Part 39

1. A solution being obtained as above, if necessary, it is strongly acidulated with tartaric acid, and the antimony thrown down as a sulphide by a stream of sulphuretted hydrogen. After warming the solution and allowing it to cool, the precipitate (TERSULPHIDE) is collected on a filter, dried, and weighed. A small portion digested in strong hydrochloric acid will completely dissolve if it be the pure sulphide; in which case the quantity of ANTIMONY sought will be equal to 71-1/2% (71·5%) of the weight of the sulphide found (very nearly).[72] Should only part of the precipitate be soluble, a known weight of it may be introduced into a flask, and a considerable quantity of fuming nitric acid added, drop by drop, and afterwards, a little hydrochloric acid, the mixture being digested, at a gentle heat, until the reaction is complete, and the whole of the sulphur is dissolved. The resulting solution diluted with water, strongly acidulated with tartaric acid, and solution of chloride of barium added as long as it disturbs the liquid, yields a precipitate, of which the weight, after it has been thoroughly washed, dried, and gently ignited, multiplied by 136, gives the quantity of SULPHUR in the sample; and which, deducted from the weight of the sulphide first found, gives the quantity of pure ANTIMONY, as before.

[Footnote 72: Tersulphide of antimony dried at 212° Fahr. still retains traces of water, which is not wholly expelled until the heat reaches 390-392°, when it acquires a black colour and a crystalline appearance.]

2. The quantity of PURE ANTIMONY in commercial samples may be determined by treating them (in powder) with nitric acid, which oxidises the antimony and leaves it in an insoluble state, whilst it dissolves the other metals. The resulting oxide is collected on a filter, washed, dried, ignited in an open porcelain crucible, and weighed--its weight multiplied by ·7898 gives the quantity of pure metal sought.

3. Dissolve a known weight of the sample in hydrochloric acid, immerse a blade of pure metallic tin in the solution, and keep the liquor acidulous, and in a state of gentle ebullition by the heat of a sand bath, when the whole of the ANTIMONY will be precipitated under the form of a black powder, and may be collected, washed, dried, and weighed. This is particularly adapted to alloys of antimony and tin. See _Tests_ (above) and _Pur._ (below).

_Pur._ The antimony of commerce generally contains a little arsenic, with variable quantities of iron, lead, sulphur, and tin. These impurities may be thus detected:--

1. (Arsenic.) By fusing the sample, in powder, mixed with about an equal weight of tartrate or bitartrate of potassium, in a covered crucible, for 2 or 3 hours, and placing the resulting button, which is an alloy of antimony and potassium, in a 'Marsh's apparatus' along with a little water, when the disengagement of hydrogen gas will commence, and may be tested in the usual manner. See ARSENIC.

2. (Iron.) Dissolve the powdered sample in nitrohydrochloric acid, dilute the solution with a large quantity of cold water, filter, and pass a current of sulphuretted hydrogen through the filtrate as long as it produces a precipitate; again filter, boil the filtered liquor for a few minutes to drive off the sulphuretted hydrogen, and then test it with ferrocyanide of potassium, which will give a blue precipitate if iron be present; or supersaturate the last filtrate with ammonia, and then add hydrosulphydrate of ammonium, when, under like conditions, a black precipitate will be formed.

3. (Lead.) Digest the powdered sample in hot nitric acid, which will dissolve out the LEAD but leave the antimony behind. The whitish powdery residuum may be washed, dried, ignited, and weighed, as above; the clear decanted liquor may now be mixed with the first washings, evaporated to dryness, the residuum re-dissolved in water, and the solution submitted to reagents (see LEAD). If lead is found to be present, a solution of sulphate of sodium may be added until it ceases to disturb the liquid, and the resulting precipitate (sulphate of lead) washed, dried, and gently ignited (alone) in a porcelain crucible; the weight of the ignited residuum furnishes a number which, multiplied by ·683, gives the weight of the LEAD sought.

