¶ ii. On the Intensity necessary for Electrolyzation.

966. It became requisite, for the comprehension of many of the conditions attending voltaic action, to determine positively, if possible, whether electrolytes could resist the action of an electric current when beneath a certain intensity? whether the intensity at which the current ceased to act would be the same for all bodies? and also whether the electrolytes thus resisting decomposition would conduct the electric current as a metal does, after they ceased to conduct as electrolytes, or would act as perfect insulators?

967. It was evident from the experiments described (904. 906.) that different bodies were decomposed with very different facilities, and apparently that they required for their decomposition currents of different intensities, resisting some, but giving way to others. But it was needful, by very careful and express experiments, to determine whether a current could really pass through, and yet not decompose an electrolyte (910.).

968. An arrangement (fig. 84.) was made, in which two glass vessels contained the same dilute sulphuric acid, sp. gr. 1.25. The plate z was amalgamated zinc, in connexion, by a platina wire a, with the platina plate e; b was a platina wire connecting the two platina plates PP'; c was a platina wire connected with the platina plate P". On the plate e was placed a piece of paper moistened in solution of iodide of potassium: the wire c was so curved that its end could be made to rest at pleasure on this paper, and show, by the evolution of iodine there, whether a current was passing; or, being placed in the dotted position, it formed a direct communication with the platina plate e, and the electricity could pass without causing decomposition. The object was to produce a current by the action of the acid on the amalgamated zinc in the first vessel A; to pass it through the acid in the second vessel B by platina electrodes, that its power of decomposing water might, if existing, be observed; and to verify the existence of the current at pleasure, by decomposition at e, without involving the continual obstruction to the current which would arise from making the decomposition there constant. The experiment, being arranged, was examined and the existence of a current ascertained by the decomposition at e; the whole was then left with the end of the wire c resting on the plate e, so as to form a constant metallic communication there.

969. After several hours, the end of the wire c was replaced on the test-paper at e: decomposition occurred, and the proof of a passing current was therefore complete. The current was very feeble compared to what it had been at the beginning of the experiment, because of a peculiar state acquired by the metal surfaces in the second vessel, which caused them to oppose the passing current by a force which they possess under these circumstances (1040.). Still it was proved, by the decomposition, that this state of the plates in the second vessel was not able entirely to stop the current determined in the first, and that was all that was needful to be ascertained in the present inquiry.

970. This apparatus was examined from time to time, and an electric current always found circulating through it, until twelve days had elapsed, during which the water in the second vessel had been constantly subject to its action. Notwithstanding this lengthened period, not the slightest appearance of a bubble upon either of the plates in that vessel occurred. From the results of the experiment, I conclude that a current had passed, but of so low an intensity as to fall beneath that degree at which the elements of water, unaided by any secondary force resulting from the capability of combination with the matter of the electrodes, or of the liquid surrounding them, separated from each other.

971. It may be supposed, that the oxygen and hydrogen had been evolved in such small quantities as to have entirely dissolved in the water, and finally to have escaped at the surface, or to have reunited into water. That the hydrogen can be so dissolved was shown in the first vessel; for after several days minute bubbles of gas gradually appeared upon a glass rod, inserted to retain the zinc and platina apart, and also upon the platina plate itself, and these were hydrogen. They resulted principally in this way:—notwithstanding the amalgamation of the zinc, the acid exerted a little direct action upon it, so that a small stream of hydrogen bubbles was continually rising from its surface; a little of this hydrogen gradually dissolved in the dilute acid, and was in part set free against the surfaces of the rod and the plate, according to the well-known action of such solid bodies in solutions of gases (623. &c.).

972. But if the gases had been evolved in the second vessel by the decomposition of water, and had tended to dissolve, still there would have been every reason to expect that a few bubbles should have appeared on the electrodes, especially on the negative one, if it were only because of its action as a nucleus on the solution supposed to be formed; but none appeared even after twelve days.

973. When a few drops only of nitric acid were added to the vessel A, fig. 84, then the results were altogether different. In less than five minutes bubbles of gas appeared on the plates P' and P" in the second vessel. To prove that this was the effect of the electric current (which by trial at c was found at the same time to be passing,) the connexion at c was broken, the plates P'P" cleared from bubbles and left in the acid of the vessel B, for fifteen minutes: during that time no bubbles appeared upon them; but on restoring the communication at c, a minute did not elapse before gas appeared in bubbles upon the plates. The proof, therefore, is most full and complete, that the current excited by dilute sulphuric acid with a little nitric acid in vessel A, has intensity enough to overcome the chemical affinity exerted between the oxygen and hydrogen of the water in the vessel B, whilst that excited by dilute sulphuric acid alone has not sufficient intensity.

