Chelating resin from functionalization of chitosan with complexing agent 8-hydroxyquinoline: application for metal ions on line preconcentration system

This study describes the functionalization of biopolymer chitosan, using the complexing agent 8-hydroxyquinoline (oxine) by reaction of diazotization. The chelating resin was characterized by degree of deacetylation, infrared, Raman spectroscopy. The efficiency of the chelating resin and accuracy of the proposed method was evaluated by the metal ion recovery technique in the analysis of potable water, lake water, seawater and a certified sample of oyster tissue. The metal ions Cd(II) and Cu(II) in the samples were previously enriched in a minicolumn and flow injection flame atomic absorption spectrometry (FI-FAAS) determined the concentrations of the analytes. The chelating resin exhibited high selectivity for Cd(II) at pH 7 and for Cu(II) at pH 10. The eluent concentration was tested by the use of HNO₃ in concentrations of 0.1-3 mol l⁻¹ maximum response was obtained at 0.5 mol l⁻¹ for Cd(II) and Cu(II), with R.S.D. values of 0.4%. The analytes gave relative standard deviations (R.S.D.) of 1.5 and 0.7% for solutions of Cd(II) and Cu(II), respectively (n = 7) containing 20 μg l⁻¹ of the metal ions, defining a high reproducibility. The limits of detection (LOD) were 0.1 μg l⁻¹ for Cd(II) and 0.4 μg l⁻¹ for Cu(II). The analytical properties of merit were obtained using the parameters previously optimized with preconcentration time of 90 s. The chelating resin showed chemical stability within a wide range of pH and the efficiency was not altered for the preconcentration of the metal ions during all the experiments.     

Synthesis of macroporous poly(vinyldiethylenetriamine) chelating resin and the enrichment—separation of rhodium and iridium

Poly(vinyldiethylenetriamine) chelating resin was synthesized from macroporous poly(vinyl chloride) and used for the enrichment-separation of rhodium and iridium. The efficiency, rate and equilibrium constant adsorption of rhodium and iridium on the resin were determined and real samples were analysed. The mechanism of rhodium and iridium enrichment is discussed.     

Sulphoxine immobilized onto chitosan microspheres by spray drying: application for metal ions preconcentration by flow injection analysis

A new chelating resin based on chitosan biopolymer modified with 5-sulphonic acid 8-hydroxyquinoline using the spray drying technique for immobilization is proposed. The chelating resin was characterized by thermogravimetric analysis (TGA) and X-ray diffraction (XRD) and surface area by nitrogen sorption. The efficiency of the chelating resin was evaluated by the preconcentration of metal ions Cu(II) and Cd(II) present in aqueous samples in trace amounts. The metal ions were previously enriched in a minicolumn and the concentrations of the analytes were determined on-line by flame atomic absorption spectrometry (FAAS). The maximum retention for Cu(II) occurred in the pH range 8-10, and for Cd(II) at pH 7. The optimum flow rate for sorption was found to be 7.2 ml min⁻¹ for the preconcentration of the metal ions. The analytes gave relative standard deviations (R.S.D.) of 0.7 and 0.6% for solutions containing 20 μg l⁻¹ of Cu(II) and 15 μg l⁻¹ of Cd (II), respectively (n=7). The enrichment factors for Cu(II) and Cd (II) were 19.1 and 13.9, respectively, and the limits of detection (LOD) were 0.2 μg l⁻¹ for Cd(II) and 0.3 μg l⁻¹ for Cu(II), using a preconcentration time of 90 s (n=11). The accuracy of the proposed method was evaluated by the metal ion recovery technique, in the analysis of potable water and water from a lake, with recoveries being between 97.2 and 107.3%.     

Determination of 232Th in seawater by ICP-MS after preconcentration and separation using a chelating resin

This article describes an analytical method for the separation, preconcentration and determination of ²³²Th in seawater samples at sub-ng/L levels using a NOBIAS CHELATE PA1 resin and a sector field (SF) inductively coupled plasma mass spectrometer (ICP-MS). The resin showed excellent adsorption of ²³²Th at a low pH of 2.4 ± 0.4 in a relatively small volume (200 mL) of seawater. ²³²Th adsorbed on the resin was easily eluted using 5 mL of 0.8 M HNO₃. An enrichment factor of 40 was achieved for ²³²Th analysis. Ethylenediamine-tetraacetic acid disodium salt dehydrate (EDTA) was used to investigate the effect of ²³²Th-binding organic ligand on the retention of ²³²Th on the chelating resin. Results obtained using acidified samples (pH of 2.4 ± 0.4) showed EDTA had no significant effect on ²³²Th recovery, indicating that at this low pH, ²³²Th was dissociated from the ²³²Th-binding organic ligand and quantitatively retained on the NOBIAS CHELATE PA1 resin. The developed analytical method was characterized by a separation and preconcentration taking approximately 4 h and a low detection limit of 0.0038 ng/L for ²³²Th, and was successfully applied to the determination of ²³²Th in seawater samples collected from coastal areas, Japan.     

