Chapter 32

1005. The superiority of the amalgamated zinc is not, however, due to any such cause, but is a very simple consequence of the state of the fluid in contact with it; for as the unprepared zinc acts directly and alone upon the fluid, whilst that which is amalgamated does not, the former (by the oxide it produces) quickly neutralizes the acid in contact with its surface, so that the progress of oxidation is retarded, whilst at the surface of the amalgamated zinc, any oxide formed is instantly removed by the free acid present, and the clean metallic surface is always ready to act with full energy upon the water. Hence its superiority (1037.). 1006. The progress of improvement in the voltaic battery and its applications, is evidently in the contrary direction at present to what it was a few years ago; for in place of increasing the number of plates, the strength of acid, and the extent altogether of the instrument, the change is rather towards its first state of simplicity, but with a far more intimate knowledge and application of the principles which govern its force and action. Effects of decomposition can now be obtained with ten pairs of plates (417.), which required five hundred or a thousand pairs for their production in the first instance. The capability of decomposing fused chlorides, iodides, and other compounds, according to the law before established (380. &c.), and the opportunity of collecting certain of the products, without any loss, by the use of apparatus of the nature of those already described (789. 814. &c.), render it probable that the voltaic battery may become a useful and even economical manufacturing instrument; for theory evidently indicates that an equivalent of a rare substance may be obtained at the expense of three or four equivalents of a very common body, namely, zinc: and practice seems thus far to justify the expectation. In this point of view I think it very likely that plates of platina or silver may be used instead of plates of copper with advantage, and that then the evil arising occasionally from solution of the copper, and its precipitation on the zinc, (by which the electromotive power of the zinc is so much injured,) will be avoided (1047.).

¶ iv. _On the Resistance of an Electrolyte to Electrolytic Action, and on Interpositions._

1007. I have already illustrated, in the simplest possible form of experiment (891. 910.), the resistance established at the place of decomposition to the force active at the exciting place. I purpose examining the effects of this resistance more generally; but it is rather with reference to their practical interference with the action and phenomena of the voltaic battery, than with any intention at this time to offer a strict and philosophical account of their nature. Their general and principal cause is the resistance of the chemical affinities to be overcome; but there are numerous other circumstances which have a joint influence with these forces (1034. 1040. &c.), each of which would require a minute examination before a correct account of the whole could be given.

1008. As it will be convenient to describe the experiments in a form different to that in which they were made, both forms shall first be explained. Plates of platina, copper, zinc, and other metals, about three quarters of an inch wide and three inches long, were associated together in pairs by means of platina wires to which they were soldered, fig. 88, the plates of one pair being either alike or different, as might be required. These were arranged in glasses, fig. 89, so as to form Volta's crown of cups. The acid or fluid in the cups never covered the whole of any plate; and occasionally small glass rods were put into the cups, between the plates, to prevent their contact. Single plates were used to terminate the series and complete the connexion with a galvanometer, or with a decomposing apparatus (899. 968. &c.), or both. Now if fig. 90 be examined and compared with fig. 91, the latter may be admitted as representing the former in its simplest condition; for the cups i, ii, and iii of the former, with their contents, are represented by the cells i, ii, and iii of the latter, and the metal plates Z and P of the former by the similar plates represented Z and P in the latter. The only difference, in fact, between the apparatus, fig. 90, and the trough represented fig. 91, is that twice the quantity of surface of contact between the metal and acid is allowed in the first to what would occur in the second.

1009. When the extreme plates of the arrangement just described, fig. 90, are connected metallically through the galvanometer _g_, then the whole represents a battery consisting of two pairs of zinc and platina plates urging a current forward, which has, however, to decompose water unassisted by any direct chemical affinity before it can be transmitted across the cell iii, and therefore before it can circulate. This decomposition of water, which is opposed to the passage of the current, may, as a matter of convenience, be considered as taking place either against the surfaces of the two platina plates which constitute the electrodes in the cell in, or against the two surfaces of that platina plate which separates the cells ii and iii, fig. 91, from each other. It is evident that if that plate were away, the battery would consist of two pairs of plates and two cells, arranged in the most favourable position for the production of a current. The platina plate therefore, which being introduced as at _x_, has oxygen evolved at one surface and hydrogen at the other (that is, if the decomposing current passes), may be considered as the cause of any obstruction arising from the decomposition of water by the electrolytic action of the current; and I have usually called it the interposed plate.

