Eighth Series. (continued 2)

987-1/2. The establishment of the principle that a certain electrolytic intensity is necessary before decomposition can be effected, is of great importance to all those considerations which arise regarding the probable effects of weak currents, such for instance as those produced by natural thermo-electricity, or natural voltaic arrangements in the earth. For to produce an effect of decomposition or of combination, a current must not only exist, but have a certain intensity before it can overcome the quiescent affinities opposed to it, otherwise it will be conducted, producing no permanent chemical effects. On the other hand, the principles are also now evident by which an opposing action can be so weakened by the juxtaposition of bodies not having quite affinity enough to cause direct action between them (913.), that a very weak current shall be able to raise the sum of actions sufficiently high, and cause chemical changes to occur.

988. In concluding this division on the intensity necessary for electrolyzation, I cannot resist pointing out the following remarkable conclusion in relation to intensity generally. It would appear that when a voltaic current is produced, having a certain intensity, dependent upon the strength of the chemical affinities by which that current is excited (916.), it can decompose a particular electrolyte without relation to the quantity of electricity passed, the intensity deciding whether the electrolyte shall give way or not. If that conclusion be confirmed, then we may arrange circumstances so that the same quantity of electricity may pass in the same time, in at the same surface, into the same decomposing body in the same state, and yet, differing in intensity, will decompose in one case and in the other not:—for taking a source of too low an intensity to decompose, and ascertaining the quantity passed in a given time, it is easy to take another source having a sufficient intensity, and reducing the quantity of electricity from it by the intervention of bad conductors to the same proportion as the former current, and then all the conditions will be fulfilled which are required to produce the result described.

¶ iii. On associated Voltaic Circles, or the Voltaic Battery.

989. Passing from the consideration of single circles (875. &c.) to their association in the voltaic battery, it is a very evident consequence, that if matters are so arranged that two sets of affinities, in place of being opposed to each other as in figg. 73. 76. (880. 891.), are made to act in conformity, then, instead of either interfering with the other, it will rather assist it. This is simply the case of two voltaic pairs of metals arranged so as to form one circuit. In such arrangements the activity of the whole is known to be increased, and when ten, or a hundred, or any larger number of such alternations are placed in conformable association with each other, the power of the whole becomes proportionally exalted, and we obtain that magnificent instrument of philosophic research, the voltaic battery.

990. But it is evident from the principles of definite action already laid down, that the quantity of electricity in the current cannot be increased with the increase of the quantity of metal oxidized and dissolved at each new place of chemical action. A single pair of zinc and platina plates throws as much electricity into the form of a current, by the oxidation of 32.5 grains of the zinc (868.) as would be circulated by the same alteration of a thousand times that quantity, or nearly five pounds of metal oxidized at the surface of the zinc plates of a thousand pairs placed in regular battery order. For it is evident, that the electricity which passes across the acid from the zinc to the platina in the first cell, and which has been associated with, or even evolved by, the decomposition of a definite portion of water in that cell, cannot pass from the zinc to the platina across the acid in the second cell, without the decomposition of the same quantity of water there, and the oxidation of the same quantity of zinc by it (924. 949.). The same result recurs in every other cell; the electro-chemical equivalent of water must be decomposed in each, before the current can pass through it; for the quantity of electricity passed and the quantity of electrolyte decomposed, must be the equivalents of each other. The action in each cell, therefore, is not to increase the quantity set in motion in any one cell, but to aid in urging forward that quantity, the passing of which is consistent with the oxidation of its own zinc; and in this way it exalts that peculiar property of the current which we endeavour to express by the term intensity, without increasing the quantity beyond that which is proportionate to the quantity of zinc oxidized in any single cell of the series.

991. To prove this, I arranged ten pairs of amalgamated zinc and platina plates with dilute sulphuric acid in the form of a battery. On completing the circuit, all the pairs acted and evolved gas at the surfaces of the platina. This was collected and found to be alike in quantity for each plate; and the quantity of hydrogen evolved at any one platina plate was in the same proportion to the quantity of metal dissolved from any one zinc plate, as was given in the experiment with a single pair (864. &c.). It was therefore certain, that, just as much electricity and no more had passed through the series of ten pair of plates as had passed through, or would have been put into motion by, any single pair, notwithstanding that ten times the quantity of zinc had been consumed.

