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320
MAGNESIUM


natural double chloride of magnesium and potassium) has commonly, after careful dehydration, been substituted for the single chloride. Graetzel's process, which was at one time employed, consisted in electrolysing the chloride in a metal crucible heated externally, the crucible itself forming the cathode, and the magnesium being deposited upon its inner surface. W. Borchers also used an externally heated metal vessel as the cathode; it is provided with a supporting collar or flange a little below the top, so that the upper part of the vessel is exposed to the cooling influence of the air, in order that a crust of solidified salt may there be formed, and so prevent the creeping of the electrolyte over the top. The carbon anode passes through the cover of a porcelain cylinder, open at the bottom, and provided with a side-tube at the top to remove the chlorine formed during electrolysis. The operation is conducted at a dull red heat (about 760° C. or 1400° F.), the current density being about 0-64 amperes per sq. in. of cathode surface, and the pressure about 7 volts. The fusing-point of the metal is about 730° C. (1350° F.), and the magnesium is therefore reduced in the form of melted globules which gradually accumulate. At intervals the current is interrupted, the cover removed, and the temperature of the vessel raised considerably above the melting-point of magnesium. The metal is then removed from the walls with the aid of an iron scraper, and the whole mass poured into a sheet-iron tray, where it solidifies. The solidified chloride is then broken up, the shots and fused masses of magnesium are picked out, run together in a plumbago Crucible without flux, and poured into a suitable mould. Smaller pieces are thrown into a bath of melted carnal lite and pressed together with an iron rod, the bath being then heated until the globules of metal float to the top, when they may be removed in perforated iron ladles, through the holes in which the fused chloride can drain away, but through which the melted magnesium cannot pass by reason of its high surface tension. The globules are then re-melted. F. Oettel (Zeit. f. Elektrochem., 1895, 2, p. 394) recommends the electrolytic preparation from carnal lite; the mineral should be freed from water and sulphates.

Magnesium is a silvery white metal possessing a high lustre. It is malleable and ductile. Sp. gr. 1-7 5. It preserves its lustre in dry air, but in moist air it becomes tarnished by the formation of a film of oxide. It melts at 632-7° C. (C. T. Heycock and F. H. Neville), and boils at about 1100°C. Magnesium and' its salts are diamagnetic. It burns brilliantly when heated in air or oxygen, or even in carbon dioxide, emitting a brilliant white light and leaving a residue of magnesia, MgO. The light is rich in the violet and ultra-violet rays, and consequently is employed in photography. The metal is also used in pyrotechny. It also burns when heated in a current of steam, which it decomposes with the liberation of hydrogen and the formation of magnesia. At high temperatures it acts as a reducing agent, reducing silica to silicon, boric acid to boron, &c. (H. Moissan, Comptes rendus, 1892, 114, p. 392). It combines directly with nitrogen, when heated in the gas, to form the nitride Mg3N2 (see ARGON). It is rapidly dissolved by dilute acids, with the evolution of hydrogen and the formation of magnesium salts. It precipitates many metals from solutions of their salts. Magnesium Oxide, magnesia, MgO, occurs native as the mineral periclase, and is formed when magnesium burns in air; it may also be prepared by the gentle ignition of the hydroxide or carbonate. It is a non-volatile and almost in fusible white powder, which slowly absorbs moisture and carbon dioxide from air, and is readily soluble in dilute acids. On account of its refractory nature, it is employed in the manufacture of crucibles, furnace linings, &c. It is also used in making hydraulic cements. A crystalline form was obtained by M. Houdard (Abst. J. C. S., 1907, ii. p. 621) by fusing the oxide and sulphide in the electric furnace. Magnesium hydroxide Mg(OH)2, occurs native as the minerals brucite and némalite, and is prepared by precipitating solutions of magnesium salts by means of caustic soda or potash. An artificial brucite was repared by A. de Schulten (Comptes rendus, 1885, 101, p. 72) by boiling magnesium chloride with caustic potash and allowing the solution to cool. Magnesium hydroxide is a white amorphous solid which is only slightly soluble in water; the solubility is, however, greatly increased by ammonium salts. It possesses an alkaline reaction and absorbs carbon dioxide. It is employed in the manufacture of Cements.

When magnesium is heated in fiuorine or chlorine or in the vapour of bromine or iodine there is a violent reaction, and the corresponding halide compounds are formed. With the exception of the fluoride, these substances are readily soluble in water and are deliquescent. The fluoride is found native as sellaite, and the bromide and iodide occur in sea water and in many mineral springs. The most important of the halide salts is the chloride which, in the hydrated form, has the formula MgCl;-6H2O. It may be prepared by dissolving the metal, its oxide, hydroxide, or carbonate in dilute hydrochloric acid, or by mixing concentrated solutions of magnesium sulphate and common salt, and cooling the mixture rapidly, when the less soluble sodium sulphate separates first. It is also formed as a by-product in the manufactured of potassium chloride from carnal lite. The hydrated salt loses water on heating, and partially decomposes into hydrochloric acid and magnesium oxychlorides. To obtain the anhydrous salt, the double magnesium ammonium chloride, MgCl;- NH4Cl-6H2O, is prepared by adding ammonium chloride to a solution of magnesium chloride. The solution is evaporated, and the residue strongly heated, when water and ammonium chloride are expelled, and anhydrous magnesium chloride remains. Magnesium chloride readily forms double salts with the alkaline chlorides. A strong solution of the chloride made into a thick paste with calcined magnesia sets in a few hours to a hard, stone-like mass, which contains an oxychloride of varying composition. Magnesium oxychloride when heated to redness in a current of air evolves a mixture of hydrochloric acid and chlorine and leaves a residue of magnesia, a reaction which is employed in the Weldon-Pechiney and Mond processes for the manufacture of chlorine.

