The chromatographic properties of transition metal complexes of pyridine-2-aldehyde-2-quinolylhydrazone

A scheme has been devised whereby PAQH complexes of iron, nickel, copper and cobalt can be separated chromatographically and determined semiquantitatively in presence of up to tenfold excesses of interfering metal ions. The visual detection limits for iron, nickel and copper were found to be 0.01 μg and for cobalt 0.007 μg per spot. Interesting relationships were observed between R_F values, decomposition temperatures and position of the absorption maxima of the adsorbed complexes.     

Room temperature ionic liquid as a novel medium for liquid/liquid extraction of metal ions

Room temperature ionic liquids (RTILs) have been used as novel solvents to replace traditional volatile organic solvents in organic synthesis, solvent extraction, and electrochemistry. The hydrophobic character and water immiscibility of certain ionic liquids allow their use in solvent extraction of hydrophobic compounds. In this work, a typical room temperature ionic liquid, 1-butyl-3-methylimidazolium hexafluorophosphate [C₄mim][PF₆], was used as an alternative solvent to study liquid/liquid extraction of heavy metal ions. Dithizone was employed as a metal chelator to form neutral metal-dithizone complexes with heavy metal ions to extract metal ions from aqueous solution into [C₄mim][PF₆]. This extraction is possible due to the high distribution ratios of the metal complexes between [C₄mim][PF₆] and aqueous phase. Since the distribution ratios of metal dithiozonates between [C₄mim][PF₆] and aqueous phase are strongly pH dependent, the extraction efficiencies of metal complexes can be manipulated by tailoring the pH value of the extraction system. Hence, the extraction, separation, and preconcentraction of heavy metal ions with the biphasic system of [C₄mim][PF₆] and aqueous phase can be achieved by controlling the pH value of the extraction system. Preliminary results indicate that the use of [C₄mim][PF₆] as an alternate solvent to replace traditional organic solvents in liquid/liquid extraction of heavy metal ions is very promising.     

Extraction behavior of trivalent lanthanoids and yttrium with bis (2,4,4-trimethylpentyl)octylphosphine oxide

The extraction behavior of yttrium and trivalent lanthanoids has been investigated from thiocyanate solutions using bis(2,4,4-trimethylpentyl)octylphosphine oxide (CYANEX 925) in xylene as an extractant by tracer techniques. The results demonstrate that these trivalent metal ions are extracted as M(SCN)₃•3CYANEX 925. The equalibrium constants of the extracted complexes have been deduced by non-linear regression analysis. The extraction behavior of trivalent lanthanoids and yttrium was found to be ambiguous since the distribution ratios of these metal ions are nonmonotinic function of atomic number (La<Y<Pm<Tm<Ho<Eu<Yb<Lu). The separation factors between these trivalent metal ions have been calculated and compared with commercially important extraction systems like tributylphosphate (TBP), trioctylphosphine oxide (TOPO), octy(phenyl)-N,N-diisobutylcarbamoylmethylphosphine oxide (CMPO) and di-2-ethylhexyl phosphoric acid (DEHPA). The possibilities for separating yttrium from trivalent lanthanoids has also been discussed.     

Adsorption behaviors of high-valence metal ions on desferrioxamine B immobilization nylon 6,6 chelate fiber under highly acidic conditions

Adsorption behaviors of the high-valence metal ions Zr(IV), Hf(IV), Ti(IV), V(V), Nb(V), Ta(V), and Mo(IV) on desferrioxamine B (DFB) immobilization nylon 6,6 chelate fiber was investigated under highly acidic conditions. Though the complexes of DFB and the high-valence metal ions were extracted without selectivity by solvent extraction, the only zirconium ions showed higher adsorption percentages than that of other high-valence metal ions on the DFB immobilization nylon 6,6 chelate fiber. Adsorption properties were caused that limited the freedom of DFB by chemical immobilization. Especially, hafnium ions and zirconium ions, which have similar chemical properties, showed different adsorption behavior in highly acidic aqueous solutions. Zirconium ions were quantitatively adsorbed up to 13.5 micromol/g.     

