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Title: On the mechanism of the HCCO + O2 reaction: Probing multiple pathways to a single product channel
Journal: Phys. Chem. Chem. Phys.
Volume: 6
Page(s): 1697 - 1705
Year: 2004
Reference type: Journal article
Squib: 2004ZOU/OSB1697-1705
Reaction:
O2 + HCCO → CO2 + CO + H·
Reaction order:
2
Rate expression:
no rate data available
Category: Experiment
Data type:
Mechanistic information only
Pressure dependence:
None reported
Experimental procedure:
Static or low flow - Data taken vs time
Excitation technique:
Flash photolysis (laser or conventional)
Time resolution:
In real time
Analytical technique:
Other (IR)
Comments:
HCCO radical (ketenyl) was generated in a flow reactor via laser photolysis of ethyl ethynyl ether at 193 nm and reacted with natural abundance O2 or 18O2. Real-time FTIR emission spectroscopy was used to monitor the CO and CO2 products. The distribution of 18O2 in the products was used to infer information about the reaction echanism. The results indicate that at least 85% of the reactive flux passes through a four-membered OCCO ring intermediate. An alternative reaction path through an energetically allowed three-membered COO ring intermediate represents less than 15% of the total reactive flux.
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