992. This truth has been proved also long ago in another way, by the action of the evolved current on a magnetic needle; the deflecting power of one pair of plates in a battery being equal to the deflecting power of the whole, provided the wires used be sufficiently large to carry the current of the single pair freely; but the cause of this equality of action could not be understood whilst the definite action and evolution of electricity (783. 869.) remained unknown.

993. The superior decomposing power of a battery over a single pair of plates is rendered evident in two ways. Electrolytes held together by an affinity so strong as to resist the action of the current from a single pair, yield up their elements to the current excited by many pairs; and that body which is decomposed by the action of one or of few pairs of metals, &c., is resolved into its ions the more readily as it is acted upon by electricity urged forward by many alternations.

994. Both these effects are, I think, easily understood. Whatever intensity may be, (and that must of course depend upon the nature of electricity, whether it consist of a fluid or fluids, or of vibrations of an ether, or any other kind or condition of matter,) there seems to be no difficulty in comprehending that the degree of intensity at which a current of electricity is evolved by a first voltaic element, shall be increased when that current is subjected to the action of a second voltaic element, acting in conformity and possessing equal powers with the first: and as the decompositions are merely opposed actions, but exactly of the same kind as those which generate the current (917.), it seems to be a natural consequence, that the affinity which can resist the force of a single decomposing action may be unable to oppose the energies of many decomposing actions, operating conjointly, as in the voltaic battery.

995. That a body which can give way to a current of feeble intensity, should give way more freely to one of stronger force, and yet involve no contradiction to the law of definite electrolytic action, is perfectly consistent. All the facts and also the theory I have ventured to put forth, tend to show that the act of decomposition opposes a certain force to the passage of the electric current; and, that this obstruction should be overcome more or less readily, in proportion to the greater or less intensity of the decomposing current, is in perfect consistency with all our notions of the electric agent.

996. I have elsewhere (947.) distinguished the chemical action of zinc and dilute sulphuric acid into two portions; that which, acting effectually on the zinc, evolves hydrogen at once upon its surface, and that which, producing an arrangement of the chemical forces throughout the electrolyte present, (in this case water,) tends to take oxygen from it, but cannot do so unless the electric current consequent thereon can have free passage, and the hydrogen be delivered elsewhere than against the zinc. The electric current depends altogether upon the second of these; but when the current can pass, by favouring the electrolytic action it tends to diminish the former and increase the latter portion.

997. It is evident, therefore, that when ordinary zinc is used in a voltaic arrangement, there is an enormous waste of that power which it is the object to throw into the form of an electric current; a consequence which is put in its strongest point of view when it is considered that three ounces and a half of zinc, properly oxidized, can circulate enough electricity to decompose nearly one ounce of water, and cause the evolution of about 2100 cubic inches of hydrogen gas. This loss of power not only takes place during the time the electrodes of the battery are in communication, being then proportionate to the quantity of hydrogen evolved against the surface of any one of the zinc plates, but includes also all the chemical action which goes on when the extremities of the pile are not in communication.

998. This loss is far greater with ordinary zinc than with the pure metal, as M. De la Rive has shown208. The cause is, that when ordinary zinc is acted upon by dilute sulphuric acid, portions of copper, lead, cadmium, or other metals which it may contain, are set free upon its surface; and these, being in contact with the zinc, form small but very active voltaic circles, which cause great destruction of the zinc and evolution of hydrogen, apparently upon the zinc surface, but really upon the surface of these incidental metals. In the same proportion as they serve to discharge or convey the electricity back to the zinc, do they diminish its power of producing an electric current which shall extend to a greater distance across the acid, and be discharged only through the copper or platina plate which is associated with it for the purpose of forming a voltaic apparatus.

999. All these evils are removed by the employment of an amalgam of zinc in the manner recommended by Mr. Kemp209, or the use of the amalgamated zinc plates of Mr. Sturgeon (863.), who has himself suggested and objected to their application in galvanic batteries; for he says, "Were it not on account of the brittleness and other inconveniences occasioned by the incorporation of the mercury with the zinc, amalgamation of the zinc surfaces in galvanic batteries would become an important improvement; for the metal would last much longer, and remain bright for a considerable time, even for several successive hours; essential considerations in the employment of this apparatus210."

