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By Jennifer Mager, G. P. Martins, Dean Mussatti

"The role of lead, at low concentrations in high pH cyanide-electrolytes, on the dissolution behavior of gold, has been a topic of scientific and industrial concern for well over a century. The recent paper by Kondos et al [1] at CANMET (1995) this continuing interest and apparent importance. Nevertheless, the mechanism(s) by which this (and other heavy metal) component influences the electrodics of this electrochemical system has still not been unequivocally demonstrated. Instead, several plausible hypotheses, by pioneering researchers in this field, have been advanced and reiterated OVer the ensuing years. While it is generally accepted, based on equilibrium elctrode-potential calculations, that reduction (or co-reduction when oxygen is present in the electrolyte) of lead on the gold surface may occur due to cementation (contact reduction), the cemented lead has never been characterized. The work presented has reexamined the role of lead in this system, by delineating the species distribution of these system components and by interpreting the results of potentiodynamic studies in conjunction with SEM analyses of a gold electrode.1. INTRODUCTIONThe leaching of gold ores in cyanide electrolytes has been practiced for well over a 100 years. Research conducted on this topic has been primarily focused on the effects of operating parameters such as concentrations of oxygen and cyanide, and the pH of the electrolyte; or the leaching behavior of carbonaceous and sulfitic gold-bearing materials.Mechanisms by which pure gold is leached in alkaline cyanide media, with oxygen serving as the oxidant, have been subjected to continual examination and re-examination in the published technical literature during this century. Recently, it has been speculated that without the presence in the electrolyte of trace heavy metals, such as lead or mercury, that gold would not be leachable. Researchers who have tackled this topic, have either considered heavy metals to be a natural occurrence in these systems and ignored the role they may serve in the leaching process, or they have deliberately focussed on controlling their concentrations in the system to undetectable limits. As a result, conflicting findings have been reported for what would appear - depending on the details provided in these reports - to be identical systems."

Jan 1, 1997

By Hojat Naderi

In this research assisted leaching of chalcopyrite using sodium peroxodisulfate was studied. Electrochemical techniques such as Tafel analysis and electrochemical impedance spectroscopy (EIS) were used to investigate the surface reactions of a chalcopyrite electrode in the presence and absence of Na2S2O8. According to the results, addition of sodium peroxodisulfate increases the current exchange of the corrosion process and prevents the formation of a passive layer on the surface of the electrode. EIS tests show the trans-passive dissolution of the passive layer on the chalcopyrite electrode in presence of Na2S2O8. Equivalent electrochemical circuits were modeled for Na2S2O8-free and -containing solutions and the model parameters were compared to determine the effect of S2O8 2− on chalcopyrite dissolution. Copper dissolution from pure chalcopyrite mineral and chalcopyrite concentrate was carried out using 15 g/L sulfuric acid solution with and without Na2S2O8. Simultaneous presence of 10 g/L ferric ion and 40 g/L peroxodisulfate salt results in about 40 and 18% of Cu extraction from chalcopyrite concentrate and pure chalcopyrite mineral, after 96 h, respectively.

