Issue 1, 2024

Direct thermodynamic characterization of solid-state reactions by isothermal calorimetry

Abstract

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.

Graphical abstract: Direct thermodynamic characterization of solid-state reactions by isothermal calorimetry

Supplementary files

Article information

Article type
Paper
Submitted
17 ago. 2023
Accepted
17 oct. 2023
First published
27 oct. 2023

Phys. Chem. Chem. Phys., 2024,26, 67-75

Direct thermodynamic characterization of solid-state reactions by isothermal calorimetry

M. Cvetnić, R. Šplajt, E. Topić, M. Rubčić and N. Bregović, Phys. Chem. Chem. Phys., 2024, 26, 67 DOI: 10.1039/D3CP03933A

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