Experimental Researches in Electricity Part 15

[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, a.s.suming 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 pa.s.sing 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 ill.u.s.tration 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 ill.u.s.tration of the views I shall venture to give, I must describe it minutely.

494. A gla.s.s 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 gla.s.s 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 gla.s.s 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 gla.s.s. In this way solution of the sulphate occupied the lower part of the gla.s.s, 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 quant.i.ty 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 a.s.sumed, 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 pota.s.sa, 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 gla.s.s 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 s.p.a.ce 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 pa.s.sing 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 gla.s.s 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 quant.i.ty 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 gla.s.s trough, connected at each end with a voltaic battery by poles equal to the section of the fluid, a part of the electricity will pa.s.s 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 quant.i.ty (377.), and that the section pa.s.ses 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 quant.i.ty 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 quant.i.ty, 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 pa.s.s 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, pota.s.sium 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 a.n.a.logy 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 a.s.sumed 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 quant.i.ty of electricity pa.s.sing, 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, a.s.sume but one electric fluid; and such must agree together in the general uniformity and character of the electric current. Others a.s.sume 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 circ.u.mstances, 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 pa.s.sage 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 pa.s.sage 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, const.i.tute the ordinary _voltaic current._

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