Effect of Temperature on Kinetic Properties of the Fe (II)/Fe (III) Redox Couple on the Surface of Pyrite

"In this study, the Fe(II)/Fe(III) redox reaction kinetics on the surface of pyrite, have been investigated in a 0.5 mol L-1 sulfuric acid solution for a temperature range of 22 to 65°C. Based on mixed potential theory, chronoamperometry is introduced to study the Fe(II)/Fe(III) kinetics by subtracting the current density of pyrite oxidation in an iron-free acidic solution from that in an iron-containing solution at the same applied polarized potential. Tafel behavior was established by this method to analyze the kinetics of the Fe(II)/Fe(III) redox reactions. The results showed that exchange current densities increased slightly with temperature, however remained on the order of 10-5 A cm-2. The activation energy for Fe(II) oxidation and Fe(III) reduction on the pyrite surfaces was calculated to be 102.0 and 32.7 kJ mol-1, respectively. Anodic transfer coefficients also increased, from 0.24 to 0.39, with increasing temperature, which indicates a weakened n-type semiconductor property at higher temperatures. Electrochemical impedance spectroscopy measurements have indicated that at lower anodic over potentials the charge transfer is the rate determining step of pyrite oxidative dissolution in sulfuric acid solution. In the presence of Fe ions, the major contribution of the total current density comes from the Fe(II)/Fe(III) redox reaction. INTRODUCTION Pyrite, an abundant sulfides mineral in the nature, is commonly considered a valueless gangue mineral frequently associated with other valuable sulfide minerals such as chalcopyrite, or metals such as gold, or coal (Lin & Say, 1999). Pyrite oxidation has been the subject of extensive research in view of gold metallurgy, as oxidation of pyrite is the initial step to break down the pyrite lattice and expose the encapsulated fine gold particles (Gasparrini, 1983). Fe(III) ion and dissolved oxygen (DO) have generally been considered as the two most important oxidants with respect to pyrite oxidation, having been studied extensively in previous research (Zheng, Allen, & Bautista, 1986; King Jr & Lewis, 1980). The process of pyrite oxidation can be viewed as a series of reactions amongst pyrite, ferrous, ferric and oxygen in which pyrite is initially oxidized by the dissolved oxygen in water forming ferrous (Eq. 1), and then the ferrous also is oxidized by he dissolved oxygen to form ferric (Eq. 2). The ferric, produced by reaction 2, then could potentially oxidize pyrite (Eq. 3) and convert to ferrous."