Experimental Researches in Electricity Part 16

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 pa.s.sing 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. Pa.s.sing 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 ma.s.s 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 pa.s.s 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 pa.s.s 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 a.n.a.logous 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 a.s.sumed 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 pa.s.sing 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 pa.s.sing 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. -- 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 circ.u.mstance 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 gla.s.s 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 circ.u.mstances, 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 surpa.s.s 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 quant.i.ty 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 circ.u.mstance, 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 quant.i.ty 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 pa.s.sing, 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 quant.i.ties, 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 pa.s.sing 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 ill.u.s.trating 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 gla.s.s 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 quant.i.ty, 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 pa.s.sed through _a b_ and A B, and that in each instance the same quant.i.ty 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 princ.i.p.ally 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 pa.s.sed, 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 gla.s.ses, these quant.i.ties 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 pa.s.sed from _a_ to _b_; in the free acid vessels, between a tenth and an eleventh pa.s.sed 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 acc.u.mulation 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 circ.u.mstances, are sufficiently obvious in these cases, where sulphuric acid is acted upon in the _same quant.i.ty_ 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 quant.i.ty 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 gla.s.s, or perhaps impurities originally in the acid,) and that they had helped in transferring the acid into _b_. But the quant.i.ty was small, and the acid was princ.i.p.ally transferred by relation to the water present.

532. I endeavoured to arrange certain experiments by which saline solutions should be decomposed against surfaces of water; and at first worked with the electric machine upon a piece of bibulous paper, or asbestus moistened in the solution, and in contact at its two extremities with pointed pieces of paper moistened in pure water, which served to carry the electric current to and from the solution in the middle piece. But I found numerous interfering difficulties. Thus, the water and solutions in the pieces of paper could not be prevented from mingling at the point where they touched.

Again, sufficient acid could be derived from the paper connected with the discharging train, or it may be even from the air itself, under the influence of electric action, to neutralize the alkali developed at the positive extremity of the decomposing solution, and so not merely prevent its appearance, but actually transfer it on to the metal termination: and, in fact, when the paper points were not allowed to touch there, and the machine was worked until alkali was evolved at the delivering or positive end of the turmeric paper, containing the sulphate of soda solution, it was merely necessary to place the opposite receiving point of the paper connected with the discharging train, which had been moistened by distilled water, upon the brown turmeric point and press them together, when the alkaline effect immediately disappeared.

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

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

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

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

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

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

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

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

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

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

[A] Even Sir Humphry Davy considered the attraction of the pole as being communicated from one particle to another of the _same_ kind (483.).

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

544. It is very difficult to find cases amongst solutions or fluids which shall ill.u.s.trate this point, because of the difficulty of finding two fluids which shall conduct, shall not mingle, and in which an element evolved from one shall not find a combinable element in the other.

_Solutions_ of acids or alkalies will not answer, because they exist by virtue of an attraction; and increasing the solubility of a body in one direction, and diminis.h.i.+ng it in the opposite, is just as good a reason for transfer, as modifying the affinity between the acids and alkalies themselves[A]. Nevertheless the case of sulphate of magnesia is in point (494. 495.), and shows that _one element or principle only_ has no power of transference or of pa.s.sing towards either pole.

[A] See the note to (670.).--_Dec. 1838._

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

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

[A] In making this experiment, care must be taken that no substance be present that can act chemically on the gold. Although I used the metal very carefully washed, and diffused through dilute sulphuric acid, yet in the first instance I obtained gold at the negative pole, and the effect was repeated when the platina poles were changed. But on examining the clear liquor in the cell, after subsidence of the metallic gold, I found a little of that metal in solution, and a little chlorine was also present. I therefore well washed the gold which had thus been subjected to voltaic action, diffused it through other pure dilute sulphuric acid, and then found, that on subjecting it to the action of the pile, not the slightest tendency to the negative pole could be perceived.

547. In support of these arguments, it may be observed, that as yet no determination of a substance to a pole, or tendency to obey the electric current, has been observed (that I am aware of,) in cases of mere mixture; i.e. a substance diffused through a fluid, but having no sensible chemical affinity with it, or with substances that may be evolved from it during the action, does not in any case seem to be affected by the electric current.

Pulverised charcoal was diffused through dilute sulphuric acid, and subjected with the solution to the action of a voltaic battery, terminated by platina poles; but not the slightest tendency of the charcoal to the negative pole could be observed, Sublimed sulphur was diffused through similar acid, and submitted to the same action, a silver plate being used as the negative pole; but the sulphur had no tendency to pa.s.s to that pole, the silver was not tarnished, nor did any sulphuretted hydrogen appear. The case of magnesia and water (495. 533.), with those of comminuted metals in certain solutions (546.), are also of this kind; and, in fact, substances which have the instant before been powerfully determined towards the pole, as magnesia from sulphate of magnesia, become entirely _indifferent to it_ the moment they a.s.sume their independent state, and pa.s.s away, diffusing themselves through the surrounding fluid.

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

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

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

[A] Philosophical Transactions, 1807, p. 1.