Kinetics of the dissolution of scheelite in aqueous Na4EDTA solutions

The reaction kinetics of the dissolution of pure scheelite (CaWO₄) particles in aqueous Na₄EDTA solutions were studied at atmospheric pressure. As expected, the dissolution rate increased with decreasing initial particle size and with increasing temperature and Na₄EDTA concentration. Further, the dissolution rate decreased as the initial solid-liquid ratio and the ionic strength of the solution were increased. The experimental results do not support the conventional shrinking-core model for a single irreversible reaction. A new shrinking-core model for multiple reactions, composed of a noninstantaneous reversible reaction (scheelite dissociation into the ions Ca²⁺ and WO ₄ ²⁻ ) and an instantaneous irreversible reaction (formation of Ca-EDTA complex), was presented. The observed dependency of the dissolution rate on the relevant operating variables was the same a the theoretical predictions based on the present shrinking-core model. The activation energy was 49800 J mol⁻¹. These findings justify the validity of the assumed kinetic model with the multiple reactions as the rate-controlling step. The dissolution rate expression was obtained as a function of the initial particle size, initial solid-liquid ratio, Na₄EDTA concentration, temperature, and ionic strength of the solution.     

Dissolution Kinetics of Ulexite in Aqueous Edta Solutions

Abstract

The dissolution kinetics of ulexite in aqueous disodium Ethylene Diamine Tetra Acidic Acid (EDTA) solutions has been investigated with respect to the effects of particle size, solution concentration, pH of solution, calcination temperature and reaction temperature. The rate of the reaction decreases as the particle size and pH of the solution increase, but the rate increases with an increase in both solution concentration and reaction temperature. The sample pre-heated at 140 °C has the highest dissolution rate. The rate of the dissolution can be expressed according to the unreacted shrinking core model with changing fluid phase concentration.

On a étudié la cinétique de dissolution de l'ulexite dans des solutions de bisodium aqueux d'EDTA, en rapport avec l'effet de taille de particule, de concentration et de pH de la solution ainsi que des températures de calcination et de réaction. Le taux de réaction diminue avec une augmentation de la taille de particule et de pH de la solution, mais le taux augmente avec une augmentation de la concentration de la solution et de la température de réaction. L'échantillon préchauffé à 140 °C a le plus haut taux de dissolution. On peut exprimer le taux de dissolution d'après le modèle de rétrécissement du noyau non réagi en fonction du changement de concentration de la phase fluide.     

Kinetics of Dissolution of Tenorite in Ammonium Media

In this work, the dissolution kinetics of tenorite (CuO) in a NH₄OH-H₂O system was studied. The studied temperature range was 5–55°C, ammonium hydroxide concentration between 0.1 and 0.75 M, and a particle size range of 5–24 µm. The stirring speed, pH of the ammonia solution, and various agents were also studied. The results indicated that the leaching of tenorite occurred quickly with a particle size of 5 µm in a 0.45 M solution of NH₄OH for a pH value equal to 10.5. Dissolution of CuO also increases as temperature and the concentration of NH₄OH increase. For concentrations less than 0.10 M, there is almost no leaching tenorite. By decreasing the particle size, the dissolution of CuO increase. Results show the stirring speed had no significant effect on the leaching rate of tenorite for values above 250 rpm. Leaching kinetics was analyzed using the model of the surface chemical reaction. The reaction rate was of the order of 2.2 with respect to the concentration of ammonium hydroxide and inversely proportional to the initial particle size. Activation energy of 59 kJ/mol was estimated for the temperature range of 5–55°C.     

Dissolution kinetics of malachite in ammonia/ammonium carbonate leaching

The leaching of oxide copper ore containing malachite, which is the unique copper mineral in the ore, by aqueous ammonia solution has been studied. The effect of leaching time, ammonium hydroxide, and ammonium carbonate concentration, pH, [NH₃]/[NH₄⁺] ratio, stirring speed, solid/liquid ratio, particle size, and temperature were investigated. The main important parameters in ammonia leaching of malachite ore are determined as leaching time, ammonia/ammonium concentration ratio, pH, solid/liquid ratio, leaching temperature, and particle size. Optimum leaching conditions from malachite ore by ammonia/ammonium carbonate solution are found as ammonia/ammonium carbonate concentrations: 5 M NH₄OH+0.3 M (NH₄)₂CO₃; solid/liquid ratio: 1:10 g/mL; leaching times: 120 min; stirring speed: 300 rpm; leaching temperature: 25 °C; particle size finer than 450 μm. More than 98% of copper was effectively recovered. During the leaching, copper dissolves as in the form of Cu(NH₃)₄⁺² complex ion, whereas gangue minerals do not react with ammonia. It was determined that interface transfer and diffusion across the product layer control the leaching process. The activation energy for dissolution was found to be 15 kJ mol⁻¹.     

