were there no cupric compounds, or if silver gave stable compounds of the higher oxide, AgO, the resemblance would be as close as that between chlorine and bromine or zinc and cadmium; but silver compounds corresponding to AgO are quite unknown. Although silver peroxide-which was regarded as AgO, but which Berthelot (1880) recognised as the sesquioxide Ag2O,-is known, still it does not form any true salts, and consequently cannot be placed along with cupric oxide. In distinction to copper, silver as a metal does not oxidise under the influence of heat; and its oxides, Ag2O and Ag2O3, easily lose oxygen (see Note 8 tri). Silver does not oxidise in air at the ordinary pressure, and is therefore classed among the so-called noble metals. It has a white colour, which is much purer than that of any other known metal, especially when the metal is chemically pure. In the arts silver is always used alloyed, because chemically-pure silver is so soft that it wears exceedingly easily, whilst when fused with a small amount of copper, it becomes very hard, without losing its colour. 13

13 There are not many soft metals; lead, tin, copper, silver, iron, and gold are somewhat soft, and potassium and sodium very soft. The metals of the alkaline earths are sonorous and hard, and many other metals are even brittle, especially bismuth and antimony. But the very slight significance which these properties have in determining the fundamental chemical properties of substances (although, however, of immense importance in the practical applications of metals) is seen from the example shown by zinc, which is hard at the ordinary temperature, soft at 100°, and brittle at 200°.

As the value of silver depends exclusively on its purity, and as there is no possibility of telling the amount of impurities alloyed with it from its external appearance, it is customary in most countries to mark an article with the amount of pure silver it contains after an accurately-made analysis known as the assay of the silver. In France the

assay of silver shows the amount of pure silver in 1,000 parts by weight; in Russia the amount of pure silver in 96 parts-that is, the assay shows the number of zolotniks (4.26 grams) of pure silver in one pound (410 grams) of alloyed silver. Russian silver is generally 84 assay-that is, contains 84 parts by weight of pure silver and 12 parts of copper and other metals. French money contains 90 p.c. (in the Russian system this will be 864 assay) by weight of silver English coins and jewellery contain 925 p.c. of silver]; the silver rouble is of 83 assay-that is, it contains 86.8 p.c. of silver-and the smaller Russian silver coinage is of 48 assay, and therefore contains 50 p.c. of silver. Silver ornaments and articles are usually made in Russia of 84 and 72 assay. As the alloys of silver and copper, especially after being subjected to the action of heat, are not so white as pure silver, they generally undergo a process known as 'blanching' (or

Silver occurs in nature, both in a native state and in certain compounds. Native silver, however, is of rather rare occurrence. A far

'pickling') after being worked up. This consists in removing the copper from the surface of the article by subjecting it to a dark-red heat and then immersing it in dilute acid. During the calcination the copper on the surface is oxidised, whilst the silver remains unchanged; the dilute acid then dissolves the copper oxides formed, and pure silver is left on the surface. The surface is dull after this treatment, owing to the removal of a portion of the metal by the acid. After being polished the article acquires the desired lustre and colour, so as to be indistinguishable from a pure silver object. In order to test a silver article, a portion of its mass must be taken, not from the surface, but to a certain depth. The methods of assay used in practice are very varied. The commonest and most often used is that known as cupellation. It is based on the difference in the oxidisability of copper, lead, and silver. The cupel is a porous cup with thick sides,

made by compressing bone ash. The porous mass of bone ash absorbs the fused oxides, especially the lead oxide, which is easily fusible, but it does not absorb the unoxidised metal. The latter collects into a globule under the action of a strong heat in the cupel, and on cooling solidifies into a button, which may then be weighed. Several cupels are placed in a muffle. A muffle is a semi-cylindrical clay vessel, shown in the accompanying drawing. The sides of the muffle are pierced with several orifices, which allow the access of air into it. The muffle is placed in a furnace, where it is strongly heated. Under the action of the air entering the muffle the copper of the silver alloy is oxidised, but as the oxide of copper is infusible, or, more strictly speaking, difficultly fusible, a certain quantity of lead is added to the alloy; the lead is also oxidised by the air at the high temperature of the muffle, and gives the very fusible lead oxide. The copper oxide then fuses with the lead oxide, and is absorbed by the cupel, whilst the silver remains as a VOL. II.

EE

If this

greater quantity of silver occurs in combination with sulphur, and especially in the form of silver sulphide, Ag2S, with lead sulphide or copper sulphide, or the ores of various other metals. The largest amount of silver is extracted from the lead in which it occurs. lead be calcined in the presence of air, it oxidises, and the resultant lead oxide, PbO (litharge' or 'silberglätte,' as it is called), melts into a mobile liquid, which is easily removed. The silver remains in an unoxidised metallic state. 14 This process is called cupellation.

bright white globule. If the weight of the alloy taken and of the silver left on the cupel be determined, it is possible to calculate the composition of the alloy. Thus the essence of cupellation consists in the separation of the oxidisable metals from silver, which does not oxidise under the action of heat. A more accurate method, based on the precipitation of silver from its solutions in the form of silver chloride, is described in detail in works on analytical chemistry.

