Experimental Researches in Electricity, Volume 1 7 – Faraday · Verses Across
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Experimental Researches in Electricity, Volume 1 7Experimental Researches in Electricity, Volume 1 (part 7)
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Literature · Science
Experimental Researches in Electricity, Volume 1 7
Experimental Researches in Electricity, Volume 1 (part 7)
FaradayEnglish
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.
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. Yet such is not the case, as has been shown by the experiments on free and combined acid (526. 528.).
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. 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.
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.
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, were those in which acids were passed through alkalies, and alkalies or earths through acids; 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.
Philosophical Transactions, 1807, p. 1.
Ibid. p, 24, &c.
551. The instances in which sulphuric acid could not be passed though baryta, or baryta through sulphuric acid, 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.
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. 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.
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.
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._
SIXTH SERIES.
§ 12. On the power of Metals and other Solids to induce the Combination of Gaseous Bodies.
Received November 30, 1833,--Read January 11, 1834.
564. The conclusion at which I have arrived in the present communication may seem to render the whole of it unfit to form part of a series of researches in electricity; since, remarkable as the phenomena are, the power which produces them is not to be considered as of an electric origin, otherwise than as all attraction of particles may have this subtile agent for their common cause. But as the effects investigated arose out of electrical researches, as they are directly connected with other effects which are of an electric nature, and must of necessity be understood and guarded against in a very extensive series of electro-chemical decompositions (707.), I have felt myself fully justified in describing them in this place.
565. Believing that I had proved (by experiments hereafter to be described (705.),) the constant and definite chemical action of a certain quantity of electricity, whatever its intensity might be, or however the circumstances of its transmission through either the body under decomposition or the more perfect conductors were varied, I endeavoured upon that result to construct a new measuring instrument, which from its use might be called, at least provisionally, a Volta-electrometer (739.).
Or Voltameter.--Dec. 1838.
566. During the course of the experiments made to render the instrument efficient, I was occasionally surprised at observing a deficiency of the gases resulting from the decompositions of water, and at last an actual disappearance of portions which had been evolved, collected, and measured. The circumstances of the disappearance were these. A glass tube, about twelve inches in length and 3/4ths of an inch in diameter, had two platina poles fixed into its upper, hermetically sealed, extremity: the poles, where they passed through the glass, were of wire; but terminated below in plates, which were soldered to the wires with gold (Plate V. fig. 56.). The tube was filled with dilute sulphuric acid, and inverted in a cup of the same fluid; a voltaic battery was connected with the two wires, and sufficient oxygen and hydrogen evolved to occupy 4/5ths of the tube, or by the graduation, 116 parts. On separating the tube from the voltaic battery the volume of gas immediately began to diminish, and in about five hours only 13-1/2 parts remained, and these ultimately disappeared.
567. It was found by various experiments, that this effect was not due to the escape or solution of the gas, nor to recombination of the oxygen or hydrogen in consequence of any peculiar condition they might be supposed to possess under the circumstances; but to be occasioned by the action of one or both of the poles within the tube upon the gas around them. On disuniting the poles from the pile after they had acted upon dilute sulphuric acid, and introducing them into separate tubes containing mixed oxygen and hydrogen, it was found that the positive pole effected the union of the gases, but the negative pole apparently not (588.). It was ascertained also that no action of a sensible kind took place between the positive pole with oxygen or hydrogen alone.
568. These experiments reduced the phenomena to the consequence of a power possessed by the platina, after it had been the positive pole of a voltaic pile, of causing the combination of oxygen and hydrogen at common, or even at low, temperatures. This effect is, as far as I am aware, altogether new, and was immediately followed out to ascertain whether it was really of an electric nature, and how far it would interfere with the determination of the quantities evolved in the cases of electro-chemical decomposition required in the fourteenth section of these Researches.
569. Several platina plates were prepared (fig. 57.). They were nearly half an inch wide, and two inches and a half long: some were 1/200dth of an inch, others not more than 1/600dth, whilst some were as much as 1/70th of an inch in thickness. Each had a piece of platina wire, about seven inches long, soldered to it by pure gold. Then a number of glass tubes were prepared: they were about nine or ten inches in length, 5/8ths of an inch in internal diameter, were sealed hermetically at one extremity, and were graduated. Into these tubes was put a mixture of two volumes of hydrogen and one of oxygen, at the water pneumatic trough, and when one of the plates described had been connected with the positive or negative pole of the voltaic battery for a given time, or had been otherwise prepared, it was introduced through the water into the gas within the tube; the whole set aside in a test-glass (fig. 58.), and left for a longer or shorter period, that the action might be observed.