Dissolution kinetics of chalcopyrite containing pyrite in water saturated with chlorine

In this work the dissolution kinetics of chalcopyrite in water saturated with chlorine have been investigated using particle size, reaction temperature and gas flow rate as parameters. It has been found that the dissolution rate decreased with an increase in particle size and reaction temperature, but increased with an increase in gas flow rate. The mechanism by which the dissolution proceeds has been deduced. It has been concluded that the dissolution is controlled by diffusion through the product layer. The activation energy was calculated as 9.06 kJ mol⁻¹.     

Kinetics of dissolution of synthetic millerite (β-NiS) in acidic potassium dichromate solutions

The dissolution rate of millerite (β-NiS) in sulphuric acid solutions containing potassium dichromate has been determined by measurement of the rate of nickel ion formation. The effects of temperature, dichromate ion concentration, pH of leaching solution and stirring speed have been investigated. Two distinct regions for dissolution of millerite were observed, below and above 50°C. The activation energy of dissolution is 23.9 and 54.6 kJ mol^?1 in these two regions, respectively. At dichromate concentrations lower than 0.05 M a first order dependence of dissolution rate on Cr₂O₇^2? ion concentration was observed, whereas for higher concentrations a half order dependence was established. The concentration of hydrogen ion affects nickel extraction from β-NiS at pH 1.4, but at lower pH this factor is less important.     

Kinetics of dissolution of synthetic scheelite by an alkaline EDTA leach solution

The dissolution rate of synthetic scheelite in an alkaline EDTA leach solution under atmospheric pressure has been determined by use of a rotating disc method. The effects of disc rotation speed, temperature, reagent concentration and pH of leach solution have been investigated. The dissolution rate was proportional to the square root of the disc rotation speed. The apparent activation energy of dissolution of synthetic scheelite was 22 kJ mol⁻¹ within the experimental temperature region of 24 to 99°C. A first order dependence of dissolution rate on EDTA concentration was observed. It has been shown from the experimental results that the dissolution reaction was controlled by the mass transfer in the aqueous solution.     

Reaction Kinetics of magnesite ore in dilute ethanoic acid

The leaching of naturally occurring magnesite in dilute ethanoic acid is achieved to optimize the reaction conditions affecting the reaction kinetics. In the current study effect of various reaction parameters (The particle size of ore, concentration of leaching agent, the reaction temperature and rate of stirring) on the dissolution of magnesium carbonate ore with aqueous solutions of acetic acid is probed. It is inferred that the rate of leaching reaction of magnesium carbonate ore in the aqueous solutions of acetic acid rises with a rise in temperature of reaction medium, acetic acid solution strength and decreases with the increase in particle size of the magnesite ore samples. The analysis of kinetic data done by the application of graphical and statistical approaches reveals that the leaching kinetics of magnesite ore in dilute solutions of acetic acid follows a surface chemically controlled mechanism. The calculated value of energy of activation for the dissolution reaction of magnesium carbonate in acetic acid is 46.39 kJ mol^–1.     

Leaching of manganese nodules in ammoniacal medium using glucose as reductant

Polymetallic Indian Ocean nodules can be leached in ammoniacal solution in the presence of glucose. The various parameters chosen for leaching studies were: amount of glucose, time, pH, temperature, concentrations of ammonia and ammonium salt, and particle size. The percentage extraction of copper, nickel and cobalt decreases when the glucose concentration is increased to more than 0.4 gramme per gramme of nodule at 338 K and 0.2 g/g at 358 K. The dissolution of copper has been found to be dependent more on the pH of the solution than on the total molarity of ammonia and the ammonium ion. Leaching temperatures above 373 K are disadvantageous for the extraction of copper and cobalt, whereas nickel extraction is about 95% even at 433 K. The rate of leaching for all three metals is independent of the particle size in the range studied. All the copper, about 90% of the nickel and 60% of the cobalt can be extracted under the following leaching conditions: temperature 358 K, time 4 h, initial ammonia concentration 2.5 M, ammonium chloride concentration 0.37 M and glucose 0.2 gramme per gramme of nodule.     

