Kinetics and mechanism of the conversion of covellite (CuS) to digenite (Cu1.8S)

Rates of conversion of covellite (CuS) to digenite (Cu_1.*S) in N₂ and various partial pressures of O₂ have been studied in the temperature range 260° to 400°C. The reaction is first order with respect to O₂ concentration in N₂?O₂ mixtures at 1 atm. The experimental activation energy for the conversion of CuS to Cu_1.8S is 23±3 kcal. In a nitrogen atmosphere, the conversion proceeds at a slower rate but with the same activation energy and leads to the formation of elemental sulfur instead of SO₂. An externally added small amount of iron powder (0.6 pct) increased the rate of conversion, but had no effect on the apparent activation energy. The rate-controlling reaction in the conversion mechanism is postulated to be Cu_1.8S→1.8Cu⁺+1.8e ^?+S at the Cu_1.8S/gas interface. Reduction of CuS by copper(I) ions and electrons occurs by a rapid reaction, 0.8 Cu⁺+0.8e ^?+CuS→Cu_1.8S at the CuS/Cu_1.8S interface, which steadily contracts with time.     

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.     

Substitution Recovery of Gold from Copper-Ethylenediamine-Thiosulfate Leaching Solution with Copper Power

The substitution method of recovering gold from thiosulfate-ethylenediamine (en)-Cu²⁺ leaching solution using copper powder was studied. The effects of reaction time, stirring speed, pH, thiosulfate concentration, en/Cu²⁺ molar ratio, Cu/Au⁺ mass ratio, and temperature on gold recovery were systematically examined. The experimental results showed that reaction time, stirring speed, thiosulfate concentration, en/Cu²⁺ molar ratio, Cu/Au⁺ mass ratio, and temperature have a significant influence on the recovery rate of gold, whereas the pH has little effect. A high gold recovery rate of 95.38% was achieved in 0.2 mol/L thiosulfate at 40°C after 40 min with a stirring speed of 400 rpm, pH of 11, en/Cu²⁺ molar ratio of 6, and Cu/Au⁺ mass ratio of 150. A kinetic study revealed that the reduction of gold-thiosulfate complex ions (Au(S₂O₃) ₂ ^3- ) on the surface of copper powder follows a first-order kinetics model with an apparent activation energy of 39.82 kJ/mol.     

Effect of suspension potential on the oxidation rate of copper concentrate in a sulfuric acid solution

A chalcopyrite concentrate containing 17 pct pyrite was oxidized in 1 mol/dm³ sulfuric acid solution at 90 °C (363.2 K). The suspension potential (Ptvs SCE, in the presence of Fe³⁺/Fe²⁺) was maintained constant in the range 0.30 to 0.65 V by controlled additions of KMnO₄ solution. The oxidation appeared to be under surface reaction control. The rate constant was nearly independent of total Fe concentration (0.01 to 0.5 mol/dm³), but increased rapidly with a rise in suspension potential until it reached a maximum at 0.40 to 0.43 V, after which there was marked decrease at around 0.45 V. Chalcopyrite in the concentrate was oxidized to form elemental sulfur over the whole of the suspension potential range, whereas the oxidation of pyrite took place only above 0.45 V and yielded sulfate ion. At 0.40 V the apparent activation energy was 47 kJ/mol. An analogy between the potential dependence of the rate and the Tafel correlation for an electrode process is discussed.     