570. The following result may be given as an illustration of the phenomenon to be investigated. Diluted sulphuric acid, of the specific gravity 1.336, was put into a glass jar, in which was placed also a large platina plate, connected with the negative end of a voltaic battery of forty pairs of four-inch plates, with double coppers, and moderately charged. One of the plates above described (569.) was then connected with the positive extremity, and immersed in the same jar of acid for five minutes, after which it was separated from the battery, washed in distilled water, and introduced through the water of the pneumatic trough into a tube containing the mixture of oxygen and hydrogen (569.). The volume of gases immediately began to lessen, the diminution proceeding more and more rapidly until about 3/4ths of the mixture had disappeared. The upper end of the tube became quite warm, the plate itself so hot that the water boiled as it rose over it; and in less than a minute a cubical inch and a half of the gases were gone, having been combined by the power of the platina, and converted into water.
571. This extraordinary influence acquired by the platina at the positive pole of the pile, is exerted far more readily and effectively on oxygen and hydrogen than on any other mixture of gases that I have tried. One volume of nitrous gas was mixed with a volume of hydrogen, and introduced into a tube with a plate which had been made positive in the dilute sulphuric acid for four minutes (570.). There was no sensible action in an hour: being left for thirty-six hours, there was a diminution of about one-eighth of the whole volume. Action had taken place, but it had been very feeble.
572. A mixture of two volumes of nitrous oxide with one volume of hydrogen was put with a plate similarly prepared into a tube (569. 570.). This also showed no action immediately; but in thirty-six hours nearly a fourth of the whole had disappeared, i.e. about half of a cubic inch. By comparison with another tube containing the same mixture without a plate, it appeared that a part of the diminution was due to solution, and the other part to the power of the platina; but the action had been very slow and feeble.
573. A mixture of one volume olefiant gas and three volumes oxygen was not affected by such a platina plate, even though left together for several days (640. 641.).
574. A mixture of two volumes carbonic oxide and one volume oxygen was also unaffected by the prepared platina plate in several days (645, &c.).
575. A mixture of equal volumes of chlorine and hydrogen was used in several experiments, with plates prepared in a similar manner (570.). Diminution of bulk soon took place; but when after thirty-six hours the experiments were examined, it was found that nearly all the chlorine had disappeared, having been absorbed, principally by the water, and that the original volume of hydrogen remained unchanged. No combination of the gases, therefore, had here taken place.
576. Reverting to the action of the prepared plates on mixtures of oxygen and hydrogen (570.), I found that the power, though gradually diminishing in all cases, could still be retained for a period, varying in its length with circumstances. When tubes containing plates (569.) were supplied with fresh portions of mixed oxygen and hydrogen as the previous portions were condensed, the action was found to continue for above thirty hours, and in some cases slow combination could be observed even after eighty hours; but the continuance of the action greatly depended upon the purity of the gases used (638.).
577. Some plates (569.) were made positive for four minutes in dilute sulphuric acid of specific gravity 1.336: they were rinsed in distilled water, after which two were put into a small bottle and closed up, whilst others were left exposed to the air. The plates preserved in the limited portion of air were found to retain their power after eight days, but those exposed to the atmosphere had lost their force almost entirely in twelve hours, and in some situations, where currents existed, in a much shorter time.
578. Plates were made positive for five minutes in sulphuric acid, specific gravity 1.336. One of these was retained in similar acid for eight minutes after separation from the battery: it then acted on mixed oxygen and hydrogen with apparently undiminished vigour. Others were left in similar acid for forty hours, and some even for eight days, after the electrization, and then acted as well in combining oxygen and hydrogen gas as those which were used immediately after electrization.
579. The effect of a solution of caustic potassa in preserving the platina plates was tried in a similar manner. After being retained in such a solution for forty hours, they acted exceedingly well on oxygen and hydrogen, and one caused such rapid condensation of the gases, that the plate became much heated, and I expected the temperature would have risen to ignition.
580. When similarly prepared plates (569.) had been put into distilled water for forty hours, and then introduced into mixed oxygen and hydrogen, they were found to act but very slowly and feebly as compared with those which had been preserved in acid or alkali. When, however, the quantity of water was but small, the power was very little impaired after three or four days. As the water had been retained in a wooden vessel, portions of it were redistilled in glass, and this was found to preserve prepared plates for a great length of time. Prepared plates were put into tubes with this water and closed up; some of them, taken out at the end of twenty-four days, were found very active on mixed oxygen and hydrogen; others, which were left in the water for fifty-three days, were still found to cause the combination of the gases. The tubes had been closed only by corks.
