Cribb, P.H., Dove, J.E., Yamazaki, S. (1992)
A Kinetic Study of the Pyrolysis of Methanol Using Shock Tube and Computer Simulation Techniques
Combust. Flame 1992, 88, 169.
Abstract
The pyrolysis of methanol in shock waves at 1800-2740 K is studied by laser schlieren densitometry and dynamic mass spectrometry. A mechanism based on literature data and the present experiments is proposed and used to interpret the results by detailed computer simulation. A set of seven rate constants to which the data are most sensitive is identified. The values of these rate constants are adjusted to fit the data, using a systematic procedure depending upon sensitivity analysis and estimated accuracy of literature values of the rate constants in the mechanism. For the initiation process at 1900-2700 K we find k=9.7E+45 T^(-8.0) exp(-376.6 kJ/mol/RT) cm3/mol s, which is the sum of the rate constants for the two channels, (-63) and (-59). The ratio of these two rates is identified. Adjusted values of the rate constants for the following reactions are also suggested.

REACTION RATE COEFFICIENTS SUGGESTED IN THIS WORK*:

GRI-Mech
Number
('-' sign
means
reverse)		 Reaction Rate Coefficient
A T^n exp(-E/RT)		 Temperature
Range
(K)
A
(mol,cm3,s)		 n
(T in K)		 E
(cal/mol)
10 O + CH3 -> H + CH2O 7.0E+13     1900-2700
-54 CH2O + M -> H + HCO + M 5.0E+16   76480 1900-2700
55 H + HCO -> H2 + CO 2.0E+14     1900-2700
-56 CH2OH + M -> H + CH2O + M 1.0E+14   25100 1900-2700
58 H + CH2O -> HCO + H2 4.0E+13   3990 1900-2700
-59 CH3OH + M -> H + CH2OH + M 2.3E+45 -8.0 90000 1900-2700
60 H + CH2OH -> H2 + CH2O 1.0E+13     1900-2700
68 H + CH3OH -> CH2OH + H2 3.0E+14   14150 1900-2700
-95 CH3OH + M -> OH + CH3 + M 7.4E+45 -8.0 90000 1900-2700
104 OH + CH3OH -> CH2OH + H2O 1.5E+13   1700 1900-2700
167 HCO + M -> H + CO + M 5.0E+13   16800 1900-2700
* see also companion paper Cribb et al. (1992b)