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Author(s):   Andersen, 0; Hurley, M.D.; Ball, J.C.; Schneider, W.F.; Wallington, T.J.; Nielsen, O.J.
Title:   CF3CH(ONO)CF3: Synthesis, IR spectrum, and use as OH radical source for kinetic and mechanistic studies
Journal:   Int. J. Chem. Kinet.
Volume:   35
Page(s):   159 - 165
Year:   2003
Comments:   ABSTRACT: The synthesis, IR spectrum, and first-principles characterization ofCF3CH(ONO)CF3 as well as its use as an OH radical source in kinetic and mechanisticstudies are reported. CF3CH(ONO)CF3 exists in two conformers corresponding to rotationabout the RCO NO bond. The more prevalent trans conformer accounts for the prominent IRabsorption features at frequencies (cm?1) of 1766 (N=O stretch), 1302, 1210, and 1119 (C-Fstretches), and 761 (O-N-O bend); the cis conformer contributes a number of distinct weakerfeatures. CF3CH(ONO)CF3 was readily photolyzed using fluorescent blacklamps to generateCF3C(O)CF3 and, by implication, OH radicals in 100% yield. CF3CH(ONO)CF3 photolysis is aconvenient source of OH radicals in the studies of the yields of CO, CO2, HCHO, and HC(O)OHproducts which can be difficult to measure using more conventional OH radical sources (e.g.,CH3ONO photolysis). CF3CH(ONO)CF3 photolysis was used to measure k(OH + C2H4)/k(OH+ C3H6) = 0.29 ± 0.01 and to establish upper limits of 16 and 6% for the molar yields of COand HC(O)OH from the reaction of OH radicals with benzene in 700 Torr of air at 296 K.
Reference type:   Journal article
Squib:   2003AND/HUR159-165

Reaction:   C2H4 + ·OH → Products
Reaction order:   2
Reference reaction:   CH3CH=CH2 + ·OH → Products
Reference reaction order:   2
Temperature:   296 K
Pressure:  0.93 bar
Rate expression:   2.9x10-1±1.0x10-2
Bath gas:   air
Category:  Experiment
Data type:   Relative rate value measured
Pressure dependence:   None reported
Experimental procedure:   Static or low flow - Data taken vs time
Excitation technique:   Sensitized photolysis
Time resolution:   In real time
Analytical technique:   Fourier transform (FTIR)
Comments:   ABSTRACT: The synthesis, IR spectrum, and first-principles characterization ofCF3CH(ONO)CF3 as well as its use as an OH radical source in kinetic and mechanisticstudies are reported. CF3CH(ONO)CF3 exists in two conformers corresponding to rotationabout the RCO NO bond. The more prevalent trans conformer accounts for the prominent IRabsorption features at frequencies (cm?1) of 1766 (N=O stretch), 1302, 1210, and 1119 (C-Fstretches), and 761 (O-N-O bend); the cis conformer contributes a number of distinct weakerfeatures. CF3CH(ONO)CF3 was readily photolyzed using fluorescent blacklamps to generateCF3C(O)CF3 and, by implication, OH radicals in 100% yield. CF3CH(ONO)CF3 photolysis is aconvenient source of OH radicals in the studies of the yields of CO, CO2, HCHO, and HC(O)OHproducts which can be difficult to measure using more conventional OH radical sources (e.g.,CH3ONO photolysis). CF3CH(ONO)CF3 photolysis was used to measure k(OH + C2H4)/k(OH+ C3H6) = 0.29 ?0.01 and to establish upper limits of 16 and 6% for the molar yields of COand HC(O)OH from the reaction of OH radicals with benzene in 700 Torr of air at 296 K.

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