581. The act of combination always seemed to diminish, or apparently exhaust, the power of the platina plate. It is true, that in most, if not all instances, the combination of the gases, at first insensible, gradually increased in rapidity, and sometimes reached to explosion; but when the latter did not happen, the rapidity of combination diminished; and although fresh portions of gas were introduced into the tubes, the combination went on more and more slowly, and at last ceased altogether. The first effect of an increase in the rapidity of combination depended in part upon the water flowing off from the platina plate, and allowing a better contact with the gas, and in part upon the heat evolved during the progress of the combination (630.). But notwithstanding the effect of these causes, diminution, and at last cessation of the power, always occurred. It must not, however, be unnoticed, that the purer the gases subjected to the action of the plate, the longer was its combining power retained. With the mixture evolved at the poles of the voltaic pile, in pure dilute sulphuric acid, it continued longest; and with oxygen and hydrogen, of perfect purity, it probably would not be diminished at all.
582. Different modes of treatment applied to the platina plate, after it had ceased to be the positive pole of the pile, affected its power very curiously. A plate which had been a positive pole in diluted sulphuric acid of specific gravity 1.336 for four or five minutes, if rinsed in water and put into mixed oxygen and hydrogen, would act very well, and condense perhaps one cubic inch and a half of gas in six or seven minutes; but if that same plate, instead of being merely rinsed, had been left in distilled water for twelve or fifteen minutes, or more, it would rarely fail, when put into the oxygen and hydrogen, of becoming, in the course of a minute or two, ignited, and would generally explode the gases. Occasionally the time occupied in bringing on the action extended to eight or nine minutes, and sometimes even to forty minutes, and yet ignition and explosion would result. This effect is due to the removal of a portion of acid which otherwise adheres firmly to the plate .
In proof that this is the case, refer to 1038.--Dec. 1838.
583. Occasionally the platina plates (569.), after being made the positive pole of the battery, were washed, wiped with filtering-paper or a cloth, and washed and wiped again. Being then introduced into mixed oxygen and hydrogen, they acted apparently as if they had been unaffected by the treatment. Sometimes the tubes containing the gas were opened in the air for an instant, and the plates put in dry; but no sensible difference in action was perceived, except that it commenced sooner.
584. The power of heat in altering the action of the prepared platina plates was also tried (595.). Plates which had been rendered positive in dilute sulphuric acid for four minutes were well-washed in water, and heated to redness in the flame of a spirit-lamp: after this they acted very well on mixed oxygen and hydrogen. Others, which had been heated more powerfully by the blowpipe, acted afterwards on the gases, though not so powerfully as the former. Hence it appears that heat does not take away the power acquired by the platina at the positive pole of the pile: the occasional diminution of force seemed always referable to other causes than the mere heat. If, for instance, the plate had not been well-washed from the acid, or if the flame used was carbonaceous, or was that of an alcohol lamp trimmed with spirit containing a little acid, or having a wick on which salt, or other extraneous matter, had been placed, then the power of the plate was quickly and greatly diminished (634. 636.).
585. This remarkable property was conferred upon platina when it was made the positive pole in sulphuric acid of specific gravity 1.336, or when it was considerably weaker, or when stronger, even up to the strength of oil of vitriol. Strong and dilute nitric acid, dilute acetic acid, solutions of tartaric, citric, and oxalic acids, were used with equal success. When muriatic acid was used, the plates acquired the power of condensing the oxygen and hydrogen, but in a much inferior degree.
586. Plates which were made positive in solution of caustic potassa did not show any sensible action upon the mixed oxygen and hydrogen. Other plates made positive in solutions of carbonates of potassa and soda exhibited the action, but only in a feeble degree.
587. When a neutral solution of sulphate of soda, or of nitre, or of chlorate of potassa, or of phosphate of potassa, or acetate of potassa, or sulphate of copper, was used, the plates, rendered positive in them for four minutes, and then washed in water, acted very readily and powerfully on the mixed oxygen and hydrogen.
588. It became a very important point, in reference to the cause of this action of the platina, to determine whether the positive pole only could confer it (567.), or whether, notwithstanding the numerous contrary cases, the negative pole might not have the power when such circumstances as could interfere with or prevent the action were avoided. Three plates were therefore rendered negative, for four minutes in diluted sulphuric acid of specific gravity 1.336, washed in distilled water, and put into mixed oxygen and hydrogen. All of them acted, though not so strongly as they would have done if they had been rendered positive. Each combined about a cubical inch and a quarter of the gases in twenty-five minutes. On every repetition of the experiment the same result was obtained; and when the plates were retained in distilled water for ten or twelve minutes, before being introduced into the gas (582.), the action was very much quickened.
