Ion-molecule reactions in the binary mixture of ethylene oxide and trioxane. II. Mechanism for reaction of ethylene oxide molecular ion with trioxane.

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The ion-molecule reactions in the binary mixture of ethylene oxide and trioxane have been studied with use of a modified time-of-flight mass spectrometer. As cross-reaction product ions, C3H5O2+, C3H6O2+, and C3H7O2+ were observed under the conditions of long delay times and elevated pressure. It was found that these ions are formed by the dissociation of unstable intermediate-complex resulting from the reaction of ethylene oxide molecular ion with trioxane. It was proposed that the complex is of cyclic structure in which positive charge is delocalized. From the consideration of isotopic distribution of the prodoct ions in ethylene-d4 oxide–trioxane mixtures, the skeletal structures of the product ions were investigated. The rate constants of the formation reactions of C3H5O2+, C3H6O2+, and C3H7O2+ in ethylene oxide–trioxane mixtures were found to be 2.20×10−10, 2.61×10−10, and 1.74×10−10 cm3 molecule−1 s−1 respectively.
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