Leaching kinetics of malachite in ammonium carbonate solutions

Leaching of malachite was conducted with ammonium carbonate as lixiviant and with temperature, lixiviant concentration, and particle size as variables. Two stages of reaction were found. In Stage I, the initial dissolution of malachite proceeds rapidly, but after about 10 pct reaction the rate is reduced by surface blockage due to the presence of a needle-structured intermediate, presumably Cu(OH)₂. Subsequently, malachite and the intermediate dissolve concurrently. In Stage II, after 90 pct reaction, essentially all of the malachite has dissolved and only the intermediate remains. It dissolves in Stage II. The activation energy is 64 kJ/mole (15.3 kcal/mole) for Stage I and 75 kJ/mole (18 kcal/mole) for Stage II. The rate of reaction in Stage I is proportional to the reciprocal of particle size and is 0.8 order with respect to the concentration of ammonium carbonate. The structures of leaching residues were studied using a scanning electron microscope. The kinetic data (activation energy and entropy), particle size and concentration dependence, residue morphology, and general leaching behavior evident from microscopic monitoring during leaching were used to develop the geometric equation for leaching in Stage I. The equation, based on a heterogeneous reaction with geometric rate control, is: 1 − (1 − α^1/3 = K₀₁/r₀/[(NH₄)₂C0₃]^0.8 exp(-64,000/RT)t. It was deduced that initial steps in reaction were: (1) release of Cu²⁺ from malachite; (2) initial complexing with ammonia to form Cu(NH₃)²⁺; and (3) subsequent complexing to produce Cu(NH₃) ₄ ²⁺ which is stable in solution at pH 8.8, the buffered pH of reaction. Stage II appears to be a similar reaction except that the reaction obeys cylindrical geometry instead of spherical geometry as in Stage I.     

Dissolution behaviour of a beryl ore for optimal industrial beryllium compound production

This study involves the leaching of the beryl ore with sulphuric acid (H₂SO₄) solution for predicting optimal beryllium extraction conditions with the aim of assessing the importance of leachant concentration, reaction temperature and particle size on the extent of dissolution. A kinetic model to represent the effects of these variables on the leaching rate was developed. It was observed that the dissolution of beryl ore increases with increasing H₂SO₄ concentration, temperature, decreasing particle size and solid to liquid ratio. At optimal leaching conditions, 89.3% of the ore was reacted by 1.25?mol/L at 75°C temperature and 120 minutes with moderate stirring, where 1612.0?mg/L Be²⁺, 786.7?mg/L Al³⁺, 98.1?mg/L Fe³⁺ and 63.4?mg/L Ag⁺ were found as major species in the leach liquor. The unleached products constituting about 10.7% were examined by X-ray diffraction (XRD) and found to contain primarily, siliceous compounds such as Xonotlite, Antigorite, Chrysolite and Kaolinite.     

Kinetics of dissolution of synthetic heazlewoodite (Ni3S2) in nitric acid solutions

The dissolution rate of heazlewoodite in nitric acid solution has been determined. The effects of nitric acid concentration, temperature, particle size, stirring intensity and addition of Cu²⁺ ions have been investigated. Solid residues after leaching were examined by SEM, X-ray diffraction and chemical analysis. In the solutions containing less than 2.0 M HNO₃, dissolution was observed to be completely inhibited after 30 min leaching time, and the rate of hydrogen sulphide production was faster than its oxidation to S⁰ and HSO₄^?. In 3 M HNO₃, an abrupt increase in dissolution rate of Ni₃S₂ was found. Two different regions of the dissolution of heazlewoodite were observed below and above 50°C. At temperatures below 50°C, the dissolution rate was very slow, even in 3.0 M HNO₃ solution, and H₂S gas was evolved. Above 50°C, the dissolution rate rapidly increased. Over the temperature interval 60–90°C in 3.0 M HNO₃ dissolution followed a linear rate law, and the activation energy was found to be 42.1 kJ mol^?1. Most of the oxidized sulphide ion was found in the solution as sulphate. The leaching rate was independent of stirring speed. The rate-controlling step of the Ni₃S₂ dissolution is the oxidation of hydrogen sulphide to elemental sulphur or sulphate ions on the Ni₃S₂ surface. Addition of small amounts of Cu²⁺ ions to the nitric acid acted as catalyst for the dissolution of Ni₃S₂. Bubbling air through the leach suspension increased the dissolution rate of Ni₃S₂ in solutions containing less than 2.0 M HNO₃.     

