The rate of sulfide oxidation by δMnO

阅读量:

48

作者:

W YaoFJ Millero

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摘要:

The rate of oxidation of hydrogen sulfide by manganese dioxide in seawater was determined as a function of pH (2.0–9.0), temperature (5–45°C), and ionic strength (0–4 M). The overall rate constant, k , in seawater at pH = 8.17 was found to be first order with respect to both sulfide and manganese dioxide: d[H2S]Tdt = k[H2S]τ[MnO2]. The rate constant, k , for seawater (S = 35.8, pH = 8.17) at 25°C was found to be 436 M 1 min 1 , or 0.0244 m 2 1 min 1 when [MnO 2 ] is expressed in surface area (m 2 /L). The energies of activation were found to be 14 ± 1 KJ mol 1 and 10 ± 1 KJ mol 1 , respectively, for pH = 8.2 and pH = 5.0 in seawater (S = 35). The rate increased from pH 2.0 to a maximum at a pH of about 5.0 and decreased at higher pH. This pH dependence was attributed to formation of a surface complex between >MnO and H 2 S. As the concentration of HS increases above pH = 5 the rate of the reaction decreases. The rate of sulfide oxidation by MnO 2 is not strongly dependent on ionic strength. The rates in 0.57 M NaCl were found to be slightly higher than the rates in seawater. Measurements made in solutions of the major sea salts indicated that Ca 2+ and Mg 2+ caused the rates to decrease, apparently by absorbing on the surface of manganese dioxide. Measurements made in artificial seawater (Na + , Mg 2+ , Ca 2+ , Cl , and SO 2 4 ) were found to be in good agreement with the measurements in actual seawater. Phosphate was found to inhibit the reaction significantly.

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DOI:

10.1016/0016-7037(93)90544-7

被引量:

100

年份:

1993

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