974. On using a strong solution of caustic potassa in the vessel A, to excite the current, it was found by the decomposing effects at e, that the current passed. But it had not intensity enough to decompose the water in the vessel B; for though left for fourteen days, during the whole of which time the current was found to be passing, still not the slightest appearance of gas appeared on the plates P'P", nor any other signs of the water having suffered decomposition.

975. Sulphate of soda in solution was then experimented with, for the purpose of ascertaining with respect to it, whether a certain electrolytic intensity was also required for its decomposition in this state, in analogy with the result established with regard to water (974). The apparatus was arranged as in fig. 85; P and Z are the platina and zinc plates dipping into a solution of common salt; a and b are platina plates connected by wires of platina (except in the galvanometer g) with P and Z; c is a connecting wire of platina, the ends of which can be made to rest either on the plates a, b, or on the papers moistened in solutions which are placed upon them; so that the passage of the current without decomposition, or with one or two decompositions, was under ready command, as far as arrangement was concerned. In order to change the anodes and cathodes at the places of decomposition, the form of apparatus fig. 86, was occasionally adopted. Here only one platina plate, c, was used; both pieces of paper on which decomposition was to be effected were placed upon it, the wires from P and Z resting upon these pieces of paper, or upon the plate c, according as the current with or without decomposition of the solutions was required.

976. On placing solution of iodide of potassium in paper at one of the decomposing localities, and solution of sulphate of soda at the other, so that the electric current should pass through both at once, the solution of iodide was slowly decomposed, yielding iodine at the anode and alkali at the cathode; but the solution of sulphate of soda exhibited no signs of decomposition, neither acid nor alkali being evolved from it. On placing the wires so that the iodide alone was subject to the action of the current (900.), it was quickly and powerfully decomposed; but on arranging them so that the sulphate of soda alone was subject to action, it still refused to yield up its elements. Finally, the apparatus was so arranged under a wet bell-glass, that it could be left for twelve hours, the current passing during the whole time through a solution of sulphate of soda, retained in its place by only two thicknesses of bibulous litmus and turmeric paper. At the end of that time it was ascertained by the decomposition of iodide of potassium at the second place of action, that the current was passing and had passed for the twelve hours, and yet no trace of acid or alkali from the sulphate of soda appeared.

977. From these experiments it may, I think, be concluded, that a solution of sulphate of soda can conduct a current of electricity, which is unable to decompose the neutral salt present; that this salt in the state of solution, like water, requires a certain electrolytic intensity for its decomposition; and that the necessary intensity is much higher for this substance than for the iodide of potassium in a similar state of solution.

978. I then experimented on bodies rendered decomposable by fusion, and first on chloride of lead. The current was excited by dilute sulphuric acid without any nitric acid between zinc and platina plates, fig. 87, and was then made to traverse a little chloride of lead fused upon glass at a, a paper moistened in solution of iodide of potassium at b, and a galvanometer at g. The metallic terminations at a and b were of platina. Being thus arranged, the decomposition at b and the deflection at g showed that an electric current was passing, but there was no appearance of decomposition at a, not even after a metallic communication at b was established. The experiment was repeated several times, and I am led to conclude that in this case the current has not intensity sufficient to cause the decomposition of the chloride of lead; and further, that, like water (974.), fused chloride of lead can conduct an electric current having an intensity below that required to effect decomposition.

979. Chloride of silver was then placed at a, fig. 87, instead of chloride of lead. There was a very ready decomposition of the solution of iodide of potassium at b, and when metallic contact was made there, very considerable deflection of the galvanometer needle at g. Platina also appeared to be dissolved at the anode of the fused chloride at a, and there was every appearance of a decomposition having been effected there.

