400. Occasionally the substances were contained in small bent tubes of green glass, and when fused, the platina poles introduced, one on each side. In such cases the same general results as those already described were procured; but a further advantage was obtained, namely, that whilst the substance was conducting and suffering decomposition, the final arrangement of the elements could be observed. Thus, iodides of potassium and lead gave iodine at the positive pole, and potassium or lead at the negative pole. Chlorides of lead and silver gave chlorine at the positive, and metals at the negative pole. Nitre and chlorate; of potassa gave oxygen, &c., at the positive, and alkali, or even potassium, at the negative pole.



401. A fourth arrangement was used for substances requiring very high temperatures for their fusion. A platina wire was connected with one pole of the battery; its extremity bent into a small ring, in the manner described by Berzelius, for blowpipe experiments; a little of the salt, glass, or other substance, was melted on this ring by the ordinary blowpipe, or even in some cases by the oxy-hydrogen blowpipe, and when the drop, retained in its place by the ring, was thoroughly hot and fluid, a platina wire from the opposite pole of the battery was made to touch it, and the effects observed.

402. The following are various substances, taken from very different classes chemically considered, which are subject to this law. The list might, no doubt, be enormously extended; but I have not had time to do more than confirm the law by a sufficient number of instances.

First, water.

Amongst oxides;—potassa, protoxide of lead, glass of antimony, protoxide of antimony, oxide of bismuth.

Chlorides of potassium, sodium, barium, strontium, calcium, magnesium, manganese, zinc, copper (proto-), lead, tin (proto-), antimony, silver.

Iodides of potassium, zinc and lead, protiodide of tin, periodide of mercury; fluoride of potassium; cyanide of potassium; sulpho-cyanide of potassium.

Salts. Chlorate of potassa; nitrates of potassa, soda, baryta, strontia, lead, copper, and silver; sulphates of soda and lead, proto-sulphate of mercury; phosphates of potassa, soda, lead, copper, phosphoric glass or acid phosphate of lime; carbonates of potassa and soda, mingled and separate; borax, borate of lead, per-borate of tin; chromate of potassa, bi-chromate of potassa, chromate of lead; acetate of potassa.

Sulphurets. Sulphuret of antimony, sulphuret of potassium made by reducing sulphate of potassa by hydrogen; ordinary sulphuret of potassa.

Silicated potassa; chameleon mineral.

403. It is highly interesting in the instances of those substances which soften before they liquefy, to observe at what period the conducting power is acquired, and to what degree it is exalted by perfect fluidity. Thus, with the borate of lead, when heated by the lamp upon glass, it becomes as soft as treacle, but it did not conduct, and it was only when urged by the blowpipe and brought to a fair red heat, that it conducted. When rendered quite liquid, it conducted with extreme facility.

404. I do not mean to deny that part of the increased conducting power in these cases of softening was probably due to the elevation of temperature (432. 445.); but I have no doubt that by far the greater part was due to the influence of the general law already demonstrated, and which in these instances came gradually, instead of suddenly, into operation.

405. The following are bodies which acquired no conducting power upon assuming the liquid state:—

Sulphur, phosphorus; iodide of sulphur, per-iodide of tin; orpiment, realgar; glacial acetic acid, mixed margaric and oleic acids, artificial camphor; caffeine, sugar, adipocire, stearine of cocoa-nut oil, spermaceti, camphor, naphthaline, resin, gum sandarach, shell lac.

406. Perchloride of tin, chloride of arsenic, and the hydrated chloride of arsenic, being liquids, had no sensible conducting power indicated by the galvanometer, nor were they decomposed.

407. Some of the above substances are sufficiently remarkable as exceptions to the general law governing the former cases. These are orpiment, realgar, acetic acid, artificial camphor, per-iodide of tin, and the chlorides of tin and arsenic. I shall have occasion to refer to these cases in the paper on Electro-chemical Decomposition.

