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A mechanistic study of the liquid phase autoxidation of nonan-5-one

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Published copy (DOI)

Author(s)

  • C J Hammond
  • J R L Smith
  • E Nagatomi
  • M S Stark
  • D J Waddington

Department/unit(s)

Publication details

JournalNEW JOURNAL OF CHEMISTRY
DatePublished - 2006
Issue number5
Volume30
Number of pages10
Pages (from-to)741-750
Original languageEnglish

Abstract

The liquid phase autoxidation of nonan-5-one has been studied as a model for the degradation of ketones formed from the oxidation of lubricants in automotive combustion engines. The oxidation, at 120 degrees C, gives a large number of products ( 32 identified), including derivatives of the substrate with an intact carbon skeleton and low molecular mass compounds, from radical fragmentations, as well as carbon oxides. The products were identified and quantified by GC-MS and GC, with the characterisation of isomers being aided by measuring the deuterium content of products from the autoxidation of 4,4,6,6-[H-2(4)]-nonan-5-one. Products arising from hydrogen atom abstraction from all the secondary C - H bonds were observed, with the main site of attack being a to the carbonyl group. The ketoalkyl, ketoperoxyl and ketoalkoxyl radicals formed in the reaction undergo radical dimerisation, disproportionation and hydrogen atom abstraction. With the ketoalkoxyl radicals the dominant pathway is beta-scission, indeed similar to 58% of the total product yield arises from this fragmentation of the alpha-ketoalkoxyl radical. Mechanisms for the formation of the observed products are proposed and used to determine the selectivity of the autoxidation for the different C - H bonds in the substrate.

    Research areas

  • FREE-RADICAL REACTIONS, NORMAL-HEXADECANE AUTOXIDATION, ABSOLUTE RATE CONSTANTS, ADDITIVE DIMERIZATIONS, LUBRICANT DEGRADATION, REACTION PATHWAYS, SUBSTITUTED TOLUENES, HYDROXYL RADICALS, ALKOXY RADICALS, OXIDATION

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