Synergic liquid/liquid extraction of lithium and sodium with 4-acyl-5-pyrazolones with bulky substituents and tri-n-octylphosphine oxide

The synergic liquid/liquid extraction of lithium and sodium with 4-acyl-5-pyrazolones having bulky substituents and tri-n-octylphosphine oxide (TOPO) is described. The maximum percentage extraction and the separation of lithium and sodium were improved by introducing bulky substituents. Quantitative extraction (? 99% ) of lithium could be achieved by adduct formation with TOPO, which enhanced the extraction much more than did triphenylphosphine oxide. The extraction decreased in the solvent order cyclohexane ? benzene ? chloroform, which is the general trend in synergic extractions.     

Studies on extraction of copper(II) with 1-phenyl-3-methyl-4-acyl-5-pyrazolone

The extraction of Cu(II) with 1-phenyl-3-methyl-4-acyl-5-pyrazolone (HA), in different organic solvents has been studied. The extraction mechanism of Cu(II) and the composition of the extracted species has been determined. Cu(II) was extracted as CuA₂, or in the presence of TOPO, as CuA₂TOPO. The extraction constants do not change regularly with increasing the length of acyl chain in the 1-phenyl-3-methyl-4-acyl-5-pyrazolone derivatives. The effect of the temperature on the extraction of Cu(II) has also been investigated.     

Solvent extraction of alkaline earth metals,and lithium with 1-phenyl-3-methyl-4-acylpyrazol-5-ones and trioctylphosphine oxide

The synergic extraction of magnesium, calcium, strongium, barium and lithium into cyclohexane or benzene containing 1-phenyl-3-methyl-4-acyl-pyrazol-5-one (HA) and tri-n-octylphosphine oxide (TOPO) was investigated as a function of pH, HA and TOPO concentration. The extracted species when the 4-benzoyl compound was used, were MA₂(TOPO)₂ (M = Mg, Ca, Sr), BaA₂(TOPO)₃ and LiA(TOPO)₂. When the 4-trifluoro-acetyl derivatives was used, the extracted species were the same except for SrA₂(TOPO)₃. Extraction constants for the synergic extractions were calculated.     

Liquid-liquid extraction separation of zinc and cadmium with 1-phenyl-3-methyl-4-acyl-5-pyrazolones and tri-n-octylphosphine oxide

The extraction of zinc and cadmium with a mixture of a 1-phenyl-3-methyl-4-acyl-5-pyrazolone and trioctylphosphine oxide (TOPO) in various solvents is described. The extraction constants for systems based on eight 4-acyl compounds (C₃C₁₈) are reported. The 1-phenyl-3-methyl-4-stearoyl-5-pyrazolone/benzene system is most effective for the mutual separation of zinc and cadmium at pH 4.5; 20 μg of zinc can be separated efficiently from 20 mg of cadmium.     

Steric effect of ortho-substituents of 1-phenyl-3-methyl-4-aroyl-5-pyrazolones on the synergic extraction of lutetium with trioctylphosphine oxide

The substituent effect of ortho-substituted 4-aroyl derivatives of 1-phenyl-3-methyl-5-pyrazolones (HA) on the adduct formation reaction between their lutetium chelates and a neutral ligand, trioctylphosphine oxide (TOPO, L), in benzene was studied using a liquid-liquid extraction system. The lutetium 4-aroyl-5-pyrazolonates react with TOPO to form LuA₃L and LuA₃L₂ types of adducts. An obvious steric hindrance of the terminal group on the adduct formation reaction was observed. Linear relationships between the acid dissociation constant of the ortho-substituted 4-aroyl-5-pyrazolone derivatives and those of the corresponding benzoic acids, between the extraction constants of lutetium and the acid dissociation constants of pyrazolones and between the adduct formation constants of TOPO and the acid dissociation constants of pyrazolones could be obtained.     