408. Boracic acid was raised to the highest possible temperature by an oxy-hydrogen flame (401.), yet it gained no conducting powers sufficient to affect the galvanometer, and underwent no apparent voltaic decomposition. It seemed to be quite as bad a conductor as air. Green bottle-glass, heated in the same manner, did not gain conducting power sensible to the galvanometer. Flint glass, when highly heated, did conduct a little and decompose; and as the proportion of potash or oxide of lead was increased in the glass, the effects were more powerful. Those glasses, consisting of boracic acid on the one hand, and oxide of lead or potassa on the other, show the assumption of conducting power upon fusion and the accompanying decomposition very well.

409. I was very anxious to try the general experiment with sulphuric acid, of about specific gravity 1.783, containing that proportion of water which gives it the power of crystallizing at 40 deg. Fahr.; but I found it impossible to obtain it so that I could be sure the whole would congeal even at 0 deg. Fahr. A ten-thousandth part of water, more or less than necessary, would, upon cooling the whole, cause a portion of uncongealable liquid to separate, and that remaining in the interstices of the solid mass, and moistening the planes of division, would prevent the correct observation of the phenomena due to entire solidification and subsequent liquefaction.

410. With regard to the substances on which conducting power is thus conferred by liquidity, the degree of power so given is generally very great. Water is that body in which this acquired power is feeblest. In the various oxides, chlorides, salts, &c. &c., it is given in a much higher degree. I have not had time to measure the conducting power in these cases, but it is apparently some hundred times that of pure water. The increased conducting power known to be given to water by the addition of salts, would seem to be in a great degree dependent upon the high conducting power of these bodies when in the liquid state, that state being given them for the time, not by heat but solution in the water[A].

[A] See a doubt on this point at 1356.—Dec. 1838.

411. Whether the conducting power of these liquefied bodies is a consequence of their decomposition or not (413.), or whether the two actions of conduction and decomposition are essentially connected or not, would introduce no difference affecting the probable accuracy of the preceding statement.

412. This general assumption of conducting power by bodies as soon as they pass from the solid to the liquid state, offers a new and extraordinary character, the existence of which, as far as I know, has not before been suspected; and it seems importantly connected with some properties and relations of the particles of matter which I may now briefly point out.

413. In almost all the instances, as yet observed, which are governed by this law, the substances experimented with have been those which were not only compound bodies, but such as contain elements known to arrange themselves at the opposite poles; and were also such as could be decomposed by the electrical current. When conduction took place, decomposition occurred; when decomposition ceased, conduction ceased also; and it becomes a fair and an important question, Whether the conduction itself may not, wherever the law holds good, be a consequence not merely of the capability, but of the act of decomposition? And that question may be accompanied by another, namely, Whether solidification does not prevent conduction, merely by chaining the particles to their places, under the influence of aggregation, and preventing their final separation in the manner necessary for decomposition?

414. But, on the other hand, there is one substance (and others may occur), the per-iodide of mercury, which, being experimented with like the others (400.), was found to insulate when solid, and to acquire conducting power when fluid; yet it did not seem to undergo decomposition in the latter case.

415. Again, there are many substances which contain elements such as would be expected to arrange themselves at the opposite poles of the pile, and therefore in that respect fitted for decomposition, which yet do not conduct. Amongst these are the iodide of sulphur, per-iodide of zinc, per-chloride of tin, chloride of arsenic, hydrated chloride of arsenic, acetic acid, orpiment, realgar, artificial camphor, &c.; and from these it might perhaps be assumed that decomposition is dependent upon conducting power, and not the latter upon the former. The true relation, however, of conduction and decomposition in those bodies governed by the general law which it is the object of this paper to establish, can only be satisfactorily made out from a far more extensive series of observations than those I have yet been able to supply[A].

[A] See 673, &c. &c.—Dec. 1838.

