Evaluation of unsymmetrical dithiodiglycolamide as novel extractant for application in selective separation of palladium(II) from aqueous solutions

A novel unsymmetrical multidentate ligand namely; N,N'-dimetyl-N,N'-didecyldithiodiglycolamide (DMD³TDGA) was synthesized and used as agent for the selective extraction of palladium(II) from hydrochloric acid solutions. A systematic investigation was carried out on the extraction of Pd(II) using DMD³TDGA. The quantitative extraction of Pd(II) with DMD³TDGA in n-dodecane is observed at ~4 M HCl. The main extracted species of Pd(II) is PdC_l2. DMD³TDGA and IR spectra of the extracted species were investigated. The extraction of palladium(II) from various concentrations of hydrochloric acid solutions in the presence of metal ions, such as Pt(IV), Rh(III), Cr(II), Ni(II), Fe(III), Nd(III), Zr(II), and Mn(II) was carried. DMD³TDGA showed very high selectivity and extractability for Pd(II). Quantitative back extraction of Pd(II) was obtained in single contact using thiourea solution. The results obtained indicated that, excellent separation of Pd(II) from the investigated metal ions can be achieved. Five successive cycles of extraction/back-extraction, indicating excellent stability and re-utilization of this new extractant can be used for selective separation of Pd(II) from other elements in hydrochloric acid medium.     

Solvent Extraction Studies of Metal-4-(2-pyridyl-azo)-Resorcinol Complexes with Potassium-Dicyclohexyl-18-crown-6 Complex

Abstract

The solvent extraction studies of Pd(II), V(V), Co(III), Cu(II), Ni(II) and Fe(II)-PAR [4 - (2-pyridyl azo)-resorcinol] complexes with dicyclohexyl-18-crown-6 have been investigated in 1,2-dichloroethane as a solvent. It was observed that the complexes of Pd(II), V(V), Co(III), Cu(II), Ni(II) and Fe(II)-PAR were extracted into organic phase. In order to investigate the effect of enthalpy and entropy in the extraction of metal-PAR complexes, an attempt has been made to explore the temperature effect. In the extraction studies, it was observed that the entropy effect is one of the major factors for the selective extraction. The shape of the complexes may be one of the causes for the extractability of metal-PAR complexes with potassium dicyclohexyl-18-crown-6. The planar palladium-PAR-SCN^? complex was easily extracted into organic phase in comparison with other complexes.     

Xylenol Orange‐Functionalized Halloysite Nanotubes as a Novel Adsorbent for Selective Solid‐phase Extraction and Determination of Trace Noble Elements

A novel method using xylenol orange‐modified halloysite nanotubes as a solid‐phase sorbent has been developed for the simultaneous preconcentration and separation of trace Au(III ) and Pd(II ) prior to their determination by inductively coupled plasma‐atomic emission spectrometry (ICP‐AES ). The experimental effects of pH , the amount of adsorbent, sample flow rate, sample volume, interfering ions, and the elution condition were investigated in detail. Au(III ) and Pd(II ) were retained on the column at pH 3, and eluted with 2.0 mL of 1.0 mol/L HCl + 2% CS (NH₂ )₂ solution. Common interfering ions did not have any impact on the adsorption, separation, and determination. An enrichment factor of 150 was obtained. The maximum adsorption capacities of the adsorbent were 41.63 and 47.82 mg/g for Au(III ) and Pd(II ), respectively, under the optimum conditions. By the definition of IUPAC , the detection limits (3σ ) of this method for Au(III ) and Pd(II ) were 0.31 and 0.27 ng/mL , and the relative standard deviations (RSDs ) were 2.7 and 3.2%, respectively (n = 8). This newly developed method was verified by certified reference materials, and has been successfully applied to the determination of trace Au(III ) and Pd(II ) in mine samples with satisfactory results. It can be confidently predicted that the method can be used for the determination trace Au(III ) and Pd(II ) in other real samples because of its high selectivity, sensitivity, and reproducibility.     

