The solvent extraction of nickel from acidic solutions using synergistic mixtures containing pyridinecarboxylate esters. Part 2: Systems based on alkylsalicylic acids

The synergistic solvent extraction of nickel and cobalt by pyridinecarboxylate esters (2-, 3- or 4-C₅H₄N.CO.OR) in admixture with 3-bromo- or 3-nitro-derivatives of 5-alkylsalicylic acids was studied. Nickel is extracted more strongly than cobalt in all cases and, for systems containing a given pyridinecarboxylate, the pH₅₀ values (pH values for 50% extraction) of both metals decrease in the order: alkylsalicylic acid > bromo-derivative > nitro-derivative. For systems containing a given salicylic acid, the separation between the pH₅₀ values for nickel and cobalt was found to increase in the order: pyridine 2-ester < 4-ester ≈ 3-ester. The extractability of divalent base metals from sulphate solutions by mixtures of isodecyl 3- or 4-pyridinecarboxylate and 3-bromo- or 3-nitro-5-nonylsalicylic acid in Shellsol K decreases through the series: Cu > Ni > Co ≈ Zn > Ca > Mg. In single-stage batch extraction experiments with a simulated leach liquor containing Ni 2·2, Cu 0·5, Ca 0·4 and Mg 5·0 g dm⁻³ (and smaller amounts of other base metals), adjustment of the equilibrium pH value to between 3·3 and 4·0 with magnesium oxide gave extractions of nickel and copper of 97–100%, with co-extractions of calcium and magnesium of <0·5 and <0·1%, respectively. Amongst the metals present in lower concentrations, manganese (2–5%) and lead (5–10%) were extracted only slightly whereas cobalt (40–80%), zinc (15–65%) and iron (100%) were more strongly extracted.     

EXTRACTION CHEMISTRY OF COBALT AND NICKEL BY DI(1-METHYLHEPTYL)PHOSPHINIC ACID

The fundamental characteristics and mechanism of extraction of cobalt (II) and nickel(II) by di-(1-methylheptyl) phosphinic acid (DMHPA) were studied. The extraction ability of cobalt(II), nickel (II) and various metals by DMHPA decreases in the order Fe(III) > Zn ? Pb(II) > Mn(II) > Cu(II) > Co(II) > Mg > Ca > Ni(II). The difference of the pH_½ values for nickel and cobalt reaches 2.06 pH units, which is apparently greater than those from extraction by di(2-ethylhexyl)phosphoric acid (DEHPA)and 2-ethyl-hexyl ester 2-ethylhexylphosphonic acid(DHEHPA).The slope analysis and IR spectroscopy reveal that the stoichiometrics of cobalt and nickel extracted species are Co(HA₂)₂ and Ni(HA₂)₂(H₂O)₂ respectively. As demonstrated by the study of the electronic spectroscopy the structure of the extracted complexes were shown as tetrahedral and octahedral configuration respectively. Furthermore, the coordination field parameters of the complexes were calculated.     

Preparations and characterizations of Ca doped Ni–Mg–Mn nanocrystalline ferrites for switching field high-frequency applications

