Study of intermediates formed in the oxidation of thiols

The oxidation of aminoethanethiol (1) was investigated in acid solutions on a glass carbon anode. It was shown that at relatively low anode potentials thiyl radicals RS^· are released into the solution, but this does not lead to binding of the oxygen in the solution. Raising the anode potential leads to binding of oxygen, which is probably due to the formation of the intermediate RS⁺. The oxidation of 1 was studied in Ce(SO₄)₂+H₂SO₄ solution. It was shown that under certain conditions the intermediate is RS⁺, which subsequently converts to a product that could not be identified as any previously described product of the oxidation of thiols. Proposals are made regarding its structure and conversion pathways.B. P. Konstantinov Institute of Nuclear Physics, Russian Academy of Sciences, 188350 Leningrad. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 2, pp. 278–288, February, 1992.     

Oxidation of thiol compounds by molecular oxygen in aqueous solutions

Side self-oxidation of thiols was studied. It was found that these reactions in neutral and alkaline solutions are induced by impurities of variable-valence metals. The ability of transition metals to catalyze oxidation of thiols changes in the order Cu > Mn > Fe > Ni Co. The plot of the self-oxidation rate vs. pH passes through a maximum whose position on the pH scale depends on both the nature of metal and the structure of the thiol oxidized. For thiols having different structures, the kinetic orders in reactions catalyzed by copper ions differently vary with pH, which is apparently associated with the formation of complexes possessing different catalytic activity.     

Complexes of Copper(I) with Dimercapto Compounds as Catalysts for Oxidation of Mercaptans and Hydrogen Sulfide with Molecular Oxygen in Aqueous Solutions

The conditions for formation of complexes of copper(I) with mercapto compounds in aqueous- alkaline solutions and the catalytic activity of these complexes in oxidation of mercaptans and hydrogen sulfide was studied. The kinetic characteristics of these catalysts were compared with those of catalysts based on cobalt phthalocyanines. A method was proposed for suppressing formation of the thiosulfate ion in oxidation of H₂S to elemental sulfur.     

Kinetics of the Catalytic Oxidation Reactions of Thiol Compounds in Aqueous Solutions in the Presence of Copper Ions

The kinetics of the catalytic oxidation reactions of thiol compounds with molecular oxygen in aqueous solutions in the presence of copper ions was studied in relation to the structures of oxidized thiols and the pH of the solution. A modified procedure used for the determination of [O₂] allowed us to obtain the kinetic characteristics of more than 30 thiols over a wide pH range. We found that weakly chelating thiols exhibited a first order of reaction with respect to [Cu⁺] and [O₂] under conditions when the [(Cu⁺)(RS^–)₂] complex occurred. In the oxidation of strongly chelating thiols in an alkaline medium, the order of reaction with respect to [Cu⁺] was equal to 2, and the rate of reaction was independent of [O₂]. We found that the introduction of small amounts of strongly chelating thiols into Cu⁺ solutions containing difficult-to-oxidize mercaptans resulted in a dramatic acceleration of mercaptan oxidation. We hypothesized that O₂ was effectively bound to the [(Cu⁺)(RS^–)₂] complexes in an alkaline medium in the case of strongly chelating thiols, and this was not the case with the complexes of weakly chelating thiols.     

Tunneling transfer of an electron in oxidation of the HS− ion by an I 3 − complex in aqueous solution

Methods of chemical kinetics have been used in a study of the mechanism of hydrogen sulfide oxidation by iodine. It has been shown that the stage of electron transfer from HS^– to the I ₃ ^/– complex proceeds through a tunneling mechanism. A proposed twinkling model of the reaction mechanism provides an explanation for the observed experimental facts: the dependence of the rate constant on the acidity, viscosity, and ionic strength of the solution; the inverse temperature dependence of the reaction rate constant; the dependence of the reaction rate constant on the concentrations of iodide ion and maleic acid, which are not involved directly in the reaction.B. P. Konstantinov Institute of Nuclear Physics, Russian Academy of Sciences, Gatchina 188350. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 3, pp. 522–536, March, 1992.     

Oxidation of aminothiols by molecular oxygen catalyzed by copper ions. Stoichiometry of the reaction

Catalysis of oxidation of aminothiols by copper ions was studied depending on the structure of aminothiols and pH of the medium. The catalytic reaction proceeds in the inner coordination sphere of Cu⁺. At pH 7—9, oxidation of bidentate aminothiols involves reduction of O₂ to H₂O₂. At pH 9—13, oxidation of chelating aminothiols is accompanied by reduction of O₂ to H₂O, whereas oxidation of weak-chelating aminothiols still proceeds by the former mechanism. In this process, the thiolate anions coordinated to the Cu⁺ ions lose one electron each and are oxidized to amino disulfides, which go from the inner sphere of the Cu⁺ complex into a solution. Procedures developed for the determination of amino disulfides, the chemiluminescence determination of H₂O₂ in the presence of aminothiols as luminescence quenchers, and a modified polarographic procedure for the determination of O₂ allowed us to establish that oxidation of aminothiols is not accompanied by catalytic decomposition of H₂O₂ that formed.     

Tamm-Frank equation derived from expressions for transient radiation

The expressions for transient radiation intensity are analyzed in the case of a plane interface when the condition of Cerenkov radiation is satisfied. It is shown that they include the expression for Vavilov-Cerenkov radiation in a transparent medium modified by the interface. Institute of Physical Research, Armenian National Academy of Sciences, Ashtarak. Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Radiofizika, Vol. 40, No. 9, pp. 1126–1144, September, 1997.