Dissolution of nickel hydroxide in ammoniacal aqueous solutions

The dissolution of nickel hydroxide in ammoniacal solutions was investigated to develop a new recycling process for nickel-metal hydride batteries. The effects of temperature, total ammonia concentration, and pH of the solution were examined in the range of 30 °C to 60 °C, 3.0 to 5.0 M, and 9.0 to 10.7, respectively. All dissolution-time curves showed sigmoidal shapes, which could be approximately expressed by the Johnson-Mehl-Avrami-Yerofeev-Kolmogrov (JMAYK) equation. The hydroxide particles were pitted, and some of them were broken into fragments in the course of the dissolution. An increase in the surface area of the hydroxide particles due to the formation of pits and fragmentation seemed to be the reason for the acceleration of dissolution in the early stage. The surface area of the hydroxide was measured by the Brunauer-Emmett-Teller (BET) method, and the dissolution rate per surface area was determined. The activation energy for the dissolution was obtained as 100±10 kJ mol⁻¹, which confirmed that the dissolution was controlled by chemical reactions at the hydroxide/liquid interface. The dissolution rate was increased by the increase in ammonia concentration, and the highest rate was observed at pH ca. 10.     

Dissolution kinetics of spent petroleum catalyst using two different acidophiles

Leaching studies using spent petroleum catalyst containing Ni, V and Mo were carried out using two different acidophiles, iron oxidizing (IOB) and sulfur oxidizing (SOB) bacteria. XRD analysis proved the existence of V in oxide form, Ni in sulfide form, Mo both in oxide and sulfide forms, and sulfur in elemental state. Both bacteria showed similar leaching kinetics at the same leaching parameters, such as pH, nutrient concentration, pulp density, particle size and temperature. The dissolution kinetics for Ni and V was much higher than Mo. Bioleaching kinetics was observed to follow dual rates, initially faster followed by a slower rate. So, dissolution mechanism was based on surface- and pore-diffusion rate. The dissolution process was found to follow 1st order kinetics. Unified dissolution rate kinetics equations were developed using 1st order rate kinetics. Various thermodynamic parameters were also calculated. Rate determining step for both the bacteria were evaluated and the average D₁ (surface) and D₂ (pore) values were found to be around 7 × 10^− 9 and 1 × 10^− 10 cm² respectively. The lower value of D₂ suggested that the pore diffusion is the rate determining step during bioleaching process.     

Open circuit potential and leaching rate of pyrite in cupric chloride solution

As a refractory gold mineral, pyrite needs to be oxidised prior to gold leaching. In this study, the effect of [Cl^?] concentration (40.6–149.8?g/L), [Cu²⁺] concentration (0.8–31.6?g/L), pH (1.5–2.5) and temperature (25–90 –C) on the pyrite leaching rate was investigated. In addition, the open circuit potential (OCP) values of pyrite in cupric chloride solution were investigated. A linear regression model was constructed to predict pyrite dissolution rate i.e. corrosion current density. It was shown that the temperature had a significant positive effect on pyrite dissolution, while increased cupric ion concentration was also shown to provide some dissolution enhancement. According to the regression analysis, pH had no effect on the corrosion current density at OCP. Dissolution rates of pyrite varied between 0.05 and 2.9?µm/h. The activation energy values varied from 20 to 90?kJ/mol, indicated that the pyrite dissolution reaction rate was controlled by the chemical reaction or mixed mechanism rather than diffusion alone. The simultaneous increase in corrosion potential and corrosion current density indicated that the anodic pyrite dissolution reaction was rate determining at OCP.     

Dissolution of MoS2 concentrate using NaClO from 283 to 373 K

This study analyses the leaching process of molybdenite (MoS₂) concentrate using sodium hypochlorite (NaClO) at temperatures ranging from 283 to 373?K. The following variables were studied: leaching time, stirring velocity, temperature, NaClO concentration, NaOH concentration, particle size and liquid:solid ratio. The optimum parameters for molybdenite dissolution were: Time?=?0.81?h, stirring speed?=?800?rev?min^??1, temperature?=?303?K, NaClO concentration?=?1.49M, NaOH concentration?=?8.01M, particle size?=?45?μm and liquid:solid ratio?=?300?:?1.?Under these conditions, molybdenite dissolution reached around 99%, while Cu and Fe recovery were insignificant. Analysis using XRD, QUESCAM and SEM showed release indices and subsequent reaction of the MoS₂ and the constituent parts of Cu and Fe.     

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.     

