Volume 2, Slice 2 Part 20 (1/2)

Antimony, like phosphorus and a.r.s.enic, 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 pa.s.sing 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 const.i.tuent elements. When pa.s.sed 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 senarmont.i.te, 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 quant.i.ty. It is decomposed by a hot solution of pota.s.sium 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 ma.s.s 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 pota.s.sium 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. Fremy), 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 ma.s.s 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 (”b.u.t.ter 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 quant.i.ty 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 ma.s.s of crystals melting at -6C. It dissociates into the trichloride and chlorine when heated. It combines with water, forming the hydrates SbCl5H2O and SbCl54H2O; it also combines with phosphorus oxychloride, hydrocyanic acid, and cyanogen chloride. In chloroform solution it combines with anhydrous oxalic acid to form a compound, Sb2Cl8(C2O4), which is to be considered as tetra-chlorstibonium oxalate

COOSbCl4

COOSbCl4

(R. Anschutz and Evans, _Annalen_, 1887, ccx.x.xix. 235). Antimonyl chloride, SbOCl, is produced by the decomposition of one part of the trichloride with four parts of water. Prepared in this way it contains a small quant.i.ty of the unaltered chloride, which can be removed by ether or carbon bisulphide. It is a white powder insoluble in water, alcohol and ether. On heating, it is converted into the oxychloride Sb4O5Cl2 (Sb2O3SbOCl). Antimony oxychloride, SbOCl3, is formed by addition of the calculated quant.i.ty of water to ice-cooled antimony pentachloride, SbCl5 + H2O = SbOCl3 + 2HCl. It forms a yellowish crystalline precipitate which in moist air goes to a thick liquid.

Compounds of composition, SbOCl32SbCl5 and SbO2Cl2SbOCl3, have also been described (W.C. Williams, _Chem. News_. 1871, xxiv. 234).

Antimony tribromide, SbBr3, and tri-iodide, SbI3, may be prepared by the action of antimony on solutions of bromine or iodine in carbon bisulphide. The tribromide is a colourless crystalline ma.s.s of specific gravity 4.148 (23), melting at 90 to 94 C. and boiling at 275.4 C. (H. Kopp). The tri-iodide forms red-coloured crystals of specific gravity 4.848 (26), melting at 165 to 167 C. and boiling at 401 C. By the action of water they give oxybromides and oxyiodides SbOBr, Sb4O5Br2, SbOI. Antimony penta-iodide, SbI5, is formed by heating antimony with excess of iodine, in a sealed tube, to a temperature not above 130C. It forms a dark brown crystalline ma.s.s, melting at 78 to 79 C., and is easily dissociated on heating.

Antimony trifluoride, SbF3, is obtained by dissolving the trioxide in aqueous hydrofluoric acid or by distilling antimony with mercuric fluoride. By rapid evaporation of its solution it may be obtained in small prisms. The pentafluoride SbF5 results when metantimonic acid is dissolved in hydrofluoric acid, and the solution is evaporated. It forms an amorphous gummy ma.s.s, which is decomposed by heat.

Oxyfluorides of composition SbOF and SbOF3 are known.

Two sulphides of antimony are definitely known, the trisulphide Sb2S3 and the pentasulphide Sb2S5; a third, the tetrasulphide Sb2S4, has also been described, but its existence is doubtful. Antimony trisulphide, Sb2S3, occurs as the mineral antimonite or stibnite, from which the commercial product is obtained by a process of liquation.

The amorphous variety may be obtained from the crystalline form by dissolving it in caustic potash or soda or in solutions of alkaline sulphides, and precipitating the hot solution by dilute sulphuric acid. The precipitate is then washed with water and dried at 100 C., by which treatment it is obtained in the anhydrous form. On precipitating antimony trichloride or tartar emetic in acid solution with sulphuretted hydrogen, an orange-red precipitate of the hydrated sulphide is obtained, which turns black on being heated to 200 C The trisulphide heated in a current of hydrogen is reduced to the metallic state; it burns in air forming the tetroxide, and is soluble in concentrated hydrochloric acid, in solutions of the caustic alkalis, and in alkaline sulphides. By the union of antimony trisulphide with basic sulphides, livers of antimony are obtained. These substances are usually prepared by fusing their components together, and are dark powders which are less soluble in water the more antimony they contain. These thioantimonites are used in the vulcanizing of rubber and in the preparation of matches. Antimony pentasulphide, Sb2S5, is prepared by precipitating a solution of the pentachloride with sulphuretted hydrogen, by decomposing ”Schlippe's salt” (q.v.) with an acid, or by pa.s.sing sulphuretted hydrogen into water containing antimonic acid. It forms a fine dark orange powder, insoluble in water, but readily soluble in aqueous solutions of the caustic alkalis and alkaline carbonates. On heating in absence of air, it decomposes into the trisulphide and sulphur.