A chelating resin containing bis(2-benzimidazolylmethyl)amine: synthesis and metal-ion uptake properties suitable for analytical application

A new stable chelating resin was synthesized by incorporating the bis(2-benzimidazolyl methyl)amine into Merrifield polymer through CN covalent bond and characterized by elemental analysis, IR and thermal study. The sorption capacity of the newly formed resin for Ag(I), Cu(II), Fe(III), Hg(II) and Pb(II) as a function of pH have been studied. The resin exhibits no affinity for alkali or alkaline earth metals. In column operation it has been observed that Ag(I) in trace quantities can be separated from different complex matrices and Hg(II) can be removed from the river water spiked with Hg(II) at usual pH of natural waters.     

强酸性阳离子交换树脂催化合成醋酸正丁酯的动力学研究

以强酸性阳离子交换树脂Amberlyst 15作为催化剂,研究了醋酸与正丁醇合成醋酸正丁酯的反应动力学;考察了搅拌速度、催化剂粒径、温度、催化剂用量,以及酸醇物质的量之比对醋酸转化率的影响;建立了拟均相动力学模型,对实验数据进行了拟合,并估算了相应的动力学参数.结果表明,由拟均相动力学模型得到的计算值与实验值吻合较好.     

A kinetic investigation of removal of chromium from aqueous solutions with a strong cation exchange resin

A kinetic investigation was performed with an ion exchange resin for chromium. A strong cation exchange resin (Amberlite IR 120) was used for removal of chromium. The effects of concentration, resin amount, and stirring speed on kinetics were investigated. The metal concentration range studied was between 5 to 160 mg/dm³ (the amount of solution was 4 dm³), the resin amount range was between 5 to 20 mg, and the stirring speed range was between 1000 to 3500 rpm. Equilibrium experiments were performed for calculation of separation factor. Kinetic studies were done using a Kressman-Kitchener stirrer reactor system and the results were compared with existing kinetic models. Two models, Nernst-Plank film diffusion control model (fdc) and solid phase diffusion control model (pdc), respectively were identified, and the dependence of the rate on parameters such as solution concentration, resin amount, stirring speed, etc. was examined for each of them. The interpretation of these data shows that the system is probably controlled by both film and particle diffusion. Correspondence: Sevgi Kocaoba, Department of Chemistry, Faculty of Art and Science, Yildiz Technical University, Davutpasa Cad. No: 127, 34210 Davutpasa-Istanbul, Turkey.     

Use of an o-aminobenzoic acid-functionalized XAD-4 copolymer resin for the separation and preconcentration of heavy metal(II) ions

XAD copolymer resins may be functionalized with heavy metal ion-selective ligands either by covalent linkage to the polymer backbone or by impregnation. These resins may be tailored to be specific for certain heavy metals by adjusting the adsorption and elution parameters, thereby enabling simple and cost-effective spectrophotometric and flame atomic absorption spectrometry (FAAS) determinations of these metals without requiring the more sophisticated coupled instrumental techniques. For the synthesis of o-aminobenzoic acid (ABA)-immobilized XAD-4 copolymer resin that is expected to preconcentrate a number of transition and heavy metals, the azo-linkage method was chosen. For this purpose the copolymer was nitrated, reduced to the corresponding amine, converted to the diazonium salt with nitrite, and reacted with o-aminobenzoic acid to produce the XAD-ABA sorbent. This sorbent was capable of preconcentrating Pb(II), Cd(II), Ni(II), Co(II) and Zn(II) from weakly acidic or neutral aqueous solution. The retained metals were eluted with 1.0 M HNO₃ from the resin column, and were subsequently determinated with by flame atomic absorption spectrometry. The developed resin preconcentration and determination method was successfully applied to the analysis of a synthetic metal mixture solution, a certified reference material (CRM) of coal sample, and brackish lake water.     

