The colors of copper-containing pigments, copper (II) oxide and malachite, and their origins in ceramic glazes were systematically examined over a wide firing temperature range using a suite of analytical and spectroscopy techniques including SEM, UV-Vis FORS, XRD, FTIR, and EPR to gain new insight into the structural and chemical transformations of the glaze during firing. The two colorants investigated were black copper (II) oxide (CuO) nanopowder and blue-green basic copper carbonate, or malachite (Cu2CO3(OH)2), both of which produce a final light blue color following firing. Additionally, silicon carbide (SiC) was used to locally reduce CuO to simulate firing glazes in a reductive environment and produce a final red color. At lower temperatures, malachite was found to decompose to form CuO at 550 °C, elucidating the reason that two different copper colorants could be used interchangeably to form the same “Robin’s Egg Blue” color. At 850 °C, a glaze sintering process occurred, resulting in the distribution of Cu2+ in a square planar geometry and an observed blue color. This structural change occurred at temperatures lower than the glaze’s melting point, indicating that complete vitrification of the glaze is not required for glaze coloration. Conversely, the reduction in Cu2+ to Cu+ through the addition of SiC did not occur until the glaze was fired above the melting temperature (1000 °C), signifying that high temperatures are required for the redox reaction to occur. This study sheds light on intermediate colorant-glaze interactions that are beneficial for understanding and predicting glaze coloring upon exposure to varying temperatures, and the results from this study can be applied to better-controlled glaze production for artists and a deeper appreciation of ceramic glaze chemistry and aesthetics.
Introducing chemical equilibrium concepts in undergraduate general chemistry promotes improved understanding of chemical reactions. We have developed an engaging laboratory experiment exploring the equilibrium of cobalt complexation in alcohols using UV−vis spectroscopy and successfully implemented in a large general chemistry class of 378 students at Brown University. The octahedral to tetrahedral (pink to blue) cobalt complex transition generates vivid visualizations, increasing students' interest in learning. The equilibrium constants can be measured using UV−vis absorption spectroscopy and the Beer−Lambert law. Vast differences in molar absorptivity coefficients between octahedral and tetrahedral geometries of cobalt complexes prompt discussions on absorptivity, orbital splitting, and color change under the purview of learning Le Chatelier's principle. Additionally, the experimental results regarding the equilibrium constant allowed students to examine possible mechanistic pathways. Student responses to conducting the experiment were positive, most notably because this experiment encouraged them to analyze their experimental results critically and propose possible reaction mechanisms and equilibrium expressions while appreciating the sharp color transition that the complexation equilibrium undergoes.
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