Ion-molecule reactions in the binary mixture of ethylene oxide and trioxane. I. Hydrogen atom and proton transfer reactions.

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The formation mechanism of protonated molecular ions by cross–reactions in ethylene oxide–trioxane mixtures has been studied with use of a modified time-of-flight mass spectrometer. The precursors of the product ions were determined by analysis of the fine structure of their ionization efficiency curves using deuterated ethylene oxide. Protonated ethylene oxide is formed by the hydrogen atom transfer reaction of ethylene oxide molecular ion with trioxane, and protonated trioxane by the proton transfer reaction of CHO+ (from ethylene oxide) with trioxane. In the ion-molecule reactions of ethylene-d4 oxide–trioxane mixtures, appreciable isotope effect was observed. The CHO+ from ethylene oxide is an important reactant ion as compared with that from trioxane in the proton transfer reaction, and CHO+ from ethylene oxide was suggested as a thermal reactive ion. The order of proton affinity could be estimated from the proton transfer reactions involving CHO+. It was found that the proton affinity of trioxane is smaller than that of ethylene oxide.
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