Mechanism and Kinetics of Hydration of CuSO4·H2O in the Presence of an Intermediate Step
Martina Cotti1,2, Amelie Stahlbuhk3, Hartmut R Fischer4
1Eindhoven Institute of Renewable Energy Systems, Eindhoven University of Technology, PO Box 513, Eindhoven 5600 MB, 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.
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