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Experimental Researches in Electricity, Volume 1 8Experimental Researches in Electricity, Volume 1 (part 8)
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Literature · Science
Experimental Researches in Electricity, Volume 1 8
Experimental Researches in Electricity, Volume 1 (part 8)
FaradayEnglish
Annales de Chimie, tom. xxiv. p. 93.
Ibid. tom. xxiii. p. 440; tom. xxiv. p. 380.
Ibid. tom. xxiv. p. 383.
610. M. Döbereiner refers the effect entirely to an electric action. He considers the platina and hydrogen as forming a voltaic element of the ordinary kind, in which the hydrogen, being very highly positive, represents the zinc of the usual arrangement, and like it, therefore, attracts oxygen and combines with it.
tom. xxiv. pp. 94, 95. Also Bibliothèque Universelle, tom. xxiv. p. 54.
611. In the two excellent experimental papers by MM. Dulong and Thenard, those philosophers show that elevation of temperature favours the action, but does not alter its character; Sir Humphry Davy's incandescent platina wire being the same phenomenon with Döbereiner's spongy platina. They show that all metals have this power in a greater or smaller degree, and that it is even possessed by such bodies as charcoal, pumice, porcelain, glass, rock crystal, &c., when their temperatures are raised; and that another of Davy's effects, in which oxygen and hydrogen had combined slowly together at a heat below ignition, was really dependent upon the property of the heated glass, which it has in common with the bodies named above. They state that liquids do not show this effect, at least that mercury, at or below the boiling point, has not the power; that it is not due to porosity; that the same body varies very much in its action, according to its state; and that many other gaseous mixtures besides oxygen and hydrogen are affected, and made to act chemically, when the temperature is raised. They think it probable that spongy platina acquires its power from contact with the acid evolved during its reduction, or from the heat itself to which it is then submitted.
Annales de Chimie, tom. xxiii. p. 440; tom. xxiv. p, 380.
612. MM. Dulong and Thenard express themselves with great caution on the theory of this action; but, referring to the decomposing power of metals on ammonia when heated to temperatures not sufficient alone to affect the alkali, they remark that those metals which in this case are most efficacious, are the least so in causing the combination of oxygen and hydrogen; whilst platina, gold, &c., which have least power of decomposing ammonia, have most power of combining the elements of water:--from which they are led to believe, that amongst gases, some tend to unite under the influence of metals, whilst others tend to separate, and that this property varies in opposite directions with the different metals. At the close of their second paper they observe, that the action is of a kind that cannot be connected with any known theory; and though it is very remarkable that the effects are transient, like those of most electrical actions, yet they state that the greater number of the results observed by them are inexplicable, by supposing them to be of a purely electric origin.
613. Dr. Fusinieri has also written on this subject, and given a theory which he considers as sufficient to account for the phenomena. He expresses the immediate cause thus: "The platina determines upon its surface a continual renovation of concrete laminæ of the combustible substance of the gases or vapours, which flowing over it are burnt, pass away, and are renewed: this combustion at the surface raises and sustains the temperature of the metal." The combustible substance, thus reduced into imperceptible laminæ, of which the concrete parts are in contact with the oxygen, is presumed to be in a state combinable with the oxygen at a much lower temperature than when it is in the gaseous state, and more in analogy with what is called the nascent condition. That combustible gases should lose their elastic state, and become concrete, assuming the form of exceedingly attenuated but solid strata, is considered as proved by facts, some of which are quoted in the Giornale di Fisica for 1824; and though the theory requires that they should assume this state at high temperatures, and though the similar films of aqueous and other matter are dissipated by the action of heat, still the facts are considered as justifying the conclusion against all opposition of reasoning.
Giornale di Fisica, &c., 1825, tom. viii. p. 259.
pp. 138, 371.
614. The power or force which makes combustible gas or vapour abandon its elastic state in contact with a solid, that it may cover the latter with a thin stratum of its own proper substance, is considered as being neither attraction nor affinity. It is able also to extend liquids and solids in concrete laminæ over the surface of the acting solid body, and consists in a repulsion, which is developed from the parts of the solid body by the simple fact of attenuation, and is highest when the attenuation is most complete. The force has a progressive development, and acts most powerfully, or at first, in the direction in which the dimensions of the attenuated mass decrease, and then in the direction of the angles or corners which from any cause may exist on the surface. This force not only causes spontaneous diffusion of gases and other substances over the surface, but is considered as very elementary in its nature, and competent to account for all the phenomena of capillarity, chemical affinity, attraction of aggregation, rarefaction, ebullition, volatilization, explosion, and other thermometric effects, as well as inflammation, detonation, &c. &c. It is considered as a form of heat to which the term native calorie is given, and is still further viewed as the principle of the two electricities and the two magnetisms.
615. I have been the more anxious to give a correct abstract of Dr. Fusinieri's view, both because I cannot form a distinct idea of the power to which he refers the phenomena, and because of my imperfect knowledge of the language in which the memoir is written. I would therefore beg to refer those who pursue the subject to the memoir itself.
616. Not feeling, however, that the problem has yet been solved, I venture to give the view which seems to me sufficient, upon known principles, to account for the effect.
617. It may be observed of this action, that, with regard to platina, it cannot be due to any peculiar, temporary condition, either of an electric or of any other nature: the activity of plates rendered either positive or negative by the pole, or cleaned with such different substances as acids, alkalies, or water; charcoal, emery, ashes, or glass; or merely heated, is sufficient to negative such an opinion. Neither does it depend upon the spongy and porous, or upon the compact and burnished, or upon the massive or the attenuated state of the metal, for in any of these states it may be rendered effective, or its action may be taken away. The only essential condition appears to be a perfectly clean and metallic surface, for whenever that is present the platina acts, whatever its form and condition in other respects may be; and though variations in the latter points will very much affect the rapidity, and therefore the visible appearances and secondary effects, of the action, i.e. the ignition of the metal and the inflammation of the gases, they, even in their most favourable state, cannot produce any effect unless the condition of a clean, pure, metallic surface be also fulfilled.
