Dichromate compounds

Chromate and dichromate compounds are suspected carcinogens (cancer-inducing agents) and should be handled carefully. 

When heated with an acidic solution of sodium dichromate, compound A forms benzoic acid. Identify compound A from its NMR spectrum. 

Chromate and dichromate compounds are carcinogens (cancer-inducingagents) and shouid be bandied very carefully. 

Addition of dilute potassium dichromate(VI) solution, K2Cr207, to a solution of hydrogen peroxide produces chromium peroxide, CrOj, as an unstable blue coloration on adding a little ether and shaking this compound transfers to the organic layer in which it is rather more stable. 

The most important compounds containing Cr(VI) are the oxide Cr03 and the oxoanions CrO, chromate(VI) and Cr20 . dichromate(VI). 

Oxidation of side chains. Aromatic nitro compounds that contain a side chain (e.g., nitro derivatives of alkyl benzenes) may be oxidised to the corresponding acids either by alkahne potassium permanganate (Section IV,9, 6) or, preferably, with a sodium dichromate - sulphuric acid mixture in which medium the nitro compound is more soluble. 

Mix 1 g. of the nitro compound with 4 g, of sodium dichromate and 10 ml. of water in a 50 ml. flask, then attach a reflux condenser to the flask. Add slowly and with shaking 7 ml. of concentrated sulphuric acid. The reaction usually starts at once if it does not, heat the flask gently to initiate the reaction. When the heat of reaction subsides, boil the mixture, cautiously at first, under reflux for 20-30 minutes. Allow to cool, dilute with 30 ml. of water, and filter oflF the precipitated acid. Purify the crude acid by extraction with sodium carbonate solution, precipitation with dUute mineral acid, and recrystaUisation from hot water, benzene, etc. 

The compound is employed inter alia as an indicator In titrations with potassium dichromate and ceric siilphate solutions. 

All compounds of chromium are colored the most important are the chromates of sodium and potassium and the dichromates and the potassium and ammonium chrome alums. The dichromates are used as oxidizing agents in quantitative analysis, also in tanning leather. 

In addition to CuCfi, some other compounds such as Cu(OAc)2, Cu(N03)2-FeCl.i, dichromate, HNO3, potassium peroxodisulfate, and Mn02 are used as oxidants of Pd(0). Also heteropoly acid salts comtaining P, Mo, V, Si, and Ge are used with PdS04 as the redox system[2]. Organic oxidants such as benzo-quinone (BQ), hydrogen peroxide and some organic peroxides are used for oxidation. Alkyl nitrites are unique oxidants which are used in some industrial... 

A compound is a cyclic ether of molecular formula C9H10O Its NMR spectrum is shown in Figure 16 10 Oxidation of the compound with sodium dichromate and sulfunc acid gave 1 2 benzenedicarboxylic acid What is the compound d... 

Sulfates of sodium are iadustriaUy important materials commonly sold ia three forms (Table 1). In the period from 1970 to 1981, > 1 million metric tons were consumed aimuaHy ia the United States. Siace then, demand has declined. In 1988 consumption dropped to 890,000 t, and ia 1994 to 610,000 t (1,2). Sodium sulfate is used principally (40%) ia the soap (qv) and detergent iadustries. Pulp and paper manufacturers consume 25%, textiles 19%, glass 5%, and miscellaneous iadustries consume 11% (3). About half of all sodium sulfate produced is a synthetic by-product of rayon, dichromate, phenol (qv), or potash (see Chromium compounds Fibers, regenerated cellulosics Potassium compounds). Sodium sulfate made as a by-product is referred to as synthetic. Sodium sulfate made from mirabilite, thenardite, or naturally occurring brine is called natural sodium sulfate. In 1994, about 300,000 t of sodium sulfate were produced as a by-product another 300,000 t were produced from natural sodium sulfate deposits (4). 

The starting materials of the aldehyde method may be sulfonated. For example. Cl Acid Blue 9 [2650-18-2] Cl Food Blue 2 (Cl 42090), is manufactured by condensing a-(A/-ethylanilino)-y -toluenesulfonic acid with o-sulfobenzaldehyde. The leuco base is oxidized with sodium dichromate to the dye, which is usually isolated as the ammonium salt. In this case, the removal of the excess amine is not necessary. However, this color caimot be used in the food sector because separation of the chromium compounds from the dye is difficult. An alternative method which gives food-grade Cl Acid Blue 9 (14) and dispenses with the use of sodium dichromate employs oxidative electrolysis of the leuco base (49). 