1010. In order to simplify the conditions, dilute sulphuric acid was first used in all the cells, and platina for the interposed plates; for then the initial intensity of the current which tends to be formed is constant, being due to the power which zinc has of decomposing water; and the opposing force of decomposition is also constant, the elements of the water being unassisted in their separation at the interposed plates by any affinity or secondary action at the electrodes (744.), arising either from the nature of the plate itself or the surrounding fluid.

1011. When only one voltaic pair of zinc and platina plates was used, the current of electricity was entirely stopped to all practical purposes by interposing one platina plate, fig. 92, i.e. by requiring of the current that it should decompose water, and evolve both its elements, before it should pass. This consequence is in perfect accordance with the views before given (910. 917. 973.). For as the whole result depends upon the opposition of forces at the places of electric excitement and electro-decomposition, and as water is the substance to be decomposed at both before the current can move, it is not to be expected that the zinc should have such powerful attraction for the oxygen, as not only to be able to take it from its associated hydrogen, but leave such a surplus of force as, passing to the second place of decomposition, should be there able to effect a second separation of the elements of water. Such an effect would require that the force of attraction between zinc and oxygen should under the circumstances be _at least_ twice as great as the force of attraction between the oxygen and hydrogen.

1012. When two pairs of zinc and platina exciting plates were used, the current was also practically stopped by one interposed platina plate, fig. 93. There was a very feeble effect of a current at first, but it ceased almost immediately. It will be referred to, with many other similar effects, hereafter (1017.).

1013. Three pairs of zinc and platina plates, fig. 94, were able to produce a current which could pass an interposed platina plate, and effect the electrolyzation of water in cell iv. The current was evident, both by the continued deflection of the galvanometer, and the production of bubbles of oxygen and hydrogen at the electrodes in cell iv. Hence the accumulated surplus force of three plates of zinc, which are active in decomposing water, is more than equal, when added together, to the force with which oxygen and hydrogen are combined in water, and is sufficient to cause the separation of these elements from each other.

1014. The three pairs of zinc and platina plates were now opposed by two intervening platina plates, fig. 95. In this case the current was stopped.

1015. Four pairs of zinc and platina plates were also neutralized by two interposed platina plates, fig. 96.

1016. Five pairs of zinc and platina, with two interposed platina plates, fig. 97, gave a feeble current; there was permanent deflection at the galvanometer, and decomposition in the cells vi and vii. But the current was very feeble; very much less than when all the intermediate plates were removed and the two extreme ones only retained: for when they were placed six inches asunder in one cell, they gave a powerful current. Hence five exciting pairs, with two interposed obstructing plates, do not give a current at all comparable to that of a single unobstructed pair.

1017. I have already said that a _very feeble current_ passed when the series included one interposed platina and two pairs of zinc and platina plates (1012.). A similarly feeble current passed in every case, and even when only one exciting pair and four intervening platina plates were used, fig. 98, a current passed which could be detected at _x_, both by chemical action on the solution of iodide of potassium, and by the galvanometer. This current I believe to be due to electricity reduced in intensity below the point requisite for the decomposition of water (970. 984.); for water can conduct electricity of such low intensity by the same kind of power which it possesses in common with metals and charcoal, though it cannot conduct electricity of higher intensity without suffering decomposition, and then opposing a new force consequent thereon. With an electric current of, or under this intensity, it is probable that increasing the number of interposed platina plates would not involve an increased difficulty of conduction.

1018. In order to obtain an idea of the additional interfering power of each added platina plate, six voltaic pairs and four intervening platinas were arranged as in fig. 99; a very feeble current then passed (985. 1017.). When one of the platinas was removed so that three intervened, a current somewhat stronger passed. With two intervening platinas a still stronger current passed; and with only one intervening platina a very fair current was obtained. But the effect of the successive plates, taken in the order of their interposition, was very different, as might be expected; for the first retarded the current more powerfully than the second, and the second more than the third.

1019. In these experiments both amalgamated and unamalgamated zinc were used, but the results generally were the same.

1020. The effects of retardation just described were altered altogether when changes were made in the _nature of the liquid_ used between the plates, either in what may be called the _exciting_ or the _retarding_ cells. Thus, retaining the exciting force the same, by still using pure dilute sulphuric acid for that purpose, if a little nitric acid were added to the liquid in the _retarding_ cells, then the transmission of the current was very much facilitated. For instance, in the experiment with one pair of exciting plates and one intervening plate (1011.), fig. 92, when a few drops of nitric acid were added to the contents of cell ii, then the current of electricity passed with considerable strength (though it soon fell from other causes (1036; 1040.),) and the same increased effect was produced by the nitric acid when many interposed plates were used.