618. The effect is evidently produced by most, if not all, solid bodies, weakly perhaps by many of them, but rising to a high degree in platina. Dulong and Thenard have very philosophically extended our knowledge of the property to its possession by all the metals, and by earths, glass, stones, &c. (611.); and every idea of its being a known and recognised electric action is in this way removed.
619. All the phenomena connected with this subject press upon my mind the conviction that the effects in question are entirely incidental and of a secondary nature; that they are dependent upon the natural conditions of gaseous elasticity, combined with the exertion of that attractive force possessed by many bodies, especially those which are solid, in an eminent degree, and probably belonging to all; by which they are drawn into association more or less close, without at the same time undergoing chemical combination, though often assuming the condition of adhesion; and which occasionally leads, under very favourable circumstances, as in the present instance, to the combination of bodies simultaneously subjected to this attraction. I am prepared myself to admit (and probably many others are of the same opinion), both with respect to the attraction of aggregation and of chemical affinity, that the sphere of action of particles extends beyond those other particles with which they are immediately and evidently in union (523.), and in many cases produces effects rising into considerable importance: and I think that this kind of attraction is a determining cause of Döbereiner's effect, and of the many others of a similar nature.
620. Bodies which become wetted by fluids with which they do not combine chemically, or in which they do not dissolve, are simple and well-known instances of this kind of attraction.
621. All those cases of bodies which being insoluble in water and not combining with it are hygrometric, and condense its vapour around or upon their surface, are stronger instances of the same power, and approach a little nearer to the cases under investigation. If pulverized clay, protoxide or peroxide of iron, oxide of manganese, charcoal, or even metals, as spongy platina or precipitated silver, be put into an atmosphere containing vapour of water, they soon become moist by virtue of an attraction which is able to condense the vapour upon, although not to combine it with, the substances; and if, as is well known, these bodies so damped be put into a dry atmosphere, as, for instance, one confined over sulphuric acid, or if they be heated, then they yield up this water again almost entirely, it not being in direct or permanent combination.
I met at Edinburgh with a case, remarkable as to its extent, of hygrometric action, assisted a little perhaps by very slight solvent power. Some turf had been well-dried by long exposure in a covered place to the atmosphere, but being then submitted to the action of a hydrostatic press, it yielded, by the mere influence of the pressure, 54 per cent. of water.
622. Still better instances of the power I refer to, because they are more analogous to the cases to be explained, are furnished by the attraction existing between glass and air, so well known to barometer and thermometer makers, for here the adhesion or attraction is exerted between a solid and gases, bodies having very different physical conditions, having no power of combination with each other, and each retaining, during the time of action, its physical state unchanged. When mercury is poured into a barometer tube, a film of air will remain between the metal and glass for months, or, as far as is known, for years, for it has never been displaced except by the action of means especially fitted for the purpose. These consist in boiling the mercury, or in other words, of forming an abundance of vapour, which coming in contact with every part of the glass and every portion of surface of the mercury, gradually mingles with, dilutes, and carries off the air attracted by, and adhering to, those surfaces, replacing it by other vapour, subject to an equal or perhaps greater attraction, but which when cooled condenses into the same liquid as that with which the tube is filled.
Fusinieri and Bellani consider the air as forming solid concrete films in these cases.--Giornale di Fisica, tom. viii, p. 262. 1825.
623. Extraneous bodies, which, acting as nuclei in crystallizing or depositing solutions, cause deposition of substances on them, when it does not occur elsewhere in the liquid, seem to produce their effects by a power of the same kind, i.e. a power of attraction extending to neighbouring particles, and causing them to become attached to the nuclei, although it is not strong enough to make them combine chemically with their substance.
624. It would appear from many cases of nuclei in solutions, and from the effects of bodies put into atmospheres containing the vapours of water, or camphor, or iodine, &c., as if this attraction were in part elective, partaking in its characters both of the attraction of aggregation and chemical affinity: nor is this inconsistent with, but agreeable to, the idea entertained, that it is the power of particles acting, not upon others with which they can immediately and intimately combine, but upon such as are either more distantly situated with respect to them, or which, from previous condition, physical constitution, or feeble relation, are unable to enter into decided union with them.
625. Then, of all bodies, the gases are those which might be expected to show some mutual action whilst jointly under the attractive influence of the platina or other solid acting substance. Liquids, such as water, alcohol, &c., are in so dense and comparatively incompressible a state, as to favour no expectation that their particles should approach much closer to each other by the attraction of the body to which they adhere, and yet that attraction must (according to its effects) place their particles as near to those of the solid wetted body as they are to each other, and in many cases it is evident that the former attraction is the stronger. But gases and vapours are bodies competent to suffer very great changes in the relative distances of their particles by external agencies; and where they are in immediate contact with the platina, the approximation of the particles to those of the metal may be very great. In the case of the hygrometric bodies referred to (621.), it is sufficient to reduce the vapour to the fluid state, frequently from atmospheres so rare that without this influence it would be needful to compress them by mechanical force into a bulk not more than 1/10th or even 1/20th of their original volume before the vapours would become liquids.
626. Another most important consideration in relation to this action of bodies, and which, as far as I am aware, has not hitherto been noticed, is the condition of elasticity under which the gases are placed against the acting surface. We have but very imperfect notions of the real and intimate conditions of the particles of a body existing in the solid, the liquid, and the gaseous state; but when we speak of the gaseous state as being due to the mutual repulsions of the particles or of their atmospheres, although we may err in imagining each particle to be a little nucleus to an atmosphere of heat, or electricity, or any other agent, we are still not likely to be in error in considering the elasticity as dependent on mutuality of action. Now this mutual relation fails altogether on the side of the gaseous particles next to the platina, and we might be led to expect à priori a deficiency of elastic force there to at least one half; for if, as Dalton has shown, the elastic force of the particles of one gas cannot act against the elastic force of the particles of another, the two being as vacua to each other, so is it far less likely that the particles of the platina can exert any influence on those of the gas against it, such as would be exerted by gaseous particles of its own kind.
