions
They show the typical Arrhenius behavior k  A exp B T 
Because of  ~ 1 k the slopes are positive
3.75
Two-step ignition
Temperature profile Ignition delay: negative temperature

n-heptane / air, 15 bar coefficient: n-heptane / air
3.76
Oxidation of alkanes
nC7H16 X•
H
•
+ XH
•
-Decomposition •
•
nC7H15 products
• • CH3• •
+ O2
R7OO • OO•
O•
O H HOO
Q7OOH •
HOO HOO
+ O2
•
OOQ7OOH •OO
HO
OQ7OOH + OH• HOO O O
+ •OH
O H • HOO HOO
O•
Chain branching
3.77
nC7H16
-Decomposition
nC7H15 products
OH
+ O2 + O2 O
R7OO HO2• + nC7H14 •
+ HO2•
OH
OH• + O O
Q7OOH •
+ •OH
Cyclic Ethers
+ O2
OH OH
OOQ7OOH O O O
OH• + •RCHO +
• • + + + •OH
CnH2n
OQ7OOH + OH•
Chain branching
3.78
nC7H16 High-temperature
mechanism (Ea ~ 125 kJ/mol)
NTC
-Decomposition
Conversion
nC7H15 products
+ O2 + O2
R7OO HO2• + nC7H14
Q7OOH OH• +
Cyclic Ethers Reactor temperature
+ O2
OOQ7OOH
OH• + •RCHO + NTC: Negative Temperature
CnH2n coefficient (nominally negative
Intermediate-temperature activation energy in the Arrhenius
OQ7OOH + OH• mechanism (Ea ~ 80 kJ/mol) equation): Increase in T leads to a
deceleration of the reaction
Chain branching
3.79
Explosion limits
 Explosion limits can be explained from the detailed reaction mechanism of the
oxidation reactions
 An explosion can be attributed to the
• exponential increase of the radical concentration or
• the fast energy release with subsequent temperature rise
and the resulting strong increase in the formation rate of the products. Therefore,
all flames must be considered as an “explosive” combustion process.
However, in stationary flames the over-all rate is limited by transport phenomena,
not by the combustion progress!
 Explosion limits: Pressure and temperature limits are observed for each specific
fuel-oxidizer mixture. They limit the stationary reaction regions. The expression
“ignition temperature” is connected to the explosion limits (see later)
 Flammability limits must be distinguished from explosion limits! They give the
upper and lower limits of the mixture composition, beyond which an explosive
flame propagation for a given state (p,T) is not possible (see chapter 5)
3.80
3.10 Examples of detailed oxidation mechanisms
For many simple fuels, like H2, CO, CH4, C2H2, C2H4, and other simple
hydrocarbons, detailed oxidation mechanisms with the respective rate
coefficients for the elementary reactions are available
They can be verified based on measured characteristic combustion properties,
like
 Explosion limits
 Laminar burning velocity
 Induction times
 Ignition temperatures
Many detailed kinetic reaction steps during hydrocarbon oxidation are still not
fully investigated (because there are thousands…)
The formation of pollutants during combustion is tightly coupled with the fuel
oxidation and can not be examined without knowledge of the respective
oxidation mechanism
3.81
Reaction mechanism of the H2/O2 system

Elementary reaction Rate coefficient
cm3mol–1s–1 or cm6mol–2s–1
The kinetics of the H2 + O2 reaction 1 H2  O2  OH  OH 2.5  1012exp(  19650 K/T )
mechanism is well known. It can be 2 H2  M  H  HM 4.4  1014exp(  48300 K/T )
1 3 O2  M  O  OM 2.0  1014T 2.5exp(  59400 K/T )
grouped in the following way:
4 H  O2  OH  O 1.2  1017T 0.91exp(  8300 K/T )
5 OH  O  H  O2 1.8  1013
1: Initiation reactions 6 O  H2  OH  H 1.5  107T 2exp(  3800 K/T )
2
2: Chain-branching and chain- 7 OH  H  O  H2 6.7  106T 2exp(  2800 K/T )
propagation reactions 8 OH  H2  H2O  H 1.0  108T 1.6exp(  1660 K/T )
3: Recombination reactions 9 OH  OH  H2O  O 1.5  109T 1.14
4: Formation and consumption of HO2 10 H  H  M  H2  M 1.8  1018T 1
3
5: Formation and consumption of H2O2 11 H  OH  M  H2O  M 2.2  1022T 2
12 H  O2  M  HO2  M 2.0  1018T 0.8
The rate coefficients of the reverse reactions 13 H  HO2  OH  OH 1.5  1014exp(  505 K/T )
can be calculated with equilibrium constants 4 14 H  HO2  H2  O2 2.5  1013exp(  350 K/T )
according to JANAF tables 15 O  HO2  OH  O2 2.0  1013
16 OH  HO2  H2O  O2 2.0  1013
17 OH  OH  M  H2O2  M 3.2  1022T 2
5 18 H  H2O2  H2O  OH 1.0  1013exp(  1800 K/T )
19 H2O2  M  OH  OH  M 3.0  1017exp(  22850 K/T )
3.82
Reaction mechanisms: Further examples
CO oxidation in the presence of H2O Thermal NO formation