416. The relation, under this law, of the conducting power for electricity to that for heat, is very remarkable, and seems to imply a natural dependence of the two. As the solid becomes a fluid, it loses almost entirely the power of conduction for heat, but gains in a high degree that for electricity; but as it reverts hack to the solid state, it gains the power of conducting heat, and loses that of conducting electricity. If, therefore, the properties are not incompatible, still they are most strongly contrasted, one being lost as the other is gained. We may hope, perhaps, hereafter to understand the physical reason of this very extraordinary relation of the two conducting powers, both of which appear to be directly connected with the corpuscular condition of the substances concerned.

417. The assumption of conducting power and a decomposable condition by liquefaction, promises new opportunities of, and great facilities in, voltaic decomposition. Thus, such bodies as the oxides, chlorides, cyanides, sulpho-cyanides, fluorides, certain vitreous mixtures, &c. &c., may be submitted to the action of the voltaic battery under new circumstances; and indeed I have already been able, with ten pairs of plates, to decompose common salt, chloride of magnesium, borax, &c. &c., and to obtain sodium, magnesium, boron, &c., in their separate states.

S 10. On Conducting Power generally.[A]

[A] In reference to this S refer to 983 in series viii., and the results connected with it.—Dec. 1838.

418. It is not my intention here to enter into an examination of all the circumstances connected with conducting power, but to record certain facts and observations which have arisen during recent inquiries, as additions to the general stock of knowledge relating to this point of electrical science.

419. I was anxious, in the first place, to obtain some idea of the conducting power of ice and solid salts for electricity of high tension (392.), that a comparison might be made between it and the large accession of the same power gained upon liquefaction. For this purpose the large electrical machine (290.) was brought into excellent action, its conductor connected with a delicate gold-leaf electrometer, and also with the platina inclosed in the ice (383.), whilst the tin case was connected with the discharging train (292.). On working the machine moderately, the gold leaves barely separated; on working it rapidly, they could be opened nearly two inches. In this instance the tin case was five-eighths of an inch in width; and as, after the experiment, the platina plate was found very nearly in the middle of the ice, the average thickness of the latter had been five-sixteenths of an inch, and the extent of surface of contact with tin and platina fourteen square inches (384.). Yet, under these circumstances, it was but just able to conduct the small quantity of electricity which this machine could evolve (371.), even when of a tension competent to open the leaves two inches; no wonder, therefore, that it could not conduct any sensible portion of the electricity of the troughs (384.), which, though almost infinitely surpassing that of the machine in quantity, had a tension so low as not to be sensible to an electrometer.

420. In another experiment, the tin case was only four-eighths of an inch in width, and it was found afterwards that the platina had been not quite one-eighth of an inch distant in the ice from one side of the tin vessel. When this was introduced into the course of the electricity from the machine (419.), the gold leaves could be opened, but not more than half an inch; the thinness of the ice favouring the conduction of the electricity, and permitting the same quantity to pass in the same time, though of a much lower tension.

421. Iodide of potassium which had been fused and cooled was introduced into the course of the electricity from the machine. There were two pieces, each about a quarter of an inch in thickness, and exposing a surface on each side equal to about half a square inch; these were placed upon platina plates, one connected with the machine and electrometer (419.), and the other with the discharging train, whilst a fine platina wire connected the two pieces, resting upon them by its two points. On working the electrical machine, it was possible to open the electrometer leaves about two-thirds of an inch.

422. As the platina wire touched only by points, the facts show that this salt is a far better conductor than ice; but as the leaves of the electrometer opened, it is also evident with what difficulty conduction, even of the small portion of electricity produced by the machine, is effected by this body in the solid state, when compared to the facility with which enormous quantities at very low tensions are transmitted by it when in the fluid state.

423. In order to confirm these results by others, obtained from the voltaic apparatus, a battery of one hundred and fifty plates, four inches square, was well-charged: its action was good; the shock from it strong; the discharge would continue from copper to copper through four-tenths of an inch of air, and the gold-leaf electrometer before used could be opened nearly a quarter of an inch.

424. The ice vessel employed (420.) was half an inch in width; as the extent of contact of the ice with the tin and platina was nearly fourteen square inches, the whole was equivalent to a plate of ice having a surface of seven square inches, of perfect contact at each side, and only one fourth of an inch thick. It was retained in a freezing mixture during the experiment.

