Homework 1 Complex kinetics. Groups of 2 (former NUS/NTU +non-Singapore).

Construct a kinetic model for methane oxidation. Include only species with 0 or 1 carbon atoms,
and 0, 1, or 2 oxygen atoms to limit the size of the network. Thermodynamic and kinetic
parameters can be obtained from the Leeds mechanism
(http://www.chem.leeds.ac.uk/Combustion/mechanisms/metan15.dat) for groups 1 and 2,
or from the GRIMech mechanism
(http://www.me.berkeley.edu/gri_mech/version30/files30/grimech30.dat) for groups 3 and 4.
Include your mechanism and the kinetic/thermodynamic parameters in the appendix of your
report.
Groups 1 and 3 will simulate a CSTR reactor, while groups 2 and 4 will look at a batch reactor.

Process variables to consider:
CH
4
/O
2
ratio in the feed. Consider stoichiometric, fuel rich and oxygen rich conditions.
Evaluate the effect of an inert gas (e.g. N
2
) on the combustion behavior (ignition) (e.g. use N
2
/O
2

=4)
Evaluate the effect of reactor heat loss (adiabatic vs. non adiabatic).
Evaluate the effect of initial pressure and temperature (batch) or inlet flowrate and temperature
(CSTR)

Discuss the following points:
1. Stability of the reacting system. Do you observe ignition, oscillations? In particular, try to
predict detonation and the stability region (p-T diagram) for methane/oxygen mixtures and
compare with experimental data, where available.
2. Plot temperature and concentrations of the key species as a function of time.
3. Discuss the reactor equations and the details of your simulations. What causes the
oscillations, if you indeed observe them?
4. Evaluate the effect of the pseudo steady state approximation on your simulated results. Is it
valid for the radicals? Can it be used for other species?
5. Calculate the reaction orders for methane, oxygen and CO
2
for 2 conditions.
6. Evaluate the sensitivity of your simulations to the kinetic parameters (e.g. by increasing the
forward and reverse rate by 10% and evaluate the effect on the predicted T, and methane
conversion).
7. Simplify the mechanism as much as possible for 2 reactive conditions, using some of the
techniques discussed in class (QSSA, pseudo equilibrium, rate based, -hypothesis).


Oscillations could be observed for H
2
combustion with the following conditions: Non-steady
state CSTR, volume =0.50 dm
3
, residence time (pV/FRT
a
) =8.0 sec, where T
a
is the feed
temperature, p the reactor pressure, and F the total molar flowrate for the feed. Reactants are fed
at the temperature T
a
and leave at the reactor temperature T. Heat loss to the environment can be
modeled using a loss coefficient of =0.8 10
-3
W/cm
3
K, and Q (W/cm
3
) = (T T
a
). For certain
T
a
, oscillation could be observed (see Figures below)

Figures