14 In America, whence the largest amount of silver is now obtained, ores are worked containing not more than p.c. of silver, whilst atp.c. its extraction is very profitable. Moreover, the extraction of silver from ores containing not more than 0:01 p.c. of this metal is sometimes profitable. The majority of the lead smelted from galena contains silver, which is extracted from it. Thus near Arras, in France, an ore is worked which contains about 65 parts of lead and 0·088 part of silver in 100 parts of ore, which corresponds with 136 parts of silver in 100,000 parts of lead. At Freiberg, in Saxony, the ore used (enriched by mechanical dressing) contains about 09 of silver, 160 of lead, and 2 of copper in 10,000 parts. In every case the lead is first extracted in the manner described in Chapter XVIII., and this lead will contain all the silver. Not unfrequently other ores of silver are mixed with lead ores, in order to obtain an argentiferous lead as the product. The extraction of small quantities of silver from lead is facilitated by the fact (Pattinson's process) that molten argentiferous lead in cooling first deposits crystals of pure lead, which fall to the bottom of the cooling vessel, whilst the proportion of silver in the unsolidified mass increases owing to the removal of the crystals of lead. The lead is enriched in this manner until it contains part of silver, and is then subjected to cupellation on a larger scale. According to Park's process, zine is added to the molten argentiferous lead, and the alloy of Pb and Zn, which first separates out on cooling, is collected. This alloy is found to contain all the silver previously contained in the lead. The addition of 0'5 p.c. of aluminium to the zinc (Rossler and Edelman) facilitates the extraction of the Ag from the resultant alloy besides preventing oxidation; for, after re-melting, nearly all the lead easily runs off (remains fluid), and leaves an alloy containing about 30 p.c. Ag and about 70 p.c. Zn. This alloy may be used as an anode in a solution of ZnCl2, when the Zn is deposited on the cathode, leaving the silver with a small amount of Pb, &c. behind. The silver can be easily obtained pure by treating it with dilute acids and cupelling.

The ores of silver which contain a larger amount of it are: silver glance, Ag2S (sp. gr. 7·2); argentiferous-copper glance, CuAgS; horn silver or chloride of silver, AgC1; argentiferous grey copper ore; polybasite, MRS, (where M-Ag, Cu, and R÷Sb, As), and argentiferous gold. The latter is the usual form in which gold is found in alluvial deposits and ores. The crystals of gold from the Berezoffsky mines in the Urals contain 90 to 95 of gold and 5 to 9 of silver, and the Altai gold contains 50 to 65 of gold and 36 to 38 of silver. The proportion of silver in native gold varies between these limits in other localities. Silver ores, which generally occur in veins, usually contain native silver and various sulphur compounds. The most famous mines in Europe are in Saxony (Freiberg), which has a yearly output of as much as 26 tons of silver, Hungary, and Bohemia (41 tons). In Russia, silver is extracted in the Altai and at Nerchinsk (17 tous). The richest silver mines known are in America, especially in Chili (as much as 70 tons), Mexico (200 tons), and more particularly in the Western States of North America. The

Commercial silver generally contains copper, and, more rarely, other metallic impurities also. Chemically pure silver is obtained either by cupellation or by subjecting ordinary silver to the following treatment. The silver is first dissolved in nitric acid, which converts it and the copper into nitrates, Cu(NO3), and AgNO,; hydrochloric acid is then added to the resultant solution (green, owing to the presence of the cupric salt), which is considerably diluted with water in order to retain the lead chloride in solution if the silver contained lead. The copper

and many other metals remain in solution, whilst the silver is precipitated as silver chloride. The precipitate is allowed to settle, and the liquid is decanted off; the precipitate is then washed and fused with sodium carbonate. A double decomposition then takes place, sodium chloride and silver carbonate being formed; but the latter decomposes into metallic silver, because the silver oxide is decomposed by heat : Ag2CO2 = Ag2 +O+ CO2. The silver chloride may also be mixed with metallic zinc, sulphuric acid, and water, and left for some time, when the zinc removes the chlorine from the silver chloride and precipitates the silver as a powder. This finely-divided silver is called 'molecular silver.' 15

