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

Literature Information

Publication Date 2016-08-16
DOI 10.1039/C6CP05064F
Impact Factor 3.676
Authors

Richmond Lee, Michelle L. Coote


View Original

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.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
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Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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