627. But the diminution of power to one-half on the side of the gaseous body towards the metal is only a slight result of what seems to me to flow as a necessary consequence of the known constitution of gases. An atmosphere of one gas or vapour, however dense or compressed, is in effect as a vacuum to another: thus, if a little water were put into a vessel containing a dry gas, as air, of the pressure of one hundred atmospheres, as much vapour of the water would rise as if it were in a perfect vacuum. Here the particles of watery vapour appear to have no difficulty in approaching within any distance of the particles of air, being influenced solely by relation to particles of their own kind; and if it be so with respect to a body having the same elastic powers as itself, how much more surely must it be so with particles, like those of the platina, or other limiting body, which at the same time that they have not these elastic powers, are also unlike it in nature! Hence it would seem to result that the particles of hydrogen or any other gas or vapour which are next to the platina, &c., must be in such contact with it as if they were in the liquid state, and therefore almost infinitely closer to it than they are to each other, even though the metal be supposed to exert no attractive influence over them.
628. A third and very important consideration in favour of the mutual action of gases under these circumstances is their perfect miscibility. If fluid bodies capable of combining together are also capable of mixture, they do combine when they are mingled, not waiting for any other determining circumstance; but if two such gases as oxygen and hydrogen are put together, though they are elements having such powerful affinity as to unite naturally under a thousand different circumstances, they do not combine by mere mixture. Still it is evident that, from their perfect association, the particles are in the most favourable state possible for combination upon the supervention of any determining cause, such either as the negative action of the platina in suppressing or annihilating, as it were, their elasticity on its side; or the positive action of the metal in condensing them against its surface by an attractive force; or the influence of both together.
629. Although there are not many distinct cases of combination under the influence of forces external to the combining particles, yet there are sufficient to remove any difficulty which might arise on that ground. Sir James Hull found carbonic acid and lime to remain combined under pressure at temperatures at which they would not have remained combined if the pressure had been removed; and I have had occasion to observe a case of direct combination in chlorine, which being compressed at common temperatures will combine with water, and form a definite crystalline hydrate, incapable either of being formed or of existing if that pressure be removed.
Philosophical Transactions, 1823, p. 161.
630. The course of events when platina acts upon, and combines oxygen and hydrogen, may be stated, according to these principles, as follows. From the influence of the circumstances mentioned (619. &c.), i.e. the deficiency of elastic power and the attraction of the metal for the gases, the latter, when they are in association with the former, are so far condensed as to be brought within the action of their mutual affinities at the existing temperature; the deficiency of elastic power, not merely subjecting them more closely to the attractive influence of the metal, but also bringing them into a more favourable state for union, by abstracting a part of that power (upon which depends their elasticity,) which elsewhere in the mass of gases is opposing their combination. The consequence of their combination is the production of the vapour of water and an elevation of temperature. But as the attraction of the platina for the water formed is not greater than for the gases, if so great, (for the metal is scarcely hygrometric,) the vapour is quickly diffused through the remaining gases; fresh portions of this latter, therefore, come into juxtaposition with the metal, combine, and the fresh vapour formed is also diffused, allowing new portions of gas to be acted upon. In this way the process advances, but is accelerated by the evolution of heat, which is known by experiment to facilitate the combination in proportion to its intensity, and the temperature is thus gradually exalted until ignition results.
631. The dissipation of the vapour produced at the surface of the platina, and the contact of fresh oxygen and hydrogen with the metal, form no difficulty in this explication. The platina is not considered as causing the combination of any particles with itself, but only associating them closely around it; and the compressed particles are as free to move from the platina, being replaced by other particles, as a portion of dense air upon the surface of the globe, or at the bottom of a deep mine, is free to move by the slightest impulse, into the upper and rarer parts of the atmosphere.
632. It can hardly be necessary to give any reasons why platina does not show this effect under ordinary circumstances. It is then not sufficiently clean (617.), and the gases are prevented from touching it, and suffering that degree of effect which is needful to commence their combination at common temperatures, and which they can only experience at its surface. In fact, the very power which causes the combination of oxygen and hydrogen, is competent, under the usual casual exposure of platina, to condense extraneous matters upon its surface, which soiling it, take away for the time its power of combining oxygen and hydrogen, by preventing their contact with it (598.).
633. Clean platina, by which I mean such as has been made the positive pole of a pile (570.), or has been treated with acid (605.), and has then been put into distilled water for twelve or fifteen minutes, has a peculiar friction when one piece is rubbed against another. It wets freely with pure water, even after it has been shaken and dried by the heat of a spirit-lamp; and if made the pole of a voltaic pile in a dilute acid, it evolves minute bubbles from every part of its surface. But platina in its common state wants that peculiar friction: it will not wet freely with water as the clean platina does; and when made the positive pole of a pile, it for a time gives off large bubbles, which seem to cling or adhere to the metal, and are evolved at distinct and separate points of the surface. These appearances and effects, as well as its want of power on oxygen and hydrogen, are the consequences, and the indications, of a soiled surface.
634. I found also that platina plates which had been cleaned perfectly soon became soiled by mere exposure to the air; for after twenty-four hours they no longer moistened freely with water, but the fluid ran up into portions, leaving part of the surface bare, whilst other plates which had been retained in water for the same time, when they were dried (580.) did moisten, and gave the other indications of a clean surface.
