Emissions of gaseous mercury from combustion sources are the major source of Hg in the atmosphere. Reactions of Hgo(g) with halogens are important because they relate to Hg and ozone loss in Antarctic and Arctic early spring ozone hole events, and the formation of mercury-halides is a method for capture of Hg emissions from combustion plants. The conversion of mercury into mercury halides has been discussed in experimenta/theoretical papers. In this study we use the thermochemistry and kinetics from published theoretical/experimental studies, to compile an elemental mechanism for the formation of HgX2, (X = Cl, Br) at atmospheric conditions. We further evaluate a Hg insertion reaction into X2 (Hg + X2 ? HgX2) at several levels of theory (B2PLYP, ?B97X, M06,M06-2X), and the aug-cc-pVTZ-PP basis set. We find initiation by halogen atoms is needed to explain the experimental conversion of Hg to HgX2; the experiments do not have this source.

Mercury oxidation via chlorine and bromine under atmospheric conditions: Thermochemistry and kinetics

245th National Meeting (2013)

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