Chromatic colours

The chromates of the alkali metals and of magnesium and calcium are soluble in water the other chromates are insoluble. The chromate ion is yellow, but some insoluble chromates are red (for example silver chromate, Ag2Cr04). Chromates are often isomorph-ous with sulphates, which suggests that the chromate ion, CrO has a tetrahedral structure similar to that of the sulphate ion, SO4 Chromates may be prepared by oxidising chromium(III) salts the oxidation can be carried out by fusion with sodium peroxide, or by adding sodium peroxide to a solution of the chromium(IIl) salt. The use of sodium peroxide ensures an alkaline solution otherwise, under acid conditions, the chromate ion is converted into the orange-coloured dichromate ion ... 

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. 

Addition of sodium peroxide to a solution gives a yellow colour of the chromate. 

The chloride is white, the bromide pale yellow and the iodide deeper yellow. These are examples (uncommon) of a coloured compound being obtained from colourless ions. The silver(I) ion intensifies colour in other cases, for example silver chromate(VI), Ag2Cr04, is brick-red while potassium chromaie(VI). K2Cr04. is yellow. 

Compounds of Tl have many similarities to those of the alkali metals TIOH is very soluble and is a strong base TI2CO3 is also soluble and resembles the corresponding Na and K compounds Tl forms colourless, well-crystallized salts of many oxoacids, and these tend to be anhydrous like those of the similarly sized Rb and Cs Tl salts of weak acids have a basic reaction in aqueous solution as a result of hydrolysis Tl forms polysulfldes (e.g. TI2S3) and polyiodides, etc. In other respects Tl resembles the more highly polarizing ion Ag+, e.g. in the colour and insolubility of its chromate, sulfide, arsenate and halides (except F), though it does not form ammine complexes in aqueous solution and its azide is not explosive. 

A. M. del Rio in 1801 claimed to have discovered the previously unknown element 23 in a sample of Mexican lead ore and, because of the red colour of the salts produced by acidification, he called it erythronium. Unfortunately he withdrew his claim when, 4 years later, it was (incorrectly) suggested by the Frenchman, H. V. Collett-Desotils, that the mineral was actually basic lead chromate. In 1830 the element was rediscovered by N. G. Sefstrom in some Swedish iron ore. Because of the richness and variety of colours found in its compounds he called it vanadium after Vanadis, the Scandinavian goddess of beauty. One year later F. Wohler established the identity of vanadium and erythro-nium. The metal itself was isolated in a reasonably pure form in 1867 by H. E. Roscoe who reduced the chloride with hydrogen, and he was... 

Full chromate passivation (Section 15.3) improves the corrosion resistance of both zinc and cadmium towards all environments and is applied for a wide range of applications. Clear and olive-coloured chromate coatings can also be applied for certain purposes. The highest degrees of corrosion protection... 

Chromating Chromating is considered in Section IS.3. The chromate film on zinc is adherent and can be drab, yellow-green or colourless in appearance the colour varies considerably with the method of application. It retards white rust , the white deposit which sometimes forms on fresh zinc surfaces which are kept under humid conditions (see Section 4.7). A chromate film is damaged by heat and if used as a basis for paint adhesion, should preferably not be heated above 10°C, nor for longer than 1 h. 

The chromate sealing treatment imparts to the anodic film a distinct yellow to brown colour, which is probably due to a basic aluminium chromate or alkali chromate adsorbed on to aluminium hydroxide. The film gives appreciable protection against marine exposure. 

The simplest method of chromate sealing involves immersion in a dilute alkali chromate or dichromate solution followed by washing retained chromate imparts a yellow colour to the film. More substantial amounts of slightly soluble chromate can be deposited in the thicker type of absorbent anodic film by a method developed by Dr. L. Whitby at High Duty Alloys Ltd. In this, anodised parts are immersed first in a boiling 30% solution of sodium chromate and then in a boiling 2% solution of zinc nitrate. Residues of the first solution in the film react with the second solution to give a substantial yellow deposit of a basic zinc chromate, probably similar in composition to zinc yellow. 

Discussion. The Mohr method cannot be applied to the titration of iodides (or of thiocyanates), because of adsorption phenomena and the difficulty of distinguishing the colour change of the potassium chromate. Eosin is a suitable... 

Molybdenum(VI), vanadium(V), mercury, and iron interfere permanganates, if present, may be removed by boiling with a little ethanol. If the ratio of vanadium to chromium does not exceed 10 1, nearly correct results may be obtained by allowing the solution to stand for 10-15 minutes after the addition of the reagent, since the vanadium-diphenylcarbazide colour fades fairly rapidly. Vanadate can be separated from chromate by adding oxine to the solution and extracting at a pH of about 4 with chloroform chromate remains in the aqueous solution. Vanadium as well as iron can be precipitated in acid solution with cupferron and thus separated from chromium (III). 

