Sulfides, of Group

By contrast with the water-soluble sulfides of Groups 1 and 2, the corresponding heavy metal sulfides of Groups 11 and 12 are amongst the least-soluble compounds known. Literature values are often wildly discordant, and care should be taken in interpreting the data. Thus, for black HgS the most acceptable value of the solubility product [Hg +][S ] is 10- mol2l-2, i.e. 

All of the Group IA and IIA metals form sulfides, some of which are used rather extensively. The sulfides of Group IIA metals consist of M2+ and S2 ions arranged in the sodium chloride type lattice (see Chapter 3). The compounds of the Group IA metals consist of M+ and S2, but as a result of there being twice as many cations as anions, the structure is of the antifluorite type (see Chapter 3). The sulfide ion is a base so there is extensive hydrolysis in solutions of the sulfides, and the solutions are basic ... 

Hi) To heterogeneous catalysis sulfides of group S(a) often show catalytic activity which may be strongly enhanced in the presence of metal centers of group B elements (c/. the important hydrodesulfurization reactions utilizing Co—Mo—S catalysts). The catalytic activity may be discussed in terms of the different electron densities at the metal centers and the sulfur atoms attached to them. 

Sulfides, S " Sulfides of group 1A alkah metals and of ammonium are soluble sulfides of group 2 A, MgS, CaS, and BaS, are sparingly soluble... 

The equilibrium is more favorable to acetone at higher temperatures. At 325°C 97% conversion is theoretically possible. The kinetics of the reaction has been studied (23). A large number of catalysts have been investigated, including copper, silver, platinum, and palladium metals, as well as sulfides of transition metals of groups 4, 5, and 6 of the periodic table. These catalysts are made with inert supports and are used at 400—600°C (24). Lower temperature reactions (315—482°C) have been successhiUy conducted using 2inc oxide-zirconium oxide combinations (25), and combinations of copper-chromium oxide and of copper and silicon dioxide (26). 

Certain base adducts of borane, such as triethylamine borane [1722-26-5] (C2H )2N BH, dimethyl sulfide borane [13292-87-OJ, (CH2)2S BH, and tetrahydrofuran borane [14044-65-6] C HgO BH, are more easily and safely handled than B2H and are commercially available. These compounds find wide use as reducing agents and in hydroboration reactions (57). A wide variety of borane reducing agents and hydroborating agents is available from Aldrich Chemical Co., Milwaukee, Wisconsin. Base displacement reactions can be used to convert one adduct to another. The relative stabiUties of BH adducts as a function of Group 15 and 16 donor atoms are P > N and S > O. This order has sparked controversy because the trend opposes the normal order estabUshed by BF. In the case of anionic nucleophiles, base displacement leads to ionic hydroborate adducts (eqs. 20,21). 

Figure 13.17 Molecular structure of some sulfides of arsenic, stressing the relationship to the AS4 tetrahedron (point group symmetry in parentheses).

Group III sulfides are much more difficult to precipitate than those of Group II. Compare, for example, the equilibrium constant for the reaction... 

The C-S bond of the sulfide end groups can be relatively weak and susceptible to thermal and photo- or radical-induced homolysis. This means that certain disulfides [for example 7-9] may act as iniferters in living radical polymerization and they can be used as precursors to block copolymers (Sections 7.5.1 and 9.3.2). 

The chalcogenides are binary compounds of a chalcogen (i.e., the elements of Group Ilb zinc, cadmium, mercury) with a less electropositive element, such as those of Group VIb (oxygen, sulfur, selenium, and tellurium). This section covers the sulfides, selenides, andtellurides. Oxides are reviewed above in Ch. 11. Most of the chalcogenides have useful optical characteristics and their applications are usually found in optics. 

Very little is known about chalcogenide halides of Group IVB elements. Although the existence of sulfide chlorides (45, 274, 329, 365) and of a selenide chloride (329) of titanium was claimed in early publications, their true composition, and even their existence, remains doubtful. They have usually been obtained by the reaction of titanium chlorides with sulfur and selenium, respectively, or with hydrogen sulfide. The synthesis of a pure compound, TiSClj, was published in 1959 (113). It is an intermediate of the reaction of TiCU with HjS. 

A few of the transition metals, including gold, platinum, and iridium, are found in nature as pure elements, but most of the others are found associated with either sulfur or oxygen. Iron, manganese, and the metals of Groups 3 to 6 (except for Mo) are most often found as oxides less often, they occur as sulfates or carbonates. Molybdenum and the metals of Groups 7 to 12 (e.xcept forMn and Fe) are most often found as sulfides. 

Gillespie RJ, Passmore J (1971) Polycations of Group VI. Acc Chem Res 4 413 19 Giggenbach WF (1974) Equilibria involving polysulfide ions in aqueous sulfide solutions up to 240 °C. Inorg Chem 13 1724-1730... 

In the previous paragraph, it has been stated that minerals have the same structure but different compositions (phenomenon of isomorphism of minerals) while some minerals have the same composition but different structures (phenomenon of polymorphism of minerals). Mineral composition and structure are both important in studying and classifying minerals. The major class of minerals - based on composition and structure - include elements, sulfides, halides, carbonates, sulfates, oxides, phosphates, and silicates. The silicate class is especially important, because silicon makes up 95% of the minerals, by volume, in the Earth s crust. Mineral classes are divided into families on the basis of the chemicals in each mineral. Families, in turn, are made of groups of minerals that have a similar structure. Groups are further divided into species. 

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