Colour excess

Group V. This group includes all the water-insoluble hydrocarbons and oxygen compounds that do not contain N or S and are soluble in cold concentrated sulphuric acid. Any changes—colour, excessive charring, evolution of gases or heat, polymerisation and precipitation of an insoluble compound— attending the dissolution of the substance should be carefully noted. 

The identification of camphene is best carried out by its conversion into isobomeol under the influence of acetic acid in the presence of sulphuric acid. In order to effect this conversion, 100 grams of the fraction containing the terpene in substantial quantity are mixed with 250 grains of glacial acetic acid and 10 grams of 50 per cent, sulphuric acid. Tne mixture is heated for two to three hours on a water-bath to a temperature of 50° to 60°. At first the liquid separates into two layers, bat soon becomes homogeneous and takes on a pale red colour. Excess of water is added, and the oil which is precipitated, and which contains the isobomeol in the form of its acetate, is well washed with water repeatedly. It is then saponified by heating with alcoholic potash solution on a water-bath. The liquid is then evaporated and extracted with water, and the residue recrystallised from petroleum ether. 

The interstellar extinction has a great effect on distance determination for stars. The B/V index derived in Chapter 2 will be distorted by the presence of interstellar dust, with an amount of radiation in the blue part of the spectrum removed. The difference between the observed colour index and the colour index on which it should have based its temperature is called the colour excess. We defined m to be the measured apparent magnitude, which must now be corrected by an amount Av and added to the distance modulus equation ... 

Reddening of the continuum by interstellar dust (which leads to excess redness, known as colour excess, relative to the spectral type from H or other line features). 

Table 29. Numbers of obvious non-Kekulean benzenoids with different colour excess (A values), classified according to symmetry...

Cd(OH) j. The hydroxide is precipitated from aqueous solution by OH", it does not dissolve in excess OH". Ignition of Cd(OH)2 or CdCO, gives CdO which varies in colour from red-brown to black because of lattice defects. 

C-jHg. A slightly coloured liquid, b.p. 90 C, obtained by a Diels-Alder reaction between cyclopcntadiene and ethyne at approximately 150°C. At temperatures in excess of 450°C it rearranges to cycloheptatriene (tropilidene). 

Boron trioxide is not particularly soluble in water but it slowly dissolves to form both dioxo(HB02)(meta) and trioxo(H3B03) (ortho) boric acids. It is a dimorphous oxide and exists as either a glassy or a crystalline solid. Boron trioxide is an acidic oxide and combines with metal oxides and hydroxides to form borates, some of which have characteristic colours—a fact utilised in analysis as the "borax bead test , cf alumina p. 150. Boric acid. H3BO3. properly called trioxoboric acid, may be prepared by adding excess hydrochloric or sulphuric acid to a hot saturated solution of borax, sodium heptaoxotetraborate, Na2B407, when the only moderately soluble boric acid separates as white flaky crystals on cooling. Boric acid is a very weak monobasic acid it is, in fact, a Lewis acid since its acidity is due to an initial acceptance of a lone pair of electrons from water rather than direct proton donation as in the case of Lowry-Bronsted acids, i.e. 

These are of two general kinds octahedral, pink complexes and tetrahedral, blue complexes. If cobalt(II) chloride is dissolved in aqueous solution, the predominant species is the hexaaquo-ion [ColHjO) ] (pink). If this solution is heated, it becomes blue, and the same effect is observed if chloride ion is added in excess. This colour change is associated with the change... 

Alkali hydroxide gives a white precipitate solubie in excess. The white precipitate, Zn(OH)2, gives the oxide when dehydrated the white yellow reversible colour change observed on heating the oxide is a useful confirmatory test. 

Three crystalline compounds, one violet, one pale green, and one deep green in colour, all have the molecular formula CrClj. 6H2O. When equal masses of the three compounds are separately treated with an excess of aqueous silver nitrate at room temperature, the masses of white precipitate produced are in the ratio 3 2 1. Suggest an explanation for these results. 

Decolorisation by Animal Charcoal. It sometimes hap pens (particularly with aromatic and heterocyclic compounds) that a crude product may contain a coloured impurity, which on recrystallisation dissolves in the boiling solvent, but is then partly occluded by crystals as they form and grow in the cooling solution. Sometimes a very tenacious occlusion may thus occur, and repeated and very wasteful recrystallisation may be necessary to eliminate the impurity. Moreover, the amount of the impurity present may be so small that the melting-point and analytical values of the compound are not sensibly affected, yet the appearance of the sample is ruined. Such impurities can usually be readily removed by boiling the substance in solution with a small quantity of finely powdered animal charcoal for a short time, and then filtering the solution while hot. The animal charcoal adsorbs the coloured impurity, and the filtrate is usually almost free from extraneous colour and deposits therefore pure crystals. This decolorisation by animal charcoal occurs most readily in aqueous solution, but can be performed in almost any organic solvent. Care should be taken not to use an excessive quantity... 

