Hydraulic Conductivity and Swelling of Nonprehydrated GCLs Permeated with Single-Species Salt Solutions

The influence of single-species salt solutions of various concentration, cation valence, and pH on swelling and hydraulic conductivity of nonprehydrated GCLs was examined. At similar concentration, swell was largest with NaCl, KCl, and LiCl solutions (monovalent cations Na+, K+, and Li+) and smallest with LaCl3 solutions (trivalent cation La3+). Intermediate swell volumes were obtained with divalent solutions (CaCl2, MgCl2, ZnCl2, and CuCl2). Analogous results were obtained from hydraulic conductivity tests. GCL specimens permeated with solutions containing divalent or trivalent cations had higher hydraulic conductivity than GCLs permeated with monovalent solutions or deionized water, unless the divalent or trivalent solutions were very dilute (≤0.01 M). Hydraulic conductivity increased as the concentration increased, and at high concentration (1 M) only small differences existed between hydraulic conductivities measured with all solutions. Swelling and hydraulic conductivity were related to size of the hydrated cation for monovalent cations, but no relationship was observed for different species of divalent and trivalent cations provided that the valence was the same. However, pH only influenced swelling and hydraulic conductivity when the pH was very low (<3) or very high (>12).     

Recovery of Cr(III) from Tannery Spent Chrome Liquor for Reuse

This paper embodies details on the extraction behavior of Cr(III) along with Al(III), Fe(III), Mg(II), Mn(II), Co(II), Ni(II), and Cu(II) from hydrochloric acid media employing the Cyanex 301-toluene system. All of these metals, except Cr(III), Mg(II), and Mn(II), are extracted into the organic phase. This property of the extractant has been used to separate Cr(III) from the binary mixtures. The partition data have been extended onto spent chrome liquor, and this waste has been treated in such a manner so that it becomes suitable for use in trivalent plating baths. The hydrolytic stability and recycling capacity has been reported. Because the concentration of Cr(III) in the waste is much lower than that required for chromium depositions in Cr(III) plating baths, a concentration step using MgO as a precipitating agent has been appended. To summarize, this paper envisages a new approach to tannery waste management that focuses on treating spent chrome liquors using a solvent extraction technique in such a manner that the waste becomes suitable for use in trivalent plating baths. This would not only help abate pollution but also recover the metal in a pure form.     

Selective separation of nickel from cobalt in ammoniacal solutions by emulsion type liquid membranes using 8-hydroxyquinoline (8-HQ) as mobile carrier

The selective separation and concentration of nickel from ammoniacal solutions containing nickel and cobalt by an emulsion liquid membrane (ELM) technique using 8-hydroxyquinoline (8-HQ) as carrier has been examined. The emulsion liquid membrane consists of a diluent (kerosene), a surfactant (ECA 4360J), a carrier (8-HQ), and a stripping solution (0.025 M EDTA solution, buffered at pH 4.0). Cobalt (II) in the 6 M ammonia feed solution was oxidised to cobalt (III) by adding H₂O₂ and the pH adjusted to 10 with hydrochloric acid (HCl). The important variables were found to be membrane composition, ammonia concentration, diluent type, surfactant concentration, extractant concentration, EDTA concentration in the stripping solution, pH of the feed and the stripping solutions, phase ratio, and treatment ratio. It was possible to selectively extract 96.5 to 99.0% of nickel from a mixture of nickel and cobalt.     

磷酸盐沉淀法除铬热力学研究

除铬是含铬电镀污泥湿法冶金过程重要步骤.针对磷酸盐沉淀法从溶液中净化除铬过程进行热力学分析,绘制了25 ℃时Me-P-H₂O(Me: Cr(III), Zn(II), Cu(II), Fe(II), Fe(III), Ni(II))系组浓度对数-pH图,利用热力学平衡图对磷酸盐沉淀法从含铁等金属元素中净化除铁和磷酸铬碱分解过程进行热力学分析.结果表明,pH值为1.0 ~ 5.0磷酸盐形成由易至难依次为Cr(III)>Fe(III) >Fe(II)>Ni(II)>Cu(II)>Zn(II); 磷酸盐沉淀法难以有效地将Cr(III)与Fe(III)分离,而可分离Cr(III)和Fe(II),且较优pH约为2;整个pH值范围Me-P-H₂O系可以分为难溶磷酸盐稳定区、Me(OH)_n稳定区; 高pH区磷酸盐中的Me转变为稳定的Me(OH)_n,实现磷酸盐碱分解.验证实验表明,加入1.1倍理论量的磷酸钠,控制沉淀pH值为2.0,铬、铁、锌、铜、镍沉淀率分别为94.12 %、5.51 %、0.33 %、0.22 %、0.34 %; 氢氧化钠分解磷酸铬时,磷、铬浸出率分别为90.63 %、5.10 %,实现磷铬有效分离.实验与理论基本相符.      

