1911 Encyclopædia Britannica/Silver

​SILVER (symbol Ag, from the Latin argentum, atomic weight 107·88 (O＝16)), a metallic chemical element, known from the earliest times and of great importance as a “noble” metal for articles of value—coinage, ornamentation and jewelry. Etymologically the word “silver” probably refers to the shining appearance or brightness of the metal. The Latin argentum is cognate with the Greek ixpyvpos, silver, which in turn is derived from apyos, shining. The Hebrew Keseph is connected with a root meaning “to be pale.” The alchemists named it Luna or Diana, and denoted it by the crescent moon; the first name has survived in lunar caustic, silver nitrate. Silver is widely diffused throughout nature, occurring in minute amount in sea-water, and in the mineral kingdom as the free metal, as an amalgam with mercury and as alloys with gold, platinum, copper and other metals. Native silver is occasionally met with in metalliferous veins, where it has been formed by the alteration of silver-bearing minerals. It crystallizes in the cubic system, but the crystals are usually distorted and indistinctly developed: twisted wire-like forms are much more common. The best crystallized specimens have been obtained from Kongsberg in Norway, large masses, weighing as much as 5 cwts., having been found. It is also found in other silver mines, especially those of Mexico, Peru and Chile; in the Lake Superior copper mining region it occurs in association with native copper. The element is a constituent of many mineral sulphides, some of which are of sufficiently frequent occurrence to rank as ores of silver. Of these the more important are noticed under Metallurgy; here we may notice the rarer minerals. Silver sulphide, Ag₂S, occurs naturally as the orthorhombic acanthite, and the cubic argentite; the telluride, Ag₂Te, named hessite, assumes cubic forms; other tellurides containing silver are petzite, (Ag,Au)₂Te, and sylvanite, AuAgTe₄. In association with antimonious and arsenious sulphides, silver sulphide forms many important minerals, which sometimes present dimorphous forms, reflecting the dimorphism of silver sulphide; moreover, the corresponding arsenious and antimonious compounds are frequently isomorphous. This is illustrated by the hexagonal pyrargyrite 3Ag₂S·Sb₂S₃, and proustite, 3Ag₂S·As₂S₃, and the monoclinic pyrostilpnite, isomeric with pyrargyrite, and xanthoconite, isomeric with proustite. Other pairs of isomorphous argentiferous minerals are: the cubic polybasite, 9Ag₂S·Sb₂S₃, and pearceite, 9Ag₂S·As₂S₃; and the germanium minerals argyrodite, 4Ag₂S·GeS₂, and canfieldite, 4Ag₂S·(Sn,Ge)S₂.

Physical Properties.—In appearance silver presents a pure white colour with a perfect metallic lustre. It is the most malleable and ductile of all metals with the exception of gold: one gramme can be drawn out into a wire 180 metres long, and the leaf can be beaten out to a thickness of 0·00025 mm.; traces of arsenic, antimony, bismuth and lead, however, make it brittle. In hardness it is superior to gold, but inferior to copper. Its specific gravity, according to G. Rose, lies between 10·514 and 10·619 at 14°; an average value is 10·57. Its specific heat is 0·05701 (Regnault) or 0·0559 (Bunsen); its coefficient of linear expansion is 0·00001921. Its thermal conductivity is, according to Wiedemann and Franz, superior to that of other metals, being in the ratio of 100 : 74 as compared with copper and 100 : 54 with gold; it is the most perfect conductor of electricity, standing to copper in the ratio 100:75, and to gold 100:73. Silver melts at about 1000°C; recent determinations give 960·7° (Heycock and Neville) and 962 (Becquerel); at higher temperatures it volatilizes with the formation of a pale blue vapour (Stas). Its vapour density has been determined at 2000°, and corresponds to a monatomic molecule. When molten, silver occludes the oxygen of the atmosphere, absorbing 20 times its own volume of the gas; the oxygen, however, is not permanently retained, for on cooling it is expelled with great violence; this phenomenon is known as the “spitting” of silver. It is prevented by preserving the molten metal from contact with air by covering the surface with non-oxidizing agents, or by traces of copper, bismuth or zinc.