Extraction of palladium(II) from hydrochloric acid solutions by (RS)-1-(4-chlorophenyl)-4,4-dimethyl-3-(1H-1,2,4-triazol-1-ylmethyl)-pentan-3-ol

The extraction properties of (RS)-1-(4-chlorophenyl)-4,4-dimethyl-3-(1H-1,2,4-triazol-1-ylmethyl)-pentan-3-ol (with chloroform as a diluent) with respect to palladium(II) were studied. Palladium(II) was found to be efficiently extracted by the reagent from 0.1–6 M HCl solutions by the coordination mechanism. The rate of palladium(II) recovery depends on the hydrochloric acid and chloride ion concentrations in the aqueous phase. Conditions for the selective separation of palladium(II) and copper(II) from nickel(II), cobalt(II), and iron(III) 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.     

Liquid Extraction of Noble Metal Ions with an α-Amino Phosphonate

The extraction of Au(III), Pt(IV), and Pd(II) ions from aqueous hydrochloric acid solutions with solutions of bis(2-ethylhexyl) N-butyl-N-octylaminomethylphosphonate in chloroform and xylene was studied. The recovery of the noble metal ions is the most efficient at low acidities of the aqueous solution, with a high selectivity of separation from the concomitant Fe(III), Cu(II), Ni(II), and Co(II) ions.     

Evaluation of ion imprinted polymers for the solid phase extraction and electrothermal atomic absorption spectrometric determination of palladium in environmental samples

The complexes of Pd(II) with ammonium pyrrolidinedithiocarbamate (APDC), N,N′-diethylthiourea (DET) and dimethylglyoxime (DMG) were prepared and imprinted into a polymeric network. The ion-imprinted polymers (IIPs) were synthesized by copolymerization of 4-vinylpyridine (VP) and styrene as functional monomers and divinylbenzene as a cross-linking agent in the presence of 2,2-azo-bis-isobutyronitrile as an initiator. The influence of sample volume, pH and flow rate on the extraction efficiency of Pd was studied under dynamic conditions. Pd(II) could be quantitatively retained on each of the studied sorbents at the pH range of 0.5 to 1.0, and eluted with an acidic solution of thiourea. The polymer with the imprinted Pd-DET-VP complex offered the highest selectivity for Pd(II) over certain matrix components, such as Pt(IV), Ni(II) and Cu(II). The low sample pH is an important advantage of the separation procedure, as it allows an effective separation of Pd(II) from complex environmental matrices. The developed separation method was successfully applied to the electrothermal atomic absorption spectrometric (ETAAS) determination of trace amounts of Pd in tap and river water, grass, and certified platinum ore (CRM SARM 7 and SARM 76) samples with reproducibility below 6.5%. The detection limit for Pd(II) obtained by ETAAS after the pre-concentration on Pd-DET-VP polymer was 0.012?ng?mL^?1 for 75?mL sample volume.     

Separation of trivalent rare earths plus sc(iii) from al,ga,in,tl, fe,ti, u and other elements by cation-exchange chromatography

A method is presented for the quantitative separation of the trivalent rare earths plus Sc(III) as a group from Al(III), Ga(III), In(III), Tl(III), Fc(III). Ti(IV), U(VI), Be(II). Mn(II), Co(II), Cu(II), Ni(II). Zn(II). and Cd(II). These elements can be eluted from a cation-exchange column with 1.75 N HCl, while the rare earth group elements are retained. Numerous other elements not investigated have low distribution coefficients in 1.75 N HCl and therefore should be separated by the same procedure; Th(IV) is retained by the column when the rare earths are elutcd with 3.0 N HCl. The only elements which partially accompany the rare earths plus Sc(III) are Zr(IV), Hf(IV), Sr(II), and Ba(II) ; these have to be separated by special procedures. The method is suitable for accurate reference analysis over a wide range of concentrations.     