阴离子交换树脂分离-原子荧光法测定色母粒中的镉

采用微波消解溶样,结合离子交换法对色母粒样品进行待测元素的提取及净化处理,利用原子荧光光度计进行镉含量的测定。研究了717型阴离子交换树脂对色母粒样品中镉的吸附及分离条件,解决了样品中铅、铜等元素的干扰问题。方法加标回收率在92.4%～117.4%之间,相对标准偏差小于3.0%。     

Application of triethylenetetramine to the separation of metal ions on selective exchange resin chelex 100

The distribution coefficients of Ca²⁺, Cu²⁺, Ni²⁺ and Pb²⁺ on Chelex 100 in the presence and absence of triethylenetetramine have been determined. Ca²⁺, Cu²⁺, Ni²⁺ and Mg²⁺, Cu²⁺, Pb²⁺ mixtures have been separated on Chelex 100 and Dowex A-1 respectively.     

Electro-adsorption of polyethyleneimine on the anion exchange membrane: Application to the nitrate removal from loaded solutions

Anion exchange membrane has been modified by fixation of polyethyleneimine. The modification has been carried out aiming to achieve a separation of anions according to their hydration radii and their sizes. The performances of the modified membranes were compared with the unmodified one by applying Donnan dialysis of nitrate ion using Cl⁻ in the strip compartment. The transfer of nitrate ions in the presence of chloride was enhanced by using immersion modified membrane. The presence of a thin layer of PEI on the strip side of the membrane improves Cl⁻ transference, by creating a chemical potential difference which increases the transfer.     

An approach by using near-infrared diffuse reflectance spectroscopy and resin adsorption for the determination of copper, cobalt and nickel ions in dilute solution

Near-infrared spectroscopy (NIRS) has been proved to be a powerful analytical tool and used in various fields, it is seldom, however, used in the analysis of metal ions in solutions. A method for quantitative determination of metal ions in solution is developed by using resin adsorption and near-infrared diffuse reflectance spectroscopy (NIRDRS). The method makes use of the resin adsorption for gathering the analytes from a dilute solution, and then NIRDRS of the adsorbate is measured. Because both the information of the metal ions and their interaction with the functional group of resin can be reflected in the spectrum, quantitative determination is achieved by using multivariate calibration technique. Taking copper (Cu²⁺), cobalt (Co²⁺) and nickel (Ni²⁺) as the analyzing targets and D401 resin as the adsorbent, partial least squares (PLS) model is built from the NIRDRS of the adsorbates. The results show that the concentrations that can be quantitatively detected are as low as 1.00, 1.98 and 1.00 mg L⁻¹ for Cu²⁺, Co²⁺ and Ni²⁺, respectively, and the coexistent ions do not influence the determination.     

Shipboard analysis of picomolar levels of manganese in seawater by chelating resin concentration and chemiluminescence detection

A new shipboard analytical method for determining picomolar levels of manganese in seawater has been developed. The method is based on a combination of chelating resin column extraction and improved chemiluminescence (CL) detection in a closed flow system. In this method, manganese in sample solution is selectively collected on newly-developed iminodiacetate-immobilized chelating resin, and then eluted with acidic solution containing hydrogen peroxide. The resulting eluent is mixed with luminol solution and aqueous ammonia after removal of iron ions by a chelating resin column, and then the mixture is introduced into the CL cell. The manganese concentration is obtained from the CL intensity. The detection limit (3SD) of manganese is 5 pmol L^–1 from 9 mL of seawater sample. The method was applied to seawater samples collected at the Okinawa Trough.     

无孔单分散亲水性中强阳离子交换树脂的制备及其在蛋白质快速分离中的应用研究

以3.0μm无孔单分散亲水性交联聚甲基丙烯酸环氧丙酯树脂为基质,将其表面经新的化学方法改性后制备了一种新型的无孔中强阳离子交换色谱填料。详细考察了该无孔填料对标准蛋白分离性能,有机溶剂、pH、流动相盐种类和流速等对蛋白质保留的影响。实验结果表明,在流速为4 mL/min时,线性梯度时间在2.0 min内可快速分离4种标准蛋白,蛋白质的保留符合阳离子交换色谱规律。将其应用于快速纯化鸡蛋清中的溶菌酶,取得较好效果。     

Use of carboxylic acid cation exchange resin in the analysis of copper in chromated wood preservative solutions

An ion exchange separation, using carboxylic acid resin, combined with a thiosulphate titration is suggested as a rapid and accurate method for the determination of copper in chromated wood preservatives.     