Synergistic extraction of iron(III) at higher concentrations in D2EHPA-TBP mixed solvent systems

The extraction of iron(III) from chloride solutions at macrolevel concentration by different solvents such as tri-n-butyl phosphate (TBP), di(2-ethylhexyl) phosphoric acid (D2EHPA), and their mixture in various proportions has been investigated at different acid concentrations. The synergistic extraction of iron(III) with a mixture of TBP and D2EHPA was studied and the results were compared with that of the extraction by individual solvent alone. An increase in the concentration of the synergist, TBP, in the D2EHPA-TBP solvent system resulted in an increase in the synergistic co-efficient value. The experimental data are treated graphically to explain the formation of organic phase extracted species, and the equilibrium extraction constants for the species are determined. It is found that a maximum of two molecules of TBP are adducted to the extracted species of the corresponding nonsynergistic system. Stripping of iron(III) with hydrochloric acid from loaded D2EHPA was found to increase with an increase in acid concentration. In the case of D2EHPA-TBP mixtures, stripping efficiency was increased with an increase in acid concentration up to a certain level and then it was decreased. The experimental results indicate that an iron exchange reaction between loaded D2EHPA and TBP proceeds during stripping at a higher concentration of hydrochloric acid (from mixed loaded solvent system). A plausible mechanism for iron(III) extraction and stripping has been discussed.     

Zn-exchange and M?ssbauer studies on the [Fe-Fe] derivatives of the purple acid Fe(III)-Zn(II)-phosphatase from kidney beans

In order to perform M?ssbauer studies, Zn(II) in the Fe(III)-Zn(II) purple acid phosphatase of the red kidney bean has been exchanged by incubating the semiapoenzyme with 57Fe(II). The resulting Fe(III)-57Fe(II) enzyme has 125% activity, compared with that of the Zn(II) enzyme. It can be oxidized by H2O2 or peroxydisulfate to the Fe(III)-57Fe(III) species with a 30-times lower activity. Incubation of the metal-free apoenzyme with 57Fe(II) in the presence of O2 leads to the 57Fe(III)-57Fe(II) species which is stable in dilute solutions, but partially oxidized during the concentration procedure to the 57Fe(III)-57Fe(III) enzyme. Limited reduction of the oxidized enzyme with ascorbate delivers a mixture of the Fe(II)-Fe(II)/Fe(III)-Fe(III) species, but not the mixed valent Fe(III)-Fe(II) species, indicating that after the transfer of the first electron the second electron of the ascorbate radical is immediately transferred to the second Fe(III). The M?ssbauer spectra of the oxidized species show at 4.2 K two quadrupole doublets with delta of 0.51 mm/s and 0.53 mm/s and delta E of 1.46 and 0.96 mm/s indicating high spin Fe(III) in two different binding sites, obviously with a higher asymmetry in the chromophoric Fe(III) site. The values are too low for a mu-oxo bridge. The mixed-valent Fe(III)-Fe(II) species shows two quadrupole doublets with delta values of 0.55 mm/s and 1.14 mm/s and delta E values of 1.43 mm/s and 3.01 mm/s at 70 K for high spin Fe(II) and Fe(III), but the signal of the Fe(II) component shows magnetic patterns at 4.2 K indicating a half-integer spin system with antiferromagnetic coupling. The Fe(II)-Fe(II) system exhibits two quadrupole doublets with delta values of 1.18 mm/s and 1.22 mm/s and with delta E values of 3.69 mm/s and 2.68 mm/s again indicating a higher asymmetry in the originally chromophoric Fe(III)-binding site. Addition of phosphate shows only minor differences in the oxidized enzyme and in the mixed valent Fe(III)-Fe(II) system. Interaction with O2 is discussed.     