1000. Zinc so prepared, even though impure, does not sensibly decompose the water of dilute sulphuric acid, but still has such affinity for the oxygen, that the moment a metal which, like copper or platina, has little or no affinity, touches it in the acid, action ensues, and a powerful and abundant electric current is produced. It is probable that the mercury acts by bringing the surface, in consequence of its fluidity, into one uniform condition, and preventing those differences in character between one spot and another which are necessary for the formation of the minute voltaic circuits referred to (998.). If any difference does exist at the first moment, with regard to the proportion of zinc and mercury, at one spot on the surface, as compared with another, that spot having the least mercury is first acted on, and, by solution of the zinc, is soon placed in the same condition as the other parts, and the whole plate rendered superficially uniform. One part cannot, therefore, act as a discharger to another; and hence all the chemical power upon the water at its surface is in that equable condition (949.), which, though it tends to produce an electric current through the liquid to another plate of metal which can act as a discharger (950.), presents no irregularities by which any one part, having weaker affinities for oxygen, can act as a discharger to another. Two excellent and important consequences follow upon this state of the metal. The first is, that the full equivalent of electricity is obtained for the oxidation of a certain quantity of zinc; the second, that a battery constructed with the zinc so prepared, and charged with dilute sulphuric acid, is active only whilst the electrodes are connected, and ceases to act or be acted upon by the acid the instant the communication is broken.

1001. I have had a small battery of ten pairs of plates thus constructed, and am convinced that arrangements of this kind will be very important, especially in the development and illustration of the philosophical principles of the instrument. The metals I have used are amalgamated zinc and platina, connected together by being soldered to platina wires, the whole apparatus having the form of the couronne des tasses. The liquid used was dilute sulphuric acid of sp. gr. 1.25. No action took place upon the metals except when the electrodes were in communication, and then the action upon the zinc was only in proportion to the decomposition in the experimental cell; for when the current was retarded there, it was retarded also in the battery, and no waste of the powers of the metal was incurred.

1002. In consequence of this circumstance, the acid in the cells remained active for a very much longer time than usual. In fact, time did not tend to lower it in any sensible degree: for whilst the metal was preserved to be acted upon at the proper moment, the acid also was preserved almost at its first strength. Hence a constancy of action far beyond what can be obtained by the use of common zinc.

1003. Another excellent consequence was the renewal, during the interval of rest, between two experiments of the first and most efficient state. When an amalgamated zinc and a platina plate, immersed in dilute sulphuric acid, are first connected, the current is very powerful, but instantly sinks very much in force, and in some cases actually falls to only an eighth or a tenth of that first produced (1036.). This is due to the acid which is in contact with the zinc becoming neutralized by the oxide formed; the continued quick oxidation of the metal being thus prevented. With ordinary zinc, the evolution of gas at its surface tends to mingle all the liquid together, and thus bring fresh acid against the metal, by which the oxide formed there can be removed. With the amalgamated zinc battery, at every cessation of the current, the saline solution against the zinc is gradually diffused amongst the rest of the liquid; and upon the renewal of contact at the electrodes, the zinc plates are found most favourably circumstanced for the production of a ready and powerful current.

1004. It might at first be imagined that amalgamated zinc would be much inferior in force to common zinc, because, of the lowering of its energy, which the mercury might be supposed to occasion over the whole of its surface; but this is not the case. When the electric currents of two pairs of platina and zinc plates were opposed, the difference being that one of the zincs was amalgamated and the other not, the current from the amalgamated zinc was most powerful, although no gas was evolved against it, and much was evolved at the surface of the unamalgamated metal. Again, as Davy has shown211, if amalgamated and unamalgamated zinc be put in contact, and dipped into dilute sulphuric acid, or other exciting fluids, the former is positive to the latter, i.e. the current passes from the amalgamated zinc, through the fluid, to the unprepared zinc. This he accounts for by supposing that "there is not any inherent and specific property in each metal which gives it the electrical character, but that it depends upon its peculiar state—on that form of aggregation which fits it for chemical change."

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 plates212. 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 subject213 and also those of Marianini214 and Hitter215, which are connected with it.

¶ 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 plates216.

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.