589. But when there was any metallic or other substance present in the acid, which could be precipitated on the negative plate, then that plate ceased to act upon the mixed oxygen and hydrogen.
590. These experiments led to the expectation that the power of causing oxygen and hydrogen to combine, which could be conferred upon any piece of platina by making it the positive pole of a voltaic pile, was not essentially dependent upon the action of the pile, or upon any structure or arrangement of parts it might receive whilst in association with it, but belonged to the platina at all times, and was always effective when the surface was perfectly clean. And though, when made the positive pole of the pile in acids, the circumstances might well be considered as those which would cleanse the surface of the platina in the most effectual manner, it did not seem impossible that ordinary operations should produce the same result, although in a less eminent degree.
591. Accordingly, a platina plate (569.) was cleaned by being rubbed with a cork, a little water, and some coal-fire ashes upon a glass plate: being washed, it was put into mixed oxygen and hydrogen, and was found to act at first slowly, and then more rapidly. In an hour, a cubical inch and a half had disappeared.
592. Other plates were cleaned with ordinary sand-paper and water; others with chalk and water; others with emery and water; others, again, with black oxide of manganese and water; and others with a piece of charcoal and water. All of these acted in tubes of oxygen and hydrogen, causing combination of the gases. The action was by no means so powerful as that produced by plates having been in communication with the battery; but from one to two cubical inches of the gases disappeared, in periods extending from twenty-five to eighty or ninety minutes.
593. Upon cleaning the plates with a cork, ground emery, and dilute sulphuric acid, they were found to act still better. In order to simplify the conditions, the cork was dismissed, and a piece of platina foil used instead; still the effect took place. Then the acid was dismissed, and a solution of potassa used, but the effect occurred as before.
594. These results are abundantly sufficient to show that the mere mechanical cleansing of the surface of the platina is sufficient to enable it to exert its combining power over oxygen and hydrogen at common temperatures.
595. I now tried the effect of heat in conferring this property upon platina (584.). Plates which had no action on the mixture of oxygen and hydrogen were heated by the flame of a freshly trimmed spirit-lamp, urged by a mouth blowpipe, and when cold were put into tubes of the mixed gases: they acted slowly at first, but after two or three hours condensed nearly all the gases.
596. A plate of platina, which was about one inch wide and two and three-quarters in length, and which had not been used in any of the preceding experiments, was curved a little so as to enter a tube, and left in a mixture of oxygen and hydrogen for thirteen hours: not the slightest action or combination of the gases occurred. It was withdrawn at the pneumatic trough from the gas through the water, heated red-hot by the spirit-lamp and blowpipe, and then returned when cold into the same portion of gas. In the course of a few minutes diminution of the gases could be observed, and in forty-five minutes about one cubical inch and a quarter had disappeared. In many other experiments platina plates when heated were found to acquire the power of combining oxygen and hydrogen.
597. But it happened not infrequently that plates, after being heated, showed no power of combining oxygen and hydrogen gases, though left undisturbed in them for two hours. Sometimes also it would happen that a plate which, having been heated to dull redness, acted feebly, upon being heated to whiteness ceased to act; and at other times a plate which, having been slightly heated, did not act, was rendered active by a more powerful ignition.
598. Though thus uncertain in its action, and though often diminishing the power given to the plates at the positive pole of the pile (584.), still it is evident that heat can render platina active, which before was inert (595.). The cause of its occasional failure appears to be due to the surface of the metal becoming soiled, either from something previously adhering to it, which is made to adhere more closely by the action of the heat, or from matter communicated from the flame of the lamp, or from the air itself. It often happens that a polished plate of platina, when heated by the spirit-lamp and a blowpipe, becomes dulled and clouded on its surface by something either formed or deposited there; and this, and much less than this, is sufficient to prevent it from exhibiting the curious power now under consideration (634. 636.). Platina also has been said to combine with carbon; and it is not at all unlikely that in processes of heating, where carbon or its compounds are present, a film of such a compound may be thus formed, and thus prevent the exhibition of the properties belonging to pure platina.
When heat does confer the property it is only by the destruction or dissipation of organic or other matter which had previously soiled the plate (632. 633. 634.).--Dec. 1838.
