Chapter 28

906. A little nitric acid was added to the liquid in the vessel _r_, so as to make a mixture which I shall call diluted nitro-sulphuric acid. On repeating the experiments with this mixture, all the substances before decomposed again gave way, and much more readily. But, besides that, many which before resisted electrolyzation, now yielded up their elements. Thus, solution of sulphate of soda, acted upon in the interstices of litmus and turmeric paper, yielded acid at the _anode_ and alkali at the _cathode_; solution of muriatic acid tinged by indigo yielded chlorine at the _anode_ and hydrogen at the _cathode_; solution of nitrate of silver yielded silver at the _cathode_. Again, fused nitre and the fused iodide and chloride of lead were decomposable by the current of this single pair of plates, though they were not by the former (903.).

907. A solution of acetate of lead was apparently not decomposed by this pair, nor did water acidulated by sulphuric acid seem at first to give way (973.).

908. The increase of intensity or power of the current produced by a simple voltaic circle, with the increase of the force of the chemical action at the exciting place, is here sufficiently evident. But in order to place it in a clearer point of view, and to show that the decomposing effect was not at all dependent, in the latter cases, upon the mere capability of evolving _more_ electricity, experiments were made in which the quantity evolved could be increased without variation in the intensity of the exciting cause. Thus the experiments in which dilute sulphuric acid was used (899.), were repeated, using large plates of zinc and platina in the acid; but still those bodies which resisted decomposition before, resisted it also under these new circumstances. Then again, where nitro-sulphuric acid was used (906.), mere wires of platina and zinc were immersed in the exciting acid; yet, notwithstanding this change, those bodies were now decomposed which resisted any current tending to be formed by the dilute sulphuric acid. For instance, muriatic acid could not be decomposed by a single pair of plates when immersed in dilute sulphuric acid; nor did making the solution of sulphuric acid strong, nor enlarging the size of the zinc and platina plates immersed in it, increase the power; but if to a weak sulphuric acid a very little nitric acid was added, then the electricity evolved had power to decompose the muriatic acid, evolving chlorine at the _anode_ and hydrogen at the _cathode_, even when mere wires of metals were used. This mode of increasing the intensity of the electric current, as it excludes the effect dependent upon many pairs of plates, or even the effect of making any one acid stronger or weaker, is at once referable to the condition and force of the chemical affinities which are brought into action, and may, both in principle and practice, be considered as perfectly distinct from any other mode.

909. The direct reference which is thus experimentally made in the simple voltaic circle of the _intensity_ of the electric current to the _intensity_ of the chemical action going on at the place where the existence and direction of the current is determined, leads to the conclusion that by using selected bodies, as fused chlorides, salts, solutions of acids, &c., which may act upon the metals employed with different degrees of chemical force; and using also metals in association with platina, or with each other, which shall differ in the degree of chemical action exerted between them and the exciting fluid or electrolyte, we shall be able to obtain a series of comparatively constant effects due to electric currents of different intensities, which will serve to assist in the construction of a scale competent to supply the means of determining relative degrees of intensity with accuracy in future researches[A].

[A] In relation to this difference and its probable cause, see considerations on inductive polarization, 1354, &c.--_Dec. 1838._

910. I have already expressed the view which I take of the decomposition in the experimental place, as being the direct consequence of the superior exertion at some other spot of the same kind of power as that to be overcome, and therefore as the result of an antagonism of forces of the _same_ nature (891. 904.). Those at the place of decomposition have a re-action upon, and a power over, the exerting or determining set proportionate to what is needful to overcome their own power; and hence a curious result of _resistance_ offered by decompositions to the original determining force, and consequently to the current. This is well shown in the cases where such bodies as chloride of lead, iodide of lead, and water would not decompose with the current produced by a single pair of zinc and platina plates in sulphuric acid (903.), although they would with a current of higher intensity produced by stronger chemical powers. In such cases no sensible portion of the current passes (967.); the action is stopped; and I am now of opinion that in the case of the law of conduction which I described in the Fourth Series of these Researches (413.), the bodies which are electrolytes in the fluid state cease to be such in the solid form, because the attractions of the particles by which they are retained in combination and in their relative position, are then too powerful for the electric current[A]. The particles retain their places; and as decomposition is prevented, the transmission of the electricity is prevented also; and although a battery of many plates may be used, yet if it be of that perfect kind which allows of no extraneous or indirect action (1000.), the whole of the affinities concerned in the activity of that battery are at the same time also suspended and counteracted.

