Strahlungschemie von Kohlenwasserstoffen. 18. Mitteilung. Hexan‐N₂O

Abstract

N2O has the following effects on the radiolysis of light and heavy hexane: It decreases the bimolecular part of the hydrogen production. A corresponding N2‐production amounts to the double of this decrease. The speed of competition is very much faster at higher temperature. The amount of CC bond split yielding alkyl radicals is decreased but not suppressed. The initial amount of hexyl radicals formed is not changed and shows no isotope effect, whereas an additional production of these radicals shows such an effect. They are probably formed by the abstraction by OH‐radicals that are products of the neutralization reaction of N2O− with the hexyl cation. This additional amount contributes mainly to the 3‐hexyl‐isomer. The part of the additional hexene formation that exceeds the amount produced by disproportionation from hexyl radicals is formed in a unimolecular process yielding water as the second product. This is a main product, hexanols and hexanones have not been found. A partial product balance involving hydrogen, hexyl and hexene is presented. The disproportionation/combination ratio for hexyl radicals is according to this balance 0.75.