A surface-stabilized ozonide triggers bromide oxidation at the aqueous solution-vapour interface
Corral Arroyo, Pablo
Andres Carignano M., Marcelo
Francisco, Joseph S.
Shepson, Paul B.
- Journal Article
Rights / licenseCreative Commons Attribution 4.0 International
Oxidation of bromide in aqueous environments initiates the formation of molecular halogen compounds, which is important for the global tropospheric ozone budget. In the aqueous bulk, oxidation of bromide by ozone involves a [Br • OOO − ] complex as intermediate. Here we report liquid jet X-ray photoelectron spectroscopy measurements that provide direct experimental evidence for the ozonide and establish its propensity for the solution-vapour interface. Theoretical calculations support these fi ndings, showing that water stabilizes the ozonide and lowers the energy of the transition state at neutral pH. Kinetic experiments con fi rm the dominance of the heterogeneous oxidation route established by this precursor at low, atmospherically relevant ozone concentrations. Taken together, our results provide a strong case of different reaction kinetics and mechanisms of reactions occurring at the aqueous phase-vapour interface compared with the bulk aqueous phase. Show more
Journal / seriesNature Communications
Pages / Article No.
PublisherNature Publishing Group
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