Dissolve a few drops of nitromethane in 10% sodium hydroxide solution. Add a few crystals of sodium nitrite and shake. Now add dilute sulphuric acid drop by drop. A brownish-red coloration develops, but fades again when an excess of acid is added. The sulphuric acid has thus liberated nitrous acid, which has in turn reacted with the nitromethane to give a nitrolic acid, the sodium salt of which is CH3NO2 + ONOH = CH(N02) N0H + HgO reddish-brown in colour, probably owing to mesomeric ions of the type ... 

O NCH NO 0 N CHN 0 An excess of sulphuric acid then converts the coloured sodium salt back to the almost colourless nitrolic acid. 

For purification, transfer the acid to a 150 ml. flask containing 60 ml. of water, boil the mixture under reflux, and then add acetic acid in 5 ml. portions down the condenser until almost all the solid has dissolved avoid an excess of acetic acid by ensuring that the solvent action of each addition is complete before the next portion is added. A small suspension of insoluble impurity may remain. Add 2 g. of animal charcoal, boil the solution again for 10-15 minutes, and then filter it through a preheated Buchner funnel. Cool and stir the filtrate, which will deposit pale cream-coloured crystals of the acid. Collect as before and if necessary repeat the recrystallisation. Yield of pure acid, 9 g. m.p. 227-229°. 

Now cork the flask securely, and shake it vigorously for about 5 minutes the solution should now have only a faint brown colour due to unchanged iodine. Cool the mixture in ice-water, pour it into a separating-funnel, and extract it twice with water to remove sodium iodide and most of the ethanol. Then shake the residual ethereal solution with a dilute aqueoussolution of sodium thiosulphate the excess of iodine is thus removed and the... 

Colorations or coloured precipitates are frequently given by the reaction of ferric chloride solution with.(i) solutions of neutral salts of acids, (ii) phenols and many of their derivatives, (iii) a few amines. If a free acid is under investigation it must first be neutralised as follows Place about 01 g. of the acid in a boiling-tube and add a slight excess of ammonia solution, i,e., until the solution is just alkaline to litmus-paper. Add a piece of unglazed porcelain and boil until the odour of ammonia is completely removed, and then cool. To the solution so obtained add a few drops of the "neutralised ferric chloride solution. Perform this test with the following acids and note the result ... 

Azo-dye formation. Dissolve 2-3 drops of aniline in 1 ml. of cone. HCl and add 3 ml. of water. Shaike to dissolve any hydrochloride which may have separated and cool in ice. Add a few drops of 20% sodium nitrite solution. Add this cold diazonium solution to a cold solution of the phenol in an excess of aqueous NaOH solution. Solutions or precipitates of azo-dyes ranging in colour from orange through scarlet to dark red, according to the phenol used, are obtained. Note in particular that i-naphthol gives a brownish-red, 2-naphthol a scarlet precipitate. Catechol decomposes. 

Ferric chloride reaction. For the success of this reaction it is important that the solution should be neutral. Excess of acid usually inhibits the production of colour or precipitate, and excess of alkali gives a reddish-brown precipitate of ferric hydroxide. A neutral solution may be made as follows ... 

Phthalein reaction. Fuse together carefully in a dry test-tube a few crystals of phthalic acid or of a phthalate and an equal quantity of ph tol moistened with 2 drops of cone. H2SO4. Cool, dissolve in water and add NaOH solution in excess the bright red colour of phenolphthalein in alkaline solution is produced. 

To a cold aqueous solution of benzoquinone, add 1 drop of sulphurous acid solution (SOj-water) the solution turns deep green-brown owing to the intermediate formation of quinhydrone, CeH402,CeIl4(0H)2. Now add excess of sulphurous acid the solution becomes colourless owing to the formation of hydroquinone. Add a few drops of FeClj solution the reaction is reversed and the deep yellow colour (distinct from that of FeCl ) is restored. 

Make a concentrated solution of anthracene in hot acetone. To about 2 ml. of this solution add a cold concentrated acetone solution of picric acid drop by drop, and note the formation of a red coloration which becomes deeper on further addition of the acid. If excess of picric acid is added, however, the solution becomes paler in colour, and this is to be avoided if possible. Boil to ensure that both components are in solution and then transfer to a small porcelain basin or watch-glass ruby-red crystals of anthracene picrate separate out on cooling. The product, however, is often contaminated with an excess of either anthracene or of picric acid, which appear as yellowish crystals. 

Weigh out accurately about 2 g. of glycine, transfer to a 250 ml. graduated flask, dissolve in distilled water, make up to the mark, and mix well. Transfer 25 ml. of the solution to a conical flask, add 2 drops of phenolphthalein, and then again add dilute sodium hydroxide very carefully until the solution is just faintly pink. No v add about 10 ml. (/. ., an excess) of the neutralised formaldehyde solution the pink colour of the phenolphthalein disappears immediately and the solution becomes markedly acid. Titrate with AI io sodium hydroxide solution until the pink colour is just restored. Repeat the process with at least two further quantities of 25 ml. of the glycine solution in order to obtain consistent readings. 

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