Experimental Researches in Electricity, Volume 1 10 – Faraday · Verses Across
Literature · Science
Experimental Researches in Electricity, Volume 1 10Experimental Researches in Electricity, Volume 1 (part 10)
18
Literature · Science
Experimental Researches in Electricity, Volume 1 10
Experimental Researches in Electricity, Volume 1 (part 10)
FaradayEnglish
773. Acetic acid.--Glacial acetic acid, when fused (405.), is not decomposed by, nor does it conduct, electricity. On adding a little water to it, still there were no signs of action; on adding more water, it acted slowly and about as pure water would do. Dilute sulphuric acid was added to it in order to make it a better conductor; then the definite proportion of hydrogen was evolved at the cathode, and a mixture of oxygen in very deficient quantity, with carbonic acid, and a little carbonic oxide, at the anode. Hence it appears that acetic acid is not electrolyzable, but that a portion of it is decomposed by the oxygen evolved at the anode, producing secondary results, varying with the strength of the acid, the intensity of the current, and other circumstances.
774. Acetates.--One of these has been referred to already, as affording only secondary results relative to the acetic acid (749.). With many of the metallic acetates the results at both electrodes are secondary (746. 750.).
Acetate of soda fused and anhydrous is directly decomposed, being, as I believe, a true electrolyte, and evolving soda and acetic acid at the cathode and anode. These however have no sensible duration, but are immediately resolved into other substances; charcoal, sodiuretted hydrogen, &c., being set free at the former, and, as far as I could judge under the circumstances, acetic acid mingled with carbonic oxide, carbonic acid, &c. at the latter.
775. Tartaric acid.--Pure solution of tartaric acid is almost as bad a conductor as pure water. On adding sulphuric acid, it conducted well, the results at the positive electrode being primary or secondary in different proportions, according to variations in the strength of the acid and the power of the electric current (752.). Alkaline tartrates gave a large proportion of secondary results at the positive electrode. The hydrogen at the negative electrode remained constant unless certain triple metallic salts were used.
776. Solutions, of salts containing other vegetable acids, as the benzoates; of sugar, gum, &c., dissolved in dilute sulphuric acid; of resin, albumen, &c., dissolved in alkalies, were in turn submitted to the electrolytic power of the voltaic current. In all these cases, secondary results to a greater or smaller extent were produced at the positive electrode.
777. In concluding this division of these Researches, it cannot but occur to the mind that the final result of the action of the electric current upon substances, placed between the electrodes, instead of being simple may be very complicated. There are two modes by which these substances may be decomposed, either by the direct force of the electric current, or by the action of bodies which that current may evolve. There are also two modes by which new compounds may be formed, i.e. by combination of the evolving substances whilst in their nascent state (658.), directly with the matter of the electrode; or else their combination with those bodies, which being contained in, or associated with, the body suffering decomposition, are necessarily present at the anode and cathode. The complexity is rendered still greater by the circumstance that two or more of these actions may occur simultaneously, and also in variable proportions to each other. But it may in a great measure be resolved by attention to the principles already laid down (747.).
778. When aqueous solutions of bodies are used, secondary results are exceedingly frequent. Even when the water is not present in large quantity, but is merely that of combination, still secondary results often ensue: for instance, it is very possible that in Sir Humphry Davy's decomposition of the hydrates of potassa and soda, a part of the potassium produced was the result of a secondary action. Hence, also, a frequent cause for the disappearance of the oxygen and hydrogen which would otherwise be evolved: and when hydrogen does not appear at the cathode in an aqueous solution, it perhaps always indicates that a secondary action has taken place there. No exception to this rule has as yet occurred to my observation.
779. Secondary actions are not confined to aqueous solutions, or cases where water is present. For instance, various chlorides acted upon, when fused (402.), by platina electrodes, have the chlorine determined electrically to the anode. In many cases, as with the chlorides of lead, potassium, barium, &c., the chlorine acts on the platina and forms a compound with it, which dissolves; but when protochloride of tin is used, the chlorine at the anode does not act upon the platina, but upon the chloride already there, forming a perchloride which rises in vapour (790. 804.). These are, therefore, instances of secondary actions of both kinds, produced in bodies containing no water.
780. The production of boron from fused borax (402. 417.) is also a case of secondary action; for boracic acid is not decomposable by electricity (408.), and it was the sodium evolved at the cathode which, re-acting on the boracic acid around it, took oxygen from it and set boron free in the experiments formerly described.
781. Secondary actions have already, in the hands of M. Becquerel, produced many interesting results in the formation of compounds; some of them new, others imitations of those occurring naturally. It is probable they may prove equally interesting in an opposite direction, i.e. as affording cases of analytic decomposition. Much information regarding the composition, and perhaps even the arrangement, of the particles of such bodies as the vegetable acids and alkalies, and organic compounds generally, will probably be obtained by submitting them to the action of nascent oxygen, hydrogen, chlorine, &c. at the electrodes; and the action seems the more promising, because of the thorough command which we possess over attendant circumstances, such as the strength of the current, the size of the electrodes, the nature of the decomposing conductor, its strength, &c., all of which may be expected to have their corresponding influence upon the final result.
782. It is to me a great satisfaction that the extreme variety of secondary results has presented nothing opposed to the doctrine of a constant and definite electro-chemical action, to the particular consideration of which I shall now proceed.
¶ vii. On the definite nature and extent of Electro-chemical Decomposition.
783. In the third series of these Researches, after proving the identity of electricities derived from different sources, and showing, by actual measurement, the extraordinary quantity of electricity evolved by a very feeble voltaic arrangement (371. 376.), I announced a law, derived from experiment, which seemed to me of the utmost importance to the science of electricity in general, and that branch of it denominated electro-chemistry in particular. The law was expressed thus: The chemical power of a current of electricity is in direct proportion to the absolute quantity of electricity which passes (377.).
