TETRAMETHYLIUM-ETHYLIA. 527 in water. Methyl iodide immediately converts this base into a magma of crystals of tetramethylium iodide. Tetramethylium Hydrated Oxide.-The iodide of this base is the principal product formed by heating methyl iodide in excess with a solution of ammonia in wood spirit or in alcohol. Since tetramethylium iodide is sparingly soluble in cold water, it may be purified from the accompanying hydriodates of methylia, dimethylia, and trimethylia, by crystallization from boiling water. Caustic potash does not liberate any of these ammonium bases from their salts; but the decomposition is easily effected by treating the aqueous solution of the salt with freshly precipitated oxide of silver. When tetramethylium iodide is treated with recently precipitated oxide of silver, iodide of silver is formed, and a hydrated tetramethylium oxide [(CH),NHO] remains in solution; it may be obtained by evaporation in vacuo, over sulphuric acid, in crystals which are deliquescent, and attract carbonic acid. Its salts crystallize well, particularly the nitrate, which forms long brilliant needles. The chloride of platinum and tetramethylium [(E,H12NCI),PtCl] crystallizes in magnificent dark orange-coloured octohedra. This hydrated tetramethylium oxide when heated breaks up into trimethylia and wood spirit: (ЄH2) ̧N,HO=(ЄH2) ̧N+¤H ̧Ð. Tetramethylium iodide in like manner, when heated, breaks triethylia and methyl iodide (EH2),NI=(ЄHg) ̧N+ЄH2I. up into When the hydrated tetramethylium oxide is treated with an additional quantity of methyl iodide, no further combination of methyl with the base occurs; but double decomposition ensues, tetramethylium iodide is formed, and wood spirit is liberated : Hydrated tetrame- Methyl iodide. Wood spirit. Tetramethylium + (CH,),NHỎ + CH_I = CH_HO + (CH,),NI. €H2I : (1377) ETHYLIA, or Ethylamine (¤‚Í‚Ñ‚ or ¤‚Í ̧‚Í‚N=45) ; Sp. gr. of liquid 0696; of vapour 1594; Rel. wt. 225; Boiling pt. 65°6 (18°.6 C.).—This base constitutes a volatile, mobile, colourless liquid, which emits an inflammable vapour of a pungent ammoniacal odour. It is miscible with water in all proportions, but, by prolonged boiling, the whole of the ethylia may be expelled. Ethylia produces results with solutions of metallic salts similar to those of methylia, from which, however, it may very be distinguished by the power possessed by ethylia of dissolving recently precipitated alumina. Wurtz has proposed to take 528 ETHYLIA DIETHYLIA-TRIETHYLIA. advantage of this property as a means of separating alumina from ferric oxide, in the operation of analysis. Ethylia displaces ammonia from its salts if evaporated with them. It yields dense white fumes with vapours of hydrochloric acid. Ethylia may be prepared in a manner similar to that directed for methylia, by acting upon cyanic or cyanuric ether with caustic potash. It may also be obtained by acting upon ethyl iodide with ammonia, in which case ethylia hydriodate is formed; the salts of ethylia do not generally crystallize with facility; they are soluble in water and in alcohol. The hydrochlorate forms colourless plates, which are fusible at 169° (76° C.). The sulphate is deliquescent, and since it is soluble in alcohol it may readily be separated from ammonium sulphate, which is insoluble in this menstruum. The double salt with platinic chloride [(Є,H,N, HCl),PtCl], crystallizes in yellow octohedra. Diethylia [ЄH1N=(Є2H¿),HN; Boiling pt. 134°·6 (57° C.)] is a colourless, volatile, inflammable liquid, powerfully alkaline, and very caustic. It may be obtained by treating ethylia with ethyl iodide in the manner already described (1373). Triethylia [H1N=(Є,H,),N; Boiling pt. 196° (91° C.)] is also a soluble, volatile, and powerful base, which forms a beautiful orange double salt with platinic chloride, crystallizing in large rhombic tables [(Є,H,),N,HC1],PtCl. Triethylia may be obtained from the foregoing base by the action of ethyl iodide upon it. The salts of tetrethylium are procured by continuing the action of ethyl iodide upon triethylia. The hydrated tetrethylium oxide is a powerful base, perfectly analogous to the corresponding compound of tetramethylium. It may be obtained in solution by treating tetrethylium iodide with oxide of