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 testandMarsh’s testdepend 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 overthe 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 anarseniccompound it must be reduced to thearseniouscondition 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 thearseniccondition, 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 thearseniousform. 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 thearseniouscondition, and the method of estimation consists in converting it into thearseniccondition 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 75.0; 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:—Thedihydride, 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. Arsenictrihydride(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°-25° C., and boil at 220° C. Water decomposes it, a small quantity of water leading to the formation of theoxybromide, AsOBr, whilst a large excess of water gives arsenious oxide, As4O6.Arsenic certainly forms two, or possibly three iodides. Thedi-iodide, As2I4or 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. Thetri-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·3As4O6·24H2O. It combines with alkaline iodides to form very unstable compounds. Thepentaiodide, 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 (0° 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 AsCl3·4NH3.Arsenic trifiuoride, 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)3, is formed. Water decomposes it into arsenious oxide and ammonia, and when heated to 60° it loses ammonia and formsarsenimide, As2(NH)3(C. Hugot,Compt. rend.1904, 139, p. 54). For AsF5, seeBer., 1906, 39, p. 67.Two oxides of arsenic are definitely known to exist, namely the trioxide (white arsenic), As4O6, and the pentoxide, As2O5, while the existence of a suboxide, As2O(?), has also been mooted. Arsenic trioxide has been known from the earliest times, and was calledHüttenrauch(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 meta-arsenites, 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 leavesa 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+ 4KHO = K2HAsO3+ K2HAsS3+ H2O. On acidifying the solution so obtained with hydrochloric acid, the whole of the arsenic is reprecipitated as trisulphide, K2HAsO3+ K2HAsS3+ 4HCl = 4KCl + 3H2O + As2S3. Arsenic pentasulphide, As2S5, can be prepared by fusing the trisulphide with the requisite amount of sulphur; it is a yellow easily-fusible solid, which in absence of air can be sublimed unchanged; it is soluble in solutions of the caustic alkalis, forming thioarsenates, which can also be obtained by the action of alkali polysulphides on orpiment. The thioarsenites and thioarsenates of the alkali metals are easily soluble in water, and are readily decomposed by the action of mineral acids. Arsenic compounds containing selenium and sulphur are known, such as arsenic seleno-sulphide, AsSeS2, and arsenic thio-selenide, AsSSe2. Arsenic phosphide, AsP, results when phosphine is passed into arsenic trichloride, being precipitated as a red-brown powder.Many organic arsenic compounds are known, analogous to those of nitrogen and phosphorus, but apparently the primary and secondary arsines, AsH2·CH3and AsH(CH3)2, do not exist, although the corresponding chlorine derivatives, AsCl2·CH3, methyl arsine chloride, and AsCl(CH4)2, dimethyl arsine chloride, are known. The tertiary arsines, such as As(CH3)3, trimethyl arsine, and the quaternary arsonium iodides and hydroxides, (CH3)4AsI and (CH3)4As·OH, tetramethyl arsonium iodide and hydroxide, have been obtained. The arsines and arsine chlorides are liquids of overpowering smell, and in some cases exert an extremely irritating action on the mucous membrane. They do not possess basic properties; the halogen in the chlorine compounds is readily replaced by oxygen, and the oxides produced behave like basic oxides. The chlorides AsCl2·CH3and AsCl(CH3)2as well as As(CH3)3are capable of combining with two atoms of chlorine, the arsenic atom apparently changing from the tri- to the penta-valent condition, and the corresponding oxygen compounds can also be oxidized to compounds containing one oxygen atom or two hydroxyl groups more, forming acids or oxides. The compounds of the type AsX5,e.g.AsCl4·CH3, AsCl3(CH3)2, on heating break down, with separation of methyl chloride and formation of compounds of the type AsX3; the breaking down taking place more readily the fewer the number of methyl groups in the compound. The dimethyl arsine (or cacodyl) compounds have been most studied. On distillation of equal parts of dry potassium acetate and arsenious oxide, a colourless liquid of unbearable smell passes over, which is spontaneously inflammable and excessively poisonous. It is sometimes called Cadet’s fuming liquid, and its composition was determined by R. Bunsen, who gave it the name cacodyl oxide (κακώδης, stinking); its formation may be shown thus:As4O6+ 8CH3CO2K = 2[(CH3)2As]2O + 4K2CO3+ 4CO2.The liquid is spontaneously inflammable owing to the presence of free cacodyl, As2(CH3)4, which is also obtained by heating the oxide with zinc clippings in an atmosphere of carbon dioxide; it is a liquid of overpowering odour, and boils at 170°C. Cacodyl oxide boils at 150° C., and on exposure to air takes up oxygen and water and passes over into the crystalline cacodylic acid, thus:[(CH3)2As]2O + H2O + O2= 2(CH3)2As·O·OH.
