Mechanism of the reaction of OH radicals with acetone and acetaldehyde at 251 and 296 K
Literature Information
Geoffrey S. Tyndall, John J. Orlando, Timothy J. Wallington, Michael D. Hurley, Masashi Goto, Masahiro Kawasaki
Photoreactors combined with FTIR analysis techniques were used to investigate the formation of acids in the reactions of OH radicals with acetone and acetaldehyde in one atmosphere of air at 296 K and 251 K. In contrast to two recent reports, we find no evidence for direct formation of either formic acid or acetic acid (<10% yield of acids in both reactions). We conclude that under atmospheric conditions the reaction of OH radicals with acetone and acetaldehyde proceeds predominantly (>90%), if not exclusively, via H-atom abstraction. In atmospheric chemistry models we recommend use of OH + CH3C(O)CH3 → CH3C(O)CH2 + H2O and OH + CH3CHO → CH3C(O) + H2O to describe the mechanism of the title reactions. Curvature in the Arrhenius plots for these reactions is most likely due to formation of a pre-reaction complex rather than a change in mechanism from carbonyl addition to abstraction.
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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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