Solid‐Liquid Extraction of Lanthanum(III), Europium(III), and Lutetium(III) by Acyl‐Hydroxypyrazoles Entrapped in Mesostructured Silica

Abstract

The solid‐liquid extraction of lanthanum(III), europium(III), and lutetium(III) by mesostructured silicas doped with 1‐phenyl‐3‐methyl‐4‐stearoyl‐5‐pyrazolone (HPMSP, bearing one chelating site) or with 1,12‐bis(1′‐phenyl‐3′‐methyl‐5′‐hydroxy‐4′‐pyrazolyl)‐dodecane‐1,12‐dione (HL‐10‐LH, bearing two chelating sites) has been studied and compared to the analogous solvent and micellar extractions in terms of the stoichiometry of the extracted complex and of the extraction efficiency. The solid‐liquid extraction order in the lanthanoid series is La<Eu<Lu; it is the usual liquid‐liquid extraction order obtained with acidic extractants. A theoretical model is used to determine the stoichiometries of the extracted complexes and the extraction yield is measured as a function of the pH, of the extractant/metal ratio (S/M) and of the volume ratio of the two phases (φ). For HPMSP, the extracted complexes involve three ligand molecules for one metal. For HL‐10‐LH, the complex stoichiometries are found to be either Ln(L‐10‐L)(L‐10‐LH) (Ln=La, Eu) or Lu₂(L‐10‐L)₃ for S/M=25, or Eu₂(L‐10‐L)₃ for S/M=5. For the first time, the synergistic solid‐liquid extraction is studied after a successful attempt at simultaneously immobilizing both extractants HL‐10‐LH and 2,4,6‐tri(2‐pyridyl)‐1,3,5‐triazine, “TPTZ”, into silica; the complex extracted in this case differs from the one obtained in solvent extraction.     

Study of the Sorption and Separation Abilities of Commercial Solid‐Phase Extraction (SPE) Cartridge Oasis MAX Towards Au(III), Pd(II), Pt(IV), and Rh(III)

Abstract

This paper presents a new, simple, and rapid procedure for the separation and preconcentration of Au, Pt, Pd, and Rh based on the adsorption of the metals on a commercial solid‐phase extraction (SPE) cartridge, Oasis MAX, which contains a polymeric resin with quaternary ammonium substituents. Adsorption studies revealed that the metal affinity towards the adsorbent ranked according to Au?Pd>Pt whereas Rh was not retained. The elution of the metals was accomplished by using 0.5 M thiourea in 1 M HCl solution. This sorbent effectively recovered Pd and Pt from a spent car catalyst sample containing large amounts of metals such as Al, Fe, and Ce.     

Coordination of cobalt(III), nickel(II), copper(II), palladium(II) and platinum(II) with N-ethyl-N′-(4′-methylthiazol-2′-yl)thiourea (HL)

Coordination complexes of formula [ML₂], [CoL₃], [Pd(HL)Cl₂], [CuLCl(H₂O)] and [CuL₂(H₂O)₂] {L=anion of N-ethyl-N^′-(4^′-methylthiazol-2′-yl)thiourea; M=Pt^II, Pd^II or Ni^II} were prepared and characterized by elemental analyses, magnetic susceptibilities, and by IR, NMR, electronic and mass spectral measurements.     

SOLVENT EXTRACTION OF ANTIMONY (III), BISMUTH (HI), LEAD (II) AND TIN (IV) WITH BIS(2,4,4-TRIMETHYLPENTYL)PHOSPHINODITHIOIC ACID (CYANEX 301®)

The solvent extraction of antimony (in), bismuth (111), lead (II) and tin (IV) from aqueous hydrochloric acid solutions by bis(2,4,4-trimethylpentyl) phosphinodithioic acid (Cyanex 301® denoted HL) in kerosene + 10 % v/v n-decanol was investigated. Lead (II), tin (IV), bismuth (III) and antimony (III) are efficiently extracted by Cyanex 301® up to about 5, 6, 9 and 11 mol.L^1? HCl, respectively. The corresponding extracted species were identified as PbL₂, SnCl₂L₂, BiL₃ and SMvj. However, it was observed that Sn (IV) can be moderately extracted from the aqueous phase by the mere mixture of kerosene and n-decanol above 9 mol.L^1?HCl. In all cases, extraction equilibrium was reached within a few minutes. Finally, a thermodynamic modelling of the extraction system was developed in the particular case of lead (II).     

