Removal of selenite from water using a synthetic dithiolate: An experimental and quantum chemical investigation

Daniel Burriss, Wenli Zou, Dieter Cremer, John Walrod, David Atwood

Research output: Contribution to journalArticlepeer-review

8 Scopus citations

Abstract

Combination of the dithiol N,N′-bis(2-mercaptoethyl)isophthalamide, abbreviated as BDTH2 and as 1, with excess H2SeO 3 in aqueous acidic (pH ≈ 1) conditions resulted in precipitation of BDT(S-Se-S) (6), with a 77Se NMR chemical shift of δ = 675 ppm, and oxidized BDT. When the reaction is conducted under basic conditions Se(IV) is reduced to red Se(0) and oxidized 1. No reaction takes place between 1 and selenate (Se(VI)) under acidic or basic conditions. Compound 6 is stable in air but decomposes to red Se(0) and the disulfide BDT(S-S) (9) with heating and in basic solutions. Mechanisms and energetics of the reactions leading to 6 in aqueous solution were unraveled by extensive calculations at the ωB97X-D/aug-cc-pVTZ-PP level of theory. NMR chemical shift calculations with the gauge-independent atomic orbital (GIAO) method for dimethyl sulfoxide as solvent confirm the generation of 6 (calculated δ value = 677 ppm). These results define the conditions and limitations of using 1 for the removal of selenite from wastewaters. Compound 6 is a rare example of a bidentate selenium dithiolate and provides insight into biological selenium toxicity.

Original languageEnglish
Pages (from-to)4010-4021
Number of pages12
JournalInorganic Chemistry
Volume53
Issue number8
DOIs
StatePublished - Apr 21 2014

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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