Deep Blue

Manganates V), hypomanganatcs, [Mn04] . Deep blue ion (Mn02 in cone. K.OH [Mn04] plus excess [SOa] ). The salts are rapidly hydrolysed. 

Dinitrogen trioxide, N2O3. Only stable in solid state (m.p. — 102 C). Pale blue solid giving deep blue liquid the gas contains some ONNO2 molecules. Prepared from NO and O2 or NO and N2O4 with freezing decomposes to NO and NO,. 

This reaction also occurs slowly when sodium is dissolved in liquid ammonia initially a deep blue solution is formed which then decomposes giving hydrogen and sodium amide. 

Solutions of alkali metals in liquid ammonia are used in organic chemistry as reducing agents. The deep blue solutions effectively contain solvated electrons (p. 126), for example... 

At room temperature ozone is a slightly blue diamagnetie gas which condenses to a deep blue liquid. It has a characteristic smell, and is toxic. Ozone is a very endothermic compound ... 

A different d orbital splitting results and the absorption now results in a deep blue colour ... 

It is readily dehydrated on warming, to give the black oxide CuO. It dissolves in excess of concentrated alkali to form blue hydroxo-cuprate(II) ions, of variable composition it is therefore slightly amphoteric. If aqueous ammonia is used to precipitate the hydroxide, the latter dissolves in excess ammonia to give the deep blue ammino complexes, for example [Cu(NH3)4(H20)2] ... 

When a copper(II) salt dissolves in water, the complex aquo-ion [Cu(H2p)6P is formed this has a distorted octahedral (tetragonal) structure, with four near water molecules in a square plane around the copper and two far water molecules, one above and one below this plane. Addition of excess ammonia replaces only the four planar water molecules, to give the deep blue complex [Cu(NH3)4(H20)2] (often written as [Cu(NHj)4] for simplicity). TTo obtain [Cu(NH3)6], water must be absent, and an anhydrous copper(II) salt must be treated with liquid ammonia. 

Metallic Derivatives, (a) Cuprous Acetylide. CujCg. Prepare an ammoniacal solution of cuprous chloride by first adding dilute ammonia to 2-3 ml. of dilute copper sulphate solution until the initial precipitate just redissolves and a clear deep-blue solution is obtained now add an aqueous solution of hydroxylamine hydrochloride drop by drop with shaking until the solution becomes first green and then completely colourless, the cupric salt being thus reduced to the cuprous derivative. 

Ferric chloride solution is then added to com ert the sodium ferrocyanide to the deep blue ferric ferrocyanide (or Prussian Blue), dilute sulphuric acid being also added to dissolve any ferrous and ferric hydroxides present in the other-... 

Ltebermann Reaction To 1 minute crystal of sodium nitrite in a clean dry test-tube add 0 5 g. of phenol and heat very gently for about 20 seconds allow to cool and add twice the volume of cone. H2S04. On rotating the tube slowly in order to mix the contents, a deep green or deep blue coloration develops (some times only after i 2 minutes). Dilute cautiously with water the solution turns red. Now add an excess of NaOH solution the green or blue coloration reappears. 

Form deep blue copper salts usually sparingly soluble in water. 

Repeat using using 1- or 2-naphthol in place of resorcinol the aqueous layer becomes deep blue, fading to green. 

Disappearance of the deep blue colour and precipitation of cuprous oxide indicates reducing agents such as ... 

Toluidine. Transient green, deep blue and then a deep blue precipitate. Usually a very fast reaction. 

Monomethylaniline. Deep blue, changing to a slate blue. 

Dissolve 1 g. of the secondary amine in 3-5 ml. of dilute hydrochloric acid or of alcohol (in the latter case, add 1 ml. of concentrated hydrochloric acid). Cool to about 5° and add 4-5 ml. of 10 per cent, sodium nitrite solution, and allow to stand for 5 minutes. Add 10 ml. of water, transfer to a small separatory funnel and extract the oil with about 20 ml. of ether. Wash the ethereal extract successively with water, dilute sodium hydroxide solution and water. Remove the ether on a previously warmed water bath no flames should be present in the vicinity. Apply Liebermann s nitroso reaction to the residual oil or solid thus. Place 1 drop or 0 01-0 02 g. of the nitroso compovmd in a dry test-tube, add 0 05 g. of phenol and warm together for 20 seconds cool, and add 1 ml. of concentrated sulphuric acid. An intense green (or greenish-blue) colouration will be developed, which changes to pale red upon pouring into 30-50 ml. of cold water the colour becomes deep blue or green upon adding excess of sodium hydroxide solution. 

P-Hydroxy-a-naphthaldehyde, Equip a 1 litre three-necked flask with a separatory funnel, a mercury-sealed mechanical stirrer, and a long (double surface) reflux condenser. Place 50 g. of p-naphthol and 150 ml. of rectified spirit in the flask, start the stirrer, and rapidly add a solution of 100 g. of sodium hydroxide in 210 ml. of water. Heat the resulting solution to 70-80° on a water bath, and place 62 g. (42 ml.) of pure chloroform in the separatory funnel. Introduce the chloroform dropwise until reaction commences (indicated by the formation of a deep blue colour), remove the water bath, and continue the addition of the chloroform at such a rate that the mixture refluxes gently (about 1 5 hours). The sodium salt of the phenolic aldehyde separates near the end of the addition. Continue the stirring for a further 1 hour. Distil off the excess of chloroform and alcohol on a water bath use the apparatus shown in Fig. II, 41, 1, but retain the stirrer in the central aperture. Treat the residue, with stirring, dropwise with concentrated hydrochloric acid until... 

