Chapter 37

The separation of the silverfrom gold is generally carried on with great precision, as the presence of the silver in the gold does not increase its value for exchange, and it can be substituted by other less valuable metals, so that the extraction of the silver, as a precious metal, from its alloy with gold, is a profitable operation. This separation is conducted by different methods. Sometimes the argentiferous gold is melted in crucibles, together with a mixture of common salt and powdered bricks. The greater portion of the silver is thus converted into the chloride, which fuses and is absorbed by the slags, from which it may be extracted by the usual methods. The silver is also extracted from gold by treating it with boiling sulphuric acid, which does not act on the gold but dissolves the silver. But if the alloy does not contain a large proportion of silver it cannot be extracted by this method or at all events the separation will be imperfect, and therefore a fresh amount of silver is added (by fusion) to the gold, in such quantity that the alloy contains twice as much silver as gold. The silver which is added is preferably such as contains gold, which is very frequently the case. The alloy thus formed is poured in a thin stream into water, by which means it is obtained in a granulated form; it is then boiled with strong sulphuric acid, three parts of acid being used to one part of alloy. The sulphuric acid extracts all the silver without acting on the gold. It is best, however, to pour off the first portion of the acid, which has dissolved the silver, and then treat the residue of still imperfectly pure gold with a fresh quantity of sulphuric acid. The gold is thus obtained in the form of powder, which is washed with water until it is quite free from silver. The silver is precipitated from the solution by means of copper, so that cupric sulphate and metallic silver are obtained. This process is carried out in many countries, as in Russia, at the Government mints.

Gold is generally used alloyed with copper; since pure gold, like pure silver, is very soft, and therefore soon worn away. In assaying or determining the amount of pure gold in such an alloy it is usual to add silver to the gold in order to make up an alloy containing three parts of silver to one of gold (this is known as quartation because the alloy contains ¼ of gold), and the resultant alloy is treated with nitric acid. If the silver be not in excess over the gold, it is not all dissolved by the nitric acid, and this is the reasonfor the quartation. The amount of pure gold (assay) is determined by weighing the gold which remains after this treatment. English gold (= 22 carats) coinage is composed of an alloy containing 91·66 p.c. of gold, but for many articles gold is frequently used containing a larger amount of foreign metals.

Pure goldmay be obtained from gold alloys by dissolving in aqua regia, and then adding ferrous sulphate to the solution or heating it with a solution of oxalic acid. These deoxidising agents reduce the gold, but not the other metals. The chlorine combined with the gold then acts like free chlorine. The gold, thus reduced, is precipitated as an exceedingly fine brown powder.[31 bis]It is then washed with water, and fused with nitre or borax. Pure gold reflects a yellow light, and in the form of very thin sheets (gold leaf), into which it can be hammered and rolled,[31 tri]it transmits a bluish-green light. The specific gravity of gold is about 19·5, the sp. gr. of gold coin is about 17·1. It fuses at 1090°—at a higher temperature than silver—and can be drawn into exceedingly fine wires or hammered into thin sheets. With its softness and ductility, gold is distinguished for its tenacity, and a gold wire two millimetres thick breaks only under a load of 68 kilograms. Gold vaporises even at a furnace heat, and imparts a greenish colour to a flame passing over it in a furnace. Gold alloys with copper almost without changing its volume.[32]In its chemicalaspect, gold presents, as is already seen from its general characteristics given above, an example of the so-called noble metals—i.e.it is incapable of being oxidised at any temperature, and its oxide is decomposed when calcined. Only chlorine and bromine combine directly with it at the ordinary temperature, but many other metals and non-metals combine with it at a red heat—for example, sulphur, phosphorus, and arsenic. Mercury dissolves it with great ease. It dissolves in potassium cyanide in the presence of air; a mixture of sulphuric acid with nitric acid dissolves it with the aid of heat, although in small quantity. It is also soluble in aqua regia and in selenic acid. Sulphuric, hydrochloric, nitric, and hydrofluoric acids and the caustic alkalis do not act on gold, but a mixture of hydrochloric acid with such oxidising agents as evolve chlorine naturally dissolves it like aqua regia.[32 bis]

