The author lays down general principles for electrolytic metallurgy. Ores must be distinguished as good and bad conductors; the former may serve directly as anodes, and are easily oxidized by the electro-negative radicals formed at their contact, and dissolve readily in the electrolyte. The bad conductors have to be placed in contact with a conducting anode, formed of an inoxidizable substance, such as platinum, manganese peroxide, or coke. In laboratory experiments a good conducting ore is electrolyzed by suspension from a platinum wire in connection with the source of electricity, and is then immersed in the bath. On an industrial scale the ore, coarsely broken up, is placed in one of the compartments of a trough divided by a diaphragm.

On the fragments of the ore which extend up outside of the electrolytic bath is laid a plate of copper connected with the positive wire. Care must be taken that this plate does not plunge into the bath, otherwise the current would not traverse the ore at all. The cathode is preferably formed of the same metal which is to be obtained. The bath should not contain organic acids. In practice the common mineral acids are employed, or their salts, selecting by preference a salt of the metal which is to be isolated. It is convenient to pass the current through the greatest possible number of small decomposition troughs, taking care that the resistance in each is not too great. With a current of one and the same intensity we obtain in n troughs n times as much metal as in a single one. To keep down the resistance of the circuit we employ poles of a large surface, i.e., plenty of ore and baths which are as good conductors as possible.

The state in which the metal is deposited at the negative pole depends on the secondary actions undergone by the electrolyte, and especially of the escape of gas. This is a function of the density, of the current, i.e., the proportion of its intensity to the surface of the cathode. If the density is too great there is an escape of hydrogen, and the metal is deposited in a spongy condition. If the density of the current falls below a certain minimum, an oxide is deposited in place of metal. The electrolytic treatment of ores often renders it possible to separate the different metals which may be present. These are deposited in succession, and are sharply separated if the electromotive power is not too great.

1. Zinc.--The zinciferous compounds--calamine, blende, and zinc ash--are all poor conductors. They are first dissolved, and the salts obtained are electrolyzed, employing anodes of coke. Blende should be roasted before it is dissolved. The electrolytic bath should be as concentrated as possible to avoid sponginess of the metal and an escape of hydrogen. In a saturated solution the formation of hydrogen decreases as the density of the current augments.

2. Lead.--Galena is a good conductor, and may be directly electrolyzed. The best bath is a solution of lead nitrate. The arborescent crystallizations extend rapidly, and must be broken from time to time to prevent the formation of a metallic connection between the anode and the cathode. The sulphur of the galena falls to the bottom of the bath, and may be separated from the gangue by solution in carbon disulphide.

3. Copper.--Native copper sulphide, though a good conductor, cannot be directly electrolyzed en account of the presence of iron sulphide, whence iron would be deposited along with the copper. The copper pyrites are roasted, dissolved in dilute sulphuric acid, and the liquid thus obtained is submitted to electrolysis.