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 testandMarsh’s testdepend 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 overthe 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 anarseniccompound it must be reduced to thearseniouscondition 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 thearseniccondition, 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 thearseniousform. 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 thearseniouscondition, and the method of estimation consists in converting it into thearseniccondition 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 75.0; 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:—Thedihydride, 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. Arsenictrihydride(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°-25° C., and boil at 220° C. Water decomposes it, a small quantity of water leading to the formation of theoxybromide, AsOBr, whilst a large excess of water gives arsenious oxide, As4O6.
Arsenic certainly forms two, or possibly three iodides. Thedi-iodide, As2I4or 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. Thetri-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·3As4O6·24H2O. It combines with alkaline iodides to form very unstable compounds. Thepentaiodide, 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 (0° 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 AsCl3·4NH3.
Arsenic trifiuoride, 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)3, is formed. Water decomposes it into arsenious oxide and ammonia, and when heated to 60° it loses ammonia and formsarsenimide, As2(NH)3(C. Hugot,Compt. rend.1904, 139, p. 54). For AsF5, seeBer., 1906, 39, p. 67.
Two oxides of arsenic are definitely known to exist, namely the trioxide (white arsenic), As4O6, and the pentoxide, As2O5, while the existence of a suboxide, As2O(?), has also been mooted. Arsenic trioxide has been known from the earliest times, and was calledHüttenrauch(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 meta-arsenites, 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 leavesa 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+ 4KHO = K2HAsO3+ K2HAsS3+ H2O. On acidifying the solution so obtained with hydrochloric acid, the whole of the arsenic is reprecipitated as trisulphide, K2HAsO3+ K2HAsS3+ 4HCl = 4KCl + 3H2O + As2S3. Arsenic pentasulphide, As2S5, can be prepared by fusing the trisulphide with the requisite amount of sulphur; it is a yellow easily-fusible solid, which in absence of air can be sublimed unchanged; it is soluble in solutions of the caustic alkalis, forming thioarsenates, which can also be obtained by the action of alkali polysulphides on orpiment. The thioarsenites and thioarsenates of the alkali metals are easily soluble in water, and are readily decomposed by the action of mineral acids. Arsenic compounds containing selenium and sulphur are known, such as arsenic seleno-sulphide, AsSeS2, and arsenic thio-selenide, AsSSe2. Arsenic phosphide, AsP, results when phosphine is passed into arsenic trichloride, being precipitated as a red-brown powder.
Many organic arsenic compounds are known, analogous to those of nitrogen and phosphorus, but apparently the primary and secondary arsines, AsH2·CH3and AsH(CH3)2, do not exist, although the corresponding chlorine derivatives, AsCl2·CH3, methyl arsine chloride, and AsCl(CH4)2, dimethyl arsine chloride, are known. The tertiary arsines, such as As(CH3)3, trimethyl arsine, and the quaternary arsonium iodides and hydroxides, (CH3)4AsI and (CH3)4As·OH, tetramethyl arsonium iodide and hydroxide, have been obtained. The arsines and arsine chlorides are liquids of overpowering smell, and in some cases exert an extremely irritating action on the mucous membrane. They do not possess basic properties; the halogen in the chlorine compounds is readily replaced by oxygen, and the oxides produced behave like basic oxides. The chlorides AsCl2·CH3and AsCl(CH3)2as well as As(CH3)3are capable of combining with two atoms of chlorine, the arsenic atom apparently changing from the tri- to the penta-valent condition, and the corresponding oxygen compounds can also be oxidized to compounds containing one oxygen atom or two hydroxyl groups more, forming acids or oxides. The compounds of the type AsX5,e.g.AsCl4·CH3, AsCl3(CH3)2, on heating break down, with separation of methyl chloride and formation of compounds of the type AsX3; the breaking down taking place more readily the fewer the number of methyl groups in the compound. The dimethyl arsine (or cacodyl) compounds have been most studied. On distillation of equal parts of dry potassium acetate and arsenious oxide, a colourless liquid of unbearable smell passes over, which is spontaneously inflammable and excessively poisonous. It is sometimes called Cadet’s fuming liquid, and its composition was determined by R. Bunsen, who gave it the name cacodyl oxide (κακώδης, stinking); its formation may be shown thus:
As4O6+ 8CH3CO2K = 2[(CH3)2As]2O + 4K2CO3+ 4CO2.