Ca-doped Ni–Mg–Mn spinel ferrites with compositions of Ni_0·5Mg_0·3Mn_0.2Ca_xFe_2-xO₄ (x = 0, 0.1, 0.2, 0.3, 0.4, 0.5) were prepared via sol-gel auto-ignition technique. TGA/DTA, FTIR, XRD, FESEM, and VSM were employed to evaluate the thermal, spectral, structural, morphological, and magnetic features of Ca-doped Ni–Mg–Mn spinel ferrites. TGA/DTA curves show the weight loss in the sample. This weight loss was attributed to the oxidation and decomposition of the sample contents at a temperature of 500 °C. XRD reveals a single-phase structure of the Ni–Mg–Mn nano ferrites. A single-phase orthorhombic structure was confirmed for Ca-doped Ni–Mg–Mn ferrites. Structural parameters such as lattice parameter, ‘da’, ‘db’, ‘dc’, and ‘dv’ were evaluated using unit cell software. The absorption peaks at 427 to 538 cm^?1 confirmed the spinel structure, which was evaluated using FTIR. FESEM analyses showed that the agglomerations increased with the doping of Ca in Ni–Mg–Mn ferrites. Remanence, Y–K angles, saturation, coercive force, magnetic squareness, magnetic moment, and anisotropy constant were determined for Ca-doped Ni–Mg–Mn spinel ferrite samples. It is noticed that saturation increases from 29.157 to 51.322 emu/g, whereas remanence increased from 5.34 to 9.40 emu/g, respectively. The permeability, anisotropy constant, and magnetic moments were also found to increase with Ca doping. However, the Y–K angles increased with Ca concentration in Ni–Mg–Mn nano ferrites. In addition, the switching field distribution (SFD) and high-frequency response of all the Ca-doped Ni–Mg–Mn samples were also evaluated. Ca-doped Ni–Mg–Mn samples are suggested to be suitable for switching, filters, inductors, and microwave absorption applications because of the superparamagnetic nature of the prepared spinel ferrites.     

Reactive solvent extraction of amino acids with cationic extractants

A mixture of amino acids (arginine, phenylalanine, alanine, glycine and aspartic acid) in solution was extracted by four acidic extractants (dinonylnaphthalenesulphonic acid (DNNSA), di(2-ethylhexyl)monothiophosphoric acid (D2EHPA(S)), di(2-ethylhexyl)phosphoric acid (D2EHPA) and Versatic 10) in toluene. The extractive capacity of the organic phase for the amino acids, using DNNSA, D2EHPA(S) and D2EHPA was found to decrease in the order arginine>phenylalanine>alanine>glycine>aspartic acid, although at low pH values phenylalanine>arginine occurred for D2EHPA(S) and D2EHPA. Separation factors derived for pairs of amino acids were in the range 2·0 (glycine–aspartic acid) to 20·1 (alanine–glycine). The extractive and loading capability of the extractants for the amino acids was found to decrease in the order DNNSA>D2EHPA(S)>D2EHPA>Versatic 10, which follows the reverse order of their respective acid dissociation constants. DNNSA was shown to be a promising extractant for the extraction and fractionation of amino acids. © 1998 SCI     

Synergistic effects in the solvent extraction of some divalent metals by mixtures of versatic 10 acid and pyridinecarboxylate esters

Pyridinecarboxylate esters were found to cause appreciable synergistic shifts in the pH₅₀ values for the extraction of some divalent base metals by solutions of Versatic 10 acid in xylene. For n-octyl 3-pyridinecarboxylate, the synergistic shifts decreased in the order Ni > Co > Cd > Cu ≈ Fe > Mn > Zn, and for the commercial extractant Acorga DS5443A in the order Ni > Cu > Co > Fe > Cd > Mn > Zn. No synergistic effects were observed for divalent lead, calcium and magnesium. On the basis of the pH₅₀ values obtained, several possible practical metal separations are suggested. No loss of metal-loading capacity was found when the organic phases were contacted with 1 M sulphuric acid for prolonged periods at 30°C. The effect of changes in the structure of a series of isomeric octyl pyridinecarboxylates is reported for one of the smaller cations studied (copper), as well as for one of the larger cations (cadmium).     

Synergistic Silver Extraction from Hydrochloric Acid Solutions with Triisobutylphosphine Sulfide in the Presence of Organic Proton-Donor Additives

