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Arsenic
1911 Encyclopedia Britannica
or (symbol As, atomic weight 75.0), a chemical element, known to the ancients in the form of its sulphides. Aristotle gave them the name crav&apace, and Theophrastus mentions them under the name ap6Evucov. The oxide known as white arsenic is mentioned by the Greek alchemist Olympiodorus, who obtained it by roasting arsenic sulphide. These substances were all known to the later alchemists, who used minerals containing arsenic in order to give a white colour to copper. Albertus Magnus was the first to state that arsenic contained a metal-like substance, although later writers considered it to be a bastard or semi-metal, and frequently called it arsenicum rex. In 1733 G. Brandt showed that white arsenic was the calx of this element, and after the downfall of the phlogiston theory the views concerning the composition of white arsenic were identical with those which are now held, namely that it is an oxide of the element.
Arsenic is found in the uncombined condition in various localities, but more generally in combination with other metals and sulphur, in the form of more or less complex sulphides. Native arsenic is usually found as granular or curvilaminar masses, with a reniform or botryoidal surface. These masses are of a dull grey colour, owing to surface tarnish; only on fresh fractures is the colour tin-white with metallic lustre. The hardness is 3.5 and the specific gravity 5'63-5'73. Crystals of arsenic belong to the rhombohedral system, and have a perfect cleavage parallel to the basal plane; natural crystals are, however, of rare occurrence, and are usually acicular in habit. Native arsenic occurs usually in metalliferous veins in association with ores of antimony, silver, &c.; the silver mines of Freiberg in Saxony, St Andreasberg in the Harz, and Chanarcillo in Chile being well-known localities. Attractive globular aggregates of well-developed radiating crystals have been found at Akatani, a village in the province Echizen, in Japan.
Arsenic is a constituent of the minerals arsenical iron, arsenical pyrites or mispickel, tin-white cobalt or smaltite, arsenical nickel, realgar, orpiment, pharmacolite and cobalt bloom, whilst it is also met with in small quantities in nearly all specimens of iron pyrites. The ordinary commercial arsenic is either the naturally occurring form, which is, however, more or less contaminated with other metals, or is the product obtained by heating arsenical pyrites, out of contact with air, in earthenware retorts which are fitted with a roll of sheet iron at the mouth, and an earthenware receiver. By this method of distillation the arsenic sublimes into the receiver, leaving a residue of iron sulphide in the retort. For further purification, it may be sublimed, after having been previously mixed with a little powdered charcoal, or it may be mixed with a small quantity of iodine and heated. It can also be obtained by the reduction of white arsenic (arsenious oxide) with carbon. An electro-metallurgical process for the extraction of arsenic from its sulphides has also been proposed (German Patent, 67,973). These compounds are brought into solution by means of polysulphides of the alkali metals and the resultant liquor run into the cathode compartment of a bath, which is divided by diaphragms into a series of anode and cathode chambers; the anode divisions being closed and gas-tight, and containing carbon or platinum electrodes. The arsenic solution is decomposed at the cathode, and the element precipitated there.
Arsenic possesses a steel-grey colour, and a decided metallic lustre; it crystallizes on sublimation and slow condensation in rhombohedra, isomorphous with those of antimony and tellurium. It is very brittle. Its specific gravity is given variously from 5.395 to 5'959; its specific heat is 0.083, and its coefficient of linear expansion 0.0000-0559 (at 40° C.). It is volatile at temperatures above 1oo° C. and rapidly vaporizes at a dull red heat. It liquefies when heated under pressure, and its melting point lies between 446° C. and 457° C. The vapour of arsenic is of a golden yellow colour, and has a garlic odour. The vapour density is 10.6 (air =1) at 564° C., corresponding to a tetratomic molecule As; at a white heat the vapour density shows a considerable lowering in value, due to the dissociation of the complex molecule.