The liquid is spontaneously inflammable owing to the presence of free cacodyl, As2(CH3)4, which is also obtained by heating the oxide with zinc clippings in an atmosphere of carbon dioxide; it is a liquid of overpowering odour, and boils at 170°C. Cacodyl oxide boils at 150° C., and on exposure to air takes up oxygen and water and passes over into the crystalline cacodylic acid, thus:
[(CH3)2As]2O + H2O + O2= 2(CH3)2As·O·OH.
Pharmacology.—Of arsenic and its compounds, arsenious acid (dose1⁄60-1⁄15gr.) and its preparation liquor arsenicalis, Fowler’s solution (dose 2-8 ♏), are in very common use. The iodide of arsenic (dose1⁄20-1⁄5gr.) is one of the ingredients of Donovan’s solution (seeMercury); and iron arsenate (dose1⁄16-¼ gr. in a pill), a mixture of ferrous and ferric arsenates with some iron oxide, is of great use in certain cases. Sodium arsenate (1⁄40-1⁄10gr.) is somewhat less commonly prescribed, though all the compounds of this metal have great value in experienced hands.
Externally, arsenious acid is a powerful caustic when applied to raw surfaces, though it has no action on the unbroken skin. Internally, unless the dose be extremely small, all preparations are severe gastro-intestinal irritants. This effect is the same however the drug be administered, as, even after subcutaneous injection, the arsenic is excreted into the stomach after absorption, and thus sets up gastritis in its passage through the mucous membrane. In minute doses it is a gastric stimulant, promoting the flow of gastric juice. It is quickly absorbed into the blood, where its presence can be demonstrated especially in the white blood corpuscles. In certain forms of anaemia it increases the number of the red corpuscles and also their haemoglobin content. None of these known effects of arsenic is sufficient to account for the profound change that a course of the drug will often produce in the condition of a patient. It has some power of affecting the general metabolism, but no wholly satisfactory explanation is forthcoming. According to Binz and Schultz its power is due to the fact that it is an oxygen-carrier, arsenious acid withdrawing oxygen from the protoplasm to form arsenic acid, which subsequently yields up its oxygen again. It is thus vaguely called an alterative, since the patient recovers under its use. It is eliminated chiefly by the urine, and to a less extent by the alimentary canal, sweat, saliva, bile, milk, tears, hair, &c., but it is also stored up in the body mainly in the liver and kidneys.
Therapeutics.—Externally arsenious acid has been much used by quack doctors to destroy morbid growths, &c., a paste or solution being applied, strong enough to kill the mass of tissue and make it slough out quickly. But many accidents have resulted from the arsenic being absorbed, and the patient thereby poisoned. Internally it is useful in certain forms of dyspepsia, but as some patients are quite unable to tolerate the drug, it must always be administered in very small doses at first, the quantity being slowly increased as tolerance is shown. Children as a rule bear it better than adults. It should never be given on an empty stomach, but always after a full meal. Certain cases of anaemia which do not yield to iron are often much improved by arsenic, though in other apparently similar ones it appears to be valueless. It is the routine treatment for pernicious anaemia and Hodgkin’s disease, though here again the drug may be of no avail. For the neuralgia and anaemia following malaria, for rheumatoid arthritis, for chorea and also asthma and hay fever, it is constantly prescribed with excellent results. Certain skin diseases, as psoriasis, pemphigus and occasionally chronic eczema, are much benefited by its use, though occasionally a too prolonged course will produce the very lesion for which under other circumstances it is a cure. A recent method of using the drug is in the form of sodium cacodylate by subcutaneous injection, and this preparation is said to be free from the cumulative effects sometimes arising after the prolonged use of the other forms. Other organic derivatives employed are sodium metharsenite and sodium anilarsenate or atoxyl; hypodermic injections of the latter have been used in the treatment of sleeping sickness. Occasionally, as among the Styrians, individuals acquire the habit of arsenic-eating, which is said to increase their weight, strength and appetite, and clears their complexion. The probable explanation is that an antitoxin is developed within them.
Toxicology and Forensic Medicine.—The commonest source of arsenical poisoning is the arsenious acid or white arsenic, which in one form is white and opaque, like flour, for which it has been mistaken with fatal results. Also, as it has little taste and no colour it is easily mixed with food for homicidal purposes. When combined with potash or soda it is used to saturate flypapers, and strong solutions can be obtained by soaking these in water; this fact has also been used with criminal intent. Copper arsenite (or Scheele’s green) used to be much employed as a pigment for wall-papers and fabrics, and toxic effects have resulted from their use. Metallic arsenic is probably not poisonous, but as it usually becomes oxidized in the alimentary canal, the usual symptoms of arsenical poisoning follow its use.
