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Title: The impact of oxygen nonstoichiometry upon partial molar thermodynamic quantities in PrBaCo{sub 2}O{sub 5+δ}

Abstract

The coulometric titration data are utilized in order to calculate changes of oxygen partial entropy and enthalpy in PrBaCo{sub 2}O{sub 5+δ} with variations of oxygen content and temperature. The thermodynamic equilibrium of the cobaltite with the ambient gas phase is analyzed based on the interface of oxygen exchange and oxidation, and the intrinsic reaction of thermal excitation of Co{sup 3+} cations. The partial thermodynamic functions of the movable oxygen in PrBaCo{sub 2}O{sub 5+δ} are shown to be interrelated with the thermodynamic parameters of the defect formation reactions. The existence of a band gap of about 0.4 eV in the electronic spectrum of the cobaltite follows from a favorable comparison of the calculated and experimental dependencies of the partial thermodynamic functions of the movable oxygen. - Graphical abstract: Partial thermodynamic functions of movable oxygen in PrBaCo{sub 2}O{sub 5+δ}. - Highlights: • Thermodynamic functions of oxygen in PrBaCo{sub 2}O{sub 5+δ} are obtained from pO{sub 2}–T–δ diagram. • The defect model is developed to describe changes in thermodynamic functions. • Thermodynamic analysis gives evidence to a band gap in PrBaCo{sub 2}O{sub 5+δ}.

Authors:
 [1]; ;  [1]
  1. Institute of Solid State Chemistry, Pervomaiskaya str.91, Yekaterinburg 620990 (Russian Federation)
Publication Date:
OSTI Identifier:
22334205
Resource Type:
Journal Article
Journal Name:
Journal of Solid State Chemistry
Additional Journal Information:
Journal Volume: 213; Other Information: Copyright (c) 2014 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.; Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 0022-4596
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; CATIONS; COBALT IONS; ENTHALPY; ENTROPY; EXCITATION; OXIDATION; OXIDES; OXYGEN; PEROVSKITE; SPECTRA; TITRATION

Citation Formats

Suntsov, A.Yu., E-mail: suntsov@ihim.uran.ru, Leonidov, I. A., Ural Federal University, Mira str.19, Ekaterinburg 620002, Patrakeev, M. V., and Kozhevnikov, V. L.. The impact of oxygen nonstoichiometry upon partial molar thermodynamic quantities in PrBaCo{sub 2}O{sub 5+δ}. United States: N. p., 2014. Web. doi:10.1016/J.JSSC.2014.02.004.
Suntsov, A.Yu., E-mail: suntsov@ihim.uran.ru, Leonidov, I. A., Ural Federal University, Mira str.19, Ekaterinburg 620002, Patrakeev, M. V., & Kozhevnikov, V. L.. The impact of oxygen nonstoichiometry upon partial molar thermodynamic quantities in PrBaCo{sub 2}O{sub 5+δ}. United States. https://doi.org/10.1016/J.JSSC.2014.02.004
Suntsov, A.Yu., E-mail: suntsov@ihim.uran.ru, Leonidov, I. A., Ural Federal University, Mira str.19, Ekaterinburg 620002, Patrakeev, M. V., and Kozhevnikov, V. L.. Thu . "The impact of oxygen nonstoichiometry upon partial molar thermodynamic quantities in PrBaCo{sub 2}O{sub 5+δ}". United States. https://doi.org/10.1016/J.JSSC.2014.02.004.
@article{osti_22334205,
title = {The impact of oxygen nonstoichiometry upon partial molar thermodynamic quantities in PrBaCo{sub 2}O{sub 5+δ}},
author = {Suntsov, A.Yu., E-mail: suntsov@ihim.uran.ru and Leonidov, I. A. and Ural Federal University, Mira str.19, Ekaterinburg 620002 and Patrakeev, M. V. and Kozhevnikov, V. L.},
abstractNote = {The coulometric titration data are utilized in order to calculate changes of oxygen partial entropy and enthalpy in PrBaCo{sub 2}O{sub 5+δ} with variations of oxygen content and temperature. The thermodynamic equilibrium of the cobaltite with the ambient gas phase is analyzed based on the interface of oxygen exchange and oxidation, and the intrinsic reaction of thermal excitation of Co{sup 3+} cations. The partial thermodynamic functions of the movable oxygen in PrBaCo{sub 2}O{sub 5+δ} are shown to be interrelated with the thermodynamic parameters of the defect formation reactions. The existence of a band gap of about 0.4 eV in the electronic spectrum of the cobaltite follows from a favorable comparison of the calculated and experimental dependencies of the partial thermodynamic functions of the movable oxygen. - Graphical abstract: Partial thermodynamic functions of movable oxygen in PrBaCo{sub 2}O{sub 5+δ}. - Highlights: • Thermodynamic functions of oxygen in PrBaCo{sub 2}O{sub 5+δ} are obtained from pO{sub 2}–T–δ diagram. • The defect model is developed to describe changes in thermodynamic functions. • Thermodynamic analysis gives evidence to a band gap in PrBaCo{sub 2}O{sub 5+δ}.},
doi = {10.1016/J.JSSC.2014.02.004},
url = {https://www.osti.gov/biblio/22334205}, journal = {Journal of Solid State Chemistry},
issn = {0022-4596},
number = ,
volume = 213,
place = {United States},
year = {2014},
month = {5}
}