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The most frequently used design of a catalytic converter is a monolithic structure (Fig.
8.1), which is coated with a washcoat that supports the catalyst material. The devel-
opment of such a catalytic converter is a complex process involving the optimization
of different physical and chemical parameters. Simple properties such as monolith
length, cell density and metal loading of the catalyst influence the performance of the
converter. Numerical simulation using detailed models for the transport and chem-
ical processes are expected to accelerate the design and optimization of automotive
catalytic converters.
In this Chapter, the modeling and numerical simulation of steady-state and transient
processes in automotive catalytic converters are discussed. First the focus is on a
122 8. AUTOMOTIVE CATALYTIC CONVERTER
CO + 1
2
O2 → CO2
Cn Hm + (n+ m4 ) O2 → n CO2 + m
2
H2 O
CO + NO → CO2 + N2 .
The simultaneous conversion of all these harmful species can only be ensured if the
exhaust gas composition is very close to the stoichiometric ratio. This requirement
is technically controlled by the lambda-sensor and accompanying electronics for en-
gine control [32]. Meanwhile, the performance of 3WCC is almost perfect after the
catalytic reaction is ignited. However, at low operating temperatures, below 570 K,
almost no conversion of the pollutant emissions occurs. Therefore, current research
and development focuses on the reduction of this start-up period.
The majority of automotive catalytic converters have a monolithic structure made
of ceramics or metals. The walls of the monolith channels are coated with the wash-
coat, usually alumina, that supports the noble metal such as platinum, palladium and
rhodium. The monoliths consist of numerous parallel channels with a diameter of ap-
proximately 1 mm to have a large catalytic surface area. For the design of a catalytic
converter, several chemical and physical properties of both the catalyst and the ex-
haust gas must be considered, for instance the cell geometry (length and diameter of
the channels, wall thickness), the composition of the noble metal and catalyst loading,
the use of catalyst promoters, and the properties of the exhaust gas (temperature,
velocity and chemical composition).
The experimental characterization of the catalytic performance of the converter is
time-consuming and requires an expensive and complex experimental setup. Numerical
simulation offers an interesting alternative for the investigation of the catalytic activity
of a converter as a function of external conditions. This method is also efficient in
analyzing the transient flow and thermal phenomena in the catalytic converter and can
14
The effect of CO2 emissions on global warming is not a topic of this work.
8.2 Three-way catalyst 123
help to understand the complex interactions between the flow field and the catalytic
surface chemistry.
In recent years, several proposals were made for the numerical simulation of cat-
alytic converters [197–202]. In most of these studies, a global model for the chemistry
was used, which neglected the complex network of chemical reactions on the catalytic
surface. An alternate approach is the description of the chemical reactions by a set of
elementary-like reaction steps describing the chemical processes on a molecular level as
discussed in Chapter 3.2 and by Chatterjee et. al for 3WCC [87, 203]. This approach
is superior to any fitted global kinetics because it can be used to predict the catalyst
behavior at different external conditions. However, also the transport processes have
to be described and coupled to the chemical reactions in an accurate manner.
Detailed models for the chemistry and the transport processes are applied in this
study of a 3WCC. The numerical simulations are carried out using the computational
tools discussed in Chapter 4. The numerically predicted conversion of pollutants is
compared with experimentally derived data.
The catalyst investigated is a commercially available tree-way catalyst [87]. The
catalyst contains 50 g/ft3 of rhodium and platinum metal with a Pt/Rh ratio of 5/1.
The noble metals were impregnated on a ceria stabilized γ-alumina washcoat. The
washcoat was supported by a cordierite monolith with a cell density of 62 cells per cm2
(400 cpsi) and a wall thickness of 0.165 mm.
At first, the transport and chemistry in a single channel of the catalytic monolith
is discussed for steady-state conditions. Then the transient behavior of the 3WCC at
real operating conditions is described.
Experimental
The experimental determination of conversion as a function of temperature in the
three-way catalyst was conducted in an isothermal laboratory-scale tube reactor.15 A
sample of 22 mm in diameter and 29 mm in length was taken from the catalyst for this
investigation. Table 8.2 summarizes the composition and the species concentrations of
the exhaust gas sample. The oxygen concentration was varied in order to simulate a
stoichiometric, rich and lean exhaust gas mixture. The λox -values are defined as the
inverse of the redox ratio [197, 201, 87]:
XNO + 2XO2
λox = . (8.1)
XCO + 9XC3 H6
With this definition λox equals unity at stoichiometric conditions, and it is larger
(smaller) than unity for lean (rich) conditions. The volumetric flow of the exhaust
gas was 15 l/min at standard conditions (298.15 K). A uniform superficial velocity of
1.35 m/s corresponds to this volumetric flow rate. The reactor was heated with a tubu-
lar furnace with a heat rate of 100 K/h, which led to an almost isothermal sample. The
15
The experiment was carried out by S. Kureti and O. Görke at the University of Karlsruhe.
124 8. AUTOMOTIVE CATALYTIC CONVERTER
Table 8.2: Composition of the simulated exhaust gas used in the experiment and
simulation.
Noble metal composition Pt/Rh, 5:1
Noble metal loading 50 g/ft3
Active noble metal surface 0.247 m2 /g
Surface ratio Pt(s)/Rh(s) 3:1
Noble metal dispersion 29.1%
Catalyst surface/geometric surface (Fcat/geo ) 70
Channel diameter 1 mm
Channel length 29 mm
Superficial velocity (STP) 1.35 m/s
Mean pore diameter (micropores) 12.29 nm
Porosity (micropores) 27.9 %
Tortuousity 3
Washcoat thickness 100 µm
Active catalyst surface/washcoat volume 7.77·105 m−1
Table 8.3: Catalyst parameters used in the numerical simulation of the 3WCC.
maximum temperature gradient over the sample was reported to be 40 K caused by the
exothermicity of the oxidation reactions. The exit species concentrations were mea-
sured in 20 K steps. The steady state of the system was ensured at each temperature
step.
The CO2 concentration in the inlet exhaust gas was zero due to experimental rea-
sons. Tests have shown that there was no difference in conversion of CO, HC and NO
in measurements whether or not CO2 was added.
After the experimental studies of the temperature-dependent conversion, the sample
was investigated with H2 chemisorption in order to obtain the properties of the active
metal phase. The active metal surface of the catalyst was 28 m2 /g and the dispersion of
the conditioned catalyst was 33%. The calculation of the ratio of active metal surface
area and geometric surface area (Fcat/geo in Eq. 3.28) of the catalyst led to a value
of 70. The ratio of the platinum to rhodium surface was chosen to be 3:1 taken from
literature [204] for a catalyst with a noble metal composition of Pt/Rh with 5:1, which
corresponds to the catalyst used for the investigations.
8.2 Three-way catalyst 125
1.0 1.0
CO - conversion
experiment
simulation
0.6 eimulation 0.6
0.4 0.4
0.2 0.2
0.0 0.0
400 600 800 1000 400 600 800 1000
T [K] T [K]
1.0
0.8 experiment
NO - conversion
simulation
0.6
0.4
0.2
0.0
400 600 800 1000
T [K]
Numerical
It can be assumed that all channels of the monolith behave essentially alike because an
isothermal sample was used in the experiment, and the inlet conditions (flow velocity
and gas composition) did not vary over the various monolith channels. Therefore,
only one channel needs to be analyzed. The single-channel is assumed to be a tube-like
reactor with the flow inside this reactor being laminar. Hence, the single channel of the
monolith can be modeled by the axisymmetric two-dimensional Navier-Stokes equations
with the axial and radial directions as spatial variables as discussed in Chapter 2.2.1.
The flow field simulation is based on the CFD code FLUENT coupled with the chemistry
module DETCHEM as described in Chapter 4.3.1.
The flow enters the computational domain with a known velocity, gas composition
and temperature given by the experimental conditions. A flat profile of the axial
velocity and a vanishing radial velocity are used in the simulation at the inlet boundary.
At the reactor exit, an outlet boundary is applied at which values for all variables are
extrapolated from the interior cells adjacent to the outlet. A structured grid is used
for the simulation. The grid has to be very fine around the catalyst entrance and the
catalytic wall to resolve the flow field and also to determine the variations in the species
concentrations due to chemical reactions at the catalytic wall. The total number of
computational cells used for the single channel were 20 cells in radial direction and 72
126 8. AUTOMOTIVE CATALYTIC CONVERTER
1.0 1.0
experiment experiment
0.8 0.8
C3H6 - conversion
CO - conversion
simulation simulation
0.6 0.6
0.4 0.4
0.2 0.2
0.0 0.0
400 600 800 1000 400 600 800 1000
T [K] T [K]
1.0
experiment
0.8
NO - conversion
simulation
0.6
0.4
0.2
0.0
400 600 800 1000
T [K]
1.0 1.0
experiment experiment
0.8 0.8
C3H6 - conversion
CO - conversion
simulation simulation
0.6 0.6
0.4 0.4
0.2 0.2
0.0 0.0
400 600 800 1000 400 600 800 1000
T [K] T [K]
1.0
experiment
0.8
NO - conversion
simulation
0.6
0.4
0.2
0.0
400 600 800 1000
T [K]
of the reaction mechanism can be found in reference [203]; the mechanism is given in
Table B.5. In the simulation, the simplified washcoat model (Chapter 3.3.2) is used
with CO as species that determines the effectiveness factor (Eq. 3.49).
The experimental conditions are applied to the simulation. Table 8.3 summarizes the
input data for the simulation; the concentrations of the incoming exhaust gas are
already given in Tab. 8.2. The gas flows at a uniform velocity into the cylindric tube.
The temperature is set to the furnace temperature.
In Fig. 8.2, the conversion data of CO, C3 H6 , and NO are shown as function of
temperature. The composition of the inlet gas mixture is lean. The conversion of
CO, C3 H6 , and NO starts at 570 K and increases up to 100% for CO and C3 H6 at
770 K and 670 K, respectively. The NO conversion shows a maximum at 630 K and
decreases at higher temperatures. The predicted conversion of all three species agree
well with the experimentally measured data. Especially the temperature behavior
of the NO conversion and the slow increase of the C3 H6 conversion is well-predicted
in the temperature range above 630 K. The simulation shows some CO conversion
at temperatures lower than 570 K. This behavior is probably caused by the missing
reactions for hydrocarbons on rhodium in the mechanism. Therefore C3 H6 cannot
128 8. AUTOMOTIVE CATALYTIC CONVERTER
C3H6 6.70E-04
0.050
5.47E-04
0.025
r [cm]
4.25E-04
0.000
3.02E-04
-0.025
1.80E-04
-0.050
0.0 0.5 1.0 1.5 2.0 2.5
5.70E-05
z [cm]
CO 1.42E-02
0.050
1.14E-02
0.025
r [cm]
8.52E-03
0.000
5.68E-03
-0.025
2.84E-03
-0.050
0.0 0.5 1.0 1.5 2.0 2.5
3.50E-06
z [cm]
CO2 2.40E-02
0.050
1.92E-02
0.025
r [cm]
1.44E-02
0.000
9.60E-03
-0.025
4.80E-03
-0.050
0.0 0.5 1.0 1.5 2.0 2.5
0.00E+00
r [cm]
NO 1.07E-03
0.050
1.00E-03
0.025
r [cm]
9.38E-04
0.000
8.72E-04
-0.025
8.06E-04
-0.050
0.0 0.5 1.0 1.5 2.0 2.5
7.40E-04
z [cm]
Figure 8.5: Mass fraction profiles in a single channel of the 3-way catalyst monolith
at 673 K; lean conditions (λox =1.8) [87]. Different scales are used in axial and radial
direction for visual clarity.
130 8. AUTOMOTIVE CATALYTIC CONVERTER
10-1 Pt(s) 10
-1
Rh - surface coverage
Pt - surface coverage
NO(Pt) O(Rh)
-2
10 10-2
O(Pt)
10-3 10-3
OH(Pt) Rh(s)
N(Pt)
10-4 10
-4 NO(Rh)
CO(Rh)
10-5 10-5
C3H6(Pt)
10-7 10
-7
0 1 2 0 1 2
z [cm] z [cm]
Figure 8.6: Pt and Rh surface coverages along the catalytic wall in a single-channel of
a 3-way catalyst monolith at 673K; lean conditions (λox =1.8) [87].
0.8
conversion
0.6
0.4
0.2
0 0.5 1 1.5 2
λ ox
t=5s
T (K)
800
767
733
700
667 t = 15 s
633
600
567
533
500
467
433
400
367
333
300
t = 100 s
YCO
0.0142
0
conversion in the outer channels is still low (not shown), since the temperature is lower
due to the heat loss into the ambient air. A large region of the converter has reached
its operating temperature after 100 s. However, the CO profile in a single-channel in
the center of the catalyst does not differ from the one at 15 s of operating time. These
results elucidate that the overall reaction rate of CO oxidation is already mass transfer
limited.
Similar simulations have been carried out for temporally and spatially varying inlet
conditions [93]. The computation of an complete driving cycle for passenger vehicles
as given by European exhaust gas legislation [196] will take approximately 10 hours
CPU-time on Apple Mac G4 processors. In these simulations, between ten and twenty
representative channels are simulated at each time step in parallel manner, i.e., each
processor solves one channel.
8.3 DeNOx catalyst 133
Monolith diameter 20 mm
Monolith length 5 - 60 mm
Single-channel diameter 1 mm
Number of channels 201
Catalytic material Pt/Al2 O3
Pt-loading 1 weight-%
Pt-dispersion 17%
Active Pt-surface 0.22 m2 /g
Active catalyst / geometric surface (Fcat/geo ) 60.44
Mean diameter of the Pt-particles 6.5 nm
BET-surface 27 m2 /g
Pore volume 0.7257 cm3 /g
Mean diameter of the micropores 4 nm
Porosity of micropores 39.5%
Mean diameter of the macropores 5.98 µm
Porosity of macropores 10%
Washcoat thickness 100µm
ness and catalyst dispersion in the different catalyst samples used. These parameters
were not experimentally determined for each single sample.
Although NO reduction at lean conditions can be achieved, most of NO (70-80%
selectivity) is converted into N2 O. The emission of laughing gas (N2 O) is currently not
limited by legislation but is is known as harmful greenhouse gas, which really is the
problem with the commercial application of the HC-SCR/Pt system. The reason for
the observed selectivity is the total high coverage of the Pt-surface while N(s)-coverage
is low. This favors the reaction NO(s) + N(s) → N2 O and lowers the probability
of N(s) recombination to molecular nitrogen. The selectivity to N2 formation could
be increased if the use of promoters led to a higher activation energy for nitrogen
desorption.
The correlation between conversion and surface coverage is revealed by Figs. 8.10
and 8.11, in which the species profiles in the single channel and the surface coverage
along the channel wall inside the washcoat are presented. The results are based on a
simulation using the Boundary-Layer model (Chapters 2.2.2 and 4.3.2) and the detailed
washcoat model (Chapter 3.3.2). The oxidation of C3 H6 occurs within the first 2 cm
channel length. The reduction of NO is limited to the first 1.5 cm channel length,
behind that, NO2 formation occurs. While the surface is mainly covered by CO at
the channel entrance, oxygen becomes the primary adsorbate downstream of an axial
position of 1.6 cm. Yet the oxygen poisoned surface is inactive for NO reduction and
leads to NO oxidation instead. Hence, the width of the reaction zone of propylene
oxidation determines the zone, in which NOx can be destroyed.
The axial surface coverage at a certain washcoat depth, 0.45µm in Fig. 8.11, really
is a simplification and does not describe the more complex picture of the interaction of
diffusion and reaction inside the washcoat. Figure 8.12 presents the surface coverages as
8.3 DeNOx catalyst 135
1.0 1.0
0.8 0.8
conversion
0.6
conversion
0.6
0.4 0.4
0.2 0.2
0.0 0.0
400 500 600 700 800 900 400 500 600 700 800 900
T [K] T [K]
1.0 1.0
0.8 0.8
conversion
0.6
conversion
0.6
0.4 0.4
0.2 0.2
0.0 0.0
400 500 600 700 800 900 400 500 600 700 800 900
T [K] T [K]
1.0 1.0
0.8 0.8
conversion
conversion
0.6 0.6
0.4 0.4
0.2 0.2
0.0 0.0
400 500 600 700 800 900 400 500 600 700 800 900
T [K] T [K]
C3H6 5.00x10
-04
0.050 -04
4.00x10
0.025
-04
r [cm]
3.00x10
0.000
-04
2.00x10
-0.025
-04
1.00x10
-0.050
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 -09
6.58x10
z [cm]
NOx 5.00x10
-04
0.050 -04
4.76x10
0.025
-04
4.52x10
r[cm]
0.000
-04
4.27x10
-0.025
-04
4.03x10
-0.050
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 -04
3.79x10
z [cm]
NO2 1.89x10
-04
0.050 -04
1.51x10
0.025
-04
r [cm]
1.13x10
0.000
-05
7.56x10
-0.025
-05
3.78x10
-0.050
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 +00
0.00x10
z [cm]
Figure 8.10: Mole fraction distribution in a single monolith channel at 570 K; other
conditions as before.
