Experimental Researches in Electricity, Volume 1

by Michael Faraday

1144. Purity of the zinc.—If pure zinc could be obtained, it would be very advantageous in the construction of the voltaic apparatus (998.). Most zincs, when put into dilute sulphuric acid, leave more or less of an insoluble matter upon the surface in the form of a crust, which contains various metals, as copper, lead, zinc, iron, cadmium, &c., in the metallic state. Such particles, by discharging part of the transferable power, render it, as to the whole battery, local; and so diminish the effect. As an indication connected with the more or less perfect action of the battery, I may mention that no gas ought to rise from the zinc plates. The more gas which is generated upon these surfaces, the greater is the local action and the less the transferable force. The investing crust is also inconvenient, by preventing the displacement and renewal of the charge upon the surface of the zinc. Such zinc as, dissolving in the cleanest manner in a dilute acid, dissolves also the slowest, is the best; zinc which contains much copper should especially be avoided. I have generally found rolled Liege or Mosselman's zinc the purest; and to the circumstance of having used such zinc in its construction attribute in part the advantage of the new battery (1134.).

1145. Foulness of the zinc plates.—After use, the plates of a battery should be cleaned from the metallic powder upon their surfaces, especially if they are employed to obtain the laws of action of the battery itself. This precaution was always attended to with the porcelain trough batteries in the experiments described (1125, &c.). If a few foul plates are mingled with many clean ones, they make the action in the different cells irregular, and the transferable power is accordingly diminished, whilst the local and wasted power is increased. No old charge containing copper should be used to excite a battery.

1146. New and old plates.—I have found voltaic batteries far more powerful when the plates were new than when they have been used two or three times; so that a new and an used battery cannot be compared together, or even a battery with itself on the first and after times of use. My trough of twenty pairs of four-inch plates, charged with acid consisting of 200 water, 4-1/2 oil of vitriol, and 4 nitric acid, lost, upon the first time of being used, 2.82 equivalents per plate. When used after the fourth time with the same charge, the loss was from 3.26 to 4.47 equivalents per plate; the average being 3.7 equivalents. The first time the forty pair of plates (1124.) were used, the loss at each plate was only 1.65 equivalent; but afterwards it became 2.16, 2.17, 2.52. The first time twenty pair of four-inch plates in porcelain troughs were used, they lost, per plate, only 3.7 equivalents; but after that, the loss was 5.25, 5.36, 5.9 equivalents. Yet in all these cases the zincs had been well-cleaned from adhering copper, &c., before each trial of power.

1147. With the rolled zinc the fall in force soon appeared to become constant, i.e. to proceed no further. But with the cast zinc plates belonging to the porcelain troughs, it appeared to continue, until at last, with the same charge, each plate lost above twice as much zinc for a given amount of action as at first. These troughs were, however, so irregular that I could not always determine the circumstances affecting the amount of electrolytic action.

1148. Vicinity of the copper and zinc.—The importance of this point in the construction of voltaic arrangements, and the greater power, as to immediate action, which is obtained when the zinc and copper surfaces are near to each other than when removed further apart, are well known. I find that the power is not only greater on the instant, but also that the sum of transferable power, in relation to the whole sum of chemical action at the plates, is much increased. The cause of this gain is very evident. Whatever tends to retard the circulation of the transferable force, (i.e. the electricity,) diminishes the proportion of such force, and increases the proportion of that which is local (996. 1120.). Now the liquid in the cells possesses this retarding power, and therefore acts injuriously, in greater or less proportion, according to the quantity of it between the zinc and copper plates, i.e. according to the distances between their surfaces. A trough, therefore, in which the plates are only half the distance asunder at which they are placed in another, will produce more transferable, and less local, force than the latter; and thus, because the electrolyte in the cells can transmit the current more readily; both the intensity and quantity of electricity is increased for a given consumption of zinc. To this circumstance mainly I attribute the superiority of the trough I have described (1134.).

1149. The superiority of double coppers over single plates also depends in part upon diminishing the resistance offered by the electrolyte between the metals. For, in fact, with double coppers the sectional area of the interposed acid becomes nearly double that with single coppers, and therefore it more freely transfers the electricity. Double coppers are, however, effective, mainly because they virtually double the acting surface of the zinc, or nearly so; for in a trough with single copper plates and the usual construction of cells, that surface of zinc which is not opposed to a copper surface is thrown almost entirely out of voltaic action, yet the acid continues to act upon it and the metal is dissolved, producing very little more than local effect (947. 996). But when by doubling the copper, that metal is opposed to the second surface of the zinc plate, then a great part of the action upon the latter is converted into transferable force, and thus the power of the trough as to quantity of electricity is highly exalted.

1150. First immersion of the plates.—The great effect produced at the first immersion of the plates, (apart from their being new or used (1146.),) I have attributed elsewhere to the unchanged condition of the acid in contact with the zinc plate (1003. 1037.): as the acid becomes neutralized, its exciting power is proportionally diminished. Hare's form of trough secures much advantage of this kind, by mingling the liquid, and bringing what may be considered as a fresh surface of acid against the plates every time it is used immediately after a rest.

1151. Number of plates.[229]—The most advantageous number of plates in a battery used for chemical decomposition, depends almost entirely upon the resistance to be overcome at the place of action; but whatever that resistance may be, there is a certain number which is more economical than either a greater or a less. Ten pairs of four-inch plates in a porcelain trough of the ordinary construction, acting in the volta-electrometer (1126.) upon dilute sulphuric acid of spec. grav. 1.314, gave an average consumption of 15.4 equivalents per plate, or 154 equivalents on the whole. Twenty pairs of the same plates, with the same acid, gave only a consumption of 5.5 per plate, or 110 equivalents upon the whole. When forty pairs of the same plates were used, the consumption was 3.54 equivalents per plate, or 141.6 upon the whole battery. Thus the consumption of zinc arranged as twenty plates was more advantageous than if arranged either as ten or as forty.

1152. Again, ten pairs of my four-inch plates (1129.) lost 6.76 each, or the whole ten 67.6 equivalents of zinc, in effecting decomposition; whilst twenty pairs of the same plates, excited by the same acid, lost 3.7 equivalents each, or on the whole 74 equivalents. In other comparative experiments of numbers, ten pairs of the three inch-plates, (1125.) lost 3.725, or 37.25 equivalents upon the whole; whilst twenty pairs lost 2.53 each, or 50.6 in all; and forty pairs lost on an average 2.21, or 88.4 altogether. In both these cases, therefore, increase of numbers had not been advantageous as to the effective production of transferable chemical power from the whole quantity of chemical force active at the surfaces of excitation (1120.).

1153. But if I had used a weaker acid or a worse conductor in the volta-electrometer, then the number of plates which would produce the most advantageous effect would have risen; or if I had used a better conductor than that really employed in the volta-electrometer, I might have reduced the number even to one; as, for instance, when a thick wire is used to complete the circuit (865., &c.). And the cause of these variations is very evident, when it is considered that each successive plate in the voltaic apparatus does not add anything to the quantity of transferable power or electricity which the first plate can put into motion, provided a good conductor be present, but tends only to exalt the intensity of that quantity, so as to make it more able to overcome the obstruction of bad conductors (994. 1158.).