[A] Refer onwards to 1705.--_Dec. 1838._

911. But referring to the _resistance_ of each single case of decomposition, it would appear that as these differ in force according to the affinities by which the elements in the substance tend to retain their places, they also would supply cases constituting a series of degrees by which to measure the initial intensities of simple voltaic or other currents of electricity, and which, combined with the scale of intensities determined by different degrees of _acting force_ (909.), would probably include a sufficient set of differences to meet almost every important case where a reference to intensity would be required.

912. According to the experiments I have already had occasion to make, I find that the following bodies are electrolytic in the order in which I have placed them, those which are first being decomposed by the current of lowest intensity. These currents were always from a single pair of plates, and may be considered as elementary _voltaic forces_.

Iodide of potassium (solution). Chloride of silver (fused). Protochloride of tin (fused). Chloride of lead (fused). Iodide of lead (fused). Muriatic acid (solution). Water, acidulated with sulphuric acid.

913. It is essential that, in all endeavours to obtain the relative electrolytic intensity necessary for the decomposition of different bodies, attention should be paid to the nature of the electrodes and the other bodies present which may favour secondary actions (986.). If in electro-decomposition one of the elements separated has an affinity for the electrode, or for bodies present in the surrounding fluid, then the affinity resisting decomposition is in part balanced by such power, and the true place of the electrolyte in a table of the above kind is not obtained: thus, chlorine combines with a positive platina electrode freely, but iodine scarcely at all, and therefore I believe it is that the fused chlorides stand first in the preceding Table. Again, if in the decomposition of water not merely sulphuric but also a little nitric acid be present, then the water is more freely decomposed, for the hydrogen at the _cathode_ is not ultimately expelled, but finds oxygen in the nitric acid, with which it can combine to produce a secondary result; the affinities opposing decomposition are in this way diminished, and the elements of the water can then be separated by a current of lower intensity.

914. Advantage may be taken of this principle to interpolate more minute degrees into the scale of initial intensities already referred to (909. 911.) than is there spoken of; for by combining the force of a current _constant_ in its intensity, with the use of electrodes consisting of matter, having more or less affinity for the elements evolved from the decomposing electrolyte, various intermediate degrees may be obtained.

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915. Returning to the consideration of the source of electricity (878. &c.), there is another proof of the most perfect kind that metallic contact has nothing to do with the _production_ of electricity in the voltaic circuit, and further, that electricity is only another mode of the exertion of chemical forces. It is, the production of the _electric spark_ before any contact of metals is made, and by the exertion of _pure and unmixed chemical forces_. The experiment, which will be described further on (956.), consists in obtaining the spark upon making contact between a plate of zinc and a plate of copper plunged into dilute sulphuric acid. In order to make the arrangement as elementary as possible, mercurial surfaces were dismissed, and the contact made by a copper wire connected with the copper plate, and then brought to touch a clean part of the zinc plate. The electric spark appeared, and it must of necessity have existed and passed _before the zinc and the copper were in contact_.

916. In order to render more distinct the principles which I have been endeavouring to establish, I will restate them in their simplest form, according to my present belief. The electricity of the voltaic pile (856. note) is not dependent either in its origin or its continuance upon the contact of the metals with each other (880. 915.). It is entirely due to chemical action (882.), and is proportionate in its intensity to the intensity of the affinities concerned in its production (908.); and in its quantity to the quantity of matter which has been chemically active during its evolution (869.). This definite production is again one of the strongest proofs that the electricity is of chemical origin.

917. As _volta-electro-generation_ is a case of mere chemical action, so _volta-electro-decomposition_ is simply a case of the preponderance of one set of chemical affinities more powerful in their nature, over another set which are less powerful: and if the instance of two opposing sets of such forces (891.) be considered, and their mutual relation and dependence borne in mind, there appears no necessity for using, in respect to such cases, any other term than chemical affinity, (though that of electricity may be very convenient,) or supposing any new agent to be concerned in producing the results; for we may consider that the powers at the two places of action are in direct communion and balanced against each other through the medium of the metals (891.), fig. 76, in a manner analogous to that in which mechanical forces are balanced against each other by the intervention of the lever (1031.).

