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Electrochemical study of chalcopyrite dissolution in sulphuric, nitric and
hydrochloric acid solutions
Tatiana das Chagas Almeida, Eric Marsalha Garcia, Hugo Walisson Alves da
Silva, Tulio Matencio, Vanessa de Freitas Cunha Lins
PII:
DOI:
Reference:

S0301-7516(16)30025-4
doi: 10.1016/j.minpro.2016.02.001
MINPRO 2861

To appear in:

International Journal of Mineral Processing

Received date:
Revised date:
Accepted date:

15 November 2014
29 January 2016
2 February 2016

Please cite this article as: Almeida, Tatiana das Chagas, Garcia, Eric Marsalha, da Silva,
Hugo Walisson Alves, Matencio, Tulio, de Freitas Cunha Lins, Vanessa, Electrochemical
study of chalcopyrite dissolution in sulphuric, nitric and hydrochloric acid solutions,
International Journal of Mineral Processing (2016), doi: 10.1016/j.minpro.2016.02.001

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ACCEPTED MANUSCRIPT
Electrochemical study of chalcopyrite dissolution in sulphuric, nitric
and hydrochloric acid solutions

T

Tatiana das Chagas Almeidaa, Eric Marsalha Garciab, Hugo Walisson Alves da Silvac,
Tulio Matenciod Vanessa de Freitas Cunha Linse
a

IP

Federal University of Rio de Janeiro, Horácio Macedo Avenue 2030, Zip Code 21941-914, Rio de
Janeiro, Brazil, tatiana das chagas @gmail.com
b

SC
R

Federal University of São João del Rey, Frei Orlando 170, São João del-Rei, Brazil, Zip Code 36307352, Belo Horizonte, Brazil, ericmgmg@hotmail.com.
c

Federal University of Minas Gerais, Antonio Carlos Avenue 6627, Zip Code 31270901, Belo Horizonte,
Brazil, hugowalisson@gmail.com.
d

NU

Laboratory of Materials and Fuel Cells, Chemistry Department, Federal University of Minas Gerais,
Antonio Carlos Avenue 6627, Belo Horizonte, Brazil, tmatencio@ufmg.br.
e

D

MA

Corrosion and Surface Engineering Laboratory, Chemical Engineering Department, Federal University
of Minas Gerais, Antonio Carlos Avenue 6627, fax number + 55 31 34091789, phone number + 55 31
34091781, Zip Code 31270901, Belo Horizonte, Brazil, vlins@deq.ufmg.br

TE

Abstract

Electrochemical and surface analyses were carried out to study the leaching of chalcopyrite in acid media,

CE
P

aiming to increase copper extraction from low-grade chalcopyrite ores. Unpublished results include the
use of electrochemical impedance spectroscopy (EIS) to characterize the dissolution resistance of
chalcopyrite surfaces in 0.1 mol∙L-1 of hydrochloric, nitric or sulphuric acids. Potentiodynamic

AC

polarization, atomic absorption spectrometry and EIS analysis showed that hydrochloric acid solutions are
more efficient leaching agents than nitric and sulphuric acids. The impedance results suggested that the
chalcopyrite dissolution is a diffusion-controlled process in hydrochloric and sulphuric acids. The use of
Raman spectroscopy and scanning electron microscopy with energy dispersive spectrometers (SEM/EDS)
allowed the partial identification of lead and bismuth sulphides as impurities. Two products were
identified on the surface of chalcopyrite after anodic polarization, i.e., sulphur in the sulphuric acid only
and covellite in all three acids.
Key words: chalcopyrite leaching; electrochemical impedance spectroscopy; acid dissolution; Raman
spectroscopy

They reported that a high-resistance passive layer grows on the chalcopyrite surface without cupric and/or ferrous ions. and has high capital for smelting and refining plants. The presence of . 2012. using sulphuric acid leaching solutions at pH 2. However. In contrast. which is an important tool for the study of surfaces (Hiroyoshi et al. Dakubo et al. and the viability for small or large plants (Dutrizac. as NU well as negative environmental impact caused by the generation of sulphur dioxide (SO2) (Prasad and Pandey. This slow kinetics is attributed to the formation of a protective layer on the mineral surface. 18% of copper extraction comes from the hydrometallurgical processes. Ghahremaninezhad et al.Introduction Chalcopyrite (CuFeS2) is the Earth’s most abundant Cu bearing mineral. and that coexistence of these ions causes the formation of another product layer and inhibits the formation of intermediate Cu2S in the active region... 2008). Despite many years of studies. as there are several challenges to be overcome. D The application of the hydrometallurgical process for the production of copper is promising but has not TE yet been consolidated. The extraction of copper from IP ore may be conducted using two different processes: the pyrometallurgical and the hydrometallurgical. and accounts for approximately T 70% of the world’s copper reserves (Li et al. where the CE P copper dissolution from chalcopyrite in an acid medium is slow at low temperatures and tends to decrease with time (Majuste et al. The difficulty of employing such a method for the hydrometallurgical extraction of copper from chalcopyrite is the leaching step.. Habashi. inhibiting continued dissolution (Córdoba et al. the formation of this layer and its characteristics are not yet fully established. (2004) studied the synergistic effect of cupric and ferrous ions on active-passive behavior during anodic dissolution of chalcopyrite in sulphuric acid solutions. 2015. 2009). using EIS technique. 2012). 2008). SC R The pyrometallurgical process has dominated the copper industry since the late nineteenth century (Dreisinger.. The hindered chalcopyrite AC dissolution process has also been reported elsewhere (Majuste et al...ACCEPTED MANUSCRIPT 1.. small initial capital expenditure required for the installation of industrial plants. This process is not suitable for the treatment of complex and low-grade ores. Few studies have used the technique of electrochemical impedance spectroscopy (EIS). Hiroyoshi et al. 2013). (2012) investigated the effectiveness of peroxodisulphate for enhancing copper leaching rates from chalcopyrite. Dakubo et al.. 2006. 1998). Cordoba et al. 2004. 2012). this scenario is changing slowly. 1992). The MA advantages of hydrometallurgy are the ability to treat complex ores with low copper content.

