A text-book of assaying

by C. Beringer; J. J. Beringer

Speises are compounds of a metal or metals with arsenic. They are chiefly of interest in the metallurgy of nickel, cobalt, and tin. They are formed by heating the metal or ore in covered crucibles with arsenic and, if necessary, a reducing agent. The product is fused with more arsenic under a slag, consisting mainly of borax. They are very fusible, brittle compounds. On exposure to the air at a red heat the arsenic and the metal simultaneously oxidize. When iron, cobalt, nickel, and copper are present in the same speise, they are eliminated in the order mentioned.

Slags from which metals are to be separated should not be too acid; at least, in those cases in which the metal is to be reduced from a compound, as well as separated from earthy impurities. Where the object is simply to get a button of metal from a substance in which it is already in the metallic state, but mixed with dross (made up of metallic oxides, such as those of zinc or iron), from which it is desired to separate it, an acid flux like borax is best; or, if the metal is easily fusible, and there would be danger of loss of metal by oxidation or volatilising, it may be melted under a layer of resin or fat. Common salt is sometimes used with a similar object, and is often useful. Under certain conditions, however, it has a tendency to cause the formation of volatile chlorides with a consequent loss of metal.

In the great majority of cases, the fusion of the metal is accompanied by reduction from the state of oxide; in these the slag should be basic. It is not easy to reduce the whole of a reducible oxide (say oxide of copper or of iron) from a slag in which it exists as a borate or silicate; there should be at least enough soda present to liberate it. When the object is to separate one metal, say copper, without reducing an unnecessary amount of another (iron) at the same time, a slag with a good deal of borax is a distinct advantage. The slag then will probably not be free from copper, so that it will be necessary to powder and mix the slag with some soda and a reducing agent, and to again fuse the slag in order to separate this residual metal. In all those cases in which the slag retains an oxide of a heavy metal, this cleaning of the slag is advisable, and in the case of rich ores necessary. Slags containing sulphides are especially apt to retain the more easily reducible metals.

The following are the ordinary and most useful fluxes:—

Soda.—The powdered bicarbonate, sold by druggists as "carbonate of soda," is generally used. It gives off its water and excess of carbonic acid readily and without fusion. Where the melting down is performed rapidly, the escaping gas is apt to cause trouble by frothing, and so causing waste of the material. Ordinary carbonate of soda, when hydrated (soda crystals), melts easily, and gives off its water with ebullition. It is unfit for use in assaying, but when dried it can be used instead of the bicarbonate. One part of the dried carbonate is equivalent to rather more than one and a half parts of the bicarbonate. From two to four parts of the flux are amply sufficient to yield a fluid slag with one part of earthy matter. This statement is also true of the fluxes which follow.

Borax is a hydrated biborate of soda, containing nearly half its weight of water. When heated it swells up, loses its water, and fuses into a glass. The swelling up may become a source of loss in the assay by pushing some of the contents out of the crucible. To avoid this, fused or dried borax may be used, in which case a little more than half the amount of borax indicated will suffice. Borax will flux almost anything, but it is especially valuable in fluxing lime, &c., and metallic oxides; as also in those cases in which it is desired to keep certain of the latter in the slag and out of the button of metal.

Oxide of Lead, in the form of red lead or litharge, is a valuable flux; it easily dissolves those metallic oxides which are either infusible or difficultly fusible of themselves, such as oxides of iron or copper. The resulting slag is strongly basic and very corrosive; no crucible will long withstand the attack of a fused mixture of oxides of lead and copper. With silicates, also, it forms very fusible double silicates; but in the absence of silicates and borates it has no action upon lime or magnesia. Whether the lead be added as litharge or as red lead, it will exist in the slag as monoxide (litharge); the excess of oxygen of the red lead is thus available for oxidising purposes. If this oxidising power is prejudicial, it may be neutralised by mixing the red lead with 1 per cent. of charcoal.

Glass: broken beakers and flasks, cleaned, dried, and powdered will do. It should be free from lead.

Fluor: fluor-spar as free as possible from other minerals, powdered. It helps to flux phosphate of lime, &c., and infusible silicates.

Lime: should be fresh and powdered. It must not be slaked. Powdered white marble (carbonate of lime) will do; but nearly double the quantity must be taken. One part of lime produces the same effect as 1.8 parts of the carbonate of lime.