Mixed solvent systems for the extraction and stripping of iron(III) from concentrated acid chloride solutions

The extraction of concentrated iron(III) from acid chloride solutions has been investigated with methyl isobutyl ketone (MIBK), tri-n-butyl phosphate (TBP), di(2-ethylhexyl) phosphoric acid (D2EHPA), and their mixtures in various proportions, at different acid concentrations. On comparing the extraction of iron(III) with mixed and individual extractant, it was found that both D2EHPA-MIBK and D2EHPA-TBP mixtures exhibit synergism, the latter having better extraction ability. The synergistic coefficients, at different initial acid concentrations for each mixed extractant system, were evaluated and compared. An increase in the concentration of MIBK and TBP in the mixed organic resulted in higher synergistic coefficient. The stripping of iron(III) from loaded D2EHPA was found to increase with the strip feed acid concentration, while from loaded organic mixtures, it initially increased and then decreased. Stripping of iron(III) from D2EHPA-MIBK loaded solvent is better then D2EHPA-TBP. The extracted iron species formed and the stripping reactions have been proposed. Ultraviolet visible spectra of the stripped organic phase support the result and the proposed mechanisms.     

厌氧环境下邻菲罗啉分光光度法测定纤维水镁石中Fe(II)与Fe(III)

纤维水镁石中同时存在有不同价态的Fe即Fe(II)与Fe(III),这对开展水镁石相关研究具有重要意义。而不同价态Fe含量测定过程中存在Fe(II)在空气中易氧化成Fe(III)而导致测定不准确的问题。针对该问题,实验采用厌氧培养箱作为操作环境,对纤维水镁石的处理均在厌氧条件下进行。利用邻菲罗啉与经盐酸羟胺还原产生的总Fe(II)显色反应原理测定纤维水镁石中的总Fe,之后测定过程中不加盐酸羟胺与邻菲罗啉反应测定溶液中的Fe(II),利用总Fe与Fe(II)的差值测定Fe(III),从而实现了邻菲罗啉分光光度法对纤维水镁石中Fe(II)与Fe(III) 的准确测定。试验发现在波长为510nm,显色体系pH值为2~5,显色时间为10min条件下,Fe(II)质量浓度在0.02~5.0mg/L范围内与其吸光度符合比尔定律,校准曲线的相关系数为0.9999。采用实验方法对两个纤维水镁石样品分别进行6次平行测定,结果显示总Fe、Fe(II)及Fe(III)的相对标准偏差(RSD,n=6)均小于1%。采用电感耦合等离子体原子发射光谱法(ICP-AES)进行全Fe测定结果对照,结果表明两种方法的测定结果保持一致。     

The dioxygenation rate in lipoxygenase catalysis is determined by the amount of iron (III) lipoxygenase in solution

The dioxygenation rate in reactions catalyzed by lipoxygenase-1 from soybeans has been measured as a function of the enzyme present in the Fe(III) form with rapid kinetic techniques. The experiments were carried out at pH 10, 25 degree C. The product concentration and the fraction of iron (III) lipoxygenase were monitored by measuring the absorbance at 243 nm and the tryptophan fluorescence at 330 nm (excitation at 287 nm), respectively. In reactions started with 1.3 microM iron (II) lipoxygenase and 9 microM linoleate, the initial rate, r(init) (estimated from the increase in absorbance over the initial 0.02 s of the reaction), is very small (4 s-1). In contrast, when the reactions are started with 1.3 microM (III) lipoxygenase, r(init) is large (150 s-1). In reactions started with mixtures of iron(II) and iron(III) lipoxygenase, r(init) is linearly related to the initial concentration of the Fe (III) enzyme form. Redistributions of the Fe(II) and Fe(III) enzyme forms during the reaction with 12 nM enzyme and 10, 50, or 100 microM linoleate appear to be directly reflected in changes in the dioxygenation rate. The observations provide solid evidence for the hypothesis that only iron (III) lipoxygenase can catalyze the hydrogen abstraction step in the dioxygenation reaction, and thus can be regarded as the active enzyme species. The observed dynamics are accurately predicted by a nonallosteric, two-step model for lipoxygenase catalysis [Schilstra et al. (1992) Biochemistry 31, 7692-7699].     

