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六价铬(Cr(VI))在含有长链季铵盐的聚合微胶囊上从水溶液中的吸附行为:动力学和热力学分析。

Cr(VI) sorption behavior from aqueous solutions onto polymeric microcapsules containing a long-chain quaternary ammonium salt: kinetics and thermodynamics analysis.

机构信息

Laboratorio de Operaciones Unitarias, Facultad de Ciencias Químicas y Farmacéuticas, Universidad de Chile, Av. Vicuña Mackenna 20, Santiago, Chile.

出版信息

J Hazard Mater. 2009 Dec 15;172(1):262-8. doi: 10.1016/j.jhazmat.2009.06.167. Epub 2009 Jul 8.

Abstract

This work studies the adsorption of Cr(VI) ions from an aqueous acid solution on hydrophobic polymeric microcapsules containing a long-chain quaternary ammonium salt-type extractant immobilized in their pore structure. The microcapsules were synthesized by adding the extractant Aliquat 336 during the in situ radical copolymerization of the monomers styrene (ST) and ethylene glycol dimethacrylate (EGDMA). The microcapsules, which had a spherical shape with a rough surface, behaved as efficient adsorbents for Cr(VI) at the tested temperatures. The results of kinetics experiments carried out at different temperatures showed that the adsorption process fits well to a pseudo-second-order with an activation energy of 82.7 kJ mol(-1), confirming that the sorption process is controlled by a chemisorption mechanism. Langmuir's isotherms were found to represent well the experimentally observed sorption data. Thermodynamics parameters, namely, changes in standard free energy (DeltaG(0)), enthalpy (DeltaH(0)), and entropy (DeltaS(0)), are also calculated. The results indicate that the chemisorption process is spontaneous and exothermic. The entropy change value measured in this study shows that metal adsorbed on microcapsules leads to a less chaotic system than a liquid-liquid extraction system.

摘要

这项工作研究了从酸性水溶液中吸附六价铬离子在含有固定在其孔结构中的长链季铵盐型萃取剂的疏水性聚合微胶囊上的吸附作用。微胶囊是通过在单体苯乙烯(ST)和乙二醇二甲基丙烯酸酯(EGDMA)的原位自由基共聚过程中添加萃取剂 Aliquat 336 合成的。微胶囊具有粗糙表面的球形形状,在测试温度下表现为对 Cr(VI) 的有效吸附剂。在不同温度下进行的动力学实验结果表明,吸附过程很好地符合假二级动力学模型,其活化能为 82.7 kJ mol(-1),证实了吸附过程受化学吸附机制控制。Langmuir 等温线很好地代表了实验观察到的吸附数据。还计算了热力学参数,即标准自由能变化(DeltaG(0))、焓变化(DeltaH(0))和熵变化(DeltaS(0))。结果表明,化学吸附过程是自发的和放热的。本研究中测量的熵变值表明,与液-液萃取系统相比,吸附在微胶囊上的金属导致系统的混乱度降低。

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