By iron

The reduction of a nitrate, for example potassium nitrate, by iron(ll) sulphate in the presence of concentrated sulphuric acid gives reasonably pure nitrogen monoxide. The mixture is warmed and at this temperature the nitrogen monoxide produced does not combine with uncharged iron(II) sulphate (see below). 

Nitro groups are readily reduced to primary amines by a variety of methods Cat alytic hydrogenation over platinum palladium or nickel is often used as is reduction by iron or tin m hydrochloric acid The ease with which nitro groups are reduced is especially useful m the preparation of arylamines where the sequence ArH ArN02 ArNH2 IS the standard route to these compounds... 

Figure 8.39 shows some results of EXAFS following absorption by iron atoms in proteins with three prototype iron-sulphur active sites. In the example in Figure 8.39(a) application of a 0.9-3.5 A filter window before Fourier retransformation shows a single wave resulting... 

N—Fe(IV)Por complexes. Oxo iron(IV) porphyrin cation radical complexes, [O—Fe(IV)Por ], are important intermediates in oxygen atom transfer reactions. Compound I of the enzymes catalase and peroxidase have this formulation, as does the active intermediate in the catalytic cycle of cytochrome P Q. Similar intermediates are invoked in the extensively investigated hydroxylations and epoxidations of hydrocarbon substrates cataly2ed by iron porphyrins in the presence of such oxidizing agents as iodosylbenzene, NaOCl, peroxides, and air. 

Lead and its alloys are generally melted, handled, and refined in cast-iron, cast-steel, welded-steel, or spun-steel melting ketdes without fear of contamination by iron (qv). Normal melting procedures require no dux cover for lead. Special reactive metal alloys require special alloying elements, duxes, or covers to prevent dross formation and loss of the alloying elements. 

Dinitrotoluene is oxidized to 2,4-dinitrobenzoic acid [610-30-0] by potassium permanganate or chromic acid, and is reduced to 2,4-diaminotoluene by iron and acetic acid. It is reduced partially by zinc chloride and hydrochloric acid to 2-amino-4-nitrotoluene [99-55-8] and by ammonium sulfide to 4-amino-2-nitrotoluene [119-32-4],... 

Concrete is commonly used, augmented by iron and lead for gamma rays and water for fast neutrons. 

Tetrapotassium peroxodiphosphate is produced by electrolysis of a solution containing dipotassium phosphate and potassium fluoride (52). Alkalinity favors the formation of the P20 g anion, whereas the PO anion is produced in larger yields in acidic solution. It is therefore possible to obtain an 80% yield of K4P20g by choosing the proper conditions. The tetrapotassium peroxodiphosphate can be crysta11i2ed from solution by evaporation of water to form a slurry. The crystals can be separated from the slurry and dried. The material is noncorrosive and cannot be catalyticaHy decomposed by iron ions. 

Tubular Fixed-Bed Reactors. Bundles of downflow reactor tubes filled with catalyst and surrounded by heat-transfer media are tubular fixed-bed reactors. Such reactors are used most notably in steam reforming and phthaUc anhydride manufacture. Steam reforming is the reaction of light hydrocarbons, preferably natural gas or naphthas, with steam over a nickel-supported catalyst to form synthesis gas, which is primarily and CO with some CO2 and CH. Additional conversion to the primary products can be obtained by iron oxide-catalyzed water gas shift reactions, but these are carried out ia large-diameter, fixed-bed reactors rather than ia small-diameter tubes (65). The physical arrangement of a multitubular steam reformer ia a box-shaped furnace has been described (1). 

Shipment nd Stora.ge, Sulfur monochloride is minimally corrosive to carbon steel and iron when dry. If it is necessary to avoid discoloration caused by iron sulfide formation or chloride stress cracking, 310 stainless steel should be used. Sulfur monochloride is shipped in tank cars, tank tmcks, and steel dmms. When wet, it behaves like hydrochloric acid and attacks steel, cast iron, aluminum, stainless steels, copper and copper alloys, and many nickel-based materials. Alloys of 62 Ni—28 Mo and 54 Ni—15 Cr—16 Mo are useful under these conditions. Under DOT HM-181 sulfur monochloride is classified as a Poison Inhalation Hazard (PIH) Zone B, as well as a Corrosive Material (DOT Hazard Class B). Shipment information is available (140). 