599. The action of alkalies and acids in giving platina this property was now experimentally examined. Platina plates (569.) having no action on mixed oxygen and hydrogen, being boiled in a solution of caustic potassa, washed, and then put into the gases, were found occasionally to act pretty well, but at other times to fail. In the latter case I concluded that the impurity upon the surface of the platina was of a nature not to be removed by the mere solvent action of the alkali, for when the plates were rubbed with a little emery, and the same solution of alkali (592.), they became active.
600. The action of acids was far more constant and satisfactory. A platina plate was boiled in dilute nitric acid: being washed and put into mixed oxygen and hydrogen gases, it acted well. Other plates were boiled in strong nitric acid for periods extending from half a minute to four minutes, and then being washed in distilled water, were found to act very well, condensing one cubic inch and a half of gas in the space of eight or nine minutes, and rendering the tube warm (570.).
601. Strong sulphuric acid was very effectual in rendering the platina active. A plate (569.) was heated in it for a minute, then washed and put into the mixed oxygen and hydrogen, upon which it acted as well as if it had been made the positive pole of a voltaic pile (570.).
602. Plates which, after being heated or electrized in alkali, or after other treatment, were found inert, immediately received power by being dipped for a minute or two, or even only for an instant, into hot oil of vitriol, and then into water.
603. When the plate was dipped into the oil of vitriol, taken out, and then heated so as to drive off the acid, it did not act, in consequence of the impurity left by the acid upon its surface.
604. Vegetable acids, as acetic and tartaric, sometimes rendered inert platina active, at other times not. This, I believe, depended upon the character of the matter previously soiling the plates, and which may easily be supposed to be sometimes of such a nature as to be removed by these acids, and at other times not. Weak sulphuric acid showed the same difference, but strong sulphuric acid (601.) never failed in its action.
605. The most favourable treatment, except that of making the plate a positive pole in strong acid, was as follows. The plate was held over a spirit-lamp flame, and when hot, rubbed with a piece of potassa fusa (caustic potash), which melting, covered the metal with a coat of very strong alkali, and this was retained fused upon the surface for a second or two: it was then put into water for four or five minutes to wash off the alkali, shaken, and immersed for about a minute in hot strong oil of vitriol; from this it was removed into distilled water, where it was allowed to remain ten or fifteen minutes to remove the last traces of acid (582.). Being then put into a mixture of oxygen and hydrogen, combination immediately began, and proceeded rapidly; the tube became warm, the platina became red-hot, and the residue of the gases was inflamed. This effect could be repeated at pleasure, and thus the maximum phenomenon could be produced without the aid of the voltaic battery.
The heat need not be raised so much as to make the alkali tarnish the platina, although if that effect does take place it does not prevent the ultimate action.
606. When a solution of tartaric or acetic acid was substituted, in this mode of preparation, for the sulphuric acid, still the plate was found to acquire the same power, and would often produce explosion in the mixed gases; but the strong sulphuric acid was most certain and powerful.
607. If borax, or a mixture of the carbonates of potash and soda, be fused on the surface of a platina plate, and that plate be well-washed in water, it will be found to have acquired the power of combining oxygen and hydrogen, but only in a moderate degree; but if, after the fusion and washing, it be dipped in the hot sulphuric acid (601.), it will become very active.
608. Other metals than platina were then experimented with. Gold and palladium exhibited the power either when made the positive pole of the voltaic battery (570.), or when acted on by hot oil of vitriol (601.). When palladium is used, the action of the battery or acid should be moderated, as that metal is soon acted upon under such circumstances. Silver and copper could not be made to show any effect at common temperatures.
609. There can remain no doubt that the property of inducing combination, which can thus be conferred upon masses of platina and other metals by connecting them with the poles of the battery, or by cleansing processes either of a mechanical or chemical nature, is the same as that which was discovered by Döbereiner, in 1823, to belong in so eminent a degree to spongy platina, and which was afterwards so well experimented upon and illustrated by MM. Dulong and Thenard, in 1823. The latter philosophers even quote experiments in which a very fine platina wire, which had been coiled up and digested in nitric, sulphuric, or muriatic acid, became ignited when put into a jet of hydrogen gas. This effect I can now produce at pleasure with either wires or plates by the processes described (570. 601. 605.); and by using a smaller plate cut so that it shall rest against the glass by a few points, and yet allow the water to flow off (fig. 59.), the loss of heat is less, the metal is assimilated somewhat to the spongy state, and the probability of failure almost entirely removed.
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Literature · Science
Experimental Researches in Electricity, Volume 1 8
