Chromium, preparation

The hardness of metallic chromium measured on Rydberg s system is 9-0, though pure chromium prepared by Moissan did not scratch... 

Pannetier s green is a synonym for a chromium oxide hydrate pigment, viridian (. v.), described as a sesquioxide of chromium prepared in a particular manner by Riffault et al. (1874). The name derives from a Parisian colour maker who, along with his assistant Binet, first prepared it about 1838 (Church, 1901). 

Chemically, carbon dioxide is not very reactive, and it is often used as an inactive gas to replace air when the latter might interact with a substance, for example in the preparation of chromium II) salts (p. 383). Very reactive metals, for example the alkali metals and magnesium can, however, continue to bum in carbon dioxide if heated sufficiently, for example... 

The reaction provides a valuable method of preparing anhydrous chlorides of metals. It has been used to prepare the anhydrous chlorides of copper(II), zinc, cadmium, chromium(III), iron(III). cobalt(Il) and nickel. 

The chromates of the alkali metals and of magnesium and calcium are soluble in water the other chromates are insoluble. The chromate ion is yellow, but some insoluble chromates are red (for example silver chromate, Ag2Cr04). Chromates are often isomorph-ous with sulphates, which suggests that the chromate ion, CrO has a tetrahedral structure similar to that of the sulphate ion, SO4 Chromates may be prepared by oxidising chromium(III) salts the oxidation can be carried out by fusion with sodium peroxide, or by adding sodium peroxide to a solution of the chromium(IIl) salt. The use of sodium peroxide ensures an alkaline solution otherwise, under acid conditions, the chromate ion is converted into the orange-coloured dichromate ion ... 

The dichromate ion oxidises iron(II) to iron(III), sulphite to sulphate ion, iodide ion to iodine and arsenic(III) to arsenic(V) (arsenate). Reduction of dichromate by sulphite can be used to prepare chrome alum, since, if sulphur dioxide is passed into potassium dichromate acidified with sulphuric acid, potassium and chromium(III) ions formed are in the correct ratio to form the alum, which appears on crystallisation ... 

Note. Both tetramethylene glycol (1 4-butanediol) and hexamethylene glycol (1 6 hexaiiediol) may be prepared more conveniently by copper-chromium oxide reduction (Section VI,6) or, for small quantities, by reduction with lithium aluminium hydride (see Section VI,10). 

Trimethylene dibromide (Section 111,35) is easily prepared from commercial trimethj lene glycol, whilst hexamethylene dibromide (1 O dibromohexane) is obtained by the red P - Br reaction upon the glycol 1 6-hexanediol is prepared by the reduction of diethyl adipate (sodium and alcohol lithium aluminium hydride or copper-chromium oxide and hydrogen under pressure). Penta-methylene dibromide (1 5-dibromopentane) is readily produced by the red P-Brj method from the commercially available 1 5 pentanediol or tetra-hydropyran (Section 111,37). Pentamethylene dibromide is also formed by the action of phosphorus pentabromide upon benzoyl piperidine (I) (from benzoyl chloride and piperidine) ... 

Anthraqiiinone may also be prepared by the oxidation of pure anthracene with a solution of chromium trioxide in glacial acetic acid ... 

This preparation illustrates the use of the copper-chromium oxide catalyst in the r uotion of esters of dibasic acids to glycols ... 

Gr. chroma, color) Discovered in 1797 by Vauquelin, who prepared the metal the next year, chromium is a steel-gray, lustrous, hard metal that takes a high polish. 

Usually, organoboranes are sensitive to oxygen. Simple trialkylboranes are spontaneously flammable in contact with air. Nevertheless, under carefully controlled conditions the reaction of organoboranes with oxygen can be used for the preparation of alcohols or alkyl hydroperoxides (228,229). Aldehydes are produced by oxidation of primary alkylboranes with pyridinium chi orochrom ate (188). Chromic acid at pH < 3 transforms secondary alkyl and cycloalkylboranes into ketones pyridinium chi orochrom ate can also be used (230,231). A convenient procedure for the direct conversion of terminal alkenes into carboxyUc acids employs hydroboration with dibromoborane—dimethyl sulfide and oxidation of the intermediate alkyldibromoborane with chromium trioxide in 90% aqueous acetic acid (232,233). 

Twelve-membered rings have been obtained using coordination catalysts. The transJmns,ds-cyc. ododec2Lti ien.e has been prepared with a tetrabutyl titanate—diethylalurninum chloride catalyst (48,49) and with a chromium-based system (50). The trans,trans,trans-isom.e-i. has been prepared with a nickel system. 

Attempts to isolate GTF from brewer s yeast have resulted in production of very active concentrates, but the substance is too labile to be obtained in the soHd state (136). However, it has been shown that GTF is a Cr(III) complex containing two coordinated nicotinate radicals and other amino acid anions (146). Active preparations containing similar complexes have been synthesi2ed (147). Chromium deficiency may also lead to atherosclerosis and peripheral neuropathy. 

Molybdenum improves the corrosion resistance of stainless steels that are alloyed with 17—29% chromium. The addition of 1—4% molybdenum results in high resistance to pitting in corrosive environments, such as those found in pulp (qv) and paper (qv) processing (33), as weU as in food preparation, petrochemical, and poUution control systems. 

Second, in the early 1950s, Hogan and Bank at Phillips Petroleum Company, discovered (3,4) that ethylene could be catalyticaHy polymerized into a sohd plastic under more moderate conditions at a pressure of 3—4 MPa (435—580 psi) and temperature of 70—100°C, with a catalyst containing chromium oxide supported on siUca (Phillips catalysts). PE resins prepared with these catalysts are linear, highly crystalline polymers of a much higher density of 0.960—0.970 g/cnr (as opposed to 0.920—0.930 g/cnf for LDPE). These resins, or HDPE, are currentiy produced on a large scale, (see Olefin polymers, HIGH DENSITY POLYETHYLENE). 

Most chromium-based catalysts are activated in the beginning of a polymerization reaction through exposure to ethylene at high temperature. The activation step can be accelerated with carbon monoxide. Phillips catalysts operate at 85—110°C (38,40), and exhibit very high activity, from 3 to 10 kg HDPE per g of catalyst (300—1000 kg HDPE/g Cr). Molecular weights and MWDs of the resins are controlled primarily by two factors, the reaction temperature and the composition and preparation procedure of the catalyst (38,39). Phillips catalysts produce HDPE with a MJM ratio of about 6—12 and MFR values of 90—120. 

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