Magnesium

Magnesium [[[symbol]] Mg, atomic weight 24.32 (0 = 16)], a metallic chemical element. The sulphate or " Epsom salts " (q.v.) was isolated in 1695 by N. Grew, while in 1707 M. B. Valentin prepared magnesia alba from the mother liquors obtained in the manufacture of nitre. Magnesia was confounded with lime until 1755, when J. Black showed that the two substances were entirely different; and in 1808 Davy pointed out that it was the oxide of a metal, which, however, he was not able to isolate. Magnesium is found widely distributed in nature, chiefly in the forms of silicate, carbonate and chloride, and occurring in the minerals olivine, hornblende, talc, asbestos, meerschaum, augite, dolomite, magnesite, carnallite, kieserite and kainite. The metal was prepared (in a state approximating to purity) by A. A. B. Bussy (Jour. de pharm. 1829, 15, p. 30; 1830, 16, p. 142), who fused the anhydrous chloride with potassium; H. Sainte Claire Deville's process, which used to be employed commercially, was essentially the same, except that sodium was substituted for potassium (Comptes rendus, 18 57, 44, p. 394), the product being further purified by redistillation. It may also be prepared by heating a mixture of carbon, oxide of iron and magnesite to bright redness; and by heating a mixture of magnesium ferrocyanide and sodium carbonate, the double cyanide formed being then decomposed by heating it with metallic zinc. Electrolytic methods have entirely superseded the older methods. The problem of magnesium reduction is in many respects similar to that of aluminium extraction, bait the lightness of the metal as compared, bulk for bulk, with its fused salts, and the readiness with which it burns when exposed to air at high temperatures, render the problem somewhat more difficult.

Moissan found that the oxide resisted reduction by carbon in the electric furnace, so that electrolysis of a fusible salt of the metal must be resorted to. Bunsen, in 1852, electrolysed fused magnesium chloride in a porcelain crucible. In later processes, carnallite (a 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 carnallite 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 carnallite; 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. 1.75. 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 lioo 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. 39 2). It combines directly with nitrogen, when heated in the gas, to form the nitride Mg 3 N 2 (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 infusible 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 nemalite, and is prepared by precipitating solutions of magnesium salts by means of caustic soda or potash. An artificial brucite was prepared 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 fluorine 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 arc 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 MgC1 2.6H 2 O. 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 manufacture of potassium chloride from carnallite. 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, MgCl2NH 4 C1.6H 2 O, 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, MgCO 3. - The normal salt is found native as the mineral magnesite, and in combination with calcium carbonate as dolomite, whilst hydromagnesite is a basic carbonate. It is not possible to prepare 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 MgCO 3.3H 2 O or Mg(CO 3 H)(OH)2H 2 O may be prepared from the carbonate by dissolving it in water charged with carbon dioxide, and then reducing the pressure (W. A. Davis, Jour. 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(CO 3 H) (OH) 2H 2 O,Mg(CO 3 H) (OH) and Mg(OH) 2. It is almost insoluble in water, but readily dissolves in ammonium salts.

Magnesium Phosphates

By - adding sodium phosphate to magnesium sulphate and allowing the mixture to stand, hexagonal needles of MgHPO 4.7H 2 O are deposited. The normal phosphate, Mg3P205, 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, MgNH 4 PO 4.6H 2 O, 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, Mg 2 P 2 0 7. Magnesium Nitrate, Mg(NO 3) 2.6H 2 O, 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, Mg 3 N 2, 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. 39 0). 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. 1 35). When heated in a current of carbon monoxide or dioxide, it is converted into oxide, some carbon and cyanogen being formed at the same time. 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, liberating sulphuretted hydrogen, and with water it gives a yellow solution which becomes colourless on exposure.

Organic Compounds

By heating magnesium filings with methyl and ethyl iodides A. Cahours (Ann. chim. phys., 1860, 58, pp. 5, 19) obtained magnesium methyl, Mg(CH 3) 2, and magnesium ethyl, Mg(C 2 H 5) 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 Gri chemistry since V. Grignard (Comptes rendus, 1900 et seq.) observed that magnesium and alkyl or aryl halides combined together in presence of anhydrous ether at ordinary R temperatures (with the appearance of brisk boiling) to form compounds of the type RMgX(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 (C 2 H 5) 2 :0:(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 the reaction. They are very unstable, and do not react in the normal manner. (V. Grignard and L. Tissier, Comptes rendus, 1901, 1 3 2, p. 558).