Oxygen equilibrium properties of chromium (III)-iron (II) hybrid hemoglobins

Cr(III)-Fe(II) hybrid hemoglobins, alpha 2(Cr) beta 2(Fe) and alpha 2(Fe) beta 2(Cr), in which hemes in either the alpha- or beta-subunits were substituted with chromium(III) protoporphyrin IX (Cr(III)(PPIX), were prepared and characterized by oxygen equilibrium measurements. Because Cr(III)PPIX binds neither oxygen molecules nor carbon monoxide, the oxygen equilibrium properties of Fe(II) subunits within these hybrids can be analyzed by a two-step oxygen equilibrium scheme. The oxygen equilibrium constants for both hybrids at the second oxygenation step agree with those for human adult hemoglobin at the last oxygenation step (at pH 6.5-8.4 with an without inositol hexaphosphate at 25 degrees C). The similarity between the effects of the Cr(III)PPIX and each subunits' oxygeme on the oxygen equilibrium properties of the counterpart Fe(II) subunits within hemoglobin indicate the utility of Cr(III)PPIX as a model for a permanently oxygenated heme within the hemoglobin molecule. We found that Cr(III)-Fe(II) hybrid hemoglobins have several advantages over cyanomet valency hybrid hemoglobins, which have been frequently used as a model system for partially oxygenated hemoglobins. In contrast to cyanomet heme, Cr(III)PPIX within hemoglobin is not subject to reduction with dithionite or enzymatic reduction systems. Therefore, we could obtain more accurate and reasonable oxygen equilibrium curves of Cr(III)-Fe(II) hybrids in the presence of an enzymatic reduction system, and we could obtain single crystals of deoxy-alpha 2(Cr) beta 2(Fe) when grown in low salt solution in the presence of polyethylene glycol 1000 and 50 mM dithionite.     

Metals extraction with carboxylic acids. II. Effect of temperature on the extraction of Cu,Ni, Co(II), Zn,Fe(III) and Co(III)

The relation between the extraction temperature and the coefficient of distribution of various metals between aqueous phases and kerosene solutions of Versatic acid has been investigated.Using a mathematical procedure, it was established that with increasing temperature the distribution coefficient changes if the composition of the metal-Versatic complex is temperature-dependent. In the case of trivalent iron a reversible increase in distribution coefficient occurs when the temperature is raised. It is suggested that this is due to a reversible depolymerization of the complex. The distribution coefficient of trivalent cobalt also increases with temperature, but here the increase is irreversible, possibly because the number of covalently bound carboxylate groups changes.In general, the distribution coefficient of metals which do not show variations in the composition of their complexes with Versatic, such as Cu, Ni, Co(II) and Zn, does not change appreciably with temperature.     

Extraction and separation of In(III), Ga(III) and Zn(II) from sulfate solution using extraction resin

The separation of In(III), Ga(III) and Zn(II) from sulfate solution has been studied using an extraction resin containing 2-ethylhexyl phosphoric acid mono(2-ethylhexyl) ester (P507 extraction resin). The effect of pH on the extraction of each metal was determined. Extraction isotherms were then constructed at selected pH. Results show that In(III) is first extracted from aqueous solutions at pH 2.0 using this resin while Ga(III) and Zn(II) are co-extracted at pH 3.0. Their separation can be carried out using HCl of different concentrations as eluants. The saturation adsorption capabilities of indium(III) and gallium(III) were evaluated as 47.2 and 31.0 mg/g or 0.41 and 0.44 mmol/g, respectively. The molar ratio of metal ion: P507 reagent on resin was about 1:3. Loaded resins can be regenerated, and the metals can be recovered selectively. Two fixed-bed columns arranged in-series were successfully used for the separation and recovery of these three metal ions from a multi-component solution.     