Chemical Properties.—Silver is not oxidized by oxygen, but resembles mercury in being oxidized by ozone. It has no action on water. It is readily soluble in dilute nitric acid, nitric oxide and silver nitrate being formed; it also dissolves in hot, strong sulphuric acid, sulphur dioxide being evolved. Hydrochloric acid forms a surface film of silver chloride; hydriodic acid ​readily dissolves it, while hydrofluoric acid is without action. Sulphuretted hydrogen is decomposed with the formation of a black coating of silver sulphide; this is the explanation of the black tarnish seen when silver is exposed to the fumes of coal gas, and other sulphuretted compounds, such as occur in eggs. The so-called “oxidized” silver is a copper-silver alloy coated superficially with a layer of the sulphides by immersion in sodium sulphide or otherwise. Silver combines with the free halogens on heating and also with sulphur.

Production.—The economic questions which attend the production of silver and the influence which gold and silver exercise on prices are treated in the articles Money and Bimetallism; the reader is referred to the former article for the history of silver production and to the topographical headings for the production of specific countries. Since the middle of the 19th century the annual production has increased: the following table gives the average annual production in 1000 oz. over certain periods:—

1841–1850.	1851–1860.	1861–1865.	1866–1870.	1871–1875.	1876–1880.	1881–1885.	1886–1890.	1891–1895.
25,090	28,792	35,402	43,052	63,318	78,777	87,272	110,356	158,942
1900.	1901.	1902.	1903.	1904.	1905.	1906.	1907.	1908.
180,093	174.851	164,560	170,128	182,262	189,830	165,640	184,894	203,186

From the metallurgical point of view, silver ores may be classified as real silver ores and argentiferous ores. The former consist of silver minerals and gangue (vein matter, country-rock). The leading silver minerals are native silver; argentite or silver glance, Ag₂S, usually containing small amounts of lead, copper and tin; dyscrasite or antimonial silver, Ag₂Sb to Ag₁₃Sb, an isomorphous mixture of silver and antimony; proustite or light red silver ore, Ag₃AsS₃; pyrargyrite or dark red silver ore, Ag₃SbS₃; stephanite, Ag₅SbS₄; miargyrite, AgSbS₂; stromeyerite, CuAgS; polybasite, 9(Cu₂S,Ag₂S)·(Sb₂S₃,As₂S₃); cerargyrite or horn silver, AgCl; bromite or bromargyrite, AgBr; embolite, Ag(Cl,Br); iodite or iodargyrite, Agl. Metalliferous products containing silver arise in many operations; the chief products which may yield silver economically are copper and lead mattes, burnt argentiferous pyrites and certain drosses and scums. Argentiferous ores consist of silver-bearing base-metal minerals and gangue. Lead and copper ores, carrying silver in some form or other, are the leading representatives. The silver is extracted from the gangue with the base metal, usually by smelting, and the two are then separated by special processes (see Lead).

Milling, i.e. amalgamation and lixiviation, is cheaper than smelting, but the yield in silver is lower. Often it is more profitable to smelt real silver ores with argentiferous ores than to mill them, the greater cost being more than balanced by the increased yield. Milling is practised mainly in isolated localities near the mine producing the ore. As any given region is opened up by railways, cheapening transportation, milling is apt to give way to smelting. Thus on the American continent, which produces the bulk of the world’s silver, milling is still prominent in S. America and Mexico, while in the United States it has to a considerable extent been replaced by smelting.

Amalgamation is based on the property of quicksilver to extract the silver from finely-pulverized ore and collect it in the form of an amalgam. When the rock has been separated from the amalgam by a washing operation, the quicksilver is recovered by distillation in an iron retort, and the remaining crude retort-silver melted into bars and shipped to a refinery, which removes the impurities, the leading one of which is copper. A silver ore is either free-milling or refractory, that is, the silver mineral is readily amalgamated or it is not. In free-milling ore the silver is present either in the native state, or as chloride or as simple sulphide. Complex silver minerals (sulph-arsenides and antimonides) which are difficult to amalgamate must be made amenable to quicksilver, and the simplest way of doing this is to convert the silver into chloride. This is imperfectly accomplished, in the wet way, by cupric and cuprous chloride solutions, but completely so, in the dry way, by roasting with salt (chloridizing roasting). According as a preliminary chloridizing roast has or has not been given, the process is classed as roast-amalgamation or raw-amalgamation. The leading raw-amalgamation processes are the Patio and Washoe; then follow the Cazo, Fondon and Krohnke; of the roast-amalgamation processes, the European Barrel or Freiberg, the Reese River and the Franck-Tina are the most important.