Kinetic Study and Mathematical Model of Hemimorphite Dissolution in Low Sulfuric Acid Solution at High Temperature

The dissolution kinetics of hemimorphite with low sulfuric acid solution was investigated at high temperature. The dissolution rate of zinc was obtained as a function of dissolution time under the experimental conditions where the effects of sulfuric acid concentration, temperature, and particle size were studied. The results showed that zinc extraction increased with an increase in temperature and sulfuric acid concentration and with a decrease in particle size. A mathematical model able to describe the process kinetics was developed from the shrinking core model, considering the change of the sulfuric acid concentration during dissolution. It was found that the dissolution process followed a shrinking core model with “ash” layer diffusion as the main rate-controlling step. This finding was supported with a linear relationship between the apparent rate constant and the reciprocal of squared particle radius. The reaction order with respect to sulfuric acid concentration was determined to be 0.7993. The apparent activation energy for the dissolution process was determined to be 44.9 kJ/mol in the temperature range of 373 K to 413 K (100 °C to 140 °C). Based on the shrinking core model, the following equation was established: $$ 1.21\ln \left( {1 - 0.83x} \right) - \left[ {1.02\ln \frac{{0.35 + \left( {1 - x} \right)^{{{2 \mathord{\left/ {\vphantom {2 3}} \right. \kern-0pt} 3}}} - 0.59\left( {1 - x} \right)^{{{1 \mathord{\left/ {\vphantom {1 3}} \right. \kern-0pt} 3}}} }}{{0.35 + \left( {1 - x} \right)^{{{2 \mathord{\left/ {\vphantom {2 3}} \right. \kern-0pt} 3}}} + 1.18\left( {1 - x} \right)^{{{1 \mathord{\left/ {\vphantom {1 3}} \right. \kern-0pt} 3}}} }} + 3.52\arctan \left( {1.96\left( {1 - x} \right)^{{{1 \mathord{\left/ {\vphantom {1 3}} \right. \kern-0pt} 3}}} - 0.58} \right)} \right] + 2.06 = 42,192.59{\text{e}}^{{ - \frac{44,900}{{{\text{R}}T}}}} t. $$      

The electrochemical property of acetylene black suspension solution with ozone bubbling and its effects on copper dissolution

The electrochemical properties of acetylene black suspension solutions containing sulfuric and hydrochloric acid were investigated both with and without ozone bubbling. It was found that the potential of the acetylene black suspension solution on Pt electrode increased with ozone bubbling. In 2.5 kg/m³ acetylene black suspension solutions with 0.5 kmol/m³ H₂SO₄ or 1 kmol/m³ HCl, the potential was maintained at more than 1.1 V (vs normal hydrogen electrode) for over 1 hour after the ozone bubbling was stopped. In contrast, the solution potentials on Pt electrode reduced to the original value that is less than 0.8 V in 0.5 kmol/m³ H₂SO₄ or 1 kmol/m³ HCl solution without acetylene black particles, in a short period of time. This phenomenon may result from the formation of extra surface functional groups on the acetylene black particles, which have been oxidized by the ozone. The potential of the acetylene black suspension solution with 0.5 kmol/m³ H₂SO₄ on Pt electrode was found to decrease with increasing temperature and pH, regardless of the amount of acetylene black. The behaviors of copper dissolution in the acetylene black suspension solution containing 0.5 kmol/m³ H₂SO₄ with ozone bubbling have also been investigated. It was found that copper dissolves much faster in the solution with acetylene black particles than without them. In addition to this, the rate of copper dissolution was found to increase with the concentration of acetylene black and the temperature below 60 °C, but decreased with an increase in pH. The copper dissolution in the suspension solution with ozone bubbling appears to proceed under chemical reaction control for these conditions.     

Reaction mechanism of gold dissolution with bromine

The dissolution of gold with elemental bromine was studied by using a rotating disc technique. The main parameters studied were bromine and bromide concentrations, stirring speed, pH, and temperature. The effect of various salts, manganese, and hydrogen peroxide was also examined. The dissolution kinetics of gold with Br₂ and NaBr mixture is complex. The reaction mechanism is a function of solution composition, which determines the kind of adsorbing species. For an excess concentration of bromide ions, the rate expression is Rate = (2k _cl7 k _al6)^1/2 K ₁₅ [Br ₃ ⁻ ] and for an excess concentration of bromine, the rate expression is Rate = (2k _c27 k _a29)^1/2 [Br⁻]^1/2 {K₂₅ [Br₂]³/(1 +K ₂₅ [Br₂]³)}^1/2 Gold in bromine solutions dissolves according to electrochemical/chemical (EC) mechanisms. The electrochemical component of the mechanism is responsible for the formation of AuBr₂. In the chemical component of the mechanism, this monovalent gold bromide disproportionates into gold and stable AuBr ₄ ⁻ , which reports into solution. With respect to pH, there are two characteristic dissolution regions. In the pH range of 1 to 7, gold dissolution rates were insensitive to pH. Above pH 7, gold dissolution rates decreased with increase of pH.