The products formed by the action of the Grignard reagent with the various types of organic compounds are usually thrown out of solution in the form of crystalline precipitates or as thick oils, and are then decomposed by ice-cold dilute sulphuric or acetic acids, the magnesium being removed as a basic halide salt.

Applications

For the formation of primary and secondary alcohols see Aldehydes and Ketones. Formaldehyde behaves abnormally with magnesium benzyl bromide (M. Tiffeneau, Comptes rendus, 1903, 1 37, p. 573), forming ortho-tolylcarbinol, CH3C6H4CH20H, and not benzylcarbinol, C 6 H 5 CH 2 CH 2 OH (cf. the reaction of formaldehyde on phenols: 0. Manasse, Ber. 18 94, 2 7, p. 2904). Acid esters yield carbinols, many of which are unstable and readily pass over into unsaturated compounds, especially when warmed with acetic anhydride: R. CO 2 R'(R") 2 R:COMgX- (R")2R;COH.

Formic ester yields a secondary alcohol under similar conditions. Acid chlorides behave in an analogous manner to esters (Grignard and Tissier, Comptes rendus, 1901, 132, p. 683). Nitriles yield ketones (the nitrogen being eliminated as ammonia), the best yields being given by the aromatic nitriles (E. Blaise, ibid., 1901, 1 33, p. 1217): RCN -->RCOR'. Acid amides also react to form ketones (C. Beis, ibid., 1903, 1 37, 575): RConh 2 - E Rr' :C(OMgX)NHMgX R'H--RCO. R'; the yield increases with the complexity of the organic residue of the acid amide. On passing a current of dry carbon dioxide over the reagent,- the gas is absorbed and the resulting compound, when decomposed by dilute acids, yields an organic acid, and similarly with carbon oxysulphide a thio-acid is obtained: RMgX-RCO 2 MgX?RCO 2 H; COS-CS(OMgX)R--RCsoh.

A Klages (Ber., 1902, 35, pp. 2633 et seq.) has shown that if one uses an excess of magnesium and of an alkyl halide with a ketone, an ethylene derivative is formed. The reaction appears to be perfectly general unless the ketone contains two ortho-substituent groups. Organo-metallic compounds can also be prepared, for example SnBr 4 +4MgBrC 6 H 5 =4MgBr2+Sn(C6H5) 4.

For a summary see A. McKenzie, B. A. Rep. 1907.

Detection

The magnesium salts may be detected by the white precipitate formed by adding sodium phosphate (in the presence of ammonia and ammonium chloride) to their solutions. The same reaction is made use of in the quantitative determination of magnesium, the white precipitate of magnesium ammonium phosphate being converted by ignition into magnesium pyrophosphate and weighed as such. The atomic weight of magnesium has been determined by many observers. J. Berzelius (Ann. chim. phys., 1820, 14, p. 375), by converting the oxide into the sulphate, obtained the value 12.62 for the equivalent. R. F. Marchand and T. Scheerer (Jour. prakt. Chsm., 1850, 50, p. 358), by ignition of the carbonate, obtained the value 24.00 for the atomic weight, whilst C. Marignac, by converting the oxide into the sulphate, obtained the value 24.37. T. W. Richards and H. G. Parker (Zeit. anorg. Chem., 1897, 13, p. have obtained the value 24.365 (0 =16).

Medicine

These salts of magnesium may be regarded as the typical saline purgatives. Their aperient action is dependent upon the minimum of irritation of the bowel, and is exercised by their abstraction from the blood of water, which passes into the bowel to act as a diluent of the salt. The stronger the solution administered, the greater is the quantity of water that passes into the bowel, a fact to be borne in mind when the salt is administered for the purpose of draining superfluous fluid from the system, as in dropsy. The oxide and carbonate of magnesium are also invaluable as antidotes, since they form insoluble compounds with oxalic acid and salts of mercury, arsenic, and copper. The result is to prevent the local corrosive action of the poison and to prevent absorption of the metals. As alkaloids are insoluble in alkaline solutions, the oxide and carbonate - especially the former - may be given in alkaloidal poisoning. The compounds of magnesium are not absorbed into the blood in any appreciable quantity, and therefore exert no remote actions upon other functions. This is fortunate, as the result of injecting a solution of a magnesium salt into a vein is rapid poisoning. Hence it is of the utmost importance to avoid the use of salts of this metal whenever it is necessary - as in diabetic coma - to increase the alkalinity of the blood rapidly. The usual doses of the oxide and carbonate of magnesium are from half a drachm to a drachm.