Gharehmaninezhad et al. EIS analysis at open circuit potential proved the existence of a thin surface layer on the T electrode. 2010. Direct leaching of chalcopyrite concentrate includes the use of sulphuric acid. 2014. 2014b. 2. D Wang et al.ACCEPTED MANUSCRIPT peroxodisulphate greatly increased copper leaching rates.. Zhang et al. and Raman spectroscopy for the characterization of the chalcopyrite surface after dissolution.. Wang et al.. 2014. The specimens were rinsed with double-distilled water and dried with analytical grade acetone 100% (Synth®). ammonia systems. Rochester.11-4246). to obtain specimens with 1. mounted in epoxy resins (Epofix®. (2012) evaluated the surface of chalcopyrite during dissolution in 0. Li et al.. Smith and Sohn. and biological processes (Venkatachalam.. D-550). in the potential range of 300-420 mV (MSE). This layer was stable up to 100 mV vs. chloride ions.5 cm thicknesses. and transpassivation potential were obtained using anodic potentiodynamic polarization tests. Firstly. once dried and hardened. 2014. 1991. MA oxygen leaching. mercury/mercury sulphate electrode (MSE) and was IP assumed to be Cu1-xFe1-yS2. The samples were. Gharehmaninezhad et al..0 cm2 of exposed areas and 0. passivation current density. Solis-Marcial et al. were mechanically wet-polished using SiC papers .Material and Methods The chalcopyrite samples were purchased from Ward’s Natural Science. Chalcopyrite electrodes were prepared as per Majuste et al. then. AC The charge transfer resistance and mechanistic information were obtained using electrochemical impedance spectroscopy. the previously SC R formed layer partially dissolved and a second layer (Cu 1-x-zS2) was formed on the surface. Feng et al. 2014a. However. Khoshkhoo et al. 2014).. Both layers showed the characteristics of passive layers at a low scan rate (0. TE Abdollahi et al. (2012). 2013. Struers). The aim of this work was to understand the chalchopyrite dissolution in hydrochloric. alcoholic acid media. 2012). Watling. both NU surface layers dissolved and active dissolution of the electrode started (Gharehmaninezhad et al. 2014.5 mol∙L-1 sulphuric acid solutions using electrochemical techniques.. A Cu wire within a glass tube was then attached to each specimen using a conductive silver paint (Dotite®. EIS. 2014.05 mV∙s-1) but acted like pseudo-passive layers at high scan rates (≥ 50 mV∙s-1). massive samples were cut using a diamond wafering blade (Buehler®.. sulphuric and nitric acids through an electrochemical study using anodic CE P potentiodynamic tests. these resin blocks. nitric acid. By increasing the potential to the range of 100-300 mV (MSE). The electrochemical parameters such as critical current density.Y. n. N. 2014..

ACCEPTED MANUSCRIPT (grit sizes 1000. Quest).27 ± 0. nitric and sulphuric acid solutions.. The chalcopyrite samples used were IP characterized in a previous work (Majuste et al.0 and 0. The analysis of the electrode surface was also made by Raman spectroscopy using a Jobin Yvon Horiba instrument (Labram HR800) equipped with a CCD detector and He-Ne laser operating at 633 nm. The reference electrode used was Ag/ AgCl. 2012). dried with analytical grade ethyl alcohol 95% (Synth®) and kept T under vacuum at room temperature (Majuste et al. the electrodes were rinsed with double-distilled water in an ultrasonic bath for 15 min. AC For the EIS analysis.05°C CE P in 0.05 μm) to obtain fresh and smooth electrode surfaces (Majuste et al.3 V (Ag/AgCl). The surface of the chalcopyrite electrode was analyzed using a scanning electron microscope (JEOL. The treatment and equivalent circuit simulation were carried out using the ZviewTM software. Atomic absorption spectroscopy MA analyses of acid solutions were performed before and after polarization tests. nitric and sulphuric acid solutions were prepared with deionized water and concentrated hydrochloric. The power used was 20 mW focused on the sample by a BX-41 Olympus microscope comprising lenses with magnifications of 10. The anodic potentiodynamic polarization and EIS were performed at room temperature 25 . Quantitative analysis of iron and copper contents in the leachates was performed using the atomic absorption NU spectrometer Hitachi-Z8200 coupled to a Hitachi graphite furnace. 2012). at a scan rate of 0. KCl (sat) and the counter electrode was platinum. 1200 and 2400) and subsequently alumina pastes (1. respectively. and Versa Studio software.10-2 Hz. The spectral resolution was 1 cm-1. SC R 0. 2012). all analytical grade reagents (Synth ®). Next.05 V∙s-1.1 mol∙L-1 of hydrochloric.1 to 1. All experiments were carried out without TE D stirring. JSM 6360 LV) with energy dispersive spectrometers (Thermo Noram.1 mol∙L-1 of hydrochloric. The anodic polarization was performed in the potential range of 0. using a Versa Stat 2 Princeton Applied Research potentiostat. Electrochemical tests were performed in a 150 mL electrochemical cell. ... An average of 10 accumulations in the acquisition time of 60 seconds was performed. nitric and sulphuric acids. 50 and 100x. the potential amplitude and frequency range were 10 mV and 105 .