By condensing arsenic vapour in a glass tube, in a current of an indifferent gas, such as hydrogen, amorphous arsenic is obtained, the deposit on the portion of the tube nearest to the source of heat being crystalline, that farther along (at a temperature of about C.) being a black amorphous solid, while still farther along the tube a grey deposit is formed. These two latter forms possess a specific gravity of 4.710 (14° C.) [A. Bettendorff, Annalen, 1867, 144, p. rro], and by heating at about 358°-360° C. pass over into the crystalline variety. Arsenic burns on heating in a current of oxygen, with a pale lavender-coloured flame, forming the trioxide. It is easily oxidized by heating with concentrated nitric acid to arsenic acid, and with concentrated sulphuric acid to arsenic trioxide; dilute nitric acid only oxidizes it to arsenious acid. It burns in an atmosphere of chlorine forming the trichloride; it also combines directly with bromine and sulphur on heating, while on fusion with alkalis it forms arsenites.
Arsenic and most of its soluble compounds are very poisonous, and consequently the methods used for the detection of arsenic are very important. For full accounts of methods used in detecting minute traces of arsenic in foods, &c., see "Report to Commission to Manchester Brewers' Central Association," the Analyst, 1900, 26, p. 8; "Report of Conjoint Committee of Society of Chemical Industry and Society of Public Analysts," the Analyst, 1902, 27, p. 48; T. E. Thorpe, Journal of the Chemical Society, 1903, 8 3, p. 774; O. Hehner and others, Journal of Society of Chemical Industry, 1902, 21, p. 94; also Adulteration.
Arsenic and arsenical compounds generally can be detected by (a) Reinsch's test: A piece of clean copper is dipped in a solution of an arsenious compound which has been previously acidified with pure hydrochloric acid. A grey film is produced on the surface of the copper, probably due to the formation of a copper arsenide. The reaction proceeds better on heating the solution. On removing, washing and gently drying the metal and heating it in a glass tube, a white crystalline sublimate is formed on the cool part of the tube; under the same conditions antimony does not produce a crystalline sublimate.
(b) Fleitmann's test and Marsh's test depend on the fact that arsenic and its compounds, when present in a solution in which hydrogen is being generated, are converted into arseniuretted hydrogen, which can be readily detected either by its action on silver nitrate solution or by its decomposition on heating. In Fleitmann's test, the solution containing the arsenious compound is mixed with pure potassium hydroxide solution and a piece of pure zinc or aluminium foil dropped in and the whole then heated. A piece of bibulous paper, moistened with silver nitrate, is held over the mouth of the tube, and if arsenic be present, a grey or black deposit is seen on the paper, due to the silver nitrate being reduced by the arseniuretted hydrogen. Antimony gives no reaction under these conditions, so that the method can be used to detect arsenic in the presence of antimony, but the test is not so delicate as either Reinsch's or Marsh's method.
In the Marsh test the solution containing the arsenious compounds is mixed with pure hydrochloric acid and placed in an apparatus in which hydrogen is generated from pure zinc and pure sulphuric acid. The arseniuretted hydrogen produced is passed through a tube containing lead acetate paper and soda-lime, and finally through a narrow glass tube, constricted at various points, and heated by a very small flame. As the arseniuretted hydrogen passes over the heated portion it is decomposed and a black deposit formed. Instead of heating the tube, the gas may be ignited at the mouth of the tube and a cold surface of porcelain or platinum placed in the flame, when a black deposit is formed on the surface. This may be distinguished from the similar antimony deposit by its ready solubility in a solution of sodium hypochlorite. A blank experiment should always be carried out in testing for small quantities of arsenic, to ensure that the materials used are quite free from traces of arsenic. It is to be noted that the presence of nitric acid interferes with the Marsh test; and also that if the arsenic is present as an arsenic compound it must be reduced to the arsenious condition by the action of sulphurous acid. Arsenic compounds can be detected in the dry way by heating in a tube with a mixture of sodium carbonate and charcoal when a deposit of black amorphous arsenic is produced on the cool part of the tube, or by conversion of the compound into the trioxide and heating with dry sodium acetate when the offensive odour of the extremely poisonous cacodyl oxide is produced. In the wet way, arsenious oxide and arsenites, acidified with hydrochloric acid, give a yellow precipitate of arsenic trisulphide on the addition of sulphuretted hydrogen; this precipitate is soluble in solutions of the alkaline hydroxides, ammonium carbonate and yellow ammonium sulphide. Under like conditions arsenates only give a precipitate on long-continued boiling.
