I. Voltaic Electricity.

268. Tension.—When a voltaic battery of 100 pairs of plates has its extremities examined by the ordinary electrometer, it is well known that they are found positive and negative, the gold leaves at the same extremity repelling each other, the gold leaves at different extremities attracting each other, even when half an inch or more of air intervenes.

269. That ordinary electricity is discharged by points with facility through air; that it is readily transmitted through highly rarefied air; and also through heated air, as for instance a flame; is due to its high tension. I sought, therefore, for similar effects in the discharge of voltaic electricity, using as a test of the passage of the electricity either the galvanometer or chemical action produced by the arrangement hereafter to be described (312. 316.).

270. The voltaic battery I had at my disposal consisted of 140 pairs of plates four inches square, with double coppers. It was insulated throughout, and diverged a gold leaf electrometer about one third of an inch. On endeavouring to discharge this battery by delicate points very nicely arranged and approximated, either in the air or in an exhausted receiver, I could obtain no indications of a current, either by magnetic or chemical action. In this, however, was found no point of discordance between voltaic and common electricity; for when a Leyden battery (291.) was charged so as to deflect the gold leaf electrometer to the same degree, the points were found equally unable to discharge it with such effect as to produce either magnetic or chemical action. This was not because common electricity could not produce both these effects (307. 310.); but because when of such low intensity the quantity required to make the effects visible (being enormously great (371. 375.),) could not be transmitted in any reasonable time. In conjunction with the other proofs of identity hereafter to be given, these effects of points also prove identity instead of difference between voltaic and common electricity.

271. As heated air discharges common electricity with far greater facility than points, I hoped that voltaic electricity might in this way also be discharged. An apparatus was therefore constructed (Plate III. fig. 46.), in which AB is an insulated glass rod upon which two copper wires, C, D, are fixed firmly; to these wires are soldered two pieces of fine platina wire, the ends of which are brought very close to each other at e, but without touching; the copper wire C was connected with the positive pole of a voltaic battery, and the wire D with a decomposing apparatus (312. 316.), from which the communication was completed to the negative pole of the battery. In these experiments only two troughs, or twenty pairs of plates, were used.

272. Whilst in the state described, no decomposition took place at the point a, but when the side of a spirit-lamp flame was applied to the two platina extremities at e, so as to make them bright red-hot, decomposition occurred; iodine soon appeared at the point a, and the transference of electricity through the heated air was established. On raising the temperature of the points e by a blowpipe, the discharge was rendered still more free, and decomposition took place instantly. On removing the source of heat, the current immediately ceased. On putting the ends of the wires very close by the side of and parallel to each other, but not touching, the effects were perhaps more readily obtained than before. On using a larger voltaic battery (270.), they were also more freely obtained.

273. On removing the decomposing apparatus and interposing a galvanometer instead, heating the points e as the needle would swing one way, and removing the heat during the time of its return (302.), feeble deflections were soon obtained: thus also proving the current through heated air; but the instrument used was not so sensible under the circumstances as chemical action.

274. These effects, not hitherto known or expected under this form, are only cases of the discharge which takes place through air between the charcoal terminations of the poles of a powerful battery, when they are gradually separated after contact. Then the passage is through heated air exactly as with common electricity, and Sir H. Davy has recorded that with the original battery of the Royal Institution this discharge passed through a space of at least four inches36. In the exhausted receiver the electricity would strike through nearly half an inch of space, and the combined effects of rarefaction and heat were such upon the inclosed air us to enable it to conduct the electricity through a space of six or seven inches.

275. The instantaneous charge of a Leyden battery by the poles of a voltaic apparatus is another proof of the tension, and also the quantity, of electricity evolved by the latter. Sir H. Davy says37, "When the two conductors from the ends of the combination were connected with a Leyden battery, one with the internal, the other with the external coating, the battery instantly became charged; and on removing the wires and making the proper connexions, either a shock or a spark could be perceived: and the least possible time of contact was sufficient to renew the charge to its full intensity."

276. In motion: i. Evolution of Heat.—The evolution of heat in wires and fluids by the voltaic current is matter of general notoriety.

277. ii. Magnetism.—No fact is better known to philosophers than the power of the voltaic current to deflect the magnetic needle, and to make magnets according to certain laws; and no effect can be more distinctive of an electrical current.

278. iii. Chemical decomposition.—The chemical powers of the voltaic current, and their subjection to certain laws, are also perfectly well known.

279. iv. Physiological effects.—The power of the voltaic current, when strong, to shock and convulse the whole animal system, and when weak to affect the tongue and the eyes, is very characteristic.

280. v. Spark.—The brilliant star of light produced by the discharge of a voltaic battery is known to all as the most beautiful light that man can produce by art.

* * * * *

281. That these effects may be almost infinitely varied, some being exalted whilst others are diminished, is universally acknowledged; and yet without any doubt of the identity of character of the voltaic currents thus made to differ in their effect. The beautiful explication of these variations afforded by Cavendish's theory of quantity and intensity requires no support at present, as it is not supposed to be doubted.

282. In consequence of the comparisons that will hereafter arise between wires carrying voltaic and ordinary electricities, and also because of certain views of the condition of a wire or any other conducting substance connecting the poles of a voltaic apparatus, it will be necessary to give some definite expression of what is called the voltaic current, in contradistinction to any supposed peculiar state of arrangement, not progressive, which the wire or the electricity within it may be supposed to assume. If two voltaic troughs PN, P'N', fig. 42, be symmetrically arranged and insulated, and the ends NP' connected by a wire, over which a magnetic needle is suspended, the wire will exert no effect over the needle; but immediately that the ends PN' are connected by another wire, the needle will be deflected, and will remain so as long as the circuit is complete. Now if the troughs merely act by causing a peculiar arrangement in the wire either of its particles or its electricity, that arrangement constituting its electrical and magnetic state, then the wire NP' should be in a similar state of arrangement before P and N' were connected, to what it is afterwards, and should have deflected the needle, although less powerfully, perhaps to one half the extent which would result when the communication is complete throughout. But if the magnetic effects depend upon a current, then it is evident why they could not be produced in any degree before the circuit was complete; because prior to that no current could exist.

283. By current, I mean anything progressive, whether it be a fluid of electricity, or two fluids moving in opposite directions, or merely vibrations, or, speaking still more generally, progressive forces. By arrangement, I understand a local adjustment of particles, or fluids, or forces, not progressive. Many other reasons might be urged in support of the view of a current rather than an arrangement, but I am anxious to avoid stating unnecessarily what will occur to others at the moment.

II. Ordinary Electricity.

284. By ordinary electricity I understand that which can be obtained from the common machine, or from the atmosphere, or by pressure, or cleavage of crystals, or by a multitude of other operations; its distinctive character being that of great intensity, and the exertion of attractive and repulsive powers, not merely at sensible but at considerable distances.

285. Tension. The attractions and repulsions at sensible distances, caused by ordinary electricity, are well known to be so powerful in certain cases, as to surpass, almost infinitely, the similar phenomena produced by electricity, otherwise excited. But still those attractions and repulsions are exactly of the same nature as those already referred to under the head Tension, Voltaic electricity (268.); and the difference in degree between them is not greater than often occurs between cases of ordinary electricity only. I think it will be unnecessary to enter minutely into the proofs of the identity of this character in the two instances. They are abundant; are generally admitted as good; and lie upon the surface of the subject: and whenever in other parts of the comparison I am about to draw, a similar case occurs, I shall content myself with a mere announcement of the similarity, enlarging only upon those parts where the great question of distinction or identity still exists.

286. The discharge of common electricity through heated air is a well-known fact. The parallel case of voltaic electricity has already been described (272, &c.).

287. In motion. i. Evolution of heat.—The heating power of common electricity, when passed through wires or other substances, is perfectly well known. The accordance between it and voltaic electricity is in this respect complete. Mr. Harris has constructed and described38 a very beautiful and sensible instrument on this principle, in which the heat produced in a wire by the discharge of a small portion of common electricity is readily shown, and to which I shall have occasion to refer for experimental proof in a future part of this paper (344.).

288. ii. Magnetism.—Voltaic electricity has most extraordinary and exalted magnetic powers. If common electricity be identical with it, it ought to have the same powers. In rendering needles or bars magnetic, it is found to agree with voltaic electricity, and the direction of the magnetism, in both cases, is the same; but in deflecting the magnetic needle, common electricity has been found deficient, so that sometimes its power has been denied altogether, and at other times distinctions have been hypothetically assumed for the purpose of avoiding the difficulty39.

289. M. Colladon, of Geneva, considered that the difference might be due to the use of insufficient quantities of common electricity in all the experiments before made on this head; and in a memoir read to the Academie des Sciences in 182640, describes experiments, in which, by the use of a battery, points, and a delicate galvanometer, he succeeded in obtaining deflections, and thus establishing identity in that respect. MM. Arago, Ampère, and Savary, are mentioned in the paper as having witnessed a successful repetition of the experiments. But as no other one has come forward in confirmation, MM. Arago, Ampère, and Savary, not having themselves published (that I am aware of) their admission of the results, and as some have not been able to obtain them, M. Colladon's conclusions have been occasionally doubted or denied; and an important point with me was to establish their accuracy, or remove them entirely from the body of received experimental research. I am happy to say that my results fully confirm those by M. Colladon, and I should have had no occasion to describe them, but that they are essential as proofs of the accuracy of the final and general conclusions I am enabled to draw respecting the magnetic and chemical action of electricity (360. 366. 367. 377. &c.).

290. The plate electrical machine I have used is fifty inches in diameter; it has two sets of rubbers; its prime conductor consists of two brass cylinders connected by a third, the whole length being twelve feet, and the surface in contact with air about 1422 square inches. When in good excitation, one revolution of the plate will give ten or twelve sparks from the conductors, each an inch in length. Sparks or flashes from ten to fourteen inches in length may easily be drawn from the conductors. Each turn of the machine, when worked moderately, occupies about 4/5ths of a second.

291. The electric battery consisted of fifteen equal jars. They are coated eight inches upwards from the bottom, and are twenty-three inches in circumference, so that each contains one hundred and eighty-four square inches of glass, coated on both sides; this is independent of the bottoms, which are of thicker glass, and contain each about fifty square inches.

292. A good discharging train was arranged by connecting metallically a sufficiently thick wire with the metallic gas pipes of the house, with the metallic gas pipes belonging to the public gas works of London; and also with the metallic water pipes of London. It was so effectual in its office as to carry off instantaneously electricity of the feeblest tension, even that of a single voltaic trough, and was essential to many of the experiments.

293. The galvanometer was one or the other of those formerly described (87. 205.), but the glass jar covering it and supporting the needle was coated inside and outside with tinfoil, and the upper part (left uncoated, that the motions of the needle might be examined,) was covered with a frame of wire-work, having numerous sharp points projecting from it. When this frame and the two coatings were connected with the discharging train (292.), an insulated point or ball, connected with the machine when most active, might be brought within an inch of any part of the galvanometer, yet without affecting the needle within by ordinary electrical attraction or repulsion.

294. In connexion with these precautions, it may be necessary to state that the needle of the galvanometer is very liable to have its magnetic power deranged, diminished, or even inverted by the passage of a shock through the instrument. If the needle be at all oblique, in the wrong direction, to the coils of the galvanometer when the shock passes, effects of this kind are sure to happen.

295. It was to the retarding power of bad conductors, with the intention of diminishing its intensity without altering its quantity, that I first looked with the hope of being able to make common electricity assume more of the characters and power of voltaic electricity, than it is usually supposed to have.

296, The coating and armour of the galvanometer were first connected with the discharging train (292.); the end B (87.) of the galvanometer wire was connected with the outside coating of the battery, and then both these with the discharging train; the end A of the galvanometer wire was connected with a discharging rod by a wet thread four feet long; and finally, when the battery (291.) had been positively charged by about forty turns of the machine, it was discharged by the rod and the thread through the galvanometer. The needle immediately moved.

297. During the time that the needle completed its vibration in the first direction and returned, the machine was worked, and the battery recharged; and when the needle in vibrating resumed its first direction, the discharge was again made through the galvanometer. By repeating this action a few times, the vibrations soon extended to above 40° on each side of the line of rest.

298. This effect could be obtained at pleasure. Nor was it varied, apparently, either in direction or degree, by using a short thick string, or even four short thick strings in place of the long fine thread. With a more delicate galvanometer, an excellent swing of the needle could be obtained by one discharge of the battery.

299. On reversing the galvanometer communications so as to pass the discharge through from B to A, the needle was equally well deflected, but in the opposite direction.

300. The deflections were in the same direction as if a voltaic current had been passed through the galvanometer, i.e. the positively charged surface of the electric battery coincided with the positive end of the voltaic apparatus (268.) and the negative surface of the former with the negative end of the latter.

301. The battery was then thrown out of use, and the communications so arranged that the current could be passed from the prime conductor, by the discharging rod held against it, through the wet string, through the galvanometer coil, and into the discharging train (292), by which it was finally dispersed. This current could be stopped at any moment, by removing the discharging rod, and either stopping the machine or connecting the prime conductor by another rod with the discharging train; and could be as instantly renewed. The needle was so adjusted, that whilst vibrating in moderate and small arcs, it required time equal to twenty-five beats of a watch to pass in one direction through the arc, and of course an equal time to pass in the other direction.

302. Thus arranged, and the needle being stationary, the current, direct from the machine, was sent through the galvanometer for twenty-five beats, then interrupted for other twenty-five beats, renewed for twenty-five beats more, again interrupted for an equal time, and so on continually. The needle soon began to vibrate visibly, and after several alternations of this kind, the vibration increased to 40° or more.

303. On changing the direction of the current through the galvanometer, the direction of the deflection of the needle was also changed. In all cases the motion of the needle was in direction the same as that caused either by the use of the electric battery or a voltaic trough (300).

304. I now rejected the wet string, and substituted a copper wire, so that the electricity of the machine passed at once into wires communicating directly with the discharging train, the galvanometer coil being one of the wires used for the discharge. The effects were exactly those obtained above (302).

305. Instead of passing the electricity through the system, by bringing the discharging rod at the end of it into contact with the conductor, four points were fixed on to the rod; when the current was to pass, they were held about twelve inches from the conductor, and when it was not to pass, they were turned away. Then operating as before (302.), except with this variation, the needle was soon powerfully deflected, and in perfect consistency with the former results. Points afforded the means by which Colladon, in all cases, made his discharges.

306. Finally, I passed the electricity first through an exhausted receiver, so as to make it there resemble the aurora borealis, and then through the galvanometer to the earth; and it was found still effective in deflecting the needle, and apparently with the same force as before.

307. From all these experiments, it appears that a current of common electricity, whether transmitted through water or metal, or rarefied air, or by means of points in common air, is still able to deflect the needle; the only requisite being, apparently, to allow time for its action: that it is, in fact, just as magnetic in every respect as a voltaic current, and that in this character therefore no distinction exists.

308. Imperfect conductors, as water, brine, acids, &c. &c. will be found far more convenient for exhibiting these effects than other modes of discharge, as by points or balls; for the former convert at once the charge of a powerful battery into a feeble spark discharge, or rather continuous current, and involve little or no risk of deranging the magnetism of the needles (294.).

309. iii. Chemical decomposition.—The chemical action of voltaic electricity is characteristic of that agent, but not more characteristic than are the laws under which the bodies evolved by decomposition arrange themselves at the poles. Dr. Wollaston showed41 that common electricity resembled it in these effects, and "that they are both essentially the same"; but he mingled with his proofs an experiment having a resemblance, and nothing more, to a case of voltaic decomposition, which however he himself partly distinguished; and this has been more frequently referred to by some, on the one hand, to prove the occurrence of electro-chemical decomposition, like that of the pile, and by others to throw doubt upon the whole paper, than the more numerous and decisive experiments which he has detailed.

310. I take the liberty of describing briefly my results, and of thus adding my testimony to that of Dr. Wollaston on the identity of voltaic and common electricity as to chemical action, not only that I may facilitate the repetition of the experiments, but also lead to some new consequences respecting electrochemical decomposition (376. 377.).

311. I first repeated Wollaston's fourth experiment42, in which the ends of coated silver wires are immersed in a drop of sulphate of copper. By passing the electricity of the machine through such an arrangement, that end in the drop which received the electricity became coated with metallic copper. One hundred turns of the machine produced an evident effect; two hundred turns a very sensible one. The decomposing action was however very feeble. Very little copper was precipitated, and no sensible trace of silver from the other pole appeared in the solution.

312. A much more convenient and effectual arrangement for chemical decompositions by common electricity, is the following. Upon a glass plate, fig. 43, placed over, but raised above a piece of white paper, so that shadows may not interfere, put two pieces of tinfoil a, b; connect one of these by an insulated wire c, or wire and string (301.) with the machine, and the other g, with the discharging train (292.) or the negative conductor; provide two pieces of fine platina wire, bent as in fig. 44, so that the part d, f shall be nearly upright, whilst the whole is resting on the three bearing points p, e, f place these as in fig. 43; the points p, n then become the decomposing poles. In this way surfaces of contact, as minute as possible, can be obtained at pleasure, and the connexion can be broken or renewed in a moment, and the substances acted upon examined with the utmost facility.

313. A coarse line was made on the glass with solution of sulphate of copper, and the terminations p and n put into it; the foil a was connected with the positive conductor of the machine by wire and wet string, so that no sparks passed: twenty turns of the machine caused the precipitation of so much copper on the end n, that it looked like copper wire; no apparent change took place at p.

314. A mixture of equal parts of muriatic acid and water was rendered deep blue by sulphate of indigo, and a large drop put on the glass, fig. 43, so that p and n were immersed at opposite sides: a single turn of the machine showed bleaching effects round p, from evolved chlorine. After twenty revolutions no effect of the kind was visible at n, but so much chlorine had been set free at p, that when the drop was stirred the whole became colourless.

315. A drop of solution of iodide of potassium mingled with starch was put into the same position at p and n; on turning the machine, iodine was evolved at p, but not at n.

316. A still further improvement in this form of apparatus consists in wetting a piece of filtering paper in the solution to be experimented on, and placing that under the points p and n, on the glass: the paper retains the substance evolved at the point of evolution, by its whiteness renders any change of colour visible, and allows of the point of contact between it and the decomposing wires being contracted to the utmost degree. A piece of paper moistened in the solution of iodide of potassium and starch, or of the iodide alone, with certain precautions (322.), is a most admirable test of electro-chemical action; and when thus placed and acted upon by the electric current, will show iodine evolved at p by only half a turn of the machine. With these adjustments and the use of iodide of potassium on paper, chemical action is sometimes a more delicate test of electrical currents than the galvanometer (273.). Such cases occur when the bodies traversed by the current are bad conductors, or when the quantity of electricity evolved or transmitted in a given time is very small.

317. A piece of litmus paper moistened in solution of common salt or sulphate of soda, was quickly reddened at p. A similar piece moistened in muriatic acid was very soon bleached at p. No effects of a similar kind took place at n.

318. A piece of turmeric paper moistened in solution of sulphate of soda was reddened at n by two or three turns of the machine, and in twenty or thirty turns plenty of alkali was there evolved. On turning the paper round, so that the spot came under p, and then working the machine, the alkali soon disappeared, the place became yellow, and a brown alkaline spot appeared in the new part under n.

319. On combining a piece of litmus with a piece of turmeric paper, wetting both with solution of sulphate of soda, and putting the paper on the glass, so that p was on the litmus and n on the turmeric, a very few turns of the machine sufficed to show the evolution of acid at the former and alkali at the latter, exactly in the manner effected by a volta-electric current.

320. All these decompositions took place equally well, whether the electricity passed from the machine to the foil a, through water, or through wire only; by contact with the conductor, or by sparks there; provided the sparks were not so large as to cause the electricity to pass in sparks from p to n, or towards n; and I have seen no reason to believe that in cases of true electro-chemical decomposition by the machine, the electricity passed in sparks from the conductor, or at any part of the current, is able to do more, because of its tension, than that which is made to pass merely as a regular current.

321. Finally, the experiment was extended into the following form, supplying in this case the tidiest analogy between common and voltaic electricity. Three compound pieces of litmus and turmeric paper (319.) were moistened in solution of sulphate of soda, and arranged on a plate of glass with platina wires, as in fig. 45. The wire m was connected with the prime conductor of the machine, the wire t with the discharging train, and the wires r and s entered into the course of the electrical current by means of the pieces of moistened paper; they were so bent as to rest each on three points, n, r, p; n, s, p, the points r and s being supported by the glass, and the others by the papers; the three terminations p, p, p rested on the litmus, and the other three n, n, n on the turmeric paper. On working the machine for a short time only, acid was evolved at all the poles or terminations p, p, p, by which the electricity entered the solution, and alkali at the other poles n, n, n, by which the electricity left the solution.

322. In all experiments of electro-chemical decomposition by the common machine and moistened papers (316.), it is necessary to be aware of and to avoid the following important source of error. If a spark passes over moistened litmus and turmeric paper, the litmus paper (provided it be delicate and not too alkaline,) is reddened by it; and if several sparks are passed, it becomes powerfully reddened. If the electricity pass a little way from the wire over the surface of the moistened paper, before it finds mass and moisture enough to conduct it, then the reddening extends as far as the ramifications. If similar ramifications occur at the termination n, on the turmeric paper, they prevent the occurrence of the red spot due to the alkali, which would otherwise collect there: sparks or ramifications from the points n will also redden litmus paper. If paper moistened by a solution of iodide of potassium (which is an admirably delicate test of electro-chemical action,) be exposed to the sparks or ramifications, or even a feeble stream of electricity through the air from either the point p or n, iodine will be immediately evolved.

323. These effects must not be confounded with those due to the true electro-chemical powers of common electricity, and must be carefully avoided when the latter are to be observed. No sparks should be passed, therefore, in any part of the current, nor any increase of intensity allowed, by which the electricity may be induced to pass between the platina wires and the moistened papers, otherwise than by conduction; for if it burst through the air, the effect referred to above (322.) ensues.

324. The effect itself is due to the formation of nitric acid by the combination of the oxygen and nitrogen of the air, and is, in fact, only a delicate repetition of Cavendish's beautiful experiment. The acid so formed, though small in quantity, is in a high state of concentration as to water, and produces the consequent effects of reddening the litmus paper; or preventing the exhibition of alkali on the turmeric paper; or, by acting on the iodide of potassium, evolving iodine.

325. By moistening a very small slip of litmus paper in solution of caustic potassa, and then passing the electric spark over its length in the air, I gradually neutralized the alkali, and ultimately rendered the paper red; on drying it, I found that nitrate of potassa had resulted from the operation, and that the paper had become touch-paper.

326. Either litmus paper or white paper, moistened in a strong solution of iodide of potassium, offers therefore a very simple, beautiful, and ready means of illustrating Cavendish's experiment of the formation of nitric acid from the atmosphere.

327. I have already had occasion to refer to an experiment (265. 309.) made by Dr. Wollaston, which is insisted upon too much, both by those who oppose and those who agree with the accuracy of his views respecting the identity of voltaic and ordinary electricity. By covering fine wires with glass or other insulating substances, and then removing only so much matter as to expose the point, or a section of the wires, and by passing electricity through two such wires, the guarded points of which were immersed in water, Wollaston found that the water could be decomposed even by the current from the machine, without sparks, and that two streams of gas arose from the points, exactly resembling, in appearance, those produced by voltaic electricity, and, like the latter, giving a mixture of oxygen and hydrogen gases. But Dr. Wollaston himself points out that the effect is different from that of the voltaic pile, inasmuch as both oxygen and hydrogen are evolved from each pole; he calls it "a very close imitation of the galvanic phenomena," but adds that "in fact the resemblance is not complete," and does not trust to it to establish the principles correctly laid down in his paper.

