The Reactions of Bromide with Ozone Towards Bromate and the Hypobromite Puzzle: A Density Functional Theory Study |
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| Authors: | Sergej Naumov Clemens von Sonntag |
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| Affiliation: | 1. Leibniz-Institut für Oberfl?chenmodifizierung (IOM) , Leipzig, Germany;2. Leibniz-Institut für Oberfl?chenmodifizierung (IOM) , Leipzig, Germany;3. Max-Planck-Institut für Bioanorganische Chemie, Mülheim an der Ruhr , Germany;4. Deutsche Projekt Union (DPU) , K?ln, Germany |
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| Abstract: | Taking the solvent water into account, the energetics of the reactions of O3 with Br? leading to BrO3 ? have been calculated by Density Functional Theory at the B3LYP/6–311+G(d)/SCRF =COSMO level. Br? reversibly forms an adduct, BrOOO?, (ΔG?=?+6 kJ mol?1) that decays spin allowed into BrO? and O2(1Δg) (ΔG?=?+13 kJ mol?1). BrO? undergoes an oxidation to BrO2 ? and a reduction to Br?. This may be accounted for if two different adducts, OBrOOO? and BrOOOO?, decay into BrO? plus O2 and Br? plus 2 O2. After cyclization, OBrOOO? may also lead to Br? plus 2 O2. |
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| Keywords: | Bromide Hypobromite Bromite Bromate Ozone Reduction Ozone Adducts Singlet Dioxygen DFT Calculation Thermodynamics Reaction Mechanism |
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