Annales de Chimie, tom, xxxv. p. 113.
784. In the further progress of the successive investigations, I have had frequent occasion to refer to the same law, sometimes in circumstances offering powerful corroboration of its truth (456. 504. 505.); and the present series already supplies numerous new cases in which it holds good (704. 722. 726. 732.). It is now my object to consider this great principle more closely, and to develope some of the consequences to which it leads. That the evidence for it may be the more distinct and applicable, I shall quote cases of decomposition subject to as few interferences from secondary results as possible, effected upon bodies very simple, yet very definite in their nature.
785. In the first place, I consider the law as so fully established with respect to the decomposition of water, and under so many circumstances which might be supposed, if anything could, to exert an influence over it, that I may be excused entering into further detail respecting that substance, or even summing up the results here (732.). I refer, therefore, to the whole of the subdivision of this series of Researches which contains the account of the volta-electrometer (704. &c.).
786. In the next place, I also consider the law as established with respect to muriatic acid by the experiments and reasoning already advanced, when speaking of that substance, in the subdivision respecting primary and secondary results (758. &c.).
787. I consider the law as established also with regard to hydriodic acid by the experiments and considerations already advanced in the preceding division of this series of Researches (767. 768.).
788. Without speaking with the same confidence, yet from the experiments described, and many others not described, relating to hydro-fluoric, hydro-cyanic, ferro-cyanic, and sulpho-cyanic acids (770. 771. 772.), and from the close analogy which holds between these bodies and the hydracids of chlorine, iodine, bromine, &c., I consider these also as coming under subjection to the law, and assisting to prove its truth.
789. In the preceding cases, except the first, the water is believed to be inactive; but to avoid any ambiguity arising from its presence, I sought for substances from which it should be absent altogether; and, taking advantage of the law of conduction already developed (380. &c.), I soon found abundance, amongst which protochloride of tin was first subjected to decomposition in the following manner. A piece of platina wire had one extremity coiled up into a small knob, and, having been carefully weighed, was sealed hermetically into a piece of bottle-glass tube, so that the knob should be at the bottom of the tube within (fig. 68.). The tube was suspended by a piece of platina wire, so that the heat of a spirit-lamp could be applied to it. Recently fused protochloride of tin was introduced in sufficient quantity to occupy, when melted, about one-half of the tube; the wire of the tube was connected with a volta-electrometer (711.), which was itself connected with the negative end of a voltaic battery; and a platina wire connected with the positive end of the same battery was dipped into the fused chloride in the tube; being however so bent, that it could not by any shake of the hand or apparatus touch the negative electrode at the bottom of the vessel. The whole arrangement is delineated in fig. 69.
790. Under these circumstances the chloride of tin was decomposed: the chlorine evolved at the positive electrode formed bichloride of tin (779.), which passed away in fumes, and the tin evolved at the negative electrode combined with the platina, forming an alloy, fusible at the temperature to which the tube was subjected, and therefore never occasioning metallic communication through the decomposing chloride. When the experiment had been continued so long as to yield a reasonable quantity of gas in the volta-electrometer, the battery connexion was broken, the positive electrode removed, and the tube and remaining chloride allowed to cool. When cold, the tube was broken open, the rest of the chloride and the glass being easily separable from the platina wire and its button of alloy. The latter when washed was then reweighed, and the increase gave the weight of the tin reduced.
791. I will give the particular results of one experiment, in illustration of the mode adopted in this and others, the results of which I shall have occasion to quote. The negative electrode weighed at first 20 grains; after the experiment, it, with its button of alloy, weighed 23.2 grains. The tin evolved by the electric current at the cathode: weighed therefore 3.2 grains. The quantity of oxygen and hydrogen collected in the volta-electrometer = 3.85 cubic inches. As 100 cubic inches of oxygen and hydrogen, in the proportions to form water, may be considered as weighing 12.92 grains, the 3.85 cubic inches would weigh 0.49742 of a grain; that being, therefore, the weight of water decomposed by the same electric current as was able to decompose such weight of protochloride of tin as could yield 3.2 grains of metal. Now 0.49742 : 3.2 :: 9 the equivalent of water is to 57.9, which should therefore be the equivalent of tin, if the experiment had been made without error, and if the electro-chemical decomposition is in this case also definite. In some chemical works 58 is given as the chemical equivalent of tin, in others 57.9. Both are so near to the result of the experiment, and the experiment itself is so subject to slight causes of variation (as from the absorption of gas in the volta-electrometer (716.), &c.), that the numbers leave little doubt of the applicability of the law of definite action in this and all similar cases of electro-decomposition.
792. It is not often I have obtained an accordance in numbers so near as that I have just quoted. Four experiments were made on the protochloride of tin, the quantities of gas evolved in the volta-electrometer being from 2.05 to 10.29 cubic inches. The average of the four experiments gave 58.53 as the electro-chemical equivalent for tin.
793. The chloride remaining after the experiment was pure protochloride of tin; and no one can doubt for a moment that the equivalent of chlorine had been evolved at the anode, and, having formed bichloride of tin as a secondary result, had passed away.
794. Chloride of lead was experimented upon in a manner exactly similar, except that a change was made in the nature of the positive electrode; for as the chlorine evolved at the anode forms no perchloride of lead, but acts directly upon the platina, it produces, if that metal be used, a solution of chloride of platina in the chloride of lead; in consequence of which a portion of platina can pass to the cathode, and would then produce a vitiated result. I therefore sought for, and found in plumbago, another substance, which could be used safely as the positive electrode in such bodies as chlorides, iodides, &c.