3 V (Ag/AgCl). A tendency to MA concentration polarization (McCafferty.1 Anodic potentiodynamic polarization The anodic polarization curves of the chalcopyrite in three types of acids are shown in Figure 1. obtained using the potentiodynamic polarization technique. 2010) for the cathodic reaction which was observed only in the nitric acid. at high cathodic CE P overvoltage. Either event will result in concentration polarization (McCafferty. In the hydrochloric acid. Another advantage of the use of sulphuric acid as a leaching agent is that the current density at the region of the protective layer is one order of magnitude higher than the current density at the region of the protective layer produced in the nitric acid. are shown in Table 1. the increased number of hydrogen gas molecules produced may be slow to diffuse away from TE the electrode surface. the energy dispersive spectrometry (EDS) and Raman spectroscopy were performed immediately after sample preparation and after anodic polarization up to T 1. The protective layer dissolves at a higher rate in sulphuric acid than in nitric acid. SC R IP 3. However the protective layer breaks at a higher potential in the sulphuric acid. the reduction of protons with hydrogen evolution occurred without inhibition until 0. When electrolytes are in the sulphuric and hydrochloric acids. 2010) to produce a protective layer was observed in the case of sulphuric acid.1 V (Ag/AgCl). an inhibition of the cathodic reaction was identified. AC The electrochemical parameters. In this medium. The chalcopyrite dissolution is facilitated in hydrochloric acid due to the lowest transpassivation potential in this medium. so does not favor the formation of a protective layer of corrosion product. The highest critical current density (McCafferty. 2010) was observed in the cathodic branch of the curve of chalcopyrite in the nitric acid. On the cathodic side of the curve in HNO3 medium. increased hydrogen evolution at large cathodic overvoltage may cause a depletion of protons near the electrode surface. The NU polarization curves obtained with a high potential range in the three acid media are useful to give a general idea of the electrochemical behavior of the electrode in the medium studied. hindering the leaching process. the dissolution of chalcopyrite is continuous after a very small region of relatively constant current. The hydrochloric acid is not an oxidizing medium. . In D addition.Results and Discussion 3.ACCEPTED MANUSCRIPT The scanning electron microscopy (SEM).

.3 V vs.↔ 2H2O (1) (2) On the increase of the cathode area.+ 26H+ + 28e- (3) CE P The CuS layer is unstable at potentials higher than 1.085 V vs. 2007): (4) 2CuFeS2 + 16H2O ↔ 2Cu2+ + Fe2(SO4)3 + SO42.+ 32H+ + 34e- (5) AC CuS + 4H20↔Cu2+ + SO42..25Cu2+ + Fe2(SO4)3 + 0.ACCEPTED MANUSCRIPT The previous reduction of the chalcopyrite surface (Figure 1) contributes to the formation of a passive or pseudo-passive layer in oxidizing acids such as sulphuric and nitric.+ 16H+ + 17e- (7) 3. where T iron is preferably oxidized. increase in the potential up to 1. 2010): 2CuFeS2 + 13H2O ↔ 0.25SO42. 2010): CuFeS2 ↔ Cu2+ + Fe3+ + 2S + 5e- (6) CuFeS2 + 8H2O ↔ Cu2+ + Fe3+ + 2SO42. Ag/AgCl. By reducing metal ions on the chalcopyrite surface. According to the literature.2 Electrochemical impedance spectroscopy . metallic iron and metallic copper regions appeared generating a galvanic pair. according to reactions (Viramontes-Gamboa et al. SHE D causes the complete release of iron from the chalcopyrite lattice into solution and the formation of a CuS TE layer on the electrode surface according to the reaction (Ghahremaninezhad et al. The metallic copper area is a cathodic region where the cathodic reactions IP occurred: SC R 2H+ + 2e. Atomic absorption spectroscopy results (Table 2) showed that after the anodic polarization up to 1. SHE. The main anodic reactions proposed in the literature for the dissolution of chalcopyrite in 1M hydrochloric acid solution are (Gharehmaninezhad et al. in sulphuric acids..+ 8H+ + 8e- The concentrations of iron and copper measured using atomic absorption spectroscopy were obtained after polarization up to 1.165 V vs.75CuS + 1. Leaching with the nitric acid resulted in the lowest leaching efficiency relative to the copper extraction. which is near the potential range described in the literature for the extraction of iron and copper from chalcopyrite. higher Cu contents and Cu/Fe ratio were obtained in the sulphuric and hydrochloric acid leaching.↔ H2 4H+ + O2 + 4e. the complete dissolution of chalcopyrite occurs by further increasing the potential.3 V vs. Therefore. a higher consumption of electrons occurs favoring the dissolution of NU chalcopyrite. MA Ag/AgCl.

