Formation of organic nitro-compounds in flowing H2O2+ NO2+ N2+ organic vapour systems. Part 3.—Effects of O2 addition on H2O2+ NO2+ N2+ alkane systems
Abstract
The effects of oxygen on the product distribution from the surface-initiated reactions in flowing mixtures of H2O2, NO2, N2 and RH, where RH = ethane, propane, n-butane and n-pentane, at 298 K have been studied. In the absence of O2, the principal products are the corresponding nitroalkane, alkyl nitrite and alkyl nitrate. In the presence of sufficiently large concentrations of O2, the predominant product is the alkyl nitrate and the only other products of significance, in some cases, are the corresponding carbonyl compounds.
The variation of the product yields with [O2]/[NO2] gives values for the rate-constant ratios k8/(k3+k4) for reaction at both primary and secondary radical sites: R + NO2(+ M)→ RNO2(+ M)(3), R + NO2(+ M)→ RONO*(+ M)(4), R + O2(+ M)→ RO2(+ M). (8) Possible mechanisms by which the products are formed are discussed.
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