O(s)
100 CO(s)
-1
10 NO(s)
surface coverage
-2 C3H5(s)
10
Pt(s)
10-3
C3H5(s1)
-4
10
0 1 2 3 4 5 6
z [cm]
Figure 8.11: Surface coverage along the catalytic channel wall inside the washcoat,
0.45µm away from the fluid/washcoat boundary, at 570 K; other conditions as before.
8.3 DeNOx catalyst 137
function of axial and radial position inside the washcoat. The CO(s) and O(s) profiles
reveal that the shift from CO(s) to O(s) coverage depends on the radial position inside
the only 100µm thick washcoat layer. Even at the washcoat entrance, a primarily
oxygen covered surface exists in 80µm washcoat depth. The other profiles reveal that
there are axial and radial variations of the surface coverages and, hence, the reaction
rates vary inside the washcoat.
CO(s) O(s)
1
surface coverage
surface coverage
0.6
0.4
0.5
0 0
0.2 1 1
2 2
0 3
m] z [c 3 100
4 z [c m] 4
r [µ 50 5 50
m] m]
r [µ
5
100 0
NO(s) N(s)
-04
surface coverage
2.0x10
surface coverage
0.1
0 1.0x10-04 0
0.05
1 1
2 +00
2
0 3 0.0x10 0 3
m] m]
4 z [c 4 z [c
r [µ 50 5 r [µ 50
m] m] 5
100 100
N2O(s) NO2(s)
-06
1.0x10
surface coverage
surface coverage
-09
3.0x10
-07
2.0x10
-09 5.0x10
0 0
-09 1 1
1.0x10 2
2
0 3 z [c 3 100
m] m]
4 z [c 4
50
r [µ 50 m]
r [µ
m] 5 5
100 0
Figure 8.12: Surface coverage with CO(s), O(s), NO(s), N(s), N2 O, and NO2 as func-
tion of axial and radial position in the washcoat layer; conditions are as before; the
fluid/washcoat boundary is at r = 0.
8.3 DeNOx catalyst 139
applied as a first step. Especially, if the simplified models involve unknown parameters,
e.g., for the description of the reaction kinetics, it is very risky to fit these parameters
to experimental data without having checked the accuracy of all the transport models.
Otherwise the fitted parameters will compensate for the errors in the transport model,
and conclusions drawn from the simulations are arbitrary.
1.0 1.0
0.8 0.8
conversion
conversion
0.6 0.6
0.4 0.4
0.2 0.2
0.0 0.0
400 500 600 700 800 900 0 2 4 6
T [K] z [cm]
1.0 1.0
0.8 0.8
conversion
conversion
0.6 0.6
0.4 0.4
0.2 0.2
0.0 0.0
0 2 4 6 0 2 4 6
z [cm] z [cm]
Figure 8.14: Comparison of conversion as function of axial position using the BL model
and PF model with mass transfer coefficients (both simulations include the detailed
washcoat model) at a temperature of 570 K (left) and 800 K (right); other conditions
are chosen as before.
140 8. AUTOMOTIVE CATALYTIC CONVERTER
1.0 1.0
0.8 0.8
conversion
conversion
0.6 0.6
0.4 0.4
0.2 0.2
0.0 0.0
400 500 600 700 800 900 400 500 600 700 800 900
T [K] T [K]
Figure 8.15: Impact of the radial mass transport in the fluid phase. Comparison
of experimentally determined conversion vs. temperature with numerical simulations
using the PF model with and without mass transfer coefficients (both simulations
include the detailed washcoat model); other conditions are chosen as before.
1.0 1.0
0.8 0.8
conversion
conversion
0.6 0.6
0.4 0.4
0.2 0.2
0.0 0.0
400 500 600 700 800 900 0 2 4 6
T [K] z [cm]
9 Conclusions
Experimental and numerical investigations were carried out to achieve a better under-
standing of the interactions between mass and heat transport and homogeneous and
heterogeneous chemical reactions in catalytic reactors. Gaseous chemically reacting
flows with heterogeneous reactions on solid surfaces are considered. The objective of
this research was the development of models and computer programs for the numerical
simulation of heterogeneous reactive flows.
In the experiments, catalytic reactors were studied for the partial and complete
oxidation of light alkanes at short contact times. The noble metals rhodium and plat-
inum served as catalyst. The conversion of the reactants and product selectivity were
determined by gas chromatography and mass spectrometry; the latter technique can
also be used for transient measurements. The temperature was determined by thermo-
couples. The reactor behavior was studied at varying conditions such as the flow rate,
temperature, dilution by an inert gas, and hydrocarbon/oxygen ratio. The experimen-
tal investigations served as basis for the development of reliable models. Experimental
data from collaborating research groups were also used as further independent sources
to judge the quality of the models applied.
A concept for modeling catalytic reactors was presented, in which all physical and
chemical processes were described as detailed as possible. These models were combined
to understand and, eventually, optimize the behavior of the catalytic reactor. The flow
field was modeled by the multi-dimensional Navier-Stokes equations coupled with an
enthalpy equation and one further governing equation for each chemical species. The
model includes temperature- and composition-dependent transport coefficients. The
chemistry in the gas phase was described by elementary-reaction mechanisms. The
heterogeneous reactions of gas-phase species on the solid surfaces were described by
multi-step reaction mechanisms, which were also based on the elementary processes.
In most previous studies, the numerical simulation of catalytic reactors is based
on simplifying assumptions, either for the flow field or the chemistry. For instance,
the flow field in tubular reactors is frequently assumed to be plug-flow-like, neglecting
any effect of radial mass transport, or the chemical processes are described by global
reactions with kinetic data fit to limited experimental measurements. Those models
can hardly be used for prediction or optimization of the reactor behavior.
In the concept presented in this work, the numerical simulations were based on the
most accurate models available. For instance, a monolithic reactors with rectangular-
shaped channel cross-sections were first modeled by a three-dimensional flow field sim-
ulation. Then, the results of these detailed simulations were compared with those of
simulations applying simpler models. This comparison allowed the potentials and lim-
itations of the simplifying assumptions to be recognized. It was found that the channel
flow in a catalytic monolith can be described by an axisymmetric flow field. Further-
more, axial diffusion can be neglected at high flow rates leading to the Boundary-Layer
equations. The simple Plug-Flow model failed to predict the reactor behavior cor-
rectly. It was also shown that an extended Plug-Flow model, which includs a radial
mass-transfer coefficient, works well for relatively slow reactions such as occurring in
automotive catalytic converters. However, this model cannot be used for very fast
142 9. CONCLUSIONS
codes such as FLUENT. The code DETCHEMCHANNEL simulates the reactive flow in
cylindrical and annular channel with catalytic active walls based on a Boundary-Layer
model. DETCHEMMONOLITH was written for the numerical simulation of the tran-
sient behavior of catalytic monoliths. In that code, the three-dimensional heat balance
equation for the monolithic structure is solved in combination of the simulation of the
reactive flows in the single channels.
The new approach for modeling catalytic reactors and the computational tools were
applied to investigate several catalytic reaction systems that have recently attracted
strong scientific and technological interest.
The catalytic partial oxidation of methane to synthesis gas on rhodium coated
monoliths at short contact times is a promising route for natural gas conversion into
more useful chemicals. The numerical simulation of this autothermally operated reac-
tor revealed fast variations of all transport properties at the catalyst entrance, where
the initially cold methane/oxygen mixture enters a ∼1300 K hot monolith. The con-
version of methane starts right at the catalyst entrance, where a strong competition
between partial and complete oxidation occurs. After 1 mm catalyst length, oxygen is
completely consumed and steam reforming is the determining reaction path. Experi-
mentally determined and numerically predicted conversion and selectivity data agreed
very well. The formation of synthesis gas was studied at varying conditions, e.g., the
syngas selectivity and methane conversion decrease with increasing flow rate. Homo-
geneous gas-phase reactions become significant at pressures above 10 bar. They lead
to a decrease in syngas selectivity and also increase the risks of flames. Light-off of the
reactor was studied by a transient two-dimensional simulation of the whole monolith,
which elucidated the impact of the temperature distribution in the monolithic structure
on overall conversion. Reactor design and scale-up can benefit from the application of
the models and computational tools developed.
The oxy-dehydrogenation of ethane to ethylene was investigated in platinum coated
monoliths at contact times of ∼5 ms. The observed performance of the ethane reac-
tor is the result of coupled heterogeneous and homogeneous chemical processes. The
valuable ethylene product of this reactor results from both homogeneous and heteroge-
neous dehydrogenation of ethane, the relative contributions of each depending on the
reactor conditions. Heat is required to drive this highly endothermic dehydrogenation.
It is concluded that this heat is provided through heterogeneous oxidation reactions
that occur very near the front of the catalytic section of the reactor. Conditions that
result in optimum reactor performance are most strongly characterized by a picture of
heterogeneous oxidation in conjunction with a relatively large contribution from homo-
geneous ethane dehydrogenation. The addition of H2 to the inlet feed of this reactor
results in surface hydrogen oxidation at the expense of surface carbon oxidation, pro-
ducing even more highly localized heat release into the gas-phase. Homogeneous ethane
dehydrogenation is also enhanced, while heterogeneous decomposition and oxidation
to CO and CO2 is diminished. The selectivity to ethylene increases because selectivity
to CO and CO2 is decreased. Desorption of radical species does not play an important
role in the initiation of homogeneous reactions under the conditions studied. Localized
heat release and high peak temperatures in the reactor are responsible for the short
residence times required to initiate the homogeneous chemistry vital to the reactor
144 9. CONCLUSIONS
References
[1] K. Christmann. Introduction to Surface Physical Chemistry. Topics in Physical Chemistry 1. Springer, New
York, 1991.
[2] D.A. Hickman and L.D. Schmidt. Production of syngas by direct catalytic oxidation of methane. Science, 259,
343–346, 1993.
[3] A.S. Bodke, D.A. Olschki, L.D. Schmidt, and E. Ranzi. High Selectivity to Ethylene by Partial Oxidation of
Ethane. Science, 285, 712–715, 1999.
[4] G. Ertl. Elementary Steps in Heterogeneous Catalysis. Angew. Chem. Int. Ed. Engl., 29, 1219–1227, 1990.
[5] K.Y. Kung, P. Chen, F. Wei, Y.R. Shen, and G.A. Somorjai. Sum-frequency generation spectroscopy study of
CO adsorption and dissociation on Pt(111) at high pressure and temperature. Surf. Sci., 463, 627–633, 2000.
[6] U. Metka, M.G. Schweitzer, H.-R. Volpp, J. Wolfrum, and J. Warnatz. In-situ detection of NO chemisorbed on
platinum using infrared-visible Sum-Frequency Generation (SFG). Zeitschr. f. Phys. Chem., 214, 865–888, 2000.
[7] Technology Vision 2020: The U.S. Chemical Industry, 1996. Report published by The American Chemical Society,
American Institute of Chemical Engineers, The Chemical Manufactures Association, The Council for Chemical
Research, The Synthetic Organic Chemical Manufactures Association.
[8] M. Huff and L.D. Schmidt. Production of Olefins by Oxidative Dehydrogenation of Propane and Butane over
Monoliths at Short Contact Times. J. Catal., 149, 127–141, 1993.
[9] A. Beretta, L. Piovesan, and P. Forzatti. An investigation on the role of a Pt/Al2 O3 catalyst in the oxidative
dehydrogenation of propane in annular reactor. J. Catal., 184, 455–468, 1999.
[10] D.A. Goetsch and L.D. Schmidt. Microsecond catalytic partial oxidation of alkanes. Science, 271, 1560–1562,
1996.
[11] D.I. Iordanoglou. Rapid Oxidation of Light Alkanes in Single Gauze Reactors. PhD thesis, Department of
Chemical Engineering and Materials Science, University of Minnesota, Minneapolis, MN, USA, 1998.
[12] R. Lødeng, O.A. Lindvåg, S. Kvisle, H. Reier-Nielsen, and A. Holmen. Short contact time oxidative dehydro-
genation of C2 and C3 alkanes over noble metal gauze catalysts. Appl. Catal. A, 187, 25–31, 1999.
[13] R.P. O’Connor and L.D. Schmidt. Catalytic partial oxidation of cyclohexane in a single-gauze reactor. J. Catal,
191, 245–256, 2000.
[14] R.P. O’Connor, L.D. Schmidt, and O. Deutschmann. Detailed Simulations of the Millisecond Partial Oxidation
of Cyclohexane in Single-Gauze Reactors: Coupled Chemistry and Fluid Dynamics. AIChE J. (submitted).
[15] R.B. Bird, W.E. Stewart, and E.N. Lightfoot. Transport Phenomena. John Wiley & Sons, Inc., New York, 1960.
[16] C.N. Satterfield. Mass Transfer in Heterogeneous Catalysis. MIT Press, Cambridge, MA, 1970.
[17] R. Aris. The Mathematical Theory of Diffusion and Reaction in Permeable Catalysts. Clarendon Press, Oxford,
1975.
[18] S.V. Patankar. Numerical Heat Transfer and Fluid Flow. McGraw-Hill, New York, 1980.
[19] M. Baerns, H. Hofmann, and A. Renken. Chemische Reaktionstechnik. Georg Thieme Verlag Stuttgart, New
York, 1992.
[20] J. Warnatz, R.W. Dibble, and U. Maas. Combustion, Physical and Chemical Fundamentals, Modeling and
Simulation, Experiments, Pullutant Formation. Springer-Verlag, New York, 1996.
[21] F. Keil. Diffusion und Chemische Reaktionen in der Gas-Feststoff-Katalyse. Springer-Verlag, Berlin, 1999.
[22] J. Warnatz. Influence of Transport Models and Boundary Conditions on Flame Structure. In N. Peters and
J. Warnatz, editors, Numerical Methods in Flame Propagation. Friedr. Vieweg and Sohn, Wiesbaden, 1982.
[23] R.J. Kee, J. Warnatz, and J.A. Miller. A FORTRAN Computer Code Package for the Evaluation of Gas Phase
Viscosities, Heat Conductivities, and Diffusion Coefficients. Sandia National Laboratories Report, SAND83-8209,
1983.
148 REFERENCES
[24] G. Dixon-Lewis. Flame structure and flame reaction kinetics. Proc. Roy. Soc. A, 307, 111–135, 1968.
[25] R.J. Kee, G. Dixon-Lewis, J. Warnatz, M.E. Coltrin, and J.A. Miller. A Fortran Computer Code Package
for the Evaluation of Gas-Phase Multicomponent Transport Properties. Sandia National Laboratories Report,
SAND86-8246, 1986.
[26] T.G. Cowling S. Chapman. Mathematical Theory of Non-Uniform Gases. Cambridge University Press, Second
Edition, 1951.
[27] M.W. Chase, C.A. Davis, J.R. Downey, D.J. Frurip, R.A. McDonald, and A.N. Syverud. JANAF Thermochemical
Tables, Third Edition. J. Phys. Chem. Ref. Data, 14, 1985.
[28] R.J. Kee, F.M. Rupley, and J.A. Miller. The Chemkin Thermodynamic Database. Sandia National Laboratories
Report, SAND87-8215, 1987.
[29] A. Burcat. Thermochemical data for combustion. In W.C. Gardiner, editor, Combustion chemistry. Springer,
New York, 1984.
[30] S.W. Benson. Thermochemical Kinetics. John Wiley & Sons, New York, 1976.
[31] S. Gordon and B.J. McBridge. Computer Programm for Calculation of Complex Chemical Equilibrium Compo-
sitions, Rocket Performance, Incident and Reflected Shocks and Chapman-Jouguet Detonations. NASA SP-273,
1971.