635. Nor was this the case with platina or metals only, but also with earthy bodies, Rock crystal and obsidian would not wet freely upon the surface, but being moistened with strong oil of vitriol, then washed, and left in distilled water to remove all the acid, they did freely become moistened, whether they were previously dry or whether they were left wet; but being dried and left exposed to the air for twenty-four hours, their surface became so soiled that water would not then adhere freely to it, but ran up into partial portions. Wiping with a cloth (even the cleanest) was still worse than exposure to air; the surface either of the minerals or metals immediately became as if it were slightly greasy. The floating upon water of small particles of metals under ordinary circumstances is a consequence of this kind of soiled surface. The extreme difficulty of cleaning the surface of mercury when it has once been soiled or greased, is due to the same cause.
636. The same reasons explain why the power of the platina plates in some circumstances soon disappear, and especially upon use: MM. Dulong and Thenard have observed the same effect with the spongy metal, as indeed have all those who have used Döbereiner's instantaneous light machines. If left in the air, if put into ordinary distilled water, if made to act upon ordinary oxygen and hydrogen, they can still find in all these cases that minute portion of impurity which, when once in contact with the surface of the platina, is retained there, and is sufficient to prevent its full action upon oxygen and hydrogen at common temperatures: a slight elevation of temperature is again sufficient to compensate this effect, and cause combination.
Annales de Chimie, tom. xxiv. p. 386.
637. No state of a solid body can be conceived more favourable for the production of the effect than that which is possessed by platina obtained from the ammonio-muriate by heat. Its surface is most extensive and pure, yet very accessible to the gases brought in contact with it: if placed in impurity, the interior, as Thenard and Dulong have observed, is preserved clean by the exterior; and as regards temperature, it is so bad a conductor of heat, because of its divided condition, that almost all which is evolved by the combination of the first portions of gas is retained within the mass, exalting the tendency of the succeeding portions to combine.
638. I have now to notice some very extraordinary interferences with this phenomenon, dependent, not upon the nature or condition of the metal or other acting solid, but upon the presence of certain substances mingled with the gases acted upon; and as I shall have occasion to speak frequently of a mixture of oxygen and hydrogen, I wish it always to be understood that I mean a mixture composed of one volume of oxygen to two volumes of hydrogen, being the proportions that form water. Unless otherwise expressed, the hydrogen was always that obtained by the action of dilute sulphuric acid on pure zinc, and the oxygen that obtained by the action of heat from the chlorate of potassa.
639. Mixtures of oxygen and hydrogen with air, containing one-fourth, one-half, and even two-thirds of the latter, being introduced with prepared platina plates (570. 605.) into tubes, were acted upon almost as well as if no air were present: the retardation was far less than might have been expected from the mere dilution and consequent obstruction to the contact of the gases with the plates. In two hours and a half nearly all the oxygen and hydrogen introduced as mixture was gone.
640. But when similar experiments were made with olefiant gas (the platina plates having been made the positive poles of a voltaic pile (570.) in acid), very different results occurred. A mixture was made of 29.2 volumes hydrogen and 14.6 volumes oxygen, being the proportions for water; and to this was added another mixture of 3 volumes oxygen and one volume olefiant gas, so that the olefiant gas formed but 1/40th part of the whole; yet in this mixture the platina plate would not act in forty-five hours. The failure was not for want of any power in the plate, for when after that time it was taken out of this mixture and put into one of oxygen and hydrogen, it immediately acted, and in seven minutes caused explosion of the gas. This result was obtained several times, and when larger proportions of olefiant gas were used, the action seemed still more hopeless.
641. A mixture of forty-nine volumes oxygen and hydrogen (638.) with one volume of olefiant gas had a well-prepared platina plate introduced. The diminution of gas was scarcely sensible at the end of two hours, during which it was watched; but on examination twenty-four hours afterwards, the tube was found blown to pieces. The action, therefore, though it had been very much retarded, had occurred at last, and risen to a maximum.
642. With a mixture of ninety-nine volumes of oxygen and hydrogen (638.) with one of olefiant gas, a feeble action was evident at the end of fifty minutes; it went on accelerating (630.) until the eighty-fifth minute, and then became so intense that the gas exploded. Here also the retarding effect of the olefiant gas was very beautifully illustrated.
643. Plates prepared by alkali and acid (605.) produced effects corresponding to those just described.
644. It is perfectly clear from these experiments, that olefiant gas, even in small quantities, has a very remarkable influence in preventing the combination of oxygen and hydrogen under these circumstances, and yet without at all injuring or affecting the power of the platina.
645. Another striking illustration of similar interference may be shown in carbonic oxide; especially if contrasted with carbonic acid. A mixture of one volume oxygen and hydrogen (638.) with four volumes of carbonic acid was affected at once by a platina plate prepared with acid, &c. (605.); and in one hour and a quarter nearly all the oxygen and hydrogen was gone. Mixtures containing less carbonic acid were still more readily affected.
646. But when carbonic oxide was substituted for the carbonic acid, not the slightest effect of combination was produced; and when the carbonic oxide was only one-eighth of the whole volume, no action occurred in forty and fifty hours. Yet the plates had not lost their power; for being taken out and put into pure oxygen and hydrogen, they acted well and at once.
647. Two volumes of carbonic oxide and one of oxygen were mingled with nine volumes of oxygen and hydrogen (638.). This mixture was not affected by a plate which had been made positive in acid, though it remained in it fifteen hours. But when to the same volumes of carbonic oxide and oxygen were added thirty-three volumes of oxygen and hydrogen, the carbonic oxide being then only 1/18th part of the whole, the plate acted, slowly at first, and at the end of forty-two minutes the gases exploded.