Zr(IV)?Fe(III), ?Ga(III), and ?Sn(IV) Binary Metal Complexes as Synergistic and Reusable Esterification Catalysts

Synergism in catalytic activity with the combined use of Hf(O‐i‐Pr)₄ or Zr(O‐i‐Pr)₄ and Fe(O‐i‐Pr)₃ for direct esterification and a very simple method for their extraction with ionic liquids for their recovery and reuse are described. This Zr(IV) Fe(III) complex is an environmentally benign catalyst due to its high turnover number, extremely mild Lewis acidity, low toxicity, reusability, and commercial availability at low cost.     

SOLVENT EXTRACTION OF Au(III), Pd(II) AND Pt(lV) WITH SULFUR-CONTAINING METHYLPHOSPHONATES AND β-KETOPHOSPHONATE

Three sulfur-containing methylphosphonates, dibutyl propylthiomethylphosphonate, (C₄H₈O)₂P(0)CH₂SC₃H₇,(DBPTMP),dibutyl propylsulfinylmethylphosphonate, (C₄H₉0)₂P(0)CH₂S(0)C₃H₇, (DBPSiMP) and dibutyl propylsulf onylmethylphosphonate, (C₄H₈O)₂P(0)CH₂S(0) C₃H₇ (DBPSiMP) were synthesized. The extraction of gold(III), palladium(II) and platinum(IV) from HCl media with the synthesized compounds and dibutyl 2-keto-3-methylbutyl-phosphonate, (C₄H₈O)₂P(0)CH₂C (0) CH(CH₃) CH₃, (DBKPP) was investigated at various mixing times and acidities. DBPTMP and DBPSiMP were found to provide nearly quantitative extraction of Au(III) and Pd(II) with short equilibration times for Pd(II) extraction. DBKPP was selective for Au(TII) over Pt(IV) and Pd(II) at high acidity. The behavior of these extractants was also examined in comparison with the corresponding monofunctional extractants, dibutyl butylphosphonate(DB‘BP’), tributyl-phosphate(TBP), dioctylsulphide(DOS) and dioctyl-sulphoxide(DOSO).     

Synthesis,characterization, thermal constant and relaxation of gadolinium(III), iron(III) and manganese(II) chelates of diethylenetriamine-bis-inositol-N,N′,N″-triacetic acid

The reaction of the bicyclic anhydride of diethylenetraiamine-pentaacetic acid (DTPAA) with inositol gave diethylenetriamine-inositol-biester-N,N^′,N″-triacetic acid (DTPA-BI) (1). (1) was characterized by FAB-MS, ¹HNMR, IR and elemental analysis. Its chelates of Gd(III), Fe(III) and Mn(II) holding promise of magnetic resonance imaging (MRI) were synthesized. Gd(III) complex was obtained from Gd₂O₃ and the acid form of (1). Thermodynamic stability constant and relaxation of Gd(III) complex with DTPA-BI were determined. The spin–lattice relaxivity (R₁=5.6 l mmol⁻¹ s⁻¹) of chelate was slightly larger than that of [GdDTPA]²⁻. The results showed that the complex is a prospective MRI agent, although thermodynamic stability constant of DTPA-BI K_[GdDTPA-BI]⁻=10^18.2 was a little less than that of [GdDTPA]²⁻ (K_[GdDTPA]²⁻=10^20.73).     

2,2′‐(Methylimino)bis(N,N‐dioctylacetamide) (MIDOA), A New Tridentate Extractant for Technetium(VII), Rhenium(VII), Palladium(II), and Plutonium(IV)