1021. This seems to be a consequence of the diminution of the difficulty of decomposing water when its hydrogen, instead of being absolutely expelled, as in the former cases, is transferred to the oxygen of the nitric acid, producing a secondary result at the _cathode_ (752.); for in accordance with the chemical views of the electric current and its action already advanced (913.), the water, instead of opposing a resistance to decomposition equal to the full amount of the force of mutual attraction between its oxygen and hydrogen, has that force counteracted in part, and therefore diminished by the attraction of the hydrogen at the _cathode_ for the oxygen of the nitric acid which surrounds it, and with which it ultimately combines instead of being evolved in its free state.

1022. When a little nitric acid was put into the exciting cells, then again the circumstances favouring the transmission of the current were strengthened, for the _intensity_ of the current itself was increased by the addition (906.). When therefore a little nitric acid was added to both the _exciting_ and the _retarding_ cells, the current of electricity passed with very considerable freedom.

1023. When dilute muriatic acid was used, it produced and transmitted a current more easily than pure dilute sulphuric acid, but not so readily as dilute nitric acid. As muriatic acid appears to be decomposed more freely than water (765.), and as the affinity of zinc for chlorine is very powerful, it might be expected to produce a current more intense than that from the use of dilute sulphuric acid; and also to transmit it more freely by undergoing decomposition at a lower intensity (912.).

1024. In relation to the effect of these interpositions, it is necessary to state that they do not appear to be at all dependent upon the size of the electrodes, or their distance from each other in the acid, except that when a current _can pass_, changes in these facilitate or retard its passage. For on repeating the experiment with one intervening and one pair of exciting plates (1011.), fig. 92, and in place of the interposed plate P using sometimes a mere wire, and sometimes very large plates (1008.), and also changing the terminal exciting plates Z and P, so that they were sometimes wires only and at others of great size, still the results were the same as those already obtained.

1025. In illustration of the effect of distance, an experiment like that described with two exciting pairs and one intervening plate (1012.), fig. 93, was arranged so that the distance between the plates in the third cell could be increased to six or eight inches, or diminished to the thickness of a piece of intervening bibulous paper. Still the result was the same in both cases, the effect not being sensibly greater, when the plates were merely separated by the paper, than when a great way apart; so that the principal opposition to the current in this case does not depend upon the _quantity_ of intervening electrolytic conductor, but on the _relation of its elements to the intensity of the current_, or to the chemical nature of the electrodes and the surrounding fluids.

1026. When the acid was sulphuric acid, _increasing its strength_ in any of the cells, caused no change in the effects; it did not produce a more intense current in the exciting cells (908.), or cause the current produced to traverse the decomposing cells more freely. But if to very weak sulphuric acid a few drops of nitric acid were added, then either one or other of those effects could be produced; and, as might be expected in a case like this, where the exciting or conducting action bore a _direct_ reference to the acid itself, increasing the strength of this (the nitric acid), also increased its powers.

1027. The _nature of the interposed plate_ was now varied to show its relation to the phenomena either of excitation or retardation, and amalgamated zinc was first substituted for platina. On employing one voltaic pair and one interposed zinc plate, fig. 100, there was as powerful a current, apparently, as if the interposed zinc plate was away. Hydrogen was evolved against P in cell ii, and against the side of the second zinc in cell i; but no gas appeared against the side of the zinc in cell ii, nor against the zinc in cell i.

1028. On interposing two amalgamated zinc plates, fig. 101, instead of one, there was still a powerful current, but interference had taken place. On using three intermediate zinc plates, fig. 102, there was still further retardation, though a good current of electricity passed.

1029. Considering the retardation as due to the inaction of the amalgamated zinc upon the dilute acid, in consequence of the slight though general effect of diminished chemical power produced by the mercury on the surface, and viewing this inaction as the circumstance which rendered it necessary that each plate should have its tendency to decompose water assisted slightly by the electric current, it was expected that plates of the metal in the unamalgamated state would probably not require such assistance, and would offer no sensible impediment to the passing of the current. This expectation was fully realized in the use of two and three interposed unamalgamated plates. The electric current passed through them as freely as if there had been no such plates in the way. They offered no obstacle, because they could decompose water without the current; and the latter had only to give direction to a part of the forces, which would have been active whether it had passed or not.