Liquid extraction of noble metal ions with bis(α-aminophosphonates)

Extraction of Au(III), Pt(IV), and Pd(II) ions from hydrochloric acid media with solutions of two bis(aminophosphonates), such as N,N-bis(dipentoxyphosphorylmethyl)octylamine and N,N′-bis[[(dioctyloxyphosphoryl)methyl]butylamine], in chloroform and xylene was investigated. Both these extractants proved to be highly effective for Au(III) ions in a wide acidity range, which allows these ions to be separated from other noble metal ions with a high degree of selectivity. At the same time, Pt(IV) and Pd(II) ions cannot be separated from one another with the extractants studied. The selectivity of their separation from Fe(III), Cu(II), Co(II), and Ni(II) metal ions is, too, not high. The reasons for these results lie in the specific structural features of the extractants, which predetermine the extraction mechanism.     

Highly efficient adsorbing noble metal ions by 3,4-dihydroxycinnamic acid-modified activated carbon

A method was established for the preconcentration of trace Au(III), Pd(II) and Pt(IV) by activated carbon modified with 3,4-dihydroxycinnamic acid. The separation and preconcentration conditions of analytes were investigated, such as effects of pH, the contacting time, the sample ?ow rate and volume, the elution condition and the interfering ions. At a pH of 1.0, the maximum static sorption capacity of the sorbent was found to be 374.8, 96.6 and 137.5 mg g^?1 for Au(III), Pd(II) and Pt(IV), respectively. The adsorbed metal ions were effectively eluted with 2.0 mL of 4% thiourea in 0.5 M HCl solution and determined by inductively coupled plasma optical emission spectrometry. The detection limit (3σ) of this method defined by IUPAC was found to be 0.12, 0.18 and 0.32 ?g L^?1 for Au(III), Pd(II) and Pt(IV), respectively. The relative standard deviation (RSD) was lower than 3.0% (n = 8) towards standard solutions. The method has been validated by analysing certified reference materials and successfully applied to the determination of trace Au(III), Pd(II) and Pt(IV) in road sediments samples.     

Liquid—liquid extraction of transition metals with acylthioacetamides

The extraction behaviour of acylthioacetamides, R¹—CO—CH₂—CS—NR²R³, was studied for a series of transition metals. The highest distribution ratios were obtained with benzoylthioacetanilide. Complexes with acylthioacetamides which were completely substituted on the amide group were extracted slowly. The ranking of the extraction characteristics is related to the different pK_a values of the compounds used. Polymerization and solvation reactions can be excluded at metal concentrations of ? 10^-3 mol dm^-3 and extractant concentrations of ?10^-1 mol dm^-3, respectively. Decreasing extractability, Cu(II) > Zn(II) > Ni(II) > Co(II) > Cd(II), corresponds to the stability constants of the extracted metal chelates. Iron(III) cannot be extracted at pH ?3; Hg(II), Pd(II), and Au(III) are extracted readily over a reasonably wide pH range. The different extraction constants for zinc(II) and cadmium(II) permit an effective separation of these ions with benzoylthioacetanilide.     

Separation of gold from Cu, Pt, Pd, Ni, Zn, Cd and Hg using triphenylarsine oxide as an extractant

A method is developed for extraction of gold(III) (75–300 g) from hydrochloric acid solution with triphenylarsine oxide dissolved in toluene as extradant. Gold(III) is determined spectrophotometrically with stannous chloride. The extraction is quantitative from 1.5–1.9M hydrochloric acid with 0.25% triphenylarsine oxide and an equilibration period of 30s. The method permits separation of gold(III) from Cu(II), Pt(IV), Pd(II), Ni(II), Zn(II), Cd(II) and Hg(II) and its spectrophotometric determination in ayurvedic medicines. The recovery and relative standard deviation obtained are >99.0% and <1.0%.     

Das Trihydrochlorid-monohydrat der N-(Pyrid-2-ylmethyl)ethylendiamin-N,N′,N′-triessigsäure und ihr Lanthan(III)-Komplex

The Trihydrochloride Monohydrate of N -(Pyrid-2-ylmethyl)ethylenediamine- N , N′ , N′ -triacetic Acid and its Lanthanum(III) Complex We report the results of the investigation of N-(pyrid-2-ylmethyl)ethylenediamine-N,N′,N′-triacetic acid (H₃pedta) and its complexes with rare earth metal ions. The X-ray crystal structures of H₃pedta · 3 HCl · H₂O and of the lanthanum(III) complex [La(pedta)(H₂O)] · 2 H₂O were determined. The complex forms a polymer, lanthanum(III) has coordination number 10, one water molecule is coordinated. The water degradation of H₃pedta · 3 HCl · H₂O and of the complex was investigated by thermoanalysis. Luminescence studies of the corresponding europium(III) complex in aqueous solution show three coordinated water molecules.     