richness of these mines may be judged from the fact that one mine in the State of Nevada (Comstock, near Washoe and the cities of Gold Hill and Virginia), which was discovered in 1859, gave an output of 400 tons in 1866. In place of cupellation, chlorination may also be employed for extracting silver from its ores. The method of chlorination consists in converting the silver in an ore into silver chloride. This is either done by a wet or by a dry method, roasting the ore with NaCl. When the silver chloride is formed, the extraction of the metal is also done by two methods. The first consists in the silver chloride being reduced to metal by means of iron in rotating barrels, with the subsequent addition of mercury which dissolves the silver, but does not act on the other metals. The mercury holding the silver in solution is distilled, when the silver remains behind. This method is called amalgamation. The other method is less frequently used, and consists in dissolving the silver chloride in sodium chloride or in sodium thiosulphate, and then precipitating the silver from the solution. The amalgamation is then carried on in rotating barrels containing the roasted ore mixed with water, iron, and mercury. The iron reduces the silver chloride by taking up the chlorine from it. The technical details of these processes are described in works on metallurgy. The extraction of AgCl by the wet method is carried on (Patera's process) by means of a solution of hyposulphite of sodium which dissolves AgCl (see Note 23), or by lixiviating with a 2 p.c. solution of a double hyposulphite of Na and Cu (obtained by adding CuSO, to Na2S2O3). The resultant solution of AgCl is first treated with soda to precipitate PbCO5, and then with Na2S, which precipitates the Ag and Au. The process should be carried on rapidly to prevent the precipitation of CuS from the solution of CuSO, and Na,S.05.

15 There is another practical method which is also suitable for separating the silver from the solutions obtained in photography, and consists in precipitating the silver by oxalic acid. In this case the amount of silver in the solution must be known, and 23 grams of oxalic acid dissolved in 400 grams of water must be added for every 60 grams of silver in solution in a litre of water. A precipitate of silver oxalate, Ag,CO4, is then obtained, which is insoluble in water but soluble in acids. Hence, if the liquid contain any free acid it must be previously freed from it by the addition of sodium carbonate.

Chemically-pure silver has an exceeding pure white colour, and a specific gravity of 10.5. Solid silver is lighter than the molten metal, and therefore a piece of silver floats on the latter: The fusingpoint of silver is about 950° C., and at the high temperature attained by the combustion of detonating gas it volatilises. 16 By employing silver reduced from silver chloride by milk sugar and caustic potash, and distilling it, Stas obtained silver purer than that obtained by any other means; in fact, this was perfectly pure silver. The vapour of silver has a very beautiful green colour, which is seen when a silver wire is placed in an oxyhydrogen flame."

It has long been known (Wöhler) that when nitrate of silver, AgNO3, reacts as an oxidising agent upon citrates and tartrates, it is able under certain conditions to give either a salt of suboxide of silver (see Note 19) or a red solution, or to give a precipitate of metallic silver reduced at the expense of the organic substances. In 1889 Carey Lea, in his researches on this class of reactions, showed that soluble The resultant precipitate of silver oxalate is dried, mixed with an equal weight of dry sodium carbonate, and thrown into a gently-heated crucible. The separation of the silver then proceeds without an explosion, whilst the silver oxalate if heated alone decomposes with explosion.

According to Stas, the best method for obtaining silver from its solutions is by the reduction of silver chloride dissolved in ammonia by means of an ammoniacal solution of cuprous thiosulphate; the silver is then precipitated in a crystalline form. A solution of ammonium sulphite may be used instead of the cuprous salt.

16 Silver is very malleable and ductile; it may be beaten into leaves 0-002 mm. in thickness. Silver wire may be made so fine that 1 gram is drawn into a wire 24 kilometres long. In this respect silver is second only to gold. A wire of 2 mm. diameter breaks under a strain of 20 kilograms.

17 In melting, silver absorbs a considerable amount of oxygen, which is disengaged on solidifying. One volume of molten silver absorbs as much as 22 volumes of oxygen. In solidifying, the silver forms cavities like the craters of a volcano, and throws off metal owing to the evolution of the gas; all these phenomena recall a volcano on a miniature scale (Dumas). Silver which contains a small quantity of copper or gold, &c., does not show this property of dissolving oxygen.

The absorption of oxygen by molten silver is, however, an oxidation, but it is at the same time a phenomenon of solution. One cubic centimetre of molten silver can dissolve twenty-two cubic centimetres of oxygen, which, even at 0°, only weighs 003 gram, whilst 1 cubic centimetre of silver weighs at least 10 grams, and therefore it is impossible to suppose that the absorption of the oxygen is attended by the formation of any definite compound (rich in oxygen) of silver and oxygen (about 45 atoms of silver to 1 of oxygen) in any other but a dissociated form, and this is the state in which substances in solution must be regarded (Chapter I.)

Le Chatelier showed that at 300° and 15 atmospheres pressure silver absorbs so much oxygen that it may be regarded as having formed the compound Ag,0, or a mixture of Ag, and Ag,O. Moreover, silver oxide, Ag2O, only decomposes at 300 under low pressures, whilst at pressures above 10 atmospheres there is no decomposition at 300 but only at 400°.

Stas showed that silver is oxidised by air in the presence of acids. V. d. Pfordten confirmed this, and showed that an acidified solution of potassium permanganate rap diy dissolves silver in the presence of air.