Chapter 20

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[A] 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.

[A] 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[A]. 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.

[A] 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[A].

[A] 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[A]; 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[B], and also by Dr. Mitchell of Philadelphia[C] 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.

[A] Quarterly Journal of Science, 1819, vol. vii. p. 106.

[B] Quarterly Journal of Science, vol. xxviii. p. 74, and Edinburgh Transactions, 1831.

[C] 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._[A] ¶ 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._

[A] 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_[A], 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.

[A] [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_[A], and that towards the west the _cathode_[B]; 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.

[A] [Greek: ano] _upwards_, and [Greek: -odos] _a way_; the way which the sun rises.

[B] [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_.[A] 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.

[A] [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_[A] which go to the _anode_ of the decomposing body; and those passing to the _cathode, cations_[B]; 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_.

[A] [Greek: aniôn] _that which goes up._ (Neuter participle.)

[B] [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.