Two-Step Reaction Mechanism of Roasting Spodumene with Potassium Sulfate.

The conventional process of lithium extraction from α-spodumene (LiAlSi2O6) is energy-intensive and associated with high byproduct management cost. Here, we investigate an alternative process route that uses potassium sulfate (K2SO4) to extract lithium while producing leucite (KAlSi2O6), a slow release fertilizer. Presenting the first-ever in situ record of the reaction of α-spodumene with potassium sulfate, we use synchrotron X-ray diffraction (XRD) and differential scanning calorimetry (DSC) to document the reaction sequence during prograde heating. From 780 °C, we observe a broad endothermic DSC peak, abnormal expansion of the α-spodumene structure, and an increase in α-(Li, K)-spodumene peak intensity during heating with potassium sulfate, indicative of the exchange between lithium and potassium in the spodumene structure. When 11 ± 1% K occupancy in the M2 site of α-(Li, K)-spodumene is reached, the mechanism changes from ion exchange to a reconstructive transformation of α-(Li, K)-spodumene into leucite, evidenced by a decrease in α-spodumene and potassium sulfate abundance concurring with formation of leucite over a narrow temperature range between 850 and 890 °C. The increasing background intensity in synchrotron XRD above 870 °C suggests that a lithium sulfate-bearing melt starts to form once >90% of α-spodumene has been converted during the reaction. This fundamental understanding of the reaction between α-spodumene and potassium sulfate will enable future development of lithium extraction routes using additives to significantly decrease energy intensity and to produce marketable byproducts from α-spodumene.

Influence of Synthesis Temperature on the Growth and Surface Morphology of Co3O4 Nanocubes for Supercapacitor Applications.

A facile hydrothermal route to control the crystal growth on the synthesis of Co3O4 nanostructures with cube-like morphologies has been reported and tested its suitability for supercapacitor applications. The chemical composition and morphologies of the as-prepared Co3O4 nanoparticles were extensively characterized using X-ray diffraction (XRD) and transmission electron microscopy (TEM). Varying the temperature caused considerable changes in the morphology, the electrochemical performance increased with rising temperature, and the redox reactions become more reversible. The results showed that the Co3O4 synthesized at a higher temperature (180 °C) demonstrated a high specific capacitance of 833 F/g. This is attributed to the optimal temperature and the controlled growth of nanocubes.

New Insights into the adsorption of aurocyanide ion on activated carbon surface: electron microscopy analysis and computational studies using fullerene-like models.

Despite decades of concerted experimental studies dedicated to providing fundamental insights into the adsorption of aurocyanide ion, Au(CN)2(-), on activated carbon (AC) surface, such a mechanism is still poorly understood and remains a contentious issue. This adsorption process is an essential unit operation for extracting gold from ores using carbon-in-pulp (CIP) technology. We hereby attempt to shed more light on the subject by employing a range of transmission electron microscopy (TEM) associated techniques. Gold-based clusters on the AC surface are observed by Z-contrast scanning TEM imaging and energy-filtered TEM element mapping and are supported by X-ray microanalysis. Density functional theory (DFT) calculations are applied to investigate this adsorption process for the first time. Fullerene-like models incorporating convex, concave, or planar structure which mimic the eclectic porous structures on the AC surface are adopted. Pentagonal, hexagonal, and heptagonal arrangements of carbon rings are duly considered in the DFT study. By determining the favored adsorption sites in water environment, a general adsorption trend of Au(CN)2(-) adsorbed on AC surface is revealed whereby concave > convex ≈ planar. The results suggest a tendency for Au(CN)2(-) ion to adsorb on the carbon sheet defects or edges rather than on the basal plane. In addition, we show that the adsorption energy of Au(CN)2(-) is approximately 5 times higher than that of OH(-) in the alkaline environment (in negative ion form), compared to only about 2 times in acidic environment (in protonated form), indicating the Au extraction process is much favored in basic condition. The overall simulation results resolve certain ambiguities about the adsorption process for earlier studies. Our findings afford crucial information which could assist in enhancing our fundamental understanding of the CIP adsorption process.

A surface adsorption/reaction mechanism for gold oxidation by copper(II) in ammoniacal thiosulfate solutions.

Literature data for gold dissolution in ammoniacal copper(II) thiosulfate solutions is reinterpreted on the basis of adsorption and mixed potential theory. The dissolution reaction appears to take place via the adsorption of copper(II)-ammonia-thiosulfate onto the gold surface, forming the adsorbed species perpendicular to Au(S2O3)nCu(NH3)-(2n-2)p. Equilibrium constants for the formation of these species from Cu(NH3)(2+)m are in the range Kads=172-510 (molar units) for m=4, n=1 or 2, and p=2 or 3. These complexes decompose with a rate constant of kAu=1.7 x 10(-4)molm(-2)s(-1), to produce Au(S2O3)(3-)2 and Cu(NH3)+(3) or Cu(NH3)+(2), where the copper(I) complexes in solution are re-equilibrated to the more stable species Cu(S2O3)3-(2) and Cu(S2O2)5-(3).

The ammine, thiosulfato, and mixed ammine/thiosulfato complexes of silver(I) and gold(I).

The M(I)-NH(3), M(I)-S(2)O(3)(2)(-), and M(I)-S(2)O(3)(2)(-)-NH(3) systems (M = Ag, Au) were studied at 25 degrees C and at I = 0.1 M (NaClO(4)) using a variety of analytical techniques. For the Ag(I)-NH(3)-S(2)O(3)(2)(-) system, AgS(2)O(3)NH(3)(-) was detected with formation constant log beta(111) (for the reaction Ag(+) + S(2)O(3)(2)(-) + NH(3) <--> AgS(2)O(3)NH(3)(-)) of 11.2, 10.4, and 10.8 on the basis of silver potentiometry, UV-vis spectrophotometry, and hydrodynamic voltammetry, respectively. Also, the values of log beta(101)(AgNH(3)(+)), log beta(102)(Ag(NH(3))(2)(+)), log beta(110)(AgS(2)O(3)(-)), and log beta(120)(Ag(S(2)O(3))(2)(3)(-)), obtained from silver potentiometry, were 3.59, 7.0, 8.97, 13.1, respectively. In the case of the ammine complexes, the log beta(101)(AgNH(3)(+)) and log beta(102)(Ag(NH(3))(2)(+)) values were found to be 3.5 and 7.1, respectively, from the UV-vis spectrophotometric experiments. The mixed species AuS(2)O(3)NH(3)(-) was detected in UV-vis spectrophotometric, hydrodynamic voltammetric, and potentiometric experiments with the stepwise formation constants (log K(111)) of -4.0, -3.5, -3.8, respectively, for the reaction Au(S(2)O(3))(2)(3)(-) + NH(3) <--> AuS(2)O(3)NH(3)(-) + S(2)O(3)(2)(-). At higher [NH(3)]/[S(2)O(3)(2)(-)] ratios (>10(5)), the formation of Au(NH(3))(2)(+) was also detected in spectrophotometric and potentiometric experiments with stepwise formation constants (log K(102)) of -5.4 and -5.3, respectively, according to the reaction AuS(2)O(3)NH(3)(-) + NH(3) <--> Au(NH(3))(2)(+) + S(2)O(3)(2)(-).