An antimony phosphide and a.r.s.enide are known, as is also a thiophosphate, SbPS4, which is prepared by heating together antimony trichloride and phosphorus pentasulphide.

Many organic compounds containing antimony are known. By distilling an alloy of antimony and sodium with mythyl iodide, mixed with sand, trimethyl stibine, Sb(CH3)3, is obtained; this combines with excess of methyl iodide to form tetramethyl stibonium iodide, Sb(CH3)4I. From this iodide the trimethyl stibine may be obtained by distillation with an alloy of pota.s.sium and antimony in a current of carbon dioxide. It is a colourless liquid, slightly soluble in water, and is spontaneously inflammable. The stibonium iodide on treatment with moist silver oxide gives the corresponding tetramethyl stibonium hydroxide, Sb(CH3)4OH, which forms deliquescent crystals, of alkaline reaction, and absorbs carbon dioxide readily. On distilling trimethyl stibine with zinc methyl, antimony tetra-methyl and penta-methyl are formed. Corresponding antimony compounds containing the ethyl group are known, as is also a tri-phenyl stibine, Sb(C6H5)3, which is prepared from antimony trichloride, sodium and monochlorbenzene. See Chung Yu w.a.n.g, _Antimony_ (1909).

_Antimony in Medicine._--So far back as Basil Valentine and Paracelsus, antimonial preparations were in great vogue as medicinal agents, and came to be so much abused that a prohibition was placed upon their employment by the Paris parlement in 1566. Metallic antimony was utilized to make goblets in which wine was allowed to stand so as to acquire emetic properties, and ”everlasting” pills of the metal, supposed to act by contact merely, were administered and recovered for future use after they had fulfilled their purpose. Antimony compounds act as irritants both externally and internally. Tartar emetic (antimony tartrate) when swallowed, acts directly on the wall of the stomach, producing vomiting, and after absorption continues this effect by its action on the medulla. It is a powerful cardiac depressant, diminis.h.i.+ng both the force and frequency of the heart's beat. It depresses respiration, and in large doses lowers temperature. It depresses the nervous system, especially the spinal cord. It is excreted by all the secretions and excretions of the body. Thus as it pa.s.ses out by the bronchial mucous membrane it increases the amount of secretion and so acts as an expectorant. On the skin its action is that of a diaph.o.r.etic, and being also excreted by the bile it acts slightly as a cholagogue.

Summed up, its action is that of an irritant, and a cardiac and nervous depressant. But on account of this depressant action it is to be avoided for women and children and rarely used for men.

_Toxicology._--Antimony is one of the ”protoplasmic” poisons, directly lethal to all living matter. In acute poisoning by it the symptoms are almost identical with those of a.r.s.enical poisoning, which is much commoner (See a.r.s.eNIC). The post-mortem appearances are also very similar, but the gastro-intestinal irritation is much less marked and inflammation of the lungs is more commonly seen. If the patient is not already vomiting freely the treatment is to use the stomach-pump, or give sulphate of zinc (gr. 10-30) by the mouth or apomorphine (gr.

1/20-1/10) subcutaneously. Frequent doses of a teaspoonful of tannin dissolved in water should be administered, together with strong tea and coffee and mucilaginous fluids. Stimulants may be given subcutaneously, and the patient should be placed in bed between warm blankets with hot-water bottles. Chronic poisoning by antimony is very rare, but resembles in essentials chronic poisoning by a.r.s.enic. In its medico-legal aspects antimonial poisoning is of little and lessening importance.

