Perfluorocarbon-based liquid-liquid extraction for separation of transition metal ions.

We report a liquid-liquid extraction system based on perfluorocarbon (fluorous-solvent extraction) that allows selective extraction of metal ions from aqueous and organic phases to a perfluorocarbon phase (FC-72) with perfluorinated beta-diketone (1,1,1,5,5,6,6,6-octafluoro-2,4-hexanedione), which can be followed by backward extraction using 1 M nitric acid.     

Selective separation of some ecotoxic transition metal ions from aqueous solutions using immobilized macrocyclic material containing solid phase extraction system

A simple flow-based method was developed for the simultaneous separation of certain transition metal ions (Co, Ni, Cu, Zn, Cd) from aqueous systems, which ions show ecotoxic effects when present at elevated concentrations. A silica-gel-bonded macrocycle system, commonly known as molecular recognition technology (MRT) gel, was used for solid phase extraction (SPE) of the target analytes. The collection behavior of the MRT-SPE system was studied based on pH. Fortified deionized water samples containing 250 μg L⁻¹ of each of the elements were treated at the flow rate of 1 mL min⁻¹. The collected analytes were then eluted by 3 M HNO₃ and analyzed using inductively coupled plasma spectrometry. Detection limits of the proposed technique were in the range of 0.004–0.040 μg L⁻¹ for the studied metal ions. The validity of this separation technique was checked with spiked ‘real’ water samples, which produced satisfactory recoveries of 96–102%. The non-destructive nature and highly selective ion-extraction capability of the SPE material are the most important aspects of the proposed method and they are the main focus of this paper.      

Study on partition equilibria of metal complexes in non-ionic micellar solutions from spectrophotometric data

The complexation equilibria for Zn(II)-8-quinolinol and Zn(II)-5,7-dichloro-2-methyl-8-quinolinol systems were studied spectrophotometrically in aqueous micellar solutions of the non-ionic surfactant Brij-35 in NaCl 0.1 M medium at 25 degrees C. The partition model, in which the different species involved in the equilibria can distribute themselves between aqueous and micellar pseudophases, was applied. Calculations were performed by means of the spdis program, developed specifically to handle multiwavelength spectrophotometric data in micellar systems. A factor analysis was applied to the spectrophotometric data in order to determine the number of species in equilibrium. A quantitative relationship was found between fluorescence intensity and the micellar solubilization of metal chelates.     

Use of portionwise extractant feeding for the extraction of metal ions from aqueous solutions with tributyl phosphate

A procedure involving portionwise extractant feeding was suggested for improving the characteristics of selective extraction of metal ions from aqueous solutions. This procedure enhances the extraction of metal ions into the organic phase, reduces the extractant consumption, and increases the distribution ratio of metals between the organic and aqueous phases and the metal separation factor in extraction.     

Removal of heavy metal ions from aqueous solutions by alkaline-earth metal phosphates

The possibility of utilization of calcium or magnesium phosphates of various composition for heavy and non-ferrous metal extraction from aqueous solutions has been studied. The efficiency of the phosphates in removal of Pb(II), Cr(III) and Fe(III) ions has been shown to decrease in the following sequence: Mg₃(PO₄)₂>MgNH₄PO₄>Ca₃(PO₄)₂>CaHPO₄>Ca₁₀(PO₄)₆(OH)₂ which is inverse to their hydrolytic stability series. It has been established that phosphates of non-apatite structure are capable of binding up to 12 mmol g⁻¹ of the named heavy metals by a chemical interaction. Hydroxyapatite interacts with the polyvalent metal ions via either the above mentioned or ion-exchange mechanism, depending on preparation method used for the apatite and the nature of metal.     

搅拌对三氯乙烯及糠醛水溶液液-液分层的影响

糠醛是用玉米芯、麦杆等农林植物纤维废料生产的重要的有机溶剂和原料。用于生产糠醇,石油化工中润滑油精制及C4、C5馏分的分离纯化。传统的糠醛精致方法是将水解后的糠醛稀溶液多次蒸馏,能耗高,作者采用液-液萃取法分离糠醛,工艺简单,能耗低。本文选择三氯乙烯为萃取剂,考察了萃取分离糠醛水溶液体系的影响因素,为进一步中试及工业放大提供参考。     

Quantitative aspects of the adsorption of metal ions from aqueous solutions to container surfaces

An attempt is made to quantify the influence of wall-adsorption in trace analysis. The retention of the aqueous phase is defined in terms of three dimensionless parameters: surface capacity/total amount in the solution, concentration of adsorbable species/total concentration, ratio of adsorption parameters. Based on the measurement of the adsorption parameters by radiotracer experiments and the initial conditions the final retention may be calculated. Time dependence may be included.     

