Chromium compounds Cr

Low Oxidation State Chromium Compounds. Cr(0) compounds are TT-bonded complexes that require electron-rich donor species such as CO and C H to stabilize the low oxidation state. A direct synthesis of Cr(CO)g, from the metal and CO, is not possible. Normally, the preparation requires an anhydrous Cr(III) salt, a reducing agent, an arene compound, carbon monoxide that may or may not be under high pressure, and an inert atmosphere (see Carbonyls). 

The corresponding chromium compounds [Cr(en)3]X3 evolve ethylenediamine [1131] and the values of E determined using non-isothermal measurements were 105 and 182 kJ mole 1 for X = Cl" and SCN", respectively. Hughes [1132] reported a value of E = 175 kJ mole"1 for X = Cl" and showed that the decomposition rate is sensitive to sample disposition. Amine evolution from both the (en) and propenediamine (pn) compounds was catalyzed by NH4C1 [1132,1133] or NH CN [1133,1285], addition of small amounts of these substances resulting in a substantial reduction of E. The influence of NH4C1 is ascribed [1132] to the dissociation products, since HC1 promoted the reaction but NH r and NH4I showed no such effect. 

Divalent chromium compounds (Cr ) (chromous compounds) including chromous chloride (CrCb) and chromous sulfate (CrS04). 

Trivalent chromium compounds (Cr )(chromic compounds) including chromic oxide (Cr203), chromic sulfate (Ct2[S04]3), chromic chloride (CrCb), chromic potassium sulfate (KCr[S04]2), and chromite ore (FeOCdCr203). 

Hexavalent chromium compounds (Cr ) including chromium trioxide (Cr03)— the anhydride of chromic acid chromates (e.g., Na2Cr04), dichromates, (e.g., Na2Cr207), and polychromates. 

The stoichiometric transfer of allenylidene ligands from one metal fragment to another metal center has been scarcely documented, the only examples known involving the allenylidene transfer from chromium compounds [Cr(=C=C= CR R )(C0)5] (R R = aryl, amino or alkoxy groups) to [W(C0)5(THF)] [9d]. DFT calculations indicate that the reaction proceeds by an associative pathway, the initial reaction step involving the coordination of W(CO)5 to the Cc(=Cp bond of the allenylidene ligand in the chromium precursor. 

Chromium is present in the environment in several different forms. The most common forms are Cr(0), Cr(III) and Cr(VI). No taste or odor is associated with chromium compounds. Cr(III) occurs naturally in the environment and is an essential nutrient. Cr(VI) and Cr(0) are generally produced by industrial processes. The metal chromium, which is the Cr(0) form, is used for making steel. Cr(VI) and Cr(III) are used for chrome plating, dyes and pigments, leather tanning by means of... 

Organochromium Catalysts. Several commercially important catalysts utilize organ ochromium compounds. Some of them are prepared by supporting bis(triphenylsilyl)chromate on siUca or siUca-alumina in a hydrocarbon slurry followed by a treatment with alkyl aluminum compounds (41). Other catalysts are based on bis(cyclopentadienyl)chromium deposited on siUca (42). The reactions between the hydroxyl groups in siUca and the chromium compounds leave various chromium species chemically linked to the siUca surface. The productivity of supported organochromium catalysts is also high, around 8—10 kg PE/g catalyst (800—1000 kg PE/g Cr). 

Ghromium(III) Compounds. Chromium (ITT) is the most stable and most important oxidation state of the element. The E° values (Table 2) show that both the oxidation of Cr(II) to Cr(III) and the reduction of Cr(VI) to Cr(III) are favored in acidic aqueous solutions. The preparation of trivalent chromium compounds from either state presents few difficulties and does not require special conditions. In basic solutions, the oxidation of Cr(II) to Cr(III) is still favored. However, the oxidation of Cr(III) to Cr(VI) by oxidants such as peroxides and hypohaUtes occurs with ease. The preparation of Cr(III) from Cr(VI) ia basic solutions requires the use of powerful reducing agents such as hydra2ine, hydrosulfite, and borohydrides, but Fe(II), thiosulfate, and sugars can be employed in acid solution. Cr(III) compounds having identical counterions but very different chemical and physical properties can be produced by controlling the conditions of synthesis. 