Chloridizing Roasting.—In a chloridizing roast chlorine produces its effect as nascent chlorine or gaseous hydrochloric acid. The leading reagents are salt (NaCl), sulphur trioxide (SO3, produced in the roasting), and steam (H 2 0). The decomposition of salt is expressed by 2NaCl+2SO₃ = Na₂SO₄+SO₂+Cl₂. In the presence of water-vapour the following reaction takes place: 2NaCl+SO₃+H₂ = Na₂SO₄+2HCl. As some water-vapour is always present, hydrochloric acid will invariably be formed with the chlorine. The roasting is carried on in hand and mechanical reverberatory furnaces, and Occasionally in muffle-furnaces. A chloridation of over 90% silver is the rule.

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Lixiviation. — Ores suited for amalgamation can, as a rule, be successfully leached. In leaching, the silver ore is subjected to the action of solvents, which dissolve the silver; from the solution the silver is precipitated and converted into a marketable product.

The leading solvents are aqueous solutions of thiosulphates, un- systematically but generally termed hyposulphites. Sodium chloride, characteristic of the Augustin process in which the ores, after a chloridizing roast, were extracted with brine, and the silver pre- cipitated by copper, has almost wholly fallen into disuse; and potassium cyanide, which has become a very important solvent for finely divided gold, is rarely used in leaching silver ores. The use of sodium hyposulphite as solvent, and sodium sulphide as precipitant, was proposed in 1846 by Hauch and in 1850 by Percy, and put into practice in 1858 by Patera {Patera process); calcium hyposulphite with calcium polysulphide was first used by Kiss in i860 (Kiss process, now obsolete) ; sodium hyposulphite with calcium poly- sulphide was adopted about 1880 by O. Hofmann (Hofmann process) ; finally, sodium hyposulphite with cuprous hyposulphite was first applied by Russell in 1884, who included in his process the acidula- tion of the first wash-water (to neutralize any harmful alkaline reaction), and the separation of lead with sodium carbonate from the silver solution previous to precipitating with sodium sulphide (see C. A. Stetefeldt, The Lixiviation of Silver Ores with Hyposulphite Solutions, &c, New York, 1888).

In all processes the silver ore is finely crushed, usually by rolls, as, because making few fines, they leave the ore in the best condition for leaching. As a. rule the ore is subjected to a preliminary chloridizing roast, though occasionally it may be leached raw. The vats in common use are circular wooden tanks, 16-20 ft. in diameter and 8-9 ft. deep if the leached ore is to be removed by sluicing, 5 ft. if by shovelling. They ha^e a false bottom, with cloth or gravel filters.

The basis of the following outline is the Patera process. The ore, supposed to have been salt-roasted, is charged loosely into the leaching vat and treated with water (to which sulphuric acid or copper sulphate may have been added), to remove soluble salts, which might later on be precipitated with the silver (base-metal chlorides), or overcharge the solution (sodium chloride and sulphate), or interfere with the solvent power (sodium sulphate). The vat is filled with water from above or below, in- and out-flow are then so regulated as to keep the ore covered with water. Any silver dissolved by the first wash-water is recovered by a. separate treatment. After the wash- water has been drained off, the ore is ready for the silver solvent. This is a solution containing up to 2 % of sodium hyposulphite, of which one part dissolves 0-485 part silver chloride, equivalent to 0-365 part metallic silver, to form double hyposulphites. Silver arsenate and antimoniate are also readily soluble, metallic silver slightly so, silver sulphide not at all. (In the Russell-process double salts: 4Na 2 S503-3Cu2S 2 03, and 8NaoSo0 3 -3Cu3S 2 3 the metallic silver and silver sulphide are readily soluble ; thus it supplements that of Patera.)