The effect of physicochemical parameters on the separation recovery of plutonium and uranium from aqueous solutions by cation exchange

The effect of physicochemical parameters such as pH, salinity (e.g. [NaCl]) and competitive cation (e.g. Ca²⁺ and Fe³⁺) concentration on the separation recovery of plutonium and uranium from aqueous solutions by cation exchange has been investigated. The investigation was performed to evaluate the applicability of cation exchange as separation and pre-concentration method prior to the radiometric analysis of uranium and plutonium isotopes in natural water samples. Application of the method to test solutions of constant radionuclide concentration and variable composition (0.1, 0.5 and 1 M NaCl; 0.1 and 0.5 M Ca(NO₃)₂; 0.1 and 1 mM FeCl₃; 10) has generally shown that: (1) the optimum pH is 4.5 for uranium and plutonium, (2) increasing salinity results in slightly lower for uranium and significantly higher chemical recovery plutonium and (3) the presence of Ca(II) cations doesn’t significantly affect the chemical recovery of both radionuclides. Contrary, the presence of Fe(III) cations ([Fe(III)] > 0.1 mM) results in significantly lower chemical recovery for both radionuclides (<50%). The later is attributed to the formation of Fe(III) colloids, which present increased chemical affinity for uranium and plutonium and hence compete with the radionuclide binding by the resin. Nevertheless, the results indicate that the method could be successfully applied to a wide range of natural waters.     

Trimerization of isobutene over cation exchange resins: Effect of physical properties of the resins and reaction conditions

Oligomerization of isobutene has been investigated using several cation exchange resins in order to produce triisobutenes that are useful feedstock for heavy alkylates and neo-acids. Trimers selectivity increases with increasing isobutene conversion. High isobutene conversion is obtained at high temperature and low space velocity by using macroporous cation exchange resins that have high concentration of sulfonic acid groups. Under selected conditions (viz., isobutene WHSV: 10 h⁻¹; temperature: 70 °C; catalyst: Amberlyst-35), the isobutene is quantitatively oligomerized with higher than or equal to 70% selectivity for trimers. The wet resin catalysts containing water or ethanol are very stable for the oligomerization up to about 70 h contrary to the gradual decrease in the conversion with dehydrated catalysts.     

A chelating resin with bis[2-(2-benzothiazolylthioethyl)sulfoxide]: Synthesis, characterization and properties for the removal of trace heavy metal ion in water samples

A new chelating resin containing bis[2-(2-benzothiazolylthioethyl)sulfoxide] was synthesized using chloromethylated polystyrene as material and characterized by elemental analysis and infrared spectra. The adsorption capacities of the newly formed resin for Hg²⁺, Ag⁺, Cu²⁺, Zn²⁺, Pb²⁺, Mn²⁺, Ni²⁺, Cd²⁺ and Fe³⁺ were investigated over the pH range 1.0-6.0. The resin exhibited no affinity for alkali or alkaline earth metal ions. The maximum adsorption capacities of the resin for Hg²⁺, Ag⁺, Cu²⁺, Zn²⁺, Pb²⁺, Mn²⁺, Ni²⁺, Cd²⁺ and Fe³⁺ were 1.49, 0.96, 0.58, 0.11, 0.37, 0, 0.24, 0.36 and 0.25 mmol g⁻¹, respectively. In column operation it had been observed that Hg²⁺ and Ag⁺ in trace quantity could be separated from different binary mixtures and Hg²⁺ could be effectively removed from industrial wastewater and the natural water spiked with Hg²⁺ at usual pH.     

On-line preconcentration using dual mini-columns for the speciation of chromium(III) and chromium(VI) and its application to water samples as studied by inductively coupled plasma-atomic emission spectrometry

On-line preconcentration system for the selective, sensitive and simultaneous determination of chromium species was investigated. Dual mini-columns containing chelating resin were utilized for the speciation and preconcentration of Cr(III) and Cr(VI) in water samples. In this system, Cr(III) was collected on first column packed with iminodiacetate resin. Cr(VI) in the effluent from the first column was reduced to Cr(III), which was collected on the second column packed with iminodiacetate resin. Hydroxyammonium chloride was examined as a potential reducing agent for Cr(VI) to Cr(III).The effects of pH, sample flow rate, column length, and interfering ions on the recoveries of Cr(III) were carefully studied. Five millilitres of a sample solution was introduced into the system. The collected species were then sequentially washed by 1 M ammonium acetate, eluted by 2 M nitric acid and measured by ICP-AES. The detection limit for Cr(III) and Cr(VI) was 0.08 and 0.15 μg l⁻¹, respectively. The total analysis time was about 9.4 min.The developed method was successfully applied to the speciation of chromium in river, tap water and wastewater samples with satisfied results.