An alternative method of removing the aniline is to add 30 ml. of concentrated sulphuric acid carefully to the steam distillate, cool the solution to 0-5°, and add a concentrated solution of sodium nitrite until a drop of the reaction mixture colours potassium iodide - starch paper a deep blue instantly. As the diazotisation approaches completion, the reaction becomes slow it will therefore be necessary to teat for excess of nitrous acid after an interval of 5 minutes, stirring all the whUe. About 12 g. of sodium nitrite are usually required. The diazotised solution is then heated on a boiling water bath for an hour (or until active evolution of nitrogen ceases), treated with a solution of 60 g. of sodium hydroxide in 200 ml. of water, the mixture steam-distilled, and the quinoline isolated from the distillate by extrsM-tion with ether as above. 

Purification of anthracene. Dissolve 0-3 g. of crude anthracene (usually yellowish in colour) in 160-200 ml. of hexane, and pass the solution through a column of activated alumina (1 5-2 X 8-10 cm.). Develop the chromatogram with 100 ml. of hexane. Examine the column in the hght of an ultra-violet lamp. A narrow, deep blue fluorescent zone (due to carbazole, m.p. 238°) will be seen near the top of the column. Immediately below this there is a yellow, non-fluorescent zone, due to naphthacene (m.p. 337°). The anthracene forms a broad, blue-violet fluorescent zone in the lower part of the column. Continue the development with hexane until fluorescent material commences to pass into the filtrate. Reject the first runnings which contain soluble impurities and yield a paraffin-hke substance upon evaporation. Now elute the column with hexane-benzene (1 1) until the yellow zone reaches the bottom region of the column. Upon concentration of the filtrate, pure anthracene, m.p. 215-216°, which is fluorescent in dayhght, is obtained. The experiment may be repeated several times in order to obtain a moderate quantity of material. 

Iodine compounds are important in organic chemistry and very useful in medicine. Iodides, and thyroxine which contains iodine, are used internally in medicine, and as a solution of KI and iodine in alcohol is used for external wounds. Potassium iodide finds use in photography. The deep blue color with starch solution is characteristic of the free element. 

Dyes for polyesters or cellulose acetate fiber-, deep blue to greenish blue shades... 

As early as 2500 bce m India indigo was used to dye cloth a deep blue The early Phoenicians discovered that a purple dye of great value Tyrian purple could be extracted from a Mediterranean sea snail The beauty of the color and its scarcity made purple the color of royalty The availability of dyestuffs underwent an abrupt change m 1856 when William Henry Perkin an 18 year old student accidentally discovered a simple way to prepare a deep purple dye which he called mauveme from extracts of coal tar This led to a search for other synthetic dyes and forged a permanent link between industry and chemical research... 

Ethyl bis-(2,4-dinitrophenyl) acetate (indicator) the stock solution is prepared by saturating a solution containing equal volumes of alcohol and acetone with the indicator pH range colorless 7.4-9.1 deep blue. This compound is available commercially. The preparation of this compound is described by Fehnel and Amstutz, Ind. Eng. Chem., Anal. Ed. 16 53 (1944), and by von Richter, Ber. 21 2470 (1888), who recommended it for the titration of orange- and red-colored solutions or dark oils in which the endpoint of phenol-phthalein is not easily visible. The indicator is an orange solid which after crystallization from benzene gives pale yellow crystals melting at 150-153.5°C, uncorrected. 

Iron, cobalt, and nickel catalyze this reaction. The rate depends on temperature and sodium concentration. At —33.5°C, 0.251 kg sodium is soluble in 1 kg ammonia. Concentrated solutions of sodium in ammonia separate into two Hquid phases when cooled below the consolute temperature of —41.6°C. The compositions of the phases depend on the temperature. At the peak of the conjugate solutions curve, the composition is 4.15 atom % sodium. The density decreases with increasing concentration of sodium. Thus, in the two-phase region the dilute bottom phase, low in sodium concentration, has a deep-blue color the light top phase, high in sodium concentration, has a metallic bronze appearance (9—13). 

A family of Ti(III) derivatives roughly parallels those of Ti(IV). Titariium(III) chelates are known, eg, titanium ttisacetylacetonate [14284-96-9] prepared in benzene from titanium trichloride, acetylacetone, and ammonia (185). This deep-blue compound is soluble in benzene but insoluble in water. 

The concentration of B ia natural Ilb diamonds is about 0.25 ppm and as much as 270 ppm ia synthesized crystals a crystal with about 10 ppm B is essentially deep blue. Dissolved nitrogen can range up to 2500 ppm atomic ia Type la natural stones and to about 500 ppm atomic for synthesized Type Ib. References 9, 14—19 provide qualifications on these data. 

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... 

Another ancient dye is the deep blue indigo [482-89-3], the presence of two bromine atoms at positions gives the dye Tyrian purple [19201 -53-7] once laboriously extracted from certain sea shells and worn by Roman emperors. 

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