Ion-Pair Solvent Extraction of EDTA Anions with Tetraalkylammonium Ions in Various Organic Solvents

Summary.  The ion-pair solvent extraction behavior of ethylenediaminetetraacetate (EDTA) anion by various tetraalkylammonium ions was investigated at 25.0 ± 0.1°C. The extraction of EDTA exceeded 90% from the basic aqueous solution into the organic solvents such as n-hexane and benzene derivatives containing tri-n-octylmethylammonium chloride, but EDTA was hardly extracted from acidic solution. Among the chemical species of EDTA in aqueous solution, edta ⁴⁻ is the most extractable one. On the other hand, the extraction of EDTA was less than 1% into chloroform and 1,2-dichloroethane even from the basic aqueous solution. The effect of the structure of alkylammonium ion was also examined. Tetra-n-hexylammonium and tetra-n-octylammonium ions could not extract EDTA even from the basic aqueous solution, while the use of tri-n-octylmethylammonium and di-n-lauryldimethylammonium ions enhances the extraction of EDTA. These results suggest that the steric hindrance in the ion-pair of alkylammonium and EDTA anion in the organic phase affects the extractability of EDTA containing ion-pair. The solution structure of ion-pair in the organic phase was calculated by MMFF force field and the steric effect in the ion-pair was also suggested. From the extraction constants obtained, the possibility of the extraction separation of EDTA has been shown. Present address: Chemistry Department, Heilongjiang University, Harbin, China     

Back extraction of lactic acid with microporous hollow fiber membrane

In this work, back extraction was considered a promising alternative to regenerate carboxylic acids of low-volatility into appropriate aqueous solution from organic phase. Identification of an efficient back extraction system for lactic acid recovery was focused on. Screening of back extraction reagents was first carried out by employing a wide variety of inorganic compounds. From the viewpoints of high stripping power, low cost and capability of simultaneously regenerating the extractant, aqueous sodium chloride solution was selected as the most suitable one for recovery of lactic acid from lactate–TOMAC (tri-n-octylmethylammonium chloride) complex. However, TOMAC and oleyl alcohol are likely to pose the troubling emulsion problem in conventional mixer–settler system. Therefore, non-dispersive back extraction of lactic acid from organic phase was attempted in a microporous hollow fiber (MHF) membrane device by aqueous NaCl solution. A satisfactory recovery was accomplished, signifying the great potential of integrating membrane back extraction with extractive fermentation process for lactic acid production.     

Reversed phase extraction chromatography using solutions of nitric acid as eluants

Approximately 40 ions have been chromatographed on thin layers of silica gel impregnated with Alamine 336-S, Alamine 336-S oxide, tri-n-octylarsine oxide, tri-n-octylphosphine oxide or tri-n-butyl phosphate, and on non-impregnated silica gel. Solutions of 0.2–15 N HNO₃ are used as eluants. R_F spectra and a number of separations are reported. The ions are classified into four groups according to their chromatographic behaviour, which is explained on the basis of anion exchange, solvation, hydrolysis and interaction with the support.Data on the extraction of HNO₃ and the co-extraction of water are reported. The behaviour of Alamine oxide and tri-n-octylarsine oxide parallels that of high-molecular-weight amines: extraction proceeds through anion exchange. Nitric acid taken up in excess of the stoichiometric amount is mainly present in the organic phase as part of the ion [O₂NO…HONO₂]⁻. On the other hand, with tri-n-octyl-phosphine oxide (TOPO) and tri-n-butyl phosphate (TBP), extraction proceeds through solvation; TOPO·HNO₃, TOPO·2HNO₃ and TBP·HNO₃ are the species present in the organic extracts.     

Solvent Modification in Ion-Pair Extraction: Effect on Sodium Nitrate Transport in Nitrobenzene Using a Crown Ether

A comparative quantitative analysis of the effect of solventmodifiers on the ion-pair extraction of an inorganic salt by a crown ether was conducted with the aim of advancing the understanding of transport of highly hydrophilic metal ions from aqueous salt solutions. Two classes of solvent modifiers that possess electron-pair donor (EPD) or hydrogen-bond donor (HBD) groups were investigated. The equilibrium constants corresponding to the extraction of sodium nitrate into nitrobenzene (NB) employing model neutral host cis-syn-cis-dicyclohexano-18-crown-6 (compound 1) with and without solvent modifier were determined using the SXLSQI computer model. For a series of EPD modifiers—including tri-n-butyl- and tri-phenylphosphate, tri-n-butyl- and tri-phenylphosphine oxide, N,N-di-n-butyl- and N,N-di-phenylacetamide—the enhancement of the NaNO₃ extraction by compound 1 was found to be dependent on the hydrogen-bond acceptance ability of the modifier as quantified by the β solvatochromic parameter. A HBD modifier 3,5-di-t-butylphenol (compound 8), which forms strong hydrogen bonds with nitrate anion in NB, exhibited even greater enhancement of the NaNO₃ extraction by compound 1. The determined extraction constants were correlated with the β- or α-solvatochromic parameters of the solvent modifiers and linear trends were observed. Hydrogen bond interaction between compound 8 and nitrate anion in the presence of the sodium-loaded crown ether in the extraction phaseswas studied by vibrational spectroscopy.     

