Tin

Tin (Lat. stannum, whence the chemical symbol "Sn"; atomic weight =117.6, 0= 16), a metallic chemical element. Being a component of bronze, it was used as a metal thousands of years prior to the dawn of history; but it does not follow that prehistoric bronzes were made from metallic tin. When the unalloyed metal was first introduced cannot be ascertained with certainty. The "tin" of the Bible (KauoLTEpos in the Septuagint) corresponds to the Hebrew bedhil, which is really a copper alloy known as early as 1600 B.C. in Egypt. All we know is that about the 1st century the Greek word Kacroircpos  designated tin, and that tin was imported from Cornwall into Italy after, if not before, the invasion of Britain by Julius Caesar. From Pliny's writings it appears that the Romans in his time did not realize the distinction between tin and lead: the former was called plumbum album or candidum to distinguish it from plumbum nigrum (lead proper). The word stannum  definitely assumed its present meaning in the 4th century (H. Kopp). By the early Greek alchemists the metal was named Hermes, but at about the beginning of the 6th century, it was termed Zeusor Jupiter, and the symbol 2(assigned to it; it was also referred to as diabolus metallorum, on account of the brittle alloys which it formed.

## Occurrence

Grains of metallic tin occur intermingled with the gold ores of Siberia, Guiana and Bolivia, and in a few other localities. Of minerals containing this element mention may be made of cassiterite or tinstone, Sn02, tin pyrites, Cu 4 SnS 4 + (Fe,Zn) 2 SnS 4; the metal also occurs in some epidotes, and in company with columbium, tantalum and other metals. Of these "tinstone" is of the greatest commercial importance. It occurs in its matrix, either in or closely associated with fissure veins or disseminated through rock masses. It is also found in the form of rolled lumps and grains, "stream tin," in alluvial gravels; the latter are secondary deposits, the products of the disintegration of the first-named primary deposits. Throughout the world, primary deposits of tinstone are in or closely connected with granite or acid eruptive rocks of the same type, its mineral associates being tourmaline, fluorspar, topaz, wolfram and arsenical pyrites, and the invariable gangue being quartz: the only exception to this mode of occurrence is to be found in Bolivia, where the tin ore occurs intimately associated with silver ores, bismuth ores and various sulphides, whilst the gangue includes barytes and certain carbonates. Over five-sixths of the world's total production is derived from secondary alluvial deposits, but all the tin obtained in Cornwall (the alluvial deposits having been worked out) and Bolivia is from vein mining, while a small portion of that yielded by Australasia comes from veins and from granitic rocks carrying disseminated tinstone.

## Production

During the 18th century the world's supply of tin was mainly drawn from the deposits of England, Saxony and Bohemia; in 1801 England produced about 2500 tons, while the supplies of Saxony and Bohemia had been greatly diminished. The English supply increased, with some oscillations, to between six and seven thousand tons annually in the period 1840-1860, when it suddenly rose to about io,000 tons, and this figure was fairly well sustained until about 1890, when a period of depression set in; the yield for 1900 was 4336 tons, and for 1905 about 4200 tons. In the opening decades of the 19th century supplies began to be drawn from Banka; in 1820 this island contributed 1200 tons; the production was increased to 12,000 tons in 1900, when a diminution set in, 9960 tons being the output during 1905. Billiton became of note in 1853 with a production of 40 tons, which increased to 6000 in 1900 and has since declined to about 3000 tons in 1905. The Straits Settlements ranked as an important producer in 1870 with 2337 tons; it now supplies the greater part of the world's supply, contributing 46,795 tons in 1900, and over 60,000 tons in 1905. Australian deposits were worked in 1872, and in the following year the production was 3000 tons; the maximum outputs were in 1881-1883, averaging 10,000 tons annually; but the supply declined to 2420 tons in 1898 and has since increased to about 5028 tons in 1905. Bolivia produced 501 tons in 1883, 10,245 in 1900 and 12,500 in 1905.

The world's supply in 1900 was 72,911 long tons; this increased in 1904 to 97,790 tons, but in 1905, principally owing to a shortage in the supplies from the Straits and Banka, the yield fell to 94,089 tons.

## Metallurgy

The operations in the metallurgy of tin may be enumerated as: (1) mining and dressing, (2) smelting, (3) refining. The first stage has for its purpose the production of a fairly pure tinstone; the second the conversion of the oxide into metallic tin; and the third preparing a tin pure enough for commercial purposes.

