Chromium, trivalent

Group 6 (VIB) Perchlorates. Both divalent and trivalent chromium perchlorate compounds [13931 -95-8 13527-21 -9] have been reported. Anhydrous chromyl perchlorate [60499-74-3] has been prepared ia the cold ... 

Cross-linked xanthan gums have also been used to reduce the permeabiUty of thief 2ones. Trivalent chromium is the preferred cross-linker (54). Cross-linker effectiveness is less at high salinity. However, Cr(III) has been used ia the field at salinities as great as 166,000 ppm total dissolved soHds (55). 

Sodium thiosulfate is still used in chrome leather tanning as a reducing agent in two-bath processes to reduce dichromate (hexavalent chromium) to chrome alum (trivalent chromium) (see Leather). 

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. 

When sufficient hydroxide is added to an aqueous solution of the trivalent chromium ion, the precipitation of a hydrous chromium (ITT) oxide,... 

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. 

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. 

Reproductive Toxicity. No data are available that impHcate either hexavalent or trivalent chromium compounds as reproductive toxins, unless exposure is by way of injection. The observed teratogenic effects of sodium dichromate(VI), chromic acid, and chromium (HI) chloride, adininistered by injection, as measured by dose-response relationships are close to the amount that would be lethal to the embryo, a common trait of many compounds (111). Reported teratogenic studies on hamsters (117,118), the mouse (119—121), and rabbits (122) have shown increased incidence of cleft palate, no effect, and testicular degeneration, respectively. Although the exposures for these experiments were provided by injections, in the final study (122) oral, inhalation, and dermal routes were also tried, and no testicular degeneration was found by these paths. 

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... 

Because the thickness of the plate deposited from trivalent baths is limited, these have only been employed for decorative appHcations. However, the bluish white deposit obtained from chromic acid baths can be closely matched by trivalent chromium baths (173). 

The compositions of the conversion baths are proprietary and vary greatly. They may contain either hexavalent or trivalent chromium (179,180), but baths containing both Cr(III) and Cr(VI) are rare. The mechanism of film formation for hexavalent baths has been studied (181,182), and it appears that the strength of the acid and its identity, as well as time and temperature, influences the film s thickness and its final properties, eg, color. The newly prepared film is a very soft, easily damaged gel, but when allowed to age, the film slowly hardens, assumes a hydrophobic character and becomes resistant to abrasion. The film s stmcture can be described as a cross-linked Cr(III) polymer, that uses anion species to link chromium centers. These anions may be hydroxide, chromate, fluoride, and/or others, depending on the composition of the bath (183). 

Spray liberated from vessels at which an electrolytic chromium process is carried on, except trivalent chromium Every 14 days while the process is being carried on... 

Corrective Action Application At a RCRA site in the southwest, a waste stream containing hexavalent chromium was reduced to the trivalent form. The trivalent chromium was then removed using ion exchange. The influent hexavalent chromium... 

Chromium lignosulfonates are the biggest contributions to heavy metals in drilling fluids. Although studies have shown minimal environmental impact, substitutes exist that can result in lower chromium levels in muds. The less used chromium lignites (trivalent chromium complexes) are similar in character and performance with less chromium. Nonchromium substitutes are effective in many situations. Typical total chromium levels in muds are 100-1000 mg/1. 

Chromium plating from hexavalent baths is carried out with insoluble lead-lead peroxide anodes, since chromium anodes would be insoluble (passive). There are three main anode reactions oxidation of water, reoxidation of Cr ions (or more probably complex polychromate compounds) produced at the cathode and gradual thickening of the PbOj film. The anode current density must balance the reduction and reoxidation of trivalent chromium so that the concentration reaches a steady state. From time to time the PbOj film is removed as it increases electrical resistance. 

Concern over the health hazards of the hexavalent chromium solutions used to form the top coat of conventional nickel plus chromium coatings have encouraged research into trivalent chromium plating solutions. A process with better throwing power and improved covering power than those of hexavalent chromium has been described by Smart etal". A process for depositing a chromium-iron, or chromium-nickel-iron alloy, has been outlined by Law. ... 

Trivalent chromium significantly impaired the reproduction of Daphnia magna at levels of 0.3 to 0.5 mg/L. 

A slight excess of base may be titrated in the previous reactions to shift the pH to a slight basic condition. This is important for the precipitation of certain metal salts (such as nickel, iron, and trivalent chromium) as hydroxides. 

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