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ANTIMONY
  

the basis of Britannia-metal, small quantities of copper, lead, zinc or bismuth being added. It is a white metal of bluish tint and is malleable and ductile. For the linings of brasses, various white metals are used, these being alloys of copper, antimony and tin, and occasionally lead.

Antimony is a silvery white, crystalline, brittle metal, and has a high lustre. Its specific gravity varies from 6·7 to 6·86; it melts at 432° C. (Dalton), and boils between 1090-1600° C. (T. Carnelley), or above 1300° (V. Meyer). Its specific heat is 0·0523 (H. Kopp). The vapour density of antimony at 1572° C. is 10·74, and at 1640° C. 9·78 (V. Meyer, Berichte, 1889, 22, p. 725), so that the antimony molecule is less complex than the molecules of the elements phosphorus and arsenic. An amorphous modification of antimony can be prepared by heating the metal in a stream of nitrogen, when it condenses in the cool part of the apparatus as a grey powder of specific gravity 6·22, melting at 614° C. and containing 98-99% of antimony (F. Hérard, Comptes Rendus, 1888, cvii. 420).

Another form of the metal, known as explosive antimony, was discovered by G. Gore (Phil. Trans., 1858, p. 185; 1859, p. 797; 1862, p. 623), on electrolysing a solution of antimony trichloride in hydrochloric acid, using a positive pole of antimony and a negative pole of copper or platinum wire. It has a specific gravity of 5·78 and always contains some unaltered antimony trichloride (from 6 to 20%, G. Gore). It is very unstable, a scratch causing it instantaneously to pass into the stable form with explosive violence and the development of much heat. Similar phenomena are exhibited in the electrolysis of solutions of antimony tribromide and tri-iodide, the product obtained from the tribromide having a specific gravity of 5·4, and containing 18-20% of antimony tribromide, whilst that from the tri-iodide has a specific gravity of 5·2-5·8 and contains about 22% of hydriodic acid and antimony tri-iodide.

The atomic weight of antimony has been determined by the analysis of the chloride, bromide and iodide. J. P. Cooke (Proc. Amer. Acad., 1878, xiii. i) and J. Bongartz (Berichte, 1883, 16, p. 1942) obtained the value 120, whilst F. Pfeiffer (Ann. Chim. et Phys. ccix. 173) obtained the value 121 from the electrolysis of the chloride.

Pure antimony is quite permanent in air at ordinary temperatures, but when heated in air or oxygen it burns, forming the trioxide. It decomposes steam at a red heat, and burns (especially when finely powdered) in chlorine. Dilute hydrochloric acid is without action on it, but on warming with the concentrated acid, antimony trichloride is formed; it dissolves in warm concentrated sulphuric acid, the sulphate Sb2(SO4)3 being formed. Nitric acid oxidizes antimony either to the trioxide Sb4O6 or the pentoxide Sb2O5, the product obtained depending on the temperature and concentration of the acid. It combines directly with sulphur and phosphorus, and is readily oxidized when heated with metallic oxides (such as litharge, mercuric oxide, manganese dioxide, &c.). Antimony and its salts may be readily detected by the orange precipitate of antimony sulphide which is produced when sulphuretted hydrogen is passed through their acid solutions, and also by the Marsh test (see Arsenic); in this latter case the black stain produced is not soluble in bleaching powder solution. Antimony compounds when heated on charcoal with sodium carbonate in the reducing flame give brittle beads of metallic antimony, and a white incrustation of the oxide. The antimonious compounds are decomposed on addition of water, with formation of basic salts.

Antimony may be estimated quantitatively by conversion into the sulphide; the precipitate obtained is dried at 100° C. and heated in a current of carbon dioxide, or it may be converted into the tetroxide by nitric acid.

Antimony, like phosphorus and arsenic, combines directly with hydrogen. The compound formed, antimoniuretted hydrogen or stibine, SbH3, may also be prepared by the action of hydrochloric acid on an alloy of antimony and zinc, or by the action of nascent hydrogen on antimony compounds. As prepared by these methods it contains a relatively large amount of hydrogen, from which it can be freed by passing through a tube immersed in liquid air, when it condenses to a white solid. It is a poisonous colourless gas, with a characteristic offensive smell. In its general behaviour it resembles arsine, burning with a violet flame and being decomposed by heat into its constituent elements. When passed into silver nitrate solution it gives a black precipitate of silver antimonide, SbAg3. It is decomposed by the halogen elements and also by sulphuretted hydrogen. All three hydrogen atoms are replaceable by organic radicals and the resulting compounds combine with compounds of the type RCl, RBr and RI to form stibonium compounds.