ANTINOMIANS (Gr. [Greek: anti], against, [Greek: nomos], law), a term apparently coined by Luther to stigmatize Johannes Agricola (q.v.) and his following, indicating an interpretation of the ant.i.thesis between law and gospel, recurrent from the earliest times. Christians being released, in important particulars, from conformity to the Old Testament polity as a whole, a real difficulty attended the settlement of the limits and the immediate authority of the remainder, known vaguely as the moral law. Indications are not wanting that St Paul's doctrine of justification by faith was, in his own day, mistaken or perverted in the interests of immoral licence. Gnostic sects approached the question in two ways. Marcionites, named by Clement of Alexandria _Ant.i.tactae_ (revolters against the Demiurge) held the Old Testament economy to be throughout tainted by its source; but they are not accused of licentiousness. Manichaeans, again, holding their spiritual being to be unaffected by the action of matter, regarded carnal sins as being, at worst, forms of bodily disease. Kindred to this latter view was the position of sundry sects of English fanatics during the Commonwealth, who denied that an elect person sinned, even when committing acts in themselves gross and evil. Different from either of these was the Antinomianism charged by Luther against Agricola. Its starting-point was a dispute with Melanchthon in 1527 as to the relation between repentance and faith. Melanchthon urged that repentance must precede faith, and that knowledge of the moral law is needed to produce repentance.

Agricola gave the initial place to faith, maintaining that repentance is the work, not of law, but of the gospel-given knowledge of the love of G.o.d. The resulting Antinomian controversy (the only one within the Lutheran body in Luther's lifetime) is not remarkable for the precision or the moderation of the combatants on either side. Agricola was apparently satisfied in conference with Luther and Melanchthon at Torgau, December 1527. His eighteen _Positiones_ of 1537 revived the controversy and made it acute. Random as are some of his statements, he was consistent in two objects: (1) in the interest of solifidian doctrine, to place the rejection of the Catholic doctrine of good works on a sure ground; (2) in the interest of the New Testament, to find all needful guidance for Christian duty in its principles, if not in its precepts. From the latter part of the 17th century charges of Antinomianism have frequently been directed against Calvinists, on the ground of their disparagement of ”deadly doing” and of ”legal preaching.” The virulent controversy between Arminian and Calvinistic Methodists produced as its ablest outcome Fletcher's _Checks to Antinomianism_ (1771-1775).

See G. Kawerau, in A. Hauck's _Realencyklopadie_ (1896); Riess, in I.

Goschler's _Dict. Encyclop. de la theol. cath._ (1858); J.H. Blunt _Dict. of Doct. and Hist. Theol._ (1872); J.C.L. Gieseler, _Ch. Hist._ (New York ed. 1868, vol. iv.).

ANTINOMY (Gr. [Greek: anti], against, [Greek: nomos], law), literally, the mutual incompatibility, real or apparent, of two laws. The term acquired a special significance in the philosophy of Kant, who used it to describe the contradictory results of applying to the universe of pure thought the categories or criteria proper to the universe of sensible perception (phenomena). These antinomies are four--two mathematical, two dynamical--connected with (1) the limitation of the universe in respect of s.p.a.ce and time, (2) the theory that the whole consists of indivisible atoms (whereas, in fact, none such exist), (3) the problem of freedom in relation to universal causality, (4) the existence of a universal being--about each of which pure reason contradicts the empirical, as thesis and ant.i.thesis. Kant claimed to solve these contradictions by saying, that in no case is the contradiction real, however really it has been intended by the opposing partisans, or must appear to the mind without critical enlightenment. It is wrong, therefore, to impute to Kant, as is often done, the view that human reason is, on ultimate subjects, at war with itself, in the sense of being impelled by equally strong arguments towards alternatives contradictory of each other. The difficulty arises from a confusion between the spheres of phenomena and noumena. In fact no rational cosmology is possible.

See John Watson, _Selections from Kant_ (trans. Glasgow, 1897), pp.

155 foll.; W. Windelband, _History of Philosophy_ (Eng. trans. 1893); H. Sidgwick, _Philos. of Kant_, lectures x. and xi. (Lond., 1905); F.

Paulsen, _I. Kant_ (Eng. trans. 1902), pp. 216 foll.