Formation of positive ions and other primary species in the oxidation of sulphides by hydroxyl radicals

Research output: Contribution to journal › Article › Research › peer review

Authors

  • Marija Bonifačić
  • Hermann Möckel
  • Detlef Bahnemann
  • K. Dieter Asmus

External Research Organisations

  • Helmholtz-Zentrum Berlin für Materialien und Energie (HZB)
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Details

Original languageEnglish
Pages (from-to)675-685
Number of pages11
JournalJournal of the Chemical Society, Perkin Transactions 2
Issue number7
Publication statusPublished - 1975
Externally publishedYes

Abstract

The oxidation of simple aliphatic sulphides [MeSMe. EtSEt. (CH2)4S] by hydroxyl radicals occurs via a complex reaction mechanism. The first step is addition of the OH· to sulphur to form R2ṠOH radicals. At low sulphide concentrations (<10-4M) R2ṠOH rapidly eliminates H2O to form a RSR(-H)·; radical which may be described by the mesomeric forms -CH-S̄- and -CH=Ṡ-. This radical is ultimately also formed at higher sulphide concentrations but via a different pathway. R2ṠOH increasingly reacts with another R2S molecule to form a short lived (R2S)2OH· radical complex which dissociates to (R2S)2+ and OH-. The (R2S)2+ complex ion seems to be relatively stable and decays essentially via equilibration to the molecular cation R2S+. This ion in its reaction with the solvent, OH- ions, and through a bimolecular process with another R2S+ cation is effectively deprotonated to form the RSR(-H)· radical. The reaction route at high concentration includes the formation of transient species with oxidizing properties; Fe(CN)64- is rapidly oxidized by (R2S)2+ [and possibly (R2S)2OH·]. The RSR(-H)· radical partially disproportionates to negative and long lived (>1 ms) positive ions. The stable oxidation product, sulphoxide, has been identified.

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Cite this

Formation of positive ions and other primary species in the oxidation of sulphides by hydroxyl radicals. / Bonifačić, Marija; Möckel, Hermann; Bahnemann, Detlef et al.
In: Journal of the Chemical Society, Perkin Transactions 2, No. 7, 1975, p. 675-685.

Research output: Contribution to journal › Article › Research › peer review

Bonifačić, M, Möckel, H, Bahnemann, D & Asmus, KD 1975, 'Formation of positive ions and other primary species in the oxidation of sulphides by hydroxyl radicals', Journal of the Chemical Society, Perkin Transactions 2, no. 7, pp. 675-685. https://doi.org/10.1039/P29750000675
Bonifačić, M., Möckel, H., Bahnemann, D., & Asmus, K. D. (1975). Formation of positive ions and other primary species in the oxidation of sulphides by hydroxyl radicals. Journal of the Chemical Society, Perkin Transactions 2, (7), 675-685. https://doi.org/10.1039/P29750000675
Bonifačić M, Möckel H, Bahnemann D, Asmus KD. Formation of positive ions and other primary species in the oxidation of sulphides by hydroxyl radicals. Journal of the Chemical Society, Perkin Transactions 2. 1975;(7):675-685. doi: 10.1039/P29750000675
Bonifačić, Marija ; Möckel, Hermann ; Bahnemann, Detlef et al. / Formation of positive ions and other primary species in the oxidation of sulphides by hydroxyl radicals. In: Journal of the Chemical Society, Perkin Transactions 2. 1975 ; No. 7. pp. 675-685.
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abstract = "The oxidation of simple aliphatic sulphides [MeSMe. EtSEt. (CH2)4S] by hydroxyl radicals occurs via a complex reaction mechanism. The first step is addition of the OH· to sulphur to form R2ṠOH radicals. At low sulphide concentrations (<10-4M) R2ṠOH rapidly eliminates H2O to form a RSR(-H)·; radical which may be described by the mesomeric forms -CH-{\=S}- and -CH=Ṡ-. This radical is ultimately also formed at higher sulphide concentrations but via a different pathway. R2ṠOH increasingly reacts with another R2S molecule to form a short lived (R2S)2OH· radical complex which dissociates to (R2S)2+ and OH-. The (R2S)2+ complex ion seems to be relatively stable and decays essentially via equilibration to the molecular cation R2S+. This ion in its reaction with the solvent, OH- ions, and through a bimolecular process with another R2S+ cation is effectively deprotonated to form the RSR(-H)· radical. The reaction route at high concentration includes the formation of transient species with oxidizing properties; Fe(CN)64- is rapidly oxidized by (R2S)2+ [and possibly (R2S)2OH·]. The RSR(-H)· radical partially disproportionates to negative and long lived (>1 ms) positive ions. The stable oxidation product, sulphoxide, has been identified.",
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T1 - Formation of positive ions and other primary species in the oxidation of sulphides by hydroxyl radicals

AU - Bonifačić, Marija

AU - Möckel, Hermann

AU - Bahnemann, Detlef

AU - Asmus, K. Dieter

N1 - Copyright: Copyright 2015 Elsevier B.V., All rights reserved.

PY - 1975

Y1 - 1975

N2 - The oxidation of simple aliphatic sulphides [MeSMe. EtSEt. (CH2)4S] by hydroxyl radicals occurs via a complex reaction mechanism. The first step is addition of the OH· to sulphur to form R2ṠOH radicals. At low sulphide concentrations (<10-4M) R2ṠOH rapidly eliminates H2O to form a RSR(-H)·; radical which may be described by the mesomeric forms -CH-S̄- and -CH=Ṡ-. This radical is ultimately also formed at higher sulphide concentrations but via a different pathway. R2ṠOH increasingly reacts with another R2S molecule to form a short lived (R2S)2OH· radical complex which dissociates to (R2S)2+ and OH-. The (R2S)2+ complex ion seems to be relatively stable and decays essentially via equilibration to the molecular cation R2S+. This ion in its reaction with the solvent, OH- ions, and through a bimolecular process with another R2S+ cation is effectively deprotonated to form the RSR(-H)· radical. The reaction route at high concentration includes the formation of transient species with oxidizing properties; Fe(CN)64- is rapidly oxidized by (R2S)2+ [and possibly (R2S)2OH·]. The RSR(-H)· radical partially disproportionates to negative and long lived (>1 ms) positive ions. The stable oxidation product, sulphoxide, has been identified.

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