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用水和2-丙醇的均相混合溶剂盐析法萃取六价铬:一项实验室研究

Extraction of chromium(VI) by salting-out with a homogeneous, mixed solvent of water and 2-propanol: a laboratory study.

作者信息

Samaratunga Sethsiri S, Nishimoto Jun, Tabata Masaaki

机构信息

Department of Chemistry, Faculty of Science and Engineering, Saga University, 1 Honjo-machi, Saga 840-8502, Japan.

出版信息

Environ Sci Pollut Res Int. 2008 Jan;15(1):27-30. doi: 10.1065/espr2006.11.359.

Abstract

BACKGROUND, AIMS AND SCOPE: Chromium enters into the aquatic environment as a result of effluent discharge from steel works, electroplating, leather tanning industries and chemical industries. As the Cr(VI) is very harmful to living organisms, it should be quickly removed from the environment when it happens to be contaminated. Therefore, the aim of this laboratory research was to develop a rapid, simple and adaptable solvent extraction system to quantitatively remove Cr(VI) from polluted waters.

METHODS

Aqueous salt-solutions containing Cr(VI) as CrO4(2-) at ppm level (4-6 ppm) were prepared. Equal volumes (5 ml) of aqueous and organic (2-PrOH) phases were mixed in a 10 ml centrifuge tube for 15 min, centrifuged and separated. Concentrations of Cr(VI), in both the aqueous and organic phases, were determined by atomic absorption spectrometry. The effects of salt and acid concentrations, and phase-contact time on the extraction of Cr(VI) were investigated. In addition, the extraction of Cr(VI) was assessed in the presence of tetramethylammonium chloride (TMAC) in 2-PrOH phase. Effects of some other metals, (Cd(II), Co(II), Cu(II), Ni(II) and Zn(II)), on the extraction of Cr(VI) were also investigated.

RESULTS AND DISCUSSION

The Cr(VI) at ppm level was extracted quantitatively by salting-out the homogeneous system of water and 2-propanol(2-PrOH) using chloride salts, namely CaCl2 or NaCl, under acidic chloride media. The extracted chemical species of Cr(VI) was confirmed to be the CrO3Cl-. The ion-pair complex extracted into the organic phase was rationalized as the solvated ion-pair complex of [2-PrOH2+, CrO3Cl-]. The complex was no longer stable. It implied the reaction between extracted species. Studies revealed that salts and acid directly participated in the formation of the above complex. Use of extracting agents (TMAC) didn't show any significant effect on the extraction of Cr(VI) under high salting-out conditions. There is no significant interference effect on the extraction of Cr(VI) by the presence of other metals. The Cr(VI) in the organic phase was back-extracted using an aqueous ammonia solution (1.6 mol dm(-3)) containing 3 mol dm(-3) NaCl. The extraction mechanism of Cr(VI) is also discussed.

CONCLUSIONS

Salting-out of homogeneous mixed solvent of 2-propanol can be employed to extract Cr(VI) quantitatively, as an ion-pair of [2-PrOH2+ * CrO3Cl-] solvated by 2-PrOH molecules. Then, the complex becomes 'solvent-like' and is readily separated into the organic phase. The increase of Cl- ion concentration in the aqueous phase favors the extraction. The 2-PrOH, salts and acid play important roles in the extraction process. There is no need to use an extracting agent at a high salting-out condition.

RECOMMENDATIONS AND PERSPECTIVES

Chromium(VI) must be quickly removed before it enters into the natural cycle. As the 2-PrOH is water-miscible in any proportion, ion-pairing between 2-PrOH2+ and CrO3Cl- becomes very fast. As a result, Cr(VI) can easily be extracted. Therefore, the method is recommended as a simple, rapid and adaptable method to quickly separate Cr(VI) from aqueous samples.

摘要

背景、目的和范围:铬因钢铁厂、电镀、皮革鞣制工业和化学工业的废水排放而进入水生环境。由于六价铬对生物体非常有害,一旦环境受到污染,就应迅速将其从环境中去除。因此,本实验室研究的目的是开发一种快速、简单且适应性强的溶剂萃取系统,以定量去除污染水中的六价铬。

方法

制备了含有百万分率(4 - 6 ppm)以铬酸根离子(CrO4(2-))形式存在的六价铬的盐水溶液。将等体积(5 ml)的水相和有机相(2 - 丙醇)在10 ml离心管中混合15分钟,然后离心分离。通过原子吸收光谱法测定水相和有机相中六价铬的浓度。研究了盐和酸的浓度以及相接触时间对六价铬萃取的影响。此外,在2 - 丙醇相中存在四甲基氯化铵(TMAC)的情况下评估了六价铬的萃取情况。还研究了一些其他金属(镉(II)、钴(II)、铜(II)、镍(II)和锌(II))对六价铬萃取的影响。

结果与讨论

在酸性氯化物介质下,使用氯化钙或氯化钠等氯化物盐对水和2 - 丙醇(2 - PrOH)的均相体系进行盐析,可定量萃取百万分率水平的六价铬。确认萃取的六价铬化学物种为三氧化铬氯(CrO3Cl-)。萃取到有机相中的离子对络合物被合理化为[2 - PrOH2 +, CrO3Cl-]的溶剂化离子对络合物。该络合物不再稳定,这意味着萃取物种之间发生了反应。研究表明,盐和酸直接参与了上述络合物的形成。在高盐析条件下,使用萃取剂(TMAC)对六价铬的萃取没有显示出任何显著影响。其他金属的存在对六价铬的萃取没有显著干扰作用。使用含有3 mol dm(-3)氯化钠的氨水溶液(1.6 mol dm(-3))对有机相中的六价铬进行反萃取。还讨论了六价铬的萃取机理。

结论

2 - 丙醇的均相混合溶剂盐析可用于定量萃取六价铬,形成由2 - 丙醇分子溶剂化的[2 - PrOH2 + * CrO3Cl-]离子对。然后,该络合物变得“类溶剂化”,易于分离到有机相中。水相中氯离子浓度增加有利于萃取。2 - 丙醇、盐和酸在萃取过程中起重要作用。在高盐析条件下无需使用萃取剂。

建议与展望

六价铬在进入自然循环之前必须迅速去除。由于2 - 丙醇能与水以任何比例互溶,2 - PrOH2 +与CrO3Cl-之间的离子配对变得非常快。因此,六价铬很容易被萃取。因此,该方法被推荐为一种简单、快速且适应性强的方法,可快速从水样中分离六价铬。

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