Revue des sciences chimiques

Transformations of Components Investigated using Multimethodical Approaches

Abstract

Vladimir L. Kasatkin

The isomorphism of S-bearing feldspathoids belonging to the cancrinite, sodalite, tugtupite, vladimirivanovite, bystrite, marinellite and scapolite structure types has been investigated using a multimethodical approach based on infrared, Raman and electron spin resonance (ESR), as well as ultraviolet, visible and near infrared (UV-Vis-near IR) absorption spectroscopy methods and involving chemical and X-ray diffraction data. Sapozhnikovite Na₈(Al₆Si₆O₂₄)(HS)₂ and sulfite and thiosulfate analogues of cancrinite are synthesized hydrothermally and characterized by means of electron microprobe analyses, powder X-ray diffraction and Raman spectroscopy. The possibility of the incorporation of significant amounts of SO₄²⁻, S₄ and SO₃²⁻ in the crystal structures of cancrisilite, sulfhydrylbystrite and marinellite, respectively, has been established for the first time. Thermal conversions of S-bearing groups in the synthetic sulfite cancrinite and sapozhnikovite analogues as well as natural vladinirivanovite and S₄^- bearing haüyne under oxidizing and reducing conditions have been studied using the multimethodical approach. The SO₄²⁻ and S²⁻ anions and the S₃^•- radical anion are the most stable S-bearing species under high-temperature conditions (in the range of 700-800°C); their ratio in the heated samples is determined by the redox conditions and charge-balance requirement. The HS⁻ and S₅²⁻ anions are stable only under highly reducing conditions.