4. (Sulphur.) The solution in nitrohydrochloric acid, when tested with either nitrate or chloride of barium, gives a white precipitate of sulphate of barium, insoluble in both water and acids, which when dried, ignited, and weighed, and the weight multiplied by ·136, gives the quantity of SULPHUR as before. In this case, as with the sulphides (see _above_), free sulphur maybe removed by digesting and washing the powdered sample in bisulphide of carbon, previous to its solution in the acid, by which the violence of the subsequent reaction will be lessened.

5. (Tin.) Two samples of equal weight are taken; the one is tested for ANTIMONY, as described above; the other is dissolved in a mixture of equal parts of hydrochloric and nitrohydrochloric acid, and a blade of zinc immersed in the solution (see _above_); the mixed precipitate of tin and antimony which forms is collected on a weighed filter, washed, dried, and weighed. The weight of antimony in the first sample subtracted from that now obtained, leaves a remainder which indicates the quantity of TIN in the original sample.

_Phys. eff., &c._ Nearly all the salts and preparations of antimony are emetic and cathartic, and in large doses poisonous--occasioning vomiting, profuse alvine dejections, acute colic, and inflammation of the stomach and bowels, often serious, though rarely resulting in death. TARTAR EMETIC and BUTTER OF ANTIMONY are those from which accidents have principally occurred.--_Ant., &c._ Copious vomiting, if it has not already occurred, should be promoted, and the recently prepared hydrated sulphide of iron administered in considerable doses, followed or accompanied by mucilaginous drinks and diuretics. If much prostration follows, wine and stimulants may be had recourse to. In the absence of hydrated sulphide of iron, a solution of tannin, or decoction of galls; cinchona, or oak bark, or even powdered cinchona, mixed with tepid water, may be administered.

_Uses._ In the _arts_, antimony enters into the composition of several useful alloys, as TYPE-METAL, PEWTER, BRITANNIA-METAL, MUSIC-PLATE METAL, &c. It is added to the alloy for concave mirrors, to give them a finer texture; to bell metal, to render it more sonorous; and to various other metals to increase their hardness and fusibility; for the latter purpose it is employed in the casting of cannon balls.

_Concluding Remarks._ In 'roasting' or oxidising the native sulphide of antimony on the bed of the reverberatory furnace, as in the common method before referred to, care must be taken to regulate and gradually raise the heat, which, until towards the end of the process, need not be extreme, and then only should it approach dull redness. Without this precaution much of the undecomposed sulphide will be lost by volatilisation. During the whole time the 'charge' should also be well stirred with an iron spatula, to ensure the constant exposure of every part of it to the atmosphere. The process is complete when the whole mass assumes a greyish-white appearance. Earthen crucibles are commonly employed for the subsequent reduction, and after being charged and covered over with ground charcoal, are heated in a reverberatory furnace. The product is the crude metallic antimony of commerce. It is generally REFINED by smelting it with about 1-8th of its weight of the refined sulphide, and about 1-4th of its weight of carbonate or sulphate of soda; but if there be much iron present, more of the sulphide--even 1-4th--may be required; for unless there be sufficient sulphur to combine with the whole of the iron, the arsenic will not be oxidised, but remain as a contamination. When cold, the metal is carefully separated from the slag, and is frequently re-fused with a little fresh carbonate of soda (1 to 1-1/2 part); after which it is cast into pigs, lumps, or ingots. The crude metal, thus treated, commonly yields 94% of REFINED METAL of tolerable purity.

Should lead have been present in the sulphide or ore, it remains after a second, or even a third fusion, although proportionately reduced in quantity; and it can only be completely separated in the humid way. It is, therefore, always desirable to select an ore free from lead.

=Antimony, Ash of.= _Syn._ ANTIMONY-ASH, CALCINED' ANTIMONY*; CI'NIS ANTIMO''NII, ANTIMO''NIUM CALCINA'TUM*, L. Prepared by roasting the common grey sulphide of antimony on an iron plate set under a chimney, to carry off the fumes. The product is a mixture of teroxide of antimony, with some unburnt sulphide, and a little antimonious acid.

_Prop., &c._ Ash-grey; emetic in small doses. Used chiefly as a cheap substitute for teroxide of antimony by the manufacturers of tartar emetic; also to make metallic antimony.