Radiochemical extraction of mercury(II) from acidic chloride solutions using dialkylsulphides

The liquid-liquid extraction behavior of Hg(II) from aqueous acidic chloride solutions has been investigated by tracer techniques using dialkylsulphides (R₂S) namely, dibutylsulphide (DBS) and dioctylsulphide (DOS) as extractants. These extraction data have been analyzed by both graphical and theoretical methods by taking into account complexation of the metal ion in the aqueous phase with inorganic ligands and all plausible complexes extracted into the organic phase. The results clearly indicate that Hg(II) is extracted into xylene as HgCl₂ ^. nDBS/nDOS (where n = 2 and 3). The equilibrium constants of the extracted complexes have been deduced by non-linear regression analysis. The separation possibilities of Hg(II) from other metal ions viz. Ca(II), Mg(II), Ba(II) and Fe((III), which are present in the industrial wastes of the chlor-alkali industry has also been discussed.     

Effect of alkali ions (Na+, K+) on the solvent extraction of uranium(VI) with a di-carboxylated calix[4] arene

The solvent extraction of uranium(VI) with a di-carboxylated calix[4]arne (LH₂) in chloroform and 1,2-dichloroethane has been studied in the presence or absence of alkali ions (M=Na⁺,K⁺). For UO ₂ ²⁺ when studied alone, a 12 (metal: ligand) extracted species is evidenced, with a rather low associated extraction equilibrium constant. The efficiency of extraction increases drastically in the presence of alkali ions, due to the formation of heteronuclear complexes. In all cases, the extracted species are found to be both 122 and 112 (UO ₂ ²⁺ MLH₂) mixed complexes, except in chloroform with K⁺, where only the latter is formed. In the case of Na⁺, mass spectrometry spectra confirm the existence of both homo and heteronuclear complexes as determined in the extraction studies.     

Liquid-liquid partition of cobalt between trilaurylamine N-oxide and aqueous thiocyanate solutions

In an attempt to gain an understanding of factors affecting the extraction of cobalt by trilaurylamine oxide, the equilibria between HX+SCN^– (where X=NO ₃ ^– , Cl^–, SO ₄ ^2– ) and benzene solutions of trilaurylamine oxide have been studied. Cobalt is quantitatively extracted by the oxide from aqueous 0.01–1M KSCN in 0.01M concentration of the acids. The extraction mechanism and the possible compositions of the extracted species are discussed. The effect of several anions on the extraction of the element from optimal aqueous solutions are reported and separation factors for a number of metal ions are given. The solvent has a potential for the group preconcentration of toxic metal ions from dilute aqueous solutions.     

Liquid-liquid extraction of some lanthanide metal ions by polyoxyalkylene systems

Polyoxyalkylene systems, namely, polypropylene glycol (PPG-1025), polyethylene glycol (PEG-600) and polybutadieneoxide (PBDO-700) dissolved in either nitrobenzene or 1,2-dichloroethane have been tested as prospective extractants for some lanthanide metal ions (Eu(3+), Pr(3+) and Er(3+)) from their aqueous solutions in the presence of picrate anions. The metal ions were quantified before and after extraction using the inductively coupled plasma emission spectrophotometry technique. The percent extraction and the distribution coefficients have indicated that pH of the aqueous phase, picrate concentration and the organic solvent are the major parameters that affect the extraction efficiency of the metal ions. The optimum pH range was found to be 3.5-5.5 and the picrate concentration should be as high as possible; however, a picrate concentration of about 0.05 M proved to be adequate for a near quantitative extraction. In all cases, nitrobenzene enhanced a higher percent extraction compared to 1,2-dichloroethane. The efficiency of the polyoxyalkylene systems to extract certain lanthanide metal ions was in the order PBDO-700>PPG-1025>PEG-600 when nitrobenzene was the organic solvent and in the order PPG-1025>PBDO-700 approximately PEG-600 when 1,2-dichloroethane used as the solvent in the organic phase. The extractability of PPG-1025 towards the lanthanide metal ions was in the order Pr(3+)>Eu(3+)>Er(3+) irrespective of the organic solvent used. The stoichiometry of the extracted polyoxyalkylene ion-pairs with the lanthanide metal ions has been estimated. Each mole of metal ions is associated with three moles of picrate anions and 13 to 14 moles of propyleneoxide units in the case of PPG-1025, and about 9 to 10 moles of ethyleneoxide units in the case of PEG-600 and 10 moles of butadieneoxide units in the case of PBDO-700.     

