Binary sulfides

Ng H-J., Kalra H., Robinson D.B., Kubota H., "Equilibrium phase properties of the toluene-hydrogen sulfide and n-heptane-hydrogen sulfide binary systems", J. Chem. Eng. Data.. 1980, 25, 51-55. 

From this literature survey it appears that despite the appearance of a relatively large number of papers concerning chemical bath deposition, most are focused on a few materials, especially sulfide binaries such as PbS, CdS, which are used for applications. If we exclude these materials, in fact the work on other compounds is often limited to a few papers, or appears in screening studies. There is a trend towards the elaboration of ternary compounds by CBD, but the competition between the formation of the binaries represent a major difficulty. It seems that the composition of the solution, especially the nature of the complexing agents used plays a role. A general... 

The (peroxo)di-iron(III) species (38b) and (38b ) " effect enantioselective sulfoxidation of aryl sulfides. In the catalytic reaction with FI2O2 as a terminal oxidant, saturation kinetics were observed with respect to both [FI2O2] and [sulfide]. The peroxo species (38b) + (38b ) generated in situ at 0°C decays in the presence of sulfide, following a saturation kinetics with respect to [sulfide]. For p-bromophenyl methyl sulfide, the ee approaches ca. 40%, providing compelling evidence for a metal-based oxidation pathway involving a (peroxo)di-iron(III)-sulfide binary complex embedded within chiral environment. 

Leu, A.-D. Carroll, J. J. Robinson, D. B. The equilibrium phase properties of the methanol-hydrogen sulfide binary system. Fluid Phase Equilib. 1992, 72, 163-172. 

Carroll, J.J., Mather, A.E. 1995. A generalized correlation for the Peng-Robinson interaction coefficients for paraffin-hydrogen sulfide binary systems. Fluid Phase Equilib. 105(2) 221-228. 

Isoprene [78-79-5] (2-methyl-1,3-butadiene) is a colorless, volatile Hquid that is soluble in most hydrocarbons but is practically insoluble in water. Isoprene forms binary azeotropes with water, methanol, methylamine, acetonitrile, methyl formate, bromoethane, ethyl alcohol, methyl sulfide, acetone, propylene oxide, ethyl formate, isopropyl nitrate, methyla1 (dimethoxymethane), ethyl ether, and / -pentane. Ternary azeotropes form with water—acetone, water—acetonitrile, and methyl formate—ethyl bromide (8). Typical properties of isoprene are Hsted in Table 1. 

Binary Compounds. The fluorides of indium are IrF [23370-59-4] IrF [37501-24-9] the tetrameric pentafluoride (IiF ) [14568-19-5], and JIrFg [7789-75-7]. Chlorides of indium include IrCl, which exists in anhydrous [10025-83-9] a- and p-forms, and as a soluble hydrate [14996-61-3], and IrCl [10025-97-5], Other haUdes include IrBr [10049-24-8], which is insoluble, and the soluble tetrahydrate IrBr -4H20 IrBr [7789-64-2]-, and Irl [7790-41-2], Iridium forms indium dioxide [12030-49-8], a poorly characteri2ed sesquioxide, 11203 [1312-46-5]-, and the hydroxides, Ir(OH)3 [54968-01-3] and Ir(OH) [25141-14-4], Other binary iridium compounds include the sulfides, IrS [12136-40-2], F2S3 [12136-42-4], IrS2 [12030-51 -2], and IrS3 [12030-52-3], as well as various selenides and teUurides. 

Treatment of the primary product with a zinc salt leads to separation of a-CySj from its coproduct CSj, and multigram amounts of its complexes [NR4]2 [20(0-0385)2] and of the eorresponding -isomer s eomplexes afford convenient starting points for the synthesis of molecular binary sulfides as indicated below. 

P4S4 is one of the most recent binary sulfides to be isolated and characterized and it exists in two structurally distinct forms.Each can be made in quantitative yield by reacting the appropriate isomer of P4S3I2 (p. 503) with [(Me3Sn)2S] in CS2 solution ... 

Transition elements, for which variable valency is energetically feasible, frequently show non-stoichiometric behaviour (variable composition) in their oxides, sulfides and related binary compounds. For small deviations from stoichiometry a thermodynamic approach is instructive, but for larger deviations structural considerations supervene, and the possibility of thermodynamically unstable but kinetically isolable phases must be considered. These ideas will be expanded in the following paragraphs but more detailed treatment must be sought elsewhere. " ... 

All three metals form a wide variety of binary chalcogenides which frequently differ both in stoichiometry and in structure from the oxides. Many have complex structures which are not easily described, and detailed discussion is therefore inappropriate. The various sulfide phases are listed in Table 22.4 phases approximating to the stoichiometry MS have the NiAs-type structure (p. 556) whereas MS2 have layer lattices related to M0S2 (p. 1018), Cdl2, or CdCl2 (p. 1212). Sometimes complex layer-sequences occur in which the 6-coordinate metal atom is alternatively octahedral and trigonal prismatic. Most of the phases exhibit... 

Beta radiation Electron emission from unstable nuclei, 26,30,528 Binary molecular compound, 41-42,190 Binding energy Energy equivalent of the mass defect measure of nuclear stability, 522,523 Bismuth (m) sulfide, 540 Blassie, Michael, 629 Blind staggers, 574 Blister copper, 539 Blood alcohol concentrations, 43t Body-centered cubic cell (BCC) A cubic unit cell with an atom at each comer and one at the center, 246 Bohrmodd Model of the hydrogen atom... 

It is also shown that theoretically a binary compound should have the sphalerite or wurzite structure instead of the sodium chloride structure if the radius ratio is less than 0.33. The oxide, sulfide, selenide and telluride of beryllium conform to this requirement, and are to be considered as ionic crystals. It is found, however, that such tetrahedral crystals are particularly apt to show deformation, and it is suggested that this is a tendency of the anion to share an electron pair with each cation. 

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. 

Despite the tremendous amount of work on the binary compounds, copper chalcogenide halides were first reported in 1969 (304). Nine compounds of selenium and tellurium have been found, and they are listed in Table 1. Copper sulfide halides are still unknown. 

Treatment of the rhenium sulfide chlorides with an excess of chlorine at temperatures above 450°C results in formation of ReCls 140). Reduction between 350 and 500°C gives binary rhenium chalcogenides 139,262). Action of water vapor on rhenium sulfide chlorides at 350-500°C produces oxysulfides 139). 

The structural chemistry of the actinides is often similar to that of lighter transition metals, such as Zr and Hf, and to that of the lanthanides however, the diffuse nature of the 5/ orbitals leads to some differences and specifically to interesting magnetic and electrical properties. The actinide sulfides are generally isostructural with the selenides, but not with the analogous tellurides. The binary chalcogenides of uranium and thorium have been discussed in detail [66], but the structural... 

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