=Antimony, Butt'er of.= See ANTIMONY, TRICHLORIDE OF.

=Antimony, Calx of.= _Syn._ CALX ANTIMO''NII, L. Sometimes applied to antimony-ash, but more commonly to crude, unwashed diaphoretic antimony.

=Antimony, Calx of= (Sul'phurated). _Syn._ ANTIMO''NII CALX SULPHURA'TA, L. _Prep._ (Hufeland.) Calcined oyster-shells, 10 parts; sulphur, 4 parts; crude antimony, 3 parts; powder, mix, and calcine in a luted crucible for an hour. Emetic, resolvent, and alterative.--_Dose_, 1 to 6 gr.; in gout, rheumatism, scrofula, &c.

=Antimony, Ce'ruse of.= _Syn._ ANTIMO''NII CERUS'SA, L. _Prep._ (Bate.) As diaphoretic antimony (over which it possesses no advantage), merely using the metal instead of the sulphide.

An old preparation made by igniting antimony in the sun's rays, by means of a lens, was called ANTIMONII CERUSSA SOLA''RIS.

=Antimony, Chlo''rides of= (kl[=o]re'-[=i]dz):--

=1. Antimony, Trichloride of.= SbCl_{2}. _Syn._ TERCHLORIDE OF ANTIMONY, ANTIMONIOUS CHLORIDE, CHLO''RIDE OF ANTIMONY, SESQUICHLORIDE OF A., BUTTER OF A., CAU'STIC ANTIMONY[dagger], &c.; ANTIMO''NII CHLORI'DUM, A. TERCHLORI'DUM, A. BU'TYRUM*, &c., L.; CHLORURE D'ANTIMOINE, BEURRE D'ANTIMOINE, &c., Fr.; ANTIMON-CHLORID, SPIESSGLANZ-BUTTER, Ger. This is the substance of which common chloride, or butter of antimony, of the shops, is an impure concentrated solution containing free acid.

_Prep._ 1. SOLID, ANHYDROUS:--

_a._ Pure commercial tersulphide of antimony, in coarse powder, 1 part; concentrated hydrochloric acid, 5 parts; are mixed in a capacious stoneware or glass vessel set under a chimney with a quick draught, to convey away the fumes, the whole being constantly stirred, and, as the effervescence slackens, a gradually increasing gentle heat applied until solution is complete; the resulting liquid is put into a retort, and distilled, until each drop of the distillate, as it falls into the aqueous liquid which has previously passed over into the receiver, produces a copious white precipitate; the receiver is then changed, and the distillation continued, when pure TRICHLORIDE OF ANTIMONY passes over, and solidifies on cooling to a white and highly crystalline mass, which must be carefully excluded from the air.

_b._ From pure metallic antimony, 2 parts; bichloride of mercury, 5 parts; both in fine powder; mixed and distilled in a retort with a large neck, by a gentle sand-heat, into a suitable receiver. Chemically pure.

2. LIQUID:--

_a._ (LIQUOR ANTIMONII CHLORIDI, B. P.) _Syn._ SOLUTION OF CHLORIDE OF ANTIMONY.

_Prep._ Take of black antimony, 1 _lb._; hydrochloric acid, 4 pints; place the black antimony in a porcelain vessel; pour upon it the hydrochloric acid, and, constantly stirring, apply to the mixture, beneath a flue with a good draught, a gentle heat, which must be gradually augmented as the evolution of gas begins to slacken, until the liquid boils. Maintain it at this temperature for fifteen minutes; then remove the vessel from the fire, and filter the liquid through calico into another vessel, returning what passes through first, that a perfectly clear solution may be obtained. Boil this down to the bulk of two pints, and preserve it in a stoppered bottle.

_Characters and Tests._ A heavy liquid, usually of a yellowish-red colour. A little of it dropped into water gives a white precipitate, and the filtered solution lets fall a copious deposit on the addition of nitrate of silver. If the white precipitate formed by water be treated with sulphuretted hydrogen it becomes orange-coloured. The specific gravity of the solution is 1·47. One fluid drachm of it mixed with a solution of a quarter of an ounce of tartaric acid in four fluid ounces of water, forms a clear solution, which, if treated with sulphuretted hydrogen, gives an orange precipitate, weighing, when washed and dried at 212°, at least 22 grains.

