Ammoniac

C2H3N. Colourless liquid with strong ammoniacal smell b.p. 56 C. Miscible with water and strongly basic. Prepared commercially from 2-aminoelhanol. Pure dry aziridine is comparatively stable but it polymerizes explosively in the presence of traces of water. Carbon dioxide is sufficiently acidic to promote polymerization. 

Dimeihylamine, C2H7N, (CH3)2NH. Colourless, inflammable liquid with an ammoniacal odour, mp -96" C, b.p. 7°C. Occurs naturally in herring brine. Prepared in the laboratory by treating nitrosodimetbyl-aniline with a hot solution of sodium hydroxide. Dimethylamine is largely used in the manufacture of other chemicals. These include the solvents dimethylacetamide and dimethyl-formamide, the rocket propellant unsym-metrical dimethylhydrazine, surface-active agents, herbicides, fungicides and rubber accelerators. 

Tollens reagent An ammoniacal solution of silver oxide which is used as a lest for aldehydes, which, unlike ketones, cause the deposition of a silver mirror. 

The soda-ammonia process occurs in two main stages. First, brine is saturated with ammonia gas and this ammoniacal brine is then treated with carbon dioxide. The equilibrium... 

JiVith ammoniacal or hydrochloric acid solution of copper(I) chloride, carbon monoxide forms the addition compound CuCl. CO. 2H2O. This reaction can be used to quantitatively remove carbon monoxide from gaseous mixtures. 

The solid readily dissolves chemically in concentrated hydrochloric acid, forming a complex, and in ammonia as the colourless, linear, complex cation [H3N -> Cu <- NHj] (cf AgCl) if air is absent (in the presence of air, this is oxidis to a blue ammino-copper(II) complex). This solution of ammoniacal copper(I) chloride is a good solvent or carbon monoxide, forming an addition compound CuCl. CO. H2O, and as such is used in gas analysis. On passing ethyne through the ammoniacal solution, a red-brown precipitate of hydrated copper(I) dicarbide (explosive when dry) is obtained ... 

In ammoniacal solution (in which the ion [AgfNHjlj]" is formed) it is readily reduced to silver (see above) by many organic compounds. The use of silver nitrate for marking clothes depends on its reduction by the material to black silver. The reduction also occurs even when the neutral solution comes in contact with the skin, and a black stain is left. Thus solid silver nitrate rubbed on the skin leaves a black deposit and so is used in surgery as a mild caustic—hence the old name for silver nitrate of lunar caustic. 

If ethyne is passed through an ammoniacal solution of silver nitrate, there is a white precipitate of silver dicarbide (cf. copperflH ... 

Note cautiously the characteristic odour of acetaldehyde which this solution possesses. Then with the solution carry out the following general tests for aldehydes described on p. 341 Test No. I (SchiflF s reagent). No. 3 (Action of sodium hydroxide). No. 4 (Reduction of ammoniacal silver nitrate). Finally perform the two special tests for acetaldehyde given on p. 344 (Nitroprusside test and the Iodoform reaction). 

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. 

Many diazonium compounds when treated with an ammoniacal cuprous Formerly known as Diphenic acid. 

Give silver mirror with ammoniacal silver nitrate. 

Reduction of ammoniacal silver nitrate. Place about 5 ml. of AgNOj solution in a thoroughly clean test-tube, and add 2-3 drops of dil. NaOH solution. Add dil. ammonia solution, drop by drop, until the precipitated silver oxide is almost redissolved, then add 2 - 3 drops of formaldehyde or acetaldehyde. A silver mirror is formed. 

Gives some of the tests for acetaldehyde, but more feebly e.g., it restores the colour to SchifF s reagent, gives a yellow resin with NaOH, and responds to the nitroprusside test. With ammoniacal AgN03, it gives a silver minor only after 2 -3 minutes warming. It does not give the iodoform reaction. 

Does not reduce ammoniacal AgNOj (except on long standing). 

Do not reduce ammoniacal AgN03 or Fehling s solution (dis tinction from aldehydes). 

Reduction of ammoniacal silver nitrate. Add a few drops of a neutral solution of a formate to ammoniacal AgNO (see Test 4, p. 342). A silver mirror or more usually a grey precipitate of metallic sih er is produced on boiling. 

Does not reduce KMnO, HgCl, or ammoniacal AgNOj. 

Reduction of ammoniacal silver nitrate. Add i drop of dil. NaOH solution to about 5 ml. of AgNO, solution, and add dil. NH solution drop by drop until the silver oxide is almost redissolved. Add AgNO, solution until a faint but permanent precipitate is obtained (see p.525). Then add 0 5 ml. of a neutral tartrate solution. Place the tube in warm water a silver mirror is formed in a few minutes. 

Does not reduce ammoniacal AgNO, solution cf. tartaric acid)... 

Reduction of ammoniacal silver nitrate. Place 2 ml. of dilute silver nitrate solution in a clean test-tube. Add 1 drop of NaOH solution and then add dil. ammonia drop by drop until the precipitate formed by the NaOH is just not redissolved. Now add 1-2 ml. of glucose solution and place the test-tube in a water-bath at 50-60° a silver mirror is produced in 1 - 2 minutes. 

Does not reduce ammoniacal silver nitrate or Fehling s solution. If, however, the sucrose solution is warmed for some time with the reagent in question, slight hydrolysis to glucose and fructose does take place and reduction then occurs occasionally samples of sucrose will rapidly give a silver mirror, presumably owing to impurities. 

Reduces ammoniacal silver nitrate, and Fehling s solution. 

Does not reduce ammoniacal silver nitrate or Fehling s solution, and does not form an osazone. 

Oxidation, (a) Ammoniacal silver nitrate. To a few ml. of ammoniacal AgNOj (preparation, p. 525), add a few drops of cold aqueous benzo quinone solution a silver mirror or (more generally) a dark precipitate of metallic silver is formed in the cold. 

Treat with ammoniacal silver nitrate solution and warm. 

Formation of silver mirror or precipitate of silver indicates reducing agent. (This is often a more sensitive test than I (a) above, and some compounds reduce ammoniacal silver nitrate but are without effect on Fehling s solution.) Given by aldehydes and chloral hydrate formates, lactates and tartrates reducing sugars benzoquinone many amines uric acid. 

Ammoniacal Silver Nitr. te. Add 1 drop of 10% aqueous NaOH solution to about 5 ml. of silver nitrate solution in a test-tube then add dilute NHg drop by drop with shaking until only a trace of undissolved Ag O remains. A number of reductions require the presence of Ag " ions. It is often advisable, therefore, after adding the ammonia to add silver nitrate solution until a faint but permanent precipitate is obtained. The solution should always be prepared in small quantities immediately before use, and any unexpended solution thrown away afterwards. If the solution is kept for some time, it may form explosive by-products. 

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