[32] E.S. Lox and B.H. Engler. Environmental catalysis. In G. Ertl, H. Knoezinger, and J. Weitkamp, editors,
Handbook of Heterogeneous Catalysis. Wiley-VCH, Weinheim, 1997.
[33] L.L. Raja, R.J. Kee, O. Deutschmann, J. Warnatz, and L.D. Schmidt. A Critical Evaluation of Navier-Stokes,
Boundary-Layer, and PLug-Flow Models of the Flow and Chemistry in a Catalytic-Combustion Monolith. Catal.
Today, 59, 47–60, 2000.
[34] H. Schlichting. Boundary-Layer Theory. 6th ed., McGraw-Hill, New York, 1968.
[36] S. Arrhenius. Über die Reaktionsgeschwindigkeit bei der Inversion von Rohrzucker durch Säuren. Z. Phys. Chem.,
4, 226, 1889.
[37] D.L. Baulch, C.J. Cobos, R.A. Cox, C. Esser, P. Frank, Th. Just, J.A. Kerr, M.J. Pilling, J. Troe, R.W. Walker,
and J. Warnatz. Evaluated Kinetic Data for Combustion Modelling. J. Phys. Chem. Ref. Data, 23, 850–851,
1994.
[38] W.C. Gardiner, editor. Combustion Chemistry. Springer, New York, 1984.
[39] U. Maas and S. Pope. Simplifying Chemical Kinetics: Intrinsic Low-Dimensional Manifolds in Composition Space.
Combust. Flame, 88, 239–264, 1992.
[40] M.E. Coltrin, R.J. Kee, G.H. Evans, E. Meeks, F.M. Rupley, and J.F. Grcar. SPIN: A Fortran Program for
Modeling One-Dimensional Rotating Disk / Stagnation - Flow Chemical Vapor Deposition Reactors. Sandia
National Laboratories Report, SAND91-8003, 1991.
[41] E. Meeks, R.J. Kee, and D.S. Dandy. Computational Simulation of Diamond Chemical Vapor Deposition in
Premixed C2 H2 /O2 /H2 and CH4 /O2 - Strained Flames. Combust. Flame, 92, 144–160, 1993.
[42] B. Ruf, F. Behrendt, O. Deutschmann, and J. Warnatz. Simulation of reactive flow in filament-assisted diamond
growth including hydrogen surface chemistry. J. Appl. Phys., 79, 7256–7263, 1996.
[43] B. Ruf, F. Behrendt, O. Deutschmann, S. Kleditzsch, and J. Warnatz. Modeling of chemical vapor deposition of
diamond films from acetylene-oxygen flames. Proc. Combust. Inst., 28, (in press), 2000.
[44] S. Kleditzsch and U. Riedel. Sensitivity Studies of Silicon Etching in Chlorine/Argon Plasmas. J. Vac. Sci.
Technol. A, 18, 2130–2136, 2000.
[45] O. Deutschmann, R. Schmidt, F. Behrendt, and J. Warnatz. Numerical modeling of catalytic combustion. Proc.
Combust. Inst., 26, 1747–1754, 1996.
[46] R.E. Hayes and S.T. Kolaczkowski. Introduction to Catalytic Combustion. Gordon and Breach Science Publ.
Amsterdam, 1997.
REFERENCES 149
[47] M.E. Coltrin, R.J. Kee, and F.M. Rupley. SURFACE CHEMKIN (Version 4.0): A Fortran Package for Analyzing
Heterogeneous Chemical Kinetics at a Solid-Surface - Gas-Phase Interface. Sandia National Laboratories Report,
SAND90-8003B, 1990.
[48] U. Metka. Untersuchung von Teilschritten der heterogenen Reaktion von CO mit NO an Platin mittels der
Summenfrequenz-Spektroskopie. Dissertation. Naturwissenschaftlich-Mathematische Gesamtfakultät. Ruprecht-
Karls-Universität Heidelberg, 2000.
[49] D.K. Zerkle, M.D. Allendorf, M. Wolf, and O. Deutschmann. Understanding Homogeneous and Heterogeneous
Contributions to the Platinum-Catalyzed Partial Oxidation of Ethane in a Short-Contact-Time Reactor. J. Catal,
196, 18–39, 2000.
[50] P. Aghalayam, Y.K. Park, and D.G. Vlachos. Construction and Optimization of Complex Surface-Reaction
Mechanisms. AIChE J., 46, 2017–2029, 2000.
[51] C.T. Campbell, G. Ertl, H. Kuipers, and J. Segner. A molecular beam of the adsorption and desorption of oxygen
from a Pt(111) surface. Surf. Sci., 107, 220–236, 1981.
[52] J.A. Dumesic, D.F. Rudd, L.M. Aparicio, J.E. Rekoske, and A. A. Trevino. The Microkinetics of Heterogeneous
Catalysis. American Chemical Society, Washington, DC, 1993.
[53] J.R. Chen and R. Gomer. Mobility of oxygen on the (110) plane of tungsten. Surf. Sci., 79, 413–444, 1979.
[54] S.C. Wang and R. Gomer. Diffusion of hydrogen, deuterium, and tritium on the (110) plane of tungsten. J.
Chem. Phys., 83, 4193–4209, 1985.
[55] D.R. Mullins, B. Roop, S.A. Castello, and J.M. White. Isotope Effects in Surface Diffusion. Hydrogen and
Deuterium on Ni(100). Surf. Sci., 186, 67–74, 1987.
[56] E.G. Seebauer, A.C.F. Kong, and L.D. Schmidt. Adsorption and Desorption of NO, CO and H2 on Pt(111):
Laser-induced Thermal Desorption Studies. Surf. Sci., 176, 134–156, 1986.
[57] E. Shustorovich. Chemisorption phenomena: analytic modeling based on perturbation theory and bond-order
conservation. Surf. Sci. Rep., 6, 1–63, 1986.
[58] E. Shustorovich. Bond making and breaking on transition-metal surfaces: theoretical projections based on bond-
order conservation. Surf. Sci., 176, L863–L872, 1986.
[59] E. Shustorovich and H. Sellers. The UBI-QEP Method: A Practical Theoretical Approach to Understanding
Chemistry on Transition Metal Surfaces. Surf. Sci. Rep., 31, 1–119, 1998.
[60] P. Sautet and J. Paul. Low temperature adsorption of ethylene and butadiene on platinum and paladium surfaces.
Catal. Lett., 9, 245–260, 1991.
[61] R.A. van Santen. Theoretical Heterogeneous Catalysis. World Scientific, Singapore, 1991.
[62] R.A. van Santen and M. Neurock. Theory of surface-chemical reactivity. In G. Ertl, H. Knoezinger, and
J. Weitkamp, editors, Hamdbook of Heterogeneous Catalysis, pages 991–1004. Wiley-VCH, Weinheim, 1997.
[63] T. Wahnström, E. Fridell, S. Ljungström, B. Hellsing, B. Kasemo, and A. Rosén. Determination of the Activation
Energy for OH Desorption in the H2 +O2 Reaction on Polycrystalline Platinum. Surf. Sci., 223, L905–912, 1989.
[64] W.R. Williams, C.M. Marks, and L.D. Schmidt. Steps in the Reaction H2 +O2 =H2 O on Pt: OH Desorption at
High Temperatures. J. Phys.Chem., 96, 5922–5931, 1992.
[65] F. Behrendt, O. Deutschmann, U. Maas, and J. Warnatz. Simulation and sensitivity analysis of the heterogeneous
oxidation of methane on a platinum foil. J. Vac. Sci. Technol. A, 13 (3), 1373–1377, 1995.
[66] O. Deutschmann. Modellierung von Reaktionen an Oberflächen und deren Kopplung mit chemisch reagierenden
Strömungen. Dissertation. Naturwissenschaftlich-Mathematische Gesamtfakultät. Ruprecht-Karls-Universität
Heidelberg, 1996.
[67] L.L. Raja, R.J. Kee, and L.R. Petzold. Simulation of the transient, compressible, gas-dynamic, behavior of
catalytic-combustion ignition in stagnation flows. Proc. Combust. Inst., 27, 2249–2257, 1998.
[68] R. Kissel-Osterrieder, F. Behrendt, J. Warnatz, U. Metka, H.-R. Volpp, and J. Wolfrum. Experimental and
theoretical investigation of the CO oxidation on platinum: Bridging the pressure and material gap. Proc. Combust.
Inst., 28, 1341–1348, 2000.
150 REFERENCES
[69] S.J. Lombardo and A.T. Bell. A Monte Carlo model for the simulation of the temperature-programmed desorption
spectra. Surf. Sci., 206, 101–123, 1988.
[70] R. Kissel-Osterrieder, F. Behrendt, and J. Warnatz. Detailed modeling of the oxidation of CO on platinum: A
monte-carlo model. Proc. Combust. Inst., 27, 2267–2274, 1998.
[71] N. Wakao and J.M. Smith. Diffusion in catalyst pellets. Chem. Eng. Sci., 17, 825, 1962.
[72] C. Rieckmann and F.J. Keil. Simulation and experiment of multicomponent diffusion and reaction in three-
diemnsional networks. Chem. Eng. Sci., 54, 3485–3493, 1999.
[73] F.J. Keil. Diffusion and reaction in porous networks. Catalysis Today, 53, 245–258, 2000.
[75] R.J. Kee, F.M. Rupley, and J.A. Miller. CHEMKIN-II: A Fortran Chemical Kinetics Package for the Analysis
of Gas-Phase Chemical Kinetics. Sandia National Laboratories Report, SAND89-8009, 1989.
[76] M.E. Coltrin, H.K. Moffata, R.J. Kee, and F.M. Rupley. CRESLAF (Version 4.0): A Fortran Pogram for
Modeling Laminar, Chemically Reacting, Boundary-Layer Flow in Cylindrical or Planar Channels. Sandia
National Laboratories Report, SAND93-0478, 1993.
[77] R.J. Kee, F.M Rupley, J.A. Miller, M.E. Coltrin, J.F. Grcar, E. Meeks, K.H. Moffat, A.E. Lutz, G. Dixon-Lewis,
M.D. Smooke, J. Warnatz, G.H. Evans, R.S. Larson, R.E. Mitchell, L.R. Petzold, W.C. Reynolds, M. Caracotsios,
W.E. Stewart, P. Glarborg, C. Wang, and O. Adigun. CHEMKIN Collection, Version 3.6. Reaction Design, Inc.,
San Diego, 2000.
[80] K.D. Devine, G.L. Hennigan, S.A. Hutchinson, A.G. Salinger, J.N. Shadid, and R.S.Tuminaro. High Performance
MP Unstructured Finite Element Simulation of Chemically Reacting Flows. Proc. of SC97, San Jose, CA, Nov.
15-21.
[81] O. Deutschmann, C. Correa, S. Tischer, D. Chatterjee, and J. Warnatz. DETCHEM, User Manual, Version
1.4.1. http://reaflow.iwr.uni-heidelberg.de/∼dmann/DETCHEM.html, 2001.
[84] J. Warnatz. Resolution of Gas Phase and Surface Combustion Chemistry into Elementary Reactions (Invited
Lecture). Proc. Combust. Inst., 24, 553–579, 1992.
[85] O. Deutschmann and L. D. Schmidt. Modeling the partial oxidation of methane in a short-contact-time reactor.
AIChE J., 44, 2465–2477, 1998.
[86] P. Deuflhard, E. Hairer, and J. Zugk. One-step and extrapolation methods for diffrenetial-algebraic systems.
Num. Math., 51, 501–516, 1987.
[87] J. Braun, T. Hauber, H. Többen, P. Zacke, D. Chatterjee, O. Deutschmann, and J. Warnatz. Influence of Physical
and Chemical Parameters on the Conversion Rate of a Catalytic Converter: A Numerical Simulation Study. SAE
paper, 2000-01-0211, 2000.
[89] D. Chatterjee, O. Deutschmann, and J. Warnatz. Simulation of HC-SCR using detailed models for chemistry and
transport, publication in preparation.
[90] Fluent Version 4.4. Fluent Inc., Lebanon, New Hampshire, 1997.
REFERENCES 151
[91] S. Tischer and O. Deutschmann. Modeling the oxy-dehydrogenation of ethane in annular recators. publication
in preparation.
[92] S. Tischer, C. Correa, and O. Deutschmann. Transient three-dimensional simulation of a catalytic combustion
monolith using detailed models for heterogeneous and homogeneous reactions and transport phenomena. 1st In-
ternatl. Conference on Structured Catalysts and Reactors, October 21-24, 2001, Delft/The Netherlands, accpeted
for publication in Catal. Today.
[93] C. Correa, S. Tischer, and O. Deutschmann. Transient three-dimensional simulation of automotve catalytic
converters. publication in preparation.
[94] A.C. Hindmarsh. Odepack, a systematized collection of ode solvers. In R.S. Stepleman et al., editor, Scientific
Computing, pages 55–64. North-Holland, Amsterdam, 1983.
[95] M. Baerns. Oxidative Coupling of Methane for the Utilization of Natural Gas. In H.I. de Lasa et al., editor,
Chemical Reactor Technology for Environmental Safe Reactors and Products, pages 283–316. Kluwer Academic
Publishers, 1993.
[96] J.A. Labinger. Apporaches to catalytic methane conversion in academic and industrial research: comparison,
competition, collaboration. QUIMICA, 48, 27, 1993.
[97] M. Belgued, H. Amariglio, P. Pareja, A. Ameriglio, and J. Saint-Just. Low Temperature Catalytic Homologation
of Methane on Platinum, Ruthenium and Cobolt. Catal. Today, 13, 437–445, 1992.
[98] F. Solymosi, A. Erdhelyi, and J. Cserenyi. A comparative study on the activation and reactions of methane on
supported metals. Catal. Lett., 16, 399–405, 1992.
[99] V.R. Choudhary, A.M. Rajput, and V.H. Rane. Low-Temperature Catalytic Selective Partial Oxidation of
Methane to CO and H2 over Ni/Yb2 O3 . J. Phys. Chem., 96, 8686, 1992.
[100] S.C. Reyes, E. Igelsia, and C.P. Kelkar. Kinetic-transport models of bimodal reaction sequences-I. Homogeneous
and heterogeneous pathways in oxidative coupling of methane. Chem. Eng. Sci., 48, 2643, 1993.
[101] M. Wolf, O. Deutschmann, F. Behrendt, and J. Warnatz. Simulation of the Oxygen-free Methane Conversion to
Higher Hydrocarbon Fuels Using a Platinum Catalyst with a Catalytically Active Carbonaceous Overlayer. In
Natural Gas Conversion V, Studies in Surface Science and Catalysis 119, pages 271–276. Elsevier, Amsterdam,
1998.
[102] R.W. Borry, E.C. Lu, Y.-H. Kim, and E. Iglesia. Non-oxidative catalytic conversion of methane with continuous
hydrogen removal. In Natural Gas Conversion V, Studies in Surface Science and Catalysis, pages 403–410.
Elsevier, Amsterdam, 1998.
[103] M. Wolf, O. Deutschmann, F. Behrendt, and J. Warnatz. Kinetic model of an oxygen-free methane conversion
on a platinum catalyst. Catal. Lett., 61, 5, 1999.
[104] L. Li, R. Borry, and E. Iglesia. Reaction-transport simulations of non-oxidative methane conversion with con-
tinuous hydrogen removal - homogeneous-heterogeneous reaction pathways. Chem. Eng. Sci., 56, 1869–1881,
2001.
[105] K. Weissermel and H.-J. Arpe. Industrielle organische Chemie. VCH Weinheim, 1988.
[106] M. Prettre, Ch. Eichner, and M. Perrin. Trans. Faraday Soc., 43, 335, 1946.
[107] D. Dissanayake, M.P. Rosynek, K.C. Kharas, and J.H. Lundsford. Partial oxidation of methane to carbon
monoxide and hydrogen over a nickel/alumina catalyst. J. Catal., 132, 117–127, 1991.
[108] A.T. Ashcroft, A.K. Cheetham, J.S. Ford, M.L.H. Green, C.P. Grey, A.J. Murrell, and P.D.F. Vernon. Selective
oxidation of methane to synthesis gas using transition catalysts. Nature, 344, 319, 1990.
[109] P.D.F. Vernon, M.L.H. Green, A.K. Cheetham, and A.T. Ashcroft. Catal. Lett., 6, 181, 1990.