_b._ (Commercial.)--_a._ Take of ash or calx of antimony, 3-1/4 _lbs._; common salt, 2 _lbs._; oil of vitriol, 1-1/2 _lb._; water, 1 _lb._; proceed as before. Prod., 2-1/2 _lbs._

_c._ From roasted sulphide or glass of antimony, 7 _lbs._; salt, 28 _lbs._; oil of vitriol, 21 _lbs._; water, 14 _lbs._; as before.

_d._ From crude sulphide of antimony (powdered), 25 _lbs._; strongest commercial hydrochloric acid, 1 _cwt._; nitric acid, 3-1/2 _lbs._; as before; the product being coloured with a little pernitrate of iron, and made up to the sp. gr. 1·4. The quality is improved, and the process more easily conducted, if the crude antimony is roasted before dissolving it in the acid. The same applies to the other formulæ.

_Prop., &c._--_a._ SOLID. When pure, and nearly free from water, it somewhat resembles butter, melts with a gentle heat, and partially crystallises on cooling; is very deliquescent, and quickly passes into an oily liquid when exposed to damp air; very soluble in strong hydrochloric acid; water, according to its quantity, more or less decomposes it. When perfectly pure and anhydrous, it forms a white and highly crystalline mass, rapidly decomposed by air and moisture.--_b._ SOLUTION. The sp. gr. of the solution of the shops varies from 1·25 to 1·4, in which state it is a transparent fuming yellow liquid (unless when artificially coloured), and extremely acid and caustic. Submitted to distillation, it at first parts with its water and excess of acid, after which the salt itself is volatilised. By changing the receiver as soon as the distillate concretes on cooling, or produces a copious white precipitate on falling into the liquid already passed over, the pure ANHYDROUS TRICHLORIDE may be readily obtained.

_Phys. eff., Ant., Lesions, &c._ See ANTIMONY.

_Uses._ In _medicine_, only externally, and chiefly as a caustic or escharotic to the wounds caused by rabid and venomous animals, and to repress excessive granulations in ulcers. In _pharmacy_, as a source of both oxychloride and oxide of antimony. The residuum in the retort when corrosive sublimate is used, is sulphide of mercury, and was formerly called CINNABAR OF ANTIMONY.

=2. Antimony, Pentachlo''ride of.= Sb_{2}Cl_{5}. _Syn._ PERCHLO''RIDE OF ANTIMONY; ANTIMO''NII PENTACHLORI'DUM, L. Prepared by passing a stream of chlorine gas over metallic antimony in fine powder, and gently heated. A mixture of TRICHLORIDE and PENTACHLORIDE OF ANTIMONY is found in the receiver, from which the latter may be separated by careful distillation. It is a colourless volatile liquid, forming a crystalline compound with a small quantity of water, but decomposed by a larger quantity.

=Antimony, Cro'cus of.= _Syn._ SAFF'RON OF ANTIMONY, LIV'ER OF A.; CRO'CUS ANTIMO''NII C. METALLO''RUM, HE'PAR ANTIMONII, L.; CROCUS D'ANTIMOINE, SAFFRAN D'A., Fr. _Prep._ 1. From black sulphide of antimony, and saltpetre, equal parts, deflagrated together by small portions at a time, and the fused mass (separated from the scoriæ) reduced to fine powder.

2. (ANT. CROCUS, Ph. L. 1788,) Sulphide of antimony, 1 lb.; nitre, 1 lb.; common salt, 1 oz.; as before.

_Prop., &c._ Its medicinal properties closely resemble those of diaphoretic antimony. It is a mixture of sulphate of potassium, antimoniate of potassium, teroxide of antimony, oxysulphide of antimony, sulphide of potassium, and undecomposed trisulphide of antimony, in variable and undetermined proportions. When repeatedly washed or boiled in water, and dried, it forms the WASHED SAFFRON OF ANTIMONY (C. A. LO'TUS, L.) of old pharmacy, and has then lost its sulphate of potassium, caustic potash, and sulphide of potassium. Formerly used to make tartar emetic. See ANTIMONY, LIVER OF.