## Mining and Dressing

The alluvial deposits are almost invariably worked opencast, those of the Malay Peninsula and Archipelago chiefly by Chinese labour: in a few instances hydraulic mining has been resorted to, and in other cases true underground mining is carried on; but the latter is both exceptional and difficult. The alluvial extracted, which in the Malay Peninsula and Archipelago carries from 5 to 60 lb of tinstone (or "black tin," as it is termed by Cornish miners) to the cubic yard of gravel, is washed in various simple sluicing appliances, by which the lighter clay, sand and stones are removed and tinstone is left behind comparatively pure, containing usually 65 to 75% of metallic tin (chemically pure tinstone contains 78.7%).

Lode tin, as tinstone derived from primary deposits is often termed, is mined in the ordinary method, the very hard gangue in which it occurs necessitating a liberal use of explosives. The veinstuff is broken small either by hand or in rock-breakers, and stamped to fine powder in stamp mills, which are practically large mechanically-worked pestles and mortars, the stamp proper weighing from 500 to moo lb. The mineral, crushed small enough to pass a sieve with perforations iu in. in diameter, leaves the stamps in suspension in water, and passes through a series of troughs in which the heavier mineral is collected; this then passes through a series of washing operations, which leaves a mixture consisting chiefly of tinstone and arsenical pyrites, which is calcined and washed again, until finally black tin containing about 60 to 65% of metal is left. The calcination is preferably effected in mechanical roasters, it being especially necessary to agitate the ore continually, otherwise it cakes. The crude tinstuff raised in Cornwall carries on an average a little over 2% of black tin. The Bolivian tin ore is treated by first extracting the silver by amalgamation, &c., and afterwards concentrating the residues; there are, however, considerable difficulties in the way of treating the poorer of these very complex ores, and several chemical processes for extracting their metallic contents have been worked out. Of the impurities of the ore the wolframite (tungstate of iron and manganese) is the most troublesome, because on account of its high specific gravity it cannot be washed away as gangue. To remove it, Oxland fuses the ore with a certain proportion of carbonate of soda, which suffices to convert the tungsten into soluble alkaline tungstate, without producing noteworthy quantities of soluble stannate from the oxide of tin; the tungstate is easily removed by treatment with water.

## 2\. Smelting

The dressed ore is smelted with carbon by one of two main methods, viz. either in the shaft furnace or the reverberatory; the former is the better suited to stream tin, the latter to lode tin, but either ore can be smelted in either way, although reverberatory practice yields a purer metal. Shaft furnace smelting is confined to those parts of the world where charcoal can still be obtained in large quantities at moderate prices. The furnace consists of a shaft, circular (or more rarely rectangular) in plan, into which alternate layers of fuel and ore are charged, an air blast being generally injected near to the bottom of the furnace through one or more tuyeres. This was the primitive process all over the world; in the East, South America and similar regions it still holds its own. In Europe, Australasia and one large works at Singapore it has been practically replaced by the reverberatory furnace process, first introduced into Cornwall about the year 1700. In this process the purified ore is mixed with about one-fifth of its weight of a noncaking coal or anthracite smalls, the mixture being moistened to prevent it from being blown off by the draught, and is then fused on the sole of a reverberatory furnace for five or six hours. The slag and metal produced are then run off and the latter is cast into bars; these are in general contaminated with iron, arsenic, copper and other impurities.

## 3\. Refining

All tin, except a small quantity produced by the shaft furnace process from exceptionally pure stream tin ore, requires refining by liquation and "boiling" before it is ready for the market. In the English process the bars are heated cautiously on an inclined hearth, when relatively pure tin runs off, while a skeleton of impure metal remains. The metal run off is further purified by poling, i.e. by stirring it with the branch of a tree - the apple tree being preferred traditionally. This operation is no doubt intended to remove the oxygen diffused throughout the metal as oxide, part of it perhaps chemically by reduction of the oxide to metal, the rest by conveying the finely diffused oxide to the surface and causing it to unite there with the oxide scum. After this the metal is allowed to rest for a time in the pot at a temperature above its freezing point and is then ladled out into ingot forms, care being taken at each stage to ladle off the top stratum. The original top stratum is the purest, and each succeeding lower stratum has a greater proportion of impurities; the lowest consists largely of a solid or semi-solid alloy of tin and iron.

