
TY  - JOUR
A1  - Greenhill, PG 
A1  - Ogrady, BV 
A1  - Gilbert, RG 
T1  - Theoretical Prediction of CH<sub>3</sub>O and CH<sub>2</sub>OH Gas-Phase Decomposition Rate Coefficients
JF  - Australian Journal of Chemistry
JO  - Aust. J. Chem.
Y1  - 1986
VL  - 39
IS  - 12
SP  - 1929
EP  - 1942
KW  - 
UR  - https://doi.org/10.1071/CH9861929 
N2  - Theoretical predictions are made for the pressure and temperature dependences of two reactions involved in methanol combustion: (A) CH3O &#8594; CH2O + H and (B) CH2OH &#8594; CH2O + H. The calculations are carried out by using RRKM theory with a Gorin model for the activated complexes, with fall-off effects being taken into account by using the master equation. Results for the high-pressure rate coefficients (s-1) are (A) 3&#215;1014 exp(-108 kJ mol-1 /RT), (B) 7&#215;1014 exp(-124 kJ mol-1 /RT) at 1000 K. For the low-pressure limiting rate coefficient (cm3 s-1) over the range 600- 1000 K (A) 8&#215;10-9 exp(-90 kJ mol-1 /RT); (B) 2&#215;10-8 exp(-108 kJ mol-1 /RT). At 1000 K, the pressure at which the fall-off rate coefficients are one-half of their limiting high-pressure values are 3x108 Pa for both reactions. Formulae for inclusion of these reactions (including fall- off effects) over the range 300-2000 K and 10-2-106 Pa in modelling complex kinetic schemes are presented. 
ER  -

