Kinetics of the Self Reaction of Cyclopentadienyl Radicals
Journal of Physical Chemistry A, ISSN: 1520-5215, Vol: 119, Issue: 28, Page: 7418-7429
2015
- 21Citations
- 27Captures
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Metrics Details
- Citations21
- Citation Indexes21
- 21
- CrossRef15
- Captures27
- Readers27
- 27
Article Description
The kinetics of the self-reaction of cyclopentadienyl radicals (c-C5H5) was studied by laser photolysis/photoionization mass spectroscopy. Overall rate constants were obtained in direct real-time experiments in the temperature region 304-600 K and at bath gas densities of (3.00-12.0) × 1016 molecules cm-3. The room-temperature value of the rate constant, (3.98 ± 0.41) × 10-10 cm3 molecule-1 s-1, is significantly higher than the rate constants for most hydrocarbon radical-radical reactions and coincides with the estimated collision rate. The observed overall c-C5H5 + c-C5H5 rate constant demonstrates an unprecedented strong negative temperature dependence: k1 = 2.9 × 10-12 exp(+1489 K/T) cm3 molecule-1 s-1, with estimated uncertainty increasing with temperature, from 13% at 304 to 32% at 600 K. Formation of C10H10 as the primary product of cyclopentadienyl self-reaction was observed. In additional experiments performed at the temperature of 800 K, formation of C10H10, C10H9, and C10H8 was observed. Final product analysis by gas chromatography/mass spectrometry detected two isomers of C10H8 at 800 K: naphthalene (major) and azulene (minor).
Bibliographic Details
American Chemical Society (ACS)
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