Reactions in the diethyl peroxide–nitric oxide system. Part III. The pressure dependence of the combination of ethoxyl radicals with nitric oxide

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.