After the silver has been dissolved by percolation, the last of the solvent still in contact with the ore is replaced by a second wash- water. The silver solution, collected in a circular precipitating vat (10 ft. in diameter and 10 ft. deep), is treated with sodium sulphide (or calcium polysulphide), unless sodium carbonate was first added to throw down any lead, present in the ore as sulphate, that had gone into solution. Silver sulphide falls out as a black mud, with about 50 % silver, and the solvent will be regenerated.

If the sodium cuprous hyposulphite was used as a solvent in addition to the simple sodium hyposulphite, cuprous sulphide will be precipitated with the silver sulphide, and the precipitate will be of lower grade. At some works the silver is precipitated with sodium sulphide, and the liquor, after having been separated from the silver sulphide, is treated with calcium polysulphide, that by the precipi- tation of calcium sulphate the accumulation of sodium sulphate may . be prevented. The precipitated silver (copper) sulphide is filtered, dried, and usually shipped to silver-lead works to be refined ; some- times it is converted into metallic silver at the works. The solution, freed from silver, is used again as solvent. Lixiviation has many advantages over amalgamation. It permits coarser crushing of the ore, the cost of plant is lower, the power required is nominal, the cost of chemicals is lower than that of quicksilver, less water is necessary, and the extraction is often higher, as silver arsenate and antimoniate are readily soluble, while they are not decomposed in amalgamation. On the other hand, silver and silver sulphide are readily amalga- mated ; and while they are not dissolved in the Patera process, they are in the Russell process.

Mention may be made of the Ziervogel process, introduced at Hettstadt in 1841 for the purpose of extracting silver from copper mattes. In principle it consists in oxidizing silver sulphide to the sulphate which is soluble in water, the silver being then precipitable by metallic copper. This process when carefully carried out, especi- ally as to the details of the roasting process whereby the silver sulphide is oxidized, yields 92 % of the silver originally present.

Electrolytic Methods. — Crude silver generally contains small amounts of copper, gold, bismuth, lead and other metals. To

eliminate these impurities, electrolytic methods have been devised; of these that of Moebius is the most important and will be described in detail.

Under his earlier patent of 1884, cast crude silver anode plates, about \ in. thick, and thin rolled silver cathodes, were suspended in a i%, slightly acid, solution of silver nitrate contained in tarred wooden tanks. The deposit from this solution even with low current- densities is pulverulent and non-coherent, and therefore during electrolysis wooden scrapers are automatically and intermittently passed over the surface of the cathode to detach the loose silver, which falls into cloth trays at the bottom of the tanks. These trays are removed at intervals, and the silver washed and cast into bars, which should contain over 99-9% of pure metal. The relatively electro-negative character of silver ensures that with moderate current densities no metal (other than precious metals) will be deposited with it ; hence, while the solution is pure a current-density of 30 amperes per sq. ft. of cathode may be used, but as copper accumulates in it, the current-density must be diminished to (say) 15 to 20 amperes per sq. ft., and a little extra nitric acid must be added, in order to prevent the co-deposition of copper. A pressure of 1 -5 volt usually suffices when the space between the electrodes is 2 in. The tanks were arranged in groups of seven on the multiple system.

Of the metals present in the anode, practically all, except gold, pass into solution, but, under the right conditions, only silver should deposit. The whole of the gold is recovered as anode slime in cloth bags surrounding the anodes. Practical results with a large plant indicate an expenditure of 1-23 electrical horse-power hours per 100 oz. (Troy) of refined silver. In later installations, under the 1895 patent, the anodes are placed horizontally on a porous tray resting within the solution above an endless silver band revolving, also horizontally, over rollers placed near the ends of a long shallow tank. The revolving band forms the cathode, and at one end makes a rubbing contact with a travelling belt placed at an angle so that the crystals of silver detached thereby from the cathode are con- veyed by it from the solution anddeposited outside.

