Oxides sulfides

Surface heterogeneity may be inferred from emission studies such as those studies by de Schrijver and co-workers on P and on R adsorbed on clay minerals [197,198]. In the case of adsorbed pyrene and its derivatives, there is considerable evidence for surface mobility (on clays, metal oxides, sulfides), as from the work of Thomas [199], de Mayo and co-workers [200], Singer [201] and Stahlberg et al. [202]. There has also been evidence for ground-state bimolecular association of adsorbed pyrene [66,203]. The sensitivity of pyrene to the polarity of its environment allows its use as a probe of surface polarity [204,205]. Pyrene or ofter emitters may be used as probes to study the structure of an adsorbate film, as in the case of Triton X-100 on silica [206], sodium dodecyl sulfate at the alumina surface [207] and hexadecyltrimethylammonium chloride adsorbed onto silver electrodes from water and dimethylformamide [208]. In all cases progressive structural changes were concluded to occur with increasing surfactant adsorption. 

In addition to the collector, polyvalent ions may show sufficiently strong adsorption on oxide, sulfide, and other minerals to act as potential-determining ions (see Ref. 98). Judicious addition of various salts, then, as well as pH control, can permit a considerable amount of selectivity. 

When the desired product is a sulfoxide sodium metaperiodate (NaI04) is an ideal reagent It oxidizes sulfides to sulfoxides m high yield but shows no tendency to oxidize sulfoxides to sulfones... 

The chlorides, bromides, nitrates, bromates, and perchlorate salts ate soluble in water and, when the aqueous solutions evaporate, precipitate as hydrated crystalline salts. The acetates, iodates, and iodides ate somewhat less soluble. The sulfates ate sparingly soluble and ate unique in that they have a negative solubitity trend with increasing temperature. The oxides, sulfides, fluorides, carbonates, oxalates, and phosphates ate insoluble in water. The oxalate, which is important in the recovery of lanthanides from solutions, can be calcined directly to the oxide. This procedure is used both in analytical and industrial apptications. 

The predominant process for manufacture of aniline is the catalytic reduction of nitroben2ene [98-95-3] ixh. hydrogen. The reduction is carried out in the vapor phase (50—55) or Hquid phase (56—60). A fixed-bed reactor is commonly used for the vapor-phase process and the reactor is operated under pressure. A number of catalysts have been cited and include copper, copper on siHca, copper oxide, sulfides of nickel, molybdenum, tungsten, and palladium—vanadium on alumina or Htbium—aluminum spinels. Catalysts cited for the Hquid-phase processes include nickel, copper or cobalt supported on a suitable inert carrier, and palladium or platinum or their mixtures supported on carbon. 

Zinc compounds are generally colorless unless the other component, eg, chromate, is colored. The lack of color of most zinc compounds in visible light is a great advantage in that they do not color paint films, plastics, mbber, cosmetics, etc. However, when excited by various types of radiation and at various temperatures, zinc oxide, sulfide, selenide [1315-09-9], and related compounds exhibit luminescence, ie, they emit colored light (see Luminescent materials). Zinc-based phosphors can be produced in many colors, depending upon the added dopants. They are used in television tubes, luminescent glasses, and various specialty products. 

Cadmium Fluoride. Elemental fluorine reacts with cadmium metal as well as the oxide, sulfide, and chloride to give CdF2 [7790-79-6]. Alternatively, treatment of CdCO with 40% HF yields a solution of CdF2, which may be evaporated to recover efflorescent crystals of the dihydrate. CdF2 has been used in phosphors, glass manufacture, nuclear reactor controls, and electric bmshes and in 1991 sold as a pure electronic grade (99.99%) at l/g. 

Cadmium Bromide. The hydrated bromide is prepared by dissolution of cadmium carbonate, oxide, sulfide, or hydroxide in hydrobromic acid. The white crystalline material is cadmium bromide tetrahydrate [13464-92-1], CdBr2 4H2O, Ai/ 29s —1492.55 kJ/mol (—356.73 kcal/mol) (3)... 

Hydrometallurigcal Processes. In hydrometaHurgical processes, metal values and by-products are recovered from aqueous solution by chemical or electrolytic processes. Values are solubilized by treating waste, ore, or concentrates. Leaching of copper ores in place by rain or natural streams and the subsequent recovery of copper from mnoff mine water as impure cement copper have been practiced since Roman times. Most hydrometaHurgical treatments have been appHed to ores or overburden in which the copper was present as oxide, mixed oxide—sulfide, or native copper. PyrometaHurgical and hydrometaHurgical processes are compared in Reference 34. 

L oss of Catalyst by Vapor Transport. The direct volatilisation of catalytic metals is generally not a factor in catalytic processes, but catalytic metal can be lost through formation of metal carbonyl oxides, sulfides, and hahdes in environments containing CO, NO, O2 and H2S, and halogens (24). 

Metal oxides, sulfides, and hydrides form a transition between acid/base and metal catalysts. They catalyze hydrogenation/dehydro-genation as well as many of the reactions catalyzed by acids, such as cracking and isomerization. Their oxidation activity is related to the possibility of two valence states which allow oxygen to be released and reabsorbed alternately. Common examples are oxides of cobalt, iron, zinc, and chromium and hydrides of precious metals that can release hydrogen readily. Sulfide catalysts are more resistant than metals to the formation of coke deposits and to poisoning by sulfur compounds their main application is in hydrodesulfurization. 

Thiobacillus thiooxidans is an aerobic organism that oxidizes various sulfur-containing compounds to form sulfuric acid. These bacteria are sometimes found near the tops of tubercles (see Chap. 3, Tubercu-lation ). There is a symbiotic relationship between Thiobacillus and sulfate reducers Thiobacillus oxidizes sulfide to sulfate, whereas the sulfate reducers convert sulfide to sulfate. It is unclear to what extent Thiobacillus directly influences corrosion processes inside tubercles. It is more likely that they indirectly increase corrosion by accelerating sulfate-reducer activity deep in the tubercles. 

Since sulfides tend to react with electrophiles, a method for protection could be quite useful. Sulfoxides can be used to protect sulfides and are easily formed by a variety of oxidants. Sulfides can be regenerated with thiols, SiC (0°, 15 min, TFA, anisole), LiBH4/Me3SiCl, DMF-S03/HSCH2CH2SH (DMF, Pyr, rt, 85% yield). 

Phosphorus oxides, sulfides, selenides and related compounds... 

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. " ... 

The processes by which metals are extracted from their ores fall within the science of metallurgy. As you might expect, the chemical reactions involved depend on the type of ore (Figure 20.2, p. 536). We consider some typical processes used to obtain metals from chloride, oxide, sulfide, or native ores. 

This element occurs in nature in the uncombined state as native copper and in the combined state as various oxides, sulfides, and carbonates. The chief mineral is chalcopyrite, CuFeS2, from which the element is extracted by roasting (heating in air) followed by reduction. The roasting reaction can be written... 

Purified mammalian- and bacterial-derived enzymes were used by Oae, Walsh and their coworkers to oxidize sulfides to sulfoxides. The emphasis in these studies was on the characteristics of the enzymes rather than on the use of the enzymes to prepare homochiral sulfoxides. 

The Alkaline-Earth Oxides, etc.—The observed and calculated inter-atomic distances for the alkaline-earth oxides, sulfides, selenides and tellurides are given in Table VIII. Except for the magnesium com-... 

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