Recovery of manganese(II) by electrodialysis with liquid membranes based on di(2-ethylhexyl)phosphoric acid

Electrodialysis membrane extraction of manganese(II) from sulfuric acid solutions with liquid membranes containing di(2-ethylhexyl)phosphoric acid and tri-n-octylamine in 1,2-dichloroethane was studied. The effect of the electrodialysis conditions and the composition of the organic phase and aqueous solutions on the transport rate of manganese(II) ions was examined. The conditions of quantitative recovery of the metal from a 0.01 M MnSO₄ solution were determined.     

Separation of uranium and thorium using tris(2-ethylhexyl) phosphate as extractant

The distribution behavior of uranium and thorium has been investigated in a biphasic system of different aqueous nitric acid concentrations and a solution of tris(2-ethylhexyl) phosphate (TEHP) inn-dodecane at 25°C. The effect of different uranium and thorium concentrations in the aqueous phase on the extraction of these metal ions is evaluated. These results indicate that TEHP is a better choice than tri-n-butyl phosphate (TBP) for the separation of²³³U from the irradiated thorium matrix.     

Electrodialysis Extraction and Electrodeposition of Lead(II) in Systems with Liquid Membranes

The extraction of lead(II) ions from nitric acid solutions through liquid membranes under galvanostatic electrodialysis with metal electrodeposition from the receiving solution of perchloric, nitric, or acetic acids is studied. The solitons of di(2-ethylhexyl)phosphoric acid with additives of tri-n-octylamine in 1,2-dichloroethane are used as liquid membranes. The effect of the current density of the electrodialysis and the composition of the initial aqueous solution and receiving solution (catholyte), as well as the composition of liquid membranes on the rate of membrane transport and electrodeposition of the lead(II) ions, is investigated. The optimal conditions of the process are determined. Fine-grained and highly adherent lead deposits are obtained on a platinum cathode during the deposition from perchloric acid solutions. It is shown that the degree of extraction of lead(II) ions from the initial aqueous solution is higher than 90% in the process, while the degree of electrodeposition amounts to 60% within 5 h of electrodialysis.

     

Extraction of polyvanadates by means of amines

The present paper is aimed at obtaining quantitative information on the extraction of polyvanadates from aqueous solutions with benzene solutions of tri-n-octylamine and Primene JMT with respect to initial pH value of aqueous solution and the ratio of volumes of the organic and aqueous phase. The predominant species in acidic solutions at concentrations in excess of 0.01 M are decavanadates. The extraction equilibria were studied within the range of pH 2–4. At this concentration of sulfuric acid the species V₁₀O₂₆(OH)^4– and V₁₀O₂₇(OH)^5– prevail. Supposing that the nonideality of the aqueous phase does not play an important role and that the activity coefficient of the amine sulfate remains constant, the nonideal behavior of the extraction system can be explained by the hydration of complexes in the organic phase. On the basis of suggested reactions and mass balance equations the comparison of experimental and calculated equilibrium data was done.     

The extraction of low-concentrations of gold(I) with 198Au as a radiotracer

The solvent extraction of gold from alkaline cyanide solution was studied by using ¹⁹⁸Au as a radiotracer. The influence of several variables on the gold extraction, including the concentration of gold, the molar ratio of extractants to gold(I), the volume percentage of cosolvent and the pH value of the aqueous phase, was investigated. The results indicated that the radioactive tracer technique is a quick, accurate, and convenient tool to investigate the extraction behavior of an element existing in low concentrations. The experimental results indicated that the studied amines, tetradecyldimethylbenzylammonium chloride, N1923 and tri-n-octylamine, could be used as extractants for the recovery of gold from aqueous alkaline cyanide solutions.     

