Part 54

TENTH SERIES.

§ 16. On an improved form of the Voltaic Battery. § 17. Some practical results respecting the construction and use of the Voltaic Battery.

Received June 16,--Read June 18, 1835.

1119. I Have lately had occasion to examine the voltaic trough practically, with a view to improvements in its construction and use; and though I do not pretend that the results have anything like the importance which attaches to the discovery of a new law or principle, I still think they are valuable, and may therefore, if briefly told, and in connexion with former papers, be worthy the approbation of the Royal Society.

§ 16. On an improved form of the Voltaic Battery.

1120. In a simple voltaic circuit (and the same is true of the battery) the chemical forces which, during their activity, give power to the instrument, are generally divided into two portions; one of these is exerted locally, whilst the other is transferred round the circle (947. 996.); the latter constitutes the electric current of the instrument, whilst the former is altogether lost or wasted. The ratio of these two portions of power may be varied to a great extent by the influence of circumstances: thus, in a battery not closed, all the action is local; in one of the ordinary construction, much is in circulation when the extremities are in communication: and in the perfect one, which I have described (1001.), all the chemical power circulates and becomes electricity. By referring to the quantity of zinc dissolved from the plates (865. 1120.), and the quantity of decomposition effected in the volta-electrometer (711. 1126,) or elsewhere, the proportions of the local and transferred actions under any particular circumstances can be ascertained, and the efficacy of the voltaic arrangement, or the waste of chemical power at its zinc plates, be accurately determined.

1121. If a voltaic battery were constructed of zinc and platina, the latter metal surrounding the former, as in the double copper arrangement, and the whole being excited by dilute sulphuric acid, then no insulating divisions of glass, porcelain or air would be required between the contiguous platina surfaces; and, provided these did not touch metallically, the same acid which, being between the zinc and platina, would excite the battery into powerful action, would, between the two surfaces of platina, produce no discharge of the electricity, nor cause any diminution of the power of the trough. This is a necessary consequence of the resistance to the passage of the current which I have shown occurs at the place of decomposition (1007. 1011.); for that resistance is fully able to stop the current, and therefore acts as insulation to the electricity of the contiguous plates, inasmuch as the current which tends to pass between them never has a higher intensity than that due to the action of a single pair.

1122. If the metal surrounding the zinc be copper (1045.), and if the acid be nitro-sulphuric acid (1020.), then a slight discharge between the two contiguous coppers does take place, provided there be no other channel open by which the forces may circulate; but when such a channel is permitted, the return or back discharge of which I speak is exceedingly diminished, in accordance with the principles laid down in the Eighth Series of these Researches.

1123. Guided by these principles I was led to the construction of a voltaic trough, in which the coppers, passing round both surfaces of the zincs, as in Wollaston's construction, should not be separated from each other except by an intervening thickness of paper, or in some other way, so as to prevent metallic contact, and should thus constitute an instrument compact, powerful, economical, and easy of use. On examining, however, what had been done before, I found that the new trough was in all essential respects the same as that invented and described by Dr. Hare, Professor in the University of Pennsylvania, to whom I have great pleasure in referring it.

1124. Dr. Hare has fully described his trough. In it the contiguous copper plates are separated by thin veneers of wood, and the acid is poured on to, or off, the plates by a quarter revolution of an axis, to which both the trough containing the plates, and another trough to collect and hold the liquid, are fixed. This arrangement I have found the most convenient of any, and have therefore adopted it. My zinc plates were cut from rolled metal, and when soldered to the copper plates had the form delineated, fig. 1. These were then bent over a gauge into the form fig. 2, and when packed in the wooden box constructed to receive them, were arranged as in fig. 3, little plugs of cork being used to keep the zinc plates from touching the copper plates, and a single or double thickness of cartridge paper being interposed between the contiguous surfaces of copper to prevent them from coming in contact. Such was the facility afforded by this arrangement, that a trough of forty pairs of plates could be unpacked in five minutes, and repacked again in half an hour; and the whole series was not more than fifteen inches in length.