Studies on Liquid/liquid Extraction of Copper Ion with Room Temperature Ionic Liquid

Room temperature ionic liquids are regarded as “Green solvents” for their nonvolatile and thermally stable properties. They are employed to replace traditional volatile organic solvents in organic synthesis, solvent extraction, and electrochemistry. In this work, a water immiscible room temperature ionic liquid, 1‐butyl‐3‐methylimidazolium hexafluorophosphate [C₄mim][PF₆], was used as an alternative solvent for liquid/liquid extraction of copper ions. Metal chelators, including dithizone, 8‐hydroxyquinoline, and 1‐(2‐pyridylazo)‐2‐naphthol, were employed to form neutral metal‐chelate complexes with copper ions so that copper ions were extracted from aqueous solution into [C₄mim][PF₆]. The parameters that affect the extraction of copper ions with this biphasic system were investigated. The extraction behavior in this novel biphasic system is shown to be consistent with that of traditional solvents. For example, the extraction with this biphasic system is strongly pH dependent. So, the extraction efficiency of coppers ion from an aqueous phase can be manipulated by tailoring the pH value of the extraction system. Hence, the extraction, separation and preconcentraction of copper ions can be accomplished by controlling the pH value of the extraction system. It appears that the use of ionic liquid as an alternate solvent system in liquid/liquid extraction of copper ions is very promising.     

Extraction of sulfuric acid with TOPO

A study on solvent extraction of sulfuric acid by tri-octylphosphine oxide (TOPO) in n-heptane has been made. Extraction coefficients of H₂SO₄ as a function of H₂SO₄ concentration in aqueous phase, and extractant concentrations in organic phase have been studied. The composition of extracted species, equilibrium constants of extraction reaction have been evaluated. These results are important for interpreting extraction equilibrium data of uranium(VI) or other metal ions with TOPO in sulfuric acid media.     

Precipitation and extraction of some bivalent metal ions with bis(diphenylphosphinyl)methane and perchlorate

The solvent extraction of alkaline-earth and some bivalent transition metal ions such as Co(2+), Ni(2+), Cu(2+), Zn(2+) and Cd(2+) with the bidentate phosphine oxide compound, bis(diphenylphosphinyl)-methane (BDPPM), and perchlorate into 1,2-dichloroethane has been investigated. When benzene is used as the solvent, the complexes consisting of metal ion, BDPPM and perchlorate are not extracted but are precipitated at the liquid-liquid interface. The precipitates have been isolated and their compositions determined.     

Lanthanoid complexes with thenoyltrifluoroacetone and 4-tert-butylcalix[4]arene-tetraacetic acid tetraethyl ester: synergistic extraction and separation

The solvent extraction of fourteen lanthanoid ions with thenoyltrifluoroacetone (HTTA) in combination with tetraethyl 4-tert-butylcalix[4]arene-tetraacetic acid tetraethyl ester (S) from a perchlorate medium at constant ionic strength was investigated. The extracted species were identified as the Ln(TTA)₃·S complexes by slope analysis. Equilibrium constants, parameters for extraction, and the synergistic and separation factors between two adjacent Ln(III) ions were determined.