[110] P.D.F. Vernon, M.L.H. Green, A.K. Cheetham, and A.T. Ashcroft. Partial oxidation of methane to synthesis gas
and carbon dioxide as an oxidizing agent for methane conversion. Catal. Today, 13, 417–426, 1992.
[111] W.J.M. Vermeiren, E. Blomsma, and P.A. Jacobs. Catalytic and thermodynamic approach of the oxyreforming
reaction of methane. Catal. Today, 13, 427–436, 1992.
152 REFERENCES
[112] V.R. Choudhary, A.M. Rajput, and B. Prabhakar. Low temperature oxidative conversion of methane to syngas
over nickel oxide - calcium oxide catalyst. Catal. Lett., 15, 363–370, 1992.
[113] V.R. Choudhary, A.M. Rajput, and B. Prabhakar. Nonequilibrium oxidative conversion of methane to carbon
monoxide and hydrogen with high selectivity and productivity over nickel/alumina at low temperatures. J. Catal.,
139, 326–328, 1993.
[114] V.R. Choudhary, A.M. Rajput, and B. Prabhakar. Low temperature oxidative conversion of methane to syngas
over cobalt/rare earth oxide catalysts. Catal. Lett., 16, 269–272, 1992.
[115] V.R. Choudhary, A.M. Rajput, and B. Prabhakar. Low temperature selective conversion of methane to carbon
monoxide and hydrogen over cobalt-magnesium oxide catalysts. Appl. Catal., 90, L1–L5, 1992.
[116] J.A. Lapszewicz and X.-Z. Jiang. Investigation of the mechanism of partial oxidation of methane to synthesis
gas. Prep. Am. Chem. Soc. Div. Pet. Chem., 37, 252–260, 1992.
[117] Y. Matsumura and J.B. Moffat. Partial Oxidation of Methane to Carbon Monoxide and Hydrogen with Molecular
Oxygen and Nitrous Oxide over Hydroxyapatite Catalysts. Catal. Lett., 148, 323, 1994.
[118] O.V. Buyevskaya, D. Wolf, and M. Baerns. Rhodium - catalyzed partial oxidation of methane to CO and h2 .
transient studies on its mechanism. Catal. Lett., 29, 249–260, 1994.
[119] K. Walter, O.V. Buyevskaya, D. Wolf, and M. Baerns. Rhodium-catalyzed partial oxidation of methane to CO
and H2 . In situ DRIFTS studies on surface intermediates. Catal. Lett., 29, 261–270, 1994.
[120] D. Wolf, M. Höhenberger, and M. Baerns. External Mass and Heat Transfer Limitations of the Partial Oxidation
of Methane over Pt/MgO - Consequences for Adiabatic Reactor Operation. Ind. Eng. Chem. Res., 36, 3345–3353,
1997.
[121] D. Wolf, M. Barre-Chassonnery, M. Höhenberger, A. van Veen, and M. Baerns. Kinetics of the Water-Gas shift
reaction and its Role in the Conversion of Methane to Syngas over a Pt/MgO Catalyst. Catal. Today, 40, 147–156,
1998.
[122] D.A. Hickman and L.D. Schmidt. Steps in CH4 Oxidation on Pt and Rh Surfaces: High Temperature Reactor
Simulation. AIChE J., 39 (7), 1164–1177, 1993.
[123] K. Heitnes, S. Lindeberg, O.A. Rokstad, and A. Holmen. Catalytic partial oxidation of methane to synthesis gas
using monolithic reactors. Catalysis Today, 21, 471–480, 1994.
[124] K. Heitnes, S. Lindeberg, O.A. Rokstad, and A. Holmen. Catalytic partial oxidation of methane to synthesis gas.
Catalysis Today, 24, 211–216, 1995.
[125] J.C. Jalibert, M. Fathi, O.A. Rokstad, and A. Holmen. Synthesis gas production by partial oxidation of metahne
from the cyclic gas-solid reaction using promoted cerium oxide. In Natural Gas Conversion VI, Studies in Surface
Science and Catalysis 136 (E. Iglesia, J.J. Spivey, T.H. Fleisch (eds.), pages 301–306. Elsevier, Amsterdam, 2001.
[126] E.P.J. Mallens, J.H.B. Hoebink, and G.B. Marin. The reaction mechanism of the partial oxidation of methane to
synthesis gas: A transient kinetic study over rhodium and a comparison with platinum. J. Catal., 167, 43–46,
1997.
[127] M. Schwiedernoch. Untersuchung zur katalytischen Partialoxidation von Methan. Diplomarbeit, Fakultät Chemie
der Ruprecht-Karls-Universität Heidelberg, 2000.
[128] O. Deutschmann, R. Schwiedernoch, L.I. Maier, and D. Chatterjee. Natural Gas Conversion in Monolithic
Catalysts: Interaction of Chemical Reactions and Transport Phenomena. In Natural Gas Conversion VI, Studies
in Surface Science and Catalysis 136 (E. Iglesia, J.J. Spivey, T.H. Fleisch (eds.), pages 215–258. Elsevier,
Amsterdam, 2001.
[129] L.D. Schmidt. University of Minnesota, Minneapolis, MN, USA, personal communication, 1997.
[130] A.S. Bodke, S.S. Bharadwaj, and L.D. Schmidt. The Effect of Ceramic Supports on Partial Oxidation of Hydro-
carbons over Noble Metal Coated Monoliths. J. Catal., 179, 138–149, 1998.
[131] J. Frauhammer, L. von Hippel, D. Arntz, and G. Eigenberger. A new reactor concept for endothermic high-
temperature reactions. Chem. Eng. Sci., 54, 3661–3670, 1999.
[132] G. Kolios, J. Frauhammer, and G. Eigenberger. Autothermal fixed-bed reactor concepts. Chem. Eng. Sci., 55,
5945–5967, 2000.
REFERENCES 153
[133] G. Veser, J. Frauhammer, and U. Friedle. Syngas formation by direct oxidation of methane - Reaction mechanisms
and new reactor concepts. Catal. Today, 61, 55–64, 2000.
[134] G. Kolios, J. Frauhammer, and G. Eigenberger. A simplified procedure for the optimal design of autothermal
reactors for endothermic high-temperature reactions. Chem. Eng. Sci., 56, 351–357, 2001.
[135] L. Basini, A. Guarinoni, K. Aasberg-Petersen, and J.H. Bak-Hansen. Catalytic partial oxidation of natural gas
at elevated pressure and low residence time. Proc. EuropCat 4, Rimini/Italy, September, 1999.
[136] L.D. Schmidt, O. Deutschmann, and C.T. Goralski, Jr. Modeling the Partial Oxidation of Methane to Syngas
at Millisecond Contact Times. In Natural Gas Conversion V, Studies in Surface Science and Catalysis, pages
685–692. Elsevier, Amsterdam, 1998.
[137] C.R.H. de Smet, M.H.J.M. de Croon, R.J. Berger, G.B. Marin, and J. C. Schouten. An experimental reactor to
study the intrinsic kinetcis of the partial oxidation of methane to synthesis gas in the presence of heat-transport
limitations. Appl. Catal. A, 187, 33, 1999.
[138] G. Veser and J. Frauhammer. Modelling steady state and ignition during catalytic methane oxidation in a
monolith reactor. Chem. Eng. Sci., 55, 2271–2286, 2000.
[139] D.A. Hickman and L.D. Schmidt. Synthesis Gas Formation by Direct Oxidation of Methane over Pt Monoliths.
J. Catal., 138, 267–282, 1992.
[140] O. Deutschmann and L.D. Schmidt. Two-dimensional modeling of partial oxidation of methane on rhodium in a
short contact time reactor. Proc. Combust. Inst., 27, 2283–2291, 1998.
[141] O. Deutschmann, L.D. Schmidt, and J. Warnatz. Simulation of reactive flow in a partial oxidation reactor with
detailed gas phase and surface chemistry models. In F. Keil, W. Mackens, H. Vos̈, and J. Werther, editors,
Scientific Computing in Chemical Engineering II. Computational Fluid Dynamics, Reaction Engineering, and
Molecular Properties, pages 368–375. Springer, 1999.
[143] V. Karbach. Validierung eines detaillierten Reaktionsmechanismus zur Oxidation von Kohlenwasserstoffen bei
hohen Temperaturen. Diplomarbeit, Fakultät Chemie der Ruprecht-Karls-Universität Heidelberg, 1997.
[144] K.L. Hohn, P.M. Witt, M.B. Davis, and L.D. Schmidt. Methane Coupling to Acetylene over Pt Coated Monoliths
at Millisecond Contact Times. Catal. Lett., 54, 113–118, 1998.
[145] D. Papadias, L. Edsberg, and P. Björnbom. Simplified Method of Effectiveness Factor Calculations for Irregular
Geometries of Washcoats; A General Case in a 3D Concentration Field. Catal. Today, 60, 11, 2000.
[146] M. Huff and L. D. Schmidt. Ethylene Formation by Oxidative Dehydrogenation of Ethane over Monoliths at Very
Short Contact Times. J. Phys. Chem., 97, 11815–11822, 1993.
[147] A.G. Dietz III and L.D. Schmidt. Effect of pressure on three catalytic partial oxidation reactions at millisecond
contact times. Catal. Lett., 33, 5–29, 1995.
[148] C. Yokoyama, S.S. Bharadwaj, and L.D. Schmidt. Platinum-tin and platinum-copper catalysts for autothermal
oxidative dehydrogenation of ethane to ethylene. Catal. Lett., 38, 181–188, 1996.
[149] P. Witt and L.D. Schmidt. Effectof flow rate on the partial oxidation of methane and ethane. J. Catal., 163,
465–475, 1996.
[150] D.W. Flick and M.C. Huff. Acetylene formation during the catalytic oxidative dehydrogenation of ethane over a
Pt-coated monoliths at short contact times. Catal. Lett., 47, 91–97, 1997.
[151] A.S. Bodke, D. Henning, L.D. Schmidt, S.S. Bharadwaj, and J. Siddall. Oxidative Dehydrogenation of Ethane
at Millisecond Contact Times: Effect of Hydrogen Addition. J. Catal., 191, 62–74, 2000.
[152] D.W. Flick and M.C. Huff. Oxidative dehydrogenation of ethane over a Pt-coated monolith versus Pt-loaded
pellets: Surface area and thermal effects. J. Catal., 178, 315–327, 1998.
[153] D.W. Flick and M.C. Huff. Oxidative dehydrogenation of ethane over supported chromium oxide and Pt modified
chromium oxide. Appl. Catal. A, 187, 13–24, 1999.
[154] E. Morales and J.H. Lundsford. Oxidative dehydrogenation of ethane over a lithium-promoted magnesium oxide
catalyst. J. Catal., 118, 255–265, 1989.
154 REFERENCES
[155] G.A. Martin, A. Bates, V. DuCarme, and C. Mirodatos. Oxidative conversion of methane and C2 hydrocarbons
on oxides: homogeneous versus heterogeneous processes. Appl. Catal., 47, 287–297, 1989.
[156] R. Burch and E.M. Crabb. Homogeneous and heterogeneous contributions to the catalytic oxidative dehydro-
genation of ethane. Appl. Catal. A, 97, 49–65, 1999.
[157] M. Baerns and O. Buyevskay. Simple chemical processes based on low molecular-mass alkanes as chemical
feedstocks. Catal. Today, 45, 13–22, 1998.
[158] R. Lødeng, O.A. Lindvåg, S. Kvisle, H. Reier-Nielsen, and A. Holmen. Oxidative dehydrogenation of ethane over
Pt and Pt/Rh gauze catalyst at very short contact times. In Natural Gas Conversion V, Studies in Surface
Science and Catalysis 119, pages 641–646. Elsevier, Amsterdam, 1998.
[159] A. Beretta, G. Groppi, L. Majocchi, and P. Forzatti. Potentialities and draw-backs of the experimental approach
to the study of high T and high GHSV kinetics. Appl. Catal. A, 187, 49–60, 1999.
[160] A. Beretta, P. Forzatti, and E. Ranzi. Production of olefins via oxidative dehydrogenation of propane in autother-
mal conditions. J. Catal., 184, 469–478, 1999.
[161] M. Huff and L.D. Schmidt. Elementary Step Model of Ethane Oxidative Dehydrogenation on Pt-Coated Mono-
liths. AIChE J., 42, 3484–3497, 1996.
[162] M.C. Huff, I.P. Androulakis, J.H. Sinfelt, and S.C. Reyes. The Contribution of Gas-Phase Reactions in the
Pt-Catalyzed Conversion of Ethane-Oxygen Mixtures. J. Catal, 191, 46–45, 2000.
[163] D.K. Zerkle, M.D. Allendorf, M. Wolf, and O. Deutschmann. Modeling of On-Line Catalyst Addition Effects in
a Short Contact Time Reactor. Proc. Combust. Inst., 28, 1365–1372, 2000.
[165] N.M. Marinov, W.J. Pitz, C.K. Westbrook, M.J. Castaldi, and S.M. Senkan. Modeling of aromatic and polycyclic
aromatic hydrocarbon formation in premixed methane and ethane flames. Combust. Sci. Technol., 116, 211–287,
1996.
[167] G. Stahl and J. Warnatz. Numerical investigation of time-dependent properties and extinction of strained
methane- and propane-air flamelets. Combust. Flame, 85, 285–299, 1991.
[168] A.E. Lutz, R.J. Kee, and J.A. Miller. A Program for Predicting Homogeneous Gas-phase Chemical Kinetics in
a Closed System with Sensitivity Analysis. Sandia National Laboratories Report No. SAND87-8248, 1987.
[169] C.K. Law F.N. Egolfopoulos, D.L. Zhu. Experimental and numerical determination of laminar flame speeds:
Mixtures of C2 - hydrocarbons with oxygen and nitrogen. Proc. Combust. Inst., 23, 471–478, 1990.
[170] R.J. Kee, J.F. Grcar, M.D. Smooke, and J.A. Miller. A FORTRAN Program for Modeling Steady Laminar
One-Dimensional Flames. Sandia National Laboratories Report No. SAND85-8240, 1985.
[171] P. Dagaut, M. Cathonnet, and J.C. Boettner. Kinetics of ethane oxidation. Int. J. Chem. Kin., 23, 437–455,
1989.
[172] M. Rinnemo, O. Deutschmann, F. Behrendt, and B. Kasemo. Experimental and Numerical Investigation of the
Catalytic Ignition of Mixtures of Hydrogen and Oxygen on Platinum. Combust. Flame, 111, 312–326, 1997.
[173] J. Warnatz, M.D. Allendorf, R.J. Kee, and M.E. Coltrin. A Model of Elementary Chemistry and Fluid Mechanics
in the Combustion of Hydrogen on Platinum Surfaces. Combust. Flame, 96, 393–406, 1994.
[174] G.B. Fisher and J.L. Gland. The Interaction of Water with the Pt(111) Surface. Surf. Sci., 94, 446–455, 1980.
[175] A.B. Anton and D.C. Cadogan. Surf. Sci. Lett., 239, L548, 1990.
[176] D. Knight. Humphry Davy: Science & Power. Blackwell Publishers, Cambridge, MA, 1992.
[177] G.B. Kauffman. Johann Wolfgang Döbereiners Feuerzeug. On the sesquicentennial Anniversary of his Death.
Platinum Metals Rev., 43, 122–128, 1999.
[178] R.A. Dalla Betta. Catalytic combustion gas turbine systems: the preferred technology for low emissions electric
power generation and co-generation. Catal. Today, 35, 129–135, 1997.
REFERENCES 155
[179] P. Forzatti and G. Groppi. Catalytic combustion for the production of energy. Catal. Today, 54, 165–180, 1999.
[180] K.-I. Fujimoto, F.H. Ribeiro, M. Avalos-Borja, and E. Iglesia. Structure and Reactivity of PdOx /ZrO2 Catalysts
for Methane Oxidation at Low Temperatures. J. Catal., 179, 431–442, 1998.
[181] G. Groppi, C. Cristiani, and P. Forzatti. Preparation and characterization of hexaaluminate materials for high -
temperature catalytic combustion. Catal., 13, 85–113, 1997.
[182] G. Saraccoa and V. Specchia. Catalytic filters for the abatement of volatile organic compounds. Chem. Eng. Sci.,
55, 897–908, 2000.
[183] L.D. Pfefferle and W.C. Pfefferle. Catalysis in Combustion. Catal. Rev.-Sci. Eng., 29, 219–267, 1987.
