Mechanism and Kinetics of Hydration of CuSO4·H2O in the Presence of an Intermediate Step

Martina Cotti; Amelie Stahlbuhk; Hartmut R Fischer; Michael Steiger; Olaf C G Adan; Henk P Huinink

doi:10.1021/acs.cgd.4c00589

Mechanism and Kinetics of Hydration of CuSO₄·H₂O in the Presence of an Intermediate Step

Cryst Growth Des. 2024 Dec 9;24(24):10082-10093. doi: 10.1021/acs.cgd.4c00589. eCollection 2024 Dec 18.

Authors

Martina Cotti^{1

2}, Amelie Stahlbuhk³, Hartmut R Fischer⁴, Michael Steiger³, Olaf C G Adan^{2

4}, Henk P Huinink^{1

2}

Affiliations

¹ Eindhoven Institute of Renewable Energy Systems, Eindhoven University of Technology, PO Box 513, Eindhoven 5600 MB, The Netherlands.
² Transport in Permeable Media group, Department of Applied Physics, Eindhoven University of Technology, PO Box 513, Eindhoven 5600 MB, The Netherlands.
³ Department of Chemistry, University of Hamburg, Martin-Luther-King-Platz 6, Hamburg 20146, Germany.
⁴ TNO Materials Solution, High Tech Campus 25, Eindhoven 5656 AE, The Netherlands.

Abstract

The hydration of salt hydrates is often described as a solution mediated nucleation and growth mechanism, occurring between a reagent and a product in thermodynamic equilibrium with each other. If a system possesses more than one hydrate phase, the kinetic pathway may involve additional mechanisms due to the formation of intermediate hydrate species. We elected CuSO₄ as our model system and analyzed the pathway leading from CuSO₄·H₂O (C1H) to CuSO₄·5H₂O (C5H), while CuSO₄·3H₂O (C3H) being a possible intermediate. We found that C1H hydration is mediated by the formation of C3H and that C5H does not nucleate directly from C1H, at the studied conditions. The hydration pathway therefore is characterized by the same mechanism occurring twice, nucleation and growth of C3H and nucleation and growth of C5H. Analysis of the hydration kinetics of C1H revealed that C5H nucleates rapidly from C3H, as if the metastability of C3H was reduced when starting from C1H. Therefore, we concluded that the hydration kinetics of C1H are probably controlled by the growth process of C5H. Despite being controlled by a single reaction process, we show that a single front 1D diffusion model is insufficient to describe the reaction kinetics at the tablet level. Understanding of these complex transformations is necessary to evaluate the suitability of these reactions for application, in particular with respect to the achieved power output.