Ammonia,oxidation leaching of chalcopyrite —reaction kinetics

The reaction for the ammonia, oxidation leaching of chalcopyrite, CuFeS₂ + 4NH₃ + 17/4 O₂ + 2 OH^- ⇌ Cu(NH₃)⁺² ₄2 + l/2Fe₂O₃ + 2 SO₄ + H₂O was studied using monosize particles in an intensely stirred reactor under moderate pressures to determine the important chemical factors which govern the kinetic response of the system. The reaction kinetics were studied at dilute solid phase concentration so that oxygen transport at the gas/liquid interface would not limit the rate. A catalytic electrochemical surface reaction was shown to control the reaction kinetics with the reaction rate determined by the following equation derived from electrochemical considerations: dα/dl=127 f/do (OH_- ^1/2 (k₁PO₁/1+k₂PO₁ (k₁+k₂(Cu⁺²)_o+k’₂α)(1-α)^2/3 (K P 1/2 Excellent agreement between theory and experiment was obtained both with regard to apparent reaction orders for oxygen, cupric, and hydroxyl, and with regard to geometric factors that influence the reaction rate. Further support for the reaction mechanism included an activation energy of approximately 10 kcal/mole obtained under a variety of experimental conditions and the fact that the initial reaction rate constant was several orders of magnitude less than predicted mass transfer coefficients. Formerly Metallurgy Graduate Student, University of Utah     

Dissolution of bornite in sulfuric acid using oxygen as oxidant

Leaching of natural bornite in a sulfuric acid solution with oxygen as oxidant was investigated using the parameters: temperature, particle size, initial concentration of ferrous, ferric and cupric ions, and using microscopic, X-ray and electronprobe microanalysis to characterize the reaction products. Additionally, stirring rate, pH and P_O2 were varied. Dissolution curves for percent copper extracted as a function of time were sigmoidal in shape with three distinct periods of reaction: induction, autocatalytic and post-autocatalytic which levelled off at 28% dissolution of copper. The length of the induction period was not reproducible, causing the dissolution curves to be shifted with respect to time. The dissolution curves in the autocatalytic and post-autocatalytic regions were reproducible, and this property was utilized to treat much of the kinetic data. The iron dissolution curves had four dissolution regions. An initial small but rapid release of iron to solution preceded the three periods just given for copper dissolution. Aside from this initial iron release, the iron and copper dissolution curves were almost identical.Stirring rate had no effect on dissolution of copper above 400 min^?1 nor did oxygen flow rate in the range 20–40 cm³/min. Dissolution rate was slightly dependent on oxygen partial pressure for P_O2 < 0.67. Hydrogen ion concentration had no effect except that sufficient acid was required to prevent hydrolysis and precipitation of iron salts.The dissolution rate was directly dependent on the reciprocal of particle diameter indicating possible surface chemical reaction control, but the activation energy of 35.9 kJ/mol (8.58 kcal/mol) for the autocatalytic region of copper dissolution is slightly too small for that, though not unreasonable. Initial addition of Fe²⁺ had a rather complex effect and markedly enhanced dissolution of copper, as also did initial addition of Fe³⁺. Microscopic analysis showed nuclei of two new phases, covellite and Cu₃FeS₄, in the induction region. The new phases grow rapidly in the autocatalytic stage, which is controlled by nuclei formation and chemical reaction. The post-autocatalytic region is characterized by complete transformation of bornite into covellite on the particle surfaces and Cu₃FeS₄ as an internal product with an X-ray spectrum very similar to that of chalcopyrite. The post-autocatalytic region is controlled by autocatalytic growth of newly formed phases. Further reaction beyond the autocatalytic region (percent copper dissolution > 28%) occurs so slowly with oxygen as oxidant that it was not studied.The rate of copper dissolution appears to be controlled by the rate of iron dissolution. Using that and the other experimental evidence a mechanism for reaction is proposed in which iron-deficient bornite, Cu₅Fe_?S₄, is formed on the surface by initial preferential iron dissolution. Labile Cu⁺ diffuses into this from Cu₅Fe_?SO₄ and unreacted bornite to produce CuS on the surface. Depletion of labile Cu⁺ ions from Cu₅FeS₄ produces Cu₃FeS₄ in the interior of the mineral particles.     