In acute poisoning the interval between the reception of the poison and the onset of symptoms ranges from ten minutes, or even less, if a strong solution be taken on an empty stomach, totwelve or more hours if the drug be taken in solid form and the stomach be full of food. The usual period, however, is from half an hour to an hour. In a typical case a sensation of heat developing into a burning pain is felt in the throat and stomach. This is soon followed by uncontrollable vomiting, and a little later by severe purging, the stools being first of all faecal but later assuming a rice water appearance and often containing blood. The patient suffers from intense thirst, which cannot be relieved, as drinking is immediately followed by rejection of the swallowed fluid. There is profound collapse, the features are sunken, the skin moist and cyanosed. The pulse is feeble and irregular, and respiration is difficult. The pain in the stomach is persistent, and cramps in the calves of the legs add to the torture. Death may be preceded by coma, but consciousness is often maintained to the end. The similarity of the symptoms to those of cholera is very marked, but if the suspicion arises it can soon be cleared up by examining any of the secretions for arsenic. More rarely the poison seems to centre itself on the nerve centres, and gastro-intestinal symptoms may be almost or quite absent. In such cases the acute collapse occurs in company with both superficial and deep anaesthesia of the limbs, and is soon followed by coma terminating in death. In criminal poisoning repeated doses are usually given, so that such cases may not be typical, but will present some of the aspects of acute and some of chronic arsenical poisoning. As regards treatment, the stomach must be washed out with warm water by means of a soft rubber tube, an emetic being also administered. Then, if available, freshly precipitated ferric hydrate must be given, which can be prepared by adding a solution of ammonia to one of iron perchloride. The precipitate is strained off, and the patient can swallow it suspended in water. While this is being obtained, magnesia, castor oil or olive oil can be given; or failing all these, copious draughts of water. The collapse must be treated with hot blankets and bottles, and subcutaneous injections of brandy, ether or strychnine. The pain can be lessened by injections of morphia.
Arsenic may be gradually absorbed into the system in very small quantities over a prolonged period, the symptoms of chronic poisoning resulting. The commonest sources used to be wall-papers, fabrics, artificial flowers and toys: also certain trades, as in the manufacture of arsenical sheep-dipping. But at the present time cases arising from these causes occur very rarely. In 1900 an outbreak of “peripheral neuritis” with various skin affections occurred in Lancashire, which was traced to beer made from glucose and invert sugar, in the preparation of which sulphuric acid contaminated with arsenic was said to have been used. But the nature of the disease in this case was decidedly obscure. The symptoms so closely resembled those ofberi-berithat it has also been suggested that the illness was the same, and was caused by the manufacture of the glucose from mouldy rice (seeBeri-Beri), though no proof of this was possible. The earliest symptoms are slight gastric disorders, loss of appetite and general malaise, followed later by colicky pains, irritation of eyelids and skin eruptions. But sooner or later peripheral neuritis develops, usually beginning with sensory disturbances, tingling, numbness, formication and occasionally cutaneous anaesthesia. Later the affected muscles become exquisitely tender, and then atrophy, while the knee-jerk or other reflex is lost. Pigmentation of the skin may occur in the later stages. Recovery is very slow, and in fatal cases death usually results from heart failure.
After acute poisoning, the stomach at apost-mortempresents signs of intense inflammation, parts or the whole of its mucous membrane being of a colour varying from dark red to bright vermilion and often corrugated. Submucous haemorrhages are usually present, but perforation is rare. The rest of the alimentary canal exhibits inflammatory changes in a somewhat lesser degree. After chronic poisoning a widely spread fatty degeneration is present. Arsenic is found in almost every part of the body, but is retained in largest amount by the liver, secondly by the kidneys. After death from chronic poisoning it is found present even in the brain and spongy bone. The detection of arsenic in criminal cases is effected either by Reinsch’s test or by Marsh’s test, the urine being the secretion analysed when available. But Reinsch’s test cannot be used satisfactorily for a quantitative determination, nor can it be used in the presence of chlorates or nitrates. And Marsh’s test is very unmanageable with organic liquids on account of the uncontrollable frothing that takes place. But in such cases the organic matter can be first destroyed by one of the various methods, usually the moist method devised by Fresenius being chosen.