of immersion in the acid solutions suggests the formation of a corrosion product on the electrode surface and an occurrence of ohmic polarization (McCafferty. NU standard deviation and variation coefficient were calculated. and causality must satisfy the K-K D relationships. The electrochemical parameters obtained from the EIS measurements are shown in Table 3. The rapid increase in potential during the SC R first 15 min. The profiles in Figure 2 were almost the same for the three acids. As compared to this work. The Nyquist diagram of chalcopyrite in the three acids is shown in Figure 3a. (2010) pointed out that the existence of chloride ions can enhance the chalcopyrite leaching rate. The standard deviations (SD) of corrosion potentials are shown in Table 3. which is a capacitance of the surface film. MA EIS was performed at a potential amplitude of 10 mV (Ag/AgCl) in relation to the stabilized open circuit potential. the potential IP stabilized and slightly varied at a rate lesser than 0. At the intermediate frequency (from 100 to 1 Hz). stability. Table 3 shows the mixed potential (open circuit potential) of chalcopyrite obtained for the three acid. R3 is the charge transfer resistance occurring within the pores of the . Any system that satisfies the priori conditions of linearity. so that TE the transformed quantities may be compared directly with their corresponding experimental values for the same parameters. The curve is ascending. with SD being greatest for leaching with hydrochloric acid. 2014). After 30 min. The equivalent circuit fitted to the EIS data is shown in Figure 4 a for the hydrochloric and sulphuric acids and in Figure 4 b for the nitric acid. Nicol et al. The highest impedance was obtained for the dissolution of chalcopyrite in the sulphuric acid.. Each test was conducted for a minimum period of 1 h. The first value at high frequencies (105 Hz) is associated with the solution resistance (R1) which was very low and similar for the three acids used (Table 3). (2011) reported the same equivalent circuit for the dissolution of chalcopyrite in electrolyte solution containing ethyl xanthate.3 mV/min.. except for the first analysis (Test 1) in hydrochloric acid starting at T 210 mV (Ag/AgCl). Yu et al. starting at a potential below 200 mV (Ag/AgCl). The K-K technique transforms the real into the imaginary component and vice versa. was also observed. The Kramers-Kroning (K-K) relationships were applied to validate experimental results. The average potential. 2010). A good agreement between the experimental and transformed impedance data for both CE P real and imaginary components validates the EIS data (Zheng et al. Dreisinger and Abed (2002) reported AC that hydrochloric acid is more efficient than sulphuric acid as the activity of Fe3+ in sulphuric acid solution is reduced due to the formation of FeSO4+. a parallel circuit was identified and a charge transfer resistance (R2) of a surface film with a constant phase element (CPE1).ACCEPTED MANUSCRIPT Measurements of open circuit potential were performed until potential stabilization (Figure 2).

The element W1 or Ws is a finite length diffusion element used in the case where one boundary CE P imposes a fixed concentration for the diffusing species. the CPE describes an ideal capacitor corresponding to an ideal flat electrode. The diffusive elements are closer to the Warburg element for the hydrochloric and sulphuric acids. In sulphuric and hydrochloric acids. In this work. Y0 is the admittance of an ideal SC R capacitance. The admittance representation of CPE is given by: T Y(ω) = Y0(jω)n = Y0 ωn cos(nΠ/2) + jY0 ωn sin(nΠ/2) (8) IP where ω is the angular frequency. other diffusive elements are useful models for diffusion when a thin film (finite diffusion) is involved. 1985). a diffusion control of the chalcopyrite . which is beneficial to the chalcopyrite dissolution. (2011) also proposed the existence of Warburg impedance for the chalcopyrite dissolution. corresponding to NU porous electrodes (Rammelt and Reinhard. 2011). The dispersion relation contained in the admittance represents a cotangent-hyperbolic function: (9) AC Y(ω) = Y0(jω)1/2 coth [B (jω)1/2] The peak in the curve of Bode diagram of phase angle (Figure 3b) is broad and can signify more than one time constant with similar values.40 (Ws-P in Table 3) for the dissolution of chalcopyrite in hydrochloric acid and n = 0. When n=1. the latter of which is considered the Warburg impedance (WsR in Table 3) related to the ionic flux across the surface film. and the CPE behavior of interfaces has been ascribed to a fractal nature (special geometry of the roughness) of the interface. j is the imaginary unit (√-1). When n=0. The maximum of the phase angle curve of the chalcopyrite in hydrochloric acid occurred at a lower angle than the maximum of chalcopyrite in nitric and sulphuric acid solutions. The impedance associated with a diffusive control of the dissolution is TE W1. indicating a more resistive behavior.ACCEPTED MANUSCRIPT surface film (Yu et al. and CPE2 is the associated capacitance.45 for the MA dissolution of chalcoprite in sulphuric acid. CPE is encountered frequently in solid state electrochemistry. and n is the parameter which characterizes deviation of the system from ideal capacitive behavior. The curve of phase angle starts around φ = 38° at low frequencies in the case of hydrochloric acid. and thus it is permeable to the diffusing species. However. Yu et al. for the CPE in series with R3 (Figure 4a). and around φ = 37° for sulphuric acid. the CPE represents a Warburg impedance related to the ionic flux across the film.. n=0.5. 1990). This type of dispersion relation is generally found in corrosion related diffusion (Boukamp. The angle associated with the Warburg element is 45o. The simulation associated with the impedance spectra indicates that the process is controlled by diffusion in the product layer in the D hydrochloric and sulphuric acids. when the semi-infinite linear diffusion occurs.