Preconcentration and separation of copper (II) with solvent extraction using N,N′-bis(2-hydroxy-5-bromo-benzyl)1,2 diaminopropane

Preconcentration and separation with solvent extraction of Cu(II) from aqueous solution using N,N′-bis(2-hydroxy-5-bromo-benzyl)1,2 diaminopropane (H₂L) as the new extractant has been studied. Separation of Cu(II) from other metal ions such as Cd(II), Ni(II), Zn(II), Pb(II), Cr(III), Co(II) and Mn(II) at aqueous solutions of various pH values and complexing agent H₂L, has been described. The possible extraction mechanism and the compositions of the extracted species have been determined. The separation factors for these metals using this reagent are reported while efficient methods for the separation of Cu(II) from other metal ions are proposed. From the loaded organic phase, Cu(II) stripping was carried out in one stage with different mineral acid solutions. The stripping efficiency was found to be quantitative in case of HNO₃ and HCl. From quantitative evaluation of the extraction equilibrium data, it has been deduced that the complex extracted is the simple 1:1 chelate, CuL. The extraction constant has a value of logK_ex=−4.05±0.04.     

Solvent extraction of Cobalt/II/ from thiocyanate solutions by sulphoxides

The extraction of cobalt/II/ from ammonium thiocyanate solutions by di-n-pentyl sulphoxide /DPSO/, di-n-octyl sulphoxide /DOSO/ and their mixtures in carbon tetrachloride has been studied. The species extracted were found to be Co/SCN/₂. 4S /where S=DOSO or DOSO/. Synergic effects have been observed which are ascribed to the formation of mixed ligand metal complexes. The influence of the metal concentration, temperature and the diluent on the extraction of cobalt/II/has been investigated.     

Use of 1-alkyl-3-methylimidazolium hexafluorophosphate room temperature ionic liquids as chelate extraction solvent with 4,4,4-trifluoro-1-(2-thienyl)-1,3-butanedione

Possible use of room temperature ionic liquids (RTILs) as chelate extraction solvent was evaluated by using 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF₆]), 1-hexyl-3-methylimidazolium hexafluorophosphate ([hmim][PF₆]) and 1-octyl-3-methylimidazolium hexafluorophosphate ([omim][PF₆]). These RTILs showed high extraction performance for divalent metal cations with 4,4,4-trifluoro-1-(2-thienyl)-1,3-butanedione (Htta). The extracted metals were back-extracted into 1 mol dm⁻³ nitric acid quantitatively. Furthermore, the extracted species were estimated as neutral hydrated complexes M(tta)₂(H₂O)_n (n= 1 or 2) for M = Ni, Cu and Pb and anionic complexes M(tta)₃⁻ for M = Mn, Co, Zn and Cd.     

Liquid–liquid extraction of Cu(II), Co(II) and Ni(II) with salicylidèneaniline from sulphate media

For a fundamental study on the development of novel extraction divalent metal, the extraction behaviour of copper(II), cobalt(II) and nickel(II) is studied with salicylidèneaniline (SAN). The phenol group in the Schiff base moiety leads to a large increase in the percentage of transition metal ions. SAN has both good reactivity towards metal ions and solubility in organic solvents. The solvent extraction of copper(II), cobalt(II) and nickel(II) with salicylidèneaniline from sulphate media is studied with the following parameters: pH, concentration of the extractant and the nature of diluent. The stoichiometry coefficients of the extracted species are determined by the slope analysis method. The extraction reaction proceeds by cation exchange mechanism and the extracted species are: CuL₂HL, CoL₂HL and NiL₂. The extaction constants are evaluated for the different diluents. Under suitable conditions of pH, the solvent extraction of cobalt(II) and nickel(II) in different diluents leads to third phase formation. This tendency is confirmed from numerical extraction constants for both metal cations (log?K _ex?=??15.10?±?0.03 for nickel(II) in CHCl₃) and (log?K _ex?=??12.56?±?0.04 for cobalt(II) in CHCl₃). The extraction efficiency is found to follow the order Cu(II)?>?Co(II)?>?Ni(II).     

