Mercury oxidation via chlorine, bromine, and iodine under atmospheric conditions: thermochemistry and kinetics.

Emissions of gaseous mercury from combustion sources are the major source of Hg in the atmosphere and in environmental waters and soils. Reactions of Hg(o)(g) with halogens are of interest because they relate to mercury and ozone depletion events in the Antarctic and Arctic early spring ozone hole events, and the formation of Hg-halides (HgX2) is a method for removal of mercury from power generation systems. Thermochemistry and kinetics from published theoretical and experimental studies in the literature and from computational chemistry are utilized to compile a mechanism of the reactions considered as contributors to the formation of HgX2 (X = Cl, Br, I) to understand the reaction paths and mechanisms under atmospheric conditions. Elementary reaction mechanisms are assembled and evaluated using thermochemistry for all species and microscopic reversibility for all reactions. Temperature and pressure dependence is determined with quantum Rice Ramsperger Kassel (RRK) analysis for k(E) and master equation analysis for fall-off. We find that reactions of mercury with a small fraction of the reactor surface or initiation by low concentrations of halogen atoms is needed to explain the experimental conversion of Hg to HgX2 in the gas phase. The models do not replicate data from experiments that do not explicitly provide an atom source. The Hg insertion reaction into X2 (Hg + X2 → HgX2) that has been reported is further studied, and we find agreement with studies that report high barriers. The high barriers prevent this insertion path from explaining the experimental data on HgX2 formation and Hg conversion under atmospheric conditions. Mechanism studies with low initial concentrations of halogen radicals show significant conversion of Hg under the experimental conditions.