ABSTRACT
The stability of magnetite under oxidizing hydrothermal conditions was evaluated at temperatures of 120, 150, 180 and 275 °C. A well-characterized sample of commercially-available magnetite with a particle size of approximately 690 nm was oxidized by dissolved oxygen (DO) under alkaline hydrothermal conditions in titanium autoclaves. In these trials, the DO was always in equilibrium with the gas phase oxygen that was air-derived and was located above the hydrothermal solution, which contained ammonium hydroxide at a pH25 °C of approximately 9.5. Samples recovered by filtration were analysed by X-ray diffraction and scanning electron microscopy, while Fe(ii)/Fe ratios were determined by titration in conjunction with spectrophotometry. Oxidation between 120 and 180 °C was found to generate high concentrations of maghemite and hematite in the product, with the latter compound having either a hexagonal bipyramidal or rhombohedral morphology. The oxidation kinetics was consistent with a diffusion controlled process. The reaction probably proceeded via the outward diffusion of ferrous ions from the magnetite, forming a magnetite/maghemite core/shell structure in conjunction with the dissolution of maghemite and reprecipitation of hematite. Oxidation at 275 °C presented different characteristics from those observed at the lower temperatures. Negligible amounts of maghemite were found, and the primary oxidation product was hematite with no specific morphologies. Moreover, the kinetics was slower than at 180 °C. This unexpected temperature effect is attributed to the rapid growth, at 275 °C, of a dense layer of hematite on the surface of the magnetite that impeded the oxidation of magnetite.
ABSTRACT
An experiment based on electrochemical reactions and pH monitoring was performed in which nickel ions were gradually formed by oxidation of a nickel metal electrode in a solution of boric acid. Based on the experimental results and aqueous speciation modeling, the evolution of pH showed the existence of significant nickel-boron complexation. A triborate nickel complex was postulated at high boric acid concentrations when polyborates are present, and the equilibrium constants were determined at 25, 50 and 70 °C. The calculated enthalpy and entropy at 25 °C for the formation of the complex from boric acid and Ni2+ ions are respectively equal to (65.6 ± 3.1) kJ·mol-1 and (0.5 ± 11.1) J·K-1·mol-1. The results of this study suggest that complexation of nickel ions by borates can significantly enhance the solubility of nickel metal and nickel oxide depending on the concentration of boric acid and pH. First principles calculations were investigated and tend to show that the complex is thermodynamically stable and the nickel cation in solution should interact more strongly with the [Formula: see text] than with boric acid.
