Effect of acidity on the extraction and kinetic stability of the copper(II)/APCD/IBMK system in strongly acidic media

The extraction of copper(II) from strongly acidic solution (0.01-8M hydrochloric acid) with ammonium 1-pyrrolidinecarbodithioate in isobutyl methyl ketone has been investigated. The shaking time needed for quantitative extraction decreases as the acidity is increased. The effect of the mutual solubility of the organic solvent and the aqueous phase is significant when the acidity of the aqueous phase is increased. The acidity of the aqueous phase mainly affects the kinetic stability of the chelate during the shaking period, rather than the decomposition of the chelating agent. The kinetic stability of the chelate apparently depends on the mole ratio of reagent to copper, the half-lives for the chelate extracted from 4M hydrochloric acid being 29.0, 40.0 and 85.0 min for reagent: metal mole ratios of 10, 100 and 1000, respectively.     

Liquid-liquid extraction of palladium(II) with N-n-octylaniline from hydrochloric acid media

N-n-Octylaniline in xylene is used for the extractive separation of palladium(II) from hydrochloric acid medium. Palladium(II) was extracted quantitatively with 10 ml of 2% reagent in xylene from 0.5-2 M hydrochloric acid medium. It was stripped from the organic phase with 1:1 ammonia and estimated spectrophotometrically with pyrimidine-2-thiol at 420 nm. The effects of metal ion, acids, reagent concentration and of various foreign ions have been investigated. The method affords binary separation of palladium(II) from iron(III), cobalt(II), nickel(II) and copper(II) and is applicable to the analysis of synthetic mixtures and alloys. The method is fast, accurate and precise.     

Application of APCD/DIBK extraction system in strongly acidic media: Determination of traces of copper and nickel in titanium metals by extraction-flame atomic-absorption spectrometry

Extraction of nickel in strongly acidic solution (0.01 approximately 8M hydrochloric acid) with ammonium 1-pyrrolidinecarbodithioate (APCD) into di-isobutyl ketone (DIBK) has been studied, and the APCD/DIBK system has been applied to simultaneous extraction and flame atomic-absorption spectrometric determination of trace amounts of copper and nickel in titanium metal. Nickel could be extracted with copper from strongly acidic solution such as up to 5M hydrochloric acid with APCD/DIBK system. The extraction from such a strongly acidic media made it possible to extract nickel with copper, since it did not require the addition of a large amount of the masking agent which prevents the hydrolysis of the matrix titanium and also prevents the extraction of nickel. Thus, they could be extracted directly from the titanium metal sample digested by concentrated hydrochloric acid with a small amount of tetrafluorohydroboric acid. Effect of coexistence of a large amount (at least 0.2 g) of iron on the extraction of both elements could be prevented by keeping most of the matrix titanium as Ti(III). With the method described here, mug/g levels of copper and nickel in titanium metal could be rapidly determined with good precision and accuracy.     

Decomposition of Cu(PCD)(2) extracted into IBMK and DIBK phases from hydrochloric acid media

The decomposition of the bis(1-pyrrolidinedithiocarbamato) copper(II) complex [Cu(PCD)(2)] extracted into isobutyl methyl ketone (IBMK) and di-isobutyl ketone (DIBK) from hydrochloric acid solution (0.01-8M) has been studied with UV-visible and ESR spectrometry. The mixed-ligand complex CuCl(PCD) is formed as an intermediate and CuCl(2) or CuCl3(-)(3), are formed as final products, in the decomposition of Cu(PCD)(2). The concentration of free hydrochloric acid dissolved in the extract has also been determined, and the effect of the free acid on the decomposition has been studied. The decomposition reaction of Cu(PCD)(2) extracted from hydrochloric acid solution can be thought of as a ligand substitution by Cl(-), and occurs with both IBMK and DIBK extraction.     

Palladium(II) extraction from hydrochloric acid solutions with diacylated triethylenetetramine

Extraction of palladium(II) with diacylated triethylenetetramine hydrochloride (with chloroform as diluent) from hydrochloric acid solutions was studied. Palladium(II) extraction from 3 mol/L HCl solutions occurs via anion-exchange mechanism. Concentrational constants were calculated and thermodynamic parameters of extraction were estimated.     

Extraction of palladium(II) from hydrochloric acid solutions with triacylated ethyleneamines

Extraction of palladium(II) from hydrochloric acid solutions with novel efficient extractants, triacylated ethyleneamines, was studied. The most effective extraction of palladium(II) was observed from 0.5–1 M HCl solutions. Extraction of palladium(II) from 1 M HCl solutions was found to occur through mixed (coordination and anion-exchange) mechanism. In the field of dominance of the anion-exchange mechanism of the extraction of palladium(II) with triacylated pentaethylenehexamine the concentration constant of palladium(II) extraction was calculated, and thermodynamic parameters of extraction were evaluated.     