91 wt.3 V (Ag/AgCl) (Figure 1) are shown in Figures 5. Fe.constant phase element) was assumed as equivalent circuit. Figure 6 shows an intergranular corrosion of chalcopyrite in the nitric acid solution. Fe (30. The EDS results showed a semi-quantitative characterization of typical chalcopyrite. 6 and 7 for leaching in the hydrochloric. Hiroyoshi et al.% of Cu. Hiroyoshi SC R et al. The authors observed a diffusion control of MA the chalcopyrite dissolution and also found that the slow dissolution step of chalcopyrite is due to the slow diffusion of iron through a passive film.%).86 wt.%).%) and Cu (34. the chalcopyrite dissolution is disadvantaged in this medium.5% variation).97 wt. presence of the Fe 2+ / Fe 3+ NU Ghahremaninezhad et al. respectively.%). such as a diffusion element. oxidizing sulphide to sulphur. In Figure 5.17 wt. A series circuit between Re (solution resistance) and a parallel R-CPE circuit (resistance . The CE P results of anodic polarization suggested a diffusion control of the cathodic reaction in nitric acids. A by-product is the TE NO(g). However. It has been postulated that the species D which reacts with sulphide is NO+ rather than NO3-. The EDS analysis of the chalcopyrite surface resulted in S (35. which further reacts with NO2(aq) and regenerated NO+ in acid media (Anderson et al. The EDS analysis of chalcopyrite surface before the polarization test in sulphuric acid revealed the following composition: S (35.10 wt.95 wt. which consisted primarily of S (34.ACCEPTED MANUSCRIPT dissolution process is proposed. 2011). Fe (30. nitric and sulphuric acid solutions. The chemical leaching of chalcopyrite in nitric acid is complex. dark regions appeared showing a localized attack of .67 wt. (2004) emphasized that the final frequency (10-1 Hz. which are deeper than the light regions is an evidence of localized corrosion for leaching in hydrochloric acid. the appearance of dark regions. 3.. and S did not change significantly (with up to 7.69 wt. (2012) used EIS to study the kinetics of chalcopyrite leaching process in the redox couple in sulphuric acids.02 wt. the wt. As the chalcopyrite in the sulphuric acid showed the highest Warburg impedance value (Table 3).3 Scanning electron microscopy and dispersive energy spectroscopy AC SEM images of chalcopyrite before and after polarization up to 1. Fe (30.%) and Cu (33.%). since they occur at lower frequencies. nitric and sulphuric acids. an intermediate frequency) probably prevented some elements from being observed.%) and Cu (33.%).%). (2004) used EIS to study the effect of Cu2+ and Fe2+ in the formation of the passive layer IP T on the surface of chalcopyrite in sulphuric acids. After polarizations with hydrochloric.

The Raman spectrum obtained for area 1 (b) is not well defined and only shows several minor broad bands between 80 and 320 cm-1. variations in iron.13 and 0. MA Figure 8 is an optical micrograph of the polished surface of chalcopyrite electrode and shows the spectrum collected from area 1 (a).% S). there is only one intense band at 294 cm-1 that corresponds to chalcopyrite (Mernagh and Trudu.ACCEPTED MANUSCRIPT the electrode surface by the leach medium. 270. 2009). and especially to elucidate possible reaction products formed by the dissolution of the electrode after polarization in 0. .. 2009) can be associated with different experimental conditions..% Bi). AC differences in geological formation conditions of samples. It is important to note that small differences in the intensity and position of these bands in the spectra. 90. Bands at TE 270. 1993). as discussed in the literature (Majuste et al. (39.. 320 and 352 cm-1 were suggested to be associated with the molecular vibrations of the Fe-S bond. 2015). Lu and Dreisinger (2013) reported high contents of impurities including Bi and Pb in a chalcopyrite concentrate. all with relatively low intensities. 320. Similarly. The measurement NU depth of Raman microspectroscopic analysis is usually at the µm scale. IP T 3. This spectrum appears to be similar to the spectra of lead and bismuth sulphides as mineral galenobismutita (PbBi2S4) and aschamalmita (Pb6Bi2S9) (RRUFF. Parker et al.4 Raman spectroscopy SC R Raman spectroscopy was used to characterize the matrix (chalcopyrite) and impurities on the surface of chalcopyrite. and the 265 cm-1 band was thought to be from the Cu-S bond (White. 2013).39 wt.1 mol∙L-1 hydrochloric. copper and sulphur contents in the chalcopyrite. 0. The SEM analysis identified a localized corrosion of the electrode surface in all electrolytes. Figure 9 presents a Raman spectrum of area 1 (b) as shown in the optical graph.11 (White. 2009). depending on the materials for analysis (Qian et al.% Pb) and (28.37 wt. 105. White.10. being intergranular in the nitric acid. The spectrum also exhibits D additional bands at 78.72 wt. and features in its crystalline structure. nitric and sulphuric acids. 1993. and comprised a lead bismuth sulphide phase (16. 320 and 359 cm-1 are reported in literature as chalcopyrite Raman bands with normalized intensities CE P of 0. This grain with color contrast in the optical image was the same as that for the EDS analysis of chalcopyrite surface after nitric acid polarization. In the range from 75 cm-1 to 550 cm-1. 2012. Mernagh and Trudu. 359 and 377 cm-1. 2008. The bands at 291.