Ionic equilibria in alkaline aqueous solutions of metal complex salts

A thermodynamic analysis of the formation conditions of metal hydroxides was performed. The areas of stable formation of metal hydroxide precipitates in the coordinates pH-metal concentration, including also solutions containing various kinds of complexing agents, were evaluated. With the precipitation of cadmium hydroxide as example, X-ray phase analysis confirmed the formation of metal hydroxide in the chemical composition areas where its formation is predicted by a thermodynamic analysis.     

Luminescence kinetics and association equilibria of lanthanide ions in aqueous solutions

Luminescence life time measurement can be used under certain conditions to determine the thermodynamic constants of complex formation between the luminescent (central ion) and ligand. The basic equations correlating the life time and the equilibria constants were derived for two cases: the time for establishing the thermodynamic equilibrium is much shorter than the life time of the excited state of the central ion; and the time for establishing the equilibrium and the life time are of the same order of magnitude.     

Organic-solvent-free systems with phase separation as efficient and safe systems for extraction of metal ions

The possibilities of using organic-solvent-free extraction systems with phase separation, based on antipyrine derivatives, are examined. Ionic associates with tin(II) and tin(IV) anionic complexes and mixed chelates of indium with antipyrine and sulfosalicylic acid are extracted into the organic phase. The suggested systems show promise for the recovery and determination of macro- and microamounts of indium, tin(II), and tin(IV) ions.     

Recovery of heavy metal ions from aqueous solutions using modified organosilicas

Sorption of Cu(II), Pb(II), Cd(II), and Zn(II) from aqueous solutions on two-component organosilicas was studied as influenced by sorbent composition, contact time, ratio of solid and liquid phases, solution pH, nature and concentration of heavy metal ions, and content of modifying agent. The degrees of sorption of these metal ions from aqueous solutions using organosilicas modified with aluminum(III) added into the siloxane matrix or with copper(II) grafted to the sorbent surface layer were compared.     

表面活性剂体系萃取分离贵金属离子的研究

研究了在TritonX 100 (NH4)2SO4 络合剂体系中,贵金属离子的萃取分离行为。考察了金属络合物的液 液两相间的分配行为及影响络合物萃取行为的各种因素,优化了萃取分离条件。实验结果表明,在pH7.0～7.5的溶液中,络合剂PAR能与Pd(Ⅱ)形成稳定的络合物,可被定量萃取,实现了Pd(Ⅱ)与Pt(Ⅵ)、Ir(Ⅵ)、Mo(Ⅵ)等混合离子间的定量分离。混合离子分离中,Pd(Ⅱ)的回收率为97.5%～100.8%。     

The liquid-liquid and liquid-solid equilibria in some binary systems containing alkali metal stearates

The characteristics are submitted of the crystallization curves of binary systems composed of sodium or potassium stearate as one component and succinic, glutaric, adipic, pimelic, suberic or azelaic acid as the other.We are grateful to the CNR (Rome) for financial aid (CT-74-00676-03).     

Correlation of liquid-liquid equilibria in aqueous and organic systems using a modified Wilson model

A modified Wilson model is extended to involve three ternary parameters per ternary to allow the model to represent ternary liquid-liquid equilibria accurately. The calculated results for 19 ternary systems obtained from the present modification are compared with the previous results obtained from other modified Wilson models. The model is further extended to treat quaternary liquid-liquid equilibria for six aqueous systems and one nonaqueous system using binary, ternary, and quaternary parameters. Mutual solubilities for 19 systems over a wide temperature range are represented with the model having temperature-dependent energy parameters.     