Philosophical Magazine, 1824, vol. lxiii. p. 241; or Silliman's Journal, vol. vii. See also a previous paper by Dr. Hare, Annals of Philosophy, 1821, vol. i. p. 329, in which he speaks of the non-necessity of insulation between the coppers.

The papers between the coppers are, for the sake of distinctness, omitted in the figure.

1125. This trough, of forty pairs of plates three inches square, was compared, as to the ignition of a platina wire, the discharge between points of charcoal, the shock on the human frame, &c., with forty pairs of four-inch plates having double coppers, and used in porcelain troughs divided into insulating cells, the strength of the acid employed to excite both being the same. In all these effects the former appeared quite equal to the latter. On comparing a second trough of the new construction, containing twenty pairs of four-inch plates, with twenty pairs of four-inch plates in porcelain troughs, excited by acid of the same strength, the new trough appeared to surpass the old one in producing these effects, especially in the ignition of wire.

1126. In these experiments the new trough diminished in its energy much more rapidly than the one on the old construction, and this was a necessary consequence of the smaller quantity of acid used to excite it, which in the case of the forty pairs of new construction was only one-seventh part of that used for the forty pairs in the porcelain troughs. To compare, therefore, both forms of the voltaic trough in their decomposing powers, and to obtain accurate data as to their relative values, experiments of the following kind were made. The troughs were charged with a known quantity of acid of a known strength; the electric current was passed through a volta-electrometer (711.) having electrodes 4 inches long and 2.3 inches in width, so as to oppose as little obstruction as possible to the current; the gases evolved were collected and measured, and gave the quantity of water decomposed. Then the whole of the charge used was mixed together, and a known part of it analyzed, by being precipitated and boiled with excess of carbonate of soda, and the precipitate well-washed, dried, ignited, and weighed. In this way the quantity of metal oxidized and dissolved by the acid was ascertained; and the part removed from each zinc plate, or from all the plates, could be estimated and compared with the water decomposed in the volta-electrometer. To bring these to one standard of comparison, I have reduced the results so as to express the loss at the plates in equivalents of zinc for the equivalent of water decomposed at the volta-electrometer: I have taken the equivalent number of water as 9, and of zinc as 32.5, and have considered 100 cubic inches of the mixed oxygen and hydrogen, as they were collected over a pneumatic trough, to result from the decomposition of 12.68 grains of water.

1127. The acids used in these experiments were three,--sulphuric, nitric, and muriatic. The sulphuric acid was strong oil of vitriol; one cubical inch of it was equivalent to 486 grains of marble. The nitric acid was very nearly pure; one cubical inch dissolved 150 grains of marble. The muriatic acid was also nearly pure, and one cubical inch dissolved 108 grains of marble. These were always mixed with water by volumes, the standard of volume being a cubical inch.

1128. An acid was prepared consisting of 200 parts water, 4-1/2 parts sulphuric acid, and 4 parts nitric acid; and with this both my trough containing forty pairs of three-inch plates, and four porcelain troughs, arranged in succession, each containing ten pairs of plates with double coppers four inches square, were charged. These two batteries were then used in succession, and the action of each was allowed to continue for twenty or thirty minutes, until the charge was nearly exhausted, the connexion with the volta-electrometer being carefully preserved during the whole time, and the acid in the troughs occasionally mixed together. In this way the former trough acted so well, that for each equivalent of water decomposed in the volta-electrometer only from 2 to 2.5 equivalents of zinc were dissolved from each plate. In four experiments the average was 2.21 equivalents for each plate, or 88.4 for the whole battery. In the experiments with the porcelain troughs, the equivalents of consumption at each plate were 3.51, or 141.6 for the whole battery. In a perfect voltaic battery of forty pairs of plates (991. 1001.) the consumption would have been one equivalent for each zinc plate, or forty for the whole.

