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Structure, thermal behavior, and dielectric properties of new cesium hydrogen sulfate arsenate: Cs2(HSO4)(H2AsO4)

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Abstract

Synthesis and structural characterization by single-crystal X-ray diffraction method, thermal behavior, and electrical proprieties are given for a new compound with a superprotonic phase transition Cs2(HSO4)(H2AsO4). The title compound crystallizes in the monoclinic system with the P21/n space group. The structure contains zigzag chains of hydrogen-bonded anion tetrahedra that extend in the [010] direction. Each tetrahedron is additionally linked to a tetrahedron neighboring chain to give a planar structure with hydrogen-bonded sheets lying parallel to (10ī). The existence of O–H and (S/As)–O bonds in the structure at room temperature has been confirmed by IR and Raman spectroscopy in the frequency ranges 4000–400 cm−1and 1200–50 cm−1, respectively. Differential scanning calorimetry analysis of the superprotonic transition in Cs2(HSO4)(H2AsO4) showed that the transformation to high temperature phase occurs at 417 K by one-step process. Thermal decomposition of the product takes place at much higher temperatures, with an onset of approximately 534 K. The superprotonic transition was also studied by impedance and modulus spectroscopy techniques. The conductivity in the high temperature phase at 423 K is 1.58 × 10−4 Ω−1 cm−1, and the activation energy for the proton transport is 0.28 eV. The conductivity relaxation parameters associated with the high disorder protonic conduction have been examined from analysis of the M”/M”max spectrum measured in a wide temperature range. Transport properties of this material appear to be due to the proton hopping mechanism.

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Nouiri, N., Jaouadi, K., Mhiri, T. et al. Structure, thermal behavior, and dielectric properties of new cesium hydrogen sulfate arsenate: Cs2(HSO4)(H2AsO4). Ionics 22, 1611–1623 (2016). https://doi.org/10.1007/s11581-016-1679-0

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  • DOI: https://doi.org/10.1007/s11581-016-1679-0

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