By Kuniaki Murase, Tetsuji Hirato, Koji Nitta, Yasuhiro Awakura

"The redox behavior of copper species in an ""ammonium imide"" room temperature molten salt was examined in order to clarify the applicability of the salt to the electroplating media of various metals. Trimethyl-n-hexylammonium bis(trifluoromethanesulfonyl)- amide (TMHA-Tf2N), having an electrochemical window of 5.6 V (50 °C), and corresponding copper(II) salt were synthesized. In TMHA-Tf2N media monovalent copper ion, Cu(I), was stable and Cu metal was oxidized, or corroded, in the presence of Cu(II) species. Cathodic electrodeposition of copper metal and anodic dissolution of it were, thus, one-electron reaction and their current efficiencies were almost 100%.IntroductionElectrodeposition of metals from aqueous solutions is an important soft process for manufacturing thin-film materials, surface finishing, and extractive metallurgy. However, the electrodeposition of base metals, such as zinc, chromium, and nickel, from aqueous media inevitably accompanies hydrogen evolution, which lowers the cathodic current efficiency of metal deposition. Since the electrodeposition of aluminium, titanium, and rare earths from aqueous media is actually impossible due to their largely negative redox potentials, nonaqueous media such as aprotic organic solvent and high-temperature molten salts have been employed for the electrodeposition of these metals. Room temperature molten salts (RTMS),1, 2) or room temperature ionic liquids, have also been developed as a promising electrolytes for the electrodeposition of base metals. In this field, chloroaluminates of alkylpyridinium or alkylimidazolium cation have been well investigated for aluminium3) or alluminium-alloy4-5) electroplating media. On the other hand, in order to avoid high hygroscopicity arising from the use of aluminium chloride, attempts have been made to combine the alkylimidazolium cations with fluorine-containing hydrophobic anions, e.g. BF4-,6) CF3SO3- (TfO-),7) (CF3SO2)2N- (Tf2N-),8) and H(HF)n-ions,9) and investigated for electrodeposition media.'°) Recently, a new series of RTMS consisting of tetraalkylammonium cations and Tf2N- anion, sometimes abbreviated as TFSI- anion, was found independently by MacFarlane et al.11, 12) and Matsumoto et al. 13) This type of RTMS, which is commonly named ""ammoniumimide"" salt, has a wide electrochemical window of ca. 5 V and, thus, the RTMS seems to be suited for practical application as a solvent for the electrodeposition process. In this paper, we report the electrochemical behavior of copper species in an ammoniumimide RTMS, trimethyl-n-hexylammonium bis(trifluoromethanesulfonyl)amide (TMHA-Tf2N)."

Jan 1, 2000

By Kenneth N. Han

Ammonia has been found to be an effective leaching reagent for gold, silver and platinum group metals in the presence of appropriate oxidants. Electrochemical and kinetic aspects of the dissolution of elemental gold in ammoniacal solutions have been investigated. The cathodic reaction of aurous di-ammine on the gold cathode has been investigated first. From this investigation, the standard electro-potential of the cathodic reaction .and hence. the Gibbs free energy of formation of the aurous di-ammine were established. The solubility of gold in ammoniacal solutions was also examined in relation to ammonia concentration, temperature and concentration of various oxidants. The anodic reaction of the gold disk in ammonia? in the presence? of various oxidants including oxygen, ozon, hypochlorite, hydrogen peroxide, cupric and cobaltic ammine, and iodine was also examined and the results have been discussed. Excellent dissolution yielding of gold and many other metals, typically better than 95% recovery in 1'-2 'hours of leaching at a temperature ranging 80°C to 190°C has been observed. Test results of the dissolution of gold from elemental state as well as other sources including sulfidic ores and scrap are presented.

Jan 1, 1998

By F. A. Schinner

The present study has investigated the leachability of cadmium sulfide minerals by Thiobacillus ferrooxidans and the electrochemical reactions involved in the process. Using a cyclic voltammetric technic and carbon-paste-CdS electrodes, it was found that the bio-oxidation of semiconductor cadmium sulfide minerals consisted of a number of intermediate electrochemical reactions. The overall reaction was found to be controlled by solid state diffusion as suggested by the chrono-amperometric and chrono-potentiometric measurements. The activation energy of solid state diffusion was determined by the Sand's method to be AE=24.3 kJ. A generalized mechanism was proposed for the bacterial oxidation of cadmium sulfide by T. ferrooxidan and an explanation given for the importance of high redox potential of leach solution versus the decomposition potential of the sulfide mineral. Furthermore, the effects of n-type or p-type character of CdS substrates relative to their bioleachability was discussed.

Jan 1, 1993

By O. Forsén

A new cell construction was designed for the study of the electrochemical behaviour of additives in conditions that simulate real copper, electrorefining. The behaviour of gelatine and thiourea was studied by applying different electrochemical methods, i.e. polarization resistance and voltametric measurements. In this study, individual galvanostatic electrolysis experiments were carried out for 120 hours. The organic additives were introduced to the electrolyte at certain intervals and their concentration was varied in the range &om zero to four ppm. An optical microscope was applied for the examination of copper cathode deposit microstructures. The results show that gelatine has a polarizing effect on the deposition potential of copper whereas even small amounts of thiourea depolarize the electrodeposition of copper. The maximum inhibitor efficiency of gelatine was obtained at a gelatine concentration of slightly lower than two ppm. When both gelatine and thiourea were present in the electrolyte, the depolarizing effect of thiourea exceeded completely the polarizing effect of gelatine. If chloride ions were added to gelatine and thiourea containing electrolyte, the electrochemical behaviour of the system was altered drastically. Chloride ions resulted in the prevailing of polarization effect caused by gelatine while the depolarizing effect of thiourea disappeared in this system. The polarizing effect of gelatine increased until chloride ion concentration of 30 ppm was reached. Also, the above electrochemical phenomena could be detected in the optical examination of copper deposit microstructure.