Intrinsic kinetics of the hydrogen reduction of Cu2S

Intrinsic kinetics of the hydrogen reduction of cuprous sulfide (Cu₂S) have been measured. Experiments were carried out in the temperature range 823 to 1023 K using a thermogravimetric analysis method. The reaction was studied in detail using both thin pellets and powder samples. The reaction followed first-order kinetics with respect to the solid reactant concentration as well as the hydrogen concentration. An activation energy of 92.0 kJ/mol (22.0 kcal/g-mole) was obtained for the reaction. Copper produced from the reaction formed filaments which sintered above about 1000 K. Is now Senior Metallurgist with Cyprus Metallurgical Process Corporation     

Leaching of bornite in acidified ferric chloride solutions

In an acidified ferric chloride solution, bornite leaches in two stages of reaction with the first being relatively much more rapid than the second; the first terminates at 28 pct copper dissolution. The first-stage dissolution reaction is electrochemical and is mixed kinetics-controlled; ferric-ion transfer through the solution boundary layer and reduction on the surface to release Cu²⁺ into solution are both important in controlling the rate. The concentration of labile Cu⁺ in the bornite lattice governs the potential of the surface reaction, and, once Cu⁺ is depleted from the original bornite, stage-I reaction ceases. The solid reaction intermediate formed is Cu₃FeS₄. Minute subcrystallites formed at the latter part of stage I leach topochemically in stage II. This reaction which commences at 28 pct Cu dissolution is characterized by a change in mechanism at about 40 pct copper dissolution, though the overall chemical equation for reaction is unchanged in stage II; cupric and ferrous ions and sulfur as a solid residue are products of reaction. The region 28 to about 40 pct Cu dissolution is designated as a transition period to stage-II reaction. Reaction rate in this period is interpreted as being controlled by reduction of Fe³⁺ on active product sulfur surface sites, and hence the reaction rate is controlled by the rate of nucleation and growth of sulfur on the Cu₃FeS₄ intermediate surfaces. Strain in the Cu₃FeS₄ crystal lattice is released during this period by diffusion from the lattice of Cu⁺ remaining from the labile copper initially present in the bornite. After about 40 pct Cu dissolution the rate of reaction is controlled by diffusion through the fully formed sulfur layer in an equiaxial geometrically controlled reaction.     

Dissolution of Cu2S in aqueous edta solutions containing oxygen

The mechanism of the reactions taking place in the heterogeneous system: synthetic polydispersive Cu₂S-ethylediaminetetraacetic acid (EDTA)—O₂—H₂O has been investigated. The partial pressure of oxygen and pH of the solution were found to exert a significant effect on the process kinetics. The dissolution rate does not depend, in practice, on the agitation rate and the EDTA concentration exerts an influence only at higher partial oxygen pressures.Dissolution of Cu₂S in aqueous EDTA solutions proceeds in two steps with the formation of CuS as an intermediate. In acid and neutral solutions the final products of dissolution are elementary sulphur and Cu(EDTA)^2- complex ion. The activation energy ΔE = 10.4kJ/mol (2.4 kcal/mol) suggests a diffusion controlled process. In alkaline solutions sulphur is oxidized to the sulphate ion and the dissolution process is kinetically controlled, ΔE = 41.4 kJ/mol (9.9 kcal/mol).     

The oxidation of thiosulfates with copper sulfate. Application to an industrial fixing bath

This paper presents the transformation of thiosulfate using Cu(II) salts, such as copper sulfate, at pH between 4 and 5. The nature and kinetics of this process were determined. In the experimental conditions employed, the reaction between thiosulfates and Cu(II) ions produces a precipitate of CuS and the remaining sulfur is oxidized to sulfate, according to the following stoichiometry: 1 mol thiosulfate reacts with 1 mol Cu²⁺ and 3 mol H₂O, generating 1 mol copper(II), 1 mol sulfate and 2 mol H₃O⁺. In the kinetic study, the apparent reaction order was ≈ 0 with respect to H₃O⁺ concentration, in the interval 1.0 · 10^? 4–1.0 · 10^? 5M H₃O⁺; of order 0.4 with respect to Cu²⁺ in the interval 0.21–0.85 g L^? 1 Cu²⁺; and of order 0 with respect to S₂O₃^2? in the interval 0.88–2 g L^?1 S₂O₃^2?. The apparent activation energy was 98 kJ mol^? 1 in the interval 15–40 °C. On the basis of this behavior an empirical mathematical model was established, that fits well with the experimental results. The thiosulfate transformation process using copper(II) sulfate was applied to an industrial fixing bath that proceeded from the photographic industry; after this, the resulting effluent contained less than 10 mg L^? 1 of thiosulfates.     

