Details
| Original language | English |
|---|---|
| Pages (from-to) | 675-685 |
| Number of pages | 11 |
| Journal | Journal of the Chemical Society, Perkin Transactions 2 |
| Issue number | 7 |
| Publication status | Published - 1975 |
| Externally published | Yes |
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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In: Journal of the Chemical Society, Perkin Transactions 2, No. 7, 1975, p. 675-685.
Research output: Contribution to journal › Article › Research › peer review
}
TY - JOUR
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.
AB - 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.
UR - http://www.scopus.com/inward/record.url?scp=20644434825&partnerID=8YFLogxK
U2 - 10.1039/P29750000675
DO - 10.1039/P29750000675
M3 - Article
AN - SCOPUS:20644434825
SP - 675
EP - 685
JO - Journal of the Chemical Society, Perkin Transactions 2
JF - Journal of the Chemical Society, Perkin Transactions 2
SN - 1472-779X
IS - 7
ER -