(Zeldovich mechanism)
Elementary reaction Rate coefficient Elementary reaction Rate coefficient

cm3mol–1s–1 or cm6mol–2s–1 cm3mol–1s–1 or cm6mol–2s–1
1 CO  O2  CO2  O 5.0  1013 exp(31800 K/T ) 1 O  N2  NO  N 1.8  10 14 exp( 38370 K/ T )
2 O  H2O  OH  OH 6.8  10 exp(9250 K/T )
13
2 N  O 2  NO  O 6.5  10 9 T exp( 3150 K/ T )
3 CO  OH  CO2  H 4.0  1012 exp(4030 K/T ) 3 N  OH  NO  H 1.4  10 11
4 H  O2  OH  O 2.2  1014 exp(8450 K/T )
5 CO  O  M  CO2  M 2.4  1015 exp(2180 K/T )
In case of the oxidation of CO, it must be

distinguished between dry and moist
oxidation. During the moist oxidation, which
is more important for practical applications,
the main oxidation proceeds from CO to
CO2 via the fast elementary reaction:
The rate coefficients of the reverse reactions can be calculated
CO + OH  CO2 + H with equilibrium constants according to JANAF tables
3.83
Reaction mechanism of CH4 oxidation
Elem. reaction Rate coeff. Unit Elem. reaction Rate coeff. Unit
The marked reactions are part of the

(pure) hydrogen oxidation mechanism
Bowman, Proc. Combust. Symp. 15, 869 (1974)
3.84
Sensitivity analysis
Within the reaction mechanism some reactions are “more important“ than others.
I.e., a small variation in their rate coefficients has an especially large impact on the
overall reaction process
The sensitivity can be determined numerically by checking the response of the total
result on small variations of a single reaction rate
For the “important reactions“ high-quality kinetics data (exact description of the rate
coefficients) is crucial
lean
Rel. sensitivity CH4 / O2 Rel. sensitivity C2H6 / O2 stoichiometric
rich
Reaction
3.85
Sensitivity analysis: n-heptane combustion
The combustion mechanisms of larger hydrocarbons are still sensitive

to the same reactions!
Mainly:
H + O2 → O + OH
CO + OH → CO2 + H
3.86
Hierarchical structure of reaction mechanisms
 A hierarchical structure of the combustion mechanism can be described

according to the observation that – no matter which hydrocarbon is burned –
a few reactions play a special role for a specific fuel
 The largest over-all throughput and the largest per-reaction energy release is
found in the core of the hierarchical structure
3.87
Methane oxidation
a) Stoichiometric b) Rich
The oxidation runs primarily via C2-HCs and ends

Step-wise oxidation here at C2H2, which must be further oxidized. Soot
Small contribution of higher HCs formation occurs via acetylene and poly-acetylenes
3.88
Ethane oxidation
Flame conditions:
p1 = 1 bar, T1 = 300 K,
stoichiometric mixture of
C2H6
The decomposition of
C2H6 primarily proceeds
via C2 hydrocarbons
3.89
3.11 Simplification of reaction mechanisms
For numerical simulations it is often necessary to reduce the number of variables

while maintaining some (reasonable) information about the chemical reaction
scheme
Therefore, reaction mechanisms are simplified by:
 Assumption of a single-step reactions (“mixed = burned“ for non-premixed flames)
 Take advantage of quasi-steady state conditions (see section 3.2.2)
 Take advantage of partial equilibria
 Simplify mechanisms based on results of a sensitivity analysis
 Mathematical reduction of complex mechanisms (“Intrinsic low-dimensional
manifolds“ ILDM)
(listed by increasing quality)
 Simplified mechanisms need experimental validation!
Background: Processes act on very different time-scales. Some of the partial
processes are so fast that they can be considered to be in equilibrium, some are
so slow that they can be neglected (frozen). Most important are reactions at
comparable rate as the transport processes
3.90
Time-scales in reacting flows
Chemical time scales Physical time scales
Slow processes 1s
i.e., NO-formation
“frozen reactions“ 10–2 s
Flow, transport
Intermediate time-scales 10–4 s turbulence
Fast time scales 10–6 s
“equilibrium reactions”
(quasi-stationary processes, 10–8 s
equilibria)
Intermediate time-scales must be fully resolved to describe interaction of