Arsenic is usually estimated either in the form of magnesium pyroarsenate or as arsenic sulphide. For the pyroarsenate method it is necessary that the arsenic should be in the arsenic condition, if necessary this can be effected by heating with nitric acid; the acid solution is then mixed with "magnesia mixture" and made strongly alkaline by the addition of ammonia. It is then allowed to stand twenty-four hours, filtered, washed with dilute ammonia, dried, ignited to constant weight and weighed, the filter paper being incinerated separately after moistening with nitric acid. From the weight of magnesium pyroarsenate obtained the weight of arsenic can be calculated.
In the sulphide method, the arsenic should be in the arsenious form. Sulphuretted hydrogen is passed through the liquid until it is thoroughly saturated, the excess of sulphuretted hydrogen is expelled from the solution by a brisk stream of carbon dioxide, and the precipitate is filtered on a Gooch crucible and washed with water containing a little sulphuretted hydrogen and dried at 100° C.; it is then well washed with small quantities of pure carbon disulphide to remove any free sulphur, again dried and weighed. Arsenic can also be estimated by volumetric methods; for this purpose it must be in the arsenious condition, and the method of estimation consists in converting it into the arsenic condition by means of a standard solution of iodine, in the presence of a cold saturated solution of sodium bicarbonate.
The atomic weight of arsenic has been determined by many different chemists. J. Berzelius, in 1818, by heating arsenious oxide with excess of sulphur obtained the value 74.3; J. Pelouze (Comptes rendus, 1845, 20, p. 1047) titrated arsenic chloride with silver solution and obtained 75o; and F. Kessler (Pogg. Ann. 1861, 113, p. 134) by converting arsenic trisulphide in hydrochloric acid solution into arsenic pentasulphide also obtained 75.0.
Compounds
Arsenic forms two hydrides: - The dihydride, As2H2, is a brown velvety powder formed when sodium or potassium arsenide is decomposed by water. It is a somewhat unstable substance, decomposing on being heated, with liberation of hydrogen. Arsenic trihydride (arsine or arseniuretted hydrogen), AsH3, is formed by decomposing zinc arsenide with dilute sulphuric acid; by the action of nascent hydrogen on arsenious compounds, and by the electrolysis of solutions of arsenious and arsenic acids; it is also a product of the action of organic matter on many arsenic compounds. It is a colourless gas of unpleasant smell, excessively poisonous, very slightly soluble in water. It easily burns, forming arsenious oxide if the combustion proceeds in an excess of air, or arsenic if the supply of air is limited; it is also decomposed into its constituent elements when heated. It liquefies at -40° C. and becomes solid at -118.9° C. (K. Olszewski). Metals such as tin, potassium and sodium, when heated in the gas, form arsenides, with liberation of hydrogen; and solutions of gold and silver salts are reduced by the gas with precipitation of metallic gold and silver. Chlorine, bromine and iodine decompose arsine readily, the action being most violent in the case of chlorine.
Arsenic tribromide, AsBr3, is formed by the direct union of arsenic and bromine, and subsequent distillation from the excess of arsenic; it forms colourless deliquescent prisms which melt at 20 0 -25° C., and boil at 220° C. Water decomposes it, a small quantity of water leading to the formation of the oxybromide, AsOBr, whilst a large excess of water gives arsenious oxide, As4O6.
