Chapter 139

SUGAR OF LEAD, properlyAcetate of lead, (Acetate de plomb;Sel de Saturne, Fr.;Essigsaures Bleioxyd,Bleizucker, Germ.) is prepared by dissolving pure litharge, with heat, in strong vinegar, made of malt, wood, or wine, till the acid be saturated. A copper boiler, rendered negatively electrical by soldering a strap of lead within it, is the best adapted to this process on the great scale. 325 parts of finely ground and sifted oxide of lead, require 575 parts of strong acetic acid, of spec. grav. 7° Baumé, for neutralization, and afford 960 parts of crystallized sugar of lead. The oxide should be gradually sprinkled into the moderately hot vinegar, with constant stirring, to prevent adhesion to the bottom; and when the proper quantity is dissolved, the solution may be weakened with some of the washings of a preceding process, to dilute the acetate, after which the whole should be heated to the boiling point, and allowed to cool slowly, in order to settle. The limpid solution is to be drawn off by a syphon, concentrated by boiling to the density of 32° B., taking care that there be always a faint excess of acid, to prevent the possibility of any basic salt being formed, which would interfere with the formation of regular crystals. Should the concentrated liquor be coloured, it may be whitened by filtration through granular bone black.Stoneware vessels, with salt glaze, answer best for crystallizers. Their edges should be smeared with candle-grease, to prevent the salt creeping over them byefflorescent vegetation. The crystals are to be drained, and dried in a stove-room very slightly heated. It deserves remark, that linen, mats, wood, and paper, imbued with sugar of lead, and strongly dried, readily take fire, and burn away like tinder. When the motherwaters cease to afford good crystals, they should be decomposed by carbonate of soda, or by lime skilfully applied, when a carbonate or an oxide will be obtained, fit for treating with fresh vinegar. The supernatant acetate of soda may be employed for the extraction of pure acetic acid.A main point in the preparation of sugar of lead, is to use a strong acid; otherwise much time and acid are wasted in concentrating the solution. This salt crystallizes in colourless, transparent, four and six sided prisms, from a moderately concentrated solution; but from a stronger solution, in small needles, which have a yellow cast if the acid has been slightly impure. It has no smell, a sweetish astringent metallic taste, a specific gravity of 2·345; it is permanent in the air at ordinary temperatures, but effloresces when heated to 95°, with the loss of its water of crystallization and some acid, falling into a powder, which passes, in the air, slowly into carbonate of lead. The crystals dissolve in 11⁄2times their weight of water at 60°, but in much less of boiling water, and in 8 parts of alcohol. The solution feebly reddens litmus paper, but has an alkaline reaction upon the colours of violets and turmeric. The constituents of the salt are, 58·71 oxide of lead, 27·08 acetic acid, and 14·21 water, in 100.Acetate of lead is much used in calico-printing. It is poisonous, and ought to be prepared and handled with attention to this circumstance.There are two subacetates of lead; the first of which, the ter-subacetate, has three atoms of base to one of acid, and is the substance long known by the name of Goulard’s extract. It may be obtained by digesting with heat a solution of the neutral acetate, upon pure litharge or massicot. The solution affords white crystalline scales, which do not taste so sweet as sugar of lead, dissolve in not less than 30 parts of water, are insoluble in alcohol, and have a decided alkaline reaction upon test paper. Carbonic acid, transmitted through the solution, precipitates the excess of the oxide of lead, in the state of a carbonate, a process long ago prescribed by Thenard for making white-lead. This subacetate consists of 88·66 of oxide, and 13·34 acid, in 100 parts. It is employed for making the orange sub-chromate of lead, as also sometimes in surgery.Asex-subacetate, containing six atoms of base, may be obtained by adding ammonia in excess to a solution of the preceding salt, and washing the precipitate with dilute water of ammonia. A white powder is thus formed, that dissolves sparingly in cold water, but gives a solution in boiling water, from which white silky needles are deposited. It consists of 92·86 oxide, and 7·14 acid.

Stoneware vessels, with salt glaze, answer best for crystallizers. Their edges should be smeared with candle-grease, to prevent the salt creeping over them byefflorescent vegetation. The crystals are to be drained, and dried in a stove-room very slightly heated. It deserves remark, that linen, mats, wood, and paper, imbued with sugar of lead, and strongly dried, readily take fire, and burn away like tinder. When the motherwaters cease to afford good crystals, they should be decomposed by carbonate of soda, or by lime skilfully applied, when a carbonate or an oxide will be obtained, fit for treating with fresh vinegar. The supernatant acetate of soda may be employed for the extraction of pure acetic acid.

A main point in the preparation of sugar of lead, is to use a strong acid; otherwise much time and acid are wasted in concentrating the solution. This salt crystallizes in colourless, transparent, four and six sided prisms, from a moderately concentrated solution; but from a stronger solution, in small needles, which have a yellow cast if the acid has been slightly impure. It has no smell, a sweetish astringent metallic taste, a specific gravity of 2·345; it is permanent in the air at ordinary temperatures, but effloresces when heated to 95°, with the loss of its water of crystallization and some acid, falling into a powder, which passes, in the air, slowly into carbonate of lead. The crystals dissolve in 11⁄2times their weight of water at 60°, but in much less of boiling water, and in 8 parts of alcohol. The solution feebly reddens litmus paper, but has an alkaline reaction upon the colours of violets and turmeric. The constituents of the salt are, 58·71 oxide of lead, 27·08 acetic acid, and 14·21 water, in 100.

Acetate of lead is much used in calico-printing. It is poisonous, and ought to be prepared and handled with attention to this circumstance.

There are two subacetates of lead; the first of which, the ter-subacetate, has three atoms of base to one of acid, and is the substance long known by the name of Goulard’s extract. It may be obtained by digesting with heat a solution of the neutral acetate, upon pure litharge or massicot. The solution affords white crystalline scales, which do not taste so sweet as sugar of lead, dissolve in not less than 30 parts of water, are insoluble in alcohol, and have a decided alkaline reaction upon test paper. Carbonic acid, transmitted through the solution, precipitates the excess of the oxide of lead, in the state of a carbonate, a process long ago prescribed by Thenard for making white-lead. This subacetate consists of 88·66 of oxide, and 13·34 acid, in 100 parts. It is employed for making the orange sub-chromate of lead, as also sometimes in surgery.

Asex-subacetate, containing six atoms of base, may be obtained by adding ammonia in excess to a solution of the preceding salt, and washing the precipitate with dilute water of ammonia. A white powder is thus formed, that dissolves sparingly in cold water, but gives a solution in boiling water, from which white silky needles are deposited. It consists of 92·86 oxide, and 7·14 acid.

SULPHATES, are saline compounds of sulphuric acid with oxidized bases. The minutest quantity of them present in any solution, may be detected by the precipitate, insoluble in nitric or muriatic acid, which they afford with nitrate or muriate of baryta. They are mostly insoluble in alcohol.

SULPHATE OF ALUMINA AND POTASSA, isalum.

SULPHATE OF AMMONIA, is a salt sometimes formed by saturating the ammonia liquor of the gas-works with sulphuric acid; and it is employed for making carbonate of ammonia. SeeAmmoniaandSal Ammoniac.

SULPHATE OF BARYTA, is the mineral called heavy-spar, which frequently forms the gangue or vein-stone of lead and other metallic ores.

SULPHATE OF COPPER,Roman or Blue Vitriol(Vitriol de Chypre, Fr.;Kupfervitriol, Germ.); is a salt composed of sulphuric acid and oxide of copper, and may be formed by boiling the concentrated acid upon the metal, in an iron pot. It is, however, a natural product of many copper mines, from which it flows out in the form of a blue water, being the result of the infiltration of water over copper pyrites, which has become oxygenated by long exposure to the air in subterranean excavations. The liquid is concentrated by heat in copper vessels, then set aside to crystallize. The salt forms in oblique four-sided tables, of a fine blue colour; has a spec. gravity of 2·104; an acerb, disagreeable, metallic taste; and, when swallowed, it causes violent vomiting. It becomes of a pale dirty blue, and effloresces slightly, on long exposure to the air; when moderately heated, it loses 36 per cent. of water, and falls into a white powder. It dissolves in 4 parts of water, at 60°, and in 2 of boiling water, but not in alcohol; the solution has an acid reaction upon litmus paper. When strongly ignited, the acid flies off, and the black oxide of copper remains. The constituents of crystallized sulphate of copper are—oxide, 31·80; acid, 32·14; and water, 36·06. Its chief employment in this country is in dyeing, and for preparing certain green pigments. SeeScheele’sandSchweinfurth Green. In France, the farmers sprinkle a weak solution of it upon their grains and seeds before sowing them, to prevent their being attacked by birds and insects.

SULPHATE OF IRON,Green vitriol,Copperas(Couperose verte, Fr.;Eisenvitriol,Schwefelsaures Eisenoxydul, Germ.); is a crystalline compound of sulphuric acid and protoxide of iron; hence called, by chemists, the protosulphate; consisting of, 26·10 of base, 29·90 of acid, and 44·00 of water, in 100 parts; or of 1 prime equivalent of protoxide, 36, + 1 of acid, 40, + 7 of water, 63, = 139. It may be prepared by dissolving iron to saturation in dilute sulphuric acid, evaporating the solution till a pellicle forms upon its surface, and setting it aside to crystallize. The copperas of commerce is made in a much cheaper way, by stratifying the pyrites found in the coalmeasures (VitriolkiesandStrahlkiesof the Germans), upon a sloping puddled platform of stone, leaving the sulphuret exposed to the weather, till, by the absorption of oxygen, it effloresces, lixiviating with water the supersulphate of iron thus formed, saturating the excess of acid with plates of old iron, then evaporating and crystallizing. The other pyrites, which occurs often crystallized, called by the GermansSchwefelkiesorEisenkies, must be deprived of a part of its sulphur by calcination, before it acquires the property of absorbing oxygen from the atmosphere, and thereby passing from a bisulphuret into a bisulphate. Alum schist very commonly contains vitriolkies, and affords, after being roasted and weather-worn, a considerable quantity of copperas, which must be carefully separated by crystallization from the alum.This liquor used formerly to be concentrated directly in leaden vessels; but the first stage of the operation is now carried on in stone canals of considerable length, vaulted over with bricks, into which the liquor is admitted, and subjected at the surface to the action of flame and heated air, from a furnace of the reverberatory kind, constructed at one end, and discharging its smoke by a high chimney raised at the other. SeeSoda Manufacture. Into this oblong trough, resting on dense clay, and rendered tight in the joints by water-cement, old iron is mixed with the liquor, to neutralize the excess of acid generated from the pyrites, as also to correct the tendency to superoxidizement in copperas, which would injure the fine green colour of the crystals. After due concentration and saturation in this surface evaporator, the solution is run off into leaden boilers, where it is brought to the proper density for affording regular crystals, which it does by slow cooling, in stone cisterns.Copperas forms sea-green, transparent, rhomboidal prisms, which are without smell, but have an astringent, acerb, inky taste; they speedily become yellowish-brown in the air, by peroxidizement of the iron, and effloresce in a warm atmosphere: they dissolve in 1·43 parts of water at 60°, in 0·27 at 190°, and in their own water of crystallization at a higher heat. This salt is extensively used in dyeing black, especially hats, in making ink and prussian blue, for reducing indigo in the blue vat, in the China blue dye, for making the German oil of vitriol, and in many chemical and medicinal preparations.There is a persulphate and subpersulphate of iron, but they belong to the domain of chemistry. The first may be formed, either by dissolving with heat one part of red oxide of iron (colcothar) in one-and-a-half of concentrated sulphuric acid, or by adding some nitric acid to a boiling-hot solution of copperas. It forms with galls and logwood a very black ink, which is apt to become brown-black. When evaporated to dryness, it appears as a dirty white pulverulent substance, which is soluble in alcohol. It consists, in 100 parts, of 39·42 of red oxide of iron, and 60·58 sulphuric acid.Hydrated peroxide of iron, prepared by precipitation with alkali from solution of the persulphate, is an excellent antidote against poisoning by arsenic. A Frenchperuquier, who had swallowed two drams of arsenious acid, was, after an interval of twenty minutes, treated with the oxide precipitated from 6 ounces of that salt by caustic potash. It was diffused in 20 quarts of weak syrup, and administered in successive doses. After repeated vomiting and purging, the patient felt no more pain, and was pronounced by the physician to be quite convalescent.In the copperas and alum works, a very large quantity of ochrey sediment is obtained; which is a peroxide of iron, containing a little sulphuric acid and alumina. This deposit, calcined in reverberatory hearths, becomes of a bright-red colour; and when ground and elutriated, in the same way as is described underwhite lead, forms a cheap pigment, in very considerable demand, calledEnglish red, in the French market.Colcothar of Vitriol, and Crocus of Mars, are old names for red oxide of iron. This brown-red powder is obtained in its purest state, by calcining dried sulphate of iron in a furnace till all its acid be expelled, and its base become peroxidized. It must be levigated, elutriated, and dried. This powder is employed extensively in the steel manufacture, for giving the finishing lustre to fine articles; it is used by silversmiths under the name of plate powder androuge; and by the opticians for polishing the specula of reflecting telescopes. Much of thecrocusin the market, is made, however, from the copperas and alum sediments, and is greatly inferior to the article prepared by the last process. The finestrougeis made by precipitating the oxide with soda, then washing and calcining the powder.An excellent powder for applying to razor-strops, is made by igniting together in a crucible equal parts of well-dried copperas and sea salt. The heat must be slowly raised and well regulated, otherwise the materials will boil over in a pasty state, and the product will be in a great measure lost. When well made, out of contact of air, it has the brilliant aspect of plumbago. It has a satiny feel, and is a truefer olegiste, similar in composition to the Elba iron ore. It requires to be ground and elutriated; after which it affords, on drying, an impalpable powder, that may be either rubbed on a strop of smooth buff leather, or mixed up with hog’s-lard or tallow into a stiff cerate.

