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Title: Kinetics of the reactions of O(3P) with CCl2=CH2, (Z)-CHCl=CHCl, and CCl2=CCl2: A temperature dependence study
Journal: J. Phys. Chem. A
Volume: 110
Page(s): 11091 - 11097
Year: 2006
Reference type: Journal article
Squib: 2006BLA/TAC11091-11097
Reaction:
O(3P) + CH2=CCl2 → Products
Reaction order:
2
Temperature:
298 - 359
K
Pressure: 2.80E-3 - 5.20E-3 bar
Rate expression:
1.82x10-10 [±1.29x10-10 cm3/molecule s] e-12630 [±970 J/mole]/RT
Category: Experiment
Data type:
Absolute value measured directly
Pressure dependence:
Rate constant is high pressure limit
Experimental procedure:
Flow tube - Data taken vs distance
Excitation technique:
Discharge
Time resolution:
In real time
Analytical technique:
Chemiluminescence
Comments:
The A-factors reported in the paper are a factor of 10 low due to typographical errors. This was confirmed through a personal communication with the authors. The values abstracted for this database have accordingly been increased from those listed in the paper.
O atoms were generated by the microwave discharge of an O2/He mixture and the concentration of O atoms monitored by measuring the chemiluminescence from the air afterglow reaction in which O(3P) reacts with NO to produce electronically excited NO2. The kinetics were determined from the O atom decay profiles.
The authors assume the mechanism is addition to the double bond and they suggest that the absence of an observed pressure effect indicates the reaction is at the high pressure limit even at a few torr under their conditions.
Uncertainties are 2 sigma and refer to precision only.
The authors propose a correlation relating the reaction addtion rates of OH and O with alkenes at 298 K:
log k(OH) = 0.57278 log k[O(3P)] - 4.095
View full bibliographic record.
Rate constant values calculated from the Arrhenius expression:
| T (K) | k(T) [cm3/molecule s] |
|---|---|
| 298 | 1.11E-12 |
| 300 | 1.15E-12 |
| 325 | 1.70E-12 |
| 350 | 2.37E-12 |
| 359 | 2.65E-12 |