The theory which I believe to be a true expression of the facts of electrochemical 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, etc., 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, etc., are evolved at the positive extremity.
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; 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 and water, against which I have effected electrochemical decomposition, is subject to doubt. In place of the term pole, I propose using that of electrode1, 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.
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....The anode2 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, etc., are evolved; and is against or opposite the positive electrode. The cathode3 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.
I shall have occasion in these Researches, also, to class bodies together according to certain relations derived from their electrical actions; 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 electrolytes4....
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 anions5 which go to the anode of the decomposing body; and those passing to the cathode, cations6; 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.
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.
It will be well understood that I am giving no option respecting the nature of the electric current now, beyond what I have done on former occasions; and that though I speak of the current as proceeding from the parts which are positive to those which are negative, 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....
I have already said, when engaged in reducing common and voltaic electricity to one standard of measurement, and again when introducing my theory of electrochemical decomposition, that the chemical decomposing action of a current is constant for a constant quantity of electricity, notwithstanding the greatest variations in its sources, in its intensity, in the size of the electrodes used, in the nature of the conductors (or non-conductors) through which it is passed, or in other circumstances. The conclusive proofs of the truth of these statements shall be given almost immediately.
I endeavoured upon this law to construct an instrument which should measure out the electricity passing through it, and which, being interposed in the course of the current used in any particular experiment, should serve at pleasure, either as a comparative standard of effect or as a positive measurer of this subtile agent.
There is no substance better fitted, under ordinary circumstances, to be the indicating body in such an instrument as water; for it is decomposed with facility when rendered a better conductor by the addition of acids or salt: its elements may in numerous cases be obtained and collected without any embarrassment from secondary action, and, being gaseous, they are in the best physical condition for separation and measurement. Water, therefore, acidulated by sulphuric acid, is the substance I shall generally refer to, although it may become expedient in peculiar cases of forms of experiment to use other bodies.
The first precaution needful in the construction of the instrument was to avoid the recombination of the evolved gases, and effect which the positive electrode has been found so capable of producing. For this purpose various forms of decomposing apparatus were used. The first consisted of straight tubes, each containing a plate and wire of platina soldered together by gold, and fixed hermetically in the glass at the closed extremity of the tube (Fig. 1). The tubes were about 8 inches long, 0.7 of an inch in diameter, and graduated. The platina were about an inch long, as wide as the tubes would permit, and adjusted as near to the mouths of the tubes as was consistent with the safe collection of the gases evolved. In certain cases, where it was required to evolve the elements upon as small a surface as possible, the metallic extremity, instead of being a plate, consisted of the wire bent into the form of a ring (Fig. 2). When these tubes were used as measurers, they were filled with dilute sulphuric acid, inverted in a basin of the same liquid (Fig. 3), and placed in an inclined position, with their mouths near to each other, that as little decomposing matter should intervene as possible; and also, in such a direction that the platina plates should be in vertical planes.
Another form of apparatus is that delineated (Fig. 4). The tube is bent in the middle; one end is closed; in that end is fixed a wire and plate, a, proceeding so far downwards, that, when in the position figured, it shall be as near angle as possible, consistently with the collection at the closed extremity of the tube, of all the gas evolved against it. The plane of this plate is also perpendicular. The other metallic termination, b, is introduced at the time decomposition is to be effected, being brought as near the angle as possible, without causing any gas to pass from it towards the closed end of the instrument. The gas evolved against it is allowed to escape.
The third form of apparatus contains both electrodes in the same tube; the transmission, therefore, of the electricity and the consequent decomposition is far more rapid than in the separate tubes. The resulting gas is the sum of the portions evolved at the two electrodes, and the instrument is better adapted than either of the former as a measurer of the quantity of voltaic electricity transmitted in ordinary cases. It consists of a straight tube (Fig. 5) closed at the upper extremity and graduated, through the sides of which pass platina wires (being fused into the glass), which are connected with two plates within. The tube is fitted by grinding into one mouth of a double-necked bottle. If the latter be one-half or two-thirds full of dilute sulphuric acid, it will, upon an inclination of the whole, flow into the tube and fill it. When an electric current is passes through the instrument, the gases evolved against the plates collect in the upper portion of the tube and are not subject to the recombining power of the platina.... [Faraday then gives details of the experiments.]
I consider the foregoing investigation as sufficient to prove the very extraordinary and important principle with respect to WATER, that when subjected to the influence of the electric current, a quantity of it is decomposed exactly proportionate to the quantity of electricity which has passed, notwithstanding the thousand variations in the conditions and circumstances under which it may at the time be placed....
The instrument offers the only actual measurer of voltaic electricity which we at present possess. For without being at all affected by variations in time or intensity, or alterations in the current itself, of any kind, or from any cause, or even of intermissions of action, it takes note with accuracy of the quantity of electricity which has passed through it, and reveals the quantity by inspection; I have therefore named it a VOLTA-ELECTROMETER....
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 conduction7 already developed, I soon found abundance, among 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, so that the knob should be at the bottom of the tube within (Fig. 9). 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, 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. 10.
Under these circumstances the chloride of tin was decomposed: the chlorine evolved at the positive electrode formed bichloride of tin, which passes 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 connetion 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.
I 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-eletrometer = 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 electochemical 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), that the numbers leave little doubt of the applicability of the law of definite action in this and all similar cases of electro-decomposition.
It is not often I have obtained an accordance in numbers so near as I have just quoted. Four experiments were made on the protochloride of tin; the quantities of gas evolved in the volta-electometer being from 2.05 to 10.29 cubic inches. The average of the four experiments gave 58.43 as the electrochemical equivalent for tin.
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 passsed away.
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, etc. The chlorine or iodine does not act upon it, but is evolved in the free state; and the plumbago has no reaction, 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.
The mean of three experiments gave the number of 100.85 as the equivalent of lead. The chemical equivalent is 103.5. The deficiency in my experiments I attribute to the solution of part of the gas 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 quantites by the action of a given quantity of electricity.
0. Faraday did not use this type of foot noting. Notes 1 thru 6 are the Greek words Faraday used. Those are coming soon.
7. The law referred to asserts "the general assumption of conducting power by bodies as soon as they pass from the solid to the liquid state."