Experimental Thermochemistry Through the Years with Application to Chalcogenides

Chalcogenides (sulfides, selenides, tellurides, arsenides, antimonides) are important in natural processes, including formation of ore deposits on Earth, early stages of planetary accretion, and formation of condensates in planetary atmospheres. Their physicochemical properties render them suitable for a wide range of industrial applications. While thermodynamic data are available for many endmembers, there are significant gaps in both thermodynamic and associated structural constraints, especially for complex systems. The continuous evolution of high temperature calorimetry into oxidative drop solution calorimetry has facilitated the measurement of enthalpies of formation and mixing and surface energies involving nonoxides, including chalcogenides. These are essential for modeling processes in nature and technology and for understanding the underlying properties that define their stabilities. This article reviews the development of these calorimetric techniques and summarizes available thermochemical data for common chalcogenides. ▪ Over the last century, calorimetric instruments and techniques have evolved to enable accurate measurement of a wide range of materials, including chalcogenides. ▪ Despite the growing interest in the thermodynamic characterization of chalcogenides, a systematic review of the available data indicates that there is still a significant scope for further research. ▪ A systematic understanding of chalcogenides will facilitate the modeling of geological environments and enable the prediction and improvement of geo-inspired materials for industrial applications.