Sulphur-Oxygen Compounds

Sulphur-Oxygen Compounds.—The i.r. spectra of matrix-isolated S2O isotopes have been measured. The photoelectron spectra of S2O, O3, and SO2 have been compared, and further experimental details of the spectrum of S2O presented.  

Rosmus, P. D. Dacre, B. Solouki, and H. Bock, Theor. Chim. Acta, 1974, 35, 129. 

The vibrational spectrum of SO2 in various matrices has been measured. Sulphur dioxide has been photochemically oxidized to SO3 on the surface of MgO in the presence of water vapour, oxygen, or N2O. The complex that gives rise to the transient yellow colour which is formed on mixing equimolar solutions of thiosulphate and sulphur dioxide has been identified as being Na2[S203(S0)2]. 

A study of the reaction of fluorine with SO2 has shown that at temperatures up to 500 °C the reaction rapidly gives sulphuryl fluoride. If the quantity of fluorine is large enough, then SFe is formed, but only slowly, and via the formation of thionyl fluoride, thionyl tetrafluoride, and pentafluorosulphur hypo-fluorite. The fluorination of SO2 by Xep2, in the presence of compounds of the type MX (M = NMe4, Cs, or K X = F or Cl), has been studied. A variety of products were observed (Table 2) and reaction mechanisms were proposed in which the Xep2 functions as a weak Lewis acid. 

The crystal structure of the 1 2 complex formed between NNN N -tetramethyl-p-phenylenediamine and SO2 has been determined. The structure consists of discrete molecular complexes containing one TMPD molecule and two SO2 molecules attached through two N—S bonds of equal lengths (2.340 and 2.337 A). The S—O distances are essentially the same as those found in solid and gaseous SO2, but the O—S—O angles are considerably contracted. 

Sulphur-Oxygen Compounds.—The crystal structure of cyclo-octasulphur oxide has been determined. The molecules consist of crown-shaped Sg rings with axially bonded oxygen atoms (38). The S—S distances vary between 2.00 and 2.20 A, and the S—O distance is 1.483 A a strong intermolecular S - O interaction was postulated.  

The first complex of sulphur monoxide (39) has been synthesized by two different routes [reactions (25) and (26)]. It is thought that the structure of (39) will be similar to that of (40), whose structure has been determined. The iridium 

The Raman spectrum of matrix-isolated S2O has been observed by preparing relatively large amounts by direct synthesis from thionyl chloride and Ag2S. The self decomposition of S2O is thought to take place by a bimolecular reaction with itself, possibly through a complex (41), which may explain why the observed products are S3 and SO2.  

A paramagnetic ion attributed to S20 has been observed by e.p.r. spectra when H2S and SO2 are allowed to react on MgO at 25 °C. The proposed mechanism for the formation of S20 involves the reaction of elemental sulphur, as S2, with oxide ions of the MgO surface. The photoelectron spectra of H2C=S=0 ° and HN=S=0 have been recorded and the ionization energies of X=S=0 derivatives compared.  

spectra of SO2 in various matrices (Ar, N2, Xe) have been recorded at low temperatures. Several isotopic species in their natural abundances were detected, and a vibrational analysis was carried out. A blue, glassy solution has been observed on 7-irradiation of SO2 in 2-methyltetrahydrofuran at -196 °C. Since the monomer radical anion of SO2 is colourless, the absorption spectrum of the blue solution was attributed to the dimer or trimer radical anion.  

Schwarz, H. D. Hausen, H. Hess, J. Handt, W. Schmelzer, and B. Krebs, Acta Cryst., 1973, B29, 2029. 

Almenningen, H. M. Seip, and P. Vassbom, Acta Chem. Scand., 1973, 27, 21. 

93 per oxygen is observed in going from sulphide to sulphite, but there is a further rise of 11.85 x 10 e.m.u. mol in going to sulphate this effect was also noted in the P-0 system. 

Crystals of SgO, produced by condensation of SOClg with crude sulphane (H2S , n = 3, 4, or 5) and recrystallization from CSg, have been shown to belong to the space group Pcfl2, with a = 13.197,= 7.973,andc = 8.096 A. The molecule SgO belongs to the point group C, the sulphur atoms form a crown-shaped ring (43) in which each set of four atoms lies approximately in 

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From Sulphur-Oxygen Compounds.—Sulphites in aqueous solution are easily reduced to hydrogen sulphide by nascent hydrogen, produced, for example, by the interaction of zinc and dilute sulphuric acid ... 

The electrochemical reaction of sulphur-oxygen compounds - Part 1. A review of literature on the electrochemical properties of sulphur/sulphur-oxygen compounds, Electrochim. Acta, 1992, 37, 2775. Pulsed potentiostatic deposition of gold from solutions of the Au(I) sulfite complex, J. Horkans and L. T. 

Group V. This group includes all the water-insoluble hydrocarbons and oxygen compounds that do not contain N or S and are soluble in cold concentrated sulphuric acid. Any changes—colour, excessive charring, evolution of gases or heat, polymerisation and precipitation of an insoluble compound— attending the dissolution of the substance should be carefully noted. 

The rest of these sulphur and oxygen compounds, with the exception of sulphurous and aulphurio acid, ore at present useless in the arte, but are valuable in a scientific point of view. 

In addition, more highly oxygenated compounds of sulphur of uncertain composition have been described (sec j . -hi), as well as an intermediate oxide of tellurium, Tc.,07 (p. 800). The following mixed sesquioxides arc also known SSeO.,. STcO i, ScTc03. 

The simpler aliphatic sulphur derivatives considered in this section are the sulphur analogues of oxygen compounds, e.g. the thiols (RSH), and the symmetrical or unsymmetrical thioethers (R-S-R or R -S-R2). Compounds derived from these two groups, where the sulphur atom can attain a higher oxidation state, are the sulphinic and sulphonic acids (R-SO-OH and R-S02 OH), the sulphox-ides (R-SO-R), and the sulphones (R-S02-R). Other compounds of interest which are considered in the following discussion are ... 

Sulphur, in accord with its similarity to oxygen, can be substituted for it in many of its compounds without essentially altering their chemical nature, and the compounds thus obtained have the same nomenclature as the corresponding oxygen compounds, except that the prefix thio or sulpho is used. Thus sulpho-salts are produced in the same manner as the oxy-salts above ... 

Uses of the Sulphides of Phosphorus.—The pentasulphide of phosphorus is used to replace the oxygen of organic compounds by sulphur thus ethyl alcohol gives ethyl mercaptan, and acetic acid thioacetic acid.4 The reactions, however, are somewhat complex thus with ethyl alcohol the first product has been shown to be diethyl-dithiophosphate, SP(SH)(OEt)s, the mercaptan being produced by a secondary reaction.5 Phosphorus pentasulphide, boiling under atmospheric or other definite pressure, has been recommended for use in constant temperature baths in place of sulphur. The compound P4S3, which is one of the most stable sulphides in diy air, but resembles phosphorus in some respects, is used as a substitute for this element in the manufacture of matches.6... 

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