The chlorine or iodine does not act upon it, but is evolved in the free state; and the plumbago has no re-action, under the circumstances, upon the fused chloride or iodide in which it is plunged. Even if a few particles of plumbago should separate by the heat or the mechanical action of the evolved gas, they can do no harm in the chloride.
795. The mean of three experiments gave the number of 100.85 as the equivalent for lead. The chemical equivalent is 103.5. The deficiency in my experiments I attribute to the solution of part of the gas (716.) in the volta-electrometer; but the results leave no doubt on my mind that both the lead and the chlorine are, in this case, evolved in definite quantities by the action of a given quantity of electricity (814. &c.).
796. Chloride of antimony.--It was in endeavouring to obtain the electro-chemical equivalent of antimony from the chloride, that I found reasons for the statement I have made respecting the presence of water in it in an earlier part of these Researches (690. 693. &c.).
797. I endeavoured to experiment upon the oxide of lead obtained by fusion and ignition of the nitrate in a platina crucible, but found great difficulty, from the high temperature required for perfect fusion, and the powerful fluxing qualities of the substance. Green-glass tubes repeatedly failed. I at last fused the oxide in a small porcelain crucible, heated fully in a charcoal fire; and, as it is was essential that the evolution of the lead at the cathode should take place beneath the surface, the negative electrode was guarded by a green-glass tube, fused around it in such a manner as to expose only the knob of platina at the lower end (fig. 70.), so that it could be plunged beneath the surface, and thus exclude contact of air or oxygen with the lead reduced there. A platina wire was employed for the positive electrode, that metal not being subject to any action from the oxygen evolved against it. The arrangement is given in fig. 71.
798. In an experiment of this kind the equivalent for the lead came out 93.17, which is very much too small. This, I believe, was because of the small interval between the positive and negative electrodes in the oxide of lead; so that it was not unlikely that some of the froth and bubbles formed by the oxygen at the anode should occasionally even touch the lead reduced at the cathode, and re-oxidize it. When I endeavoured to correct this by having more litharge, the greater heat required to keep it all fluid caused a quicker action on the crucible, which was soon eaten through, and the experiment stopped.
799. In one experiment of this kind I used borate of lead (408. 673.). It evolves lead, under the influence of the electric current, at the anode, and oxygen at the cathode; and as the boracic acid is not either directly (408.) or incidentally decomposed during the operation, I expected a result dependent on the oxide of lead. The borate is not so violent a flux as the oxide, but it requires a higher temperature to make it quite liquid; and if not very hot, the bubbles of oxygen cling to the positive electrode, and retard the transfer of electricity. The number for lead came out 101.29, which is so near to 103.5 as to show that the action of the current had been definite.
800. Oxide of bismuth.--I found this substance required too high a temperature, and acted too powerfully as a flux, to allow of any experiment being made on it, without the application of more time and care than I could give at present.
801. The ordinary protoxide of antimony, which consists of one proportional of metal and one and a half of oxygen, was subjected to the action of the electric current in a green-glass tube (789.), surrounded by a jacket of platina foil, and heated in a charcoal fire. The decomposition began and proceeded very well at first, apparently indicating, according to the general law (679. 697.), that this substance was one containing such elements and in such proportions as made it amenable to the power of the electric current. This effect I have already given reasons for supposing may be due to the presence of a true protoxide, consisting of single proportionals (696. 693.). The action soon diminished, and finally ceased, because of the formation of a higher oxide of the metal at the positive electrode. This compound, which was probably the peroxide, being infusible and insoluble in the protoxide, formed a crystalline crust around the positive electrode; and thus insulating it, prevented the transmission of the electricity. Whether, if it had been fusible and still immiscible, it would have decomposed, is doubtful, because of its departure from the required composition (697.). It was a very natural secondary product at the positive electrode (779.). On opening the tube it was found that a little antimony had been separated at the negative electrode; but the quantity was too small to allow of any quantitative result being obtained.
This paragraph is subject to the corrective note now appended to paragraph 696.--Dec. 1838.
802. Iodide of lead.--This substance can be experimented with in tubes heated by a spirit-lamp (789.); but I obtained no good results from it, whether I used positive electrodes of platina or plumbago. In two experiments the numbers for the lead came out only 75.46 and 73.45, instead of 103.5. This I attribute to the formation of a periodide at the positive electrode, which, dissolving in the mass of liquid iodide, came in contact with the lead evolved at the negative electrode, and dissolved part of it, becoming itself again protiodide. Such a periodide does exist; and it is very rarely that the iodide of lead formed by precipitation, and well-washed, can be fused without evolving much iodine, from the presence of this percompound; nor does crystallization from its hot aqueous solution free it from this substance. Even when a little of the protiodide and iodine are merely rubbed together in a mortar, a portion of the periodide is formed. And though it is decomposed by being fused and heated to dull redness for a few minutes, and the whole reduced to protiodide, yet that is not at all opposed to the possibility, that a little of that which is formed in great excess of iodine at the anode, should be carried by the rapid currents in the liquid into contact with the cathode.
803. This view of the result was strengthened by a third experiment, where the space between the electrodes was increased to one third of an inch; for now the interfering effects were much diminished, and the number of the lead came out 89.04; and it was fully confirmed by the results obtained in the cases of transfer to be immediately described (818.).
The experiments on iodide of lead therefore offer no exception to the general law under consideration, but on the contrary may, from general considerations, be admitted as included in it.
804. Protiodide of tin.--This substance, when fused (402.), conducts and is decomposed by the electric current, tin is evolved at the anode, and periodide of tin as a secondary result (779. 790.) at the cathode. The temperature required for its fusion is too high to allow of the production of any results fit for weighing.
