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On the isostructural and superprotonic Cs5H3(SO4)4·xH2O transformations: physical or chemical nature?

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Abstract

For over 20 years, researchers have agreed that when pentacesium trihydrogen tetrasulfate hydrate (Cs5H3(SO4)4·xH2O) is heated through 141 °C, the observed conductivity increase corresponds to a physical transformation: a first-order superprotonic phase transition. A careful high-temperature phase behavior examination of this acid salt was performed by means of simultaneous thermogravimetric and differential scanning calorimetry, conventional and modulated differential scanning calorimetry, and impedance spectroscopy. The results present evidence that this transformation is of chemical, instead of physical nature. The conductivity increase is an exclusive consequence of a partial thermal decomposition, where liquid water (dissolving part of the surface salt) and hygroscopic cesium pyrosulfate (Cs2S2O7), as decomposition products, behave like a polymer electrolyte membrane where the proton transport mechanism includes the vehicle type, using hydronium (H3O+) as a charge carrier. Additionally, it was found that the intermediate temperature transformation (so-called isostructural phase transition) at around 87 °C is also of chemical nature.

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Acknowledgements

We are grateful to Professor Bengt-Erik Mellander (Department of Applied Physics, Chalmers University of Technology, Gothenburg-Sweden) for the useful discussions about the design of the project that led to this contribution.

Funding

This work was supported by the Department of Research at Universidad del Atlántico (research project No. CB40-FGI2016, Grant No. 000721-10-05-2017).

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Authors and Affiliations

  1. GFM, Department of Physics, Faculty of Basic Sciences, Universidad del Atlántico, Km. 7 Antigua vía Puerto Colombia, Barranquilla, Colombia

    E. Ortiz, V. Mendoza-Estrada & J. Romero

  2. Department of Natural and Exact Sciences, Universidad de la Costa, Barranquilla, Colombia

    V. Mendoza-Estrada

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  1. E. Ortiz
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Correspondence to E. Ortiz.

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Ortiz, E., Mendoza-Estrada, V. & Romero, J. On the isostructural and superprotonic Cs5H3(SO4)4·xH2O transformations: physical or chemical nature?. Ionics 24, 2673–2680 (2018). https://doi.org/10.1007/s11581-017-2408-z

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