Silver -, salt

SELECTIVE OXIDATIONS OF HYDROXY STEROIDS / 241 VIII. SILVER SALTS 

The use of silver (II) salts, particularly argentic picolinate, as reagents for hydroxyl oxidation has also been disclosed recently. The reaction may be run in acid, neutral or basic media in aqueous or polar organic solvents at room or slightly elevated temperatures. Primary alcohols may be oxidized to aldehydes or acids depending on the conditions used. Amines and trivalent phosphorous compounds are more sensitive to oxidation with this reagent than are hydroxyl groups. 

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Anlhraquinone-2-su phonic acid. The sodium salt, commonly called silver salt , is used for the preparation of alizarin and 2-aminoanthraquinone and to prepare Fieser s solution. Aminoanthraquinone derivatives are the basis of many dyestuffs. 

Fieser s solution An aqueous alkaline solution of sodium anthraquinone -sulphonale (silver salt) reduced with sodium dithionite, Na2S204, and used as a scrubbing solution for partially removing O2 from, e.g., N2. 

One prevalent strategy for this involves tire use of a phase transfer agent, such as tetraoctyl ammonium bromide, to bring gold and silver salts into an organic phase [12, and. Reduction of tire metal salts... 

All the silver halides are sensitive to light, decomposing eventually to silver. In sunlight, silver chloride turns first violet and finally black. The use of these compounds in photography depends on this (see below). (All silver salts are, in fact, photosensitive—the neck of a silver nitrate bottle is black owing to a deposit of silver.)... 

It was known in the sixteenth century that silver salts were photosensitive, but it was not until the beginning of the nineteenth century, when Herschel found that silver chloride was soluble in sodium thiosulphate, that photography became possible. 

Silver nitrate, the most common silver salt, is obtained by dissolving the metal in nitric acid ... 

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... 

By the action of alkyl halides on the silver salt of the acid. 

This method is to be recommended when only a small quantity of the acid is availa ble, since both the conversion of the acid into its silver salt (p. 445) and of the latter to the ester give almost quantitative yields. 

To obtain the free acid, the ester is hydrolysed by ethanolic potash to the dipotassium salt, which is converted into the insoluble silver salt. A hot aqueous... 

In similar circumstances, silver salts leave a residue of metallic silver lead and copper salts usually leave a residue of the corresponding oxide calcium and barium salts leave a resirlne of the carbonate or oxide. Identify the metal in all such cases by the usual tests of qualitative inorganic analysis. Metals other than the above are seldom encountered in elementan qualitative analysis. 

REACTIONS AND IDENTIFICATION 325 drop. JNote that the white precipitate of silver salts turns black (showing the presence of silver cyanide). Now add an excess of mercurous nitrate the black precipitate redissolves, but the silver halide remains undissolved. 

I. Molecular Weight of Acids by Analysis of Silver Salts. 

The silver salts of most carboxylic acids are only sparingly soluble in cold water, and hence are readily prepared. Moreover they very rarely contain water of crystallisation, and therefore when dried can be analysed without further treatment. The analysis itself is simple, rapid and accurate, because gentle ignition of a weighed quantity of the silver salt in a crucible drives off the organic matter, leaving a residue of pure metallic silver. 

Since the silver salts of the carboxylic acids are usually soluble in dilute nitric acid, they must be prepared by treating an aqueous solution of a neutral salt of the acid (and not the free acid itself) with silver nitrate solution. It is not practicable to attempt to neutralise the acid with sodium or potassium hydroxide solution, because the least excess of alkali would subsequently cause the white silver salt to be contaminated with brown silver oxide. The general method used therefore to obtain a neutral solution j to dissolve the acid in a small excess of ammonia solution, and then to boil the solution until all free... 

The Molecular weight of the acid itself is clearly equal to that of the silver salt minus the atomic weight of sih er plus the weight of hydrogen displaced by G X 107-9 ... 

From the silver salt. By refluxing the dry silver salt with an alkyl halide in anhydrous ether, benzene or absolute alcohol solution, for example ... 

The method is generally applicable when other modes of esterification are either slow, inefficient, or likely to cause isomerisation it is, however, time-consuming and expensive. Small quantities of acid impurities are sometimes produced, hence it is advisable to wash the ester with saturated sodium bicarbonate solution. The silver salt can usually be prepared by dissolving the acid in the calculated quantity of standard ammonium hydroxide solution and... 

Preparation of silver maleate. Dissolve 65 g. of pure maleic acid (Section 111,143) in the calculated quantity of carefully standardised 3-5N aqueous ammonia solution in a 1-htre beaker and add, whilst stirring mechanically, a solution of 204 g. of silver nitrate in 200 ml. of water. Filter oflf the precipitated silver maleate at the pump, wash it with distilled water, and press well with the back of a large flat glass stopper. Dry in an electric oven at 50-60° to constant weight. The yield of the dry silver salt is 150 g. Store in a vacuum desiccator in the dark. 

Saccharic acid. Use the filtrate A) from the above oxidation of lactose or, alternatively, employ the product obtained by evaporating 10 g. of glucose with 100 ml. of nitric acid, sp. gr. 1 15, until a syrupy residue remains and then dissolving in 30 ml. of water. Exactly neutralise at the boiling point with a concentrated solution of potassium carbonate, acidify with acetic acid, and concentrate again to a thick syrup. Upon the addition of 50 per cent, acetic acid, acid potassium saccharate sepa rates out. Filter at the pump and recrystaUise from a small quantity of hot water to remove the attendant oxahc acid. It is necessary to isolate the saccharic acid as the acid potassium salt since the acid is very soluble in water. The purity may be confirmed by conversion into the silver salt (Section 111,103) and determination of the silver content by ignition. 

Sodium anthraquinone-p-sulphonate ( silver salt ). Place 60 g. of fuming sulphuric acid (40-50 per cent. SO3) in a 250 or 500 ml. round-bottomed flask and add 50 g. of dry, finely-powdered anthra-quinone (Section IV,145). Fit an air condenser to the flask and heat the mixture slowly in an oil bath, with occasional shaking, so that at the end of 1 hour the temperature has reached 160°. Allow to cool and pour the warm mixture carefully into a 2 litre beaker containing 500 g. of crushed ice. Boil for about 15 minutes and filter off the unchanged anthraquinone at the pump. Neutralise the hot filtrate with sodium hydroxide and allow to cool, when the greater part of the sodium anthra-quinone-p-sulphonate separates as silvery glistening plates ( silver salt ). Filter these with suction and dry upon filter paper or upon a porous plate. A second crop of crystals may be isolated by concentration of the trate to half the original volume. The yield is 40-45 g. 

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. 

Hydrazinothiazoles form stable complexes with Mn ", Ni. Cd Cu ", Co ", Fe ", and Fe " this property was used to detect small amounts of these salts in mixtures by paper chromatography (547, 548). Some infrared features of the complexes formed with the silver salts and with the mercuric salts have been reported (1583). 

Silver All silver salts are insoluble. Exceptions AgNOg and AgC104 AgC2H302 and ... 

Acetylene Bromine, chlorine, brass, copper and copper salts, fluorine, mercury and mercury salts, nitric acid, silver and silver salts, alkali hydrides, potassium metal... 

For Volhard methods identified by an asterisk ( ) the precipitated silver salt must be removed before carrying out the back titration. 

If a mixture of an insoluble silver salt and Ag2S is used to make the membrane, then the membrane potential also responds to the concentration of the anion of the added silver salt. Thus, pellets made from a mixture of Ag2S and AgCl can serve as a Ck ion-selective electrode, with a cell potential of... 

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