Jan 1, 1995

By E. Fockedey

he destruction of free cyanide on a Co3O4 doped carbon felt was studied. The experiments were done with an eiectrochemical filter press cell on dilute alkaline solutions containing 250 mg/l NaCN. No chloride ions were added to the solutions. The cobalt oxide protects the felt against corrosion and has a catalytic effect on the degradation of the cyanide. This kind of electrode allows working with current density as high as 1200 Aim without any visible degradation of the felt. The most interesting results were obtained with a current density of 400 Aim' at which the cyanide concentration can be lowered to 5 mg/l with a current efficiency of more than 70 % and a specific energy consumption of about 10 kWh/ kg CN.

Jan 1, 1998

By G. Lissens

In this work the electrochemical combustion of dissolved organic species in a single compartment cell containing a titanium mesh cathode and a boron doped diamond anode has been studied, The organic molecules involved were complexing agents such as EDTA (ethylenediaminetetraacetic acid) or NTA (nitrilotriacetic acid) used in metal plating shops and bright nickel plating bath additives, From batch experiments, it is shown that complete decomplexing of EDTA and NIA is feasible. Complete TOC (Total Organic Carbon) removal from solutions containing 0.01 M EDTA, 0.02 M NTA and bright nickel plating bath additives could also be achieved. Recycling experiments show that decomplexing of EDTA and NTA solutions can be obtained at an average electrical energy input of ~20kWh.kg-1 of complexing agent. Decomplexing rates of respectively 3.l3 mmol.Ah-1 for EDTA and NTA have been obtained, The Instantaneous Current Efficiency (ICE) was 71% for EDTA and 95% by NTA, Simultaneous recovery of Cu from a 0.01 M Cu-EDTA solution has also been evaluated. A solution (1.8 dm3) containing 0.01 M EDTA and 528 ppm of Cu was treated in a single compartment cell at a current density of 2 A.dm-2. 73% of the TOC could be removed and a final copper concentration of 8 ppm was obtained.

Jan 1, 2003

By I. Gaballah

The electrochemical behavior of a chalcopyrite concentrate having a high pyrite content was studied in HC1 by potentiodynamic, potentiostatic and galvanostatic experiments using a cell having separate anodic and cathodic compartments. Anodic oxidation of chalcopyrite particles was realized both by their contact with the cunent feeder and by reaction with ferric and cupric ions. An increase of current leads to a more selective dissolution of chalcopyrite. Surface passivation was observed after an electrolysis time related to the cell current. Cathodic reduction of chalcopyrite concentrate seems to be more promising. Almost complete conversion of chalcopyrite to a copper sulfide (Cui.8.S) is observed, whereas no reaction of the pyrite was detected. This confirms the possible selective dissolution of copper from the chalcopyrite concentrate. Copper sulfide obtained by cathodic reduction was leached using a cupric chloride solution.

Jan 1, 1994

By Luis Cáceres, Genny Leinenweber

"We have designed a planar perpendicular flow cell for electrochemical measurement of a mineral available as a fine powder. The working electrode consisting of mineral powder supported on a carbon paste surface as a 4 mm diameter disk, was concentrically positioned inside a vertical tubular reactor. The counter electrode was a 316L tube embedded in the body cell. The supportive media was a 1.2:1 mixture of candle wax and graphite powder respectively, which is a good electrical conductor. The concentrate electrode as a film attached on a carbon paste disk was prepared rubbing the surface carbon paste against dried powdered mineral. An Ag/AgCl 1 M KCl cell as a reference electrode was attached to the body cell by using a fast coupling fitting. A stable flow rate was achieved using a frequency inverter to drive the pump motor. The flow through the cell verified to be laminar due to the Reynolds number in the cell flow passage. Cyclic voltammetry from - 1200 a 600 mVSAgE were measured using a carbon paste with and without mineral attached to the surface. The main findings of this work were: a). Electrochemical measurement of mineral powder in contact with flowing samples was easily achieved using ground mineral. This is important where massive samples are not available. b). The voltammetric curve features of ground mineral coincided with reported data. c). The working electrode could be quickly replaced while maintaining very good reproducibility."