Alloy scrap containing chiefly copper with, say 5 or 6% of gold, and other metals, and up to 40 or 50% of silver, is often treated electrolytically. Obviously, with modifications, the Moebius process could be applied. Other systems have been devised. Borchers uses the alloy, granulated, in an anode chamber separated from the cathode cell by a porous partition through which the current, but not electrolyte, can pass freely. The anode residue is collected in the angular bottom of the tank, the electrolyte passes from the anode chamber to a series of tanks in which the more electro-negative constituents (silver, &c.) are chemically separated, and thence to the cathode chamber, where the copper is deposited electrolytically, thence it passes again to the anode chamber and so completes the cycle. In one form of the apparatus a rotating cathode is used. Dietzel has described (Zeitschrift fur Elektrochem., 1899, vol. vi. p. 81) the working of his, somewhat similar, process at Pforzheim, where about 130 ft of the alloy was being treated by it daily in 1899. The alloy is cast into anode plates about -J in. thick, and placed in the anode chamber beneath the cathode cell, and separated from it by linen cloth. In the upper compartment are two large revolving horizontal cathode cylinders. Acidified copper nitrate solution is run into this cell, copper is deposited, and the more or less spent solution then passes through the linen partition, and, taking up metal from the anodes by electrolytic solution, is run out of the trough through a series of _ vessels filled with copper by which the silver _ is precipitated by simple exchange; after acidification the resulting silver-free copper solution is returned to the cathode cell for the deposition of the copper, the solution being employed again and again until too impure for use.

Chemically Pure Silver. — Even the best " fine " silver of commerce contains a few thousandth-parts of copper or other base metal. To produce perfectly pure metal the usual method is to first prepare pure chloride and then to reduce the chloride to metal. This may be effected by mixing the dry chloride with one-fifth of its weight of pure quicklime or one-third of its weight of dry sodium carbonate, and fusing the mixture in a fire-clay crucible at a bright red heat. In either case we obtain a regulus of silver lying under a fused slag of chloride. The fused metal is best granulated by pouring it into a mass of cold water. A convenient wet method for small quantities is to boil the recently precipitated chloride (which must have been produced and washed in the cold) with caustic soda and just enough sugar to reduce the silver oxide (Ag 2 0) transitorily produced. The silver in this case is obtained as a yellowish grey heavy powder, which is easily washed by decantation; but it tends to retain unreduced chloride, which can be removed only by fusion with carbonate of soda.

Stas in his stoichiometric determinations employed the following process as yielding a metal which comes nearer ideal purity. Slightly cupriferous silver is made into dry nitrate and the latter fused to ​reduce any platinum nitrate that may be present to metal. The fused mass is dissolved in dilute ammonia and diluted to about fifty times the weight of the silver it contains. The filtered (blue) solution is now mixed with an excess of solution of ammonium sulphite, and allowed to stand. After twenty-four hours about one-half of the silver has separated out in crystals ; from the mother-liquor the rest comes down promptly on application of a water-bath heat. The rationale of the process is that the sulphite hardly acts upon the dis- solved oxide of silver, but it reduces some of the cupric oxide to cuprous oxide, which reduces its equivalent of silver oxide to silver and reforming cupric oxide which passes through the same cycle.

Alloys of Silver. — Silver readily alloys with many metals, and the admixture generally differs in physical properties from the pure metal. Thus arsenic, antimony, bismuth, tin or zinc render the metal brittle, so that it fractures under a die or rolling mill; copper, on. the other hand, increases its hardness, makes it tougher and more readily fusible. Consequently copper-silver alloys receive extensive application for coinage and jewelry. The composition of the alloy is stated in terms of its " fineness," the proportion of silver in iooo parts of alloy. Generally copper-silver alloys separate into two layers of different composition on fusion; an exception is the alloy Ag 3 Cu 2 , investigated by A. I. F. Levol, corresponding to a fineness of 719, which remained perfectly homogeneous.

The extent to which the properties of silver are modified by addition of copper depends on the fineness of the alloy produced. The addition of even three parts of copper to one of silver does not quite obliterate the whiteness of the noble metal. According to Kamarsch, the relative abrasion suffered by silver coins of the degrees of fineness named is as follows : —

Fineness .... 312 750 900 993

Abrasion .... I 2-3 3-9 9-5

The same observer established the following relation between fine- ness p and specific gravity of alloys containing from 375 to 875 of silver per 1000: — sp. gr. =0-001647 />+8-833.

The fusing points of all copper-silver alloys lies below that of pure copper; that of British standard silver is lower than even that of pure silver

Compounds of Silver.