328. This experiment is neither more nor less than a repetition, in a refined manner, of that made by Dr. Pearson in 179743, and previously by MM. Paets Van Troostwyk and Deiman in 1789 or earlier. That the experiment should never be quoted as proving true electro-chemical decomposition, is sufficiently evident from the circumstance, that the law which regulates the transference and final place of the evolved bodies (278. 309.) has no influence here. The water is decomposed at both poles independently of each other, and the oxygen and hydrogen evolved at the wires are the elements of the water existing the instant before in those places. That the poles, or rather points, have no mutual decomposing dependence, may be shown by substituting a wire, or the finger, for one of them, a change which does not at all interfere with the other, though it stops all action at the changed pole. This fact may be observed by turning the machine for some time; for though bubbles will rise from the point left unaltered, in quantity sufficient to cover entirely the wire used for the other communication, if they could be applied to it, yet not a single bubble will appear on that wire.

329. When electro-chemical decomposition takes place, there is great reason to believe that the quantity of matter decomposed is not proportionate to the intensity, but to the quantity of electricity passed (320.). Of this I shall be able to offer some proofs in a future part of this paper (375. 377.). But in the experiment under consideration, this is not the case. If, with a constant pair of points, the electricity be passed from the machine in sparks, a certain proportion of gas is evolved; but if the sparks be rendered shorter, less gas is evolved; and if no sparks be passed, there is scarcely a sensible portion of gases set free. On substituting solution of sulphate of soda for water, scarcely a sensible quantity of gas could be procured even with powerful sparks, and nearly none with the mere current; yet the quantity of electricity in a given time was the same in all these cases.

330. I do not intend to deny that with such an apparatus common electricity can decompose water in a manner analogous to that of the voltaic pile; I believe at present that it can. But when what I consider the true effect only was obtained, the quantity of gas given off was so small that I could not ascertain whether it was, as it ought to be, oxygen at one wire and hydrogen at the other. Of the two streams one seemed more copious than the other, and on turning the apparatus round, still the same side in relation to the machine; gave the largest stream. On substituting solution of sulphate of soda for pure water (329.), these minute streams were still observed. But the quantities were so small, that on working the machine for half an hour I could not obtain at either pole a bubble of gas larger than a small grain of sand. If the conclusion which I have drawn (377.) relating to the amount of chemical action be correct, this ought to be the case.

331. I have been the more anxious to assign the true value of this experiment as a test of electro-chemical action, because I shall have occasion to refer to it in cases of supposed chemical action by magneto-electric and other electric currents (336. 346.) and elsewhere. But, independent of it, there cannot be now a doubt that Dr. Wollaston was right in his general conclusion; and that voltaic and common electricity have powers of chemical decomposition, alike in their nature, and governed by the same law of arrangement.

332. iv. Physiological effects.—The power of the common electric current to shock and convulse the animal system, and when weak to affect the tongue and the eyes, may be considered as the same with the similar power of voltaic electricity, account being taken of the intensity of the one electricity and duration of the other. When a wet thread was interposed in the course of the current of common electricity from the battery (291.) charged by eight or ten44 revolutions of the machine in good action (290.), and the discharge made by platina spatulas through the tongue or the gums, the effect upon the tongue and eyes was exactly that of a momentary feeble voltaic circuit.

333. v. Spark.—The beautiful flash of light attending the discharge of common electricity is well known. It rivals in brilliancy, if it does not even very much surpass, the light from the discharge of voltaic electricity; but it endures for an instant only, and is attended by a sharp noise like that of a small explosion. Still no difficulty can arise in recognising it to be the same spark as that from the voltaic battery, especially under certain circumstances. The eye cannot distinguish the difference between a voltaic and a common electricity spark, if they be taken between amalgamated surfaces of metal, at intervals only, and through the same distance of air.

334. When the Leyden battery (291.) was discharged through a wet string placed in some part of the circuit away from the place where the spark was to pass, the spark was yellowish, flamy, having a duration sensibly longer than if the water had not been interposed, was about three-fourths of an inch in length, was accompanied by little or no noise, and whilst losing part of its usual character had approximated in some degree to the voltaic spark. When the electricity retarded by water was discharged between pieces of charcoal, it was exceedingly luminous and bright upon both surfaces of the charcoal, resembling the brightness of the voltaic discharge on such surfaces. When the discharge of the unretarded electricity was taken upon charcoal, it was bright upon both the surfaces, (in that respect resembling the voltaic spark,) but the noise was loud, sharp, and ringing.

335. I have assumed, in accordance, I believe, with the opinion of every other philosopher, that atmospheric electricity is of the same nature with ordinary electricity (284.), and I might therefore refer to certain published statements of chemical effects produced by the former as proofs that the latter enjoys the power of decomposition in common with voltaic electricity. But the comparison I am drawing is far too rigorous to allow me to use these statements without being fully assured of their accuracy; yet I have no right to suppress them, because, if accurate, they establish what I am labouring to put on an undoubted foundation, and have priority to my results.

336. M. Bonijol of Geneva45 is said to have constructed very delicate apparatus for the decomposition of water by common electricity. By connecting an insulated lightning rod with his apparatus, the decomposition of the water proceeded in a continuous and rapid manner even when the electricity of the atmosphere was not very powerful. The apparatus is not described; but as the diameter of the wire is mentioned as very small, it appears to have been similar in construction to that of Wollaston (327.); and as that does not furnish a case of true polar electro-chemical decomposition (328.), this result of M. Bonijol does not prove the identity in chemical action of common and voltaic electricity.

337. At the same page of the Bibliothèque Universelle, M. Bonijol is said to have decomposed, potash, and also chloride of silver, by putting them into very narrow tubes and passing electric sparks from an ordinary machine over them. It is evident that these offer no analogy to cases of true voltaic decomposition, where the electricity only decomposes when it is conducted by the body acted upon, and ceases to decompose, according to its ordinary laws, when it passes in sparks. These effects are probably partly analogous to that which takes place with water in Pearson's or Wollaston's apparatus, and may be due to very high temperature acting on minute portions of matter; or they may be connected with the results in air (322.). As nitrogen can combine directly with oxygen under the influence of the electric spark (324.), it is not impossible that it should even take it from the potassium of the potash, especially as there would be plenty of potassa in contact with the acting particles to combine with the nitric acid formed. However distinct all these actions may be from true polar electro-chemical decompositions, they are still highly important, and well-worthy of investigation.

338. The late Mr. Barry communicated a paper to the Royal Society46 last year, so distinct in the details, that it would seem at once to prove the identity in chemical action of common and voltaic electricity; but, when examined, considerable difficulty arises in reconciling certain of the effects with the remainder. He used two tubes, each having a wire within it passing through the closed end, as is usual for voltaic decompositions. The tubes were filled with solution of sulphate of soda, coloured with syrup of violets, and connected by a portion of the same solution, in the ordinary manner; the wire in one tube was connected by a gilt thread with the string of an insulated electrical kite, and the wire in the other tube by a similar gilt thread with the ground. Hydrogen soon appeared in the tube connected with the kite, and oxygen in the other, and in ten minutes the liquid in the first tube was green from the alkali evolved, and that in the other red from free acid produced. The only indication of the strength or intensity of the atmospheric electricity is in the expression, "the usual shocks were felt on touching the string."

339. That the electricity in this case does not resemble that from any ordinary source of common electricity, is shown by several circumstances. Wollaston could not effect the decomposition of water by such an arrangement, and obtain the gases in separate vessels, using common electricity; nor have any of the numerous philosophers, who have employed such an apparatus, obtained any such decomposition, either of water or of a neutral salt, by the use of the machine. I have lately tried the large machine (290.) in full action for a quarter of an hour, during which time seven hundred revolutions were made, without producing any sensible effects, although the shocks that it would then give must have been far more powerful and numerous than could have been taken, with any chance of safety, from an electrical kite-string; and by reference to the comparison hereafter to be made (371.), it will be seen that for common electricity to have produced the effect, the quantity must have been awfully great, and apparently far more than could have been conducted to the earth by a gilt thread, and at the same time only have produced the "usual shocks."

340. That the electricity was apparently not analogous to voltaic electricity is evident, for the "usual shocks" only were produced, and nothing like the terrible sensation due to a voltaic battery, even when it has a tension so feeble as not to strike through the eighth of an inch of air.

341. It seems just possible that the air which was passing by the kite and string, being in an electrical state sufficient to produce the "usual shocks" only, could still, when the electricity was drawn off below, renew the charge, and so continue the current. The string was 1500 feet long, and contained two double threads. But when the enormous quantity which must have been thus collected is considered (371. 376.), the explanation seems very doubtful. I charged a voltaic battery of twenty pairs of plates four inches square with double coppers very strongly, insulated it, connected its positive extremity with the discharging train (292.), and its negative pole with an apparatus like that of Mr. Barry, communicating by a wire inserted three inches into the wet soil of the ground. This battery thus arranged produced feeble decomposing effects, as nearly as I could judge answering the description Mr. Barry has given. Its intensity was, of course, far lower than the electricity of the kite-string, but the supply of quantity from the discharging train was unlimited. It gave no shocks to compare with the "usual shocks" of a kite-string.

342. Mr. Barry's experiment is a very important one to repeat and verify. If confirmed, it will be, as far as I am aware, the first recorded case of true electro-chemical decomposition of water by common electricity, and it will supply a form of electrical current, which, both in quantity and intensity, is exactly intermediate with those of the common electrical machine and the voltaic pile.

III. Magneto-Electricity.

343. Tension.—The attractions and repulsions due to the tension of ordinary electricity have been well observed with that evolved by magneto-electric induction. M. Pixii, by using an apparatus, clever in its construction and powerful in its action47, was able to obtain great divergence of the gold leaves of an electrometer48.

344. In motion: i. Evolution of Heat.—The current produced by magneto-electric induction can heat a wire in the manner of ordinary electricity. At the British Association of Science at Oxford, in June of the present year, I had the pleasure, in conjunction with Mr. Harris, Professor Daniell, Mr. Duncan, and others, of making an experiment, for which the great magnet in the museum, Mr. Harris's new electrometer (287.), and the magneto-electric coil described in my first paper (34.), were put in requisition. The latter had been modified in the manner I have elsewhere described49 so as to produce an electric spark when its contact with the magnet was made or broken. The terminations of the spiral, adjusted so as to have their contact with each other broken when the spark was to pass, were connected with the wire in the electrometer, and it was found that each time the magnetic contact was made and broken, expansion of the air within the instrument occurred, indicating an increase, at the moment, of the temperature of the wire.

345. ii. Magnetism.—These currents were discovered by their magnetic power.

346. iii. Chemical decomposition.—I have made many endeavours to effect chemical decomposition by magneto-electricity, but unavailingly. In July last I received an anonymous letter (which has since been published50,) describing a magneto-electric apparatus, by which the decomposition of water was effected. As the term "guarded points" is used, I suppose the apparatus to have been Wollaston's (327. &c.), in which case the results did not indicate polar electro-chemical decomposition. Signor Botto has recently published certain results which he has obtained51; but they are, as at present described, inconclusive. The apparatus he used was apparently that of Dr. Wollaston, which gives only fallacious indications (327. &c.). As magneto-electricity can produce sparks, it would be able to show the effects proper to this apparatus. The apparatus of M. Pixii already referred to (343.) has however, in the hands of himself52 and M. Hachctte53, given decisive chemical results, so as to complete this link in the chain of evidence. Water was decomposed by it, and the oxygen and hydrogen obtained in separate tubes according to the law governing volta-electric and machine-electric decomposition.

347. iv. Physiological effects.—A frog was convulsed in the earliest experiments on these currents (56.). The sensation upon the tongue, and the flash before the eyes, which I at first obtained only in a feeble degree (56.), have been since exalted by more powerful apparatus, so as to become even disagreeable.

348. v. Spark.—The feeble spark which I first obtained with these currents (32.), has been varied and strengthened by Signori Nobili and Antinori, and others, so as to leave no doubt as to its identity with the common electric spark.

IV. Thermo-Electricity.

349. With regard to thermo-electricity, (that beautiful form of electricity discovered by Seebeck,) the very conditions under which it is excited are such as to give no ground for expecting that it can be raised like common electricity to any high degree of tension; the effects, therefore, due to that state are not to be expected. The sum of evidence respecting its analogy to the electricities already described, is, I believe, as follows:—Tension. The attractions and repulsions due to a certain degree of tension have not been observed. In currents: i. Evolution of Heat. I am not aware that its power of raising temperature has been observed. ii. Magnetism. It was discovered, and is best recognised, by its magnetic powers. iii. Chemical decomposition has not been effected by it. iv. Physiological effects. Nobili has shown54 that these currents are able to cause contractions in the limbs of a frog. v. Spark. The spark has not yet been seen.

350. Only those effects are weak or deficient which depend upon a certain high degree of intensity; and if common electricity be reduced in that quality to a similar degree with the thermo-electricity, it can produce no effects beyond the latter.

V. Animal Electricity.

351. After an examination of the experiments of Walsh55 Ingenhousz56, Cavendish57, Sir H. Davy58, and Dr. Davy59, no doubt remains on my mind as to the identity of the electricity of the torpedo with common and voltaic electricity; and I presume that so little will remain on the minds of others as to justify my refraining from entering at length into the philosophical proofs of that identity. The doubts raised by Sir H. Davy have been removed by his brother Dr. Davy; the results of the latter being the reverse of those of the former. At present the sum of evidence is as follows:—

352. Tension.—No sensible attractions or repulsions due to tension have been observed.

353. In motion: i. Evolution of Heat; not yet observed; I have little or no doubt that Harris's electrometer would show it (287. 359.).

354. ii. Magnetism.—Perfectly distinct. According to Dr. Davy60, the current deflected the needle and made magnets under the same law, as to direction, which governs currents of ordinary and voltaic electricity.

355. iii. Chemical decomposition.—Also distinct; and though Dr. Davy used an apparatus of similar construction with that of Dr. Wollaston (327.), still no error in the present case is involved, for the decompositions were polar, and in their nature truly electro-chemical. By the direction of the magnet it was found that the under surface of the fish was negative, and the upper positive; and in the chemical decompositions, silver and lead were precipitated on the wire connected with the under surface, and not on the other; and when these wires were either steel or silver, in solution of common salt, gas (hydrogen?) rose from the negative wire, but none from the positive.

356. Another reason for the decomposition being electrochemical is, that a Wollaston's apparatus constructed with wires, coated by sealing-wax, would most probably not have decomposed water, even in its own peculiar way, unless the electricity had risen high enough in intensity to produce sparks in some part of the circuit; whereas the torpedo was not able to produce sensible sparks. A third reason is, that the purer the water in Wollaston's apparatus, the more abundant is the decomposition; and I have found that a machine and wire points which succeeded perfectly well with distilled water, failed altogether when the water was rendered a good conductor by sulphate of soda, common salt, or other saline bodies. But in Dr. Davy's experiments with the torpedo, strong solutions of salt, nitrate of silver, and superacetate of lead were used successfully, and there is no doubt with more success than weaker ones.

357. iv. Physiological effects.—These are so characteristic, that by them the peculiar powers of the torpedo and gymnotus are principally recognised.

358. v. Spark.—The electric spark has not yet been obtained, or at least I think not; but perhaps I had better refer to the evidence on this point. Humboldt, speaking of results obtained by M. Fahlberg, of Sweden, says, "This philosopher has seen an electric spark, as Walsh and Ingenhousz had done before him in London, by placing the gymnotus in the air, and interrupting the conducting chain by two gold leaves pasted upon glass, and a line distant from each other61." I cannot, however, find any record of such an observation by either Walsh or Ingenhousz, and do not know where to refer to that by M. Fahlberg. M. Humboldt could not himself perceive any luminous effect.

Again, Sir John Leslie, in his dissertation on the progress of mathematical and physical science, prefixed to the seventh edition of the Encyclopædia Britannica, Edinb. 1830, p. 622, says, "From a healthy specimen" of the Silurus electricus, meaning rather the gymnotus, "exhibited in London, vivid sparks were drawn in a darkened room"; but he does not say he saw them himself, nor state who did see them; nor can I find any account of such a phenomenon; so that the statement is doubtful62.

359. In concluding this summary of the powers of torpedinal electricity, I cannot refrain from pointing out the enormous absolute quantity of electricity which the animal must put in circulation at each effort. It is doubtful whether any common electrical machine has as yet been able to supply electricity sufficient in a reasonable time to cause true electro-chemical decomposition of water (330. 339.), yet the current from the torpedo has done it. The same high proportion is shown by the magnetic effects (296. 371.). These circumstances indicate that the torpedo has power (in the way probably that Cavendish describes,) to continue the evolution for a sensible time, so that its successive discharges rather resemble those of a voltaic arrangement, intermitting in its action, than those of a Leyden apparatus, charged and discharged many times in succession. In reality, however, there is no philosophical difference between these two cases.

360. The general conclusion which must, I think, be drawn from this collection of facts is, that electricity, whatever may be its source, is identical in its nature. The phenomena in the five kinds or species quoted, differ, not in their character but only in degree; and in that respect vary in proportion to the variable circumstances of quantity and intensity63 which can at pleasure be made to change in almost any one of the kinds of electricity, as much as it does between one kind and another.

Table of the experimental Effects common to the Electricities derived from different Sources64.

¶ i. New conditions of Electro-chemical Decomposition.

453. The tension of machine electricity causes it, however small in quantity, to pass through any length of water, solutions, or other substances classing with these as conductors, as fast as it can be produced, and therefore, in relation to quantity, as fast as it could have passed through much shorter portions of the same conducting substance. With the voltaic battery the case is very different, and the passing current of electricity supplied by it suffers serious diminution in any substance, by considerable extension of its length, but especially in such bodies as those mentioned above.

454. I endeavoured to apply this facility of transmitting the current of electricity through any length of a conductor, to an investigation of the transfer of the elements in a decomposing body, in contrary directions, towards the poles. The general form of apparatus used in these experiments has been already described (312. 316); and also a particular experiment (319.), in which, when a piece of litmus paper and a piece of turmeric paper were combined and moistened in solution of sulphate of soda, the point of the wire from the machine (representing the positive pole) put upon the litmus paper, and the receiving point from the discharging train (292. 316.), representing the negative pole, upon the turmeric paper, a very few turns of the machine sufficed to show the evolution of acid at the former, and alkali at the latter, exactly in the manner effected by a volta-electric current.

455. The pieces of litmus and turmeric paper were now placed each upon a separate plate of glass, and connected by an insulated string four feet long, moistened in the same solution of sulphate of soda: the terminal decomposing wire points were placed upon the papers as before. On working the machine, the same evolution of acid and alkali appeared as in the former instance, and with equal readiness, notwithstanding that the places of their appearance were four feet apart from each other. Finally, a piece of string, seventy feet long, was used. It was insulated in the air by suspenders of silk, so that the electricity passed through its entire length: decomposition took place exactly as in former cases, alkali and acid appearing at the two extremities in their proper places.

456. Experiments were then made both with sulphate of soda and iodide of potassium, to ascertain if any diminution of decomposing effect was produced by such great extension as those just described of the moist conductor or body under decomposition; but whether the contact of the decomposing point connected with the discharging train was made with turmeric paper touching the prime conductor, or with other turmeric paper connected with it through the seventy feet of string, the spot of alkali for an equal number of turns of the machine had equal intensity of colour. The same results occurred at the other decomposing wire, whether the salt or the iodide were used; and it was fully proved that this great extension of the distance between the poles produced no effect whatever on the amount of decomposition, provided the same quantity of electricity were passed in both cases (377.).

457. The negative point of the discharging train, the turmeric paper, and the string were then removed; the positive point was left resting upon the litmus paper, and the latter touched by a piece of moistened string held in the hand. A few turns of the machine evolved acid at the positive point as freely as before.

458. The end of the moistened string, instead of being held in the hand, was suspended by glass in the air. On working the machine the electricity proceeded from the conductor through the wire point to the litmus paper, and thence away by the intervention of the string to the air, so that there was (as in the last experiment) but one metallic pole; still acid was evolved there as freely as in any former case.

459. When any of these experiments were repeated with electricity from the negative conductor, corresponding effects were produced whether one or two decomposing wires were used. The results were always constant, considered in relation to the direction of the electric current.

460. These experiments were varied so as to include the action of only one metallic pole, but that not the pole connected with the machine. Turmeric paper was moistened in solution of sulphate of soda, placed upon glass, and connected with the discharging train (292.) by a decomposing wire (312.); a piece of wet string was hung from it, the lower extremity of which was brought opposite a point connected with the positive prime conductor of the machine. The machine was then worked for a few turns, and alkali immediately appeared at the point of the discharging train which rested on the turmeric paper. Corresponding effects took place at the negative conductor of a machine.

461. These cases are abundantly sufficient to show that electrochemical decomposition does not depend upon the simultaneous action of two metallic poles, since a single pole might be used, decomposition ensue, and one or other of the elements liberated, pass to the pole, according as it was positive or negative. In considering the course taken by, and the final arrangement of, the other element, I had little doubt that I should find it had receded towards the other extremity, and that the air itself had acted as a pole, an expectation which was fully confirmed in the following manner.

462. A piece of turmeric paper, not more than 0.4 of an inch in length and 0.5 of an inch in width, was moistened with sulphate of soda and placed upon the edge of a glass plate opposite to, and about two inches from, a point connected with the discharging train (Plate IV. fig. 47.); a piece of tinfoil, resting upon the same glass plate, was connected with the machine, and also with the turmeric paper, by a decomposing wire a (312.). The machine was then worked, the positive electricity passing into the turmeric paper at the point p, and out at the extremity n. After forty or fifty turns of the machine, the extremity n was examined, and the two points or angles found deeply coloured by the presence of free alkali (fig. 48.).

463. A similar piece of litmus paper, dipped in solution of sulphate of soda n, fig. 49, was now supported upon the end of the discharging train a, and its extremity brought opposite to a point p, connected with the conductor of the machine. After working the machine for a short time, acid was developed at both the corners towards the point, i.e. at both the corners receiving the electricities from the air. Every precaution was taken to prevent this acid from being formed by sparks or brushes passing through the air (322.); and these, with the accompanying general facts, are sufficient to show that the acid was really the result of electro-chemical decomposition (466.).

464. Then a long piece of turmeric paper, large at one end and pointed at the other, was moistened in the saline solution, and immediately connected with the conductor of the machine, so that its pointed extremity was opposite a point upon the discharging train. When the machine was worked, alkali was evolved at that point; and even when the discharging train was removed, and the electricity left to be diffused and carried off altogether by the air, still alkali was evolved where the electricity left the turmeric paper.

465. Arrangements were then made in which no metallic communication with the decomposing matter was allowed, but both poles (if they might now be called by that name) formed of air only. A piece of turmeric paper a fig. 50, and a piece of litmus paper b, were dipped in solution of sulphate of soda, put together so as to form one moist pointed conductor, and supported on wax between two needle points, one, p, connected by a wire with the conductor of the machine, and the other, n, with the discharging train. The interval in each case between the points was about half an inch; the positive point p was opposite the litmus paper; the negative point n opposite the turmeric. The machine was then worked for a time, upon which evidence of decomposition quickly appeared, for the point of the litmus b became reddened from acid evolved there, and the point of the turmeric a red from a similar and simultaneous evolution of alkali.

466. Upon turning the paper conductor round, so that the litmus point should now give off the positive electricity, and the turmeric point receive it, and working the machine for a short time, both the red spots disappeared, and as on continuing the action of the machine no red spot was re-formed at the litmus extremity, it proved that in the first instance (463.) the effect was not due to the action of brushes or mere electric discharges causing the formation of nitric acid from the air (322.).