1037. This effect I was ultimately able to refer to the state of the film of fluid in contact with the zinc plate in cell i. The acid of that film is instantly neutralized by the oxide formed; the oxidation of the zinc cannot, of course, go on with the same facility as before; and the chemical action being thus interrupted, the voltaic action diminishes with it. The time of the rest was required for the diffusion of the liquid, and its replacement by other acid. From the serious influence of this cause in experiments with single pairs of plates of different metals, in which I was at one time engaged, and the extreme care required to avoid it, I cannot help feeling a strong suspicion that it interferes more frequently and extensively than experimenters are aware of, and therefore direct their attention to it.

1038. In considering the effect in delicate experiments of this source of irregularity of action, in the voltaic apparatus, it must be remembered that it is only that very small portion of matter which is directly in contact with the oxidizable metal which has to be considered with reference to the change of its nature; and this portion is not very readily displaced from its position upon the surface of the metal (582. 605.), especially if that metal be rough and irregular. In illustration of this effect, I will quote a remarkable experiment. A burnished platina plate (569.) was put into hot strong sulphuric acid for an instant only: it was then put into distilled water, moved about in it, taken out, and wiped dry: it was put into a second portion of distilled water, moved about in it, and again wiped: it was put into a third portion of distilled water, in which it was moved about for nearly eight seconds; it was then, without wiping, put into a fourth portion of distilled water, where it was allowed to remain five minutes. The two latter portions of water were then tested for sulphuric acid; the third gave no sensible appearance of that substance, but the fourth gave indications which were not merely evident, but abundant for the circumstances under which it had been introduced. The result sufficiently shows with what difficulty that portion of the substance which is in contact with the metal leaves it; and as the contact of the fluid formed against the plate in the voltaic circuit must be as intimate and as perfect as possible, it is easy to see how quickly and greatly it must vary from the general fluid in the cells, and how influential in diminishing the force of the battery this effect must be.

1039. In the ordinary voltaic pile, the influence of this effect will occur in all variety of degrees. The extremities of a trough of twenty pairs of plates of Wollaston's construction were connected with the volta-electrometer, fig. 66. (711.), of the Seventh Series of these Researches, and after five minutes the number of bubbles of gas issuing from the extremity of the tube, in consequence of the decomposition of the water, noted. Without moving the plates, the acid between the copper and zinc was agitated by the introduction of a feather. The bubbles were immediately evolved more rapidly, above twice the number being produced in the same portion of time as before. In this instance it is very evident that agitation by a feather must have been a very imperfect mode of restoring the acid in the cells against the plates towards its first equal condition; and yet imperfect as the means were, they more than doubled the power of the battery. The first effect of a battery which is known to be so superior to the degree of action which the battery can sustain, is almost entirely due to the favourable condition of the acid in contact with the plates.

1040. A second cause of diminution in the force of the voltaic battery, consequent upon its own action, is that extraordinary state of the surfaces of the metals (969.) which was first described, I believe, by Ritter217, to which he refers the powers of his secondary piles, and which has been so well experimented upon by Marianini, and also by A. De la Rive. If the apparatus, fig. 103. (1096.), be left in action for an hour or two, with the wire 3 in contact with the plate p, so as to allow a free passage for the current, then, though the contact be broken for ten or twelve minutes, still, upon its renewal, only a feeble current will pass, not at all equal in force to what might be expected. Further, if P^{1} and P^{2} be connected by a metal wire, a powerful momentary current will pass from P^{2} to P^{1} through the acid, and therefore in the reverse direction to that produced by the action of the zinc in the arrangement; and after this has happened, the general current can pass through the whole of the system as at first, but by its passage again restores the plates P^{2} and P^{1} into the former opposing condition. This, generally, is the fact described by Ritter, Marianini, and De la Rive. It has great opposing influence on the action of a pile, especially if the latter consist of but a small number of alternations, and has to pass its current through many interpositions. It varies with the solution in which the interposed plates are immersed, with the intensity of the current, the strength of the pile, the time of action, and especially with accidental discharges of the plates by inadvertent contacts or reversions of the plates during experiments, and must be carefully watched in every endeavour to trace the source, strength, and variations of the voltaic current. Its effect was avoided in the experiments already described (1036. &c.), by making contact between the plates P^{1} and P^{2} before the effect dependent upon the state of the solution in contact with the zinc plate was observed, and by other precautions.

1041. When an apparatus like fig. 98. (1017.) with several platina plates was used, being connected with a battery able to force a current through them, the power which they acquired, of producing a reversed current, was very considerable.

