Iron as oxidant

The filtrate is subjected to electrolysis to estimate the copper, and then boiled, and ammonia is added to precipitate the iron as oxide. The precipitate is dissolved in sulphuric acid, reduced by zinc, and the iron is estimated by titration against potassium permanganate. 

Earlier work using lead(IV) azide or persulfate mediated by iron as oxidant has been reviewed this last procedure, a radical redox one, can woric very well (Scheme 47). Dienes can undergo 1,4-addition with lead(IV) azide reactions with steroid alkenes are varied (refs. 152,154 and references cited therein, and Section 3.5.11) but can yield the 1,2-adducts. 

Terry (1893) gives methods for producing the red iron oxide pigment, copperas red, from either soiuce [natural copperas] is an acid sulphate of iron, which is leached out and neutralised by addition of iron in the form of scrap. The neutral sulphate is crystalhsed out of the liquor, and calcined in a muffle furnace, the shade of the ultimate product being governed by the degree of duration of the roasting. Alternatively, waste-product copperas was neutralised by the addition of scrap iron and hme was added to throw down the iron as oxide the material was then calcined. 

Aluminium is obtained on a large scale by the electrolysis of the oxide, dissolved in fused cryolite The oxide, occurring naturally as bauxite, AI2O3.2H2O, usually contains silica and iron(III) oxide as impurities. These must be removed first, since aluminium, once prepared, cannot be freed of other metals (which will be deposited on electrolysis) by refining it. The crude oxide is dissolved under pressure in caustic soda solution the aluminium oxide and silica dissolve and the ironflll) oxide is left ... 

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. 

Reaction (13.4) is exothermic and reversible, and begins at about 700 K by Le Chatelier s Principle, more iron is produced higher up the furnace (cooler) than below (hotter). In the hotter region (around 900 K), reaction (13.5) occurs irreversibly, and the iron(II) oxide formed is reduced by the coke [reaction (13.6)] further down. The limestone forms calcium oxide which fuses with earthy material in the ore to give a slag of calcium silicate this floats on the molten iron (which falls to the bottom of the furnace) and can bo run off at intervals. The iron is run off and solidified as pigs —boat-shaped pieces about 40 cm long. 

If an aqueous solution of an iron(lll) salt is treated with alkali, a red-brown precipitate of iron(III) hydroxide is obtained this is probably best represented as FeO(OH). On strong heating it gives the red oxide Fe203. Iron(III) oxide, Fc20, occurs naturally as haematite, and can also be prepared by strong heating of iron(II) sulphate ... 

The mixed oxide Fc304 (tri-iron tetroxide) is a black solid, which occurs naturally as magnetite it is formed when iron(III) oxide is strongly heated, and its structure is effectively made up of oxide (O ) and iron(II) and iron(III) ions. 

Iron. As with copper, some dozen or more materials are used as fertilizer Hon sources. These include ferrous and ferric oxides and sulfides and ferrous ammonium phosphate [10101 -60-7] ferrous ammonium sulfate [10045-89-3] frits, and chelates. In many instances, organic chelates are more effective than inorganic materials. Recommended appHcation rates range widely according to both type of micronutrient used and crop. Quantities of Fe range from as low as 0.5 kg/hm as chelates for vegetables to as much as a few hundred kg/hm as ferrous sulfate for some grains. 

Minerals. Iron-bearing minerals are numerous and are present in most soils and rocks. However only a few minerals are important sources of iron and thus called ores. Table 2 shows the principle iron-bearing minerals. Hematite is the most plentiful iron mineral mined, followed by magnetite, goethite, siderite, ilmenite, and pyrite. Siderite is unimportant in the United States, but is an important source of iron in Europe. Tlmenite is normally mined for titania with iron as a by-product. Pyrite is roasted to recover sulfur in the form of sulfur dioxide, leaving iron oxide as a by-product. 

Iron(III) hydroxide [1309-33-7], FeH02, is a red-brown amorphous material that forms when a strong base is added to a solution of an iron(III) salt. It is also known as hydrated iron(III) oxide. The fully hydrated Fe(OH)3 has not been isolated. The density of the material varies between 3.4-3.9 g/cm, depending on its extent of hydration. It is insoluble in water and alcohol, but redissolves in acid. Iron(III) hydroxide loses water to form Fe203. Iron(III) hydroxide is used as an absorbent in chemical processes, as a pigment, and in abrasives. Salt-free iron(III) hydroxide can be obtained by hydrolysis of iron(III) alkoxides. 

The abihty of iron to exist in two stable oxidation states, ie, the ferrous, Fe ", and ferric, Fe ", states in aqueous solutions, is important to the role of iron as a biocatalyst (79) (see Iron compounds). Although the cytochromes of the electron-transport chain contain porphyrins like hemoglobin and myoglobin, the iron ions therein are involved in oxidation—reduction reactions (78). Catalase is a tetramer containing four atoms of iron peroxidase is a monomer having one atom of iron. The iron in these enzymes also undergoes oxidation and reduction (80). 

