A kinetic study of the oxidation of pyridine
โ Scribed by Emi Ikeda; Patricia Nicholls; John C. Mackie
- Publisher
- Elsevier Science
- Year
- 2000
- Tongue
- English
- Weight
- 190 KB
- Volume
- 28
- Category
- Article
- ISSN
- 1540-7489
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โฆ Synopsis
Oxidation of pyridine has been studied behind reflected shock waves in a single-pulse shock tube. Four mixtures of pyridine and oxygen have been studied diluted in argon. The studied equivalence ratios were โซืกโฌ 4.82, 2.33, 1.21, and 0.60, ranging from very fuel rich to fuel lean. The temperature range was from 1000 to 2200 K, pressures ranged from 8.0 to 20 atm, and reaction residence times behind the reflected shock front ranged from 600 to 1100 ls. In the richest mixture, non-oxygenated products were similar to those produced in pyrolysis, except that N 2 and pyrrole, products not observed in pyrolysis, were also formed. At the lowest temperatures at which products could be detected (1200 K approximately), CO was the principal product of oxidation. Its yield profile with temperature was strongly dependent on the initial oxygen concentration. Molecular nitrogen was observed at all equivalence ratios, but its yield was maximum in the near stoichiometric mixture. NO was only produced in significant quantities in the near stoichiometric and lean mixtures. From kinetic modeling studies it was concluded that the oxidation is initiated both by unimolecular C-H bond fission and bimolecular reaction with O 2 to form the ortho-pyridyl radical which can further react with oxygenated species to give the pyridoxy radical. Pyridoxy undergoes CO elimination producing pyrrolyl radicals from which pyrrole arises. Other reactions important in the mechanism involve O abstraction and addition reactions with pyridine and ring scission reactions of pyridoxy. The predictions of a kinetic model are tested against experimental product profiles obtained with values of โซืกโฌ 1.21 and 0.60.
๐ SIMILAR VOLUMES
Pyrogallol (1,2.3-benzentriol, 1) reacts with dioxygen in weakly alkaline solutions to form purpurogallin (2,3,4,6-tetrahydroxy-5H-benzocycloheptene-5-one, 2) which then reacts to form purpurogalloquinone (3) which then decays to a product absorbing at 440 nm. The formation of 3 requires 1.5 mol O2