Part 43

868. What, then, follows as a necessary consequence of the whole experiment? Why, this: that the chemical action upon 32.31 parts, or one equivalent of zinc, in this simple voltaic circle, was able to evolve such quantity of electricity in the form of a current, as, passing through water, should decompose 9 parts, or one equivalent of that substance: and considering the definite relations of electricity as developed in the preceding parts of the present paper, the results prove that the quantity of electricity which, being naturally associated with the particles of matter, gives them their combining power, is able, when thrown into a current, to separate those particles from their state of combination; or, in other words, that the electricity which decomposes, and that which is evolved by the decomposition of a certain quantity of matter, are alike.

869. The harmony which this theory of the definite evolution and the equivalent definite action of electricity introduces into the associated theories of definite proportions and electrochemical affinity, is very great. According to it, the equivalent weights of bodies are simply those quantities of them which contain equal quantities of electricity, or have naturally equal electric powers; it being the ELECTRICITY which determines the equivalent number, because it determines the combining force. Or, if we adopt the atomic theory or phraseology, then the atoms of bodies which are equivalents to each other in their ordinary chemical action, have equal quantities of electricity naturally associated with them. But I must confess I am jealous of the term atom; for though it is very easy to talk of atoms, it is very difficult to form a clear idea of their nature, especially when compound bodies are under consideration.

870. I cannot refrain from recalling here the beautiful idea put forth, I believe, by Berzelius (703.) in his development of his views of the electro-chemical theory of affinity, that the heat and light evolved during cases of powerful combination are the consequence of the electric discharge which is at the moment taking place. The idea is in perfect accordance with the view I have taken of the quantity of electricity associated with the particles of matter.

871. In this exposition of the law of the definite action of electricity, and its corresponding definite proportion in the particles of bodies, I do not pretend to have brought, as yet, every case of chemical or electro-chemical action under its dominion. There are numerous considerations of a theoretical nature, especially respecting the compound particles of matter and the resulting electrical forces which they ought to possess, which I hope will gradually receive their development; and there are numerous experimental cases, as, for instance, those of compounds formed by weak affinities, the simultaneous decomposition of water and salts, &c., which still require investigation. But whatever the results on these and numerous other points may be, I do not believe that the facts which I have advanced, or even the general laws deduced from them, will suffer any serious change; and they are of sufficient importance to justify their publication, though much may yet remain imperfect or undone. Indeed, it is the great beauty of our science, CHEMISTRY, that advancement in it, whether in a degree great or small, instead of exhausting the subjects of research, opens the doors to further and more abundant knowledge, overflowing with beauty and utility, to those who will be at the easy personal pains of undertaking its experimental investigation.

872. The definite production of electricity (868.) in association with its definite action proves, I think, that the current of electricity in the voltaic pile: is sustained by chemical decomposition, or rather by chemical action, and not by contact only. But here, as elsewhere (857.), I beg to reserve my opinion as to the real action of contact, not having yet been able to make up my mind as to whether it is an exciting cause of the current, or merely necessary to allow of the conduction of electricity, otherwise generated, from one metal to the other.

873. But admitting that chemical action is the source of electricity, what an infinitely small fraction of that which is active do we obtain and employ in our voltaic batteries! Zinc and platina wires, one-eighteenth of an inch in diameter and about half an inch long, dipped into dilute sulphuric acid, so weak that it is not sensibly sour to the tongue, or scarcely to our most delicate test-papers, will evolve more electricity in one-twentieth of a minute (860.) than any man would willingly allow to pass through his body at once. The chemical action of a grain of water upon four grains of zinc can evolve electricity equal in quantity to that of a powerful thunder-storm (868. 861.). Nor is it merely true that the quantity is active; it can be directed and made to perform its full equivalent duty (867. &c.). Is there not, then, great reason to hope and believe that, by a closer experimental investigation of the principles which govern the development and action of this subtile agent, we shall be able to increase the power of our batteries, or invent new instruments which shall a thousandfold surpass in energy those which we at present possess?