Extraction of thorium(IV) by a mixture of 1-phenyl-3-methyl-4-benzoyl-5-pyrazolone and tri-n-octyl phosphine oxide

The extraction behavior of Th(IV) from dilute nitric as well as perchloric acid medium using 1-phenyl-3-methyl-4-benzoyl-5-pyrazolone (PMBP) and its mixture with tri-n-octyl phosphine oxide (TOPO) was investigated. The species of the type Th(X)(PMBP)₃·(HPMBP) and Th(X)(PMBP)₃·(TOPO) were extracted for the binary and ternary extraction systems, respectively, where X=NO₃− or ClO₄−. The presence of 1.25·10⁻⁵M Th carrier in the aqueous phase resulted in the extracted species of the type of Th(PMBP)₄ and Th(PMBP)₄·(TOPO), respectively. The extraction constant (logk _ex ) for the binary species Th(PMBP)₄ was found to be 6.89±0.01 while the overall extraction constant (logK) for the ternary species Th(PMBP)₄·(TOPO) was calculated to be 13.17±0.06.     

PMTFP与中性磷萃取剂对钇(Ⅲ)的协同萃取

本文用萃取法测定了(Ⅰ)Y(Ⅲ)/0.5MNaClO_4/PMTFP—C_6H_6和(Ⅱ)Y(Ⅲ)/0.5MNaClO_4/PMTFP—TBP—C_6H_6及(Ⅲ)Y(Ⅲ)/0.5MNaClO_4/PMTFP—TOPO—C_6H_6体系的萃取平衡常数和协苹平衡常数,结果如下: 体系(Ⅰ)的1gK3_(30)=-3.36;体系(Ⅱ)的1gK_(32)=4.47; 体系(Ⅲ)的1gK_(31)=6.65、1gK_(32)=9.08。     

Mixed ligand chelate extraction of lanthanides with 1-phenyl-3-methyl-4-octanoyl-5-pyrazolone systems

The equilibrium extraction behavior for a series of representative trivalent lanthanide ions, Pr, Eu, and Yb, using chloroform solutions containing 1-phenyl-3-methyl-4-octanoyl-5-pyrazolone (HPMOP), either alone or combined with 1,10-phenanthroline (phen), trioctylphosphine oxide (TOPO) or methyltrioctylaromonium chloride (R₃R'NCl), is studied. The results demonstrate that these lanthanides are extracted as LnP₃, or in the presence of phen or TOPO. as LnP₃ · phen or LnP₃ · TOPO, or in the presence of R₃R'NCl, as R₃R'NLnP₄. The effects of phen, TOPO, and R₃R—NCl on the extraction of lanthanide ions with HPMOP are more pronounced than their effects with 8-quinolinol or 5,7-dibromo-8-quinolinol.     

4,4''''-癸二酰-双-(1-苯基-3-甲基-5-吡唑啉酮)和中性磷萃取剂对铀(Ⅵ)的协同萃取

或许是考虑到溶解度的原因,迄今应用4,4′-癸二酰-双-(1-苯基-3-甲基-5-吡唑啉酮)(简称为DBPMP或H_2A)所进行的萃取研究,都是采用氯仿作为稀释剂。然而,氯仿属于A型受电子溶剂,能和具有给电子原子氧的DBPMP及中性磷萃取剂TBP或TOPO生成分子间氢键而缔合,从而降低萃取的分配比。若改用N型惰性溶剂作为稀     

Solvent Extraction of Alkaline Earths with 1-Phenyl -3-Methyl 4 Stearoylpyrazol - 5 - One and Topo

Abstract

The synergic extraction of Ca, Sr, and Ba ions from aqueous solutions into cyclohexane or benzene containing 1- pheny 1 - 3 - methyl - 4 - stearoylpyrazol - 5 - one (HPMSP) and TOPO has been studied. Quantitative extraction (log D>2) was attained at pH>5.4 for Ca, pH>6.5 for Sr, and pH>7.3 for Ba when cyclohexane containing 0.05 M HPMSP and 0.01 M TOPO was used, and the corresoponding values for benzene were 6.5, 7.8, and 8.4. Extracted species were M(PMSP)₂(TOPO)₃ (M=Ca, Sr, Ba) for cyclohexane and Ca(PMSP)₂(TOPO)₃ and Sr (or Ba) (PMSP)₂(TOPO)₂ for benzene.     

