Pyrite elements

Earlier work on the isotopic compositions of pyrite, elemental sulfur, and organic sulfur in coals from Japan, Australia, and Germany (107-110) was summarized by Nielsen (102). Smith and Batts (110) showed that organic sulfur in Australian coals ranging in age from Permian to Tertiary has a large isotopic variation (+2.9 to +24%c) in coals with more than % sulfur, whereas organic sulfur in low-sulfur coals (less than 1% sulfur) has a narrow isotopic composition between +4.6 and +7.3%o. The relatively uniform isotopic... 

Each of these elements occurs naturally as a sulphide ore arsenic as realgar As S,, orpiment As, Sg and arsenical pyrites with approximate formula FeAsS antimony as stibnite Sb2S3 and bismuth as B12S3. 

Many of these sulphides occur naturally, for example iron(ll) sulphide, FeS (magnetic pyrites), and antimony(III) sulphide, Sb S, (stibnite). They can usually be prepared by the direct combination of the elements, effected by heating, but this rarely produces a pure stoichiometric compound and the product often contains a slight excess of the metal, or of sulphur. 

After aluminium, iron is the most abundant metal and the fourth most abundant of all the elements it occurs chiefly as oxides (for example haematite (FCjO,), magnetite (lodestonej (FC3O4) and as iron pyrites FeSj- Free iron is found in meteorites, and it is probable that primitive man used this source of iron for tools and weapons. The extraction of iron began several thousand years ago, and it is still the most important metal in everyday life because of its abundance and cheapness, and its ability to be cast, drawn and forged for a variety of uses. 

Total 1991 world production of sulfur in all forms was 55.6 x 10 t. The largest proportion of this production (41.7%) was obtained by removal of sulfur compounds from petroleum and natural gas (see Sulfurremoval and recovery). Deep mining of elemental sulfur deposits by the Frasch hot water process accounted for 16.9% of world production mining of elemental deposits by other methods accounted for 5.0%. Sulfur was also produced by roasting iron pyrites (17.6%) and as a by-product of the smelting of nonferrous ores (14.0%). The remaining 4.8% was produced from unspecified sources. 

World resources of sulfur have been summarized (110,111). Sources, ie, elemental deposits, natural gas, petroleum, pyrites, and nonferrous sulfides are expected to last only to the end of the twenty-first century at the world consumption rate of 55.6 x 10 t/yr of the 1990s. However, vast additional resources of sulfur, in the form of gypsum, could provide much further extension but would require high energy consumption for processing. 

Sulfur constitutes about 0.052 wt % of the earth s cmst. The forms in which it is ordinarily found include elemental or native sulfur in unconsohdated volcanic rocks, in anhydrite over salt-dome stmctures, and in bedded anhydrite or gypsum evaporate basin formations combined sulfur in metal sulfide ores and mineral sulfates hydrogen sulfide in natural gas organic sulfur compounds in petroleum and tar sands and a combination of both pyritic and organic sulfur compounds in coal (qv). 

Noranda Process. When pyrites are heated to about 540°C in the absence of oxygen, about half of the sulfur content in the pyrites evolves in the elemental form. Noranda Mines Ltd. and BatteUe Memorial Institute developed a process based on this property to recover elemental sulfur from pyrite (27). The first commercial plant was built at Welland, Ontario, in 1954 but operated on an experimental basis for only a few years before being closed for economic reasons. 

At the beginning of the twentieth century, the world s sulfur demand of about two million metric tons was met by sulfur produced from elemental deposits in Sicily, Italy, and from pyrite mined on the Iberian Peninsula. By 1995, sulfur was recovered in more than 78 countries. 

The principal direct raw materials used to make sulfuric acid are elemental sulfur, spent (contaminated and diluted) sulfuric acid, and hydrogen sulfide. Elemental sulfur is by far the most widely used. In the past, iron pyrites or related compounds were often used but as of the mid-1990s this type of raw material is not common except in southern Africa, China, Ka2akhstan, Spain, Russia, and Ukraine (96). A large amount of sulfuric acid is also produced as a by-product of nonferrous metal smelting, ie, roasting sulfide ores of copper, lead, molybdenum, nickel, 2inc, or others. 

The pyritic sulfur in coal can undergo reaction with sulfate solutions to release elemental sulfur (see Sulfurremoval and recovery). Processes to reduce the sulfur content of coal have been sought (75). The reaction of coal and sulfuric acid has been used to produce cation exchangers, but it was not very efficient and is no longer employed. Efforts have turned to the use of hot concentrated alkaH in a process called Gravimelt. 

The pyrites and marcasite structures can be thought of as containing 82 units though the variability of the interatomic distance and other properties suggest substantial deviation from a purely ionic description. Numerous higher polysulfides S have been characterized, particularly for the more electropositive elements Na, K, Ba, etc. They are yellow at room temperature, turn dark red on being heated, and may be thought of as salts of the polysulfanes... 

Selenium was isolated some 35 y after tellurium and, since the new element resembled tellurium, it was named from the Greek askrivr], selene, the moon. The discovery was made in 1817 by the Swedish chemist J. J. Berzelius (discoverer of Si, Ce and Th) and J. G. Gahn (discoverer of Mn) they observed a reddish-brown deposit during the burning of sulfur obtained from Fahlun copper pyrites, and showed it to be volatile and readily reducible to the new element. 

Ruthenium and osmium form only disulfides. These have the pyrite structure and are diamagnetic semiconductors this implies that they contain M . RuSc2, RuTc2, OsSc2 and OsTc2 are very similar. All 6 dichalcogenides are obtained directly from the elements. 

Sulfur is widely distributed as sulfide ores, which include galena, PbS cinnabar, HgS iron pyrite, FeS, and sphalerite, ZnS (Fig. 15.11). Because these ores are so common, sulfur is a by-product of the extraction of a number of metals, especially copper. Sulfur is also found as deposits of the native element (called brimstone), which are formed by bacterial action on H,S. The low melting point of sulfur (115°C) is utilized in the Frasch process, in which superheated water is used to melt solid sulfur underground and compressed air pushes the resulting slurry to the surface. Sulfur is also commonly found in petroleum, and extracting it chemically has been made inexpensive and safe by the use of heterogeneous catalysts, particularly zeolites (see Section 13.14). One method used to remove sulfur in the form of H2S from petroleum and natural gas is the Claus process, in which some of the H2S is first oxidized to sulfur dioxide ... 

Iron, Fe, the most widely used of all the d-metals, is the most abundant element on Earth and the second most abundant metal in the Earth s crust (after aluminum). Its principal ores are the oxides hematite, Fe203, and magnetite, Fc C)4. The sulfide mineral pyrite, FeS2 (see Fig. 15.11), is widely available, but it is not used in steelmaking because the sulfur is difficult to remove. 

The magnetic criterion is particularly valuable because it provides a basis for differentiating sharply between essentially ionic and essentially electron-pair bonds Experimental data have as yet been obtained for only a few of the interesting compounds, but these indicate that oxides and fluorides of most metals are ionic. Electron-pair bonds are formed by most of the transition elements with sulfur, selenium, tellurium, phosphorus, arsenic and antimony, as in the sulfide minerals (pyrite, molybdenite, skutterudite, etc.). The halogens other than fluorine form electron-pair bonds with metals of the palladium and platinum groups and sometimes, but not always, with iron-group metals. 

Chalcopyrite or copper pyrite, CuFeS2, is one of the major ores of copper, estimated to account for about 50% of all the element s deposits. Compounds of the chalcopyrite type of the general formula ABC2 (with A = Cu, Ag B = Al, Ga, In ... 

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