Properties of electrolyte solutions relevant to high concentration chloride leaching. II. Density, viscosity and heat capacity of mixed aqueous solutions of magnesium chloride and nickel chloride measured to 90 °C

Results of density and viscosity measurements for aqueous solutions of MgCl₂ (0.5–3.5 mol L^− 1) and MgCl₂ + 10% NiCl₂ (0.5–3.5 mol L^− 1) at temperatures of 25, 60 and 90 °C show an almost linear increase in density with total concentration, while low nickel contents and temperature have comparatively small effects. Viscosities of MgCl₂ solutions rise sharply at 25 °C but are significantly lower at 90 °C. The viscosity of 3–4 mol kg^− 1 MgCl₂ at 90 °C is similar to water at 25 °C. Nickel has no significant effect on the viscosity of these solutions.Results of heat capacity measurements for aqueous solutions of MgCl₂ (0.5–3.5 mol L^− 1) and MgCl₂ + 10% NiCl₂ (0.5–3.5 mol L^− 1) at temperatures of 60 and 90 °C show that the heat capacities of these solution decrease significantly with total concentration, while the effects of low nickel contents and temperature are again comparatively small.     

Properties of electrolyte solutions relevant to high concentration chloride leaching I. Mixed aqueous solutions of hydrochloric acid and magnesium chloride

A computer code based on a Pitzer model has been developed for the comprehensive prediction of the thermodynamic properties of MgCl₂–HCl aqueous solutions over a wide range of conditions from 25 to 120 °C and from 0–350 g L^− 1 chloride. This code was applied to the calculation of (i) water activities and mean ionic activity coefficients for mixed aqueous solutions of hydrochloric acid and magnesium chloride over a wide range of concentrations and to 100 °C, (ii) solubilities of MgCl₂·6H₂O in MgCl₂–HCl solutions to 80 °C, (iii) partial pressures of HCl(g) and H₂O(g) over MgCl₂–HCl aqueous solutions at various temperatures and (iv) partial pressures of HCl(g) at the normal boiling point of these mixed electrolyte solutions. The model predictions are in excellent agreement with available experimental data and confirm evidence from the literature that MgCl₂(aq) and HCl(aq) mix almost ideally at constant water activity.     

Adsorption behavior of Cd(II) from aqueous solutions onto gel-type weak acid resin

The adsorption and desorption behaviors of Cd(II) on gel-type weak acid resin (GTWAR) have been investigated. The influence of operational conditions such as contact time, initial concentration of Cd(II), initial pH of solution and temperature on the adsorption of Cd(II) has also been examined. The results show that the optimal adsorption condition of GTWAR for Cd(II) is achieved at pH = 5.95 in HAc–NaAc medium. The maximum uptake capacity of Cd(II) is 282 mg/g GTWAR at 298 K. The adsorption of Cd(II) follows the Langmuir isotherm and Freundlich isotherm, and the correlation coefficients have been evaluated. Even kinetics on the adsorption of Cd(II) has been studied. The apparent activation energy E_a and adsorption rate constant k₂₉₈ values are 2.95 kJ/mol and 3.02 × 10^− 5 s^− 1, respectively. The calculation data of thermodynamic parameters which ΔS value of 110 J/(mol K) and ΔH value of 13.1 kJ/mol indicate the endothermic nature of the adsorption process. Whilst, a decrease of Gibb's free energy (ΔG) with increasing temperature indicates the spontaneous nature of the adsorption process. Finally, Cd(II) can be eluted by using 0.5 mol/L HCl solution and the gel-type weak acid resin can be regenerated and reused. The sample was described by IR spectroscopy and scanning electron micrographs (SEM).     

