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Manuscript II 2019.05.28 without ref field codes.pdf (977.78 kB)

BrHgO• + C2H4 and BrHgO• + HCHO in Atmospheric Oxidation of Mercury: Determining Rate Constants of Reactions with Pre-Reactive Complexes and a Bifurcation

preprint
submitted on 13.06.2019, 00:52 and posted on 13.06.2019, 15:13 by Khoa T. Lam, Curtis J. Wilhelmsen, Theodore Dibble
Models suggest BrHgONO to be the major Hg(II) species formed in the global oxidation of Hg(0), and BrHgONO undergoes rapid photolysis to produce the thermally stable radical BrHgO•. We previously used quantum chemistry to demonstrate that BrHgO• can, like OH radical, readily can abstract hydrogen atoms from sp3-hybridized carbon atoms as well as add to NO and NO2. In the present work, we reveal that BrHgO• can also add to C2H4 to form BrHgOCH2CH2•, although this addition appears to proceed with a lower rate constant than the analogous addition of •OH to C2H4. Additionally, BrHgO• can readily react with HCHO in two different ways: either by addition to the carbon or by abstraction of a hydrogen atom. The minimum energy path for the BrHgO• + HCHO reaction bifurcates, forming two pre-reactive complexes, each of which passes over a separate transition state to form a different product.

Funding

National Science Foundation award number 1609848

History

Email Address of Submitting Author

tsdibble@esf.edu

Institution

SUNY College of Environmental Science and Forestry

Country

USA

ORCID For Submitting Author

0000-0002-0023-8233

Declaration of Conflict of Interest

No conflict of interest

Version Notes

Second version, but the first was not uploaded to ChemRxiv.

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