Procedure. Prepare a 0.25 per cent solution of diphenylcarbazide in 50 per cent acetone as required. The test solution may contain from 0.2 to 0.5 part per million of chromate. To about 15 mL of this solution add sufficient 3M sulphuric acid to make the concentration about 0.1M when subsequently diluted to 25 mL, add 1 mL of the diphenylcarbazide reagent and make up to 25 mL with water. Match the colour produced against standards prepared from 0.0002M potassium dichromate solution. A green filter having the transmission maximum at about 540 nm may be used. 

Figure 6. Chromatism is due to the wavelength dependence of the index of refraction and produces coloured, diffuse and/or elongated images. For simplicity reasons, the off-axis image in the figure above is shown with pure lateral chromatism in reality both axial and lateral chromatisms would combine.

Stintzing, F.C., Trichterborn, J., and Carle, R., Characterisation of anthocyanin-beta-lain mixtures for food colouring by chromatic and HPLC-DAD-MS analyses. Food Chem., 94, 296, 2006. 

Zinc chromate, an inorganic colouring agent for rubber. 

The end points of precipitation titrations can be variously detected. An indicator exhibiting a pronounced colour change with the first excess of the titrant may be used. The Mohr method, involving the formation of red silver chromate with the appearance of an excess of silver ions, is an important example of this procedure, whilst the Volhard method, which uses the ferric thiocyanate colour as an indication of the presence of excess thiocyanate ions, is another. A series of indicators known as adsorption indicators have also been utilized. These consist of organic dyes such as fluorescein which are used in silver nitrate titrations. When the equivalence point is passed the excess silver ions are adsorbed on the precipitate to give a positively charged surface which attracts and adsorbs fluoresceinate ions. This adsorption is accompanied by the appearance of a red colour on the precipitate surface. Finally, the electroanalytical methods described in Chapter 6 may be used to scan the solution for metal ions. Table 5.12 includes some examples of substances determined by silver titrations and Table 5.13 some miscellaneous precipitation methods. Other examples have already been mentioned under complexometric titrations. 

Strongly basic antibiotics may be precipitated by formation of the coloured reineckate salt which may then be determined spectrophotometri-cally 65. Bickfordl66 dissolved the precipitated neomycin reineckate in acetone and has successfully used this procedure to assay neomycin extracted from topical formulations. Roushdi et al 73 preferred to oxidise the precipitate with potassium permanganate and then colorimetrically estimate the chromate produced with diphenylcarbazide. 

After the copper oxide-lead chromate layer has been placed in position clean the tube very carefully with a large pad of cotton wool continuing until the wool is no longer coloured by the lead... 

In actual practice, however, such titrations are more or less restricted to those involving precipitation of Ag+ with anions, for instance halogens (Cl , Br, I-) and thiocyanate (SCN-). Generally, it is quite difficult and tedious to locate the exact point at which further addition of reagent affords no more precipitation. Therefore, the choice and wisdom of a chemical reaction is preferably sought so as to result in either a coloured solution or a coloured precipitate at the end point. A typical instance may be cited by application of potassium chromate (K2Cr04) solution in the above case whereby any extra drop of silver nitrate, after all the chloride has been precipitated, immediately causes precipitation of red chromate showing that the end point has been duly achieved. 

In actual practice, the concentration of chromate produces an intense yellow colour to such an extent that the end point is masked. Therefore, normally concentrations of 5 x 10 3 M are employed in analytical procedures. It suggests that [Ag+] shall be > 1.3 / 10 5 M at the end-point thereby introducing a positive determinate error. However, it has been proved experimentally that even with concentrations as low as 2 x 10 3 M, the extent of error caused is negligibly small. 

Procedure Weigh accurately about 4 g of chloral hydrate and dissolve in 10 ml of DW and add 30 ml of N sodium hydroxide solution. Allow the resulting mixture to stand for 2 minutes, and then titrate with N sulphuric acid, employing phenolphthalein solution as indicator till a colour change from pink to colourless is achieved. Titrate the neutralized liquid thus obtained with 0.1 N silver nitrate using potassium chromate solution as indicator till precipitation of red chromate is obtained, Add, now 2/15th of the amount of 0.1 N silver nitrate used to the amount of N sulphuric acid used in the first titration and deduct the figure so obtained... 

In this state, chromium compounds are usually coloured yellow or red (but due to charge transfer (p. 60) and not to the presence of d electrons on the chromium ion). The only halide known is the unstable chromium(VI) fluoride CrF6, a yellow solid. However, oxide halides are known, for example Cr02Cl2 ( chromyl chloride ), formed as a red vapour when concentrated sulphuric acid is added to a chromate(VI) (or dichromate) mixed with a chloride ... 

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