Effect of phosphate on lead removal during a copper recycling process from wastes using ammoniacal chloride solution

Techniques for the removal of lead have been studied in order to develop a hydrometallurgical copper recycling process consisting of copper leaching from wastes using an ammoniacal chloride solution and subsequent copper electrowinning. The solubility of Pb(II) in the ammoniacal chloride solution increased with ammonia concentration; this was attributable to the formation of a lead ammine complex. The lead dissolution was depressed from the order of 10^− 3 M to the order or 10^− 5 M by the addition of phosphate into the leaching solution because of the precipitation of chloropyromorphite (Pb₅(PO₄)₃Cl), while no significant effect was observed by the addition of carbonate. Linear sweep voltammetry and potentiostatic electrolysis in the solution containing Pb(II) revealed that lead was deposited during the copper electrowinning, even in the potential region more positive than the equilibrium redox potential for the Pb/Pb(II) couple on the lead electrode, because of the alloy formation with copper. In a galvanostatic electrolysis, however, the lead content at the electrodeposited copper cathode was found to be lower than 5 ppm at the current density range of 125–400 A/m², when the Pb(II) concentration in the electrolyte was 5 × 10^− 5 M. Since this Pb(II) concentration was achieved by the phosphate addition, these results indicated the effectiveness of phosphate for lead removal in the copper recycling process using the ammoniacal chloride solution.     

Extraction of Fe(III) from hydrochloric acid solutions using Amberlite XAD-7 resin impregnated with trioctylphosphine oxide (Cyanex 921)

Ferric ions were efficiently removed from HCl solutions using Amberlite XAD-7 resin impregnated with trioctylphosphine oxide (Cyanex 921). Iron was removed under the form HFeCl₄ through direct binding on the resin or by extraction with Cyanex 921 involving a solvation mechanism. High concentrations of HCl and intermediary extractant loadings were required for maximum sorption efficiency and rationale use of the extractant. At intermediary extractant loading (in the range 300–450 mg Cyanex 921 g^− 1) the maximum sorption capacity increased with extractant loading. Maximum sorption capacity slightly increased with temperature, the reaction is endothermic and the enthalpy change was found close to − 30.8 kJ mol^− 1. Sorption isotherms were fitted with the Langmuir equation and maximum sorption capacity reached values as high as 20–22 mg Fe g^− 1 in 3 M HCl solutions. Despite the good fit of experimental data with the pseudo second-order rate equation, sorption kinetics was controlled by the resistance to intraparticle diffusion. The intraparticle diffusion coefficient (D_e) varying in the range 1.2 × 10^− 11–4.7 × 10^− 10 m² min^− 1 was found to increase with metal concentration and with temperature, while varying the extractant loading it reached a maximum at a loading close to 453 mg Cyanex 921 g^− 1. The desorption of Fe(III) can be achieved using 0.1 M solutions of nitric acid, sulfuric acid, sodium sulfate and even water, maintaining high efficiencies for sorption and desorption for at least 5 cycles.     

Palladium(II) complexes adsorption from the chloride solutions with macrocomponent addition using strongly basic anion exchange resins, type 1

The use of the strongly basic anion exchange resins, type 1 such as Lewatit MP-500 and Lewatit MP-500A for palladium(II) complexes adsorption has been investigated. The adsorption process was carried out from the chloride solutions with macrocomponent (sodium chloride) addition (x M HCl–1.0 M NaCl; x M HCl–2.0 M NaCl) where the concentration of hydrochloric acid was constant and equal to x = 0; 0.1; 0.5; 1.0; and 2.0 M, respectively. The breakthrough curves of Pd(II) were determined and the sorption parameters (weight and bed distribution coefficients, working anion exchange capacity) were calculated. The pseudo-second kinetic order was applied in kinetic studies as well as to calculate the kinetic parameters. The values of the working anion exchange capacities (0.029 g/cm³; 0.028 g/cm³) for Lewatit MP-500 and Lewatit MP-500A (0.028 g/cm³; 0.027 g/cm³) in the 1.0 M NaCl and 0.1 M HCl–1.0 M NaCl solutions, respectively are really close and in other solutions under discussion Lewatit MP-500 possess slightly higher values of capacities, and therefore is insignificantly more efficient in the adsorption process of palladium(II) ions than Lewatit MP-500A. The equilibrium adsorption capacities changed in the range 8.84–9.99 and 8.40–9.38 mg/g for Lewatit MP-500 as well as 8.12–9.57 and 7.26–8.85 mg/g for Lewatit MP-500A in the chloride x M HCl-1.0 M NaCl and x M HCl-2.0 M NaCl solutions, respectively. The adsorption process proceeds according to the pseudo-second kinetic order.     