918. All the facts show us that that power commonly called chemical affinity, can be communicated to a distance through the metals and certain forms of carbon; that the electric current is only another form of the forces of chemical affinity; that its power is in proportion to the chemical affinities producing it; that when it is deficient in force it may be helped by calling in chemical aid, the want in the former being made up by an equivalent of the latter; that, in other words, _the forces termed chemical affinity and electricity are one and the same._

919. When the circumstances connected with the production of electricity in the ordinary voltaic circuit are examined and compared, it appears that the source of that agent, always meaning the electricity which circulates and completes the current in the voltaic apparatus, and gives that apparatus power and character (947. 996.), exists in the chemical action which takes place directly between the metal and the body with which it combines, and not at all in the subsequent action of the substance so produced with the acid present[A]. Thus, when zinc, platina, and dilute sulphuric acid are used, it is the union of the zinc with the oxygen of the water which determines the current; and though the acid is essential to the removal of the oxide so formed, in order that another portion of zinc may act on another portion of water, it does not, by combination with that oxide, produce any sensible portion of the current of electricity which circulates; for the quantity of electricity is dependent upon the quantity of zinc oxidized, and in definite proportion to it: its intensity is in proportion to the intensity of the chemical affinity of the zinc for the oxygen under the circumstances, and is scarcely, if at all, affected by the use of either strong or weak acid (908.).

[A] Wollaston, Philosophical Transactions, 1801, p. 427.

920. Again, if zinc, platina, and muriatic acid are used, the electricity appears to be dependent upon the affinity of the zinc for the chlorine, and to be circulated in exact proportion to the number of particles of zinc and chlorine which unite, being in fact an equivalent to them.

921. But in considering this oxidation, or other direct action upon the METAL itself, as the cause and source of the electric current, it is of the utmost importance to observe that the oxygen or other body must be in a peculiar condition, namely, in the state of _combination_; and not only so, but limited still further to such a state of combination and in such proportions as will constitute an _electrolyte_ (823.). A pair of zinc and platina plates cannot be so arranged in oxygen gas as to produce a current of electricity, or act as a voltaic circle, even though the temperature may be raised so high as to cause oxidation of the zinc far more rapidly than if the pair of plates were plunged into dilute sulphuric acid; for the oxygen is not part of an electrolyte, and cannot therefore conduct the forces onwards by decomposition, or even as metals do by itself. Or if its gaseous state embarrass the minds of some, then liquid chlorine may be taken. It does not excite a current of electricity through the two plates by combining with the zinc, for its particles cannot transfer the electricity active at the point of combination across to the platina. It is not a conductor of itself, like the metals; nor is it an electrolyte, so as to be capable of conduction during decomposition, and hence there is simple chemical action at the spot, and no electric current[A].

[A] I do not mean to affirm that no traces of electricity ever appear in such cases. What I mean is, that no electricity is evolved in any way, due or related to the causes which excite voltaic electricity, or proportionate to them. That which does appear occasionally is the smallest possible fraction of that which the acting matter could produce if arranged so as to act voltaically, probably not the one hundred thousandth, or even the millionth part, and is very probably altogether different in its source.

922. It might at first be supposed that a conducting body not electrolytic, might answer as the third substance between the zinc and the platina; and it is true that we have some such capable of exerting chemical action upon the metals. They must, however, be chosen from the metals themselves, for there are no bodies of this kind except those substances and charcoal. To decide the matter by experiment, I made the following arrangement. Melted tin was put into a glass tube bent into the form of the letter V, fig. 78, so as to fill the half of each limb, and two pieces of thick platina wire, _p_, _w_, inserted, so as to have their ends immersed some depth in the tin: the whole was then allowed to cool, and the ends _p_ and _w_ connected with a delicate galvanometer. The part of the tube at _x_ was now reheated, whilst the portion _y_ was retained cool. The galvanometer was immediately influenced by the thermo-electric current produced. The heat was steadily increased at _x_, until at last the tin and platina combined there; an effect which is known to take place with strong chemical action and high ignition; but not the slightest additional effect occurred at the galvanometer. No other deflection than that due to the thermo-electric current was observable the whole time. Hence, though a conductor, and one capable of exerting chemical action on the tin, was used, yet, not being an _electrolyte_, not the slightest effect of an electrical current could be observed (947.).

923. From this it seems apparent that the peculiar character and condition of an electrolyte is _essential_ in one part of the voltaic circuit; and its nature being considered, good reasons appear why it and it alone should be effectual. An electrolyte is always a compound body: it can conduct, but only whilst decomposing. Its conduction depends upon its decomposition and the _transmission of its particles_ in directions parallel to the current; and so intimate is this connexion, that if their transition be stopped, the current is stopped also; if their course be changed, its course and direction change with them; if they proceed in one direction, it has no power to proceed in any other than a direction invariably dependent on them. The particles of an electrolytic body are all so mutually connected, are in such relation with each other through their whole extent in the direction of the current, that if the last is not disposed of, the first is not at liberty to take up its place in the new combination which the powerful affinity of the most active metal tends to produce; and then the current itself is stopped; for the dependencies of the current and the decomposition are so mutual, that whichsoever be originally determined, i.e. the motion of the particles or the motion of the current, the other is invariable in its concomitant production and its relation to it.