Oxidation of sulfur dioxide in aqueous solution, as in clouds, can be catalyzed synergistically by iron and manganese (225). Ammonia can be used to scmb sulfur dioxide from gas streams in the presence of air. The product is largely ammonium sulfate formed by oxidation in the absence of any catalyst (226). The oxidation of SO2 catalyzed by nitrogen oxides was important in the eady processes for manufacture of sulfuric acid (qv). Sulfur dioxide reacts with chlorine or bromine forming sulfuryl chloride or bromide [507-16 ]. 

Iron Precipitation. Rich sulfide ore or Hquated antimony sulfide (cmde antimony) is reduced to metal by iron precipitation. This process, consisting essentially of heating molten antimony sulfide ia cmcibles with slightly more than the theoretical amount of fine iron scrap, depends on the abihty of iron to displace antimony from molten antimony sulfide. Sodium sulfate and carbon are added to produce sodium sulfide, or salt is added to form a light fusible matte with iron sulfide and to faciHtate separation of the metal. Because the metal so formed contains considerable iron and some sulfur, a second fusion with some Hquated antimony sulfide and salt foHows for purification. 

In the glass (qv) and ceramic industry (see Ceramics), barite can be used both as a flux, to promote melting at a lower temperature or to increase the production rate, and as an additive to increase the refractive index of glass. The viscosity of barite-containing glass often needs to be raised. Alumina in the form of feldspar is sometimes used. To offset any color produced by iron from the barite addition, more decolorizer may be needed. When properly used, barytes help reduce seed, increase toughness and brilliancy, and reduce annealing time. Barite is also a raw material for the manufacture of other barium chemicals. 

For practical reasons, the blast furnace hearth is divided into two principal zones the bottom and the sidewalls. Each of these zones exhibits unique problems and wear mechanisms. The largest refractory mass is contained within the hearth bottom. The outside diameters of these bottoms can exceed 16 or 17 m and their depth is dependent on whether underhearth cooling is utilized. When cooling is not employed, this refractory depth usually is determined by mathematical models these predict a stabilization isotherm location which defines the limit of dissolution of the carbon by iron. Often, this depth exceeds 3 m of carbon. However, because the stabilization isotherm location is also a function of furnace diameter, often times thermal equiHbrium caimot be achieved without some form of underhearth cooling. 

This wear is caused primarily from high thermal and mechanical stress, chemical attack, attack by iron and slag, oxidation, and severe thermal shock. Thus the design of the hearth wall and the concepts employed ate just as important as the carbon or graphite materials chosen for the refractory material. Despite their benefits and properties, no carbon or graphite material can overcome the problems of an improper hearth wall design concept. 

This reaction is catalyzed by iron, and extensive research, including surface science experiments, has led to an understanding of many of the details (72). The adsorption of H2 on iron is fast, and the adsorption of N2 is slow and characterized by a substantial activation energy. N2 and H2 are both dis so datively adsorbed. Adsorption of N2 leads to reconstmction of the iron surface and formation of stmctures called iron nitrides that have depths of several atomic layers with compositions of approximately Fe N. There is a bulk compound Fe N, but it is thermodynamically unstable when the surface stmcture is stable. Adsorbed species such as the intermediates NH and NH2 have been identified spectroscopically. 

