Cribb, P.H., Dove, J.E., Yamazaki, S. (1992)
A Kinetic Study of the Oxidation of Methanol Using Shock Tube
and Computer Simulation Techniques
Combust. Flame 1992, 88, 186.
Abstract
The reaction of methanol with oxygen is studied by shock tube techniques at
1800-2800 K in five gas mixtures ranging in composition from lean to rich.
Measurements are made by laser schlieren densitometry and dynamic mass
spectrometry. At high temperatures, the shock-wave-initiated reaction consists
qualitatively of two steps. In the first step, methanol decomposes with very
little consumption of oxygen, forming H2, radicals, and some stable products (CO
and H2O). In the second step, the H2/O2 reaction takes place accompanied,
especially in lean mixtures, by the oxidation of CO. At the lower end of the
temperature range of measurements, the two steps tend to merge. A comprehensive
mechanism based on literature data and the present experiments is proposed and
used to interpret the experimental results by detailed computer simulation.
Sensitivity analysis is used to identify a set of seven elementary reactions to
whose rate constants the results are most sensitive: (-95), (-59), (104), (10), (167), (55), and (38). New values of the rate constants of
these reactions are suggested by systematically fitting the results of these
experiments and of a similar study of methanol pyrolysis. The fitting procedure
makes use of sensitivity analysis and the estimated accuracy of the literature
values of the rate constants in the mechanism.
REACTION RATE COEFFICIENTS SUGGESTED IN THIS WORK:
See the companion paper Cribb et al. (1992a)