The black oxide of copper thus obtained, is an economical form of employing that metal for the production of the sulphate; 100 pounds of it, with 1221⁄2 of sulphuric acid diluted with water, produce 3121⁄2 pounds of crystallized sulphate of copper. A leaden boiler is best adapted for that operation. 100 pounds of silver are precipitable from its solution in nitric acid, by 29 of copper. If more be needed, it is a proof that a wasteful excess of acid has existed in the solution.
In parting by nitric acid, the gold generally retains a little silver; as is proved by the cloud of chloride of silver which it affords, at the end of some hours, when dissolved in aqua regia. And on the other hand, the silver retains a little gold. These facts induced M. Dizé, when he was inspector of the French mint, to adopt some other process, which would give more accurate analytical results; and after numerous experiments, he ascertained that sulphuric acid presented great advantages in this point of view, since with it he succeeded in detecting, in silver, quantities of gold which had eluded the other plan of parting. The suggestion of M. Dizé has been since universally adopted in France. M. Costell, about nine or ten years ago, erected in Pomeroy-street, Old Kent-road, a laboratory upon the French plan, for parting by sulphuric acid; but he was not successful in his enterprise; and since he relinquished the business, Mr. Matheson introduced the same system into our Royal Mint, under the management of M. Costell’s French operatives. In the Parisian refineries, gold, to the amount of one-thousandth part of the weight, has been extracted from all the silver which had been previously parted by the nitric acid process; being 3500 francs in value upon every thousand kilogrammes of silver.
I shall give first a general outline of the method of parting by sulphuric acid, and then describe its details as I have lately seen them executed upon a magnificent scale in an establishment near Paris.
The most suitable alloy for refining gold, by the sulphuric-acid process, is the compound of gold, silver, and copper, having a standard quality, by the cupel, of from 900 to 950 millièmes, and containing one-fifth of its weight of gold. The best proportions of the three metals are the following:—silver, 725; gold, 200; copper, 75; = 1000. It has been found that alloys which contain more copper, afford solutions that hold some anhydrous sulphate of that metal in solution, which prevents the gold from being readily separated; and that alloys containing more gold, are not acted on easily by the sulphuric acid. The refiner ought, therefore, when at all convenient, to reduce the alloys that he has to treat, to the above-stated proportions. He may effect this purpose either by fusing the coarser alloys with nitre in a crucible, or by adding finer alloy, or even fine silver, or finally, by subjecting the coarser alloys to a previous cupellation with lead on the great scale. As to gold or silver bullion, which contains lead and other easily oxidizable metals besides copper, the refiner ought always to avoid treating them by sulphuric acid; and should separate, first of all, these foreign metals by the agency of nitre, if they exist in minute quantity; but if in larger, he should have recourse to the cupel. Great advantage will therefore be derived from the judicious preparation of the alloy to be refined.
For an alloy of the above description, the principal Parisian refiners are in the habit of employing thrice its weight of sulphuric acid, in order to obtain a clear solution of sulphate of silver, which does not too suddenly concrete on cooling, so as to obstruct its discharge from the alembic by decantation. A small increase in the quantity of copper, calls for a considerable increase in the quantity of acid.
Generally speaking, one-half of the sulphuric acid strictly required for converting the silver and copper into sulphates, is decomposed into sulphurous acid, which is lost to the manufacturer, unless he has recourse to the agency of nitrous acid.
The process for silver containing but little gold, consists of five different operations.
1. Upon several furnaces, one foot in diameter, egg-shaped alembics of platinum are mounted, into each of which are put 3 kilogrammes (8 lbs. troy) of the granulated silver, containing a few grains of gold per pound, and 6 kilogrammes of concentrated sulphuric acid. The alembics are covered with conical capitals, ending in bent tubes, which conduct the acid vapours into lead pipes of condensation; and the furnaces are erected under a proper hood. As the cold acid is inoperative, it must be set a boiling, at which temperature it gives up one atom of its oxygen to the metal, and is transformed into sulphurous acid, which escapes in a gaseous state. Some of the undecomposed sulphuric acid immediately combines with the oxide into a sulphate, which subsides, in the state of a crystalline powder, to the bottom of the vessel. The solution goes on vigorously, with a copious disengagement of sulphurous acid gas, only during the two or three first hours; after which it proceeds slowly, and is not completed till after a digestion of nearly twelve hours more. During the ebullition a considerable quantity of sulphuric acid vapour escapes along with the sulphurous acid gas; the former of which is readily condensed in a large leaden receiver immersed in a cistern of cold water, if need be. It has been proposed to condense the sulphurous acid, by leading it over extensive surfaces of lime-pap, as in the coal-gas purifiers.
2. When the whole silver has been converted into sulphate, this is to be emptied out of the alembic into water contained in a round-bottomed receiver lined with lead, and diluted till the density of the solution marks from 15° to 20° Baumé. The small portion of gold, in the form of a brown powder, which remains undissolved, having been allowed to settle to the bottom, the supernatant solution of silver is to be decanted carefully off into a leaden cistern, and the powder being repeatedly edulcorated with water, the washings are to be added to it. The silver is now to be precipitated by plunging plates of copper in the solution, and the magma which falls is to be well washed, and freed from the residuary particles of sulphate of copper by powerful compression.
3. The silver, precipitated and dried as above described, is melted in a crucible, and cast into an ingot.