To test the purity of the metal the tin-smelter heats the bars to a certain temperature just below the fusing point, and then strikes them with a hammer or lets them fall on a stone floor from a given height. If the tin is pure it splits into a mass of granular strings. Tin which has been thus manipulated and proved incidentally to be very pure is sold as grain tin. A lower quality goes by the name of block tin. Of the several commercial varieties Banka tin is the purest; it is indeed almost chemically pure. Next comes English grain tin.

For the preparation of chemically pure tin two methods are employed. (I) Commercially pure tin is treated with nitric acid, which converts the tin proper into the insoluble metastannic acid, while the copper, iron, &c., become nitrates; the metastannic acid is washed first with dilute nitric acid, then with water, and is lastly dried and reduced by fusion with black flux or potassium cyanide. (2) A solution of pure stannous chloride in very dilute hydrochloric acid is reduced with an electric current. According to Stolba, beautiful crystals of pure tin can be obtained as follows: A platinum basin, coated over with wax or paraffin outside, except a small circle at the very lowest point, is placed on a plate of amalgamated zinc, lying on the bottom of a beaker, and is filled with a solution of pure stannous chloride. The beaker also is cautiously filled with acidulated water up to a point beyond the edge of the platinum basin.

The whole is then left to itself, when crystals of tin gradually separate out on the bottom of the basin.

## Properties

An ingot of tin is pure white (except for a slight tinge of blue); the colour depends, however, upon the temperature at which it is poured - if too low, the surface is dull, if too high, iridescent. It exhibits considerable lustre and is not subject to tarnishing on exposure to normal air. The metal is pretty soft and easily flattened out under the hammer, but almost devoid of tenacity. That it is elastic, with narrow limits, is proved by its clear ring when struck with a hard body in circumstances permitting of free vibration. The specific gravity of cast tin is 7.29, of rolled tin 7.299, and of electrically deposited tin 7.143 to 7.178. A tin ingot is distinctly crystalline; hence the characteristic crackling noise, or "cry" of tin, which a bar of tin gives out when being bent. This structure can be rendered visible by superficial etching with dilute acid; and as the minuter crystals dissolve more quickly than the larger ones, the surface assumes a frosted appearance (moiree metallique). The metal is dimorphous: by cooling molten tin at ordinary air temperature tetragonal crystals are obtained, while by cooling at a temperature just below the melting point rhombic forms are produced, When exposed for a sufficient time to very low temperatures (to - 39° C. for 14 hours), tin becomes so brittle that it falls into a grey powder, termed the grey modification, under a pestle; it indeed sometimes crumbles into powder spontaneously. At ordinary temperatures tin proves fairly ductile under the hammer, and its ductility seems to increase as the temperature rises up to about 100° C. At some temperature near its fusing point it becomes brittle, and still more brittle from - 14° C. downwards. Iron renders the metal hard and brittle; arsenic, antimony and bismuth (up to 0.5%) reduce its tenacity; copper and lead (1 to 2%) make it harder and stronger but impair its malleability; and stannous oxide reduces its tenacity. Tin fuses at about 230° C.; at a red heat it begins to volatilize slowly; at 1600° to 1800° C. it boils. The hot vapour produced combines with the oxygen of the air into white oxide, Sn02. Its coefficient of linear expansion between 0° and 100° is 0.002717; its specific heat 0.0562; its thermal and electrical conductivities are 145 to 152 and '14.5 to 140. i respectively compared to silver as two.