Extraction of ternary complexes of thorium(IV) with 3-phenyl-4-benzoyl-5-isoxazolone and neutral donors from nitric acid medium

The extraction behaviour of thorium(IV) from aqueous nitric acid employing 3-phenyl-4-benzoyl-5-isoxazolone (HPBI) in the presence of tri-n-octyl phosphine oxide (TOPO) as well as tri-n-butyl phosphate (TBP) in xylene medium was investigated. The extraction constant (log k(ex)) for the binary organic phase species Th(PBI)(4) was determined to be 8.26 which is by far the largest amongst the corresponding values known for other beta-diketones. The overall extraction constant (log K) for the ternary species Th(PBI)(4) TBP and Th(PBI)(4).2TOPO were estimated to be 14.96 and 20.96 respectively. An inverse correlation of the adduct formation constant (log K(s)) with the pK(a) of the beta-diketones, 2-thenoyltrifluoroacetone, 1-phenyl-3-methyl-4-benzoyl-5-pyrazolone and HPBI, was observed. The steric as well as the electronic effects of adduct formation have been discussed. Analytical application of HPBI for the separation of (234)Th radiotracer from natural uranium (99.3% (238)U) has been suggested.     

The separation of zinc(II) and cadmium(II) by liquid-liquid extraction

The extraction of Zn(II) and Cd(II) from thiocyanate solutions with bis-2-ethylhexyl sulphoxide (B₂EHSO) in benzene as an extractant has been studied by tracer techniques. For comparison, extraction has also been carried out with tributylphosphate (TBP). The extraction data have been analysed by both graphical and theoretical methods by taking into account complexation of the metal in the aqueous phase by inorganic ligands and plausible complexes extracted into the organic phase. The results demonstrate that Zn(II) is extracted as Zn(SCN)₂·2B2EHSO and Zn(SCN)₂·2TBP. In the case of Cd(II), the extracted species are Cd(SCN)₂·4B2EHSO/4TBP. The synergistic extraction of Zn(II) and Cd(II) with mixtures of 1-phenyl-3-methyl-4-benzoyl-pyrazolone-5 (HPMBP) and B2EHSO or TBP or trioctylphosphine oxide (TOPO) from acetate buffer solutions has also been investigated. Zn(II) is extracted as Zn(PMBP)₂·B2EHSO/TBP/TOPO. On the other hand, Cd(II) is found to be not extracted with these mixed-ligand systems under the experimental conditions. These results also demonstrate the mutual separation of Zn(II) and Cd(II) using the synergistic extraction with HPMBP in the presence of various neutral oxodonors.     

Solvent extraction of lanthanum(III), europium(III) and lutetium(III) with fluorinated 1-phenyl-3-methyl-4-benzoyl-5-pyrazolones into chloroform

A series of chelating reagents, 1-phenyl-3-methyl-4-(2-fluorobenzoyl)-5-pyrazolone, 1-phenyl-3-methyl-4-(3-fluorobenzoyl)-5-pyrazolone and 1-phenyl-3-methyl-4-(4-fluorobenzoyl)-5-pyrazolone, has been synthesized. The extraction of Ln(III), (Ln = La, Eu and Lu) into chloroform with these reagents at 30 +/- 1 degrees has been studied. The composition of the complexes extracted has been determined by the slope method, and the extraction constants K(ex), were measured. The presence of the fluorine atom in the reagents does not make the K(ex), values much different from those obtained with the parent pyrazolone.     

Synthesis and potentiometric selectivity study of new spiro-14-crown-4 derivatives

Abstract

Four new compounds with 14-crown-4 attached to spirocyclopentane or spirocyclohexane were synthesized and tested for potentiometric selectivity for lithium ion in polyvinyl chloride membrane electrodes. Four plasticizers were studied and the addition of tri-octylphosphine oxide (TOPO) was investigated. One ionophore exhibited a sodium/lithium selectivity, K^pot _Li,Na by the matched potential method of 0.0028 in the presence of 1% TOPO, using o-nitro-phenylphenyl ether as plasticizer. Selectivities are reported for sodium, potassium, nickel, cobalt, barium and calcium.     

Synergic solvent extraction studies of gadolinium using a combination of the di(2-ethylhexyl)phosphoric acid and three adductants into kerosine/chloroform

The equilibrium extraction behaviour of Gd(III) using a chloroform/kerosine solution containing di(2-ethylhexyl)phosphoric acid (HDEHP), either alone or combined with one of three adductants, 1,10-phenanthroline monohydrate (phen), alpha,alpha'-dipyridyl(2,2'-bipyridine) (bipy) or trioctylphosphine oxide (TOPO) is described. The enhancement of the extraction by addition of such neutral adductants is explained in terms of adduct formation of the metal chelate in the organic phase. Among the three synergistic mixtures, 1,10-phenanthroline is the most promising for the extraction of the last member of light lanthanoids, gadolinium. Gadolinium ions are found to be extracted in the absence of phen, bipy or TOPO; the species was M(HA(2))(3) but M(HA(2))(3))(phen)(2) was found when phen was added and M(HA(2))(3)(bipy), M(HA(2))(3)(bipy)(2) was found when bipy was added and M(HA(2))(3)(TOPO) was found when TOPO was added. The compositions of the extracted species are obtained from the slope analysis method. pH (1 2 ) values were also obtained. The stoichiometry, extraction constants and stability constants of these systems were determined. Synergistic extraction can be carried out at lower pH.     