Jan 1, 2014

By Kirsten Corin, Margreth Tadie, Michael Nicol, Cyril O’Connor, Jenny Wiese

"The recovery of base metal sulfides has been emphasized in the study of the flotation of platinum group minerals (PGMs). However, in some ore bodies such as the Platreef of the Bushveld Complex, sulfide minerals do not make up the majority of the more significant PGM mineralization. It is therefore important to develop a fundamental understanding of how non-sulfide and sulfide PGMs respond respectively to the current reagents being used in the flotation of these minerals. The interactions between platinum and palladium sulfides and tellurides with the thiol collectors, ethyl xanthate and diethyl dithiophosphate, have been studied using the electrochemical techniques of mineral rest potential and voltammetry measurements. The differences in the interaction between the two types of minerals with these reagents were of key interest. Rest potential measurements indicated stronger electrochemical interactions of the minerals with ethyl xanthate than diethyl dithiophosphate. These measurements also indicated that there are different forms of oxidized collector present on the mineral surfaces after interaction with ethyl xanthates. Voltammetry measurements support these observations and suggest differences of adsorption on Pt and Pd sulfides than on Pt and Pd tellurides. Voltammetry also showed that there was minimal electrochemical interaction between the Pt and Pd minerals and diethyl dithiophosphate."

Jan 1, 2014

By M. Girgis

The behavior of arsenic III during electrolytic refining of copper in acidic copper ?sulphate electrolytes was studied by different electrochemical methods such as, linear potential sweep, cyclic voltammetry, chronoamperometry and chronopotentiometry. The study showed that arsenic behaves as a depolarizing ion and has a deleterious effect on copper deposit. Three substrates; Pb, Cu and Ag were used during the refining process and the electrode kinetics were found similar for both Cu and Pb electrodes while a little difference was found for the Ag electrode. A microscopic study by scanning electron microscope was undertaken to show the influence of arsenic on deposit's morphology. Surface analyses of the deposit were carried out by some electronspectroscopic techniques such as Auger electron spectroscopy (AES) and X-ray photoelectron spectroscopy (XPS). The results showed that arsenic coexists with copper deposit at potential?~ -0.25 V.

Jan 1, 1987

By F. Rashchi, A. Ghahreman, J. Moghaddam, S. Karimi

"In this work, the kinetics of ferric-ferrous redox reaction on a passivated sphalerite electrode is studied by the application of chronoamperometry method in 0.5 mol L-1 H2SO4 solution. The electrochemical behaviour of ferric and ferrous couple was investigated on two sphalerite minerals acquired from two different geological regions (Iran and Canada). The carbon paste electrode (CPE) of sphalerite was initially prepared and passivated in 0.5 mol L-1 H2SO4 solution and after reaching the steady-state condition, ferric and ferrous sulfate solution was added. The registered current density differences between the current density of the passivated electrode and that of the electrode in the iron salts added solution were interpreted for kinetics of ferric-ferrous reduction-oxidation reaction. The equilibrium potential for ferric-ferrous couple on sphalerites surface was about 500 mV vs. Ag/AgCl. The exchange current density (i0) for ferric-ferrous redox reactions on the sphalerite samples had the same magnitude of 10–6 A cm–2. The electrochemical impedance spectroscopy (EIS) measurements at 550 mV vs. Ag/AgCl illustrated that sphalerite oxidation was controlled by two charge transfer process in both of Fe-free and Fe-containing solutions. The charge transfer resistance remarkably decreased when Fe salts added to the 0.5 mol L-1 H2SO4 solution, owing to the ferric-ferrous redox reactions being the predominant reactions on sphalerite surface.INTRODUCTION Direct atmospheric leaching processes for sphalerite concentrates are performed by reduction of an oxidant (e.g. ferric ion and oxygen) and oxidation of sphalerite to zinc ions. Oxygen could be an oxidizing agent as well, but the concentration of oxygen is very low in the solution. The role of ferric ions is predominate in this oxidation (Babu, Sahu, & Pandey, 2002). The oxidation reaction for sphalerite in the presence of ferric in can be presented as follows (Lampinen, Laari, & Turunen, 2015):"