2,2′‐(Methylimino)bis(N,N‐dioctylacetamide) (MIDOA) was developed as a new extractant for technetium. MIDOA has a similar backbone to TODGA, N,N,N′,N′‐tetraoctyldiglycolamide, where the nitrogen atom bearing a methyl group replaces the ether oxygen in TODGA. MIDOA is highly lipophilic and ready to use in the HNO₃–n‐dodecane extraction system. The distribution ratio (D) for Tc(VII) is extremely high. In addition, Cr(VI), Re(VII), Mo(VI), W(VI), Pd(II), and Pu(IV) are well extracted by MIDOA. MIDOA has high selectivity toward certain oxometallates. The D(Tc) values decrease gradually with HNO₃, H⁺, and NO₃ ^? concentrations, and the log D vs log [MIDOA] dependence indicates the species extracted to be the 1:1 metal‐ligand complex. It is clear that MIDDA [2,2′‐(methylimino)bis(N,N‐didodecylacetamide)] and IDDA [2,2′‐(imino)bis(N,N‐didodecylacetamide)], which have structures analogous to MIDOA, have similar extraction behavior to that of MIDOA.     

Modeling of facilitated transport of Cr(III) using (RNH3+HSO4−) ionic liquid and pseudo-emulsion hollow fiber strip dispersion (PEHFSD) technology

The permeation of chromium (III) using PEHFSD technology and the ionic liquid (RNH₃⁺HSO₄^?), formed by reaction of the primary amine PRIMENE JMT and sulphuric acid, dissolved in n-decane as mobile carrier has been investigated. The alkaline feed solution containing Cr(III) was passed through the tube side, and pseudo-emulsions of the ionic liquid + n-decane + n-decanol and sulphuric acid were passed through the shell side in counter-current mode and using a single hollow fiber module for extraction and stripping. In this advanced membrane technology, the aqueous acidic strip solution is dispersed in the organic membrane solution in a tank with an impeller stirrer to form a strip dispersion. The pseudo-emulsion phase is circulated from the tank to the membrane module to provide a constant supply of the organic solution to the membrane micropores. Factors affecting chromium permeability, such as hydrodynamic conditions, carrier concentration in the organic phase, metal and NaOH concentrations in the feed phase, have been analyzed. A model is reported describing the transport mechanism, whereas the experimental data are quantitatively explained by mathematical equations describing the rate of transport. Different rate-controlling processes take place as long as the metal transport occurs.     

Electrospray Ionization Mass Spectrometry Investigation of BTBP – Lanthanide(III) and Actinide(III) Complexes

In the framework of nuclear waste reprocessing, the separation processes of minor actinides from fission products are developed using liquid‐liquid extraction. To gain an understanding of the mechanism involved in the extraction process, a complex formation of actinides and lanthanides with BTBPs (6,6′‐bis(5,6‐dialkyl‐1,2,4‐triazin‐3‐yl)‐2,2′‐bipyridines) was characterized using the Electrospray Ionization Mass Spectrometry (ESI‐MS) technique. This study was carried out to compare the influence of diluents and side groups of the extractants on complex formation. Three different diluents, nitrobenzene, octanol and cyclohexanone, and two extractants, C5‐BTBP and CyMe₄‐BTBP, were selected for this experiment. It was found that the change of the diluent and of the substituent on the BTBP moiety does not modify the stoichiometry of the complexes which is L₂M(NO₃)₃. It is proposed that one nitrate is directly coordinated to the metal ion, the two other anions probably remaining in the outer coordination sphere. The difference observed in extracting properties is probably due to the solvation of the complexes by the diluent. The noncovalent force that holds complexes together are likely to be largely governed by electrostatic interactions even if the hydrophobic exterior of the complexes plays an important role in the complexation/extraction mechanism. The study of the stability of the ions in the gas phase shows that the C5‐BTBP ligand has a labile hydrogen atom, which is a fragility point of C5‐BTBP.     

The separation and recovery of copper(Ⅱ), nickel(Ⅱ), cobalt(Ⅱ), zinc(Ⅱ),and cadmium(Ⅱ) in a sulfate-based solution using a mixture of Versatic 10 acid and Mextral 984H