467. If the combined litmus and turmeric paper in this experiment be considered as constituting a conductor independent of the machine or the discharging train, and the final places of the elements evolved be considered in relation to this conductor, then it will be found that the acid collects at the negative or receiving end or pole of the arrangement, and the alkali at the positive or delivering extremity.

468. Similar litmus and turmeric paper points were now placed upon glass plates, and connected by a string six feet long, both string and paper being moistened in solution of sulphate of soda; a needle point connected with the machine was brought opposite the litmus paper point, and another needle point connected with the discharging train brought opposite the turmeric paper. On working the machine, acid appeared on the litmus, and alkali on the turmeric paper; but the latter was not so abundant as in former cases, for much of the electricity passed off from the string into the air, and diminished the quantity discharged at the turmeric point.

469. Finally, a series of four small compound conductors, consisting of litmus and turmeric paper (fig. 51.) moistened in solution of sulphate of soda, were supported on glass rods, in a line at a little distance from each other, between the points p and n of the machine and discharging train, so that the electricity might pass in succession through them, entering in at the litmus points b, b, and passing out at the turmeric points a, a. On working the machine carefully, so as to avoid sparks and brushes (322.), I soon obtained evidence of decomposition in each of the moist conductors, for all the litmus points exhibited free acid, and the turmeric points equally showed free alkali.

470. On using solutions of iodide of potassium, acetate of lead, &c., similar effects were obtained; but as they were all consistent with the results above described, I refrain from describing the appearances minutely.

471. These cases of electro-chemical decomposition are in their nature exactly of the same kind as those affected under ordinary circumstances by the voltaic battery, notwithstanding the great differences as to the presence or absence, or at least as to the nature of the parts usually called poles; and also of the final situation of the elements eliminated at the electrified boundary surfaces (467.). They indicate at once an internal action of the parts suffering decomposition, and appear to show that the power which is effectual in separating the elements is exerted there, and not at the poles. But I shall defer the consideration of this point for a short time (493. 518.), that I may previously consider another supposed condition of electro-chemical decomposition83.

¶ ii. Influence of Water in Electro-chemical Decomposition.

472. It is the opinion of several philosophers, that the presence of water is essential in electro-chemical decomposition, and also for the evolution of electricity in the voltaic battery itself. As the decomposing cell is merely one of the cells of the battery, into which particular substances are introduced for the purpose of experiment, it is probable that what is an essential condition in the one case is more or less so in the other. The opinion, therefore, that water is necessary to decomposition, may have been founded on the statement made by Sir Humphry Davy, that "there are no fluids known, except such as contain water, which are capable of being made the medium of connexion between the metals or metal of the voltaic apparatus84:" and again, "when any substance rendered fluid by heat, consisting of water, oxygen, and inflammable or metallic matter, is exposed to those wires, similar phenomena (of decomposition) occur85."

473. This opinion has, I think, been shown by other philosophers not to be accurate, though I do not know where to refer for a contradiction of it. Sir Humphry Davy himself said in 180186, that dry nitre, caustic potash and soda are conductors of galvanism when rendered fluid by a high degree of heat, but he must have considered them, or the nitre at least, as not suffering decomposition, for the statements above were made by him eleven years subsequently. In 1826 he also pointed out, that bodies not containing water, as fused litharge and chlorate of potassa, were sufficient to form, with platina and zinc, powerful electromotive circles87; but he is here speaking of the production of electricity in the pile, and not of its effects when evolved; nor do his words at all imply that any correction of his former distinct statements relative to decomposition was required.

474. I may refer to the last series of these Experimental Researches (380. 402.) as setting the matter at rest, by proving that there are hundreds of bodies equally influential with water in this respect; that amongst binary compounds, oxides, chlorides, iodides, and even sulphurets (402.) were effective; and that amongst more complicated compounds, cyanides and salts, of equal efficacy, occurred in great numbers (402.).

475. Water, therefore, is in this respect merely one of a very numerous class of substances, instead of being the only one and essential; and it is of that class one of the worst as to its capability of facilitating conduction and suffering decomposition. The reasons why it obtained for a time an exclusive character which it so little deserved are evident, and consist, in the general necessity of a fluid condition (394.); in its being the only one of this class of bodies existing in the fluid state at common temperatures; its abundant supply as the great natural solvent; and its constant use in that character in philosophical investigations, because of its having a smaller interfering, injurious, or complicating action upon the bodies, either dissolved or evolved, than any other substance.

476. The analogy of the decomposing or experimental cell to the other cells of the voltaic battery renders it nearly certain that any of those substances which are decomposable when fluid, as described in my last paper (402.), would, if they could be introduced between the metallic plates of the pile, be equally effectual with water, if not more so. Sir Humphry Davy found that litharge and chlorate of potassa were thus effectual88. I have constructed various voltaic arrangements, and found the above conclusion to hold good. When any of the following substances in a fused state were interposed between copper and platina, voltaic action more or less powerful was produced. Nitre; chlorate of potassa; carbonate of potassa; sulphate of soda; chloride of lead, of sodium, of bismuth, of calcium; iodide of lead; oxide of bismuth; oxide of lead: the electric current was in the same direction as if acids had acted upon the metals. When any of the same substances, or phosphate of soda, were made to act on platina and iron, still more powerful voltaic combinations of the same kind were produced. When either nitrate of silver or chloride of silver was the fluid substance interposed, there was voltaic action, but the electric current was in the reverse direction.

¶ iii. Theory of Electro-chemical Decomposition.

477. The extreme beauty and value of electro-chemical decompositions have given to that power which the voltaic pile possesses of causing their occurrence an interest surpassing that of any other of its properties; for the power is not only intimately connected with the continuance, if not with the production, of the electrical phenomena, but it has furnished us with the most beautiful demonstrations of the nature of many compound bodies; has in the hands of Becquerel been employed in compounding substances; has given us several new combinations, and sustains us with the hope that when thoroughly understood it will produce many more.

478. What may be considered as the general facts of electrochemical decomposition are agreed to by nearly all who have written on the subject. They consist in the separation of the decomposable substance acted upon into its proximate or sometimes ultimate principles, whenever both poles of the pile are in contact with that substance in a proper condition; in the evolution of these principles at distant points, i.e. at the poles of the pile, where they are either finally set free or enter into union with the substance of the poles; and in the constant determination of the evolved elements or principles to particular poles according to certain well-ascertained laws.

479. But the views of men of science vary much as to the nature of the action by which these effects are produced; and as it is certain that we shall be better able to apply the power when we really understand the manner in which it operates, this difference of opinion is a strong inducement to further inquiry. I have been led to hope that the following investigations might be considered, not as an increase of that which is doubtful, but a real addition to this branch of knowledge.

480. It will be needful that I briefly state the views of electro-chemical decomposition already put forth, that their present contradictory and unsatisfactory state may be seen before I give that which seems to me more accurately to agree with facts; and I have ventured to discuss them freely, trusting that I should give no offence to their high-minded authors; for I felt convinced that if I were right, they would be pleased that their views should serve as stepping-stones for the advance of science; and that if I were wrong, they would excuse the zeal which misled me, since it was exerted for the service of that great cause whose prosperity and progress they have desired.

481. Grotthuss, in the year 1805, wrote expressly on the decomposition of liquids by voltaic electricity89. He considers the pile as an electric magnet, i.e. as an attractive and repulsive agent; the poles having attractive and repelling powers. The pole from whence resinous electricity issues attracts hydrogen and repels oxygen, whilst that from which vitreous electricity proceeds attracts oxygen and repels hydrogen; so that each of the elements of a particle of water, for instance, is subject to an attractive and a repulsive force, acting in contrary directions, the centres of action of which are reciprocally opposed. The action of each force in relation to a molecule of water situated in the course of the electric current is in the inverse ratio of the square of the distance at which it is exerted, thus giving (it is stated) for such a molecule a constant force90. He explains the appearance of the elements at a distance from each other by referring to a succession of decompositions and recompositions occurring amongst the intervening particles91, and he thinks it probable that those which are about to separate at the poles unite to the two electricities there, and in consequence become gases92.

482. Sir Humphry Davy's celebrated Bakerian Lecture on some chemical agencies of electricity was read in November 1806, and is almost entirely occupied in the consideration of electro-chemical decompositions. The facts are of the utmost value, and, with the general points established, are universally known. The mode of action by which the effects take place is stated very generally, so generally, indeed, that probably a dozen precise schemes of electro-chemical action might be drawn up, differing essentially from each other, yet all agreeing with the statement there given.

483. When Sir Humphry Davy uses more particular expressions, he seems to refer the decomposing effects to the attractions of the poles. This is the case in the "general expression of facts" given at pp. 28 and 29 of the Philosophical Transactions for 1807, also at p. 30. Again at p. 160 of the Elements of Chemical Philosophy, he speaks of the great attracting powers of the surfaces of the poles. He mentions the probability of a succession of decompositions and recompositions throughout the fluid,—agreeing in that respect with Grotthuss93; and supposes that the attractive and repellent agencies may be communicated from the metallic surfaces throughout the whole of the menstruum94, being communicated from one particle to another particle of the same kind95, and diminishing in strength from the place of the poles to the middle point, which is necessarily neutral96. In reference to this diminution of power at increased distances from the poles, he states that in a circuit of ten inches of water, solution of sulphate of potassa placed four inches from the positive pole, did not decompose; whereas when only two inches from that pole, it did render up its elements97.

484. When in 1826 Sir Humphry Davy wrote again on this subject, he stated that he found nothing to alter in the fundamental theory laid down in the original communication98, and uses the terms attraction and repulsion apparently in the same sense as before99.

485. Messrs. Riffault and Chompré experimented on this subject in 1807. They came to the conclusion that the voltaic current caused decompositions throughout its whole course in the humid conductor, not merely as preliminary to the recompositions spoken of by Grotthuss and Davy, but producing final separation of the elements in the course of the current, and elsewhere than at the poles. They considered the negative current as collecting and carrying the acids, &c. to the positive pole, and the positive current as doing the same duty with the bases, and collecting them at the negative pole. They likewise consider the currents as more powerful the nearer they are to their respective poles, and state that the positive current is superior in power to the negative current100.

486. M. Biot is very cautious in expressing an opinion as to the cause of the separation of the elements of a compound body101. But as far as the effects can be understood, he refers them to the opposite electrical states of the portions of the decomposing substance in the neighbourhood of the two poles. The fluid is most positive at the positive pole; that state gradually diminishes to the middle distance, where the fluid is neutral or not electrical; but from thence to the negative pole it becomes more and more negative102. When a particle of salt is decomposed at the negative pole, the acid particle is considered as acquiring a negative electrical state from the pole, stronger than that of the surrounding undecomposed particles, and is therefore repelled from amongst them, and from out of that portion of the liquid towards the positive pole, towards which also it is drawn by the attraction of the pole itself and the particles of positive undecomposed fluid around it103.

487. M. Biot does not appear to admit the successive decompositions and recompositions spoken of by Grotthuss, Davy, &c. &c.; but seems to consider the substance whilst in transit as combined with, or rather attached to, the electricity for the time104, and though it communicates this electricity to the surrounding undecomposed matter with which it is in contact, yet it retains during the transit a little superiority with respect to that kind which it first received from the pole, and is, by virtue of that difference, carried forward through the fluid to the opposite pole105.

488. This theory implies that decomposition takes place at both poles upon distinct portions of fluid, and not at all in the intervening parts. The latter serve merely as imperfect conductors, which, assuming an electric state, urge particles electrified more highly at the poles through them in opposite directions, by virtue of a series of ordinary electrical attractions and repulsions106.

489. M.A. de la Rive investigated this subject particularly, and published a paper on it in 1825107. He thinks those who have referred the phenomena to the attractive powers of the poles, rather express the general fact than give any explication of it. He considers the results as due to an actual combination of the elements, or rather of half of them, with the electricities passing from the poles in consequence of a kind of play of affinities between the matter and electricity108. The current from the positive pole combining with the hydrogen, or the bases it finds there, leaves the oxygen and acids at liberty, but carries the substances it is united with across to the negative pole, where, because of the peculiar character of the metal as a conductor109, it is separated from them, entering the metal and leaving the hydrogen or bases upon its surface. In the same manner the electricity from the negative pole sets the hydrogen and bases which it finds there, free, but combines with the oxygen and acids, carries them across to the positive pole, and there deposits them110. In this respect M. de la Rive's hypothesis accords in part with that of MM. Riffault and Chompré (485.).

490. M. de la Rive considers the portions of matter which are decomposed to be those contiguous to both poles111. He does not admit with others the successive decompositions and recompositions in the whole course of the electricity through the humid conductor112, but thinks the middle parts are in themselves unaltered, or at least serve only to conduct the two contrary currents of electricity and matter which set off from the opposite poles113. The decomposition, therefore, of a particle of water, or a particle of salt, may take place at either pole, and when once effected, it is final for the time, no recombination taking place, except the momentary union of the transferred particle with the electricity be so considered.

491. The latest communication that I am aware of on the subject is by M. Hachette: its date is October 1832114. It is incidental to the description of the decomposition of water by the magneto-electric currents (346.). One of the results of the experiment is, that "it is not necessary, as has been supposed, that for the chemical decomposition of water, the action of the two electricities, positive and negative, should be simultaneous."

492. It is more than probable that many other views of electro-chemical decomposition may have been published, and perhaps amongst them some which, differing from those above, might, even in my own opinion, were I acquainted with them, obviate the necessity for the publication of my views. If such be the case, I have to regret my ignorance of them, and apologize to the authors.

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493. That electro-chemical decomposition does not depend upon any direct attraction and repulsion of the poles (meaning thereby the metallic terminations either of the voltaic battery, or ordinary electrical machine arrangements (312.),) upon the elements in contact with or near to them, appeared very evident from the experiments made in air (462, 465, &c.), when the substances evolved did not collect about any poles, but, in obedience to the direction of the current, were evolved, and I would say ejected, at the extremities of the decomposing substance. But notwithstanding the extreme dissimilarity in the character of air and metals, and the almost total difference existing between them as to their mode of conducting electricity, and becoming charged with it, it might perhaps still be contended, although quite hypothetically, that the bounding portions of air were now the surfaces or places of attraction, as the metals had been supposed to be before. In illustration of this and other points, I endeavoured to devise an arrangement by which I could decompose a body against a surface of water, as well as against air or metal, and succeeded in doing so unexceptionably in the following manner. As the experiment for very natural reasons requires many precautions, to be successful, and will be referred to hereafter in illustration of the views I shall venture to give, I must describe it minutely.

494. A glass basin (fig. 52.), four inches in diameter and four inches deep, had a division of mica a, fixed across the upper part so as to descend one inch and a half below the edge, and be perfectly water-tight at the sides: a plate of platina b, three inches wide, was put into the basin on one side of the division a, and retained there by a glass block below, so that any gas produced by it in a future stage of the experiment should not ascend beyond the mica, and cause currents in the liquid on that side. A strong solution of sulphate of magnesia was carefully poured without splashing into the basin, until it rose a little above the lower edge of the mica division a, great care being taken that the glass or mica on the unoccupied or c side of the division in the figure, should not be moistened by agitation of the solution above the level to which it rose. A thin piece of clean cork, well-wetted in distilled water, was then carefully and lightly placed on the solution at the c side, and distilled water poured gently on to it until a stratum the eighth of an inch in thickness appeared over the sulphate of magnesia; all was then left for a few minutes, that any solution adhering to the cork might sink away from it, or be removed by the water on which it now floated; and then more distilled water was added in a similar manner, until it reached nearly to the top of the glass. In this way solution of the sulphate occupied the lower part of the glass, and also the upper on the right-hand side of the mica; but on the left-hand side of the division a stratum of water from c to d, one inch and a half in depth, reposed upon it, the two presenting, when looked through horizontally, a comparatively definite plane of contact. A second platina pole e, was arranged so as to be just under the surface of the water, in a position nearly horizontal, a little inclination being given to it, that gas evolved during decomposition might escape: the part immersed was three inches and a half long by one inch wide, and about seven-eighths of an inch of water intervened between it and the solution of sulphate of magnesia.

495. The latter pole e was now connected with the negative end of a voltaic battery, of forty pairs of plates four inches square, whilst the former pole b was connected with the positive end. There was action and gas evolved at both poles; but from the intervention of the pure water, the decomposition was very feeble compared to what the battery would have effected in a uniform solution. After a little while (less than a minute,) magnesia also appeared at the negative side: it did not make its appearance at the negative metallic pole, but in the water, at the plane where the solution and the water met; and on looking at it horizontally, it could be there perceived lying in the water upon the solution, not rising more than the fourth of an inch above the latter, whilst the water between it and the negative pole was perfectly clear. On continuing the action, the bubbles of hydrogen rising upwards from the negative pole impressed a circulatory movement on the stratum of water, upwards in the middle, and downwards at the side, which gradually gave an ascending form to the cloud of magnesia in the part just under the pole, having an appearance as if it were there attracted to it; but this was altogether an effect of the currents, and did not occur until long after the phenomena looked for were satisfactorily ascertained.

496. After a little while the voltaic communication was broken, and the platina poles removed with as little agitation as possible from the water and solution, for the purpose of examining the liquid adhering to them. The pole c, when touched by turmeric paper, gave no traces of alkali, nor could anything but pure water be found upon it. The pole b, though drawn through a much greater depth and quantity of fluid, was found so acid as to give abundant evidence to litmus paper, the tongue, and other tests. Hence there had been no interference of alkaline salts in any way, undergoing first decomposition, and then causing the separation of the magnesia at a distance from the pole by mere chemical agencies. This experiment was repeated again and again, and always successfully.

497. As, therefore, the substances evolved in cases of electrochemical decomposition may be made to appear against air (465. 469.),—which, according to common language, is not a conductor, nor is decomposed, or against water (495.), which is a conductor, and can be decomposed,—as well as against the metal poles, which are excellent conductors, but undecomposable, there appears but little reason to consider the phenomena generally, as due to the attraction or attractive powers of the latter, when used in the ordinary way, since similar attractions can hardly be imagined in the former instances.

498. It may be said that the surfaces of air or of water in these cases become the poles, and exert attractive powers; but what proof is there of that, except the fact that the matters evolved collect there, which is the point to be explained, and cannot be justly quoted as its own explanation? Or it may be said, that any section of the humid conductor, as that in the present case, where the solution and the water meet, may be considered as representing the pole. But such does not appear to me to be the view of those who have written on the subject, certainly not of some of them, and is inconsistent with the supposed laws which they have assumed, as governing the diminution of power at increased distances from the poles.

499. Grotthuss, for instance, describes the poles as centres of attractive and repulsive forces (481.), these forces varying inversely as the squares of the distances, and says, therefore, that a particle placed anywhere between the poles will be acted upon by a constant force. But the compound force, resulting from such a combination as he supposes, would be anything but a constant force; it would evidently be a force greatest at the poles, and diminishing to the middle distance. Grotthuss is right, however, in the fact, according to my experiments (502. 505.), that the particles are acted upon by equal force everywhere in the circuit, when the conditions of the experiment are the simplest possible; but the fact is against his theory, and is also, I think, against all theories that place the decomposing effect in the attractive power of the poles.

500. Sir Humphry Davy, who also speaks of the diminution of power with increase of distance from the poles115 (483.), supposes, that when both poles are acting on substances to decompose them, still the power of decomposition diminishes to the middle distance. In this statement of fact he is opposed to Grotthuss, and quotes an experiment in which sulphate of potassa, placed at different distances from the poles in a humid conductor of constant length, decomposed when near the pole, but not when at a distance. Such a consequence would necessarily result theoretically from considering the poles as centres of attraction and repulsion; but I have not found the statement borne out by other experiments (505.); and in the one quoted by him the effect was doubtless due to some of the many interfering causes of variation which attend such investigations.

501. A glass vessel had a platina plate fixed perpendicularly across it, so as to divide it into two cells: a head of mica was fixed over it, so as to collect the gas it might evolve during experiments; then each cell, and the space beneath the mica, was filled with dilute sulphuric acid. Two poles were provided, consisting each of a platina wire terminated by a plate of the same metal; each was fixed into a tube passing through its upper end by an air-tight joint, that it might be moveable, and yet that the gas evolved at it might be collected. The tubes were filled with the acid, and one immersed in each cell. Each platina pole was equal in surface to one side of the dividing plate in the middle glass vessel, and the whole might be considered as an arrangement between the poles of the battery of a humid decomposable conductor divided in the middle by the interposed platina diaphragm. It was easy, when required, to draw one of the poles further up the tube, and then the platina diaphragm was no longer in the middle of the humid conductor. But whether it were thus arranged at the middle, or towards one side, it always evolved a quantity of oxygen and hydrogen equal to that evolved by both the extreme plates116.

502. If the wires of a galvanometer be terminated by plates, and these be immersed in dilute acid, contained in a regularly formed rectangular glass trough, connected at each end with a voltaic battery by poles equal to the section of the fluid, a part of the electricity will pass through the instrument and cause a certain deflection. And if the plates are always retained at the same distance from each other and from the sides of the trough, are always parallel to each other, and uniformly placed relative to the fluid, then, whether they are immersed near the middle of the decomposing solution, or at one end, still the instrument will indicate the same deflection, and consequently the same electric influence.

503. It is very evident, that when the width of the decomposing conductor varies, as is always the case when mere wires or plates, as poles, are dipped into or are surrounded by solution, no constant expression can be given as to the action upon a single particle placed in the course of the current, nor any conclusion of use, relative to the supposed attractive or repulsive force of the poles, be drawn. The force will vary as the distance from the pole varies; as the particle is directly between the poles, or more or less on one side; and even as it is nearer to or further from the sides of the containing vessels, or as the shape of the vessel itself varies; and, in fact, by making variations in the form of the arrangement, the force upon any single particle may be made to increase, or diminish, or remain constant, whilst the distance between the particle and the pole shall remain the same; or the force may be made to increase, or diminish, or remain constant, either as the distance increases or as it diminishes.

504. From numerous experiments, I am led to believe the following general expression to be correct; but I purpose examining it much further, and would therefore wish not to be considered at present as pledged to its accuracy. The sum of chemical decomposition is constant for any section taken across a decomposing conductor, uniform in its nature, at whatever distance the poles may be from each other or from the section; or however that section may intersect the currents, whether directly across them, or so oblique as to reach almost from pole to pole, or whether it be plane, or curved, or irregular in the utmost degree; provided the current of electricity be retained constant in quantity (377.), and that the section passes through every part of the current through the decomposing conductor.

505. I have reason to believe that the statement might be made still more general, and expressed thus: That for a constant quantity of electricity, whatever the decomposing conductor may be, whether water, saline solutions, acids, fused bodies, &c., the amount of electro-chemical action is also a constant quantity, i.e. would always be equivalent to a standard chemical effect founded upon ordinary chemical affinity. I have this investigation in hand, with several others, and shall be prepared to give it in the next series but one of these Researches.

506. Many other arguments might be adduced against the hypotheses of the attraction of the poles being the cause of electro-chemical decomposition; but I would rather pass on to the view I have thought more consistent with facts, with this single remark; that if decomposition by the voltaic battery depended upon the attraction of the poles, or the parts about them, being stronger than the mutual attraction of the particles separated, it would follow that the weakest electrical attraction was stronger than, if not the strongest, yet very strong chemical attraction, namely, such as exists between oxygen and hydrogen, potassium and oxygen, chlorine and sodium, acid and alkali, &c., a consequence which, although perhaps not impossible, seems in the present state of the subject very unlikely.

