Mechanisms of oxidation of organosulfur compounds by ferrate(VI)

Virender K. Sharma, George W. Luther, Frank J Millero

Research output: Contribution to journalArticle

80 Citations (Scopus)

Abstract

The oxidation of organosulfur compounds requires the transfer of oxygen atoms and is important in decontamination of chemical warfare agents, desulfurization of fossil fuel for high quality, deodorization of wastewater and sludge, and remediation of industrial effluents. The kinetics of the oxidation of organosulfur compounds (sulfur-containing amino acids, aliphatic and aromatic thiols, and mercaptans) by the environmentally-friendly oxidant, ferrate(VI) FeO42-, was quantitatively examined in this study using a kinetic model considering possible reactions among the species of ferrate(VI) and organosulfur compounds. The ratios of ferrate(VI) to the various organosulfur compounds for the one oxygen-atom transfer were 0.50 and 0.67 for Fe(II) and Fe(III) as final products, respectively. The second-order rate constants for the oxidation of organosulfur compounds by protonated ferrate(VI) HFeO4- ion were correlated with thermodynamic 1-e - and 2-e - reduction potentials in order to understand the mechanisms of the reactions. The oxidation of the compounds involved a 1-e - transfer step from Fe(VI) to Fe(V), followed by 2-e - transfer to Fe(III) as the reduced product (Fe(VI)→Fe(V)→Fe(III)). The 2-e - transfer steps resulted in the formation of Fe(II) (Fe(VI)→Fe(IV)→Fe(II)). Conclusions drawn from the correlations are consistent with the experimentally determined stoichiometries and products of the reactions. The calculated half-lives for the oxidation were in the range of ms to s at a dose of 10mg K 2FeO 4L -1 and hence ferrate(VI) has a great potential in treating organosulfur compounds present in water and wastewater.

Original languageEnglish (US)
Pages (from-to)1083-1089
Number of pages7
JournalChemosphere
Volume82
Issue number8
DOIs
StatePublished - Feb 2011

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oxidation
Oxidation
Waste Water
Sulfhydryl Compounds
Wastewater
Oxygen Compounds
Chemical Warfare Agents
Chemical warfare
Oxygen
Fossil Fuels
Sulfur Amino Acids
Sulfur Compounds
Atoms
Kinetics
Decontamination
Sulfur compounds
Sewage sludge
wastewater
kinetics
Desulfurization

Keywords

  • Clean fuel
  • Electron transfer
  • Ferrate
  • Oxygen-atom transfer
  • Remediation

ASJC Scopus subject areas

  • Environmental Chemistry
  • Chemistry(all)

Cite this

Mechanisms of oxidation of organosulfur compounds by ferrate(VI). / Sharma, Virender K.; Luther, George W.; Millero, Frank J.

In: Chemosphere, Vol. 82, No. 8, 02.2011, p. 1083-1089.

Research output: Contribution to journalArticle

Sharma, Virender K. ; Luther, George W. ; Millero, Frank J. / Mechanisms of oxidation of organosulfur compounds by ferrate(VI). In: Chemosphere. 2011 ; Vol. 82, No. 8. pp. 1083-1089.
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N2 - The oxidation of organosulfur compounds requires the transfer of oxygen atoms and is important in decontamination of chemical warfare agents, desulfurization of fossil fuel for high quality, deodorization of wastewater and sludge, and remediation of industrial effluents. The kinetics of the oxidation of organosulfur compounds (sulfur-containing amino acids, aliphatic and aromatic thiols, and mercaptans) by the environmentally-friendly oxidant, ferrate(VI) FeO42-, was quantitatively examined in this study using a kinetic model considering possible reactions among the species of ferrate(VI) and organosulfur compounds. The ratios of ferrate(VI) to the various organosulfur compounds for the one oxygen-atom transfer were 0.50 and 0.67 for Fe(II) and Fe(III) as final products, respectively. The second-order rate constants for the oxidation of organosulfur compounds by protonated ferrate(VI) HFeO4- ion were correlated with thermodynamic 1-e - and 2-e - reduction potentials in order to understand the mechanisms of the reactions. The oxidation of the compounds involved a 1-e - transfer step from Fe(VI) to Fe(V), followed by 2-e - transfer to Fe(III) as the reduced product (Fe(VI)→Fe(V)→Fe(III)). The 2-e - transfer steps resulted in the formation of Fe(II) (Fe(VI)→Fe(IV)→Fe(II)). Conclusions drawn from the correlations are consistent with the experimentally determined stoichiometries and products of the reactions. The calculated half-lives for the oxidation were in the range of ms to s at a dose of 10mg K 2FeO 4L -1 and hence ferrate(VI) has a great potential in treating organosulfur compounds present in water and wastewater.

AB - The oxidation of organosulfur compounds requires the transfer of oxygen atoms and is important in decontamination of chemical warfare agents, desulfurization of fossil fuel for high quality, deodorization of wastewater and sludge, and remediation of industrial effluents. The kinetics of the oxidation of organosulfur compounds (sulfur-containing amino acids, aliphatic and aromatic thiols, and mercaptans) by the environmentally-friendly oxidant, ferrate(VI) FeO42-, was quantitatively examined in this study using a kinetic model considering possible reactions among the species of ferrate(VI) and organosulfur compounds. The ratios of ferrate(VI) to the various organosulfur compounds for the one oxygen-atom transfer were 0.50 and 0.67 for Fe(II) and Fe(III) as final products, respectively. The second-order rate constants for the oxidation of organosulfur compounds by protonated ferrate(VI) HFeO4- ion were correlated with thermodynamic 1-e - and 2-e - reduction potentials in order to understand the mechanisms of the reactions. The oxidation of the compounds involved a 1-e - transfer step from Fe(VI) to Fe(V), followed by 2-e - transfer to Fe(III) as the reduced product (Fe(VI)→Fe(V)→Fe(III)). The 2-e - transfer steps resulted in the formation of Fe(II) (Fe(VI)→Fe(IV)→Fe(II)). Conclusions drawn from the correlations are consistent with the experimentally determined stoichiometries and products of the reactions. The calculated half-lives for the oxidation were in the range of ms to s at a dose of 10mg K 2FeO 4L -1 and hence ferrate(VI) has a great potential in treating organosulfur compounds present in water and wastewater.

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KW - Electron transfer

KW - Ferrate

KW - Oxygen-atom transfer

KW - Remediation

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