Magnesium Carbonate, MgCO3.-The normal salt is found native as the mineral magnetite, and in combination with calcium carbonate as dolomite, whilst hydromagnesite is a basic carbonate. It is not possible to pre are the normal carbonate by precipitating magnesium salts with sodium carbonate. C. Marignac has prepared it by the action of calcium carbonate on magnesium chloride. A salt MgCO3-3H2O or Mg(CO3H)(OH)~2H2O may be prepared from the carbonate by dissolving it in water charged with carbon dioxide, and then reducing the pressure (W. A. Davis, four. Soc. Chem. Ind. 1906, 25, p. 788). The carbonate is not easily soluble in dilute acids, but is readily soluble in water containing carbon dioxide. Magnesia alba, a white bulky precipitate obtained by adding sodium carbonate to Epsom salts, is a mixture of Mg(CO3H) (OH)-2H2O, Mg(CO3H) (OH) and Mg(OH)2. It is almost insoluble in water, but readily dissolves in ammonium salts.

Magnesium Phosphates.-Bygadding sodium phosphate to magnesium sulphate and allowing the mixture to stand, hexagonal needles of MgHPO4-7H2O are deposited. The normal phosphate, Mg3P2Og, is found in some guanos, and as the mineral wagnerite. It may be prepared by adding normal sodium phosphate to a magnesium salt and boiling the precipitate with a solution of magnesium sulphate. It is a white amorphous powder, readily soluble in acids. Magnesium ammonium phosphate, MgNH4PO4-6H2O, is found as the mineral struvite and in some guanos; it occurs also in urinary calculi and is formed in the putrefaction of urine. It is prepared by adding sodium phosphate to magnesium sulphate in the presence of ammonia and ammonium chloride. When heated to 100° C., 'it loses five molecules of water of crystallization, and at a higher temperature loses the remainder of the water and also ammonia, leaving a residue of magnesium pyrophosphate, , Mg2P2O7. Magnesium Nitrate, Mg(N 3)2-6H2O, IS a colourless, deliquescent, crystalline solid obtained by dissolving magnesium or its carbonate in nitric acid, and concentrating the solution. The crystals melt at 90° C. Magnesium Nitride, Mg3N2, is obtained as a greenish-yellow amorphous mass by passing a current of nitrogen or ammonia over heated magnesium (F. Briegleb and A. Geuther, Ann., 1862, 123, p. 228; see also W. Eidmann and L. Moeser, Ber., 1901, 34, p. 390). When heated in dry oxygen it becomes incandescent, forming magnesia. Water decomposes it with liberation of ammonia and formation of magnesium hydroxide. The chlorides of nickel, cobalt, chromium, iron and mercury are converted into nitrides when heated with it, whilst the chlorides of copper and platinum are reduced to the metals (A. Smits, Rec. Pays Bas, 1896, 15, p. 135). Magnesium sulphide, MgS, may be obtained, mixed with some unaltered metal and some magnesia, as a hard brown mass by heating magnesia, in sulphur vapour. It slowly decomposes in moist air. Magnesium sulphate, MgSO, , occurs (with IH2O) 'as Kieserite. A hexahydrate is also known. The salt may be obtained from Kieserite: formerly it wa; prepared by treating magnetite or dolomite with sulphuric aci .

Organic Compounds.-By heating magnesium filings with methyl and ethyl iodides A. Cahours (Ann. ehim. phys., 1860, 58, pp. 5, 19) obtained magnesium methyl, Mg(CH3)2, and magnesium ethyl, Mg(C2H5)2', as colourless, strongly smelling, mobile liquids, which are spontaneously inflammable and are readily decomposed by water. The compounds formed by the action of magnesium on alkyl iodides in the cold have been largely used in synthetic organic an "ard chemistry since V. Grignard (Comptes rendus, 1900 et Ref ent seq.) observed that magnesium and alkyl or arylhalides g combined together in presence of anhydrous ether at ordinary temperatures (with the appearance of brisk boiling) to form compounds of the type RM gX(R = an alkyl or aryl group and X = halogen). These compounds are insoluble in ether, are non-inflammable and exceedingly reactive. A. V. Baeyer (Ber., 1902, 35, p. 1201) regards them as oxonium salts containing tetravalent oxygen (C2H5)2:O:(MgR) (X), whilst W. Tschelinzeff (Ber., 1906, 39, p. 773) considers that they contain two molecules of ether. In preparing the Grignard reagent the commencement of the reaction is accelerated by a trace of iodine. W. Tschelinzeff (Ber., 1904, 37, p. 4534) showed that the ether may be replaced by benzene containing a small quantity of ether or anisole, or a few drops of a tertiary amine. With unsaturated alkyl halides the products are only slightly soluble in ether, and two molecules of the alkyl compound are brought into