[184] K.E. Brenan, S.L. Campbell, and L.R. Petzold. Numerical Solution of Initial-Value Problems in Differential-
Algebraic Equations. 2nd ed., SIAM, Philadelphia, 1998.
[185] O. Deutschmann, F. Behrendt, and J. Warnatz. Modelling and Simulation of Heterogeneous Oxidation of Methane
on a Platinum Foil. Catal. Today, 21, 461–470, 1994.
[186] W.M. Kays and M.E. Crawford. Convective Heat and Mass Transfer. McGraw-Hill, New York, 1980.
[187] R.E. Hayes and S.T. Kolaczkowski. A study of Nusselt and Sherwood numbers in a monolith reactor. Catalysis
Today, 47, 295–303, 1999.
[188] M. Frenklach. GRI-Mech – An Optimized Detailed Chemical Reaction Mechanism for Methane Combustion. GRI
Report No. GRI-95/0058, 1995.
[189] G. Veser and L.D. Schmidt. Ignition and Extinction in the Catalytic Oxidation of Hydrocarbons over Platinum.
AIChE J., 42, 1077–1087, 1996.
[190] G. Veser, J. Frauhammer, L.D. Schmidt, and G. Eigenberger. Catalytic ignition during methane oxidation on
platinum: Experiments and modeling. In Dynamics of Surfaces and Reaction Kinetics in Hetergeneous Catalysis,
Studies in Surface Science and Catalysis 109, pages 273–284. Elsevier, Amsterdam, 1997.
[191] O. Deutschmann, L. Maier, U. Riedel, J. Warnatz, A.H. Stroemanna, and R.W. Dibble. Hydrogen asssisted
catalytic combustion of methane on platinum. Catal. Today, 59, 141–140, 2000.
[192] D.L. Baulch, C.J. Cobos, R.A. Cox, C. Esser, P. Frank, Th. Just, J.A. Kerr, M.J. Pilling, J. Troe, R.W. Walker,
and J. Warnatz. Evaluated Kinetic Data for Combustion Modelling. J. Phys. Chem. Ref. Data, 21, 11, 1992.
[193] C.T. Goralski and L.D. Schmidt. Lean catalytic combustion of alkanes at short contact times. Catal. Lett., 42,
47–55, 1996.
[194] J. Redenius, L.D. Schmidt, and O. Deutschmann. Millisecond Catalytic Wall Reactors: I. Radiant Burner.
[195] R.M. Heck and R.J Farrauto. Catalytic Air Pollution Control. Van Nostrand Reinhold, New York, 1995.
[197] G.C. Koltsakis, P.A. Konstantinidis, and A.M. Stamatelos. Development and application range of mathematical
models for 3-way catalytic converters. Appl. Catal. B: Environmental, 12, 161–191, 1997.
[198] T. Kirchner and G. Eigenberger. On the dynamic behavior of automotive catalysts. Catal. Today, 28, 3, 1997.
[199] G.P. Ansell, P.S. Bennett, J.P. Cox, J.C. Frost, P.G. Gray, A.-M. Jones, R.R. Rajaram, A.P. Walker, M. Litorell,
and G. Smedler. The development of a model capable of predicting diesel lean NOx catalyst performance under
transient conditions. Appl. Catal. B, 10, 183, 1996.
[200] A.L. Boehman. Numerical Modeling of NO Reduction over Cu-ZSM-5 under Lean Conditions. SAE paper,
970752, 1997.
[201] C.N. Montreuil, S.C. Williams, and A.A. Adamczyk. Modeling current generation catalytic converters; laboratory,
experiments and kinetic parameter optimization-steady state kinetics. SAE-paper, 980881, 1992.
[202] S.-J. Jeong and W.-S. Kim. A numerical approach to investigate transient thermal and conversion characteristics
of automotive catalytic converter. SAE-paper, 980881, 1998.
156 REFERENCES
[203] D. Chatterjee, O. Deutschmann, and J. Warnatz. Detailed surface reaction mechanism in a 3-way catalyst.
Faraday Discussions, accepted for publication.
[204] E. Rogermond, N. Essayem, R. Frety, V. Perrichon, M. Primet, M. Chevrier, C. Gouthier, and F. Mathis.
Characterization of model three-way catalysts. J. Catal., 186, 414, 1999.
[205] S.H. Oh, G.B. Fisher, J.E. Carpenter, and D.W. Goodman. Comparative Kinetic Study of CO-O2 and CO-NO
Reactions over Single Crystal and Supported Rhodium Catalysts. J. Catal., 100, 360, 1986.
[206] E.I. Altman and R.J. Gorte. A temperature-Programmed Desoprtion study of NO on Rh Particles Supported on
α-Al2 O3 (0001). J. Catal., 113, 185, 1988.
[207] A. Fritz and V. Pichon. The current state of research on automotive lean NOx catalysis. Appl. Catal., 13, 1,
1997.
[208] R.J. Farrauto and E.M. Heck. Catalytic converter: State of the art and perspectives. Catal. Today, 51, 351,
1999.
[210] V. Schulz, O. Deutschmann, L.D. Schmidt, and J. Warnatz. Process optimization of reactive systems modeled by
elementary reactions. In F. Keil, W. Mackens, H. Vos̈, and J. Werther, editors, Scientific Computing in Chemical
Engineering II. Simulation, Image Processing, Optimization, and Control, pages 354–361. Springer, 1999.
[211] M.v. Schwerin, O. Deutschmann, , and V. Schulz. Process optimization of reactive systems by partiallly reduced
sqp methods. Computer & Chemical Engineering, 24, 89–97, 2000.
[212] V. Schulz. Reduced SQP methods for large-scale optimal control problems in DAE with application to path plan-
ning problems for satellite mounted robots. Dissertation. Naturwissenschaftlich-Mathematische Gesamtfakultät.
Ruprecht-Karls-Universität Heidelberg, 1996.
[213] S. Großhans, O. Deutschmann, V. Schulz, and H.G. Bock. Optimal control of a reactive stagnation point flow on
a catalytic surface. publication in preparation.
157
Reaction A β Ea
1. O2 + H
OH + O 2.000 · 1014 0.0 70.3
2. H2 + O
OH + H 5.060 · 104 2.7 26.3
3. H2 + OH
H2 O + H 1.000 · 108 1.6 13.8
4. OH + OH
H2 O + O 1.500 · 109 1.1 0.4
5. H + O2 + M(1)
HO2 + M(1) 2.300 · 1018 −0.8 0.0
6. HO2 + H
OH + OH 1.500 · 1014 0.0 4.2
7. HO2 + H
H2 + O2 2.500 · 1013 0.0 2.9
8. HO2 + H
H2 O + O 3.000 · 1013 0.0 7.2
9. HO2 + O
OH + O2 1.800 · 1013 0.0 −1.7
10. HO2 + OH
H2 O + O2 6.000 · 1013 0.0 0.0
11. HO2 + HO2
H2 O2 + O2 2.500 · 1011 0.0 −5.2
12. OH + OH + M(1)
H2 O2 + M(1) 3.250 · 1022 −2.0 0.0
13. H 2 O2 + H
H2 + HO2 1.700 · 1012 0.0 15.7
14. H2 O2 + OH
H2 O + HO2 5.400 · 1012 0.0 4.2
15. CO + OH
CO2 + H 6.000 · 106 1.5 −3.1
16. CO + HO2
CO2 + OH 1.500 · 1014 0.0 98.7
17. CO + O + M(1)
CO2 + M(1) 7.100 · 1013 0.0 −19.0
18. CO + O2
CO2 + O 2.500 · 1012 0.0 200.0
19. CHO + M(1)
CO + H + M(1) 7.100 · 1014 0.0 70.3
20. CHO + O2
CO + HO2 3.000 · 1012 0.0 0.0
21. CH2 O + M(1)
CHO + H + M(1) 5.000 · 1016 0.0 320.0
22. CH2 O + H
CHO + H2 2.300 · 1010 1.1 13.7
23. CH2 O + O
CHO + OH 4.150 · 1011 0.6 11.6
24. CH2 O + OH
CHO + H2 O 3.400 · 109 1.2 −1.9
25. CH2 O + HO2
CHO + H2 O2 3.000 · 1012 0.0 54.7
26. CH2 O + CH3
CHO + CH4 1.000 · 1011 0.0 25.5
27. CH2 O + O2
CHO + HO2 6.000 · 1013 0.0 170.7
158 A. GAS-PHASE REACTION MECHANISMS
Reaction A β Ea
28. CH3 + O
CH2 O + H 8.430 · 1013 0.0 0.0
29. CH4 + M(2)
CH3 + H + M(2) 2.400 · 1016 0.0 439.0
Low: 1.290 · 1018 0.0 380.0
Troe: 0.000 1.350 · 1003 1.0 7830.0
30. CH3 + OH → CH3 O + H 2.260 · 1014 0.0 64.8
31. CH3 O + H → CH3 + OH 4.750 · 1016 −0.1 88.0
32. CH3 + O2 → CH2 O + OH 3.300 · 1011 0.0 37.4
33. CH3 + HO2
CH3 O + OH 1.800 · 1013 0.0 0.0
34. CH3 + HO2
CH4 + O2 3.600 · 1012 0.0 0.0
35. CH3 + CH3 → C2 H4 + H2 1.000 · 1016 0.0 134.0
36. CH3 + CH3 + M(1)
C2 H6 + M(1) 3.610 · 1013 0.0 0.0
Low: 3.630 · 1041 −7.0 11.6
Troe: 0.620 7.300 · 1001 1180.0 0.0
37. CH3 O + M(1)
CH2 O + H + M(1) 5.000 · 1013 0.0 105.0
38. CH3 O + H
CH2 O + H2 1.800 · 1013 0.0 0.0
39. CH3 O + O2
CH2 O + HO2 4.000 · 1010 0.0 8.9
40. CH3 O + O
O2 + CH3 1.100 · 1013 0.0 0.0
41. CH4 + H
H2 + CH3 1.300 · 104 3.0 33.6
42. CH4 + O
OH + CH3 6.923 · 108 1.6 35.5
43. CH4 + OH
H2 O + CH3 1.600 · 107 1.8 11.6
44. CH4 + HO2
H2 O2 + CH3 1.100 · 1013 0.0 103.1
45. C2 H3 + M(1)
C2 H2 + H + M(1) 1.900 · 1014 0.0 166.3
Low: 1.000 · 1042 −7.5 190.4
Troe: 0.350 0.000 · 1000 0.0 0.0
46. C2 H3 + OH
C2 H2 + H2 O 5.000 · 1013 0.0 0.0
47. C2 H3 + H
C2 H2 + H2 1.200 · 1013 0.0 0.0
48. C2 H3 + O2
CH2 O + CHO 2.300 · 1012 0.0 −2.3
49. C2 H4 + M(1)
C2 H2 + H2 + M(1) 7.500 · 1017 0.0 332.0
50. C2 H4 + M(1)
C2 H3 + H + M(1) 0.850 · 1018 0.0 404.0
51. C2 H4 + H
C2 H3 + H2 0.540 · 1015 0.0 62.9
52. C2 H4 + O
CHO + CH3 2.420 · 106 2.1 0.0
53. C2 H4 + OH
C2 H3 + H2 O 2.200 · 1013 0.0 24.9
54. C2 H4 + H + M(1) → C2 H5 + M(1) 3.970 · 109 1.3 5.4
Low: 6.980 · 1018 0.0 3.2
Troe: 0.760 4.000 · 1001 1025.0 0.0
55. C2 H5 + M(1) → C2 H4 + H + M(1) 8.200 · 1013 0.0 166.8
Low: 3.400 · 1017 0.0 139.6
Troe: 0.750 9.700 · 1001 1379.0 0.0
56. C2 H5 + H
CH3 + CH3 3.000 · 1013 0.0 0.0
57. C2 H5 + O2
C2 H4 + HO2 1.100 · 1010 0.0 −6.3
58. C2 H5 + CH3
C2 H4 + CH4 1.140 · 1012 0.0 0.0
59. C2 H5 + C2 H5
C2 H4 + C2 H6 1.400 · 1012 0.0 0.0
60. C2 H6 + H
C2 H5 + H2 1.400 · 109 1.5 31.1
61. C2 H6 + O
C2 H5 + OH 1.000 · 109 1.5 24.4
62. C2 H6 + OH
C2 H5 + H2 O 7.200 · 106 2.0 3.6
63. C2 H6 + HO2
C2 H5 + H2 O2 1.700 · 1013 0.0 85.9
64. C2 H6 + O2
C2 H5 + HO2 6.000 · 1013 0.0 217.0
65. C2 H6 + CH3
C2 H5 + CH4 1.500 · 10−7 6.0 25.4
H2 H2 O O2 N2 CO CO2 CH4
M(1) 1.00 6.50 0.40 0.40 0.75 1.50 3.00
M(2) 1.00 6.50 0.40 0.40 0.75 1.50 0.66
A.2 Oxy-dehydrogenation of ethane 159
Reaction A β Ea
1. OH + H2
H + H2 O 2.140 · 108 1.5 14.4
2. O + OH
O2 + H 2.020 · 1014 −0.4 0.0
3. O + H2
OH + H 5.060 · 104 2.7 26.3
4. H + O2 + M(1)
HO2 + M(1) 4.520 · 1013 0.0 0.0
