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Evaluation of the electrochemical behavior of carbon paste

electrode (CPE) with chalcopyrite (CuFeS2) in the

presence of ferrous ions
Delfino, F.A.A.; Bevilaqua, D.; Fujivara, C. S.; Benedetti, A. V.
Universidade Estadual Paulista
Rua Prof.Francisco Degni, 55 Araraquara SP - Brasil
The chalcopyrite mineral sulfide (CuFeS2) is one of the sources for obtaining copper,
particularly by pyrometallurgical processes. The requirement of using a corrosive
process with high cost is due to slow kinetic of chalcopyrite dissolution. However, the
biohydrometallurgy, economically and environmentally favorable process, has been
developed as an alternative. This process uses microorganisms, especially the
acidophilic bacteria Acidithiobacillus ferroxidans, which are capable of promoting the
oxidation of minerals sulfides and the recovery of copper. In the specific case of
CuFeS2, bacteria oxidize Fe2+ to Fe3+ ions, which attack the mineral sulfide. However,
the presence of Fe3+ ions increases the redox potential and can cause the precipitation
of non-stoichiometric sulfides, sulfur and jarosite hindering the removal of copper. In
this context, the control of the redox potential through the couple Fe 3+/ Fe2+ can be an
alternative for process improvement. In this work we present an electrochemical study
using carbon paste electrode (CPE) with CuFeS2 in different concentrations of Fe2+
ions in order to evaluate the possible interaction between these ions and mineral sulfide
in the absence of bacteria. Measurements of Electrochemical Impedance Spectroscopy
(EIS) were performed for 97 h using CPE-graphite and CPE-CuFeS2 in T&K medium
without the addition of Fe2+. Sequentially, the CPE-CuFeS2 was analyzed using T&K
medium with [Fe2+] = 0.1, 0.2 or 0.3 mol L-1. The CPE-graphite showed a capacitive
behavior with high modulus impedance value. The Bode plots showed one time
constant in the region of low frequency possibly related to the graphite response. In the
case of CPE-CuFeS2 in T&K medium one time constant in the region of low
frequencies was observed which was attributed to the chalcopyrite response. This time
constant showed a phase angle around -60o and tends to increase with the immersion
time. This time constant is probably related to the oxidation of the mineral surface
(elemental sulfur formation, and iron and/or copper dissolution) in acidic medium (pH
1.8), which decreases the surface electroactivity. As cathodic reaction probably both
the H+ and O2 may be reduced. For the solution of Fe2+ 0.1 mol L-1 no significant
changes in the EIS spectra was observed. For the solutions with 0.2 and 0.3 mol L -1 of
Fe2+ a single time constant was observed during the test which may be related to iron
oxidation. The diffusion characteristic observed in the EIS spectra of chalcopyrite
diminished in 0.2 mol L-1 Fe2+, and almost disappeared in 0.3 mol/L Fe2+. It is possible
that the main process in the presence of iron(II) ions is their oxidation. On the other
hand, it is possible that Fe2+ reacts with CuFeS2 and cause partial dissolution of the
mineral sulfide, making it still more refractory. More electrochemical and microscopy
studies are in progress to elucidate the interaction between chalcopyrite and ferrous