425. The order of arrangement in the course of the electric current was as follows. The positive pole of the battery was connected by a wire with the platina plate in the ice; the plate was in contact with the ice, the ice with the tin jacket, the jacket with a wire, which communicated with a piece of tin foil, on which rested one end of a bent platina wire (312.), the other or decomposing end being supported on paper moistened with solution of iodide of potassium (316.): the paper was laid flat on a platina spatula connected with the negative end of the battery. All that part of the arrangement between the ice vessel and the decomposing wire point, including both these, was insulated, so that no electricity might pass through the latter which had not traversed the former also.

426. Under these circumstances, it was found that, a pale brown spot of iodine was slowly formed under the decomposing platina point, thus indicating that ice could conduct a little of the electricity evolved by a voltaic battery charged up to the degree of intensity indicated by the electrometer. But it is quite evident that notwithstanding the enormous quantity of electricity which the battery could furnish, it was, under present circumstances, a very inferior instrument to the ordinary machine; for the latter could send as much through the ice as it could carry, being of a far higher intensity, i.e. able to open the electrometer leaves half an inch or more (419. 420.).

427. The decomposing wire and solution of iodide of potassium were then removed, and replaced by a very delicate galvanometer (205.); it was so nearly astatic, that it vibrated to and fro in about sixty-three beats of a watch giving one hundred and fifty beats in a minute. The same feebleness of current as before was still indicated; the galvanometer needle was deflected, but it required to break and make contact three or four times (297.), before the effect was decided.

428. The galvanometer being removed, two platina plates were connected with the extremities of the wires, and the tongue placed between them, so that the whole charge of the battery, so far as the ice would let it pass, was free to go through the tongue. Whilst standing on the stone floor, there was shock, &c., but when insulated, I could feel no sensation. I think a frog would have been scarcely, if at all, affected.

429. The ice was now removed, and experiments made with other solid bodies, for which purpose they were placed under the end of the decomposing wire instead of the solution of iodide of potassium (125.). For instance, a piece of dry iodide of potassium was placed on the spatula connected with the negative pole of the battery, and the point of the decomposing wire placed upon it, whilst the positive end of the battery communicated with the latter. A brown spot of iodine very slowly appeared, indicating the passage of a little electricity, and agreeing in that respect with the results obtained by the use of the electrical machine (421.). When the galvanometer was introduced into the circuit at the same time with the iodide, it was with difficulty that the action of the current on it could be rendered sensible.

430. A piece of common salt previously fused and solidified being introduced into the circuit was sufficient almost entirely to destroy the action on the galvanometer. Fused and cooled chloride of lead produced the same effect. The conducting power of these bodies, when fluid, is very great (395. 402.).

431. These effects, produced by using the common machine and the voltaic battery, agree therefore with each other, and with the law laid down in this paper (394.); and also with the opinion I have supported, in the Third Series of these Researches, of the identity of electricity derived from different sources (360.).

432. The effect of heat in increasing the conducting power of many substances, especially for electricity of high tension, is well known. I have lately met with an extraordinary case of this kind, for electricity of low tension, or that of the voltaic pile, and which is in direct contrast with the influence of heat upon metallic bodies, as observed and described by Sir Humphry Davy[A].

[A] Philosophical Transactions, 1821, p. 131.

433. The substance presenting this effect is sulphuret of silver. It was made by fusing a mixture of precipitated silver and sublimed sulphur, removing the film of silver by a file from the exterior of the fused mass, pulverizing the sulphuret, mingling it with more sulphur, and fusing it again in a green glass tube, so that no air should obtain access during the process. The surface of the sulphuret being again removed by a file or knife, it was considered quite free from uncombined silver.