As regards the compounds of gold, they belong, as was said above, to the types AuX3and AuX.Auric chlorideorgold trichloride, AuCl3, which is formed when gold is dissolved in aqua regia, belongs to the former and higher of these types. The solution of this substance in water has a yellow colour, and it may be obtained pure by evaporating the solution in aqua regia to dryness, but not to the point of decomposition. If the evaporation proceed to the point of crystallisation, a compound of gold chloride and hydrochloric acid, AuHCl4, is obtained, like the allied compounds of platinum; but it easily parts with the acid and leaves auric chloride, which fuses into a red-brown liquid, and then solidifies to a crystalline mass. If dry chlorine be passed over gold in powder it forms a mixture of aurous and auric chlorides, but the aurous chloride is also decomposed by water into gold and auric chloride. Auric chloride crystallises from its solutions as AuCl3,2H2O, which easily loses water, and the dry chloride loses two-thirds of its chlorine at 185°, forming aurous chloride, whilstabove 300° the latter chloride also loses its chlorine and leaves metallic gold. Auric chloride is the usual form in which gold occurs in solutions, and in which its salts are used in the arts and for chemical purposes. It is soluble in water, alcohol, and ether. Light has a reducing action on these solutions, and after a time metallic gold is deposited upon the sides of vessels containing the solution. Hydrogen when nascent, and even in a gaseous form, reduces gold from this solution to a metallic state. The reduction is more conveniently and usually effected by ferrous sulphate, and in general by the action of ferrous salts.[33]

If a solution of potassium hydroxide be added to a solution of auric chloride, a precipitate is first formed, which re-dissolves in an excess of the alkali. On being evaporated under the receiver of an air-pump, this solution yields yellow crystals, which present the same composition as the double salts AuMCl4, with the substitution of the chlorine by oxygen—that is to say,potassium aurate, AuKO2, is formed in crystals containing 3H2O. The solution has a distinctly alkaline reaction.Auric oxide, Au2O3, separates when this alkaline solution is boiled with an excess of sulphuric acid. But it then still retains some alkali; however, it may be obtained in a pure state as a brown powder by dissolving in nitric acid and diluting with water. The brown powder decomposes below 250° into gold and oxygen. It is insoluble in water and in many acids, but it dissolves in alkalis, which shows the acid character of this oxide. An hydroxide, Au(OH)3may be obtained as a brown powder by adding magnesium oxide to a solution of auric chloride and treating the resultant precipitate of magnesium aurate with nitric acid. This hydroxide loses water at 100°, and gives auric oxide.[34]

The starting-point of the compounds of the type AuX[35]isgold monochlorideoraurous chloride, AuCl, which is formed, as mentioned above, by heating auric chloride at 185°. Aurous chloride forms a yellowish-white powder; this, when heated with water, is decomposed into metallic gold and auric chloride, which passes into solution: 3AuCl = AuCl3+ 2Au. This decomposition is accelerated by the action of light. Hence it is obvious that the compounds corresponding with aurous oxide are comparatively unstable. But this only refers to the simple compounds AuX; some of the complex compounds, on the contrary, form the most stable compounds of gold. Such, for example, is the cyanide of gold and potassium, AuK(CN)2. It is formed, for instance, when finely-divided gold dissolves in the presence of air in a solution of potassium cyanide: 4KCN + 2Au + H2O + O = 2KAu(CN)2+ 2KHO (this reaction also proceeds with solid pieces of gold, although very slowly). The same compound is formed in solution when many compounds of gold are mixed with potassium cyanide, because if a higher compound of gold be taken, it is reducedby the potassium cyanide into aurous oxide, which dissolves in potassium cyanide and forms KAu(CN)2. This substance is soluble in water, and gives a colourless solution, which can be kept for a long time, and is employed in electro-gilding—that is, for coating other metallic objects with a layer of gold, which is deposited if the object be connected with the negative pole of a battery and the positive pole consist of a gold plate. When an electric current is passed between them, the gold from the latter will dissolve, whilst a coating of gold from the solution will be deposited on the object.


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