Part 27

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. 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.

See now in relation to this subject, 1627-1645.--Dec. 1838.

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.

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

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

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

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

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.

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.

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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.