This liquor used formerly to be concentrated directly in leaden vessels; but the first stage of the operation is now carried on in stone canals of considerable length, vaulted over with bricks, into which the liquor is admitted, and subjected at the surface to the action of flame and heated air, from a furnace of the reverberatory kind, constructed at one end, and discharging its smoke by a high chimney raised at the other. SeeSoda Manufacture. Into this oblong trough, resting on dense clay, and rendered tight in the joints by water-cement, old iron is mixed with the liquor, to neutralize the excess of acid generated from the pyrites, as also to correct the tendency to superoxidizement in copperas, which would injure the fine green colour of the crystals. After due concentration and saturation in this surface evaporator, the solution is run off into leaden boilers, where it is brought to the proper density for affording regular crystals, which it does by slow cooling, in stone cisterns.

Copperas forms sea-green, transparent, rhomboidal prisms, which are without smell, but have an astringent, acerb, inky taste; they speedily become yellowish-brown in the air, by peroxidizement of the iron, and effloresce in a warm atmosphere: they dissolve in 1·43 parts of water at 60°, in 0·27 at 190°, and in their own water of crystallization at a higher heat. This salt is extensively used in dyeing black, especially hats, in making ink and prussian blue, for reducing indigo in the blue vat, in the China blue dye, for making the German oil of vitriol, and in many chemical and medicinal preparations.

There is a persulphate and subpersulphate of iron, but they belong to the domain of chemistry. The first may be formed, either by dissolving with heat one part of red oxide of iron (colcothar) in one-and-a-half of concentrated sulphuric acid, or by adding some nitric acid to a boiling-hot solution of copperas. It forms with galls and logwood a very black ink, which is apt to become brown-black. When evaporated to dryness, it appears as a dirty white pulverulent substance, which is soluble in alcohol. It consists, in 100 parts, of 39·42 of red oxide of iron, and 60·58 sulphuric acid.

Hydrated peroxide of iron, prepared by precipitation with alkali from solution of the persulphate, is an excellent antidote against poisoning by arsenic. A Frenchperuquier, who had swallowed two drams of arsenious acid, was, after an interval of twenty minutes, treated with the oxide precipitated from 6 ounces of that salt by caustic potash. It was diffused in 20 quarts of weak syrup, and administered in successive doses. After repeated vomiting and purging, the patient felt no more pain, and was pronounced by the physician to be quite convalescent.

In the copperas and alum works, a very large quantity of ochrey sediment is obtained; which is a peroxide of iron, containing a little sulphuric acid and alumina. This deposit, calcined in reverberatory hearths, becomes of a bright-red colour; and when ground and elutriated, in the same way as is described underwhite lead, forms a cheap pigment, in very considerable demand, calledEnglish red, in the French market.

Colcothar of Vitriol, and Crocus of Mars, are old names for red oxide of iron. This brown-red powder is obtained in its purest state, by calcining dried sulphate of iron in a furnace till all its acid be expelled, and its base become peroxidized. It must be levigated, elutriated, and dried. This powder is employed extensively in the steel manufacture, for giving the finishing lustre to fine articles; it is used by silversmiths under the name of plate powder androuge; and by the opticians for polishing the specula of reflecting telescopes. Much of thecrocusin the market, is made, however, from the copperas and alum sediments, and is greatly inferior to the article prepared by the last process. The finestrougeis made by precipitating the oxide with soda, then washing and calcining the powder.

An excellent powder for applying to razor-strops, is made by igniting together in a crucible equal parts of well-dried copperas and sea salt. The heat must be slowly raised and well regulated, otherwise the materials will boil over in a pasty state, and the product will be in a great measure lost. When well made, out of contact of air, it has the brilliant aspect of plumbago. It has a satiny feel, and is a truefer olegiste, similar in composition to the Elba iron ore. It requires to be ground and elutriated; after which it affords, on drying, an impalpable powder, that may be either rubbed on a strop of smooth buff leather, or mixed up with hog’s-lard or tallow into a stiff cerate.

SULPHATE OF LIME. SeeGypsum.

SULPHATE OF MAGNESIA,Epsom Salt(Sel amer, Fr.;Bittersalz, Germ.); exists in sea-water, as also in the waters of Saidschütz, Sedlitz, and Püllna; and in many saline springs, besides Epsom in Surrey, whence it has derived its trivial name, and from which it was first extracted, in the year 1695, and continued to be so, till modern chemistry pointed out cheaper and more abundant sources of this useful purgative salt. The sulphate of magnesia, occasionally found effloresced on the surface of minerals in crystalline filaments, was calledhaarsalz(hair salt) by the older writers. The bittern of the Scotch sea-salt works is muriate of magnesia, mixed, with a little sulphate of magnesia and chloride of sodium. If the proper decomposing quantity (found by trial) of sulphate of soda be added to it, and the mixed solution be evaporated at the temperature of 122° F., chloride of sodium will form by double affinity, and fall down in cubical crystals; while the solution of sulphate of magnesia which remains, being evaporated to the proper point, will afford regular crystals in four-sided prisms with four-sided acuminations. Or, if bittern be treated in a retort with the equivalent quantity of sulphuric acid, the muriatic acid may be distilled off into a series of Woulfe’s bottles, and the sulphate of magnesia, soda, and lime, will remain in the retort, from which mixture the sulphate of magnesia may be separated by filtration and crystallization.Magnesian limestone being digested with as much muriatic acid as will dissolve out its lime only, will, after washing, afford, with the equivalent quantity of sulphuric acid, a pure sulphate of magnesia; and this is certainly the simplest and most profitable process for manufacturing this salt upon the great scale. Many prepare it directly, by digesting upon magnesian limestone the equivalent saturating quantity of dilute sulphuric acid. The sulphate of lime being separated by subsidence, the supernatant solution of sulphate of magnesia is evaporated and crystallized.This salt is composed of, magnesia 16·72, sulphuric acid 32·39, and water 50·89. When free from muriate, it tends to effloresce in the air. It dissolves in 4 parts of water at 32°, in 3 parts at 60°, in 1·4 at 200°, and in its own water of crystallization at a higher heat.

Magnesian limestone being digested with as much muriatic acid as will dissolve out its lime only, will, after washing, afford, with the equivalent quantity of sulphuric acid, a pure sulphate of magnesia; and this is certainly the simplest and most profitable process for manufacturing this salt upon the great scale. Many prepare it directly, by digesting upon magnesian limestone the equivalent saturating quantity of dilute sulphuric acid. The sulphate of lime being separated by subsidence, the supernatant solution of sulphate of magnesia is evaporated and crystallized.

This salt is composed of, magnesia 16·72, sulphuric acid 32·39, and water 50·89. When free from muriate, it tends to effloresce in the air. It dissolves in 4 parts of water at 32°, in 3 parts at 60°, in 1·4 at 200°, and in its own water of crystallization at a higher heat.

SULPHATE OF MANGANESE, is prepared on the great scale for the calico-printers, by exposing the peroxide of the metal and pitcoal ground together, and made into a paste with sulphuric acid, to a heat of 400° F. On lixiviating the calcined mass, a solution of the salt is obtained, which is to be evaporated and crystallized. It forms pale amethyst-coloured prisms, which have an astringent bitter taste, dissolve in 21⁄2parts of water, and consist of, protoxide of manganese 31·93, sulphuric acid 35·87, and water 32·20, in 100 parts.

SULPHATE OF MERCURY, is a white salt which is used in making corrosive sublimate. SeeMercury. The subsulphate, calledTurbith Mineral, is a pale yellow pigment, and may be prepared by washing the white sulphated peroxide with hot water, which resolves it into the soluble supersulphate, and the insoluble subsulphate, orTurbith. It is poisonous.

SULPHATE OF POTASSA, is obtained by first igniting and then crystallizing the residuum of the distillation of nitric acid from nitre.

SULPHATE OF SODA, is commonly called Glauber’s salt, from the name of the chemist who first prepared it. It is obtained by igniting and then crystallizing the residuum of the distillation of muriatic acid from common salt. It crystallizes in channelled 6-sided prisms. SeeSoda Manufacture.

SULPHATE OF ZINC, called alsoWhite Vitriol, is commonly prepared in the Harz, by washing the calcined and effloresced sulphuret of zinc or blende, on the same principle as green and blue vitriol are obtained from the sulphurets of iron and copper. Pure sulphate of zinc may be made most readily by dissolving the metal in dilute sulphuric acid, evaporating and crystallizing the solution. It forms prismatic crystals, which have an astringent, disagreeable, metallic taste; they effloresce in a dry air, dissolve in 2·3 parts of water at 60°, and consist of—oxide of zinc, 28·29; acid, 28·18; water, 43·53. Sulphate of zinc is used for preparing drying oils for varnishes, and in the reserve or resist pastes of the calico-printer.

SULPHITES, are a class of salts, consisting of sulphurous acid, combined in equivalent proportions with the oxidized bases.

SULPHOSELS, is the name given by Berzelius to a class of salts which may be prepared as follows:—1. Dissolve a salt consisting of an oxide and an acid (anoxisalt), in a very small quantity of water, and pass through the solution a stream of sulphuretted hydrogen, till the salt be entirely decomposed. In this operation, theoxisaltis transformed into asulphosalt, by the sulphur of the compound gas; while its hydrogen forms water with the oxygen of the saline base. This process is applicable only to the metallic salts; and among these, not to the nitrates, carbonates, or phosphates. 2. Another method of preparingsulphosaltsis, to add to a watery solution of sulphuret ofpotassium, an electro-negative metallic sulphuret, which will dissolve in the liquid till the sulphuret of potassium be saturated. This saline compound is to be employed to effect double decompositions with the oxisalts; that is, to convert the radical of another base, combined with anoxacid, into a sulphosalt. 3. If the electro-negative sulphuret be put in powder into a solution of the hydrosulphuret of potassa, it will dissolve and expel the sulphuretted hydrogen with effervescence; just as carbonic acid is displaced by a stronger acid. For his other three methods of preparingsulphosalts, see hisElements, vol. iii. p. 336, Fr. translation.