Leaching of enargite in H2SO4–NaCl–O2 media

This paper discusses the leaching of enargite (Cu₃AsS₄) in sulfuric acid–sodium chloride solution using oxygen as oxidant at atmospheric pressure. The dissolution of arsenic from enargite in this medium proceeds with elemental sulfur as a reaction product according to:2Cu₃AsS₄ + 6H₂SO₄ + 5.5O₂ → 6CuSO₄ + 2H₃AsO₄ + 8S° + 3H₂OThe dissolution rate of arsenic was found to be very slow. About 6% of arsenic was dissolved in 7 h of leaching at 100 °C in a solution containing 0.25 M H₂SO₄ and 1.5 M NaCl under a flow of oxygen of 0.3 l/min.The kinetics of arsenic dissolution is well represented by a shrinking core model for spherical particles controlled by surface reaction. An apparent energy of activation of 65 kJ/mol was obtained for the temperature range 80 to 100 °C.     

Leaching kinetics of ionic rare-earth in ammonia-nitrogen wastewater system added with impurity inhibitors

Ammonia-nitrogen wastewater is produced during the dressing and smelting process of rare-earth ores.Such wastewater includes a very high concentration of NH4＋, as well as other ions（e.g., NH4＋, RE3＋, Al3＋, Fe3＋, Ca2＋, Cl–, and Si O32–） with a p H of 5.4–5.6.Its direct discharge will pollute, yet it can be recycled and used as a leaching reagent for ionic rare-earth ores.In this study, leaching kinetics studies of both rare earth ions and impurity ion Al3＋ were conducted in the ammonia-nitrogen wastewater system with the aid of impurity inhibitors.Results showed that the leaching process of rare-earth followed the internal diffusion kinetic model.When the temperature was 298 K and the concentration of NH4＋ was 0.3 mol/L, the leaching reaction rate constant of ionic rare-earth was 1.72 and the apparent activation energy was 9.619 k J/mol.The leaching rate was higher than that of conventional leaching system with ammonium sulfate, which indicated that ammonia-nitrogen wastewater system and the addition of impurity inhibitors could promote ionic rare-earth leaching.The leaching kinetic process of impurity Al3＋ did not follow either internal diffusion kinetic model or chemical reaction control, but the hybrid control model which was affected by a number of process factors.Thus, during the industrial production the leaching of impurity ions could be reduced by increasing the concentration of impurity inhibitors, reducing the leaching temperature to a proper range, accelerating the seepage velocity of leaching solution, or increasing the leaching rate of rare earths.     

Electrowinning of Copper in the Presence of Anodic Depolarisers - A Review

Abstract

Alternative anodic reactions have been investigated to reduce the cell voltage and hence energy consumption in the electrowinning of copper. It is necessary to avoid oxygen evolution reaction at the anode, which requires a high potential of 2 V in order to reduce the cell voltage. An extensive literature review reveals that the cell voltage can be reduced by using various ionic couples, such as Fe²⁺/Fe³⁺, Cu²⁺/Cu¹⁺. Addition of cobalt, soluble sulfites and sulfur dioxide to the electrolyte modifies the anodic reaction. Examination of several electrode materials for anodic oxidation confirms that graphite is the most suitable material. Some fundamental studies on the anodic oxidation of sulfur dioxide have also been reviewed.     