Low: 1.050 · 1019 −1.2 0.0
5. H + O 2 + H2
HO2 + H2 4.520 · 1013 0.0 0.0
Low: 1.520 · 1019 −1.13 0.0
6. H + O 2 + H2 O
HO2 + H2 O 4.520 · 1013 0.0 0.0
Low: 2.100 · 10223 −2.4 0.0
7. OH + HO2
H2 O + O2 2.130 · 1028 −4.8 14.6
8. OH + HO2
H2 O + O2 9.100 · 1014 0.0 45.9
9. H + HO2
OH + OH 1.500 · 1014 0.0 4.2
10. H + HO2
H2 + O2 8.450 · 1011 0.7 5.2
11. H + HO2
O + H2 O 3.010 · 1013 0.0 7.2
12. O + HO2
O2 + OH 3.250 · 1013 0.0 0.0
13. OH + OH
O + H2 O 3.570 · 104 2.4 −8.8
14. H + H + M(2)
H2 + M(2) 1.000 · 1018 −1.0 0.0
15. H + H + H2
H2 + H2 9.200 · 1016 −0.6 0.0
16. H + H + H2 O
H2 + H2 O 6.000 · 1019 −1.2 0.0
17. H + OH + M(3)
H2 O + M(3) 2.210 · 1022 −2.0 0.0
18. H + O + M(3)
OH + M(3) 4.710 · 1018 −1.0 0.0
19. O+O+M
O2 + M 1.890 · 1013 0.0 −7.5
20. HO2 + HO2
H2 O2 + O2 4.200 · 1014 0.0 50.1
21. HO2 + HO2
H2 O2 + O2 1.300 · 1011 0.0 −6.8
22. OH + OH + M
H2 O2 + M 1.240 · 1014 −0.4 0.0
Low: 3.040 · 1030 −4.6 8.4
Troe: 0.470 1.000 · 1002 2.0 · 1003 1.0 · 1015
23. H2 O2 + H
HO2 + H2 1.980 · 106 2.0 10.2
24. H2 O2 + H
OH + H2 O 3.070 · 1013 0.0 17.6
25. H2 O2 + O
OH + HO2 9.550 · 106 2.0 16.6
26. H2 O2 + OH
H2 O + HO2 2.400 · 100 4.0 −9.0
27. CH3 + CH3 + M(4)
C2 H6 + M(4) 9.220 · 1016 −1.2 2.7
Low: 1.140 · 1036 −5.3 7.1
Troe: 0.405 1.120 · 1003 69.6 1.0 · 1015
28. CH3 + H + M(4)
CH4 + M(4) 2.140 · 1015 −0.4 0.0
Low: 3.31 · 1030 −4.0 8.8
Troe: 0.000 1.0 · 10−15 1.0 · 10−15 40.0
29. CH4 + H
CH3 + H2 2.200 · 104 3.0 36.6
30. CH4 + OH
CH3 + H2 O 4.190 · 106 2.0 10.7
31. CH4 + O
CH3 + OH 6.920 · 108 1.6 35.5
32. CH4 + HO2
CH3 + H2 O2 1.120 · 1013 0.0 103.1
33. CH3 + HO2
CH3 O + OH 7.000 · 1012 0.0 0.0
34. CH3 + HO2
CH4 + O2 3.000 · 1012 0.0 0.0
35. CH3 + O
CH2 O + H 8.000 · 1013 0.0 0.0
36. CH3 + O2
CH3 O + O 1.450 · 1013 0.0 122.2
37. CH3 + O2
CH2 O + OH 2.510 · 1011 0.0 61.3
38. CH3 O + H
CH3 + OH 1.000 · 1014 0.0 0.0
39. CH3 + OH
3-CH2 + H2 O 3.000 · 106 2.0 10.5
40. CH3 + OH
CH2 O + H2 5.480 · 1013 0.0 12.5
41. CH3 + OH
CH2 O + H2 2.250 · 1013 0.0 18.0
42. CH3 + H
3-CH2 + H2 9.000 · 1013 0.0 63.2
43. CH3 + M
3-CH2 + H + M 1.960 · 1016 0.0 382.5
160 A. GAS-PHASE REACTION MECHANISMS
Reaction A β Ea
44. CH2 O + H + M(5)
CH3 O + M(5) 5.400 · 1011 0.5 10.9
Low: 1.50 · 1030 −4.8 23.0
Troe: 0.758 9.400 · 1001 1555 4200
45. CH3 O + H
CH2 O + H2 2.000 · 1013 0.0 0.0
46. CH3 O + OH
CH2 O + H2 O 1.000 · 1013 0.0 0.0
47. CH3 O + O
CH2 O + OH 1.000 · 1013 0.0 0.0
48. CH3 O + O2
CH2 O + HO2 6.300 · 1010 0.0 10.9
49. CH2 O + OH
CHO + H2 O 2.000 · 1013 0.0 0.0
50. CH2 O + H
CH2 O + H 2.000 · 1014 0.0 0.0
51. CH2 O + O
CO2 + H + H 5.000 · 1013 0.0 0.0
52. CH2 O + O
CO + OH + H 3.000 · 1013 0.0 0.0
53. CH2 O + O2
CO2 + H + OH 5.000 · 1012 0.0 0.0
54. CH2 O + O2
CO2 + H2 O 3.000 · 1013 0.0 0.0
55. 3-CH2 + OH
CH2 O + H 2.500 · 1013 0.0 0.0
56. 3-CH2 + CO2
CH2 O + CO 1.100 · 1011 0.0 4.2
57. 3-CH2 + O
CO + H + H 5.000 · 1013 0.0 0.0
58. 3-CH2 + O
CO + H2 3.000 · 1013 0.0 0.0
59. 3-CH2 + O2
CH2 O + O 3.290 · 1021 −3.3 12.0
60. 3-CH2 + O2
CO2 + H + H 3.290 · 1021 −3.3 12.0
61. 3-CH2 + O2
CO2 + H2 1.010 · 1021 −3.3 6.3
62. 3-CH2 + O2
CO + H2 O 7.280 · 1019 −2.5 7.6
63. 3-CH2 + O2
CHO + OH 1.290 · 1020 −3.3 1.2
64. 3-CH2 + CH3
C2 H4 + H 4.000 · 1013 0.0 0.0
65. 3-CH2 + 3-CH2
C2 H2 + H + H 4.000 · 1013 0.0 0.0
66. 3-CH2 + HCCO
C2 H3 + CO 3.000 · 1013 0.0 0.0
67. CH2 O + OH
CHO + H2 O 3.430 · 109 1.2 −1.9
68. CH2 O + H
CHO + H2 2.190 · 108 1.8 12.6
69. CH2 O + M
CHO + H + M 3.310 · 1016 0.0 338.9
70. CH2 O + O
CHO + OH 1.800 · 1013 0.0 12.9
71. CHO + O2
HO2 + CO 7.580 · 1012 0.0 1.7
72. CHO + M(6)
H + CO + M(6) 1.860 · 1017 −1.0 71.1
73. CHO + OH
H2 O + CO 1.000 · 1014 0.0 0.0
74. CHO + H
CO + H2 1.190 · 1013 0.2 0.0
75. CHO + O
CO + OH 3.000 · 1013 0.0 0.0
76. CHO + O
CO2 + H 3.000 · 1013 0.0 0.0
77. CO + OH
CO2 + H 9.420 · 103 2.2 −9.8
78. CO + O + M
CO2 + M 6.170 · 1014 0.0 12.6
79. CO + O2
CO2 + O 2.530 · 1012 0.0 199.5
80. CO + HO2
CO2 + OH 5.800 · 1013 0.0 96.0
81. C2 H6 + CH3
C2 H5 + CH4 5.500 · 10−1 4.0 34.7
82. C2 H6 + H
C2 H5 + H2 5.400 · 102 3.5 21.8
83. C2 H6 + O
C2 H5 + OH 3.000 · 107 2.0 21.4
84. C2 H6 + OH
C2 H5 + H2 O 7.230 · 106 2.0 3.6
85. C2 H5 + H
C2 H4 + H2 1.250 · 1014 0.0 33.5
86. C2 H5 + H
CH3 + CH3 3.000 · 1013 0.0 0.0
87. C2 H5 + H
C2 H6 7.000 · 1013 0.0 0.0
88. C2 H5 + OH
C2 H4 + H2 O 4.000 · 1013 0.0 0.0
89. C2 H5 + O
CH3 + CH2 O 1.000 · 1014 0.0 0.0
90. C2 H5 + HO2
CH3 + CH2 O + OH 3.000 · 1013 0.0 0.0
91. C2 H5 + O2
C2 H4 + HO2 3.000 · 1020 −2.9 28.3
92. C2 H5 + O2
C2 H4 + HO2 2.120 · 10−6 6.0 39.7
93. C2 H4 + H
C2 H3 + H2 3.360 · 10−7 6.0 7.1
94. C2 H4 + OH
C2 H3 + H2 O 2.020 · 1013 0.0 24.8
95. C2 H4 + O
CH3 + CHO 1.020 · 107 1.9 0.7
96. C2 H4 + O
CH2 CHO + H 3.390 · 106 1.9 0.7
97. C2 H4 + CH3
C2 H3 + CH4 6.620 · 100 3.7 39.7
98. C2 H4 + H + M(4)
C2 H5 + M(4) 1.080 · 1012 0.5 7.6
Low: 1.11 · 1034 −5.0 18.5
Troe: 1.00 1.0 · 10−15 95 200
99. C2 H4 + M
C2 H2 + H2 + M 1.800 · 1013 0.0 318.0
Low: 1.5 · 1015 0.0 232.7
A.2 Oxy-dehydrogenation of ethane 161
Reaction A β Ea
100. C2 H3 + H + M(5)
C2 H4 + M(5) 6.100 · 1012 0.3 1.2
Low: 9.80 · 1029 −3.86 13.9
Troe: 0.782 2.080 · 1002 2663 6095
101. C2 H3 + H
C2 H2 + H2 4.000 · 1013 0.0 0.0
102. C2 H3 + O
CH2 CO + H 3.000 · 1013 0.0 0.0
103. C2 H3 + O2
CH2 O + CHO 1.700 · 1029 −5.3 27.2
104. C2 H3 + O2
CH2 CHO + O 3.500 · 1014 −0.6 22.0
105. C2 H3 + O2
C2 H2 + HO2 2.120 · 10−6 6.0 39.7
106. C2 H3 + OH
C2 H2 + H2 O 2.000 · 1013 0.0 0.0
107. C2 H3 + CH3
C2 H2 + CH4 2.000 · 1013 0.0 0.0
108. C2 H3 + C2 H3
C2 H4 + C2 H2 1.450 · 1013 0.0 0.0
109. C2 H2 + OH
CH2 CO + H 2.180 · 10−4 4.5 −4.2
110. C2 H2 + OH
CH2 CO + H 2.000 · 1011 0.0 0.0
111. C2 H2 + OH
CH3 + CO 4.830 · 10−4 4.0 −8.4
112. C2 H2 + O
3-CH2 + CO 6.120 · 106 2.0 7.9
113. C2 H2 + O
HCCO + H 1.430 · 107 2.0 7.9
114. C2 H2 + O2
HCCO + OH 4.000 · 107 1.5 125.9
115. C2 H2 + H + M(4)
C2 H3 + M(4) 3.110 · 1011 0.6 10.8
Low: 2.25 · 1040 −7.27 27.6
Troe: 1.00 1.0 · 10−15 675 1.0 · 1015
116. CH2 CHO + H
CH2 CO + H2 4.000 · 1013 0.0 0.0
117. CH2 CHO + O
CH2 O + CHO 1.000 · 1014 0.0 0.0
118. CH2 CHO + OH
CH2 CO + H2 O 3.000 · 1013 0.0 0.0
119. CH2 CHO + O2
CH2 O + CO + OH 3.000 · 1010 0.0 0.0
120. CH2 CHO + CH3 → C2 H5 + CO + H 4.900 · 1014 −0.5 0.0
121. CH2 CHO
CH2 CO + H 3.950 · 1038 −7.6 188.8
122. CH2 CO + O
CO2 + 3-CH2 1.750 · 1012 0.0 5.6
123. CH2 CO + H
CH3 + CO 7.000 · 1012 0.0 12.6
124. CH2 CO + H
HCCO + H2 2.000 · 1014 0.0 33.5
125. CH2 CO + O
HCCO + OH 1.000 · 1013 0.0 33.5
126. CH2 CO + OH
HCCO + H2 O 1.000 · 1013 0.0 8.4
127. 3-CH2 + CO + M(5)
CH2 CO + M(5) 8.100 · 1011 0.5 18.9
Low: 1.90 · 1033 −5.11 29.7
Troe: 0.591 2.750 · 1002 1226 5185.0
128. HCCO + O
H + CO + CO 8.000 · 1013 0.0 0.0
129. HCCO + O2
CHO + CO + O 2.500 · 108 1.0 0.0
130. HCCO + O2
CO2 + CHO 2.400 · 1011 0.0 −3.6
131. HCCO + HCCO
C2 H2 + CO + CO 1.000 · 1013 0.0 0.0
H2 O H2 CH4 CO2 CO
M(1) 0.00 0.00 10.00 3.80 1.90
M(2) 0.00 0.00 1.00 1.00 1.00
M(3) 6.40 1.00 1.00 1.00 1.00
M(4) 5.00 2.00 1.00 3.00 2.00
M(5) 5.00 1.00 1.00 1.00 1.00
M(6) 5.00 1.87 2.81 3.00 1.87
162 B. SURFACE REACTION MECHANISMS
Reaction A / S0 β /µ Ea /
I Adsorption
1. H2 + Rh(s) + Rh(s) → H(s) + H(s) 8.400 · 1018 1.0 0.0
θRh(s) -1.0
2. O2 + Rh(s1) + Rh(s1) → O(s1) + O(s1) 1.300 · 1017 1.0 0.0
θRh(s1) -1.0
3. CH4 + Rh(s) + Rh(s) → CH3 (s) + H(s) 1.100 · 1018 1.0 21.0
θRh(s) -1.0
4. H2 O + Rh(s) → H2 O(s) 4.600 · 109 1.0 0.0
5. CO + Rh(s) → CO(s) 1.200 · 1010 1.0 0.0
II Desorption
6. H(s) + H(s) → Rh(s) + Rh(s) + H2 3.000 · 1021 0.0 75.4
θH(s) -1.0
7. O(s1) + O(s1) → Rh(s1) + Rh(s1) + O2 3.000 · 1021 0.0 293.3
θO(s1) -1.0
8. H2 O(s) → H2 O + Rh(s) 1.000 · 1013 0.0 45.2
9. CO(s) → CO + Rh(s) 4.000 · 1013 0.0 132.4
θCO(s) 44.0
10. OH(s) → OH + Rh(s) 8.100 · 1011 0.0 142.5
III Surface reactions
11. O(s1) + H(s) → OH(s) + Rh(s1) 4.200 · 1021 0.0 83.8
12. OH(s) + Rh(s1) → O(s1) + H(s) 6.000 · 1021 0.0 21.0
13. H(s) + OH(s) → H2 O(s) + Rh(s) 1.800 · 1026 0.0 33.5
14. H2 O(s) + Rh(s) → H(s) + OH(s) 3.000 · 1023 0.0 155.0
15. OH(s) + OH(s) → H2 O(s) + O(s) 2.400 · 1024 0.0 62.8
16. O(s) + Rh(s1) → Rh(s) + O(s1) 3.700 · 1021 0.0 0.0
17. C(s) + O(s1) → CO(s) + Rh(s1) 3.000 · 1022 0.0 62.8
18. CO(s) + Rh(s1) → C(s) + O(s1) 6.000 · 1019 0.0 167.6
19. CO(s) + O(s1) → CO2 + Rh(s) + Rh(s1) 6.000 · 1020 0.0 104.7
20. CH3 (s) + Rh(s) → CH2 (s) + H(s) 3.700 · 1021 0.0 0.0
21. CH2 (s) + Rh(s) → CH(s) + H(s) 3.700 · 1021 0.0 0.0
22. CH(s) + Rh(s) → C(s) + H(s) 3.700 · 1021 0.0 0.0
The suffixes (s) and (s1) denote different adsorption sites, the latter one available for oxygen adsorption only.
Reaction steps 3. and 20.-22. represent only one recation in the original mechanism being first order in Rh(s). Splitting
up this reaction in an adsorption step, again being first order in Rh(s), and fast consecutive decomposition steps (20.-22.)
does not change any results.
