Experimental Researches in Electricity, Vol. 1 · Michael Faraday

Series V: On Electro-Chemical Decomposition (Part 2)

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

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

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

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

512. MM. Riffault and Chompré, for instance, consider the positive and negative currents each as causing decomposition, and state that the positive current is more powerful than the negative 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. ¶ 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.

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

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

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

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

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

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

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

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

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

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

544. It is very difficult to find cases amongst solutions or fluids which shall illustrate this point, because of the difficulty of finding two fluids which shall conduct, shall not mingle, and in which an element evolved from one shall not find a combinable element in the other. Solutions of acids or alkalies will not answer, because they exist by virtue of an attraction; and increasing the solubility of a body in one direction, and diminishing it in the opposite, is just as good a reason for transfer, as modifying the affinity between the acids and alkalies 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 passing 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 pass towards it, and so will acid; but these are not substances having such chemical relation to the platina as, even under the favourable condition superinduced by the current (518. 524.), to combine with it; the platina therefore remains where it was first placed, and has no tendency to pass towards the negative pole. But if a plate of iron, zinc or copper, be substituted for the platina, then the oxygen and acid can combine with these, and the metal immediately begins to travel (as an oxide) to the opposite pole, and is finally deposited there. Or if, retaining the platina pole, a fused chloride, as of lead, zinc, silver, &c., be substituted for the sulphuric acid, then, as the platina finds an element it can combine with, it enters into union, acts as other elements do in cases of voltaic decomposition, is rapidly transferred across the melted matter, and expelled at the negative pole.

546. I can see but little reason in the theories referring the electro-chemical decomposition to the attractions and repulsions of the poles, and I can perceive none in M. de la Rive's theory, why the metal of the positive pole should not be transferred across the intervening conductor, and deposited at the negative pole, even when it cannot act chemically upon the element of the fluid surrounding it. It cannot be referred to the attraction of cohesion preventing such an effect; for if the pole be made of the lightest spongy platina, the effect is the same. Or if gold precipitated by sulphate of iron be diffused through the solution, still accumulation of it at the negative pole will not take place; and yet the attraction of cohesion is almost perfectly overcome, the particles are in it so small as to remain for hours in suspension, and are perfectly free to move by the slightest impulse towards either pole; and if in relation by chemical affinity to any substance present, are powerfully determined to the negative 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 pass to that pole, the silver was not tarnished, nor did any sulphuretted hydrogen appear. The case of magnesia and water (495. 533.), with those of comminuted metals in certain solutions (546.), are also of this kind; and, in fact, substances which have the instant before been powerfully determined towards the pole, as magnesia from sulphate of magnesia, become entirely indifferent to it the moment they assume their independent state, and pass away, diffusing themselves through the surrounding fluid.

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

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

550. Some of the most beautiful and surprising cases of electro-chemical decomposition and transfer which Sir Humphry Davy described in his celebrated paper[A], were those in which acids were passed 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 illustration of the difference between the theory I have ventured, and those previously existing, cannot be offered than the views they respectively give of such facts as these.

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

[B] Ibid. p, 24, &c.

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

[A] Philosophical Transactions, 1807, p. 25, &c.

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

[A] At 681 and 757 of Series VII, will be found corrections of the statement here made respecting sulphur and sulphuric acid. At present there is no well-ascertained fact which proves that the same body can go directly to either of the two poles at pleasure.--Dec. 1838.

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

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

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

[A] Refer for proof of the truth of this supposition to 748, 752, &c.--Dec. 1838.

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

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

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

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

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

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

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

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

Royal Institution, June 1833.

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End of part 10 of 31