ARSENIUS(c.354-450), an anchorite, said to have been born of a noble Roman family, who achieved a high reputation for his knowledge of Greek and Roman literature. He was appointed by Theodosius the Great, tutor of the young princes Arcadius and Honorius, but at the age of forty he retired to Egypt, where for forty years he lived in monastic seclusion at Scetis in the Thebais, under the spiritual guidance of St John the Dwarf. He is said to have gained the admiration of his fellows by the extreme rigour of his asceticism. The remainder of his life he spent at Canopus, and Troë near Memphis, where he died at the age of ninety-five. Of his writings two collections of admonitory maxims are extant: the first,Διδασκαλία καὶ παραίνεσις, containing instructions for monks, is published with a Latin version by Fr. Combefis inAuctarium biblioth. patr. novissim.(Paris, 1672), pp. 301 f.; the second is a collection of forty-four wise sayings put together by his friends under the title ofἈποφθέγματα(see Cotelerius,Eccl. graec. monum., 1677, i. pp. 353-372). In the Roman Catholic Church his festival is on the 19th of July, in the Orthodox Eastern Church on the 8th of May. His biography by Simeon Metaphrastes is largely fiction.
ARSENIUS AUTORIANUS(13th century), patriarch of Constantinople, lived about the middle of the 13th century. He received his education in Nicaea at a monastery of which he later became the abbot, though not in orders. Subsequently he gave himself up to a life of solitary asceticism in a Bithynian monastery, and is said, probably wrongly, to have remained some time in a monastery on Mount Athos. From this seclusion he was inA.D.1255 called by Theodore II. Lascaris to the position of patriarch at Nicaea, and four years later, on that emperor’s death, became joint guardian of his son John. His fellow-guardian Georgios Mouzalon was immediately murdered by Michael Palaeologus, who assumed the position of tutor. Arsenius then took refuge in the monastery of Paschasius, retaining his office of patriarch but refusing to discharge its duties. Nicephorus of Ephesus was appointed in his stead. In 1261 Michael, having recovered Constantinople, induced Arsenius again to undertake the office of patriarch, but soon incurred his severe censure by ordering the young prince John to be blinded. Arsenius went so far as to excommunicate the emperor, who, having vainly sought for pardon, took refuge in false accusations against Arsenius and caused him to be banished to Proconnesus, where some years afterwards (according to Fabricius in 1264; others say in 1273) he died. Throughout these years he declined to remove the sentence of excommunication which he had passed upon Michael, and after his death, when the new patriarch Josephus gave absolution to the emperor, the quarrel was carried on between the “Arsenites” and the “Josephists.” The “Arsenian schism” lasted till 1315, when reconciliation was effected by the patriarch Niphon (see Gibbon,Decline and Fall of the Roman Empire, ed. J.B. Bury, 1898, vol. vi. 467 foll.). Arsenius is said to have prepared from the decisions of the councils and the works of the Fathers a summary of divine laws under the titleSynopsis Canonum. This was published (Greek original and Latin version) by G. Voël and H. Justel inBibliotheca Jur. Canon. Vet.(Paris, 1661), 749 foll. Some hold that theSynopsiswas the work of another Arsenius, a monk of Athos (see L. Petit in Vacant’sDict. théol. cathol.i. col. 1994); the ascription depends on whether the patriarch Arsenius did or did not sojourn at Mount Athos.
See Georgius Pachymeres ii. 15, iii.passim, iv. 1-16; Nicephorus Gregoras iii. 1, iv. 1; for the will of Arsenius see Cotelerius,Monumenta, ii. 168.
See Georgius Pachymeres ii. 15, iii.passim, iv. 1-16; Nicephorus Gregoras iii. 1, iv. 1; for the will of Arsenius see Cotelerius,Monumenta, ii. 168.
ARSES,Persian king, youngest son of Artaxerxes III., was raised to the throne in 338B.C.by Bagoas (q.v.), who hadmurdered his father and all his brothers. But when the young king tried to make himself independent, Bagoas killed him too, with all his children, in the third year of his reign (336) (Diod. 17.5; Strabo 15. 736; Trogus, Prol. x., Alexander’s despatch to Darius III.; Arrian ii. 14. 5, and the chronographers). In Plutarch,De fort. Alex.ii. 3. 5, he is calledOarses; in Johannes Antioch. p. 38,Arsamos; in the canon of Ptolemy,Aroges(by Elias of Nisibis,Pīrūz); in a chronological tablet from Babylon (Brit. Mus. Sp. ii. 71,Zeitschrift für Assyriologie, viii. 176, x. 64) he is abbreviated intoAr. SeePersia:Ancient History.
(Ed. M.)
ARSINOË,the name of four Egyptian princesses of the Ptolemaic dynasty. The name was introduced into the Ptolemaic dynasty by the mother of Ptolemy I. This Arsinoë was originally a mistress of Philip II. of Macedon, who presented her to a Macedonian soldier Loqus shortly before Ptolemy was born. It was, therefore, assumed by the Macedonians that the Ptolemaic house was really descended from Philip (seePtolemies).