507. The view which M. de la Rive has taken (489.), and also MM. Riffault and Chompré (485.), of the manner in which electro-chemical decomposition is effected, is very different to that already considered, and is not affected by either the arguments or facts urged against the latter. Considering it as stated by the former philosopher, it appears to me to be incompetent to account for the experiments of decomposition against surfaces of air (462. 469.) and water (495.), which I have described; for if the physical differences between metals and humid conductors, which M. de la Rive supposes to account for the transmission of the compound of matter and electricity in the latter, and the transmission of the electricity only with the rejection of the matter in the former, be allowed for a moment, still the analogy of air to metal is, electrically considered, so small, that instead of the former replacing the latter (462.), an effect the very reverse might have been expected. Or if even that were allowed, the experiment with water (495.), at once sets the matter at rest, the decomposing pole being now of a substance which is admitted as competent to transmit the assumed compound of electricity and matter.

508. With regard to the views of MM. Riffault and Chompré (485.), the occurrence of decomposition alone in the course of the current is so contrary to the well-known effects obtained in the forms of experiment adopted up to this time, that it must be proved before the hypothesis depending on it need be considered.

509. The consideration of the various theories of electro-chemical decomposition, whilst it has made me diffident, has also given me confidence to add another to the number; for it is because the one I have to propose appears, after the most attentive consideration, to explain and agree with the immense collection of facts belonging to this branch of science, and to remain uncontradicted by, or unopposed to, any of them, that I have been encouraged to give it.

510. Electro-chemical decomposition is well known to depend essentially upon the current of electricity. I have shown that in certain cases (375.) the decomposition is proportionate to the quantity of electricity passing, whatever may be its intensity or its source, and that the same is probably true for all cases (377.), even when the utmost generality is taken on the one hand, and great precision of expression on the other (505.).

511. In speaking of the current, I find myself obliged to be still more particular than on a former occasion (283.), in consequence of the variety of views taken by philosophers, all agreeing in the effect of the current itself. Some philosophers, with Franklin, assume but one electric fluid; and such must agree together in the general uniformity and character of the electric current. Others assume two electric fluids; and here singular differences have arisen.

512. MM. Riffault and Chompré, for instance, consider the positive and negative currents each as causing decomposition, and state that the positive current is more powerful than the negative current117, the nitrate of soda being, under similar circumstances, decomposed by the former, but not by the latter.

513. M. Hachette states118 that "it is not necessary, as has been believed, that the action of the two electricities, positive and negative, should be simultaneous for the decomposition of water." The passage implying, if I have caught the meaning aright, that one electricity can be obtained, and can be applied in effecting decompositions, independent of the other.

514. The view of M. de la Rive to a certain extent agrees with that of M. Hachette, for he considers that the two electricities decompose separate portions of water (490.)119. In one passage he speaks of the two electricities as two influences, wishing perhaps to avoid offering a decided opinion upon the independent existence of electric fluids; but as these influences are considered as combining with the elements set free as by a species of chemical affinity, and for the time entirely masking their character, great vagueness of idea is thus introduced, inasmuch as such a species of combination can only be conceived to take place between things having independent existences. The two elementary electric currents, moving in opposite directions, from pole to pole, constitute the ordinary voltaic current.

515. M. Grotthuss is inclined to believe that the elements of water, when about to separate at the poles, combine with the electricities, and so become gases. M. de la Rive's view is the exact reverse of this: whilst passing through the fluid, they are, according to him, compounds with the electricities; when evolved at the poles, they are de-electrified.

516. I have sought amongst the various experiments quoted in support of these views, or connected with electro-chemical decompositions or electric currents, for any which might be considered as sustaining the theory of two electricities rather than that of one, but have not been able to perceive a single fact which could be brought forward for such a purpose: or, admitting the hypothesis of two electricities, much less have I been able to perceive the slightest grounds for believing that one electricity in a current can be more powerful than the other, or that it can be present without the other, or that one can be varied or in the slightest degree affected, without a corresponding variation in the other120. If, upon the supposition of two electricities, a current of one can be obtained without the other, or the current of one be exalted or diminished more than the other, we might surely expect some variation either of the chemical or magnetical effects, or of both; but no such variations have been observed. If a current be so directed that it may act chemically in one part of its course, and magnetically in another, the two actions are always found to take place together. A current has not, to my knowledge, been produced which could act chemically and not magnetically, nor any which can act on the magnet, and not at the same time chemically121.

517. Judging from facts only, there is not as yet the slightest reason for considering the influence which is present in what we call the electric current,—whether in metals or fused bodies or humid conductors, or even in air, flame, and rarefied elastic media,—as a compound or complicated influence. It has never been resolved into simpler or elementary influences, and may perhaps best be conceived of as an axis of power having contrary forces, exactly equal in amount, in contrary directions.

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518. Passing to the consideration of electro-chemical decomposition, it appears to me that the effect is produced by an internal corpuscular action, exerted according to the direction of the electric current, and that it is due to a force either super to, or giving direction to the ordinary chemical affinity of the bodies present. The body under decomposition may be considered as a mass of acting particles, all those which are included in the course of the electric current contributing to the final effect; and it is because the ordinary chemical affinity is relieved, weakened, or partly neutralized by the influence of the electric current in one direction parallel to the course of the latter, and strengthened or added to in the opposite direction, that the combining particles have a tendency to pass in opposite courses.

519. In this view the effect is considered as essentially dependent upon the mutual chemical affinity of the particles of opposite kinds. Particles aa, fig. 53, could not be transferred or travel from one pole N towards the other P, unless they found particles of the opposite kind bb, ready to pass in the contrary direction: for it is by virtue of their increased affinity for those particles, combined with their diminished affinity for such as are behind them in their course, that they are urged forward: and when any one particle a, fig. 54, arrives at the pole, it is excluded or set free, because the particle b of the opposite kind, with which it was the moment before in combination, has, under the superinducing influence of the current, a greater attraction for the particle a', which is before it in its course, than for the particle a, towards which its affinity has been weakened.

520. As far as regards any single compound particle, the case may be considered as analogous to one of ordinary decomposition, for in fig. 54, a may be conceived to be expelled from the compound ab by the superior attraction of a' for b, that superior attraction belonging to it in consequence of the relative position of a'b and a to the direction of the axis of electric power (517.) superinduced by the current. But as all the compound particles in the course of the current, except those actually in contact with the poles, act conjointly, and consist of elementary particles, which, whilst they are in one direction expelling, are in the other being expelled, the case becomes more complicated, but not more difficult of comprehension.

521. It is not here assumed that the acting particles must be in a right line between the poles. The lines of action which may be supposed to represent the electric currents passing through a decomposing liquid, have in many experiments very irregular forms; and even in the simplest case of two wires or points immersed as poles in a drop or larger single portion of fluid, these lines must diverge rapidly from the poles; and the direction in which the chemical affinity between particles is most powerfully modified (519. 520.) will vary with the direction of these lines, according constantly with them. But even in reference to these lines or currents, it is not supposed that the particles which mutually affect each other must of necessity be parallel to them, but only that they shall accord generally with their direction. Two particles, placed in a line perpendicular to the electric current passing in any particular place, are not supposed to have their ordinary chemical relations towards each other affected; but as the line joining them is inclined one way to the current their mutual affinity is increased; as it is inclined in the other direction it is diminished; and the effect is a maximum, when that line is parallel to the current122.

522. That the actions, of whatever kind they may be, take place frequently in oblique directions is evident from the circumstance of those particles being included which in numerous cases are not in a line between the poles. Thus, when wires are used as poles in a glass of solution, the decompositions and recompositions occur to the right or left of the direct line between the poles, and indeed in every part to which the currents extend, as is proved by many experiments, and must therefore often occur between particles obliquely placed as respects the current itself; and when a metallic vessel containing the solution is made one pole, whilst a mere point or wire is used for the other, the decompositions and recompositions must frequently be still more oblique to the course of the currents.

523. The theory which I have ventured to put forth (almost) requires an admission, that in a compound body capable of electro-chemical decomposition the elementary particles have a mutual relation to, and influence upon each other, extending beyond those with which they are immediately combined. Thus in water, a particle of hydrogen in combination with oxygen is considered as not altogether indifferent to other particles of oxygen, although they are combined with other particles of hydrogen; but to have an affinity or attraction towards them, which, though it does not at all approach in force, under ordinary circumstances, to that by which it is combined with its own particle, can, under the electric influence, exerted in a definite direction, be made even to surpass it. This general relation of particles already in combination to other particles with which they are not combined, is sufficiently distinct in numerous results of a purely chemical character; especially in those where partial decompositions only take place, and in Berthollet's experiments on the effects of quantity upon affinity: and it probably has a direct relation to, and connexion with, attraction of aggregation, both in solids and fluids. It is a remarkable circumstance, that in gases and vapours, where the attraction of aggregation ceases, there likewise the decomposing powers of electricity apparently cease, and there also the chemical action of quantity is no longer evident. It seems not unlikely, that the inability to suffer decomposition in these cases may be dependent upon the absence of that mutual attractive relation of the particles which is the cause of aggregation.

524. I hope I have now distinctly stated, although in general terms, the view I entertain of the cause of electro-chemical decomposition, as far as that cause can at present be traced and understood. I conceive the effects to arise from forces which are internal, relative to the matter under decomposition—and not external, as they might be considered, if directly dependent upon the poles. I suppose that the effects are due to a modification, by the electric current, of the chemical affinity of the particles through or by which that current is passing, giving them the power of acting more forcibly in one direction than in another, and consequently making them travel by a series of successive decompositions and recompositions in opposite directions, and finally causing their expulsion or exclusion at the boundaries of the body under decomposition, in the direction of the current, and that in larger or smaller quantities, according as the current is more or less powerful (377.). I think, therefore, it would be more philosophical, and more directly expressive of the facts, to speak of such a body, in relation to the current passing through it, rather than to the poles, as they are usually called, in contact with it; and say that whilst under decomposition, oxygen, chlorine, iodine, acids, &c., are rendered at its negative extremity, and combustibles, metals, alkalies, bases, &c., at its positive extremity (467.), I do not believe that a substance can be transferred in the electric current beyond the point where it ceases to find particles with which it can combine; and I may refer to the experiments made in air (465.) and in water (495.), already quoted, for facts illustrating these views in the first instance; to which I will now add others.

525. In order to show the dependence of the decomposition and transfer of elements upon the chemical affinity of the substances present, experiments were made upon sulphuric acid in the following manner. Dilute sulphuric acid was prepared: its specific gravity was 1.0212. A solution of sulphate of soda was also prepared, of such strength that a measure of it contained exactly as much sulphuric acid as an equal measure of the diluted acid just referred to. A solution of pure soda, and another of pure ammonia, were likewise prepared, of such strengths that a measure of either should be exactly neutralized by a measure of the prepared sulphuric acid.

526. Four glass cups were then arranged, as in fig. 55; seventeen measures of the free sulphuric acid (525.) were put into each of the vessels a and b, and seventeen measures of the solution of sulphate of soda into each of the vessels A and B. Asbestus, which had been well-washed in acid, acted upon by the voltaic pile, well-washed in water, and dried by pressure, was used to connect a with b and A with B, the portions being as equal as they could be made in quantity, and cut as short as was consistent with their performing the part of effectual communications, b and A were connected by two platina plates or poles soldered to the extremities of one wire, and the cups a and B were by similar platina plates connected with a voltaic battery of forty pairs of plates four inches square, that in a being connected with the negative, and that in B with the positive pole. The battery, which was not powerfully charged, was retained in communication above half an hour. In this manner it was certain that the same electric current had passed through a b and A B, and that in each instance the same quantity and strength of acid had been submitted to its action, but in one case merely dissolved in water, and in the other dissolved and also combined with an alkali.

527. On breaking the connexion with the battery, the portions of asbestus were lifted out, and the drops hanging at the ends allowed to fall each into its respective vessel. The acids in a and b were then first compared, for which purpose two evaporating dishes were balanced, and the acid from a put into one, and that from b into the other; but as one was a little heavier than the other, a small drop was transferred from the heavier to the lighter, and the two rendered equal in weight. Being neutralized by the addition of the soda solution (525.), that from a, or the negative vessel, required 15 parts of the soda solution, and that from b, or the positive vessel, required 16.3 parts. That the sum of these is not 34 parts is principally due to the acid removed with the asbestus; but taking the mean of 15.65 parts, it would appear that a twenty-fourth part of the acid originally in the vessel a had passed, through the influence of the electric current, from a into b.

528. In comparing the difference of acid in A and B, the necessary equality of weight was considered as of no consequence, because the solution was at first neutral, and would not, therefore, affect the test liquids, and all the evolved acid would be in B, and the free alkali in A. The solution in A required 3.2 measures of the prepared acid (525.) to neutralize it, and the solution in B required also 3.2 measures of the soda solution (525.) to neutralize it. As the asbestus must have removed a little acid and alkali from the glasses, these quantities are by so much too small; and therefore it would appear that about a tenth of the acid originally in the vessel A had been transferred into B during the continuance of the electric action.

529. In another similar experiment, whilst a thirty-fifth part of the acid passed from a to b; in the free acid vessels, between a tenth and an eleventh passed from A to B in the combined acid vessels. Other experiments of the same kind gave similar results.

530. The variation of electro-chemical decomposition, the transfer of elements and their accumulation at the poles, according as the substance submitted to action consists of particles opposed more or less in their chemical affinity, together with the consequent influence of the latter circumstances, are sufficiently obvious in these cases, where sulphuric acid is acted upon in the same quantity by the same electric current, but in one case opposed to the comparatively weak affinity of water for it, and in the other to the stronger one of soda. In the latter case the quantity transferred is from two and a half to three times what it is in the former; and it appears therefore very evident that the transfer is greatly dependent upon the mutual action of the particles of the decomposing bodies123.

531. In some of the experiments the acid from the vessels a and b was neutralized by ammonia, then evaporated to dryness, heated to redness, and the residue examined for sulphates. In these cases more sulphate was always obtained from a than from b; showing that it had been impossible to exclude saline bases (derived from the asbestus, the glass, or perhaps impurities originally in the acid,) and that they had helped in transferring the acid into b. But the quantity was small, and the acid was principally transferred by relation to the water present.

532. I endeavoured to arrange certain experiments by which saline solutions should be decomposed against surfaces of water; and at first worked with the electric machine upon a piece of bibulous paper, or asbestus moistened in the solution, and in contact at its two extremities with pointed pieces of paper moistened in pure water, which served to carry the electric current to and from the solution in the middle piece. But I found numerous interfering difficulties. Thus, the water and solutions in the pieces of paper could not be prevented from mingling at the point where they touched. Again, sufficient acid could be derived from the paper connected with the discharging train, or it may be even from the air itself, under the influence of electric action, to neutralize the alkali developed at the positive extremity of the decomposing solution, and so not merely prevent its appearance, but actually transfer it on to the metal termination: and, in fact, when the paper points were not allowed to touch there, and the machine was worked until alkali was evolved at the delivering or positive end of the turmeric paper, containing the sulphate of soda solution, it was merely necessary to place the opposite receiving point of the paper connected with the discharging train, which had been moistened by distilled water, upon the brown turmeric point and press them together, when the alkaline effect immediately disappeared.

533. The experiment with sulphate of magnesia already described (495.) is a case in point, however, and shows most clearly that the sulphuric acid and magnesia contributed to each other's transfer and final evolution, exactly as the same acid and soda affected each other in the results just given (527, &c.); and that so soon as the magnesia advanced beyond the reach of the acid, and found no other substance with which it could combine, it appeared in its proper character, and was no longer able to continue its progress towards the negative pole.

* * * * *

534. The theory I have ventured to put forth appears to me to explain all the prominent features of electro-chemical decomposition in a satisfactory manner.

535. In the first place, it explains why, in all ordinary cases, the evolved substances appear only at the poles; for the poles are the limiting surfaces of the decomposing substance, and except at them, every particle finds other particles having a contrary tendency with which it can combine.

536. Then it explains why, in numerous cases, the elements or evolved substances are not retained by the poles; and this is no small difficulty in those theories which refer the decomposing effect directly to the attractive power of the poles. If, in accordance with the usual theory, a piece of platina be supposed to have sufficient power to attract a particle of hydrogen from the particle of oxygen with which it was the instant before combined, there seems no sufficient reason, nor any fact, except those to be explained, which show why it should not, according to analogy with all ordinary attractive forces, as those of gravitation, magnetism, cohesion, chemical affinity, &c. retain that particle which it had just before taken from a distance and from previous combination. Yet it does not do so, but allows it to escape freely. Nor does this depend upon its assuming the gaseous state, for acids and alkalies, &c. are left equally at liberty to diffuse themselves through the fluid surrounding the pole, and show no particular tendency to combine with or adhere to the latter. And though there are plenty of cases where combination with the pole does take place, they do not at all explain the instances of non-combination, and do not therefore in their particular action reveal the general principle of decomposition.

537. But in the theory that I have just given, the effect appears to be a natural consequence of the action: the evolved substances are expelled from the decomposing mass (518. 519.), not drawn out by an attraction which ceases to act on one particle without any assignable reason, while it continues to act on another of the same kind: and whether the poles be metal, water, or air, still the substances are evolved, and are sometimes set free, whilst at others they unite to the matter of the poles, according to the chemical nature of the latter, i.e. their chemical relation to those particles which are leaving the substance under operation.

538. The theory accounts for the transfer of elements in a manner which seems to me at present to leave nothing unexplained; and it was, indeed, the phenomena of transfer in the numerous cases of decomposition of bodies rendered fluid by heat (380. 402.), which, in conjunction with the experiments in air, led to its construction. Such cases as the former where binary compounds of easy decomposability are acted upon, are perhaps the best to illustrate the theory.

539. Chloride of lead, for instance, fused in a bent tube (400.), and decomposed by platina wires, evolves lead, passing to what is usually called the negative pole, and chlorine, which being evolved at the positive pole, is in part set free, and in part combines with the platina. The chloride of platina formed, being soluble in the chloride of lead, is subject to decomposition, and the platina itself is gradually transferred across the decomposing matter, and found with the lead at the negative pole.

540. Iodide of lead evolves abundance of lead at the negative pole, and abundance of iodine at the positive pole.

541. Chloride of silver furnishes a beautiful instance, especially when decomposed by silver wire poles. Upon fusing a portion of it on a piece of glass, and bringing the poles into contact with it, there is abundance of silver evolved at the negative pole, and an equal abundance absorbed at the positive pole, for no chlorine is set free: and by careful management, the negative wire may be withdrawn from the fused globule as the silver is reduced there, the latter serving as the continuation of the pole, until a wire or thread of revived silver, five or six inches in length, is produced; at the same time the silver at the positive pole is as rapidly dissolved by the chlorine, which seizes upon it, so that the wire has to be continually advanced as it is melted away. The whole experiment includes the action of only two elements, silver and chlorine, and illustrates in a beautiful manner their progress in opposite directions, parallel to the electric current, which is for the time giving a uniform general direction to their mutual affinities (524.).

542. According to my theory, an element or a substance not decomposable under the circumstances of the experiment, (as for instance, a dilute acid or alkali,) should not be transferred, or pass from pole to pole, unless it be in chemical relation to some other element or substance tending to pass in the opposite direction, for the effect is considered as essentially due to the mutual relation of such particles. But the theories attributing the determination of the elements to the attractions and repulsions of the poles require no such condition, i.e. there is no reason apparent why the attraction of the positive pole, and the repulsion of the negative pole, upon a particle of free acid, placed in water between them, should not (with equal currents of electricity) be as strong as if that particle were previously combined with alkali; but, on the contrary, as they have not a powerful chemical affinity to overcome, there is every reason to suppose they would be stronger, and would sooner bring the acid to rest at the positive pole124. Yet such is not the case, as has been shown by the experiments on free and combined acid (526. 528.).

543. Neither does M. de la Rive's theory, as I understand it, require that the particles should be in combination: it does not even admit, where there are two sets of particles capable of combining with and passing by each other, that they do combine, but supposes that they travel as separate compounds of matter and electricity. Yet in fact the free substance cannot travel, the combined one can.

544. It is very difficult to find cases amongst solutions or fluids which shall illustrate this point, because of the difficulty of finding two fluids which shall conduct, shall not mingle, and in which an element evolved from one shall not find a combinable element in the other. Solutions of acids or alkalies will not answer, because they exist by virtue of an attraction; and increasing the solubility of a body in one direction, and diminishing it in the opposite, is just as good a reason for transfer, as modifying the affinity between the acids and alkalies themselves125. Nevertheless the case of sulphate of magnesia is in point (494. 495.), and shows that one element or principle only has no power of transference or of passing towards either pole.

545. Many of the metals, however, in their solid state, offer very fair instances of the kind required. Thus, if a plate of platina be used as the positive pole in a solution of sulphuric acid, oxygen will pass towards it, and so will acid; but these are not substances having such chemical relation to the platina as, even under the favourable condition superinduced by the current (518. 524.), to combine with it; the platina therefore remains where it was first placed, and has no tendency to pass towards the negative pole. But if a plate of iron, zinc or copper, be substituted for the platina, then the oxygen and acid can combine with these, and the metal immediately begins to travel (as an oxide) to the opposite pole, and is finally deposited there. Or if, retaining the platina pole, a fused chloride, as of lead, zinc, silver, &c., be substituted for the sulphuric acid, then, as the platina finds an element it can combine with, it enters into union, acts as other elements do in cases of voltaic decomposition, is rapidly transferred across the melted matter, and expelled at the negative pole.

546. I can see but little reason in the theories referring the electro-chemical decomposition to the attractions and repulsions of the poles, and I can perceive none in M. de la Rive's theory, why the metal of the positive pole should not be transferred across the intervening conductor, and deposited at the negative pole, even when it cannot act chemically upon the element of the fluid surrounding it. It cannot be referred to the attraction of cohesion preventing such an effect; for if the pole be made of the lightest spongy platina, the effect is the same. Or if gold precipitated by sulphate of iron be diffused through the solution, still accumulation of it at the negative pole will not take place; and yet the attraction of cohesion is almost perfectly overcome, the particles are in it so small as to remain for hours in suspension, and are perfectly free to move by the slightest impulse towards either pole; and if in relation by chemical affinity to any substance present, are powerfully determined to the negative pole126.

547. In support of these arguments, it may be observed, that as yet no determination of a substance to a pole, or tendency to obey the electric current, has been observed (that I am aware of,) in cases of mere mixture; i.e. a substance diffused through a fluid, but having no sensible chemical affinity with it, or with substances that may be evolved from it during the action, does not in any case seem to be affected by the electric current. Pulverised charcoal was diffused through dilute sulphuric acid, and subjected with the solution to the action of a voltaic battery, terminated by platina poles; but not the slightest tendency of the charcoal to the negative pole could be observed, Sublimed sulphur was diffused through similar acid, and submitted to the same action, a silver plate being used as the negative pole; but the sulphur had no tendency to pass to that pole, the silver was not tarnished, nor did any sulphuretted hydrogen appear. The case of magnesia and water (495. 533.), with those of comminuted metals in certain solutions (546.), are also of this kind; and, in fact, substances which have the instant before been powerfully determined towards the pole, as magnesia from sulphate of magnesia, become entirely indifferent to it the moment they assume their independent state, and pass away, diffusing themselves through the surrounding fluid.

548. There are, it is true, many instances of insoluble bodies being acted upon, as glass, sulphate of baryta, marble, slate, basalt, &c., but they form no exception; for the substances they give up are in direct and strong relation as to chemical affinity with those which they find in the surrounding solution, so that these decompositions enter into the class of ordinary effects.