酶催化分光荧光法测定环境水中痕量铬(Ⅵ)

铬（Ⅳ）对血红蛋白模拟酶催化荧光体系具有强烈的猝灭作用, 据此建立了一种酶催化分光荧光法测定铬（Ⅳ）的新方法。研究了溶液酸度、L-酪氨酸浓度、血红蛋白浓度、H₂O₂浓度及反应时间等因素对体系的影响。在pH10.4的NH₃·H₂O-NH₄Cl缓冲溶液中, 当L-酪氨酸、血红蛋白和H₂O₂的浓度分别为1.4×10^-4mol/L、1.0×10^-6mol/L和3.5×10^-5mol/L时, 测定铬（Ⅳ）的线性范围为2.0×10^-6～1.0×10^-4mol/L, 检出限为1.1×10^-8mol/L。1000倍NO₃^-、SO₄^2-、Na⁺、K⁺、Cl^-、Br^-, 300倍PO₄^3-、Al³⁺、NH₄⁺, 50倍Mn²⁺、Mg²⁺、Fe²⁺、Cu²⁺, 1倍Fe³⁺对铬（Ⅳ）的测定没有干扰。干扰较大的Fe³⁺, 可加入过量的柠檬酸掩蔽。对浓度为4.8×10^-5mol/L的铬（Ⅳ）进行11次平行测定, 其相对标准偏差为2.8%。该法已成功地应用于环境水样中铬（Ⅳ）含量的测定。     

Studies on the effect of addition of silver ions on the direct oxidation of pyrite

The nature of the reaction between Ag⁺ and pyrite in 0.25 M H₂SO₄ solutions has been investigated in order to determine whether Ag⁺ can enhance the ferric sulfate leaching of this mineral. Analysis of reacted pyrite particles using scanning electron microscopy, X-ray photoelectron spectroscopy (XPS), and low-angle X-ray diffraction (XRD) indicates that elemental silver and elemental sulfur are the primary surface species formed by this interaction. Rest potential measurements of a pyrite electrode immersed in a solution containing 10⁻² M Ag⁺ are also consistent with what is expected for the deposition of metallic silver. Furthermore, the XRD data reveal that, at the most, only minor amounts of Ag₂S are being produced. The presence of Ag₂O has also been detected, but this is due to oxidation of silver after the experiment is complete and while the particles are being transferred for surface analysis. When 1 M ferric sulfate is contacted with pyrite which has been pretreated in a AgNO₃ solution, most of the silver immediately redissolves and does not redeposit while ferric ions are present. This indicates that the kinetics of the transfer reaction between Ag⁺ and pyrite is slower than the reaction between Fe³⁺ and pyrite and suggests that Ag⁺ does not likely enhance the ferric sulfate leaching.     

A novel cyclic process using CaSO4/CaS pellets for converting sulfur dioxide to elemental sulfur without generating secondary pollutants: Part II. Hydrogen reduction of calcium-sulfate pellets to calcium sulfide

The reduction of calcium sulfate to produce calcium sulfide is a part of the cyclic process for converting sulfur dioxide to elemental sulfur that is described in Part I. The kinetics of the hydrogen reduction of nickel-catalyzed calcium-sulfate pellets were investigated using a thermogravimetric analysis (TGA) technique at reaction temperatures between 1023 and 1088 K and hydrogen partial pressures between 12.9 and 86.1 kPa. The reactivity of nickel-catalyzed calcium-sulfate pellets was demonstrated by the conversion of 70 pct fresh nickel-catalyzed calcium sulfate to calcium sulfide in 20 minutes at 1073 K under a hydrogen partial pressure of 86.1 kPa. Furthermore, the reactivity remained relatively intact after ten cycles of reactions and regenerations. This observed characteristic of the pellets is important because the solids must be reusable for repeated cycles to avoid generating secondary pollutants. The nucleation and growth rate expression was found to be useful in describing the kinetics of the reaction, which had an activation energy of about 167 kJ/mol (∼40 kcal/mol) in all reaction cycles except for the first regenerated samples that were lower at 146 kJ/mol (35 kcal/mol). The reaction order with respect to hydrogen partial pressure was 0.22 in all cycles with the exception of the first regenerated sample for which it was 0.37.     