924. Consider, then, water as an electrolyte and also as an oxidizing body. The attraction of the zinc for the oxygen is greater, under the circumstances, than that of the oxygen for the hydrogen; but in combining with it, it tends to throw into circulation a current of electricity in a certain direction. This direction is consistent (as is found by innumerable experiments) with the transfer of the hydrogen from the zinc towards the platina, and the transfer in the opposite direction of fresh oxygen from the platina towards the zinc; so that the current _can pass_ in that one line, and, whilst it passes, can consist with and favour the renewal of the conditions upon the surface of the zinc, which at first determined both the combination and circulation. Hence the continuance of the action there, and the continuation of the current. It therefore appears quite as essential that there should be an electrolyte in the circuit, in order that the action may be transferred forward, in a _certain constant direction,_ as that there should be an oxidizing or other body capable of acting directly on the metal; and it also appears to be essential that these two should merge into one, or that the principle directly active on the metal by chemical action should be one of the _ions_ of the electrolyte used. Whether the voltaic arrangement be excited by solution of acids, or alkalies, or sulphurets, or by fused substances (476.), this principle has always hitherto, as far as I am aware, been an _anion_ (943.); and I anticipate, from a consideration of the principles of electric action, that it must of necessity be one of that class of bodies.

925. If the action of the sulphuric acid used in the voltaic circuit be considered, it will be found incompetent to produce any sensible portion of the electricity of the current by its combination with the oxide formed, for this simple reason, it is deficient in a most essential condition: it forms no part of an electrolyte, nor is it in relation with any other body present in the solution which will permit of the mutual transfer of the particles and the consequent transfer of the electricity. It is true, that as the plane at which the acid is dissolving the oxide of zinc formed by the action of the water, is in contact with the metal zinc, there seems no difficulty in considering how the oxide there could communicate an electrical state, proportionate to its own chemical action on the acid, to the metal, which is a conductor without decomposition. But on the side of the acid there is no substance to complete the circuit: the water, as water, cannot conduct it, or at least only so small a proportion that it is merely an incidental and almost inappreciable effect (970.); and it cannot conduct it as an electrolyte, because an electrolyte conducts in consequence of the _mutual_ relation and action of its particles; and neither of the elements of the water, nor even the water itself, as far as we can perceive, are _ions_ with respect to the sulphuric acid (848.)[A].

[A] It will be seen that I here agree with Sir Humphry Davy, who has experimentally supported the opinion that acids and alkalies in combining do not produce any current of electricity. Philosophical Transactions, 1826, p. 398.

926. This view of the secondary character of the sulphuric acid as an agent in the production of the voltaic current, is further confirmed by the fact, that the current generated and transmitted is directly and exactly proportional to the quantity of water decomposed and the quantity of zinc oxidized (868. 991.), and is the same as that required to decompose the same quantity of water. As, therefore, the decomposition of the water shows that the electricity has passed by its means, there remains no other electricity to be accounted for or to be referred to any action other than that of the zinc and the water on each other.

927. The general case (for it includes the former one (924.),) of acids and bases, may theoretically be stated in the following manner. Let _a_, fig. 79, be supposed to be a dry oxacid, and _b_ a dry base, in contact at _c_, and in electric communication at their extremities by plates of platina _pp_, and a platina wire _w_. If this acid and base were fluid, and combination took place at _c_, with an affinity ever so vigorous, and capable of originating an electric current, the current could not circulate in any important degree; because, according to the experimental results, neither _a_ nor _b_ could conduct without being decomposed, for they are either electrolytes or else insulators, under all circumstances, except to very feeble and unimportant currents (970. 986.). Now the affinities at _c_ are not such as tend to cause the _elements_ either of _a_ or _b_ to separate, but only such as would make the two bodies combine together as a whole; the point of action is, therefore, insulated, the action itself local (921. 947.), and no current can be formed.

928. If the acid and base be dissolved in water, then it is possible that a small portion of the electricity due to chemical action may be conducted by the water without decomposition (966. 984.); but the quantity will be so small as to be utterly disproportionate to that due to the equivalents of chemical force; will be merely incidental; and, as it does not involve the essential principles of the voltaic pile, it forms no part of the phenomena at present under investigation[A].