434. When a piece of this sulphuret, half an inch in thickness, was put between surfaces of platina, terminating the poles of a voltaic battery of twenty pairs of four-inch plates, a galvanometer being also included in the circuit, the needle was slightly deflected, indicating a feeble conducting power. On pressing the platina poles and sulphuret together with the fingers, the conducting power increased as the whole became warm. On applying a lamp under the sulphuret between the poles, the conducting power rose rapidly with the heat, and at last-the galvanometer needle jumped into a fixed position, and the sulphuret was found conducting in the manner of a metal. On removing the lamp and allowing the heat to fall, the effects were reversed, the needle at first began to vibrate a little, then gradually left its transverse direction, and at last returned to a position very nearly that which it would take when no current was passing through the galvanometer.

435. Occasionally, when the contact of the sulphuret with the platina poles was good, the battery freshly charged, and the commencing temperature not too low, the mere current of electricity from the battery was sufficient to raise the temperature of the sulphuret; and then, without any application of extraneous heat, it went on increasing conjointly in temperature and conducting power, until the cooling influence of the air limited the effects. In such cases it was generally necessary to cool the whole purposely, to show the returning series of phenomena.

436. Occasionally, also, the effects would sink of themselves, and could not be renewed until a fresh surface of the sulphuret had been applied to the positive pole. This was in consequence of peculiar results of decomposition, to which I shall have occasion to revert in the section on Electro-chemical Decomposition, and was conveniently avoided by inserting the ends of two pieces of platina wire into the opposite extremities of a portion of sulphuret fused in a glass tube, and placing this arrangement between the poles of the battery.

437. The hot sulphuret of silver conducts sufficiently well to give a bright spark with charcoal, &c. &c., in the manner of a metal.

438. The native grey sulphuret of silver, and the ruby silver ore, both presented the same phenomena. The native malleable sulphuret of silver presented precisely the same appearances as the artificial sulphuret.

439. There is no other body with which I am acquainted, that, like sulphuret of silver, can compare with metals in conducting power for electricity of low tension when hot, but which, unlike them, during cooling, loses in power, whilst they, on the contrary, gain. Probably, however, many others may, when sought for, be found[A].

[A] See now on this subject, 1340, 1341.—Dec. 1838.

440. The proto-sulphuret of iron, the native per-sulphuret of iron, arsenical sulphuret of iron, native yellow sulphuret of copper and iron, grey artificial sulphuret of copper, artificial sulphuret of bismuth, and artificial grey sulphuret of tin, all conduct the voltaic battery current when cold, more or less, some giving sparks like the metals, others not being sufficient for that high effect. They did not seem to conduct better when heated, than before; but I had not time to enter accurately into the investigation of this point. Almost all of them became much heated by the transmission of the current, and present some very interesting phenomena in that respect. The sulphuret of antimony does not conduct the same current sensibly either hot or cold, but is amongst those bodies acquiring conducting power when fused (402.). The sulphuret of silver and perhaps some others decompose whilst in the solid state; but the phenomena of this decomposition will be reserved for its proper place in the next series of these Researches.

441. Notwithstanding the extreme dissimilarity between sulphuret of silver and gases or vapours, I cannot help suspecting the action of heat upon them to be the same, bringing them all into the same class as conductors of electricity, although with those great differences in degree, which are found to exist under common circumstances. When gases are heated, they increase in conducting power, both for common and voltaic electricity (271.); and it is probable that if we could compress and condense them at the same time, we should still further increase their conducting power. Cagniard de la Tour has shown that a substance, for instance water, may be so expanded by heat whilst in the liquid state, or condensed whilst in the vaporous state, that the two states shall coincide at one point, and the transition from one to the other be so gradual that no line of demarcation can be pointed out[A]; that, in fact, the two states shall become one;—which one state presents us at different times with differences in degree as to certain properties and relations; and which differences are, under ordinary circumstances, so great as to be equivalent to two different states.

[A] Annales de Chimie, xxi. pp. 127, 178.

442. I cannot but suppose at present that at that point where the liquid and the gaseous state coincide, the conducting properties are the same for both; but that they diminish as the expansion of the matter into a rarer form takes place by the removal of the necessary pressure; still, however, retaining, as might be expected, the capability of having what feeble conducting power remains, increased by the action of heat.