. with additional bands at 472.ACCEPTED MANUSCRIPT After polarization up to 1. however. Although the position of this band is similar to the sulphur band at 472 NU cm-1. Based on previously published work. 246 and 187 . This 471 cm-1 band did not appear on the polished electrode surface (without the presence of corrosion products). Area 2. and appears with T different intensities in the marked areas. and additional very weak bands at 437. which explains the reduction in the intensity of the typical chalcopyrite vibrational band at 294 cm-1. respectively. Anderson et al. The optical micrograph of the chalcopyrite electrode after anodic polarization in sulphuric acid showed a different staining (Figure 12). under the optical microscope (with Raman spectroscopy) were formed on the chalcopyrite surface (Figure 10). 2011). This suggests that a corrosion product. and the Raman spectra were collected to characterize these distinct areas. D Raman spectra of the chalcopyrite electrode performed after polarization in the nitric acid were obtained TE for the areas with different colors (green. These three new bands from area 2 are typical of sulphur. 2009). despite of the color contrast under the optical microscope. as compared to that for area 2 and increases in the 471 cm-1 band. possibly covellite as discussed above. Earlier publications have reported that the sulphur formed during the leaching in nitric acid media is oxidized to sulphate via reactions with NO(g) and oxygen (Prasad and Pandey. Areas 3 and 4 showed decreases in signal intensity from the 294 cm-1 band SC R typical of chalcopyrite. the intensity of this band is higher IP than that for other areas. characteristic of sulphur. White. Elemental sulphur (S8) with orthorhombic crystal structure shows very strong bands at 219 and 472 cm-1 (Parker et al. it is suggested that covellite may be a corrosion product formed on the chalcopyrite surface leached in hydrochloric acid. red and purple) as shown in Figure 11.3 V (Ag/AgCl) in the hydrochloric acid. The Raman spectrum of covellite (CuS) shows bands at wave MA numbers 471 and 263 cm-1 (Mernagh and Trudu. A strong band of the chalcopyrite at 294 cm-1 is still evident after anodic polarization. may have formed. suggests that the band at 471 cm-1 is due to the presence of another phase. 1998. as compared to those for areas (3) and (4). suggesting similar surface compositions within the two areas. regions with different colors. Sulphur was not identified after anodic polarization AC in nitric acid. showed a quite different spectrum. The spectra (Figure 12) for the areas 3 and 4 were the same. 1991. In the yellowish area (area 2). the absence of the band at 219 cm-1. suggesting the growth of a surface film. 219 and 153 cm-1 . 1993) with strong and weak intensities. Venkatachalam.. 2008. A less intense band can be seen at 153 cm-1. It was found that the three areas all showed sharp decreases in intensity of the chalcopyrite band at 294 cm-1 and increases in CE P the intensities of the bands in the range of 471 to 475 cm-1.

