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Hydrometallurgy 93 (2008) 8896

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Hydrometallurgy
j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / h yd r o m e t

Leaching of chalcopyrite with ferric ion. Part II: Effect of redox potential
E.M. Crdoba a, J.A. Muoz b, M.L. Blzquez b, F. Gonzlez b, A. Ballester b,
a b

Escuela de Ingeniera Metalrgica y Ciencia de los Materiales, Facultad de Ingenieras Fsico-Qumicas, Universidad Industrial de Santander, Bucaramanga, Colombia Departamento de Ciencia de Materiales e Ingeniera Metalrgica, Facultad de Ciencias Qumicas, Universidad Complutense de Madrid, 28040 Madrid, Spain

A R T I C L E

I N F O

A B S T R A C T
This paper reports the effect of redox potential (or Fe3+/Fe2+ ratio) on chalcopyrite leaching. The relationship between redox potential and other variables (iron concentration and temperature) is also evaluated. Leaching tests were performed in stirred Erlenmeyer asks with 0.5 g of pure chalcopyrite and 100 mL of a Fe3+/Fe2+ sulphate solution. The redox potential ranged between 300 and 600 mV Ag/AgCl for the solution at a pH 1.8, 180 rpm, with temperatures at 35 C or 68 C. The results show that although ferric ion is responsible for the oxidation of chalcopyrite, ferrous ion has an important role in that it controls precipitation and nucleation of jarosites, which ultimately causes passivation of this sulphide. Chalcopyrite dissolves through the formation of an intermediary product (covellite, CuS) that is later oxidized by ferric ion, releasing Cu2+ ions. 2008 Elsevier B.V. All rights reserved.

Available online 2 May 2008 Keywords: Chalcopyrite Ferric leaching Redox potential

1. Introduction Chalcopyrite, the most abundant mineral in copper ore bodies, is also the most recalcitrant to hydrometallurgical processes (Dutrizac, 1978), and for that reason copper is mainly extracted by pyrometallurgy. However, the depletion of ore deposits and declining mineral grades has encouraged the development of hydrometallurgical processes for the treatment of chalcopyrite. The dissolution of chalcopyrite by ferric ion is normally depicted by the following chemical reactions (Dutrizac and MacDonald, 1974): CuFeS2 4Fe3 YCu2 5Fe2 2S1

(Burkin, 1969), copper polysulphide with a decit of iron with respect to chalcopyrite (Ammou-Chokroum et al., 1977 and Hackl et al., 1995), or elemental sulphur (reaction (1)) (Muoz et al., 1979; Majima et al., 1985 and Dutrizac, 1989). In addition, several authors have concluded that the chalcopyrite dissolution rate depends on the redox potential of the solution, the best results being achieved under moderately oxidizing conditions (Kametani and Aoki, 1985; Hiroyoshi et al., 2001; Okamoto et al., 2003). Hiroyoshi et al. have proposed a model reaction involving the intermediate reduction of chalcopyrite by ferrous ion to Cu2S and later oxidation by ferric ion to release cupric ions: CuFeS2 3Cu2 3Fe2 Y2Cu2 S 4Fe3 : 3

CuFeS2 4Fe3 3O2 2H2 OYCu2 5Fe2 2H2 SO4 :

The release of cuprous ion does not occur in a single step. A Pourbaix diagram (Garrels and Christ, 1965) for the CuFeS2H2O system would show the stability elds of several sulphides such as Cu5FeS4, CuS or Cu2S between the stability elds of chalcopyrite and of its dissolution. After almost a century of research into the mechanisms of chalcopyrite leaching, no unanimous theory has been proposed to account for its slow kinetics. Nevertheless, there is consensus as to the formation of a passivating layer on the chalcopyrite surface that slows oxidation. The main theories were discussed in part I. Most of them point to the formation of a diffusion layer surrounding the chalcopyrite during dissolution, consisting of: bimetallic sulphide
Corresponding author. Tel.: +34 91 3944339; fax: +34 91 3944357. E-mail address: ambape@quim.ucm.es (A. Ballester). 0304-386X/$ see front matter 2008 Elsevier B.V. All rights reserved. doi:10.1016/j.hydromet.2008.04.016

