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Mechanisms of Interactions Involving Formation and Rupture of S-s bOnds in Inorganic Sulphur Oxo-Derivative Systems

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Mechanisms of ten redox interactions involving inorganic sulphur oxo-derivative systems thiosulphate (SbSaO32-) and polythionate (O3-Sa(Sb)nSaO3-) have been investigated where Sa is a sulphur centre directly coordinated by oxygens and one sulphur-b (Sb); Sb is a sulphur atom either directly bonded to Sa or any one of the others catenated to one adjacent to Sa. The degree of lability of the S-S bonds of these systems towards the hydroxyl anion is a function of its concentration and also of other species in the medium. In a weak concentration of hydroxyl anion medium, iodine effects only breakage of the π(Sa-Sb) bond of SbSaO32-. One electron from this bond migrates to Sa and another to Sb to give S*bS*aO32-. An electron from one anionic oxygen reduces the oxidant. Then one electron from this oxygen pairs with the Sa unpaired electron to form a new π(Sa-O) bond and highly reactive S*bSaO3- radicals, two of which couple to form the Sb-Sb bond of the tetrathionate anion (O3-Sa(Sb)2SaO3-). However, above a minimum OH- concentration for some interactions, the Sa=Sb bond completely breaks to yield SaO32- and Sb such that in the presence of iodine, nascent oxygen (O) and H- from OH- oxidizes SaO32-/Sb to SaO42-/SbO42- and reduces iodine respectively. In the absence of an oxidant, OH- reduces two-thirds of Sb to Sb2- with a concomitant yield of •OH which oxidizes a third of Sb to S6O32- leaving SaO32- intact. In the absence of an oxidant and where there is a minimum of 3:1 OH-:S4O62- ratio, OH- effects production of S*bSaO3-, S*aO3-, and Sb species by symmetrical and asymmetrical cleavage of S4O62-. S*bSaO3- changes to S*bS*aO3-, then to S*bS*aO32- by acquiring an electron from OH-, and finally to SbSaO32-; SaO32- forms in a similar manner from S*aO3-; and SbO32- is formed on oxidation of Sb by •OH. However, in the presence of iodine, a strong OH- concentration effects complete rupture of all S-S bonds and oxidation of all sulphurs eventually to SaO42-/SbO42- via OH- which interacts directly with S*aO3- while 0 and H- from it oxidizes Sb and reduces iodine respectively. Further, in the presence of various reductants (e.g. CN-, Aso2- used in this work), a mild and strong OH- concentration also effects complete rupture of all S-S bonds of S4O62- and then leads to products determined by the nature of the reductants.

Affiliations: 1: Inorganic Research Laboratory, Department of Chemistry, Makerere University, P.O. Box 7062, Kampala, Uganda


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