Forms of sulfur

Sulfur occurs in both inorganic and organic forms as shown in Table 11.2. The general forms of inorganic sulfur in the environment fall into three major categories  

Minerals containing sulfur include galena (PbSj), gypsum (CaS04), jarosite (Fe2S), barite (BaS04), and pyrite (FeSj). 

FIGURE 11.2 Organic sulfur constituents in Louisiana marsh soils, present as acid-volatile sulfides (AVS) elemental sulfur (S ) pyrite (FeSj), and HCl-soluble forms. (Modified from Krairapanond et al., 1992.) 

In plant, animal, and microbial tissue (as essential components of amino acids and proteins) 

In soil and sediments as humic material (naturally occurring soil and sediment organic matter) 

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The major part of the sulfur contained in crude petroleum is distributed between the heavy cuts and residues (Table 8.10) in the form of sulfur compounds of the naphthenophenanthrene or naphthenoanthracene type, or in the form of benzothiophenes, that is, molecules having one or several naphthenic and aromatic rings that usually contain a single sulfur atom. 

Eleven isotopes of sulfur exist. None of the four isotopes that in nature are radioactive. A finely divided form of sulfur, known as flowers of sulfur, is obtained by sublimation. 

We also developed a number of other useful new fluorinating reagents. They ineluded a convenient in situ form of sulfur tetrafluoride in pyridinium polyhydrogen fluoride, selenium tetrafluoride, and ey-anurie fluoride. We introdueed uranium hexafluoride (UFg), depleted from the U-235 isotope, which is an abundant by-product of enrichment plants, as an effective fluorinating agent. 

Resources of Sulfur. In most of the technologies employed to convert phosphate rock to phosphate fertilizer, sulfur, in the form of sulfuric acid, is vital. Treatment of rock with sulfuric acid is the procedure for producing ordinary superphosphate fertilizer, and treatment of rock using a higher proportion of sulfuric acid is the first step in the production of phosphoric acid, a production intermediate for most other phosphate fertilizers. Over 1.8 tons of sulfur is consumed by the world fertilizer industry for each ton of fertilizer phosphoms produced, ie, 0.8 t of sulfur for each ton of total 13.7 X 10 t of sulfur consumed in the United States for all purposes in 1991, 60% was for the production of phosphate fertilizers (109). Worldwide the percentage was probably even higher. 

Minerals. Iron-bearing minerals are numerous and are present in most soils and rocks. However only a few minerals are important sources of iron and thus called ores. Table 2 shows the principle iron-bearing minerals. Hematite is the most plentiful iron mineral mined, followed by magnetite, goethite, siderite, ilmenite, and pyrite. Siderite is unimportant in the United States, but is an important source of iron in Europe. Tlmenite is normally mined for titania with iron as a by-product. Pyrite is roasted to recover sulfur in the form of sulfur dioxide, leaving iron oxide as a by-product. 

Upon solidification of molten sulfur, Stt rapidly changes into S]l, which is converted into SL, although at a much slower rate. The molecular stmcture of Stt is that of an octatomic sulfur chain (1,2). The symbol S]1 designates long, polymerized chains of elemental sulfur. SX is perhaps the most characteristic molecular form of sulfur, namely, that of a crown-shaped, octatomic sulfur ring designated in more recent Hterature as (3). The allotropes have different solubiUty in carbon disulfide. Stt and SX are soluble in carbon disulfide, whereas S]1 does not dissolve in this solvent. 

Sulfur crystallizes in at least two distinct systems the rhombic and the monoclinic forms. Rhombic sulfur, Sa, is stable at atmospheric pressures up to 95.5°C, at which transition to monoclinic sulfur, SP, takes place. Monoclinic sulfur is then stable up to its natural melting point of 114.5°C. The basic molecular unit of both of these crystalline forms of sulfur is the octatomic sulfur ring Other forms of sohd sulfur include hexatomic sulfur as well as... 

Many terms are used to describe the commercial forms of sulfur. The most common of these terms, along with brief descriptions and typical uses or references, are as follows. 

Other Uses. Other uses include intermediate chemical products. Overall, these uses account for 15—20% of sulfur consumption, largely in the form of sulfuric acid but also some elemental sulfur that is used directly, as in mbber vulcanization. Sulfur is also converted to sulfur trioxide and thiosulfate for use in improving the efficiency of electrostatic precipitators and limestone/lime wet flue-gas desulfurization systems at power stations (68). These miscellaneous uses, especially those involving sulfuric acid, are intimately associated with practically all elements of the industrial and chemical complexes worldwide. 