Nicol and Lzaro (2003) have proposed a different mechanism to explain the chalcopyrite dissolution at low redox potentials. Kametani and Aoki identied a critical potential around 0.45 V vs. SCE, associated with the onset of pyrite oxidation. A relatively low redox potential has also been reported to have a favorable effect during bioleaching (Barr et al., 1992). These authors observed low redox potentials (400 to 450 mV SCE) after addition of ferrous ion, which sped up the bioleaching kinetics of a copper concentrate. Third et al. (2000, 2002) concluded that high ferric ion concentrations or high redox potentials inhibited the bioleaching of chalcopyrite, but they did not determine the cause of passivation. Temperature is another factor which directly affects chalcopyrite leaching rate. The high values of activation energy found by different authors: 71 kJ/mol (Dutrizac et al., 1969), 84 kJ/mol (Muoz et al., 1979), 88 kJ/mol (Hirato et al., 1987); clearly demonstrate the need of high temperatures to break down bonds in the chalcopyrite crystal lattice. In this study, the relationship between temperature and

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leaching kinetics is evaluated at 35 and 68 C, given that these temperatures are appropriate in bioleaching processes with mesophilic and thermophilic bacteria respectively. This research was prompted by the debate as to the relative inuence of ferrous ion and of a low redox potential on chalcopyrite dissolution. The specic aim was to study the role play by ferric and ferrous ions, which control the potential, during leaching. 2. Materials and methods 2.1. Solids All tests were performed with a chalcopyrite mineral (approximately 80% CuFeS2) from Messina, Transvaal (South Africa). Table 1 shows the chemical composition of this mineral. The main impurities were pyrite (FeS2), siderite (FeCO3) and silica (SiO2), as determined by X-ray analysis (Fig. 1). The mineral was dry-ground using a ball mill. The particle size distribution was determined by laser pulse. The average particle size was around 70 m. Additionally a BET surface area of 0.07 m2/g was determined. 2.2. Leaching solutions The different redox potentials of solutions were obtained by mixing ferric and ferrous sulphates while keeping total iron concentration constant at 5 g/L (in some tests 0.5 g/L) and pH at 1.8. Stock solutions of ferric sulphate were prepared with 0 K (modied 9 K medium of Silverman and Lundgren,1959) and Norris (Norris and Barr,1985) nutrient mediums for the tests at 35 C and 68 C respectively, which are normally used during bioleaching at these temperatures. 2.3. Leaching tests All leaching tests were performed in an orbital shaker at 180 rpm and 35 or 68 C using 250 mL Erlenmeyer asks covered with hydrophobic cotton so as to admit oxygen while reducing water loss through evaporation. A low pulp density of 0.5% (100 mL of leaching solution and 0.5 g of mineral) was chosen to avoid sharp changes in the redox potential of the liquid medium during the onset of leaching. Periodically, water evaporation was restored, pH adjusted when above the initial value, redox potential recorded and 1 mL samples removed from the liquid to obtain kinetic information on metal dissolution. Copper and total iron concentration were determined by atomic absorption spectroscopy and ferrous ion concentration using a photocolorimetric method based on the formation of a reddish colored complex of Fe2+ with orthophenantroline which was analyzed in an UVvis spectrophotometer at a wavelength of 510 nm. Finally, solid residues were characterized by XRD and SEM-EDS. 3. Results and discussion 3.1. Inuence of redox potential The inuence of redox potential on the chalcopyrite dissolution rate was tested at 35 C and 68 C. The redox potential values studied were 300, 400, 500 and 600 mV vs. Ag/AgCl.
Table 1 Chemical composition of the mineral tested Element Copper Iron Sulphur Zinc Lead Content (%) 27.36 29.65 34.30 0.31 0.02

Fig. 1. X-ray diffractogram patter of the starting mineral.