We studied the separation and recovery of copper(Ⅱ), nickel(Ⅱ), cobalt(Ⅱ), zinc(Ⅱ), and cadmium(Ⅱ) from magnesium and calcium, using synergistic solvent extraction(SSX) in a typical hydrometallurgical waste solution. A mixture of Versatic 10 acid and Mextral 984 H, diluted with Mextral DT100, was used to obtain fundamental data on p H and distribution isotherms, as well as the kinetics of extraction and stripping. We also investigated the main effects and interactions of common solvent extraction factors: the extraction p H at equilibrium, the temperature, and the extractant concentration. The synergistic effect for extracting metals was confirmed. The results showed that the addition of Mextral 984 H enhanced the separation factors of copper, nickel, cobalt,zinc, and cadmium over magnesium and calcium. Compared with Versatic 10 acid alone, for a mixture of0.5 mol·L~(-1) Versatic 10 acid/0.5 mol·L~(-1)Mextral 984 H, Δp H50 values of copper, nickel, cobalt, zinc, and cadmium were found to be N 2.0, 3.30, 2.85, 0.95, and 1.32 p H units, respectively. The Δp H_(50)(Zn–Mg)and Δp H_(50)(Zn–Ca)values were 3.27 and 2.25, respectively, indicating easy separation and recovery of copper, nickel, zinc, cobalt,and cadmium. The extraction and stripping of copper, cobalt, zinc, and cadmium were fast, with 90% of the metal transferred in 2 min. We next studied whether the metals could be stripped from the extracted liquid selectively in sequence, by using sulfuric acid at different concentrations. The influence of the molecular structure of the oxime and carboxylic acid components upon the synergistic effects was identified by numerical analysis.Excellent separation of copper, nickel, cobalt, and zinc over magnesium and calcium was achieved with this synergistic solvent extraction system.     

Mössbauer Spectroscopy Study of Macromolecular Complexes of Polycarbosilazane Coordinated with Fe(II), Fe(III) and Mixed Valence Fe(II-III) Chlorides

A series of iron-polyethylenediaminecarbosilazane (PEDCSZ-Fe) macromolecular chloride macromolecular complexes were prepared by the reaction of Fe(II), Fe(III), and mixed valence Fe(II-III) chlorides with polyethylenediaminecarbosilazane matrix in toluene under inert atmosphere. The mixed valence macromolecular complexes composed of three different ratios of Fe(II)/Fe(III) (1:2, 1:1, and 2:1). Mössbauer spectra were recorded for the samples at room temperature. The spectra of the PEDCSZ-Fe(II) and PEDCSZ-Fe(III) macromolecular complexes showed pure paramagnetic phase, whereas, the spectra for the mixed valence PEDCSZ-Fe(II-III) showed both magnetic and paramagnetic splitting. The magnetic splitting is so broad such that it was fitted with three magnetic sextets and one quadrupole doublet. The relative intensity of the magnetic phase was the highest for the PEDCSZ-Fe(II-III) with 1:1 ratio. The magnetic phase could be attributed to an iron oxide phase (Fe₃O₄ or FeOOH phase) in a fine powder form as it is clear from the Mössbauer parameters. The XRD patterns of the PEDCSZ-Fe(II-III) with 1:1 ratio contained additional diffraction peaks similar to those observed for Fe₃O₄ in a fine particle form.     

新元素钔(Mendelevium),原子序数101

A.乔尔索(A.Ghiorso)等在今年四月宣布他们首先完成了原子序数101的元素的合成及其化学鉴定。用非常强而密的氦离子(即α质点)轰击一个很小的99~(253)靶,因而产生少数能自动分裂的原子,这些原子在阳离子交换树脂柱冲到准铥(Eka-Tu)的位置。进行实验时曾用了特殊的技巧。在克罗宽(Crocker)实验室60吋电子旋迴加速器的一个特殊位置上,使非常集中而又平行的48百万电子伏特(Mev)的氦离子流(在1/32×1/4吋的面积上是10微安培)通过递降吸收器,再通过千分之二吋厚     

Is the Coagulation-Filtration Process with Fe(III) Efficient for As(III) Removal from Groundwaters?

The coagulation–filtration process using Fe(III) salts is the most frequently practiced technology for As(V) removal in full scale water treatment plants. The co-existing As(III) is usually oxidized to As(V) prior to removal. Nonetheless, research studies applying high As(III) initial concentrations showed significant As(III) removal capacities, however, the efficiency of the process for initial As(III) concentrations commonly encountered in drinking water, i.e., 10-100 μg/L is not sufficiently investigated. The experimental results of this study indicated that the coagulation–filtration process using Fe(III) can safely meet the drinking water regulation limit of 10 μg/L, only when the initial As(III) concentration is < 25 μg/L and the Fe(III) dose ≥ 5 mg/L, for experiments performed with NSF challenge water. The limitations for efficient As(III) removal are attributed to the fact that As(III), under circumneutral pH values is mostly present with the uncharged H₃AsO₃ form, which is not efficiently adsorbed onto iron oxy hydroxides (FeOOH), the product of Fe(III) hydrolysis. Adsorption isotherms data were best fitted to BET model, indicating multi-layer adsorption and low affinity of As(III) for Fe(III) hydroxides.     