SULPHUR;Brimstone(Soufre, Fr.;Schwefel, Germ.); is a simple combustible, solid, non-metallic, of a peculiar yellow colour, very brittle, melting at the temperature of 226° Fahr., and possessing, after it has been fused, a specific gravity of 1·99. When held in a warm hand, a roll of sulphur emits a crackling sound, by the fracture of its interior parts; and when it is rubbed, it emits a peculiar well-known smell, and acquires at the same time negative electricity. When heated to the temperature of 560° F. it takes fire, burns away with a dull blue flame of a suffocating odour, and leaves no residuum. When more strongly heated, sulphur burns with a vivid white flame. It is not affected by air or water.Sulphur is an abundant product of nature; existing sometimes pure or merely mixed, and at others in intimate chemical combination with oxygen, and various metals, forming sulphates and sulphurets. See Ores ofCopper,Iron,Lead, &c., under these metals.Sulphur refining retortFig.1100.represents one of the cast-iron retorts used at Marseilles for refining sulphur, wherein it is melted and converted into vapours, which are led into a large chamber for condensation. The bodya, of the retort is an iron pot, 3 feet in diameter outside, 22 inches deep, half an inch thick, which weighs 14 cwt., and receives a charge of 8 cwt. of crude sulphur. The grate is 8 inches under its bottom, whence the flame rises and plays round its sides. A cast-iron capitalb, being luted to the pot, and covered with sand, the opening in front is shut with an iron plate. The chamberd, is 23 feet long, 11 feet wide, and 13 feet high, with walls 32 inches thick. In the roof, at each gable, valves or flap-doors,e, 10 inches square, are placed at the bottom of the chimneyc. The cords for opening the valves are led down to the side of the furnace. The entrance to the chamber is shut with an iron door. In the wall opposite to the retorts, there are two apertures near the floor, for taking out the sulphur. Each of the two retorts belonging to a chamber is charged with 71⁄2or 8 cwts. of sulphur; but one is fired first, and with a gentle heat, lest the brimstone froth should overflow; but when the fumes begin to rise copiously, with a stronger flame. The distillation commences within an hour of kindling the fire, and is completed in six hours. Three hours after putting fire to the first retort, the second is in like manner set in operation.When the process of distillation is resumed, after having been some time suspended, explosions may be apprehended, from the presence of atmospherical air; to obviate the danger of which, the flap-doors must be opened every 10 minutes; but they should remain closed during the setting of the retorts, and the reflux of sulphurous fumes or acid should be carried off by a draught-hood over the retorts. The distillation is carried on without interruption during the week, the charges being repeated four times in the day. By the third day, the chamber acquires such a degree of heat as to preserve the sulphur in a liquid state; on the sixth, its temperature becoming nearly 300° F., gives the sulphur a dark hue, on which account the furnace is allowed to cool on the Sunday. The fittest distilling temperature is about 248°. The sulphur is drawn off through two iron pipes cast in the iron doors of the orifices on the side of the chamber opposite to the furnace. The iron stoppers being taken out of the mouths of the pipes, the sulphur is allowed to run along an iron spout placed over red-hot charcoal, into the appropriate wooden moulds.Native sulphurin its pure state is solid, brittle, transparent, yellow, or yellow borderingon green, and of a glassy lustre when newly broken. It occurs frequently in crystalline masses, and sometimes in complete and regular crystals, which are all derivable from the rhomboidal octahedron. The fracture is usually conchoidal and shining. Its specific gravity is 2·072, exceeding somewhat the density of melted sulphur. It possesses a very considerable refractive power; and doubles the images of objects even across two parallel faces. Sulphur, crystallized by artificial means, presents a very remarkable phenomenon; for by varying the processes, crystals are obtained whose forms belong to two different systems of crystallization. The red tint, so common in the crystals of Sicily, and of volcanic districts, has been ascribed by some mineralogists to the presence of realgar, and by others to iron; but Stromeyer has found the sublimed orange-red sulphur of Vulcano, one of the Lipari islands, to result from a natural combination of sulphur and selenium.It is extracted from the minerals containing it, at Solfatara, by the following process:—Ten earthen pots, of about a yard in height, and 41⁄2gallons imperial in capacity, bulging in the middle, are ranged in a furnace called a gallery; five being set on the one side, and five on the other. These are so distributed in the body of the walls of the gallery, that their belly projects partly without, and partly within, while their top rises out of the vault of the roof. The pots are filled with lumps of the sulphur ore of the size of the fist; their tops are closed with earthenware lids, and from their shoulder proceeds a pipe of about 2 inches diameter, which bends down, and enters into another covered pot, with a hole in its bottom, standing over a tub filled with water. On applying heat to the gallery, the sulphur melts, volatilizes, and runs down in a liquid state into the tubs, where it congeals. When one operation is finished, the pots are re-charged, and the process is repeated.In Saxony and Bohemia, the sulphurets of iron and copper are introduced into large earthenware pipes, which traverse a furnace-gallery; and the sulphur exhaled flows into pipes filled with cold water, on the outside of the furnace. 900 parts of sulphuret afford from 100 to 150 of sulphur, and a residuum of metallic protosulphuret. SeeMetallurgyandCopper.Volcanic sulphur is purer than that extracted from pyrites; and as the latter is commonly mixed with arsenic, and some other metallic impregnations, sulphuric acid made of it would not answer for many purposes of the arts; though a tolerably good sulphuric acid may be made directly from the combustion of pyrites, instead of sulphur, in the lead chambers. The present high price of the Sicilian sulphur is a great encouragement to its extraction from pyrites. It is said that the common English brimstone, such as was extracted from the copper pyrites of the Parys mine of Anglesey, contained fully a fifteenth of residuum, insoluble in boiling oil of turpentine, which was chiefly orpiment; while the fine Sicilian sulphur, now imported in vast quantities by the manufacturers of oil of vitriol, contains not more than 3 per cent. of foreign matter, chiefly earthy, but not at all arsenical.Sulphur has been known from the most remote antiquity. From its kindling at a moderate temperature, it is employed for readily procuring fire, and lighting by its flame other bodies not so combustible. At Paris, the preparation of sulphur matches constitutes a considerable branch of industry. The sulphurous acid formed by the combustion of sulphur in the atmospheric air, is employed to bleach woollen and silken goods, as also cotton stockings; to disinfect vitiated air, though it is inferior in power to nitric acid vapour and chlorine; to kill mites, moths, and other destructive insects in collections of zoology; and to counteract too rapid fermentation in wine-vats, &c. As the same acid gas has the property of suddenly extinguishing flame, sulphur has been thrown into a chimney on fire, with the best effect; a handful of it being sometimes sufficient. Sulphur is also employed for cementing iron bars in stone; for taking impressions from seals and cameos, for which purpose it is kept previously melted for some time, to give the casts an appearance of bronze. Its principal uses, however, are for the manufactures of vermillion, or cinnabar, gunpowder, and sulphuric acid.SeeMetallurgy,page 823, for the description of Gahn’s furnace for extracting sulphur from pyrites.Pyrites as a bi-sulphuret, consisting of 45·5 parts of iron, and 54·5 of sulphur, may, by proper chemical means, be made to give off one half of its sulphur, or about 27 per cent.; but great care must be taken not to generate sulphurous acid, as is done very wastefully by the Fahlun and the Goslar processes. By the latter, indeed, not more than 1 or 2 parts of sulphur are obtained, by roasting 100 parts of the pyritous ores of the Rammelsberg mines. In these cases, the sulphur is burned, instead of being sublimed. The residuum of the operation, when it is well conducted, is black sulphuret of iron, which may be profitably employed for making copperas. The apparatus for extracting sulphur from pyrites should admit no more air than is barely necessary to promote the sublimation.—Sicily produced last year 70,000 tons of sulphur, and Tuscany1200; of which Great Britain consumed 46,000; France, 18,000; other places, 6000. In 1820, Great Britain consumed only 5000 tons.

Sulphur is an abundant product of nature; existing sometimes pure or merely mixed, and at others in intimate chemical combination with oxygen, and various metals, forming sulphates and sulphurets. See Ores ofCopper,Iron,Lead, &c., under these metals.

Sulphur refining retort

Fig.1100.represents one of the cast-iron retorts used at Marseilles for refining sulphur, wherein it is melted and converted into vapours, which are led into a large chamber for condensation. The bodya, of the retort is an iron pot, 3 feet in diameter outside, 22 inches deep, half an inch thick, which weighs 14 cwt., and receives a charge of 8 cwt. of crude sulphur. The grate is 8 inches under its bottom, whence the flame rises and plays round its sides. A cast-iron capitalb, being luted to the pot, and covered with sand, the opening in front is shut with an iron plate. The chamberd, is 23 feet long, 11 feet wide, and 13 feet high, with walls 32 inches thick. In the roof, at each gable, valves or flap-doors,e, 10 inches square, are placed at the bottom of the chimneyc. The cords for opening the valves are led down to the side of the furnace. The entrance to the chamber is shut with an iron door. In the wall opposite to the retorts, there are two apertures near the floor, for taking out the sulphur. Each of the two retorts belonging to a chamber is charged with 71⁄2or 8 cwts. of sulphur; but one is fired first, and with a gentle heat, lest the brimstone froth should overflow; but when the fumes begin to rise copiously, with a stronger flame. The distillation commences within an hour of kindling the fire, and is completed in six hours. Three hours after putting fire to the first retort, the second is in like manner set in operation.

When the process of distillation is resumed, after having been some time suspended, explosions may be apprehended, from the presence of atmospherical air; to obviate the danger of which, the flap-doors must be opened every 10 minutes; but they should remain closed during the setting of the retorts, and the reflux of sulphurous fumes or acid should be carried off by a draught-hood over the retorts. The distillation is carried on without interruption during the week, the charges being repeated four times in the day. By the third day, the chamber acquires such a degree of heat as to preserve the sulphur in a liquid state; on the sixth, its temperature becoming nearly 300° F., gives the sulphur a dark hue, on which account the furnace is allowed to cool on the Sunday. The fittest distilling temperature is about 248°. The sulphur is drawn off through two iron pipes cast in the iron doors of the orifices on the side of the chamber opposite to the furnace. The iron stoppers being taken out of the mouths of the pipes, the sulphur is allowed to run along an iron spout placed over red-hot charcoal, into the appropriate wooden moulds.

Native sulphurin its pure state is solid, brittle, transparent, yellow, or yellow borderingon green, and of a glassy lustre when newly broken. It occurs frequently in crystalline masses, and sometimes in complete and regular crystals, which are all derivable from the rhomboidal octahedron. The fracture is usually conchoidal and shining. Its specific gravity is 2·072, exceeding somewhat the density of melted sulphur. It possesses a very considerable refractive power; and doubles the images of objects even across two parallel faces. Sulphur, crystallized by artificial means, presents a very remarkable phenomenon; for by varying the processes, crystals are obtained whose forms belong to two different systems of crystallization. The red tint, so common in the crystals of Sicily, and of volcanic districts, has been ascribed by some mineralogists to the presence of realgar, and by others to iron; but Stromeyer has found the sublimed orange-red sulphur of Vulcano, one of the Lipari islands, to result from a natural combination of sulphur and selenium.

