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Rate constants for the reactions of isobutyl, neopentyl, cyclopentyl, and cyclohexyl radicals with molecular oxygen

✍ Scribed by Dihua Wu; Kyle D. Bayes

Publisher: John Wiley and Sons
Year: 1986
Tongue: English
Weight: 415 KB
Volume: 18
Category: Article
ISSN: 0538-8066
DOI: 10.1002/kin.550180505

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✦ Synopsis

Rate constants have been measured for the reactions of four hydrocarbon radicals with O2 in the gas phase at room temperature. Laser flash photolysis was used to generate low concentrations of radicals. A photoionization mass spectrometer followed the radical loss as a function of time. The measured pseudo first-order decay rate of the radical and the absolute oxygen concentration were combined to give the absolute rate constants (in units of lo-'' cm3 molec-' s -I ) : isobutyl (2.9 -C 0.7); neopentyl (1.6 * 0.3); cyclopentyl (17 2 3); and cyclohexyl(14 2 2). The cycloalkyl radicals have rate constants similar to those of other secondary radicals. However, the isobutyl and neopentyl radicals react more slowly than similar primary radicals. These new rate constants are compared in Figure 2 with the recently published correlation of reactive cross section with radical ionization potential.

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