Silver chloride extraction from hydrochloric acid solutions with triisobutylphosphine sulfide (CYANEX 471, L) in the presence of organic proton-donor additives (HR) was studied. Both alkyl-, bromo-, nitro-substituted phenols, and organic acids of various structures were used as additives. A new synergistic effect (S) was found to take place in the presence of the additives. The degree of the synergistic effect in the systems containing phenols decreases in the series 4-nitrophenol > 4-bromophenol > 4-tert-butylphenol > 2,6-dimethylphenol > 2-methyl-6-cyclohexylphenol > 2,6-bis(tert-butyl) phenol. In the systems containing organic acids, the following series is observed: dinonylnaphthalenesulfonic acid (DNNSA) > 4-tert-butylphenol > caprylic acid > di(2-ethylhexyl)phosphoric acid > bis(2,4,4-trimethylpentyl)phosphinic acid. Based on the analysis of the extraction data and the IR and NMR spectra of the extracts, it was concluded that an increase in the silver extraction with CYANEX 471 in the presence of HR is due to the formation of the compound [AgCl?2L?HR] in the organic phase. It was shown that a mixture of CYANEX 471 and 4-tert-butylphenol can be used for the highly selective extraction of silver from hydrochloric acid solutions containing metal impurities (Ni, Cu, Co, Zn, Fe(III), and Na). The mixtures of CYANEX 471 with alkylphenols or DNNSA, in which the high synergistic effects (S ≥ 10 and ≥ 50, respectively) take place, can efficiently be used for processing different industrial silver chloride solutions.     

Steam reforming of ethanol on Ni–CeO2–ZrO2 catalysts: Effect of doping with copper, cobalt and calcium

Steam reforming (SR) and oxidative steam reforming (OSR) of ethanol were investigated over undoped and Cu, Co and Ca doped Ni/CeO₂–ZrO₂ catalyst in the temperature range of 400–650 °C. The nickel loading was kept fixed at 30 wt.% and the loading of Cu and Co was varied from 2 to 10 wt% whereas the Ca loading was varied from 5 to 15 wt.%. The catalysts were characterized by various techniques, such as surface area, temperature programmed reduction, X-Ray diffraction and H₂ chemisorption. For Cu and Co doped catalyst, CuO and Co₃O₄ phases were detected at high loading whereas for Ca doped catalyst, no separate phase of CaO was found. The reducibility and the metal support interactions were different for doped catalysts and varied with the amount and nature of dopants. The hydrogen uptake, nickel dispersion and nickel surface area was reduced with the metal loading and for the Co loaded catalysts the dispersion of Ni and nickel surface area was very low. For Cu and Ca doped catalysts, the activity was increased significantly and the main products were H₂, CO, CH₄ and CO₂. However, the Co doped catalysts showed poor activity and a relatively large amount of C₂H₄, C₂H₆, CH₃CHO and CH₃COCH₃ were obtained. For SR, the maximum enhancement in catalytic activity was obtained with in the order of NCu5. For Cu–Ni catalysts, CH₃CHO decomposition and reforming reaction was faster than ethanol dehydrogenation reaction. Addition of Cu and Ca enhanced the water gas shift (WGS) and acetaldehyde reforming reactions, as a result the selectivity to CO₂ and H₂ were increased and the selectivity to CH₃CHO was reduced significantly. The maximum hydrogen selectivity was obtained for Catalyst N (93.4%) at 650 °C whereas nearly the same selectivity to hydrogen (89%) was obtained for NCa10 catalyst at 550 °C. In OSR, the catalytic activity was in the order N > NCu5 > NCa15 > NCo5. In the presence of oxygen, oxidation of ethanol was appreciable together with ethanol dehydrogenation. For SR reaction, the highest hydrogen yield was obtained on the undoped catalyst at 600 °C. However, with calcium doping the hydrogen yields are higher than the undoped catalyst in the temperature range of 400–550 °C.     

Simultaneous oxidative conversion and CO2 or steam reforming of methane to syngas over CoO–NiO–MgO catalyst