Thermodynamics of complex formation in dimethyl sulfoxide with ligands coordinating via N,P, As,Sb, OR Bi : III. A comparison between aromatic and aliphatic amines and phosphines

The stabilities of the complexes formed by silver(I), cadmium(II) and zinc(II) with tri-n-butylamine and tri-n-butylphosphine have been determined in dimethyl sulfoxide (DMSO). For the two latter metal ions, it has also been found that complexes are not formed in appreciable amounts with the triphenyl compounds Ph₃X, X = N, P and, in the case of cadmium(II), also As.From these and earlier measurements referring to DMSO as well as aqueous solutions, it was found that the stepwise stability constants increase by roughly one power of ten for each aromatic ring replaced by an aliphatic group, evidently as a consequence of the improved donor properties of the coordinating atoms. Further, for ligands of the same type, the stabilities are always markedly lower in DMSO than in aqueous solution. This is certainly due to the fact that the solvent molecules compete more strongly for the coordination sites in DMSO than in water, as reflected by the larger heats of solvation found in the former solvent for the metal ions concerned.     

The extraction of trace amounts of gold from different aqueous mineral acid solutions by diphenyl-2-pyridylmethane dissolved in chloroform

Diphenyl-2-pyridylmethane, a high molecular weight substituted pyridine has been examined and found to be a useful solvent extraction reagent. Its behaviour is similar to amines in that it forms salts with mineral acids. The acid ionization constant (pK_BH ⁺) determined spectrophotometrically has a value of 4.41±0.06 at 25 °C. A study of the partition behaviour of trace amounts of gold between mineral acid solutions and 0.1M diphenyl-2-pyridylmethane dissolved in chloroform indicates that the metal can be quantitatively extracted from dilute mineral acid solutions and also from concentrated hydrochloric acid media in a single extraction. Attempts have been made to gain an understanding of factors affecting the extraction of gold. Common anions have little effect on extraction in concentrations upto 1M. Separation factors of a number of metal ions relative to gold are reported for three mineral acid systems; and gold has been estimated in some synthetic samples using neutron activation technique by prior extraction with 0.1M solution of diphenyl-2-pyridylmethane dissolved in chloroform.     

Extraction of rare-earth,yttrium, and scandium perchlorates by podands bearing diphenylphosphorylacetamide terminal groups

Partition of trace amounts of metal (La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y, and Sc) perchlorates was studied between aqueous HClO₄ solutions and dichloroethane solutions of phosphorus podands bearing two Ph₂P(O)CH₂C(O)NH-terminal groups linked via di-and triethylene glycol spacers. The stoichiometry of extracted complexes was determined. The efficiency of metal ion recovery to the organic phase was studied as a function of aqueous HClO₄ concentration and nature of the organic solvent. The compounds synthesized have higher metal extraction capacities in HClO₄ solutions than (dibutylcarbamoyl)diphenylphoshine oxide. The utility of macroporous polymer sorbents impregnated by these podands for extracting and concentrating rare earth(III) and scandium(III) ions from aqueous perchlorate solutions was demonstrated.     

Complexation of trivalent lanthanoid ions with 4-benzoyl-3-phenyl-5-isoxazolone and p-tert-butylcalix[4]arene fitted with phosphinoyl pendant arms in solution during synergistic solvent extraction and structural study of solid complexes by IR and NMR

The liquid extraction of 14 lanthanoids with a 4-benzoyl-3-phenyl-5-isoxazolone (HPBI) alone in CHCl₃ as a diluent from perchlorate medium at constant ionic strength μ = 0.1 is investigated. The synergistic solvent extraction of five selected lanthanoid ions (La³⁺, Nd³⁺, Eu³⁺, Ho³⁺ and Lu³⁺) with 4-benzoyl-3-phenyl-5-isoxazolone (HPBI) and 5,11,17,23-tetra-tert-butyl-25,26,27,28-tetrakis-(dimethylphosphinoylmethoxy)calix[4]arene, (S) in CHCl₃ has been studied too. The stoichiometry of the extracted species was characterised by a classical log–log plot analysis. It was found that the composition of the extracted species with HPBI are Ln(PBI)₃ and in the presence of the phosphorus-containing calix[4]arene the lanthanoid ions have been extracted as [Ln(PBI)₃S₂]. The values of the equilibrium constants and the separation factors have been calculated. The influence of the synergistic agent on the extraction process has been discussed.