805. Iodide of potassium was subjected to electrolytic action in a tube, like that in fig. 68. (789.). The negative electrode was a globule of lead, and I hoped in this way to retain the potassium, and obtain results that could be weighed and compared with the volta-electrometer indication; but the difficulties dependent upon the high temperature required, the action upon the glass, the fusibility of the platina induced by the presence of the lead, and other circumstances, prevented me from procuring such results. The iodide was decomposed with the evolution of iodine at the anode, and of potassium at the cathode, as in former cases.
806. In some of these experiments several substances were placed in succession, and decomposed simultaneously by the same electric current: thus, protochloride of tin, chloride of lead, and water, were thus acted on at once. It is needless to say that the results were comparable, the tin, lead, chlorine, oxygen, and hydrogen evolved being definite in quantity and electro-chemical equivalents to each other.
807. Let us turn to another kind of proof of the definite chemical action of electricity. If any circumstances could be supposed to exert an influence over the quantity of the matters evolved during electrolytic action, one would expect them to be present when electrodes of different substances, and possessing very different chemical affinities for such matters, were used. Platina has no power in dilute sulphuric acid of combining with the oxygen at the anode, though the latter be evolved in the nascent state against it. Copper, on the other hand, immediately unites with the oxygen, as the electric current sets it free from the hydrogen; and zinc is not only able to combine with it, but can, without any help from the electricity, abstract it directly from the water, at the same time setting torrents of hydrogen free. Yet in cases where these three substances were used as the positive electrodes in three similar portions of the same dilute sulphuric acid, specific gravity 1.336, precisely the same quantity of water was decomposed by the electric current, and precisely the same quantity of hydrogen set free at the cathodes of the three solutions.
808. The experiment was made thus. Portions of the dilute sulphuric acid were put into three basins. Three volta-electrometer tubes, of the form figg. 60. 62. were filled with the same acid, and one inverted in each basin (707.). A zinc plate, connected with the positive end of a voltaic battery, was dipped into the first basin, forming the positive electrode there, the hydrogen, which was abundantly evolved from it by the direct action of the acid, being allowed to escape. A copper plate, which dipped into the acid of the second basin, was connected with the negative electrode of the first basin; and a platina plate, which dipped into the acid of the third basin, was connected with the negative electrode of the second basin. The negative electrode of the third basin was connected with a volta-electrometer (711.), and that with the negative end of the voltaic battery.
809. Immediately that the circuit was complete, the electro-chemical action commenced in all the vessels. The hydrogen still rose in, apparently, undiminished quantities from the positive zinc electrode in the first basin. No oxygen was evolved at the positive copper electrode in the second basin, but a sulphate of copper was formed there; whilst in the third basin the positive platina electrode evolved pure oxygen gas, and was itself unaffected. But in all the basins the hydrogen liberated at the negative platina electrodes was the same in quantity, and the same with the volume of hydrogen evolved in the volta-electrometer, showing that in all the vessels the current had decomposed an equal quantity of water. In this trying case, therefore, the chemical action of electricity proved to be perfectly definite.
810. A similar experiment was made with muriatic acid diluted with its bulk of water. The three positive electrodes were zinc, silver, and platina; the first being able to separate and combine with the chlorine without the aid of the current; the second combining with the chlorine only after the current had set it free; and the third rejecting almost the whole of it. The three negative electrodes were, as before, platina plates fixed within glass tubes. In this experiment, as in the former, the quantity of hydrogen evolved at the cathodes was the same for all, and the same as the hydrogen evolved in the volta-electrometer. I have already given my reasons for believing that in these experiments it is the muriatic acid which is directly decomposed by the electricity (764.); and the results prove that the quantities so decomposed are perfectly definite and proportionate to the quantity of electricity which has passed.
811. In this experiment the chloride of silver formed in the second basin retarded the passage of the current of electricity, by virtue of the law of conduction before described (394.), so that it had to be cleaned off four or five times during the course of the experiment; but this caused no difference between the results of that vessel and the others.
812. Charcoal was used as the positive electrode in both sulphuric and muriatic acids (808. 810.); but this change produced no variation of the results. A zinc positive electrode, in sulphate of soda or solution of common salt, gave the same constancy of operation.
813. Experiments of a similar kind were then made with bodies altogether in a different state, i.e. with fused chlorides, iodides, &c. I have already described an experiment with fused chloride of silver, in which the electrodes were of metallic silver, the one rendered negative becoming increased and lengthened by the addition of metal, whilst the other was dissolved and eaten away by its abstraction. This experiment was repeated, two weighed pieces of silver wire being used as the electrodes, and a volta-electrometer included in the circuit. Great care was taken to withdraw the negative electrodes so regularly and steadily that the crystals of reduced silver should not form a metallic communication beneath the surface of the fused chloride. On concluding the experiment the positive electrode was re-weighed, and its loss ascertained. The mixture of chloride of silver, and metal, withdrawn in successive portions at the negative electrode, was digested in solution of ammonia, to remove the chloride, and the metallic silver remaining also weighed: it was the reduction at the cathode, and exactly equalled the solution at the anode; and each portion was as nearly as possible the equivalent to the water decomposed in the volta-electrometer.
814. The infusible condition of the silver at the temperature used, and the length and ramifying character of its crystals, render the above experiment difficult to perform, and uncertain in its results. I therefore wrought with chloride of lead, using a green-glass tube, formed as in fig. 72. A weighed platina wire was fused into the bottom of a small tube, as before described (789.). The tube was then bent to an angle, at about half an inch distance from the closed end; and the part between the angle and the extremity being softened, was forced upward, as in the figure, so as to form a bridge, or rather separation, producing two little depressions or basins a, b, within the tube. This arrangement was suspended by a platina wire, as before, so that the heat of a spirit-lamp could be applied to it, such inclination being given to it as would allow all air to escape during the fusion of the chloride of lead. A positive electrode was then provided, by bending up the end of a platina wire into a knot, and fusing about twenty grains of metallic lead on to it, in a small closed tube of glass, which was afterwards broken away. Being so furnished, the wire with its lead was weighed, and the weight recorded.