Determination of Cd(II), Co(II), Cu(II), Ni(II), and Pb(II) Ions by FAAS after Separation/Preconcentration using Amberlite XAD‐1180 Chelating Resin Chemically Modified with o‐Aminophenol

Abstract

The use of a newly synthesized chelating resin with an o‐aminophenol–type functional groups and Amberlite XAD‐1180–type supporting material for separation/preconcentration of trace metal ions from various water samples was described. Amberlite XAD‐1180‐o‐aminophenol chelating resin (XAD‐o‐AP) was synthesized using Amberlite XAD‐1180 resin as solid support and o‐aminophenol as the chelating ligand. The determination of Cd(II), Co(II), Cu(II), Ni(II), and Pb(II) ions was made by flame atomic absorption spectrometry (FAAS). Studying with model solutions for the optimization of the method was based on the measurement of recovery values (between 92–106%) of the analyte elements. Some analytical parameters such as pH (6.0), volume of the sample (～250 mL), effect of matrix ions, flow rates of the sample (2.5 mL min^?1) and elution solutions (2.5 mL min^?1), concentration, type and volume of the eluent (4 mol L^?1 HNO₃, 20 mL) were investigated. The detection limit (3s/b, n=20) and the relative standard deviation (n=7) of the method were found to be in the range 0.9–4.3 µg L^?1 and 4.4–5.5%, respectively. The proposed method was successfully applied to the real samples such as wastewater, boiler feeding water and a certified reference material (Estuarine water, LGC 6016).     

Di-μ-hydroxy macrocyclic ytterbium(III) complex

The mononuclear [YbracL]Cl₃·2H₂O and dinuclear [Yb₂(OH)₂Cl₂(racL)₂]Cl₂·4CH₃OH·2H₂O complexes of the macrocyclic ligand L derived from trans-1,2-diaminocyclohexane and 2,6-diformylpyridine have been obtained. The formation of the dinuclear species upon addition of hydroxide to the [YbracL]Cl₃·2H₂O or the enantiopure [YbrrrrL(NO₃)₂](NO₃) has been followed using ¹H NMR spectroscopy. The X-ray crystal structure of [Yb₂(OH)₂Cl₂(racL)₂]Cl₂·4CH₃OH·2H₂O complex has been determined. The complex is a dimer consisting of two macrocyclic units. The Yb(III) ion is coordinated by six nitrogen atoms of the macrocyclic ligand, two bridging OH groups and chloride anions. The chiral macrocycle L in this complex exhibits twist-bent conformation of approximate C₂ symmetry.     

Dispersion of liquid–liquid phase by a jet-induced gas–liquid–liquid mixing column developed for separation of organic pollutants

This article presents the gas and liquid entrainment and its dispersion in a gas–liquid–liquid mixing column. The variations in phase entrainment is observed with the change in the paraffin liquid and kerosene volume fraction from 5% to 35% due to the increase in the flow resistance with increase in the effective viscosity of the liquid–liquid mixture. The degree of dispersion is enunciated based on the axial dispersion model and the flow resistance of the phases in the column. A correlation is proposed to interpret the entrainment of phase as a function of operating variables within the range of experimental conditions.     

Pastille摇椅(1967年)Pastille(Gyro),1967

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Chelation behavior of N′-(4-(dimethylamino)benzylidene)-2-oxo-2H-chromene-3-carbohydrazide towards Cd(П), Zn(П), Ni(П), Hg(П), Cu(П) and Co(П) metal ions in presence of SiO2

Silicon - A series of Cd(П), Zn(П), Ni(П), Hg(П), Cu(П) and Co(П) complexes with N′-(4-(dimethylamino)benzylidene)-2-oxo-2H-chromene-3-carbohydrazide (HAL)...