Dithiodiglycolamide: novel ligand with highest selectivity and extractability for palladium

A novel multidentate ligand N,N,N′,N′-tetra(2-ethylhexyl) dithiodiglycolamide DTDGA has been synthesized and studied for its extraction behavior towards various elements present in high level liquid waste (HLW). The extractant showed remarkable extractability and selectivity for palladium vis a vis other metal ions present in HLW. The distribution ratio as well as the separation factor for palladium was found to be the highest reported so far thus making this extractant one of the most promising candidates for effective separation of palladium from HLW.     

Reversed phase partition chromatographic separation of divalent copper with N-n-octylaniline on silica gel

A novel separation method was developed for the extraction and chromatographic separation of copper(II). The quantative extraction of 25.0–125.0 μg copper(II) has been observed from 0.05 to 0.25 mol/L of ascorbic acid at pH 9.0–12.0 with 0.087 mol/L N-n-octylaniline (liquid anion exchanger) coated on silica gel at a flow rate of 1.0 ml/min. The extracted metal ion has been recovered by eluting with 25.0 ml of 1.0 mol/L hydrochloric acid and determined spectrophotometrically by rubeanic acid method. The various influencing parameters viz. acid concentrations, reagent concentration, eluates effect of pH, and effect of flow rate on extraction were studied. The method is free from large number of interferences from cations and anions. A scheme for mutual separation of copper(II), gold(III) and bismuth(III) has been developed. Copper(II) has been separated from ayurvedic (Herbal) medicine and synthetic mixtures corresponding to alloy. The log–log plot of N-n-octylaniline concentration versus the distribution coefficient indicates that the probable extracted species is [.     

Selective back-extraction and preconcentration of zinc(II) from metal-1,3,5-triketone extracts prior to its determination by flame atomic absorption spectrometry

A simple back-extraction method was developed for the separation and preconcentration of trace levels of zinc from different matrices. Ethyl-2-(4-methoxybenzoyl)-3-(4-methoxyphenyl)-3-oxopropanoylcarbamate (EMPC) was used as a new complexing agent for the extraction of zinc(II) from the aqueous sample phase to the methyl isobutyl ketone (MIBK) phase as Zn(EMPC)₂ complexes. The Zn(II) can be selectively stripped with 1?mL of 0.5?mol?L^?1 HCl from Mⁿ⁺(EMPC)_n complexes [Ag(I), Al(III), Cd(II), Cr(III), Cu(II), Fe(II), Fe(III), Mn(II), Ni(II), Pb(II) and Pd(II)] which dissolved in MIBK phase. Some experimental parameters, which are important for the whole extraction process, including pH, sample volume, shaking time, amount of the EMPC reagent, amount of MIBK, ionic strength, and type of back-extractant were investigated. The recovery for Zn(II) was greater than 95%. The detection limit of the method was found to be 0.2?µg?L ^{? 1} and the relative standard deviation as 6.4%. The concentrations of Zn(II) in the certified reference materials (LGC6019 river water and NIST-1547 peach leaves) by the presented method were in good agreement with the certified values. The proposed method was succesfully applied to the determination of zinc in some natural waters, rice, hair, soil, and tea samples.     

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.     

