P. Kouřím
Jul 1, 1969
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Journal
International Journal for Radiation Physics and Chemistry
Abstract
Abstract 1-Octene was γ-irradiated both pure and in the presence of scavengers, and the structure and origin of the individual dimers formed were studied. In pure octene the composition of the dimer mixture was found to be, in principle, similar to the analogous products identified by other authors in irradiated 1-butene and 1-hexene. The main dimeric product constituting more than one-third of the dimer fraction is n-hexadecene (G = 0·55). Approximately one-half of the total dimer yield originates in radical reactions as evidenced by the results with the solutions of oxygen or benzoquinone. The dienes which are almost completely of radical origin result from the combination of the allylic type octenyl radicals, while the saturated dimers are formed by the addition of the octyl radicals to octene. The yields of the isomeric 1- and 2-octyl radicals are in the ratio of approximately 1 : 3·5. The molecular ions C8H16+ react with octene partly in a condensation reaction—by this reaction all n-hexadecene and a minor part of 7-methylpentadecene are formed—partly in a proton transfer reaction. The former is about twice as probable as the latter. They are both inhibited by ammonia; the rate constant for the transfer of proton from C8H16+ to ammonia is about thirty times higher than that for the ion-molecule condensation with octene. The G(H2) values, compiled from a number of published papers, when plotted as a function of the C-atom number (n) of straight-chain terminal olefins, give a straight line; this can be expressed as G(H2) = 0·46+0·06n. Some further aspects of the H2 formation in the radiolysis of olefins are briefly discussed.