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[二氧化锰对五氯苯酚的氧化作用]

[Oxidation of pentachlorophenol by manganese dioxide].

作者信息

Zhao Ling, Peng Ping-an, Huang Wei-lin

机构信息

State Key Laboratory of Organic Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640, China.

出版信息

Huan Jing Ke Xue. 2006 Jul;27(7):1388-92.

Abstract

This study examined the oxidative transformation kinetics of pentachlorophenol (PCP) by manganese dioxide (MnO2) at pH 4.12 solution using manganese dioxide as an oxidant. This study also discussed the influence of pH on the reaction kinetics. Results show that PCP has highly susceptible to oxidation by manganese dioxide. The loss of PCP slows as the reaction progresses and deviates from the simple pseudo-first-order kinetics but follows complex reaction kinetics when experiments were performed at a constant pH and with an enough excess of MnO2. Furthermore, the reaction rate of PCP decreases significantly as the pH of the reaction mixture increases from 3.5 to 6.6. Using solvent extraction and GC-MS analysis, one minor and two major products were detected. The minor product is the mixture of tetrachloro-1, 4-hydroquinone and tetrachlorocatechol, and the two major products are dimeric products that formed by coupling of pentachlorophenoxy radicals. Furthermore, the two major products are structural isomers, resembling each other except for the position of nine chloride atoms on the aromatic ring. On the basis of the surface reaction kinetics and product identification observed in this study, the reaction scheme for PCP oxidation by manganese dioxide is tentatively

摘要

本研究以二氧化锰为氧化剂,考察了在pH 4.12的溶液中二氧化锰对五氯苯酚(PCP)的氧化转化动力学。本研究还讨论了pH对反应动力学的影响。结果表明,PCP极易被二氧化锰氧化。随着反应的进行,PCP的损失减缓,偏离了简单的准一级动力学,但在恒定pH和足够过量的MnO₂条件下进行实验时,遵循复杂的反应动力学。此外,随着反应混合物的pH从3.5增加到6.6,PCP的反应速率显著降低。通过溶剂萃取和GC-MS分析,检测到一种次要产物和两种主要产物。次要产物是四氯-1,4-对苯二酚和四氯邻苯二酚的混合物,两种主要产物是由五氯苯氧基自由基偶联形成的二聚产物。此外,这两种主要产物是结构异构体,除了芳环上九个氯原子的位置外彼此相似。基于本研究中观察到的表面反应动力学和产物鉴定,初步提出了二氧化锰氧化PCP的反应方案

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