Water-Soluble Trivalent Chromium Compounds. Most water-soluble Cr(III) compounds are produced from the reduction of sodium dichromate or chromic acid solutions. This route is less expensive than dissolving pure chromium metal, it uses high quaHty raw materials that are readily available, and there is more processing fiexibiHty. Finished products from this manufacturing method are marketed as crystals, powders, and Hquid concentrates. 

Acute and Chronic Toxicity. Although chromium displays nine oxidation states, the low oxidation state compounds, -II to I, all require Special conditions for existence and have very short lifetimes in a normal environment. This is also tme for most organ ochromium compounds, ie, compounds containing Cr—C bonds. Chromium compounds that exhibit stabiUty under the usual ambient conditions are limited to oxidation states II, III, IV, V, and VI. Only Cr(III) and Cr(VI) compounds are produced in large quantities and are accessible to most of the population. Therefore, the toxicology of chromium compounds has been historically limited to these two states, and virtually all of the available information is about compounds of Cr(III) and/or Cr(VI) (59,104). However, there is some indication that Cr(V) may play a role in chromium toxicity (59,105—107). Reference 104 provides an overview and summary of the environmental, biological, and medical effects of chromium and chromium compounds as of the late 1980s. 

The primary routes of entry for animal exposure to chromium compounds are inhalation, ingestion, and, for hexavalent compounds, skin penetration. This last route is more important in industrial exposures. Most hexavalent chromium compounds are readily absorbed, are more soluble than trivalent chromium in the pH range 5 to 7, and react with cell membranes. Although hexavalent compounds are more toxic than those of Cr(III), an overexposure to compounds of either oxidation state may lead to inflammation and irritation of the eyes, skin, and the mucous membranes associated with the respiratory and gastrointestinal tracts. Skin ulcers and perforations of nasal septa have been observed in some industrial workers after prolonged exposure to certain hexavalent chromium compounds (108—110), ie, to chromic acid mist or sodium and potassium dichromate. 

Prolonged contact with certain chromium compounds may produce allergic reactions and dermatitis in some individuals (114). The initial response is usually caused by exposure to Cr(VI) compounds, but once the allergy is estabUshed, it is extended to the trivalent compounds (111,115). There is also limited evidence of possible chromium associated occupational asthma, but there is insufficient data to estimate a dose for assumed chromium-induced asthma. Reference 116 provides a summary and discussion of chromium hypersensitivity. 

Workplace. The Occupational Safety and Health Administration (OHSA) has estabUshed workplace permissible exposure limits (PEL) for chromium metal and three forms of chromium compounds. OSHA s PEL for chromic acid and chromates is 0.1 mg/m 3 both a ceiling, ie, no exposure above this concentration is allowed, and an 8-h time-weighted average (TWA). Chromium metal and insoluble chromium salts have an 8-h TWA PEL of 1.0 mg/m Cr, and the same standard is 0.5 mg/m Cr for soluble Cr(III) and Cr(II) compounds (144). 

The NIOSH recommended exposure limit for carcinogenic hexavalent chromium is 1 lg/m Cr(VI) as a 10-h TWA, and for noncarcinogenic Cr(VI) the 10-h TWA is 25 lg/m Cr(VI), including a 15-min maximum exposure of 50 lg/m Cr(VI). According to NIOSH, the noncarcinogenic Cr(VI) compounds are chromic acid and the chromates and dichromates of sodium, potassium, lithium, mbidium, cesium, and ammonia. NIOSH considers any hexavalent chromium compound that does not appear on the preceding Hst carcinogenic (145). 

Metal Finishing and Corrosion Control. The exceptional corrosion protection provided by electroplated chromium and the protective film created by applying chromium surface conversion techniques to many active metals, has made chromium compounds valuable to the metal finishing industry. Cr(VI) compounds have dominated the formulas employed for electroplating (qv) and surface conversion, but the use of Cr(III) compounds is growing in both areas because of the health and safety problems associated with hexavalent chromium and the low toxicity of trivalent chromium (see... 

