Molten and glassy tellurium(IV) oxosulfato complexes in the TeO2 –K2S2O7 system studied by Raman spectroscopy: Stoichiometry, vibrational properties and molecular structure

Angelos G. Kalampounias, George Tsilomelekis, Soghomon Boghosian

Research output: Contribution to journalArticlepeer-review

3 Scopus citations

Abstract

Tellurium(IV) oxide dissolves in molten potassium pyrosulfate following a reaction that leads to TeIV oxosulfato complexes. High temperature Raman spectroscopy is used under static equilibrium conditions at temperatures of 550 – 740oC for inferring the structural properties of the complex(es) formed in TeO2-K2S2O7 molten mixtures (XTeO2 0 = 0 – 0.70) under O2 atmosphere. The composition effects on the Raman spectra together with the outcome of a quantitative exploitation of the relative Raman band intensities point to a 3:1 TeO2:K2S2O7 stoichiometry, which combined with the observed vibrational properties is suggestive of a (Te=O)3O2(SO4)2 2- structural formula for the simplest building unit formed. A 3-fold coordination around Te becomes evident comprising an oxide ligand and two oxygen atoms bridging to adjacent Te or S atoms. A gradual association of building units takes place with increasing XTeO2 0. Cooling results in formation of stable glasses with a concomitant change in the coordination number of TeIV from 3 to 4 by means of a structural mechanism suggestively involving a TeO2/2(=O)→ TeO4/2 transformation. Totally ten bands are attributed to the TeIV oxosulfato complex; the most characteristic ones pertain to the 1040 cm-1 band assigned to symmetric stretching unidentate sulphate and to the 850 cm-1 band assigned to Te=O terminal stretching, the latter band being attenuated on going from the molten to the glassy state due to the TeO2/2(=O)→ TeO4/2 interconversion.

Original languageEnglish (US)
Pages (from-to)85-90
Number of pages6
JournalVibrational Spectroscopy
Volume97
DOIs
StatePublished - Jul 2018

All Science Journal Classification (ASJC) codes

  • Spectroscopy

Keywords

  • Glasses
  • Molten salts
  • Oxo Te complexes
  • Oxo-sulfato
  • Raman spectra
  • Te(IV) complexes
  • Tellurium–oxygen bond

Fingerprint

Dive into the research topics of 'Molten and glassy tellurium(IV) oxosulfato complexes in the TeO<sub>2</sub> –K<sub>2</sub>S<sub>2</sub>O<sub>7</sub> system studied by Raman spectroscopy: Stoichiometry, vibrational properties and molecular structure'. Together they form a unique fingerprint.

Cite this