At 35 C the effect of the initial redox potential was negligible, with very low copper extractions (b2.5 %) in all cases (Fig. 2). The low reactivity of the chalcopyrite surface is consistent with low consumption of the oxidizing agent (Fe3+). The evolution of the redox potential with time shows that Fe3+/Fe2+ solutions tend towards equilibrium. This equilibrium potential, in a range of 400500 mV vs. Ag/AgCl, is presumably related to the standard potential of the Fe3+/Fe2+ couple. The value normally cited in the literature is 771 mV vs. SHE or 564 mV vs. Ag/AgCl (Dry and Bryson, 1988; Lowson, 1982); however, Cabral and Ignatiadis (2001) obtained experimentally a lower value (644 mV vs. SHE or 437 mV vs. Ag/AgCl) while assuming that the ratio of activity coefcients of both ion species, Fe3+ and Fe2+, was equal to unity. This standard potential value is within the equilibrium potential range observed in the present study.

Fig. 2. Inuence of redox potential on the chalcopyrite leaching at 35 C and [Fe]Total = 5 g/L.

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90 E.M. Crdoba et al. / Hydrometallurgy 93 (2008) 8896 Table 2 EDS microanalysis of chalcopyrite leaching residues (results in weight percent) Test 35 C 400 mV 35 C 600 mV 68 C 400 mV 68 C 600 mV Chalcopyrite surface Original Attacked Precipitate Attacked Precipitate Attacked Precipitate Attacked Precipitate S 30.80 30.50 33.48 34.17 23.25 30.81 18.89 33.30 14.49 Fe 32.24 32.96 27.46 29.18 23.08 27.44 31.35 27.34 34.10 Cu 36.96 36.54 29.75 31.49 18.19 29.14 1.05 29.31 0.72 O K

SEM examination of leaching residues did not show apparently passivating layers on the chalcopyrite surface. The micrographs (Fig. 3) show very clean surfaces with small amounts of a precipitate that is insufcient to affect the reactivity of chalcopyrite. EDS microanalysis of these residues are shown in Table 2. At low potential (400 mV), the composition of the attacked chalcopyrite surface was practically identical to the unattacked surface except for the presence of a small oxidized precipitate. At high potential (600 mV), an oxidized jarositetype compound was detected on the mineral surface, presumably potassium jarosite. X-ray diffractograms of these residues (Fig. 4) show the presence of several products: elemental sulphur (probably formed by reaction (1)), covellite (formed possibly by chalcopyrite transformation, as will be discussed later), goethite (only at low potential) and potassium jarosite. The las two compounds are presumably formed by ferric ion hydrolysis, according to the following reactions: Fe2 SO4 3 4H2 OY2FeOOH 3H2 SO4 4

9.31 5.16 34.18 12.32 46.33 9.84 46.46

1.30 0.29 2.38 0.21 4.23

K 3Fe3 2SO2 6H2 OYKFe3 SO4 2 OH6 6H : 4

At high temperature (68 C), unlike at 35 C, the effect of the initial redox potential was very pronounced (Fig. 5). At lower initial redox potentials (Einitial 400 mV), the chalcopyrite dissolution rate was very fast during the rst 5 days of leaching, and 80 or 90 % Cu extraction was achieved (Fig. 5a). This successful leaching coincided with potential values lower than approximately 450 mV (Fig. 5b) and values of the Fe3+/Fe2+ ratio lower than unity (Fig. 5c). For times longer than 5 days, the potential rose to 500 mV and the Fe3+/Fe2+ ratio increased appreciably. Under these new conditions in the leaching medium, chalcopyrite dissolution stopped. These observations tend to support the hypothesis of Hiroyoshi et al. (1997, 1999, 2000, 2001), according to which chalcopyrite leaching with ferric sulphate is catalysed by ferrous ion. Furthermore, in agreement with Hiroyoshi's results, there is a critical redox potential value of 413 mV vs. Ag/AgCl above which chalcopyrite dissolution slows down.