Associative Organotin Polymers. 2. Solution Properties of Symmetric Trialkyltin Fluorides

The solubilities and viscosities of four novel symmetric tri-n-alkyltin fluorides in various organic solvents were studied. It is shown that these compounds do behave as transient polymers. Increasing the length of the n-alkyl chain beyond n-butyl imparts considerable solubility to this class of associative polymers and offers no steric hindrance to polymer chain formation. The effects of concentration, solvent type, temperature, and brine on the solution viscosities were also studied. These associative polymers effectively viscosify compressed gases (having liquid-like densities), such as propane and n-butane. They can therefore be used in enhanced oil recovery operations as well as in fracturing of oil wells.     

On the separation of Co and Ni from chloride media withAliquat 336-TBP andAliquat 336-TOPO

Summary The extraction behaviour of Co and Ni chlorides withAliquat 336-TBP andAliquat 336-TOPO (Aliquat 336: tri-n-octylmethylammonium chloride,TBP: tri-n-butylphosphate,TOPO: tri-n-octylphosphine oxide) was investigated. The synergistic action ofTOPO in the extraction of Co and Ni withAliquat 336 manifested itself in an increase of the distribution ratio of Co with increasing ofTOPO concentration at constantAliquat 336 concentration without deterioration of the separation factor Co/Ni which still was above 200. Mixed complexes of the general formulaMeCl_2+mA_mB_n (Me: Co or Ni,A:Aliquat 336, A:TBP orTOPO) withm ranging from 2 to 5 andn from 1 to 3 were present in the organic phase of both systems. The coexistence of several synergistic Co/Ni species in the equilibrium organic phase is reported for the first time.

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Zur Abtrennung von Co und Ni aus chloridhaltigen Medien mitAliquat 336-TBP undAliquat 336-TOPO

Zusammenfassung Das Extraktionsverhalten von Kobalt- und Nickelchloriden mitAliquat 336-TBP undAliquat 336-TOPO (Aliquat 336: Tri-n-octylmethylammoniumchlorid,TBP: Tri-n-butylphosphat,TOPO: Tri-n-octylphosphinoxid) wurde untersucht. Die synergistische Wirkung vonTOPO bei der Extraktion von Co und Ni mitAliquat 336 manifestiert sich in einer Erhöhung des Verteilungsverhältnisses von Co mit steigenderTOPO-Konzentration, ohne daß dadurch der Co/Ni-Trennfaktor verschlechtert wird (> 200). Für beide Systeme konnten in der organischen Phase gemischte Komplexe der allgemeinen FormelMeCl_2+m A _mB_n nachgewiesen werden (Me: Co oder Ni,A:Aliquat 336,B:TBP orderTOPO,m : 2–5,n: 1–3). Zum ersten Mal wird über die Koexistenz verschiedener synergistischer Co/Ni-Spezies in der organischen Phase im Gleichgewicht berichtet.

     

Ion-pair extraction of some sympathomimetics: Description of an extraction model for terbutaline and investigation of some factors influencing the recovery of sympathomimetics

The ion-pair formation of terbutaline, a resorcinolamine, was studied during extraction into ethyl acetate, a slightly polar organic solvent. Factors influencing the extraction, e.g., the concentration of various ions in the aqueous phase, are considered. Terbutaline is extracted as a simple ion-pair without the formation of higher adducts. The extraction of some Sympathomimetics is also described with respect to the nature of the organic solvent, the drug and the extracting anion. Factor analysis is applied to the data, and the reliability of predicted values is discussed. A search for a correlation between the factor analysis parameters characterizing the aqueous—organic phase systems and their physical properties led to a correlation between these parameters and interfacial tension; this result is explained by the macroscopic model of a solid surface (i.e., of the extracted compound) in contact with two fluids.     

Electrodialysis Separation of Copper(II) and Platinum(IV) with Liquid Membranes Based on Di(2-Ethylhexyl)Phosphoric Acid

Separation of copper(II) and platinum(IV) in extraction from binary acid chloride solutions with liquid membranes containing technical-grade di(2-ethylhexyl)phosphoric acid with addition of tri-n-octyl amine in 1,2-dichloroethane under the conditions of the galvanostatic electrodialysis was studied. The influence exerted by the current density and composition of aqueous solutions and liquid membranes on the rate and selectivity of copper(II) extraction was analyzed. The optimal conditions of metal separation were determined.     

Thermodynamic study of extraction of cerium(III) and yttrium(III) with tributyl phosphate

To increase the efficiency of hydrometallurgical processing of lean rare-earth raw material, the effect of salt anion and metal cation on the characteristics of Ce(III) and Y(III) recovery from dilute aqueous solutions with tri-n-butyl phosphate was studied on the basis of the thermodynamic theory of extraction.Translated from Zhurnal Prikladnoi Khimii, Vol. 77, No. 9, 2004, pp. 1430–1434.Original Russian Text Copyright © 2004 by Chirkst, Litvinova, Chistyakov, Ionova.     