In addition to heavy hydrocarbons and water vapor, natural gas often contains other contaminants that may have to be removed. Carbon dioxide (CO2), hydrogen sulfide (H2S), and other sulfur compounds such as mercaptans are compounds that may require complete or partial removal for acceptance by a gas purchaser. These compounds are known as acid gases. H2S combined with water forms a weak form of sulfuric acid, while CO2 and water forms carbonic acid, thus the term acid gas. ... 

Figure 15.27 Structure of the monomeric, trimeric and chain-polymeric forms of sulfur trioxide.

The electron configuration in the valence orbitals of the sulfur atom (3s 3p4) suggests that it will form two covalent bonds by making use of two half-filled 3p orbitals. This is, in fact, observed in the molecule S8, which is present in the common forms of solid sulfur. The S8 molecules assume the form of a puckered ring, as shown in Figure 20-3. As with the phosphorus, the stability of this crystalline form of sulfur is due to van der Waals forces between discrete molecules. 

In Fig. 8.8, we see that sulfur can exist in any of four phases two solid phases (rhombic and monoclinic sulfur), one liquid phase, and one vapor phase. There are three triple points in the diagram, where various combinations of these phases, such as monoclinic solid, liquid, and vapor or monoclinic solid, rhombic solid, and liquid, coexist. However, four phases in mutual equilibrium (such as the vapor, liquid, and rhombic and monoclinic solid forms of sulfur, all in mutual equilibrium) in a one-component system has never been observed, and thermodynamics can be used to prove that such a quadruple point cannot exist. 

FIGURE 15.12 One of the two most common forms of sulfur is the blocklike rhombic form (a). It differs from the needlelike monoclinic sulfur tb) in the manner in which the S8 rings are stacked together. 

Elemental sulfur is a yellow, tasteless, almost odorless, insoluble, nonmetallic molecular solid of crownlike S8 rings (9). The two common crystal forms of sulfur are monoclinic sulfur and rhombic sulfur. The more stable form under normal conditions is rhombic sulfur, which forms beautiful yellow crystals (Fig. 15.12). At low temperatures, sulfur vapor consists mainly of S8 molecules. At temperatures above 720°C, the vapor has a blue tint from the S, molecules that form. The latter are paramagnetic, like O,. 

The most oxidized form of sulfur, S(+VI), is predominantly sulfate, SOl. Sulfate particles ranging in composition from pure sulfuric acid (H2SO4) to fully neutralized ammonium sulfate ((NH4)2S04) are ubiquitous constituents of the atmosphere (see Chapter 7). 

Finally, there is a major flux of sulfur through the atmosphere in both seasalt particles ( 140 Tg S/yr) and terrestrial dust ( 20 Tg S/ yr). In each case, the form of sulfur is sulfate, originating mostly as the mineral gypsum in the... 

As well as rejecting certain metal ions, oxidising equivalents in the form of sulfur (later oxygen) had to be rejected. 

Although use of radio and stable isotope labels involving the trio of covalently-bonded nitrogenous functions in 3 and in 78, provided evidence that isocyano is the precursor of the isothiocyano and formamido groups [30, 81], it remains to be shown that a biosynthetic equivalent of the in vitro chemically-proven fusion process between isocyano and free sulfur (e.g., cf. Introduction) exists in the cells of sponges. In marine biota, various ionic forms of sulfur in a number of oxidation states, as well as organo-polysulfides are known. However, any association with the isonitrile group and a sulfated species has yet to be established. 

The usual form of sulfur is known as the rhombic form, which is stable at temperatures up to about 105 °C. Above that temperature, the monoclinic structure is stable. A plastic form of sulfur can be obtained by pouring liquid sulfur into water to cool it quickly, but on standing it is converted to the rhombic form. On a molecular level, the element exists as S8 rings that have the structure... 

Hydrogen sulfide is a well known general metabolite produced on sulfate reduction by certain bacteria. Moreover, organic forms of sulfur can give rise to HS , hence H2S in certain bacteria. Thus, cysteine desulfhydrase (EC 4.4.1.1, cystathionine y-lyase) converts L-cysteine to H2S, pyruvate, and NH3. This enzyme shows a requirement for pyridoxal phosphate and the unstable ami-noacrylic acid is an intermediate (Equation 1) in the reaction ... 

A simplified series of reactions between a hafnium salt and sulfuric acid is given in Fig. 4.3. The reactions showcase important facets of thin-film synthesis (but do not address the precise identities of intermediates or complexities of aqueous hafnium chemistry.) In the first step, a hafnium oxide chloride crystal hydrate is dissolved in water to disperse small hafnium-hydroxo molecular clusters. Sulfato ligands are subsequently added in the form of sulfuric acid. Since sulfato binds more strongly than chloro, hafnium-hydroxo-sulfato aqueous species are created. Under mild heating, these species readily poly-... 

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