As noted earlier, various researchers have also observed better chalcopyrite dissolution rates at low redox potentials at 30 C (Okamoto et al., 2003) and at 90 C (Kametani and Aoki, 1985). Kametani and Aoki determined a critical potential of 458 mV vs. Ag/ AgCl, and detected by XRD the presence of CuS in the leaching residues, working at a very low potential (338 mV vs. Ag/AgCl). SEM micrographs of the leaching residue at 68 C and an initial redox potential of 400 mV (Fig. 6a) show chalcopyrite particles surrounded by a precipitate identied by XRD as a mixture of potassium jarosite, elemental sulphur and goethite (Fig. 7a). Although this composition was similar to the leaching tests at 35 C, the amount of precipitate was greater at 68 C. EDS microanalyses (Table 2) of that leaching residue indicate an enrichment in potassium jarosite. Under more oxidizing conditions (Einitial 500 mV), copper extractions were lower than 35 C (Fig. 5a). The low-magnication backscattered electron micrograph of the residue at 600 mV (Fig. 6b), shows few bright areas corresponding to clean chalcopyrite surfaces and many dark areas corresponding to chalcopyrite covered

Fig. 3. SEM micrographs of the leaching residues at 35 C and [Fe]Total = 5 g/L: a) Einitial = 400 mV and b) Einitial = 600 mV.

Fig. 4. X-ray diffractograms of the leaching residues at 35 C and [Fe]Total = 5 g/L: a) Einitial = 400 mV and b) Einitial = 600 mV.

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Fig. 5. Inuence of redox potential on the chalcopyrite leaching at 68 C and [Fe]Total = 5 g/L.

by a diffusion layer. That lm formed on chalcopyrite particles is clearly observed at higher magnication in Fig. 6c. the low porosity of that layer would explain the poor results obtained at high redox

potentials. XRD analysis (Fig. 7b) and EDS microanalysis (Table 2) point to that the diffusion layer consisted mainly of potassium jarosite. Those differences were also related to a higher iron precipitation, during the initial stages, at high than at low potentials (Fig. 5d). Assuming that nucleation of jarosites on mineral particles (heterogeneous nucleation) was more important than nucleation out of solution (homogeneous nucleation, that fast iron precipitation at high potentials caused the rapid passivation of chalcopyrite. At low potentials, the fast leaching kinetics initial stage was followed by another very slow (Fig. 5a) and related to an abundant iron precipitation (Fig. 5d). That would explain the presence of jarosite

Fig. 6. SEM micrographs of the leaching residues at 68 C and [Fe]Total =5 g/L: a)Einitial =400 mV, b) Einitial =600 mV and c) circled particle in (b) at higher magnication.

Fig. 7. X-ray diffractograms of the leaching residues at 68 C and [Fe]Total = 5 g/L: a) Einitial = 400 mV and b) Einitial = 600 mV.

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and goethite in the leaching residues at low potential (Fig. 6a), like in experiments at high potentials (Fig. 6b). X-ray diffractograms of the residues also show the presence of sulphur, although in a smaller proportion than jarosite (Fig. 7). The passivating nature of jarosites is in good agreement with thermodynamic data. For the dissolution of jarosite at 25 C, Baron and Palmer (1996) determined: KFe3 SO4 2 OH6 6H YK 3Fe3 2SO2 6H2 O 4
11

the solubility product constant, Ksp = 10 , and the free energy of jarosite formation, Gf, 3309.8 kJ/mol. These values are indicative of the very low solubility and high stability of jarosites. Casas et al. (2000) noted that jarosite formation in ferric sulphate solutions starts from iron hydroxides, like Fe(OH)3, formed by hydrolysis of ferric ion. The presence of goethite (FeOOH) in some residues in the present study tends to conrm that hypothesis. The action of goethite as activating agent in the formation of jarosite may be depicted as follows: 2 Fe3 K 2SO2 FeOOHs 4 4H2 OYKFe3 SO4 2 OH6 3H :