## Industrial Applications

Commercially pure tin is used for making such apparatus as evaporating basins, infusion pots, stills, &c. It is also employed for making two varieties of tin-foil - one for the silvering of mirrors (see Mirror), the other for wrapping up chocolate, toilet soap, tobacco, &c. The mirror foil must contain some copper to prevent it from being too readily amalgamated by the mercury. For making tin-foil the metal is rolled into thin sheets, pieces of which are beaten out with a wooden mallet. As pure tin does not tarnish in the air and is proof against acid liquids, such as vinegar, lime juice, &c., it is utilized for culinary and domestic vessels. But it is expensive, and tin vessels have to be made very heavy to give them sufficient stability of form; hence it is generally employed merely as a protecting coating for utensils made essentially of copper or iron. The tinning of a copper basin is an easy operation. The basin, made scrupulously clean, is heated to beyond the fusing point of tin. Molten tin is then poured in, a little powdered salammoniac added, and the tin spread over the inside with a bunch of tow. The sal-ammoniac removes the last unavoidable film of oxide, leaving a purely metallic surface, to .which the tin adheres firmly. For tinning small objects of copper or brass (i.e. pins, hooks, &c.) a wet-way process is followed. One part of cream of tartar, two of alum and two of common salt are dissolved in boiling water, and the solution is boiled with granulated metallic tin (or, better, mixed with a little stannous chloride) to produce a tin solution; and into this the articles are put at a boiling heat. In the absence of metallic tin there is no visible change; but, as soon as the metal is introduced, an electrolytic action sets in and the articles get coated over with a firmly adhering film of tin. Tinning wrought iron is effected by immersion. The most important form of the operation is making tinned from ordinary sheet iron (making what is called "sheet tin"). This process was mentioned by Agricola; it was practised in Bohemia in 1620, and in England a century, later. The iron plates, having been carefully cleaned with sand and hydrochloric or sulphuric acid, and lastly with water, are plunged into heated tallow to drive away the water without oxidation of the metal. They are next steeped in a bath, first of molten ferruginous, then of pure tin. They are then taken out and kept suspended in hot tallow to enable the surplus tin to run off. The tin of the second bath dissolves iron gradually and becomes fit for the first bath. To tin cast-iron articles they must be decarburetted superficially by ignition within a bath of ferric oxide (powdered haematite or similar material), then cleaned with acid, and tinned by immersion, as explained above. (See TIN-Plate.) By far the greater part of the tin produced metallurgically is used for making tin alloys (see Pewter, Bronze).

Compounds of Tin.  Tin forms two well-marked series of salts, in one of which it is divalent, these salts being derived from stannous oxide, SnO, in the other it is tetravalent, this series being derived from stannic oxide, Sn02.

Stannous Oxide, SnO, is obtained in the hydrated form Sn20(OH)2 from a solution of stannous chloride by addition of sodium carbonate; it forms a white precipitate, which can be washed with air-free water and dried at 80° C. without much change by oxidation; if it be heated in carbon dioxide the black SnO remains. Precipitated stannous hydrate dissolves readily in caustic potash; if the solution is evaporated quickly it suffers decomposition, with formation of metal and stannate, 2SnO+2KOH = K2Sn03+Sn+H20. If it is evaporated slowly, anhydrous stannous oxide crystallizes out in forms which are combinations of the cube and dodecahedron. Dry stannous oxide, if touched with a glowing body, catches fire and burns to stannic oxide, Sn02. Stannous oxalate when heated by itself in a tube leaves stannous oxide.

Stannic Oxide, Sn0 2. - This, if the term is taken to include the hydrates, exists in a variety of forms. (I) Tinstone (see above and also Cassiterite) is proof against all acids. Its disintegration for analytical purposes can be effected by fusion with caustic alkali in silver basins, with the formation of soluble stannate, or by fusion with sulphur and sodium carbonate, with the formation of a soluble thiostannate. (2) A similar oxide (flores jovis) is produced by burning tin in air at high temperatures or exposing any of the hydrates to a strong red heat. Such tin-ash, as it is called, is used for the polishing of optical glasses. Flores stanni is a finely divided mixture of the metal and oxide obtained by fusing the metal in the presence of air for some time. (3) Metastannic acid (generally written H10Sn5015, to account for the complicated composition of metastannates, e.g. the sodium salt H8Na2Sn501E) is the white compound produced from the metal by means of nitric acid. It is insoluble in water and in nitric acid and apparently so in hydrochloric acid; but if heated with this last for some time it passes into a compound, which, after the acid mother liquor has been decanted off, dissolves in water. The solution when subjected to distillation behaves very much like a physical solution of the oxide in hydrochloric acid, while a solution of orthostannic acid in hydrochloric acid behaves like a solution of SnC1 4 in water, i.e. gives off no hydrochloric acid, and no precipitate of hydrated Sn02. Metastannic acid is distinguished from orthostannic acid by its insolubility in nitric and sulphuric acids. The salts are obtained by the action of alkalies on the acid. (4) Orthostannic acid is obtained as a white precipitate on the addition of sodium carbonate or the exact quantity of precipitated calcium carbonate to a solution of the chloride. This acid, H 2 Sn0 3, is readily soluble in acids forming stannic salts, and in caustic potash and soda, with the formation of orthostannates. Of these sodium stannate, Na2Sn03, is produced industrially by heating tin with Chile saltpetre and caustic soda, or by fusing very finely powdered tinstone with caustic soda in iron vessels. A solution of the pure salt yields fine prisms of the composition Na2Sn03+10H20, which effloresce in the air. The salt is used as a mordant in dyeing and calico-printing. Alkaline and other stannates when treated with aqueous hydrofluoric acid are converted into fluostannates (e.g. K 2 SnO 3 into K2SnF6), which are closely analogous to, and isomorphous with, fluosilicates.