silver. If this solution be allowed to evaporate in vacuo over sulphuric acid, the base forms long hair-like needles, which are very deliquescent, and absorb carbonic acid with great avidity. A strong solution of the base may be boiled without undergoing decomposition, but if evaporated to dryness over the water-bath, it becomes decomposed as soon as the water is nearly all expelled. A solution of the base acts powerfully upon the cuticle, and it saponifies the fats as readily as potash, forming soft soaps. The tetrethylium oxide is not liberated from its iodide by the action of potash; on adding a solution of potash to one of the iodide of the base, a crystalline mass of the pure tetrethylium iodide is separated, as it is less soluble in alkaline liquids than in pure water: even when boiled with the concentrated solution of potash for some hours, no decomposition is effected; but it is decomposed SEPARATION OF ALCOHOL BASES. 529 with facility by the salts of silver, or by the freshly precipitated oxide of silver. Analogous reactions with potash and oxide of silver are found to occur with a large number of other ammonium bases.* The hydrated tetrethylium oxide when heated breaks up, not into its alcohol and triethylia, like the methylium base, but into olefiant gas, water, and triethylia, which is in accordance with the usual mode of decomposition of these bases (H ̧),N,HO= ¤ ̧Н ̧+H2→+(¤‚H.),N. 2 5/3 The iodides of the ammonium bases combine with an additional quantity of iodine, and form crystallizable compounds which may be obtained by mixing a solution of iodine in alcohol with the alcoholic solution of the iodide of the base. The triiodide of tetrethylium (ЄH)'N,I, crystallizes in dark violet brilliant prisms. The pentiodide (E,H,),N,I, forms tabular plates of a brilliant metallic lustre and a dark greenish grey colour. These compounds are very sparingly soluble in water, and may be employed to separate the ammonium compounds from those of the ammonia series of alcohol bases. The iodine may be removed by treatment with sulphuretted hydrogen. Bases derived from other Alcohols. (1378) Tritylia, or Propylamine (Є,H,,H,N) is isomeric with trimethylia; it is one of the bases obtained by Anderson during *Hofmann finds that the mixed ethyl bases may be completely and readily separated when in their anhydrous form, by treating them with oxalic ether. Ethylia is thus converted into a beautiful sparingly soluble crystallizable_compound, diethyloxamide, with liberation of alcohol; diethylia furnishes ethyloxamic ether, an oily liquid which boils at a high temperature, alcohol being here also liberated from the oxalic ether; and triethylia remains unaltered :— On distilling the result of the reaction of oxalic ether on the mixed anhydrous bases, triethylia passes over pure. The crystals of diethyloxamide are purified by crystallization from boiling water, and when decomposed by potash yield pure ethylia. The oily diethyloxamic ether when cooled to 32° deposits a few crystals of diethyloxamide; if decanted from these and distilled, and the portions collected which come over at 500° (260° C.), the product is pure diethyloxamic ether; and this when distilled with caustic potash furnishes pure diethylia. Carey Lea takes advantage of the difference in the solubility of the carbazotates of the different ethyl bases to effect their separation. 530 ALCOHOL BASES OBTAINED FROM PHOSPHORUS. 4 the destructive distillation of bones; and the same chemist has likewise procured from Dippel's oil another base, which he termed petinine, but which corresponds to tetrylia or butyria (¤H„HN), the alkali of tetrylic alcohol; it also occurs mixed with amylia in the distillate when wool or flannel is distilled with caustic potash. These bases are liquid and volatile. A series of bases corresponding to those from methylic and ethylic alcohols has also been obtained from fousel oil. Their basic powers are smaller than those of the ethyl and methyl series, and they present no particular points of interest. Amylia (Є¿H11, H,N) is a very light, colourless, inflammable liquid, which boils at 203° (95° C.), and is of sp. gr. 0.750. It is soluble in water in all proportions. Horn when distilled with caustic potash was found by Limpricht to yield 4 or 5 per cent. of this base. Its salts crystallize readily. (1379) The alcohol from castor oil (octylic alcohol) also yields a well-marked base, octylia or caprylia (ЄH17,H,N); and even the alcohol of palmitic acid, ethal, has been made to yield a compound ammonia in which all the three atoms of hydrogen have given place to the hydrocarbon cetyl, thus forming tricetylia (Є16H33)3N, which crystallizes in white fusible needles, freely soluble in boiling alcohol. Its salts are not soluble in water, but they crystallize readily from boiling alcohol and from ether. 