These results point to that passivation of chalcopyrite during leaching is due to the formation of a layer of jarosite which prevents transportation of both electrons and ion species between the mineral surface and the leaching medium. Furthermore, the precipitation of iron, and hence the formation of jarosites, is directly related to the redox potential of the solution. Thus, redox potentials higher than the critical value (between 400 and 500 mV) favor Fe3+ precipitation as jarosite and the subsequent chalcopyrite passivation. The above observation is supported by Bigham et al. (1996) in that the stability eld of potassium jarosite at pH lower than 2 is located at potentials higher than 563 mV vs. Ag/AgCl. Thus, the closer the redox potential of the leaching solution is to the beginning of the stability eld of the jarosite, the faster it will precipitate. As in tests at 35 C (Fig. 2), the kinetics curves at 68 C (Fig. 5) show that the Fe3+/Fe2+ ratio or the redox potential of the leaching solution tends asymptotically towards an equilibrium value of approximately 480 mV vs. Ag/AgCl. Only a few researchers have mentioned this trend for leaching solutions of ferric sulphate. Of these, Dutrizac (1983) noted that whereas the amount of jarosite formed increased with ferric ion concentration, the Feprecipitated/Fedissolved ratio did not, concluding that the solution tends toward equilibrium. Precipitation of iron from ferric sulphate solutions, then, is difcult to control since it occurs spontaneously until the system reaches equilibrium. The leaching results at 68 C seem to demonstrate that precipitation and nucleation of jarosites on mineral particles would occur even in tests with the fastest kinetics. Intermediate products were not detected in the long-term tests, probably because of a jarosite lm covering the particles. In order to generate residues to identify possible intermediate products, new leaching tests were performed at shorter times (1 h, 5 h and 1 day). Figs. 8 and 9 show micrographs and X-ray diffractograms of leaching residues at 68 C and Einitial = 400 mV with short attack-time. Chalcopyrite surface transformations began at times as short as 1 h (Fig. 8a). EDS microanalysis of precipitate shown in that gure (named precipitate in Table 3) indicates an impoverishment of iron and an enrichment of copper and sulphur. The XRD diffractogram of the residue (Fig. 9a) evidences the formation of three products: elemental sulphur, goethite and covellite. The last compound (CuS) would be related to the EDS analysis of zone named precipitate in Fig. 8a. Micrographs of the 5 h leaching residue (Fig. 8b) show small quantities of a precipitate over particles. EDS microanalyses (Table 3)

show again an enrichment of copper and sulphur on the chalcopyrite surface and the presence of an oxidized compound in the zone named precipitate, probably goethite. The diffractogram of that residue (Fig. 9b) reveals the presence of the same three products found at 1 h: elemental sulphur, goethite and covellite. Finally, the growth of a product over the chalcopyrite surface seems to start after 1 day of attack (Fig. 8c). EDS microanalyses (Table 3) of that product indicate the presence of oxidized compounds containing potassium and phosphorus in its composition. Two additional products were detected by XRD (Fig. 9c): potassium jarosite and ferric hydroxyphosphate. The fact that goethite formed prior to the formation of jarosite conrms the hypothesis that jarosite formation starts from Fe3+ hydro-oxidized compounds like goethite. Even although the proportion of ferric hydroxyphosphate detected in the residue after 1 day of leaching is small, like jarosite it can be passivating. In fact, its chemical composition (Fe4(PO4)3(OH)3) may be related to the alunite group (AB3(XO4)2(OH)6), as in the case of jarosite (Lowson, 1982), where A stands for cations such as Na+, K+, H3O+, NH+, 4 Pb2+ or Ag+; B stands for Fe3+ or Al3+, and XO4 usually for SO4, PO4 or AsO4. Another noteworthy nding was an increase of the CuS/chalcopyrite ratio, at least during the rst day of attack, as shown in the diffractogram.

Fig. 8. SEM micrographs of the leaching residues at 68 C, [Fe]Total = 5 g/L, Einitial = 400 mV and short times: a) 1 h, b) 5 h and c) 1 day.

