Determination of the gas-phase decomposition rate constants of heptyl-1 and heptyl-2 hydroperoxides C7H15OOH

1982 ◽  
Vol 14 (12) ◽  
pp. 1325-1337 ◽  
Author(s):  
K. A. Sahetchian ◽  
A. Heiss ◽  
R. Rigny ◽  
R. I. Ben-aïm
Keyword(s):  
Gas Phase ◽  
Decomposition Rate ◽  
Rate Constants ◽  
Phase Decomposition

Theoretical Prediction of CH3O and CH2OH Gas-Phase Decomposition Rate Coefficients

1986 ◽  
Vol 39 (12) ◽  
pp. 1929 ◽  
Author(s):  
PG Greenhill ◽  
BV Ogrady ◽  
RG Gilbert
Keyword(s):  
High Pressure ◽  
Theoretical Prediction ◽  
Gas Phase ◽  
Decomposition Rate ◽  
Rate Coefficient ◽  
Rate Coefficients ◽  
Phase Decomposition ◽  
Kinetic Schemes ◽  
Theoretical Predictions ◽  
Temperature Dependences

Theoretical predictions are made for the pressure and temperature dependences of two reactions involved in methanol combustion: (A) CH3O → CH2O + H and (B) CH2OH → 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) 3×1014 exp(-108 kJ mol-1 /RT), (B) 7×1014 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) 8×10-9 exp(-90 kJ mol-1 /RT); (B) 2×10-8 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.

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