A colloidal or soluble stannic acid is obtained by dialysing a mixture of tin tetrachloride and alkali, or of sodium stannate and hydrochloric acid. On heating it is converted into colloidal metastannic acid.

A hydrated tin trioxide, Sn03, was obtained by Spring by adding barium dioxide to a solution of stannous chloride and hydrochloric acid; the solution is dialysed, and the colloidal solution is evaporated to form a white mass of 2Sn03H20.

Stannous Chloride, SnC1 2, can only be obtained pure by heating pure tin in a current of pure dry hydrochloric acid gas. It is a white solid, fusing at 250° C. to an oily liquid which boils at 606°, and volatilizing at a red heat in nitrogen, a vacuum or hydrochloric acid, without decomposition. The vapour density below 700° C. corresponds to Sn2C14, above Soo° C. to nearly SnCl 2. The chloride readily combines with water to form a crystallizable hydrate SnCl 2.2H 2 O, known as "tin salt" or "tin crystals." This salt is also formed by dissolving tin in strong hydrochloric acid and allowing it to crystallize, and is industrially prepared by passing sufficiently hydrated hydrochloric acid gas over granulated tin contained in stoneware bottles and evaporating the concentrated solution produced in tin basins over granulated tin. The basin itself is not attacked. The crystals are very soluble in cold water, and if the salt is really pure a small proportion of water forms a clear solution; but on adding much water most of the salt is decomposed, with the formation of a precipitate of oxychloride, 2Sn(OH)ClH20. According to Michel and Kraft, one litre of cold saturated solution of tin crystals weighs 1827 grammes and contains 1333 grammes of SnCl 2. The same oxychloride is produced when the moist crystals, or their solution, are exposed to the air. Hence all tin crystals as kept in the laboratory give with water a turbid solution, which contains stannic in addition to stannous chloride. The complete conversion of stannous into stannic chloride may be effected by a great many reagents - for instance, by chlorine (bromine, iodine) readily; by mercuric chloride in the heat, with precipitation of calomel or metallic mercury; by ferric chloride in the heat, with formation of ferrous chloride; by arsenious chloride in strongly hydrochloric solutions, with precipitation of chocolate-brown metallic arsenic. All these reactions are available as tests for "stannosum" or the respective agents. In opposition to stannous chloride, even sulphurous acid (solution) behaves as an oxidizing agent. If the two reagents are mixed a precipitate of yellow stannic sulphide is produced. A strip of metallic zinc when placed in a solution of stannous chloride precipitates the tin in crystals and takes its place in the solution. Stannous chloride is largely used in the laboratory as a reducing agent, in dyeing as a mordant.

Stannic Chloride, SnC1 4, named by Andreas Libavius in 1605 Spiritus argenti vivi sublimate from its preparation by distilling tin or its amalgam with corrosive sublimate, and afterwards termed Spiritus fumans Libavii, is obtained by passing dry chlorine over granulated tin contained in a retort; the tetrachloride distils over as a heavy liquid, from which the excess of chlorine is easily removed by shaking with a small quantity of tin filings and re-distilling. It is a colourless fuming liquid of specific gravity 2.269 at o°; it freezes at - 33° C., and boils at I13.9°. The chloride unites energetically with water to form crystalline hydrates (e.g. SnC1 4.3H 2 O), easily soluble in water. With one-third its weight of water it forms the so-called "butter of tin." It combines readily with alkaline and other chlorides to form double salts, e.g. M 2 SnC1 61 analogous to the chloroplatinates; the salt (NH 4) 2 SnC1 6 is known industrially as - "pink salt" on account of its use as a mordant to produce a pink colour. The oxymuriate of tin used by dyers is SnCl4.5H20. The plain chloride solution is similarly used. It is usually prepared by dissolving the metal in aqua regia.