There are three known oxides of antimony, the trioxide Sb4O6 which is capable of combining with both acids and bases to form salts, the tetroxide Sb2O4 and the pentoxide Sb2O5. Antimony trioxide occurs as the minerals valentinite and senarmontite, and can be artificially prepared by burning antimony in air; by heating the metal in steam to a bright red heat; by oxidizing melted antimony with litharge; by decomposing antimony trichloride with an aqueous solution of sodium carbonate, or by the action of dilute nitric acid on the metal. It is a white powder, almost insoluble in water, and when volatilized, condenses in two crystalline forms, either octahedral or prismatic. It is insoluble in sulphuric and nitric acids, but is readily soluble in hydrochloric and tartaric acids and in solutions of the caustic alkalies. On strongly heating in air it is converted into the tetroxide. The corresponding hydroxide, orthoantimonious acid, Sb(OH)3, can be obtained in a somewhat impure form by precipitating tartar emetic with dilute sulphuric acid; or better by decomposing antimonyl tartaric acid with sulphuric acid and drying the precipitated white powder at 100° C. Antimony tetroxide is formed by strongly heating either the trioxide or pentoxide. It is a nonvolatile white powder, and has a specific gravity of 6·6952; it is insoluble in water and almost so in acids—concentrated hydrochloric acid dissolving a small quantity. It is decomposed by a hot solution of potassium bitartrate. Antimony pentoxide is obtained by repeatedly evaporating antimony with nitric acid and heating the resulting antimonic acid to a temperature not above 275° C.; by heating antimony with red mercuric oxide until the mass becomes yellow (J. Berzelius); or by evaporating antimony trichloride to dryness with nitric acid. It is a pale yellow powder (of specific gravity 6·5), which on being heated strongly gives up oxygen and forms the tetroxide. It is insoluble in water, but dissolves slowly in hydrochloric acid. It possesses a feeble acid character, giving metantimoniates when heated with alkaline carbonates.

Orthoantimonic acid, H3SbO4, is obtained by the decomposition of its potassium salt with nitric acid (A. Geuther); or by the addition of water to the pentachloride, the precipitate formed being dried over sulphuric acid (P. Conrad, Chem. News, 1879, xl. 198). It is a white powder almost insoluble in water and nitric acid, and when heated, is first converted into metantimonic acid, HSbO3, and then into the pentoxide Sb2O5. Pyroantimonic acid, H4Sb2O7 (the metantimonic acid of E. Frémy), is obtained by decomposing antimony pentachloride with hot water, and drying the precipitate so obtained at 100° C. It is a white powder which is more soluble in water and acids than orthoantimonic acid. It forms two series of salts, of the types M2H2Sb2O7 and M4Sb2O7. Metantimonic acid, HSbO3, can be obtained by heating orthoantimonic acid to 175° C., or by long fusion of antimony with antimony sulphide and nitre. The fused mass is extracted with water, nitric acid is added to the solution, and the precipitate obtained washed with water (J. Berzelius). It is a white powder almost insoluble in water. On standing with water for some time it is slowly converted into the ortho-acid.

Compounds of antimony with all the halogen elements are known, one atom of the metal combining with three or five atoms of the halogen, except in the case of bromine, where only the tribromide is known. The majority of these halide compounds are decomposed by water, with the formation of basic salts. Antimony trichloride (“Butter of Antimony”), SbCl3, is obtained by burning the metal in chlorine; by distilling antimony with excess of mercuric chloride; and by fractional distillation of antimony tetroxide or trisulphide in hydrochloric acid solution. It is a colourless deliquescent solid of specific gravity 3·06; it melts at 73·2° C. (H. Kopp) to a colourless oil; and boils at 223° (H. Capitaine). It is soluble in alcohol and in carbon bisulphide, and also in a small quantity of water; but with an excess of water it gives a precipitate of various oxychlorides, known as powder of algaroth (q.v.). These precipitated oxychlorides on continued boiling with water lose all their chlorine and ultimately give a residue of antimony trioxide. It combines with chlorides of the alkali metals to form double salts, and also with barium, calcium, strontium, and magnesium chlorides. Antimony pentachloride, SbCl5 is prepared by heating the trichloride in a current of chlorine. It is a nearly colourless fuming liquid of unpleasant smell, which can be solidified to a mass of crystals melting at −6°C. It dissociates into the trichloride and chlorine when heated. It combines with water, forming the hydrates SbCl5·H2O and SbCl5·4H2O; it also combines with phosphorus oxychloride, hydrocyanic acid, and cyanogen chloride. In chloroform solution it combines with anhydrous oxalic