=Antimony, Crude.= Native sulphide of antimony melted from the gangue.

=Antimony, Diaphoret'ic.= _Syn._ CALX OF ANTIMONY, CALCINED' A., ANTIMO''NIATE OF POT'ASH, STIB'IATED KA'LI[dagger], DIAPHORETIC MIN'ERAL[dagger], &c.; ANTIMO''NIUM DIAPHORET'ICUM, A. CALCINA'TUM, CALX ANTIMO''NII, C. A. ANGLO''RUM[dagger], POTAS'SÆ ANTIMO''NIAS, KALI STIB'ICUM[dagger], &c., L. var.; ANTIMOINE DIAPHORÉTIQUE, BIANTIMONIATE DE POTASSE, Fr. An old preparation with numerous synonyms, of which the first two of the above are those which are now chiefly in use.

_Prep._ 1. Sulphide of antimony, 1 part; nitre, 3 parts; powder, mix, and deflagrate by spoonfuls in a red-hot crucible, then calcine for half an hour, and when cold powder the residuum.

2. WASHED DIAPHORETIC A., W. CALX OF A.; ANTIMONIUM DIAPHORETICUM LO'TUM, A. D. ABLU'TUM (Ph. Bor. 1847), A. CALCINA'TUM (Ph. L. 1788); ANTIMOINE DIAPHORÉTIQUE LAVÉ, &c., Fr.:--_a._ (Ph. L. 1788.) As the last, but the powder is subsequently deprived of soluble matter by repeated washings with water, after which it is collected and dried.

_b._ (Ph. Bor. 1847.) Metallic antimony, 1 part; nitre, 2 parts; as above, but drying the washed powder at a heat not exceeding 104° F.

_Prop., &c._ A white or greyish-white powder, without either smell or taste; gently diaphoretic and laxative; its activity greatly depending on the quantity of acid in the stomach.--_Dose_, 1 to 6 gr., or even 10 gr.; for _horses_, 1 to 3 or 4 _dr._ It was formerly in high repute; but is now almost superseded by the present pharmacop[oe]ial preparations.

=Antimony, E'thiops of.= _Syn._ Æ'THIOPS ANTIMONIA'LIS, L. _Prep._ 1. From metallic mercury, 1 part; sulphide of antimony, 2 parts; triturated together until the globules of the former entirely disappear.--2. Sulphide of antimony, 3 parts; black sulphide of mercury, 2 parts; triturated together for some time. An old remedy in certain skin diseases, still highly esteemed by some provincial practitioners.--_Dose_, 3 to 5 gr., gradually increased to 20 or 30 gr.

=Antimony, Flow'ers of.= _Syn._ FLO''RES ANTIMO''NII, L.; FLEURS D'ANTIMOINE, Fr. _Prep._ Throw powdered sulphide of antimony, by spoonfuls at a time, into an ignited tubulated retort with a short and very wide neck, until as many 'flowers' collect in the receiver as are required. An impure oxysulphide of antimony, with variable portions of trioxide, and undecomposed tersulphide. Emetic in doses of 1 to 3 grains.

=Antimony, Flowers of (Ar'gentine).= [-[)i]n.] _Syn._ WHITE OX'IDE OF ANTIMONY, SNOW OF A.[dagger]; ANTIMO''NII FLO''RES ARGENTI'NI, A. NIX[dagger], L.; FLEURS ARGENTINE D'ANTIMOINE, OXYDE BLANC D'ANTIMOINE, Fr. _Prep._ Melt metallic antimony in a vessel freely exposed to the air, and furnished with a cool place for the 'flowers' to rest on, and collect them as deposited; or, and what is better, heat the metal to a full red or white heat in a covered crucible, and then suddenly expose it to the air, when it will inflame, and the oxidised vapour condense as 'flowers' on any cool surface (as a partially inverted wide-mouthed flask) held at a little distance over it. The product is TRIOXIDE OF ANTIMONY in a crystalline form, and received the name of argentine flowers from its silvery whiteness and beauty.