1. Daughter of Lysimachus, king of Thrace, first wife of Ptolemy II. Philadelphus (285-247B.C.). Accused of conspiring against her husband, who perhaps already contemplated marriage with his sister, also named Arsinoë, she was banished to Coptos, in Upper Egypt. Her son Ptolemy was afterwards king under the title of Euergetes. It is supposed by some (e.g.Niebuhr,Kleine Schriften; cf. Ehrlichs,De Callimachi hymnis) that she is to be identified with the Arsinoë who became wife of Magas, king of Cyrene, and that she married him after her exile to Coptos. But this hypothesis is apparently without foundation. Magas before his death had betrothed his daughter Berenice to the son of his brother Ptolemy II. Philadelphus, but Arsinoë, disliking the projected alliance, induced Demetrius the Fair, son of Demetrius Poliorcetes, to accept the throne of Cyrene as husband of Berenice. She herself, however, fell in love with the young prince, and Berenice in revenge formed a conspiracy, and, having slain Demetrius, married Ptolemy’s son (seeBerenice, 3).
2. Daughter of Ptolemy I. Soter and Berenice. Born about 316B.C., she married Lysimachus, king of Thrace, who made over to her the territories of his divorced wife, Amastris. To secure the succession for her own children she brought about the murder of her stepson Agathocles. Lysandra, the wife of Agathocles, took refuge with Seleucus, king of Syria, who made war upon Lysimachus and defeated him (281). After her husband’s death Arsinoë fled to Ephesus and afterwards to Cassandreia in Macedonia. Seleucus, who had seized Lysimachus’s kingdom, was murdered in 281 by Ptolemy Ceraunus (half-brother of Arsinoë), who thus became master of Thrace and Macedonia. To obtain possession of Cassandreia, he offered his hand in marriage to Arsinoë, and being admitted into the town, killed her two younger sons and banished her to Samothrace. Escaping to Egypt, she became the wife of her full brother Ptolemy II., the first instance of the practice (afterwards common) of the Greek kings of Egypt marrying their sisters. She was a woman of a masterful character and won great influence. Her husband, though she bore him no children, was devoted to her and paid her all possible honour after her death in 271. He gave her name to a number of cities, and also to a district (nome) of Egypt.1It is related that he ordered the architect Dinochares to build a temple in her honour in Alexandria; in order that her statue, made of iron, might appear to be suspended in the air, the roof was to consist of an arch of loadstones (Pliny,Hist. Nat.xxxiv. 42). Coins were also struck, showing her crowned and veiled on the obverse, with a double cornucopia on the reverse. She was worshipped as a goddess under the title ofΘεὰ φιλάδελφος, and she and her husband asΘεοὶ ἄδελφοι(Justin xxiv. 2, 3; Pausanias i. 7).
See von Prott,Rhein. Mus.liii. (1898), pp. 460 f.
See von Prott,Rhein. Mus.liii. (1898), pp. 460 f.
3. Daughter of Ptolemy III. Euergetes, sister and wife of Ptolemy IV. Philopator. She seems to be erroneously called Eurydice by Justin (xxx. 2), and Cleopatra by Livy (xxvii. 4). Her presence greatly encouraged the troops at the battle of Raphia (217), in which Antiochus the Great was defeated. Her husband put her to death to please his mistress Agathocleia, a Samian dancer (between 210 and 205). She was worshipped asΘεὰ φιλοπάτωρ; she and her husband asΘεοὶ φιλοπάτορες(Polybius v. 83, 84, xv. 25-33).
4. Youngest daughter of Ptolemy XIII. Auletes, and sister of the famous Cleopatra. During the siege of Alexandria by Julius Caesar (48) she was recognized as queen by the inhabitants, her brother, the young Ptolemy, being then held captive by Caesar. Caesar took her with him to Rome as a precaution. After Caesar’s triumph she was allowed to return to Alexandria. After the battle of Philippi she was put to death at Miletus (or in the temple of Artemis at Ephesus) by order of Mark Antony, at the request of her sister Cleopatra (Dio Cassius xlii. 39; Caesar,Bell. civ.iii. 112; Appian,Bell. civ.v. 9).
Authorities.—For general authorities see articlePtolemies. The article “Arsinoë” in Pauly-Wissowa’sRealencyclopädiecontains a full list of those who bore the name, and also of the numerous towns which were called after the various princesses.
Authorities.—For general authorities see articlePtolemies. The article “Arsinoë” in Pauly-Wissowa’sRealencyclopädiecontains a full list of those who bore the name, and also of the numerous towns which were called after the various princesses.
1The appendix to pt. ii. of the Tebtunis series of papyri (Grenfell, Hunt and Goodspeed, 1907) contains a lengthy account of the topography of the Arsinoite nome.