Stannous Fluoride, SnF 2, is obtained as small, white monoclinic tables by evaporating a solution of stannous oxide in hydrofluoric acid in a vacuum. Stannic Fluoride, SnF 4, is obtained in solution by dissolving hydrated stannic oxide in hydrofluoric acid; it forms a characteristic series of salts, the stannofluorides, M 2 SnF 6, isomorphous with the silico-, titano-, germanoand zirconofluorides. Stannous bromide, SnBr 2, is a light yellow substance formed from tin and hydrobromic acid. Stannic bromide, SnBr 4, is a white crystalline mass, melting at 33° and boiling at 201°, obtained by the combination of tin and bromine, preferably in carbon bisulphide solution. Stannous iodide, Sn12, forms yellow red needles, and is obtained from potassium iodide and stannous chloride. Stannic iodide, Sn14, forms red octahedra and is prepared similarly to stannic bromide. Both iodides combine with ammonia.

Stannous sulphide, SnS, is obtained as a lead-grey mass by heating tin with sulphur, and as a brown precipitate by adding sulphuretted hydrogen to a stannous solution; this is soluble in ammonium polysulphide, and dries to a black powder. Stannic sulphide, SnS 2, is obtained by heating a mixture of tin (or, better, tin amalgam), sulphur and sal-ammoniac in proper proportions in the beautiful form of aurum musivum (mosaic gold) - a solid consisting of golden yellow, metallic lustrous scales, and used chiefly as a yellow "bronze" for plaster-of-Paris statuettes, &c. The yellow precipitate of stannic sulphide obtained by adding sulphuretted hydrogen to a stannic solution readily dissolves in solutions of the alkaline sulphides to form thiostannates of the formula M 2 SnS 31 the free acid, H2SnS3, may be obtained as an almost black powder by drying the yellow precipitate formed when hydrochloric acid is added to a solution of a thiostannate.

## Analysis

Tin compounds when heated on charcoal with sodium carbonate or potassium cyanide in the reducing blowpipe flame yield the metal and a scanty ring of white Sn02. Stannous salt solutions yield a brown precipitate of SnS with sulphuretted hydrogen, which is insoluble in cold dilute acids and in real sulphide of ammonium, (NH 4) 2 S; but the yellow, or the colourless reagent on addition of sulphur, dissolves the precipitate as SnS 2 salt. The solution on acidification yields a yellow precipitate of this sulphide. Stannic salt solutions give a yellow precipitate of SnS 2 with sulphuretted hydrogen, which is insoluble in cold dilute acids but readily soluble in sulphide of ammonium, and is re-precipitated therefrom as SnS2 on acidification. Only stannous salts (not stannic) give a precipitate of calomel in mercuric chloride solution. A mixture of stannous and stannic chloride, when added to a sufficient quantity of solution of chloride of gold, gives an intensely purple precipitate of gold purple (purple of Cassius). The test is very delicate, although the colour is not in all cases a pure purple. Tin is generally quantitatively estimated as the dioxide. The solutions are oxidized, precipitated with ammonia, the precipitate dissolved in hydrochloric acid, and re-thrown down by boiling with sodium sulphate. The precipitate is filtered, washed, dried and ignited.

BIBLIOGRAPHY. - FOr the history of tin and statistics of its production, &c., see Bernard Neumann, Die Metalle (1904); A. Rossing, Geschichte der Metalle (1901). For its chemistry see Roscoe and Schorlemmer, Treatise on Inorganic Chemistry, vol. ii.; H. Moissan, Traite de chimie minerale; 0\. Dammer, Handbuch der anorganischen Chemie. For its production and metallurgy see Sydney Fawns, Tin Deposits of the World; A. G. Charleton, Tin Mining; Henry Louis, The Production of Tin, and C. Schnabel, Handbook of Metallurgy (English trans. by Louis, 1907). General statistical information, and improvements in the metallurgy, &c., are recorded annually in The Mineral Industry.