It is extracted from the minerals containing it, at Solfatara, by the following process:—

Ten earthen pots, of about a yard in height, and 41⁄2gallons imperial in capacity, bulging in the middle, are ranged in a furnace called a gallery; five being set on the one side, and five on the other. These are so distributed in the body of the walls of the gallery, that their belly projects partly without, and partly within, while their top rises out of the vault of the roof. The pots are filled with lumps of the sulphur ore of the size of the fist; their tops are closed with earthenware lids, and from their shoulder proceeds a pipe of about 2 inches diameter, which bends down, and enters into another covered pot, with a hole in its bottom, standing over a tub filled with water. On applying heat to the gallery, the sulphur melts, volatilizes, and runs down in a liquid state into the tubs, where it congeals. When one operation is finished, the pots are re-charged, and the process is repeated.

In Saxony and Bohemia, the sulphurets of iron and copper are introduced into large earthenware pipes, which traverse a furnace-gallery; and the sulphur exhaled flows into pipes filled with cold water, on the outside of the furnace. 900 parts of sulphuret afford from 100 to 150 of sulphur, and a residuum of metallic protosulphuret. SeeMetallurgyandCopper.

Volcanic sulphur is purer than that extracted from pyrites; and as the latter is commonly mixed with arsenic, and some other metallic impregnations, sulphuric acid made of it would not answer for many purposes of the arts; though a tolerably good sulphuric acid may be made directly from the combustion of pyrites, instead of sulphur, in the lead chambers. The present high price of the Sicilian sulphur is a great encouragement to its extraction from pyrites. It is said that the common English brimstone, such as was extracted from the copper pyrites of the Parys mine of Anglesey, contained fully a fifteenth of residuum, insoluble in boiling oil of turpentine, which was chiefly orpiment; while the fine Sicilian sulphur, now imported in vast quantities by the manufacturers of oil of vitriol, contains not more than 3 per cent. of foreign matter, chiefly earthy, but not at all arsenical.

Sulphur has been known from the most remote antiquity. From its kindling at a moderate temperature, it is employed for readily procuring fire, and lighting by its flame other bodies not so combustible. At Paris, the preparation of sulphur matches constitutes a considerable branch of industry. The sulphurous acid formed by the combustion of sulphur in the atmospheric air, is employed to bleach woollen and silken goods, as also cotton stockings; to disinfect vitiated air, though it is inferior in power to nitric acid vapour and chlorine; to kill mites, moths, and other destructive insects in collections of zoology; and to counteract too rapid fermentation in wine-vats, &c. As the same acid gas has the property of suddenly extinguishing flame, sulphur has been thrown into a chimney on fire, with the best effect; a handful of it being sometimes sufficient. Sulphur is also employed for cementing iron bars in stone; for taking impressions from seals and cameos, for which purpose it is kept previously melted for some time, to give the casts an appearance of bronze. Its principal uses, however, are for the manufactures of vermillion, or cinnabar, gunpowder, and sulphuric acid.

SeeMetallurgy,page 823, for the description of Gahn’s furnace for extracting sulphur from pyrites.

Pyrites as a bi-sulphuret, consisting of 45·5 parts of iron, and 54·5 of sulphur, may, by proper chemical means, be made to give off one half of its sulphur, or about 27 per cent.; but great care must be taken not to generate sulphurous acid, as is done very wastefully by the Fahlun and the Goslar processes. By the latter, indeed, not more than 1 or 2 parts of sulphur are obtained, by roasting 100 parts of the pyritous ores of the Rammelsberg mines. In these cases, the sulphur is burned, instead of being sublimed. The residuum of the operation, when it is well conducted, is black sulphuret of iron, which may be profitably employed for making copperas. The apparatus for extracting sulphur from pyrites should admit no more air than is barely necessary to promote the sublimation.—Sicily produced last year 70,000 tons of sulphur, and Tuscany1200; of which Great Britain consumed 46,000; France, 18,000; other places, 6000. In 1820, Great Britain consumed only 5000 tons.

SULPHURATION, is the process by which woollen, silk, and cotton goods are exposed to the vapours of burning sulphur, or to sulphurous acid gas. In the articleStraw-hat Manufacture, I have described a simple and cheap apparatus, well adapted to this operation.Sulphuring-rooms are sometimes constructed upon a great scale, in which blankets, shawls, and woollen clothes may be suspended freely upon poles or cords. The floor should be flagged with a sloping pavement, to favour the drainage of the water that drops down from the moistened cloth. The iron or stoneware vessels, in which the sulphur is burned, are set in the corners of the apartment. They should be increased in number according to the dimensions of the place, and distributed uniformly over it. The windows and the entrance door must be made to shut hermetically close. In the lower part of the door, there should be a small opening, with a sliding shutter, which may be raised or lowered by the mechanism of a cord passing over a pulley.The aperture by which the sulphurous acid and azotic gases are let off, in order to carry on the combustion, should be somewhat larger than the opening at the bottom. A lofty chimney carries the noxious gases above the building, and diffuses them over a wide space, their ascension being promoted by means of a draught-pipe of iron, connected with an ordinary stove, provided with a valve to close its orifice when not kindled.When the chamber is to be used, the goods are hung up, and a small fire is made in the draught-stove. The proper quantity of sulphur being next put into the shallow pans, it is kindled, the entrance door is closed, as well as its shutter, while a vent-hole near the ground is opened by drawing its cord, which passes over a pulley. After a few minutes, when the sulphur is fully kindled, that vent-hole must be almost entirely shut, by relaxing the cord; when the whole apparatus is to be let alone for a sufficient time.The object of the preceding precautions is to prevent the sulphurous acid gas escaping from the chamber by the seams of the principal doorway. This is secured by closing it imperfectly, so that it may admit of the passage of somewhat more air than can enter by the upper seams, and the smallest quantity of fresh air that can support the combustion. The velocity of the current of air may be increased at pleasure, by enlarging the under vent-hole a little, and quickening the fire of the draught-stove.Before opening the entrance door of the apartment, for the discharge of the goods, a small fire must be lighted in the draught furnace, the vent-hole must be thrown entirely open, and the sliding shutter of the door must be slid up, gradually more and more every quarter of an hour, and finally left wide open for a proper time. By this means the air of the chamber will become soon respirable.

Sulphuring-rooms are sometimes constructed upon a great scale, in which blankets, shawls, and woollen clothes may be suspended freely upon poles or cords. The floor should be flagged with a sloping pavement, to favour the drainage of the water that drops down from the moistened cloth. The iron or stoneware vessels, in which the sulphur is burned, are set in the corners of the apartment. They should be increased in number according to the dimensions of the place, and distributed uniformly over it. The windows and the entrance door must be made to shut hermetically close. In the lower part of the door, there should be a small opening, with a sliding shutter, which may be raised or lowered by the mechanism of a cord passing over a pulley.

The aperture by which the sulphurous acid and azotic gases are let off, in order to carry on the combustion, should be somewhat larger than the opening at the bottom. A lofty chimney carries the noxious gases above the building, and diffuses them over a wide space, their ascension being promoted by means of a draught-pipe of iron, connected with an ordinary stove, provided with a valve to close its orifice when not kindled.

When the chamber is to be used, the goods are hung up, and a small fire is made in the draught-stove. The proper quantity of sulphur being next put into the shallow pans, it is kindled, the entrance door is closed, as well as its shutter, while a vent-hole near the ground is opened by drawing its cord, which passes over a pulley. After a few minutes, when the sulphur is fully kindled, that vent-hole must be almost entirely shut, by relaxing the cord; when the whole apparatus is to be let alone for a sufficient time.

The object of the preceding precautions is to prevent the sulphurous acid gas escaping from the chamber by the seams of the principal doorway. This is secured by closing it imperfectly, so that it may admit of the passage of somewhat more air than can enter by the upper seams, and the smallest quantity of fresh air that can support the combustion. The velocity of the current of air may be increased at pleasure, by enlarging the under vent-hole a little, and quickening the fire of the draught-stove.

Before opening the entrance door of the apartment, for the discharge of the goods, a small fire must be lighted in the draught furnace, the vent-hole must be thrown entirely open, and the sliding shutter of the door must be slid up, gradually more and more every quarter of an hour, and finally left wide open for a proper time. By this means the air of the chamber will become soon respirable.

SULPHURETTED HYDROGEN, is a gas, composed of one part of hydrogen and sixteen parts of sulphur, by weight. Its specific gravity is 1·1912, compared to air = 1·0000. It is the active constituent of the sulphureous mineral waters. When breathed, it is very deleterious to animal life; and being nearly twice as dense as air, it may be poured from its generating bottle into cavities; a scheme successfully employed by M. Thenard to destroy rats in their holes.