The sulphur deposit reduces the anode area and the current density increases. 1969. 4.5 to 1. 2008. Hiroyoshi et al.5 V D vs.5V (SHE). Hiroyoshi et al.. 2009). Majima et al. Harvey and Butler. The highest Warburg impedance was obtained for the . For leaching in the nitric acid.ACCEPTED MANUSCRIPT cm-1. The covellite identified on the surface of the chalcopyrite after polarization tests in hydrochloric and nitric AC acids is a semiconductor (different to sulphur) allowing the transport of ions and electrons through the corrosion product film. 1976. Muñoz et al.. MA Elemental sulphur has been detected as a product of dissolution of chalcopyrite in acid media by means of different techniques (White.5 V (SHE). The dissolution of chalcopyrite in sulphuric acid occurred with the formation of sulphur (area 2) and T showed no intense band at 471 cm-1 for areas (3) and (4). S2. indicating the IP formation of covellite. White. bornite (S1) oxidizes to covellite.. (1982) conducted a study of the anodic dissolution of chalcopyrite in sulphuric acids based on thermodynamic analysis and proposed the formation of two intermediates. S1 and S2. CE P (2004) reported that in the passive region the Cu2S is not formed and only the passive elemental sulphur layer growths according to the direct oxidation of chalcopyrite. Linge. 1985). but rather vibrations at 268 cm-1. The S1 product was responsible for the passivation of the sample potential near 0.. 1986. 1979. 1976. and has been proposed as bornite (Cu5FeS4). a concentration polarization was identified in the cathodic branch of the polarization curve. The formation of NU elemental sulphur on the surface of chalcopyrite may have also contributed to the increase in transpassivation potential. 2012). At higher potential than 0. The bands in the 100–300 cm−1 region are due to S–S–S bending and the bands in the 400–500 cm−1 region are due to S–S stretching (Ozin. (2004) using EIS to study the dissolution of chalcopyrite in TE the sulphuric acid reported the growth of a passive layer of elemental sulphur of high resistance on the surface of chalcopyrite in sulphuric acid and in the absence of ferrous and cupric ions. 1979. (CuS) and subsequently to elemental sulphur (S). Its formation has been reported in a wide potential range of 0. Warren et al. Jones and Peters. pH (Majuste et al. 2009. Biegler and Swift.Conclusions The results of potentiodynamic anodic polarization show that the chalcopyrite dissolution is favored in the hydrochloric acid. SC R Sulphur identified as a corrosion product on the chalcopyrite surface in the sulphuric acid may be responsible for the higher passivation current density observed in this medium relative to the other acidic media. Parker et al.

O. An update on the NSC pressure oxidation of combined AC copper and molybdenum concentrates. Coordination of Improvement of Higher Education Personnel. Anodic electrochemistry of chalcopyrite.. Mesophilic CE P and thermophilic bioleaching of copper from a chalcopyrite-containing molybdenite concentrate. Soc.A. 25-32. 68-73. Farrell. Electrochem... Leaching of chalcopyrite with ferric ion. 545554. Twidwell. 2012.Z. C. 1985.. Noaparast. J.. 2014. F.A.. Córdoba. Research Support Foundation of Minas Gerais State. Ballester. M. D. Boukamp. Computer Aided Acquisition of Corrosion Data.. Hydrometallurgy 66. L. Anderson.. . Z. IP T The characterization study of the electrodes by SEM / EDS and Raman spectroscopy revealed that the chalcopyrite electrode presents cavities.H. Miner. H. NU Acknowledgement The authors are grateful to the Brazilian government agencies: National Council for Scientific and MA Technological Development. J. Manafi. 146. A fundamental study of the reductive leaching of chalcopyrite using metallic iron part I: kinetic analysis. 128. The use of Raman SC R micro-spectroscopy allowed the identification of two corrosion products formed after polarization up to 1. T.. 2008. Shafaei.C.. J. Dreisinger.3 V (Ag/AgCl).. The EIS results at low frequency region suggest that the dissolution of chalcopyrite is controlled by the diffusion through the product layer in sulphuric and hydrochloric acids. Process. N. A.L. Muñoz. Applied Electrochem 9. J.. 6th International Seminar on Copper Hydrometallurgy. M. The authors thank Dr. T. and covellite in the nitric and hydrochloric acids. Niemelä. Tuovinen. to their valuable D contribution. Int. Daniel Majuste.. Biegler. Swift. Peroxodisulphate assisted leaching of chalcopyrite. González...M. from the Federal University of Minas Gerais. F. Virginia Simpatico Teixeira Ciminelli and Dr. 2002.. D.. fractures and impurities on its surface. 1-14. Hydrometallurgy 93. 85-3. B.. J.. Part I: General aspects.I. Dakubo. Hydrometallurgy 121-124. S. 81-87. 1979.. Fayram.. 37-57. S. Abed.A. sulphur formed in the sulphuric acid. E. 2011. Blázquez. faults. Baygents. TE References Abdollahi..ACCEPTED MANUSCRIPT dissolution of chalcopyrite in the sulphuric acid.

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Figure 10 – Optical micrograph of chalcopyrite electrode after polarization in HCl solution and Raman spectra of areas 2. 3 and 4.3 V(Ag/AgCl) in 0. 3 and 4.1mol/L HNO3 at 25° C. Figure 7 – SEM micrograph of chalcopyrite (a) after polishing (b) after polarization in solution of CE P 0.ACCEPTED MANUSCRIPT Figure Captions Figure 1 – Anodic polarization curves of chalcopyrite from 0.region 1 (b). AC Figure 9 . . HNO3 and H2SO4 at room temperature. potential amplitude of 10mV and frequency range were of 105 10-2 Hz.1mol/L HCl at 25° C.1mol/L H2SO4 at 25° C. Figure 11 – Optical micrograph of chalcopyrite electrode after polarization in HNO 3 solution and Raman spectra of areas 2. MA Figure 5 – SEM micrograph of chalcopyrite (a) after polishing (b) after polarization in solution of 0. 3 and 4. IP T Figure 2 – Open circuit potential in function of time in 0. Figure 12 . Figure 8 – Optical micrograph and Raman spectrum of chalcopyrite electrode after polishing and before polarization tests .Optical micrograph of chalcopyrite electrode after polarization in H 2SO4 solution and Raman spectra of areas 2. D Figure 6 – SEM micrograph of chalcopyrite (a) after polishing (b) after polarization in solution of TE 0. HNO3 and H2SO4 at room temperature and scan rate of 50 mV.1mol/L aqueous solution of HCl. NU Figure 4 – Equivalent circuit fitted to the EIS data: (a) for the solutions of hydrochloric and sulphuric acids and (b) for the nitric acid. HNO3 and H2SO4 at room temperature.1mol/L aqueous solutions of HCl.1mol/L aqueous solutions of HCl.Optical micrograph and Raman spectra of chalcopyrite electrode after polishing and before polarization tests .s-1.1 V(Ag/AgCl) to 1.region 1 (a). SC R Figure 3 – Nyquist (a) and Bode (b) diagrams of chalcopyrite in 0.