815. Chloride of lead was now introduced into the tube, and carefully fused. The leaded electrode was also introduced; after which the metal, at its extremity, soon melted. In this state of things the tube was filled up to c with melted chloride of lead; the end of the electrode to be rendered negative was in the basin b, and the electrode of melted lead was retained in the basin a, and, by connexion with the proper conducting wire of a voltaic battery, was rendered positive. A volta-electrometer was included in the circuit.
816. Immediately upon the completion of the communication with the voltaic battery, the current passed, and decomposition proceeded. No chlorine was evolved at the positive electrode; but as the fused chloride was transparent, a button of alloy could be observed gradually forming and increasing in size at b, whilst the lead at a could also be seen gradually to diminish. After a time, the experiment was stopped; the tube allowed to cool, and broken open; the wires, with their buttons, cleaned and weighed; and their change in weight compared with the indication of the volta-electrometer.
817. In this experiment the positive electrode had lost just as much lead as the negative one had gained (795.), and the loss and gain were very nearly the equivalents of the water decomposed in the volta-electrometer, giving for lead the number 101.5. It is therefore evident, in this instance, that causing a strong affinity, or no affinity, for the substance evolved at the anode, to be active during the experiment (807.), produces no variation in the definite action of the electric current.
818. A similar experiment was then made with iodide of lead, and in this manner all confusion from the formation of a periodide avoided (803.). No iodine was evolved during the whole action, and finally the loss of lead at the anode was the same as the gain at the cathode, the equivalent number, by comparison with the result in the volta-electrometer, being 103.5.
819. Then protochloride of tin was subjected to the electric current in the same manner, using of course, a tin positive electrode. No bichloride of tin was now formed (779. 790.). On examining the two electrodes, the positive had lost precisely as much as the negative had gained; and by comparison with the volta-electrometer, the number for tin came out 59.
820. It is quite necessary in these and similar experiments to examine the interior of the bulbs of alloy at the ends of the conducting wires; for occasionally, and especially with those which have been positive, they are cavernous, and contain portions of the chloride or iodide used, which must be removed before the final weight is ascertained. This is more usually the case with lead than tin.
821. All these facts combine into, I think, an irresistible mass of evidence, proving the truth of the important proposition which I at first laid down, namely, that the chemical power of a current of electricity is in direct proportion to the absolute quantity of electricity which passes (377. 783.). They prove, too, that this is not merely true with one substance, as water, but generally with all electrolytic bodies; and, further, that the results obtained with any one substance do not merely agree amongst themselves, but also with those obtained from other substances, the whole combining together into one series of definite electro-chemical actions (505.). I do not mean to say that no exceptions will appear: perhaps some may arise, especially amongst substances existing only by weak affinity; but I do not expect that any will seriously disturb the result announced. If, in the well-considered, well-examined, and, I may surely say, well-ascertained doctrines of the definite nature of ordinary chemical affinity, such exceptions occur, as they do in abundance, yet, without being allowed to disturb our minds as to the general conclusion, they ought also to be allowed if they should present themselves at this, the opening of a new view of electro-chemical action; not being held up as obstructions to those who may be engaged in rendering that view more and more perfect, but laid aside for a while, in hopes that their perfect and consistent explanation will ultimately appear.
822. The doctrine of definite electro-chemical action just laid down, and, I believe, established, leads to some new views of the relations and classifications of bodies associated with or subject to this action. Some of these I shall proceed to consider.
823. In the first place, compound bodies may be separated into two great classes, namely, those which are decomposable by the electric current, and those which are not: of the latter, some are conductors, others non-conductors, of voltaic electricity. The former do not depend for their decomposability upon the nature of their elements only; for, of the same two elements, bodies may be formed, of which one shall belong to one class and another to the other class; but probably on the proportions also (697.). It is further remarkable, that with very few, if any, exceptions (414. 691.), these decomposable bodies are exactly those governed by the remarkable law of conduction I have before described (694.); for that law does not extend to the many compound fusible substances that are excluded from this class. I propose to call bodies of this, the decomposable class, Electrolytes (664.).
I mean here by voltaic electricity, merely electricity from a most abundant source, but having very small intensity.
824. Then, again, the substances into which these divide, under the influence of the electric current, form an exceedingly important general class. They are combining bodies; are directly associated with the fundamental parts of the doctrine of chemical affinity; and have each a definite proportion, in which they are always evolved during electrolytic action. I have proposed to call these bodies generally ions, or particularly anions and cations, according as they appear at the anode or cathode (665.); and the numbers representing the proportions in which they are evolved electro-chemical equivalents. Thus hydrogen, oxygen, chlorine, iodine, lead, tin are ions; the three former are anions, the two metals are cations, and 1, 8, 3, 125, 104, 58, are their electro-chemical equivalents nearly.
825. A summary of certain points already ascertained respecting electrolytes, ions, and electro-chemical equivalents, may be given in the following general form of propositions, without, I hope, including any serious error.
826. i. A single ion, i.e. one not in combination with another, will have no tendency to pass to either of the electrodes, and will be perfectly indifferent to the passing current, unless it be itself a compound of more elementary ions, and so subject to actual decomposition. Upon this fact is founded much of the proof adduced in favour of the new theory of electro-chemical decomposition, which I put forth in a former series of these Researches (518. &c.).
827. ii. If one ion be combined in right proportions (697.) with another strongly opposed to it in its ordinary chemical relations, i.e. if an anion be combined with a cation, then both will travel, the one to the anode, the other to the cathode, of the decomposing body (530, 542. 547.).
