Sulfides production of metal

KOL] Kolthoff, I. M., The solubilities and solubility products of metallic sulfides in water, J. Phys. Chem., 35, (1931), 2711-2721. Cited on pages 180,263. 

Hexamethyldisilthiane or bis(trimethylsilyl)sulfide, (Me3Si)2S, is a colourless, moisture-sensitive, flammable liquid (b.p. 160 °C) with a strong stench, ft was first prepared from trimethylsilyl chloride and silver sulfide by Eaborn in 1950 but cheaper, more convenient syntheses facilitated its commercial production. The compound has many applications in organic synthesis, e.g. reduction, sulfuration and silylation reactions and in the production of metal sulfide-based electronic devices, semiconductors, nanoparticles and quantum dots. ... 

Arsenic is another element with different bioavailabiUty in its different redox states. Arsenic is not known to be an essential nutrient for eukaryotes, but arsenate (As(V)) and arsenite (As(III)) are toxic, with the latter being rather more so, at least to mammals. Nevertheless, some microorganisms grow at the expense of reducing arsenate to arsenite (81), while others are able to reduce these species to more reduced forms. In this case it is known that the element can be immobilized as an insoluble polymetallic sulfide by sulfate reducing bacteria, presumably adventitiously due to the production of hydrogen sulfide (82). Indeed many contaminant metal and metalloid ions can be immobilized as metal sulfides by sulfate reducing bacteria. 

Corrosion products and deposits. All sulfate reducers produce metal sulfides as corrosion products. Sulfide usually lines pits or is entrapped in material just above the pit surface. When freshly corroded surfaces are exposed to hydrochloric acid, the rotten-egg odor of hydrogen sulfide is easily detected. Rapid, spontaneous decomposition of metal sulfides occurs after sample removal, as water vapor in the air adsorbs onto metal surfaces and reacts with the metal sulfide. The metal sulfides are slowly converted to hydrogen sulfide gas, eventually removing all traces of sulfide (Fig. 6.11). Therefore, only freshly corroded surfaces contain appreciable sulfide. More sensitive spot tests using sodium azide are often successful at detecting metal sulfides at very low concentrations on surfaces. 

Many of the most important naturally occurring minerals and ores of the metallic elements are sulfides (p. 648), and the recovery of metals from these ores is of major importance. Other metal sulfides, though they do not occur in nature, can be synthesized by a variety of preparative methods, and many have important physical or chemical properties which have led to their industrial production. Again, the solubility relations of metal sulfides in aqueous solution form the basis of the most widely used scheme of elementary qualitative analysis. These various more general considerations will be briefly discussed before the systematic structural chemistry of metal sulfides is summarized. 

Sulfur for commercial purposes is derived mainly from native elemental sulfur mined by the Frasch process. Large quantities of sulfur are also recovered from the roasting of metal sulfides and the refining of crude oil, i.e., from the sulfur by-products of purified sour natural gas and petroleum (the designation sour is generally associated with high-sulfur petroleum products). Reserves of elemental sulfur in evaporite and volcanic deposits and of sulfur associated with natural gas,... 

Important results and a detailed insight into aqueous chemical deposition processes have been reported and discussed elsewhere for CdSe [248, 249] and ZnS [250, 251] target products. We should note also the work of Davies et al. [252] who described an alternative method for the chemical growth of metal sulfides and selenides on the basis of polysulfide or polyselenide solutions (containing hexa- and tetra-chalcogen anions) formed by the dissolution of sulfur or selenium in hydrazine monohydrate. ... 

The solubility product (JCsp) for the precipitation of metal sulfide (MmSn) from a solution containing m Mz+ and n S2 ions is... 

A catalytic example of C-S bond breakage in benzothiophene has been reported by Bianchini [47], A catalytic desulfurisation was not yet achieved at the time as this is thermodynamically not feasible at such mild temperatures because of the relative stability of metal sulfides formed. Bianchini used a water-soluble catalyst in a two-phase system of heptane-methanol/water mixtures in which the product 2-ethylthiophenol is extracted into the basic aqueous layer containing NaOH. Figure 2.43 gives the reaction scheme and the catalyst. The 16-electron species Na(sulfos)RhH is suggested to be the catalyst. Note that a hydrodesulfurisation has not yet been achieved in this reaction because a thiol is the product. Under more forcing conditions the formation of H2S has been observed for various systems. 

The most important applications of hydrogen sulfide involve the production of sodium sulfide and other inorganic sulfides. Hydrogen sulfide obtained as a by-product often is converted into sulfuric acid. It also is used in organic synthesis to make thiols or mercaptans. Other applications are in metallurgy for extracting nickel, copper, and cobalt as sulfides from their minerals and in classical qualitative analytical methods for precipitation of many metals (see Reactions). It also is used in producing heavy water for nuclear reactors. 

It is no wonder that the particles are spherical but crystalline, if one considers the formation mechanism. The rather smooth surface of the spherical magnetite may be due to the rapid contact recrystallization of the constituent primary particles (5), forming the rigid polycrystalline structure. Flowever, it must be noted that polycrystalline spheres are also prepared by normal deposition of monomeric solute, as shown in the formation of the uniform spherical polycrystalline particles of metal sulfides in Chapters 3.1-3.3. Thus, while we may be able to predict the final particle shape and structure from the formation mechanism, it is risky to conclude the formation mechanism only from characterization of the product. As a rule, scrupulous analyses are needed for concluding the growth mechanism in a particle system. 