648. These experiments were extended to various gases and vapours, the general results of which may be given as follow. Oxygen, hydrogen, nitrogen, and nitrous oxide, when used to dilute the mixture of oxygen and hydrogen, did not prevent the action of the plates even when they made four-fifths of the whole volume of gas acted upon. Nor was the retardation so great in any case as might have been expected from the mere dilution of the oxygen and hydrogen, and the consequent mechanical obstruction to its contact with the platina. The order in which carbonic acid and these substances seemed to stand was as follows, the first interfering least with the action; nitrous oxide, hydrogen, carbonic acid, nitrogen, oxygen: but it is possible the plates were not equally well prepared in all the cases, and that other circumstances also were unequal; consequently more numerous experiments would be required to establish the order accurately.
649. As to cases of retardation, the powers of olefiant gas and carbonic oxide have been already described. Mixtures of oxygen and hydrogen, containing from 1/16th to 1/20th of sulphuretted hydrogen or phosphuretted hydrogen, seemed to show a little action at first, but were not further affected by the prepared plates, though in contact with them for seventy hours. When the plates were removed they had lost all power over pure oxygen and hydrogen, and the interference of these gases was therefore of a different nature from that of the two former, having permanently affected the plate.
650. A small piece of cork was dipped in sulphuret of carbon and passed up through water into a tube containing oxygen and hydrogen (638.), so as to diffuse a portion of its vapour through the gases. A plate being introduced appeared at first to act a little, but after sixty-one hours the diminution was very small. Upon putting the same plate into a pure mixture of oxygen and hydrogen, it acted at once and powerfully, having apparently suffered no diminution of its force.
651. A little vapour of ether being mixed with the oxygen and hydrogen retarded the action of the plate, but did not prevent it altogether. A little of the vapour of the condensed oil-gas liquor retarded the action still more, but not nearly so much as an equal volume of olefiant gas would have done. In both these cases it was the original oxygen and hydrogen which combined together, the ether and the oil-gas vapour remaining unaffected, and in both cases the plates retained the power of acting on fresh oxygen and hydrogen.
Philosophical Transactions, 1825, p.440.
652. Spongy platina was then used in place of the plates, and jets of hydrogen mingled with the different gases thrown against it in air. The results were exactly of the same kind, although presented occasionally in a more imposing form. Thus, mixtures of one volume of olefiant gas or carbonic oxide with three of hydrogen could not heat the spongy platina when the experiments were commenced at common temperatures; but a mixture of equal volumes of nitrogen and hydrogen acted very well, causing ignition. With carbonic acid the results were still more striking. A mixture of three volumes of that gas with one of hydrogen caused ignition of the platina, yet that mixture would not continue to burn from the jet when attempts were made to light it by a taper. A mixture even of seven volumes of carbonic acid and one of hydrogen will thus cause the ignition of cold spongy platina, and yet, as if to supply a contrast, than which none can be greater, it cannot burn at a taper, but causes the extinction of the latter. On the other hand, the mixtures of carbonic oxide or olefiant gas, which can do nothing with the platina, are inflamed by the taper, burning well.
653. Hydrogen mingled with the vapour of ether or oil-gas liquor causes the ignition of the spongy platina. The mixture with oil-gas burns with a flame far brighter than that of the mixture of hydrogen and olefiant gas already referred to, so that it would appear that the retarding action of the hydrocarbons is not at all in proportion merely to the quantity of carbon present.
654. In connexion with these interferences, I must state, that hydrogen itself, prepared from steam passed over ignited iron, was found when mingled with oxygen to resist the action of platina. It had stood over water seven days, and had lost all fetid smell; but a jet of it would not cause the ignition of spongy platina, commencing at common temperatures; nor would it combine with oxygen in a tube either under the influence of a prepared plate or of spongy platina. A mixture of one volume of this gas with three of pure hydrogen, and the due proportion of oxygen, was not affected by plates after fifty hours. I am inclined to refer the effect to carbonic oxide present in the gas, but have not had time to verify the suspicion. The power of the plates was not destroyed (640. 646.).
655. Such are the general facts of these remarkable interferences. Whether the effect produced by such small quantities of certain gases depends upon any direct action which they may exert upon the particles of oxygen and hydrogen, by which the latter are rendered less inclined to combine, or whether it depends upon their modifying the action of the plate temporarily (for they produce no real change on it), by investing it through the agency of a stronger attraction than that of the hydrogen, or otherwise, remains to be decided by more extended experiments.
656. The theory of action which I have given for the original phenomena appears to me quite sufficient to account for all the effects by reference to known properties, and dispenses with the assumption of any new power of matter. I have pursued this subject at some length, as one of great consequence, because I am convinced that the superficial actions of matter, whether between two bodies, or of one piece of the same body, and the actions of particles not directly or strongly in combination, are becoming daily more and more important to our theories of chemical as well as mechanical philosophy. In all ordinary cases of combustion it is evident that an action of the kind considered, occurring upon the surface of the carbon in the fire, and also in the bright part of a flame, must have great influence over the combinations there taking place.
As a curious illustration of the influence of mechanical forces over chemical affinity, I will quote the refusal of certain substances to effloresce when their surfaces are perfect, which yield immediately upon the surface being broken, If crystals of carbonate of soda, or phosphate of soda, or sulphate of soda, having no part of their surfaces broken, be preserved from external violence, they will not effloresce. I have thus retained crystals of carbonate of soda perfectly transparent and unchanged from September 1827 to January 1833; and crystals of sulphate of soda from May 1832 to the present time, November 1833. If any part of the surface were scratched or broken, then efflorescence began at that part, and covered the whole. The crystals were merely placed in evaporating basins and covered with paper.