chemistry and transport, fast and slow processes can be simplified
3.91
Partial equilibria
k1
Example: H + O2 OH +O k1 [H] [O2] = k2 [OH] [O]
k2
k3
O + H2 OH +H k3 [O] [H2] = k4 [OH] [H]
k4
k5
OH + H2 H2O +H k5 [OH] [H2] = k6 [H2O] [H]
k6
1/2
k1 k3k52 [O2] [H2]3
[H] = k k k 2 [H O]2
2 4 6 2
k1 k5 [O2] [H2]
[O] =
k2k6 [H2O]
k1 k3 1/2
[OH] = k k
2 4
 The radical concentrations are directly derived from the stable species
concentrations
3.92
ILDM
Intrinsic low-dimensional manifolds Example:
nH2O / mol/kg
(ILDM): Methane oxidation
Mathematical reduction of the set of
equations that describes all variables
(concentrations) not by removing
apparently “unimportant“ reactions but
by mathematical dimension reduction
Example CH4 oxidation:

After a short initial period nCO2
(< 50 µs, see lower plots) species
concentration are closely correlated
and move “together” towards the
global equilibrium composition (red
dot).
t > 5 ms t > 50 µs
3.93
Chapter 3: Essentials
 Reaction rate / rate of change of concentrations

 Reaction order / reaction molecularity
 Global reaction / elementary reaction
 T, p, x-dependence of the reaction rate / Arrhenius law
 Measurement strategies
 Reverse reaction: Equilibrium
 Subsequent reactions: Quasi-stationarity
 Radical chain reaction: Chain propagation / chain branching
 Explosion condition, explosion limits
 Ignition delay, two-step ignition
 Detailed mechanisms, hierarchical structure of mechanisms
 Sensitivity, simplification of mechanisms
3.94

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3 Chemical kinetics of gas-phase reactions

3.1 Basic concepts

Chemical kinetics describe

The kinetics of combustion reactions is an important field of the general chemical

Concentration and reaction rate

Through a systematic analysis of –RA(t = 0)

The reaction progress is measured through the increase of the concentration or

The experimentally-determined dependences often give indications about the way

 The reaction order  is an experimental value that is not necessarily integer

 Not every reaction mechanism can be globally represented by a reaction order

Rare. The reaction rate is independent

Typical in radioactive decay:

Half-life period is independent

Second-order reaction: Examples

Data evaluation: First or second order?

Analysis of experimental data

First order Second order

 Slow reactions (1/k ~ minutes): Batch reactor

Detection methods for gas-phase concentrations

 Stable reaction partners

Investigation of short-lived intermediates

Determination of reaction rates of combustion-relevant

Effects of probes inserted Optical diagnostics:

Fast reactions can be studied in

via Shock wave

b) Reflected wave Reflected shock wave

Sampling of molecules and particles at 5

different positions downstream of the flame 4

2 Conc Sn(CH3)4 = 823 ppm

Experimental investigations yield:

Stoichiometric reaction equation: Stoichiometric reaction equation:

Measured reaction rate: Measured reaction rate:

dHI dHBr  k H2  Br  2

In this case, the reaction equation does

H2  Br2  2 HBr Global reaction equation

The detailed kinetics in case of the HBr-formation is known:

 The kinetics of the HBr formation from H2 and Br2 follows

Only few global reactions proceed in one

According to a molecular dynamics view, an

The molecularity of a Bimolecular reactions:

The activated complex is a

Uni- and trimolecular reactions

Elementary reactions with a higher molecularity than 3 can be neglected

The reaction progress of an elementary reaction can be described through the

1 V Definition of the reaction progress variable (cf. chapter 2)

Rate of change of concentrations

The reaction rate Rj of an elementary reaction j is defined as the temporal variation

Through a transformation of the above equation, one obtains the change in

3.5 Dependences of the reaction rate Rj

The reaction rate Rj of an elementary reaction is a function of temperature,

This dependence can be written in form of a product:

For elementary reactions, the function Fj (depending on the molecularity of the

R j T,c i   k j T   c i  ij mol cm–3 s–1

k (T )  k0 exp   Ea RmT  k0: Frequency factor

 The Arrhenius law is universally valid for elementary reactions

Examples of Arrhenius diagrams

In tables you often find the activation

Elementary reaction H + O2 → OH + O Thermal decomposition of CH4

Rate coefficient / cm3mol–1s–1

Example for temperature-independent reactions:

Rate coefficients for many elementary reactions can be found in:

Reaction rate according to Arrhenius A  BC  j

: Mean collision cross-section