2017-Sustainable Industrial Processing Summit
SIPS 2017 Volume 3. Gaune-Escard Intl. Symp. / Molten Salt and Ionic Liquid
| Editors: | Kongoli F, Fehrmann R, Gadzuric S, Gong W, Seddon KR, Malyshev V, Iwata S |
| Publisher: | Flogen Star OUTREACH |
| Publication Year: | 2017 |
| Pages: | 151 pages |
| ISBN: | 978-1-987820-65-2 |
| ISSN: | 2291-1227 (Metals and Materials Processing in a Clean Environment Series) |
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Electrical Conductivity and Raman Spectra of Molten GaCl3 – PCl5 Mixtures
Alexander Salyulev1; Alexei Potapov1; Emma Vovkotrub1;1INSTITUTE OF HIGH TEMPERATURE ELECTROCHEMISTRY, Ekaterinburg, Russian Federation;
Type of Paper: Regular
Id Paper: 45
Topic: 13
Abstract:
Molten GaCl3 - PCl5 mixtures are of practical interest, for example in new power sources design.
In this work we first measured the electrical conductivity of GaCl3 - PCl5 mixtures. The measurements were carried out using quartz capillary cells with Ni- or W-electrodes at the input frequency of 10 kHz. For the first time Raman spectra of the mixtures were obtained by the Renishaw U1000 spectrometer with Ar+ - laser. All measurements were carried out in sealed off cells.
In spite of the fact that upon melting individual GaCl3 and PCl5 salts form molecular melts with a very low conductivity (k < 1•10-7 S/cm), we found that the conductivity of GaCl3 - PCl5 mixtures is higher by several orders of magnitude (2•10-3 - 1•10-1 S/cm at 20-340 °C) than that of individual molten GaCl3 and PCl5. This is caused by the interaction of GaCl3 and PCl5 molecules, which results in their ionization and formation of PCl4+ complex cations and GaCl4-, Ga2Cl7- anions.
Based on spectroscopic data, we found that in the GaCl3 - PCl5 system as the phosphorus pentachloride concentration gradually increases from 0 to 100% the liquid phase composition changes as follows:
Molecular Ionic Ionic Molecular
melt melt melt melt
Ga2Cl6 = PCl4+ + GaCl4- = PCl4+ + Ga2Cl7- = PCl5 .
Keywords: GaCl3 - PCl5 melts, electrical conductivity, Raman spectra