Adsorption of rhenium(VII) on 4-amino-1,2,4-triazole resin

The adsorption properties of 4-amino-1,2,4-triazole resin (4-ATR) for Re(VII) were investigated by static and dynamic adsorption–desorption measurements with ultraviolet–visible spectroscopy. The influence of conditions such as temperature, initial solution pH and contact time on the adsorption curve was studied. It was found that the 4-amino-1,2,4-triazole resin was suitable for adsorption of Re(VII). The saturated adsorption capacity was 354 mg·g^− 1resin at pH 2.6 in HAc–NaAc medium at 298 K. The adsorption rate constant was k₂₉₈ = 8.2 × 10^− 5 s^− 1. The adsorption behavior of 4-ATR for Re(VII) obeyed the Freundlich empirical equation; whilst changes in adsorption with temperature gave an enthalpy change ΔH  = − 11.8 kJ·mol^− 1. The molar ratio of the functional group of 4-ATR to Re(VII) was about 2:1. Re(VII) adsorbed on 4-ATR was eluted by 1.0 ~ 5.0 mol·L^− 1 HCl with 100% quantitative elution in 4.0 mol·L^− 1 HCl solution. The resin can be regenerated and reused without apparent decrease in adsorption capacity.     

Comparative leaching of a sulfidic gold ore in ionic liquid and aqueous acid with thiourea and halides using Fe(III) or HSO5 oxidant

The leaching of gold, silver and base metals from a sulfidic gold ore in the presence of an oxidant (peroxomonosulfate (HSO₅⁻) or iron(III)) and leaching agent (thiourea, chloride, bromide or iodide) is compared in 1-butyl-3-methylimidazolium hydrogen sulfate (bmimHSO₄) and chloride (bmimCl) ionic liquids, as well as in aqueous saturated K₂SO₄ as the solvent medium. Over 85% of gold and silver was recovered in the presence of HSO₅⁻/ thiourea at 25–50 °C in both bmimHSO₄ and bmimCl, with silver recovery significantly enhanced compared with that from aqueous sulfate medium. The leaching efficiency with HSO₅⁻ was similar to that with Fe(III) as oxidant in bmimHSO₄ and was far superior in bmimCl. With HSO₅⁻ /halide ion (Cl⁻, Br⁻, I⁻) as leaching agent, gold and silver recovery in bmimHSO₄, bmimCl or saturated aqueous K₂SO₄ improved from Cl⁻ to Br⁻ to I⁻, but only I⁻ gave a high recovery in the bmimCl ionic liquid due to the particular stability of the iodo complex anion in this medium. However, recovery was significantly higher than in an aqueous medium. Negligible recovery of base metals occurred in the ionic liquid medium, making it highly selective for Au and Ag. Concentration dependence studies with respect to halide and oxidant have defined optimum conditions for gold and silver recovery.     

Solubility prediction of malachite in aqueous ammoniacal ammonium chloride solutions at 25 °C

The solubility of malachite in the presence of ammonia, ammonium chloride and their mixed solution is calculated by a geochemical modeling code and is measured in a series of dissolution experiments using synthetic malachite at 25 °C. The simulated results show a good agreement with the experimental data gained at 25 °C. The predicted and experimental results indicate that the precipitate CuO limits the copper solubility in aqueous ammonia and Cu(OH)_1.5Cl_0.5 in aqueous ammonium chloride. For a mixed solution containing ammonia and ammonium chloride, highest copper solubility can be achieved by adjusting the [NH₃]/[NH₄Cl] ratio to about 2:1. The thermodynamic model presented rationalises the interactions between the different components and predicts the influence of changes in the concentration of ammonia and ammonium chloride on the copper solubility of malachite.     