3. Alcohol Bases obtained from phosphuretted, arseniuretted, and antimoniuretted hydrogen. (1380) The first column of the table of bases given (p. 524) includes three substances which do not possess basic properties, but which present the closest analogy in composition with ammonia; viz., phosphuretted, arseniuretted, and antimoniuretted hydrogen. Each of them contains three atoms of hydrogen, and one atom of its characteristic component; and they may be looked upon as analogues, or representatives of ammonia, in which the nitrogen has been displaced respectively by phosphorus, arsenicum, and antimony. Widely as these three elements differ from nitrogen in their separate form, they yet exhibit a considerable analogy with it in their mode of entering into combination; all three of them forming not only corresponding compounds with three atoms of hydrogen, but, like nitrogen, all of them yielding with oxygen, anhydrides which contain five atoms of oxygen, and which when united with the elements of water furnish powerful acids (442). PHOSPHOTRIETHYLIA, OR TRIETHYLPHOSPHINE. 531 Neither arseniuretted nor antimoniuretted hydrogen exhibits any basic properties, and the only indication of basic power in the case of phosphuretted hydrogen consists in the formation of volatile crystalline bodies with hydrobromic and hydriodic acids (454); yet it has been shown by P. Thénard, that if the hydrogen of phosphuretted hydrogen be displaced by methyl or by ethyl, powerful bases may be procured, formed upon the type of ammonia, but containing phosphorus instead of nitrogen, and ethyl or methyl in the place of hydrogen. Hofmann and Cahours have investigated these compounds more minutely (Phil. Trans. 1857), and have described a method by which they may be obtained with certainty. The process introduced by the chemists last named, for the preparation of these phosphorised bases consists in mixing phosphorous chloride (PCI) with zinc-methyl, zinc-ethyl, &c., when zincic chloride is formed, whilst the new base is produced. Many of these bases have a most offensive odour, and the vapour of several of them when mixed with atmospheric air, or with oxygen, takes fire, especially if the temperature be slightly raised. But not only may phosphorised bases (EH ̧) ̧Р; (¤ ̧Н¿) ̧Р; (Є¿H11),P, &c., analogous to ammonia, be formed, but by treating these new bases with iodide of ethyl, of methyl, or of amyl, iodides of ammonium bases analogous to that of tetrethylium may be obtained; and by the action of oxide of silver upon these iodides, hydrates of the new ammonium bases may be procured. 11 3/3 5/3 (1381) Phosphotriethylia, or Triethylphosphine [(E,H;)',P=118]; Sp. gr. of liquid 0812; Boiling pt. 261° (127° C.).-This interesting compound is a colourless transparent liquid of high refracting power, insoluble in water, but freely soluble in alcohol and in ether. It has a benumbing odour, which, when largely diluted, greatly resembles that of hyacinths. The reaction by which it is formed may be represented by the following equation :— 2 PCI ̧ + 3 [(Є2H2),Zn] = 3 ZnCl2 + 2 [(¤‚H¿) ̧P]. In order to prepare phosphotriethylia, the arrangement of apparatus represented in the annexed figure (Fig. 388) was adopted : a is a gas-bottle for generating carbonic anhydride; b a washbottle containing sulphuric acid; c a reservoir of carbonic anhydride; da bent tube containing phosphorous trichloride; e a receiver; ƒ a retort containing a solution of zinc-ethyl in ether; g a reservoir for the phosphorous chloride, the supply being regulated by a glass stop-cock. The whole apparatus is first filled with dry gaseous carbonic anhydride. The tube in c, which at |