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 of air. Other metals, except the silver and gold, also oxidize, and are carried by the melted litharge into the cupel. If the lead is therefore rightly proportioned to the standard of alloy, the resulting button will consist of only gold and silver, and these are separated by the operation of parting, which consists in boiling the alloy (after rolling it to a thin plate) in strong nitric acid, which dissolves the silver and leaves the gold as a coherent sponge. To effect this parting properly, the proportion of silver to gold should be as 3 to 1. The operation by which the alloy is brought to this standard is termed quartation or inquartation, and consists in fusing the alloy in a cupel with lead and the quantity of fine silver or fine gold necessary to bring it to the desired composition.

Lead.—The “dry” or fire assay for lead is largely used for the valuation of lead ores, although it is being gradually replaced by volumetric methods. One part of the ore is mixed with from three to five parts of a flux of the following composition:— The mixture is charged into a clay crucible and heated for twenty minutes at a good red heat. When the mixture has been in a tranquil state of fusion for a few minutes it is poured into a mould. When cold, the button is hammered, cleaned carefully from slag, and weighed. The proportion is calculated from the amount of ore used, and the result is expressed in parts in a hundred or percentage of the ore. Various impurities, such as copper, antimony and sulphur, go into the lead button, so that the result is generally too high. The most accurate method for the determination of lead in ores is the gravimetric method, in which it is weighed as lead sulphate after the various impurities have been separated. Nearly all lead ores contain more or less sulphur; and as in the process of solution in nitric acid this is oxidized to sulphuric acid which unites with the lead to form the very insoluble lead sulphate, it is simpler to add sulphuric acid to convert all the lead into sulphate and then evaporate until the nitric acid is expelled. The salts of iron, copper, &c., are then dissolved in water and filtered from the insoluble silica, lead sulphate, and calcium sulphate, which are washed with dilute sulphuric acid. The insoluble matter is treated with a hot solution of alkaline ammonium acetate, which dissolves the lead sulphate, the other materials being separated by filtration. The lead sulphate, re-precipitated in the filtrate by an excess of sulphuric acid and alcohol, is then filtered on an asbestos felt in a Gooch crucible, washed with dilute sulphuric acid and alcohol, ignited, and weighed. Lead sulphate contains 68·30% of metallic lead.

There are several volumetric methods for assaying lead ores, but the best known is that based on the precipitation of lead by ammonium molybdate in an acetic acid solution. The lead sulphate, obtained as described above and dissolved in ammonium acetate, is acidulated with acetic acid diluted with hot water and heated to boiling-point. A standardized solution of ammonium molybdate is then added from a burette. As long as the solution contains lead, the addition of the molybdate solution causes a precipitation of white lead molybdate. An excess of the precipitant is shown by a drop of the solution imparting a yellow colour to a solution of tannin, prepared by dissolving one part of tannin in 300 of water; drops of this solution are placed on a white porcelain plate, and as the precipitant is added to the lead solution a drop of the latter is removed from time to time on a glass stirring-rod and added to one of the drops on the porcelain plate. The appearance of a yellow colour shows that all the lead has been precipitated and that the solution contains an excess of molybdate. From the reading of the burette the lead is calculated. The molybdate solution should be of such a strength that 1 cc. will precipitate 0·01 gramme of lead. It is standardized by dissolving a weighed amount of lead sulphate in ammonium acetate and proceeding as described above.

Zinc.—Chemically the ores of zinc consist of the silicates, carbonates, oxides, and sulphides of zinc associated with other metals, some of which complicate the methods of assay. The most modern and the most generally accepted method is volumetric, and is based on the reaction between zinc chloride and potassium ferrocyanide, by which insoluble zinc ferrocyanide and soluble potassium chloride are formed; the presence of the slightest excess of potassium ferrocyanide is shown by a brownish tint being imparted by the solution to a drop of uranium nitrate. The ore (0·5 gramme) is digested with a mixture of potassium nitrate and nitric acid. A saturated solution of potassium chlorate in strong nitric acid is added, and the mass evaporated to dryness. It is then heated with a mixture of ammonium chloride and ammonia, filtered and washed with a hot dilute solution of the same mixture. The filtrate diluted to 200 cc. is carefully neutralized with hydrochloric acid, and excess of 6 cc. of the strong acid is added, and the solution saturated with hydrogen sulphide, which precipitates the copper and cadmium, metals which would otherwise interfere. Without filtering, the standard solution is added from a burette, and from time to time a drop of the solution is removed on the glass stirring-rod and added to a drop or two of a strong solution of uranium nitrate, previously placed on a white porcelain plate. The appearance of a brown tint in one of these tests shows the end of the reaction. When cadmium is not present the copper may be precipitated by boiling the acidulated ammoniacal solution with test lead and titrating, as before described, without removing the lead and copper from the solution. The ferrocyanide solution is standardized by dissolving 1 gramme of pure zinc in 6 cc. of hydrochloric acid, adding ammonium chloride, and titrating as before. This method is modified in practice by the character of the ores, carbonates and silicates free from sulphides being decomposed by hydrochloric acid, with the addition of a little nitric acid.

Copper.—The fire assay for copper ores was abandoned years ago and the electrolytic method took its place; this in turn is now largely replaced by volumetric methods. In the electrolytic method from 0·5 to 5 grammes of ore are treated in a flask or beaker, with a mixture of 10 cc. of nitric and 10 cc. of sulphuric acid, until thoroughly decomposed. When this liquid is cold it is diluted with cold water, heated until all the soluble salts are dissolved, transferred to a tall, narrow beaker, and diluted to about 150 cc. The electrodes are attached to a frame connected with the battery and the beaker is placed on a stool, which can be raised so that the electrodes are immersed in the liquid and reach the bottom of the beaker. The electrodes consist of two cylinders of platinum (placed one inside the other) about 75 mm. high, the smaller of the two 37 mm. and the larger 50 mm. in diameter, both pierced with 10 to 12 holes 5 mm. in diameter, evenly distributed over the surfaces to facilitate diffusion of the liquids. The surfaces of the cylinders are roughened with a sand blast to increase the areas and make the deposited metals adhere more firmly. Each cylinder has a platinum wire fused to the upper circumference to connect with a clamp from which a wire leads to the proper pole of the battery. The smaller cylinder is generally the negative electrode on which the copper is deposited. The framework carrying the clamps is arranged so that a number of determinations may be made at one time, the wires from the clamps running from a rheostat, so arranged that currents of any strength may be used simultaneously. The cylinder, having been carefully weighed, is placed in position, the beaker containing the solution is adjusted, and the current passed until all the copper is precipitated. This generally requires from two to twelve hours. The cylinders are then removed from the solution and washed with distilled water, the one holding the deposited copper being washed with alcohol, dried and weighed; the increase in weight represents the copper contents of the ore. The deposited copper should be firmly adherent and bright rosy red in colour. Silver, arsenic and cadmium, if present, are precipitated with the copper and affect the accuracy of the results; they should be removed by special methods.

Volumetric methods are more expeditious and require less apparatus. The potassium cyanide method is based on the fact that, when potassium cyanide is added to an ammoniacal solution of a salt of copper, the insoluble copper cyanide is