Chromium Blue

Schreiber, H. D. (1978) Chromium, blue diopside, and experimental petrology. Contrib. Mineral. Petrol., 66,341-2 [see Ikeda Yagi (1977,1982)]. 

This complex, or a dehydronated ( deprotonated ) form may be an intermediate in various reactions. The formation of this Chromium Blue is an excellent test for Cr about 0.5 mM may be detected readily, especially if the ether is used, but this does not extract the products of neutral or alkaline solutions. 

Chromium(IJ) chloride, chromous chloride, CrCl2- White solid (Cr plus HCl gas) dissolving to give a blue solution. Forms hydrates, widely used as a reducing agent. 

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 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). 

Most mordant dyes are monoazo stmctures. The most important feature of this class of dyes is excellent fastness to light and washing. Mordant dyes are available ia aU shades of the spectmm with the exceptioa of bright violets, blues, and greens. To be useful, the metal complexes must be stable, ie, must not demetallize when subjected to dyebath conditions and aU aftertreatment processes, especially repeated washings. Chromium forms stable chelate rings with mordant dyes which are not affected by treatment with either weak acid or alkaU (see Coordination compounds). 

Premetallized Dyes. Although discovered in 1912, the 1 1 chromium complexes known as Palatine Fast (BASF) and Neolan (Ciba) dyes had httie practical use as wool dyes until 1920 when it was found that a strongly acidic dyebath (pH ca 2.0) (51) was requited to obtain satisfactory dyeing and acceptable fastness properties. Dyes of this type exemplified by Neolan Blue 2G [6370-12-3] (57) (Cl Acid Blue 158A Cl 15050) are stiU in use despite the damage to the wool caused by the strong acid in the dyebath. 

Chemical Properties. The valence states of chromium are +2, +3, and +6, the latter two being the most common. The +2 and +3 states are basic, whereas the +6 is acidic, forming ions of the type CrO (chromates) and (Cr203 [ (dichromates). The blue—white metal is refractory and very hard. 

Ghromium(II) Compounds. The Cr(II) salts of nonoxidizing mineral acids are prepared by the dissolution of pure electrolytic chromium metal ia a deoxygenated solution of the acid. It is also possible to prepare the simple hydrated salts by reduction of oxygen-free, aqueous Cr(III) solutions using Zn or Zn amalgam, or electrolyticaHy (2,7,12). These methods yield a solution of the blue Cr(H2 0)g cation. The isolated salts are hydrates that are isomorphous with and compounds. Examples are chromous sulfate heptahydrate [7789-05-17, CrSO 7H20, chromous chloride hexahydrate... 

When hydrogen peroxide is added to an acid solution of Cr(VI), a deep blue color, iadicating the formation of chromium (VI) oxide diperoxide [35262-77-2] is observed. This compound is metastable and rapidly decomposes to Cr(III) and oxygen at room temperature. The reaction... 

Clear-bright and blue-bright chromium conversion colors are thin films (qv) and may be obtained from both Cr(III) and Cr(VI) conversion baths. The perceived colors are actually the result of interference phenomena. Iridescent yellows, browns, bron2es, oHve drabs, and blacks are only obtained from hexavalent conversion baths, and the colors are Hsted in the order of increasing film thickness. Generally, the thicker the film, the better the corrosion protection (see Eilmdepositiontechniques). 

Chrornium—cobalt—alurninum oxide [68187-11-1]—Cl Pigment Blue 36, Cl No. 77343. A blue—green pigment obtained by calcining a mixture of chromium oxide, cobalt carbonate, and aluminum oxide. It may contain small amounts (<1% each) of oxides of barium, boron, siUcon, and nickel. 

A wide variety of greens ranging from blue to yellow in shade ate based on cobalt in combination with chromium, aluminum, titanium, nickel, magnesium, antimony, or zinc. These are brighter than the chromium oxides. 

Titanate Pigments. When a nickel salt and antimony oxide are calcined with mtile titanium dioxide at just below 1000°C, some of the added metals diffuse into the titanium dioxide crystal lattice and a yellow color results. In a similar manner, a buff may be produced with chromium and antimony a green, with cobalt and nickel and a blue, with cobalt and aluminum. These pigments are relatively weak but have extreme heat resistance and outdoor weatherabihty, eg, the yellow is used where a light cadmium could not be considered. They are compatible with most resins. 

Pigment Blue 36 chromium —cobalt—aluminum oxide [68187-11-1] 11M2)... 

Acid—mordant dyes have characteristics similar to those of acid dyes which have a relatively low molecular weight, anionic substituents, and an affinity to polyamide fibers and mordant dyes. In general, brilliant shades caimot be obtained by acid—mordant dyes because they are used as their chromium mordant by treatment with dichromate in the course of the dyeing procedure. However, because of their excellent fastness for light and wet treatment, they are predominandy used to dye wool in heavy shades (navy blue, brown, and black). In terms of chemical constitution, most of the acid—mordant dyes are azo dyes some are triphenyhnethane dyes and very few anthraquinone dyes are used in this area. Cl Mordant Black 13 [1324-21 -6] (183) (Cl 63615) is one of the few examples of currentiy produced anthraquinone acid—mordant dyes. It is prepared by condensation of purpurin with aniline in the presence of boric acid, followed by sulfonation and finally by conversion to the sodium salt (146,147). 

Copper and chromium are used for complexing a number of dyes such as the coppered direct and reactive dyes for cotton and metaUi2ed and neutral metal complex acid dyes for nylon, wool, etc. Examples are Direct Blue 218 [28407-37-6] (Cl 24401) (317), Reactive Violet 2 [8063-57-8] (Cl 18157) (318), and Acid Black 52 [5610-64-0] (Cl 15711) (319). 

Chromium (II) chloride (anhydrous) [10049-05-5] M 122.9, m 824 , d]" 2.75, Obtained from the dihydrate by heating in vacuo at 180°. It is a very hygroscopic white powder which dissolves in H2O to give a sky blue solution. Stable in dry air but oxidises rapidly in moist air and should be stored in air tight containers. It sublimes at 800° in a current of HCl gas and cooled in the presence of HCl gas. Alternatively it can be washed with air-free Et20 and dried at 110-120°. [Inorg Synth 3 150 1950.]... 

A 500-ml three-necked flask fitted with a mechanical stirrer and a nitrogen inlet and outlet is charged with 30 g (approx. 0.055 mole) of hydrated chromium (III) sulfate, 200 ml of distilled water, 7.5 g (0.12 g-atom) of mossy zinc, and 0.4 ml (5.4 g, 0.03 g-atom) of mercury. The flask is flushed with nitrogen for 30 minutes and a nitrogen atmosphere is maintained. The mixture is then heated to about 80° with stirring for 30 minutes to initiate reaction. Then the mixture is stirred at room temperature for an additional 30 hours, by which time the green mixture has been converted to a clear blue solution. Solutions prepared as above are about 0.55 M in chromium (II) and are indefinitely stable if protected from oxygen. 

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