Effect of washing on the kinetic stability of the copper(II)/APCD/IBMK system in strongly acidic media

The extraction behaviour of copper(II) with ammonium 1-pyrrolidinecarbodithioate in isobutyl methyl ketone has been investigated at various acidities of the aqueous phase. The chelate is produced even under strongly acidic conditions (0.01-6M), and if the organic phase is washed with water it remains stable for at least 1 hr. The extraction is quantitative over the entire range of acidity.     

The extraction of copper(II) from hydrochloric acid by solutions of tetra-n-hexylammonium chloride in ethylene dichloride

In marked contrast to the behaviour of copper(I), the extraction of copper(II) by solutions of tetra-n-hexylammonium chloride in ethylene dichloride is very small from 1.0 M chloride and although it increases with concentration it does not reach 90% until the chloride concentration exceeds 4 M. By varying such parameters as [Cl^-], [NR₄⁺Cl^-]_org. and the total amount of copper in the system, it was shown that the distribution equilibria could best be explained by postulating the presence of binuclear complexes Cu₂Cl₆^2- and Cu₂Cl₇^3- in addition to mononuclear complexes in the aqueous phase, while only mononuclear species such as NR₄₊CuCl₃^-and (NR₄⁺)₂CuCl₄^2- are extracted. A linear relationship is predicted between the reciprocal of the distribution ratio and the total amount of copper present at equilibrium in the aqueous phase and confirmed by the experimental results.     

Extraction of actinium with di (2-ethylhexyl) phosphoric acid from hydrochloric and nitric acid solutions

The extraction of actinium with HDEHP from Cl^– and NO ₃ ^– systems has been investigated. It was found that extraction of actinium from HCl solutions is much better than from HNO₃ solutions. Stability constants of the actinium complexes Ac(X^–)²⁺, X^–=Cl^– or NO ₃ ^– , were determined. Our results show that actinium formed less stable complexes with Cl^– than with NO ₃ ^– ligands.     

Extraction of Cu(II) from hydrochloric acid media by Amberlite LA-1 hydrochloride dissolved in 1,2-dichloroethane

The extraction of hydrogen chloride by a secondary amine (B), Amberlite LA-1, dissolved in 1,2-dichloroethane was studied by two-phase potentiometric titration. The results, treated by a general minimizing program, indicate dimerization: 2BHCl(BCHl)₂. The equilibrium constant of this reaction was calculated. The extraction of cu(II) from 6M hydrochloric acid by Amberlite LA-1 hydrochloride (BCHl) dissolved in 1,2-dichloroethane, was also studied. The extraction of cu(II) can be explained as due to formation of two species, (BCHl)₂ CuCl₂ and (BCHl)₃ CuCl₂, in the organic phase. The formation constants of these species were calculated.     

Solvent extraction of copper(II) with chlorendic acid

The solvent extraction of Cu(II) with chlorendic acid has been studied The composition of the extracted species appears to be a function of pH. In the pH range 3.2-4.6, a monomeric species exists [Cu(II)(L(2-)], while at pH values greater than 4.5, a dimer in the form of [Cu(II)(L(2-)). H(2)L](2) and/or [Cu(II)(HL(-))(2)](2) is extracted.     

Extraction of copper(II) from ammonium chloride solutions with capric acid

Extraction of copper(II) with capric acid from ammonium chloride solutions was examined. The composition of the complex extracted was determined and it was found that the extraction process can be adequately described by the equation: 2Cu_(a)²⁺ + 3(HR)_2,(0) ⇌ (CuR₂·HR)_2,(0) + 4H_(a)⁺     

Ion exchange extraction of platinum(IV) and palladium(II) from hydrochloric acid solutions

Sorption concentration of platinum(II, IV) and palladium(II) from freshly prepared and aged two-yearold hydrochloric acid solutions by a series of anion exchangers with different functional groups and of different physical structure of Purolite and CYBBER grades was studied. The high sorption ability of the ion exchangers in relation to the extracted chlorocomplexes of noble metals is shown. It was demonstrated that palladium(II) from all tested ion exchangers can be completely desorbed with thiourea solutions acidified with hydrochloric acid, while complete desorption of platinum is achieved only from Purolite S 985 anion exchanger of the complexforming type and Purolite A 111 weak base anion exchanger.     

