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tions of mercurous salts with hydrochloric acid or with metallic chlorides. A precipitate of calomel is also obtained by reducing a boiling aqueous solution of corrosive sublimate, HgCl2, with sulphurous anhydride. It is likewise produced by heating corrosive sublimate with mercury.22bis Calomel may be distilled (although in so doing it decomposes and recombines on cooling from a state of vapour); its vapour density equals 118 compared with hydrogen (= 1) (see Note 23). In the solid state its specific gravity is 7.0; it crystallises in rhombic prisms, is colourless, but has a yellowish tint, turns brown from the action of light, and when boiled with hydrochloric acid decomposes into mercury and corrosive sublimate. It is used as a strong purgative. Corrosive sublimate or mercuric chloride, HgCl2, can be obtained from or converted into calomel by many methods.23 An excess of chlorine (for instance, aqua regia) converts calomel and also mercury into corrosive sublimate. It owes its name corrosive sublimate to its volatility, and, in medicine up to the present day, it is termed Mercurius sublimatus seu corrosivus. The vapour density, compared with hydrogen (= 1) is 135 ; therefore its molecule contains HgCl,. It forms colourless prismatic crystals of the rhombic system, boils at 307°, and is soluble in alcohol. It is usually prepared by subliming a mixture of mercuric sulphate with common salt, HgSO4 + 2NaCl
=Na_S04+HgCl.. Corrosive sublimate combines with mercuric oxide, forming an oxychloride or basic salt, 23bis of the composition HgC1,,2HgO (magnesium and zinc form similar compounds). This compound is obtained by mixing a solution of corrosive sublimate with mercuric oxide or with a solution of sodium bicarbonate. In general, with both mercurous and mercuric salts, there is a marked tendency to form basic salts.24
22 bis Calomel (in Japanese 'Keyfun ') has been prepared in Japan and China) for many centuries, by heating mercury in clay crucibles with sea salt, which contains MgCl, and gives HCI. The vapour of the mercury reacts with this HCl and the oxygen of the air and forms calomel: 2Hg + 2HCl + 0 = HgCl2 + H2O. The calomel collects on the lid of the crucible in the form of a sublimate (Divers, 1894).
23 HgCl, is partially converted into calomel even in the act of dissolving in ordinary water, especially under the action of light.
23 bis As feebly energetic bases (for instance, the oxides MgO, ZnO, PbO, CuO, A1,03, Bi203, &c.), mercuric oxide (see Notes 20, 21) and mercurous oxide easily give basic salts, which are usually directly formed by the action of water on the normal salt, according to the general equation (for mercuric compounds, RX,) :
nRX, + mH.,O) = 2mHX + (n -m)RX.MRO
neutral salt water acid basic salt or else are produced directly from the normal salt and the oxide or its hydroxide. Thus mercurous nitrate, when treated with water, forms basic salts of the composition 6(HgNO3),Hg,0,H,O, 2(HONO3), Hg.,0,H.,O, and 3(HgNO3),Hg,0,H,O, the first two of which crystallise well. Naturally it is possible either to refer similar salts to the type of hydrates-for instance, the second salt to the hydrate N2O5,4H20-or to view it as a compound, HgNO3, HgHO, but our present knowledge of basic salts is not sufficiently complete to admit of generalisations. However, it is already possible to view the subject in the following aspects: (1) basic salts are principally formed from feeble bases : (2) certain metals (mentioned above) form them with particular ease, so that one of the causes of the formation of many basic salts must depend on the property of the metal itself; (3) those bases which readily form basic salts as a rule also readily form
Mercury has a remarkable power of forming very unstable compounds with ammonia, in which the mercury replaces the hydrogen, and, if a mercuric compound be taken, its atom occupies the place of two atoms of the hydrogen in the ammonia. Thus Plantamour and Hirtzel showed that precipitated mercuric oxide dried at a gentle heat, when continuously heated (up to 100°-150°) in a stream of double salts; (4) in the formation of basic salts, as also everywhere in chemistry, where sufficient facts have accumulated, we clearly see the conditions of equally balanced heterogeneous systems, such as we saw, for instance, in the formation of double salts, crystallo-hydrates, &c.
