Chapter 19

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 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[B]; 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.

[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 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[A].

[A] 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[A]. 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.

[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.

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[A], 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.

[A] 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[A], 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.

[A] 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.