Other metal complexes such as 2,2 -bipyridine complexes of Rh and Ir are efficient electrocatalysts for the reduction of C02 in acetonitrile.134 In the production of formate the current efficiency is up to 80%. Electrochemical reduction catalyzed by mono- and dinuclear Rh complexes affords formic acid in aqueous acetonitrile, or oxalate in the absence of water.135 The latter reaction, that is, the reduction of C02 directed toward C-C bond formation, has attracted great interest.131 An exceptional example136 is the use of metal-sulfide clusters of Ir and Co to catalyze selectively the electrochemical reduction of C02 to oxalate without the accompanying disproportionation to CO and CO2-. 

In the presence of hydrogen sulfide produced by anaerobic bacterial activity, particularly sulfate reducers, conditions are created whereby sulfides of copper and zinc could be formed. The partition of these metals between the sulfide phase and the organic phase depends on the relation between the stability constants of the complexes and the solubility product of the sulfides of these metals. Elements with small solubility products of their sulfides and low stability constants of their chelates would be expected to go into the sulfide phase when hydrogen sulfide is present. Copper is typical of such elements. Chalcocite has a solubility product of about 10" ° and covellite about 10"44, whereas the most stable chelates of copper have stability constants of about 10" Consequently, copper could be expected to be accumulated as the sulfide. Zinc sulfide has a much larger solubility product however, the stability of its chelates is lower. From the fact that zinc appears to be completely associated with the inorganic fraction of coal, it can be assumed that the relation between the solubility product of any of its sulfides and its chelates favors formation of the sulfide. Iron could be expected to follow a similar pattern. 

Ferrous iron in this reaction can be replaced by any of the metal ions freed in the oxic reactions to form a number of metal sulfides. This system is highly dependent on the availability of sulfate. When sulfate is exhausted by precipitating metal sulfides, processes move into the anoxic methanic state (13, 27). Methane production is strongly bacterially mediated following a general reaction similar to eq 9 (21, 28). 

When solutions of soluble ionic compounds are mixed, an insoluble compound will precipitate if the ion product (IP) for the insoluble compound exceeds its fCsp. The IP is defined in the same way as /equilibrium concentrations. Certain metal cations can be separated by selective precipitation of metal sulfides. Selective precipitation is important in qualitative analysis, a procedure for identifying the ions present in an unknown solution. 

The solubility product for CuS is very low ( sp = 10 19 as written) so that the presence of sulfide in water acts to immobilize Cu (and many other metals) and reduce effective exposure. The formation of metal sulfides is important in anaerobic soil and sediment, stagnant ponds and basins, and many industrial and domestic sewage treatment plants and discharges. Co-precipitation of metals also can be a very important removal process in natural waters. In aerobic systems, the precipitation of hydrous... 

Oxidative dissolution of metal-sulfides (e.g., pyrite, FeS2) is a complex process involving surface adsorption of the oxidant (Fe3+, 02), surface electron transfer, and surface product formation and detachment. The overall oxidation process, without considering the detailed mechanisms, is demonstrated below using pyrite (FeS2) (Evangelou, 1995b) ... 

Reductive Precipitation. Reductive precipitation involves the production of reduced species with limited solubility. An example of reductive precipitation in the environment involves the reduction of S04 to H2S and the precipitation of metals as metal-sulfides. In nature, the process of reductive precipitation is mostly microbiologically controlled. Production of H2S is the rate-controlling reaction of metal-sulfide precipitate formation. 

A catalyst is usually requires in the formation of H2S. Metal sulfides are the most common catalysts used in the laboratory or in large-scale production of H2S. The catalytic activity of metal sulfides is linked to the metal-sulfur bond strength. 

A third type of metal sulfide nanoparticle stabilized by GSH is Ag2S. Ag2S nanoparticle synthesis is challenging particularly in aqueous media due to the tendency to form bulk material rather than discrete nanoparticles. Mehra et al. have developed a standard synthesis for efficient production of this material. In this synthesis, silver ions are reacted with GSH to form a Ag(I)-(GSH) complex (where n is undetermined) and after sufficient reaction time, the inorganic sulfide is added to the solution in stoichiometric amounts to... 

Virion templates of TMV were also used in combination with different synthetic routes for CdS, PbS, and Fe oxide nanoparticles. Nanoparticle-virion tubules were prepared by reacting a buffered solution of TMV in CdCl2 (pH 7) or TMV in Pb(N03)2 (pH 5) with H2S gas. The formation of metal sulfide nanoparticles occurred over 6 hours as observed by a uniform coating of CdS and PbS nanocrystals on the TMV surface from TEM analysis. Selected area electron diffraction of the mineralized products indicated a zinc blende crystal stracture for CdS particles and a rock salt structure for single domain PbS nanocrystals. The iron oxide nanoparticles were mineralized by the TMV templates by the oxidative hydrolysis of an Fe VFe acidic solution with NaOH. Consequently, a mineral coating of irregular ferrihydrite particles grew on the surface to a thickness of 2 nm. 

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