1042. Weak and exhausted charges should never be used at the same time with strong and fresh ones in the different cells of a trough, or the different troughs of a battery: the fluid in all the cells should be alike, else the plates in the weaker cells, in place of assisting, retard the passage of the electricity generated in, and transmitted across, the stronger cells. Each zinc plate so circumstanced has to be assisted in decomposing power before the whole current can pass between it and the liquid. So, that, if in a battery of fifty pairs of plates, ten of the cells contain a weaker charge than the others, it is as if ten decomposing plates were opposed to the transit of the current of forty pairs of generating plates (1031.). Hence a serious loss of force, and hence the reason why, if the ten pairs of plates were removed, the remaining forty pairs would be much more powerful than the whole fifty.

1043. Five similar troughs, of ten pairs of plates each, were prepared, four of them with a good uniform charge of acid, and the fifth with the partially neutralized acid of a used battery. Being arranged in right order, and connected with a volta-electrometer (711.), the whole fifty pairs of plates yielded 1.1 cubic inch of oxygen and hydrogen in one minute: but on moving one of the connecting wires so that only the four well-charged troughs should be included in the circuit, they produced with the same volta-electrometer 8.4 cubical inches of gas in the same time. Nearly seven-eighths of the power of the four troughs had been lost, therefore, by their association with the fifth trough.

1044. The same battery of fifty pairs of plates, after being thus used, was connected with a volta-electrometer (711.), so that by quickly shifting the wires of communication, the current of the whole of the battery, or of any portion of it, could be made to pass through the instrument for given portions of time in succession. The whole of the battery evolved 0.9 of a cubic inch of oxygen and hydrogen in half a minute; the forty plates evolved 4.6 cubic inches in the same time; the whole then evolved 1 cubic inch in the half-minute; the ten weakly charged evolved 0.4 of a cubic inch in the time given: and finally the whole evolved 1.15 cubic inch in the standard time. The order of the observations was that given: the results sufficiently show the extremely injurious effect produced by the mixture of strong and weak charges in the same battery218.

1045. In the same manner associations of strong and weak pairs of plates should be carefully avoided. A pair of copper and platina plates arranged in accordance with a pair of zinc and platina plates in dilute sulphuric acid, were found to stop the action of the latter, or even of two pairs of the latter, as effectually almost as an interposed plate of platina (1011.), or as if the copper itself had been platina. It, in fact, became an interposed decomposing plate, and therefore a retarding instead of an assisting pair.

1046. The reversal, by accident or otherwise, of the plates in a battery has an exceedingly injurious effect. It is not merely the counteraction of the current which the reversed plates can produce, but their effect also in retarding even as indifferent plates, and requiring decomposition to be effected upon their surface, in accordance with the course of the current, before the latter can pass. They oppose the current, therefore, in the first place, as interposed platina plates would do (1011-1018.); and to this they add a force of opposition as counter-voltaic plates. I find that, in a series of four pairs of zinc and platina plates in dilute sulphuric acid, if one pair be reversed, it very nearly neutralizes the power of the whole.

1047. There are many other causes of reaction, retardation, and irregularity in the voltaic battery. Amongst them is the not unusual one of precipitation of copper upon the zinc in the cells, the injurious effect of which has before been adverted to (1006.). But their interest is not perhaps sufficient to justify any increase of the length of this paper, which is rather intended to be an investigation of the theory of the voltaic pile than a particular account of its practical application219.

Note.—Many of the views and experiments in this Series of my Experimental Researches will be seen at once to be corrections and extensions of the theory of electro-chemical decomposition, given in the Fifth and Seventh Series of these Researches. The expressions I would now alter are those which concern the independence of the evolved elements in relation to the poles or electrodes, and the reference of their evolution to powers entirely internal (524. 537. 661.). The present paper fully shows my present views; and I would refer to paragraphs 891. 904. 910. 917. 918. 947. 963. 1007. 1031. &c., as stating what they are. I hope this note will be considered as sufficient in the way of correction at present; for I would rather defer revising the whole theory of electro-chemical decomposition until I can obtain clearer views of the way in which the power under consideration can appear at one time as associated with particles giving them their chemical attraction, and at another as free electricity (493. 957.).—M.F.

Royal Institution,

March 31st, 1834.