443. I venture to give the following summary of the conditions of electric conduction in bodies, not however without fearing that I may have omitted some important points[A].

[A] See now in relation to this subject, 1320—1242.—Dec. 1838.

444. All bodies conduct electricity in the same manner from metals to lac and gases, but in very different degrees.

445. Conducting power is in some bodies powerfully increased by heat, and in others diminished, yet without our perceiving any accompanying essential electrical difference, either in the bodies or in the changes occasioned by the electricity conducted.

446. A numerous class of bodies, insulating electricity of low intensity, when solid, conduct it very freely when fluid, and are then decomposed by it.

447. But there are many fluid bodies which do not sensibly conduct electricity of this low intensity; there are some which conduct it and are not decomposed; nor is fluidity essential to decomposition[A].

[A] See the next series of these Experimental Researches.

448. There is but one body yet discovered[A] which, insulating a voltaic current when solid, and conducting it when fluid, is not decomposed in the latter case (414.).

[A] It is just possible that this case may, by more delicate experiment, hereafter disappear. (See now, 1340, 1341, in relation to this note.—Dec. 1838.)

449. There is no strict electrical distinction of conduction which can, as yet, be drawn between bodies supposed to be elementary, and those known to be compounds.

Royal Institution, April 15, 1833.



FIFTH SERIES.

S 11. On Electro-chemical Decomposition. P i. New conditions of Electro-chemical Decomposition. P ii. Influence of Water in Electro-chemical Decomposition. P iii. Theory of Electro-chemical Decomposition.

Received June 18,—Read June 20, 1833.

S 11. On Electro-chemical Decomposition.[A]

[A] Refer to the note after 1047, Series viii.—Dec. 1838.

450. I have in a recent series of these Researches (265.) proved (to my own satisfaction, at least,) the identity of electricities derived from different sources, and have especially dwelt upon the proofs of the sameness of those obtained by the use of the common electrical machine and the voltaic battery.

451. The great distinction of the electricities obtained from these two sources is the very high tension to which the small quantity obtained by aid of the machine may be raised, and the enormous quantity (371. 376.) in which that of comparatively low tension, supplied by the voltaic battery, may be procured; but as their actions, whether magnetical, chemical, or of any other nature, are essentially the same (360.), it appeared evident that we might reason from the former as to the manner of action of the latter; and it was, to me, a probable consequence, that the use of electricity of such intensity as that afforded by the machine, would, when applied to effect and elucidate electro-chemical decomposition, show some new conditions of that action, evolve new views of the internal arrangements and changes of the substances under decomposition, and perhaps give efficient powers over matter as yet undecomposed.

452. For the purpose of rendering the bearings of the different parts of this series of researches more distinct, I shall divide it into several heads.

P 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 decomposition[A].

[A] I find (since making and describing these results,) from a note to Sir Humphry Davy's paper in the Philosophical Transactions, 1807, p. 31, that that philosopher, in repeating Wollaston's experiment of the decomposition of water by common electricity (327. 330.) used an arrangement somewhat like some of those I have described. He immersed a guarded platina point connected with the machine in distilled water, and dissipated the electricity from the water into the air by moistened filaments of cotton. In this way he states that he obtained oxygen and hydrogen separately from each other. This experiment, had I known of it, ought to have been quoted in an earlier series of these Researches (342.); but it does not remove any of the objections I have made to the use of Wollaston's apparatus as a test of true chemical action (331.).

P 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 apparatus[A]:" 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) occur[B]."

[A] Elements of Chemical Philosophy, p. 160, &c.

[B] Ibid. pp. 144, 145.

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 1801[A], 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 circles[B]; 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.

[A] Journal of the Royal Institution, 1802, p. 53.

[B] Philosophical Transactions, 1826, p. 406.

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 effectual[A]. 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.

[A] Philosophical Transactions, 1826, p. 406.

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 electricity[A]. 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 force[B]. 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 particles[C], 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 gases[D].

[A] Annales de Chimie, 1806, tom, lviii. p. 64.

