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Mechanisms of oxidation of organosulfur compounds by ferrate(VI).
Chemosphere. 2011 Feb; 82(8):1083-9.C

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) FeO(4)(2-), 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) HFeO(4)(-) 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(2)FeO(4)L(-1) and hence ferrate(VI) has a great potential in treating organosulfur compounds present in water and wastewater.

Authors+Show Affiliations

Chemistry Department and Center of Ferrate Excellence, Florida Institute of Technology, 150 West University Boulevard, Melbourne, FL 32901, USA. vsharma@fit.eduNo affiliation info availableNo affiliation info available

Pub Type(s)

Journal Article
Research Support, Non-U.S. Gov't
Research Support, U.S. Gov't, Non-P.H.S.

Language

eng

PubMed ID

21215423

Citation

Sharma, Virender K., et al. "Mechanisms of Oxidation of Organosulfur Compounds By Ferrate(VI)." Chemosphere, vol. 82, no. 8, 2011, pp. 1083-9.
Sharma VK, Luther GW, Millero FJ. Mechanisms of oxidation of organosulfur compounds by ferrate(VI). Chemosphere. 2011;82(8):1083-9.
Sharma, V. K., Luther, G. W., & Millero, F. J. (2011). Mechanisms of oxidation of organosulfur compounds by ferrate(VI). Chemosphere, 82(8), 1083-9. https://doi.org/10.1016/j.chemosphere.2010.12.053
Sharma VK, Luther GW, Millero FJ. Mechanisms of Oxidation of Organosulfur Compounds By Ferrate(VI). Chemosphere. 2011;82(8):1083-9. PubMed PMID: 21215423.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Mechanisms of oxidation of organosulfur compounds by ferrate(VI). AU - Sharma,Virender K, AU - Luther,George W,3rd AU - Millero,Frank J, Y1 - 2011/01/06/ PY - 2010/10/27/received PY - 2010/12/10/revised PY - 2010/12/10/accepted PY - 2011/1/11/entrez PY - 2011/1/11/pubmed PY - 2011/3/11/medline SP - 1083 EP - 9 JF - Chemosphere JO - Chemosphere VL - 82 IS - 8 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) FeO(4)(2-), 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) HFeO(4)(-) 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(2)FeO(4)L(-1) and hence ferrate(VI) has a great potential in treating organosulfur compounds present in water and wastewater. SN - 1879-1298 UR - https://www.unboundmedicine.com/medline/citation/21215423/Mechanisms_of_oxidation_of_organosulfur_compounds_by_ferrate_VI__ L2 - https://linkinghub.elsevier.com/retrieve/pii/S0045-6535(10)01458-X DB - PRIME DP - Unbound Medicine ER -