CO₂ reforming, oxidative conversion and simultaneous oxidative conversion and CO₂ or steam reforming of methane to syngas (CO and H₂) over NiO–CoO–MgO (Co: Ni: Mg=0·5: 0·5:1·0) solid solution at 700–850°C and high space velocity (5·1×10⁵ cm³ g⁻¹ h⁻¹ for oxidative conversion and 4·5×10⁴ cm³ g⁻¹ h⁻¹ for oxy-steam or oxy-CO₂ reforming) for different CH₄/O₂ (1·8–8·0) and CH₄/CO₂ or H₂O (1·5–8·4) ratios have been thoroughly investigated. Because of the replacement of 50 mol% of the NiO by CoO in NiO–MgO (Ni/Mg=1·0), the performance of the catalyst in the methane to syngas conversion process is improved; the carbon formation on the catalyst is drastically reduced. The CoO–NiO–MgO catalyst shows high methane conversion activity (methane conversion >80%) and high selectivity for both CO and H₂ in the oxy-CO₂ reforming and oxy-steam reforming processes at ⩾800°C. The oxy-steam or CO₂ reforming process involves the coupling of the exothermic oxidative conversion and endothermic CO₂ or steam reforming reactions, making these processes highly energy efficient and also safe to operate. These processes can be made thermoneutral or mildly exothermic or mildly endothermic by manipulating the process conditions (viz. temperature and/or CH₄/O₂ ratio in the feed). © 1998 Society of Chemistry Industry     

Biosorption of heavy metals (Cd,Cu, Ni,Pb, Zn) by chemically-reinforced biomass of marine algae

Particles of two different sizes (0·105–0·295 mm and 0·84–1.00 mm diameter) of two marine algae, Sargassum fluitans and Ascophyllum nodosum, were crosslinked with formaldehyde (FA), glutaraldehyde (GA) or embedded in polyethylene imine (PEI), followed by glutaraldehyde crosslinking. They were used for equilibrium sorption uptake studies with cadmium, copper, nickel, lead and zinc. The metal uptake by larger particles (0·84–1·00 mm) was higher than that by smaller particles (0·105–0·295 mm). The order of adsorption for S. fluitans biomass particles was Pb > Cd > Cu > Ni > Zn, for A. nodosum copper and cadmium change places. Uptakes of metals range from q_max = 378 mg Pb g^?1 for S. fluitans (FA, big particles), to q_max = 89 mg Zn g^?1 for S. fluitans (FA, small particles) as the best sorption performance for each metal. Generally, S. fluitans is a better sorbent material for a given metal, size and modification, although there were several exceptions in which metal sorption by A. nodosum was higher. The metal uptake for different chemical modifications showed the order GA > FA > PEI. A comparison of different sorption models revealed that the Langmuir sorption model fitted the experimental data best.     

Use of gypsum/brucite mixed precipitate instead of gypsum in Portland cement

The possibility of replacing the natural gypsum used in cement production by a chemical precipitate consisting of gypsum (CaSO₄ ·2H₂O) and brucite (Mg(OH)₂), was investigated. This precipitate is a by‐product of a new hydrometallurgical process, which was developed in order to treat economically low‐grade nickel oxide ores. More specifically, it is obtained by hydrolytic precipitation of magnesium at temperatures not exceeding 80 °C, from sulfate solutions which result from heap leaching of nickel oxide ores with dilute sulfuric acid at ambient temperature, using calcium hydroxide as a neutralizing agent. The mixture generally consists of 20–30% non‐fibrous magnesium hydroxide, 60–75% gypsum and any excess of calcium hydroxide, depending on the precipitation conditions. In the present work, a mixture was produced by hydrolytic precipitation at 25 °C, using 1.1 times the stoichiometric quantity of Ca(OH)₂ required to precipitate all of the magnesium. The possibility of using the above precipitate as a substitute for gypsum in cement was examined by testing four different cement mixtures, one reference sample, containing 4.5% gypsum and 0.5% anhydrite ((PC)_Ref) and another three with 4.1%, 5.2% and 6.3% of gypsum/brucite mixed precipitate ((PC)_B/G), in the place of gypsum. All samples were tested by determining the grindability, setting time, expansion and compressive strength. The results of the physico‐mechanical tests showed that the replacement of natural gypsum by the above precipitate did not affect negatively the quality of the produced cements. Copyright © 2005 Society of Chemical Industry     

Sorption enhanced steam methane reforming by Ni/CaO/mayenite combined systems: Overview of experimental results from European research project ASCENT

