587. When a neutral solution of sulphate of soda, or of nitre, or of chlorate of pota.s.sa, or of phosphate of pota.s.sa, or acetate of pota.s.sa, 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 circ.u.mstances 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 repet.i.tion 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 a.s.sociation 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 circ.u.mstances 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 gla.s.s 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 _pota.s.sa_ 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[A].
[A] 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 pota.s.sa, 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 s.p.a.ce 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 pota.s.sa 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[A]: 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.
[A] 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 subst.i.tuted, 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 circ.u.mstances. 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 ma.s.ses 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 Dobereiner[A], in 1823, to belong in so eminent a degree to spongy platina, and which was afterwards so well experimented upon and ill.u.s.trated by MM. Dulong and Thenard[B], 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[C]. 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 gla.s.s by a few points, and yet allow the water to flow off (fig. 59.), the loss of heat is less, the metal is a.s.similated somewhat to the spongy state, and the probability of failure almost entirely removed.
[A] Annales de Chimie, tom. xxiv. p. 93.
[B] Ibid. tom. xxiii. p. 440; tom. xxiv. p. 380.
[C] Ibid. tom. xxiv. p. 383.
610. M. Dobereiner 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[A].
[A] tom. xxiv. pp. 94, 95. Also Bibliotheque Universelle, tom. xxiv.
p. 54.
611. In the two excellent experimental papers by MM. Dulong and Thenard[A], 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 Dobereiner"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, gla.s.s, 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 gla.s.s, 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.
[A] 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[A]. He expresses the immediate cause thus: "The platina determines upon its surface a continual renovation of _concrete laminae_ of the combustible substance of the gases or vapours, which flowing over it are burnt, pa.s.s away, and are renewed: this combustion at the surface raises and sustains the temperature of the metal." The combustible substance, thus reduced into imperceptible laminae, 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 a.n.a.logy with what is called the nascent condition. That combustible gases should lose their elastic state, and become concrete, a.s.suming 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[B]; and though the theory requires that they should a.s.sume 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.
[A] Giornale di Fisica, &c., 1825, tom. viii. p. 259.
[B] 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 laminae 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 ma.s.s 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 gla.s.s; 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 ma.s.sive 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, gla.s.s, 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 a.s.sociation more or less close, without at the same time undergoing chemical combination, though often a.s.suming the condition of adhesion; and which occasionally leads, under very favourable circ.u.mstances, 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 Dobereiner"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[A].
[A] I met at Edinburgh with a case, remarkable as to its extent, of hygrometric action, a.s.sisted 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 a.n.a.logous to the cases to be explained, are furnished by the attraction existing between gla.s.s 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[A]. When mercury is poured into a barometer tube, a film of air will remain between the metal and gla.s.s 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 gla.s.s 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.
[A] 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.