1129. Similar experiments were made with two voltaic batteries, one containing twenty pairs of four-inch plates, arranged as I have described (1124.), and the other twenty pairs of four-inch plates in porcelain troughs. The average of five experiments with the former was a consumption of 3.7 equivalents of zinc from each plate, or 74 from the whole: the average of three experiments with the latter was 5.5 equivalents from each plate, or 110 from the whole: to obtain this conclusion two experiments were struck out, which were much against the porcelain troughs, and in which some unknown deteriorating influence was supposed to be accidentally active. In all the experiments, care was taken not to compare new and old plates together, as that would have introduced serious errors into the conclusions (1146.).

1130. When ten pairs of the new arrangement were used, the consumption of zinc at each plate was 6.76 equivalents, or 67.6 for the whole. With ten pairs of the common construction, in a porcelain trough, the zinc oxidized was, upon an average, 15.5 equivalents each plate, or 155 for the entire trough.

1131. No doubt, therefore, can remain of the equality or even the great superiority of this form of voltaic battery over the best previously in use, namely, that with double coppers, in which the cells are insulated. The insulation of the coppers may therefore be dispensed with; and it is that circumstance which principally permits of such other alterations in the construction of the trough as gives it its practical advantages.

1132. The advantages of this form of trough are very numerous and great. i. It is exceedingly compact, for 100 pairs of plates need not occupy a trough of more than three feet in length, ii. By Dr. Hare's plan of making the trough turn upon copper pivots which rest upon copper bearings, the latter afford fixed terminations; and these I have found it very convenient to connect with two cups of mercury, fastened in the front of the stand of the instrument. These fixed terminations give the great advantage of arranging an apparatus to be used in connexion with the battery before the latter is put into action, iii. The trough is put into readiness for use in an instant, a single jug of dilute acid being sufficient for the charge of 100 pairs of four-inch plates, iv. On making the trough pass through a quarter of a revolution, it becomes active, and the great advantage is obtained of procuring for the experiment the effect of the first contact of the zinc and acid, which is twice or sometimes even thrice that which the battery can produce a minute or two after (1036. 1150.). v. When the experiment is completed, the acid can be at once poured from between the plates, so that the battery is never left to waste during an unconnected state of its extremities; the acid is not unnecessarily exhausted; the zinc is not uselessly consumed; and, besides avoiding these evils, the charge is mixed and rendered uniform, which produces a great and good result (1039.); and, upon proceeding to a second experiment, the important effect of first contact is again obtained. vi. The saving of zinc is very great. It is not merely that, whilst in action, the zinc performs more voltaic duty (1128. 1129.), but all the destruction which takes place with the ordinary forms of battery between the experiments is prevented. This saving is of such extent, that I estimate the zinc in the new form of battery to be thrice as effective as that in the ordinary form. vii. The importance of this saving of metal is not merely that the value of the zinc is saved, but that the battery is much lighter and more manageable; and also that the surfaces of the zinc and copper plates may be brought much nearer to each other when the battery is constructed, and remain so until it is worn out: the latter is a very important advantage (1148.). viii. Again, as, in consequence of the saving, thinner plates will perform the duty of thick ones, rolled zinc may be used; and I have found rolled zinc superior to cast zinc in action; a superiority which I incline to attribute to its greater purity (1144.). ix. Another advantage is obtained in the economy of the acid used, which is proportionate to the diminution of the zinc dissolved. x. The acid also is more easily exhausted, and is in such small quantity that there is never any occasion to return an old charge into use. The acid of old charges whilst out of use, often dissolves portions of copper from the black flocculi usually mingled with it, which are derived from the zinc; now any portion of copper in solution in the charge does great harm, because, by the local action of the acid and zinc, it tends to precipitate upon the latter, and diminish its voltaic efficacy (1145.). xi. By using a due mixture of nitric and sulphuric acid for the charge (1139.), no gas is evolved from the troughs; so that a battery of several hundred pairs of plates may, without inconvenience, be close to the experimenter. xii. If, during a series of experiments, the acid becomes exhausted, it can be withdrawn, and replaced by other acid with the utmost facility; and after the experiments are concluded, the great advantage of easily washing the plates is at command. And it appears to me, that in place of making, under different circumstances, mutual sacrifices of comfort, power, and economy, to obtain a desired end, all are at once obtained by Dr. Hare's form of trough.

