Reactions in the diethyl peroxide–nitric oxide system. Part III. The pressure dependence of the combination of ethoxyl radicals with nitric oxide
- 1 January 1966
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in Journal of the Chemical Society B: Physical Organic
- p. 640-643
- https://doi.org/10.1039/j29660000640
Abstract
The combination of ethoxyl radicals with nitric oxide has been studied at low pressures in a flow system at 200°, in comparison with the hydrogen abstraction reaction forming nitroxyl and acetaldehyde. The combination reaction is in the transition zone between second- and third-order at effective total reactor pressures of 0·08–1·6 mm. of diethyl peroxide as third body. The results can be explained on a simple energy-transfer basis. The third-order rate constant is 3 × 1018 mole–2 cm.6 sec.–1, the “half-rate pressure” 0·2 mm., and the lifetime of the energised ethyl nitrite molecule 5 × 10–7 sec. The efficiencies of nitric oxide and neopentane in energy transfer are about 0·05 and 0·6, respectively, relative to diethyl peroxide.Keywords
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