1030. Interposed plates of copper were then employed. These seemed at first to occasion no obstruction, but after a few minutes the current almost entirely ceased. This effect appears due to the surfaces taking up that peculiar condition (1010.) by which they tend to produce a reverse current; for when one or more of the plates were turned round, which could easily be effected with the couronne des tasses form of experiment, fig. 90, then the current was powerfully renewed for a few moments, and then again ceased. Plates of platina and copper, arranged as a voltaic pile with dilute sulphuric acid, could not form a voltaic trough competent to act for more than a _few_ minutes, because of this peculiar counteracting effect.

1031. All these effects of retardation, exhibited by decomposition against surfaces for which the evolved elements have more or less affinity, or are altogether deficient in attraction, show generally, though beautifully, the chemical relations and source of the current, and also the balanced state of the affinities at the places of excitation and decomposition. In this way they add to the mass of evidence in favour of the identity of the two; for they demonstrate, as it were, the antagonism of the _chemical powers_ at the electromotive part with the _chemical powers_ at the interposed parts; they show that the first are _producing_ electric effects, and the second _opposing_ them; they bring the two into direct relation; they prove that either can determine the other, thus making what appears to be cause and effect convertible, and thereby demonstrating that both chemical and electrical action are merely two exhibitions of one single agent or power (916. &c.).

1032. It is quite evident, that as water and other electrolytes can conduct electricity without suffering decomposition (986.), when the electricity is of sufficiently low intensity, it may not be asserted as absolutely true in all cases, that whenever electricity passes through an electrolyte, it produces a definite effect of decomposition. But the quantity of electricity which can pass in a given time through an electrolyte without causing decomposition, is so small as to bear no comparison to that required in a case of very moderate decomposition, and with electricity above the intensity required for electrolyzation, I have found no sensible departure as yet from the law of _definite electrolytic action_ developed in the preceding series of these Researches (783. &c.).

1033. I cannot dismiss this division of the present Paper without making a reference to the important experiments of M. Aug. De la Rive on the effects of interposed plates[A]. As I have had occasion to consider such plates merely as giving rise to new decompositions, and in that way only causing obstruction to the passage of the electric current, I was freed from the necessity of considering the peculiar effects described by that philosopher. I was the more willing to avoid for the present touching upon these, as I must at the same time have entered into the views of Sir Humphry Davy upon the same subject[B] and also those of Marianini[C] and Hitter[D], which are connected with it.

[A] Annales de Chimie, tom. xxviii. p 190; and Mémoires de Génève.

[B] Philosophical Transactions, 1826, p. 413.

[C] Annales de Chimie, tom. xxxiii. pp. 117, 119, &c.

[D] Journal de Physique, tom. lvii. pp. 319, 350.

¶ v. _General Remarks on the active Voltaic Battery._

1034. When the ordinary voltaic battery is brought into action, its very activity produces certain effects, which re-act upon it, and cause serious deterioration of its power. These render it an exceedingly inconstant instrument as to the _quantity_ of effect which it is capable of producing. They are already, in part, known and understood; but as their importance, and that of certain other coincident results, will be more evident by reference to the principles and experiments already stated and described, I have thought it would be useful, in this investigation of the voltaic pile, to notice them briefly here.

1035. When the battery is in action, it causes such substances to be formed and arranged in contact with the plates as very much weaken its power, or even tend to produce a counter current. They are considered by Sir Humphry Davy as sufficient to account for the phenomena of Ritter's secondary piles, and also for the effects observed by M.A. De la Rive with interposed platina plates[A].

[A] Philosophical Transactions, 1826, p. 113.

1036. I have already referred to this consequence (1003.), as capable, in some cases, of lowering the force of the current to one-eighth or one-tenth of what it was at the first moment, and have met with instances in which its interference was very great. In an experiment in which one voltaic pair and one interposed platina plate were used with dilute sulphuric acid in the cells fig. 103, the wires of communication were so arranged, that the end of that marked 3 could be placed at pleasure upon paper moistened in the solution of iodide of potassium at _x_, or directly upon the platina plate there. If, after an interval during which the circuit had not been complete, the wire 3 were placed upon the paper, there was evidence of a current, decomposition ensued, and the galvanometer was affected. If the wire 3 were made to touch the metal of _p_, a comparatively strong sudden current was produced, affecting the galvanometer, but lasting only for a moment; the effect at the galvanometer ceased, and if the wire 3 were placed on the paper at _x_, no signs of decomposition occurred. On raising the wire 3, and breaking the circuit altogether for a while, the apparatus resumed its first power, requiring, however, from five to ten minutes for this purpose; and then, as before, on making contact between 3 and _p_, there was again a momentary current, and immediately all the effects apparently ceased.