828. iii. If, therefore, an ion pass towards one of the electrodes, another ion must also be passing simultaneously to the other electrode, although, from secondary action, it may not make its appearance (743.).
829. iv. A body decomposable directly by the electric current, i.e. an electrolyte, must consist of two ions, and must also render them up during the act of decomposition.
830. v. There is but one electrolyte composed of the same two elementary ions; at least such appears to be the fact (697.), dependent upon a law, that only single electro-chemical equivalents of elementary ions can go to the electrodes, and not multiples.
831. vi. A body not decomposable when alone, as boracic acid, is not directly decomposable by the electric current when in combination (780.). It may act as an ion going wholly to the anode or cathode, but does not yield up its elements, except occasionally by a secondary action. Perhaps it is superfluous for me to point out that this proposition has no relation to such cases as that of water, which, by the presence of other bodies, is rendered a better conductor of electricity, and therefore is more freely decomposed.
832. vii. The nature of the substance of which the electrode is formed, provided it be a conductor, causes no difference in the electro-decomposition, either in kind or degree (807. 813.): but it seriously influences, by secondary action (714.), the state in which the finally appear. Advantage may be taken of this principle in combining and ions collecting such ions as, if evolved in their free state, would be unmanageable.
It will often happen that the electrodes used may be of such a nature as, with the fluid in which they are immersed, to produce an electric current, either according with or opposing that of the voltaic arrangement used, and in this way, or by direct chemical action, may sadly disturb the results. Still, in the midst of all these confusing effects, the electric current, which actually passes in any direction through the body suffering decomposition, will produce its own definite electrolytic action.
833. viii. A substance which, being used as the electrode, can combine with the ion evolved against it, is also, I believe, an ion, and combines, in such cases, in the quantity represented by its electro-chemical equivalent. All the experiments I have made agree with this view; and it seems to me, at present, to result as a necessary consequence. Whether, in the secondary actions that take place, where the ion acts, not upon the matter of the electrode, but on that which is around it in the liquid (744.), the same consequence follows, will require more extended investigation to determine.
834. ix. Compound ions are not necessarily composed of electro-chemical equivalents of simple ions. For instance, sulphuric acid, boracic acid, phosphoric acid, are ions, but not electrolytes, i.e. not composed of electro-chemical equivalents of simple ions.
835. x. Electro-chemical equivalents are always consistent; i.e. the same number which represents the equivalent of a substance A when it is separating from a substance B, will also represent A when separating from a third substance C. Thus, 8 is the electro-chemical equivalent of oxygen, whether separating from hydrogen, or tin, or lead; and 103.5 is the electrochemical equivalent of lead, whether separating from oxygen, or chlorine, or iodine.
836. xi. Electro-chemical equivalents coincide, and are the same, with ordinary chemical equivalents.
837. By means of experiment and the preceding propositions, a knowledge of ions and their electro-chemical equivalents may be obtained in various ways.
838. In the first place, they may be determined directly, as has been done with hydrogen, oxygen, lead, and tin, in the numerous experiments already quoted.
839. In the next place, from propositions ii. and iii., may be deduced the knowledge of many other ions, and also their equivalents. When chloride of lead was decomposed, platina being used for both electrodes (395.), there could remain no more doubt that chlorine was passing to the anode, although it combined with the platina there, than when the positive electrode, being of plumbago (794.), allowed its evolution in the free state; neither could there, in either case, remain any doubt that for every 103.5 parts of lead evolved at the cathode, 36 parts of chlorine were evolved at the anode, for the remaining chloride of lead was unchanged. So also, when in a metallic solution one volume of oxygen, or a secondary compound containing that proportion, appeared at the anode, no doubt could arise that hydrogen, equivalent to two volumes, had been determined to the cathode, although, by a secondary action, it had been employed in reducing oxides of lead, copper, or other metals, to the metallic state. In this manner, then, we learn from the experiments already described in these Researches, that chlorine, iodine, bromine, fluorine, calcium, potassium, strontium, magnesium, manganese, &c., are ions and that their electro-chemical equivalents are the same as their ordinary chemical equivalents.
840. Propositions iv. and v. extend our means of gaining information. For if a body of known chemical composition is found to be decomposable, and the nature of the substance evolved as a primary or even a secondary result (743. 777.) at one of the electrodes, be ascertained, the electro-chemical equivalent of that body may be deduced from the known constant composition of the substance evolved. Thus, when fused protiodide of tin is decomposed by the voltaic current (804.), the conclusion may be drawn, that both the iodine and tin are ions, and that the proportions in which they combine in the fused compound express their electro-chemical equivalents. Again, with respect to the fused iodide of potassium (805.), it is an electrolyte; and the chemical equivalents will also be the electro-chemical equivalents.
841. If proposition viii. sustain extensive experimental investigation, then it will not only help to confirm the results obtained by the use of the other propositions, but will give abundant original information of its own.
842. In many instances, the secondary results obtained by the action of the evolved ion on the substances present in the surrounding liquid or solution, will give the electro-chemical equivalent. Thus, in the solution of acetate of lead, and, as far as I have gone, in other proto-salts subjected to the reducing action of the nascent hydrogen at the cathode, the metal precipitated has been in the same quantity as if it had been a primary product, (provided no free hydrogen escaped there,) and therefore gave accurately the number representing its electro-chemical equivalent.
843. Upon this principle it is that secondary results may occasionally be used as measurers of the volta-electric current (706. 740.); but there are not many metallic solutions that answer this purpose well: for unless the metal is easily precipitated, hydrogen will be evolved at the cathode and vitiate the result. If a soluble peroxide is formed at the anode, or if the precipitated metal crystallize across the solution and touch the positive electrode, similar vitiated results are obtained. I expect to find in some salts, as the acetates of mercury and zinc, solutions favourable for this use.
