Silver salts, solubility

Although the data for the silver halides suggest that silver(I) fluoride is likely to be more soluble than the other silver halides (which is in fact the case), the hydration enthalpies for the sodium halides almost exactly balance the lattice energies. What then is the driving force which makes these salts soluble, and which indeed must be responsible for the solution process where this is endothermic We have seen on p. 66 the relationship AG = — TAS and... 

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. 

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... 

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. 

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. 

These salts are corrosive and are to be considered toxic because of the presence of Ag+ ions. The American Conference of Government Industrial Hygienists (ACGIH) (1992—1993) has adopted TWA values of 0.01 mg/m for silver metal and 0.01 mg/m for soluble silver salts. TWA for fluorides as F ions is 2.5 mg/m. The MSDS should be consulted prior to use. Skin contact and inhalation should be avoided. 

Only three simple silver salts, ie, the fluoride, nitrate, and perchlorate, are soluble to the extent of at least one mole per Hter. Silver acetate, chlorate, nitrite, and sulfate are considered to be moderately soluble. AH other silver salts are, at most, spatingly soluble the sulfide is one of the most iasoluble salts known. SHver(I) also forms stable complexes with excess ammonia, cyanide, thiosulfate, and the haUdes. Complex formation often results ia the solubilization of otherwise iasoluble salts. Silver bromide and iodide are colored, although the respective ions are colorless. This is considered to be evidence of the partially covalent nature of these salts. 

Organic Acid Salts. Slightly soluble or insoluble silver salts are precipitated when mono- and dicarboxylic aliphatic acids or their anions are... 

Perhalates. Whereas silver perchlorate [7783-93-9] AgClO, and silver periodate [15606-77-6] AglO, are well known, silver perbromate [54494-97-2] AgBrO, has more recendy been described (18). Silver perchlorate is prepared from silver oxide and perchloric acid, or by treating silver sulfate with barium perchlorate. Silver perchlorate is one of the few silver salts that is appreciably soluble in organic solvents such as glycerol, toluene, and chlorobenzene. 

Many other metal thiosulfates, eg, magnesium thiosulfate [10124-53-5] and its hexahydrate [13446-30-5] have been prepared on a laboratory scale, but with the exception of the calcium, barium [35112-53-9] and lead compounds, these are of Httle commercial or technical interest. Although thaHous [13453-46-8] silver, lead, and barium thiosulfates are only slightly soluble, other metal thiosulfates are usually soluble in water. The lead and silver salts are anhydrous the others usually form more than one hydrate. Aqueous solutions are stable at low temperatures and in the absence of air. The chemical properties are those of thiosulfates and the respective cation. 

In a linear complex, the coordination number is 2, corresponding to one group on each side of the central atom. The silver-ammonia complex, which generally forms when a very slightly soluble silver salt such as silver chloride dissolves in aqueous ammonia, is an example, as shown in Figure 22-6. Another example of a linear com-... 

These reactions take place with sparingly soluble silver salts, and hence provide a method for the determination of the halide ions Cl", Br, I-, and the thiocyanate ion SCN ". The anion is first precipitated as the silver salt, the latter dissolved in a solution of [Ni(CN)4]2", and the equivalent amount of nickel thereby set free is determined by rapid titration with EDTA using an appropriate indicator (murexide, bromopyrogallol red). 

The method may be applied to those anions (e.g. chloride, bromide, and iodide) which are completely precipitated by silver and are sparingly soluble in dilute nitric acid. Excess of standard silver nitrate solution is added to the solution containing free nitric acid, and the residual silver nitrate solution is titrated with standard thiocyanate solution. This is sometimes termed the residual process. Anions whose silver salts are slightly soluble in water, but which are soluble in nitric acid, such as phosphate, arsenate, chromate, sulphide, and oxalate, may be precipitated in neutral solution with an excess of standard silver nitrate solution. The precipitate is filtered off, thoroughly washed, dissolved in dilute nitric acid, and the silver titrated with thiocyanate solution. Alternatively, the residual silver nitrate in the filtrate from the precipitation may be determined with thiocyanate solution after acidification with dilute nitric acid. 

Discussion. The theory of the titration of cyanides with silver nitrate solution has been given in Section 10.44. All silver salts except the sulphide are readily soluble in excess of a solution of an alkali cyanide, hence chloride, bromide, and iodide do not interfere. The only difficulty in obtaining a sharp end point lies in the fact that silver cyanide is often precipitated in a curdy form which does not readily re-dissolve, and, moreover, the end point is not easy to detect with accuracy. 

Silver(I) does not disproportionate in aqueous solution and, in almost all its compounds, silver has oxidation number +1. Apart from silver nitrate, AgN03, and silver fluoride, silver salts are generally only sparingly soluble in water. Silver nitrate is the most important compound of silver and the starting point for the manufacture of silver halides for use in photography. 

Other metallic elements form ionic compounds with cation charges ranging from -F1 to + 3. Aluminum nitrate nonahydrate, A1 (N03)3 9 H2 O, is composed of cations, NO3 anions, and water molecules. Silver nitrate (AgNO ), which contains Ag cations, is a soluble silver salt that is used in silver plating. 

Silver salts demonstrate how complexation enhances solubility. Figure 18-13 shows that silver will precipitate or dissolve in aqueous solution depending on the species that are present. Starting with a solution of silver nitrate, addition of aqueous NaCl causes AgCl to precipitate ... 

It is widely recognized that the solvent in which any chemical reaction takes place is not merely a passive medium in which relevant molecules perform the solvent itself makes an essential contribution to the reaction. The character of the solvent will determine which chemical species are soluble enough to enter solution and hence to react, and which species are insoluble, and thus precipitate out of solution, thereby being prevented from undergoing further chemical change. In the case of water, as will be seen, polar and ionic species are the ones that most readily dissolve. But even so, mere polarity or ionic character is not sufficient to ensure solubility. Solubility depends on a number of subtle energetic factors, and the possible interactions between water and silver chloride, for example, do not fulfil the requirements despite the ionic nature of the silver salt. Hence silver chloride is almost completely insoluble in water. 

Various silver salts can be reduced to silver metal readily at temperatures well below 200 °C through different pathways [32]. We therefore used silver salt as nucleation inducing agent. Ag(acac) was used because of its good solubility in diphenyl ether. The morphology evolution of Pt multipods and nanoparticles was followed by TEM. 

The tests for metallic and acid radicals in chemical analysis are essentially tests for ions. For example, all soluble silver salts release silver ions in solution in water likewise, all... 

Rather than utilizing complete transmetallation reactions, mixed metal silver(i) aryl complexes 8-11 were obtained from the reaction of soluble silver salts with arylgold(i) complexes possessing ancillary phosphine or arsine ligands, as shown in Scheme l.29,30... 

All silver salts are insoluble. Exceptions AgN03 and AgCl04 AgC2H302 and Ag2SQ4 are moderately soluble. 

Silver occurs naturally in several oxidation states, the most common being elemental silver (Ag°) and the monovalent ion (Ag+). Soluble silver salts are, in general, more toxic than insoluble salts. In natural waters, the soluble monovalent species is the form of environmental concern. Sorption is the dominant process that controls silver partitioning in water and its movements in soils and sediments. As discussed later, silver enters the animal body through inhalation, ingestion, mucous membranes, and broken skin. The interspecies differences in the ability of animals to accumulate, retain, and eliminate silver are large. Almost all of the total silver intake is usually... 

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