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The Formation and Stability of the [FePy3Cl3]· Py Clathrate in the Pyridine–Iron(III) Chloride System: Phase Diagram and Solid–Gas Equilibria Study

  • Andrew G. Ogienko
  • Elissa A. Ukraintseva
  • Tatyana A. Chingina
  • Vladislav Yu. Komarov
  • Andrey Yu. Manakov
Article

Abstract

The phase diagram of the pyridine–iron(III) chloride system has been studied for the 223–423 K temperature and 0–56 mass-% concentration ranges using differential thermal analysis (DTA) and solubility techniques. A solid with the highest pyridine content formed in the system was found to be an already known clathrate compound, [FePy3Cl3]·Py. The clathrate melts incongruently at 346.9 ± 0.3 K with the destruction of the host complex: [FePy3Cl3]·Py(solid)=[FePy2Cl3](solid) + liquor. The thermal dissociation of the clathrate with the release of pyridine into the gaseous phase (TGA) occurs in a similar way: [FePy3Cl3]·Py(solid)=[FePy2Cl3](solid) + 2 Py(gas). Thermodynamic parameters of the clathrate dissociation have been determined from the dependence of the pyridine vapour pressure over the clathrate samples versus temperature (tensimetric method). The dependence experiences a change at 327 K indicating a polymorphous transformation occurring at this temperature. For the process \({1 \over 2}[\hbox{FePy}_{3}\hbox{Cl}_{3}]\cdot \hbox{Py}_{\rm (solid)} = {1 \over 2}[\hbox{FePy}_{2}\hbox{Cl}_{3}]_{\rm (solid)} + \hbox{Py}_{\rm (gas)}\) in the range 292–327 K, ΔH \(^{0}_{298}\)=70.8 ± 0.8 kJ/mol, ΔS \(^{0}_{298}\)=197 ± 3 J/(mol K), ΔG \(^{0}_{298}\)=12.2 ± 0.1 kJ/mol; in the range 327–368 K, ΔH \(^{0}_{298}\)=44.4 ± 1.3 kJ/mol, ΔS \(^{0}_{298}\)=116 ± 4 J/(mol K), ΔG \(^{0}_{298}\)=9.9 ± 0.3 kJ/mol.

Keywords

iron(III) chloride phase diagram pyridine thermodynamic parameters vapour pressure Werner clathrates 

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Copyright information

© Springer 2005

Authors and Affiliations

  • Andrew G. Ogienko
    • 1
  • Elissa A. Ukraintseva
    • 1
  • Tatyana A. Chingina
    • 1
  • Vladislav Yu. Komarov
    • 1
  • Andrey Yu. Manakov
    • 1
  1. 1.Nikolaev Institute of Inorganic Chemistry SB RASNovosibirskRussian Federation

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