657. The condition of elasticity upon the exterior of the gaseous or vaporous mass already referred to (626. 627.), must be connected directly with the action of solid bodies, as nuclei, on vapours, causing condensation upon them in preference to any condensation in the vapours themselves; and in the well-known effect of nuclei on solutions a similar condition may have existence (623.), for an analogy in condition exists between the parts of a body in solution, and those of a body in the vaporous or gaseous state. This thought leads us to the consideration of what are the respective conditions at the surfaces of contact of two portions of the same substance at the same temperature, one in the solid or liquid, and the other in the vaporous state; as, for instance, steam and water. It would seem that the particles of vapour next to the particles of liquid are in a different relation to the latter to what they would be with respect to any other liquid or solid substance; as, for instance, mercury or platina, if they were made to replace the water, i.e. if the view of independent action which I have taken (626. 627.) as a consequence of Dalton's principles, be correct. It would also seem that the mutual relation of similar particles, and the indifference of dissimilar particles which Dalton has established as a matter of fact amongst gases and vapours, extends to a certain degree amongst solids and fluids, that is, when they are in relation by contact with vapours, either of their own substance or of other bodies. But though I view these points as of great importance with respect to the relations existing between different substances and their physical constitution in the solid, liquid, or gaseous state, I have not sufficiently considered them to venture any strong opinions or statements here.
In reference to this paragraph and also 626, see a correction by Dr. C. Henry, in his valuable paper on this curious subject. Philosophical Magazine, 1835. vol. vi. p. 305.--Dec. 1838.
658. There are numerous well-known cases, in which substances, such as oxygen and hydrogen, act readily in their nascent state, and produce chemical changes which they are not able to effect if once they have assumed the gaseous condition. Such instances are very common at the poles of the voltaic pile, and are, I think, easily accounted for, if it be considered that at the moment of separation of any such particle it is entirely surrounded by other particles of a different kind with which it is in close contact, and has not yet assumed those relations and conditions which it has in its fully developed state, and which it can only assume by association with other particles of its own kind. For, at the moment, its elasticity is absent, and it is in the same relation to particles with which it is in contact, and for which it has an affinity, as the particles of oxygen and hydrogen are to each other on the surface of clean platina (626. 627.).
659. The singular effects of retardation produced by very small quantities of some gases, and not by large quantities of others (640. 645. 652.), if dependent upon any relation of the added gas to the surface of the solid, will then probably be found immediately connected with the curious phenomena which are presented by different gases when passing through narrow tubes at low pressures, which I observed many years ago; and this action of surfaces must, I think, influence the highly interesting phenomena of the diffusion of gases, at least in the form in which it has been experimented upon by Mr. Graham in 1829 and 1831, and also by Dr. Mitchell of Philadelphia in 1830. It seems very probable that if such a substance as spongy platina were used, another law for the diffusion of gases under the circumstances would come out than that obtained by the use of plaster of Paris.
Quarterly Journal of Science, 1819, vol. vii. p. 106.
Quarterly Journal of Science, vol. xxviii. p. 74, and Edinburgh Transactions, 1831.
Journal of the Royal Institution for 1831, p. 101.
660. I intended to have followed this section by one on the secondary piles of Ritter, and the peculiar properties of the poles of the pile, or of metals through which electricity has passed, which have been observed by Ritter, Van Marum, Yelin, De la Rive, Marianini, Berzelius, and others. It appears to me that all these phenomena bear a satisfactory explanation on known principles, connected with the investigation just terminated, and do not require the assumption of any new state or new property. But as the experiments advanced, especially those of Marianini, require very careful repetition and examination, the necessity of pursuing the subject of electro-chemical decomposition obliges me for a time to defer the researches to which I have just referred.
_Royal Institution,
November 30, 1833._
SEVENTH SERIES.
§ 11. On Electro-chemical Decomposition, continued. ¶ iv. On some general conditions of Electro-decomposition. ¶ v. On a new Measurer of Volta-electricity. ¶ vi. On the primary or secondary character of bodies evolved in Electro-decomposition. ¶ vii. On the definite nature and extent of Electro-chemical Decompositions. § 13. On the absolute quantity of Electricity associated with the particles or atoms of Matter.
Refer to the note after 1047, Series VIII.--Dec. 1838.
Received January 9,--Read January 23, February 6 and 13, 1834.
Preliminary.
661. The theory which I believe to be a true expression of the facts of electro-chemical decomposition, and which I have therefore detailed in a former series of these Researches, is so much at variance with those previously advanced, that I find the greatest difficulty in stating results, as I think, correctly, whilst limited to the use of terms which are current with a certain accepted meaning. Of this kind is the term pole, with its prefixes of positive and negative, and the attached ideas of attraction and repulsion. The general phraseology is that the positive pole attracts oxygen, acids, &c., or more cautiously, that it determines their evolution upon its surface; and that the negative pole acts in an equal manner upon hydrogen, combustibles, metals, and bases. According to my view, the determining force is not at the poles, but within the body under decomposition; and the oxygen and acids are rendered at the negative extremity of that body, whilst hydrogen, metals, &c., are evolved at the positive extremity (518. 524.).
662. To avoid, therefore, confusion and circumlocution, and for the sake of greater precision of expression than I can otherwise obtain, I have deliberately considered the subject with two friends, and with their assistance and concurrence in framing them, I purpose henceforward using certain other terms, which I will now define. The poles, as they are usually called, are only the doors or ways by which the electric current passes into and out of the decomposing body (556.); and they of course, when in contact with that body, are the limits of its extent in the direction of the current. The term has been generally applied to the metal surfaces in contact with the decomposing substance; but whether philosophers generally would also apply it to the surfaces of air (465. 471.) and water (493.), against which I have effected electro-chemical decomposition, is subject to doubt. In place of the term pole, I propose using that of Electrode, and I mean thereby that substance, or rather surface, whether of air, water, metal, or any other body, which bounds the extent of the decomposing matter in the direction of the electric current.
[Greek: elektron], and [Greek: -odos] a way.