Work Package 4 (WP4) of the European research project ASCENT developed combined sorbent-catalyst materials (CSCM) for sorption enhanced steam methane reforming (SESMR), based on nickel (Ni) and calcium oxide (CaO). This work summarizes the whole experimental study carried out in ASCENT WP4 on Ni/CaO/mayenite systems obtained from wet mixing and wet impregnation synthesis methods. Effects from Ni precursor (Ni (CH₃COO)₂ · 4H₂O or Ni(NO₃)₂ · 6H₂O), Ni load (from 3 wt%-10 wt%), and free CaO load (from 0 wt%-54 wt%) were investigated for 26 materials by means of characterizations and reforming reactivity tests in a packed-bed microreactor (650°C, 1 atm). Thanks to comparative analyses of the results, evidence emerged about the detrimental influence of low Ni/CaO ratio on the reforming catalytic activity of solid inventories, made of CSCM or even of the raw mixing of CaO-mayenite and Ni-mayenite particles. Catalytic materials were active towards reforming only when derived from Ni(NO₃)₂ · 6H₂O. Based on this, the best CSCM (with the lowest free CaO content and the highest Ni load from nickel nitrate) was chosen to further study its industrial applicability by multicycle SESMR/sorbent-regeneration tests in a bench-scale packed-bed rig and attrition tests according to ASTM D5757-11. The CSCM was stable and active for 200 cycles with regenerations in N₂ at 850°C, while a progressive loss of its activity occurred with regenerations in CO₂ at 925°C as the cycle number increased due to Ni sintering. Its performance in the attrition tests was comparable to that of calcined dolomite.     

Synthesis,extraction, and anti‐bacterial studies of some new bis‐1,2,4‐triazole derivatives part I

A series of new bis triazole Schiff base derivatives (4) were prepared in good yields by treatment of 4‐amino‐3,5‐diphenyl‐4H‐1,2,4‐triazole (3) with bisaldehydes (1). Schiff bases (4) were reduced with NaBH₄ to afford the corresponding bisaminotriazoles (5). All the new compounds were characterized by IR, ¹H NMR and ¹³C NMR spectral data. Their overall extraction (log K_ex) constants for 1 : 1 (M : L) complexes and CHCl₃/H₂O systems were determined at 25 ± 0.1°C to investigate the relationship between structure and selectivity toward various metal cations. The extraction equilibrium constants were estimated using CHCl₃/H₂O membrane transfer with inductively coupled plasma‐atomic emission spectroscopy spectroscopy. The stability sequence of the triazole derivatives in CHCl₃ for the metal cations was exhibited a characteristic preference order of extractability to metal ions [Fe(III) > Cu(II) > Pb(II) > Co(II) > Ni(II) > Mn(II) > Zn(II) > Mg(II) > Ca(II)]. The compounds were tested for anti‐microbial activity applying agar diffusion technique for 11 bacteria. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Generation of H2 gas from polystyrene and poly(vinyl alcohol) by milling and heating with Ni(OH)2 and Ca(OH)2

A two-step process to generate H₂ gas; first by milling polystyrene (PS) or poly(vinyl alcohol) (PVA) with Ni(OH)₂ and Ca(OH)₂, followed by heating of the milled product in the second-step was performed in this work. Polymer and hydroxide mixtures obtained after milling for 60 min and heating to 700 °C showed H₂, CH₄, H₂O, CO, and CO₂ as the main gaseous products with H₂ as the dominant gas generated between 350 and 500 °C. Analysis of the gaseous products by TG-MS and gas-chromatography, and solid products by TG-DTA and XRD shows that CO₂ gas was fixed as CaCO₃ at temperatures between 350 to 600 °C allowing generation of H₂ gas with concentrations over 95% for PS and over 98% for PVA. The results in this study show that milling of solid based hydrocarbon compounds with nickel and calcium hydroxides allows dispersion of nickel to hydrocarbon surfaces and facilitates C-C bond rupture in polymer(s) during heating at temperatures below 500 °C, at the same time calcium adsorbs CO₂. This process could be developed to treat hydrocarbon based wastes such as plastics, biomass or combinations at low temperatures avoiding syngas purification and separation steps.     