874. Here for a while I must leave the consideration of the definite chemical action of electricity. But before I dismiss this series of experimental Researches, I would call to mind that, in a former series, I showed the current of electricity was also definite in its magnetic action (216. 366. 367. 376. 377.); and, though this result was not pursued to any extent, I have no doubt that the success which has attended the development of the chemical effects is not more than would accompany an investigation of the magnetic phenomena.

Royal Institution, December 31st, 1833.

EIGHTH SERIES.

§14. On the Electricity of the Voltaic Pile; its source, quantity, intensity, and general characters. ¶ i. On simple Voltaic Circles. ¶ ii. On the intensity necessary for Electrolyzation. ¶ iii. On associated Voltaic Circles, or the Voltaic Battery. ¶ iv. On the resistance of an Electrolyte to Electrolytic action. ¶ v. General remarks on the active Voltaic Battery.

Received April 7,--Read June 5, 1831.

¶ i. On simple Voltaic Circles.

875. The great question of the source of electricity, in the voltaic pile has engaged the attention of so many eminent philosophers, that a man of liberal mind and able to appreciate their powers would probably conclude, although he might not have studied the question, that the truth was somewhere revealed. But if in pursuance of this impression he were induced to enter upon the work of collating results and conclusions, he would find such contradictory evidence, such equilibrium of opinion, such variation and combination of theory, as would leave him in complete doubt respecting what he should accept as the true interpretation of nature: he would be forced to take upon himself the labour of repeating and examining the facts, and then use his own judgement on them in preference to that of others.

876. This state of the subject must, to those who have made up their minds on the matter, be my apology for entering upon its investigation. The views I have taken of the definite action of electricity in decomposing bodies (783.), and the identity of the power so used with the power to be overcome (855.), founded not on a mere opinion or general notion, but on facts which, being altogether new, were to my mind precise and conclusive, gave me, as I conceived, the power of examining the question with advantages not before possessed by any, and which might compensate, on my part, for the superior clearness and extent of intellect on theirs. Such are the considerations which have induced me to suppose I might help in deciding the question, and be able to render assistance in that great service of removing doubtful knowledge. Such knowledge is the early morning light of every advancing science, and is essential to its development; but the man who is engaged in dispelling that which is deceptive in it, and revealing more clearly that which is true, is as useful in his place, and as necessary to the general progress of the science, as he who first broke through the intellectual darkness, and opened a path into knowledge before unknown to man.

877. The identity of the force constituting the voltaic current or electrolytic agent, with that which holds the elements of electrolytes together (855.), or in other words with chemical affinity, seemed to indicate that the electricity of the pile itself was merely a mode of exertion, or exhibition, or existence of true chemical action, or rather of its cause; and I have consequently already said that I agree with those who believe that the supply of electricity is due to chemical powers (857.).

878. But the great question of whether it is originally due to metallic contact or to chemical action, i.e. whether it is the first or the second which originates and determines the current, was to me still doubtful; and the beautiful and simple experiment with amalgamated zinc and platina, which I have described minutely as to its results (863, &c.), did not decide the point; for in that experiment the chemical action does not take place without the contact of the metals, and the metallic contact is inefficient without the chemical action. Hence either might be looked upon as the determining cause of the current.

879. I thought it essential to decide this question by the simplest possible forms of apparatus and experiment, that no fallacy might be inadvertently admitted. The well-known difficulty of effecting decomposition by a single pair of plates, except in the fluid exciting them into action (863.), seemed to throw insurmountable obstruction in the way of such experiments; but I remembered the easy decomposability of the solution of iodide of potassium (316.), and seeing no theoretical reason, if metallic contact was not essential, why true electro-decomposition should not be obtained without it, even in a single circuit, I persevered and succeeded.

880. A plate of zinc, about eight inches long and half an inch wide, was cleaned and bent in the middle to a right angle, fig. 73 a, Plate VI. A plate of platina, about three inches long and half an inch wide, was fastened to a platina wire, and the latter bent as in the figure, b. These two pieces of metal were arranged together as delineated, but as yet without the vessel c, and its contents, which consisted of dilute sulphuric acid mingled with a little nitric acid. At x a piece of folded bibulous paper, moistened in a solution of iodide of potassium, was placed on the zinc, and was pressed upon by the end of the platina wire. When under these circumstances the plates were dipped into the acid of the vessel c, there was an immediate effect at x, the iodide being decomposed, and iodine appearing at the anode (663.), i.e. against the end of the platina wire.