844. After the first experimental investigations to establish the definite chemical action of electricity, I have not hesitated to apply the more strict results of chemical analysis to correct the numbers obtained as electrolytic results. This, it is evident, may be done in a great number of cases, without using too much liberty towards the due severity of scientific research. The series of numbers representing electro-chemical equivalents must, like those expressing the ordinary equivalents of chemically acting bodies, remain subject to the continual correction of experiment and sound reasoning.
845. I give the following brief Table of ions and their electro-chemical equivalents, rather as a specimen of a first attempt than as anything that can supply the want which must very quickly be felt, of a full and complete tabular account of this class of bodies. Looking forward to such a table as of extreme utility (if well-constructed) in developing the intimate relation of ordinary chemical affinity to electrical actions, and identifying the two, not to the imagination merely, but to the conviction of the senses and a sound judgement, I may be allowed to express a hope, that the endeavour will always be to make it a table of real, and not hypothetical, electro-chemical equivalents; for we shall else overrun the facts, and lose all sight and consciousness of the knowledge lying directly in our path.
846. The equivalent numbers do not profess to be exact, and are taken almost entirely from the chemical results of other philosophers in whom I could repose more confidence, as to these points, than in myself.
848. This Table might be further arrange into groups of such substances as either act with, or replace, each other. Thus, for instance, acids and bases act in relation to each other; but they do not act in association with oxygen, hydrogen, or elementary substances. There is indeed little or no doubt that, when the electrical relations of the particles of matter come to be closely examined, this division must be made. The simple substances, with cyanogen, sulpho-cyanogen, and one or two other compound bodies, will probably form the first group; and the acids and bases, with such analogous compounds as may prove to be ions, the second group. Whether these will include all ions, or whether a third class of more complicated results will be required, must be decided by future experiments.
849. It is probable that all our present elementary bodies are ions, but that is not as yet certain. There are some, such as carbon, phosphorus, nitrogen, silicon, boron, alumium, the right of which to the title of ion it is desirable to decide as soon as possible. There are also many compound bodies, and amongst them alumina and silica, which it is desirable to class immediately by unexceptionable experiments. It is also possible, that all combinable bodies, compound as well as simple, may enter into the class of ions; but at present it does not seem to me probable. Still the experimental evidence I have is so small in proportion to what must gradually accumulate around, and bear upon, this point, that I am afraid to give a strong opinion upon it.
850. I think I cannot deceive myself in considering the doctrine of definite electro-chemical action as of the utmost importance. It touches by its facts more directly and closely than any former fact, or set of facts, have done, upon the beautiful idea, that ordinary chemical affinity is a mere consequence of the electrical attractions of the particles of different kinds of matter; and it will probably lead us to the means by which we may enlighten that which is at present so obscure, and either fully demonstrate the truth of the idea, or develope that which ought to replace it.
851. A very valuable use of electro-chemical equivalents will be to decide, in cases of doubt, what is the true chemical equivalent, or definite proportional, or atomic number of a body; for I have such conviction that the power which governs electro-decomposition and ordinary chemical attractions is the same; and such confidence in the overruling influence of those natural laws which render the former definite, as to feel no hesitation in believing that the latter must submit to them also. Such being the case, I can have, no doubt that, assuming hydrogen as 1, and dismissing small fractions for the simplicity of expression, the equivalent number or atomic weight of oxygen is 8, of chlorine 36, of bromine 78.4, of lead 103.5, of tin 59, &c., notwithstanding that a very high authority doubles several of these numbers.
§ 13. On the absolute quantity of Electricity associated with the particles or atoms of Matter.
852. The theory of definite electrolytical or electro-chemical action appears to me to touch immediately upon the absolute quantity of electricity or electric power belonging to different bodies. It is impossible, perhaps, to speak on this point without committing oneself beyond what present facts will sustain; and yet it is equally impossible, and perhaps would be impolitic, not to reason upon the subject. Although we know nothing of what an atom is, yet we cannot resist forming some idea of a small particle, which represents it to the mind; and though we are in equal, if not greater, ignorance of electricity, so as to be unable to say whether it is a particular matter or matters, or mere motion of ordinary matter, or some third kind of power or agent, yet there is an immensity of facts which justify us in believing that the atoms of matter are in some way endowed or associated with electrical powers, to which they owe their most striking qualities, and amongst them their mutual chemical affinity. As soon as we perceive, through the teaching of Dalton, that chemical powers are, however varied the circumstances in which they are exerted, definite for each body, we learn to estimate the relative degree of force which resides in such bodies: and when upon that knowledge comes the fact, that the electricity, which we appear to be capable of loosening from its habitation for a while, and conveying from place to place, whilst it retains its chemical force, can be measured out, and being so measured is found to be as definite in its action as any of those portions which, remaining associated with the particles of matter, give them their chemical relation; we seem to have found the link which connects the proportion of that we have evolved to the proportion of that belonging to the particles in their natural state.
853. Now it is wonderful to observe how small a quantity of a compound body is decomposed by a certain portion of electricity. Let us, for instance, consider this and a few other points in relation to water. One grain of water, acidulated to facilitate conduction, will require an electric current to be continued for three minutes and three quarters of time to effect its decomposition, which current must be powerful enough to retain a platina wire 1/104 of an inch in thickness, red-hot, in the air during the whole time; and if interrupted anywhere by charcoal points, will produce a very brilliant and constant star of light. If attention be paid to the instantaneous discharge of electricity of tension, as illustrated in the beautiful experiments of Mr. Wheatstone, and to what I have said elsewhere on the relation of common and voltaic electricity (371. 375.), it will not be too much to say that this necessary quantity of electricity is equal to a very powerful flash of lightning. Yet we have it under perfect command; can evolve, direct, and employ it at pleasure; and when it has performed its full work of electrolyzation, it has only separated the elements of a single grain of water.