The mercuric salts often form double salts (confirming the third thesis), and mercuric chloride easily combines with ammonia, forming Hg(NH4),C1,, or in general HgCl.,n MCI. If a mixture of mercurous and potassium sulphates be dissolved in dilute sulphuric acid, the solution easily yields large colourless crystals of a double salt of the composition K.,804,3HgSO4,2H2O. Boullay obtained crystalline compounds of mercuric chloride with hydrochloric acid, and mercuric iodide with hydriodic acid ; and Thomsen describes the compound HgBr.,,HBr,4H.,O as a well-crystallised salt, melting at 13°, and having, in a molten state, a specific gravity 3:17 and a high index of refraction. Moreover, the capacity of salts for forining basic compounds has been considerably cleared up since the investigation (by Würtz, Lorenz, and others) of glycol, C,H,OH)2 (and of polyatomic alcohols resembling it), because the ethers C,H X.), corresponding with it, are capable of forming compounds containing C. H X.,nC,H,O.
On the other hand, there is reason to think that the property of forming basic salts is connected with the polymerisation of bases, especially colloidal ones (see the chapter on Silica, Lead Salts, and Tungstic Acid).
24 Mercuric iodide, HgL, is obtained first as a yellow, and then as a red, precipitate on mixing solutions of mercuric salts and potassium iodide, and is soluble in an excess of the latter (in consequence of the formation of the double salt, HgKIZ); of ammonium chloride (for a similar reason), &c. It crystallises at the ordinary temperature in square prisms of a red colour. On being heated, these change into yellow rhombic crystals, isomorphous with mercuric chloride. This yellow form of mercuric iodide is very unstable, and when cooled and triturated easily again assumes the more stable red form. When fused, a yellow liquid is obtained. Mercuric cyanide, Hg(CN)2, forms one of the most stable metallic cyanides. It is obtained by dissolving mercuric oxide in prussic acid, and by boiling Prussian blue with water and mercuric oxide, ferric oxide being then obtained in the precipitate. Mercuric cyanide is a colourless crystalline substance, soluble in water, and distinguished by its great stability; sulphuric acid does not liberate prussic acid from it, and even caustic potash does not remove the cyanogen (a complex salt is probably produced), but the halogen acids disengage HCN. Like the chloride, it combines with mercuric oxide, forming the oxycyanide, Hg2O(CN)2, and it shows a very marked tendency to form double compounds--for example, K.Hg(CN). The alkali chlorides and jodides form similar compounds-for instance, the salt HgKI(CN), crystallises very well, and is produced by directly mixing solutions of potassium iodide and mercuric cyanide.
Wells (1889) and Vare obtained and investigated many such double salts, and showed the possibility of the formation, not only of HgCl,MCI and HgC1,2MC1 where M is a metal of the alkalis--for example, Cs—but also of HgC1,3MC1,2(HgCl2)MC), and in general nHgX2mMX, where X stands for various haloids.
dry ammonia, leaves a brown powder of mercuric nitride, N, 143, according to the equation 3HgO + 2NH3=N,Hg3+3H,0.24bis This substance, which is attacked by water, acids, and alkalis (giving a white powder), is very explosive when struck or rubbed, evolving nitrogen, proving that the bond between the mercury and the nitrogen is very feeble.25 By the action of liquefied ammonia on yellow mercuric
24 bis See Chapter XIX., Note 6 bis: Hg3P. In studying the metallic nitrides it is necessary to keep the corresponding phosphides in mind.
