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Title: Theoretical and experimental investigation of the UV cross section and kinetics of the methyl formate peroxy radical
Journal: J. Phys. Chem. A
Volume: 107
Page(s): 5306 - 5316
Year: 2003
Reference type: Journal article
Squib: 2003HAN/LI5306-5316
Reaction:
methyl formate radical + O2 → CO2 + ·OH + HOCH
Reaction order:
2
Temperature:
298
K
Pressure: 1.33E-2 - 0.27 bar
Rate expression:
1.0 [±1.0 cm3/molecule s]
Category: Experiment
Data type:
Derived from fitting to a complex mechanism
Pressure dependence:
Rate constant is pressure independent
Experimental procedure:
Static or low flow - Data taken vs time
Excitation technique:
Flash photolysis (laser or conventional)
Time resolution:
In real time
Analytical technique:
Vis-UV absorption
Comments:
This is a composite reaction involving both CH3OC(O)O2 and O2CH2OC(O)H. Radicals generated from reaction of Cl or F atoms with methyl formate. Initial halogen atom concentration determined by substituting ethane for methyl formate and measuring the absorption due to the ethyl peroxy radical. At low pressures, ~10 Torr, approximately 18% of methyl formate peroxy radicals dissociate into OH and CH2O, decreasing to about 2% at 200 Torr.
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