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Author(s):   Hansen, J.C.; Li, Y.; Rosado-Reyes, C.M.; Francisco, J.S.; Szente, J.J.; Maricq, M.M.
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 + O2CO2 + ·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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