I have not stated the length of wire used, because I find by experiment, as would be expected in theory, that it is indifferent. The same quantity of electricity which, passed in a given time, can heat an inch of platina wire of a certain diameter red-hot, can also heat a hundred, a thousand, or any length of the same wire to the same degree, provided the cooling circumstances are the same for every part in all cases. This I have proved by the volta-electrometer. I found that whether half an inch or eight inches were retained at one constant temperature of dull redness, equal quantities of water were decomposed in equal times. When the half-inch was used, only the centre portion of wire was ignited. A fine wire may even be used as a rough but ready regulator of a voltaic current; for if it be made part of the circuit, and the larger wires communicating with it be shifted nearer to or further apart, so as to keep the portion of wire in the circuit sensibly at the same temperature, the current passing through it will be nearly uniform.
Literary Gazette, 1833, March 1 and 8. Philosophical Magazine, 1833, p. 201. L'Institut, 1833, p.261.
854. On the other hand, the relation between the conduction of the electricity and the decomposition of the water is so close, that one cannot take place without the other. If the water is altered only in that small degree which consists in its having the solid instead of the fluid state, the conduction is stopped, and the decomposition is stopped with it. Whether the conduction be considered as depending upon the decomposition, or not (443. 703.), still the relation of the two functions is equally intimate and inseparable.
855. Considering this close and twofold relation, namely, that without decomposition transmission of electricity does not occur; and, that for a given definite quantity of electricity passed, an equally definite and constant quantity of water or other matter is decomposed; considering also that the agent, which is electricity, is simply employed in overcoming electrical powers in the body subjected to its action; it seems a probable, and almost a natural consequence, that the quantity which passes is the equivalent of, and therefore equal to, that of the particles separated; i.e. that if the electrical power which holds the elements of a grain of water in combination, or which makes a grain of oxygen and hydrogen in the right proportions unite into water when they are made to combine, could be thrown into the condition of a current, it would exactly equal the current required for the separation of that grain of water into its elements again.
856. This view of the subject gives an almost overwhelming idea of the extraordinary quantity or degree of electric power which naturally belongs to the particles of matter; but it is not inconsistent in the slightest degree with the facts which can be brought to bear on this point. To illustrate this I must say a few words on the voltaic pile.
By the term voltaic pile, I mean such apparatus or arrangement of metals as up to this time have been called so, and which contain water, brine, acids, or other aqueous solutions or decomposable substances (476.), between their plates. Other kinds of electric apparatus may be hereafter invented, and I hope to construct some not belonging to the class of instruments discovered by Volta.
857. Intending hereafter to apply the results given in this and the preceding series of Researches to a close investigation of the source of electricity in the voltaic instrument, I have refrained from forming any decided opinion on the subject; and without at all meaning to dismiss metallic contact, or the contact of dissimilar substances, being conductors, but not metallic, as if they had nothing to do with the origin of the current,
I still am fully of opinion with Davy, that it is at least continued by chemical action, and that the supply constituting the current is almost entirely from that source.
858. Those bodies which, being interposed between the metals of the voltaic pile, render it active, are all of them electrolytes (476.); and it cannot but press upon the attention of every one engaged in considering this subject, that in those bodies (so essential to the pile) decomposition and the transmission of a current are so intimately connected, that one cannot happen without the other. This I have shown abundantly in water, and numerous other cases (402. 476.). If, then, a voltaic trough have its extremities connected by a body capable of being decomposed, as water, we shall have a continuous current through the apparatus; and whilst it remains in this state we may look at the part where the acid is acting upon the plates, and that where the current is acting upon the water, as the reciprocals of each other. In both parts we have the two conditions inseparable in such bodies as these, namely, the passing of a current, and decomposition; and this is as true of the cells in the battery as of the water cell; for no voltaic battery has as yet been constructed in which the chemical action is only that of combination: decomposition is always included, and is, I believe, an essential chemical part.
859. But the difference in the two parts of the connected battery, that is, the decomposition or experimental cell, and the acting cells, is simply this. In the former we urge the current through, but it, apparently of necessity, is accompanied by decomposition: in the latter we cause decompositions by ordinary chemical actions, (which are, however, themselves electrical,) and, as a consequence, have the electrical current; and as the decomposition dependent upon the current is definite in the former case, so is the current associated with the decomposition also definite in the latter (862. &c.).
860. Let us apply this in support of what I have surmised respecting the enormous electric power of each particle or atom of matter (856.). I showed in a former series of these Researches on the relation by measure of common and voltaic electricity, that two wires, one of platina and one of zinc, each one-eighteenth of an inch in diameter, placed five-sixteenths of an inch apart, and immersed to the depth of five-eighths of an inch in acid, consisting of one drop of oil of vitriol and four ounces of distilled water at a temperature of about 60° Fahr., and connected at the other extremities by a copper wire eighteen feet long, and one-eighteenth of an inch in thickness, yielded as much electricity in little more than three seconds of time as a Leyden battery charged by thirty turns of a very large and powerful plate electric machine in full action (371.). This quantity, though sufficient if passed at once through the head of a rat or cat to have killed it, as by a flash of lightning, was evolved by the mutual action of so small a portion of the zinc wire and water in contact with it, that the loss of weight sustained by either would be inappreciable by our most delicate instruments; and as to the water which could be decomposed by that current, it must have been insensible in quantity, for no trace of hydrogen appeared upon the surface of the platina during those three seconds.
Spotted a mistake or have an idea?
Literature · Science
Experimental Researches in Electricity, Volume 1 11
