EXTRACTION OF ANIONIC CADMIUM COMPLEXES WITH ORGANIC SOLUTIONS OF QUATERNARY AMMONIUM SALTS

Yulia I. Matyushkina, A. A. Shabarin
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引用次数: 1

Abstract

The anion-exchange extraction of thiocyanate, chloride and iodide cadmium complexes by solutions of quaternary ammonium salts chlorides in organic solvents (toluene, carbon tetrachloride, ethyl acetate, isobutyl alcohol, nitrobenzene) was studied. Extraction involves solutions of alkyl dimethylbenzylammonium chlorides (R-N+(CH3)2-CH2C6H5-Cl-) and alkyl dimethylethyl-benzylammonium (R-N+(CH3)2-CH2-CH2C6H5-Cl-), where R is a straight alkyl chain, mainly C12 - C14. The composition of the cadmium anionic complexes was established by the analysis of the calibration curves E = f (pCCd (II)) constructed from cadmium sulfate solutions against the background of various contents of thiocyanate, chloride and iodide ions (ndicator electrode - ion-selective electrode with a membrane, which based on a nitrobenzene solution of tetradecylammonium bromide). The extraction process is estimated quantitatively using a distribution coefficient (D). The value of D is calculated taking into account the cadmium concentration in the aqueous phase before and after extraction. The dependence of the distribution coefficient on the organic solvent dielectric constant, the concentration and stability of the anionic complexes of cadmium is shown. So, for the indicated cadmium acidocomplexes, the minimum D values were obtained using low-polar toluene and carbon tetrachloride, and the maximum values were obtained using highly polar isobutyl alcohol and nitrobenzene. If the concentration of cadmium (II) is reduced by a factor of 100 for the cadmium rhodanide and iodide complexes, the value of D decreases by 1.6-1.9 times, for the chloride complex, by 1.2 times in the case of polar isobutyl alcohol and nitrobenzene, and 2.9-3.5 times in the case of low-polar solvents. It was experimentally established that in the series [Cd(SCN)4]2- - [CdI4]2-- [CdCl4]2- the value of D decreases for all the studied systems. The observed regularity is related both to the stability of the corresponding cadmium (II) complexes in aqueous solutions and to their hydrophobicity.
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季铵盐有机溶液萃取阴离子镉配合物
研究了季铵盐氯化物在有机溶剂(甲苯、四氯化碳、乙酸乙酯、异丁醇、硝基苯)中的阴离子交换萃取硫氰酸盐、氯化物和碘化镉配合物。萃取采用烷基二甲基苄基氯化铵(R- n +(CH3)2-CH2C6H5-Cl-)和烷基二甲基乙基苄基铵(R- n +(CH3)2-CH2-CH2C6H5-Cl-)溶液,其中R为直烷基链,主要为C12 - C14。通过分析不同硫氰酸盐、氯离子和碘离子背景下的硫酸镉溶液(指示电极-带膜离子选择电极,以硝基苯十四烷基溴化铵溶液为基础)构建的校准曲线E = f (pCCd (II)),确定了镉阴离子配合物的组成。通过分配系数(D)对萃取过程进行定量估计。D值的计算考虑了萃取前后水相中镉的浓度。研究了镉离子的分布系数与有机溶剂介电常数、镉离子离子配合物的浓度和稳定性的关系。因此,对于指示的镉酸配合物,使用低极性甲苯和四氯化碳获得的D值最小,使用高极性异丁醇和硝基苯获得的D值最大。如果罗达尼镉和碘化物络合物的镉(II)浓度降低100倍,则氯络合物的D值降低1.6-1.9倍,极性异丁醇和硝基苯的D值降低1.2倍,低极性溶剂的D值降低2.9-3.5倍。实验证明,在[Cd(SCN)4]2- - [CdI4]2-- [CdCl4]2-系列中,所有研究体系的D值都减小。所观察到的规律性与相应的镉(II)配合物在水溶液中的稳定性和它们的疏水性有关。
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