Purification of Nickel Sulfate by Batch Cooling Crystallization

Cooling crystallization was successfully carried out in a batch cooling crystallizer from impure acidic solutions to recover nickel as nickel sulfate salt with three different cooling rates. The compositions of the solutions included impurities of sodium, magnesium, chloride, and sulfuric acid to mimic industrial nickel electrowinning process solutions. The results show that NiSO₄·6H₂O mainly crystallized, and its solubility and purity decreased with the increase in the mass ratio of chloride to sulfate. Cooling rates did not have a significant influence on crystal purity; however, it did affect the filter cake moisture; lower moisture can be obtained with a lower cooling rate. The sequence of impurity removal efficiency from high to low was Cl > Na > Mg.     

ION-EXCHANGE PROPERTIES OF HYDROUS TITANIUM DIOXIDE WITH A FIBROUS FORM OBTAINED FROM POTASSIUM DITITANATE

ABSTRACT

Ion-exchange properties of a new type of hydrous titanium dioxide with a fibrous form, which was obtained from potassium dititanate (K₂O(TiO₂)2), have been studied. The pH titration curve snowed that this material behaved as a bifunctional ion-exchanger. Distribution coefficients of some divalent metal ions on this material were measured as a function of pH and the selectivity series were found to be Ba > Sr > Ca > Mg for alkaline earth metal ions and Cu > Zn > Mn > Co > Ni for divalent transition metal ions. Large separation factors were obtained between some metal ion pairs and the mutual separations such as Cu from Sr, Ca, Mg, Co and Ni, and Mg from Ba and Zn have been achieved on columns of this material.     

New catalysts for poly(ethylene terephthalate)-bisphenol a polycarbonate reactive blending

The effects of various catalysts on the reactive blending of poly(ethylene terephthalate) (PET) and bisphenol A polycarbonate (PC) was investigated. The various catalysts employed for PET syntheses, Ti(OBu)4, SmL₃, EuL₃, Ca + Sb, CeAc₃, Er(NO₃)₃·B₁₂C₄ and Tb (acac)₃·diPy (where L is o-formylphenolate; B₁₂C₄ is a crown ether, benzo-12-crown-4; acac is acetylacetonate; and diPy is 2,2′-dipyridyl) have shown a different catalytic activity toward exchange reactions. Solubility tests, in solvents able to separate unreacted PET and PC, and selective degradation of the PC segments, combined with ¹H NMR spectroscopy and size exclusion chromatography, made it possible to order the catalysts according to their catalytic activity: Ti(OBu)4 ? SmL₃ > EuL₃ > Ca + Sb > CeAc₃～Er(NO₃)·B₁₂C₄ > Tb (Acac)₃·diPy ≈ 0. © 1995 John Wiley & Sons, Inc.     

Chaleurs de dissolution et de protonation de la piperazine et de ses derives dans divers melanges eau-ethanol

The thermodynamic functions ΔG⁰_n, ΔH⁰_n and ΔS⁰_n for the protonation of piperazine (Pz), 2-methylpiperazine (2MPz), N-methyl-piperazine (NMPz) and N-phenyl-piperazine (NPPz) have been determined by potentiometric and calorimetric procedures at 25°C in mixtures of water-ethanol with 73·4 and 85·4% ethanol by weight (I = 0·1M NaClO₄). The values obtained, also the heats of dissolution of these diamines in the similar mixtures with 0%, 52%, 73·4%, 85·4% and 100% ethanol are advanced as evidence for the important solvation properties of the nitrogen doner.     