Stability of 3CaO · Al2O3 · 6H2O in KOH + K2CO3 + H2O system for chromate production

In the novel clean chromate production process, the alkali liquor recycled to decompose the chromite ore mainly consists of KOH and K₂CO₃ which accumulates aluminium impurity and affects the quality of the product greatly. Aluminium impurity can be removed by adding CaO to precipitate as 3CaO · Al₂O₃ · 6H₂O (C₃AH₆). A study of the effects of various parameters, such as KOH concentration, K₂CO₃ concentration and temperature on the behaviour of C₃AH₆ show that C₃AH₆ is decomposed to 3CaO · Al₂O₃ · CaCO₃ · 11H₂O and CaCO₃ below 150 g L^− 1 KOH, and decomposed to Ca(OH)₂ above 150 g L^− 1 KOH. With K₂CO₃ concentration increasing, C₃AH₆ decomposes significantly, which results in more CaCO₃ or 3CaO · Al₂O₃ · CaCO₃ · 11H₂O produced. Temperature has a large positive effect on the decomposition of C₃AH₆ at 45 g L^− 1 KOH but has no significant effect at 150 g L^− 1 KOH. The optimal condition for removing aluminium impurity in the KOH + K₂CO₃ + H₂O system is 150 g L^− 1 KOH, 50 g L^− 1 K₂CO₃ and 80 °C.     

Some physicochemical properties of aluminum and iron chloride solutions

Some physicochemical properties of aluminum and iron chloride solutions are considered. The density and viscosity of aluminum and iron chlorides are plotted as functions of the FeCl₃/(FeCl₃ + AlCl₃) ratio and temperature, and pH of aluminum hydroxochlorides is plotted as a function of the Al₂O₃ content in a solution and its basicity (ratio of contents Al/Cl). The joint solubility of aluminum hydroxochloride and sodium chloride in water has been analyzed.     

Preparation and properties of fine hematite powders by hydrolysis of iron carboxylate solutions

Submicrometer, crystalline hematite (α-Fe₂O₃) particles were prepared by hydrolysis of organic iron carboxylate solutions using water at 175 °C for 30 minutes. The particle size of hematite was significantly dependent on the liquid-phase stirring speed and the organic compositions. The precipitation rate of hematite from the organic solution followed first-order kinetics. The precipitation rate increased markedly with increasing temperature, and the activation energy for the process was 94.6 kJ mol⁻¹. At 220 °C, the hydrolysis of iron carboxylate solution led to a mixture of hematite and magnetite (Fe₃O₄). The iron oxides prepared at 175 °C to 220 °C were found to be free from organic contamination by the starting material.     

Solubilities,densities and electrical conductivities of aqueous copper(I) and copper(II) chlorides in solutions containing other chlorides such as iron,zinc, sodium and hydrogen chlorides

With a view to industrial applications, solubilities, densities and electrical conductivities of aqueous copper(I) and copper(II) chlorides were measured in solutions containing other chlorides like those of iron, zinc, sodium and hydrogen.In these solutions copper(I) chloride shows a behaviour similar to that observed in pure CuClNaClHCl solutions. Increasing the FeCl₂ concentration decreases the solubility of CuCl less than increasing the ZnCl₂ concentrations does. Moreover, increasing total Cl^? concentration increases CuCl solubility if Cl^? is added as FeCl₂ and decreases CuCl solubility if Cl^? is added as ZnCl₂. NaCl solubility remains unchanged by FeCl₂ additions and is increased by ZnCl₂ additions.Copper(II) chloride also shows in these solutions a behaviour similar to that observed in pure CuCl₂NaClHCl solutions. FeCl₃ additions decrease CuCl₂ · 2 H₂O solubility in a more drastic manner than ZnCl₂ additions. However, NaCl additions have a much higher effect.These results can be qualitatively interpreted when taking into account the relative Cl^? donor or acceptor character of the constituent chloride salts of the solution.FeCl₂ additions slightly decrease the electrical conductivity of Cu(I) solutions. However, this can easily be compensated by a slight increase in temperature or in acidity.     