663. The surfaces at which, according to common phraseology, the electric current enters and leaves a decomposing body, are most important places of action, and require to be distinguished apart from the poles, with which they are mostly, and the electrodes, with which they are always, in contact. Wishing for a natural standard of electric direction to which I might refer these, expressive of their difference and at the same time free from all theory, I have thought it might be found in the earth. If the magnetism of the earth be due to electric currents passing round it, the latter must be in a constant direction, which, according to present usage of speech, would be from east to west, or, which will strengthen this help to the memory, that in which the sun appears to move. If in any case of electro-decomposition we consider the decomposing body as placed so that the current passing through it shall be in the same direction, and parallel to that supposed to exist in the earth, then the surfaces at which the electricity is passing into and out of the substance would have an invariable reference, and exhibit constantly the same relations of powers. Upon this notion we purpose calling that towards the east the anode, and that towards the west the cathode; and whatever changes may take place in our views of the nature of electricity and electrical action, as they must affect the natural standard referred to, in the same direction, and to an equal amount with any decomposing substances to which these terms may at any time be applied, there seems no reason to expect that they will lead to confusion, or tend in any way to support false views. The anode is therefore that surface at which the electric current, according to our present expression, enters: it is the negative extremity of the decomposing body; is where oxygen, chlorine, acids, &c., are evolved; and is against or opposite the positive electrode. The cathode is that surface at which the current leaves the decomposing body, and is its positive extremity; the combustible bodies, metals, alkalies, and bases, are evolved there, and it is in contact with the negative electrode.
[Greek: ano] upwards, and [Greek: -odos] a way; the way which the sun rises.
[Greek: kata] downwards, and [Greek: -odos] a way; the way which the sun sets.
664. I shall have occasion in these Researches, also, to class bodies together according to certain relations derived from their electrical actions (822.); and wishing to express those relations without at the same time involving the expression of any hypothetical views, I intend using the following names and terms. Many bodies are decomposed directly by the electric current, their elements being set free; these I propose to call electrolytes. Water, therefore, is an electrolyte. The bodies which, like nitric or sulphuric acids, are decomposed in a secondary manner (752. 757.), are not included under this term. Then for electro-chemically decomposed, I shall often use the term electrolyzed, derived in the same way, and implying that the body spoken of is separated into its components under the influence of electricity: it is analogous in its sense and sound to analyse, which is derived in a similar manner. The term electrolytical will be understood at once: muriatic acid is electrolytical, boracic acid is not.
[Greek: elektron], and [Greek: lyo], soluo. N. Electrolyte, V. Electrolyze.
665. Finally, I require a term to express those bodies which can pass to the electrodes, or, as they are usually called, the poles. Substances are frequently spoken of as being electro-negative, or electro-positive, according as they go under the supposed influence of a direct attraction to the positive or negative pole. But these terms are much too significant for the use to which I should have to put them; for though the meanings are perhaps right, they are only hypothetical, and may be wrong; and then, through a very imperceptible, but still very dangerous, because continual, influence, they do great injury to science, by contracting and limiting the habitual views of those engaged in pursuing it. I propose to distinguish such bodies by calling those anions which go to the anode of the decomposing body; and those passing to the cathode, cations; and when I have occasion to speak of these together, I shall call them ions. Thus the chloride of lead is an electrolyte, and when electrolyzed evolves the two ions, chlorine and lead, the former being an anion, and the latter a cation.
[Greek: aniôn] that which goes up. (Neuter participle.)
[Greek: katiôn] that which goes down.
666. These terms being once well-defined, will, I hope, in their use enable me to avoid much periphrasis and ambiguity of expression. I do not mean to press them into service more frequently than will be required, for I am fully aware that names are one thing and science another.
667. It will be well understood that I am giving no opinion respecting the nature of the electric current now, beyond what I have done on former occasions (283. 517.); and that though I speak of the current as proceeding from the parts which are positive to those which are negative (663.), it is merely in accordance with the conventional, though in some degree tacit, agreement entered into by scientific men, that they may have a constant, certain, and definite means of referring to the direction of the forces of that current.
[Since this paper was read, I have changed some of the terms which were first proposed, that I might employ only such as were at the same time simple in their nature, clear in their reference, and free from hypothesis.
¶ iv. On some general conditions of Electro-chemical Decomposition.
669. From the period when electro-chemical decomposition was first effected to the present time, it has been a remark, that those elements which, in the ordinary phenomena of chemical affinity, were the most directly opposed to each other, and combined with the greatest attractive force, were those which were the most readily evolved at the opposite extremities of the decomposing bodies (549.).
670. If this result was evident when water was supposed to be essential to, and was present in, almost every case of such decomposition (472.), it is far more evident now that it has been shown and proved that water is not necessarily concerned in the phenomena (474.), and that other bodies much surpass it in some of the effects supposed to be peculiar to that substance.
671. Water, from its constitution and the nature of its elements, and from its frequent presence in cases of electrolytic action, has hitherto stood foremost in this respect. Though a compound formed by very powerful affinity, it yields up its elements under the influence of a very feeble electric current; and it is doubtful whether a case of electrolyzation can occur, where, being present, it is not resolved into its first principles.
672. The various oxides, chlorides, iodides, and salts, which I have shown are decomposable by the electric current when in the liquid state, under the same general law with water (402.), illustrate in an equally striking manner the activity, in such decompositions, of elements directly and powerfully opposed to each other by their chemical relations.
673. On the other hand, bodies dependent on weak affinities very rarely give way. Take, for instance, glasses: many of those formed of silica, lime, alkali, and oxide of lead, may be considered as little more than solutions of substances one in another. If bottle-glass be fused, and subjected to the voltaic pile, it does not appear to be at all decomposed (408.). If flint glass, which contains substances more directly opposed, be operated upon, it suffers some decomposition; and if borate of lead glass, which is a definite chemical compound, be experimented with, it readily yields up its elements (408.).
