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The Peroxymonocarbonate Anion HCO[sub.4][sup.−] as an Effective Oxidant in the Gas Phase: A Mass Spectrometric and Theoretical Study on the Reaction with SO[sub.2]
The peroxymonocarbonate anion, HCO[sub.4] [sup.−], the covalent adduct between the carbon dioxide and hydrogen peroxide anion, effectively reacts with SO[sub.2] in the gas phase following three oxidative routes. Mass spectrometric and electronic structure calculations show that sulphur dioxide is oxidised through a common intermediate to the hydrogen sulphate anion, sulphur trioxide, and sulphur trioxide anion as primary products through formal HO[sub.2] [sup.−], oxygen atom, and oxygen ion transfers. The hydrogen sulphite anion is also formed as a secondary product from the oxygen atom transfer path. The uncommon nucleophilic behaviour of HCO[sub.4] [sup.−] is disclosed by the Lewis acidic properties of SO[sub.2], an amphiphilic molecule that forms intermediates with characteristic and diagnostic geometries with peroxymonocarbonate.