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concluded that covellite forms either aerobically or anaerobically through the reaction: CuFeS2 Cu2 Y2CuS Fe2 : 12

Moreover, this transformation speeds up with temperature. Kametani and Aoki, 1985, also found CuS in chalcopyrite leaching residues carried out at a redox potential lower than 0.33 V vs. SCE. All this suggests, then, that CuS only forms at low redox potentials. Additionally, CuS formation can also occur during chalcopyrite leaching by direct reaction between cupric ions and previouslyformed elemental sulphur, as follows: 3Cu2 4H2 O 4S-Y3CuS HSO 7H : 4 13

Nevertheless, the authors favor the idea that although this reaction is thermodynamically possible, it does not occur because of the hydrophobic nature of the elemental sulphur (Dutrizac and MacDonald, 1974). Therefore, chemical reactions (8) and (12) become kinetically more favorable. 3.2. Inuence of iron concentration The results reported in the previous section showed that precipitation and nucleation of jarosites on mineral particles led to passivation of chalcopyrite. In a rst attempt to explain and control passivation, it was decided to study the effect of total iron concentration. Fig. 10 depicts the kinetics curves obtained during the leaching of chalcopyrite at 68 C at two different iron concentrations: 0.5 and 5 g FeTotal/L. Total iron concentration plays an important role in the process: Reducing total iron concentration from 5 to 0.5 g Fe/L has a negative effect on copper dissolution at low redox potential (400 mV) and practically has no effect at high redox potential (600 mV). The SEM study of the leaching residue at high potential and low iron concentration showed chalcopyrite surfaces free of passivating layers (Fig. 11). The X-ray diffractogram of this residue (Fig. 12) conrmed the same compounds previously detected with 5 g/L of Fe (Fig. 7b): S, jarosite, goethite and ferric hydroxyphosphate, the last two being more important in this case. These results indicate that in the Fe3+/ Fe2+ couple the ion closely related to chalcopyrite dissolution is Fe3+. The role of Fe2+, then, would be to achieve rapid equilibrium of the Fe3+/Fe2+ couple in solution, thus controlling hydrolysis of the ferric ion, which could be ultimately responsible for the passivation of chalcopyrite. The positive effect observed in chalcopyrite leaching at 68 C when iron concentration was increased from 0.5 to 5 g/L (or from 0.009 to 0.09 M) suggests that the process is at least partially controlled by the diffusion of ions towards the chalcopyrite surface. That is consistent with the ndings of Hirato et al. (1987) that the dissolution rate at 70 C increases with ferric ion concentration up to 0.1 M, while above that value the enhancement is negligible.

Fig. 9. X-ray diffractograms of the leaching residues at 68 C, [Fe]Total = 5 g/L, Einitial = 400 mV and short times: a) 1 h, b) 5 h and c) 1 day.

The presence of CuS in the leaching products at short times suggests that chalcopyrite dissolves in two steps. First it oxidizes, forming CuS as an intermediary product: CuFeS2 2Fe3 YCuS 3Fe2 S-: 8

Then, covellite is oxidized by ferric sulphate, releasing Cu2+ ions: CuS 2Fe3 YCu2 2Fe2 S9

Also, we cannot rule out an initial reduction of chalcopyrite (reaction (3)), as proposed by Hiroyoshi et al. (2001), followed by oxidation of chalcocite to covellite by ferric sulphate through the formation of copper-decient intermediate products, as reported by Ferron (2003) in a study on the leaching of secondary copper minerals: Cu2 S Fe2 SO4 3 YCuSO4 2FeSO4 CuS Cu2 S Y Cu1;931;96 S Y Cu1;80 S Y CuS :
djujerite digenite covellite

Table 3 EDS microanalysis of chalcopyrite leaching residues at 68 C, [Fe]Total = 5 g/L, Einitial = 400 mV and short times (results in weight percent) Time 1h Chalcopyrite surface Original Attacked Precipitate Attacked Precipitate Attacked Precipitate S 30.80 30.16 34.06 37.32 28.99 32.84 12.39 Fe 32.24 31.99 8.87 29.64 28.76 29.74 23.91 Cu 36.96 36.33 48.76 33.04 30.38 33.05 4.45 O 1.52 8.31 11.87 4.37 54.68 K P

10

chalcocite

11

5h 1 day

Some researchers have detected the formation of covellite from chalcopyrite under reducing conditions. Jang and Wadsworth, 1993,

3.92

0.65

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Fig. 12. X-ray diffractogram of the leaching residue at 68 C, Einitial = 600 mV and [Fe]Total = 0.5 g/L.