Synthesis of chromogenic crown ethers and liquid-liquid extraction of alkali metal ions

New crown ethers carrying a pendent phenolic chromophore were synthesized. These crown ethers, on dissociation of the phenolic proton, provide lipophilic anions which can extract alkali metal cations into 1,2-dichloroethane by forming highly-colored uncharged metal complexes. Structural effects on the extraction were studied for possible use of these crown ethers as extraction—spectrophotometric reagents selective for alkali metals. The following factors are discussed in detail: (i) nature of the crown ether ring (ring size. aza-crown or standard crown ether), (ii) nature of the pendent phenolic group, and (iii) geometry between the crown ether center and pendent phenolic group. 15-Crown-5 or smaller ring-sized reagents favored the extraction of lithium ion when the basicity of the pendent phenolate was relatively high and a six-membered “chelate” ring was possible for the phenolate and the crown ether-bound metal. 15-Crown-5 type reagents were sodium-selective when an eight-membered “chelate” ring was possible between the phenolate and the crown ether-bound metal. 18-Crown-6 type reagents were generally potassium-selective. However, these selectivities were not absolute, and other structural parameters, steric and conformational, must be considered to explain in detail the selectivities of the individual reagents.     

Granulated sulfur-containing sorbents for recovery of heavy metal ions from aqueous solutions

Granulated sorbents that can recover zinc salts from aqueous solutions were produced by poly-condensation of organochlorine wastes from manufacture of epichlorohydrin with sodium polysulfide on the surface of ash-and-slag particles formed at thermal power plants in the system constituted by aqueous hydrazine and an alkali.     

Sorption investigation on the removal of metal ions from aqueous solutions using chelating terpolymer resin

A novel chelating terpolymer resin has been synthesized from anthranilic acid, phenylhydrazine, and formaldehyde by condensation in glacial acetic acid. The structure of the chelating resin was clearly elucidated by use of a variety of spectral techniques, for example FTIR, and ¹H and ¹³C NMR spectroscopy. The average molecular weight of the terpolymer resin was determined by gel-permeation chromatography. The empirical formula and empirical weight of the resin were determined by elemental analysis. The physicochemical properties of the terpolymer resin were determined. Scanning electron microscopy was used to establish the surface features of the chelating resin. The ion-exchange behaviour of the resin for specific metal ions, viz. Fe³⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺, and Pb²⁺, was evaluated by a batch equilibrium method. The study was extended to three variations: evaluation of metal ion uptake in the presence of different electrolytes at different concentrations; evaluation of metal ion uptake at different pH; and evaluation of metal ion uptake at different times. Further, the reusability of the resin was also determined to assess the efficiency of the resin after a few cycles of sorption. From the results it was observed that the resin acts as an effective chelating ion-exchanger.     

Sorption characteristics and separation of tellurium ions from aqueous solutions using nano-TiO2

Titanium dioxide nanoparticles (nano-TiO₂) were employed for the sorption of Te(IV) ions from aqueous solution. A detailed study of the process was performed by varying the sorption time, pH, and temperature. The sorption was found to be fast, equilibrium was reached within 8 min. When the concentration of Te(IV) was below 40 mg L⁻¹, at least 97% of tellurium was adsorbed by nano-TiO₂ in the pH range of 1-2 and 8-9. The sorbed Te(IV) ions were desorbed with 2.0 mL of 0.5 mol L⁻¹ NaOH. The sorption data could be well interpreted by the Langmuir model with the maximum adsorption capacity of 32.75 mg g⁻¹ (20 ± 0.1 °C) of Te(IV) on nano-TiO₂. The kinetics and thermodynamics of the sorption of Te(IV) onto nano-TiO₂ were also studied. The kinetic experimental data properly correlated with the second-order kinetic model (k₂ = 0.0368 g mg⁻¹ min⁻¹, 293 K). The overall rate process appeared to be influenced by both boundary layer diffusion and intra-particle diffusion. The mean energy of adsorption was calculated to be 17.41 kJ mol⁻¹ from the Dubinin-Radushkevich (D-R) adsorption isotherm at room temperature. Moreover, the thermodynamic parameters for the sorption were estimated, and the ΔH⁰ and ΔG⁰ values indicated the exothermic and spontaneous nature of the sorption process, respectively. Finally, Nano-TiO₂ as sorbent was successfully applied to the separation of Te(IV) from the environmental samples with satisfactory results (recoveries >95%, relative standard deviations was 2.0%).     

Sorption of metal ions from multicomponent aqueous solutions by activated carbons produced from waste

Activated carbons produced by thermal treatment of a mixture of sunflower husks, low-grade coal, and refinery waste were studied as adsorbents of transition ion metals from aqueous solutions of various compositions. The optimal conditions and the mechanism of sorption, as well as the structure of the sorbents, were studied.