ChemInform Abstract: RATE CONSTANTS FOR THE REACTION OF HYDROXYL RADICALS WITH PROPYLENE AND THE BUTENES OVER THE TEMPERATURE RANGE 297-425.DEG.K

1976 ◽  
Vol 7 (2) ◽  
pp. no-no
Author(s):  
R. ATKINSON ◽  
J. N. JUN. PITTS
Keyword(s):  
Hydroxyl Radicals ◽  
Rate Constants ◽  
Temperature Range

MECHANISM AND KINETICS OF THE CH3CH2C(O)OCH2CH3 + OH REACTION: A THEORETICAL STUDY

2011 ◽  
Vol 10 (05) ◽  
pp. 691-709 ◽  
Author(s):  
CONG HOU ◽  
CHENG-GANG CI ◽  
TONG-YIN JIN ◽  
YONG-XIA WANG ◽  
JING-YAO LIUM
Keyword(s):  
Rate Constants ◽  
Hydrogen Abstraction ◽  
Negative Temperature ◽  
State Theory ◽  
Measured Temperature ◽  
Temperature Range ◽  
Global Rate ◽  
Abstraction Reaction ◽  
Lower Temperature ◽  
Kinetic Calculations

The hydrogen abstraction reaction of CH 3 CH 2 C(O)OCH 2 CH 3 + OH has been studied theoretically by dual-level direct dynamics method. Six H-abstraction channels were found for this reaction. The required potential energy surface information for the kinetic calculations was obtained at the MCG3-MPWB//M06-2X/aug-cc-pVDZ level. The rate constants were calculated by the improved canonical variational transition-state theory with small-curvature tunneling correction (ICVT/SCT) approach in the temperature range of 200–2000 K. It is shown that the "methylene H-abstraction" from the alkoxy end of the ester CH 3 CH 2 C(O)OCH 2 CH 3 is the dominant channel at lower temperature (< 400 K), while the other channels from the acetyl end should be taken into account as the temperature increases and become the competitive ones at higher temperature. The calculated global rate constants are in good agreement with the experimental ones in the measured temperature range and exhibit a negative temperature dependence below 500 K. A four-parameter rate constant expression was fitted from the calculated kinetic data between 200–2000 K.

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