A New Extraction System Based on Isopropyl Salicylate and Trioctylphosphine Oxide for Separating Alkali Metals

It was established that isopropyl salicylate can be used similarly to 1,3-diketones as a key component for a new efficient extraction system for selective separation of alkali metal cations. According to DFT modeling of complexes of isopropyl salicylate and 1,3-diketone with alkali metal cations (Li⁺, Na⁺, K⁺), six-membered metallacycles are formed whose stability decreases along the series Li > Na > K, which results in the observed enhanced affinity to lithium. The extraction ability of isopropyl salicylate is manifested in the presence of trioctylphosphine oxide (TOPO). The newly obtained complexes of isopropyl salicylate with alkali metal cations as well as their extracts in a mixture with TOPO are characterized by means of FT-IR, Raman, and NMR spectroscopy. The probable structure of the extracted lithium complex is presumed and the role of TOPO in the extraction process is investigated in detail. Extraction experiments showed extremely high separation coefficients for Li/Na and Li/K pairs in the extraction from a model multi-component solution.     

三辛基氧化膦(TOPO)萃取铟的研究

本文研究了三辛基氧化膦(TOPO)自盐酸溶液中萃取铟的性能,其萃取率是随酸度的增加而增加。与P_(350)和TBP相比较,萃取能力大小顺序为:TOPO>P_(350)>TBP经斜率法和化学分析法研究确定,TOPO白盐酸溶液中萃取铟的反应为:In_((a))~(3+)+H_((a))~++4Cl_((a))~-+2TOPO_((o))F(?)HInCl_4·2TOPO_((o))IR和NMR研究证明:铟是以H[InCl_4]形式被萃入TOPO有机相中的。     

Extraction of mercury(II) from aqueous thiocyanate solutions with 5-(4-pyridyl)nonane in benzene, and its subsequent atomic-absorption spectrometric determination

Tracer ( approximately 10(-8)M) mercury(II) can be quantitatively extracted with 5-(4-pyridyl)nonane in benzene from aqueous thiocyanate solutions that are up to 6M in HCl, 1M in H(2)SO(4) or 0.25M in HNO(3), in a single extraction. Optimal conditions for the extraction are given, based on a critical study of the relevant factors such as the effects of the acids, thiocyanate, salting-out and complexing agents and the reagent concentration. The mechanism underlying these extractions is discussed on the basis of the results obtained from partition and slope-analysis data. The extraction of the metal as Hg(PyN)(2)(SCN)(2) is indicated. The extracted mercury can be stripped from the non-aqueous layer with various aqueous solutions, including nitric acid (2M), sodium citrate ( 1M) and sodium thiosulphate (0.1 M). Common salts do not depress the extraction. Distribution coefficients and separation factors of several elements relative to mercury(II) are reported for media that contain the optimal concentrations of the mineral acids and are in 0.2M in potassium thiocyanate. The data have been applied for the determination of mercury in soil and water samples by atomic-absorption spectrometry.     

Studies on extraction of manganese(II) with 1-phenyl-3-methyl-4-acyl-5-pyrazolone

The extraction of Mn(II) with 1-phenyl-3-methyl-4-acyl-5-pyrazolone (HA) in MIBK has been studied. Mn(II) is extracted as MnA(2). The extraction constant for each 4-acyl compound was calculated. The effect of temperature on the extraction of Mn(II) has also been investigated.     

The solvent extraction of europium and barium with 1-aryl-3-methyl-4-aroyl-5-pyrazolones

Eleven 1-aryl-3-methyl-4-aroyl-5-pyrazolone derivatives were synthesized. Their acid dissociation constants were determined spectrophotometrically; there was a linear relationship between them and Hammett's σ values. Europium and barium ions were readily extracted into benzene and n-octyl alcohol, respectively, at very low pH.