Metal sulfides, reactions

The main commercial methods of producing S02(g) are the direct combustion of sulfur, reaction (22.19), and the roasting of metal sulfides, reaction (22.20) ... 

Direct splitting requires temperatures above 977°C. Yields of around 30% at 1127°C are possible by equiUbrium. The use of catalysts to promote the reaction can lower the temperature to around the 327—727°C range. A number of transition metal sulfides and disulfides are being studied as potential catalysts (185). Thermal decomposition of H2S at 1130°C over a Pt—Co catalyst with about 25% H2 recovery has been studied. 

Roasting ofSulRdes. Most nonferrous metals occur in nature mainly as sulfides. These cannot be easily reduced directly to the metal. Burning metallic sulfides in air transforms them into oxides or sulfates which are more easily reduced. The sulfur is released as sulfur dioxide, as shown by the foHowing typical reaction for a divalent metal, M ... 

This reaction is strongly exothermic and proceeds spontaneously from left to right for most common metallic sulfides under normal roasting conditions, ie, in air, because P q + Pq = - 20 kPa (0.2 atm) at temperatures ranging from 650 to 1000°C. The physical chemistry of the roasting process is more complex than indicated by equation 3 alone. Sulfur trioxide is also formed,... 

This reaction is cataly2ed by silica, bauxite, and various metal sulfides. The usual catalyst is activated alumina, which also cataly2es the reduction by methane (228). Molybdenum compounds on alumina are especially effective catalysts for the hydrogen sulfide reaction (229). 

Metal Ion-Promoted Reactions of Thiols. Metal ion-promoted reactions of thiols have been reviewed (53). The bulk of the coverage concerns metal ion promoted aspects of sulfur chemistry. The main topics of interest are the formation of sulfenamides, sulfides, and disulfides using metal-mediated reactions. 

Other method thiosulfates have been prepared by reaction of suspensions of the metal sulfide with sulfur dioxide. However, these thiosulfates are... 

Lithium—Aluminum/Metal Sulfide Batteries. The use of high temperature lithium ceUs for electric vehicle appUcations has been under development since the 1970s. Advances in the development of lithium aUoy—metal sulfide batteries have led to the Li—Al/FeS system, where the foUowing ceU reaction occurs. 

Catalysis by Metal Sulfides. Metal sulfides such as M0S2, WS2, and many others catalyze numerous reactions that are catalyzed by metals (98). The metal sulfides are typically several orders of magnitude less active than the metals, but they have the unique advantage of not being poisoned by sulfur compounds. They are thus good catalysts for appHcations with sulfur-containing feeds, including many fossil fuels. 

Chlorination of OCT with chlorine at 90°C in the presence of L-type 2eohtes as catalyst reportedly gives a 56% yield of 2,5-dichlorotoluene (79). Pure 2,5-dichlorotoluene is also available from the Sandmeyer reaction on 2-amino-5-chlorotoluene. 3,4-Dichlorotoluene (l,2-dichloro-4-methylben2ene) is formed in up to 40% yield in the chlorination of PCT cataly2ed by metal sulfides or metal halide—sulfur compound cocatalyst systems (80). 

The synthetic pigment is produced by one of several related procedures. The best quahty product is made by reaction of an aqueous solution of CdSO or CdCl with a solution of an alkaline metal sulfide or H2S. Zn, Se, or Hg may be added to the CdS to produce shade vatiations. After precipitation, the color is filtered, washed, and calcined in an inert atmosphere at 500—600°C. 

Reactions of the various sulfides of arsenic call for little further comment. AS2S3 bums when heated in air to give AS2O3 and SO2. Chlorine converts it to ASCI3 and S2CI2. It is insoluble in water but dissolves readily in aqueous alkali or alkali-metal sulfide solutions to give thioarsenites ... 

As noted above, the roasting of most metal sulfides yields either the oxide or sulfate. However, a few metals can be obtained directly by oxidation of their sulfides, and these all have the characteristic property that their oxides are much less stable than SO2. Examples are Cu, Ag, Hg and the platinum metals. In addition, metallic Pb can be extracted by partial oxidation of galena to form a sulfate (the Scotch hearth or Newnham process, p. 370). The oversimplified reaction is ... 

Metal sulfides can be prepared in the laboratory or on an industrial scale by a number of reactions pure products are rarely obtained without considerable refinement and nonstoichiometric phases abound (p. 679). The more important preparative routes include ... 

In type A reaction soluble sulfide ions combine with metal ions to form a precipitate of insoluble metal sulfide. Sulfur s oxidation state of minus two does not change in this reaction. The reaction is... 

The ionization energy of the sulfur atom shows that it is even more reluctant than phosphorus to lose electrons. The common compounds of sulfur are the sulfides, which may be formed by reactions of elemental sulfur with a large number of metals. Typical reactions are... 

It is also often taken for granted that many of the Earth s subsystems are exposed to free oxygen (O2), leading to a range of one-way reactions of reduced materials (such as organic carbon or metal sulfides) to an oxidized form. As pointed out many times in earlier chapters, the oxidation-reduction status of the planet is the consequence of the dynamic interactions of biogeochemical cycles. As is the case with the acid-base balances, there is considerable sensitivity to perturbations of "redox" conditions, sometimes dramatically as in the case of bodies of water that suddenly become anaerobic because of eutrophication. Another extreme... 

Kolis et al. reported the synthesis of some metal sulfide salts of homolep-tic lanthanide ammine complexes using supercritical ammonia as a reaction medium (Scheme 12) [49]. They proposed that these reactions proceed via a... 

The preparation of some polychalcogenide solids can be achieved at 200-450 °C by molten salt (flux) methods. The reaction of tin with alkali metal sulfides in the presence of Ss at 200-450 °C gives a variety of alkali metal tin sulfides depending on the ratio of the starting materials, the reaction temperature, and the alkah metals (Scheme 30) [90]. These alkali metal tin sul-... 

To overcome some of the problems associated with aqueous media, non-aqueous systems with cadmium salt and elemental sulfur dissolved in solvents such as DMSO, DMF, and ethylene glycol have been used, following the method of Baranski and Fawcett [48-50], The study of CdS electrodeposition on Hg and Pt electrodes in DMSO solutions using cyclic voltammetry (at stationary electrodes) and pulse polarography (at dropping Hg electrodes) provided evidence that during deposition sulfur is chemisorbed at these electrodes and that formation of at least a monolayer of metal sulfide is probable. Formation of the initial layer of CdS involved reaction of Cd(II) ions with the chemisorbed sulfur or with a pre-existing layer of metal sulfide. 

In their pioneering work on the formation of photoelectrochemically active metal sulfides by oxidation of the parent metal electrode. Miller and Heller [29] reported the anodic formation of polycrystalline Bi2S3 on a bismuth metal electrode in a sodium polysulfide cell, wherein this electrode was used in situ as photoanode. When a Bi metal electrode is anodized in aqueous sulfide solutions a surface film is formed by the reaction... 

---