Reduction of Sulfur Dioxide on Carbons Catalyzed by Salts

Abstract: The reduction of SO₂ on different carbons in the presence of the nitrates and sulfides of sodium, potassium and calcium and potassium polysulfides was studied. The presence of salts increased the initial rate 2-5 fold for all of them and did not change the product distribution. The catalysis was not determined by the cation and there was no difference in the catalytic reactivity between nitrates and sulfides. The sulfur content of the activated carbon increased during the reaction on account of the stable reactive intermediates in the reduction of SO₂. In the presence of NaNO₃ or Na₂S, the amount of sulfur incorporated was in the molar ratio Na:S = 3 ± 0.3, and the XPS spectra of the residual carbon showed an increase of ca. 9% of the non-oxidized form of sulfur in the intermediates. In the absence of salt, it is proposed that after the adsorption of SO₂ on the carbon, a 1,3,2-dioxathiolane or 1,2-oxathietene 2-oxide are formed and that decompose to produce CO₂ and atomic sulfur. The non-oxidized sulfur intermediate would be an episulfide 3, formed from the reaction of the atomic sulfur with the nearest double bond and followed by consecutive reactions of insertion of atomic sulfur to form a trisulfide. Extrusion of S₂ from the trisulfide would regenerate the episulfide, establishing a sulfidedisulfide-trisulfide equilibrium that worked as a capture-release cycle of sulfur. In the presence of salt, the results are consistent with the assumption that the episulfide 3 reacts with the corresponding sulfide anion to form a disulfide anion, which upon reaction with atomic sulfur forms a trisulfide anion that decomposes releasing diatomic sulfur S₂, transporting the sulfur and generating a thiolate that is part of the catalytic cycle.