SULPHURIC ACID,Vitriolic Acid, orOil of Vitriol(Acid sulfurique, Fr.;Schwefelsaüre, Germ.). This important product, the agent of many chemical operations, was formerly procured by the distillation of dried sulphate of iron, calledgreenvitriol, whence the corrosive liquid which came over, having an oily consistence, was denominated oil of vitriol. This method has been superseded in Great Britain, France, and most other countries, by the combustion of sulphur along with nitre, in large leaden chambers; but as the former process, which is still practised at Bleyl in Bohemia, and Nordhausen in Saxony, gives birth to some interesting results, I shall describe it briefly.Into a long horizontal furnace, or gallery of brickwork, a series of earthenware retorts, of a pear shape, is arranged, with curved necks fitted into stoneware bottles or condensers. Each retort is charged with sulphate of iron, which has been previously heated to moderate redness. The first product of the distillation, a slightly acidulous phlegm, is allowed to escape; then the retort and receiver are securely luted together. The fire is now raised, and urged briskly for 36 hours, whereby the strong sulphuric acid is expelled, in the form of heavy white vapours, which condense in the cold receiver into an oily-looking liquid. The latter portions, when received in a separate refrigerator, frequently concrete into a crystalline mass, formerly called glacial oil of vitriol. About 64 pounds of strong acid may be obtained from 600 pounds of copperas. It is brown-coloured; and varies in specific-gravity from 1·842 to 1·896. Its boiling point is so low as 120° Fahr. When re-distilled in a glass retort, into a receiver surrounded with ice, a very moderate heat sends over white fumes, which condense into a soft solid, in silky filaments, like asbestos, tough, and difficult to cut. When this is exposed tothe air, it emits copious fumes of sulphuric (not sulphurous) acid. It burns holes in paper as rapidly as a red-hot iron. Dropped in small quantities into water, it excites a hissing noise, like ignited metal; and in larger quantities, it occasions an explosion. By dropping a fragment of it into a poised phial containing water, and stoppering instantly, to prevent the ejection of liquid, by the ebullition which always ensues, I got a dilute acid, containing a known portion of the solid acid, from the specific gravity of which, as well as from its saturating power, I ascertained that the above solid sulphuric acid was truly anhydrous (void of water), consisting of 1 equivalent proportion of sulphur, and 3 of oxygen; or, by weight, of 16 of the former, and 24 of the latter. This acid makes a red solution of indigo.The production of sulphuric acid from sulphur and nitre may be elegantly illustrated by means of a glass globe with a stoppered hole at its side, and four bent glass tubes inserted into a leaden cap in its upper orifice. The first tube is to be connected with a heated matrass, disengaging sulphurous acid from copper filings and sulphuric acid; the second with a retort, disengaging more slowly deutoxide of azote (nitric oxide) from copper filings and nitric acid; the third with a vessel for furnishing steam in a moderate current towards the end of the process, when no water has been previously admitted into the balloon; the fourth tube may be upright, and terminate in a small funnel. Through the opening in the side of the globe, atmospherical air is to be admitted from time to time, by removing the stopper; after which, the residuary lighter azote may be allowed to escape by the funnel orifice.The nitric oxide first absorbs oxygen from the air, becomes, in consequence, nitrous acid vapour, which giving up one third of its oxygen to the sulphurous acid, converts this, with the aid of water, into sulphuric acid, while itself returning to the state of nitric oxide, is again qualified to take oxygen from the air, and to transfer it to the sulphurous acid gas; and thus in perpetual rotation. These oxygenating and disoxygenating processes continue until nearly the whole oxygen of the atmospheric air contained in the globe is consumed. Were there little aqueous vapour present, those gases would soon cease to operate upon each other; for though the nitric oxide became nitrous acid, this would oxygenate little of the sulphurous acid, because the three substances would condense into white crystals upon the sides of the balloon, like hoar frost upon a window-pane in winter. These indicate a deficiency of aqueous vapour, and an excess of nitrous acid. On the admission of steam, the crystals disappear, the sulphuric acid is liquefied, the nitrous acid is converted into nitric acid and nitric oxide; the former of which combines with the water, while the latter is converted by the atmospheric oxygen into nitrous acid vapour. A certain quantity of water is therefore requisite to prevent the formation of that crystalline compound, which condenses the nitrous acid, and renders it inoperative in transforming fresh portions of sulphurous acid into sulphuric. On these principles alone is it possible to oxygenate the sulphurous acid, by the nitrous acid resuming and surrendering a dose of oxygen, in perpetual alternation.It was MM. Clement and Desormes who first had the sagacity to trace these complicated changes. They showed that nitrous acid gas and sulphurous acid gas mixed, react on each other through the intervention of moisture; that there resulted thence a combination of sulphuric acid, deutoxide of azote (nitrous gas), and water; that this crystalline compound was instantly destroyed by more water, with the separation of the sulphuric acid in a liquid state, and the disengagement of nitrous gas; that this gas re-constituted nitrous acid at the expense of the atmospheric oxygen of the leaden chamber, and thus brought matters to their primary condition. From this point, starting again, the particles of sulphur in the sulphurous acid, through the agency of water, became fully oxygenated by the nitrous acid, and fell down in heavy drops of sulphuric acid, while the nitrous gas derived from the nitrous acid, had again recourse to the air for its lost dose of oxygen. This beautiful interchange of the oxygenous principle was found to go on, in their experiments, till either the sulphurous acid, or oxygen in the air, was exhausted.They verified this proposition, with regard to what occurs in sulphuric acid chambers, by mixing in a crystal globe the three substances, deutoxide of azote, sulphurous acid, and atmospheric air. The immediate production of red vapours indicated the transformation of the deutoxide into nitrous acid gas; and now the introduction of a very little water caused the properreaction, for opaque vapours rose, which deposited white star-form crystals on the surface of the glass. The gases were once more transparent and colourless; but another addition of water melted these crystals with effervescence, when ruddy vapours appeared. In this manner the phenomena were made to alternate, till the oxygen of the included air was expended, or all the sulphurous acid was converted into sulphuric. The residuary gases were found to be nitrous acid gas, and azote, without sulphurous acid gas; while unctuous sulphuric acid bedewed the inner surface of the globe. Hence, they justly concluded their new theory of the manufacture of oil of vitriol to be demonstrated.In consequence of their discovery, the manufacture of this acid has received suchimprovements, that a nearly double product of it may now be obtained from the same weight of materials. Indeed, the economy may be reckoned to be much greater; for one half of the more costly ingredient, the nitre, formerly employed with a given weight of sulphur, suffices at present.In the manufacture of sulphuric acid upon the great scale, two different systems of working were long prevalent; the intermittent or periodical, and the continuous or uniform. Both were carried on in large leaden chambers. In the former, the chambers were closed during the period of combustion and gaseous combination, but were opened from time to time to introduce fresh atmospheric air. This method is, I believe, generally abandoned now, on account of the difficulties and delays attending it, though it afforded large products in skilful hands. In the latter, a continuous current of air is allowed to enter at the oven in front of the chamber for the combustion of the sulphur, and there is a constant escape of nitrogen gas, with a little sulphurous acid gas, at the remote end of the roof.Sulphuric acid chamberFig.1101.represents a sulphuric acid chamber,a,a, are the brick or stone pillars upon which it rests;b,b, are the sustaining wooden beams or joists;c, is the chimney for the discharge of the nitrogen;d, is the roof, ande, the sole of the hearth for the combustion of the sulphur;f, is the cylindrical tunnel, or pipe of lead or cast iron, for conducting the gasiform materials into the chamber;g, is the steam-boiler; andh, the steam-pipe. That plan is variously modified, by different oil-of-vitriol makers in this country and in France. Very frequently, the ovene,d, is not situated under the chamber, but is built at the end of it, as ati, and arched over with brick, the crown being 9 inches thick. The pipef, 18 inches in diameter, is then placed outside of the chamber, being inserted into a brick chimney, and, turning rectangularly, enters it oppositek. The sole of the hearthe, is a thick plate of cast iron (not hollowed as shown in the figure), 5 or 6 feet long, and 3 or 4 broad, with a small fireplace constructed beneath it, whose smoke-flue runs outwards, under the floor, to the side wall of the building. The oven is in this case about 2 feet in height, from the sole to the roof; and it has an iron door, about 12 inches by 15, which slides up and down in a tightly-fitted iron frame. This door is frequently placed in the side of the oven, parallel to the long side of the leaden chamber. A stout collar of lead is bolted to the chamber, where the pipe enters it. At the middle of the side of the chamber, about 2 feet above the ground, a leaden trough is fixed, which serves as a syphon-funnel and water-trap for introducing water to the acid gases.Several manufacturers divide the chamber into a series of rectangular compartments, by parallel leaden screens, 10 or 12 feet asunder, and allow these compartments to communicate by a narrow opening, or a hole 1 foot square, in the top and bottom of each screen alternately. Thus the fumes, which enter from the chimney-pipe overk, will be forced, by the screen atb, to descend to 1, and pass through the opening there, to get into the second compartment, whence they will escape near the top at 2, thus circulating up and down, so as to occasion a complete agitation and intermixture of their heterogeneous particles. Into the side of the chamber, opposite to the centre of each compartment, a lead pipe enters, and proceeds towards the middle of the area, terminating in a narrow orifice, for discharging a jet of high-pressure steam from a boiler loaded with 40 pounds upon the square inch. This boiler should be placed under a shed exterior to the building. It deserves to be noted, that the incessant tremors produced in this pipe by the escape of the steam, cause the orifice to contract, and eventually to close almost entirely, just as the point of a glass tube does when exposed directly to the flame of a blowpipe. Provision should therefore be made against this event, by the chemical engineer.Equidistant between the middle point and each end of the chamber, two round holes are cut out in its side, about 16 inches in diameter, and 2 feet from the floor; the sheetlead being folded back over the face of the strong deals which strengthen the chamber in that place. The edges of the holes are bevelled outwards, so as to fit a large conical plug of wood faced with lead, called a man-hole door. One or other of these doors is opened from time to time, to allow the superintendent to inspect the process, or workmen to enter, after the chamber is well ventilated, for the purpose of making repairs. The joists or tie-beams, that bind the rafters of the roof of both the leaden chamber and the house, must be at least 7 inches deep, by 3 broad, and of such length as to have their ends supported upon the outer wall, or the columnar supports of the roof, in case a number of chambers are enclosed together in parallel ranges under a vast shed. These beams, which lie two feet apart, suspend the leaden roof, by means of leaden straps, soldered to its upper surface and edges. The sides of the chamber are sustained by means of similar leaden straps affixed to the wooden posts (uprights), 4 inches broad by 3 thick, placed two or three feet apart along the sides of the chamber; resting on the ground below, and mortised into the tie-beams above. Some chambers rest upon a sand-floor; but they are preferably placed upon wooden joists, supported by pillars stretching over an open area, as shown in the figure, into which the workmen may descend readily, to examine the bottom.The outletc, on the top of the chamber, is sometimes joined to a long pipe of lead laid nearly horizontally, with a slight inclination upwards, along the roof, for favouring the condensation and return of acid matter.At the extremityl, of the chamber, which, having a downward slope of 1 inch in every 20 feet, should stand from 3 to 6 inches (according to its length) lower thani, one leg of an inverted syphon pipe is fixed by fusion, into which the liquid of the chamber passing, will show by its altitude the depth on the bottom within. From the cup-shaped orifice of that bent-up pipe, the acid of the chamber is drawn off by an ordinary leaden syphon into the concentration pans.The sheet lead of which the sides and top are made, should weigh from 5 to 6 pounds per square foot; that of the bottom should be nearly of double thickness.Having now detailed, with sufficient minuteness, the construction of the chamber, I shall next describe the mode of operating with it. There are at least two plans at present in use for burning the sulphur continuously in the oven. In the one, the sulphur is laid on the hearthe, (or rather on the flat hearth in the separate oven, above described,) and is kindled by a slight fire placed under it; which fire, however, is allowed to go out after the first day, because the oven becomes by that time sufficiently heated by the sulphur flames to carry on the subsequent combustion. Upon the hearth, an iron tripod is set, supporting, a few inches above it, a hemispherical cast-iron bowl (basin) charged with nitre and its decomposing proportion of strong sulphuric acid. In the other plan, 12 parts of bruised sulphur, and 1 of nitre, are mixed in a leaden trough on the floor with 1 of strong sulphuric acid, and the mixture is shovelled through the sliding iron door upon the hot hearth. The successive charges of sulphur are proportioned, of course, to the size of the chamber. In one of the largest, which is 120 feet long, 20 broad, and 16 high, 12 cwt. are burned in the course of 24 hours, divided into 6 charges, every fourth hour, of 2 cwt. each. In chambers of one-sixth greater capacity, containing 1400 metres cube, 1 ton of sulphur is burned in 24 hours. This immense production was first introduced at Chaunay and Dieuze, under the management of M. Clement-Desormes. The bottom of the chamber should be covered at first with a thin stratum of sulphuric acid, of spec. grav. 1·07, which decomposes nitrous acid into oxygen and nitrous gas; but not with mere water, which would absorb the nitrous acid vapours, and withdraw them from their aerial sphere of action. The vapour of nitric acid, disengaged from the nitre on the hearth of the oven, when brought into intimate contact with the sulphurous acid, either gives up oxygen to it, becomes itself nitrous gas, and converts it into sulphuric acid; or combines with the sulphurous acid into the crystalline compound above described, which, the moment it meets with moisture, is decomposed into sulphuric acid and nitrous gas. The atmospherical oxygen of the chamber immediately reconverts this gas into nitrous or nitric acid fumes, which are again ready, with the co-operation of sulphurous acid gas and aqueous vapour, to produce fresh quantities of hydrous sulphuric acid (oil of vitriol) and nitrous gas. At low temperatures, this curious play of chemical affinities has a great tendency to form the crystalline compound, and to deposit it in a crust of considerable thickness (from one-half to one inch) on the sides of the chamber, so as to render the process inoperative. A circumstance of this kind occurred, in a very striking manner, during winter, in a manufacture of oil of vitriol in Russia; and it has sometimes occurred, to a moderate extent, in Scotland. It is called, at Marseilles, themaladie des chambres. It may be certainly prevented, by maintaining the interior of the chamber, by a jet of steam, at a temperature of 100° F. When these crystals fall into the dilute acid at the bottom, they are decomposed with a violent effervescence, and a hissing gurgling noise, somewhat like that of a tun of beer in brisk fermentation.M. Clement-Desormes demonstrated the proposition relative to the influence of temperature by a decisive experiment. He took a glass globe, furnished with three tubulures, and put a bit of ice into it. Through the first opening he then introduced sulphurous acid gas; through the second, oxygen; and through the third, nitrous gas (deutoxide of azote). While the globe was kept cool, by being plunged in iced water, no sulphuric acid was formed, though all the ingredients essential to its production were present. But on exposing the globe to a temperature of 100° Fahr., the four bodies began immediately to react on each other, and oil of vitriol was condensed in visiblestriæ.The introduction of steam is a modern invention, which has vastly facilitated and increased the production of oil of vitriol. It serves, by powerful agitation, not only to mix the different gaseous molecules intimately together, but to impel them against each other, and thus bring them within the sphere of their mutual chemical attraction. This is its mechanical effect. Its chemical agency is still more important. By supplying moisture at every point of the immense included space, it determines the formation of hydrous sulphuric acid, from the compound of nitric, nitrous, sulphurous, and dry sulphuric acids. No sooner is this reaction accomplished, than the nitrous gas resumes its oxygen, from the continuous atmospherical current, and becomes again fit to operate a like round of transmutations with sulphurous acid, steam, and oxygen. The nitrogen (azote), which ought to be the only residuum in aperfectlyregulated vitriol chamber, escapes, by its relative lightness, at the openingc, in the roof, or, more properly speaking, is displaced by the influx of the heavier gases at the entrance-pipe.On the intermittent plan, after the consumption of each charge, and condensation of the product, the chamber was opened, and freely ventilated, so as to expel the residuary azote, and replenish it with fresh atmospheric air. In this system there were four distinct stages or periods:—1. Combustion for two hours; 2. Admission of steam, and settling, for an hour and a half; 3. Conversion, for three hours, during which interval the drops of strong acid were heard falling like heavy hailstones on the bottom; 4. Purging of the chamber, for three quarters of an hour.By the continuous method, sulphuric acid may be currently obtained in the chambers, of the specific gravity 1·350, or 1·450 at most; for, when stronger, it absorbs and retains permanently much nitrous acid gas; but by the intermittent, so dense as 1·550, or even 1·620; whence in a district where fuel is high priced, as near Paris, this method recommended itself by economy in the concentration of the acid. In Great Britain, and even in most parts of France, however, where time, workmen’s wages, and interest of capital, are the paramount considerations, manufacturers do not find it for their interest in general to raise the density of the acid in the chambers above 1·400, or at most 1·500; as the further increase goes on at a retarded rate, and its concentration from 1·400 to 1·600, in leaden pans, costs very little.At about the specific gravity of 1·35, in Great Britain, the liquid of the chambers is run off, by the syphon above described, into a leaden gutter or spout, which discharges it into a series of rectangular vessels made of large sheets of lead, of 12 or 14 lbs. to the square foot, simply folded up at the angles into pans 8 or 10 inches deep, resting upon a grate made of a pretty close row of wrought-iron bars of considerable strength, under which the flame of a furnace plays. Where coals are very cheap, each pan may have a separate fire; but where they are somewhat dear, the flame, after passing under the lowest pan of the range, which contains the strongest acid (at about 1·600), proceeds upwards with a slight slope to heat the pans of weaker acid, which, as it concentrates, is gradually run down by syphons to replenish the lower pans, in proportion as their aqueous matter is dissipated. The 3 or 4 pans constituting the range are thus placed in a straight line, but each at a different level, terrace-like;en gradins, as the French say.When the acid has thereby acquired the density of 1·650, or 1·700 at most, it must be removed from the leaden evaporators, because, when of greater strength, it would begin to corrode them; and it is transferred into leaden coolers, or run through a long refrigeratory worm-pipe surrounded by cold water. In this state it is introduced into glass or platinum retorts, to undergo a final concentration, up to the specific gravity of 1·842, or even occasionally 1·845, in consequence of slight saline impurities. When glass retorts are used, they are set in a long sand-bath over a gallery furnace, resting on fire tiles, under which a powerful flame plays; and as the flue gradually ascends from the fireplace, near to which it is most distant from the tiles; to the remoter end, the heat acts with tolerable equality on the first and last retort in the range. When platinum stills are employed, they are fitted into the inside of cast-iron pots, which protect the thin bottom and sides of the precious metal. The fire being applied directly to the iron, causes a safe, rapid, and economical concentration of the acid. The iron pots, with their platinum interior, filled with concentrated boiling-hot oil of vitriol, are lifted out of the fire-seat by tackle, and let down into a cistern of cold water, to effect the speedy refrigeration of the acid, and facilitate its transvasion into carboys packed in osier baskets lined with straw. Sometimes, however, the acid is cooled by running itslowly off through a long platinum syphon, surrounded by another pipe filled with cold water.Fig.1102.shows my contrivance for this purpose.SyphonThe under stopcocka, being shut, and the legb, being plunged to nearly the bottom of the still, the worm is to be filled with concentrated cold acid through the funnelc. If that stopcock is now shut, andaopened, the acid will flow out in such quantity as to rarefy the small portion of air in the upper part of the pipeb, sufficiently to make the hot acid rise up over the bend, and set the syphon in action. The flow of the fluid is to be so regulated by the stopcocka, that it may be greatly cooled in its passage by the surrounding cold water in the vesself, which may be replenished by means of the tube and funneld, and overflow ate.A manufacturer of acid in Scotland, who burns in each chamber 210 pounds of sulphur in 24 hours, being at the rate of 420 pounds for 20,000 cubic feet (= nearly 2000 metres cube) has a product of nearly 3 pounds of concentrated oil of vitriol for every pound of sulphur and twelfth of a pound of nitre. The advantage of his process results, I conceive, from the lower concentration of the acid in the chambers, which favours its more rapid production.The platinum retort admits of from 4 to 6 operations in a day, when it is well mounted and managed. It has a capital of platinum, furnished with a short neck, which conducts the disengaged vapours into a lead worm of condensation; and the liquid thus obtained is returned into the lead pans. Great care must be taken to prevent any particles of lead from getting into the platinum vessel, since at the temperature of boiling sulphuric acid, the lead unites with the precious metal, and thus causes holes in the retort. These must be repaired by soldering-on a plate of platinum with gold.Before the separate oven or hearth for burning the sulphur in contact with the nitre was adopted, this combustible mixture was introduced into the chamber itself, spread on iron trays or earthen pans, supported above the water on iron stands. But this plan was very laborious and unproductive. It is no longer followed.One of the characters of the good quality of sulphuric acid, is its dissolving indigo without altering its fine blue colour.Sulphuric acid, when well prepared, is a colourless and inodorous liquid, of an oily aspect, possessing a specific gravity, in its most concentrated state, of 1·842, when redistilled, but as found in commerce, of 1·845. It is eminently acid and corrosive, so that a single drop will communicate the power of reddening litmus to a gallon of water, and will produce an ulcer of the skin when allowed to remain upon it. If swallowed in its strongest state, in even a small quantity, it acts so furiously on the throat and stomach as to cause intolerable agony and speedy death. Watery diluents, mixed with chalk or magnesia, are the readiest antidotes. At a temperature of about 600° F., or a few degrees below the melting point of lead, it boils and distils over like water. This is the best method of procuring sulphuric acid free from the saline and metallic matters with which it is sometimes contaminated.The affinity of sulphuric acid for water is so strong that, when exposed in an open saucer, it imbibes one-third of its weight from the atmosphere in 24 hours, and fully six times its weight in a few months. Hence it should be kept excluded from the air. If four parts, by weight, of the strongest acid be suddenly mixed with one part of water, both being at 50° F., the temperature of the mixture will rise to 300°; while, on the other hand, if four parts of ice be mixed with one of sulphuric acid, they immediately liquefy and sink the thermometer to 4° below zero. From the great attraction existing between this acid and water, a saucer of it is employed to effect the rapid condensation of aqueous vapour as it exhales from a cup of water placed over it; both standing under the exhausted receiver of an air-pump. By the cold produced by this unchecked evaporation in vacuo, the water is speedily frozen.To determine the purity of sulphuric acid, let it be slowly heated to the boiling point of water, and if any volatile acid matter be present, it will evaporate, with its characteristic smell. The presence of saline impurity, which is the common one, is discovered by evaporating a given weight of it in a small capsule of platinum placed on red-hot cinders. If more than two grains remain out of 500, the acid may be reckoned to beimpure. The best test for sulphuric acid, and the soluble salts into which it enters, is the nitrate of baryta, of which 182 parts are equivalent to 49 of the strongest liquid acid, or to 40 of the dry, as it exists in crystallized sulphate of potassa. One twenty thousandth part of a grain of the acid may be detected by the grayish-white cloud which baryta forms with it. 100 parts of the concentrated acid are neutralized by 143 parts of dry carbonate of potassa, and by 110 of dry carbonate of soda, both perfectly pure.Of all the acids, the sulphuric is most extensively used in the arts, and is, in fact, the primary agent for obtaining almost all the others, by disengaging them from their saline combinations. In this way, nitric, muriatic, tartaric, acetic, and many other acids, are procured. It is employed in the direct formation of alum, of the sulphates of copper, zinc, potassa, soda; in that of sulphuric ether, of sugar by the saccharification of starch, and in the preparation of phosphorus, &c. It serves also for opening the pores of skins in tanning, for clearing the surfaces of metals, for determining the nature of several salts by the acid characters that are disengaged, &c.According to the analysis of Dr. Thomson, the crystalline compound deposited occasionally in the leaden chambers above described consists of—Sulphurous acid0·6387,or3atoms.Sulphuric acid0·5290,2Nitric acid0·3450,1atom.Water0·0733,1Sulphate of lead0·0140.He admits that the proportion of water is a little uncertain; and that the presence of sulphurous acid was not proved by direct analysis. When heated with water, the crystalline matter disengages nitrous gas in abundance; lets fall some sulphate of lead; and the liquid is found to be sulphuric acid. When heated without water, it is decomposed with emission of nitrous gas and fuming nitric acid; leaving a liquid which, mixed with water, produces a brisk effervescence, consisting chiefly of nitrous gas.The followingTableshows the quantity of concentrated and dry sulphuric acid in 100 parts of dilute, at different densities, by my experiments, published in the Quarterly Journal of Science, for October, 1817:—Liquid.Sp. grav.Dry.1001·846081·54991·843880·72981·841579·90971·839179·09961·836678·28951·834077·46941·828876·65931·823575·83921·818175·02911·802674·20901·807073·39891·798672·57881·790171·75871·781570·94861·772870·12851·764069·31841·754068·49831·742567·68821·731566·86811·720066·05801·708065·23791·697264·42781·686063·60771·674462·78761·662461·97751·650061·15741·641560·34731·632159·52721·620458·71711·609057·89701·597557·08691·586856·26681·576055·45671·564854·63661·550353·82651·539053·00641·528052·18631·517051·37621·506650·55611·496049·74601·486048·92591·476048·11581·466047·29571·456046·48561·446045·66551·436044·85541·426544·03531·417043·22521·407342·40511·397741·58501·388440·77491·378839·95481·369739·14471·361238·32461·353037·51451·344036·69441·334535·88431·325535·06421·316534·25411·308033·43401·299932·61391·291331·80381·282630·98371·274030·17361·265429·35351·257228·54341·249027·72331·240926·91321·233426·09311·226025·28301·218424·46291·210823·65281·203222·83271·195622·01261·187621·20251·179220·38241·170619·57231·162618·75221·154917·94211·148017·12201·141016·31191·133015·49181·124614·68171·116513·86161·109013·05151·101912·23141·095311·41131·088710·60121·08099·78111·07438·97101·06828·1591·06147·3481·05446·5271·04775·7161·04054·8951·03364·0841·02683·2631·02062·44621·01401·6311·00740·8154