Preparation and characterization of spherical nickel-doped carbonized resin as hydrogenation catalysts: II. Thermal decomposition of resin and preparation of metal-doped catalysts with different nickel loadings

A series of spherical nickel and calcium-doped carbonized resins (Ni-Ca/C), containing Ni metal from 0% to 12% with nearly monodisperse Ni particles distributed from 9 Å to 20 Å and having microporous structure with specific surface area from 510 m²/g to 650 m²/g and high catalytic activity for hydrogenation, were prepared by carbonizing nickel and calcium-doped bead-shaped polymer-D152 Amberlytes (Ni-Ca/D152) having different nickel loadings by exchanging calcium-doped Dl52 resins (Ca/D152) with Ni²⁺ of different contents in solution as well as C₂H₅OH solution. The advantage of exchanging Ca/D152 with (x = 1-6) solution is to make bead-shaped Ni-Ca/C with low nickel loadings, and exchanging with Ni²⁺ (C₂H₅OH, H₂O) solution is preferable to make bead-shaped Ni-Ca/C with high nickel loadings. To increase the understanding of the pyrolysis mechanism of Ni-Ca/D152, GC, DTA, TGA, XRD and elemental analysis were used to investigate the carbonization process and properties of Ni-Ca/C. Nickel and calcium in D152 significantly accelerated the carbonization process and the steam activation process of carbonized resin. The thermal decomposition of D152 mainly occurred between 380 °C and 520 °C. The reduction of nickel ion to metallic nickel and the formation of CaCO₃ from Ca(OH)₂ and CO₂ took place in the carbonization process at 500 °C and below.     

The Influence of Extractant Structure on the Solvent Extraction of Uranium(VI) and Thorium(IV) from Nitrate Media by Dialkyl Sulphoxides

The solvent extraction of uranium(VI) and thorium(IV) from sodium nitrate solutions (0·20–6·00 M ) by a series of dialkyl sulphoxides with different structures was studied. For sulphoxides with n-alkyl groups (R₂SO, where R = n-hexyl, n-octyl and n-decyl) using 0·20 M solutions in xylene, the extractions of both uranium and thorium are relatively high, and the values of the separation factor β_Th^U are correspondingly low (≈20). Replacement of an n-hexyl group by a cyclohexyl group has little effect on metal extraction, whilst the introduction of a second cyclohexyl group causes a slight decrease in extraction. Similarly, there is little variation in the extraction of uranium and thorium through the series of asymmetrical compounds RR′SO, where R = n-octyl and R′ = cyclopentyl, cyclohexyl or cyclooctyl. When two aromatic (phenyl) rings are introduced into the sulphoxide, however, the extraction of both metals falls to zero. For the series of isomeric compounds R₂SO with C₈ alkyl groups, the separation factors increase in the order: R = n-octyl, 2-ethylhexyl, 2-octyl, 3-octyl, which is also the order of increasing steric bulk of the alkyl group. For these compounds, slope analysis studies are consistent with the formulation of the extracted metal complexes as UO₂(NO₃)₂(R₂SO)₂ and Th(NO₃)₄(R₂SO)₃. © 1997 SCI.     

COBALT–NICKEL SEPARATION: THE EXTRACTION OF COBALT(II) AND NICKEL(II) WITH BIS(2-ETHYLHEXYL) PHOSPHINIC ACID (PIA-8) IN TOLUENE

The extraction behaviour of cobalt(II) and nickel(II) from sulfate solutions with bis(2-ethylhexyl) phosphinic acid (PIA-8) in toluene has been studied. Quantitative extraction of Co(II) was observed at pH 5.0–5.9 while that of Ni(II) at pH 6.8–7.0 with 0.03 M PIA-8 in toluene. The difference in pH_0.5 for Co(II) and Ni(II) was 1.9. The stoichiometry of the extracted species were determined by slope analysis method. The extraction reaction proceeds by cation exchange mechanism and the extracted species were Co · R₂(HR)₂ and Ni · R₂ · 2(HR)₂. Temperature dependance of the extraction equilibrium constants were determined to estimate the apparent thermodynamic functions (ΔG, ΔS and ΔH). The method was used for separation of cobalt(II) and nickel(II). Cobalt(II) was separated from nickel even at 1:20 (Co:Ni) ratio. The separation of cobalt(II) from nickel(II) was favoured with the increase in temperature.