Silver forms one perfectly characterized oxide, Ag 2 0, from which is derived a series of stable salts, and probably several less perfectly known ones. Argentic or silver oxide, Ag20, is obtained as a dark brown precipitate by adding potash to a solution of a silver salt; on drying at 6o°-8o° it becomes almost black. It is also obtained by digesting freshly precipitated silver chloride with potash. It is sparingly soluble in water (one part in 3000) ; and the moist oxide frequently behaves as the hydroxide, AgOH, i.e. it converts alkyl haloids into alcohols. It begins to decompose into silver and oxygen at 250 . Silver peroxide, AgO, appears under certain conditions as minute octahedra when a solution of silver nitrate is electrolysed, or as an amorphous crust in the electrolysis of dilute sulphuric acid between silver electrodes. It readily decomposes into silver and oxygen. It dissolves in ammonia with the liberation of nitrogen and the formation of silver oxide, Ag 2 0; and in sulphuric acid forming a fairly stable dark green liquid which, on dilution, gives off oxygen and forms silver sulphate. It is doubtful whether the pure compound has been obtained. The compound obtained from silver nitrate always contains nitrogen; it appears to have the constant composition Ag 7 NOn, and has been named silver peroxynitrate. Similarly the sulphate yields 5Ag 2 2 , 2Ag 2 S0 7 , silver peroxysulphate, and the fluoride the peroxyfluorides' AguFsOis, Ag 7 FO s . The sesquioxide, Ag<03, is supposed to be formed when silver peroxide is treated with ammonia (Watson, Jour. Chem. Soc, 1906, 89, p 578).

Silver chloride, AgCl, constitutes the mineral cerargyrite or horn silver; mixed with clay it is the butter-milk ore of the German miners. Early names for it are Lac argenti and Luna cornea, the first referring to its form when freshly precipitated, the latter to its ap- pearance after fusion. It is readily obtained as a white curdy precipitate by adding a solution of a chloride to a soluble silver salt It is almost insoluble in water, soluble in 50,000 parts of nitric acid, and more soluble in strong hydrochloric acid and solutions of alkaline chlorides. It readily dissolves in ammonia, the solution, on evapora- tion, yielding rhombic crystals of 2AgCl-3NH s ; it also dissolves in sodium thiosulphate and potassium cyanide solutions. On exposure to light it rapidly darkens, a behaviour utilized in photography (q.v.). Abney and Baker have shown that the pure dry chloride does not blacken when exposed in a vacuous tube to light, and that the blackening is due to absorption of oxygen accompanied by a loss of chlorine. Hydrogen peroxide is also formed. It melts at about 460 to a clear yellow liquid, which, on cooling, solidifies to a trans- lucent resinous mass. It is reduced to metallic silver by certain metals — zinc, iron, &c. — in the presence of water, by fusion with alkaline carbonates or cyanides, by heating in a current of hydrogen, or by digestion with strong potash solution, or with potassium carbonate and grape sugar. Silver bromide, AgBr, constitutes the

mineral bromargyrite or bromyrite, found in Mexico and Chile. It is obtained as a yellowish white precipitate by mixing solutions of a bromide and a silver salt. It is very slightly soluble in nitric acid, and less soluble in ammonia than the chloride. It melts at 427°, and darkens on exposure to air. The minerals embolite, mega- bromite and microbromite, occurring in Chile, are variable mixtures of the chloride and bromide. Silver iodide. Agl, occurs in nature as the mineral iodargyrite or iodyrite, forming hexagonal crystals, or yellowish green plates. It is obtained as a light yellow powder by dissolving the metal in hydriodic acid, or by precipitating a silver salt with a soluble iodide. It is very slightly soluble in acids and ammonia, and almost insoluble in alkaline chlorides; potassium iodide, however, dissolves it to form Agl-KI. Silver iodide is dimorphous; at ordinary temperatures the stable form is hexa- gonal; on heating to about 138 the colour changes from deep yellow to yellowish-white with the formation of cubic crystals. Silver fluoride, AgF, is obtained as quadratic octahedra, with one molecule of water, by dissolving the oxide or carbonate in hydrofluoric acid. It is deliquescent, and dissolves in half its weight of water to form a strongly alkaline liquid. It is not decomposed by sunlight. It melts at 435 and, on cooling, forms a yellow transparent mass. In addition to the salts described above there exist sub-salts. Silver nitrate, AgNOs, one of the most important silver salts, is obtained by dissolving the metal in moderately dilute nitric acid; on evaporation it separates in the anhydrous form as colourless triclinic plates. It dissolves in water, alcohol and ether. It stains the skin and hair black: an ethereal solution having been employed as a dye for the hair. Mixed with gum arabic it forms a marking ink for linen. It fuses at 218°; and when cast in quill-like moulds, it constitutes the lunar caustic of medicine, principally used as a cauterizing agent.

