Mechanism of H_2S Oxidation by Ferric Oxide and Hydroxide Surfaces

摘要

The interaction of H_2S with the surface of either α-Fe_2O_3 or amorphous ferric hydroxide at low temperatures has been characterized using FTIR and quantified using volumetric methods. The mechanism of the interaction of H_2S with either reagent is ionic and involves heterolytic dissociation of H_2S and exchange of S~(2-) and SH~- anions for O~(2-) or OH~-. Subsequently water is eliminated and, in coupled redox reactions, sulfide is oxidized to elemental sulfur and Fe~(3+) cations are reduced to Fe~(2+). Initially, almost all the surface sites can interact readily with H_2S, to form a layer of iron sulfides. Over longer reaction times reaction occurs with deeper sites, to form bulk sulfides. Regeneration of ferric (hydr)oxide by oxidation with oxygen converts Fe~(2+) to Fe~(3+), and S~(2-) anions are replaced by O~(2-) with formation of elemental sulfur. The surface species involved in each reaction have been characterized using FTIR and, for the first time, direct evidence has been obtained for the presence of SH~- anions as very reactive intermediates.