Into a long horizontal furnace, or gallery of brickwork, a series of earthenware retorts, of a pear shape, is arranged, with curved necks fitted into stoneware bottles or condensers. Each retort is charged with sulphate of iron, which has been previously heated to moderate redness. The first product of the distillation, a slightly acidulous phlegm, is allowed to escape; then the retort and receiver are securely luted together. The fire is now raised, and urged briskly for 36 hours, whereby the strong sulphuric acid is expelled, in the form of heavy white vapours, which condense in the cold receiver into an oily-looking liquid. The latter portions, when received in a separate refrigerator, frequently concrete into a crystalline mass, formerly called glacial oil of vitriol. About 64 pounds of strong acid may be obtained from 600 pounds of copperas. It is brown-coloured; and varies in specific-gravity from 1·842 to 1·896. Its boiling point is so low as 120° Fahr. When re-distilled in a glass retort, into a receiver surrounded with ice, a very moderate heat sends over white fumes, which condense into a soft solid, in silky filaments, like asbestos, tough, and difficult to cut. When this is exposed tothe air, it emits copious fumes of sulphuric (not sulphurous) acid. It burns holes in paper as rapidly as a red-hot iron. Dropped in small quantities into water, it excites a hissing noise, like ignited metal; and in larger quantities, it occasions an explosion. By dropping a fragment of it into a poised phial containing water, and stoppering instantly, to prevent the ejection of liquid, by the ebullition which always ensues, I got a dilute acid, containing a known portion of the solid acid, from the specific gravity of which, as well as from its saturating power, I ascertained that the above solid sulphuric acid was truly anhydrous (void of water), consisting of 1 equivalent proportion of sulphur, and 3 of oxygen; or, by weight, of 16 of the former, and 24 of the latter. This acid makes a red solution of indigo.

