Part 31

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.

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.