Silver nitrate reaction

Review oxidation-reduction reactions as discussed in Chapter 3. Explain why the copper/silver nitrate reaction in this activity is an oxidation-reduction reaction. 

The original Marsh test involved burning and deposition of the arsenic upon a cold surface. Nowadays the mirror test is usually applied. The silver nitrate reaction (sometimes known as Hofmann s test) is very useful as a confirmatory test. 

Thiosulphate will be detected in the preliminary test with dilute sulphuric acid if it is found, it should be eliminated by heating the original mixture with dilute sulphuric acid until no more sulphur dioxide is evolved, evaporating the residual mixture just to dryness and then heating with 1-5m sodium carbonate solution, etc. The occurrence of thiosulphates in mixtures is comparatively rare and hence this special treatment prior to making the soda extract is rarely necessary. The interference of the S2Of ion with the silver nitrate reaction may... 

Silver Nitrate Reaction. The distillate is treated with nitric acid and silver nitrate the presence of hydrocyanic acid is shown by a white precipitate, which should be stable to the light, and readily soluble in ammonia and potassium hydroxide. 

Primary alcohols do not react at room temperature therefore, the alcohol is seen simply to dissolve. Secondary alcohols react slowly, whereas tertiary, benzylic, and allylic alcohols react instantly. These relative reactivities are explained on the same basis as the silver nitrate reaction, which is discussed in Experiment 52B. Primary carbocations are unstable and do not form under the conditions of this test hence, no results are observed for primary alcohols. 

Addition of silver nitrate to a solution of a bromide in nitric acid produces a cream-coloured precipitate of silver bromide, soluble in ammonia (but not so readily as silver chloride). The reaction may be used quantitatively, as for a chloride. 

In the former, it gives precipitates with halides (except the fluoride), cyanides, thiocyanates, chromates(VI), phosphate(V), and most ions of organic acids. The silver salts of organic acids are obtained as white precipitates on adding silver nitrate to a neutral solution of the acid. These silver salts on ignition leave silver. When this reaction is carried out quantitatively, it provides a means of determining the basicity of the acid... 

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). 

I. Reaction with cold silver nitrate solution. Add 2 ml. of 10% aqueous AgNOg solution to i ml. of methyl iodide and shake vigorously a yellow precipitate of Agl is formed in the cold. Add an excess of dil. HNO3 to show that the precipitate does not dissolve.f... 

Aromatic aldehydes react with the dimedone reagent (Section 111,70,2). All aromatic aldehydes (i) reduce ammoniacal silver nitrate solution and (ii) restore the colour of SchifiF s reagent many react with sodium bisulphite solution. They do not, in general, reduce Fehling s solution or Benedict s solution. Unlike aliphatic aldehydes, they usually undergo the Cannizzaro reaction (see Section IV,123) under the influence of sodium hydroxide solution. For full experimental details of the above tests, see under Ali-phalic Aldehydes, Section 111,70. They are easily oxidised by dilute alkaline permanganate solution at the ordinary temperature after removal of the manganese dioxide by sulphur dioxide or by sodium bisulphite, the acid can be obtained by acidification of the solution. 

Alternatively, treat a solution of 3 9 g. of the 6is-diazo ketone in 50 ml. of warm dioxan with 15 ml. of 20 per cent, aqueous ammonia and 3 ml. of 10 per cent, aqueous silver nitrate under reflux in a 250 or 500 ml. flask on a water bath. Nitrogen is gently evolved for a few minutes, followed by a violent reaction and the production of a dark brown and opaque mixture. Continue the heating for 30 minutes on the water bath and filter hot the diamide of decane-1 lO dicarboxyhc acid is deposited on cooling. Filter this off and dry the yield is 3 -1 g., m.p. 182-184°, raised to 184-185° after recrystallisation from 25 per cent, aqueous acetic add. Hydrolyse the diamide (1 mol) by refluxing for 2-5 hours with 3N potassium hydroxide (4 mols) acidify and recrystaUise the acid from 20 per cent, acetic acid. The yield of decane-1 10-dicarboxyhc acid, m.p. 127-128°, is almost quantitative. 

Reaction with alcoholic silver nitrate. To carry out the test, treat 2 ml. of a 2 per cent, solution of silver nitrate in alcohol with 1 or 2 drops (or 0 05 g.) of the compound. If no appreciable precipitate appears at the laboratory temperature, heat on a boiling water bath for several minutes. Some organic acids give insoluble silver salts, hence it is advisable to add 1 drop of dilute (5 per cent.) nitric acid at the conclusion of the test most silver salts of organic acids are soluble in nitric acid. 

Strike couldn t find any decent nitroethane synths except for a couple of Chemical Abstract articles. One suggestion is to treat 1.5 moles of Na2C02 with 1 mole of sodium ethylsulfite and 0.0645 moles of K2CO3 at 125-130°C. Another route would be to use silver nitrate and ethyl iodide [8 p119]. This type of reaction has been used to nitrate other paraffins and would probably work. 

TrialkyIboranes (p. 9), which can be synthesized from olefins and diborane, undergo alkyl coupling on oxidation with alkaline silver nitrate via short-lived silver organyls. Two out of three alkyl substituents are coupled in this reaction. Terminal olefins may be coupled by this reaction sequence in 40 - 80% yield. With non-terminal olefins yields drop to 30 - 50% (H.C. Brown, 1972C, 1975). 

Acetylene can be deterrnined volumetricaHy by absorption in Aiming sulfuric acid (or more conveniently in sulfuric acid activated with silver sulfate) or by reaction with silver nitrate in solution and titration of the nitric acid formed ... 

Sahcylaldehyde is readily oxidized, however, to sahcyhc acid by reaction with solutions of potassium permanganate, or aqueous silver oxide suspension. 4-Hydroxybenzaldehyde can be oxidized to 4-hydroxybenzoic acid with aqueous silver nitrate (44). Organic peracids, in basic organic solvents, can also be used for these transformations into benzoic acids (45). Another type of oxidation is the reaction of sahcylaldehyde with alkaline potassium persulfate, which yields 2,5-dihydroxybenzaldehyde (46). 

Silver Carbonate. Silver carbonate, Ag2C02, is produced by the addition of an alkaline carbonate solution to a concentrated solution of silver nitrate. The pH and temperature of the reaction must be carefully controlled to prevent the formation of silver oxide. A suspension of Ag2C02 is slightly basic because of the extensive hydrolysis of the ions present. Heating soHd Ag2C02 to 218°C gives Ag20 and CO2. 

Silver Permanganate. Silver permanganate [7783-98-4] AgMnO, is a violet soHd formed when a potassium permanganate solution is added to a silver nitrate solution. It decomposes upon heating, exposure to light, or by reaction with alcohol. 

Catalysts. Silver and silver compounds are widely used in research and industry as catalysts for oxidation, reduction, and polymerization reactions. Silver nitrate has been reported as a catalyst for the preparation of propylene oxide (qv) from propylene (qv) (58), and silver acetate has been reported as being a suitable catalyst for the production of ethylene oxide (qv) from ethylene (qv) (59). The solubiUty of silver perchlorate in organic solvents makes it a possible catalyst for polymerization reactions, such as the production of butyl acrylate polymers in dimethylformamide (60) or the polymerization of methacrylamide (61). Similarly, the solubiUty of silver tetrafiuoroborate in organic solvents has enhanced its use in the synthesis of 3-pyrrolines by the cyclization of aHenic amines (62). 

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