164 B. SURFACE REACTION MECHANISMS
Reaction A / S0 β /µ Ea /
I Adsorption
1. H2 + Rh(s) + Rh(s) → H(s) + H(s) S0 = 1.0 · 10−2 0.0 0.0
2. O2 + Rh(s) + Rh(s) → O(s) + O(s) S0 = 1.0 · 10−2 0.0 0.0
3. CH4 + Rh(s) → CH4 (s) S0 = 8.0 · 10−3 0.0 0.0
4. H2 O + Rh(s) → H2 O(s) S0 = 1.0 · 10−1 0.0 0.0
5. CO2 + Rh(s) → CO2 (s) S0 = 1.0 · 10−5 0.0 0.0
6. CO + Rh(s) → CO(s) S0 = 5.0 · 10−1 0.0 0.0
II Desorption
7. H(s) + H(s) → Rh(s) + Rh(s) + H2 3.000 · 1021 0.0 77.8
8. O(s) + O(s) → Rh(s) + Rh(s) + O2 1.300 · 1022 0.0 355.2
9. H2 O(s) → H2 O + Rh(s) 3.000 · 1013 0.0 45.0
10. CO(s) → CO + Rh(s) 3.500 · 1013 0.0 133.4
11. CO2 (s) → CO2 + Rh(s) 1.000 · 1013 0.0 21.7
12. CH4 (s) → CH4 + Rh(s) 1.000 · 1013 0.0 25.1
III Surface reactions
13. H(s) + O(s) → OH(s) + Rh(s) 5.000 · 1022 0.0 83.7
14. OH(s) + Rh(s) → H(s) + O(s) 3.000 · 1020 0.0 37.7
15. H(s) + OH(s) → H2 O(s) + Rh(s) 3.000 · 1020 0.0 33.5
16. H2 O(s) + Rh(s) → H(s) + OH(s) 5.000 · 1022 0.0 106.4
17. OH(s) + OH(s) → H2 O(s) + O(s) 3.000 · 1021 0.0 100.8
18. H2 O(s) + O(s) → OH(s) + OH(s) 3.000 · 1021 0.0 224.2
19. C(s) + O(s) → CO(s) + Rh(s) 3.000 · 1022 0.0 97.9
20. CO(s) + Rh(s) → C(s) + O(s) 2.500 · 1021 0.0 169.0
21. CO(s) + O(s) → CO2 (s) + Rh(s) 1.400 · 1020 0.0 121.6
22. CO2 (s) + Rh(s) → CO(s) + O(s) 3.000 · 1021 0.0 115.3
23. CH4 (s) + Rh(s) → CH3 (s) + H(s) 3.700 · 1021 0.0 61.0
24. CH3 (s) + H(s) → CH4 (s) + Rh(s) 3.700 · 1021 0.0 51.0
25. CH3 (s) + Rh(s) → CH2 (s) + H(s) 3.700 · 1024 0.0 103.0
26. CH2 (s) + H(s) → CH3 (s) + Rh(s) 3.700 · 1021 0.0 44.0
27. CH2 (s) + Rh(s) → CH(s) + H(s) 3.700 · 1024 0.0 100.0
28. CH(s) + H(s) → CH2 (s) + Rh(s) 3.700 · 1021 0.0 68.0
29. CH(s) + Rh(s) → C(s) + H(s) 3.700 · 1021 0.0 21.0
30. C(s) + H(s) → CH(s) + Rh(s) 3.700 · 1021 0.0 172.8
31. CH4 (s) + O(s) → CH3 (s) + OH(s) 1.700 · 1024 0.0 80.3
32. CH3 (s) + OH(s) → CH4 (s) + O(s) 3.700 · 1021 0.0 24.3
33. CH3 (s) + O(s) → CH2 (s) + OH(s) 3.700 · 1024 0.0 120.3
34. CH2 (s) + OH(s) → CH3 (s) + O(s) 3.700 · 1021 0.0 15.1
35. CH2 (s) + O(s) → CH(s) + OH(s) 3.700 · 1024 0.0 158.4
36. CH(s) + OH(s) → CH2 (s) + O(s) 3.700 · 1021 0.0 36.8
37. CH(s) + O(s) → C(s) + OH(s) 3.700 · 1021 0.0 30.1
38. C(s) + OH(s) → CH(s) + O(s) 3.700 · 1021 0.0 145.5
B.3 Oxy-dehydrogenation of ethane on platinum 165
Reaction A / S0 β /µ Ea /
I Adsorption
1. H + Pt(s) → H(s) S 0 = 1.0 · 10−0 0.0 0.0
2.. H2 + Pt(s) + Pt(s) → H(s) + H(s) S 0 = 4.6 · 10−2 0.0 0.0
θPt(s) -1.0
3. H2 + C(s) → CH2 (s) S 0 = 4.0 · 10−2 0.0 29.7
θC(s) -4.6
4. O + Pt(s) → O(s) S 0 = 1.0 · 10−0 0.0 0.0
5. O2 + Pt(s) + Pt(s) → O(s) + O(s) 1.891 · 1021 −0.5 0.0
6. OH + Pt(s) → OH(s) S 0 = 1.0 · 10−0 0.0 0.0
7. H2 O + Pt(s) → H2 O(s) S 0 = 7.5 · 10−1 0.0 0.0
8. CO + Pt(s) → CO(s) S 0 = 8.4 · 10−1 0.0 0.0
9. CO2 + Pt(s) → CO2 (s) S 0 = 5.0 · 10−3 0.0 0.0
10. CH3 + Pt(s) → CH3 (s) S 0 = 1.0 · 10−0 0.0 0.0
11. CH4 + C(s) → CHCH3 (s) S 0 = 7.0 · 10−9 0.0 23.0
θC(s) -47.5
12. CH4 + Pt(s) + Pt(s) → CH3 (s) + H(s) S 0 = 9.0 · 10−4 0.0 72.2
13. CH4 + O(s) + Pt(s) → CH3 (s) + OH(s) 5.000 · 1018 0.7 42.0
θO(s) -8.0
14. CH4 + OH(s) + Pt(s) → CH3 (s) + H2 O(s) S0 = 1.0 · 10−0 0.0 10.0
15. C2 H2 + Pt(s) → C2 H2 (s) S0 = 5.0 · 10−2 0.0 0.0
16. C2 H4 + Pt(s) → C2 H4 (s) S0 = 1.5 · 10−2 0.0 0.0
17. C2 H5 + Pt(s) → C2 H5 (s) S0 = 1.0 · 10−0 0.0 0.0
18. C2 H6 + Pt(s) + Pt(s) → C2 H6 (s) S0 = 1.5 · 10−2 0.0 0.0
II Desorption
19. H(s) → H + Pt(s) 6.000 · 1013 0.0 254.4
θH(s) 5.0
20. H(s) + H(s) → Pt(s) + Pt(s) + H2 3.700 · 1021 0.0 67.4
θH(s) 10.0
21. CH2 (s) → C(s) + H2 7.690 · 1013 0.0 25.1
θC(s) -50.0
22. O(s) → O + Pt(s) 1.000 · 1013 0.0 358.8
θO(s) 94.1
23. O(s) + O(s) → Pt(s) + Pt(s) + O2 3.700 · 1021 0.0 227.4
θO(s) 188.3
24. OH(s) → OH + Pt(s) 5.000 · 1013 0.0 251.1
θO(s) 167.4
25. H2 O(s) → H2 O + Pt(s) 4.500 · 1012 0.0 41.8
26. CO(s) → CO + Pt(s) 2.500 · 1016 0.0 146.0
θCO(s) 33.0
27. CO2 (s) → CO2 + Pt(s) 1.000 · 1013 0.0 27.1
28. CH3 (s) → Pt(s) + CH3 1.000 · 1013 0.0 163.0
29. CH3 (s) + H(s) → CH4 + Pt(s) + Pt(s) 1.500 · 1020 0.0 50.0
30. CH3 (s) + H2 O(s) → CH4 + OH(s) + Pt(s) 2.500 · 1020 0.0 23.0
θH(s) 50.0
31. CH3 (s) + OH(s) → CH4 + O(s) + Pt(s) 3.700 · 1021 0.0 85.9
32. C2 H2 (s) → Pt(s) + C2 H2 1.000 · 1012 0.0 58.6
33. C2 H4 (s) → Pt(s) + C2 H4 1.000 · 1013 0.0 50.2
34. CHCH3 (s) → C(s) + CH4 1.000 · 1010 0.0 25.5
θC(s) -47.5
35. C2 H5 (s) → Pt(s) + C2 H5 1.000 · 1013 0.0 173.0
36. C2 H6 (s) → Pt(s) + Pt(s) + C2 H6 1.000 · 1013 0.0 20.9
166 B. SURFACE REACTION MECHANISMS
Reaction A / S0 β /µ Ea /
III Surface reactions
37. H(s) + O(s) → OH(s) + Pt(s) 1.280 · 1021 0.0 11.2
38. OH(s) + Pt(s) → H(s) + O(s) 7.390 · 1019 0.0 77.3
θO(s) 73.2
39. H(s) + OH(s) → H2 O(s) + Pt(s) 2.040 · 1021 0.0 66.2
40. H2 O(s) + Pt(s) → H(s) + OH(s) 1.150 · 1019 0.0 101.4
θO(s) -167.4
41. OH(s) + OH(s) → H2 O(s) + O(s) 7.400 · 1020 0.0 74.0
42. H2 O(s) + O(s) → OH(s) + OH(s) 1.000 · 1020 0.0 43.1
θO(s) -240.6
43. C(s) + O(s) → CO(s) + Pt(s) 3.700 · 1019 0.0 0.0
44. CO(s) + Pt(s) → C(s) + O(s) 3.700 · 1019 0.0 236.5
θCO(s) 33.0
45. CO(s) + O(s) → CO2 (s) + Pt(s) 3.700 · 1019 0.0 117.6
θCO(s) 33.0
46. CO2 (s) + Pt(s) → CO(s) + O(s) 3.700 · 1019 0.0 173.3
θO(s) -94.1
47. CO(s) + OH(s) → CO2 (s) + H(s) 2.000 · 1019 0.0 38.7
θCO(s) 30.0
48. CO2 (s) + H(s) → CO(s) + OH(s) 2.000 · 1019 0.0 28.3
49. CH3 (s) + Pt(s) → CH2 (s) + H(s) 1.262 · 1022 0.0 70.3
50. CH2 (s) + H(s) → CH3 (s) + Pt(s) 3.090 · 1022 0.0 0.0
θH(s) 2.8
51. CH2 (s) + Pt(s) → CH(s) + H(s) 7.314 · 1022 0.0 58.9
θC(s) -50.0
52. CH(s) + H(s) → CH2 (s) + Pt(s) 3.090 · 1022 0.0 0.0
θH(s) 2.8
53. CH(s) + Pt(s) → C(s) + H(s) 3.090 · 1022 0.0 0.0
θH(s) 2.8
54. C(s) + H(s) → CH(s) + Pt(s) 1.248 · 1022 0.0 138.0
55. C2 H6 (s) + O(s) → C2 H5 (s) + OH(s) + Pt(s) 3.700 · 1021 0.0 25.1
56. C2 H5 (s) + OH(s) + Pt(s) → C2 H6 (s) + O(s) 1.350 · 1030 0.0 77.4
57. C2 H4 (s) → CHCH3 (s) 1.000 · 1013 0.0 83.3
58. CHCH3 (s) → C2 H4 (s) 1.000 · 1013 0.0 75.3
59. C2 H5 (s) + H(s) → C2 H6 (s) 3.700 · 1021 0.0 41.8
60. C2 H6 (s) → C2 H5 (s) + H(s) 7.000 · 1012 0.0 57.7
61. CH3 (s) + CH3 (s) → C2 H6 (s) 1.000 · 1021 0.0 14.5
62. C2 H6 (s) → CH3 (s) + CH3 (s) 1.000 · 1013 0.0 89.0
63. C2 H5 (s) + Pt(s) → CHCH3 (s) + H(s) 1.000 · 1022 0.0 54.4
64. CHCH3 (s) + H(s) → C2 H5 (s) + Pt(s) 1.000 · 1021 0.0 29.3
65. CHCH3 (s) + Pt(s) → CCH3 (s) + H(s) 2.000 · 1022 0.0 99.1
66. CCH3 (s) + H(s) → CHCH3 (s) + Pt(s) 3.700 · 1021 0.0 75.3
67. CHCH3 (s) + Pt(s) → CHCH2 (s) + H(s) 3.700 · 1021 0.0 128.5
68. CHCH2 (s) + H(s) → CHCH3 (s) + Pt(s) 3.700 · 1021 0.0 57.3
69. C2 H4 (s) + Pt(s) → CHCH2 (s) + H(s) 3.700 · 1021 0.0 112.7
70. CHCH2 (s) + H(s) → C2 H4 (s) + Pt(s) 3.700 · 1021 0.0 33.5
71. CHCH2 (s) + Pt(s) → CCH2 (s) + H(s) 3.700 · 1021 0.0 121.3
72. CCH2 (s) + H(s) → CHCH2 (s) + Pt(s) 3.700 · 1021 0.0 51.7
73. CCH3 (s) + Pt(s) → CH3 (s) + C(s) 3.700 · 1021 0.0 46.9
θC(s) -50.0
74. CH3 (s) + C(s) → CCH3 (s) + Pt(s) 3.700 · 1021 0.0 46.0
75. C2 H2 (s) → CCH2 (s) 1.000 · 1013 0.0 61.5
76. CCH2 (s) → C2 H2 (s) 1.000 · 1013 0.0 4.2
77. CCH3 (s) → CHCH2 (s) 1.000 · 1013 0.0 176.0
78. CHCH2 (s) → CCH3 (s) 1.000 · 1013 0.0 128.6
79. C2 H2 (s) + Pt(s) → CCH(s) + H(s) 3.700 · 1021 0.0 133.5
80. CCH(s) + H(s) → C2 H2 (s) + Pt(s) 3.700 · 1021 0.0 66.9
81. CCH(s) + Pt(s) → CH(s) + C(s) 3.700 · 1021 0.0 125.1
82. CH(s) + C(s) → CCH(s) + Pt(s) 3.700 · 1021 0.0 121.3
B.4 Oxidation of hydrogen, carbon monoxide, and methane on platinum 167
Reaction A / S0 β /µ Ea /
I AdsorPtion
1. H2 + Pt(s) + Pt(s) → H(s) + H(s) S 0 = 4.6 · 10−2 0.0 0.0
θPt(s) -1.0
2. H + Pt(s) → H(s) S 0 = 1.0 · 10−0 0.0 0.0
3. O2 + Pt(s) + Pt(s) → O(s) + O(s) 1.800 · 1021 −0.5 0.0
4. O2 + Pt(s) + Pt(s) → O(s) + O(s) S 0 = 2.3 · 10−2 0.0 0.0
5. CH4 + Pt(s) + Pt(s) → CH3 (s) + H(s) S 0 = 1.0 · 10−2 0.0 0.0
θPt(s) 0.3
6. O + Pt(s) → O(s) S 0 = 1.0 · 10−0 0.0 0.0
7. H2 O + Pt(s) → H2 O(s) S 0 = 7.5 · 10−1 0.0 0.0
8. CO + Pt(s) → CO(s) S 0 = 8.4 · 10−1 0.0 0.0
θPt(s) 1.0
9. OH + Pt(s) → OH(s) S 0 = 1.0 · 10−0 0.0 0.0
II DesorPtion
10. H(s) + H(s) → Pt(s) + Pt(s) + H2 3.700 · 1021 0.0 67.4
θH(s) 6.0
11. O(s) + O(s) → Pt(s) + Pt(s) + O2 3.700 · 1021 0.0 213.0
θO(s) 60.0
12. H2 O(s) → H2 O + Pt(s) 1.000 · 1013 0.0 40.3
13. OH(s) → OH + Pt(s) 1.000 · 1013 0.0 192.8
14. CO(s) → CO + Pt(s) 1.000 · 1013 0.0 125.5
15. CO2 (s) → CO2 + Pt(s) 1.000 · 1013 0.0 20.5
16. O(s) + H(s)
OH(s) + Pt(s) 3.700 · 1021 0.0 11.5
III Surface reactions
17. H(s) + OH(s)
H2 O(s) + Pt(s) 3.700 · 1021 0.0 17.4
18. OH(s) + OH(s)
H2 O(s) + O(s) 3.700 · 1021 0.0 48.2
19. CO(s) + O(s) → CO2 (s) + Pt(s) 3.700 · 1021 0.0 105.0
20. C(s) + O(s) → CO(s) + Pt(s) 3.700 · 1021 0.0 62.8
21. CO(s) + Pt(s) → C(s) + O(s) 1.000 · 1018 0.0 184.0
22. CH3 (s) + Pt(s) → CH2 (s) + H(s) 3.700 · 1021 0.0 20.0
23. CH2 (s) + Pt(s) → CH(s) + H(s) 3.700 · 1021 0.0 20.0
24. CH(s) + Pt(s) → C(s) + H(s) 3.700 · 1021 0.0 20.0
Reaction A / S0 β /µ Ea /
C3 H6 /CO - oxidation on Pt
I Adsorption
1. O2 + Pt(s) + Pt(s) → O(s) + O(s) S 0 = 7.0 · 10−2 0.0 0.0
2. C3 H6 + Pt(s) + Pt(s) → C3 H6 (s) S 0 = 9.8 · 10−1 0.0 0.0
3. C3 H6 + O(s) + Pt(s) → C3 H5 (s) + OH(s) S 0 = 5.0 · 10−2 0.0 0.0
θPt(s) -0.9
4. H2 + Pt(s) + Pt(s) → H(s) + H(s) S 0 = 4.6 · 10−2 0.0 0.0
θPt(s) -1.0
5. H2 O + Pt(s) → H2 O(s) S 0 = 7.5 · 10−1 0.0 0.0
6. CO2 + Pt(s) → CO2 (s) S 0 = 5.0 · 10−3 0.0 0.0
7. CO + Pt(s) → CO(s) S 0 = 8.4 · 10−1 0.0 0.0
II Desorption
8. O(s) + O(s) → O2 + Pt(s) + Pt(s) 3.70 · 1021 0.0 232.2
θO(s) 90.0
9. C3 H6 (s) → C3 H6 + Pt(s) + Pt(s) 1.00 · 1013 0.0 72.7
10. C3 H5 (s) + OH(s) → C3 H6 + O(s) + Pt(s) 3.70 · 1021 0.0 31.0
11. H(s) + H(s) → H2 + Pt(s) + Pt(s) 3.70 · 1021 0.0 67.4
θH(s) 6.0
12. H2 O(s) → Pt(s) + H2 O 1.00 · 1013 0.0 40.3
13. CO(s) → CO + Pt(s) 1.00 · 1013 0.0 136.4
θCO(s) 33.0
14. CO2 (s) → CO2 + Pt(s) 1.00 · 1013 0.0 27.1
III Surface reactions
IIIa C3 H5 (s)-oxidation (global reaction)
15. C3 H5 (s) + 5O(s) → 3C(s) + 5OH(s) 3.70 · 1021 0.0 95.0
IIIb C3 H6 (s) -decomposition
16. C3 H6 (s) → CC2 H5 (s) + H(s) 1.00 · 1013 0.0 75.4