The production of sulphuric acid from sulphur and nitre may be elegantly illustrated by means of a glass globe with a stoppered hole at its side, and four bent glass tubes inserted into a leaden cap in its upper orifice. The first tube is to be connected with a heated matrass, disengaging sulphurous acid from copper filings and sulphuric acid; the second with a retort, disengaging more slowly deutoxide of azote (nitric oxide) from copper filings and nitric acid; the third with a vessel for furnishing steam in a moderate current towards the end of the process, when no water has been previously admitted into the balloon; the fourth tube may be upright, and terminate in a small funnel. Through the opening in the side of the globe, atmospherical air is to be admitted from time to time, by removing the stopper; after which, the residuary lighter azote may be allowed to escape by the funnel orifice.

The nitric oxide first absorbs oxygen from the air, becomes, in consequence, nitrous acid vapour, which giving up one third of its oxygen to the sulphurous acid, converts this, with the aid of water, into sulphuric acid, while itself returning to the state of nitric oxide, is again qualified to take oxygen from the air, and to transfer it to the sulphurous acid gas; and thus in perpetual rotation. These oxygenating and disoxygenating processes continue until nearly the whole oxygen of the atmospheric air contained in the globe is consumed. Were there little aqueous vapour present, those gases would soon cease to operate upon each other; for though the nitric oxide became nitrous acid, this would oxygenate little of the sulphurous acid, because the three substances would condense into white crystals upon the sides of the balloon, like hoar frost upon a window-pane in winter. These indicate a deficiency of aqueous vapour, and an excess of nitrous acid. On the admission of steam, the crystals disappear, the sulphuric acid is liquefied, the nitrous acid is converted into nitric acid and nitric oxide; the former of which combines with the water, while the latter is converted by the atmospheric oxygen into nitrous acid vapour. A certain quantity of water is therefore requisite to prevent the formation of that crystalline compound, which condenses the nitrous acid, and renders it inoperative in transforming fresh portions of sulphurous acid into sulphuric. On these principles alone is it possible to oxygenate the sulphurous acid, by the nitrous acid resuming and surrendering a dose of oxygen, in perpetual alternation.

It was MM. Clement and Desormes who first had the sagacity to trace these complicated changes. They showed that nitrous acid gas and sulphurous acid gas mixed, react on each other through the intervention of moisture; that there resulted thence a combination of sulphuric acid, deutoxide of azote (nitrous gas), and water; that this crystalline compound was instantly destroyed by more water, with the separation of the sulphuric acid in a liquid state, and the disengagement of nitrous gas; that this gas re-constituted nitrous acid at the expense of the atmospheric oxygen of the leaden chamber, and thus brought matters to their primary condition. From this point, starting again, the particles of sulphur in the sulphurous acid, through the agency of water, became fully oxygenated by the nitrous acid, and fell down in heavy drops of sulphuric acid, while the nitrous gas derived from the nitrous acid, had again recourse to the air for its lost dose of oxygen. This beautiful interchange of the oxygenous principle was found to go on, in their experiments, till either the sulphurous acid, or oxygen in the air, was exhausted.

They verified this proposition, with regard to what occurs in sulphuric acid chambers, by mixing in a crystal globe the three substances, deutoxide of azote, sulphurous acid, and atmospheric air. The immediate production of red vapours indicated the transformation of the deutoxide into nitrous acid gas; and now the introduction of a very little water caused the properreaction, for opaque vapours rose, which deposited white star-form crystals on the surface of the glass. The gases were once more transparent and colourless; but another addition of water melted these crystals with effervescence, when ruddy vapours appeared. In this manner the phenomena were made to alternate, till the oxygen of the included air was expended, or all the sulphurous acid was converted into sulphuric. The residuary gases were found to be nitrous acid gas, and azote, without sulphurous acid gas; while unctuous sulphuric acid bedewed the inner surface of the globe. Hence, they justly concluded their new theory of the manufacture of oil of vitriol to be demonstrated.

In consequence of their discovery, the manufacture of this acid has received suchimprovements, that a nearly double product of it may now be obtained from the same weight of materials. Indeed, the economy may be reckoned to be much greater; for one half of the more costly ingredient, the nitre, formerly employed with a given weight of sulphur, suffices at present.

In the manufacture of sulphuric acid upon the great scale, two different systems of working were long prevalent; the intermittent or periodical, and the continuous or uniform. Both were carried on in large leaden chambers. In the former, the chambers were closed during the period of combustion and gaseous combination, but were opened from time to time to introduce fresh atmospheric air. This method is, I believe, generally abandoned now, on account of the difficulties and delays attending it, though it afforded large products in skilful hands. In the latter, a continuous current of air is allowed to enter at the oven in front of the chamber for the combustion of the sulphur, and there is a constant escape of nitrogen gas, with a little sulphurous acid gas, at the remote end of the roof.

Sulphuric acid chamber

Fig.1101.represents a sulphuric acid chamber,a,a, are the brick or stone pillars upon which it rests;b,b, are the sustaining wooden beams or joists;c, is the chimney for the discharge of the nitrogen;d, is the roof, ande, the sole of the hearth for the combustion of the sulphur;f, is the cylindrical tunnel, or pipe of lead or cast iron, for conducting the gasiform materials into the chamber;g, is the steam-boiler; andh, the steam-pipe. That plan is variously modified, by different oil-of-vitriol makers in this country and in France. Very frequently, the ovene,d, is not situated under the chamber, but is built at the end of it, as ati, and arched over with brick, the crown being 9 inches thick. The pipef, 18 inches in diameter, is then placed outside of the chamber, being inserted into a brick chimney, and, turning rectangularly, enters it oppositek. The sole of the hearthe, is a thick plate of cast iron (not hollowed as shown in the figure), 5 or 6 feet long, and 3 or 4 broad, with a small fireplace constructed beneath it, whose smoke-flue runs outwards, under the floor, to the side wall of the building. The oven is in this case about 2 feet in height, from the sole to the roof; and it has an iron door, about 12 inches by 15, which slides up and down in a tightly-fitted iron frame. This door is frequently placed in the side of the oven, parallel to the long side of the leaden chamber. A stout collar of lead is bolted to the chamber, where the pipe enters it. At the middle of the side of the chamber, about 2 feet above the ground, a leaden trough is fixed, which serves as a syphon-funnel and water-trap for introducing water to the acid gases.

Several manufacturers divide the chamber into a series of rectangular compartments, by parallel leaden screens, 10 or 12 feet asunder, and allow these compartments to communicate by a narrow opening, or a hole 1 foot square, in the top and bottom of each screen alternately. Thus the fumes, which enter from the chimney-pipe overk, will be forced, by the screen atb, to descend to 1, and pass through the opening there, to get into the second compartment, whence they will escape near the top at 2, thus circulating up and down, so as to occasion a complete agitation and intermixture of their heterogeneous particles. Into the side of the chamber, opposite to the centre of each compartment, a lead pipe enters, and proceeds towards the middle of the area, terminating in a narrow orifice, for discharging a jet of high-pressure steam from a boiler loaded with 40 pounds upon the square inch. This boiler should be placed under a shed exterior to the building. It deserves to be noted, that the incessant tremors produced in this pipe by the escape of the steam, cause the orifice to contract, and eventually to close almost entirely, just as the point of a glass tube does when exposed directly to the flame of a blowpipe. Provision should therefore be made against this event, by the chemical engineer.

Equidistant between the middle point and each end of the chamber, two round holes are cut out in its side, about 16 inches in diameter, and 2 feet from the floor; the sheetlead being folded back over the face of the strong deals which strengthen the chamber in that place. The edges of the holes are bevelled outwards, so as to fit a large conical plug of wood faced with lead, called a man-hole door. One or other of these doors is opened from time to time, to allow the superintendent to inspect the process, or workmen to enter, after the chamber is well ventilated, for the purpose of making repairs. The joists or tie-beams, that bind the rafters of the roof of both the leaden chamber and the house, must be at least 7 inches deep, by 3 broad, and of such length as to have their ends supported upon the outer wall, or the columnar supports of the roof, in case a number of chambers are enclosed together in parallel ranges under a vast shed. These beams, which lie two feet apart, suspend the leaden roof, by means of leaden straps, soldered to its upper surface and edges. The sides of the chamber are sustained by means of similar leaden straps affixed to the wooden posts (uprights), 4 inches broad by 3 thick, placed two or three feet apart along the sides of the chamber; resting on the ground below, and mortised into the tie-beams above. Some chambers rest upon a sand-floor; but they are preferably placed upon wooden joists, supported by pillars stretching over an open area, as shown in the figure, into which the workmen may descend readily, to examine the bottom.

The outletc, on the top of the chamber, is sometimes joined to a long pipe of lead laid nearly horizontally, with a slight inclination upwards, along the roof, for favouring the condensation and return of acid matter.

At the extremityl, of the chamber, which, having a downward slope of 1 inch in every 20 feet, should stand from 3 to 6 inches (according to its length) lower thani, one leg of an inverted syphon pipe is fixed by fusion, into which the liquid of the chamber passing, will show by its altitude the depth on the bottom within. From the cup-shaped orifice of that bent-up pipe, the acid of the chamber is drawn off by an ordinary leaden syphon into the concentration pans.

The sheet lead of which the sides and top are made, should weigh from 5 to 6 pounds per square foot; that of the bottom should be nearly of double thickness.