=Antimony, Flowers of (Helmont's).= _Syn._ FLO''RES ANTIMO''NII HELMON'TII. An old preparation formed by dissolving sulphide of antimony in aqua regia, expelling the free water and acid by heat, and subliming the residuum with an equal weight of sal ammoniac. Violently emetic, even in small doses, and unfit for internal use.

=Antimony, Flowers of (Red).= _Syn._ FLO''RES ANTIMO''NII RU'BRI, L. From sulphide of antimony, and sal ammoniac, both in fine powder, mixed and sublimed together. Resembles the last.

=Antimony, Ful'minating.= See FULMINATING COMPOUNDS.

=Antimony, Glass of.= _Syn._ VIT'RIFIED ANTIMONY*, V. OX'IDE OF A.*, GREY O. OF A.*; ANTIMO''NII VIT'RUM, ANTIMO''NIUM VITRIFICA'TUM, A. VITRIFAC'TUM (Ph. L. 1788), OX'YDUM ANTIMONII VITRIFICATUM, &c., L.; VERRE D'ANTIMOINE, OXYSULFURE D'ANTIMOINE SILICATÉ, Fr. _Prep._ (Ph. L. 1788.) Roast sulphide of antimony in a shallow earthen vessel, over a moderate fire, stirring it constantly with an iron rod, until it turns whitish-grey and ceases to emit fumes at a red heat; put the residuum into a covered crucible which it shall only two thirds fill, and expose it to an intense heat (gradually raised), until it fuses, then pour it out on an iron plate. If calcined too much, a little more crude antimony may be added to make it run well.

_Comp., Prop., &c._ A mixture of sulphide and oxide of antimony contaminated with a little silica and iron. In fine powder it is emetic, in doses of 1 to 3 gr.; but owing to the uncertainty and violence of its operation, is now seldom employed. It has been used as a cheap source of the TEROXIDE by the manufacturers of tartar emetic.

=Antimony, Glass of (Cera''ted).= _Syn._ ANTIMO''NII VIT'RUM CERA'TUM, L. _Prep._ (Dr Young & Ph. L. 1746.) Glass of antimony, in very fine powder, 1 oz.; yellow wax, 1 dr.; melt together in an iron ladle, and keep it over a gentle fire free from flame (constantly stirring) for about half an hour, or until it acquires a snuff colour, then pour it out on a piece of white paper (or a plate), and when cold, powder it.--_Dose_, 2 to 10 gr., in dysentery, &c.

=Antimony, Li'ver of.= _Syn._ HE'PAR ANTIMO''NII, L.; HÉPAR D'ANTIMOINE, OXYSULFURE D'ANTIMOINE SILICATÉ, Fr. _Prep._ From sulphide of antimony, 1 part; and dry carbonate of sodium or potassium, 2 parts; melted together, and heated until it acquires the proper colour, and then cooled and powdered.

_Comp., Uses, &c._ A mixture of trioxide of antimony, sulphide of potassium, carbonate of potassium, and undecomposed trisulphide of antimony. It is chiefly used by farriers, in doses of 1 to 2 dr., as an alterative purge for horses, in greasy heels, &c.; and sometimes by chemists, as a source of the crude oxide. Crocus of antimony, before noticed, sometimes passes under the name, and is sold for it.

=Antimony, Ore of.= _Syn._ ANTIMONY-ORE. Native sulphide of antimony.

=Antimony, Oxide of.= The B. P. name for Antimony, Trioxide of (which _see_).

=Antimony, Oxides of.= Antimony forms with oxygen three definite compounds, viz the--

Trioxide or antimonious oxide Sb_{2}O_{3}

Tetroxide or antimonoso-antimonic { or oxide Sb_{2}O_{4} {Sb_{2}O_{3}. {Sb_{2}O_{5}

Pentoxide or antimonic oxide Sb_{2}O_{5}