Speciation of the Fe(II)–Fe(III)–H2SO4–H2O system at 25 and 50 °C

This work presents theoretical and experimental results on the speciation of the Fe(II)–Fe(III)–H₂SO₄–H₂O system in concentrated solutions (up to 2.2 m H₂SO₄ and 1.3 m Fe). The aim was to study the chemical equilibria of iron at 25 and 50 °C in synthetic aqueous sulphuric acid solutions that contain dissolved ferric and ferrous ion species. Raman spectroscopy, volumetric titration and conductivity measurements have been carried out in order to study the presence of specific ions and to characterize the ionic equilibrium. A thermochemical equilibrium model incorporating an extended Debye–Hückel relationship was used to calculate the activities of ionic species in solution. Model calculations were compared with experimental results. Model simulations indicate that anions, cations and neutral complexes coexisted in the studied system, where the dominant species were HSO₄⁻, H⁺, Fe²⁺ and FeH(SO₄)₂⁰. This indicated that these solutions showed a high buffer capacity due to the existence of bisulphate ions (HSO₄⁻), which presented the highest concentration. A decrease in the concentration of H⁺ and Fe³⁺ took place with increasing temperature due to the formation of complex species. Standard equilibrium constants for the formation of FeH(SO₄)₂⁰ were obtained in this work: log K_f⁰ = 8.1 ± 0.3 at 25 °C and 10.0 ± 0.3 at 50 °C.     

Comparative study of dewatering characteristics of metal precipitates generated during treatment synthetic polymetallic and AMD solutions

The sludge dewatering characteristics expressed in terms of settling, filtration and centrifugation of metal precipitates generated during treatment of polymetallic solutions and synthetic acid mine drainage have been evaluated in this research. Results show that dewatering properties of metallic sludge vary depending on the type of matrix (Cl⁻; SO₄²⁻), precipitating agent, and metals present in effluent. Metal hydroxides (at pH 10.0) and metal phosphates precipitates (at pH 7.0) are amorphous in nature, thus difficult to dewater. In these treatment methods, the substitution of chloride matrix by sulphate one improves considerably dewatering properties (specific resistance to filtration = 6.60 × 10¹³ and 2.35 × 10¹³ m/kg for the chloride and sulphate matrix, respectively). In the case of sulphide and carbonate treatments (pH 8.0), precipitates obtained are semi crystalline, and crystalline form, respectively, and no influence of the matrix was detected on dewatering characteristics.     

Thermochemical Study on Ternary Solid Complex of La(Gly)2 (Ala)3 Cl3 ·2H2O (s)

The complex of lanthanum chloride with Glycine and Alanine, La(Gly)₂(Ala)₃Cl₃ · 2H₂O, was synthesized and characterized by IR, elementary analysis, thermogravimetric analysis, and chemical analysis. The dissolution enthalpies of LaCl₃ · 7H₂O(s), 2Gly(s) + 3Ala(s) and La(Gly)₂(Ala)₃Cl₃ · 2H₂O(s) were determined in 2 mol · L⁻¹ HCl by a solution-reaction isoperibol calorimeter. By designing a thermochemical cycle in terms of Hess' Law and through calculation, the reaction enthalpy of lanthanum chloride seven-hydrate with Glycine and Alanine was obtained: Δ_rH^θ_m(298.15 K) = (29.652 ± 0.504) kJ · mol⁻¹, and the standard enthalpy of formation of La(Gly)₂(Ala)₃Cl₃ · 2H₂O(s) Δ_fH^θ_m[La(Gly)₂ (Ala)₃Cl₃ · 2H₂O, s, 298.15 K] = −4467.6 ± 8.3 kJ · mol⁻¹.     