Having now detailed, with sufficient minuteness, the construction of the chamber, I shall next describe the mode of operating with it. There are at least two plans at present in use for burning the sulphur continuously in the oven. In the one, the sulphur is laid on the hearthe, (or rather on the flat hearth in the separate oven, above described,) and is kindled by a slight fire placed under it; which fire, however, is allowed to go out after the first day, because the oven becomes by that time sufficiently heated by the sulphur flames to carry on the subsequent combustion. Upon the hearth, an iron tripod is set, supporting, a few inches above it, a hemispherical cast-iron bowl (basin) charged with nitre and its decomposing proportion of strong sulphuric acid. In the other plan, 12 parts of bruised sulphur, and 1 of nitre, are mixed in a leaden trough on the floor with 1 of strong sulphuric acid, and the mixture is shovelled through the sliding iron door upon the hot hearth. The successive charges of sulphur are proportioned, of course, to the size of the chamber. In one of the largest, which is 120 feet long, 20 broad, and 16 high, 12 cwt. are burned in the course of 24 hours, divided into 6 charges, every fourth hour, of 2 cwt. each. In chambers of one-sixth greater capacity, containing 1400 metres cube, 1 ton of sulphur is burned in 24 hours. This immense production was first introduced at Chaunay and Dieuze, under the management of M. Clement-Desormes. The bottom of the chamber should be covered at first with a thin stratum of sulphuric acid, of spec. grav. 1·07, which decomposes nitrous acid into oxygen and nitrous gas; but not with mere water, which would absorb the nitrous acid vapours, and withdraw them from their aerial sphere of action. The vapour of nitric acid, disengaged from the nitre on the hearth of the oven, when brought into intimate contact with the sulphurous acid, either gives up oxygen to it, becomes itself nitrous gas, and converts it into sulphuric acid; or combines with the sulphurous acid into the crystalline compound above described, which, the moment it meets with moisture, is decomposed into sulphuric acid and nitrous gas. The atmospherical oxygen of the chamber immediately reconverts this gas into nitrous or nitric acid fumes, which are again ready, with the co-operation of sulphurous acid gas and aqueous vapour, to produce fresh quantities of hydrous sulphuric acid (oil of vitriol) and nitrous gas. At low temperatures, this curious play of chemical affinities has a great tendency to form the crystalline compound, and to deposit it in a crust of considerable thickness (from one-half to one inch) on the sides of the chamber, so as to render the process inoperative. A circumstance of this kind occurred, in a very striking manner, during winter, in a manufacture of oil of vitriol in Russia; and it has sometimes occurred, to a moderate extent, in Scotland. It is called, at Marseilles, themaladie des chambres. It may be certainly prevented, by maintaining the interior of the chamber, by a jet of steam, at a temperature of 100° F. When these crystals fall into the dilute acid at the bottom, they are decomposed with a violent effervescence, and a hissing gurgling noise, somewhat like that of a tun of beer in brisk fermentation.

M. Clement-Desormes demonstrated the proposition relative to the influence of temperature by a decisive experiment. He took a glass globe, furnished with three tubulures, and put a bit of ice into it. Through the first opening he then introduced sulphurous acid gas; through the second, oxygen; and through the third, nitrous gas (deutoxide of azote). While the globe was kept cool, by being plunged in iced water, no sulphuric acid was formed, though all the ingredients essential to its production were present. But on exposing the globe to a temperature of 100° Fahr., the four bodies began immediately to react on each other, and oil of vitriol was condensed in visiblestriæ.

The introduction of steam is a modern invention, which has vastly facilitated and increased the production of oil of vitriol. It serves, by powerful agitation, not only to mix the different gaseous molecules intimately together, but to impel them against each other, and thus bring them within the sphere of their mutual chemical attraction. This is its mechanical effect. Its chemical agency is still more important. By supplying moisture at every point of the immense included space, it determines the formation of hydrous sulphuric acid, from the compound of nitric, nitrous, sulphurous, and dry sulphuric acids. No sooner is this reaction accomplished, than the nitrous gas resumes its oxygen, from the continuous atmospherical current, and becomes again fit to operate a like round of transmutations with sulphurous acid, steam, and oxygen. The nitrogen (azote), which ought to be the only residuum in aperfectlyregulated vitriol chamber, escapes, by its relative lightness, at the openingc, in the roof, or, more properly speaking, is displaced by the influx of the heavier gases at the entrance-pipe.

On the intermittent plan, after the consumption of each charge, and condensation of the product, the chamber was opened, and freely ventilated, so as to expel the residuary azote, and replenish it with fresh atmospheric air. In this system there were four distinct stages or periods:—1. Combustion for two hours; 2. Admission of steam, and settling, for an hour and a half; 3. Conversion, for three hours, during which interval the drops of strong acid were heard falling like heavy hailstones on the bottom; 4. Purging of the chamber, for three quarters of an hour.

By the continuous method, sulphuric acid may be currently obtained in the chambers, of the specific gravity 1·350, or 1·450 at most; for, when stronger, it absorbs and retains permanently much nitrous acid gas; but by the intermittent, so dense as 1·550, or even 1·620; whence in a district where fuel is high priced, as near Paris, this method recommended itself by economy in the concentration of the acid. In Great Britain, and even in most parts of France, however, where time, workmen’s wages, and interest of capital, are the paramount considerations, manufacturers do not find it for their interest in general to raise the density of the acid in the chambers above 1·400, or at most 1·500; as the further increase goes on at a retarded rate, and its concentration from 1·400 to 1·600, in leaden pans, costs very little.

At about the specific gravity of 1·35, in Great Britain, the liquid of the chambers is run off, by the syphon above described, into a leaden gutter or spout, which discharges it into a series of rectangular vessels made of large sheets of lead, of 12 or 14 lbs. to the square foot, simply folded up at the angles into pans 8 or 10 inches deep, resting upon a grate made of a pretty close row of wrought-iron bars of considerable strength, under which the flame of a furnace plays. Where coals are very cheap, each pan may have a separate fire; but where they are somewhat dear, the flame, after passing under the lowest pan of the range, which contains the strongest acid (at about 1·600), proceeds upwards with a slight slope to heat the pans of weaker acid, which, as it concentrates, is gradually run down by syphons to replenish the lower pans, in proportion as their aqueous matter is dissipated. The 3 or 4 pans constituting the range are thus placed in a straight line, but each at a different level, terrace-like;en gradins, as the French say.

When the acid has thereby acquired the density of 1·650, or 1·700 at most, it must be removed from the leaden evaporators, because, when of greater strength, it would begin to corrode them; and it is transferred into leaden coolers, or run through a long refrigeratory worm-pipe surrounded by cold water. In this state it is introduced into glass or platinum retorts, to undergo a final concentration, up to the specific gravity of 1·842, or even occasionally 1·845, in consequence of slight saline impurities. When glass retorts are used, they are set in a long sand-bath over a gallery furnace, resting on fire tiles, under which a powerful flame plays; and as the flue gradually ascends from the fireplace, near to which it is most distant from the tiles; to the remoter end, the heat acts with tolerable equality on the first and last retort in the range. When platinum stills are employed, they are fitted into the inside of cast-iron pots, which protect the thin bottom and sides of the precious metal. The fire being applied directly to the iron, causes a safe, rapid, and economical concentration of the acid. The iron pots, with their platinum interior, filled with concentrated boiling-hot oil of vitriol, are lifted out of the fire-seat by tackle, and let down into a cistern of cold water, to effect the speedy refrigeration of the acid, and facilitate its transvasion into carboys packed in osier baskets lined with straw. Sometimes, however, the acid is cooled by running itslowly off through a long platinum syphon, surrounded by another pipe filled with cold water.Fig.1102.shows my contrivance for this purpose.

Syphon

The under stopcocka, being shut, and the legb, being plunged to nearly the bottom of the still, the worm is to be filled with concentrated cold acid through the funnelc. If that stopcock is now shut, andaopened, the acid will flow out in such quantity as to rarefy the small portion of air in the upper part of the pipeb, sufficiently to make the hot acid rise up over the bend, and set the syphon in action. The flow of the fluid is to be so regulated by the stopcocka, that it may be greatly cooled in its passage by the surrounding cold water in the vesself, which may be replenished by means of the tube and funneld, and overflow ate.

A manufacturer of acid in Scotland, who burns in each chamber 210 pounds of sulphur in 24 hours, being at the rate of 420 pounds for 20,000 cubic feet (= nearly 2000 metres cube) has a product of nearly 3 pounds of concentrated oil of vitriol for every pound of sulphur and twelfth of a pound of nitre. The advantage of his process results, I conceive, from the lower concentration of the acid in the chambers, which favours its more rapid production.

The platinum retort admits of from 4 to 6 operations in a day, when it is well mounted and managed. It has a capital of platinum, furnished with a short neck, which conducts the disengaged vapours into a lead worm of condensation; and the liquid thus obtained is returned into the lead pans. Great care must be taken to prevent any particles of lead from getting into the platinum vessel, since at the temperature of boiling sulphuric acid, the lead unites with the precious metal, and thus causes holes in the retort. These must be repaired by soldering-on a plate of platinum with gold.

Before the separate oven or hearth for burning the sulphur in contact with the nitre was adopted, this combustible mixture was introduced into the chamber itself, spread on iron trays or earthen pans, supported above the water on iron stands. But this plan was very laborious and unproductive. It is no longer followed.

One of the characters of the good quality of sulphuric acid, is its dissolving indigo without altering its fine blue colour.

Sulphuric acid, when well prepared, is a colourless and inodorous liquid, of an oily aspect, possessing a specific gravity, in its most concentrated state, of 1·842, when redistilled, but as found in commerce, of 1·845. It is eminently acid and corrosive, so that a single drop will communicate the power of reddening litmus to a gallon of water, and will produce an ulcer of the skin when allowed to remain upon it. If swallowed in its strongest state, in even a small quantity, it acts so furiously on the throat and stomach as to cause intolerable agony and speedy death. Watery diluents, mixed with chalk or magnesia, are the readiest antidotes. At a temperature of about 600° F., or a few degrees below the melting point of lead, it boils and distils over like water. This is the best method of procuring sulphuric acid free from the saline and metallic matters with which it is sometimes contaminated.

The affinity of sulphuric acid for water is so strong that, when exposed in an open saucer, it imbibes one-third of its weight from the atmosphere in 24 hours, and fully six times its weight in a few months. Hence it should be kept excluded from the air. If four parts, by weight, of the strongest acid be suddenly mixed with one part of water, both being at 50° F., the temperature of the mixture will rise to 300°; while, on the other hand, if four parts of ice be mixed with one of sulphuric acid, they immediately liquefy and sink the thermometer to 4° below zero. From the great attraction existing between this acid and water, a saucer of it is employed to effect the rapid condensation of aqueous vapour as it exhales from a cup of water placed over it; both standing under the exhausted receiver of an air-pump. By the cold produced by this unchecked evaporation in vacuo, the water is speedily frozen.

To determine the purity of sulphuric acid, let it be slowly heated to the boiling point of water, and if any volatile acid matter be present, it will evaporate, with its characteristic smell. The presence of saline impurity, which is the common one, is discovered by evaporating a given weight of it in a small capsule of platinum placed on red-hot cinders. If more than two grains remain out of 500, the acid may be reckoned to beimpure. The best test for sulphuric acid, and the soluble salts into which it enters, is the nitrate of baryta, of which 182 parts are equivalent to 49 of the strongest liquid acid, or to 40 of the dry, as it exists in crystallized sulphate of potassa. One twenty thousandth part of a grain of the acid may be detected by the grayish-white cloud which baryta forms with it. 100 parts of the concentrated acid are neutralized by 143 parts of dry carbonate of potassa, and by 110 of dry carbonate of soda, both perfectly pure.

Of all the acids, the sulphuric is most extensively used in the arts, and is, in fact, the primary agent for obtaining almost all the others, by disengaging them from their saline combinations. In this way, nitric, muriatic, tartaric, acetic, and many other acids, are procured. It is employed in the direct formation of alum, of the sulphates of copper, zinc, potassa, soda; in that of sulphuric ether, of sugar by the saccharification of starch, and in the preparation of phosphorus, &c. It serves also for opening the pores of skins in tanning, for clearing the surfaces of metals, for determining the nature of several salts by the acid characters that are disengaged, &c.

According to the analysis of Dr. Thomson, the crystalline compound deposited occasionally in the leaden chambers above described consists of—

He admits that the proportion of water is a little uncertain; and that the presence of sulphurous acid was not proved by direct analysis. When heated with water, the crystalline matter disengages nitrous gas in abundance; lets fall some sulphate of lead; and the liquid is found to be sulphuric acid. When heated without water, it is decomposed with emission of nitrous gas and fuming nitric acid; leaving a liquid which, mixed with water, produces a brisk effervescence, consisting chiefly of nitrous gas.

The followingTableshows the quantity of concentrated and dry sulphuric acid in 100 parts of dilute, at different densities, by my experiments, published in the Quarterly Journal of Science, for October, 1817:—

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