Blue 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. 

CH3)2N]3P0. M.p. 4°C, b.p. 232"C, dielectric constant 30 at 25 C. Can be prepared from dimethylamine and phosphorus oxychloride. Used as an aprotic solvent, similar to liquid ammonia in solvent power but easier to handle. Solvent for organolithium compounds, Grignard reagents and the metals lithium, sodium and potassium (the latter metals give blue solutions). 

Schweizer s reagent The dark blue solution obtained by dissolving Cu(OH)2 in concentrated ammonia solution. Used as a solvent for cellulose, the cellulose is precipitated on acidification. Used in the cuprammonium process for the manufacture of rayon. 

The alkali metals have the interesting property of dissolving in some non-aqueous solvents, notably liquid ammonia, to give clear coloured solutions which are excellent reducing agents and are often used as such in organic chemistry. Sodium (for example) forms an intensely blue solution in liquid ammonia and here the outer (3s) electron of each sodium atom is believed to become associated with the solvent ammonia in some way, i.e. the system is Na (solvent) + e" (sohem). 

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... 

If excess chloride ion is added to a blue solution containing... 

If copper is treated with a solution of dinitrogen tetroxide in ethyl ethanoate (acetate), a blue solution is obtained, which on evapora-... 

When cobalt(II) chloride was dissolved in water, a pink solution A was formed. The addition of concentrated hydrochloric acid to A gave a blue solution B. If solution A was treated with concentrated ammonia solution a blue-green precipitate was formed upon addition of further ammonia solution followed by the passage of air through the mixture, an orange-red solution C was produced. 

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. 

CH,),CHNO, -h HONO = (CH,),C(NO)NO, -h H,0 producing a blue solution. A tertiary nitro paraffin such as trimethylnitro-methane, (CH )jCNO, gives no reaction with nitrous acid. 

Make up a methylene-blue solution by grinding 0 1 g. with water and making up to i litre with water. 

Place 5 ml. of milk in each of two test-tubes A and B. Boil the milk in B thoroughly for 2 minutes to destroy the enzyme, and cool. Then in each test-tube place i ml. of the acetaldehyde solution and i ml of the methylene-blue solution. Mix gently by inverting the tubes avoid shaking with air. Now place A and B in a water-bath maintained at 40-50. After a time (usually about 20 minutes) the dye in A is completely decolorised except at the surface, while B is unaffected. 

Sots i. Prepared by addition as much of a solution of 1.5 g of lithium in 75 ml of liquid NH3 to 1 1 of the commercial product as to cause a uniformly blue solution, for a least 1 min. The liquid is subsequently distilled two times at 10-20 mmHg. 

Dissolve 2 g dye in 1 L water. The blue solution is oxidized to pale red. 

The dark blue solution containing 5—10% of cellulose with a DP of 1000—2000 is filtered through a series of plate-and-frame filter presses using fine mesh metal screens to remove any particles that might block the spinneret holes. It is then deaerated under vacuum and stored ready for spinning. Unlike viscose dope, the cuprammonium cellulose [9050-09-3] solution is relatively stable. 

For solvent extraction of a tetravalent vanadium oxyvanadium cation, the leach solution is acidified to ca pH 1.6—2.0 by addition of sulfuric acid, and the redox potential is adjusted to —250 mV by heating and reaction with iron powder. Vanadium is extracted from the blue solution in ca six countercurrent mixer—settler stages by a kerosene solution of 5—6 wt % di-2-ethyIhexyl phosphoric acid (EHPA) and 3 wt % tributyl phosphate (TBP). The organic solvent is stripped by a 15 wt % sulfuric acid solution. The rich strip Hquor containing ca 50—65 g V20 /L is oxidized batchwise initially at pH 0.3 by addition of sodium chlorate then it is heated to 70°C and agitated during the addition of NH to raise the pH to 0.6. Vanadium pentoxide of 98—99% grade precipitates, is removed by filtration, and then is fused and flaked. 

Phosphoms determination involves the conversion of phosphoms to soluble phosphate by digesting the coal ash with a mixture of sulfuric, nitric, and hydrofluoric acids (18). Phosphate is precipitated as ammonium phosphomolybdate, which may be reduced to give a blue solution that is determined colorimetricaHy or volumetricaHy (D2795) (18). 

Alkannin occurs in the roots of the plant as the alkah-sensitive ester of angelic acid (62). It may be extracted from the roots by using boiling light petroleum ether. Treatment of this extract with dilute sodium hydroxide gives a blue solution from which the dye is precipitated by the addition of acid. The cmde product is purified by vacuum sublimation (63). Its stmcture (11) is a hydroxylated naphthoquinone with a long, unsaturated side chain (64,65) it has the (3)-configuration. 

After the addition is complete, stirring is continued at -30°C for 10 min to produce a grey-blue or dark blue solution of the cuprate (Note 51. 

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.]... 

The general reaction procedure and apparatus used are exactly as described in Procedure 2. Ammonia (465 ml) is distilled into a 2-liter reaction flask and to this is added 165mlofisopropylalcoholandasolutionof30g(0.195 mole) of 17/ -estradiol 3-methyl ether (mp 118.5-120°) in 180 ml of tetrahydrofuran. The steroid is only partially soluble in the mixture. A 5 g portion of sodium (26 g, 1.13 g-atoms total) is added to the stirred mixture and the solid dissolves in the light blue solution within several min. As additional metal is added, the mixture becomes dark blue and a solid (matted needles) separates. Stirring is inefficient for a few minutes until the mass of crystals breaks down. All of the sodium is consumed after 1 hr and 120 ml of methanol is then added to the mixture with care. The product is isolated as in Procedure 4h 2. After being air-dried, the solid weighs 32.5 g (ca. 100% for a monohydrate). A sample of the material is dried for analysis and analyzed as described in Procedure 2 enol ether, 91% unreduced aromatics, 0.3%. The crude product may be crystallized from acetone-water or preferably from hexane. 

Ammoniacal aiptous chloride is made as follows Eoil up copper oxide and metallic copper with cone hydrochloric acid for a short time until the liquid is nearly colourless, and pour the liquid into water. The white cuprous chloride is washed once or twice by decantation and dissolved in a strong solution of ammonium chloride. When required a little ammonia is added sufficient to give a clear blue solution... 

Add to 2 01 3 c c. of the solution two nr three drops of copper siiljihate,. and then eaiistie soda, until a deal blue solution is olitained, and lusit to boiling. Red ( ujirous ovidc is piocipi-tated. 

The presence of a nitmso-coinpound may be detected as follows. Melt together a niiniite quantity of nitrosophenol and a few crystals of [ilienol. Add ahout 2 c.c. concentrated sulphuric acid and waiin ciy gently. A blue solution is obtained, which changes to red on dilution with water, and back to blue on adding alkali (Liebermann s nitioso reaction sec Reaction, p. 180). Sec AppL Hiiix, ]). 280. 

Europium and Yb display further similarity with the alkaline earth metals in dissolving in liquid ammonia to give intense blue solutions, characteristic of solvated electrons and presumably also containing [Ln(NH3)x]. The solutions are strongly reducing and decompose on standing with the precipitation of orange Eu(NH2)2 and brown Yb(NH2)2 (always contaminated with Yb(NH2)3) which are isostructural with the Ca and Sr amides. 

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