549. It may be expressed as a general consequence, that the more directly bodies are opposed to each other in chemical affinity, the more ready is their separation from each other in cases of electro-chemical decomposition, i.e. provided other circumstances, as insolubility, deficient conducting power, proportions, &c., do not interfere. This is well known to be the case with water and saline solutions; and I have found it to be equally true with dry chlorides, iodides, salts, &c., rendered subject to electro-chemical decomposition by fusion (402.). So that in applying the voltaic battery for the purpose of decomposing bodies not yet resolved into forms of matter simpler than their own, it must be remembered, that success may depend not upon the weakness, or failure upon the strength, of the affinity by which the elements sought for are held together, but contrariwise; and then modes of application may be devised, by which, in association with ordinary chemical powers, and the assistance of fusion (394. 417.), we may be able to penetrate much further than at present into the constitution of our chemical elements.

550. Some of the most beautiful and surprising cases of electro-chemical decomposition and transfer which Sir Humphry Davy described in his celebrated paper127, were those in which acids were passed through alkalies, and alkalies or earths through acids128; and the way in which substances having the most powerful attractions for each other were thus prevented from combining, or, as it is said, had their natural affinity destroyed or suspended throughout the whole of the circuit, excited the utmost astonishment. But if I be right in the view I have taken of the effects, it will appear, that that which made the wonder, is in fact the essential condition of transfer and decomposition, and that the more alkali there is in the course of an acid, the more will the transfer of that acid be facilitated from pole to pole; and perhaps a better illustration of the difference between the theory I have ventured, and those previously existing, cannot be offered than the views they respectively give of such facts as these.

551. The instances in which sulphuric acid could not be passed though baryta, or baryta through sulphuric acid129, because of the precipitation of sulphate of baryta, enter within the pale of the law already described (380. 412.), by which liquidity is so generally required for conduction and decomposition. In assuming the solid state of sulphate of baryta, these bodies became virtually non-conductors to electricity of so low a tension as that of the voltaic battery, and the power of the latter over them was almost infinitely diminished.

552. The theory I have advanced accords in a most satisfactory manner with the fact of an element or substance finding its place of rest, or rather of evolution, sometimes at one pole and sometimes at the other. Sulphur illustrates this effect very well130. When sulphuric acid is decomposed by the pile, sulphur is evolved at the negative pole; but when sulphuret of silver is decomposed in a similar way (436.), then the sulphur appears at the positive pole; and if a hot platina pole be used so as to vaporize the sulphur evolved in the latter case, then the relation of that pole to the sulphur is exactly the same as the relation of the same pole to oxygen upon its immersion in water. In both cases the element evolved is liberated at the pole, but not retained by it; but by virtue of its elastic, uncombinable, and immiscible condition passes away into the surrounding medium. The sulphur is evidently determined in these opposite directions by its opposite chemical relations to oxygen and silver; and it is to such relations generally that I have referred all electro-chemical phenomena. Where they do not exist, no electro-chemical action can take place. Where they are strongest, it is most powerful; where they are reversed, the direction of transfer of the substance is reversed with them.

553. Water may be considered as one of those substances which can be made to pass to either pole. When the poles are immersed in dilute sulphuric acid (527.), acid passes towards the positive pole, and water towards the negative pole; but when they are immersed in dilute alkali, the alkali passes towards the negative pole, and water towards the positive pole.

554. Nitrogen is another substance which is considered as determinable to either pole; but in consequence of the numerous compounds which it forms, some of which pass to one pole, and some to the other, I have not always found it easy to determine the true circumstances of its appearance. A pure strong solution of ammonia is so bad a conductor of electricity that it is scarcely more decomposable than pure water; but if sulphate of ammonia be dissolved in it, then decomposition takes place very well; nitrogen almost pure, and in some cases quite, is evolved at the positive pole, and hydrogen at the negative pole.

555. On the other hand, if a strong solution of nitrate of ammonia be decomposed, oxygen appears at the positive pole, and hydrogen, with sometimes nitrogen, at the negative pole. If fused nitrate of ammonia be employed, hydrogen appears at the negative pole, mingled with a little nitrogen. Strong nitric acid yields plenty of oxygen at the positive pole, but no gas (only nitrous acid) at the negative pole. Weak nitric acid yields the oxygen and hydrogen of the water present, the acid apparently remaining unchanged. Strong nitric acid with nitrate of ammonia dissolved in it, yields a gas at the negative pole, of which the greater part is hydrogen, but apparently a little nitrogen is present. I believe, that in some of these cases a little nitrogen appeared at the negative pole. I suspect, however, that in all these, and in all former cases, the appearance of the nitrogen at the positive or negative pole is entirely a secondary effect, and not an immediate consequence of the decomposing power of the electric current131.

556. A few observations on what are called the poles of the voltaic battery now seem necessary. The poles are merely the surfaces or doors by which the electricity enters into or passes out of the substance suffering decomposition. They limit the extent of that substance in the course of the electric current, being its terminations in that direction: Hence the elements evolved pass so far and no further.

557. Metals make admirable poles, in consequence of their high conducting power, their immiscibility with the substances generally acted upon, their solid form, and the opportunity afforded of selecting such as are not chemically acted upon by ordinary substances.

558. Water makes a pole of difficult application, except in a few cases (494.), because of its small conducting power, its miscibility with most of the substances acted upon, and its general relation to them in respect to chemical affinity. It consists of elements, which in their electrical and chemical relations are directly and powerfully opposed, yet combining to produce a body more neutral in its character than any other. So that there are but few substances which do not come into relation, by chemical affinity, with water or one of its elements; and therefore either the water or its elements are transferred and assist in transferring the infinite variety of bodies which, in association with it, can be placed in the course of the electric current. Hence the reason why it so rarely happens that the evolved substances rest at the first surface of the water, and why it therefore does not exhibit the ordinary action of a pole.

559. Air, however, and some gases are free from the latter objection, and may be used as poles in many cases (461, &c.); but, in consequence of the extremely low degree of conducting power belonging to them, they cannot be employed with the voltaic apparatus. This limits their use; for the voltaic apparatus is the only one as yet discovered which supplies sufficient quantity of electricity (371. 376.) to effect electro-chemical decomposition with facility.

560. When the poles are liable to the chemical action of the substances evolved, either simply in consequence of their natural relation to them, or of that relation aided by the influence of the current (518.), then they suffer corrosion, and the parts dissolved are subject to transference, in the same manner as the particles of the body originally under decomposition. An immense series of phenomena of this kind might be quoted in support of the view I have taken of the cause of electro-chemical decomposition, and the transfer and evolution of the elements. Thus platina being made the positive and negative poles in a solution of sulphate of soda, has no affinity or attraction for the oxygen, hydrogen, acid, or alkali evolved, and refuses to combine with or retain them. Zinc can combine with the oxygen and acid; at the positive pole it does combine, and immediately begins to travel as oxide towards the negative pole. Charcoal, which cannot combine with the metals, if made the negative pole in a metallic solution, refuses to unite to the bodies which are ejected from the solution upon its surface; but if made the positive pole in a dilute solution of sulphuric acid, it is capable of combining with the oxygen evolved there, and consequently unites with it, producing both carbonic acid and carbonic oxide in abundance.

561. A great advantage is frequently supplied, by the opportunity afforded amongst the metals of selecting a substance for the pole, which shall or shall not be acted upon by the elements to be evolved. The consequent use of platina is notorious. In the decomposition of sulphuret of silver and other sulphurets, a positive silver pole is superior to a platina one, because in the former case the sulphur evolved there combines with the silver, and the decomposition of the original sulphuret is rendered evident; whereas in the latter case it is dissipated, and the assurance of its separation at the pole not easily obtained.

562. The effects which take place when a succession of conducting decomposable and undecomposable substances are placed in the electric circuit, as, for instance, of wires and solutions, or of air and solutions (465, 469.), are explained in the simplest possible manner by the theoretical view I have given. In consequence of the reaction of the constituents of each portion of decomposable matter, affected as they are by the supervention of the electric current (524.), portions of the proximate or ultimate elements proceed in the direction of the current as far as they find matter of a contrary kind capable of effecting their transfer, and being equally affected by them; and where they cease to find such matter, they are evolved in their free state, i.e. upon the surfaces of metal or air bounding the extent of decomposable matter in the direction of the current.

563. Having thus given my theory of the mode in which electro-chemical decomposition is effected, I will refrain for the present from entering upon the numerous general considerations which it suggests, wishing first to submit it to the test of publication and discussion.

Royal Institution,

June 1833.

¶ iv. On some general conditions of Electro-chemical Decomposition.

669. From the period when electro-chemical decomposition was first effected to the present time, it has been a remark, that those elements which, in the ordinary phenomena of chemical affinity, were the most directly opposed to each other, and combined with the greatest attractive force, were those which were the most readily evolved at the opposite extremities of the decomposing bodies (549.).

670. If this result was evident when water was supposed to be essential to, and was present in, almost every case of such decomposition (472.), it is far more evident now that it has been shown and proved that water is not necessarily concerned in the phenomena (474.), and that other bodies much surpass it in some of the effects supposed to be peculiar to that substance.

671. Water, from its constitution and the nature of its elements, and from its frequent presence in cases of electrolytic action, has hitherto stood foremost in this respect. Though a compound formed by very powerful affinity, it yields up its elements under the influence of a very feeble electric current; and it is doubtful whether a case of electrolyzation can occur, where, being present, it is not resolved into its first principles.

672. The various oxides, chlorides, iodides, and salts, which I have shown are decomposable by the electric current when in the liquid state, under the same general law with water (402.), illustrate in an equally striking manner the activity, in such decompositions, of elements directly and powerfully opposed to each other by their chemical relations.

673. On the other hand, bodies dependent on weak affinities very rarely give way. Take, for instance, glasses: many of those formed of silica, lime, alkali, and oxide of lead, may be considered as little more than solutions of substances one in another161. If bottle-glass be fused, and subjected to the voltaic pile, it does not appear to be at all decomposed (408.). If flint glass, which contains substances more directly opposed, be operated upon, it suffers some decomposition; and if borate of lead glass, which is a definite chemical compound, be experimented with, it readily yields up its elements (408.).

674. But the result which is found to be so striking in the instances quoted is not at all borne out by reference to other cases where a similar consequence might have been expected. It may be said, that my own theory of electro-chemical decomposition would lead to the expectation that all compound bodies should give way under the influence of the electric current with a facility proportionate to the strength of the affinity by which their elements, either proximate or ultimate, are combined. I am not sure that that follows as a consequence of the theory; but if the objection is supposed to be one presented by the facts, I have no doubt it will be removed when we obtain a more intimate acquaintance with, and precise idea of, the nature of chemical affinity and the mode of action of an electric current over it (518. 524.): besides which, it is just as directly opposed to any other theory of electro-chemical decomposition as the one I have propounded; for if it be admitted, as is generally the case, that the more directly bodies are opposed to each other in their attractive forces, the more powerfully do they combine, then the objection applies with equal force to any of the theories of electrolyzation which have been considered, and is an addition to those which I have taken against them.

675. Amongst powerful compounds which are not decomposed, boracic acids stand prominent (408.). Then again, the iodide of sulphur, and the chlorides of sulphur, phosphorus, and carbon, are not decomposable under common circumstances, though their elements are of a nature which would lead to a contrary expectation. Chloride of antimony (402. 690.), the hydro-carbons, acetic acid, ammonia, and many other bodies undecomposable by the voltaic pile, would seem to be formed by an affinity sufficiently strong to indicate that the elements were so far contrasted in their nature as to sanction the expectation that, the pile would separate them, especially as in some cases of mere solution (530. 544.), where the affinity must by comparison be very weak, separation takes place162.

676. It must not be forgotten, however, that much of this difficulty, and perhaps the whole, may depend upon the absence of conducting power, which, preventing the transmission of the current, prevents of course the effects due to it. All known compounds being non-conductors when solid, but conductors when liquid, are decomposed, with perhaps the single exception at present known of periodide of mercury (679. 691.)163; and even water itself, which so easily yields up its elements when the current passes, if rendered quite pure, scarcely suffers change, because it then becomes a very bad conductor.

677. If it should hereafter be proved that the want of decomposition in those cases where, from chemical considerations, it might be so strongly expected (669, 672. 674.), is due to the absence or deficiency of conducting power, it would also at the same time be proved that decomposition depends upon conduction, and not the latter upon the former (413.); and in water this seems to be very nearly decided. On the other hand, the conclusion is almost irresistible, that in electrolytes the power of transmitting the electricity across the substance is dependent upon their capability of suffering decomposition; taking place only whilst they are decomposing, and being proportionate to the quantity of elements separated (821.). I may not, however, stop to discuss this point experimentally at present.

678. When a compound contains such elements as are known to pass towards the opposite extremities of the voltaic pile, still the proportions in which they are present appear to be intimately connected with capability in the compound of suffering or resisting decomposition. Thus, the protochloride of tin readily conducts, and is decomposed (402.), but the perchloride neither conducts nor is decomposed (406.). The protiodide of tin is decomposed when fluid (402.); the periodide is not (405.). The periodide of mercury when fused is not decomposed (691.), even though it does conduct. I was unable to contrast it with the protiodide, the latter being converted into mercury and periodide by heat.

679. These important differences induced me to look more closely to certain binary compounds, with a view of ascertaining whether a law regulating the decomposability according to some relation of the proportionals or equivalents of the elements, could be discovered. The proto compounds only, amongst those just referred to, were decomposable; and on referring to the substances quoted to illustrate the force and generality of the law of conduction and decomposition which I discovered (402.), it will be found that all the oxides, chlorides, and iodides subject to it, except the chloride of antimony and the periodide of mercury, (to which may now perhaps be added corrosive sublimate,) are also decomposable, whilst many per compounds of the same elements, not subject to the law, were not so (405. 406.).

680. The substances which appeared to form the strongest exceptions to this general result were such bodies as the sulphuric, phosphoric, nitric, arsenic, and other acids.

681. On experimenting with sulphuric acid, I found no reason to believe that it was by itself a conductor of, or decomposable by, electricity, although I had previously been of that opinion (552.). When very strong it is a much worse conductor than if diluted164. If then subjected to the action of a powerful battery, oxygen appears at the anode, or positive electrode, although much is absorbed (728.), and hydrogen and sulphur appear at the cathode, or negative electrode. Now the hydrogen has with me always been pure, not sulphuretted, and has been deficient in proportion to the sulphur present, so that it is evident that when decomposition occurred water must have been decomposed. I endeavoured to make the experiment with anhydrous sulphuric acid; and it appeared to me that, when fused, such acid was not a conductor, nor decomposed; but I had not enough of the dry acid in my possession to allow me to decide the point satisfactorily. My belief is, that when sulphur appears during the action of the pile on sulphuric acid, it is the result of a secondary action, and that the acid itself is not electrolyzable (757.).

682. Phosphoric acid is, I believe, also in the same condition; but I have found it impossible to decide the point, because of the difficulty of operating on fused anhydrous phosphoric acid. Phosphoric acid which has once obtained water cannot be deprived of it by heat alone. When heated, the hydrated acid volatilizes. Upon subjecting phosphoric acid, fused upon the ring end of a wire (401.), to the action of the voltaic apparatus, it conducted, and was decomposed; but gas, which I believe to be hydrogen, was always evolved at the negative electrode, and the wire was not affected as would have happened had phosphorus been separated. Gas was also evolved at the positive electrode. From all the facts, I conclude it was the water and not the acid which was decomposed.

683. Arsenic acid. This substance conducted, and was decomposed; but it contained water, and I was unable at the time to press the investigation so as to ascertain whether a fusible anhydrous arsenic acid could be obtained. It forms, therefore, at present no exception to the general result.

684. Nitrous acid, obtained by distilling nitrate of lead, and keeping it in contact with strong sulphuric acid, was found to conduct and decompose slowly. But on examination there were strong reasons for believing that water was present, and that the decomposition and conduction depended upon it. I endeavoured to prepare a perfectly anhydrous portion, but could not spare the time required to procure an unexceptionable result.

685. Nitric acid is a substance which I believe is not decomposed directly by the electric current. As I want the facts in illustration of the distinction existing between primary and secondary decomposition, I will merely refer to them in this place (752.).

686. That these mineral acids should confer facility of conduction and decomposition on water, is no proof that they are competent to favour and suffer these actions in themselves. Boracic acid does the same thing, though not decomposable. M. de la Rive has pointed out that chlorine has this power also; but being to us an elementary substance, it cannot be due to its capability of suffering decomposition.

687. Chloride of sulphur does not conduct, nor is it decomposed. It consists of single proportionals of its elements, but is not on that account an exception to the rule (679.), which does not affirm that all compounds of single proportionals of elements are decomposable, but that such as are decomposable are so constituted.

688. Protochloride of phosphorus does not conduct nor become decomposed.

689. Protochloride of carbon does not conduct nor suffer decomposition. In association with this substance, I submitted the hydro-chloride of carbon from olefiant gas and chlorine to the action of the electric current; but it also refused to conduct or yield up its elements.

600. With regard to the exceptions (679.), upon closer examination some of them disappear. Chloride of antimony (a compound of one proportional of antimony and one and a half of chlorine) of recent preparation was put into a tube (fig. 68.) (789.), and submitted when fused to the action of the current, the positive electrode being of plumbago. No electricity passed, and no appearance of decomposition was visible at first; but when the positive and negative electrodes were brought very near each other in the chloride, then a feeble action occurred and a feeble current passed. The effect altogether was so small (although quite amenable to the law before given (394.)), and so unlike the decomposition and conduction occurring in all the other cases, that I attribute it to the presence of a minute quantity of water, (for which this and many other chlorides have strong attractions, producing hydrated chlorides,) or perhaps of a true protochloride consisting of single proportionals (695, 796.).

691. Periodide of mercury being examined in the same manner, was found most distinctly to insulate whilst solid, but conduct when fluid, according to the law of liquido-conduction (402.); but there was no appearance of decomposition. No iodine appeared at the anode, nor mercury or other substance at the cathode. The case is, therefore, no exception to the rule, that only compounds of single proportionals are decomposable; but it is an exception, and I think the only one, to the statement, that all bodies subject to the law of liquido-conduction are decomposable. I incline, however, to believe, that a portion of protiodide of mercury is retained dissolved in the periodide, and that to its slow decomposition the feeble conducting power is due. Periodide would be formed, as a secondary result, at the anode; and the mercury at the cathode would also form, as a secondary result, protiodide. Both these bodies would mingle with the fluid mass, and thus no final separation appear, notwithstanding the continued decomposition.

692. When perchloride of mercury was subjected to the voltaic current, it did not conduct in the solid state, but it did conduct when fluid. I think, also, that in the latter case it was decomposed; but there are many interfering circumstances which require examination before a positive conclusion can be drawn165.

693. When the ordinary protoxide of antimony is subjected to the voltaic current in a fused state, it also is decomposed, although the effect from other causes soon ceases (402, 801.). This oxide consists of one proportional of antimony and one and a half of oxygen, and is therefore an exception to the general law assumed. But in working with this oxide and the chloride, I observed facts which lead me to doubt whether the compounds usually called the protoxide and the protochloride do not often contain other compounds, consisting of single proportions, which are the true proto compounds, and which, in the case of the oxide, might give rise to the decomposition above described.

694. The ordinary sulphuret of antimony its considered as being the compound with the smallest quantity of sulphur, and analogous in its proportions to the ordinary protoxide. But I find that if it be fused with metallic antimony, a new sulphuret is formed, containing much more of the metal than the former, and separating distinctly, when fused, both from the pure metal on the one hand, and the ordinary gray sulphuret on the other. In some rough experiments, the metal thus taken up by the ordinary sulphuret of antimony was equal to half the proportion of that previously in the sulphuret, in which case the new sulphuret would consist of single proportionals.

695. When this new sulphuret was dissolved in muriatic acid, although a little antimony separated, yet it appeared to me that a true protochloride, consisting of single proportionals, was formed, and from that by alkalies, &c., a true protoxide, consisting also of single proportionals, was obtainable. But I could not stop to ascertain this matter strictly by analysis.

696. I believe, however, that there is such an oxide; that it is often present in variable proportions in what is commonly called protoxide, throwing uncertainty upon the results of its analysis, and causing the electrolytic decomposition above described166.

697. Upon the whole, it appears probable that all those binary compounds of elementary bodies which are capable of being electrolyzed when fluid, but not whilst solid, according to the law of liquido-conduction (394.), consist of single proportionals of their elementary principles; and it may be because of their departure from this simplicity of composition, that boracic acid, ammonia, perchlorides, periodides, and many other direct compounds of elements, are indecomposable.

698. With regard to salts and combinations of compound bodies, the same simple relation does not appear to hold good. I could not decide this by bisulphates of the alkalies, for as long as the second proportion of acid remained, water was retained with it. The fused salts conducted, and were decomposed; but hydrogen always appeared at the negative electrode.

699. A biphosphate of soda was prepared by heating, and ultimately fusing, the ammonia-phosphate of soda. In this case the fused bisalt conducted, and was decomposed; but a little gas appeared at the negative electrode; and though I believe the salt itself was electrolyzed, I am not quite satisfied that water was entirely absent.

700. Then a biborate of soda was prepared; and this, I think, is an unobjectionable case. The salt, when fused, conducted, and was decomposed, and gas appeared at both electrodes: even when the boracic acid was increased to three proportionals, the same effect took place.

701. Hence this class of compound combinations does not seem to be subject to the same simple law as the former class of binary combinations. Whether we may find reason to consider them as mere solutions of the compound of single proportionals in the excess of acid, is a matter which, with some apparent exceptions occurring amongst the sulphurets, must be left for decision by future examination.

702. In any investigation of these points, great care must be taken to exclude water; for if present, secondary effects are so frequently produced as often seemingly to indicate an electro-decomposition of substances, when no true result of the kind has occurred (742, &c.).

703. It is evident that all the cases in which decomposition does not occur, may depend upon the want of conduction (677. 413.); but that does not at all lessen the interest excited by seeing the great difference of effect due to a change, not in the nature of the elements, but merely in their proportions; especially in any attempt which may be made to elucidate and expound the beautiful theory put forth by Sir Humphry Davy167, and illustrated by Berzelius and other eminent philosophers, that ordinary chemical affinity is a mere result of the electrical attractions of the particles of matter.

¶ v. On a new measure of Volta-electricity.

704. I have already said, when engaged in reducing common and voltaic electricity to one standard of measurement (377.), and again when introducing my theory of electro-chemical decomposition (504. 505. 510.), that the chemical decomposing action of a current is constant for a constant quantity of electricity, notwithstanding the greatest variations in its sources, in its intensity, in the size of the electrodes used, in the nature of the conductors (or non-conductors (307.)) through which it is passed, or in other circumstances. The conclusive proofs of the truth of these statements shall be given almost immediately (783, &c.).

705. I endeavoured upon this law to construct an instrument which should measure out the electricity passing through it, and which, being interposed in the course of the current used in any particular experiment, should serve at pleasure, either as a comparative standard of effect, or as a positive measurer of this subtile agent.

706. There is no substance better fitted, under ordinary circumstances, to be the indicating body in such an instrument than water; for it is decomposed with facility when rendered a better conductor by the addition of acids or salts; its elements may in numerous cases be obtained and collected without any embarrassment from secondary action, and, being gaseous, they are in the best physical condition for separation and measurement. Water, therefore, acidulated by sulphuric acid, is the substance I shall generally refer to, although it may become expedient in peculiar cases or forms of experiment to use other bodies (843.).

