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Enthalpy increments and redox thermodynamics of SrFeO3−δ

Published online by Cambridge University Press:  30 August 2019

Vladimir Sereda Open the ORCID record for Vladimir Sereda [Opens in a new window] ,
Anton Sednev ,
Dmitry Tsvetkov  and
Andrey Zuev
Vladimir Sereda*
Affiliation:
Department of Physical and Inorganic Chemistry, Institute of Natural Sciences and Mathematics, Ural Federal University, Yekaterinburg 620002, Russia; and Department of Solid State Electrochemistry, Institute of High-Temperature Electrochemistry UB RAS, Yekaterinburg 620137, Russia
Anton Sednev
Affiliation:
Department of Physical and Inorganic Chemistry, Institute of Natural Sciences and Mathematics, Ural Federal University, Yekaterinburg 620002, Russia; and Department of Solid State Electrochemistry, Institute of High-Temperature Electrochemistry UB RAS, Yekaterinburg 620137, Russia
Dmitry Tsvetkov
Affiliation:
Department of Physical and Inorganic Chemistry, Institute of Natural Sciences and Mathematics, Ural Federal University, Yekaterinburg 620002, Russia
Andrey Zuev
Affiliation:
Department of Physical and Inorganic Chemistry, Institute of Natural Sciences and Mathematics, Ural Federal University, Yekaterinburg 620002, Russia
*
a)Address all correspondence to this author. e-mail: vladimir.sereda@urfu.ru
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Abstract

Enthalpy increments, $\Delta _{298}^T{H^0}$, for highly nonstoichiometric SrFeO3−δ (δ = 0.18–0.41) were obtained between 373 and 1273 K in air using drop calorimetry. The analysis of the $\Delta _{298}^T{H^0}\left( T \right)$ dependence at lower temperatures allowed evaluating the enthalpy of tetragonal to cubic ${{I4} / {mmm}} \,{\tf="TeX CM Bold Maths Symbols"\char33}\, Pm\bar{3}m$ phase transition at 560 K, 1.57 kJ/mol, and the Maier–Kelley function for $\Delta _{298}^T{H^0}\left( T \right)$ of tetragonal SrFeO3−δ (space group ${{I4} / {mmm}}$). Combined investigation of oxygen nonstoichiometry $\bolddelta \left( T \right)$ dependence, measured by thermogravimetry, and higher-temperature $\Delta _{298}^T{H^0}\left( T \right)$ of cubic SrFeO3−δ (space group $Pm\bar{3}m$) yielded the temperature-dependent reduction (oxygen release) enthalpy, $\Delta H_{{\rm{red}}}^{\rm{0}}$. Calorimetrically-determined $\Delta H_{{\rm{red}}}^{\rm{0}}$ of SrFeO3−δ increases from 65 ± 7 kJ/mol O at 873–973 K to 84 ± 7 kJ/mol O at 1073–1273 K, which may indicate that the short-range vacancy ordering in SrFeO3−δ is hampered at higher temperatures.

Keywords

calorimetryoxideoxidation
Type
Invited Paper
Information
Journal of Materials Research , Volume 34 , Issue 19: Focus Issue: Thermodynamics of Complex Solids , 14 October 2019 , pp. 3288 - 3295
Copyright
Copyright © Materials Research Society 2019 

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