物理化学学报 >> 2006, Vol. 22 >> Issue (06): 761-763.doi: 10.3866/PKU.WHXB20060623

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水相中•HS的光谱表征及其与氧气的反应研究

房豪杰;董文博;张仁熙;侯惠奇   

  1. 复旦大学环境科学研究所, 上海 200433
  • 收稿日期:2005-12-27 修回日期:2006-02-09 发布日期:2006-05-31
  • 通讯作者: 董文博;侯惠奇 E-mail:wbdong@fudan.edu.cn, fdesi@fudan.edu.cn

Spectrum of •HS and Its Reactions with Oxygen in Aqueous Solution

FANG Hao-Jie;DONG Wen-Bo;ZHANG Ren-Xi;HOU Hui-Qi   

  1. Institute of Environment Science, Fudan University, Shanghai 200433, P. R. China
  • Received:2005-12-27 Revised:2006-02-09 Published:2006-05-31
  • Contact: DONG Wen-Bo;HOU Hui-Qi E-mail:wbdong@fudan.edu.cn, fdesi@fudan.edu.cn

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摘要： 利用激光光解-瞬态吸收技术探讨了水相•HS自由基的产生及其在水溶液中的化学行为. 实验中利用•OH与H2S反应以及266 nm激光直接光解HS−两种途径产生了•HS, 通过光谱解析, 得到了•HS的紫外-可见吸收光谱： 吸收范围为220~300 nm, 最大吸收在220 nm, 并且在250~270 nm有肩峰. 进一步的研究结果表明, 氧气饱和的水溶液中,•HS的化学行为非常活泼, 它首先与O2反应生成•SO2−, •SO2−继续与O2发生电子转移反应生成SO2和•O2−, 后者在酸性条件下会很快地质子化生成•HO2.

关键词: 激光光解-瞬态吸收, •, HS, 水相, H2S

Abstract: The 266 nm laser photolysis formation and chemical behavior of •HS in aqueous solution have been studied by laser photolysis-transient absorption technique. The 266 nm laser photolysis of H2O2 leads to the formation of •OH, which reacts with H2S to produce •HS, while solutions of HS− can also be directly photolyzed with 266 nm laser pulses to produce •HS radical. The transient UV-Vis absorption spectrum of •HS has been attributed to 220~300 nm with a maximum absorption at 220 nm and a shoulder at 250~270 nm. The chemical behavior of •HS is very active in oxygen saturated aqueous solution:•HS will first react with oxygen to form •SO2−, which further reacts with another oxygen molecule with the production of SO2 and •O2−. In acid solution, •O2− immediately protonates to form •HO2.

Key words: Laser photolysis- transient absorption, •, HS, Aqueous phase, H2S