707. The first precaution needful in the construction of the instrument was to avoid the recombination of the evolved gases, an effect which the positive electrode has been found so capable of producing (571.). For this purpose various forms of decomposing apparatus were used. The first consisted of straight tubes, each containing a plate and wire of platina soldered together by gold, and fixed hermetically in the glass at the closed extremity of the tube (Plate V. fig. 60.). The tubes were about eight inches long, 0.7 of an inch in diameter, and graduated. The platina plates were about an inch long, as wide as the tubes would permit, and adjusted as near to the mouths of the tubes as was consistent with the safe collection of the gases evolved. In certain cases, where it was required to evolve the elements upon as small a surface as possible, the metallic extremity, instead of being a plate, consisted of the wire bent into the form of a ring (fig. 61.). When these tubes were used as measurers, they were filled with the dilute sulphuric acid, inverted in a basin of the same liquid (fig. 62.), and placed in an inclined position, with their mouths near to each other, that as little decomposing matter should intervene as possible; and also, in such a direction that the platina plates should be in vertical planes (720).

708. Another form of apparatus is that delineated (fig. 63.). The tube is bent in the middle; one end is closed; in that end is fixed a wire and plate, a, proceeding so far downwards, that, when in the position figured, it shall be as near to the angle as possible, consistently with the collection, at the closed extremity of the tube, of all the gas evolved against it. The plane of this plate is also perpendicular (720.). The other metallic termination, b, is introduced at the time decomposition is to be effected, being brought as near the angle as possible, without causing any gas to pass from it towards the closed end of the instrument. The gas evolved against it is allowed to escape.

709. The third form of apparatus contains both electrodes in the same tube; the transmission, therefore, of the electricity, and the consequent decomposition, is far more rapid than in the separate tubes. The resulting gas is the sum of the portions evolved at the two electrodes, and the instrument is better adapted than either of the former as a measurer of the quantity of voltaic electricity transmitted in ordinary cases. It consists of a straight tube (fig. 64.) closed at the upper extremity, and graduated, through the sides of which pass platina wires (being fused into the glass), which are connected with two plates within. The tube is fitted by grinding into one mouth of a double-necked bottle. If the latter be one-half or two-thirds full of the dilute sulphuric acid (706.), it will, upon inclination of the whole, flow into the tube and fill it. When an electric current is passed through the instrument, the gases evolved against the plates collect in the upper portion of the tube, and are not subject to the recombining power of the platina.

710. Another form of the instrument is given at fig. 65.

711. A fifth form is delineated (fig. 66.). This I have found exceedingly useful in experiments continued in succession for days together, and where large quantities of indicating gas were to be collected. It is fixed on a weighted foot, and has the form of a small retort containing the two electrodes: the neck is narrow, and sufficiently long to deliver gas issuing from it into a jar placed in a small pneumatic trough. The electrode chamber, sealed hermetically at the part held in the stand, is five inches in length, and 0.6 of an inch in diameter; the neck about nine inches in length, and 0.4 of an inch in diameter internally. The figure will fully indicate the construction.

712. It can hardly be requisite to remark, that in the arrangement of any of these forms of apparatus, they, and the wires connecting them with the substance, which is collaterally subjected to the action of the same electric current, should be so far insulated as to ensure a certainty that all the electricity which passes through the one shall also be transmitted through the other.

* * * * *

713. Next to the precaution of collecting the gases, if mingled, out of contact with the platinum, was the necessity of testing the law of a definite electrolytic action, upon water at least, under all varieties of condition; that, with a conviction of its certainty, might also be obtained a knowledge of those interfering circumstances which would require to be practically guarded against.

714. The first point investigated was the influence or indifference of extensive variations in the size of the electrodes, for which purpose instruments like those last described (709. 710. 711.) were used. One of these had plates 0.7 of an inch wide, and nearly four inches long; another had plates only 0.5 of an inch wide, and 0.8 of an inch long; a third had wires 0.02 of an inch in diameter, and three inches long; and a fourth, similar wires only half an inch in length. Yet when these were filled with dilute sulphuric acid, and, being placed in succession, had one common current of electricity passed through them, very nearly the same quantity of gas was evolved in all. The difference was sometimes in favour of one and sometimes on the side of another; but the general result was that the largest quantity of gases was evolved at the smallest electrodes, namely, those consisting merely of platina wires.

715. Experiments of a similar kind were made with the single-plate, straight tubes (707.), and also with the curved tubes (708.), with similar consequences; and when these, with the former tubes, were arranged together in various ways, the result, as to the equality of action of large and small metallic surfaces when delivering and receiving the same current of electricity, was constantly the same. As an illustration, the following numbers are given. An instrument with two wires evolved 74.3 volumes of mixed gases; another with plates 73.25 volumes; whilst the sum of the oxygen and hydrogen in two separate tubes amounted to 73.65 volumes. In another experiment the volumes were 55.3, 55.3, and 54.4.

716. But it was observed in these experiments, that in single-plate tubes (707.) more hydrogen was evolved at the negative electrode than was proportionate to the oxygen at the positive electrode; and generally, also, more than was proportionate to the oxygen and hydrogen in a double-plate tube. Upon more minutely examining these effects, I was led to refer them, and also the differences between wires and plates (714.), to the solubility of the gases evolved, especially at the positive electrode.

717. When the positive and negative electrodes are equal in surface, the bubbles which rise from them in dilute sulphuric acid are always different in character. Those from the positive plate are exceedingly small, and separate instantly from every part of the surface of the metal, in consequence of its perfect cleanliness (633.); whilst in the liquid they give it a hazy appearance, from their number and minuteness; are easily carried down by currents, and therefore not only present far greater surface of contact with the liquid than larger bubbles would do, but are retained a much longer time in mixture with it. But the bubbles at the negative surface, though they constitute twice the volume of the gas at the positive electrode, are nevertheless very inferior in number. They do not rise so universally from every part of the surface, but seem to be evolved at different parts; and though so much larger, they appear to cling to the metal, separating with difficulty from it, and when separated, instantly rising to the top of the liquid. If, therefore, oxygen and hydrogen had equal solubility in, or powers of combining with, water under similar circumstances, still under the present conditions the oxygen would be far the most liable to solution; but when to these is added its well-known power of forming a compound with water, it is no longer surprising that such a compound should be produced in small quantities at the positive electrode; and indeed the blenching power which some philosophers have observed in a solution at this electrode, when chlorine and similar bodies have been carefully excluded, is probably due to the formation there, in this manner, of oxywater.

718. That more gas was collected from the wires than from the plates, I attribute to the circumstance, that as equal quantities were evolved in equal times, the bubbles at the wires having been more rapidly produced, in relation to any part of the surface, must have been much larger; have been therefore in contact with the fluid by a much smaller surface, and for a much shorter time than those at the plates; hence less solution and a greater amount collected.

719. There was also another effect produced, especially by the use of large electrodes, which was both a consequence and a proof of the solution of part of the gas evolved there. The collected gas, when examined, was found to contain small portions of nitrogen. This I attribute to the presence of air dissolved in the acid used for decomposition. It is a well-known fact, that when bubbles of a gas but slightly soluble in water or solutions pass through them, the portion of this gas which is dissolved displaces a portion of that previously in union with the liquid: and so, in the decompositions under consideration, as the oxygen dissolves, it displaces a part of the air, or at least of the nitrogen, previously united to the acid; and this effect takes place most extensively with large plates, because the gas evolved at them is in the most favourable condition for solution,

720. With the intention of avoiding this solubility of the gases as much as possible, I arranged the decomposing plates in a vertical position (707. 708.), that the bubbles might quickly escape upwards, and that the downward currents in the fluid should not meet ascending currents of gas. This precaution I found to assist greatly in producing constant results, and especially in experiments to be hereafter referred to, in which other liquids than dilute sulphuric acid, as for instance solution of potash, were used.

721. The irregularities in the indications of the measurer proposed, arising from the solubility just referred to, are but small, and may be very nearly corrected by comparing the results of two or three experiments. They may also be almost entirely avoided by selecting that solution which is found to favour them in the least degree (728.); and still further by collecting the hydrogen only, and using that as the indicating gas; for being much less soluble than oxygen, being evolved with twice the rapidity and in larger bubbles (717.), it can be collected more perfectly and in greater purity.

722. From the foregoing and many other experiments, it results that variation in the size of the electrodes causes no variation in the chemical action of a given quantity of electricity upon water.

723. The next point in regard to which the principle of constant electro-chemical action was tested, was variation of intensity. In the first place, the preceding experiments were repeated, using batteries of an equal number of plates, strongly and weakly charged; but the results were alike. They were then repeated, using batteries sometimes containing forty, and at other times only five pairs of plates; but the results were still the same. Variations therefore in the intensity, caused by difference in the strength of charge, or in the number of alternations used, produced no difference as to the equal action of large and small electrodes.

724. Still these results did not prove that variation in the intensity of the current was not accompanied by a corresponding variation in the electro-chemical effects, since the actions at all the surfaces might have increased or diminished together. The deficiency in the evidence is, however, completely supplied by the former experiments on different-sized electrodes; for with variation in the size of these, a variation in the intensity must have occurred. The intensity of an electric current traversing conductors alike in their nature, quality, and length, is probably as the quantity of electricity passing through a given sectional area perpendicular to the current, divided by the time (360. note); and therefore when large plates were contrasted with wires separated by an equal length of the same decomposing conductor (714.), whilst one current of electricity passed through both arrangements, that electricity must have been in a very different state, as to tension, between the plates and between the wires; yet the chemical results were the same.

725. The difference in intensity, under the circumstances described, may be easily shown practically, by arranging two decomposing apparatus as in fig. 67, where the same fluid is subjected to the decomposing power of the same current of electricity, passing in the vessel A. between large platina plates, and in the vessel B. between small wires. If a third decomposing apparatus, such as that delineated fig. 66. (711.), be connected with the wires at ab, fig. 67, it will serve sufficiently well, by the degree of decomposition occurring in it, to indicate the relative state of the two plates as to intensity; and if it then be applied in the same way, as a test of the state of the wires at a'b', it will, by the increase of decomposition within, show how much greater the intensity is there than at the former points. The connexions of P and N with the voltaic battery are of course to be continued during the whole time.

726. A third form of experiment, in which difference of intensity was obtained, for the purpose of testing the principle of equal chemical action, was to arrange three volta-electrometers, so that after the electric current had passed through one, it should divide into two parts, each of which should traverse one of the remaining instruments, and should then reunite. The sum of the decomposition in the two latter vessels was always equal to the decomposition in the former vessel. But the intensity of the divided current could not be the same as that it had in its original state; and therefore variation of intensity has no influence on the results if the quantity of electricity remain the same. The experiment, in fact, resolves itself simply into an increase in the size of the electrodes (725.).

727. The third point, in respect to which the principle of equal electro-chemical action on water was tested, was variation of the strength of the solution used. In order to render the water a conductor, sulphuric acid had been added to it (707.); and it did not seem unlikely that this substance, with many others, might render the water more subject to decomposition, the electricity remaining the same in quantity. But such did not prove to be the case. Diluted sulphuric acid, of different strengths, was introduced into different decomposing apparatus, and submitted simultaneously to the action of the same electric current (714.). Slight differences occurred, as before, sometimes in one direction, sometimes in another; but the final result was, that exactly the same quantity of water was decomposed in all the solutions by the same quantity of electricity, though the sulphuric acid in some was seventy-fold what it was in others. The strengths used were of specific gravity 1.495, and downwards.

728. When an acid having a specific gravity of about 1.336 was employed, the results were most uniform, and the oxygen and hydrogen (716.) most constantly in the right proportion to each other. Such an acid gave more gas than one much weaker acted upon by the same current, apparently because it had less solvent power. If the acid were very strong, then a remarkable disappearance of oxygen took place; thus, one made by mixing two measures of strong oil of vitriol with one of water, gave forty-two volumes of hydrogen, but only twelve of oxygen. The hydrogen was very nearly the same with that evolved from acid of the specific gravity 1.232. I have not yet had time to examine minutely the circumstances attending the disappearance of the oxygen in this case, but imagine it is due to the formation of oxywater, which Thenard has shown is favoured by the presence of acid.

729. Although not necessary for the practical use of the instrument I am describing, yet as connected with the important point of constant chemical action upon water, I now investigated the effects produced by an electro-electric current passing through aqueous solutions of acids, salts, and compounds, exceedingly different from each other in their nature, and found them to yield astonishingly uniform results. But many of them which are connected with a secondary action will be more usefully described hereafter (778.).

730. When solutions of caustic potassa or soda, or sulphate of magnesia, or sulphate of soda, were acted upon by the electric current, just as much oxygen and hydrogen was evolved from them as from the diluted sulphuric acid, with which they were compared. When a solution of ammonia, rendered a better conductor by sulphate of ammonia (554.), or a solution of subcarbonate of potassa was experimented with, the hydrogen evolved was in the same quantity as that set free from the diluted sulphuric acid with which they were compared. Hence changes in the nature of the solution do not alter the constancy of electrolytic action upon water.

731. I have already said, respecting large and small electrodes, that change of order caused no change in the general effect (715.). The same was the case with different solutions, or with different intensities; and however the circumstances of an experiment might be varied, the results came forth exceedingly consistent, and proved that the electro-chemical action was still the same.

732. I consider the foregoing investigation as sufficient to prove the very extraordinary and important principle with respect to WATER, that when subjected to the influence of the electric current, a quantity of it is decomposed exactly proportionate to the quantity of electricity which has passed, notwithstanding the thousand variations in the conditions and circumstances under which it may at the time be placed; and further, that when the interference of certain secondary effects (742. &c.), together with the solution or recombination of the gas and the evolution of air, are guarded against, the products of the decomposition may be collected with such accuracy, as to afford a very excellent and valuable measurer of the electricity concerned in their evolution.

733. The forms of instrument which I have given, figg. 64, 65, 66. (709. 710. 711.), are probably those which will be found most useful, as they indicate the quantity of electricity by the largest volume of gases, and cause the least obstruction to the passage of the current. The fluid which my present experience leads me to prefer, is a solution of sulphuric acid of specific gravity about 1.336, or from that to 1.25; but it is very essential that there should be no organic substance, nor any vegetable acid, nor other body, which, by being liable to the action of the oxygen or hydrogen evolved at the electrodes (773. &c.), shall diminish their quantity, or add other gases to them.

734. In many cases when the instrument is used as a comparative standard, or even as a measurer, it may be desirable to collect the hydrogen only, as being less liable to absorption or disappearance in other ways than the oxygen; whilst at the same time its volume is so large, as to render it a good and sensible indicator. In such cases the first and second form of apparatus have been used, figg. 62, 63. (707. 708.). The indications obtained were very constant, the variations being much smaller than in those forms of apparatus collecting both gases; and they can also be procured when solutions are used in comparative experiments, which, yielding no oxygen or only secondary results of its action, can give no indications if the educts at both electrodes be collected. Such is the case when solutions of ammonia, muriatic acid, chlorides, iodides, acetates or other vegetable salts, &c., are employed.

735. In a few cases, as where solutions of metallic salts liable to reduction at the negative electrode are acted upon, the oxygen may be advantageously used as the measuring substance. This is the case, for instance, with sulphate of copper.

736. There are therefore two general forms of the instrument which I submit as a measurer of electricity; one, in which both the gases of the water decomposed are collected (709. 710. 711.); and the other, in which a single gas, as the hydrogen only, is used (707. 708.). When referred to as a comparative instrument, (a use I shall now make of it very extensively,) it will not often require particular precaution in the observation; but when used as an absolute measurer, it will be needful that the barometric pressure and the temperature be taken into account, and that the graduation of the instruments should be to one scale; the hundredths and smaller divisions of a cubical inch are quite fit for this purpose, and the hundredth may be very conveniently taken as indicating a DEGREE of electricity.

737. It can scarcely be needful to point out further than has been done how this instrument is to be used. It is to be introduced into the course of the electric current, the action of which is to be exerted anywhere else, and if 60° or 70° of electricity are to be measured out, either in one or several portions, the current, whether strong or weak, is to be continued until the gas in the tube occupies that number of divisions or hundredths of a cubical inch. Or if a quantity competent to produce a certain effect is to be measured, the effect is to be obtained, and then the indication read off. In exact experiments it is necessary to correct the volume of gas for changes in temperature and pressure, and especially for moisture168. For the latter object the volta-electrometer (fig. 66.) is most accurate, as its gas can be measured over water, whilst the others retain it over acid or saline solutions.

738. I have not hesitated to apply the term degree (736.), in analogy with the use made of it with respect to another most important imponderable agent, namely, heat; and as the definite expansion of air, water, mercury, &c., is there made use of to measure heat, so the equally definite evolution of gases is here turned to a similar use for electricity.

739. The instrument offers the only actual measurer of voltaic electricity which we at present possess. For without being at all affected by variations in time or intensity, or alterations in the current itself, of any kind, or from any cause, or even of intermissions of action, it takes note with accuracy of the quantity of electricity which has passed through it, and reveals that quantity by inspection; I have therefore named it a VOLTA-ELECTROMETER.

740. Another mode of measuring volta-electricity may be adopted with advantage in many cases, dependent on the quantities of metals or other substances evolved either as primary or as secondary results; but I refrain from enlarging on this use of the products, until the principles on which their constancy depends have been fully established (791. 848.);

741. By the aid of this instrument I have been able to establish the definite character of electro-chemical action in its most general sense; and I am persuaded it will become of the utmost use in the extensions of the science which these views afford. I do not pretend to have made its detail perfect, but to have demonstrated the truth of the principle, and the utility of the application169.

¶ vi. On the primary or secondary character of the bodies evolved at the Electrodes.

742. Before the volta-electrometer could be employed in determining, as a general law, the constancy of electro-decomposition, it became necessary to examine a distinction, already recognised among scientific men, relative to the products of that action, namely, their primary or secondary character; and, if possible, by some general rule or principle, to decide when they were of the one or the other kind. It will appear hereafter that great mistakes inspecting electro-chemical action and its consequences have arisen from confounding these two classes of results together.

743. When a substance under decomposition yields at the electrodes those bodies uncombined and unaltered which the electric current has separated, then they may be considered as primary results, even though themselves compounds. Thus the oxygen and hydrogen from water are primary results; and so also are the acid and alkali (themselves compound bodies) evolved from sulphate of soda. But when the substances separated by the current are changed at the electrodes before their appearance, then they give rise to secondary results, although in many cases the bodies evolved are elementary.

744. These secondary results occur in two ways, being sometimes due to the mutual action of the evolved substance and the matter of the electrode, and sometimes to its action upon the substances contained in the body itself under decomposition. Thus, when carbon is made the positive electrode in dilute sulphuric acid, carbonic oxide and carbonic acid occasionally appear there instead of oxygen; for the latter, acting upon the matter of the electrode, produces these secondary results. Or if the positive electrode, in a solution of nitrate or acetate of lead, be platina, then peroxide of lead appears there, equally a secondary result with the former, but now depending upon an action of the oxygen on a substance in the solution. Again, when ammonia is decomposed by platina electrodes, nitrogen appears at the anode170; but though an elementary body, it is a secondary result in this case, being derived from the chemical action of the oxygen electrically evolved there, upon the ammonia in the surrounding solution (554.). In the same manner when aqueous solutions of metallic salts are decomposed by the current, the metals evolved at the cathode, though elements, are always secondary results, and not immediate consequences of the decomposing power of the electric current.

745. Many of these secondary results are extremely valuable; for instance, all the interesting compounds which M. Becquerel has obtained by feeble electric currents are of this nature; but they are essentially chemical, and must, in the theory of electrolytic action, be carefully distinguished from those which are directly due to the action of the electric current.

746. The nature of the substances evolved will often lead to a correct judgement of their primary or secondary character, but is not sufficient alone to establish that point. Thus, nitrogen is said to be attracted sometimes by the positive and sometimes by the negative electrode, according to the bodies with which it may be combined (554. 555.), and it is on such occasions evidently viewed as a primary result171; but I think I shall show, that, when it appears at the positive electrode, or rather at the anode, it is a secondary result (748.). Thus, also, Sir Humphry Davy172, and with him the great body of chemical philosophers, (including myself,) have given the appearance of copper, lead, tin, silver, gold, &c., at the negative electrode, when their aqueous solutions were acted upon by the voltaic current, as proofs that the metals, as a class, were attracted to that surface; thus assuming the metal, in each case, to be a primary result. These, however, I expect to prove, are all secondary results; the mere consequence of chemical action, and no proofs either of the attraction or of the law announced respecting their places173.

747. But when we take to our assistance the law of constant electro-chemical action already proved with regard to water (732.), and which I hope to extend satisfactorily to all bodies (821.), and consider the quantities as well as the nature of the substances set free, a generally accurate judgement of the primary or secondary character of the results may be formed: and this important point, so essential to the theory of electrolyzation, since it decides what are the particles directly under the influence of the current, (distinguishing them from such as are not affected,) and what are the results to be expected, may be established with such degree of certainty as to remove innumerable ambiguities and doubtful considerations from this branch of the science.

748. Let us apply these principles to the case of ammonia, and the supposed determination of nitrogen to one or the other electrode (554. 555,). A pure strong solution of ammonia is as bad a conductor, and therefore as little liable to electrolyzation, as pure water; but when sulphate of ammonia is dissolved in it, the whole becomes a conductor; nitrogen almost and occasionally quite pure is evolved at the anode, and hydrogen at the cathode; the ratio of the volume of the former to that of the latter varying, but being as 1 to about 3 or 4. This result would seem at first to imply that the electric current had decomposed ammonia, and that the nitrogen had been determined towards the positive electrode. But when the electricity used was measured out by the volta-electrometer (707. 736.), it was found that the hydrogen obtained was exactly in the proportion which would have been supplied by decomposed water, whilst the nitrogen had no certain or constant relation whatever. When, upon multiplying experiments, it was found that, by using a stronger or weaker solution, or a more or less powerful battery, the gas evolved at the anode was a mixture of oxygen and nitrogen, varying both in proportion and absolute quantity, whilst the hydrogen at the cathode remained constant, no doubt could be entertained that the nitrogen at the anode was a secondary result, depending upon the chemical action of the nascent oxygen, determined to that surface by the electric current, upon the ammonia in solution. It was the water, therefore, which was electrolyzed, not the ammonia. Further, the experiment gives no real indication of the tendency of the element nitrogen to either one electrode or the other; nor do I know of any experiment with nitric acid, or other compounds of nitrogen, which shows the tendency of this element, under the influence of the electric current, to pass in either direction along its course.

749. As another illustration of secondary results, the effects on a solution of acetate of potassa, may be quoted. When a very strong solution was used, more gas was evolved at the anode than at the cathode, in the proportion of 4 to 3 nearly: that from the anode was a mixture of carbonic oxide and carbonic acid; that from the cathode pure hydrogen. When a much weaker solution was used, less gas was evolved at the anode than at the cathode; and it now contained carburetted hydrogen, as well as carbonic oxide and carbonic acid. This result of carburetted hydrogen at the positive electrode has a very anomalous appearance, if considered as an immediate consequence of the decomposing power of the current. It, however, as well as the carbonic oxide and acid, is only a secondary result; for it is the water alone which suffers electro-decomposition, and it is the oxygen eliminated at the anode which, reacting on the acetic acid, in the midst of which it is evolved, produces those substances that finally appear there. This is fully proved by experiments with the volta-electrometer (707.); for then the hydrogen evolved from the acetate at the cathode is always found to be definite, being exactly proportionate to the electricity which has passed through the solution, and, in quantity, the same as the hydrogen evolved in the volta-electrometer itself. The appearance of the carbon in combination with the hydrogen at the positive electrode, and its non-appearance at the negative electrode, are in curious contrast with the results which might have been expected from the law usually accepted respecting the final places of the elements.

