Experimental Researches in Electricity, Volume 1

by Michael Faraday

901. Protochloride of tin, when fused and placed at x, was also readily decomposed, yielding perchloride of tin at the anode (779.), and tin at the cathode.

902. Fused chloride of silver, placed at x, was also easily decomposed; chlorine was evolved at the anode, and brilliant metallic silver, either in films upon the surface of the liquid, or in crystals beneath, evolved at the cathode.

903. Water acidulated with sulphuric acid, solution of muriatic acid, solution of sulphate of soda, fused nitre, and the fused chloride and iodide of lead were not decomposed by this single pair of plates, excited only by dilute sulphuric acid.

904. These experiments give abundant proofs that a single pair of plates can electrolyze bodies and separate their elements. They also show in a beautiful manner the direct relation and opposition of the chemical affinities concerned at the two points of action. In those cases where the sum of the opposing affinities at x was sufficiently beneath the sum of the acting affinities in v, decomposition took place; but in those cases where they rose higher, decomposition was effectually resisted and the current ceased to pass (891.).

905. It is however, evident, that the sum of acting affinities in v may be increased by using other fluids than dilute sulphuric acid, in which latter case, as I believe, it is merely the affinity of the zinc for the oxygen already combined with hydrogen in the water that is exerted in producing the electric current (919.): and when the affinities are so increased, the view I am supporting leads to the conclusion, that bodies which resisted in the preceding experiments would then be decomposed, because of the increased difference between their affinities and the acting affinities thus exalted. This expectation was fully confirmed in the following manner.

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[191].

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[192]. 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.