Mechanism and rate constants for complete series reactions of 19 fluorophenols with atomic H

Fluorine-containing halogenated fluorophenol may have efect as intermediate species involved in the formation of polyfluorinated dibenzo-p-dioxin/dibenzofurans(PFDDs/Fs). The mechanism for the atomic H initiated reactions with complete series of nineteen fluorophenol congeners was studies using the density functional theory. At the MPWB1K/6-31+G(d,p) level, the geometries and frequencies of reactants, transition states, and products were obtained, and the accurate energetic values were acquired at the MPWB1K/6-311+G(3df,2p) level. The rate constants were evaluated by the canonical variational transition-state theory with the small curvature tunneling contribution over a wide temperature range of 600–1000 K. The study shows that the intramolecular hydrogen-bond in the ortho-substituted FPs as well as the inductive efect of the electron-withdrawing fluorine and steric repulsion of multiple substitutions may ultimately be responsible for the relative strength of the O–H bonds in FPs. The results can be used for further studies on PFDD/Fs formation mechanism.     

胺基修饰的大孔树脂吸附黄连素的研究

为了提高大孔吸附树脂对黄连素的吸附能力,根据黄连素结构特点,对具有苯乙烯骨架的H109树脂进行了胺基修饰.考察了胺基修饰后的特征基团、孔径和比表面积的变化,并测试了经胺基修饰后树脂对黄连素的吸附效果,确定了最佳吸附温度和初始pH.同时,对吸附过程进行吸附动力学和热力学的拟合与分析.红外扫描结果表明:胺基修饰成功,吸附过程中树脂上的胺基与黄连素分子中的醚基形成了氢键;胺基修饰后的HX树脂的孔径和比表面积有所增大,比吸附量比胺基修饰前增加7.9mg·g-1.HX树脂对黄连素的最佳吸附条件为30℃、初始pH值8.吸附过程可以采用伪二级动力学模型和Freundlich吸附等温线进行描述.     

阴离子聚丙烯酰胺(APAM)和聚二甲基二烯丙基氯化铵(HCA)对给水厂污泥水分分布的影响及其与污泥颗粒的作用机制

为比较APAM和HCA对给水厂污泥调理的效果并探究其作用机制,测定了污泥调理前后的毛细吸水时间（CST）、污泥比阻（SRF）、溶解性有机污染物含量（DOC）、Zeta电位和絮体粒径的变化情况,并结合三维荧光谱图、液相-有机碳联用（LC-OCD）、热重差热法（TG-DTA）以及傅立叶红外（FTIR）的变化进行分析.结果表明,APAM和HCA的最佳投加量分别为0.05和0.10 g·L^-1,与之对应的CST分别从71.0 s降到25.8 s和37.6 s,SRF从9.72×10¹² m·kg^-1降到4.18×10¹² m·kg^-1和5.70×10¹² m·kg^-1,APAM的调理效果占优.HCA仅可释放毛细水,而APAM可释放污泥的毛细水和表面吸附水.APAM通过氢键的吸附架桥形成大块絮体以改善污泥脱水性能,Zeta电位的升高和有机物的变化显示出电中和及去水化作用是HCA的主要调理机制.本研究结果可为给水厂污泥脱水有机药剂的选择提供数据基础.     

氧氟沙星在碳纳米管上的吸附机制研究

碳纳米管吸附氧氟沙星(OFL)是控制其在水体中归趋的一种有效方法.本研究讨论了多壁碳纳米管及其共混酸处理产物(MWCNTs和MWCNTs-O)对于氧氟沙星的吸附过程.考察了吸附动力学、吸附等温线、pH的影响和解吸过程.结果表明,吸附动力学曲线符合准二级动力学模型,OFL在MWCNTs-O上的平衡吸附量较大;Langmuir模型和Freundlich模型都能很好拟合吸附过程;pH在6.0~10.0时,平衡吸附量下降很快;解吸过程出现了解吸滞后现象,在MWCNTs-O上更为明显.吸附热力学分析表明OFL在碳纳米管上的吸附作用力为分子间作用力,MWCNTs-O上较多含氧官能团的引入为OFL分子的吸附提供了较多的吸附点,有利于OFL分子和碳纳米管之间形成相对作用力较强的氢键,该作用力主导了OFL在碳纳米管上的吸附,解释了试验现象.