Mechanistic insights into ozone-initiated oxidative degradation of saturated hydrocarbons and polymers

Richmond Lee, Michelle L. Coote

Research output: Contribution to journalArticlepeer-review

17 Citations (Scopus)

Abstract

Accurate quantum chemical calculations were employed to investigate the mechanism of ozone-initiated oxidation of C-H bonds of saturated hydrocarbons and polymers. Step wise hydrogen atom abstraction generates the first resting state the trihydroxide -COOOH, which undergoes decomposition to produce the free radical species alkoxyl -CO and peroxyl OOH thereby setting off a complex chain of radical processes. The H transfer from peroxyl radical to alkoxyl allows formation of inactive alcohol and the singlet excited dioxygen. Other competitive processes include the self fragmentation or β-scission of the alkoxyl -CO to give rise to a carbonyl (ketone or aldehyde) and a C-centred free radical species. Tertiary C-H bonds are most susceptible to O3 oxidation followed by secondary and primary. Among the polymers studied, poly(styrene) is the least resistant to C-H bond ozonation, followed by poly(propylene), poly(methacrylate), poly(methyl methacrylate) and poly(vinyl chloride). Calculations also reveal catalytic effects of water in promoting the C-H bond oxidation process in polymer systems without competing H-bond donor groups.

Original languageEnglish
Pages (from-to)24663-24671
Number of pages9
JournalPhysical Chemistry Chemical Physics
Volume18
Issue number35
DOIs
Publication statusPublished - 2016
Externally publishedYes

Keywords

  • quantum chemical
  • ozone
  • oxidation
  • hydrocarbons
  • polymers
  • hydrogen
  • atom
  • trihydroxide
  • alkoxyl
  • peroxyl
  • free radical

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