Experimental study of polysulfane stability in gaseous hydrogen sulfideстатья
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Аннотация:The solubility of sulfur in gaseous hydrogen sulfide has been studied in the H2S-S system. Experiments were carried out at temperatures between 50 and 290 degrees C and pressures up to 200 bars. The experimentally determined concentrations of sulfur in the gas phase are 6-7 orders of magnitude higher than the corresponding concentrations calculated for a system free of hydrogen sulfide. The results of experiments show significant interaction between S and H2S. These interactions can be of two kind: solvation by hydrogen sulfide (solubility), as with formation of new stable gaseous chemical compounds, like polysulfanes (chemical reaction). The data obtained can be reasonably well described by the formation of a H2S . S compound. Thermodynamic parameters for polysulfanes and equilibrium compositions of the S-H2S system have been calculated ab initio for the experimental conditions. At temperatures above 170 degrees C, results (of calculations) are in good agreement with experimental data, although the difference between the calculated and experimental mole fraction of the sulfur in the gas phase reaches 2 orders of magnitude at 125-170 degrees C. It is theorized that sulfur solubility in gaseous H2S is related to two main chemical reactions, dominated in the different temperature ranges: sulfur solvation by H2S (125-170 degrees C) and polysulfane formation (200-290 degrees C). Copyright (C) 1998 Elsevier Science Ltd.