[B] Ibid. pp. 66, 67, also tom. lxiii. p. 20.

[C] Ibid. tom. lviii. p. 68, tom, lxiii. p. 20.

[D] Ibid. tom. lxiii. p. 34.

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 Grotthuss[A]; and supposes that the attractive and repellent agencies may be communicated from the metallic surfaces throughout the whole of the menstruum[B], being communicated from one particle to another particle of the same kind[C], and diminishing in strength from the place of the poles to the middle point, which is necessarily neutral[D]. 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 elements[E].

[A] Philosophical Transactions, 1807, pp. 29, 30.

[B] Ibid. p. 39.

[C] Ibid. p. 29.

[D] Ibid. p. 42.

[E] Ibid. p. 42.

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 communication[A], and uses the terms attraction and repulsion apparently in the same sense as before[B].

[A] Philosophical Transactions, 1826, p. 383.

[B] Ibid. pp. 389, 407, 115.

485. Messrs. Riffault and Chompre 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 current[A].

[A] Annales de Chimie, 1807, tom. lxiii. p. 83, &c.

486. M. Biot is very cautious in expressing an opinion as to the cause of the separation of the elements of a compound body[A]. 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 negative[B]. 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 it[C].

[A] Precis Elementaire de Physique, 3me edition, 1824, tom. i. p. 641.

[B] Ibid. p. 637.

[C] Ibid. pp. 641, 642.

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 time[A], 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 pole[B].

[A] Precis Elementaire de Physique, 3me edition, 1824, tom. i. p. 636.

[B] Ibid. p, 642.

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 repulsions[A].

[A] Precis Elementaire de Physique, 3me edition, 1824, tom. i. pp. 638, 642.

489. M.A. de la Rive investigated this subject particularly, and published a paper on it in 1825[A]. 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 electricity[B]. 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 conductor[C], 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 them[D]. In this respect M. de la Rive's hypothesis accords in part with that of MM. Riffault and Chompre (485.).

[A] Annales de Chimie, tom, xxviii. p. 190.

[B] Ibid. pp. 200, 202.

[C] Ibid. p. 202.

[D] Ibid. p. 201.

490. M. de la Rive considers the portions of matter which are decomposed to be those contiguous to both poles[A]. He does not admit with others the successive decompositions and recompositions in the whole course of the electricity through the humid conductor[B], 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 poles[C]. 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.

[A] Annales de Chimie, tom, xxviii. pp. 197, 198.

[B] Ibid. pp. 192, 199.

[C] Ibid. p. 200.

491. The latest communication that I am aware of on the subject is by M. Hachette: its date is October 1832[A]. 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."

[A] Annales de Chimie, tom, xxviii. tom. li. p. 73.

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.

* * * * *

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 poles[A] (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.

[A] Philosophical Transactions, 1807, p. 42.

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 plates[A].

[A] There are certain precautions, in this and such experiments, which can only be understood and guarded against by a knowledge of the phenomena to be described in the first part of the Sixth Series of these Researches.

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 Chompre (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 Chompre (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 Chompre, for instance, consider the positive and negative currents each as causing decomposition, and state that the positive current is more powerful than the negative current[A], the nitrate of soda being, under similar circumstances, decomposed by the former, but not by the latter.

[A] Annales de Chimie, 1807, tom, lxiii. p. 84.

513. M. Hachette states[A] 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.

[A] Annales de Chimie, 1832, tom. li. p. 73.

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.)[A]. 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.

[A] Annales de Chimie, 1825, tom, xxviii. pp. 197, 201.

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 other[A]. 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 chemically[B].

[A] See now in relation to this subject, 1627-1645.—Dec. 1838.

[B] Thermo-electric currents are of course no exception, because when they fail to act chemically they also fail to be currents.

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.

* * * * *

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 current[A].

[A] In reference to this subject see now electrolytic induction and discharge, Series XII. P viii. 1343-1351, &c.—Dec. 1838.

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 bodies[A].

[A] See the note to (675.),—Dec. 1838.

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.