1The appendix to pt. ii. of the Tebtunis series of papyri (Grenfell, Hunt and Goodspeed, 1907) contains a lengthy account of the topography of the Arsinoite nome.
ARSINOITHERIUM(so called from the Egyptian queen Arsinoë), a gigantic horned mammal from the Middle Eocene beds of the Fayum, Egypt, representing a sub-order of Ungulata, called Barypoda. The skull is remarkable for carrying a huge pair of horn-cores above the muzzle, which seem to be the enlarged nasal bones, and a rudimentary pair farther back; the front horn-cores, like the rest of the skull, consist of a mere shell of bone, and were probably clothed in life with horny sheaths. The teeth form a continuous even series, the small canines being crowded between the incisors and premolars; the crowns of the cheek-series are tall (hypsodont), with a distinctive pattern of their own. Although the brain is relatively larger, the bones of the limbs, especially the short, five-toed feet, approximate to those of the Amblypoda and Proboscidea; but in the articulation of the astragalus with both the navicular and cuboidArsinoitheriumis nearer the former than the latter group.
It is probable, however, that these resemblances are mainly due to parallelism in development, and are in all three cases adaptations necessary to support the enormous weight of the body. On the other hand, the marked resemblance of the structure of the tarsus is probably indicative of descent from nearly allied condylarthrous ancestors (seePhenacodus). No importance can be attached to the presence of horns as an indication of affinity betweenArsinoitheriumand the Amblypoda; and there are important differences in the structure of the skulls of the two, notably in the external auditory meatus, the occiput, the premaxillae, the palatal foramina and the lower jaw.
From the ProboscideaArsinoitheriumdiffers broadly in skull structure, in the form of the cheek-teeth, and in the persistence of the complete dental series of forty-four without gaps or enlargement of particular teeth. Whether there is any relationship with the Hyracoidea cannot be determined until we are acquainted with the forerunners ofArsinoitherium, which is evidently a highly specialized type.
It may be added that as the name Barypoda has been used at an earlier date for another group of animals, the alternative title Embrithopoda has been suggested in case the former should be considered barred.
See C.W. Andrews,Descriptive Catalogue of the Tertiary Vertebrata of the Fayum, British Museum(1906).
See C.W. Andrews,Descriptive Catalogue of the Tertiary Vertebrata of the Fayum, British Museum(1906).
(R. L.*)
ARSON(from Lat.ardere, to burn), a crime which has been described as the malicious and voluntary burning of the house of another (3 Co.Inst.66). At common law in England it is an offence of the degree of felony. In the Roman civil law arson was punishable by death. It appears early in the history of English law, being known in ancient laws by the term ofboernet. It is mentioned by Cnut as one of the bootless crimes, and under the Saxon laws was punishable by death. The sentence of death for arson was, says Stephen (Commentaries, iv. 89), in the reign of Edward I. executed by a kind oflex talionis, for the incendiaries were burnt to death; a punishment which was inflicted also underthe Gothic institutions. Death continued to be the penalty at least down to the reign of King John, according to a reported case (Gloucester Pleas, pl. 216), but in course of time the penalty became that of other common-law felonies, death by the gallows. It is one of the earliest crimes in which themens rea, or criminal intent, was taken special notice of. Bracton deals at length with themala conscientia, which he says is necessary for this crime, and contrasts it withnegligentia(f. 146 b), while in many early indictments malice aforethought (malitia praecogitata) appears. Arson was deprived of “benefit of clergy” under the Tudors, while an act of 8 Henry VI. c. 6 (1429) made the wilful burning of houses, under particular circumstances, high treason, but acts of 1 Ed. VI. c. 12 (1547) and 1 Mary (1553) reduced it to an ordinary felony. The English law concerning arson was consolidated by 7 & 8 Geo. IV. c. 30, which was repealed and re-enacted by the Malicious Damage Act 1861.
The common-law offence of arson (which has been greatly enlarged by the act of 1861) required some part of the house to be actually burnt; neither a bare intention nor even an actual attempt by putting fire in or towards it will constitute the offence, if no part was actually burnt, but the burning of any part, however trifling, is sufficient, and the offence is complete even if the fire is put out or goes out of itself. The burning must be malicious and wilful, otherwise it is only a trespass. If a man by wilfully setting fire to his own house burn the house of his neighbour also, it will be a felony, even though the primary intention of the party was to burn his own house only. The wordhouse, in the definition of the offence at common law, extends not only to dwelling-houses, “but to all out-houses which are parcel thereof, though not adjoining thereto.” Barns with corn and hay in them, though distant from a house, are within the definition.
