Reactivity of hydrogen sulfide toward organic compounds with sulfur-sulfur bonds

Abstract

The presence of organic molecules containing sulfur-sulfur bonds was documented in the water columns and sediments of the natural aquatic systems as well as in fossil fuels. These compounds range from small molecules of volatile organic compounds to polysulfide cross-linked macromolecules in the sediments. While processes leading to formation of these compounds were intensively studied during the last decades, kinetics and mechanisms of reactions which lead to their decomposition are poorly understood. In this work, the kinetics and products of the reactions of dimethyl disulfide, dimethyl trisulfide, and cyclic polysulfide lenthionine (1,2,3,5,6-pentathiepane) with hydrogen sulfide at the environmental pH and temperature ranges were studied. It was shown that at pH ≥ 5, the reaction of bisulfide anion (HS–) rather than that of hydrogen sulfide controls the overall reaction rates. The activation energy and the order of the reaction with respect to bisulfide anion is dimethyl disulfide– < dimethyl trisulfide < lenthionine, while the order of the reaction with respect to organosulfur compounds is lenthionine < dimethyl trisulfide < dimethyl disulfide. The obtained results suggest that bisulfide anion is responsible for fast decomposition of organosulfur compounds in aphotic natural aquatic systems. This observation leads to the conclusion that sulfurization of sedimentary organic matter during the early diagenesis is not an unidirectional but a dynamic process, and concentrations of organic compounds with sulfur-sulfur bonds are controlled by the polysulfide to sulfide sulfur concentrations ratio in the sedimentary pore waters. In addition, the cyclic polysulfides were shown to be more stable than their linear analogs that results in preferential preservation of these compounds during the maturation process.