25 Hg3N., is similar in composition to Mg3N2, &c. (Chapter XIV.) The readiness with which mercuric nitride explodes shows that the connection between the nitrogen and the mercury is very unstable, and explains the circumstance that the so-called mercury fulminate, or fulminating mercury, is an exceedingly explosive substance. This substance is prepared in large quantities for explosive mixtures; it enters into the composition of percussion caps, which explode when struck, and ignite gunpowder. Mercury fulminate was discovered by Howard, and from that time has been prepared in the following way: one part of mercury is dissolved in twelve parts of nitric acid, of sp. gr. 1.36, and when the whole of the mercury is dissolved, 55 parts of 90 p.c. alcohol are added, and the mass is shaken. A reaction then commences, accompanied by a rise in temperature due to the oxidation of the alcohol. As a matter of fact, many oxidation products are produced during the action of the nitric acid on the alcohol (glycollic acid, ethers, &c.) When the reaction becomes tolerably vigorous, the same quantity of alcohol is added as at the commencement, when a grey precipitate of the fulminate separates. This salt has the composition C.,Hg(NO,)N. It explodes when struck or heated. The mercury in it may be replaced by other metals- for instance, copper or zinc, and also silver. The silver salt, C. Ag:(NO,)N, is obtained in a precisely analogous manner, and is even more explosive. Under the action of alkali chlorides, only half the silver is replaced by the alkali metal, but if the whole of the silver be replaced by an alkali metal, then the salt decomposes. This is evidently because combinations of this kind proceed in virtue of the formation of substances in which mercury, and metals akin to it, are connected in an unstable way with nitrogen. Potassium and other light metals are incapable of entering into such connection and therefore, the substitution of potassium for mercury entails the splitting-up of the combination. Investigations of the fulminates were carried on by Gay-Lussac and Liebig, but only the investigations of L. N. Shishkoff fully cleared up the composition and relation of these substances to the other carbon compounds. Shishkoff showed that fulminates correspond with the nitro-acid, C,H,(NO,)N. The explosiveness of the group depends partly on its containing at the same time NO, and carbon; we already know that all such nitrogen compounds are explosive. If we imagine that the NO, is replaced by hydrogen, we shall have a substance of the composition C,H;N. This is acetonitrile--that is, acetic acid + NH3--2H.,0, or ethenyl nitrile, as shown in Chapter VI. The formation of an acetic compound by the action of nitric acid on alcohol is easily understood, because acetic acid is produced by the oxidation of alcohol, and the production of the elements of ammonia, indispensable for the formation of a nitrile, is accounted for by the fact that nitric acid under the action of reducing substances in many cases forms ammonia. Moreover a certain analogy has been found between fulminating acid and hydroxylamine, but details upon this subject must be looked for in works on organic chemistry. The explosiveness of fulminating mercury, the rapidity of its decomposition (gunpowder, and even guncotton, burn more slowly and explode less violently), and the force of its explosion, are such that a small quantity (loosely covered) will shatter massive objects.
The investigations of Abel on the communication of explosion from one substance to another are remarkable. If guncotton be ignited in an open space, it burns quietly; but if fulminating mercury be exploded by the side of it, the decomposition of the guncotton is effected instantaneously, and it then shatters the objects upon which it lies, so rapid is oxide Weitz also obtained an explosive compound, dimercurammonium hydroxide, N,Hg,0, which corresponds with an ammonium oxide, (NH,),0, in which the whole of the hydrogen is replaced by mercury. A solution of ammonia reacts with mercuric oxide, forming the hydroxide, NHg, OH, to which a whole series of salts, NHg,X, correspond ; these are generally insoluble in water and capable of decomposing with an explosion. But salts of the same type, but with one atom of mercury, NH,HgX, are more frequently and more easily formed ; they were principally studied by Kane, although known much earlier. Thus, if ammonia be added to a solution of corrosive sublimate (or, still better, in reverse order), a precipitate is obtained known as white precipitate (Mercurius pracipitatus albus) or mercurammonium chloride, NH,HgCl, which may also be regarded not only as sal-ammoniac with the substitution of H., by mercury, but also as HgX2, where one X represents Cl and the other X represents the ammonia radicle, HgCl, + 2NH, = NH, HgCl + NH,Cl. When heated, mercurammonium chloride decomposes, yielding mercurous chloride; when heated with dry hydrochloric acid it forms ammonium chloride and mercuric chloride. Other simple and double salts of mercurammonium, NH,HgX, are also known. Pici (1890) showed that all the compounds HgH,NX may be regarded as compounds of the above-named Hg,NX with NH X because their sum equals 2HgH, X.25bis
the decomposition. Abel explains this by supposing that the explosion of the fulminating salt brings the molecules of guncotton into a uniform or as it were harmonious state of vibration, which causes the rapid decomposition of the whole mass. This rapid decomposition of explosive substances defines the distinction between explosion and combustion. Besides this, Berthelot showed that from that form of powerful molecular concussion which takes place during the explosion of fulminating mercury, the state of strain and stability of equilibrium of substances which are endothermal, or capable of decomposing with the disengagement of heat-for instance, cyanogen, nitro compounds, nitrous oxide, &c.-is generally destroyed. Thorpe showed that carbon bisulphide, (S., also an endothermal substance, decomposes into sulphur and charcoal, when fulminating inercury is exploded in contact with it.