Extraction of chromium (III) from spent tanning baths

Extraction of chromium(III) from a model spent tanning bath of the leather industry has been investigated using ammoniated and non-ammoniated di(2-ethylhexyl)phosphoric acid (D2EHPA) and bis(2,4,4-trimethylpentyl)phosphinic acid (Cyanex® 272). Chromium extraction of 95% by 15% (v/v) D2EHPA, 10% (v/v) isodecanol in kerosene and 86.1% by 15% (v/v) Cyanex® 272, 10% (v/v) p-nonylphenol in kerosene was obtained at equilibrium pH values of 4.0 and 5.0, respectively. The separation of small amounts of iron (III) and aluminium (III) present in the solution along with the Cr(III), was also examined and it was found that Cyanex® 272 was a better reagent than D2EHPA. The slow kinetics of extraction and stripping observed in the case of AI(III) was advantageous for its separation from Fe(III) at low pH values. Difficulties faced in the stripping of loaded metals were also studied because only about 80% chromium recovery by 8 M HCl was obtained from both solvents. The incomplete stripping of the metal may be a result of the formation of a stable species in the organic phase and needs further investigation. The Cr(III) can be recovered as chloride from the strip liquor and recycled for retanning purposes.     

Iron(III) removal from base-metal electrolyte solutions by solvent extraction

The use of a novel synergistic solvent extraction mixture based on an alkylated derivative of 8-hydroxyquinoline (Kelex 100) and di(2-ethylhexyl) phosphoric acid (D2EHPA) for the selective removal of iron(III) from strong sulphuric acid solutions is described. Stripping of the iron from the loaded organic solvent is effected by reacting with hydrogen to reduce iron(III) to iron(II), which subsequently is easily stripped with a weak acid solution. The applicability of the process for iron removal from an actual copper electrolyte is also demonstrated.     

The extraction of iron(III) from aqueous acid solutions by di(2-ethylhexyl)phosphoric acid

The extraction of iron(III) from aqueous solutions containing sulphuric, hydrochloric and nitric acids by di(2-ethylhexyl)phosphoric acid (DEHPA) in kerosene has been investigated under different conditions. As a result, it is found that although extraction is dominated by an ion-exchange reaction, the rate of iron(III) extraction from sulphuric acid solutions to reach equilibrium is relatively slow in comparison with that from hydrochloric or nitric acid solutions. In the extraction from aqueous solutions containing hydrochloric or nitric acid, however, the DEHPA combines with iron(III) according to the solvating reaction at higher aqueous acidity. From studies on the rate of the extraction from sulphuric acid solutions, examined under non-equilibrium, it is confirmed that dependencies of extraction rate on hydrogen ion and DEHPA concentrations are in the first and inverse first orders, respectively. The hydrolyzed species is considered to interpret the extraction mechanism in this system.     

Concentration of Cu(II), Co(II), and Ni(II) ions with <Emphasis Type="Italic">N</Emphasis>-(2-hydroxyethyl)alkyl amines

Regularities of the recovery of Cu(II), Co(II), and Ni(II) ions from ammonia solutions by N-(2-hydroxyethyl)alkyl amines (HEA), namely, regions of pH values of maximal recovery of M(II), the influence of the radical length in the HEA series, and precipitation time, were investigated. It is found by conductometric titration that the ratios in complexes are [Cu(II)] : [HEA] = 2 : 1, 1 : 1, and 1 : 2; [Co(II)] : [HEA] = 1 : 1 and 1 : 2; and [Ni(II)] : [HEA] = 1 : 1 and 1 : 2. Complexes of N-(2-hydroxyethyl)dodecyl amine with Cu(II) and Ni(II) ions are isolated and identified. Their composition is confirmed by the data of IR spectroscopy and elemental analysis. Using N-(2-hydroxyethyl)dodecylamine, a reagent of the HEA series,, which is optimal in regards to the totality of its properties, as an example, the effectiveness of compounds as collectors during the removal of nonferrous metals from waste waters by the ion flotation method is shown. The maximal degree of recovery of the M(II) ions from ammonia solutions by this method is 99.4% for Cu(II) ions (C _res = 0.34 mg/L), 96.8% for Co(II) (C _res = 1.55 mg/L), and 99% for Ni(II) (C _res = 0.60 mg/L).     