Jan 1, 2017

By M. L. Free

Electrowinning is directly impacted by many parameters that include electrolyte composition, voltage, current density, contact resistance, temperature, electrode spacing, and fluid flow as well as many other interrelated factors. The effects of these parameters are primarily related to thermodynamics, mass transport, and electrochemical kinetics. In this study thermodynamic, mass transport, and electrochemical kinetic equations are simultaneously solved to determine the effects of such parameters on electrowinning current efficiency, power consumption, electrodeposit morphology, and electrodeposit distribution. Modeling predictions will be compared with experimental results.

Jan 1, 2006

By H. C. E. Regidor, M. G. Mena, H. D. Mendoza

Cyanidation leaching has always been the most widely used method of extraction of gold in the world. Its low cost and high selectivity has made it the prevalent choice for mining companies, and even for the small scale miners. The use of cyanidation in small scale mining has been an issue for the longest time, mainly due to the operation’s lack of safety measures, health care or environmental protection regulations. In pursuit of more environmentally friendly methods of extraction of gold, several alternative extraction processes have been explored, one of which is chlorination. The chlorination process is advantageous when recovering refractory gold locked in sulfides, as it simultaneously oxidizes the surrounding sulfides as well as dissolve any gold exposed to the lixiviant. This research was conducted to study and develop a safer alternative way of extraction of gold from small scale mining operations, without compromising the recovery of gold. In this study, a variation of the chlorination process has been employed for a refractory flotation concentrate wherein the majority of the gold is locked in sulfides. Hypochlorite-bearing reagents were used as the leaching reagents, and the method developed was a 2-stage leaching process in differing pH conditions. The solution pH and Eh was monitored all throughout the runs, and aliquot samples were taken at time intervals for analysis. SEM-EDS imaging was used to determine the mode of oxidation of the chlorination process, and the image obtained showed that the oxidized layer followed the shape of the particle, suggesting a diffusion controlled process. XRD analysis of the sample before and halfway through leaching further confirmed the oxidation of the sulfides. The amount of gold dissolved in the aqueous solution and in the solid residue were used as the basis for the determination of the recovery of gold. An average gold recovery of up to 84.38% was obtained using the developed method in just 7 hours of leaching. This method was then employed for a pilot-plant scale test and a gold recovery of 79.2% was obtained.

Jan 1, 2018

By Melvin H. Miles

"Considerable research has been conducted on the anodic oxidation of methanol in fuel cells. The electrochemical reduction of carbon dioxide in aqueous solutions to form methanol is the same reaction in reverse, i.e. CO2 + 6 H+ + 6 e- ? CH3OH + H2O. The same catalysts and conditions may operate for both reaction directions. This carbon dioxide reduction reaction, however, must be able to compete with the electrochemical reduction of water to form hydrogen gas. Thermodynamically, the reduction of CO2 to form CH3OH is slightly more favorable than the reduction of water. The use of nearly neutral electrolytes rather than acidic electrolytes makes the reduction of CO2 kinetically more favorable. The thermodynamics of various reaction steps are presented. Similarities exist with the electrochemical reduction of CO2 and the green-plant photosynthesis process that converts CO2 to carbohydrates.IntroductionVirtually all of the oxygen in the earth’s atmosphere is of biological origin having been generated by green-plant photosynthesis from water and carbon dioxide [1]. The net reaction can be represented byCO2 + H2O ? O2 + [CH2O] (carbohydrates, etc.) (1)Chlorophyll and enzymes promote this reaction, and the energy required comes from sunlight. The actual photosynthesis process is a complex multistage reaction and requires 469 kJ mol-1 of energy supplied by the sun. Isotope tracer experiments using 18O have shown that both the oxygen atoms in the O2 molecule originate from H2O, whereas oxygen atoms in the carbohydrates come from CO2 [1]. The total amount of water on the earth is split by photosynthesis and reconstituted by respiration and combustion once every 2 million years or so. The photosynthetically generated oxygen gas temporarily enters the atmosphere and is recycled about once every 2000 years [1]. The carbon dioxide is partly recycled in the atmosphere and oceans after an average residence time of 300 years and is partly fixed by precipitation of CaCO3 and other carbonate minerals [1]."