Philosophical Transactions, 1830, p. 49.
674. But the result which is found to be so striking in the instances quoted is not at all borne out by reference to other cases where a similar consequence might have been expected. It may be said, that my own theory of electro-chemical decomposition would lead to the expectation that all compound bodies should give way under the influence of the electric current with a facility proportionate to the strength of the affinity by which their elements, either proximate or ultimate, are combined. I am not sure that that follows as a consequence of the theory; but if the objection is supposed to be one presented by the facts, I have no doubt it will be removed when we obtain a more intimate acquaintance with, and precise idea of, the nature of chemical affinity and the mode of action of an electric current over it (518. 524.): besides which, it is just as directly opposed to any other theory of electro-chemical decomposition as the one I have propounded; for if it be admitted, as is generally the case, that the more directly bodies are opposed to each other in their attractive forces, the more powerfully do they combine, then the objection applies with equal force to any of the theories of electrolyzation which have been considered, and is an addition to those which I have taken against them.
675. Amongst powerful compounds which are not decomposed, boracic acids stand prominent (408.). Then again, the iodide of sulphur, and the chlorides of sulphur, phosphorus, and carbon, are not decomposable under common circumstances, though their elements are of a nature which would lead to a contrary expectation. Chloride of antimony (402. 690.), the hydro-carbons, acetic acid, ammonia, and many other bodies undecomposable by the voltaic pile, would seem to be formed by an affinity sufficiently strong to indicate that the elements were so far contrasted in their nature as to sanction the expectation that, the pile would separate them, especially as in some cases of mere solution (530. 544.), where the affinity must by comparison be very weak, separation takes place.
With regard to solution, I have met with some reasons for supposing that it will probably disappear as a cause of transference, and intend resuming the consideration at a convenient opportunity.
676. It must not be forgotten, however, that much of this difficulty, and perhaps the whole, may depend upon the absence of conducting power, which, preventing the transmission of the current, prevents of course the effects due to it. All known compounds being non-conductors when solid, but conductors when liquid, are decomposed, with perhaps the single exception at present known of periodide of mercury (679. 691.); and even water itself, which so easily yields up its elements when the current passes, if rendered quite pure, scarcely suffers change, because it then becomes a very bad conductor.
See now, 1340, 1341.--Dec. 1838.
677. If it should hereafter be proved that the want of decomposition in those cases where, from chemical considerations, it might be so strongly expected (669, 672. 674.), is due to the absence or deficiency of conducting power, it would also at the same time be proved that decomposition depends upon conduction, and not the latter upon the former (413.); and in water this seems to be very nearly decided. On the other hand, the conclusion is almost irresistible, that in electrolytes the power of transmitting the electricity across the substance is dependent upon their capability of suffering decomposition; taking place only whilst they are decomposing, and being proportionate to the quantity of elements separated (821.). I may not, however, stop to discuss this point experimentally at present.
678. When a compound contains such elements as are known to pass towards the opposite extremities of the voltaic pile, still the proportions in which they are present appear to be intimately connected with capability in the compound of suffering or resisting decomposition. Thus, the protochloride of tin readily conducts, and is decomposed (402.), but the perchloride neither conducts nor is decomposed (406.). The protiodide of tin is decomposed when fluid (402.); the periodide is not (405.). The periodide of mercury when fused is not decomposed (691.), even though it does conduct. I was unable to contrast it with the protiodide, the latter being converted into mercury and periodide by heat.
679. These important differences induced me to look more closely to certain binary compounds, with a view of ascertaining whether a law regulating the decomposability according to some relation of the proportionals or equivalents of the elements, could be discovered. The proto compounds only, amongst those just referred to, were decomposable; and on referring to the substances quoted to illustrate the force and generality of the law of conduction and decomposition which I discovered (402.), it will be found that all the oxides, chlorides, and iodides subject to it, except the chloride of antimony and the periodide of mercury, (to which may now perhaps be added corrosive sublimate,) are also decomposable, whilst many per compounds of the same elements, not subject to the law, were not so (405. 406.).
680. The substances which appeared to form the strongest exceptions to this general result were such bodies as the sulphuric, phosphoric, nitric, arsenic, and other acids.
681. On experimenting with sulphuric acid, I found no reason to believe that it was by itself a conductor of, or decomposable by, electricity, although I had previously been of that opinion (552.). When very strong it is a much worse conductor than if diluted. If then subjected to the action of a powerful battery, oxygen appears at the anode, or positive electrode, although much is absorbed (728.), and hydrogen and sulphur appear at the cathode, or negative electrode. Now the hydrogen has with me always been pure, not sulphuretted, and has been deficient in proportion to the sulphur present, so that it is evident that when decomposition occurred water must have been decomposed. I endeavoured to make the experiment with anhydrous sulphuric acid; and it appeared to me that, when fused, such acid was not a conductor, nor decomposed; but I had not enough of the dry acid in my possession to allow me to decide the point satisfactorily. My belief is, that when sulphur appears during the action of the pile on sulphuric acid, it is the result of a secondary action, and that the acid itself is not electrolyzable (757.).
De la Rive.
682. Phosphoric acid is, I believe, also in the same condition; but I have found it impossible to decide the point, because of the difficulty of operating on fused anhydrous phosphoric acid. Phosphoric acid which has once obtained water cannot be deprived of it by heat alone. When heated, the hydrated acid volatilizes. Upon subjecting phosphoric acid, fused upon the ring end of a wire (401.), to the action of the voltaic apparatus, it conducted, and was decomposed; but gas, which I believe to be hydrogen, was always evolved at the negative electrode, and the wire was not affected as would have happened had phosphorus been separated. Gas was also evolved at the positive electrode. From all the facts, I conclude it was the water and not the acid which was decomposed.
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Literature · Science
Experimental Researches in Electricity, Volume 1 9