Synergistic effect of tri-<Emphasis Type="Italic">n</Emphasis>-butyl phosphate (TBP) or tri-<Emphasis Type="Italic">n</Emphasis>-octyl phosphine oxide (TOPO) with didodecylphosphoric acid (HDDPA) on extraction of uranium(VI) and thorium(IV) ions

Importance of removal of radioactive elements from wastewater was the motivation behind this work. Synergistic solvent extraction of U(VI) and Th(IV) ions from perchlorate solution using didodecylphosphoric acid (HDDPA) incorporated with tri-n-butyl phosphate (TBP) or tri-n-octylphosphine oxide (TOPO) as a synergists have been studied for the first time. The effects of HDDPA concentration, synergist’s concentration, pH values and temperature on the extraction process have been studied. The thermodynamic parameters of the extraction process for these ions were calculated. It was found that the synergistic contribution of TOPO is higher than TBP in the extraction of Th(IV) and U(VI).     

Fast atom bombardment mass spectra of some alkylammonium 4-toluenesulfonate salts

The fast atom bombardment positive ion mass spectra of low molecular weight alkylammonium 4-toluenesulfonate salts are dominated by cluster ions of the type [(AB)_nA]⁺ or [(AB)_nH]⁺, where A is a cation, B an anion, n an integer from 0 to 4. With one exception the base peak is the cation A⁺.     

Fluorimetric determinations by ion-pair extraction : Part V. Studies on ion-pair extraction with the fluorescent anion 9,10-dimethoxyanthracene-2-sulphonate

The fluorescent anion 9,10-dimethoxyanthracene-2-sulphonate has been studied in ion-pair extractions. Its ability to extract amines and quaternary ammonium compounds was investigated by fluorimetric determination of extraction and dissociation constants with methylene chloride as organic phase for two amines (amitriptyline and protriptyline) and two quaternary ammonium ions (tetrabutyl-and tetrapropylammonium). The optical properties of the anion and its ion pairs were characterized by quantum yield of fluorescence and a fluorescence sensitivity index. The determination of two of the ion pairs was studied, both after extraction to an organic phase and after a subsequent back-extraction of the anion component to an aqueous phase. Recoveries and standard deviations are given.     

Nitrosation of Dodecahydro-closo-Dodecaborate Anions in Aqueous and Nonaqueous Solutions

Nitrosation of dodecahydro-closo-dodecaborate anions with nitrous acid in an aqueous solution and with isoamyl nitrite and nitrosyl chloride in nonaqueous solutions was studied. The main reaction product is the mononitrosoundecahydro-closo-dodecaborate anion. Conditions were selected for the preparation of the nitroso-substituted anion in the highest yield as alkylammonium, tetraphenylphosphonium, and alkali-metal salts. The salts were studied using IR, UV, and ¹¹B NMR spectroscopy.     

Ion-exchange rate limitation on a polymer-supported phase transfer catalytic reaction

The ion-exchange rate limitation on the kinetics of the series substitution reactions between hexachlorocyclotriphosphazene (NPCl₂)₃ and 2,2,2-trifluoroethanol (HOCH₂CF₃) by polystyrene-bound tri-n-butylammonium ion in an organic solvent/alkaline solution was studied. It was found that the diffusional limitation involves both ion diffusion and organic reactant diffusion within the catalyst pellet. The displacement reaction rate of (NPCl₂)₃ in the organic phase was limited by the particle diffusion and the intrinsic reactivity together. The film diffusion in the bulk solution limited the rate of ion exchange. The mass transport of the ion-exchange step in the aqueous phase was not improved by increasing the concentration of NaOCH₂CF₃. Drastic kinetic rate improvement was achieved with proper adjustment of the volume of the aqueous solution which was a low concentration of salt in the aqueous phase.     

Ligand-accelerated liquid membrane extraction of metal ions

A method has been developed to enhance the liquid membrane extraction of heavy metals such as cobalt, copper and nickel. The method consists of introducing anion ligands, such as acetate, to the aqueous solution containing metal ions. In the absence of a ligand in the aqueous phase, it takes about 15 min for a 80% cobalt recovery, while only 2 min are needed for a 95% recovery with the addition of 0.1 M acetate in the feed solution. The ligand effects on liquid membrane extraction are rationalized in terms of the labile nature of the ligand—metal complexes, the distribution coefficients of the metal ions, the interfacial and surface tensions, and by the nuclear magnetic r̀esonance (NMR) spectra of the metal—organic complexes.