Extraction of vanadium from direct acid leach solution of converter vanadium slag

Direct acid leaching of converter vanadium slag by titanium dioxide waste is eco-friendly and efficient, but with low selectivity. This novel technique can result in a vanadium solution which contains chromium(III), aluminium(III), magnesium(II), manganese(II) and high amount of iron(II) and iron(III). Bis (2-ethylhexyl) phosphoric acid (D2EHPA) and tri-butyl-phosphate (TBP) diluted with sulphonated kerosene were applied for vanadium extraction from the multi-element leach solution. The effects of the initial pH, concentration of D2EHPA, ratio of organic to aqueous phase, and the extraction time on the extraction efficiency of vanadium were investigated in saponification and unsaponifiable systems, respectively. The results showed that the vanadium extraction percentage can be up to 97% and the iron extraction percentage can be less than 10% in a thirteen-stage counter-current simulation test and the separation coefficient between vanadium and iron can reach to 109.8. Furthermore, vanadium(IV) can also be separated from other impurities such as aluminium(III), magnesium(II), manganese(II), chromium(III) efficiently. The loaded organic phase was stripped by 184?g?L^?1 sulphuric acid solution in a three-stage counter-current stripping process and with the total vanadium stripping percentage of greater than 99.5%. In the end, the vanadium pentoxide products with a purity of 99.14% were obtained.     

The interaction of antitumor-active anthraquinones with biologically important redox couples: I. Spectrophotometric investigation of the interaction of carminic acid and mitoxantrone with the iron (II, III) and copper (I, II) redox couples

Studying the interaction of antitumor-active anthraquinones with biologically important redox couples is important in understanding the possible reductive or oxidative mode of metabolism of these antineoplastic agents coupled with the formation of free radicals. The interactions of such anthraquinones, i.e., carminic acid (CA) and mitoxantrone (Mx) with iron(II, III) and copper(I, II) redox couples in oxygenated and deaerated solutions, were investigated by UV-Visible and IR-spectroscopy. The superoxide radical reagent, nitroblue tetrazolium (NBT), was added to the metal and anthraquinone solutions and their binary mixtures at varying pH. Formazan, the reduction product of NBT, was produced mainly as a result of Fe(II)-NBT and Fe(II)-Mx-NBT interactions. The ternary mixtures of the lower valencies of iron and copper with CA and NBT exhibited intensive charge-transfer bands in the visible region, while metal-Mx-NBT combinations did not produce such bands, possibly due to the blockage of the redox-active aminoethanolamine side-chains of Mx through coordination with the metals. Copper-Mx combinations showed an oxygen sensitivity as spectral evidence was obtained for the oxidative transformation of Mx to the cyclic primary metabolite. The results were evaluated in regard to the possible oxidative activation of the studied anthracenediones with iron and copper systems.     

The effect of Fe(II) and Fe(III) on the efficiency of copper electrowinning from dilute acid Cu(II) sulphate solutions with the chemelec cell: Part I. Cathodic and anodic polarisation studies

The results are presented from an investigation into the effect of the Fe(III) and Fe(II) concentration on the current efficiency for copper electrowinning using the Chemelec cell. The results are from polarisation studies of acidic sulphate electrolytes containing Cu(II), Fe(II) and Fe(III). The mass transfer coefficients for these cationic species are determined, and the effect of using different anode materials on the overvoltage for the oxidation of Fe(II) and oxygen evolution is also examined.     

Extraction of gold(III) in hydrochloric acid solution using monoamide compounds

The extraction and separation properties of Au(III) using two monoamide compounds, N,N-di-n-octylacetamide (DOAA) and N,N-di-n-octyllauramide (DOLA), which have different side chain lengths attached to the carbonyl carbon (CH₃ for DOAA and n-C₁₁H₂₃ for DOLA), were investigated. The solvent extraction of some precious and base metals (Au(III), Pd(II), Pt(IV), Rh(III), Fe(III), Cu(II), Ni(II) and Zn(II)) in HCl solutions was carried out using DOAA and DOLA diluted with n-dodecane and 2-ethylhexanol. A good selectivity for Au(III) extraction with 0.5 M extractant is obtained at lower HCl concentrations (< 3.0 M) in both systems. The extractability of Au(III) with DOAA is greater than that with DOLA. In the 0.5 M DOAA–3.0 M HCl system, a third phase is formed when the Au(III) concentration in the initial aqueous phase is over 39 g/L. In contrast, third phase formation is not found in the 0.5 M DOLA–3.0 M HCl system, and its loading capacity of Au(III) is about 79 g/L. The Au(III) extracted in the organic phase is effectively back-extracted by 1.0 M thiourea in 1.0 M HCl solution in both systems, while some thiourea is precipitated using the organic phase containing 20 g/L of Au(III). The back extraction of Au(III) using water is poor in the DOAA system, but possible in the DOLA system.