Fig. 10. Inuence of iron concentration on the chalcopyrite leaching at 68 C.

3.3. Inuence of temperature The effect of temperature was very pronounced, with negligible copper dissolution at 35 C after 13 days of leaching (b3%) vs. almost complete mineral dissolution at 68 C (Figs. 2 and 5). Thermal activation therefore plays an important role in this process. The effect of temperature in the leaching of chalcopyrite with ferric sulphate was evaluated by calculating the activation energy in the experimental temperature range of 35 C to 68 C. Four assays were performed at 35, 46, 57 and 68 C, while all other experimental conditions were constant, i.e.: 0.5% pulp density, Einitial = 400 mV and [Fe]Total = 5 g/L. The activation energy was calculated from the kinetic constants and the semilogarithmic plot of the Arrhenius equation. First, the fraction of reacted chalcopyrite was plotted vs. time for each temperature (Fig. 13). Then, linear curves were plotted using the simplied shrinking core model proposed by Sohn and Wadsworth (1979), according to the following expression: 1 1 X 1=3 k t 14

68 C was zero (Fig. 13), probably due to the precipitation of jarosites, and so they were removed from the linear regression. According to Eq. (14), the slopes of the curves in Fig. 14 correspond to the following kinetic constant values: 0.0006, 0.0044, 0.0319 and 0.0732 days 1 for 35, 46, 57 and 68 C respectively. Most chemical reactions obey the Arrhenius equation (Logan, 2000; Levenspiel, 2004) and it was used to determine the effect of temperature on the leaching of chalcopyrite: k A eEa =RT 15

where X is the fraction of reacted chalcopyrite, k the kinetic constant and t time. That equation is represented graphically in Fig. 14. The slope of the nal experimental data for the kinetic curves at 57 C and

where Ea is the activation energy, A the pre-exponential factor with the same units as the kinetic constant k, R the universal gas constant (8.314 J.K 1.mol 1) and T the absolute temperature (K). Then, the logarithm of the kinetic constant is a linear function of the inverse of temperature. Table 4 shows the values represented in the Arrhenius plot in Fig. 15. The activation energy for chalcopyrite dissolution, deduced from the slope of the straight line of the Arrhenius plot, was appreciably higher (130.7 kJ/mol) than that reported by other researchers (71 88 kJ/mol) in the range of temperature between 50 and 94 C and in sulphate medium (Dutrizac et al. (1969), Muoz et al. (1979), Hirato et al. (1987). Those differences could be attributed to the temperature range assayed. The kinetic curves show that chalcopyrite dissolution is negligible at 35 C, and that the energy barrier responsible for the slow copper dissolution rate could be overcome at 68 C. However, the enhancement of copper extraction is less pronounced above a certain temperature (N50 C). Based on the parameters established by Moore (1990) to elucidate reaction mechanisms in different chemical processes, the high activation energy value registered in this study (130.7 kJ/mol) indicates that during the rst stage of chalcopyrite leaching, when the kinetics is approximately linear, the system is under chemical control. Therefore, the main drawback of chalcopyrite dissolution

Fig. 11. SEM micrograph of the leaching residue at 68 C, Einitial = 600 mV and [Fe]Total = 0.5 g/L.

Fig. 13. Inuence of temperature on the chalcopyrite leaching at Einitial = 400 mV.

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Fig. 15. Arrhenius plot. Fig. 14. Variation of 1 (1 X)

1/3

over time.

