Direct thermodynamic characterization of solid-state reactions by isothermal calorimetry
Literature Information
Marija Cvetnić, Robert Šplajt, Edi Topić, Mirta Rubčić, Nikola Bregović
Despite the growing importance of solid-state reactions, their thermodynamic characterization has largely remained unexplored. This is in part due to the lack of methodology for measuring the heat effects related to reactions between solid reactants. We address here this gap and report on the first direct thermodynamic study of chemical reactions between solid reactants by isothermal calorimetry. Three reaction classes, cationic host–guest complex formation, molecular co-crystallization, and Baeyer–Villiger oxidation were investigated, showcasing the versatility of the devised methodology to provide detailed insight into the enthalpy changes related to various reactions. The reliability of the method was confirmed by correlation with the values obtained via solution calorimetry using Hess's law. The thermodynamic characterization of solid-state reactions described here will enable a deeper understanding of the factors governing solid-state processes.
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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.












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