750. If the salt in solution be an acetate of lead, then the results at both electrodes are secondary, and cannot be used to estimate or express the amount of electro-chemical action, except by a circuitous process (843.). In place of oxygen or even the gases already described (749.), peroxide of lead now appears at the positive, and lead itself at the negative electrode. When other metallic solutions are used, containing, for instance, peroxides, as that of copper, combined with this or any other decomposable acid, still more complicated results will be obtained; which, viewed as direct results of the electro-chemical action, will, in their proportions, present nothing but confusion, but will appear perfectly harmonious and simple if they be considered as secondary results, and will accord in their proportions with the oxygen and hydrogen evolved from water by the action of a definite quantity of electricity.

751. I have experimented upon many bodies, with a view to determine whether the results were primary or secondary. I have been surprised to find how many of them, in ordinary cases, are of the latter class, and how frequently water is the only body electrolyzed in instances where other substances have been supposed to give way. Some of these results I will give in as few words as possible.

752. Nitric acid.—When very strong, it conducted well, and yielded oxygen at the positive electrode. No gas appeared at the negative electrode; but nitrous acid, and apparently nitric oxide, were formed there, which, dissolving, rendered the acid yellow or red, and at last even effervescent, from the spontaneous separation of nitric oxide. Upon diluting the acid with its bulk or more of water, gas appeared at the negative electrode. Its quantity could be varied by variations, either in the strength of the acid or of the voltaic current: for that acid from which no gas separated at the cathode, with a weak voltaic battery, did evolve gas there with a stronger; and that battery which evolved no gas there with a strong acid, did cause its evolution with an acid more dilute. The gas at the anode was always oxygen; that at the cathode hydrogen. When the quantity of products was examined by the volta-electrometer (707.), the oxygen, whether from strong or weak acid, proved to be in the same proportion as from water. When the acid was diluted to specific gravity 1.24, or less, the hydrogen also proved to be the same in quantity as from water. Hence I conclude that the nitric acid does not undergo electrolyzation, but the water only; that the oxygen at the anode is always a primary result, but that the products at the cathode are often secondary, and due to the reaction of the hydrogen upon the nitric acid.

753. Nitre.—A solution of this salt yields very variable results, according as one or other form of tube is used, or as the electrodes are large or small. Sometimes the whole of the hydrogen of the water decomposed may be obtained at the negative electrode; at other times, only a part of it, because of the ready formation of secondary results. The solution is a very excellent conductor of electricity.

754. Nitrate of ammonia, in aqueous solution, gives rise to secondary results very varied and uncertain in their proportions.

755. Sulphurous acid.—Pure liquid sulphurous acid does not conduct nor suffer decomposition by the voltaic current174, but, when dissolved in water, the solution acquires conducting power, and is decomposed, yielding oxygen at the anode, and hydrogen and sulphur at the cathode.

756. A solution containing sulphuric acid in addition to the sulphurous acid, was a better conductor. It gave very little gas at either electrode: that at the anode was oxygen, that at the cathode pure hydrogen. From the cathode also rose a white turbid stream, consisting of diffused sulphur, which soon rendered the whole solution milky. The volumes of gases were in no regular proportion to the quantities evolved from water in the voltameter. I conclude that the sulphurous acid was not at all affected by the electric current in any of these cases, and that the water present was the only body electro-chemically decomposed; that, at the anode, the oxygen from the water converted the sulphurous acid into sulphuric acid, and, at the cathode, the hydrogen electrically evolved decomposed the sulphurous acid, combining with its oxygen, and setting its sulphur free. I conclude that the sulphur at the negative electrode was only a secondary result; and, in fact, no part of it was found combined with the small portion of hydrogen which escaped when weak solutions of sulphurous acid were used.

757. Sulphuric acid.—I have already given my reasons for concluding that sulphuric acid is not electrolyzable, i.e. not decomposable directly by the electric current, but occasionally suffering by a secondary action at the cathode from the hydrogen evolved there (681.). In the year 1800, Davy considered the sulphur from sulphuric acid as the result of the action of the nascent hydrogen175. In 1804, Hisinger and Berzelius stated that it was the direct result of the action of the voltaic pile176, an opinion which from that time Davy seems to have adopted, and which has since been commonly received by all. The change of my own opinion requires that I should correct what I have already said of the decomposition of sulphuric acid in a former series of these Researches (552.): I do not now think that the appearance of the sulphur at the negative electrode is an immediate consequence of electrolytic action.

758. Muriatic acid.—A strong solution gave hydrogen at the negative electrode, and chlorine only at the positive electrode; of the latter, a part acted on the platina and a part was dissolved. A minute bubble of gas remained; it was not oxygen, but probably air previously held in solution.

759. It was an important matter to determine whether the chlorine was a primary result, or only a secondary product, due to the action of the oxygen evolved from water at the anode upon the muriatic acid; i.e. whether the muriatic acid was electrolyzable, and if so, whether the decomposition was definite.

760. The muriatic acid was gradually diluted. One part with six of water gave only chlorine at the anode. One part with eight of water gave only chlorine; with nine of water, a little oxygen appeared with the chlorine; but the occurrence or non-occurrence of oxygen at these strengths depended, in part, on the strength of the voltaic battery used. With fifteen parts of water, a little oxygen, with much chlorine, was evolved at the anode. As the solution was now becoming a bad conductor of electricity, sulphuric acid was added to it: this caused more ready decomposition, but did not sensibly alter the proportion of chlorine and oxygen.

761. The muriatic acid was now diluted with 100 times its volume of dilute sulphuric acid. It still gave a large proportion of chlorine at the anode, mingled with oxygen; and the result was the same, whether a voltaic battery of 40 pairs of plates or one containing only 5 pairs were used. With acid of this strength, the oxygen evolved at the anode was to the hydrogen at the cathode, in volume, as 17 is to 64; and therefore the chlorine would have been 30 volumes, had it not been dissolved by the fluid.

762. Next with respect to the quantity of elements evolved. On using the volta-electrometer, it was found that, whether the strongest or the weakest muriatic acid were used, whether chlorine alone or chlorine mingled with oxygen appeared at the anode, still the hydrogen evolved at the cathode was a constant quantity, i.e. exactly the same as the hydrogen which the same quantity of electricity could evolve from water.

763. This constancy does not decide whether the muriatic acid is electrolyzed or not, although it proves that if so, it must be in definite proportions to the quantity of electricity used. Other considerations may, however, be allowed to decide the point. The analogy between chlorine and oxygen, in their relations to hydrogen, is so strong, as to lead almost to the certainty, that, when combined with that element, they would perform similar parts in the process of electro-decomposition. They both unite with it in single proportional or equivalent quantities; and the number of proportionals appearing to have an intimate and important relation to the decomposability of a body (697.), those in muriatic acid, as well as in water, are the most favourable, or those perhaps even necessary, to decomposition. In other binary compounds of chlorine also, where nothing equivocal depending on the simultaneous presence of it and oxygen is involved, the chlorine is directly eliminated at the anode by the electric current. Such is the case with the chloride of lead (395.), which may be justly compared with protoxide of lead (402.), and stands in the same relation to it as muriatic acid to water. The chlorides of potassium, sodium, barium, &c., are in the same relation to the protoxides of the same metals and present the same results under the influence of the electric current (402.).

764. From all the experiments, combined with these considerations, I conclude that muriatic acid is decomposed by the direct influence of the electric current, and that the quantities evolved are, and therefore the chemical action is, definite for a definite quantity of electricity. For though I have not collected and measured the chlorine, in its separate state, at the anode, there can exist no doubt as to its being proportional to the hydrogen at the cathode; and the results are therefore sufficient to establish the general law of constant electro-chemical action in the case of muriatic acid.

765. In the dilute acid (761.), I conclude that a part of the water is electro-chemically decomposed, giving origin to the oxygen, which appears mingled with the chlorine at the anode. The oxygen may be viewed as a secondary result; but I incline to believe that it is not so; for, if it were, it might be expected in largest proportion from the stronger acid, whereas the reverse is the fact. This consideration, with others, also leads me to conclude that muriatic acid is more easily decomposed by the electric current than water; since, even when diluted with eight or nine times its quantity of the latter fluid, it alone gives way, the water remaining unaffected.

766. Chlorides.—On using solutions of chlorides in water,—for instance, the chlorides of sodium or calcium,—there was evolution of chlorine only at the positive electrode, and of hydrogen, with the oxide of the base, as soda or lime, at the negative electrode. The process of decomposition may be viewed as proceeding in two or three ways, all terminating in the same results. Perhaps the simplest is to consider the chloride as the substance electrolyzed, its chlorine being determined to and evolved at the anode, and its metal passing to the cathode, where, finding no more chlorine, it acts upon the water, producing hydrogen and an oxide as secondary results. As the discussion would detain me from more important matter, and is not of immediate consequence, I shall defer it for the present. It is, however, of great consequence to state, that, on using the volta-electrometer, the hydrogen in both cases was definite; and if the results do not prove the definite decomposition of chlorides, (which shall be proved elsewhere,—789. 794. 814.,) they are not in the slightest degree opposed to such a conclusion, and do support the general law.

767. Hydriodic acid.—A solution of hydriodic acid was affected exactly in the same manner as muriatic acid. When strong, hydrogen was evolved at the negative electrode, in definite proportion to the quantity of electricity which had passed, i.e. in the same proportion as was evolved by the same current from water; and iodine without any oxygen was evolved at the positive electrode. But when diluted, small quantities of oxygen appeared with the iodine at the anode, the proportion of hydrogen at the cathode remaining undisturbed.

768. I believe the decomposition of the hydriodic acid in this case to be direct, for the reasons already given respecting muriatic acid (763. 764.).

769. Iodides.—A solution of iodide of potassium being subjected to the voltaic current, iodine appeared at the positive electrode (without any oxygen), and hydrogen with free alkali at the negative electrode. The same observations as to the mode of decomposition are applicable here as were made in relation to the chlorides when in solution (766.).

770. Hydro-fluoric acid and fluorides.—Solution of hydrofluoric acid did not appear to be decomposed under the influence of the electric current: it was the water which gave way apparently. The fused fluorides were electrolysed (417.); but having during these actions obtained fluorine in the separate state, I think it better to refer to a future series of these Researches, in which I purpose giving a fuller account of the results than would be consistent with propriety here177.

771. Hydro-cyanic acid in solution conducts very badly. The definite proportion of hydrogen (equal to that from water) was set free at the cathode, whilst at the anode a small quantity of oxygen was evolved and apparently a solution of cyanogen formed. The action altogether corresponded with that on a dilute muriatic or hydriodic acid. When the hydrocyanic acid was made a better conductor by sulphuric acid, the same results occurred.

Cyanides.—With a solution of the cyanide of potassium, the result was precisely the same as with a chloride or iodide. No oxygen was evolved at the positive electrode, but a brown solution formed there. For the reasons given when speaking of the chlorides (766.), and because a fused cyanide of potassium evolves cyanogen at the positive electrode178, I incline to believe that the cyanide in solution is directly decomposed.

772. Ferro-cyanic acid and the ferro-cyanides, as also sulpho-cyanic acid and the sulpho-cyanides, presented results corresponding with those just described (771.).

773. Acetic acid.—Glacial acetic acid, when fused (405.), is not decomposed by, nor does it conduct, electricity. On adding a little water to it, still there were no signs of action; on adding more water, it acted slowly and about as pure water would do. Dilute sulphuric acid was added to it in order to make it a better conductor; then the definite proportion of hydrogen was evolved at the cathode, and a mixture of oxygen in very deficient quantity, with carbonic acid, and a little carbonic oxide, at the anode. Hence it appears that acetic acid is not electrolyzable, but that a portion of it is decomposed by the oxygen evolved at the anode, producing secondary results, varying with the strength of the acid, the intensity of the current, and other circumstances.

774. Acetates.—One of these has been referred to already, as affording only secondary results relative to the acetic acid (749.). With many of the metallic acetates the results at both electrodes are secondary (746. 750.).

Acetate of soda fused and anhydrous is directly decomposed, being, as I believe, a true electrolyte, and evolving soda and acetic acid at the cathode and anode. These however have no sensible duration, but are immediately resolved into other substances; charcoal, sodiuretted hydrogen, &c., being set free at the former, and, as far as I could judge under the circumstances, acetic acid mingled with carbonic oxide, carbonic acid, &c. at the latter.

775. Tartaric acid.—Pure solution of tartaric acid is almost as bad a conductor as pure water. On adding sulphuric acid, it conducted well, the results at the positive electrode being primary or secondary in different proportions, according to variations in the strength of the acid and the power of the electric current (752.). Alkaline tartrates gave a large proportion of secondary results at the positive electrode. The hydrogen at the negative electrode remained constant unless certain triple metallic salts were used.

776. Solutions, of salts containing other vegetable acids, as the benzoates; of sugar, gum, &c., dissolved in dilute sulphuric acid; of resin, albumen, &c., dissolved in alkalies, were in turn submitted to the electrolytic power of the voltaic current. In all these cases, secondary results to a greater or smaller extent were produced at the positive electrode.

777. In concluding this division of these Researches, it cannot but occur to the mind that the final result of the action of the electric current upon substances, placed between the electrodes, instead of being simple may be very complicated. There are two modes by which these substances may be decomposed, either by the direct force of the electric current, or by the action of bodies which that current may evolve. There are also two modes by which new compounds may be formed, i.e. by combination of the evolving substances whilst in their nascent state (658.), directly with the matter of the electrode; or else their combination with those bodies, which being contained in, or associated with, the body suffering decomposition, are necessarily present at the anode and cathode. The complexity is rendered still greater by the circumstance that two or more of these actions may occur simultaneously, and also in variable proportions to each other. But it may in a great measure be resolved by attention to the principles already laid down (747.).

778. When aqueous solutions of bodies are used, secondary results are exceedingly frequent. Even when the water is not present in large quantity, but is merely that of combination, still secondary results often ensue: for instance, it is very possible that in Sir Humphry Davy's decomposition of the hydrates of potassa and soda, a part of the potassium produced was the result of a secondary action. Hence, also, a frequent cause for the disappearance of the oxygen and hydrogen which would otherwise be evolved: and when hydrogen does not appear at the cathode in an aqueous solution, it perhaps always indicates that a secondary action has taken place there. No exception to this rule has as yet occurred to my observation.

779. Secondary actions are not confined to aqueous solutions, or cases where water is present. For instance, various chlorides acted upon, when fused (402.), by platina electrodes, have the chlorine determined electrically to the anode. In many cases, as with the chlorides of lead, potassium, barium, &c., the chlorine acts on the platina and forms a compound with it, which dissolves; but when protochloride of tin is used, the chlorine at the anode does not act upon the platina, but upon the chloride already there, forming a perchloride which rises in vapour (790. 804.). These are, therefore, instances of secondary actions of both kinds, produced in bodies containing no water.

780. The production of boron from fused borax (402. 417.) is also a case of secondary action; for boracic acid is not decomposable by electricity (408.), and it was the sodium evolved at the cathode which, re-acting on the boracic acid around it, took oxygen from it and set boron free in the experiments formerly described.

781. Secondary actions have already, in the hands of M. Becquerel, produced many interesting results in the formation of compounds; some of them new, others imitations of those occurring naturally179. It is probable they may prove equally interesting in an opposite direction, i.e. as affording cases of analytic decomposition. Much information regarding the composition, and perhaps even the arrangement, of the particles of such bodies as the vegetable acids and alkalies, and organic compounds generally, will probably be obtained by submitting them to the action of nascent oxygen, hydrogen, chlorine, &c. at the electrodes; and the action seems the more promising, because of the thorough command which we possess over attendant circumstances, such as the strength of the current, the size of the electrodes, the nature of the decomposing conductor, its strength, &c., all of which may be expected to have their corresponding influence upon the final result.

782. It is to me a great satisfaction that the extreme variety of secondary results has presented nothing opposed to the doctrine of a constant and definite electro-chemical action, to the particular consideration of which I shall now proceed.

¶ vii. On the definite nature and extent of Electro-chemical Decomposition.

783. In the third series of these Researches, after proving the identity of electricities derived from different sources, and showing, by actual measurement, the extraordinary quantity of electricity evolved by a very feeble voltaic arrangement (371. 376.), I announced a law, derived from experiment, which seemed to me of the utmost importance to the science of electricity in general, and that branch of it denominated electro-chemistry in particular. The law was expressed thus: The chemical power of a current of electricity is in direct proportion to the absolute quantity of electricity which passes (377.).

784. In the further progress of the successive investigations, I have had frequent occasion to refer to the same law, sometimes in circumstances offering powerful corroboration of its truth (456. 504. 505.); and the present series already supplies numerous new cases in which it holds good (704. 722. 726. 732.). It is now my object to consider this great principle more closely, and to develope some of the consequences to which it leads. That the evidence for it may be the more distinct and applicable, I shall quote cases of decomposition subject to as few interferences from secondary results as possible, effected upon bodies very simple, yet very definite in their nature.

785. In the first place, I consider the law as so fully established with respect to the decomposition of water, and under so many circumstances which might be supposed, if anything could, to exert an influence over it, that I may be excused entering into further detail respecting that substance, or even summing up the results here (732.). I refer, therefore, to the whole of the subdivision of this series of Researches which contains the account of the volta-electrometer (704. &c.).

786. In the next place, I also consider the law as established with respect to muriatic acid by the experiments and reasoning already advanced, when speaking of that substance, in the subdivision respecting primary and secondary results (758. &c.).

787. I consider the law as established also with regard to hydriodic acid by the experiments and considerations already advanced in the preceding division of this series of Researches (767. 768.).

788. Without speaking with the same confidence, yet from the experiments described, and many others not described, relating to hydro-fluoric, hydro-cyanic, ferro-cyanic, and sulpho-cyanic acids (770. 771. 772.), and from the close analogy which holds between these bodies and the hydracids of chlorine, iodine, bromine, &c., I consider these also as coming under subjection to the law, and assisting to prove its truth.

789. In the preceding cases, except the first, the water is believed to be inactive; but to avoid any ambiguity arising from its presence, I sought for substances from which it should be absent altogether; and, taking advantage of the law of conduction already developed (380. &c.), I soon found abundance, amongst which protochloride of tin was first subjected to decomposition in the following manner. A piece of platina wire had one extremity coiled up into a small knob, and, having been carefully weighed, was sealed hermetically into a piece of bottle-glass tube, so that the knob should be at the bottom of the tube within (fig. 68.). The tube was suspended by a piece of platina wire, so that the heat of a spirit-lamp could be applied to it. Recently fused protochloride of tin was introduced in sufficient quantity to occupy, when melted, about one-half of the tube; the wire of the tube was connected with a volta-electrometer (711.), which was itself connected with the negative end of a voltaic battery; and a platina wire connected with the positive end of the same battery was dipped into the fused chloride in the tube; being however so bent, that it could not by any shake of the hand or apparatus touch the negative electrode at the bottom of the vessel. The whole arrangement is delineated in fig. 69.

790. Under these circumstances the chloride of tin was decomposed: the chlorine evolved at the positive electrode formed bichloride of tin (779.), which passed away in fumes, and the tin evolved at the negative electrode combined with the platina, forming an alloy, fusible at the temperature to which the tube was subjected, and therefore never occasioning metallic communication through the decomposing chloride. When the experiment had been continued so long as to yield a reasonable quantity of gas in the volta-electrometer, the battery connexion was broken, the positive electrode removed, and the tube and remaining chloride allowed to cool. When cold, the tube was broken open, the rest of the chloride and the glass being easily separable from the platina wire and its button of alloy. The latter when washed was then reweighed, and the increase gave the weight of the tin reduced.

791. I will give the particular results of one experiment, in illustration of the mode adopted in this and others, the results of which I shall have occasion to quote. The negative electrode weighed at first 20 grains; after the experiment, it, with its button of alloy, weighed 23.2 grains. The tin evolved by the electric current at the cathode: weighed therefore 3.2 grains. The quantity of oxygen and hydrogen collected in the volta-electrometer = 3.85 cubic inches. As 100 cubic inches of oxygen and hydrogen, in the proportions to form water, may be considered as weighing 12.92 grains, the 3.85 cubic inches would weigh 0.49742 of a grain; that being, therefore, the weight of water decomposed by the same electric current as was able to decompose such weight of protochloride of tin as could yield 3.2 grains of metal. Now 0.49742 : 3.2 :: 9 the equivalent of water is to 57.9, which should therefore be the equivalent of tin, if the experiment had been made without error, and if the electro-chemical decomposition is in this case also definite. In some chemical works 58 is given as the chemical equivalent of tin, in others 57.9. Both are so near to the result of the experiment, and the experiment itself is so subject to slight causes of variation (as from the absorption of gas in the volta-electrometer (716.), &c.), that the numbers leave little doubt of the applicability of the law of definite action in this and all similar cases of electro-decomposition.

792. It is not often I have obtained an accordance in numbers so near as that I have just quoted. Four experiments were made on the protochloride of tin, the quantities of gas evolved in the volta-electrometer being from 2.05 to 10.29 cubic inches. The average of the four experiments gave 58.53 as the electro-chemical equivalent for tin.

793. The chloride remaining after the experiment was pure protochloride of tin; and no one can doubt for a moment that the equivalent of chlorine had been evolved at the anode, and, having formed bichloride of tin as a secondary result, had passed away.

794. Chloride of lead was experimented upon in a manner exactly similar, except that a change was made in the nature of the positive electrode; for as the chlorine evolved at the anode forms no perchloride of lead, but acts directly upon the platina, it produces, if that metal be used, a solution of chloride of platina in the chloride of lead; in consequence of which a portion of platina can pass to the cathode, and would then produce a vitiated result. I therefore sought for, and found in plumbago, another substance, which could be used safely as the positive electrode in such bodies as chlorides, iodides, &c. The chlorine or iodine does not act upon it, but is evolved in the free state; and the plumbago has no re-action, under the circumstances, upon the fused chloride or iodide in which it is plunged. Even if a few particles of plumbago should separate by the heat or the mechanical action of the evolved gas, they can do no harm in the chloride.

795. The mean of three experiments gave the number of 100.85 as the equivalent for lead. The chemical equivalent is 103.5. The deficiency in my experiments I attribute to the solution of part of the gas (716.) in the volta-electrometer; but the results leave no doubt on my mind that both the lead and the chlorine are, in this case, evolved in definite quantities by the action of a given quantity of electricity (814. &c.).

796. Chloride of antimony.—It was in endeavouring to obtain the electro-chemical equivalent of antimony from the chloride, that I found reasons for the statement I have made respecting the presence of water in it in an earlier part of these Researches (690. 693. &c.).

797. I endeavoured to experiment upon the oxide of lead obtained by fusion and ignition of the nitrate in a platina crucible, but found great difficulty, from the high temperature required for perfect fusion, and the powerful fluxing qualities of the substance. Green-glass tubes repeatedly failed. I at last fused the oxide in a small porcelain crucible, heated fully in a charcoal fire; and, as it is was essential that the evolution of the lead at the cathode should take place beneath the surface, the negative electrode was guarded by a green-glass tube, fused around it in such a manner as to expose only the knob of platina at the lower end (fig. 70.), so that it could be plunged beneath the surface, and thus exclude contact of air or oxygen with the lead reduced there. A platina wire was employed for the positive electrode, that metal not being subject to any action from the oxygen evolved against it. The arrangement is given in fig. 71.

798. In an experiment of this kind the equivalent for the lead came out 93.17, which is very much too small. This, I believe, was because of the small interval between the positive and negative electrodes in the oxide of lead; so that it was not unlikely that some of the froth and bubbles formed by the oxygen at the anode should occasionally even touch the lead reduced at the cathode, and re-oxidize it. When I endeavoured to correct this by having more litharge, the greater heat required to keep it all fluid caused a quicker action on the crucible, which was soon eaten through, and the experiment stopped.