25 bis The capacity for replacing hydrogen in chloride of ammonium by metals also belongs to Zn and Cd. Kvasnik (1892), by the action of ammonia upon alcoholic solutions of CaCl, and ZnCl2, obtained substances of the general formula M(NH3C1),, formed as it were from two molecules of sal-ammoniac by the substitution of two atoms of hydrogen by a diatomic metal. These substances appear as white, finely crystalline powders. Under the action of heat half the ammonia passes off, and a compound of the composition MCINH,Cl is formed. The compounds of cadmium and zinc are distinguished from each other by the former being more volatile than the latter.
We may further remark that in the series Mg, Zn, Cd, and Hg the capacity io form double salts of diverse composition increases with the atomic weight. Thus, according to Wells and Walden's observations (1893), the ratio n: m for the type nMCImRCI, (M=K, Li, Na ... R= Mg, Zn ... ) is for Mg 1: 1, for Zn 3:1, 2:1, and 1: 1; for ca, besides this, salts are known with the ratio 4:1, and for Hg 3:1, 2:1, 1:1, 2:3, 1: 2, and 1: 5.
Mercury as a liquid metal is capable of dissolving other metals and forming metallic solutions. These are generally called "amalgams.' The formation of these solutions is often accompanied by the development of a large amount of heat--for instance, when potassium and sodium are dissolved (Chapter XII., Note 39); but sometimes heat is absorbed, as, for instance, when lead is dissolved. It is evident that phenomena of this kind are exceedingly similar to the phenomena accompanying the dissolution of salts and other substances in water, but here it is easy to demonstrate that which is far more difficult to observe in the case of salts : the solution of metals in mercury is accompanied by the formation of definite chemical compounds of the mercury with the metals dissolved. This is shown by the fact that when pressed (best of all in chamois leather) such solutions leave solid, definite compounds of mercury with metals. It is, however, very difficult to obtain them in a pure state, on account of the difficulty of separating the last traces of mercury, which is mechanically distributed between the crystals of the compounds. Nevertheless, in many cases such compounds have undoubtedly been obtained, and their existence is clearly shown by the evident crystalline structure and characteristic appearance of many amalgams Thus, for instance, if about 2} p.c. of sodium be dissolved in mercury, a hard, crystalline amalgam is obtained, very friable and little changeable in air. It contains the compound NaHg5 (Chapter XII., Note 39). Water decomposes it, with the evolution of hydrogen, but more slowly than other sodium amalgams, and this action of water only shows that the bond between the sodium and the mercury is weak, just like the connection between mercury and many other elements--for instance, nitrogen. Mercury directly and easily dissolves potassium, sodium, zinc, cadmium, tin, gold, bismuth, lead, &c., and from such solutions or alloys it is in most cases easy to extract definite compounds, thus, for instance, the compounds of mercury and silver have the compositions HgAg and Ag,Hg3. Objects made of copper when rubbed with mercury become covered with a white coating of that metal, which slowly forms an amalgam ; silver acts in the same way, but more slowly, and platinum combines with mercury with still greater difficulty. This metal only readily forms an amalgam when in the form of a fine powder. If salts of platinum in solution are poured on to an amalgam of sodium, the latter element reduces the platinum, and the platinum separated is dissolved by the mercury. Almost all metals readily form amalgams if their solutions are decomposed by a galvanic current, where mercury forms the negative pole. In this way an amalgam may even be made with iron, although iron in a mass does not dissolve in