17. CC2 H5 (s) + H(s) → C3 H6 (s) 3.70 · 1021 0.0 48.8
18. CC2 H5 (s) + Pt(s) → C2 H3 (s) + CH2 (s) 3.70 · 1021 0.0 108.2
19. C2 H3 (s) + CH2 (s) → CC2 H5 (s) + Pt(s) 3.70 · 1021 0.0 3.2
20. C2 H3 (s) + Pt(s) → CH3 (s) + C(s) 3.70 · 1021 0.0 46.0
21. CH3 (s) + C(s) → C2 H3 (s) + Pt(s) 3.70 · 1021 0.0 46.9
IIIc CHx -decomposition
22. CH3 (s) + Pt(s) → CH2 (s) + H(s) 1.26 · 1022 0.0 70.4
23. CH2 (s) + H(s) → CH3 (s) + Pt(s) 3.09 · 1022 0.0 0.0
24. CH2 (s) + Pt(s) → CH(s) + H(s) 7.00 · 1022 0.0 59.2
25. CH(s) + H(s) → CH2 (s) + Pt(s) 3.09 · 1022 0.0 0.0
26. CH(s) + Pt(s) → C(s) + H(s) 3.09 · 1022 0.0 0.0
27. C(s) + H(s) → CH(s) + Pt(s) 1.25 · 1022 0.0 138.0
IIId C2 Hx -oxidation
28. C2 H3 (s) + O(s) → CH3 CO(s) + Pt(s) 3.70 · 1019 0.0 62.3
29. CH3 CO(s) + Pt(s) → C2 H3 (s) + O(s) 3.70 · 1021 0.0 196.7
θO(s) -45.0
30. CH3 (s) + CO(s) → CH3 CO(s) + Pt(s) 3.70 · 1021 0.0 82.9
31. CH3 CO(s) + Pt(s) → CH3 (s) + CO(s) 3.70 · 1021 0.0 0.0
θCO(s) -33.0
B.5 Mechanism for a three-way catalyst 169
Reaction A / S0 β /µ Ea /
IIIe CHx -oxidation
32. CH3 (s) + O(s) → CH2 (s) + OH(s) 3.70 · 1021 0.0 36.6
33. CH2 (s) + OH(s) → CH3 (s) + O(s) 3.70 · 1021 0.0 25.1
34. CH2 (s) + O(s) → CH(s) + OH(s) 3.70 · 1021 0.0 25.1
35. CH(s) + OH(s) → CH2 (s) + O(s) 3.70 · 1021 0.0 25.2
36. CH(s) + O(s) → C(s) + OH(s) 3.70 · 1021 0.0 25.1
37. C(s) + OH(s) → CH(s) + O(s) 3.70 · 1021 0.0 224.8
IIIf H, OH, H2 O - reactions
38. O(s) + H(s) → OH(s) + Pt(s) 3.70 · 1021 0.0 11.5
39. OH(s) + Pt(s) → O(s) + H(s) 5.77 · 1022 0.0 74.9
40. H(s) + OH(s) → H2 O(s) + Pt(s) 3.70 · 1021 0.0 17.4
41. H2 O(s) + Pt(s) → H(s) + OH(s) 3.66 · 1021 0.0 73.6
42. OH(s) + OH(s) → H2 O(s) + O(s) 3.70 · 1021 0.0 48.2
43. H2 O(s) + O(s) → OH(s) + OH(s) 2.35 · 1020 0.0 41.0
IIIg CO-oxidation
44. CO(s) + O(s) → CO2 (s) + Pt(s) 3.70 · 1020 0.0 108.0
θCO(s) 33.0
θNO(s) -90.0
45. CO2 (s) + Pt(s) → CO(s) + O(s) 3.70 · 1021 0.0 165.1
θO(s) -45.0
46. C(s) + O(s) → CO(s) + Pt(s) 3.70 · 1021 0.0 0.0
θCO(s) -33.0
47. CO(s) + Pt(s) → C(s) + O(s) 3.70 · 1021 0.0 218.5
θO(s) -45.0
NO - reduction on Pt
I Adsorption
48. NO + Pt(s) → NO(s) 8.50 · 10−1 0.0 0.0
II Desorption
49. NO(s) → NO + Pt(s) 1.00 · 1016 0.0 140.0
50. N(s) + N(s) → N2 + Pt(s) + Pt(s) 3.70 · 1021 0.0 113.9
θCO(s) 75.0
III NO - surface reactions
51. NO(s) + Pt(s) → N(s) + O(s) 5.00 · 1020 0.0 107.8
θCO(s) -3.0
52. N(s) + O(s) → NO(s) + Pt(s) 3.70 · 1021 0.0 128.1
θO(s) 45.0
NO/CO - reactions on Rh
I Adsorption
53. O2 + Rh(s) + Rh(s) → O(Rh) + O(Rh) 1.00 · 10−2 0.0 0.0
θRh(s) -1.0
54. CO + Rh(s) → CO(Rh) 5.00 · 10−1 0.0 0.0
55. NO + Rh(s) → NO(Rh) 5.00 · 10−1 0.0 0.0
II Desorption
56. O(Rh) + O(Rh) → O2 + Rh(s) + Rh(s) 3.00 · 1021 0.0 293.3
57. CO(Rh) → CO + Rh(s) 1.00 · 1014 0.0 132.3
θN(Rh) 41.9
θCO(Rh) 18.8
58. NO(Rh) → NO + Rh(s) 5.00 · 1013 0.0 108.9
59. N(Rh) + N(Rh) → N2 + Rh(S) + Rh(S) 1.11 · 1019 0.0 136.9
θN(Rh) 16.7
III NO/CO-surface reactions
60. CO(Rh) + O(Rh) → CO2 + Rh(s) + Rh(s) 3.70 · 1020 0.0 59.9
61. NO(Rh) + Rh(s) → N(Rh) + O(Rh) 2.22 · 1022 0.0 79.5
Reaction 15. is a complex fast reaction that takes place if sufficient O(s) is available for Reaction 3. Reaction 15. is
first order in O(s) and C3 H5 (s).
170 B. SURFACE REACTION MECHANISMS
Reaction A / S0 β /µ Ea /
C3 H6 - oxidation
I Adsorption
1. O2 + Pt(s) + Pt(s) → O(s) + O(s) S 0 = 7.0 · 10−2 0.0 0.0
2. C3 H6 + Pt(s) + Pt(s) → C3 H6 (s) S 0 = 9.8 · 10−1 0.0 0.0
3. C3 H6 + O(s) + Pt(s) → C3 H5 (s) + OH(s) S 0 = 5.0 · 10−2 0.0 0.0
θPt(s) -0.9
4. H2 + Pt(s) + Pt(s) → H(s) + H(s) S 0 = 4.6 · 10−2 0.0 0.0
θPt(s) -1.0
5. H2 O + Pt(s) → H2 O(s) S0 = 7.5 · 10−1 0.0 0.0
6. OH + Pt(s) → OH(s) S0 = 1.0 · 10−0 0.0 0.0
7. CO2 + Pt(s) → CO2 (s) S0 = 5.0 · 10−3 0.0 0.0
8. CO + Pt(s) → CO(s) S0 = 8.4 · 10−1 0.0 0.0
II Desorption
9. O(s) + O(s) → O2 + Pt(s) + Pt(s) 3.70 · 1021 0.0 232.2
θO(s) 90.0
10. C3 H6 (s) → C3 H6 + Pt(s) + Pt(s) 1.00 · 1013 0.0 72.7
11. C3 H5 (s) + OH(s) → C3 H6 + O(s) + Pt(s) 3.70 · 1021 0.0 31.0
12. H(s) + H(s) → H2 + Pt(s) + Pt(s) 3.70 · 1021 0.0 67.4
θH(s) 6.0
13. H2 O(s) → Pt(s) + H2 O 1.00 · 1013 0.0 40.3
14. OH(s) → Pt(s) + OH 1.00 · 1013 0.0 251.4
15. CO(s) → CO + Pt(s) 1.00 · 1013 0.0 146.4
θCO(s) 33.0
16. CO2 (s) → CO2 + Pt(s) 1.00 · 1013 0.0 27.1
III Surface reactions
IIIa C3 H5 (s)-oxidation (global reaction)
17. C3 H5 (s) + 5O(s) → 3C(s) + 5OH(s) 3.70 · 1021 0.0 95.0
IIIb C3 H6 (s) -decomposition
18. C3 H6 (s) → CC2 H5 (s) + H(s) 1.00 · 1013 0.0 75.4
19. CC2 H5 (s) + H(s) → C3 H6 (s) 3.70 · 1021 0.0 48.8
20. CC2 H5 (s) + Pt(s) → C2 H3 (s) + CH2 (s) 3.70 · 1021 0.0 108.2
21. C2 H3 (s) + CH2 (s) → CC2 H5 (s) + Pt(s) 3.70 · 1021 0.0 3.2
22. C2 H3 (s) + Pt(s) → CH3 (s) + C(s) 3.70 · 1021 0.0 46.0
23. CH3 (s) + C(s) → C2 H3 (s) + Pt(s) 3.70 · 1021 0.0 46.9
24. CH3 (s) + Pt(s) → CH2 (s) + H(s) 1.26 · 1022 0.0 70.4
25. CH2 (s) + H(s) → CH3 (s) + Pt(s) 3.09 · 1022 0.0 0.0
26. CH2 (s) + Pt(s) → CH(s) + H(s) 7.00 · 1022 0.0 59.2
27. CH(s) + H(s) → CH2 (s) + Pt(s) 3.09 · 1022 0.0 0.0
28. CH(s) + Pt(s) → C(s) + H(s) 3.09 · 1022 0.0 0.0
29. C(s) + H(s) → CH(s) + Pt(s) 1.25 · 1022 0.0 138.0
IIIc CHx -decomposition
IIId C2 Hx -oxidation
30. C2 H3 (s) + O(s) → CH3 CO(s) + Pt(s) 3.70 · 1019 0.0 62.3
31. CH3 CO(s) + Pt(s) → C2 H3 (s) + O(s) 3.70 · 1021 0.0 196.7
θO(s) -45.0
32. CH3 (s) + CO(s) → CH3 CO(s) + Pt(s) 3.70 · 1021 0.0 92.9
33. CH3 CO(s) + Pt(s) → CH3 (s) + CO(s) 3.70 · 1021 0.0 0.0
θCO(s) -33.0
B.6 HC-SCR on Pt/Al2 O3 171
Reaction A / S0 β /µ Ea /
IIIe CHx -oxidation
34. CH3 (s) + O(s) → CH2 (s) + OH(s) 3.70 · 1021 0.0 36.6
35. CH2 (s) + OH(s) → CH3 (s) + O(s) 3.70 · 1021 0.0 25.1
36. CH2 (s) + O(s) → CH(s) + OH(s) 3.70 · 1021 0.0 25.1
37. CH(s) + OH(s) → CH2 (s) + O(s) 3.70 · 1021 0.0 25.2
38. CH(s) + O(s) → C(s) + OH(s) 3.70 · 1021 0.0 25.1
39. C(s) + OH(s) → CH(s) + O(s) 3.70 · 1021 0.0 224.8
IIIf H, OH, H2 O reactions
40. O(s) + H(s) → OH(s) + Pt(s) 3.70 · 1021 0.0 11.5
41. OH(s) + Pt(s) → O(s) + H(s) 5.77 · 1022 0.0 74.9
42. H(s) + OH(s) → H2 O(s) + Pt(s) 3.70 · 1021 0.0 17.4
43. H2 O(s) + Pt(s) → H(s) + OH(s) 3.66 · 1021 0.0 73.6
44. OH(s) + OH(s) → H2 O(s) + O(s) 3.70 · 1021 0.0 48.2
45. H2 O(s) + O(s) → OH(s) + OH(s) 2.35 · 1020 0.0 41.0
IIIg CO-oxidation
46. CO(s) + O(s) → CO2 (s) + Pt(s) 1.00 · 1018 0.0 108.0
θCO(s) 33.0
θNO(s) -90.0
47. CO2 (s) + Pt(s) → CO(s) + O(s) 3.70 · 1021 0.0 155.1
θO(s) -45.0
48. C(s) + O(s) → CO(s) + Pt(s) 3.70 · 1021 0.0 0.0
θCO(s) -33.0
49. CO(s) + Pt(s) → C(s) + O(s) 3.70 · 1021 0.0 228.5
θO(s) -45.0
NO - reduction and oxidation
I Adsorption
50. NO + Pt(s) → NO(s) 8.50 · 10−1 0.0 0.0
51. NO2 + Pt(s) → NO2 (s) 9.00 · 10−1 0.0 0.0
52. N2 O + Pt(s) → N2 O(s) 2.50 · 10−2 0.0 0.0
II Desorption
53. NO(s) → NO + Pt(s) 1.00 · 1016 0.0 140.0
θO(s) 10.0
54. NO2 (s) → NO2 + Pt(s) 1.00 · 1013 0.0 60.0
55. N(s) + N(s) → N2 + Pt(s) + Pt(s) 3.70 · 1021 0.0 113.9
θCO(s) 75.0
56. N2 O(s) → N2 O + Pt(s) 1.00 · 1013 0.0 54.4
III NO-surface reactions
57. NO + O(s) → NO2 (s) 1.40 · 1010 0.5 97.5
θO(s) 45.0
58. NO2 (s) → NO + O(s) 1.00 · 1013 0.0 98.7
59. NO(s) + Pt(s) → N(s) + O(s) 4.00 · 1021 0.0 107.8
θCO(s) -3.0
60. N(s) + O(s) → NO(s) + Pt(s) 3.70 · 1021 0.0 128.1
θO(s) 45.0
61. NO(s) + N(s) → N2 O(s) + Pt(s) 1.00 · 1021 0.0 90.9
62. N2 O(s) + Pt(s) → NO(s) + N(s) 3.70 · 1021 0.0 66.9
Reaction 17. is a complex fast reaction that takes place if sufficient O(s) is available for Reaction 3. Reaction 17. is
first order in O(s) and C3 H5 (s).
Acknowledgments
First and foremost, I would like to thank Professor Jürgen Warnatz for his continuous
scientific and personal support of my work. He is a great mentor, who not only pointed
me in the right direction but also provided enough freedom for my own thoughts and
creativity.
The research described in this work is unthinkable without a strong research group,
with which I enjoyed working. In particular, I would like to thank Steffen Tischer
for programming the boundary-layer code, Dr. Chrys Correa for programming the
monolith code, and Daniel Chatterjee for modeling automotive catalytic converters.
Renate Schwiedernoch set up the reactor for experimental investigations of short-
contact-time catalysis in an impressively short time. I acknowledge Dr. Luba Maier’s
development of reaction mechanisms and Oliver Grosshans’ work on optimization.
For assistance in various software and hardware problems, I appreciate the help of
Stefan Kleditzsch, Volker Karbach, Tillman Katzenmeier, and Markus Nullmeier.
I also would like to thank my former colleagues Dr. Markus Wolf, Dr. Christian
Taut, and Dr. Ralf Kissel-Osterrieder. I thank Professor Frank Behrendt and Dr.
Uwe Riedel for their long-lasting colleagueship. Ingrid Hellwig and Barbara Werner
are acknowledged for their supportive secretarial work. I would also like to thank
all members of the research group Reactive Flows at the Interdisciplinary Center
for Scientific Computing at Heidelberg University for their collaboration and a very
conducive working environment.
Professor Jürgen Wolfrum, Dr. Hans-Robert Volpp, and Dr. Uwe Metka (PCI,
Heidelberg University) were very kind to provide the space and technical support for
the experimental study. I also like to thank them for a fruitful collaboration in the
Sonderforschungsbereich 359.
The experimental data for the studies on automotive catalytic converters were
provided by Professor W. Weissweiler, Erik Frank, and Dr. Sven Kureti (University
of Karlsruhe).
I thank Chrys, Steffen, Ryan, Jeremy, and Keith for proof-reading the manuscript.
The research presented in this work was funded by the Deutsche Forschungsge-
meinschaft (Postdoctoral fellowship, SFB 359, Sachbeihilfen), Forschungsverbund
Verbrennungskraftmaschinen, Bundesland Baden-Württemberg, US Department of
Energy, Eberspächer GmbH & Co, and Conoco Inc. I very much appreciate the
financial support.
I would like to thank my parents and my daughter Franziska for their love, and all my
friends for being there.