The extraction of Zn(II), Cd(II) and Pb(II) from hydrochloric acid media by amberlite LA-2 hydrochloride dissolved in 1,2-dichloroethane

The extraction of HC1 by the secondary amine (B), known as Amberlite LA-2, dissolved in 1,2-dichloroethane and the aggregation of BHC1 have been studied by using a two-phase potentiometric titration technique. The experimental data, treated by a general minimizing program, indicate dimerization: 2 BHClright harpoon over left harpoon(BHCl)(2). The equilibrium constant of this reaction was calculated. The extraction of ZnCl(2), CdCl(2) and PbCl(2) from 0.2,0.5, 1.0 and 2.0M HCl, and 1MNaCl by Amberlite LA-2 hydrochloride (BHCl), dissolved in 1,2-dichloroethane, has been studied. The complexes (BHCl)(2)ZnCl(2), (BHCl)(2)CdCl(2) and (BHCl)(2)PbCl(2) were found to exist, irrespective of the composition of the aqueous phase. The formation constant of the first was calculated.     

Extraction of rhodium(III) with sulfoxides from hydrochloric acid solutions

Extraction of rhodium(III) from hydrochloric acid solutions with dihexyl sulfoxide (DHSO) and with petroleum sulfoxides (PSOs) was studied, and the optimal conditions for its recovery were found. At a phase contact time of up to 0.5 h, the extraction of rhodium(III) with sulfoxides occurred mainly by an ionassociation scenario. If the phase contact time exceeds 0.5 h, a mixed extraction scenario predominated to form the extracted complexes (L · H⁺) · [RhCl₄L₂]-(DHSO)_o and PSO (LH⁺) · [RhCl₄(H₂O) · L]⁻. The protonation of the extraction agents occurred at the donor oxygen atoms of the sulfoxide group. When rhodium was extracted with PSOs, the coordination of the extractant molecule in the inner coordination sphere of the acido complex to the metal ion occurred through the donor sulfur atom of the sulfoxide group, while with the use of DHSO, through the donor atoms of sulfur and oxygen of the sulfoxide group. Electronic, ¹H NMR, and IR spectroscopy and elemental analysis were used to determine the composition of the extracted compounds and suggest their structure.     

Extraction of lead(II) and copper(II) from salicylate media by tributylphosphine oxide.

Tributylphosphine oxide (TBPO) is proposed as an extractant for the extraction of lead(II) and copper(II) from salicylate media. The optimum conditions were evaluated by varying the experimental parameters, such as the pH, sodium salicylate concentration, tributylphosphine oxide (TBPO) concentration, shaking period and various diluents. The probable extracted species, deduced from log-log plots were Pb(HSal)2.2TBPO and Cu(HSal)2.2TBPO. The extraction took place through a solvation mechanism. The method permits the binary separation of lead(II) and copper(II) from commonly associated elements as well as the mutual separation of lead(II) and copper(II). The method is applicable to the determination of lead(II) and copper(II) in various alloys as well as environmental and pharmaceutical samples.     

Iridium(IV) extraction with petroleum sulfoxides from hydrochloric acid solutions

Iridium(IV) extraction with petroleum sulfoxides (PSO) from hydrochloric acid solutions is studied. Optimum conditions of extraction are chosen. It is shown that in the investigated extraction systems for a phase contact time of 30 min, iridium(IV) is extracted by the ion-associative mechanism. Electronic, ¹H NMR, and IR-spectroscopy, and elemental analysis are used to establish the structure of the extracted compound.     

The extraction of copper(I), lead(II) and tin(IV) from hydrochloric acid by solutions of tetra-n-hexylammonium chloride in ethylene dichloride

Copper(I) is strongly extracted from chloride media as the ion-pair NR₄+CuCl₃-by solutions of tetra-n-hexylammonium chloride (NR₄+Cl-) in ethylene dichloride. The distribution coefficient decreases from ca. 100 in 1 M chloride but is still as high as 13 in 10 M chloride. The extraction of lead(II) is shown to be due to the partition of the ion-pair (NR₄+PbCI₃-). The percentage of 0.0018 M lead extracted is 98% from 0.58 M hydrochloric acid and falls to 38% from 7.8 M acid. The distribution coefficient decreases rapidly with the total lead concentration. The extractions of tin(IV) increased to a maximum of 99.5% in ca. 5 M hydrochloric acid but decreased rapidly above 6 M acid. It proved impossible to identify the extractable species.     

Extraction of rhodium(III) with petroleum sulfoxides from hydrochloric acid solutions

Extraction of rhodium(III) from hydrochloric acid solutions with petroleum sulfoxides was studied. The optimal conditions of its recovery were found. The composition and structure of the compound being extracted was determined by electronic absorption, ¹H NMR, and IR spectroscopies and elemental analysis.