799. In one experiment of this kind I used borate of lead (408. 673.). It evolves lead, under the influence of the electric current, at the anode, and oxygen at the cathode; and as the boracic acid is not either directly (408.) or incidentally decomposed during the operation, I expected a result dependent on the oxide of lead. The borate is not so violent a flux as the oxide, but it requires a higher temperature to make it quite liquid; and if not very hot, the bubbles of oxygen cling to the positive electrode, and retard the transfer of electricity. The number for lead came out 101.29, which is so near to 103.5 as to show that the action of the current had been definite.

800. Oxide of bismuth.—I found this substance required too high a temperature, and acted too powerfully as a flux, to allow of any experiment being made on it, without the application of more time and care than I could give at present.

801. The ordinary protoxide of antimony, which consists of one proportional of metal and one and a half of oxygen, was subjected to the action of the electric current in a green-glass tube (789.), surrounded by a jacket of platina foil, and heated in a charcoal fire. The decomposition began and proceeded very well at first, apparently indicating, according to the general law (679. 697.), that this substance was one containing such elements and in such proportions as made it amenable to the power of the electric current. This effect I have already given reasons for supposing may be due to the presence of a true protoxide, consisting of single proportionals (696. 693.). The action soon diminished, and finally ceased, because of the formation of a higher oxide of the metal at the positive electrode. This compound, which was probably the peroxide, being infusible and insoluble in the protoxide, formed a crystalline crust around the positive electrode; and thus insulating it, prevented the transmission of the electricity. Whether, if it had been fusible and still immiscible, it would have decomposed, is doubtful, because of its departure from the required composition (697.). It was a very natural secondary product at the positive electrode (779.). On opening the tube it was found that a little antimony had been separated at the negative electrode; but the quantity was too small to allow of any quantitative result being obtained180.

802. Iodide of lead.—This substance can be experimented with in tubes heated by a spirit-lamp (789.); but I obtained no good results from it, whether I used positive electrodes of platina or plumbago. In two experiments the numbers for the lead came out only 75.46 and 73.45, instead of 103.5. This I attribute to the formation of a periodide at the positive electrode, which, dissolving in the mass of liquid iodide, came in contact with the lead evolved at the negative electrode, and dissolved part of it, becoming itself again protiodide. Such a periodide does exist; and it is very rarely that the iodide of lead formed by precipitation, and well-washed, can be fused without evolving much iodine, from the presence of this percompound; nor does crystallization from its hot aqueous solution free it from this substance. Even when a little of the protiodide and iodine are merely rubbed together in a mortar, a portion of the periodide is formed. And though it is decomposed by being fused and heated to dull redness for a few minutes, and the whole reduced to protiodide, yet that is not at all opposed to the possibility, that a little of that which is formed in great excess of iodine at the anode, should be carried by the rapid currents in the liquid into contact with the cathode.

803. This view of the result was strengthened by a third experiment, where the space between the electrodes was increased to one third of an inch; for now the interfering effects were much diminished, and the number of the lead came out 89.04; and it was fully confirmed by the results obtained in the cases of transfer to be immediately described (818.).

The experiments on iodide of lead therefore offer no exception to the general law under consideration, but on the contrary may, from general considerations, be admitted as included in it.

804. Protiodide of tin.—This substance, when fused (402.), conducts and is decomposed by the electric current, tin is evolved at the anode, and periodide of tin as a secondary result (779. 790.) at the cathode. The temperature required for its fusion is too high to allow of the production of any results fit for weighing.

805. Iodide of potassium was subjected to electrolytic action in a tube, like that in fig. 68. (789.). The negative electrode was a globule of lead, and I hoped in this way to retain the potassium, and obtain results that could be weighed and compared with the volta-electrometer indication; but the difficulties dependent upon the high temperature required, the action upon the glass, the fusibility of the platina induced by the presence of the lead, and other circumstances, prevented me from procuring such results. The iodide was decomposed with the evolution of iodine at the anode, and of potassium at the cathode, as in former cases.

806. In some of these experiments several substances were placed in succession, and decomposed simultaneously by the same electric current: thus, protochloride of tin, chloride of lead, and water, were thus acted on at once. It is needless to say that the results were comparable, the tin, lead, chlorine, oxygen, and hydrogen evolved being definite in quantity and electro-chemical equivalents to each other.

* * * * *

807. Let us turn to another kind of proof of the definite chemical action of electricity. If any circumstances could be supposed to exert an influence over the quantity of the matters evolved during electrolytic action, one would expect them to be present when electrodes of different substances, and possessing very different chemical affinities for such matters, were used. Platina has no power in dilute sulphuric acid of combining with the oxygen at the anode, though the latter be evolved in the nascent state against it. Copper, on the other hand, immediately unites with the oxygen, as the electric current sets it free from the hydrogen; and zinc is not only able to combine with it, but can, without any help from the electricity, abstract it directly from the water, at the same time setting torrents of hydrogen free. Yet in cases where these three substances were used as the positive electrodes in three similar portions of the same dilute sulphuric acid, specific gravity 1.336, precisely the same quantity of water was decomposed by the electric current, and precisely the same quantity of hydrogen set free at the cathodes of the three solutions.

808. The experiment was made thus. Portions of the dilute sulphuric acid were put into three basins. Three volta-electrometer tubes, of the form figg. 60. 62. were filled with the same acid, and one inverted in each basin (707.). A zinc plate, connected with the positive end of a voltaic battery, was dipped into the first basin, forming the positive electrode there, the hydrogen, which was abundantly evolved from it by the direct action of the acid, being allowed to escape. A copper plate, which dipped into the acid of the second basin, was connected with the negative electrode of the first basin; and a platina plate, which dipped into the acid of the third basin, was connected with the negative electrode of the second basin. The negative electrode of the third basin was connected with a volta-electrometer (711.), and that with the negative end of the voltaic battery.

809. Immediately that the circuit was complete, the electro-chemical action commenced in all the vessels. The hydrogen still rose in, apparently, undiminished quantities from the positive zinc electrode in the first basin. No oxygen was evolved at the positive copper electrode in the second basin, but a sulphate of copper was formed there; whilst in the third basin the positive platina electrode evolved pure oxygen gas, and was itself unaffected. But in all the basins the hydrogen liberated at the negative platina electrodes was the same in quantity, and the same with the volume of hydrogen evolved in the volta-electrometer, showing that in all the vessels the current had decomposed an equal quantity of water. In this trying case, therefore, the chemical action of electricity proved to be perfectly definite.

810. A similar experiment was made with muriatic acid diluted with its bulk of water. The three positive electrodes were zinc, silver, and platina; the first being able to separate and combine with the chlorine without the aid of the current; the second combining with the chlorine only after the current had set it free; and the third rejecting almost the whole of it. The three negative electrodes were, as before, platina plates fixed within glass tubes. In this experiment, as in the former, the quantity of hydrogen evolved at the cathodes was the same for all, and the same as the hydrogen evolved in the volta-electrometer. I have already given my reasons for believing that in these experiments it is the muriatic acid which is directly decomposed by the electricity (764.); and the results prove that the quantities so decomposed are perfectly definite and proportionate to the quantity of electricity which has passed.

811. In this experiment the chloride of silver formed in the second basin retarded the passage of the current of electricity, by virtue of the law of conduction before described (394.), so that it had to be cleaned off four or five times during the course of the experiment; but this caused no difference between the results of that vessel and the others.

812. Charcoal was used as the positive electrode in both sulphuric and muriatic acids (808. 810.); but this change produced no variation of the results. A zinc positive electrode, in sulphate of soda or solution of common salt, gave the same constancy of operation.

813. Experiments of a similar kind were then made with bodies altogether in a different state, i.e. with fused chlorides, iodides, &c. I have already described an experiment with fused chloride of silver, in which the electrodes were of metallic silver, the one rendered negative becoming increased and lengthened by the addition of metal, whilst the other was dissolved and eaten away by its abstraction. This experiment was repeated, two weighed pieces of silver wire being used as the electrodes, and a volta-electrometer included in the circuit. Great care was taken to withdraw the negative electrodes so regularly and steadily that the crystals of reduced silver should not form a metallic communication beneath the surface of the fused chloride. On concluding the experiment the positive electrode was re-weighed, and its loss ascertained. The mixture of chloride of silver, and metal, withdrawn in successive portions at the negative electrode, was digested in solution of ammonia, to remove the chloride, and the metallic silver remaining also weighed: it was the reduction at the cathode, and exactly equalled the solution at the anode; and each portion was as nearly as possible the equivalent to the water decomposed in the volta-electrometer.

814. The infusible condition of the silver at the temperature used, and the length and ramifying character of its crystals, render the above experiment difficult to perform, and uncertain in its results. I therefore wrought with chloride of lead, using a green-glass tube, formed as in fig. 72. A weighed platina wire was fused into the bottom of a small tube, as before described (789.). The tube was then bent to an angle, at about half an inch distance from the closed end; and the part between the angle and the extremity being softened, was forced upward, as in the figure, so as to form a bridge, or rather separation, producing two little depressions or basins a, b, within the tube. This arrangement was suspended by a platina wire, as before, so that the heat of a spirit-lamp could be applied to it, such inclination being given to it as would allow all air to escape during the fusion of the chloride of lead. A positive electrode was then provided, by bending up the end of a platina wire into a knot, and fusing about twenty grains of metallic lead on to it, in a small closed tube of glass, which was afterwards broken away. Being so furnished, the wire with its lead was weighed, and the weight recorded.

815. Chloride of lead was now introduced into the tube, and carefully fused. The leaded electrode was also introduced; after which the metal, at its extremity, soon melted. In this state of things the tube was filled up to c with melted chloride of lead; the end of the electrode to be rendered negative was in the basin b, and the electrode of melted lead was retained in the basin a, and, by connexion with the proper conducting wire of a voltaic battery, was rendered positive. A volta-electrometer was included in the circuit.

816. Immediately upon the completion of the communication with the voltaic battery, the current passed, and decomposition proceeded. No chlorine was evolved at the positive electrode; but as the fused chloride was transparent, a button of alloy could be observed gradually forming and increasing in size at b, whilst the lead at a could also be seen gradually to diminish. After a time, the experiment was stopped; the tube allowed to cool, and broken open; the wires, with their buttons, cleaned and weighed; and their change in weight compared with the indication of the volta-electrometer.

817. In this experiment the positive electrode had lost just as much lead as the negative one had gained (795.), and the loss and gain were very nearly the equivalents of the water decomposed in the volta-electrometer, giving for lead the number 101.5. It is therefore evident, in this instance, that causing a strong affinity, or no affinity, for the substance evolved at the anode, to be active during the experiment (807.), produces no variation in the definite action of the electric current.

818. A similar experiment was then made with iodide of lead, and in this manner all confusion from the formation of a periodide avoided (803.). No iodine was evolved during the whole action, and finally the loss of lead at the anode was the same as the gain at the cathode, the equivalent number, by comparison with the result in the volta-electrometer, being 103.5.

819. Then protochloride of tin was subjected to the electric current in the same manner, using of course, a tin positive electrode. No bichloride of tin was now formed (779. 790.). On examining the two electrodes, the positive had lost precisely as much as the negative had gained; and by comparison with the volta-electrometer, the number for tin came out 59.

820. It is quite necessary in these and similar experiments to examine the interior of the bulbs of alloy at the ends of the conducting wires; for occasionally, and especially with those which have been positive, they are cavernous, and contain portions of the chloride or iodide used, which must be removed before the final weight is ascertained. This is more usually the case with lead than tin.

821. All these facts combine into, I think, an irresistible mass of evidence, proving the truth of the important proposition which I at first laid down, namely, that the chemical power of a current of electricity is in direct proportion to the absolute quantity of electricity which passes (377. 783.). They prove, too, that this is not merely true with one substance, as water, but generally with all electrolytic bodies; and, further, that the results obtained with any one substance do not merely agree amongst themselves, but also with those obtained from other substances, the whole combining together into one series of definite electro-chemical actions (505.). I do not mean to say that no exceptions will appear: perhaps some may arise, especially amongst substances existing only by weak affinity; but I do not expect that any will seriously disturb the result announced. If, in the well-considered, well-examined, and, I may surely say, well-ascertained doctrines of the definite nature of ordinary chemical affinity, such exceptions occur, as they do in abundance, yet, without being allowed to disturb our minds as to the general conclusion, they ought also to be allowed if they should present themselves at this, the opening of a new view of electro-chemical action; not being held up as obstructions to those who may be engaged in rendering that view more and more perfect, but laid aside for a while, in hopes that their perfect and consistent explanation will ultimately appear.

* * * * *

822. The doctrine of definite electro-chemical action just laid down, and, I believe, established, leads to some new views of the relations and classifications of bodies associated with or subject to this action. Some of these I shall proceed to consider.

823. In the first place, compound bodies may be separated into two great classes, namely, those which are decomposable by the electric current, and those which are not: of the latter, some are conductors, others non-conductors, of voltaic electricity181. The former do not depend for their decomposability upon the nature of their elements only; for, of the same two elements, bodies may be formed, of which one shall belong to one class and another to the other class; but probably on the proportions also (697.). It is further remarkable, that with very few, if any, exceptions (414. 691.), these decomposable bodies are exactly those governed by the remarkable law of conduction I have before described (694.); for that law does not extend to the many compound fusible substances that are excluded from this class. I propose to call bodies of this, the decomposable class, Electrolytes (664.).

824. Then, again, the substances into which these divide, under the influence of the electric current, form an exceedingly important general class. They are combining bodies; are directly associated with the fundamental parts of the doctrine of chemical affinity; and have each a definite proportion, in which they are always evolved during electrolytic action. I have proposed to call these bodies generally ions, or particularly anions and cations, according as they appear at the anode or cathode (665.); and the numbers representing the proportions in which they are evolved electro-chemical equivalents. Thus hydrogen, oxygen, chlorine, iodine, lead, tin are ions; the three former are anions, the two metals are cations, and 1, 8, 3, 125, 104, 58, are their electro-chemical equivalents nearly.

825. A summary of certain points already ascertained respecting electrolytes, ions, and electro-chemical equivalents, may be given in the following general form of propositions, without, I hope, including any serious error.

826. i. A single ion, i.e. one not in combination with another, will have no tendency to pass to either of the electrodes, and will be perfectly indifferent to the passing current, unless it be itself a compound of more elementary ions, and so subject to actual decomposition. Upon this fact is founded much of the proof adduced in favour of the new theory of electro-chemical decomposition, which I put forth in a former series of these Researches (518. &c.).

827. ii. If one ion be combined in right proportions (697.) with another strongly opposed to it in its ordinary chemical relations, i.e. if an anion be combined with a cation, then both will travel, the one to the anode, the other to the cathode, of the decomposing body (530, 542. 547.).

828. iii. If, therefore, an ion pass towards one of the electrodes, another ion must also be passing simultaneously to the other electrode, although, from secondary action, it may not make its appearance (743.).

829. iv. A body decomposable directly by the electric current, i.e. an electrolyte, must consist of two ions, and must also render them up during the act of decomposition.

830. v. There is but one electrolyte composed of the same two elementary ions; at least such appears to be the fact (697.), dependent upon a law, that only single electro-chemical equivalents of elementary ions can go to the electrodes, and not multiples.

831. vi. A body not decomposable when alone, as boracic acid, is not directly decomposable by the electric current when in combination (780.). It may act as an ion going wholly to the anode or cathode, but does not yield up its elements, except occasionally by a secondary action. Perhaps it is superfluous for me to point out that this proposition has no relation to such cases as that of water, which, by the presence of other bodies, is rendered a better conductor of electricity, and therefore is more freely decomposed.

832. vii. The nature of the substance of which the electrode is formed, provided it be a conductor, causes no difference in the electro-decomposition, either in kind or degree (807. 813.): but it seriously influences, by secondary action (714.), the state in which the finally appear. Advantage may be taken of this principle in combining and ions collecting such ions as, if evolved in their free state, would be unmanageable182.

833. viii. A substance which, being used as the electrode, can combine with the ion evolved against it, is also, I believe, an ion, and combines, in such cases, in the quantity represented by its electro-chemical equivalent. All the experiments I have made agree with this view; and it seems to me, at present, to result as a necessary consequence. Whether, in the secondary actions that take place, where the ion acts, not upon the matter of the electrode, but on that which is around it in the liquid (744.), the same consequence follows, will require more extended investigation to determine.

834. ix. Compound ions are not necessarily composed of electro-chemical equivalents of simple ions. For instance, sulphuric acid, boracic acid, phosphoric acid, are ions, but not electrolytes, i.e. not composed of electro-chemical equivalents of simple ions.

835. x. Electro-chemical equivalents are always consistent; i.e. the same number which represents the equivalent of a substance A when it is separating from a substance B, will also represent A when separating from a third substance C. Thus, 8 is the electro-chemical equivalent of oxygen, whether separating from hydrogen, or tin, or lead; and 103.5 is the electrochemical equivalent of lead, whether separating from oxygen, or chlorine, or iodine.

836. xi. Electro-chemical equivalents coincide, and are the same, with ordinary chemical equivalents.

837. By means of experiment and the preceding propositions, a knowledge of ions and their electro-chemical equivalents may be obtained in various ways.

838. In the first place, they may be determined directly, as has been done with hydrogen, oxygen, lead, and tin, in the numerous experiments already quoted.

839. In the next place, from propositions ii. and iii., may be deduced the knowledge of many other ions, and also their equivalents. When chloride of lead was decomposed, platina being used for both electrodes (395.), there could remain no more doubt that chlorine was passing to the anode, although it combined with the platina there, than when the positive electrode, being of plumbago (794.), allowed its evolution in the free state; neither could there, in either case, remain any doubt that for every 103.5 parts of lead evolved at the cathode, 36 parts of chlorine were evolved at the anode, for the remaining chloride of lead was unchanged. So also, when in a metallic solution one volume of oxygen, or a secondary compound containing that proportion, appeared at the anode, no doubt could arise that hydrogen, equivalent to two volumes, had been determined to the cathode, although, by a secondary action, it had been employed in reducing oxides of lead, copper, or other metals, to the metallic state. In this manner, then, we learn from the experiments already described in these Researches, that chlorine, iodine, bromine, fluorine, calcium, potassium, strontium, magnesium, manganese, &c., are ions and that their electro-chemical equivalents are the same as their ordinary chemical equivalents.

840. Propositions iv. and v. extend our means of gaining information. For if a body of known chemical composition is found to be decomposable, and the nature of the substance evolved as a primary or even a secondary result (743. 777.) at one of the electrodes, be ascertained, the electro-chemical equivalent of that body may be deduced from the known constant composition of the substance evolved. Thus, when fused protiodide of tin is decomposed by the voltaic current (804.), the conclusion may be drawn, that both the iodine and tin are ions, and that the proportions in which they combine in the fused compound express their electro-chemical equivalents. Again, with respect to the fused iodide of potassium (805.), it is an electrolyte; and the chemical equivalents will also be the electro-chemical equivalents.

841. If proposition viii. sustain extensive experimental investigation, then it will not only help to confirm the results obtained by the use of the other propositions, but will give abundant original information of its own.

842. In many instances, the secondary results obtained by the action of the evolved ion on the substances present in the surrounding liquid or solution, will give the electro-chemical equivalent. Thus, in the solution of acetate of lead, and, as far as I have gone, in other proto-salts subjected to the reducing action of the nascent hydrogen at the cathode, the metal precipitated has been in the same quantity as if it had been a primary product, (provided no free hydrogen escaped there,) and therefore gave accurately the number representing its electro-chemical equivalent.

843. Upon this principle it is that secondary results may occasionally be used as measurers of the volta-electric current (706. 740.); but there are not many metallic solutions that answer this purpose well: for unless the metal is easily precipitated, hydrogen will be evolved at the cathode and vitiate the result. If a soluble peroxide is formed at the anode, or if the precipitated metal crystallize across the solution and touch the positive electrode, similar vitiated results are obtained. I expect to find in some salts, as the acetates of mercury and zinc, solutions favourable for this use.

844. After the first experimental investigations to establish the definite chemical action of electricity, I have not hesitated to apply the more strict results of chemical analysis to correct the numbers obtained as electrolytic results. This, it is evident, may be done in a great number of cases, without using too much liberty towards the due severity of scientific research. The series of numbers representing electro-chemical equivalents must, like those expressing the ordinary equivalents of chemically acting bodies, remain subject to the continual correction of experiment and sound reasoning.

845. I give the following brief Table of ions and their electro-chemical equivalents, rather as a specimen of a first attempt than as anything that can supply the want which must very quickly be felt, of a full and complete tabular account of this class of bodies. Looking forward to such a table as of extreme utility (if well-constructed) in developing the intimate relation of ordinary chemical affinity to electrical actions, and identifying the two, not to the imagination merely, but to the conviction of the senses and a sound judgement, I may be allowed to express a hope, that the endeavour will always be to make it a table of real, and not hypothetical, electro-chemical equivalents; for we shall else overrun the facts, and lose all sight and consciousness of the knowledge lying directly in our path.

846. The equivalent numbers do not profess to be exact, and are taken almost entirely from the chemical results of other philosophers in whom I could repose more confidence, as to these points, than in myself.

847. TABLE OF IONS.

848. This Table might be further arrange into groups of such substances as either act with, or replace, each other. Thus, for instance, acids and bases act in relation to each other; but they do not act in association with oxygen, hydrogen, or elementary substances. There is indeed little or no doubt that, when the electrical relations of the particles of matter come to be closely examined, this division must be made. The simple substances, with cyanogen, sulpho-cyanogen, and one or two other compound bodies, will probably form the first group; and the acids and bases, with such analogous compounds as may prove to be ions, the second group. Whether these will include all ions, or whether a third class of more complicated results will be required, must be decided by future experiments.

849. It is probable that all our present elementary bodies are ions, but that is not as yet certain. There are some, such as carbon, phosphorus, nitrogen, silicon, boron, alumium, the right of which to the title of ion it is desirable to decide as soon as possible. There are also many compound bodies, and amongst them alumina and silica, which it is desirable to class immediately by unexceptionable experiments. It is also possible, that all combinable bodies, compound as well as simple, may enter into the class of ions; but at present it does not seem to me probable. Still the experimental evidence I have is so small in proportion to what must gradually accumulate around, and bear upon, this point, that I am afraid to give a strong opinion upon it.

850. I think I cannot deceive myself in considering the doctrine of definite electro-chemical action as of the utmost importance. It touches by its facts more directly and closely than any former fact, or set of facts, have done, upon the beautiful idea, that ordinary chemical affinity is a mere consequence of the electrical attractions of the particles of different kinds of matter; and it will probably lead us to the means by which we may enlighten that which is at present so obscure, and either fully demonstrate the truth of the idea, or develope that which ought to replace it.

851. A very valuable use of electro-chemical equivalents will be to decide, in cases of doubt, what is the true chemical equivalent, or definite proportional, or atomic number of a body; for I have such conviction that the power which governs electro-decomposition and ordinary chemical attractions is the same; and such confidence in the overruling influence of those natural laws which render the former definite, as to feel no hesitation in believing that the latter must submit to them also. Such being the case, I can have, no doubt that, assuming hydrogen as 1, and dismissing small fractions for the simplicity of expression, the equivalent number or atomic weight of oxygen is 8, of chlorine 36, of bromine 78.4, of lead 103.5, of tin 59, &c., notwithstanding that a very high authority doubles several of these numbers.