Investigation of the complexation of metal-ions by strong ligands in fresh and marine water

SCOPE: The detection and investigation of metal ions bound in strong complexes in natural waters is a difficult task, due to low concentration of the metal ions themselves, and also of the strong ligands, which, moreover, are often not of a well-defined composition. Here, a method is proposed for the investigation of the speciation of metal ions in natural waters. OBJECTIVE AND METHOD: It is based on the sorption of metal ions on strongly sorbing ion exchange resins, i.e. complexing resins. For this reason the method is called Resin Titration. It has been shown in previous investigations that the concentration of metal ion totally sorbed by a particular resin, and its reaction coefficient in the solution phase in the presence of the resin, can be determined from the sorption data using a simple relationship. Here, a data treatment (the Ruzic linearization method) is proposed for also determining the concentration of the ligands responsible for the complex in equilibrium with the resin. RESULTS: The method was applied to data obtained by Resin Titration of a freshwater and a seawater. Copper(II) and aluminium(III) were considered, using Chelex 100 as a titrant, due to its strong sorbing properties towards these metal ions. The results were: the total metal concentration in equilibrium with the resin, the side reaction coefficients, and the concentration of ligands. In all these cases the ligands forming very strong complexes were found to be at concentration lower than that of the metals. CONCLUSION: The Ruzic linearization method allows the determination of the concentration of the ligands forming very strong complexes in equilibrium with Chelex 100. The reaction coefficient was better determined by the calculation method previously proposed for RT. The ligands responsible for the strong complexes were found to be at low concentration, often lower than that of the metal ions considered. The metal in the original sample is partly bound to these ligands, since the complexes are very strong. Only a part of the metal is linked to weaker ligands, or free.     

飞灰颗粒物介导活性氧氧化损伤与金属离子浸取浓度的关系研究

本文利用脱氧核糖氧化法考察了飞灰颗粒物氧化能力与络合剂及盐酸浸取颗粒物上金属浓度的关系。结果表明,代表氧化损伤程度指标的脱氧核糖氧化物,通过硫代巴比妥酸似丙二醛加合物显色反应,其吸光度值与飞灰颗粒物被浸取剂盐酸及氨三乙酸作用后的金属离子铁、锌、镉、铅和锰的浓度显著相关。基于铁在自然环境中的高含量及在活性氧催化反应中的特殊性,本文认为二乙三氨五乙酸、乙二胺四乙酸及柠檬酸浸取液中的金属浓度不能很好地表     

络合滴定－阳极溶出伏安法测定腐植酸与金属络合物的稳定常数

以金属离子络合滴定－阳极溶出伏安法（ＡＳＶ法）测定得出湘江底泥、灵石风化煤和德都泥炭３种腐植酸分别与Ｐｂ、Ｃｄ的络合稳定常数、络合容量和分子量３个参数．并探讨了可能的误差来源及消除方法。     

四氯乙烯替代四氯化碳作为油类萃取剂的研究

油类萃取剂四氯化碳对人体毒性较大，且对大气臭氧层有着严重的破坏作用。实验尝试用低毒的四氯乙烯替代四氯化碳作为油测定的萃取剂。经两者在检出限、线性、精密度、质控样品测定，以及萃取效率试验、加标回收试验的比较。结果表明：改进方法代替标准方法基本可行。四氯乙烯较之其他替代品具有一定的优越性。     

从废催化剂中回收钼的新工艺

确定了用新型复合浸取剂从废催化剂中回收钼的最佳工艺条件废催化剂颗粒度１００目焙烧温度７５０℃,焙烧时间１ｈ复合浸取剂中助浸剂质量为５％,浸取固液质量比１：３,浸取温度６０℃,浸取时间６ｈ,在该条件下,钼的浸取率达到９２．７％～９５．５％。     

氟污染土壤中有效态氟提取剂的选择

通过对1.00mol/L NH4Cl、0.02mol/L NH4Cl、0.01mol/L CaCl2和H2O四种提取剂对污染土壤中元素氟的提取能力的分析比较,以及土壤性质与提取量的相关分析,确定了1.00mol/LNH4Cl为提取污染土壤中有效态氟最适宜的提取剂,为测定污染土壤中有效态氟含量,科学、合理评价氟的生态效应提供参考。     

富马酸生产废水的资源化研究

用PCW-7-甲苯络合萃取剂处理富马酸废水,萃取液用碱液反萃回收,每立方米废水可回收9kg富马酸,其含量大于97％。研究了影响萃取效果的相关因素．确定了适宜的工艺条件。     

苯甲酸生产残液中锰、钴和镍的提取及分离

探讨了苯甲酸生产残液中锰、钴和镍的提取及分离方法。首先采用酸溶液提取残液中的金属元素;然后通过氨水沉淀法分离锰;最后使用p507萃取剂分离钴和镍。实验结果表明:当苯甲酸生产残液中锰、钴和镍的质量分数分别为0.085 0%,0.307 1%,0.015 5%时,在硫酸浓度为2.0 mol/L、过氧化氢溶液质量分数为25%的条件下,锰、钴和镍的提取率分别为88.59%,87.77%,86.50%;当氨水浓度为2 mol/L时,锰的沉淀率达94.24%;在平衡水相p H为4、p507萃取剂皂化率为60%、油相中p507萃取剂的体积分数为15%的条件下,钴萃取率达87.53%,镍萃取率仅为8.46%,钴镍分离系数为68.70。     

Removal of metal ions from the complexed solutions in fixed bed using a strong-acid ion exchange resin

Fixed bed removal of equimolar metal ions (Co²⁺, Ni²⁺, Mn²⁺, Sr²⁺) from aqueous solutions using a strong-acid resin was examined. The solution contained a water-soluble complexing agent including ethylenediaminetetraacetic acid, nitrilotriacetic acid, and citric acid. Experiments were performed under different solution pH and molar concentration ratios of complexing agent to the total metals. It was shown from batch studies that the equilibrium exchange of metals and the resin mainly depended on solution pH, and partly on the type of complexing agent used. A mass transfer model was proposed to describe the breakthrough curves of the resin bed, which contained two parameters (τ and k) estimated from the observed breakthrough data. The calculated breakthrough curves agreed well with the measured ones (standard deviation <6%). In fixed bed tests at low pH (=2), the type of complexing agent had little effect on the breakthrough data. For a given complexing agent, the metal with a larger overall formation constant (K_f) showed a smaller exchange capacity. For a given metal ion, the complexing agent with a larger K_f also revealed a smaller exchange capacity.     

土壤中有效态稀土元素提取剂的选择

 通过0.01mol/LHCl，0.05mol/LHCl，1.0mol/L NH₄Oac（pH7.0），1.0mol/LNH₄NO₃（pH7.0），1.0mol/LHOAc/NH₄Oac（pH4.8），1.0mol/LNH₄Cl（pH7.0）6种提取剂对20种土壤中有效态稀土元素测定结果的比较，以及将测定结果同土壤特性、土壤中稀土元素形态进行相关分析，并通过黑麦草土培试验进行了生物评价，确定了1.0mol/LNH₄NO₃（pH7.0）为提取土壤中有效态稀土元素的最佳提取剂．