would be the strong chemical bonding of the crystal lattice, which requires a high input of energy to the system. These ndings support the hypothesis of Hiskey (1993) that the transport of electrons through vacants is very poor due to the n-type semiconductivity of chalcopyrite, and hence the rst step during chalcopyrite oxidation is the consumption of vacants to favor electron transportation through the crystal lattice. Thus, a great deal of the energy applied to the system in the form of heat is consumed by the displacement of ions from the bulk of the particle to the surface, eliminating surface vacants and favoring the transport of electrons through the chalcopyrite surface. At the same time, increasing iron concentration from 0.5 to 5 g/L improves the leaching rate at 68 C (Fig. 10), and so the diffusion of ferric ion to the chalcopyrite surface may also control the process. Researchers have not reached a consensus on the control steps governing chalcopyrite leaching. Our ndings are similar to those reported by Linge (1976) and Hirato et al. (1987) with a linear branch in the copper kinetic curve. Nevertheless, many researchers (Dutrizac et al., 1969; Ferreira and Burkin, 1975; Muoz et al., 1979; Parker et al., 1981; Kametani and Aoki, 1985; Hackl et al., 1995, etc.) have obtained parabolic kinetics with an initial linear branch, similar to our results but with very varied conclusions. This variety in the hypotheses to be found in the literature reects a lack of agreement on the mechanisms of chalcopyrite dissolution. These results seem to indicate that hydrolysis and precipitation of Fe3+ has a main role in chalcopyrite passivation in ferric solutions by preventing the contact between the mineral surface ant the oxidizing agent in solution. Decreasing pH or removing some ions that favor iron precipitation could be a way to prevent ferric ion hydrolysis. However, our attempts in that direction (results not shown) have not solved the problem of chalcopyrite passivation. Copper dissolution rate decreased when pH was reduced from 0.5 to 2.0, perhaps because of that the species responsible for the oxidation of chalcopyrite is not properly Fe3+ but probably Fe(SO4) (Crdoba, 2005). Furthermore, the removal of 2 monovalent cations (K+, Na+ or NH+) from solution neither prevents 4 hydrolysis and precipitation of iron as goethite and hydronium jarosite that, like potassium jarosite, also tend to nucleate over chalcopyrite particles.

On the other hand, minority iron-bearing minerals in the starting mineral (siderite and pyrite) could have an important role in leaching kinetics. Siderite is quickly dissolved in acidic media, increasing the iron concentration in solution: FeCO3 H2 SO4 YFeSO4 CO2 H2 O: 16

In the case of pyrite, there are evidences that this sulphide only dissolves when chalcopyrite is already passivated. Moreover, pyrite rest potential is higher than that of chalcopyrite and, therefore, pyrite enhances dissolution chalcopyrite through galvanic contact. Finally, the comparison between studies on chalcopyrite leaching is a difcult task because of differences in experimental conditions used. However, unlike at high temperature, chalcopyrite dissolution and ferric ion hydrolysis kinetics are very slow processes at low temperature (35 C). 4. Conclusions 1. The redox potential is a key factor in the leaching of chalcopyrite. A high potential at the onset of leaching provokes rapid passivation of chalcopyrite. 2. Ferric/ferrous sulphate leaching solutions tend to reach equilibrium when the activities of the two ions are equal, which is associated with a critical potential of approximately 450 mV. When the redox potential is very high initially, that tendency to equilibrium favors rapid precipitation of ferric ion as jarosite and consequently passivation of chalcopyrite. 3. The activation energy during chalcopyrite leaching was 130.7 kJ/ mol, which is a clear demonstration of the importance of thermal activation in this process. 4. Increasing the iron concentration from 0.5 to 5 g/L had a positive effect in the chalcopyrite leaching at 68 C. 5. Chalcopyrite dissolves through the intermediate formation of covellite, CuS, which is later oxidized by ferric ion to release Cu2+ ions: CuFeS2 2Fe3 YCuS 3Fe2 S-

CuS 2Fe3 YCu2 2Fe2 S-:

Table 4 Values represented in the Arrhenius plot of Fig. 15 T (K) 308 319 330 341 k (days 1) 0.0006 0.0044 0.0319 00732 k (s 1) 6.9444 10 5.0926 10 8 3.6921 10 7 8.4722 10 7
9

6. The elemental sulphur that forms during chalcopyrite leaching is porous and does not form a passivating layer on the chalcopyrite surface.
1000 / T (K 1) 3.25 3.13 3.03 2.93 ln k (s 1) 18.79 16.79 14.81 13.98

References
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Author's personal copy

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