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Thermodynamic stability of CaThF6(cr) by transpiration and e.m.f. techniques

Authors
  • Mukherjee, Sumanta1, 2
  • Dawar, Rimpi1, 3
  • Phapale, S.1, 3
  • Dash, S.1, 2
  • Mishra, R.1, 3
  • 1 Bhabha Atomic Research Centre, Homi Bhabha National Institute (HBNI), Trombay, Mumbai, 400085, India , Trombay, Mumbai (India)
  • 2 Bhabha Atomic Research Centre, Fuel Chemistry Division, Trombay, Mumbai, 400085, India , Trombay, Mumbai (India)
  • 3 Bhabha Atomic Research Centre, Chemistry Division, Trombay, Mumbai, 400085, India , Trombay, Mumbai (India)
Type
Published Article
Journal
Journal of Thermal Analysis and Calorimetry
Publisher
Springer Netherlands
Publication Date
Dec 04, 2018
Volume
137
Issue
2
Pages
667–677
Identifiers
DOI: 10.1007/s10973-018-7950-z
Source
Springer Nature
Keywords
License
Yellow

Abstract

In the present paper, we report the standard molar Gibbs energy of formation for CaThF6 measured by gas equilibration and e.m.f. methods. The HF(g) vapour pressure over the equilibrium reaction: CaThF6cr+2H2Og=CaF2cr+ThO2cr+4HFg\documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$${\text{CaThF}}_{6} \left( {\text{cr}} \right) + 2 {\text{H}}_{ 2} {\text{O}}\left( {\text{g}} \right) = {\text{CaF}}_{2} \left( {\text{cr}} \right) + {\text{ThO}}_{2} \left( {\text{cr}} \right) + 4{\text{HF}}\left( {\text{g}} \right)$$\end{document} has been measured using transpiration technique. The above reaction mechanism has been established employing TG and XRD techniques. A fluoride e.m.f. cell: (−)Pt, CaF2(cr) + ThOF2(cr) + CaThF6(cr) |CaF2(cr)| NiO(cr) + NiF2(cr), Pt(+) has been constructed to measure Gibbs energy of formation of CaThF6 (cr) using CaF2 (cr) as a solid electrolyte. The isobaric heat capacity Cpm∘T\documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$${\text{Cp}}_{\text{m}}^{{\circ }} \left( T \right)$$\end{document} of the compound has been measured using differential scanning calorimetric technique. Based on the experimental results, thermodynamic functions for CaThF6 have been generated.

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