Mechanistic insights into ozone-initiated oxidative degradation of saturated hydrocarbons and polymers
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Lee, Richmond; Coote, Michelle
Description
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...[Show more]
dc.contributor.author | Lee, Richmond | |
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dc.contributor.author | Coote, Michelle | |
dc.date.accessioned | 2020-09-02T06:50:25Z | |
dc.date.available | 2020-09-02T06:50:25Z | |
dc.identifier.issn | 1463-9076 | |
dc.identifier.uri | http://hdl.handle.net/1885/209247 | |
dc.description.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. | |
dc.description.sponsorship | We gratefully acknowledge generous allocations of supercomputing time on the National Facility of the National Computational Infrastructure (NCI), and financial support from the Australian Research Council (ARC). We also thank Dr Rika Kobayashi from NCI for advice on the CCSD(T) calculations | |
dc.format.mimetype | application/pdf | |
dc.language.iso | en_AU | |
dc.publisher | Royal Society of Chemistry | |
dc.rights | © the Owner Societies 2016 | |
dc.source | Physical chemistry chemical physics : PCCP | |
dc.title | Mechanistic insights into ozone-initiated oxidative degradation of saturated hydrocarbons and polymers | |
dc.type | Journal article | |
local.identifier.citationvolume | 18 | |
dc.date.issued | 2016-09-21 | |
local.publisher.url | http://pubs.rsc.org/en/Journals/JournalIssues/CP | |
local.type.status | Accepted Version | |
local.contributor.affiliation | Lee, R., Research School of Chemistry, The Australian National University | |
local.contributor.affiliation | Coote, Michelle, Research School of Chemistry, The Australian National University | |
dc.relation | http://purl.org/au-research/grants/arc/CE140100012 | |
local.identifier.essn | 1463-9084 | |
local.bibliographicCitation.issue | 35 | |
local.bibliographicCitation.startpage | 24663 | |
local.bibliographicCitation.lastpage | 24671 | |
local.identifier.doi | 10.1039/c6cp05064f | |
dcterms.accessRights | Open Access | |
dc.provenance | https://v2.sherpa.ac.uk/id/publication/18031..."The Accepted Version can be archived in a Non-Commercial Repository. 12 months embargo" from SHERPA/RoMEO site (as at 2/09/2020). | |
Collections | ANU Research Publications |
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