The dissolution of galena in ferric chloride media

The dissolution of galena (PbS) in ferric chloride-hydrochloric acid media has been investigated over the temperature range 28 to 95 °C and for alkali chloride concentrations from 0 to 4.0 M. Rapid parabolic kinetics were observed under all conditions, together with predominantly (>95 pet) elemental sulfur formation. The leaching rate decreased slightly with increasing FeCl₃ concentrations in the range 0.1 to 2.0 M, and was essentially independent of the concentration of the FeCl₂ reaction product. The rate was relatively insensitive to HCl concentrations <3.0 M, but increased systematically with increasing concentrations of alkali or alkaline earth chlorides. Most significantly, the leaching rate decreased sharply and linearly with increasing initial concentrations of PbCl₂ in the ferric chloride leaching media containing either 0.0 or 3.0 M NaCl. Although the apparent activation energy was in the range 40 to 45 kJ/mol (∼10 kcal/mol), this value was reduced to 16 kJ/mol (3.5 kcal/mol) when the influence of the solubility of lead chloride on the reaction rate was taken into consideration. The experimental results are consistent with rate control by the outward diffusion of the PbCl₂ reaction product through the solution trapped in pores in the constantly thickening elemental sulfur layer formed on the surface of the galena.     

Adsorption of Ce（ Ⅳ ） Anionic Nitrato Complexes onto Anion Exchangers and Its Application for Ce （Ⅳ） Separation from Rare Earths （ Ⅲ ）

Ceriumis one of the cheapest[1]and most abun-dant rare earths (RE) .However ,high purityis usual-ly required for its utilization in industry , where it isusedfor sulfur control insteels ,pyrophoric alloys ,ce-ramic ,catalyst support ,polishing powders ,etc .In its minerals ,as well as in the spent nuclearfuel ,ceriumis accompanied by other RE.They basi-cally exist in solution as stable RE(Ⅲ) species ,which makes their mutual separation rather difficult .In contrast to other RE, Ce(Ⅲ) can…     

Possible Involvement of NADPH Oxidase in Lanthanide Cation-Induced Superoxide Anion Generation in BY-2 Tobacco Cell Suspension Culture

A rapid and concentration-dependent generation of superoxide anion (·O-2), measured with a superoxide-specific Cypridina luciferin-derived chemiluminescent reagent, was observed when two lanthanide salts (LaCl3 and GdCl3) were added to tobacco (Nicotiana tabacum) cell suspension culture.Addition of superoxide dismutase (480 U·ml-1) and Tiron (5 μmol·L-1) to cell culture suspension decreases the level of lanthanide cation-induced ·O-2 generation, suggesting that ·O-2 generation is extra-cellular.Pretreatment of the cell culture suspension with diphenyleneiodonium (10 and 50 μmol·L-1), quinacrine (1 and 5 mmol·L-1) and imidazol (10 mmol·L-1), inhibitors of NADPH oxidase, notably inhibits the generation of superoxide induced by lanthanide cation, implying the possible involvement of activation of NADPH oxidase.In addition, addition of SHAM (1 and 5 mmol·L-1), azide (0.2 and 1 mmol·L-1), inhibitor of peroxidase, has no influence on ·O-2 generation.     

Solubility of titanium nitride in delta iron

Titanium nitride in microalloyed steels can be formed already in delta iron, as can be shown by thermodynamical calculations basing on measurements of the solubility in austenite or in the melt. The solubility products calculated with respect to delta iron differ up to one order of magnitude. Therefore, between 1420 and 1510°C a direct measurement was performed on pure Fe–Ti–N alloys yielding a solubility product (related to the composition TiN_1,0) of log L_TiN^α/δ = ?17205/T + 5.56. It is identical with that one calculated from the solubility in liquid iron. The differing results of calculations basing on the solubility in austenite are attributed to incorrect data of the Gibbs free solution energy of titanium in austenite. Starting from the present measurements and from the data reported with respect to pure titanium and to the nitrogen solubility a Gibbs free solution energy G_Ti,γ^H(x) – G_Ti,γ^R = ?40294 ? 13.66. T[J/mole] was deduced which is more negative than previous data.