Silver sulphide, Ag 2 S, constitutes the mineral argentite or silver glance, and may be obtained by heating silver with sulphur, or by precipitating a silver salt with sulphuretted hydrogen. Thus ob- tained it is a brownish solid, which readily fuses and resolidifies to a soft leaden-grey mass. It forms with silver nitrate the yellowish green solid, Ag 2 S-AgNC>3, and with silver sulphate the orange-red powder, Ag 2 S-Ag 2 S04. Silver sulphate, Ag 2 SO<, is obtained as white crystals, sparingly soluble in water, by dissolving the metal in strong sulphuric acid, sulphur dioxide being evolved, or by adding strong sulphuric acid to a solution of the nitrate. It combines with ammonia to form the readily soluble 2NH 3 -Ag 2 S04. Silver selenide, Ag 2 Se, resembles the sulphide. It occurs in the minerals naumannite, PbSe-Ag 2 Se, and eukairite, Ag 2 Se-Cu 2 Se. The telluride, Ag 2 Te, occurs in nature as the mineral hessite.

Fulminating silver is an extremely explosive black powder, first obtained in 1788 by Berthelot, who acted with ammonia on silver oxide (prepared by adding lime water to a silver solution). When dry it explodes even on touching with a feather. It appears to be silver nitride AgaN, but it usually contains free silver and sometimes hydrogen. It is to be distinguished from silver fulminate (see Fulminic Acid). The nitride AgN 3 , silver azoimide (q.v.), is also highly explosive.

See j. Percy, Metallurgy of Silver and Gold (London, 1880), part i. ; T. Egleston, The Metallurgy of Silver, Gold and Mercury (New York, 1887-1890), part i. ; M. Eissler, The Metallurgy of Silver (London, 1891); H. F. Collins, The Metallurgy of Lead and Silver (London, 1900), part ii. ; H. O. Hofman, Hydrometallurgy of Silver (1907); C. Schnabel, Metallurgy, translated by H. Louis, 2nd ed. vol. i. (I905)-

Medicinal Use.

Two salts of silver are used in the British pharmacopoeia. (1) Argenti nitras (United States and British pharmacopoeia), lunar caustic, incompatible with alkalis, chlorides, acids, except nitric and acetic, potassium iodide and arsenical solutions. From the nitrate are made (a) argenti nitras indurata, toughened caustic, containing 19 parts of silver nitrate and one of potassium nitrate fused together into cylindrical rods; (b) Argenti nitras mitigatus, mitigated caustic, in which 1 part of silver nitrate and 2 parts of potassium nitrate are fused together into rods or cones. (2) Argenti oxidum, incompatible with chlorides, organic substances, phenol, creosote, &c, with which it forms explosive compounds.

Therapeutics. — Externally the nitrate has a caustic action, destroying the superficial tissues and separating the part acted on as a slough. Its action is limited. It may be" employed to destroy warts or small growths, to reduce exuberant granulations or it may be applied to bites. In granular lids and various forms of ophthalmia solutions of silver nitrate (2 grs. to I fl. oz.) are employed. A I % solution is also used as a prophylactic for ophthalmia neonatorum. The effects of the nitrate being both astringent and stimulating as well as bactericidal, solutions of it are used to paint indolent ulcers, and in chronic pharyngitis or laryngitis. Salts of silver are most useful as an injection in subacute and chronic gonorrhoea, either the nitrate (1 to 5% solution) being employed, or protargol, which is a proteid compound containing 8 % of silver nitrate, is used in I % solution; they also benefit in leucorrhoea. In pruritus of the ​