Iron Oxide Yellows. From a chemical point of view, synthetic iron oxide yellows, also known as iron gelbs, are based on the iron(III) oxide—hydroxide, a-FeO(OH), known as goethite. Color varies from light yellows to dark buffs and is primarily determined by particle size, which is usually between 0.1 and 0.8 p.m. Because of their resistance to alkahes, these are used by the building industry to color cement. Thermally, iron oxide yellows are stable up to 177°C above this temperature they dehydrate to iron(III) oxide ... 

Pyrotechnic mixtures may also contain additional components that are added to modify the bum rate, enhance the pyrotechnic effect, or serve as a binder to maintain the homogeneity of the blended mixture and provide mechanical strength when the composition is pressed or consoHdated into a tube or other container. These additional components may also function as oxidizers or fuels in the composition, and it can be anticipated that the heat output, bum rate, and ignition sensitivity may all be affected by the addition of another component to a pyrotechnic composition. An example of an additional component is the use of a catalyst, such as iron oxide, to enhance the decomposition rate of ammonium perchlorate. Diatomaceous earth or coarse sawdust may be used to slow up the bum rate of a composition, or magnesium carbonate (an acid neutralizer) may be added to help stabilize mixtures that contain an acid-sensitive component such as potassium chlorate. Binders include such materials as dextrin (partially hydrolyzed starch), various gums, and assorted polymers such as poly(vinyl alcohol), epoxies, and polyesters. Polybutadiene mbber binders are widely used as fuels and binders in the soHd propellant industry. The production of colored flames is enhanced by the presence of chlorine atoms in the pyrotechnic flame, so chlorine donors such as poly(vinyl chloride) or chlorinated mbber are often added to color-producing compositions, where they also serve as fuels. 

Another process, which also generates elemental sulfur as a by-product, has been patented by Envirotech Research Center in Salt Lake City (29). In the Electroslurry process, a ball mill finely grinds a chalcopyrite concentrate, which reacts with an acidic copper sulfate solution for iron removal. The Hquor is electrolyzed and the iron is oxidized to the ferric form. This latter step leaches copper from the copper sulfide for deposition on the cathode. Elemental sulfur is recovered at the same time. 

Catalysts. In industrial practice the composition of catalysts are usuaUy very complex. Tellurium is used in catalysts as a promoter or stmctural component (84). The catalysts are used to promote such diverse reactions as oxidation, ammoxidation, hydrogenation, dehydrogenation, halogenation, dehalogenation, and phenol condensation (85—87). Tellurium is added as a passivation promoter to nickel, iron, and vanadium catalysts. A cerium teUurium molybdate catalyst has successfliUy been used in a commercial operation for the ammoxidation of propylene to acrylonitrile (88). 

Metal Incendiaries. Metal incendiaries include those of magnesium in various forms, and powdered or granular aluminum mixed with powdered iron(III) oxide. Magnesium is a soft metal which, when raised to its ignition temperature, bums vigorously in air. It is used in either soHd or powdered form as an incendiary filling, and in alloyed form as the casing for small incendiary bombs. 

Russia and the RepubHc of South Africa account for more than half the world s chromite ore production. Almost all of the world s known reserves of chromium are located in the southeastern region of the continent of Africa. South Africa has 84% and Zimbabwe 11% of these reserves. The United States is completely dependent on imports for all of its chromium (4). The chromite s constitution varies with the source of the ore, and this variance can be important to processing. Typical ores are from 20 to 26 wt % Cr, from 10 to 25 wt % Fe, from 5 to 15 wt % Mg, from 2 to 10 wt % Al, and between 0.5 and 5 wt % Si Other elements that may be present are Mn, Ca, Ti, Ni, and V. AH of these elements are normally reported as oxides iron is present as both Fe(II) andFe(III) (5,6). 

Cobalt is the thirtieth most abundant element on earth and comprises approximately 0.0025% of the earth s cmst (3). It occurs in mineral form as arsenides, sulfides, and oxides trace amounts are also found in other minerals of nickel and iron as substitute ions (4). Cobalt minerals are commonly associated with ores of nickel, iron, silver, bismuth, copper, manganese, antimony, and 2iac. Table 1 Hsts the principal cobalt minerals and some corresponding properties. A complete listing of cobalt minerals is given ia Reference 4. 

Copper is one of the twenty-seven elements known to be essential to humans (69—72) (see Mineral nutrients). The daily recommended requirement for humans is 2.5—5.0 mg (73). Copper is probably second only to iron as an oxidation catalyst and oxygen carrier in humans (74). It is present in many proteins, such as hemocyanin [9013-32-3] galactose oxidase [9028-79-9] ceruloplasmin [9031 -37-2] dopamine -hydroxylase, monoamine oxidase [9001-66-5] superoxide dismutase [9054-89-17, and phenolase (75,76). Copper aids in photosynthesis and other oxidative processes in plants. 

A successful procedure for the formation of 2,5-di-t-butylfuran involves reaction of the parent heterocycle with f-butyl chloride in the presence of iron(III) chloride and iron(III) oxide. Iron(III) oxide acts as a hydrogen chloride scavenger and at the same time regenerates the catalyst. Concurrent polymerization normally deactivates the catalyst (82CI(L)603). 

---