The deep violet color of pentaphenylbismuth and certain other pentaarylbismuth compounds has been the subject of considerable speculation. It has been shown by x-ray diffraction (173) that the bismuth atom in pentaphenylbismuth is square—pyramidal. WeU-formed crystals are dichromic, appearing violet when viewed in one plane but colorless in another plane. The nature of the chromophore has been suggested to be a charge-transfer transition by excitation of the four long equatorial bonds ... 

Sihcon carbide is comparatively stable. The only violent reaction occurs when SiC is heated with a mixture of potassium dichromate and lead chromate. Chemical reactions do, however, take place between sihcon carbide and a variety of compounds at relatively high temperatures. Sodium sihcate attacks SiC above 1300°C, and SiC reacts with calcium and magnesium oxides above 1000°C and with copper oxide at 800°C to form the metal sihcide. Sihcon carbide decomposes in fused alkahes such as potassium chromate or sodium chromate and in fused borax or cryohte, and reacts with carbon dioxide, hydrogen, ak, and steam. Sihcon carbide, resistant to chlorine below 700°C, reacts to form carbon and sihcon tetrachloride at high temperature. SiC dissociates in molten kon and the sihcon reacts with oxides present in the melt, a reaction of use in the metallurgy of kon and steel (qv). The dense, self-bonded type of SiC has good resistance to aluminum up to about 800°C, to bismuth and zinc at 600°C, and to tin up to 400°C a new sihcon nitride-bonded type exhibits improved resistance to cryohte. 

Cleavage of an alkenoic acid can be carried out with permanganate, a permanganate—periodate mixture, periodate or with nitric acid, dichromate, ozone, or, if the unsaturation is first converted to a dihydroxy compound, lead tetraacetate (71,73). Oxidative ozonolysis is a process for the manufacture of azelaic acid [123-99-9] and pelargonic acid (74). 

In addition to the Zachariasen and radius ratio rules, for oxides the electronegativity of the predominant cation should be between 1.7 and 2.1 (7). If the cation electronegativity is too high, the compound tends to form molecules or discrete polyatomic ions rather than a connected network. For example, CrO satisfies the radius ratio rule, but the highly electronegative Cr ions promote the formation of discrete dichromate(VI) ions, Cr202 , in the presence of other oxides. 

The primary Cr—O bonded species is cbromium (VT) oxide, CrO, which is better known as chromic acid [1115-74-5], the commercial and common name. This compound also has the aliases chromic trioxide and chromic acid anhydride and shows some similarity to SO. The crystals consist of infinite chains of vertex-shared CrO tetrahedra and are obtained as an orange-red precipitate from the addition of sulfuric acid to the potassium or sodium dichromate(VI). Completely dry CrO is very dark red to red purple, but the compound is deflquescent and even traces of water give the normal mby red color. Cbromium (VT) oxide is a very powerful oxidi2er and contact with oxidi2able organic compounds may cause fires or explosions. 

The dichromate(VI) salts may be obtained by the addition of acid to the chromate(VI) salts. However, they are better prepared by adding one-half the acid equivalent of a metal hydrate, oxide, or carbonate to an aqueous solution of CrO, then removing the water and/or CO2. Most dichromates(VI) are water-soluble, and the salts contain water(s) of hydration. However, the normal salts of K, Cs, and Rb are anhydrous. Dichromate(VI) compounds of the colorless cations are generally orange-red. The geometry of Ci2 is described as two tetrahedral CrO linked by the shared odd oxygen (72). 

Manufacture The primary iadustrial compounds of chromium made directly from chromite ore are sodium chromate, sodium dichromate, and chromic acid. Secondary chromium compounds produced ia quantity include potassium dichromate, potassium chromate, and ammonium dichromate. 

The neutralized, alumina-free sodium chromate solution may be marketed as a solution of 40° Bh (specific gravity = 1.38), evaporated to dryness, or crystallized to give a technical grade of sodium chromate or sodium chromate tetrahydrate [1003-82-9] Na2Cr04 4H2O. If the fuel for the kilns contains sulfur, the product contains sodium sulfate as an impurity. This compound is isomorphous with sodium chromate and hence difficult to separate. High purity sodium chromate must be made from purified sodium dichromate. 

Sodium chromate can be converted to the dichromate by a continuous process treating with sulfuric acid, carbon dioxide, or a combination of these two (Fig. 2). Evaporation of the sodium dichromate Hquor causes the precipitation of sodium sulfate and/or sodium bicarbonate, and these compounds are removed before the final sodium dichromate crystallization. The recovered sodium sulfate may be used for other purposes, and the sodium bicarbonate can replace some of the soda ash used for the roasting operation (76). The dichromate mother Hquor may be returned to the evaporators, used to adjust the pH of the leach, or marketed, usually as 69% sodium dichromate solution. 

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. 

---