980. A further proof of decomposition was obtained in the following manner. The platina wires in the fused chloride at a were brought very near together (metallic contact having been established at b), and left so; the deflection at the galvanometer indicated the passage of a current, feeble in its force, but constant. After a minute or two, however, the needle would suddenly be violently affected, and indicate a current as strong as if metallic contact had taken place at a. This I actually found to be the case, for the silver reduced by the action of the current crystallized in long delicate spiculæ, and these at last completed the metallic communication; and at the same time that they transmitted a more powerful current than the fused chloride, they proved that electro-chemical decomposition of that chloride had been going on. Hence it appears, that the current excited by dilute sulphuric acid between zinc and platina, has an intensity above that required to electrolyze the fused chloride of silver when placed between platina electrodes, although it has not intensity enough to decompose chloride of lead under the same circumstances.

981. A drop of water placed at a instead of the fused chlorides, showed as in the former case (970.), that it could conduct a current unable to decompose it, for decomposition of the solution of iodide at b occurred after some time. But its conducting power was much below that of the fused chloride of lead (978.).

982. Fused nitre at a conducted much better than water: I was unable to decide with certainty whether it was electrolyzed, but I incline to think not, for there was no discoloration against the platina at the cathode. If sulpho-nitric acid had been used in the exciting vessel, both the nitre and the chloride of lead would have suffered decomposition like the water (906.).

983. The results thus obtained of conduction without decomposition, and the necessity of a certain electrolytic intensity for the separation of the ions of different electrolytes, are immediately connected with the experiments and results given in § 10. of the Fourth Series of these Researches (418. 423. 444. 419.). But it will require a more exact knowledge of the nature of intensity, both as regards the first origin of the electric current, and also the manner in which it may be reduced, or lowered by the intervention of longer or shorter portions of bad conductors, whether decomposable or not, before their relation can be minutely and fully understood.

984. In the case of water, the experiments I have as yet made, appear to show, that, when the electric current is reduced in intensity below the point required for decomposition, then the degree of conduction is the same whether sulphuric acid, or any other of the many bodies which can affect its transferring power as an electrolyte, are present or not. Or, in other words, that the necessary electrolytic intensity for water is the same whether it be pure, or rendered a better conductor by the addition of these substances; and that for currents of less intensity than this, the water, whether pure or acidulated, has equal conducting power. An apparatus, fig. 84, was arranged with dilute sulphuric acid in the vessel A, and pure distilled water in the vessel B. By the decomposition at c, it appeared as if water was a better conductor than dilute sulphuric acid for a current of such low intensity as to cause no decomposition. I am inclined, however, to attribute this apparent superiority of water to variations in that peculiar condition of the platina electrodes which is referred to further on in this Series (1040.), and which is assumed, as far as I can judge, to a greater degree in dilute sulphuric acid than in pure water. The power therefore, of acids, alkalies, salts, and other bodies in solution, to increase conducting power, appears to hold good only in those cases where the electrolyte subject to the current suffers decomposition, and loses all influence when the current transmitted has too low an intensity to affect chemical change. It is probable that the ordinary conducting power of an electrolyte in the solid state (419.) is the same as that which it possesses in the fluid state for currents, the tension of which is beneath the due electrolytic intensity.

985. Currents of electricity, produced by less than eight or ten series of voltaic elements, can be reduced to that intensity at which water can conduct them without suffering decomposition, by causing them to pass through three or four vessels in which water shall be successively interposed between platina surfaces. The principles of interference upon which this effect depends, will be described hereafter (1009. 1018.), but the effect may be useful in obtaining currents of standard intensity, and is probably applicable to batteries of any number of pairs of plates.

986. As there appears every reason to expect that all electrolytes will be found subject to the law which requires an electric current of a certain intensity for their decomposition, but that they will differ from each other in the degree of intensity required, it will be desirable hereafter to arrange them in a table, in the order of their electrolytic intensities. Investigations on this point must, however, be very much extended, and include many more bodies than have been here mentioned before such a table can be constructed. It will be especially needful in such experiments, to describe the nature of the electrodes used, or, if possible, to select such as, like platina or plumbago in certain cases, shall have no power of assisting the separation of the ions to be evolved (913).

987. Of the two modes in which bodies can transmit the electric forces, namely, that which is so characteristically exhibited by the metals, and usually called conduction, and that in which it is accompanied by decomposition, the first appears common to all bodies, although it occurs with almost infinite degrees of difference; the second is at present distinctive of the electrolytes. It is, however, just possible that it may hereafter be extended to the metals; for their power of conducting without decomposition may, perhaps justly, be ascribed to their requiring a very high electrolytic intensity for their decomposition.

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.