881. As long as the lower ends of the plates remained in the acid the electric current continued, and the decomposition proceeded at x. On removing the end of the wire from place to place on the paper, the effect was evidently very powerful; and on placing a piece of turmeric paper between the white paper and zinc, both papers being moistened with the solution of iodide of potassium, alkali was evolved at the cathode (663.) against the zinc, in proportion to the evolution of iodine at the anode. Hence the decomposition was perfectly polar, and decidedly dependent upon a current of electricity passing from the zinc through the acid to the platina in the vessel c, and back from the platina through the solution to the zinc at the paper x.

882. That the decomposition at x was a true electrolytic action, due to a current determined by the state of things in the vessel c, and not dependent upon any mere direct chemical action of the zinc and platina on the iodide, or even upon any current which the solution of iodide might by its action on those metals tend to form at x, was shown, in the first place, by removing the vessel c and its acid from the plates, when all decomposition at x ceased, and in the next by connecting the metals, either in or out of the acid, together, when decomposition of the iodide at x occurred, but in a reverse order; for now alkali appeared against the end of the platina wire, and the iodine passed to the zinc, the current being the contrary of what it was in the former instance, and produced directly by the difference of action of the solution in the paper on the two metals. The iodine of course combined with the zinc.

883. When this experiment was made with pieces of zinc amalgamated over the whole surface (863.), the results were obtained with equal facility and in the same direction, even when only dilute sulphuric acid was contained in the vessel c (fig. 73.). Whichsoever end of the zinc was immersed in the acid, still the effects were the same: so that if, for a moment, the mercury might be supposed to supply the metallic contact, the inversion of the amalgamated piece destroys that objection. The use of unamalgamated zinc (880.) removes all possibility of doubt.

The following is a more striking mode of making the above elementary experiment. Prepare a plate of zinc, ten or twelve inches long and two inches wide, and clean it thoroughly: provide also two discs of clean platina, about one inch and a half in diameter:--dip three or four folds of bibulous paper into a strong solution of iodide of potassium, place them on the clean zinc at one end of the plate, and put on them one of the platina discs: finally dip similar folds of paper or a piece of linen cloth into a mixture of equal parts nitric acid and water, and place it at the other end of the zinc plate with the second platina disc upon it. In this state of things no change at the solution of the iodide will be perceptible; but if the two discs be connected by a platina (or any other) wire for a second or two, and then that over the iodide be raised, it will be found that the whole of the surface beneath is deeply stained with evolved iodine.--Dec. 1838.

884 When, in pursuance of other views (930.), the vessel c was made to contain a solution of caustic potash in place of acid, still the same results occurred. Decomposition of the iodide was effected freely, though there was no metallic contact of dissimilar metals, and the current of electricity was in the same direction as when acid was used at the place of excitement.

885. Even a solution of common salt in the glass c could produce all these effects.

886. Having made a galvanometer with platina wires, and introduced it into the course of the current between the platina plate and the place of decomposition x, it was affected, giving indications of currents in the same direction as those shown to exist by the chemical action.

887. If we consider these results generally, they lead to very important conclusions. In the first place, they prove, in the most decisive manner, that metallic contact is not necessary for the production of the voltaic current. In the next place, they show a most extraordinary mutual relation of the chemical affinities of the fluid which excites the current, and the fluid which is decomposed by it.

888. For the purpose of simplifying the consideration, let us take the experiment with amalgamated zinc. The metal so prepared exhibits no effect until the current can pass: it at the same time introduces no new action, but merely removes an influence which is extraneous to those belonging either to the production or the effect of the electric current under investigation (1000.); an influence also which, when present, tends only to confuse the results.

889. Let two plates, one of amalgamated zinc and the other of platina, be placed parallel to each other (fig. 74.), and introduce a drop of dilute sulphuric acid, y, between them at one end: there will be no sensible chemical action at that spot unless the two plates are connected somewhere else, as at PZ, by a body capable of conducting electricity. If that body be a metal or certain forms of carbon, then the current passes, and, as it circulates through the fluid at y, decomposition ensues.