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Inorganic polysulfide anions Sn2− and the related radical anions Sn·− play an important role in the redox reactions of elemental sulfur and therefore also in the geobiochemical sulfur cycle. This chapter describes the preparation of the solid polysulfides with up to eight sulfur atoms and univalent cations, as well as their solid...
The sulfanes H2Sn form a long series of homologous chain-like molecules, starting with hydrogen sulfide and running at least up to H2S35. These molecules are the parent compounds of numerous derivatives with either organic or inorganic substituents. In this chapter the preparation, structures, physical and chemical properties as well as the spectra of the sulfanes with ≥2...
Sulfur is the element with the largest number of solid allotropes. Most of these consist of unbranched cyclic molecules with ring sizes ranging from 6 to 20. In addition, polymeric allotropes are known which are believed to consist of chains in a random coil or helical conformation. Furthermore, several high-pressure allotropes have been characterized. In this chapter the preparation, crystal structures,...
SulfurSulfur sols are colloidalcolloidal solutions of elemental sulfur or of sulfur-rich compounds. The particles in these solutions have diameters of 0.1–1.0 μm and consist either of S8 molecules (hydrophobic sulfur sols)hydrophobic sulfur sol or of chain-like sulfur compounds with hydrophilic end groups like sulfonate or functionalized organic groups (hydrophilic sulfur sols)hydrophilic sulfur sol...
Sulfur vaporSulfur vapor at temperatures of between 200 and 1000 °C consists of all molecules with 2–10 atoms, some of which exist as two or more isomersS4 isomer. Extensive mass spectrometric investigations and vapor pressure measurements provided reliable thermodynamicsulfur vaporspeciationthermodynamic data for the various dissociation reactions S8 S8 ⇌8/n Sn...
The molecular composition as well as the physical properties (including spectra) of liquid sulfurLiquid Sulfurproperties are reviewed starting with a historic Introduction to explain the terms π-sulfurπ-Sulfurproperties and μ-sulfurμ-sulfurproperties. At all temperatures the melt contains homocyclic rings of between 6 and at least 35 atoms with S8 as the majority species as well as polymeric sulfurpolymeric...
Sulfur is the element with the largest number of binary oxides. In this chapter the lower sulfur oxides are reviewed most of which contain more sulfur than oxygen atoms per molecule and all have at least one sulfur-sulfur bond. They may exist as gaseous compounds consisting of small molecules (S2O, S2O2), as crystalline materials (S6O, S7O, S7O2, S8O, S9O, S10O), or as polymeric non-stoichiometric...
Molecular spectroscopy is one of the most important means to characterize the various species in solid, liquid and gaseous elemental sulfur. In this chapter the vibrational, UV-Vis and mass spectra of sulfur molecules with between 2 and 20 atoms are critically reviewed together with the spectra of liquid sulfur and of solid allotropes including polymeric and high-pressure phases. In particular, low...
Despite more than 200 years of sulfur research the chemistry of elemental sulfur and sulfur-rich compounds is still full of “white spots” which have to be filled in with solid knowledge and reliable data. This situation is parti- larly regrettable since elemental sulfur is one of the most important raw - terials of the chemical industry produced in record-breaking quantities of ca. 35 million tons...
The sodium–sulfur (NAS) battery is a candidate for energy storage and load leveling in power systems, by using the reversible reduction of elemental sulfur by sodium metal to give a liquid mixture of polysulfides (Na2Sn) at approximately 320 °C. We investigated a large number of reactions possibly occurring in such sodium polysulfide melts by using density functional calculations at the G3X(MP2)/B3LYP/6‐31+G(2df,p)...
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