The different varieties of the offence are specified in the Malicious Damage Act 1861. The following crimes are thereby made felonies: (1) setting fire to any church, chapel, meeting-house or other place of divine worship; (2) setting fire to a dwelling-house, any person being therein; (3) setting fire to a house, out-house, manufactory, farm-building, &c., with intent to impose and defraud any person; (4) setting fire to buildings appertaining to any railway, port, dock or harbour; or (5) setting fire to any public building. In these cases the act provides that the person convicted shall be liable, at the discretion of the court, to be kept in penal servitude for life, or for any term not less than three years (altered tofiveyears by the Penal Servitude Acts Amendment Act 1864), or to be imprisoned for any time not exceeding two years, with or without hard labour, and, if a male under sixteen years of age, with or without whipping. Setting fire to other buildings, and setting fire to goods in buildings under such circumstances that, if the building were thereby set fire to, the offence would amount to felony, are subject to the punishments last enumerated, with this exception that the period of penal servitude is limited to fourteen years. The attempt to set fire to any building, or any matter or thing not enumerated above, is punishable as a felony. Russell says (Crimes, p. 1781) that the term building is no doubt very indefinite, but it was used in 9 & 10 Vict. c. 25, s. 2; and it was thought much better to adopt this term and leave it to be interpreted as each case might arise, than to attempt to define; as any such attempt would probably have failed in producing any expression more certain than the term “building” itself. InR.v.Manning, 1872 (L.R. 1 C.C.R. 338), it was held that an unfinished house was a building within the meaning of the act. The setting fire to crops of hay, grass, corn, &c., is punishable by penal servitude for any period not exceeding fourteen years, but setting fire to stacks of the same, or any cultivated vegetable produce, or to peat, coals, &c., is regarded as a more serious offence, and the penal servitude may be for life. For the attempt to commit the last two offences penal servitude is limited to seven years. Setting fire to mines of coal, anthracite or other mineral fuel is visited with the full measure of penalty, and in the case of an attempt the penal servitude is limited to fourteen years. By the Dockyards, &c., Protection Act 1772 it is a felony punishable by death wilfully and maliciously to set fire to any of His Majesty’s ships or vessels of war, or any of His Majesty’s arsenals, magazines, dockyards, rope-yards, victualling offices or buildings therein, or any timber, material, stores or ammunition of war therein or in any part of His Majesty’s dominions. If the person guilty of the offence is a person subject to naval discipline, he is triable by court-martial, and if found guilty, a sentence of capital punishment may be passed. The Malicious Damage Act 1861, s. 43, also includes as a felony the setting fire to any ship or vessel, with intent to prejudice any owner or part owner of the vessel, or of any goods on the same, or any person who has underwritten any policy of insurance on the vessel, or upon any goods on board the same.
In Scotland the offence equivalent to arson in England is known by the more expressive name of fire-raising. The crime was punishable capitally by old consuetudinary law, but it is now no longer capital, and may be tried in the sheriff court (50 & 51 Vict. c. 35, s. 56). Formerly the public prosecutor had the privilege of declining to demand capital punishment, and he invariably did so.Wilful fire-raising, which is the most heinous form of the crime, requires the raising of fire, without any lawful object, but with the deliberate intention of destroying certain premises or things, whether directly by the application of fire thereto, or indirectly by its application to something contained in or forming part of or communicating with them; also the intention to destroy premises or things of a certain description (much as mentioned above); and such premises or things must be the property of another than the accused.Wicked, culpable and reckless fire-raisingdiffers from wilful fire-raising in that the fire is raisedwithoutthe deliberate intention of destroying premises or things, but while the accused was engaged in some unlawful act, or while he was in such a state of passion, excitement or recklessness as not to care what results might follow from his acts.
United States.—The same general principles apply to this crime in American law. In some states by statute the intent to injure or defraud must be shown,e.g.when the property is insured. In New York one who wilfully burns property (including a vessel or its cargo) with intent to defraud or prejudice the insurer thereof, though the offence of arson is not committed, is punishable by imprisonment for not more than five years (N.Y. Pen. Code, ss. 575, 578). There must be an intent to destroy the building (ibid.s. 490; California Code, s. 447). An agreement to commit arson is conspiracy (ibid.s. 171). Killing a person in committing the crime of arson is murder in the first degree (ibid.s. 183); this is so in California, even where the crime is merely an attempt to commit arson (Cal. Pen. Code, s. 189). Explosion of a house by gunpowder or dynamite is arson (Texas Pen. Code, art. 761), but a charge of arson by “burning” will not be sustained by proof of exploding by dynamite, even though part of the building is burnt by the explosion (Landersv.State[Tex.], 47 S.W. 1008).