1133. But there are some disadvantages which I have not yet had time to overcome, though I trust they will finally be conquered. One is the extreme difficulty of making a wooden trough constantly water-tight under the alternations of wet and dry to which the voltaic instrument is subject. To remedy this evil, Mr. Newman is now engaged in obtaining porcelain troughs. The other disadvantage is a precipitation of copper on the zinc plates. It appears to me to depend mainly on the circumstance that the papers between the coppers retain acid when the trough is emptied; and that this acid slowly acting on the copper, forms a salt, which gradually mingles with the next charge, and is reduced on the zinc plate by the local action (1120.): the power of the whole battery is then reduced. I expect that by using slips of glass or wood to separate the coppers at their edges, their contact can be sufficiently prevented, and the space between them be left so open that the acid of a charge can be poured and washed out, and so be removed from every part of the trough when the experiments in which the latter is used are completed.

1134. The actual superiority of the troughs which I have constructed on this plan, I believe to depend, first and principally, on the closer approximation of the zinc and copper surfaces;--in my troughs they are only one-tenth of an inch apart (1148.);--and, next, on the superior quality of the rolled zinc above the cast zinc used in the construction of the ordinary pile. It cannot be that insulation between the contiguous coppers is a disadvantage, but I do not find that it is any advantage; for when, with both the forty pairs of three-inch plates and the twenty pairs of four-inch plates, I used papers well-soaked in wax, these being so large that when folded at the edges they wrapped over each other, so as to make cells as insulating as those of the porcelain troughs, still no sensible advantage in the chemical action was obtained.

A single paper thus prepared could insulate the electricity of a trough of forty pairs of plates.

1135. As, upon principle, there must be a discharge of part of the electricity from the edges of the zinc and copper plates at the sides of the trough, I should prefer, and intend having, troughs constructed with a plate or plates of crown glass at the sides of the trough: the bottom will need none, though to glaze that and the ends would be no disadvantage. The plates need not be fastened in, but only set in their places; nor need they be in large single pieces.

§ 17. Some practical results respecting the construction and use of the Voltaic Battery (1034. &c.).

1136. The electro-chemical philosopher is well acquainted with some practical results obtained from the voltaic battery by MM.. Gay-Lussac and Thenard, and given in the first forty-five pages of their 'Recherches Physico-Chimiques'. Although the following results are generally of the same nature, yet the advancement made in this branch of science of late years, the knowledge of the definite action of electricity, and the more accurate and philosophical mode of estimating the results by the equivalents of zinc consumed, will be their sufficient justification.

1137. Nature and strength of the acid.--My battery of forty pairs of three-inch plates was charged with acid consisting of 200 parts water and 9 oil of vitriol. Each plate lost, in the average of the experiments, 4.66 equivalents of zinc for the equivalent of water decomposed in the volta-electrometer, or the whole battery 186.4 equivalents of zinc. Being charged with a mixture of 200 water and 16 of the muriatic acid, each plate lost 3.8, equivalents of zinc for the water decomposed, or the whole battery 152 equivalents of zinc. Being charged with a mixture of 200 water and 8 nitric acid, each plate lost 1.85, equivalents of zinc for one equivalent of water decomposed, or the whole battery 74.16 equivalents of zinc. The sulphuric and muriatic acids evolved much hydrogen at the plates in the trough; the nitric acid no gas whatever. The relative strengths of the original acids have already been given (1127.); but a difference in that respect makes no important difference in the results when thus expressed by equivalents (1140.).

1138. Thus nitric acid proves to be the best for this purpose; its superiority appears to depend upon its favouring the electrolyzation of the liquid in the cells of the trough upon the principles already explained (905. 973, 1022.), and consequently favouring the transmission of the electricity, and therefore the production of transferable power (1120.).