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Rate constants of sulfate radical anion reactions with organic molecules: A review

Wojnárovits, László, Takács, Erzsébet
Chemosphere 2019 v.220 pp. 1014-1032
aromatic compounds, chemical bonding, electron transfer, models, moieties, photolysis, radiolysis, reaction mechanisms, sulfates
The rate constants of sulfate radical anion reaction (kSO4−) with about 230 organic molecules of environmental interest are tabulated and discussed, together with both the methods of rate constant determinations and the reaction mechanisms. kSO4−’s were collected from the original publications. The highest values in the ∼109 M−1 s−1 range are published for aromatic molecules. There is a tendency that electron donating substituents increase and electron withdrawing substituents decrease these values. There are just a few compounds with rate constants established using different techniques in different laboratories. kSO4−’s determined in different laboratories by the direct techniques, pulse radiolysis or laser flash photolysis, in most cases agree reasonably. The values determined by competitive experimental techniques, by complex kinetics calculations, or by modelling show a large scatter. Some of these techniques seem to be questionable for kSO4− determination. The sulfate radical anion reacts with ketone and amine moieties of molecules by electron transfer. The same mechanism is also suggested for the reaction with aromatic rings. However, in a few cases addition to the double bond and sulfate anion elimination reactions were distinguished. A typical reaction with the aliphatic parts of the molecule is H-abstraction.