Behavior of Metals in Different Electrolytes
| Caustic Potash | Hydrochloric Acid | Potassium Sulphide |
| + Zinc | + Zinc | + Zinc |
| Tin | Cadmium | Copper |
| Cadmium | Tin | Cadmium |
| Antimony | Lead | Tin |
| Lead | Iron | Silver |
| Bismuth | Copper | Antimony |
| Iron | Bismuth | Lead |
| Copper | Nickel | Bismuth |
| Nickel | Silver | Nickel |
| - Silver | - Antimony | - Iron |
It is important to remember that in all cells, no matter what elements or what electrolyte are used, the electrode which is consumed is the one that becomes negatively charged and its terminal, therefore, becomes the negative terminal or pole, while the electrode which is not consumed is the one that becomes positively charged, and its terminal is, therefore, the positive terminal or pole of the cell. However, because the current in the electrolyte flows from the consumed plate to the unconsumed plate, the consumed plate is called the positive plate and the unconsumed, the negative. This is likely to become confusing, but if one remembers that the active plate is the positive plate, because it sends forth positive ions in the electrolyte, and, therefore, itself becomes negatively charged, one will have the proper basis always to determine the direction of the current flow, which is the important thing.
Polarization. If the simple cell already described have its terminals connected by a wire for some time, it will be found that the current rapidly weakens until it ceases to be manifest. This weakening results from two causes: first, the hydrogen gas which is liberated in the action of the cell is deposited in a layer on the copper plate, thereby covering the plate and reducing the area of contact with the liquid. This increases the internal resistance of the cell, since hydrogen is a non-conductor. Second, the plate so covered becomes in effect a hydrogen electrode, and hydrogen stands high as an electro-positive element. There is, therefore, actual reduction in the electromotive force of the cell, as well as an increase in internal resistance. This phenomenon is known as polarization, and in commercial cells means must be taken to prevent such action as far as possible.
The means by which polarization of cells is prevented or reduced in practice may be divided into three general classes:
First—mechanical means. If the hydrogen bubbles be simply brushed away from the surface of the electrode the resistance and the counter polarity which they cause will be diminished. The same result may be secured if air be blown into the solution through a tube, or if the liquid be kept agitated. If the surface of the electrode be roughened or covered with points, the bubbles collect more freely at the points and are more quickly carried away to the surface of the liquid. These means are, however, hardly practical except in cells for laboratory use.
Second—chemical means. If a highly oxidizing substance be added to the electrolyte, it will destroy the hydrogen bubbles by combining with them while they are in a nascent state, and this will prevent the increase in internal resistance and the opposing electromotive force. Such substances are bichromate of potash, nitric acid, and chlorine, and are largely used.
Third—electro-chemical means. Double cells, arranged to separate the elements and liquids by means of porous partitions or by gravity, may be so arranged that solid copper is liberated instead of hydrogen at a point where the current leaves the liquid, thereby entirely obviating polarization. This method also is largely used.
Local Action. When a simple cell stands idle, i.e., with its circuit open, small hydrogen bubbles may be noticed rising from the zinc electrode instead of from copper, as is the case where the circuit is closed. This is due to impurities in the zinc plate, such as particles of iron, tin, arsenic, carbon, etc. Each of these particles acts with the surrounding zinc just as might be expected of any pair of dissimilar elements opposed to each other in an electrolyte; in other words, they constitute small voltaic cells. Local currents, therefore, are generated, circulating between the two adjacent metals, and, as a result, the zinc plate and the electrolyte are needlessly wasted and the general condition of the cell is impaired. This is called local action.