Arsenic certainly forms two, or possibly three iodides. The di-iodide, As2I4 or AsI2 which is prepared by heating one part of arsenic with two parts of iodine, in a sealed tube to 230° C., forms dark cherry red prisms, which are easily oxidized, and are readily decomposed by water. The tri-iodide, AsI3 prepared by subliming arsenic and iodine together in a retort, by leading arsine into an alcoholic iodine solution, or by boiling powdered arsenic and iodine with water, filtering and evaporating, forms brick-red hexagonal tables, of specific gravity 4.39, soluble in alcohol, ether and benzene, and in a large excess of water; in the presence of a small quantity of water, it is decomposed with formation of hydriodic acid and an insoluble basic salt of the composition 4AsOI. 3As406.24H2O. It combines with alkaline iodides to form very unstable compounds. The pentaiodide, AsI5, appears to be formed when a mixture of one part of arsenic and seven parts of iodine is heated to 190° C., but on dissolving the resulting product in carbon bisulphide and crystallizing from this solvent, only the tri-iodide is obtained.
Arsenic trichloride, AsCl3, is prepared by distilling white arsenic with concentrated sulphuric acid and common salt, or by the direct union of arsenic with chlorine, or from the action of phosphorus pentachloride on white arsenic. It is a colourless oily heavy liquid of specific gravity 2.205 (o° C.), which, when pure and free from chlorine, solidifies at - 18°C., and boils at 132 °C. It is very poisonous and decomposes in moist air with evolution of white fumes. With a little water it forms arsenic oxychloride, AsOCl, and with excess of water it is completely decomposed into hydrochloric acid and white arsenic. It combines directly with ammonia to form a solid compound variously given as AsCl3.3NH3 or 2AsCl3.7NH3, or AsCl3.4NH3Arsenic trifluoride, AsF3, is prepared by distilling white arsenic with fluorspar and sulphuric acid, or by heating arsenic tribromide with ammonium fluoride; it is a colourless liquid of specific gravity 2.73, boiling at 63° C; it fumes in air, and in contact with the skin produces painful wounds. It is decomposed by water into arsenious and hydrofluoric acids, and absorbs ammonia forming the compound 2AsF3.5NH3 By the action of gaseous ammonia on arsenious halides at -30° C. to -40° C., arsenamide, As(NH2) is formed. Water decomposes it into arsenious oxide and ammonia, and when heated to 60° it loses ammonia and forms arsenimide, As2(NH)3 (C. Hugot, Compt. rend. 1904, 1 39, p. 54). For AsF5, see Ber., 1906, 39, p. 67.
Two oxides of arsenic are definitely known to exist, namely the trioxide (white arsenic), As406, and the pentoxide, As205, while the existence of a suboxide, As20</sub>(?), has also been mooted. Arsenic trioxide has been known from the earliest times, and was called Huettenrauch (furnace-smoke) by Basil Valentine. It occurs naturally in the mineral claudetite, and can be artificially prepared by burning arsenic in air or oxygen. It is obtained commercially by roasting arsenical pyrites in either a Brunton's or Oxland's rotatory calciner, the crude product being collected in suitable condensing chambers, and afterwards refined by resublimation, usually in reverberatory furnaces, the foreign matter being deposited in a long flue leading to the condensing chambers. White arsenic exists in two crystalline forms (octahedral and prismatic) and one amorphous form; the octahedral form is produced by the rapid cooling of arsenic vapour, or by cooling a warm saturated solution in water, or by crystallization from hydrochloric acid, and also by the gradual transition of the amorphous variety, this last phenomenon being attended by the evolution of heat. Its specific gravity is 3.7; it is only slightly soluble in cold water, but is more soluble in hot water, the solution reacting faintly acid. The prismatic variety of the oxide can be obtained by crystallization from a saturated boiling solution in potassium hydroxide, or by the crystallization of a solution of silver arsenite in nitric acid. Its specific gravity is 4.15. In the amorphous condition it can be obtained by condensing the vapour of the oxide at as high a temperature as possible, when a vitreous mass is produced, which melts at 200° C., has a specific gravity of 3.68-3.798, and is more soluble in water than the crystalline variety.
