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Slow oxidation of hydrocarbons in the gas phase II. Neopentane

✍ Scribed by A. P. Zeelenberg

Publisher
Elsevier Science
Year
2010
Tongue
English
Weight
420 KB
Volume
81
Category
Article
ISSN
0165-0513

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✦ Synopsis

Abstract

The slow oxidation of neopentane has been investigated in a static system at 260Β°. Analysis by means of gas‐liquid chromatography (GLC) during the early stages of the combustion showed the presence of isobutene, acetone, isobutyraldehyde, pivalaldehyde, methanol, neopentyl alcohol, isobutene oxide, 3,3‐dimethyloxetane, propene, carbon dioxide, acetaldehyde, propene oxide, isopropyl alcohol, t‐butyl alcohol and water.

The formation of these products can be rationalized by a mechanism involving oxidation cycles with occasional chain branching. Oxidation cycles are thought to consist of three distinct steps, viz. (I) Oxygenation of alkyl radicals to yield peroxy radicals, (II) Intramolecular decomposition of peroxy radicals with formation of products and oxy radicals and (III) Interaction of the latter with the hydrocarbon to yield hydroxylic products and alkyl radicals. It would appear that in step (II) a C‐C bond is broken more readily than a C‐H bond. Chain branching is assumed to proceed via the hydroperoxide.

Isomerization of neopentyl radicals and dimerization reactions of radicals do not occur.

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