Jan 1, 2008

By Zhongning Shi, Ramana G. Reddy, Min Li, Zhaowen Wang

Electrodeposition of cobalt from cobalt tetrafluoroborate (Co(BF4)2) was investigated using 1- butyl-3-methylimidazolium tetrafluoroborate (BMIMBF4) ionic liquid. The experiments were conducted at 353 K. Chronoamperometry experiments confirm that the electrodeposition of cobalt on tungsten electrode proceeds via three-dimensional instantaneous nucleation with diffusion-controlled growth process. The average diffusion coefficient of Co(II) was found to be 7.5 × 10-8 cm2s-1 at 353 K, which is in good agreement with the estimated value from cyclic voltammetry. The electrochemical deposit was characterized using SEM-EDS and XRD methods. The SEM image shows formation of a dense and compact deposit at - 0.75 V. The EDS and XRD analysis confirm that the obtained deposit is pure cobalt metal.

Jan 1, 2015

By J. Howarth

Two electrochemical processing methodologies have been used to electrogenerate bromine-laden solutions for gold-leaching purposes. In the first process, a laboratory-scale cell in which the anode and cathode compartments were separated by a cation-exchange membrane was employed. The bromine produced by electrolysis of a 4% bromide solution was used to leach gold from a low-grade ore. The pregnant leach solution was then returned to the cell to recommence the cycle. High current efficiencies (90-93%) were maintained over six cycles. In the second process, an undivided hypochlorite generating cell (Chloropac"') was used to generate bromine from a simulated leach solution. Electrolyses were performed on a pilot-scale (100-150 gallons) with solutions containing different levels of bromide ion. The current efficiencies were also high (80-90%) and unaffected by the bromide concentration (over the range 2.5-5%) provided the electrolysis was run to low conversion « 15%). The Chloropac module was capable of delivering 0.6 kg bromine per hour at a power cost of $0.09 per kg. Using these figures, a detailed economic assessment for a 1000 metric tonnes (MT) per day gold ore processing plant was made. Electrolytic regeneration of bromine in a gold leach/recovery circuit dramatically improves the process economics over cyanidation.

Jan 1, 1991

By Q. G. Liu

New solid-state electrochemical sensors 1;.1sing Li2SO4-Ag2SO4 electrolytes have been developed to measure SO2 and/or SO3 in gas mixtures. Silver embedded in part of the electrolyte is used as the reference electrode. Although single-phase electrolyte sensors yield accurate results for one to two days, a two-phase electrolyte cell exhibits excellent long-term chemical stability. For example, stable and accurate potent iometric responses have been obtained over a six mo.nth period. The. advantages of the two-phase electrolyte ( 23 mol% Ay 2SO4 ) cell include excellent mechanical strength on temperature cycling and an insensitivity to compositional variations in the electrolyte and to temperature fluctuations. Experimental tests have shown excell.ent results in SO2-air. mixtures with the SO2 concentration ranging from 3 to 10,000 ppm (vol). However, the SO2 concentration range was limited by a lack of standard gas mixtures, and our sensor cells can be used to measure S02 concentrations significantly less than or larger than our experimental range. Results also indicate that the presence of significant concentrations of CO2 and H2O in the gas mixture has no effect on the sensor response. Thus the two-phase electrolyte ( 23 mol% Ag2S04) sensor has exceptional selectivity, reliability and long-term chemical and mechanical stability.

Jan 1, 1985

By Tomás Vargas

The catalytic influence of a pure strain of Thiobacillus ferrooxidans (ATCC 19859) on the dissolution of natural pyrite crystals was studied using electrochemical techniques. The results showed that this microorganism catalyze the leaching of pyrite by both, oxidizing ferrous iron in solution and depolarizing the reduction of ferric ion on this sulfide. In addition, studies of bacterial corrosion under applied potential showed that pitting on the pyrite surface centers on weak sites of the sulfide structure in which bacteria has attached, but occurs only when the ferric iron in solution induces an adequate level of anodic polarization on the mineral.

Jan 1, 1992