Oxidation of Fe (II) in sulfuric acid solutions with dissolved molecular oxygen

The oxidation of Fe(II) with dissolved molecular oxygen was studied in sulfuric acid solutions containing 0.2 mol · dm⁻³ FeSO₄ at temperatures ranging from 343 to 363 K. In solutions of sulfuric acid above 0.4 mol · dm⁻³, the oxidation of Fe (II) was found to proceed through two parallel paths. In one path the reaction rate was proportional to both [Fe⁻²⁺]² andp _{o 2} exhibiting an activation energy of 51.6 · kJ mol⁻¹. In another path the reaction rate was proportional to [Fe²⁺]², [SO ₄ ^{2 −}], andp _{o 2} with an activation energy of 144.6 kJ · mol⁻¹. A reaction mechanism in which the SO ₄ ^{2 −} ions play an important role was proposed for the oxidation of Fe(II). In dilute solutions of sulfuric acid below 0.4 mol · dm⁻³, the rate of the oxidation reaction was found to be proportional to both [Fe(II)]² andp _{o 2}, and was also affected by [H⁺] and [SO ₄ ^{2 −}]. The decrease in [H⁺] resulted in the increase of reaction rate. The discussion was further extended to the effect of Fe (III) on the oxidation reaction of Fe (II).     

Reduction of Fe<Subscript>2</Subscript>MoO<Subscript>4</Subscript> by hydrogen gas

In the present work, the reduction kinetics of iron molybdate (Fe₂MoO₄) by hydrogen gas was investigated by thermogravimetric analyses (TGA). Both isothermal and nonisothermal experiments were conducted. By using fine particles, very shallow powder bed, and high hydrogen flow rate, the study could be focused on the chemical reaction. The activation energy obtained from the isothermal experiments was found to be 173.5 kJ/mol, which was in reasonable agreement with the value of 158.3 kJ/mol obtained from the nonisothermal experiments. The reduction product was found to be an intermetallic compound, Fe₂Mo, of microcrystalline structure.     

Oxidation of mixed copper-iron sulfide

. A rectangular plate of mixed copper-iron sulfide composed of bornite (Cu₅FeS₄) and troilite (FeS) was oxidized in an O₂-Ar mixed gas stream at 1023 to 1123 K. At the start of the oxidation, iron was preferentially oxidized with the rapid formation of a dense Fe₃O₄ layer of about 10 μm thickness on the sample surface, without the evolution of SO₂ gas. Following this reaction, layers of both Fe₃O₄ and Fe₂O₃ grew on the sulfide surface in accordance with the parabolic rate law. The diffusion of iron through the oxide layers was assumed to control the oxidation rate during this stage. The effect of oxygen partial pressure on the parabolic rate constants was minor and an apparent activation energy of 126 kJ/mol was obtained. During the later stages of the reaction, when the sulfur activity in the inner sulfide core increased, the oxidation proceeded irregularly to the interior of the remaining sulfide with the formation of a porous oxide and the evolution of gaseous SO2. The remaining sulfide core was found to be a mixture of bornite (Cu₅FeS₄) and djurleite (Cu_1.96S). H. TSUKADA, former Graduate Student at Kyoto University     

The leaching of galena in cupric chloride media

The kinetics of dissolution of galena (PbS) in CuCl₂-HCl-NaCl media have been investigated using the rotating disk technique. Rapid nonlinear kinetics are observed over the temperature range 45 °C to 90 °C and for NaCl concentrations from 0 to 4.0 M. The leaching rate is in-dependent of CuCl₂ concentrations >0.1 M but increases with increasing concentrations of either HC1 or NaCl. The leaching rate decreases with the accumulation of either the PbCl₂ or CuCl reaction product in the leaching medium but is insensitive to the disk rotation speed. The apparent activation energy for the rate controlling process is 33 kJ/mol, and this value falls to about 15 kJ/mol when interpreted as a dissolution rate for PbCl₂, whose solubility increases with temperature. The above observations are shown to be consistent with rate control by the outward diffusion of the PbCl₂ and CuCl reaction products through the solution trapped in the pores of the constantly thickening elemental sulfur layer which forms on the surface of the galena. CANMET, Energy, Mines, and Resources Canada, 555 Booth Street, Ottawa, ON, K1A 0G1, Canada.