Arsenious oxide is very poisonous. It acts as a reducing agent; it is not convertible into the pentoxide by the direct action of oxygen; and its solution is reduced by many metals (e.g. zinc, tin and cadmium) with precipitation of arsenic and formation of arseniuretted hydrogen. The solution of arsenious oxide in water reacts acid towards litmus and contains tribasic arsenious acid, although on evaporation of the solution the trioxide is obtained and not the free acid. The salts of the acid are, however, very stable, and are known as arsenites. Of these salts several series are known, namely the ortho-arsenites, which are derivatives of the acid H3AsO3, the metaarsenites, derivatives of HAsO2, and the pyro-arsenites, derivatives of H4As2O5. The arsenites of the alkali metals are soluble in water, those of the other metals are insoluble in water, but are readily soluble in acids. A neutral solution of an arsenite gives a yellow precipitate of silver arsenite, Ag3AsO3, with silver nitrate solution, and a yellowish-green precipitate (Scheele's green) of cupric hydrogen arsenite, CuHAsO3, with copper sulphate solution. By the action of oxidizing agents such as nitric acid, iodine solution, &c., arsenious acid is readily converted into arsenic acid, in the latter case the reaction proceeding according to the equation H3AsO3 +I2 + H2O = H3AsO4 + 2HI. Arsenic pentoxide, As2O5, is most easily obtained by oxidation of a solution of arsenious acid with nitric acid; the solution on concentration deposits the compound 2H3AsO4.H2O (below 15° C.), which on being heated to a dark red heat loses its water of crystallization and leaves a white vitreous mass of the pentoxide. This substance dissolves slowly in water, forming arsenic acid; by heating to redness it decomposes into arsenic and oxygen. It deliquesces in moist air, and is easily reduced to arsenic by heating with carbon.
Arsenic acid, H3AsO4, is prepared as shown above, the compound 2H3AsO4.H2O on being heated to 100° C. parting with its water of crystallization and leaving a residue of the acid, which crystallizes in needles. On heating to 180° C. it loses water and yields pyroarsenic acid, H4As2O7, which at 200° C. loses more water and leaves a crystalline mass of meta-arsenic acid, HAsO3 These latter two acids are only stable in the solid state; they dissolve readily in water with evolution of heat and immediate transformation into the ortho-arsenic acid. The salts of arsenic acid, termed arsenates, are isomorphous with the phosphates, and in general character and reactions resemble the phosphates very closely; thus both series of salts give similar precipitates with "magnesia mixture" and with ammonium molybdate solution, but they can be distinguished by their behaviour with silver nitrate solution, arsenates giving a reddish-brown precipitate,whilst phosphates give a yellow precipitate.
There are three known compounds of arsenic and sulphur, namely, realgar As2S2, orpiment As2S3, and arsenic pentasulphide As2S5.
Realgar occurs native in orange prisms of specific gravity 3.5; it is prepared artificially by fusing together arsenic and sulphur, but the resulting products vary somewhat in composition; it is readily fusible and sublimes unchanged, and burns on heating in a current of oxygen, forming arsenic trioxide and sulphur dioxide.
Orpiment (auri pigmentum) occurs native in pale yellow rhombic prisms, and can be obtained in the amorphous form by passing a current of sulphuretted hydrogen gas through a solution of arsenious oxide or an arsenite, previously acidified with dilute hydrochloric acid. It melts easily and volatilizes. It burns on heating in air, and is soluble in solutions of alkaline hydroxides and carbonates, forming thioarsenites, As2S3 + 4KOH = K2HAsO3 + K2HAsS3 + 1H2O. On acidifying the solution so obtained with hydrochloric acid,
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Chisholm, Hugh, General Editor. Entry for 'Arsenic'. 1911 Encyclopedia Britanica. https://www.studylight.org/encyclopedias/eng/bri/a/arsenic.html. 1910.
