Abstract
Mercury is a persistent environmental pollutant arising from anthropogenic and natural sources. Gaseous oxidized mercury (GOM) is significantly more water soluble than elemental Hg and should be the main form responsible for deposition unto environmental sinks, however, the speciation of GOM is poorly understood due to its relatively low concentrations and labile nature. We investigated ion-molecule chemistry of gas-phase HgCl2 with SF6 -, CO3 -, and CO2·O2 - reagent ions by ion-drift chemical ionization mass spectrometry. Additionally, DFT and ab-initio computations coupled with rate constant calculations based on average dipole orientation (ADO) theory were used to evaluate the product stability, elucidate reaction pathways and corroborate experimental results. We found that the reaction of HgCl2 with SF6 -, CO3 -, and CO2·O2 - forms HgCl2·F- , HgCl2·CO3 -, HgCl2O- , and HgCl2O2 - product ions. These reactions are efficient in converting gaseous oxidized mercury to molecular ions, although competing reactions with O3, NOx, and H2O may limit their application in atmospheric applications. The calculated stability of the complexes is in the 11 to 57 kcal-mol-1range.
Original language | English (US) |
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State | Published - 2018 |
Event | 2018 Spring Technical Meeting of the Eastern States Section of the Combustion Institute, ESSCI 2018 - State College, United States Duration: Mar 4 2018 → Mar 7 2018 |
Other
Other | 2018 Spring Technical Meeting of the Eastern States Section of the Combustion Institute, ESSCI 2018 |
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Country/Territory | United States |
City | State College |
Period | 3/4/18 → 3/7/18 |
All Science Journal Classification (ASJC) codes
- Mechanical Engineering
- Physical and Theoretical Chemistry
- General Chemical Engineering
Keywords
- And ADO theory
- Detection of oxidized mercury
- Reaction thermochemistry