Methylene chloride is one of the more stable of the chlorinated hydrocarbon solvents. Its initial thermal degradation temperature is 120°C in dry air (1). This temperature decreases as the moisture content increases. The reaction produces mainly HCl with trace amounts of phosgene. Decomposition under these conditions can be inhibited by the addition of small quantities (0.0001—1.0%) of phenoHc compounds, eg, phenol, hydroquinone, -cresol, resorcinol, thymol, and 1-naphthol (2). Stabilization may also be effected by the addition of small amounts of amines (3) or a mixture of nitromethane and 1,4-dioxane. The latter diminishes attack on aluminum and inhibits kon-catalyzed reactions of methylene chloride (4). The addition of small amounts of epoxides can also inhibit aluminum reactions catalyzed by iron (5). On prolonged contact with water, methylene chloride hydrolyzes very slowly, forming HCl as the primary product. On prolonged heating with water in a sealed vessel at 140—170°C, methylene chloride yields formaldehyde and hydrochloric acid as shown by the following equation (6). 

Homolytic oxaziridine decomposition can be easily initiated by iron(II) ion in acidic media. Catalytic amounts are sufficient because chain reactions proceed. The reaction proceeds obviously in the case of 2-r-alkyloxaziridines like (56), where it yields the isomeric acid amide (111) (57JA5739). 

In spirooxaziridines like (114), /3-scission proceeds with ring opening. Stoichiometric amounts of iron(II) salt in acidic solution lead to the dicarboxylic acid derivative (115). The radical undergoes some interesting reactions with added unsaturated compounds. For example, pyridine yields a mixture of 2- and 4-alkylation products in 80% yield. Catalytic amounts of iron(II) ion are sufficient here since the adduct of the radical with pyridine is oxidized by iron(III) ion to the final product (116), thus regenerating iron(II) ion (68TL5609). 

Because of analogy of radical formation by iron(II) ion from either peroxides or oxaziridines, the latter were proposed repeatedly as initiators of radical chains, e.g. in styrene polymerization and in treatment of unsaturated polyesters. Oxaziridines appear to be easier to prepare than peroxides and to be less hazardous in handling (76MI50801). 

Oxidation of /U-cresol afforded a triphenol 22 which is approximately half the molecule. The central hydroxyl of the triphenol could be selectively methylated and then the compound was ort/ro-brominated and bridged using 1,3-dibromopropane to give 23. Metallation with butyllithium followed by iron catalyzed coupling afforded the macrocycle as indicated. 

Most commercial liquid ammonia contains up to several ppm of colloidal iron compounds, possibly the iron oxide catalyst commonly used in manufacturing ammonia. Reduction converts these compounds to colloidal iron which strongly catalyzes the reaction between alcohols and sodium and potassium. The reaction of lithium with alcohols is also catalyzed by iron but to a markedly lesser degree. The data in Table 1-4 illustrate the magnitude of these catalytic effects. The data of Table 1-5 emphasize how less than 1 ppm... 

At the time of the explosion, the wooden stagings were being replaced by iron ones, but the work was going slowly, as the materials needed were rationed and the Munitions Works Board had classified the change as desirable but not absolutely necessary. 

Allylation of perfluoroalkyl halides with allylsilanes is catalyzed by iron or ruthenium carbonyl complexes [77S] (equation 119) Alkenyl-, allyl-, and alkynyl-stannanes react with perfluoroalkyl iodides 111 the presence ot a palladium complex to give alkenes and alkynes bearing perfluoroalkyl groups [139] (equation 120)... 

Bismuth oeeurs mainly as bismite (a-Bi203), bismuthinite (Bi2S3) and bismutite [(Bi0)2C03] very oeeasionally it oeeurs native, in assoeiation with Pb, Ag or Co ores. The main eommereial souree of the element is as a byproduet from Pb/Zn and Cu plants, from whieh it is obtained by special processes dependent on the nature of the main product. Sulfide ores are roasted to the oxide and then reduced by iron or charcoal. Because of its low mp, very low solubiUty in Fe, and fairly high oxidative stability in air, Bi can be melted and cast (like Pb) in iron and steel vessels. Like Sb, the metal is too brittle to roll, draw, or extrude at room temperature, but above 225°C Bi can be worked quite well. 

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