D MA NU SC R IP T ACCEPTED MANUSCRIPT AC CE P TE Figure 1 .

TE D MA NU SC R IP T ACCEPTED MANUSCRIPT AC CE P Figure 2 .

AC Figure 3 CE P TE D MA NU SC R IP T ACCEPTED MANUSCRIPT .

T ACCEPTED MANUSCRIPT AC CE P TE D MA NU SC R IP Figure 4a .

IP T ACCEPTED MANUSCRIPT AC CE P TE D MA NU SC R Figure 4b .

SC R IP T ACCEPTED MANUSCRIPT AC CE P TE D MA NU Figure 5 .

SC R IP T ACCEPTED MANUSCRIPT AC CE P TE D MA NU Figure 6 .

SC R IP T ACCEPTED MANUSCRIPT AC CE P TE D MA NU Figure 7 .

NU SC R IP T ACCEPTED MANUSCRIPT AC CE P TE D MA Figure 8 .

SC R IP T ACCEPTED MANUSCRIPT AC CE P TE D MA NU Figure 9 .

NU SC R IP T ACCEPTED MANUSCRIPT AC CE P TE D MA Figure 10 .

NU SC R IP T ACCEPTED MANUSCRIPT AC CE P TE D MA Figure 11 .

NU SC R IP T ACCEPTED MANUSCRIPT AC CE P TE D MA Figure 12 .

1.2x10-6 357±21 388±27 31 H2SO4 6.6x10-5±1.4x10-4±3.ACCEPTED MANUSCRIPT Table 1 – Electrochemical parameters obtaining using anodic polarization technique Solution icrit.4x10-5±1.2x10-6 1.) (mV) SC R IP T (A/cm2) ipass.2x10-4±7.9x10-7 389±35 525±31 136 AC CE P TE D MA NU HCl .3x10-5±4.79x10-5±8. (Etransp. Epass.8x10-5 1. Etransp.2x10-6 397±28 750±67 353 HNO3 6.4x10-6 1.- (A/cm2) (mV) (mV) Epass.

18±0.21x10-6 0.58 AC CE P TE D MA NU HCl .54x10-6 0.01 3.39x10-6 1.20±0.22±0.01 3.28±0.02 5.17x10-6 0.14±0.55 H2SO4 0.ACCEPTED MANUSCRIPT Table 2 – Fe and Cu concentrations after anodic polarization tests Fe Fe Cu Cu solution concentration concentration concentration (mg/L) (mol/L) (mol/L) SC R IP (mg/L) Cu/Fe concentration ratio T Acid (molar ratio) 0.01 4.01 3.32±0.24 HNO3 0.01 2.08x10-6 1.92x10-6 0.

T(F∙sn∙cm-2) 1.3 6000±759 12518±751 4000±240 R3(Ω∙cm2) 12000±480 167290±4942 12341±1309 Ws-P 0.8x10-4 2.7x10-5 1. T(F∙sn∙cm-2) 2.5±0.4034 CPE1.ACCEPTED MANUSCRIPT Table 3 – Open circuit potential and the electrochemical parameters obtaining from EIS R2(Ω∙cm2) IP 7.1x10-6 Chi-squared 2.3x10-4 1.1x10-5 2.5 D Emixed(mV) Ag/AgCl HCl 202 (±27) T measurements 0.4513 .7±0.2±0.4x10-5 4.5x10-5 CPE2.6 SC R R1(Ω∙cm2) HNO3 209 (±4) H2SO4 220 (±10) 5.8x10-4 MA TE CE P AC NU 8.3x10-5 1.

AC CE P Graphical abstract TE D MA NU SC R IP T ACCEPTED MANUSCRIPT .

.► Sulphur AC CE P TE D MA NU and covellite were identified as corrosion products on the mineral surface.ACCEPTED MANUSCRIPT Highlights ► The acid dissolution of chalcopyrite is studied using electrochemical impedance IP T spectroscopy. ► Lead and bismuth sulphides were identified as impurities on the mineral surface. ► The hydrochloric acid is a more efficient leaching agent than nitric and SC R sulphuric acids. ► Dissolution of chalcopyrite is controlled by diffusion. ►Potentiodynamic polarization of chalcopyrite in acid media was performed.