Chromium-containing wood preservatives and their chemical compositions are Hsted ia Table 13 (199). Chromium compounds have a triple function ia wood preservation (200). Most importantiy, after impregnation of the wood the Cr(VI) compounds used ia the formulations react with the wood extractives and the other preservative salts to produce relatively insoluble complexes from which preservative leaches only very slowly. This mechanism has been studied in the laboratory (201—206) and the field (207). Finally, although most of the chromium is reduced to chromium (ITT), there is probably some slight contribution of the chromium (VT) to the preservative value (208). 

C) 370/656X brittleness after exposure to temperatures between about 700 to 1. OSO-F. stainless steels. chromium stainless steels, over 13% Cr and any 400 Series martensitic chromium stainless steels low in carbon content (high Cr/C ratio). complex chromium compound, possibly a chromium-phosphorus compound. chromium steels at temperatures above about 700 F (370 C) keep carbon up in martensitic chromium steels and limit Cr to 13% max. 

Chromium compounds as catalysts, 188 Chromium oxide in catalytic converter, 62 Chromium oxide catalysts, 175-184 formation of active component, 176,177 of Cr-C bonds, 177, 178 propagation centers formation of, 175-178 number of, 197, 198 change in, 183, 184 reduction of active component, 177 Clear Air Act of 1970, 59, 62 Cobalt oxide in catalytic converter, 62 Cocatalysts, 138-141, 152-154 Competitive reactions, 37-43 Copper chromite, oxidation of CO over, 86-88... 

Decomposition of the metal ammines have probably been most extensively investigated. Some qualitative features of the thermal decomposition of metal ammine compounds are conveniently illustrated [1116— 1118] by the somewhat contrasting behaviour of the compounds [Cr(NH3)6]X3 and [Co(NH3)6]X3 where X is Cl- or Br . During decomposition of the chromium compound, the oxidation number of the metal remains unchanged, viz. 

Reaction involves more than a single step. The relative thermal stabilities of the hexammine salts, as determined by the temperatures of onset of the reaction, are Cl" > Br for the cobalt compounds but Br" > Cl" > I" for the chromium compounds. When X = NOi, rapid oxidation developed into an exothermic explosive reaction of both the Cr and the Co salts. 

The related chromium compound [1140], trans-[Cr(pn)2Br2]Br H20, undergoes rapid dehydration at 395 419 K by a first-order process for which E = 96 kJ mole-1 and this is accompanied by some 10% isomerization to the cis compound. At higher temperatures, 433-473 K, the residual anhydrous trans compound isomerizes in the solid state this is also a first-order process and E = 180 kJ mole-1. 

The Phillips Cr/silica catalyst is prepared by impregnating a chromium compound (commonly chromic acid) onto a support material, most commonly a wide-pore silica, and then calcining in oxygen at 923 K. In the industrial process, the formation of the propagation centers takes place by reductive interaction of Cr(VI) with the monomer (ethylene) at about 423 K [4]. This feature makes the Phillips catalyst unique among all the olefin polymerization catalysts, but also the most controversial one [17]. 

Although Cr(VI) oxidants are very versatile and efficient, they have one drawback, which becomes especially serious in larger-scale work the toxicity and environmental hazards associated with chromium compounds. The reagents are used in stoichiometric or excess amount and the Cr(III) by-products must be disposed of safely. 

Among warm-blooded organisms, hexavalent chromium was fatal to dogs in 3 months at 100 mg/kg in their food and killed most mammalian experimental animals at injected doses of 1 to 5 mg Cr/kg body weight, but it had no measurable effect on chickens at dietary levels of 100 mg/kg over a 32-day period. Trivalent chromium compounds were generally less toxic than hexavalent chromium compounds, but significant differences may occur in uptake of anionic and cationic CL3 species, and this difference may affect survival. 

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