Blue dichromate

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. 

Addition of hydrogen peroxide to a solution of a dichromate yields the blue colour of "peroxochromic acid. This is a test for soluble chromates and dichromates. 

Hydrogen peroxide with a chromate or a dichromate gives a blue colour. 

Oxidation, (i) Dissolve 5 g. of potassium dichromate in 20 ml. of dil. H2SO4 in a 100 ml. bolt-head flask. Cool and add 1 ml. of methanol. Fit the flask with a reflux water-condenser and warm gently a vigorous reaction soon occurs and the solution turns green. The characteristic pungent odour of formaldehyde is usually detected at this stage. Continue to heat for 3 minutes and then fit the flask with a knee-tube (Fig. 59, p. 100) and distil off a few ml. Test the distillate with blue litmus-paper to show that it is definitely acid. Then apply Test 3 p. 350) for formic acid. (The reflux-distillation apparatus (Fig. 38, p. 63) can conveniently be used for this test.)... 

Coloured oxidation products, (a) Dissolve a few small crystals of triphenylamine in i ml. of cone. H2SO4 (cf. footnote, p. 376). Add 2 drops of cone. HNO3 to about 10 ml. of water, mix, and add i drop of this diluted HNO3 to the triphenylamine solution an intense greenish-blue coloration is produced. Dimethylaniline when treated in this way turns a deep dichromate colour. 

Absolute diethyl ether. The chief impurities in commercial ether (sp. gr. 0- 720) are water, ethyl alcohol, and, in samples which have been exposed to the air and light for some time, ethyl peroxide. The presence of peroxides may be detected either by the liberation of iodine (brown colouration or blue colouration with starch solution) when a small sample is shaken with an equal volume of 2 per cent, potassium iodide solution and a few drops of dilute hydrochloric acid, or by carrying out the perchromio acid test of inorganic analysis with potassium dichromate solution acidified with dilute sulphuric acid. The peroxides may be removed by shaking with a concentrated solution of a ferrous salt, say, 6-10 g. of ferrous salt (s 10-20 ml. of the prepared concentrated solution) to 1 litre of ether. The concentrated solution of ferrous salt is prepared either from 60 g. of crystallised ferrous sulphate, 6 ml. of concentrated sulphuric acid and 110 ml. of water or from 100 g. of crystallised ferrous chloride, 42 ml. of concentrated hydiochloric acid and 85 ml. of water. Peroxides may also be removed by shaking with an aqueous solution of sodium sulphite (for the removal with stannous chloride, see Section VI,12). 

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). 

Synthesis. The method of synthesis for Methylene Blue described in reference 14 is stiU the stepwise method of choice for thiazine dyes. /V,/V-Dimethy1-y-pheny1ene diamine [99-98-9], CgH22N2, reacts with sodium thiosulfate [7772-98-7] to form the thiosulfonic acid which condenses with /V, /V-dimetby1 ani1 ine [121 -69-7], CgH N, in the presence of sodium dichromate [10588-01-9] to the indamine, then with copper sulfate [18939-61 -2] and sodium dichromate to Methylene Blue (26). 

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. 

Ferric ammonium ferrocyanide—The blue pigment obtained by oxidising under acidic conditions with sodium dichromate the acid-digested precipitate resulting from mixing solutions of ferrous sulfate and sodium ferrocyanide ia the presence of ammonium sulfate. The oxidized product is filtered, washed, and dried. The pigment consists principally of ferric ammonium ferrocyanide with small amounts of ferric ferrocyanide and ferric sodium ferrocyanide. 

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). 

Mention should be made of one of the earliest internal indicators. This is a 1 per cent solution of diphenylamine in concentrated sulphuric acid, and was introduced for the titration of iron(II) with potassium dichromate solution. An intense blue-violet coloration is produced at the end point. The addition of phosphoric(V) acid is desirable, for it lowers the formal potential of the Fe(III)-Fe(II) system so that the equivalence point potential coincides more nearly with that of the indicator. The action of diphenylamine (I) as an indicator depends upon its oxidation first into colourless diphenylbenzidine (II), which is the real indicator and is reversibly further oxidised to diphenylbenzidine violet (III). Diphenylbenzidine violet undergoes further oxidation if it is allowed to stand with excess of dichromate solution this further oxidation is irreversible, and red or yellow products of unknown composition are produced. 

Caffeine Xanthine derivatives Purines Purines, pyrimidines Purines Chloraminc-T Iron (111) chloride followed by iodine Silver nitrate followed by sodium dichromate Fluorescein Silver nitrate followed by bromophenol blue... 

The industrial production of Prussian blue is based on the reaction in aqueous solution of sodium hexacyanoferrate(n), Na4Fe(CN)6, with iron(n) sulfate, FeS04-7H20 in the presence of an ammonium salt, which results initially in the formation of the colourless insoluble iron(n) hexa-cyanoferrate(n) (Berlin white). Prussian blue is generated by subsequent oxidation with a dichromate or chlorate. 

Some ionic crystals. Nickel(ll) nitrate (Ni(N03)2.6H20, green), potassium dichromate (K2Cr207, orange), copper(ll) sulfate (CuS04.5H20 blue)... 

Experiments—Pass hydrogen sulphide slowly into the most concentrated aqueous solution of Bindschedler s green obtainable, until after some time the colour has changed to yellowish-red. Now add dilute hydrochloric acid and the solution of 0-3 g. of sodium dichromate. Precipitate the methylene blue formed by adding zinc chloride solution. 

This is prepared by passing dry hydrogen chloride over chromium, or hydrogen over anhydrous chromium(III) chloride. It is a white solid. If pure chromium is dissolved in dilute hydrochloric acid in the absence of air, a blue solution of the hydrated chloride, containing the hexaaquo-ion [Cr(H20)6]2+. is obtained. The same solution is also obtained by reduction of the + 6 oxidation state (through the + 3) using a solution of a dichromate(VI) and reducing with zinc and hydrochloric acid ... 

The reaction of alcohol with orange dichromate ions to produce blue-green chromium(III) ions is used in the Breathalyzer test, a test that measures the presence of alcohol in a person s breath. How could a colorimeter be used in this analysis ... 

Dichromated gelatin. This material is particularly sensitive to light in the blue and UV regions, but not the red. They are used to produce volume holograms that approach the theoretical limit in diffraction efficiencies. 

Cautiously add, with stirring, 15 ml of. sulfuric acid, 5 ml of phosphoric acid, and 6 to 8 drops of Na diphenylamine sulfonate indicator soln (0.2g/100 ml of w). Titrate slowly with 0.05N std K dichromate soln until the pure grn color changes to a gray-green. Then add the dichromate one drop at a time until the first tinge of purple or violet-blue appears... 

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