Liquid-liquid extraction and recovery of indium using Cyanex 923

The extraction of In(III) from HCl, H₂SO₄, and HNO₃ media using a 0.20 mol l⁻¹ Cyanex 923 solution in toluene is investigated. In(III) is quantitatively extracted over a fairly wide range of HCl molarity while from H₂SO₄ and HNO₃ media the extraction is quantitative at low acid concentration. The extracted metal ion has been recovered by stripping with 1.0 mol l⁻¹ H₂SO₄. The stoichiometry of the In(III): Cyanex 923 complex is observed to be 1:2. The extraction of In(III) is insignificantly changed in diluents namely toluene, n-hexane, kerosene (160-200 °C), cyclohexane, and xylene having more or less the same dielectric constants, whereas, it decreases with increasing polarity of diluents such as cyclohexanone and chloroform. The extractant is stable towards prolonged acid contact and there is a negligible loss in its extraction efficiency even after recycling for 20 times. The extraction behavior of some commonly associated metal ions namely V(IV), Ti(IV), Al(III), Cr(III), Fe(III), Ga(III), Sb(III), Tl(III), Mn(II), Fe(II), Cu(II), Zn(II), Cd(II), Pb(II), and Tl(I) has also been investigated. Based on the partition data the conditions have been identified for attaining some binary separations of In(III). These conditions are extended for the recovery of pure indium from zinc blend, zinc plating mud, and galena. The recovery of the metal ions is around 95% with purity approximately 99%.     

Tuning the diglycolamides for modifier-free minor actinide partitioning

The unsymmetrical diglycolamides (DGAs) such as N,N-dihexyl-N′,N′-dioctyl-3-oxapentane-1,5-diamide (DHDODGA), N,N-didecyl-N′,N′-dioctyl-3-oxapentane-1,5-diamide (D²DODGA), N,N-didodecyl-N′,N′-dioctyl-3-oxapentane-1,5-diamide (D³DODGA), were synthesized, and characterized by IR, NMR, and mass spectroscopic techniques. The extraction behaviour of Am(III), Eu(III), and Sr(II) by the solutions of these unsymmetrical DGAs in n-dodecane was studied as a function of concentration of nitric acid and DGA. The distribution ratio of Am(III) and Eu(III) increased with increase in the concentration of nitric acid; whereas, the distribution ratio of Sr(II) reached a maximum at 4 M nitric acid followed by decrease at higher acidities. The extraction of Am(III) and Eu(III) in 0.1 M DGA/n-dodecane decreased in the order DHDODGA > D²DODGA > D³DODGA. However, the order changed upon lowering the concentration of DGA. The third-phase formation behaviour of nitric acid and neodymium(III) in 0.1 M DGA/n-dodecane was studied as a function of concentration of nitric acid. The limiting organic concentration of nitric acid and neodymium increased with increase in the chain length of alkyl group attached to amidic nitrogen. Near stoichiometric amount of neodymium(III) was loaded in 0.1 M D³DODGA/n-dodecane without the formation of third-phase from 3 to 4 M nitric acid medium. The study revealed that the unsymmetrical diglycolamides D²DODGA and D³DODGA are superior candidates for partitioning the minor actinides from high-level liquid waste.     

Solvent extraction of zinc by 2-hexylpyridine in benzene from aqueous mineral acid — Thiocyanate media

Solvent extraction of Zn(II) by 2-hexylpyridine (HPy) in benzene has been studied from aqueous mineral acid—thiocyanate media. The extraction, though dependent on the acidity of the aqueous phase, is poor from mineral acids (HCl, HNO₃ or H₂SO₄). Addition of 0.02M KSCN to the aqueous phase enhances the distribution ratio by a factor of almost one thousand. The stoichiometry of the extracted complex established by the usual slope analysis method indicates that an ionic type complex, e.g. Zn(SCN)₄·(HPyH)₂, is responsible for extraction. Complexing anions like acetate, oxalate or citrate at 1 M concentration mask the extraction of Zn(II) almost completely. Separation factors determined at optimal conditions (0.1M HPy in benzene −0.05M H₂SO₄+0.2M SCN⁻) indicate that Zn(II), along with Hg(II), can be separated in a single extraction from a number of metals, e.g. Cs(I), Sr(II), Ln(III), Y(III), Cr(III) and (VI). Other metals of interest like Cu(II), Co(II), Fe(III), Mo(VI), U(VI) and Tc(VII) are coextracted but the separation factors are large enough to allow separation in a multistage extraction process.